crystallography, spectroscopy and theory Acta Crystallographica Section C

Crystal Structure Communications ISSN 0108-2701

Structure, magnetism and colour in simple bis(phosphine)nickel(II) dihalide complexes: an experimental and theoretical investigation Madeleine Schultz,a* Philipp-Nikolaus Plessow,b Frank Romingerb and Laura Weigelb

very close to square planar and very weakly paramagnetic in the solid state and in solution, while the maroon [1,2-bis(ditert-butylphosphanyl)ethane-2P,P0 ]dibromidonickel(II), [NiBr2(C18H40P2] or (dtbpe-2P)NiBr2, is isostructural with the diiodide in the solid state, and displays paramagnetism intermediate between that of the dichloride and the diiodide in the solid state and in solution. Density functional calculations demonstrate that distortion from an ideal square plane for these complexes occurs on a flat potential energy surface. The calculations reproduce the observed structures and colours, and explain the trends observed for these and similar complexes. Although theoretical investigation identified magnetic-dipole-allowed excitations that are characteristic for temperature-independent paramagnetism (TIP), theory predicts the molecules to be diamagnetic.

a

School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology, Gardens Point QLD 4000, Australia, and bOrganisch-Chemisches Institut, Universita¨t Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany Correspondence e-mail: [email protected]

Keywords: magnetic properties; UV–Vis spectroscopy; X-ray diffraction; phosphane ligands; density functional calculations; temperature-independent paramagnetism; crystal structure.

Received 28 August 2013 Accepted 8 November 2013

1. Introduction

The complex [1,2-bis(di-tert-butylphosphanyl)ethane-2P,P0 ]diiodidonickel(II), [NiI2(C18H40P2] or (dtbpe-2P)NiI2, [dtbpe is 1,2-bis(di-tert-butylphosphanyl)ethane], is bright blue– green in the solid state and in solution, but, contrary to the structure predicted for a blue or green nickel(II) bis(phosphine) complex, it is found to be close to square planar in the solid state. The solution structure is deduced to be similar, because the optical spectra measured in solution and in the solid state contain similar absorptions. In solution at room temperature, no 31P{1H} NMR resonance is observed, but the very small solid-state magnetic moment at temperatures down to 4 K indicates that the weak paramagnetism of this nickel(II) complex can be ascribed to temperature independent paramagnetism, and that the complex has no unpaired electrons. The red [1,2-bis(di-tert-butylphosphanyl)ethane-2P,P0 ]dichloridonickel(II), [NiCl2(C18H40P2] or (dtbpe-2P)NiCl2, is

Figure 1 Crystal field splitting diagrams for square-planar (left) and tetrahedral (right) geometries with d8 occupation. Acta Cryst. (2013). C69, 1437–1447

It is axiomatic in the chemistry of nickel(II) complexes with four ligands that orange and red examples are square planar and diamagnetic, while green and blue examples are tetrahedral and paramagnetic (Cotton et al., 1999; Hayter & Humiec, 1965). The magnetism can be explained by a simple crystal field model as resulting from the eight valence electrons occupying the d orbitals, split by the different crystal fields of the two geometries as shown in Fig. 1. For a squareplanar geometry, the dx2–y2 orbital lies at much higher energy than the other d orbitals and so the ground state is expected to be diamagnetic. For a tetrahedral geometry, paramagnetism results from single occupation of two of the degenerate dxy, dxz and dyz orbitals, leading to a triplet ground state.

A few exceptions to the ‘square planar equals diamagnetic’ rule for NiII have been reported, involving N—P—O chelating ligands (Bru¨ck et al., 1996; Fro¨mmel et al., 1992); these squareplanar paramagnetic complexes are green or blue. The origin of their paramagnetism has been deduced through theoretical investigations to lie in the strong  bonding of the amide group, which leads to a smaller gap between the two highest energy orbitals. In combination with the relatively large pairing energy of NiII, this can lead to a high-spin ground state, depending on the ligands (Bridgeman, 2008).

doi:10.1107/S0108270113030692

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crystallography, spectroscopy and theory The colours of transition metal complexes result largely from electronic transitions within the d orbitals. In the vast majority of four-coordinate NiII complexes, square-planar diamagnetic examples are observed to be red or orange, while tetrahedral paramagnetic complexes are green or blue (Hayter & Humiec, 1965). For the C2v symmetric squareplanar complexes, the colour has been ascribed to the 1A1 ! 1 B2 transition (Jarrett & Sadler, 1991; van Hecke & Horrocks, 1966). A solution square-planar (diamagnetic)–tetrahedral (paramagnetic) equilibrium for complexes of the type Ni(PR3)2X2 was first proposed 50 years ago (Hayter & Humiec, 1962). In that work, Ni(PEtPh2)2Br2 is found to crystallize either in a green tetrahedral paramagnetic form or in a red square-planar diamagnetic form, depending on the solvent used. The dichloride forms such red crystals while the diiodide forms a brown–red tetrahedral paramagnetic structure. For the simplest member of this series, Ni(PPh3)2Cl2, first reported 55 years ago (Venanzi, 1958), crystals can be grown of either the blue–green tetrahedral or the red square-planar isomer, depending on the solvent used (Corain et al., 1985). In this work, we focus on neutral complexes of the type P2NiX2, with P2 being a bidentate diphosphine ligand and X a halide. With the bidentate ligand bis(diphenylphosphanyl)propane (dppp), the three dihalides, (dppp-2P)NiX2 (X = Cl, Br and I), are found to be diamagnetic and red (Cl and Br) or purple (I) in the solid state, but show paramagnetism in solution, increasing in the order Cl < Br < I, which can be attributed to an equilibrium between structures with singlet and triplet ground states (van Hecke & Horrocks, 1966). Only the crystal structure of the dichloride has been reported, and it is square planar in the solid state (Bomfim et al., 2003). The analogous complexes of bis(diphenylphosphanyl)ethane, (dppe-2P)NiX2 (X = Cl, Br and I), with an ethylene rather than a propylene bridge between the P atoms, are reported to be red (Cl and Br) and deep purple (I), and diamagnetic in the solid state and in solution at all temperatures (van Hecke & Horrocks, 1966), although the initial report of (dppe-2P)NiCl2 indicated that it showed variable amounts of paramagnetism (Booth & Chatt, 1965). The structures of the dichloride and dibromide have been reported multiple times and the compounds are always square planar (Beaudoin et al., 2001; Bomfim et al., 2003; Busby et al., 1993; Rahn et al., 1989; Spek et al., 1987). However, the same complexes (dppe2P)NiX2 (X = Cl, Br and I) have also been reported to exhibit temperature-independent paramagnetism in the solid state (Hudson et al., 1968; Jarrett & Sadler, 1991), while being diamagnetic in solution (Jarrett & Sadler, 1991). A search of the Cambridge Structural Database (CSD; Version 5.34; Allen, 2002) shows that all 25 reported Ni(P–P)X2 complexes involving bidentate ligands of this type that have been characterized crystallographically are cisoriented and square planar, including some with heteroatoms in the ligand (Lavanant et al., 2008), and have very long chelate rings (up to eight members) (Pandarus et al., 2008). All dichloride and dibromide complexes that have been crystallographically characterized are described as red or orange. To

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date, only one NiII bis(phosphine) diiodide has been characterized crystallographically; this square-planar complex is described as purple (Angulo, Bouwman, Lutz et al., 2001). In published reports of distorted square-planar complexes, the distortion has usually been measured by defining two planes based on the metal and the ligand pairs (in these cases, P/P0 /Ni and X/X0 /Ni) and measuring the dihedral angle between these planes (Martin et al., 1991; Miedaner et al., 1991). This method is easy to define and calculate but has the major disadvantage that the planes may be tilted as well as rotated with respect to each other. That is, this method measures a mixture of pyramidalization and tetrahedral distortion. In complexes with unsymmetrical ligands, the pyramidalization frequently makes a larger contribution to the observed angle than the tetrahedral distortion. In this work, we use the mean of the two P  P  X  X torsion angles to describe deviations from ideal square-planar geometry. Bidentate bis(phosphanyl)ethanes with alkyl substituents such as methyl (dmpe), ethyl (depe) and cyclohexyl (dcpe) have long been used in nickel chemistry. In recent years, interest has moved to the more bulky tert-butyl substituent on the ligand bis(di-tert-butylphosphanyl)ethane (dtbpe). The compound (dtbpe-2P)NiCl2 has been used as a starting material for nickel complexes with interesting properties by Po¨rschke (Bach et al., 1999) and Hillhouse (Anderson et al., 2010; Kitiachvili et al., 2004; Mindiola & Hillhouse, 2001; Waterman & Hillhouse, 2008). In Po¨rschke’s reported synthesis, it is described as red and paramagnetic, based on the lack of observation of a 31P{1H} NMR resonance. This observation seemed to contradict the general rule of red NiII complexes being square planar and diamagnetic, and so warranted further investigation. The related nickel(I) dimer, [(dtbpe2P)NiCl]2, has been reported by Hillhouse, and is found to be tetrahedral; interestingly, oxidation of a single nickel centre leads to a structure in which both nickel centres are almost square planar (Mindiola et al., 2003). It was therefore of interest to resolve the issue of structure and magnetism for the rather simple complex (dtbpe2P)NiCl2 and its homologues (dtbpe-2P)NiBr2 and (dtbpe2P)NiI2. Experimental techniques, including spectroscopy and X-ray crystallography, have been supplemented by the use of density functional theory to probe the molecular structure, the predicted electronic ground state and the expected electronic absorptions. To validate our theoretical methods we also prepared and characterized (dppe-2P)NiI2. During the course of our investigations we became interested in the theoretical study of the temperature-independent paramagnetism of these molecules and the results of this study are also reported.

2. Results and discussion 2.1. Synthesis

The synthesis of the dichloride and diiodide complexes, (dtbpe-2P)NiX2 (X = Cl and I) and (dppe-2P)NiI2 proceeded in high yield from the corresponding anhydrous nickel

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crystallography, spectroscopy and theory Table 1 ˚ ) and angles ( ) for (dtbpe-2P)NiX2 and (dppe-2P)NiI22H2O. Computed values (BP86/def2-TZVP) are given in italics. The Important bond lengths (A calculated values are for the P conformation in all cases, although for the dtbpe diiodide this is not the global minimum, as described in the text. Ligands

dtbpeCl (with CHCl3)

dtbpeCl (solvent-free)a

dtbpeCl

dtbpeBr

dtbpeBr

dtbpeI

dtbpeI

˚) Ni1—P1 (A ˚) Ni1—P2 (A ˚) Ni1—X1 (A ˚) Ni1—X2 (A P1—Ni1—P2 ( ) X1—Ni1—X2 ( ) Mean of P  P  X  X torsion angles ( )

2.2049 (9) 2.1986 (9) 2.2150 (10) 2.1997 (9) 90.96 (3) 89.46 (4) 2.38 (4)

2.1975 (10); 2.1971 (10) 2.2037 (10); 2.2021 (10) 2.2018 (10); 2.1941 (11) 2.2125 (11); 2.2090 (11) 90.82 (4); 90.95 (4) 91.16 (4); 90.47 (4) 9.48 (4); 5.73 (4)

2.191 2.191 2.216 2.216 92.9 91.2 4.7

2.2256 (16) 2.2186 (16) 2.3638 (9) 2.3537 (10) 90.10 (6) 89.82 (3) 19.33 (4)

2.206 2.206 2.368 2.368 92.7 89.8 9.0

2.2377 (11) 2.2389 (10) 2.5626 (5) 2.5377 (5) 90.30 (4) 88.507 (16) 19.56 (2)

2.225 2.225 2.564 2.564 91.9 88.8 24.3

dppeI

dppeI

2.1582 (18) 2.1733 (18) 2.5240 (9) 2.5216 (9) 86.51 (7) 94.93 (3) 2.27 (4)

2.163 2.163 2.542 2.542 89.2 94.9 2.8

Note: (a) data for two chemically equivalent but crystallographically unique molecules in the asymmetric unit.

halides and bis(phosphine) ligands in refluxing ethanol, while the bromide was prepared from NiBr2(PPh3)2 in toluene. The compounds are quite air stable as solids [although (dtbpe2P)NiI2 decomposes in the solid state over years], but they decompose in solution in air over a period of a few hours. The Scheme shows the connectivity of the complexes studied in this work. 2.2. Characterization 2.2.1. Crystal and molecular structures. The solid-state structures of the four compounds were determined by X-ray crystallography at 200 K. A structure of the dichloride has previously been provided as a personal communication to the CSD with two molecules of chloroform in the asymmetric unit, with a mean of the P  P  Cl  Cl torsion angles of 11 (Batsanov et al., 2009). We were able to obtain X-ray quality crystals of the dichloride with and without chloroform, both with different space groups and unit-cell parameters from those of the structure in the CSD. Table 1 contains important bond distances and angles for the five crystal structures. Fig. 2 shows one of the two chemically equivalent but crystallographically unique molecules in the asymmetric unit of solvent-free (dtbpe-2P)NiCl2. A view of (dtbpe-2P)NiI2 is shown in Fig. 3. The dibromide is isostructural with the diiodide.

Figure 3 The molecular structure of (dtbpe-2P)NiI2, with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity. The C atom labels used are different to those used in the actual refinement model.

It can be seen from Figs. 2 and 3 that the halide atoms are not in the plane formed by the NiII and two P atoms; the means of the two P  P  X  X torsion angles for each structure are provided in Table 1. The distortion from square planarity for the dibromide and diiodide, over 19 , is greater than in any analogous complex in the CSD; the only other values above 15 are found for complexes with a propylene rather than an ethylene tether in the bis(phosphine) ligand (Angulo, Bouwman, Lok et al., 2001). Examples of crystallographically characterized nickel(II) bis(phosphine) dihalide complexes are relatively common; nearly 60 structures can be found in the CSD, although several complexes have been reported in multiple modifications. Compared with the typical distances and angles for those reported structures, the bond distances and angles are slightly unusual in the four dtbpe structures here. In particular, with Table 2 max values for (dtbpe-2P)NiX2 (X = Cl, Br and I) in solution and the solid state (nm). Extinction coefficients (M1 cm1) for the solution spectra are provided in parentheses. Compound

Figure 2

2

The molecular structure of (dtbpe-2P)NiCl2 (one of two unique molecules in the asymmetric unit), with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity. The C atom labels used are different to those used in the actual refinement model. Acta Cryst. (2013). C69, 1437–1447

(dtbpe- P)NiCl2 (dtbpe-2P)NiCl2 (dtbpe-2P)NiBr2 (dtbpe-2P)NiBr2 (dtbpe-2P)NiI2 (dtbpe-2P)NiI2

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Form

max (")

max (")

Colour

solution solid solution solid solution solid

351 (1800) 323 417 (340) 425 391 (3050) 396

495 (790) 491 523 (420) 550 606 (817) 602

bright red bright red maroon maroon blue–green deep green

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Figure 4 The molecular structure of (dtbpe-2P)NiCl2 (second of two unique molecules in the asymmetric unit), with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity. The C atom labels used are different to those used in the actual refinement model.

an ethylene bridge between the two P atoms (23 structures in the CSD), P—Ni—P angles of around 87 are more common than the value of 90 observed in the current dtbpe structures, ˚ observed here are and the Ni—P bond distances of 2.2 A somewhat longer than is found for complexes with other substituents on the P atom, where Ni—P distances of around ˚ are more usual. The bond distances and angles in the 2.15 A structure of (dppe-2P)NiI2 reported here fall exactly in the normal ranges. Thus, the steric bulk of the tert-butyl groups appears to be putting pressure on the coordination environment. However, the Ni—X distances are not changed in the dtbpe structures from those observed in structures with less bulky ligands. A steric explanation for the non-zero torsion angles, which is consistent with the changes to bond distances and angles just described, can be found in the orientation of the tert-butyl groups of the dtbpe ligand. As can be seen from the structures in Figs. 2 and 3, the four tert-butyl groups are not equivalent in

Figure 5 Schematic representation of principal conformations of (dtbpe-2P)NiX2 and their relationship through backbone-inversion without tert-butyl substituent rotation, or through rotation of the halide ligands.

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the crystals. The (dtbpe-2P)Ni fragment possesses pseudo-C2 symmetry, so that the pairs of tert-butyl groups that are transformed into one another by rotation are nearly symmetry equivalent. Two of the tert-butyl groups (C_A and C_A0 ) are in a perfectly staggered conformation with respect to the other substituents on the P atom and each of these has one methyl group (C_A1 and C_A0 1) pointing towards the halide ligands. The other two tert-butyl groups are slightly rotated with respect to a staggered conformation (C_B and C_B0 ), and none of their methyl groups point at the halide ligands (Figs. 2 and 3). This results in openings in the coordination environment across one, but not the other, diagonal looking along the axis from Ni to the mid-point of P1  P2 (the view in Figs. 2 and 3). In all but one of the dtbpe structures, the two halide ligands are notably distorted into these openings, as can be seen in Figs. 2 and 3. We define a positive dihedral distortion (mean of the P  P  X  X torsion angles) as one in which the halide ligands are moved towards the described opening. A negative dihedral distortion is then rotation of the halide ligands towards the nearest methyl groups. Such a negative distortion has been observed once in these structures, viz. in the second unique molecule in the asymmetric unit of the solvent free dichloride, a view of which is shown in Fig. 4. The fact that in most cases the direction of distortion is apparently determined by the tert-butyl groups implies that it is of steric origin. Because the Ni—I and Ni—Br distances are longer than the Ni—Cl distance, the larger halide ligands are closer to the region where the methyl H atoms are found, and so more sensitive to this steric effect. This explains the lower distortion in the dichloride and the existence of the sterically unexpected conformation shown in Fig. 4. In the absence of the steric pressure caused by the tert-butyl groups, such as in (dppe-2P)NiI2, no distortion from squareplanar geometry is observed. This is consistent with the square-planar structures previously reported for compounds of this type, which have significantly less bulky substituents on phosphorus. The ethylene backbone of the dtbpe ligand can be oriented parallel to the diagonal opening from C_B to C_B0 in which the halide ligands fit, which we call the P conformation and which is the conformation observed in the structures in Figs. 2 and 3, or in the opposite direction, the O conformation. Alternatively, the halide ligands can be oriented towards the closest methyl groups, as seen in Fig. 4, which we call the K conformation. These structural possibilities and their interconversions are summarized in Fig. 5. Only the P and K conformations have been observed crystallographically. However, in the calculations discussed below, minima were located for the P and O conformations. 2.2.2. Optical spectroscopy. The colours of the three dtbpe compounds are very different; the dichloride is deep red, the dibromide maroon and the diiodide is deep blue–green. The optical spectra were measured in dichloromethane solution and in the solid state using diffuse reflectance on a powdered sample and transmittance on thin films. Fig. 6 contains the solution spectra, while Table 2 provides the observed max values for both solution and solid-state measurements.

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crystallography, spectroscopy and theory Table 3 31

P{1H} chemical shift and 1/2 as a function of temperature.

(dtbpe-2P)NiCl2 in CDCl2CDCl2 Temperature (K) Peak position () Peak width at half height (Hz)

243 86 20

298 88 120

313 92 210

333 103 300

353 123 480

(dtbpe-2P)NiBr2 in CD2Cl2 Temperature (K) Peak position () Peak width at half height (Hz)

223 93.4 30

253 94.2 120

273 97.5 230

298 109 480

313 124 700

1

Figure 6 Optical spectra of (dtbpe-2P)NiX2 (X = Cl, Br and I) in solution.

It can be seen from Table 2 that the positions of the absorptions are almost unchanged on going from the solution to the solid-state spectra, and the characteristic double absorption of the dibromide appears in both spectra. This indicates that the structures are very likely the same in solution as those determined in the solid state. For this reason, a solution equilibrium between the square-planar and tetrahedral forms is considered unlikely, although we cannot rule it out. No band is observed in any of the spectra in the range 800– 1000 nm for freshly prepared and recrystallized complexes. A band in this region is reported to result from the 3T1 ! 3A2 transition of the tetrahedral isomer (van Hecke & Horrocks, 1966), and its absence speaks against the existence of a solution equilibrium between the two geometries. A band was observed in solution at 913 nm and in the solid state at 937 nm for samples of the (dtpbe-2P)NiI2 that had partially decomposed. It is worth noting that freshly prepared samples of the diiodide appear blue–green, and as the samples stand in solution in air they become visibly more green within minutes. The dibromide and dichloride decompose more slowly in air, in solution over hours, and lose colour as they do so. 2.2.3. Magnetism. The magnetism of the three dtbpe complexes was measured in the solid state at room temperature using a Gouy balance, and then at temperatures from 4– 300 K using a SQUID magnetometer. Only extremely small values that did not vary with temperature were recorded for freshly recrystallized samples of the dibromide (0.2 BM at room temperature) and diiodide (0.4 BM at room temperature), while the dichloride appeared diamagnetic, with a small negative value recorded at room temperature. Low magnetic moments in the range 0.1–0.4 BM recorded for complexes of the type (dppe-2P)NiX2 (X = Cl, Br and I) were originally ascribed to some oxidation of the complexes (Hudson et al., 1968); however, they may derive from the temperature-independent paramagnetism in pure samples, as has subsequently been reported (Jarrett & Sadler, 1991). The 1H NMR spectra of the three dtbpe complexes at room temperature in CD2Cl2 solution indicate that they vary from very slightly (dichloride: 1/2 = 100 Hz at room temperature) to somewhat paramagnetic; in a solution of the diiodide complex, no 31P signal is observed. The temperature dependence of the Acta Cryst. (2013). C69, 1437–1447

H NMR and 31P{1H} spectra for the dichloride and dibromide was measured; all become sharper at lower temperatures and broader at higher temperatures, as well as moving to lower field with increasing temperature. Fig. 7 contains a chemical shift versus 1/T plot for the 31P{1H} resonance of the dibromide; similar data were obtained for the dichloride. Table 3 presents the variable temperature NMR data. Non-linear plots of chemical shift versus 1/T indicate that the behaviour is non-Curie–Weiss. Multiple attempts to quantify the solution magnetism using the Evans method were unsuccessful (Evans, 1959); due to the low magnetic moments, only extremely small changes in chemical shift were observed and no quantitative data could be obtained. Sophisticated NMR methods are now available for the interpretation of paramagnetic complexes (Cremer & Burger, 2003; Ko¨hler, 2011). However, to date with these methods the NMR data could not be fitted to an equilibrium between a paramagnetic (tetrahedral) and a diamagnetic (square planar) complex, as has been done for related systems (Pignolet & Horrocks, 1969). 2.2.4. Density functional theory. Structure optimizations were carried out for singlet closed-shell and triplet (unrestricted Kohn–Sham) ground states using TURBOMOLE (Bauernschmitt & Ahlrichs, 1996; Bauernschmitt et al., 1997; Deglmann et al., 2004; Eichkorn et al., 1995; Eichkorn et al., 1997; Furche & Ahlrichs, 2002; Furche & Rappoport, 2005; Ha¨ser & Ahlrichs, 1989; Ha¨ttig & Ko¨hn, 2002; Ha¨ttig & Weigend, 2000; Scha¨fer et al., 1992; Treutler & Ahlrichs, 1995; TURBOMOLE, 2012; Weigend, 2006; Weigend & Ahlrichs, 2005; Weigend et al., 1998, 2003). Although the wavefunctions with Sz = 1h at UHF/UKS level are not eigenfunctions of S2, we will refer to them as triplet wavefunctions because they show only moderate spin-contamination, typically the devia-

Figure 7 Temperature dependence of 31P{1H} chemical shift of a CD2Cl2 solution of (dtbpe-2P)NiBr2.

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crystallography, spectroscopy and theory Table 4 Comparison of calculated and observed max values to which the colour of the complex is attributed (nm). The calculated absorption for a molecule that is restricted to a planar geometry is given in parentheses.

Calculated P Calculated O Observed (solution)

(dtbpe-2P)NiCl2

(dtbpe-2P)NiBr2

(dtbpe-2P)NiI2

505 (505) 506 (505) 495

530 (529) 535 (527) 523

582 (562) 580 (559) 606

tion from = 2h 2 is about 0.01 h 2. The triplet-optimized structures show a pseudo-tetrahedral coordination on the Ni atom, which is significantly different from that observed in the crystal structures. In terms of energy, triplet and singlet ground-state energies for the corresponding optimized structures are similar. The singlet–triplet splitting varies systematically with the amount of Hartree–Fock (HF) exchange used in the exchange–correlation functional, where more HF exchange favours the triplet ground state. The triplet UHF wavefunction itself is lower in energy than the singlet RHF wave function even for (DFT) singlet optimized structures. Based on the calculations, it can therefore not be excluded that the pseudo-tetrahedral structure with a triplet ground state is significantly populated in an equilibrium in solution. Unless otherwise noted, energies are discussed at the B3LYP/ def2-TZVPP//BP86/def2-TZVP level of theory (Becke, 1988, 1993; Dirac, 1929; Lee et al., 1988; Perdew, 1986; Slater, 1951; Vosko et al., 1980). Since the crystal structure as well as the magnetic properties in solution indicate that the singlet structure dominates, only singlet states will be discussed in the following. The structural possibilities discussed above lead to two distinctive minima for conformations of the (dtbpe-2P)NiX2 complexes depicted in Fig. 5. The ethylene backbone is found to be oriented parallel with (P) or opposite to (O) the opening in the coordination environment created by the tert-butyl groups; no minimum was found for the K conformation. The energy barrier required for inversion of the ethylene backbone is very low (< 25 kJ mol1) in all cases. The energy of O relative to P is 7 (Cl), 1 (Br) and 3 kJ mol1 (I). Figs. 8–10 show a relaxed potential surface for the distortion of the complexes out of planarity in each conformation. It can be seen that the

Figure 9 Relative energies in kJ mol1 of the (dtbpe-2P)NiBr2 P and O structures. The angle is the mean of the two P  P  X  X torsion angles (BP86/ def2-TZVP level of theory).

minimum found for the O isomer is in all cases the more distorted one, and the distortion angles increase in the order Cl < Br < I. The planar structures have the shortest Ni—X distances and the distorted structures exhibit miniscule changes in the Ni—X distances, with distances elongated ˚ for the dichloride, dibromide around 0.004, 0.006 and 0.015 A and diiodide, respectively. The diiodide complex is the only one for which P and O have a minimum structure at similar distortion angles of around 23 , slightly greater than the crystallographically observed angle of 19.56 (2) . As explained above, all but one of the crystal structures correspond to the P isomers, and the bond distances and angles for the calculated minimum energy P structures are given in Table 1. It can be seen from that table that the calculations reproduce the bond distances and angles of the observed structures well, in particular the elongation of the Ni—P bond compared with those in the structures with less bulky phosphine ligands described above. The distortion from planarity is also found for the minimum-energy structures. The calculations indicate that this is a very soft potential surface and also that flipping the backbone conformation (P to O) is a low-energy process. The existence of at least three different crystalline modifications of the dichloride with four different

Figure 8

Figure 10

Relative energies in kJ mol1 of the (dtbpe-2P)NiCl2 P and O structures. The angle is the mean of the two P  P  X  X torsion angles (BP86/ def2-TZVP level of theory).

Relative energies in kJ mol1 of the (dtbpe-2P)NiI2 P and O structures. The angle is the mean of the two P  P  X  X torsion angles (BP86/ def2-TZVP level of theory).

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crystallography, spectroscopy and theory Table 5 Comparison of reported solution max and calculated (B3LYP/def2TVPP//BP86/def2-TZVP) values for nickel halide complexes bearing phenyl-substituted bis(phosphine) ligands. Values for which the groundstate structure has been optimized with Grimme’s empirical dispersion correction are given in parentheses. Complex

Reported (van Hecke & Horrocks, 1966)

Calculated

(dppe-2P)NiCl2 (dppe-2P)NiBr2 (dppe-2P)NiI2 (dppp-2P)NiCl2 (dppp-2P)NiBr2 (dppp-2P)NiI2

463 481 521 470 490 559a

488 (459) 506 (493) 536 (529) 490 515 550

Note: (a) in solution, this complex undergoes a square-planar–tetrahedral equilibrium so the observed value for the square-planar complex as a Nujol mull has been used (van Hecke & Horrocks, 1966).

distortion angles supports the notion that the distortion is on a flat energy surface, and that packing effects will significantly affect the observed structure. Using the calculated minimum structures, the vertical excitation spectra (showing the energy differences between ground and excited states at ground state geometry) were calculated at the B3LYP/def2-TZVPP//BP86/def2-TZVP level of linear response-time-dependent density functional theory (TDDFT) within the adiabatic approximation. Other choices of functionals for excitation or geometry optimization did not significantly change the relative positions of the excitations under consideration, but moved their absolute positions. The chosen methodology showed the best agreement with the absolute positions of excitations observed experimentally. The colour was attributed to the most intense absorption in the region with highest spectral sensitivity to human visual perception, in the range 650–450 nm. The computed excitation energies are in good agreement with experiment (Table 4). The location of the main absorption differs between P and O isomers by less than 5 nm. For the dibromide and dichloride, the distortion of the minimum structures with respect to planarity changes the excitation energy only very slightly. In the case of the diiodide, the restriction to planarity leads to a blue shift of 20 nm. The change of the total electron density associated with this excitation is metal-centred and implies a dxy to dx2–y2 transition in all studied complexes of P-type. Fig. 11 shows the calculated energies of the excited states of the P isomers for the different dihalide complexes. Based on these TDDFT calculations, the excitation cannot be attributed to a simple transition from one occupied to one virtual orbital. Instead, there are several occupied to LUMO (lowest unoccupied molecular orbital) contributions. The LUMO is the antibonding combination of metal dx2–y2 and halide p-orbitals. The most important contributing occupied orbitals are bonding or non-bonding combinations of the dxymetal and p-halide orbitals. In all cases, the HOMO-2 (highest occupied molecular orbital) has the largest contribution, for the less distorted complexes it is about 60%. The red shift of the main absorption on going from the dichloride complex to the dibromide complex and from a planar diiodide complex to the actual distorted diiodide complex (see Table 4 and Fig. 11) is reflected in the increasing Acta Cryst. (2013). C69, 1437–1447

orbital energies of contributing occupied orbitals and decreasing LUMO orbital energy. This can be rationalized in terms of higher p-orbital energies of the heavier halogen atoms and less overlap of halogen p-orbitals with metal orbitals, which results in weaker bonding and antibonding character. The influence of distortion can be understood in terms of further reduced overlap in bonding and antibonding orbitals. This dependence on the halide ligand is also predicted by the spectrochemical series. To verify this methodology, calculations were used to predict the positions of the corresponding absorptions of analogous complexes with phenylsubstituted bis(phosphine) ligands, which have colours, structures and magnetism as described in the introduction and above. Table 5 summarizes the results. As can be seen from Tables 4 and 5, the computed wavelengths are systematically red-shifted by around 10–20 nm so that the observed trends both in terms of bis(phosphine) ligand (dtbpe > dppp > dppe) and halide ligand (I > Br > Cl) are correctly predicted. This is illustrated in Fig. 12. In general, the agreement of calculated absorptions with experiment is somewhat worse for phenyl-substituted ligands compared with dtbpe. A reason for this could be dispersion interactions between the phenyl rings, which influences the structures of the complexes. Indeed, if the geometry is optimized with Grimme’s dispersion correction (Grimme et al., 2010) and the excitation energy then recomputed [B3LYP/ def2-TZVPP//BP86-D3/def2-SV(P)], the values for dtbpe change less than those for phenyl-containing bis(phosphines). Although the results obtained are somewhat improved, this should not be overinterpreted. Effects of dispersion interactions on the structures with phenyl-substituted ligands probably influence the excitation energies to a degree comparable to the deviations between experiment and theory. The calculations also show that as compared to dtbpe, dppe complexes have a more stable singlet ground state, while dppp complexes have a more stable triplet ground state. This is in agreement with the fact that an equilibrium between molecules with singlet and triplet ground states has been observed for the complexes (dppp-2P)NiX2 (van Hecke & Horrocks, 1966). As above, the calculated singlet–triplet splitting varies with the amount of HF-exchange used, while the ligand dependence is the same for all functionals. 2.2.5. Temperature-independent paramagnetism. Small magnetic moments are difficult to measure experimentally and are sensitive to impurities from compounds with higher magnetic moments (Walter et al., 2006). In particular, temperature-independent paramagnetism (TIP) is difficult to measure accurately, particularly for compounds that can decompose to products with temperature-dependent paramagnetism, such as the nickel complexes in this study. We have investigated TIP in detail for the nickel phosphine complexes introduced above using DFT/TDDFT and for model complexes also using coupled cluster calculations; an extensive discussion is given in the Supporting information. We conclude that planar d8 nickel complexes can, based on simple crystalfield arguments and based on our DFT and ab initio calculations, be expected to have paramagnetic contributions to the

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Figure 11 Energy of the excited state of the P isomer (top line) for the different dtbpe halide complexes, including the planarized diiodide complex; difference between the density of the excited and ground states of the dichloride and diiodide (left and right diagrams at top; red: negative; blue: positive). Energies of orbitals that contribute most to the excitation are also depicted, along with plots of the orbitals for the dichloride and diiodide. All energies are given in eV.

magnetizability comparable to those of the molecules for which TIP is well established (such as BH and isoelectronic molecules) (Fowler & Steiner, 1992, 1993; Pelloni et al., 2009; Ruud et al., 1995; Sauer et al., 1993; Stevens & Lipscomb, 1965). The magnitude of the individual contributions is similar and the corresponding excitations can be understood in terms of simple orbital considerations. However, the nickel bis(phosphine) complexes have a much greater number of atoms

and electrons and therefore a much larger diamagnetic contribution, which overcompensates this paramagnetic part by far, so no TIP is expected according to these calculations. The calculations therefore suggest that the small paramagnetism observed in experiments is due to conventional temperature-dependent paramagnetism of species that are present only in very small concentrations. These are likely pseudo-tetrahedral nickel bis(phosphine) complexes with triplet ground states that either result from decomposition, or exist in equilibrium with the near planar complexes, at concentrations too low to be observed by optical spectroscopy.

3. Conclusions

Figure 12 Comparison of the experimentally observed and calculated wavelengths of the main absorption of complexes P2NiX2 as a function of bis(phosphine) and halide ligand (nm).

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The crystal structures and spectroscopic and magnetic properties of the compounds (dtbpe-2P)NiX2 are not as straightforward as their rather simple chemical structures would suggest. Density functional theory indicates that the distortions from square planarity observed in the solid state lie on a very flat energy surface. Good agreement between theory and experiment was observed for the geometries and colours of the complexes. The colour of the diiodide, while somewhat unexpected, does not indicate a tetrahedral structure and is

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Acta Cryst. (2013). C69, 1437–1447

crystallography, spectroscopy and theory the result of the reduced excitation energy for this combination of sterically hindered ligand and heavy halide. Experiments showed weak paramagnetism similar to that previously found in dppe complexes and attributed in those reports to TIP. Theory does not predict TIP for these complexes because the calculated paramagnetic contribution is outweighed by the diamagnetic component. Traces of paramagnetic impurities, or an equilibrium between planar (singlet) and pseudo-tetrahedral (triplet) complexes, are more likely responsible for the observed magnetism according to our calculations, and cannot be ruled out on the basis of the experiments.

4. Experimental 4.1. Synthetic details

For the preparation of (dtbpe-2P)NiCl2, anhydrous nickel dichloride (0.20 g, 1.5 mmol) was suspended in ethanol (20 ml) and a solution of dtbpe (0.50 g, 1.6 mmol) in ethanol (30 ml) was added. The resulting mixture was heated under reflux for 4 h, during which time the colour changed from orange to deep red. Upon cooling, a red solid product was obtained (yield 0.50 g, 1.1 mmol, 74%). Recrystallization from CH2Cl2 led to the formation of solvent-free X-ray-quality crystals. Recrystallization from CHCl3 led to the formation of X-ray quality crystals of (dtbpe-2P)NiCl22CHCl3, which lose solvent readily. The compound is air stable as a solid but decomposes over hours in solution. When heated to 523 K the compound loses colour irreversibly but it does not melt to 573 K. Analysis calculated for C18H40Cl2NiP2: C 48.25, H 9.00, P 13.83%; found: C 48.14, H 8.96, P 13.83%. UV–Vis: solution: 351 (1800), 495 (790) nm; solid: 323, 491 nm. MS (FAB): 448 (M+), 411 (M  Cl)+ (with correct isotope patterns). 1H NMR (500 MHz, CDCl3, 298 K):  1.71 (br d, 4H, CH2CH2), 1.58 (br d, 36H, t-Bu). 31P{1H} NMR (202 MHz, CDCl3, 298 K):  89.5 (1/2 = 300 Hz). For the preparation of (dtbpe-2P)NiBr2, NiBr2(PPh3)2 (0.70 g, 0.94 mmol) and dtbpe (0.30 g, 0.94 mmol) were weighed into separate Schlenk flasks. Toluene (20 ml) was added to both flasks which were warmed slightly. The dtbpe solution was added to the green nickel suspension via cannula, and the resulting deep-red mixture was heated to reflux. The toluene was removed in vacuo and the product was extracted into CH2Cl2 and filtered through Celite, then the CH2Cl2 was also removed under dynamic vacuum. The PPh3 was washed out with hexane and deep-maroon microcrystals suitable for X-ray crystallography were collected (yield 0.35 g, 0.65 mmol, 69%). The compound decomposes without melting at 543 K. Analysis calculated for C18H40Br2NiP2: C 40.26, H 7.51, P 11.54%; found: C 40.03, H 7.37, P 11.41%. UV–Vis: solution: 417 (340), 523 (420) nm; solid: 550, 425 nm. MS (FAB): 457 (M  Br)+ (correct isotope pattern). 1H NMR (500 MHz, CDCl3, 298 K):  1.7 (br, 4H, CH2CH2), 1.5 (br, 36H, t-Bu). 31P{1H} NMR (202 MHz, CDCl3, 298 K):  100 (1/2 = 240 Hz). (dtbpe-2P)NiI2 was prepared as deep-blue–green crystals in exactly the same manner as the dichloride analogue, starting Acta Cryst. (2013). C69, 1437–1447

from NiI2 (yield 60%). It turns black and melts at 544–545 K. The 1H NMR spectrum contains very broad peaks and no 31P resonance is observed at room temperature. Analysis calculated for C18H40I2NiP2: C 34.26, H 6.39, P 9.82%; found: C 34.22, H 6.49, P 9.80%. UV–Vis: solution: 391 (3050), 606 (817) nm; solid: 396, 602 nm. MS (FAB): 630 (M+), 503 (M  I)+ (correct isotope pattern). (dppe-2P)NiI2CH2Cl2, was prepared according to the published procedure of Hudson et al. (1968) and crystallized from dichloromethane to provide the solvated crystals. 4.2. X-ray crystallography

Crystal data, data collection and structure refinement details are summarized in Table 6. For (dtbpe-2P)NiCl22CHCl3, H atoms were placed at calculated positions and refined as riding atoms, with Uiso values set at 1.5Ueq of the respective parent atom for CH3 groups (refined with free rotation) and at 1.2Ueq for all other groups. Both chloroform solvent molecules were disordered and were refined as the superposition of two orientations. The solvent molecules were restrained to have threefold local symmetry and to have similar bond lengths and angles within and across both molecules. The site-occupation factors were refined and gave values for the major orientations of 0.831 (10) and 0.852 (8). The atoms of the minor orientations were only refined isotropically. For (dtbpe-2P)NiCl2, most H atoms were located in a difference map; they were placed at calculated positions and were refined as riding atoms, with Uiso values set at 1.2 Ueq of the respective parent atoms for CH2 groups and at 1.5Ueq with free rotation for CH3 groups. One tert-butyl group in one of the two independent molecules was refined with a disorder model of two different conformations. These two superimposed orientations were restrained to have a local threefold rotational symmetry and similar bond lengths and angles. The site-occupation factors were refined and gave a value of 0.605 (13) for the major conformation. For (dtbpe-2P)NiBr2, H atoms were placed at calculated positions and refined as riding atoms, with Uiso values set at 1.2Ueq of the respective parent atoms for CH2 groups and at 1.5Ueq (with free rotation) for CH3 groups. For (dtbpe-2P)NiI2, all H atoms were located in a difference map but then placed at calculated positions and refined as riding atoms, with Uiso values set at 1.2Ueq of the respective parent atoms for CH2 groups and at 1.5Ueq (with free rotation) for CH3 groups. For (dppe-2P)NiI2CH2Cl2, H atoms could not be located in a difference map; they were placed at calculated positions and were refined as riding atoms, with Uiso values set at 1.2Ueq of their respective parent atoms. For the DCM solvent molecule, the two C—Cl distances were restrained to be similar. The anisotropic displacement parameters for this solvent molecule were refined with rigid bond restraints. We are grateful to Professor Dr Peter Hofmann, in whose laboratories most of this work was undertaken. We also thank

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crystallography, spectroscopy and theory Table 6 Experimental details.

Crystal data Chemical formula Mr Crystal system, space group Temperature (K) ˚) a, b, c (A , , ( ) ˚ 3) V (A Z Radiation type

(mm1) Crystal size (mm) Data collection Diffractometer Absorption correction Tmin, Tmax No. of measured, independent and observed [I > 2 (I)] reflections Rint ˚ 1) (sin /)max (A Refinement R[F 2 > 2 (F 2)], wR(F 2), S No. of reflections No. of parameters No. of restraints H-atom treatment ˚ 3)  max,  min (e A Absolute structure Absolute structure parameter

(dtpbe-2P)NiCl22CHCl3, (I)

(dtpbe-2P)NiCl2, (II)

(dtpbe-2P)NiBr2, (III)

[NiCl2(C18H40P2)]2CHCl3 686.78 Monoclinic, C2/c 200 17.2040 (3), 18.2618 (3), 20.2538 (4) 90, 94.572 (1), 90 6343.0 (2) 8 Mo K 1.40 0.42  0.40  0.15

[NiCl2(C18H40P2)] 448.05 Monoclinic, P21 200 11.1034 (7), 15.1216 (9), 14.5301 (9) 90, 109.965 (1), 90 2293.0 (2) 4 Mo K 1.22 0.20  0.08  0.07

[NiBr2(C18H40P2)] 536.97 Monoclinic, Cc 200 20.3765 (14), 8.1817 (6), 14.7392 (10) 90, 112.272 (1), 90 2273.9 (3) 4 Mo K 4.51 0.22  0.16  0.12

Bruker SMART CCD area-detector diffractometer Multi-scan (SADABS; Sheldrick, 2008a) 0.61, 0.83 32371, 7308, 5638

Bruker APEXII Quazar diffractometer Multi-scan (SADABS; Sheldrick, 2008a) 0.793, 0.920 30373, 11668, 9616

Bruker SMART CCD area-detector diffractometer Multi-scan (SADABS; Sheldrick, 2008a) 0.42, 0.67 3740, 3024, 2676

0.047 0.650

0.037 0.676

0.032 0.649

0.054, 0.129, 1.09 7308 326 132 H-atom parameters constrained 1.20, 0.64 – –

0.045, 0.096, 1.03 11668 479 67 H-atom parameters constrained 0.51, 0.43 Flack (1983), 5558 Friedel pairs 0.497 (11)

0.034, 0.079, 0.99 3024 220 2 H-atom parameters constrained 0.58, 0.50 Flack (1983), 542 Friedel pairs 0.033 (12)

(dtpbe-2P)NiI2, (IV)

(dppp-2P)NiI2CH2Cl2, (V)

Crystal data Chemical formula Mr Crystal system, space group Temperature (K) ˚) a, b, c (A

[NiI2(C18H40P2)] 630.95 Monoclinic, Cc 200 20.4783 (9), 8.3037 (4), 14.9472 (7)

, , ( ) ˚ 3) V (A Z Radiation type

(mm1) Crystal size (mm)

90, 110.999 (1), 90 2372.90 (19) 4 Mo K 3.55 0.12  0.08  0.05

[NiI2(C26H24P2)]CH2Cl2 795.83 Tetragonal, I41cd 200 26.3705 (17), 26.3705 (17), 16.7900 (11) 90, 90, 90 11675.8 (17) 16 Mo K 3.09 0.33  0.07  0.05

Data collection Diffractometer

Bruker APEXII Quazar diffractometer Multi-scan (SADABS; Sheldrick, 2008a) 0.675, 0.842 12902, 4689, 4404

Multi-scan (SADABS; Sheldrick, 2008a) 0.652, 0.850 109821, 7839, 7131

0.024 0.646

0.063 0.685

Refinement R[F 2 > 2 (F 2)], wR(F 2), S No. of reflections No. of parameters No. of restraints H-atom treatment ˚ 3)  max,  min (e A Absolute structure

0.024, 0.048, 1.05 4689 221 2 H-atom parameters constrained 0.51, 0.48 Flack (1983), 2238 Friedel pairs

Absolute structure parameter

0.115 (14)

0.035, 0.075, 1.04 7839 307 5 H-atom parameters constrained 1.32, 1.26 Flack x determined using 3206 quotients (Parsons & Flack, 2004) 0.004 (7)

Absorption correction Tmin, Tmax No. of measured, independent and observed [I > 2 (I)] reflections Rint ˚ 1) (sin /)max (A

Bruker APEX diffractometer

Computer programs: SMART (Bruker, 2001), APEX2 (Bruker, 2005), SAINT (Bruker, 2001, 2005), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b) and SHELXTL (Sheldrick, 2008b).

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crystallography, spectroscopy and theory Professor Keith Murray and Dr Boujemaa Moubaraki who assisted with the SQUID measurements. PP is supported by CaRLa, which is co-financed by Heidelberg University, the State of Baden–Wu¨rttemberg and BASF SE. Their support is gratefully acknowledged. Supplementary data for this paper are available from the IUCr electronic archives (Reference: FA3325). Services for accessing these data are described at the back of the journal.

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supplementary materials Acta Cryst. (2013). C69, 1437-1447

[doi:10.1107/S0108270113030692]

Structure, magnetism and colour in simple bis(phosphine)nickel(II) dihalide complexes: an experimental and theoretical investigation Madeleine Schultz, Philipp-Nikolaus Plessow, Frank Rominger and Laura Weigel Computing details Data collection: SMART (Bruker, 2001) for msc6, msc11; APEX2 (Bruker, 2005) for lw27, lw23, lw29. Cell refinement: SMART (Bruker, 2001) for msc6, msc11; SAINT (Bruker, 2005) for lw27, lw23, lw29. Data reduction: SAINT (Bruker, 2001) for msc6, msc11; SAINT (Bruker, 2005) for lw27, lw23, lw29. For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b). (msc6) [1,2-Bis(di-tert-butylphosphanyl)ethane-κ2P,P′]dichloridonickel(II) chloroform disolvate Crystal data [NiCl2(C18H40P2)]·2CHCl3 Mr = 686.78 Monoclinic, C2/c a = 17.2040 (3) Å b = 18.2618 (3) Å c = 20.2538 (4) Å β = 94.572 (1)° V = 6343.0 (2) Å3 Z=8

F(000) = 2848 Dx = 1.438 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 7319 reflections µ = 1.40 mm−1 T = 200 K Polyhedron, red 0.42 × 0.40 × 0.15 mm

Data collection Bruker SMART CCD area-detector diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω scans Absorption correction: multi-scan (SADABS; Sheldrick, 2008a) Tmin = 0.61, Tmax = 0.83

32371 measured reflections 7308 independent reflections 5638 reflections with I > 2σ(I) Rint = 0.047 θmax = 27.5°, θmin = 1.6° h = −22→22 k = −23→23 l = −26→26

Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.054 wR(F2) = 0.129 S = 1.09 7308 reflections 326 parameters 132 restraints

Acta Cryst. (2013). C69, 1437-1447

Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained

sup-1

supplementary materials w = 1/[σ2(Fo2) + (0.0417P)2 + 25.352P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.001

Δρmax = 1.20 e Å−3 Δρmin = −0.64 e Å−3

Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

Ni1 P1 P2 Cl1 Cl2 C9 H9A H9B C10 H10A H10B C11 C12 H12A H12B H12C C13 H13A H13B H13C C14 H14A H14B H14C C15 C16 H16A H16B H16C C17 H17A H17B H17C

x

y

z

Uiso*/Ueq

0.73904 (2) 0.74269 (5) 0.73218 (5) 0.73926 (6) 0.74224 (7) 0.7545 (2) 0.7309 0.8108 0.7166 (3) 0.7382 0.6599 0.8307 (2) 0.8494 (3) 0.8061 0.8567 0.8972 0.8212 (3) 0.8697 0.8096 0.7784 0.9002 (3) 0.9460 0.9114 0.8874 0.6504 (2) 0.6572 (3) 0.6738 0.6958 0.6065 0.6235 (3) 0.5722 0.6611 0.6198

0.00993 (2) 0.12608 (5) 0.04086 (5) −0.10701 (5) −0.02311 (5) 0.17882 (19) 0.2279 0.1856 0.14080 (19) 0.1612 0.1509 0.1536 (2) 0.2353 (3) 0.2643 0.2471 0.2466 0.1370 (3) 0.1492 0.0849 0.1664 0.1089 (3) 0.1183 0.1232 0.0566 0.1637 (2) 0.2434 (3) 0.2715 0.2491 0.2615 0.1177 (4) 0.1349 0.1225 0.0663

0.30173 (2) 0.33156 (4) 0.19651 (4) 0.27272 (5) 0.40635 (4) 0.25551 (18) 0.2596 0.2502 0.19459 (17) 0.1546 0.1913 0.38836 (19) 0.3825 (3) 0.3973 0.3362 0.4102 0.4613 (2) 0.4878 0.4664 0.4763 0.3671 (3) 0.3978 0.3222 0.3677 0.36434 (18) 0.3830 (3) 0.3453 0.4209 0.3948 0.4211 (3) 0.4324 0.4598 0.4075

0.02831 (11) 0.03154 (19) 0.03277 (19) 0.0479 (2) 0.0509 (3) 0.0435 (9) 0.052* 0.052* 0.0438 (9) 0.053* 0.053* 0.0440 (8) 0.0677 (13) 0.101* 0.101* 0.101* 0.0647 (13) 0.097* 0.097* 0.097* 0.0666 (13) 0.100* 0.100* 0.100* 0.0430 (8) 0.0810 (17) 0.121* 0.121* 0.121* 0.0820 (17) 0.123* 0.123* 0.123*

Acta Cryst. (2013). C69, 1437-1447

Occ. ( 2σ(I)

sup-7

supplementary materials k = −19→20 l = −19→19

Rint = 0.037 θmax = 28.7°, θmin = 1.5° h = −15→15 Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.045 wR(F2) = 0.096 S = 1.03 11668 reflections 479 parameters 67 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ2(Fo2) + (0.0328P)2 + 1.7022P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.001 Δρmax = 0.51 e Å−3 Δρmin = −0.43 e Å−3 Absolute structure: Flack (1983), ???? Friedel pairs Absolute structure parameter: 0.497 (11)

Special details Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

Ni1_1 Cl1_1 Cl2_1 P1_1 P2_1 C9_1 H9A_1 H9B_1 C10_1 H10A_1 H10B_1 C11_1 C12_1 H12A_1 H12B_1 H12C_1 C13_1 H13A_1 H13B_1 H13C_1 C14_1

x

y

z

Uiso*/Ueq

0.46480 (4) 0.56346 (9) 0.29424 (10) 0.37696 (9) 0.63105 (9) 0.5015 (4) 0.4597 0.5528 0.5891 (4) 0.6684 0.5472 0.3417 (4) 0.4413 (5) 0.4380 0.4224 0.5271 0.3523 (6) 0.4411 0.3261 0.2963 0.2106 (4)

1.04090 (3) 0.94644 (7) 0.95426 (7) 1.12973 (6) 1.12983 (6) 1.2119 (3) 1.2676 1.1898 1.2309 (3) 1.2587 1.2734 1.0762 (3) 1.0029 (3) 0.9607 0.9720 1.0290 1.1414 (4) 1.1616 1.1120 1.1923 1.0326 (3)

0.47529 (3) 0.41005 (7) 0.43790 (8) 0.55408 (7) 0.50540 (6) 0.6146 (3) 0.6231 0.6805 0.5588 (3) 0.6031 0.5057 0.6604 (3) 0.7020 (4) 0.6499 0.7548 0.7278 0.7437 (4) 0.7726 0.7939 0.7177 0.6299 (3)

0.02289 (10) 0.0386 (2) 0.0424 (2) 0.0253 (2) 0.02363 (19) 0.0348 (9) 0.042* 0.042* 0.0354 (9) 0.042* 0.042* 0.0366 (9) 0.0552 (13) 0.083* 0.083* 0.083* 0.0700 (17) 0.105* 0.105* 0.105* 0.0501 (11)

Acta Cryst. (2013). C69, 1437-1447

Occ. ( 2σ(I) Rint = 0.032 θmax = 27.5°, θmin = 2.7° h = −26→13 k = −4→10 l = −17→18

Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.034 wR(F2) = 0.079 S = 0.99 3024 reflections 220 parameters 2 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ2(Fo2) + (0.0502P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.004 Δρmax = 0.57 e Å−3 Δρmin = −0.50 e Å−3 Absolute structure: Flack (1983), ???? Friedel pairs Absolute structure parameter: 0.033 (12)

Special details Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Acta Cryst. (2013). C69, 1437-1447

sup-18

supplementary materials Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

Br1 Br2 Ni3 P4 P5 C1 H1A H1B C3 C2 H2A H2B C11 C14 H14A H14B H14C C13 H13A H13B H13C C12 H12A H12B H12C C10 H10A H10B H10C C9 H9A H9B H9C C8 H8A H8B H8C C7 C15 C6 H6A H6B H6C C18 H18A H18B H18C

x

y

z

Uiso*/Ueq

0.86806 (3) 0.69196 (4) 0.78552 (4) 0.86805 (8) 0.71332 (8) 0.8370 (3) 0.8575 0.8541 0.9609 (3) 0.7561 (3) 0.7372 0.7432 0.7094 (3) 0.6740 (4) 0.6235 0.6795 0.6964 0.6728 (5) 0.6924 0.6811 0.6217 0.7858 (4) 0.7858 0.8106 0.8100 0.7998 (4) 0.7638 0.7983 0.7903 0.9260 (4) 0.9231 0.9740 0.9151 0.8889 (4) 0.9363 0.8872 0.8537 0.8727 (3) 0.6208 (3) 0.9953 (3) 0.9992 1.0427 0.9660 0.5971 (4) 0.5480 0.6280 0.6005

0.23380 (6) 0.23502 (9) 0.34430 (7) 0.50060 (16) 0.39128 (17) 0.5523 (7) 0.4740 0.6629 0.4275 (7) 0.5483 (7) 0.6568 0.5289 0.1981 (7) 0.0552 (7) 0.0787 −0.0446 0.0399 0.2236 (8) 0.3210 0.1279 0.2381 0.1450 (8) 0.0441 0.2312 0.1258 0.7792 (7) 0.6997 0.8739 0.8147 0.8221 (7) 0.9255 0.7774 0.8414 0.6687 (7) 0.6207 0.7721 0.5931 0.7005 (7) 0.4818 (7) 0.5201 (7) 0.6362 0.4755 0.5078 0.5732 (8) 0.6100 0.6680 0.4995

0.56885 (4) 0.49396 (5) 0.62955 (5) 0.73702 (10) 0.70768 (11) 0.8353 (4) 0.8900 0.8605 0.8114 (4) 0.8008 (4) 0.7735 0.8582 0.7758 (4) 0.7080 (5) 0.6733 0.7470 0.6604 0.8494 (6) 0.8891 0.8923 0.8135 0.8339 (5) 0.8697 0.8805 0.7887 0.6417 (6) 0.6041 0.6003 0.6990 0.7428 (5) 0.7079 0.7625 0.8012 0.5835 (5) 0.6026 0.5491 0.5401 0.6753 (5) 0.6466 (5) 0.9083 (4) 0.8947 0.9447 0.9474 0.7209 (6) 0.6880 0.7468 0.7749

0.02888 (16) 0.0412 (2) 0.01845 (17) 0.0179 (3) 0.0198 (3) 0.0228 (13) 0.027* 0.027* 0.0242 (13) 0.0242 (13) 0.029* 0.029* 0.0251 (13) 0.0314 (15) 0.047* 0.047* 0.047* 0.0419 (19) 0.063* 0.063* 0.063* 0.0363 (16) 0.054* 0.054* 0.054* 0.0356 (16) 0.053* 0.053* 0.053* 0.0313 (14) 0.047* 0.047* 0.047* 0.0318 (15) 0.048* 0.048* 0.048* 0.0248 (14) 0.0312 (14) 0.0317 (15) 0.048* 0.048* 0.048* 0.0433 (19) 0.065* 0.065* 0.065*

Acta Cryst. (2013). C69, 1437-1447

sup-19

supplementary materials C17 H17A H17B H17C C16 H16A H16B H16C C5 H5A H5B H5C C4 H4A H4B H4C

0.6229 (4) 0.5758 0.6369 0.6573 0.5645 (3) 0.5791 0.5191 0.5593 1.0111 (3) 1.0578 1.0162 0.9910 0.9571 (4) 0.9296 1.0052 0.9342

0.6035 (9) 0.6519 0.5469 0.6899 0.3520 (8) 0.2872 0.4054 0.2801 0.4395 (7) 0.3949 0.5542 0.3768 0.2448 (7) 0.2345 0.2030 0.1817

0.5693 (6) 0.5364 0.5209 0.6008 0.5971 (5) 0.5520 0.5605 0.6472 0.7539 (5) 0.7941 0.7386 0.6929 0.8375 (5) 0.8792 0.8728 0.7772

0.0433 (18) 0.065* 0.065* 0.065* 0.0351 (15) 0.053* 0.053* 0.053* 0.0315 (14) 0.047* 0.047* 0.047* 0.0327 (15) 0.049* 0.049* 0.049*

Atomic displacement parameters (Å2)

Br1 Br2 Ni3 P4 P5 C1 C3 C2 C11 C14 C13 C12 C10 C9 C8 C7 C15 C6 C18 C17 C16 C5 C4

U11

U22

U33

U12

U13

U23

0.0324 (4) 0.0304 (4) 0.0198 (4) 0.0185 (8) 0.0188 (8) 0.020 (3) 0.020 (3) 0.022 (3) 0.027 (3) 0.031 (4) 0.048 (5) 0.032 (4) 0.032 (4) 0.030 (4) 0.038 (4) 0.022 (4) 0.018 (3) 0.022 (4) 0.025 (4) 0.021 (4) 0.019 (3) 0.017 (3) 0.037 (4)

0.0317 (3) 0.0645 (5) 0.0197 (3) 0.0179 (6) 0.0195 (7) 0.026 (3) 0.024 (3) 0.022 (3) 0.024 (3) 0.023 (3) 0.045 (4) 0.035 (3) 0.028 (3) 0.021 (3) 0.033 (3) 0.023 (3) 0.032 (3) 0.032 (3) 0.038 (4) 0.044 (4) 0.043 (4) 0.033 (3) 0.029 (3)

0.0267 (3) 0.0278 (4) 0.0166 (3) 0.0177 (7) 0.0214 (7) 0.028 (3) 0.027 (3) 0.032 (3) 0.024 (3) 0.039 (4) 0.040 (4) 0.036 (4) 0.047 (4) 0.036 (4) 0.024 (3) 0.034 (4) 0.039 (4) 0.031 (4) 0.070 (5) 0.056 (5) 0.039 (4) 0.046 (4) 0.027 (4)

0.0010 (3) −0.0184 (4) −0.0038 (3) −0.0012 (6) −0.0025 (6) −0.008 (3) 0.000 (3) −0.005 (3) −0.009 (3) −0.008 (3) −0.013 (4) −0.007 (3) 0.008 (3) 0.000 (3) 0.000 (3) −0.001 (2) 0.006 (3) −0.007 (3) −0.003 (3) 0.004 (3) −0.006 (3) 0.003 (3) 0.003 (3)

0.0159 (3) 0.0100 (3) 0.0076 (3) 0.0075 (6) 0.0082 (6) 0.016 (3) 0.007 (3) 0.014 (3) 0.009 (3) 0.013 (3) 0.026 (4) 0.006 (3) 0.015 (4) 0.005 (3) 0.011 (3) 0.016 (3) 0.005 (3) −0.002 (3) 0.022 (4) 0.005 (3) 0.006 (3) 0.014 (3) 0.007 (3)

−0.0055 (3) −0.0205 (3) −0.0040 (3) −0.0016 (6) −0.0030 (6) −0.009 (3) −0.002 (3) −0.007 (3) 0.001 (2) −0.007 (3) −0.002 (3) 0.008 (3) 0.013 (3) −0.004 (3) 0.009 (3) 0.001 (2) 0.002 (3) −0.004 (3) −0.016 (4) 0.019 (4) −0.004 (3) 0.003 (3) 0.001 (3)

Geometric parameters (Å, º) Br1—Ni3 Br2—Ni3 Ni3—P5 Ni3—P4

Acta Cryst. (2013). C69, 1437-1447

2.3638 (9) 2.3537 (10) 2.2186 (16) 2.2256 (16)

C10—H10B C10—H10C C9—C7 C9—H9A

0.9800 0.9800 1.530 (9) 0.9800

sup-20

supplementary materials P4—C1 P4—C3 P4—C7 P5—C2 P5—C11 P5—C15 C1—C2 C1—H1A C1—H1B C3—C6 C3—C4 C3—C5 C2—H2A C2—H2B C11—C12 C11—C14 C11—C13 C14—H14A C14—H14B C14—H14C C13—H13A C13—H13B C13—H13C C12—H12A C12—H12B C12—H12C C10—C7 C10—H10A

1.837 (5) 1.889 (6) 1.891 (6) 1.841 (6) 1.890 (6) 1.904 (6) 1.529 (8) 0.9900 0.9900 1.532 (8) 1.553 (7) 1.559 (8) 0.9900 0.9900 1.529 (10) 1.529 (8) 1.546 (9) 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 1.519 (9) 0.9800

C9—H9B C9—H9C C8—C7 C8—H8A C8—H8B C8—H8C C15—C17 C15—C16 C15—C18 C6—H6A C6—H6B C6—H6C C18—H18A C18—H18B C18—H18C C17—H17A C17—H17B C17—H17C C16—H16A C16—H16B C16—H16C C5—H5A C5—H5B C5—H5C C4—H4A C4—H4B C4—H4C

0.9800 0.9800 1.533 (8) 0.9800 0.9800 0.9800 1.526 (9) 1.530 (9) 1.546 (9) 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800

P5—Ni3—P4 P5—Ni3—Br2 P4—Ni3—Br2 P5—Ni3—Br1 P4—Ni3—Br1 Br2—Ni3—Br1 C1—P4—C3 C1—P4—C7 C3—P4—C7 C1—P4—Ni3 C3—P4—Ni3 C7—P4—Ni3 C2—P5—C11 C2—P5—C15 C11—P5—C15 C2—P5—Ni3 C11—P5—Ni3 C15—P5—Ni3 C2—C1—P4 C2—C1—H1A

90.10 (6) 91.35 (5) 166.65 (5) 165.85 (5) 92.01 (5) 89.82 (3) 100.6 (3) 106.0 (3) 109.4 (3) 107.48 (19) 123.47 (18) 108.4 (2) 106.9 (3) 100.7 (3) 110.0 (3) 106.72 (19) 107.51 (19) 123.7 (2) 112.5 (4) 109.1

C7—C10—H10C H10A—C10—H10C H10B—C10—H10C C7—C9—H9A C7—C9—H9B H9A—C9—H9B C7—C9—H9C H9A—C9—H9C H9B—C9—H9C C7—C8—H8A C7—C8—H8B H8A—C8—H8B C7—C8—H8C H8A—C8—H8C H8B—C8—H8C C10—C7—C9 C10—C7—C8 C9—C7—C8 C10—C7—P4 C9—C7—P4

109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 107.6 (5) 107.2 (5) 110.2 (5) 107.6 (4) 113.7 (5)

Acta Cryst. (2013). C69, 1437-1447

sup-21

supplementary materials P4—C1—H1A C2—C1—H1B P4—C1—H1B H1A—C1—H1B C6—C3—C4 C6—C3—C5 C4—C3—C5 C6—C3—P4 C4—C3—P4 C5—C3—P4 C1—C2—P5 C1—C2—H2A P5—C2—H2A C1—C2—H2B P5—C2—H2B H2A—C2—H2B C12—C11—C14 C12—C11—C13 C14—C11—C13 C12—C11—P5 C14—C11—P5 C13—C11—P5 C11—C14—H14A C11—C14—H14B H14A—C14—H14B C11—C14—H14C H14A—C14—H14C H14B—C14—H14C C11—C13—H13A C11—C13—H13B H13A—C13—H13B C11—C13—H13C H13A—C13—H13C H13B—C13—H13C C11—C12—H12A C11—C12—H12B H12A—C12—H12B C11—C12—H12C H12A—C12—H12C H12B—C12—H12C C7—C10—H10A C7—C10—H10B H10A—C10—H10B

109.1 109.1 109.1 107.8 107.0 (5) 108.3 (5) 107.5 (5) 112.8 (4) 108.4 (4) 112.6 (4) 114.2 (4) 108.7 108.7 108.7 108.7 107.6 106.1 (5) 107.8 (6) 109.2 (5) 107.2 (4) 113.4 (4) 112.9 (4) 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5

C8—C7—P4 C17—C15—C16 C17—C15—C18 C16—C15—C18 C17—C15—P5 C16—C15—P5 C18—C15—P5 C3—C6—H6A C3—C6—H6B H6A—C6—H6B C3—C6—H6C H6A—C6—H6C H6B—C6—H6C C15—C18—H18A C15—C18—H18B H18A—C18—H18B C15—C18—H18C H18A—C18—H18C H18B—C18—H18C C15—C17—H17A C15—C17—H17B H17A—C17—H17B C15—C17—H17C H17A—C17—H17C H17B—C17—H17C C15—C16—H16A C15—C16—H16B H16A—C16—H16B C15—C16—H16C H16A—C16—H16C H16B—C16—H16C C3—C5—H5A C3—C5—H5B H5A—C5—H5B C3—C5—H5C H5A—C5—H5C H5B—C5—H5C C3—C4—H4A C3—C4—H4B H4A—C4—H4B C3—C4—H4C H4A—C4—H4C H4B—C4—H4C

110.2 (4) 109.0 (6) 108.5 (6) 107.1 (5) 107.7 (4) 112.6 (4) 111.8 (5) 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5

P5—Ni3—P4—C1 Br2—Ni3—P4—C1 Br1—Ni3—P4—C1 P5—Ni3—P4—C3 Br2—Ni3—P4—C3

8.1 (2) 104.3 (3) −157.9 (2) 124.2 (2) −139.5 (3)

C11—P5—C2—C1 C15—P5—C2—C1 Ni3—P5—C2—C1 C2—P5—C11—C12 C15—P5—C11—C12

88.6 (5) −156.4 (4) −26.2 (5) −64.1 (5) −172.6 (4)

Acta Cryst. (2013). C69, 1437-1447

sup-22

supplementary materials Br1—Ni3—P4—C3 P5—Ni3—P4—C7 Br2—Ni3—P4—C7 Br1—Ni3—P4—C7 P4—Ni3—P5—C2 Br2—Ni3—P5—C2 Br1—Ni3—P5—C2 P4—Ni3—P5—C11 Br2—Ni3—P5—C11 Br1—Ni3—P5—C11 P4—Ni3—P5—C15 Br2—Ni3—P5—C15 Br1—Ni3—P5—C15 C3—P4—C1—C2 C7—P4—C1—C2 Ni3—P4—C1—C2 C1—P4—C3—C6 C7—P4—C3—C6 Ni3—P4—C3—C6 C1—P4—C3—C4 C7—P4—C3—C4 Ni3—P4—C3—C4 C1—P4—C3—C5 C7—P4—C3—C5 Ni3—P4—C3—C5 P4—C1—C2—P5

−41.8 (2) −106.09 (19) −9.8 (3) 87.90 (19) 7.7 (2) −159.0 (2) 106.3 (3) −106.7 (2) 86.5 (2) −8.1 (3) 123.4 (2) −43.4 (2) −138.0 (3) −156.4 (4) 89.8 (4) −26.0 (5) −34.3 (5) 77.0 (5) −153.7 (3) 84.0 (4) −164.7 (4) −35.4 (5) −157.2 (4) −45.9 (5) 83.4 (4) 34.1 (6)

Ni3—P5—C11—C12 C2—P5—C11—C14 C15—P5—C11—C14 Ni3—P5—C11—C14 C2—P5—C11—C13 C15—P5—C11—C13 Ni3—P5—C11—C13 C1—P4—C7—C10 C3—P4—C7—C10 Ni3—P4—C7—C10 C1—P4—C7—C9 C3—P4—C7—C9 Ni3—P4—C7—C9 C1—P4—C7—C8 C3—P4—C7—C8 Ni3—P4—C7—C8 C2—P5—C15—C17 C11—P5—C15—C17 Ni3—P5—C15—C17 C2—P5—C15—C16 C11—P5—C15—C16 Ni3—P5—C15—C16 C2—P5—C15—C18 C11—P5—C15—C18 Ni3—P5—C15—C18

50.2 (5) 179.3 (4) 70.7 (5) −66.5 (5) 54.5 (6) −54.0 (6) 168.8 (5) −56.1 (5) −163.8 (4) 59.0 (5) 62.9 (5) −44.8 (5) 178.0 (4) −172.7 (4) 79.6 (5) −57.6 (5) 84.2 (5) −163.2 (5) −34.3 (6) −155.6 (5) −43.0 (5) 85.8 (5) −34.9 (5) 77.7 (5) −153.5 (4)

(lw23) [1,2-Bis(di-tert-butylphosphanyl)ethane-κ2P,P′]diiodidonickel(II) Crystal data [NiI2(C18H40P2)] Mr = 630.95 Monoclinic, Cc a = 20.4783 (9) Å b = 8.3037 (4) Å c = 14.9472 (7) Å β = 110.999 (1)° V = 2372.90 (19) Å3 Z=4

F(000) = 1248 Dx = 1.766 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 8357 reflections θ = 2.7–27.1° µ = 3.55 mm−1 T = 200 K Plate, green 0.12 × 0.08 × 0.05 mm

Data collection Bruker APEXII Quazar diffractometer Radiation source: ImuS microsource Mirror monochromator φ and ω scans Absorption correction: multi-scan (SADABS; Sheldrick, 2008a) Tmin = 0.675, Tmax = 0.842

Acta Cryst. (2013). C69, 1437-1447

12902 measured reflections 4689 independent reflections 4404 reflections with I > 2σ(I) Rint = 0.024 θmax = 27.3°, θmin = 2.1° h = −26→25 k = −10→10 l = −19→19

sup-23

supplementary materials Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.024 wR(F2) = 0.048 S = 1.05 4689 reflections 221 parameters 2 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ2(Fo2) + (0.0211P)2 + 0.1993P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.002 Δρmax = 0.51 e Å−3 Δρmin = −0.48 e Å−3 Absolute structure: Flack (1983), ???? Friedel pairs Absolute structure parameter: 0.115 (14)

Special details Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

Ni1 I1 I2 P1 P2 C9 H9A H9B C10 H10A H10B C11 C12 H12A H12B H12C C13 H13A H13B H13C C14 H14A H14B H14C

x

y

z

Uiso*/Ueq

0.26145 (3) 0.172476 (12) 0.358381 (14) 0.33593 (5) 0.18075 (5) 0.2951 (2) 0.3131 0.3090 0.21552 (19) 0.1967 0.1985 0.3405 (2) 0.3784 (3) 0.4278 0.3570 0.3747 0.2653 (2) 0.2429 0.2393 0.2653 0.3741 (2) 0.3716 0.3490 0.4232

0.33973 (5) 0.21579 (3) 0.22306 (4) 0.38903 (12) 0.49559 (11) 0.5450 (5) 0.6517 0.5277 0.5465 (5) 0.4689 0.6549 0.2015 (5) 0.2315 (5) 0.2546 0.3235 0.1356 0.1525 (5) 0.2369 0.1378 0.0513 0.0580 (5) −0.0376 0.0374 0.0826

0.47078 (3) 0.535269 (14) 0.614557 (17) 0.39516 (7) 0.36569 (7) 0.3053 (3) 0.3328 0.2491 0.2721 (3) 0.2187 0.2469 0.3244 (3) 0.2547 (4) 0.2907 0.2136 0.2149 0.2663 (3) 0.2195 0.3095 0.2325 0.3893 (3) 0.3497 0.4329 0.4265

0.01521 (11) 0.02594 (7) 0.03692 (9) 0.0174 (2) 0.0145 (2) 0.0231 (9) 0.028* 0.028* 0.0204 (9) 0.024* 0.024* 0.0250 (9) 0.0349 (12) 0.052* 0.052* 0.052* 0.0361 (11) 0.054* 0.054* 0.054* 0.0300 (10) 0.045* 0.045* 0.045*

Acta Cryst. (2013). C69, 1437-1447

sup-24

supplementary materials C15 C16 H16A H16B H16C C17 H17A H17B H17C C18 H18A H18B H18C C21 C22 H22A H22B H22C C23 H23A H23B H23C C24 H24A H24B H24C C25 C26 H26A H26B H26C C27 H27A H27B H27C C28 H28A H28B H28C

0.4278 (2) 0.4505 (2) 0.4208 0.4459 0.4994 0.4840 (2) 0.5279 0.4912 0.4687 0.4263 (2) 0.4106 0.3940 0.4733 0.0885 (2) 0.03674 (19) −0.0079 0.0293 0.0556 0.0589 (2) 0.0877 0.0596 0.0107 0.0926 (2) 0.1148 0.1203 0.0453 0.1756 (2) 0.1255 (2) 0.1264 0.0780 0.1400 0.2482 (2) 0.2610 0.2818 0.2486 0.1551 (2) 0.1890 0.1084 0.1548

0.4799 (5) 0.5723 (6) 0.6674 0.5022 0.6061 0.3523 (5) 0.4054 0.2876 0.2822 0.5994 (6) 0.5445 0.6874 0.6430 0.4260 (5) 0.4410 (5) 0.3916 0.5551 0.3860 0.5204 (5) 0.4996 0.6358 0.4860 0.2490 (4) 0.1865 0.2393 0.2077 0.6925 (4) 0.8147 (4) 0.9146 0.7706 0.8374 0.7656 (5) 0.7998 0.6853 0.8589 0.6634 (5) 0.5904 0.6150 0.7661

0.4544 (3) 0.3813 (4) 0.3591 0.3266 0.4116 0.5000 (3) 0.5380 0.4495 0.5416 0.5310 (4) 0.5778 0.5010 0.5635 0.2892 (3) 0.3412 (3) 0.3022 0.3514 0.4032 0.1948 (3) 0.1559 0.2088 0.1596 0.2635 (3) 0.3223 0.2222 0.2296 0.4262 (3) 0.3598 (3) 0.3952 0.3364 0.3054 0.4632 (4) 0.4089 0.5010 0.5035 0.5137 (3) 0.5582 0.4932 0.5458

0.0273 (9) 0.0441 (14) 0.066* 0.066* 0.066* 0.0297 (10) 0.045* 0.045* 0.045* 0.0402 (12) 0.060* 0.060* 0.060* 0.0202 (9) 0.0263 (9) 0.039* 0.039* 0.039* 0.0286 (10) 0.043* 0.043* 0.043* 0.0267 (10) 0.040* 0.040* 0.040* 0.0202 (9) 0.0302 (11) 0.045* 0.045* 0.045* 0.0354 (11) 0.053* 0.053* 0.053* 0.0267 (10) 0.040* 0.040* 0.040*

Atomic displacement parameters (Å2)

Ni1 I1 I2 P1 P2 C9 C10

U11

U22

U33

U12

U13

U23

0.0166 (2) 0.02948 (17) 0.02744 (18) 0.0153 (5) 0.0143 (5) 0.020 (2) 0.025 (2)

0.0164 (2) 0.02720 (13) 0.0586 (2) 0.0195 (5) 0.0150 (5) 0.027 (2) 0.022 (2)

0.0130 (2) 0.02349 (16) 0.02348 (17) 0.0184 (5) 0.0142 (5) 0.024 (2) 0.013 (2)

0.0028 (2) −0.00220 (13) 0.01514 (16) 0.0025 (4) 0.0008 (4) 0.0013 (18) 0.0081 (17)

0.00576 (19) 0.01234 (13) 0.00762 (14) 0.0072 (4) 0.0052 (4) 0.0095 (18) 0.0059 (18)

0.0025 (2) 0.00151 (13) 0.01616 (15) 0.0026 (4) 0.0002 (4) 0.0042 (17) 0.0080 (16)

Acta Cryst. (2013). C69, 1437-1447

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supplementary materials C11 C12 C13 C14 C15 C16 C17 C18 C21 C22 C23 C24 C25 C26 C27 C28

0.027 (2) 0.039 (3) 0.035 (3) 0.031 (3) 0.016 (2) 0.023 (3) 0.014 (2) 0.020 (2) 0.015 (2) 0.014 (2) 0.020 (2) 0.027 (2) 0.023 (2) 0.034 (3) 0.030 (3) 0.041 (3)

0.024 (2) 0.039 (3) 0.030 (2) 0.026 (2) 0.033 (2) 0.041 (3) 0.044 (3) 0.039 (3) 0.028 (2) 0.031 (2) 0.034 (2) 0.029 (2) 0.014 (2) 0.015 (2) 0.025 (2) 0.0180 (19)

0.025 (2) 0.037 (3) 0.037 (3) 0.036 (3) 0.032 (2) 0.066 (4) 0.030 (2) 0.054 (3) 0.016 (2) 0.031 (2) 0.027 (2) 0.020 (2) 0.025 (2) 0.038 (3) 0.050 (3) 0.023 (2)

0.0058 (18) 0.012 (2) 0.008 (2) 0.0072 (19) 0.0011 (18) −0.006 (2) 0.0023 (19) −0.007 (2) 0.0013 (17) 0.0003 (17) 0.0017 (18) −0.0053 (18) 0.0019 (16) 0.0093 (19) −0.0039 (19) 0.0030 (18)

0.0109 (19) 0.027 (2) 0.005 (2) 0.016 (2) 0.0072 (18) 0.012 (3) 0.0067 (18) 0.005 (2) 0.0026 (17) 0.0050 (18) 0.0020 (19) 0.0028 (19) 0.0113 (19) 0.008 (2) 0.012 (2) 0.013 (2)

−0.0010 (17) 0.006 (2) −0.012 (2) 0.0007 (19) 0.0027 (19) 0.014 (3) 0.005 (2) −0.018 (2) 0.0009 (17) 0.0021 (18) 0.0002 (19) −0.0076 (17) −0.0056 (15) 0.0033 (18) −0.009 (2) −0.0046 (17)

Geometric parameters (Å, º) Ni1—P1 Ni1—P2 Ni1—I2 Ni1—I1 P1—C9 P1—C11 P1—C15 P2—C10 P2—C25 P2—C21 C9—C10 C9—H9A C9—H9B C10—H10A C10—H10B C11—C12 C11—C13 C11—C14 C12—H12A C12—H12B C12—H12C C13—H13A C13—H13B C13—H13C C14—H14A C14—H14B C14—H14C C15—C18 C15—C17 C15—C16 C16—H16A Acta Cryst. (2013). C69, 1437-1447

2.2377 (11) 2.2389 (10) 2.5377 (5) 2.5626 (5) 1.837 (4) 1.904 (4) 1.923 (4) 1.832 (4) 1.889 (4) 1.914 (4) 1.524 (5) 0.9900 0.9900 0.9900 0.9900 1.526 (6) 1.529 (6) 1.535 (5) 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 1.524 (6) 1.533 (6) 1.538 (6) 0.9800

C16—H16C C17—H17A C17—H17B C17—H17C C18—H18A C18—H18B C18—H18C C21—C22 C21—C24 C21—C23 C22—H22A C22—H22B C22—H22C C23—H23A C23—H23B C23—H23C C24—H24A C24—H24B C24—H24C C25—C27 C25—C26 C25—C28 C26—H26A C26—H26B C26—H26C C27—H27A C27—H27B C27—H27C C28—H28A C28—H28B C28—H28C

0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 1.526 (5) 1.529 (5) 1.536 (5) 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 1.514 (6) 1.529 (6) 1.530 (6) 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800 0.9800

sup-26

supplementary materials C16—H16B

0.9800

P1—Ni1—P2 P1—Ni1—I2 P2—Ni1—I2 P1—Ni1—I1 P2—Ni1—I1 I2—Ni1—I1 C9—P1—C11 C9—P1—C15 C11—P1—C15 C9—P1—Ni1 C11—P1—Ni1 C15—P1—Ni1 C10—P2—C25 C10—P2—C21 C25—P2—C21 C10—P2—Ni1 C25—P2—Ni1 C21—P2—Ni1 C10—C9—P1 C10—C9—H9A P1—C9—H9A C10—C9—H9B P1—C9—H9B H9A—C9—H9B C9—C10—P2 C9—C10—H10A P2—C10—H10A C9—C10—H10B P2—C10—H10B H10A—C10—H10B C12—C11—C13 C12—C11—C14 C13—C11—C14 C12—C11—P1 C13—C11—P1 C14—C11—P1 C11—C12—H12A C11—C12—H12B H12A—C12—H12B C11—C12—H12C H12A—C12—H12C H12B—C12—H12C C11—C13—H13A C11—C13—H13B H13A—C13—H13B C11—C13—H13C H13A—C13—H13C

90.30 (4) 91.70 (3) 166.29 (3) 165.63 (3) 92.90 (3) 88.507 (16) 105.72 (19) 100.02 (18) 109.99 (18) 106.49 (13) 108.02 (13) 124.78 (14) 105.62 (18) 100.64 (17) 109.55 (18) 106.13 (12) 108.55 (13) 124.53 (13) 113.4 (3) 108.9 108.9 108.9 108.9 107.7 114.3 (2) 108.7 108.7 108.7 108.7 107.6 108.1 (4) 109.6 (3) 106.5 (3) 112.6 (3) 107.0 (3) 112.6 (3) 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5

Acta Cryst. (2013). C69, 1437-1447

C15—C16—H16C H16A—C16—H16C H16B—C16—H16C C15—C17—H17A C15—C17—H17B H17A—C17—H17B C15—C17—H17C H17A—C17—H17C H17B—C17—H17C C15—C18—H18A C15—C18—H18B H18A—C18—H18B C15—C18—H18C H18A—C18—H18C H18B—C18—H18C C22—C21—C24 C22—C21—C23 C24—C21—C23 C22—C21—P2 C24—C21—P2 C23—C21—P2 C21—C22—H22A C21—C22—H22B H22A—C22—H22B C21—C22—H22C H22A—C22—H22C H22B—C22—H22C C21—C23—H23A C21—C23—H23B H23A—C23—H23B C21—C23—H23C H23A—C23—H23C H23B—C23—H23C C21—C24—H24A C21—C24—H24B H24A—C24—H24B C21—C24—H24C H24A—C24—H24C H24B—C24—H24C C27—C25—C26 C27—C25—C28 C26—C25—C28 C27—C25—P2 C26—C25—P2 C28—C25—P2 C25—C26—H26A C25—C26—H26B

109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 108.5 (3) 108.0 (3) 107.4 (3) 112.9 (3) 108.0 (3) 111.9 (3) 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 108.3 (3) 106.6 (3) 109.5 (3) 107.8 (3) 113.8 (3) 110.6 (3) 109.5 109.5

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supplementary materials H13B—C13—H13C C11—C14—H14A C11—C14—H14B H14A—C14—H14B C11—C14—H14C H14A—C14—H14C H14B—C14—H14C C18—C15—C17 C18—C15—C16 C17—C15—C16 C18—C15—P1 C17—C15—P1 C16—C15—P1 C15—C16—H16A C15—C16—H16B H16A—C16—H16B

109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.3 (4) 107.6 (4) 106.9 (3) 108.8 (3) 112.8 (3) 111.3 (3) 109.5 109.5 109.5

H26A—C26—H26B C25—C26—H26C H26A—C26—H26C H26B—C26—H26C C25—C27—H27A C25—C27—H27B H27A—C27—H27B C25—C27—H27C H27A—C27—H27C H27B—C27—H27C C25—C28—H28A C25—C28—H28B H28A—C28—H28B C25—C28—H28C H28A—C28—H28C H28B—C28—H28C

109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5

P2—Ni1—P1—C9 I2—Ni1—P1—C9 I1—Ni1—P1—C9 P2—Ni1—P1—C11 I2—Ni1—P1—C11 I1—Ni1—P1—C11 P2—Ni1—P1—C15 I2—Ni1—P1—C15 I1—Ni1—P1—C15 P1—Ni1—P2—C10 I2—Ni1—P2—C10 I1—Ni1—P2—C10 P1—Ni1—P2—C25 I2—Ni1—P2—C25 I1—Ni1—P2—C25 P1—Ni1—P2—C21 I2—Ni1—P2—C21 I1—Ni1—P2—C21 C11—P1—C9—C10 C15—P1—C9—C10 Ni1—P1—C9—C10 P1—C9—C10—P2 C25—P2—C10—C9 C21—P2—C10—C9 Ni1—P2—C10—C9 C9—P1—C11—C12 C15—P1—C11—C12 Ni1—P1—C11—C12 C9—P1—C11—C13 C15—P1—C11—C13 Ni1—P1—C11—C13

7.78 (14) −158.66 (14) 110.72 (18) −105.39 (14) 88.17 (14) −2.4 (2) 123.03 (16) −43.41 (16) −134.03 (18) 8.05 (14) 106.49 (18) −157.93 (14) −105.07 (14) −6.6 (2) 88.94 (14) 123.67 (16) −137.90 (18) −42.32 (16) 88.5 (3) −157.2 (3) −26.2 (3) 35.0 (4) 88.4 (3) −157.6 (3) −26.7 (3) 55.1 (4) −52.0 (4) 168.8 (3) −63.6 (3) −170.7 (3) 50.1 (3)

C9—P1—C11—C14 C15—P1—C11—C14 Ni1—P1—C11—C14 C9—P1—C15—C18 C11—P1—C15—C18 Ni1—P1—C15—C18 C9—P1—C15—C17 C11—P1—C15—C17 Ni1—P1—C15—C17 C9—P1—C15—C16 C11—P1—C15—C16 Ni1—P1—C15—C16 C10—P2—C21—C22 C25—P2—C21—C22 Ni1—P2—C21—C22 C10—P2—C21—C24 C25—P2—C21—C24 Ni1—P2—C21—C24 C10—P2—C21—C23 C25—P2—C21—C23 Ni1—P2—C21—C23 C10—P2—C25—C27 C21—P2—C25—C27 Ni1—P2—C25—C27 C10—P2—C25—C26 C21—P2—C25—C26 Ni1—P2—C25—C26 C10—P2—C25—C28 C21—P2—C25—C28 Ni1—P2—C25—C28

179.7 (3) 72.5 (3) −66.6 (3) 84.3 (3) −164.8 (3) −34.0 (4) −154.2 (3) −43.3 (3) 87.5 (3) −34.1 (3) 76.9 (3) −152.3 (3) −156.1 (3) −45.2 (3) 85.7 (3) 83.9 (3) −165.1 (3) −34.3 (3) −34.1 (3) 76.9 (3) −152.2 (2) −57.3 (3) −164.9 (3) 56.1 (3) 62.8 (3) −44.8 (4) 176.3 (3) −173.5 (3) 78.9 (3) −60.0 (3)

Acta Cryst. (2013). C69, 1437-1447

sup-28

supplementary materials (lw29) [1,2-Bis(diphenylphosphanyl)ethane-κ2P,P′]diiodidonickel(II) dichloromethane monosolvate Crystal data Dx = 1.811 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 9238 reflections θ = 2.4–27.8° µ = 3.09 mm−1 T = 200 K Needle, violet 0.33 × 0.07 × 0.05 mm

[NiI2(C26H24P2)]·CH2Cl2 Mr = 795.83 Tetragonal, I41cd a = 26.3705 (17) Å c = 16.7900 (11) Å V = 11675.8 (17) Å3 Z = 16 F(000) = 6176 Data collection Bruker APEX diffractometer Radiation source: sealed tube φ and ω scans Absorption correction: multi-scan (SADABS; Sheldrick, 2008a) Tmin = 0.652, Tmax = 0.850 109821 measured reflections

7839 independent reflections 7131 reflections with I > 2σ(I) Rint = 0.063 θmax = 29.1°, θmin = 1.5° h = −36→36 k = −36→36 l = −22→22

Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.035 wR(F2) = 0.075 S = 1.04 7839 reflections 307 parameters 5 restraints Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained w = 1/[σ2(Fo2) + (0.0204P)2 + 71.4066P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.002 Δρmax = 1.32 e Å−3 Δρmin = −1.26 e Å−3 Absolute structure: Flack x determined using 3206 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004) Absolute structure parameter: −0.004 (7)

Special details Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

Ni1 I1 I2 P1 P2 C9 H9A H9B C10 H10A

x

y

z

Uiso*/Ueq

0.28453 (3) 0.23025 (2) 0.34232 (2) 0.33005 (6) 0.23797 (6) 0.2906 (3) 0.3120 0.2655 0.2640 (3) 0.2363

1.00312 (3) 1.05229 (2) 0.96692 (2) 0.96805 (6) 1.03270 (6) 0.9621 (3) 0.9539 0.9346 1.0122 (3) 1.0083

0.32327 (5) 0.42006 (3) 0.42855 (3) 0.23176 (10) 0.22710 (10) 0.1424 (4) 0.0956 0.1495 0.1299 (4) 0.0906

0.02110 (15) 0.03191 (10) 0.03574 (11) 0.0209 (3) 0.0222 (3) 0.0273 (14) 0.033* 0.033* 0.0275 (14) 0.033*

Acta Cryst. (2013). C69, 1437-1447

sup-29

supplementary materials H10B C11 C12 H12 C13 H13 C14 H14 C15 H15 C16 H16 C21 C22 H22 C23 H23 C24 H24 C25 H25 C26 H26 C31 C32 H32 C33 H33 C34 H34 C35 H35 C36 H36 C41 C42 H42 C43 H43 C44 H44 C45 H45 C46 H46 C51 H51A H51B Cl1

0.2883 0.3575 (3) 0.4077 (3) 0.4303 0.4251 (3) 0.4594 0.3932 (4) 0.4054 0.3430 (4) 0.3208 0.3259 (3) 0.2917 0.3806 (2) 0.3958 (3) 0.3814 0.4322 (3) 0.4423 0.4539 (3) 0.4791 0.4389 (3) 0.4536 0.4023 (3) 0.3923 0.1743 (3) 0.1382 (3) 0.1459 0.0915 (3) 0.0668 0.0803 (3) 0.0485 0.1161 (3) 0.1084 0.1624 (3) 0.1867 0.2344 (3) 0.1910 (3) 0.1614 0.1923 (4) 0.1626 0.2351 (4) 0.2349 0.2784 (4) 0.3082 0.2782 (3) 0.3081 0.1612 (7) 0.1651 0.1246 0.1907 (2)

Acta Cryst. (2013). C69, 1437-1447

1.0378 0.9055 (2) 0.8949 (3) 0.9217 0.8453 (3) 0.8381 0.8066 (3) 0.7727 0.8166 (3) 0.7899 0.8658 (3) 0.8729 1.0109 (2) 1.0497 (3) 1.0526 1.0845 (3) 1.1113 1.0798 (3) 1.1032 1.0419 (3) 1.0391 1.0069 (3) 0.9804 1.0062 (3) 1.0263 (3) 1.0556 1.0027 (4) 1.0164 0.9597 (3) 0.9433 0.9407 (3) 0.9116 0.9638 (3) 0.9501 1.1014 (3) 1.1283 (3) 1.1116 1.1809 (3) 1.2000 1.2059 (3) 1.2418 1.1790 (3) 1.1962 1.1266 (3) 1.1078 0.8227 (5) 0.7885 0.8309 0.8642 (2)

0.1096 0.2422 (4) 0.2251 (4) 0.2121 0.2269 (5) 0.2136 0.2478 (5) 0.2490 0.2671 (6) 0.2819 0.2645 (5) 0.2782 0.2024 (4) 0.2528 (4) 0.3044 0.2280 (5) 0.2623 0.1525 (5) 0.1355 0.1034 (5) 0.0519 0.1275 (4) 0.0926 0.2245 (4) 0.1712 (5) 0.1406 0.1641 (5) 0.1289 0.2074 (5) 0.2012 0.2600 (5) 0.2910 0.2676 (5) 0.3034 0.2191 (4) 0.2384 (5) 0.2569 0.2297 (6) 0.2408 0.2057 (6) 0.2010 0.1885 (6) 0.1717 0.1957 (5) 0.1846 0.1681 (10) 0.1445 0.1680 0.1089 (3)

0.033* 0.0257 (13) 0.0330 (15) 0.040* 0.0416 (19) 0.050* 0.046 (2) 0.055* 0.052 (2) 0.062* 0.0411 (18) 0.049* 0.0246 (13) 0.0345 (16) 0.041* 0.044 (2) 0.053* 0.045 (2) 0.053* 0.0423 (19) 0.051* 0.0331 (16) 0.040* 0.0269 (13) 0.0359 (15) 0.043* 0.0436 (18) 0.052* 0.045 (2) 0.054* 0.0414 (19) 0.050* 0.0323 (15) 0.039* 0.0274 (14) 0.0339 (16) 0.041* 0.051 (2) 0.061* 0.053 (2) 0.064* 0.048 (2) 0.058* 0.0362 (17) 0.043* 0.154 (7) 0.184* 0.184* 0.167 (3)

sup-30

supplementary materials Cl2

0.18145 (19)

0.81989 (16)

0.2668 (4)

0.144 (2)

Atomic displacement parameters (Å2)

Ni1 I1 I2 P1 P2 C9 C10 C11 C12 C13 C14 C15 C16 C21 C22 C23 C24 C25 C26 C31 C32 C33 C34 C35 C36 C41 C42 C43 C44 C45 C46 C51 Cl1 Cl2

U11

U22

U33

U12

U13

U23

0.0225 (4) 0.0372 (2) 0.0360 (2) 0.0208 (7) 0.0230 (8) 0.030 (3) 0.030 (3) 0.032 (3) 0.032 (4) 0.036 (4) 0.069 (6) 0.059 (6) 0.038 (4) 0.023 (3) 0.040 (4) 0.047 (5) 0.040 (4) 0.039 (4) 0.034 (4) 0.028 (3) 0.030 (3) 0.029 (3) 0.036 (4) 0.044 (5) 0.029 (4) 0.034 (4) 0.038 (4) 0.057 (6) 0.066 (6) 0.055 (5) 0.035 (4) 0.142 (15) 0.154 (4) 0.106 (3)

0.0240 (4) 0.0334 (2) 0.0478 (3) 0.0214 (7) 0.0241 (8) 0.029 (3) 0.037 (4) 0.021 (3) 0.031 (4) 0.044 (5) 0.026 (4) 0.029 (4) 0.027 (4) 0.024 (3) 0.036 (4) 0.043 (5) 0.048 (5) 0.052 (5) 0.038 (4) 0.029 (3) 0.044 (4) 0.064 (5) 0.051 (5) 0.039 (4) 0.033 (4) 0.026 (3) 0.026 (3) 0.031 (4) 0.027 (4) 0.034 (4) 0.028 (4) 0.051 (8) 0.197 (5) 0.076 (3)

0.0168 (3) 0.0251 (2) 0.0234 (2) 0.0204 (7) 0.0194 (7) 0.022 (3) 0.016 (3) 0.023 (3) 0.035 (4) 0.045 (4) 0.042 (4) 0.067 (6) 0.059 (5) 0.026 (3) 0.027 (3) 0.042 (4) 0.045 (5) 0.037 (4) 0.027 (3) 0.024 (3) 0.034 (4) 0.038 (4) 0.048 (5) 0.041 (4) 0.035 (4) 0.022 (3) 0.038 (4) 0.065 (6) 0.067 (6) 0.056 (6) 0.046 (5) 0.268 (16) 0.151 (4) 0.250 (6)

−0.0008 (3) 0.00113 (18) 0.0068 (2) −0.0004 (6) 0.0016 (6) 0.000 (3) 0.002 (3) −0.001 (3) 0.008 (3) 0.015 (3) 0.006 (4) −0.001 (4) −0.007 (3) 0.001 (2) −0.012 (3) −0.023 (4) −0.013 (4) −0.011 (4) −0.008 (3) −0.001 (3) −0.002 (3) 0.000 (4) −0.013 (4) −0.016 (4) −0.002 (3) 0.000 (3) 0.003 (3) 0.006 (4) −0.003 (4) −0.010 (4) −0.001 (3) −0.020 (8) −0.114 (4) 0.015 (2)

0.0018 (3) 0.00645 (19) −0.00453 (19) 0.0019 (6) 0.0007 (6) 0.004 (3) 0.002 (3) 0.001 (3) 0.003 (3) 0.001 (3) −0.012 (4) −0.009 (5) 0.005 (4) −0.002 (2) 0.002 (3) 0.001 (4) 0.000 (3) 0.006 (3) 0.009 (3) 0.005 (3) −0.004 (3) −0.006 (3) 0.009 (4) 0.009 (4) 0.004 (3) −0.005 (3) 0.002 (3) 0.007 (5) 0.009 (5) −0.004 (4) −0.003 (3) −0.074 (16) 0.066 (3) −0.009 (4)

−0.0008 (3) −0.00370 (19) 0.0015 (2) −0.0012 (6) −0.0006 (6) −0.007 (3) −0.002 (3) −0.001 (2) 0.004 (3) 0.001 (4) 0.000 (3) 0.001 (4) 0.001 (4) 0.002 (2) −0.001 (3) −0.003 (4) 0.015 (4) 0.010 (4) −0.003 (3) −0.004 (3) −0.004 (4) −0.009 (4) −0.022 (4) −0.006 (3) −0.001 (3) −0.002 (3) −0.001 (3) −0.004 (4) −0.002 (4) −0.001 (4) 0.003 (3) 0.017 (12) −0.106 (4) 0.053 (3)

Geometric parameters (Å, º) Ni1—P1 Ni1—P2 Ni1—I2 Ni1—I1 P1—C11 P1—C21 P1—C9 P2—C41

Acta Cryst. (2013). C69, 1437-1447

2.1582 (18) 2.1733 (18) 2.5216 (9) 2.5240 (9) 1.811 (7) 1.816 (7) 1.832 (7) 1.818 (7)

C24—C25 C24—H24 C25—C26 C25—H25 C26—H26 C31—C36 C31—C32 C32—C33

1.353 (12) 0.9500 1.395 (10) 0.9500 0.9500 1.368 (10) 1.408 (10) 1.385 (10)

sup-31

supplementary materials P2—C31 P2—C10 C9—C10 C9—H9A C9—H9B C10—H10A C10—H10B C11—C12 C11—C16 C12—C13 C12—H12 C13—C14 C13—H13 C14—C15 C14—H14 C15—C16 C15—H15 C16—H16 C21—C26 C21—C22 C22—C23 C22—H22 C23—C24 C23—H23

1.820 (7) 1.851 (6) 1.512 (9) 0.9900 0.9900 0.9900 0.9900 1.383 (10) 1.387 (10) 1.388 (10) 0.9500 1.370 (12) 0.9500 1.387 (13) 0.9500 1.375 (11) 0.9500 0.9500 1.385 (9) 1.388 (10) 1.390 (10) 0.9500 1.397 (12) 0.9500

C32—H32 C33—C34 C33—H33 C34—C35 C34—H34 C35—C36 C35—H35 C36—H36 C41—C42 C41—C46 C42—C43 C42—H42 C43—C44 C43—H43 C44—C45 C44—H44 C45—C46 C45—H45 C46—H46 C51—Cl1 C51—Cl2 C51—H51A C51—H51B

0.9500 1.379 (13) 0.9500 1.385 (13) 0.9500 1.372 (10) 0.9500 0.9500 1.385 (10) 1.389 (10) 1.394 (11) 0.9500 1.365 (13) 0.9500 1.375 (13) 0.9500 1.387 (11) 0.9500 0.9500 1.670 (14) 1.743 (15) 0.9900 0.9900

P1—Ni1—P2 P1—Ni1—I2 P2—Ni1—I2 P1—Ni1—I1 P2—Ni1—I1 I2—Ni1—I1 C11—P1—C21 C11—P1—C9 C21—P1—C9 C11—P1—Ni1 C21—P1—Ni1 C9—P1—Ni1 C41—P2—C31 C41—P2—C10 C31—P2—C10 C41—P2—Ni1 C31—P2—Ni1 C10—P2—Ni1 C10—C9—P1 C10—C9—H9A P1—C9—H9A C10—C9—H9B P1—C9—H9B H9A—C9—H9B

86.51 (7) 90.04 (5) 176.51 (6) 173.72 (6) 88.49 (5) 94.93 (3) 107.5 (3) 103.1 (3) 104.3 (3) 123.0 (2) 109.6 (2) 107.7 (2) 109.4 (3) 104.2 (3) 102.1 (3) 116.2 (2) 113.7 (2) 109.9 (2) 107.5 (4) 110.2 110.2 110.2 110.2 108.5

C22—C23—C24 C22—C23—H23 C24—C23—H23 C25—C24—C23 C25—C24—H24 C23—C24—H24 C24—C25—C26 C24—C25—H25 C26—C25—H25 C21—C26—C25 C21—C26—H26 C25—C26—H26 C36—C31—C32 C36—C31—P2 C32—C31—P2 C33—C32—C31 C33—C32—H32 C31—C32—H32 C34—C33—C32 C34—C33—H33 C32—C33—H33 C33—C34—C35 C33—C34—H34 C35—C34—H34

119.7 (8) 120.1 120.1 119.9 (8) 120.0 120.0 120.9 (8) 119.6 119.6 120.0 (7) 120.0 120.0 119.3 (7) 120.8 (6) 119.6 (5) 119.1 (8) 120.4 120.4 120.9 (8) 119.5 119.5 119.1 (7) 120.4 120.4

Acta Cryst. (2013). C69, 1437-1447

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supplementary materials C9—C10—P2 C9—C10—H10A P2—C10—H10A C9—C10—H10B P2—C10—H10B H10A—C10—H10B C12—C11—C16 C12—C11—P1 C16—C11—P1 C11—C12—C13 C11—C12—H12 C13—C12—H12 C14—C13—C12 C14—C13—H13 C12—C13—H13 C13—C14—C15 C13—C14—H14 C15—C14—H14 C16—C15—C14 C16—C15—H15 C14—C15—H15 C15—C16—C11 C15—C16—H16 C11—C16—H16 C26—C21—C22 C26—C21—P1 C22—C21—P1 C21—C22—C23 C21—C22—H22 C23—C22—H22

107.8 (4) 110.1 110.1 110.1 110.1 108.5 118.6 (7) 123.1 (5) 118.2 (6) 120.1 (7) 119.9 119.9 120.3 (8) 119.8 119.8 120.3 (8) 119.9 119.9 119.1 (8) 120.5 120.5 121.5 (8) 119.2 119.2 119.3 (7) 120.2 (5) 120.4 (5) 120.3 (7) 119.9 119.9

C36—C35—C34 C36—C35—H35 C34—C35—H35 C31—C36—C35 C31—C36—H36 C35—C36—H36 C42—C41—C46 C42—C41—P2 C46—C41—P2 C41—C42—C43 C41—C42—H42 C43—C42—H42 C44—C43—C42 C44—C43—H43 C42—C43—H43 C43—C44—C45 C43—C44—H44 C45—C44—H44 C44—C45—C46 C44—C45—H45 C46—C45—H45 C45—C46—C41 C45—C46—H46 C41—C46—H46 Cl1—C51—Cl2 Cl1—C51—H51A Cl2—C51—H51A Cl1—C51—H51B Cl2—C51—H51B H51A—C51—H51B

120.4 (8) 119.8 119.8 121.1 (7) 119.4 119.4 120.4 (7) 122.5 (6) 117.0 (5) 117.8 (8) 121.1 121.1 122.0 (9) 119.0 119.0 119.9 (8) 120.0 120.0 119.4 (8) 120.3 120.3 120.3 (8) 119.8 119.8 116.9 (9) 108.1 108.1 108.1 108.1 107.3

C11—P1—C9—C10 C21—P1—C9—C10 Ni1—P1—C9—C10 P1—C9—C10—P2 C41—P2—C10—C9 C31—P2—C10—C9 Ni1—P2—C10—C9 C21—P1—C11—C12 C9—P1—C11—C12 Ni1—P1—C11—C12 C21—P1—C11—C16 C9—P1—C11—C16 Ni1—P1—C11—C16 C16—C11—C12—C13 P1—C11—C12—C13 C11—C12—C13—C14 C12—C13—C14—C15 C13—C14—C15—C16

177.8 (5) −70.0 (5) 46.4 (5) −46.2 (5) 154.2 (5) −92.0 (5) 29.0 (5) −3.4 (7) 106.5 (6) −131.9 (5) −180.0 (6) −70.1 (6) 51.5 (7) 2.9 (11) −173.7 (6) −1.8 (13) 0.2 (13) 0.4 (14)

C22—C21—C26—C25 P1—C21—C26—C25 C24—C25—C26—C21 C41—P2—C31—C36 C10—P2—C31—C36 Ni1—P2—C31—C36 C41—P2—C31—C32 C10—P2—C31—C32 Ni1—P2—C31—C32 C36—C31—C32—C33 P2—C31—C32—C33 C31—C32—C33—C34 C32—C33—C34—C35 C33—C34—C35—C36 C32—C31—C36—C35 P2—C31—C36—C35 C34—C35—C36—C31 C31—P2—C41—C42

−0.2 (11) 176.0 (6) 0.3 (13) −146.0 (6) 104.1 (6) −14.2 (6) 40.9 (7) −69.1 (6) 172.6 (5) 0.4 (11) 173.7 (6) −1.0 (12) 1.5 (13) −1.4 (12) −0.3 (11) −173.5 (6) 0.8 (12) 22.0 (7)

Acta Cryst. (2013). C69, 1437-1447

sup-33

supplementary materials C14—C15—C16—C11 C12—C11—C16—C15 P1—C11—C16—C15 C11—P1—C21—C26 C9—P1—C21—C26 Ni1—P1—C21—C26 C11—P1—C21—C22 C9—P1—C21—C22 Ni1—P1—C21—C22 C26—C21—C22—C23 P1—C21—C22—C23 C21—C22—C23—C24 C22—C23—C24—C25 C23—C24—C25—C26

0.7 (14) −2.3 (13) 174.4 (7) 68.9 (6) −40.2 (6) −155.3 (5) −114.9 (6) 136.0 (6) 20.9 (6) 0.5 (12) −175.8 (6) −0.8 (13) 0.8 (14) −0.6 (14)

C10—P2—C41—C42 Ni1—P2—C41—C42 C31—P2—C41—C46 C10—P2—C41—C46 Ni1—P2—C41—C46 C46—C41—C42—C43 P2—C41—C42—C43 C41—C42—C43—C44 C42—C43—C44—C45 C43—C44—C45—C46 C44—C45—C46—C41 C42—C41—C46—C45 P2—C41—C46—C45

130.5 (6) −108.4 (6) −160.8 (5) −52.3 (6) 68.8 (6) 3.1 (11) −179.7 (6) −2.3 (14) 0.8 (16) −0.1 (15) 0.9 (13) −2.5 (11) −179.8 (6)

Important bond lengths (Å) and angles (°) for (dtbpe-κ2P)NiX2 and (dppe-κ2P)NiI2.2H2O. Computed values (BP86/def2TZVP) are given in italics. The calculated values are for the P conformation in all cases although for the dtbpe diiodide this is not the global minimum, as described in the text. Ligands

dtbpeCl (with CHCl3)

Ni—P1 (Å) 2.205 (1) Ni—P2 (Å) 2.199 (1) Ni—X1 (Å) 2.215 (1) Ni—X2 (Å) 2.200 (1) P1—Ni— 90.95 (4) P2 (°) X1—Ni— 89.47 (4) X2 (°) Mean of P···P···X···X 2.3 torsion angles (°)

dtbpeCl (solventfree)a 2.197 (1); 2.197 (1) 2.202 (1); 2.204 (1) 2.194 (1); 2.202 (1) 2.209 (1); 2.212 (1) 90.95 (4); 90.82 (4) 90.47 (4); 91.16 (4) 9.5; -5.7

dtbpeCl

dtbpeBr

dtbpeBr

dtbpeI

dtbpeI

dppeI

dppeI

2.191

2.237 (2)

2.206

2.238 (1)

2.225

2.160 (2)

2.163

2.191

2.211 (2)

2.206

2.239 (1)

2.225

2.173 (2)

2.163

2.216

2.363 (1)

2.368

2.563 (1)

2.564

2.5243 (9) 2.542

2.216

2.357 (1)

2.368

2.538 (1)

2.564

2.522 (1)

2.542

92.9

90.01 (6)

92.7

90.3 (1)

91.9

86.49 (7)

89.2

91.2

89.76 (4)

89.8

88.51 (2)

88.8

94.93 (3)

94.9

4.7

19.2

9.0

19.7

24.3

2.2

2.8

Note: (a) data for two chemically equivalent but crystallographically unique molecules in the asymmetric unit.

λmax values for (dtbpe-κ2P)NiX2 (X = Cl, Br, I) in solution and the solid state (nm). Extinction coefficients (M-1 cm-1) for the solution spectra are provided in parentheses. Compound (dtbpe-κ2P)NiCl2 (dtbpe-κ2P)NiCl2 (dtbpe-κ2P)NiBr2 (dtbpe-κ2P)NiBr2 (dtbpe-κ2P)NiI2 (dtbpe-κ2P)NiI2

Form solution solid solution solid solution solid

Acta Cryst. (2013). C69, 1437-1447

λmax (ε) 351 (1800) 323 417 (340) 425 391 (3050) 396

λmax (ε) 495 (790) 491 523 (420) 550 606 (817) 602

Colour bright red bright red maroon maroon blue-green deep green

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supplementary materials 31

P{1H} chemical shift and ν1/2 as a function of temperature.

(dtbpe-κ2P)NiCl2 in CDCl2CDCl2 Temperature (K) 243 Peak position (δ) 86 Peak width at half 20 height (Hz) (dtbpe-κ2P)NiBr2 in CD2Cl2 Temperature (K) 223 Peak position (δ) 93.4 Peak width at half 30 height (Hz)

298 88

313 92

333 103

353 123

120

210

300

480

253 94.2

273 97.5

298 109

313 124

120

230

480

700

Comparison of calculated and observed λmax values to which the colour of the complex is attributed (nm). The calculated absorption for a molecule that is restricted to a planar geometry is given in parentheses.

Calculated P Calculated O Observed (solution)

(dtbpe-κ2P)NiCl2 505 (505) 506 (505) 495

(dtbpe-κ2P)NiBr2 530 (529) 535 (527) 523

(dtbpe-κ2P)NiI2 582 (562) 580 (559) 606

Comparison of reported solution λmax and calculated (B3LYP/def2-TVPP//BP86/def2-TZVP) values for nickel halide complexes bearing phenyl-substituted bis(phosphine) ligands. Values for which the ground-state structure has been optimized with Grimme's empirical dispersion correction are given in parentheses. Complex (dppe-κ2P)NiCl2 (dppe-κ2P)NiBr2 (dppe-κ2P)NiI2 (dppp-κ2P)NiCl2 (dppp-κ2P)NiBr2 (dppp-κ2P)NiI2

Reported (van Hecke & Horrocks, 19669997) 463 481 521 470 490 559a

Calculated 488 (459) 506 (493) 536 (529) 490 515 550

Note: (a) in solution, this complex undergoes a square-planar–tetrahedral equilibrium so the observed value for the square-planar complex as a Nujol mull has been used (van Hecke & Horrocks, 19667).

Acta Cryst. (2013). C69, 1437-1447

sup-35

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Structure, magnetism and colour in simple bis(phosphine)nickel(II) dihalide complexes: an experimental and theoretical investigation.

The complex [1,2-bis(di-tert-butylphosphanyl)ethane-κ(2)P,P']diiodidonickel(II), [NiI2(C18H40P2] or (dtbpe-κ(2)P)NiI2, [dtbpe is 1,2-bis(di-tert-butyl...
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