research papers
ISSN 2052-5206
Synthesis and structural elucidation of new complexes of 2,4- and 3,5-dimethyl diphenyldithiophosphates with cobalt(II) Sandeep Kumar,a Ruchi Khajuria,a Amanpreet Kaur Jassal,b Maninder S. Hundalb and Sushil K. Pandeya*
Received 26 November 2014 Accepted 25 February 2015
Edited by N. B. Bolotina, Russian Academy of Sciences, Russia Keywords: diphenyldithiophosphate; chromophore; donor stabilized. CCDC references: 1051253; 1051254; 1051255; 1051256 Supporting information: this article has supporting information at journals.iucr.org/b
a
Department of Chemistry, University of Jammu, Jammu 180 006, India, and bDepartment of Chemistry, Guru Nanak Dev University, Amritsar 143 005, India. *Correspondence e-mail: [email protected]
A new series of donor-stabilized addition complexes of cobalt(II) with disubstituted diphenyldithiophosphates [{(ArO)2PS2}2CoL2] {Ar = 2,4(CH3)2C6H3 [(1)–(3)] and 3,5-(CH3)2C6H3 [(4)–(6)]; L = C5H5N [(1), (4)], 3,4(CH3)2C5H3N [(2), (5)] and 4-(C2H5)C5H4N [(3), (6)]} were successfully isolated and characterized by elemental analyses, magnetic moment measurements, IR and single-crystal X-ray analysis. Complexes (3), (4) and (5) crystallize in the monoclinic space groups P21/n, P21/n and P21/c, respectively, whereas complex (6) crystallizes in the triclinic space group P1 . X-ray diffraction analysis of complexes (3)–(6) reveals a six-coordinated distorted octahedral geometry for the CoS4N2 chromophore defined by two chelating diphenyldithiophosphate anions as well as two N-donor ligands. Two diphenyldithiophosphate ligands are coordinated to the cobalt ion as a bidentate ligand chelating via the two thiolate S atoms. Each of them forms a four-membered chelate ring in the equatorial plane. The N atoms from two donor ligands are axially coordinated to the Co atom in a mutually trans position.
1. Introduction
# 2015 International Union of Crystallography
Acta Cryst. (2015). B71, 221–227
Transition metal sulfides have received great attention in the field of material science because of their thermoelectric and photoelectric properties, and many other potential applications (Pan et al., 2013). The chemistry of dithiophosphate complexes of transition metals continues to be of great interest because of their striking structural features and diversified applications. The dithiophosphato derivatives of transition metals find extensive applications in lubrication engineering (So et al., 1993) and plastic industries (Kim et al., 2010). Cobalt dithiophosphates are known to have a significant antiwear effect on chrome alloy steel compared with the other metallic dithiophosphates. Also, cobalt dithiophosphates have a characteristic property of thermal sensitivity in color which is shown by a color change from brown to blue over a certain temperature (Moon & Kwon, 1979). The 1,1dithiolate ligands are versatile in nature and coordination complexes with cobalt have been reported in the literature (Cavell et al., 1972; Hoskins & Williams, 1975; Hoskins et al., 1976; Jørgensen, 1962; Lebedda & Palmer, 1971; Malatesta & Pizzotti, 1945; Micu-Semeniuc et al., 1979; Tripathi & Singh, 1999; Yamada et al., 1978). In these complexes, the dithiophosphate ligand moieties are normally bidentate. X-ray crystal structures have been reported for a number of cobalt complexes with dialkyl dithiophosphates including Co[S2P(OMe)2]3 (McConnell & Schwartz, 1972), Co[S2P(OPri)2]3 (Zu et al., 2002), [Co{S2P(OMe)2}2PPh3] http://dx.doi.org/10.1107/S205252061500390X
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research papers (Shimoi et al., 1979), [NMe4][CoCl{S2P(OMe)2}2] (Kirschbaum et al., 1990), Co[S2P(OEt)2]30.5H2O (Sheng-Zhi, 1999), [Co{S2P(OEt)2}2(C5H5N)2] (Xu et al., 1989), [Co{S2P(OCy)2}2(C5H5N)2] (He et al., 2002) and [Co{S2P(OEt)2}2(C24H26O2N4)] (Williams & Robson, 1981). There are also some reports available on the adducts of alkylene dithiphosphates of cobalt(II) (Bajia, Butcher et al., 2009). Cobalt dithiophosphate complexes with nitrogen- or phosphoruscontaining Lewis bases display distorted trigonal bipyramidal or octahedral geometry around the central metal atom. In the trigonal bipyramidal geometry, the dithiophosphate moieties chelate axially and equatorially to the cobalt (Shimoi et al., 1982), usually with the hetero-atom of the Lewis base on the equatorial plane (Shimoi et al., 1982). However, adducts of cobalt(II) with analogous aromatic ligands have been less studied (Bajia, Drake et al., 2009) and a literature survey reveals that there is no report available on donor-stabilized complexes of cobalt(II) with disubstituted diphenyldithiophosphates. Continuing our interest in various dithiophosphate ligands (Khajuria et al., 2014; Kumar, Khajuria, Gupta et al., 2014; Kumar, Khajuria, Jassal et al., 2014) led us to work on the reactions of addition complexes of cobalt(II) diphenyldithiophosphate with nitrogen donor moieties to study the influence of different donor ligands on the cobalt(II) diphenyldithiophosphate complexes. Thus, we report here on the synthesis, spectroscopic and single-crystal X-ray analysis of addition complexes of cobalt(II) 2,4- and 3,5-dimethyl diphenyldithiophosphates with N donor ligands.
2. Experimental 2.1. Materials and instrumentation
Solvents were distilled and dried using standard methods before use. Chloroform (Thomas Baker, b.p. 334 K) was dried over P2O5. All the disubstituted phenols were procured from Sigma Aldrich and used without purification. The sodium salts of disubstituted O,O0 -diphenyldithiophosphate, i.e. {(2,4CH3)2C6H3O}2PS2Na and {(3,5-CH3)2C6H3O}2PS2Na, were synthesized according to a literature procedure (Khajuria et al., 2014). Moisture was carefully excluded for the synthesis of ligands throughout the experimental manipulations by using standard Schlenk techniques. Cobalt was estimated using the pyridine thiocyanate method (Vogel, 1991). Elemental analyses (C, H, N, S) were conducted using the Vario EL-III elemental analyser (Indian Institute of Integrative Medicine, Jammu). IR spectra were recorded in the range 4000–340 cm1 on a Shimadzu FT–IR spectrophotometer (Department of Chemistry, University of Jammu, India).
Purple-colored solid precipitates were formed immediately. After 30 min of stirring at room temperature the reaction contents were filtered using a sintered glass disk to obtain the complex [{(2,4-CH3)2C6H3O}2PS2]2Co(C5H5N)2 (1) as a purple powdery solid. The complex was recrystallized from a chloroform/n-hexane (3:1) mixture at room temperature. Yield: 91%; m.p. 397–399 K (dec). Anal.: calc. for C42H46N2O4P2S4Co: C 56.55, H 5.20, S 14.38, N 3.14, Co 6.61; found: C 56.52, H 5.15, S 14.34, N 3.10, Co 6.54. IR (KBr): 1609 m [C—N], 1120 s [(P)—O—C], 885 s [P—O—(C)], 680 s [P—S]asym, 595 m [P—S]sym, 444 w [Co—S], 359 w [Co—N] cm1; eff = 5.0 B.M. 2.2.2. [{(2,4-CH3)2C6H3O}2PS2]2Co{3,4-(CH3)2C5H3N}2 (2). Compound (2) was obtained as a purple solid by a
similar procedure as described for compound (1) using Co(NO3)26H2O (0.20 g, 0.68 mmol), 3,4-dimethylpyridine (0.147 g, 1.37 mmol) and {(2,4-CH3)2C6H3O}2PS2Na (0.50 g, 1.38 mmol). The resulting solid was recrystallized from a chloroform/n-hexane mixture at room temperature. Yield: 89%; m.p. 395398 K (dec.). Anal.: calc. for C46H54N2O4P2S4Co: C 56.28, H 5.74, S 13.53, N 2.95, Co 6.22; found: C 56.22, H 5.68, S 13.47, N 2.90, Co 6.17. IR (KBr): 1598 m [C—N], 1130 s [(P)—O—C], 875 s [P—O—(C)], 680 s [P—S]asym, 584 m [P—S]sym, 420 w [Co—S], 362 w [Co—N] cm1; eff = 4.9 B.M. 2.2.3. [{(2,4-CH3)2C6H3O}2PS2]2Co{4-(C2H5)C5H4N}2 (3). Compound (3) was obtained as a purple solid by a similar procedure as described for compound (1) using Co(NO3)26H2O (0.20 g, 0.68 mmol), 4-ethylpyridine (0.147 g, (0.50 g, 1.37 mmol) and {(2,4-CH3)2C6H3O}2PS2Na 1.38 mmol). The resulting solid was recrystallized from a chloroform/n-hexane mixture at room temperature. Yield: 92%; m.p. 393395 K (dec). Anal.: calc. for C46H54N2O4P2S4Co: C 56.28, H 5.74, S 13.53, N 2.95, Co 6.22; found: C 56.24, H 5.69, S 13.49, N 2.92, Co 6.19. IR (KBr): 1615 m [C—N], 1116 s [(P)—O—C], 890 s [P—O—(C)], 691 s [P—S]asym, 588 m [P—S]sym, 435 w [Co—S], 345 w [Co—N] cm1; eff = 5.2 B.M. 2.2.4. [{(3,5-CH3)2C6H3O}2PS2]2Co(C5H5N)2 (4). Complex (4) was obtained as a purple solid by a similar procedure to that described for complex (1) using Co(NO3)26H2O (0.20 g, 0.68 mmol), pyridine (0.147 g, 1.37 mmol) and {(3,5CH3)2C6H3O}2PS2Na (0.50 g, 1.38 mmol). The resulting solid was recrystallized from a chloroform/n-hexane mixture at room temperature. Yield 92%; m.p. 411413 K (dec.). Anal.: calc. for C42H46N2O4P2S4Co: C 56.55, H 5.20, S 14.38, N 3.14, Co 6.61; found: C 56.49, H 5.17, S 14.32, N 3.11, Co 6.57. IR (KBr): 1612 m [C—N], 1126 s [(P)—O—C], 889 s [P—O— (C)], 675 s [P—S]asym, 592 m [P—S]sym, 432 w [Co—S], 352 w [Co—N] cm1; eff = 4.9 B.M.
2.2. Synthesis
2.2.5. [{(3,5-CH3)2C6H3O}2PS2]2Co{3,4-(CH3)2C5H3N}2 (5). Complex (5) was obtained as a purple solid by a similar
2.2.1. [{(2,4-CH3)2C6H3O}2PS2]2Co(C5H5N)2 (1). To a stirred aqueous solution of Co(NO3)26H2O (0.20 g, 0.68 mmol) was added pyridine (0.108 g, 1.37 mmol), followed by the addition of an aqueous solution (10 ml) of {(2,4CH3)2C6H3O}2PS2Na (0.50 g, 1.38 mmol) in a 1:2 molar ratio.
procedure to that described for complex (1) using Co(NO3)26H2O (0.20 g, 0.68 mmol), 3,4–dimethylpyridine (0.147 g, 1.37 mmol) and {(3,5-CH3)2C6H3O}2PS2Na (0.50 g, 1.38 mmol). The resulting solid was recrystallized from a chloroform/n-hexane mixture at room temperature. Yield:
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Acta Cryst. (2015). B71, 221–227
research papers Table 1 Summary of the crystal structure, data collection and structure refinement parameters for complexes (3)–(6). Experiments were carried out at 296 K with Mo K radiation. (3)
(4)
(5)
(6)
, , ( )
C46H54CoN2O4P2S4 948.06 Monoclinic, P21/n 10.254 (3), 15.557 (5), 15.444 (6) 90, 102.287 (5), 90
C42H46CoN2O4P2S4 891.96 Monoclinic, P21/n 11.8107 (6), 14.4211 (9), 12.8807 (7) 90, 104.929 (2), 90
C46H54CoN2O4P2S4 948.06 Monoclinic, P21/c 8.0404 (7), 16.3777 (13), 18.9182 (14) 90, 98.074 (4), 90
˚ 3) V (A Z (mm1) Crystal size (mm)
2407.2 (14) 2 0.64 0.15 0.12 0.08
2119.8 (2) 2 0.72 0.10 0.07 0.05
2466.5 (3) 2 0.62 0.12 0.09 0.06
C46H54CoN2O4P2S4 948.06 Triclinic, P1 9.5631 (7), 9.8309 (6), 14.2326 (9) 99.290 (3), 98.602 (3), 112.994 (3) 1181.83 (14) 1 0.65 0.12 0.09 0.06
Bruker APEXII CCD Multi-scan 0.626, 0.746 19 203, 5308, 3263
Bruker APEXII CCD Multi-scan 0.648, 0.746 22 789, 6024, 5025
Bruker APEXII CCD Multi-scan 0.637, 0.746 21 225, 5402, 4132
Bruker APEXII CCD Multi-scan 0.650, 0.746 24 294, 5258, 3991
0.066 0.649
0.020 0.701
0.040 0.640
0.042 0.643
0.073, 0.256, 1.01 5308 273 1 0.66, 0.58
0.030, 0.087, 1.03 6024 254 0 0.31, 0.28
0.036, 0.106, 0.93 5402 274 0 0.25, 0.36
0.036, 0.092, 1.04 5258 273 0 0.33, 0.23
Crystal data Chemical formula Mr Crystal system, space group ˚) a, b, c (A
Data collection Diffractometer Absorption correction Tmin, Tmax No. of measured, independent and observed [I > 2(I)] reflections Rint ˚ 1) (sin /)max (A Refinement R[F2 > 2(F2)], wR(F2), S No. of reflections No. of parameters No. of restraints ˚ 3) max, min (e A
Computer programs: Bruker APEX2, Bruker SAINT, SIR92 (Altomare et al., 1993), SHELXL2014, SHELXL97 (Sheldrick, 2008), SHELXTL (Bruker, 2003).
90%; m.p. 408411 K (dec.). Anal.: calc. for C46H54N2O4P2S4Co: C 56.28, H 5.74, S 13.53, N 2.95, Co 6.22; found: C 56.25, H 5.70, S 13.51, N 2.88, Co 6.16. IR (KBr): 1612 m [C— N], 1134 s [(P)—O—C], 852 s [P—O—(C)], 684 s [P— S]asym, 578 m [P—S]sym, 424 w [Co—S], 356 w [Co—N] cm1; eff = 5.2 B.M. 2.2.6. [{(3,5-CH3)2C6H3O}2PS2]2Co{4-(C2H5)C5H4N}2 (6). Complex (6) was obtained as a purple solid by a similar procedure to that described for complex (1) using Co(NO3)26H2O (0.20 g, 0.68 mmol), 4-ethylpyridine (0.147 g, (0.50 g, 1.37 mmol) and {(3,5-CH3)2C6H3O}2PS2Na 1.38 mmol). The resulting solid was recrystallized from a chloroform/n-hexane mixture at room temperature. Yield: 92%; m.p. 401–404 K (dec.). Anal.: calc. for C46H54N2O4P2S4Co: C 56.28, H 5.74, S 13.53, N 2.95, Co 6.22; found: C 56.23, H 5.67, S 13.46, N 2.90, Co 6.20. IR (KBr): 1614 m [C— N], 1132 s [(P)—O—C], 883 s [P—O—(C)], 686 s [P— S]asym, 592 m [P—S]sym, 457 w [Co—S], 347 w [Co—N] cm1; eff = 5.1 B.M. 2.3. Crystallography data collection and refinement
Crystallization of complexes (3)–(6) was executed by very slow evaporation of their saturated solution in chloroform/nhexane mixture (3:1) at room temperature yielding suitable purple colored and rectangular shaped single crystals for Xray analysis. X-ray data of complexes (3)–(6) were collected Acta Cryst. (2015). B71, 221–227
on a Bruker APEXII CCD diffractometer (Department of Chemistry, Guru Nanak Dev University, Amritsar, India) ˚ ) at room temperature. The data using Mo K ( = 0.71069 A were processed by SAINT correcting for Lorentz and polarization effects. An empirical absorption correction was applied using SADABS from Bruker. The solution was obtained by direct methods, using SIR92 (Altomare et al., 1993) and refined by full-matrix least-squares refinement methods (Sheldrick, 2008) based on F2, using SHELX97. All non-H atoms were refined anisotropically. All calculations were performed using the WinGX package (Farrugia, 1999). Molecular drawings were obtained using DIAMOND, Version 2.1 (Brandenburg, 1998). Crystallographic data, details of the data collection, structure solution and refinements are listed in Table 1.
3. Results and discussion Donor-stabilized addition complexes of cobalt(II) with disubstituted diphenyldithiophosphates were prepared by the reaction of an aqueous solution of Co(NO3)26H2O and Lewis bases followed by the addition of a 1:2 stiochiometric amount of [{(ArO)2PS2Na] according to the scheme below. The precipitated purple solid complexes were separated by filtration and repeatedly washed with water. These complexes were found to be soluble in all common organic solvents.
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research papers Table 2
Table 4
˚ ) and angles ( ) for complex (3). Selected bonds lengths (A
˚ ) and angles ( ) for complex (5). Selected bonds lengths (A
Co1—S1 Co1—S2 P1—O1 P1—O2 P1—S2
2.5026 (13) 2.5425 (13) 1.608 (3) 1.602 (3) 1.9696 (17)
P1—S1 Co1—N1i Co1—S1i Co1—S2i
1.9702 (17) 2.168 (4) 2.5026 (13) 2.5425 (13)
O2—P1—S2 O1—P1—S2 O2—P1—S1 O1—P1—S1 S2—P1—S1 P1—S1—Co1 P1—S2—Co1 N1—Co1—N1i N1—Co1—S1 N1i—Co1—S1 N1—Co1—S1i
106.42 (14) 113.65 (14) 114.25 (14) 110.51 (13) 112.98 (7) 83.15 (5) 82.11 (5) 179.999 (1) 90.52 (10) 89.48 (10) 89.48 (10)
N1i—Co1—S1i S1—Co1—S1i N1—Co1—S2 N1i—Co1—S2 S1—Co1—S2 S1i—Co1—S2 N1—Co1—S2i N1i—Co1—S2i S1—Co1—S2i S1i—Co1—S2i S2—Co1—S2i
90.52 (10) 180.0 89.73 (10) 90.27 (10) 81.25 (4) 98.75 (4) 90.27 (10) 89.73 (10) 98.75 (4) 81.25 (4) 180.0
Symmetry code: (i) x þ 1; y; z þ 1.
Co1—S1 Co1—S2 P1—O1 P1—O2 P1—S2i P1—S1
2.5123 (6) 2.5520 (5) 1.6013 (15) 1.6068 (15) 1.9629 (7) 1.9709 (7)
P1i—S2 Co1—N1i Co1—N1 Co1—S1i Co1—S2i
1.9630 (7) 2.1522 (16) 2.1521 (16) 2.5123 (6) 2.5521 (5)
O1—P1—O2 O1—P1—S2i O2—P1—S2i O1—P1—S1 O2—P1—S1 S2i—P1—S1 P1—S1—Co1 P1i—S2—Co1 N1—Co1—N1i N1—Co1—S1i N1i—Co1—S1i N1—Co1—S1
97.64 (8) 108.12 (6) 111.58 (6) 111.97 (6) 111.55 (6) 114.68 (3) 82.12 (2) 81.23 (2) 180.00 (5) 88.68 (5) 91.32 (5) 91.32 (5)
N1i—Co1—S1 S1i—Co1—S1 N1—Co1—S2 N1i—Co1—S2 S1i—Co1—S2 S1—Co1—S2 N1—Co1—S2i N1i—Co1—S2i S1i—Co1—S2i S1—Co1—S2i S2—Co1—S2i
88.68 (5) 180.0 91.23 (4) 88.77 (4) 81.673 (16) 98.326 (16) 88.77 (4) 91.23 (4) 98.328 (16) 81.673 (16) 180.0
Symmetry code: (i) x þ 1; y; z.
Table 3 ˚ ) and angles ( ) for complex (4). Selected bonds lengths (A Co1—S1 Co1—S2 P1—O1 P1—O2 P1—S1
2.5708 (4) 2.5065 (4) 1.5954 (11) 1.5966 (11) 1.9721 (5)
P1—S2 Co1—N1i Co1—N1 Co1—S2i Co1—S1i
1.9748 (5) 2.1827 (12) 2.1827 (12) 2.5065 (4) 2.5708 (4)
P1—S1—Co1 P1—S2—Co1 S1—P1—S2 O1—P1—S1 O1—P1—S2 O1—P1—O2 O2—P1—S1 O2—P1—S2 N1—Co1—S2i N1i—Co1—S2 N1—Co1—S2 N1i—Co1—N1
80.956 (17) 82.582 (16) 112.52 (2) 113.68 (5) 106.15 (5) 98.03 (6) 112.19 (5) 113.31 (5) 90.89 (3) 90.89 (3) 89.11 (3) 180.0
S2i—Co1—S1 S2—Co1—S1 S2i—Co1—S1i S2—Co1—S1i S2i—Co1—S2 N1i—Co1—S1 N1—Co1—S1 N1i—Co1—S1i N1—Co1—S1i N1i—Co1—S2i S1—Co1—S1i
99.465 (13) 80.536 (13) 80.536 (13) 99.464 (13) 180.0 88.56 (3) 91.44 (3) 91.44 (3) 88.56 (3) 89.11 (3) 180.0
Symmetry code: (i) x þ 1; y; z þ 2.
Table 5 ˚ ) and angles ( ) for complex (6). Selected bonds lengths (A S1—Co1 S2—Co1 S1—P1i S2—P1 O1—P1 O2—P1
2.5512 (5) 2.5510 (6) 1.9712 (8) 1.9750 (8) 1.6051 (15) 1.5989 (14)
P1—S1i Co1—N1i N1—Co1 Co1—S2i Co1—S1i
1.9712 (8) 2.1523 (16) 2.1523 (16) 2.5510 (6) 2.5512 (5)
P1i—S1—Co1 P1—S2—Co1 O2—P1—O1 O2—P1—S1i O1—P1—S1i O2—P1—S2 O1—P1—S2 S1i—P1—S2 N1i—Co1—N1 N1i—Co1—S2 N1—Co1—S2 S1i—Co1—S1
81.66 (2) 81.59 (2) 98.00 (8) 112.95 (6) 112.31 (6) 106.33 (6) 112.76 (7) 113.37 (4) 179.999 (1) 90.26 (5) 89.74 (5) 179.999 (1)
N1i—Co1—S2i N1—Co1—S2i S2—Co1—S2i N1i—Co1—S1i N1—Co1—S1i S2—Co1—S1i S2i—Co1—S1i N1i—Co1—S1 N1—Co1—S1 S2—Co1—S1 S2i—Co1—S1
89.74 (5) 90.26 (5) 180.0 89.23 (5) 90.77 (5) 80.532 (18) 99.467 (18) 90.77 (5) 89.23 (5) 99.468 (19) 80.533 (18)
Symmetry code: (i) x; y þ 2; z þ 2.
3.1. IR spectra
IR spectra were interpreted on the basis of relevant literature reports (Bajia, Butcher et al., 2009; Bajia, Drake et al., 2009; Bajia et al., 2010). Two strong intensity bands were observed in the regions 1134–1120 and 890–852 cm1, which may be ascribed to the [(P)—O—C] and [P—O—(C)] vibrations of the diphenyldithiophosphate moiety, respectively. The bands in regions 686–675 and 595–578 cm1 are attributed to asymmetric and symmetric stretching modes of PS2 groups, respectively. The value of [asym sym] is less than 100 cm1, which signifies the bidentate binding mode of diphenyldithiophosphate ligands. The appearance of a new
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band for [Co—S] in the region 457–420 cm1 (Bajia, Butcher et al., 2009; Bajia, Drake et al., 2009) in the spectra of these complexes is also indicative of the formation of the cobalt– sulfur bond. This is supported by X-ray analysis of the complexes. The presence of a direct bond of the N donor atom of Lewis bases to the cobalt metal ion can be supported by the existence of the band at 362–345 cm1, which may be assigned to the [Co—N] vibration (Bajia, Butcher et al., 2009, Bajia, Drake et al., 2009). The bands in the region 1615–1598 cm1 have been assigned for [C—N] stretching vibrations of the aromatic ring of the N donor ligands. 3.2. Magnetic moment
The magnetic moment of adducts (1)–(6) fall in the range 4.9–5.2 B.M. at 298 K, which corresponds to octahedral geometry of the complexes. These values are similar to the
Synthesis and structural elucidation of new complexes
Acta Cryst. (2015). B71, 221–227
research papers values found in the literature reported adducts of bis(O,O0 ditolyldithiophosphato)cobalt(II) (Bajia, Drake et al., 2009; Bajia et al., 2010)
3.3. Crystal and molecular structures of complexes (3)–(6)
X-ray diffraction structure analysis reveals that complexes (3), (4) and (5) crystallize in the monoclinic space groups P21/n, P21/n and P21/c, respectively, whereas complex (6) crystallizes in the triclinic space group P1 : Selected bond distances and bond angles for complexes (3)–(6) are listed in Tables 2–5. The single-crystal X-ray analysis reveals that the Co atom has occupied the crystallographic inversion center and has distorted octahedral coordination geometry around
Figure 1 Molecular structure of [{(2,4-CH3)2C6H3O}2PS2]2Co{4-(C2H5)C5H4N}2 (3) with displacement ellipsoids drawn at the 40% probability level and only the atoms of the asymmetric unit are labeled.
the cobalt metal center. A view of the coordination environment around the cobalt(II) ion in complexes (3)–(6) is shown in Figs. 1–4. The Co atom is six-coordinated by the tertiary N donor atom of two pyridine/3,4-dimethylpyridine/4-ethylpyridine molecules and four S atoms of two coordinated dithiophosphate ligands which are situated in the equatorial plane. ˚ in complex (3), The Co—N bond distances [2.168 (4) A ˚ ˚ in complex (5) 2.1827 (12) A in complex (4), 2.1521 (16) A ˚ and 2.1523 (16) A in complex (6)] are in good agreement with the Co—N bond distances reported in corresponding octahedral complexes such as [Co{S2P(OC6H4Me-p)2}2(C5H5N)2] ˚ ; Bajia, Drake et al., 2009] and Co{S2P(OC6H4Me[2.162 (2) A ˚ ; Bajia et al., 2010]. However, p)2}2(NC5H4Me-3)2 [2.174 (3) A these bond distances are found to be slightly larger when compared with values observed in trigonal bipyramidal complexes such as [Co{S2P(OC6H4CH3-p)2}2(NH3)] ˚ ; Bajia, Drake et al., 2009], [Co(S2POC[2.052 (2) A ˚] [2.059 (4) A and Me2CH2CHMeO)2(2-CH3–NC5H4)] ˚; [Co(S2POCMe2CH2CHMeO)2(3-CH3–NC5H4)] [2.068 (3) A Bajia, Butcher et al., 2009]. The Co—S1 and Co—S2 bond ˚ , for lengths for complex (3) are 2.5026 (13) and 2.5425 (13) A ˚ complex (4) are 2.5708 (4) and 2.5065 (4) A, for complex (5) ˚ , and for complex (6) are are 2.5123 (6) and 2.5520 (5) A ˚ 2.5512 (5) and 2.5510 (6) A, which are comparable with those of [Co{S2P(OC6H4Me-p)2}2(C5H5N)2] [2.5053 (8) and ˚ ; Bajia, Drake et al., 2009] and Co{S2P(OC6H4Me2.5735 (8) A ˚ ; Bajia et al., p)2}2(NC5H4Me-3)2 [2.5322 (9) and 2.5085 (9) A 2010]. However, these bond distances are longer than that of the Co—Sequatorial bond distance of trigonal bipyramidal complexes [Co(S2POCMe2CH2CHMeO)2(2-CH3–NC5H4)] ˚ ] and [Co(S2POCMe2CH2CHMeO)2(3-CH3– [2.357 (1) A ˚ ; Bajia, Butcher et al., 2009], but the Co— NC5H4)] [2.368 (1) A Saxial bond distances are comparable. In complex (4) it is found that the longer Co—S1 bond is accompanied by a relatively
Figure 2
Figure 3
Molecular structure of [{(3,5-CH3)2C6H3O}2PS2]2Co(C5H5N)2 (4) with displacement ellipsoids drawn at the 40% probability level and only the atoms of the asymmetric unit are labeled.
Molecular structure of [{(3,5-CH3)2C6H3O}2PS2]2Co{3,4-(CH3)2C5H3N}2 (5) with displacement ellipsoids drawn at the 40% probability level and only the atoms of the asymmetric unit are labeled.
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research papers ˚ ] and the shorter Co—S1 shorter P1—S1 bond [1.9721 (5) A ˚ ], whereas in bond by a longer P1—S2 bond [1.9748 (5) A complex (5) the shorter Co—S1 bond is accompanied by a ˚ ] and the longer relatively longer P1—S1 bond [1.9709 (7) A ˚ ]. Co—S1 bond by a shorter P1—S2 bond [1.9629 (7) A However, in the case of complex (6) both the Co—S1 and Co—S2 bond distances are almost the same value and the P1—S1 and P1—S2 bond distances are 1.9712 (8) and ˚ . The P—S bond distances in complexes (3)–(6) 1.9750 (8) A are akin to the bond distances found in the octahedral complex [Co{S2P(OC6H4Me-p)2}2(C5H5N)2] [1.974 (1) and ˚ ; Bajia, Drake et al., 2009], but slightly shorter than 1.970 (1) A the P1—S1 and marginally longer than the P1—S2 bond distances observed in trigonal bipyramidal complexes [Co(S2POCMe2CH2CHMeO)2(3-CH3–NC5H4)] [1.999 (1) and ˚; 1.955 (1) A Bajia, Butcher et al., 2009] and ˚; [Co{S2P(OC6H4CH3-p)2}2(NH3)] [1.9937 (9) and 1.9616 (9) A Bajia, Drake et al., 2009]. The phosphorus–sulfur bond lengths in complexes (3)–(6) fall between the bond lengths of P—S and P S bonds, since the phosphorus–sulfur bond distances of complexes (3)–(6) are marginally shorter than the single P—S bonds found in [Ni(S2P{O}OCH2CH2Ph)(dppe)] ˚ ; Li et al., 2014] and larger than the [2.042 (2) and 2.038 (2) A ˚; P S bond observed in HS2POCMe2CMe2O [1.923 (2) A Drake et al., 2000] and also intermediate between hypothetical ˚ ) and double (1.94 A ˚ ) P—S bonds (Lawton & single (2.14 A Kokotailo, 1969). This is evidence of delocalization of the electron density over the four-membered metallocycles [CoS2P]. The P atoms in dithiophosphato groups are in a tetrahedral neighbouring [O2S2] environment.
The N—Co—S bond angles in complexes (3)–(6) are in the ranges 89.48 (10)–90.52 (10), 89.11 (3)–91.44 (3), 91.23 (4)– 91.32 (5) and 89.23 (5)–89.74 (5) , respectively, showing only slight variation from a regular octahedral geometry. These N—Co—S bond angles are found to be comparable to the angles found in [Co{S2P(OC6H4Me-p)2}2(C5H5N)2] [88.82 (6)– 91.23 (6) ; Bajia, Drake et al., 2009], but smaller than the angles found in the trigonal bipyramidal complex [Co(S2POCMe2CH2CHMeO)2(3-CH3–NC5H4)] [97.57 (7) and 110.73( 8) ; Bajia, Butcher et al., 2009]. The S2—Co1—S1 bond angle in complex (3) is 81.25 (4) , in complex (4) is 80.536 (13) , in complex (5) is 81.673 (16) and in complex (6) is 80.533 (18) , which are in good agreement with the angles found in complexes [Co{S2P(OC6H4Me-p)2}2(C5H5N)2] [80.18 (3) ; Bajia, Drake et al., 2009] and [Co(S2POCMe2CH2CHMeO)2(3-CH3–NC5H4)] [81.48 (4) ; Bajia, i Butcher et al., 2009]. The S1 —Co1—S1, S2—Co1—S2i and N1i—Co1—N1 bond angles for complexes (3)–(6) are 180 , required by symmetry. In complex (4), S2—Co1—S1 and S2i— Co1—S1i bite angles [80.536 (13) ] and the S2i—Co1—S1 and S2—Co1—S1i [99.464 (13)o] inter-ligand angles show the greatest deviation from 90 and a similar trend is observed in complexes (3), (5) and (6).
4. Conclusion Donor-stabilized adducts of cobalt(II) diphenyldithiophosphates have been synthesized and characterized by elemental analysis, magnetic moment and IR. Single-crystal X-ray analysis reveals that the geometry around the cobalt metal center is distorted octahedral for the CoS4N2 chromophore. The diphenyldithiophosphate ligands are coordinated to the cobalt ion as a bidentate via two thiolate S atoms. Each of them forms a four-membered chelate ring in the equatorial plane. The N atoms from two donor ligands are axially coordinated to the Co atom. The magnetic moments values of complexes are consistent with the distorted octahedral geometry established by single-crystal X-ray structure analysis.
Acknowledgements The authors are grateful to Professor Geeta Hundal, Department of Chemistry, Guru Nanak Dev University, Amritsar, India, for her valuable suggestions.
References
Figure 4 Molecular structure of [{(3,5-CH3)2C6H3O}2PS2]2Co{4-(C2H5)C5H4N}2 (6) with displacement ellipsoids drawn at the 40% probability level and only the atoms of the asymmetric unit are labeled.
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Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. Bajia, S., Butcher, R. J., Drake, J. E. & Ratnani, R. (2009). Polyhedron, 28, 1556–1560. Bajia, S. C., Drake, J. E., Light, M. E., Nirwan, M., Pandey, S. K. & Ratnani, R. (2009). Polyhedron, 28, 85–90. Bajia, S., Mishra, A., Butcher, R. J. & Ojha, K. G. (2010). J. Coord. Chem. 63, 4271–4279. Brandenburg, K. (1998). DIAMOND, Version 2.1. Crystal Impact GbR, Bonn, Germany. Bruker (2003). SHELXTL, Version 6.14. Bruker AXS Inc., Madison, Wisconsin, USA.
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Acta Cryst. (2015). B71, 221–227
research papers Cavell, R. G., Day, E. D., Byers, W. & Watkins, P. M. (1972). Inorg. Chem. 11, 1759–1772. Drake, J. E., Khasrou, L. N., Mislankar, A. G. & Ratnani, R. (2000). Polyhedron, 19, 407–412. Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. He, M. Q., Shen, X. P., Zhang, W. L., Wu, Y. L., Cheng, X. N. & Yu, Y. P. (2002). Chin. J. Inorg. Chem. 18, 739–743. Hoskins, B. F., Robson, R. & Williams, G. A. (1976). Inorg. Chim. Acta, 16, 121–133. Hoskins, B. F. & Williams, G. A. (1975). Aust. J. Chem. 28, 2593–2605. Jørgensen, C. K. (1962). Acta Chem. Scand. 16, 2017–2024. Khajuria, R., Kumar, S., Syed, A., Kour, G., Anthal, S., Gupta, V. K., Kant, R. & Pandey, S. K. (2014). J. Coord. Chem. 67, 2925–2941. Kim, B. H., Mourhatch, R. & Aswath, P. B. (2010). Wear, 268, 579– 591. Kirschbaum, K., Bo¨nnighausen, U., Gesing, E., Greiwe, K., Kuhlmann, U., Strasdeit, H., Krebs, B. & Henkel, G. (1990). Z. Naturforsch. B, 45, 245–247. Kumar, S., Khajuria, R., Gupta, V. K., Kant, R. & Pandey, S. K. (2014). Polyhedron, 72, 140–146. Kumar, S., Khajuria, R., Jassal, A. K., Hundal, G., Hundal, M. S. & Pandey, S. K. (2014). Acta Cryst. B70, 761–767. Lawton, S. L. & Kokotailo, G. T. (1969). Inorg. Chem. 8, 2410– 2421. Lebedda, J. D. & Palmer, R. A. (1971). Inorg. Chem. 10, 2704– 2710.
Acta Cryst. (2015). B71, 221–227
Li, Y., Xie, B., Zou, L. K., Lin, X., Yang, Y., Zhu, S. & Wang, T. (2014). Polyhedron, 67, 490–494. Malatesta, L. & Pizzotti, R. (1945). Chim. Ind. (Milan), 27, 6–9. McConnell, J. F. & Schwartz, A. (1972). Acta Cryst. B28, 1546–1550. Micu-Semeniuc, R., Dumitrescu-Silaghi, L. & Haiduc, I. (1979). Inorg. Chim. Acta, 33, 281–285. Moon, T. J. & Kwon, O. K. (1979). J. Korean Chem. Soc. 23, 52–58. Pan, S., Zhu, J. & Liu, X. (2013). New J. Chem. 37, 654–662. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Sheng-Zhi, H. (1999). Jiegou Huaxue, 18, 476. Shimoi, M., Ouchi, A., Sato, S. & Saito, Y. (1979). Chem. Lett. 8, 319– 320. Shimoi, M., Ouchi, A., Uehiro, T., Yoshino, Y., Sato, S. & Saito, Y. (1982). Bull. Chem. Soc. Jpn, 55, 2371–2377. So, H., Lin, Y. C., Huang, G. G. S. & Chang, T. S. T. (1993). Wear, 166, 17–26. Tripathi, U. N. & Singh, M. S. (1999). J. Indian Chem. Soc. 76, 360– 361. Vogel, A. I. (1991). A Textbook of Quantitative Chemical Analysis, 5th ed. London: BLBS and Longman. Williams, G. A. & Robson, R. (1981). Aust. J. Chem. 34, 65–79. Xu, Z., Lin, J.-H, Yu, Y.-P, Xu, J., You, X.-Z., Liu, S.-X. & Lin, C.-C. (1989). Huaxue Xuebao, 47, 623–627. Yamada, Y., Shimoi, M. & Quchi, A. (1978). Chem. Lett. 7, 867–870. Zu, B. H., Liu, S. T., Wu, B. F. & Hu, X. (2002). Huaxue Yanjiu Yu Yingyong, 14, 671–674.
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ISSN 2052-5206
Synthesis and structural elucidation of new complexes of 2,4- and 3,5-dimethyl diphenyldithiophosphates with cobalt(II) Sandeep Kumar,a Ruchi Khajuria,a Amanpreet Kaur Jassal,b Maninder S. Hundalb and Sushil K. Pandeya*
Received 26 November 2014 Accepted 25 February 2015
Edited by N. B. Bolotina, Russian Academy of Sciences, Russia Keywords: diphenyldithiophosphate; chromophore; donor stabilized. CCDC references: 1051253; 1051254; 1051255; 1051256 Supporting information: this article has supporting information at journals.iucr.org/b
a
Department of Chemistry, University of Jammu, Jammu 180 006, India, and bDepartment of Chemistry, Guru Nanak Dev University, Amritsar 143 005, India. *Correspondence e-mail: [email protected]
A new series of donor-stabilized addition complexes of cobalt(II) with disubstituted diphenyldithiophosphates [{(ArO)2PS2}2CoL2] {Ar = 2,4(CH3)2C6H3 [(1)–(3)] and 3,5-(CH3)2C6H3 [(4)–(6)]; L = C5H5N [(1), (4)], 3,4(CH3)2C5H3N [(2), (5)] and 4-(C2H5)C5H4N [(3), (6)]} were successfully isolated and characterized by elemental analyses, magnetic moment measurements, IR and single-crystal X-ray analysis. Complexes (3), (4) and (5) crystallize in the monoclinic space groups P21/n, P21/n and P21/c, respectively, whereas complex (6) crystallizes in the triclinic space group P1 . X-ray diffraction analysis of complexes (3)–(6) reveals a six-coordinated distorted octahedral geometry for the CoS4N2 chromophore defined by two chelating diphenyldithiophosphate anions as well as two N-donor ligands. Two diphenyldithiophosphate ligands are coordinated to the cobalt ion as a bidentate ligand chelating via the two thiolate S atoms. Each of them forms a four-membered chelate ring in the equatorial plane. The N atoms from two donor ligands are axially coordinated to the Co atom in a mutually trans position.
1. Introduction
# 2015 International Union of Crystallography
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Transition metal sulfides have received great attention in the field of material science because of their thermoelectric and photoelectric properties, and many other potential applications (Pan et al., 2013). The chemistry of dithiophosphate complexes of transition metals continues to be of great interest because of their striking structural features and diversified applications. The dithiophosphato derivatives of transition metals find extensive applications in lubrication engineering (So et al., 1993) and plastic industries (Kim et al., 2010). Cobalt dithiophosphates are known to have a significant antiwear effect on chrome alloy steel compared with the other metallic dithiophosphates. Also, cobalt dithiophosphates have a characteristic property of thermal sensitivity in color which is shown by a color change from brown to blue over a certain temperature (Moon & Kwon, 1979). The 1,1dithiolate ligands are versatile in nature and coordination complexes with cobalt have been reported in the literature (Cavell et al., 1972; Hoskins & Williams, 1975; Hoskins et al., 1976; Jørgensen, 1962; Lebedda & Palmer, 1971; Malatesta & Pizzotti, 1945; Micu-Semeniuc et al., 1979; Tripathi & Singh, 1999; Yamada et al., 1978). In these complexes, the dithiophosphate ligand moieties are normally bidentate. X-ray crystal structures have been reported for a number of cobalt complexes with dialkyl dithiophosphates including Co[S2P(OMe)2]3 (McConnell & Schwartz, 1972), Co[S2P(OPri)2]3 (Zu et al., 2002), [Co{S2P(OMe)2}2PPh3] http://dx.doi.org/10.1107/S205252061500390X
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research papers (Shimoi et al., 1979), [NMe4][CoCl{S2P(OMe)2}2] (Kirschbaum et al., 1990), Co[S2P(OEt)2]30.5H2O (Sheng-Zhi, 1999), [Co{S2P(OEt)2}2(C5H5N)2] (Xu et al., 1989), [Co{S2P(OCy)2}2(C5H5N)2] (He et al., 2002) and [Co{S2P(OEt)2}2(C24H26O2N4)] (Williams & Robson, 1981). There are also some reports available on the adducts of alkylene dithiphosphates of cobalt(II) (Bajia, Butcher et al., 2009). Cobalt dithiophosphate complexes with nitrogen- or phosphoruscontaining Lewis bases display distorted trigonal bipyramidal or octahedral geometry around the central metal atom. In the trigonal bipyramidal geometry, the dithiophosphate moieties chelate axially and equatorially to the cobalt (Shimoi et al., 1982), usually with the hetero-atom of the Lewis base on the equatorial plane (Shimoi et al., 1982). However, adducts of cobalt(II) with analogous aromatic ligands have been less studied (Bajia, Drake et al., 2009) and a literature survey reveals that there is no report available on donor-stabilized complexes of cobalt(II) with disubstituted diphenyldithiophosphates. Continuing our interest in various dithiophosphate ligands (Khajuria et al., 2014; Kumar, Khajuria, Gupta et al., 2014; Kumar, Khajuria, Jassal et al., 2014) led us to work on the reactions of addition complexes of cobalt(II) diphenyldithiophosphate with nitrogen donor moieties to study the influence of different donor ligands on the cobalt(II) diphenyldithiophosphate complexes. Thus, we report here on the synthesis, spectroscopic and single-crystal X-ray analysis of addition complexes of cobalt(II) 2,4- and 3,5-dimethyl diphenyldithiophosphates with N donor ligands.
2. Experimental 2.1. Materials and instrumentation
Solvents were distilled and dried using standard methods before use. Chloroform (Thomas Baker, b.p. 334 K) was dried over P2O5. All the disubstituted phenols were procured from Sigma Aldrich and used without purification. The sodium salts of disubstituted O,O0 -diphenyldithiophosphate, i.e. {(2,4CH3)2C6H3O}2PS2Na and {(3,5-CH3)2C6H3O}2PS2Na, were synthesized according to a literature procedure (Khajuria et al., 2014). Moisture was carefully excluded for the synthesis of ligands throughout the experimental manipulations by using standard Schlenk techniques. Cobalt was estimated using the pyridine thiocyanate method (Vogel, 1991). Elemental analyses (C, H, N, S) were conducted using the Vario EL-III elemental analyser (Indian Institute of Integrative Medicine, Jammu). IR spectra were recorded in the range 4000–340 cm1 on a Shimadzu FT–IR spectrophotometer (Department of Chemistry, University of Jammu, India).
Purple-colored solid precipitates were formed immediately. After 30 min of stirring at room temperature the reaction contents were filtered using a sintered glass disk to obtain the complex [{(2,4-CH3)2C6H3O}2PS2]2Co(C5H5N)2 (1) as a purple powdery solid. The complex was recrystallized from a chloroform/n-hexane (3:1) mixture at room temperature. Yield: 91%; m.p. 397–399 K (dec). Anal.: calc. for C42H46N2O4P2S4Co: C 56.55, H 5.20, S 14.38, N 3.14, Co 6.61; found: C 56.52, H 5.15, S 14.34, N 3.10, Co 6.54. IR (KBr): 1609 m [C—N], 1120 s [(P)—O—C], 885 s [P—O—(C)], 680 s [P—S]asym, 595 m [P—S]sym, 444 w [Co—S], 359 w [Co—N] cm1; eff = 5.0 B.M. 2.2.2. [{(2,4-CH3)2C6H3O}2PS2]2Co{3,4-(CH3)2C5H3N}2 (2). Compound (2) was obtained as a purple solid by a
similar procedure as described for compound (1) using Co(NO3)26H2O (0.20 g, 0.68 mmol), 3,4-dimethylpyridine (0.147 g, 1.37 mmol) and {(2,4-CH3)2C6H3O}2PS2Na (0.50 g, 1.38 mmol). The resulting solid was recrystallized from a chloroform/n-hexane mixture at room temperature. Yield: 89%; m.p. 395398 K (dec.). Anal.: calc. for C46H54N2O4P2S4Co: C 56.28, H 5.74, S 13.53, N 2.95, Co 6.22; found: C 56.22, H 5.68, S 13.47, N 2.90, Co 6.17. IR (KBr): 1598 m [C—N], 1130 s [(P)—O—C], 875 s [P—O—(C)], 680 s [P—S]asym, 584 m [P—S]sym, 420 w [Co—S], 362 w [Co—N] cm1; eff = 4.9 B.M. 2.2.3. [{(2,4-CH3)2C6H3O}2PS2]2Co{4-(C2H5)C5H4N}2 (3). Compound (3) was obtained as a purple solid by a similar procedure as described for compound (1) using Co(NO3)26H2O (0.20 g, 0.68 mmol), 4-ethylpyridine (0.147 g, (0.50 g, 1.37 mmol) and {(2,4-CH3)2C6H3O}2PS2Na 1.38 mmol). The resulting solid was recrystallized from a chloroform/n-hexane mixture at room temperature. Yield: 92%; m.p. 393395 K (dec). Anal.: calc. for C46H54N2O4P2S4Co: C 56.28, H 5.74, S 13.53, N 2.95, Co 6.22; found: C 56.24, H 5.69, S 13.49, N 2.92, Co 6.19. IR (KBr): 1615 m [C—N], 1116 s [(P)—O—C], 890 s [P—O—(C)], 691 s [P—S]asym, 588 m [P—S]sym, 435 w [Co—S], 345 w [Co—N] cm1; eff = 5.2 B.M. 2.2.4. [{(3,5-CH3)2C6H3O}2PS2]2Co(C5H5N)2 (4). Complex (4) was obtained as a purple solid by a similar procedure to that described for complex (1) using Co(NO3)26H2O (0.20 g, 0.68 mmol), pyridine (0.147 g, 1.37 mmol) and {(3,5CH3)2C6H3O}2PS2Na (0.50 g, 1.38 mmol). The resulting solid was recrystallized from a chloroform/n-hexane mixture at room temperature. Yield 92%; m.p. 411413 K (dec.). Anal.: calc. for C42H46N2O4P2S4Co: C 56.55, H 5.20, S 14.38, N 3.14, Co 6.61; found: C 56.49, H 5.17, S 14.32, N 3.11, Co 6.57. IR (KBr): 1612 m [C—N], 1126 s [(P)—O—C], 889 s [P—O— (C)], 675 s [P—S]asym, 592 m [P—S]sym, 432 w [Co—S], 352 w [Co—N] cm1; eff = 4.9 B.M.
2.2. Synthesis
2.2.5. [{(3,5-CH3)2C6H3O}2PS2]2Co{3,4-(CH3)2C5H3N}2 (5). Complex (5) was obtained as a purple solid by a similar
2.2.1. [{(2,4-CH3)2C6H3O}2PS2]2Co(C5H5N)2 (1). To a stirred aqueous solution of Co(NO3)26H2O (0.20 g, 0.68 mmol) was added pyridine (0.108 g, 1.37 mmol), followed by the addition of an aqueous solution (10 ml) of {(2,4CH3)2C6H3O}2PS2Na (0.50 g, 1.38 mmol) in a 1:2 molar ratio.
procedure to that described for complex (1) using Co(NO3)26H2O (0.20 g, 0.68 mmol), 3,4–dimethylpyridine (0.147 g, 1.37 mmol) and {(3,5-CH3)2C6H3O}2PS2Na (0.50 g, 1.38 mmol). The resulting solid was recrystallized from a chloroform/n-hexane mixture at room temperature. Yield:
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research papers Table 1 Summary of the crystal structure, data collection and structure refinement parameters for complexes (3)–(6). Experiments were carried out at 296 K with Mo K radiation. (3)
(4)
(5)
(6)
, , ( )
C46H54CoN2O4P2S4 948.06 Monoclinic, P21/n 10.254 (3), 15.557 (5), 15.444 (6) 90, 102.287 (5), 90
C42H46CoN2O4P2S4 891.96 Monoclinic, P21/n 11.8107 (6), 14.4211 (9), 12.8807 (7) 90, 104.929 (2), 90
C46H54CoN2O4P2S4 948.06 Monoclinic, P21/c 8.0404 (7), 16.3777 (13), 18.9182 (14) 90, 98.074 (4), 90
˚ 3) V (A Z (mm1) Crystal size (mm)
2407.2 (14) 2 0.64 0.15 0.12 0.08
2119.8 (2) 2 0.72 0.10 0.07 0.05
2466.5 (3) 2 0.62 0.12 0.09 0.06
C46H54CoN2O4P2S4 948.06 Triclinic, P1 9.5631 (7), 9.8309 (6), 14.2326 (9) 99.290 (3), 98.602 (3), 112.994 (3) 1181.83 (14) 1 0.65 0.12 0.09 0.06
Bruker APEXII CCD Multi-scan 0.626, 0.746 19 203, 5308, 3263
Bruker APEXII CCD Multi-scan 0.648, 0.746 22 789, 6024, 5025
Bruker APEXII CCD Multi-scan 0.637, 0.746 21 225, 5402, 4132
Bruker APEXII CCD Multi-scan 0.650, 0.746 24 294, 5258, 3991
0.066 0.649
0.020 0.701
0.040 0.640
0.042 0.643
0.073, 0.256, 1.01 5308 273 1 0.66, 0.58
0.030, 0.087, 1.03 6024 254 0 0.31, 0.28
0.036, 0.106, 0.93 5402 274 0 0.25, 0.36
0.036, 0.092, 1.04 5258 273 0 0.33, 0.23
Crystal data Chemical formula Mr Crystal system, space group ˚) a, b, c (A
Data collection Diffractometer Absorption correction Tmin, Tmax No. of measured, independent and observed [I > 2(I)] reflections Rint ˚ 1) (sin /)max (A Refinement R[F2 > 2(F2)], wR(F2), S No. of reflections No. of parameters No. of restraints ˚ 3) max, min (e A
Computer programs: Bruker APEX2, Bruker SAINT, SIR92 (Altomare et al., 1993), SHELXL2014, SHELXL97 (Sheldrick, 2008), SHELXTL (Bruker, 2003).
90%; m.p. 408411 K (dec.). Anal.: calc. for C46H54N2O4P2S4Co: C 56.28, H 5.74, S 13.53, N 2.95, Co 6.22; found: C 56.25, H 5.70, S 13.51, N 2.88, Co 6.16. IR (KBr): 1612 m [C— N], 1134 s [(P)—O—C], 852 s [P—O—(C)], 684 s [P— S]asym, 578 m [P—S]sym, 424 w [Co—S], 356 w [Co—N] cm1; eff = 5.2 B.M. 2.2.6. [{(3,5-CH3)2C6H3O}2PS2]2Co{4-(C2H5)C5H4N}2 (6). Complex (6) was obtained as a purple solid by a similar procedure to that described for complex (1) using Co(NO3)26H2O (0.20 g, 0.68 mmol), 4-ethylpyridine (0.147 g, (0.50 g, 1.37 mmol) and {(3,5-CH3)2C6H3O}2PS2Na 1.38 mmol). The resulting solid was recrystallized from a chloroform/n-hexane mixture at room temperature. Yield: 92%; m.p. 401–404 K (dec.). Anal.: calc. for C46H54N2O4P2S4Co: C 56.28, H 5.74, S 13.53, N 2.95, Co 6.22; found: C 56.23, H 5.67, S 13.46, N 2.90, Co 6.20. IR (KBr): 1614 m [C— N], 1132 s [(P)—O—C], 883 s [P—O—(C)], 686 s [P— S]asym, 592 m [P—S]sym, 457 w [Co—S], 347 w [Co—N] cm1; eff = 5.1 B.M. 2.3. Crystallography data collection and refinement
Crystallization of complexes (3)–(6) was executed by very slow evaporation of their saturated solution in chloroform/nhexane mixture (3:1) at room temperature yielding suitable purple colored and rectangular shaped single crystals for Xray analysis. X-ray data of complexes (3)–(6) were collected Acta Cryst. (2015). B71, 221–227
on a Bruker APEXII CCD diffractometer (Department of Chemistry, Guru Nanak Dev University, Amritsar, India) ˚ ) at room temperature. The data using Mo K ( = 0.71069 A were processed by SAINT correcting for Lorentz and polarization effects. An empirical absorption correction was applied using SADABS from Bruker. The solution was obtained by direct methods, using SIR92 (Altomare et al., 1993) and refined by full-matrix least-squares refinement methods (Sheldrick, 2008) based on F2, using SHELX97. All non-H atoms were refined anisotropically. All calculations were performed using the WinGX package (Farrugia, 1999). Molecular drawings were obtained using DIAMOND, Version 2.1 (Brandenburg, 1998). Crystallographic data, details of the data collection, structure solution and refinements are listed in Table 1.
3. Results and discussion Donor-stabilized addition complexes of cobalt(II) with disubstituted diphenyldithiophosphates were prepared by the reaction of an aqueous solution of Co(NO3)26H2O and Lewis bases followed by the addition of a 1:2 stiochiometric amount of [{(ArO)2PS2Na] according to the scheme below. The precipitated purple solid complexes were separated by filtration and repeatedly washed with water. These complexes were found to be soluble in all common organic solvents.
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Table 4
˚ ) and angles ( ) for complex (3). Selected bonds lengths (A
˚ ) and angles ( ) for complex (5). Selected bonds lengths (A
Co1—S1 Co1—S2 P1—O1 P1—O2 P1—S2
2.5026 (13) 2.5425 (13) 1.608 (3) 1.602 (3) 1.9696 (17)
P1—S1 Co1—N1i Co1—S1i Co1—S2i
1.9702 (17) 2.168 (4) 2.5026 (13) 2.5425 (13)
O2—P1—S2 O1—P1—S2 O2—P1—S1 O1—P1—S1 S2—P1—S1 P1—S1—Co1 P1—S2—Co1 N1—Co1—N1i N1—Co1—S1 N1i—Co1—S1 N1—Co1—S1i
106.42 (14) 113.65 (14) 114.25 (14) 110.51 (13) 112.98 (7) 83.15 (5) 82.11 (5) 179.999 (1) 90.52 (10) 89.48 (10) 89.48 (10)
N1i—Co1—S1i S1—Co1—S1i N1—Co1—S2 N1i—Co1—S2 S1—Co1—S2 S1i—Co1—S2 N1—Co1—S2i N1i—Co1—S2i S1—Co1—S2i S1i—Co1—S2i S2—Co1—S2i
90.52 (10) 180.0 89.73 (10) 90.27 (10) 81.25 (4) 98.75 (4) 90.27 (10) 89.73 (10) 98.75 (4) 81.25 (4) 180.0
Symmetry code: (i) x þ 1; y; z þ 1.
Co1—S1 Co1—S2 P1—O1 P1—O2 P1—S2i P1—S1
2.5123 (6) 2.5520 (5) 1.6013 (15) 1.6068 (15) 1.9629 (7) 1.9709 (7)
P1i—S2 Co1—N1i Co1—N1 Co1—S1i Co1—S2i
1.9630 (7) 2.1522 (16) 2.1521 (16) 2.5123 (6) 2.5521 (5)
O1—P1—O2 O1—P1—S2i O2—P1—S2i O1—P1—S1 O2—P1—S1 S2i—P1—S1 P1—S1—Co1 P1i—S2—Co1 N1—Co1—N1i N1—Co1—S1i N1i—Co1—S1i N1—Co1—S1
97.64 (8) 108.12 (6) 111.58 (6) 111.97 (6) 111.55 (6) 114.68 (3) 82.12 (2) 81.23 (2) 180.00 (5) 88.68 (5) 91.32 (5) 91.32 (5)
N1i—Co1—S1 S1i—Co1—S1 N1—Co1—S2 N1i—Co1—S2 S1i—Co1—S2 S1—Co1—S2 N1—Co1—S2i N1i—Co1—S2i S1i—Co1—S2i S1—Co1—S2i S2—Co1—S2i
88.68 (5) 180.0 91.23 (4) 88.77 (4) 81.673 (16) 98.326 (16) 88.77 (4) 91.23 (4) 98.328 (16) 81.673 (16) 180.0
Symmetry code: (i) x þ 1; y; z.
Table 3 ˚ ) and angles ( ) for complex (4). Selected bonds lengths (A Co1—S1 Co1—S2 P1—O1 P1—O2 P1—S1
2.5708 (4) 2.5065 (4) 1.5954 (11) 1.5966 (11) 1.9721 (5)
P1—S2 Co1—N1i Co1—N1 Co1—S2i Co1—S1i
1.9748 (5) 2.1827 (12) 2.1827 (12) 2.5065 (4) 2.5708 (4)
P1—S1—Co1 P1—S2—Co1 S1—P1—S2 O1—P1—S1 O1—P1—S2 O1—P1—O2 O2—P1—S1 O2—P1—S2 N1—Co1—S2i N1i—Co1—S2 N1—Co1—S2 N1i—Co1—N1
80.956 (17) 82.582 (16) 112.52 (2) 113.68 (5) 106.15 (5) 98.03 (6) 112.19 (5) 113.31 (5) 90.89 (3) 90.89 (3) 89.11 (3) 180.0
S2i—Co1—S1 S2—Co1—S1 S2i—Co1—S1i S2—Co1—S1i S2i—Co1—S2 N1i—Co1—S1 N1—Co1—S1 N1i—Co1—S1i N1—Co1—S1i N1i—Co1—S2i S1—Co1—S1i
99.465 (13) 80.536 (13) 80.536 (13) 99.464 (13) 180.0 88.56 (3) 91.44 (3) 91.44 (3) 88.56 (3) 89.11 (3) 180.0
Symmetry code: (i) x þ 1; y; z þ 2.
Table 5 ˚ ) and angles ( ) for complex (6). Selected bonds lengths (A S1—Co1 S2—Co1 S1—P1i S2—P1 O1—P1 O2—P1
2.5512 (5) 2.5510 (6) 1.9712 (8) 1.9750 (8) 1.6051 (15) 1.5989 (14)
P1—S1i Co1—N1i N1—Co1 Co1—S2i Co1—S1i
1.9712 (8) 2.1523 (16) 2.1523 (16) 2.5510 (6) 2.5512 (5)
P1i—S1—Co1 P1—S2—Co1 O2—P1—O1 O2—P1—S1i O1—P1—S1i O2—P1—S2 O1—P1—S2 S1i—P1—S2 N1i—Co1—N1 N1i—Co1—S2 N1—Co1—S2 S1i—Co1—S1
81.66 (2) 81.59 (2) 98.00 (8) 112.95 (6) 112.31 (6) 106.33 (6) 112.76 (7) 113.37 (4) 179.999 (1) 90.26 (5) 89.74 (5) 179.999 (1)
N1i—Co1—S2i N1—Co1—S2i S2—Co1—S2i N1i—Co1—S1i N1—Co1—S1i S2—Co1—S1i S2i—Co1—S1i N1i—Co1—S1 N1—Co1—S1 S2—Co1—S1 S2i—Co1—S1
89.74 (5) 90.26 (5) 180.0 89.23 (5) 90.77 (5) 80.532 (18) 99.467 (18) 90.77 (5) 89.23 (5) 99.468 (19) 80.533 (18)
Symmetry code: (i) x; y þ 2; z þ 2.
3.1. IR spectra
IR spectra were interpreted on the basis of relevant literature reports (Bajia, Butcher et al., 2009; Bajia, Drake et al., 2009; Bajia et al., 2010). Two strong intensity bands were observed in the regions 1134–1120 and 890–852 cm1, which may be ascribed to the [(P)—O—C] and [P—O—(C)] vibrations of the diphenyldithiophosphate moiety, respectively. The bands in regions 686–675 and 595–578 cm1 are attributed to asymmetric and symmetric stretching modes of PS2 groups, respectively. The value of [asym sym] is less than 100 cm1, which signifies the bidentate binding mode of diphenyldithiophosphate ligands. The appearance of a new
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band for [Co—S] in the region 457–420 cm1 (Bajia, Butcher et al., 2009; Bajia, Drake et al., 2009) in the spectra of these complexes is also indicative of the formation of the cobalt– sulfur bond. This is supported by X-ray analysis of the complexes. The presence of a direct bond of the N donor atom of Lewis bases to the cobalt metal ion can be supported by the existence of the band at 362–345 cm1, which may be assigned to the [Co—N] vibration (Bajia, Butcher et al., 2009, Bajia, Drake et al., 2009). The bands in the region 1615–1598 cm1 have been assigned for [C—N] stretching vibrations of the aromatic ring of the N donor ligands. 3.2. Magnetic moment
The magnetic moment of adducts (1)–(6) fall in the range 4.9–5.2 B.M. at 298 K, which corresponds to octahedral geometry of the complexes. These values are similar to the
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research papers values found in the literature reported adducts of bis(O,O0 ditolyldithiophosphato)cobalt(II) (Bajia, Drake et al., 2009; Bajia et al., 2010)
3.3. Crystal and molecular structures of complexes (3)–(6)
X-ray diffraction structure analysis reveals that complexes (3), (4) and (5) crystallize in the monoclinic space groups P21/n, P21/n and P21/c, respectively, whereas complex (6) crystallizes in the triclinic space group P1 : Selected bond distances and bond angles for complexes (3)–(6) are listed in Tables 2–5. The single-crystal X-ray analysis reveals that the Co atom has occupied the crystallographic inversion center and has distorted octahedral coordination geometry around
Figure 1 Molecular structure of [{(2,4-CH3)2C6H3O}2PS2]2Co{4-(C2H5)C5H4N}2 (3) with displacement ellipsoids drawn at the 40% probability level and only the atoms of the asymmetric unit are labeled.
the cobalt metal center. A view of the coordination environment around the cobalt(II) ion in complexes (3)–(6) is shown in Figs. 1–4. The Co atom is six-coordinated by the tertiary N donor atom of two pyridine/3,4-dimethylpyridine/4-ethylpyridine molecules and four S atoms of two coordinated dithiophosphate ligands which are situated in the equatorial plane. ˚ in complex (3), The Co—N bond distances [2.168 (4) A ˚ ˚ in complex (5) 2.1827 (12) A in complex (4), 2.1521 (16) A ˚ and 2.1523 (16) A in complex (6)] are in good agreement with the Co—N bond distances reported in corresponding octahedral complexes such as [Co{S2P(OC6H4Me-p)2}2(C5H5N)2] ˚ ; Bajia, Drake et al., 2009] and Co{S2P(OC6H4Me[2.162 (2) A ˚ ; Bajia et al., 2010]. However, p)2}2(NC5H4Me-3)2 [2.174 (3) A these bond distances are found to be slightly larger when compared with values observed in trigonal bipyramidal complexes such as [Co{S2P(OC6H4CH3-p)2}2(NH3)] ˚ ; Bajia, Drake et al., 2009], [Co(S2POC[2.052 (2) A ˚] [2.059 (4) A and Me2CH2CHMeO)2(2-CH3–NC5H4)] ˚; [Co(S2POCMe2CH2CHMeO)2(3-CH3–NC5H4)] [2.068 (3) A Bajia, Butcher et al., 2009]. The Co—S1 and Co—S2 bond ˚ , for lengths for complex (3) are 2.5026 (13) and 2.5425 (13) A ˚ complex (4) are 2.5708 (4) and 2.5065 (4) A, for complex (5) ˚ , and for complex (6) are are 2.5123 (6) and 2.5520 (5) A ˚ 2.5512 (5) and 2.5510 (6) A, which are comparable with those of [Co{S2P(OC6H4Me-p)2}2(C5H5N)2] [2.5053 (8) and ˚ ; Bajia, Drake et al., 2009] and Co{S2P(OC6H4Me2.5735 (8) A ˚ ; Bajia et al., p)2}2(NC5H4Me-3)2 [2.5322 (9) and 2.5085 (9) A 2010]. However, these bond distances are longer than that of the Co—Sequatorial bond distance of trigonal bipyramidal complexes [Co(S2POCMe2CH2CHMeO)2(2-CH3–NC5H4)] ˚ ] and [Co(S2POCMe2CH2CHMeO)2(3-CH3– [2.357 (1) A ˚ ; Bajia, Butcher et al., 2009], but the Co— NC5H4)] [2.368 (1) A Saxial bond distances are comparable. In complex (4) it is found that the longer Co—S1 bond is accompanied by a relatively
Figure 2
Figure 3
Molecular structure of [{(3,5-CH3)2C6H3O}2PS2]2Co(C5H5N)2 (4) with displacement ellipsoids drawn at the 40% probability level and only the atoms of the asymmetric unit are labeled.
Molecular structure of [{(3,5-CH3)2C6H3O}2PS2]2Co{3,4-(CH3)2C5H3N}2 (5) with displacement ellipsoids drawn at the 40% probability level and only the atoms of the asymmetric unit are labeled.
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research papers ˚ ] and the shorter Co—S1 shorter P1—S1 bond [1.9721 (5) A ˚ ], whereas in bond by a longer P1—S2 bond [1.9748 (5) A complex (5) the shorter Co—S1 bond is accompanied by a ˚ ] and the longer relatively longer P1—S1 bond [1.9709 (7) A ˚ ]. Co—S1 bond by a shorter P1—S2 bond [1.9629 (7) A However, in the case of complex (6) both the Co—S1 and Co—S2 bond distances are almost the same value and the P1—S1 and P1—S2 bond distances are 1.9712 (8) and ˚ . The P—S bond distances in complexes (3)–(6) 1.9750 (8) A are akin to the bond distances found in the octahedral complex [Co{S2P(OC6H4Me-p)2}2(C5H5N)2] [1.974 (1) and ˚ ; Bajia, Drake et al., 2009], but slightly shorter than 1.970 (1) A the P1—S1 and marginally longer than the P1—S2 bond distances observed in trigonal bipyramidal complexes [Co(S2POCMe2CH2CHMeO)2(3-CH3–NC5H4)] [1.999 (1) and ˚; 1.955 (1) A Bajia, Butcher et al., 2009] and ˚; [Co{S2P(OC6H4CH3-p)2}2(NH3)] [1.9937 (9) and 1.9616 (9) A Bajia, Drake et al., 2009]. The phosphorus–sulfur bond lengths in complexes (3)–(6) fall between the bond lengths of P—S and P S bonds, since the phosphorus–sulfur bond distances of complexes (3)–(6) are marginally shorter than the single P—S bonds found in [Ni(S2P{O}OCH2CH2Ph)(dppe)] ˚ ; Li et al., 2014] and larger than the [2.042 (2) and 2.038 (2) A ˚; P S bond observed in HS2POCMe2CMe2O [1.923 (2) A Drake et al., 2000] and also intermediate between hypothetical ˚ ) and double (1.94 A ˚ ) P—S bonds (Lawton & single (2.14 A Kokotailo, 1969). This is evidence of delocalization of the electron density over the four-membered metallocycles [CoS2P]. The P atoms in dithiophosphato groups are in a tetrahedral neighbouring [O2S2] environment.
The N—Co—S bond angles in complexes (3)–(6) are in the ranges 89.48 (10)–90.52 (10), 89.11 (3)–91.44 (3), 91.23 (4)– 91.32 (5) and 89.23 (5)–89.74 (5) , respectively, showing only slight variation from a regular octahedral geometry. These N—Co—S bond angles are found to be comparable to the angles found in [Co{S2P(OC6H4Me-p)2}2(C5H5N)2] [88.82 (6)– 91.23 (6) ; Bajia, Drake et al., 2009], but smaller than the angles found in the trigonal bipyramidal complex [Co(S2POCMe2CH2CHMeO)2(3-CH3–NC5H4)] [97.57 (7) and 110.73( 8) ; Bajia, Butcher et al., 2009]. The S2—Co1—S1 bond angle in complex (3) is 81.25 (4) , in complex (4) is 80.536 (13) , in complex (5) is 81.673 (16) and in complex (6) is 80.533 (18) , which are in good agreement with the angles found in complexes [Co{S2P(OC6H4Me-p)2}2(C5H5N)2] [80.18 (3) ; Bajia, Drake et al., 2009] and [Co(S2POCMe2CH2CHMeO)2(3-CH3–NC5H4)] [81.48 (4) ; Bajia, i Butcher et al., 2009]. The S1 —Co1—S1, S2—Co1—S2i and N1i—Co1—N1 bond angles for complexes (3)–(6) are 180 , required by symmetry. In complex (4), S2—Co1—S1 and S2i— Co1—S1i bite angles [80.536 (13) ] and the S2i—Co1—S1 and S2—Co1—S1i [99.464 (13)o] inter-ligand angles show the greatest deviation from 90 and a similar trend is observed in complexes (3), (5) and (6).
4. Conclusion Donor-stabilized adducts of cobalt(II) diphenyldithiophosphates have been synthesized and characterized by elemental analysis, magnetic moment and IR. Single-crystal X-ray analysis reveals that the geometry around the cobalt metal center is distorted octahedral for the CoS4N2 chromophore. The diphenyldithiophosphate ligands are coordinated to the cobalt ion as a bidentate via two thiolate S atoms. Each of them forms a four-membered chelate ring in the equatorial plane. The N atoms from two donor ligands are axially coordinated to the Co atom. The magnetic moments values of complexes are consistent with the distorted octahedral geometry established by single-crystal X-ray structure analysis.
Acknowledgements The authors are grateful to Professor Geeta Hundal, Department of Chemistry, Guru Nanak Dev University, Amritsar, India, for her valuable suggestions.
References
Figure 4 Molecular structure of [{(3,5-CH3)2C6H3O}2PS2]2Co{4-(C2H5)C5H4N}2 (6) with displacement ellipsoids drawn at the 40% probability level and only the atoms of the asymmetric unit are labeled.
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Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. Bajia, S., Butcher, R. J., Drake, J. E. & Ratnani, R. (2009). Polyhedron, 28, 1556–1560. Bajia, S. C., Drake, J. E., Light, M. E., Nirwan, M., Pandey, S. K. & Ratnani, R. (2009). Polyhedron, 28, 85–90. Bajia, S., Mishra, A., Butcher, R. J. & Ojha, K. G. (2010). J. Coord. Chem. 63, 4271–4279. Brandenburg, K. (1998). DIAMOND, Version 2.1. Crystal Impact GbR, Bonn, Germany. Bruker (2003). SHELXTL, Version 6.14. Bruker AXS Inc., Madison, Wisconsin, USA.
Synthesis and structural elucidation of new complexes
Acta Cryst. (2015). B71, 221–227
research papers Cavell, R. G., Day, E. D., Byers, W. & Watkins, P. M. (1972). Inorg. Chem. 11, 1759–1772. Drake, J. E., Khasrou, L. N., Mislankar, A. G. & Ratnani, R. (2000). Polyhedron, 19, 407–412. Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. He, M. Q., Shen, X. P., Zhang, W. L., Wu, Y. L., Cheng, X. N. & Yu, Y. P. (2002). Chin. J. Inorg. Chem. 18, 739–743. Hoskins, B. F., Robson, R. & Williams, G. A. (1976). Inorg. Chim. Acta, 16, 121–133. Hoskins, B. F. & Williams, G. A. (1975). Aust. J. Chem. 28, 2593–2605. Jørgensen, C. K. (1962). Acta Chem. Scand. 16, 2017–2024. Khajuria, R., Kumar, S., Syed, A., Kour, G., Anthal, S., Gupta, V. K., Kant, R. & Pandey, S. K. (2014). J. Coord. Chem. 67, 2925–2941. Kim, B. H., Mourhatch, R. & Aswath, P. B. (2010). Wear, 268, 579– 591. Kirschbaum, K., Bo¨nnighausen, U., Gesing, E., Greiwe, K., Kuhlmann, U., Strasdeit, H., Krebs, B. & Henkel, G. (1990). Z. Naturforsch. B, 45, 245–247. Kumar, S., Khajuria, R., Gupta, V. K., Kant, R. & Pandey, S. K. (2014). Polyhedron, 72, 140–146. Kumar, S., Khajuria, R., Jassal, A. K., Hundal, G., Hundal, M. S. & Pandey, S. K. (2014). Acta Cryst. B70, 761–767. Lawton, S. L. & Kokotailo, G. T. (1969). Inorg. Chem. 8, 2410– 2421. Lebedda, J. D. & Palmer, R. A. (1971). Inorg. Chem. 10, 2704– 2710.
Acta Cryst. (2015). B71, 221–227
Li, Y., Xie, B., Zou, L. K., Lin, X., Yang, Y., Zhu, S. & Wang, T. (2014). Polyhedron, 67, 490–494. Malatesta, L. & Pizzotti, R. (1945). Chim. Ind. (Milan), 27, 6–9. McConnell, J. F. & Schwartz, A. (1972). Acta Cryst. B28, 1546–1550. Micu-Semeniuc, R., Dumitrescu-Silaghi, L. & Haiduc, I. (1979). Inorg. Chim. Acta, 33, 281–285. Moon, T. J. & Kwon, O. K. (1979). J. Korean Chem. Soc. 23, 52–58. Pan, S., Zhu, J. & Liu, X. (2013). New J. Chem. 37, 654–662. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Sheng-Zhi, H. (1999). Jiegou Huaxue, 18, 476. Shimoi, M., Ouchi, A., Sato, S. & Saito, Y. (1979). Chem. Lett. 8, 319– 320. Shimoi, M., Ouchi, A., Uehiro, T., Yoshino, Y., Sato, S. & Saito, Y. (1982). Bull. Chem. Soc. Jpn, 55, 2371–2377. So, H., Lin, Y. C., Huang, G. G. S. & Chang, T. S. T. (1993). Wear, 166, 17–26. Tripathi, U. N. & Singh, M. S. (1999). J. Indian Chem. Soc. 76, 360– 361. Vogel, A. I. (1991). A Textbook of Quantitative Chemical Analysis, 5th ed. London: BLBS and Longman. Williams, G. A. & Robson, R. (1981). Aust. J. Chem. 34, 65–79. Xu, Z., Lin, J.-H, Yu, Y.-P, Xu, J., You, X.-Z., Liu, S.-X. & Lin, C.-C. (1989). Huaxue Xuebao, 47, 623–627. Yamada, Y., Shimoi, M. & Quchi, A. (1978). Chem. Lett. 7, 867–870. Zu, B. H., Liu, S. T., Wu, B. F. & Hu, X. (2002). Huaxue Yanjiu Yu Yingyong, 14, 671–674.
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