Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 14–21
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Quantum chemical computations, vibrational spectroscopic studies, NLO and NBO/NLMO analysis of o-chlorobenzohydrazide E. Gobinath a, R. John Xavier b,⇑ a b
Department of Physics, Jayaram College of Engineering and Technology, Tiruchirappalli 621 014, India PG and Research Department of Physics, Periyar EVR College (Autonomous), Tiruchirappalli 620 023, India
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
The FT-IR and FT-Raman spectra of
the title compound have been recorded. Optimized geometry, vibrational frequencies are obtained. The first hyperpolarizability has been determined. The FMOs have been visualized. Stability of the molecule has been analyzed using NBO and NLMO analysis.
a r t i c l e
i n f o
Article history: Received 15 December 2013 Received in revised form 5 March 2014 Accepted 18 March 2014 Available online 27 March 2014 Keywords: o-Chlorobenzohydrazide FT-IR FT-Raman NMR NBO NLMO
a b s t r a c t The molecular vibrations of o-chlorobenzohydrazide (OCBH) have been investigated in polycrystalline sample, at room temperature, by recording Fourier transform infrared (FT-IR) and FT-Raman spectroscopies. The complete vibrational assignment and analysis of the fundamental modes was carried out using the experimental data and quantum chemical studies. The observed vibrational data were compared with the wavenumbers derived theoretically for the optimized geometry of the compound from the HF and DFT/B3LYP calculations employing 6-311++G(d,p) basis set. The 1H and 13C NMR chemical shifts have been simulated. Thermodynamic properties have been calculated at different temperatures. HOMO–LUMO energy gap has been calculated. The intramolecular contacts have been interpreted using Natural Bond Orbital (NBO) and Natural Localized Molecular Orbital (NLMO) analysis. Ó 2014 Elsevier B.V. All rights reserved.
Introduction Hydrazides are a class of organic compounds sharing a common functional group characterized by a nitrogen to nitrogen covalent bond with 4 substituent and at least one of them being an acyl group [1]. They have been known to associate with antibacterial, antifungal, anthelmintic, anticonvulsant, antimicrobial, ⇑ Corresponding author. Tel.: +91 431 2705674. E-mail address: [email protected] (R.J. Xavier). http://dx.doi.org/10.1016/j.saa.2014.03.026 1386-1425/Ó 2014 Elsevier B.V. All rights reserved.
antitubercular, antitumor, analgesic, anti-inflammatory, antimalarial, and antidiabetic activities, etc. Hydrazides are important starting materials for wide range of derivatives utilized in pharmaceutical products. Hydrazides and their derivatives are present in many of bioactive heterocyclic compounds that are of wide interest due to their diverse biological and clinical applications [2–6] and they have been subjected to intense research because of their interesting characteristics [7–10]. p-Hydroxy benzohydrazide moiety and its analogs seemed to be suitable parent compounds upon which variety of biological activities were reported such as
E. Gobinath, R.J. Xavier / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 14–21
antitumor [11], antianginal [12], antitubercular [13], antihypertensive [14] and antibacterial [15]. Up to now, to the best of our knowledge, no detailed spectroscopic investigation has been carried out on the title compound, o-chlorobenzohydrazide [OCBH]. Therefore in this paper we report our experimental and theoretical vibrational spectroscopic investigations made on OCBH, by recording the FT-IR and FT-Raman spectra and analyzing them with the help of quantum chemical computations made using ab initio HF and DFT-B3LYP methods. To have a better understanding on the title compound and its vibrational spectra, we also report the geometrical structure, thermodynamic properties and important electronic properties like charges on the molecule, HOMO–LUMO energies and second order perturbation energies calculated by NBO/NLMO analysis.
Experimental details The fine polycrystalline sample of OCBH was purchased from commercial sources with a stated purity of 98% and they were used as such without further purification. The room temperature Fourier transform infrared spectra of the title compound was measured in the region 4000–400 cm1 at a resolution of ±1 cm1 using a JASCO FT/IR – 6300 spectrometer. KBr pellets were used in the spectral measurements. Boxcar apodization was used for 250 averaged interferograms collector for both the sample and background. The FT-Raman spectrum of the title compound was recorded on a BRUKER RFS 100/S model interferometer equipped with an FRA106 FT-Raman accessory in the 3500–50 cm1 Stokes region using the 1064 nm line of Nd: YAG laser for excitation, operating at 150mW power. The reported wave numbers are believed to be accurate within ±4 cm1.
Computational details The entire quantum chemical calculations of the title compound OCBH have been performed by DFT (B3LYP) method with 6-311++G(d,p) basis set using the Gaussian 09W program [16]. The optimized structural parameters have been evaluated for the calculations of vibrational frequencies by assuming Cs point group symmetry. Initial geometry generated from the standard geometrical parameters was minimized without any constraint on the potential energy surface at Hartree–Fock level adopting the standard 6-311++G(d,p) basis set. This geometry was then re-optimized again at DFT level employing the Becke 3LYP keyword, which invokes Becke’s three parameter-hybrid method [17] using the correlation function of Lee et al. [18] implemented with the same basis set for better description of the bonding properties. The optimized structural parameters were used in the vibrational frequency calculations. Multiple scaling of the force constants were performed in accordance with the SQM procedure [19,20] using relative scaling in the natural internal coordinate representation [21,22], so as to have the observed data in line with the experimental ones. Transformations of the force field, and the subsequent normal coordinate analysis (NCA) including the least square refinement of the scaling factors, calculation of the potential energy distribution (PED) and the prediction of IR and Raman intensities were done on a PC with the MOLVIB Program (Version V7.0-G77) written by Sundius [23–25]. Further, the important theromodynamic properties and the electronic properties of the title compounds have been computed theoretically by B3LYP method with 6-311++G(d,p) basis set.
15
Results and discussion Molecular geometry and structural properties The molecular structure and numbering of the atoms of OCBH are shown in Fig. 1. The global minimum energies obtained by ab initio HF and DFT/B3LYP with 6-311++G(d,p) basis set for OCBH are calculated as 912.511 and 916.018 Hartrees, respectively. The optimized geometrical parameters have been obtained using the above methods and they are presented in Table 1 with the experimental X-ray diffraction [26] bond lengths and bond angles of a similar compound. The internal coordinates and local symmetry coordinates of OCBH are shown in Supplementary Tables S1 and S2, respectively. As the charge distribution on the molecule has an important influence on the vibrational spectra, the natural population analysis (NPA) charge distribution of OCBH was calculated by B3LYP/6311++G(d,p) method and presented in Table 2. Thermodynamic properties Table 3 gives the thermodynamic properties like standard heat capacities, standard entropies and the standard enthalpy changes of the title compound in gas phase at different temperatures calculated by B3LYP/6-311++G(d,p) method. Fig. 2 depicts the correlation of heat capacity at constant pressure (Cp), entropy (S) and enthalpy charge (DH0 ? T) with temperature. The corresponding fitting equations with fitting factors (R2) are as follows.
Sm ¼ 9:604 106 T 2 þ 0:1512T þ 56:138 ðR2 ¼ 0:9999Þ
C p ¼ 5:8207 105 T 2 þ 0:1328T þ 5:1608 ðR2 ¼ 0:9996Þ
DHm ¼ y ¼ 3:455 105 T 2 þ 0:0558T þ 2:8013 ðR2 ¼ 0:9996Þ From the table it is observed that the thermodynamic functions are increasing with temperature since the molecular vibrations increase with temperature. Vibrational analysis The OCBH molecule contains 18 atoms and hence it has 48 modes (3N 6) of vibrations. Out of these 48 modes, 33 are
Fig. 1. Molecular structure of o-chlorobenzohydrazide along with numbering of atoms.
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Table 1 Experimental (XRD) and optimized geometrical parameters (bond length, bond angle, dihedral angle) of o-chlorobenzohydrazide obtained by HF and B3LYP methods. Parameters
Experimentala
HF
B3LYP
ATOM
HF
B3LYP
6-311G++(d,p)
6-311++G(d,p)
C1 C2 C3 C4 C5 C6 C7 O8 N9 H10 N11 H12 H13 Cl14 H15 H16 H17 H18
0.15986 0.01268 0.20274 0.16455 0.18387 0.14824 0.81680 0.68690 0.51735 0.38473 0.61610 0.34180 0.34728 0.01439 0.21138 0.19843 0.19875 0.20749
0.15200 0.03093 0.21555 0.18131 0.19603 0.16425 0.66293 0.58945 0.45178 0.38086 0.63275 0.34979 0.35367 0.00913 0.22085 0.20974 0.20978 0.21731
Bond length (Å) C1–C2 C1–C6 C1–C7 C2–C3 C2–Cl14 C3–C4 C3–H15 C4–C5 C4–H16 C5–C6 C5–H17 C6–H18 C7–O8 C7–N9 N9–H10 N9–N11 N11–H12 N11–H13
1.385 1.380 1.473 1.386 – 1.377 0.930 1.379 0.930 1.378 0.930 0.930 1.229 1.365 0.860 1.372 – –
1.384 1.389 1.511 1.384 1.747 1.383 1.073 1.385 1.075 1.382 1.075 1.075 1.193 1.353 0.994 1.384 0.998 0.998
1.396 1.400 1.513 1.392 1.764 1.392 1.083 1.394 1.084 1.391 1.084 1.084 1.219 1.367 1.011 1.402 1.014 1.015
Bond angle (°) C1–C2–C3 C2–C3–C4 C3–C4–C5 C4–C5–C6 C1–C6–C5 C2–C1–C6 C2–C1–C7 C6–C1–C7 C1–C2–Cl14 C3–C2–Cl14 C2–C3–H15 C4–C3–H15 C3–C4–H16 C5–C4–H16 C4–C5–H17 C6–C5–H17 C1–C6–H18 C5–C6–H18 C1–C7–O8 C1–C7–N9 O8–C7–N9 C7–N9–H10 C7–N9–N11 H10–N9–N11 N9–N11–H12 N9–N11–H13 H12–N11–H13
121.1 120.0 119.20 120.50 121.11 118.1 123.4 118.5 – – 120.0 120.0 120.4 120.4 119.80 119.80 119.50 119.50 121.7 115.7 122.5 – – – – – –
121.30 119.49 120.10 119.77 120.89 118.44 123.78 117.68 120.42 118.27 119.66 120.85 119.55 120.35 120.31 119.92 118.94 120.17 120.74 117.46 121.71 116.28 127.89 115.83 111.50 111.53 110.52
121.55 119.41 120.10 119.81 121.09 118.02 124.25 117.55 120.42 118.01 119.66 120.93 119.48 120.41 120.29 119.90 118.53 120.38 120.90 117.42 121.62 116.12 128.23 115.56 110.79 110.62 109.85
Dihedral angle (°) C6–C1–C2–Cl14 C7–C1–C2–C3 C2–C1–C6–H18 C7–C1–C6–C5 C2–C1–C7–O8 C2–C1–C7–N9 C6–C1–C7–O8 C6–C1–C7–N9 C1–C2–C3–H15 Cl14–C2–C3–C4 C2–C3–C4–H16 H15–C3–C4–C5 C3–C4–C5–H17 H16–C4–C5 –C6 C4–C5–C6–H18 H17–C5–C6–C1 C1–C7–N9–H10 O8–C7–N9–N11 C7–N9–N11–H12 C7–N9–N11–H13 H10–N9–N11–H12 H10–N9–N11–H13
– – – – – – – – – – – – – – – – – – – – – –
–178.15 176.95 178.07 177.79 107.34 75.73 68.92 108.01 179.41 179.15 179.89 179.00 179.23 179.51 178.44 179.73 179.00 177.38 58.26 65.83 121.22 114.69
–177.68 175.67 178.81 176.75 111.95 70.92 62.95 114.17 179.24 178.86 179.84 178.79 179.24 179.43 178.22 179.57 178.58 174.89 54.02 68.04 122.36 115.57
For numbering of atoms refer Fig. 1. a Values are taken from Ref. [26].
Table 2 The NPA charge distribution of o-chlorobenzohydrazide calculated by HF and B3LYP methods using 6-311++G(d,p) basis set.
Table 3 Thermodynamic properties of o-chlorobenzohydrazide at different temperatures calculated by B3LYP/6-311++G(d,p) method. T (K)
S°m (cal mol–1 K–1)
C°p (cal mol–1 K–1)
DH°m (kcal mol–1)
100 200 298.15 300 400 500 600 700 800 900 1000
71.331 86.933 102.045 102.332 118.020 134.032 150.309 166.779 183.383 200.069 216.802
18.104 28.897 39.436 39.628 49.391 57.5410 64.099 69.370 73.670 77.238 80.240
9.702 14.997 21.944 22.086 30.311 39.375 49.101 59.367 70.077 81.155 92.543
in-plane (A0 species) and 15 are out-of-plane (A00 species). Vibrational spectral assignments of the title compound was performed on the recorded FT-IR and FT-Raman spectra based on the theoretically predicted wavenumbers by ab initio HF and DFT/B3LYP levels using 6-311++G(d,p) basis set and are presented in Table 4. The observed FTIR and FT-Raman spectra of OCBH are presented in Fig. 3. Normally, the vibrational frequencies obtained by quantum chemical calculations with unscaled ab initio and DFT force field are greater than the experimental values due to the facts of the electron correlation approximate treatment, the anharmonicity effect and basis set deficiency, etc., [27]. In order to improve the calculated values in agreement with the experimental values, it is necessary to scale down the calculated harmonic frequencies. After scaling, the theoretical frequencies will match well with the experimental ones. Carbon–Hydrogen vibrations The aromatic C–H ring stretching vibrations are normally found between 3100 and 3000 cm1 [28]. C–H stretching modes of OCBH are observed in IR spectra at 3056, 3024 cm1, in Raman spectra at 3071, 3059 and 3010 cm1. The in-plane bending modes are observed at 1191, 1055, 991, 899 and 896 cm1 in OCBH. All the above are in good agreement with the calculated wave numbers by HF and B3LYP methods. Carbon–Carbon vibrations The aromatic ring carbon–carbon stretching modes are expected in the range 1650–1200 cm1 [29]. In OCBH, the infrared active bands at 1646, 1594, 1433, 1339 cm1 and Raman active
Entropy (Cal/Mol-Kelvin)
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17
a
200 180 160 140 120 100 80 60
100
200
300
400
500
600
700
800
900
1000
700
800
900
1000
700
800
900
1000
Heat capacity (Cal/Mol-Kelvin)
Temperature (K) 90 80 70 60 50 40 30 20 10
b
100
200
300
400
500
600
Enthalphy (kcal/mol)
Temperature (K) 100
c
80 60 40 20 0
100
200
300
400
500
600
Temperature (K) Fig. 2. Correlation graph for for o-chlorobenzohydrazide. (a) Entropy and temperature. (b) Heat capacity and temperature. (c) Enthalpy and temperature.
bands at 1651, 1597, 1329 and 1321 cm1 have been ascribed to C–C stretching mode. The computed values for the above in both HF and B3LYP methods are found to be in good agreement with the observed ones as shown in Table 4. Carbon–Chlorine vibrations The vibrations belonging to C–X (X = F, Cl, Br) bonds which are formed between the ring and the halogen atoms are worth to discuss, since mixing of vibrations are possible due to the lowering of molecular symmetry and the presence of heavy atoms. Further, the C–Cl absorption is observed in the broad region between 859 and 550 cm1 [30–35]. In OCBH, an FT-IR band at 651 cm1 is assigned to C-Cl stretching vibration. The Raman bands at 310 cm1 and at 289 cm1 have been assigned to in-plane and out-of-plane bending vibrations, respectively and they are found to be in line with the computed wavenumbers. Keto group (–CO) vibrations Ketones, aldehydes and amides generally show IR absorption at 1750–1650 cm1. Conjugation, ring size, hydrogen bonding, steric and electronic effects often result in significant shifts in CO absorption frequencies [9,36]. Accordingly, FT-Raman band at 1719 cm1 in OCBH has been assigned to –CO stretching mode of vibration and they are found to be consistent with the calculated wavenumbers. Similarly, the wavenumbers of in-plane and out-of-plane bending mode of vibrations are also in line with the computed wavenumbers. Hydrazide group (–NH–NH2) vibrations The frequencies of amino group appear around 3500– 3300 cm1 for NH2 stretching, 1700–1600 cm1 for scissoring and 1150–900 cm1 for rocking deformations [37]. NH2 asymmetric stretching mode is observed at 3286 and at 3285 cm1 in OCBH.
NH2 symmetric stretching is observed at 3185 cm1 and the –NH stretching mode is observed at 3302 cm1 in OCBH. These are found to be in line with the computed values as well as the literatures [38,39]. In addition, the NH2 group has scissoring, rocking, wagging and torsional modes of vibration. All the above modes have been assigned for the title molecule and they are given in Table 4 along with their PED values. NMR chemical shifts The isotropic chemical shifts are frequently used as an aid in identification of reactive organic as well as ionic species [40]. The Gauge-including atomic orbital (GIAO) 1H and 13C chemical shift calculations of the title compound has been made on the optimized geometry using B3LYP/6-311++G(d,p) method and presented in Table 5. The 1H NMR is interesting since the hydrogen atom is the smallest of all atoms and its chemical shift will be more susceptible to intermolecular interactions. The chemical shifts of N–H protons have been identified between 9.52 ppm to 10.51 ppm where as the C–H protons have shifts ranging from 4.57 ppm to 7.08 ppm. The typical range of 13C NMR chemical shift in organic molecules is greater than 100 ppm [41,42]. As shown in Table 5, the chemical shifts of carbon atoms are ranging from 106.55 to 189.40 ppm. NLO properties The potential application of the title compound in the field of nonlinear optics (NLO) demands the investigation of its structural and bonding features contributing to the hyperpolarizability enhancement. First hyperpolarizability is a third rank tensor that can be described by 3 3 3 matrix. The 27 components of 3D matrix can be reduced to 10 components due to the Kleinmann
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Table 4 Experimental and calculated (unscaled and scaled) HF/6-311++G(d,p) and B3LYP/6-311++G(d,p) level vibrational frequencies (cm1), IR intensity (km mol1), Raman activity (Å4 amu1), force constant (mdyne Å1) and probable assignments of o-chlorobenzohydrazide. No
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48.
Symm. species Cs
A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A00 A0 A0 A00 A00 A0 A00 A00 A0 A00 A00 A00 A0 A00 A00 A00 A00 A00 A00 A00
Experimental frequencies (cm1)
HF/6-311++G(d,p)
B3LYP/6-311++G(d,p)
Characterization of normal modes with PED (%)
FTIR
FTRaman
Unscaled
Scaled
IR Intensity
Raman intensity
Unscaled
Scaled
IR intensity
Raman intensity
– 3286 3185 – 3056 3024 – – – 1646 1594 1568 1520 1433 1339 – – 1257 – 1162 – 1136 1055 1036 991 982 899 873 786 755 – 720 669 651 – – 473 – – – – – – – – – – –
3302 3285 – 3071 3059 – 3010 1719 1651 – 1597 1571 – – – 1329 1321 – 1191 1165 1140 – – 1037 – – 896 – – – 742 725 – – 553 551 – 447 406 364 310 289 231 200 163 141 – –
3862 3838 3744 3366 3355 3343 3331 1923 1838 1784 1751 1636 1609 1585 1495 1445 1388 1341 1312 1235 1229 1182 1139 1123 1115 1080 983 971 869 841 822 808 733 686 639 619 531 499 454 421 336 311 280. 182 155 141 106 50
3330 3316 3211 3096 3083 3047 3034 1740 1673 1668 1626 1589 1537 1456 1351 1332 1329 1272 1211 1189 1163 1152 1073 1064 1008 990 918 895 809 776 761 733 683 669 567 562 494 467 428 381 324 295 243 221 167 142 101 52
71.78 12.62 1.00 4.66 9.82 6.20 0.52 521.02 18.99 20.67 7.17 21.55 39.22 35.20 279.84 2.25 6.08 6.94 0.83 15.22 16.72 5.30 29.17 9.43 0.52 2.04 14.46 229.50 42.36 50.70 18.71 5.75 14.94 1.62 13.30 149.09 6.49 9.83 12.89 2.10 3.71 2.96 4.87 0.43 2.22 3.14 1.42 1.98
1.29 0.31 0.86 3.23 1.99 1.49 0.86 1.30 0.37 1.71 1.30 0.16 0.29 0.08 0.27 0.26 0.08 0.89 0.05 0.56 0.32 1.18 0.34 7.15 0.21 0.02 0.08 0.59 0.65 0.15 0.51 0.19 5.08 1.36 0.91 0.32 0.67 5.52 4.34 1.95 0.65 0.31 2.24 2.86 2.66 1.47 34.06 100
3597 3572 3485 3203 3195 3184 3174 1735 1692 1652 1605 1586 1465 1453 1376 1328 1316 1284 1223 1186 1148 1138 1058 1050 1000 966 881 874 785 763 755 729 680 634 587 583 483 460 416 390 302 282 254 170 149 142 98 51
3309 3291 3189 3077 3063 3030 3016 1725 1656 1642 1599 1574 1526 1438 1346 1330 1324 1260 1199 1172 1143 1139 1057 1040 996 985 901 876 790 759 748 724 673 655 556 552 476 450 409 367 307 284 239 194 155 143 98 57
53.12 10.3 3.18 3.82 7.33 3.83 0.70 360.64 18.84 13.75 6.69 10.22 44.41 14.04 223.50 2.39 0.53 5.07 1.27 0.21 3.31 16.74 4.25 39.20 0.14 1.41 12.66 200.73 33.60 3.25 55.63 1.36 16.35 1.12 8.61 120.81 5.87 9.18 11.56 1.56 5.60 6.59 6.44 1.03 0.98 0.61 1.81 2.23
1.32 0.29 0.92 3.12 1.65 1.28 0.70 1.63 0.35 1.82 0.48 0.75 0.14 0.38 0.61 0.31 0.32 0.04 0.99 0.53 0.15 0.94 2.65 3.19 0.03 0.01 0.05 0.92 0.49 0.26 0.19 0.10 3.15 1.15 1.00 0.42 0.93 4.05 2.80 1.12 0.42 0.45 2.01 2.45 2.03 2.76 30.86 100
NH (100) NH2 ass (100) NH2 ss (100) CH (100) CH (100) CH (100) CH (100) CO (96) CC (92) CC (90) CC (89) NN (90) NH2 sciss (89) CC (85), CN (15) CC (87), NN (11) CC (83), Rsymd (10) CC (81) CN (81) bCH (79), CC (19) NH2 rock (78) Rtrigd (72), CC (21) bNH (79), CC (19) bCH (81), CCl (17) Rsymd (69), CC (21) bCH (67), Rtrigd (23) Rasymd (69), Rtrigd(19) bCH (65) bNN (63) NH2 wag (73) bCC (67) bCN (63) xNH (59) xCH (60) CCl (81) xCH (57), xCO (21) xCH (59), tRsym (19) bCO (73), Rtrigd (21) xCH (61), xCC (23) tRtrig (63), tRasym (21) xCO (57), xCCl (17) bCCl (59), Rsymd(23) xCCl (60), tRasym(21) xNN (56), xCC (23) xCC (55), xCH (17) tRsym (61), tRtrig (23) xCN (59), xCC (20) tRasym (63), xCH (19) NH2 twist (69)
For the notations used, see Supplementary Table S2.
where
Urea is one of the prototypical molecules used in the study of the NLO properties of molecular systems. Therefore it was used frequently as a threshold value for comparative purposes. The calculated value of b for OCBH is 0.223 1030 esu which is slightly lower than that of Urea (0.3728 1030 esu). Besides the hyperpolarizability, other important properties of the title compound like dipole moment, polarizability have also been computed and presented in the Table 6.
bx ¼ bxxx þ bxyy þ bxzz
HOMO–LUMO analysis
symmetry [43,44]. The output from Gaussian 03 provides 10 components of this matrix as bxxx, bxxy, bxyy, byyy, bxxz, bxyz, byyz, bxzz, byzz, bzzz, respectively and they are given in Table 6. The components of the first hyperpolarizability can be calculated using the following equations.
b ¼ b2x þ b2y þ b2z
by ¼ byyy þ bxxy þ byzz bz ¼ bzzz þ bxxz þ byyz
The most important orbitals in a molecule that determine the way the molecule interacts with other species are, the frontier molecular orbitals (FMOs), called highest occupied molecular
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Table 5 The chemical shielding and shift (GIAO method) for o-chlorobenzohydrazide calculated by B3LYP/6-311++G(d,p) method. ATOM
Chemical shift (ppm)
ATOM
Chemical shift (ppm)
H10 H12 H13 H15 H16 H17 H18
9.52 10.49 10.51 7.98 4.63 4.57 7.08
C1 C2 C3 C4 C5 C6 C7
156.91 115.86 157.78 185.40 189.40 176.94 106.55
Eð2Þ ¼ DEij ¼ qi ¼
Fig. 3. Observed FT-IR spectra and FT-Raman spectra of o-chlorobenzohydrazide.
orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). They are the key parameter in determining molecular properties, molecular electrical transport properties [45,46]. Moreover, the Eigen value of HOMO characterizes the ability of donating electron and the Eigen value of LUMO characterizes the ability of accepting electron. The energy gap between HOMO and LUMO reflects the chemical stability and they are responsible for chemical and spectroscopic properties of the molecule [47,48]. The energy of the four important FMOs such as the second highest (HOMO1) and highest occupied MO (HOMO), the lowest (LUMO) and the second lowest unoccupied MO (LUMO+1) have been calculated and the pictorial illustrations of the FMOs of OCBH have been given in Supplementary Fig. 1. In OCBH, there are 45 occupied molecular orbitals and the energy gap between HOMO and LUMO orbital is 0.21102 a.u.
Fði; jÞ
2
ei ej
where qi is the donor orbital occupancy, ei, ej are diagonal elements (orbital energies) and F(i, j) is the off-diagonal NBO Fock matrix clement. In Table 7 the perturbation energies of significant donor–acceptor interactions are comparatively presented for OCBH. The larger the E(2) value, the intense is the interaction between electron donors and electron acceptors. In OCBH, the interactions initiated by the donor NBOs like BD (2) C1–C2, BD (2) C3–C4, BD (2) C5–C6 and NBOs due to lone pairs of O8, N9 and Cl14 are giving substantial stabilization to the structure. Above all, the interaction between antibonding orbitals namely, BD (2) C1–C2 ? BD (2) C5–C6 is giving the most possible stabilization to OCBH since it has the most E(2) value around 262.81 kcal/mol. The Natural Localized Molecular Orbital (NLMO) analysis has been carried out since they show how bonding in a molecule is composed from orbitals localized on different atoms. The derivation of NLMOs from NBOs gives direct insight into the nature of the localized molecular orbital’s ‘‘delocalization tails’’ [51,35]. Table 6 Electric dipole moment, Polarizability and Hyperpolarizability of o-chlorobenzohydrazide by B3LYP with the basic set 6-311++G(d,p) level. Parameters
Value
Dipole moment (Debye)
lx ly lz Mtotal
2.6952 0.4607 3.0893 4.1255
Polarizability (a)
axx ayy azz axy axz ayz aTotal1024
65.2359 69.7708 78.0259 2.4577 1.1891 4.5027 71.010867
Anisotropic tensor A B C
252.296094 27.7285554 209.333713
NBO/NLMO analysis Natural Bond Orbital (NBO) analysis provides an efficient method for studying interesting features of molecular structure. They give strong insight in the intra and inter molecular bonding and interaction among bonds, and also provide a convenient basis for investigation of charge transfer or conjugative interactions in molecular system [49]. Another useful aspect of NBO method is that it gives information about interactions in both filled and virtual orbital spaces that could help to have a detailed analysis of intra and intermolecular interactions. The second order Fock matrix was carried out to evaluate the donor–acceptor interactions in the NBO analysis [50]. For each donor NBO (i) and acceptor NBO (j), the stabilization energy associated with i ? j delocalization can be estimated as,
Hyper polarisability (b) bxxx byyy bzzz bxyy byxx bzxx bxzz byzz bzyy bTotal ( 1030 esu)
4.4903 1.8681 7.1513 5.7598 2.1692 0.0119 3.9544 9.7271 9.5865 0.223
20
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Table 7 Significant donor–acceptor interactions and second order perturbation energies of o-chlorobenzohydrazide calculated by B3LYP method using 6-311++G(d,p) basis set. Donor NBO (i)
Acceptor NBO (j)
BD (2) C1–C2
BD BD BD BD BD BD BD BD BD BD BD BD
BD (2) C3–C4 BD (2) C5–C6 LP (2) O8 LP (1) N9 LP (1) Cl14 BD (2) C1–C2 BD (2) C7–O8 a b c
(2) (2) (1) (2) (2) (2) (1) (1) (2) (2) (2) (2)
E(2)
C3–C4 C5–C6 C1–C2 C5–C6 C1–C2 C3–C4 C1–C7 C7–N9 C7–O8 C1–C2 C5–C6 C7–O8
a
(kcal/mol)
19.31 18.37 20.91 19.46 22.43 21.16 21.54 25.70 32.30 12.78 262.81 32.55
Ej Ei
b
(a.u)
0.31 0.31 0.28 0.29 0.28 0.28 0.65 0.73 0.42 0.34 0.01 0.37
F(i, j)
c
(a.u)
0.069 0.067 0.069 0.067 0.071 0.070 0.107 0.124 0.106 0.065 0.086 0.257
E(2) means energy of hyperconjucative interactions. Energy difference between donor and acceptor i and j NBO orbitals. F(i, j) is the Fock matrix element between i and j NBO orbitals.
Table 8 Significant NLMO’s occupancy, percentage from parent NBO and atomic hybrid contributions of o-chlorobenzohydrazide calculated at B3LYP level using 6-311++G(d,p) basis set. Bond
Occupancy
% from parent NBO
Hybrid contributions Atom
%
BD(2) C1–C2
2.00000
84.1144
C1 C2 C3 C4 C5 C6
41.130 42.989 5.939 1.515 1.532 5.976
BD(2) C3–C4
2.00000
81.9373
C1 C2 C3 C4 C5 C6
4.134 4.039 38.969 43.037 7.375 2.191
BD(2) C5–C6
2.00000
81.0910
C1 C2 C3 C4 C5 C6
4.880 4.822 4.379 4.687 40.496 40.600
LP (2) O8
2.00000
92.2727
C1 C7 O8 N9
1.570 3.778 92.273 1.541
LP (1) N9
2.00000
85.6034
C7 O8 N9
8.773 4.132 85.604
Table 8 shows the comparative study of significant NLMO’s occupancy, percentage from parent NBO and atomic hybrid contributions of OCBH calculated at B3LYP level using 6-311++G(d,p) basis set. The most delocalized NLMO is BD (2) C5–C6 for OCBH. It has around 81.09% contribution from the localized parent NBO and has a delocalization tail of 18.91% consists of the hybrids from C1, C2, C3 and C4. The other most delocalized NLMOs in OCBH are BD (2) C3–C4, BD (2) C1–C2 and NLMOs due to lone pairs of O8 and N9. The significant amount of delocalization tail of an NLMO indicates that they are strongly delocalized into the vicinal regions. This delocalization can also be observed in the perturbation theory energy analysis given in Table 7. Conclusion In the present work, FT-IR and FT-Raman spectra of the title compound o-chlorobenozohydrazide have been recorded and
compared with the theoretically constructed spectra using HF and DFT/B3LYP methods with 6-311++G(d,p) basis set. All the fundamental modes of the optimized structure have been assigned precisely on the basis of potential energy distribution (PED) and close agreement between the experimental and scaled frequencies were achieved. The molecular structural parameters like bond length and bond angle, thermodynamic properties have been determined from ab initio and DFT calculations using 6-311 ++G(d,p) basis set. The computed geometrical parameters are compared with the observed X-ray diffraction data of similar compound. The frontier molecular orbitals have been visualized and the HOMO–LUMO energy gap has been calculated. The stability and intramolecular interactions have been interpreted by NBO/NLMO analysis and the transactions give stabilization to the structure have been identified by second order perturbation energy calculations. The calculation of first hyperpolarizability reveals that the title compound possesses comparable NLO properties. Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.saa.2014.03.026. References [1] M. Nic, J. Jirat, B. Kosata (Eds.). ‘‘Hydrazides’’. IUPAC Compendium of Chemical Terminology (Online ed.), 2006. doi:10.1351/gold book. ISBN 0-9678550-9-8. [2] I. Mir, M.T. Siddiqui, A. Comrie, Tetrahedron 26 (22) (1970) 5235–5238. [3] E. Degener, H. Scheinplug, H.G. Schemelzer, Brit. Patent No. 1035, 474 (1967). [4] R. Cavier, R. Rips, J. Med. Chem. 8 (5) (1965) 706–708. [5] D.L. Trepanier, E.R. Wagner, G. Harris, A.D. Rudzik, J. Med. Chem. 9 (6) (1996) 881–885. [6] M. Goyal, N. Mahadevan, D. Kaushik, Int. J. Rec. Adv. Pharm. Res. 2 (2011) 27– 29. [7] E. Gobinath, R.J. Xavier, Spectrochim. Acta Part A Mol. Biomol. Spectrosc. 115 (2013) 815–822. [8] V. Vimalraj, S. Vijayalakshmi, S. Umayaparvathi, A.R. Krishnan, Spectrochim. Acta Part A 78 (2011) 670–675. [9] V. Arjunan, T. Rani, C.V. Mythili, S. Mohan, Spectrochim. Acta Part A Mol. Biomol. Spectrosc. 79 (2011) 486–496. [10] J. Zhang, T. Zhang, K. Yu, Struct. Chem. 17 (2006) 249–254. [11] K.K. Vijayaraj, B. Narayana, B.V. Ashalatha, N. Suchetha Kumari, B.K. Sarojini, Eur. J. Med. Chem. 42 (2007) 425–429. [12] A.H. Abadi, A.A.H. Eissa, G.S. Hassan, Chem. Pharm. Bull. 51 (7) (2003) 838– 844. [13] C.G. Bonde, N.J. Gaikwad, Bioorg. Med. Chem. 12 (2004) 2151–2161. [14] S.V. Bhandari, A.A. Patil, V. Sarkate, S.G. Gore, K.G. Bothra, Bioorg. Med. Chem. 17 (2009) 390–400. [15] K. Sugano, H. Hamada, M. Machida, H. Ushio, J. Biomol. Screen. 6 (2001) 189– 196. [16] H.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, R. Nakajima, Y. Honda, O. Kilao, H. Nakai, T.
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Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy journal homepage: www.elsevier.com/locate/saa
Quantum chemical computations, vibrational spectroscopic studies, NLO and NBO/NLMO analysis of o-chlorobenzohydrazide E. Gobinath a, R. John Xavier b,⇑ a b
Department of Physics, Jayaram College of Engineering and Technology, Tiruchirappalli 621 014, India PG and Research Department of Physics, Periyar EVR College (Autonomous), Tiruchirappalli 620 023, India
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
The FT-IR and FT-Raman spectra of
the title compound have been recorded. Optimized geometry, vibrational frequencies are obtained. The first hyperpolarizability has been determined. The FMOs have been visualized. Stability of the molecule has been analyzed using NBO and NLMO analysis.
a r t i c l e
i n f o
Article history: Received 15 December 2013 Received in revised form 5 March 2014 Accepted 18 March 2014 Available online 27 March 2014 Keywords: o-Chlorobenzohydrazide FT-IR FT-Raman NMR NBO NLMO
a b s t r a c t The molecular vibrations of o-chlorobenzohydrazide (OCBH) have been investigated in polycrystalline sample, at room temperature, by recording Fourier transform infrared (FT-IR) and FT-Raman spectroscopies. The complete vibrational assignment and analysis of the fundamental modes was carried out using the experimental data and quantum chemical studies. The observed vibrational data were compared with the wavenumbers derived theoretically for the optimized geometry of the compound from the HF and DFT/B3LYP calculations employing 6-311++G(d,p) basis set. The 1H and 13C NMR chemical shifts have been simulated. Thermodynamic properties have been calculated at different temperatures. HOMO–LUMO energy gap has been calculated. The intramolecular contacts have been interpreted using Natural Bond Orbital (NBO) and Natural Localized Molecular Orbital (NLMO) analysis. Ó 2014 Elsevier B.V. All rights reserved.
Introduction Hydrazides are a class of organic compounds sharing a common functional group characterized by a nitrogen to nitrogen covalent bond with 4 substituent and at least one of them being an acyl group [1]. They have been known to associate with antibacterial, antifungal, anthelmintic, anticonvulsant, antimicrobial, ⇑ Corresponding author. Tel.: +91 431 2705674. E-mail address: [email protected] (R.J. Xavier). http://dx.doi.org/10.1016/j.saa.2014.03.026 1386-1425/Ó 2014 Elsevier B.V. All rights reserved.
antitubercular, antitumor, analgesic, anti-inflammatory, antimalarial, and antidiabetic activities, etc. Hydrazides are important starting materials for wide range of derivatives utilized in pharmaceutical products. Hydrazides and their derivatives are present in many of bioactive heterocyclic compounds that are of wide interest due to their diverse biological and clinical applications [2–6] and they have been subjected to intense research because of their interesting characteristics [7–10]. p-Hydroxy benzohydrazide moiety and its analogs seemed to be suitable parent compounds upon which variety of biological activities were reported such as
E. Gobinath, R.J. Xavier / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 14–21
antitumor [11], antianginal [12], antitubercular [13], antihypertensive [14] and antibacterial [15]. Up to now, to the best of our knowledge, no detailed spectroscopic investigation has been carried out on the title compound, o-chlorobenzohydrazide [OCBH]. Therefore in this paper we report our experimental and theoretical vibrational spectroscopic investigations made on OCBH, by recording the FT-IR and FT-Raman spectra and analyzing them with the help of quantum chemical computations made using ab initio HF and DFT-B3LYP methods. To have a better understanding on the title compound and its vibrational spectra, we also report the geometrical structure, thermodynamic properties and important electronic properties like charges on the molecule, HOMO–LUMO energies and second order perturbation energies calculated by NBO/NLMO analysis.
Experimental details The fine polycrystalline sample of OCBH was purchased from commercial sources with a stated purity of 98% and they were used as such without further purification. The room temperature Fourier transform infrared spectra of the title compound was measured in the region 4000–400 cm1 at a resolution of ±1 cm1 using a JASCO FT/IR – 6300 spectrometer. KBr pellets were used in the spectral measurements. Boxcar apodization was used for 250 averaged interferograms collector for both the sample and background. The FT-Raman spectrum of the title compound was recorded on a BRUKER RFS 100/S model interferometer equipped with an FRA106 FT-Raman accessory in the 3500–50 cm1 Stokes region using the 1064 nm line of Nd: YAG laser for excitation, operating at 150mW power. The reported wave numbers are believed to be accurate within ±4 cm1.
Computational details The entire quantum chemical calculations of the title compound OCBH have been performed by DFT (B3LYP) method with 6-311++G(d,p) basis set using the Gaussian 09W program [16]. The optimized structural parameters have been evaluated for the calculations of vibrational frequencies by assuming Cs point group symmetry. Initial geometry generated from the standard geometrical parameters was minimized without any constraint on the potential energy surface at Hartree–Fock level adopting the standard 6-311++G(d,p) basis set. This geometry was then re-optimized again at DFT level employing the Becke 3LYP keyword, which invokes Becke’s three parameter-hybrid method [17] using the correlation function of Lee et al. [18] implemented with the same basis set for better description of the bonding properties. The optimized structural parameters were used in the vibrational frequency calculations. Multiple scaling of the force constants were performed in accordance with the SQM procedure [19,20] using relative scaling in the natural internal coordinate representation [21,22], so as to have the observed data in line with the experimental ones. Transformations of the force field, and the subsequent normal coordinate analysis (NCA) including the least square refinement of the scaling factors, calculation of the potential energy distribution (PED) and the prediction of IR and Raman intensities were done on a PC with the MOLVIB Program (Version V7.0-G77) written by Sundius [23–25]. Further, the important theromodynamic properties and the electronic properties of the title compounds have been computed theoretically by B3LYP method with 6-311++G(d,p) basis set.
15
Results and discussion Molecular geometry and structural properties The molecular structure and numbering of the atoms of OCBH are shown in Fig. 1. The global minimum energies obtained by ab initio HF and DFT/B3LYP with 6-311++G(d,p) basis set for OCBH are calculated as 912.511 and 916.018 Hartrees, respectively. The optimized geometrical parameters have been obtained using the above methods and they are presented in Table 1 with the experimental X-ray diffraction [26] bond lengths and bond angles of a similar compound. The internal coordinates and local symmetry coordinates of OCBH are shown in Supplementary Tables S1 and S2, respectively. As the charge distribution on the molecule has an important influence on the vibrational spectra, the natural population analysis (NPA) charge distribution of OCBH was calculated by B3LYP/6311++G(d,p) method and presented in Table 2. Thermodynamic properties Table 3 gives the thermodynamic properties like standard heat capacities, standard entropies and the standard enthalpy changes of the title compound in gas phase at different temperatures calculated by B3LYP/6-311++G(d,p) method. Fig. 2 depicts the correlation of heat capacity at constant pressure (Cp), entropy (S) and enthalpy charge (DH0 ? T) with temperature. The corresponding fitting equations with fitting factors (R2) are as follows.
Sm ¼ 9:604 106 T 2 þ 0:1512T þ 56:138 ðR2 ¼ 0:9999Þ
C p ¼ 5:8207 105 T 2 þ 0:1328T þ 5:1608 ðR2 ¼ 0:9996Þ
DHm ¼ y ¼ 3:455 105 T 2 þ 0:0558T þ 2:8013 ðR2 ¼ 0:9996Þ From the table it is observed that the thermodynamic functions are increasing with temperature since the molecular vibrations increase with temperature. Vibrational analysis The OCBH molecule contains 18 atoms and hence it has 48 modes (3N 6) of vibrations. Out of these 48 modes, 33 are
Fig. 1. Molecular structure of o-chlorobenzohydrazide along with numbering of atoms.
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Table 1 Experimental (XRD) and optimized geometrical parameters (bond length, bond angle, dihedral angle) of o-chlorobenzohydrazide obtained by HF and B3LYP methods. Parameters
Experimentala
HF
B3LYP
ATOM
HF
B3LYP
6-311G++(d,p)
6-311++G(d,p)
C1 C2 C3 C4 C5 C6 C7 O8 N9 H10 N11 H12 H13 Cl14 H15 H16 H17 H18
0.15986 0.01268 0.20274 0.16455 0.18387 0.14824 0.81680 0.68690 0.51735 0.38473 0.61610 0.34180 0.34728 0.01439 0.21138 0.19843 0.19875 0.20749
0.15200 0.03093 0.21555 0.18131 0.19603 0.16425 0.66293 0.58945 0.45178 0.38086 0.63275 0.34979 0.35367 0.00913 0.22085 0.20974 0.20978 0.21731
Bond length (Å) C1–C2 C1–C6 C1–C7 C2–C3 C2–Cl14 C3–C4 C3–H15 C4–C5 C4–H16 C5–C6 C5–H17 C6–H18 C7–O8 C7–N9 N9–H10 N9–N11 N11–H12 N11–H13
1.385 1.380 1.473 1.386 – 1.377 0.930 1.379 0.930 1.378 0.930 0.930 1.229 1.365 0.860 1.372 – –
1.384 1.389 1.511 1.384 1.747 1.383 1.073 1.385 1.075 1.382 1.075 1.075 1.193 1.353 0.994 1.384 0.998 0.998
1.396 1.400 1.513 1.392 1.764 1.392 1.083 1.394 1.084 1.391 1.084 1.084 1.219 1.367 1.011 1.402 1.014 1.015
Bond angle (°) C1–C2–C3 C2–C3–C4 C3–C4–C5 C4–C5–C6 C1–C6–C5 C2–C1–C6 C2–C1–C7 C6–C1–C7 C1–C2–Cl14 C3–C2–Cl14 C2–C3–H15 C4–C3–H15 C3–C4–H16 C5–C4–H16 C4–C5–H17 C6–C5–H17 C1–C6–H18 C5–C6–H18 C1–C7–O8 C1–C7–N9 O8–C7–N9 C7–N9–H10 C7–N9–N11 H10–N9–N11 N9–N11–H12 N9–N11–H13 H12–N11–H13
121.1 120.0 119.20 120.50 121.11 118.1 123.4 118.5 – – 120.0 120.0 120.4 120.4 119.80 119.80 119.50 119.50 121.7 115.7 122.5 – – – – – –
121.30 119.49 120.10 119.77 120.89 118.44 123.78 117.68 120.42 118.27 119.66 120.85 119.55 120.35 120.31 119.92 118.94 120.17 120.74 117.46 121.71 116.28 127.89 115.83 111.50 111.53 110.52
121.55 119.41 120.10 119.81 121.09 118.02 124.25 117.55 120.42 118.01 119.66 120.93 119.48 120.41 120.29 119.90 118.53 120.38 120.90 117.42 121.62 116.12 128.23 115.56 110.79 110.62 109.85
Dihedral angle (°) C6–C1–C2–Cl14 C7–C1–C2–C3 C2–C1–C6–H18 C7–C1–C6–C5 C2–C1–C7–O8 C2–C1–C7–N9 C6–C1–C7–O8 C6–C1–C7–N9 C1–C2–C3–H15 Cl14–C2–C3–C4 C2–C3–C4–H16 H15–C3–C4–C5 C3–C4–C5–H17 H16–C4–C5 –C6 C4–C5–C6–H18 H17–C5–C6–C1 C1–C7–N9–H10 O8–C7–N9–N11 C7–N9–N11–H12 C7–N9–N11–H13 H10–N9–N11–H12 H10–N9–N11–H13
– – – – – – – – – – – – – – – – – – – – – –
–178.15 176.95 178.07 177.79 107.34 75.73 68.92 108.01 179.41 179.15 179.89 179.00 179.23 179.51 178.44 179.73 179.00 177.38 58.26 65.83 121.22 114.69
–177.68 175.67 178.81 176.75 111.95 70.92 62.95 114.17 179.24 178.86 179.84 178.79 179.24 179.43 178.22 179.57 178.58 174.89 54.02 68.04 122.36 115.57
For numbering of atoms refer Fig. 1. a Values are taken from Ref. [26].
Table 2 The NPA charge distribution of o-chlorobenzohydrazide calculated by HF and B3LYP methods using 6-311++G(d,p) basis set.
Table 3 Thermodynamic properties of o-chlorobenzohydrazide at different temperatures calculated by B3LYP/6-311++G(d,p) method. T (K)
S°m (cal mol–1 K–1)
C°p (cal mol–1 K–1)
DH°m (kcal mol–1)
100 200 298.15 300 400 500 600 700 800 900 1000
71.331 86.933 102.045 102.332 118.020 134.032 150.309 166.779 183.383 200.069 216.802
18.104 28.897 39.436 39.628 49.391 57.5410 64.099 69.370 73.670 77.238 80.240
9.702 14.997 21.944 22.086 30.311 39.375 49.101 59.367 70.077 81.155 92.543
in-plane (A0 species) and 15 are out-of-plane (A00 species). Vibrational spectral assignments of the title compound was performed on the recorded FT-IR and FT-Raman spectra based on the theoretically predicted wavenumbers by ab initio HF and DFT/B3LYP levels using 6-311++G(d,p) basis set and are presented in Table 4. The observed FTIR and FT-Raman spectra of OCBH are presented in Fig. 3. Normally, the vibrational frequencies obtained by quantum chemical calculations with unscaled ab initio and DFT force field are greater than the experimental values due to the facts of the electron correlation approximate treatment, the anharmonicity effect and basis set deficiency, etc., [27]. In order to improve the calculated values in agreement with the experimental values, it is necessary to scale down the calculated harmonic frequencies. After scaling, the theoretical frequencies will match well with the experimental ones. Carbon–Hydrogen vibrations The aromatic C–H ring stretching vibrations are normally found between 3100 and 3000 cm1 [28]. C–H stretching modes of OCBH are observed in IR spectra at 3056, 3024 cm1, in Raman spectra at 3071, 3059 and 3010 cm1. The in-plane bending modes are observed at 1191, 1055, 991, 899 and 896 cm1 in OCBH. All the above are in good agreement with the calculated wave numbers by HF and B3LYP methods. Carbon–Carbon vibrations The aromatic ring carbon–carbon stretching modes are expected in the range 1650–1200 cm1 [29]. In OCBH, the infrared active bands at 1646, 1594, 1433, 1339 cm1 and Raman active
Entropy (Cal/Mol-Kelvin)
E. Gobinath, R.J. Xavier / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 14–21 220
17
a
200 180 160 140 120 100 80 60
100
200
300
400
500
600
700
800
900
1000
700
800
900
1000
700
800
900
1000
Heat capacity (Cal/Mol-Kelvin)
Temperature (K) 90 80 70 60 50 40 30 20 10
b
100
200
300
400
500
600
Enthalphy (kcal/mol)
Temperature (K) 100
c
80 60 40 20 0
100
200
300
400
500
600
Temperature (K) Fig. 2. Correlation graph for for o-chlorobenzohydrazide. (a) Entropy and temperature. (b) Heat capacity and temperature. (c) Enthalpy and temperature.
bands at 1651, 1597, 1329 and 1321 cm1 have been ascribed to C–C stretching mode. The computed values for the above in both HF and B3LYP methods are found to be in good agreement with the observed ones as shown in Table 4. Carbon–Chlorine vibrations The vibrations belonging to C–X (X = F, Cl, Br) bonds which are formed between the ring and the halogen atoms are worth to discuss, since mixing of vibrations are possible due to the lowering of molecular symmetry and the presence of heavy atoms. Further, the C–Cl absorption is observed in the broad region between 859 and 550 cm1 [30–35]. In OCBH, an FT-IR band at 651 cm1 is assigned to C-Cl stretching vibration. The Raman bands at 310 cm1 and at 289 cm1 have been assigned to in-plane and out-of-plane bending vibrations, respectively and they are found to be in line with the computed wavenumbers. Keto group (–CO) vibrations Ketones, aldehydes and amides generally show IR absorption at 1750–1650 cm1. Conjugation, ring size, hydrogen bonding, steric and electronic effects often result in significant shifts in CO absorption frequencies [9,36]. Accordingly, FT-Raman band at 1719 cm1 in OCBH has been assigned to –CO stretching mode of vibration and they are found to be consistent with the calculated wavenumbers. Similarly, the wavenumbers of in-plane and out-of-plane bending mode of vibrations are also in line with the computed wavenumbers. Hydrazide group (–NH–NH2) vibrations The frequencies of amino group appear around 3500– 3300 cm1 for NH2 stretching, 1700–1600 cm1 for scissoring and 1150–900 cm1 for rocking deformations [37]. NH2 asymmetric stretching mode is observed at 3286 and at 3285 cm1 in OCBH.
NH2 symmetric stretching is observed at 3185 cm1 and the –NH stretching mode is observed at 3302 cm1 in OCBH. These are found to be in line with the computed values as well as the literatures [38,39]. In addition, the NH2 group has scissoring, rocking, wagging and torsional modes of vibration. All the above modes have been assigned for the title molecule and they are given in Table 4 along with their PED values. NMR chemical shifts The isotropic chemical shifts are frequently used as an aid in identification of reactive organic as well as ionic species [40]. The Gauge-including atomic orbital (GIAO) 1H and 13C chemical shift calculations of the title compound has been made on the optimized geometry using B3LYP/6-311++G(d,p) method and presented in Table 5. The 1H NMR is interesting since the hydrogen atom is the smallest of all atoms and its chemical shift will be more susceptible to intermolecular interactions. The chemical shifts of N–H protons have been identified between 9.52 ppm to 10.51 ppm where as the C–H protons have shifts ranging from 4.57 ppm to 7.08 ppm. The typical range of 13C NMR chemical shift in organic molecules is greater than 100 ppm [41,42]. As shown in Table 5, the chemical shifts of carbon atoms are ranging from 106.55 to 189.40 ppm. NLO properties The potential application of the title compound in the field of nonlinear optics (NLO) demands the investigation of its structural and bonding features contributing to the hyperpolarizability enhancement. First hyperpolarizability is a third rank tensor that can be described by 3 3 3 matrix. The 27 components of 3D matrix can be reduced to 10 components due to the Kleinmann
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Table 4 Experimental and calculated (unscaled and scaled) HF/6-311++G(d,p) and B3LYP/6-311++G(d,p) level vibrational frequencies (cm1), IR intensity (km mol1), Raman activity (Å4 amu1), force constant (mdyne Å1) and probable assignments of o-chlorobenzohydrazide. No
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48.
Symm. species Cs
A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A0 A00 A0 A0 A00 A00 A0 A00 A00 A0 A00 A00 A00 A0 A00 A00 A00 A00 A00 A00 A00
Experimental frequencies (cm1)
HF/6-311++G(d,p)
B3LYP/6-311++G(d,p)
Characterization of normal modes with PED (%)
FTIR
FTRaman
Unscaled
Scaled
IR Intensity
Raman intensity
Unscaled
Scaled
IR intensity
Raman intensity
– 3286 3185 – 3056 3024 – – – 1646 1594 1568 1520 1433 1339 – – 1257 – 1162 – 1136 1055 1036 991 982 899 873 786 755 – 720 669 651 – – 473 – – – – – – – – – – –
3302 3285 – 3071 3059 – 3010 1719 1651 – 1597 1571 – – – 1329 1321 – 1191 1165 1140 – – 1037 – – 896 – – – 742 725 – – 553 551 – 447 406 364 310 289 231 200 163 141 – –
3862 3838 3744 3366 3355 3343 3331 1923 1838 1784 1751 1636 1609 1585 1495 1445 1388 1341 1312 1235 1229 1182 1139 1123 1115 1080 983 971 869 841 822 808 733 686 639 619 531 499 454 421 336 311 280. 182 155 141 106 50
3330 3316 3211 3096 3083 3047 3034 1740 1673 1668 1626 1589 1537 1456 1351 1332 1329 1272 1211 1189 1163 1152 1073 1064 1008 990 918 895 809 776 761 733 683 669 567 562 494 467 428 381 324 295 243 221 167 142 101 52
71.78 12.62 1.00 4.66 9.82 6.20 0.52 521.02 18.99 20.67 7.17 21.55 39.22 35.20 279.84 2.25 6.08 6.94 0.83 15.22 16.72 5.30 29.17 9.43 0.52 2.04 14.46 229.50 42.36 50.70 18.71 5.75 14.94 1.62 13.30 149.09 6.49 9.83 12.89 2.10 3.71 2.96 4.87 0.43 2.22 3.14 1.42 1.98
1.29 0.31 0.86 3.23 1.99 1.49 0.86 1.30 0.37 1.71 1.30 0.16 0.29 0.08 0.27 0.26 0.08 0.89 0.05 0.56 0.32 1.18 0.34 7.15 0.21 0.02 0.08 0.59 0.65 0.15 0.51 0.19 5.08 1.36 0.91 0.32 0.67 5.52 4.34 1.95 0.65 0.31 2.24 2.86 2.66 1.47 34.06 100
3597 3572 3485 3203 3195 3184 3174 1735 1692 1652 1605 1586 1465 1453 1376 1328 1316 1284 1223 1186 1148 1138 1058 1050 1000 966 881 874 785 763 755 729 680 634 587 583 483 460 416 390 302 282 254 170 149 142 98 51
3309 3291 3189 3077 3063 3030 3016 1725 1656 1642 1599 1574 1526 1438 1346 1330 1324 1260 1199 1172 1143 1139 1057 1040 996 985 901 876 790 759 748 724 673 655 556 552 476 450 409 367 307 284 239 194 155 143 98 57
53.12 10.3 3.18 3.82 7.33 3.83 0.70 360.64 18.84 13.75 6.69 10.22 44.41 14.04 223.50 2.39 0.53 5.07 1.27 0.21 3.31 16.74 4.25 39.20 0.14 1.41 12.66 200.73 33.60 3.25 55.63 1.36 16.35 1.12 8.61 120.81 5.87 9.18 11.56 1.56 5.60 6.59 6.44 1.03 0.98 0.61 1.81 2.23
1.32 0.29 0.92 3.12 1.65 1.28 0.70 1.63 0.35 1.82 0.48 0.75 0.14 0.38 0.61 0.31 0.32 0.04 0.99 0.53 0.15 0.94 2.65 3.19 0.03 0.01 0.05 0.92 0.49 0.26 0.19 0.10 3.15 1.15 1.00 0.42 0.93 4.05 2.80 1.12 0.42 0.45 2.01 2.45 2.03 2.76 30.86 100
NH (100) NH2 ass (100) NH2 ss (100) CH (100) CH (100) CH (100) CH (100) CO (96) CC (92) CC (90) CC (89) NN (90) NH2 sciss (89) CC (85), CN (15) CC (87), NN (11) CC (83), Rsymd (10) CC (81) CN (81) bCH (79), CC (19) NH2 rock (78) Rtrigd (72), CC (21) bNH (79), CC (19) bCH (81), CCl (17) Rsymd (69), CC (21) bCH (67), Rtrigd (23) Rasymd (69), Rtrigd(19) bCH (65) bNN (63) NH2 wag (73) bCC (67) bCN (63) xNH (59) xCH (60) CCl (81) xCH (57), xCO (21) xCH (59), tRsym (19) bCO (73), Rtrigd (21) xCH (61), xCC (23) tRtrig (63), tRasym (21) xCO (57), xCCl (17) bCCl (59), Rsymd(23) xCCl (60), tRasym(21) xNN (56), xCC (23) xCC (55), xCH (17) tRsym (61), tRtrig (23) xCN (59), xCC (20) tRasym (63), xCH (19) NH2 twist (69)
For the notations used, see Supplementary Table S2.
where
Urea is one of the prototypical molecules used in the study of the NLO properties of molecular systems. Therefore it was used frequently as a threshold value for comparative purposes. The calculated value of b for OCBH is 0.223 1030 esu which is slightly lower than that of Urea (0.3728 1030 esu). Besides the hyperpolarizability, other important properties of the title compound like dipole moment, polarizability have also been computed and presented in the Table 6.
bx ¼ bxxx þ bxyy þ bxzz
HOMO–LUMO analysis
symmetry [43,44]. The output from Gaussian 03 provides 10 components of this matrix as bxxx, bxxy, bxyy, byyy, bxxz, bxyz, byyz, bxzz, byzz, bzzz, respectively and they are given in Table 6. The components of the first hyperpolarizability can be calculated using the following equations.
b ¼ b2x þ b2y þ b2z
by ¼ byyy þ bxxy þ byzz bz ¼ bzzz þ bxxz þ byyz
The most important orbitals in a molecule that determine the way the molecule interacts with other species are, the frontier molecular orbitals (FMOs), called highest occupied molecular
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Table 5 The chemical shielding and shift (GIAO method) for o-chlorobenzohydrazide calculated by B3LYP/6-311++G(d,p) method. ATOM
Chemical shift (ppm)
ATOM
Chemical shift (ppm)
H10 H12 H13 H15 H16 H17 H18
9.52 10.49 10.51 7.98 4.63 4.57 7.08
C1 C2 C3 C4 C5 C6 C7
156.91 115.86 157.78 185.40 189.40 176.94 106.55
Eð2Þ ¼ DEij ¼ qi ¼
Fig. 3. Observed FT-IR spectra and FT-Raman spectra of o-chlorobenzohydrazide.
orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). They are the key parameter in determining molecular properties, molecular electrical transport properties [45,46]. Moreover, the Eigen value of HOMO characterizes the ability of donating electron and the Eigen value of LUMO characterizes the ability of accepting electron. The energy gap between HOMO and LUMO reflects the chemical stability and they are responsible for chemical and spectroscopic properties of the molecule [47,48]. The energy of the four important FMOs such as the second highest (HOMO1) and highest occupied MO (HOMO), the lowest (LUMO) and the second lowest unoccupied MO (LUMO+1) have been calculated and the pictorial illustrations of the FMOs of OCBH have been given in Supplementary Fig. 1. In OCBH, there are 45 occupied molecular orbitals and the energy gap between HOMO and LUMO orbital is 0.21102 a.u.
Fði; jÞ
2
ei ej
where qi is the donor orbital occupancy, ei, ej are diagonal elements (orbital energies) and F(i, j) is the off-diagonal NBO Fock matrix clement. In Table 7 the perturbation energies of significant donor–acceptor interactions are comparatively presented for OCBH. The larger the E(2) value, the intense is the interaction between electron donors and electron acceptors. In OCBH, the interactions initiated by the donor NBOs like BD (2) C1–C2, BD (2) C3–C4, BD (2) C5–C6 and NBOs due to lone pairs of O8, N9 and Cl14 are giving substantial stabilization to the structure. Above all, the interaction between antibonding orbitals namely, BD (2) C1–C2 ? BD (2) C5–C6 is giving the most possible stabilization to OCBH since it has the most E(2) value around 262.81 kcal/mol. The Natural Localized Molecular Orbital (NLMO) analysis has been carried out since they show how bonding in a molecule is composed from orbitals localized on different atoms. The derivation of NLMOs from NBOs gives direct insight into the nature of the localized molecular orbital’s ‘‘delocalization tails’’ [51,35]. Table 6 Electric dipole moment, Polarizability and Hyperpolarizability of o-chlorobenzohydrazide by B3LYP with the basic set 6-311++G(d,p) level. Parameters
Value
Dipole moment (Debye)
lx ly lz Mtotal
2.6952 0.4607 3.0893 4.1255
Polarizability (a)
axx ayy azz axy axz ayz aTotal1024
65.2359 69.7708 78.0259 2.4577 1.1891 4.5027 71.010867
Anisotropic tensor A B C
252.296094 27.7285554 209.333713
NBO/NLMO analysis Natural Bond Orbital (NBO) analysis provides an efficient method for studying interesting features of molecular structure. They give strong insight in the intra and inter molecular bonding and interaction among bonds, and also provide a convenient basis for investigation of charge transfer or conjugative interactions in molecular system [49]. Another useful aspect of NBO method is that it gives information about interactions in both filled and virtual orbital spaces that could help to have a detailed analysis of intra and intermolecular interactions. The second order Fock matrix was carried out to evaluate the donor–acceptor interactions in the NBO analysis [50]. For each donor NBO (i) and acceptor NBO (j), the stabilization energy associated with i ? j delocalization can be estimated as,
Hyper polarisability (b) bxxx byyy bzzz bxyy byxx bzxx bxzz byzz bzyy bTotal ( 1030 esu)
4.4903 1.8681 7.1513 5.7598 2.1692 0.0119 3.9544 9.7271 9.5865 0.223
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Table 7 Significant donor–acceptor interactions and second order perturbation energies of o-chlorobenzohydrazide calculated by B3LYP method using 6-311++G(d,p) basis set. Donor NBO (i)
Acceptor NBO (j)
BD (2) C1–C2
BD BD BD BD BD BD BD BD BD BD BD BD
BD (2) C3–C4 BD (2) C5–C6 LP (2) O8 LP (1) N9 LP (1) Cl14 BD (2) C1–C2 BD (2) C7–O8 a b c
(2) (2) (1) (2) (2) (2) (1) (1) (2) (2) (2) (2)
E(2)
C3–C4 C5–C6 C1–C2 C5–C6 C1–C2 C3–C4 C1–C7 C7–N9 C7–O8 C1–C2 C5–C6 C7–O8
a
(kcal/mol)
19.31 18.37 20.91 19.46 22.43 21.16 21.54 25.70 32.30 12.78 262.81 32.55
Ej Ei
b
(a.u)
0.31 0.31 0.28 0.29 0.28 0.28 0.65 0.73 0.42 0.34 0.01 0.37
F(i, j)
c
(a.u)
0.069 0.067 0.069 0.067 0.071 0.070 0.107 0.124 0.106 0.065 0.086 0.257
E(2) means energy of hyperconjucative interactions. Energy difference between donor and acceptor i and j NBO orbitals. F(i, j) is the Fock matrix element between i and j NBO orbitals.
Table 8 Significant NLMO’s occupancy, percentage from parent NBO and atomic hybrid contributions of o-chlorobenzohydrazide calculated at B3LYP level using 6-311++G(d,p) basis set. Bond
Occupancy
% from parent NBO
Hybrid contributions Atom
%
BD(2) C1–C2
2.00000
84.1144
C1 C2 C3 C4 C5 C6
41.130 42.989 5.939 1.515 1.532 5.976
BD(2) C3–C4
2.00000
81.9373
C1 C2 C3 C4 C5 C6
4.134 4.039 38.969 43.037 7.375 2.191
BD(2) C5–C6
2.00000
81.0910
C1 C2 C3 C4 C5 C6
4.880 4.822 4.379 4.687 40.496 40.600
LP (2) O8
2.00000
92.2727
C1 C7 O8 N9
1.570 3.778 92.273 1.541
LP (1) N9
2.00000
85.6034
C7 O8 N9
8.773 4.132 85.604
Table 8 shows the comparative study of significant NLMO’s occupancy, percentage from parent NBO and atomic hybrid contributions of OCBH calculated at B3LYP level using 6-311++G(d,p) basis set. The most delocalized NLMO is BD (2) C5–C6 for OCBH. It has around 81.09% contribution from the localized parent NBO and has a delocalization tail of 18.91% consists of the hybrids from C1, C2, C3 and C4. The other most delocalized NLMOs in OCBH are BD (2) C3–C4, BD (2) C1–C2 and NLMOs due to lone pairs of O8 and N9. The significant amount of delocalization tail of an NLMO indicates that they are strongly delocalized into the vicinal regions. This delocalization can also be observed in the perturbation theory energy analysis given in Table 7. Conclusion In the present work, FT-IR and FT-Raman spectra of the title compound o-chlorobenozohydrazide have been recorded and
compared with the theoretically constructed spectra using HF and DFT/B3LYP methods with 6-311++G(d,p) basis set. All the fundamental modes of the optimized structure have been assigned precisely on the basis of potential energy distribution (PED) and close agreement between the experimental and scaled frequencies were achieved. The molecular structural parameters like bond length and bond angle, thermodynamic properties have been determined from ab initio and DFT calculations using 6-311 ++G(d,p) basis set. The computed geometrical parameters are compared with the observed X-ray diffraction data of similar compound. The frontier molecular orbitals have been visualized and the HOMO–LUMO energy gap has been calculated. The stability and intramolecular interactions have been interpreted by NBO/NLMO analysis and the transactions give stabilization to the structure have been identified by second order perturbation energy calculations. The calculation of first hyperpolarizability reveals that the title compound possesses comparable NLO properties. Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.saa.2014.03.026. References [1] M. Nic, J. Jirat, B. Kosata (Eds.). ‘‘Hydrazides’’. IUPAC Compendium of Chemical Terminology (Online ed.), 2006. doi:10.1351/gold book. ISBN 0-9678550-9-8. [2] I. Mir, M.T. Siddiqui, A. Comrie, Tetrahedron 26 (22) (1970) 5235–5238. [3] E. Degener, H. Scheinplug, H.G. Schemelzer, Brit. Patent No. 1035, 474 (1967). [4] R. Cavier, R. Rips, J. Med. Chem. 8 (5) (1965) 706–708. [5] D.L. Trepanier, E.R. Wagner, G. Harris, A.D. Rudzik, J. Med. Chem. 9 (6) (1996) 881–885. [6] M. Goyal, N. Mahadevan, D. Kaushik, Int. J. Rec. Adv. Pharm. Res. 2 (2011) 27– 29. [7] E. Gobinath, R.J. Xavier, Spectrochim. Acta Part A Mol. Biomol. Spectrosc. 115 (2013) 815–822. [8] V. Vimalraj, S. Vijayalakshmi, S. Umayaparvathi, A.R. Krishnan, Spectrochim. Acta Part A 78 (2011) 670–675. [9] V. Arjunan, T. Rani, C.V. Mythili, S. Mohan, Spectrochim. Acta Part A Mol. Biomol. Spectrosc. 79 (2011) 486–496. [10] J. Zhang, T. Zhang, K. Yu, Struct. Chem. 17 (2006) 249–254. [11] K.K. Vijayaraj, B. Narayana, B.V. Ashalatha, N. Suchetha Kumari, B.K. Sarojini, Eur. J. Med. Chem. 42 (2007) 425–429. [12] A.H. Abadi, A.A.H. Eissa, G.S. Hassan, Chem. Pharm. Bull. 51 (7) (2003) 838– 844. [13] C.G. Bonde, N.J. Gaikwad, Bioorg. Med. Chem. 12 (2004) 2151–2161. [14] S.V. Bhandari, A.A. Patil, V. Sarkate, S.G. Gore, K.G. Bothra, Bioorg. Med. Chem. 17 (2009) 390–400. [15] K. Sugano, H. Hamada, M. Machida, H. Ushio, J. Biomol. Screen. 6 (2001) 189– 196. [16] H.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, R. Nakajima, Y. Honda, O. Kilao, H. Nakai, T.
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