Abstract
C18H16N4O2, triclinic, P1̅ (no. 2), a = 10.9734(4) Å, b = 11.8835(5) Å, c = 13.0996(5) Å, α = 78.581(2)°, β = 78.542(1)°, γ = 83.725(2)°, V = 1636.68(11) Å3, Z = 4, Rgt(F) = 0.0439, wRref(F2) = 0.1182, T = 100 K.
The asymmetric unit of the title crystal structure is shown in the figure. Tables 1–3 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.
Data collection and handling.
| Crystal: | Colourless, plate, size 0.178×0.347×0.410 mm |
| Wavelength: | Mo Kα radiation (0.71073 Å) |
| μ: | 0.88 cm−1 |
| Diffractometer, scan mode: | Bruker APEX-II, φ and ω scans |
| 2θmax: | 50° |
| N(hkl)measured, N(hkl)unique: | 40044, 5750 |
| Criterion for Iobs, N(hkl)gt: | Iobs > 2 σ(Iobs), 4675 |
| N(param)refined: | 451 |
| Programs: | SHELX [7], Bruker programs [8] |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).
| Atom | Site | x | y | z | Uiso |
|---|---|---|---|---|---|
| H(1AA) | 2i | 0.3989 | 0.9858 | 0.1086 | 0.025 |
| H(2AA) | 2i | 0.3450 | 1.1676 | 0.1526 | 0.031 |
| H(3AA) | 2i | 0.3884 | 1.2063 | 0.3091 | 0.036 |
| H(4AA) | 2i | 0.4854 | 1.0632 | 0.4213 | 0.043 |
| H(5AA) | 2i | 0.5393 | 0.8807 | 0.3788 | 0.033 |
| H(8AA) | 2i | 0.5371 | 0.8174 | 0.0438 | 0.018 |
| H(11A) | 2i | 0.6117 | 0.2578 | 0.1455 | 0.021 |
| H(13A) | 2i | 0.7678 | 0.2856 | −0.1254 | 0.023 |
| H(14A) | 2i | 0.8839 | 0.1436 | −0.2078 | 0.027 |
| H(16A) | 2i | 0.8149 | −0.0889 | 0.0655 | 0.027 |
| H(17A) | 2i | 0.7001 | 0.0556 | 0.1483 | 0.024 |
| H(18A) | 2i | 0.9963 | −0.2255 | −0.1329 | 0.053 |
| H(18B) | 2i | 0.8641 | −0.2111 | −0.0571 | 0.053 |
| H(18C) | 2i | 0.9879 | −0.1811 | −0.0239 | 0.053 |
| H(1BA) | 2i | 0.9869 | 0.3610 | 0.6087 | 0.025 |
| H(2BA) | 2i | 1.1729 | 0.2708 | 0.6551 | 0.031 |
| H(3BA) | 2i | 1.2264 | 0.2894 | 0.8147 | 0.034 |
| H(4BA) | 2i | 1.0989 | 0.4055 | 0.9236 | 0.032 |
| H(5BA) | 2i | 0.9127 | 0.4955 | 0.8776 | 0.025 |
| H(8BA) | 2i | 0.8197 | 0.4991 | 0.5461 | 0.020 |
| H(11B) | 2i | 0.2279 | 0.6009 | 0.6502 | 0.024 |
| H(13B) | 2i | 0.2439 | 0.8286 | 0.4196 | 0.023 |
| H(14B) | 2i | 0.0759 | 0.9436 | 0.3625 | 0.024 |
| H(16B) | 2i | −0.1612 | 0.7654 | 0.6025 | 0.031 |
| H(17B) | 2i | 0.0070 | 0.6528 | 0.6602 | 0.029 |
| H(18D) | 2i | −0.2312 | 1.0462 | 0.3417 | 0.047 |
| H(18E) | 2i | −0.1126 | 0.9707 | 0.2921 | 0.047 |
| H(18F) | 2i | −0.0949 | 1.0657 | 0.3581 | 0.047 |
| H(1NB) | 2i | 0.710(2) | 0.533(2) | 0.847(2) | 0.015(5) |
| H(3NA) | 2i | 0.548(2) | 0.438(2) | 0.154(2) | 0.038(7) |
| H(3NB) | 2i | 0.425(2) | 0.553(2) | 0.656(2) | 0.029(6) |
| H(1NA) | 2i | 0.525(2) | 0.696(2) | 0.349(2) | 0.034(6) |
Fractional coordinates and atomic displacement parameters (Å2).
| Atom | Site | x | y | z | U11 | U22 | U33 | U12 | U13 | U23 |
|---|---|---|---|---|---|---|---|---|---|---|
| O(1A) | 2i | 0.6754(1) | 0.6129(1) | −0.03495(9) | 0.0281(7) | 0.0192(7) | 0.0113(7) | −0.0042(6) | −0.0011(5) | −0.0033(5) |
| O(2A) | 2i | 0.9288(1) | −0.0631(1) | −0.1369(1) | 0.0360(8) | 0.0173(8) | 0.0341(8) | 0.0041(6) | 0.0005(7) | −0.0084(6) |
| N(1A) | 2i | 0.5241(1) | 0.7037(1) | 0.2805(1) | 0.0233(8) | 0.0137(9) | 0.0098(8) | −0.0020(7) | −0.0017(6) | −0.0035(6) |
| N(2A) | 2i | 0.5609(1) | 0.6104(1) | 0.2355(1) | 0.0212(8) | 0.0151(9) | 0.0126(8) | −0.0027(6) | −0.0025(6) | −0.0040(6) |
| N(3A) | 2i | 0.6023(1) | 0.4617(1) | 0.0911(1) | 0.0201(8) | 0.0159(9) | 0.0118(8) | −0.0020(7) | 0.0004(6) | −0.0049(6) |
| N(4A) | 2i | 0.6624(1) | 0.3827(1) | 0.0303(1) | 0.0178(8) | 0.0170(9) | 0.0155(8) | −0.0011(6) | −0.0021(6) | −0.0061(7) |
| C(1A) | 2i | 0.4165(2) | 1.0012(2) | 0.1725(2) | 0.020(1) | 0.021(1) | 0.022(1) | −0.0018(8) | −0.0026(8) | −0.0026(8) |
| C(2A) | 2i | 0.3845(2) | 1.1092(2) | 0.1984(2) | 0.024(1) | 0.017(1) | 0.031(1) | 0.0032(8) | −0.0001(8) | 0.0011(9) |
| C(3A) | 2i | 0.4102(2) | 1.1322(2) | 0.2912(2) | 0.039(1) | 0.014(1) | 0.031(1) | 0.0006(9) | 0.010(1) | −0.0079(9) |
| C(4A) | 2i | 0.4678(2) | 1.0471(2) | 0.3577(2) | 0.067(2) | 0.022(1) | 0.019(1) | −0.004(1) | −0.004(1) | −0.0073(9) |
| C(5A) | 2i | 0.4999(2) | 0.9387(2) | 0.3326(2) | 0.047(1) | 0.016(1) | 0.017(1) | 0.0019(9) | −0.0058(9) | −0.0032(8) |
| C(6A) | 2i | 0.4743(2) | 0.9145(2) | 0.2393(1) | 0.0162(9) | 0.016(1) | 0.0161(9) | −0.0029(8) | 0.0027(7) | −0.0017(7) |
| C(7A) | 2i | 0.5101(2) | 0.8014(2) | 0.2088(1) | 0.0154(9) | 0.015(1) | 0.0143(9) | −0.0016(7) | −0.0036(7) | −0.0006(7) |
| C(8A) | 2i | 0.5382(2) | 0.7693(2) | 0.1108(1) | 0.0180(9) | 0.017(1) | 0.0109(9) | −0.0017(8) | −0.0049(7) | 0.0005(7) |
| C(9A) | 2i | 0.5688(2) | 0.6508(2) | 0.1312(1) | 0.0158(9) | 0.018(1) | 0.0102(8) | −0.0036(7) | −0.0040(7) | −0.0032(7) |
| C(10A) | 2i | 0.6187(2) | 0.5745(2) | 0.0544(1) | 0.0160(9) | 0.019(1) | 0.0126(9) | −0.0024(8) | −0.0058(7) | −0.0028(7) |
| C(11A) | 2i | 0.6579(2) | 0.2770(2) | 0.0757(1) | 0.0170(9) | 0.020(1) | 0.0140(9) | −0.0035(8) | −0.0007(7) | −0.0016(8) |
| C(12A) | 2i | 0.7230(2) | 0.1859(2) | 0.0214(1) | 0.0148(9) | 0.017(1) | 0.0192(9) | −0.0033(8) | −0.0044(7) | −0.0037(8) |
| C(13A) | 2i | 0.7780(2) | 0.2100(2) | −0.0862(1) | 0.023(1) | 0.015(1) | 0.019(1) | −0.0044(8) | −0.0019(8) | −0.0003(8) |
| C(14A) | 2i | 0.8463(2) | 0.1258(2) | −0.1353(2) | 0.026(1) | 0.020(1) | 0.020(1) | −0.0051(9) | 0.0011(8) | −0.0043(8) |
| C(15A) | 2i | 0.8609(2) | 0.0137(2) | −0.0792(2) | 0.019(1) | 0.020(1) | 0.027(1) | −0.0003(8) | −0.0035(8) | −0.0074(9) |
| C(16A) | 2i | 0.8059(2) | −0.0128(2) | 0.0270(2) | 0.024(1) | 0.015(1) | 0.027(1) | −0.0010(8) | −0.0062(8) | 0.0001(8) |
| C(17A) | 2i | 0.7378(2) | 0.0736(2) | 0.0757(2) | 0.021(1) | 0.020(1) | 0.0173(9) | −0.0045(8) | −0.0028(8) | −0.0011(8) |
| C(18A) | 2i | 0.9456(2) | −0.1793(2) | −0.0835(2) | 0.038(1) | 0.021(1) | 0.046(1) | 0.005(1) | −0.004(1) | −0.008(1) |
| O(1B) | 2i | 0.6097(1) | 0.6655(1) | 0.46739(9) | 0.0239(7) | 0.0299(8) | 0.0121(7) | −0.0035(6) | −0.0032(5) | 0.0020(6) |
| O(2B) | 2i | −0.1646(1) | 0.9240(1) | 0.4473(1) | 0.0206(7) | 0.0274(8) | 0.0342(8) | 0.0050(6) | −0.0080(6) | −0.0047(6) |
| N(1B) | 2i | 0.7166(1) | 0.5271(1) | 0.7795(1) | 0.0175(8) | 0.0171(9) | 0.0094(8) | −0.0007(6) | −0.0036(6) | −0.0020(6) |
| N(2B) | 2i | 0.6177(1) | 0.5736(1) | 0.7350(1) | 0.0188(8) | 0.0142(8) | 0.0126(8) | −0.0009(6) | −0.0041(6) | −0.0020(6) |
| N(3B) | 2i | 0.4469(1) | 0.6048(1) | 0.5977(1) | 0.0186(8) | 0.0180(9) | 0.0137(8) | −0.0020(7) | −0.0044(6) | 0.0017(7) |
| N(4B) | 2i | 0.3597(1) | 0.6697(1) | 0.5436(1) | 0.0213(9) | 0.0168(9) | 0.0173(8) | 0.0009(7) | −0.0071(6) | −0.0013(7) |
| C(1B) | 2i | 1.0092(2) | 0.3695(2) | 0.6731(2) | 0.019(1) | 0.021(1) | 0.022(1) | −0.0045(8) | −0.0018(8) | −0.0031(8) |
| C(2B) | 2i | 1.1195(2) | 0.3157(2) | 0.7006(2) | 0.016(1) | 0.023(1) | 0.037(1) | −0.0013(8) | 0.0001(8) | −0.0048(9) |
| C(3B) | 2i | 1.1518(2) | 0.3278(2) | 0.7948(2) | 0.017(1) | 0.026(1) | 0.040(1) | −0.0050(9) | −0.0090(9) | 0.003(1) |
| C(4B) | 2i | 1.0754(2) | 0.3958(2) | 0.8600(2) | 0.025(1) | 0.030(1) | 0.026(1) | −0.0079(9) | −0.0110(9) | 0.0017(9) |
| C(5B) | 2i | 0.9651(2) | 0.4494(2) | 0.8326(2) | 0.022(1) | 0.021(1) | 0.020(1) | −0.0033(8) | −0.0041(8) | −0.0015(8) |
| C(6B) | 2i | 0.9305(2) | 0.4361(2) | 0.7390(1) | 0.0171(9) | 0.013(1) | 0.0189(9) | −0.0041(7) | −0.0034(7) | 0.0020(7) |
| C(7B) | 2i | 0.8128(2) | 0.4899(2) | 0.7089(1) | 0.0174(9) | 0.013(1) | 0.0135(9) | −0.0039(7) | −0.0007(7) | −0.0024(7) |
| C(8B) | 2i | 0.7740(2) | 0.5141(2) | 0.6122(1) | 0.020(1) | 0.016(1) | 0.0120(9) | −0.0013(8) | −0.0004(7) | −0.0035(7) |
| C(9B) | 2i | 0.6534(2) | 0.5652(2) | 0.6328(1) | 0.0185(9) | 0.012(1) | 0.0113(9) | −0.0039(7) | −0.0015(7) | −0.0016(7) |
| C(10B) | 2i | 0.5692(2) | 0.6152(2) | 0.5575(1) | 0.023(1) | 0.013(1) | 0.0123(9) | −0.0008(8) | −0.0033(7) | −0.0043(7) |
| C(11B) | 2i | 0.2461(2) | 0.6575(2) | 0.5880(2) | 0.025(1) | 0.016(1) | 0.019(1) | −0.0043(8) | −0.0035(8) | −0.0010(8) |
| C(12B) | 2i | 0.1433(2) | 0.7283(2) | 0.5459(2) | 0.022(1) | 0.017(1) | 0.021(1) | −0.0014(8) | −0.0044(8) | −0.0065(8) |
| C(13B) | 2i | 0.1617(2) | 0.8156(2) | 0.4570(1) | 0.018(1) | 0.020(1) | 0.0188(9) | −0.0022(8) | −0.0027(7) | −0.0052(8) |
| C(14B) | 2i | 0.0618(2) | 0.8837(2) | 0.4225(2) | 0.025(1) | 0.017(1) | 0.0180(9) | −0.0001(8) | −0.0053(8) | −0.0044(8) |
| C(15B) | 2i | −0.0593(2) | 0.8643(2) | 0.4757(2) | 0.023(1) | 0.018(1) | 0.027(1) | 0.0028(8) | −0.0088(8) | −0.0098(8) |
| C(16B) | 2i | −0.0789(2) | 0.7782(2) | 0.5651(2) | 0.019(1) | 0.024(1) | 0.033(1) | −0.0012(8) | 0.0004(8) | −0.0045(9) |
| C(17B) | 2i | 0.0213(2) | 0.7115(2) | 0.5992(2) | 0.026(1) | 0.018(1) | 0.025(1) | −0.0054(8) | −0.0024(8) | 0.0015(8) |
| C(18B) | 2i | −0.1497(2) | 1.0083(2) | 0.3524(2) | 0.031(1) | 0.031(1) | 0.032(1) | 0.008(1) | −0.0130(9) | −0.005(1) |
Source of material
The synthesis of N′-(4-methoxybenzylidene)-5-phenyl-1H-pyrazole-3-carbohydrazide was carried out by our reported procedure [6]. To a solution of 5-phenyl-1H-pyrazole-3-carbohydrazide (1 mmol, 202 mg), in 10 mL of ethanol, was added an equimolar amount of the 4-methoxybenzaldehyde in the presence of acetic acid. The mixture was maintained under reflux for 2 h. Then, the mixture was poured in cold water, and the precipitate formed was filtered out and washed with ethanol. Single crystals of the title compound were obtained on slow evaporation of the solvent (DMF). Yield 82%; M.p. 276–278 °C; IR (KBr, ν(cm−1)): 3214 (NH), 1656 (C = O), 1603 (N = CH); 1H-NMR (300 MHz, DMSO-d6: δ = 3.78 (s, 3H, OCH3), 7.00 (s, 1H, CH-pz), 7.21 (d, J = 8.7Hz, 2H, H—Ar), 7.36–7.48 (m, 5H, H—Ar), 7.64 (d, J = 8.7Hz, 2H, H—Ar), 8.44 (s, 1H, NHCO), 11.59 (s, 1H, N = CH), 13.80 (s, 1H, NH-pz); 13C-NMR (75 MHz, DMSO-d6: δ = 55.75, 103.87, 114.79, 125.81, 127.44, 128.50, 129.16, 129.50, 130.11, 144.15, 147.27, 148.02, 158.49, 161.26.; MS (ESI): m/z = 321 (M—H+).
Experimental details
The hydrogen atoms were idealized and refined using a riding model with the help of SHELX (AFIX 43 or 137 option) [7].
Discussion
Pyrazole are an important class of heterocyclic compounds and many pyrazole derivatives are reported to have a broad spectrum of biological properties, including anti-inflammatory and antimicrobial activities [1], anticancer [2], antidepressant [3], anticonvulsant [4] and antiviral properties [5]. Because of these various interesting fields of application as well as their fairly assessable path of synthesis, the pyrazole ring became a center of attraction for organic chemist.
The asymmetric unit of the title structure contain two independent molecules. The pyrazole rings (N1/N2/C7/C8/C9) and (N1a/N2a/C7a/C8a/C9a) make dihedral angles of 25.77(2)° and 19.24(4)° with the phenyl ring C1—C6 and C1a-C6a in molecules A and B, respectively. The title structure shows four hydrogen bonds and between N1B—H1NB⋯O1Ai, N3A—H3NA⋯N2Bii, N3B—H3NB⋯N2Aii and C3A—H3AA⋯N2Biii with symmetry codes: (i) x, y, z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+2, −z+1. These hydrogen bonds connect the two crystallographically independent molecules into a complex chain structure. These chains run along the [001] direction and interact with adjacent chains by van der Waals forces only.
Funding source: Deanship of Scientific Research
Award Identifier / Grant number: PRG-1437-29
Funding statement: The authors extend their sincere appreciation to the Deanship of Scientific Research at king Saud University for its funding this Prolific Research group (PRG-1437-29).
Acknowledgements:
The authors extend their sincere appreciation to the Deanship of Scientific Research at king Saud University for its funding this Prolific Research group (PRG-1437-29).
References
1. Sharma, P. K.; Kumar, S.; Kumar, P.; Kaushik, P.; Kaushik, D.; Dhingra, Y.; Aneja, K. R.: Synthesis and biological evaluation of some pyrazolylpyrazolines as anti-inflammatory–antimicrobial agents. Eur. J. Med. Chem. 45 (2010) 2650–2655.10.1016/j.ejmech.2010.01.059Search in Google Scholar PubMed
2. Zheng, L.-W.; Shao, J.-H.; Zhao, B.-X.; Miao, J.-Y.: Synthesis of novel pyrazolo[1,5-alpyrazin-4(5H)-one derivatives and their inhibition against growth of A549 and H322 lung cancer cells. Bioorg. Med. Chem. Lett. 21 (2011) 3909–3913.10.1016/j.bmcl.2011.05.035Search in Google Scholar PubMed
3. Chae, E.; Shin, Y.-J.; Ryu, E.-J.; Ji, M. K.; Ryune, C. N.; Lee, K.-H.; Jeong, H. J. K.; Choi, S.-J.; Yeonjung, S. O.; Kyung, P.; Chun-Eung, S. Y.: Discovery of biological evaluation of pyrazole/imidazole amides as mGlu5 receptor negative allosteric modulators. Bioorg. Med. Chem. Lett. 23 (2013) 2134–2139.10.1016/j.bmcl.2013.01.116Search in Google Scholar PubMed
4. Kaushik, D.; Khan, S. A.; Chawla, G.; Kumar, S.: N′-[(5-chloro-3-methyl-1-phenyl-1H-pyrazol-4-yl)methylene] 2/4-substituted hydrazides: synthesis and anticonvulsant activity. Eur. J. Med. Chem. 45 (2010) 3943–3949.10.1016/j.ejmech.2010.05.049Search in Google Scholar PubMed
5. El-Sabbagh, O. I.; Baraka, M. M.; Ibrahim, S. M.; Pannecouque, C.; Andrei, G.; Snoeck, R.; Balzarini, J.; Rashad Adel, A.: Synthesis and antiviral activity of new pyrazole and thiazole derivatives. Eur. J. Med. Chem. 44 (2009) 3746–3753.10.1016/j.ejmech.2009.03.038Search in Google Scholar PubMed
6. Karrouchi, K.; Doudach, L.; Chemlal, L.; Mohamed, K.; Taoufik, J.; Cherrah, Y.; Radi, S.; Faouzi, M. E.; Ansar, M.: Synthesis and pharmacological evaluation of some new pyrazole derivatives. J. Pharm. Res. 8 (2014) 1171–1177.Search in Google Scholar
7. Sheldrick, G. M.: SHELXL 2014: Program for crystal structure solution; University of Göttingen, Göttingen, Germany, 2014..Search in Google Scholar
8. Bruker: SAINT-Plus, SHELXTL and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA, 2004.Search in Google Scholar
©2016 Khalid Karrouchi et al., published by De Gruyter.
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