Z. Kristallogr. NCS 228 (2013) 395-396 / DOI 10.1524/ncrs.2013.0198
395
© by Oldenbourg Wissenschaftsverlag, München
Crystal structure of (Z)-4-benzyl-N'-(4-chloro-2-oxoindolin-3-ylidene)piperazine-1-carbothiohydrazide, C20H20ClN5OS Bei-Bei Mao, Ai-Min Li, Chong-Qing Wan and Sheng-Li Cao* Department of Chemistry, Capital Normal University, Beijing 100048, P. R. China Received May 07, 2013, accepted June 19, 2013, available online August 27, 2013, CCDC no. 931452
Abstract C20H20ClN5OS, triclinic, P1 (no. 2), a = 8.668(1) Å, b = 8.733(1) Å, c = 13.554(2) Å, a = 94.673(9)°, b = 94.73(1)°, g = 101.841(9)°, V = 995.6 Å3, Z = 2, Rgt(F) = 0.0410, wRref(F2) = 0.1118, T = 296 K. Table 1. Data collection and handling. Crystal: Wavelength: m: Diffractometer, scan mode: 2qmax: N(hkl)measured, N(hkl)unique: Criterion for Iobs, N(hkl)gt: N(param)refined: Programs:
orange blocks, size 0.20´0.25´0.30 mm Mo Ka radiation (0.71073 Å) 3.18 cm-1 Bruker APEXII CCD, j and w 50.02° 9742, 3312 Iobs > 2 s(Iobs), 2486 253 SHELX [8]
Source of material A mixture of the 4-chloroindoline-2,3-dione (0.18 g, 1.0 mmol) and 4-benzylpiperazine-1-carbothiohydrazide (0.25 g, 1.0 mmol) in absolute methanol (20 mL) was stirred at room temperature for 3 days. Thin layer chromatography (TLC) of the solution indicated the end of the reaction (Rf = 0.40, dichloromethane/methanol = 95:5, v/v). The precipitates were collected by filtration and dried in air, which was purified by recrystallization from ethanol to give the title compound (yield 40%; m.p. 497-498 K). Yellow single crystals suitable for X-ray diffraction were grown from a mixture of dichloromethane and methanol (5:1, v/v) by slow evaporation at room temperature. Experimental details Accidentally only 94.5% data completeness was achieved.
Discussion Substituted indolin-2-ones have been identified as a versatile scaffold which exhibit diverse chemotherapeutic activities such as anticancer, antiviral and many others properties [1-3]. Among them, 1H-indole-2,3-dioxo-3-thiosemicarbazones have in general been reported to possess antitumour activities [3, 4]. Our previous studies have revealed the promising cytotoxic properties of various piperazine-1-carbothiohydrazide-based derivatives of indolin-2-one [5]. With the effort to obtain new and more potential antitumor agents, we synthesized the title compound. The dihedral angles between the indol-2-one ring and the benzene ring is 39.08(3)°, while the bridging piperazine ring links to the indol2-one via C9–N3–N2 atoms and to the benzene ring via a methylene group, and adopts a chair conformation. The double bond lengths between C7 and N2 (1.301(3) Å) are in agreement with those analog reported [6, 7]. Furthermore, there are two N– H···O hydrogen bonds (D···A = 2.742(3) Å, ÐD–H···A = 137°). An intramolecular hydrogen bond between N3 and O1 shows a very acute angle whereas the intermolecular N1–H1···O1i hydrogen bond shows typical values (D···A = 2.876(3) Å, ÐD–H···A = 167°) (Figure). By these hydrogen-bonding interactions, the molecules were linked to form a dimer in the crystal structure. Symmetry codes i: –x, –y+2, –z+1. Table 2. Atomic coordinates and displacement parameters (in Å2). Atom
Site
x
H(1A) H(3A) H(4A) H(5A) H(6A) H(10A) H(10B) H(11A) H(11B) H(12A) H(12B) H(13A) H(13B) H(14A) H(14B) H(16A) H(17A) H(18A) H(19A) H(20A)
2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i
0.0393 0.1418 0.0934 0.1936 0.2893 0.5052 0.4135 0.2872 0.4715 0.2379 0.1427 0.1726 0.3577 0.2487 0.3138 0.3893 0.5998 0.8093 0.8153 0.6095
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* Correspondence author (e-mail:
[email protected])
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y 0.8953 0.8199 0.7229 0.5060 0.3605 0.6012 0.6141 0.3500 0.3648 0.2943 0.3056 0.5415 0.5600 0.1048 0.0843 0.0329 -0.0707 -0.0843 0.0038 0.1029
z
Uiso
0.4242 0.7336 0.2608 0.2106 0.3257 0.8567 0.7538 0.7449 0.7559 0.9935 0.8918 0.9906 1.0029 0.8053 0.9136 0.6698 0.6152 0.7272 0.8905 0.9454
0.066 0.056 0.072 0.075 0.072 0.067 0.067 0.064 0.064 0.071 0.071 0.072 0.072 0.079 0.079 0.094 0.115 0.115 0.106 0.087
C20H20ClN5OS
396 Table 3. Atomic coordinates and displacement parameters (in Å2). Atom
Site
x
S(1) Cl(1) N(1) N(2) N(3) N(4) N(5) O(1) C(1) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) C(10) C(11) C(12) C(13) C(14) C(15) C(16) C(17) C(18) C(19) C(20)
2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i
0.05793(9) 0.31820(9) 0.0773(2) 0.1980(2) 0.1676(2) 0.2733(2) 0.3714(2) 0.0552(2) 0.2456(3) 0.1856(3) 0.1303(3) 0.1316(3) 0.1915(3) 0.2486(3) 0.1641(3) 0.0932(3) 0.1752(3) 0.4068(3) 0.3832(3) 0.2424(3) 0.2624(3) 0.3402(3) 0.4763(3) 0.4741(4) 0.6008(5) 0.7258(5) 0.7293(4) 0.6060(4)
y 0.76182(8) 0.37334(8) 0.8268(2) 0.6443(2) 0.7318(2) 0.5968(2) 0.3059(2) 0.9216(2) 0.4860(3) 0.6148(3) 0.7012(3) 0.6635(3) 0.5344(3) 0.4467(3) 0.6894(3) 0.8273(3) 0.6891(3) 0.5621(3) 0.3878(3) 0.3456(3) 0.5198(3) 0.1354(3) 0.0767(3) 0.0262(4) -0.0354(4) -0.0431(4) 0.0086(4) 0.0678(3)
z
U11
U22
U33
0.91305(5) 0.53250(5) 0.4551(1) 0.6633(1) 0.7430(1) 0.8656(1) 0.8795(1) 0.6159(1) 0.4477(2) 0.4802(2) 0.4076(2) 0.3073(2) 0.2781(2) 0.3470(2) 0.5765(2) 0.5547(2) 0.8390(2) 0.8143(2) 0.7896(2) 0.9326(2) 0.9579(2) 0.8544(2) 0.8144(2) 0.7148(2) 0.6819(3) 0.7489(4) 0.8459(3) 0.8785(2)
0.0642(5) 0.0831(6) 0.064(2) 0.042(1) 0.053(1) 0.051(1) 0.052(1) 0.072(1) 0.046(2) 0.041(1) 0.047(2) 0.061(2) 0.062(2) 0.060(2) 0.040(1) 0.047(2) 0.045(2) 0.045(2) 0.046(2) 0.060(2) 0.066(2) 0.063(2) 0.060(2) 0.079(2) 0.108(3) 0.075(3) 0.084(3) 0.080(2)
0.0668(5) 0.0598(4) 0.055(1) 0.042(1) 0.041(1) 0.062(1) 0.054(1) 0.057(1) 0.045(1) 0.041(1) 0.047(1) 0.064(2) 0.066(2) 0.051(2) 0.042(1) 0.047(1) 0.044(1) 0.062(2) 0.061(2) 0.070(2) 0.073(2) 0.056(2) 0.046(2) 0.065(2) 0.063(2) 0.052(2) 0.067(2) 0.061(2)
0.0584(4) 0.0783(4) 0.053(1) 0.054(1) 0.052(1) 0.056(1) 0.061(1) 0.0545(9) 0.065(2) 0.052(1) 0.055(1) 0.053(1) 0.056(2) 0.069(2) 0.051(1) 0.053(1) 0.052(1) 0.070(2) 0.062(1) 0.058(1) 0.054(1) 0.082(2) 0.076(2) 0.083(2) 0.108(3) 0.164(4) 0.126(3) 0.085(2)
Acknowledgments. The authors are grateful to National Natural Science Foundation of China (project No. 20972099), the 973 project 2013CB911000, and Beijing Municipal Commission of Education (project No. KZ201210028035) for financial support.
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U12 0.0327(4) 0.0373(4) 0.029(1) 0.016(1) 0.022(1) 0.028(1) 0.023(1) 0.037(1) 0.010(1) 0.009(1) 0.011(1) 0.010(2) 0.006(2) 0.012(1) 0.014(1) 0.018(1) 0.014(1) 0.025(1) 0.022(1) 0.027(2) 0.037(2) 0.014(2) 0.014(1) 0.000(2) -0.004(2) 0.016(2) 0.039(2) 0.031(2)
U13 0.0141(3) 0.0192(4) 0.001(1) 0.0100(9) 0.0084(9) 0.010(1) 0.014(1) 0.0051(9) 0.010(1) 0.007(1) 0.003(1) 0.002(1) 0.009(1) 0.014(1) 0.006(1) 0.004(1) 0.004(1) 0.014(1) 0.015(1) 0.016(1) 0.013(1) 0.016(2) 0.014(1) 0.010(2) 0.048(3) 0.039(3) 0.019(2) 0.011(2)
U23 0.0070(3) 0.0141(3) 0.011(1) 0.0079(9) 0.0096(9) 0.020(1) 0.019(1) 0.0063(8) 0.005(1) 0.004(1) 0.004(1) 0.008(1) -0.005(1) -0.007(1) 0.007(1) 0.008(1) 0.008(1) 0.026(1) 0.018(1) 0.025(1) 0.019(1) 0.019(1) 0.011(1) 0.001(2) -0.018(2) 0.001(2) 0.012(2) 0.017(2)
5. Lin, H.-H.; Wu, W.-Y.; Cao, S.-L.; Liao, J.; Ma, L.; Gao, M.; Li, Z.-F.; Xu, X.: Synthesis and antiproliferative evaluation of piperazine-1carbothiohydrazide derivatives of indolin-2-one. Bioorg. Med. Chem. Lett. 23 (2013) 3304-3307. 6. Bacchi, A.; Carcelli, M.; Pelagatti, P.; Pelizzi, G.; Rodriguez-Arguelles, M. C.; Rogolino, D.; Solinas, C.; Zani, F.: Antimicrobial and mutagenic properties of organotin(IV) complexes with isatin and N-alkylisatin bisthiocarbonohydrazones. J. Inorg. Biochem. 99 (2005) 397-408. 7. Labisbal, E.; Sousa-Pedrares, A.; Kaminsky, W.; West, D. X.: Structure of N-Methylisatin N(4)-Dimethylthiosemicarbazone and its Electrochemically Synthesized 6-Coordinate Cadmium(II) Complex. Z. Naturforsch. B. 57 (2002) 908-913. 8. Sheldrick, G. M.: A short history of SHELX. Acta Crystallogr. A64 (2008) 112-122.
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