Abstract
C22H31N5O4S2, triclinic, P1̅ (no. 2), a = 9.0366(1) Å, b = 10.3253(2) Å, c = 14.9997(2) Å, α = 72.790(1)°, β = 82.301(1)°, γ = 71.080(1)°, V = 1263.54(3) Å3, Z = 2, Rgt(F) = 0.0443, wRref(F2) = 0.1294, T = 271 K.
The crystal structure is shown in the figure. Tables 1 and 2 contain details on crystal structure and measurement conditions and a list of the atoms including atomic coordinates and displacement parameters.
Crystal: | Block, clear reddish red |
Size: | 0.30 × 0.25 × 0.20 mm |
Wavelength: | Cu Kα radiation (1.54184 Å) |
μ: | 2.22 mm−1 |
Diffractometer, scan mode: | XtaLAB Pro, ω-scans |
θmax, completeness: | 66.6°, >98% |
N(hkl)measured, N(hkl)unique, Rint: | 13898, 4400, 0.025 |
Criterion for Iobs, N(hkl)gt: | Iobs > 2 σ(Iobs), 3901 |
N(param)refined: | 303 |
Programs: | CrysAlisPro [1], SHELX [2], OLEX2 [3] |
Atom | x | y | z | Uiso*/Ueq |
---|---|---|---|---|
S1 | 0.86259(7) | 0.72163(6) | 0.56844(4) | 0.06572(19) |
S2 | 0.93686(8) | 0.86122(7) | 0.36715(5) | 0.0788(2) |
O1 | 0.5294(2) | 0.16350(18) | 0.74428(11) | 0.0721(4) |
O2 | 0.7827(2) | 0.52608(19) | 0.29371(11) | 0.0746(5) |
O3 | 0.2372(2) | 0.7811(2) | −0.08058(11) | 0.0815(5) |
O4 | 0.0215(2) | 0.7585(3) | 0.00940(12) | 0.1034(7) |
N1 | 0.8318(2) | 0.64173(19) | 0.42569(13) | 0.0613(4) |
H1 | 0.8411 | 0.6384 | 0.3685 | 0.074* |
N2 | 0.77230(19) | 0.54791(18) | 0.49205(12) | 0.0550(4) |
N3 | 0.6714(2) | 0.34697(19) | 0.36750(12) | 0.0585(4) |
N4 | 0.4210(2) | 0.48759(19) | 0.21774(11) | 0.0549(4) |
N5 | 0.2416(2) | 0.7144(2) | 0.07638(12) | 0.0717(5) |
C1 | 0.9309(3) | 0.8618(3) | 0.57635(19) | 0.0747(6) |
H1A | 0.8610 | 0.9517 | 0.5452 | 0.112* |
H1B | 1.0339 | 0.8515 | 0.5473 | 0.112* |
H1C | 0.9346 | 0.8575 | 0.6409 | 0.112* |
C2 | 0.8765(2) | 0.7405(2) | 0.44860(15) | 0.0579(5) |
C3 | 0.7254(2) | 0.4627(2) | 0.46264(14) | 0.0526(5) |
C4 | 0.6583(2) | 0.35330(19) | 0.52068(14) | 0.0490(4) |
C5 | 0.6230(2) | 0.3128(2) | 0.61511(14) | 0.0525(5) |
H5A | 0.6407 | 0.3597 | 0.6550 | 0.063* |
C10 | 0.4475(4) | 0.0634(3) | 0.7820(2) | 0.0938(9) |
H10A | 0.4346 | 0.0483 | 0.8485 | 0.141* |
H10B | 0.5053 | −0.0247 | 0.7679 | 0.141* |
H10C | 0.3465 | 0.0983 | 0.7553 | 0.141* |
C6 | 0.5602(2) | 0.1999(2) | 0.64948(14) | 0.0549(5) |
C7 | 0.5325(3) | 0.1314(2) | 0.58972(16) | 0.0597(5) |
H7A | 0.4907 | 0.0561 | 0.6138 | 0.072* |
C8 | 0.5664(3) | 0.1735(2) | 0.49432(16) | 0.0612(5) |
H8A | 0.5475 | 0.1274 | 0.4543 | 0.073* |
C9 | 0.6282(2) | 0.2847(2) | 0.46057(14) | 0.0527(5) |
C11 | 0.7318(2) | 0.4538(2) | 0.36337(15) | 0.0590(5) |
C12 | 0.6606(3) | 0.2983(3) | 0.28722(16) | 0.0703(6) |
H12A | 0.7067 | 0.1959 | 0.3021 | 0.084* |
H12B | 0.7210 | 0.3402 | 0.2347 | 0.084* |
C13 | 0.4939(3) | 0.3362(2) | 0.25879(16) | 0.0685(6) |
H13A | 0.4933 | 0.2851 | 0.2141 | 0.082* |
H13B | 0.4311 | 0.3040 | 0.3134 | 0.082* |
C14 | 0.2526(3) | 0.5167(3) | 0.21277(17) | 0.0761(7) |
H14A | 0.2079 | 0.4891 | 0.2754 | 0.091* |
H14B | 0.2346 | 0.4593 | 0.1769 | 0.091* |
C15 | 0.1712(3) | 0.6701(3) | 0.16869(17) | 0.0870(9) |
H15A | 0.0610 | 0.6836 | 0.1638 | 0.104* |
H15B | 0.1800 | 0.7277 | 0.2073 | 0.104* |
C16 | 0.4081(3) | 0.6899(3) | 0.07957(17) | 0.0688(6) |
H16A | 0.4257 | 0.7487 | 0.1145 | 0.083* |
H16B | 0.4519 | 0.7166 | 0.0166 | 0.083* |
C17 | 0.4889(3) | 0.5361(3) | 0.12496(15) | 0.0657(6) |
H17A | 0.4809 | 0.4786 | 0.0861 | 0.079* |
H17B | 0.5990 | 0.5231 | 0.1297 | 0.079* |
C18 | 0.1726(3) | 0.7530(2) | −0.00518(15) | 0.0608(5) |
C19 | −0.0854(3) | 0.8048(3) | −0.06525(18) | 0.0785(7) |
C20 | −0.0390(6) | 0.7027(7) | −0.1223(5) | 0.190(3) |
H20A | 0.0729 | 0.6630 | −0.1241 | 0.285* |
H20B | −0.0737 | 0.7507 | −0.1847 | 0.285* |
H20C | −0.0861 | 0.6280 | −0.0954 | 0.285* |
C21 | −0.2374(4) | 0.7999(9) | −0.0160(3) | 0.246(4) |
H21A | −0.2250 | 0.7084 | 0.0279 | 0.368* |
H21B | −0.3127 | 0.8156 | −0.0606 | 0.368* |
H21C | −0.2732 | 0.8725 | 0.0165 | 0.368* |
C22 | −0.0854(6) | 0.9457(5) | −0.1267(4) | 0.186(3) |
H22A | −0.1071 | 1.0121 | −0.0899 | 0.278* |
H22B | −0.1645 | 0.9774 | −0.1718 | 0.278* |
H22C | 0.0152 | 0.9392 | −0.1584 | 0.278* |
Source of material
The title compound was synthesized via a three-step synthetic protocol. The reaction of 5-methoxyindoline-2,3-dione (0.9 g, 5 mmol) with 1,2-dibromoethane (2.8 g,15 mmol) in 15 mL of N,N-dimethylformamide (DMF) in the presence of potassium carbonate (1.0 g, 7.2 mmol) at 40–50 °C gave 1-(2-bromoethyl)indoline-2,3-dione [4]. Next, 1-(2-bromoethyl)indoline-2,3-dione (0.6 g, 2.0 mmol) was reacted with tert-butyl piperazine-1-carboxylate (1.1 g, 0.6 mmol) in DMF (5 mL) for 12 h at room temperature to yield 1-((4-(tert-butyloxycarbonyl)piperazin-1-yl)ethyl)-5-methoxyindolin-2,3-dione. Finally, condensation of 1-((4-(tert-butyloxycarbonyl)piperazin-1-yl)-5-methoxyindolin-2,3-dione (0.4 g, 1 mmol) with methyl hydrazinecarbodithioate (0.1 g, 1 mmol) in 5 mL methanol at room temperature for 12 h gave a solid, which was collected by filtration and dried in air. The crude product was purified by recrystallization from methanol (yield 60%; m.p. 421–423 K). Crystals of the title compound were obtained by slow evaporation of the mixed solvent dichloromethane and methanol (5:1, v/v).
Experimental details
H atoms were placed in calculated positions. The Uiso values of the hydrogen atoms of methyl groups were set to 1.5Ueq(C) and the Uiso values of all other hydrogen atoms were set to 1.2Ueq(C, N).
Discussion
Indolin-2-one derivatives exhibit promising antitumor activity by targeting different biomacromolecules [5, 6] , of which 3-hydrazinoindolin-2-one derivatives have particularly attracted intensive attention [7, 8] . In our previous work, methyl hydrazinecarbodithioate derivatives of 5-fluoro-1-(2-morpholinoethyl)indolin-2-one and 5-methoxy-1-(2-morpholinoethyl)indolin-2-one were used as ligands to achieve two new Pt(II) complexes, which exhibited cytotoxicity against cancer cells by inducing apoptosis [9].
As a continuous work, herein we report a new methyl hydrazinecarbodithioate derivative. X-ray single-crystal diffraction analysis revealed that the hydrazinecarbodithioate and the indolin-2-moieties are almost coplanar. Intramolecular hydrogen bonding (D⋯A = 2.742(2) Å) occurs between the O2 atom and N1—H1 group. The indolin-2-one ring system links to piperazine ring (chair configuration) via a –CH2–CH2– bridge with the N3–C12–C13–N4 torsion angle of 69.7(3)°. The bond length of C3=N2 (1.292(3) Å) and the angle of N2–C3–C11 (127.5(2)°) are in agreement with those of the structure of an analogous hydrazinecarbodithioate (1.288(4) Å, 128.1(3)°) [10]. Furthermore, there is a torsion angle O4—C18—N5—C15 of 5.8(4)°.
Acknowledgements
The authors are grateful to the 973 project (Grant no. 2013CB911002) for financial support.
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©2018 Xin-Hong Li et al., published by De Gruyter, Berlin/Boston
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