Literature DB >> 21589138

Ethyl 3-[2-(p-tolyl-carbamothio-yl)hydrazinyl-idene]butano-ate.

Yan-Ling Zhang¹, Xu-Feng Hou, Fu-Juan Zhang, Feng-Ling Yang.

Abstract

The title compound, C(14)H(19)N(3)O(2)S, was obtained from a condensation reaction of N-(p-tol-yl)hydrazinecarbothio-amide and ethyl acetoacetate. The mol-ecule assumes an E configuration; the thio-semicarbazide and ester groups are located on the opposite sides of the C=N bond. The almost planar thio-semicarbazide unit (r.m.s. deviation = 0.0130 Å) is tilted at a dihedral angle of 49.54 (12)° with respect to the benzene ring. Inter-molecular N-H⋯N and N-H⋯S hydrogen bonding stabilizes the crystal structure. The eth-oxy group of the ester unit is disordered over two positions, with a site-occupancy ratio of 0.680 (10):0.320 (10).

Entities: CellLine Chemical Disease Gene

Year: 2010 PMID： 21589138 PMCID： PMC3009117 DOI： 10.1107/S160053681004290X

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For biological applications of thiosemicarbazones, see: Okabe et al. (1993 ▶); Hu et al. (2006 ▶). For related structures, see: Zhang et al. (2005 ▶); Shan & Zhang (2006 ▶).

Experimental

Crystal data

C14H19N3O2S M = 293.38 Orthorhombic, a = 14.1747 (3) Å b = 25.1439 (4) Å c = 17.4381 (2) Å V = 6215.08 (17) Å3 Z = 16 Cu Kα radiation μ = 1.90 mm−1 T = 293 K 0.20 × 0.18 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.703, T max = 0.726 6852 measured reflections 2775 independent reflections 2380 reflections with I > 2σ(I) R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.057 wR(F 2) = 0.175 S = 1.07 2775 reflections 199 parameters H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.33 e Å−3 Δρmin = −0.37 e Å−3 Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL. Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681004290X/xu5056sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S160053681004290X/xu5056Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₁₄H₁₉N₃O₂S	F(000) = 2496
M_r = 293.38	D_x = 1.254 Mg m⁻³
Orthorhombic, Ibca	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -I 2b 2c	Cell parameters from 4042 reflections
a = 14.1747 (3) Å	θ = 3.1–72.2°
b = 25.1439 (4) Å	µ = 1.90 mm⁻¹
c = 17.4381 (2) Å	T = 293 K
V = 6215.08 (17) Å³	Prismatic, colorless
Z = 16	0.20 × 0.18 × 0.18 mm

Oxford Diffraction Xcalibur Eos Gemini diffractometer	2775 independent reflections
Radiation source: fine-focus sealed tube	2380 reflections with I > 2σ(I)
graphite	R_int = 0.018
ω scans	θ_max = 67.0°, θ_min = 3.5°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −16→13
T_min = 0.703, T_max = 0.726	k = −30→29
6852 measured reflections	l = −20→10

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.175	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.111P)² + 3.488P] where P = (F_o² + 2F_c²)/3
2775 reflections	(Δ/σ)_max = 0.001
199 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.89584 (5)	0.56086 (3)	0.67758 (3)	0.0567 (3)
N1	0.84677 (12)	0.51980 (8)	0.54081 (10)	0.0426 (4)
N2	0.78883 (13)	0.47864 (8)	0.64691 (10)	0.0468 (5)
H2B	0.7853	0.4742	0.6957	0.056*
N3	0.74049 (14)	0.44509 (7)	0.59763 (10)	0.0456 (5)
C1	0.88957 (13)	0.55867 (8)	0.49298 (12)	0.0405 (5)
C2	0.93995 (16)	0.54086 (9)	0.42997 (11)	0.0449 (5)
H2A	0.9461	0.5046	0.4210	0.054*
C3	0.98110 (17)	0.57697 (10)	0.38031 (13)	0.0521 (6)
H3A	1.0146	0.5646	0.3381	0.063*
C4	0.97320 (18)	0.63105 (10)	0.39238 (14)	0.0569 (6)
C5	0.9206 (2)	0.64823 (10)	0.45486 (15)	0.0595 (6)
H5A	0.9137	0.6845	0.4636	0.071*
C6	0.87831 (18)	0.61255 (10)	0.50432 (14)	0.0513 (5)
H6A	0.8423	0.6249	0.5452	0.062*
C7	1.0220 (3)	0.66988 (14)	0.33947 (19)	0.0859 (10)
H7A	1.0114	0.7055	0.3573	0.129*
H7B	0.9970	0.6662	0.2886	0.129*
H7C	1.0885	0.6627	0.3389	0.129*
C8	0.84189 (14)	0.51858 (9)	0.61720 (11)	0.0420 (5)
C9	0.68544 (16)	0.41050 (9)	0.62652 (13)	0.0479 (5)
C10	0.6300 (2)	0.37820 (11)	0.56998 (17)	0.0627 (7)
H10A	0.6424	0.3924	0.5193	0.075*
H10B	0.5636	0.3838	0.5805	0.075*
C11	0.6470 (3)	0.31894 (13)	0.56713 (19)	0.0735 (8)
C12	0.6676 (2)	0.40351 (14)	0.71046 (17)	0.0765 (9)
H12A	0.7242	0.3913	0.7350	0.115*
H12B	0.6183	0.3778	0.7178	0.115*
H12C	0.6489	0.4369	0.7324	0.115*
O1	0.6285 (3)	0.29160 (13)	0.5138 (2)	0.1299 (13)
C13	0.7213 (7)	0.2436 (2)	0.6246 (4)	0.113 (3)	0.680 (10)
H13A	0.7212	0.2299	0.5726	0.135*	0.680 (10)
H13B	0.7831	0.2372	0.6466	0.135*	0.680 (10)
C14	0.6501 (10)	0.2163 (3)	0.6696 (5)	0.143 (4)	0.680 (10)
H14A	0.6632	0.1789	0.6701	0.214*	0.680 (10)
H14B	0.5891	0.2224	0.6473	0.214*	0.680 (10)
H14C	0.6509	0.2297	0.7211	0.214*	0.680 (10)
O2	0.7016 (4)	0.30089 (13)	0.6237 (2)	0.0891 (18)	0.680 (10)
C13'	0.6327 (18)	0.2371 (11)	0.6442 (15)	0.138 (8)*	0.320 (10)
H13C	0.6033	0.2200	0.6005	0.165*	0.320 (10)
H13D	0.5973	0.2272	0.6896	0.165*	0.320 (10)
C14'	0.7322 (16)	0.2172 (10)	0.6520 (14)	0.137 (7)*	0.320 (10)
H14D	0.7318	0.1792	0.6561	0.206*	0.320 (10)
H14E	0.7603	0.2322	0.6972	0.206*	0.320 (10)
H14F	0.7680	0.2276	0.6078	0.206*	0.320 (10)
O2'	0.6275 (10)	0.2960 (5)	0.6341 (7)	0.115 (4)*	0.320 (10)
H1N	0.8246 (18)	0.4946 (12)	0.5181 (15)	0.046 (7)*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0723 (5)	0.0606 (4)	0.0371 (4)	−0.0171 (3)	−0.0054 (2)	−0.0039 (2)
N1	0.0470 (9)	0.0466 (10)	0.0342 (9)	−0.0067 (8)	−0.0016 (7)	−0.0005 (7)
N2	0.0538 (10)	0.0543 (11)	0.0322 (8)	−0.0077 (8)	0.0016 (7)	0.0029 (7)
N3	0.0515 (10)	0.0467 (10)	0.0386 (9)	−0.0045 (8)	−0.0002 (8)	0.0017 (7)
C1	0.0393 (10)	0.0482 (11)	0.0341 (10)	−0.0022 (8)	−0.0036 (7)	0.0046 (8)
C2	0.0517 (11)	0.0466 (11)	0.0365 (10)	−0.0001 (9)	0.0001 (9)	0.0009 (8)
C3	0.0532 (12)	0.0639 (14)	0.0392 (11)	−0.0003 (11)	0.0042 (9)	0.0060 (10)
C4	0.0628 (14)	0.0594 (14)	0.0486 (12)	−0.0090 (12)	−0.0029 (11)	0.0148 (10)
C5	0.0755 (15)	0.0432 (12)	0.0599 (14)	0.0016 (11)	−0.0050 (12)	0.0069 (10)
C6	0.0582 (12)	0.0512 (12)	0.0447 (11)	0.0072 (10)	0.0020 (10)	0.0012 (10)
C7	0.105 (3)	0.080 (2)	0.0724 (18)	−0.0259 (19)	0.0066 (18)	0.0257 (16)
C8	0.0431 (10)	0.0485 (11)	0.0343 (10)	0.0003 (8)	−0.0005 (8)	0.0004 (8)
C9	0.0478 (11)	0.0475 (11)	0.0483 (12)	−0.0010 (9)	0.0000 (9)	0.0068 (9)
C10	0.0680 (15)	0.0528 (14)	0.0674 (16)	−0.0119 (12)	−0.0098 (13)	0.0079 (12)
C11	0.087 (2)	0.0642 (17)	0.0695 (17)	−0.0118 (15)	−0.0066 (15)	−0.0055 (14)
C12	0.0829 (19)	0.090 (2)	0.0560 (15)	−0.0268 (17)	0.0156 (14)	0.0096 (14)
O1	0.172 (3)	0.098 (2)	0.120 (2)	0.027 (2)	−0.048 (2)	−0.0389 (19)
C13	0.166 (7)	0.061 (3)	0.111 (5)	0.016 (4)	0.012 (5)	0.013 (3)
C14	0.250 (13)	0.073 (4)	0.106 (5)	−0.010 (6)	0.047 (7)	0.013 (4)
O2	0.130 (4)	0.0540 (18)	0.083 (2)	0.0084 (19)	−0.021 (2)	0.0044 (15)

S1—C8	1.680 (2)	C10—C11	1.510 (4)
N1—C8	1.334 (3)	C10—H10A	0.9700
N1—C1	1.421 (3)	C10—H10B	0.9700
N1—H1N	0.81 (3)	C11—O1	1.186 (4)
N2—C8	1.357 (3)	C11—O2'	1.332 (12)
N2—N3	1.386 (3)	C11—O2	1.333 (5)
N2—H2B	0.8600	C12—H12A	0.9600
N3—C9	1.272 (3)	C12—H12B	0.9600
C1—C6	1.378 (3)	C12—H12C	0.9600
C1—C2	1.385 (3)	C13—C14	1.450 (13)
C2—C3	1.384 (3)	C13—O2	1.468 (7)
C2—H2A	0.9300	C13—H13A	0.9700
C3—C4	1.381 (4)	C13—H13B	0.9700
C3—H3A	0.9300	C14—H14A	0.9600
C4—C5	1.389 (4)	C14—H14B	0.9600
C4—C7	1.511 (3)	C14—H14C	0.9600
C5—C6	1.381 (4)	C13'—O2'	1.49 (3)
C5—H5A	0.9300	C13'—C14'	1.50 (4)
C6—H6A	0.9300	C13'—H13C	0.9700
C7—H7A	0.9600	C13'—H13D	0.9700
C7—H7B	0.9600	C14'—H14D	0.9600
C7—H7C	0.9600	C14'—H14E	0.9600
C9—C12	1.496 (3)	C14'—H14F	0.9600
C9—C10	1.500 (4)

C8—N1—C1	128.61 (19)	C11—C10—H10B	107.8
C8—N1—H1N	116.7 (18)	H10A—C10—H10B	107.1
C1—N1—H1N	114.7 (18)	O1—C11—O2'	113.0 (6)
C8—N2—N3	119.19 (16)	O1—C11—O2	120.8 (4)
C8—N2—H2B	120.4	O2'—C11—O2	47.5 (6)
N3—N2—H2B	120.4	O1—C11—C10	124.2 (3)
C9—N3—N2	118.29 (19)	O2'—C11—C10	111.4 (6)
C6—C1—C2	119.4 (2)	O2—C11—C10	113.8 (3)
C6—C1—N1	122.8 (2)	C9—C12—H12A	109.5
C2—C1—N1	117.6 (2)	C9—C12—H12B	109.5
C3—C2—C1	120.1 (2)	H12A—C12—H12B	109.5
C3—C2—H2A	119.9	C9—C12—H12C	109.5
C1—C2—H2A	119.9	H12A—C12—H12C	109.5
C4—C3—C2	121.1 (2)	H12B—C12—H12C	109.5
C4—C3—H3A	119.4	C14—C13—O2	109.7 (8)
C2—C3—H3A	119.4	C14—C13—H13A	109.7
C3—C4—C5	118.0 (2)	O2—C13—H13A	109.7
C3—C4—C7	120.4 (3)	C14—C13—H13B	109.7
C5—C4—C7	121.6 (3)	O2—C13—H13B	109.7
C6—C5—C4	121.4 (2)	H13A—C13—H13B	108.2
C6—C5—H5A	119.3	C13—C14—H14A	109.5
C4—C5—H5A	119.3	C13—C14—H14B	109.5
C1—C6—C5	119.9 (2)	H14A—C14—H14B	109.5
C1—C6—H6A	120.0	C13—C14—H14C	109.5
C5—C6—H6A	120.0	H14A—C14—H14C	109.5
C4—C7—H7A	109.5	H14B—C14—H14C	109.5
C4—C7—H7B	109.5	C11—O2—C13	116.9 (5)
H7A—C7—H7B	109.5	O2'—C13'—C14'	113 (2)
C4—C7—H7C	109.5	O2'—C13'—H13C	109.0
H7A—C7—H7C	109.5	C14'—C13'—H13C	109.0
H7B—C7—H7C	109.5	O2'—C13'—H13D	109.0
N1—C8—N2	115.26 (19)	C14'—C13'—H13D	109.0
N1—C8—S1	125.98 (17)	H13C—C13'—H13D	107.8
N2—C8—S1	118.75 (15)	C13'—C14'—H14D	109.5
N3—C9—C12	124.8 (2)	C13'—C14'—H14E	109.5
N3—C9—C10	115.5 (2)	H14D—C14'—H14E	109.5
C12—C9—C10	119.4 (2)	C13'—C14'—H14F	109.5
C9—C10—C11	118.2 (2)	H14D—C14'—H14F	109.5
C9—C10—H10A	107.8	H14E—C14'—H14F	109.5
C11—C10—H10A	107.8	C11—O2'—C13'	121.6 (14)
C9—C10—H10B	107.8

C8—N2—N3—C9	−174.7 (2)	N3—N2—C8—S1	176.99 (15)
C8—N1—C1—C6	−44.9 (3)	N2—N3—C9—C12	0.8 (4)
C8—N1—C1—C2	138.9 (2)	N2—N3—C9—C10	175.7 (2)
C6—C1—C2—C3	2.1 (3)	N3—C9—C10—C11	116.9 (3)
N1—C1—C2—C3	178.3 (2)	C12—C9—C10—C11	−67.9 (4)
C1—C2—C3—C4	0.2 (3)	C9—C10—C11—O1	−158.9 (4)
C2—C3—C4—C5	−1.6 (4)	C9—C10—C11—O2'	60.4 (7)
C2—C3—C4—C7	177.4 (2)	C9—C10—C11—O2	8.7 (5)
C3—C4—C5—C6	0.9 (4)	O1—C11—O2—C13	−11.8 (7)
C7—C4—C5—C6	−178.2 (3)	O2'—C11—O2—C13	82.2 (9)
C2—C1—C6—C5	−2.8 (3)	C10—C11—O2—C13	−180.0 (5)
N1—C1—C6—C5	−178.9 (2)	C14—C13—O2—C11	−90.3 (9)
C4—C5—C6—C1	1.3 (4)	O1—C11—O2'—C13'	30.6 (18)
C1—N1—C8—N2	174.30 (19)	O2—C11—O2'—C13'	−80.9 (16)
C1—N1—C8—S1	−6.5 (3)	C10—C11—O2'—C13'	175.9 (14)
N3—N2—C8—N1	−3.8 (3)	C14'—C13'—O2'—C11	77 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N3ⁱ	0.81 (3)	2.54 (3)	3.300 (3)	155 (2)
N2—H2B···S1ⁱⁱ	0.86	2.85	3.5572 (18)	141

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N3ⁱ	0.81 (3)	2.54 (3)	3.300 (3)	155 (2)
N2—H2B⋯S1ⁱⁱ	0.86	2.85	3.5572 (18)	141

Symmetry codes: (i) ; (ii) .

2 in total

1. Synthesis and anticancer activity of thiosemicarbazones.

Authors: Wei-xiao Hu; Wei Zhou; Chun-nian Xia; Xi Wen
Journal: Bioorg Med Chem Lett Date: 2006-02-03 Impact factor: 2.823

2. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

2 in total