Eth-oxy-carbonyl-methyl 3-(4-chloro-benzyl-idene)dithio-carbazate.

Mol-ecules of the title compound, C(12)H(13)ClN(2)O(2)S(2), are linked into centrosymmetric dimers by pairs of inter-molecular N-H⋯S hydrogen bonds. In the crystal structure, there are π-π stacking inter-actions between symmetry-related benzene rings with a centroid-centroid distance of 3.7305 (13) Å, a perpendicular distance between the planes of 3.2851 (9) Å and a slippage of 1.768 Å. The structure is further stabilized by weak inter-molecular C-H⋯O hydrogen bonds.

Related literature

For the biological activity of related compounds, see: Gülerman et al. (2001 ▶); Duran et al. (2002 ▶). For related structures, see: Tabatabaee et al. (2006 ▶, 2007 ▶, 2008 ▶, 2009 ▶).

Experimental

Crystal data

C12H13ClN2O2S2

M = 316.81

Triclinic,

a = 7.3425 (3) Å

b = 10.3894 (4) Å

c = 10.6457 (5) Å

α = 116.535 (2)°

β = 95.049 (2)°

γ = 94.955 (2)°

V = 716.50 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.56 mm−1

T = 173 K

0.12 × 0.08 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer with APEXII CCD

Absorption correction: multi-scan (SORTAV; Blessing, 1997 ▶) T min = 0.936, T max = 0.967

12341 measured reflections

3996 independent reflections

3361 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.104

S = 1.09

3996 reflections

173 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.26 e Å−3

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶); data reduction: SCALEPACK (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681003549X/lh5124sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681003549X/lh5124Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H13ClN2O2S2	Z = 2
Mr = 316.81	F(000) = 328
Triclinic, P1	Dx = 1.468 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3425 (3) Å	Cell parameters from 3737 reflections
b = 10.3894 (4) Å	θ = 1.0–29.6°
c = 10.6457 (5) Å	µ = 0.56 mm−1
α = 116.535 (2)°	T = 173 K
β = 95.049 (2)°	Block, colorless
γ = 94.955 (2)°	0.12 × 0.08 × 0.06 mm
V = 716.50 (5) Å3

Nonius KappaCCD diffractometer with APEXII CCD	3996 independent reflections
Radiation source: fine-focus sealed tube	3361 reflections with I > 2σ(I)
graphite	Rint = 0.031
ω and φ scans	θmax = 29.7°, θmin = 2.2°
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	h = −10→10
Tmin = 0.936, Tmax = 0.967	k = −14→14
12341 measured reflections	l = −14→14

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)] = 0.045	Hydrogen site location: difference Fourier map
wR(F2) = 0.104	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0252P)2 + 0.6628P] where P = (Fo2 + 2Fc2)/3
3996 reflections	(Δ/σ)max < 0.001
173 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.26 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	Uiso*/Ueq
Cl1	0.89852 (9)	0.10405 (6)	0.44205 (7)	0.04491 (16)
S1	0.37647 (8)	0.94428 (5)	0.28183 (6)	0.03285 (14)
S2	0.37807 (7)	0.61903 (5)	0.12742 (5)	0.02750 (12)
O1	−0.0267 (2)	0.65882 (18)	0.13349 (16)	0.0355 (3)
O2	−0.0309 (2)	0.76565 (17)	−0.00860 (17)	0.0348 (3)
N1	0.5839 (2)	0.65588 (17)	0.36811 (18)	0.0251 (3)
N2	0.5413 (2)	0.78764 (17)	0.38235 (17)	0.0259 (3)
H2N	0.5813	0.8681	0.4610	0.031*
C1	0.7182 (2)	0.5188 (2)	0.4706 (2)	0.0224 (3)
C2	0.8110 (3)	0.5168 (2)	0.5894 (2)	0.0260 (4)
H2	0.8383	0.6039	0.6763	0.031*
C3	0.8640 (3)	0.3890 (2)	0.5824 (2)	0.0280 (4)
H3	0.9271	0.3880	0.6637	0.034*
C4	0.8236 (3)	0.2634 (2)	0.4555 (2)	0.0292 (4)
C5	0.7266 (3)	0.2612 (2)	0.3364 (2)	0.0306 (4)
H5	0.6973	0.1733	0.2505	0.037*
C6	0.6734 (3)	0.3889 (2)	0.3448 (2)	0.0263 (4)
H6	0.6057	0.3884	0.2642	0.032*
C7	0.6691 (3)	0.6550 (2)	0.4777 (2)	0.0244 (4)
H7	0.7005	0.7428	0.5636	0.029*
C8	0.4379 (3)	0.7910 (2)	0.2744 (2)	0.0238 (4)
C9	0.2345 (3)	0.6622 (2)	0.0105 (2)	0.0291 (4)
H9A	0.2984	0.7477	0.0061	0.035*
H9B	0.2172	0.5795	−0.0861	0.035*
C10	0.0471 (3)	0.6945 (2)	0.0554 (2)	0.0281 (4)
C11	−0.2133 (3)	0.8016 (3)	0.0258 (3)	0.0419 (5)
H11A	−0.2092	0.8571	0.1298	0.050*
H11B	−0.3024	0.7118	−0.0090	0.050*
C12	−0.2709 (4)	0.8910 (3)	−0.0444 (3)	0.0506 (6)
H12A	−0.3951	0.9147	−0.0251	0.061*
H12B	−0.2716	0.8359	−0.1470	0.061*
H12C	−0.1839	0.9809	−0.0071	0.061*

	U11	U22	U33	U12	U13	U23
Cl1	0.0472 (3)	0.0344 (3)	0.0633 (4)	0.0143 (2)	0.0028 (3)	0.0306 (3)
S1	0.0483 (3)	0.0196 (2)	0.0283 (3)	0.0074 (2)	−0.0043 (2)	0.01017 (19)
S2	0.0359 (3)	0.0192 (2)	0.0239 (2)	0.00528 (18)	0.00303 (19)	0.00682 (18)
O1	0.0363 (8)	0.0418 (9)	0.0338 (8)	0.0012 (7)	0.0033 (6)	0.0230 (7)
O2	0.0362 (8)	0.0390 (8)	0.0361 (8)	0.0066 (7)	0.0033 (6)	0.0233 (7)
N1	0.0275 (8)	0.0193 (7)	0.0301 (8)	0.0055 (6)	0.0036 (6)	0.0124 (7)
N2	0.0331 (9)	0.0173 (7)	0.0253 (8)	0.0037 (6)	0.0000 (6)	0.0087 (6)
C1	0.0212 (8)	0.0232 (8)	0.0266 (9)	0.0048 (7)	0.0044 (7)	0.0143 (7)
C2	0.0254 (9)	0.0293 (9)	0.0253 (9)	0.0058 (7)	0.0051 (7)	0.0136 (8)
C3	0.0243 (9)	0.0367 (10)	0.0311 (10)	0.0070 (8)	0.0045 (7)	0.0219 (9)
C4	0.0263 (9)	0.0290 (10)	0.0405 (11)	0.0073 (8)	0.0071 (8)	0.0223 (9)
C5	0.0365 (11)	0.0243 (9)	0.0306 (10)	0.0066 (8)	0.0039 (8)	0.0121 (8)
C6	0.0293 (9)	0.0270 (9)	0.0251 (9)	0.0046 (7)	0.0013 (7)	0.0144 (8)
C7	0.0238 (8)	0.0215 (8)	0.0268 (9)	0.0047 (7)	0.0048 (7)	0.0098 (7)
C8	0.0274 (9)	0.0207 (8)	0.0239 (9)	0.0030 (7)	0.0045 (7)	0.0108 (7)
C9	0.0361 (10)	0.0271 (9)	0.0215 (9)	0.0003 (8)	0.0013 (8)	0.0098 (8)
C10	0.0336 (10)	0.0238 (9)	0.0237 (9)	−0.0009 (8)	−0.0020 (8)	0.0099 (8)
C11	0.0372 (12)	0.0431 (13)	0.0504 (14)	0.0093 (10)	0.0063 (10)	0.0252 (12)
C12	0.0539 (16)	0.0440 (14)	0.0556 (16)	0.0164 (12)	0.0016 (13)	0.0237 (13)

Cl1—C4	1.739 (2)	C3—C4	1.380 (3)
S1—C8	1.6618 (19)	C3—H3	0.9500
S2—C8	1.7548 (19)	C4—C5	1.389 (3)
S2—C9	1.792 (2)	C5—C6	1.382 (3)
O1—C10	1.201 (2)	C5—H5	0.9500
O2—C10	1.339 (2)	C6—H6	0.9500
O2—C11	1.455 (3)	C7—H7	0.9500
N1—C7	1.279 (2)	C9—C10	1.513 (3)
N1—N2	1.375 (2)	C9—H9A	0.9900
N2—C8	1.337 (2)	C9—H9B	0.9900
N2—H2N	0.8800	C11—C12	1.493 (3)
C1—C2	1.392 (2)	C11—H11A	0.9900
C1—C6	1.398 (3)	C11—H11B	0.9900
C1—C7	1.462 (2)	C12—H12A	0.9800
C2—C3	1.388 (3)	C12—H12B	0.9800
C2—H2	0.9500	C12—H12C	0.9800
C8—S2—C9	100.82 (9)	C1—C7—H7	120.1
C10—O2—C11	115.16 (17)	N2—C8—S1	122.37 (14)
C7—N1—N2	116.85 (16)	N2—C8—S2	112.84 (13)
C8—N2—N1	118.65 (16)	S1—C8—S2	124.78 (11)
C8—N2—H2N	120.7	C10—C9—S2	113.36 (14)
N1—N2—H2N	120.7	C10—C9—H9A	108.9
C2—C1—C6	119.06 (17)	S2—C9—H9A	108.9
C2—C1—C7	120.29 (17)	C10—C9—H9B	108.9
C6—C1—C7	120.66 (16)	S2—C9—H9B	108.9
C3—C2—C1	120.73 (18)	H9A—C9—H9B	107.7
C3—C2—H2	119.6	O1—C10—O2	123.7 (2)
C1—C2—H2	119.6	O1—C10—C9	126.00 (19)
C4—C3—C2	118.96 (18)	O2—C10—C9	110.25 (17)
C4—C3—H3	120.5	O2—C11—C12	107.7 (2)
C2—C3—H3	120.5	O2—C11—H11A	110.2
C3—C4—C5	121.55 (18)	C12—C11—H11A	110.2
C3—C4—Cl1	119.71 (15)	O2—C11—H11B	110.2
C5—C4—Cl1	118.73 (16)	C12—C11—H11B	110.2
C6—C5—C4	119.01 (19)	H11A—C11—H11B	108.5
C6—C5—H5	120.5	C11—C12—H12A	109.5
C4—C5—H5	120.5	C11—C12—H12B	109.5
C5—C6—C1	120.63 (17)	H12A—C12—H12B	109.5
C5—C6—H6	119.7	C11—C12—H12C	109.5
C1—C6—H6	119.7	H12A—C12—H12C	109.5
N1—C7—C1	119.89 (17)	H12B—C12—H12C	109.5
N1—C7—H7	120.1
C7—N1—N2—C8	−174.09 (18)	C2—C1—C7—N1	−179.95 (18)
C6—C1—C2—C3	2.1 (3)	C6—C1—C7—N1	0.2 (3)
C7—C1—C2—C3	−177.71 (18)	N1—N2—C8—S1	179.15 (14)
C1—C2—C3—C4	0.1 (3)	N1—N2—C8—S2	−1.3 (2)
C2—C3—C4—C5	−1.9 (3)	C9—S2—C8—N2	177.22 (15)
C2—C3—C4—Cl1	176.88 (15)	C9—S2—C8—S1	−3.25 (16)
C3—C4—C5—C6	1.5 (3)	C8—S2—C9—C10	−73.08 (15)
Cl1—C4—C5—C6	−177.31 (16)	C11—O2—C10—O1	1.6 (3)
C4—C5—C6—C1	0.8 (3)	C11—O2—C10—C9	179.48 (17)
C2—C1—C6—C5	−2.6 (3)	S2—C9—C10—O1	−20.3 (3)
C7—C1—C6—C5	177.28 (18)	S2—C9—C10—O2	161.95 (14)
N2—N1—C7—C1	179.74 (16)	C10—O2—C11—C12	175.16 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···S1i	0.88	2.52	3.3669 (17)	161
C3—H3···O1ii	0.95	2.48	3.410 (2)	166
C9—H9B···O1iii	0.99	2.55	3.153 (3)	119
C9—H9A···S1	0.99	2.69	3.066 (2)	103

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯S1i	0.88	2.52	3.3669 (17)	161
C3—H3⋯O1ii	0.95	2.48	3.410 (2)	166
C9—H9B⋯O1iii	0.99	2.55	3.153 (3)	119

Symmetry codes: (i) ; (ii) ; (iii) .