(E)-Methyl 3-(2-nitro-benzyl-idene)dithio-carbazate.

The asymmetric unit of the title compound, C(9)H(9)N(3)O(2)S(2), contains two independent mol-ecules, A and B, with similar bond dimensions. In both mol-ecules, the nitro group is tilted with respect to the aromatic ring [dihedral angles 32.0 (1)° in mol-ecule A and 34.0 (1)° in mol-ecule B]. The dithio-carbazate unit is nearly coplanar with the aromatic ring in both mol-ecules. For mol-ecule B, pairs of mol-ecules are linked by N-H⋯O and C-H⋯O hydrogen bonds about a centre of symmetry to form a dimer, whereas mol-ecules A are not involved in hydrogen bonding in the crystal structure.

Related literature

For general background, see: Okabe et al. (1993 ▶); Hu et al. (2001 ▶). For related structures, see: Chen et al. (2007 ▶); Shan & Zhang, 2006 ▶; Zhang et al. 2005 ▶). For synthesis, see: Hu et al. (2001 ▶).

Experimental

Crystal data

C9H9N3O2S2

M = 255.31

Triclinic,

a = 7.5261 (12) Å

b = 10.7128 (16) Å

c = 14.5343 (17) Å

α = 78.588 (6)°

β = 87.095 (5)°

γ = 84.612 (6)°

V = 1143.0 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.45 mm−1

T = 291 (2) K

0.36 × 0.30 × 0.16 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.795, T max = 0.930

11206 measured reflections

5127 independent reflections

3773 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.116

S = 1.10

5127 reflections

291 parameters

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.31 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680706059X/ng2380sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680706059X/ng2380Isup2.hkl

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

C9H9N3O2S2	Z = 4
Mr = 255.31	F000 = 528
Triclinic, P1	Dx = 1.484 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 7.5261 (12) Å	Cell parameters from 8768 reflections
b = 10.7128 (16) Å	θ = 3.5–25.2º
c = 14.5343 (17) Å	µ = 0.45 mm−1
α = 78.588 (6)º	T = 291 (2) K
β = 87.095 (5)º	Prism, yellow
γ = 84.612 (6)º	0.36 × 0.30 × 0.16 mm
V = 1143.0 (3) Å3

Rigaku R-AXIS RAPID IP diffractometer	5127 independent reflections
Radiation source: fine-focus sealed tube	3773 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.024
Detector resolution: 10.00 pixels mm-1	θmax = 27.4º
T = 294(2) K	θmin = 3.0º
ω scans	h = −9→9
Absorption correction: multi-scan(ABSCOR; Higashi, 1995)	k = −13→13
Tmin = 0.795, Tmax = 0.930	l = −18→18
11206 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041	H-atom parameters constrained
wR(F2) = 0.116	w = 1/[σ2(Fo2) + (0.0526P)2 + 0.2566P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max = 0.002
5127 reflections	Δρmax = 0.32 e Å−3
291 parameters	Δρmin = −0.31 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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
S1	−0.10244 (10)	0.28477 (6)	0.50066 (5)	0.0686 (2)
S2	−0.04064 (8)	0.25046 (5)	0.29873 (4)	0.05480 (17)
S11	0.67348 (9)	0.86939 (5)	0.15976 (5)	0.06155 (19)
S12	0.62739 (8)	0.64462 (5)	0.06773 (4)	0.05198 (16)
N1	0.1634 (3)	0.88846 (18)	0.18824 (14)	0.0555 (5)
N2	0.0369 (2)	0.50343 (16)	0.26593 (12)	0.0470 (4)
N3	−0.0124 (3)	0.46023 (17)	0.35805 (13)	0.0545 (5)
H3N	−0.0185	0.5114	0.3970	0.065*
N11	0.3762 (3)	0.30552 (17)	0.50958 (12)	0.0499 (4)
N12	0.5421 (2)	0.52269 (15)	0.24812 (12)	0.0420 (4)
N13	0.5836 (3)	0.64538 (16)	0.24503 (12)	0.0477 (4)
H13N	0.5823	0.6745	0.2961	0.057*
O1	0.1188 (3)	1.00252 (16)	0.16247 (14)	0.0801 (6)
O2	0.2133 (3)	0.84171 (18)	0.26726 (13)	0.0751 (5)
O11	0.4082 (3)	0.23524 (18)	0.58419 (12)	0.0875 (7)
O12	0.3194 (3)	0.41716 (15)	0.50380 (12)	0.0646 (5)
C1	0.1201 (3)	0.67717 (18)	0.14835 (14)	0.0404 (4)
C2	0.1581 (3)	0.80514 (18)	0.12003 (14)	0.0427 (4)
C3	0.1920 (3)	0.8603 (2)	0.02687 (15)	0.0496 (5)
H3	0.2125	0.9463	0.0103	0.060*
C4	0.1951 (3)	0.7869 (2)	−0.04046 (16)	0.0535 (5)
H4	0.2187	0.8226	−0.1031	0.064*
C5	0.1629 (3)	0.6593 (2)	−0.01493 (16)	0.0532 (5)
H5	0.1668	0.6091	−0.0605	0.064*
C6	0.1251 (3)	0.6061 (2)	0.07770 (16)	0.0494 (5)
H6	0.1025	0.5205	0.0933	0.059*
C7	0.0663 (3)	0.6209 (2)	0.24519 (15)	0.0480 (5)
H7	0.0539	0.6708	0.2911	0.058*
C8	−0.0516 (3)	0.3381 (2)	0.38814 (16)	0.0504 (5)
C9	−0.0977 (4)	0.0963 (2)	0.3612 (2)	0.0689 (7)
H9A	−0.0182	0.0664	0.4121	0.103*
H9B	−0.0869	0.0369	0.3193	0.103*
H9C	−0.2183	0.1032	0.3857	0.103*
C11	0.4580 (3)	0.32678 (17)	0.33941 (13)	0.0382 (4)
C12	0.4033 (3)	0.25252 (18)	0.42419 (13)	0.0390 (4)
C13	0.3699 (3)	0.12543 (18)	0.43353 (15)	0.0453 (5)
H13	0.3341	0.0789	0.4914	0.054*
C14	0.3904 (3)	0.06946 (19)	0.35602 (16)	0.0514 (5)
H14	0.3677	−0.0155	0.3608	0.062*
C15	0.4450 (3)	0.1400 (2)	0.27100 (16)	0.0511 (5)
H15	0.4585	0.1020	0.2185	0.061*
C16	0.4798 (3)	0.2658 (2)	0.26259 (15)	0.0451 (5)
H16	0.5186	0.3109	0.2048	0.054*
C17	0.5029 (3)	0.45918 (19)	0.32906 (14)	0.0454 (5)
H17	0.5028	0.4967	0.3816	0.054*
C18	0.6263 (3)	0.72055 (18)	0.16279 (14)	0.0427 (5)
C19	0.6919 (4)	0.7682 (3)	−0.02735 (17)	0.0663 (7)
H19A	0.5985	0.8366	−0.0368	0.099*
H19B	0.7119	0.7340	−0.0836	0.099*
H19C	0.7996	0.8002	−0.0124	0.099*

	U11	U22	U33	U12	U13	U23
S1	0.0862 (5)	0.0596 (4)	0.0520 (3)	−0.0072 (3)	0.0147 (3)	0.0049 (3)
S2	0.0588 (3)	0.0460 (3)	0.0564 (3)	−0.0097 (3)	0.0041 (3)	−0.0011 (2)
S11	0.0834 (4)	0.0354 (3)	0.0657 (4)	−0.0174 (3)	0.0141 (3)	−0.0080 (3)
S12	0.0637 (4)	0.0490 (3)	0.0444 (3)	−0.0098 (3)	−0.0008 (3)	−0.0096 (2)
N1	0.0720 (13)	0.0434 (10)	0.0562 (12)	−0.0216 (9)	0.0085 (10)	−0.0167 (9)
N2	0.0487 (10)	0.0401 (9)	0.0482 (10)	−0.0041 (8)	0.0011 (8)	0.0004 (7)
N3	0.0682 (12)	0.0446 (10)	0.0471 (10)	−0.0055 (9)	0.0062 (9)	−0.0023 (8)
N11	0.0681 (12)	0.0432 (10)	0.0405 (9)	−0.0102 (9)	0.0001 (9)	−0.0114 (8)
N12	0.0511 (10)	0.0315 (8)	0.0441 (9)	−0.0073 (7)	−0.0019 (8)	−0.0068 (7)
N13	0.0674 (12)	0.0347 (8)	0.0425 (9)	−0.0142 (8)	0.0037 (8)	−0.0078 (7)
O1	0.1226 (17)	0.0372 (9)	0.0830 (13)	−0.0105 (10)	0.0093 (12)	−0.0194 (9)
O2	0.1115 (16)	0.0655 (11)	0.0557 (11)	−0.0289 (11)	−0.0109 (10)	−0.0178 (9)
O11	0.164 (2)	0.0608 (11)	0.0367 (9)	−0.0046 (12)	−0.0097 (11)	−0.0065 (8)
O12	0.0928 (13)	0.0452 (9)	0.0593 (10)	−0.0055 (9)	0.0089 (9)	−0.0219 (7)
C1	0.0378 (10)	0.0347 (9)	0.0481 (11)	−0.0036 (8)	−0.0020 (8)	−0.0063 (8)
C2	0.0452 (11)	0.0369 (10)	0.0475 (11)	−0.0076 (8)	0.0004 (9)	−0.0105 (8)
C3	0.0563 (13)	0.0400 (11)	0.0509 (12)	−0.0102 (9)	0.0048 (10)	−0.0038 (9)
C4	0.0555 (13)	0.0572 (13)	0.0467 (12)	−0.0055 (11)	0.0023 (10)	−0.0085 (10)
C5	0.0584 (13)	0.0542 (13)	0.0519 (13)	−0.0078 (11)	−0.0006 (11)	−0.0206 (10)
C6	0.0528 (12)	0.0370 (10)	0.0610 (13)	−0.0088 (9)	−0.0024 (10)	−0.0139 (10)
C7	0.0537 (12)	0.0409 (11)	0.0491 (12)	−0.0083 (9)	−0.0005 (10)	−0.0067 (9)
C8	0.0464 (11)	0.0455 (11)	0.0530 (12)	−0.0008 (9)	0.0043 (10)	0.0027 (10)
C9	0.0703 (16)	0.0472 (13)	0.0838 (19)	−0.0125 (12)	0.0040 (14)	0.0016 (12)
C11	0.0435 (10)	0.0327 (9)	0.0396 (10)	−0.0055 (8)	−0.0058 (8)	−0.0079 (8)
C12	0.0455 (11)	0.0346 (9)	0.0385 (10)	−0.0037 (8)	−0.0069 (8)	−0.0096 (8)
C13	0.0546 (12)	0.0329 (10)	0.0476 (11)	−0.0077 (9)	−0.0073 (10)	−0.0026 (8)
C14	0.0628 (14)	0.0309 (10)	0.0635 (14)	−0.0070 (9)	−0.0164 (11)	−0.0113 (9)
C15	0.0617 (14)	0.0444 (11)	0.0527 (12)	0.0000 (10)	−0.0101 (10)	−0.0230 (10)
C16	0.0522 (12)	0.0437 (11)	0.0417 (10)	−0.0062 (9)	−0.0022 (9)	−0.0129 (9)
C17	0.0615 (13)	0.0379 (10)	0.0398 (10)	−0.0119 (9)	−0.0023 (9)	−0.0110 (8)
C18	0.0462 (11)	0.0357 (10)	0.0457 (11)	−0.0050 (8)	0.0023 (9)	−0.0072 (8)
C19	0.0759 (17)	0.0732 (17)	0.0450 (12)	−0.0097 (14)	0.0031 (12)	0.0006 (11)

S1—C8	1.660 (2)	C3—H3	0.9300
S2—C8	1.742 (3)	C4—C5	1.385 (3)
S2—C9	1.800 (2)	C4—H4	0.9300
S11—C18	1.657 (2)	C5—C6	1.381 (3)
S12—C18	1.736 (2)	C5—H5	0.9300
S12—C19	1.797 (2)	C6—H6	0.9300
N1—O2	1.221 (3)	C7—H7	0.9300
N1—O1	1.225 (2)	C9—H9A	0.9600
N1—C2	1.464 (3)	C9—H9B	0.9600
N2—C7	1.272 (3)	C9—H9C	0.9600
N2—N3	1.372 (2)	C11—C12	1.394 (3)
N3—C8	1.350 (3)	C11—C16	1.396 (3)
N3—H3N	0.8600	C11—C17	1.466 (3)
N11—O11	1.212 (2)	C12—C13	1.387 (3)
N11—O12	1.220 (2)	C13—C14	1.373 (3)
N11—C12	1.461 (3)	C13—H13	0.9300
N12—C17	1.273 (3)	C14—C15	1.380 (3)
N12—N13	1.371 (2)	C14—H14	0.9300
N13—C18	1.345 (2)	C15—C16	1.378 (3)
N13—H13N	0.8600	C15—H15	0.9300
C1—C6	1.391 (3)	C16—H16	0.9300
C1—C2	1.403 (3)	C17—H17	0.9300
C1—C7	1.470 (3)	C19—H19A	0.9600
C2—C3	1.387 (3)	C19—H19B	0.9600
C3—C4	1.369 (3)	C19—H19C	0.9600
C8—S2—C9	101.93 (12)	N3—C8—S2	113.24 (16)
C18—S12—C19	101.57 (11)	S1—C8—S2	126.39 (13)
O2—N1—O1	123.3 (2)	S2—C9—H9A	109.5
O2—N1—C2	118.83 (19)	S2—C9—H9B	109.5
O1—N1—C2	117.9 (2)	H9A—C9—H9B	109.5
C7—N2—N3	115.10 (19)	S2—C9—H9C	109.5
C8—N3—N2	120.7 (2)	H9A—C9—H9C	109.5
C8—N3—H3N	119.7	H9B—C9—H9C	109.5
N2—N3—H3N	119.7	C12—C11—C16	116.26 (17)
O11—N11—O12	122.41 (19)	C12—C11—C17	123.88 (18)
O11—N11—C12	118.20 (18)	C16—C11—C17	119.74 (18)
O12—N11—C12	119.38 (17)	C13—C12—C11	123.03 (19)
C17—N12—N13	115.97 (17)	C13—C12—N11	115.63 (18)
C18—N13—N12	120.58 (17)	C11—C12—N11	121.34 (17)
C18—N13—H13N	119.7	C14—C13—C12	118.95 (19)
N12—N13—H13N	119.7	C14—C13—H13	120.5
C6—C1—C2	116.07 (19)	C12—C13—H13	120.5
C6—C1—C7	120.58 (18)	C13—C14—C15	119.60 (19)
C2—C1—C7	123.24 (19)	C13—C14—H14	120.2
C3—C2—C1	122.61 (19)	C15—C14—H14	120.2
C3—C2—N1	116.12 (17)	C16—C15—C14	121.1 (2)
C1—C2—N1	121.27 (18)	C16—C15—H15	119.5
C4—C3—C2	119.33 (19)	C14—C15—H15	119.5
C4—C3—H3	120.3	C15—C16—C11	121.1 (2)
C2—C3—H3	120.3	C15—C16—H16	119.5
C3—C4—C5	119.7 (2)	C11—C16—H16	119.5
C3—C4—H4	120.1	N12—C17—C11	119.89 (18)
C5—C4—H4	120.1	N12—C17—H17	120.1
C6—C5—C4	120.4 (2)	C11—C17—H17	120.1
C6—C5—H5	119.8	N13—C18—S11	120.14 (16)
C4—C5—H5	119.8	N13—C18—S12	113.32 (14)
C5—C6—C1	121.75 (19)	S11—C18—S12	126.54 (12)
C5—C6—H6	119.1	S12—C19—H19A	109.5
C1—C6—H6	119.1	S12—C19—H19B	109.5
N2—C7—C1	119.6 (2)	H19A—C19—H19B	109.5
N2—C7—H7	120.2	S12—C19—H19C	109.5
C1—C7—H7	120.2	H19A—C19—H19C	109.5
N3—C8—S1	120.37 (19)	H19B—C19—H19C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N13—H13N···O11i	0.86	2.16	3.014 (3)	174
C17—H17···O12i	0.93	2.55	3.373 (3)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N13—H13N⋯O11i	0.86	2.16	3.014 (3)	174
C17—H17⋯O12i	0.93	2.55	3.373 (3)	148

Symmetry code: (i) .