(E)-1-(2-Nitro-benzyl-idene)-4-phenyl-thio-semicarbazide.

In the title mol-ecule, C(14)H(12)N(4)O(2)S, the conformation about the imine bond is trans. The dihedral angle between the two rings is 88.22 (11)°. An intra-molecular N-H⋯N contact occurs. The crystal structure features N-H⋯S and C-H⋯O hydrogen bonds.

Related literature

For background to thio­semicarbazone derivatives, see: Shaabani et al. (2011 ▶); Sardari et al. (1999 ▶). For applications of imine bonds in synthesis, see: Plech et al. (2011 ▶); Tada et al. (2011 ▶); Sriram et al. (2007 ▶). For related structures, see: Jian & Li (2006a ▶,b ▶); Fang et al. (2007 ▶).

Experimental

Crystal data

C14H12N4O2S

M = 300.35

Triclinic,

a = 7.4050 (7) Å

b = 8.4239 (8) Å

c = 12.2363 (10) Å

α = 90.382 (7)°

β = 93.974 (7)°

γ = 110.004 (8)°

V = 715.14 (12) Å3

Z = 2

Mo Kα radiation

μ = 0.24 mm−1

T = 298 K

0.38 × 0.35 × 0.32 mm

Data collection

Stoe IPDS II diffractometer

Absorption correction: numerical (X-RED and X-SHAPE; Stoe & Cie (2005 ▶) T min = 0.910, T max = 0.930

7967 measured reflections

3832 independent reflections

2715 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.128

S = 1.03

3832 reflections

202 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.26 e Å−3

Δρmin = −0.23 e Å−3

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812026803/bt5899sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812026803/bt5899Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812026803/bt5899Isup3.cml

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

C14H12N4O2S	Z = 2
Mr = 300.35	F(000) = 312
Triclinic, P1	Dx = 1.395 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4050 (7) Å	Cell parameters from 7967 reflections
b = 8.4239 (8) Å	θ = 2.6–29.2°
c = 12.2363 (10) Å	µ = 0.24 mm−1
α = 90.382 (7)°	T = 298 K
β = 93.974 (7)°	Prism, yellow
γ = 110.004 (8)°	0.38 × 0.35 × 0.32 mm
V = 715.14 (12) Å3

Stoe IPDS II diffractometer	3832 independent reflections
Radiation source: fine-focus sealed tube	2715 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
Detector resolution: 0.15 mm pixels mm-1	θmax = 29.2°, θmin = 2.6°
rotation method scans	h = −10→10
Absorption correction: numerical (X-RED and X-SHAPE; Stoe & Cie (2005)	k = −11→10
Tmin = 0.910, Tmax = 0.930	l = −15→16
7967 measured reflections

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0528P)2 + 0.223P] where P = (Fo2 + 2Fc2)/3
3832 reflections	(Δ/σ)max = 0.005
202 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

Experimental. shape of crystal determined optically

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
C1	0.2544 (3)	0.5115 (3)	0.51143 (14)	0.0381 (4)
C2	0.2249 (3)	0.5628 (3)	0.40645 (15)	0.0509 (5)
H2	0.2076	0.4892	0.3465	0.061*
C3	0.2213 (4)	0.7226 (3)	0.39147 (18)	0.0609 (6)
H3	0.2007	0.7575	0.3212	0.073*
C4	0.2482 (4)	0.8319 (3)	0.48040 (19)	0.0597 (6)
H4	0.2457	0.9404	0.4700	0.072*
C5	0.2790 (3)	0.7805 (3)	0.58510 (17)	0.0479 (5)
H5	0.2977	0.8559	0.6442	0.057*
C6	0.2826 (3)	0.6186 (2)	0.60429 (14)	0.0366 (4)
C7	0.3227 (3)	0.5732 (3)	0.71685 (14)	0.0406 (4)
H7	0.388 (3)	0.492 (3)	0.7285 (18)	0.052 (6)*
C8	0.2886 (3)	0.6664 (2)	0.99057 (14)	0.0372 (4)
C9	0.1339 (3)	0.8556 (2)	1.06241 (14)	0.0375 (4)
C10	0.2729 (3)	0.9819 (3)	1.12422 (16)	0.0469 (5)
H10	0.4023	1.0094	1.1118	0.056*
C11	0.2178 (4)	1.0678 (3)	1.20523 (17)	0.0530 (5)
H11	0.3108	1.1530	1.2475	0.064*
C12	0.0278 (4)	1.0282 (3)	1.22337 (17)	0.0517 (5)
H12	−0.0080	1.0859	1.2782	0.062*
C13	−0.1108 (3)	0.9032 (3)	1.16084 (18)	0.0514 (5)
H13	−0.2402	0.8768	1.1732	0.062*
C14	−0.0578 (3)	0.8164 (3)	1.07917 (16)	0.0441 (5)
H14	−0.1512	0.7325	1.0362	0.053*
O1	0.2599 (4)	0.2612 (3)	0.43801 (14)	0.0824 (6)
O2	0.2395 (4)	0.2728 (2)	0.60884 (14)	0.0829 (6)
N1	0.2507 (3)	0.3363 (2)	0.52080 (13)	0.0453 (4)
N2	0.2793 (2)	0.6465 (2)	0.79714 (12)	0.0395 (4)
N3	0.3341 (3)	0.6036 (2)	0.89882 (12)	0.0433 (4)
H3B	0.411 (3)	0.546 (3)	0.9056 (18)	0.042 (6)*
N4	0.1877 (3)	0.7690 (2)	0.97626 (13)	0.0469 (4)
H4B	0.150 (3)	0.782 (3)	0.916 (2)	0.053 (7)*
S1	0.35639 (10)	0.60896 (8)	1.11356 (4)	0.05372 (19)

	U11	U22	U33	U12	U13	U23
C1	0.0429 (10)	0.0444 (11)	0.0292 (8)	0.0173 (9)	0.0053 (7)	−0.0006 (7)
C2	0.0620 (14)	0.0657 (15)	0.0267 (8)	0.0237 (12)	0.0059 (8)	0.0002 (9)
C3	0.0796 (17)	0.0730 (17)	0.0355 (10)	0.0323 (14)	0.0075 (10)	0.0168 (10)
C4	0.0784 (17)	0.0517 (13)	0.0568 (13)	0.0310 (13)	0.0111 (12)	0.0180 (11)
C5	0.0622 (14)	0.0456 (12)	0.0411 (10)	0.0246 (11)	0.0072 (9)	0.0003 (9)
C6	0.0413 (10)	0.0440 (10)	0.0278 (8)	0.0185 (9)	0.0049 (7)	−0.0004 (7)
C7	0.0536 (12)	0.0448 (11)	0.0295 (8)	0.0255 (10)	−0.0008 (8)	−0.0045 (7)
C8	0.0494 (11)	0.0370 (10)	0.0281 (8)	0.0190 (9)	0.0010 (7)	−0.0027 (7)
C9	0.0547 (12)	0.0367 (10)	0.0281 (8)	0.0247 (9)	0.0037 (7)	0.0017 (7)
C10	0.0467 (12)	0.0527 (13)	0.0433 (10)	0.0194 (10)	0.0061 (9)	−0.0046 (9)
C11	0.0640 (15)	0.0501 (13)	0.0444 (11)	0.0199 (11)	0.0005 (10)	−0.0139 (9)
C12	0.0698 (15)	0.0571 (13)	0.0395 (10)	0.0352 (12)	0.0114 (10)	−0.0032 (9)
C13	0.0521 (13)	0.0590 (14)	0.0493 (11)	0.0248 (11)	0.0152 (10)	0.0095 (10)
C14	0.0541 (12)	0.0363 (10)	0.0407 (10)	0.0147 (9)	0.0008 (9)	0.0021 (8)
O1	0.1373 (19)	0.0725 (12)	0.0507 (10)	0.0532 (13)	0.0082 (10)	−0.0205 (9)
O2	0.155 (2)	0.0529 (11)	0.0455 (9)	0.0410 (12)	0.0083 (11)	0.0041 (8)
N1	0.0516 (10)	0.0481 (10)	0.0377 (8)	0.0193 (8)	0.0037 (7)	−0.0076 (7)
N2	0.0534 (10)	0.0419 (9)	0.0275 (7)	0.0222 (8)	0.0021 (6)	−0.0007 (6)
N3	0.0664 (12)	0.0493 (10)	0.0259 (7)	0.0359 (10)	−0.0009 (7)	−0.0034 (6)
N4	0.0751 (13)	0.0546 (11)	0.0257 (7)	0.0425 (10)	−0.0017 (7)	−0.0034 (7)
S1	0.0844 (4)	0.0706 (4)	0.0259 (2)	0.0526 (3)	0.0011 (2)	0.0008 (2)

C1—C2	1.385 (3)	C9—C14	1.374 (3)
C1—C6	1.405 (2)	C9—C10	1.377 (3)
C1—N1	1.472 (3)	C9—N4	1.432 (2)
C2—C3	1.369 (3)	C10—C11	1.386 (3)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.379 (3)	C11—C12	1.365 (3)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.384 (3)	C12—C13	1.374 (3)
C4—H4	0.9300	C12—H12	0.9300
C5—C6	1.394 (3)	C13—C14	1.389 (3)
C5—H5	0.9300	C13—H13	0.9300
C6—C7	1.470 (2)	C14—H14	0.9300
C7—N2	1.273 (2)	O1—N1	1.209 (2)
C7—H7	0.97 (2)	O2—N1	1.202 (2)
C8—N4	1.327 (2)	N2—N3	1.371 (2)
C8—N3	1.349 (2)	N3—H3B	0.87 (2)
C8—S1	1.6799 (18)	N4—H4B	0.79 (3)
C2—C1—C6	122.28 (19)	C10—C9—N4	120.05 (19)
C2—C1—N1	116.16 (17)	C9—C10—C11	119.3 (2)
C6—C1—N1	121.55 (16)	C9—C10—H10	120.4
C3—C2—C1	119.5 (2)	C11—C10—H10	120.4
C3—C2—H2	120.2	C12—C11—C10	120.4 (2)
C1—C2—H2	120.2	C12—C11—H11	119.8
C2—C3—C4	120.11 (19)	C10—C11—H11	119.8
C2—C3—H3	119.9	C11—C12—C13	120.19 (19)
C4—C3—H3	119.9	C11—C12—H12	119.9
C3—C4—C5	120.2 (2)	C13—C12—H12	119.9
C3—C4—H4	119.9	C12—C13—C14	120.0 (2)
C5—C4—H4	119.9	C12—C13—H13	120.0
C4—C5—C6	121.7 (2)	C14—C13—H13	120.0
C4—C5—H5	119.1	C9—C14—C13	119.4 (2)
C6—C5—H5	119.1	C9—C14—H14	120.3
C5—C6—C1	116.22 (17)	C13—C14—H14	120.3
C5—C6—C7	119.24 (17)	O2—N1—O1	122.1 (2)
C1—C6—C7	124.48 (17)	O2—N1—C1	119.95 (16)
N2—C7—C6	119.59 (17)	O1—N1—C1	117.90 (18)
N2—C7—H7	121.3 (13)	C7—N2—N3	115.10 (15)
C6—C7—H7	119.1 (13)	C8—N3—N2	120.88 (16)
N4—C8—N3	116.38 (16)	C8—N3—H3B	118.3 (14)
N4—C8—S1	124.22 (13)	N2—N3—H3B	120.3 (14)
N3—C8—S1	119.39 (14)	C8—N4—C9	125.10 (16)
C14—C9—C10	120.63 (17)	C8—N4—H4B	118.8 (17)
C14—C9—N4	119.25 (19)	C9—N4—H4B	116.1 (17)
C6—C1—C2—C3	−0.5 (3)	C11—C12—C13—C14	0.2 (3)
N1—C1—C2—C3	178.3 (2)	C10—C9—C14—C13	−1.3 (3)
C1—C2—C3—C4	0.4 (4)	N4—C9—C14—C13	−178.36 (18)
C2—C3—C4—C5	0.0 (4)	C12—C13—C14—C9	0.6 (3)
C3—C4—C5—C6	−0.4 (4)	C2—C1—N1—O2	−166.3 (2)
C4—C5—C6—C1	0.4 (3)	C6—C1—N1—O2	12.5 (3)
C4—C5—C6—C7	177.9 (2)	C2—C1—N1—O1	14.0 (3)
C2—C1—C6—C5	0.1 (3)	C6—C1—N1—O1	−167.2 (2)
N1—C1—C6—C5	−178.62 (18)	C6—C7—N2—N3	−175.80 (18)
C2—C1—C6—C7	−177.3 (2)	N4—C8—N3—N2	0.6 (3)
N1—C1—C6—C7	4.0 (3)	S1—C8—N3—N2	179.32 (15)
C5—C6—C7—N2	27.7 (3)	C7—N2—N3—C8	−176.8 (2)
C1—C6—C7—N2	−155.0 (2)	N3—C8—N4—C9	−176.5 (2)
C14—C9—C10—C11	1.1 (3)	S1—C8—N4—C9	4.9 (3)
N4—C9—C10—C11	178.15 (19)	C14—C9—N4—C8	−115.2 (2)
C9—C10—C11—C12	−0.2 (3)	C10—C9—N4—C8	67.7 (3)
C10—C11—C12—C13	−0.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···S1i	0.87 (2)	2.51 (2)	3.3664 (18)	168.8 (19)
N4—H4B···N2	0.79 (3)	2.29 (2)	2.642 (2)	108 (2)
C7—H7···O2	0.97 (2)	2.26 (2)	2.703 (3)	106.5 (16)
C11—H11···O1ii	0.93	2.60	3.214 (3)	125

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯S1i	0.87 (2)	2.51 (2)	3.3664 (18)	168.8 (19)
N4—H4B⋯N2	0.79 (3)	2.29 (2)	2.642 (2)	108 (2)
C11—H11⋯O1ii	0.93	2.60	3.214 (3)	125

Symmetry codes: (i) ; (ii) .