(E)-4-Chloro­benzyl 3-(3-nitro­benzyl­idene)dithio­carbazate

Li, H.-Q.; Luo, Y.; Li, D.-D.; Zhu, H.-L.

doi:10.1107/S1600536809047953

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3101

doi:10.1107/S1600536809047953

Open

access

(E)-4-Chlorobenzyl 3-(3-nitrobenzylidene)dithiocarbazate

Huan-Qiu Li,^a Yin Luo,^a Dong-Dong Li ^a and Hai-Liang Zhu ^a ^*

^aState Key Laboratory of Pharmaceutical Biotechnology, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: owengoal13@163.com

(Received 9 November 2009; accepted 12 November 2009; online 14 November 2009)

In the title compound, C₁₅H₁₂ClN₃O₂S₂, the dihedral angle between the aromatic rings is 89.71 (10)°. In the crystal, inversion dimers linked by pairs of N—H⋯S hydrogen bonds occur.

Related literature

For background to the chemistry of carbodithioates, see: Tarafder et al. (2002 ).

Experimental

Crystal data

C₁₅H₁₂ClN₃O₂S₂
M_r = 365.85
Monoclinic, P 2₁ /n
a = 10.175 (2) Å
b = 8.4958 (17) Å
c = 19.318 (4) Å
β = 105.01 (3)°
V = 1613.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 293 K
0.25 × 0.15 × 0.15 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.884, T_max = 0.928
10135 measured reflections
3086 independent reflections
2538 reflections with I > 2σ(I)
R_int = 0.019
200 standard reflections every 3 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.086
S = 1.08
3086 reflections
212 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S2ⁱ	0.83 (2)	2.73 (2)	3.4565 (18)	147.7 (18)
Symmetry code: (i) -x+2, -y+2, -z.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809047953/hb5222sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809047953/hb5222Isup2.hkl

checkCIF report

Related literature top

For background to the chemistry of carbodithioates, see: Tarafder et al. (2002).

Experimental top

A mixture of benzyl hydrazinecarbodithioate (396 mg, 2 mmol), 3-nitrobenzaldehyde (302 mg, 2 mmol) was stirred in methanol (10 ml) for 1 h. After keeping the filtrate in air for 7 d, yellow blocks of (I) were formed.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The structure of (I) showing 50% displacement ellipsoids.

(E)-4-Chlorobenzyl 3-(3-nitrobenzylidene)dithiocarbazate top

Crystal data top

C₁₅H₁₂ClN₃O₂S₂	F(000) = 752
M_r = 365.85	D_x = 1.507 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 10.175 (2) Å	θ = 9–12°
b = 8.4958 (17) Å	µ = 0.51 mm⁻¹
c = 19.318 (4) Å	T = 293 K
β = 105.01 (3)°	Block, yellow
V = 1613.0 (6) Å³	0.25 × 0.15 × 0.15 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	2538 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
Graphite monochromator	θ_max = 26.0°, θ_min = 2.1°
ω/2θ scans	h = −12→11
Absorption correction: ψ scan (North et al., 1968)	k = −10→10
T_min = 0.884, T_max = 0.928	l = −23→23
10135 measured reflections	200 standard reflections every 3 reflections
3086 independent reflections	intensity decay: 1%

Refinement top

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0407P)² + 0.5179P] where P = (F_o² + 2F_c²)/3
3086 reflections	(Δ/σ)_max = 0.003
212 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

C₁₅H₁₂ClN₃O₂S₂	V = 1613.0 (6) Å³
M_r = 365.85	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.175 (2) Å	µ = 0.51 mm⁻¹
b = 8.4958 (17) Å	T = 293 K
c = 19.318 (4) Å	0.25 × 0.15 × 0.15 mm
β = 105.01 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	2538 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.019
T_min = 0.884, T_max = 0.928	200 standard reflections every 3 reflections
10135 measured reflections	intensity decay: 1%
3086 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.49 e Å⁻³
3086 reflections	Δρ_min = −0.44 e Å⁻³
212 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.88396 (19)	0.8024 (2)	0.29108 (9)	0.0425 (4)
C2	0.9588 (2)	0.6812 (3)	0.33047 (11)	0.0549 (5)
H2	1.0335	0.6410	0.3170	0.066*
C3	0.9240 (2)	0.6188 (3)	0.38966 (11)	0.0590 (5)
H3	0.9749	0.5375	0.4158	0.071*
C4	0.8134 (2)	0.6784 (3)	0.40920 (10)	0.0508 (5)
C5	0.7369 (2)	0.7970 (3)	0.37079 (11)	0.0565 (5)
H5	0.6619	0.8364	0.3843	0.068*
C6	0.7724 (2)	0.8578 (3)	0.31159 (10)	0.0509 (5)
H6	0.7198	0.9376	0.2851	0.061*
C7	0.9279 (2)	0.8774 (2)	0.23026 (9)	0.0481 (5)
H7A	1.0261	0.8896	0.2433	0.058*
H7B	0.8873	0.9810	0.2206	0.058*
C8	0.96762 (18)	0.8426 (2)	0.09548 (9)	0.0379 (4)
C9	0.8344 (2)	0.6100 (2)	−0.05521 (9)	0.0435 (4)
H9	0.8960	0.6424	−0.0804	0.052*
C10	0.72835 (18)	0.49645 (19)	−0.08815 (9)	0.0377 (4)
C11	0.74117 (18)	0.41334 (19)	−0.14820 (8)	0.0364 (4)
H11	0.8164	0.4281	−0.1664	0.044*
C12	0.63997 (18)	0.30863 (19)	−0.18004 (8)	0.0363 (4)
C13	0.52623 (19)	0.2843 (2)	−0.15556 (10)	0.0442 (4)
H13	0.4591	0.2138	−0.1784	0.053*
C14	0.5144 (2)	0.3672 (3)	−0.09628 (10)	0.0515 (5)
H14	0.4385	0.3524	−0.0786	0.062*
C15	0.6144 (2)	0.4724 (2)	−0.06269 (10)	0.0480 (5)
H15	0.6051	0.5275	−0.0226	0.058*
Cl1	0.77017 (6)	0.60320 (8)	0.48441 (3)	0.0716 (2)
H1	0.974 (2)	0.822 (3)	−0.0005 (11)	0.050 (6)*
N1	0.94398 (17)	0.77726 (19)	0.03009 (8)	0.0448 (4)
N2	0.84407 (16)	0.66553 (17)	0.00735 (8)	0.0423 (4)
N3	0.65325 (16)	0.22357 (18)	−0.24405 (8)	0.0425 (4)
O1	0.74879 (15)	0.25400 (16)	−0.26884 (7)	0.0530 (4)
O2	0.56589 (15)	0.12601 (19)	−0.27048 (8)	0.0667 (4)
S1	0.87573 (5)	0.75559 (6)	0.15042 (2)	0.04588 (15)
S2	1.07801 (5)	0.98879 (6)	0.11887 (2)	0.04813 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0481 (11)	0.0450 (10)	0.0339 (8)	−0.0057 (8)	0.0095 (8)	−0.0079 (8)
C2	0.0586 (13)	0.0574 (12)	0.0536 (11)	0.0094 (10)	0.0232 (10)	−0.0032 (10)
C3	0.0710 (15)	0.0550 (12)	0.0506 (12)	0.0065 (11)	0.0152 (10)	0.0067 (9)
C4	0.0549 (12)	0.0612 (12)	0.0362 (9)	−0.0174 (10)	0.0114 (8)	−0.0053 (9)
C5	0.0443 (11)	0.0792 (15)	0.0484 (11)	−0.0008 (11)	0.0166 (9)	−0.0039 (11)
C6	0.0464 (11)	0.0605 (12)	0.0442 (10)	0.0040 (9)	0.0091 (8)	0.0001 (9)
C7	0.0577 (12)	0.0491 (11)	0.0389 (9)	−0.0120 (9)	0.0149 (8)	−0.0094 (8)
C8	0.0423 (10)	0.0372 (9)	0.0337 (8)	−0.0012 (7)	0.0089 (7)	0.0011 (7)
C9	0.0534 (11)	0.0424 (10)	0.0369 (9)	−0.0059 (8)	0.0156 (8)	−0.0009 (8)
C10	0.0447 (10)	0.0361 (9)	0.0327 (8)	0.0001 (7)	0.0105 (7)	0.0009 (7)
C11	0.0401 (10)	0.0376 (9)	0.0330 (8)	0.0016 (7)	0.0119 (7)	0.0030 (7)
C12	0.0417 (10)	0.0353 (9)	0.0312 (8)	0.0050 (7)	0.0082 (7)	0.0000 (7)
C13	0.0412 (10)	0.0468 (10)	0.0437 (10)	−0.0042 (8)	0.0094 (8)	−0.0050 (8)
C14	0.0455 (11)	0.0659 (13)	0.0485 (11)	−0.0049 (10)	0.0218 (9)	−0.0070 (9)
C15	0.0534 (12)	0.0546 (11)	0.0402 (10)	−0.0017 (9)	0.0197 (8)	−0.0091 (9)
Cl1	0.0795 (4)	0.0922 (5)	0.0438 (3)	−0.0314 (3)	0.0171 (3)	0.0014 (3)
N1	0.0569 (10)	0.0442 (9)	0.0360 (8)	−0.0148 (7)	0.0169 (7)	−0.0038 (7)
N2	0.0525 (9)	0.0395 (8)	0.0354 (7)	−0.0078 (7)	0.0124 (7)	−0.0027 (6)
N3	0.0437 (9)	0.0431 (8)	0.0388 (8)	0.0061 (7)	0.0073 (7)	−0.0050 (7)
O1	0.0554 (9)	0.0634 (9)	0.0457 (7)	0.0008 (7)	0.0231 (7)	−0.0067 (6)
O2	0.0573 (9)	0.0734 (10)	0.0703 (10)	−0.0139 (8)	0.0183 (7)	−0.0364 (8)
S1	0.0549 (3)	0.0488 (3)	0.0358 (2)	−0.0159 (2)	0.0151 (2)	−0.00558 (19)
S2	0.0555 (3)	0.0466 (3)	0.0414 (3)	−0.0161 (2)	0.0111 (2)	−0.0018 (2)

Geometric parameters (Å, º) top

C1—C6	1.379 (3)	C9—N2	1.277 (2)
C1—C2	1.385 (3)	C9—C10	1.464 (2)
C1—C7	1.503 (3)	C9—H9	0.9300
C2—C3	1.387 (3)	C10—C15	1.387 (3)
C2—H2	0.9300	C10—C11	1.393 (2)
C3—C4	1.373 (3)	C11—C12	1.379 (2)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.369 (3)	C12—C13	1.375 (3)
C4—Cl1	1.745 (2)	C12—N3	1.468 (2)
C5—C6	1.385 (3)	C13—C14	1.376 (3)
C5—H5	0.9300	C13—H13	0.9300
C6—H6	0.9300	C14—C15	1.383 (3)
C7—S1	1.8186 (18)	C14—H14	0.9300
C7—H7A	0.9700	C15—H15	0.9300
C7—H7B	0.9700	N1—N2	1.377 (2)
C8—N1	1.343 (2)	N1—H1	0.83 (2)
C8—S2	1.6571 (18)	N3—O1	1.218 (2)
C8—S1	1.7495 (18)	N3—O2	1.226 (2)

C6—C1—C2	118.19 (18)	N2—C9—H9	119.3
C6—C1—C7	120.93 (18)	C10—C9—H9	119.3
C2—C1—C7	120.79 (18)	C15—C10—C11	119.20 (16)
C1—C2—C3	121.03 (19)	C15—C10—C9	122.19 (16)
C1—C2—H2	119.5	C11—C10—C9	118.59 (16)
C3—C2—H2	119.5	C12—C11—C10	118.58 (16)
C4—C3—C2	119.2 (2)	C12—C11—H11	120.7
C4—C3—H3	120.4	C10—C11—H11	120.7
C2—C3—H3	120.4	C13—C12—C11	122.78 (16)
C5—C4—C3	120.97 (19)	C13—C12—N3	119.02 (16)
C5—C4—Cl1	119.35 (17)	C11—C12—N3	118.17 (15)
C3—C4—Cl1	119.68 (17)	C12—C13—C14	118.20 (17)
C4—C5—C6	119.2 (2)	C12—C13—H13	120.9
C4—C5—H5	120.4	C14—C13—H13	120.9
C6—C5—H5	120.4	C13—C14—C15	120.57 (18)
C1—C6—C5	121.4 (2)	C13—C14—H14	119.7
C1—C6—H6	119.3	C15—C14—H14	119.7
C5—C6—H6	119.3	C14—C15—C10	120.67 (17)
C1—C7—S1	109.93 (13)	C14—C15—H15	119.7
C1—C7—H7A	109.7	C10—C15—H15	119.7
S1—C7—H7A	109.7	C8—N1—N2	121.50 (16)
C1—C7—H7B	109.7	C8—N1—H1	118.1 (15)
S1—C7—H7B	109.7	N2—N1—H1	118.0 (15)
H7A—C7—H7B	108.2	C9—N2—N1	115.23 (15)
N1—C8—S2	120.64 (14)	O1—N3—O2	123.12 (15)
N1—C8—S1	113.72 (13)	O1—N3—C12	118.93 (15)
S2—C8—S1	125.62 (10)	O2—N3—C12	117.94 (16)
N2—C9—C10	121.48 (17)	C8—S1—C7	100.92 (8)

C6—C1—C2—C3	−1.0 (3)	C11—C12—C13—C14	−0.7 (3)
C7—C1—C2—C3	175.56 (18)	N3—C12—C13—C14	−178.84 (17)
C1—C2—C3—C4	0.1 (3)	C12—C13—C14—C15	0.2 (3)
C2—C3—C4—C5	0.6 (3)	C13—C14—C15—C10	0.1 (3)
C2—C3—C4—Cl1	−178.96 (16)	C11—C10—C15—C14	0.0 (3)
C3—C4—C5—C6	−0.3 (3)	C9—C10—C15—C14	178.26 (18)
Cl1—C4—C5—C6	179.27 (16)	S2—C8—N1—N2	−174.10 (14)
C2—C1—C6—C5	1.4 (3)	S1—C8—N1—N2	7.3 (2)
C7—C1—C6—C5	−175.24 (18)	C10—C9—N2—N1	−176.76 (16)
C4—C5—C6—C1	−0.7 (3)	C8—N1—N2—C9	−178.30 (17)
C6—C1—C7—S1	−102.99 (19)	C13—C12—N3—O1	174.50 (16)
C2—C1—C7—S1	80.5 (2)	C11—C12—N3—O1	−3.7 (2)
N2—C9—C10—C15	16.4 (3)	C13—C12—N3—O2	−4.7 (2)
N2—C9—C10—C11	−165.39 (17)	C11—C12—N3—O2	177.13 (16)
C15—C10—C11—C12	−0.5 (2)	N1—C8—S1—C7	−177.81 (14)
C9—C10—C11—C12	−178.76 (15)	S2—C8—S1—C7	3.71 (15)
C10—C11—C12—C13	0.8 (3)	C1—C7—S1—C8	−167.97 (14)
C10—C11—C12—N3	178.97 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S2ⁱ	0.83 (2)	2.73 (2)	3.4565 (18)	147.7 (18)

Symmetry code: (i) −x+2, −y+2, −z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂ClN₃O₂S₂
M_r	365.85
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	10.175 (2), 8.4958 (17), 19.318 (4)
β (°)	105.01 (3)
V (Å³)	1613.0 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.51
Crystal size (mm)	0.25 × 0.15 × 0.15

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.884, 0.928
No. of measured, independent and observed [I > 2σ(I)] reflections	10135, 3086, 2538
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.086, 1.08
No. of reflections	3086
No. of parameters	212
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.44

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S2ⁱ	0.83 (2)	2.73 (2)	3.4565 (18)	147.7 (18)

Symmetry code: (i) −x+2, −y+2, −z.

Acknowledgements

This work was financed by a grant from the National Natural Science Foundation of China (project 30772627) and the China Postdoctoral Science Foundation (project 20080441043).

References

Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tarafder, M. T. H., Chew, K.-B., Crouse, K. C., Ali, A. M., Yamin, B. M. & Fun, H.-K. (2002). Polyhedron, 21, 2683–2690. Web of Science CSD CrossRef CAS Google Scholar