organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

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

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[Tarafder, M. T. H., Chew, K.-B., Crouse, K. C., Ali, A. M., Yamin, B. M. & Fun, H.-K. (2002). Polyhedron, 21, 2683-2690.]).

[Scheme 1]

Experimental

Crystal data
  • C15H12ClN3O2S2

  • Mr = 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[North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.]) Tmin = 0.884, Tmax = 0.928

  • 10135 measured reflections

  • 3086 independent reflections

  • 2538 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.49 e Å−3

  • Δρmin = −0.44 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Enraf-Nonius (1989). CAD-4 Software. Enraf-Nonius, Delft, The Netherlands.]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995[Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

The H atoms were positioned geometrically (C—H = 0.93–0.96 Å) and refined as riding, with Uiso(H) = 1.2Ueq(C).

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
[Figure 1] Fig. 1. The structure of (I) showing 50% displacement ellipsoids.
(E)-4-Chlorobenzyl 3-(3-nitrobenzylidene)dithiocarbazate top
Crystal data top
C15H12ClN3O2S2F(000) = 752
Mr = 365.85Dx = 1.507 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 10.175 (2) Åθ = 9–12°
b = 8.4958 (17) ŵ = 0.51 mm1
c = 19.318 (4) ÅT = 293 K
β = 105.01 (3)°Block, yellow
V = 1613.0 (6) Å30.25 × 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 tubeRint = 0.019
Graphite monochromatorθmax = 26.0°, θmin = 2.1°
ω/2θ scansh = 1211
Absorption correction: ψ scan
(North et al., 1968)
k = 1010
Tmin = 0.884, Tmax = 0.928l = 2323
10135 measured reflections200 standard reflections every 3 reflections
3086 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0407P)2 + 0.5179P]
where P = (Fo2 + 2Fc2)/3
3086 reflections(Δ/σ)max = 0.003
212 parametersΔρmax = 0.49 e Å3
0 restraintsΔρmin = 0.44 e Å3
Crystal data top
C15H12ClN3O2S2V = 1613.0 (6) Å3
Mr = 365.85Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.175 (2) ŵ = 0.51 mm1
b = 8.4958 (17) ÅT = 293 K
c = 19.318 (4) Å0.25 × 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)
Rint = 0.019
Tmin = 0.884, Tmax = 0.928200 standard reflections every 3 reflections
10135 measured reflections intensity decay: 1%
3086 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.086H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.49 e Å3
3086 reflectionsΔρmin = 0.44 e Å3
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
xyzUiso*/Ueq
C10.88396 (19)0.8024 (2)0.29108 (9)0.0425 (4)
C20.9588 (2)0.6812 (3)0.33047 (11)0.0549 (5)
H21.03350.64100.31700.066*
C30.9240 (2)0.6188 (3)0.38966 (11)0.0590 (5)
H30.97490.53750.41580.071*
C40.8134 (2)0.6784 (3)0.40920 (10)0.0508 (5)
C50.7369 (2)0.7970 (3)0.37079 (11)0.0565 (5)
H50.66190.83640.38430.068*
C60.7724 (2)0.8578 (3)0.31159 (10)0.0509 (5)
H60.71980.93760.28510.061*
C70.9279 (2)0.8774 (2)0.23026 (9)0.0481 (5)
H7A1.02610.88960.24330.058*
H7B0.88730.98100.22060.058*
C80.96762 (18)0.8426 (2)0.09548 (9)0.0379 (4)
C90.8344 (2)0.6100 (2)0.05521 (9)0.0435 (4)
H90.89600.64240.08040.052*
C100.72835 (18)0.49645 (19)0.08815 (9)0.0377 (4)
C110.74117 (18)0.41334 (19)0.14820 (8)0.0364 (4)
H110.81640.42810.16640.044*
C120.63997 (18)0.30863 (19)0.18004 (8)0.0363 (4)
C130.52623 (19)0.2843 (2)0.15556 (10)0.0442 (4)
H130.45910.21380.17840.053*
C140.5144 (2)0.3672 (3)0.09628 (10)0.0515 (5)
H140.43850.35240.07860.062*
C150.6144 (2)0.4724 (2)0.06269 (10)0.0480 (5)
H150.60510.52750.02260.058*
Cl10.77017 (6)0.60320 (8)0.48441 (3)0.0716 (2)
H10.974 (2)0.822 (3)0.0005 (11)0.050 (6)*
N10.94398 (17)0.77726 (19)0.03009 (8)0.0448 (4)
N20.84407 (16)0.66553 (17)0.00735 (8)0.0423 (4)
N30.65325 (16)0.22357 (18)0.24405 (8)0.0425 (4)
O10.74879 (15)0.25400 (16)0.26884 (7)0.0530 (4)
O20.56589 (15)0.12601 (19)0.27048 (8)0.0667 (4)
S10.87573 (5)0.75559 (6)0.15042 (2)0.04588 (15)
S21.07801 (5)0.98879 (6)0.11887 (2)0.04813 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0481 (11)0.0450 (10)0.0339 (8)0.0057 (8)0.0095 (8)0.0079 (8)
C20.0586 (13)0.0574 (12)0.0536 (11)0.0094 (10)0.0232 (10)0.0032 (10)
C30.0710 (15)0.0550 (12)0.0506 (12)0.0065 (11)0.0152 (10)0.0067 (9)
C40.0549 (12)0.0612 (12)0.0362 (9)0.0174 (10)0.0114 (8)0.0053 (9)
C50.0443 (11)0.0792 (15)0.0484 (11)0.0008 (11)0.0166 (9)0.0039 (11)
C60.0464 (11)0.0605 (12)0.0442 (10)0.0040 (9)0.0091 (8)0.0001 (9)
C70.0577 (12)0.0491 (11)0.0389 (9)0.0120 (9)0.0149 (8)0.0094 (8)
C80.0423 (10)0.0372 (9)0.0337 (8)0.0012 (7)0.0089 (7)0.0011 (7)
C90.0534 (11)0.0424 (10)0.0369 (9)0.0059 (8)0.0156 (8)0.0009 (8)
C100.0447 (10)0.0361 (9)0.0327 (8)0.0001 (7)0.0105 (7)0.0009 (7)
C110.0401 (10)0.0376 (9)0.0330 (8)0.0016 (7)0.0119 (7)0.0030 (7)
C120.0417 (10)0.0353 (9)0.0312 (8)0.0050 (7)0.0082 (7)0.0000 (7)
C130.0412 (10)0.0468 (10)0.0437 (10)0.0042 (8)0.0094 (8)0.0050 (8)
C140.0455 (11)0.0659 (13)0.0485 (11)0.0049 (10)0.0218 (9)0.0070 (9)
C150.0534 (12)0.0546 (11)0.0402 (10)0.0017 (9)0.0197 (8)0.0091 (9)
Cl10.0795 (4)0.0922 (5)0.0438 (3)0.0314 (3)0.0171 (3)0.0014 (3)
N10.0569 (10)0.0442 (9)0.0360 (8)0.0148 (7)0.0169 (7)0.0038 (7)
N20.0525 (9)0.0395 (8)0.0354 (7)0.0078 (7)0.0124 (7)0.0027 (6)
N30.0437 (9)0.0431 (8)0.0388 (8)0.0061 (7)0.0073 (7)0.0050 (7)
O10.0554 (9)0.0634 (9)0.0457 (7)0.0008 (7)0.0231 (7)0.0067 (6)
O20.0573 (9)0.0734 (10)0.0703 (10)0.0139 (8)0.0183 (7)0.0364 (8)
S10.0549 (3)0.0488 (3)0.0358 (2)0.0159 (2)0.0151 (2)0.00558 (19)
S20.0555 (3)0.0466 (3)0.0414 (3)0.0161 (2)0.0111 (2)0.0018 (2)
Geometric parameters (Å, º) top
C1—C61.379 (3)C9—N21.277 (2)
C1—C21.385 (3)C9—C101.464 (2)
C1—C71.503 (3)C9—H90.9300
C2—C31.387 (3)C10—C151.387 (3)
C2—H20.9300C10—C111.393 (2)
C3—C41.373 (3)C11—C121.379 (2)
C3—H30.9300C11—H110.9300
C4—C51.369 (3)C12—C131.375 (3)
C4—Cl11.745 (2)C12—N31.468 (2)
C5—C61.385 (3)C13—C141.376 (3)
C5—H50.9300C13—H130.9300
C6—H60.9300C14—C151.383 (3)
C7—S11.8186 (18)C14—H140.9300
C7—H7A0.9700C15—H150.9300
C7—H7B0.9700N1—N21.377 (2)
C8—N11.343 (2)N1—H10.83 (2)
C8—S21.6571 (18)N3—O11.218 (2)
C8—S11.7495 (18)N3—O21.226 (2)
C6—C1—C2118.19 (18)N2—C9—H9119.3
C6—C1—C7120.93 (18)C10—C9—H9119.3
C2—C1—C7120.79 (18)C15—C10—C11119.20 (16)
C1—C2—C3121.03 (19)C15—C10—C9122.19 (16)
C1—C2—H2119.5C11—C10—C9118.59 (16)
C3—C2—H2119.5C12—C11—C10118.58 (16)
C4—C3—C2119.2 (2)C12—C11—H11120.7
C4—C3—H3120.4C10—C11—H11120.7
C2—C3—H3120.4C13—C12—C11122.78 (16)
C5—C4—C3120.97 (19)C13—C12—N3119.02 (16)
C5—C4—Cl1119.35 (17)C11—C12—N3118.17 (15)
C3—C4—Cl1119.68 (17)C12—C13—C14118.20 (17)
C4—C5—C6119.2 (2)C12—C13—H13120.9
C4—C5—H5120.4C14—C13—H13120.9
C6—C5—H5120.4C13—C14—C15120.57 (18)
C1—C6—C5121.4 (2)C13—C14—H14119.7
C1—C6—H6119.3C15—C14—H14119.7
C5—C6—H6119.3C14—C15—C10120.67 (17)
C1—C7—S1109.93 (13)C14—C15—H15119.7
C1—C7—H7A109.7C10—C15—H15119.7
S1—C7—H7A109.7C8—N1—N2121.50 (16)
C1—C7—H7B109.7C8—N1—H1118.1 (15)
S1—C7—H7B109.7N2—N1—H1118.0 (15)
H7A—C7—H7B108.2C9—N2—N1115.23 (15)
N1—C8—S2120.64 (14)O1—N3—O2123.12 (15)
N1—C8—S1113.72 (13)O1—N3—C12118.93 (15)
S2—C8—S1125.62 (10)O2—N3—C12117.94 (16)
N2—C9—C10121.48 (17)C8—S1—C7100.92 (8)
C6—C1—C2—C31.0 (3)C11—C12—C13—C140.7 (3)
C7—C1—C2—C3175.56 (18)N3—C12—C13—C14178.84 (17)
C1—C2—C3—C40.1 (3)C12—C13—C14—C150.2 (3)
C2—C3—C4—C50.6 (3)C13—C14—C15—C100.1 (3)
C2—C3—C4—Cl1178.96 (16)C11—C10—C15—C140.0 (3)
C3—C4—C5—C60.3 (3)C9—C10—C15—C14178.26 (18)
Cl1—C4—C5—C6179.27 (16)S2—C8—N1—N2174.10 (14)
C2—C1—C6—C51.4 (3)S1—C8—N1—N27.3 (2)
C7—C1—C6—C5175.24 (18)C10—C9—N2—N1176.76 (16)
C4—C5—C6—C10.7 (3)C8—N1—N2—C9178.30 (17)
C6—C1—C7—S1102.99 (19)C13—C12—N3—O1174.50 (16)
C2—C1—C7—S180.5 (2)C11—C12—N3—O13.7 (2)
N2—C9—C10—C1516.4 (3)C13—C12—N3—O24.7 (2)
N2—C9—C10—C11165.39 (17)C11—C12—N3—O2177.13 (16)
C15—C10—C11—C120.5 (2)N1—C8—S1—C7177.81 (14)
C9—C10—C11—C12178.76 (15)S2—C8—S1—C73.71 (15)
C10—C11—C12—C130.8 (3)C1—C7—S1—C8167.97 (14)
C10—C11—C12—N3178.97 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S2i0.83 (2)2.73 (2)3.4565 (18)147.7 (18)
Symmetry code: (i) x+2, y+2, z.

Experimental details

Crystal data
Chemical formulaC15H12ClN3O2S2
Mr365.85
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)10.175 (2), 8.4958 (17), 19.318 (4)
β (°) 105.01 (3)
V3)1613.0 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.51
Crystal size (mm)0.25 × 0.15 × 0.15
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.884, 0.928
No. of measured, independent and
observed [I > 2σ(I)] reflections
10135, 3086, 2538
Rint0.019
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.086, 1.08
No. of reflections3086
No. of parameters212
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H1···S2i0.83 (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

First citationEnraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.  Google Scholar
First citationHarms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.  Google Scholar
First citationNorth, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.  CrossRef IUCr Journals Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationTarafder, 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

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds