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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3080.
Published online 2009 November 14. doi:  10.1107/S1600536809045723
PMCID: PMC2971807

(E)-Benzyl 3-(3-nitro­benzyl­idene)dithio­carbazate

Abstract

In the title compound, C15H13N3O2S2, the dihedral angle between the aromatic rings is 87.8 (2)°. In the crystal, inversion dimers occur linked by pairs of N—H(...)S hydrogen bonds.

Related literature

For background to carbodithio­ates, see: Tarafder et al. (2002 [triangle]).

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Object name is e-65-o3080-scheme1.jpg

Experimental

Crystal data

  • C15H13N3O2S2
  • M r = 331.40
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3080-efi1.jpg
  • a = 5.2175 (10) Å
  • b = 26.213 (5) Å
  • c = 11.887 (2) Å
  • β = 90.67 (3)°
  • V = 1625.6 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.34 mm−1
  • T = 293 K
  • 0.30 × 0.30 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.906, T max = 0.967
  • 9486 measured reflections
  • 2788 independent reflections
  • 951 reflections with I > 2σ(I)
  • R int = 0.097
  • 200 standard reflections every 3 reflections intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.106
  • S = 0.73
  • 2788 reflections
  • 211 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.15 e Å−3
  • Δρmin = −0.16 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809045723/hb5203sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809045723/hb5203Isup2.hkl

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

Acknowledgments

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).

supplementary crystallographic information

Experimental

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

Refinement

The N-bound N atom was located in a difference map and freely refined. The other H atoms were positioned geometrically (C—H = 0.93 Å for the aromatic H atoms and C—H = 0.96 Å for the aliphatic H atoms) and were refined as riding, with Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.2Ueq(N).

Figures

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

Crystal data

C15H13N3O2S2F(000) = 688
Mr = 331.40Dx = 1.354 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 5.2175 (10) Åθ = 9–12°
b = 26.213 (5) ŵ = 0.34 mm1
c = 11.887 (2) ÅT = 293 K
β = 90.67 (3)°Block, yellow
V = 1625.6 (6) Å30.30 × 0.30 × 0.10 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer951 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.097
graphiteθmax = 25.0°, θmin = 1.9°
ω/2θ scansh = −6→5
Absorption correction: ψ scan (North et al., 1968)k = −31→29
Tmin = 0.906, Tmax = 0.967l = −14→14
9486 measured reflections200 standard reflections every 3 reflections
2788 independent reflections intensity decay: 1%

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 0.73w = 1/[σ2(Fo2) + (0.0448P)2] where P = (Fo2 + 2Fc2)/3
2788 reflections(Δ/σ)max < 0.001
211 parametersΔρmax = 0.15 e Å3
0 restraintsΔρmin = −0.16 e Å3

Special details

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)

xyzUiso*/Ueq
C11.5564 (10)0.38939 (18)1.0058 (4)0.1065 (16)
H11.66130.37870.94770.128*
C21.5833 (10)0.36729 (18)1.1102 (5)0.1215 (18)
H21.70700.34231.12220.146*
C31.4312 (11)0.38176 (19)1.1951 (4)0.0986 (14)
H31.44910.36681.26580.118*
C41.2549 (11)0.4177 (2)1.1770 (4)0.1203 (18)
H41.14740.42751.23490.144*
C51.2307 (9)0.44050 (17)1.0726 (5)0.1170 (17)
H51.10950.46611.06160.140*
C61.3817 (9)0.42606 (17)0.9862 (4)0.0740 (11)
C71.3604 (11)0.4511 (2)0.8717 (4)0.0893 (15)
C81.0763 (8)0.45488 (13)0.6740 (3)0.0662 (10)
C90.5747 (8)0.38503 (16)0.5578 (3)0.0740 (12)
H90.54120.40630.49670.089*
C100.4214 (8)0.33846 (15)0.5727 (3)0.0648 (10)
C110.2307 (8)0.32751 (16)0.4958 (3)0.0716 (11)
H110.19400.34990.43710.086*
C120.0946 (8)0.28268 (18)0.5071 (4)0.0763 (12)
C130.1352 (9)0.24961 (16)0.5946 (4)0.0997 (15)
H130.03890.21990.60140.120*
C140.3244 (9)0.26178 (18)0.6727 (4)0.1020 (15)
H140.35630.23990.73290.122*
C150.4658 (8)0.30577 (16)0.6623 (3)0.0838 (12)
H150.59170.31360.71560.101*
H1A0.851 (7)0.4589 (13)0.540 (3)0.100 (15)*
N10.8928 (7)0.43995 (14)0.6035 (3)0.0779 (10)
N20.7523 (7)0.39663 (13)0.6274 (3)0.0739 (9)
N3−0.1075 (8)0.27046 (17)0.4218 (4)0.0953 (12)
O1−0.1536 (6)0.30218 (13)0.3506 (3)0.1166 (11)
O2−0.2120 (8)0.22932 (15)0.4285 (3)0.1572 (16)
S11.1060 (2)0.41799 (4)0.79464 (9)0.0806 (4)
S21.2592 (2)0.50568 (4)0.64490 (9)0.0898 (4)
H7A1.508 (7)0.4456 (14)0.827 (3)0.109 (17)*
H7B1.308 (8)0.4842 (16)0.871 (3)0.14 (2)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.121 (4)0.107 (4)0.092 (4)0.028 (3)0.039 (3)0.019 (3)
C20.128 (4)0.128 (4)0.109 (4)0.051 (3)0.027 (4)0.034 (4)
C30.108 (4)0.102 (4)0.085 (4)0.000 (3)−0.004 (3)0.005 (3)
C40.135 (5)0.142 (5)0.084 (4)0.029 (4)0.022 (3)−0.002 (3)
C50.123 (4)0.132 (4)0.097 (4)0.060 (3)0.015 (3)0.008 (3)
C60.070 (3)0.076 (3)0.076 (3)−0.005 (2)−0.005 (3)−0.001 (3)
C70.077 (4)0.109 (5)0.082 (4)−0.009 (3)−0.010 (3)0.016 (3)
C80.063 (3)0.068 (3)0.068 (3)−0.002 (2)0.001 (2)0.007 (2)
C90.080 (3)0.078 (3)0.064 (3)−0.005 (3)0.002 (3)0.005 (2)
C100.063 (3)0.063 (3)0.068 (3)−0.006 (2)0.006 (2)0.000 (2)
C110.068 (3)0.079 (3)0.067 (3)−0.007 (3)0.003 (3)0.005 (2)
C120.070 (3)0.089 (4)0.069 (3)−0.012 (3)−0.002 (3)0.000 (3)
C130.103 (4)0.089 (3)0.107 (4)−0.033 (3)−0.017 (3)0.027 (3)
C140.111 (4)0.087 (4)0.108 (4)−0.020 (3)−0.015 (3)0.035 (3)
C150.094 (3)0.078 (3)0.079 (3)−0.006 (3)−0.013 (2)0.012 (3)
N10.080 (3)0.079 (3)0.075 (3)−0.010 (2)−0.008 (2)0.015 (2)
N20.076 (3)0.068 (2)0.077 (2)−0.005 (2)0.002 (2)0.0053 (19)
N30.096 (3)0.097 (4)0.094 (3)−0.010 (3)−0.005 (3)0.000 (3)
O10.114 (3)0.127 (3)0.108 (2)−0.019 (2)−0.031 (2)0.016 (2)
O20.180 (4)0.141 (3)0.150 (3)−0.082 (3)−0.045 (3)0.017 (3)
S10.0798 (8)0.0879 (8)0.0741 (7)−0.0113 (6)0.0010 (6)0.0101 (6)
S20.0950 (9)0.0826 (8)0.0917 (8)−0.0215 (7)−0.0063 (6)0.0142 (6)

Geometric parameters (Å, °)

C1—C61.343 (5)C9—N21.272 (4)
C1—C21.375 (5)C9—C101.471 (5)
C1—H10.9300C9—H90.9300
C2—C31.346 (5)C10—C111.373 (4)
C2—H20.9300C10—C151.384 (5)
C3—C41.332 (5)C11—C121.380 (5)
C3—H30.9300C11—H110.9300
C4—C51.381 (5)C12—C131.368 (5)
C4—H40.9300C12—N31.489 (5)
C5—C61.355 (5)C13—C141.384 (5)
C5—H50.9300C13—H130.9300
C6—C71.514 (5)C14—C151.375 (5)
C7—S11.823 (5)C14—H140.9300
C7—H7A0.95 (4)C15—H150.9300
C7—H7B0.91 (4)N1—N21.383 (4)
C8—N11.324 (4)N1—H1A0.93 (3)
C8—S21.676 (4)N3—O11.208 (4)
C8—S11.735 (4)N3—O21.212 (4)
C6—C1—C2121.3 (4)N2—C9—H9119.6
C6—C1—H1119.3C10—C9—H9119.6
C2—C1—H1119.3C11—C10—C15119.7 (4)
C3—C2—C1120.2 (5)C11—C10—C9118.9 (4)
C3—C2—H2119.9C15—C10—C9121.3 (4)
C1—C2—H2119.9C10—C11—C12118.9 (4)
C4—C3—C2119.3 (5)C10—C11—H11120.6
C4—C3—H3120.3C12—C11—H11120.6
C2—C3—H3120.3C13—C12—C11122.5 (4)
C3—C4—C5120.5 (5)C13—C12—N3118.9 (4)
C3—C4—H4119.8C11—C12—N3118.5 (4)
C5—C4—H4119.8C12—C13—C14117.8 (4)
C6—C5—C4120.8 (4)C12—C13—H13121.1
C6—C5—H5119.6C14—C13—H13121.1
C4—C5—H5119.6C15—C14—C13120.8 (4)
C1—C6—C5117.9 (4)C15—C14—H14119.6
C1—C6—C7120.6 (5)C13—C14—H14119.6
C5—C6—C7121.6 (5)C14—C15—C10120.2 (4)
C6—C7—S1106.9 (3)C14—C15—H15119.9
C6—C7—H7A113 (2)C10—C15—H15119.9
S1—C7—H7A104 (2)C8—N1—N2119.6 (4)
C6—C7—H7B116 (3)C8—N1—H1A121 (2)
S1—C7—H7B104 (3)N2—N1—H1A119 (2)
H7A—C7—H7B113 (4)C9—N2—N1116.5 (4)
N1—C8—S2120.9 (3)O1—N3—O2124.9 (5)
N1—C8—S1114.5 (3)O1—N3—C12117.6 (4)
S2—C8—S1124.6 (3)O2—N3—C12117.5 (5)
N2—C9—C10120.9 (4)C8—S1—C7102.0 (2)
C6—C1—C2—C30.8 (8)N3—C12—C13—C14179.9 (4)
C1—C2—C3—C4−0.1 (8)C12—C13—C14—C150.1 (7)
C2—C3—C4—C5−1.0 (8)C13—C14—C15—C10−0.4 (6)
C3—C4—C5—C61.4 (8)C11—C10—C15—C141.7 (6)
C2—C1—C6—C5−0.4 (7)C9—C10—C15—C14−178.3 (3)
C2—C1—C6—C7178.1 (4)S2—C8—N1—N2177.2 (2)
C4—C5—C6—C1−0.7 (7)S1—C8—N1—N2−2.9 (4)
C4—C5—C6—C7−179.2 (4)C10—C9—N2—N1177.3 (3)
C1—C6—C7—S196.1 (5)C8—N1—N2—C9178.3 (3)
C5—C6—C7—S1−85.4 (5)C13—C12—N3—O1174.2 (4)
N2—C9—C10—C11179.7 (3)C11—C12—N3—O1−4.7 (6)
N2—C9—C10—C15−0.3 (5)C13—C12—N3—O2−6.3 (6)
C15—C10—C11—C12−2.8 (5)C11—C12—N3—O2174.8 (4)
C9—C10—C11—C12177.2 (3)N1—C8—S1—C7−177.5 (3)
C10—C11—C12—C132.6 (6)S2—C8—S1—C72.4 (3)
C10—C11—C12—N3−178.5 (3)C6—C7—S1—C8173.1 (4)
C11—C12—C13—C14−1.3 (6)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···S2i0.93 (3)2.45 (4)3.365 (4)170 (3)

Symmetry codes: (i) −x+2, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5203).

References

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

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography