organic compounds
(E)-Benzyl 3-(3-nitrobenzylidene)dithiocarbazate
aState Key Laboratory of Pharmaceutical Biotechnology, Nanjing University, Nanjing 210093, People's Republic of China
*Correspondence e-mail: hailiang_zhu@163.com
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.
Experimental
Crystal data
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Refinement
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Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell 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
10.1107/S1600536809045723/hb5203sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809045723/hb5203Isup2.hkl
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.
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).
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell
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).C15H13N3O2S2 | F(000) = 688 |
Mr = 331.40 | Dx = 1.354 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 5.2175 (10) Å | θ = 9–12° |
b = 26.213 (5) Å | µ = 0.34 mm−1 |
c = 11.887 (2) Å | T = 293 K |
β = 90.67 (3)° | Block, yellow |
V = 1625.6 (6) Å3 | 0.30 × 0.30 × 0.10 mm |
Z = 4 |
Enraf–Nonius CAD-4 diffractometer | 951 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.097 |
Graphite monochromator | θmax = 25.0°, θmin = 1.9° |
ω/2θ scans | h = −6→5 |
Absorption correction: ψ scan (North et al., 1968) | k = −31→29 |
Tmin = 0.906, Tmax = 0.967 | l = −14→14 |
9486 measured reflections | 200 standard reflections every 3 reflections |
2788 independent reflections | intensity decay: 1% |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.73 | w = 1/[σ2(Fo2) + (0.0448P)2] where P = (Fo2 + 2Fc2)/3 |
2788 reflections | (Δ/σ)max < 0.001 |
211 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C15H13N3O2S2 | V = 1625.6 (6) Å3 |
Mr = 331.40 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.2175 (10) Å | µ = 0.34 mm−1 |
b = 26.213 (5) Å | T = 293 K |
c = 11.887 (2) Å | 0.30 × 0.30 × 0.10 mm |
β = 90.67 (3)° |
Enraf–Nonius CAD-4 diffractometer | 951 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.097 |
Tmin = 0.906, Tmax = 0.967 | 200 standard reflections every 3 reflections |
9486 measured reflections | intensity decay: 1% |
2788 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.73 | Δρmax = 0.15 e Å−3 |
2788 reflections | Δρmin = −0.16 e Å−3 |
211 parameters |
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 | 1.5564 (10) | 0.38939 (18) | 1.0058 (4) | 0.1065 (16) | |
H1 | 1.6613 | 0.3787 | 0.9477 | 0.128* | |
C2 | 1.5833 (10) | 0.36729 (18) | 1.1102 (5) | 0.1215 (18) | |
H2 | 1.7070 | 0.3423 | 1.1222 | 0.146* | |
C3 | 1.4312 (11) | 0.38176 (19) | 1.1951 (4) | 0.0986 (14) | |
H3 | 1.4491 | 0.3668 | 1.2658 | 0.118* | |
C4 | 1.2549 (11) | 0.4177 (2) | 1.1770 (4) | 0.1203 (18) | |
H4 | 1.1474 | 0.4275 | 1.2349 | 0.144* | |
C5 | 1.2307 (9) | 0.44050 (17) | 1.0726 (5) | 0.1170 (17) | |
H5 | 1.1095 | 0.4661 | 1.0616 | 0.140* | |
C6 | 1.3817 (9) | 0.42606 (17) | 0.9862 (4) | 0.0740 (11) | |
C7 | 1.3604 (11) | 0.4511 (2) | 0.8717 (4) | 0.0893 (15) | |
C8 | 1.0763 (8) | 0.45488 (13) | 0.6740 (3) | 0.0662 (10) | |
C9 | 0.5747 (8) | 0.38503 (16) | 0.5578 (3) | 0.0740 (12) | |
H9 | 0.5412 | 0.4063 | 0.4967 | 0.089* | |
C10 | 0.4214 (8) | 0.33846 (15) | 0.5727 (3) | 0.0648 (10) | |
C11 | 0.2307 (8) | 0.32751 (16) | 0.4958 (3) | 0.0716 (11) | |
H11 | 0.1940 | 0.3499 | 0.4371 | 0.086* | |
C12 | 0.0946 (8) | 0.28268 (18) | 0.5071 (4) | 0.0763 (12) | |
C13 | 0.1352 (9) | 0.24961 (16) | 0.5946 (4) | 0.0997 (15) | |
H13 | 0.0389 | 0.2199 | 0.6014 | 0.120* | |
C14 | 0.3244 (9) | 0.26178 (18) | 0.6727 (4) | 0.1020 (15) | |
H14 | 0.3563 | 0.2399 | 0.7329 | 0.122* | |
C15 | 0.4658 (8) | 0.30577 (16) | 0.6623 (3) | 0.0838 (12) | |
H15 | 0.5917 | 0.3136 | 0.7156 | 0.101* | |
H1A | 0.851 (7) | 0.4589 (13) | 0.540 (3) | 0.100 (15)* | |
N1 | 0.8928 (7) | 0.43995 (14) | 0.6035 (3) | 0.0779 (10) | |
N2 | 0.7523 (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) | |
S1 | 1.1060 (2) | 0.41799 (4) | 0.79464 (9) | 0.0806 (4) | |
S2 | 1.2592 (2) | 0.50568 (4) | 0.64490 (9) | 0.0898 (4) | |
H7A | 1.508 (7) | 0.4456 (14) | 0.827 (3) | 0.109 (17)* | |
H7B | 1.308 (8) | 0.4842 (16) | 0.871 (3) | 0.14 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.121 (4) | 0.107 (4) | 0.092 (4) | 0.028 (3) | 0.039 (3) | 0.019 (3) |
C2 | 0.128 (4) | 0.128 (4) | 0.109 (4) | 0.051 (3) | 0.027 (4) | 0.034 (4) |
C3 | 0.108 (4) | 0.102 (4) | 0.085 (4) | 0.000 (3) | −0.004 (3) | 0.005 (3) |
C4 | 0.135 (5) | 0.142 (5) | 0.084 (4) | 0.029 (4) | 0.022 (3) | −0.002 (3) |
C5 | 0.123 (4) | 0.132 (4) | 0.097 (4) | 0.060 (3) | 0.015 (3) | 0.008 (3) |
C6 | 0.070 (3) | 0.076 (3) | 0.076 (3) | −0.005 (2) | −0.005 (3) | −0.001 (3) |
C7 | 0.077 (4) | 0.109 (5) | 0.082 (4) | −0.009 (3) | −0.010 (3) | 0.016 (3) |
C8 | 0.063 (3) | 0.068 (3) | 0.068 (3) | −0.002 (2) | 0.001 (2) | 0.007 (2) |
C9 | 0.080 (3) | 0.078 (3) | 0.064 (3) | −0.005 (3) | 0.002 (3) | 0.005 (2) |
C10 | 0.063 (3) | 0.063 (3) | 0.068 (3) | −0.006 (2) | 0.006 (2) | 0.000 (2) |
C11 | 0.068 (3) | 0.079 (3) | 0.067 (3) | −0.007 (3) | 0.003 (3) | 0.005 (2) |
C12 | 0.070 (3) | 0.089 (4) | 0.069 (3) | −0.012 (3) | −0.002 (3) | 0.000 (3) |
C13 | 0.103 (4) | 0.089 (3) | 0.107 (4) | −0.033 (3) | −0.017 (3) | 0.027 (3) |
C14 | 0.111 (4) | 0.087 (4) | 0.108 (4) | −0.020 (3) | −0.015 (3) | 0.035 (3) |
C15 | 0.094 (3) | 0.078 (3) | 0.079 (3) | −0.006 (3) | −0.013 (2) | 0.012 (3) |
N1 | 0.080 (3) | 0.079 (3) | 0.075 (3) | −0.010 (2) | −0.008 (2) | 0.015 (2) |
N2 | 0.076 (3) | 0.068 (2) | 0.077 (2) | −0.005 (2) | 0.002 (2) | 0.0053 (19) |
N3 | 0.096 (3) | 0.097 (4) | 0.094 (3) | −0.010 (3) | −0.005 (3) | 0.000 (3) |
O1 | 0.114 (3) | 0.127 (3) | 0.108 (2) | −0.019 (2) | −0.031 (2) | 0.016 (2) |
O2 | 0.180 (4) | 0.141 (3) | 0.150 (3) | −0.082 (3) | −0.045 (3) | 0.017 (3) |
S1 | 0.0798 (8) | 0.0879 (8) | 0.0741 (7) | −0.0113 (6) | 0.0010 (6) | 0.0101 (6) |
S2 | 0.0950 (9) | 0.0826 (8) | 0.0917 (8) | −0.0215 (7) | −0.0063 (6) | 0.0142 (6) |
C1—C6 | 1.343 (5) | C9—N2 | 1.272 (4) |
C1—C2 | 1.375 (5) | C9—C10 | 1.471 (5) |
C1—H1 | 0.9300 | C9—H9 | 0.9300 |
C2—C3 | 1.346 (5) | C10—C11 | 1.373 (4) |
C2—H2 | 0.9300 | C10—C15 | 1.384 (5) |
C3—C4 | 1.332 (5) | C11—C12 | 1.380 (5) |
C3—H3 | 0.9300 | C11—H11 | 0.9300 |
C4—C5 | 1.381 (5) | C12—C13 | 1.368 (5) |
C4—H4 | 0.9300 | C12—N3 | 1.489 (5) |
C5—C6 | 1.355 (5) | C13—C14 | 1.384 (5) |
C5—H5 | 0.9300 | C13—H13 | 0.9300 |
C6—C7 | 1.514 (5) | C14—C15 | 1.375 (5) |
C7—S1 | 1.823 (5) | C14—H14 | 0.9300 |
C7—H7A | 0.95 (4) | C15—H15 | 0.9300 |
C7—H7B | 0.91 (4) | N1—N2 | 1.383 (4) |
C8—N1 | 1.324 (4) | N1—H1A | 0.93 (3) |
C8—S2 | 1.676 (4) | N3—O1 | 1.208 (4) |
C8—S1 | 1.735 (4) | N3—O2 | 1.212 (4) |
C6—C1—C2 | 121.3 (4) | N2—C9—H9 | 119.6 |
C6—C1—H1 | 119.3 | C10—C9—H9 | 119.6 |
C2—C1—H1 | 119.3 | C11—C10—C15 | 119.7 (4) |
C3—C2—C1 | 120.2 (5) | C11—C10—C9 | 118.9 (4) |
C3—C2—H2 | 119.9 | C15—C10—C9 | 121.3 (4) |
C1—C2—H2 | 119.9 | C10—C11—C12 | 118.9 (4) |
C4—C3—C2 | 119.3 (5) | C10—C11—H11 | 120.6 |
C4—C3—H3 | 120.3 | C12—C11—H11 | 120.6 |
C2—C3—H3 | 120.3 | C13—C12—C11 | 122.5 (4) |
C3—C4—C5 | 120.5 (5) | C13—C12—N3 | 118.9 (4) |
C3—C4—H4 | 119.8 | C11—C12—N3 | 118.5 (4) |
C5—C4—H4 | 119.8 | C12—C13—C14 | 117.8 (4) |
C6—C5—C4 | 120.8 (4) | C12—C13—H13 | 121.1 |
C6—C5—H5 | 119.6 | C14—C13—H13 | 121.1 |
C4—C5—H5 | 119.6 | C15—C14—C13 | 120.8 (4) |
C1—C6—C5 | 117.9 (4) | C15—C14—H14 | 119.6 |
C1—C6—C7 | 120.6 (5) | C13—C14—H14 | 119.6 |
C5—C6—C7 | 121.6 (5) | C14—C15—C10 | 120.2 (4) |
C6—C7—S1 | 106.9 (3) | C14—C15—H15 | 119.9 |
C6—C7—H7A | 113 (2) | C10—C15—H15 | 119.9 |
S1—C7—H7A | 104 (2) | C8—N1—N2 | 119.6 (4) |
C6—C7—H7B | 116 (3) | C8—N1—H1A | 121 (2) |
S1—C7—H7B | 104 (3) | N2—N1—H1A | 119 (2) |
H7A—C7—H7B | 113 (4) | C9—N2—N1 | 116.5 (4) |
N1—C8—S2 | 120.9 (3) | O1—N3—O2 | 124.9 (5) |
N1—C8—S1 | 114.5 (3) | O1—N3—C12 | 117.6 (4) |
S2—C8—S1 | 124.6 (3) | O2—N3—C12 | 117.5 (5) |
N2—C9—C10 | 120.9 (4) | C8—S1—C7 | 102.0 (2) |
C6—C1—C2—C3 | 0.8 (8) | N3—C12—C13—C14 | 179.9 (4) |
C1—C2—C3—C4 | −0.1 (8) | C12—C13—C14—C15 | 0.1 (7) |
C2—C3—C4—C5 | −1.0 (8) | C13—C14—C15—C10 | −0.4 (6) |
C3—C4—C5—C6 | 1.4 (8) | C11—C10—C15—C14 | 1.7 (6) |
C2—C1—C6—C5 | −0.4 (7) | C9—C10—C15—C14 | −178.3 (3) |
C2—C1—C6—C7 | 178.1 (4) | S2—C8—N1—N2 | 177.2 (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—N1 | 177.3 (3) |
C1—C6—C7—S1 | 96.1 (5) | C8—N1—N2—C9 | 178.3 (3) |
C5—C6—C7—S1 | −85.4 (5) | C13—C12—N3—O1 | 174.2 (4) |
N2—C9—C10—C11 | 179.7 (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—O2 | 174.8 (4) |
C9—C10—C11—C12 | 177.2 (3) | N1—C8—S1—C7 | −177.5 (3) |
C10—C11—C12—C13 | 2.6 (6) | S2—C8—S1—C7 | 2.4 (3) |
C10—C11—C12—N3 | −178.5 (3) | C6—C7—S1—C8 | 173.1 (4) |
C11—C12—C13—C14 | −1.3 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···S2i | 0.93 (3) | 2.45 (4) | 3.365 (4) | 170 (3) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C15H13N3O2S2 |
Mr | 331.40 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 5.2175 (10), 26.213 (5), 11.887 (2) |
β (°) | 90.67 (3) |
V (Å3) | 1625.6 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.34 |
Crystal size (mm) | 0.30 × 0.30 × 0.10 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.906, 0.967 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9486, 2788, 951 |
Rint | 0.097 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.106, 0.73 |
No. of reflections | 2788 |
No. of parameters | 211 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.15, −0.16 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···S2i | 0.93 (3) | 2.45 (4) | 3.365 (4) | 170 (3) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
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
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