organic compounds
(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
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
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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/S1600536809047953/hb5222sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809047953/hb5222Isup2.hkl
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.
The H atoms were positioned geometrically (C—H = 0.93–0.96 Å) and refined as riding, with Uiso(H) = 1.2Ueq(C).
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).C15H12ClN3O2S2 | F(000) = 752 |
Mr = 365.85 | Dx = 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 |
Enraf–Nonius CAD-4 diffractometer | 2538 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 26.0°, θmin = 2.1° |
ω/2θ scans | h = −12→11 |
Absorption correction: ψ scan (North et al., 1968) | k = −10→10 |
Tmin = 0.884, Tmax = 0.928 | l = −23→23 |
10135 measured reflections | 200 standard reflections every 3 reflections |
3086 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)] = 0.032 | 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(Fo2) + (0.0407P)2 + 0.5179P] where P = (Fo2 + 2Fc2)/3 |
3086 reflections | (Δ/σ)max = 0.003 |
212 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
C15H12ClN3O2S2 | V = 1613.0 (6) Å3 |
Mr = 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)° |
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 = 0.928 | 200 standard reflections every 3 reflections |
10135 measured reflections | intensity decay: 1% |
3086 independent reflections |
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 | Δρmax = 0.49 e Å−3 |
3086 reflections | Δρmin = −0.44 e Å−3 |
212 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 | 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) |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.884, 0.928 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10135, 3086, 2538 |
Rint | 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 |
Δρmax, Δρmin (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).
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
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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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