PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2477.
Published online 2008 November 29. doi:  10.1107/S1600536808039408
PMCID: PMC2959849

Benzyl N′-benzhydrylidene­hydrazine­carbodithio­ate

Abstract

In the title mol­ecule, C21H18N2S2, the C=N—N angle of 117.6 (2)° is significantly smaller than the ideal value of 120° expected for sp 2-hybridized N atoms. This is probably a consequence of repulsion between the nitro­gen lone pairs and the adjacent N atom, as suggested in Zheng, Qiu, Lin & Liu [Acta Cryst. (2006), E62, o1913–o1914]. The two neighbouring benzene rings form a dihedral angle of 75.95 (3)° with each other, while subtending dihedral angles of 84.18 (3) and 8.44 (2)° with the third ring in the structure.

Related literature

For related literature on ligands derived from S-benzyl­dithio­carbazate (SBDTC), see: Ali et al. (2002 [triangle], 2008 [triangle]); Crouse et al. (2004 [triangle]); Tarafder et al. (2001 [triangle], 2008 [triangle]); Zheng et al. (2006 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2477-scheme1.jpg

Experimental

Crystal data

  • C21H18N2S2
  • M r = 362.49
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2477-efi1.jpg
  • a = 20.2903 (14) Å
  • b = 9.0951 (6) Å
  • c = 10.5818 (7) Å
  • β = 103.9240 (10)°
  • V = 1895.4 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.29 mm−1
  • T = 295 (2) K
  • 0.12 × 0.10 × 0.06 mm

Data collection

  • Bruker APEX2 CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.967, T max = 0.983
  • 9776 measured reflections
  • 3363 independent reflections
  • 2191 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 0.116
  • S = 1.05
  • 3363 reflections
  • 214 parameters
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; 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.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808039408/bg2222sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808039408/bg2222Isup2.hkl

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

Acknowledgments

This project was supported by the Postgraduate Foundation of Taishan University (No. Y03–1–13).

supplementary crystallographic information

Comment

In recent years, the interesting coordination chemistry and increasingly relevant biomedical properties of ligands derived from S-benzyldithiocarbazate(SBDTC) have received much attention (Ali et al., 2002, 2008; Crouse et al., 2004; Tarafder et al., 2001, 2008). In order to search for new ligands derived from SBDTC, the title compound C21H18N2S2 (I) was synthesized and its crystal structure determined. Fig 1 shows a molecular diagram of (I), where bond lengths and angles are basically in normal ranges (Allen et al., 1987). The C=N bond length of 1.293 (3) Å(C9=N2) shows double-bond character. The C=N—N angle of 117.6 (2) ° is significantly smaller than the ideal value of 120 ° expected for sp2-hybridized N atoms. This is probably a consequence of repulsion between the nitrogen lone pairs and the adjacent N atom (Zheng et al., 2006). The C10—C15, C16—C21 benzene rings are oriented at 84.18 (3) °, 8.44 (2) ° with respect to the C1—C6 one. The dihedral angle formed by the C10—C15 and C16—C21 rings is 75.95 (3) °.

Experimental

The title compound was synthesized by the reaction of Hydrazinecarbodithioic acid benzyl ester(1 mmol, 198.3 mg) with Diphenyl-methanone(1 mmol, 182.2 mg) in ethanol(15 ml) under reflux conditions (338 K) for 5 h. The solvent was removed and the solid product recrystallized from tetrahydrofuran. After six days yellow crystals suitable for X-ray diffraction study were obtained.

Refinement

All H atoms were placed in idealized positions (C—H = 0.93— 0.97 Å, N—H = 0.86 Å) and refined as riding atoms. For those bound to C, Uiso(H) = 1.2 or 1.5Ueq(C). while for those bound to N, Uiso(H) = 1.2 Ueq(N).

Figures

Fig. 1.
The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level.

Crystal data

C21H18N2S2F000 = 760
Mr = 362.49Dx = 1.270 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1615 reflections
a = 20.2903 (14) Åθ = 3.0–22.7º
b = 9.0951 (6) ŵ = 0.29 mm1
c = 10.5818 (7) ÅT = 295 (2) K
β = 103.9240 (10)ºBlock, yellow
V = 1895.4 (2) Å30.12 × 0.10 × 0.06 mm
Z = 4

Data collection

Bruker APEX2 CCD area-detector diffractometer3363 independent reflections
Radiation source: fine-focus sealed tube2191 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.039
T = 295(2) Kθmax = 25.1º
[var phi] and ω scansθmin = 2.1º
Absorption correction: multi-scan(SADABS; Bruker, 2005)h = −24→24
Tmin = 0.967, Tmax = 0.983k = −10→10
9776 measured reflectionsl = −11→12

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.116  w = 1/[σ2(Fo2) + (0.0462P)2 + 0.2919P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
3363 reflectionsΔρmax = 0.22 e Å3
214 parametersΔρmin = −0.23 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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
S10.29194 (4)0.73862 (8)0.23650 (8)0.0593 (2)
S20.15831 (4)0.59677 (8)0.10325 (8)0.0636 (3)
N10.17341 (11)0.8548 (2)0.2139 (2)0.0539 (6)
H10.12990.86300.19090.065*
N20.21181 (11)0.9673 (2)0.2809 (2)0.0508 (6)
C10.39011 (8)0.5783 (2)0.1752 (2)0.0578 (8)
C20.41212 (13)0.6495 (2)0.0766 (2)0.0836 (10)
H20.38070.69090.00700.100*
C30.48112 (15)0.6589 (3)0.0820 (3)0.1024 (13)
H30.49580.70650.01600.123*
C40.52811 (9)0.5971 (3)0.1861 (3)0.1042 (14)
H40.57430.60340.18970.125*
C50.50611 (11)0.5259 (3)0.2847 (3)0.1084 (14)
H50.53760.48450.35430.130*
C60.43711 (12)0.5165 (3)0.2793 (2)0.0868 (11)
H60.42240.46890.34520.104*
C70.31560 (14)0.5689 (3)0.1698 (4)0.0709 (9)
H7A0.30650.48570.22040.085*
H7B0.28980.55660.08050.085*
C80.20349 (13)0.7318 (3)0.1840 (2)0.0475 (7)
C90.18138 (13)1.0901 (3)0.2909 (2)0.0450 (6)
C100.22361 (13)1.2075 (3)0.3651 (2)0.0449 (6)
C110.29263 (14)1.1870 (3)0.4165 (3)0.0603 (8)
H110.31291.09970.40000.072*
C120.33158 (15)1.2931 (3)0.4912 (3)0.0714 (9)
H120.37771.27700.52560.086*
C130.30214 (17)1.4240 (3)0.5153 (3)0.0718 (9)
H130.32841.49590.56640.086*
C140.23479 (16)1.4474 (3)0.4641 (3)0.0664 (8)
H140.21531.53620.47920.080*
C150.19518 (15)1.3404 (3)0.3898 (3)0.0554 (7)
H150.14911.35740.35590.067*
C160.10755 (13)1.1135 (3)0.2328 (2)0.0437 (6)
C170.05888 (14)1.0439 (3)0.2829 (3)0.0564 (7)
H170.07230.98290.35500.068*
C18−0.00925 (15)1.0638 (3)0.2275 (3)0.0653 (8)
H18−0.04141.01760.26340.078*
C19−0.02962 (16)1.1503 (3)0.1210 (3)0.0664 (9)
H19−0.07571.16320.08390.080*
C200.01760 (16)1.2191 (3)0.0678 (3)0.0670 (8)
H200.00351.2776−0.00580.080*
C210.08623 (15)1.2016 (3)0.1237 (3)0.0569 (7)
H210.11811.24910.08800.068*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0445 (4)0.0491 (4)0.0788 (6)0.0040 (3)0.0042 (4)−0.0127 (4)
S20.0521 (5)0.0564 (5)0.0746 (6)−0.0006 (4)0.0000 (4)−0.0137 (4)
N10.0414 (13)0.0488 (13)0.0692 (16)0.0060 (11)0.0091 (12)−0.0080 (12)
N20.0458 (14)0.0466 (13)0.0590 (15)0.0028 (11)0.0109 (11)−0.0066 (12)
C10.0502 (18)0.0447 (16)0.075 (2)0.0061 (14)0.0092 (16)−0.0101 (16)
C20.079 (3)0.085 (2)0.083 (3)0.004 (2)0.012 (2)0.005 (2)
C30.092 (3)0.112 (3)0.113 (3)−0.017 (3)0.043 (3)−0.008 (3)
C40.056 (2)0.103 (3)0.157 (4)−0.003 (2)0.032 (3)−0.015 (3)
C50.055 (2)0.116 (3)0.142 (4)0.008 (2)0.000 (2)0.022 (3)
C60.057 (2)0.096 (3)0.105 (3)0.004 (2)0.013 (2)0.022 (2)
C70.0489 (18)0.0562 (18)0.106 (3)0.0071 (15)0.0148 (17)−0.0217 (19)
C80.0460 (16)0.0449 (15)0.0490 (16)0.0064 (13)0.0061 (13)0.0026 (13)
C90.0434 (15)0.0456 (15)0.0471 (16)0.0044 (13)0.0131 (13)0.0009 (13)
C100.0455 (16)0.0438 (14)0.0474 (16)−0.0001 (13)0.0149 (13)0.0013 (13)
C110.0478 (18)0.0486 (16)0.085 (2)−0.0010 (14)0.0170 (16)−0.0034 (17)
C120.0443 (18)0.069 (2)0.096 (3)−0.0064 (16)0.0091 (17)−0.006 (2)
C130.068 (2)0.066 (2)0.081 (2)−0.0139 (18)0.0166 (19)−0.0177 (18)
C140.065 (2)0.0560 (18)0.078 (2)0.0044 (16)0.0167 (18)−0.0150 (17)
C150.0504 (17)0.0555 (17)0.0610 (19)0.0064 (14)0.0148 (15)−0.0089 (15)
C160.0435 (16)0.0386 (14)0.0478 (16)0.0057 (12)0.0087 (13)−0.0025 (13)
C170.0494 (18)0.0600 (18)0.0606 (18)0.0050 (14)0.0145 (15)0.0111 (15)
C180.0477 (19)0.075 (2)0.074 (2)−0.0001 (16)0.0154 (16)0.0044 (19)
C190.0477 (19)0.065 (2)0.078 (2)0.0080 (16)−0.0017 (17)−0.0048 (18)
C200.067 (2)0.066 (2)0.060 (2)0.0142 (17)−0.0012 (17)0.0090 (17)
C210.0591 (19)0.0528 (16)0.0591 (18)0.0061 (15)0.0148 (15)0.0070 (15)

Geometric parameters (Å, °)

S1—C81.747 (3)C10—C111.388 (4)
S1—C71.810 (3)C10—C151.391 (3)
S2—C81.643 (3)C11—C121.371 (4)
N1—C81.348 (3)C11—H110.9300
N1—N21.375 (3)C12—C131.383 (4)
N1—H10.8600C12—H120.9300
N2—C91.293 (3)C13—C141.360 (4)
C1—C21.3900C13—H130.9300
C1—C61.3900C14—C151.381 (4)
C1—C71.501 (3)C14—H140.9300
C2—C31.3900C15—H150.9300
C2—H20.9300C16—C171.381 (4)
C3—C41.3900C16—C211.386 (3)
C3—H30.9300C17—C181.377 (4)
C4—C51.3900C17—H170.9300
C4—H40.9300C18—C191.355 (4)
C5—C61.3900C18—H180.9300
C5—H50.9300C19—C201.373 (4)
C6—H60.9300C19—H190.9300
C7—H7A0.9700C20—C211.385 (4)
C7—H7B0.9700C20—H200.9300
C9—C101.472 (3)C21—H210.9300
C9—C161.491 (3)
C8—S1—C7101.19 (13)C11—C10—C9121.0 (2)
C8—N1—N2120.4 (2)C15—C10—C9121.1 (2)
C8—N1—H1119.8C12—C11—C10121.3 (3)
N2—N1—H1119.8C12—C11—H11119.4
C9—N2—N1117.6 (2)C10—C11—H11119.4
C2—C1—C6120.0C11—C12—C13119.8 (3)
C2—C1—C7120.0 (2)C11—C12—H12120.1
C6—C1—C7120.0 (2)C13—C12—H12120.1
C3—C2—C1120.0C14—C13—C12119.9 (3)
C3—C2—H2120.0C14—C13—H13120.0
C1—C2—H2120.0C12—C13—H13120.0
C2—C3—C4120.0C13—C14—C15120.5 (3)
C2—C3—H3120.0C13—C14—H14119.7
C4—C3—H3120.0C15—C14—H14119.7
C5—C4—C3120.0C14—C15—C10120.6 (3)
C5—C4—H4120.0C14—C15—H15119.7
C3—C4—H4120.0C10—C15—H15119.7
C4—C5—C6120.0C17—C16—C21118.4 (3)
C4—C5—H5120.0C17—C16—C9121.1 (2)
C6—C5—H5120.0C21—C16—C9120.5 (2)
C5—C6—C1120.0C18—C17—C16120.9 (3)
C5—C6—H6120.0C18—C17—H17119.5
C1—C6—H6120.0C16—C17—H17119.5
C1—C7—S1107.18 (18)C19—C18—C17120.2 (3)
C1—C7—H7A110.3C19—C18—H18119.9
S1—C7—H7A110.3C17—C18—H18119.9
C1—C7—H7B110.3C18—C19—C20120.1 (3)
S1—C7—H7B110.3C18—C19—H19119.9
H7A—C7—H7B108.5C20—C19—H19119.9
N1—C8—S2121.0 (2)C19—C20—C21120.1 (3)
N1—C8—S1112.58 (19)C19—C20—H20119.9
S2—C8—S1126.42 (15)C21—C20—H20119.9
N2—C9—C10116.3 (2)C20—C21—C16120.2 (3)
N2—C9—C16122.8 (2)C20—C21—H21119.9
C10—C9—C16120.9 (2)C16—C21—H21119.9
C11—C10—C15117.9 (3)
C8—N1—N2—C9170.5 (2)C16—C9—C10—C153.9 (4)
C6—C1—C2—C30.0C15—C10—C11—C121.1 (4)
C7—C1—C2—C3179.7 (2)C9—C10—C11—C12−176.6 (3)
C1—C2—C3—C40.0C10—C11—C12—C13−0.7 (5)
C2—C3—C4—C50.0C11—C12—C13—C14−0.4 (5)
C3—C4—C5—C60.0C12—C13—C14—C151.0 (5)
C4—C5—C6—C10.0C13—C14—C15—C10−0.6 (5)
C2—C1—C6—C50.0C11—C10—C15—C14−0.5 (4)
C7—C1—C6—C5−179.7 (2)C9—C10—C15—C14177.3 (2)
C2—C1—C7—S1−83.8 (2)N2—C9—C16—C1770.2 (3)
C6—C1—C7—S195.8 (2)C10—C9—C16—C17−109.1 (3)
C8—S1—C7—C1164.8 (2)N2—C9—C16—C21−107.4 (3)
N2—N1—C8—S2−179.69 (18)C10—C9—C16—C2173.4 (3)
N2—N1—C8—S1−1.2 (3)C21—C16—C17—C18−1.2 (4)
C7—S1—C8—N1−175.2 (2)C9—C16—C17—C18−178.8 (3)
C7—S1—C8—S23.2 (2)C16—C17—C18—C191.1 (4)
N1—N2—C9—C10179.0 (2)C17—C18—C19—C20−0.1 (5)
N1—N2—C9—C16−0.3 (4)C18—C19—C20—C21−0.7 (4)
N2—C9—C10—C112.3 (4)C19—C20—C21—C160.6 (4)
C16—C9—C10—C11−178.4 (2)C17—C16—C21—C200.3 (4)
N2—C9—C10—C15−175.4 (2)C9—C16—C21—C20178.0 (2)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BG2222).

References

  • Ali, M. A., Baker, H. J. H. A., Mirza, A. H., Smith, S. J., Gahan, L. R. & Bernhardt, P. V. (2008). Polyhedron, 27, 71–79.
  • Ali, M. A., Mirza, A. H., Butcher, R. J., Tarafder, M. T. H., Keat, T. B., Ali, A. M. & Manaf, A. (2002). J. Inorg. Biochem.92, 141–148. [PubMed]
  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Bruker (2005). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Crouse, K. A., Chew, K.-B., Tarafder, M. T. H., Kasbollah, A., Ali, A. M., Yamin, B. M. & Fun, H.-K. (2004). Polyhedron, 23, 161–168.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Tarafder, M. T. H., Islam, M. T., Islam, M. A. A. A. A., Chantrapromma, S. & Fun, H.-K. (2008). Acta Cryst. E64, m416–m417. [PMC free article] [PubMed]
  • Tarafder, M. T. H., Kasbollah, A., Crouse, K. A., Ali, A. M., Yamin, B. M. & Fun, H.-K. (2001). Polyhedron, 20, 2363–2370.
  • Zheng, P.-W., Qiu, Q.-M., Lin, Y.-Y. & Liu, K.-F. (2006). Acta Cryst. E62, o1913–o1914.

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