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Volume 61 
Part 8 
Pages o2441-o2443  
August 2005  

Received 17 May 2005
Accepted 1 July 2005
Online 9 July 2005

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© International Union of Crystallography 2005

Key indicators
Single-crystal X-ray study
T = 150 K
Mean [sigma](C-C) = 0.003 Å
Disorder in main residue
R = 0.039
wR = 0.047
Data-to-parameter ratio = 9.8
Details

Benzyl N-[1-(furan-2-yl)ethylidene]hydrazinecarbodithioate

Teng-Jin Khoo,a*+ Andrew R. Cowley,b David J. Watkin,b Karen A. Crousea and M. T. H. Tarafderc

aDepartment of Chemistry, Universiti Putra Malaysia, 43400 UPM, Selangor, Malaysia,bChemical Crystallography, Chemistry Research Laboratory, 12 Mansfield Road, Oxford OX1 3TA, England, and cDepartment of Chemistry, Rajshahi University, Rajshahi 6205, Bangladesh
Correspondence e-mail: teng.khoo@chem.ox.ac.uk

The title compound, C14H12N2S2O, contains a dithiocarbazate group. The phenyl ring is disordered and perpendicular [dihedral angle of 48.0 (3)°] to the rest of the molecule, which is planar.

Comment

Dithiocarbazate derivatives have been widely studied and have great potential biological activity as anticancer and antimicrobial drugs (Bharti et al., 2000[Bharti, N., Maurya, M. R., Naqvi, F., Bhattacharya, A., Bhattacharya, S. & Azam, A. (2000). Eur. J. Med. Chem. 35, 481-486.]) and in radiopharmaceutical applications (Boschi et al., 2003[Boschi, A., Bolzati, C., Uccelli, L. & Duatti, A. (2003). Nucl. Med. Biol. 30, 381-387.]). This functional group is of particular interest because it is easily tuned by reaction with different aldehydes or ketones to give varied geometries for chelation to transition metals. In the structure of the title compound, (I)[link], we were interested in studying the effect of introducing a furan ring to determine if it can also participate in chelation to a metal centre. The previously reported CdII complex of this ligand (Tarafder et al., 2002b[Tarafder, M. T. H., Khoo, T.-J., Crouse, K. A., Ali, A. M., Yamin, B. M.,& Fun, H.-K. (2002b). Polyhedron, 21, 2691-2698.]) indicated that it only forms a bis-chelating bidentate ligand without O coordination. The biological activity of the compound and its analytical characterization have also been reported (Tarafder et al., 2002a[Tarafder, M. T. H., Khoo, T.-J., Crouse, K. A., Ali, A. M., Yamin, B. M. & Fun, H.-K. (2002a). Polyhedron, 21, 2547-2554.]).

[Scheme 1]

Compound (I)[link] (Figs. 1[link]-3[link][link]) crystallizes in the unprotonated thione form with a C=S bond length of 1.664 (2) Å, which is slightly longer than that previously reported for a dithiocarbazate Schiff base [1.6503 (17) Å; Chan et al., 2003[Chan, M.-H. E., Crouse, K. A., Tarafder, M. T. H. & Yamin, B. M. (2003). Acta Cryst. E59, o628-629.]]. This is in accordance with other experimental characterizations, which indicate that this type of compound forms the thione tautomer in the solid state. The formation of the CdII complex occurs through coordination at the azomethane N atom and thiolate S atom (Tarafder et al., 2002b[Tarafder, M. T. H., Khoo, T.-J., Crouse, K. A., Ali, A. M., Yamin, B. M.,& Fun, H.-K. (2002b). Polyhedron, 21, 2691-2698.]) but does not show any bond-length change: N1-N2 = 1.381 (2) Å in (I)[link].

The molecule crystallizes in the conformer in which the N1-N2 bond adopts a trans geometry with respect to C12=S2, while the S-benzyl group adopts a cis geometry. The furan and phenyl groups are cis to each other across N2/N1/C12/S1. The C13=N2 bond [1.289 (3) Å] is formed from the condensation reaction. The C14 methyl group is cis to the furyl O atom in this free ligand but transforms to trans upon chelation to CdII (Tarafder et al., 2002b[Tarafder, M. T. H., Khoo, T.-J., Crouse, K. A., Ali, A. M., Yamin, B. M.,& Fun, H.-K. (2002b). Polyhedron, 21, 2691-2698.]), even though the O atom does not coordinate to the metal centre. The S1-C12=S2 angle is maintained at 125.22 (12)° after coordination [125.22 (12)° in (I)].

[Figure 1]
Figure 1
The molecular structure of (I)[link]. with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Both disorder components are shown. H atoms have been omitted.
[Figure 2]
Figure 2
A projection along the a axis of part of the packing of (I)[link], showing that the phenyl groups form a layer in the crystal structure. The alternative orientations of the phenyl C atoms are coloured red and blue.
[Figure 3]
Figure 3
A projection along the b axis of a section of the crystal structure of (I)[link]. The alternative orientations of the phenyl C atoms are coloured red and blue. Note that if alternate red and blue phenyl groups are selected in any layer, there are no short intermolecular clashes.

Experimental

The Schiff base ligand was prepared according to the literature method of Tarafder et al. (2002a[Tarafder, M. T. H., Khoo, T.-J., Crouse, K. A., Ali, A. M., Yamin, B. M. & Fun, H.-K. (2002a). Polyhedron, 21, 2547-2554.]). S-Benzyldithiocarbazate (1.98 g, 0.1 mol) in absolute ethanol (40 ml) was added to an equimolar quantity of 2-furylmethylketone in absolute ethanol (50 ml). The mixture was heated over a steam bath for 10 min and then cooled to 273 K in an ice bath. The Schiff base which precipitated was filtered, washed with cold ethanol and dried in vacuo over silica gel, giving a dark-orange product (yield 80%, m.p 406 K). Yellow single crystals of (I)[link], suitable for X-ray analysis, were obtained by slow evaporation of an ethanol solution over a period of three weeks.

Crystal data

  • C14H14N2OS2

  • Mr = 290.41

  • Monoclinic, P 21 /c

  • a = 4.7347 (1) Å

  • b = 32.6510 (7) Å

  • c = 9.3959 (2) Å

  • [beta] = 109.0305 (9)°

  • V = 1373.15 (5) Å3

  • Z = 4

  • Dx = 1.405 Mg m-3

  • Mo K[alpha] radiation

  • Cell parameters from 2559 reflections

  • [theta] = 5-27°

  • [mu] = 0.38 mm-1

  • T = 150 K

  • Block, yellow

  • 0.40 × 0.30 × 0.30 mm
Data collection

  • Nonius KappaCCD area-detector diffractometer

  • [omega] scans

  • Absorption correction: multi-scan(DENZO and SCALEPACK; Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.])Tmin = 0.89, Tmax = 0.89

  • 5121 measured reflections

  • 3055 independent reflections

  • 2036 reflections with I > 3[sigma](I)

  • Rint = 0.019

  • [theta]max = 27.5°

  • h = -6 [rightwards arrow] 6

  • k = -38 [rightwards arrow] 42

  • l = -12 [rightwards arrow] 12
Refinement

  • Refinement on F

  • R[F2 > 2[sigma](F2)] = 0.039

  • wR(F2) = 0.047

  • S = 1.09

  • 2036 reflections

  • 208 parameters

  • H-atom parameters constrained

  • Chebychev polynomial, with Ai coefficients 1.29, 0.798, 1.02

  • ([Delta]/[sigma])max < 0.001

  • [Delta][rho]max = 0.37 e Å-3

  • [Delta][rho]min = -0.27 e Å-3

Table 1
Selected geometric parameters (Å, °)[link]

C12-N1 1.343 (3)
C12-S1 1.749 (2)
C12-S2 1.664 (2)
C13-N2 1.289 (3)
C15-C16 1.344 (3)
C15-O1 1.374 (2)
C16-C17 1.423 (3)
C17-C18 1.330 (3)
C18-O1 1.364 (3)
N1-N2 1.381 (2)
N1-C12-S1 113.77 (15)
N1-C12-S2 121.00 (16)
S1-C12-S2 125.22 (12)
C14-C13-N2 125.2 (2)
C15-C13-N2 115.42 (18)
C12-N1-N2 119.35 (17)
C12-N1-H3 119.4
N1-N2-C13 116.37 (18)
C15-O1-C18 106.40 (16)
C11-S1-C12 101.75 (10)

The phenyl group was seen to be disordered. The site occupancy factors for the two orientations refined to 0.508 (4):0.492 (4), in close agreement with the value of 0.5:0.5 which would be required by strict alternation of the two orientations in each molecular layer (Figs. 2[link] and 3[link]). All H atoms (including those of the disordered phenyl group) were located in a difference map, but those attached to C atoms were repositioned geometrically. All H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C-H in the range 0.93-98 and N-H = 0.85 Å) and isotropic atomic displacement parameters [Uiso(H) in the range 1.2-1.5 times Ueq of the parent atom], after which they were refined with riding constraints.

Data collection: COLLECT (Nonius, 2001[Nonius (2001). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003[Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, C. K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487.]); molecular graphics: CAMERON (Watkin et al., 1996[Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England.]); software used to prepare material for publication: CRYSTALS.

Acknowledgements

KTJ gratefully acknowledges MOSTI, Malaysia, for an attachment grant under an NSF scholarship, and the Chemical Crystallography Laboratory, University of Oxford, for instrumental facilities.

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. [details]
Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, C. K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487. [details]
Bharti, N., Maurya, M. R., Naqvi, F., Bhattacharya, A., Bhattacharya, S. & Azam, A. (2000). Eur. J. Med. Chem. 35, 481-486. [CrossRef] [PubMed]
Boschi, A., Bolzati, C., Uccelli, L. & Duatti, A. (2003). Nucl. Med. Biol. 30, 381-387. [ISI] [CrossRef] [PubMed] [ChemPort]
Chan, M.-H. E., Crouse, K. A., Tarafder, M. T. H. & Yamin, B. M. (2003). Acta Cryst. E59, o628-629. [details]
Nonius (2001). COLLECT. Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.
Tarafder, M. T. H., Khoo, T.-J., Crouse, K. A., Ali, A. M., Yamin, B. M. & Fun, H.-K. (2002a). Polyhedron, 21, 2547-2554. [CrossRef] [ChemPort]
Tarafder, M. T. H., Khoo, T.-J., Crouse, K. A., Ali, A. M., Yamin, B. M.,& Fun, H.-K. (2002b). Polyhedron, 21, 2691-2698. [CrossRef] [ChemPort]
Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England.

Acta Cryst (2005). E61, o2441-o2443   [ doi:10.1107/S1600536805020969 ]