(E)-2-[1-(1-Benzothio­phen-3-yl)ethyl­idene]hydrazinecarbothio­amide methanol hemisolvate

Safa’a Fares Kayed; Yang Farina; Mohammad Kassim; Jim Simpson

doi:10.1107/S160053680801297X

. 2008 May 10;64(Pt 6):o1022–o1023. doi: 10.1107/S160053680801297X

(E)-2-[1-(1-Benzothiophen-3-yl)ethylidene]hydrazinecarbothioamide methanol hemisolvate

Safa’a Fares Kayed ^a, Yang Farina ^a,^*, Mohammad Kassim ^a, Jim Simpson ^b

PMCID: PMC2961618 PMID: 21202547

Abstract

The asymmetric unit of the title compound, C₁₁H₁₁N₃S₂·0.5CH₄O, contains four thiosemicarbazone molecules and two methanol solvent molecules. Each hydrazinecarbothioamide molecule adopts an E configuration with respect to the C=N double bond and is stabilized by an intramolecular N—H⋯N hydrogen bond, resulting in an S(5) ring motif. In the crystal structure, an extensive network of N—H⋯O, N—H⋯N, O—H⋯S and N—H⋯S hydrogen bonds and weak C—H⋯O, C—H⋯N and C—H⋯S contacts together with an S⋯S [3.5958 (14) Å] and a C—H⋯π interaction form a three-dimensional network.

Related literature

For related structures, see: de Lima et al. (2002 ▶); Işık et al. (2006 ▶). For reference structural data, see: Allen et al. (1987 ▶). For graph-set analysis of hydrogen bonding, see: Bernstein et al., (1995 ▶).

Experimental

Crystal data

C₁₁H₁₁N₃S₂·0.5CH₄O
M _r = 265.38
Monoclinic,
a = 18.9438 (12) Å
b = 17.7076 (11) Å
c = 15.4145 (10) Å
β = 107.238 (3)°
V = 4938.5 (5) Å³
Z = 16
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 92 (2) K
0.31 × 0.20 × 0.13 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T _min = 0.777, T _max = 0.947
65034 measured reflections
10871 independent reflections
8171 reflections with I > 2σ(I)
R _int = 0.086

Refinement

R[F ² > 2σ(F ²)] = 0.067
wR(F ²) = 0.203
S = 1.03
10871 reflections
655 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.71 e Å⁻³
Δρ_min = −2.31 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: APEX2 and SAINT (Bruker, 2006 ▶); data reduction: SAINT (Bruker, 2006 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶) and TITAN2000 (Hunter & Simpson, 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and TITAN2000; molecular graphics: SHELXTL (Sheldrick, 2008 ▶), ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ▶) and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680801297X/hb2725sup1.cif

e-64-o1022-sup1.cif^{(32.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680801297X/hb2725Isup2.hkl

e-64-o1022-Isup2.hkl^{(531.6KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3A—H3N2⋯N1A	0.843 (10)	2.29 (4)	2.641 (4)	105 (3)
N3B—H3N3⋯N1B	0.838 (10)	2.21 (4)	2.617 (4)	110 (3)
N3C—H3N5⋯N1C	0.842 (10)	2.22 (5)	2.543 (4)	102 (4)
N3D—H3N7⋯N1D	0.841 (10)	2.29 (5)	2.643 (4)	105 (4)
N3A—H3N1⋯S2Bⁱ	0.839 (10)	2.500 (14)	3.325 (3)	168 (4)
N3B—H3N4⋯S2Aⁱⁱ	0.839 (10)	2.62 (2)	3.367 (3)	149 (4)
N2B—H2NB⋯S2Aⁱⁱⁱ	0.839 (10)	2.585 (13)	3.412 (3)	169 (4)
N3C—H3N6⋯S2A^iv	0.840 (10)	2.76 (4)	3.352 (3)	129 (4)
N3C—H3N6⋯N3B^v	0.840 (10)	2.72 (3)	3.468 (5)	149 (5)
N2C—H2NC⋯S2C^vi	0.842 (10)	2.60 (2)	3.392 (3)	158 (4)
N3D—H3N8⋯S2A^iv	0.840 (10)	2.738 (15)	3.563 (3)	168 (4)
N3D—H3N7⋯O1S	0.841 (10)	2.26 (3)	2.967 (6)	142 (4)
O1S—H1S⋯S2C^vi	0.84	2.64	3.471 (5)	169
O2S—H2S⋯S2D^vii	0.84	2.97	3.389 (6)	113
C3A—H3A⋯S2A^iv	0.95	2.97	3.762 (4)	142
C10A—H10A⋯S2B^viii	0.98	2.91	3.613 (3)	129
C2B—H2B⋯O1S^ix	0.95	2.36	3.282 (7)	163
C2S—H2S1⋯N2D^vii	0.98	2.74	3.266 (9)	115
C10B—H10F⋯C_g^x	0.98	2.91	3.594 (4)	129

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) . Cg is the centroid of C1B–C6B.

Acknowledgments

We thank the Universiti Kebangsaan Malaysia and the Ministry of Higher Education, Malaysia, for supporting this research through grant UKM-ST-01-FRGS0022-2006. We also thank the University of Otago for the purchase of the diffractometer.

supplementary crystallographic information

Comment

Structures similar to the title compound, (I), have been reported including the thiosemicarbazone derived from 2-acetylthiophene (Lima et al., 2002); and a pryazoline derivative (Işık et al., 2006).

The asymmetric unit of (I) contains four molecules, labeled A—D (Figs 1—4) and two methanol solvate molecules, with the complete assemblage shown in Fig. 5. Each molecule adopts an E configuration with respect to the C=N bond and bond distances and angles are normal (Allen et al., 1987). Intramolecular N3—H···N1 hydrogen bonds (Table 1) form between each of the the NH₂ groups and the imine N atoms generating S(5) ring motifs (Bernstein et al., 1995). These contribute to the planarity of the molecules.

In the crystal of (I), N2—H2···S2 hydrogen bonds generate centrosymmetric R²₂(8) rings in molecules A—C. For molecule D, C2S—H2S1···S2D hydrogen bonding to a methanol solvate within the asymmetric unit obviates such an interaction. Other N—H···O, N—H···N, O—H···S and N—H···S hydrogen bonds together with weak C—H···O, C—H···N and C—H···S contacts, an S···S interaction (d(S1D···S1Bⁱ) = 3.5958 (14) Å; i = x, 3/2 - y, -1/2 + z) and a C10B—H10F···Cgⁱⁱ interaction (ii = -x, 1 - y, -z; Cg is the centroid of the C1B···C6B ring) form a complex three dimensional network (Fig 6).

Experimental

A 1:1 mixture of 2-acetylbenzothiophene and thiosemicarbazide was heated under reflux in ethanol for 2 h. The solid product which separated upon cooling was filtered and recrystallized from a 1:1 mixture of acetonitrile and methanol to afford colourless, blocks of (I) in 68% yield (m.p. 483–485 K).