(E)-2-[1-(1-Benzothio­phen-2-yl)ethyl­idene]-N-phenyl­hydrazinecarboxamide

Safa’a Faris Kayed; Yang Farina; Jim Simpson; Ibrahim Baba

doi:10.1107/S1600536811037457

. 2011 Sep 20;67(Pt 10):o2687–o2688. doi: 10.1107/S1600536811037457

(E)-2-[1-(1-Benzothiophen-2-yl)ethylidene]-N-phenylhydrazinecarboxamide

Safa’a Faris Kayed ^a,^*, Yang Farina ^a, Jim Simpson ^b, Ibrahim Baba ^a

PMCID: PMC3201294 PMID: 22058789

Abstract

The title compound, C₁₇H₁₅N₃OS, crystallizes with two unique molecules, denoted 1 and 2, in the asymmetric unit. The two molecules are closely similar and overlay with an r.m.s. deviation of 0.053 Å. Both molecules adopt E configurations with respect to the C=N bonds. The dihedral angles between the benzothiophene groups and N-bound phenyl rings are 36.36 (9)° for molecule 1 and 29.71 (9)° for molecule 2. The C=N—NH—C(O)NH ethylidene–hydrazinecarboxamide units are also reasonably planar, with r.m.s. deviations of 0.061 and 0.056 Å, respectively, for the two molecules. The methyl substituents lie 0.338 (3) and 0.396 (3) Å, respectively, from these planes. The C=N—NH—C(O)NH planes are inclined to the phenyl rings at 13.65 (11) and 15.56 (11)°, respectively, in molecules 1 and 2. This conformation is enhanced by weak intramolecular C—H⋯O hydrogen bonds between ortho-H atoms of the two phenyl rings and the carbonyl O atoms, which generate S(6) rings in each molecule. In the crystal, pairs of molecules are linked by pairs of intermolecular N—H⋯O hydrogen bonds into dimers. Alternating dimers are further interconnected by weak C—H⋯O contacts into zigzag rows along b. The rows are stacked along a by C—H⋯π contacts involving the benzene ring from molecule 2 and the thiophene ring from molecule 1 of adjacent benzothiophene units.

Related literature

For background to the biological activity of semicarbazones, see: Alam et al. (2010 ▶); Sharma et al. (2006 ▶); Siji et al. (2010 ▶); Sriram et al. (2004 ▶). For related structures, see: Beraldo et al. (2001 ▶); Fun et al. (2009a ▶,b ▶); Mendoza-Meroño et al. (2011 ▶). For graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₇H₁₅N₃OS
M _r = 309.38
Triclinic,
a = 9.8858 (3) Å
b = 13.2737 (5) Å
c = 13.6121 (8) Å
α = 113.961 (3)°
β = 98.153 (3)°
γ = 107.778 (2)°
V = 1480.02 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 89 K
0.38 × 0.14 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.826, T _max = 1.000
25263 measured reflections
8650 independent reflections
5747 reflections with I > 2σ(I)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.147
S = 1.07
8650 reflections
411 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: APEX2 and SAINT (Bruker, 2009 ▶); data reduction: SAINT; 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 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ▶), PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811037457/tk2786sup1.cif

e-67-o2687-sup1.cif^{(37KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037457/tk2786Isup2.hkl

e-67-o2687-Isup2.hkl^{(423.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811037457/tk2786Isup3.cml

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

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

Cg1 is the centroid of the S11, C11, C12, C13, C18 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N12—H12N⋯O21	0.97 (2)	1.91 (2)	2.847 (2)	162.1 (19)
N22—H22N⋯O11	0.89 (2)	1.99 (2)	2.840 (2)	158 (2)
C113—H113⋯O11	0.95	2.29	2.886 (2)	120
C213—H213⋯O21	0.95	2.26	2.871 (2)	121
C15—H15⋯O11ⁱ	0.95	2.62	3.435 (2)	144
C24—H24⋯Cg1ⁱⁱ	0.95	2.80	3.482 (2)	130

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

We wish to thank Universiti Kebangsaan Malaysia and the Ministry of Higher Education, Malaysia, for supporting this research through grants UKM-ST-01-FRGS0022–2006 and UKM-GUP-NBT-08–27-112. We also thank the University of Otago for the purchase of the diffractometer.

supplementary crystallographic information

Comment

Semicarbazones are of considerable interest because of their wide spectrum of biological applications, and display anticonvulsant (Alam et al., 2010), antitubercular (Sriram et al., 2004) and antimicrobial activity (Siji et al., 2010). The biological activity of semicarbazones is considered to be due to their ability to form chelate complexes with transition metals (Sharma et al., 2006).In view of the importance of these compounds, we report here the structure of the title semicarbazone derivative (Fig. 1).

The asymmetric unit of the title compound contains two molecules, 1 and 2. The benzothiophene group and the C9=N1—N2—C11(O1)N3 semicarbazone units are almost coplanar with N1—C9—C1—S1 torsion angles of -13.0 (2)° for 1 and -9.3 (2)° for 2. The phenyl rings show somewhat greater coplanarity with the semicarbazone linking units the C11—N3—C12—C13 angles being -13.3 (3)° for 1 and 5.4 (3)° for 2. The dihedral angles between the benzothiophene groups and the phenyl rings are 36.36 (7)° for 1 and 29.71 (8)° for 2. Both molecules adopt E configurations with respect to the C=N bonds. There are no important differences in the bond lengths and angles between the two unique molecules which overlay with an r.m.s. deviation of 0.053 Å (Macrae et al., 2008). The bond distances and angles are in a good agreement with values reported for similar structures (Beraldo et al., 2001; Fun et al., 2009a,b; Mendoza-Meroño et al. 2011). Intramolecular C113–H113···O11 and C113–H113···O11 hydrogen bonds are observed in both molecules and generate S(6) rings (Bernstein et al. 1995).

In the crystal structure, intermolecular N12—H12N···O21 and N22—H22N···O11 hydrogen bonds (Table 1) link the molecules into dimers (Fig. 2). A weak C110—H11A..O21 interaction further strengthens the dimer unit for molecule 1. Alternating dimers are further interconnected by weak C15–H15···O11 contacts generating zigzag rows along b. C24—H24..π contacts to the S11, C11, C12, C13, C18 thiophene rings of adjacent molecules form stacks along a, (Fig. 3).

Experimental

4-Phenyl-3-semicarbazide (1.51 g, 10 mmol) was dissolved in boiling ethanol (40 ml). A solution of 2-acetylbenzothiophene (1.77 g, 10 mmol) in ethanol (30 ml) was added to the 4-phenylsemicarbazide solution followed by the addition of three drops of sulphuric acid. The mixture was heated under reflux with stirring for 2 h. The solid product which separated upon cooling was filtered and recrystallized from a 1:1 mixture of dimethylsulphoxide and ethanol.