N′-[(E)-(4-Bromo-2-thienyl)methyl­ene]isonicotinohydrazide

Zahid Shafiq; Muhammad Yaqub; M Nawaz Tahir; Abid Hussain; M Saeed Iqbal

doi:10.1107/S160053680903709X

. 2009 Sep 19;65(Pt 10):o2496. doi: 10.1107/S160053680903709X

N′-[(E)-(4-Bromo-2-thienyl)methylene]isonicotinohydrazide

Zahid Shafiq ^a, Muhammad Yaqub ^a, M Nawaz Tahir ^b,^*, Abid Hussain ^a, M Saeed Iqbal ^c

PMCID: PMC2970269 PMID: 21577946

Abstract

In title compound, C₁₁H₈BrN₃OS, the dihedral angle between the two aromatic rings is 27.61 (14)° and the Br atom is disordered over two sites with an occupancy ratio of 0.804 (2):0.196 (2). In the crystal, the molecules are linked by N—H⋯O, C—H⋯O and C—H⋯N interactions, resulting in chains.

Related literature

For related structures, see: Jing et al. (2007 ▶); Shafiq et al. (2009 ▶); Wang et al. (2007 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₁H₈BrN₃OS
M _r = 310.17
Orthorhombic,
a = 14.3507 (6) Å
b = 48.732 (2) Å
c = 7.2115 (3) Å
V = 5043.3 (4) Å³
Z = 16
Mo Kα radiation
μ = 3.41 mm⁻¹
T = 296 K
0.26 × 0.14 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.567, T _max = 0.666
12209 measured reflections
2837 independent reflections
1954 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.113
S = 1.04
2837 reflections
158 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.48 e Å⁻³
Absolute structure: Flack (1983 ▶), 1205 Friedal Pairs
Flack parameter: −0.002 (13)

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680903709X/hb5101sup1.cif

e-65-o2496-sup1.cif^{(16.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680903709X/hb5101Isup2.hkl

e-65-o2496-Isup2.hkl^{(136.7KB, 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
N2—H2⋯O1ⁱ	0.86	2.08	2.920 (4)	165
C7—H7⋯O1ⁱ	0.93	2.52	3.318 (5)	144
C11—H11⋯N1ⁱⁱ	0.93	2.60	3.277 (7)	130

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

Acknowledgments

AH greatfully acknowledges the the Higher Education Commission, Islamabad, Pakistan, for providing him with a scholarship under the Indigenous PhD Program (PIN 063–121531-PS3–127).

supplementary crystallographic information

Comment

In continuation of synthesizing various derivatives of 4-bromothiophene-2-carbaldehyde (Shafiq et al., 2009), the title compound (I, Fig. 1), has been prepared. The metal complexes of (I) have been prepared and the biological studies of all the compounds are in progress.

The crystal structure of (II) N'-((thiophen-3-yl)methylene)isonicotinohydrazide (Jing et al., 2007) and (III) (E)-N'-((5-methylthiophen-2-yl)methylene)isonicotinohydrazide (Wang et al., 2007) have been published. The title compound (I) differs from both due to substitution moiety of bromo.

We have recently reported the crystal structure of (IV) N'-[(E)-(4-bromothiophen-2-yl)methylidene]benzohydrazide (Shafiq et al., 2009). Due to change of benzene ring (IV) with the pyridine (I) ring, the crystal structure has been substantially changed. The title compound crystalizes with single molecule, whereas in (IV) there are two molecules along with fractional quantity of water. In (I), the dihedral angle between two aromatic rings A (C1—C3/N1/C4/C5) and B (C8—C11/S1) is 27.61 (14)°. The molecules of present compound are stabilized in the form of polymeric chains extending along the diagonal of crystallographic ac-plane. The list of strong H-bondings is given in Table 1. Due to the heterocyclic rings, the Br-Atom is disordered over two sites with occupancy ratio of 0.804:0.196. There exist R₂¹(6) ring motif (Bernstein et al., 1995) due to intermolecular H-bonding of type C—H···O and N—H···O (Fig. 2).

Experimental

To a hot stirred solution of isoniazid (1.37 g, 0.01 mol) in ethanol (15 ml) was added 4-bromothiophene-2-carbaldehyde (1.91 g, 0.01 mol). The resultant mixture was then heated under reflux. After an hour precipitates were formed. The reaction mixture was further heated about 30 min for the completion of the reaction which was monitored through TLC. Then it was allowed to cool to room temperature, filtered and washed with hot ethanol. The crude material was recrystallized in (1:3 v/v) 1,4-dioxan:ethanol, to afford light yellow needles of (I).