N′-[(3-Methyl-2-thien­yl)carbon­yl]isonicotinohydrazide

H S Naveenkumar; Amirin Sadikun; Pazilah Ibrahim; Jia Hao Goh; Hoong-Kun Fun

doi:10.1107/S1600536809033030

. 2009 Aug 26;65(Pt 9):o2235–o2236. doi: 10.1107/S1600536809033030

N′-[(3-Methyl-2-thienyl)carbonyl]isonicotinohydrazide

H S Naveenkumar ^a, Amirin Sadikun ^a,^‡, Pazilah Ibrahim ^a, Jia Hao Goh ^b, Hoong-Kun Fun ^b,^*,^§

PMCID: PMC2969908 PMID: 21577634

Abstract

In the title compound, C₁₂H₁₁N₃O₂S, the pyridine ring is inclined to the thiophene ring, forming a dihedral angle of 34.96 (7)°. The mean plane through the hydrazide unit forms dihedral angles of 21.57 (8) and 53.08 (8)°, respectively, with the pyridine and thiophene rings. The two O atoms are twisted away from each other, as indicated by the C—N—N—C torsion angle of −81.27 (15)°. In the crystal structure, molecules are linked into an extended three-dimensional network by intermolecular N—H⋯N, N—H⋯O and C—H⋯O hydrogen bonds. The crystal structure also features a short S⋯O [3.2686 (10) Å] interaction and a weak intermolecular C—H⋯π interaction.

Related literature

For general background to and application of isoniazid derivatives, see: Janin (2007 ▶); Maccari et al. (2005 ▶); Slayden et al. (2000 ▶). For the preparation of the title compound, see: Besra et al. (1993 ▶). For bond-length data, see: Allen et al. (1987 ▶). For a closely related structure, see: Naveenkumar et al. (2009 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₂H₁₁N₃O₂S
M _r = 261.30
Orthorhombic,
a = 8.9206 (1) Å
b = 10.7552 (2) Å
c = 12.4934 (2) Å
V = 1198.65 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 100 K
0.58 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.861, T _max = 0.961
17333 measured reflections
4355 independent reflections
4078 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.097
S = 1.05
4355 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.43 e Å⁻³
Absolute structure: Flack (1983 ▶), 1856 Friedel pairs
Flack parameter: −0.04 (6)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033030/is2451sup1.cif

e-65-o2235-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033030/is2451Isup2.hkl

e-65-o2235-Isup2.hkl^{(213.4KB, 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—H1N2⋯N1ⁱ	0.86	2.14	2.9068 (17)	149
N3—H1N3⋯O2ⁱⁱ	0.86	1.99	2.8034 (15)	158
C4—H4A⋯O1ⁱⁱⁱ	0.93	2.58	3.2047 (17)	125
C10—H10A⋯O2^iv	0.93	2.51	3.3928 (19)	159
C11—H11A⋯Cg1^v	0.93	2.80	3.3760 (17)	121

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) . Cg1 is centroid of the C1/C2/N1/C3–C5 ring.

Acknowledgments

This research was supported by Universiti Sains Malaysia (USM) under the University Research Grant (No. 1001/PFARMASI/815005). HKF and JHG thank USM for the Research University Golden Goose Grant (No. 1001/PFIZIK/811012). HSNK and JHG thank USM for the award of a USM Fellowship.

supplementary crystallographic information

Comment

In the search of new compounds, isoniazid derivatives have been found to possess potential tuberculostatic activity (Janin, 2007; Maccari et al., 2005; Slayden et al., 2000). As a part of a current work on synthesis of such derivatives, in this paper we present the crystal structure of the title compound, (I) which was synthesized in our lab.

In (I), the pyridine ring (C1/C2/N1/C3-C5) is inclined to the thiophene ring (C8-C11/S1), forming a dihedral angle of 34.96 (7)° (Fig. 1). The mean plane through the hydrazide unit (C7/N2/N3/O2) forms dihedral angles of 21.57 (8) and 53.08 (8)°, respectively, with the pyridine and thiophene rings. The O1 and O2 atoms are twisted away from each other as indicated by torsion angle C6–N2–N3–C7 [-81.27 (15)°]. The bond lengths (Allen et al., 1987) and angles are comparable to a closely related structure (Naveenkumar et al., 2009).

In the crystal structure (Fig. 2), the molecules are linked into an extended three-dimensional network by intermolecular C4—H4A···O1, C10—H10A···O2, N2—H1N2···N1 and N3—H1N3···O2 hydrogen bonds (Table 1). The crystal structure is further stabilized by short S1···O2 interactions of 3.2686 (10) Å [symmetry code: 1/2+x, 3/2-y, -z] and by weak intermolecular C11—H11A···Cg1 interactions (Table 1; Cg1 is the centroid of the pyridine ring).

Experimental

Compound (I) was prepared following the procedure by literature (Besra et al., 1993). Dry dichloromethane (30 ml) and 4-dimethylaminopyridine (4-DMAP) (1.2 eq) was added to 3-methylthiophene-2-carbonyl chloride followed by isoniazid (1.1 eq). The reaction mixture was kept in an ice bath for 1 h and then left stirring under nitrogen atmosphere overnight at room temperature. Dichloromethane (20 ml) was added to the reaction mixture, which was then washed with water, and the organic layer dried over anhydrous sodium sulphate. The solvent was removed under reduced pressure to afford the crude product which was purified by column chromatography and recrystallized from ethanol to afford colorless single crystals.