(E)-2-(2,3-Dimethyl­anilino)-N′-(thio­phen-2-yl­methyl­idene)benzohydrazide

Hoong-Kun Fun; Tze Shyang Chia; Mashooq A Bhat; Mohamed A Al-Omar; Hatem A Abdel-Aziz

doi:10.1107/S160053681203259X

. 2012 Jul 25;68(Pt 8):o2524–o2525. doi: 10.1107/S160053681203259X

(E)-2-(2,3-Dimethylanilino)-N′-(thiophen-2-ylmethylidene)benzohydrazide

Hoong-Kun Fun ^a,^*,^‡, Tze Shyang Chia ^a, Mashooq A Bhat ^b, Mohamed A Al-Omar ^b, Hatem A Abdel-Aziz ^b

PMCID: PMC3414973 PMID: 22904960

Abstract

In the title compound, C₂₀H₁₉N₃OS, the central benzene ring makes dihedral angles of 45.36 (9) and 55.33 (9)° with the thiophene ring and the dimethyl-substituted benzene ring, respectively. The dihedral angle between the thiophene ring and dimethyl-substituted benzene ring is 83.60 (9)°. The thiophene ring and the benzene ring are twisted from the mean plane of the C(=O)—N—N=C bridge [maximum deviation = 0.0860 (13) Å], with dihedral angles of 23.86 (9) and 24.77 (8)°, respectively. An intramolecular N—H⋯O hydrogen bond generates an S(6) ring. In the crystal, molecules are linked by N—H⋯O and C—H⋯O hydrogen bonds to the same acceptor atom, forming sheets lying parallel to the bc plane. The crystal packing also features C—H⋯π interactions.

Related literature

For background to the chemistry and biological activity of diaryl amines, see: Reddy et al. (2010 ▶). For related structures, see: Bhat et al. (2012a ▶,b ▶,c ▶); Wang et al. (2010 ▶); Tian et al. (2010 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For reference bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₂₀H₁₉N₃OS
M _r = 349.44
Monoclinic,
a = 14.0922 (14) Å
b = 15.9682 (15) Å
c = 8.1338 (8) Å
β = 105.344 (2)°
V = 1765.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 100 K
0.34 × 0.07 × 0.04 mm

Data collection

Bruker APEX DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.936, T _max = 0.992
14626 measured reflections
5082 independent reflections
3338 reflections with I > 2σ(I)
R _int = 0.067

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.128
S = 1.01
5082 reflections
236 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 datablock(s) global, I. DOI: 10.1107/S160053681203259X/hb6898sup1.cif

e-68-o2524-sup1.cif^{(27.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681203259X/hb6898Isup2.hkl

e-68-o2524-Isup2.hkl^{(248.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681203259X/hb6898Isup3.cml

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

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

Cg1 and Cg2 are the centroids of the S1/C15–C18 and C1–C6 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O1ⁱ	0.89 (2)	1.96 (2)	2.808 (2)	160 (2)
N1—H1N1⋯O1	0.85 (2)	2.02 (3)	2.704 (2)	137 (2)
C1—H1A⋯O1ⁱⁱ	0.95	2.58	3.410 (2)	146
C3—H3A⋯Cg1ⁱⁱⁱ	0.95	2.98	3.732 (2)	137
C9—H9A⋯Cg2^iv	0.95	2.84	3.649 (2)	144

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

Acknowledgments

HKF and TSC thank Universiti Sains Malaysia (USM) for a Research University Grant (No. 1001/PFIZIK/811160). TSC thanks the Malaysian government and USM for the award of a Research Fellowship. The authors thank the Deanship of Scientific Research and the Research Center, College of Pharmacy, King Saud University, for funding and facilities.

supplementary crystallographic information

Comment

In view of the importance of the chemistry and biological activity of diaryl amines (Reddy et al., 2010) and in continuation to our interest in the chemistry of hydrazones (Bhat et al., 2012a,b,c), we report herein the crystal structure of the title compound.

The asymmetric unit of the title compound is shown in Fig. 1. The central benzene ring [C7–C12] makes dihedral angles of 45.36 (9)° and 55.33 (9)° with the thiophene ring [S1/C15–C18] and dimethyl-substituted benzene ring [C1–C6], respectively. The dihedral angle between the thiophene ring and C1–C6 benzene ring is 83.60 (9)°. The thiophene ring and C7–C12 benzene ring are twisted from the mean plane of C13(═O1)—N2—N3═C14 bridge [maximum deviation = 0.0860 (13) Å at atom N3] with dihedral angles of 23.86 (9)° and 24.77 (8)°, respectively. An intramolecular N1—H1N1···O1 hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995) in the molecule. Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to those found in related structures (Tian et al., 2010; Wang et al., 2010).

In the crystal (Fig. 2), molecules are linked by N2—H1N2···O1 and C1—H1A···O1 hydrogen bonds, with the same O atom acting as the acceptor, into sheets parallel to bc plane. The crystal packing also features C—H···π interactions (Table 1), involving Cg1 and Cg2 which are the centroids of S1/C15–C18 and C1–C6 rings, respectively.

Experimental

The title compound was prepared by the reaction of thiophene-2-carbaldehyde (0.11 g, 1 mmol) and 2-[(2,3-dimethylphenylamine)]benzohydrazide (0.25 g, 1 mmol) in ethanol (25 ml). After stirring at room temperature for 3 h, the resulting mixture was concentrated under reduced pressure. The precipitate was washed with cold ethanol to afford the title compound. Yellow needles were recrystallized from ethanol solution by the slow evaporation of the solvent at room temperature after several days.