N-(2-Chloro­phen­yl)-N′-(2-methyl­phen­yl)succinamide

B S Saraswathi; Sabine Foro; B Thimme Gowda

doi:10.1107/S1600536811035616

. 2011 Sep 14;67(Pt 10):o2579. doi: 10.1107/S1600536811035616

N-(2-Chlorophenyl)-N′-(2-methylphenyl)succinamide

B S Saraswathi ^a, Sabine Foro ^b, B Thimme Gowda ^a,^*

PMCID: PMC3201445 PMID: 22065708

Abstract

In the title compound, C₁₇H₁₇ClN₂O₂, the asymmetric unit contains half a molecule with a centre of symmetry at the mid-point of the central C—C bond. The conformations of the amide O atoms are anti to the methylene atoms. Further, the N—H bonds in the amide fragments are anti to the ortho-chloro/methyl groups in the adjacent benzene rings. The dihedral angle between the benzene ring and the NH—C(O)—CH₂ segment in the two halves of the molecule is 62.0 (2)°. In the crystal, a series of N—H⋯O intermolecular hydrogen bonds link the molecules into column-like infinite chains along the a axis. The methyl and Cl groups are disordered with respect to the ortho positions of the benzene ring, with site-occupation factors of 0.5 each.

Related literature

For our studies on the effects of substituents on the structures of N-(aryl)-amides, see: Bhat & Gowda (2000 ▶); Gowda et al. (2007a ▶); Saraswathi et al. (2011a ▶,b ▶,c ▶); and on the structures of N-(aryl)-methanesulfonamides, see: Gowda et al. (2007b ▶). For similar structures, see: Pierrot et al. (1984 ▶). For restrained geometry, see: Nardelli (1999 ▶).

Experimental

Crystal data

C₁₇H₁₇ClN₂O₂
M _r = 316.78
Monoclinic,
a = 11.541 (3) Å
b = 7.908 (2) Å
c = 8.798 (2) Å
β = 102.55 (2)°
V = 783.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 293 K
0.48 × 0.04 × 0.04 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.889, T _max = 0.990
2598 measured reflections
1391 independent reflections
824 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.105
wR(F ²) = 0.164
S = 1.28
1391 reflections
112 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811035616/vm2112sup1.cif

e-67-o2579-sup1.cif^{(14.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035616/vm2112Isup2.hkl

e-67-o2579-Isup2.hkl^{(68.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811035616/vm2112Isup3.cml

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
N1—H1N⋯O1ⁱ	0.85 (2)	2.00 (2)	2.846 (5)	170 (5)

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Symmetry code: (i) Inline graphic .

Acknowledgments

BSS thanks the University Grants Commission, Government of India, New Delhi for the award of a research fellowship under its faculty improvement programme.

supplementary crystallographic information

Comment

The amide and sulfonamide moieties are important constituents of many biologically significant compounds. As part of our studies on the substituent effects on the structures of this class of compounds (Bhat & Gowda, 2000; Gowda et al., 2007a,b; Saraswathi et al., 2011a,b,c), in the present work, the structure of N-(2-Chlorophenyl),N-(2-methylphenyl)-succinamide (I) has been determined (Fig.1). The asymmetric unit of (I) contains half a molecule with a center of symmetry at the mid-point of the central C—C bond, similar to that obseved in bis(2-chlorophenylaminocarbonylmethyl)disulfide (II) (Pierrot et al., 1984), N-(3-Chlorophenyl),N-(3-methylphenyl)- succinamide (III) (Saraswathi et al., 2011c), N,N-bis(2-chlorophenyl)-succinamide (IV) (Saraswathi et al., 2011b) and N,N-bis(2-methylphenyl)-succinamide dihydrate (V) (Saraswathi et al., 2011a).

The conformations of the amide O atoms are anti to the H atoms attached to the adjacent C atoms. Further, the conformations of the N—H bonds in the amide fragments are anti to the ortho- chloro/methyl groups in the adjacent benzene rings, similar to that observed with respect to the meta-chloro/methyl groups in (III), and the anti conformations observed with respect to the ortho-methyl groups in (V), but contrary to the syn conformations observed between the N—H bonds in the amide fragments and the ortho-chloro groups in the adjacent benzene rings of (IV).

Further, C1—N1—C7—C8 and C1a—N1a—C7a—C8a segments in (I) are nearly linear, similar to those observed in (III), (IV) and (V). The torsion angles of C2—C1—N1—C7 and C6—C1—N1—C7 are -64.3 (8)° and 115.8 (6)°, compared to the values of -43.2 (4)° and 138.6 (3)° in (III), -47.6 (6)° and 133.7 (4)° in (IV) and -64.0 (4)° and 117.6 (3)° in (V).

The dihedral angle between the benzene ring and the NH—C(O)—CH₂ segment in the two halves of the molecule is 62.0 (2)°, compared to the values of 43.5 (1)° in (III), 47.0 (2)° in (IV) and 62.1 (2)° in (V).

The packing of molecules in the crystal linked by of N—H···O hydrogen bonds (Table 1) is shown in Fig. 2.

Experimental

Succinic anhydride (0.01 mol) in toluene (25 ml) was treated drop wise with 2-chloroaniline (0.01 mol) also in toluene (20 ml) with constant stirring. The resulting mixture was stirred for one hour and set aside for an additional hour at room temperature for completion of the reaction. The mixture was then treated with dilute hydrochloric acid to remove unreacted 2-chloroaniline. The resultant solid N-(2-chlorophenyl)-succinamic acid was filtered under suction and washed thoroughly with water to remove the unreacted succinic anhydride and succinic acid. The compound was recrystallized to constant melting point from ethanol. The purity of the compound was checked by elemental analysis and characterized by its infrared and NMR spectra.

The N-(2-chlorophenyl)succinamic acid obtained was then treated with phosphorous oxychloride and excess of 2-methylaniline at room temperature with constant stirring. The resultant mixture was stirred for 4 h, kept aside for additional 6 h for completion of the reaction and poured slowly into crushed ice with constant stirring. It was kept aside for a day. The resultant solid, N-(2-chlorophenyl), N-(2-methylphenyl)-succinamide was filtered under suction, washed thoroughly with water, dilute sodium hydroxide solution and finally with water. It was recrystallized to constant melting point from a mixture of acetone and toluene (3:1 v/v). The compound was characterized by its infrared and NMR spectra.

Needle like colorless single crystals used in X-ray diffraction studies were grown in a mixture of acetone and toluene (3:1 v/v) at room temperature.