N,N′-Bis(3-chloro­phen­yl)malonamide

Vinola Z Rodrigues; Sabine Foro; B Thimme Gowda

doi:10.1107/S1600536811031333

. 2011 Aug 11;67(Pt 9):o2278. doi: 10.1107/S1600536811031333

N,N′-Bis(3-chlorophenyl)malonamide

Vinola Z Rodrigues ^a, Sabine Foro ^b, B Thimme Gowda ^a,^*

PMCID: PMC3200632 PMID: 22058926

Abstract

The asymmetric unit of the title compound, C₁₅H₁₂Cl₂N₂O₂, contains two independent molecules. In both independent molecules, the N—H bond in one of the amide fragments is anti to the meta-chloro group of the adjacent benzene ring and that in the other amide group is syn to the other meta-chloro group. Furthermore, in both molecules, each amide group is almost coplanar with the adjacent phenyl ring, making dihedral angles of 10.5 (2) and 8.7 (2)° in one molecule and 9.0 (2) and 9.6 (2)° in the other. The planes of the amide groups are inclined at dihedral angles of 83.4 (1) and 87.4 (1)° in the two molecules. In the crystal, molecules are linked into a chain by intermolecular N—H⋯O hydrogen bonds.

Related literature

For our studies on the effects of substituents on the structures and other aspects of N-(aryl)-amides, see: Arjunan et al. (2004 ▶); Gowda et al. (2010 ▶); Saraswathi et al. (2011 ▶), on N-(aryl)-methanesulfonamides, see: Gowda et al. (2007 ▶) and on N-chloro-arylsulfonamides, see: Gowda & Kumar (2003 ▶).

Experimental

Crystal data

C₁₅H₁₂Cl₂N₂O₂
M _r = 323.17
Monoclinic,
a = 10.9209 (8) Å
b = 16.416 (1) Å
c = 17.490 (1) Å
β = 105.260 (6)°
V = 3025.0 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 293 K
0.48 × 0.28 × 0.24 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.819, T _max = 0.903
12003 measured reflections
5164 independent reflections
2767 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.114
S = 0.96
5164 reflections
391 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.29 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/S1600536811031333/nc2242sup1.cif

e-67-o2278-sup1.cif^{(24.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811031333/nc2242Isup2.hkl

e-67-o2278-Isup2.hkl^{(252.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811031333/nc2242Isup3.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⋯O3	0.84 (2)	2.11 (2)	2.950 (3)	176 (3)
N2—H2N⋯O4ⁱ	0.87 (2)	2.11 (2)	2.961 (3)	169 (3)
N3—H3N⋯O1ⁱⁱ	0.85 (2)	2.09 (2)	2.939 (3)	173 (2)
N4—H4N⋯O2	0.85 (2)	2.12 (2)	2.947 (3)	168 (3)

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

Acknowledgments

VZR thanks the University Grants Commission, Government of India, New Delhi, for award of an RFSMS research fellowship.

supplementary crystallographic information

Comment

The amide and sulfonamide moieties are important constituents of many biologically significant compounds. As a part of studying the substituent effects on the structures and other aspects of N-(aryl)-amides (Arjunan et al., 2004, Gowda et al., 2010, Saraswathi et al., 2011); N-(aryl)-methanesulfonamides (Gowda et al., 2007) and N-chloro-arylsulfonamides (Gowda & Kumar, 2003), in the present work, the structure of N,N-bis(3-chlorophenyl)-malonamide (I) has been determined (Fig.1). The asymmetric unit of (I) contains two independent molecules. The conformations of all the N—H, C=O and C—H bonds in the central amide and aliphatic segments are anti to their adjacent bonds. Further, in both of the independent molecules, the N—H bonds in the amide fragments are anti to the meta-chloro groups in one of the adjacent benzene rings and syn to the meta-chloro group in the other, in contrast to the syn conformations of the N—H bonds with respect to the meta-methyl groups in the adjacent benzene rings of N,N-bis(3-methylphenyl)-malonamide (II)(Gowda et al., 2010) and anti conformations of the N—H bonds with respect to the meta-chloro groups in N,N- bis(3-chlorophenyl)-succinamide (III) (Saraswathi et al., 2011).

In the geometry of the molecule, each amide group is almost coplanar with the adjacent phenyl rings, as indicated by the dihedral angles of 10.5 (2)°, 8.7 (2)° (molecule 1) and 9.0 (2)°, 9.6 (2)° (molecule 2), compared to the value of 9.2 (2)° in (II). The planes of amide groups are inclined at angles of 83.4 (1)° (molecule 1) and 87.4 (1)° (molecule 2), in contrast to the value of 68.5 (1)° in (II). The phenyl rings of the two molecules make a dihedral angle of 21.5 (1)°.

In the crystal, the molecules are linked into chains by intermolecular N–H···O hydrogen bonding as shown in Fig. 2 (Table 1) .

Experimental

Malonic acid (0.3 mol) in dichloromethane (30 ml) was treated with m-chloroaniline (0.6 mol) in dichloromethane (30 ml), dropwise with stirring. The resulting mixture was stirred for 3 hrs and kept aside for 12 hrs for the completion of reaction and evaporation of the solvent, dichloromethane. The product obtained was added to crushed ice to obtain the precipitate. The latter was thoroughly washed with water and then with saturated sodium bicarbonate solution and washed again with water. It was then given a wash with 2 N HCl. It was again washed with water, filtered, dried and recrystallized to the constant melting point from ethanol.

Prism like colorless single crystals of the title compound used in X-ray diffraction studies were obtained by a slow evaporation of its ehanolic solution at room temperature.