N-(2,5-Dichloro­phen­yl)maleamic acid

K Shakuntala; B Thimme Gowda; Miroslav Tokarčík; Jozef Kožíšek

doi:10.1107/S1600536809048715

. 2009 Nov 18;65(Pt 12):o3119. doi: 10.1107/S1600536809048715

N-(2,5-Dichlorophenyl)maleamic acid

K Shakuntala ^a, B Thimme Gowda ^a,^*, Miroslav Tokarčík ^b, Jozef Kožíšek ^b

PMCID: PMC2972031 PMID: 21578844

Abstract

The asymmetric unit of the title compound, C₁₀H₇Cl₂NO₃, contains two independent molecules. The molecular conformation of each maleamic unit is stabilized by an intramolecular O—H⋯O_carbonyl hydrogen bond owing to the anti disposition of the participating entities. The mean planes through the benzene ring and the amido group are inclined at angles of 45.7 (1) and 40.8 (1)° in the two molecules. In the crystal, the independent molecules self-associate via N—H⋯O hydrogen bonds into zigzag ribbons propagating along the a axis. The ribbons are weakly coupled by C—H⋯π and C—H⋯O interactions.

Related literature

For related structures, see: Gowda, Foro et al. (2009 ▶); Gowda, Tokarčík et al. (2009a ▶,b ▶); Leiserowitz (1976 ▶); Lo & Ng (2009 ▶); Prasad et al. (2002 ▶). graphic file with name e-65-o3119-scheme1.jpg

Experimental

Crystal data

C₁₀H₇Cl₂NO₃
M _r = 260.07
Orthorhombic,
a = 13.1618 (2) Å
b = 14.6993 (2) Å
c = 22.8406 (3) Å
V = 4418.95 (11) Å³
Z = 16
Mo Kα radiation
μ = 0.58 mm⁻¹
T = 295 K
0.40 × 0.33 × 0.24 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction: analytical (CrysAlis Pro ; Oxford Diffraction, 2009 ▶) T _min = 0.836, T _max = 0.892
61823 measured reflections
4191 independent reflections
3514 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.079
S = 1.08
4191 reflections
289 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: CrysAlis Pro (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis Pro ; data reduction: CrysAlis Pro ; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2002 ▶); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009 ▶) and WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809048715/tk2578sup1.cif

e-65-o3119-sup1.cif^{(20.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809048715/tk2578Isup2.hkl

e-65-o3119-Isup2.hkl^{(201.3KB, 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
N1—H1N⋯O3ⁱ	0.86	2.07	2.8938 (17)	160
N2—H2N⋯O6ⁱⁱ	0.86	2.09	2.9263 (17)	164
O2—H2A⋯O1	0.82	1.68	2.4979 (15)	175
O5—H5A⋯O4	0.82	1.68	2.4846 (15)	166
C7—H7⋯Cg2	0.93	2.77	3.6745 (15)	163
C18—H18⋯O5ⁱⁱⁱ	0.93	2.58	3.4186 (19)	151

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg2 is the centroid of the C15–C20 ring.

Acknowledgments

MT and JK thank the Grant Agency of the Slovak Republic (VEGA 1/0817/08) and Structural Funds, Interreg IIIA, for financial support in purchasing the diffractometer.

supplementary crystallographic information

Comment

As a part of studying the effect of ring- and side-chain substitutions on the crystal structures of biologically significant amides (Gowda, Foro et al., 2009; Gowda, Tokarčík et al., 2009a,b; Prasad et al., 2002), the crystal structure of N-(2,5-dichlorophenyl)-maleamic acid (I) has been determined. The asymmetric unit of (I) contains two independent molecules (Fig. 1). The conformations of the N—H and C=O bonds in the amide segment of the structure are anti to each other, and those of the amide-O atom and the carbonyl-O atom of the acid segment are also anti to each other. The anti conformation of the C=O and O—H bonds of the acid group is comparatively rare and has been observed previously in N-phenylmaleamic acid (Lo & Ng, 2009), N-(2,6-dimethylphenyl)maleamic acid (Gowda, Tokarčík et al., 2009a), and N-(3,4-dimethylphenyl)maleamic acid (Gowda, Tokarčík et al., 2009b). The various modes of interlinking carboxylic acids by hydrogen bonds is described elsewhere (Leiserowitz, 1976). Each maleamic moiety includes a short intramolecular hydrogen O–H···O bond (Table 1). The mean planes through the phenyl ring and the amido group –NHCO– form dihedral angles of 45.7 (1) and 40.8 (1) ° in the first and second molecules, respectively. All non-hydrogen atoms of the maleamic moiety in the first molecule fit very well to a plane, having the r.m.s. deviation of fitted atoms 0.013 Å. The mean plane through the maleamic moiety in the second molecule has a r.m.s. deviation of 0.098 Å. In the crystal structure, intermolecular N–H···O hydrogen bonds link self-associated molecules into two distinct zig-zag ribbons propagating in the [1 0 0] direction (Fig. 2). These ribbons are weakly coupled by a C—H···π interaction, with atom C7-H acting as the donor and the aryl ring C15—C20 as the acceptor. The centroid of the C15—C20 ring is denoted Cg2 in the Table 1.

Experimental

A solution of maleic anhydride (0.025 mol) in toluene (25 ml) was treated drop-wise with a solution of 2,5-dichloroaniline (0.025 mol) also in toluene (20 ml) with constant stirring. The resulting mixture was warmed with stirring for 30 min and set aside for an additional 30 min at room temperature for completion of the reaction. The mixture was then treated with dilute hydrochloric acid to remove the unreacted 2,5-dichloroaniline. The resultant solid N-(2,5-dichlorophenyl)maleamic acid was filtered under suction and washed thoroughly with water to remove the unreacted maleic anhydride and maleic acid. It was recrystallized to constant melting point from ethanol. Colourless crystals were grown by slow evaporation (room temperature) of an ethanol solution of (I).