N-(3,5-Dichloro­phen­yl)maleamic acid

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

doi:10.1107/S1600536809051484

. 2009 Dec 4;66(Pt 1):o51. doi: 10.1107/S1600536809051484

N-(3,5-Dichlorophenyl)maleamic acid

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

PMCID: PMC2980102 PMID: 21580154

Abstract

In the title compound, C₁₀H₇Cl₂NO₃, the asymmetric unit contains four independent molecules, which are linked to each other by N—H⋯O hydrogen bonds. The molecular structure is stabilized by a short intramolecular O—H⋯O hydrogen bond within each maleamic acid unit. In the crystal, the molecules are linked into networks through N—H⋯O hydrogen bonds and intermolecular C—Cl⋯O=C contacts [Cl⋯O = 3.0897 (12) and 3.0797 (13) Å].

Related literature

For studies on the effect of ring- and side-chain substitutions on the crystal structures of amides, see: Gowda, Foro et al. (2009 ▶); Gowda, Tokarčík et al. (2009 ▶); Lo & Ng (2009 ▶); Prasad et al. (2002 ▶); Shakuntala et al. (2009 ▶). For short halogen–oxygen contacts, see: Fourmigué (2009 ▶). Kubicki (2004 ▶).

Experimental

Crystal data

C₁₀H₇Cl₂NO₃
M _r = 260.07
Triclinic,
a = 8.13786 (12) Å
b = 16.5293 (3) Å
c = 17.4170 (3) Å
α = 103.4502 (17)°
β = 100.6466 (15)°
γ = 99.5964 (15)°
V = 2184.79 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.58 mm⁻¹
T = 295 K
0.59 × 0.51 × 0.22 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction: analytical (CrysAlis PRO, Oxford Diffraction, 2009 ▶) T _min = 0.728, T _max = 0.887
46919 measured reflections
8204 independent reflections
6694 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.088
S = 1.09
8204 reflections
581 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.38 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/S1600536809051484/dn2519sup1.cif

e-66-00o51-sup1.cif^{(27.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809051484/dn2519Isup2.hkl

e-66-00o51-Isup2.hkl^{(393.2KB, 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
N11—H11⋯O33ⁱ	0.86	2.07	2.9254 (17)	172
N21—H21⋯O13	0.86	2.05	2.8748 (18)	161
N31—H31⋯O43	0.86	2.09	2.9244 (19)	165
N41—H41⋯O23	0.86	2.07	2.9186 (18)	168
O12—H12A⋯O11	0.82	1.65	2.4680 (18)	175
O22—H22A⋯O21	0.82	1.64	2.4613 (17)	177
O32—H32A⋯O31	0.82	1.66	2.4772 (17)	177
O42—H42A⋯O41	0.82	1.65	2.4684 (18)	172

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Symmetry code: (i) Inline graphic .

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

In the present work, 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., 2009; Shakuntala et al., 2009; Prasad et al., 2002), the crystal structure of N-(3,5-dichlorophenyl)maleamic acid (I) has been determined.

The asymmetric unit of (I) contains four independent molecules linked to each other through N-H···O intermolecular hydrogen bonds(Table 1, 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. But the amide O atom is anti to the H atom attached to the adjacent C atom, while the carboxyl O atom is syn to the H atom attached to its adjacent C atom (Fig.1). In the structure of (I), relatively rare anti conformation of the C=O and O—H bonds of the acid group has been observed, similar to that obsrved in N-phenylmaleamic acid (Lo & Ng, 2009), N-(3,4-dimethylphenyl)maleamic acid, N-(2,4,6-trimethylphenyl)- maleamic acid (Gowda,Tokarčík et al., 2009) and N-(2,5-dichlorophenyl)maleamic acid (Shakuntala et al., 2009).

Each maleamic unit includes a short intramolecular hydrogen O—H···O bond (Table 1). Bond lengths C12–C13 =1.329 (2), C22–C23 =1.336 (2), C32–C33 =1.335 (2) and C42–C43 =1.329 (2)Å clearly indicate the double bond character.

The dihedral angles between the dichloro-substituted phenyl ring and the amido group –NHCO– are 4.5 (3), 8.4 (2), 10.4 (2) and 8.3 (3)° in the four independent molecules.

In the crystal structure, the intermolecular N–H···O hydrogen bonds link the molecules into infinite chain running parallel to the [-1 1 1] vector. The relatively short Cl···O contacts build up a two-dimensional network. Part of the crystal structure is shown in Fig. 2. The molecule containing the amido atom N11 forms an inversion dimer, which is is stabilized by two short Cl···O contacts with the length of 3.0897 (12)Å. Another short Cl···O contact between the atoms Cl12 and O41(iii) has the length of 3.0797 (13) Å. [Symmetry code (iii): x, y-1, z-1].

Our data for the C–Cl···O halogen bonds are in agreement with the observations of others (Kubicki, 2004; Fourmigué 2009).

Experimental

The solution of maleic anhydride (0.025 mol) in toluene (25 ml) was treated dropwise with the solution of 3,5-dichloroaniline (0.025 mol) also in toluene (20 ml) with constant stirring. The resulting mixture was warmed with stirring for over 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 3,5-dichloroaniline. The resultant solid N-(3,5-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. The purity of the compound was checked by elemental analysis and characterized by its infrared spectra. Colourless single crystals used in X-ray diffraction studies were grown in an ethanol solution by slow evaporation at room temperature.