N-(2,4,5-Trichloro­phen­yl)maleamic acid

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

doi:10.1107/S1600536809052520

. 2009 Dec 16;66(Pt 1):o182–o183. doi: 10.1107/S1600536809052520

N-(2,4,5-Trichlorophenyl)maleamic acid

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

PMCID: PMC2980077 PMID: 21580067

Abstract

The title compound, C₁₀H₆Cl₃NO₃, crystallizes with two independent molecules in the asymmetric unit. The molecular structure is stabilized by a short intramolecular O—H⋯O hydrogen bond within the maleamic unit. In the crystal, each molecule self-associates via N—H⋯O hydrogen bonds into chains, each running along the b axis. Two short intermolecular Cl⋯O contacts [3.1267 (15) and 3.0523 (12) Å] and C—H⋯O interactions interconnect these chains into a three-dimensional network.

Related literature

For studies on the effect of ring- and side-chain substitutions on the crystal structures of amides, see: Gowda et al. (2009 ▶, 2010 ▶); Lo & Ng (2009 ▶); Prasad et al. (2002 ▶); Shakuntala et al. (2009 ▶). For the concept of orthogonality of halogen and hydrogen bonds, see: Voth et al. (2009 ▶). For a review on short halogen–oxygen contacts, see: Fourmigué (2009 ▶); Kubicki (2004 ▶).

Experimental

Crystal data

C₁₀H₆Cl₃NO₃
M _r = 294.51
Monoclinic,
a = 10.8979 (2) Å
b = 11.0225 (2) Å
c = 19.4739 (3) Å
β = 95.4761 (9)°
V = 2328.57 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.78 mm⁻¹
T = 295 K
0.34 × 0.25 × 0.22 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Ruby Gemini detector
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.794, T _max = 0.852
49446 measured reflections
4424 independent reflections
3825 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.079
S = 1.06
4424 reflections
315 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.32 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/S1600536809052520/tk2591sup1.cif

e-66-0o182-sup1.cif^{(21.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809052520/tk2591Isup2.hkl

e-66-0o182-Isup2.hkl^{(212.4KB, 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
O2—H2A⋯O1	0.82	1.69	2.5080 (15)	175
O5—H5A⋯O4	0.82	1.72	2.5332 (17)	175
N1—H1N⋯O3ⁱ	0.77 (2)	2.30 (2)	3.0356 (18)	161.2 (19)
N2—H2N⋯O6ⁱⁱ	0.81 (2)	2.481 (19)	3.0775 (19)	131.3 (16)
N1—H1N⋯Cl1	0.77 (2)	2.56 (2)	2.9628 (14)	114.2 (17)
N2—H2N⋯Cl4	0.81 (2)	2.519 (18)	2.9476 (14)	114.3 (15)
C2—H2⋯O3ⁱ	0.93	2.29	3.123 (2)	149
C12—H12⋯O2	0.93	2.47	3.330 (2)	154

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

Table 2. Halogen-bond geometry (Å, °).

C—Cl⋯O	Cl⋯O	C—Cl⋯O
C9—Cl3⋯O6ⁱⁱⁱ	3.1267 (15)	158.99 (6)
C16—Cl4⋯O1	3.0523 (12)	159.62 (7)

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Symmetry code: (iii) 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. KS 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

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 et al., 2009, 2010; Shakuntala et al., 2009; Prasad et al., 2002), the crystal structure of N-(2,4,5-trichlorophenyl)-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 the amide-O atom and the carbonyl-O atom of the acid segment are also anti to each other. Further, the amide-O atom is anti to the H atom attached to the adjacent C atom, while the carbonyl-O atom is syn to the H atom attached to its adjacent C atom (Fig.1). In the structure, a rare anti conformation of the C=O and O—H bonds of the acid group has been observed, similar to that observed in N-phenylmaleamic acid (Lo & Ng, 2009), N-(2,5-dichlorophenyl)maleamic acid (Shakuntala et al., 2009), N-(3,5-dichlorophenyl)maleamic acid (Gowda et al., 2010) and N-(2,4,6-dimethylphenyl)maleamic acid (Gowda et al., 2009). Further, the conformation of the N—H bond is syn to the 2-Cl in the phenyl ring, while it is anti to the 5-Cl in the ring. Each maleamic unit includes a short intramolecular hydrogen O—H···O bond (Table 1). The bond lengths of C2–C3 and C12–C13 (i.e. 1.329 (2) and 1.328 (2) Å) clearly indicate double bond character.

In both the molecules, the dihedral angle between the amido group –NHCO– and the tri-substituted phenyl ring is 6.1 (3)°. The two N—H···O hydrogen bonds have quite different geometry, as seen in the N—H···O angles (Table 1). Remarkably small N2—H2N···O6ⁱⁱ angle of 131.3 (16)° can be attributed to the competing effect of the neighbouring C9—Cl3···O6ⁱⁱⁱ halogen bond. The angle Cl3···O6ⁱⁱⁱ···H2N =78.24 (6)° is close to 90° and can be interpreted within the concept of orthogonality of halogen and hydrogen bonds (Voth et al., 2009). The N1—H1N···O3ⁱ hydrogen bond with the angle of 161.2 (19)° is much less influenced by the near C6—Cl1···O3ⁱ halogen bond, which is weaker as indicated by the Cl1···O3ⁱ contact of 3.2372 (13) A. [Symmetry codes: (i) -x + 1, y + 1/2, -z + 3/2; (ii) -x, y + 1/2, -z + 3/2; (iii) x, -y + 1/2, z - 1/2.]

In the crystal of (I), the intermolecular N–H···O hydrogen bonds link the molecules, which self-associate, into infinite chains running along the b axis. These chains are connected through relatively short Cl···O contacts: Cl4···O1 =3.0523 (12), Cl3···O6(iii) =3.1267 (15) Å. [Symmetry codes: (iii) x, -y + 1/2, z - 1/2].(iii) x, -y + 1/2, z - 1/2] as well as C–H···O contacts to consolidate the crystal packing. Fig. 2 outlines part of the crystal structure of (I) with the N–H···O hydrogen bonding and Cl···O contacts highlighted. The data for the C–Cl···O halogen bonds are in agreement with others (Kubicki, 2004; Fourmigué, 2009).

Experimental

The solution of maleic anhydride (0.025 mol) in toluene (25 ml) was treated drop-wise with the solution of 2,4,5-trichloroaniline (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 2,4,5-trichloroaniline. The resultant solid N-(2,4,5-trichlorophenyl)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.