N-(4-Chloro-2-methyl-phen-yl)maleamic acid.

In the mol-ecular structure of the title compound, C(11)H(10)ClNO(3), the conformation of the N-H bond in the amide segment is syn to the ortho-methyl group in the phenyl ring. The C=O and O-H bonds of the acid group are in the relatively rare anti position with respect to each other. This is an obvious consequence of the hydrogen bond donated to the amide carbonyl group. The central oxobutenoic acid core C(=O)-C=C-C-OH is twisted by 31.65 (6)° out of the plane of the 4-chloro-2-methyl-phenyl ring. An intra-molecular O-H⋯O hydrogen bond occurs. In the crystal, N-H⋯O hydrogen bonds link the mol-ecules into infinite chains running along the a axis.

Related literature

For studies on the effects of substituents on the structures and other aspects of N-(ar­yl)-amides, see: Gowda et al. (2000 ▶, 2010 ▶); Prasad et al. (2002 ▶), on N-(ar­yl)-methane­sulfonamides, see: Jayalakshmi & Gowda (2004 ▶), on N-(ar­yl)-aryl­sulfonamides, see: Shetty & Gowda (2005 ▶) and on N-chloro­aryl­sulfonamides, see: Gowda & Kumar (2003 ▶). For modes of inter­linking carb­oxy­lic acids by hydrogen bonds, see: Leiserowitz (1976 ▶)

Experimental

Crystal data

C11H10ClNO3

M = 239.65

Orthorhombic,

a = 12.1310 (11) Å

b = 7.3990 (7) Å

c = 25.466 (2) Å

V = 2285.7 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.33 mm−1

T = 295 K

0.45 × 0.35 × 0.25 mm

Data collection

Oxford Diffraction Xcalibur diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.865, T max = 0.918

17740 measured reflections

1819 independent reflections

1642 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.089

S = 1.02

1819 reflections

154 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.19 e Å−3

Δρmin = −0.27 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: DIAMOND (Brandenburg, 2002 ▶); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009 ▶) and WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811047817/bq2317sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811047817/bq2317Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811047817/bq2317Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C11H10ClNO3	Dx = 1.393 Mg m−3
Mr = 239.65	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 1819 reflections
a = 12.1310 (11) Å	θ = 3.6–24.4°
b = 7.3990 (7) Å	µ = 0.33 mm−1
c = 25.466 (2) Å	T = 295 K
V = 2285.7 (3) Å3	Plate, colourless
Z = 8	0.45 × 0.35 × 0.25 mm
F(000) = 992

Oxford Diffraction Xcalibur diffractometer	1819 independent reflections
Radiation source: fine-focus sealed tube	1642 reflections with I > 2σ(I)
graphite	Rint = 0.025
Detector resolution: 0 pixels mm-1	θmax = 24.4°, θmin = 3.6°
ω scans with κ offsets	h = −14→13
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −8→8
Tmin = 0.865, Tmax = 0.918	l = −29→28
17740 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0445P)2 + 0.9459P] where P = (Fo2 + 2Fc2)/3
1819 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.19 e Å−3
2 restraints	Δρmin = −0.27 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
C1	0.29051 (13)	0.3610 (2)	0.08033 (7)	0.0428 (4)
C2	0.31769 (14)	0.3019 (3)	0.02624 (7)	0.0485 (5)
H2	0.3925	0.2917	0.0188	0.058*
C3	0.25011 (15)	0.2612 (3)	−0.01329 (6)	0.0505 (5)
H3	0.2860	0.2317	−0.0444	0.061*
C4	0.12845 (15)	0.2543 (3)	−0.01670 (7)	0.0496 (5)
C5	0.37645 (12)	0.4444 (2)	0.16488 (6)	0.0368 (4)
C6	0.46315 (13)	0.5525 (2)	0.18298 (6)	0.0383 (4)
C7	0.46319 (14)	0.6020 (2)	0.23578 (6)	0.0431 (4)
H7	0.5205	0.6723	0.2489	0.052*
C8	0.37918 (14)	0.5481 (2)	0.26889 (6)	0.0410 (4)
C9	0.29334 (14)	0.4439 (2)	0.25077 (7)	0.0449 (4)
H9	0.2366	0.4097	0.2732	0.054*
C10	0.29265 (14)	0.3907 (2)	0.19860 (7)	0.0429 (4)
H10	0.2357	0.3185	0.1861	0.051*
C11	0.55428 (15)	0.6166 (3)	0.14712 (7)	0.0517 (5)
H11A	0.5937	0.5141	0.1336	0.078*
H11B	0.6039	0.6927	0.1664	0.078*
H11C	0.5231	0.6837	0.1185	0.078*
N1	0.37789 (11)	0.38698 (19)	0.11129 (5)	0.0406 (4)
H1	0.4407 (8)	0.369 (2)	0.0965 (6)	0.046 (5)*
O1	0.19506 (10)	0.3884 (2)	0.09562 (5)	0.0656 (4)
O2	0.06813 (10)	0.2998 (3)	0.02376 (5)	0.0746 (5)
H2A	0.1092 (19)	0.340 (3)	0.0519 (7)	0.098 (8)*
O3	0.08638 (11)	0.2036 (2)	−0.05732 (5)	0.0700 (4)
Cl1	0.38181 (4)	0.61481 (7)	0.334722 (17)	0.0585 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0340 (9)	0.0542 (10)	0.0401 (9)	−0.0017 (8)	−0.0029 (7)	−0.0048 (8)
C2	0.0339 (9)	0.0681 (12)	0.0436 (10)	−0.0021 (8)	0.0016 (7)	−0.0083 (9)
C3	0.0436 (9)	0.0720 (12)	0.0359 (9)	−0.0057 (9)	0.0018 (8)	−0.0065 (9)
C4	0.0438 (10)	0.0691 (12)	0.0358 (10)	−0.0091 (9)	−0.0067 (8)	0.0037 (9)
C5	0.0355 (8)	0.0380 (8)	0.0370 (9)	0.0011 (7)	−0.0049 (7)	−0.0031 (7)
C6	0.0355 (8)	0.0360 (8)	0.0434 (9)	−0.0009 (7)	−0.0029 (7)	−0.0012 (7)
C7	0.0441 (10)	0.0389 (9)	0.0463 (10)	−0.0041 (8)	−0.0090 (8)	−0.0061 (7)
C8	0.0509 (10)	0.0366 (8)	0.0356 (9)	0.0025 (8)	−0.0047 (7)	−0.0026 (7)
C9	0.0473 (10)	0.0460 (9)	0.0415 (9)	−0.0040 (8)	0.0030 (7)	0.0015 (8)
C10	0.0410 (9)	0.0452 (9)	0.0425 (9)	−0.0094 (8)	−0.0028 (7)	−0.0027 (7)
C11	0.0440 (10)	0.0592 (11)	0.0519 (11)	−0.0133 (9)	0.0002 (8)	−0.0048 (9)
N1	0.0321 (8)	0.0517 (9)	0.0380 (8)	−0.0033 (6)	−0.0008 (6)	−0.0070 (6)
O1	0.0350 (7)	0.1178 (13)	0.0441 (7)	0.0058 (7)	−0.0029 (5)	−0.0196 (7)
O2	0.0374 (7)	0.1425 (15)	0.0439 (8)	−0.0093 (8)	−0.0041 (6)	−0.0140 (9)
O3	0.0527 (8)	0.1129 (12)	0.0444 (7)	−0.0126 (8)	−0.0140 (6)	−0.0092 (8)
Cl1	0.0767 (4)	0.0599 (3)	0.0388 (3)	−0.0056 (2)	−0.0028 (2)	−0.00955 (19)

C1—O1	1.238 (2)	C6—C11	1.510 (2)
C1—O1	1.238 (2)	C7—C8	1.382 (2)
C1—N1	1.335 (2)	C7—H7	0.9300
C1—C2	1.482 (2)	C8—C9	1.375 (2)
C2—C3	1.333 (2)	C8—Cl1	1.7478 (16)
C2—H2	0.9300	C9—C10	1.386 (2)
C3—C4	1.479 (3)	C9—H9	0.9300
C3—H3	0.9300	C10—H10	0.9300
C4—O3	1.213 (2)	C11—H11A	0.9600
C4—O2	1.308 (2)	C11—H11B	0.9600
C5—C10	1.389 (2)	C11—H11C	0.9600
C5—C6	1.400 (2)	N1—H1	0.861 (5)
C5—N1	1.429 (2)	O1—O1	0.000 (5)
C6—C7	1.394 (2)	O2—H2A	0.920 (5)
O1—C1—O1	0.00 (12)	C8—C7—H7	119.6
O1—C1—N1	122.22 (16)	C6—C7—H7	119.6
O1—C1—N1	122.22 (16)	C9—C8—C7	121.03 (15)
O1—C1—C2	123.26 (15)	C9—C8—Cl1	119.60 (13)
O1—C1—C2	123.26 (15)	C7—C8—Cl1	119.37 (13)
N1—C1—C2	114.50 (14)	C8—C9—C10	119.05 (16)
C3—C2—C1	129.17 (16)	C8—C9—H9	120.5
C3—C2—H2	115.4	C10—C9—H9	120.5
C1—C2—H2	115.4	C9—C10—C5	120.47 (15)
C2—C3—C4	131.75 (17)	C9—C10—H10	119.8
C2—C3—H3	114.1	C5—C10—H10	119.8
C4—C3—H3	114.1	C6—C11—H11A	109.5
O3—C4—O2	121.08 (16)	C6—C11—H11B	109.5
O3—C4—C3	118.71 (17)	H11A—C11—H11B	109.5
O2—C4—C3	120.21 (15)	C6—C11—H11C	109.5
C10—C5—C6	120.67 (15)	H11A—C11—H11C	109.5
C10—C5—N1	120.95 (14)	H11B—C11—H11C	109.5
C6—C5—N1	118.36 (14)	C1—N1—C5	126.65 (14)
C7—C6—C5	117.92 (15)	C1—N1—H1	114.9 (12)
C7—C6—C11	120.05 (15)	C5—N1—H1	118.4 (12)
C5—C6—C11	122.03 (15)	O1—O1—C1	0(10)
C8—C7—C6	120.85 (15)	C4—O2—H2A	113.1 (17)
O1—C1—C2—C3	−3.2 (3)	C6—C7—C8—Cl1	−179.45 (13)
O1—C1—C2—C3	−3.2 (3)	C7—C8—C9—C10	0.9 (3)
N1—C1—C2—C3	178.4 (2)	Cl1—C8—C9—C10	−179.48 (13)
C1—C2—C3—C4	−2.4 (4)	C8—C9—C10—C5	−1.1 (3)
C2—C3—C4—O3	−176.3 (2)	C6—C5—C10—C9	0.2 (3)
C2—C3—C4—O2	2.7 (4)	N1—C5—C10—C9	178.60 (15)
C10—C5—C6—C7	0.8 (2)	O1—C1—N1—C5	1.3 (3)
N1—C5—C6—C7	−177.59 (14)	O1—C1—N1—C5	1.3 (3)
C10—C5—C6—C11	−178.68 (16)	C2—C1—N1—C5	179.73 (16)
N1—C5—C6—C11	2.9 (2)	C10—C5—N1—C1	34.9 (3)
C5—C6—C7—C8	−1.0 (2)	C6—C5—N1—C1	−146.67 (17)
C11—C6—C7—C8	178.52 (16)	N1—C1—O1—O1	0.00 (10)
C6—C7—C8—C9	0.1 (3)	C2—C1—O1—O1	0.00 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3i	0.86 (1)	2.10 (1)	2.9556 (19)	174.(2)
O2—H2A···O1	0.92 (1)	1.57 (1)	2.4797 (17)	171 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3i	0.86 (1)	2.10 (1)	2.9556 (19)	174 (2)
O2—H2A⋯O1	0.92 (1)	1.57 (1)	2.4797 (17)	171 (3)

Symmetry code: (i) .