N-(2,4,5-Trichloro-phen-yl)maleamic acid.

The title compound, C(10)H(6)Cl(3)NO(3), crystallizes with two independent mol-ecules in the asymmetric unit. The mol-ecular structure is stabilized by a short intra-molecular O-H⋯O hydrogen bond within the maleamic unit. In the crystal, each mol-ecule self-associates via N-H⋯O hydrogen bonds into chains, each running along the b axis. Two short inter-molecular Cl⋯O contacts [3.1267 (15) and 3.0523 (12) Å] and C-H⋯O inter-actions inter-connect 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 = 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

Δρmax = 0.28 e Å−3

Δρmin = −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 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809052520/tk2591sup1.cif

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

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

C10H6Cl3NO3	F(000) = 1184
Mr = 294.51	Dx = 1.68 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 30027 reflections
a = 10.8979 (2) Å	θ = 1.8–29.5°
b = 11.0225 (2) Å	µ = 0.78 mm−1
c = 19.4739 (3) Å	T = 295 K
β = 95.4761 (9)°	Block, colourless
V = 2328.57 (7) Å3	0.34 × 0.25 × 0.22 mm
Z = 8

Oxford Diffraction Xcalibur diffractometer with a Ruby Gemini detector	4424 independent reflections
graphite	3825 reflections with I > 2σ(I)
Detector resolution: 10.434 pixels mm-1	Rint = 0.022
ω scans	θmax = 25.7°, θmin = 1.9°
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2009)	h = −13→13
Tmin = 0.794, Tmax = 0.852	k = −13→13
49446 measured reflections	l = −23→23

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0464P)2 + 0.5233P] where P = (Fo2 + 2Fc2)/3
4424 reflections	(Δ/σ)max = 0.001
315 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.32 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	0.44390 (14)	0.49367 (14)	0.63260 (8)	0.0359 (3)
C2	0.49027 (16)	0.44723 (15)	0.70185 (8)	0.0435 (4)
H2	0.5531	0.4921	0.7254	0.052*
C3	0.45354 (16)	0.34984 (16)	0.73449 (8)	0.0437 (4)
H3	0.4945	0.3395	0.7782	0.052*
C4	0.36034 (14)	0.25383 (14)	0.71553 (8)	0.0353 (3)
C5	0.47664 (14)	0.65859 (13)	0.55063 (8)	0.0338 (3)
C6	0.55197 (15)	0.75667 (14)	0.53696 (8)	0.0390 (4)
C7	0.52840 (17)	0.82580 (15)	0.47808 (9)	0.0447 (4)
H7	0.5787	0.8917	0.4705	0.054*
C8	0.43056 (16)	0.79770 (15)	0.43042 (8)	0.0418 (4)
C9	0.35753 (15)	0.69853 (15)	0.44191 (8)	0.0385 (4)
C10	0.37961 (15)	0.63019 (14)	0.50161 (8)	0.0374 (3)
H10	0.3289	0.5645	0.5090	0.045*
N1	0.50133 (13)	0.59440 (12)	0.61283 (7)	0.0364 (3)
H1N	0.5504 (19)	0.6210 (18)	0.6398 (10)	0.047 (6)*
O1	0.36099 (12)	0.44379 (11)	0.59559 (6)	0.0524 (3)
O2	0.29633 (10)	0.25568 (10)	0.65501 (6)	0.0440 (3)
H2A	0.3156	0.3154	0.6334	0.053*
O3	0.34614 (11)	0.17281 (10)	0.75610 (6)	0.0439 (3)
Cl1	0.67690 (5)	0.79432 (5)	0.59434 (2)	0.06029 (15)
Cl2	0.40225 (5)	0.88690 (4)	0.35759 (3)	0.06031 (15)
Cl3	0.23559 (4)	0.65766 (5)	0.38355 (2)	0.05600 (14)
C11	−0.01578 (14)	0.08037 (14)	0.62405 (8)	0.0356 (3)
C12	0.05760 (15)	0.08711 (15)	0.69170 (8)	0.0405 (4)
H12	0.1200	0.1450	0.6953	0.049*
C13	0.04666 (15)	0.02176 (16)	0.74809 (8)	0.0429 (4)
H13	0.1058	0.0398	0.7843	0.051*
C14	−0.04107 (16)	−0.07430 (17)	0.76485 (9)	0.0468 (4)
C15	−0.04415 (14)	0.19115 (14)	0.51309 (7)	0.0348 (3)
C16	−0.00319 (16)	0.29029 (15)	0.47665 (8)	0.0393 (4)
C17	−0.05759 (17)	0.32085 (16)	0.41215 (8)	0.0450 (4)
H17	−0.0298	0.3880	0.3892	0.054*
C18	−0.15340 (16)	0.25164 (15)	0.38159 (8)	0.0410 (4)
C19	−0.19375 (15)	0.15206 (15)	0.41656 (8)	0.0374 (3)
C20	−0.14062 (15)	0.12225 (14)	0.48168 (8)	0.0380 (4)
H20	−0.1696	0.0557	0.5046	0.046*
N2	0.01228 (14)	0.16733 (13)	0.57959 (7)	0.0393 (3)
H2N	0.0613 (18)	0.2172 (17)	0.5962 (9)	0.044 (5)*
O4	−0.09307 (13)	0.00116 (12)	0.60847 (6)	0.0572 (4)
O5	−0.12126 (16)	−0.11735 (15)	0.71730 (7)	0.0818 (5)
H5A	−0.1146	−0.0818	0.6808	0.098*
O6	−0.03687 (14)	−0.11161 (13)	0.82354 (7)	0.0629 (4)
Cl4	0.11807 (5)	0.37788 (4)	0.51289 (2)	0.05662 (14)
Cl5	−0.22020 (5)	0.29035 (5)	0.30038 (2)	0.06325 (15)
Cl6	−0.31341 (4)	0.06298 (4)	0.38018 (2)	0.05475 (14)

	U11	U22	U33	U12	U13	U23
C1	0.0387 (8)	0.0346 (8)	0.0336 (8)	−0.0062 (6)	−0.0006 (6)	−0.0020 (6)
C2	0.0481 (10)	0.0433 (9)	0.0364 (8)	−0.0128 (7)	−0.0103 (7)	−0.0004 (7)
C3	0.0486 (10)	0.0459 (9)	0.0335 (8)	−0.0075 (8)	−0.0123 (7)	0.0040 (7)
C4	0.0341 (8)	0.0345 (8)	0.0363 (8)	0.0035 (6)	−0.0014 (6)	0.0018 (7)
C5	0.0366 (8)	0.0325 (8)	0.0326 (7)	−0.0023 (6)	0.0044 (6)	−0.0035 (6)
C6	0.0420 (9)	0.0372 (8)	0.0376 (8)	−0.0096 (7)	0.0035 (7)	−0.0066 (7)
C7	0.0546 (10)	0.0372 (9)	0.0435 (9)	−0.0113 (7)	0.0107 (8)	−0.0004 (7)
C8	0.0498 (10)	0.0393 (9)	0.0372 (8)	0.0034 (7)	0.0095 (7)	0.0047 (7)
C9	0.0371 (8)	0.0426 (9)	0.0354 (8)	0.0011 (7)	0.0007 (7)	−0.0016 (7)
C10	0.0367 (8)	0.0378 (8)	0.0373 (8)	−0.0074 (7)	0.0012 (7)	0.0012 (7)
N1	0.0387 (7)	0.0359 (7)	0.0331 (7)	−0.0101 (6)	−0.0049 (6)	−0.0018 (6)
O1	0.0594 (8)	0.0510 (7)	0.0427 (6)	−0.0255 (6)	−0.0165 (6)	0.0126 (5)
O2	0.0467 (7)	0.0429 (6)	0.0398 (6)	−0.0156 (5)	−0.0099 (5)	0.0095 (5)
O3	0.0487 (7)	0.0372 (6)	0.0441 (6)	−0.0003 (5)	−0.0035 (5)	0.0105 (5)
Cl1	0.0609 (3)	0.0657 (3)	0.0520 (3)	−0.0323 (2)	−0.0066 (2)	−0.0027 (2)
Cl2	0.0741 (3)	0.0548 (3)	0.0516 (3)	0.0010 (2)	0.0036 (2)	0.0191 (2)
Cl3	0.0502 (3)	0.0696 (3)	0.0451 (2)	−0.0060 (2)	−0.01197 (19)	0.0054 (2)
C11	0.0355 (8)	0.0389 (8)	0.0320 (8)	−0.0030 (7)	0.0002 (6)	0.0020 (6)
C12	0.0358 (8)	0.0466 (9)	0.0377 (8)	−0.0102 (7)	−0.0041 (7)	0.0043 (7)
C13	0.0402 (9)	0.0516 (10)	0.0347 (8)	−0.0073 (7)	−0.0081 (7)	0.0046 (7)
C14	0.0491 (10)	0.0495 (10)	0.0403 (9)	−0.0074 (8)	−0.0043 (8)	0.0098 (8)
C15	0.0392 (8)	0.0366 (8)	0.0278 (7)	−0.0015 (6)	−0.0002 (6)	−0.0009 (6)
C16	0.0424 (9)	0.0405 (9)	0.0341 (8)	−0.0096 (7)	−0.0008 (7)	−0.0007 (7)
C17	0.0541 (10)	0.0454 (9)	0.0346 (8)	−0.0102 (8)	−0.0006 (7)	0.0069 (7)
C18	0.0465 (9)	0.0473 (9)	0.0282 (7)	−0.0003 (7)	−0.0024 (7)	0.0022 (7)
C19	0.0386 (8)	0.0404 (9)	0.0325 (8)	−0.0033 (7)	−0.0006 (6)	−0.0039 (6)
C20	0.0419 (9)	0.0375 (8)	0.0339 (8)	−0.0056 (7)	0.0006 (7)	0.0010 (6)
N2	0.0435 (8)	0.0411 (8)	0.0316 (7)	−0.0117 (6)	−0.0057 (6)	0.0031 (6)
O4	0.0698 (8)	0.0597 (8)	0.0385 (6)	−0.0307 (7)	−0.0139 (6)	0.0111 (6)
O5	0.0967 (12)	0.0929 (12)	0.0499 (8)	−0.0596 (10)	−0.0235 (8)	0.0280 (8)
O6	0.0715 (9)	0.0722 (9)	0.0433 (7)	−0.0173 (7)	−0.0040 (6)	0.0210 (6)
Cl4	0.0632 (3)	0.0586 (3)	0.0450 (2)	−0.0288 (2)	−0.0107 (2)	0.0078 (2)
Cl5	0.0709 (3)	0.0774 (3)	0.0373 (2)	−0.0156 (3)	−0.0160 (2)	0.0162 (2)
Cl6	0.0557 (3)	0.0606 (3)	0.0443 (2)	−0.0203 (2)	−0.0140 (2)	0.0024 (2)

C1—O1	1.2304 (18)	C11—O4	1.2309 (19)
C1—N1	1.349 (2)	C11—N2	1.346 (2)
C1—C2	1.485 (2)	C11—C12	1.476 (2)
C2—C3	1.329 (2)	C12—C13	1.328 (2)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.489 (2)	C13—C14	1.484 (2)
C3—H3	0.9300	C13—H13	0.9300
C4—O3	1.2121 (18)	C14—O6	1.211 (2)
C4—O2	1.3111 (18)	C14—O5	1.301 (2)
C5—C10	1.391 (2)	C15—C20	1.390 (2)
C5—C6	1.398 (2)	C15—C16	1.399 (2)
C5—N1	1.406 (2)	C15—N2	1.404 (2)
C6—C7	1.380 (2)	C16—C17	1.379 (2)
C6—Cl1	1.7274 (16)	C16—Cl4	1.7315 (16)
C7—C8	1.380 (3)	C17—C18	1.381 (2)
C7—H7	0.9300	C17—H17	0.9300
C8—C9	1.383 (2)	C18—C19	1.385 (2)
C8—Cl2	1.7292 (16)	C18—Cl5	1.7301 (16)
C9—C10	1.387 (2)	C19—C20	1.382 (2)
C9—Cl3	1.7240 (16)	C19—Cl6	1.7292 (16)
C10—H10	0.9300	C20—H20	0.9300
N1—H1N	0.77 (2)	N2—H2N	0.81 (2)
O2—H2A	0.8200	O5—H5A	0.8200
O1—C1—N1	122.38 (14)	O4—C11—N2	122.58 (14)
O1—C1—C2	123.03 (14)	O4—C11—C12	123.73 (14)
N1—C1—C2	114.58 (13)	N2—C11—C12	113.65 (14)
C3—C2—C1	128.39 (15)	C13—C12—C11	128.82 (15)
C3—C2—H2	115.8	C13—C12—H12	115.6
C1—C2—H2	115.8	C11—C12—H12	115.6
C2—C3—C4	133.25 (15)	C12—C13—C14	132.80 (15)
C2—C3—H3	113.4	C12—C13—H13	113.6
C4—C3—H3	113.4	C14—C13—H13	113.6
O3—C4—O2	120.49 (14)	O6—C14—O5	120.67 (16)
O3—C4—C3	119.25 (14)	O6—C14—C13	118.86 (16)
O2—C4—C3	120.25 (13)	O5—C14—C13	120.47 (15)
C10—C5—C6	117.71 (14)	C20—C15—C16	117.90 (14)
C10—C5—N1	123.25 (14)	C20—C15—N2	123.35 (14)
C6—C5—N1	119.04 (14)	C16—C15—N2	118.74 (14)
C7—C6—C5	121.26 (15)	C17—C16—C15	121.51 (15)
C7—C6—Cl1	118.52 (13)	C17—C16—Cl4	118.70 (13)
C5—C6—Cl1	120.22 (12)	C15—C16—Cl4	119.79 (12)
C6—C7—C8	120.35 (15)	C16—C17—C18	119.95 (15)
C6—C7—H7	119.8	C16—C17—H17	120.0
C8—C7—H7	119.8	C18—C17—H17	120.0
C7—C8—C9	119.22 (15)	C17—C18—C19	119.22 (14)
C7—C8—Cl2	119.33 (13)	C17—C18—Cl5	119.50 (13)
C9—C8—Cl2	121.46 (13)	C19—C18—Cl5	121.28 (13)
C8—C9—C10	120.56 (15)	C20—C19—C18	120.96 (15)
C8—C9—Cl3	121.27 (13)	C20—C19—Cl6	118.32 (12)
C10—C9—Cl3	118.16 (13)	C18—C19—Cl6	120.72 (12)
C9—C10—C5	120.85 (14)	C19—C20—C15	120.44 (15)
C9—C10—H10	119.6	C19—C20—H20	119.8
C5—C10—H10	119.6	C15—C20—H20	119.8
C1—N1—C5	127.17 (14)	C11—N2—C15	128.30 (14)
C1—N1—H1N	115.5 (15)	C11—N2—H2N	114.0 (13)
C5—N1—H1N	117.3 (15)	C15—N2—H2N	117.0 (13)
C4—O2—H2A	109.5	C14—O5—H5A	109.5
O1—C1—C2—C3	0.1 (3)	O4—C11—C12—C13	−7.6 (3)
N1—C1—C2—C3	−178.97 (18)	N2—C11—C12—C13	174.36 (18)
C1—C2—C3—C4	1.6 (3)	C11—C12—C13—C14	−2.5 (3)
C2—C3—C4—O3	179.39 (19)	C12—C13—C14—O6	−173.1 (2)
C2—C3—C4—O2	0.8 (3)	C12—C13—C14—O5	6.7 (3)
C10—C5—C6—C7	2.3 (2)	C20—C15—C16—C17	1.2 (2)
N1—C5—C6—C7	−177.16 (15)	N2—C15—C16—C17	−177.78 (16)
C10—C5—C6—Cl1	−178.08 (12)	C20—C15—C16—Cl4	−179.11 (13)
N1—C5—C6—Cl1	2.4 (2)	N2—C15—C16—Cl4	1.9 (2)
C5—C6—C7—C8	−1.3 (3)	C15—C16—C17—C18	−1.2 (3)
Cl1—C6—C7—C8	179.06 (13)	Cl4—C16—C17—C18	179.12 (14)
C6—C7—C8—C9	−0.9 (3)	C16—C17—C18—C19	0.1 (3)
C6—C7—C8—Cl2	179.30 (13)	C16—C17—C18—Cl5	−179.56 (14)
C7—C8—C9—C10	2.0 (2)	C17—C18—C19—C20	0.8 (3)
Cl2—C8—C9—C10	−178.14 (13)	Cl5—C18—C19—C20	−179.46 (13)
C7—C8—C9—Cl3	−178.97 (13)	C17—C18—C19—Cl6	180.00 (14)
Cl2—C8—C9—Cl3	0.9 (2)	Cl5—C18—C19—Cl6	−0.3 (2)
C8—C9—C10—C5	−1.0 (2)	C18—C19—C20—C15	−0.8 (3)
Cl3—C9—C10—C5	179.95 (12)	Cl6—C19—C20—C15	−179.99 (12)
C6—C5—C10—C9	−1.1 (2)	C16—C15—C20—C19	−0.2 (2)
N1—C5—C10—C9	178.32 (15)	N2—C15—C20—C19	178.71 (15)
O1—C1—N1—C5	1.4 (3)	O4—C11—N2—C15	5.9 (3)
C2—C1—N1—C5	−179.53 (15)	C12—C11—N2—C15	−176.01 (16)
C10—C5—N1—C1	5.1 (3)	C20—C15—N2—C11	−1.6 (3)
C6—C5—N1—C1	−175.47 (15)	C16—C15—N2—C11	177.28 (16)

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

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)

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

Symmetry codes: (i) ; (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)

Symmetry code: (iii)