4-Chloro-anilinium 3-carb-oxy-prop-2-enoate.

In the title compound, C(6)H(7)ClN(+)·C(4)H(3)O(4) (-), the cations and anions lie on mirror planes and hence only half of the mol-ecules are present in the asymmeric unit. The 4-chloro-anilinium cation and hydrogen maleate anion in the asymmetric unit are each planar and are oriented at an angle of 15.6 (1)° to one another and perpendicular to the b axis. A characterestic intra-molecular O-H⋯O hydrogen bond, forming an S(7) motif, is observed in the maleate anion. In the crystal, the cations and anions are linked by N-H⋯O hydrogen bonds, forming layers in the ab plane. The aromatic rings of the cations are sandwiched between hydrogen-bonded chains and rings formed through the amine group of the cation and maleate anions, leading to alternate hydro-phobic (z = 0 or 1) and hydro-philic layers (z = 1/2) along the c axis.

Related literature

For related structures, see: Anitha et al. (2011 ▶); Balamurugan et al. (2010 ▶); Ploug-Sørenson & Andersen (1985 ▶); Rahmouni et al. (2010 ▶); Smith et al. (2005 ▶, 2007 ▶, 2009 ▶). For the importance of 4-chloro­aniline, see: Ashford (2011 ▶); Amoa (2007 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C6H7ClN+·C4H3O4 −

M = 243.64

Monoclinic,

a = 3.8932 (3) Å

b = 9.1841 (6) Å

c = 14.8394 (9) Å

β = 93.664 (12)°

V = 529.51 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.36 mm−1

T = 293 K

0.21 × 0.18 × 0.15 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

5030 measured reflections

998 independent reflections

921 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.106

S = 1.06

998 reflections

89 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.27 e Å−3

Δρmin = −0.18 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL/PC (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL/PC; molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL/PC.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812008458/sj5203sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812008458/sj5203Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812008458/sj5203Isup3.cml

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

C6H7ClN+·C4H3O4−	F(000) = 252
Mr = 243.64	Dx = 1.528 Mg m−3Dm = 1.53 (1) Mg m−3Dm measured by Flotation technique using a liquid-mixture of carbon tetrachloride and bromoform
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 2243 reflections
a = 3.8932 (3) Å	θ = 2.4–24.7°
b = 9.1841 (6) Å	µ = 0.36 mm−1
c = 14.8394 (9) Å	T = 293 K
β = 93.664 (12)°	Block, colourless
V = 529.51 (6) Å3	0.21 × 0.18 × 0.15 mm
Z = 2

Bruker SMART APEX CCD area-detector diffractometer	921 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.026
Graphite monochromator	θmax = 25.0°, θmin = 2.6°
ω scans	h = −4→4
5030 measured reflections	k = −10→10
998 independent reflections	l = −17→17

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0648P)2 + 0.1135P] where P = (Fo2 + 2Fc2)/3
998 reflections	(Δ/σ)max < 0.001
89 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.18 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
N1	0.1795 (5)	0.2500	0.31121 (14)	0.0544 (5)
C1	−0.2237 (6)	0.2500	0.04426 (15)	0.0483 (5)
C2	−0.1599 (4)	0.37969 (18)	0.08748 (12)	0.0548 (4)
H2	−0.2080	0.4672	0.0577	0.066*
C3	−0.0243 (4)	0.37952 (18)	0.17517 (11)	0.0523 (4)
H3	0.0214	0.4668	0.2053	0.063*
C4	0.0427 (5)	0.2500	0.21759 (14)	0.0443 (5)
Cl1	−0.38471 (18)	0.2500	−0.06702 (4)	0.0710 (3)
H1N	0.314 (6)	0.332 (3)	0.3260 (16)	0.094 (8)*
H2N	0.020 (11)	0.2500	0.344 (3)	0.108 (14)*
C11	0.6247 (4)	0.57400 (16)	0.36908 (10)	0.0442 (4)
C12	0.8034 (4)	0.67786 (17)	0.43181 (10)	0.0443 (4)
H12	0.9374	0.6353	0.4788	0.053*
O1	0.4349 (3)	0.61939 (12)	0.30237 (9)	0.0630 (4)
O2	0.6665 (3)	0.44284 (12)	0.38410 (8)	0.0570 (4)
H1O	0.413 (11)	0.7500	0.295 (3)	0.129 (15)*

	U11	U22	U33	U12	U13	U23
N1	0.0412 (10)	0.0708 (15)	0.0505 (11)	0.000	−0.0032 (8)	0.000
C1	0.0444 (11)	0.0501 (13)	0.0498 (12)	0.000	−0.0020 (9)	0.000
C2	0.0614 (10)	0.0408 (10)	0.0610 (10)	−0.0006 (7)	−0.0045 (8)	0.0064 (7)
C3	0.0575 (9)	0.0409 (9)	0.0579 (9)	−0.0049 (7)	−0.0016 (7)	−0.0041 (7)
C4	0.0330 (9)	0.0508 (12)	0.0490 (11)	0.000	0.0017 (8)	0.000
Cl1	0.0805 (5)	0.0748 (5)	0.0552 (4)	0.000	−0.0161 (3)	0.000
C11	0.0455 (8)	0.0350 (8)	0.0520 (9)	0.0001 (6)	0.0026 (6)	−0.0033 (6)
C12	0.0484 (8)	0.0362 (8)	0.0472 (8)	0.0023 (6)	−0.0058 (6)	0.0014 (6)
O1	0.0742 (8)	0.0419 (7)	0.0691 (8)	−0.0007 (6)	−0.0256 (6)	−0.0081 (5)
O2	0.0683 (7)	0.0308 (6)	0.0711 (8)	0.0001 (5)	−0.0017 (6)	−0.0044 (5)

N1—C4	1.456 (3)	C3—H3	0.9300
N1—H1N	0.94 (2)	C4—C3i	1.3632 (19)
N1—H2N	0.82 (4)	C11—O2	1.2339 (19)
C1—C2	1.368 (2)	C11—O1	1.2674 (18)
C1—C2i	1.368 (2)	C11—C12	1.476 (2)
C1—Cl1	1.728 (2)	C12—C12ii	1.325 (3)
C2—C3	1.373 (2)	C12—H12	0.9300
C2—H2	0.9300	O1—H1O	1.207 (5)
C3—C4	1.3632 (19)
C4—N1—H1N	112.8 (15)	C2—C3—H3	120.3
C4—N1—H2N	109 (3)	C3i—C4—C3	121.5 (2)
H1N—N1—H2N	107 (2)	C3i—C4—N1	119.22 (10)
C2—C1—C2i	121.1 (2)	C3—C4—N1	119.22 (10)
C2—C1—Cl1	119.46 (11)	O2—C11—O1	121.72 (14)
C2i—C1—Cl1	119.46 (11)	O2—C11—C12	117.76 (14)
C1—C2—C3	119.39 (15)	O1—C11—C12	120.53 (14)
C1—C2—H2	120.3	C12ii—C12—C11	130.27 (8)
C3—C2—H2	120.3	C12ii—C12—H12	114.9
C4—C3—C2	119.30 (15)	C11—C12—H12	114.9
C4—C3—H3	120.3	C11—O1—H1O	115 (2)
C2i—C1—C2—C3	1.1 (4)	C2—C3—C4—N1	−178.68 (18)
Cl1—C1—C2—C3	−178.44 (14)	O2—C11—C12—C12ii	−179.82 (9)
C1—C2—C3—C4	−0.3 (3)	O1—C11—C12—C12ii	0.04 (18)
C2—C3—C4—C3i	−0.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2	0.94 (2)	1.87 (2)	2.764 (2)	158 (2)
N1—H2N···O2iii	0.82 (4)	2.34 (3)	2.928 (2)	129 (1)
N1—H2N···O2iv	0.82 (4)	2.34 (3)	2.928 (2)	129 (1)
O1—H1O···O1ii	1.21 (1)	1.21 (1)	2.399 (2)	167 (1)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2	0.94 (2)	1.87 (2)	2.764 (2)	158 (2)
N1—H2N⋯O2i	0.82 (4)	2.34 (3)	2.928 (2)	129 (1)
N1—H2N⋯O2ii	0.82 (4)	2.34 (3)	2.928 (2)	129 (1)
O1—H1O⋯O1iii	1.21 (1)	1.21 (1)	2.399 (2)	167 (1)

Symmetry codes: (i) ; (ii) ; (iii) .