4-Hy­droxy­anilinium 2-chloro­acetate

Wang, Y.-C.

doi:10.1107/S1600536812021411

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1883

doi:10.1107/S1600536812021411

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4-Hydroxyanilinium 2-chloroacetate

Ying-Chun Wang ^a ^*

^aCollege of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: chenxinyuanseu@yahoo.com.cn

(Received 7 May 2012; accepted 11 May 2012; online 26 May 2012)

In the crystal of the title salt, C₆H₈NO⁺·C₂H₂ClO₂⁻, the 4-hydroxyanilinium cation links to adjacent chloroacetate anions via N—H⋯O and O—H⋯O hydrogen bonds; weak C—H⋯O interactions also occur between the anions and cations.

Related literature

For the structures and properties of related compounds, see: Chen et al. (2001 ); Wang et al. (2002 ); Xue et al. (2002 ); Huang et al. (1999 ); Zhang et al. (2001 ); Ye et al. (2008 ).

Experimental

Crystal data

C₆H₈NO⁺·C₂H₂ClO₂⁻
M_r = 203.62
Monoclinic, P 2₁ /c
a = 10.702 (3) Å
b = 4.5242 (10) Å
c = 19.357 (7) Å
β = 96.825 (2)°
V = 930.6 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 173 K
0.10 × 0.05 × 0.05 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.910, T_max = 1.000
6248 measured reflections
2122 independent reflections
1699 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.104
S = 1.09
2122 reflections
119 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3	0.91	1.86	2.755 (3)	166
N1—H1B⋯O2ⁱ	0.91	1.87	2.777 (3)	171
N1—H1C⋯O2ⁱⁱ	0.91	1.90	2.762 (2)	157
O1—H1⋯O3ⁱⁱⁱ	0.82	1.87	2.683 (2)	172
C8—H8A⋯O1^iv	0.99	2.38	3.319 (3)	159
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y+2, -z+1; (iii) -x, -y+1, -z+1; (iv) -x, -y+2, -z+1.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812021411/xu5534sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812021411/xu5534Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812021411/xu5534Isup3.cml

checkCIF report

Comment top

Simple organic salts containing strong intrermolecular H-bonds have attracted an attention as materials which display ferroelectric-paraelectric phase transitions (Chen et al., 2001; Huang et al., 1999; Zhang et al., 2001). With the purpose of obtaining phase transition crystals of organic salts, various organic molecules have been studied and a series of new crystal materials have been elaborated (Wang et al., 2002; Xue et al., 2002; Ye et al., 2008). Herewith, we present the synthesis and crystal structure of the title compound, 4-hydroxyanilinium 2-chloroacetate.

In the title compound (Fig. 1), the bond lengths and angles have normal values. The asymmetric unit was composed of one 4-hydroxyanilinium cation and one 2-chloroacetate anion. The protonated N atom was involved in strong intramolecular N—H···O hydrogen bonds with the N···O distances of 2.777 (3)Å, 2.762 (2)Å and 2.755 (3)Å, respectively. The N—H···O and O—H···O H-bonding interactions connected the ion units into a 2D network parallel to the ab-plane. The weak intermolecular C8—H8A···O1 interaction was presented in the crystal structure with C8···O1 = 3.319 (3)Å.

Related literature top

For the structures and properties of related compounds, see: Chen et al. (2001); Wang et al. (2002); Xue et al. (2002); Huang et al. (1999); Zhang et al. (2001); Ye et al. (2008).

Experimental top

The 2-chloroacetic acid (10 mmol), 4-aminophenol (10 mmol) and ethanol (50 mL) were added into a 100 mL flask. The mixture was stirred at 333 K for 2 h, and then the precipitate was filtered out. Colourless crystals suitable for X-ray diffraction were obtained by slow evaporation of the solution.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of the asymmetric unit with the atomic numbering scheme. The displacement ellipsoids were drawn at the 30% probability level.

4-Hydroxyanilinium 2-chloroacetate top

Crystal data top

C₆H₈NO⁺·C₂H₂ClO₂⁻	F(000) = 424
M_r = 203.62	D_x = 1.453 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2122 reflections
a = 10.702 (3) Å	θ = 2.7–27.5°
b = 4.5242 (10) Å	µ = 0.38 mm⁻¹
c = 19.357 (7) Å	T = 173 K
β = 96.825 (2)°	Block, colorless
V = 930.6 (5) Å³	0.10 × 0.05 × 0.05 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	2122 independent reflections
Radiation source: fine-focus sealed tube	1699 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 2.7°
CCD profile fitting scans	h = −12→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −5→5
T_min = 0.910, T_max = 1.000	l = −25→23
6248 measured reflections

Refinement top

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.041P)² + 0.4P] where P = (F_o² + 2F_c²)/3
2122 reflections	(Δ/σ)_max < 0.001
119 parameters	Δρ_max = 0.31 e Å⁻³
4 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₆H₈NO⁺·C₂H₂ClO₂⁻	V = 930.6 (5) Å³
M_r = 203.62	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.702 (3) Å	µ = 0.38 mm⁻¹
b = 4.5242 (10) Å	T = 173 K
c = 19.357 (7) Å	0.10 × 0.05 × 0.05 mm
β = 96.825 (2)°

Data collection top

Rigaku Mercury2 diffractometer	2122 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1699 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.045
6248 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	4 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 1.09	Δρ_max = 0.31 e Å⁻³
2122 reflections	Δρ_min = −0.31 e Å⁻³
119 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.41622 (5)	1.32273 (13)	0.29181 (3)	0.02016 (16)
O3	0.29262 (14)	0.7514 (4)	0.42037 (8)	0.0222 (4)
O2	0.48355 (14)	0.9420 (4)	0.41518 (8)	0.0188 (4)
N1	0.37140 (16)	0.5601 (4)	0.55354 (10)	0.0163 (4)
H1A	0.3555	0.6038	0.5074	0.024*
H1B	0.4170	0.3902	0.5590	0.024*
H1C	0.4158	0.7104	0.5760	0.024*
O1	−0.08865 (14)	0.4356 (4)	0.66202 (9)	0.0250 (4)
H1	−0.1461	0.3684	0.6347	0.037*
C2	0.1616 (2)	0.3348 (6)	0.54972 (13)	0.0223 (5)
H2A	0.1781	0.2289	0.5094	0.027*
C7	0.3694 (2)	0.9122 (5)	0.39246 (11)	0.0163 (5)
C1	0.2513 (2)	0.5212 (5)	0.58293 (12)	0.0164 (5)
C6	0.2298 (2)	0.6739 (6)	0.64231 (12)	0.0204 (5)
H6A	0.2929	0.7995	0.6651	0.025*
C4	0.0232 (2)	0.4565 (5)	0.63473 (12)	0.0184 (5)
C5	0.1148 (2)	0.6413 (6)	0.66814 (12)	0.0235 (5)
H5A	0.0989	0.7458	0.7088	0.028*
C3	0.0466 (2)	0.3032 (6)	0.57581 (13)	0.0231 (5)
H3A	−0.0159	0.1760	0.5531	0.028*
C8	0.3133 (2)	1.0670 (5)	0.32664 (12)	0.0191 (5)
H8A	0.2366	1.1738	0.3364	0.023*
H8B	0.2873	0.9156	0.2909	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0217 (3)	0.0185 (3)	0.0211 (3)	−0.0005 (2)	0.0056 (2)	0.0027 (2)
O3	0.0177 (8)	0.0311 (10)	0.0180 (8)	−0.0054 (7)	0.0023 (7)	0.0060 (7)
O2	0.0146 (8)	0.0172 (8)	0.0236 (9)	−0.0023 (7)	−0.0018 (6)	0.0011 (7)
N1	0.0141 (9)	0.0171 (10)	0.0177 (10)	−0.0021 (8)	0.0020 (7)	0.0020 (8)
O1	0.0135 (8)	0.0374 (11)	0.0245 (9)	−0.0036 (8)	0.0041 (7)	0.0002 (8)
C2	0.0221 (12)	0.0226 (12)	0.0232 (12)	−0.0053 (11)	0.0066 (10)	−0.0074 (10)
C7	0.0161 (11)	0.0166 (11)	0.0165 (11)	0.0005 (9)	0.0035 (9)	−0.0015 (9)
C1	0.0126 (10)	0.0173 (12)	0.0193 (12)	−0.0005 (9)	0.0023 (9)	0.0059 (9)
C6	0.0158 (11)	0.0267 (13)	0.0181 (11)	−0.0025 (10)	−0.0012 (9)	−0.0015 (10)
C4	0.0135 (10)	0.0217 (12)	0.0197 (12)	0.0005 (9)	0.0012 (9)	0.0069 (10)
C5	0.0191 (11)	0.0338 (15)	0.0175 (12)	−0.0009 (11)	0.0014 (9)	−0.0015 (10)
C3	0.0183 (11)	0.0225 (12)	0.0285 (13)	−0.0089 (10)	0.0027 (10)	−0.0057 (11)
C8	0.0169 (11)	0.0197 (12)	0.0205 (12)	−0.0036 (10)	0.0012 (9)	0.0031 (10)

Geometric parameters (Å, º) top

Cl1—C8	1.784 (2)	C2—H2A	0.9500
O3—C7	1.265 (3)	C7—C8	1.514 (3)
O2—C7	1.256 (3)	C1—C6	1.384 (3)
N1—C1	1.477 (3)	C6—C5	1.390 (3)
N1—H1A	0.9100	C6—H6A	0.9500
N1—H1B	0.9100	C4—C3	1.383 (3)
N1—H1C	0.9100	C4—C5	1.389 (3)
O1—C4	1.368 (3)	C5—H5A	0.9500
O1—H1	0.8203	C3—H3A	0.9500
C2—C1	1.378 (3)	C8—H8A	0.9900
C2—C3	1.392 (3)	C8—H8B	0.9900

C1—N1—H1A	109.5	C1—C6—H6A	120.4
C1—N1—H1B	109.5	C5—C6—H6A	120.4
H1A—N1—H1B	109.5	O1—C4—C3	122.4 (2)
C1—N1—H1C	109.5	O1—C4—C5	117.6 (2)
H1A—N1—H1C	109.5	C3—C4—C5	119.9 (2)
H1B—N1—H1C	109.5	C4—C5—C6	120.2 (2)
C4—O1—H1	113.6	C4—C5—H5A	119.9
C1—C2—C3	119.4 (2)	C6—C5—H5A	119.9
C1—C2—H2A	120.3	C4—C3—C2	120.1 (2)
C3—C2—H2A	120.3	C4—C3—H3A	119.9
O2—C7—O3	124.5 (2)	C2—C3—H3A	119.9
O2—C7—C8	121.14 (19)	C7—C8—Cl1	114.65 (16)
O3—C7—C8	114.38 (19)	C7—C8—H8A	108.6
C2—C1—C6	121.2 (2)	Cl1—C8—H8A	108.6
C2—C1—N1	118.9 (2)	C7—C8—H8B	108.6
C6—C1—N1	119.9 (2)	Cl1—C8—H8B	108.6
C1—C6—C5	119.2 (2)	H8A—C8—H8B	107.6

C3—C2—C1—C6	1.0 (4)	C1—C6—C5—C4	0.3 (4)
C3—C2—C1—N1	−178.1 (2)	O1—C4—C3—C2	179.3 (2)
C2—C1—C6—C5	−1.0 (4)	C5—C4—C3—C2	−0.3 (4)
N1—C1—C6—C5	178.2 (2)	C1—C2—C3—C4	−0.4 (4)
O1—C4—C5—C6	−179.3 (2)	O2—C7—C8—Cl1	−7.3 (3)
C3—C4—C5—C6	0.3 (4)	O3—C7—C8—Cl1	173.97 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3	0.91	1.86	2.755 (3)	166
N1—H1B···O2ⁱ	0.91	1.87	2.777 (3)	171
N1—H1C···O2ⁱⁱ	0.91	1.90	2.762 (2)	157
O1—H1···O3ⁱⁱⁱ	0.82	1.87	2.683 (2)	172
C8—H8A···O1^iv	0.99	2.38	3.319 (3)	159

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z+1; (iii) −x, −y+1, −z+1; (iv) −x, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₆H₈NO⁺·C₂H₂ClO₂⁻
M_r	203.62
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	10.702 (3), 4.5242 (10), 19.357 (7)
β (°)	96.825 (2)
V (Å³)	930.6 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.10 × 0.05 × 0.05

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.910, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6248, 2122, 1699
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.104, 1.09
No. of reflections	2122
No. of parameters	119
No. of restraints	4
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.31

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3	0.91	1.86	2.755 (3)	166.0
N1—H1B···O2ⁱ	0.91	1.87	2.777 (3)	171.1
N1—H1C···O2ⁱⁱ	0.91	1.90	2.762 (2)	156.6
O1—H1···O3ⁱⁱⁱ	0.82	1.87	2.683 (2)	171.6
C8—H8A···O1^iv	0.99	2.38	3.319 (3)	159

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z+1; (iii) −x, −y+1, −z+1; (iv) −x, −y+2, −z+1.

Acknowledgements

This work was supported by a start-up grant from Southeast University, China.

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