4-(Carboxy­meth­yl)anilinium chloride

Kechout, H.; Belhouas, R.; Bouacida, S.; Merazig, H.

doi:10.1107/S1600536809021849

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Pages o1563-o1564

doi:10.1107/S1600536809021849

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4-(Carboxymethyl)anilinium chloride

Habiba Kechout,^a Ratiba Belhouas,^b ^* Sofiane Bouacida ^a and Hocine Merazig ^a

^aUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, CHEMS, Faculté des Sciences Exactes, Département de Chimie, Université Mentouri Constantine, 25000 Algeria, and ^bFaculté de Chimie, USTHB, BP32 El-Alia, Bab-Ezzouar, Alger, Algeria
^*Correspondence e-mail: belhouas.ratiba@yahoo.fr

(Received 2 June 2009; accepted 9 June 2009; online 13 June 2009)

In the crystal of the title compound, C₈H₁₀NO₂⁺·Cl⁻, alternating layers of hydrophobic and hydrophilic zones stack along the c axis. The chloride anions are sandwiched between the 4-(carboxymethyl)anilinium layers, forming intermolecular O—H⋯Cl and N—H⋯Cl hydrogen bonds with the ammonium and carboxyl groups of the cations. In addition, intermolecular N—H⋯O and weak C—H⋯O and C—H⋯Cl hydrogen bonds help stabilize the crystal structure.

Related literature

For our ongoing studies of hydrogen-bonding interactions in the crystal structures of protonated amines, see: Benslimane et al. (2007 ); Bouacida et al. (2005a ,b ,c , 2006 , 2007 , 2008 , 2009 ). For amino acids in which the amino N atom is protonated, see: Bouacida et al. (2006); Rademeyer (2004a ,b ). For a related structure, see: Benslimane et al. (2007). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₁₀NO₂⁺·Cl⁻
M_r = 187.62
Monoclinic, P 2₁ /n
a = 4.4982 (4) Å
b = 11.0790 (11) Å
c = 17.7120 (17) Å
β = 95.429 (3)°
V = 878.73 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 100 K
0.44 × 0.12 × 0.1 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.809, T_max = 0.962
7536 measured reflections
2006 independent reflections
1785 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.08
S = 1.03
2006 reflections
113 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Cl1ⁱ	0.82	2.20	3.0087 (13)	171
N1—H1A⋯O2ⁱⁱ	0.89	1.98	2.8517 (17)	167
N1—H1B⋯Cl1ⁱⁱⁱ	0.89	2.41	3.2285 (13)	152
N1—H1C⋯Cl1^iv	0.89	2.26	3.1516 (14)	174
C2—H2⋯O2ⁱⁱ	0.93	2.49	3.2338 (18)	137
C3—H3⋯Cl1	0.93	2.82	3.7481 (15)	175
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and DIAMOND (Brandenburg & Berndt, 2001 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809021849/lh2838sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809021849/lh2838Isup2.hkl

checkCIF report

Comment top

The title compound, was prepared as part of our ongoing studies of hydrogen-bonding interactions in the crystal structure of protonated amines (Bouacida et al., 2005a,b,c, 2006, 2007, 2008, 2009).

The molecular structure of (I), and the atomic numbering used, is illustrated in Fig. 1. All bond distances (Allen et al., 1987) and angles are within the ranges of accepted values. The amino N atom is protonated as in previously reported amino acids (Bouacida & al., 2006; Rademeyer, 2004a,b). The layered crystal packing of (I) is shown in Fig. 2, in which cations form alterning layers of 4-(carboxymethyl)anilinium of hydrophobic and hydrophilic zones along the c axis, and the chloride ions are located between these layers. In the structure, two types of classical hydrogen bonds are observed, viz. cation–anion and cation–cation (Fig. 3). The 4-(carboxymethyl)anilinium cations and the chloride anions form hydrogen-bonded double layers at z = 0 and z = 1/2, linked by N—H···Cl, C—H···Cl and O—H···Cl hydrogen bonds. Additional hydrogen-bonding parameters are listed in Table 1. These interaction bonds link the cations and the anions together, forming a three-dimensional network and reinforcing the cohesion of the ionic structure.

Related literature top

For our ongoing studies of hydrogen-bonding interactions in the crystal structures of protonated amines, see: Benslimane et al. (2007); Bouacida et al. (2005a,b,c, 2006, 2007, 2008, 2009). For amino acids in which the amino N atom is protonated, see: Bouacida et al. (2006); Rademeyer (2004a,b). For a related structure, see: Benslimane et al. (2007). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was crystallized by slow evaporation of an aqueous solution of 4-aminophenyl acetic acid, tin(II) chloride dihydrate and hydrochloric acid in a molar ratio of 5:5:1. White stick-like crystals were obtained after two weeks.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The asymmetric unit of the title compound with the atomic labelling scheme. Displacement are drawn at the 50% probability level.
	Fig. 2. Part of the crystal structure illustrating the molecular layers, viewed along the b axis.
	Fig. 3. Part of the crystal structure with hydrogen bonds shown as dashed lines, viewed along the a axis.

4-(Carboxymethyl)anilinium chloride top

Crystal data top

C₈H₁₀NO₂⁺·Cl⁻	F(000) = 392
M_r = 187.62	D_x = 1.418 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3208 reflections
a = 4.4982 (4) Å	θ = 2.3–27.4°
b = 11.0790 (11) Å	µ = 0.39 mm⁻¹
c = 17.7120 (17) Å	T = 100 K
β = 95.429 (3)°	Stick, white
V = 878.73 (14) Å³	0.44 × 0.12 × 0.1 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	1785 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
CCD rotation images, thin slices scans	θ_max = 27.5°, θ_min = 3.7°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −5→5
T_min = 0.809, T_max = 0.962	k = −14→14
7536 measured reflections	l = −22→22
2006 independent 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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.08	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0283P)² + 0.5301P] where P = (F_o² + 2F_c²)/3
2006 reflections	(Δ/σ)_max = 0.001
113 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₈H₁₀NO₂⁺·Cl⁻	V = 878.73 (14) Å³
M_r = 187.62	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.4982 (4) Å	µ = 0.39 mm⁻¹
b = 11.0790 (11) Å	T = 100 K
c = 17.7120 (17) Å	0.44 × 0.12 × 0.1 mm
β = 95.429 (3)°

Data collection top

Bruker APEXII diffractometer	2006 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1785 reflections with I > 2σ(I)
T_min = 0.809, T_max = 0.962	R_int = 0.040
7536 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.08	H-atom parameters constrained
S = 1.03	Δρ_max = 0.30 e Å⁻³
2006 reflections	Δρ_min = −0.22 e Å⁻³
113 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Cl1	0.33999 (7)	0.14718 (3)	0.035821 (18)	0.01567 (11)
O1	0.7756 (3)	0.59938 (11)	0.02054 (6)	0.0270 (3)
H1	0.7238	0.6660	0.0040	0.040*
O2	0.5016 (3)	0.65210 (10)	0.11399 (6)	0.0257 (3)
N1	0.3016 (3)	0.37706 (11)	0.40929 (7)	0.0145 (3)
H1A	0.1824	0.3128	0.4051	0.022*
H1B	0.1969	0.4414	0.4212	0.022*
H1C	0.4494	0.3642	0.4455	0.022*
C1	0.4271 (3)	0.39836 (13)	0.33671 (8)	0.0126 (3)
C2	0.3601 (3)	0.32006 (13)	0.27659 (8)	0.0148 (3)
H2	0.2377	0.2535	0.2817	0.018*
C3	0.4804 (3)	0.34312 (13)	0.20801 (8)	0.0155 (3)
H3	0.4373	0.2911	0.1672	0.019*
C4	0.6631 (3)	0.44257 (13)	0.19984 (8)	0.0145 (3)
C5	0.7279 (3)	0.51913 (14)	0.26215 (8)	0.0176 (3)
H5	0.8524	0.5853	0.2576	0.021*
C6	0.6098 (3)	0.49813 (14)	0.33049 (8)	0.0166 (3)
H6	0.6522	0.5499	0.3714	0.020*
C7	0.7903 (3)	0.46817 (14)	0.12557 (8)	0.0180 (3)
H7A	0.7456	0.4006	0.0916	0.022*
H7B	1.0060	0.4744	0.1347	0.022*
C8	0.6709 (3)	0.58249 (14)	0.08711 (8)	0.0157 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01972 (19)	0.01379 (19)	0.01353 (18)	0.00041 (13)	0.00178 (13)	0.00186 (12)
O1	0.0392 (7)	0.0206 (6)	0.0239 (6)	0.0128 (5)	0.0181 (5)	0.0103 (5)
O2	0.0361 (7)	0.0226 (6)	0.0203 (6)	0.0151 (5)	0.0123 (5)	0.0061 (5)
N1	0.0169 (6)	0.0146 (6)	0.0124 (6)	−0.0011 (5)	0.0034 (5)	−0.0013 (5)
C4	0.0141 (6)	0.0146 (7)	0.0150 (7)	0.0054 (5)	0.0026 (5)	0.0034 (5)
C1	0.0131 (6)	0.0142 (7)	0.0108 (6)	0.0020 (5)	0.0025 (5)	0.0023 (5)
C6	0.0173 (7)	0.0163 (7)	0.0160 (7)	−0.0025 (6)	0.0003 (5)	−0.0027 (6)
C3	0.0190 (7)	0.0138 (7)	0.0137 (7)	0.0024 (6)	0.0011 (5)	−0.0020 (5)
C7	0.0199 (7)	0.0173 (7)	0.0178 (7)	0.0043 (6)	0.0071 (6)	0.0034 (6)
C8	0.0156 (7)	0.0161 (7)	0.0157 (7)	0.0003 (6)	0.0034 (5)	0.0007 (6)
C5	0.0152 (7)	0.0173 (7)	0.0206 (7)	−0.0039 (6)	0.0032 (5)	0.0013 (6)
C2	0.0161 (6)	0.0123 (7)	0.0159 (7)	−0.0021 (6)	0.0014 (5)	0.0000 (6)

Geometric parameters (Å, º) top

O1—C8	1.3234 (17)	C1—C6	1.388 (2)
O1—H1	0.8200	C6—C5	1.387 (2)
O2—C8	1.2121 (18)	C6—H6	0.9300
N1—C1	1.4709 (17)	C3—C2	1.399 (2)
N1—H1A	0.8900	C3—H3	0.9300
N1—H1B	0.8900	C7—C8	1.512 (2)
N1—H1C	0.8900	C7—H7A	0.9700
C4—C3	1.390 (2)	C7—H7B	0.9700
C4—C5	1.401 (2)	C5—H5	0.9300
C4—C7	1.5100 (19)	C2—H2	0.9300
C1—C2	1.384 (2)

C8—O1—H1	109.5	C4—C3—H3	119.5
C1—N1—H1A	109.5	C2—C3—H3	119.5
C1—N1—H1B	109.5	C4—C7—C8	113.72 (12)
H1A—N1—H1B	109.5	C4—C7—H7A	108.8
C1—N1—H1C	109.5	C8—C7—H7A	108.8
H1A—N1—H1C	109.5	C4—C7—H7B	108.8
H1B—N1—H1C	109.5	C8—C7—H7B	108.8
C3—C4—C5	118.62 (13)	H7A—C7—H7B	107.7
C3—C4—C7	121.06 (13)	O2—C8—O1	123.32 (14)
C5—C4—C7	120.33 (13)	O2—C8—C7	124.41 (13)
C2—C1—C6	121.69 (13)	O1—C8—C7	112.27 (12)
C2—C1—N1	119.89 (12)	C6—C5—C4	121.20 (14)
C6—C1—N1	118.42 (12)	C6—C5—H5	119.4
C5—C6—C1	118.77 (13)	C4—C5—H5	119.4
C5—C6—H6	120.6	C1—C2—C3	118.67 (13)
C1—C6—H6	120.6	C1—C2—H2	120.7
C4—C3—C2	121.05 (13)	C3—C2—H2	120.7

C2—C1—C6—C5	−0.1 (2)	C4—C7—C8—O1	−176.97 (13)
N1—C1—C6—C5	−179.72 (13)	C1—C6—C5—C4	0.7 (2)
C5—C4—C3—C2	0.7 (2)	C3—C4—C5—C6	−1.0 (2)
C7—C4—C3—C2	−179.38 (13)	C7—C4—C5—C6	179.07 (13)
C3—C4—C7—C8	113.71 (16)	C6—C1—C2—C3	−0.2 (2)
C5—C4—C7—C8	−66.37 (18)	N1—C1—C2—C3	179.42 (12)
C4—C7—C8—O2	3.9 (2)	C4—C3—C2—C1	−0.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1ⁱ	0.82	2.20	3.0087 (13)	171
N1—H1A···O2ⁱⁱ	0.89	1.98	2.8517 (17)	167
N1—H1B···Cl1ⁱⁱⁱ	0.89	2.41	3.2285 (13)	152
N1—H1C···Cl1^iv	0.89	2.26	3.1516 (14)	174
C2—H2···O2ⁱⁱ	0.93	2.49	3.2338 (18)	137
C3—H3···Cl1	0.93	2.82	3.7481 (15)	175

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

Experimental details

Crystal data
Chemical formula	C₈H₁₀NO₂⁺·Cl⁻
M_r	187.62
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	4.4982 (4), 11.0790 (11), 17.7120 (17)
β (°)	95.429 (3)
V (Å³)	878.73 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.44 × 0.12 × 0.1

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.809, 0.962
No. of measured, independent and observed [I > 2σ(I)] reflections	7536, 2006, 1785
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.08, 1.03
No. of reflections	2006
No. of parameters	113
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.22

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SIR2002 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Berndt, 2001), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1ⁱ	0.8200	2.2000	3.0087 (13)	171.00
N1—H1A···O2ⁱⁱ	0.8900	1.9800	2.8517 (17)	167.00
N1—H1B···Cl1ⁱⁱⁱ	0.8900	2.4100	3.2285 (13)	152.00
N1—H1C···Cl1^iv	0.8900	2.2600	3.1516 (14)	174.00
C2—H2···O2ⁱⁱ	0.9300	2.4900	3.2338 (18)	137.00
C3—H3···Cl1	0.9300	2.8200	3.7481 (15)	175.00

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

Acknowledgements

The authors are grateful to Dr Thierry Roisnel, Centre de Diffractométrie X (CDIFX) de Rennes, Université de Rennes 1, France, for data-collection facilities. SB thanks Université A. Mira de Béjaia, Algeria, for financial support.

References

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