4-Carb­oxy­anilinium chloride

Han, L.-J.; Yang, S.-P.; Tao, X.; Ma, Y.-F.

doi:10.1107/S1600536811046721

organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3247

https://doi.org/10.1107/S1600536811046721

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4-Carboxyanilinium chloride

Li-Jun Han,^a ^* Shu-Ping Yang,^b Xin Tao ^b and Yuan-Feng Ma ^b

^aDepartment of Mathematics and Science, Huaihai Institute of Technology, Lianyungang 222005, People's Republic of China, and ^bDepartment of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005, People's Republic of China
^*Correspondence e-mail: spyang69320@yahoo.cn

(Received 1 November 2011; accepted 5 November 2011; online 9 November 2011)

In the title salt, C₇H₈NO₂⁺·Cl⁻, the cation and anion are linked by an O—H⋯Cl hydrogen bond. The three-dimensional crystal structure is stabilized by N—H⋯O and N—H⋯Cl hydrogen bonds.

Related literature

For related structures, see: Athimoolam & Natarajan (2007 ); Gracin & Fischer (2005 ).

Experimental

Crystal data

C₇H₈NO₂⁺·Cl⁻
M_r = 173.59
Monoclinic, P 2₁ /c
a = 5.601 (5) Å
b = 8.269 (5) Å
c = 17.118 (5) Å
β = 96.371 (5)°
V = 787.9 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 298 K
0.50 × 0.40 × 0.30 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.814, T_max = 0.882
4205 measured reflections
1299 independent reflections
1210 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.192
S = 1.26
1299 reflections
133 parameters
All H-atom parameters refined
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Cl1	0.99 (8)	2.10 (8)	3.059 (4)	164 (6)
N1—H1A⋯Cl1ⁱ	0.85 (6)	2.33 (6)	3.154 (6)	165 (5)
N1—H1B⋯O2ⁱⁱ	0.88 (9)	2.05 (8)	2.823 (6)	145 (7)
N1—H1B⋯Cl1ⁱⁱⁱ	0.88 (9)	2.70 (9)	3.289 (5)	125 (6)
N1—H1C⋯Cl1ⁱⁱ	0.96 (8)	2.26 (8)	3.215 (5)	172 (6)
Symmetry codes: (i) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811046721/wn2458sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811046721/wn2458Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811046721/wn2458Isup3.cml

checkCIF report

Comment top

We intended to prepare a cerium(III) complex of p-aminobenzoic acid. However, we obtained crystals of the title salt, and we report here its crystal structure.

In the title salt, the asymmetric unit consists of one p-aminobenzoic acid cation and one chloride anion (Fig. 1).

The amine group is protonated and the C4—N1 bond length is 1.471 (7) Å. In the crystal structure of 4-carboxyanilinium(2R, 3R)-tartrate (Athimoolam & Natarajan, 2007) the amine group is also protonated and the values of the corresponding C—N bond lengths are 1.464 (6) Å and 1.476 (5) Å.

In the crystal structures of the α-polymorph of p-aminobenzoic acid (Athimoolam & Natarajan, 2007) and β-polymorph of p-aminobenzoic acid (Gracin & Fischer, 2005) the amino group is not protonated. For the α-polymorph the C—N distance is 1.372 (5) Å; for the β-polymorph the distance is 1.408 (3) Å.

The hydrogen bonds listed in Table 1 result in a crystal structure generated by inversion and glide symmetry (Fig. 2).

Related literature top

For related structures, see: Athimoolam & Natarajan (2007); Gracin & Fischer (2005).

Experimental top

To a solution containing p-aminobenzoic acid (1.37 g, 10 mmol) in ethanol (30 ml), a solution of cerium(III) chloride (1.24 g, 5 mmol) in methanol (15 ml) was added with stirring for 2 h at 323 K, and then the solution was filtered. Colourless crystals suitable for X-ray crystal structure analysis were obtained from the filtered solution over a period of two weeks.

Structure description top

We intended to prepare a cerium(III) complex of p-aminobenzoic acid. However, we obtained crystals of the title salt, and we report here its crystal structure.

In the title salt, the asymmetric unit consists of one p-aminobenzoic acid cation and one chloride anion (Fig. 1).

The hydrogen bonds listed in Table 1 result in a crystal structure generated by inversion and glide symmetry (Fig. 2).

For related structures, see: Athimoolam & Natarajan (2007); Gracin & Fischer (2005).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title structure. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are shown as spheres of arbitrary radius.
	Fig. 2. Part of the crystal structure, with hydrogen bonds shown as dashed lines. For clarity, H atoms not involved in the hydrogen bonds have been omitted. [Symmetry code:(*).1 - x, 1 - y, 1 - z (#). 1 + x, 1/2 - y, 1/2 + z,(&). x, 1/2 - y, 1/2 + z].

4-Carboxyanilinium chloride top

Crystal data top

C₇H₈NO₂⁺·Cl⁻	F(000) = 360
M_r = 173.59	D_x = 1.463 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3678 reflections
a = 5.601 (5) Å	θ = 2.4–29.3°
b = 8.269 (5) Å	µ = 0.43 mm⁻¹
c = 17.118 (5) Å	T = 298 K
β = 96.371 (5)°	Block, yellow
V = 787.9 (9) Å³	0.50 × 0.40 × 0.30 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	1299 independent reflections
Radiation source: fine-focus sealed tube	1210 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
φ and ω scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −6→6
T_min = 0.814, T_max = 0.882	k = −9→7
4205 measured reflections	l = −20→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.054	All H-atom parameters refined
wR(F²) = 0.192	w = 1/[σ²(F_o²) + (0.0616P)² + 2.6608P] where P = (F_o² + 2F_c²)/3
S = 1.26	(Δ/σ)_max < 0.001
1299 reflections	Δρ_max = 0.49 e Å⁻³
133 parameters	Δρ_min = −0.34 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.075 (12)

Crystal data top

C₇H₈NO₂⁺·Cl⁻	V = 787.9 (9) Å³
M_r = 173.59	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.601 (5) Å	µ = 0.43 mm⁻¹
b = 8.269 (5) Å	T = 298 K
c = 17.118 (5) Å	0.50 × 0.40 × 0.30 mm
β = 96.371 (5)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1299 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1210 reflections with I > 2σ(I)
T_min = 0.814, T_max = 0.882	R_int = 0.030
4205 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.192	All H-atom parameters refined
S = 1.26	Δρ_max = 0.49 e Å⁻³
1299 reflections	Δρ_min = −0.34 e Å⁻³
133 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
C1	0.5758 (9)	0.2824 (5)	0.5157 (3)	0.0322 (11)
C2	0.3637 (8)	0.1926 (6)	0.4999 (3)	0.0332 (11)
C3	0.3059 (9)	0.1230 (6)	0.4273 (3)	0.0367 (12)
C4	0.4607 (8)	0.1434 (5)	0.3701 (3)	0.0314 (11)
C5	0.6671 (9)	0.2347 (6)	0.3835 (3)	0.0362 (12)
C6	0.7245 (9)	0.3053 (6)	0.4564 (3)	0.0376 (12)
C7	0.6379 (9)	0.3487 (6)	0.5964 (3)	0.0348 (11)
N1	0.4043 (9)	0.0640 (6)	0.2933 (3)	0.0374 (10)
O1	0.8194 (7)	0.4512 (5)	0.6027 (2)	0.0488 (11)
O2	0.5313 (8)	0.3078 (5)	0.6508 (2)	0.0573 (12)
Cl1	0.9009 (2)	0.60977 (15)	0.76491 (7)	0.0407 (5)
H1	0.858 (13)	0.482 (9)	0.659 (5)	0.09 (2)*
H1A	0.279 (10)	0.006 (6)	0.293 (3)	0.032 (14)*
H1B	0.393 (14)	0.131 (11)	0.253 (5)	0.09 (3)*
H1C	0.545 (14)	0.002 (9)	0.286 (4)	0.08 (2)*
H2	0.262 (9)	0.183 (6)	0.541 (3)	0.034 (13)*
H3	0.175 (10)	0.067 (6)	0.419 (3)	0.033 (13)*
H5	0.780 (10)	0.249 (6)	0.347 (3)	0.042 (15)*
H6	0.863 (9)	0.363 (6)	0.465 (3)	0.026 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.035 (3)	0.030 (2)	0.033 (2)	0.0025 (19)	0.008 (2)	0.0034 (19)
C2	0.028 (2)	0.039 (3)	0.034 (2)	0.001 (2)	0.008 (2)	0.006 (2)
C3	0.033 (3)	0.035 (3)	0.045 (3)	−0.004 (2)	0.013 (2)	0.003 (2)
C4	0.033 (2)	0.028 (2)	0.035 (2)	0.0035 (19)	0.009 (2)	0.0035 (18)
C5	0.035 (3)	0.040 (3)	0.036 (3)	0.000 (2)	0.013 (2)	0.005 (2)
C6	0.033 (3)	0.037 (3)	0.046 (3)	−0.007 (2)	0.015 (2)	−0.001 (2)
C7	0.031 (2)	0.038 (2)	0.034 (2)	0.002 (2)	0.002 (2)	0.003 (2)
N1	0.036 (2)	0.041 (2)	0.035 (2)	−0.004 (2)	0.006 (2)	0.0016 (19)
O1	0.054 (2)	0.054 (2)	0.039 (2)	−0.0211 (19)	0.0078 (19)	−0.0046 (17)
O2	0.059 (3)	0.080 (3)	0.035 (2)	−0.025 (2)	0.014 (2)	−0.0088 (19)
Cl1	0.0353 (8)	0.0408 (8)	0.0459 (8)	0.0035 (5)	0.0043 (5)	−0.0016 (5)

Geometric parameters (Å, º) top

C1—C6	1.395 (6)	C5—C6	1.383 (7)
C1—C2	1.402 (7)	C5—H5	0.94 (5)
C1—C7	1.491 (7)	C6—H6	0.91 (5)
C2—C3	1.374 (7)	C7—O2	1.209 (6)
C2—H2	0.96 (5)	C7—O1	1.319 (6)
C3—C4	1.389 (6)	N1—H1A	0.85 (6)
C3—H3	0.87 (6)	N1—H1B	0.88 (9)
C4—C5	1.378 (7)	N1—H1C	0.96 (8)
C4—N1	1.471 (7)	O1—H1	0.99 (8)

C6—C1—C2	119.6 (5)	C6—C5—H5	116 (3)
C6—C1—C7	121.8 (5)	C5—C6—C1	120.1 (5)
C2—C1—C7	118.6 (4)	C5—C6—H6	118 (3)
C3—C2—C1	120.4 (4)	C1—C6—H6	121 (3)
C3—C2—H2	122 (3)	O2—C7—O1	124.0 (5)
C1—C2—H2	117 (3)	O2—C7—C1	121.8 (5)
C2—C3—C4	119.0 (5)	O1—C7—C1	114.2 (4)
C2—C3—H3	118 (3)	C4—N1—H1A	111 (3)
C4—C3—H3	123 (3)	C4—N1—H1B	114 (5)
C5—C4—C3	121.7 (5)	H1A—N1—H1B	111 (6)
C5—C4—N1	119.1 (4)	C4—N1—H1C	104 (5)
C3—C4—N1	119.1 (4)	H1A—N1—H1C	113 (6)
C4—C5—C6	119.3 (4)	H1B—N1—H1C	103 (6)
C4—C5—H5	125 (3)	C7—O1—H1	109 (4)

C6—C1—C2—C3	2.1 (7)	C4—C5—C6—C1	0.7 (8)
C7—C1—C2—C3	−176.9 (4)	C2—C1—C6—C5	−2.3 (7)
C1—C2—C3—C4	−0.1 (7)	C7—C1—C6—C5	176.6 (5)
C2—C3—C4—C5	−1.6 (7)	C6—C1—C7—O2	−167.9 (5)
C2—C3—C4—N1	177.7 (4)	C2—C1—C7—O2	11.1 (7)
C3—C4—C5—C6	1.4 (7)	C6—C1—C7—O1	10.8 (7)
N1—C4—C5—C6	−177.9 (5)	C2—C1—C7—O1	−170.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1	0.99 (8)	2.10 (8)	3.059 (4)	164 (6)
N1—H1A···Cl1ⁱ	0.85 (6)	2.33 (6)	3.154 (6)	165 (5)
N1—H1B···O2ⁱⁱ	0.88 (9)	2.05 (8)	2.823 (6)	145 (7)
N1—H1B···Cl1ⁱⁱⁱ	0.88 (9)	2.70 (9)	3.289 (5)	125 (6)
N1—H1C···Cl1ⁱⁱ	0.96 (8)	2.26 (8)	3.215 (5)	172 (6)

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

Experimental details

Crystal data
Chemical formula	C₇H₈NO₂⁺·Cl⁻
M_r	173.59
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	5.601 (5), 8.269 (5), 17.118 (5)
β (°)	96.371 (5)
V (Å³)	787.9 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.43
Crystal size (mm)	0.50 × 0.40 × 0.30

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.814, 0.882
No. of measured, independent and observed [I > 2σ(I)] reflections	4205, 1299, 1210
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.192, 1.26
No. of reflections	1299
No. of parameters	133
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.34

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Berndt, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1	0.99 (8)	2.10 (8)	3.059 (4)	164 (6)
N1—H1A···Cl1ⁱ	0.85 (6)	2.33 (6)	3.154 (6)	165 (5)
N1—H1B···O2ⁱⁱ	0.88 (9)	2.05 (8)	2.823 (6)	145 (7)
N1—H1B···Cl1ⁱⁱⁱ	0.88 (9)	2.70 (9)	3.289 (5)	125 (6)
N1—H1C···Cl1ⁱⁱ	0.96 (8)	2.26 (8)	3.215 (5)	172 (6)

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

Acknowledgements

The project was supported by the Natural Science Foundation of Huaihai Institute of Technology, China (No. Z2009019).

References

Athimoolam, S. & Natarajan, S. (2007). Acta Cryst. C63, o514–o517. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
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Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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