4-Chloro­anilinium bromide

Zhao, M.-M.

doi:10.1107/S1600536812024993

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2022

https://doi.org/10.1107/S1600536812024993

Open

access

4-Chloroanilinium bromide

Min-Min Zhao ^a ^*

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

(Received 29 May 2012; accepted 1 June 2012; online 13 June 2012)

In the title compound, C₆H₇ClN⁺·Br⁻, the amino N atom is protonated. All non-H atoms of the cation are essentially coplanar [r.m.s. deviation = 0.004 (3) Å]. In the crystal, N—H⋯Br hydrogen bonds connect the ions, forming a ribbon-like structure propagating along [010].

Related literature

For the structures and properties of related compounds, see: Fu et al. (2011a ,b ,c ); Wang et al. (2002 ); Xue et al. (2002 ); Ye et al. (2008 ).

Experimental

Crystal data

C₆H₇ClN⁺·Br⁻
M_r = 208.49
Triclinic, $[P \overline 1]$
a = 4.3989 (2) Å
b = 6.2553 (2) Å
c = 13.8907 (8) Å
α = 91.4000 (8)°
β = 93.580 (1)°
γ = 101.967 (1)°
V = 372.91 (3) Å³
Z = 2
Mo Kα radiation
μ = 5.78 mm⁻¹
T = 153 K
0.10 × 0.05 × 0.05 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.910, T_max = 1.000
3843 measured reflections
1647 independent reflections
1435 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.103
S = 1.11
1647 reflections
83 parameters
H-atom parameters constrained
Δρ_max = 0.84 e Å⁻³
Δρ_min = −1.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Br1ⁱ	0.89	2.59	3.467 (4)	167
N1—H1B⋯Br1ⁱⁱ	0.89	2.52	3.370 (4)	161
N1—H1C⋯Br1ⁱⁱⁱ	0.89	2.46	3.312 (4)	161
Symmetry codes: (i) x+1, y-1, z; (ii) x+1, y, z; (iii) -x+1, -y+1, -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: https://doi.org/10.1107/S1600536812024993/aa2066sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812024993/aa2066Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812024993/aa2066Isup3.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 (Fu et al., 2011a, b, c). 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).

In the title compound (Fig. 1), the bond lengths and angles have normal values. The asymmetric unit is composed of one 4-chloroanilinium cation and one Br^- anion. The protonated N atom is involved in strong intermolecular N—H···Br hydrogen bonds (Table 1) which connect the ions into a 2D network parallel to the ab–plane (Fig. 2). The crystal packing is further stabilized by aromatic π–π interactions between the benzene rings of the neighbouring cations with the Cg···Cg distances of 4.399 (1)Å (Cg is the centroid of the benzene ring).

Related literature top

For the structures and properties of related compounds, see: Fu et al. (2011a,b,c); Wang et al. (2002); Xue et al. (2002); Ye et al. (2008).

Experimental top

The HBr (1 mL, 2 mol/L), 4-chloroaniline (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.

Structure description top

For the structures and properties of related compounds, see: Fu et al. (2011a,b,c); Wang et al. (2002); Xue et al. (2002); Ye et al. (2008).

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.
	Fig. 2. The crystal packing of the title compound viewed along the a axis showing the H–bonding and π–π interactions (dashed line), Cg is the centroid of the benzene ring.

4-Chloroanilinium bromide top

Crystal data top

C₆H₇ClN⁺·Br⁻	Z = 2
M_r = 208.49	F(000) = 204
Triclinic, P1	D_x = 1.857 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.3989 (2) Å	Cell parameters from 1674 reflections
b = 6.2553 (2) Å	θ = 3.0–27.5°
c = 13.8907 (8) Å	µ = 5.78 mm⁻¹
α = 91.4000 (8)°	T = 153 K
β = 93.580 (1)°	Block, colourless
γ = 101.967 (1)°	0.10 × 0.05 × 0.05 mm
V = 372.91 (3) Å³

Data collection top

Rigaku Mercury CCD diffractometer	1647 independent reflections
Radiation source: fine-focus sealed tube	1435 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 2.9°
CCD profile fitting scans	h = −5→5
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −8→8
T_min = 0.910, T_max = 1.000	l = −18→18
3843 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.044P)²] where P = (F_o² + 2F_c²)/3
1647 reflections	(Δ/σ)_max < 0.001
83 parameters	Δρ_max = 0.84 e Å⁻³
0 restraints	Δρ_min = −1.47 e Å⁻³

Crystal data top

C₆H₇ClN⁺·Br⁻	γ = 101.967 (1)°
M_r = 208.49	V = 372.91 (3) Å³
Triclinic, P1	Z = 2
a = 4.3989 (2) Å	Mo Kα radiation
b = 6.2553 (2) Å	µ = 5.78 mm⁻¹
c = 13.8907 (8) Å	T = 153 K
α = 91.4000 (8)°	0.10 × 0.05 × 0.05 mm
β = 93.580 (1)°

Data collection top

Rigaku Mercury CCD diffractometer	1647 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1435 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.056
3843 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.11	Δρ_max = 0.84 e Å⁻³
1647 reflections	Δρ_min = −1.47 e Å⁻³
83 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s 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	0.6759 (3)	0.27570 (19)	0.99710 (9)	0.0205 (3)
N1	1.1049 (9)	0.2261 (6)	0.6017 (3)	0.0136 (8)
H1A	1.2142	0.1217	0.5980	0.020*
H1B	1.2258	0.3545	0.5904	0.020*
H1C	0.9437	0.1973	0.5580	0.020*
C1	0.7915 (11)	0.2566 (8)	0.8806 (4)	0.0154 (10)
Br1	0.41356 (10)	0.76145 (7)	0.58041 (3)	0.01335 (18)
C2	0.7543 (11)	0.4182 (7)	0.8164 (3)	0.0155 (10)
H2A	0.6637	0.5329	0.8352	0.019*
C3	0.8537 (11)	0.4061 (7)	0.7241 (4)	0.0151 (10)
H3A	0.8289	0.5113	0.6798	0.018*
C4	0.9907 (10)	0.2340 (7)	0.6991 (3)	0.0113 (9)
C5	1.0258 (11)	0.0722 (7)	0.7620 (3)	0.0151 (10)
H5A	1.1156	−0.0428	0.7430	0.018*
C6	0.9254 (11)	0.0842 (7)	0.8533 (4)	0.0159 (10)
H6A	0.9471	−0.0233	0.8968	0.019*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0316 (7)	0.0169 (6)	0.0146 (6)	0.0075 (5)	0.0080 (5)	−0.0018 (5)
N1	0.018 (2)	0.011 (2)	0.012 (2)	0.0037 (16)	−0.0009 (17)	−0.0014 (16)
C1	0.017 (2)	0.014 (2)	0.015 (3)	0.0028 (19)	0.002 (2)	−0.0045 (19)
Br1	0.0165 (3)	0.0087 (3)	0.0154 (3)	0.00395 (18)	0.00213 (18)	−0.00161 (17)
C2	0.020 (2)	0.011 (2)	0.018 (3)	0.0072 (19)	0.004 (2)	−0.0033 (19)
C3	0.018 (2)	0.009 (2)	0.019 (3)	0.0018 (19)	0.001 (2)	0.0029 (19)
C4	0.013 (2)	0.009 (2)	0.010 (2)	−0.0007 (17)	0.0002 (18)	−0.0041 (18)
C5	0.019 (2)	0.011 (2)	0.017 (3)	0.0065 (19)	0.003 (2)	−0.0043 (19)
C6	0.023 (3)	0.008 (2)	0.016 (3)	0.0023 (19)	−0.001 (2)	0.0000 (19)

Geometric parameters (Å, º) top

Cl1—C1	1.735 (5)	C2—H2A	0.9300
N1—C4	1.476 (6)	C3—C4	1.385 (6)
N1—H1A	0.8900	C3—H3A	0.9300
N1—H1B	0.8900	C4—C5	1.379 (6)
N1—H1C	0.8900	C5—C6	1.375 (7)
C1—C6	1.388 (6)	C5—H5A	0.9300
C1—C2	1.392 (6)	C6—H6A	0.9300
C2—C3	1.385 (7)

C4—N1—H1A	109.5	C4—C3—C2	118.6 (4)
C4—N1—H1B	109.5	C4—C3—H3A	120.7
H1A—N1—H1B	109.5	C2—C3—H3A	120.7
C4—N1—H1C	109.5	C5—C4—C3	122.5 (4)
H1A—N1—H1C	109.5	C5—C4—N1	119.2 (4)
H1B—N1—H1C	109.5	C3—C4—N1	118.3 (4)
C6—C1—C2	120.9 (5)	C6—C5—C4	118.7 (4)
C6—C1—Cl1	119.8 (4)	C6—C5—H5A	120.6
C2—C1—Cl1	119.2 (4)	C4—C5—H5A	120.6
C3—C2—C1	119.3 (4)	C5—C6—C1	120.0 (4)
C3—C2—H2A	120.4	C5—C6—H6A	120.0
C1—C2—H2A	120.4	C1—C6—H6A	120.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1ⁱ	0.89	2.59	3.467 (4)	167
N1—H1B···Br1ⁱⁱ	0.89	2.52	3.370 (4)	161
N1—H1C···Br1ⁱⁱⁱ	0.89	2.46	3.312 (4)	161

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

Experimental details

Crystal data
Chemical formula	C₆H₇ClN⁺·Br⁻
M_r	208.49
Crystal system, space group	Triclinic, P1
Temperature (K)	153
a, b, c (Å)	4.3989 (2), 6.2553 (2), 13.8907 (8)
α, β, γ (°)	91.4000 (8), 93.580 (1), 101.967 (1)
V (Å³)	372.91 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.78
Crystal size (mm)	0.10 × 0.05 × 0.05

Data collection
Diffractometer	Rigaku Mercury CCD
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	3843, 1647, 1435
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.103, 1.11
No. of reflections	1647
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.84, −1.47

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···Br1ⁱ	0.89	2.59	3.467 (4)	167.4
N1—H1B···Br1ⁱⁱ	0.89	2.52	3.370 (4)	160.5
N1—H1C···Br1ⁱⁱⁱ	0.89	2.46	3.312 (4)	160.7

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

Acknowledgements

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

References

Fu, D.-W., Zhang, W., Cai, H.-L., Zhang, Y., Ge, J.-Z., Xiong, R.-G. & Huang, S. P. D. (2011a). J. Am. Chem. Soc. 133, 12780–12786. Web of Science CSD CrossRef CAS PubMed Google Scholar
Fu, D.-W., Zhang, W., Cai, H.-L., Zhang, Y., Ge, J.-Z., Xiong, R.-G., Huang, S. P. D. & Nakamura, T. (2011b). Angew. Chem. Int. Ed. 50, 11947–11951. Web of Science CSD CrossRef CAS Google Scholar
Fu, D.-W., Zhao, M.-M. & Ge, J.-Z. (2011c). J. Mol. Struct. 1006, 227–233. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, L.-Z., Wang, X.-S., Li, Y.-H., Bai, Z.-P., Xiong, R.-G., Xiong, M. & Li, G.-W. (2002). Chinese J. Inorg. Chem. 18, 1191–1194. CAS Google Scholar
Xue, X., Abrahams, B. F., Xiong, R.-G. & You, X.-Z. (2002). Aust. J. Chem. 55, 495–497. CSD CrossRef CAS Google Scholar
Ye, Q., Fu, D.-W., Hang, T., Xiong, R.-G., Chan, P. W. H. & Huang, S. P. D. (2008). Inorg. Chem. 47, 772–774. Web of Science CSD CrossRef PubMed CAS Google Scholar