2,6-Dibromo-4-butyl­anilinium chloride

Zhao, L.; Feng, L.-P.

doi:10.1107/S1600536810047811

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3266

https://doi.org/10.1107/S1600536810047811

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2,6-Dibromo-4-butylanilinium chloride

Liang Zhao ^a ^* and Li-Ping Feng ^a

^aDepartment of Chemical & Environmental Engineering, Anyang Institute of Technology, Anyang 455000, People's Republic of China
^*Correspondence e-mail: ayitzhao@yahoo.com.cn

(Received 12 November 2010; accepted 17 November 2010; online 24 November 2010)

In the crystal structure of the title salt, C₁₀H₁₄Br₂N⁺·Cl⁻, the organic cations and chloride anions are linked into one-dimensional chains parallel to the a axis by N—H⋯Cl and N—H⋯Br hydrogen bonds.

Related literature

For general background to supramolecular self-assembly chemisty, see: Lehn Lehn (1995 ); Scheiner (1997 ).

Experimental

Crystal data

C₁₀H₁₄Br₂N⁺·Cl⁻
M_r = 343.49
Triclinic, $[P \overline 1]$
a = 4.9785 (10) Å
b = 8.7844 (18) Å
c = 14.898 (3) Å
α = 86.29 (3)°
β = 87.58 (3)°
γ = 87.17 (3)°
V = 648.9 (2) Å³
Z = 2
Mo Kα radiation
μ = 6.42 mm⁻¹
T = 298 K
0.10 × 0.03 × 0.03 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.910, T_max = 1.000
6685 measured reflections
2959 independent reflections
1843 reflections with I > 2σ(I)
R_int = 0.073

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.159
S = 1.04
2959 reflections
128 parameters
7 restraints
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯Cl1ⁱ	0.89	2.59	3.240 (5)	130
N1—H1D⋯Cl1ⁱⁱ	0.89	2.68	3.136 (5)	113
N1—H1C⋯Br1ⁱⁱⁱ	0.89	2.82	3.517 (5)	135
N1—H1B⋯Br1	0.89	2.51	3.094 (5)	124
N1—H1B⋯Cl1	0.89	2.72	3.212 (6)	116
Symmetry codes: (i) -x, -y, -z; (ii) -x+1, -y, -z; (iii) x-1, y, z.

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/S1600536810047811/rz2526sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810047811/rz2526Isup2.hkl

checkCIF report

Comment top

In recent years there has been a rapidly increasing interest in the construction of various kinds of supramolecular systems for understanding molecular self-assembly principles and for designing molecular recognition. A supramolecular system generally refers to an assembly of molecules which are not covalently connected but assembled by other weak intermolecular interactions, such as hydrogen bonds (Lehn, 1995; Scheiner, 1997). We report here the crystal structure of the title compound, 2,6-dibromo-4-butylanilinium chloride.

In the title compound (Fig.1), the butyl group is approximately orthogonal to the benzene plane, as indicated by the torsion angles C1—C6—C7—C8 and C5—C6—C7—C8 of 76.2 (11) and -102.7 (10)°, respectively. The Br1, Br2 and N1 substituents are displaced by 0.0842 (8), 0.1142 (8) and -0.005 (5) Å, respectively, with respect to the benzene ring. Bond lengths and angles lie within normal ranges. In the crystal structure, the organic cations and Cl^- anions are linked by N—H···Cl and N—H···Br hydrogen bonds (Table 1) to form one-dimensional chains along the a axis (Fig. 2).

Related literature top

For general background to supramolecular self-assembly chemisty, see: Lehn Lehn (1995); Scheiner (1997).

Experimental top

The title compound was purchased from ALFA AESAR. The compound (3 mmol) was dissolved in ethanol (20 ml) and the solution allowed to evaporate to obtain colourless block-shaped crystals of the title compound suitable for X-ray analysis.

Structure description top

For general background to supramolecular self-assembly chemisty, see: Lehn Lehn (1995); Scheiner (1997).

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 title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Partial crystal packing of the title compound showing a chain formed along the a axis. H atoms not involved in hydrogen bonding (dashed lines) are omitted for clarity.

2,6-Dibromo-4-butylanilinium chloride top

Crystal data top

C₁₀H₁₄Br₂N⁺·Cl⁻	Z = 2
M_r = 343.49	F(000) = 336
Triclinic, P1	D_x = 1.758 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.9785 (10) Å	Cell parameters from 2959 reflections
b = 8.7844 (18) Å	θ = 3.5–27.5°
c = 14.898 (3) Å	µ = 6.42 mm⁻¹
α = 86.29 (3)°	T = 298 K
β = 87.58 (3)°	Block, colourless
γ = 87.17 (3)°	0.10 × 0.03 × 0.03 mm
V = 648.9 (2) Å³

Data collection top

Rigaku Mercury2 diffractometer	2959 independent reflections
Radiation source: fine-focus sealed tube	1843 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.073
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.5°
CCD profile fitting scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −11→11
T_min = 0.910, T_max = 1.000	l = −19→19
6685 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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.159	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0602P)² + 0.1405P] where P = (F_o² + 2F_c²)/3
2959 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.74 e Å⁻³
7 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

C₁₀H₁₄Br₂N⁺·Cl⁻	γ = 87.17 (3)°
M_r = 343.49	V = 648.9 (2) Å³
Triclinic, P1	Z = 2
a = 4.9785 (10) Å	Mo Kα radiation
b = 8.7844 (18) Å	µ = 6.42 mm⁻¹
c = 14.898 (3) Å	T = 298 K
α = 86.29 (3)°	0.10 × 0.03 × 0.03 mm
β = 87.58 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2959 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1843 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.073
6685 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	7 restraints
wR(F²) = 0.159	H-atom parameters constrained
S = 1.04	Δρ_max = 0.74 e Å⁻³
2959 reflections	Δρ_min = −0.59 e Å⁻³
128 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
Br1	0.72826 (13)	0.30511 (8)	0.02752 (5)	0.0481 (3)
Br2	−0.07834 (15)	0.10595 (9)	0.28643 (5)	0.0591 (3)
C6	0.3280 (15)	0.5078 (8)	0.2416 (5)	0.0510 (18)
C3	0.3104 (12)	0.2297 (6)	0.1577 (4)	0.0380 (15)
C5	0.4948 (15)	0.4763 (7)	0.1683 (5)	0.0533 (19)
H5A	0.6159	0.5483	0.1463	0.064*
C2	0.1509 (13)	0.2581 (7)	0.2341 (5)	0.0399 (15)
N1	0.2929 (10)	0.0916 (5)	0.1091 (4)	0.0414 (13)
H1B	0.4105	0.0939	0.0624	0.062*
H1C	0.1273	0.0870	0.0895	0.062*
H1D	0.3304	0.0099	0.1457	0.062*
C4	0.4871 (13)	0.3411 (7)	0.1268 (4)	0.0426 (16)
C1	0.1564 (14)	0.3928 (8)	0.2748 (5)	0.0503 (18)
H1A	0.0447	0.4087	0.3253	0.060*
Cl1	0.2000 (3)	0.13452 (17)	−0.10326 (12)	0.0454 (4)
C7	0.332 (2)	0.6574 (9)	0.2856 (6)	0.074 (2)
H7A	0.4159	0.7317	0.2438	0.088*
H7B	0.1476	0.6943	0.2976	0.088*
C8	0.475 (2)	0.6474 (10)	0.3703 (8)	0.100 (3)
H8A	0.6534	0.6011	0.3588	0.120*
H8B	0.3813	0.5790	0.4131	0.120*
C9	0.507 (3)	0.7949 (12)	0.4139 (8)	0.121 (3)
H9A	0.5983	0.8641	0.3707	0.145*
H9B	0.3291	0.8403	0.4266	0.145*
C10	0.656 (3)	0.7844 (12)	0.4977 (8)	0.124 (3)
H10A	0.7705	0.8690	0.4979	0.185*
H10B	0.7628	0.6905	0.5015	0.185*
H10C	0.5302	0.7869	0.5484	0.185*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0415 (4)	0.0531 (4)	0.0507 (5)	−0.0095 (3)	−0.0033 (3)	−0.0037 (3)
Br2	0.0639 (5)	0.0619 (5)	0.0529 (6)	−0.0181 (4)	0.0049 (4)	−0.0073 (4)
C6	0.065 (5)	0.044 (4)	0.045 (5)	−0.003 (4)	−0.011 (4)	−0.009 (3)
C3	0.042 (3)	0.030 (3)	0.044 (4)	−0.003 (3)	−0.012 (3)	−0.008 (3)
C5	0.064 (5)	0.034 (4)	0.063 (5)	−0.008 (3)	−0.019 (4)	0.002 (3)
C2	0.047 (4)	0.034 (3)	0.039 (4)	−0.004 (3)	−0.003 (3)	−0.002 (3)
N1	0.039 (3)	0.033 (3)	0.053 (4)	−0.007 (2)	−0.002 (3)	−0.010 (2)
C4	0.046 (4)	0.044 (4)	0.038 (4)	0.008 (3)	−0.012 (3)	0.001 (3)
C1	0.052 (4)	0.057 (4)	0.042 (4)	−0.001 (4)	0.003 (4)	−0.013 (3)
Cl1	0.0441 (9)	0.0400 (8)	0.0535 (11)	−0.0059 (7)	−0.0057 (8)	−0.0093 (7)
C7	0.109 (7)	0.044 (4)	0.070 (6)	−0.012 (4)	0.000 (6)	−0.013 (4)
C8	0.129 (8)	0.065 (6)	0.112 (10)	0.000 (6)	−0.036 (7)	−0.039 (6)
C9	0.181 (9)	0.080 (5)	0.111 (7)	−0.013 (6)	−0.050 (6)	−0.043 (5)
C10	0.183 (9)	0.083 (5)	0.113 (7)	−0.011 (6)	−0.049 (6)	−0.041 (5)

Geometric parameters (Å, º) top

Br1—C4	1.898 (7)	C1—H1A	0.9300
Br2—C2	1.907 (6)	C7—C8	1.473 (12)
C6—C5	1.377 (10)	C7—H7A	0.9700
C6—C1	1.407 (10)	C7—H7B	0.9700
C6—C7	1.507 (10)	C8—C9	1.504 (12)
C3—C2	1.389 (9)	C8—H8A	0.9700
C3—C4	1.391 (8)	C8—H8B	0.9700
C3—N1	1.461 (7)	C9—C10	1.474 (15)
C5—C4	1.378 (9)	C9—H9A	0.9700
C5—H5A	0.9300	C9—H9B	0.9700
C2—C1	1.365 (9)	C10—H10A	0.9600
N1—H1B	0.8900	C10—H10B	0.9600
N1—H1C	0.8900	C10—H10C	0.9600
N1—H1D	0.8900

C5—C6—C1	117.0 (6)	C8—C7—C6	113.8 (7)
C5—C6—C7	121.8 (7)	C8—C7—H7A	108.8
C1—C6—C7	121.2 (7)	C6—C7—H7A	108.8
C2—C3—C4	117.2 (5)	C8—C7—H7B	108.8
C2—C3—N1	122.6 (5)	C6—C7—H7B	108.8
C4—C3—N1	120.1 (6)	H7A—C7—H7B	107.7
C6—C5—C4	121.8 (7)	C7—C8—C9	116.7 (9)
C6—C5—H5A	119.1	C7—C8—H8A	108.1
C4—C5—H5A	119.1	C9—C8—H8A	108.1
C1—C2—C3	121.7 (6)	C7—C8—H8B	108.1
C1—C2—Br2	118.2 (5)	C9—C8—H8B	108.1
C3—C2—Br2	120.2 (4)	H8A—C8—H8B	107.3
C3—N1—H1B	109.5	C10—C9—C8	116.4 (10)
C3—N1—H1C	109.5	C10—C9—H9A	108.2
H1B—N1—H1C	109.5	C8—C9—H9A	108.2
C3—N1—H1D	109.5	C10—C9—H9B	108.2
H1B—N1—H1D	109.5	C8—C9—H9B	108.2
H1C—N1—H1D	109.5	H9A—C9—H9B	107.4
C5—C4—C3	121.1 (6)	C9—C10—H10A	109.5
C5—C4—Br1	119.1 (5)	C9—C10—H10B	109.5
C3—C4—Br1	119.8 (5)	H10A—C10—H10B	109.5
C2—C1—C6	121.1 (6)	C9—C10—H10C	109.5
C2—C1—H1A	119.4	H10A—C10—H10C	109.5
C6—C1—H1A	119.4	H10B—C10—H10C	109.5

C1—C6—C5—C4	2.6 (11)	C2—C3—C4—Br1	175.9 (5)
C7—C6—C5—C4	−178.4 (7)	N1—C3—C4—Br1	−5.7 (8)
C4—C3—C2—C1	3.2 (9)	C3—C2—C1—C6	−1.0 (10)
N1—C3—C2—C1	−175.1 (6)	Br2—C2—C1—C6	177.7 (5)
C4—C3—C2—Br2	−175.5 (4)	C5—C6—C1—C2	−1.9 (10)
N1—C3—C2—Br2	6.1 (8)	C7—C6—C1—C2	179.1 (7)
C6—C5—C4—C3	−0.4 (10)	C5—C6—C7—C8	−102.7 (10)
C6—C5—C4—Br1	−178.9 (5)	C1—C6—C7—C8	76.2 (11)
C2—C3—C4—C5	−2.5 (9)	C6—C7—C8—C9	175.0 (10)
N1—C3—C4—C5	175.9 (6)	C7—C8—C9—C10	−178.9 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···Cl1ⁱ	0.89	2.59	3.240 (5)	130
N1—H1D···Cl1ⁱⁱ	0.89	2.68	3.136 (5)	113
N1—H1C···Br1ⁱⁱⁱ	0.89	2.82	3.517 (5)	135
N1—H1B···Br1	0.89	2.51	3.094 (5)	124
N1—H1B···Cl1	0.89	2.72	3.212 (6)	116

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₄Br₂N⁺·Cl⁻
M_r	343.49
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	4.9785 (10), 8.7844 (18), 14.898 (3)
α, β, γ (°)	86.29 (3), 87.58 (3), 87.17 (3)
V (Å³)	648.9 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	6.42
Crystal size (mm)	0.10 × 0.03 × 0.03

Data collection
Diffractometer	Rigaku Mercury2
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	6685, 2959, 1843
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.159, 1.04
No. of reflections	2959
No. of parameters	128
No. of restraints	7
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.59

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—H1C···Cl1ⁱ	0.89	2.59	3.240 (5)	130.4
N1—H1D···Cl1ⁱⁱ	0.89	2.68	3.136 (5)	113.3
N1—H1C···Br1ⁱⁱⁱ	0.89	2.82	3.517 (5)	135
N1—H1B···Br1	0.89	2.51	3.094 (5)	123.5
N1—H1B···Cl1	0.89	2.72	3.212 (6)	116.3

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

Acknowledgements

This work was supported by a School start-up grant to LZ.

References

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar