2,4,6-Trimethyl­anilinium bromide

Cui, L.-J.; Xu, H.-J.

doi:10.1107/S1600536809034497

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2376

doi:10.1107/S1600536809034497

Open

access

2,4,6-Trimethylanilinium bromide

Li-Jing Cui ^a and Hai-Jun Xu ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: xuhj@seu.edu.cn

(Received 27 August 2009; accepted 28 August 2009; online 9 September 2009)

In the title compound, C₉H₁₄N⁺·Br⁻, an intramolecular N—H⋯Br interaction links the anion to the cation. In the crystal structure, intermolecular N—H⋯Br interactions link the molecules into a three-dimensional network.

Related literature

For related structures, see: Lemmerer & Billing (2007 ); Long et al. (2007 ).

Experimental

Crystal data

C₉H₁₄N⁺·Br⁻
M_r = 216.11
Orthorhombic, P b c a
a = 10.399 (2) Å
b = 18.720 (4) Å
c = 10.282 (2) Å
V = 2001.6 (7) Å³
Z = 8
Mo Kα radiation
μ = 4.05 mm⁻¹
T = 294 K
0.2 × 0.2 × 0.2 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.88, T_max = 1.000
18944 measured reflections
2292 independent reflections
1627 reflections with I > 2σ(I)
R_int = 0.099

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.122
S = 1.00
2292 reflections
113 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Br1ⁱ	0.84 (5)	2.58 (5)	3.376 (4)	157 (4)
N1—H1B⋯Br1	0.94 (6)	2.47 (6)	3.391 (4)	168 (4)
N1—H1C⋯Br1ⁱⁱ	1.01 (5)	2.32 (5)	3.292 (4)	162 (4)
Symmetry codes: (i) -x, -y, -z+1; (ii) $[-x+{\script{1\over 2}}, -y, z-{\script{1\over 2}}]$ .

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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809034497/hk2763sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034497/hk2763Isup2.hkl

checkCIF report

Comment top

The crystal structure of the title compound is reported herein as part of a study of 2,4,6-trimethylanilinium halide salts. The other halide salts have been reported, previously (Lemmerer & Billing, 2007; Long et al., 2007).

The asymmetric unit of the title compound, (Fig. 1), contains one 2,4,6 -trimethylbenzenaminium cation and one bromide anion. The intramolecular N-H···Br interaction (Table 1) links the anion to the cation.

In the crystal structure, intra- and intermolecular N-H···Br interactions (Table 1) link the molecules into a three-dimensional network.

Related literature top

For related structures, see: Lemmerer & Billing (2007); Long et al. (2007).

Experimental top

For the preparation of the title compound, 2,4,6-trimethylaniline (3 mmol) was dissolved in ethanol (6 ml), and concentrated hydrobromic acid was added dropwise to dissolve the solid phase persisting in a mixture of bismuth tricbromide (3 mmol) and water (5 ml). The two solutions were then mixed and stirred for 15 min. The resulting precipitate was filtered off and dissolved in hydrobromic acid. Colorless crystals suitable for X-ray analysis were formed after several weeks by slow evaporation of the solvent at room temperature.

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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Hydrogen bond is shown as dashed line.

2,4,6-Trimethylanilinium bromide top

Crystal data top

C₉H₁₄N⁺·Br⁻	F(000) = 880
M_r = 216.11	D_x = 1.434 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1647 reflections
a = 10.399 (2) Å	θ = 3.0–27.6°
b = 18.720 (4) Å	µ = 4.05 mm⁻¹
c = 10.282 (2) Å	T = 294 K
V = 2001.6 (7) Å³	Prism, colorless
Z = 8	0.2 × 0.2 × 0.2 mm

Data collection top

Rigaku SCXmini diffractometer	2292 independent reflections
Radiation source: fine-focus sealed tube	1627 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.099
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −13→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −24→24
T_min = 0.88, T_max = 1.000	l = −13→13
18944 measured reflections

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)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.122	w = 1/[σ²(F_o²) + (0.0437P)² + 2.8318P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2292 reflections	Δρ_max = 0.37 e Å⁻³
113 parameters	Δρ_min = −0.41 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: 0.0097 (8)

Crystal data top

C₉H₁₄N⁺·Br⁻	V = 2001.6 (7) Å³
M_r = 216.11	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.399 (2) Å	µ = 4.05 mm⁻¹
b = 18.720 (4) Å	T = 294 K
c = 10.282 (2) Å	0.2 × 0.2 × 0.2 mm

Data collection top

Rigaku SCXmini diffractometer	2292 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1627 reflections with I > 2σ(I)
T_min = 0.88, T_max = 1.000	R_int = 0.099
18944 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.37 e Å⁻³
2292 reflections	Δρ_min = −0.41 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
Br1	0.10008 (4)	0.00542 (2)	0.69604 (4)	0.0471 (2)
N1	0.1859 (4)	0.0634 (2)	0.3959 (4)	0.0420 (9)
H1A	0.113 (4)	0.058 (2)	0.361 (5)	0.053 (14)*
H1B	0.171 (5)	0.042 (3)	0.477 (6)	0.085 (18)*
H1C	0.249 (4)	0.033 (3)	0.346 (4)	0.052 (12)*
C1	0.2218 (4)	0.1388 (2)	0.4055 (4)	0.0364 (9)
C2	0.3168 (4)	0.1578 (2)	0.4945 (4)	0.0466 (11)
C3	0.3457 (4)	0.2299 (3)	0.5046 (4)	0.0563 (13)
H3A	0.4063	0.2440	0.5659	0.068*
C4	0.2896 (5)	0.2813 (3)	0.4289 (5)	0.0545 (12)
C5	0.2005 (4)	0.2595 (2)	0.3376 (5)	0.0523 (11)
H5A	0.1630	0.2935	0.2837	0.063*
C6	0.1650 (4)	0.1883 (2)	0.3237 (4)	0.0416 (10)
C7	0.3892 (4)	0.1028 (3)	0.5721 (5)	0.0747 (17)
H7A	0.3565	0.0561	0.5525	0.112*
H7B	0.3786	0.1123	0.6633	0.112*
H7C	0.4789	0.1050	0.5503	0.112*
C8	0.3257 (6)	0.3597 (3)	0.4419 (6)	0.0892 (19)
H8A	0.2766	0.3874	0.3811	0.134*
H8B	0.4157	0.3655	0.4240	0.134*
H8C	0.3077	0.3756	0.5287	0.134*
C9	0.0696 (5)	0.1680 (3)	0.2198 (5)	0.0656 (14)
H9A	0.0422	0.2102	0.1744	0.098*
H9B	−0.0035	0.1454	0.2592	0.098*
H9C	0.1093	0.1356	0.1596	0.098*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0419 (3)	0.0519 (3)	0.0473 (3)	−0.00391 (19)	−0.00179 (18)	0.0025 (2)
N1	0.035 (2)	0.048 (2)	0.043 (2)	−0.0016 (17)	−0.0005 (18)	0.0009 (18)
C1	0.033 (2)	0.041 (2)	0.035 (2)	−0.0008 (17)	0.0048 (17)	0.0004 (18)
C2	0.037 (2)	0.065 (3)	0.038 (2)	−0.011 (2)	−0.0016 (19)	0.005 (2)
C3	0.052 (3)	0.078 (3)	0.039 (3)	−0.027 (3)	0.001 (2)	−0.012 (2)
C4	0.061 (3)	0.050 (3)	0.053 (3)	−0.016 (2)	0.012 (2)	−0.006 (2)
C5	0.050 (2)	0.049 (3)	0.058 (3)	0.001 (2)	0.002 (2)	0.010 (2)
C6	0.035 (2)	0.050 (2)	0.040 (2)	−0.0016 (19)	−0.0005 (18)	0.0021 (19)
C7	0.050 (3)	0.100 (4)	0.074 (4)	−0.025 (3)	−0.024 (3)	0.037 (3)
C8	0.108 (5)	0.059 (3)	0.101 (5)	−0.031 (3)	0.005 (4)	−0.016 (3)
C9	0.060 (3)	0.078 (3)	0.058 (3)	−0.018 (3)	−0.024 (2)	0.018 (3)

Geometric parameters (Å, º) top

N1—C1	1.464 (5)	C6—C1	1.383 (5)
N1—H1A	0.84 (5)	C6—C5	1.391 (6)
N1—H1B	0.94 (6)	C6—C9	1.507 (6)
N1—H1C	1.01 (5)	C7—H7A	0.9600
C2—C3	1.387 (6)	C7—H7B	0.9600
C2—C1	1.393 (5)	C7—H7C	0.9600
C2—C7	1.504 (6)	C8—H8A	0.9600
C3—H3A	0.9300	C8—H8B	0.9600
C4—C3	1.368 (6)	C8—H8C	0.9600
C4—C8	1.521 (7)	C9—H9A	0.9600
C5—C4	1.380 (6)	C9—H9B	0.9600
C5—H5A	0.9300	C9—H9C	0.9600

C1—N1—H1A	112 (3)	C1—C6—C5	117.8 (4)
C1—N1—H1B	114 (3)	C1—C6—C9	122.9 (4)
C1—N1—H1C	114 (3)	C5—C6—C9	119.3 (4)
H1A—N1—H1B	100 (4)	C2—C7—H7A	109.5
H1A—N1—H1C	108 (4)	C2—C7—H7B	109.5
H1B—N1—H1C	108 (4)	C2—C7—H7C	109.5
C2—C1—N1	118.1 (4)	H7A—C7—H7B	109.5
C6—C1—N1	119.7 (4)	H7A—C7—H7C	109.5
C6—C1—C2	122.1 (4)	H7B—C7—H7C	109.5
C1—C2—C7	122.0 (4)	C4—C8—H8A	109.5
C3—C2—C1	116.8 (4)	C4—C8—H8B	109.5
C3—C2—C7	121.1 (4)	C4—C8—H8C	109.5
C2—C3—H3A	118.3	H8A—C8—H8B	109.5
C4—C3—C2	123.3 (4)	H8A—C8—H8C	109.5
C4—C3—H3A	118.3	H8B—C8—H8C	109.5
C3—C4—C5	117.8 (4)	C6—C9—H9A	109.5
C3—C4—C8	121.5 (5)	C6—C9—H9B	109.5
C5—C4—C8	120.7 (5)	C6—C9—H9C	109.5
C4—C5—C6	122.0 (4)	H9A—C9—H9B	109.5
C4—C5—H5A	119.0	H9A—C9—H9C	109.5
C6—C5—H5A	119.0	H9B—C9—H9C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1ⁱ	0.84 (5)	2.58 (5)	3.376 (4)	157 (4)
N1—H1B···Br1	0.94 (6)	2.47 (6)	3.391 (4)	168 (4)
N1—H1C···Br1ⁱⁱ	1.01 (5)	2.32 (5)	3.292 (4)	162 (4)

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

Experimental details

Crystal data
Chemical formula	C₉H₁₄N⁺·Br⁻
M_r	216.11
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	294
a, b, c (Å)	10.399 (2), 18.720 (4), 10.282 (2)
V (Å³)	2001.6 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	4.05
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.88, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	18944, 2292, 1627
R_int	0.099
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.122, 1.00
No. of reflections	2292
No. of parameters	113
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.41

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	0.84 (5)	2.58 (5)	3.376 (4)	157 (4)
N1—H1B···Br1	0.94 (6)	2.47 (6)	3.391 (4)	168 (4)
N1—H1C···Br1ⁱⁱ	1.01 (5)	2.32 (5)	3.292 (4)	162 (4)

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

References

Lemmerer, A. & Billing, D. G. (2007). Acta Cryst. E63, o929–o931. Web of Science CSD CrossRef IUCr Journals Google Scholar
Long, S., Siegler, M. & Li, T. (2007). Acta Cryst. E63, o3080. Web of Science CSD CrossRef IUCr Journals 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

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2376

doi:10.1107/S1600536809034497

Open

access