3-(2-Bromo­benz­yl)-1-methyl-1H-imidazol-3-ium bromide

Dong, J.-Y.; You, T.-P.

doi:10.1107/S1600536811019842

organic compounds

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Volume 67| Part 7| July 2011| Page o1568

doi:10.1107/S1600536811019842

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3-(2-Bromobenzyl)-1-methyl-1H-imidazol-3-ium bromide

Jian-Yu Dong ^a and Tian-Pa You ^a ^*

^aDepartment of Chemistry, University of Science & Technology of China, Hefei, Anhui 230026, People's Republic of China
^*Correspondence e-mail: jianyud@mail.ustc.edu.cn

(Received 14 May 2011; accepted 25 May 2011; online 4 June 2011)

In the title compound, C₁₁H₁₂BrN₂⁺·Br⁻, the imidazole and phenyl rings are nearly perpendicular, making a dihedral angle of 87.71 (7)°. The crystal structure is stabilized by non-classical intermolecular C—H⋯Br hydrogen bonds and inversion-related molecules are linked through π–π interactions between the imidazole ring systems [centroid–centroid distance = 3.472 (6) Å].

Related literature

Imidazolium salts are used to obtain transition metal complexes of N-heterocyclic carbenes, which have become an important class of catalysts in organometallic chemistry and organic synthesis, see: Marion & Nolan (2008 ); Herrmann (2002 ); Qin et al. (2006 ). For related structures, Guo et al. (2008 ); Liu et al. (2003 ).

Experimental

Crystal data

C₁₁H₁₂BrN₂⁺·Br⁻
M_r = 332.05
Orthorhombic, P b c a
a = 8.4548 (10) Å
b = 13.9166 (13) Å
c = 20.831 (2) Å
V = 2451.1 (5) Å³
Z = 8
Mo Kα radiation
μ = 6.58 mm⁻¹
T = 298 K
0.42 × 0.40 × 0.21 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.169, T_max = 0.339
9279 measured reflections
2158 independent reflections
1530 reflections with I > 2σ(I)
R_int = 0.126

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.130
S = 1.19
2158 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯Br2ⁱ	0.97	2.86	3.662 (6)	141
Symmetry code: (i) x+1, y, z.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811019842/ff2011sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811019842/ff2011Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811019842/ff2011Isup3.cdx

Supporting information file. DOI: 10.1107/S1600536811019842/ff2011Isup4.cml

checkCIF report

Comment top

Imidazolium salts or its derivatives are used as ionic liquids, and in many organic transformations. They are used to obtain transition metal complexes of N-heterocyclic carbenes which have become a very important class of catalysts in organometallic chemistry and organic synthesis (Herrmann, 2002, Marion & Nolan, 2008). We here report the crystal structure of the title compound.

Bond lengths and angles in the title molecule (Fig. 1) are within normal ranges. The imidazole and the phenyl ring are nearly perpendicular, with a dihedral angle of 87.71 (2)°.

The molecular structure is stabilized by C—H···Br hydrogen bonds (Table 1). The crystal structure is stabilized by π-π interactions between the imidazole ring systems of the inversion related molecules, with a Cg1···Cg1ⁱ distance of 3.472 (6) Å [symmetry code: (i) 1-x, -y, 1-z].

Related literature top

Imidazolium salts are used to obtain transition metal complexes of N-heterocyclic carbenes, which have become an important class of catalysts in organometallic chemistry and organic synthesis, see: Marion & Nolan (2008); Herrmann et al. (2002); Qin et al. (2006). For related structures, Guo et al. (2008); Liu et al. (2003).

Experimental top

1-methyl-1H-imidazole (0.615 g, 7.5 mmol) and 1-bromo-2-(bromomethyl)benzene (1.25 g, 5 mmol) in 20 ml of dioxane were refluxed for 12 h. After cooling the solution to room temperature, the mixture was filtered and afforded a colorless solid. Colourless single crystals suitable for X-ray diffraction were obtained by recrystallization from acetonitrile and diethyl ether.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids.

3-(2-Bromobenzyl)-1-methyl-1H-imidazol-3-ium bromide top

Crystal data top

C₁₁H₁₂BrN₂⁺·Br⁻	D_x = 1.800 Mg m⁻³
M_r = 332.05	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 992 reflections
a = 8.4548 (10) Å	θ = 2.6–25.2°
b = 13.9166 (13) Å	µ = 6.58 mm⁻¹
c = 20.831 (2) Å	T = 298 K
V = 2451.1 (5) Å³	Block, colourless
Z = 8	0.42 × 0.40 × 0.21 mm
F(000) = 1296

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	2158 independent reflections
Radiation source: fine-focus sealed tube	1530 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.126
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→9
T_min = 0.169, T_max = 0.339	k = −15→16
9279 measured reflections	l = −15→24

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)] = 0.064	H-atom parameters constrained
wR(F²) = 0.130	w = 1/[σ²(F_o²) + (0.0439P)² + 1.6882P] where P = (F_o² + 2F_c²)/3
S = 1.19	(Δ/σ)_max < 0.001
2158 reflections	Δρ_max = 0.74 e Å⁻³
138 parameters	Δρ_min = −0.65 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0051 (4)

Crystal data top

C₁₁H₁₂BrN₂⁺·Br⁻	V = 2451.1 (5) Å³
M_r = 332.05	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.4548 (10) Å	µ = 6.58 mm⁻¹
b = 13.9166 (13) Å	T = 298 K
c = 20.831 (2) Å	0.42 × 0.40 × 0.21 mm

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	2158 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1530 reflections with I > 2σ(I)
T_min = 0.169, T_max = 0.339	R_int = 0.126
9279 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 1.19	Δρ_max = 0.74 e Å⁻³
2158 reflections	Δρ_min = −0.65 e Å⁻³
138 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	0.76580 (9)	0.05373 (6)	0.26368 (5)	0.0618 (4)
Br2	0.09361 (7)	0.16571 (5)	0.46240 (4)	0.0464 (3)
N1	0.6110 (5)	0.0692 (4)	0.4078 (3)	0.0320 (14)
N2	0.4228 (6)	−0.0365 (4)	0.4189 (3)	0.0346 (14)
C1	0.4546 (7)	0.0545 (5)	0.4031 (3)	0.0329 (17)
H1	0.3803	0.1002	0.3908	0.039*
C2	0.5601 (8)	−0.0806 (5)	0.4353 (4)	0.0444 (19)
H2	0.5716	−0.1438	0.4490	0.053*
C3	0.6759 (8)	−0.0158 (5)	0.4282 (4)	0.0434 (19)
H3	0.7827	−0.0267	0.4359	0.052*
C4	0.6935 (7)	0.1600 (5)	0.3952 (4)	0.0393 (19)
H4A	0.8059	0.1473	0.3913	0.047*
H4B	0.6785	0.2026	0.4315	0.047*
C5	0.6377 (6)	0.2087 (5)	0.3363 (4)	0.0337 (18)
C6	0.6590 (7)	0.1733 (5)	0.2750 (4)	0.041 (2)
C7	0.6039 (9)	0.2206 (8)	0.2210 (4)	0.061 (2)
H7	0.6185	0.1945	0.1803	0.073*
C8	0.5265 (10)	0.3076 (8)	0.2288 (6)	0.069 (3)
H8	0.4887	0.3404	0.1930	0.083*
C9	0.5056 (9)	0.3454 (7)	0.2885 (6)	0.068 (3)
H9	0.4543	0.4040	0.2933	0.082*
C10	0.5604 (8)	0.2968 (5)	0.3419 (4)	0.049 (2)
H10	0.5454	0.3233	0.3824	0.059*
C11	0.2652 (7)	−0.0794 (6)	0.4187 (4)	0.056 (2)
H11A	0.1878	−0.0308	0.4279	0.084*
H11B	0.2599	−0.1288	0.4508	0.084*
H11C	0.2442	−0.1068	0.3773	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0619 (5)	0.0619 (6)	0.0615 (8)	−0.0090 (4)	0.0169 (4)	−0.0205 (5)
Br2	0.0390 (4)	0.0502 (5)	0.0500 (7)	0.0086 (3)	−0.0099 (3)	0.0048 (4)
N1	0.030 (3)	0.041 (3)	0.025 (4)	0.007 (3)	−0.002 (2)	0.000 (3)
N2	0.041 (3)	0.035 (3)	0.029 (4)	−0.001 (3)	0.002 (3)	0.000 (3)
C1	0.031 (3)	0.045 (4)	0.023 (5)	0.006 (3)	−0.005 (3)	0.002 (3)
C2	0.049 (4)	0.042 (4)	0.043 (6)	0.010 (4)	0.003 (3)	0.002 (4)
C3	0.041 (4)	0.056 (5)	0.034 (5)	0.020 (4)	−0.003 (3)	0.003 (4)
C4	0.034 (3)	0.045 (4)	0.039 (6)	−0.005 (3)	−0.005 (3)	−0.003 (4)
C5	0.025 (3)	0.039 (4)	0.037 (6)	−0.011 (3)	−0.002 (3)	0.004 (4)
C6	0.032 (3)	0.044 (4)	0.048 (6)	−0.019 (3)	0.004 (3)	−0.002 (4)
C7	0.055 (5)	0.094 (7)	0.033 (6)	−0.031 (5)	0.003 (4)	0.013 (5)
C8	0.051 (5)	0.087 (8)	0.069 (9)	−0.010 (5)	−0.003 (5)	0.045 (6)
C9	0.057 (5)	0.066 (6)	0.081 (9)	0.003 (4)	0.010 (5)	0.030 (6)
C10	0.045 (4)	0.051 (5)	0.052 (7)	−0.005 (3)	0.000 (4)	0.005 (4)
C11	0.045 (4)	0.062 (5)	0.060 (7)	−0.015 (4)	0.001 (4)	−0.005 (5)

Geometric parameters (Å, º) top

Br1—C6	1.908 (7)	C5—C6	1.380 (10)
N1—C1	1.342 (7)	C5—C10	1.393 (9)
N1—C3	1.372 (8)	C6—C7	1.385 (11)
N1—C4	1.466 (8)	C7—C8	1.386 (13)
N2—C1	1.336 (9)	C7—H7	0.9300
N2—C2	1.357 (8)	C8—C9	1.362 (14)
N2—C11	1.460 (8)	C8—H8	0.9300
C1—H1	0.9300	C9—C10	1.382 (12)
C2—C3	1.338 (10)	C9—H9	0.9300
C2—H2	0.9300	C10—H10	0.9300
C3—H3	0.9300	C11—H11A	0.9600
C4—C5	1.480 (10)	C11—H11B	0.9600
C4—H4A	0.9700	C11—H11C	0.9600
C4—H4B	0.9700

C1—N1—C3	106.5 (6)	C10—C5—C4	118.9 (7)
C1—N1—C4	126.0 (5)	C5—C6—C7	122.6 (8)
C3—N1—C4	127.5 (5)	C5—C6—Br1	119.2 (6)
C1—N2—C2	108.6 (5)	C7—C6—Br1	118.2 (7)
C1—N2—C11	124.8 (6)	C6—C7—C8	118.6 (9)
C2—N2—C11	126.6 (6)	C6—C7—H7	120.7
N2—C1—N1	109.0 (5)	C8—C7—H7	120.7
N2—C1—H1	125.5	C9—C8—C7	120.4 (9)
N1—C1—H1	125.5	C9—C8—H8	119.8
C3—C2—N2	107.1 (6)	C7—C8—H8	119.8
C3—C2—H2	126.5	C8—C9—C10	120.2 (9)
N2—C2—H2	126.5	C8—C9—H9	119.9
C2—C3—N1	108.8 (6)	C10—C9—H9	119.9
C2—C3—H3	125.6	C9—C10—C5	121.3 (9)
N1—C3—H3	125.6	C9—C10—H10	119.3
N1—C4—C5	113.1 (5)	C5—C10—H10	119.3
N1—C4—H4A	109.0	N2—C11—H11A	109.5
C5—C4—H4A	109.0	N2—C11—H11B	109.5
N1—C4—H4B	109.0	H11A—C11—H11B	109.5
C5—C4—H4B	109.0	N2—C11—H11C	109.5
H4A—C4—H4B	107.8	H11A—C11—H11C	109.5
C6—C5—C10	116.9 (7)	H11B—C11—H11C	109.5
C6—C5—C4	124.2 (7)

C2—N2—C1—N1	1.3 (8)	N1—C4—C5—C10	114.2 (7)
C11—N2—C1—N1	−179.2 (7)	C10—C5—C6—C7	−1.5 (9)
C3—N1—C1—N2	−0.9 (8)	C4—C5—C6—C7	179.4 (6)
C4—N1—C1—N2	−179.3 (6)	C10—C5—C6—Br1	179.4 (4)
C1—N2—C2—C3	−1.1 (8)	C4—C5—C6—Br1	0.3 (8)
C11—N2—C2—C3	179.4 (7)	C5—C6—C7—C8	1.0 (10)
N2—C2—C3—N1	0.5 (9)	Br1—C6—C7—C8	−179.8 (5)
C1—N1—C3—C2	0.3 (8)	C6—C7—C8—C9	0.0 (11)
C4—N1—C3—C2	178.6 (7)	C7—C8—C9—C10	−0.5 (12)
C1—N1—C4—C5	−44.1 (9)	C8—C9—C10—C5	0.0 (11)
C3—N1—C4—C5	137.9 (7)	C6—C5—C10—C9	1.0 (10)
N1—C4—C5—C6	−66.7 (8)	C4—C5—C10—C9	−179.9 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···Br2ⁱ	0.97	2.86	3.662 (6)	141

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂BrN₂⁺·Br⁻
M_r	332.05
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	8.4548 (10), 13.9166 (13), 20.831 (2)
V (Å³)	2451.1 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	6.58
Crystal size (mm)	0.42 × 0.40 × 0.21

Data collection
Diffractometer	Bruker SMART 1K CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.169, 0.339
No. of measured, independent and observed [I > 2σ(I)] reflections	9279, 2158, 1530
R_int	0.126
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.130, 1.19
No. of reflections	2158
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.65

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···Br2ⁱ	0.97	2.86	3.662 (6)	141

Symmetry code: (i) x+1, y, z.

Acknowledgements

The authors thank the National Natural Science Foundation of China (20872129).

References

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