4,5-Dibromo-1,2-dimethyl-1H-imidazol-3-ium bromide

Bahnous, M.; Bouraiou, A.; Bouacida, S.; Roisnel, T.; Belfaitah, A.

doi:10.1107/S1600536812015310

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1391

doi:10.1107/S1600536812015310

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4,5-Dibromo-1,2-dimethyl-1H-imidazol-3-ium bromide

Mebarek Bahnous,^a Abdelmalek Bouraiou,^b Sofiane Bouacida,^a ^* Thierry Roisnel ^c and Ali Belfaitah ^b

^aUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, CHEMS, Université Mentouri-Constantine, 25000 Algeria, ^bLaboratoire des Produits Naturels d'Origine Végétale et de Synthèse Organique, PHYSYNOR, Université Mentouri-Constantine, 25000 Constantine, Algeria, and ^cCentre de Difractométrie X, UMR 6226 CNRS Unité Sciences Chimiques de Rennes, Université de Rennes I, 263 Avenue du Général Leclerc, 35042 Rennes, France
^*Correspondence e-mail: bouacida_sofiane@yahoo.fr

(Received 28 March 2012; accepted 7 April 2012; online 13 April 2012)

In the title salt, C₅H₇Br₂N₂⁺·Br⁻, the cation and anion are connected by an N—H⋯Br hydrogen bond. In the crystal, there are intercalated layers parallel to (10-2) in which bromide ions are located between the cations. Weak intermolecular C—H⋯Br hydrogen bonds are also observed.

Related literature

For the preparation of the title compound using the Ortoleva–King reaction, see: King (1944 ). For applications of C,N-substituted haloimidazole derivatives, see: Reepmeyer et al. (1975 ); Zamora et al. (2003 ); Schmidt & Schieffer (2003 ); Mashkovskii (2005 ); Amini et al. (2007 ).

Experimental

Crystal data

C₅H₇Br₂N₂⁺·Br⁻
M_r = 334.86
Monoclinic, P 2₁ /c
a = 5.5938 (3) Å
b = 11.2522 (6) Å
c = 14.4864 (9) Å
β = 104.571 (3)°
V = 882.48 (9) Å³
Z = 4
Mo Kα radiation
μ = 13.64 mm⁻¹
T = 150 K
0.31 × 0.22 × 0.17 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.058, T_max = 0.098
7565 measured reflections
2032 independent reflections
1747 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.060
S = 1.03
2032 reflections
94 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.86 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5⋯Br3ⁱ	0.88	2.35	3.216 (3)	168
C6—H6A⋯Br2ⁱⁱ	0.96	2.90	3.796 (3)	156
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x+1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and DIAMOND (Brandenburg & Berndt, 2001 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812015310/lh5448sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812015310/lh5448Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812015310/lh5448Isup3.cml

checkCIF report

Comment top

Imidazole is an important synthon for the synthesis of diverse derivatives and various condensed heterocycles. The C,N-substituted haloimidazole derivatives have shown a high pharmacological activity (Zamora et al., 2003; Schmidt et al., 2003) and some have found practical use in medicine (Mashkovskii, 2005; Amini et al., 2007; Reepmeyer et al., 1975). Halo- and dihaloimidazoles form salts with mineral acids and picrates. The nitrates and picrates, which crystallize readily from water and alcohols, are quite often used for the additional characterization of compounds being studied. In this paper, we report the structure determination of 4,5-dibromo-1,2-dimethyl-1H-imidazolium bromide (I) resulting from an unexpected reaction of 1,2-dimethyl-1H-imidazole with bromine in acetone in a modified Ortoleva-King conditions reaction (King, 1944).

The molecular structure of (I) is shown in Fig. 1. The asymmetric unit of title molecule, (C₅H₇N₂Br₂)⁺, Br^-, contains a 4,5-dibromo-1,2-dimethylimidazolium cation and bromide anion linked by an intermolecular N—H···Br hydrogen bond. The crystal packing can be described as intercalated layers parallel to (102) in which bromide ions are located between cations (Fig. 2). Further stabilization is provided by weak intermoleculer C—H···Br hydrogen bonds (Fig. 3).

Related literature top

For the preparation of the title compound using the Ortoleva–King reaction, see: King (1944). For applications of C,N-substituted haloimidazole derivatives, see: Reepmeyer et al. (1975); Zamora et al. (2003); Schmidt & Schieffer (2003); Mashkovskii (2005); Amini et al. (2007).

Experimental top

Compound (I) was obtained from reaction of 4,5-dibromo-1,2-dimethyl-1H-imidazole dissolved in acetone with 1 eq. of bromine. After stirring at 303K during 1 h, a colorless suspension was obtained and a white solid was filtered off. A suitable crystal was obtained by slow evaporation at room temperature of a solution of (I) in a MeOH/CHCl₃ mixture.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Part of the crystal structure viewed along the b axis.
	Fig. 3. Part of the crystal structure showing hydrogen bonds [N—H···Br (in red), C—H···Br (in blue)] as dashed lines.

4,5-Dibromo-1,2-dimethyl-1H-imidazol-3-ium bromide top

Crystal data top

C₅H₇Br₂N₂⁺·Br⁻	F(000) = 624
M_r = 334.86	D_x = 2.52 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3086 reflections
a = 5.5938 (3) Å	θ = 2.9–27.5°
b = 11.2522 (6) Å	µ = 13.64 mm⁻¹
c = 14.4864 (9) Å	T = 150 K
β = 104.571 (3)°	Prism, colourless
V = 882.48 (9) Å³	0.31 × 0.22 × 0.17 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	1747 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
CCD rotation images, thin slices scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −6→7
T_min = 0.058, T_max = 0.098	k = −14→12
7565 measured reflections	l = −18→17
2032 independent 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)] = 0.027	H-atom parameters constrained
wR(F²) = 0.060	w = 1/[σ²(F_o²) + (0.0201P)² + 0.142P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.002
2032 reflections	Δρ_max = 0.63 e Å⁻³
94 parameters	Δρ_min = −0.86 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: 0.0075 (4)

Crystal data top

C₅H₇Br₂N₂⁺·Br⁻	V = 882.48 (9) Å³
M_r = 334.86	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.5938 (3) Å	µ = 13.64 mm⁻¹
b = 11.2522 (6) Å	T = 150 K
c = 14.4864 (9) Å	0.31 × 0.22 × 0.17 mm
β = 104.571 (3)°

Data collection top

Bruker APEXII diffractometer	2032 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1747 reflections with I > 2σ(I)
T_min = 0.058, T_max = 0.098	R_int = 0.050
7565 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.060	H-atom parameters constrained
S = 1.03	Δρ_max = 0.63 e Å⁻³
2032 reflections	Δρ_min = −0.86 e Å⁻³
94 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	0.52217 (6)	0.60967 (3)	0.40218 (2)	0.01621 (11)
Br2	0.12689 (6)	0.86245 (3)	0.44145 (2)	0.01726 (11)
N2	0.7783 (5)	0.7167 (2)	0.57813 (19)	0.0142 (6)
N5	0.5520 (5)	0.8641 (3)	0.5998 (2)	0.0171 (6)
H5	0.4987	0.9266	0.6251	0.021*
C1	0.7626 (6)	0.8069 (3)	0.6365 (2)	0.0163 (7)
C3	0.5709 (6)	0.7178 (3)	0.5019 (2)	0.0141 (7)
C4	0.4301 (6)	0.8096 (3)	0.5154 (2)	0.0140 (7)
C6	0.9445 (7)	0.8397 (3)	0.7253 (2)	0.0222 (8)
H6A	0.9879	0.7706	0.7647	0.033*
H6B	0.8745	0.8986	0.7587	0.033*
H6C	1.0896	0.8713	0.7103	0.033*
C7	0.9765 (7)	0.6294 (3)	0.5945 (3)	0.0214 (8)
H7A	1.1062	0.6531	0.6483	0.032*
H7B	1.0403	0.6242	0.5390	0.032*
H7C	0.9137	0.5532	0.6069	0.032*
Br3	0.58756 (6)	0.58078 (3)	0.77871 (2)	0.01713 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0170 (2)	0.01589 (19)	0.01515 (19)	0.00097 (14)	0.00295 (14)	−0.00101 (12)
Br2	0.01324 (19)	0.0185 (2)	0.01989 (19)	0.00293 (14)	0.00389 (14)	0.00221 (13)
N2	0.0086 (14)	0.0175 (15)	0.0156 (14)	−0.0021 (12)	0.0013 (11)	0.0037 (11)
N5	0.0193 (16)	0.0141 (15)	0.0185 (15)	−0.0040 (12)	0.0060 (12)	−0.0026 (11)
C1	0.0153 (18)	0.0171 (18)	0.0162 (17)	−0.0055 (14)	0.0031 (14)	0.0020 (14)
C3	0.0124 (17)	0.0172 (17)	0.0123 (16)	−0.0017 (14)	0.0022 (13)	0.0011 (13)
C4	0.0107 (17)	0.0173 (18)	0.0138 (16)	−0.0015 (14)	0.0029 (13)	−0.0020 (13)
C6	0.021 (2)	0.025 (2)	0.0182 (18)	−0.0087 (16)	0.0008 (15)	−0.0019 (15)
C7	0.0156 (19)	0.023 (2)	0.024 (2)	0.0058 (15)	0.0019 (16)	0.0075 (14)
Br3	0.0163 (2)	0.0161 (2)	0.01874 (19)	−0.00155 (13)	0.00405 (14)	−0.00052 (13)

Geometric parameters (Å, º) top

Br1—C3	1.855 (3)	C1—C6	1.472 (5)
Br2—C4	1.861 (3)	C3—C4	1.343 (5)
N2—C1	1.338 (4)	C6—H6A	0.9600
N2—C3	1.386 (4)	C6—H6B	0.9600
N2—C7	1.456 (4)	C6—H6C	0.9600
N5—C1	1.329 (4)	C7—H7A	0.9600
N5—C4	1.385 (4)	C7—H7B	0.9600
N5—H5	0.8800	C7—H7C	0.9600

C1—N2—C3	108.8 (3)	N5—C4—Br2	122.8 (2)
C1—N2—C7	125.3 (3)	C1—C6—H6A	109.5
C3—N2—C7	125.9 (3)	C1—C6—H6B	109.5
C1—N5—C4	109.2 (3)	H6A—C6—H6B	109.5
C1—N5—H5	125.4	C1—C6—H6C	109.5
C4—N5—H5	125.4	H6A—C6—H6C	109.5
N5—C1—N2	107.9 (3)	H6B—C6—H6C	109.5
N5—C1—C6	125.2 (3)	N2—C7—H7A	109.5
N2—C1—C6	127.0 (3)	N2—C7—H7B	109.5
C4—C3—N2	107.1 (3)	H7A—C7—H7B	109.5
C4—C3—Br1	129.9 (2)	N2—C7—H7C	109.5
N2—C3—Br1	123.0 (2)	H7A—C7—H7C	109.5
C3—C4—N5	107.0 (3)	H7B—C7—H7C	109.5
C3—C4—Br2	130.2 (2)

C4—N5—C1—N2	−0.3 (4)	C1—N2—C3—Br1	178.4 (2)
C4—N5—C1—C6	179.1 (3)	C7—N2—C3—Br1	−3.8 (5)
C3—N2—C1—N5	0.4 (4)	N2—C3—C4—N5	0.0 (4)
C7—N2—C1—N5	−177.4 (3)	Br1—C3—C4—N5	−178.5 (2)
C3—N2—C1—C6	−179.0 (3)	N2—C3—C4—Br2	−179.7 (2)
C7—N2—C1—C6	3.2 (5)	Br1—C3—C4—Br2	1.7 (5)
C1—N2—C3—C4	−0.2 (4)	C1—N5—C4—C3	0.2 (4)
C7—N2—C3—C4	177.5 (3)	C1—N5—C4—Br2	180.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···Br3ⁱ	0.88	2.35	3.216 (3)	168
C6—H6A···Br2ⁱⁱ	0.96	2.90	3.796 (3)	156

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x+1, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₅H₇Br₂N₂⁺·Br⁻
M_r	334.86
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	5.5938 (3), 11.2522 (6), 14.4864 (9)
β (°)	104.571 (3)
V (Å³)	882.48 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	13.64
Crystal size (mm)	0.31 × 0.22 × 0.17

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.058, 0.098
No. of measured, independent and observed [I > 2σ(I)] reflections	7565, 2032, 1747
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.060, 1.03
No. of reflections	2032
No. of parameters	94
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.86

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SIR2002 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Berndt, 2001), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···Br3ⁱ	0.88	2.35	3.216 (3)	168.00
C6—H6A···Br2ⁱⁱ	0.96	2.90	3.796 (3)	156.00

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x+1, −y+3/2, z+1/2.

Acknowledgements

We are grateful to all personel of the PHYSYNOR Laboratory, Université Mentouri-Constantine, Algeria, for their assistance. Thanks are due to the MESRS (Ministére de l'Enseignement Supérieur et de la Recherche Scientifique - Algérie) for financial support.

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