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Acta Cryst. (2009). E65, o2321    [ doi:10.1107/S1600536809034175 ]

1,3-Diallyl-2-methylbenzimidazolium bromide dihydrate

H. Ennajih, R. Bouhfid, H. Zouihri, E. M. Essassi and S. W. Ng

Abstract top

The bonds in the five-membered ring of the title hydrated salt, C14H17N2+·Br-·2H2O, are delocalized. The cation lies on a special position of m site symmetry such that the mirror plane passes through the imidazolyl-methyl bond and is perpendicular to the plane of the cation. The anion lies on another special position of 2 site symmetry. The anion and uncoordinated water molecule are linked into a chain by O-H...O hydrogen bonds. One of the water O atoms is disordered over two sites of equal occupancy.

Related literature top

For the crystal structure of 1,3-diallylbenzimidazolium bromide, see: Holtgrewe et al. (2009). For those of the 1-allyl-3-(cyanobenzyl)benzimidazolium bromide and its hydrate, see: Xu et al. (2008); Xu & Ye (2008).

Experimental top

2-Methylbenzimidazole (1 g, 7.5 mmol), potassium carbonate (1.55 g, 11.25 mmol) and tetra-n-butylammonium bromide (0.18 g, 0.75 mmol) were stirred in N,N-dimethylformamide (50 ml) for an hour. To this suspension was added ally bromide (1.96 ml, 22.5 mmol); the mixture was stirred for two days. The mixture was filtered and the solvent removed under vacuum. The residue was crystallized from ethanol to give yellow crystals in 60% yield; m.p. 516–518 K. The formulation was established by 1H– and 13C-NMR spectroscopic analysis.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 to 0.97 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C). The methyl H-atoms lie on general positions,and are disordered; their occupancies are all 0.5.

The water H-atoms were located in a difference Fourier map and were refined with distance restraints (O–H 0.85±0.01 Å; H···H 1.39±0.01 Å). That hydrogen-bonded to Br1 is ordered whereas the other is disordered over two positions of 0.5 site occupancy. The isotropic temperature factors of the three H-atoms were refined.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of [C14H19N2O][Br].H2O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The disorder in the water molecule is not shown. The unlabeled atoms are related to the labeled ones by the x, 1 – y, z symmetry operation.
1,3-Diallyl-2-methylbenzimidazolium bromide dihydrate top
Crystal data top
C14H17N2+·Br−·2H2OF(000) = 680
Mr = 329.24Dx = 1.402 Mg m−3
Monoclinic, C2/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yCell parameters from 7035 reflections
a = 13.2888 (2) Åθ = 3.6–24.3°
b = 16.8763 (2) ŵ = 2.64 mm−1
c = 7.3897 (1) ÅT = 295 K
β = 109.773 (1)°Prism, yellow
V = 1559.54 (4) Å30.4 × 0.3 × 0.2 mm
Z = 4
Data collection top
Bruker APEXII
diffractometer		1851 independent reflections
Radiation source: fine-focus sealed tube1497 reflections with I > 2σ(I)
graphiteRint = 0.024
φ and ω scansθmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −14→17
Tmin = 0.403, Tmax = 0.590k = −21→19
11870 measured reflectionsl = −8→9
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085H atoms treated by a mixture of independent and constrained refinement
S = 0.95 w = 1/[σ2(Fo2) + (0.06P)2 + 0.349P]
where P = (Fo2 + 2Fc2)/3
1851 reflections(Δ/σ)max = 0.001
103 parametersΔρmax = 0.31 e Å−3
6 restraintsΔρmin = −0.18 e Å−3
Crystal data top
C14H17N2+·Br−·2H2OV = 1559.54 (4) Å3
Mr = 329.24Z = 4
Monoclinic, C2/mMo Kα radiation
a = 13.2888 (2) ŵ = 2.64 mm−1
b = 16.8763 (2) ÅT = 295 K
c = 7.3897 (1) Å0.4 × 0.3 × 0.2 mm
β = 109.773 (1)°
Data collection top
Bruker APEXII
diffractometer		1497 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		Rint = 0.024
Tmin = 0.403, Tmax = 0.590θmax = 27.5°
11870 measured reflectionsStandard reflections: 0
1851 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.027H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.085Δρmax = 0.31 e Å−3
S = 0.95Δρmin = −0.18 e Å−3
1851 reflectionsAbsolute structure: ?
103 parametersFlack parameter: ?
6 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Br10.00000.691870 (15)0.50000.05502 (14)
O10.07379 (17)0.58143 (11)0.9005 (3)0.0787 (5)
H110.055 (2)0.6089 (13)0.796 (2)0.084 (9)*
H120.086 (3)0.5342 (9)0.874 (5)0.075 (18)*0.50
H130.021 (2)0.582 (2)0.942 (5)0.10 (2)*0.50
N10.34476 (11)0.56471 (8)0.6215 (2)0.0381 (3)
C10.1655 (2)0.50000.4821 (5)0.0557 (7)
H1A0.13860.44730.48410.083*0.50
H1B0.14720.51760.35140.083*0.50
H1C0.13430.53510.55070.083*0.50
C20.2831 (2)0.50000.5747 (4)0.0393 (5)
C30.45113 (13)0.54109 (10)0.7010 (2)0.0375 (4)
C40.54525 (15)0.58475 (12)0.7654 (3)0.0487 (5)
H40.54540.63990.76460.058*
C50.63843 (16)0.54125 (14)0.8307 (3)0.0562 (5)
H50.70340.56790.87620.067*
C60.30794 (16)0.64801 (10)0.5930 (3)0.0457 (4)
H6A0.23850.65040.49250.055*
H6B0.35760.67910.55170.055*
C70.30000 (19)0.68243 (11)0.7729 (3)0.0509 (5)
H70.25270.65920.82540.061*
C80.3551 (2)0.74283 (14)0.8607 (3)0.0640 (6)
H8A0.40310.76730.81150.077*
H8B0.34680.76180.97290.077*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0512 (2)0.04358 (19)0.0763 (2)0.0000.02951 (16)0.000
O10.0922 (14)0.0556 (11)0.0888 (13)−0.0055 (9)0.0312 (12)0.0044 (9)
N10.0389 (8)0.0313 (7)0.0430 (8)0.0003 (6)0.0122 (6)0.0006 (6)
C10.0375 (14)0.0427 (15)0.082 (2)0.0000.0133 (14)0.000
C20.0392 (13)0.0351 (13)0.0433 (13)0.0000.0135 (11)0.000
C30.0385 (9)0.0402 (9)0.0329 (8)−0.0015 (7)0.0109 (7)−0.0002 (7)
C40.0459 (10)0.0509 (11)0.0466 (10)−0.0100 (8)0.0124 (8)−0.0048 (8)
C50.0398 (10)0.0764 (13)0.0470 (10)−0.0110 (10)0.0076 (8)−0.0070 (9)
C60.0497 (10)0.0306 (9)0.0526 (10)0.0022 (8)0.0120 (8)0.0076 (7)
C70.0527 (12)0.0383 (10)0.0654 (13)0.0045 (8)0.0248 (10)0.0033 (8)
C80.0748 (15)0.0484 (12)0.0691 (14)−0.0005 (11)0.0248 (12)−0.0055 (10)
Geometric parameters (Å, °) top
O1—H110.86 (1)C3—C41.390 (3)
O1—H120.85 (1)C4—C51.379 (3)
O1—H130.86 (1)C4—H40.9300
N1—C21.339 (2)C5—C5i1.392 (5)
N1—C31.393 (2)C5—H50.9300
N1—C61.480 (2)C6—C71.487 (3)
C1—C21.479 (4)C6—H6A0.9700
C1—H1A0.9600C6—H6B0.9700
C1—H1B0.9600C7—C81.294 (3)
C1—H1C0.9600C7—H70.9300
C2—N1i1.339 (2)C8—H8A0.9300
C3—C3i1.387 (4)C8—H8B0.9300
H11—O1—H12108.7 (16)C5—C4—C3115.81 (19)
H11—O1—H13106.6 (16)C5—C4—H4122.1
H12—O1—H13109.4 (17)C3—C4—H4122.1
C2—N1—C3108.70 (15)C4—C5—C5i122.17 (12)
C2—N1—C6126.45 (16)C4—C5—H5118.9
C3—N1—C6124.84 (15)C5i—C5—H5118.9
C2—C1—H1A109.5N1—C6—C7111.34 (15)
C2—C1—H1B109.5N1—C6—H6A109.4
H1A—C1—H1B109.5C7—C6—H6A109.4
C2—C1—H1C109.5N1—C6—H6B109.4
H1A—C1—H1C109.5C7—C6—H6B109.4
H1B—C1—H1C109.5H6A—C6—H6B108.0
N1—C2—N1i109.3 (2)C8—C7—C6123.8 (2)
N1—C2—C1125.33 (11)C8—C7—H7118.1
N1i—C2—C1125.33 (11)C6—C7—H7118.1
C3i—C3—C4122.02 (12)C7—C8—H8A120.0
C3i—C3—N1106.63 (9)C7—C8—H8B120.0
C4—C3—N1131.31 (17)H8A—C8—H8B120.0
C3—N1—C2—N1i0.3 (2)C6—N1—C3—C4−2.1 (3)
C6—N1—C2—N1i179.79 (12)C3i—C3—C4—C5−0.5 (2)
C3—N1—C2—C1−178.4 (2)N1—C3—C4—C5−177.78 (17)
C6—N1—C2—C11.0 (4)C3—C4—C5—C5i0.5 (2)
C2—N1—C3—C3i−0.20 (15)C2—N1—C6—C798.5 (2)
C6—N1—C3—C3i−179.67 (13)C3—N1—C6—C7−82.1 (2)
C2—N1—C3—C4177.40 (19)N1—C6—C7—C8118.6 (2)
Symmetry codes: (i) x, −y+1, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H11···Br10.86 (1)2.49 (1)3.351 (2)178 (2)
O1—H13···O1ii0.86 (1)1.98 (1)2.822 (5)166 (4)
O1—H12···O1i0.85 (1)1.97 (2)2.748 (4)152 (3)
Symmetry codes: (ii) −x, y, −z+2; (i) x, −y+1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H11···Br10.86 (1)2.49 (1)3.351 (2)178 (2)
O1—H13···O1i0.86 (1)1.98 (1)2.822 (5)166 (4)
O1—H12···O1ii0.85 (1)1.97 (2)2.748 (4)152 (3)
Symmetry codes: (i) −x, y, −z+2; (ii) x, −y+1, z.
Acknowledgements top

We thank Université Mohammed V-Agdal and the University of Malaya for supporting this study.

references
References top

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2009). publCIF. In preparation.

Xu, X.-B., Fu, R. & Ye, Q. (2008). Acta Cryst. E64, o109.

Xu, X.-B. & Ye, Q. (2008). Acta Cryst. E64, o23.