PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2321.
Published online 2009 September 5. doi:  10.1107/S1600536809034175
PMCID: PMC2970382

1,3-Diallyl-2-methyl­benzimidazolium bromide dihydrate

Abstract

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

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

An external file that holds a picture, illustration, etc.
Object name is e-65-o2321-scheme1.jpg

Experimental

Crystal data

  • C14H17N2 +·Br·2H2O
  • M r = 329.24
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2321-efi1.jpg
  • a = 13.2888 (2) Å
  • b = 16.8763 (2) Å
  • c = 7.3897 (1) Å
  • β = 109.773 (1)°
  • V = 1559.54 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.64 mm−1
  • T = 295 K
  • 0.4 × 0.3 × 0.2 mm

Data collection

  • Bruker APEXII diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.403, T max = 0.590
  • 11870 measured reflections
  • 1851 independent reflections
  • 1497 reflections with I > 2σ(I)
  • R int = 0.024

Refinement

  • R[F 2 > 2σ(F 2)] = 0.027
  • wR(F 2) = 0.085
  • S = 0.95
  • 1851 reflections
  • 103 parameters
  • 6 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.18 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809034175/sj2636sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034175/sj2636Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Experimental

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

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.

Figures

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 ...

Crystal data

C14H17N2+·Br·2H2OF(000) = 680
Mr = 329.24Dx = 1.402 Mg m3
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 mm1
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

Bruker APEXII diffractometer1851 independent reflections
Radiation source: fine-focus sealed tube1497 reflections with I > 2σ(I)
graphiteRint = 0.024
[var phi] 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

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 = 0.95w = 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 Å3
6 restraintsΔρmin = −0.18 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2636).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2005). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Holtgrewe, H., Diedrich, C., Pape, T., Grimme, S. & Hahn, F. E. (2009). Eur. J. Org. Chem. pp. 3116–3124.
  • Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2009). publCIF In preparation.
  • Xu, X.-B., Fu, R. & Ye, Q. (2008). Acta Cryst. E64, o109. [PMC free article] [PubMed]
  • Xu, X.-B. & Ye, Q. (2008). Acta Cryst. E64, o23. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography