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Acta Cryst. (2008). E64, o2225    [ doi:10.1107/S1600536808034764 ]

1-[6-(Hydroxymethyl)-2-pyridyl]-3-(2,4,6-trimethylbenzyl)-1H-imidazol-3-ium bromide

C. Zhou, X.-G. Zhou, Y.-P. Qiu and M.-M. Luo

Abstract top

In the title compound, C19H22N3O+·Br-, the imidazole ring is approximately coplanar with the pyridine ring [dihedral angle = 0.88 (13)°] and nearly perpendicular to the benzene ring [dihedral angle = 81.70 (13)°]. O-H...Br and C-H...Br hydrogen bonding helps to stabilize the crystal structure.

Comment top

The range of N-heterocyclic carbenes (NHCs) is expanding rapidly since many homogeneous catalysts rely on NHC-based supporting ligands for steric and electronic control. Recently the study of [C, O] chelating NHC ligands have attracted increasing attention. The bonding between the NHC and metal can be enhanced by alkoxide or phenoxide as a sidearm through the incorporation of chelating anionic oxygen (Liddle et al., 2007; Ren et al., 2007). These kind of ligands are of great significance to early metal catalysis and carbene chemistry (Arnold & Wilson, 2007; Chianese & Crabtree, 2005; Dyson et al., 2008; Patel et al., 2006). The title compound, a stable precursor imidazolium salt of a tridentate alkoxide-functionalized NHC ligands, was synthesized in moderate yield by reacting [6-(1H-imidazol-1-yl)pyridin-2-yl]methanol with 2-(bromomethyl)-1,3,5-trimethylbenzene in acetonitrile.

In the title compound (Fig. 1), the pyridine and imidazole rings are coplanar, the dihedral angle between the plane of the pyridine ring and the plane of the imidazole ring is 0.88°. In addition, the dihedral angle between the imidazole ring and the benzene ring is 81.70 °. This might be a result of intermolecular O—H···Br interactions and steric effects. The O—H···Br and C—H···Br hydrogen bonding (Table 1) helps to stabilize the crystal structure.

Related literature top

For general background, see: Liddle et al. (2007); Ren et al. (2007); Arnold & Wilson (2007); Chianese & Crabtree (2005); Dyson et al. (2008); Patel et al. (2006). For synthesis, see: Hosseinzadeh et al. (2006).

Experimental top

[6-(1H-Imidazol-1-yl)pyridin-2-yl]methanol was prepared with the reported methods (Hosseinzadeh et al., 2006). The title compound was synthesized by dissolving [6-(1H-imidazol-1-yl)pyridin-2-yl]methanol (0.35 g, 2.0 mmol) and 2-(bromomethyl)-1,3,5-trimethylbenzene (0.85 g, 4.0 mmol) in 10 ml of acetonitrile. The mixture was stirred at 333 K for 15 h and the resulting precipitate was filtered, washed with ether. After removal of the solvent in vacuo the off-white crude product was purified by flash chromatography (CH2Cl2/CH3OH (5/1, v/v)) to afford the product as a white solid (0.60 g, 77%). Colorless single crystals suitable for X-ray diffraction were obtained at ambient temperature by slow evaporation of a CH2Cl2/CH3OH solution (5/1, v/v)) over a period of several days.

Refinement top

All H atom were positioned geometrically with C—H = 0.93 Å (aromatic) or 0.96 Å (methyl) and O—H = 0.82 Å, and refined using a riding model with 1.5Ueq(C) for methyl and Uiso(H) = 1.2Ueq(C,O) for others.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. Dashed line indicates the O—H···Br hydrogen bonding.
1-[6-(Hydroxymethyl)-2-pyridyl]-3-(2,4,6-trimethylbenzyl)-1H-imidazol- 3-ium bromide top
Crystal data top
C19H22N3O+·Br−F(000) = 800
Mr = 388.31Dx = 1.410 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3980 reflections
a = 11.2315 (3) Åθ = 2.8–26.7°
b = 11.5390 (3) ŵ = 2.26 mm−1
c = 14.3673 (4) ÅT = 296 K
β = 100.833 (2)°Block, colourless
V = 1828.82 (9) Å30.50 × 0.48 × 0.40 mm
Z = 4
Data collection top
Bruker SAMRT CCD area-detector
diffractometer		4184 independent reflections
Radiation source: fine-focus sealed tube2287 reflections with I > 2σ(I)
graphiteRint = 0.048
φ and ω scansθmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −14→14
Tmin = 0.320, Tmax = 0.405k = −13→14
13818 measured reflectionsl = −17→18
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.05P)2 + 0.57P]
where P = (Fo2 + 2Fc2)/3
4184 reflections(Δ/σ)max < 0.001
220 parametersΔρmax = 0.41 e Å−3
0 restraintsΔρmin = −0.60 e Å−3
Crystal data top
C19H22N3O+·Br−V = 1828.82 (9) Å3
Mr = 388.31Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.2315 (3) ŵ = 2.26 mm−1
b = 11.5390 (3) ÅT = 296 K
c = 14.3673 (4) Å0.50 × 0.48 × 0.40 mm
β = 100.833 (2)°
Data collection top
Bruker SAMRT CCD area-detector
diffractometer		4184 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2287 reflections with I > 2σ(I)
Tmin = 0.320, Tmax = 0.405Rint = 0.048
13818 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.116Δρmax = 0.41 e Å−3
S = 1.01Δρmin = −0.60 e Å−3
4184 reflectionsAbsolute structure: ?
220 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Br1−0.28302 (3)0.00291 (3)−0.05646 (2)0.05606 (10)
O1−0.21350 (16)0.2315 (2)0.07160 (15)0.0662 (7)
H1A−0.24780.19200.02710.099*
N10.09397 (17)0.27426 (17)0.18365 (14)0.0321 (5)
N20.28135 (17)0.30337 (16)0.27893 (14)0.0305 (5)
N30.44633 (17)0.20953 (17)0.27441 (14)0.0334 (5)
C10.1546 (2)0.3348 (2)0.25443 (17)0.0316 (6)
C20.1075 (2)0.4190 (2)0.3045 (2)0.0445 (8)
H2A0.15470.45740.35530.053*
C3−0.0135 (3)0.4434 (3)0.2752 (2)0.0531 (9)
H3A−0.05070.49890.30680.064*
C4−0.0795 (2)0.3852 (2)0.1986 (2)0.0444 (8)
H4A−0.16060.40340.17640.053*
C5−0.0234 (2)0.2998 (2)0.15572 (18)0.0356 (7)
C6−0.0886 (2)0.2276 (2)0.0752 (2)0.0445 (8)
H6A−0.07030.25630.01600.053*
H6B−0.06080.14800.08320.053*
C70.3316 (2)0.2205 (2)0.23424 (18)0.0346 (6)
H7A0.29190.17750.18300.042*
C80.3694 (2)0.3481 (2)0.34984 (18)0.0380 (7)
H8A0.35980.40750.39160.046*
C90.4719 (2)0.2892 (2)0.34690 (18)0.0384 (7)
H9A0.54660.30020.38660.046*
C100.5327 (2)0.1277 (2)0.24373 (18)0.0376 (7)
H10A0.58770.17070.21210.045*
H10B0.48800.07400.19820.045*
C110.6055 (2)0.0601 (2)0.32432 (17)0.0312 (6)
C120.7292 (2)0.0816 (2)0.35423 (17)0.0320 (6)
C130.7950 (2)0.0118 (2)0.42336 (17)0.0339 (6)
H13A0.87750.02610.44270.041*
C140.7435 (2)−0.0781 (2)0.46487 (18)0.0368 (7)
C150.6197 (2)−0.0969 (2)0.43645 (18)0.0370 (7)
H15A0.5830−0.15630.46450.044*
C160.5498 (2)−0.0293 (2)0.36734 (18)0.0336 (7)
C170.4158 (2)−0.0533 (3)0.3403 (2)0.0470 (8)
H17A0.3971−0.12410.36960.070*
H17B0.3935−0.06040.27270.070*
H17C0.37130.00940.36150.070*
C180.7936 (2)0.1776 (2)0.3128 (2)0.0466 (8)
H18A0.87920.17210.33670.070*
H18B0.76430.25110.33030.070*
H18C0.77830.17080.24500.070*
C190.8180 (3)−0.1551 (3)0.5387 (2)0.0521 (8)
H19A0.9026−0.13850.54230.078*
H19B0.8026−0.23480.52150.078*
H19C0.7963−0.14080.59920.078*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0685 (2)0.04819 (17)0.04329 (16)−0.00279 (17)−0.01057 (14)−0.00348 (15)
O10.0395 (11)0.0820 (15)0.0724 (15)−0.0069 (11)−0.0020 (11)−0.0294 (12)
N10.0311 (11)0.0305 (11)0.0330 (12)−0.0008 (9)0.0022 (9)0.0017 (9)
N20.0304 (11)0.0302 (11)0.0296 (11)0.0007 (9)0.0021 (9)0.0001 (9)
N30.0290 (11)0.0338 (11)0.0346 (12)0.0002 (9)−0.0014 (9)0.0000 (9)
C10.0312 (13)0.0309 (13)0.0324 (14)0.0006 (11)0.0049 (11)0.0053 (11)
C20.0388 (15)0.0424 (15)0.0495 (17)0.0016 (13)0.0011 (13)−0.0122 (13)
C30.0433 (17)0.0473 (16)0.068 (2)0.0062 (14)0.0089 (15)−0.0158 (16)
C40.0314 (14)0.0379 (15)0.0611 (19)0.0021 (12)0.0015 (13)−0.0063 (14)
C50.0373 (14)0.0316 (13)0.0365 (15)−0.0057 (11)0.0031 (12)0.0074 (11)
C60.0367 (15)0.0509 (17)0.0420 (16)−0.0047 (13)−0.0029 (13)−0.0032 (14)
C70.0336 (14)0.0359 (14)0.0319 (14)−0.0010 (12)−0.0001 (11)−0.0012 (12)
C80.0393 (14)0.0377 (14)0.0341 (15)−0.0042 (12)0.0000 (12)−0.0040 (12)
C90.0355 (14)0.0402 (15)0.0360 (15)−0.0055 (12)−0.0023 (12)−0.0051 (12)
C100.0335 (14)0.0437 (15)0.0342 (15)0.0039 (12)0.0030 (12)−0.0027 (12)
C110.0303 (13)0.0309 (13)0.0317 (14)0.0014 (11)0.0042 (11)−0.0022 (11)
C120.0311 (13)0.0320 (13)0.0336 (14)−0.0019 (11)0.0077 (11)−0.0022 (11)
C130.0246 (12)0.0404 (15)0.0356 (13)−0.0004 (12)0.0031 (10)−0.0022 (12)
C140.0416 (15)0.0386 (14)0.0306 (14)0.0082 (12)0.0073 (12)0.0002 (12)
C150.0408 (14)0.0341 (14)0.0383 (15)−0.0060 (12)0.0131 (12)0.0037 (12)
C160.0325 (13)0.0332 (14)0.0359 (14)−0.0008 (11)0.0087 (11)−0.0080 (11)
C170.0353 (15)0.0474 (16)0.0582 (19)−0.0060 (13)0.0088 (14)−0.0031 (15)
C180.0364 (15)0.0491 (17)0.0519 (18)−0.0067 (13)0.0018 (13)0.0090 (14)
C190.0507 (17)0.0587 (18)0.0465 (18)0.0092 (15)0.0079 (14)0.0163 (15)
Geometric parameters (Å, °) top
O1—C61.394 (3)C10—C111.504 (3)
O1—H1A0.8200C10—H10A0.9700
N1—C11.314 (3)C10—H10B0.9700
N1—C51.336 (3)C11—C121.398 (3)
N2—C71.335 (3)C11—C161.408 (4)
N2—C81.380 (3)C12—C131.380 (3)
N2—C11.447 (3)C12—C181.505 (4)
N3—C71.315 (3)C13—C141.377 (4)
N3—C91.378 (3)C13—H13A0.9300
N3—C101.479 (3)C14—C151.390 (3)
C1—C21.372 (4)C14—C191.510 (4)
C2—C31.373 (4)C15—C161.385 (3)
C2—H2A0.9300C15—H15A0.9300
C3—C41.380 (4)C16—C171.509 (3)
C3—H3A0.9300C17—H17A0.9600
C4—C51.377 (4)C17—H17B0.9600
C4—H4A0.9300C17—H17C0.9600
C5—C61.500 (3)C18—H18A0.9600
C6—H6A0.9700C18—H18B0.9600
C6—H6B0.9700C18—H18C0.9600
C7—H7A0.9300C19—H19A0.9600
C8—C91.344 (3)C19—H19B0.9600
C8—H8A0.9300C19—H19C0.9600
C9—H9A0.9300
C6—O1—H1A109.5C11—C10—H10A108.9
C1—N1—C5117.0 (2)N3—C10—H10B108.9
C7—N2—C8108.3 (2)C11—C10—H10B108.9
C7—N2—C1123.3 (2)H10A—C10—H10B107.8
C8—N2—C1128.4 (2)C12—C11—C16119.5 (2)
C7—N3—C9108.4 (2)C12—C11—C10120.7 (2)
C7—N3—C10125.0 (2)C16—C11—C10119.8 (2)
C9—N3—C10126.6 (2)C13—C12—C11119.0 (2)
N1—C1—C2126.0 (2)C13—C12—C18118.8 (2)
N1—C1—N2113.4 (2)C11—C12—C18122.2 (2)
C2—C1—N2120.6 (2)C14—C13—C12122.6 (2)
C1—C2—C3116.2 (2)C14—C13—H13A118.7
C1—C2—H2A121.9C12—C13—H13A118.7
C3—C2—H2A121.9C13—C14—C15117.9 (2)
C2—C3—C4119.8 (3)C13—C14—C19121.6 (2)
C2—C3—H3A120.1C15—C14—C19120.4 (2)
C4—C3—H3A120.1C16—C15—C14121.5 (2)
C5—C4—C3118.8 (3)C16—C15—H15A119.2
C5—C4—H4A120.6C14—C15—H15A119.2
C3—C4—H4A120.6C15—C16—C11119.3 (2)
N1—C5—C4122.1 (2)C15—C16—C17119.0 (2)
N1—C5—C6114.9 (2)C11—C16—C17121.7 (2)
C4—C5—C6123.0 (2)C16—C17—H17A109.5
O1—C6—C5110.7 (2)C16—C17—H17B109.5
O1—C6—H6A109.5H17A—C17—H17B109.5
C5—C6—H6A109.5C16—C17—H17C109.5
O1—C6—H6B109.5H17A—C17—H17C109.5
C5—C6—H6B109.5H17B—C17—H17C109.5
H6A—C6—H6B108.1C12—C18—H18A109.5
N3—C7—N2109.0 (2)C12—C18—H18B109.5
N3—C7—H7A125.5H18A—C18—H18B109.5
N2—C7—H7A125.5C12—C18—H18C109.5
C9—C8—N2106.7 (2)H18A—C18—H18C109.5
C9—C8—H8A126.7H18B—C18—H18C109.5
N2—C8—H8A126.7C14—C19—H19A109.5
C8—C9—N3107.6 (2)C14—C19—H19B109.5
C8—C9—H9A126.2H19A—C19—H19B109.5
N3—C9—H9A126.2C14—C19—H19C109.5
N3—C10—C11113.2 (2)H19A—C19—H19C109.5
N3—C10—H10A108.9H19B—C19—H19C109.5
C5—N1—C1—C22.5 (4)C7—N3—C9—C80.4 (3)
C5—N1—C1—N2−178.8 (2)C10—N3—C9—C8178.4 (2)
C7—N2—C1—N1−0.3 (3)C7—N3—C10—C11−132.4 (2)
C8—N2—C1—N1−179.0 (2)C9—N3—C10—C1149.8 (3)
C7—N2—C1—C2178.5 (2)N3—C10—C11—C12−109.5 (3)
C8—N2—C1—C2−0.2 (4)N3—C10—C11—C1673.4 (3)
N1—C1—C2—C3−2.0 (4)C16—C11—C12—C132.1 (4)
N2—C1—C2—C3179.4 (2)C10—C11—C12—C13−175.0 (2)
C1—C2—C3—C4−0.8 (4)C16—C11—C12—C18−178.5 (2)
C2—C3—C4—C52.8 (4)C10—C11—C12—C184.4 (4)
C1—N1—C5—C4−0.2 (4)C11—C12—C13—C14−0.5 (4)
C1—N1—C5—C6−179.6 (2)C18—C12—C13—C14−179.8 (2)
C3—C4—C5—N1−2.4 (4)C12—C13—C14—C15−1.2 (4)
C3—C4—C5—C6177.0 (3)C12—C13—C14—C19178.5 (2)
N1—C5—C6—O1160.1 (2)C13—C14—C15—C161.2 (4)
C4—C5—C6—O1−19.3 (4)C19—C14—C15—C16−178.5 (3)
C9—N3—C7—N2−0.9 (3)C14—C15—C16—C110.4 (4)
C10—N3—C7—N2−179.0 (2)C14—C15—C16—C17−179.4 (2)
C8—N2—C7—N31.0 (3)C12—C11—C16—C15−2.1 (4)
C1—N2—C7—N3−177.9 (2)C10—C11—C16—C15175.0 (2)
C7—N2—C8—C9−0.8 (3)C12—C11—C16—C17177.7 (2)
C1—N2—C8—C9178.1 (2)C10—C11—C16—C17−5.2 (4)
N2—C8—C9—N30.2 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···Br10.822.493.227 (2)151
C7—H7A···Br1i0.932.753.598 (2)152
C8—H8A···Br1ii0.932.893.745 (2)154
C10—H10B···Br1i0.972.913.813 (2)155
Symmetry codes: (i) −x, −y, −z; (ii) −x, y+1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···Br10.822.493.227 (2)151
C7—H7A···Br1i0.932.753.598 (2)152
C8—H8A···Br1ii0.932.893.745 (2)154
C10—H10B···Br1i0.972.913.813 (2)155
Symmetry codes: (i) −x, −y, −z; (ii) −x, y+1/2, −z+1/2.
Acknowledgements top

Financial support of this work b the Natural Science Foundation of Sichuan Province of China is gratefully acknowledged.

references
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