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Acta Crystallogr Sect E Struct Rep Online. 2009 September 1; 65(Pt 9): o2178.
Published online 2009 August 19. doi:  10.1107/S1600536809031602
PMCID: PMC2970015

1-Benzyl-3-(2-methoxy­phen­yl)imidazolium tetra­fluoro­borate

Abstract

In the title compound, C17H17N2O+·BF4 , the central imidazolium ring makes dihedral angles of 74.58 (9) and 40.10 (6)° with the phenyl and 2-methoxy­phenyl rings, respectively. In the crystal, a strong π–π inter­action is observed between the imidazolium and 2-methoxy­phenyl rings, with a centroid–centroid distance of 3.5115 (15) Å. In addition, C—H(...)F and C—H(...)O hydrogen bonds and C—H(...)π inter­actions involving the ­phenyl ring are observed.

Related literature

For the synthesis, see: Liu et al.. (2003 [triangle]). For general background to N-heterocyclic carbenes, see: Arduengo et al. (1991 [triangle]). For the biological activity of imidazolium salts, see: Vik et al. (2007 [triangle]); Demberelnyamba et al. (2004 [triangle]); Dallas et al. (2007 [triangle]); Ballistreri et al. (2004 [triangle]).

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Object name is e-65-o2178-scheme1.jpg

Experimental

Crystal data

  • C17H17N2O+·BF4
  • M r = 352.14
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2178-efi1.jpg
  • a = 7.1880 (13) Å
  • b = 15.114 (3) Å
  • c = 15.358 (3) Å
  • V = 1668.4 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 93 K
  • 0.40 × 0.33 × 0.33 mm

Data collection

  • Rigaku SPIDER diffractometer
  • Absorption correction: none
  • 13633 measured reflections
  • 2197 independent reflections
  • 2069 reflections with I > 2σ(I)
  • R int = 0.032

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.116
  • S = 1.00
  • 2197 reflections
  • 227 parameters
  • H-atom parameters constrained
  • Δρmax = 0.85 e Å−3
  • Δρmin = −0.19 e Å−3

Data collection: RAPID-AUTO (Rigaku/MSC, 2004 [triangle]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809031602/ci2870sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809031602/ci2870Isup2.hkl

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

Acknowledgments

The authors thank the Fund Projects of Sichuan Educational Department (grant No. 2005 A104).

supplementary crystallographic information

Comment

Since the synthesis and isolation of the first stable, crystalline N-heterocyclic carbene (NHC) was disclosed by Arduengo et al. (1991) scientists have paid much attention to this field. In recent years, a large number of N-heterocyclic carbene (NHC) precursors have been synthesized 1,3-Disubstituted imidazolium salts are potential precursors for the synthesis of various transition metal NHCs. In addition, a number of biological activities of imidazolium salts have been reported including antimicrobial, antifungal, antitumor activities (Vik et al., 2007; Demberelnyamba et al., 2004; Dallas et al., 2007; Ballistreri et al., 2004). We report here crystal structure of a NHC precursor, the title compound.

Bond lengths and angles in title molecule (Fig. 1) are normal. The imidazolium ring makes dihedral angles of 74.58 (9)° and 40.10 (6)°, respectively, with the phenyl ring and 2-methoxyphenyl ring. The methoxy group is slightly twisted away from the attached ring [C17—O1—C16—C15 = -7.8 (4)°].

In the crystal, there are strong π-π interactions between imidazolium and 2-methoxyphenyl rings, with a Cg2···Cg2ii distance of 3.5115 (15) Å [symmetry code: (ii) x - 1/2, 1/2 - y, 1 - z] where Cg2 and Cg3 are centroids of the imidazolium and methoxyphenyl rings, respectively. In addition, C—H···F and C—H···O hydrogen bonds and C—H···π interactions involving the C1—C6 phenyl ring are observed (Table 1).

Experimental

The title compound was prepared according to the reported procedure of Liu et al.. (2003). Colourless single crystals suitable for X-ray diffraction were obtained by recrystallization from dichloromethane and petroleum ether.

Refinement

H atoms were placed in calculated positions [C—H = 0.95–0.99 Å] and refined using a riding model, with Uiso(H) = 1.2Ueq(C).

Figures

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

Crystal data

C17H17N2O+·BF4F(000) = 728
Mr = 352.14Dx = 1.402 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 5660 reflections
a = 7.1880 (13) Åθ = 3.0–27.5°
b = 15.114 (3) ŵ = 0.12 mm1
c = 15.358 (3) ÅT = 93 K
V = 1668.4 (5) Å3Block, colourless
Z = 40.40 × 0.33 × 0.33 mm

Data collection

Rigaku SPIDER diffractometer2069 reflections with I > 2σ(I)
Radiation source: Rotating AnodeRint = 0.032
graphiteθmax = 27.5°, θmin = 3.0°
ω scansh = −9→9
13633 measured reflectionsk = −19→19
2197 independent reflectionsl = −19→15

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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.068P)2 + 0.46P] where P = (Fo2 + 2Fc2)/3
2197 reflections(Δ/σ)max = 0.001
227 parametersΔρmax = 0.85 e Å3
0 restraintsΔρmin = −0.18 e Å3

Special details

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)

xyzUiso*/Ueq
B10.6858 (5)0.1082 (2)0.2432 (2)0.0349 (7)
F10.7005 (2)0.18357 (10)0.29508 (10)0.0360 (4)
F20.7661 (3)0.03715 (11)0.28690 (12)0.0520 (5)
F30.7771 (3)0.12215 (13)0.16519 (11)0.0601 (6)
F40.4996 (3)0.09039 (13)0.22721 (13)0.0555 (6)
O10.6091 (3)0.27395 (12)0.65713 (11)0.0314 (4)
N10.4482 (3)0.45145 (13)0.48559 (13)0.0226 (4)
N20.4930 (3)0.31030 (12)0.49196 (12)0.0203 (4)
C10.6888 (4)0.63622 (15)0.48138 (17)0.0291 (5)
H10.64860.64020.42260.035*
C20.8534 (5)0.67656 (17)0.5060 (2)0.0390 (7)
H20.92620.70750.46420.047*
C30.9113 (5)0.67162 (19)0.5918 (2)0.0453 (8)
H31.02370.69960.60910.054*
C40.8069 (5)0.6263 (2)0.6522 (2)0.0460 (8)
H40.84710.62320.71110.055*
C50.6423 (5)0.58515 (17)0.62717 (18)0.0359 (6)
H50.57100.55350.66890.043*
C60.5814 (4)0.59003 (16)0.54127 (16)0.0264 (5)
C70.4059 (4)0.54316 (16)0.51345 (18)0.0289 (5)
H7A0.31670.54190.56260.035*
H7B0.34750.57580.46470.035*
C80.5203 (3)0.42622 (15)0.40606 (16)0.0230 (5)
H80.54580.46380.35790.028*
C90.5478 (3)0.33788 (15)0.40976 (15)0.0211 (5)
H90.59560.30150.36460.025*
C100.4336 (3)0.38076 (16)0.53617 (15)0.0227 (5)
H100.38830.38030.59430.027*
C110.4976 (3)0.22050 (15)0.52293 (15)0.0213 (5)
C120.4486 (3)0.15283 (16)0.46744 (16)0.0235 (5)
H120.41160.16570.40940.028*
C130.4533 (3)0.06574 (16)0.49642 (18)0.0288 (5)
H130.42080.01880.45820.035*
C140.5056 (4)0.04793 (17)0.58102 (19)0.0317 (6)
H140.5070−0.01160.60100.038*
C150.5562 (3)0.11531 (17)0.63726 (18)0.0305 (6)
H150.59180.10190.69530.037*
C160.5549 (3)0.20287 (16)0.60874 (15)0.0246 (5)
C170.6499 (5)0.2592 (2)0.74763 (17)0.0423 (7)
H17A0.53850.23690.77710.051*
H17B0.68850.31510.77460.051*
H17C0.75040.21580.75290.051*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
B10.0408 (16)0.0351 (15)0.0287 (15)0.0150 (14)−0.0110 (14)−0.0110 (13)
F10.0441 (9)0.0332 (8)0.0308 (8)0.0046 (7)0.0012 (7)−0.0122 (7)
F20.0711 (13)0.0394 (9)0.0455 (11)0.0217 (9)−0.0260 (10)−0.0105 (8)
F30.0828 (15)0.0669 (13)0.0306 (10)0.0258 (12)0.0078 (10)−0.0132 (9)
F40.0473 (10)0.0555 (11)0.0638 (13)0.0119 (10)−0.0236 (10)−0.0256 (10)
O10.0325 (10)0.0403 (10)0.0214 (9)−0.0103 (8)−0.0031 (8)0.0036 (7)
N10.0221 (9)0.0230 (9)0.0228 (10)0.0009 (8)0.0009 (8)−0.0030 (8)
N20.0206 (9)0.0208 (9)0.0194 (9)−0.0025 (7)0.0009 (8)0.0011 (7)
C10.0393 (13)0.0219 (10)0.0261 (13)0.0020 (11)−0.0057 (11)0.0006 (10)
C20.0464 (16)0.0290 (13)0.0415 (16)−0.0099 (12)−0.0037 (14)0.0027 (11)
C30.0506 (18)0.0347 (14)0.0504 (18)−0.0131 (13)−0.0161 (15)−0.0031 (13)
C40.065 (2)0.0432 (16)0.0298 (15)−0.0067 (16)−0.0153 (15)−0.0046 (13)
C50.0518 (17)0.0313 (12)0.0245 (13)−0.0014 (13)0.0000 (13)−0.0046 (10)
C60.0333 (13)0.0212 (10)0.0247 (12)0.0035 (10)−0.0001 (10)−0.0039 (9)
C70.0308 (12)0.0237 (11)0.0321 (14)0.0052 (10)0.0025 (11)−0.0077 (10)
C80.0252 (11)0.0238 (10)0.0200 (11)−0.0005 (9)0.0021 (10)−0.0004 (9)
C90.0220 (11)0.0225 (10)0.0187 (11)0.0002 (9)0.0019 (9)0.0000 (9)
C100.0214 (10)0.0265 (11)0.0202 (11)−0.0009 (9)0.0030 (9)−0.0009 (9)
C110.0150 (9)0.0244 (10)0.0245 (12)−0.0011 (9)0.0010 (9)0.0044 (9)
C120.0181 (10)0.0250 (11)0.0275 (13)0.0007 (9)−0.0002 (9)0.0017 (9)
C130.0233 (11)0.0254 (11)0.0377 (15)−0.0009 (10)0.0034 (11)0.0012 (10)
C140.0242 (11)0.0274 (11)0.0435 (15)0.0009 (10)0.0027 (12)0.0092 (11)
C150.0218 (11)0.0378 (13)0.0321 (14)0.0019 (10)−0.0002 (10)0.0134 (11)
C160.0179 (10)0.0328 (12)0.0230 (12)−0.0045 (10)−0.0004 (9)0.0038 (9)
C170.0478 (17)0.0537 (17)0.0253 (14)−0.0128 (15)−0.0092 (13)0.0070 (13)

Geometric parameters (Å, °)

B1—F31.382 (4)C5—H50.95
B1—F41.388 (4)C6—C71.509 (4)
B1—F21.392 (3)C7—H7A0.99
B1—F11.394 (3)C7—H7B0.99
O1—C161.363 (3)C8—C91.351 (3)
O1—C171.438 (3)C8—H80.95
N1—C101.325 (3)C9—H90.95
N1—C81.381 (3)C10—H100.95
N1—C71.482 (3)C11—C121.377 (3)
N2—C101.333 (3)C11—C161.406 (3)
N2—C91.387 (3)C12—C131.390 (3)
N2—C111.439 (3)C12—H120.95
C1—C21.383 (4)C13—C141.379 (4)
C1—C61.389 (4)C13—H130.95
C1—H10.95C14—C151.384 (4)
C2—C31.385 (4)C14—H140.95
C2—H20.95C15—C161.394 (3)
C3—C41.376 (5)C15—H150.95
C3—H30.95C17—H17A0.98
C4—C51.391 (5)C17—H17B0.98
C4—H40.95C17—H17C0.98
C5—C61.392 (4)
F3—B1—F4109.5 (2)C6—C7—H7B109.6
F3—B1—F2109.8 (3)H7A—C7—H7B108.1
F4—B1—F2109.6 (3)C9—C8—N1106.9 (2)
F3—B1—F1109.6 (3)C9—C8—H8126.5
F4—B1—F1109.4 (2)N1—C8—H8126.5
F2—B1—F1108.9 (2)C8—C9—N2107.1 (2)
C16—O1—C17117.6 (2)C8—C9—H9126.5
C10—N1—C8109.00 (19)N2—C9—H9126.5
C10—N1—C7124.7 (2)N1—C10—N2108.67 (19)
C8—N1—C7126.2 (2)N1—C10—H10125.7
C10—N2—C9108.33 (19)N2—C10—H10125.7
C10—N2—C11126.33 (19)C12—C11—C16121.0 (2)
C9—N2—C11125.33 (19)C12—C11—N2119.4 (2)
C2—C1—C6121.1 (2)C16—C11—N2119.7 (2)
C2—C1—H1119.5C11—C12—C13119.9 (2)
C6—C1—H1119.5C11—C12—H12120.0
C1—C2—C3119.6 (3)C13—C12—H12120.0
C1—C2—H2120.2C14—C13—C12119.6 (2)
C3—C2—H2120.2C14—C13—H13120.2
C4—C3—C2120.3 (3)C12—C13—H13120.2
C4—C3—H3119.8C13—C14—C15121.1 (2)
C2—C3—H3119.8C13—C14—H14119.5
C3—C4—C5120.0 (3)C15—C14—H14119.5
C3—C4—H4120.0C14—C15—C16120.1 (2)
C5—C4—H4120.0C14—C15—H15120.0
C4—C5—C6120.4 (3)C16—C15—H15120.0
C4—C5—H5119.8O1—C16—C15125.1 (2)
C6—C5—H5119.8O1—C16—C11116.4 (2)
C1—C6—C5118.7 (3)C15—C16—C11118.4 (2)
C1—C6—C7120.9 (2)O1—C17—H17A109.5
C5—C6—C7120.4 (2)O1—C17—H17B109.5
N1—C7—C6110.4 (2)H17A—C17—H17B109.5
N1—C7—H7A109.6O1—C17—H17C109.5
C6—C7—H7A109.6H17A—C17—H17C109.5
N1—C7—H7B109.6H17B—C17—H17C109.5
C6—C1—C2—C3−0.6 (4)C9—N2—C10—N10.1 (3)
C1—C2—C3—C40.5 (5)C11—N2—C10—N1−179.0 (2)
C2—C3—C4—C50.1 (5)C10—N2—C11—C12139.7 (2)
C3—C4—C5—C6−0.5 (5)C9—N2—C11—C12−39.2 (3)
C2—C1—C6—C50.2 (4)C10—N2—C11—C16−41.3 (3)
C2—C1—C6—C7−177.6 (2)C9—N2—C11—C16139.7 (2)
C4—C5—C6—C10.4 (4)C16—C11—C12—C130.8 (3)
C4—C5—C6—C7178.2 (3)N2—C11—C12—C13179.7 (2)
C10—N1—C7—C696.0 (3)C11—C12—C13—C140.6 (4)
C8—N1—C7—C6−79.3 (3)C12—C13—C14—C15−1.0 (4)
C1—C6—C7—N189.0 (3)C13—C14—C15—C160.0 (4)
C5—C6—C7—N1−88.8 (3)C17—O1—C16—C15−7.8 (4)
C10—N1—C8—C90.4 (3)C17—O1—C16—C11173.7 (2)
C7—N1—C8—C9176.3 (2)C14—C15—C16—O1−177.2 (2)
N1—C8—C9—N2−0.4 (3)C14—C15—C16—C111.4 (4)
C10—N2—C9—C80.2 (3)C12—C11—C16—O1176.9 (2)
C11—N2—C9—C8179.3 (2)N2—C11—C16—O1−2.0 (3)
C8—N1—C10—N2−0.3 (3)C12—C11—C16—C15−1.7 (3)
C7—N1—C10—N2−176.3 (2)N2—C11—C16—C15179.4 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C7—H7B···F3i0.992.303.268 (3)167
C8—H8···F4i0.952.343.220 (3)154
C9—H9···F10.952.213.122 (3)161
C10—H10···F1ii0.952.373.236 (3)150
C10—H10···F2ii0.952.383.221 (3)147
C12—H12···O1ii0.952.573.292 (3)133
C14—H14···F3iii0.952.483.274 (3)140
C13—H13···Cg1ii0.942.613.460 (3)149

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2870).

References

  • Arduengo, A. J., Harlow, R. L. & Kline, M. (1991). J. Am. Chem. Soc.113, 361–363.
  • Ballistreri, F. P., Barresi, V., Benedetti, P., Caltabiano, G., Fortuna, C. G., Longo, M. L. & Musumarra, G. (2004). Bioorg. Med. Chem.12, 1689–1695. [PubMed]
  • Dallas, A., Kuhtz, H., Farrell, A., Quilty, B. & Nolan, K. (2007). Tetrahedron Lett.48, 1017–1021.
  • Demberelnyamba, D., Kim, K. S., Choi, S., Park, S. Y., Lee, H., Kim, C. J. & Yoo, I. D. (2004). Bioorg. Med. Chem.12, 853–857. [PubMed]
  • Liu, J. P., Chen, J. B., Zhao, J. F., Zhao, Y. H., li, L. & Zhang, H. B. (2003). Synthesis, pp. 2661–2666.
  • Rigaku/MSC (2004). RAPID-AUTO and CrystalStructure Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Vik, A., Hedner, E., Charnock, C., Tangen, L. W., Samuelsen, Ø., Larsson, R., Bohlin, L. & Gundersen, L.-L. (2007). Bioorg. Med. Chem.15, 4016–4037. [PubMed]

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