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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2803.
Published online 2009 October 23. doi:  10.1107/S1600536809042366
PMCID: PMC2971265

4-(4-Fluoro­phen­yl)-1-methoxy­methyl-2-phenyl-1H-imidazole

Abstract

In the crystal structure of the title compound, C17H15FN2O, the mol­ecules form a three-dimensional network stabilized by π–π inter­actions between two imidazole rings related by a centre of symmetry. The distance between the centroids is 3.5488 (8) Å. The imidazole ring makes dihedral angles of 14.30 (7) and 33.39 (7)° with the 4-fluoro­phenyl ring and the phenyl ring, respectively.

Related literature

For the preparation of diaryl­imidazoles, see: Li et al. (2002 [triangle]). For synthesis of and with related diarylimidazoles, see: Liverton et al. (1999 [triangle]); Kawasaki et al. (1996 [triangle]).

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Object name is e-65-o2803-scheme1.jpg

Experimental

Crystal data

  • C17H15FN2O
  • M r = 282.31
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2803-efi1.jpg
  • a = 10.524 (1) Å
  • b = 11.248 (1) Å
  • c = 11.981 (1) Å
  • β = 92.206 (3)°
  • V = 1417.2 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 173 K
  • 0.40 × 0.30 × 0.10 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: none
  • 37183 measured reflections
  • 3319 independent reflections
  • 2745 reflections with I > 2σ(I)
  • R int = 0.043

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.106
  • S = 1.07
  • 3319 reflections
  • 191 parameters
  • H-atom parameters constrained
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: APEX2 (Bruker, 2006 [triangle]); cell refinement: SAINT (Bruker, 2006 [triangle]); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809042366/bt5098sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809042366/bt5098Isup2.hkl

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

Acknowledgments

The authors would like to thank the Federal Ministry of Education and Research, Germany, Merckle GmbH, Ulm, Germany, and the Fonds der Chemischen Industrie, Germany, for their generous support of this work.

supplementary crystallographic information

Comment

Metallated imidazole intermediates can be widely used in the preparation of imidazole derivatives. To avoid N-metallation, N-protection of the imidazole is necessary. Our approach was a direct regioselective N-protection of the diarylimidazole. The regioselectivity is controlled by the steric effect of the aryl substituent in C-4 position. The title compound forms a three dimensional network stabilized by π-π interactions between two symmetry related imidazole nuclei. The distance between the centroids is 3.5488 (8) Å. The imidazole ring makes dihedral angles of 14.30 (7)° and 33.39 (7)° to the 4-fluorophenyl ring and the phenyl ring, respectively.

Experimental

4-(4-fluorophenyl)-2-phenyl-1H-imidazole (3 g 13 mmol) was dissolved in dry THF (30 ml). After cooling to 273 K sodium bis(trimetyl silyl)amide (8.2 ml, 16 mmol) was added dropwise. The reaction mixture was stirred for 30 min at this temperature. Methoxymethylchloride (2.1M in toluene) (12 ml, 25 mmol) was added dropwise. Stirring was continued at 273 K for 30 min and further 60 min at room temperature. Then concentrated aqueous ammonium chloride solution (30 ml) was added, the reaction mixture was stirred for 1 h. After extraction with ethyl acetate the organic layer was washed twice with water, dried over sodium sulfate and evaporated under reduced pressure. The crude product was purified by flash chromatography to yield 4-(4-fluorophenyl)-1-(methoxymethyl)-2-phenyl-1H-imidazole (42%).

Refinement

Hydrogen atoms were placed at calculated positions with C—H = 0.95 Å (aromatic) or 0.98–0.99 Å (sp3 C-atom) and refined in the riding-model approximation with isotropic displacement parameters (set at 1.2–1.5 times of the Ueq of the parent atom).

Figures

Fig. 1.
View of compound I. Displacement ellipsoids are drawn at the 50% probability level.

Crystal data

C17H15FN2OF(000) = 592
Mr = 282.31Dx = 1.323 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ynCell parameters from 9878 reflections
a = 10.524 (1) Åθ = 2.4–27.6°
b = 11.2480 (11) ŵ = 0.09 mm1
c = 11.9810 (12) ÅT = 173 K
β = 92.206 (3)°Needle, colourless
V = 1417.2 (2) Å30.40 × 0.30 × 0.10 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer2745 reflections with I > 2σ(I)
Radiation source: sealed TubeRint = 0.043
graphiteθmax = 27.7°, θmin = 2.5°
CCD scanh = −13→13
37183 measured reflectionsk = −14→14
3319 independent reflectionsl = −15→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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H-atom parameters constrained
S = 1.07w = 1/[σ2(Fo2) + (0.0415P)2 + 0.5423P] where P = (Fo2 + 2Fc2)/3
3319 reflections(Δ/σ)max = 0.001
191 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = −0.17 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
C10.37469 (12)0.48140 (11)0.36743 (10)0.0272 (3)
N20.47445 (10)0.45452 (9)0.30842 (8)0.0284 (2)
C30.55709 (12)0.54982 (10)0.32055 (10)0.0268 (3)
C40.50522 (12)0.63404 (11)0.38760 (10)0.0289 (3)
H40.54230.70790.40930.035*
N50.38931 (10)0.59103 (9)0.41746 (8)0.0281 (2)
C60.26578 (12)0.40118 (11)0.38101 (10)0.0282 (3)
C70.14177 (12)0.44168 (12)0.39029 (11)0.0348 (3)
H70.12460.52460.38930.042*
C80.04297 (14)0.36122 (14)0.40103 (13)0.0414 (3)
H8−0.04130.38960.40820.050*
C90.06605 (14)0.23974 (14)0.40139 (12)0.0424 (3)
H9−0.00190.18520.40970.051*
C100.18894 (14)0.19848 (13)0.38951 (12)0.0390 (3)
H100.20510.11540.38790.047*
C110.28813 (13)0.27826 (11)0.37999 (11)0.0323 (3)
H110.37230.24940.37270.039*
C120.68112 (12)0.55033 (10)0.26877 (10)0.0270 (3)
C130.70870 (13)0.46715 (11)0.18610 (11)0.0318 (3)
H130.64540.41180.16180.038*
C140.82693 (13)0.46451 (11)0.13935 (11)0.0342 (3)
H140.84530.40760.08370.041*
C150.91715 (13)0.54576 (12)0.17496 (11)0.0334 (3)
C160.89444 (13)0.62991 (12)0.25570 (12)0.0370 (3)
H160.95820.68560.27840.044*
C170.77620 (13)0.63091 (12)0.30265 (11)0.0340 (3)
H170.75930.68750.35900.041*
F181.03312 (8)0.54292 (8)0.12881 (8)0.0482 (2)
C190.30688 (12)0.64839 (12)0.49708 (10)0.0312 (3)
H19A0.26920.58660.54450.037*
H19B0.35910.70120.54640.037*
O200.20865 (9)0.71516 (8)0.44560 (8)0.0363 (2)
C210.25020 (16)0.82639 (13)0.40291 (12)0.0446 (4)
H21A0.28890.87370.46390.067*
H21B0.17720.86940.36940.067*
H21C0.31300.81250.34600.067*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0285 (6)0.0255 (6)0.0277 (6)0.0024 (5)0.0004 (4)0.0019 (4)
N20.0283 (5)0.0269 (5)0.0302 (5)0.0001 (4)0.0024 (4)0.0008 (4)
C30.0284 (6)0.0253 (6)0.0265 (6)0.0001 (5)−0.0001 (4)0.0030 (4)
C40.0293 (6)0.0260 (6)0.0315 (6)−0.0014 (5)0.0017 (5)0.0010 (5)
N50.0294 (5)0.0259 (5)0.0291 (5)0.0012 (4)0.0026 (4)−0.0001 (4)
C60.0287 (6)0.0290 (6)0.0269 (6)−0.0012 (5)0.0016 (4)−0.0001 (5)
C70.0311 (7)0.0337 (7)0.0394 (7)0.0012 (5)0.0013 (5)−0.0020 (5)
C80.0294 (7)0.0493 (9)0.0458 (8)−0.0034 (6)0.0047 (6)−0.0048 (6)
C90.0398 (8)0.0453 (8)0.0424 (8)−0.0156 (6)0.0044 (6)−0.0012 (6)
C100.0477 (8)0.0295 (7)0.0395 (7)−0.0060 (6)0.0000 (6)0.0004 (5)
C110.0328 (7)0.0294 (6)0.0346 (6)0.0004 (5)0.0008 (5)−0.0005 (5)
C120.0291 (6)0.0245 (6)0.0275 (6)0.0009 (5)0.0019 (4)0.0047 (4)
C130.0350 (7)0.0277 (6)0.0327 (6)−0.0038 (5)0.0029 (5)−0.0005 (5)
C140.0398 (7)0.0288 (6)0.0345 (6)0.0000 (5)0.0095 (5)−0.0013 (5)
C150.0302 (7)0.0327 (7)0.0380 (7)0.0012 (5)0.0092 (5)0.0053 (5)
C160.0340 (7)0.0326 (7)0.0447 (8)−0.0070 (5)0.0056 (6)−0.0033 (6)
C170.0351 (7)0.0295 (6)0.0377 (7)−0.0020 (5)0.0058 (5)−0.0043 (5)
F180.0380 (5)0.0473 (5)0.0609 (6)−0.0051 (4)0.0216 (4)−0.0058 (4)
C190.0341 (7)0.0293 (6)0.0305 (6)0.0043 (5)0.0060 (5)0.0008 (5)
O200.0355 (5)0.0292 (5)0.0444 (5)0.0070 (4)0.0049 (4)0.0032 (4)
C210.0661 (10)0.0279 (7)0.0394 (7)0.0026 (7)−0.0033 (7)0.0026 (6)

Geometric parameters (Å, °)

C1—N21.3231 (15)C11—H110.9500
C1—N51.3772 (16)C12—C171.3987 (18)
C1—C61.4727 (17)C12—C131.4010 (17)
N2—C31.3844 (15)C13—C141.3844 (18)
C3—C41.3691 (17)C13—H130.9500
C3—C121.4666 (17)C14—C151.3738 (19)
C4—N51.3725 (16)C14—H140.9500
C4—H40.9500C15—F181.3595 (15)
N5—C191.4637 (15)C15—C161.3808 (19)
C6—C71.3907 (18)C16—C171.3853 (18)
C6—C111.4026 (18)C16—H160.9500
C7—C81.3882 (19)C17—H170.9500
C7—H70.9500C19—O201.4014 (15)
C8—C91.388 (2)C19—H19A0.9900
C8—H80.9500C19—H19B0.9900
C9—C101.387 (2)O20—C211.4266 (17)
C9—H90.9500C21—H21A0.9800
C10—C111.3846 (19)C21—H21B0.9800
C10—H100.9500C21—H21C0.9800
N2—C1—N5111.07 (11)C17—C12—C13118.20 (12)
N2—C1—C6123.78 (11)C17—C12—C3121.21 (11)
N5—C1—C6125.09 (11)C13—C12—C3120.56 (11)
C1—N2—C3105.97 (10)C14—C13—C12120.95 (12)
C4—C3—N2109.53 (11)C14—C13—H13119.5
C4—C3—C12128.82 (11)C12—C13—H13119.5
N2—C3—C12121.62 (11)C15—C14—C13118.77 (12)
C3—C4—N5106.71 (11)C15—C14—H14120.6
C3—C4—H4126.6C13—C14—H14120.6
N5—C4—H4126.6F18—C15—C14118.59 (12)
C4—N5—C1106.72 (10)F18—C15—C16118.90 (12)
C4—N5—C19124.72 (11)C14—C15—C16122.51 (12)
C1—N5—C19128.27 (11)C15—C16—C17118.19 (12)
C7—C6—C11118.81 (12)C15—C16—H16120.9
C7—C6—C1123.02 (12)C17—C16—H16120.9
C11—C6—C1118.13 (11)C16—C17—C12121.38 (12)
C8—C7—C6120.16 (13)C16—C17—H17119.3
C8—C7—H7119.9C12—C17—H17119.3
C6—C7—H7119.9O20—C19—N5113.27 (10)
C9—C8—C7120.70 (14)O20—C19—H19A108.9
C9—C8—H8119.7N5—C19—H19A108.9
C7—C8—H8119.7O20—C19—H19B108.9
C10—C9—C8119.54 (13)N5—C19—H19B108.9
C10—C9—H9120.2H19A—C19—H19B107.7
C8—C9—H9120.2C19—O20—C21113.37 (11)
C11—C10—C9120.04 (13)O20—C21—H21A109.5
C11—C10—H10120.0O20—C21—H21B109.5
C9—C10—H10120.0H21A—C21—H21B109.5
C10—C11—C6120.72 (13)O20—C21—H21C109.5
C10—C11—H11119.6H21A—C21—H21C109.5
C6—C11—H11119.6H21B—C21—H21C109.5
N5—C1—N2—C30.12 (13)C9—C10—C11—C6−0.7 (2)
C6—C1—N2—C3−177.34 (11)C7—C6—C11—C10−0.84 (19)
C1—N2—C3—C4−0.04 (13)C1—C6—C11—C10−178.34 (12)
C1—N2—C3—C12178.28 (10)C4—C3—C12—C1713.98 (19)
N2—C3—C4—N5−0.04 (13)N2—C3—C12—C17−163.99 (11)
C12—C3—C4—N5−178.21 (11)C4—C3—C12—C13−168.03 (12)
C3—C4—N5—C10.11 (13)N2—C3—C12—C1314.00 (17)
C3—C4—N5—C19174.26 (11)C17—C12—C13—C140.16 (19)
N2—C1—N5—C4−0.15 (13)C3—C12—C13—C14−177.89 (11)
C6—C1—N5—C4177.27 (11)C12—C13—C14—C15−0.4 (2)
N2—C1—N5—C19−174.02 (11)C13—C14—C15—F18−179.97 (12)
C6—C1—N5—C193.40 (19)C13—C14—C15—C160.1 (2)
N2—C1—C6—C7−146.46 (13)F18—C15—C16—C17−179.40 (12)
N5—C1—C6—C736.44 (18)C14—C15—C16—C170.6 (2)
N2—C1—C6—C1130.93 (17)C15—C16—C17—C12−0.8 (2)
N5—C1—C6—C11−146.17 (12)C13—C12—C17—C160.49 (19)
C11—C6—C7—C81.54 (19)C3—C12—C17—C16178.53 (12)
C1—C6—C7—C8178.91 (12)C4—N5—C19—O2099.09 (14)
C6—C7—C8—C9−0.7 (2)C1—N5—C19—O20−88.05 (15)
C7—C8—C9—C10−0.8 (2)N5—C19—O20—C21−76.19 (14)
C8—C9—C10—C111.5 (2)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT5098).

References

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  • Liverton, N. J., Butcher, J. W., Claiborne, C. F., Claremon, D. A., Libby, B. E., Nguyen, K. T., Pitzenberger, S. M., Selnick, H. G., Smith, G. R., Tebben, A., Vacca, J. P., Varga, S. L., Agarwal, L., Dancheck, K., Forsyth, A. J., Fletcher, D. S., Frantz, B., Hanlon, W. A., Harper, C. F., Hofsess, S. J., Kostura, M., Lin, J., Luell, S., O’Neill, E. A., Orevillo, C. J., Pang, M., Sahly, S., Visco, D. M. & O’Keefe, S. J. (1999). J. Med. Chem. 42, 2180–2190. [PubMed]
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