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Acta Crystallogr Sect E Struct Rep Online. 2008 March 1; 64(Pt 3): o589.
Published online 2008 February 15. doi:  10.1107/S1600536808003711
PMCID: PMC2960858

5-(4-Bromo­benzyl­idene)-5H-dibenzo[a,d][7]annulene

Abstract

The tricyclic system of the title compound, C22H15Br, has a concave shape, with a dihedral angle between the benzene ring planes of 48.68 (1)°.

Related literature

For related literature, see: Allen et al. (1987 [triangle]); Bergmann & Solomonovici (1970 [triangle]); Larson (1970 [triangle]).

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Object name is e-64-0o589-scheme1.jpg

Experimental

Crystal data

  • C22H15Br
  • M r = 359.26
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o589-efi1.jpg
  • a = 8.4857 (5) Å
  • b = 19.0479 (8) Å
  • c = 10.6808 (5) Å
  • β = 104.6802 (16)°
  • V = 1670.03 (14) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.46 mm−1
  • T = 296 (1) K
  • 0.57 × 0.46 × 0.29 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.227, T max = 0.489
  • 8896 measured reflections
  • 3792 independent reflections
  • 2462 reflections with F 2 > 2σ(F 2)
  • R int = 0.051

Refinement

  • R[F 2 > 2σ(F 2)] = 0.053
  • wR(F 2) = 0.140
  • S = 1.00
  • 3792 reflections
  • 209 parameters
  • H-atom parameters constrained
  • Δρmax = 0.83 e Å−3
  • Δρmin = −0.93 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 [triangle]); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 [triangle]); program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablocks globbal, I. DOI: 10.1107/S1600536808003711/gk2131sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808003711/gk2131Isup2.hkl

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

Acknowledgments

The author acknowledges the help of Professor Jian-Ming Gu of Zhejiang University.

supplementary crystallographic information

Comment

The title compound was synthesized through Wittig–Horner reaction (Bergmann & Solomonovici, 1970).

The molecular structure is shown in Fig. 1. The bond lengths and angles are generally within normal ranges (Allen et al.,1987). Packing diagram is given in Fig. 2. The seven-membered ring is in a boat conformation. The dihedral angle between the benzene A (C1–C6) and the plane defined by the atoms C9/C14/C17 /C22 is 29.5 (1)°. Benzene C (C9–C14) and benzene D (C17–C22) form with the plane defined by C9/C14/C17/C22 dihedral angles of 24.1 (1)° and 26.4 (1)°, respectively, while the dihedral angle between them is 48.68 (1)°. The crystal packing (Fig. 2) is mainly stabilized by van der Waals forces.

Experimental

The title compound was synthesized by treating solution of (4-bromo-benzyl)-phosphonic acid diethyl ester (1.53 g, 5 mmol) and dibenzo[a,d]cyclohepten-5-one (1.03 g, 5 mmol) in 100 ml anhydrous THF under nitrogen with solid potassium tert-butoxide (1.68 g, 15 mmol) which was added in one portion. The mixture was refluxed with stirring for 10 h. Solvent was removed by rotary evaporation. The residue was purified by column chromatography (silica gel) using n-hexane as eluent. Colorless crystals were obtained by slow evaporation of a dichloromethane solution.

Refinement

The H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å and Uiso = 1.2Ueq(C).

Figures

Fig. 1.
Molecular structure of of the title compound with displacement ellipsoids shown at the 50% probability level.
Fig. 2.
Crystal packing diagram of the title compound.

Crystal data

C22H15BrF000 = 728.00
Mr = 359.26Dx = 1.429 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71075 Å
Hall symbol: -P 2ybcCell parameters from 8966 reflections
a = 8.4857 (5) Åθ = 3.2–27.4º
b = 19.0479 (8) ŵ = 2.47 mm1
c = 10.6808 (5) ÅT = 296 (1) K
β = 104.6802 (16)ºChunk, colourless
V = 1670.03 (14) Å30.57 × 0.46 × 0.29 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer2462 reflections with F2 > 2σ(F2)
Detector resolution: 10.00 pixels mm-1Rint = 0.051
ω scansθmax = 27.4º
Absorption correction: multi-scan(ABSCOR; Higashi, 1995)h = 0→10
Tmin = 0.227, Tmax = 0.489k = 0→24
8896 measured reflectionsl = −13→13
3792 independent reflections

Refinement

Refinement on F2  w = 1/[0.001Fo2 + 6.2σ(Fo2)]/(4Fo2)
R[F2 > 2σ(F2)] = 0.053(Δ/σ)max < 0.001
wR(F2) = 0.140Δρmax = 0.83 e Å3
S = 1.01Δρmin = −0.93 e Å3
3792 reflectionsExtinction correction: Larson (1970)
209 parametersExtinction coefficient: 351 (32)
H-atom parameters constrained

Special details

Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

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

xyzUiso*/Ueq
Br10.09761 (6)0.48750 (2)−0.21051 (4)0.08526 (18)
C10.2486 (4)0.54224 (18)−0.0874 (3)0.0574 (10)
C20.2994 (4)0.51963 (18)0.0385 (3)0.0618 (11)
C30.4098 (4)0.55959 (17)0.1270 (3)0.0586 (11)
C40.4709 (4)0.62248 (17)0.0924 (2)0.0482 (9)
C50.4180 (4)0.64341 (19)−0.0356 (3)0.0588 (11)
C60.3069 (4)0.60356 (19)−0.1258 (3)0.0616 (11)
C70.5914 (4)0.66577 (17)0.1840 (3)0.0516 (10)
C80.6033 (4)0.67805 (17)0.3102 (2)0.0481 (9)
C90.7365 (3)0.72298 (16)0.3866 (2)0.0450 (9)
C100.7624 (4)0.78939 (18)0.3398 (3)0.0561 (10)
C110.8893 (4)0.83153 (19)0.4062 (3)0.0612 (11)
C120.9902 (4)0.8091 (2)0.5201 (3)0.0654 (12)
C130.9669 (4)0.7436 (2)0.5676 (3)0.0618 (11)
C140.8397 (4)0.69947 (17)0.5039 (3)0.0502 (9)
C150.8235 (4)0.63084 (18)0.5605 (3)0.0560 (10)
C160.6901 (4)0.59282 (18)0.5526 (3)0.0573 (10)
C170.5221 (4)0.61096 (17)0.4876 (2)0.0493 (9)
C180.3957 (5)0.58558 (19)0.5374 (3)0.0643 (12)
C190.2344 (5)0.6034 (2)0.4844 (4)0.0720 (14)
C200.1960 (5)0.6485 (2)0.3806 (3)0.0673 (13)
C210.3170 (4)0.67289 (18)0.3276 (3)0.0550 (10)
C220.4800 (4)0.65368 (14)0.3770 (2)0.0459 (9)
H20.25990.47780.06370.074*
H30.44440.54410.21210.070*
H50.45760.6850−0.06180.071*
H60.27250.6183−0.21140.074*
H70.66960.68750.15010.062*
H100.69350.80550.26300.067*
H110.90600.87530.37310.073*
H121.07400.83780.56540.078*
H131.03770.72830.64410.074*
H150.92000.61100.60870.067*
H160.70570.54930.59350.069*
H180.42090.55570.60860.077*
H190.15280.58500.51870.086*
H200.08860.66240.34650.081*
H210.28980.70300.25680.066*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0863 (4)0.0690 (3)0.0828 (3)−0.0041 (2)−0.0113 (2)−0.0165 (2)
C10.061 (2)0.0547 (19)0.057 (2)0.0027 (17)0.0150 (18)−0.0078 (16)
C20.075 (2)0.0516 (19)0.059 (2)−0.0067 (18)0.0163 (19)−0.0031 (16)
C30.072 (2)0.058 (2)0.0442 (19)−0.0005 (18)0.0113 (18)0.0038 (15)
C40.047 (2)0.0511 (17)0.0476 (18)−0.0003 (15)0.0138 (15)−0.0006 (14)
C50.065 (2)0.060 (2)0.050 (2)−0.0063 (18)0.0130 (18)0.0094 (15)
C60.068 (2)0.067 (2)0.046 (2)0.0006 (19)0.0055 (18)−0.0010 (16)
C70.047 (2)0.0579 (19)0.0488 (19)−0.0013 (15)0.0106 (16)0.0042 (15)
C80.045 (2)0.0513 (18)0.0462 (19)0.0033 (14)0.0092 (15)0.0039 (14)
C90.0390 (18)0.0527 (17)0.0451 (17)−0.0027 (14)0.0137 (14)−0.0061 (14)
C100.054 (2)0.062 (2)0.053 (2)−0.0040 (17)0.0153 (17)0.0009 (16)
C110.059 (2)0.059 (2)0.067 (2)−0.0109 (18)0.0178 (19)−0.0059 (17)
C120.054 (2)0.072 (2)0.069 (2)−0.0145 (18)0.012 (2)−0.0151 (19)
C130.046 (2)0.076 (2)0.057 (2)0.0030 (18)0.0017 (17)−0.0032 (18)
C140.0395 (19)0.0592 (19)0.0508 (19)0.0018 (15)0.0095 (15)−0.0089 (15)
C150.052 (2)0.058 (2)0.054 (2)0.0050 (17)0.0062 (17)0.0034 (16)
C160.068 (2)0.0480 (18)0.053 (2)0.0076 (17)0.0106 (18)0.0045 (14)
C170.056 (2)0.0462 (17)0.0474 (19)−0.0015 (15)0.0160 (17)−0.0048 (13)
C180.074 (2)0.065 (2)0.060 (2)−0.005 (2)0.028 (2)0.0046 (17)
C190.065 (2)0.086 (2)0.075 (2)−0.017 (2)0.036 (2)−0.012 (2)
C200.051 (2)0.084 (2)0.069 (2)0.002 (2)0.021 (2)−0.016 (2)
C210.050 (2)0.062 (2)0.053 (2)0.0002 (17)0.0117 (17)−0.0066 (16)
C220.046 (2)0.0461 (17)0.0466 (17)−0.0028 (14)0.0123 (15)−0.0064 (13)

Geometric parameters (Å, °)

Br1—C11.899 (3)C17—C221.404 (4)
C1—C21.372 (4)C18—C191.384 (5)
C1—C61.371 (5)C19—C201.375 (5)
C2—C31.379 (4)C20—C211.374 (6)
C3—C41.392 (4)C21—C221.399 (4)
C4—C51.386 (4)C2—H20.930
C4—C71.475 (4)C3—H30.930
C5—C61.390 (4)C5—H50.930
C7—C81.346 (4)C6—H60.930
C8—C91.486 (4)C7—H70.930
C8—C221.482 (5)C10—H100.930
C9—C101.398 (4)C11—H110.930
C9—C141.408 (4)C12—H120.930
C10—C111.386 (4)C13—H130.930
C11—C121.367 (4)C15—H150.930
C12—C131.378 (5)C16—H160.930
C13—C141.401 (4)C18—H180.930
C14—C151.461 (4)C19—H190.930
C15—C161.328 (5)C20—H200.930
C16—C171.461 (4)C21—H210.930
C17—C181.398 (6)
Br1—C1—C2119.7 (2)C8—C22—C17121.8 (2)
Br1—C1—C6119.4 (2)C8—C22—C21119.2 (2)
C2—C1—C6120.9 (3)C17—C22—C21119.1 (3)
C1—C2—C3119.2 (3)C1—C2—H2120.4
C2—C3—C4121.8 (3)C3—C2—H2120.4
C3—C4—C5117.4 (2)C2—C3—H3119.1
C3—C4—C7123.2 (2)C4—C3—H3119.1
C5—C4—C7119.4 (3)C4—C5—H5119.3
C4—C5—C6121.3 (3)C6—C5—H5119.3
C1—C6—C5119.3 (3)C1—C6—H6120.3
C4—C7—C8128.7 (3)C5—C6—H6120.3
C7—C8—C9120.2 (3)C4—C7—H7115.7
C7—C8—C22123.0 (2)C8—C7—H7115.7
C9—C8—C22116.6 (2)C9—C10—H10119.6
C8—C9—C10119.4 (2)C11—C10—H10119.6
C8—C9—C14121.4 (2)C10—C11—H11119.9
C10—C9—C14119.2 (2)C12—C11—H11119.9
C9—C10—C11120.9 (2)C11—C12—H12120.2
C10—C11—C12120.3 (3)C13—C12—H12120.2
C11—C12—C13119.7 (3)C12—C13—H13119.0
C12—C13—C14121.9 (3)C14—C13—H13119.0
C9—C14—C13118.1 (3)C14—C15—H15115.5
C9—C14—C15123.4 (2)C16—C15—H15115.5
C13—C14—C15118.5 (2)C15—C16—H16116.0
C14—C15—C16129.0 (3)C17—C16—H16116.0
C15—C16—C17127.9 (3)C17—C18—H18118.9
C16—C17—C18119.2 (3)C19—C18—H18118.9
C16—C17—C22123.1 (3)C18—C19—H19120.3
C18—C17—C22117.7 (3)C20—C19—H19120.3
C17—C18—C19122.2 (3)C19—C20—H20120.2
C18—C19—C20119.4 (4)C21—C20—H20120.2
C19—C20—C21119.7 (3)C20—C21—H21119.1
C20—C21—C22121.8 (3)C22—C21—H21119.1
Br1—C1—C2—C3179.7 (3)C10—C9—C14—C13−1.3 (5)
Br1—C1—C6—C5−179.7 (3)C10—C9—C14—C15−179.6 (3)
C2—C1—C6—C5−0.5 (6)C14—C9—C10—C111.0 (5)
C6—C1—C2—C30.4 (6)C9—C10—C11—C12−1.0 (6)
C1—C2—C3—C40.2 (5)C10—C11—C12—C131.2 (6)
C2—C3—C4—C5−0.7 (5)C11—C12—C13—C14−1.5 (6)
C2—C3—C4—C7−178.8 (3)C12—C13—C14—C91.5 (5)
C3—C4—C5—C60.7 (5)C12—C13—C14—C15180.0 (2)
C3—C4—C7—C8−37.4 (5)C9—C14—C15—C16−30.8 (6)
C5—C4—C7—C8144.6 (3)C13—C14—C15—C16150.9 (4)
C7—C4—C5—C6178.8 (3)C14—C15—C16—C17−2.0 (6)
C4—C5—C6—C1−0.1 (4)C15—C16—C17—C18−148.6 (3)
C4—C7—C8—C9179.2 (3)C15—C16—C17—C2230.7 (5)
C4—C7—C8—C22−6.3 (5)C16—C17—C18—C19176.9 (3)
C7—C8—C9—C1051.4 (4)C16—C17—C22—C86.1 (4)
C7—C8—C9—C14−127.2 (3)C16—C17—C22—C21−174.9 (3)
C7—C8—C22—C17123.5 (3)C18—C17—C22—C8−174.6 (3)
C7—C8—C22—C21−55.6 (4)C18—C17—C22—C214.5 (4)
C9—C8—C22—C17−61.8 (4)C22—C17—C18—C19−2.5 (5)
C9—C8—C22—C21119.2 (3)C17—C18—C19—C20−1.2 (6)
C22—C8—C9—C10−123.5 (3)C18—C19—C20—C212.8 (6)
C22—C8—C9—C1457.9 (4)C19—C20—C21—C22−0.7 (5)
C8—C9—C10—C11−177.6 (3)C20—C21—C22—C8176.0 (3)
C8—C9—C14—C13177.3 (3)C20—C21—C22—C17−3.1 (4)
C8—C9—C14—C15−1.0 (5)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2131).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst.32, 115–119.
  • Bergmann, D. E. & Solomonovici, A. (1970). Synthesis, 2, 183–189.
  • Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst.36, 1487.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Larson, A. C. (1970). Crystallographic Computing, edited by F. R. Ahmed, S. R. Hall & C. P. Huber, pp. 291–294. Copenhagen: Munksgaard.
  • Rigaku (1998). PROCESS-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2004). CrystalStructure Rigaku/MSC, The Woodlands, Texas, USA.

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