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Acta Cryst. (2008). E64, o589    [ doi:10.1107/S1600536808003711 ]

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

R.-H. Zheng

Abstract top

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)°.

Comment top

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.

Related literature top

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

Experimental top

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 top

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).

Computing details top

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

Figures top
[Figure 1] Fig. 1. Molecular structure of of the title compound with displacement ellipsoids shown at the 50% probability level.
[Figure 2] Fig. 2. Crystal packing diagram of the title compound.
5-(4-Bromobenzylidene)-5H-dibenzo[a,d][7]annulene top
Crystal data top
C22H15BrF000 = 728.00
Mr = 359.26Dx = 1.429 Mg m−3
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 mm−1
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 top
Rigaku R-AXIS RAPID
diffractometer		2462 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 top
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 Å−3
S = 1.01Δρmin = −0.93 e Å−3
3792 reflectionsExtinction correction: Larson (1970)
209 parametersExtinction coefficient: 351 (32)
H-atom parameters constrained
Crystal data top
C22H15BrV = 1670.03 (14) Å3
Mr = 359.26Z = 4
Monoclinic, P21/cMo Kα
a = 8.4857 (5) ŵ = 2.47 mm−1
b = 19.0479 (8) ÅT = 296 (1) K
c = 10.6808 (5) Å0.57 × 0.46 × 0.29 mm
β = 104.6802 (16)º
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3792 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2462 reflections with F2 > 2σ(F2)
Tmin = 0.227, Tmax = 0.489Rint = 0.051
8896 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.053209 parameters
wR(F2) = 0.140H-atom parameters constrained
S = 1.01Δρmax = 0.83 e Å−3
3792 reflectionsΔρmin = −0.93 e Å−3
Special details top

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) top
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) top
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, °) top
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)
references
References top

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.