organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

aSchool of Pharmaceutical and Chemical Engineering, Taizhou University, Linhai 317000, People's Republic of China
*Correspondence e-mail: zrh1977@126.com

(Received 15 January 2008; accepted 3 February 2008; online 15 February 2008)

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[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.]); Bergmann & Solomonovici (1970[Bergmann, D. E. & Solomonovici, A. (1970). Synthesis, 2, 183-189.]); Larson (1970[Larson, A. C. (1970). Crystallographic Computing, edited by F. R. Ahmed, S. R. Hall & C. P. Huber, pp. 291-294. Copenhagen: Munksgaard.]).

[Scheme 1]

Experimental

Crystal data
  • C22H15Br

  • Mr = 359.26

  • Monoclinic, P 21 /c

  • 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[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.227, Tmax = 0.489

  • 8896 measured reflections

  • 3792 independent reflections

  • 2462 reflections with F2 > 2σ(F2)

  • Rint = 0.051

Refinement
  • R[F2 > 2σ(F2)] = 0.053

  • wR(F2) = 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[Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004[Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.]); program(s) used to solve structure: SIR97 (Altomare et al., 1999[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.]); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003[Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: CrystalStructure.

Supporting information


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
C22H15BrF(000) = 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 = 3.2–27.4°
b = 19.0479 (8) ŵ = 2.47 mm1
c = 10.6808 (5) ÅT = 296 K
β = 104.6802 (16)°Chunk, 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 = 27.4°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 010
Tmin = 0.227, Tmax = 0.489k = 024
8896 measured reflectionsl = 1313
3792 independent reflections
Refinement top
Refinement on F2H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.053 w = 1/[0.001Fo2 + 6.2σ(Fo2)]/(4Fo2)
wR(F2) = 0.140(Δ/σ)max < 0.001
S = 1.01Δρmax = 0.83 e Å3
3792 reflectionsΔρmin = 0.93 e Å3
209 parametersExtinction correction: Larson (1970)
0 restraintsExtinction coefficient: 351 (32)
Crystal data top
C22H15BrV = 1670.03 (14) Å3
Mr = 359.26Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.4857 (5) ŵ = 2.47 mm1
b = 19.0479 (8) ÅT = 296 K
c = 10.6808 (5) Å0.57 × 0.46 × 0.29 mm
β = 104.6802 (16)°
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)] = 0.0530 restraints
wR(F2) = 0.140H-atom parameters constrained
S = 1.01Δρmax = 0.83 e Å3
3792 reflectionsΔρmin = 0.93 e Å3
209 parameters
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*
H50.45760.68500.06180.071*
H60.27250.61830.21140.074*
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, º) 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—C131.3 (5)
Br1—C1—C6—C5179.7 (3)C10—C9—C14—C15179.6 (3)
C2—C1—C6—C50.5 (6)C14—C9—C10—C111.0 (5)
C6—C1—C2—C30.4 (6)C9—C10—C11—C121.0 (6)
C1—C2—C3—C40.2 (5)C10—C11—C12—C131.2 (6)
C2—C3—C4—C50.7 (5)C11—C12—C13—C141.5 (6)
C2—C3—C4—C7178.8 (3)C12—C13—C14—C91.5 (5)
C3—C4—C5—C60.7 (5)C12—C13—C14—C15180.0 (2)
C3—C4—C7—C837.4 (5)C9—C14—C15—C1630.8 (6)
C5—C4—C7—C8144.6 (3)C13—C14—C15—C16150.9 (4)
C7—C4—C5—C6178.8 (3)C14—C15—C16—C172.0 (6)
C4—C5—C6—C10.1 (4)C15—C16—C17—C18148.6 (3)
C4—C7—C8—C9179.2 (3)C15—C16—C17—C2230.7 (5)
C4—C7—C8—C226.3 (5)C16—C17—C18—C19176.9 (3)
C7—C8—C9—C1051.4 (4)C16—C17—C22—C86.1 (4)
C7—C8—C9—C14127.2 (3)C16—C17—C22—C21174.9 (3)
C7—C8—C22—C17123.5 (3)C18—C17—C22—C8174.6 (3)
C7—C8—C22—C2155.6 (4)C18—C17—C22—C214.5 (4)
C9—C8—C22—C1761.8 (4)C22—C17—C18—C192.5 (5)
C9—C8—C22—C21119.2 (3)C17—C18—C19—C201.2 (6)
C22—C8—C9—C10123.5 (3)C18—C19—C20—C212.8 (6)
C22—C8—C9—C1457.9 (4)C19—C20—C21—C220.7 (5)
C8—C9—C10—C11177.6 (3)C20—C21—C22—C8176.0 (3)
C8—C9—C14—C13177.3 (3)C20—C21—C22—C173.1 (4)
C8—C9—C14—C151.0 (5)

Experimental details

Crystal data
Chemical formulaC22H15Br
Mr359.26
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)8.4857 (5), 19.0479 (8), 10.6808 (5)
β (°) 104.6802 (16)
V3)1670.03 (14)
Z4
Radiation typeMo Kα
µ (mm1)2.47
Crystal size (mm)0.57 × 0.46 × 0.29
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.227, 0.489
No. of measured, independent and
observed [F2 > 2σ(F2)] reflections
8896, 3792, 2462
Rint0.051
(sin θ/λ)max1)0.648
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.140, 1.01
No. of reflections3792
No. of parameters209
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.83, 0.93

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SIR97 (Altomare et al., 1999), CRYSTALS (Betteridge et al., 2003), ORTEP-3 for Windows (Farrugia, 1997).

 

Acknowledgements

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

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CrossRef Web of Science Google Scholar
First citationAltomare, 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.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationBergmann, D. E. & Solomonovici, A. (1970). Synthesis, 2, 183–189.  CrossRef CAS Google Scholar
First citationBetteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487.  Web of Science CrossRef IUCr Journals Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationHigashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationLarson, A. C. (1970). Crystallographic Computing, edited by F. R. Ahmed, S. R. Hall & C. P. Huber, pp. 291–294. Copenhagen: Munksgaard.  Google Scholar
First citationRigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku/MSC (2004). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.  Google Scholar

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