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

Zheng, R.-H.

doi:10.1107/S1600536808003711

organic compounds

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ISSN: 2056-9890

Volume 64| Part 3| March 2008| Page o589

doi:10.1107/S1600536808003711

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

Ren-Hua Zheng ^a ^*

^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 ); Bergmann & Solomonovici (1970 ); Larson (1970 ).

Experimental

Crystal data

C₂₂H₁₅Br
M_r = 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 ) T_min = 0.227, T_max = 0.489
8896 measured reflections
3792 independent reflections
2462 reflections with F² > 2σ(F²)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.140
S = 1.00
3792 reflections
209 parameters
H-atom parameters constrained
Δρ_max = 0.83 e Å⁻³
Δρ_min = −0.93 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; 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.

Supporting information

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

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

checkCIF report

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.

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

	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.

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

Crystal data top

C₂₂H₁₅Br	F(000) = 728.00
M_r = 359.26	D_x = 1.429 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 8966 reflections
a = 8.4857 (5) Å	θ = 3.2–27.4°
b = 19.0479 (8) Å	µ = 2.47 mm⁻¹
c = 10.6808 (5) Å	T = 296 K
β = 104.6802 (16)°	Chunk, colourless
V = 1670.03 (14) Å³	0.57 × 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^-1	R_int = 0.051
ω scans	θ_max = 27.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = 0→10
T_min = 0.227, T_max = 0.489	k = 0→24
8896 measured reflections	l = −13→13
3792 independent reflections

Refinement top

Refinement on F²	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.053	w = 1/[0.001F_o² + 6.2σ(F_o²)]/(4F_o²)
wR(F²) = 0.140	(Δ/σ)_max < 0.001
S = 1.01	Δρ_max = 0.83 e Å⁻³
3792 reflections	Δρ_min = −0.93 e Å⁻³
209 parameters	Extinction correction: Larson (1970)
0 restraints	Extinction coefficient: 351 (32)

Crystal data top

C₂₂H₁₅Br	V = 1670.03 (14) Å³
M_r = 359.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.4857 (5) Å	µ = 2.47 mm⁻¹
b = 19.0479 (8) Å	T = 296 K
c = 10.6808 (5) Å	0.57 × 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)
T_min = 0.227, T_max = 0.489	R_int = 0.051
8896 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.140	H-atom parameters constrained
S = 1.01	Δρ_max = 0.83 e Å⁻³
3792 reflections	Δρ_min = −0.93 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Br1	0.09761 (6)	0.48750 (2)	−0.21051 (4)	0.08526 (18)
C1	0.2486 (4)	0.54224 (18)	−0.0874 (3)	0.0574 (10)
C2	0.2994 (4)	0.51963 (18)	0.0385 (3)	0.0618 (11)
C3	0.4098 (4)	0.55959 (17)	0.1270 (3)	0.0586 (11)
C4	0.4709 (4)	0.62248 (17)	0.0924 (2)	0.0482 (9)
C5	0.4180 (4)	0.64341 (19)	−0.0356 (3)	0.0588 (11)
C6	0.3069 (4)	0.60356 (19)	−0.1258 (3)	0.0616 (11)
C7	0.5914 (4)	0.66577 (17)	0.1840 (3)	0.0516 (10)
C8	0.6033 (4)	0.67805 (17)	0.3102 (2)	0.0481 (9)
C9	0.7365 (3)	0.72298 (16)	0.3866 (2)	0.0450 (9)
C10	0.7624 (4)	0.78939 (18)	0.3398 (3)	0.0561 (10)
C11	0.8893 (4)	0.83153 (19)	0.4062 (3)	0.0612 (11)
C12	0.9902 (4)	0.8091 (2)	0.5201 (3)	0.0654 (12)
C13	0.9669 (4)	0.7436 (2)	0.5676 (3)	0.0618 (11)
C14	0.8397 (4)	0.69947 (17)	0.5039 (3)	0.0502 (9)
C15	0.8235 (4)	0.63084 (18)	0.5605 (3)	0.0560 (10)
C16	0.6901 (4)	0.59282 (18)	0.5526 (3)	0.0573 (10)
C17	0.5221 (4)	0.61096 (17)	0.4876 (2)	0.0493 (9)
C18	0.3957 (5)	0.58558 (19)	0.5374 (3)	0.0643 (12)
C19	0.2344 (5)	0.6034 (2)	0.4844 (4)	0.0720 (14)
C20	0.1960 (5)	0.6485 (2)	0.3806 (3)	0.0673 (13)
C21	0.3170 (4)	0.67289 (18)	0.3276 (3)	0.0550 (10)
C22	0.4800 (4)	0.65368 (14)	0.3770 (2)	0.0459 (9)
H2	0.2599	0.4778	0.0637	0.074*
H3	0.4444	0.5441	0.2121	0.070*
H5	0.4576	0.6850	−0.0618	0.071*
H6	0.2725	0.6183	−0.2114	0.074*
H7	0.6696	0.6875	0.1501	0.062*
H10	0.6935	0.8055	0.2630	0.067*
H11	0.9060	0.8753	0.3731	0.073*
H12	1.0740	0.8378	0.5654	0.078*
H13	1.0377	0.7283	0.6441	0.074*
H15	0.9200	0.6110	0.6087	0.067*
H16	0.7057	0.5493	0.5935	0.069*
H18	0.4209	0.5557	0.6086	0.077*
H19	0.1528	0.5850	0.5187	0.086*
H20	0.0886	0.6624	0.3465	0.081*
H21	0.2898	0.7030	0.2568	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0863 (4)	0.0690 (3)	0.0828 (3)	−0.0041 (2)	−0.0113 (2)	−0.0165 (2)
C1	0.061 (2)	0.0547 (19)	0.057 (2)	0.0027 (17)	0.0150 (18)	−0.0078 (16)
C2	0.075 (2)	0.0516 (19)	0.059 (2)	−0.0067 (18)	0.0163 (19)	−0.0031 (16)
C3	0.072 (2)	0.058 (2)	0.0442 (19)	−0.0005 (18)	0.0113 (18)	0.0038 (15)
C4	0.047 (2)	0.0511 (17)	0.0476 (18)	−0.0003 (15)	0.0138 (15)	−0.0006 (14)
C5	0.065 (2)	0.060 (2)	0.050 (2)	−0.0063 (18)	0.0130 (18)	0.0094 (15)
C6	0.068 (2)	0.067 (2)	0.046 (2)	0.0006 (19)	0.0055 (18)	−0.0010 (16)
C7	0.047 (2)	0.0579 (19)	0.0488 (19)	−0.0013 (15)	0.0106 (16)	0.0042 (15)
C8	0.045 (2)	0.0513 (18)	0.0462 (19)	0.0033 (14)	0.0092 (15)	0.0039 (14)
C9	0.0390 (18)	0.0527 (17)	0.0451 (17)	−0.0027 (14)	0.0137 (14)	−0.0061 (14)
C10	0.054 (2)	0.062 (2)	0.053 (2)	−0.0040 (17)	0.0153 (17)	0.0009 (16)
C11	0.059 (2)	0.059 (2)	0.067 (2)	−0.0109 (18)	0.0178 (19)	−0.0059 (17)
C12	0.054 (2)	0.072 (2)	0.069 (2)	−0.0145 (18)	0.012 (2)	−0.0151 (19)
C13	0.046 (2)	0.076 (2)	0.057 (2)	0.0030 (18)	0.0017 (17)	−0.0032 (18)
C14	0.0395 (19)	0.0592 (19)	0.0508 (19)	0.0018 (15)	0.0095 (15)	−0.0089 (15)
C15	0.052 (2)	0.058 (2)	0.054 (2)	0.0050 (17)	0.0062 (17)	0.0034 (16)
C16	0.068 (2)	0.0480 (18)	0.053 (2)	0.0076 (17)	0.0106 (18)	0.0045 (14)
C17	0.056 (2)	0.0462 (17)	0.0474 (19)	−0.0015 (15)	0.0160 (17)	−0.0048 (13)
C18	0.074 (2)	0.065 (2)	0.060 (2)	−0.005 (2)	0.028 (2)	0.0046 (17)
C19	0.065 (2)	0.086 (2)	0.075 (2)	−0.017 (2)	0.036 (2)	−0.012 (2)
C20	0.051 (2)	0.084 (2)	0.069 (2)	0.002 (2)	0.021 (2)	−0.016 (2)
C21	0.050 (2)	0.062 (2)	0.053 (2)	0.0002 (17)	0.0117 (17)	−0.0066 (16)
C22	0.046 (2)	0.0461 (17)	0.0466 (17)	−0.0028 (14)	0.0123 (15)	−0.0064 (13)

Geometric parameters (Å, º) top

Br1—C1	1.899 (3)	C17—C22	1.404 (4)
C1—C2	1.372 (4)	C18—C19	1.384 (5)
C1—C6	1.371 (5)	C19—C20	1.375 (5)
C2—C3	1.379 (4)	C20—C21	1.374 (6)
C3—C4	1.392 (4)	C21—C22	1.399 (4)
C4—C5	1.386 (4)	C2—H2	0.930
C4—C7	1.475 (4)	C3—H3	0.930
C5—C6	1.390 (4)	C5—H5	0.930
C7—C8	1.346 (4)	C6—H6	0.930
C8—C9	1.486 (4)	C7—H7	0.930
C8—C22	1.482 (5)	C10—H10	0.930
C9—C10	1.398 (4)	C11—H11	0.930
C9—C14	1.408 (4)	C12—H12	0.930
C10—C11	1.386 (4)	C13—H13	0.930
C11—C12	1.367 (4)	C15—H15	0.930
C12—C13	1.378 (5)	C16—H16	0.930
C13—C14	1.401 (4)	C18—H18	0.930
C14—C15	1.461 (4)	C19—H19	0.930
C15—C16	1.328 (5)	C20—H20	0.930
C16—C17	1.461 (4)	C21—H21	0.930
C17—C18	1.398 (6)

Br1—C1—C2	119.7 (2)	C8—C22—C17	121.8 (2)
Br1—C1—C6	119.4 (2)	C8—C22—C21	119.2 (2)
C2—C1—C6	120.9 (3)	C17—C22—C21	119.1 (3)
C1—C2—C3	119.2 (3)	C1—C2—H2	120.4
C2—C3—C4	121.8 (3)	C3—C2—H2	120.4
C3—C4—C5	117.4 (2)	C2—C3—H3	119.1
C3—C4—C7	123.2 (2)	C4—C3—H3	119.1
C5—C4—C7	119.4 (3)	C4—C5—H5	119.3
C4—C5—C6	121.3 (3)	C6—C5—H5	119.3
C1—C6—C5	119.3 (3)	C1—C6—H6	120.3
C4—C7—C8	128.7 (3)	C5—C6—H6	120.3
C7—C8—C9	120.2 (3)	C4—C7—H7	115.7
C7—C8—C22	123.0 (2)	C8—C7—H7	115.7
C9—C8—C22	116.6 (2)	C9—C10—H10	119.6
C8—C9—C10	119.4 (2)	C11—C10—H10	119.6
C8—C9—C14	121.4 (2)	C10—C11—H11	119.9
C10—C9—C14	119.2 (2)	C12—C11—H11	119.9
C9—C10—C11	120.9 (2)	C11—C12—H12	120.2
C10—C11—C12	120.3 (3)	C13—C12—H12	120.2
C11—C12—C13	119.7 (3)	C12—C13—H13	119.0
C12—C13—C14	121.9 (3)	C14—C13—H13	119.0
C9—C14—C13	118.1 (3)	C14—C15—H15	115.5
C9—C14—C15	123.4 (2)	C16—C15—H15	115.5
C13—C14—C15	118.5 (2)	C15—C16—H16	116.0
C14—C15—C16	129.0 (3)	C17—C16—H16	116.0
C15—C16—C17	127.9 (3)	C17—C18—H18	118.9
C16—C17—C18	119.2 (3)	C19—C18—H18	118.9
C16—C17—C22	123.1 (3)	C18—C19—H19	120.3
C18—C17—C22	117.7 (3)	C20—C19—H19	120.3
C17—C18—C19	122.2 (3)	C19—C20—H20	120.2
C18—C19—C20	119.4 (4)	C21—C20—H20	120.2
C19—C20—C21	119.7 (3)	C20—C21—H21	119.1
C20—C21—C22	121.8 (3)	C22—C21—H21	119.1

Br1—C1—C2—C3	179.7 (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—C11	1.0 (5)
C6—C1—C2—C3	0.4 (6)	C9—C10—C11—C12	−1.0 (6)
C1—C2—C3—C4	0.2 (5)	C10—C11—C12—C13	1.2 (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—C9	1.5 (5)
C3—C4—C5—C6	0.7 (5)	C12—C13—C14—C15	180.0 (2)
C3—C4—C7—C8	−37.4 (5)	C9—C14—C15—C16	−30.8 (6)
C5—C4—C7—C8	144.6 (3)	C13—C14—C15—C16	150.9 (4)
C7—C4—C5—C6	178.8 (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—C9	179.2 (3)	C15—C16—C17—C22	30.7 (5)
C4—C7—C8—C22	−6.3 (5)	C16—C17—C18—C19	176.9 (3)
C7—C8—C9—C10	51.4 (4)	C16—C17—C22—C8	6.1 (4)
C7—C8—C9—C14	−127.2 (3)	C16—C17—C22—C21	−174.9 (3)
C7—C8—C22—C17	123.5 (3)	C18—C17—C22—C8	−174.6 (3)
C7—C8—C22—C21	−55.6 (4)	C18—C17—C22—C21	4.5 (4)
C9—C8—C22—C17	−61.8 (4)	C22—C17—C18—C19	−2.5 (5)
C9—C8—C22—C21	119.2 (3)	C17—C18—C19—C20	−1.2 (6)
C22—C8—C9—C10	−123.5 (3)	C18—C19—C20—C21	2.8 (6)
C22—C8—C9—C14	57.9 (4)	C19—C20—C21—C22	−0.7 (5)
C8—C9—C10—C11	−177.6 (3)	C20—C21—C22—C8	176.0 (3)
C8—C9—C14—C13	177.3 (3)	C20—C21—C22—C17	−3.1 (4)
C8—C9—C14—C15	−1.0 (5)

Experimental details

Crystal data
Chemical formula	C₂₂H₁₅Br
M_r	359.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.4857 (5), 19.0479 (8), 10.6808 (5)
β (°)	104.6802 (16)
V (Å³)	1670.03 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.47
Crystal size (mm)	0.57 × 0.46 × 0.29

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.227, 0.489
No. of measured, independent and observed [F² > 2σ(F²)] reflections	8896, 3792, 2462
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.140, 1.01
No. of reflections	3792
No. of parameters	209
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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

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