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Acta Cryst. (2007). E63, o3966    [ doi:10.1107/S1600536807035702 ]

3,4-Bis(4-bromophenyl)-2,5-diphenylcyclopenta-2,4-dienone

A. Schwarzer and E. Weber

Abstract top

The title compound, C29H18Br2O, crystallizes as black-violet plates. The molecule displays a paddle-wheel conformation and the crystal packing is stabilized by C-H...[pi] (C-H...[pi] distances in the range 2.7-2.9 Å) and C-H...Br contacts.

Comment top

The molecular geometry is best described by a paddle-wheel fashion, due to steric hindrance of the neighbouring aryl rings. The crystal packing is dominated by intramolecular C—H···π interactions. These intermolecular contacts, where π is an aromatic-ring centroid, with H···π distances ranging from 2.67 to 2.90 Å give rise to the formation of molecular chains extended along the a and b axis. Furthermore, unusual C—H···Br contacts forming a three-dimensional network can be observed (Figure 2).

Related literature top

The paddle-wheel conformation is also a typical feature of the parent substance tetraphenylcyclone (Barnes et al., 1991; Alvarez-Toledano et al., 1997) and the related compound phencyclone (Ruffani et al., 2006), both involving C—H···π contacts in the crystal packing, similar to the title compound. For related literature, see: Dilthey et al. (1935).

Experimental top

The title compound was synthesized according to the procedure described by Dilthey et al. (1935) from 1,2-bis(4-bromophenyl) ethane-1,2-dione, dibenzyl ketone and finely powdered potassium hydroxide in ethanol. Recrystallization from ethyl acetate yielded 72% dark-violet crystals.

Refinement top

The H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95 Å, and Uiso = 1.2–1.5 Ueq(parent atom).

Computing details top

Data collection: APEX2 (Bruker, YEAR?); cell refinement: SMART (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Perspective view of (I), showing 50% probability displacement ellipsoids for the non-H atoms.
[Figure 2] Fig. 2. Packing diagram of (I), viewed down the b axis, with C—H···Br contacts as broken lines.
3,4-Bis(4-bromophenyl)-2,5-diphenylcyclopenta-2,4-dienone top
Crystal data top
C29H18Br2OF000 = 1080
Mr = 542.25Dx = 1.586 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
a = 10.0677 (4) ÅCell parameters from 5575 reflections
b = 9.6526 (4) Åθ = 2.5–28.7º
c = 23.6791 (9) ŵ = 3.59 mm−1
β = 99.193 (2)ºT = 93 (2) K
V = 2271.57 (16) Å3Plate, dark-violet
Z = 40.20 × 0.19 × 0.18 mm
Data collection top
Bruker KappaCCD APEXII area-detector
diffractometer		3999 independent reflections
Radiation source: fine-focus sealed tube3578 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.024
T = 93(2) Kθmax = 25.0º
φ and ω scansθmin = 1.7º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −11→11
Tmin = 0.534, Tmax = 0.564k = −11→11
21955 measured reflectionsl = −23→28
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.019H-atom parameters constrained
wR(F2) = 0.047  w = 1/[σ2(Fo2) + (0.0196P)2 + 1.357P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.002
3999 reflectionsΔρmax = 0.34 e Å−3
289 parametersΔρmin = −0.26 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C29H18Br2OV = 2271.57 (16) Å3
Mr = 542.25Z = 4
Monoclinic, P21/cMo Kα
a = 10.0677 (4) ŵ = 3.59 mm−1
b = 9.6526 (4) ÅT = 93 (2) K
c = 23.6791 (9) Å0.20 × 0.19 × 0.18 mm
β = 99.193 (2)º
Data collection top
Bruker KappaCCD APEXII area-detector
diffractometer		3999 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		3578 reflections with I > 2σ(I)
Tmin = 0.534, Tmax = 0.564Rint = 0.024
21955 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.019289 parameters
wR(F2) = 0.047H-atom parameters constrained
S = 1.06Δρmax = 0.34 e Å−3
3999 reflectionsΔρmin = −0.26 e Å−3
Special details top

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 > 2sigma(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) top
xyzUiso*/Ueq
O11.11380 (13)0.81448 (14)0.50405 (5)0.0234 (3)
Br10.453140 (18)0.255240 (19)0.278725 (8)0.02000 (6)
Br21.088680 (19)0.50624 (2)0.125864 (7)0.02318 (6)
C11.06412 (18)0.74769 (18)0.46290 (7)0.0171 (4)
C20.92780 (18)0.67815 (18)0.45385 (7)0.0156 (4)
C30.91426 (18)0.61459 (18)0.40263 (7)0.0152 (4)
C41.03677 (18)0.64253 (18)0.37486 (7)0.0147 (4)
C51.12617 (18)0.71972 (18)0.40982 (7)0.0155 (4)
C61.25237 (18)0.78587 (18)0.39981 (7)0.0156 (4)
C71.26415 (19)0.84047 (18)0.34603 (8)0.0173 (4)
H71.19120.83200.31540.021*
C81.38078 (19)0.90662 (19)0.33701 (8)0.0203 (4)
H81.38720.94340.30030.024*
C91.48880 (19)0.91968 (19)0.38138 (8)0.0220 (4)
H91.56900.96470.37500.026*
C101.47859 (19)0.86662 (19)0.43476 (8)0.0217 (4)
H101.55210.87530.46510.026*
C111.36124 (19)0.80057 (19)0.44427 (8)0.0187 (4)
H111.35500.76520.48120.022*
C120.83491 (18)0.68419 (19)0.49612 (7)0.0154 (4)
C130.82388 (18)0.80643 (19)0.52658 (7)0.0178 (4)
H130.87950.88330.52130.021*
C140.73240 (19)0.8167 (2)0.56443 (8)0.0203 (4)
H140.72590.90020.58500.024*
C150.65065 (19)0.7056 (2)0.57225 (8)0.0217 (4)
H150.58710.71330.59770.026*
C160.6614 (2)0.5828 (2)0.54287 (8)0.0220 (4)
H160.60570.50620.54840.026*
C170.75368 (19)0.57192 (19)0.50535 (7)0.0186 (4)
H170.76160.48720.48570.022*
C180.80114 (18)0.52985 (18)0.37389 (7)0.0142 (4)
C190.66960 (18)0.58029 (18)0.36437 (7)0.0162 (4)
H190.65170.67040.37740.019*
C200.56437 (18)0.50109 (19)0.33620 (8)0.0173 (4)
H200.47510.53630.32960.021*
C210.59257 (18)0.36977 (18)0.31805 (7)0.0153 (4)
C220.72124 (19)0.31713 (19)0.32679 (8)0.0217 (4)
H220.73830.22670.31380.026*
C230.82536 (19)0.39715 (19)0.35460 (8)0.0211 (4)
H230.91440.36140.36060.025*
C241.04490 (18)0.59994 (18)0.31555 (7)0.0147 (4)
C250.94423 (18)0.63988 (19)0.27082 (7)0.0173 (4)
H250.86710.68730.27930.021*
C260.95508 (18)0.61145 (19)0.21434 (8)0.0183 (4)
H260.88710.64040.18410.022*
C271.06679 (19)0.54023 (18)0.20290 (7)0.0166 (4)
C281.16667 (18)0.49671 (18)0.24641 (8)0.0171 (4)
H281.24220.44690.23770.021*
C291.15549 (18)0.52640 (18)0.30265 (8)0.0164 (4)
H291.22360.49650.33270.020*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0216 (7)0.0311 (8)0.0170 (7)−0.0036 (6)0.0015 (6)−0.0078 (6)
Br10.01865 (11)0.01994 (11)0.02038 (10)−0.00453 (8)−0.00005 (7)−0.00154 (7)
Br20.02779 (12)0.02861 (11)0.01347 (10)−0.00723 (9)0.00428 (8)−0.00567 (8)
C10.0184 (10)0.0169 (9)0.0155 (9)0.0032 (8)0.0011 (8)0.0006 (8)
C20.0164 (10)0.0137 (9)0.0162 (9)0.0014 (8)0.0011 (7)0.0006 (7)
C30.0160 (10)0.0143 (9)0.0154 (9)0.0033 (7)0.0022 (7)0.0019 (7)
C40.0150 (9)0.0132 (9)0.0155 (9)0.0035 (7)0.0013 (7)0.0008 (7)
C50.0153 (9)0.0164 (9)0.0144 (9)0.0035 (7)0.0010 (7)0.0017 (7)
C60.0151 (10)0.0145 (9)0.0174 (9)0.0028 (7)0.0029 (7)−0.0028 (7)
C70.0199 (10)0.0149 (9)0.0169 (9)0.0012 (8)0.0023 (7)−0.0028 (7)
C80.0268 (11)0.0171 (9)0.0187 (9)0.0013 (8)0.0091 (8)−0.0024 (8)
C90.0176 (10)0.0192 (10)0.0311 (11)−0.0013 (8)0.0096 (8)−0.0034 (8)
C100.0161 (10)0.0218 (10)0.0261 (10)0.0027 (8)−0.0001 (8)−0.0042 (8)
C110.0198 (10)0.0183 (9)0.0180 (9)0.0021 (8)0.0030 (8)0.0000 (7)
C120.0147 (9)0.0197 (9)0.0111 (8)0.0032 (8)−0.0006 (7)0.0005 (7)
C130.0165 (10)0.0193 (9)0.0168 (9)−0.0010 (8)0.0002 (7)−0.0007 (7)
C140.0212 (10)0.0239 (10)0.0148 (9)0.0049 (8)0.0003 (8)−0.0040 (8)
C150.0201 (10)0.0320 (11)0.0138 (9)0.0041 (9)0.0052 (8)0.0026 (8)
C160.0247 (11)0.0247 (10)0.0167 (9)−0.0027 (9)0.0039 (8)0.0053 (8)
C170.0249 (11)0.0167 (9)0.0140 (9)0.0025 (8)0.0026 (8)0.0008 (7)
C180.0168 (10)0.0149 (9)0.0114 (9)−0.0007 (7)0.0033 (7)0.0011 (7)
C190.0200 (10)0.0138 (9)0.0155 (9)0.0021 (8)0.0049 (7)−0.0012 (7)
C200.0142 (9)0.0202 (10)0.0180 (9)0.0024 (8)0.0037 (7)0.0028 (7)
C210.0165 (10)0.0165 (9)0.0127 (9)−0.0046 (8)0.0013 (7)0.0006 (7)
C220.0224 (11)0.0154 (10)0.0267 (10)0.0025 (8)0.0025 (8)−0.0055 (8)
C230.0139 (10)0.0204 (10)0.0282 (11)0.0042 (8)0.0013 (8)−0.0031 (8)
C240.0156 (9)0.0133 (9)0.0149 (9)−0.0023 (7)0.0018 (7)−0.0008 (7)
C250.0157 (10)0.0171 (9)0.0192 (9)0.0011 (8)0.0029 (7)−0.0004 (7)
C260.0168 (10)0.0194 (10)0.0169 (9)−0.0025 (8)−0.0027 (8)0.0019 (7)
C270.0220 (10)0.0147 (9)0.0132 (9)−0.0066 (8)0.0036 (7)−0.0025 (7)
C280.0164 (10)0.0154 (9)0.0205 (10)−0.0004 (8)0.0054 (8)−0.0012 (7)
C290.0160 (10)0.0159 (9)0.0163 (9)0.0001 (8)−0.0010 (7)0.0002 (7)
Geometric parameters (Å, °) top
O1—C11.208 (2)C14—C151.382 (3)
Br1—C211.9084 (17)C14—H140.9500
Br2—C271.9006 (17)C15—C161.387 (3)
C1—C21.512 (3)C15—H150.9500
C1—C51.514 (2)C16—C171.388 (3)
C2—C31.347 (2)C16—H160.9500
C2—C121.476 (2)C17—H170.9500
C3—C181.477 (2)C18—C231.394 (3)
C3—C41.512 (2)C18—C191.395 (3)
C4—C51.346 (3)C19—C201.388 (3)
C4—C241.478 (2)C19—H190.9500
C5—C61.475 (3)C20—C211.382 (3)
C6—C111.400 (3)C20—H200.9500
C6—C71.401 (2)C21—C221.376 (3)
C7—C81.383 (3)C22—C231.381 (3)
C7—H70.9500C22—H220.9500
C8—C91.392 (3)C23—H230.9500
C8—H80.9500C24—C291.395 (3)
C9—C101.383 (3)C24—C251.398 (2)
C9—H90.9500C25—C261.386 (3)
C10—C111.392 (3)C25—H250.9500
C10—H100.9500C26—C271.381 (3)
C11—H110.9500C26—H260.9500
C12—C171.396 (3)C27—C281.385 (3)
C12—C131.397 (3)C28—C291.384 (3)
C13—C141.388 (3)C28—H280.9500
C13—H130.9500C29—H290.9500
O1—C1—C2126.91 (16)C16—C15—H15120.0
O1—C1—C5126.30 (17)C15—C16—C17119.96 (18)
C2—C1—C5106.78 (15)C15—C16—H16120.0
C3—C2—C12130.15 (17)C17—C16—H16120.0
C3—C2—C1106.79 (15)C16—C17—C12120.68 (17)
C12—C2—C1123.06 (15)C16—C17—H17119.7
C2—C3—C18128.82 (16)C12—C17—H17119.7
C2—C3—C4109.77 (16)C23—C18—C19118.60 (16)
C18—C3—C4121.41 (15)C23—C18—C3119.83 (16)
C5—C4—C24127.24 (16)C19—C18—C3121.56 (16)
C5—C4—C3110.06 (15)C20—C19—C18121.17 (16)
C24—C4—C3122.44 (15)C20—C19—H19119.4
C4—C5—C6130.49 (16)C18—C19—H19119.4
C4—C5—C1106.56 (15)C21—C20—C19118.40 (17)
C6—C5—C1122.44 (15)C21—C20—H20120.8
C11—C6—C7118.40 (17)C19—C20—H20120.8
C11—C6—C5120.93 (16)C22—C21—C20121.80 (17)
C7—C6—C5120.62 (16)C22—C21—Br1117.45 (13)
C8—C7—C6120.76 (17)C20—C21—Br1120.75 (14)
C8—C7—H7119.6C21—C22—C23119.32 (17)
C6—C7—H7119.6C21—C22—H22120.3
C7—C8—C9120.38 (18)C23—C22—H22120.3
C7—C8—H8119.8C22—C23—C18120.71 (17)
C9—C8—H8119.8C22—C23—H23119.6
C10—C9—C8119.55 (18)C18—C23—H23119.6
C10—C9—H9120.2C29—C24—C25118.80 (16)
C8—C9—H9120.2C29—C24—C4121.12 (16)
C9—C10—C11120.43 (18)C25—C24—C4119.98 (16)
C9—C10—H10119.8C26—C25—C24121.12 (17)
C11—C10—H10119.8C26—C25—H25119.4
C10—C11—C6120.49 (17)C24—C25—H25119.4
C10—C11—H11119.8C27—C26—C25118.67 (17)
C6—C11—H11119.8C27—C26—H26120.7
C17—C12—C13118.57 (16)C25—C26—H26120.7
C17—C12—C2121.74 (16)C26—C27—C28121.49 (16)
C13—C12—C2119.66 (16)C26—C27—Br2119.80 (14)
C14—C13—C12120.64 (17)C28—C27—Br2118.67 (14)
C14—C13—H13119.7C29—C28—C27119.46 (17)
C12—C13—H13119.7C29—C28—H28120.3
C15—C14—C13120.14 (17)C27—C28—H28120.3
C15—C14—H14119.9C28—C29—C24120.42 (17)
C13—C14—H14119.9C28—C29—H29119.8
C14—C15—C16119.99 (17)C24—C29—H29119.8
C14—C15—H15120.0
O1—C1—C2—C3−179.45 (18)C17—C12—C13—C14−1.1 (3)
C5—C1—C2—C31.50 (19)C2—C12—C13—C14176.79 (17)
O1—C1—C2—C120.1 (3)C12—C13—C14—C15−0.2 (3)
C5—C1—C2—C12−178.90 (15)C13—C14—C15—C161.0 (3)
C12—C2—C3—C18−0.8 (3)C14—C15—C16—C17−0.4 (3)
C1—C2—C3—C18178.75 (17)C15—C16—C17—C12−0.9 (3)
C12—C2—C3—C4178.56 (17)C13—C12—C17—C161.7 (3)
C1—C2—C3—C4−1.88 (19)C2—C12—C17—C16−176.19 (17)
C2—C3—C4—C51.7 (2)C2—C3—C18—C23−126.7 (2)
C18—C3—C4—C5−178.89 (16)C4—C3—C18—C2354.0 (2)
C2—C3—C4—C24−172.90 (16)C2—C3—C18—C1954.6 (3)
C18—C3—C4—C246.5 (2)C4—C3—C18—C19−124.71 (18)
C24—C4—C5—C61.8 (3)C23—C18—C19—C20−0.2 (3)
C3—C4—C5—C6−172.48 (17)C3—C18—C19—C20178.54 (16)
C24—C4—C5—C1173.62 (16)C18—C19—C20—C210.5 (3)
C3—C4—C5—C1−0.63 (19)C19—C20—C21—C22−0.5 (3)
O1—C1—C5—C4−179.53 (18)C19—C20—C21—Br1−179.71 (13)
C2—C1—C5—C4−0.47 (19)C20—C21—C22—C230.2 (3)
O1—C1—C5—C6−6.9 (3)Br1—C21—C22—C23179.40 (14)
C2—C1—C5—C6172.18 (16)C21—C22—C23—C180.2 (3)
C4—C5—C6—C11−147.57 (19)C19—C18—C23—C22−0.2 (3)
C1—C5—C6—C1141.7 (3)C3—C18—C23—C22−178.92 (17)
C4—C5—C6—C735.0 (3)C5—C4—C24—C2956.6 (3)
C1—C5—C6—C7−135.76 (18)C3—C4—C24—C29−129.80 (18)
C11—C6—C7—C80.3 (3)C5—C4—C24—C25−119.9 (2)
C5—C6—C7—C8177.85 (16)C3—C4—C24—C2553.7 (2)
C6—C7—C8—C90.2 (3)C29—C24—C25—C26−2.1 (3)
C7—C8—C9—C10−0.3 (3)C4—C24—C25—C26174.47 (17)
C8—C9—C10—C110.0 (3)C24—C25—C26—C271.1 (3)
C9—C10—C11—C60.5 (3)C25—C26—C27—C280.3 (3)
C7—C6—C11—C10−0.7 (3)C25—C26—C27—Br2−177.38 (13)
C5—C6—C11—C10−178.20 (16)C26—C27—C28—C29−0.8 (3)
C3—C2—C12—C1735.5 (3)Br2—C27—C28—C29176.94 (13)
C1—C2—C12—C17−144.03 (18)C27—C28—C29—C24−0.2 (3)
C3—C2—C12—C13−142.4 (2)C25—C24—C29—C281.6 (3)
C1—C2—C12—C1338.1 (2)C4—C24—C29—C28−174.91 (16)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C28—H28···Br1i0.952.873.6920 (18)146
C22—H22···Br2ii0.952.973.6386 (19)129
C15—H15···Br1iii0.953.033.8556 (18)146
Symmetry codes: (i) x+1, y, z; (ii) −x+2, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C28—H28···Br1i0.952.873.6920 (18)146
C22—H22···Br2ii0.952.973.6386 (19)129
C15—H15···Br1iii0.953.033.8556 (18)146
Symmetry codes: (i) x+1, y, z; (ii) −x+2, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z+1.
references
References top

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