Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110052297/gz3187sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110052297/gz3187Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110052297/gz3187IIsup3.hkl |
CCDC references: 813513; 813514
For related literature, see: Brammer et al. (2001); Clar (1964, 1972); Frisch (2004); Gupta et al. (1991); Lahti (1988); Wilcox, Lahti, Rocca, Halpern & Meinwald (1978); Zimmerman & Wilson (1992).
Compounds (I) and (II) were prepared and purified according to the published method of Wilcox et al. (1978). X-ray quality crystals of (I) were obtained by the slow evaporation of a benzene–methanol solution (Solvent ratio?) of the compound, while for (II), slow diffusion of hexane into a chloroform solution was used.
H atoms were placed in calculated positions, with C—H = 0.95 Å, and included as riding, with Uiso(H) = 1.2Ueq(C).
For both compounds, data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008b); program(s) used to refine structure: SHELXTL (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).
C30H21Br·0.5(C6H6) | F(000) = 2056 |
Mr = 500.43 | Dx = 1.407 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 9917 reflections |
a = 11.633 (1) Å | θ = 2.2–27.8° |
b = 26.665 (2) Å | µ = 1.76 mm−1 |
c = 15.2364 (14) Å | T = 100 K |
β = 91.513 (1)° | Slat, colourless |
V = 4724.7 (7) Å3 | 0.36 × 0.14 × 0.03 mm |
Z = 8 |
Bruker SMART APEX CCD area-detector diffractometer | 10288 independent reflections |
Radiation source: fine-focus sealed tube | 7141 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
ϕ and ω scans | θmax = 27.0°, θmin = 1.5° |
Absorption correction: integration (SADABS; Sheldrick, 2008a) | h = −14→14 |
Tmin = 0.501, Tmax = 0.956 | k = −34→34 |
39415 measured reflections | l = −18→19 |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0489P)2 + 0.9303P] where P = (Fo2 + 2Fc2)/3 |
10288 reflections | (Δ/σ)max = 0.002 |
613 parameters | Δρmax = 0.52 e Å−3 |
0 restraints | Δρmin = −0.67 e Å−3 |
C30H21Br·0.5(C6H6) | V = 4724.7 (7) Å3 |
Mr = 500.43 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.633 (1) Å | µ = 1.76 mm−1 |
b = 26.665 (2) Å | T = 100 K |
c = 15.2364 (14) Å | 0.36 × 0.14 × 0.03 mm |
β = 91.513 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 10288 independent reflections |
Absorption correction: integration (SADABS; Sheldrick, 2008a) | 7141 reflections with I > 2σ(I) |
Tmin = 0.501, Tmax = 0.956 | Rint = 0.051 |
39415 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.52 e Å−3 |
10288 reflections | Δρmin = −0.67 e Å−3 |
613 parameters |
Experimental. The diffraction data were collected in three sets of 606 frames (0.3° width in omega) at phi = 0, 120 and 240°. A scan time of 60 sec/frame was used. |
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 > σ(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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.77630 (2) | 0.557611 (12) | 0.61691 (2) | 0.03742 (9) | |
C1 | 0.9371 (2) | 0.54588 (11) | 0.60390 (17) | 0.0303 (6) | |
C2 | 0.9819 (2) | 0.49956 (11) | 0.63107 (17) | 0.0302 (6) | |
C3 | 1.0997 (2) | 0.49190 (11) | 0.62132 (18) | 0.0332 (7) | |
H3 | 1.1333 | 0.4611 | 0.6398 | 0.040* | |
C4 | 1.1682 (2) | 0.52871 (12) | 0.58507 (19) | 0.0366 (7) | |
H4 | 1.2479 | 0.5227 | 0.5782 | 0.044* | |
C5 | 1.1211 (2) | 0.57370 (11) | 0.55907 (18) | 0.0341 (7) | |
H5 | 1.1691 | 0.5985 | 0.5342 | 0.041* | |
C6 | 1.0043 (2) | 0.58396 (11) | 0.56832 (17) | 0.0309 (6) | |
C7 | 0.9578 (2) | 0.63282 (11) | 0.54127 (17) | 0.0320 (7) | |
H7 | 0.8795 | 0.6343 | 0.5222 | 0.038* | |
C8 | 1.0187 (2) | 0.67575 (11) | 0.54162 (17) | 0.0324 (7) | |
H8 | 1.0968 | 0.6735 | 0.5610 | 0.039* | |
C9 | 0.9777 (2) | 0.72502 (11) | 0.51550 (17) | 0.0288 (6) | |
C10 | 0.8706 (2) | 0.73291 (11) | 0.46912 (17) | 0.0305 (6) | |
H10 | 0.8265 | 0.7048 | 0.4497 | 0.037* | |
C11 | 0.8311 (2) | 0.77994 (11) | 0.45253 (17) | 0.0322 (7) | |
H11 | 0.7591 | 0.7841 | 0.4225 | 0.039* | |
C12 | 0.8945 (2) | 0.82304 (11) | 0.47874 (17) | 0.0300 (6) | |
C13 | 0.8532 (2) | 0.87224 (11) | 0.46499 (19) | 0.0368 (7) | |
H13 | 0.7803 | 0.8773 | 0.4368 | 0.044* | |
C14 | 0.9168 (3) | 0.91245 (12) | 0.4917 (2) | 0.0407 (7) | |
H14 | 0.8872 | 0.9453 | 0.4832 | 0.049* | |
C15 | 1.0259 (3) | 0.90581 (12) | 0.5317 (2) | 0.0424 (8) | |
H15 | 1.0707 | 0.9342 | 0.5482 | 0.051* | |
C16 | 1.0678 (2) | 0.85879 (12) | 0.54692 (19) | 0.0381 (7) | |
H16 | 1.1412 | 0.8547 | 0.5748 | 0.046* | |
C17 | 1.0034 (2) | 0.81602 (11) | 0.52181 (17) | 0.0304 (6) | |
C18 | 1.0418 (2) | 0.76665 (11) | 0.53869 (17) | 0.0307 (6) | |
H18 | 1.1147 | 0.7619 | 0.5671 | 0.037* | |
C19 | 0.9109 (2) | 0.45993 (11) | 0.66984 (17) | 0.0306 (6) | |
H19 | 0.8416 | 0.4697 | 0.6968 | 0.037* | |
C20 | 0.9376 (2) | 0.41145 (11) | 0.66952 (17) | 0.0305 (6) | |
H20 | 1.0078 | 0.4029 | 0.6427 | 0.037* | |
C21 | 0.8725 (2) | 0.36989 (11) | 0.70527 (16) | 0.0282 (6) | |
C22 | 0.9116 (2) | 0.32139 (11) | 0.69422 (17) | 0.0287 (6) | |
H22 | 0.9817 | 0.3164 | 0.6648 | 0.034* | |
C23 | 0.8519 (2) | 0.27891 (11) | 0.72466 (16) | 0.0273 (6) | |
C24 | 0.8927 (2) | 0.22958 (11) | 0.71252 (17) | 0.0319 (6) | |
H24 | 0.9639 | 0.2243 | 0.6849 | 0.038* | |
C25 | 0.8303 (2) | 0.18913 (12) | 0.74035 (19) | 0.0366 (7) | |
H25 | 0.8583 | 0.1560 | 0.7322 | 0.044* | |
C26 | 0.7242 (2) | 0.19705 (12) | 0.78125 (19) | 0.0380 (7) | |
H26 | 0.6807 | 0.1690 | 0.7997 | 0.046* | |
C27 | 0.6831 (2) | 0.24417 (12) | 0.79478 (18) | 0.0339 (7) | |
H27 | 0.6120 | 0.2487 | 0.8229 | 0.041* | |
C28 | 0.7464 (2) | 0.28659 (11) | 0.76696 (16) | 0.0297 (6) | |
C29 | 0.7061 (2) | 0.33651 (11) | 0.77913 (17) | 0.0317 (7) | |
H29 | 0.6358 | 0.3420 | 0.8079 | 0.038* | |
C30 | 0.7671 (2) | 0.37644 (11) | 0.75013 (17) | 0.0307 (6) | |
H30 | 0.7390 | 0.4094 | 0.7599 | 0.037* | |
Br2 | 0.29053 (2) | −0.017046 (11) | 0.644906 (19) | 0.03384 (9) | |
C31 | 0.4513 (2) | −0.00494 (11) | 0.62992 (17) | 0.0292 (6) | |
C32 | 0.5184 (2) | −0.04274 (11) | 0.59283 (17) | 0.0300 (6) | |
C33 | 0.6352 (2) | −0.03220 (11) | 0.58331 (18) | 0.0348 (7) | |
H33 | 0.6833 | −0.0566 | 0.5576 | 0.042* | |
C34 | 0.6818 (2) | 0.01290 (11) | 0.61049 (19) | 0.0376 (7) | |
H34 | 0.7615 | 0.0191 | 0.6036 | 0.045* | |
C35 | 0.6136 (2) | 0.04915 (11) | 0.64771 (18) | 0.0335 (7) | |
H35 | 0.6475 | 0.0798 | 0.6672 | 0.040* | |
C36 | 0.4958 (2) | 0.04155 (11) | 0.65722 (17) | 0.0288 (6) | |
C37 | 0.4238 (2) | 0.08140 (11) | 0.69382 (17) | 0.0296 (6) | |
H37 | 0.3553 | 0.0718 | 0.7220 | 0.035* | |
C38 | 0.4485 (2) | 0.12996 (11) | 0.68989 (17) | 0.0297 (6) | |
H38 | 0.5192 | 0.1385 | 0.6639 | 0.036* | |
C39 | 0.3792 (2) | 0.17183 (11) | 0.72102 (16) | 0.0267 (6) | |
C40 | 0.2748 (2) | 0.16481 (11) | 0.76624 (17) | 0.0287 (6) | |
H40 | 0.2506 | 0.1318 | 0.7803 | 0.034* | |
C41 | 0.2089 (2) | 0.20475 (11) | 0.78968 (17) | 0.0298 (6) | |
H41 | 0.1399 | 0.1991 | 0.8201 | 0.036* | |
C42 | 0.2421 (2) | 0.25465 (11) | 0.76930 (16) | 0.0270 (6) | |
C43 | 0.1739 (2) | 0.29656 (11) | 0.78928 (18) | 0.0329 (7) | |
H43 | 0.1037 | 0.2918 | 0.8187 | 0.039* | |
C44 | 0.2073 (2) | 0.34388 (11) | 0.76705 (18) | 0.0357 (7) | |
H44 | 0.1597 | 0.3717 | 0.7803 | 0.043* | |
C45 | 0.3117 (2) | 0.35164 (11) | 0.72472 (18) | 0.0348 (7) | |
H45 | 0.3345 | 0.3847 | 0.7099 | 0.042* | |
C46 | 0.3806 (2) | 0.31196 (11) | 0.70470 (17) | 0.0304 (6) | |
H46 | 0.4510 | 0.3177 | 0.6761 | 0.036* | |
C47 | 0.3476 (2) | 0.26231 (10) | 0.72624 (16) | 0.0258 (6) | |
C48 | 0.4140 (2) | 0.22012 (10) | 0.70293 (16) | 0.0270 (6) | |
H48 | 0.4844 | 0.2252 | 0.6740 | 0.032* | |
C49 | 0.4701 (2) | −0.09069 (11) | 0.56281 (17) | 0.0322 (7) | |
H49 | 0.3906 | −0.0917 | 0.5470 | 0.039* | |
C50 | 0.5304 (2) | −0.13311 (11) | 0.55622 (17) | 0.0312 (6) | |
H50 | 0.6097 | −0.1318 | 0.5725 | 0.037* | |
C51 | 0.4847 (2) | −0.18145 (11) | 0.52599 (17) | 0.0300 (6) | |
C52 | 0.5486 (2) | −0.22448 (11) | 0.53899 (16) | 0.0294 (6) | |
H52 | 0.6236 | −0.2218 | 0.5647 | 0.035* | |
C53 | 0.5062 (2) | −0.27245 (11) | 0.51529 (16) | 0.0285 (6) | |
C54 | 0.5704 (2) | −0.31674 (11) | 0.52893 (18) | 0.0339 (7) | |
H54 | 0.6456 | −0.3148 | 0.5547 | 0.041* | |
C55 | 0.5259 (2) | −0.36234 (12) | 0.50548 (18) | 0.0370 (7) | |
H55 | 0.5710 | −0.3917 | 0.5138 | 0.044* | |
C56 | 0.4135 (2) | −0.36620 (12) | 0.46905 (19) | 0.0372 (7) | |
H56 | 0.3824 | −0.3982 | 0.4546 | 0.045* | |
C57 | 0.3493 (2) | −0.32390 (12) | 0.45451 (18) | 0.0344 (7) | |
H57 | 0.2740 | −0.3267 | 0.4293 | 0.041* | |
C58 | 0.3935 (2) | −0.27609 (11) | 0.47653 (16) | 0.0286 (6) | |
C59 | 0.3304 (2) | −0.23152 (11) | 0.46116 (17) | 0.0311 (7) | |
H59 | 0.2563 | −0.2334 | 0.4336 | 0.037* | |
C60 | 0.3734 (2) | −0.18604 (11) | 0.48490 (17) | 0.0307 (6) | |
H60 | 0.3288 | −0.1568 | 0.4740 | 0.037* | |
C61 | 0.4781 (3) | 0.52358 (17) | 0.6356 (2) | 0.0604 (11) | |
H61 | 0.4677 | 0.5279 | 0.5740 | 0.072* | |
C62 | 0.4930 (3) | 0.47631 (16) | 0.6702 (3) | 0.0731 (13) | |
H62 | 0.4910 | 0.4478 | 0.6327 | 0.088* | |
C63 | 0.5109 (3) | 0.47041 (14) | 0.7591 (3) | 0.0651 (12) | |
H63 | 0.5239 | 0.4380 | 0.7832 | 0.078* | |
C64 | 0.5099 (3) | 0.51170 (16) | 0.8129 (3) | 0.0605 (10) | |
H64 | 0.5208 | 0.5079 | 0.8746 | 0.073* | |
C65 | 0.4931 (3) | 0.55848 (15) | 0.7775 (3) | 0.0625 (11) | |
H65 | 0.4917 | 0.5869 | 0.8149 | 0.075* | |
C66 | 0.4785 (3) | 0.56446 (14) | 0.6904 (2) | 0.0559 (10) | |
H66 | 0.4683 | 0.5971 | 0.6666 | 0.067* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.02334 (15) | 0.04529 (19) | 0.04387 (18) | 0.00255 (13) | 0.00549 (12) | 0.00533 (14) |
C1 | 0.0210 (14) | 0.0441 (18) | 0.0261 (15) | 0.0008 (12) | 0.0030 (11) | −0.0031 (12) |
C2 | 0.0281 (15) | 0.0389 (17) | 0.0238 (15) | −0.0018 (12) | 0.0013 (11) | −0.0032 (12) |
C3 | 0.0287 (15) | 0.0391 (17) | 0.0317 (16) | −0.0004 (13) | 0.0005 (12) | −0.0028 (13) |
C4 | 0.0250 (15) | 0.047 (2) | 0.0378 (17) | −0.0001 (13) | 0.0023 (12) | −0.0052 (14) |
C5 | 0.0266 (15) | 0.0438 (18) | 0.0320 (16) | −0.0037 (13) | 0.0060 (12) | −0.0014 (13) |
C6 | 0.0310 (15) | 0.0419 (18) | 0.0200 (14) | −0.0017 (13) | 0.0022 (11) | −0.0007 (12) |
C7 | 0.0250 (15) | 0.0469 (19) | 0.0243 (15) | 0.0027 (13) | 0.0018 (11) | 0.0013 (13) |
C8 | 0.0243 (14) | 0.0491 (19) | 0.0238 (15) | 0.0026 (13) | 0.0033 (11) | 0.0052 (13) |
C9 | 0.0209 (14) | 0.0453 (18) | 0.0204 (14) | 0.0011 (12) | 0.0031 (10) | −0.0002 (12) |
C10 | 0.0211 (14) | 0.0434 (18) | 0.0269 (15) | −0.0033 (12) | 0.0017 (11) | −0.0013 (13) |
C11 | 0.0227 (14) | 0.053 (2) | 0.0211 (14) | 0.0003 (13) | 0.0000 (11) | −0.0029 (13) |
C12 | 0.0236 (14) | 0.0444 (18) | 0.0220 (14) | 0.0013 (13) | 0.0038 (11) | −0.0051 (12) |
C13 | 0.0278 (15) | 0.049 (2) | 0.0338 (17) | 0.0078 (14) | −0.0014 (12) | −0.0026 (14) |
C14 | 0.0363 (17) | 0.0409 (19) | 0.0448 (19) | 0.0049 (14) | −0.0015 (14) | −0.0046 (15) |
C15 | 0.0350 (17) | 0.047 (2) | 0.0454 (19) | −0.0039 (15) | −0.0014 (14) | −0.0104 (15) |
C16 | 0.0261 (15) | 0.056 (2) | 0.0320 (16) | −0.0005 (14) | −0.0025 (12) | −0.0075 (14) |
C17 | 0.0205 (14) | 0.0461 (18) | 0.0248 (15) | 0.0014 (13) | 0.0059 (11) | −0.0023 (13) |
C18 | 0.0190 (14) | 0.0505 (19) | 0.0226 (14) | 0.0014 (13) | 0.0020 (11) | −0.0003 (13) |
C19 | 0.0233 (14) | 0.0414 (17) | 0.0273 (15) | −0.0001 (12) | 0.0011 (11) | −0.0022 (13) |
C20 | 0.0235 (14) | 0.0445 (18) | 0.0236 (15) | −0.0013 (13) | 0.0015 (11) | −0.0016 (12) |
C21 | 0.0259 (14) | 0.0388 (17) | 0.0199 (14) | 0.0004 (12) | −0.0012 (11) | 0.0001 (12) |
C22 | 0.0207 (14) | 0.0424 (18) | 0.0229 (14) | 0.0006 (12) | −0.0005 (11) | 0.0039 (12) |
C23 | 0.0205 (13) | 0.0418 (17) | 0.0194 (13) | 0.0007 (12) | −0.0059 (10) | 0.0022 (12) |
C24 | 0.0248 (14) | 0.0436 (18) | 0.0271 (15) | 0.0020 (13) | −0.0041 (11) | 0.0065 (13) |
C25 | 0.0354 (17) | 0.0429 (18) | 0.0311 (16) | 0.0051 (14) | −0.0064 (13) | 0.0058 (13) |
C26 | 0.0349 (17) | 0.049 (2) | 0.0301 (16) | −0.0086 (15) | −0.0053 (13) | 0.0111 (14) |
C27 | 0.0253 (15) | 0.052 (2) | 0.0245 (15) | −0.0046 (14) | −0.0013 (11) | 0.0056 (13) |
C28 | 0.0240 (14) | 0.0470 (18) | 0.0180 (14) | −0.0013 (13) | −0.0028 (10) | 0.0026 (12) |
C29 | 0.0223 (14) | 0.0511 (19) | 0.0218 (14) | 0.0021 (13) | 0.0004 (11) | −0.0023 (13) |
C30 | 0.0246 (14) | 0.0443 (18) | 0.0232 (14) | 0.0034 (13) | −0.0017 (11) | −0.0040 (12) |
Br2 | 0.02115 (14) | 0.04324 (18) | 0.03725 (17) | 0.00112 (12) | 0.00310 (11) | −0.00184 (13) |
C31 | 0.0238 (14) | 0.0405 (17) | 0.0234 (14) | 0.0027 (12) | 0.0026 (11) | 0.0060 (12) |
C32 | 0.0270 (15) | 0.0430 (18) | 0.0201 (14) | 0.0054 (13) | 0.0013 (11) | 0.0036 (12) |
C33 | 0.0268 (15) | 0.0449 (19) | 0.0330 (16) | 0.0093 (13) | 0.0060 (12) | 0.0024 (13) |
C34 | 0.0209 (14) | 0.049 (2) | 0.0429 (18) | 0.0056 (14) | 0.0072 (12) | 0.0081 (15) |
C35 | 0.0270 (15) | 0.0392 (17) | 0.0342 (16) | 0.0013 (13) | −0.0009 (12) | 0.0087 (13) |
C36 | 0.0227 (14) | 0.0387 (17) | 0.0249 (14) | 0.0022 (12) | 0.0002 (11) | 0.0090 (12) |
C37 | 0.0231 (14) | 0.0404 (17) | 0.0252 (15) | 0.0008 (12) | 0.0021 (11) | 0.0065 (12) |
C38 | 0.0211 (14) | 0.0436 (18) | 0.0245 (14) | 0.0010 (12) | 0.0022 (11) | 0.0054 (12) |
C39 | 0.0191 (13) | 0.0404 (17) | 0.0205 (13) | 0.0021 (12) | −0.0027 (10) | 0.0036 (12) |
C40 | 0.0225 (14) | 0.0394 (17) | 0.0242 (14) | −0.0032 (12) | 0.0010 (11) | 0.0046 (12) |
C41 | 0.0217 (14) | 0.0467 (18) | 0.0210 (14) | −0.0007 (13) | 0.0024 (11) | 0.0002 (12) |
C42 | 0.0194 (13) | 0.0431 (17) | 0.0185 (13) | −0.0010 (12) | −0.0014 (10) | −0.0020 (12) |
C43 | 0.0227 (14) | 0.0490 (19) | 0.0270 (15) | 0.0003 (13) | 0.0021 (11) | −0.0087 (13) |
C44 | 0.0298 (16) | 0.0434 (19) | 0.0339 (16) | 0.0058 (14) | −0.0022 (12) | −0.0122 (14) |
C45 | 0.0343 (16) | 0.0350 (17) | 0.0351 (16) | −0.0053 (13) | −0.0005 (13) | −0.0037 (13) |
C46 | 0.0243 (14) | 0.0414 (18) | 0.0254 (15) | −0.0069 (13) | 0.0010 (11) | −0.0034 (12) |
C47 | 0.0206 (13) | 0.0389 (17) | 0.0178 (13) | −0.0037 (12) | −0.0028 (10) | −0.0024 (11) |
C48 | 0.0196 (13) | 0.0408 (17) | 0.0206 (13) | −0.0020 (12) | 0.0012 (10) | 0.0015 (12) |
C49 | 0.0267 (15) | 0.0485 (19) | 0.0213 (14) | 0.0013 (13) | 0.0013 (11) | −0.0008 (13) |
C50 | 0.0222 (14) | 0.0498 (19) | 0.0217 (14) | 0.0040 (13) | 0.0023 (11) | −0.0018 (13) |
C51 | 0.0220 (14) | 0.0496 (19) | 0.0186 (14) | 0.0021 (13) | 0.0013 (10) | −0.0016 (12) |
C52 | 0.0188 (13) | 0.0488 (18) | 0.0206 (14) | 0.0027 (13) | 0.0026 (10) | −0.0009 (12) |
C53 | 0.0196 (13) | 0.0454 (18) | 0.0204 (14) | −0.0009 (12) | 0.0014 (10) | 0.0021 (12) |
C54 | 0.0242 (15) | 0.052 (2) | 0.0253 (15) | 0.0015 (14) | −0.0013 (11) | 0.0046 (13) |
C55 | 0.0328 (16) | 0.0454 (19) | 0.0326 (16) | 0.0027 (14) | −0.0033 (13) | 0.0060 (14) |
C56 | 0.0342 (17) | 0.0450 (19) | 0.0324 (16) | −0.0069 (14) | −0.0017 (13) | 0.0028 (14) |
C57 | 0.0233 (15) | 0.053 (2) | 0.0265 (15) | −0.0040 (14) | −0.0005 (11) | 0.0043 (14) |
C58 | 0.0216 (14) | 0.0479 (18) | 0.0167 (13) | −0.0012 (13) | 0.0042 (10) | 0.0011 (12) |
C59 | 0.0180 (13) | 0.055 (2) | 0.0207 (14) | 0.0018 (13) | 0.0002 (10) | −0.0005 (13) |
C60 | 0.0227 (14) | 0.0467 (18) | 0.0226 (14) | 0.0080 (13) | 0.0024 (11) | 0.0002 (13) |
C61 | 0.037 (2) | 0.093 (3) | 0.051 (2) | −0.015 (2) | 0.0044 (16) | 0.001 (2) |
C62 | 0.067 (3) | 0.064 (3) | 0.090 (3) | −0.025 (2) | 0.040 (2) | −0.030 (3) |
C63 | 0.048 (2) | 0.052 (3) | 0.096 (3) | 0.0156 (19) | 0.023 (2) | 0.019 (2) |
C64 | 0.044 (2) | 0.077 (3) | 0.060 (2) | −0.011 (2) | −0.0093 (17) | 0.014 (2) |
C65 | 0.077 (3) | 0.057 (2) | 0.054 (2) | −0.018 (2) | 0.019 (2) | −0.0016 (19) |
C66 | 0.050 (2) | 0.060 (2) | 0.059 (2) | 0.0125 (18) | 0.0192 (18) | 0.0110 (19) |
Br1—C1 | 1.912 (3) | C33—H33 | 0.9500 |
C1—C2 | 1.399 (4) | C34—C35 | 1.382 (4) |
C1—C6 | 1.400 (4) | C34—H34 | 0.9500 |
C2—C3 | 1.397 (4) | C35—C36 | 1.397 (4) |
C2—C19 | 1.474 (4) | C35—H35 | 0.9500 |
C3—C4 | 1.388 (4) | C36—C37 | 1.472 (4) |
C3—H3 | 0.9500 | C37—C38 | 1.328 (4) |
C4—C5 | 1.373 (4) | C37—H37 | 0.9500 |
C4—H4 | 0.9500 | C38—C39 | 1.463 (4) |
C5—C6 | 1.396 (4) | C38—H38 | 0.9500 |
C5—H5 | 0.9500 | C39—C48 | 1.380 (4) |
C6—C7 | 1.466 (4) | C39—C40 | 1.424 (3) |
C7—C8 | 1.346 (4) | C40—C41 | 1.365 (4) |
C7—H7 | 0.9500 | C40—H40 | 0.9500 |
C8—C9 | 1.450 (4) | C41—C42 | 1.422 (4) |
C8—H8 | 0.9500 | C41—H41 | 0.9500 |
C9—C18 | 1.378 (4) | C42—C43 | 1.408 (4) |
C9—C10 | 1.432 (4) | C42—C47 | 1.422 (3) |
C10—C11 | 1.357 (4) | C43—C44 | 1.366 (4) |
C10—H10 | 0.9500 | C43—H43 | 0.9500 |
C11—C12 | 1.417 (4) | C44—C45 | 1.405 (4) |
C11—H11 | 0.9500 | C44—H44 | 0.9500 |
C12—C13 | 1.411 (4) | C45—C46 | 1.367 (4) |
C12—C17 | 1.424 (4) | C45—H45 | 0.9500 |
C13—C14 | 1.359 (4) | C46—C47 | 1.419 (4) |
C13—H13 | 0.9500 | C46—H46 | 0.9500 |
C14—C15 | 1.405 (4) | C47—C48 | 1.415 (4) |
C14—H14 | 0.9500 | C48—H48 | 0.9500 |
C15—C16 | 1.363 (4) | C49—C50 | 1.336 (4) |
C15—H15 | 0.9500 | C49—H49 | 0.9500 |
C16—C17 | 1.412 (4) | C50—C51 | 1.464 (4) |
C16—H16 | 0.9500 | C50—H50 | 0.9500 |
C17—C18 | 1.412 (4) | C51—C52 | 1.379 (4) |
C18—H18 | 0.9500 | C51—C60 | 1.428 (4) |
C19—C20 | 1.330 (4) | C52—C53 | 1.414 (4) |
C19—H19 | 0.9500 | C52—H52 | 0.9500 |
C20—C21 | 1.456 (4) | C53—C54 | 1.410 (4) |
C20—H20 | 0.9500 | C53—C58 | 1.427 (4) |
C21—C22 | 1.383 (4) | C54—C55 | 1.366 (4) |
C21—C30 | 1.430 (4) | C54—H54 | 0.9500 |
C22—C23 | 1.413 (4) | C55—C56 | 1.410 (4) |
C22—H22 | 0.9500 | C55—H55 | 0.9500 |
C23—C24 | 1.412 (4) | C56—C57 | 1.368 (4) |
C23—C28 | 1.416 (4) | C56—H56 | 0.9500 |
C24—C25 | 1.373 (4) | C57—C58 | 1.412 (4) |
C24—H24 | 0.9500 | C57—H57 | 0.9500 |
C25—C26 | 1.413 (4) | C58—C59 | 1.413 (4) |
C25—H25 | 0.9500 | C59—C60 | 1.357 (4) |
C26—C27 | 1.362 (4) | C59—H59 | 0.9500 |
C26—H26 | 0.9500 | C60—H60 | 0.9500 |
C27—C28 | 1.420 (4) | C61—C66 | 1.373 (5) |
C27—H27 | 0.9500 | C61—C62 | 1.376 (6) |
C28—C29 | 1.425 (4) | C61—H61 | 0.9500 |
C29—C30 | 1.359 (4) | C62—C63 | 1.374 (6) |
C29—H29 | 0.9500 | C62—H62 | 0.9500 |
C30—H30 | 0.9500 | C63—C64 | 1.373 (5) |
Br2—C31 | 1.917 (3) | C63—H63 | 0.9500 |
C31—C32 | 1.403 (4) | C64—C65 | 1.371 (5) |
C31—C36 | 1.403 (4) | C64—H64 | 0.9500 |
C32—C33 | 1.399 (4) | C65—C66 | 1.343 (5) |
C32—C49 | 1.465 (4) | C65—H65 | 0.9500 |
C33—C34 | 1.379 (4) | C66—H66 | 0.9500 |
C2—C1—C6 | 123.2 (2) | C33—C34—C35 | 120.5 (3) |
C2—C1—Br1 | 118.1 (2) | C33—C34—H34 | 119.7 |
C6—C1—Br1 | 118.7 (2) | C35—C34—H34 | 119.7 |
C3—C2—C1 | 117.1 (3) | C34—C35—C36 | 121.1 (3) |
C3—C2—C19 | 119.9 (3) | C34—C35—H35 | 119.4 |
C1—C2—C19 | 122.9 (2) | C36—C35—H35 | 119.4 |
C4—C3—C2 | 120.9 (3) | C35—C36—C31 | 117.0 (3) |
C4—C3—H3 | 119.5 | C35—C36—C37 | 120.3 (3) |
C2—C3—H3 | 119.5 | C31—C36—C37 | 122.7 (2) |
C5—C4—C3 | 120.3 (3) | C38—C37—C36 | 124.1 (2) |
C5—C4—H4 | 119.9 | C38—C37—H37 | 118.0 |
C3—C4—H4 | 119.9 | C36—C37—H37 | 118.0 |
C4—C5—C6 | 121.6 (3) | C37—C38—C39 | 127.4 (2) |
C4—C5—H5 | 119.2 | C37—C38—H38 | 116.3 |
C6—C5—H5 | 119.2 | C39—C38—H38 | 116.3 |
C5—C6—C1 | 116.9 (3) | C48—C39—C40 | 118.5 (2) |
C5—C6—C7 | 119.9 (3) | C48—C39—C38 | 118.7 (2) |
C1—C6—C7 | 123.2 (2) | C40—C39—C38 | 122.7 (3) |
C8—C7—C6 | 124.4 (3) | C41—C40—C39 | 121.0 (3) |
C8—C7—H7 | 117.8 | C41—C40—H40 | 119.5 |
C6—C7—H7 | 117.8 | C39—C40—H40 | 119.5 |
C7—C8—C9 | 126.9 (3) | C40—C41—C42 | 121.0 (2) |
C7—C8—H8 | 116.6 | C40—C41—H41 | 119.5 |
C9—C8—H8 | 116.6 | C42—C41—H41 | 119.5 |
C18—C9—C10 | 117.8 (3) | C43—C42—C47 | 118.9 (3) |
C18—C9—C8 | 119.2 (2) | C43—C42—C41 | 122.5 (2) |
C10—C9—C8 | 123.0 (3) | C47—C42—C41 | 118.5 (2) |
C11—C10—C9 | 120.9 (3) | C44—C43—C42 | 120.9 (3) |
C11—C10—H10 | 119.6 | C44—C43—H43 | 119.5 |
C9—C10—H10 | 119.6 | C42—C43—H43 | 119.5 |
C10—C11—C12 | 121.8 (3) | C43—C44—C45 | 120.3 (3) |
C10—C11—H11 | 119.1 | C43—C44—H44 | 119.8 |
C12—C11—H11 | 119.1 | C45—C44—H44 | 119.8 |
C13—C12—C11 | 122.7 (3) | C46—C45—C44 | 120.5 (3) |
C13—C12—C17 | 119.1 (3) | C46—C45—H45 | 119.8 |
C11—C12—C17 | 118.2 (3) | C44—C45—H45 | 119.8 |
C14—C13—C12 | 120.6 (3) | C45—C46—C47 | 120.5 (3) |
C14—C13—H13 | 119.7 | C45—C46—H46 | 119.8 |
C12—C13—H13 | 119.7 | C47—C46—H46 | 119.8 |
C13—C14—C15 | 120.6 (3) | C48—C47—C46 | 122.1 (2) |
C13—C14—H14 | 119.7 | C48—C47—C42 | 119.0 (2) |
C15—C14—H14 | 119.7 | C46—C47—C42 | 118.8 (2) |
C16—C15—C14 | 120.3 (3) | C39—C48—C47 | 121.8 (2) |
C16—C15—H15 | 119.8 | C39—C48—H48 | 119.1 |
C14—C15—H15 | 119.8 | C47—C48—H48 | 119.1 |
C15—C16—C17 | 120.8 (3) | C50—C49—C32 | 124.4 (3) |
C15—C16—H16 | 119.6 | C50—C49—H49 | 117.8 |
C17—C16—H16 | 119.6 | C32—C49—H49 | 117.8 |
C18—C17—C16 | 122.8 (3) | C49—C50—C51 | 125.6 (3) |
C18—C17—C12 | 118.7 (3) | C49—C50—H50 | 117.2 |
C16—C17—C12 | 118.6 (3) | C51—C50—H50 | 117.2 |
C9—C18—C17 | 122.5 (3) | C52—C51—C60 | 118.1 (3) |
C9—C18—H18 | 118.7 | C52—C51—C50 | 119.8 (2) |
C17—C18—H18 | 118.7 | C60—C51—C50 | 122.1 (3) |
C20—C19—C2 | 124.2 (3) | C51—C52—C53 | 122.2 (2) |
C20—C19—H19 | 117.9 | C51—C52—H52 | 118.9 |
C2—C19—H19 | 117.9 | C53—C52—H52 | 118.9 |
C19—C20—C21 | 127.9 (3) | C54—C53—C52 | 122.7 (2) |
C19—C20—H20 | 116.1 | C54—C53—C58 | 118.8 (3) |
C21—C20—H20 | 116.1 | C52—C53—C58 | 118.5 (2) |
C22—C21—C30 | 117.5 (2) | C55—C54—C53 | 120.7 (3) |
C22—C21—C20 | 119.3 (2) | C55—C54—H54 | 119.6 |
C30—C21—C20 | 123.2 (3) | C53—C54—H54 | 119.6 |
C21—C22—C23 | 122.9 (2) | C54—C55—C56 | 120.6 (3) |
C21—C22—H22 | 118.5 | C54—C55—H55 | 119.7 |
C23—C22—H22 | 118.5 | C56—C55—H55 | 119.7 |
C24—C23—C22 | 122.3 (2) | C57—C56—C55 | 120.0 (3) |
C24—C23—C28 | 119.5 (3) | C57—C56—H56 | 120.0 |
C22—C23—C28 | 118.2 (3) | C55—C56—H56 | 120.0 |
C25—C24—C23 | 120.6 (3) | C56—C57—C58 | 120.8 (3) |
C25—C24—H24 | 119.7 | C56—C57—H57 | 119.6 |
C23—C24—H24 | 119.7 | C58—C57—H57 | 119.6 |
C24—C25—C26 | 119.6 (3) | C57—C58—C59 | 122.4 (2) |
C24—C25—H25 | 120.2 | C57—C58—C53 | 119.0 (3) |
C26—C25—H25 | 120.2 | C59—C58—C53 | 118.6 (3) |
C27—C26—C25 | 121.2 (3) | C60—C59—C58 | 121.4 (2) |
C27—C26—H26 | 119.4 | C60—C59—H59 | 119.3 |
C25—C26—H26 | 119.4 | C58—C59—H59 | 119.3 |
C26—C27—C28 | 120.2 (3) | C59—C60—C51 | 121.2 (3) |
C26—C27—H27 | 119.9 | C59—C60—H60 | 119.4 |
C28—C27—H27 | 119.9 | C51—C60—H60 | 119.4 |
C23—C28—C27 | 118.9 (3) | C66—C61—C62 | 119.7 (4) |
C23—C28—C29 | 119.1 (3) | C66—C61—H61 | 120.1 |
C27—C28—C29 | 122.1 (3) | C62—C61—H61 | 120.1 |
C30—C29—C28 | 120.9 (3) | C63—C62—C61 | 119.8 (4) |
C30—C29—H29 | 119.5 | C63—C62—H62 | 120.1 |
C28—C29—H29 | 119.5 | C61—C62—H62 | 120.1 |
C29—C30—C21 | 121.4 (3) | C64—C63—C62 | 119.6 (4) |
C29—C30—H30 | 119.3 | C64—C63—H63 | 120.2 |
C21—C30—H30 | 119.3 | C62—C63—H63 | 120.2 |
C32—C31—C36 | 123.3 (2) | C65—C64—C63 | 119.8 (4) |
C32—C31—Br2 | 118.8 (2) | C65—C64—H64 | 120.1 |
C36—C31—Br2 | 117.9 (2) | C63—C64—H64 | 120.1 |
C33—C32—C31 | 116.7 (3) | C66—C65—C64 | 120.7 (4) |
C33—C32—C49 | 120.5 (3) | C66—C65—H65 | 119.7 |
C31—C32—C49 | 122.7 (2) | C64—C65—H65 | 119.7 |
C34—C33—C32 | 121.3 (3) | C65—C66—C61 | 120.3 (4) |
C34—C33—H33 | 119.3 | C65—C66—H66 | 119.8 |
C32—C33—H33 | 119.3 | C61—C66—H66 | 119.8 |
C6—C1—C2—C3 | −0.1 (4) | Br2—C31—C32—C49 | 1.7 (4) |
Br1—C1—C2—C3 | −179.7 (2) | C31—C32—C33—C34 | 1.0 (4) |
C6—C1—C2—C19 | 179.0 (3) | C49—C32—C33—C34 | 179.4 (3) |
Br1—C1—C2—C19 | −0.6 (4) | C32—C33—C34—C35 | −0.3 (4) |
C1—C2—C3—C4 | −0.8 (4) | C33—C34—C35—C36 | −1.3 (4) |
C19—C2—C3—C4 | −179.9 (3) | C34—C35—C36—C31 | 2.0 (4) |
C2—C3—C4—C5 | 0.8 (4) | C34—C35—C36—C37 | −177.6 (3) |
C3—C4—C5—C6 | 0.2 (4) | C32—C31—C36—C35 | −1.2 (4) |
C4—C5—C6—C1 | −1.1 (4) | Br2—C31—C36—C35 | 178.47 (19) |
C4—C5—C6—C7 | 178.9 (3) | C32—C31—C36—C37 | 178.3 (2) |
C2—C1—C6—C5 | 1.1 (4) | Br2—C31—C36—C37 | −2.0 (3) |
Br1—C1—C6—C5 | −179.4 (2) | C35—C36—C37—C38 | 25.9 (4) |
C2—C1—C6—C7 | −178.9 (3) | C31—C36—C37—C38 | −153.6 (3) |
Br1—C1—C6—C7 | 0.7 (4) | C36—C37—C38—C39 | 177.1 (2) |
C5—C6—C7—C8 | −28.7 (4) | C37—C38—C39—C48 | −173.4 (3) |
C1—C6—C7—C8 | 151.3 (3) | C37—C38—C39—C40 | 4.0 (4) |
C6—C7—C8—C9 | 179.8 (2) | C48—C39—C40—C41 | 1.4 (4) |
C7—C8—C9—C18 | 165.0 (3) | C38—C39—C40—C41 | −176.0 (2) |
C7—C8—C9—C10 | −12.6 (4) | C39—C40—C41—C42 | 0.3 (4) |
C18—C9—C10—C11 | −3.2 (4) | C40—C41—C42—C43 | 177.3 (2) |
C8—C9—C10—C11 | 174.4 (2) | C40—C41—C42—C47 | −2.0 (4) |
C9—C10—C11—C12 | 1.1 (4) | C47—C42—C43—C44 | 0.7 (4) |
C10—C11—C12—C13 | −177.6 (3) | C41—C42—C43—C44 | −178.6 (3) |
C10—C11—C12—C17 | 1.4 (4) | C42—C43—C44—C45 | −0.9 (4) |
C11—C12—C13—C14 | 179.7 (3) | C43—C44—C45—C46 | 0.5 (4) |
C17—C12—C13—C14 | 0.6 (4) | C44—C45—C46—C47 | 0.1 (4) |
C12—C13—C14—C15 | 1.4 (4) | C45—C46—C47—C48 | 177.0 (2) |
C13—C14—C15—C16 | −2.2 (5) | C45—C46—C47—C42 | −0.3 (4) |
C14—C15—C16—C17 | 0.9 (5) | C43—C42—C47—C48 | −177.5 (2) |
C15—C16—C17—C18 | −178.0 (3) | C41—C42—C47—C48 | 1.9 (4) |
C15—C16—C17—C12 | 1.1 (4) | C43—C42—C47—C46 | −0.1 (4) |
C13—C12—C17—C18 | 177.3 (2) | C41—C42—C47—C46 | 179.2 (2) |
C11—C12—C17—C18 | −1.8 (4) | C40—C39—C48—C47 | −1.5 (4) |
C13—C12—C17—C16 | −1.9 (4) | C38—C39—C48—C47 | 176.1 (2) |
C11—C12—C17—C16 | 179.1 (2) | C46—C47—C48—C39 | −177.4 (2) |
C10—C9—C18—C17 | 2.8 (4) | C42—C47—C48—C39 | −0.1 (4) |
C8—C9—C18—C17 | −174.9 (2) | C33—C32—C49—C50 | 26.1 (4) |
C16—C17—C18—C9 | 178.8 (3) | C31—C32—C49—C50 | −155.6 (3) |
C12—C17—C18—C9 | −0.3 (4) | C32—C49—C50—C51 | −179.6 (2) |
C3—C2—C19—C20 | −24.3 (4) | C49—C50—C51—C52 | −166.7 (3) |
C1—C2—C19—C20 | 156.6 (3) | C49—C50—C51—C60 | 11.7 (4) |
C2—C19—C20—C21 | −179.3 (3) | C60—C51—C52—C53 | −1.8 (4) |
C19—C20—C21—C22 | 176.4 (3) | C50—C51—C52—C53 | 176.6 (2) |
C19—C20—C21—C30 | −2.0 (4) | C51—C52—C53—C54 | −179.5 (2) |
C30—C21—C22—C23 | 0.3 (4) | C51—C52—C53—C58 | 0.1 (4) |
C20—C21—C22—C23 | −178.2 (2) | C52—C53—C54—C55 | 179.6 (3) |
C21—C22—C23—C24 | 179.7 (2) | C58—C53—C54—C55 | 0.1 (4) |
C21—C22—C23—C28 | 1.1 (4) | C53—C54—C55—C56 | −1.5 (4) |
C22—C23—C24—C25 | −177.8 (2) | C54—C55—C56—C57 | 1.9 (4) |
C28—C23—C24—C25 | 0.8 (4) | C55—C56—C57—C58 | −0.8 (4) |
C23—C24—C25—C26 | 0.2 (4) | C56—C57—C58—C59 | 179.0 (3) |
C24—C25—C26—C27 | −0.9 (4) | C56—C57—C58—C53 | −0.7 (4) |
C25—C26—C27—C28 | 0.6 (4) | C54—C53—C58—C57 | 1.0 (4) |
C24—C23—C28—C27 | −1.1 (4) | C52—C53—C58—C57 | −178.5 (2) |
C22—C23—C28—C27 | 177.5 (2) | C54—C53—C58—C59 | −178.6 (2) |
C24—C23—C28—C29 | 179.8 (2) | C52—C53—C58—C59 | 1.8 (4) |
C22—C23—C28—C29 | −1.6 (4) | C57—C58—C59—C60 | 178.3 (2) |
C26—C27—C28—C23 | 0.4 (4) | C53—C58—C59—C60 | −2.0 (4) |
C26—C27—C28—C29 | 179.5 (3) | C58—C59—C60—C51 | 0.3 (4) |
C23—C28—C29—C30 | 0.6 (4) | C52—C51—C60—C59 | 1.6 (4) |
C27—C28—C29—C30 | −178.5 (3) | C50—C51—C60—C59 | −176.8 (2) |
C28—C29—C30—C21 | 1.0 (4) | C66—C61—C62—C63 | −1.6 (6) |
C22—C21—C30—C29 | −1.4 (4) | C61—C62—C63—C64 | 2.2 (6) |
C20—C21—C30—C29 | 177.0 (2) | C62—C63—C64—C65 | −1.1 (6) |
C36—C31—C32—C33 | −0.2 (4) | C63—C64—C65—C66 | −0.6 (6) |
Br2—C31—C32—C33 | −179.92 (19) | C64—C65—C66—C61 | 1.2 (6) |
C36—C31—C32—C49 | −178.6 (2) | C62—C61—C66—C65 | −0.1 (6) |
C30H17Br | F(000) = 928 |
Mr = 457.35 | Dx = 1.586 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9963 reflections |
a = 19.749 (3) Å | θ = 2.6–28.7° |
b = 13.2672 (17) Å | µ = 2.16 mm−1 |
c = 7.3108 (9) Å | T = 100 K |
β = 90.021 (2)° | Parallelepiped, yellow |
V = 1915.5 (4) Å3 | 0.16 × 0.07 × 0.04 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 4390 independent reflections |
Radiation source: fine-focus sealed tube | 3829 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ϕ and ω scans | θmax = 27.5°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a) | h = −25→25 |
Tmin = 0.764, Tmax = 0.919 | k = −17→17 |
16471 measured reflections | l = −9→9 |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0306P)2 + 1.5496P] where P = (Fo2 + 2Fc2)/3 |
4390 reflections | (Δ/σ)max = 0.002 |
280 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C30H17Br | V = 1915.5 (4) Å3 |
Mr = 457.35 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 19.749 (3) Å | µ = 2.16 mm−1 |
b = 13.2672 (17) Å | T = 100 K |
c = 7.3108 (9) Å | 0.16 × 0.07 × 0.04 mm |
β = 90.021 (2)° |
Bruker SMART APEX CCD area-detector diffractometer | 4390 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a) | 3829 reflections with I > 2σ(I) |
Tmin = 0.764, Tmax = 0.919 | Rint = 0.028 |
16471 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.43 e Å−3 |
4390 reflections | Δρmin = −0.32 e Å−3 |
280 parameters |
Experimental. The diffraction data were collected in three sets of 606 frames (0.3° width in omega) at phi = 0, 120 and 240°. A scan time of 60 sec/frame was used. |
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 > σ(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. H atoms were placed in calculated positions (C—H = 0.95 Å) and included as riding contributions with isotropic displacement parameters 1.2 times those of the attached C atoms. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.503111 (9) | 0.645530 (15) | 0.35216 (3) | 0.02390 (7) | |
C1 | 0.59584 (9) | 0.64305 (15) | 0.2749 (3) | 0.0177 (4) | |
C2 | 0.63023 (9) | 0.73485 (14) | 0.2628 (2) | 0.0168 (4) | |
C3 | 0.59744 (10) | 0.83047 (15) | 0.2869 (3) | 0.0202 (4) | |
H3 | 0.5538 | 0.8335 | 0.3412 | 0.024* | |
C4 | 0.62817 (10) | 0.91569 (15) | 0.2331 (3) | 0.0214 (4) | |
H4 | 0.6033 | 0.9770 | 0.2331 | 0.026* | |
C5 | 0.69743 (10) | 0.91674 (14) | 0.1756 (2) | 0.0183 (4) | |
C6 | 0.72771 (11) | 1.00913 (14) | 0.1185 (3) | 0.0217 (4) | |
H6 | 0.7005 | 1.0679 | 0.1074 | 0.026* | |
C7 | 0.79453 (11) | 1.01424 (15) | 0.0798 (3) | 0.0228 (4) | |
H7 | 0.8130 | 1.0747 | 0.0313 | 0.027* | |
C8 | 0.83752 (10) | 0.92988 (15) | 0.1110 (2) | 0.0197 (4) | |
C9 | 0.90859 (11) | 0.93813 (16) | 0.0922 (3) | 0.0243 (4) | |
H9 | 0.9275 | 0.9987 | 0.0451 | 0.029* | |
C10 | 0.95069 (11) | 0.86065 (16) | 0.1406 (3) | 0.0253 (4) | |
H10 | 0.9982 | 0.8664 | 0.1224 | 0.030* | |
C11 | 0.92330 (10) | 0.77259 (16) | 0.2173 (3) | 0.0212 (4) | |
H11 | 0.9525 | 0.7207 | 0.2594 | 0.025* | |
C12 | 0.85418 (9) | 0.76130 (15) | 0.2316 (2) | 0.0179 (4) | |
H12 | 0.8365 | 0.7012 | 0.2838 | 0.021* | |
C13 | 0.80880 (9) | 0.83661 (14) | 0.1709 (2) | 0.0164 (4) | |
C14 | 0.73574 (10) | 0.82768 (14) | 0.1830 (2) | 0.0159 (4) | |
C15 | 0.69954 (9) | 0.73222 (14) | 0.2031 (2) | 0.0152 (3) | |
C16 | 0.72728 (9) | 0.63963 (14) | 0.1484 (2) | 0.0150 (3) | |
H16 | 0.7724 | 0.6389 | 0.1032 | 0.018* | |
C17 | 0.69192 (9) | 0.54836 (14) | 0.1569 (2) | 0.0154 (3) | |
C18 | 0.62258 (9) | 0.55056 (14) | 0.2189 (2) | 0.0170 (4) | |
C19 | 0.58142 (10) | 0.46240 (15) | 0.2015 (3) | 0.0220 (4) | |
H19 | 0.5376 | 0.4608 | 0.2552 | 0.026* | |
C20 | 0.60464 (10) | 0.38160 (15) | 0.1091 (3) | 0.0239 (4) | |
H20 | 0.5746 | 0.3274 | 0.0844 | 0.029* | |
C21 | 0.67309 (10) | 0.37509 (14) | 0.0470 (3) | 0.0198 (4) | |
C22 | 0.69352 (11) | 0.28761 (15) | −0.0522 (3) | 0.0232 (4) | |
H22 | 0.6608 | 0.2378 | −0.0824 | 0.028* | |
C23 | 0.75859 (11) | 0.27448 (15) | −0.1038 (3) | 0.0226 (4) | |
H23 | 0.7706 | 0.2190 | −0.1792 | 0.027* | |
C24 | 0.80905 (10) | 0.34358 (14) | −0.0453 (3) | 0.0202 (4) | |
C25 | 0.87833 (11) | 0.32227 (16) | −0.0788 (3) | 0.0246 (4) | |
H25 | 0.8902 | 0.2657 | −0.1519 | 0.029* | |
C26 | 0.92825 (11) | 0.38174 (17) | −0.0077 (3) | 0.0267 (5) | |
H26 | 0.9744 | 0.3670 | −0.0323 | 0.032* | |
C27 | 0.91101 (10) | 0.46476 (16) | 0.1019 (3) | 0.0236 (4) | |
H27 | 0.9457 | 0.5046 | 0.1556 | 0.028* | |
C28 | 0.84415 (10) | 0.48879 (14) | 0.1320 (3) | 0.0188 (4) | |
H28 | 0.8337 | 0.5454 | 0.2064 | 0.023* | |
C29 | 0.79055 (9) | 0.43186 (14) | 0.0558 (2) | 0.0170 (4) | |
C30 | 0.71928 (9) | 0.45265 (14) | 0.0873 (2) | 0.0165 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.01296 (10) | 0.02711 (11) | 0.03163 (12) | 0.00136 (8) | 0.00380 (7) | −0.00150 (8) |
C1 | 0.0124 (8) | 0.0238 (10) | 0.0168 (9) | 0.0012 (7) | 0.0015 (6) | 0.0012 (7) |
C2 | 0.0164 (9) | 0.0212 (9) | 0.0129 (8) | 0.0027 (7) | −0.0016 (6) | −0.0010 (7) |
C3 | 0.0165 (9) | 0.0245 (10) | 0.0196 (9) | 0.0045 (7) | −0.0021 (7) | −0.0045 (8) |
C4 | 0.0237 (10) | 0.0185 (9) | 0.0221 (10) | 0.0060 (8) | −0.0048 (8) | −0.0054 (8) |
C5 | 0.0237 (10) | 0.0170 (9) | 0.0142 (9) | 0.0003 (7) | −0.0034 (7) | −0.0022 (7) |
C6 | 0.0322 (11) | 0.0140 (9) | 0.0189 (9) | 0.0018 (8) | −0.0036 (8) | −0.0035 (7) |
C7 | 0.0356 (11) | 0.0162 (9) | 0.0165 (9) | −0.0054 (8) | 0.0000 (8) | −0.0005 (7) |
C8 | 0.0278 (10) | 0.0189 (9) | 0.0125 (8) | −0.0046 (8) | −0.0001 (7) | −0.0022 (7) |
C9 | 0.0302 (11) | 0.0233 (10) | 0.0192 (9) | −0.0111 (9) | 0.0027 (8) | −0.0002 (8) |
C10 | 0.0203 (10) | 0.0326 (11) | 0.0230 (10) | −0.0080 (9) | 0.0006 (8) | −0.0023 (9) |
C11 | 0.0202 (9) | 0.0240 (10) | 0.0193 (9) | −0.0006 (8) | 0.0001 (7) | −0.0013 (8) |
C12 | 0.0200 (9) | 0.0198 (9) | 0.0140 (8) | −0.0027 (7) | 0.0008 (7) | −0.0009 (7) |
C13 | 0.0202 (9) | 0.0173 (9) | 0.0118 (8) | −0.0025 (7) | 0.0010 (7) | −0.0031 (7) |
C14 | 0.0203 (9) | 0.0164 (9) | 0.0110 (8) | −0.0003 (7) | −0.0008 (7) | −0.0010 (7) |
C15 | 0.0157 (8) | 0.0182 (9) | 0.0116 (8) | 0.0008 (7) | −0.0014 (6) | 0.0007 (7) |
C16 | 0.0145 (8) | 0.0187 (9) | 0.0117 (8) | 0.0001 (7) | −0.0005 (6) | 0.0005 (7) |
C17 | 0.0156 (8) | 0.0178 (9) | 0.0127 (8) | 0.0013 (7) | −0.0006 (6) | 0.0004 (7) |
C18 | 0.0161 (9) | 0.0195 (9) | 0.0153 (9) | −0.0007 (7) | −0.0010 (7) | 0.0021 (7) |
C19 | 0.0162 (9) | 0.0226 (10) | 0.0272 (10) | −0.0022 (8) | 0.0018 (7) | 0.0032 (8) |
C20 | 0.0215 (10) | 0.0196 (10) | 0.0305 (11) | −0.0046 (8) | −0.0009 (8) | 0.0029 (8) |
C21 | 0.0223 (10) | 0.0171 (9) | 0.0199 (9) | −0.0002 (7) | −0.0010 (7) | 0.0031 (7) |
C22 | 0.0303 (11) | 0.0158 (9) | 0.0235 (10) | −0.0021 (8) | −0.0036 (8) | 0.0004 (8) |
C23 | 0.0356 (11) | 0.0147 (9) | 0.0174 (9) | 0.0033 (8) | −0.0007 (8) | −0.0008 (7) |
C24 | 0.0270 (10) | 0.0179 (9) | 0.0156 (9) | 0.0041 (8) | 0.0013 (7) | 0.0028 (7) |
C25 | 0.0308 (11) | 0.0220 (10) | 0.0208 (10) | 0.0085 (8) | 0.0060 (8) | 0.0003 (8) |
C26 | 0.0222 (10) | 0.0297 (11) | 0.0283 (11) | 0.0084 (8) | 0.0072 (8) | 0.0022 (9) |
C27 | 0.0199 (10) | 0.0239 (10) | 0.0271 (10) | 0.0017 (8) | 0.0008 (8) | 0.0026 (8) |
C28 | 0.0205 (9) | 0.0168 (9) | 0.0190 (9) | 0.0023 (7) | 0.0012 (7) | 0.0013 (7) |
C29 | 0.0210 (9) | 0.0160 (9) | 0.0141 (8) | 0.0010 (7) | 0.0023 (7) | 0.0028 (7) |
C30 | 0.0192 (9) | 0.0167 (9) | 0.0135 (8) | 0.0010 (7) | −0.0003 (7) | 0.0023 (7) |
Br1—C1 | 1.9170 (18) | C15—C16 | 1.403 (3) |
C1—C2 | 1.397 (3) | C16—C17 | 1.399 (3) |
C1—C18 | 1.397 (3) | C16—H16 | 0.9500 |
C2—C3 | 1.435 (3) | C17—C18 | 1.443 (2) |
C2—C15 | 1.437 (2) | C17—C30 | 1.471 (3) |
C3—C4 | 1.342 (3) | C18—C19 | 1.430 (3) |
C3—H3 | 0.9500 | C19—C20 | 1.348 (3) |
C4—C5 | 1.431 (3) | C19—H19 | 0.9500 |
C4—H4 | 0.9500 | C20—C21 | 1.429 (3) |
C5—C14 | 1.404 (3) | C20—H20 | 0.9500 |
C5—C6 | 1.427 (3) | C21—C30 | 1.406 (3) |
C6—C7 | 1.351 (3) | C21—C22 | 1.427 (3) |
C6—H6 | 0.9500 | C22—C23 | 1.351 (3) |
C7—C8 | 1.423 (3) | C22—H22 | 0.9500 |
C7—H7 | 0.9500 | C23—C24 | 1.420 (3) |
C8—C9 | 1.415 (3) | C23—H23 | 0.9500 |
C8—C13 | 1.430 (3) | C24—C25 | 1.419 (3) |
C9—C10 | 1.368 (3) | C24—C29 | 1.433 (3) |
C9—H9 | 0.9500 | C25—C26 | 1.365 (3) |
C10—C11 | 1.404 (3) | C25—H25 | 0.9500 |
C10—H10 | 0.9500 | C26—C27 | 1.404 (3) |
C11—C12 | 1.377 (3) | C26—H26 | 0.9500 |
C11—H11 | 0.9500 | C27—C28 | 1.376 (3) |
C12—C13 | 1.414 (3) | C27—H27 | 0.9500 |
C12—H12 | 0.9500 | C28—C29 | 1.415 (3) |
C13—C14 | 1.450 (3) | C28—H28 | 0.9500 |
C14—C15 | 1.462 (3) | C29—C30 | 1.453 (3) |
C2—C1—C18 | 124.29 (17) | C17—C16—C15 | 123.36 (17) |
C2—C1—Br1 | 117.91 (14) | C17—C16—H16 | 118.3 |
C18—C1—Br1 | 117.55 (14) | C15—C16—H16 | 118.3 |
C1—C2—C3 | 122.92 (17) | C16—C17—C18 | 118.05 (16) |
C1—C2—C15 | 117.45 (17) | C16—C17—C30 | 123.25 (16) |
C3—C2—C15 | 119.25 (17) | C18—C17—C30 | 118.35 (16) |
C4—C3—C2 | 120.29 (18) | C1—C18—C19 | 121.97 (17) |
C4—C3—H3 | 119.9 | C1—C18—C17 | 117.93 (17) |
C2—C3—H3 | 119.9 | C19—C18—C17 | 119.69 (17) |
C3—C4—C5 | 121.78 (18) | C20—C19—C18 | 120.11 (18) |
C3—C4—H4 | 119.1 | C20—C19—H19 | 119.9 |
C5—C4—H4 | 119.1 | C18—C19—H19 | 119.9 |
C14—C5—C6 | 120.56 (18) | C19—C20—C21 | 121.96 (19) |
C14—C5—C4 | 119.72 (17) | C19—C20—H20 | 119.0 |
C6—C5—C4 | 119.68 (17) | C21—C20—H20 | 119.0 |
C7—C6—C5 | 120.92 (18) | C30—C21—C22 | 121.21 (18) |
C7—C6—H6 | 119.5 | C30—C21—C20 | 120.21 (18) |
C5—C6—H6 | 119.5 | C22—C21—C20 | 118.57 (18) |
C6—C7—C8 | 120.65 (18) | C23—C22—C21 | 121.07 (19) |
C6—C7—H7 | 119.7 | C23—C22—H22 | 119.5 |
C8—C7—H7 | 119.7 | C21—C22—H22 | 119.5 |
C9—C8—C7 | 121.04 (18) | C22—C23—C24 | 120.03 (18) |
C9—C8—C13 | 119.36 (18) | C22—C23—H23 | 120.0 |
C7—C8—C13 | 119.53 (18) | C24—C23—H23 | 120.0 |
C10—C9—C8 | 121.31 (19) | C25—C24—C23 | 119.76 (18) |
C10—C9—H9 | 119.3 | C25—C24—C29 | 119.88 (18) |
C8—C9—H9 | 119.3 | C23—C24—C29 | 120.27 (18) |
C9—C10—C11 | 119.60 (19) | C26—C25—C24 | 121.03 (19) |
C9—C10—H10 | 120.2 | C26—C25—H25 | 119.5 |
C11—C10—H10 | 120.2 | C24—C25—H25 | 119.5 |
C12—C11—C10 | 120.19 (19) | C25—C26—C27 | 119.70 (19) |
C12—C11—H11 | 119.9 | C25—C26—H26 | 120.2 |
C10—C11—H11 | 119.9 | C27—C26—H26 | 120.2 |
C11—C12—C13 | 121.83 (18) | C28—C27—C26 | 120.4 (2) |
C11—C12—H12 | 119.1 | C28—C27—H27 | 119.8 |
C13—C12—H12 | 119.1 | C26—C27—H27 | 119.8 |
C12—C13—C8 | 117.16 (17) | C27—C28—C29 | 122.08 (18) |
C12—C13—C14 | 123.62 (17) | C27—C28—H28 | 119.0 |
C8—C13—C14 | 118.94 (17) | C29—C28—H28 | 119.0 |
C5—C14—C13 | 117.71 (17) | C28—C29—C24 | 116.68 (17) |
C5—C14—C15 | 117.99 (17) | C28—C29—C30 | 124.13 (17) |
C13—C14—C15 | 124.29 (16) | C24—C29—C30 | 118.96 (17) |
C16—C15—C2 | 118.67 (17) | C21—C30—C29 | 117.15 (17) |
C16—C15—C14 | 122.58 (16) | C21—C30—C17 | 117.76 (17) |
C2—C15—C14 | 118.39 (16) | C29—C30—C17 | 125.08 (17) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C30H21Br·0.5(C6H6) | C30H17Br |
Mr | 500.43 | 457.35 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/c |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 11.633 (1), 26.665 (2), 15.2364 (14) | 19.749 (3), 13.2672 (17), 7.3108 (9) |
β (°) | 91.513 (1) | 90.021 (2) |
V (Å3) | 4724.7 (7) | 1915.5 (4) |
Z | 8 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.76 | 2.16 |
Crystal size (mm) | 0.36 × 0.14 × 0.03 | 0.16 × 0.07 × 0.04 |
Data collection | ||
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Integration (SADABS; Sheldrick, 2008a) | Multi-scan (SADABS; Sheldrick, 2008a) |
Tmin, Tmax | 0.501, 0.956 | 0.764, 0.919 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 39415, 10288, 7141 | 16471, 4390, 3829 |
Rint | 0.051 | 0.028 |
(sin θ/λ)max (Å−1) | 0.639 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.101, 1.01 | 0.030, 0.073, 1.06 |
No. of reflections | 10288 | 4390 |
No. of parameters | 613 | 280 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.52, −0.67 | 0.43, −0.32 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008b).
C7—C8 | 1.346 (4) | C14—C15 | 1.405 (4) |
C9—C18 | 1.378 (4) | C15—C16 | 1.363 (4) |
C9—C10 | 1.432 (4) | C16—C17 | 1.412 (4) |
C10—C11 | 1.357 (4) | C17—C18 | 1.412 (4) |
C11—C12 | 1.417 (4) | C19—C20 | 1.330 (4) |
C12—C13 | 1.411 (4) | C21—C22 | 1.383 (4) |
C12—C17 | 1.424 (4) | C39—C48 | 1.380 (4) |
C13—C14 | 1.359 (4) | C51—C52 | 1.379 (4) |
C3—C4 | 1.342 (3) | C16—C17 | 1.399 (3) |
C4—C5 | 1.431 (3) | C17—C30 | 1.471 (3) |
C5—C14 | 1.404 (3) | C19—C20 | 1.348 (3) |
C5—C6 | 1.427 (3) | C20—C21 | 1.429 (3) |
C6—C7 | 1.351 (3) | C21—C30 | 1.406 (3) |
C7—C8 | 1.423 (3) | C21—C22 | 1.427 (3) |
C8—C9 | 1.415 (3) | C22—C23 | 1.351 (3) |
C8—C13 | 1.430 (3) | C23—C24 | 1.420 (3) |
C9—C10 | 1.368 (3) | C24—C25 | 1.419 (3) |
C10—C11 | 1.404 (3) | C24—C29 | 1.433 (3) |
C11—C12 | 1.377 (3) | C25—C26 | 1.365 (3) |
C12—C13 | 1.414 (3) | C26—C27 | 1.404 (3) |
C13—C14 | 1.450 (3) | C27—C28 | 1.376 (3) |
C14—C15 | 1.462 (3) | C28—C29 | 1.415 (3) |
C15—C16 | 1.403 (3) | C29—C30 | 1.453 (3) |
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9-Bromodinaphth[1,2-a:2',1'-j]anthracene, (II), has been studied as a model for coronaphenes, a subset of the benzannelated annulene family of polycyclic aromatic hydrocarbons (PAHs) (Wilcox et al. 1978). As part of this work, molecular mechanics computations (Lahti, 1988) were performed which indicated the presence of a Clar-type (Clar, 1964, 1972) localized structure, rather than extensive superaromatic delocalization around the perimeter. The previous study also envisaged using the reactivity of the Br atom at the 9-position to connect a strongly nonplanar PAH to other functionalities at this site, with the expectation that its presence would have a significant effect on the packing of such derivatives in the solid state. To confirm the predictions of the earlier molecular mechanics calculations, the structure of (II) was determined at low temperature to obtain accurate C—C bond distances, as well as to provide a benchmark for the crystal packing of derivatives of (II).
Compound (II) was readily prepared by the solution photocyclization of 2-bromo-1,3-bis[2-(2-naphthyl)vinyl]benzene, (I). The ease of photocyclization of (I) to form (II) requires (I) to undergo cis–trans isomerization with conformational flexiblity in solution, so it was also of interest to determine the solid-state structure of (I).
In the crystal structure, (I) exists in an extended (vinyl groups and ipso-C atoms of the naphthyl groups close to coplanarity with the central six-membered ring) though significantly twisted conformation (Fig. 1) for each of the independent molecules in the asymmetric unit. The primary difference between these is different orientations of the naphthyl groups with respect to the central six-membered ring. The dihedral angle between the mean planes of the naphthyl groups in (I) (molecule 1) is 52.7 (5)°, while in molecule 2 it is 55.7 (5)°. As shown in Fig. 2, the packing consists of offset stacks of molecules with interdigitated ends, such that there are significant C—H···π interactions in the interdigitated region. Close contacts include C11—H11—Cg1(1 - x, 1 - y, 1 - z) (2.70 Å and 148°), C27—H27—Cg2(3/2 - x, -1/2 + y, 3/2 - z) (2.72 Å and 149°), C43—H43—Cg3(1/2 - x, 1/2 + y, 3/2 - z) (2.70 Å and 149°) and C57—H57—Cg4(1 - x, -y, 1 - z) (2.77 Å and 157°) (Cg1–Cg4 are the centroids of the C39—C48, C9—C18, C51—C52 and C21—C22 bonds, respectively). As is evident from Table 1, there is a distinct alternation of C—C bond distances in the naphthyl groups (shown in full for the one consisting of atoms C9–C18; the others show comparable values), indicating a concentration of π density in the shorter bonds and thereby favoring the formation of C—H···π interactions with individual C—C bonds rather than with the six-membered ring as a whole. This manner of packing leaves relatively large voids between the stacks, which are filled by solvent benzene molecules.
Compound (II) adopts a `manta-ray'-shaped conformation in the crystal structure (Fig. 3b), presumably in part due to attempted relief of the structurally constrained close contacts between three H atoms in the interior of the molecule (H12···H16 = 2.01 Å, H12···H28 = 2.14 Å and H16···H28 = 1.89 Å). This conformation lends itself to efficient packing in the crystal structure, as shown in Fig. 4, with an offset π-stacking involving the C3–C7 portion of one molecule with the C1/C17/C18/C29/C30 portion of an adjacent one and with the C—Br bonds parallel. The intermolecular contact distance is about 3.36 Å. In addition, adjacent zigzag stacks with opposite concavity and C—Br bond orientation are connected via C—H···π interactions involving C23—H23 with the centroid Cg5 of the C28—C29 bond in a neighboring stack (H23—Cg5 = 2.77 Å and C23—H23—Cg5 = 159°). Additionally, there are attractive inter-stack C20—H20—Br1 interactions (H20—Br1 = 2.90 Å and C20—H20—Br1 = 159°) (Brammer, et al., 2001).
The distinct alternation of C—C bond lengths of (II) in the two wings (Table 2) confirms the results of the earlier molecular mechanics calculations. Those computations also showed that a helical C2 structure for (II) had a slightly lower energy than the approximate Cs structure found in the solid state. The earlier structural computations were confirmed as part of the present work by RB3LYP/6-31G*, RB3LYP/cc-pVDZ//6-31G* and RB3LYP/cc-pVDZ hybrid density functional computations on (II) using GAUSSIAN03 (Frisch et al., 2004), which show that the C2 geometry is more stable than the Cs one by, respectively, 10.0, 10.9 and 10.5 kJ mol-1 (no zero-point energy corrections). We presume that this slight energy difference is overcome by the more favorable packing afforded by the Cs geometry. The effective `thickness' of the observed conformation is ca 2 Å, while that of the helical geometry would be ca 4 Å. The effective `filled space' in the structure of (II) is 73.7%.
In what appears to be the only crystal structure of an analogous compound reported to date, 9,18-dimethoxynaphtph[1,2-a:2',1'-j]anthracene, (III) (Gupta et al., 1991), was also found to have a Cs structure rather than a helical one, with a computationally estimated preference of 14.2 kJ mol-1. It is tempting to suggest that the increase in internal congestion as a result of replacing atom H16 by a methoxy group forces a preference for the Cs geometry. However, the similar compounds, (IV) (see scheme; X = CH, N) (Zimmerman & Wilson, 1992), have helical conformations. We think that these comparison cases support the notion that the helical and Cs conformations are sufficiently similar in energy that which one will be found in the solid state in any particular instance will be dependent on packing forces.