2-Bromo-1,3-bis­[2-(2-naphthyl)vinyl]benzene benzene hemisolvate and 9-bromo­dinaphth[1,2-a:2',1'-j]anthracene

2-Bromo-1,3-bis­[2-(2-naphthyl)vinyl]benzene benzene hemisolvate, C₃₀H₂₁Br·0.5C₆H₆, (I), with two formula units in the asymmetric unit, exists in the crystal structure in a conformation in which the trans (2-naphthyl)vinyl substituents on the central bromo­benzene moiety appear as nearly fully extended `wings', while 9-bromo­dinaphth[1,2-a:2',1'-j]anthracene, C<sub>30</sub>H<sub>17</sub>Br, (II), adopts a highly nonplanar `manta-ray' shape, with the H atoms in the inter­ior of the mol­ecule within van der Waals contact distances. The packing of the significantly twisted mol­ecules of (I) generates large voids which are filled by benzene solvent mol­ecules, while mol­ecules of (II) stack compactly with all C-Br bonds parallel within the stack.

S1. Comment

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 C_s 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 C_s 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 C_s 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 C_s 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 C_s 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 C_s 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.

Related literature

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).

S2. Experimental

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.

S3. Refinement

H atoms were placed in calculated positions, with C—H = 0.95 Å, and included as riding, with U_iso(H) = 1.2U_eq(C).

Computing details

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).

Figures

	Fig. 1. A perspective view of (I), with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The packing in (I), viewed down a. Only those H atoms involved in the C—H···π interactions are included.
	Fig. 3. (a) Perspective view of (II), with displacement ellipsoids drawn at the 50% probability level. (b) A view of (II) along the Br1—C1 bond [The quality of this is rather poor - please provide a sharper image].
	Fig. 4. (a) The packing in (II), viewed down c. (b) The packing in (II), viewed approximately down a. Only those H atoms involved in C—H···Br interactions are included.

(I) 2-Bromo-1,3-bis[2-(2-naphthyl)vinyl]benzene benzene hemisolvate

Crystal data

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) Å^3	0.36 × 0.14 × 0.03 mm
Z = 8

Data collection

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

Refinement on F^2	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0489P)^2 + 0.9303P] where P = (Fo^2 + 2Fc^2)/3
10288 reflections	(Δ/σ)max = 0.002
613 parameters	Δρmax = 0.52 e Å^−3
0 restraints	Δρmin = −0.67 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

(II) 9-bromodinaphth[1,2-a:2',1'-j]anthracene

Crystal data

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) Å^3	0.16 × 0.07 × 0.04 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.073	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0306P)^2 + 1.5496P] where P = (Fo^2 + 2Fc^2)/3
4390 reflections	(Δ/σ)max = 0.002
280 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)