4,4'-Dibromo-7,7'-dimeth-oxy-1,1'-spiro-biindane.

In the title compound, C(19)H(18)Br(2)O(2), the dihedral angle between the two benzene rings of the spiro-biindane molecule is 70.44 (8)°. In the crystal, mol-ecules are inter-connected along the c axis by C-H⋯O hydrogen bonds and π-π stacking [centroid-centroid distance = 3.893 (2) Å] inter-actions, forming an infinite chain structure. The chains are further inter-connected through another set of C-H⋯O hydrogen bonds, forming layers approximately parallel to the bc plane.

Related literature

For studies on spiranes, see: Srivastava et al. (1992 ▶); Chan et al. (1997 ▶); Ding et al. (2009 ▶). For 1,1′-spiro­biindane and its analogs, see: Brewster & Prudence (1973 ▶); Birman et al. (1999 ▶).

Experimental

Crystal data

C19H18Br2O2

M = 438.15

Triclinic,

a = 8.3487 (3) Å

b = 10.4831 (3) Å

c = 11.6293 (4) Å

α = 112.047 (2)°

β = 105.559 (2)°

γ = 94.280 (2)°

V = 891.11 (5) Å3

Z = 2

Mo Kα radiation

μ = 4.56 mm−1

T = 296 K

0.40 × 0.16 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.263, T max = 0.659

9917 measured reflections

3090 independent reflections

2470 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.081

S = 1.05

3090 reflections

208 parameters

H-atom parameters constrained

Δρmax = 0.51 e Å−3

Δρmin = −0.41 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: APEX2 and SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810046519/zq2071sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810046519/zq2071Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C19H18Br2O2	Z = 2
Mr = 438.15	F(000) = 436
Triclinic, P1	Dx = 1.633 Mg m−3
a = 8.3487 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.4831 (3) Å	Cell parameters from 9917 reflections
c = 11.6293 (4) Å	θ = 2.2–25.0°
α = 112.047 (2)°	µ = 4.56 mm−1
β = 105.559 (2)°	T = 296 K
γ = 94.280 (2)°	Block, orange
V = 891.11 (5) Å3	0.40 × 0.16 × 0.10 mm

Bruker APEXII CCD area-detector diffractometer	3090 independent reflections
Radiation source: fine-focus sealed tube	2470 reflections with I > 2σ(I)
graphite	Rint = 0.016
ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −9→9
Tmin = 0.263, Tmax = 0.659	k = −12→12
9917 measured reflections	l = −12→13

Refinement on F2	Primary atom site location: structure-invariant direct methods
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) = 0.081	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0381P)2 + 0.4917P] where P = (Fo2 + 2Fc2)/3
3090 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.51 e Å−3
0 restraints	Δρmin = −0.41 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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.

	x	y	z	Uiso*/Ueq
Br1	1.10416 (5)	−0.01254 (4)	0.77083 (5)	0.08981 (17)
Br2	0.47345 (5)	0.80256 (3)	0.72566 (4)	0.07264 (15)
O1	0.5993 (3)	0.3495 (2)	0.9166 (2)	0.0653 (6)
O2	0.4765 (2)	0.18707 (19)	0.5868 (2)	0.0529 (5)
C1	0.9460 (4)	0.1024 (3)	0.8190 (3)	0.0584 (8)
C2	0.8577 (4)	0.0773 (3)	0.8944 (3)	0.0627 (9)
H2A	0.8767	0.0061	0.9227	0.075*
C3	0.7404 (4)	0.1577 (3)	0.9285 (3)	0.0578 (8)
H3A	0.6811	0.1406	0.9802	0.069*
C4	0.7105 (4)	0.2636 (3)	0.8863 (3)	0.0502 (7)
C5	0.7982 (3)	0.2868 (3)	0.8074 (3)	0.0442 (6)
C6	0.9173 (3)	0.2067 (3)	0.7741 (3)	0.0503 (7)
C7	0.9965 (4)	0.2507 (4)	0.6906 (4)	0.0648 (9)
H7A	1.0008	0.1700	0.6160	0.078*
H7B	1.1103	0.3053	0.7403	0.078*
C8	0.8773 (4)	0.3406 (4)	0.6466 (3)	0.0584 (8)
H8A	0.7945	0.2843	0.5614	0.070*
H8B	0.9414	0.4179	0.6410	0.070*
C9	0.7877 (3)	0.3968 (3)	0.7517 (3)	0.0453 (6)
C10	0.8785 (4)	0.5453 (3)	0.8581 (3)	0.0596 (8)
H10A	0.8676	0.5560	0.9420	0.072*
H10B	0.9981	0.5610	0.8671	0.072*
C11	0.7909 (4)	0.6495 (3)	0.8117 (3)	0.0605 (8)
H11A	0.7849	0.7308	0.8851	0.073*
H11B	0.8498	0.6804	0.7625	0.073*
C12	0.6173 (4)	0.5641 (3)	0.7261 (3)	0.0446 (6)
C13	0.4707 (4)	0.6077 (3)	0.6789 (3)	0.0477 (7)
C14	0.3237 (4)	0.5120 (3)	0.6013 (3)	0.0533 (7)
H14A	0.2257	0.5423	0.5707	0.064*
C15	0.3202 (4)	0.3699 (3)	0.5681 (3)	0.0498 (7)
H15A	0.2200	0.3052	0.5150	0.060*
C16	0.4663 (3)	0.3244 (3)	0.6142 (3)	0.0420 (6)
C17	0.6141 (3)	0.4225 (3)	0.6941 (2)	0.0394 (6)
C18	0.5014 (7)	0.3249 (5)	0.9914 (6)	0.1131 (17)
H18A	0.4297	0.3928	1.0065	0.170*
H18B	0.5755	0.3330	1.0738	0.170*
H18C	0.4326	0.2322	0.9444	0.170*
C19	0.3276 (4)	0.0840 (3)	0.5120 (4)	0.0867 (13)
H19A	0.3532	−0.0069	0.5001	0.130*
H19B	0.2833	0.0871	0.4281	0.130*
H19C	0.2449	0.1017	0.5568	0.130*

	U11	U22	U33	U12	U13	U23
Br1	0.0726 (3)	0.0841 (3)	0.1278 (4)	0.0397 (2)	0.0242 (2)	0.0606 (3)
Br2	0.0993 (3)	0.0474 (2)	0.0780 (3)	0.02663 (18)	0.0233 (2)	0.03427 (17)
O1	0.0935 (16)	0.0611 (13)	0.0655 (14)	0.0282 (12)	0.0445 (13)	0.0362 (12)
O2	0.0505 (11)	0.0347 (10)	0.0600 (13)	0.0049 (9)	0.0086 (10)	0.0121 (9)
C1	0.0479 (16)	0.0516 (17)	0.069 (2)	0.0128 (14)	0.0002 (16)	0.0302 (16)
C2	0.064 (2)	0.0506 (18)	0.069 (2)	0.0021 (16)	−0.0034 (17)	0.0378 (17)
C3	0.070 (2)	0.0525 (17)	0.0519 (18)	0.0023 (16)	0.0104 (16)	0.0307 (15)
C4	0.0597 (17)	0.0444 (15)	0.0418 (16)	0.0028 (14)	0.0080 (14)	0.0199 (13)
C5	0.0469 (15)	0.0413 (14)	0.0388 (15)	0.0037 (12)	0.0019 (12)	0.0195 (12)
C6	0.0423 (15)	0.0500 (16)	0.0544 (18)	0.0049 (13)	0.0030 (13)	0.0261 (14)
C7	0.0532 (18)	0.074 (2)	0.082 (2)	0.0226 (16)	0.0233 (17)	0.0453 (19)
C8	0.0534 (17)	0.071 (2)	0.069 (2)	0.0182 (16)	0.0219 (16)	0.0454 (18)
C9	0.0450 (15)	0.0450 (15)	0.0470 (16)	0.0048 (12)	0.0066 (13)	0.0264 (13)
C10	0.0592 (18)	0.0503 (17)	0.060 (2)	−0.0016 (15)	−0.0029 (15)	0.0294 (15)
C11	0.067 (2)	0.0455 (16)	0.061 (2)	0.0013 (15)	0.0026 (17)	0.0274 (15)
C12	0.0552 (16)	0.0408 (14)	0.0401 (15)	0.0061 (13)	0.0114 (13)	0.0223 (12)
C13	0.0643 (18)	0.0431 (15)	0.0461 (16)	0.0183 (14)	0.0188 (15)	0.0273 (13)
C14	0.0542 (17)	0.0606 (19)	0.0566 (18)	0.0230 (16)	0.0177 (15)	0.0341 (16)
C15	0.0428 (15)	0.0515 (17)	0.0507 (17)	0.0052 (13)	0.0079 (13)	0.0219 (14)
C16	0.0488 (15)	0.0396 (14)	0.0392 (15)	0.0096 (12)	0.0152 (13)	0.0171 (12)
C17	0.0459 (14)	0.0409 (14)	0.0343 (14)	0.0087 (12)	0.0114 (12)	0.0195 (12)
C18	0.155 (4)	0.104 (3)	0.152 (5)	0.057 (3)	0.111 (4)	0.080 (3)
C19	0.060 (2)	0.0456 (19)	0.131 (4)	0.0056 (17)	0.026 (2)	0.015 (2)

Br1—C1	1.907 (3)	C9—C17	1.515 (4)
Br2—C13	1.903 (3)	C9—C10	1.551 (4)
O1—C4	1.364 (4)	C10—C11	1.539 (4)
O1—C18	1.417 (4)	C10—H10A	0.9700
O2—C16	1.367 (3)	C10—H10B	0.9700
O2—C19	1.408 (4)	C11—C12	1.502 (4)
C1—C2	1.368 (5)	C11—H11A	0.9700
C1—C6	1.389 (4)	C11—H11B	0.9700
C2—C3	1.381 (5)	C12—C17	1.384 (4)
C2—H2A	0.9300	C12—C13	1.386 (4)
C3—C4	1.386 (4)	C13—C14	1.367 (4)
C3—H3A	0.9300	C14—C15	1.387 (4)
C4—C5	1.392 (4)	C14—H14A	0.9300
C5—C6	1.390 (4)	C15—C16	1.390 (4)
C5—C9	1.517 (3)	C15—H15A	0.9300
C6—C7	1.493 (4)	C16—C17	1.386 (4)
C7—C8	1.538 (4)	C18—H18A	0.9600
C7—H7A	0.9700	C18—H18B	0.9600
C7—H7B	0.9700	C18—H18C	0.9600
C8—C9	1.554 (4)	C19—H19A	0.9600
C8—H8A	0.9700	C19—H19B	0.9600
C8—H8B	0.9700	C19—H19C	0.9600
C4—O1—C18	117.9 (3)	C9—C10—H10A	110.5
C16—O2—C19	118.4 (2)	C11—C10—H10B	110.5
C2—C1—C6	120.7 (3)	C9—C10—H10B	110.5
C2—C1—Br1	119.1 (2)	H10A—C10—H10B	108.7
C6—C1—Br1	120.1 (3)	C12—C11—C10	102.8 (2)
C1—C2—C3	120.1 (3)	C12—C11—H11A	111.2
C1—C2—H2A	120.0	C10—C11—H11A	111.2
C3—C2—H2A	120.0	C12—C11—H11B	111.2
C2—C3—C4	120.4 (3)	C10—C11—H11B	111.2
C2—C3—H3A	119.8	H11A—C11—H11B	109.1
C4—C3—H3A	119.8	C17—C12—C13	119.5 (3)
O1—C4—C3	124.6 (3)	C17—C12—C11	110.9 (2)
O1—C4—C5	116.1 (2)	C13—C12—C11	129.6 (3)
C3—C4—C5	119.3 (3)	C14—C13—C12	120.5 (2)
C6—C5—C4	120.2 (2)	C14—C13—Br2	119.9 (2)
C6—C5—C9	111.3 (2)	C12—C13—Br2	119.6 (2)
C4—C5—C9	128.4 (3)	C13—C14—C15	120.3 (3)
C1—C6—C5	119.2 (3)	C13—C14—H14A	119.9
C1—C6—C7	129.8 (3)	C15—C14—H14A	119.9
C5—C6—C7	111.0 (2)	C14—C15—C16	120.0 (3)
C6—C7—C8	103.2 (2)	C14—C15—H15A	120.0
C6—C7—H7A	111.1	C16—C15—H15A	120.0
C8—C7—H7A	111.1	O2—C16—C17	116.2 (2)
C6—C7—H7B	111.1	O2—C16—C15	124.6 (2)
C8—C7—H7B	111.1	C17—C16—C15	119.2 (2)
H7A—C7—H7B	109.1	C12—C17—C16	120.6 (2)
C7—C8—C9	106.4 (2)	C12—C17—C9	111.2 (2)
C7—C8—H8A	110.5	C16—C17—C9	128.2 (2)
C9—C8—H8A	110.5	O1—C18—H18A	109.5
C7—C8—H8B	110.5	O1—C18—H18B	109.5
C9—C8—H8B	110.5	H18A—C18—H18B	109.5
H8A—C8—H8B	108.6	O1—C18—H18C	109.5
C17—C9—C5	118.2 (2)	H18A—C18—H18C	109.5
C17—C9—C10	101.5 (2)	H18B—C18—H18C	109.5
C5—C9—C10	111.8 (2)	O2—C19—H19A	109.5
C17—C9—C8	111.6 (2)	O2—C19—H19B	109.5
C5—C9—C8	101.4 (2)	H19A—C19—H19B	109.5
C10—C9—C8	112.7 (2)	O2—C19—H19C	109.5
C11—C10—C9	106.1 (2)	H19A—C19—H19C	109.5
C11—C10—H10A	110.5	H19B—C19—H19C	109.5
C6—C1—C2—C3	−1.1 (5)	C17—C9—C10—C11	−26.4 (3)
Br1—C1—C2—C3	−178.9 (2)	C5—C9—C10—C11	−153.3 (3)
C1—C2—C3—C4	0.4 (5)	C8—C9—C10—C11	93.2 (3)
C18—O1—C4—C3	−3.1 (5)	C9—C10—C11—C12	25.7 (3)
C18—O1—C4—C5	176.9 (4)	C10—C11—C12—C17	−15.2 (3)
C2—C3—C4—O1	−179.0 (3)	C10—C11—C12—C13	164.8 (3)
C2—C3—C4—C5	1.0 (4)	C17—C12—C13—C14	0.0 (4)
O1—C4—C5—C6	178.4 (3)	C11—C12—C13—C14	180.0 (3)
C3—C4—C5—C6	−1.5 (4)	C17—C12—C13—Br2	178.7 (2)
O1—C4—C5—C9	0.8 (4)	C11—C12—C13—Br2	−1.3 (4)
C3—C4—C5—C9	−179.2 (3)	C12—C13—C14—C15	−0.5 (4)
C2—C1—C6—C5	0.5 (5)	Br2—C13—C14—C15	−179.2 (2)
Br1—C1—C6—C5	178.3 (2)	C13—C14—C15—C16	0.3 (4)
C2—C1—C6—C7	−179.3 (3)	C19—O2—C16—C17	176.6 (3)
Br1—C1—C6—C7	−1.5 (5)	C19—O2—C16—C15	−3.3 (4)
C4—C5—C6—C1	0.8 (4)	C14—C15—C16—O2	−179.7 (3)
C9—C5—C6—C1	178.8 (2)	C14—C15—C16—C17	0.5 (4)
C4—C5—C6—C7	−179.4 (3)	C13—C12—C17—C16	0.8 (4)
C9—C5—C6—C7	−1.4 (3)	C11—C12—C17—C16	−179.2 (3)
C1—C6—C7—C8	165.1 (3)	C13—C12—C17—C9	178.2 (2)
C5—C6—C7—C8	−14.7 (4)	C11—C12—C17—C9	−1.8 (3)
C6—C7—C8—C9	24.5 (3)	O2—C16—C17—C12	179.1 (2)
C6—C5—C9—C17	138.9 (3)	C15—C16—C17—C12	−1.0 (4)
C4—C5—C9—C17	−43.4 (4)	O2—C16—C17—C9	2.1 (4)
C6—C5—C9—C10	−103.8 (3)	C15—C16—C17—C9	−178.0 (3)
C4—C5—C9—C10	74.0 (4)	C5—C9—C17—C12	140.4 (3)
C6—C5—C9—C8	16.5 (3)	C10—C9—C17—C12	17.7 (3)
C4—C5—C9—C8	−165.7 (3)	C8—C9—C17—C12	−102.6 (3)
C7—C8—C9—C17	−151.6 (3)	C5—C9—C17—C16	−42.4 (4)
C7—C8—C9—C5	−24.9 (3)	C10—C9—C17—C16	−165.1 (3)
C7—C8—C9—C10	94.8 (3)	C8—C9—C17—C16	74.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C18i—H18Ai···O1	0.96	2.56	3.416 (6)	149
C19ii—H19Aii···O2	0.96	2.52	3.365 (2)	147

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C18i—H18Ai⋯O1	0.96	2.56	3.416 (6)	149
C19ii—H19Aii⋯O2	0.96	2.52	3.365 (2)	147

Symmetry codes: (i) ; (ii) .