7,14-Bis(4-bromo-phen-yl)-2,11,11-trimethyl-1,4,10,12-tetra-oxa-dispiro-[4.2.5.2]penta-decane-9,13-dione.

In the mol-ecule of the title compound, C(26)H(26)Br(2)O(6), the cyclo-hexane ring is in a chair conformation, while the five-membered and 1,3-dioxane rings both adopt envelope conformations. The dihedral angle between the benzene rings is 77.21 (3)°. In the crystal structure, weak inter-molecular C-H⋯O inter-actions link the mol-ecules into centrosymmetric dimers, forming R(2) (2)(14) ring motifs. One of the Br atoms, the methyl C and H atoms, and the C atom bonded to the methyl group of the five-membered ring are disordered over two positions. The Br atoms were refined with occupancies of 0.51 (4) and 0.49 (4), while the C and H atoms were refined with occupancies of 0.320 (18) and 0.680 (18).

Related literature

For general background, see: Davidson & Bernhard (1948 ▶); Meldrum (1908 ▶); Muller et al. (2005 ▶); Ramachary et al. (2003 ▶); Tietze & Beifuss (1993 ▶); Tietze et al. (2001 ▶). For related structures, see: Chande & Khanwelkar (2005 ▶); Ramachary & Barbas (2004 ▶). For bond-length data, see: Allen et al. (1987 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C26H26Br2O6

M = 594.29

Triclinic,

a = 7.356 (3) Å

b = 12.590 (5) Å

c = 14.852 (6) Å

α = 69.787 (6)°

β = 87.415 (7)°

γ = 79.243 (6)°

V = 1267.8 (9) Å3

Z = 2

Mo Kα radiation

μ = 3.24 mm−1

T = 298 K

0.18 × 0.11 × 0.09 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.594, T max = 0.759

6454 measured reflections

4330 independent reflections

1413 reflections with I > 2σ(I)

R int = 0.060

Refinement

R[F 2 > 2σ(F 2)] = 0.073

wR(F 2) = 0.146

S = 1.00

4330 reflections

327 parameters

H-atom parameters constrained

Δρmax = 0.44 e Å−3

Δρmin = −0.32 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809014251/hk2666sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014251/hk2666Isup2.hkl

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

C26H26Br2O6	Z = 2
Mr = 594.29	F(000) = 600
Triclinic, P1	Dx = 1.557 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.356 (3) Å	Cell parameters from 920 reflections
b = 12.590 (5) Å	θ = 2.6–25.3°
c = 14.852 (6) Å	µ = 3.24 mm−1
α = 69.787 (6)°	T = 298 K
β = 87.415 (7)°	Prism, colorless
γ = 79.243 (6)°	0.18 × 0.11 × 0.09 mm
V = 1267.8 (9) Å3

Bruker SMART CCD area-detector diffractometer	4330 independent reflections
Radiation source: fine-focus sealed tube	1413 reflections with I > 2σ(I)
graphite	Rint = 0.060
φ and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→4
Tmin = 0.594, Tmax = 0.759	k = −14→14
6454 measured reflections	l = −17→16

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.073	H-atom parameters constrained
wR(F2) = 0.146	w = 1/[σ2(Fo2) + (0.038P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
4330 reflections	Δρmax = 0.44 e Å−3
327 parameters	Δρmin = −0.32 e Å−3
Primary atom site location: structure-invariant direct methods

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. Atom C25 is disordered over two sites, C25 and C25', for which occupation factors were refined and converged to 0.320 (18) and 0.680 (18), respectively. Atom Br2 is disordered over two sites, Br2 and Br2', for which occupation factors were refined and converged to 0.51 (4) and 0.49 (4), respectively

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	−0.42012 (15)	0.06501 (8)	1.10942 (7)	0.0968 (5)
Br2	0.153 (4)	0.9617 (10)	0.6351 (8)	0.129 (4)	0.51 (4)
Br2'	0.052 (4)	0.9718 (7)	0.6478 (10)	0.133 (4)	0.49 (4)
O1	0.0177 (8)	0.4886 (5)	0.8942 (4)	0.0710 (15)
O2	−0.2101 (7)	0.5229 (5)	0.7764 (4)	0.0800 (16)
O3	0.2839 (8)	0.3774 (4)	0.9013 (4)	0.0636 (16)
O4	−0.1776 (7)	0.4473 (4)	0.6644 (4)	0.0771 (17)
O5	0.2593 (9)	0.2562 (5)	0.5545 (4)	0.1010 (19)
O6	0.4502 (10)	0.2393 (5)	0.6762 (4)	0.0924 (17)
C1	0.1367 (14)	0.4189 (7)	0.8619 (6)	0.057 (2)
C2	−0.1683 (13)	0.5300 (8)	0.8662 (7)	0.067 (2)
C3	−0.1111 (14)	0.4561 (7)	0.7342 (7)	0.068 (2)
C4	0.0841 (11)	0.4000 (6)	0.7706 (6)	0.0578 (18)
C5	0.1176 (11)	0.2655 (6)	0.7948 (5)	0.0652 (19)
H5	0.2411	0.2357	0.8250	0.078*
C6	0.1253 (13)	0.2337 (7)	0.7058 (6)	0.084 (2)
H6A	0.0047	0.2600	0.6740	0.100*
H6B	0.1540	0.1505	0.7239	0.100*
C7	0.2707 (14)	0.2862 (7)	0.6355 (7)	0.082 (2)
C8	0.2277 (12)	0.4198 (7)	0.6086 (6)	0.081 (2)
H8A	0.3187	0.4532	0.5636	0.098*
H8B	0.1068	0.4498	0.5772	0.098*
C9	0.2306 (11)	0.4533 (6)	0.6926 (6)	0.069 (2)
H9	0.3536	0.4200	0.7227	0.083*
C10	−0.2069 (13)	0.6528 (7)	0.8562 (6)	0.106 (3)
H10A	−0.3337	0.6847	0.8365	0.158*
H10B	−0.1274	0.6932	0.8089	0.158*
H10C	−0.1845	0.6603	0.9167	0.158*
C11	−0.2822 (11)	0.4550 (6)	0.9417 (5)	0.076 (2)
H11A	−0.4112	0.4804	0.9241	0.114*
H11B	−0.2618	0.4611	1.0029	0.114*
H11C	−0.2454	0.3763	0.9454	0.114*
C12	−0.0149 (12)	0.2112 (6)	0.8688 (6)	0.0561 (19)
C13	0.0441 (12)	0.1672 (6)	0.9644 (6)	0.068 (2)
H13	0.1648	0.1672	0.9807	0.081*
C14	−0.0782 (13)	0.1233 (6)	1.0353 (6)	0.072 (2)
H14	−0.0391	0.0948	1.0993	0.087*
C15	−0.2547 (13)	0.1210 (6)	1.0128 (7)	0.064 (2)
C16	−0.3171 (11)	0.1642 (6)	0.9171 (6)	0.067 (2)
H16	−0.4377	0.1640	0.9009	0.080*
C17	−0.1928 (13)	0.2069 (6)	0.8477 (6)	0.069 (2)
H17	−0.2311	0.2340	0.7836	0.083*
C18	0.2047 (12)	0.5829 (6)	0.6711 (6)	0.061 (2)
C19	0.3090 (12)	0.6205 (7)	0.7226 (6)	0.078 (2)
H19	0.4012	0.5686	0.7645	0.094*
C20	0.2792 (13)	0.7354 (7)	0.7134 (6)	0.093 (3)
H20	0.3513	0.7617	0.7481	0.111*
C21	0.1409 (15)	0.8104 (7)	0.6517 (7)	0.085 (3)
C22	0.0427 (13)	0.7738 (7)	0.5975 (6)	0.081 (2)
H22	−0.0453	0.8257	0.5530	0.097*
C23	0.0739 (12)	0.6600 (7)	0.6087 (6)	0.072 (2)
H23	0.0037	0.6344	0.5725	0.086*
C24	0.4398 (14)	0.2316 (9)	0.5185 (7)	0.130 (3)
H24A	0.4661	0.2965	0.4645	0.156*
H24B	0.4542	0.1642	0.4994	0.156*
C25	0.5598 (15)	0.2100 (9)	0.6036 (8)	0.119 (3)	0.320 (18)
H25	0.5957	0.2858	0.5774	0.142*	0.320 (18)
C26	0.755 (3)	0.147 (3)	0.602 (2)	0.160 (9)	0.320 (18)
H26A	0.8223	0.1402	0.6583	0.240*	0.320 (18)
H26B	0.8157	0.1889	0.5459	0.240*	0.320 (18)
H26C	0.7525	0.0714	0.6009	0.240*	0.320 (18)
C25'	0.5598 (15)	0.2100 (9)	0.6036 (8)	0.119 (3)	0.680 (18)
H25'	0.6610	0.2537	0.5858	0.142*	0.680 (18)
C26'	0.633 (3)	0.0856 (14)	0.6492 (12)	0.201 (8)	0.680 (18)
H26D	0.6963	0.0725	0.7082	0.302*	0.680 (18)
H26E	0.7168	0.0596	0.6068	0.302*	0.680 (18)
H26F	0.5318	0.0441	0.6624	0.302*	0.680 (18)

	U11	U22	U33	U12	U13	U23
Br1	0.0912 (9)	0.0934 (8)	0.1038 (8)	−0.0385 (6)	0.0252 (6)	−0.0232 (6)
Br2	0.173 (10)	0.061 (2)	0.150 (3)	−0.016 (4)	−0.045 (5)	−0.030 (2)
Br2'	0.173 (10)	0.047 (2)	0.170 (4)	−0.003 (4)	−0.049 (6)	−0.027 (2)
O1	0.065 (4)	0.081 (3)	0.077 (3)	0.006 (3)	−0.006 (3)	−0.048 (3)
O2	0.070 (4)	0.094 (3)	0.079 (3)	0.013 (3)	−0.007 (3)	−0.047 (3)
O3	0.058 (4)	0.055 (3)	0.076 (4)	−0.003 (3)	−0.012 (3)	−0.022 (3)
O4	0.070 (4)	0.078 (4)	0.084 (4)	−0.002 (3)	−0.025 (3)	−0.032 (3)
O5	0.110 (4)	0.106 (4)	0.085 (4)	0.006 (3)	0.006 (3)	−0.043 (3)
O6	0.106 (4)	0.095 (4)	0.086 (4)	−0.005 (3)	0.007 (3)	−0.049 (3)
C1	0.059 (4)	0.055 (4)	0.066 (4)	−0.015 (4)	0.003 (4)	−0.028 (3)
C2	0.059 (5)	0.078 (5)	0.072 (5)	0.008 (5)	−0.022 (5)	−0.042 (4)
C3	0.075 (4)	0.060 (4)	0.074 (4)	−0.017 (4)	−0.005 (4)	−0.027 (4)
C4	0.059 (4)	0.054 (3)	0.069 (4)	−0.012 (3)	0.003 (3)	−0.031 (3)
C5	0.073 (4)	0.062 (4)	0.072 (4)	−0.014 (3)	0.004 (4)	−0.037 (3)
C6	0.095 (4)	0.070 (4)	0.087 (4)	−0.008 (4)	0.002 (4)	−0.032 (4)
C7	0.094 (5)	0.081 (4)	0.078 (5)	0.001 (4)	0.005 (4)	−0.046 (4)
C8	0.090 (4)	0.077 (4)	0.078 (4)	−0.016 (4)	0.001 (4)	−0.028 (4)
C9	0.080 (4)	0.060 (4)	0.074 (4)	−0.018 (3)	0.006 (4)	−0.028 (3)
C10	0.107 (7)	0.088 (6)	0.116 (7)	0.019 (6)	−0.015 (6)	−0.044 (6)
C11	0.067 (6)	0.090 (6)	0.082 (6)	−0.012 (5)	−0.002 (5)	−0.045 (5)
C12	0.055 (4)	0.054 (4)	0.072 (4)	−0.016 (4)	0.001 (4)	−0.035 (3)
C13	0.063 (5)	0.061 (4)	0.080 (5)	−0.015 (4)	0.002 (4)	−0.024 (4)
C14	0.074 (6)	0.062 (4)	0.082 (5)	−0.016 (4)	0.003 (5)	−0.024 (4)
C15	0.063 (5)	0.056 (4)	0.079 (5)	−0.024 (4)	0.004 (5)	−0.026 (4)
C16	0.057 (5)	0.066 (5)	0.089 (6)	−0.034 (4)	0.003 (5)	−0.028 (4)
C17	0.081 (5)	0.061 (4)	0.071 (4)	−0.016 (4)	−0.007 (4)	−0.027 (4)
C18	0.072 (4)	0.053 (4)	0.064 (4)	−0.016 (4)	−0.003 (4)	−0.026 (3)
C19	0.085 (5)	0.064 (4)	0.089 (5)	−0.027 (4)	−0.012 (4)	−0.021 (4)
C20	0.108 (6)	0.064 (5)	0.104 (5)	−0.025 (5)	−0.037 (5)	−0.017 (5)
C21	0.106 (6)	0.045 (4)	0.101 (6)	−0.021 (5)	−0.022 (5)	−0.013 (4)
C22	0.098 (6)	0.049 (4)	0.088 (5)	−0.010 (4)	−0.030 (5)	−0.011 (4)
C23	0.083 (5)	0.057 (4)	0.075 (4)	−0.021 (4)	−0.009 (4)	−0.016 (4)
C24	0.113 (6)	0.148 (6)	0.118 (6)	0.004 (6)	0.001 (6)	−0.044 (5)
C25	0.106 (5)	0.123 (5)	0.106 (5)	0.021 (5)	0.010 (4)	−0.037 (4)
C26	0.156 (15)	0.138 (14)	0.150 (14)	0.013 (14)	0.011 (14)	−0.026 (13)
C25'	0.106 (5)	0.123 (5)	0.106 (5)	0.021 (5)	0.010 (4)	−0.037 (4)
C26'	0.179 (13)	0.184 (12)	0.180 (12)	0.009 (11)	0.044 (11)	−0.011 (11)

Br1—C15	1.870 (8)	C11—H11A	0.9600
Br2—C21	1.853 (12)	C11—H11B	0.9600
Br2'—C21	1.997 (15)	C11—H11C	0.9600
O1—C1	1.316 (9)	C12—C17	1.374 (10)
O1—C2	1.397 (9)	C12—C13	1.391 (10)
O2—C3	1.313 (9)	C13—C14	1.386 (9)
O2—C2	1.419 (8)	C13—H13	0.9300
O3—C1	1.193 (9)	C14—C15	1.363 (10)
O4—C3	1.213 (9)	C14—H14	0.9300
O5—C7	1.390 (8)	C15—C16	1.400 (10)
O5—C24	1.428 (9)	C16—C17	1.380 (9)
O6—C7	1.411 (9)	C16—H16	0.9300
O6—C25	1.426 (9)	C17—H17	0.9300
C1—C4	1.534 (10)	C18—C23	1.355 (10)
C2—C10	1.475 (10)	C18—C19	1.356 (10)
C2—C11	1.525 (10)	C19—C20	1.381 (10)
C3—C4	1.510 (11)	C19—H19	0.9300
C4—C5	1.577 (9)	C20—C21	1.376 (11)
C4—C9	1.604 (9)	C20—H20	0.9300
C5—C12	1.503 (9)	C21—C22	1.347 (10)
C5—C6	1.504 (9)	C22—C23	1.360 (10)
C5—H5	0.9800	C22—H22	0.9300
C6—C7	1.535 (10)	C23—H23	0.9300
C6—H6A	0.9700	C24—C25	1.492 (10)
C6—H6B	0.9700	C24—H24A	0.9700
C7—C8	1.562 (10)	C24—H24B	0.9700
C8—C9	1.450 (9)	C25—C26	1.512 (16)
C8—H8A	0.9700	C25—H25	0.9800
C8—H8B	0.9700	C26—H26A	0.9600
C9—C18	1.526 (9)	C26—H26B	0.9600
C9—H9	0.9800	C26—H26C	0.9600
C10—H10A	0.9600	C26'—H26D	0.9600
C10—H10B	0.9600	C26'—H26E	0.9600
C10—H10C	0.9600	C26'—H26F	0.9600
C1—O1—C2	126.5 (8)	H11A—C11—H11C	109.5
C3—O2—C2	126.0 (7)	H11B—C11—H11C	109.5
C7—O5—C24	110.3 (8)	C17—C12—C13	118.4 (8)
C7—O6—C25	105.9 (8)	C17—C12—C5	123.7 (8)
O3—C1—O1	119.5 (9)	C13—C12—C5	117.8 (8)
O3—C1—C4	122.3 (9)	C14—C13—C12	119.5 (8)
O1—C1—C4	118.1 (8)	C14—C13—H13	120.3
O1—C2—O2	113.3 (7)	C12—C13—H13	120.3
O1—C2—C10	106.9 (8)	C15—C14—C13	121.1 (9)
O2—C2—C10	107.4 (7)	C15—C14—H14	119.4
O1—C2—C11	107.3 (7)	C13—C14—H14	119.4
O2—C2—C11	107.5 (7)	C14—C15—C16	120.5 (8)
C10—C2—C11	114.8 (8)	C14—C15—Br1	120.7 (8)
O4—C3—O2	118.2 (10)	C16—C15—Br1	118.8 (7)
O4—C3—C4	122.9 (9)	C17—C16—C15	117.4 (8)
O2—C3—C4	118.8 (9)	C17—C16—H16	121.3
C3—C4—C1	114.0 (8)	C15—C16—H16	121.3
C3—C4—C5	111.8 (7)	C12—C17—C16	123.0 (9)
C1—C4—C5	106.2 (6)	C12—C17—H17	118.5
C3—C4—C9	110.4 (7)	C16—C17—H17	118.5
C1—C4—C9	104.9 (6)	C23—C18—C19	119.1 (8)
C5—C4—C9	109.2 (6)	C23—C18—C9	123.1 (8)
C12—C5—C6	114.8 (6)	C19—C18—C9	117.7 (8)
C12—C5—C4	111.2 (6)	C18—C19—C20	120.4 (9)
C6—C5—C4	112.0 (6)	C18—C19—H19	119.8
C12—C5—H5	106.0	C20—C19—H19	119.8
C6—C5—H5	106.0	C21—C20—C19	118.7 (9)
C4—C5—H5	106.0	C21—C20—H20	120.6
C5—C6—C7	112.4 (7)	C19—C20—H20	120.6
C5—C6—H6A	109.1	C22—C21—C20	120.7 (8)
C7—C6—H6A	109.1	C22—C21—Br2	126.7 (9)
C5—C6—H6B	109.1	C20—C21—Br2	111.0 (10)
C7—C6—H6B	109.1	C22—C21—Br2'	115.6 (9)
H6A—C6—H6B	107.9	C20—C21—Br2'	123.3 (9)
O5—C7—O6	108.0 (7)	Br2—C21—Br2'	22.3 (3)
O5—C7—C6	107.4 (8)	C21—C22—C23	119.1 (9)
O6—C7—C6	110.3 (8)	C21—C22—H22	120.4
O5—C7—C8	110.5 (7)	C23—C22—H22	120.4
O6—C7—C8	111.3 (8)	C18—C23—C22	121.8 (9)
C6—C7—C8	109.1 (7)	C18—C23—H23	119.1
C9—C8—C7	111.6 (7)	C22—C23—H23	119.1
C9—C8—H8A	109.3	O5—C24—C25	101.7 (8)
C7—C8—H8A	109.3	O5—C24—H24A	111.4
C9—C8—H8B	109.3	C25—C24—H24A	111.4
C7—C8—H8B	109.3	O5—C24—H24B	111.4
H8A—C8—H8B	108.0	C25—C24—H24B	111.4
C8—C9—C18	114.6 (7)	H24A—C24—H24B	109.3
C8—C9—C4	112.0 (6)	O6—C25—C24	109.5 (9)
C18—C9—C4	109.8 (6)	O6—C25—C26	133.7 (15)
C8—C9—H9	106.6	C24—C25—C26	116.0 (13)
C18—C9—H9	106.6	O6—C25—H25	93.0
C4—C9—H9	106.6	C24—C25—H25	93.0
C2—C10—H10A	109.5	C26—C25—H25	93.0
C2—C10—H10B	109.5	C25—C26—H26A	109.5
H10A—C10—H10B	109.5	C25—C26—H26B	109.5
C2—C10—H10C	109.5	H26A—C26—H26B	109.5
H10A—C10—H10C	109.5	C25—C26—H26C	109.5
H10B—C10—H10C	109.5	H26A—C26—H26C	109.5
C2—C11—H11A	109.5	H26B—C26—H26C	109.5
C2—C11—H11B	109.5	H26D—C26'—H26E	109.5
H11A—C11—H11B	109.5	H26D—C26'—H26F	109.5
C2—C11—H11C	109.5	H26E—C26'—H26F	109.5

D—H···A	D—H	H···A	D···A	D—H···A
C23—H23···O5i	0.93	2.60	3.286 (2)	131

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C23—H23⋯O5i	0.93	2.60	3.286 (2)	131

Symmetry code: (i) .