7,14-Bis(4-bromo­phen­yl)-2,11,11-trimethyl-1,4,10,12-tetra­oxa­dispiro­[4.2.5.2]penta­decane-9,13-dione

Peng, J.; Ma, N.; Zhang, G.

doi:10.1107/S1600536809014251

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1151

doi:10.1107/S1600536809014251

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7,14-Bis(4-bromophenyl)-2,11,11-trimethyl-1,4,10,12-tetraoxadispiro[4.2.5.2]pentadecane-9,13-dione

Ju-hua Peng,^a ^* Ning Ma ^b and Ge Zhang ^b

^aLianyungang Teachers' College, Lianyungang 222006, People's Republic of China, and ^bSchool of Chemistry and Chemical Engineering, Xuzhou Normal University, Xuzhou 221116, People's Republic of China
^*Correspondence e-mail: mollingmn1984@yahoo.com.cn

(Received 10 April 2009; accepted 16 April 2009; online 30 April 2009)

In the molecule of the title compound, C₂₆H₂₆Br₂O₆, the cyclohexane 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 intermolecular C—H⋯O interactions link the molecules into centrosymmetric dimers, forming R₂²(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_r = 594.29
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.073
wR(F²) = 0.146
S = 1.00
4330 reflections
327 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.32 e Å⁻³

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) -x, -y+1, -z+1.

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.

Supporting information

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

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

checkCIF report

Comment top

Over the past few decades, Meldrum's acid (2,2-dimethyl-1,3-dioxane-4,6-dione) (Tietze & Beifuss, 1993; Tietze et al., 2001) has been used as a versatile organic reagent (Ramachary et al., 2003; Muller et al., 2005) and its derivatives are very useful building blocks in synthetic organic chemistry (Davidson & Bernhard, 1948; Meldrum, 1908). Spirocyclic compounds including a Meldrum's acid unit are attractive intermediates in the syntheses of natural products and in medicinal chemistry. Thus, the synthesis of new highly substituted spiro ring system with a Meldrum's acid unit has attracted widespread attention (Ramachary & Barbas, 2004; Chande & Khanwelkar, 2005). We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C4-C9) is not planar, having total puckering amplitude, Q_T, of 0.576 (3) Å and chair conformation [ϕ = -150.30 (3) and θ = 3.77 (3) °] (Cremer & Pople, 1975). Rings D (C12-C17) and E (C18-C23) are, of course, planar, and they are oriented at a dihedral angle of D/E = 77.21 (3)°. Rings B (O1/O2/C1-C4) and C (O5/O6/C7/C24/C25) adopt envelope conformations, with atoms C2 and O5 displaced by -0.184 (3) and -0.291 (3) Å from the planes of the other rings atoms.

In the crystal structure, weak intermolecular C-H···O interactions (Table 1) link the molecules into centrosymmetric dimers forming R₂²(14) ring motifs (Fig. 2) (Bernstein et al., 1995), in which they may be effective in the stabilization of the structure.

Related literature top

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 top

The title compound was prepared by the reaction of 1,2-diarylidenehydrazine (2 mmol), Meldrum's acid (5 mmol), HOAc (4 mL) and (S)-1,2-propanediol (8 ml). Upon completion, the reaction mixture was cooled to room temperature, and introduced into water. The solid was collected by washing with water. The combined solid was purified by ethanol.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

7,14-Bis(4-bromophenyl)-2,11,11-trimethyl-1,4,10,12- tetraoxadispiro[4.2.5.2]pentadecane-9,13-dione top

Crystal data top

C₂₆H₂₆Br₂O₆	Z = 2
M_r = 594.29	F(000) = 600
Triclinic, P1	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.038P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
4330 reflections	Δρ_max = 0.44 e Å⁻³
327 parameters	Δρ_min = −0.32 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

C₂₆H₂₆Br₂O₆	γ = 79.243 (6)°
M_r = 594.29	V = 1267.8 (9) Å³
Triclinic, P1	Z = 2
a = 7.356 (3) Å	Mo Kα radiation
b = 12.590 (5) Å	µ = 3.24 mm⁻¹
c = 14.852 (6) Å	T = 298 K
α = 69.787 (6)°	0.18 × 0.11 × 0.09 mm
β = 87.415 (7)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4330 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1413 reflections with I > 2σ(I)
T_min = 0.594, T_max = 0.759	R_int = 0.060
6454 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.073	327 parameters
wR(F²) = 0.146	H-atom parameters constrained
S = 1.00	Δρ_max = 0.44 e Å⁻³
4330 reflections	Δρ_min = −0.32 e Å⁻³

Special details top

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

Refinement. 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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₆H₂₆Br₂O₆
M_r	594.29
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.356 (3), 12.590 (5), 14.852 (6)
α, β, γ (°)	69.787 (6), 87.415 (7), 79.243 (6)
V (Å³)	1267.8 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.24
Crystal size (mm)	0.18 × 0.11 × 0.09

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.594, 0.759
No. of measured, independent and observed [I > 2σ(I)] reflections	6454, 4330, 1413
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.073, 0.146, 1.00
No. of reflections	4330
No. of parameters	327
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.32

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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) −x, −y+1, −z+1.

Acknowledgements

We thank the Natural Science Foundation of China (grant No. 20672090) and the Natural Science Foundation of Jiangsu Province (grant No. BK2006033).

References

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

7,14-Bis(4-bromo­phen­yl)-2,11,11-tri­methyl-1,4,10,12-tetra­oxa­di­spiro­[4.2.5.2]penta­decane-9,13-dione

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

7,14-Bis(4-bromophenyl)-2,11,11-trimethyl-1,4,10,12-tetraoxadispiro[4.2.5.2]pentadecane-9,13-dione