5-Bromo-spiro-[1,2-dioxane-4,4'-tricyclo-[4.3.1.1]undeca-ne]-3'-ol.

The title compound, C(14)H(21)BrO(3), comprises a seven- (C(7)) and three six-membered (1 × O(2)C(4) and 2 × C(6)) rings, and each adopts a conformation based on a chair. Stability to the mol-ecular structure is afforded by an intra-molecular O-H⋯Br hydrogen bond. In the crystal structure, mol-ecules are arranged into a helical supra-molecular chain along the b axis, linked by C-H⋯O inter-actions, where the O-atom acceptor is one of the dioxane O atoms. The crystal studied was found to be a racemic twin. The major component was present 94% of the time.

Related literature

For the background to endoperoxides, see: Casteel (1999 ▶); Tang et al. (2004 ▶). For the potential of simple 1,2-dioxines and ep­oxy-1,2-dioxanes as novel anti­malarial and anti­fungal agents, see: Taylor et al. (2004 ▶); Crespo et al. (2008 ▶); Macreadie et al. (2006 ▶, 2008 ▶); Avery et al. (2007 ▶). For the synthesis of related compounds, see: Robinson (2003 ▶).

Experimental

Crystal data

C14H21BrO3

M = 317.22

Monoclinic,

a = 8.6199 (7) Å

b = 6.6370 (5) Å

c = 11.7171 (9) Å

β = 105.426 (2)°

V = 646.19 (9) Å3

Z = 2

Mo Kα radiation

μ = 3.18 mm−1

T = 293 K

0.19 × 0.11 × 0.08 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.657, T max = 1

4618 measured reflections

2140 independent reflections

2063 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.094

S = 1.04

2140 reflections

167 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.77 e Å−3

Δρmin = −0.49 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: PATTY in DIRDIF92 (Beurskens et al., 1992 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809054762/hb5281sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809054762/hb5281Isup2.hkl

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

C14H21BrO3	F(000) = 328
Mr = 317.22	Dx = 1.630 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2yb	Cell parameters from 2705 reflections
a = 8.6199 (7) Å	θ = 2.5–29.5°
b = 6.6370 (5) Å	µ = 3.18 mm−1
c = 11.7171 (9) Å	T = 293 K
β = 105.426 (2)°	Block, colourless
V = 646.19 (9) Å3	0.19 × 0.11 × 0.08 mm
Z = 2

Bruker SMART CCD diffractometer	2140 independent reflections
Radiation source: fine-focus sealed tube	2063 reflections with I > 2σ(I)
graphite	Rint = 0.040
ω scans	θmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
Tmin = 0.657, Tmax = 1	k = −5→8
4618 measured reflections	l = −14→15

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0714P)2 + 0.0296P] where P = (Fo2 + 2Fc2)/3
2140 reflections	(Δ/σ)max = 0.001
167 parameters	Δρmax = 0.77 e Å−3
2 restraints	Δρmin = −0.49 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Br	0.03137 (4)	0.40212 (10)	0.92113 (2)	0.03533 (13)
O1	−0.0876 (3)	0.3711 (5)	0.5673 (2)	0.0309 (6)
O2	−0.1461 (3)	0.5051 (5)	0.6461 (3)	0.0346 (6)
O3	0.1635 (3)	0.0061 (4)	0.8367 (2)	0.0295 (6)
H3o	0.1331	0.0876	0.8811	0.044*
C1	0.1666 (4)	0.3109 (5)	0.7167 (2)	0.0183 (6)
C2	0.0084 (4)	0.2208 (5)	0.6406 (3)	0.0241 (7)
H2A	0.0326	0.1130	0.5908	0.029*
H2B	−0.0521	0.1619	0.6923	0.029*
C3	−0.0120 (4)	0.6195 (6)	0.7095 (4)	0.0313 (8)
H3A	−0.0476	0.7184	0.7593	0.038*
H3B	0.0332	0.6933	0.6534	0.038*
C4	0.1193 (4)	0.4853 (5)	0.7878 (3)	0.0227 (6)
H4	0.2159	0.5693	0.8202	0.027*
C5	0.2688 (4)	0.1354 (5)	0.7913 (3)	0.0206 (6)
C6	0.4047 (4)	0.2092 (6)	0.8964 (3)	0.0254 (7)
H6A	0.3659	0.3262	0.9317	0.031*
H6B	0.4291	0.1026	0.9564	0.031*
C7	0.5598 (4)	0.2675 (6)	0.8661 (3)	0.0259 (7)
H7	0.6410	0.3026	0.9406	0.031*
C8	0.5395 (4)	0.4492 (5)	0.7823 (3)	0.0270 (7)
H8A	0.6464	0.4966	0.7801	0.032*
H8B	0.4874	0.5584	0.8145	0.032*
C9	0.4400 (3)	0.4049 (7)	0.6548 (2)	0.0257 (6)
H9	0.4676	0.5136	0.6057	0.031*
C10	0.2557 (4)	0.4135 (7)	0.6318 (2)	0.0241 (6)
H10A	0.2098	0.3566	0.5528	0.029*
H10B	0.2258	0.5563	0.6272	0.029*
C11	0.6215 (4)	0.0862 (7)	0.8115 (3)	0.0328 (8)
H11A	0.6336	−0.0298	0.8649	0.039*
H11B	0.7268	0.1167	0.7987	0.039*
C12	0.5010 (4)	0.0371 (6)	0.6937 (3)	0.0296 (7)
H12	0.5392	−0.0842	0.6601	0.035*
C13	0.4948 (5)	0.2104 (7)	0.6087 (4)	0.0342 (9)
H13A	0.4205	0.1768	0.5321	0.041*
H13B	0.6019	0.2305	0.5965	0.041*
C14	0.3364 (4)	−0.0107 (6)	0.7144 (3)	0.0264 (7)
H14A	0.3432	−0.1445	0.7508	0.032*
H14B	0.2578	−0.0196	0.6369	0.032*

	U11	U22	U33	U12	U13	U23
Br	0.03383 (19)	0.0473 (2)	0.02721 (17)	−0.00431 (19)	0.01216 (12)	−0.00797 (18)
O1	0.0285 (10)	0.0314 (16)	0.0266 (10)	0.0015 (13)	−0.0033 (8)	0.0014 (11)
O2	0.0235 (12)	0.0337 (15)	0.0430 (15)	0.0023 (11)	0.0027 (11)	−0.0026 (12)
O3	0.0362 (14)	0.0220 (13)	0.0307 (13)	−0.0085 (11)	0.0096 (11)	0.0070 (10)
C1	0.0191 (13)	0.0172 (14)	0.0163 (12)	−0.0015 (12)	0.0005 (11)	0.0006 (11)
C2	0.0251 (15)	0.0206 (16)	0.0221 (15)	−0.0037 (14)	−0.0015 (12)	−0.0012 (12)
C3	0.0270 (17)	0.0204 (17)	0.0436 (19)	−0.0016 (14)	0.0046 (15)	−0.0023 (15)
C4	0.0210 (14)	0.0211 (14)	0.0253 (15)	−0.0039 (13)	0.0047 (12)	−0.0030 (12)
C5	0.0238 (14)	0.0177 (15)	0.0189 (13)	−0.0021 (13)	0.0029 (11)	0.0014 (11)
C6	0.0296 (16)	0.0264 (17)	0.0171 (13)	0.0002 (14)	0.0005 (12)	0.0018 (12)
C7	0.0252 (15)	0.0264 (18)	0.0218 (14)	0.0012 (14)	−0.0013 (12)	−0.0012 (13)
C8	0.0248 (14)	0.0221 (18)	0.0318 (15)	−0.0052 (12)	0.0035 (12)	−0.0022 (13)
C9	0.0252 (13)	0.0274 (15)	0.0249 (12)	−0.005 (2)	0.0075 (10)	0.0022 (19)
C10	0.0275 (13)	0.0235 (15)	0.0204 (11)	−0.0014 (17)	0.0051 (10)	0.0058 (15)
C11	0.0257 (16)	0.032 (2)	0.0355 (18)	0.0069 (15)	−0.0003 (14)	−0.0029 (16)
C12	0.0258 (16)	0.0273 (17)	0.0339 (17)	0.0035 (14)	0.0049 (14)	−0.0106 (15)
C13	0.0317 (18)	0.047 (2)	0.0264 (15)	−0.0014 (17)	0.0117 (13)	−0.0060 (16)
C14	0.0318 (16)	0.0157 (14)	0.0285 (16)	−0.0014 (14)	0.0024 (13)	−0.0049 (13)

Br—C4	1.987 (3)	C7—C11	1.524 (5)
O1—C2	1.428 (4)	C7—C8	1.535 (5)
O1—O2	1.465 (4)	C7—H7	0.9900
O2—C3	1.417 (5)	C8—C9	1.540 (4)
O3—C5	1.449 (4)	C8—H8A	0.9800
O3—H3O	0.8400	C8—H8B	0.9800
C1—C2	1.538 (4)	C9—C13	1.522 (6)
C1—C4	1.543 (5)	C9—C10	1.540 (4)
C1—C10	1.566 (4)	C9—H9	0.9900
C1—C5	1.577 (4)	C10—H10A	0.9800
C2—H2A	0.9800	C10—H10B	0.9800
C2—H2B	0.9800	C11—C12	1.526 (5)
C3—C4	1.537 (5)	C11—H11A	0.9800
C3—H3A	0.9800	C11—H11B	0.9800
C3—H3B	0.9800	C12—C13	1.513 (6)
C4—H4	0.9900	C12—C14	1.535 (5)
C5—C6	1.537 (4)	C12—H12	0.9900
C5—C14	1.539 (5)	C13—H13A	0.9800
C6—C7	1.522 (5)	C13—H13B	0.9800
C6—H6A	0.9800	C14—H14A	0.9800
C6—H6B	0.9800	C14—H14B	0.9800
C2—O1—O2	106.6 (2)	C8—C7—H7	108.2
C3—O2—O1	106.6 (3)	C7—C8—C9	114.2 (3)
C5—O3—H3O	100.1	C7—C8—H8A	108.7
C2—C1—C4	106.5 (3)	C9—C8—H8A	108.7
C2—C1—C10	108.0 (2)	C7—C8—H8B	108.7
C4—C1—C10	105.2 (3)	C9—C8—H8B	108.7
C2—C1—C5	108.2 (3)	H8A—C8—H8B	107.6
C4—C1—C5	116.4 (2)	C13—C9—C8	111.2 (3)
C10—C1—C5	112.2 (3)	C13—C9—C10	111.8 (3)
O1—C2—C1	111.1 (3)	C8—C9—C10	116.4 (3)
O1—C2—H2A	109.4	C13—C9—H9	105.5
C1—C2—H2A	109.4	C8—C9—H9	105.5
O1—C2—H2B	109.4	C10—C9—H9	105.5
C1—C2—H2B	109.4	C9—C10—C1	122.0 (3)
H2A—C2—H2B	108.0	C9—C10—H10A	106.8
O2—C3—C4	111.8 (3)	C1—C10—H10A	106.8
O2—C3—H3A	109.3	C9—C10—H10B	106.8
C4—C3—H3A	109.3	C1—C10—H10B	106.8
O2—C3—H3B	109.3	H10A—C10—H10B	106.7
C4—C3—H3B	109.3	C7—C11—C12	108.6 (3)
H3A—C3—H3B	107.9	C7—C11—H11A	110.0
C3—C4—C1	111.8 (3)	C12—C11—H11A	110.0
C3—C4—Br	104.8 (2)	C7—C11—H11B	110.0
C1—C4—Br	115.2 (2)	C12—C11—H11B	110.0
C3—C4—H4	108.3	H11A—C11—H11B	108.4
C1—C4—H4	108.3	C13—C12—C11	109.2 (3)
Br—C4—H4	108.3	C13—C12—C14	112.9 (3)
O3—C5—C6	108.2 (3)	C11—C12—C14	109.6 (3)
O3—C5—C14	102.3 (3)	C13—C12—H12	108.3
C6—C5—C14	110.1 (3)	C11—C12—H12	108.3
O3—C5—C1	109.2 (2)	C14—C12—H12	108.3
C6—C5—C1	113.8 (3)	C12—C13—C9	111.8 (3)
C14—C5—C1	112.6 (2)	C12—C13—H13A	109.3
C7—C6—C5	115.1 (3)	C9—C13—H13A	109.3
C7—C6—H6A	108.5	C12—C13—H13B	109.3
C5—C6—H6A	108.5	C9—C13—H13B	109.3
C7—C6—H6B	108.5	H13A—C13—H13B	107.9
C5—C6—H6B	108.5	C12—C14—C5	118.2 (3)
H6A—C6—H6B	107.5	C12—C14—H14A	107.8
C6—C7—C11	108.9 (3)	C5—C14—H14A	107.8
C6—C7—C8	113.0 (3)	C12—C14—H14B	107.8
C11—C7—C8	110.2 (3)	C5—C14—H14B	107.8
C6—C7—H7	108.2	H14A—C14—H14B	107.1
C11—C7—H7	108.2
C2—O1—O2—C3	71.9 (3)	C1—C5—C6—C7	−83.6 (4)
O2—O1—C2—C1	−70.2 (3)	C5—C6—C7—C11	−58.4 (4)
C4—C1—C2—O1	56.4 (3)	C5—C6—C7—C8	64.3 (4)
C10—C1—C2—O1	−56.1 (4)	C6—C7—C8—C9	−70.6 (4)
C5—C1—C2—O1	−177.8 (3)	C11—C7—C8—C9	51.5 (4)
O1—O2—C3—C4	−63.0 (4)	C7—C8—C9—C13	−47.0 (4)
O2—C3—C4—C1	52.4 (4)	C7—C8—C9—C10	82.7 (4)
O2—C3—C4—Br	−73.1 (3)	C13—C9—C10—C1	83.5 (4)
C2—C1—C4—C3	−45.5 (3)	C8—C9—C10—C1	−45.8 (6)
C10—C1—C4—C3	69.0 (3)	C2—C1—C10—C9	−142.2 (4)
C5—C1—C4—C3	−166.2 (3)	C4—C1—C10—C9	104.4 (4)
C2—C1—C4—Br	74.1 (3)	C5—C1—C10—C9	−23.0 (5)
C10—C1—C4—Br	−171.44 (19)	C6—C7—C11—C12	65.3 (4)
C5—C1—C4—Br	−46.6 (3)	C8—C7—C11—C12	−59.2 (4)
C2—C1—C5—O3	−42.1 (3)	C7—C11—C12—C13	64.5 (4)
C4—C1—C5—O3	77.7 (3)	C7—C11—C12—C14	−59.6 (4)
C10—C1—C5—O3	−161.2 (3)	C11—C12—C13—C9	−61.1 (4)
C2—C1—C5—C6	−163.1 (3)	C14—C12—C13—C9	61.2 (4)
C4—C1—C5—C6	−43.4 (4)	C8—C9—C13—C12	51.4 (4)
C10—C1—C5—C6	77.8 (4)	C10—C9—C13—C12	−80.6 (4)
C2—C1—C5—C14	70.8 (3)	C13—C12—C14—C5	−73.5 (4)
C4—C1—C5—C14	−169.5 (3)	C11—C12—C14—C5	48.5 (4)
C10—C1—C5—C14	−48.3 (3)	O3—C5—C14—C12	−154.2 (3)
O3—C5—C6—C7	154.8 (3)	C6—C5—C14—C12	−39.3 (4)
C14—C5—C6—C7	43.8 (4)	C1—C5—C14—C12	88.7 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3o···Br	0.84	2.36	3.128 (3)	153
C2—H2a···O1i	0.98	2.59	3.560 (4)	171
C14—H14b···O1i	0.98	2.56	3.513 (4)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3o⋯Br	0.84	2.36	3.128 (3)	153
C2—H2a⋯O1i	0.98	2.59	3.560 (4)	171
C14—H14b⋯O1i	0.98	2.56	3.513 (4)	165

Symmetry code: (i) .