7-Bromo-9-(2-hy-droxy-4,4-dimethyl-6-oxocyclo-hex-1-en-1-yl)-3,3-dimethyl-2,3,4,9-tetra-hydro-1H-xanthen-1-one.

In the xanthene ring system of the title compound, C(23)H(25)BrO(4), the 4H-pyran ring is almost planar [maximum deviation = 0.040 (3) Å] and the cyclo-hexene ring adopts a sofa conformation. The cyclo-hexene ring attached to the xanthene system is puckered [Q(T) = 0.427 (3) Å, θ = 55.0 (4) ° and ϕ = 164.4 (6) °]. In the crystal, mol-ecules are linked to each other by O-H⋯O and C-H⋯O hydrogen bonds.

Related literature

For the biological and pharmaceutical properties of xanthenes, see: Mohamed et al. (2012 ▶); Hilderbrand & Weissleder (2007 ▶); Shchekotikhin & Nikolaeva (2006 ▶); Fan et al. (2005 ▶). For related structures, see: Abdelhamid et al. (2011 ▶); Mohamed et al. (2011 ▶); Reddy et al. (2009 ▶); Çelik et al. (2009 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C23H25BrO4

M = 445.33

Orthorhombic,

a = 15.6869 (4) Å

b = 11.0215 (2) Å

c = 23.0217 (16) Å

V = 3980.3 (3) Å3

Z = 8

Cu Kα radiation

μ = 3.04 mm−1

T = 150 K

0.12 × 0.08 × 0.02 mm

Data collection

Rigaku RAPID II diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2001) ▶ T min = 0.712, T max = 0.942

17325 measured reflections

3507 independent reflections

2728 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.107

S = 1.07

3507 reflections

260 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.46 e Å−3

Δρmin = −0.49 e Å−3

Data collection: CrystalClear (Rigaku, 2001) ▶; cell refinement: CrystalClear; data reduction: CrystalClear; 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: WinGX (Farrugia, 1999 ▶) and PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812021034/hg5218sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812021034/hg5218Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812021034/hg5218Isup3.cml

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

C23H25BrO4	F(000) = 1840
Mr = 445.33	Dx = 1.486 Mg m−3
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 18929 reflections
a = 15.6869 (4) Å	θ = 1–66°
b = 11.0215 (2) Å	µ = 3.04 mm−1
c = 23.0217 (16) Å	T = 150 K
V = 3980.3 (3) Å3	Needle, yellow
Z = 8	0.12 × 0.08 × 0.02 mm

Rigaku RAPID II diffractometer	2728 reflections with I > 2σ(I)
Confocal optics monochromator	Rint = 0.044
ω scans	θmax = 66.6°, θmin = 3.8°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2001)	h = −9→18
Tmin = 0.712, Tmax = 0.942	k = −13→10
17325 measured reflections	l = −27→24
3507 independent reflections

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0414P)2 + 5.2275P] where P = (Fo2 + 2Fc2)/3
3507 reflections	(Δ/σ)max < 0.001
260 parameters	Δρmax = 0.46 e Å−3
1 restraint	Δρmin = −0.49 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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	0.07678 (2)	0.50005 (3)	0.19670 (1)	0.0308 (1)
O1	0.01721 (13)	0.28166 (19)	−0.03953 (8)	0.0236 (6)
O2	−0.16483 (15)	−0.0333 (2)	0.02080 (10)	0.0333 (8)
O3	−0.08661 (14)	0.0562 (2)	0.16973 (10)	0.0344 (8)
O4	−0.20527 (13)	0.3144 (2)	0.03091 (9)	0.0277 (7)
C1	−0.00638 (18)	0.2718 (3)	0.06462 (13)	0.0199 (9)
C2	0.01035 (19)	0.3253 (3)	0.11834 (13)	0.0242 (10)
C3	0.06030 (19)	0.4281 (3)	0.12230 (13)	0.0257 (10)
C4	0.0976 (2)	0.4792 (3)	0.07358 (14)	0.0269 (10)
C5	0.08353 (19)	0.4256 (3)	0.02032 (14)	0.0251 (10)
C6	0.03110 (18)	0.3246 (3)	0.01653 (12)	0.0206 (9)
C7	−0.04024 (18)	0.1897 (3)	−0.04743 (13)	0.0206 (9)
C8	−0.05102 (19)	0.1632 (3)	−0.11080 (12)	0.0229 (9)
C9	−0.13785 (19)	0.1051 (3)	−0.12419 (13)	0.0261 (10)
C10	−0.1512 (2)	0.0005 (3)	−0.08121 (13)	0.0250 (10)
C11	−0.13510 (19)	0.0305 (3)	−0.01845 (13)	0.0242 (9)
C12	−0.07972 (18)	0.1326 (3)	−0.00369 (13)	0.0196 (9)
C13	−0.06495 (18)	0.1619 (3)	0.05977 (12)	0.0198 (9)
C14	−0.14483 (18)	0.1801 (3)	0.09634 (12)	0.0215 (9)
C15	−0.14520 (19)	0.1221 (3)	0.15319 (13)	0.0249 (9)
C16	−0.2167 (2)	0.1536 (3)	0.19457 (13)	0.0294 (10)
C17	−0.30235 (19)	0.1796 (3)	0.16603 (13)	0.0228 (9)
C18	−0.28827 (19)	0.2733 (3)	0.11776 (13)	0.0229 (9)
C19	−0.20994 (19)	0.2527 (3)	0.08139 (13)	0.0211 (9)
C91	−0.1364 (2)	0.0560 (3)	−0.18629 (13)	0.0339 (11)
C92	−0.2094 (2)	0.1994 (3)	−0.11809 (15)	0.0306 (11)
C171	−0.3643 (2)	0.2305 (3)	0.21100 (15)	0.0341 (11)
C172	−0.3390 (2)	0.0633 (3)	0.14004 (15)	0.0315 (11)
H2	−0.01290	0.29060	0.15260	0.0290*
H4	0.13220	0.54960	0.07680	0.0320*
H4O	−0.2481 (16)	0.353 (3)	0.0282 (15)	0.0370*
H5	0.10960	0.45770	−0.01360	0.0300*
H8A	−0.00510	0.10770	−0.12360	0.0280*
H8B	−0.04550	0.23960	−0.13310	0.0280*
H10A	−0.21060	−0.02860	−0.08500	0.0300*
H10B	−0.11310	−0.06720	−0.09240	0.0300*
H13	−0.03350	0.09150	0.07690	0.0240*
H16A	−0.19950	0.22580	0.21730	0.0350*
H16B	−0.22400	0.08560	0.22220	0.0350*
H17A	−0.37500	0.16920	0.24100	0.0510*
H17B	−0.41820	0.25180	0.19190	0.0510*
H17C	−0.33960	0.30300	0.22890	0.0510*
H17D	−0.34360	0.00140	0.17040	0.0470*
H17E	−0.30120	0.03400	0.10910	0.0470*
H17F	−0.39560	0.07990	0.12390	0.0470*
H18A	−0.33870	0.27310	0.09190	0.0280*
H18B	−0.28440	0.35480	0.13570	0.0280*
H91A	−0.12660	0.12300	−0.21350	0.0510*
H91B	−0.19110	0.01720	−0.19500	0.0510*
H91C	−0.09040	−0.00370	−0.19010	0.0510*
H92A	−0.19830	0.26770	−0.14430	0.0460*
H92B	−0.21150	0.22870	−0.07790	0.0460*
H92C	−0.26410	0.16200	−0.12820	0.0460*

	U11	U22	U33	U12	U13	U23
Br1	0.0299 (2)	0.0320 (2)	0.0305 (2)	−0.0014 (2)	−0.0083 (1)	−0.0056 (1)
O1	0.0219 (11)	0.0251 (12)	0.0237 (10)	−0.0080 (10)	0.0012 (9)	−0.0007 (9)
O2	0.0342 (13)	0.0301 (13)	0.0356 (13)	−0.0122 (11)	0.0017 (11)	0.0040 (10)
O3	0.0290 (12)	0.0449 (16)	0.0292 (12)	0.0110 (12)	0.0030 (10)	0.0121 (11)
O4	0.0230 (11)	0.0304 (14)	0.0298 (11)	0.0080 (10)	0.0034 (10)	0.0097 (10)
C1	0.0140 (14)	0.0170 (16)	0.0286 (15)	0.0020 (12)	−0.0039 (12)	0.0004 (12)
C2	0.0201 (15)	0.0278 (19)	0.0246 (16)	0.0025 (14)	−0.0041 (13)	0.0000 (13)
C3	0.0203 (15)	0.0274 (19)	0.0294 (16)	0.0031 (14)	−0.0072 (13)	−0.0052 (14)
C4	0.0175 (15)	0.027 (2)	0.0361 (18)	−0.0034 (14)	−0.0038 (13)	0.0018 (14)
C5	0.0194 (15)	0.0262 (19)	0.0298 (16)	−0.0042 (14)	−0.0012 (13)	0.0005 (14)
C6	0.0146 (14)	0.0227 (17)	0.0244 (15)	−0.0016 (13)	−0.0005 (12)	−0.0015 (13)
C7	0.0156 (14)	0.0189 (17)	0.0274 (15)	0.0018 (13)	−0.0022 (12)	−0.0021 (13)
C8	0.0197 (15)	0.0247 (18)	0.0244 (15)	−0.0020 (14)	0.0010 (12)	−0.0014 (13)
C9	0.0212 (15)	0.0275 (19)	0.0295 (16)	−0.0036 (14)	−0.0035 (13)	−0.0022 (14)
C10	0.0208 (16)	0.0229 (18)	0.0312 (17)	−0.0041 (14)	−0.0024 (13)	−0.0030 (13)
C11	0.0196 (15)	0.0231 (18)	0.0299 (16)	−0.0008 (14)	−0.0018 (13)	0.0015 (13)
C12	0.0153 (14)	0.0169 (16)	0.0266 (15)	−0.0001 (12)	0.0009 (12)	0.0002 (12)
C13	0.0157 (14)	0.0202 (17)	0.0235 (15)	0.0012 (13)	−0.0020 (12)	0.0029 (12)
C14	0.0170 (15)	0.0218 (17)	0.0256 (15)	−0.0004 (13)	−0.0034 (12)	0.0032 (13)
C15	0.0212 (15)	0.0271 (18)	0.0264 (16)	0.0006 (15)	−0.0017 (13)	0.0043 (13)
C16	0.0242 (17)	0.039 (2)	0.0250 (16)	0.0009 (16)	0.0011 (13)	0.0027 (14)
C17	0.0196 (15)	0.0239 (18)	0.0248 (15)	0.0030 (13)	0.0020 (13)	0.0031 (13)
C18	0.0201 (15)	0.0237 (18)	0.0250 (16)	0.0023 (14)	0.0002 (13)	0.0018 (13)
C19	0.0219 (15)	0.0185 (16)	0.0229 (15)	−0.0033 (13)	0.0002 (13)	0.0032 (12)
C91	0.038 (2)	0.034 (2)	0.0298 (17)	−0.0031 (18)	−0.0031 (15)	−0.0053 (15)
C92	0.0225 (16)	0.031 (2)	0.0384 (19)	0.0004 (15)	−0.0053 (14)	0.0039 (15)
C171	0.0276 (18)	0.040 (2)	0.0347 (18)	0.0081 (17)	0.0074 (15)	0.0039 (16)
C172	0.0234 (17)	0.031 (2)	0.0400 (19)	−0.0016 (16)	−0.0006 (14)	0.0069 (16)

Br1—C3	1.905 (3)	C17—C18	1.533 (4)
O1—C6	1.392 (3)	C17—C172	1.527 (5)
O1—C7	1.368 (4)	C17—C171	1.527 (4)
O2—C11	1.236 (4)	C18—C19	1.504 (4)
O3—C15	1.232 (4)	C2—H2	0.9500
O4—C19	1.349 (4)	C4—H4	0.9500
O4—H4O	0.80 (3)	C5—H5	0.9500
C1—C6	1.382 (4)	C8—H8A	0.9900
C1—C13	1.524 (4)	C8—H8B	0.9900
C1—C2	1.395 (4)	C10—H10A	0.9900
C2—C3	1.381 (5)	C10—H10B	0.9900
C3—C4	1.385 (4)	C13—H13	1.0000
C4—C5	1.379 (5)	C16—H16A	0.9900
C5—C6	1.387 (4)	C16—H16B	0.9900
C7—C12	1.339 (4)	C18—H18A	0.9900
C7—C8	1.497 (4)	C18—H18B	0.9900
C8—C9	1.536 (4)	C91—H91A	0.9800
C9—C91	1.529 (4)	C91—H91B	0.9800
C9—C92	1.536 (4)	C91—H91C	0.9800
C9—C10	1.534 (4)	C92—H92A	0.9800
C10—C11	1.504 (4)	C92—H92B	0.9800
C11—C12	1.462 (4)	C92—H92C	0.9800
C12—C13	1.514 (4)	C171—H17A	0.9800
C13—C14	1.523 (4)	C171—H17B	0.9800
C14—C15	1.457 (4)	C171—H17C	0.9800
C14—C19	1.342 (4)	C172—H17D	0.9800
C15—C16	1.512 (4)	C172—H17E	0.9800
C16—C17	1.523 (4)	C172—H17F	0.9800
C6—O1—C7	118.6 (2)	C3—C2—H2	120.00
C19—O4—H4O	107 (2)	C3—C4—H4	121.00
C2—C1—C13	120.9 (3)	C5—C4—H4	121.00
C6—C1—C13	122.2 (3)	C4—C5—H5	120.00
C2—C1—C6	116.9 (3)	C6—C5—H5	120.00
C1—C2—C3	120.8 (3)	C7—C8—H8A	109.00
Br1—C3—C4	120.1 (2)	C7—C8—H8B	109.00
C2—C3—C4	121.3 (3)	C9—C8—H8A	109.00
Br1—C3—C2	118.6 (2)	C9—C8—H8B	109.00
C3—C4—C5	118.6 (3)	H8A—C8—H8B	108.00
C4—C5—C6	119.7 (3)	C9—C10—H10A	108.00
O1—C6—C1	122.2 (3)	C9—C10—H10B	108.00
O1—C6—C5	115.1 (3)	C11—C10—H10A	108.00
C1—C6—C5	122.7 (3)	C11—C10—H10B	108.00
O1—C7—C12	123.6 (3)	H10A—C10—H10B	108.00
C8—C7—C12	126.1 (3)	C1—C13—H13	107.00
O1—C7—C8	110.4 (2)	C12—C13—H13	107.00
C7—C8—C9	112.1 (2)	C14—C13—H13	107.00
C8—C9—C10	107.8 (2)	C15—C16—H16A	108.00
C8—C9—C91	108.8 (2)	C15—C16—H16B	108.00
C10—C9—C91	109.8 (3)	C17—C16—H16A	108.00
C10—C9—C92	110.5 (3)	C17—C16—H16B	109.00
C91—C9—C92	109.6 (3)	H16A—C16—H16B	107.00
C8—C9—C92	110.3 (3)	C17—C18—H18A	109.00
C9—C10—C11	115.6 (3)	C17—C18—H18B	109.00
O2—C11—C10	120.9 (3)	C19—C18—H18A	109.00
C10—C11—C12	119.5 (3)	C19—C18—H18B	109.00
O2—C11—C12	119.5 (3)	H18A—C18—H18B	108.00
C7—C12—C11	117.5 (3)	C9—C91—H91A	109.00
C11—C12—C13	118.7 (3)	C9—C91—H91B	109.00
C7—C12—C13	123.7 (3)	C9—C91—H91C	109.00
C1—C13—C12	109.4 (2)	H91A—C91—H91B	110.00
C1—C13—C14	110.5 (3)	H91A—C91—H91C	109.00
C12—C13—C14	115.8 (2)	H91B—C91—H91C	109.00
C13—C14—C15	116.3 (3)	C9—C92—H92A	109.00
C13—C14—C19	124.3 (3)	C9—C92—H92B	109.00
C15—C14—C19	119.3 (3)	C9—C92—H92C	109.00
O3—C15—C16	119.6 (3)	H92A—C92—H92B	110.00
C14—C15—C16	117.9 (3)	H92A—C92—H92C	109.00
O3—C15—C14	122.3 (3)	H92B—C92—H92C	109.00
C15—C16—C17	115.2 (2)	C17—C171—H17A	109.00
C16—C17—C171	109.8 (2)	C17—C171—H17B	109.00
C16—C17—C172	110.1 (3)	C17—C171—H17C	109.00
C16—C17—C18	108.2 (2)	H17A—C171—H17B	109.00
C18—C17—C172	109.6 (3)	H17A—C171—H17C	109.00
C171—C17—C172	109.5 (3)	H17B—C171—H17C	110.00
C18—C17—C171	109.6 (3)	C17—C172—H17D	109.00
C17—C18—C19	114.8 (3)	C17—C172—H17E	109.00
O4—C19—C18	116.6 (3)	C17—C172—H17F	109.00
C14—C19—C18	124.7 (3)	H17D—C172—H17E	109.00
O4—C19—C14	118.7 (3)	H17D—C172—H17F	110.00
C1—C2—H2	120.00	H17E—C172—H17F	109.00
C7—O1—C6—C5	−173.8 (3)	C9—C10—C11—O2	160.4 (3)
C6—O1—C7—C8	175.6 (2)	C9—C10—C11—C12	−23.0 (4)
C7—O1—C6—C1	4.8 (4)	O2—C11—C12—C7	171.7 (3)
C6—O1—C7—C12	−4.8 (4)	O2—C11—C12—C13	−3.8 (4)
C6—C1—C2—C3	1.7 (4)	C10—C11—C12—C7	−5.0 (4)
C13—C1—C2—C3	−177.0 (3)	C10—C11—C12—C13	179.5 (3)
C2—C1—C13—C12	173.4 (3)	C7—C12—C13—C1	5.4 (4)
C2—C1—C13—C14	44.7 (4)	C7—C12—C13—C14	131.1 (3)
C6—C1—C13—C12	−5.3 (4)	C11—C12—C13—C1	−179.4 (3)
C6—C1—C13—C14	−134.0 (3)	C11—C12—C13—C14	−53.7 (4)
C2—C1—C6—O1	−178.1 (3)	C1—C13—C14—C15	−98.9 (3)
C2—C1—C6—C5	0.4 (5)	C1—C13—C14—C19	75.5 (4)
C13—C1—C6—O1	0.6 (5)	C12—C13—C14—C15	135.9 (3)
C13—C1—C6—C5	179.1 (3)	C12—C13—C14—C19	−49.6 (4)
C1—C2—C3—Br1	177.5 (2)	C13—C14—C15—O3	−4.1 (5)
C1—C2—C3—C4	−2.1 (5)	C13—C14—C15—C16	170.6 (3)
Br1—C3—C4—C5	−179.3 (2)	C19—C14—C15—O3	−178.8 (3)
C2—C3—C4—C5	0.4 (5)	C19—C14—C15—C16	−4.1 (4)
C3—C4—C5—C6	1.7 (5)	C13—C14—C19—O4	−0.2 (5)
C4—C5—C6—O1	176.5 (3)	C13—C14—C19—C18	−178.7 (3)
C4—C5—C6—C1	−2.1 (5)	C15—C14—C19—O4	174.1 (3)
O1—C7—C8—C9	−155.2 (3)	C15—C14—C19—C18	−4.4 (5)
C12—C7—C8—C9	25.3 (4)	O3—C15—C16—C17	−151.6 (3)
O1—C7—C12—C11	−175.9 (3)	C14—C15—C16—C17	33.6 (4)
O1—C7—C12—C13	−0.7 (5)	C15—C16—C17—C18	−50.9 (4)
C8—C7—C12—C11	3.5 (5)	C15—C16—C17—C171	−170.5 (3)
C8—C7—C12—C13	178.8 (3)	C15—C16—C17—C172	68.9 (3)
C7—C8—C9—C10	−48.8 (3)	C16—C17—C18—C19	42.1 (3)
C7—C8—C9—C91	−167.8 (3)	C171—C17—C18—C19	161.8 (3)
C7—C8—C9—C92	71.9 (3)	C172—C17—C18—C19	−78.0 (3)
C8—C9—C10—C11	48.9 (3)	C17—C18—C19—O4	165.1 (3)
C91—C9—C10—C11	167.2 (3)	C17—C18—C19—C14	−16.3 (4)
C92—C9—C10—C11	−71.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O2i	0.80 (3)	1.86 (3)	2.650 (3)	170 (3)
C8—H8A···O3ii	0.99	2.54	3.514 (4)	167
C13—H13···O3	1.00	2.33	2.807 (4)	108

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4O⋯O2i	0.80 (3)	1.86 (3)	2.650 (3)	170 (3)
C8—H8A⋯O3ii	0.99	2.54	3.514 (4)	167

Symmetry codes: (i) ; (ii) .