(2R,4R)-2-Hydr-oxy-4-(2-methoxy-phen-yl)bicyclo-[3.3.1]nonan-9-one.

The title compound, C(16)H(20)O(3), contains a bicyclic ring system with two chiral centers. The crystal structure is stabilized by inter-molecular O-H⋯O hydrogen bonds. The absolute configuration was established by the stereo-selectivity of the asymmetric organocatalysis.

Related literature

A similar structure is described by Cao et al. (2007 ▶). For general background to organocatalysis, see: List et al. (2000 ▶, 2001 ▶); Notz et al. (2001 ▶).

Experimental

Crystal data

C16H20O3

M = 260.33

Orthorhombic,

a = 6.9378 (5) Å

b = 12.5291 (11) Å

c = 16.0726 (14) Å

V = 1397.1 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 296 K

0.47 × 0.32 × 0.29 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.945, T max = 0.976

13314 measured reflections

1840 independent reflections

1211 reflections with F 2 > 2σ(F 2)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.061

S = 1.00

1840 reflections

173 parameters

H-atom parameters constrained

Δρmax = 0.16 e Å−3

Δρmin = −0.13 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 2006 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶), and Larson (1970 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809028980/zl2227sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028980/zl2227Isup2.hkl

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

C16H20O3	F(000) = 560.00
Mr = 260.33	Dx = 1.238 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: P 2ac 2ab	Cell parameters from 8871 reflections
a = 6.9378 (5) Å	θ = 3.0–27.4°
b = 12.5291 (11) Å	µ = 0.08 mm−1
c = 16.0726 (14) Å	T = 296 K
V = 1397.1 (2) Å3	Chunk, colorless
Z = 4	0.47 × 0.32 × 0.29 mm

Rigaku R-AXIS RAPID diffractometer	1211 reflections with F2 > 2σ(F2)
Detector resolution: 10.00 pixels mm-1	Rint = 0.034
ω scans	θmax = 27.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→8
Tmin = 0.945, Tmax = 0.976	k = −16→16
13314 measured reflections	l = −20→20
1840 independent reflections

Refinement on F2	w = 1/[1.01σ(Fo2)]/(4Fo2)
R[F2 > 2σ(F2)] = 0.032	(Δ/σ)max < 0.001
wR(F2) = 0.061	Δρmax = 0.16 e Å−3
S = 1.00	Δρmin = −0.13 e Å−3
1840 reflections	Extinction correction: Larson (1970), equation 22
173 parameters	Extinction coefficient: 649 (27)
H-atom parameters constrained

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

	x	y	z	Uiso*/Ueq
O1	0.3084 (2)	−0.19303 (10)	0.07830 (9)	0.0638 (4)
O2	−0.1217 (2)	−0.10943 (12)	0.00114 (9)	0.0622 (4)
O3	−0.10291 (19)	0.08144 (11)	0.23327 (8)	0.0593 (4)
C1	0.1869 (2)	0.03037 (14)	0.12399 (11)	0.0390 (5)
C2	0.3817 (2)	−0.00912 (14)	0.09036 (12)	0.0457 (5)
C3	0.3617 (2)	−0.10201 (16)	0.02981 (12)	0.0476 (5)
C4	0.2100 (2)	−0.08335 (16)	−0.03793 (12)	0.0472 (5)
C5	0.2559 (3)	0.00623 (18)	−0.10098 (12)	0.0601 (6)
C6	0.2481 (3)	0.11937 (17)	−0.06523 (13)	0.0657 (7)
C7	0.0787 (3)	0.13738 (16)	−0.00841 (12)	0.0599 (6)
C8	0.0362 (2)	0.04651 (14)	0.05297 (12)	0.0433 (5)
C9	0.0240 (2)	−0.05569 (16)	0.00463 (12)	0.0440 (5)
C10	0.1996 (2)	0.12898 (14)	0.17882 (11)	0.0388 (5)
C11	0.3544 (2)	0.19787 (16)	0.17853 (12)	0.0519 (6)
C12	0.3625 (3)	0.28667 (17)	0.23012 (12)	0.0653 (7)
C13	0.2124 (3)	0.30819 (18)	0.28234 (13)	0.0632 (7)
C14	0.0528 (3)	0.24199 (16)	0.28470 (12)	0.0527 (6)
C15	0.0475 (2)	0.15310 (14)	0.23345 (12)	0.0437 (5)
C16	−0.2463 (2)	0.0914 (2)	0.29575 (13)	0.0707 (7)
H1	0.1366	−0.0270	0.1593	0.047*
H3	0.4868	−0.1155	0.0035	0.057*
H4	0.1918	−0.1502	−0.0687	0.057*
H8	−0.0897	0.0599	0.0785	0.052*
H11	0.4567	0.1845	0.1426	0.062*
H12	0.4697	0.3312	0.2291	0.078*
H13	0.2174	0.3679	0.3167	0.076*
H14	−0.0495	0.2570	0.3202	0.063*
H21	0.4604	−0.0320	0.1369	0.055*
H22	0.4448	0.0495	0.0619	0.055*
H51	0.3847	−0.0058	−0.1226	0.072*
H52	0.1634	0.0017	−0.1461	0.072*
H61	0.3655	0.1322	−0.0341	0.079*
H62	0.2399	0.1696	−0.1110	0.079*
H71	−0.0348	0.1477	−0.0427	0.072*
H72	0.1032	0.2016	0.0236	0.072*
H101	0.3263	−0.2488	0.0498	0.077*
H161	−0.3243	0.0282	0.2967	0.085*
H162	−0.1856	0.1007	0.3489	0.085*
H163	−0.3260	0.1522	0.2839	0.085*

	U11	U22	U33	U12	U13	U23
O1	0.0884 (9)	0.0367 (7)	0.0664 (9)	0.0155 (8)	0.0188 (8)	0.0031 (7)
O2	0.0536 (7)	0.0633 (10)	0.0698 (10)	−0.0144 (8)	−0.0018 (8)	−0.0159 (9)
O3	0.0580 (7)	0.0607 (9)	0.0591 (9)	−0.0141 (8)	0.0173 (7)	−0.0219 (7)
C1	0.0433 (9)	0.0327 (10)	0.0410 (10)	0.0023 (8)	0.0029 (8)	−0.0021 (8)
C2	0.0448 (10)	0.0422 (11)	0.0502 (12)	0.0061 (10)	−0.0038 (9)	−0.0003 (10)
C3	0.0494 (11)	0.0398 (11)	0.0537 (12)	0.0076 (10)	0.0110 (10)	−0.0023 (10)
C4	0.0553 (11)	0.0392 (11)	0.0472 (11)	−0.0009 (10)	0.0070 (10)	−0.0121 (9)
C5	0.0638 (13)	0.0677 (14)	0.0488 (12)	0.0024 (13)	0.0070 (11)	0.0001 (11)
C6	0.0879 (16)	0.0525 (14)	0.0566 (14)	−0.0027 (14)	−0.0052 (13)	0.0114 (12)
C7	0.0857 (15)	0.0436 (12)	0.0503 (12)	0.0147 (12)	−0.0154 (12)	−0.0024 (11)
C8	0.0421 (9)	0.0428 (11)	0.0452 (10)	0.0068 (9)	−0.0030 (9)	−0.0122 (10)
C9	0.0454 (10)	0.0447 (11)	0.0420 (11)	−0.0015 (10)	−0.0025 (9)	−0.0042 (10)
C10	0.0491 (10)	0.0333 (10)	0.0341 (9)	0.0000 (9)	−0.0037 (9)	−0.0003 (8)
C11	0.0595 (12)	0.0452 (11)	0.0509 (12)	−0.0091 (11)	0.0081 (10)	−0.0048 (10)
C12	0.0772 (14)	0.0512 (14)	0.0675 (15)	−0.0229 (13)	0.0124 (13)	−0.0159 (12)
C13	0.0856 (15)	0.0440 (13)	0.0600 (14)	−0.0115 (13)	0.0037 (13)	−0.0156 (11)
C14	0.0650 (13)	0.0442 (12)	0.0488 (12)	0.0023 (11)	0.0065 (11)	−0.0104 (10)
C15	0.0519 (11)	0.0396 (11)	0.0397 (11)	−0.0022 (9)	−0.0024 (10)	−0.0023 (10)
C16	0.0503 (12)	0.0801 (17)	0.0816 (16)	−0.0057 (13)	0.0152 (12)	−0.0221 (14)

O1—C3	1.430 (2)	O1—H101	0.846
O2—C9	1.216 (2)	C1—H1	0.980
O3—C15	1.376 (2)	C2—H21	0.970
O3—C16	1.419 (2)	C2—H22	0.970
C1—C2	1.537 (2)	C3—H3	0.980
C1—C8	1.561 (2)	C4—H4	0.980
C1—C10	1.520 (2)	C5—H51	0.970
C2—C3	1.523 (2)	C5—H52	0.970
C3—C4	1.533 (2)	C6—H61	0.970
C4—C5	1.545 (2)	C6—H62	0.970
C4—C9	1.501 (2)	C7—H71	0.970
C5—C6	1.531 (3)	C7—H72	0.970
C6—C7	1.505 (3)	C8—H8	0.980
C7—C8	1.535 (2)	C11—H11	0.930
C8—C9	1.500 (2)	C12—H12	0.930
C10—C11	1.378 (2)	C13—H13	0.930
C10—C15	1.406 (2)	C14—H14	0.930
C11—C12	1.389 (2)	C16—H161	0.960
C12—C13	1.365 (3)	C16—H162	0.960
C13—C14	1.384 (3)	C16—H163	0.960
C14—C15	1.386 (2)
C15—O3—C16	118.18 (15)	O1—C3—H3	109.1
C2—C1—C8	111.91 (14)	C2—C3—H3	109.1
C2—C1—C10	114.46 (14)	C4—C3—H3	109.1
C8—C1—C10	110.96 (14)	C3—C4—H4	108.4
C1—C2—C3	112.99 (15)	C5—C4—H4	108.4
O1—C3—C2	106.53 (15)	C9—C4—H4	108.4
O1—C3—C4	109.33 (15)	C4—C5—H51	108.1
C2—C3—C4	113.56 (16)	C4—C5—H52	108.1
C3—C4—C5	115.78 (16)	C6—C5—H51	108.1
C3—C4—C9	107.58 (15)	C6—C5—H52	108.1
C5—C4—C9	107.97 (16)	H51—C5—H52	109.5
C4—C5—C6	114.78 (17)	C5—C6—H61	108.5
C5—C6—C7	113.23 (18)	C5—C6—H62	108.5
C6—C7—C8	115.36 (16)	C7—C6—H61	108.5
C1—C8—C7	115.97 (15)	C7—C6—H62	108.5
C1—C8—C9	107.82 (15)	H61—C6—H62	109.5
C7—C8—C9	108.12 (15)	C6—C7—H71	108.0
O2—C9—C4	124.46 (18)	C6—C7—H72	108.0
O2—C9—C8	122.92 (17)	C8—C7—H71	108.0
C4—C9—C8	112.62 (15)	C8—C7—H72	108.0
C1—C10—C11	123.56 (16)	H71—C7—H72	109.5
C1—C10—C15	119.53 (16)	C1—C8—H8	108.2
C11—C10—C15	116.91 (17)	C7—C8—H8	108.2
C10—C11—C12	122.11 (19)	C9—C8—H8	108.2
C11—C12—C13	119.6 (2)	C10—C11—H11	118.9
C12—C13—C14	120.6 (2)	C12—C11—H11	118.9
C13—C14—C15	119.12 (19)	C11—C12—H12	120.2
O3—C15—C10	115.32 (16)	C13—C12—H12	120.2
O3—C15—C14	123.07 (17)	C12—C13—H13	119.7
C10—C15—C14	121.60 (17)	C14—C13—H13	119.7
C3—O1—H101	109.0	C13—C14—H14	120.4
C2—C1—H1	106.3	C15—C14—H14	120.4
C8—C1—H1	106.3	O3—C16—H161	109.5
C10—C1—H1	106.3	O3—C16—H162	109.5
C1—C2—H21	108.6	O3—C16—H163	109.5
C1—C2—H22	108.6	H161—C16—H162	109.5
C3—C2—H21	108.6	H161—C16—H163	109.5
C3—C2—H22	108.6	H162—C16—H163	109.5
H21—C2—H22	109.5
C16—O3—C15—C10	170.27 (16)	C5—C4—C9—C8	−62.1 (2)
C16—O3—C15—C14	−8.4 (2)	C9—C4—C5—C6	50.9 (2)
C2—C1—C8—C7	−67.5 (2)	C4—C5—C6—C7	−42.5 (2)
C2—C1—C8—C9	53.83 (19)	C5—C6—C7—C8	42.9 (2)
C8—C1—C2—C3	−47.7 (2)	C6—C7—C8—C1	69.4 (2)
C2—C1—C10—C11	19.8 (2)	C6—C7—C8—C9	−51.8 (2)
C2—C1—C10—C15	−160.11 (16)	C1—C8—C9—O2	116.16 (19)
C10—C1—C2—C3	−175.04 (15)	C1—C8—C9—C4	−63.67 (19)
C8—C1—C10—C11	−108.0 (2)	C7—C8—C9—O2	−117.7 (2)
C8—C1—C10—C15	72.1 (2)	C7—C8—C9—C4	62.4 (2)
C10—C1—C8—C7	61.7 (2)	C1—C10—C11—C12	−179.26 (18)
C10—C1—C8—C9	−176.97 (14)	C1—C10—C15—O3	1.2 (2)
C1—C2—C3—O1	−71.93 (19)	C1—C10—C15—C14	179.90 (17)
C1—C2—C3—C4	48.5 (2)	C11—C10—C15—O3	−178.77 (16)
O1—C3—C4—C5	−174.64 (15)	C11—C10—C15—C14	−0.0 (2)
O1—C3—C4—C9	64.54 (19)	C15—C10—C11—C12	0.7 (2)
C2—C3—C4—C5	66.5 (2)	C10—C11—C12—C13	−0.9 (3)
C2—C3—C4—C9	−54.3 (2)	C11—C12—C13—C14	0.4 (3)
C3—C4—C5—C6	−69.7 (2)	C12—C13—C14—C15	0.2 (3)
C3—C4—C9—O2	−116.3 (2)	C13—C14—C15—O3	178.22 (18)
C3—C4—C9—C8	63.5 (2)	C13—C14—C15—C10	−0.4 (2)
C5—C4—C9—O2	118.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H101···O2i	0.85	1.99	2.8268 (19)	171
O1ii—H101ii···O2	0.85	1.99	2.8268 (19)	171
C14—H14···O1iii	0.93	2.51	3.434 (2)	176

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H101⋯O2i	0.85	1.99	2.8268 (19)	171
O1ii—H101ii⋯O2	0.85	1.99	2.8268 (19)	171
C14—H14⋯O1iii	0.93	2.51	3.434 (2)	176

Symmetry codes: (i) ; (ii) ; (iii) .