rac-(1S,11S,15S)-1-Hydroxy­methyl­bicyclo­[9.3.1]penta­decan-15-ol

The mol­ecule of the title compound, C₁₆H₃₀O₂, features a trans-fused bicyclic system. The six-membered ring has a chair conformation. The mol­ecules are linked via an O—H...O hydrogen bond [O...O = 2.7696 (11) Å and O—H...O = 174.2 (13)°] to form chains along the b axis. An intra­molecular O—H...O hydrogen bond [O...O = 2.6722 (11) Å and O—H...O = 148.4 (13)°] is present.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.036
• wR factor = 0.090
• Data-to-parameter ratio = 19.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C1     -   C14     ..       5.27 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C1     -   C16     ..       5.65 su
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C16 H30 O2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

In order to study the reductive ring fragmentation (Marshall & Scanio, 1965) of keto-bridged bicyclic esters, ethyl 12-iodo-15-oxobicyclo[9.3.1]pentadecane-1-carboxylate (Fresu et al., 2004) was treated with lithium aluminium hydride. Surprisingly, the title compound, (I), isolated in 58% yield after extractive work-up, was found to result from deiodation and complete reduction of all carbonyl groups to alcohol functionalities. Reduction of the C15 keto group to alcohol gave only one epimer at the new stereogenic centre. The configuration had to be clarified by X-ray crystallography.

S2. Experimental

A solution of ethyl 12-iodo-15-oxobicyclo[9.3.1]pentadecane-1-carboxylate (1.6 g, 3.8 mmol) in tetrahydrofuran (30 ml) was treated with LiAlH₄ (2.8 g, 7.62 mmol). The resulting suspension was heated under reflux for 16 h. Upon cooling to ambient temperature, water (100 ml) was carefully added, followed by HCl (concentrated) until a homogeneous solution was obtained. The solution was extracted with diethyl ether (3 × 30 ml). The combined ether layers were dried over MgSO₄ and the solvent was removed to yield 0.56 g (2.2 mmol, 58%) of the title compound. ¹H NMR: 3.75 (d, 1H, ³J = 10.7 Hz, H15), 3.48 (t, 2H, ³J = 11.2 Hz, CH₂), 2.72 (s, OH), 2.25 (m, 3H, CH₂), 2.00–1.88 (m, 8H, CH₂), 1.78–1.54 (m, 4H, CH₂), 1.51–1.37 (m, 4H, CH₂), 1.26–1.09 (m, 2H, CH₂), 0.98–0.88 (m, 4H, CH₂). ¹³C NMR: 82.72 (C15), 72.13 (C16), 43.10 (CH₂), 34.87 (CH₂), 34.32 (C11), 33.18 (CH₂), 29.97 (CH₂), 29.85 (CH₂), 27.41 (CH₂), 25.79 (CH₂), 24.20 (CH₂), 23.56 (CH₂), 22.66 (CH₂), 22.05 (CH₂), 21.09 (CH₂), 19.84 (CH₂). IR (neat): 3265 (s), 2927 (s), 2917 (s), 2852 (s), 1473 (m), 1463 (m), 1086 (m), 1050 (m), 1019 (m). LR–MS: 236 (M - H₂O, 100), 218 (8), 205 (24), 109 (14), 95 (23), 81 (24), 67 (20), 55 (28), 41 (33), 29 (8).

S3. Refinement

The hydroxy H atoms were refined isotropically and the remaining H atoms were placed in calculated positions (C—H = 0.97–0.98 Å) with U_iso values constrained to be 1.2 times U_eq of the carrier atom.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97, PARST95 (Nardelli, 1995) and PLATON (Spek, 2001).

Figures

Fig. 1. View of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are draown at the 30% probability level.

rac-(1S,11S,15S)-1-Hydroxymethylbicyclo[9.3.1]pentadecan-15-ol

Crystal data

C16H30O2	F(000) = 568
Mr = 254.40	Dx = 1.133 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 12034 reflections
a = 13.0319 (7) Å	θ = 2.9–27.5°
b = 8.4862 (4) Å	µ = 0.07 mm^−1
c = 14.4047 (9) Å	T = 291 K
β = 110.539 (3)°	Block, colourless
V = 1491.77 (14) Å^3	0.20 × 0.10 × 0.05 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	1996 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.023
Graphite monochromator	θmax = 27.5°, θmin = 2.9°
Detector resolution: 19 vertical, 18 horizontal pixels mm^-1	h = −16→16
296 frames via ω–rotation (Δω=1°) and two times 55 s per frame (two sets at different κ–angles) scans	k = −10→10
12034 measured reflections	l = −18→17
3393 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.090	w = 1/[σ^2(Fo^2) + (0.0478P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.90	(Δ/σ)max < 0.001
3393 reflections	Δρmax = 0.19 e Å^−3
172 parameters	Δρmin = −0.14 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.012 (3)

Special details

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. 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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	−0.10174 (6)	0.13418 (9)	0.20536 (5)	0.0409 (2)
H1	−0.0544 (11)	0.0681 (16)	0.2393 (10)	0.068 (4)*
O2	−0.06241 (6)	0.43668 (10)	0.17857 (6)	0.0527 (2)
H2	−0.0663 (11)	0.3485 (19)	0.2109 (11)	0.077 (5)*
C1	−0.15612 (8)	0.25184 (12)	0.03967 (7)	0.0374 (3)
C2	−0.27356 (9)	0.30746 (12)	0.02644 (8)	0.0406 (3)
H2A	−0.2895	0.3982	−0.0173	0.049*
H2B	−0.3236	0.2245	−0.0080	0.049*
C3	−0.30136 (9)	0.35199 (12)	0.11760 (8)	0.0447 (3)
H3A	−0.2833	0.4621	0.1328	0.054*
H3B	−0.2557	0.2904	0.1736	0.054*
C4	−0.42131 (9)	0.32646 (13)	0.10606 (9)	0.0494 (3)
H4A	−0.4372	0.3874	0.1564	0.059*
H4B	−0.4674	0.3665	0.0419	0.059*
C5	−0.45137 (9)	0.15446 (13)	0.11461 (9)	0.0492 (3)
H5A	−0.5299	0.1474	0.0992	0.059*
H5B	−0.4336	0.0931	0.0655	0.059*
C6	−0.39400 (12)	0.08198 (13)	0.21577 (9)	0.0569 (4)
H6A	−0.4209	0.1329	0.2630	0.068*
H6B	−0.3163	0.1048	0.2357	0.068*
C7	−0.40828 (12)	−0.09589 (14)	0.22229 (11)	0.0623 (4)
H7A	−0.3807	−0.1264	0.2916	0.075*
H7B	−0.4859	−0.1201	0.1962	0.075*
C8	−0.35087 (10)	−0.19493 (14)	0.16704 (10)	0.0567 (3)
H8A	−0.3773	−0.1626	0.0981	0.068*
H8B	−0.3718	−0.3042	0.1692	0.068*
C9	−0.22551 (10)	−0.18487 (14)	0.20681 (9)	0.0514 (3)
H9A	−0.2036	−0.0894	0.2458	0.062*
H9B	−0.1965	−0.2735	0.2507	0.062*
C10	−0.17471 (10)	−0.18478 (12)	0.12647 (9)	0.0465 (3)
H10A	−0.2014	−0.2762	0.0845	0.056*
H10B	−0.0960	−0.1960	0.1578	0.056*
C11	−0.19829 (9)	−0.03730 (11)	0.06066 (7)	0.0382 (3)
H11	−0.2723	−0.0012	0.0528	0.046*
C12	−0.19636 (10)	−0.07353 (14)	−0.04244 (8)	0.0513 (3)
H12A	−0.1251	−0.1163	−0.0357	0.062*
H12B	−0.2506	−0.1542	−0.0726	0.062*
C13	−0.21878 (11)	0.06651 (15)	−0.11067 (9)	0.0573 (3)
H13A	−0.2960	0.0928	−0.1314	0.069*
H13B	−0.2028	0.0385	−0.1695	0.069*
C14	−0.15155 (10)	0.21074 (14)	−0.06305 (8)	0.0504 (3)
H14A	−0.1778	0.3004	−0.1068	0.061*
H14B	−0.0758	0.1926	−0.0564	0.061*
C15	−0.11959 (9)	0.10017 (11)	0.10302 (7)	0.0355 (3)
H15	−0.0485	0.0695	0.0995	0.043*
C16	−0.07199 (10)	0.38332 (13)	0.08201 (8)	0.0488 (3)
H16A	−0.0008	0.3460	0.0842	0.059*
H16B	−0.0916	0.4724	0.0370	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0495 (5)	0.0345 (4)	0.0335 (4)	0.0046 (4)	0.0082 (4)	0.0016 (3)
O2	0.0583 (6)	0.0404 (5)	0.0504 (5)	−0.0124 (4)	0.0080 (4)	−0.0030 (4)
C1	0.0398 (6)	0.0366 (6)	0.0346 (6)	0.0002 (4)	0.0116 (5)	0.0032 (4)
C2	0.0432 (7)	0.0351 (5)	0.0404 (6)	0.0051 (5)	0.0109 (5)	0.0063 (5)
C3	0.0484 (7)	0.0340 (6)	0.0522 (7)	0.0004 (5)	0.0183 (5)	−0.0052 (5)
C4	0.0477 (8)	0.0425 (7)	0.0590 (8)	0.0098 (5)	0.0202 (6)	0.0012 (5)
C5	0.0391 (7)	0.0486 (7)	0.0592 (8)	−0.0003 (5)	0.0163 (6)	−0.0011 (6)
C6	0.0704 (9)	0.0474 (7)	0.0577 (8)	0.0056 (6)	0.0283 (7)	−0.0002 (6)
C7	0.0656 (9)	0.0546 (8)	0.0754 (9)	−0.0019 (6)	0.0354 (7)	0.0101 (7)
C8	0.0592 (8)	0.0364 (6)	0.0777 (9)	−0.0101 (6)	0.0279 (7)	−0.0005 (6)
C9	0.0586 (8)	0.0386 (6)	0.0547 (7)	−0.0007 (6)	0.0170 (6)	0.0088 (5)
C10	0.0477 (7)	0.0315 (5)	0.0557 (7)	0.0031 (5)	0.0122 (6)	−0.0016 (5)
C11	0.0386 (6)	0.0337 (5)	0.0409 (6)	0.0029 (5)	0.0123 (5)	−0.0024 (5)
C12	0.0550 (8)	0.0498 (7)	0.0472 (7)	−0.0008 (6)	0.0156 (6)	−0.0117 (6)
C13	0.0712 (9)	0.0640 (8)	0.0377 (7)	0.0051 (6)	0.0204 (6)	−0.0071 (6)
C14	0.0545 (8)	0.0579 (7)	0.0414 (7)	0.0049 (6)	0.0201 (6)	0.0072 (6)
C15	0.0363 (6)	0.0357 (6)	0.0343 (6)	0.0038 (4)	0.0121 (5)	−0.0001 (4)
C16	0.0499 (7)	0.0435 (6)	0.0517 (8)	−0.0048 (5)	0.0162 (6)	0.0066 (6)

Geometric parameters (Å, º)

O1—C15	1.4387 (12)	C7—H7B	0.9700
O1—H1	0.850 (14)	C8—C9	1.5323 (16)
O2—C16	1.4259 (14)	C8—H8A	0.9700
O2—H2	0.892 (16)	C8—H8B	0.9700
C1—C16	1.5329 (15)	C9—C10	1.5216 (16)
C1—C14	1.5415 (15)	C9—H9A	0.9700
C1—C2	1.5482 (15)	C9—H9B	0.9700
C1—C15	1.5529 (14)	C10—C11	1.5346 (14)
C2—C3	1.5272 (15)	C10—H10A	0.9700
C2—H2A	0.9700	C10—H10B	0.9700
C2—H2B	0.9700	C11—C12	1.5254 (15)
C3—C4	1.5282 (15)	C11—C15	1.5316 (14)
C3—H3A	0.9700	C11—H11	0.9800
C3—H3B	0.9700	C12—C13	1.5041 (17)
C4—C5	1.5274 (16)	C12—H12A	0.9700
C4—H4A	0.9700	C12—H12B	0.9700
C4—H4B	0.9700	C13—C14	1.5213 (17)
C5—C6	1.5153 (17)	C13—H13A	0.9700
C5—H5A	0.9700	C13—H13B	0.9700
C5—H5B	0.9700	C14—H14A	0.9700
C6—C7	1.5277 (16)	C14—H14B	0.9700
C6—H6A	0.9700	C15—H15	0.9800
C6—H6B	0.9700	C16—H16A	0.9700
C7—C8	1.5223 (18)	C16—H16B	0.9700
C7—H7A	0.9700
C15—O1—H1	106.3 (9)	H8A—C8—H8B	107.5
C16—O2—H2	103.9 (9)	C10—C9—C8	114.02 (10)
C16—C1—C14	106.47 (9)	C10—C9—H9A	108.7
C16—C1—C2	111.42 (9)	C8—C9—H9A	108.7
C14—C1—C2	108.68 (9)	C10—C9—H9B	108.7
C16—C1—C15	109.90 (9)	C8—C9—H9B	108.7
C14—C1—C15	105.63 (8)	H9A—C9—H9B	107.6
C2—C1—C15	114.27 (8)	C9—C10—C11	115.09 (9)
C3—C2—C1	119.48 (9)	C9—C10—H10A	108.5
C3—C2—H2A	107.4	C11—C10—H10A	108.5
C1—C2—H2A	107.4	C9—C10—H10B	108.5
C3—C2—H2B	107.4	C11—C10—H10B	108.5
C1—C2—H2B	107.4	H10A—C10—H10B	107.5
H2A—C2—H2B	107.0	C12—C11—C15	107.70 (9)
C2—C3—C4	114.43 (9)	C12—C11—C10	111.65 (9)
C2—C3—H3A	108.7	C15—C11—C10	114.46 (8)
C4—C3—H3A	108.7	C12—C11—H11	107.6
C2—C3—H3B	108.7	C15—C11—H11	107.6
C4—C3—H3B	108.7	C10—C11—H11	107.6
H3A—C3—H3B	107.6	C13—C12—C11	114.28 (9)
C5—C4—C3	114.09 (9)	C13—C12—H12A	108.7
C5—C4—H4A	108.7	C11—C12—H12A	108.7
C3—C4—H4A	108.7	C13—C12—H12B	108.7
C5—C4—H4B	108.7	C11—C12—H12B	108.7
C3—C4—H4B	108.7	H12A—C12—H12B	107.6
H4A—C4—H4B	107.6	C12—C13—C14	113.07 (10)
C6—C5—C4	114.30 (10)	C12—C13—H13A	109.0
C6—C5—H5A	108.7	C14—C13—H13A	109.0
C4—C5—H5A	108.7	C12—C13—H13B	109.0
C6—C5—H5B	108.7	C14—C13—H13B	109.0
C4—C5—H5B	108.7	H13A—C13—H13B	107.8
H5A—C5—H5B	107.6	C13—C14—C1	113.88 (9)
C5—C6—C7	115.50 (11)	C13—C14—H14A	108.8
C5—C6—H6A	108.4	C1—C14—H14A	108.8
C7—C6—H6A	108.4	C13—C14—H14B	108.8
C5—C6—H6B	108.4	C1—C14—H14B	108.8
C7—C6—H6B	108.4	H14A—C14—H14B	107.7
H6A—C6—H6B	107.5	O1—C15—C11	113.95 (8)
C8—C7—C6	114.88 (10)	O1—C15—C1	109.99 (8)
C8—C7—H7A	108.5	C11—C15—C1	111.89 (8)
C6—C7—H7A	108.5	O1—C15—H15	106.9
C8—C7—H7B	108.5	C11—C15—H15	106.9
C6—C7—H7B	108.5	C1—C15—H15	106.9
H7A—C7—H7B	107.5	O2—C16—C1	115.15 (9)
C7—C8—C9	115.39 (11)	O2—C16—H16A	108.5
C7—C8—H8A	108.4	C1—C16—H16A	108.5
C9—C8—H8A	108.4	O2—C16—H16B	108.5
C7—C8—H8B	108.4	C1—C16—H16B	108.5
C9—C8—H8B	108.4	H16A—C16—H16B	107.5
C16—C1—C2—C3	−64.44 (12)	C16—C1—C14—C13	172.11 (10)
C14—C1—C2—C3	178.55 (9)	C2—C1—C14—C13	−67.76 (12)
C15—C1—C2—C3	60.88 (12)	C15—C1—C14—C13	55.28 (12)
C1—C2—C3—C4	−151.40 (9)	C12—C11—C15—O1	−172.22 (8)
C2—C3—C4—C5	76.72 (12)	C10—C11—C15—O1	−47.43 (12)
C3—C4—C5—C6	64.69 (14)	C12—C11—C15—C1	62.22 (11)
C4—C5—C6—C7	−170.85 (11)	C10—C11—C15—C1	−173.00 (9)
C5—C6—C7—C8	69.06 (16)	C16—C1—C15—O1	55.06 (11)
C6—C7—C8—C9	64.77 (16)	C14—C1—C15—O1	169.54 (8)
C7—C8—C9—C10	−141.70 (11)	C2—C1—C15—O1	−71.05 (11)
C8—C9—C10—C11	67.67 (12)	C16—C1—C15—C11	−177.23 (9)
C9—C10—C11—C12	−152.13 (10)	C14—C1—C15—C11	−62.74 (11)
C9—C10—C11—C15	85.20 (12)	C2—C1—C15—C11	56.66 (12)
C15—C11—C12—C13	−53.46 (12)	C14—C1—C16—O2	−179.03 (9)
C10—C11—C12—C13	−179.92 (10)	C2—C1—C16—O2	62.62 (12)
C11—C12—C13—C14	48.22 (15)	C15—C1—C16—O2	−65.09 (12)
C12—C13—C14—C1	−49.80 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.892 (16)	1.871 (16)	2.6722 (11)	148.4 (13)
O1—H1···O2^i	0.850 (14)	1.922 (15)	2.7696 (11)	174.2 (13)

Symmetry code: (i) −x, y−1/2, −z+1/2.