(1R*,11R*)-Bi­cyclo­[9.4.1]­hexa­decane-12,16-dione

The title compound, C₁₆H₂₆O₂, (I), prepared by oxidation of (1R*,11R*)-12-hydroxy­bi­cyclo­[9.4.1]­hexa­decan-16-one using pyridinium dichromate, has a trans configuration of the two fused rings and represents an interesting precursor for the synthesis of macrocyclic structures.

S1. Experimental

Following the procedure of Fu & Cook (1992), a suspension of (1R^*,11R^*)-12-hydroxybicyclo[9.4.1]hexadecan-16-one (1.89 g, 7.5 mmol) and pyridiniumdichromate (5.64 g, 15.0 mmol) in dry dichloromethane (20 ml) was stirred at room temperature for 16 h. After filtration of the salts, the solution was evaporated und filtered through a short column with silica gel using n-hexane/MTBE (1:1) as eluent. The crude product (1.71 g) was recrystallized from 10 ml n-hexane to give 1.41 g (5.6 mmol, 75%) (1R^*,11R^*)-bicyclo[9.4.1]hexadecane-12,16-dione as colourless crystals. Analysis calculated for C₁₆H₂₆O₂ (250.37 g mol⁻¹): C 76.8, H 10.5%; found: C 76.8, H 10.6%. MS (EI, 70 eV): m/z (%) = 250 (M⁺, 39), 232 (10), 222 (36), 179 (7), 134 (6), 123 (19), 110 (30), 95 (32), 83 (29), 67 (34), 55 (100). IR (KBr): ñ (cm⁻¹) = 2932 (s), 2893 (s), 2859 (s), 1722 (s), 1692 (s), 1444 (s), 1336 (s), 1260 (s), 1139 (s). ¹H NMR (400 MHz, CDCl₃): δ (p.p.m.) = 1.00–1.43 (14H), 1.67 (m, 5H), 1.97 (m, 3H), 2.39 (m, 1H), 2.48 (m, 1H), 2.82 (tt^*, ³J = 11.6 Hz, ³J = 2.6 Hz, 1H), 3.13 (dd, ³J = 11.9 Hz, ³J = 3.1 Hz, 1H). ¹³C NMR (100 MHz, CDCl₃): δ (p.p.m.) = 21.5 (CH₂), 21.6 (CH₂), 22.2 (CH₂), 23.6 (CH₂), 23.6 (CH₂), 23.9 (CH₂), 24.1 (CH₂), 26.7 (CH₂), 27.2 (CH₂), 31.8 (CH₂), 37.4 (CH₂), 43.2 (CH₂), 46.9 (CH), 69.3 (CH), 209.2 (Cq), 214.5 (Cq). M.p: 380 K.

Computing details

Data collection: Nonius KappaCCD; cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997), PARST95 (Nardelli, 1995).

(I)

Crystal data

C16H26O2	Z = 2
Mr = 250.37	F(000) = 276
Triclinic, P1	Dx = 1.137 Mg m^−3
a = 8.0114 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.8149 (7) Å	Cell parameters from 8200 reflections
c = 10.2505 (8) Å	θ = 2.7–25.0°
α = 107.919 (2)°	µ = 0.07 mm^−1
β = 106.039 (4)°	T = 291 K
γ = 91.831 (4)°	Parallelepiped, colourless
V = 731.00 (9) Å^3	0.50 × 0.25 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer	1284 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.023
Graphite monochromator	θmax = 25.0°, θmin = 2.7°
Detector resolution: 10 vertical, 18 horizontal pixels mm^-1	h = −8→8
360 frames via ω–rotation (Δω=1°) and two times 10 s per frame scans	k = −11→11
8200 measured reflections	l = −12→11
2389 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 0.92	Calculated w = 1/[σ^2(Fo^2) + (0.049P)^2] where P = (Fo^2 + 2Fc^2)/3
2389 reflections	(Δ/σ)max < 0.001
163 parameters	Δρmax = 0.13 e Å^−3
0 restraints	Δρmin = −0.12 e Å^−3

Special details

Experimental. The data collection covered almost the whole spere of reciprocal space. The crystal to detector distance was 2.8 cm. Crystal decay was monitored by repeating the initial frames at the end of data collection. Analysing the duplicate reflections there was no indication for any decay.

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
C1	0.1952 (2)	0.75960 (19)	0.51699 (18)	0.0575 (5)
H1	0.2261	0.8497	0.5017	0.069*
C2	−0.0026 (2)	0.7141 (2)	0.4492 (2)	0.0756 (6)
H2A	−0.0325	0.6255	0.4656	0.091*
H2B	−0.0625	0.7878	0.4985	0.091*
C3	−0.0720 (2)	0.6898 (2)	0.2884 (2)	0.0722 (6)
H3A	−0.0039	0.6236	0.2398	0.087*
H3B	−0.1921	0.6438	0.2533	0.087*
C4	−0.0669 (2)	0.8249 (2)	0.2476 (2)	0.0724 (6)
H4A	0.0517	0.8746	0.2885	0.087*
H4B	−0.1418	0.8882	0.2905	0.087*
C5	−0.1244 (2)	0.7993 (2)	0.0862 (2)	0.0883 (7)
H5A	−0.1301	0.8920	0.0709	0.106*
H5B	−0.2414	0.7466	0.0445	0.106*
C6	−0.0049 (2)	0.7162 (2)	0.0074 (2)	0.0818 (6)
H6A	0.0080	0.6267	0.0287	0.098*
H6B	−0.0607	0.6913	−0.0952	0.098*
C7	0.1762 (3)	0.7969 (2)	0.0451 (2)	0.0759 (6)
H7A	0.2037	0.8675	0.1407	0.091*
H7B	0.1738	0.8491	−0.0217	0.091*
C8	0.3213 (3)	0.7007 (2)	0.0415 (2)	0.0744 (6)
H8A	0.4263	0.7567	0.0466	0.089*
H8B	0.2869	0.6226	−0.0498	0.089*
C9	0.3647 (2)	0.6356 (2)	0.16358 (18)	0.0608 (5)
H9A	0.2583	0.5856	0.1636	0.073*
H9B	0.4452	0.5652	0.1462	0.073*
C10	0.4460 (2)	0.74927 (19)	0.30971 (18)	0.0557 (5)
H10A	0.5585	0.7911	0.3120	0.067*
H10B	0.3718	0.8257	0.3206	0.067*
C11	0.47294 (19)	0.69576 (18)	0.43765 (18)	0.0522 (5)
H11	0.5365	0.6117	0.4193	0.063*
C12	0.5847 (2)	0.8075 (2)	0.5766 (2)	0.0607 (5)
O1	0.67578 (16)	0.90795 (17)	0.57420 (14)	0.0854 (5)
C13	0.5790 (3)	0.7919 (2)	0.7161 (2)	0.0853 (7)
H13A	0.6898	0.8348	0.7892	0.102*
H13B	0.5628	0.6902	0.7052	0.102*
C14	0.4303 (3)	0.8649 (2)	0.7644 (2)	0.0863 (7)
H14A	0.4353	0.9612	0.7572	0.104*
H14B	0.4500	0.8753	0.8649	0.104*
C15	0.2466 (3)	0.7855 (2)	0.6793 (2)	0.0813 (6)
H15A	0.1627	0.8406	0.7178	0.098*
H15B	0.2381	0.6929	0.6940	0.098*
C16	0.2998 (2)	0.6455 (2)	0.45123 (18)	0.0512 (4)
O2	0.24747 (15)	0.51790 (15)	0.41355 (14)	0.0704 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0692 (12)	0.0523 (12)	0.0671 (13)	0.0193 (9)	0.0352 (9)	0.0280 (10)
C2	0.0684 (13)	0.0682 (14)	0.1131 (18)	0.0172 (10)	0.0537 (12)	0.0376 (13)
C3	0.0464 (10)	0.0636 (14)	0.1058 (18)	0.0102 (9)	0.0211 (10)	0.0282 (12)
C4	0.0581 (11)	0.0659 (15)	0.0960 (17)	0.0205 (10)	0.0234 (11)	0.0291 (12)
C5	0.0697 (13)	0.0795 (16)	0.1002 (18)	0.0194 (11)	−0.0035 (12)	0.0328 (14)
C6	0.0806 (14)	0.0792 (16)	0.0629 (13)	0.0119 (12)	−0.0064 (11)	0.0167 (12)
C7	0.1004 (15)	0.0739 (15)	0.0573 (12)	0.0112 (12)	0.0188 (11)	0.0316 (11)
C8	0.0917 (14)	0.0757 (15)	0.0601 (13)	0.0138 (12)	0.0318 (11)	0.0202 (11)
C9	0.0614 (11)	0.0607 (13)	0.0611 (13)	0.0155 (9)	0.0234 (9)	0.0158 (11)
C10	0.0489 (9)	0.0558 (12)	0.0641 (12)	0.0075 (8)	0.0195 (8)	0.0199 (10)
C11	0.0483 (10)	0.0463 (11)	0.0603 (12)	0.0143 (8)	0.0122 (8)	0.0181 (10)
C12	0.0515 (11)	0.0499 (13)	0.0712 (15)	0.0151 (10)	0.0096 (10)	0.0138 (11)
O1	0.0634 (8)	0.0798 (11)	0.0937 (11)	−0.0017 (8)	0.0214 (7)	0.0049 (9)
C13	0.1036 (16)	0.0723 (16)	0.0636 (14)	0.0215 (13)	−0.0038 (12)	0.0243 (12)
C14	0.138 (2)	0.0744 (16)	0.0508 (13)	0.0207 (15)	0.0317 (13)	0.0232 (12)
C15	0.1211 (18)	0.0738 (16)	0.0694 (15)	0.0214 (13)	0.0485 (13)	0.0333 (13)
C16	0.0598 (10)	0.0470 (12)	0.0523 (11)	0.0130 (9)	0.0147 (8)	0.0253 (10)
O2	0.0724 (8)	0.0490 (9)	0.0957 (10)	0.0109 (7)	0.0281 (7)	0.0294 (8)

Geometric parameters (Å, º)

C1—C16	1.523 (2)	C8—H8A	0.9700
C1—C15	1.535 (2)	C8—H8B	0.9700
C1—C2	1.532 (2)	C9—C10	1.516 (2)
C1—H1	0.9800	C9—H9A	0.9700
C2—C3	1.525 (2)	C9—H9B	0.9700
C2—H2A	0.9700	C10—C11	1.522 (2)
C2—H2B	0.9700	C10—H10A	0.9700
C3—C4	1.510 (2)	C10—H10B	0.9700
C3—H3A	0.9700	C11—C16	1.514 (2)
C3—H3B	0.9700	C11—C12	1.518 (2)
C4—C5	1.526 (3)	C11—H11	0.9800
C4—H4A	0.9700	C12—O1	1.218 (2)
C4—H4B	0.9700	C12—C13	1.497 (3)
C5—C6	1.518 (3)	C13—C14	1.530 (3)
C5—H5A	0.9700	C13—H13A	0.9700
C5—H5B	0.9700	C13—H13B	0.9700
C6—C7	1.520 (3)	C14—C15	1.528 (3)
C6—H6A	0.9700	C14—H14A	0.9700
C6—H6B	0.9700	C14—H14B	0.9700
C7—C8	1.523 (2)	C15—H15A	0.9700
C7—H7A	0.9700	C15—H15B	0.9700
C7—H7B	0.9700	C16—O2	1.2136 (19)
C8—C9	1.537 (2)
C16—C1—C15	108.33 (13)	C7—C8—H8B	108.7
C16—C1—C2	111.89 (15)	C9—C8—H8B	108.7
C15—C1—C2	110.25 (14)	H8A—C8—H8B	107.6
C16—C1—H1	108.8	C10—C9—C8	112.33 (15)
C15—C1—H1	108.8	C10—C9—H9A	109.1
C2—C1—H1	108.8	C8—C9—H9A	109.1
C3—C2—C1	115.53 (14)	C10—C9—H9B	109.1
C3—C2—H2A	108.4	C8—C9—H9B	109.1
C1—C2—H2A	108.4	H9A—C9—H9B	107.9
C3—C2—H2B	108.4	C11—C10—C9	115.38 (14)
C1—C2—H2B	108.4	C11—C10—H10A	108.4
H2A—C2—H2B	107.5	C9—C10—H10A	108.4
C4—C3—C2	114.94 (16)	C11—C10—H10B	108.4
C4—C3—H3A	108.5	C9—C10—H10B	108.4
C2—C3—H3A	108.5	H10A—C10—H10B	107.5
C4—C3—H3B	108.5	C16—C11—C12	111.48 (14)
C2—C3—H3B	108.5	C16—C11—C10	111.32 (12)
H3A—C3—H3B	107.5	C12—C11—C10	112.14 (15)
C3—C4—C5	114.84 (17)	C16—C11—H11	107.2
C3—C4—H4A	108.6	C12—C11—H11	107.2
C5—C4—H4A	108.6	C10—C11—H11	107.2
C3—C4—H4B	108.6	O1—C12—C13	120.95 (19)
C5—C4—H4B	108.6	O1—C12—C11	120.59 (18)
H4A—C4—H4B	107.5	C13—C12—C11	118.46 (18)
C4—C5—C6	114.29 (14)	C12—C13—C14	111.32 (14)
C4—C5—H5A	108.7	C12—C13—H13A	109.4
C6—C5—H5A	108.7	C14—C13—H13A	109.4
C4—C5—H5B	108.7	C12—C13—H13B	109.4
C6—C5—H5B	108.7	C14—C13—H13B	109.4
H5A—C5—H5B	107.6	H13A—C13—H13B	108.0
C7—C6—C5	114.55 (18)	C13—C14—C15	115.11 (17)
C7—C6—H6A	108.6	C13—C14—H14A	108.5
C5—C6—H6A	108.6	C15—C14—H14A	108.5
C7—C6—H6B	108.6	C13—C14—H14B	108.5
C5—C6—H6B	108.6	C15—C14—H14B	108.5
H6A—C6—H6B	107.6	H14A—C14—H14B	107.5
C6—C7—C8	114.25 (17)	C14—C15—C1	115.01 (15)
C6—C7—H7A	108.7	C14—C15—H15A	108.5
C8—C7—H7A	108.7	C1—C15—H15A	108.5
C6—C7—H7B	108.7	C14—C15—H15B	108.5
C8—C7—H7B	108.7	C1—C15—H15B	108.5
H7A—C7—H7B	107.6	H15A—C15—H15B	107.5
C7—C8—C9	114.03 (14)	O2—C16—C11	121.02 (15)
C7—C8—H8A	108.7	O2—C16—C1	120.88 (15)
C9—C8—H8A	108.7	C11—C16—C1	118.08 (16)
C16—C1—C2—C3	−61.4 (2)	C10—C11—C12—C13	161.64 (13)
C15—C1—C2—C3	178.01 (15)	O1—C12—C13—C14	92.3 (2)
C1—C2—C3—C4	−69.34 (19)	C11—C12—C13—C14	−87.2 (2)
C2—C3—C4—C5	175.92 (14)	C12—C13—C14—C15	73.4 (2)
C3—C4—C5—C6	−65.2 (2)	C13—C14—C15—C1	−58.0 (2)
C4—C5—C6—C7	−67.5 (2)	C16—C1—C15—C14	71.1 (2)
C5—C6—C7—C8	146.78 (16)	C2—C1—C15—C14	−166.14 (16)
C6—C7—C8—C9	−70.3 (2)	C12—C11—C16—O2	−130.88 (17)
C7—C8—C9—C10	−67.1 (2)	C10—C11—C16—O2	103.08 (18)
C8—C9—C10—C11	173.13 (12)	C12—C11—C16—C1	47.65 (19)
C9—C10—C11—C16	−65.09 (17)	C10—C11—C16—C1	−78.39 (17)
C9—C10—C11—C12	169.24 (13)	C15—C1—C16—O2	86.43 (19)
C16—C11—C12—O1	−143.44 (16)	C2—C1—C16—O2	−35.3 (2)
C10—C11—C12—O1	−17.9 (2)	C15—C1—C16—C11	−92.10 (17)
C16—C11—C12—C13	36.1 (2)	C2—C1—C16—C11	146.16 (14)