In the title compound, C
13H
22O
3, the asymmetric unit has two independent molecules linked by a strong O-H
O hydrogen bond. The cyclohexane ring is
trans fused to the cyclopentane ring bridged through an ethyl moiety. The hydroxyl groups act as donors as well as acceptors, resulting in an extensive two-dimensional hydrogen-bonded network in the (011) plane. Intermolecular O-H
O bonds between centrosymmetrically related molecules form a four-membered supramolecular assembly, leading to infinite chains parallel to the [01
] direction, crosslinked in the [100] direction.
Supporting information
CCDC reference: 193424
A solution of
(1RS,2RS,8RS)-2-hydroxy-7,7-dimethyltricyclo[6.2.1.01,6]undec-5-ene (0.31 g,
1.6 mmol) and OsO4 (0.41 g, 1.6 mmol) in pyridine (6 ml) was stored at room
temperature for 5 d. A saturated aqueous solution of sodium hydrogen sulfite
(20 ml) was then added to the reaction mixture, and stirring was continued at
room temperature for 3 h. Water (20 ml) was added and the product was
extracted with ether. The ether extract was washed with dilute HCl and then
water, and then dried. The residue remaining upon evaporation of the solvent
was crystallized from a mixture of ether and light petroleum (1:1) to furnish
the title triol, (II) (0.3 g, 82%) (m.p. 451–453 K). Elemental analysis,
calculated for C13H22O3, requires: C 68.99, H 9.80%; found: C 68.85, H
9.92%.
H atoms were placed geometrically and were treated as riding using the
appropriate instructions in SHELXL97 (Sheldrick, 1997). The hydroxyl H
atoms were constrained using the HFIX 147 instruction, with the O—H
distances fixed at 0.82 Å and the C—O—H angles tetrahedral; for the
idealized methyl groups, the HFIX 137 instruction was used, with C—H =
0.96–0.98 Å. Please check added constraints.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1995); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1995); program(s) used to solve structure: MULTAN88 (Debaerdemaeker et al., 1988); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1995) and WinGX (Farrugia, 1999); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).
(1SR,2RS,5RS,6SR,8RS)-7,7-dimethyltricyclo[6.2.1.0
1,6]undecane-2,5,6-triol
top
Crystal data top
C13H22O3 | Z = 4 |
Mr = 226.31 | F(000) = 496 |
Triclinic, P1 | Dx = 1.241 Mg m−3 |
Hall symbol: -P 1 | Melting point: 453K K |
a = 9.812 (2) Å | Mo Kα radiation, λ = 0.71070 Å |
b = 11.141 (1) Å | Cell parameters from 18 reflections |
c = 11.443 (2) Å | θ = 6.9–8.1° |
α = 82.47 (1)° | µ = 0.09 mm−1 |
β = 77.56 (1)° | T = 293 K |
γ = 89.46 (1)° | Block, colourless |
V = 1210.8 (3) Å3 | 0.5 × 0.4 × 0.3 mm |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.015 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 1.8° |
Graphite monochromator | h = −11→11 |
ω/2θ scans | k = −13→0 |
4499 measured reflections | l = −13→13 |
4259 independent reflections | 3 standard reflections every 150 reflections |
2972 reflections with I > 2σ(I) | intensity decay: −1.1% |
Refinement top
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.156 | H-atom parameters not refined |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0577P)2 + 0.9623P] where P = (Fo2 + 2Fc2)/3 |
4259 reflections | (Δ/σ)max = 0.014 |
299 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
Crystal data top
C13H22O3 | γ = 89.46 (1)° |
Mr = 226.31 | V = 1210.8 (3) Å3 |
Triclinic, P1 | Z = 4 |
a = 9.812 (2) Å | Mo Kα radiation |
b = 11.141 (1) Å | µ = 0.09 mm−1 |
c = 11.443 (2) Å | T = 293 K |
α = 82.47 (1)° | 0.5 × 0.4 × 0.3 mm |
β = 77.56 (1)° | |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.015 |
4499 measured reflections | 3 standard reflections every 150 reflections |
4259 independent reflections | intensity decay: −1.1% |
2972 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.156 | H-atom parameters not refined |
S = 1.10 | Δρmax = 0.24 e Å−3 |
4259 reflections | Δρmin = −0.21 e Å−3 |
299 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1A | 0.7141 (3) | 0.2593 (2) | 0.9184 (2) | 0.0303 (6) | |
C2A | 0.6901 (3) | 0.2018 (2) | 0.8106 (2) | 0.0336 (6) | |
H2A | 0.7796 | 0.1978 | 0.7535 | 0.040* | |
C3A | 0.6296 (3) | 0.0742 (3) | 0.8510 (3) | 0.0410 (7) | |
H3A1 | 0.6222 | 0.0370 | 0.7806 | 0.049* | |
H3A2 | 0.5363 | 0.0784 | 0.9002 | 0.049* | |
C4A | 0.7192 (3) | −0.0050 (2) | 0.9236 (3) | 0.0383 (7) | |
H4A1 | 0.6725 | −0.0828 | 0.9531 | 0.046* | |
H4A2 | 0.8078 | −0.0191 | 0.8709 | 0.046* | |
C5A | 0.7465 (3) | 0.0526 (2) | 1.0304 (2) | 0.0306 (6) | |
H5A | 0.6579 | 0.0596 | 1.0880 | 0.037* | |
C6A | 0.8121 (3) | 0.1796 (2) | 0.9847 (2) | 0.0281 (6) | |
C7A | 0.8437 (3) | 0.2627 (3) | 1.0796 (2) | 0.0383 (7) | |
C8A | 0.7786 (3) | 0.3848 (3) | 1.0373 (3) | 0.0409 (7) | |
H8A | 0.8228 | 0.4562 | 1.0561 | 0.049* | |
C9A | 0.6201 (3) | 0.3799 (3) | 1.0801 (3) | 0.0490 (8) | |
H9A1 | 0.5797 | 0.4578 | 1.0608 | 0.059* | |
H9A2 | 0.5926 | 0.3545 | 1.1664 | 0.059* | |
C10A | 0.5768 (3) | 0.2844 (3) | 1.0080 (3) | 0.0396 (7) | |
H10A | 0.5062 | 0.3157 | 0.9651 | 0.048* | |
H10B | 0.5408 | 0.2113 | 1.0610 | 0.048* | |
C11A | 0.7907 (3) | 0.3824 (2) | 0.9017 (2) | 0.0363 (7) | |
H11A | 0.8866 | 0.3808 | 0.8573 | 0.044* | |
H11B | 0.7417 | 0.4481 | 0.8651 | 0.044* | |
C12A | 1.0010 (3) | 0.2824 (3) | 1.0680 (3) | 0.0561 (9) | |
H12A | 1.0422 | 0.3190 | 0.9875 | 0.084* | |
H12B | 1.0435 | 0.2058 | 1.0843 | 0.084* | |
H12C | 1.0156 | 0.3345 | 1.1248 | 0.084* | |
C13A | 0.7803 (4) | 0.2134 (3) | 1.2117 (3) | 0.0587 (10) | |
H13A | 0.6836 | 0.1927 | 1.2200 | 0.088* | |
H13B | 0.7882 | 0.2742 | 1.2623 | 0.088* | |
H13C | 0.8294 | 0.1426 | 1.2355 | 0.088* | |
O1A | 0.59473 (19) | 0.2694 (2) | 0.74991 (18) | 0.0453 (5) | |
H1A | 0.6369 | 0.3255 | 0.7029 | 0.068* | |
O2A | 0.84002 (19) | −0.01982 (17) | 1.08956 (18) | 0.0385 (5) | |
H2A1 | 0.7973 | −0.0787 | 1.1316 | 0.058* | |
O3A | 0.93661 (17) | 0.16502 (17) | 0.89587 (15) | 0.0319 (4) | |
H3A | 0.9861 | 0.1147 | 0.9245 | 0.048* | |
C1B | 0.7940 (3) | 0.6323 (2) | 0.5335 (2) | 0.0300 (6) | |
C2B | 0.8156 (3) | 0.5029 (2) | 0.5043 (2) | 0.0330 (6) | |
H2B | 0.9074 | 0.4977 | 0.4509 | 0.040* | |
C3B | 0.7034 (3) | 0.4690 (2) | 0.4412 (3) | 0.0359 (6) | |
H3B1 | 0.6133 | 0.4672 | 0.4967 | 0.043* | |
H3B2 | 0.7205 | 0.3884 | 0.4186 | 0.043* | |
C4B | 0.6993 (3) | 0.5582 (3) | 0.3280 (3) | 0.0396 (7) | |
H4B1 | 0.7835 | 0.5499 | 0.2673 | 0.048* | |
H4B2 | 0.6203 | 0.5372 | 0.2956 | 0.048* | |
C5B | 0.6875 (3) | 0.6889 (2) | 0.3516 (2) | 0.0313 (6) | |
H5B | 0.5961 | 0.6992 | 0.4039 | 0.038* | |
C6B | 0.8003 (2) | 0.7213 (2) | 0.4158 (2) | 0.0280 (6) | |
C7B | 0.7980 (3) | 0.8496 (2) | 0.4626 (3) | 0.0362 (7) | |
C8B | 0.8150 (3) | 0.8138 (3) | 0.5955 (3) | 0.0426 (7) | |
H8B | 0.8596 | 0.8772 | 0.6269 | 0.051* | |
C9B | 0.6780 (3) | 0.7643 (3) | 0.6783 (3) | 0.0531 (9) | |
H9B1 | 0.6023 | 0.8200 | 0.6727 | 0.064* | |
H9B2 | 0.6867 | 0.7480 | 0.7617 | 0.064* | |
C10B | 0.6553 (3) | 0.6465 (3) | 0.6274 (3) | 0.0387 (7) | |
H10C | 0.5762 | 0.6530 | 0.5887 | 0.046* | |
H10D | 0.6393 | 0.5781 | 0.6909 | 0.046* | |
C11B | 0.8977 (3) | 0.6965 (3) | 0.5892 (2) | 0.0391 (7) | |
H11C | 0.9049 | 0.6565 | 0.6682 | 0.047* | |
H11D | 0.9896 | 0.7082 | 0.5365 | 0.047* | |
C12B | 0.9221 (3) | 0.9312 (3) | 0.3914 (3) | 0.0434 (7) | |
H12D | 1.0079 | 0.8942 | 0.4026 | 0.065* | |
H12E | 0.9155 | 1.0087 | 0.4201 | 0.065* | |
H12F | 0.9203 | 0.9417 | 0.3071 | 0.065* | |
C13B | 0.6646 (3) | 0.9206 (3) | 0.4549 (3) | 0.0571 (9) | |
H13D | 0.6635 | 0.9908 | 0.4956 | 0.086* | |
H13E | 0.5845 | 0.8700 | 0.4927 | 0.086* | |
H13F | 0.6625 | 0.9453 | 0.3718 | 0.086* | |
O1B | 0.8074 (2) | 0.41898 (19) | 0.61185 (18) | 0.0459 (6) | |
H1B | 0.8856 | 0.3947 | 0.6156 | 0.069* | |
O2B | 0.6974 (2) | 0.76823 (19) | 0.23988 (18) | 0.0438 (5) | |
H2B1 | 0.6220 | 0.7690 | 0.2199 | 0.066* | |
O3B | 0.93444 (17) | 0.70004 (17) | 0.33988 (16) | 0.0320 (4) | |
H3B | 0.9459 | 0.7466 | 0.2767 | 0.048* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1A | 0.0273 (13) | 0.0295 (14) | 0.0315 (14) | 0.0018 (11) | −0.0054 (11) | 0.0037 (11) |
C2A | 0.0269 (14) | 0.0401 (16) | 0.0325 (14) | −0.0007 (12) | −0.0084 (11) | 0.0033 (12) |
C3A | 0.0406 (16) | 0.0428 (17) | 0.0409 (17) | −0.0081 (13) | −0.0133 (13) | −0.0019 (13) |
C4A | 0.0371 (16) | 0.0312 (15) | 0.0445 (17) | −0.0042 (12) | −0.0060 (13) | −0.0019 (13) |
C5A | 0.0257 (13) | 0.0296 (14) | 0.0328 (14) | 0.0024 (11) | −0.0027 (11) | 0.0031 (11) |
C6A | 0.0261 (13) | 0.0300 (14) | 0.0249 (13) | −0.0015 (11) | −0.0016 (10) | 0.0018 (11) |
C7A | 0.0480 (17) | 0.0338 (15) | 0.0349 (15) | 0.0013 (13) | −0.0119 (13) | −0.0068 (12) |
C8A | 0.0490 (18) | 0.0320 (16) | 0.0428 (17) | 0.0007 (13) | −0.0105 (14) | −0.0076 (13) |
C9A | 0.055 (2) | 0.0422 (18) | 0.0481 (18) | 0.0172 (15) | −0.0045 (15) | −0.0102 (15) |
C10A | 0.0314 (15) | 0.0378 (16) | 0.0446 (17) | 0.0053 (12) | −0.0009 (13) | 0.0004 (13) |
C11A | 0.0376 (16) | 0.0318 (15) | 0.0367 (15) | 0.0021 (12) | −0.0067 (12) | 0.0037 (12) |
C12A | 0.058 (2) | 0.056 (2) | 0.067 (2) | −0.0009 (17) | −0.0346 (18) | −0.0182 (18) |
C13A | 0.097 (3) | 0.0470 (19) | 0.0328 (17) | 0.0111 (19) | −0.0162 (18) | −0.0059 (14) |
O1A | 0.0314 (11) | 0.0587 (14) | 0.0440 (12) | −0.0064 (9) | −0.0166 (9) | 0.0144 (10) |
O2A | 0.0324 (10) | 0.0347 (11) | 0.0427 (11) | 0.0016 (8) | −0.0055 (9) | 0.0120 (9) |
O3A | 0.0251 (9) | 0.0370 (11) | 0.0300 (10) | 0.0044 (8) | −0.0032 (8) | 0.0045 (8) |
C1B | 0.0242 (13) | 0.0374 (15) | 0.0271 (13) | −0.0014 (11) | −0.0049 (11) | 0.0000 (11) |
C2B | 0.0262 (13) | 0.0340 (15) | 0.0342 (14) | −0.0005 (11) | −0.0033 (11) | 0.0067 (12) |
C3B | 0.0363 (15) | 0.0290 (14) | 0.0426 (16) | −0.0040 (12) | −0.0084 (13) | −0.0047 (12) |
C4B | 0.0429 (17) | 0.0405 (17) | 0.0394 (16) | −0.0067 (13) | −0.0183 (13) | −0.0040 (13) |
C5B | 0.0286 (14) | 0.0351 (15) | 0.0296 (14) | −0.0008 (11) | −0.0094 (11) | 0.0030 (11) |
C6B | 0.0220 (13) | 0.0332 (14) | 0.0275 (13) | 0.0007 (11) | −0.0035 (10) | −0.0023 (11) |
C7B | 0.0359 (15) | 0.0307 (15) | 0.0418 (16) | −0.0041 (12) | −0.0072 (13) | −0.0058 (12) |
C8B | 0.0457 (18) | 0.0488 (18) | 0.0337 (15) | −0.0103 (14) | −0.0038 (13) | −0.0145 (13) |
C9B | 0.055 (2) | 0.059 (2) | 0.0406 (18) | −0.0038 (16) | 0.0060 (15) | −0.0172 (16) |
C10B | 0.0327 (15) | 0.0457 (17) | 0.0336 (15) | −0.0046 (13) | 0.0003 (12) | −0.0023 (13) |
C11B | 0.0366 (15) | 0.0540 (19) | 0.0258 (14) | −0.0103 (13) | −0.0080 (12) | 0.0011 (13) |
C12B | 0.0503 (18) | 0.0342 (16) | 0.0468 (18) | −0.0105 (13) | −0.0133 (14) | −0.0040 (13) |
C13B | 0.053 (2) | 0.0416 (19) | 0.079 (2) | 0.0132 (15) | −0.0128 (18) | −0.0182 (18) |
O1B | 0.0318 (11) | 0.0540 (13) | 0.0431 (12) | 0.0025 (10) | −0.0043 (9) | 0.0194 (10) |
O2B | 0.0408 (12) | 0.0500 (13) | 0.0408 (11) | −0.0068 (10) | −0.0198 (9) | 0.0126 (9) |
O3B | 0.0263 (9) | 0.0381 (11) | 0.0277 (10) | 0.0012 (8) | −0.0020 (8) | 0.0033 (8) |
Geometric parameters (Å, º) top
C1A—C2A | 1.524 (4) | C1B—C2B | 1.524 (4) |
C1A—C11A | 1.539 (4) | C1B—C11B | 1.538 (4) |
C1A—C6A | 1.552 (3) | C1B—C6B | 1.555 (3) |
C1A—C10A | 1.555 (4) | C1B—C10B | 1.562 (4) |
C2A—O1A | 1.434 (3) | C2B—O1B | 1.433 (3) |
C2A—C3A | 1.521 (4) | C2B—C3B | 1.517 (4) |
C2A—H2A | 0.9800 | C2B—H2B | 0.9800 |
C3A—C4A | 1.533 (4) | C3B—C4B | 1.533 (4) |
C3A—H3A1 | 0.9700 | C3B—H3B1 | 0.9700 |
C3A—H3A2 | 0.9700 | C3B—H3B2 | 0.9700 |
C4A—C5A | 1.525 (4) | C4B—C5B | 1.515 (4) |
C4A—H4A1 | 0.9700 | C4B—H4B1 | 0.9700 |
C4A—H4A2 | 0.9700 | C4B—H4B2 | 0.9700 |
C5A—O2A | 1.436 (3) | C5B—O2B | 1.441 (3) |
C5A—C6A | 1.539 (3) | C5B—C6B | 1.523 (4) |
C5A—H5A | 0.9800 | C5B—H5B | 0.9800 |
C6A—O3A | 1.434 (3) | C6B—O3B | 1.449 (3) |
C6A—C7A | 1.596 (4) | C6B—C7B | 1.589 (4) |
C7A—C12A | 1.536 (4) | C7B—C13B | 1.535 (4) |
C7A—C13A | 1.535 (4) | C7B—C12B | 1.541 (4) |
C7A—C8A | 1.561 (4) | C7B—C8B | 1.565 (4) |
C8A—C9A | 1.526 (4) | C8B—C9B | 1.529 (4) |
C8A—C11A | 1.535 (4) | C8B—C11B | 1.534 (4) |
C8A—H8A | 0.9800 | C8B—H8B | 0.9800 |
C9A—C10A | 1.543 (4) | C9B—C10B | 1.541 (4) |
C9A—H9A1 | 0.9700 | C9B—H9B1 | 0.9700 |
C9A—H9A2 | 0.9700 | C9B—H9B2 | 0.9700 |
C10A—H10A | 0.9700 | C10B—H10C | 0.9700 |
C10A—H10B | 0.9700 | C10B—H10D | 0.9700 |
C11A—H11A | 0.9700 | C11B—H11C | 0.9700 |
C11A—H11B | 0.9700 | C11B—H11D | 0.9700 |
C12A—H12A | 0.9600 | C12B—H12D | 0.9600 |
C12A—H12B | 0.9600 | C12B—H12E | 0.9600 |
C12A—H12C | 0.9600 | C12B—H12F | 0.9600 |
C13A—H13A | 0.9600 | C13B—H13D | 0.9600 |
C13A—H13B | 0.9600 | C13B—H13E | 0.9600 |
C13A—H13C | 0.9600 | C13B—H13F | 0.9600 |
O1A—H1A | 0.8200 | O1B—H1B | 0.8200 |
O2A—H2A1 | 0.8200 | O2B—H2B1 | 0.8200 |
O3A—H3A | 0.8200 | O3B—H3B | 0.8200 |
| | | |
C2A—C1A—C11A | 121.4 (2) | C2B—C1B—C11B | 121.8 (2) |
C2A—C1A—C6A | 110.0 (2) | C2B—C1B—C6B | 110.2 (2) |
C11A—C1A—C6A | 99.5 (2) | C11B—C1B—C6B | 99.8 (2) |
C2A—C1A—C10A | 113.5 (2) | C2B—C1B—C10B | 112.7 (2) |
C11A—C1A—C10A | 100.6 (2) | C11B—C1B—C10B | 100.4 (2) |
C6A—C1A—C10A | 110.6 (2) | C6B—C1B—C10B | 110.9 (2) |
O1A—C2A—C3A | 107.5 (2) | O1B—C2B—C3B | 108.5 (2) |
O1A—C2A—C1A | 112.0 (2) | O1B—C2B—C1B | 111.2 (2) |
C3A—C2A—C1A | 110.6 (2) | C3B—C2B—C1B | 109.3 (2) |
O1A—C2A—H2A | 108.9 | O1B—C2B—H2B | 109.3 |
C3A—C2A—H2A | 108.9 | C3B—C2B—H2B | 109.3 |
C1A—C2A—H2A | 108.9 | C1B—C2B—H2B | 109.3 |
C2A—C3A—C4A | 112.2 (2) | C2B—C3B—C4B | 112.2 (2) |
C2A—C3A—H3A1 | 109.2 | C2B—C3B—H3B1 | 109.2 |
C4A—C3A—H3A1 | 109.2 | C4B—C3B—H3B1 | 109.2 |
C2A—C3A—H3A2 | 109.2 | C2B—C3B—H3B2 | 109.2 |
C4A—C3A—H3A2 | 109.2 | C4B—C3B—H3B2 | 109.2 |
H3A1—C3A—H3A2 | 107.9 | H3B1—C3B—H3B2 | 107.9 |
C5A—C4A—C3A | 112.5 (2) | C5B—C4B—C3B | 113.3 (2) |
C5A—C4A—H4A1 | 109.1 | C5B—C4B—H4B1 | 108.9 |
C3A—C4A—H4A1 | 109.1 | C3B—C4B—H4B1 | 108.9 |
C5A—C4A—H4A2 | 109.1 | C5B—C4B—H4B2 | 108.9 |
C3A—C4A—H4A2 | 109.1 | C3B—C4B—H4B2 | 108.9 |
H4A1—C4A—H4A2 | 107.8 | H4B1—C4B—H4B2 | 107.7 |
O2A—C5A—C4A | 110.5 (2) | O2B—C5B—C4B | 110.2 (2) |
O2A—C5A—C6A | 109.2 (2) | O2B—C5B—C6B | 110.5 (2) |
C4A—C5A—C6A | 109.1 (2) | C4B—C5B—C6B | 110.5 (2) |
O2A—C5A—H5A | 109.3 | O2B—C5B—H5B | 108.5 |
C4A—C5A—H5A | 109.3 | C4B—C5B—H5B | 108.5 |
C6A—C5A—H5A | 109.3 | C6B—C5B—H5B | 108.5 |
O3A—C6A—C5A | 107.1 (2) | O3B—C6B—C5B | 107.8 (2) |
O3A—C6A—C1A | 106.38 (19) | O3B—C6B—C1B | 104.52 (19) |
C5A—C6A—C1A | 110.3 (2) | C5B—C6B—C1B | 110.6 (2) |
O3A—C6A—C7A | 110.3 (2) | O3B—C6B—C7B | 111.3 (2) |
C5A—C6A—C7A | 119.3 (2) | C5B—C6B—C7B | 119.3 (2) |
C1A—C6A—C7A | 102.8 (2) | C1B—C6B—C7B | 102.3 (2) |
C12A—C7A—C13A | 107.7 (3) | C13B—C7B—C12B | 107.1 (2) |
C12A—C7A—C8A | 109.1 (2) | C13B—C7B—C8B | 112.7 (3) |
C13A—C7A—C8A | 112.7 (2) | C12B—C7B—C8B | 109.6 (2) |
C12A—C7A—C6A | 112.0 (2) | C13B—C7B—C6B | 113.8 (2) |
C13A—C7A—C6A | 114.0 (2) | C12B—C7B—C6B | 111.8 (2) |
C8A—C7A—C6A | 101.2 (2) | C8B—C7B—C6B | 101.9 (2) |
C9A—C8A—C11A | 99.9 (2) | C9B—C8B—C11B | 99.7 (2) |
C9A—C8A—C7A | 110.9 (2) | C9B—C8B—C7B | 111.5 (3) |
C11A—C8A—C7A | 103.7 (2) | C11B—C8B—C7B | 103.2 (2) |
C9A—C8A—H8A | 113.7 | C9B—C8B—H8B | 113.7 |
C11A—C8A—H8A | 113.7 | C11B—C8B—H8B | 113.7 |
C7A—C8A—H8A | 113.7 | C7B—C8B—H8B | 113.7 |
C8A—C9A—C10A | 102.2 (2) | C8B—C9B—C10B | 102.1 (2) |
C8A—C9A—H9A1 | 111.3 | C8B—C9B—H9B1 | 111.4 |
C10A—C9A—H9A1 | 111.3 | C10B—C9B—H9B1 | 111.4 |
C8A—C9A—H9A2 | 111.3 | C8B—C9B—H9B2 | 111.4 |
C10A—C9A—H9A2 | 111.3 | C10B—C9B—H9B2 | 111.4 |
H9A1—C9A—H9A2 | 109.2 | H9B1—C9B—H9B2 | 109.2 |
C9A—C10A—C1A | 104.1 (2) | C9B—C10B—C1B | 104.2 (2) |
C9A—C10A—H10A | 110.9 | C9B—C10B—H10C | 110.9 |
C1A—C10A—H10A | 110.9 | C1B—C10B—H10C | 110.9 |
C9A—C10A—H10B | 110.9 | C9B—C10B—H10D | 110.9 |
C1A—C10A—H10B | 110.9 | C1B—C10B—H10D | 110.9 |
H10A—C10A—H10B | 108.9 | H10C—C10B—H10D | 108.9 |
C8A—C11A—C1A | 94.4 (2) | C8B—C11B—C1B | 94.4 (2) |
C8A—C11A—H11A | 112.8 | C8B—C11B—H11C | 112.8 |
C1A—C11A—H11A | 112.8 | C1B—C11B—H11C | 112.8 |
C8A—C11A—H11B | 112.8 | C8B—C11B—H11D | 112.8 |
C1A—C11A—H11B | 112.8 | C1B—C11B—H11D | 112.8 |
H11A—C11A—H11B | 110.3 | H11C—C11B—H11D | 110.3 |
C7A—C12A—H12A | 109.5 | C7B—C12B—H12D | 109.5 |
C7A—C12A—H12B | 109.5 | C7B—C12B—H12E | 109.5 |
H12A—C12A—H12B | 109.5 | H12D—C12B—H12E | 109.5 |
C7A—C12A—H12C | 109.5 | C7B—C12B—H12F | 109.5 |
H12A—C12A—H12C | 109.5 | H12D—C12B—H12F | 109.5 |
H12B—C12A—H12C | 109.5 | H12E—C12B—H12F | 109.5 |
C7A—C13A—H13A | 109.5 | C7B—C13B—H13D | 109.5 |
C7A—C13A—H13B | 109.5 | C7B—C13B—H13E | 109.5 |
H13A—C13A—H13B | 109.5 | H13D—C13B—H13E | 109.5 |
C7A—C13A—H13C | 109.5 | C7B—C13B—H13F | 109.5 |
H13A—C13A—H13C | 109.5 | H13D—C13B—H13F | 109.5 |
H13B—C13A—H13C | 109.5 | H13E—C13B—H13F | 109.5 |
C2A—O1A—H1A | 109.5 | C2B—O1B—H1B | 109.5 |
C5A—O2A—H2A1 | 109.5 | C5B—O2B—H2B1 | 109.5 |
C6A—O3A—H3A | 109.5 | C6B—O3B—H3B | 109.5 |
| | | |
C11A—C1A—C2A—O1A | −67.4 (3) | C10B—C1B—C2B—O1B | −54.3 (3) |
C6A—C1A—C2A—O1A | 177.2 (2) | C11B—C1B—C2B—C3B | −175.3 (2) |
C10A—C1A—C2A—O1A | 52.6 (3) | C6B—C1B—C2B—C3B | −59.1 (3) |
C11A—C1A—C2A—C3A | 172.7 (2) | C10B—C1B—C2B—C3B | 65.4 (3) |
C6A—C1A—C2A—C3A | 57.3 (3) | O1B—C2B—C3B—C4B | 177.1 (2) |
C10A—C1A—C2A—C3A | −67.3 (3) | C1B—C2B—C3B—C4B | 55.7 (3) |
O1A—C2A—C3A—C4A | −176.8 (2) | C2B—C3B—C4B—C5B | −53.1 (3) |
C1A—C2A—C3A—C4A | −54.3 (3) | C3B—C4B—C5B—O2B | 174.6 (2) |
C2A—C3A—C4A—C5A | 53.9 (3) | C3B—C4B—C5B—C6B | 52.2 (3) |
C3A—C4A—C5A—O2A | −175.2 (2) | O2B—C5B—C6B—O3B | −63.8 (3) |
C3A—C4A—C5A—C6A | −55.2 (3) | C4B—C5B—C6B—O3B | 58.4 (3) |
O2A—C5A—C6A—O3A | 63.7 (3) | O2B—C5B—C6B—C1B | −177.5 (2) |
C4A—C5A—C6A—O3A | −57.2 (3) | C4B—C5B—C6B—C1B | −55.2 (3) |
O2A—C5A—C6A—C1A | 179.1 (2) | O2B—C5B—C6B—C7B | 64.3 (3) |
C4A—C5A—C6A—C1A | 58.2 (3) | C4B—C5B—C6B—C7B | −173.4 (2) |
O2A—C5A—C6A—C7A | −62.4 (3) | C2B—C1B—C6B—O3B | −55.9 (2) |
C4A—C5A—C6A—C7A | 176.8 (2) | C11B—C1B—C6B—O3B | 73.4 (2) |
C2A—C1A—C6A—O3A | 55.6 (3) | C10B—C1B—C6B—O3B | 178.5 (2) |
C11A—C1A—C6A—O3A | −72.9 (2) | C2B—C1B—C6B—C5B | 59.8 (3) |
C10A—C1A—C6A—O3A | −178.2 (2) | C11B—C1B—C6B—C5B | −170.9 (2) |
C2A—C1A—C6A—C5A | −60.1 (3) | C10B—C1B—C6B—C5B | −65.7 (3) |
C11A—C1A—C6A—C5A | 171.3 (2) | C2B—C1B—C6B—C7B | −172.1 (2) |
C10A—C1A—C6A—C5A | 66.0 (3) | C11B—C1B—C6B—C7B | −42.8 (2) |
C2A—C1A—C6A—C7A | 171.6 (2) | C10B—C1B—C6B—C7B | 62.4 (3) |
C11A—C1A—C6A—C7A | 43.0 (2) | C5B—C6B—C7B—C13B | 9.4 (3) |
C10A—C1A—C6A—C7A | −62.2 (3) | C1B—C6B—C7B—C13B | −112.9 (3) |
O3A—C6A—C7A—C12A | −12.1 (3) | O3B—C6B—C7B—C12B | 14.5 (3) |
C5A—C6A—C7A—C12A | 112.4 (3) | O3B—C6B—C7B—C13B | 135.9 (2) |
C1A—C6A—C7A—C12A | −125.2 (2) | C5B—C6B—C7B—C12B | −112.0 (3) |
O3A—C6A—C7A—C13A | −134.7 (3) | C1B—C6B—C7B—C12B | 125.6 (2) |
C5A—C6A—C7A—C13A | −10.2 (4) | O3B—C6B—C7B—C8B | −102.4 (2) |
C1A—C6A—C7A—C13A | 112.2 (3) | C5B—C6B—C7B—C8B | 131.0 (2) |
O3A—C6A—C7A—C8A | 104.1 (2) | C1B—C6B—C7B—C8B | 8.7 (2) |
C5A—C6A—C7A—C8A | −131.4 (2) | C13B—C7B—C8B—C9B | 44.7 (3) |
C1A—C6A—C7A—C8A | −9.0 (2) | C12B—C7B—C8B—C9B | 163.8 (2) |
C12A—C7A—C8A—C9A | −163.7 (3) | C6B—C7B—C8B—C9B | −77.6 (3) |
C13A—C7A—C8A—C9A | −44.1 (3) | C13B—C7B—C8B—C11B | 150.9 (2) |
C6A—C7A—C8A—C9A | 78.0 (3) | C12B—C7B—C8B—C11B | −90.0 (3) |
C12A—C7A—C8A—C11A | 89.9 (3) | C6B—C7B—C8B—C11B | 28.6 (3) |
C13A—C7A—C8A—C11A | −150.5 (3) | C11B—C8B—C9B—C10B | −43.0 (3) |
C6A—C7A—C8A—C11A | −28.3 (3) | C7B—C8B—C9B—C10B | 65.5 (3) |
C11A—C8A—C9A—C10A | 42.4 (3) | C8B—C9B—C10B—C1B | 8.4 (3) |
C7A—C8A—C9A—C10A | −66.5 (3) | C2B—C1B—C10B—C9B | 160.0 (2) |
C8A—C9A—C10A—C1A | −7.9 (3) | C11B—C1B—C10B—C9B | 28.9 (3) |
C2A—C1A—C10A—C9A | −160.5 (2) | C6B—C1B—C10B—C9B | −75.9 (3) |
C11A—C1A—C10A—C9A | −29.2 (3) | C9B—C8B—C11B—C1B | 60.5 (2) |
C6A—C1A—C10A—C9A | 75.3 (3) | C7B—C8B—C11B—C1B | −54.4 (2) |
C9A—C8A—C11A—C1A | −60.0 (2) | C2B—C1B—C11B—C8B | −179.2 (2) |
C7A—C8A—C11A—C1A | 54.5 (2) | C6B—C1B—C11B—C8B | 59.5 (2) |
C2A—C1A—C11A—C8A | −179.9 (2) | C10B—C1B—C11B—C8B | −54.0 (2) |
C6A—C1A—C11A—C8A | −59.3 (2) | O1A—C2A—C5A—O2A | 175.0 (4) |
C10A—C1A—C11A—C8A | 54.0 (2) | O1A—C2A—C6A—O3A | −132.2 (3) |
C11B—C1B—C2B—O1B | 65.0 (3) | O1B—C2B—C5B—O2B | −175.0 (4) |
C6B—C1B—C2B—O1B | −178.8 (2) | O1B—C2B—C6B—O3B | 128.3 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···O1B | 0.82 | 1.99 | 2.754 (3) | 154 |
O3A—H3A···O2A | 0.82 | 2.45 | 2.826 (2) | 109 |
O3B—H3B···O2B | 0.82 | 2.57 | 2.861 (3) | 103 |
O2B—H2B1···O1Ai | 0.82 | 2.12 | 2.876 (3) | 154 |
O2A—H2A1···O2Bii | 0.82 | 2.09 | 2.908 (3) | 177 |
O3A—H3A···O2Aiii | 0.82 | 1.99 | 2.733 (2) | 151 |
O1B—H1B···O3Biv | 0.82 | 2.17 | 2.971 (3) | 166 |
O3B—H3B···O3Aiv | 0.82 | 2.17 | 2.940 (2) | 155 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z+1; (iii) −x+2, −y, −z+2; (iv) −x+2, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | C13H22O3 |
Mr | 226.31 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.812 (2), 11.141 (1), 11.443 (2) |
α, β, γ (°) | 82.47 (1), 77.56 (1), 89.46 (1) |
V (Å3) | 1210.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.5 × 0.4 × 0.3 |
|
Data collection |
Diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4499, 4259, 2972 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.156, 1.10 |
No. of reflections | 4259 |
No. of parameters | 299 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.24, −0.21 |
Selected geometric parameters (Å, º) topC1A—C2A | 1.524 (4) | C1B—C2B | 1.524 (4) |
C2A—O1A | 1.434 (3) | C2B—O1B | 1.433 (3) |
C5A—O2A | 1.436 (3) | C5B—O2B | 1.441 (3) |
C6A—O3A | 1.434 (3) | C6B—O3B | 1.449 (3) |
C6A—C7A | 1.596 (4) | C6B—C7B | 1.589 (4) |
C7A—C8A | 1.561 (4) | C7B—C8B | 1.565 (4) |
| | | |
C2A—C1A—C6A | 110.0 (2) | C2B—C1B—C6B | 110.2 (2) |
C11A—C1A—C6A | 99.5 (2) | C11B—C1B—C6B | 99.8 (2) |
C11A—C1A—C10A | 100.6 (2) | C11B—C1B—C10B | 100.4 (2) |
C1A—C6A—C7A | 102.8 (2) | C1B—C6B—C7B | 102.3 (2) |
C8A—C7A—C6A | 101.2 (2) | C8B—C7B—C6B | 101.9 (2) |
| | | |
C6A—C1A—C2A—O1A | 177.2 (2) | C6B—C1B—C2B—O1B | −178.8 (2) |
O1A—C2A—C3A—C4A | −176.8 (2) | O1B—C2B—C3B—C4B | 177.1 (2) |
C3A—C4A—C5A—O2A | −175.2 (2) | C3B—C4B—C5B—O2B | 174.6 (2) |
O2A—C5A—C6A—O3A | 63.7 (3) | O2B—C5B—C6B—O3B | −63.8 (3) |
C4A—C5A—C6A—O3A | −57.2 (3) | C4B—C5B—C6B—O3B | 58.4 (3) |
O2A—C5A—C6A—C1A | 179.1 (2) | O2B—C5B—C6B—C1B | −177.5 (2) |
C2A—C1A—C6A—O3A | 55.6 (3) | C2B—C1B—C6B—O3B | −55.9 (2) |
C10A—C1A—C6A—O3A | −178.2 (2) | C10B—C1B—C6B—O3B | 178.5 (2) |
O3A—C6A—C7A—C12A | −12.1 (3) | O3B—C6B—C7B—C12B | 14.5 (3) |
O3A—C6A—C7A—C13A | −134.7 (3) | O3B—C6B—C7B—C13B | 135.9 (2) |
C1A—C6A—C7A—C8A | −9.0 (2) | C1B—C6B—C7B—C8B | 8.7 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···O1B | 0.82 | 1.99 | 2.754 (3) | 154 |
O3A—H3A···O2A | 0.82 | 2.45 | 2.826 (2) | 109 |
O3B—H3B···O2B | 0.82 | 2.57 | 2.861 (3) | 103 |
O2B—H2B1···O1Ai | 0.82 | 2.12 | 2.876 (3) | 154 |
O2A—H2A1···O2Bii | 0.82 | 2.09 | 2.908 (3) | 177 |
O3A—H3A···O2Aiii | 0.82 | 1.99 | 2.733 (2) | 151 |
O1B—H1B···O3Biv | 0.82 | 2.17 | 2.971 (3) | 166 |
O3B—H3B···O3Aiv | 0.82 | 2.17 | 2.940 (2) | 155 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z+1; (iii) −x+2, −y, −z+2; (iv) −x+2, −y+1, −z+1. |
Khusimone, (I), a norsesquiterpene ketone containing a tricyclo[6.2.1.01,5]undecane skeleton, is one of the main olfactively important constituents of vetiver oil (Büchi et al., 1977). In connection with our studies directed towards the synthesis and characterization of bridged ring systems related to tricyclic sesquiterpenes (Das et al., 1996; Pati et al., 2000), the title tricyclic triol, (II), has been synthesized. This triol possesses the requisite structural features for a potential intermediate in a total synthesis of khusimone. The structure determination of (II) was undertaken in order to establish the relative stereochemistries of the five asymmetric centres (C1, C2, C5, C6 and C8), and to devise the subsequent sequence of reactions leading to the total synthesis of (I). \sch
Compound (II) consists of a cyclohexane ring trans fused to a cyclopentane ring bridged via an ethyl moiety. The asymmetric unit of (II) contains two crystallographically independent molecules, A and B (Fig. 1), with almost similar geometries. Equivalent bond distances and angles in the two molecules agree within experimental limits. In both molecules, the torsion angles (Table 1) about the C2A—C3A, C4A—C5A, C2B—C3B and C4B—C5B bonds indicate the equatorial orientations of the two hydroxyl groups at the C2 and C5 positions, while the axial orientation of the OH group at the ring junction C atom (C6A and C6B) is evident from the torsion angles about the C5A—C6A and C5B—C6B bonds.
The two methyl groups at C7A and C7B are in almost syn-periplanar and gauche orientations with respect to the C6A—O3A and C6B—O3B bonds [O3A—C6A—C7A—C12A -12.1 (3), O3B—C6B—C7B—C12B 14.5 (3), O3A—C6A—C7A—C13A -134.7 (3) and O3B—O6B—C7B—C13B 135.9 (2)°].
The C—C [1.515 (4)–1.596 (4) Å] and C—O [1.433 (3)–1.449 (3) Å] bond distances agree well with the corresponding values reported in the literature (Allen et al., 1987). The lengthening of the C3C—CC2O bond distances [C6A—C7A 1.596 (4) Å in molecule A and C6B—C7B 1.589 (4) Å in molecule B] compared with other C—C bond lengths (Table 1) is consistant with observations in related tricycloundecane structures (Pati et al., 2002).
The C1—C6 cyclohexane ring displays a chair conformation, with puckering parameters (Cremer & Pople, 1975) Q = 0.586 (3) Å, q2 = 0.051 (3) Å, q3 = -0.584 (3) Å and θ = 175.1 (3)° for molecule A, and Q = 0.579 (3) Å, q2 = 0.060 (3) Å, q3 = 0.576 (3) Å and θ = 5.9 (3)° for molecule B. The cyclopentane ring (C1/C6/C7/C8/C11) adopts an almost envelope conformation, with atom C11 deviating by 0.877 (4) Å in both molecules A and B from the least-squares plane through the remaining endocyclic atoms.
The dihedral angles between the planar parts of the fused cyclohexane and cyclopentane rings are 16.3 (2)° in molecule A and 18.2 (1)° in molecule B. The other five-membered ring (C1/C10/C8/C9/C11), with ring puckering parameters q2 = 0.606 (3) Å and ϕ = -43.4 (3)° (for molecule A) and q2 = 0.613 (3) Å and ϕ = 136.4 (3)° (for molecule B), also assumes a distorted envelope conformation, with atom C11 displaced from the ring plane by 0.884 (4) Å in molecule A and 0.887 (4) Å in molecule B. The molecule of (II) has five chiral centres (C1, C2, C5, C6 and C8) and, from the centrosymmetric space group, it follows that the crystal is a racemate.
Intramolecular O—H···O hydrogen bonds (Table 2) influence the conformation of the two independent molecules of (II), A and B. In addition, each hydroxyl group in the molecule acts as a potential donor as well as an acceptor in an extensive intermolecular hydrogen-bond network. The resulting hydrogen-bonded supramolecular structure is of considerable complexity. A similar supramolecular network, solely controlled by hydrogen bonds between hydroxyl groups, has been reported by Deák et al. (2001).
A simplified description of the supramolecular assembly in (II), in terms of tetramolecular motifs leading to parallel chains and the connections between such chains, can be visualized as follows. The two molecules in the asymmetric unit, A and B, are linked via a strong O1A—H1A···O1B(x, y, z) hydrogen bond (Table 2 and Fig. 1). The intermolecular O—H···O hydrogen bonds between the molecules in the asymmetric unit and their centrosymmetrically related counterparts, O2B-H2B1···O1A(1 - x, 1 - y, 1 - z), result in the formation of a four-membered A2B2 aggregate in the structure (Fig. 2). These supramolecular A2B2 units, connected through O2A-H2A1···O2B(x, y - 1, 1 + z) hydrogen bonds, give rise to infinite ABAB··· chains parallel to the [011] direction (Fig. 3). These chains are interlinked by O3A—H3A···O2A(2 - x, -y, 2 - z), O1B—H1B···O3B(2 - x, 1 - y, 1 - z) and O3B—H3B···O3A(2 - x, 1 - y, 1 - z) hydrogen bonds to complete the two-dimensional supramolecular network in the (011) plane.