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cis-Verbenol (alternative name: 4,6,6-trimethylbicyclo[3.1.1]hept-3-en-2-ol), C
10H
16O, forms an orthorhombic
P2
12
12
1 crystal that contains three molecules per asymmetric unit. These three molecules form hydrogen-bonded helices parallel to the shortest axis of the lattice. The O
O distances associated with the hydrogen bonds are 2.760 (3), 2.760 (3) and 2.766 (3) Å.
Supporting information
CCDC reference: 144629
Verbenol was obtained from Aldrich as a 50+% enantiomeric excess
(1S,2S,5S/1R,2R,5R) mixture and used as received.
Reported enantiomeric excess was determined by Aldrich using chiral stationary
phase gas chromatography. A 0.6/0.4 (e.s.d. 0.1)
1S,2S,5S/1R,2R,5R enantiomeric ratio was
determined in our lab by polarimetry on a sample dissolved in acetone. The
enantiomeric content is a measure of the bulk material and a corresponding
value for the individual crystal could not be determined with the methods
used. A verbenol purity of 94% was found by gas chromatography on an achiral
stationary phase. Crystals of (I) (m.p. 341.5–346.5 K) were prepared by slow
evaporation of a solution in 100% methanol.
Hydroxy H atoms were located and refined isotropically. All other H atoms were
refined as riding models on the appropriate C atoms using the SHELXL97
(Sheldrick, 1997) restraints and assigned isotropic displacement parameters of
1.5 for methyl H and 1.2 for all others.
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX (Farrugia, 1998) and ORTEP-3 for Windows (Farrugia 1997); software used to prepare material for publication: ORTEP-3 for Windows.
Crystal data top
C10H16O | Dx = 1.089 Mg m−3 |
Mr = 152.23 | Melting point: 341.5-346.5 K K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.0115 (1) Å | Cell parameters from 252 reflections |
b = 18.7691 (6) Å | θ = 4.1–25.0° |
c = 21.1681 (7) Å | µ = 0.07 mm−1 |
V = 2785.71 (13) Å3 | T = 200 K |
Z = 12 | Prism, colorless |
F(000) = 1008 | 0.20 × 0.14 × 0.13 mm |
Data collection top
Nonius KappaCCD diffractometer | Rint = 0.042 |
ϕ + ω scan | θmax = 24.8°, θmin = 4.1° |
13724 measured reflections | h = −8→7 |
2717 independent reflections | k = −22→22 |
2360 reflections with I > 2σ(I) | l = −24→24 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.047 | Calculated w = 1/[σ2(Fo2) + (0.0812P)2 + 0.6806P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.127 | (Δ/σ)max < 0.001 |
S = 1.05 | Δρmax = 0.24 e Å−3 |
2717 reflections | Δρmin = −0.23 e Å−3 |
310 parameters | |
Crystal data top
C10H16O | V = 2785.71 (13) Å3 |
Mr = 152.23 | Z = 12 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.0115 (1) Å | µ = 0.07 mm−1 |
b = 18.7691 (6) Å | T = 200 K |
c = 21.1681 (7) Å | 0.20 × 0.14 × 0.13 mm |
Data collection top
Nonius KappaCCD diffractometer | 2360 reflections with I > 2σ(I) |
13724 measured reflections | Rint = 0.042 |
2717 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.127 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.24 e Å−3 |
2717 reflections | Δρmin = −0.23 e Å−3 |
310 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.9297 (3) | 0.13325 (11) | 0.69441 (12) | 0.0461 (6) | |
HO1 | 0.841 (6) | 0.161 (2) | 0.6964 (19) | 0.062 (12)* | |
C1 | 1.0130 (4) | −0.04798 (15) | 0.61378 (14) | 0.0365 (7) | |
H1 | 1.0619 | −0.0889 | 0.5882 | 0.044* | |
C2 | 0.8642 (4) | −0.00134 (16) | 0.58270 (14) | 0.0391 (7) | |
C3 | 0.7918 (4) | 0.05117 (17) | 0.61743 (15) | 0.0406 (7) | |
H3 | 0.6978 | 0.0819 | 0.6001 | 0.049* | |
C4 | 0.8597 (4) | 0.06179 (15) | 0.68452 (15) | 0.0392 (7) | |
H4 | 0.7497 | 0.0535 | 0.7137 | 0.047* | |
C5 | 1.0155 (4) | 0.00809 (15) | 0.70005 (14) | 0.0373 (7) | |
H5 | 1.0687 | 0.0113 | 0.7438 | 0.045* | |
C6 | 1.1669 (4) | 0.00033 (15) | 0.64610 (14) | 0.0370 (7) | |
C7 | 0.9383 (5) | −0.06603 (16) | 0.68093 (15) | 0.0421 (7) | |
H7A | 0.798 | −0.0708 | 0.6839 | 0.051* | |
H7B | 1.0041 | −0.1065 | 0.7015 | 0.051* | |
C8 | 0.8104 (6) | −0.0148 (2) | 0.51534 (16) | 0.0590 (10) | |
H8A | 0.8805 | −0.0563 | 0.4995 | 0.089* | |
H8B | 0.8425 | 0.0271 | 0.4898 | 0.089* | |
H8C | 0.673 | −0.0239 | 0.5126 | 0.089* | |
C9 | 1.2399 (5) | 0.06494 (17) | 0.61060 (17) | 0.0447 (8) | |
H9A | 1.1316 | 0.0935 | 0.5959 | 0.067* | |
H9B | 1.3155 | 0.0493 | 0.5742 | 0.067* | |
H9C | 1.3197 | 0.0938 | 0.6387 | 0.067* | |
C10 | 1.3407 (5) | −0.04280 (19) | 0.66881 (18) | 0.0538 (9) | |
H10A | 1.297 | −0.085 | 0.6919 | 0.081* | |
H10B | 1.419 | −0.0132 | 0.6967 | 0.081* | |
H10C | 1.4166 | −0.0577 | 0.6323 | 0.081* | |
O1' | 0.5930 (3) | 0.20817 (12) | 0.68225 (12) | 0.0439 (6) | |
HO1' | 0.530 (7) | 0.200 (2) | 0.707 (2) | 0.068 (16)* | |
C1' | 0.6466 (5) | 0.38039 (16) | 0.58602 (15) | 0.0467 (8) | |
H1' | 0.6871 | 0.4274 | 0.5684 | 0.056* | |
C2' | 0.4952 (5) | 0.38247 (17) | 0.63741 (15) | 0.0462 (8) | |
C3' | 0.4337 (5) | 0.32051 (17) | 0.65885 (15) | 0.0422 (7) | |
H3' | 0.3381 | 0.3189 | 0.6906 | 0.051* | |
C4' | 0.5152 (5) | 0.25252 (16) | 0.63289 (15) | 0.0398 (7) | |
H4' | 0.4107 | 0.2256 | 0.6113 | 0.048* | |
C5' | 0.6702 (5) | 0.26843 (15) | 0.58467 (14) | 0.0390 (7) | |
H5' | 0.7321 | 0.2258 | 0.5651 | 0.047* | |
C6' | 0.8094 (5) | 0.32900 (17) | 0.60630 (15) | 0.0427 (8) | |
C7' | 0.5842 (6) | 0.32335 (17) | 0.53745 (14) | 0.0478 (8) | |
H7'1 | 0.6515 | 0.3261 | 0.4964 | 0.057* | |
H7'2 | 0.4445 | 0.3194 | 0.5317 | 0.057* | |
C8' | 0.4249 (8) | 0.45320 (19) | 0.66133 (19) | 0.0738 (13) | |
H8'1 | 0.4891 | 0.4917 | 0.6384 | 0.111* | |
H8'2 | 0.4528 | 0.4573 | 0.7065 | 0.111* | |
H8'3 | 0.2869 | 0.4567 | 0.6546 | 0.111* | |
C9' | 0.8807 (5) | 0.33147 (19) | 0.67444 (16) | 0.0524 (9) | |
H9'1 | 0.9801 | 0.2954 | 0.6804 | 0.079* | |
H9'2 | 0.7744 | 0.3219 | 0.7033 | 0.079* | |
H9'3 | 0.9334 | 0.3788 | 0.6834 | 0.079* | |
C10' | 0.9832 (6) | 0.3339 (2) | 0.56249 (19) | 0.0629 (10) | |
H10D | 0.9408 | 0.3325 | 0.5184 | 0.094* | |
H10E | 1.0689 | 0.2937 | 0.5707 | 0.094* | |
H10F | 1.051 | 0.3787 | 0.5704 | 0.094* | |
O1'' | 0.2623 (3) | 0.18282 (14) | 0.74930 (11) | 0.0459 (6) | |
HO1'' | 0.180 (7) | 0.167 (2) | 0.731 (2) | 0.059 (13)* | |
C1'' | 0.3540 (5) | 0.20439 (17) | 0.92741 (15) | 0.0447 (8) | |
H1'' | 0.4054 | 0.2024 | 0.9714 | 0.054* | |
C2'' | 0.2085 (5) | 0.14812 (17) | 0.90990 (15) | 0.0415 (7) | |
C3'' | 0.1318 (5) | 0.15230 (17) | 0.85232 (16) | 0.0423 (8) | |
H3'' | 0.0392 | 0.1185 | 0.8391 | 0.051* | |
C4'' | 0.1939 (4) | 0.21129 (16) | 0.80842 (15) | 0.0411 (7) | |
H4'' | 0.0809 | 0.2422 | 0.7995 | 0.049* | |
C5'' | 0.3461 (5) | 0.25668 (15) | 0.83877 (15) | 0.0405 (7) | |
H5'' | 0.3941 | 0.2972 | 0.8125 | 0.049* | |
C6'' | 0.5040 (4) | 0.21154 (17) | 0.87321 (15) | 0.0386 (7) | |
C7'' | 0.2725 (5) | 0.27704 (18) | 0.90547 (17) | 0.0516 (9) | |
H7''1 | 0.3366 | 0.319 | 0.9243 | 0.062* | |
H7''2 | 0.132 | 0.2809 | 0.9087 | 0.062* | |
C8'' | 0.1587 (6) | 0.0908 (2) | 0.95609 (18) | 0.0659 (11) | |
H8''1 | 0.2314 | 0.0978 | 0.9951 | 0.099* | |
H8''2 | 0.1901 | 0.0442 | 0.9379 | 0.099* | |
H8''3 | 0.0219 | 0.0928 | 0.9655 | 0.099* | |
C9'' | 0.5812 (5) | 0.14423 (16) | 0.84258 (17) | 0.0422 (7) | |
H9''1 | 0.4747 | 0.1139 | 0.8293 | 0.063* | |
H9''2 | 0.6606 | 0.1184 | 0.873 | 0.063* | |
H9''3 | 0.6582 | 0.157 | 0.8056 | 0.063* | |
C10'' | 0.6759 (5) | 0.2577 (2) | 0.8924 (2) | 0.0587 (10) | |
H10G | 0.6305 | 0.3017 | 0.9123 | 0.088* | |
H10H | 0.751 | 0.2695 | 0.8548 | 0.088* | |
H10I | 0.7557 | 0.2313 | 0.9224 | 0.088* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0368 (12) | 0.0359 (11) | 0.0656 (15) | 0.0028 (10) | −0.0063 (11) | −0.0101 (11) |
C1 | 0.0377 (16) | 0.0336 (14) | 0.0383 (16) | −0.0034 (13) | −0.0008 (13) | −0.0003 (13) |
C2 | 0.0328 (15) | 0.0436 (16) | 0.0410 (16) | −0.0082 (14) | −0.0050 (13) | 0.0034 (14) |
C3 | 0.0282 (14) | 0.0443 (17) | 0.0493 (18) | −0.0006 (13) | −0.0087 (13) | 0.0042 (15) |
C4 | 0.0318 (15) | 0.0403 (15) | 0.0455 (17) | −0.0030 (13) | 0.0007 (14) | −0.0042 (14) |
C5 | 0.0396 (16) | 0.0392 (15) | 0.0333 (15) | −0.0007 (13) | −0.0022 (13) | 0.0027 (12) |
C6 | 0.0307 (14) | 0.0358 (15) | 0.0447 (17) | 0.0025 (13) | −0.0018 (13) | 0.0012 (13) |
C7 | 0.0475 (18) | 0.0381 (16) | 0.0408 (17) | −0.0031 (14) | 0.0010 (16) | 0.0049 (14) |
C8 | 0.059 (2) | 0.071 (2) | 0.047 (2) | −0.006 (2) | −0.0155 (17) | −0.0008 (18) |
C9 | 0.0332 (16) | 0.0446 (17) | 0.056 (2) | −0.0061 (14) | −0.0004 (15) | 0.0046 (15) |
C10 | 0.0433 (19) | 0.0534 (19) | 0.064 (2) | 0.0101 (17) | −0.0126 (17) | 0.0005 (17) |
O1' | 0.0389 (12) | 0.0440 (12) | 0.0489 (14) | 0.0083 (10) | 0.0076 (11) | 0.0147 (11) |
C1' | 0.062 (2) | 0.0352 (15) | 0.0431 (17) | −0.0099 (16) | −0.0064 (17) | 0.0067 (14) |
C2' | 0.060 (2) | 0.0392 (16) | 0.0392 (17) | 0.0105 (16) | −0.0045 (16) | 0.0030 (14) |
C3' | 0.0383 (17) | 0.0460 (18) | 0.0423 (16) | 0.0091 (15) | −0.0011 (14) | 0.0062 (14) |
C4' | 0.0374 (16) | 0.0361 (15) | 0.0458 (17) | −0.0029 (14) | −0.0002 (14) | 0.0057 (13) |
C5' | 0.0440 (17) | 0.0390 (16) | 0.0340 (15) | −0.0026 (14) | 0.0029 (14) | −0.0040 (13) |
C6' | 0.0432 (18) | 0.0440 (17) | 0.0409 (17) | −0.0072 (15) | 0.0000 (14) | −0.0001 (14) |
C7' | 0.058 (2) | 0.0517 (18) | 0.0338 (16) | −0.0019 (17) | −0.0062 (15) | 0.0019 (14) |
C8' | 0.111 (4) | 0.049 (2) | 0.061 (2) | 0.026 (2) | 0.001 (3) | −0.0006 (18) |
C9' | 0.048 (2) | 0.058 (2) | 0.051 (2) | −0.0095 (17) | −0.0081 (17) | −0.0034 (17) |
C10' | 0.053 (2) | 0.076 (3) | 0.060 (2) | −0.014 (2) | 0.0110 (19) | 0.006 (2) |
O1'' | 0.0361 (12) | 0.0638 (15) | 0.0378 (12) | −0.0074 (11) | −0.0006 (10) | −0.0047 (11) |
C1'' | 0.0406 (17) | 0.0554 (18) | 0.0381 (16) | 0.0014 (15) | 0.0001 (15) | −0.0077 (15) |
C2'' | 0.0341 (16) | 0.0507 (18) | 0.0396 (17) | 0.0001 (14) | 0.0062 (14) | −0.0017 (14) |
C3'' | 0.0300 (16) | 0.0479 (18) | 0.0490 (19) | −0.0032 (14) | 0.0067 (15) | −0.0033 (15) |
C4'' | 0.0322 (15) | 0.0464 (16) | 0.0446 (17) | 0.0050 (13) | −0.0014 (13) | −0.0013 (14) |
C5'' | 0.0390 (16) | 0.0322 (14) | 0.0502 (18) | 0.0038 (13) | −0.0007 (15) | 0.0008 (13) |
C6'' | 0.0294 (15) | 0.0423 (16) | 0.0443 (17) | −0.0015 (13) | −0.0029 (13) | −0.0041 (14) |
C7'' | 0.0465 (19) | 0.0478 (18) | 0.060 (2) | 0.0071 (15) | 0.0025 (17) | −0.0163 (16) |
C8'' | 0.064 (3) | 0.077 (3) | 0.056 (2) | −0.008 (2) | 0.015 (2) | 0.0103 (19) |
C9'' | 0.0336 (16) | 0.0420 (16) | 0.0508 (18) | 0.0042 (13) | −0.0004 (15) | −0.0017 (14) |
C10'' | 0.0431 (19) | 0.060 (2) | 0.073 (3) | −0.0106 (18) | −0.0092 (18) | −0.0115 (19) |
Geometric parameters (Å, º) top
O1—C4 | 1.444 (3) | C5'—H5' | 1 |
O1—HO1 | 0.81 (4) | C6'—C9' | 1.527 (5) |
C1—C2 | 1.512 (4) | C6'—C10' | 1.534 (5) |
C1—C7 | 1.552 (4) | C7'—H7'1 | 0.99 |
C1—C6 | 1.567 (4) | C7'—H7'2 | 0.99 |
C1—H1 | 1 | C8'—H8'1 | 0.98 |
C2—C3 | 1.330 (4) | C8'—H8'2 | 0.98 |
C2—C8 | 1.496 (4) | C8'—H8'3 | 0.98 |
C3—C4 | 1.511 (4) | C9'—H9'1 | 0.98 |
C3—H3 | 0.95 | C9'—H9'2 | 0.98 |
C4—C5 | 1.522 (4) | C9'—H9'3 | 0.98 |
C4—H4 | 1 | C10'—H10D | 0.98 |
C5—C7 | 1.547 (4) | C10'—H10E | 0.98 |
C5—C6 | 1.566 (4) | C10'—H10F | 0.98 |
C5—H5 | 1 | O1''—C4'' | 1.443 (4) |
C6—C9 | 1.516 (4) | O1''—HO1'' | 0.75 (5) |
C6—C10 | 1.540 (4) | C1''—C2'' | 1.515 (4) |
C7—H7A | 0.99 | C1''—C7'' | 1.550 (5) |
C7—H7B | 0.99 | C1''—C6'' | 1.562 (4) |
C8—H8A | 0.98 | C1''—H1'' | 1 |
C8—H8B | 0.98 | C2''—C3'' | 1.334 (5) |
C8—H8C | 0.98 | C2''—C8'' | 1.496 (5) |
C9—H9A | 0.98 | C3''—C4'' | 1.509 (4) |
C9—H9B | 0.98 | C3''—H3'' | 0.95 |
C9—H9C | 0.98 | C4''—C5'' | 1.509 (4) |
C10—H10A | 0.98 | C4''—H4'' | 1 |
C10—H10B | 0.98 | C5''—C7'' | 1.551 (5) |
C10—H10C | 0.98 | C5''—C6'' | 1.573 (4) |
O1'—C4' | 1.443 (4) | C5''—H5'' | 1 |
O1'—HO1' | 0.70 (4) | C6''—C9'' | 1.520 (4) |
C1'—C2' | 1.521 (5) | C6''—C10'' | 1.539 (4) |
C1'—C7' | 1.547 (4) | C7''—H7''1 | 0.99 |
C1'—C6' | 1.555 (5) | C7''—H7''2 | 0.99 |
C1'—H1' | 1 | C8''—H8''1 | 0.98 |
C2'—C3' | 1.321 (5) | C8''—H8''2 | 0.98 |
C2'—C8' | 1.504 (5) | C8''—H8''3 | 0.98 |
C3'—C4' | 1.503 (4) | C9''—H9''1 | 0.98 |
C3'—H3' | 0.95 | C9''—H9''2 | 0.98 |
C4'—C5' | 1.521 (4) | C9''—H9''3 | 0.98 |
C4'—H4' | 1 | C10''—H10G | 0.98 |
C5'—C7' | 1.557 (4) | C10''—H10H | 0.98 |
C5'—C6' | 1.567 (4) | C10''—H10I | 0.98 |
| | | |
C4—O1—HO1 | 110 (3) | C9'—C6'—C5' | 120.1 (3) |
C2—C1—C7 | 107.0 (3) | C10'—C6'—C5' | 111.2 (3) |
C2—C1—C6 | 109.3 (2) | C1'—C6'—C5' | 85.0 (2) |
C7—C1—C6 | 87.6 (2) | C1'—C7'—C5' | 85.5 (2) |
C2—C1—H1 | 116.4 | C1'—C7'—H7'1 | 114.4 |
C7—C1—H1 | 116.4 | C5'—C7'—H7'1 | 114.4 |
C6—C1—H1 | 116.4 | C1'—C7'—H7'2 | 114.4 |
C3—C2—C8 | 123.7 (3) | C5'—C7'—H7'2 | 114.4 |
C3—C2—C1 | 116.8 (3) | H7'1—C7'—H7'2 | 111.5 |
C8—C2—C1 | 119.4 (3) | C2'—C8'—H8'1 | 109.5 |
C2—C3—C4 | 119.8 (3) | C2'—C8'—H8'2 | 109.5 |
C2—C3—H3 | 120.1 | H8'1—C8'—H8'2 | 109.5 |
C4—C3—H3 | 120.1 | C2'—C8'—H8'3 | 109.5 |
O1—C4—C3 | 111.5 (3) | H8'1—C8'—H8'3 | 109.5 |
O1—C4—C5 | 109.9 (2) | H8'2—C8'—H8'3 | 109.5 |
C3—C4—C5 | 110.0 (2) | C6'—C9'—H9'1 | 109.5 |
O1—C4—H4 | 108.5 | C6'—C9'—H9'2 | 109.5 |
C3—C4—H4 | 108.5 | H9'1—C9'—H9'2 | 109.5 |
C5—C4—H4 | 108.5 | C6'—C9'—H9'3 | 109.5 |
C4—C5—C7 | 106.7 (2) | H9'1—C9'—H9'3 | 109.5 |
C4—C5—C6 | 113.0 (2) | H9'2—C9'—H9'3 | 109.5 |
C7—C5—C6 | 87.9 (2) | C6'—C10'—H10D | 109.5 |
C4—C5—H5 | 115.3 | C6'—C10'—H10E | 109.5 |
C7—C5—H5 | 115.3 | H10D—C10'—H10E | 109.5 |
C6—C5—H5 | 115.3 | C6'—C10'—H10F | 109.5 |
C9—C6—C10 | 108.0 (3) | H10D—C10'—H10F | 109.5 |
C9—C6—C5 | 121.1 (3) | H10E—C10'—H10F | 109.5 |
C10—C6—C5 | 111.0 (2) | C4''—O1''—HO1'' | 109 (3) |
C9—C6—C1 | 118.6 (3) | C2''—C1''—C7'' | 107.0 (3) |
C10—C6—C1 | 112.2 (2) | C2''—C1''—C6'' | 109.5 (2) |
C5—C6—C1 | 84.6 (2) | C7''—C1''—C6'' | 87.3 (2) |
C5—C7—C1 | 85.7 (2) | C2''—C1''—H1'' | 116.4 |
C5—C7—H7A | 114.4 | C7''—C1''—H1'' | 116.4 |
C1—C7—H7A | 114.4 | C6''—C1''—H1'' | 116.4 |
C5—C7—H7B | 114.4 | C3''—C2''—C8'' | 123.1 (3) |
C1—C7—H7B | 114.4 | C3''—C2''—C1'' | 117.0 (3) |
H7A—C7—H7B | 111.5 | C8''—C2''—C1'' | 119.9 (3) |
C2—C8—H8A | 109.5 | C2''—C3''—C4'' | 119.3 (3) |
C2—C8—H8B | 109.5 | C2''—C3''—H3'' | 120.3 |
H8A—C8—H8B | 109.5 | C4''—C3''—H3'' | 120.3 |
C2—C8—H8C | 109.5 | O1''—C4''—C5'' | 110.1 (3) |
H8A—C8—H8C | 109.5 | O1''—C4''—C3'' | 111.0 (3) |
H8B—C8—H8C | 109.5 | C5''—C4''—C3'' | 110.8 (3) |
C6—C9—H9A | 109.5 | O1''—C4''—H4'' | 108.3 |
C6—C9—H9B | 109.5 | C5''—C4''—H4'' | 108.3 |
H9A—C9—H9B | 109.5 | C3''—C4''—H4'' | 108.3 |
C6—C9—H9C | 109.5 | C4''—C5''—C7'' | 106.9 (3) |
H9A—C9—H9C | 109.5 | C4''—C5''—C6'' | 113.0 (2) |
H9B—C9—H9C | 109.5 | C7''—C5''—C6'' | 86.8 (2) |
C6—C10—H10A | 109.5 | C4''—C5''—H5'' | 115.5 |
C6—C10—H10B | 109.5 | C7''—C5''—H5'' | 115.5 |
H10A—C10—H10B | 109.5 | C6''—C5''—H5'' | 115.5 |
C6—C10—H10C | 109.5 | C9''—C6''—C10'' | 107.6 (3) |
H10A—C10—H10C | 109.5 | C9''—C6''—C1'' | 118.8 (3) |
H10B—C10—H10C | 109.5 | C10''—C6''—C1'' | 112.4 (3) |
C4'—O1'—HO1' | 115 (4) | C9''—C6''—C5'' | 120.0 (3) |
C2'—C1'—C7' | 107.2 (3) | C10''—C6''—C5'' | 111.7 (3) |
C2'—C1'—C6' | 109.3 (2) | C1''—C6''—C5'' | 85.0 (2) |
C7'—C1'—C6' | 87.8 (2) | C1''—C7''—C5'' | 86.2 (2) |
C2'—C1'—H1' | 116.3 | C1''—C7''—H7''1 | 114.3 |
C7'—C1'—H1' | 116.3 | C5''—C7''—H7''1 | 114.3 |
C6'—C1'—H1' | 116.3 | C1''—C7''—H7''2 | 114.3 |
C3'—C2'—C8' | 123.7 (3) | C5''—C7''—H7''2 | 114.3 |
C3'—C2'—C1' | 116.8 (3) | H7''1—C7''—H7''2 | 111.4 |
C8'—C2'—C1' | 119.5 (3) | C2''—C8''—H8''1 | 109.5 |
C2'—C3'—C4' | 119.9 (3) | C2''—C8''—H8''2 | 109.5 |
C2'—C3'—H3' | 120.1 | H8''1—C8''—H8''2 | 109.5 |
C4'—C3'—H3' | 120.1 | C2''—C8''—H8''3 | 109.5 |
O1'—C4'—C3' | 111.7 (3) | H8''1—C8''—H8''3 | 109.5 |
O1'—C4'—C5' | 109.2 (3) | H8''2—C8''—H8''3 | 109.5 |
C3'—C4'—C5' | 110.5 (2) | C6''—C9''—H9''1 | 109.5 |
O1'—C4'—H4' | 108.4 | C6''—C9''—H9''2 | 109.5 |
C3'—C4'—H4' | 108.4 | H9''1—C9''—H9''2 | 109.5 |
C5'—C4'—H4' | 108.4 | C6''—C9''—H9''3 | 109.5 |
C4'—C5'—C7' | 106.5 (3) | H9''1—C9''—H9''3 | 109.5 |
C4'—C5'—C6' | 113.0 (2) | H9''2—C9''—H9''3 | 109.5 |
C7'—C5'—C6' | 87.0 (2) | C6''—C10''—H10G | 109.5 |
C4'—C5'—H5' | 115.6 | C6''—C10''—H10H | 109.5 |
C7'—C5'—H5' | 115.6 | H10G—C10''—H10H | 109.5 |
C6'—C5'—H5' | 115.6 | C6''—C10''—H10I | 109.5 |
C9'—C6'—C10' | 108.0 (3) | H10G—C10''—H10I | 109.5 |
C9'—C6'—C1' | 118.8 (3) | H10H—C10''—H10I | 109.5 |
C10'—C6'—C1' | 112.3 (3) | | |
| | | |
C7—C1—C2—C3 | 44.9 (3) | C2'—C1'—C6'—C10' | −170.1 (3) |
C6—C1—C2—C3 | −48.6 (3) | C7'—C1'—C6'—C10' | 82.5 (3) |
C7—C1—C2—C8 | −136.8 (3) | C2'—C1'—C6'—C5' | 79.1 (3) |
C6—C1—C2—C8 | 129.7 (3) | C7'—C1'—C6'—C5' | −28.4 (2) |
C8—C2—C3—C4 | −178.1 (3) | C4'—C5'—C6'—C9' | 42.1 (4) |
C1—C2—C3—C4 | 0.1 (4) | C7'—C5'—C6'—C9' | 148.8 (3) |
C2—C3—C4—O1 | 124.5 (3) | C4'—C5'—C6'—C10' | 169.6 (3) |
C2—C3—C4—C5 | 2.4 (4) | C7'—C5'—C6'—C10' | −83.7 (3) |
O1—C4—C5—C7 | −173.5 (2) | C4'—C5'—C6'—C1' | −78.5 (3) |
C3—C4—C5—C7 | −50.5 (3) | C7'—C5'—C6'—C1' | 28.2 (2) |
O1—C4—C5—C6 | −78.6 (3) | C2'—C1'—C7'—C5' | −81.0 (3) |
C3—C4—C5—C6 | 44.4 (3) | C6'—C1'—C7'—C5' | 28.6 (2) |
C4—C5—C6—C9 | 40.9 (4) | C4'—C5'—C7'—C1' | 84.8 (3) |
C7—C5—C6—C9 | 148.2 (3) | C6'—C5'—C7'—C1' | −28.3 (2) |
C4—C5—C6—C10 | 168.9 (2) | C7''—C1''—C2''—C3'' | 44.7 (4) |
C7—C5—C6—C10 | −83.8 (3) | C6''—C1''—C2''—C3'' | −48.5 (4) |
C4—C5—C6—C1 | −79.4 (3) | C7''—C1''—C2''—C8'' | −136.1 (3) |
C7—C5—C6—C1 | 27.9 (2) | C6''—C1''—C2''—C8'' | 130.7 (3) |
C2—C1—C6—C9 | −43.2 (3) | C8''—C2''—C3''—C4'' | −178.8 (3) |
C7—C1—C6—C9 | −150.4 (3) | C1''—C2''—C3''—C4'' | 0.4 (4) |
C2—C1—C6—C10 | −170.2 (3) | C2''—C3''—C4''—O1'' | 124.5 (3) |
C7—C1—C6—C10 | 82.7 (3) | C2''—C3''—C4''—C5'' | 1.9 (4) |
C2—C1—C6—C5 | 79.4 (3) | O1''—C4''—C5''—C7'' | −172.8 (2) |
C7—C1—C6—C5 | −27.8 (2) | C3''—C4''—C5''—C7'' | −49.6 (3) |
C4—C5—C7—C1 | 85.3 (3) | O1''—C4''—C5''—C6'' | −79.0 (3) |
C6—C5—C7—C1 | −28.1 (2) | C3''—C4''—C5''—C6'' | 44.2 (3) |
C2—C1—C7—C5 | −81.3 (2) | C2''—C1''—C6''—C9'' | −42.9 (4) |
C6—C1—C7—C5 | 28.1 (2) | C7''—C1''—C6''—C9'' | −150.0 (3) |
C7'—C1'—C2'—C3' | 44.7 (4) | C2''—C1''—C6''—C10'' | −169.8 (3) |
C6'—C1'—C2'—C3' | −49.1 (4) | C7''—C1''—C6''—C10'' | 83.2 (3) |
C7'—C1'—C2'—C8' | −135.8 (3) | C2''—C1''—C6''—C5'' | 78.8 (3) |
C6'—C1'—C2'—C8' | 130.4 (3) | C7''—C1''—C6''—C5'' | −28.3 (2) |
C8'—C2'—C3'—C4' | −178.8 (3) | C4''—C5''—C6''—C9'' | 41.7 (4) |
C1'—C2'—C3'—C4' | 0.7 (5) | C7''—C5''—C6''—C9'' | 148.8 (3) |
C2'—C3'—C4'—O1' | 123.9 (3) | C4''—C5''—C6''—C10'' | 169.0 (3) |
C2'—C3'—C4'—C5' | 2.1 (4) | C7''—C5''—C6''—C10'' | −83.9 (3) |
O1'—C4'—C5'—C7' | −173.4 (2) | C4''—C5''—C6''—C1'' | −78.8 (3) |
C3'—C4'—C5'—C7' | −50.2 (3) | C7''—C5''—C6''—C1'' | 28.3 (2) |
O1'—C4'—C5'—C6' | −79.6 (3) | C2''—C1''—C7''—C5'' | −80.9 (3) |
C3'—C4'—C5'—C6' | 43.7 (3) | C6''—C1''—C7''—C5'' | 28.7 (2) |
C2'—C1'—C6'—C9' | −42.7 (4) | C4''—C5''—C7''—C1'' | 84.7 (3) |
C7'—C1'—C6'—C9' | −150.2 (3) | C6''—C5''—C7''—C1'' | −28.5 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—HO1···O1′ | 0.81 (4) | 1.97 (4) | 2.760 (3) | 162 (4) |
O1′—HO1′···O1′′ | 0.70 (4) | 2.11 (5) | 2.760 (3) | 156 (5) |
O1′′—HO1′′···O1i | 0.75 (5) | 2.02 (5) | 2.766 (3) | 170 (4) |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data |
Chemical formula | C10H16O |
Mr | 152.23 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 200 |
a, b, c (Å) | 7.0115 (1), 18.7691 (6), 21.1681 (7) |
V (Å3) | 2785.71 (13) |
Z | 12 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.20 × 0.14 × 0.13 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13724, 2717, 2360 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.590 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.127, 1.05 |
No. of reflections | 2717 |
No. of parameters | 310 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.23 |
Selected geometric parameters (Å, º) topO1—C4 | 1.444 (3) | O1''—C4'' | 1.443 (4) |
O1'—C4' | 1.443 (4) | | |
| | | |
O1—C4—C3 | 111.5 (3) | O1''—C4''—C3'' | 111.0 (3) |
O1'—C4'—C3' | 111.7 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—HO1···O1' | 0.81 (4) | 1.97 (4) | 2.760 (3) | 162 (4) |
O1'—HO1'···O1'' | 0.70 (4) | 2.11 (5) | 2.760 (3) | 156 (5) |
O1''—HO1''···O1i | 0.75 (5) | 2.02 (5) | 2.766 (3) | 170 (4) |
Symmetry code: (i) x−1, y, z. |
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Verbenol is a monoterpene alcohol with four known stereoisomers (Dictionary of Natural Products, 1994). Two enantiomers, (1R,2S,5R) and (1S,2R,5S), are oils and are diastereoisomers of the two solid enantiomeric structures, (1R,2R,5R) and (1S,2S,5S), of which the latter, (I), is studied here. Recent solid-state NMR studies have demonstrated that verbenol exhibits multiple resonances per carbon position in the molecular structure, suggesting polymorphism or multiple molecules per asymmetric unit (Harper & Grant, 1999). An X-ray analysis was performed on (I) to clarify these structural variations and to characterize the associated hydrogen-bonding features. \scheme
The arrangement of the three molecules of the asymmetric unit for (I) is shown in Fig. 1. The crystal of (I) consists of helical hydrogen-bonded chains lying parallel to the shortest axis. The three distinct molecules per asymmetric unit differ primarily in the conformations of the hydrogen-bonded region of verbenol, with C3—C4—O—H dihedral angles of 55, 69 and 74°. All other differences in heavy atom angles, both dihedral and geminal, and in bond lengths were modest between the three unique verbenol molecules, with respective variations of less than 2° and 0.013 Å. Four asymmetric units compose the unit cell arrangement shown in Fig. 2.
Monofunctional alcohols frequently form chains, rings and helices. Such arrangements often contain more than one molecule per asymmetric unit (Brock & Duncan, 1994). The present X-ray structure of verbenol corresponds to a previously described sterol monoalcohol structure (Brock et al., 1994) in the number of molecules per asymmetric unit, general hydrogen-bonding arrangement and space group. Similar hydrogen-bonded helices containing three molecules per asymmetric unit have also been observed in other monoalcohols (Singelenberg & van Eijck, 1987; Zavodnik & Bel'skii, 1987; Escobar & Wittke, 1984), although with different space groups. Solid state NMR analyses demonstrate that other preparations of solid verbenol powder samples contain a second minor polymorph with four molecules per asymmetric unit (Harper & Grant, 1999). A single-crystal of this second structure could not be isolated and hence has not been subjected to X-ray analysis.