Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800020079/bt6000sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536800020079/bt6000Isup2.hkl |
CCDC reference: 155906
Crystals of the title compound were obtained by sublimation of a bulk sample under ambient pressure and temperature. Due to the high vapor pressure of the compound, it also sublimes during the diffraction experiment. Thus, in order to minimize the rate of sublimation, the crystal was completely encapsulated in a thin layer of epoxy glue. This strategy was sufficient to allow data collection over a period of a few days.
All data was employed in the refinement with the exception of the (1,1,2) reflection which had strongly negative intensity. During the course of the refinement, the disorder in the C(Me)2(CH2)3 backbone of the seven-membered ring became apparent. This disorder was modelled by introducing two (CH2)3 moieties anchored at both ends to the undisordered fragment of the molecule (C71/C81/C91 and C72/C82/C92), the occupation factors of which were allowed to refine. While bond-length restraints were introduced during the initial phases of the disordered refinement to minimize the likelyhood of a divergent refinement, these proved to be unnecessary and were removed during the final cycles of least-squares refinement. Though under this model the two methyl groups of the C(Me)2 moiety may also be expected to be disordered, a model taking this aspect into account failed to yield lower residuals. H atoms were placed in geometrically idealized positions and given a common displacement parameter by class (methyl group H atoms, all others), which were allowed to refine. The final value of Uiso(H) for the methyl group H atoms is 0.141 (4) Å2, and for all other H atoms is 0.095 (3) Å2.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997).
Fig. 1. View of (I) illustrating the numbering scheme (30% probability displacement ellipsoids). The minor fraction of the disordered atoms C71, C81 and C91 have been omitted. |
C15H22O | Dx = 1.077 Mg m−3 |
Mr = 218.33 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, P212121 | Cell parameters from 99 reflections |
a = 6.628 (1) Å | θ = 8.0–27.3° |
b = 10.218 (1) Å | µ = 0.50 mm−1 |
c = 19.889 (1) Å | T = 293 K |
V = 1347.0 (3) Å3 | Block, colorless |
Z = 4 | 0.4 × 0.4 × 0.3 mm |
F(000) = 480 |
Serial diffractometer | Rint = 0.041 |
ω/2θ scans | θmax = 67.6°, θmin = 4.5° |
Absorption correction: empirical (using intensity measurements) via ψ scans ((North et al., 1968) using XEMP (Siemens, 1990) | h = −6→7 |
Tmin = 0.827, Tmax = 0.866 | k = −12→12 |
2270 measured reflections | l = −23→23 |
1911 independent reflections | 3 standard reflections every 97 reflections |
1666 reflections with I > 2σ(I) | intensity decay: 1% |
Refinement on F2 | w = 1/[σ2(Fo2) + (0.0858P)2 + 0.0511P] where P = (Fo2 + 2Fc2)/3 |
Least-squares matrix: full | (Δ/σ)max = 0.001 |
R[F2 > 2σ(F2)] = 0.050 | Δρmax = 0.12 e Å−3 |
wR(F2) = 0.132 | Δρmin = −0.14 e Å−3 |
S = 1.07 | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1911 reflections | Extinction coefficient: 0.0052 (12) |
176 parameters | Absolute structure: Flack (1983) |
0 restraints | Absolute structure parameter: not reliably determined [−0.7 (6)] |
H-atom parameters constrained |
C15H22O | V = 1347.0 (3) Å3 |
Mr = 218.33 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 6.628 (1) Å | µ = 0.50 mm−1 |
b = 10.218 (1) Å | T = 293 K |
c = 19.889 (1) Å | 0.4 × 0.4 × 0.3 mm |
Serial diffractometer | 1666 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ scans ((North et al., 1968) using XEMP (Siemens, 1990) | Rint = 0.041 |
Tmin = 0.827, Tmax = 0.866 | 3 standard reflections every 97 reflections |
2270 measured reflections | intensity decay: 1% |
1911 independent reflections |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.132 | Δρmax = 0.12 e Å−3 |
S = 1.07 | Δρmin = −0.14 e Å−3 |
1911 reflections | Absolute structure: Flack (1983) |
176 parameters | Absolute structure parameter: not reliably determined [−0.7 (6)] |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | 0.7435 (3) | 0.5483 (2) | 0.46305 (11) | 0.1032 (7) | |
C1 | 0.5760 (3) | 0.5489 (2) | 0.43741 (11) | 0.0706 (6) | |
C2 | 0.4529 (4) | 0.6664 (2) | 0.43026 (12) | 0.0739 (6) | |
H2 | 0.5013 | 0.7476 | 0.4439 | 0.095 (3)* | |
C3 | 0.2689 (4) | 0.6543 (2) | 0.40359 (10) | 0.0685 (6) | |
C31 | 0.1219 (5) | 0.7633 (3) | 0.39466 (13) | 0.0932 (8) | |
H31A | 0.0104 | 0.7514 | 0.4249 | 0.141 (4)* | |
H31B | 0.0735 | 0.7637 | 0.3492 | 0.141 (4)* | |
H31C | 0.1871 | 0.8452 | 0.4042 | 0.141 (4)* | |
C4 | 0.2094 (3) | 0.5195 (2) | 0.38143 (10) | 0.0654 (6) | |
H4 | 0.0766 | 0.5116 | 0.3602 | 0.095 (3)* | |
C5 | 0.3913 (3) | 0.4655 (2) | 0.34020 (10) | 0.0644 (6) | |
H5 | 0.4690 | 0.5392 | 0.3223 | 0.095 (3)* | |
C6 | 0.3674 (4) | 0.3624 (2) | 0.28532 (13) | 0.0837 (7) | |
C61 | 0.2627 (7) | 0.4305 (4) | 0.22528 (16) | 0.1334 (14) | |
H61A | 0.2533 | 0.3705 | 0.1883 | 0.141 (4)* | |
H61B | 0.3401 | 0.5056 | 0.2119 | 0.141 (4)* | |
H61C | 0.1298 | 0.4578 | 0.2384 | 0.141 (4)* | |
C62 | 0.5757 (6) | 0.3206 (4) | 0.26353 (18) | 0.1190 (12) | |
H62A | 0.5649 | 0.2598 | 0.2269 | 0.141 (4)* | |
H62B | 0.6437 | 0.2794 | 0.3005 | 0.141 (4)* | |
H62C | 0.6510 | 0.3959 | 0.2493 | 0.141 (4)* | |
C71 | 0.2145 (19) | 0.2555 (10) | 0.2987 (6) | 0.098 (3) | 0.565 (14) |
H71A | 0.0800 | 0.2919 | 0.2945 | 0.095 (3)* | 0.565 (14) |
H71B | 0.2291 | 0.1881 | 0.2647 | 0.095 (3)* | 0.565 (14) |
C81 | 0.2355 (19) | 0.1934 (7) | 0.3674 (4) | 0.105 (3) | 0.565 (14) |
H81A | 0.1565 | 0.1136 | 0.3690 | 0.095 (3)* | 0.565 (14) |
H81B | 0.3757 | 0.1706 | 0.3752 | 0.095 (3)* | 0.565 (14) |
C91 | 0.167 (2) | 0.2825 (15) | 0.4200 (8) | 0.094 (5) | 0.565 (14) |
H91A | 0.1715 | 0.2321 | 0.4613 | 0.095 (3)* | 0.565 (14) |
H91B | 0.0255 | 0.2982 | 0.4108 | 0.095 (3)* | 0.565 (14) |
C72 | 0.295 (3) | 0.2293 (16) | 0.3175 (8) | 0.106 (4) | 0.435 (14) |
H72A | 0.2717 | 0.1662 | 0.2819 | 0.095 (3)* | 0.435 (14) |
H72B | 0.4011 | 0.1954 | 0.3461 | 0.095 (3)* | 0.435 (14) |
C82 | 0.1036 (19) | 0.2432 (10) | 0.3587 (5) | 0.096 (4) | 0.435 (14) |
H82A | 0.0323 | 0.1603 | 0.3586 | 0.095 (3)* | 0.435 (14) |
H82B | 0.0170 | 0.3078 | 0.3376 | 0.095 (3)* | 0.435 (14) |
C92 | 0.146 (3) | 0.2866 (13) | 0.4358 (11) | 0.075 (4) | 0.435 (14) |
H92A | 0.0186 | 0.2941 | 0.4596 | 0.095 (3)* | 0.435 (14) |
H92B | 0.2262 | 0.2202 | 0.4580 | 0.095 (3)* | 0.435 (14) |
C10 | 0.2574 (3) | 0.4183 (2) | 0.43794 (11) | 0.0682 (6) | |
C101 | 0.2191 (4) | 0.4569 (3) | 0.51137 (11) | 0.0833 (7) | |
H10A | 0.0786 | 0.4764 | 0.5174 | 0.141 (4)* | |
H10B | 0.2981 | 0.5327 | 0.5223 | 0.141 (4)* | |
H10C | 0.2567 | 0.3857 | 0.5403 | 0.141 (4)* | |
C11 | 0.4774 (3) | 0.4276 (2) | 0.41107 (11) | 0.0665 (6) | |
H11 | 0.5576 | 0.3472 | 0.4132 | 0.095 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0654 (11) | 0.1316 (16) | 0.1126 (14) | −0.0036 (11) | −0.0180 (10) | −0.0206 (12) |
C1 | 0.0560 (12) | 0.0910 (15) | 0.0649 (11) | −0.0036 (11) | −0.0026 (10) | −0.0031 (11) |
C2 | 0.0859 (17) | 0.0690 (13) | 0.0668 (12) | −0.0056 (12) | −0.0046 (13) | −0.0065 (10) |
C3 | 0.0822 (17) | 0.0703 (12) | 0.0530 (9) | 0.0134 (12) | 0.0073 (12) | 0.0036 (9) |
C31 | 0.115 (2) | 0.0872 (16) | 0.0778 (14) | 0.0329 (16) | 0.0104 (15) | 0.0097 (13) |
C4 | 0.0529 (11) | 0.0794 (13) | 0.0638 (11) | −0.0003 (10) | −0.0059 (10) | 0.0037 (10) |
C5 | 0.0616 (12) | 0.0661 (11) | 0.0655 (11) | −0.0043 (11) | −0.0018 (10) | −0.0037 (9) |
C6 | 0.0855 (16) | 0.0822 (15) | 0.0833 (15) | −0.0123 (14) | 0.0031 (14) | −0.0230 (12) |
C61 | 0.165 (4) | 0.144 (3) | 0.0909 (19) | −0.007 (3) | −0.036 (2) | −0.037 (2) |
C62 | 0.120 (3) | 0.127 (2) | 0.109 (2) | 0.008 (2) | 0.021 (2) | −0.046 (2) |
C71 | 0.116 (8) | 0.077 (4) | 0.101 (6) | −0.025 (4) | −0.025 (5) | −0.013 (4) |
C81 | 0.120 (6) | 0.070 (3) | 0.125 (6) | −0.017 (4) | −0.007 (5) | 0.013 (3) |
C91 | 0.067 (5) | 0.125 (8) | 0.091 (10) | −0.014 (4) | 0.015 (5) | 0.028 (5) |
C72 | 0.110 (11) | 0.103 (9) | 0.105 (9) | −0.024 (7) | 0.000 (6) | −0.036 (7) |
C82 | 0.089 (6) | 0.075 (4) | 0.123 (7) | −0.020 (4) | 0.002 (5) | −0.014 (4) |
C92 | 0.099 (9) | 0.059 (5) | 0.068 (7) | −0.015 (4) | 0.025 (4) | 0.010 (3) |
C10 | 0.0576 (12) | 0.0760 (13) | 0.0709 (12) | 0.0017 (11) | 0.0026 (11) | 0.0119 (10) |
C101 | 0.0750 (14) | 0.1046 (17) | 0.0703 (13) | 0.0082 (15) | 0.0099 (11) | 0.0212 (12) |
C11 | 0.0563 (12) | 0.0705 (12) | 0.0727 (12) | 0.0053 (10) | −0.0030 (10) | 0.0022 (9) |
O1—C1 | 1.222 (3) | C6—C71 | 1.514 (12) |
C1—C2 | 1.458 (3) | C6—C61 | 1.546 (5) |
C1—C11 | 1.496 (3) | C6—C72 | 1.579 (17) |
C2—C3 | 1.336 (4) | C71—C81 | 1.512 (16) |
C3—C31 | 1.491 (3) | C81—C91 | 1.459 (17) |
C3—C4 | 1.498 (3) | C91—C10 | 1.553 (15) |
C4—C5 | 1.559 (3) | C72—C82 | 1.52 (2) |
C4—C10 | 1.560 (3) | C82—C92 | 1.62 (2) |
C5—C6 | 1.525 (3) | C92—C10 | 1.537 (15) |
C5—C11 | 1.569 (3) | C10—C101 | 1.534 (3) |
C6—C62 | 1.509 (5) | C10—C11 | 1.556 (3) |
O1—C1—C2 | 123.6 (2) | C5—C6—C72 | 109.6 (5) |
O1—C1—C11 | 122.6 (2) | C61—C6—C72 | 124.4 (7) |
C2—C1—C11 | 113.78 (19) | C81—C71—C6 | 113.6 (8) |
C3—C2—C1 | 118.2 (2) | C91—C81—C71 | 111.0 (10) |
C2—C3—C31 | 125.1 (2) | C81—C91—C10 | 127.1 (11) |
C2—C3—C4 | 116.2 (2) | C82—C72—C6 | 113.2 (13) |
C31—C3—C4 | 118.7 (2) | C72—C82—C92 | 113.1 (12) |
C3—C4—C5 | 106.07 (18) | C10—C92—C82 | 110.5 (12) |
C3—C4—C10 | 110.09 (16) | C101—C10—C92 | 99.9 (8) |
C5—C4—C10 | 89.24 (16) | C101—C10—C91 | 112.6 (6) |
C6—C5—C4 | 122.73 (19) | C92—C10—C91 | 12.9 (13) |
C6—C5—C11 | 120.70 (19) | C101—C10—C11 | 117.80 (19) |
C4—C5—C11 | 84.03 (15) | C92—C10—C11 | 119.7 (8) |
C62—C6—C71 | 117.3 (5) | C91—C10—C11 | 109.7 (6) |
C62—C6—C5 | 107.8 (2) | C101—C10—C4 | 118.83 (19) |
C71—C6—C5 | 116.2 (5) | C92—C10—C4 | 117.5 (8) |
C62—C6—C61 | 108.4 (3) | C91—C10—C4 | 110.4 (6) |
C71—C6—C61 | 99.2 (5) | C11—C10—C4 | 84.44 (15) |
C5—C6—C61 | 106.8 (2) | C1—C11—C10 | 109.86 (19) |
C62—C6—C72 | 98.7 (7) | C1—C11—C5 | 105.62 (18) |
C71—C6—C72 | 26.2 (5) | C10—C11—C5 | 89.02 (15) |
Experimental details
Crystal data | |
Chemical formula | C15H22O |
Mr | 218.33 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 6.628 (1), 10.218 (1), 19.889 (1) |
V (Å3) | 1347.0 (3) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.50 |
Crystal size (mm) | 0.4 × 0.4 × 0.3 |
Data collection | |
Diffractometer | Serial diffractometer |
Absorption correction | Empirical (using intensity measurements) via ψ scans ((North et al., 1968) using XEMP (Siemens, 1990) |
Tmin, Tmax | 0.827, 0.866 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2270, 1911, 1666 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.600 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.132, 1.07 |
No. of reflections | 1911 |
No. of parameters | 176 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.12, −0.14 |
Absolute structure | Flack (1983) |
Absolute structure parameter | not reliably determined [−0.7 (6)] |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997).
C5—C4—C10 | 89.24 (16) | C11—C10—C4 | 84.44 (15) |
C4—C5—C11 | 84.03 (15) | C10—C11—C5 | 89.02 (15) |
Continuing our structural and synthetic studies of the effects of ring strain on the properties of carbocyclic natural products (White & Lee, 1997), we report here the structure of vulgarone B, (I). This sesquiterpene was isolated as the major terpenoid component (ca 40%) of the essential oil of Artemisia douglasiana Bess., a plant that occurs widely in Western Oregon. An extract of this plant has been found to possess potent insecticidal and gastropod repellent activity. Previously, vulgarone B was isolated along with its isomer vulgarone A as a minor constituent of the oil of the medicinal plant Chrysanthemum vulgare (L.) Bernh, [Tanacetum vulgare (L)] (Uchio et al., 1977). It has also been obtained from the volatile oil of cultivars of Santolina chamaecyparcissus L. (Baig et al., 1989).
The structure of vulgarone B, including its absolute configuration, had earlier been deduced from spectroscopic evidence and by chemical correlation with the related sesquiterpene (+)-α-longipinene (Uchio, 1978). The results from our X-ray single-crystal diffraction experiment confirm the assigned structure. We also attempted to determine the absolute configuration of vulgarone B from the diffraction data, but, due to the small magnitude of the anomalous scattering components, the refined value of the absolute structure parameter could not be reliably determined. This is reflected in the fact that the model shown in Fig. 1 yields a value of -0.7 (6) for this parameter, whereas the inverted model yields a value of 1.7 (6). Further, since the absolute structure derived from the model shown is identical to the previously deduced configuration for this molecule (Uchio, 1978), we find it reasonable to conclude that this is the true configuration of vulgarone B.
All the observed intramolecular distances and angles are well within the expected values. The most interesting feature of the molecule is the four-membered ring, in which all four atoms are stereogenic. Opposite corners of this ring are the bridgehead C atoms that are components of two other rings, i.e. a seven-membered cycle and a six-membered ring. The six-membered ring contains a C═C\sb C═O moiety, which should force five of the six atoms in the ring to be planar. This is found to be correct; atoms O1, C1, C2, C3, C31, C4 and C11 are nearly coplanar, with a maximum deviation from the mean plane of 0.028 (2) Å by atom C2. This geometric constraint also causes a slight distortion of the four-membered ring, in which the bridgehead C atoms of the six-membered ring have moved toward each other. This is reflected in the C\sb C\sb C angles within the ring, which are identical pairwise at about 84 and 89° as shown in Table 1.