Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801016932/cf6114sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801016932/cf6114Isup2.hkl |
CCDC reference: 176007
(1R)-(-)-Fenchone (98%) was obtained from the Aldrich company and used without further purification. The crystal was grown in a 0.3 mm glass capillary tube at 260 K (a temperature only slightly less than the melting point of the solid in the capillary tube). With the axis of the capillary parallel to the ϕ axis and horizontal on the instrument, the crystal was obtained by moving a plug of solid material up and down the tube (the movement being controlled with the standard height adjustment of the goniometer head). The length of the cylindrical crystal was not estimated, but it exceeded the 0.35 mm diameter of the collimator. Data were collected at 150 K.
Hydrogen atoms were placed geometrically and refined using a riding model with an isotropic displacement parameter fixed at 1.2 times Ueq for the carbon to which they are attached. The absolute configuration could not be determined reliably and was assigned according to the known configuration of the sample. Friedel pairs were merged prior to merging in P21; the reported value of Rint corresponds to subsequent merging of equivalent reflections in this space group.
Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Sheldrick, 1993) and CAMERON (Watkin et al., 1996); software used to prepare material for publication: SHELXL97.
C10H16O | Dx = 1.135 Mg m−3 |
Mr = 152.23 | Melting point: 278 K |
Monoclinic, P21 | Mo Kα radiation, λ = 0.7107 Å |
a = 6.0520 (7) Å | Cell parameters from 2665 reflections |
b = 10.2748 (7) Å | θ = 1.0–25.0° |
c = 7.1621 (9) Å | µ = 0.07 mm−1 |
β = 91.335 (4)° | T = 150 K |
V = 445.24 (8) Å3 | Cylinder, colourless |
Z = 2 | 0.15 mm (radius) |
F(000) = 168 |
Nonius KappaCCD diffractometer | 757 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.078 |
Thin–slice ω and ϕ scans | θmax = 25.0°, θmin = 4.0° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −7→7 |
Tmin = 0.783, Tmax = 1.000 | k = −12→10 |
2506 measured reflections | l = −6→8 |
821 independent reflections |
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.157 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.1005P)2 + 0.0865P] where P = (Fo2 + 2Fc2)/3 |
821 reflections | (Δ/σ)max = 0.001 |
103 parameters | Δρmax = 0.19 e Å−3 |
1 restraint | Δρmin = −0.22 e Å−3 |
C10H16O | V = 445.24 (8) Å3 |
Mr = 152.23 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.0520 (7) Å | µ = 0.07 mm−1 |
b = 10.2748 (7) Å | T = 150 K |
c = 7.1621 (9) Å | 0.15 mm (radius) |
β = 91.335 (4)° |
Nonius KappaCCD diffractometer | 821 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 757 reflections with I > 2σ(I) |
Tmin = 0.783, Tmax = 1.000 | Rint = 0.078 |
2506 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 1 restraint |
wR(F2) = 0.157 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.19 e Å−3 |
821 reflections | Δρmin = −0.22 e Å−3 |
103 parameters |
Experimental. Grown in situ in a 0.3 mm Lindemann tube at 260 K. The absolute structure was assigned from the known configuration of the material and Friedel pairs were merged for refinement. |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.3206 (5) | 0.6557 (3) | 0.9979 (4) | 0.0382 (8) | |
C1 | 0.2451 (6) | 0.7491 (4) | 0.6890 (5) | 0.0288 (9) | |
C2 | 0.2344 (6) | 0.7388 (3) | 0.8999 (5) | 0.0269 (8) | |
C3 | 0.0983 (6) | 0.8536 (4) | 0.9685 (5) | 0.0282 (8) | |
C4 | 0.0405 (6) | 0.9233 (4) | 0.7811 (5) | 0.0270 (8) | |
H4 | −0.0912 | 0.9818 | 0.7855 | 0.032* | |
C5 | 0.2476 (6) | 0.9870 (4) | 0.7011 (5) | 0.0297 (9) | |
H5A | 0.3206 | 1.0451 | 0.7939 | 0.036* | |
H5B | 0.2107 | 1.0375 | 0.5868 | 0.036* | |
C6 | 0.3949 (6) | 0.8690 (4) | 0.6567 (5) | 0.0312 (8) | |
H6A | 0.5269 | 0.8666 | 0.7409 | 0.037* | |
H6B | 0.4436 | 0.8722 | 0.5257 | 0.037* | |
C7 | 0.0140 (6) | 0.8069 (4) | 0.6455 (5) | 0.0294 (8) | |
H7A | −0.1073 | 0.7476 | 0.6800 | 0.035* | |
H7B | −0.0048 | 0.8345 | 0.5136 | 0.035* | |
C8 | 0.3129 (8) | 0.6255 (4) | 0.5892 (6) | 0.0380 (10) | |
H8A | 0.3125 | 0.6410 | 0.4542 | 0.057* | |
H8B | 0.2084 | 0.5557 | 0.6171 | 0.057* | |
H8C | 0.4617 | 0.6000 | 0.6320 | 0.057* | |
C9 | −0.1120 (7) | 0.8032 (4) | 1.0608 (5) | 0.0331 (9) | |
H9A | −0.1984 | 0.7514 | 0.9703 | 0.050* | |
H9B | −0.2007 | 0.8771 | 1.1022 | 0.050* | |
H9C | −0.0710 | 0.7489 | 1.1686 | 0.050* | |
C10 | 0.2299 (7) | 0.9334 (4) | 1.1118 (5) | 0.0354 (9) | |
H10A | 0.3686 | 0.9623 | 1.0572 | 0.053* | |
H10B | 0.2626 | 0.8798 | 1.2222 | 0.053* | |
H10C | 0.1433 | 1.0095 | 1.1481 | 0.053* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0414 (17) | 0.0372 (16) | 0.0360 (15) | 0.0090 (13) | 0.0021 (11) | 0.0087 (13) |
C1 | 0.0282 (19) | 0.033 (2) | 0.0250 (19) | 0.0018 (15) | 0.0037 (14) | 0.0006 (15) |
C2 | 0.0249 (18) | 0.0267 (17) | 0.0292 (18) | −0.0019 (14) | 0.0024 (14) | 0.0023 (16) |
C3 | 0.0284 (18) | 0.0318 (19) | 0.0246 (16) | −0.0006 (16) | 0.0051 (13) | 0.0005 (15) |
C4 | 0.0278 (18) | 0.0279 (17) | 0.0254 (17) | 0.0028 (15) | 0.0022 (13) | 0.0031 (15) |
C5 | 0.034 (2) | 0.0290 (18) | 0.0264 (19) | −0.0005 (15) | 0.0051 (15) | 0.0035 (14) |
C6 | 0.0312 (19) | 0.0349 (19) | 0.0277 (17) | 0.0028 (17) | 0.0067 (14) | 0.0015 (17) |
C7 | 0.0284 (19) | 0.0330 (18) | 0.0267 (18) | 0.0014 (15) | 0.0001 (14) | −0.0036 (15) |
C8 | 0.043 (2) | 0.036 (2) | 0.036 (2) | 0.0057 (18) | 0.0070 (17) | −0.0060 (18) |
C9 | 0.031 (2) | 0.0334 (19) | 0.035 (2) | −0.0015 (16) | 0.0112 (15) | 0.0000 (16) |
C10 | 0.039 (2) | 0.038 (2) | 0.0298 (19) | −0.0048 (19) | 0.0029 (16) | −0.0033 (17) |
O1—C2 | 1.216 (4) | C5—H5B | 0.990 |
C1—C2 | 1.517 (5) | C6—H6A | 0.990 |
C1—C8 | 1.518 (5) | C6—H6B | 0.990 |
C1—C7 | 1.545 (5) | C7—H7A | 0.990 |
C1—C6 | 1.550 (5) | C7—H7B | 0.990 |
C2—C3 | 1.527 (5) | C8—H8A | 0.980 |
C3—C10 | 1.524 (5) | C8—H8B | 0.980 |
C3—C9 | 1.538 (5) | C8—H8C | 0.980 |
C3—C4 | 1.554 (5) | C9—H9A | 0.980 |
C4—C5 | 1.537 (5) | C9—H9B | 0.980 |
C4—C7 | 1.546 (5) | C9—H9C | 0.980 |
C4—H4 | 1.000 | C10—H10A | 0.980 |
C5—C6 | 1.542 (6) | C10—H10B | 0.980 |
C5—H5A | 0.990 | C10—H10C | 0.980 |
C2—C1—C8 | 115.4 (3) | C1—C6—H6A | 110.8 |
C2—C1—C7 | 99.7 (3) | C5—C6—H6B | 110.8 |
C8—C1—C7 | 118.7 (3) | C1—C6—H6B | 110.8 |
C2—C1—C6 | 104.0 (3) | H6A—C6—H6B | 108.9 |
C8—C1—C6 | 115.4 (3) | C1—C7—C4 | 95.2 (3) |
C7—C1—C6 | 101.2 (3) | C1—C7—H7A | 112.7 |
O1—C2—C1 | 126.6 (3) | C4—C7—H7A | 112.7 |
O1—C2—C3 | 125.7 (3) | C1—C7—H7B | 112.7 |
C1—C2—C3 | 107.6 (3) | C4—C7—H7B | 112.7 |
C10—C3—C2 | 110.8 (3) | H7A—C7—H7B | 110.2 |
C10—C3—C9 | 108.5 (3) | C1—C8—H8A | 109.5 |
C2—C3—C9 | 109.6 (3) | C1—C8—H8B | 109.5 |
C10—C3—C4 | 115.9 (3) | H8A—C8—H8B | 109.5 |
C2—C3—C4 | 100.9 (3) | C1—C8—H8C | 109.5 |
C9—C3—C4 | 110.8 (3) | H8A—C8—H8C | 109.5 |
C5—C4—C7 | 99.7 (3) | H8B—C8—H8C | 109.5 |
C5—C4—C3 | 110.5 (3) | C3—C9—H9A | 109.5 |
C7—C4—C3 | 101.8 (3) | C3—C9—H9B | 109.5 |
C5—C4—H4 | 114.4 | H9A—C9—H9B | 109.5 |
C7—C4—H4 | 114.4 | C3—C9—H9C | 109.5 |
C3—C4—H4 | 114.4 | H9A—C9—H9C | 109.5 |
C4—C5—C6 | 102.8 (3) | H9B—C9—H9C | 109.5 |
C4—C5—H5A | 111.2 | C3—C10—H10A | 109.5 |
C6—C5—H5A | 111.2 | C3—C10—H10B | 109.5 |
C4—C5—H5B | 111.2 | H10A—C10—H10B | 109.5 |
C6—C5—H5B | 111.2 | C3—C10—H10C | 109.5 |
H5A—C5—H5B | 109.1 | H10A—C10—H10C | 109.5 |
C5—C6—C1 | 104.5 (3) | H10B—C10—H10C | 109.5 |
C5—C6—H6A | 110.8 | ||
C8—C1—C2—O1 | 18.3 (6) | C10—C3—C4—C7 | 154.5 (3) |
C7—C1—C2—O1 | 146.6 (4) | C2—C3—C4—C7 | 34.8 (3) |
C6—C1—C2—O1 | −109.2 (4) | C9—C3—C4—C7 | −81.3 (3) |
C8—C1—C2—C3 | −162.7 (3) | C7—C4—C5—C6 | −41.2 (3) |
C7—C1—C2—C3 | −34.3 (4) | C3—C4—C5—C6 | 65.4 (4) |
C6—C1—C2—C3 | 69.9 (3) | C4—C5—C6—C1 | 7.8 (3) |
O1—C2—C3—C10 | 55.6 (5) | C2—C1—C6—C5 | −74.6 (3) |
C1—C2—C3—C10 | −123.5 (3) | C8—C1—C6—C5 | 158.0 (3) |
O1—C2—C3—C9 | −64.2 (5) | C7—C1—C6—C5 | 28.5 (3) |
C1—C2—C3—C9 | 116.8 (3) | C2—C1—C7—C4 | 53.7 (3) |
O1—C2—C3—C4 | 178.9 (4) | C8—C1—C7—C4 | 179.8 (3) |
C1—C2—C3—C4 | −0.1 (4) | C6—C1—C7—C4 | −52.8 (3) |
C10—C3—C4—C5 | 49.3 (4) | C5—C4—C7—C1 | 58.1 (3) |
C2—C3—C4—C5 | −70.4 (4) | C3—C4—C7—C1 | −55.3 (3) |
C9—C3—C4—C5 | 173.5 (3) |
Experimental details
Crystal data | |
Chemical formula | C10H16O |
Mr | 152.23 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 150 |
a, b, c (Å) | 6.0520 (7), 10.2748 (7), 7.1621 (9) |
β (°) | 91.335 (4) |
V (Å3) | 445.24 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.15 (radius) |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.783, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2506, 821, 757 |
Rint | 0.078 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.157, 1.10 |
No. of reflections | 821 |
No. of parameters | 103 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.22 |
Computer programs: COLLECT (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), XP (Sheldrick, 1993) and CAMERON (Watkin et al., 1996), SHELXL97.
Fenchone (I) occurs in nature and may be extracted from fennel oil and thuja oil. An account of its history and the determination of its structure using the techniques of classical organic chemistry is given by Simonsen & Owen (1947). This work forms part of a continuing study devoted to improving the techniques for determining the crystal structures of substances which are liquids at room temperature (see, for example, Davies & Bond, 2001).