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The low-temperature crystal stuctures of D- and DL-camphoric anhydride, C10H14O3, have been determined by X-ray diffraction methods. Although the two enantiomers crystallize in different space groups, the cell volumes and densities are essentially the same. The six-membered rings deviate significantly from planarity, both exhibiting half-boat conformations. The dihedral angle between the six- and five-membered rings is 80.3 (1)° in both cases. The main difference in the molecular stuctures can be described by two torsion angles associated with the H atoms of the methyl substituents. The packing of the racemic and chiral structures are essentially the same.
Supporting information
Commercially available (I) and (II) were purchased and crystallized from benzene
and toluene, respectively, by slow evaporation at room temperature.
H atoms were located from difference Fourier maps and refined isotropically. The
C—H distances range from 0.91 (2) to 1.02 (2) Å. Due to the absence of
suitable anomolous scatteres within (I), the determination of the absolute
configuration was not possible from our X-ray data. Friedel opposites were
therefore merged before the refinement.
For both compounds, data collection: SMART (Bruker, 1997); cell refinement: SAINT-Plus (Bruker, 1997); data reduction: SAINT-Plus (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Shelsrick, 1997); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).
(I) (1
R)-1,8,8-Trimethyl-3-oxabicyclo[3.2.1]octane-2,4-dione
top
Crystal data top
C10H14O3 | Dx = 1.316 Mg m−3 |
Mr = 182.21 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 8192 reflections |
a = 6.4262 (3) Å | θ = 2.4–29.9° |
b = 11.0841 (4) Å | µ = 0.10 mm−1 |
c = 12.9142 (5) Å | T = 110 K |
V = 919.86 (6) Å3 | Rectangular block, colourless |
Z = 4 | 0.45 × 0.4 × 0.3 mm |
F(000) = 392 | |
Data collection top
Brukers SMART CCD area-detector diffractometer | Rint = 0.021 |
Detector resolution: 0.75 pixels mm-1 | θmax = 26.4°, θmin = 2.4° |
ω scans | h = 0→8 |
11128 measured reflections | k = 0→13 |
1103 independent reflections | l = 0→16 |
1090 reflections with I > 2σ(I) | |
Refinement top
Refinement on F2 | 174 parameters |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.029 | Cal w = 1/[σ2(Fo2) + (0.0548P)2 + 0.088P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.072 | (Δ/σ)max = 0.001 |
S = 1.11 | Δρmax = 0.20 e Å−3 |
1103 reflections | Δρmin = −0.20 e Å−3 |
Crystal data top
C10H14O3 | V = 919.86 (6) Å3 |
Mr = 182.21 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.4262 (3) Å | µ = 0.10 mm−1 |
b = 11.0841 (4) Å | T = 110 K |
c = 12.9142 (5) Å | 0.45 × 0.4 × 0.3 mm |
Data collection top
Brukers SMART CCD area-detector diffractometer | 1090 reflections with I > 2σ(I) |
11128 measured reflections | Rint = 0.021 |
1103 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.029 | 174 parameters |
wR(F2) = 0.072 | All H-atom parameters refined |
S = 1.11 | Δρmax = 0.20 e Å−3 |
1103 reflections | Δρmin = −0.20 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | −0.41254 (15) | −0.42254 (9) | −0.05444 (7) | 0.0212 (2) | |
O2 | −0.40437 (18) | −0.55783 (11) | 0.07026 (8) | 0.0304 (3) | |
O3 | −0.44800 (17) | −0.31127 (9) | −0.19501 (8) | 0.0278 (3) | |
C1 | −0.0790 (2) | −0.53040 (11) | −0.02361 (9) | 0.0180 (3) | |
C2 | −0.3068 (2) | −0.51016 (12) | 0.00295 (10) | 0.0203 (3) | |
C3 | −0.3326 (2) | −0.37385 (11) | −0.14613 (10) | 0.0188 (3) | |
C4 | −0.1093 (2) | −0.40161 (11) | −0.16907 (10) | 0.0182 (3) | |
C5 | 0.0244 (2) | −0.32934 (12) | −0.09029 (11) | 0.0222 (3) | |
C6 | 0.0370 (2) | −0.41185 (13) | 0.00581 (10) | 0.0220 (3) | |
C7 | −0.0623 (2) | −0.53546 (11) | −0.14420 (10) | 0.0169 (3) | |
C8 | −0.2144 (2) | −0.62333 (12) | −0.19523 (11) | 0.0215 (3) | |
C9 | 0.1590 (2) | −0.56685 (13) | −0.17943 (11) | 0.0234 (3) | |
C10 | 0.0023 (3) | −0.64059 (14) | 0.03417 (12) | 0.0277 (3) | |
H4 | −0.085 (3) | −0.3795 (14) | −0.2394 (12) | 0.018 (4)* | |
H5A | −0.037 (3) | −0.2486 (16) | −0.0755 (12) | 0.024 (4)* | |
H5B | 0.163 (3) | −0.3184 (16) | −0.1179 (15) | 0.030 (5)* | |
H6A | 0.176 (3) | −0.4320 (17) | 0.0221 (15) | 0.029 (4)* | |
H6B | −0.027 (3) | −0.3731 (15) | 0.0682 (13) | 0.025 (4)* | |
H8A | −0.204 (3) | −0.6164 (16) | −0.2674 (14) | 0.030 (5)* | |
H8B | −0.359 (3) | −0.6087 (18) | −0.1756 (16) | 0.032 (5)* | |
H8C | −0.181 (3) | −0.7091 (16) | −0.1742 (13) | 0.026 (4)* | |
H9A | 0.254 (3) | −0.5216 (18) | −0.1463 (15) | 0.029 (5)* | |
H9B | 0.166 (3) | −0.5510 (16) | −0.2549 (15) | 0.032 (5)* | |
H9C | 0.188 (3) | −0.6552 (18) | −0.1664 (14) | 0.033 (5)* | |
H10A | 0.160 (3) | −0.6431 (16) | 0.0231 (14) | 0.028 (4)* | |
H10B | −0.061 (3) | −0.7154 (16) | 0.0084 (15) | 0.031 (5)* | |
H10C | −0.021 (3) | −0.6309 (17) | 0.1076 (16) | 0.037 (5)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0169 (4) | 0.0252 (5) | 0.0216 (4) | −0.0034 (4) | 0.0019 (4) | 0.0026 (4) |
O2 | 0.0257 (5) | 0.0421 (6) | 0.0236 (5) | 0.0038 (4) | 0.0059 (4) | −0.0046 (5) |
O3 | 0.0266 (5) | 0.0247 (5) | 0.0320 (5) | 0.0012 (4) | −0.0039 (4) | 0.0062 (4) |
C1 | 0.0162 (6) | 0.0197 (6) | 0.0181 (6) | −0.0011 (5) | −0.0004 (5) | −0.0013 (5) |
C2 | 0.0196 (7) | 0.0242 (6) | 0.0171 (6) | −0.0044 (5) | −0.0003 (5) | −0.0019 (5) |
C3 | 0.0205 (6) | 0.0164 (6) | 0.0196 (6) | −0.0033 (5) | −0.0007 (5) | −0.0006 (5) |
C4 | 0.0184 (6) | 0.0174 (6) | 0.0186 (6) | −0.0004 (5) | 0.0023 (5) | −0.0006 (5) |
C5 | 0.0199 (6) | 0.0189 (6) | 0.0277 (7) | −0.0036 (5) | 0.0000 (6) | −0.0032 (6) |
C6 | 0.0183 (7) | 0.0256 (6) | 0.0221 (6) | −0.0059 (5) | −0.0012 (5) | −0.0034 (6) |
C7 | 0.0150 (6) | 0.0165 (6) | 0.0192 (6) | −0.0024 (4) | 0.0012 (5) | 0.0002 (5) |
C8 | 0.0219 (7) | 0.0198 (6) | 0.0227 (6) | −0.0052 (5) | −0.0005 (5) | −0.0019 (6) |
C9 | 0.0182 (6) | 0.0247 (6) | 0.0273 (7) | −0.0054 (6) | 0.0032 (6) | 0.0019 (6) |
C10 | 0.0273 (7) | 0.0288 (7) | 0.0271 (7) | 0.0067 (6) | −0.0021 (6) | 0.0030 (6) |
Geometric parameters (Å, º) top
O1—C2 | 1.3980 (17) | C5—H5B | 0.97 (2) |
O1—C3 | 1.3989 (16) | C6—H6A | 0.94 (2) |
O2—C2 | 1.1950 (17) | C6—H6B | 1.001 (18) |
O3—C3 | 1.1954 (17) | C7—C8 | 1.5293 (19) |
C1—C2 | 1.5201 (19) | C7—C9 | 1.5327 (18) |
C1—C10 | 1.5236 (18) | C8—H8A | 0.938 (18) |
C1—C6 | 1.5578 (18) | C8—H8B | 0.98 (2) |
C1—C7 | 1.5620 (17) | C8—H8C | 1.012 (18) |
C3—C4 | 1.4975 (19) | C9—H9A | 0.90 (2) |
C4—C7 | 1.5478 (17) | C9—H9B | 0.992 (19) |
C4—C5 | 1.5541 (18) | C9—H9C | 1.01 (2) |
C4—H4 | 0.954 (16) | C10—H10A | 1.03 (2) |
C5—C6 | 1.544 (2) | C10—H10B | 0.981 (18) |
C5—H5A | 0.995 (18) | C10—H10C | 0.97 (2) |
| | | |
C2—O1—C3 | 122.57 (10) | C5—C6—H6B | 111.8 (10) |
C2—C1—C10 | 109.75 (12) | C1—C6—H6B | 111.3 (10) |
C2—C1—C6 | 106.34 (10) | H6A—C6—H6B | 108.0 (16) |
C10—C1—C6 | 113.12 (11) | C8—C7—C9 | 108.70 (11) |
C2—C1—C7 | 107.25 (10) | C8—C7—C4 | 113.34 (11) |
C10—C1—C7 | 115.84 (11) | C9—C7—C4 | 109.70 (11) |
C6—C1—C7 | 103.91 (10) | C8—C7—C1 | 114.11 (11) |
O2—C2—O1 | 115.95 (13) | C9—C7—C1 | 111.59 (11) |
O2—C2—C1 | 127.18 (13) | C4—C7—C1 | 99.15 (10) |
O1—C2—C1 | 116.81 (11) | C7—C8—H8A | 109.3 (12) |
O3—C3—O1 | 116.31 (13) | C7—C8—H8B | 113.0 (12) |
O3—C3—C4 | 127.52 (13) | H8A—C8—H8B | 108.3 (17) |
O1—C3—C4 | 116.10 (11) | C7—C8—H8C | 110.3 (11) |
C3—C4—C7 | 110.07 (11) | H8A—C8—H8C | 109.1 (15) |
C3—C4—C5 | 107.13 (10) | H8B—C8—H8C | 106.8 (16) |
C7—C4—C5 | 104.49 (10) | C7—C9—H9A | 111.2 (13) |
C3—C4—H4 | 107.1 (11) | C7—C9—H9B | 107.2 (12) |
C7—C4—H4 | 114.3 (10) | H9A—C9—H9B | 109.7 (17) |
C5—C4—H4 | 113.5 (10) | C7—C9—H9C | 110.0 (12) |
C6—C5—C4 | 104.47 (10) | H9A—C9—H9C | 109.7 (18) |
C6—C5—H5A | 113.5 (9) | H9B—C9—H9C | 109.1 (16) |
C4—C5—H5A | 111.8 (10) | C1—C10—H10A | 107.0 (10) |
C6—C5—H5B | 108.8 (11) | C1—C10—H10B | 111.6 (11) |
C4—C5—H5B | 109.4 (12) | H10A—C10—H10B | 109.9 (16) |
H5A—C5—H5B | 108.7 (15) | C1—C10—H10C | 109.8 (12) |
C5—C6—C1 | 106.17 (10) | H10A—C10—H10C | 106.9 (17) |
C5—C6—H6A | 111.7 (12) | H10B—C10—H10C | 111.4 (17) |
C1—C6—H6A | 107.9 (12) | | |
| | | |
C3—O1—C2—O2 | −168.79 (11) | C6—C1—C10—H10C | 62.92 (1.30) |
C3—O1—C2—C1 | 13.84 (16) | C7—C1—C10—H10A | 67.07 (1.14) |
C10—C1—C2—O2 | 11.46 (18) | C7—C1—C10—H10B | −53.20 (1.21) |
C6—C1—C2—O2 | −111.22 (15) | C7—C1—C10—H10C | −177.26 (1.29) |
C7—C1—C2—O2 | 138.08 (14) | C3—C4—C5—H5A | −36.94 (1.10) |
C10—C1—C2—O1 | −171.50 (12) | C3—C4—C5—H5B | −157.36 (1.23) |
C6—C1—C2—O1 | 65.82 (13) | C7—C4—C5—H5A | −153.71 (1.09) |
C7—C1—C2—O1 | −44.88 (14) | C7—C4—C5—H5B | 85.87 (1.23) |
C2—O1—C3—O3 | 170.88 (12) | H4—C4—C5—C6 | −155.76 (1.08) |
C2—O1—C3—C4 | −11.85 (16) | H4—C4—C5—H5A | 81.06 (1.54) |
O3—C3—C4—C7 | −140.87 (13) | H4—C4—C5—H5B | −39.36 (1.64) |
O1—C3—C4—C7 | 42.21 (14) | H4—C4—C7—C1 | 169.98 (1.09) |
O3—C3—C4—C5 | 106.09 (14) | H4—C4—C7—C8 | −68.68 (1.09) |
O1—C3—C4—C5 | −70.82 (13) | H4—C4—C7—C9 | 53.01 (1.09) |
C3—C4—C5—C6 | 86.25 (13) | C4—C5—C6—H6A | 120.33 (1.31) |
C7—C4—C5—C6 | −30.53 (14) | C4—C5—C6—H6B | −118.51 (1.10) |
C4—C5—C6—C1 | 2.99 (14) | H5A—C5—C6—C1 | 125.02 (1.11) |
C2—C1—C6—C5 | −87.82 (12) | H5A—C5—C6—H6A | −117.64 (1.72) |
C10—C1—C6—C5 | 151.64 (12) | H5A—C5—C6—H6B | 3.53 (1.57) |
C7—C1—C6—C5 | 25.19 (13) | H5B—C5—C6—C1 | −113.79 (1.23) |
C3—C4—C7—C8 | 51.86 (14) | H5B—C5—C6—H6B | 124.72 (1.65) |
C5—C4—C7—C8 | 166.59 (11) | H5B—C5—C6—H6A | 3.55 (1.80) |
C3—C4—C7—C9 | 173.55 (10) | C1—C7—C8—H8A | 174.94 (1.24) |
C5—C4—C7—C9 | −71.72 (12) | C1—C7—C8—H8B | 54.35 (1.35) |
C3—C4—C7—C1 | −69.48 (12) | C1—C7—C8—H8C | −65.09 (1.11) |
C5—C4—C7—C1 | 45.25 (13) | C4—C7—C8—H8A | 62.43 (1.24) |
C2—C1—C7—C8 | −51.26 (14) | C4—C7—C8—H8B | −58.15 (1.35) |
C10—C1—C7—C8 | 71.67 (16) | C4—C7—C8—H8C | −177.59 (1.10) |
C6—C1—C7—C8 | −163.62 (11) | C9—C7—C8—H8A | −59.82 (1.24) |
C2—C1—C7—C9 | −174.95 (11) | C9—C7—C8—H8B | 179.59 (1.34) |
C10—C1—C7—C9 | −52.02 (16) | C9—C7—C8—H8C | 60.15 (1.11) |
C6—C1—C7—C9 | 72.69 (13) | C1—C7—C9—H9A | −47.90 (1.37) |
C2—C1—C7—C4 | 69.52 (12) | C1—C7—C9—H9B | −167.79 (1.18) |
C10—C1—C7—C4 | −167.55 (11) | C1—C7—C9—H9C | 73.76 (1.22) |
C6—C1—C7—C4 | −42.84 (12) | C4—C7—C9—H9A | 60.97 (1.37) |
C2—C1—C10—H10A | −171.33 (1.13) | C4—C7—C9—H9B | −58.93 (1.18) |
C2—C1—C10—H10B | 68.40 (1.21) | C4—C7—C9—H9C | −177.37 (1.22) |
C2—C1—C10—H10C | −55.66 (1.30) | C8—C7—C9—H9A | −174.60 (1.37) |
C6—C1—C10—H10A | −52.75 (1.14) | C8—C7—C9—H9B | 65.50 (1.18) |
C6—C1—C10—H10B | −173.02 (1.21) | C8—C7—C9—H9C | −52.94 (1.23) |
(II) (
R/
S)-1,8,8-Trimethyl-3-oxabicyclo[3.2.1]octane-2,4-dione
top
Crystal data top
C10H14O3 | F(000) = 392 |
Mr = 182.21 | Dx = 1.313 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 6.4152 (4) Å | Cell parameters from 8192 reflections |
b = 11.4413 (8) Å | θ = 2.2–30.1° |
c = 12.5623 (8) Å | µ = 0.10 mm−1 |
β = 91.9680° | T = 110 K |
V = 921.51 (10) Å3 | Rectangular block, colourless |
Z = 4 | 0.5 × 0.45 × 0.3 mm |
Data collection top
Bruckers SMART CCD area-detector diffractometer | Rint = 0.012 |
Detector resolution: 0.75 pixels mm-1 | θmax = 26.4° |
ω scans | h = −7→7 |
11276 measured reflections | k = 0→14 |
1875 independent reflections | l = 0→15 |
1825 reflections with I > 2σ(I) | |
Refinement top
Refinement on F2 | 174 parameters |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.032 | w = 1/[σ2(Fo2) + (0.0403P)2 + 0.3112P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.081 | (Δ/σ)max = 0.001 |
S = 1.06 | Δρmax = 0.35 e Å−3 |
1875 reflections | Δρmin = −0.17 e Å−3 |
Crystal data top
C10H14O3 | V = 921.51 (10) Å3 |
Mr = 182.21 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.4152 (4) Å | µ = 0.10 mm−1 |
b = 11.4413 (8) Å | T = 110 K |
c = 12.5623 (8) Å | 0.5 × 0.45 × 0.3 mm |
β = 91.9680° | |
Data collection top
Bruckers SMART CCD area-detector diffractometer | 1825 reflections with I > 2σ(I) |
11276 measured reflections | Rint = 0.012 |
1875 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | 174 parameters |
wR(F2) = 0.081 | All H-atom parameters refined |
S = 1.06 | Δρmax = 0.35 e Å−3 |
1875 reflections | Δρmin = −0.17 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.11225 (11) | 0.67221 (6) | 0.45800 (6) | 0.02161 (18) | |
O2 | 0.13006 (12) | 0.81147 (7) | 0.57870 (6) | 0.0289 (2) | |
O3 | 0.12307 (12) | 0.55693 (7) | 0.31747 (6) | 0.0295 (2) | |
C1 | −0.20971 (15) | 0.78513 (8) | 0.48998 (7) | 0.0188 (2) | |
C2 | 0.01948 (15) | 0.76254 (9) | 0.51441 (7) | 0.0199 (2) | |
C3 | 0.01820 (16) | 0.62310 (8) | 0.36619 (8) | 0.0205 (2) | |
C4 | −0.20542 (15) | 0.65516 (8) | 0.34346 (8) | 0.0196 (2) | |
C5 | −0.33578 (16) | 0.59093 (9) | 0.42730 (8) | 0.0231 (2) | |
C6 | −0.33062 (16) | 0.67362 (9) | 0.52465 (8) | 0.0219 (2) | |
C7 | −0.24227 (15) | 0.78614 (8) | 0.36642 (7) | 0.0181 (2) | |
C8 | −0.09264 (17) | 0.86681 (9) | 0.30874 (8) | 0.0239 (2) | |
C9 | −0.46702 (17) | 0.81945 (10) | 0.33370 (9) | 0.0246 (2) | |
C10 | −0.27696 (18) | 0.89523 (10) | 0.54756 (9) | 0.0265 (2) | |
H4 | −0.2417 (19) | 0.6336 (11) | 0.2703 (10) | 0.021 (3)* | |
H5A | −0.278 (2) | 0.5114 (12) | 0.4436 (10) | 0.029 (3)* | |
H5B | −0.478 (2) | 0.5795 (12) | 0.3983 (11) | 0.030 (3)* | |
H6A | −0.473 (2) | 0.6973 (12) | 0.5428 (10) | 0.027 (3)* | |
H6B | −0.264 (2) | 0.6367 (12) | 0.5877 (10) | 0.026 (3)* | |
H8A | −0.120 (2) | 0.8619 (12) | 0.2330 (12) | 0.034 (3)* | |
H8B | 0.054 (2) | 0.8466 (13) | 0.3228 (11) | 0.034 (3)* | |
H8C | −0.112 (2) | 0.9488 (13) | 0.3333 (11) | 0.035 (4)* | |
H9A | −0.570 (2) | 0.7780 (12) | 0.3751 (11) | 0.032 (3)* | |
H9B | −0.493 (2) | 0.8008 (12) | 0.2585 (12) | 0.035 (4)* | |
H9C | −0.485 (2) | 0.9038 (13) | 0.3433 (10) | 0.031 (3)* | |
H10A | −0.431 (2) | 0.9027 (12) | 0.5386 (11) | 0.034 (4)* | |
H10B | −0.210 (2) | 0.9661 (13) | 0.5179 (11) | 0.036 (4)* | |
H10C | −0.243 (2) | 0.8890 (13) | 0.6235 (12) | 0.035 (4)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0182 (3) | 0.0232 (4) | 0.0233 (4) | −0.0005 (3) | −0.0017 (3) | 0.0033 (3) |
O2 | 0.0272 (4) | 0.0346 (4) | 0.0245 (4) | −0.0049 (3) | −0.0048 (3) | −0.0022 (3) |
O3 | 0.0303 (4) | 0.0269 (4) | 0.0314 (4) | −0.0050 (3) | 0.0029 (3) | 0.0081 (3) |
C1 | 0.0195 (5) | 0.0186 (5) | 0.0183 (5) | 0.0005 (4) | 0.0009 (3) | 0.0010 (4) |
C2 | 0.0226 (5) | 0.0204 (5) | 0.0168 (4) | 0.0022 (4) | 0.0013 (4) | −0.0001 (4) |
C3 | 0.0237 (5) | 0.0170 (5) | 0.0208 (5) | 0.0013 (4) | 0.0009 (4) | 0.0007 (4) |
C4 | 0.0215 (5) | 0.0178 (5) | 0.0192 (5) | −0.0009 (4) | −0.0023 (4) | 0.0005 (4) |
C5 | 0.0216 (5) | 0.0188 (5) | 0.0288 (5) | 0.0028 (4) | −0.0011 (4) | −0.0023 (4) |
C6 | 0.0208 (5) | 0.0226 (5) | 0.0224 (5) | 0.0050 (4) | 0.0025 (4) | −0.0006 (4) |
C7 | 0.0191 (5) | 0.0173 (5) | 0.0180 (4) | 0.0014 (3) | −0.0004 (3) | 0.0017 (4) |
C8 | 0.0263 (6) | 0.0222 (5) | 0.0232 (5) | 0.0050 (4) | 0.0022 (4) | −0.0003 (4) |
C9 | 0.0226 (5) | 0.0258 (5) | 0.0250 (5) | 0.0033 (4) | −0.0028 (4) | 0.0050 (4) |
C10 | 0.0303 (6) | 0.0245 (5) | 0.0248 (5) | −0.0048 (4) | 0.0025 (4) | 0.0049 (4) |
Geometric parameters (Å, º) top
O1—C2 | 1.3976 (12) | C5—H5B | 0.981 (14) |
O1—C3 | 1.4008 (12) | C6—H6A | 0.985 (14) |
O2—C2 | 1.1956 (13) | C6—H6B | 0.983 (13) |
O3—C3 | 1.1952 (12) | C7—C8 | 1.5317 (13) |
C1—C2 | 1.5139 (13) | C7—C9 | 1.5337 (13) |
C1—C10 | 1.5224 (13) | C8—H8A | 0.963 (14) |
C1—C7 | 1.5591 (13) | C8—H8B | 0.982 (15) |
C1—C6 | 1.5628 (13) | C8—H8C | 0.997 (15) |
C3—C4 | 1.4986 (13) | C9—H9A | 0.976 (14) |
C4—C7 | 1.5457 (13) | C9—H9B | 0.978 (15) |
C4—C5 | 1.5522 (14) | C9—H9C | 0.981 (14) |
C4—H4 | 0.972 (12) | C10—H10A | 0.993 (14) |
C5—C6 | 1.5456 (15) | C10—H10B | 0.997 (15) |
C5—H5A | 1.001 (14) | C10—H10C | 0.974 (15) |
| | | |
C2—O1—C3 | 122.36 (8) | C5—C6—H6B | 111.8 (8) |
C2—C1—C10 | 109.51 (8) | C1—C6—H6B | 111.6 (8) |
C2—C1—C7 | 107.40 (7) | H6A—C6—H6B | 108.2 (10) |
C10—C1—C7 | 115.88 (8) | C8—C7—C9 | 108.79 (8) |
C2—C1—C6 | 106.98 (8) | C8—C7—C4 | 113.18 (8) |
C10—C1—C6 | 113.05 (8) | C9—C7—C4 | 109.84 (8) |
C7—C1—C6 | 103.46 (8) | C8—C7—C1 | 114.25 (8) |
O2—C2—O1 | 115.83 (9) | C9—C7—C1 | 111.17 (8) |
O2—C2—C1 | 127.34 (9) | C4—C7—C1 | 99.35 (7) |
O1—C2—C1 | 116.80 (8) | C7—C8—H8A | 109.6 (8) |
O3—C3—O1 | 116.20 (9) | C7—C8—H8B | 112.8 (8) |
O3—C3—C4 | 127.55 (9) | H8A—C8—H8B | 107.8 (11) |
O1—C3—C4 | 116.17 (8) | C7—C8—H8C | 109.4 (8) |
C3—C4—C7 | 110.69 (8) | H8A—C8—H8C | 109.9 (12) |
C3—C4—C5 | 106.82 (8) | H8B—C8—H8C | 107.3 (12) |
C7—C4—C5 | 104.07 (8) | C7—C9—H9A | 112.4 (8) |
C3—C4—H4 | 108.3 (7) | C7—C9—H9B | 109.5 (8) |
C7—C4—H4 | 112.9 (7) | H9A—C9—H9B | 108.2 (11) |
C5—C4—H4 | 113.8 (7) | C7—C9—H9C | 109.2 (8) |
C6—C5—C4 | 104.46 (8) | H9A—C9—H9C | 109.0 (11) |
C6—C5—H5A | 113.4 (7) | H9B—C9—H9C | 108.5 (11) |
C4—C5—H5A | 111.4 (7) | C1—C10—H10A | 108.3 (8) |
C6—C5—H5B | 111.7 (8) | C1—C10—H10B | 111.3 (8) |
C4—C5—H5B | 109.1 (8) | H10A—C10—H10B | 109.2 (11) |
H5A—C5—H5B | 106.7 (11) | C1—C10—H10C | 110.3 (8) |
C5—C6—C1 | 106.05 (8) | H10A—C10—H10C | 107.8 (11) |
C5—C6—H6A | 110.9 (8) | H10B—C10—H10C | 109.9 (12) |
C1—C6—H6A | 108.2 (8) | | |
| | | |
C3—O1—C2—O2 | −166.59 (9) | C6—C1—C10—H10A | −53.3 (9) |
C3—O1—C2—C1 | 15.18 (13) | C6—C1—C10—H10B | −173.4 (9) |
C10—C1—C2—O2 | 9.17 (14) | C6—C1—C10—H10C | 64.5 (9) |
C7—C1—C2—O2 | 135.78 (10) | C7—C1—C10—H10A | 65.9 (9) |
C6—C1—C2—O2 | −113.69 (11) | C7—C1—C10—H10B | −54.2 (9) |
C10—C1—C2—O1 | −172.82 (8) | C7—C1—C10—H10C | −176.4 (9) |
C7—C1—C2—O1 | −46.21 (11) | O1—C3—C4—H4 | 165.4 (7) |
C6—C1—C2—O1 | 64.32 (10) | O3—C3—C4—H4 | −18.0 (8) |
C2—O1—C3—O3 | 171.02 (9) | C3—C4—C5—H5A | −37.0 (8) |
C2—O1—C3—C4 | −11.84 (13) | C3—C4—C5—H5B | −154.6 (8) |
O3—C3—C4—C7 | −142.28 (10) | C7—C4—C5—H5A | −154.1 (8) |
O1—C3—C4—C7 | 40.97 (11) | C7—C4—C5—H5B | 88.3 (9) |
O3—C3—C4—C5 | 105.04 (12) | H4—C4—C5—C6 | −154.7 (8) |
O1—C3—C4—C5 | −71.71 (10) | H4—C4—C5—H5A | 82.5 (10) |
C3—C4—C5—C6 | 85.83 (9) | H4—C4—C5—H5B | −35.1 (10) |
C7—C4—C5—C6 | −31.32 (10) | H4—C4—C7—C1 | 170.2 (8) |
C4—C5—C6—C1 | 3.50 (10) | H4—C4—C7—C8 | −68.2 (8) |
C2—C1—C6—C5 | −88.09 (9) | H4—C4—C7—C9 | 53.6 (8) |
C10—C1—C6—C5 | 151.28 (9) | C4—C5—C6—H6A | 120.7 (8) |
C7—C1—C6—C5 | 25.15 (10) | C4—C5—C6—H6B | −118.3 (8) |
C3—C4—C7—C8 | 53.40 (11) | H5A—C5—C6—C1 | 125.0 (8) |
C5—C4—C7—C8 | 167.82 (8) | H5A—C5—C6—H6A | −117.8 (10) |
C3—C4—C7—C9 | 175.20 (8) | H5A—C5—C6—H6B | 3.1 (10) |
C5—C4—C7—C9 | −70.38 (9) | H5B—C5—C6—C1 | −114.4 (9) |
C3—C4—C7—C1 | −68.16 (9) | H5B—C5—C6—H6A | 2.9 (10) |
C5—C4—C7—C1 | 46.27 (9) | H5B—C5—C6—H6B | 123.81 |
C2—C1—C7—C8 | −51.29 (10) | C1—C7—C8—H8A | 179.01 |
C10—C1—C7—C8 | 71.47 (11) | C1—C7—C8—H8B | 58.87 |
C6—C1—C7—C8 | −164.22 (8) | C1—C7—C8—H8C | −60.49 |
C2—C1—C7—C9 | −174.88 (8) | C4—C7—C8—H8A | 66.3 (9) |
C10—C1—C7—C9 | −52.13 (11) | C4—C7—C8—H8B | −53.9 (9) |
C6—C1—C7—C9 | 72.18 (10) | C4—C7—C8—H8C | −173.2 (9) |
C2—C1—C7—C4 | 69.49 (9) | C9—C7—C8—H8A | −56.1 (9) |
C10—C1—C7—C4 | −167.76 (9) | C9—C7—C8—H8B | −176.3 (9) |
C6—C1—C7—C4 | −43.45 (9) | C9—C7—C8—H8C | 64.4 (9) |
C2—C1—C6—H6A | 152.9 (8) | C1—C7—C9—H9A | −45.7 (9) |
C2—C1—C6—H6B | 33.9 (8) | C1—C7—C9—H9B | −166.0 (9) |
C7—C1—C6—H6A | −93.9 (8) | C1—C7—C9—H9C | 75.5 (9) |
C7—C1—C6—H6B | 147.1 (8) | C4—C7—C9—H9A | 63.3 (9) |
C10—C1—C6—H6A | 32.2 (8) | C4—C7—C9—H9B | −57.0 (9) |
C10—C1—C6—H6B | −86.73 | C4—C7—C9—H9C | −175.6 (9) |
C2—C1—C10—H10A | −172.5 (9) | C8—C7—C9—H9A | −172.3 (9) |
C2—C1—C10—H10B | 67.5 (9) | C8—C7—C9—H9B | 67.4 (9) |
C2—C1—C10—H10C | −54.7 (9) | C8—C7—C9—H9C | −51.2 (9) |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C10H14O3 | C10H14O3 |
Mr | 182.21 | 182.21 |
Crystal system, space group | Orthorhombic, P212121 | Monoclinic, P21/n |
Temperature (K) | 110 | 110 |
a, b, c (Å) | 6.4262 (3), 11.0841 (4), 12.9142 (5) | 6.4152 (4), 11.4413 (8), 12.5623 (8) |
α, β, γ (°) | 90, 90, 90 | 90, 91.9680, 90 |
V (Å3) | 919.86 (6) | 921.51 (10) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.10 |
Crystal size (mm) | 0.45 × 0.4 × 0.3 | 0.5 × 0.45 × 0.3 |
|
Data collection |
Diffractometer | Brukers SMART CCD area-detector diffractometer | Bruckers SMART CCD area-detector diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11128, 1103, 1090 | 11276, 1875, 1825 |
Rint | 0.021 | 0.012 |
(sin θ/λ)max (Å−1) | 0.625 | 0.625 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.072, 1.11 | 0.032, 0.081, 1.06 |
No. of reflections | 1103 | 1875 |
No. of parameters | 174 | 174 |
No. of restraints | ? | ? |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.20, −0.20 | 0.35, −0.17 |
Selected geometric parameters (Å, º) for (I) topO1—C2 | 1.3980 (17) | C1—C7 | 1.5620 (17) |
O1—C3 | 1.3989 (16) | C3—C4 | 1.4975 (19) |
O2—C2 | 1.1950 (17) | C4—C7 | 1.5478 (17) |
O3—C3 | 1.1954 (17) | C4—C5 | 1.5541 (18) |
C1—C2 | 1.5201 (19) | C5—C6 | 1.544 (2) |
C1—C10 | 1.5236 (18) | C7—C8 | 1.5293 (19) |
C1—C6 | 1.5578 (18) | C7—C9 | 1.5327 (18) |
| | | |
C2—O1—C3 | 122.57 (10) | O1—C3—C4 | 116.10 (11) |
C2—C1—C10 | 109.75 (12) | C3—C4—C7 | 110.07 (11) |
C2—C1—C6 | 106.34 (10) | C3—C4—C5 | 107.13 (10) |
C10—C1—C6 | 113.12 (11) | C7—C4—C5 | 104.49 (10) |
C2—C1—C7 | 107.25 (10) | C6—C5—C4 | 104.47 (10) |
C10—C1—C7 | 115.84 (11) | C5—C6—C1 | 106.17 (10) |
C6—C1—C7 | 103.91 (10) | C8—C7—C9 | 108.70 (11) |
O2—C2—O1 | 115.95 (13) | C8—C7—C4 | 113.34 (11) |
O2—C2—C1 | 127.18 (13) | C9—C7—C4 | 109.70 (11) |
O1—C2—C1 | 116.81 (11) | C8—C7—C1 | 114.11 (11) |
O3—C3—O1 | 116.31 (13) | C9—C7—C1 | 111.59 (11) |
O3—C3—C4 | 127.52 (13) | C4—C7—C1 | 99.15 (10) |
| | | |
C3—O1—C2—C1 | 13.84 (16) | O1—C3—C4—C7 | 42.21 (14) |
C7—C1—C2—O1 | −44.88 (14) | C3—C4—C7—C1 | −69.48 (12) |
C2—O1—C3—C4 | −11.85 (16) | C2—C1—C7—C4 | 69.52 (12) |
Selected geometric parameters (Å, º) for (II) topO1—C2 | 1.3976 (12) | C1—C6 | 1.5628 (13) |
O1—C3 | 1.4008 (12) | C3—C4 | 1.4986 (13) |
O2—C2 | 1.1956 (13) | C4—C7 | 1.5457 (13) |
O3—C3 | 1.1952 (12) | C4—C5 | 1.5522 (14) |
C1—C2 | 1.5139 (13) | C5—C6 | 1.5456 (15) |
C1—C10 | 1.5224 (13) | C7—C8 | 1.5317 (13) |
C1—C7 | 1.5591 (13) | C7—C9 | 1.5337 (13) |
| | | |
C2—O1—C3 | 122.36 (8) | O1—C3—C4 | 116.17 (8) |
C2—C1—C10 | 109.51 (8) | C3—C4—C7 | 110.69 (8) |
C2—C1—C7 | 107.40 (7) | C3—C4—C5 | 106.82 (8) |
C10—C1—C7 | 115.88 (8) | C7—C4—C5 | 104.07 (8) |
C2—C1—C6 | 106.98 (8) | C6—C5—C4 | 104.46 (8) |
C10—C1—C6 | 113.05 (8) | C5—C6—C1 | 106.05 (8) |
C7—C1—C6 | 103.46 (8) | C8—C7—C9 | 108.79 (8) |
O2—C2—O1 | 115.83 (9) | C8—C7—C4 | 113.18 (8) |
O2—C2—C1 | 127.34 (9) | C9—C7—C4 | 109.84 (8) |
O1—C2—C1 | 116.80 (8) | C8—C7—C1 | 114.25 (8) |
O3—C3—O1 | 116.20 (9) | C9—C7—C1 | 111.17 (8) |
O3—C3—C4 | 127.55 (9) | C4—C7—C1 | 99.35 (7) |
| | | |
C3—O1—C2—C1 | 15.18 (13) | O1—C3—C4—C7 | 40.97 (11) |
C7—C1—C2—O1 | −46.21 (11) | C3—C4—C7—C1 | −68.16 (9) |
C2—O1—C3—C4 | −11.84 (13) | C2—C1—C7—C4 | 69.49 (9) |
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The physical properties of several camphor derivatives have been extensively studied, especially in relation to their chiroptical features which is affected by the nature of the substituent attached to the bicyclic ring in the bridgehead position (Yager & Morgan, 1935; Williams & Symth, 1962; Mjojo & Welsh, 1992; Mora & Fitch, 1997). We report hete the low-temperature structural data for D-camphoric anhydride, (I), and DL-camphoric anhydride, (II). The former was reinvestigated for comparison.
The corresponding internuclear distances and angles of the two molecules are statistically equal and all geometrical parameters of the low-temperature structure of (I) compare well with those obtained earlier based on room-temperature data (Wichmann et al., 1987). The conformation of the six-membered rings were determined in terms of their ring-puckering parameters (Cremer & Pople, 1975); (I): Q = 0.637 (1) Å, θ = 45.6 (1)° and ϕ = -3.1 (1)°; (II): Q = 0.628 (1) Å, θ = 45.1° and ϕ = -5.1 (1)°. These values indicate that the rings adopt half-boat conformations. The groups of atoms C7/C3/C2/C1 and C1/C6/C5/C4 lie in the least-squares planes of their respective six- and five-membered rings. In both structures, the planes form an angle of 80.3 (1)°.
Weak C—H···O type hydrogen bonds connect molecules of the same chirality, forming linear chains. These columns of D—L, (I), and D—D, (II), isomers are held together by even weaker contacts giving rise to a remarkable similarity in the packing. This observation does not support the conclusion by Brock et al. (1991) that the racemic crystal tend to be denser than its chiral counterpart.