Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105010267/tr1124sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105010267/tr1124Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105010267/tr1124IIsup3.hkl |
CCDC references: 273075; 273076
Compounds (I) and (II) were synthesized by condensing the dilithium salt of 3-methylenecyclohexanecarboxylic acid with, respectively, dicyclobutylmethanone (Erickson et al., 1966) or cyclopentanone, following the synthetic sequence reported for the other members of this family of compounds (Carrasco et al., 2001). Analysis for compound (I): m.p. 448–449 K; 1H NMR (300 MHz, MeOD, δ, p.p.m.): 3.67 (d, J = 11.5 Hz, 1H), 3.62 (d, J = 11.5 Hz, 1H), 3.23 (m, 1H), 2.61 (m, 1H), 2.47 (d, J = 11.8 Hz, 1H), 2.27 (m, 3H), 2.12 (m, 2H), 1.99 (m, 3H), 1.74 (m, 8H), 1.58 (m, 2H), 1.40 (d, J = 11.8 Hz, 1H); 13C NMR (75.4 MHz, MeOD, δ, p.p.m.): 17.7, 18.1, 19.5, 26.2, 26.7, 27.4, 31.9, 32.8, 40.4, 41.1, 44.6, 47.6, 56.9, 67.3, 82.4, 86.4, 176.2; IR (KBr, νmax, cm−1): 3398, 2950, 2363, 1701, 1651, 1540, 1458, 1251, 1167, 1123, 995. Analysis for compound (II): m.p. 426–427 K; 1H NMR (300 MHz, MeOD, δ, p.p.m.): 3.48 (d, J = 11.7 Hz, 1H), 3.42 (d, J = 11.7 Hz, 1H), 2.50 (d, J = 11.4 Hz, 1H), 2.20 (m, 2H), 1.95 (m, 2H), 1.73 (m, 5H), 1.59 (d, J = 11.4 Hz, 1H), 1.50 (m, 4H), 1.40 (dd, J1 = 12.4, J2 = 5.8 Hz, 1H); 13C NMR (75.4 MHz, MeOD, δ, p.p.m.): 19.7, 24.1, 24.5, 31.7, 31.8, 32.0, 39.2, 40.6, 55.6, 66.4, 82.3, 94.1, 176.0; IR (KBr, νmax, cm−1): 3749, 3380, 2956, 2870, 2361, 2337, 1703, 1456, 1339, 1257, 1157, 1046, 1002. Single crystals of (I) and (II), suitable for X-ray analysis, were grown at room temperature from a damp carbon tetrachloride–2,2,4-trimethylpentane mixture (Ratio?).
All H atoms were located in difference Fourier maps and subsequently allowed to refine as riding models on their respective C and O atoms, with C—H = 0.99 (CH2) or 1.00 Å (CH) and O—H = 0.84 Å, and with Uiso(H) = 1.2Ueq(C, O). The molecules of (II) (Fig. 2) exhibit positional disorder in the carboxylic acid H atom [pp(H4) = 0.59 (3), pp(H3) = 0.41 (3)] and in the cyclopentane ring [pp(C11A) = 0.58 (2), pp(C11B) = 0.42 (2)]. The bond distances around the disordered atoms C11A/B (Fig. 2) in the cyclopentane ring were restrained using the DFIX command based on the average Csp3—Csp3 value (Allen et al., 1987). Attempted free refinement led to unrealistic geometrical parameters.
For both compounds, data collection: KappaCCD Server Software (Nonius, 2000); cell refinement: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Xtal3.6 (Hall et al., 1999) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97, WinGX (Farrugia, 1999) and PLATON.
C17H26O4 | Z = 2 |
Mr = 294.38 | F(000) = 320 |
Triclinic, P1 | Dx = 1.270 Mg m−3 |
Hall symbol: -P 1 | Melting point = 448–449 K |
a = 8.757 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.807 (3) Å | Cell parameters from 3531 reflections |
c = 11.769 (6) Å | θ = 1.8–27.5° |
α = 84.073 (11)° | µ = 0.09 mm−1 |
β = 75.766 (13)° | T = 170 K |
γ = 61.044 (9)° | Prism, colourless |
V = 769.7 (5) Å3 | 0.45 × 0.10 × 0.10 mm |
Nonius KappaCCD area-detector diffractometer | 3087 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Horizontally mounted graphite crystal monochromator | θmax = 27.5°, θmin = 1.8° |
Detector resolution: 9 pixels mm-1 | h = 0→11 |
ϕ and ω scans | k = −9→11 |
3531 measured reflections | l = −14→15 |
3531 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.058 | H-atom parameters constrained |
wR(F2) = 0.176 | w = 1/[σ2(Fo2) + (0.1125P)2 + 0.2845P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
3531 reflections | Δρmax = 0.45 e Å−3 |
191 parameters | Δρmin = −0.46 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.155 (15) |
C17H26O4 | γ = 61.044 (9)° |
Mr = 294.38 | V = 769.7 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.757 (3) Å | Mo Kα radiation |
b = 8.807 (3) Å | µ = 0.09 mm−1 |
c = 11.769 (6) Å | T = 170 K |
α = 84.073 (11)° | 0.45 × 0.10 × 0.10 mm |
β = 75.766 (13)° |
Nonius KappaCCD area-detector diffractometer | 3087 reflections with I > 2σ(I) |
3531 measured reflections | Rint = 0.000 |
3531 independent reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.176 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.45 e Å−3 |
3531 reflections | Δρmin = −0.46 e Å−3 |
191 parameters |
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 | 0.59693 (14) | 0.05265 (14) | 0.30781 (10) | 0.0200 (3) | |
O2 | 0.92296 (16) | −0.30382 (17) | 0.10000 (11) | 0.0309 (3) | |
H2 | 0.8770 | −0.3421 | 0.0636 | 0.037* | |
O3 | 0.29920 (19) | 0.29624 (18) | 0.02871 (13) | 0.0386 (4) | |
O4 | 0.23644 (16) | 0.51195 (16) | 0.14536 (11) | 0.0273 (3) | |
H4 | 0.1491 | 0.5655 | 0.1133 | 0.033* | |
C1 | 0.7211 (2) | −0.0218 (2) | 0.19675 (14) | 0.0212 (4) | |
C2 | 0.8680 (2) | 0.0310 (2) | 0.17486 (16) | 0.0275 (4) | |
H2A | 0.9478 | −0.0129 | 0.0967 | 0.033* | |
H2B | 0.9409 | −0.0221 | 0.2344 | 0.033* | |
C3 | 0.7878 (2) | 0.2285 (3) | 0.18076 (17) | 0.0297 (4) | |
H3A | 0.8802 | 0.2605 | 0.1376 | 0.036* | |
H3B | 0.7569 | 0.2650 | 0.2637 | 0.036* | |
C4 | 0.6200 (2) | 0.3296 (2) | 0.13016 (16) | 0.0257 (4) | |
H4A | 0.6576 | 0.3377 | 0.0442 | 0.031* | |
H4B | 0.5516 | 0.4491 | 0.1635 | 0.031* | |
C5 | 0.4952 (2) | 0.2454 (2) | 0.15573 (14) | 0.0201 (4) | |
C6 | 0.6079 (2) | 0.0610 (2) | 0.10563 (14) | 0.0216 (4) | |
H6A | 0.6824 | 0.0566 | 0.0264 | 0.026* | |
H6B | 0.5331 | 0.0063 | 0.1030 | 0.026* | |
C7 | 0.3343 (2) | 0.3519 (2) | 0.10279 (14) | 0.0227 (4) | |
C8 | 0.7969 (2) | −0.2171 (2) | 0.20617 (15) | 0.0253 (4) | |
H8A | 0.8571 | −0.2579 | 0.2726 | 0.030* | |
H8B | 0.6980 | −0.2465 | 0.2220 | 0.030* | |
C9 | 0.4385 (2) | 0.2104 (2) | 0.28944 (14) | 0.0180 (3) | |
C10 | 0.4054 (2) | 0.3516 (2) | 0.37322 (14) | 0.0199 (4) | |
H10 | 0.4928 | 0.3955 | 0.3394 | 0.024* | |
C11 | 0.2179 (2) | 0.5105 (2) | 0.41273 (15) | 0.0247 (4) | |
H11A | 0.2033 | 0.6177 | 0.3697 | 0.030* | |
H11B | 0.1173 | 0.4879 | 0.4141 | 0.030* | |
C12 | 0.2589 (2) | 0.5020 (2) | 0.53405 (15) | 0.0275 (4) | |
H12A | 0.1597 | 0.5124 | 0.6006 | 0.033* | |
H12B | 0.3032 | 0.5829 | 0.5443 | 0.033* | |
C13 | 0.4086 (2) | 0.3133 (2) | 0.50419 (15) | 0.0239 (4) | |
H13A | 0.3718 | 0.2246 | 0.5363 | 0.029* | |
H13B | 0.5229 | 0.2873 | 0.5232 | 0.029* | |
C14 | 0.2765 (2) | 0.1767 (2) | 0.31482 (14) | 0.0191 (4) | |
H14 | 0.1725 | 0.2844 | 0.2957 | 0.023* | |
C15 | 0.2119 (2) | 0.1175 (2) | 0.43764 (15) | 0.0226 (4) | |
H15A | 0.3098 | 0.0403 | 0.4772 | 0.027* | |
H15B | 0.1147 | 0.2138 | 0.4905 | 0.027* | |
C16 | 0.1464 (2) | 0.0212 (2) | 0.37677 (17) | 0.0287 (4) | |
H16A | 0.0193 | 0.0899 | 0.3720 | 0.034* | |
H16B | 0.1728 | −0.0956 | 0.4081 | 0.034* | |
C17 | 0.2798 (2) | 0.0194 (2) | 0.26333 (16) | 0.0265 (4) | |
H17A | 0.2310 | 0.0459 | 0.1921 | 0.032* | |
H17B | 0.3978 | −0.0866 | 0.2516 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0165 (6) | 0.0222 (6) | 0.0162 (6) | −0.0054 (5) | −0.0031 (4) | 0.0002 (4) |
O2 | 0.0232 (6) | 0.0342 (7) | 0.0251 (7) | −0.0029 (6) | −0.0071 (5) | −0.0107 (5) |
O3 | 0.0370 (8) | 0.0336 (8) | 0.0387 (8) | −0.0035 (6) | −0.0230 (7) | −0.0080 (6) |
O4 | 0.0246 (6) | 0.0240 (6) | 0.0284 (7) | −0.0056 (5) | −0.0107 (5) | 0.0005 (5) |
C1 | 0.0163 (7) | 0.0259 (8) | 0.0159 (7) | −0.0060 (7) | −0.0020 (6) | −0.0022 (6) |
C2 | 0.0184 (8) | 0.0370 (10) | 0.0238 (9) | −0.0107 (7) | −0.0041 (7) | −0.0004 (7) |
C3 | 0.0235 (9) | 0.0391 (10) | 0.0304 (10) | −0.0190 (8) | −0.0034 (7) | 0.0010 (8) |
C4 | 0.0253 (9) | 0.0303 (9) | 0.0228 (8) | −0.0167 (7) | −0.0018 (7) | 0.0048 (7) |
C5 | 0.0197 (8) | 0.0238 (8) | 0.0158 (7) | −0.0100 (7) | −0.0035 (6) | 0.0010 (6) |
C6 | 0.0183 (7) | 0.0251 (8) | 0.0161 (8) | −0.0065 (7) | −0.0033 (6) | −0.0004 (6) |
C7 | 0.0228 (8) | 0.0253 (8) | 0.0174 (8) | −0.0101 (7) | −0.0039 (6) | 0.0019 (6) |
C8 | 0.0211 (8) | 0.0254 (9) | 0.0212 (8) | −0.0039 (7) | −0.0057 (7) | −0.0022 (7) |
C9 | 0.0143 (7) | 0.0198 (8) | 0.0176 (7) | −0.0063 (6) | −0.0040 (6) | 0.0011 (6) |
C10 | 0.0193 (8) | 0.0216 (8) | 0.0195 (8) | −0.0104 (7) | −0.0032 (6) | −0.0010 (6) |
C11 | 0.0254 (9) | 0.0221 (8) | 0.0251 (9) | −0.0097 (7) | −0.0047 (7) | −0.0041 (7) |
C12 | 0.0297 (9) | 0.0291 (9) | 0.0237 (9) | −0.0141 (8) | −0.0029 (7) | −0.0067 (7) |
C13 | 0.0260 (8) | 0.0271 (9) | 0.0202 (8) | −0.0133 (7) | −0.0058 (7) | −0.0014 (6) |
C14 | 0.0165 (7) | 0.0206 (8) | 0.0199 (8) | −0.0088 (6) | −0.0030 (6) | −0.0010 (6) |
C15 | 0.0222 (8) | 0.0255 (8) | 0.0213 (8) | −0.0137 (7) | −0.0020 (6) | 0.0004 (6) |
C16 | 0.0280 (9) | 0.0319 (9) | 0.0313 (10) | −0.0195 (8) | −0.0028 (7) | −0.0018 (7) |
C17 | 0.0262 (9) | 0.0302 (9) | 0.0280 (9) | −0.0175 (7) | −0.0024 (7) | −0.0063 (7) |
O1—C1 | 1.452 (2) | C8—H8B | 0.9900 |
O1—C9 | 1.4559 (18) | C9—C10 | 1.538 (2) |
O2—C8 | 1.437 (2) | C9—C14 | 1.540 (2) |
O2—H2 | 0.8400 | C10—C13 | 1.548 (2) |
O3—C7 | 1.209 (2) | C10—C11 | 1.551 (2) |
O4—C7 | 1.318 (2) | C10—H10 | 1.0000 |
O4—H4 | 0.8400 | C11—C12 | 1.542 (3) |
C1—C8 | 1.517 (2) | C11—H11A | 0.9900 |
C1—C6 | 1.525 (2) | C11—H11B | 0.9900 |
C1—C2 | 1.527 (2) | C12—C13 | 1.545 (2) |
C2—C3 | 1.530 (3) | C12—H12A | 0.9900 |
C2—H2A | 0.9900 | C12—H12B | 0.9900 |
C2—H2B | 0.9900 | C13—H13A | 0.9900 |
C3—C4 | 1.537 (2) | C13—H13B | 0.9900 |
C3—H3A | 0.9900 | C14—C17 | 1.553 (2) |
C3—H3B | 0.9900 | C14—C15 | 1.552 (2) |
C4—C5 | 1.552 (2) | C14—H14 | 1.0000 |
C4—H4A | 0.9900 | C15—C16 | 1.536 (2) |
C4—H4B | 0.9900 | C15—H15A | 0.9900 |
C5—C7 | 1.512 (2) | C15—H15B | 0.9900 |
C5—C6 | 1.523 (2) | C16—C17 | 1.539 (3) |
C5—C9 | 1.576 (2) | C16—H16A | 0.9900 |
C6—H6A | 0.9900 | C16—H16B | 0.9900 |
C6—H6B | 0.9900 | C17—H17A | 0.9900 |
C8—H8A | 0.9900 | C17—H17B | 0.9900 |
C1—O1—C9 | 110.78 (12) | O1—C9—C5 | 102.20 (12) |
C8—O2—H2 | 109.5 | C10—C9—C5 | 114.21 (13) |
C7—O4—H4 | 109.5 | C14—C9—C5 | 111.94 (12) |
O1—C1—C8 | 106.61 (13) | C9—C10—C13 | 120.77 (14) |
O1—C1—C6 | 104.38 (12) | C9—C10—C11 | 121.96 (13) |
C8—C1—C6 | 114.91 (14) | C13—C10—C11 | 88.25 (12) |
O1—C1—C2 | 109.48 (13) | C9—C10—H10 | 108.0 |
C8—C1—C2 | 111.58 (14) | C13—C10—H10 | 108.0 |
C6—C1—C2 | 109.49 (14) | C11—C10—H10 | 108.0 |
C1—C2—C3 | 110.99 (14) | C12—C11—C10 | 88.57 (13) |
C1—C2—H2A | 109.4 | C12—C11—H11A | 113.9 |
C3—C2—H2A | 109.4 | C10—C11—H11A | 113.9 |
C1—C2—H2B | 109.4 | C12—C11—H11B | 113.9 |
C3—C2—H2B | 109.4 | C10—C11—H11B | 113.9 |
H2A—C2—H2B | 108.0 | H11A—C11—H11B | 111.1 |
C2—C3—C4 | 114.51 (15) | C11—C12—C13 | 88.66 (13) |
C2—C3—H3A | 108.6 | C11—C12—H12A | 113.9 |
C4—C3—H3A | 108.6 | C13—C12—H12A | 113.9 |
C2—C3—H3B | 108.6 | C11—C12—H12B | 113.9 |
C4—C3—H3B | 108.6 | C13—C12—H12B | 113.9 |
H3A—C3—H3B | 107.6 | H12A—C12—H12B | 111.1 |
C3—C4—C5 | 113.42 (14) | C12—C13—C10 | 88.55 (12) |
C3—C4—H4A | 108.9 | C12—C13—H13A | 113.9 |
C5—C4—H4A | 108.9 | C10—C13—H13A | 113.9 |
C3—C4—H4B | 108.9 | C12—C13—H13B | 113.9 |
C5—C4—H4B | 108.9 | C10—C13—H13B | 113.9 |
H4A—C4—H4B | 107.7 | H13A—C13—H13B | 111.1 |
C7—C5—C6 | 112.72 (14) | C9—C14—C17 | 123.64 (13) |
C7—C5—C4 | 110.09 (14) | C9—C14—C15 | 120.77 (13) |
C6—C5—C4 | 106.73 (13) | C17—C14—C15 | 87.09 (13) |
C7—C5—C9 | 111.74 (13) | C9—C14—H14 | 107.8 |
C6—C5—C9 | 101.15 (12) | C17—C14—H14 | 107.8 |
C4—C5—C9 | 114.07 (13) | C15—C14—H14 | 107.8 |
C5—C6—C1 | 99.49 (13) | C16—C15—C14 | 87.98 (13) |
C5—C6—H6A | 111.9 | C16—C15—H15A | 114.0 |
C1—C6—H6A | 111.9 | C14—C15—H15A | 114.0 |
C5—C6—H6B | 111.9 | C16—C15—H15B | 114.0 |
C1—C6—H6B | 111.9 | C14—C15—H15B | 114.0 |
H6A—C6—H6B | 109.6 | H15A—C15—H15B | 111.2 |
O3—C7—O4 | 123.40 (15) | C15—C16—C17 | 88.18 (13) |
O3—C7—C5 | 123.5 (2) | C15—C16—H16A | 114.0 |
O4—C7—C5 | 113.1 (1) | C17—C16—H16A | 114.0 |
O2—C8—C1 | 111.04 (15) | C15—C16—H16B | 114.0 |
O2—C8—H8A | 109.4 | C17—C16—H16B | 114.0 |
C1—C8—H8A | 109.4 | H16A—C16—H16B | 111.2 |
O2—C8—H8B | 109.4 | C16—C17—C14 | 87.86 (13) |
C1—C8—H8B | 109.4 | C16—C17—H17A | 114.0 |
H8A—C8—H8B | 108.0 | C14—C17—H17A | 114.0 |
O1—C9—C10 | 107.66 (12) | C16—C17—H17B | 114.0 |
O1—C9—C14 | 109.81 (12) | C14—C17—H17B | 114.0 |
C10—C9—C14 | 110.57 (13) | H17A—C17—H17B | 111.2 |
C9—O1—C1—C8 | −140.50 (13) | C4—C5—C9—O1 | −78.74 (15) |
C9—O1—C1—C6 | −18.48 (16) | C7—C5—C9—C10 | −88.47 (16) |
C9—O1—C1—C2 | 98.66 (14) | C6—C5—C9—C10 | 151.37 (13) |
O1—C1—C2—C3 | −55.16 (18) | C4—C5—C9—C10 | 37.20 (18) |
C8—C1—C2—C3 | −172.94 (14) | C7—C5—C9—C14 | 38.14 (18) |
C6—C1—C2—C3 | 58.71 (18) | C6—C5—C9—C14 | −82.02 (15) |
C1—C2—C3—C4 | −36.8 (2) | C4—C5—C9—C14 | 163.82 (13) |
C2—C3—C4—C5 | 37.1 (2) | C14—C9—C10—C13 | 72.33 (17) |
C3—C4—C5—C7 | −179.77 (15) | C5—C9—C10—C13 | −160.35 (14) |
C3—C4—C5—C6 | −57.12 (18) | O1—C9—C10—C11 | −156.9 (1) |
C3—C4—C5—C9 | 53.70 (19) | O1—C9—C10—C13 | −47.6 (2) |
C7—C5—C6—C1 | −165.16 (13) | C14—C9—C10—C11 | −36.9 (2) |
C4—C5—C6—C1 | 73.85 (15) | C5—C9—C10—C11 | 90.41 (18) |
C9—C5—C6—C1 | −45.70 (15) | C9—C10—C11—C12 | 144.09 (15) |
O1—C1—C6—C5 | 40.14 (15) | C13—C10—C11—C12 | 18.3 (1) |
C8—C1—C6—C5 | 156.54 (14) | C10—C11—C12—C13 | −18.4 (1) |
C2—C1—C6—C5 | −76.98 (15) | C11—C12—C13—C10 | 18.4 (1) |
C6—C5—C7—O3 | 0.0 (2) | C11—C10—C13—C12 | −18.3 (1) |
C4—C5—C7—O3 | 119.07 (19) | C9—C10—C13—C12 | −145.03 (15) |
C9—C5—C7—O3 | −113.10 (19) | C10—C9—C14—C17 | −167.78 (15) |
C6—C5—C7—O4 | −179.78 (14) | C5—C9—C14—C17 | 63.66 (19) |
C4—C5—C7—O4 | −60.73 (18) | C10—C9—C14—C15 | −58.81 (18) |
C9—C5—C7—O4 | 67.10 (18) | C5—C9—C14—C15 | 172.63 (13) |
O1—C1—C8—O2 | −179.8 (1) | C9—C14—C15—C16 | −150.16 (15) |
C6—C1—C8—O2 | 65.11 (18) | O1—C9—C14—C15 | 59.9 (2) |
C2—C1—C8—O2 | −60.28 (18) | O1—C9—C14—C17 | −49.1 (2) |
C1—O1—C9—C10 | −131.20 (13) | C17—C14—C15—C16 | −22.2 (1) |
C1—O1—C9—C14 | 108.37 (14) | C14—C15—C16—C17 | 22.4 (1) |
C1—O1—C9—C5 | −10.59 (15) | C15—C16—C17—C14 | −22.4 (1) |
C7—C5—C9—O1 | 155.58 (13) | C15—C14—C17—C16 | 22.2 (1) |
C6—C5—C9—O1 | 35.42 (14) | C9—C14—C17—C16 | 147.70 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3i | 0.84 | 1.96 | 2.718 (2) | 149 |
O4—H4···O2ii | 0.84 | 1.78 | 2.585 (2) | 159 |
Symmetry codes: (i) −x+1, −y, −z; (ii) x−1, y+1, z. |
C13H20O4 | F(000) = 520 |
Mr = 240.29 | Dx = 1.325 Mg m−3 |
Monoclinic, P21/c | Melting point = 426–427 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 10.850 (3) Å | Cell parameters from 2589 reflections |
b = 7.050 (2) Å | θ = 1.9–27.0° |
c = 15.790 (5) Å | µ = 0.10 mm−1 |
β = 94.207 (10)° | T = 170 K |
V = 1204.6 (6) Å3 | Sphere, colourless |
Z = 4 | 0.50 × 0.50 × 0.45 × 0.48 (radius) mm |
Nonius KappaCCD diffractometer | 2377 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Horizontally mounted graphite crystal monochromator | θmax = 27.0°, θmin = 1.9° |
Detector resolution: 9 pixels mm-1 | h = 0→13 |
ϕ and ω scans | k = 0→8 |
2589 measured reflections | l = −20→20 |
2589 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.154 | w = 1/[σ2(Fo2) + (0.111P)2 + 0.2862P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2589 reflections | Δρmax = 0.40 e Å−3 |
169 parameters | Δρmin = −0.31 e Å−3 |
4 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.20 (2) |
C13H20O4 | V = 1204.6 (6) Å3 |
Mr = 240.29 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.850 (3) Å | µ = 0.10 mm−1 |
b = 7.050 (2) Å | T = 170 K |
c = 15.790 (5) Å | 0.50 × 0.50 × 0.45 × 0.48 (radius) mm |
β = 94.207 (10)° |
Nonius KappaCCD diffractometer | 2377 reflections with I > 2σ(I) |
2589 measured reflections | Rint = 0.000 |
2589 independent reflections |
R[F2 > 2σ(F2)] = 0.049 | 4 restraints |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.40 e Å−3 |
2589 reflections | Δρmin = −0.31 e Å−3 |
169 parameters |
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 | Occ. (<1) | |
O1 | 0.13635 (8) | 0.30263 (13) | 0.21188 (5) | 0.0167 (3) | |
O2 | −0.03979 (10) | 0.60592 (14) | 0.15469 (7) | 0.0257 (3) | |
H2 | −0.0746 | 0.6534 | 0.1955 | 0.031* | |
O4 | 0.34127 (10) | 0.53952 (16) | 0.00803 (7) | 0.0319 (3) | |
H4 | 0.4068 | 0.5750 | −0.0124 | 0.038* | 0.59 (3) |
O3 | 0.46810 (10) | 0.31811 (17) | 0.06462 (8) | 0.0354 (3) | |
H3 | 0.5168 | 0.3722 | 0.0334 | 0.042* | 0.41 (3) |
C1 | 0.05326 (11) | 0.29888 (17) | 0.13460 (8) | 0.0153 (3) | |
C2 | 0.02615 (12) | 0.09101 (18) | 0.11289 (8) | 0.0202 (3) | |
H2A | −0.0216 | 0.0829 | 0.0571 | 0.024* | |
H2B | −0.0245 | 0.0350 | 0.1562 | 0.024* | |
C3 | 0.14693 (13) | −0.02116 (19) | 0.10985 (9) | 0.0221 (3) | |
H3A | 0.1294 | −0.1404 | 0.0781 | 0.027* | |
H3B | 0.1770 | −0.0557 | 0.1685 | 0.027* | |
C4 | 0.25003 (12) | 0.08583 (19) | 0.06831 (9) | 0.0210 (3) | |
H4A | 0.2363 | 0.0749 | 0.0058 | 0.025* | |
H4B | 0.3304 | 0.0257 | 0.0856 | 0.025* | |
C5 | 0.25576 (11) | 0.29843 (18) | 0.09305 (8) | 0.0164 (3) | |
C6 | 0.12997 (11) | 0.38679 (17) | 0.06746 (8) | 0.0159 (3) | |
H6A | 0.1323 | 0.5269 | 0.0717 | 0.019* | |
H6B | 0.0991 | 0.3492 | 0.0093 | 0.019* | |
C7 | 0.36254 (12) | 0.39101 (19) | 0.05278 (8) | 0.0191 (3) | |
C8 | −0.06329 (12) | 0.40772 (18) | 0.15102 (8) | 0.0190 (3) | |
H8A | −0.1280 | 0.3809 | 0.1051 | 0.023* | |
H8B | −0.0941 | 0.3652 | 0.2054 | 0.023* | |
C9 | 0.26348 (11) | 0.33108 (18) | 0.19093 (8) | 0.0166 (3) | |
C10 | 0.34971 (13) | 0.2026 (2) | 0.24727 (9) | 0.0240 (4) | |
H10A | 0.4190 | 0.1569 | 0.2152 | 0.029* | 0.58 (2) |
H10B | 0.3039 | 0.0915 | 0.2669 | 0.029* | 0.58 (2) |
H10C | 0.3135 | 0.0746 | 0.2524 | 0.029* | 0.42 (2) |
H10D | 0.4314 | 0.1906 | 0.2236 | 0.029* | 0.42 (2) |
C11A | 0.3987 (8) | 0.3238 (7) | 0.3234 (4) | 0.0363 (14) | 0.58 (2) |
H11A | 0.3857 | 0.2583 | 0.3774 | 0.044* | 0.58 (2) |
H11B | 0.4881 | 0.3491 | 0.3208 | 0.044* | 0.58 (2) |
C11B | 0.3616 (11) | 0.3029 (7) | 0.3336 (3) | 0.039 (2) | 0.42 (2) |
H11C | 0.3062 | 0.2437 | 0.3731 | 0.046* | 0.42 (2) |
H11D | 0.4477 | 0.2952 | 0.3590 | 0.046* | 0.42 (2) |
C12 | 0.32478 (14) | 0.5097 (2) | 0.31658 (10) | 0.0301 (4) | |
H12A | 0.2463 | 0.4989 | 0.3444 | 0.036* | 0.58 (2) |
H12B | 0.3734 | 0.6172 | 0.3418 | 0.036* | 0.58 (2) |
H12C | 0.2490 | 0.5410 | 0.3450 | 0.036* | 0.42 (2) |
H12D | 0.3918 | 0.5958 | 0.3385 | 0.036* | 0.42 (2) |
C13 | 0.30171 (13) | 0.5316 (2) | 0.22038 (9) | 0.0233 (3) | |
H13A | 0.3776 | 0.5729 | 0.1944 | 0.028* | |
H13B | 0.2349 | 0.6242 | 0.2059 | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0141 (5) | 0.0224 (5) | 0.0139 (5) | −0.0020 (3) | 0.0023 (3) | 0.0016 (3) |
O2 | 0.0316 (6) | 0.0197 (5) | 0.0276 (6) | 0.0021 (4) | 0.0138 (4) | −0.0031 (4) |
O4 | 0.0238 (6) | 0.0341 (6) | 0.0387 (7) | 0.0003 (4) | 0.0094 (5) | 0.0193 (5) |
O3 | 0.0179 (5) | 0.0423 (7) | 0.0474 (7) | 0.0055 (4) | 0.0126 (5) | 0.0194 (5) |
C1 | 0.0154 (6) | 0.0179 (6) | 0.0128 (6) | −0.0009 (4) | 0.0013 (4) | 0.0003 (4) |
C2 | 0.0210 (7) | 0.0185 (7) | 0.0214 (7) | −0.0031 (5) | 0.0037 (5) | −0.0020 (5) |
C3 | 0.0250 (7) | 0.0159 (6) | 0.0261 (7) | 0.0001 (5) | 0.0059 (5) | −0.0006 (5) |
C4 | 0.0225 (7) | 0.0191 (7) | 0.0220 (7) | 0.0038 (5) | 0.0069 (5) | −0.0002 (5) |
C5 | 0.0148 (6) | 0.0188 (6) | 0.0160 (6) | 0.0014 (4) | 0.0037 (5) | 0.0030 (4) |
C6 | 0.0159 (6) | 0.0175 (6) | 0.0147 (6) | 0.0012 (4) | 0.0038 (5) | 0.0022 (4) |
C7 | 0.0174 (6) | 0.0227 (7) | 0.0176 (6) | 0.0013 (5) | 0.0046 (5) | 0.0033 (5) |
C8 | 0.0172 (6) | 0.0203 (7) | 0.0198 (6) | 0.0002 (5) | 0.0043 (5) | −0.0005 (5) |
C9 | 0.0142 (6) | 0.0198 (7) | 0.0160 (6) | −0.0011 (4) | 0.0037 (5) | 0.0022 (4) |
C10 | 0.0192 (7) | 0.0312 (8) | 0.0214 (7) | 0.0042 (5) | 0.0001 (5) | 0.0053 (5) |
C11A | 0.040 (3) | 0.041 (2) | 0.0254 (19) | 0.0053 (17) | −0.0117 (19) | 0.0020 (15) |
C11B | 0.032 (4) | 0.062 (4) | 0.021 (2) | 0.003 (2) | −0.005 (2) | 0.002 (2) |
C12 | 0.0248 (8) | 0.0409 (9) | 0.0243 (8) | −0.0052 (6) | −0.0003 (6) | −0.0076 (6) |
C13 | 0.0216 (7) | 0.0244 (7) | 0.0238 (7) | −0.0058 (5) | 0.0012 (5) | −0.0017 (5) |
O1—C9 | 1.4558 (14) | C6—H6B | 0.9900 |
O1—C1 | 1.4632 (14) | C8—H8A | 0.9900 |
O2—C8 | 1.4208 (17) | C8—H8B | 0.9900 |
O2—H2 | 0.8400 | C9—C13 | 1.5355 (19) |
O4—H4 | 0.8400 | C9—C10 | 1.5377 (18) |
O3—C7 | 1.257 (2) | C10—C11B | 1.533 (4) |
O4—C7 | 1.275 (2) | C10—C11A | 1.537 (4) |
O3—H3 | 0.8400 | C10—H10A | 0.9900 |
C1—C8 | 1.5176 (17) | C10—H10B | 0.9900 |
C1—C6 | 1.5265 (17) | C10—H10C | 0.9900 |
C1—C2 | 1.5287 (18) | C10—H10D | 0.9900 |
C2—C3 | 1.5344 (19) | C11A—C12 | 1.536 (4) |
C2—H2A | 0.9900 | C11A—H11A | 0.9900 |
C2—H2B | 0.9900 | C11A—H11B | 0.9900 |
C3—C4 | 1.5356 (19) | C11B—C12 | 1.530 (5) |
C3—H3A | 0.9900 | C11B—H11C | 0.9900 |
C3—H3B | 0.9900 | C11B—H11D | 0.9900 |
C4—C5 | 1.5491 (19) | C12—C13 | 1.529 (2) |
C4—H4A | 0.9900 | C12—H12A | 0.9900 |
C4—H4B | 0.9900 | C12—H12B | 0.9900 |
C5—C7 | 1.5102 (17) | C12—H12C | 0.9900 |
C5—C6 | 1.5275 (17) | C12—H12D | 0.9900 |
C5—C9 | 1.5588 (17) | C13—H13A | 0.9900 |
C6—H6A | 0.9900 | C13—H13B | 0.9900 |
C9—O1—C1 | 110.43 (9) | C13—C9—C5 | 115.46 (10) |
C8—O2—H2 | 109.5 | C10—C9—C5 | 118.22 (11) |
C7—O4—H4 | 109.5 | C11B—C10—C9 | 104.5 (3) |
C7—O3—H3 | 109.5 | C9—C10—C11A | 106.60 (17) |
O1—C1—C8 | 108.57 (10) | C11B—C10—H10A | 126.0 |
O1—C1—C6 | 103.76 (10) | C9—C10—H10A | 110.4 |
C8—C1—C6 | 114.64 (10) | C11A—C10—H10A | 110.4 |
O1—C1—C2 | 107.52 (10) | C9—C10—H10B | 110.4 |
C8—C1—C2 | 111.96 (10) | C11A—C10—H10B | 110.4 |
C6—C1—C2 | 109.83 (10) | H10A—C10—H10B | 108.6 |
C1—C2—C3 | 110.51 (10) | C11B—C10—H10C | 110.8 |
C1—C2—H2A | 109.5 | C9—C10—H10C | 110.8 |
C3—C2—H2A | 109.5 | H10A—C10—H10C | 93.7 |
C1—C2—H2B | 109.5 | C11B—C10—H10D | 110.8 |
C3—C2—H2B | 109.5 | C9—C10—H10D | 110.8 |
H2A—C2—H2B | 108.1 | H10B—C10—H10D | 122.3 |
C2—C3—C4 | 114.26 (11) | H10C—C10—H10D | 108.9 |
C2—C3—H3A | 108.7 | C12—C11A—C10 | 105.7 (2) |
C4—C3—H3A | 108.7 | C12—C11A—H11A | 110.6 |
C2—C3—H3B | 108.7 | C10—C11A—H11A | 110.6 |
C4—C3—H3B | 108.7 | C12—C11A—H11B | 110.6 |
H3A—C3—H3B | 107.6 | C10—C11A—H11B | 110.6 |
C3—C4—C5 | 112.61 (10) | H11A—C11A—H11B | 108.7 |
C3—C4—H4A | 109.1 | C12—C11B—C10 | 106.2 (3) |
C5—C4—H4A | 109.1 | C12—C11B—H11C | 110.5 |
C3—C4—H4B | 109.1 | C10—C11B—H11C | 110.5 |
C5—C4—H4B | 109.1 | C12—C11B—H11D | 110.5 |
H4A—C4—H4B | 107.8 | C10—C11B—H11D | 110.5 |
C7—C5—C6 | 114.24 (10) | H11C—C11B—H11D | 108.7 |
C7—C5—C4 | 109.25 (10) | C13—C12—C11B | 107.0 (2) |
C6—C5—C4 | 108.02 (10) | C13—C12—C11A | 101.6 (3) |
C7—C5—C9 | 111.51 (10) | C13—C12—H12A | 111.4 |
C6—C5—C9 | 100.61 (9) | C11B—C12—H12A | 94.1 |
C4—C5—C9 | 113.03 (10) | C11A—C12—H12A | 111.4 |
C1—C6—C5 | 99.95 (10) | C13—C12—H12B | 111.4 |
C1—C6—H6A | 111.8 | C11B—C12—H12B | 122.3 |
C5—C6—H6A | 111.8 | C11A—C12—H12B | 111.4 |
C1—C6—H6B | 111.8 | H12A—C12—H12B | 109.3 |
C5—C6—H6B | 111.8 | C13—C12—H12C | 110.3 |
H6A—C6—H6B | 109.5 | C11B—C12—H12C | 110.3 |
O3—C7—O4 | 122.98 (12) | C11A—C12—H12C | 127.2 |
O3—C7—C5 | 118.7 (1) | H12B—C12—H12C | 94.7 |
O4—C7—C5 | 118.4 (1) | C13—C12—H12D | 110.3 |
O2—C8—C1 | 110.79 (10) | C11B—C12—H12D | 110.3 |
O2—C8—H8A | 109.5 | C11A—C12—H12D | 97.6 |
C1—C8—H8A | 109.5 | H12A—C12—H12D | 121.7 |
O2—C8—H8B | 109.5 | H12C—C12—H12D | 108.6 |
C1—C8—H8B | 109.5 | C12—C13—C9 | 103.23 (11) |
H8A—C8—H8B | 108.1 | C12—C13—H13A | 111.1 |
O1—C9—C13 | 107.30 (10) | C9—C13—H13A | 111.1 |
O1—C9—C10 | 109.51 (10) | C12—C13—H13B | 111.1 |
C13—C9—C10 | 103.15 (11) | C9—C13—H13B | 111.1 |
O1—C9—C5 | 102.83 (9) | H13A—C13—H13B | 109.1 |
C9—O1—C1—C8 | −139.28 (10) | C7—C5—C9—O1 | 158.29 (10) |
C9—O1—C1—C6 | −16.93 (12) | C6—C5—C9—O1 | 36.77 (11) |
C9—O1—C1—C2 | 99.40 (11) | C4—C5—C9—O1 | −78.17 (12) |
O1—C1—C2—C3 | −52.37 (13) | C7—C5—C9—C13 | 41.78 (14) |
C8—C1—C2—C3 | −171.54 (10) | C6—C5—C9—C13 | −79.74 (12) |
C6—C1—C2—C3 | 59.91 (13) | C4—C5—C9—C13 | 165.33 (11) |
C1—C2—C3—C4 | −40.09 (15) | C7—C5—C9—C10 | −81.00 (14) |
C2—C3—C4—C5 | 39.86 (16) | C6—C5—C9—C10 | 157.49 (11) |
C3—C4—C5—C7 | 177.59 (11) | C4—C5—C9—C10 | 42.55 (15) |
C3—C4—C5—C6 | −57.59 (14) | O1—C9—C10—C11A | −95.2 (4) |
C3—C4—C5—C9 | 52.81 (15) | O1—C9—C10—C11B | −77.2 (5) |
O1—C1—C6—C5 | 39.50 (11) | C13—C9—C10—C11A | 18.8 (5) |
C8—C1—C6—C5 | 157.73 (10) | C9—C10—C11A—C12 | 8.4 (7) |
C2—C1—C6—C5 | −75.20 (12) | C10—C11A—C12—C13 | −32.3 (6) |
C7—C5—C6—C1 | −165.93 (11) | C11A—C12—C13—C9 | 44.3 (4) |
C4—C5—C6—C1 | 72.29 (12) | C10—C9—C13—C12 | −39.2 (1) |
C9—C5—C6—C1 | −46.36 (11) | C13—C9—C10—C11B | 36.9 (5) |
C6—C5—C7—O3 | −174.24 (12) | C9—C10—C11B—C12 | −20.1 (8) |
C4—C5—C7—O3 | −53.13 (17) | C10—C11B—C12—C13 | −4.3 (8) |
C9—C5—C7—O3 | 72.53 (16) | C11B—C12—C13—C9 | 27.0 (5) |
C6—C5—C7—O4 | 5.56 (18) | C5—C9—C10—C11B | 165.6 (5) |
C4—C5—C7—O4 | 126.66 (13) | C5—C9—C10—C11A | 147.5 (4) |
C9—C5—C7—O4 | −107.67 (14) | C11B—C10—C11A—C12 | −77.3 (9) |
O1—C1—C8—O2 | 72.76 (12) | C11A—C10—C11B—C12 | 79.0 (9) |
C6—C1—C8—O2 | −42.72 (14) | C10—C11B—C12—C11A | −78.8 (9) |
C2—C1—C8—O2 | −168.69 (10) | C10—C11A—C12—C11B | 77.5 (9) |
C1—O1—C9—C13 | 109.70 (11) | O1—C9—C13—C12 | 76.38 (12) |
C1—O1—C9—C10 | −139.01 (10) | C5—C9—C13—C12 | −169.68 (11) |
C1—O1—C9—C5 | −12.49 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.84 | 1.96 | 2.790 (1) | 170 |
O3—H3···O4ii | 0.84 | 1.83 | 2.636 (2) | 162 |
O4—H4···O3ii | 0.84 | 1.80 | 2.636 (2) | 171 |
C12—H12D···O3iii | 0.99 | 2.60 | 3.561 (2) | 163 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z; (iii) −x+1, y+1/2, −z+1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C17H26O4 | C13H20O4 |
Mr | 294.38 | 240.29 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 170 | 170 |
a, b, c (Å) | 8.757 (3), 8.807 (3), 11.769 (6) | 10.850 (3), 7.050 (2), 15.790 (5) |
α, β, γ (°) | 84.073 (11), 75.766 (13), 61.044 (9) | 90, 94.207 (10), 90 |
V (Å3) | 769.7 (5) | 1204.6 (6) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.10 |
Crystal size (mm) | 0.45 × 0.10 × 0.10 | 0.50 × 0.50 × 0.45 × 0.48 (radius) |
Data collection | ||
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3531, 3531, 3087 | 2589, 2589, 2377 |
Rint | 0.000 | 0.000 |
(sin θ/λ)max (Å−1) | 0.650 | 0.639 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.176, 1.03 | 0.049, 0.154, 1.05 |
No. of reflections | 3531 | 2589 |
No. of parameters | 191 | 169 |
No. of restraints | 0 | 4 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.46 | 0.40, −0.31 |
Computer programs: KappaCCD Server Software (Nonius, 2000), HKL DENZO and SCALEPACK (Otwinowski & Minor 1997), HKL DENZO and SCALEPACK, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), Xtal3.6 (Hall et al., 1999) and PLATON (Spek, 2003), SHELXL97, WinGX (Farrugia, 1999) and PLATON.
O3—C7 | 1.209 (2) | O4—C7 | 1.318 (2) |
O3—C7—C5 | 123.5 (2) | O4—C7—C5 | 113.1 (1) |
O1—C1—C8—O2 | −179.8 (1) | O1—C9—C14—C15 | 59.9 (2) |
O1—C9—C10—C11 | −156.9 (1) | O1—C9—C14—C17 | −49.1 (2) |
O1—C9—C10—C13 | −47.6 (2) | C17—C14—C15—C16 | −22.2 (1) |
C13—C10—C11—C12 | 18.3 (1) | C14—C15—C16—C17 | 22.4 (1) |
C10—C11—C12—C13 | −18.4 (1) | C15—C16—C17—C14 | −22.4 (1) |
C11—C12—C13—C10 | 18.4 (1) | C15—C14—C17—C16 | 22.2 (1) |
C11—C10—C13—C12 | −18.3 (1) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3i | 0.84 | 1.96 | 2.718 (2) | 149 |
O4—H4···O2ii | 0.84 | 1.78 | 2.585 (2) | 159 |
Symmetry codes: (i) −x+1, −y, −z; (ii) x−1, y+1, z. |
O3—C7 | 1.257 (2) | O4—C7 | 1.275 (2) |
O3—C7—C5 | 118.7 (1) | O4—C7—C5 | 118.4 (1) |
O1—C1—C8—O2 | 72.76 (12) | C11A—C12—C13—C9 | 44.3 (4) |
O1—C9—C10—C11A | −95.2 (4) | C10—C9—C13—C12 | −39.2 (1) |
O1—C9—C10—C11B | −77.2 (5) | C13—C9—C10—C11B | 36.9 (5) |
C13—C9—C10—C11A | 18.8 (5) | C9—C10—C11B—C12 | −20.1 (8) |
C9—C10—C11A—C12 | 8.4 (7) | C10—C11B—C12—C13 | −4.3 (8) |
C10—C11A—C12—C13 | −32.3 (6) | C11B—C12—C13—C9 | 27.0 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.84 | 1.96 | 2.790 (1) | 170 |
O3—H3···O4ii | 0.84 | 1.83 | 2.636 (2) | 162 |
O4—H4···O3ii | 0.84 | 1.80 | 2.636 (2) | 171 |
C12—H12D···O3iii | 0.99 | 2.60 | 3.561 (2) | 163 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z; (iii) −x+1, y+1/2, −z+1/2. |
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We have reported that compounds possessing axially oriented hydroxyl/carboxylic acid functions might create, by incorporation of water molecules, three-dimensional tubular structures in the crystalline state. Compounds (I) and (II) were considered to be promising candidates, since their respective homologues, (III) and (IV), have been shown to adopt hydrated tubular structures in the solid state (Carrasco et al., 2001). The crystal structures of compounds (I) and (II), reported in this paper, reveal a lack of hydration water molecules, although they were crystallized in a water-saturated atmosphere. To date, compound (IV) is the only one of this series which crystallizes in the anhydrous and hydrated forms in the absence or presence of water atmosphere, respectively.
The molecular structures of compounds (I) and (II) are displayed in Figs. 1 and 2, respectively. In (I), the cyclobutane rings are puckered (Table 1), with dihedral angles of 26.1 (2) (C13/C10/C11 and C11/C12/C13 planes) and 31.7 (1)° (C15/C14/C17 and C15/C16/C17 planes). The oxolane ring, in both compounds, presents a distorted 4T5 half-chair toward an E5 envelope conformation, according to the puckering parameters (Cremer & Pople, 1975) and the notation of Giacovazzo et al. (1992) for the C1/O1/C9/C5/C6 sequence [ϕ2 = −50.1 (2) and −51.7 (1)°]. The cyclohexane presents a distorted 1C4 towards 1E conformation [C6/C1/C2/C3/C4/C5; ϕ = 0.4 (3) and 1.8 (3)°, and θ = 27.0 (3) and 23.8 (1)°].
The molecules of (II) exhibit positional disorder in the cyclopentane ring and in the carboxylic acid group (Fig. 2). The cyclopentane ring adopts two conformations, namely 5T4 and 5E for molecules A [ϕ2 = 133.3 (6)°], and between 5T1 and E1 for molecules B [ϕ2 = 173.9 (11)°], for the C9/C10/C11A/C11B/C12/C13 sequence. In the carboxylic acid group, the C—O distances and O—C—C angle are significantly different from those in (I) (Tables 1 and 3), although in good agreement with the values previously reported for the disordered group (Carrasco et al., 2001).
The O—H···O hydrogen-bonding motifs may be described as double-strand ladders in (I) and sheets in (II) (Figs. 3 and 4), which are closely related to the anti and gauche conformations of the hydroxyl group with respect to the oxolane bridge (Tables 1 and 3). As observed previously (Carrasco et al., 2001), the anti conformation gives one-dimensional assemblies, while a gauche conformation gives either one- or two-dimensional assemblies.
The supramolecular structure in (I) also differs from that in (II), in the absence of the centrosymmetric R22(8) motif (Tables 2 and 4). In (I), the carboxylic acid group acts as both a donor to the hydroxyl group, forming strands, and as an acceptor, joining two strands into a step-ladder structure (Nguyen et al., 2001) of alternating R22(16) and R44(12) motifs. Each strand (Fig. 3) contains only one enantiomer, related only by translation, whereas the step-ladder is formed by one strand of one handedness and one strand of opposite handedness, giving rise to an achiral ladder. A similar supramolecular structure is present in the anhydrous form of compound (IV) and in the homologues (V) and (VI) (Carrasco et al., 2001), which have two fewer C atoms. No other weak interactions, except van der Waals interactions, are observed between ladders (Fig. 5).
In compound (II), the H-atom disorder does not affect the supramolecular structure, since the carboxylic acid group interacts strongly with itself, forming the acid-to-acid hydrogen-bonding R22(8) motif (Leiserowitz, 1976; Etter, 1990; Bernstein et al., 1995). This dimeric association, linked by hydroxyl-to-ether hydrogen bonds, results in sheets (Fig. 4) that are further joined via C—H···O interactions into a three-dimensional network (Table 4 and dashed lines in Fig. 6). The formation of the R22(8) motif is prevented in the related analogues with two-dimensional structures (Carrasco et al., 2001).
Comparison with the previously reported hydroxy–acid analogues confirms that the relative positions of the hydroxyl and carboxylic acid groups, together with the molecular size, can lead to a range of hydrogen-bonded supramolecular structures with various dimensionalities. The reliability of the axially oriented hydroxyl/carboxylic acid functions in giving anhydrous layers reduces the design of the last remaining dimension to the incorporation of water molecules.