The title diketo acid, (1
R,3a
S,6a
S,7
R,9
S)-(−)-α,3a,7-trimethyl-5,8-dioxo-1,4-ethanoperhydropentalene-1-acetic acid (C
15H
20O
4), is shown to aggregate in the crystal structure as acid-to-ketone hydrogen-bonding catemers, whose chains follow 2
1 screw axes from each carboxyl to a ketone in a neighbouring molecule [O
O = 2.7472 (13) Å and O
H—O = 172.7 (17)°]. Two parallel counterdirectional screw-related single-strand hydrogen-bonding chains pass through the cell in the a direction. Six intermolecular C—H
O=C close contacts are found. Comparisons are drawn with a diastereomer having the opposite configuration at the methylated chiral centre adjacent to the carboxyl group.
Supporting information
CCDC reference: 611215
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.002 Å
- R factor = 0.025
- wR factor = 0.066
- Data-to-parameter ratio = 9.2
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT708_ALERT_1_A D-H..A Calc 172.8(17), Rep 1727(17), Dev.. 914.24 Sigma
O4 -H4 -O1 1.555 1.555 4.456
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97
PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.36 Ratio
PLAT480_ALERT_4_C Long H...A H-Bond Reported H11B .. O2 .. 2.65 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3A .. O3 .. 2.67 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6A .. O3 .. 2.65 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H9A .. O4 .. 2.67 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 1
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 69.24
From the CIF: _reflns_number_total 2321
Count of symmetry unique reflns 1451
Completeness (_total/calc) 159.96%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 870
Fraction of Friedel pairs measured 0.600
Are heavy atom types Z>Si present no
1 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
7 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
6 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
(1
R,3aS,6aS,7
R,9S)-(-)-
α,3a,7-trimethyl-5,8-dioxo-1,4-
ethanoperhydropentalene-1-acetic acid'
top
Crystal data top
C15H20O4 | Dx = 1.317 Mg m−3 |
Mr = 264.31 | Melting point: 424 K |
Orthorhombic, P212121 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 7889 reflections |
a = 8.3801 (2) Å | θ = 3.5–68.3° |
b = 12.5398 (2) Å | µ = 0.77 mm−1 |
c = 12.6852 (2) Å | T = 100 K |
V = 1333.02 (4) Å3 | Parallelepiped, colourless |
Z = 4 | 0.50 × 0.34 × 0.26 mm |
F(000) = 568 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2321 independent reflections |
Radiation source: fine-focus sealed tube | 2320 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
φ and ω scans | θmax = 69.2°, θmin = 5.0° |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | h = −10→7 |
Tmin = 0.750, Tmax = 0.820 | k = −14→14 |
15403 measured reflections | l = −14→14 |
Refinement top
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.025 | w = 1/[σ2(Fo2) + (0.0435P)2 + 0.3883P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.066 | (Δ/σ)max < 0.001 |
S = 0.98 | Δρmax = 0.21 e Å−3 |
2321 reflections | Δρmin = −0.16 e Å−3 |
253 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0065 (5) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), with 950 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.02 (15) |
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. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 1.14506 (11) | 0.39121 (7) | 0.70118 (7) | 0.0190 (2) | |
O2 | 0.95141 (14) | 0.17671 (8) | 0.91770 (8) | 0.0296 (3) | |
O3 | 0.73503 (11) | 0.34672 (7) | 0.40368 (7) | 0.0203 (2) | |
O4 | 0.84988 (12) | 0.19150 (7) | 0.44684 (7) | 0.0185 (2) | |
H4 | 0.782 (2) | 0.1709 (14) | 0.4018 (15) | 0.030 (5)* | |
C1 | 0.87342 (15) | 0.37129 (10) | 0.63724 (10) | 0.0152 (3) | |
C2 | 0.75242 (16) | 0.46516 (10) | 0.63621 (10) | 0.0172 (3) | |
H2A | 0.8074 (19) | 0.5350 (13) | 0.6420 (12) | 0.018 (4)* | |
H2B | 0.6986 (17) | 0.4610 (11) | 0.5717 (12) | 0.011 (3)* | |
C3 | 0.63359 (16) | 0.44360 (11) | 0.72692 (10) | 0.0192 (3) | |
H3A | 0.6419 (18) | 0.5026 (12) | 0.7797 (11) | 0.013 (3)* | |
H3B | 0.523 (2) | 0.4405 (13) | 0.7019 (13) | 0.022 (4)* | |
C3A | 0.67768 (16) | 0.33365 (11) | 0.77273 (9) | 0.0177 (3) | |
C4 | 0.80962 (16) | 0.33636 (11) | 0.85842 (10) | 0.0175 (3) | |
H4A | 0.7690 (18) | 0.3505 (12) | 0.9273 (13) | 0.015 (4)* | |
C5 | 0.88472 (16) | 0.22579 (10) | 0.84861 (10) | 0.0196 (3) | |
C6 | 0.86504 (18) | 0.18840 (11) | 0.73454 (10) | 0.0193 (3) | |
H6A | 0.967 (2) | 0.1755 (14) | 0.7049 (13) | 0.025 (4)* | |
H6B | 0.806 (2) | 0.1209 (13) | 0.7346 (13) | 0.022 (4)* | |
C6A | 0.77071 (16) | 0.27819 (10) | 0.68215 (10) | 0.0169 (3) | |
H6AA | 0.6968 (18) | 0.2542 (12) | 0.6247 (12) | 0.016 (4)* | |
C7 | 0.94270 (16) | 0.41824 (10) | 0.83122 (10) | 0.0177 (3) | |
H7A | 0.892 (2) | 0.4885 (14) | 0.8272 (12) | 0.023 (4)* | |
C8 | 1.00268 (15) | 0.39464 (9) | 0.72008 (10) | 0.0148 (3) | |
C9 | 0.95204 (15) | 0.34666 (10) | 0.52941 (9) | 0.0149 (3) | |
H9A | 1.0327 (18) | 0.2935 (12) | 0.5410 (11) | 0.011 (3)* | |
C10 | 0.83327 (15) | 0.29750 (10) | 0.45385 (9) | 0.0151 (3) | |
C11 | 1.02581 (16) | 0.44569 (11) | 0.47779 (10) | 0.0171 (3) | |
H11A | 1.0710 (18) | 0.4254 (12) | 0.4100 (13) | 0.017 (4)* | |
H11B | 1.108 (2) | 0.4776 (13) | 0.5243 (13) | 0.019 (4)* | |
H11C | 0.944 (2) | 0.4979 (13) | 0.4623 (12) | 0.021 (4)* | |
C12 | 1.07672 (17) | 0.42128 (11) | 0.91236 (11) | 0.0212 (3) | |
H12A | 1.132 (2) | 0.3529 (15) | 0.9161 (14) | 0.030 (4)* | |
H12B | 1.034 (2) | 0.4399 (15) | 0.9830 (16) | 0.037 (5)* | |
H12C | 1.154 (2) | 0.4738 (15) | 0.8949 (14) | 0.029 (4)* | |
C13 | 0.53463 (18) | 0.26979 (12) | 0.81207 (10) | 0.0236 (3) | |
H13A | 0.481 (2) | 0.3067 (15) | 0.8684 (15) | 0.031 (5)* | |
H13B | 0.566 (2) | 0.1979 (16) | 0.8382 (15) | 0.035 (5)* | |
H13C | 0.457 (2) | 0.2576 (13) | 0.7560 (14) | 0.023 (4)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0169 (5) | 0.0213 (5) | 0.0188 (5) | 0.0004 (4) | −0.0009 (4) | −0.0032 (4) |
O2 | 0.0450 (6) | 0.0225 (5) | 0.0214 (5) | 0.0026 (5) | −0.0066 (5) | 0.0042 (4) |
O3 | 0.0203 (5) | 0.0210 (5) | 0.0196 (5) | −0.0004 (4) | −0.0045 (4) | 0.0019 (4) |
O4 | 0.0185 (5) | 0.0184 (5) | 0.0186 (4) | 0.0003 (4) | −0.0018 (4) | −0.0036 (4) |
C1 | 0.0176 (6) | 0.0141 (6) | 0.0141 (6) | −0.0003 (5) | −0.0013 (5) | −0.0002 (5) |
C2 | 0.0183 (7) | 0.0182 (6) | 0.0151 (6) | 0.0022 (6) | −0.0012 (5) | −0.0005 (5) |
C3 | 0.0171 (7) | 0.0240 (7) | 0.0166 (6) | 0.0035 (5) | 0.0008 (5) | −0.0031 (5) |
C3A | 0.0179 (6) | 0.0214 (7) | 0.0138 (6) | 0.0005 (5) | 0.0007 (5) | −0.0029 (5) |
C4 | 0.0213 (7) | 0.0199 (7) | 0.0113 (6) | −0.0003 (5) | 0.0008 (5) | −0.0009 (5) |
C5 | 0.0221 (7) | 0.0190 (7) | 0.0177 (6) | −0.0031 (5) | 0.0008 (5) | 0.0025 (5) |
C6 | 0.0240 (7) | 0.0163 (7) | 0.0175 (6) | −0.0008 (6) | 0.0016 (5) | 0.0003 (5) |
C6A | 0.0188 (6) | 0.0184 (6) | 0.0134 (6) | −0.0022 (5) | 0.0003 (5) | −0.0017 (5) |
C7 | 0.0201 (6) | 0.0163 (6) | 0.0166 (6) | 0.0019 (6) | −0.0013 (5) | −0.0011 (5) |
C8 | 0.0186 (7) | 0.0093 (5) | 0.0166 (6) | 0.0014 (5) | −0.0015 (5) | 0.0002 (5) |
C9 | 0.0150 (6) | 0.0161 (6) | 0.0138 (6) | 0.0018 (5) | −0.0004 (5) | −0.0001 (4) |
C10 | 0.0157 (6) | 0.0169 (6) | 0.0126 (6) | −0.0007 (5) | 0.0039 (5) | 0.0012 (5) |
C11 | 0.0183 (6) | 0.0183 (6) | 0.0145 (6) | −0.0015 (6) | 0.0004 (5) | 0.0000 (5) |
C12 | 0.0227 (7) | 0.0244 (7) | 0.0165 (6) | −0.0008 (6) | −0.0028 (5) | −0.0017 (5) |
C13 | 0.0227 (7) | 0.0320 (8) | 0.0161 (6) | −0.0034 (6) | 0.0026 (6) | −0.0012 (6) |
Geometric parameters (Å, º) top
O1—C8 | 1.2178 (17) | C5—C6 | 1.5300 (18) |
O2—C5 | 1.2080 (17) | C6—C6A | 1.5279 (18) |
O3—C10 | 1.2098 (15) | C6—H6A | 0.945 (18) |
O4—C10 | 1.3394 (16) | C6—H6B | 0.981 (17) |
O4—H4 | 0.847 (19) | C6A—H6AA | 1.002 (15) |
C1—C8 | 1.5373 (17) | C7—C12 | 1.5239 (18) |
C1—C9 | 1.5493 (17) | C7—C8 | 1.5258 (17) |
C1—C2 | 1.5537 (17) | C7—H7A | 0.979 (18) |
C1—C6A | 1.5583 (17) | C9—C10 | 1.5131 (18) |
C2—C3 | 1.5456 (18) | C9—C11 | 1.5340 (17) |
C2—H2A | 0.992 (16) | C9—H9A | 0.960 (15) |
C2—H2B | 0.936 (15) | C11—H11A | 0.974 (17) |
C3—C3A | 1.5412 (19) | C11—H11B | 0.991 (17) |
C3—H3A | 1.001 (15) | C11—H11C | 0.968 (18) |
C3—H3B | 0.984 (18) | C12—H12A | 0.976 (19) |
C3A—C13 | 1.5256 (19) | C12—H12B | 0.99 (2) |
C3A—C4 | 1.5508 (18) | C12—H12C | 0.949 (19) |
C3A—C6A | 1.5530 (17) | C13—H13A | 0.962 (19) |
C4—C5 | 1.5278 (19) | C13—H13B | 0.996 (19) |
C4—C7 | 1.5547 (19) | C13—H13C | 0.977 (18) |
C4—H4A | 0.955 (16) | | |
| | | |
C10—O4—H4 | 106.1 (12) | C6—C6A—C1 | 115.18 (11) |
C8—C1—C9 | 109.99 (10) | C3A—C6A—C1 | 102.26 (10) |
C8—C1—C2 | 108.75 (10) | C6—C6A—H6AA | 114.5 (9) |
C9—C1—C2 | 114.91 (10) | C3A—C6A—H6AA | 111.2 (8) |
C8—C1—C6A | 106.38 (10) | C1—C6A—H6AA | 107.5 (9) |
C9—C1—C6A | 114.09 (10) | C12—C7—C8 | 112.72 (11) |
C2—C1—C6A | 102.13 (10) | C12—C7—C4 | 113.29 (11) |
C3—C2—C1 | 106.36 (10) | C8—C7—C4 | 108.25 (10) |
C3—C2—H2A | 113.5 (9) | C12—C7—H7A | 109.3 (10) |
C1—C2—H2A | 111.4 (9) | C8—C7—H7A | 105.6 (9) |
C3—C2—H2B | 109.3 (9) | C4—C7—H7A | 107.2 (10) |
C1—C2—H2B | 106.2 (9) | O1—C8—C7 | 120.77 (11) |
H2A—C2—H2B | 109.8 (13) | O1—C8—C1 | 123.30 (11) |
C3A—C3—C2 | 106.43 (10) | C7—C8—C1 | 115.88 (11) |
C3A—C3—H3A | 113.1 (8) | C10—C9—C11 | 108.94 (10) |
C2—C3—H3A | 108.9 (9) | C10—C9—C1 | 111.15 (10) |
C3A—C3—H3B | 108.2 (10) | C11—C9—C1 | 112.76 (10) |
C2—C3—H3B | 112.1 (10) | C10—C9—H9A | 106.1 (8) |
H3A—C3—H3B | 108.1 (13) | C11—C9—H9A | 110.1 (9) |
C13—C3A—C3 | 113.86 (11) | C1—C9—H9A | 107.6 (8) |
C13—C3A—C4 | 110.03 (10) | O3—C10—O4 | 122.82 (12) |
C3—C3A—C4 | 114.56 (11) | O3—C10—C9 | 124.96 (11) |
C13—C3A—C6A | 113.67 (11) | O4—C10—C9 | 112.21 (11) |
C3—C3A—C6A | 104.00 (10) | C9—C11—H11A | 108.8 (9) |
C4—C3A—C6A | 99.82 (10) | C9—C11—H11B | 110.7 (9) |
C5—C4—C3A | 102.51 (10) | H11A—C11—H11B | 111.2 (13) |
C5—C4—C7 | 106.61 (11) | C9—C11—H11C | 110.4 (9) |
C3A—C4—C7 | 111.74 (10) | H11A—C11—H11C | 105.8 (13) |
C5—C4—H4A | 113.0 (9) | H11B—C11—H11C | 109.9 (13) |
C3A—C4—H4A | 113.0 (9) | C7—C12—H12A | 111.1 (11) |
C7—C4—H4A | 109.7 (9) | C7—C12—H12B | 110.6 (11) |
O2—C5—C4 | 126.43 (12) | H12A—C12—H12B | 109.4 (15) |
O2—C5—C6 | 125.45 (12) | C7—C12—H12C | 111.1 (11) |
C4—C5—C6 | 108.10 (11) | H12A—C12—H12C | 107.4 (15) |
C6A—C6—C5 | 103.97 (10) | H12B—C12—H12C | 107.0 (16) |
C6A—C6—H6A | 114.8 (10) | C3A—C13—H13A | 110.8 (11) |
C5—C6—H6A | 109.3 (10) | C3A—C13—H13B | 112.0 (11) |
C6A—C6—H6B | 112.0 (10) | H13A—C13—H13B | 108.2 (15) |
C5—C6—H6B | 108.5 (10) | C3A—C13—H13C | 111.6 (10) |
H6A—C6—H6B | 107.9 (14) | H13A—C13—H13C | 107.9 (14) |
C6—C6A—C3A | 105.54 (10) | H13B—C13—H13C | 106.1 (15) |
| | | |
C8—C1—C2—C3 | −82.91 (12) | C2—C1—C6A—C6 | −156.31 (11) |
C9—C1—C2—C3 | 153.34 (11) | C8—C1—C6A—C3A | 71.52 (12) |
C6A—C1—C2—C3 | 29.27 (12) | C9—C1—C6A—C3A | −167.03 (10) |
C1—C2—C3—C3A | −4.83 (13) | C2—C1—C6A—C3A | −42.42 (12) |
C2—C3—C3A—C13 | −146.00 (11) | C5—C4—C7—C12 | −67.36 (13) |
C2—C3—C3A—C4 | 86.13 (13) | C3A—C4—C7—C12 | −178.61 (11) |
C2—C3—C3A—C6A | −21.76 (13) | C5—C4—C7—C8 | 58.42 (13) |
C13—C3A—C4—C5 | 77.39 (13) | C3A—C4—C7—C8 | −52.83 (14) |
C3—C3A—C4—C5 | −152.82 (11) | C12—C7—C8—O1 | −7.51 (17) |
C6A—C3A—C4—C5 | −42.40 (12) | C4—C7—C8—O1 | −133.63 (12) |
C13—C3A—C4—C7 | −168.80 (11) | C12—C7—C8—C1 | 169.96 (11) |
C3—C3A—C4—C7 | −39.01 (15) | C4—C7—C8—C1 | 43.85 (14) |
C6A—C3A—C4—C7 | 71.42 (12) | C9—C1—C8—O1 | −1.44 (16) |
C3A—C4—C5—O2 | −152.78 (14) | C2—C1—C8—O1 | −128.07 (13) |
C7—C4—C5—O2 | 89.69 (16) | C6A—C1—C8—O1 | 122.59 (13) |
C3A—C4—C5—C6 | 28.72 (13) | C9—C1—C8—C7 | −178.84 (10) |
C7—C4—C5—C6 | −88.81 (12) | C2—C1—C8—C7 | 54.52 (13) |
O2—C5—C6—C6A | 178.99 (14) | C6A—C1—C8—C7 | −54.81 (13) |
C4—C5—C6—C6A | −2.49 (14) | C8—C1—C9—C10 | 166.09 (10) |
C5—C6—C6A—C3A | −24.98 (13) | C2—C1—C9—C10 | −70.82 (13) |
C5—C6—C6A—C1 | 86.99 (12) | C6A—C1—C9—C10 | 46.66 (14) |
C13—C3A—C6A—C6 | −74.89 (13) | C8—C1—C9—C11 | −71.25 (13) |
C3—C3A—C6A—C6 | 160.75 (11) | C2—C1—C9—C11 | 51.84 (15) |
C4—C3A—C6A—C6 | 42.21 (12) | C6A—C1—C9—C11 | 169.32 (10) |
C13—C3A—C6A—C1 | 164.30 (11) | C11—C9—C10—O3 | −44.88 (16) |
C3—C3A—C6A—C1 | 39.94 (12) | C1—C9—C10—O3 | 79.95 (15) |
C4—C3A—C6A—C1 | −78.61 (11) | C11—C9—C10—O4 | 134.20 (11) |
C8—C1—C6A—C6 | −42.37 (13) | C1—C9—C10—O4 | −100.97 (12) |
C9—C1—C6A—C6 | 79.08 (13) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O1i | 0.847 (19) | 1.90 (2) | 2.7472 (13) | 172,7 (17) |
C11—H11B···O2ii | 0.991 (17) | 2.650 (16) | 3.1916 (17) | 114.5 (11) |
C3—H3A···O3iii | 1.001 (15) | 2.666 (15) | 3.6268 (16) | 161.1 (12) |
C6—H6A···O3iv | 0.945 (18) | 2.652 (18) | 3.5891 (17) | 171.4 (14) |
C7—H7A···O3iii | 0.979 (18) | 2.519 (18) | 3.4278 (16) | 154.3 (13) |
C9—H9A···O3iv | 0.960 (15) | 2.542 (16) | 3.4964 (15) | 172.6 (11) |
C9—H9A···O4iv | 0.960 (15) | 2.669 (15) | 3.3816 (16) | 131.3 (11) |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) −x+2, y+1/2, −z+3/2; (iii) −x+3/2, −y+1, z+1/2; (iv) x+1/2, −y+1/2, −z+1. |