Annonalide (3β,20-epoxy-3α,16-dihydroxy-15-oxo-7-pimaren-19,6β-olide, C20H26O6, 1) is the major (9βH)-pimarane diterpene isolated from tubers of Cassimirella ampla, and it exhibits cytotoxic properties upon interaction with ctDNA. We have prepared new derivatives of 1 by modification of the (9βH)-pimarane backbone and report here the semisynthesis and absolute configuration of a novel rearranged 19,20-δ-lactone (9βH)-pimarane. Our approach was the reduction of the carbonyl groups of 1 with sodium borohydride, at positions C15 (no stereoselectivity) and C3 (stereoselective reduction), followed by rearrangement of the 6,19-γ-lactone ring into the six-membered 19,20-δ-lactone ring in 4a (3β,6β,16-trihydroxy-7-pimaren-19,20β-olide monohydrate, C20H30O6·H2O). The absolute structure of the new compound, 4a, was determined unambiguously with a Flack parameter x of −0.01 (11), supporting the stereochemistry assignment of 1 redetermined here. Besides the changes in the pattern of covalent bonds caused by reduction and lactone rearrangement, the conformation of one of the three fused cyclohexane rings is profoundly different in 4a, adopting a chair conformation instead of the boat shape found in 1. Furthermore, the intramolecular hydrogen bond present in 1 is lost in new compound 4a, due to hydrogen bonding between the 3-OH group and the solvent water molecule.
Supporting information
CCDC references: 1852916; 1544714
For both structures, data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012).
13-Hydroxy-5-(2-hydroxyacetyl)-5,12-dimethyl-10,14-dioxapentacyclo[11.2.2.1
{1,9}.0{2,7}.0
{12,18}]octadec-7-en-11-one (compound_1)
top
Crystal data top
C20H26O6 | Dx = 1.354 Mg m−3 |
Mr = 362.41 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 2644 reflections |
a = 6.6712 (3) Å | θ = 2.5–21.5° |
b = 11.9999 (5) Å | µ = 0.10 mm−1 |
c = 22.2073 (8) Å | T = 296 K |
V = 1777.78 (13) Å3 | Needle, colourless |
Z = 4 | 0.28 × 0.11 × 0.08 mm |
F(000) = 776 | |
Data collection top
Bruker APEXII CCD diffractometer | 2363 reflections with I > 2σ(I) |
CCD scans | Rint = 0.054 |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | θmax = 25.1°, θmin = 1.9° |
Tmin = 0.601, Tmax = 0.992 | h = −7→7 |
8148 measured reflections | k = −9→14 |
3080 independent reflections | l = −26→25 |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.061 | w = 1/[σ2(Fo2) + (0.081P)2 + 0.4497P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.164 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 0.31 e Å−3 |
3080 reflections | Δρmin = −0.27 e Å−3 |
237 parameters | Absolute structure: Flack x determined using 791 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
0 restraints | Absolute structure parameter: 0.1 (10) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O6 | −0.1966 (5) | 0.2471 (3) | 0.20866 (14) | 0.0517 (9) | |
O2 | −0.2503 (5) | 0.1843 (3) | 0.06324 (14) | 0.0513 (9) | |
O5 | −0.4147 (6) | 0.3351 (3) | 0.09337 (17) | 0.0647 (11) | |
O1 | −0.1766 (6) | 0.4353 (3) | 0.19939 (16) | 0.0635 (11) | |
H1 | −0.2906 | 0.4335 | 0.1856 | 0.095* | |
O3 | 0.4005 (15) | −0.3499 (4) | 0.0574 (2) | 0.149 (3) | |
C3 | −0.0773 (8) | 0.3367 (4) | 0.1850 (2) | 0.0494 (12) | |
C4 | −0.0581 (8) | 0.3164 (4) | 0.1166 (2) | 0.0441 (11) | |
C5 | 0.0713 (7) | 0.2112 (4) | 0.10705 (19) | 0.0394 (10) | |
H5 | 0.203 | 0.233 | 0.0914 | 0.047* | |
C10 | 0.0980 (7) | 0.1499 (4) | 0.16722 (18) | 0.0369 (10) | |
C9 | 0.1759 (7) | 0.0310 (4) | 0.15811 (19) | 0.0398 (11) | |
H9 | 0.1392 | −0.0107 | 0.1944 | 0.048* | |
C11 | 0.4035 (8) | 0.0199 (4) | 0.1515 (2) | 0.0516 (13) | |
H11A | 0.4692 | 0.0543 | 0.1857 | 0.062* | |
H11B | 0.447 | 0.0583 | 0.1153 | 0.062* | |
C12 | 0.4642 (8) | −0.1038 (4) | 0.1477 (3) | 0.0553 (13) | |
H12A | 0.4333 | −0.1398 | 0.1857 | 0.066* | |
H12B | 0.6079 | −0.1087 | 0.1415 | 0.066* | |
C13 | 0.3566 (8) | −0.1671 (4) | 0.0962 (2) | 0.0492 (12) | |
C15 | 0.3988 (8) | −0.2915 (4) | 0.1001 (2) | 0.0526 (13) | |
C20 | −0.1061 (7) | 0.1397 (4) | 0.1984 (2) | 0.0471 (12) | |
H20A | −0.1948 | 0.095 | 0.1736 | 0.057* | |
H20B | −0.0892 | 0.1018 | 0.2366 | 0.057* | |
C19 | −0.2590 (9) | 0.2832 (4) | 0.09157 (19) | 0.0457 (12) | |
C6 | −0.0413 (8) | 0.1463 (4) | 0.0591 (2) | 0.0464 (12) | |
H6 | 0.011 | 0.169 | 0.0197 | 0.056* | |
C7 | −0.0250 (8) | 0.0234 (4) | 0.0634 (2) | 0.0498 (13) | |
H7 | −0.0906 | −0.0196 | 0.0346 | 0.06* | |
C8 | 0.0779 (7) | −0.0284 (4) | 0.1059 (2) | 0.0429 (11) | |
C14 | 0.1268 (7) | −0.1511 (4) | 0.1033 (2) | 0.0487 (12) | |
H14A | 0.058 | −0.185 | 0.0695 | 0.058* | |
H14B | 0.0814 | −0.1873 | 0.1399 | 0.058* | |
C17 | 0.4241 (11) | −0.1258 (5) | 0.0348 (3) | 0.0730 (18) | |
H18A | 0.3985 | −0.0473 | 0.0316 | 0.11* | |
H18B | 0.565 | −0.1395 | 0.03 | 0.11* | |
H18C | 0.3514 | −0.1647 | 0.0039 | 0.11* | |
C18 | 0.0168 (11) | 0.4178 (4) | 0.0818 (2) | 0.0650 (16) | |
H18D | 0.1451 | 0.4401 | 0.0973 | 0.097* | |
H18E | 0.0293 | 0.3993 | 0.0399 | 0.097* | |
H18F | −0.0769 | 0.478 | 0.0864 | 0.097* | |
C1 | 0.2258 (8) | 0.2228 (4) | 0.2076 (2) | 0.0495 (12) | |
H1A | 0.3575 | 0.2325 | 0.1899 | 0.059* | |
H1B | 0.2422 | 0.1874 | 0.2466 | 0.059* | |
C2 | 0.1248 (8) | 0.3368 (4) | 0.2155 (2) | 0.0549 (14) | |
H2A | 0.1083 | 0.3528 | 0.2581 | 0.066* | |
H2B | 0.2086 | 0.3945 | 0.1981 | 0.066* | |
C16 | 0.4381 (17) | −0.3474 (5) | 0.1564 (3) | 0.112 (3) | |
H16A | 0.558 | −0.315 | 0.1739 | 0.134* | |
H16B | 0.328 | −0.3312 | 0.1836 | 0.134* | |
O4 | 0.4632 (8) | −0.4609 (3) | 0.1547 (2) | 0.0832 (14) | |
H4 | 0.503 | −0.4793 | 0.1212 | 0.125* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O6 | 0.053 (2) | 0.065 (2) | 0.0366 (18) | 0.0094 (18) | 0.0081 (16) | 0.0049 (16) |
O2 | 0.053 (2) | 0.061 (2) | 0.0407 (18) | 0.0075 (19) | −0.0149 (16) | −0.0080 (15) |
O5 | 0.058 (2) | 0.079 (2) | 0.057 (2) | 0.019 (2) | −0.0135 (19) | −0.011 (2) |
O1 | 0.078 (3) | 0.066 (2) | 0.046 (2) | 0.025 (2) | −0.0127 (19) | −0.0160 (17) |
O3 | 0.311 (10) | 0.076 (3) | 0.060 (3) | 0.036 (5) | 0.001 (5) | −0.016 (2) |
C3 | 0.055 (3) | 0.055 (3) | 0.038 (3) | 0.006 (3) | −0.002 (2) | −0.006 (2) |
C4 | 0.050 (3) | 0.049 (2) | 0.034 (2) | 0.001 (2) | −0.003 (2) | 0.000 (2) |
C5 | 0.040 (3) | 0.049 (2) | 0.029 (2) | −0.004 (2) | 0.004 (2) | 0.0006 (19) |
C10 | 0.038 (2) | 0.047 (2) | 0.026 (2) | −0.004 (2) | −0.0012 (19) | −0.0018 (18) |
C9 | 0.040 (3) | 0.047 (2) | 0.032 (2) | −0.004 (2) | −0.002 (2) | 0.000 (2) |
C11 | 0.040 (3) | 0.054 (3) | 0.061 (3) | −0.007 (2) | −0.006 (3) | −0.008 (3) |
C12 | 0.044 (3) | 0.053 (3) | 0.068 (3) | −0.005 (3) | −0.010 (3) | −0.009 (3) |
C13 | 0.052 (3) | 0.052 (3) | 0.044 (3) | 0.006 (3) | 0.006 (2) | −0.004 (2) |
C15 | 0.053 (3) | 0.056 (3) | 0.049 (3) | 0.002 (3) | 0.001 (3) | −0.010 (2) |
C20 | 0.045 (3) | 0.062 (3) | 0.034 (2) | 0.001 (3) | 0.005 (2) | 0.003 (2) |
C19 | 0.054 (3) | 0.056 (3) | 0.027 (2) | 0.001 (3) | −0.006 (2) | −0.004 (2) |
C6 | 0.055 (3) | 0.056 (3) | 0.028 (2) | 0.007 (3) | −0.004 (2) | −0.003 (2) |
C7 | 0.055 (3) | 0.058 (3) | 0.037 (2) | 0.002 (3) | −0.013 (2) | −0.015 (2) |
C8 | 0.037 (3) | 0.051 (3) | 0.040 (2) | −0.009 (2) | 0.002 (2) | −0.007 (2) |
C14 | 0.048 (3) | 0.047 (3) | 0.051 (3) | −0.008 (3) | −0.006 (2) | −0.004 (2) |
C17 | 0.091 (5) | 0.073 (4) | 0.055 (3) | 0.006 (4) | 0.024 (3) | 0.006 (3) |
C18 | 0.093 (5) | 0.052 (3) | 0.050 (3) | −0.009 (3) | 0.000 (3) | 0.014 (3) |
C1 | 0.054 (3) | 0.052 (3) | 0.042 (3) | −0.001 (3) | −0.013 (2) | −0.005 (2) |
C2 | 0.065 (4) | 0.058 (3) | 0.042 (3) | 0.002 (3) | −0.012 (2) | −0.014 (2) |
C16 | 0.214 (10) | 0.063 (4) | 0.058 (4) | 0.047 (5) | −0.024 (5) | −0.004 (3) |
O4 | 0.102 (4) | 0.060 (2) | 0.087 (3) | 0.016 (3) | −0.017 (3) | 0.001 (2) |
Geometric parameters (Å, º) top
O6—C3 | 1.437 (6) | C13—C17 | 1.520 (7) |
O6—C20 | 1.442 (6) | C13—C15 | 1.521 (7) |
O2—C19 | 1.345 (6) | C13—C14 | 1.553 (7) |
O2—C6 | 1.469 (6) | C15—C16 | 1.443 (8) |
O5—C19 | 1.212 (6) | C20—H20A | 0.97 |
O1—C3 | 1.394 (6) | C20—H20B | 0.97 |
O1—H1 | 0.82 | C6—C7 | 1.482 (7) |
O3—C15 | 1.180 (6) | C6—H6 | 0.98 |
C3—C2 | 1.509 (7) | C7—C8 | 1.322 (7) |
C3—C4 | 1.544 (6) | C7—H7 | 0.93 |
C4—C19 | 1.504 (7) | C8—C14 | 1.509 (6) |
C4—C18 | 1.525 (7) | C14—H14A | 0.97 |
C4—C5 | 1.544 (7) | C14—H14B | 0.97 |
C5—C6 | 1.518 (6) | C17—H18A | 0.96 |
C5—C10 | 1.536 (6) | C17—H18B | 0.96 |
C5—H5 | 0.98 | C17—H18C | 0.96 |
C10—C1 | 1.516 (6) | C18—H18D | 0.96 |
C10—C9 | 1.531 (6) | C18—H18E | 0.96 |
C10—C20 | 1.532 (6) | C18—H18F | 0.96 |
C9—C8 | 1.510 (6) | C1—C2 | 1.535 (7) |
C9—C11 | 1.532 (7) | C1—H1A | 0.97 |
C9—H9 | 0.98 | C1—H1B | 0.97 |
C11—C12 | 1.541 (7) | C2—H2A | 0.97 |
C11—H11A | 0.97 | C2—H2B | 0.97 |
C11—H11B | 0.97 | C16—O4 | 1.373 (7) |
C12—C13 | 1.548 (7) | C16—H16A | 0.97 |
C12—H12A | 0.97 | C16—H16B | 0.97 |
C12—H12B | 0.97 | O4—H4 | 0.82 |
| | | |
C3—O6—C20 | 112.2 (3) | C10—C20—H20A | 109.2 |
C19—O2—C6 | 110.1 (4) | O6—C20—H20B | 109.2 |
C3—O1—H1 | 109.5 | C10—C20—H20B | 109.2 |
O1—C3—O6 | 106.7 (4) | H20A—C20—H20B | 107.9 |
O1—C3—C2 | 108.7 (4) | O5—C19—O2 | 120.4 (5) |
O6—C3—C2 | 109.4 (4) | O5—C19—C4 | 128.0 (4) |
O1—C3—C4 | 113.5 (4) | O2—C19—C4 | 111.6 (4) |
O6—C3—C4 | 106.8 (4) | O2—C6—C7 | 112.0 (4) |
C2—C3—C4 | 111.6 (4) | O2—C6—C5 | 105.5 (4) |
C19—C4—C18 | 108.5 (4) | C7—C6—C5 | 115.5 (4) |
C19—C4—C5 | 103.4 (4) | O2—C6—H6 | 107.9 |
C18—C4—C5 | 113.6 (4) | C7—C6—H6 | 107.9 |
C19—C4—C3 | 109.3 (4) | C5—C6—H6 | 107.9 |
C18—C4—C3 | 113.6 (4) | C8—C7—C6 | 123.4 (4) |
C5—C4—C3 | 108.0 (4) | C8—C7—H7 | 118.3 |
C6—C5—C10 | 114.9 (4) | C6—C7—H7 | 118.3 |
C6—C5—C4 | 103.8 (4) | C7—C8—C14 | 122.9 (4) |
C10—C5—C4 | 109.7 (3) | C7—C8—C9 | 123.5 (4) |
C6—C5—H5 | 109.4 | C14—C8—C9 | 113.4 (4) |
C10—C5—H5 | 109.4 | C8—C14—C13 | 109.8 (4) |
C4—C5—H5 | 109.4 | C8—C14—H14A | 109.7 |
C1—C10—C9 | 115.1 (4) | C13—C14—H14A | 109.7 |
C1—C10—C20 | 106.2 (4) | C8—C14—H14B | 109.7 |
C9—C10—C20 | 106.7 (4) | C13—C14—H14B | 109.7 |
C1—C10—C5 | 107.6 (4) | H14A—C14—H14B | 108.2 |
C9—C10—C5 | 111.8 (3) | C13—C17—H18A | 109.5 |
C20—C10—C5 | 109.2 (4) | C13—C17—H18B | 109.5 |
C8—C9—C10 | 113.2 (4) | H18A—C17—H18B | 109.5 |
C8—C9—C11 | 108.3 (4) | C13—C17—H18C | 109.5 |
C10—C9—C11 | 115.5 (4) | H18A—C17—H18C | 109.5 |
C8—C9—H9 | 106.4 | H18B—C17—H18C | 109.5 |
C10—C9—H9 | 106.4 | C4—C18—H18D | 109.5 |
C11—C9—H9 | 106.4 | C4—C18—H18E | 109.5 |
C9—C11—C12 | 110.5 (4) | H18D—C18—H18E | 109.5 |
C9—C11—H11A | 109.6 | C4—C18—H18F | 109.5 |
C12—C11—H11A | 109.6 | H18D—C18—H18F | 109.5 |
C9—C11—H11B | 109.6 | H18E—C18—H18F | 109.5 |
C12—C11—H11B | 109.6 | C10—C1—C2 | 109.6 (4) |
H11A—C11—H11B | 108.1 | C10—C1—H1A | 109.8 |
C11—C12—C13 | 113.0 (4) | C2—C1—H1A | 109.8 |
C11—C12—H12A | 109 | C10—C1—H1B | 109.8 |
C13—C12—H12A | 109 | C2—C1—H1B | 109.8 |
C11—C12—H12B | 109 | H1A—C1—H1B | 108.2 |
C13—C12—H12B | 109 | C3—C2—C1 | 109.9 (4) |
H12A—C12—H12B | 107.8 | C3—C2—H2A | 109.7 |
C17—C13—C15 | 108.4 (4) | C1—C2—H2A | 109.7 |
C17—C13—C12 | 111.4 (5) | C3—C2—H2B | 109.7 |
C15—C13—C12 | 110.7 (4) | C1—C2—H2B | 109.7 |
C17—C13—C14 | 110.0 (5) | H2A—C2—H2B | 108.2 |
C15—C13—C14 | 107.4 (4) | O4—C16—C15 | 117.3 (5) |
C12—C13—C14 | 108.8 (4) | O4—C16—H16A | 108 |
O3—C15—C16 | 114.8 (5) | C15—C16—H16A | 108 |
O3—C15—C13 | 122.6 (5) | O4—C16—H16B | 108 |
C16—C15—C13 | 122.6 (5) | C15—C16—H16B | 108 |
O6—C20—C10 | 111.9 (4) | H16A—C16—H16B | 107.2 |
O6—C20—H20A | 109.2 | C16—O4—H4 | 109.5 |
| | | |
C20—O6—C3—O1 | −178.1 (4) | C14—C13—C15—C16 | −89.2 (8) |
C20—O6—C3—C2 | −60.7 (5) | C3—O6—C20—C10 | 2.4 (5) |
C20—O6—C3—C4 | 60.2 (5) | C1—C10—C20—O6 | 57.5 (5) |
O1—C3—C4—C19 | −73.5 (5) | C9—C10—C20—O6 | −179.2 (4) |
O6—C3—C4—C19 | 43.8 (5) | C5—C10—C20—O6 | −58.2 (5) |
C2—C3—C4—C19 | 163.3 (4) | C6—O2—C19—O5 | 171.3 (4) |
O1—C3—C4—C18 | 47.8 (7) | C6—O2—C19—C4 | −7.0 (5) |
O6—C3—C4—C18 | 165.0 (4) | C18—C4—C19—O5 | −65.7 (7) |
C2—C3—C4—C18 | −75.5 (6) | C5—C4—C19—O5 | 173.4 (5) |
O1—C3—C4—C5 | 174.7 (4) | C3—C4—C19—O5 | 58.6 (6) |
O6—C3—C4—C5 | −68.0 (5) | C18—C4—C19—O2 | 112.5 (5) |
C2—C3—C4—C5 | 51.4 (5) | C5—C4—C19—O2 | −8.4 (5) |
C19—C4—C5—C6 | 19.5 (5) | C3—C4—C19—O2 | −123.2 (4) |
C18—C4—C5—C6 | −97.8 (5) | C19—O2—C6—C7 | 146.2 (4) |
C3—C4—C5—C6 | 135.3 (4) | C19—O2—C6—C5 | 19.8 (5) |
C19—C4—C5—C10 | −103.8 (4) | C10—C5—C6—O2 | 96.0 (4) |
C18—C4—C5—C10 | 138.9 (4) | C4—C5—C6—O2 | −23.8 (5) |
C3—C4—C5—C10 | 12.0 (5) | C10—C5—C6—C7 | −28.1 (6) |
C6—C5—C10—C1 | 175.8 (4) | C4—C5—C6—C7 | −148.0 (4) |
C4—C5—C10—C1 | −67.7 (5) | O2—C6—C7—C8 | −120.1 (5) |
C6—C5—C10—C9 | 48.5 (5) | C5—C6—C7—C8 | 0.7 (8) |
C4—C5—C10—C9 | 165.0 (4) | C6—C7—C8—C14 | −167.9 (5) |
C6—C5—C10—C20 | −69.3 (5) | C6—C7—C8—C9 | 5.5 (8) |
C4—C5—C10—C20 | 47.2 (5) | C10—C9—C8—C7 | 16.1 (7) |
C1—C10—C9—C8 | −164.9 (4) | C11—C9—C8—C7 | −113.3 (6) |
C20—C10—C9—C8 | 77.6 (4) | C10—C9—C8—C14 | −169.9 (4) |
C5—C10—C9—C8 | −41.6 (5) | C11—C9—C8—C14 | 60.6 (5) |
C1—C10—C9—C11 | −39.2 (6) | C7—C8—C14—C13 | 113.5 (5) |
C20—C10—C9—C11 | −156.7 (4) | C9—C8—C14—C13 | −60.5 (5) |
C5—C10—C9—C11 | 84.1 (5) | C17—C13—C14—C8 | −67.7 (5) |
C8—C9—C11—C12 | −56.3 (6) | C15—C13—C14—C8 | 174.5 (4) |
C10—C9—C11—C12 | 175.5 (4) | C12—C13—C14—C8 | 54.6 (5) |
C9—C11—C12—C13 | 55.9 (6) | C9—C10—C1—C2 | −176.9 (4) |
C11—C12—C13—C17 | 67.4 (6) | C20—C10—C1—C2 | −59.1 (5) |
C11—C12—C13—C15 | −171.9 (4) | C5—C10—C1—C2 | 57.7 (5) |
C11—C12—C13—C14 | −54.1 (6) | O1—C3—C2—C1 | 172.3 (4) |
C17—C13—C15—O3 | −28.6 (9) | O6—C3—C2—C1 | 56.2 (5) |
C12—C13—C15—O3 | −151.1 (7) | C4—C3—C2—C1 | −61.7 (6) |
C14—C13—C15—O3 | 90.2 (8) | C10—C1—C2—C3 | 4.7 (6) |
C17—C13—C15—C16 | 152.0 (7) | O3—C15—C16—O4 | −3.0 (13) |
C12—C13—C15—C16 | 29.5 (9) | C13—C15—C16—O4 | 176.5 (6) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O5 | 0.82 | 2.5 | 3.084 (5) | 129 |
O1—H1···O4i | 0.82 | 2.19 | 2.883 (6) | 143 |
O4—H4···O5ii | 0.82 | 2.38 | 2.917 (6) | 124 |
Symmetry codes: (i) x−1, y+1, z; (ii) x+1, y−1, z. |
5-(1,2-Dihydroxyethyl]-9,17-dihydroxy-5,11-dimethyl-13-\
oxatetracyclo[9.3.3.0
1,10.0
2,7]heptadec-7-en-12-one monohydrate (compound_4a)
top
Crystal data top
C20H30O6·H2O | Dx = 1.336 Mg m−3 |
Mr = 384.45 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, P21212 | Cell parameters from 3033 reflections |
a = 11.7555 (14) Å | θ = 4.4–67.6° |
b = 20.224 (2) Å | µ = 0.83 mm−1 |
c = 8.0385 (11) Å | T = 296 K |
V = 1911.1 (4) Å3 | Prism, colourless |
Z = 4 | 0.32 × 0.15 × 0.10 mm |
F(000) = 832 | |
Data collection top
Bruker APEXII CCD diffractometer | 2594 reflections with I > 2σ(I) |
CCD scans | Rint = 0.045 |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | θmax = 68.2°, θmin = 4.4° |
Tmin = 0.737, Tmax = 0.921 | h = −13→13 |
9565 measured reflections | k = −23→23 |
3311 independent reflections | l = −9→6 |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.046 | w = 1/[σ2(Fo2) + (0.0845P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.137 | (Δ/σ)max = 0.002 |
S = 1.05 | Δρmax = 0.22 e Å−3 |
3311 reflections | Δρmin = −0.24 e Å−3 |
250 parameters | Absolute structure: Flack x determined using 917 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
0 restraints | Absolute structure parameter: −0.01 (11) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O4 | −0.5239 (3) | 0.1565 (2) | 0.5057 (4) | 0.0830 (11) | |
H4 | −0.5579 | 0.1333 | 0.4385 | 0.125* | |
O1W | 0.3841 (3) | −0.08743 (18) | 1.1393 (5) | 0.0773 (11) | |
H1W | 0.457 (5) | −0.102 (3) | 1.106 (8) | 0.116* | |
H2W | 0.347 (5) | −0.116 (3) | 1.193 (9) | 0.116* | |
O6 | 0.2595 (2) | 0.21115 (12) | 1.0532 (4) | 0.0535 (7) | |
O3 | −0.3079 (2) | 0.18204 (13) | 0.3655 (3) | 0.0500 (7) | |
H3 | −0.2865 | 0.2203 | 0.3538 | 0.075* | |
O2 | 0.2769 (2) | 0.18946 (12) | 0.6913 (3) | 0.0482 (7) | |
H2 | 0.3308 | 0.1812 | 0.6299 | 0.072* | |
O1 | 0.3591 (3) | 0.04459 (16) | 1.2152 (4) | 0.0699 (9) | |
H1 | 0.3779 | 0.0057 | 1.2065 | 0.105* | |
O5 | 0.4318 (3) | 0.17254 (14) | 1.0392 (5) | 0.0751 (10) | |
C16 | −0.4223 (3) | 0.1240 (3) | 0.5568 (6) | 0.0703 (14) | |
H16A | −0.4115 | 0.0846 | 0.4899 | 0.084* | |
H16B | −0.4300 | 0.1103 | 0.6720 | 0.084* | |
C15 | −0.3202 (3) | 0.1676 (2) | 0.5399 (5) | 0.0479 (9) | |
H15 | −0.3357 | 0.2091 | 0.5985 | 0.058* | |
C13 | −0.2090 (3) | 0.13804 (18) | 0.6106 (4) | 0.0398 (8) | |
C14 | −0.1143 (3) | 0.19067 (17) | 0.5975 (4) | 0.0416 (9) | |
H14A | −0.0969 | 0.1984 | 0.4811 | 0.050* | |
H14B | −0.1414 | 0.2319 | 0.6446 | 0.050* | |
C8 | −0.0079 (3) | 0.16978 (16) | 0.6866 (4) | 0.0371 (8) | |
C7 | 0.0887 (3) | 0.15998 (17) | 0.6081 (4) | 0.0415 (8) | |
H7 | 0.0904 | 0.1692 | 0.4948 | 0.050* | |
C6 | 0.1959 (3) | 0.13531 (17) | 0.6852 (4) | 0.0396 (8) | |
H6 | 0.2272 | 0.1006 | 0.6135 | 0.048* | |
C5 | 0.1751 (3) | 0.10561 (16) | 0.8587 (4) | 0.0357 (8) | |
H5 | 0.1430 | 0.0614 | 0.8412 | 0.043* | |
C4 | 0.2861 (3) | 0.09611 (17) | 0.9583 (4) | 0.0401 (8) | |
C19 | 0.3321 (4) | 0.16216 (18) | 1.0137 (5) | 0.0506 (10) | |
C20 | 0.1410 (3) | 0.21167 (18) | 1.0025 (5) | 0.0449 (9) | |
H20A | 0.1340 | 0.2390 | 0.9039 | 0.054* | |
H20B | 0.0967 | 0.2324 | 1.0899 | 0.054* | |
C17 | −0.1750 (3) | 0.0755 (2) | 0.5146 (5) | 0.0524 (10) | |
H17A | −0.1655 | 0.0861 | 0.3990 | 0.079* | |
H17B | −0.1048 | 0.0586 | 0.5583 | 0.079* | |
H17C | −0.2335 | 0.0427 | 0.5264 | 0.079* | |
C12 | −0.2251 (3) | 0.12299 (19) | 0.7966 (5) | 0.0451 (9) | |
H12A | −0.2576 | 0.1616 | 0.8500 | 0.054* | |
H12B | −0.2793 | 0.0871 | 0.8078 | 0.054* | |
C11 | −0.1160 (3) | 0.10403 (18) | 0.8883 (4) | 0.0452 (9) | |
H11A | −0.1328 | 0.0975 | 1.0053 | 0.054* | |
H11B | −0.0874 | 0.0626 | 0.8441 | 0.054* | |
C9 | −0.0250 (3) | 0.15693 (17) | 0.8707 (4) | 0.0378 (8) | |
H9 | −0.0571 | 0.1976 | 0.9178 | 0.045* | |
C3 | 0.2589 (3) | 0.0560 (2) | 1.1203 (5) | 0.0484 (9) | |
H3A | 0.2278 | 0.0130 | 1.0873 | 0.058* | |
C2 | 0.1724 (4) | 0.0901 (2) | 1.2283 (4) | 0.0551 (10) | |
H2A | 0.2047 | 0.1305 | 1.2729 | 0.066* | |
H2B | 0.1524 | 0.0616 | 1.3209 | 0.066* | |
C1 | 0.0659 (3) | 0.1064 (2) | 1.1279 (4) | 0.0470 (9) | |
H1A | 0.0155 | 0.1328 | 1.1965 | 0.056* | |
H1B | 0.0267 | 0.0655 | 1.1017 | 0.056* | |
C18 | 0.3753 (3) | 0.05838 (19) | 0.8587 (5) | 0.0509 (10) | |
H18A | 0.3446 | 0.0165 | 0.8245 | 0.076* | |
H18B | 0.3961 | 0.0836 | 0.7623 | 0.076* | |
H18C | 0.4413 | 0.0512 | 0.9266 | 0.076* | |
C10 | 0.0891 (3) | 0.14398 (16) | 0.9648 (4) | 0.0369 (8) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O4 | 0.0368 (17) | 0.127 (3) | 0.086 (2) | 0.0117 (19) | −0.0003 (15) | 0.031 (2) |
O1W | 0.069 (2) | 0.074 (2) | 0.089 (2) | 0.0153 (19) | 0.0203 (19) | 0.0232 (19) |
O6 | 0.0449 (17) | 0.0399 (14) | 0.0757 (17) | 0.0003 (12) | −0.0139 (14) | −0.0154 (14) |
O3 | 0.0512 (17) | 0.0487 (15) | 0.0500 (13) | −0.0058 (13) | −0.0075 (12) | 0.0081 (12) |
O2 | 0.0395 (15) | 0.0459 (14) | 0.0592 (14) | −0.0041 (12) | 0.0062 (12) | 0.0076 (13) |
O1 | 0.065 (2) | 0.077 (2) | 0.0685 (16) | 0.0089 (17) | −0.0245 (16) | 0.0128 (17) |
O5 | 0.048 (2) | 0.0454 (15) | 0.132 (3) | −0.0037 (14) | −0.023 (2) | −0.0110 (19) |
C16 | 0.032 (3) | 0.092 (3) | 0.087 (3) | 0.002 (2) | −0.001 (2) | 0.039 (3) |
C15 | 0.041 (2) | 0.050 (2) | 0.0531 (18) | 0.0046 (18) | 0.0021 (17) | 0.0046 (19) |
C13 | 0.036 (2) | 0.0381 (18) | 0.0458 (17) | 0.0031 (16) | 0.0003 (15) | 0.0002 (17) |
C14 | 0.043 (2) | 0.0390 (19) | 0.0428 (16) | −0.0022 (17) | 0.0015 (15) | 0.0073 (16) |
C8 | 0.041 (2) | 0.0312 (17) | 0.0386 (16) | −0.0049 (16) | 0.0005 (15) | 0.0016 (15) |
C7 | 0.042 (2) | 0.046 (2) | 0.0368 (15) | −0.0015 (18) | 0.0018 (15) | 0.0060 (16) |
C6 | 0.041 (2) | 0.0373 (18) | 0.0407 (17) | −0.0046 (16) | 0.0039 (15) | −0.0002 (16) |
C5 | 0.038 (2) | 0.0268 (16) | 0.0421 (16) | −0.0031 (15) | 0.0026 (15) | −0.0025 (15) |
C4 | 0.042 (2) | 0.0311 (17) | 0.0476 (17) | 0.0004 (16) | −0.0011 (16) | −0.0006 (17) |
C19 | 0.047 (3) | 0.037 (2) | 0.068 (2) | 0.0014 (19) | −0.013 (2) | −0.001 (2) |
C20 | 0.043 (2) | 0.0408 (19) | 0.0514 (17) | 0.0035 (17) | −0.0050 (16) | −0.0084 (17) |
C17 | 0.047 (2) | 0.050 (2) | 0.060 (2) | 0.0033 (19) | −0.0058 (19) | −0.0124 (19) |
C12 | 0.043 (2) | 0.044 (2) | 0.0484 (18) | −0.0066 (17) | 0.0026 (17) | 0.0041 (18) |
C11 | 0.046 (2) | 0.047 (2) | 0.0426 (16) | −0.0113 (18) | 0.0031 (16) | 0.0064 (17) |
C9 | 0.038 (2) | 0.0358 (17) | 0.0393 (16) | −0.0004 (16) | 0.0049 (14) | −0.0020 (16) |
C3 | 0.049 (2) | 0.044 (2) | 0.0513 (18) | −0.0001 (19) | −0.0096 (18) | 0.008 (2) |
C2 | 0.065 (3) | 0.063 (2) | 0.0371 (16) | 0.000 (2) | −0.0040 (18) | 0.0058 (19) |
C1 | 0.050 (2) | 0.056 (2) | 0.0355 (16) | 0.0009 (19) | 0.0043 (16) | 0.0013 (18) |
C18 | 0.050 (3) | 0.040 (2) | 0.063 (2) | 0.0059 (18) | 0.001 (2) | 0.000 (2) |
C10 | 0.041 (2) | 0.0342 (17) | 0.0356 (15) | −0.0028 (16) | 0.0016 (15) | −0.0012 (15) |
Geometric parameters (Å, º) top
O4—C16 | 1.425 (5) | C5—C4 | 1.542 (5) |
O4—H4 | 0.8200 | C5—H5 | 0.9800 |
O1W—H1W | 0.95 (6) | C4—C19 | 1.508 (5) |
O1W—H2W | 0.84 (6) | C4—C18 | 1.524 (5) |
O6—C19 | 1.345 (5) | C4—C3 | 1.568 (5) |
O6—C20 | 1.451 (5) | C20—C10 | 1.529 (5) |
O3—C15 | 1.440 (4) | C20—H20A | 0.9700 |
O3—H3 | 0.8200 | C20—H20B | 0.9700 |
O2—C6 | 1.452 (4) | C17—H17A | 0.9600 |
O2—H2 | 0.8200 | C17—H17B | 0.9600 |
O1—C3 | 1.422 (5) | C17—H17C | 0.9600 |
O1—H1 | 0.8200 | C12—C11 | 1.528 (5) |
O5—C19 | 1.208 (5) | C12—H12A | 0.9700 |
C16—C15 | 1.496 (6) | C12—H12B | 0.9700 |
C16—H16A | 0.9700 | C11—C9 | 1.519 (5) |
C16—H16B | 0.9700 | C11—H11A | 0.9700 |
C15—C13 | 1.546 (5) | C11—H11B | 0.9700 |
C15—H15 | 0.9800 | C9—C10 | 1.562 (5) |
C13—C17 | 1.534 (5) | C9—H9 | 0.9800 |
C13—C12 | 1.537 (5) | C3—C2 | 1.504 (6) |
C13—C14 | 1.544 (5) | C3—H3A | 0.9800 |
C14—C8 | 1.502 (5) | C2—C1 | 1.525 (5) |
C14—H14A | 0.9700 | C2—H2A | 0.9700 |
C14—H14B | 0.9700 | C2—H2B | 0.9700 |
C8—C7 | 1.314 (5) | C1—C10 | 1.540 (5) |
C8—C9 | 1.517 (4) | C1—H1A | 0.9700 |
C7—C6 | 1.490 (5) | C1—H1B | 0.9700 |
C7—H7 | 0.9300 | C18—H18A | 0.9600 |
C6—C5 | 1.538 (4) | C18—H18B | 0.9600 |
C6—H6 | 0.9800 | C18—H18C | 0.9600 |
C5—C10 | 1.534 (5) | | |
| | | |
C16—O4—H4 | 109.5 | C10—C20—H20A | 108.4 |
H1W—O1W—H2W | 113 (6) | O6—C20—H20B | 108.4 |
C19—O6—C20 | 123.2 (3) | C10—C20—H20B | 108.4 |
C15—O3—H3 | 109.5 | H20A—C20—H20B | 107.4 |
C6—O2—H2 | 109.5 | C13—C17—H17A | 109.5 |
C3—O1—H1 | 109.5 | C13—C17—H17B | 109.5 |
O4—C16—C15 | 112.0 (4) | H17A—C17—H17B | 109.5 |
O4—C16—H16A | 109.2 | C13—C17—H17C | 109.5 |
C15—C16—H16A | 109.2 | H17A—C17—H17C | 109.5 |
O4—C16—H16B | 109.2 | H17B—C17—H17C | 109.5 |
C15—C16—H16B | 109.2 | C11—C12—C13 | 114.6 (3) |
H16A—C16—H16B | 107.9 | C11—C12—H12A | 108.6 |
O3—C15—C16 | 106.8 (3) | C13—C12—H12A | 108.6 |
O3—C15—C13 | 110.6 (3) | C11—C12—H12B | 108.6 |
C16—C15—C13 | 114.7 (3) | C13—C12—H12B | 108.6 |
O3—C15—H15 | 108.2 | H12A—C12—H12B | 107.6 |
C16—C15—H15 | 108.2 | C9—C11—C12 | 111.6 (3) |
C13—C15—H15 | 108.2 | C9—C11—H11A | 109.3 |
C17—C13—C12 | 111.0 (3) | C12—C11—H11A | 109.3 |
C17—C13—C14 | 110.3 (3) | C9—C11—H11B | 109.3 |
C12—C13—C14 | 107.0 (3) | C12—C11—H11B | 109.3 |
C17—C13—C15 | 110.7 (3) | H11A—C11—H11B | 108.0 |
C12—C13—C15 | 109.3 (3) | C8—C9—C11 | 107.8 (3) |
C14—C13—C15 | 108.5 (3) | C8—C9—C10 | 112.8 (3) |
C8—C14—C13 | 112.0 (3) | C11—C9—C10 | 116.2 (3) |
C8—C14—H14A | 109.2 | C8—C9—H9 | 106.5 |
C13—C14—H14A | 109.2 | C11—C9—H9 | 106.5 |
C8—C14—H14B | 109.2 | C10—C9—H9 | 106.5 |
C13—C14—H14B | 109.2 | O1—C3—C2 | 108.9 (3) |
H14A—C14—H14B | 107.9 | O1—C3—C4 | 111.1 (3) |
C7—C8—C14 | 122.2 (3) | C2—C3—C4 | 112.3 (3) |
C7—C8—C9 | 123.8 (3) | O1—C3—H3A | 108.1 |
C14—C8—C9 | 113.8 (3) | C2—C3—H3A | 108.1 |
C8—C7—C6 | 125.6 (3) | C4—C3—H3A | 108.1 |
C8—C7—H7 | 117.2 | C3—C2—C1 | 110.4 (3) |
C6—C7—H7 | 117.2 | C3—C2—H2A | 109.6 |
O2—C6—C7 | 108.4 (3) | C1—C2—H2A | 109.6 |
O2—C6—C5 | 111.6 (3) | C3—C2—H2B | 109.6 |
C7—C6—C5 | 111.9 (3) | C1—C2—H2B | 109.6 |
O2—C6—H6 | 108.3 | H2A—C2—H2B | 108.1 |
C7—C6—H6 | 108.3 | C2—C1—C10 | 114.3 (3) |
C5—C6—H6 | 108.3 | C2—C1—H1A | 108.7 |
C10—C5—C6 | 114.3 (3) | C10—C1—H1A | 108.7 |
C10—C5—C4 | 109.4 (3) | C2—C1—H1B | 108.7 |
C6—C5—C4 | 112.6 (3) | C10—C1—H1B | 108.7 |
C10—C5—H5 | 106.7 | H1A—C1—H1B | 107.6 |
C6—C5—H5 | 106.7 | C4—C18—H18A | 109.5 |
C4—C5—H5 | 106.7 | C4—C18—H18B | 109.5 |
C19—C4—C18 | 110.6 (3) | H18A—C18—H18B | 109.5 |
C19—C4—C5 | 110.2 (3) | C4—C18—H18C | 109.5 |
C18—C4—C5 | 111.8 (3) | H18A—C18—H18C | 109.5 |
C19—C4—C3 | 106.6 (3) | H18B—C18—H18C | 109.5 |
C18—C4—C3 | 108.5 (3) | C20—C10—C5 | 107.4 (3) |
C5—C4—C3 | 108.9 (3) | C20—C10—C1 | 110.1 (3) |
O5—C19—O6 | 116.5 (3) | C5—C10—C1 | 109.9 (3) |
O5—C19—C4 | 123.5 (4) | C20—C10—C9 | 106.8 (3) |
O6—C19—C4 | 119.7 (4) | C5—C10—C9 | 112.4 (3) |
O6—C20—C10 | 115.6 (3) | C1—C10—C9 | 110.1 (3) |
O6—C20—H20A | 108.4 | | |
| | | |
O4—C16—C15—O3 | −63.3 (5) | C14—C13—C12—C11 | −53.3 (4) |
O4—C16—C15—C13 | 173.8 (4) | C15—C13—C12—C11 | −170.6 (3) |
O3—C15—C13—C17 | −57.3 (4) | C13—C12—C11—C9 | 56.2 (4) |
C16—C15—C13—C17 | 63.5 (5) | C7—C8—C9—C11 | −118.5 (4) |
O3—C15—C13—C12 | −179.8 (3) | C14—C8—C9—C11 | 57.6 (4) |
C16—C15—C13—C12 | −59.0 (4) | C7—C8—C9—C10 | 11.1 (5) |
O3—C15—C13—C14 | 63.9 (4) | C14—C8—C9—C10 | −172.8 (3) |
C16—C15—C13—C14 | −175.3 (4) | C12—C11—C9—C8 | −54.4 (4) |
C17—C13—C14—C8 | −67.1 (4) | C12—C11—C9—C10 | 178.0 (3) |
C12—C13—C14—C8 | 53.6 (4) | C19—C4—C3—O1 | −62.3 (4) |
C15—C13—C14—C8 | 171.4 (3) | C18—C4—C3—O1 | 56.8 (4) |
C13—C14—C8—C7 | 116.7 (4) | C5—C4—C3—O1 | 178.8 (3) |
C13—C14—C8—C9 | −59.5 (4) | C19—C4—C3—C2 | 60.0 (4) |
C14—C8—C7—C6 | −176.0 (3) | C18—C4—C3—C2 | 179.2 (3) |
C9—C8—C7—C6 | −0.2 (6) | C5—C4—C3—C2 | −58.9 (4) |
C8—C7—C6—O2 | −109.2 (4) | O1—C3—C2—C1 | 177.0 (3) |
C8—C7—C6—C5 | 14.4 (5) | C4—C3—C2—C1 | 53.5 (4) |
O2—C6—C5—C10 | 81.9 (4) | C3—C2—C1—C10 | −51.8 (5) |
C7—C6—C5—C10 | −39.8 (4) | O6—C20—C10—C5 | −44.9 (4) |
O2—C6—C5—C4 | −43.7 (4) | O6—C20—C10—C1 | 74.8 (4) |
C7—C6—C5—C4 | −165.5 (3) | O6—C20—C10—C9 | −165.7 (3) |
C10—C5—C4—C19 | −56.3 (4) | C6—C5—C10—C20 | −65.7 (3) |
C6—C5—C4—C19 | 72.0 (4) | C4—C5—C10—C20 | 61.6 (3) |
C10—C5—C4—C18 | −179.8 (3) | C6—C5—C10—C1 | 174.4 (3) |
C6—C5—C4—C18 | −51.5 (4) | C4—C5—C10—C1 | −58.3 (4) |
C10—C5—C4—C3 | 60.3 (3) | C6—C5—C10—C9 | 51.4 (4) |
C6—C5—C4—C3 | −171.4 (3) | C4—C5—C10—C9 | 178.8 (3) |
C20—O6—C19—O5 | 168.2 (4) | C2—C1—C10—C20 | −63.6 (4) |
C20—O6—C19—C4 | −18.1 (5) | C2—C1—C10—C5 | 54.6 (4) |
C18—C4—C19—O5 | −28.6 (6) | C2—C1—C10—C9 | 179.0 (3) |
C5—C4—C19—O5 | −152.8 (4) | C8—C9—C10—C20 | 81.8 (3) |
C3—C4—C19—O5 | 89.2 (5) | C11—C9—C10—C20 | −153.0 (3) |
C18—C4—C19—O6 | 158.1 (3) | C8—C9—C10—C5 | −35.7 (4) |
C5—C4—C19—O6 | 33.9 (5) | C11—C9—C10—C5 | 89.4 (4) |
C3—C4—C19—O6 | −84.1 (4) | C8—C9—C10—C1 | −158.6 (3) |
C19—O6—C20—C10 | 24.0 (5) | C11—C9—C10—C1 | −33.5 (4) |
C17—C13—C12—C11 | 67.0 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O1W | 0.82 | 1.96 | 2.754 (5) | 163 |
O2—H2···O4i | 0.82 | 2.04 | 2.855 (4) | 172 |
O3—H3···O2ii | 0.82 | 2 | 2.821 (4) | 174 |
O4—H4···O1iii | 0.82 | 2.72 | 3.532 (5) | 171 |
O1W—H1W···O1iv | 0.95 (6) | 2.61 (6) | 3.200 (5) | 121 (5) |
O1W—H1W···O5iv | 0.95 (6) | 2.01 (6) | 2.881 (4) | 153 (5) |
O1W—H2W···O3v | 0.84 (6) | 1.98 (7) | 2.787 (4) | 160 (6) |
Symmetry codes: (i) x+1, y, z; (ii) x−1/2, −y+1/2, −z+1; (iii) x−1, y, z−1; (iv) −x+1, −y, z; (v) −x, −y, z+1. |