The title compound, C
22H
28O
5, is a commercial therapeutic agent of the steroid class. Both independent molecules in the asymmetric unit have six-membered
A rings that are planar, while the
B and
C rings adopt normal chair conformations. The five-membered
D ring is in a 13
![[beta]](/logos/entities/beta_rmgif.gif)
,14
![[alpha]](/logos/entities/alpha_rmgif.gif)
-half-chair conformation, and the
B/
C and
C/
D ring junctions are in
trans positions. Cohesion in the crystal is provided by O-H
![...](/logos/entities/ctdot_rmgif.gif)
O hydrogen bonds, which generate chains of molecules that are organized in a plane that lies along the crystallographic
b axis.
Supporting information
CCDC reference: 211741
Compound (I) was obtained from LABORATORIOS GADOR SA, Buenos Aires, Argentina. Crystals suitable for X-ray diffraction were obtained via slow evaporation from an aqueous solution.
The positional parameters of the hydroxyl atoms H17 and H21 were refined with the distances to their carrier atoms restrained to 0.85 Å and Uiso equal to 1.5Ueq(O). H atoms attached to C atoms were constrained, with C—H distances of 0.98 Å for primary, 0.99 Å for secondary, 1 Å for tertiary and 0.95 Å for aromatic H atoms, and refined in a riding model with their isotropic thermal parameters constrained to 1.2 times larger than those of their hosts. For the final refinement, because the molecule lacks a significant anomalous scatterer at the Mo Kα wavelength, Friedel pairs were merged using the MERG 4 instruction implemented in SHELXL97. The correct enantiomer was chosen to agree with the known chirality of the steroid (Rausser et al., 1966).
Data collection: COLLECT (Nonius, 1997–2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and Scalepak (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1991); software used to prepare material for publication: PARST (Nardelli, 1995) and WinGX (Farrugia, 1999).
Crystal data top
C22H28O5 | F(000) = 800 |
Mr = 372.44 | Dx = 1.31 Mg m−3 |
Monoclinic, P21 | Melting point = 473–478 K |
Hall symbol: P 2yb | Mo Kα radiation, λ = 0.71073 Å |
a = 11.4372 (4) Å | Cell parameters from 3579 reflections |
b = 7.8901 (3) Å | θ = 1.0–25.0° |
c = 21.1268 (9) Å | µ = 0.09 mm−1 |
β = 97.896 (2)° | T = 120 K |
V = 1888.42 (13) Å3 | Needle, colorless |
Z = 4 | 0.18 × 0.06 × 0.02 mm |
Data collection top
Nonius KappaCCD diffractometer | Rint = 0.050 |
ϕ scans and ω scans with κ offsets | θmax = 25.0°, θmin = 3.2° |
6178 measured reflections | h = −13→13 |
3583 independent reflections | k = −9→7 |
2757 reflections with I > 2σ(I) | l = −25→24 |
Refinement top
Refinement on F2 | H atoms treated by a mixture of independent and constrained refinement |
Least-squares matrix: full | w = 1/[σ2(Fo2)] |
R[F2 > 2σ(F2)] = 0.044 | (Δ/σ)max = 0.001 |
wR(F2) = 0.099 | Δρmax = 0.18 e Å−3 |
S = 1.05 | Δρmin = −0.19 e Å−3 |
3583 reflections | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
500 parameters | Extinction coefficient: 0.033 (3) |
5 restraints | |
Crystal data top
C22H28O5 | V = 1888.42 (13) Å3 |
Mr = 372.44 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 11.4372 (4) Å | µ = 0.09 mm−1 |
b = 7.8901 (3) Å | T = 120 K |
c = 21.1268 (9) Å | 0.18 × 0.06 × 0.02 mm |
β = 97.896 (2)° | |
Data collection top
Nonius KappaCCD diffractometer | 2757 reflections with I > 2σ(I) |
6178 measured reflections | Rint = 0.050 |
3583 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 5 restraints |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.18 e Å−3 |
3583 reflections | Δρmin = −0.19 e Å−3 |
500 parameters | |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1A | 0.1997 (3) | 0.3784 (5) | 0.33142 (17) | 0.0302 (9) | |
H1A | 0.2486 | 0.3692 | 0.2987 | 0.036* | |
C1B | 0.5283 (4) | 0.1504 (5) | 0.89312 (18) | 0.0316 (10) | |
H1B | 0.4925 | 0.2445 | 0.87 | 0.038* | |
C2A | 0.1774 (3) | 0.2384 (5) | 0.36251 (17) | 0.0330 (10) | |
H2A | 0.2109 | 0.1341 | 0.3515 | 0.04* | |
C2B | 0.6238 (3) | 0.1805 (5) | 0.93548 (17) | 0.0325 (10) | |
H2B | 0.6522 | 0.2932 | 0.9419 | 0.039* | |
C3A | 0.1025 (3) | 0.2404 (5) | 0.41323 (18) | 0.0337 (10) | |
C3B | 0.6847 (3) | 0.0427 (5) | 0.97196 (17) | 0.0309 (9) | |
C4A | 0.0422 (3) | 0.3984 (5) | 0.42203 (18) | 0.0334 (10) | |
H4A | −0.0144 | 0.4005 | 0.451 | 0.04* | |
C4B | 0.6375 (3) | −0.1258 (5) | 0.96047 (17) | 0.0323 (10) | |
H4B | 0.6764 | −0.2178 | 0.9835 | 0.039* | |
C5A | 0.0626 (3) | 0.5426 (5) | 0.39110 (16) | 0.0288 (9) | |
C5B | 0.5403 (3) | −0.1582 (5) | 0.91834 (17) | 0.0292 (9) | |
C6A | −0.0013 (3) | 0.7037 (5) | 0.40223 (17) | 0.0313 (9) | |
H6A | 0.0546 | 0.7855 | 0.4254 | 0.038* | |
H6B | −0.0638 | 0.6796 | 0.4291 | 0.038* | |
C6B | 0.4949 (4) | −0.3355 (5) | 0.90545 (17) | 0.0348 (10) | |
H6C | 0.4138 | −0.3446 | 0.9166 | 0.042* | |
H6D | 0.5457 | −0.4166 | 0.9324 | 0.042* | |
C7A | −0.0568 (3) | 0.7816 (5) | 0.33896 (17) | 0.0327 (10) | |
H7A | −0.091 | 0.8932 | 0.3474 | 0.039* | |
H7B | −0.1217 | 0.7077 | 0.3193 | 0.039* | |
C7B | 0.4943 (4) | −0.3799 (5) | 0.83468 (17) | 0.0337 (10) | |
H7C | 0.5767 | −0.389 | 0.8257 | 0.04* | |
H7D | 0.4562 | −0.4918 | 0.826 | 0.04* | |
C8A | 0.0328 (3) | 0.8043 (5) | 0.29221 (16) | 0.0265 (9) | |
H8A | 0.0954 | 0.8843 | 0.3117 | 0.032* | |
C8B | 0.4293 (3) | −0.2484 (5) | 0.79002 (16) | 0.0258 (9) | |
H8B | 0.3432 | −0.2527 | 0.7941 | 0.031* | |
C9A | 0.0915 (3) | 0.6319 (5) | 0.28122 (16) | 0.0271 (9) | |
H9A | 0.0254 | 0.5537 | 0.2649 | 0.033* | |
C9B | 0.4766 (3) | −0.0672 (5) | 0.80735 (16) | 0.0263 (9) | |
H9B | 0.5621 | −0.0697 | 0.802 | 0.032* | |
C10A | 0.1527 (3) | 0.5502 (5) | 0.34485 (17) | 0.0295 (9) | |
C10B | 0.4732 (3) | −0.0202 (5) | 0.87923 (16) | 0.0272 (9) | |
C11A | 0.1692 (4) | 0.6447 (5) | 0.22734 (17) | 0.0318 (10) | |
C11B | 0.4197 (3) | 0.0604 (5) | 0.75856 (17) | 0.0292 (9) | |
C12A | 0.1100 (4) | 0.7219 (5) | 0.16516 (16) | 0.0311 (9) | |
H12A | 0.0428 | 0.6505 | 0.1465 | 0.037* | |
H12B | 0.167 | 0.7297 | 0.134 | 0.037* | |
C12B | 0.4358 (3) | 0.0220 (5) | 0.69022 (16) | 0.0297 (9) | |
H12C | 0.5207 | 0.025 | 0.6856 | 0.036* | |
H12D | 0.3945 | 0.1084 | 0.6614 | 0.036* | |
C13A | 0.0663 (3) | 0.8994 (5) | 0.18027 (16) | 0.0260 (9) | |
C13B | 0.3848 (3) | −0.1553 (5) | 0.67214 (16) | 0.0251 (8) | |
C14A | −0.0234 (3) | 0.8779 (5) | 0.22817 (16) | 0.0261 (9) | |
H14A | −0.0852 | 0.7963 | 0.209 | 0.031* | |
C14B | 0.4454 (3) | −0.2849 (5) | 0.72050 (16) | 0.0287 (9) | |
H14B | 0.532 | −0.277 | 0.7182 | 0.034* | |
C15A | −0.0807 (3) | 1.0501 (5) | 0.22907 (16) | 0.0303 (9) | |
H15A | −0.0324 | 1.1265 | 0.2593 | 0.036* | |
H15B | −0.1604 | 1.0405 | 0.242 | 0.036* | |
C15B | 0.4042 (3) | −0.4544 (5) | 0.69034 (16) | 0.0312 (9) | |
H15C | 0.3242 | −0.483 | 0.7 | 0.037* | |
H15D | 0.4591 | −0.5466 | 0.7063 | 0.037* | |
C16A | −0.0884 (3) | 1.1184 (5) | 0.15971 (17) | 0.0289 (9) | |
H16A | −0.1722 | 1.1054 | 0.1395 | 0.035* | |
C16B | 0.4034 (3) | −0.4271 (5) | 0.61704 (16) | 0.0298 (9) | |
H16B | 0.4767 | −0.4819 | 0.6058 | 0.036* | |
C17A | −0.0124 (3) | 0.9921 (5) | 0.12496 (16) | 0.0255 (9) | |
C17B | 0.4198 (3) | −0.2313 (5) | 0.60916 (16) | 0.0272 (9) | |
C18A | 0.1736 (3) | 1.0074 (6) | 0.20684 (17) | 0.0343 (10) | |
H18A | 0.1473 | 1.1213 | 0.2168 | 0.051* | |
H18B | 0.228 | 1.0151 | 0.1749 | 0.051* | |
H18C | 0.2141 | 0.9546 | 0.2458 | 0.051* | |
C18B | 0.2505 (3) | −0.1485 (6) | 0.67085 (17) | 0.0323 (10) | |
H18D | 0.217 | −0.0637 | 0.6396 | 0.048* | |
H18E | 0.232 | −0.1175 | 0.7133 | 0.048* | |
H18F | 0.2165 | −0.2598 | 0.6588 | 0.048* | |
C19A | 0.2594 (3) | 0.6596 (6) | 0.37593 (18) | 0.0357 (10) | |
H19A | 0.3181 | 0.6682 | 0.3463 | 0.054* | |
H19B | 0.2955 | 0.6059 | 0.4157 | 0.054* | |
H19C | 0.2317 | 0.7733 | 0.3852 | 0.054* | |
C19B | 0.3463 (3) | −0.0105 (6) | 0.89654 (18) | 0.0360 (10) | |
H19D | 0.3021 | 0.0779 | 0.8709 | 0.054* | |
H19E | 0.3494 | 0.0166 | 0.942 | 0.054* | |
H19F | 0.3069 | −0.12 | 0.8877 | 0.054* | |
C20A | 0.0598 (3) | 1.0702 (6) | 0.07606 (17) | 0.0296 (9) | |
C20B | 0.3531 (3) | −0.1461 (5) | 0.55025 (16) | 0.0309 (9) | |
C21A | 0.0591 (3) | 0.9786 (5) | 0.01302 (17) | 0.0338 (10) | |
H21C | 0.0794 | 0.858 | 0.0213 | 0.041* | |
H21D | −0.0213 | 0.9835 | −0.0113 | 0.041* | |
C21B | 0.4223 (3) | −0.0232 (6) | 0.51536 (17) | 0.0369 (10) | |
H21E | 0.4602 | 0.062 | 0.546 | 0.044* | |
H21F | 0.4855 | −0.0851 | 0.4974 | 0.044* | |
C22A | −0.0596 (4) | 1.3063 (5) | 0.15932 (18) | 0.0344 (10) | |
H22A | 0.0211 | 1.3247 | 0.1806 | 0.052* | |
H22B | −0.1151 | 1.3688 | 0.182 | 0.052* | |
H22C | −0.0661 | 1.3465 | 0.1151 | 0.052* | |
C22B | 0.2999 (4) | −0.5138 (5) | 0.57646 (18) | 0.0371 (10) | |
H22D | 0.3042 | −0.4928 | 0.5311 | 0.056* | |
H22E | 0.2256 | −0.4683 | 0.5875 | 0.056* | |
H22F | 0.3032 | −0.6361 | 0.5847 | 0.056* | |
O3A | 0.0924 (3) | 0.1119 (4) | 0.44623 (14) | 0.0479 (8) | |
O3B | 0.7728 (2) | 0.0717 (4) | 1.01224 (12) | 0.0402 (7) | |
O11A | 0.2722 (2) | 0.6003 (4) | 0.23357 (12) | 0.0389 (7) | |
O11B | 0.3640 (2) | 0.1841 (4) | 0.77205 (12) | 0.0377 (7) | |
O17A | −0.0898 (2) | 0.8660 (4) | 0.09262 (12) | 0.0310 (7) | |
H17A | −0.138 (3) | 0.926 (5) | 0.0647 (17) | 0.047* | |
O17B | 0.5435 (2) | −0.1936 (4) | 0.61015 (12) | 0.0311 (7) | |
H17B | 0.563 (3) | −0.271 (5) | 0.5838 (17) | 0.047* | |
O20A | 0.1170 (2) | 1.1993 (4) | 0.08735 (12) | 0.0378 (7) | |
O20B | 0.2488 (2) | −0.1672 (4) | 0.53174 (12) | 0.0368 (7) | |
O21A | 0.1409 (2) | 1.0515 (4) | −0.02443 (12) | 0.0371 (7) | |
H21A | 0.111 (4) | 1.148 (4) | −0.042 (2) | 0.056* | |
O21B | 0.3500 (2) | 0.0604 (4) | 0.46558 (13) | 0.0427 (8) | |
H21B | 0.278 (3) | 0.040 (7) | 0.468 (2) | 0.064* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1A | 0.029 (2) | 0.036 (3) | 0.0241 (19) | 0.0033 (19) | −0.0014 (16) | 0.0016 (19) |
C1B | 0.039 (2) | 0.028 (2) | 0.028 (2) | 0.0005 (19) | 0.0044 (18) | −0.0028 (18) |
C2A | 0.034 (2) | 0.032 (2) | 0.033 (2) | 0.0046 (19) | 0.0031 (18) | 0.002 (2) |
C2B | 0.034 (2) | 0.032 (2) | 0.030 (2) | −0.0011 (19) | 0.0029 (18) | −0.0020 (19) |
C3A | 0.037 (2) | 0.029 (2) | 0.035 (2) | −0.002 (2) | 0.0023 (18) | 0.006 (2) |
C3B | 0.032 (2) | 0.033 (2) | 0.028 (2) | −0.001 (2) | 0.0043 (17) | −0.0029 (19) |
C4A | 0.031 (2) | 0.039 (3) | 0.031 (2) | 0.002 (2) | 0.0058 (17) | 0.006 (2) |
C4B | 0.035 (2) | 0.036 (3) | 0.026 (2) | 0.0040 (19) | 0.0034 (17) | 0.0036 (19) |
C5A | 0.028 (2) | 0.033 (2) | 0.0240 (19) | 0.0029 (19) | −0.0002 (15) | −0.0006 (19) |
C5B | 0.031 (2) | 0.034 (2) | 0.0233 (19) | 0.0000 (19) | 0.0072 (16) | 0.0046 (18) |
C6A | 0.037 (2) | 0.033 (2) | 0.025 (2) | 0.0055 (19) | 0.0095 (17) | 0.0037 (19) |
C6B | 0.041 (2) | 0.032 (2) | 0.030 (2) | 0.000 (2) | 0.0001 (18) | 0.0040 (19) |
C7A | 0.034 (2) | 0.033 (3) | 0.033 (2) | 0.0052 (19) | 0.0115 (17) | 0.0046 (19) |
C7B | 0.044 (2) | 0.029 (2) | 0.029 (2) | 0.0017 (19) | 0.0050 (18) | 0.0057 (19) |
C8A | 0.030 (2) | 0.024 (2) | 0.0266 (19) | 0.0029 (18) | 0.0070 (16) | 0.0050 (17) |
C8B | 0.026 (2) | 0.028 (2) | 0.0242 (19) | 0.0020 (17) | 0.0068 (15) | 0.0076 (17) |
C9A | 0.030 (2) | 0.028 (2) | 0.0234 (19) | 0.0008 (17) | 0.0068 (16) | 0.0012 (17) |
C9B | 0.027 (2) | 0.026 (2) | 0.0245 (19) | −0.0029 (17) | 0.0008 (15) | 0.0005 (17) |
C10A | 0.029 (2) | 0.031 (2) | 0.028 (2) | 0.0015 (18) | 0.0031 (15) | 0.0025 (19) |
C10B | 0.026 (2) | 0.031 (2) | 0.026 (2) | 0.0018 (18) | 0.0049 (16) | 0.0008 (18) |
C11A | 0.036 (2) | 0.030 (2) | 0.029 (2) | 0.005 (2) | 0.0043 (17) | −0.0011 (19) |
C11B | 0.030 (2) | 0.026 (2) | 0.030 (2) | −0.0012 (19) | 0.0011 (16) | 0.0017 (19) |
C12A | 0.035 (2) | 0.034 (2) | 0.0244 (19) | 0.0048 (19) | 0.0055 (17) | −0.0006 (18) |
C12B | 0.034 (2) | 0.028 (2) | 0.0275 (19) | −0.0008 (18) | 0.0063 (16) | 0.0058 (18) |
C13A | 0.030 (2) | 0.026 (2) | 0.0230 (19) | 0.0015 (17) | 0.0053 (16) | 0.0013 (17) |
C13B | 0.027 (2) | 0.026 (2) | 0.0228 (18) | −0.0001 (17) | 0.0052 (15) | 0.0018 (17) |
C14A | 0.025 (2) | 0.030 (2) | 0.0238 (19) | −0.0010 (17) | 0.0068 (15) | 0.0017 (18) |
C14B | 0.030 (2) | 0.032 (2) | 0.0252 (19) | 0.0014 (18) | 0.0075 (16) | 0.0038 (18) |
C15A | 0.033 (2) | 0.029 (2) | 0.031 (2) | 0.0074 (19) | 0.0106 (16) | 0.0045 (19) |
C15B | 0.038 (2) | 0.030 (2) | 0.027 (2) | 0.004 (2) | 0.0076 (17) | 0.0007 (19) |
C16A | 0.030 (2) | 0.030 (2) | 0.026 (2) | 0.0012 (18) | 0.0026 (16) | −0.0033 (18) |
C16B | 0.032 (2) | 0.030 (2) | 0.0278 (19) | −0.0025 (19) | 0.0076 (16) | −0.0017 (18) |
C17A | 0.031 (2) | 0.023 (2) | 0.0225 (19) | −0.0003 (17) | 0.0031 (16) | 0.0001 (17) |
C17B | 0.023 (2) | 0.036 (2) | 0.0236 (19) | −0.0027 (17) | 0.0051 (16) | 0.0013 (18) |
C18A | 0.034 (2) | 0.042 (3) | 0.027 (2) | −0.004 (2) | 0.0048 (17) | 0.001 (2) |
C18B | 0.029 (2) | 0.037 (3) | 0.032 (2) | 0.0024 (19) | 0.0059 (17) | 0.003 (2) |
C19A | 0.031 (2) | 0.044 (3) | 0.031 (2) | −0.001 (2) | 0.0000 (17) | 0.000 (2) |
C19B | 0.033 (2) | 0.043 (3) | 0.032 (2) | 0.005 (2) | 0.0063 (17) | −0.005 (2) |
C20A | 0.028 (2) | 0.033 (3) | 0.027 (2) | 0.002 (2) | 0.0034 (16) | 0.0035 (19) |
C20B | 0.033 (2) | 0.038 (3) | 0.023 (2) | −0.001 (2) | 0.0084 (17) | −0.0038 (19) |
C21A | 0.035 (2) | 0.039 (3) | 0.030 (2) | −0.004 (2) | 0.0121 (18) | 0.001 (2) |
C21B | 0.037 (2) | 0.045 (3) | 0.028 (2) | 0.001 (2) | 0.0008 (18) | 0.012 (2) |
C22A | 0.043 (2) | 0.032 (2) | 0.027 (2) | 0.005 (2) | 0.0046 (18) | 0.0033 (19) |
C22B | 0.047 (3) | 0.029 (2) | 0.036 (2) | −0.006 (2) | 0.0099 (19) | −0.002 (2) |
O3A | 0.055 (2) | 0.0391 (19) | 0.0532 (19) | 0.0036 (15) | 0.0189 (15) | 0.0137 (16) |
O3B | 0.0390 (16) | 0.0412 (19) | 0.0375 (15) | 0.0000 (14) | −0.0044 (13) | −0.0030 (14) |
O11A | 0.0340 (17) | 0.048 (2) | 0.0356 (15) | 0.0119 (14) | 0.0086 (12) | 0.0066 (14) |
O11B | 0.0446 (18) | 0.0316 (17) | 0.0356 (16) | 0.0075 (14) | 0.0011 (13) | −0.0009 (13) |
O17A | 0.0339 (16) | 0.0311 (17) | 0.0270 (14) | −0.0012 (13) | 0.0002 (11) | 0.0001 (13) |
O17B | 0.0262 (14) | 0.0382 (17) | 0.0301 (14) | −0.0002 (13) | 0.0084 (11) | −0.0013 (13) |
O20A | 0.0451 (18) | 0.0341 (18) | 0.0358 (15) | −0.0052 (15) | 0.0115 (13) | −0.0004 (14) |
O20B | 0.0312 (16) | 0.0464 (19) | 0.0315 (15) | −0.0022 (14) | 0.0000 (12) | 0.0053 (14) |
O21A | 0.0419 (17) | 0.0396 (19) | 0.0320 (15) | 0.0014 (15) | 0.0134 (12) | 0.0057 (14) |
O21B | 0.0378 (17) | 0.052 (2) | 0.0385 (15) | 0.0005 (16) | 0.0061 (13) | 0.0203 (15) |
Geometric parameters (Å, º) top
C1A—C2A | 1.328 (5) | C13A—C18A | 1.535 (5) |
C1A—C10A | 1.500 (6) | C13A—C14A | 1.547 (5) |
C1A—H1A | 0.95 | C13A—C17A | 1.556 (5) |
C1B—C2B | 1.335 (5) | C13B—C18B | 1.534 (5) |
C1B—C10B | 1.498 (6) | C13B—C14B | 1.541 (5) |
C1B—H1B | 0.95 | C13B—C17B | 1.561 (5) |
C2A—C3A | 1.461 (5) | C14A—C15A | 1.509 (5) |
C2A—H2A | 0.95 | C14A—H14A | 1 |
C2B—C3B | 1.454 (6) | C14B—C15B | 1.528 (6) |
C2B—H2B | 0.95 | C14B—H14B | 1 |
C3A—O3A | 1.245 (5) | C15A—C16A | 1.552 (5) |
C3A—C4A | 1.449 (6) | C15A—H15A | 0.99 |
C3B—O3B | 1.248 (4) | C15A—H15B | 0.99 |
C3B—C4B | 1.443 (6) | C15B—C16B | 1.562 (5) |
C4A—C5A | 1.348 (5) | C15B—H15C | 0.99 |
C4A—H4A | 0.95 | C15B—H15D | 0.99 |
C4B—C5B | 1.350 (5) | C16A—C22A | 1.518 (6) |
C4B—H4B | 0.95 | C16A—C17A | 1.569 (5) |
C5A—C6A | 1.501 (5) | C16A—H16A | 1 |
C5A—C10A | 1.515 (5) | C16B—C22B | 1.526 (5) |
C5B—C6B | 1.504 (6) | C16B—C17B | 1.568 (6) |
C5B—C10B | 1.511 (5) | C16B—H16B | 1 |
C6A—C7A | 1.528 (5) | C17A—O17A | 1.440 (4) |
C6A—H6A | 0.99 | C17A—C20A | 1.537 (5) |
C6A—H6B | 0.99 | C17B—O17B | 1.443 (4) |
C6B—C7B | 1.535 (5) | C17B—C20B | 1.524 (5) |
C6B—H6C | 0.99 | C18A—H18A | 0.98 |
C6B—H6D | 0.99 | C18A—H18B | 0.98 |
C7A—C8A | 1.528 (5) | C18A—H18C | 0.98 |
C7A—H7A | 0.99 | C18B—H18D | 0.98 |
C7A—H7B | 0.99 | C18B—H18E | 0.98 |
C7B—C8B | 1.525 (5) | C18B—H18F | 0.98 |
C7B—H7C | 0.99 | C19A—H19A | 0.98 |
C7B—H7D | 0.99 | C19A—H19B | 0.98 |
C8A—C14A | 1.530 (5) | C19A—H19C | 0.98 |
C8A—C9A | 1.549 (5) | C19B—H19D | 0.98 |
C8A—H8A | 1 | C19B—H19E | 0.98 |
C8B—C14B | 1.532 (5) | C19B—H19F | 0.98 |
C8B—C9B | 1.555 (5) | C20A—O20A | 1.217 (5) |
C8B—H8B | 1 | C20A—C21A | 1.514 (5) |
C9A—C11A | 1.541 (5) | C20B—O20B | 1.214 (4) |
C9A—C10A | 1.566 (5) | C20B—C21B | 1.507 (5) |
C9A—H9A | 1 | C21A—O21A | 1.427 (4) |
C9B—C11B | 1.522 (5) | C21A—H21C | 0.99 |
C9B—C10B | 1.569 (5) | C21A—H21D | 0.99 |
C9B—H9B | 1 | C21B—O21B | 1.409 (4) |
C10A—C19A | 1.565 (5) | C21B—H21E | 0.99 |
C10B—C19B | 1.547 (5) | C21B—H21F | 0.99 |
C11A—O11A | 1.219 (4) | C22A—H22A | 0.98 |
C11A—C12A | 1.520 (5) | C22A—H22B | 0.98 |
C11B—O11B | 1.220 (5) | C22A—H22C | 0.98 |
C11B—C12B | 1.511 (5) | C22B—H22D | 0.98 |
C12A—C13A | 1.535 (5) | C22B—H22E | 0.98 |
C12A—H12A | 0.99 | C22B—H22F | 0.98 |
C12A—H12B | 0.99 | O17A—H17A | 0.89 (3) |
C12B—C13B | 1.543 (5) | O17B—H17B | 0.88 (3) |
C12B—H12C | 0.99 | O21A—H21A | 0.89 (3) |
C12B—H12D | 0.99 | O21B—H21B | 0.85 (3) |
| | | |
C2A—C1A—C10A | 124.0 (4) | C14A—C13A—C17A | 100.1 (3) |
C2A—C1A—H1A | 118 | C18B—C13B—C14B | 113.2 (3) |
C10A—C1A—H1A | 118 | C18B—C13B—C12B | 108.4 (3) |
C2B—C1B—C10B | 125.1 (4) | C14B—C13B—C12B | 108.5 (3) |
C2B—C1B—H1B | 117.5 | C18B—C13B—C17B | 111.8 (3) |
C10B—C1B—H1B | 117.5 | C14B—C13B—C17B | 99.5 (3) |
C1A—C2A—C3A | 121.7 (4) | C12B—C13B—C17B | 115.3 (3) |
C1A—C2A—H2A | 119.1 | C15A—C14A—C8A | 117.4 (3) |
C3A—C2A—H2A | 119.1 | C15A—C14A—C13A | 103.7 (3) |
C1B—C2B—C3B | 120.7 (4) | C8A—C14A—C13A | 112.6 (3) |
C1B—C2B—H2B | 119.6 | C15A—C14A—H14A | 107.5 |
C3B—C2B—H2B | 119.6 | C8A—C14A—H14A | 107.5 |
O3A—C3A—C4A | 123.2 (4) | C13A—C14A—H14A | 107.5 |
O3A—C3A—C2A | 120.7 (4) | C15B—C14B—C8B | 119.5 (3) |
C4A—C3A—C2A | 116.1 (4) | C15B—C14B—C13B | 102.7 (3) |
O3B—C3B—C4B | 122.2 (4) | C8B—C14B—C13B | 114.1 (3) |
O3B—C3B—C2B | 120.5 (4) | C15B—C14B—H14B | 106.6 |
C4B—C3B—C2B | 117.3 (3) | C8B—C14B—H14B | 106.6 |
C5A—C4A—C3A | 123.2 (4) | C13B—C14B—H14B | 106.6 |
C5A—C4A—H4A | 118.4 | C14A—C15A—C16A | 105.6 (3) |
C3A—C4A—H4A | 118.4 | C14A—C15A—H15A | 110.6 |
C5B—C4B—C3B | 122.7 (4) | C16A—C15A—H15A | 110.6 |
C5B—C4B—H4B | 118.6 | C14A—C15A—H15B | 110.6 |
C3B—C4B—H4B | 118.6 | C16A—C15A—H15B | 110.6 |
C4A—C5A—C6A | 121.2 (3) | H15A—C15A—H15B | 108.7 |
C4A—C5A—C10A | 121.6 (4) | C14B—C15B—C16B | 104.6 (3) |
C6A—C5A—C10A | 117.2 (3) | C14B—C15B—H15C | 110.8 |
C4B—C5B—C6B | 121.9 (4) | C16B—C15B—H15C | 110.8 |
C4B—C5B—C10B | 122.3 (4) | C14B—C15B—H15D | 110.8 |
C6B—C5B—C10B | 115.7 (3) | C16B—C15B—H15D | 110.8 |
C5A—C6A—C7A | 110.9 (3) | H15C—C15B—H15D | 108.9 |
C5A—C6A—H6A | 109.5 | C22A—C16A—C15A | 111.1 (3) |
C7A—C6A—H6A | 109.5 | C22A—C16A—C17A | 118.9 (3) |
C5A—C6A—H6B | 109.5 | C15A—C16A—C17A | 104.9 (3) |
C7A—C6A—H6B | 109.5 | C22A—C16A—H16A | 107.1 |
H6A—C6A—H6B | 108.1 | C15A—C16A—H16A | 107.1 |
C5B—C6B—C7B | 110.1 (3) | C17A—C16A—H16A | 107.1 |
C5B—C6B—H6C | 109.6 | C22B—C16B—C15B | 113.2 (3) |
C7B—C6B—H6C | 109.6 | C22B—C16B—C17B | 118.5 (3) |
C5B—C6B—H6D | 109.6 | C15B—C16B—C17B | 104.9 (3) |
C7B—C6B—H6D | 109.6 | C22B—C16B—H16B | 106.5 |
H6C—C6B—H6D | 108.2 | C15B—C16B—H16B | 106.5 |
C6A—C7A—C8A | 112.2 (3) | C17B—C16B—H16B | 106.5 |
C6A—C7A—H7A | 109.2 | O17A—C17A—C20A | 108.0 (3) |
C8A—C7A—H7A | 109.2 | O17A—C17A—C13A | 106.6 (3) |
C6A—C7A—H7B | 109.2 | C20A—C17A—C13A | 112.6 (3) |
C8A—C7A—H7B | 109.2 | O17A—C17A—C16A | 108.5 (3) |
H7A—C7A—H7B | 107.9 | C20A—C17A—C16A | 116.3 (3) |
C8B—C7B—C6B | 112.6 (3) | C13A—C17A—C16A | 104.3 (3) |
C8B—C7B—H7C | 109.1 | O17B—C17B—C20B | 107.5 (3) |
C6B—C7B—H7C | 109.1 | O17B—C17B—C13B | 105.9 (3) |
C8B—C7B—H7D | 109.1 | C20B—C17B—C13B | 111.6 (3) |
C6B—C7B—H7D | 109.1 | O17B—C17B—C16B | 109.4 (3) |
H7C—C7B—H7D | 107.8 | C20B—C17B—C16B | 117.9 (3) |
C7A—C8A—C14A | 112.3 (3) | C13B—C17B—C16B | 103.9 (3) |
C7A—C8A—C9A | 109.7 (3) | C13A—C18A—H18A | 109.5 |
C14A—C8A—C9A | 109.8 (3) | C13A—C18A—H18B | 109.5 |
C7A—C8A—H8A | 108.3 | H18A—C18A—H18B | 109.5 |
C14A—C8A—H8A | 108.3 | C13A—C18A—H18C | 109.5 |
C9A—C8A—H8A | 108.3 | H18A—C18A—H18C | 109.5 |
C7B—C8B—C14B | 110.6 (3) | H18B—C18A—H18C | 109.5 |
C7B—C8B—C9B | 110.8 (3) | C13B—C18B—H18D | 109.5 |
C14B—C8B—C9B | 108.3 (3) | C13B—C18B—H18E | 109.5 |
C7B—C8B—H8B | 109 | H18D—C18B—H18E | 109.5 |
C14B—C8B—H8B | 109 | C13B—C18B—H18F | 109.5 |
C9B—C8B—H8B | 109 | H18D—C18B—H18F | 109.5 |
C11A—C9A—C8A | 111.0 (3) | H18E—C18B—H18F | 109.5 |
C11A—C9A—C10A | 115.2 (3) | C10A—C19A—H19A | 109.5 |
C8A—C9A—C10A | 112.6 (3) | C10A—C19A—H19B | 109.5 |
C11A—C9A—H9A | 105.7 | H19A—C19A—H19B | 109.5 |
C8A—C9A—H9A | 105.7 | C10A—C19A—H19C | 109.5 |
C10A—C9A—H9A | 105.7 | H19A—C19A—H19C | 109.5 |
C11B—C9B—C8B | 110.3 (3) | H19B—C19A—H19C | 109.5 |
C11B—C9B—C10B | 115.7 (3) | C10B—C19B—H19D | 109.5 |
C8B—C9B—C10B | 113.0 (3) | C10B—C19B—H19E | 109.5 |
C11B—C9B—H9B | 105.6 | H19D—C19B—H19E | 109.5 |
C8B—C9B—H9B | 105.6 | C10B—C19B—H19F | 109.5 |
C10B—C9B—H9B | 105.6 | H19D—C19B—H19F | 109.5 |
C1A—C10A—C5A | 112.3 (3) | H19E—C19B—H19F | 109.5 |
C1A—C10A—C19A | 107.4 (3) | O20A—C20A—C21A | 120.6 (3) |
C5A—C10A—C19A | 108.2 (3) | O20A—C20A—C17A | 121.9 (3) |
C1A—C10A—C9A | 109.8 (3) | C21A—C20A—C17A | 117.5 (3) |
C5A—C10A—C9A | 107.9 (3) | O20B—C20B—C21B | 119.3 (3) |
C19A—C10A—C9A | 111.3 (3) | O20B—C20B—C17B | 124.2 (3) |
C1B—C10B—C5B | 111.8 (3) | C21B—C20B—C17B | 116.5 (3) |
C1B—C10B—C19B | 107.0 (3) | O21A—C21A—C20A | 111.8 (3) |
C5B—C10B—C19B | 109.2 (3) | O21A—C21A—H21C | 109.3 |
C1B—C10B—C9B | 109.6 (3) | C20A—C21A—H21C | 109.3 |
C5B—C10B—C9B | 106.3 (3) | O21A—C21A—H21D | 109.3 |
C19B—C10B—C9B | 112.9 (3) | C20A—C21A—H21D | 109.3 |
O11A—C11A—C12A | 121.2 (3) | H21C—C21A—H21D | 107.9 |
O11A—C11A—C9A | 123.3 (3) | O21B—C21B—C20B | 111.8 (3) |
C12A—C11A—C9A | 115.6 (3) | O21B—C21B—H21E | 109.3 |
O11B—C11B—C12B | 121.3 (3) | C20B—C21B—H21E | 109.3 |
O11B—C11B—C9B | 124.0 (3) | O21B—C21B—H21F | 109.3 |
C12B—C11B—C9B | 114.7 (3) | C20B—C21B—H21F | 109.3 |
C11A—C12A—C13A | 107.8 (3) | H21E—C21B—H21F | 107.9 |
C11A—C12A—H12A | 110.2 | C16A—C22A—H22A | 109.5 |
C13A—C12A—H12A | 110.2 | C16A—C22A—H22B | 109.5 |
C11A—C12A—H12B | 110.2 | H22A—C22A—H22B | 109.5 |
C13A—C12A—H12B | 110.2 | C16A—C22A—H22C | 109.5 |
H12A—C12A—H12B | 108.5 | H22A—C22A—H22C | 109.5 |
C11B—C12B—C13B | 109.1 (3) | H22B—C22A—H22C | 109.5 |
C11B—C12B—H12C | 109.9 | C16B—C22B—H22D | 109.5 |
C13B—C12B—H12C | 109.9 | C16B—C22B—H22E | 109.5 |
C11B—C12B—H12D | 109.9 | H22D—C22B—H22E | 109.5 |
C13B—C12B—H12D | 109.9 | C16B—C22B—H22F | 109.5 |
H12C—C12B—H12D | 108.3 | H22D—C22B—H22F | 109.5 |
C12A—C13A—C18A | 108.4 (3) | H22E—C22B—H22F | 109.5 |
C12A—C13A—C14A | 107.5 (3) | C17A—O17A—H17A | 103 (3) |
C18A—C13A—C14A | 113.0 (3) | C17B—O17B—H17B | 100 (3) |
C12A—C13A—C17A | 116.3 (3) | C21A—O21A—H21A | 109 (3) |
C18A—C13A—C17A | 111.4 (3) | C21B—O21B—H21B | 110 (3) |
| | | |
C10A—C1A—C2A—C3A | 0.5 (6) | C11B—C12B—C13B—C18B | 67.3 (4) |
C10B—C1B—C2B—C3B | 1.1 (6) | C11B—C12B—C13B—C14B | −56.0 (4) |
C1A—C2A—C3A—O3A | −172.5 (4) | C11B—C12B—C13B—C17B | −166.5 (3) |
C1A—C2A—C3A—C4A | 7.6 (6) | C7A—C8A—C14A—C15A | 60.3 (4) |
C1B—C2B—C3B—O3B | −178.9 (3) | C9A—C8A—C14A—C15A | −177.4 (3) |
C1B—C2B—C3B—C4B | −0.2 (6) | C7A—C8A—C14A—C13A | −179.3 (3) |
O3A—C3A—C4A—C5A | 172.7 (4) | C9A—C8A—C14A—C13A | −57.1 (4) |
C2A—C3A—C4A—C5A | −7.4 (6) | C12A—C13A—C14A—C15A | −168.1 (3) |
O3B—C3B—C4B—C5B | 178.1 (3) | C18A—C13A—C14A—C15A | 72.4 (4) |
C2B—C3B—C4B—C5B | −0.6 (5) | C17A—C13A—C14A—C15A | −46.2 (3) |
C3A—C4A—C5A—C6A | −179.5 (3) | C12A—C13A—C14A—C8A | 63.9 (4) |
C3A—C4A—C5A—C10A | −0.8 (6) | C18A—C13A—C14A—C8A | −55.6 (4) |
C3B—C4B—C5B—C6B | 177.9 (3) | C17A—C13A—C14A—C8A | −174.1 (3) |
C3B—C4B—C5B—C10B | 0.4 (6) | C7B—C8B—C14B—C15B | 59.4 (5) |
C4A—C5A—C6A—C7A | −128.7 (4) | C9B—C8B—C14B—C15B | −178.9 (3) |
C10A—C5A—C6A—C7A | 52.5 (4) | C7B—C8B—C14B—C13B | −178.7 (3) |
C4B—C5B—C6B—C7B | −119.9 (4) | C9B—C8B—C14B—C13B | −57.0 (4) |
C10B—C5B—C6B—C7B | 57.7 (4) | C18B—C13B—C14B—C15B | 69.5 (4) |
C5A—C6A—C7A—C8A | −52.9 (5) | C12B—C13B—C14B—C15B | −170.1 (3) |
C5B—C6B—C7B—C8B | −52.7 (4) | C17B—C13B—C14B—C15B | −49.3 (3) |
C6A—C7A—C8A—C14A | 178.5 (3) | C18B—C13B—C14B—C8B | −61.3 (4) |
C6A—C7A—C8A—C9A | 56.1 (4) | C12B—C13B—C14B—C8B | 59.0 (4) |
C6B—C7B—C8B—C14B | 172.2 (3) | C17B—C13B—C14B—C8B | 179.9 (3) |
C6B—C7B—C8B—C9B | 52.1 (4) | C8A—C14A—C15A—C16A | 160.3 (3) |
C7A—C8A—C9A—C11A | 172.0 (3) | C13A—C14A—C15A—C16A | 35.4 (4) |
C14A—C8A—C9A—C11A | 48.2 (4) | C8B—C14B—C15B—C16B | 165.4 (3) |
C7A—C8A—C9A—C10A | −57.1 (4) | C13B—C14B—C15B—C16B | 38.0 (3) |
C14A—C8A—C9A—C10A | 179.1 (3) | C14A—C15A—C16A—C22A | −139.8 (3) |
C7B—C8B—C9B—C11B | 174.4 (3) | C14A—C15A—C16A—C17A | −10.2 (4) |
C14B—C8B—C9B—C11B | 52.9 (4) | C14B—C15B—C16B—C22B | −141.8 (3) |
C7B—C8B—C9B—C10B | −54.3 (4) | C14B—C15B—C16B—C17B | −11.2 (4) |
C14B—C8B—C9B—C10B | −175.8 (3) | C12A—C13A—C17A—O17A | 39.8 (4) |
C2A—C1A—C10A—C5A | −8.3 (5) | C18A—C13A—C17A—O17A | 164.7 (3) |
C2A—C1A—C10A—C19A | 110.5 (4) | C14A—C13A—C17A—O17A | −75.6 (3) |
C2A—C1A—C10A—C9A | −128.3 (4) | C12A—C13A—C17A—C20A | −78.5 (4) |
C4A—C5A—C10A—C1A | 8.3 (5) | C18A—C13A—C17A—C20A | 46.4 (4) |
C6A—C5A—C10A—C1A | −172.9 (3) | C14A—C13A—C17A—C20A | 166.1 (3) |
C4A—C5A—C10A—C19A | −110.0 (4) | C12A—C13A—C17A—C16A | 154.5 (3) |
C6A—C5A—C10A—C19A | 68.8 (4) | C18A—C13A—C17A—C16A | −80.6 (3) |
C4A—C5A—C10A—C9A | 129.5 (4) | C14A—C13A—C17A—C16A | 39.2 (3) |
C6A—C5A—C10A—C9A | −51.8 (4) | C22A—C16A—C17A—O17A | −140.2 (3) |
C11A—C9A—C10A—C1A | −55.4 (4) | C15A—C16A—C17A—O17A | 94.9 (3) |
C8A—C9A—C10A—C1A | 175.8 (3) | C22A—C16A—C17A—C20A | −18.2 (5) |
C11A—C9A—C10A—C5A | −178.1 (3) | C15A—C16A—C17A—C20A | −143.2 (3) |
C8A—C9A—C10A—C5A | 53.1 (4) | C22A—C16A—C17A—C13A | 106.4 (4) |
C11A—C9A—C10A—C19A | 63.4 (4) | C15A—C16A—C17A—C13A | −18.5 (4) |
C8A—C9A—C10A—C19A | −65.4 (4) | C18B—C13B—C17B—O17B | 166.7 (3) |
C2B—C1B—C10B—C5B | −1.1 (5) | C14B—C13B—C17B—O17B | −73.5 (3) |
C2B—C1B—C10B—C19B | 118.4 (4) | C12B—C13B—C17B—O17B | 42.2 (4) |
C2B—C1B—C10B—C9B | −118.8 (4) | C18B—C13B—C17B—C20B | 50.0 (4) |
C4B—C5B—C10B—C1B | 0.3 (5) | C14B—C13B—C17B—C20B | 169.8 (3) |
C6B—C5B—C10B—C1B | −177.3 (3) | C12B—C13B—C17B—C20B | −74.5 (4) |
C4B—C5B—C10B—C19B | −117.9 (4) | C18B—C13B—C17B—C16B | −78.1 (4) |
C6B—C5B—C10B—C19B | 64.5 (4) | C14B—C13B—C17B—C16B | 41.7 (3) |
C4B—C5B—C10B—C9B | 120.0 (4) | C12B—C13B—C17B—C16B | 157.5 (3) |
C6B—C5B—C10B—C9B | −57.6 (4) | C22B—C16B—C17B—O17B | −139.1 (3) |
C11B—C9B—C10B—C1B | −55.6 (4) | C15B—C16B—C17B—O17B | 93.6 (3) |
C8B—C9B—C10B—C1B | 175.8 (3) | C22B—C16B—C17B—C20B | −15.8 (5) |
C11B—C9B—C10B—C5B | −176.7 (3) | C15B—C16B—C17B—C20B | −143.2 (3) |
C8B—C9B—C10B—C5B | 54.8 (4) | C22B—C16B—C17B—C13B | 108.2 (3) |
C11B—C9B—C10B—C19B | 63.6 (4) | C15B—C16B—C17B—C13B | −19.2 (4) |
C8B—C9B—C10B—C19B | −65.0 (4) | O17A—C17A—C20A—O20A | 167.1 (3) |
C8A—C9A—C11A—O11A | 127.2 (4) | C13A—C17A—C20A—O20A | −75.4 (5) |
C10A—C9A—C11A—O11A | −2.4 (6) | C16A—C17A—C20A—O20A | 44.9 (5) |
C8A—C9A—C11A—C12A | −51.1 (4) | O17A—C17A—C20A—C21A | −14.0 (4) |
C10A—C9A—C11A—C12A | 179.3 (3) | C13A—C17A—C20A—C21A | 103.5 (4) |
C8B—C9B—C11B—O11B | 122.7 (4) | C16A—C17A—C20A—C21A | −136.2 (3) |
C10B—C9B—C11B—O11B | −7.1 (5) | O17B—C17B—C20B—O20B | 172.1 (4) |
C8B—C9B—C11B—C12B | −56.5 (4) | C13B—C17B—C20B—O20B | −72.2 (5) |
C10B—C9B—C11B—C12B | 173.6 (3) | C16B—C17B—C20B—O20B | 47.9 (5) |
O11A—C11A—C12A—C13A | −121.0 (4) | O17B—C17B—C20B—C21B | −10.5 (4) |
C9A—C11A—C12A—C13A | 57.4 (4) | C13B—C17B—C20B—C21B | 105.2 (4) |
O11B—C11B—C12B—C13B | −121.4 (4) | C16B—C17B—C20B—C21B | −134.7 (4) |
C9B—C11B—C12B—C13B | 57.9 (4) | O20A—C20A—C21A—O21A | 6.5 (5) |
C11A—C12A—C13A—C18A | 61.7 (4) | C17A—C20A—C21A—O21A | −172.5 (3) |
C11A—C12A—C13A—C14A | −60.7 (4) | O20B—C20B—C21B—O21B | 3.3 (5) |
C11A—C12A—C13A—C17A | −171.8 (3) | C17B—C20B—C21B—O21B | −174.3 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O17A—H17A···O3Bi | 0.89 (3) | 1.81 (3) | 2.694 (4) | 173 (4) |
O17B—H17B···O21Bii | 0.88 (3) | 2.03 (3) | 2.889 (4) | 165 (4) |
O21A—H21A···O17Aiii | 0.89 (3) | 2.03 (3) | 2.888 (4) | 163 (4) |
O21B—H21B···O20B | 0.85 (3) | 2.17 (5) | 2.638 (4) | 115 (4) |
O21B—H21B···O3A | 0.85 (3) | 2.19 (4) | 2.946 (4) | 149 (5) |
C1A—H1A···O11A | 0.95 | 2.32 | 2.915 (5) | 120 |
C1B—H1B···O11B | 0.95 | 2.41 | 2.970 (5) | 117 |
C18A—H18B···O20A | 0.98 | 2.55 | 2.937 (4) | 104 |
C18B—H18D···O20B | 0.98 | 2.50 | 2.942 (4) | 107 |
C19A—H19A···O11A | 0.98 | 2.43 | 3.067 (4) | 122 |
C19B—H19D···O11B | 0.98 | 2.44 | 3.076 (5) | 122 |
Symmetry codes: (i) x−1, y+1, z−1; (ii) −x+1, y−1/2, −z+1; (iii) −x, y+1/2, −z. |
Experimental details
Crystal data |
Chemical formula | C22H28O5 |
Mr | 372.44 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 120 |
a, b, c (Å) | 11.4372 (4), 7.8901 (3), 21.1268 (9) |
β (°) | 97.896 (2) |
V (Å3) | 1888.42 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.18 × 0.06 × 0.02 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6178, 3583, 2757 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.099, 1.05 |
No. of reflections | 3583 |
No. of parameters | 500 |
No. of restraints | 5 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.18, −0.19 |
Selected geometric parameters (Å, º) topC3A—O3A | 1.245 (5) | C17B—O17B | 1.443 (4) |
C3B—O3B | 1.248 (4) | C20A—O20A | 1.217 (5) |
C11A—O11A | 1.219 (4) | C20B—O20B | 1.214 (4) |
C11B—O11B | 1.220 (5) | C21A—O21A | 1.427 (4) |
C17A—O17A | 1.440 (4) | C21B—O21B | 1.409 (4) |
| | | |
C4A—C5A—C10A—C9A | 129.5 (4) | C16B—C17B—C20B—O20B | 47.9 (5) |
C4B—C5B—C10B—C9B | 120.0 (4) | O20A—C20A—C21A—O21A | 6.5 (5) |
O17A—C17A—C20A—O20A | 167.1 (3) | C17A—C20A—C21A—O21A | −172.5 (3) |
C16A—C17A—C20A—O20A | 44.9 (5) | O20B—C20B—C21B—O21B | 3.3 (5) |
O17B—C17B—C20B—O20B | 172.1 (4) | C17B—C20B—C21B—O21B | −174.3 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O17A—H17A···O3Bi | 0.89 (3) | 1.81 (3) | 2.694 (4) | 173 (4) |
O17B—H17B···O21Bii | 0.88 (3) | 2.03 (3) | 2.889 (4) | 165 (4) |
O21A—H21A···O17Aiii | 0.89 (3) | 2.03 (3) | 2.888 (4) | 163 (4) |
O21B—H21B···O20B | 0.85 (3) | 2.17 (5) | 2.638 (4) | 115 (4) |
O21B—H21B···O3A | 0.85 (3) | 2.19 (4) | 2.946 (4) | 149 (5) |
C1A—H1A···O11A | 0.95 | 2.32 | 2.915 (5) | 120 |
C1B—H1B···O11B | 0.95 | 2.41 | 2.970 (5) | 117 |
C18A—H18B···O20A | 0.98 | 2.55 | 2.937 (4) | 104 |
C18B—H18D···O20B | 0.98 | 2.50 | 2.942 (4) | 107 |
C19A—H19A···O11A | 0.98 | 2.43 | 3.067 (4) | 122 |
C19B—H19D···O11B | 0.98 | 2.44 | 3.076 (5) | 122 |
Symmetry codes: (i) x−1, y+1, z−1; (ii) −x+1, y−1/2, −z+1; (iii) −x, y+1/2, −z. |
Corticosteroids constitute a class of compounds that are able to exert several physiologic and metabolic activities; in particular, the glucocorticoids can affect the lipid, carbohydrate and protein metabolism and, with a lesser potency, the electrolyte balance (Goodman & Gilman, 1993). The title compound, meprednisone, (I), is a steroid anti-inflammatory treatment that is indicated for rheumatic, collagen and skin diseases and possesses an anti-inflammatory potency equivalent to six times that of cortisone. Meprednisone, the 16β-methyl analogue of prednisone (Δ1 cortisone or 17α,21-dihydroxy-pregna-1,4-diene-3,11,20-trione), has been developed because of the observation that the replacement of the steroid D-ring by a methyl group changes (decreases) the Na+ retention characteristics of the compound (Rausser et al., 1966). The structure of prednisone, (II), has been determined by single-crystal X-ray crystallography, and the data have been deposited with the Cambridge Structural Database (CSD, Allen & Kennard, 1993) with refcode PRGDOL (Tseikinsky et al., 1979). The present work, which is part of an ongoing study aimed at the determination of the three-dimensional structures of biologically active compounds (Vega et al., 2001), reports on (I).
Compound (I) crystallized in the space group P21, with two independent molecules in the asymmetric unit (see Fig. 1). In the steroid nucleus, the A-ring is planar, whereas the other six-membered rings deviate significantly from planarity and adopt conformations close to chair. The Cremer & Pople (1975) ring puckering parameters are as follows for molecules (I)A and (I)B, respectively: for ring B, QT is 0.547 (4) and 0.562 (3) Å, θ2 is 174.9 (4) and 176.8 (3), and ϕ2 is 15 (4) and 126 (7)°, and for ring C, QT is 0.589 (4) and 0.583 (4) Å, θ2 is 170.4 (3) and 177.8 (3), and ϕ2 is 58 (2) and 68 (9)°. In these four rings, the asymmetry parameters indicate the presence of three mirror planes and a twofold axis that is typical of the ideal chair conformation (Duax et al., 1976). The five-membered D-ring is in a 13β, 14α half-chair conformation with ring puckering parameters of q2 = 0.454 (4) and 0.484 (4) Å and ϕ2 = 11.9 (4) and 12.8 (4)° [(I)A and (I)B, respectively], while the asymmetry parameters are DS(C13) = 0.075 (2) and 0.085 (2) and D2(C13–C14) = 0.026 (2) and 0.024 (2) for (I)A and (I)B, respectively.
A molecular superposition of (I)A on (I)B, using XP (Sheldrick, 1991), gave an r.m.s. deviation of 0.30 Å. As shown in Fig. 2, the molecules differ considerably at the location of atoms O3 (O3A—O3B deviation of 0.791 Å), O11 (0.479 Å) and O21 (0.459 Å). In (I)B, the mean plane of the A-ring is 43.76 (7)° from the least-squares C5···C17 reference plane (Duax et al., 1976); however, in (I)A the dihedral angle is 30.95 (8)°, and consequently O3B lies ca 1 Å further from the C5···C17 reference plane than O3A [2.708 (3) versus 1.743 (2) Å]. This dissimilarity could be an effect of the intermolecular interactions in which the O3 atoms take part. The donor···acceptor distances and the angles of the hydrogen bonds differ by 0.25 Å and 25° (Table 2), thus making the O3B interaction stronger than that of O3A. In (II), atom O3 is contacted weakly to a C atom (D···A = 3.379 Å, H···A = 2.615° and D—H···A 126°). Therefore, the geometry exhibited by molecule (I)A probably arises from the maximization of the O3A hydrogen-bond interaction by a decrease of the donor···acceptor distance, with the concomitant displacement of the A-ring (see also Fig. 3). The deviation of the C11 plane (C9—C11—C12—O11) is 2° greater with respect to the main plane of the chair (C8—C9—C12—C13) in (I)B than in (I)A, the dihedral angles being 52.66 (13)° and 50.61 (16)°, respectively. The weak C1···O11 and C19···O11 hydrogen bonds could exert an effect, but this circumstance seems unlikely because the bonds are comparable in both independent molecules (Table 2). Therefore, a distant effect caused by the corresponding A-ring could be the most plausible explanation. The orientation of the C20 plane (C17—C20—O20—C21) with respect to the C5—C17 reference plane agrees well in both independent molecules, the values of the dihedral angles being 70.9 (1)° and 70.5 (1)° [(I)A and (I)B, resepctively]; thus, O17A and O17B are separated from the C20 plane by 1.593 (2) Å and 1.752 (3) Å, respectively. Concerning the C20 plane, the orientation of O21, as indicated by the torsion angle O20—C20—C21—O21, is plus synperiplanar [6.2 (5)° and 3.8 (5)° for (I)A and (I)B, respectively]. From Table 2, it is evident that O21B, unlike O21A, participates in an intramolecular interaction with O20B, thus forming a five-membered ring.
The comparison of (I) and (II) in XP indicated that the latter is closer to (I)B than to (I)A, the r.m.s. deviations being 0.14 Å and 0.28 Å, respectively. In the superposition between (I)B and (II), the major differences were encountered within the O20—C20—C21—O21 chain, namely for atoms O20 (0.319 Å), C21 (0.255 Å) and O21 (0.248 Å). However, in the superposition with (I)A, the major deviations occurred for atoms O3 (0.824 Å), O20 (0.452 Å) and O11 (0.388 Å). As with (II), O20 is plus synclinal with respect to the C16—C17 bond, the C16—C17—C20—O20 torsion angles being 44.9 (4), 47.9 (2) and 33.2° [(I)A, (I)B and II,respectively]. Note that O20 is further from C16 in (I) than in (II), possibly as a result of the steric hindrance introduced on the O atom by the members of the methyl group. Very weak C—H···O hydrogen bonds can have an effect. The C18···O20 interactions could be regarded as attractive contacts (Table 2), whereas, because of the bent geometry, the C22···O20 interactions (average D···A = 2.872 Å, H···A = 2.609 Å and D—H···A = 96°) could be considered to be repulsive ones, so that the net effect is the enlargement of the O20···C16 distance in (I). In (II), there is a very weak C16···O20 hydrogen bond (D···A = 2.855 Å, H···A = 2.404 Å and D—H···A = 107°), which was not observed in (I).
The longitudinal twist of the steroid nucleus, measured by the value of the pseudo-torsion angle C19—C10···C13—C18 (Duax et al., 1976), is similar in both independent molecules [2.6 (3)° and 2.7 (3)° for (I)A and (I)B, respectively], and this angle is somewhat smaller than that in (II) [4.6°]. In addition, the mutual orientation between O17 and C18 is in good agreement in the three structures, as shown by the value of the torsion angle C18—C13—C17—O17 [164.6 (2), 166.7 (4) and 165.4° for (I)A, (I)B and (II)]. The structural cohesion in the crystal of (I) is achieved through O—H···O -type hydrogen bonds. As shown in Fig. 3, chains are formed by the two independent molecules, which are linked via O21B···O3A hydrogen bonds, and by the two molecules and translated neighbors via O17A···O3B(x − 1, y + 1, z − 1) hydrogen bonds. The chains are propagated by O21A···O17A(-x, y + 1/2, −z) and O17B···O21B(-x + 1, y − 1/2, −z + 1) hydrogen bonds through the crystallographic twofold axis. The propagation direction is nearly perpendicular to the largest dimension of the steroid, and thus the chains are arranged into planes parallel to the b axis.