Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807059545/bt2615sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807059545/bt2615Isup2.hkl |
CCDC reference: 673037
Key indicators
- Single-crystal X-ray study
- T = 166 K
- Mean (C-C) = 0.004 Å
- R factor = 0.042
- wR factor = 0.114
- Data-to-parameter ratio = 10.9
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT220_ALERT_2_B Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.61 Ratio PLAT222_ALERT_3_B Large Non-Solvent H Ueq(max)/Ueq(min) ... 4.20 Ratio
Alert level C PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 3
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 28.01 From the CIF: _reflns_number_total 3595 Count of symmetry unique reflns 3634 Completeness (_total/calc) 98.93% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4 ... S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C5 ... R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C6 ... S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C8 ... S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C9 ... R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C10 ... S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C12 ... S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C13 ... S
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 9 ALERT level G = General alerts; check 8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Auphan (1995); Beato (1995); Besedovsky (1986); Näther & Je\&s (2006); Suitchmezian et al. (2006a,b,c); Winiski et al. (2007).
Betamethasone valerate (9-Fluor-11β,21-dihydroxy-16β-methyl-3,20 -dioxypregna-1,4-dien-17-ylpentanoat) was obtained from Symbiotec Pharmalab (India) as an enantiomeric pure compound. This compound was recrystallized at 70°C in an teflon lined steel autoclave. On cooling, single crystals of the title compound were obtained. The product is obtained as a pure phase, which was proven by comparison of the experimental X-ray powder pattern with that, calculated from single-crystal data.
The C—H hydrogen atoms were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined with fixed isotropic displacement parameters [Uiso(H)= 1.2*Ueq(C) or 1.5*Ueq(C) for methyl groups] using a riding model with d(C—H) = 0.95 Å for olefin, 1.00 Å for methin, 0.99 Å for methylen and 0.98 Å for methyl H atoms. The position of the hydroxyl hydrogen atoms were located in difference map but they were positioned with idealized geometry allowed to rotate but not to tip with d(O—H) = 0.84 Å and refined with fixed isotropic displacement parameters [Uiso(H)= 1.5*Ueq(O)] using a riding model. Because no strong anomalous scattering atoms are present, the absolute structure and absolute configuration cannot be determined. Therefore, Friedel opposites were merged prior to refinement and the absolute configuration was assigned base on the known absolute configuration of the starting material.
Data collection: IPDS (Stoe & Cie, 1998); cell refinement: IPDS (Stoe & Cie, 1998); data reduction: IPDS (Stoe & Cie, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1998); software used to prepare material for publication: CIFTAB in SHELXTL (Bruker AXS, 1998).
C27H37FO6·CH4O | Dx = 1.261 Mg m−3 Dm = N Mg m−3 Dm measured by not measured |
Mr = 508.61 | Melting point: not measured K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.9980 (5) Å | Cell parameters from 16982 reflections |
b = 15.7885 (9) Å | θ = 2.4–28.0° |
c = 16.9696 (12) Å | µ = 0.09 mm−1 |
V = 2678.7 (3) Å3 | T = 166 K |
Z = 4 | Needles, colorless |
F(000) = 1096 | 0.15 × 0.10 × 0.04 mm |
STOE IPDS-1 diffractometer | 3009 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.049 |
Graphite monochromator | θmax = 28.0°, θmin = 2.4° |
Phi scans | h = −13→12 |
16982 measured reflections | k = −19→20 |
3595 independent reflections | l = −22→22 |
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)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.0728P)2 + 0.2844P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
3595 reflections | Δρmax = 0.37 e Å−3 |
330 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.015 (3) |
C27H37FO6·CH4O | V = 2678.7 (3) Å3 |
Mr = 508.61 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.9980 (5) Å | µ = 0.09 mm−1 |
b = 15.7885 (9) Å | T = 166 K |
c = 16.9696 (12) Å | 0.15 × 0.10 × 0.04 mm |
STOE IPDS-1 diffractometer | 3009 reflections with I > 2σ(I) |
16982 measured reflections | Rint = 0.049 |
3595 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.37 e Å−3 |
3595 reflections | Δρmin = −0.17 e Å−3 |
330 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 | 0.4547 (2) | 0.35867 (12) | 0.46094 (11) | 0.0447 (5) | |
O2 | 0.7591 (2) | 0.33239 (10) | 0.10538 (10) | 0.0341 (4) | |
H1O1 | 0.7493 | 0.3492 | 0.0588 | 0.051* | |
O3 | 0.86752 (19) | 0.07486 (12) | −0.10976 (11) | 0.0373 (4) | |
O4 | 0.6562 (2) | 0.11246 (12) | −0.19919 (10) | 0.0395 (4) | |
O5 | 0.60803 (17) | 0.02899 (11) | 0.02422 (11) | 0.0339 (4) | |
H1O5 | 0.6045 | −0.0240 | 0.0281 | 0.051* | |
O6 | 0.6920 (3) | 0.23945 (14) | −0.14560 (12) | 0.0545 (6) | |
O7 | 0.2372 (3) | 0.11731 (13) | 0.05510 (12) | 0.0538 (6) | |
H1O7 | 0.2171 | 0.1575 | 0.0853 | 0.081* | |
F1 | 0.56997 (13) | 0.19207 (9) | 0.22638 (8) | 0.0293 (3) | |
C1 | 0.5279 (3) | 0.34132 (15) | 0.40401 (14) | 0.0321 (5) | |
C2 | 0.5175 (3) | 0.38628 (15) | 0.32881 (14) | 0.0299 (5) | |
H2 | 0.4524 | 0.4296 | 0.3228 | 0.036* | |
C3 | 0.5977 (3) | 0.36759 (14) | 0.26878 (14) | 0.0286 (5) | |
H3 | 0.5844 | 0.3969 | 0.2205 | 0.034* | |
C4 | 0.7082 (2) | 0.30293 (16) | 0.27228 (13) | 0.0296 (5) | |
C5 | 0.6905 (2) | 0.23474 (14) | 0.20552 (12) | 0.0244 (4) | |
C6 | 0.6600 (2) | 0.27067 (14) | 0.12304 (12) | 0.0252 (4) | |
H6 | 0.5718 | 0.3003 | 0.1259 | 0.030* | |
C7 | 0.6487 (2) | 0.20086 (14) | 0.06002 (13) | 0.0247 (4) | |
H7A | 0.5648 | 0.1689 | 0.0687 | 0.030* | |
H7B | 0.6431 | 0.2277 | 0.0074 | 0.030* | |
C8 | 0.7664 (2) | 0.13873 (13) | 0.06056 (12) | 0.0233 (4) | |
C9 | 0.7443 (2) | 0.05480 (14) | 0.01248 (13) | 0.0264 (5) | |
C10 | 0.8411 (3) | −0.01119 (15) | 0.05322 (15) | 0.0328 (5) | |
H10 | 0.7855 | −0.0621 | 0.0656 | 0.039* | |
C11 | 0.8794 (3) | 0.02912 (16) | 0.13355 (14) | 0.0331 (5) | |
H11A | 0.8719 | −0.0128 | 0.1767 | 0.040* | |
H11B | 0.9719 | 0.0514 | 0.1323 | 0.040* | |
C12 | 0.7776 (2) | 0.10131 (14) | 0.14435 (13) | 0.0265 (5) | |
H12 | 0.6896 | 0.0742 | 0.1565 | 0.032* | |
C13 | 0.8021 (2) | 0.16737 (15) | 0.20797 (13) | 0.0288 (5) | |
H13 | 0.8897 | 0.1957 | 0.1973 | 0.035* | |
C14 | 0.8090 (3) | 0.12488 (18) | 0.28931 (14) | 0.0397 (6) | |
H14A | 0.8886 | 0.0876 | 0.2912 | 0.048* | |
H14B | 0.7288 | 0.0889 | 0.2965 | 0.048* | |
C15 | 0.8168 (3) | 0.1888 (2) | 0.35744 (15) | 0.0459 (7) | |
H15A | 0.8055 | 0.1585 | 0.4081 | 0.055* | |
H15B | 0.9062 | 0.2158 | 0.3576 | 0.055* | |
C16 | 0.7115 (3) | 0.25614 (17) | 0.35066 (14) | 0.0331 (5) | |
C17 | 0.6280 (3) | 0.27433 (17) | 0.40949 (14) | 0.0347 (6) | |
H17 | 0.6339 | 0.2424 | 0.4568 | 0.042* | |
C18 | 0.8407 (3) | 0.35432 (19) | 0.26525 (16) | 0.0401 (6) | |
H18A | 0.9170 | 0.3155 | 0.2676 | 0.060* | |
H18B | 0.8464 | 0.3950 | 0.3087 | 0.060* | |
H18C | 0.8419 | 0.3848 | 0.2150 | 0.060* | |
C19 | 0.8963 (2) | 0.18166 (14) | 0.03324 (13) | 0.0267 (4) | |
H19A | 0.9695 | 0.1404 | 0.0341 | 0.040* | |
H19B | 0.9176 | 0.2288 | 0.0687 | 0.040* | |
H19C | 0.8847 | 0.2032 | −0.0205 | 0.040* | |
C20 | 0.9629 (3) | −0.04336 (18) | 0.00755 (17) | 0.0410 (6) | |
H20A | 0.9336 | −0.0683 | −0.0424 | 0.062* | |
H20B | 1.0095 | −0.0863 | 0.0389 | 0.062* | |
H20C | 1.0237 | 0.0040 | −0.0031 | 0.062* | |
C21 | 0.7607 (3) | 0.06993 (14) | −0.07560 (13) | 0.0293 (5) | |
C22 | 0.6305 (3) | 0.08233 (18) | −0.12067 (15) | 0.0359 (6) | |
H22A | 0.5816 | 0.0279 | −0.1233 | 0.043* | |
H22B | 0.5735 | 0.1236 | −0.0924 | 0.043* | |
C23 | 0.6882 (3) | 0.19431 (19) | −0.20325 (16) | 0.0395 (6) | |
C24 | 0.7145 (3) | 0.2230 (2) | −0.28574 (17) | 0.0492 (8) | |
H24A | 0.6439 | 0.1999 | −0.3206 | 0.059* | |
H24B | 0.8012 | 0.1994 | −0.3034 | 0.059* | |
C25 | 0.7181 (3) | 0.3179 (2) | −0.29465 (18) | 0.0492 (7) | |
H25A | 0.6345 | 0.3417 | −0.2726 | 0.059* | |
H25B | 0.7935 | 0.3403 | −0.2631 | 0.059* | |
C26 | 0.7331 (5) | 0.3483 (2) | −0.37817 (19) | 0.0616 (9) | |
H26A | 0.8181 | 0.3262 | −0.3999 | 0.074* | |
H26B | 0.6591 | 0.3249 | −0.4103 | 0.074* | |
C27 | 0.7325 (6) | 0.4429 (3) | −0.3852 (3) | 0.0842 (14) | |
H27A | 0.7415 | 0.4589 | −0.4408 | 0.126* | |
H27B | 0.8075 | 0.4664 | −0.3551 | 0.126* | |
H27C | 0.6482 | 0.4652 | −0.3644 | 0.126* | |
C28 | 0.3002 (3) | 0.0530 (2) | 0.09857 (19) | 0.0468 (7) | |
H28A | 0.3839 | 0.0746 | 0.1209 | 0.070* | |
H28B | 0.3195 | 0.0049 | 0.0639 | 0.070* | |
H28C | 0.2410 | 0.0345 | 0.1413 | 0.070* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0559 (13) | 0.0369 (9) | 0.0414 (10) | 0.0089 (9) | 0.0246 (9) | 0.0001 (8) |
O2 | 0.0466 (11) | 0.0262 (8) | 0.0294 (8) | −0.0058 (8) | 0.0022 (8) | 0.0026 (6) |
O3 | 0.0330 (10) | 0.0468 (11) | 0.0322 (9) | 0.0017 (8) | 0.0091 (7) | −0.0023 (8) |
O4 | 0.0453 (11) | 0.0422 (10) | 0.0309 (9) | 0.0044 (9) | −0.0036 (8) | −0.0048 (8) |
O5 | 0.0265 (9) | 0.0286 (8) | 0.0467 (10) | −0.0063 (7) | 0.0078 (7) | −0.0001 (8) |
O6 | 0.0805 (17) | 0.0417 (11) | 0.0412 (11) | −0.0009 (11) | 0.0090 (11) | −0.0043 (9) |
O7 | 0.0847 (17) | 0.0376 (10) | 0.0392 (10) | 0.0193 (11) | −0.0032 (11) | 0.0084 (8) |
F1 | 0.0257 (7) | 0.0326 (7) | 0.0295 (7) | 0.0000 (6) | 0.0054 (5) | 0.0035 (5) |
C1 | 0.0343 (13) | 0.0287 (11) | 0.0333 (12) | 0.0015 (10) | 0.0064 (10) | −0.0052 (9) |
C2 | 0.0299 (13) | 0.0234 (10) | 0.0366 (12) | 0.0041 (9) | 0.0015 (10) | −0.0032 (9) |
C3 | 0.0311 (12) | 0.0261 (10) | 0.0284 (11) | −0.0004 (9) | −0.0020 (9) | −0.0015 (9) |
C4 | 0.0273 (12) | 0.0370 (12) | 0.0245 (10) | 0.0042 (10) | 0.0009 (8) | −0.0014 (9) |
C5 | 0.0221 (11) | 0.0283 (10) | 0.0228 (9) | 0.0003 (9) | 0.0029 (8) | 0.0023 (8) |
C6 | 0.0254 (11) | 0.0259 (10) | 0.0243 (10) | 0.0048 (9) | 0.0002 (8) | 0.0023 (8) |
C7 | 0.0240 (11) | 0.0271 (10) | 0.0230 (9) | 0.0030 (9) | −0.0003 (8) | 0.0023 (8) |
C8 | 0.0221 (11) | 0.0241 (9) | 0.0237 (9) | 0.0023 (8) | 0.0027 (8) | 0.0023 (8) |
C9 | 0.0233 (11) | 0.0246 (10) | 0.0314 (11) | −0.0010 (9) | 0.0057 (9) | 0.0001 (8) |
C10 | 0.0320 (13) | 0.0263 (11) | 0.0402 (13) | 0.0047 (10) | 0.0076 (10) | 0.0027 (9) |
C11 | 0.0348 (14) | 0.0309 (11) | 0.0336 (12) | 0.0128 (10) | 0.0039 (10) | 0.0059 (9) |
C12 | 0.0269 (12) | 0.0263 (10) | 0.0263 (10) | 0.0058 (9) | 0.0042 (9) | 0.0048 (8) |
C13 | 0.0268 (12) | 0.0354 (12) | 0.0243 (10) | 0.0094 (9) | 0.0004 (9) | 0.0033 (9) |
C14 | 0.0453 (16) | 0.0471 (15) | 0.0267 (11) | 0.0214 (13) | −0.0002 (11) | 0.0070 (10) |
C15 | 0.0485 (17) | 0.0626 (18) | 0.0266 (11) | 0.0278 (15) | −0.0038 (11) | 0.0038 (12) |
C16 | 0.0343 (14) | 0.0396 (13) | 0.0255 (11) | 0.0092 (11) | −0.0037 (9) | −0.0015 (10) |
C17 | 0.0448 (15) | 0.0361 (13) | 0.0233 (10) | 0.0066 (11) | 0.0021 (10) | −0.0013 (9) |
C18 | 0.0303 (14) | 0.0520 (16) | 0.0381 (13) | −0.0047 (12) | −0.0011 (11) | −0.0109 (12) |
C19 | 0.0248 (11) | 0.0281 (11) | 0.0272 (10) | −0.0024 (9) | 0.0022 (8) | 0.0015 (9) |
C20 | 0.0403 (15) | 0.0383 (14) | 0.0444 (14) | 0.0138 (12) | 0.0049 (12) | −0.0032 (11) |
C21 | 0.0321 (13) | 0.0254 (10) | 0.0306 (11) | −0.0016 (9) | 0.0042 (9) | −0.0048 (8) |
C22 | 0.0342 (14) | 0.0407 (13) | 0.0328 (12) | 0.0001 (11) | 0.0010 (10) | −0.0056 (10) |
C23 | 0.0354 (14) | 0.0465 (15) | 0.0365 (13) | 0.0094 (12) | 0.0024 (11) | −0.0023 (11) |
C24 | 0.0498 (19) | 0.0592 (18) | 0.0386 (14) | 0.0138 (15) | 0.0078 (13) | 0.0033 (13) |
C25 | 0.0459 (18) | 0.0598 (18) | 0.0419 (15) | −0.0004 (15) | 0.0050 (13) | −0.0012 (13) |
C26 | 0.069 (2) | 0.071 (2) | 0.0439 (16) | 0.002 (2) | 0.0097 (17) | 0.0088 (15) |
C27 | 0.093 (3) | 0.070 (2) | 0.089 (3) | 0.008 (3) | 0.026 (3) | 0.034 (2) |
C28 | 0.0436 (17) | 0.0467 (15) | 0.0502 (16) | 0.0134 (13) | 0.0040 (13) | 0.0122 (13) |
O1—C1 | 1.243 (3) | C12—H12 | 1.0000 |
O2—C6 | 1.421 (3) | C13—C14 | 1.536 (3) |
O2—H1O1 | 0.8400 | C13—H13 | 1.0000 |
O3—C21 | 1.217 (3) | C14—C15 | 1.537 (4) |
O4—C23 | 1.333 (4) | C14—H14A | 0.9900 |
O4—C22 | 1.438 (3) | C14—H14B | 0.9900 |
O5—C9 | 1.436 (3) | C15—C16 | 1.499 (4) |
O5—H1O5 | 0.8400 | C15—H15A | 0.9900 |
O6—C23 | 1.211 (3) | C15—H15B | 0.9900 |
O7—C28 | 1.404 (3) | C16—C17 | 1.333 (3) |
O7—H1O7 | 0.8400 | C17—H17 | 0.9500 |
F1—C5 | 1.426 (3) | C18—H18A | 0.9800 |
C1—C17 | 1.459 (4) | C18—H18B | 0.9800 |
C1—C2 | 1.464 (3) | C18—H18C | 0.9800 |
C2—C3 | 1.329 (3) | C19—H19A | 0.9800 |
C2—H2 | 0.9500 | C19—H19B | 0.9800 |
C3—C4 | 1.505 (3) | C19—H19C | 0.9800 |
C3—H3 | 0.9500 | C20—H20A | 0.9800 |
C4—C16 | 1.522 (3) | C20—H20B | 0.9800 |
C4—C18 | 1.558 (4) | C20—H20C | 0.9800 |
C4—C5 | 1.573 (3) | C21—C22 | 1.523 (4) |
C5—C6 | 1.541 (3) | C22—H22A | 0.9900 |
C5—C13 | 1.542 (3) | C22—H22B | 0.9900 |
C6—C7 | 1.540 (3) | C23—C24 | 1.495 (4) |
C6—H6 | 1.0000 | C24—C25 | 1.506 (5) |
C7—C8 | 1.532 (3) | C24—H24A | 0.9900 |
C7—H7A | 0.9900 | C24—H24B | 0.9900 |
C7—H7B | 0.9900 | C25—C26 | 1.504 (4) |
C8—C19 | 1.537 (3) | C25—H25A | 0.9900 |
C8—C12 | 1.544 (3) | C25—H25B | 0.9900 |
C8—C9 | 1.572 (3) | C26—C27 | 1.498 (6) |
C9—C21 | 1.523 (3) | C26—H26A | 0.9900 |
C9—C10 | 1.581 (3) | C26—H26B | 0.9900 |
C10—C20 | 1.531 (4) | C27—H27A | 0.9800 |
C10—C11 | 1.552 (4) | C27—H27B | 0.9800 |
C10—H10 | 1.0000 | C27—H27C | 0.9800 |
C11—C12 | 1.539 (3) | C28—H28A | 0.9800 |
C11—H11A | 0.9900 | C28—H28B | 0.9800 |
C11—H11B | 0.9900 | C28—H28C | 0.9800 |
C12—C13 | 1.521 (3) | ||
C6—O2—H1O1 | 109.5 | C13—C14—H14B | 109.0 |
C23—O4—C22 | 114.3 (2) | C15—C14—H14B | 109.0 |
C9—O5—H1O5 | 109.5 | H14A—C14—H14B | 107.8 |
C28—O7—H1O7 | 109.5 | C16—C15—C14 | 111.9 (2) |
O1—C1—C17 | 120.9 (2) | C16—C15—H15A | 109.2 |
O1—C1—C2 | 121.9 (2) | C14—C15—H15A | 109.2 |
C17—C1—C2 | 117.1 (2) | C16—C15—H15B | 109.2 |
C3—C2—C1 | 121.2 (2) | C14—C15—H15B | 109.2 |
C3—C2—H2 | 119.4 | H15A—C15—H15B | 107.9 |
C1—C2—H2 | 119.4 | C17—C16—C15 | 122.3 (2) |
C2—C3—C4 | 124.3 (2) | C17—C16—C4 | 122.4 (2) |
C2—C3—H3 | 117.9 | C15—C16—C4 | 115.2 (2) |
C4—C3—H3 | 117.9 | C16—C17—C1 | 122.6 (2) |
C3—C4—C16 | 112.32 (19) | C16—C17—H17 | 118.7 |
C3—C4—C18 | 105.5 (2) | C1—C17—H17 | 118.7 |
C16—C4—C18 | 107.5 (2) | C4—C18—H18A | 109.5 |
C3—C4—C5 | 110.70 (19) | C4—C18—H18B | 109.5 |
C16—C4—C5 | 107.44 (19) | H18A—C18—H18B | 109.5 |
C18—C4—C5 | 113.38 (19) | C4—C18—H18C | 109.5 |
F1—C5—C6 | 103.42 (17) | H18A—C18—H18C | 109.5 |
F1—C5—C13 | 106.20 (17) | H18B—C18—H18C | 109.5 |
C6—C5—C13 | 114.95 (18) | C8—C19—H19A | 109.5 |
F1—C5—C4 | 103.86 (16) | C8—C19—H19B | 109.5 |
C6—C5—C4 | 115.12 (18) | H19A—C19—H19B | 109.5 |
C13—C5—C4 | 111.82 (18) | C8—C19—H19C | 109.5 |
O2—C6—C7 | 113.29 (18) | H19A—C19—H19C | 109.5 |
O2—C6—C5 | 107.81 (18) | H19B—C19—H19C | 109.5 |
C7—C6—C5 | 112.45 (18) | C10—C20—H20A | 109.5 |
O2—C6—H6 | 107.7 | C10—C20—H20B | 109.5 |
C7—C6—H6 | 107.7 | H20A—C20—H20B | 109.5 |
C5—C6—H6 | 107.7 | C10—C20—H20C | 109.5 |
C8—C7—C6 | 113.44 (18) | H20A—C20—H20C | 109.5 |
C8—C7—H7A | 108.9 | H20B—C20—H20C | 109.5 |
C6—C7—H7A | 108.9 | O3—C21—C9 | 124.9 (2) |
C8—C7—H7B | 108.9 | O3—C21—C22 | 120.2 (2) |
C6—C7—H7B | 108.9 | C9—C21—C22 | 114.9 (2) |
H7A—C7—H7B | 107.7 | O4—C22—C21 | 110.8 (2) |
C7—C8—C19 | 111.41 (17) | O4—C22—H22A | 109.5 |
C7—C8—C12 | 107.84 (17) | C21—C22—H22A | 109.5 |
C19—C8—C12 | 112.66 (18) | O4—C22—H22B | 109.5 |
C7—C8—C9 | 115.37 (19) | C21—C22—H22B | 109.5 |
C19—C8—C9 | 109.53 (17) | H22A—C22—H22B | 108.1 |
C12—C8—C9 | 99.53 (16) | O6—C23—O4 | 122.4 (3) |
O5—C9—C21 | 106.5 (2) | O6—C23—C24 | 124.9 (3) |
O5—C9—C8 | 107.51 (18) | O4—C23—C24 | 112.6 (2) |
C21—C9—C8 | 111.22 (17) | C23—C24—C25 | 113.6 (3) |
O5—C9—C10 | 109.46 (18) | C23—C24—H24A | 108.9 |
C21—C9—C10 | 117.8 (2) | C25—C24—H24A | 108.9 |
C8—C9—C10 | 104.02 (19) | C23—C24—H24B | 108.9 |
C20—C10—C11 | 112.6 (2) | C25—C24—H24B | 108.9 |
C20—C10—C9 | 119.0 (2) | H24A—C24—H24B | 107.7 |
C11—C10—C9 | 105.36 (18) | C26—C25—C24 | 114.5 (3) |
C20—C10—H10 | 106.4 | C26—C25—H25A | 108.6 |
C11—C10—H10 | 106.4 | C24—C25—H25A | 108.6 |
C9—C10—H10 | 106.4 | C26—C25—H25B | 108.6 |
C12—C11—C10 | 104.20 (19) | C24—C25—H25B | 108.6 |
C12—C11—H11A | 110.9 | H25A—C25—H25B | 107.6 |
C10—C11—H11A | 110.9 | C27—C26—C25 | 113.1 (3) |
C12—C11—H11B | 110.9 | C27—C26—H26A | 109.0 |
C10—C11—H11B | 110.9 | C25—C26—H26A | 109.0 |
H11A—C11—H11B | 108.9 | C27—C26—H26B | 109.0 |
C13—C12—C11 | 119.1 (2) | C25—C26—H26B | 109.0 |
C13—C12—C8 | 113.76 (18) | H26A—C26—H26B | 107.8 |
C11—C12—C8 | 102.81 (17) | C26—C27—H27A | 109.5 |
C13—C12—H12 | 106.8 | C26—C27—H27B | 109.5 |
C11—C12—H12 | 106.8 | H27A—C27—H27B | 109.5 |
C8—C12—H12 | 106.8 | C26—C27—H27C | 109.5 |
C12—C13—C14 | 110.2 (2) | H27A—C27—H27C | 109.5 |
C12—C13—C5 | 109.73 (19) | H27B—C27—H27C | 109.5 |
C14—C13—C5 | 110.97 (19) | O7—C28—H28A | 109.5 |
C12—C13—H13 | 108.6 | O7—C28—H28B | 109.5 |
C14—C13—H13 | 108.6 | H28A—C28—H28B | 109.5 |
C5—C13—H13 | 108.6 | O7—C28—H28C | 109.5 |
C13—C14—C15 | 113.0 (2) | H28A—C28—H28C | 109.5 |
C13—C14—H14A | 109.0 | H28B—C28—H28C | 109.5 |
C15—C14—H14A | 109.0 |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1O1···O7i | 0.84 | 2.01 | 2.845 (3) | 176 |
O5—H1O5···O1ii | 0.84 | 1.95 | 2.773 (2) | 165 |
O7—H1O7···O6iii | 0.84 | 1.94 | 2.771 (3) | 171 |
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) −x+1, y−1/2, −z+1/2; (iii) x−1/2, −y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C27H37FO6·CH4O |
Mr | 508.61 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 166 |
a, b, c (Å) | 9.9980 (5), 15.7885 (9), 16.9696 (12) |
V (Å3) | 2678.7 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.15 × 0.10 × 0.04 |
Data collection | |
Diffractometer | STOE IPDS1 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16982, 3595, 3009 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.114, 1.03 |
No. of reflections | 3595 |
No. of parameters | 330 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.17 |
Computer programs: IPDS (Stoe & Cie, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Bruker, 1998), CIFTAB in SHELXTL (Bruker AXS, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1O1···O7i | 0.84 | 2.01 | 2.845 (3) | 175.5 |
O5—H1O5···O1ii | 0.84 | 1.95 | 2.773 (2) | 164.7 |
O7—H1O7···O6iii | 0.84 | 1.94 | 2.771 (3) | 170.8 |
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) −x+1, y−1/2, −z+1/2; (iii) x−1/2, −y+1/2, −z. |
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Glucocorticoids belong to the most effective drugs against inflammatory and auto immune deseases (Auphan, 1995; Besedovsky, 1986; Beato, 1995; Winiski et al., 2007). Surprisingly, their polymorphism is only minor investigated. Therefore, we started systematic investigations on the polymorphism and pseudopolymorphism of these drugs (Suitchmezian et al., 2006a; Suitchmezian et al., 2006b; Suitchmezian et al., 2006c; Näther et al., 2006).
Within this project we also investigated betamethasone valerate, also known as 9-fluoro-11β,21-dihydroxy-16β-methyl-3,20 -dioxypregna-1,4-dien-17-ylpentanoat, (II) (see Fig 3). For this compound we found an methanol solvate, which is still unknown. During our attempts to crystallize this solvate at higher temperatures, we obtained single crystals of the title compound, (I), which formed by a movement of the pentanoat group to position 21. To identify this product in all further investigations by X-ray powder diffraction, the single-crystal structure of this solvate was determined.
In the crystal structure of the title compound, (I), (Fig. 1) the molecules are connected via O—H ··· O hydrogen bonding between the hydroxyl hydrogen atom at O5 and the carbonyl oxygen atom O1 (Tab.1). The molecules are additionally connected by O—H···O hydrogen bonding between the hydroxyl hydrogen atom at O2 and the hydroxyl oxygen atom O7 of the solvent molecules and between the hydroxyl hydrogen atom attached to O7 and the carbonyl oxygen atom O6 (Fig. 2). This, the methanol molecules act as acceptors and donors. In the direction of the a axis channels are formed in which the methanol molecules are located (Fig. 2).