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The title keto acid crystallizes as a solvate, C21H25FO4·C2H4O2, with two mol­ecules each of steroid and acetic acid per asymmetric unit. The former are approximately parallel, with opposite end-to-end orientation, and form translational carboxyl-to-ketone hydrogen-bonding catemers [O...O = 2.679 (6) and 2.650 (5) Å, and O—H...O = 165 and 162°] that involve the 3-ketone group and follow the a axis. The acetic acid mol­ecules are paired by hydrogen bonding, and neither they nor the F atom nor the 11-ketone group play any overt role in the hydrogen-bonding scheme of the steroid. Intermolecular C—H...O=C close contacts involving three different neighboring mol­ecules exist to the 11-ketone group, the steroidal carboxyl group and one of the acetic acid molecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103007121/fr1413sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103007121/fr1413Isup2.hkl
Contains datablock I

CCDC reference: 214181

Comment top

In keto carboxylic acids, centrosymmetric acid pairing that excludes the ketone dominates the hydrogen-bonding modes. However, in chiral non-racemates, that prevalence yields to non-centrosymmetric patterns and, particularly when significant conformational restrictions are present, the incidence of acid-to-ketone catemers rises dramatically (Brunskill et al., 1997). In our study of these hydrogen-bonding modes we have therefore often sought keto acids with terpenoid origins as subject materials, and we now report the crystal structure and hydrogen-bonding behavior of the title steroid, (I). Compound (I) is related to a synthetic anti-inflammatory glucocorticoid and is the ninth in our series of steroidal keto acid structures.

Fig. 1 shows the asymmetric unit with its steroid numbering. The second molecule, (I'), oriented approximately parallel to (I), has primed numbering. (I') differs from (I) only by rotation of the acid about the C17—C20 bond, the only significant conformational option present. The carboxyl group in both (I) and (I') is turned so that the C16—C17 bond lies near the carboxyl plane, with the CO bond turned toward C16. In (I), the C16—C17—C20—O3 torsion angle is −12.6 (9)°, while in (I') it is −2.5 (9)°. The dihedral angle between the carboxyl (C17—C20—O3—O4) and ketone planes (C2—C3—C4—O1) is 14.2 (4)° for (I) and 9.8 (4)° for (I'). In both (I) and (I'), the three angular methyl groups are all staggered relative to the C atoms to which they are attached (C10, C13 and C16), without discernible disorder. The A-ring is highly planar (Thompson et al., 1999), with none of its six C atoms deviating from the average plane by more than 0.032 (4) Å in either (I) or (I').

Complete or partial averaging of C—O bond lengths and C—C—O angles by disorder is frequent in carboxyl dimers (Leiserowitz, 1976), but cannot occur in catemeric hydrogen bonding, whose geometry precludes the disordering processes. In (I), these lengths are 1.195 (7) and 1.335 (8) Å, with angles of 126.8 (7) and 111.4 (6)°; the lengths are 1.208 (7) and 1.333 (7) Å and the angles are 125.3 (6) and 112.9 (5)° for (I'). Our own survey of 56 keto acid structures that are not acid dimers gives average values of 1.200 (10) and 1.32 (2) Å and 124.5 (14) and 112.7 (17)° for these lengths and angles, in agreement with typical values of 1.21 and 1.31 Å and 123 and 112° cited for highly ordered dimeric carboxyl groups (Borthwick, 1980). The acetic acid molecules are paired, by hydrogen bonding, as dimers in which disorder is possible. However, by the usual criterion of averaging or partial averaging in C—O bond lengths and C—C—O angles, one of the acetic acid molecules appears significantly more ordered than the other. In (I), these lengths are 1.201 (9) and 1.270 (10) Å, with angles of 121.2 (9) and 116.3 (8)°, while in (I'), the lengths are 1.238 (9) and 1.268 (11) Å and the angles are 120.7 (9) and 116.9 (9)°. In the absence of any obvious mechanism by which two coupled halves of such a dimer might display different degrees of disorder, the significance of these differences is not apparent.

Fig. 2 shows one of the two asymmetric units within the cell, with extracellular molecules included to illustrate the counter-directional hydrogen-bonding chains created by the catemeric acid- to-ketone hydrogen bonding among translationally related molecules [O···O = 2.679 (6) and 2.650 (5) Å for (I) and (I'), respectively; O—H···O = 165.2 and 161.6° for (I) and (I'), respectively]. The second asymmetric unit (not shown) is screw-related to the first (in b) and generates a second pair of catemers screw-related to those shown. The net result is two translational chains of molecules oriented in each direction along a, including one counter-directional pair of catemers of type (I) and another pair of type (I').

Except for the complexity arising here because Z' is 2, this catemeric hydrogen-bonding arrangement closely resembles those found for 3-oxoandrosta-1,4-diene-17β-carboxylic acid (Thompson et al., 1999) and 3,11-dioxoandrost-4-ene-17β-carboxylic acid (Newman et al., 2002), which share important structural features with (I). In both those cases, as in (I), hydrogen bonding extends catemerically from the carboxyl to the 3-ketone group, and the units of the hydrogen-bonding chain are translationally related. Because the catemers in (I) are translational, the intermolecular dihedral angle between the ketone and carboxyl planes for each hydrogen bond is the same as the corresponding intramolecular dihedral angle.

Neither the acetic acid molecule nor the F atom plays any obvious role in the steroid's hydrogen-bonding scheme. It appears that the acetic acid serves to fill a void left by the stacking and hydrogen bonding of the steroid molecules. This idea is reinforced by the apparent ease with which (I) loses solvent, as evidenced by the odor of acetic acid that accumulates in closed vials of (I). The occupancy of the acetic acid molecules in (I) was 0.969 (6), based on refinement optimization for all atoms in both acetic acid molecules. The observed hydrogen bonding involves only the A-ring ketone, with the 11-keto function also playing no part in the hydrogen bonding. We have now examined 3-ketosteroids with additional ketone functionality at either the 6- (B-ring) or the 11-position (C-ring) but have yet to observe any involvement of those functions in the hydrogen-bonding schemes.

Within the 2.7 Å range, which we employ as our standard criterion (Steiner, 1997)?, three non-bonded intermolecular C—H···OC packing interactions exist for molecule (I) of the steroid, one for the C-ring ketone (2.66 Å to H7'B in a screw-related neighbor) and two for the carboxyl group (2.68 Å to H23F and 2.60 Å to H4A in different translationally related neighbors). In addition, molecule (I') has a 2.57 Å contact between O3' and H4'A in a translationally related neighbor. Two close contacts exist for O5' in acetic acid (2.67 Å to H7B and 2.63 Å to H12B to neighbors related by a translation and a screw, respectively). Using compiled data for a large number of C—H···O contacts, Steiner & Desiraju (1998) have found significant statistical directionality, even as far out as 3.0 Å, and conclude that these are legitimately viewed as `weak hydrogen bonds', with a greater contribution to packing forces than simple van der Waals attractions.

The solid-state (KBr) infrared spectrum of (I) displays absorption at 1720 (COOH and 11-ketone) and 1662 cm−1 (3-ketone), with alkene absorption at 1610 cm−1. In CHCl3 solution, these peaks appear at 1723, 1667 and 1630 cm−1.

Experimental top

Compound (I), not previously reported, is related to dexamethasone, a synthetic anti-inflammatory glucocorticoid. (+)-9α-Fluoro-11β,21-dihydroxy-16α-methyl-3,20-dioxopregna- 1,4-diene (21-deoxydexamethasone), of known relative and absolute stereochemistry (Dupont, et al., 1974; Joly, et al., 1974), was purchased from Steraloids Inc., Newport, RI, USA, and subjected to cleavage by sodium periodate in aqueous dioxane. Jones oxidation of the resulting hydroxy acid yielded (I), which was crystallized from acetic acid (mp 563 K, with loss of acetic acid and whitening from lower temperatures).

Refinement top

Friedel-related data were averaged. All steroid H atoms for (I) and (I') were found in electron-density difference maps, but H atoms bound to C atoms were placed in calculated positions? (0.97 Å for methylene H atoms, 0.98 Å for methine H atoms, 0.93 Å for vinyl H atoms and 0.96 Å for methyl H atoms) and allowed to refine as riding atoms on their respective C atoms. The displacement parameters of these H atoms were fixed at 1.2Ueq of their respective C atoms. For each acetic acid molecule, the carboxyl H atom and one methyl H atom were found in electron-density difference maps; the remaining methyl H atoms were generated geometrically. Methyl H atoms were placed 0.96 Å from the methyl C atoms, and carboxyl H atoms were placed 0.82 Å from their respective O atoms. These H atoms were allowed to refine as riding atoms on their respective parent atoms, with displacement parameters fixed at 1.2Ueq(C) for methyl H atoms and 1.5Ueq(O) for carboxyl H atoms. After refinement, the occupancy of the acetic acid molecules was optimized by fixing all previously refined positional and displacement-parameter values and independently refining the occupancy of the acetic acid atoms as a single group. The absolute configuration was not determined.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXP97 (Sheldrick, 1997a); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of the title compound, with the steroidal numbering shown for molecule (I'); molecule (I) has identical but unprimed numbering. Displacement ellipsoids are shown at the 20% probability level.
[Figure 2] Fig. 2. A partial packing diagram, showing the two molecules of the asymmetric unit, with extracellular molecules included to illustrate one of the two sets of counter-directional translational catemers passing through the cell in the a direction. All H atoms bound to C atoms have been omitted for clarity. Displacement ellipsoids are shown at the 20% probability level.
'9-α-fluoro-16-α-methyl-3,11-dioxoandrosta-1,4-diene-17β- carboxylic acid' top
Crystal data top
C21H25FO4·C2H4O2F(000) = 896
Mr = 420.46Dx = 1.287 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 31 reflections
a = 12.823 (3) Åθ = 2.9–10.2°
b = 11.269 (4) ŵ = 0.10 mm1
c = 15.407 (4) ÅT = 296 K
β = 102.860 (15)°Thin five-sided plate, colorless
V = 2170.5 (11) Å30.48 × 0.32 × 0.08 mm
Z = 4
Data collection top
Siemens P4
diffractometer
2608 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.051
Graphite monochromatorθmax = 25.0°, θmin = 2.3°
2θ/θ scansh = 1515
Absorption correction: analytical
Sheldrick, 1997
k = 1313
Tmin = 0.963, Tmax = 0.993l = 1818
8416 measured reflections3 standard reflections every 97 reflections
4036 independent reflections intensity decay: variation <4%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.059H-atom parameters constrained
wR(F2) = 0.146 w = 1/[σ2(Fo2) + (0.0724P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
4036 reflectionsΔρmax = 0.28 e Å3
542 parametersΔρmin = 0.18 e Å3
1 restraintExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0061 (17)
Crystal data top
C21H25FO4·C2H4O2V = 2170.5 (11) Å3
Mr = 420.46Z = 4
Monoclinic, P21Mo Kα radiation
a = 12.823 (3) ŵ = 0.10 mm1
b = 11.269 (4) ÅT = 296 K
c = 15.407 (4) Å0.48 × 0.32 × 0.08 mm
β = 102.860 (15)°
Data collection top
Siemens P4
diffractometer
2608 reflections with I > 2σ(I)
Absorption correction: analytical
Sheldrick, 1997
Rint = 0.051
Tmin = 0.963, Tmax = 0.9933 standard reflections every 97 reflections
8416 measured reflections intensity decay: variation <4%
4036 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0591 restraint
wR(F2) = 0.146H-atom parameters constrained
S = 1.06Δρmax = 0.28 e Å3
4036 reflectionsΔρmin = 0.18 e Å3
542 parameters
Special details top

Experimental. 'crystal mounted on glass fiber using cyanoacrylate cement'

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
xyzUiso*/Ueq
F10.0493 (2)0.5035 (3)0.1348 (2)0.0579 (9)
F1'0.6869 (2)0.6472 (3)0.60451 (19)0.0415 (7)
O10.3024 (3)0.6077 (4)0.1999 (3)0.0730 (14)
O20.2184 (3)0.6098 (4)0.3119 (4)0.0774 (15)
O30.5654 (4)0.3290 (5)0.1748 (4)0.0829 (15)
O40.5051 (3)0.5100 (5)0.1374 (3)0.0777 (15)
H4B0.56730.52800.15980.117*
O1'1.0295 (3)0.7026 (3)0.5220 (3)0.0547 (11)
O2'0.5180 (3)0.6056 (4)0.4127 (3)0.0559 (11)
O3'0.1907 (3)0.4830 (4)0.6594 (3)0.0767 (14)
O4'0.2312 (3)0.6447 (4)0.5914 (3)0.0701 (13)
H4'B0.16590.64900.57530.105*
C10.0204 (5)0.6175 (5)0.2729 (5)0.0573 (17)
H1A0.03270.67480.28850.069*
C20.1195 (5)0.6532 (6)0.2478 (4)0.0603 (17)
H2A0.13330.73420.24840.072*
C30.2086 (5)0.5736 (6)0.2193 (4)0.0536 (16)
C40.1805 (5)0.4471 (6)0.2189 (4)0.0559 (16)
H4A0.23550.39250.20090.067*
C50.0813 (4)0.4066 (5)0.2429 (4)0.0484 (15)
C60.0547 (5)0.2785 (6)0.2387 (4)0.0532 (16)
H6A0.11890.23460.21210.064*
H6B0.02810.24850.29850.064*
C70.0301 (4)0.2590 (6)0.1837 (4)0.0534 (16)
H7A0.05020.17590.18630.064*
H7B0.00020.27880.12200.064*
C80.1300 (4)0.3347 (5)0.2176 (4)0.0408 (13)
H8A0.16470.30790.27760.049*
C90.0990 (4)0.4667 (5)0.2223 (4)0.0417 (13)
C100.0128 (4)0.4886 (6)0.2782 (4)0.0477 (14)
C110.2003 (4)0.5447 (6)0.2463 (5)0.0537 (16)
C120.2782 (5)0.5323 (5)0.1863 (4)0.0525 (15)
H12A0.34050.58210.20730.063*
H12B0.24470.55560.12590.063*
C130.3111 (4)0.3993 (5)0.1894 (3)0.0416 (14)
C140.2097 (4)0.3233 (5)0.1580 (4)0.0418 (13)
H14A0.17380.35270.09900.050*
C150.2532 (5)0.2010 (6)0.1445 (4)0.0540 (16)
H15A0.20240.15650.10030.065*
H15B0.26850.15670.19990.065*
C160.3568 (5)0.2253 (6)0.1120 (4)0.0580 (17)
H16A0.41600.18500.15240.070*
C170.3762 (4)0.3599 (6)0.1211 (4)0.0520 (16)
H17A0.34490.39720.06370.062*
C180.3738 (4)0.3681 (6)0.2844 (4)0.0510 (15)
H18A0.39470.28610.28650.077*
H18B0.32920.38160.32580.077*
H18C0.43640.41710.29980.077*
C190.0595 (5)0.4596 (7)0.3782 (4)0.0603 (18)
H19A0.00600.47400.41170.091*
H19B0.12050.50900.40040.091*
H19C0.08060.37770.38410.091*
C200.4916 (5)0.3939 (7)0.1472 (4)0.0574 (17)
C210.3513 (7)0.1797 (8)0.0167 (5)0.091 (3)
H21A0.41740.19690.00000.137*
H21B0.29350.21830.02380.137*
H21C0.33940.09550.01480.137*
C221.0145 (6)0.3992 (9)0.8961 (5)0.081 (2)
C231.1144 (7)0.4533 (9)0.8811 (6)0.105 (3)
H23A1.09760.52520.84730.158*
H23B1.14910.39880.84880.158*
H23C1.16130.47110.93740.158*
C1'0.7533 (4)0.6423 (5)0.4439 (4)0.0415 (13)
H1'A0.69540.67440.40340.050*
C2'0.8464 (4)0.6978 (5)0.4557 (4)0.0418 (13)
H2'A0.85080.76760.42450.050*
C3'0.9417 (4)0.6531 (5)0.5158 (4)0.0447 (14)
C4'0.9288 (4)0.5461 (5)0.5654 (4)0.0463 (14)
H4'A0.98830.51540.60490.056*
C5'0.8356 (4)0.4905 (5)0.5567 (4)0.0423 (13)
C6'0.8237 (4)0.3844 (6)0.6126 (4)0.0560 (16)
H6'A0.89150.36740.65310.067*
H6'B0.80370.31580.57450.067*
C7'0.7379 (4)0.4076 (5)0.6660 (4)0.0519 (16)
H7'A0.76270.46900.70980.062*
H7'B0.72660.33590.69750.062*
C8'0.6305 (4)0.4467 (5)0.6043 (4)0.0393 (12)
H8'A0.60280.37990.56520.047*
C9'0.6478 (4)0.5516 (4)0.5458 (3)0.0350 (12)
C10'0.7354 (4)0.5306 (4)0.4919 (3)0.0371 (12)
C11'0.5381 (4)0.5986 (5)0.4926 (4)0.0395 (13)
C12'0.4570 (4)0.6279 (5)0.5476 (4)0.0390 (13)
H12C0.39000.65250.50900.047*
H12D0.48320.69210.58850.047*
C13'0.4398 (4)0.5166 (5)0.5992 (3)0.0390 (13)
C14'0.5472 (4)0.4782 (5)0.6580 (3)0.0393 (12)
H14B0.57530.54710.69460.047*
C15'0.5197 (4)0.3859 (6)0.7213 (4)0.0524 (15)
H15C0.57290.38500.77700.063*
H15D0.51530.30740.69500.063*
C16'0.4085 (4)0.4258 (6)0.7367 (4)0.0523 (15)
H16B0.35700.36170.71680.063*
C17'0.3754 (4)0.5346 (5)0.6739 (4)0.0428 (13)
H17B0.40300.60610.70740.051*
C18'0.3855 (4)0.4203 (5)0.5334 (4)0.0508 (15)
H18D0.42560.40880.48850.076*
H18E0.31410.44500.50600.076*
H18F0.38280.34730.56490.076*
C19'0.7004 (5)0.4331 (5)0.4199 (4)0.0564 (16)
H19D0.75540.42220.38730.085*
H19E0.63530.45690.37970.085*
H19F0.68890.35980.44820.085*
C20'0.2575 (4)0.5490 (6)0.6421 (4)0.0503 (15)
C21'0.4088 (5)0.4540 (8)0.8326 (4)0.076 (2)
H21D0.33850.47850.83710.114*
H21E0.45880.51670.85310.114*
H21F0.42930.38460.86850.114*
C22'0.7586 (7)0.2860 (9)0.9620 (5)0.081 (2)
C23'0.6602 (7)0.2464 (10)0.9900 (6)0.110 (3)
H23D0.67560.17601.02570.165*
H23E0.60500.22970.93830.165*
H23F0.63660.30801.02420.165*
O50.9290 (5)0.4418 (8)0.8647 (6)0.160 (4)
O61.0254 (5)0.3034 (6)0.9404 (4)0.1044 (19)
H6C0.96780.28450.95110.157*
O5'0.8425 (5)0.2273 (5)0.9814 (4)0.0943 (17)
O6'0.7506 (5)0.3789 (8)0.9139 (6)0.152 (3)
H6'C0.80830.39290.90150.227*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F10.0469 (18)0.066 (2)0.061 (2)0.0075 (17)0.0140 (16)0.0117 (19)
F1'0.0373 (16)0.0326 (16)0.0571 (18)0.0012 (14)0.0163 (14)0.0086 (15)
O10.043 (2)0.080 (3)0.094 (3)0.008 (2)0.010 (2)0.018 (3)
O20.051 (3)0.065 (3)0.121 (4)0.019 (2)0.030 (3)0.041 (3)
O30.047 (3)0.074 (3)0.126 (4)0.013 (3)0.015 (3)0.005 (3)
O40.041 (2)0.087 (4)0.104 (4)0.000 (3)0.015 (2)0.033 (3)
O1'0.036 (2)0.046 (3)0.083 (3)0.0012 (19)0.017 (2)0.003 (2)
O2'0.043 (2)0.072 (3)0.051 (3)0.004 (2)0.0054 (19)0.007 (2)
O3'0.037 (2)0.076 (3)0.119 (4)0.005 (2)0.020 (2)0.027 (3)
O4'0.038 (2)0.056 (3)0.119 (4)0.001 (2)0.023 (2)0.029 (3)
C10.056 (4)0.038 (4)0.086 (5)0.003 (3)0.034 (3)0.010 (3)
C20.051 (4)0.056 (4)0.084 (5)0.001 (3)0.036 (3)0.003 (4)
C30.046 (4)0.063 (4)0.055 (4)0.003 (3)0.017 (3)0.009 (3)
C40.038 (3)0.070 (4)0.066 (4)0.016 (3)0.023 (3)0.011 (4)
C50.045 (3)0.051 (4)0.057 (4)0.008 (3)0.027 (3)0.005 (3)
C60.048 (3)0.049 (4)0.067 (4)0.008 (3)0.023 (3)0.006 (3)
C70.040 (3)0.054 (4)0.068 (4)0.010 (3)0.018 (3)0.012 (3)
C80.039 (3)0.038 (3)0.047 (3)0.006 (3)0.013 (2)0.000 (3)
C90.035 (3)0.040 (3)0.050 (3)0.000 (3)0.010 (2)0.001 (3)
C100.038 (3)0.049 (4)0.059 (4)0.009 (3)0.019 (3)0.007 (3)
C110.037 (3)0.044 (4)0.083 (5)0.000 (3)0.018 (3)0.003 (4)
C120.039 (3)0.043 (3)0.080 (4)0.002 (3)0.022 (3)0.009 (3)
C130.035 (3)0.052 (4)0.040 (3)0.002 (3)0.013 (2)0.007 (3)
C140.036 (3)0.048 (3)0.042 (3)0.000 (3)0.010 (2)0.002 (3)
C150.048 (3)0.056 (4)0.060 (4)0.006 (3)0.016 (3)0.014 (3)
C160.047 (3)0.073 (5)0.057 (4)0.008 (3)0.018 (3)0.009 (4)
C170.042 (3)0.063 (4)0.051 (4)0.004 (3)0.011 (3)0.004 (3)
C180.048 (3)0.052 (4)0.050 (3)0.005 (3)0.007 (3)0.001 (3)
C190.060 (4)0.069 (5)0.057 (4)0.015 (3)0.024 (3)0.018 (4)
C200.034 (3)0.074 (5)0.070 (4)0.005 (3)0.022 (3)0.010 (4)
C210.103 (6)0.106 (7)0.075 (5)0.005 (5)0.042 (5)0.026 (5)
C220.066 (5)0.096 (7)0.077 (5)0.004 (5)0.007 (4)0.017 (5)
C230.091 (6)0.105 (7)0.124 (7)0.010 (6)0.030 (5)0.010 (6)
C1'0.040 (3)0.038 (3)0.050 (3)0.008 (3)0.016 (2)0.001 (3)
C2'0.037 (3)0.034 (3)0.057 (3)0.001 (3)0.014 (3)0.002 (3)
C3'0.044 (3)0.043 (3)0.051 (3)0.007 (3)0.021 (3)0.005 (3)
C4'0.037 (3)0.041 (3)0.063 (4)0.009 (3)0.014 (3)0.007 (3)
C5'0.035 (3)0.035 (3)0.063 (3)0.012 (3)0.023 (3)0.001 (3)
C6'0.044 (3)0.048 (4)0.081 (4)0.019 (3)0.025 (3)0.023 (3)
C7'0.041 (3)0.047 (4)0.071 (4)0.012 (3)0.019 (3)0.016 (3)
C8'0.033 (3)0.030 (3)0.059 (3)0.005 (2)0.018 (2)0.001 (3)
C9'0.031 (3)0.028 (3)0.045 (3)0.003 (2)0.006 (2)0.005 (3)
C10'0.035 (3)0.027 (3)0.051 (3)0.006 (2)0.014 (2)0.001 (3)
C11'0.032 (3)0.037 (3)0.049 (4)0.002 (2)0.007 (3)0.009 (3)
C12'0.034 (3)0.031 (3)0.053 (3)0.003 (2)0.011 (2)0.001 (3)
C13'0.034 (3)0.034 (3)0.049 (3)0.002 (2)0.010 (2)0.000 (3)
C14'0.034 (3)0.038 (3)0.047 (3)0.004 (2)0.012 (2)0.000 (3)
C15'0.055 (3)0.055 (4)0.050 (3)0.007 (3)0.017 (3)0.012 (3)
C16'0.041 (3)0.060 (4)0.060 (4)0.006 (3)0.020 (3)0.007 (3)
C17'0.030 (3)0.044 (3)0.055 (3)0.005 (3)0.012 (2)0.003 (3)
C18'0.044 (3)0.044 (4)0.064 (4)0.006 (3)0.012 (3)0.006 (3)
C19'0.064 (4)0.044 (4)0.068 (4)0.008 (3)0.029 (3)0.015 (3)
C20'0.035 (3)0.049 (4)0.074 (4)0.005 (3)0.026 (3)0.006 (4)
C21'0.065 (4)0.102 (6)0.066 (4)0.004 (4)0.027 (4)0.005 (4)
C22'0.079 (6)0.094 (7)0.067 (5)0.002 (5)0.009 (4)0.002 (5)
C23'0.093 (6)0.144 (9)0.106 (7)0.012 (7)0.049 (5)0.012 (7)
O50.080 (4)0.169 (7)0.218 (8)0.018 (5)0.006 (5)0.111 (7)
O60.094 (4)0.104 (5)0.113 (4)0.000 (4)0.019 (3)0.027 (4)
O5'0.081 (4)0.084 (4)0.110 (4)0.001 (3)0.003 (3)0.007 (3)
O6'0.085 (4)0.151 (7)0.211 (8)0.019 (5)0.016 (5)0.083 (7)
Geometric parameters (Å, º) top
F1—C91.419 (6)C22—O61.269 (10)
F1'—C9'1.424 (6)C22—C231.483 (11)
O1—C31.235 (7)C23—H23A0.9600
O2—C111.227 (7)C23—H23B0.9600
O3—C201.197 (7)C23—H23C0.9600
O4—C201.332 (8)C1'—C2'1.324 (7)
O4—H4B0.8200C1'—C10'1.503 (8)
O1'—C3'1.241 (6)C1'—H1'A0.9300
O2'—C11'1.202 (6)C2'—C3'1.450 (7)
O3'—C20'1.208 (7)C2'—H2'A0.9300
O4'—C20'1.330 (7)C3'—C4'1.457 (8)
O4'—H4'B0.8200C4'—C5'1.330 (7)
C1—C21.306 (8)C4'—H4'A0.9300
C1—C101.511 (9)C5'—C6'1.501 (8)
C1—H1A0.9300C5'—C10'1.511 (7)
C2—C31.442 (9)C6'—C7'1.536 (7)
C2—H2A0.9300C6'—H6'A0.9700
C3—C41.471 (10)C6'—H6'B0.9700
C4—C51.324 (8)C7'—C8'1.553 (7)
C4—H4A0.9300C7'—H7'A0.9700
C5—C61.488 (9)C7'—H7'B0.9700
C5—C101.522 (8)C8'—C14'1.532 (7)
C6—C71.536 (8)C8'—C9'1.534 (7)
C6—H6A0.9700C8'—H8'A0.9800
C6—H6B0.9700C9'—C11'1.555 (7)
C7—C81.530 (7)C9'—C10'1.556 (7)
C7—H7A0.9700C10'—C19'1.555 (8)
C7—H7B0.9700C11'—C12'1.517 (7)
C8—C141.523 (7)C12'—C13'1.526 (8)
C8—C91.546 (8)C12'—H12C0.9700
C8—H8A0.9800C12'—H12D0.9700
C9—C111.544 (8)C13'—C14'1.533 (7)
C9—C101.563 (7)C13'—C18'1.541 (7)
C10—C191.559 (8)C13'—C17'1.572 (7)
C11—C121.512 (8)C14'—C15'1.520 (8)
C12—C131.555 (8)C14'—H14B0.9800
C12—H12A0.9700C15'—C16'1.563 (7)
C12—H12B0.9700C15'—H15C0.9700
C13—C141.543 (7)C15'—H15D0.9700
C13—C181.545 (7)C16'—C21'1.511 (8)
C13—C171.546 (8)C16'—C17'1.560 (8)
C14—C151.517 (8)C16'—H16B0.9800
C14—H14A0.9800C17'—C20'1.491 (7)
C15—C161.545 (8)C17'—H17B0.9800
C15—H15A0.9700C18'—H18D0.9600
C15—H15B0.9700C18'—H18E0.9600
C16—C171.538 (9)C18'—H18F0.9600
C16—C211.543 (9)C19'—H19D0.9600
C16—H16A0.9800C19'—H19E0.9600
C17—C201.495 (8)C19'—H19F0.9600
C17—H17A0.9800C21'—H21D0.9600
C18—H18A0.9600C21'—H21E0.9600
C18—H18B0.9600C21'—H21F0.9600
C18—H18C0.9600C22'—O5'1.241 (10)
C19—H19A0.9600C22'—O6'1.275 (11)
C19—H19B0.9600C22'—C23'1.490 (12)
C19—H19C0.9600C23'—H23D0.9600
C21—H21A0.9600C23'—H23E0.9600
C21—H21B0.9600C23'—H23F0.9600
C21—H21C0.9600O6—H6C0.8200
C22—O51.196 (9)O6'—H6'C0.8200
C20—O4—H4B109.5C2'—C1'—C10'124.0 (5)
C20'—O4'—H4'B109.5C2'—C1'—H1'A118.0
C2—C1—C10123.8 (6)C10'—C1'—H1'A118.0
C2—C1—H1A118.1C1'—C2'—C3'122.0 (5)
C10—C1—H1A118.1C1'—C2'—H2'A119.0
C1—C2—C3123.4 (7)C3'—C2'—H2'A119.0
C1—C2—H2A118.3O1'—C3'—C2'120.9 (5)
C3—C2—H2A118.3O1'—C3'—C4'122.6 (5)
O1—C3—C2122.9 (6)C2'—C3'—C4'116.4 (5)
O1—C3—C4121.8 (6)C5'—C4'—C3'122.8 (5)
C2—C3—C4115.2 (6)C5'—C4'—H4'A118.6
C5—C4—C3123.6 (6)C3'—C4'—H4'A118.6
C5—C4—H4A118.2C4'—C5'—C6'121.4 (5)
C3—C4—H4A118.2C4'—C5'—C10'122.6 (5)
C4—C5—C6122.5 (6)C6'—C5'—C10'116.0 (5)
C4—C5—C10121.8 (6)C5'—C6'—C7'110.4 (5)
C6—C5—C10115.7 (5)C5'—C6'—H6'A109.6
C5—C6—C7111.1 (5)C7'—C6'—H6'A109.6
C5—C6—H6A109.4C5'—C6'—H6'B109.6
C7—C6—H6A109.4C7'—C6'—H6'B109.6
C5—C6—H6B109.4H6'A—C6'—H6'B108.1
C7—C6—H6B109.4C6'—C7'—C8'111.4 (5)
H6A—C6—H6B108.0C6'—C7'—H7'A109.4
C8—C7—C6112.0 (5)C8'—C7'—H7'A109.4
C8—C7—H7A109.2C6'—C7'—H7'B109.4
C6—C7—H7A109.2C8'—C7'—H7'B109.4
C8—C7—H7B109.2H7'A—C7'—H7'B108.0
C6—C7—H7B109.2C14'—C8'—C9'110.4 (4)
H7A—C7—H7B107.9C14'—C8'—C7'111.5 (4)
C14—C8—C7111.7 (4)C9'—C8'—C7'110.7 (4)
C14—C8—C9108.9 (4)C14'—C8'—H8'A108.0
C7—C8—C9110.3 (4)C9'—C8'—H8'A108.0
C14—C8—H8A108.6C7'—C8'—H8'A108.0
C7—C8—H8A108.6F1'—C9'—C8'106.6 (4)
C9—C8—H8A108.6F1'—C9'—C11'103.1 (4)
F1—C9—C11103.7 (4)C8'—C9'—C11'109.8 (4)
F1—C9—C8107.6 (4)F1'—C9'—C10'105.1 (4)
C11—C9—C8110.3 (4)C8'—C9'—C10'114.4 (4)
F1—C9—C10104.7 (4)C11'—C9'—C10'116.5 (4)
C11—C9—C10116.0 (5)C1'—C10'—C5'112.1 (4)
C8—C9—C10113.5 (5)C1'—C10'—C19'107.0 (4)
C1—C10—C5111.9 (5)C5'—C10'—C19'109.1 (4)
C1—C10—C19107.2 (5)C1'—C10'—C9'110.0 (4)
C5—C10—C19109.0 (5)C5'—C10'—C9'107.5 (4)
C1—C10—C9110.4 (5)C19'—C10'—C9'111.1 (4)
C5—C10—C9108.0 (5)O2'—C11'—C12'122.7 (5)
C19—C10—C9110.4 (4)O2'—C11'—C9'121.6 (5)
O2—C11—C12121.9 (5)C12'—C11'—C9'115.6 (5)
O2—C11—C9122.1 (5)C11'—C12'—C13'108.0 (4)
C12—C11—C9115.9 (6)C11'—C12'—H12C110.1
C11—C12—C13106.4 (5)C13'—C12'—H12C110.1
C11—C12—H12A110.5C11'—C12'—H12D110.1
C13—C12—H12A110.5C13'—C12'—H12D110.1
C11—C12—H12B110.5H12C—C12'—H12D108.4
C13—C12—H12B110.5C12'—C13'—C14'109.0 (4)
H12A—C12—H12B108.6C12'—C13'—C18'109.4 (4)
C14—C13—C18113.3 (4)C14'—C13'—C18'113.9 (4)
C14—C13—C1799.9 (4)C12'—C13'—C17'115.9 (4)
C18—C13—C17109.5 (4)C14'—C13'—C17'98.8 (4)
C14—C13—C12108.8 (4)C18'—C13'—C17'109.7 (4)
C18—C13—C12109.2 (5)C15'—C14'—C8'118.5 (5)
C17—C13—C12116.1 (5)C15'—C14'—C13'105.5 (4)
C15—C14—C8118.4 (5)C8'—C14'—C13'112.9 (4)
C15—C14—C13103.7 (4)C15'—C14'—H14B106.4
C8—C14—C13113.3 (4)C8'—C14'—H14B106.4
C15—C14—H14A106.9C13'—C14'—H14B106.4
C8—C14—H14A106.9C14'—C15'—C16'104.5 (5)
C13—C14—H14A106.9C14'—C15'—H15C110.9
C14—C15—C16104.6 (5)C16'—C15'—H15C110.9
C14—C15—H15A110.8C14'—C15'—H15D110.9
C16—C15—H15A110.8C16'—C15'—H15D110.9
C14—C15—H15B110.8H15C—C15'—H15D108.9
C16—C15—H15B110.8C21'—C16'—C17'112.5 (5)
H15A—C15—H15B108.9C21'—C16'—C15'113.9 (5)
C17—C16—C21112.8 (6)C17'—C16'—C15'105.3 (4)
C17—C16—C15106.2 (5)C21'—C16'—H16B108.3
C21—C16—C15112.9 (6)C17'—C16'—H16B108.3
C17—C16—H16A108.3C15'—C16'—H16B108.3
C21—C16—H16A108.3C20'—C17'—C16'113.9 (5)
C15—C16—H16A108.3C20'—C17'—C13'115.7 (4)
C20—C17—C16114.1 (5)C16'—C17'—C13'103.8 (4)
C20—C17—C13113.3 (5)C20'—C17'—H17B107.7
C16—C17—C13104.1 (5)C16'—C17'—H17B107.7
C20—C17—H17A108.4C13'—C17'—H17B107.7
C16—C17—H17A108.4C13'—C18'—H18D109.5
C13—C17—H17A108.4C13'—C18'—H18E109.5
C13—C18—H18A109.5H18D—C18'—H18E109.5
C13—C18—H18B109.5C13'—C18'—H18F109.5
H18A—C18—H18B109.5H18D—C18'—H18F109.5
C13—C18—H18C109.5H18E—C18'—H18F109.5
H18A—C18—H18C109.5C10'—C19'—H19D109.5
H18B—C18—H18C109.5C10'—C19'—H19E109.5
C10—C19—H19A109.5H19D—C19'—H19E109.5
C10—C19—H19B109.5C10'—C19'—H19F109.5
H19A—C19—H19B109.5H19D—C19'—H19F109.5
C10—C19—H19C109.5H19E—C19'—H19F109.5
H19A—C19—H19C109.5O3'—C20'—O4'121.9 (5)
H19B—C19—H19C109.5O3'—C20'—C17'125.2 (6)
O3—C20—O4121.9 (6)O4'—C20'—C17'112.8 (5)
O3—C20—C17126.5 (7)C16'—C21'—H21D109.5
O4—C20—C17111.6 (6)C16'—C21'—H21E109.5
C16—C21—H21A109.5H21D—C21'—H21E109.5
C16—C21—H21B109.5C16'—C21'—H21F109.5
H21A—C21—H21B109.5H21D—C21'—H21F109.5
C16—C21—H21C109.5H21E—C21'—H21F109.5
H21A—C21—H21C109.5O5'—C22'—O6'122.1 (9)
H21B—C21—H21C109.5O5'—C22'—C23'121.0 (9)
O5—C22—O6122.7 (9)O6'—C22'—C23'116.8 (9)
O5—C22—C23121.2 (9)C22'—C23'—H23D109.5
O6—C22—C23116.0 (8)C22'—C23'—H23E109.5
C22—C23—H23A109.5H23D—C23'—H23E109.5
C22—C23—H23B109.5C22'—C23'—H23F109.5
H23A—C23—H23B109.5H23D—C23'—H23F109.5
C22—C23—H23C109.5H23E—C23'—H23F109.5
H23A—C23—H23C109.5C22—O6—H6C109.5
H23B—C23—H23C109.5C22'—O6'—H6'C109.5
C10—C1—C2—C32.1 (10)C10'—C1'—C2'—C3'1.5 (8)
C1—C2—C3—O1176.3 (6)C1'—C2'—C3'—O1'175.8 (5)
C1—C2—C3—C40.8 (9)C1'—C2'—C3'—C4'2.4 (7)
O1—C3—C4—C5177.0 (6)O1'—C3'—C4'—C5'177.7 (6)
C2—C3—C4—C50.1 (10)C2'—C3'—C4'—C5'0.4 (8)
C3—C4—C5—C6177.6 (6)C3'—C4'—C5'—C6'176.5 (5)
C3—C4—C5—C103.4 (10)C3'—C4'—C5'—C10'2.4 (8)
C4—C5—C6—C7125.4 (6)C4'—C5'—C6'—C7'121.6 (6)
C10—C5—C6—C755.6 (7)C10'—C5'—C6'—C7'57.4 (7)
C5—C6—C7—C854.1 (7)C5'—C6'—C7'—C8'53.9 (7)
C6—C7—C8—C14175.0 (5)C6'—C7'—C8'—C14'176.1 (5)
C6—C7—C8—C953.7 (7)C6'—C7'—C8'—C9'52.7 (6)
C14—C8—C9—F161.7 (5)C14'—C8'—C9'—F1'61.5 (5)
C7—C8—C9—F161.2 (5)C7'—C8'—C9'—F1'62.5 (5)
C14—C8—C9—C1150.7 (6)C14'—C8'—C9'—C11'49.6 (5)
C7—C8—C9—C11173.7 (5)C7'—C8'—C9'—C11'173.5 (4)
C14—C8—C9—C10177.1 (4)C14'—C8'—C9'—C10'177.2 (4)
C7—C8—C9—C1054.2 (6)C7'—C8'—C9'—C10'53.2 (6)
C2—C1—C10—C55.1 (9)C2'—C1'—C10'—C5'1.3 (7)
C2—C1—C10—C19114.3 (7)C2'—C1'—C10'—C19'118.4 (6)
C2—C1—C10—C9125.4 (6)C2'—C1'—C10'—C9'120.8 (5)
C4—C5—C10—C15.7 (8)C4'—C5'—C10'—C1'3.2 (7)
C6—C5—C10—C1175.3 (5)C6'—C5'—C10'—C1'175.8 (5)
C4—C5—C10—C19112.7 (6)C4'—C5'—C10'—C19'115.2 (6)
C6—C5—C10—C1966.3 (6)C6'—C5'—C10'—C19'65.8 (6)
C4—C5—C10—C9127.4 (6)C4'—C5'—C10'—C9'124.2 (5)
C6—C5—C10—C953.6 (6)C6'—C5'—C10'—C9'54.8 (6)
F1—C9—C10—C157.9 (6)F1'—C9'—C10'—C1'58.1 (5)
C11—C9—C10—C155.7 (7)C8'—C9'—C10'—C1'174.6 (4)
C8—C9—C10—C1174.9 (5)C11'—C9'—C10'—C1'55.4 (6)
F1—C9—C10—C564.7 (6)F1'—C9'—C10'—C5'64.3 (5)
C11—C9—C10—C5178.3 (5)C8'—C9'—C10'—C5'52.3 (5)
C8—C9—C10—C552.4 (6)C11'—C9'—C10'—C5'177.7 (4)
F1—C9—C10—C19176.3 (5)F1'—C9'—C10'—C19'176.4 (4)
C11—C9—C10—C1962.7 (6)C8'—C9'—C10'—C19'67.1 (5)
C8—C9—C10—C1966.7 (6)C11'—C9'—C10'—C19'62.9 (6)
F1—C9—C11—O2122.6 (6)F1'—C9'—C11'—O2'122.6 (5)
C8—C9—C11—O2122.4 (6)C8'—C9'—C11'—O2'124.1 (5)
C10—C9—C11—O28.4 (8)C10'—C9'—C11'—O2'8.1 (7)
F1—C9—C11—C1259.8 (6)F1'—C9'—C11'—C12'60.7 (5)
C8—C9—C11—C1255.2 (7)C8'—C9'—C11'—C12'52.6 (6)
C10—C9—C11—C12174.0 (5)C10'—C9'—C11'—C12'175.2 (4)
O2—C11—C12—C13119.5 (6)O2'—C11'—C12'—C13'119.8 (6)
C9—C11—C12—C1358.1 (6)C9'—C11'—C12'—C13'56.9 (6)
C11—C12—C13—C1458.6 (6)C11'—C12'—C13'—C14'58.6 (5)
C11—C12—C13—C1865.5 (6)C11'—C12'—C13'—C18'66.6 (5)
C11—C12—C13—C17170.2 (5)C11'—C12'—C13'—C17'168.8 (4)
C7—C8—C14—C1558.9 (7)C9'—C8'—C14'—C15'179.2 (5)
C9—C8—C14—C15179.0 (5)C7'—C8'—C14'—C15'55.7 (6)
C7—C8—C14—C13179.4 (5)C9'—C8'—C14'—C13'56.8 (6)
C9—C8—C14—C1357.3 (6)C7'—C8'—C14'—C13'179.7 (4)
C18—C13—C14—C1570.4 (6)C12'—C13'—C14'—C15'167.7 (4)
C17—C13—C14—C1546.0 (5)C18'—C13'—C14'—C15'69.9 (6)
C12—C13—C14—C15168.1 (5)C17'—C13'—C14'—C15'46.4 (5)
C18—C13—C14—C859.2 (6)C12'—C13'—C14'—C8'61.4 (6)
C17—C13—C14—C8175.6 (5)C18'—C13'—C14'—C8'61.0 (6)
C12—C13—C14—C862.3 (6)C17'—C13'—C14'—C8'177.2 (4)
C8—C14—C15—C16160.1 (5)C8'—C14'—C15'—C16'159.9 (5)
C13—C14—C15—C1633.6 (6)C13'—C14'—C15'—C16'32.3 (6)
C14—C15—C16—C177.8 (6)C14'—C15'—C16'—C21'119.2 (6)
C14—C15—C16—C21116.3 (7)C14'—C15'—C16'—C17'4.4 (6)
C21—C16—C17—C2091.1 (7)C21'—C16'—C17'—C20'84.9 (6)
C15—C16—C17—C20144.7 (5)C15'—C16'—C17'—C20'150.5 (5)
C21—C16—C17—C13144.9 (5)C21'—C16'—C17'—C13'148.4 (5)
C15—C16—C17—C1320.8 (6)C15'—C16'—C17'—C13'23.9 (5)
C14—C13—C17—C20165.0 (5)C12'—C13'—C17'—C20'76.0 (6)
C18—C13—C17—C2045.8 (7)C14'—C13'—C17'—C20'167.9 (5)
C12—C13—C17—C2078.3 (7)C18'—C13'—C17'—C20'48.5 (7)
C14—C13—C17—C1640.5 (5)C12'—C13'—C17'—C16'158.5 (4)
C18—C13—C17—C1678.6 (6)C14'—C13'—C17'—C16'42.3 (5)
C12—C13—C17—C16157.2 (5)C18'—C13'—C17'—C16'77.0 (5)
C16—C17—C20—O313.0 (9)C16'—C17'—C20'—O3'2.1 (9)
C13—C17—C20—O3105.8 (8)C13'—C17'—C20'—O3'118.0 (7)
C16—C17—C20—O4167.9 (5)C16'—C17'—C20'—O4'177.7 (5)
C13—C17—C20—O473.2 (7)C13'—C17'—C20'—O4'62.2 (7)

Experimental details

Crystal data
Chemical formulaC21H25FO4·C2H4O2
Mr420.46
Crystal system, space groupMonoclinic, P21
Temperature (K)296
a, b, c (Å)12.823 (3), 11.269 (4), 15.407 (4)
β (°) 102.860 (15)
V3)2170.5 (11)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.48 × 0.32 × 0.08
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correctionAnalytical
Sheldrick, 1997
Tmin, Tmax0.963, 0.993
No. of measured, independent and
observed [I > 2σ(I)] reflections
8416, 4036, 2608
Rint0.051
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.059, 0.146, 1.06
No. of reflections4036
No. of parameters542
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.28, 0.18

Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXP97 (Sheldrick, 1997a), SHELXL97.

 

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