9α-Chloro-16α-methyl-3,11-dioxo­androsta-1,4,6-triene-17β-carboxylic acid pinacolone solvate: catemeric hydrogen bonding and pinacolone solvation in a steroidal diketo acid derived from a commercial glucocorticoid

Azim, I.; Davison, M.; Dufort, M.D.V.; Lalancette, R.A.; Thompson, H.W.

doi:10.1107/S1600536807021435

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9α-Chloro-16α-methyl-3,11-dioxoandrosta-1,4,6-triene-17β-carboxylic acid pinacolone solvate: catemeric hydrogen bonding and pinacolone solvation in a steroidal diketo acid derived from a commercial glucocorticoid

I. Azim, M. Davison, M. D. V. Dufort, R. A. Lalancette and H. W. Thompson

The title ketocarboxylic acid, synthesized from the anti-inflammatory clocortolone pivalate, crystallizes as C₂₁H₂₃ClO₄·C₆H₁₂O, with one molecule of steroid and one of 3,3-dimethylbutanone per asymmetric unit. The carboxyl group is highly ordered and the steroid molecules form translational carboxyl-to-ketone hydrogen-bonding catemers [O

O = 2.682 (3) Å and O—H

O = 158°] that utilize the 3-ketone group, with one chain proceeding in the [110] direction and the other in the [ $\overline{1}$ 10] direction. One close intermolecular C—H

O=C contact is present, which involves the solvent O atom, but neither it nor the Cl atom nor the 11-ketone group play any role in the classical hydrogen bonding.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807021435/lh2378sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807021435/lh2378Isup2.hkl Contains datablock I

CCDC reference: 651404

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.004 Å
R factor = 0.046
wR factor = 0.121
Data-to-parameter ratio = 11.4

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......       0.92

Author Response: Even though we collected data out to 0.84 \%A resolution, the crystal diffracted poorly beyond 0.89 \%A resolution, where more than 27% of the missing data lie. Above 0.89 \%A resolution, we collected 95% of the theoretical data. Larger crystals are not obtainable, and we can only rely on the current data set.


Alert level B
PLAT027_ALERT_3_B _diffrn_reflns_theta_full (too) Low ............      66.40 Deg.

Alert level C
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl1    ..  O2      ..       3.05 Ang.

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           66.40
           From the CIF: _reflns_number_total               3494
           Count of symmetry unique reflns         2247
           Completeness (_total/calc)            155.50%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1247
           Fraction of Friedel pairs measured     0.555
           Are heavy atom types Z>Si present        yes
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 C13    = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C14    = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C16    = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C17    = .          S
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   1 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   9 ALERT level G = General alerts; check

   7 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
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Our study of hydrogen-bonding modes in ketocarboxylic acids often employs terpenoids as subjects, and we now report the structure and aggregation mode of the title steroid, (I), derived from a commercial topical anti-inflammatory glucocorticoid.

Fig. 1 shows the asymmetric unit. The only significant conformational option involves the carboxyl, whose plane lies near the C16—C17 bond, with the C=O bond turned toward C16; the C16—C17—C20—O3 torsion angle = 2.55 (4)°. The A-ring is highly planar (Thompson et al., 1999), with C10 only 0.095 (2) Å out of the average plane for all six ring atoms. The C6—C7 double bond plane (C5—C6—C7—C8) lies at a 13.27 (2)° dihedral angle to this average A-ring plane.

Complete or partial averaging of C—O bond lengths and C—C—O angles, frequent in carboxyl dimers, cannot occur in acid-to-ketone catemers, whose geometry precludes the disordering processes required. In (I), which is catemeric, these values are ones typical of highly ordered dimeric carboxyls.

Fig. 2 illustrates the chains created by the acid-to-ketone H bonding among translationally related steroid molecules (Table 2). This arrangement closely resembles those found in other steroid keto acids that share important structural features with (I). We have now examined a half-dozen 3-ketosteroids with additional ketones in various positions but have yet to observe any involvement of those additional functions in the H-bonding schemes.

Neither the solvate nor the Cl atom nor the C11 ketone plays any direct role in the H bonding. However, in the stacking of adjacent steroid molecules there is an intermolecular contact of 3.044 Å between the Cl and O2 atoms, and within the 2.6 Å range surveyed for non-bonded intermolecular C—H···O packing interactions, one close contact was found involving the solvent oxygen; the solvent occupancy is 100%.

Three-dimensionally, strings of screw-related solvate molecules, associating with each other only via van der Waals' contacts, extend along the b axis, forming sheets in the ab plane. Each solvate sheet is sandwiched between a sheet of [110] catemers and one of [-110] catemers, where it is stabilized by the close C—H···O=C steroid contacts.

We characterize the geometry of H bonding to carbonyls using a combination of H···O=C angle and H···O=C—C torsional angle. These describe the approach of the acid H atom to the O in terms of its deviation from, respectively, C=O axiality (ideal = 120°) and planarity with the carbonyl (ideal = 0°). In (I) the values for these two angles are 130 and -23°.

Related literature top

For the A-ring geometry of a related steroid dienone, see: Thompson et al. (1999)

Experimental top

Compound (I), previously unreported, was synthesized from (+)-9α-chloro-6α-fluoro-11β,21-dihydroxy-16α-methylpregna- 1,4-diene-3,20-dione 21-pivalate (clocortolone pivalate), of known rotation and absolute stereochemistry, a synthetic topical anti-inflammatory glucocorticoid obtained from DFB Pharmaceuticals, Fort Worth, Texas, USA. Preparatory to C20—C21 bond cleavage, the ester function was removed reductively with diisobutylaluminum hydride; this was successful but failed to avoid dehydrofluorination. Following oxidation with pyridinium dichromate in CH₂Cl₂, NaIO₄ cleavage provided a low yield of (I), which was crystallized from pinacolone, to give material of X-ray quality, mp ca 512 K. The ¹H NMR spectrum showed five vinyl peaks (δ 5.8–7.8), confirming the loss of fluorine. The solid-state (KBr) IR spectrum of (I) displays C=O absorptions at 1716, 1654 and 1648 cm^-1, with an alkene absorption at 1595 cm^-1. In CDCl₃ solution, where dimers predominate, these peaks appear at 1704, 1656 & 1607 cm^-1.

Structure description top

For the A-ring geometry of a related steroid dienone, see: Thompson et al. (1999)

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS (Sheldrick, 2004); program(s) used to refine structure: SHELXL (Sheldrick, 2004); molecular graphics: SHELXTL (Sheldrick, 2004); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. A view of compound (I) with its steroid numbering. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates a hydrogen bond.
	Fig. 2. A packing diagram with extracellular molecules included to illustrate the two translational catemers passing through the cell, the first in the [110] direction, and the second in the [-110] direction. All C-bound H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 30% probability level.

9α-Chloro-16α-methyl-3,11-dioxoandrosta-1,4,6-triene-17β-carboxylic acid top

Crystal data top

C₂₁H₂₃ClO₄·C₆H₁₂O	F(000) = 508
M_r = 475.00	D_x = 1.303 Mg m⁻³
Monoclinic, P2₁	Melting point: 512 K
Hall symbol: P 2yb	Cu Kα radiation, λ = 1.54178 Å
a = 6.5000 (4) Å	Cell parameters from 6186 reflections
b = 11.3153 (5) Å	θ = 6.8–66.4°
c = 16.4559 (8) Å	µ = 1.69 mm⁻¹
β = 90.716 (4)°	T = 100 K
V = 1210.23 (11) Å³	Triangular plate, colourless
Z = 2	0.51 × 0.46 × 0.13 mm

Data collection top

Bruker SMART CCD APEXII area-detector diffractometer	3494 independent reflections
Radiation source: fine-focus sealed tube	3358 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
φ and ω scans	θ_max = 66.4°, θ_min = 6.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −7→6
T_min = 0.480, T_max = 0.811	k = −13→13
6187 measured reflections	l = −19→18

Refinement top

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)] = 0.046	H-atom parameters constrained
wR(F²) = 0.121	w = 1/[σ²(F_o²) + (0.0924P)² + 0.1345P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
3494 reflections	Δρ_max = 0.37 e Å⁻³
306 parameters	Δρ_min = −0.33 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1425 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.026 (15)

Crystal data top

C₂₁H₂₃ClO₄·C₆H₁₂O	V = 1210.23 (11) Å³
M_r = 475.00	Z = 2
Monoclinic, P2₁	Cu Kα radiation
a = 6.5000 (4) Å	µ = 1.69 mm⁻¹
b = 11.3153 (5) Å	T = 100 K
c = 16.4559 (8) Å	0.51 × 0.46 × 0.13 mm
β = 90.716 (4)°

Data collection top

Bruker SMART CCD APEXII area-detector diffractometer	3494 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	3358 reflections with I > 2σ(I)
T_min = 0.480, T_max = 0.811	R_int = 0.026
6187 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.121	Δρ_max = 0.37 e Å⁻³
S = 1.08	Δρ_min = −0.33 e Å⁻³
3494 reflections	Absolute structure: Flack (1983), 1425 Friedel pairs
306 parameters	Absolute structure parameter: 0.026 (15)
1 restraint

Special details top

Experimental. Crystal mounted on cryoloop using Paratone-N

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.84202 (9)	0.70938 (6)	0.22592 (3)	0.02168 (18)
O1	0.9050 (4)	0.2425 (2)	0.20777 (14)	0.0348 (6)
C1	0.5626 (5)	0.4870 (3)	0.19898 (18)	0.0226 (6)
H1	0.4746	0.5245	0.1603	0.027*
O2	0.3017 (3)	0.69661 (19)	0.19372 (12)	0.0256 (4)
C2	0.6607 (5)	0.3887 (3)	0.17632 (18)	0.0245 (6)
H2	0.6285	0.3541	0.1251	0.029*
O3	0.2612 (3)	1.2072 (2)	0.37098 (11)	0.0265 (4)
C3	0.8170 (5)	0.3330 (3)	0.22881 (19)	0.0249 (6)
O4	0.2583 (4)	1.1318 (2)	0.24547 (13)	0.0326 (6)
H4	0.1654	1.1824	0.2380	0.049*
C4	0.8666 (4)	0.3938 (3)	0.30430 (18)	0.0210 (6)
H4A	0.9724	0.3624	0.3383	0.025*
C5	0.7692 (4)	0.4927 (2)	0.32825 (17)	0.0184 (6)
O5	0.5009 (4)	0.3998 (2)	0.98335 (15)	0.0389 (6)
C6	0.8388 (5)	0.5560 (3)	0.40089 (18)	0.0246 (6)
H6	0.9289	0.5169	0.4380	0.029*
C7	0.7810 (5)	0.6669 (3)	0.41736 (17)	0.0223 (6)
H7	0.8429	0.7070	0.4621	0.027*
C8	0.6205 (4)	0.7297 (2)	0.36684 (15)	0.0167 (6)
H8	0.4855	0.7124	0.3928	0.020*
C9	0.6052 (4)	0.6794 (2)	0.27984 (16)	0.0179 (6)
C10	0.5831 (4)	0.5415 (2)	0.28173 (17)	0.0190 (6)
C11	0.4376 (4)	0.7476 (2)	0.23028 (16)	0.0181 (6)
C12	0.4479 (5)	0.8818 (3)	0.23319 (17)	0.0210 (6)
H12A	0.3261	0.9158	0.2050	0.025*
H12B	0.5727	0.9096	0.2052	0.025*
C13	0.4534 (4)	0.9227 (2)	0.32201 (17)	0.0166 (6)
C14	0.6402 (4)	0.8645 (2)	0.36483 (17)	0.0180 (6)
H14	0.7643	0.8837	0.3320	0.022*
C15	0.6619 (4)	0.9307 (2)	0.44546 (17)	0.0206 (6)
H15A	0.8070	0.9311	0.4645	0.025*
H15B	0.5760	0.8936	0.4877	0.025*
C16	0.5865 (4)	1.0584 (2)	0.42656 (17)	0.0189 (6)
H16	0.4672	1.0758	0.4624	0.023*
C17	0.5061 (4)	1.0545 (2)	0.33729 (16)	0.0191 (6)
H17	0.6222	1.0766	0.3010	0.023*
C18	0.2481 (4)	0.8926 (3)	0.36221 (18)	0.0224 (6)
H18A	0.1399	0.9444	0.3405	0.034*
H18B	0.2609	0.9040	0.4211	0.034*
H18C	0.2125	0.8100	0.3507	0.034*
C19	0.3888 (5)	0.5055 (3)	0.32943 (19)	0.0237 (6)
H19A	0.2673	0.5430	0.3047	0.036*
H19B	0.4034	0.5313	0.3860	0.036*
H19C	0.3728	0.4194	0.3277	0.036*
C20	0.3295 (5)	1.1397 (2)	0.32129 (17)	0.0208 (6)
C21	0.7482 (5)	1.1537 (3)	0.44052 (19)	0.0267 (7)
H21A	0.7892	1.1547	0.4980	0.040*
H21B	0.6909	1.2308	0.4254	0.040*
H21C	0.8686	1.1369	0.4072	0.040*
C22	0.4332 (6)	0.6001 (3)	0.9566 (3)	0.0463 (10)
H22A	0.4548	0.6448	1.0070	0.069*
H22B	0.3242	0.6378	0.9240	0.069*
H22C	0.5610	0.5990	0.9256	0.069*
C23	0.3712 (5)	0.4758 (3)	0.97662 (18)	0.0273 (7)
C24	0.1458 (5)	0.4496 (3)	0.98863 (19)	0.0292 (7)
C25	0.0240 (6)	0.4828 (4)	0.9108 (2)	0.0414 (9)
H25A	0.0370	0.5679	0.9008	0.062*
H25B	−0.1214	0.4626	0.9176	0.062*
H25C	0.0791	0.4391	0.8645	0.062*
C26	0.1127 (7)	0.3193 (3)	1.0063 (3)	0.0482 (10)
H26A	0.1727	0.2718	0.9628	0.072*
H26B	−0.0351	0.3030	1.0094	0.072*
H26C	0.1792	0.2989	1.0582	0.072*
C27	0.0596 (5)	0.5230 (4)	1.0594 (2)	0.0364 (8)
H27A	0.1228	0.4966	1.1107	0.055*
H27B	−0.0899	0.5123	1.0618	0.055*
H27C	0.0909	0.6067	1.0508	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0178 (3)	0.0224 (3)	0.0250 (3)	0.0013 (3)	0.0035 (2)	0.0021 (3)
O1	0.0356 (13)	0.0275 (13)	0.0412 (13)	0.0152 (9)	−0.0107 (10)	−0.0111 (9)
C1	0.0178 (16)	0.0226 (15)	0.0272 (15)	0.0005 (10)	−0.0044 (11)	−0.0007 (11)
O2	0.0185 (10)	0.0239 (11)	0.0342 (10)	0.0045 (8)	−0.0073 (8)	−0.0058 (9)
C2	0.0223 (16)	0.0245 (15)	0.0265 (15)	0.0027 (12)	−0.0043 (12)	−0.0038 (12)
O3	0.0261 (11)	0.0235 (10)	0.0299 (10)	0.0068 (10)	−0.0011 (8)	−0.0025 (10)
C3	0.0218 (17)	0.0200 (15)	0.0328 (16)	0.0021 (12)	0.0003 (12)	−0.0003 (12)
O4	0.0359 (14)	0.0296 (12)	0.0319 (12)	0.0191 (10)	−0.0089 (10)	−0.0068 (10)
C4	0.0163 (15)	0.0186 (13)	0.0278 (14)	−0.0020 (10)	−0.0042 (11)	0.0050 (11)
C5	0.0166 (15)	0.0173 (14)	0.0214 (14)	−0.0009 (10)	0.0015 (10)	0.0048 (11)
O5	0.0308 (14)	0.0413 (14)	0.0446 (15)	0.0055 (11)	0.0005 (11)	0.0051 (11)
C6	0.0231 (16)	0.0263 (16)	0.0242 (15)	0.0057 (11)	−0.0034 (12)	0.0035 (12)
C7	0.0224 (16)	0.0223 (14)	0.0221 (14)	0.0003 (11)	−0.0027 (11)	−0.0002 (11)
C8	0.0130 (13)	0.0171 (15)	0.0198 (12)	0.0002 (10)	0.0012 (9)	0.0014 (10)
C9	0.0089 (13)	0.0207 (16)	0.0240 (13)	0.0026 (9)	0.0015 (9)	0.0030 (10)
C10	0.0145 (15)	0.0170 (15)	0.0255 (14)	0.0006 (10)	0.0016 (11)	−0.0003 (11)
C11	0.0158 (15)	0.0224 (14)	0.0162 (12)	0.0042 (10)	0.0007 (10)	−0.0019 (10)
C12	0.0212 (16)	0.0207 (15)	0.0210 (14)	0.0050 (11)	−0.0029 (11)	0.0015 (11)
C13	0.0148 (15)	0.0138 (14)	0.0211 (14)	0.0031 (10)	−0.0010 (10)	0.0005 (11)
C14	0.0099 (14)	0.0198 (14)	0.0242 (14)	0.0011 (10)	−0.0005 (10)	0.0036 (11)
C15	0.0186 (16)	0.0183 (14)	0.0248 (15)	0.0013 (11)	−0.0027 (11)	0.0014 (11)
C16	0.0155 (15)	0.0161 (14)	0.0249 (15)	0.0010 (10)	0.0008 (11)	−0.0018 (11)
C17	0.0174 (16)	0.0185 (15)	0.0215 (14)	−0.0002 (10)	0.0014 (11)	0.0000 (11)
C18	0.0149 (16)	0.0213 (14)	0.0311 (16)	0.0007 (11)	0.0010 (12)	−0.0024 (12)
C19	0.0194 (16)	0.0185 (15)	0.0334 (16)	−0.0036 (11)	0.0034 (12)	0.0009 (12)
C20	0.0205 (16)	0.0135 (14)	0.0285 (15)	−0.0003 (10)	0.0004 (11)	−0.0004 (11)
C21	0.0236 (17)	0.0224 (15)	0.0340 (16)	−0.0009 (12)	−0.0040 (12)	0.0011 (13)
C22	0.034 (2)	0.033 (2)	0.072 (3)	−0.0071 (15)	0.0062 (18)	0.0003 (18)
C23	0.0264 (17)	0.0324 (17)	0.0231 (15)	0.0025 (13)	−0.0024 (12)	0.0001 (12)
C24	0.0266 (18)	0.0301 (18)	0.0308 (17)	−0.0005 (13)	0.0006 (13)	−0.0052 (13)
C25	0.028 (2)	0.061 (2)	0.0349 (19)	0.0022 (16)	−0.0027 (15)	−0.0053 (17)
C26	0.046 (2)	0.028 (2)	0.071 (3)	−0.0023 (17)	0.0167 (19)	0.0008 (19)
C27	0.033 (2)	0.0396 (19)	0.0369 (18)	−0.0018 (16)	0.0031 (14)	−0.0051 (16)

Geometric parameters (Å, º) top

Cl1—C9	1.818 (3)	C14—H14	1.0000
O1—C3	1.226 (4)	C15—C16	1.556 (4)
C1—C2	1.338 (4)	C15—H15A	0.9900
C1—C10	1.500 (4)	C15—H15B	0.9900
C1—H1	0.9500	C16—C21	1.521 (4)
O2—C11	1.209 (4)	C16—C17	1.554 (4)
C2—C3	1.467 (4)	C16—H16	1.0000
C2—H2	0.9500	C17—C20	1.520 (4)
O3—C20	1.208 (4)	C17—H17	1.0000
C3—C4	1.453 (4)	C18—H18A	0.9800
O4—C20	1.328 (4)	C18—H18B	0.9800
O4—H4	0.8400	C18—H18C	0.9800
C4—C5	1.347 (4)	C19—H19A	0.9800
C4—H4A	0.9500	C19—H19B	0.9800
C5—C6	1.461 (4)	C19—H19C	0.9800
C5—C10	1.527 (4)	C21—H21A	0.9800
O5—C23	1.209 (4)	C21—H21B	0.9800
C6—C7	1.338 (4)	C21—H21C	0.9800
C6—H6	0.9500	C22—C23	1.501 (5)
C7—C8	1.504 (4)	C22—H22A	0.9800
C7—H7	0.9500	C22—H22B	0.9800
C8—C14	1.532 (4)	C22—H22C	0.9800
C8—C9	1.543 (3)	C23—C24	1.510 (5)
C8—H8	1.0000	C24—C26	1.519 (5)
C9—C11	1.557 (3)	C24—C27	1.542 (5)
C9—C10	1.567 (4)	C24—C25	1.544 (5)
C10—C19	1.550 (4)	C25—H25A	0.9800
C11—C12	1.521 (4)	C25—H25B	0.9800
C12—C13	1.533 (4)	C25—H25C	0.9800
C12—H12A	0.9900	C26—H26A	0.9800
C12—H12B	0.9900	C26—H26B	0.9800
C13—C18	1.535 (4)	C26—H26C	0.9800
C13—C14	1.544 (3)	C27—H27A	0.9800
C13—C17	1.550 (4)	C27—H27B	0.9800
C14—C15	1.528 (4)	C27—H27C	0.9800

C2—C1—C10	123.9 (3)	C21—C16—C17	112.7 (2)
C2—C1—H1	118.0	C21—C16—C15	114.4 (2)
C10—C1—H1	118.0	C17—C16—C15	105.3 (2)
C1—C2—C3	121.4 (3)	C21—C16—H16	108.1
C1—C2—H2	119.3	C17—C16—H16	108.1
C3—C2—H2	119.3	C15—C16—H16	108.1
O1—C3—C4	122.5 (3)	C20—C17—C13	114.7 (2)
O1—C3—C2	121.0 (3)	C20—C17—C16	112.9 (2)
C4—C3—C2	116.4 (3)	C13—C17—C16	104.6 (2)
C20—O4—H4	109.5	C20—C17—H17	108.1
C5—C4—C3	122.9 (3)	C13—C17—H17	108.1
C5—C4—H4A	118.5	C16—C17—H17	108.1
C3—C4—H4A	118.5	C13—C18—H18A	109.5
C4—C5—C6	120.4 (3)	C13—C18—H18B	109.5
C4—C5—C10	121.7 (3)	H18A—C18—H18B	109.5
C6—C5—C10	117.9 (2)	C13—C18—H18C	109.5
C7—C6—C5	122.7 (3)	H18A—C18—H18C	109.5
C7—C6—H6	118.6	H18B—C18—H18C	109.5
C5—C6—H6	118.6	C10—C19—H19A	109.5
C6—C7—C8	121.7 (3)	C10—C19—H19B	109.5
C6—C7—H7	119.2	H19A—C19—H19B	109.5
C8—C7—H7	119.2	C10—C19—H19C	109.5
C7—C8—C14	115.1 (2)	H19A—C19—H19C	109.5
C7—C8—C9	112.0 (2)	H19B—C19—H19C	109.5
C14—C8—C9	110.6 (2)	O3—C20—O4	123.5 (3)
C7—C8—H8	106.1	O3—C20—C17	124.6 (3)
C14—C8—H8	106.1	O4—C20—C17	111.9 (2)
C9—C8—H8	106.1	C16—C21—H21A	109.5
C8—C9—C11	109.9 (2)	C16—C21—H21B	109.5
C8—C9—C10	110.7 (2)	H21A—C21—H21B	109.5
C11—C9—C10	116.1 (2)	C16—C21—H21C	109.5
C8—C9—Cl1	109.82 (17)	H21A—C21—H21C	109.5
C11—C9—Cl1	104.06 (18)	H21B—C21—H21C	109.5
C10—C9—Cl1	105.89 (18)	C23—C22—H22A	109.5
C1—C10—C5	111.5 (2)	C23—C22—H22B	109.5
C1—C10—C19	106.7 (2)	H22A—C22—H22B	109.5
C5—C10—C19	107.2 (2)	C23—C22—H22C	109.5
C1—C10—C9	113.5 (2)	H22A—C22—H22C	109.5
C5—C10—C9	107.3 (2)	H22B—C22—H22C	109.5
C19—C10—C9	110.3 (2)	O5—C23—C22	119.9 (3)
O2—C11—C12	121.6 (3)	O5—C23—C24	121.6 (3)
O2—C11—C9	121.7 (3)	C22—C23—C24	118.5 (3)
C12—C11—C9	116.6 (2)	C23—C24—C26	110.9 (3)
C11—C12—C13	109.4 (2)	C23—C24—C27	110.8 (3)
C11—C12—H12A	109.8	C26—C24—C27	108.9 (3)
C13—C12—H12A	109.8	C23—C24—C25	109.4 (3)
C11—C12—H12B	109.8	C26—C24—C25	108.9 (3)
C13—C12—H12B	109.8	C27—C24—C25	107.9 (3)
H12A—C12—H12B	108.2	C24—C25—H25A	109.5
C12—C13—C18	109.5 (2)	C24—C25—H25B	109.5
C12—C13—C14	108.4 (2)	H25A—C25—H25B	109.5
C18—C13—C14	113.1 (2)	C24—C25—H25C	109.5
C12—C13—C17	116.6 (2)	H25A—C25—H25C	109.5
C18—C13—C17	109.6 (2)	H25B—C25—H25C	109.5
C14—C13—C17	99.5 (2)	C24—C26—H26A	109.5
C15—C14—C8	118.4 (2)	C24—C26—H26B	109.5
C15—C14—C13	104.5 (2)	H26A—C26—H26B	109.5
C8—C14—C13	111.7 (2)	C24—C26—H26C	109.5
C15—C14—H14	107.2	H26A—C26—H26C	109.5
C8—C14—H14	107.2	H26B—C26—H26C	109.5
C13—C14—H14	107.2	C24—C27—H27A	109.5
C14—C15—C16	104.8 (2)	C24—C27—H27B	109.5
C14—C15—H15A	110.8	H27A—C27—H27B	109.5
C16—C15—H15A	110.8	C24—C27—H27C	109.5
C14—C15—H15B	110.8	H27A—C27—H27C	109.5
C16—C15—H15B	110.8	H27B—C27—H27C	109.5
H15A—C15—H15B	108.9

C10—C1—C2—C3	−7.1 (5)	Cl1—C9—C11—C12	−68.6 (3)
C1—C2—C3—O1	179.5 (3)	O2—C11—C12—C13	124.3 (3)
C1—C2—C3—C4	−3.2 (5)	C9—C11—C12—C13	−53.1 (3)
O1—C3—C4—C5	−179.3 (3)	C11—C12—C13—C18	−66.3 (3)
C2—C3—C4—C5	3.3 (4)	C11—C12—C13—C14	57.4 (3)
C3—C4—C5—C6	−174.2 (3)	C11—C12—C13—C17	168.6 (2)
C3—C4—C5—C10	6.5 (4)	C7—C8—C14—C15	−50.5 (3)
C4—C5—C6—C7	164.4 (3)	C9—C8—C14—C15	−178.7 (2)
C10—C5—C6—C7	−16.3 (4)	C7—C8—C14—C13	−172.0 (2)
C5—C6—C7—C8	7.1 (5)	C9—C8—C14—C13	59.8 (3)
C6—C7—C8—C14	−152.4 (3)	C12—C13—C14—C15	167.6 (2)
C6—C7—C8—C9	−24.9 (4)	C18—C13—C14—C15	−70.8 (3)
C7—C8—C9—C11	−179.9 (2)	C17—C13—C14—C15	45.3 (3)
C14—C8—C9—C11	−50.0 (3)	C12—C13—C14—C8	−63.2 (3)
C7—C8—C9—C10	50.6 (3)	C18—C13—C14—C8	58.4 (3)
C14—C8—C9—C10	−179.5 (2)	C17—C13—C14—C8	174.5 (2)
C7—C8—C9—Cl1	−66.0 (3)	C8—C14—C15—C16	−156.8 (2)
C14—C8—C9—Cl1	63.9 (2)	C13—C14—C15—C16	−31.8 (3)
C2—C1—C10—C5	15.5 (4)	C14—C15—C16—C21	−119.1 (3)
C2—C1—C10—C19	−101.3 (3)	C14—C15—C16—C17	5.2 (3)
C2—C1—C10—C9	136.9 (3)	C12—C13—C17—C20	78.0 (3)
C4—C5—C10—C1	−15.0 (4)	C18—C13—C17—C20	−47.1 (3)
C6—C5—C10—C1	165.7 (2)	C14—C13—C17—C20	−165.8 (2)
C4—C5—C10—C19	101.5 (3)	C12—C13—C17—C16	−157.8 (2)
C6—C5—C10—C19	−77.8 (3)	C18—C13—C17—C16	77.2 (3)
C4—C5—C10—C9	−139.9 (3)	C14—C13—C17—C16	−41.6 (3)
C6—C5—C10—C9	40.7 (3)	C21—C16—C17—C20	−86.3 (3)
C8—C9—C10—C1	178.7 (2)	C15—C16—C17—C20	148.4 (2)
C11—C9—C10—C1	52.5 (3)	C21—C16—C17—C13	148.4 (2)
Cl1—C9—C10—C1	−62.3 (3)	C15—C16—C17—C13	23.1 (3)
C8—C9—C10—C5	−57.6 (3)	C13—C17—C20—O3	122.2 (3)
C11—C9—C10—C5	176.3 (2)	C16—C17—C20—O3	2.5 (4)
Cl1—C9—C10—C5	61.4 (2)	C13—C17—C20—O4	−58.0 (3)
C8—C9—C10—C19	58.9 (3)	C16—C17—C20—O4	−177.7 (2)
C11—C9—C10—C19	−67.2 (3)	O5—C23—C24—C26	−1.9 (4)
Cl1—C9—C10—C19	177.93 (18)	C22—C23—C24—C26	178.6 (4)
C8—C9—C11—O2	−128.4 (3)	O5—C23—C24—C27	119.2 (3)
C10—C9—C11—O2	−1.9 (4)	C22—C23—C24—C27	−60.3 (4)
Cl1—C9—C11—O2	114.0 (3)	O5—C23—C24—C25	−122.0 (3)
C8—C9—C11—C12	49.0 (3)	C22—C23—C24—C25	58.6 (4)
C10—C9—C11—C12	175.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O1ⁱ	0.84	1.88	2.682 (3)	158
C2—H2···O5ⁱⁱ	0.95	2.52	3.331 (4)	143

Symmetry codes: (i) x−1, y+1, z; (ii) x, y, z−1.

Experimental details

Crystal data
Chemical formula	C₂₁H₂₃ClO₄·C₆H₁₂O
M_r	475.00
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	6.5000 (4), 11.3153 (5), 16.4559 (8)
β (°)	90.716 (4)
V (Å³)	1210.23 (11)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	1.69
Crystal size (mm)	0.51 × 0.46 × 0.13

Data collection
Diffractometer	Bruker SMART CCD APEXII area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.480, 0.811
No. of measured, independent and observed [I > 2σ(I)] reflections	6187, 3494, 3358
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.121, 1.08
No. of reflections	3494
No. of parameters	306
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.33
Absolute structure	Flack (1983), 1425 Friedel pairs
Absolute structure parameter	0.026 (15)

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2005), SAINT, SHELXS (Sheldrick, 2004), SHELXL (Sheldrick, 2004), SHELXTL (Sheldrick, 2004), SHELXTL.

Selected geometric parameters (Å, º) top

O3—C20	1.208 (4)	O4—C20	1.328 (4)

O3—C20—C17	124.6 (3)	O4—C20—C17	111.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O1ⁱ	0.84	1.88	2.682 (3)	158
C2—H2···O5ⁱⁱ	0.95	2.52	3.331 (4)	143

Symmetry codes: (i) x−1, y+1, z; (ii) x, y, z−1.

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