Crystal chemistry of some synthetic 2-oxa-steroids: conformation, packing motifs and isostructurality

The crystal structures of six synthetic 2-oxa-steroids (A-ring lactone steroids) have been determined by single-crystal X-ray diffraction. The conformation and hydrogen bonding in these oxa-steroids is compared with packing motifs in the natural steroids and the anabolic agent, Anavar^®. O—H...O hydrogen bonding with lactone carbonyl O is the preferred arrangement in molecules with a C—OH group. The donor H atoms of A, B and D rings participate in C—H...O interactions with lactone carbonyl O and D-ring hydroxyl/ketone O acceptor atoms. The conformation of the lactone ring in these analogues is different from the natural androgens because replacement of the C2-methylene group by an O atom changes the geometry of the A ring. Two structurally related lactone steroids provide the first example of O—H...O/C—H...O interaction mimicry and furthermore the two components form a binary solid solution. The O—H...O and C—H...O hydrogen bonds in 2-oxa-steroid crystal structures are analysed and the observed preferences discussed in terms of geometric and chemical factors.

Computing details

Data collection: Kuma KM-4 for (10), (11), (12), (13), (14), (15); KUMA KM-4 for (22). Cell refinement: Kuma KM-4 for (10), (11), (12), (13), (14), (15); KUMA KM-4 for (22). Data reduction: Kuma KM-4 for (10), (11), (12), (13), (14), (15); KUMA KM-4 for (22). Program(s) used to solve structure: SHELX97 (Sheldrick, 1997) for (10), (22); SHELXS97 (Sheldrick, 1990) for (11), (12), (14); SHELXS86 (Sheldrick, 1990) for (13), (15). Program(s) used to refine structure: SHELX97 (Sheldrick, 1997) for (10), (22); SHELXL97 (Sheldrick, 1997) for (11), (12), (14); SHELXL93 (Sheldrick, 1993) for (13), (15). For all compounds, molecular graphics: ORTEP and PLUTO. Software used to prepare material for publication: SHELX97 for (10), (22); SHELXL93 for (11), (12), (13), (14), (15).

Figures

(10) 2-Oxa-4-androsten-3,17-dione

Crystal data

C18H24O3	F(000) = 312
Mr = 288.37	Dx = 1.218 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2y1	Cell parameters from 62 reflections
a = 6.2321 (3) Å	θ = 19–51°
b = 9.9264 (6) Å	µ = 0.65 mm^−1
c = 12.8120 (8) Å	T = 293 K
β = 97.079 (5)°	Cubic, colourless
V = 786.54 (8) Å^3	0.45 × 0.30 × 0.20 mm
Z = 2

Data collection

KM-4 diffractometer	Rint = 0.014
Radiation source: fine-focus sealed tube	θmax = 70.1°, θmin = 3.5°
Graphite monochromator	h = 0→7
ω–2θ scans	k = 0→12
1685 measured reflections	l = −15→15
1597 independent reflections	2 standard reflections every 100 reflections
1434 reflections with I > 2σ(I)	intensity decay: less than 2%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.092	Calculated w = 1/[σ^2(Fo^2) + (0.0527P)^2 + 0.0545P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.011
1597 reflections	Δρmax = 0.10 e Å^−3
190 parameters	Δρmin = −0.13 e Å^−3
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.1 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	1.1263 (4)	0.2306 (2)	0.22518 (19)	0.0696 (6)
H11	1.0335	0.2052	0.1618	0.082*
H12	1.2515	0.2762	0.2039	0.096*
O2	1.1971 (3)	0.11026 (19)	0.28226 (16)	0.0858 (5)
C3	1.3028 (4)	0.1287 (3)	0.3798 (2)	0.0839 (8)
O3	1.3906 (4)	0.0318 (3)	0.4234 (2)	0.1192 (9)
C4	1.2911 (4)	0.2600 (3)	0.42700 (19)	0.0754 (7)
H4	1.3897	0.2809	0.4853	0.096*
C5	1.1458 (3)	0.3527 (3)	0.39113 (16)	0.0624 (5)
C6	1.1056 (4)	0.4757 (3)	0.45224 (15)	0.0747 (7)
H61	1.2257	0.4889	0.5070	0.094*
H62	0.9762	0.4624	0.4860	0.077*
C7	1.0780 (4)	0.6012 (3)	0.38444 (15)	0.0686 (6)
H71	1.2151	0.6241	0.3605	0.089*
H72	1.0351	0.6759	0.4261	0.109*
C8	0.9081 (3)	0.5802 (2)	0.28952 (13)	0.0523 (4)
H8	0.7689	0.5599	0.3142	0.064*
C9	0.9741 (3)	0.4610 (2)	0.22410 (13)	0.0486 (4)
H9	1.1171	0.4839	0.2049	0.052*
C10	1.0048 (3)	0.3277 (2)	0.28776 (15)	0.0563 (5)
C11	0.8260 (4)	0.4432 (2)	0.11926 (16)	0.0616 (5)
H111	0.8866	0.3744	0.0778	0.098*
H112	0.6851	0.4123	0.1339	0.063*
C12	0.7983 (4)	0.5734 (2)	0.05511 (14)	0.0603 (5)
H121	0.9353	0.5984	0.0319	0.069*
H122	0.6943	0.5592	−0.0067	0.085*
C13	0.7212 (3)	0.6853 (2)	0.12066 (15)	0.0527 (5)
C14	0.8830 (3)	0.7043 (2)	0.21968 (14)	0.0531 (4)
H14	1.0239	0.7179	0.1948	0.062*
C15	0.8219 (5)	0.8404 (3)	0.26368 (19)	0.0817 (7)
H151	0.9420	0.8791	0.3092	0.091*
H152	0.6984	0.8320	0.3025	0.073*
C16	0.7662 (6)	0.9251 (3)	0.1642 (2)	0.0938 (9)
H161	0.6415	0.9817	0.1705	0.169*
H162	0.8872	0.9823	0.1524	0.122*
C17	0.7175 (3)	0.8266 (2)	0.07520 (17)	0.0637 (5)
O17	0.6860 (3)	0.8564 (2)	−0.01645 (13)	0.0850 (5)
C18	0.4875 (3)	0.6608 (3)	0.1442 (2)	0.0760 (7)
H181	0.4822	0.5797	0.1847	0.102*
H182	0.3937	0.6520	0.0793	0.099*
H183	0.4410	0.7356	0.1834	0.092*
C19	0.7893 (3)	0.2667 (3)	0.3118 (2)	0.0752 (6)
H191	0.8165	0.1831	0.3487	0.080*
H192	0.6977	0.2508	0.2471	0.104*
H193	0.7193	0.3282	0.3545	0.063*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0730 (13)	0.0606 (14)	0.0757 (13)	0.0066 (11)	0.0110 (10)	0.0072 (11)
O2	0.0834 (11)	0.0667 (11)	0.1062 (13)	0.0127 (9)	0.0075 (10)	0.0180 (10)
C3	0.0568 (12)	0.095 (2)	0.1014 (19)	0.0119 (13)	0.0153 (12)	0.0369 (17)
O3	0.0904 (14)	0.1103 (18)	0.155 (2)	0.0298 (13)	0.0053 (14)	0.0537 (17)
C4	0.0576 (11)	0.0976 (19)	0.0712 (14)	0.0064 (12)	0.0090 (10)	0.0258 (14)
C5	0.0543 (10)	0.0811 (15)	0.0530 (10)	−0.0029 (11)	0.0116 (8)	0.0166 (11)
C6	0.0819 (14)	0.100 (2)	0.0411 (9)	0.0057 (14)	0.0020 (9)	0.0047 (11)
C7	0.0782 (14)	0.0805 (15)	0.0448 (10)	−0.0049 (13)	−0.0012 (9)	−0.0077 (11)
C8	0.0553 (10)	0.0615 (12)	0.0408 (8)	−0.0068 (8)	0.0083 (7)	−0.0014 (8)
C9	0.0465 (8)	0.0562 (11)	0.0433 (8)	−0.0067 (8)	0.0062 (7)	0.0018 (8)
C10	0.0502 (9)	0.0601 (12)	0.0595 (11)	−0.0037 (9)	0.0103 (8)	0.0103 (10)
C11	0.0697 (12)	0.0580 (12)	0.0535 (10)	−0.0012 (10)	−0.0064 (9)	−0.0089 (9)
C12	0.0679 (12)	0.0682 (13)	0.0423 (8)	0.0057 (10)	−0.0037 (8)	−0.0058 (9)
C13	0.0517 (10)	0.0570 (12)	0.0492 (9)	−0.0029 (8)	0.0051 (8)	−0.0006 (8)
C14	0.0583 (9)	0.0553 (10)	0.0456 (9)	−0.0075 (9)	0.0066 (7)	−0.0039 (8)
C15	0.114 (2)	0.0639 (14)	0.0647 (14)	0.0024 (15)	−0.0001 (13)	−0.0144 (12)
C16	0.134 (3)	0.0586 (15)	0.0852 (18)	−0.0001 (16)	−0.0031 (17)	−0.0017 (13)
C17	0.0624 (11)	0.0655 (13)	0.0630 (13)	0.0036 (10)	0.0065 (9)	0.0064 (11)
O17	0.1050 (12)	0.0829 (12)	0.0662 (9)	0.0225 (11)	0.0070 (8)	0.0178 (9)
C18	0.0518 (10)	0.0865 (17)	0.0903 (15)	−0.0026 (11)	0.0115 (10)	0.0031 (14)
C19	0.0569 (11)	0.0755 (14)	0.0938 (16)	−0.0102 (11)	0.0120 (10)	0.0222 (14)

Geometric parameters (Å, º)

C1—O2	1.441 (3)	C11—C12	1.530 (3)
C1—C10	1.515 (3)	C11—H111	0.9700
C1—H11	0.9700	C11—H112	0.9700
C1—H12	0.9700	C12—C13	1.506 (3)
O2—C3	1.351 (3)	C12—H121	0.9700
C3—O3	1.209 (3)	C12—H122	0.9700
C3—C4	1.442 (4)	C13—C17	1.518 (3)
C4—C5	1.333 (4)	C13—C14	1.532 (2)
C4—H4	0.9300	C13—C18	1.543 (3)
C5—C6	1.488 (4)	C14—C15	1.530 (3)
C5—C10	1.517 (3)	C14—H14	0.9800
C6—C7	1.516 (4)	C15—C16	1.531 (4)
C6—H61	0.9700	C15—H151	0.9700
C6—H62	0.9700	C15—H152	0.9700
C7—C8	1.525 (3)	C16—C17	1.504 (4)
C7—H71	0.9700	C16—H161	0.9700
C7—H72	0.9700	C16—H162	0.9700
C8—C14	1.520 (3)	C17—O17	1.203 (3)
C8—C9	1.535 (3)	C18—H181	0.9600
C8—H8	0.9800	C18—H182	0.9600
C9—C11	1.543 (2)	C18—H183	0.9600
C9—C10	1.554 (3)	C19—H191	0.9600
C9—H9	0.9800	C19—H192	0.9600
C10—C19	1.538 (3)	C19—H193	0.9600
O2—C1—C10	113.61 (18)	C12—C11—H112	109.0
O2—C1—H11	108.8	C9—C11—H112	109.0
C10—C1—H11	108.8	H111—C11—H112	107.8
O2—C1—H12	108.8	C13—C12—C11	110.23 (16)
C10—C1—H12	108.8	C13—C12—H121	109.6
H11—C1—H12	107.7	C11—C12—H121	109.6
C3—O2—C1	116.2 (2)	C13—C12—H122	109.6
O3—C3—O2	117.5 (3)	C11—C12—H122	109.6
O3—C3—C4	124.6 (3)	H121—C12—H122	108.1
O2—C3—C4	117.8 (2)	C12—C13—C17	117.27 (17)
C5—C4—C3	123.1 (2)	C12—C13—C14	109.27 (17)
C5—C4—H4	118.4	C17—C13—C14	100.43 (17)
C3—C4—H4	118.4	C12—C13—C18	111.52 (19)
C4—C5—C6	122.5 (2)	C17—C13—C18	104.50 (19)
C4—C5—C10	119.0 (2)	C14—C13—C18	113.48 (17)
C6—C5—C10	118.45 (19)	C8—C14—C15	120.75 (16)
C5—C6—C7	112.79 (16)	C8—C14—C13	113.39 (17)
C5—C6—H61	109.0	C15—C14—C13	104.22 (18)
C7—C6—H61	109.0	C8—C14—H14	105.8
C5—C6—H62	109.0	C15—C14—H14	105.8
C7—C6—H62	109.0	C13—C14—H14	105.8
H61—C6—H62	107.8	C14—C15—C16	102.67 (19)
C6—C7—C8	111.3 (2)	C14—C15—H151	111.2
C6—C7—H71	109.4	C16—C15—H151	111.2
C8—C7—H71	109.4	C14—C15—H152	111.2
C6—C7—H72	109.4	C16—C15—H152	111.2
C8—C7—H72	109.4	H151—C15—H152	109.1
H71—C7—H72	108.0	C17—C16—C15	106.1 (2)
C14—C8—C7	111.67 (18)	C17—C16—H161	110.5
C14—C8—C9	108.57 (14)	C15—C16—H161	110.5
C7—C8—C9	109.55 (18)	C17—C16—H162	110.5
C14—C8—H8	109.0	C15—C16—H162	110.5
C7—C8—H8	109.0	H161—C16—H162	108.7
C9—C8—H8	109.0	O17—C17—C16	125.0 (2)
C8—C9—C11	113.07 (16)	O17—C17—C13	126.5 (2)
C8—C9—C10	113.18 (14)	C16—C17—C13	108.53 (18)
C11—C9—C10	112.40 (16)	C13—C18—H181	109.5
C8—C9—H9	105.8	C13—C18—H182	109.5
C11—C9—H9	105.8	H181—C18—H182	109.5
C10—C9—H9	105.8	C13—C18—H183	109.5
C1—C10—C5	107.02 (17)	H181—C18—H183	109.5
C1—C10—C19	111.2 (2)	H182—C18—H183	109.5
C5—C10—C19	108.43 (16)	C10—C19—H191	109.5
C1—C10—C9	107.54 (15)	C10—C19—H192	109.5
C5—C10—C9	109.84 (17)	H191—C19—H192	109.5
C19—C10—C9	112.70 (17)	C10—C19—H193	109.5
C12—C11—C9	112.75 (17)	H191—C19—H193	109.5
C12—C11—H111	109.0	H192—C19—H193	109.5
C9—C11—H111	109.0

(11) 2-Oxa-5-alpha-androstane-3,17-dione

Crystal data

C18H26O3	Dx = 1.219 Mg m^−3
Mr = 290.39	Melting point = 160–162 K
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 91 reflections
a = 6.3180 (4) Å	θ = 14–51°
b = 6.4489 (5) Å	µ = 0.64 mm^−1
c = 38.841 (3) Å	T = 293 K
V = 1582.5 (2) Å^3	Prism, colourless
Z = 4	0.45 × 0.40 × 0.10 mm
F(000) = 632

Data collection

KM-4 diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 70.2°, θmin = 4.6°
Graphite monochromator	h = −7→7
ω–2θ scans	k = −7→7
1736 measured reflections	l = −47→44
1736 independent reflections	2 standard reflections every 100 reflections
1567 reflections with I > 2σ(I)	intensity decay: less than 2%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.031	w = 1/[σ^2(Fo^2) + (0.0488P)^2 + 0.243P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.089	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.16 e Å^−3
1736 reflections	Δρmin = −0.11 e Å^−3
219 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0047 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.2 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	−0.0582 (3)	0.9326 (3)	0.79506 (4)	0.0419 (4)
H11	−0.1541	0.8198	0.8006	0.049 (6)*
H12	−0.1372	1.0612	0.7966	0.044 (6)*
O2	0.0174 (2)	0.9068 (2)	0.76001 (3)	0.0481 (4)
C3	0.2001 (3)	0.9911 (3)	0.74977 (5)	0.0434 (5)
O3	0.2510 (3)	0.9691 (2)	0.72007 (3)	0.0592 (4)
C4	0.3376 (3)	1.1024 (3)	0.77508 (4)	0.0451 (5)
H41	0.3670	1.2396	0.7660	0.064 (7)*
H42	0.4715	1.0293	0.7765	0.059 (7)*
C5	0.2509 (3)	1.1270 (3)	0.81162 (4)	0.0352 (4)
H51	0.1533	1.2451	0.8112	0.042 (6)*
C6	0.4217 (3)	1.1785 (3)	0.83763 (4)	0.0442 (5)
H61	0.4944	1.3042	0.8307	0.054 (6)*
H62	0.5246	1.0670	0.8384	0.056 (6)*
C7	0.3253 (3)	1.2087 (3)	0.87310 (5)	0.0450 (5)
H71	0.2349	1.3302	0.8728	0.050 (6)*
H72	0.4376	1.2331	0.8897	0.061 (6)*
C8	0.1962 (3)	1.0214 (3)	0.88445 (4)	0.0361 (4)
H81	0.2915	0.9021	0.8864	0.046 (5)*
C9	0.0231 (3)	0.9695 (3)	0.85760 (4)	0.0340 (4)
H91	−0.0666	1.0930	0.8559	0.034 (5)*
C10	0.1199 (3)	0.9361 (3)	0.82138 (4)	0.0338 (4)
C11	−0.1218 (3)	0.7931 (3)	0.86941 (5)	0.0462 (5)
H111	−0.0416	0.6649	0.8696	0.042 (5)*
H112	−0.2358	0.7775	0.8529	0.069 (7)*
C12	−0.2171 (4)	0.8281 (4)	0.90522 (5)	0.0563 (6)
H121	−0.3133	0.9452	0.9046	0.072 (8)*
H122	−0.2967	0.7064	0.9122	0.081 (9)*
C13	−0.0421 (4)	0.8694 (3)	0.93091 (5)	0.0482 (5)
C14	0.0900 (3)	1.0552 (3)	0.91907 (4)	0.0415 (5)
H141	−0.0102	1.1695	0.9157	0.040 (5)*
C15	0.2217 (4)	1.1123 (4)	0.95089 (5)	0.0565 (6)
H151	0.2702	1.2548	0.9498	0.070 (7)*
H152	0.3430	1.0213	0.9533	0.064 (7)*
C16	0.0632 (5)	1.0812 (4)	0.98048 (5)	0.0692 (7)
H161	0.1313	1.0147	0.9999	0.087 (9)*
H162	0.0062	1.2134	0.9880	0.102 (11)*
C17	−0.1103 (4)	0.9451 (4)	0.96620 (5)	0.0620 (7)
O17	−0.2762 (3)	0.9051 (4)	0.98011 (4)	0.0924 (7)
C18	0.2467 (4)	0.7335 (3)	0.81936 (5)	0.0482 (5)
H181	0.3180	0.7259	0.7976	0.071 (8)*
H182	0.1523	0.6177	0.8216	0.076 (8)*
H183	0.3491	0.7301	0.8376	0.089 (10)*
C19	0.0895 (5)	0.6716 (4)	0.93745 (6)	0.0620 (7)
H191	0.1647	0.6348	0.9169	0.083 (9)*
H192	−0.0031	0.5601	0.9439	0.120 (13)*
H193	0.1888	0.6968	0.9557	0.097 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0450 (10)	0.0502 (10)	0.0304 (9)	−0.0044 (10)	−0.0018 (8)	−0.0018 (8)
O2	0.0584 (8)	0.0559 (8)	0.0300 (7)	−0.0073 (8)	−0.0012 (6)	−0.0041 (6)
C3	0.0540 (11)	0.0420 (10)	0.0343 (10)	0.0099 (9)	0.0010 (8)	0.0027 (7)
O3	0.0779 (10)	0.0664 (9)	0.0332 (7)	0.0125 (9)	0.0114 (7)	−0.0028 (6)
C4	0.0453 (10)	0.0535 (11)	0.0365 (9)	−0.0023 (10)	0.0061 (8)	0.0037 (9)
C5	0.0365 (9)	0.0348 (9)	0.0341 (9)	0.0017 (8)	0.0010 (8)	0.0011 (7)
C6	0.0414 (10)	0.0498 (11)	0.0413 (10)	−0.0075 (10)	0.0001 (8)	−0.0006 (9)
C7	0.0491 (11)	0.0467 (10)	0.0391 (10)	−0.0054 (10)	−0.0046 (9)	−0.0042 (8)
C8	0.0401 (9)	0.0373 (9)	0.0310 (9)	0.0044 (8)	−0.0030 (7)	−0.0004 (7)
C9	0.0364 (9)	0.0349 (8)	0.0307 (8)	0.0035 (8)	0.0002 (7)	0.0025 (7)
C10	0.0386 (9)	0.0325 (8)	0.0302 (9)	0.0028 (8)	−0.0003 (7)	−0.0007 (7)
C11	0.0482 (11)	0.0533 (12)	0.0370 (10)	−0.0108 (10)	−0.0006 (8)	0.0064 (9)
C12	0.0550 (12)	0.0701 (15)	0.0439 (11)	−0.0092 (13)	0.0097 (10)	0.0108 (10)
C13	0.0596 (12)	0.0517 (11)	0.0335 (10)	0.0085 (11)	0.0049 (9)	0.0077 (8)
C14	0.0515 (11)	0.0423 (10)	0.0305 (9)	0.0108 (10)	−0.0015 (8)	0.0003 (7)
C15	0.0735 (14)	0.0613 (13)	0.0347 (10)	0.0085 (13)	−0.0089 (10)	−0.0064 (9)
C16	0.1018 (19)	0.0726 (15)	0.0332 (11)	0.0162 (17)	0.0051 (12)	−0.0040 (11)
C17	0.0812 (16)	0.0685 (15)	0.0364 (11)	0.0185 (14)	0.0123 (11)	0.0118 (11)
O17	0.0992 (14)	0.1262 (17)	0.0519 (10)	0.0060 (16)	0.0323 (10)	0.0120 (11)
C18	0.0624 (13)	0.0364 (9)	0.0459 (11)	0.0109 (10)	0.0055 (10)	0.0009 (8)
C19	0.0915 (18)	0.0492 (12)	0.0453 (12)	0.0135 (14)	0.0004 (12)	0.0102 (10)

Geometric parameters (Å, º)

C1—O2	1.452 (2)	C10—C18	1.535 (2)
C1—C10	1.520 (2)	C11—C12	1.532 (3)
C1—H11	0.9700	C11—H111	0.9700
C1—H12	0.9700	C11—H112	0.9700
O2—C3	1.337 (3)	C12—C13	1.513 (3)
C3—O3	1.206 (2)	C12—H121	0.9700
C3—C4	1.496 (3)	C12—H122	0.9700
C4—C5	1.529 (2)	C13—C17	1.518 (3)
C4—H41	0.9700	C13—C14	1.531 (3)
C4—H42	0.9700	C13—C19	1.544 (3)
C5—C6	1.515 (2)	C14—C15	1.535 (3)
C5—C10	1.531 (2)	C14—H141	0.9800
C5—H51	0.9800	C15—C16	1.538 (3)
C6—C7	1.519 (3)	C15—H151	0.9700
C6—H61	0.9700	C15—H152	0.9700
C6—H62	0.9700	C16—C17	1.510 (4)
C7—C8	1.523 (3)	C16—H161	0.9700
C7—H71	0.9700	C16—H162	0.9700
C7—H72	0.9700	C17—O17	1.207 (3)
C8—C14	1.519 (2)	C18—H181	0.9600
C8—C9	1.548 (2)	C18—H182	0.9600
C8—H81	0.9800	C18—H183	0.9600
C9—C11	1.530 (3)	C19—H191	0.9600
C9—C10	1.549 (2)	C19—H192	0.9600
C9—H91	0.9800	C19—H193	0.9600
O2—C1—C10	112.88 (16)	C9—C11—C12	113.45 (17)
O2—C1—H11	109.0	C9—C11—H111	108.9
C10—C1—H11	109.0	C12—C11—H111	108.9
O2—C1—H12	109.0	C9—C11—H112	108.9
C10—C1—H12	109.0	C12—C11—H112	108.9
H11—C1—H12	107.8	H111—C11—H112	107.7
C3—O2—C1	121.09 (15)	C13—C12—C11	109.70 (18)
O3—C3—O2	117.83 (19)	C13—C12—H121	109.7
O3—C3—C4	122.0 (2)	C11—C12—H121	109.7
O2—C3—C4	120.09 (16)	C13—C12—H122	109.7
C3—C4—C5	116.85 (16)	C11—C12—H122	109.7
C3—C4—H41	108.1	H121—C12—H122	108.2
C5—C4—H41	108.1	C12—C13—C17	116.40 (19)
C3—C4—H42	108.1	C12—C13—C14	109.76 (16)
C5—C4—H42	108.1	C17—C13—C14	100.03 (18)
H41—C4—H42	107.3	C12—C13—C19	110.9 (2)
C6—C5—C4	112.72 (15)	C17—C13—C19	105.69 (17)
C6—C5—C10	113.33 (14)	C14—C13—C19	113.75 (19)
C4—C5—C10	109.88 (14)	C8—C14—C13	113.22 (16)
C6—C5—H51	106.8	C8—C14—C15	120.54 (17)
C4—C5—H51	106.8	C13—C14—C15	103.96 (16)
C10—C5—H51	106.8	C8—C14—H141	106.0
C5—C6—C7	110.33 (16)	C13—C14—H141	106.0
C5—C6—H61	109.6	C15—C14—H141	106.0
C7—C6—H61	109.6	C14—C15—C16	102.58 (19)
C5—C6—H62	109.6	C14—C15—H151	111.3
C7—C6—H62	109.6	C16—C15—H151	111.3
H61—C6—H62	108.1	C14—C15—H152	111.3
C6—C7—C8	112.08 (16)	C16—C15—H152	111.3
C6—C7—H71	109.2	H151—C15—H152	109.2
C8—C7—H71	109.2	C17—C16—C15	105.90 (17)
C6—C7—H72	109.2	C17—C16—H161	110.6
C8—C7—H72	109.2	C15—C16—H161	110.6
H71—C7—H72	107.9	C17—C16—H162	110.6
C14—C8—C7	112.27 (15)	C15—C16—H162	110.6
C14—C8—C9	108.40 (15)	H161—C16—H162	108.7
C7—C8—C9	110.81 (14)	O17—C17—C16	126.2 (2)
C14—C8—H81	108.4	O17—C17—C13	125.6 (3)
C7—C8—H81	108.4	C16—C17—C13	108.2 (2)
C9—C8—H81	108.4	C10—C18—H181	109.5
C11—C9—C8	112.44 (14)	C10—C18—H182	109.5
C11—C9—C10	113.90 (15)	H181—C18—H182	109.5
C8—C9—C10	111.29 (14)	C10—C18—H183	109.5
C11—C9—H91	106.2	H181—C18—H183	109.5
C8—C9—H91	106.2	H182—C18—H183	109.5
C10—C9—H91	106.2	C13—C19—H191	109.5
C1—C10—C5	104.21 (14)	C13—C19—H192	109.5
C1—C10—C18	109.82 (16)	H191—C19—H192	109.5
C5—C10—C18	112.94 (15)	C13—C19—H193	109.5
C1—C10—C9	108.70 (14)	H191—C19—H193	109.5
C5—C10—C9	109.07 (13)	H192—C19—H193	109.5
C18—C10—C9	111.76 (14)

(12) 17-Hydroxy-2-oxaandrost-4-ene-3-one

Crystal data

C18H26O3	Dx = 1.232 Mg m^−3
Mr = 290.39	Melting point = 200–202 K
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 41 reflections
a = 14.241 (2) Å	θ = 18–63°
b = 9.4401 (9) Å	µ = 0.65 mm^−1
c = 11.648 (2) Å	T = 293 K
V = 1565.9 (4) Å^3	Prism, colourless
Z = 4	0.70 × 0.70 × 0.25 mm
F(000) = 632

Data collection

KM-4 diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 70.1°, θmin = 4.9°
Graphite monochromator	h = 0→17
ω–2θ scans	k = 0→11
1722 measured reflections	l = 0→14
1722 independent reflections	2 standard reflections every 100 reflections
1592 reflections with I > 2σ(I)	intensity decay: less than 2.7

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.031	w = 1/[σ^2(Fo^2) + (0.0602P)^2 + 0.1629P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.096	(Δ/σ)max = 0.001
S = 1.07	Δρmax = 0.17 e Å^−3
1722 reflections	Δρmin = −0.10 e Å^−3
222 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0078 (8)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.2 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.11952 (16)	−0.3651 (2)	0.4163 (2)	0.0589 (6)
H11	0.1084	−0.3944	0.4950	0.090 (9)*
H12	0.0600	−0.3695	0.3760	0.053 (6)*
O2	0.18402 (12)	−0.46399 (14)	0.36346 (15)	0.0642 (4)
C3	0.21884 (15)	−0.4286 (2)	0.2612 (2)	0.0567 (5)
O3	0.25854 (15)	−0.5203 (2)	0.20574 (16)	0.0787 (5)
C4	0.21500 (15)	−0.2819 (2)	0.22666 (17)	0.0536 (5)
H4	0.2292	−0.2588	0.1510	0.079 (8)*
C5	0.19175 (13)	−0.1782 (2)	0.29920 (16)	0.0439 (4)
C6	0.20792 (16)	−0.0256 (2)	0.2710 (2)	0.0569 (5)
H61	0.2197	−0.0167	0.1893	0.077 (8)*
H62	0.2635	0.0070	0.3112	0.080 (8)*
C7	0.12539 (16)	0.0687 (2)	0.30335 (19)	0.0577 (5)
H71	0.0735	0.0503	0.2516	0.069 (7)*
H72	0.1434	0.1672	0.2944	0.074 (7)*
C8	0.09342 (13)	0.04366 (17)	0.42640 (16)	0.0414 (4)
H8	0.1450	0.0675	0.4786	0.056 (6)*
C9	0.06817 (12)	−0.11419 (18)	0.44190 (15)	0.0395 (4)
H9	0.0215	−0.1355	0.3826	0.055 (6)*
C10	0.15385 (13)	−0.21237 (17)	0.41638 (15)	0.0406 (4)
C11	0.02079 (17)	−0.1477 (2)	0.55675 (19)	0.0554 (5)
H111	−0.0029	−0.2440	0.5547	0.065 (7)*
H112	0.0673	−0.1423	0.6174	0.074 (8)*
C12	−0.06016 (14)	−0.0471 (2)	0.58509 (19)	0.0532 (5)
H121	−0.1112	−0.0626	0.5314	0.075 (8)*
H122	−0.0833	−0.0673	0.6617	0.065 (7)*
C13	−0.02915 (13)	0.10649 (18)	0.57877 (16)	0.0428 (4)
C14	0.00826 (13)	0.13264 (18)	0.45747 (16)	0.0444 (4)
H14	−0.0419	0.1044	0.4046	0.053 (6)*
C15	0.01574 (18)	0.2947 (2)	0.4492 (2)	0.0666 (6)
H151	0.0082	0.3265	0.3705	0.101 (10)*
H152	0.0758	0.3278	0.4781	0.098 (10)*
C16	−0.06548 (18)	0.3475 (2)	0.5251 (2)	0.0695 (7)
H161	−0.0422	0.4120	0.5833	0.080 (9)*
H162	−0.1119	0.3967	0.4790	0.080 (8)*
C17	−0.10878 (14)	0.2162 (2)	0.58098 (19)	0.0536 (5)
H171	−0.1603	0.1822	0.5324	0.062 (6)*
O17	−0.14533 (12)	0.25201 (18)	0.69021 (15)	0.0662 (4)
H17	−0.182 (2)	0.178 (3)	0.716 (3)	0.082 (9)*
C18	0.23351 (15)	−0.1962 (2)	0.50425 (18)	0.0557 (5)
H181	0.2099	−0.2158	0.5798	0.092 (9)*
H182	0.2574	−0.1011	0.5017	0.081 (8)*
H183	0.2830	−0.2615	0.4862	0.084 (8)*
C19	0.04137 (16)	0.1407 (3)	0.67298 (19)	0.0659 (6)
H191	0.0614	0.2374	0.6657	0.097 (10)*
H192	0.0947	0.0792	0.6661	0.088 (9)*
H193	0.0125	0.1271	0.7466	0.086 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0628 (12)	0.0356 (9)	0.0783 (14)	−0.0029 (9)	0.0173 (11)	−0.0079 (9)
O2	0.0727 (9)	0.0387 (7)	0.0812 (11)	0.0029 (7)	0.0126 (9)	−0.0108 (7)
C3	0.0528 (11)	0.0573 (11)	0.0600 (12)	0.0011 (10)	−0.0076 (10)	−0.0222 (10)
O3	0.0894 (11)	0.0731 (10)	0.0735 (10)	0.0243 (9)	−0.0054 (9)	−0.0337 (9)
C4	0.0518 (10)	0.0641 (12)	0.0450 (10)	0.0024 (9)	−0.0024 (8)	−0.0106 (9)
C5	0.0403 (8)	0.0460 (9)	0.0455 (9)	−0.0038 (7)	−0.0008 (7)	−0.0034 (8)
C6	0.0621 (12)	0.0504 (11)	0.0582 (12)	−0.0044 (9)	0.0164 (10)	0.0066 (9)
C7	0.0671 (12)	0.0451 (10)	0.0611 (12)	−0.0002 (10)	0.0131 (11)	0.0154 (9)
C8	0.0424 (8)	0.0327 (8)	0.0492 (9)	−0.0019 (7)	−0.0010 (7)	0.0019 (7)
C9	0.0416 (8)	0.0333 (7)	0.0437 (8)	−0.0026 (7)	0.0015 (7)	0.0009 (7)
C10	0.0456 (9)	0.0323 (8)	0.0438 (8)	−0.0018 (7)	0.0005 (7)	−0.0028 (7)
C11	0.0681 (12)	0.0370 (8)	0.0612 (12)	0.0062 (9)	0.0215 (10)	0.0096 (8)
C12	0.0558 (11)	0.0410 (9)	0.0627 (12)	0.0007 (9)	0.0171 (10)	0.0025 (9)
C13	0.0432 (8)	0.0369 (8)	0.0484 (9)	0.0040 (7)	−0.0047 (8)	−0.0039 (7)
C14	0.0448 (9)	0.0346 (8)	0.0536 (10)	0.0016 (7)	−0.0044 (8)	0.0043 (8)
C15	0.0757 (15)	0.0357 (9)	0.0883 (16)	0.0063 (10)	0.0100 (13)	0.0084 (11)
C16	0.0763 (14)	0.0408 (10)	0.0913 (17)	0.0153 (10)	0.0014 (14)	0.0003 (12)
C17	0.0491 (10)	0.0463 (10)	0.0654 (12)	0.0104 (8)	−0.0066 (9)	−0.0098 (9)
O17	0.0647 (8)	0.0569 (9)	0.0771 (10)	0.0094 (8)	0.0083 (8)	−0.0195 (8)
C18	0.0584 (11)	0.0564 (11)	0.0524 (10)	0.0148 (10)	−0.0081 (9)	−0.0075 (9)
C19	0.0615 (12)	0.0758 (15)	0.0604 (12)	0.0148 (12)	−0.0153 (10)	−0.0172 (12)

Geometric parameters (Å, º)

C1—O2	1.447 (2)	C11—H111	0.9700
C1—C10	1.523 (2)	C11—H112	0.9700
C1—H11	0.9700	C12—C13	1.517 (2)
C1—H12	0.9700	C12—H121	0.9700
O2—C3	1.332 (3)	C12—H122	0.9700
C3—O3	1.220 (3)	C13—C19	1.522 (3)
C3—C4	1.443 (3)	C13—C14	1.530 (3)
C4—C5	1.335 (3)	C13—C17	1.536 (2)
C4—H4	0.9300	C14—C15	1.537 (3)
C5—C6	1.495 (3)	C14—H14	0.9800
C5—C10	1.503 (3)	C15—C16	1.539 (3)
C6—C7	1.522 (3)	C15—H151	0.9700
C6—H61	0.9700	C15—H152	0.9700
C6—H62	0.9700	C16—C17	1.530 (3)
C7—C8	1.522 (3)	C16—H161	0.9700
C7—H71	0.9700	C16—H162	0.9700
C7—H72	0.9700	C17—O17	1.416 (3)
C8—C14	1.519 (2)	C17—H171	0.9800
C8—C9	1.543 (2)	O17—H17	0.92 (3)
C8—H8	0.9800	C18—H181	0.9600
C9—C11	1.531 (3)	C18—H182	0.9600
C9—C10	1.561 (2)	C18—H183	0.9600
C9—H9	0.9800	C19—H191	0.9600
C10—C18	1.536 (3)	C19—H192	0.9600
C11—C12	1.530 (3)	C19—H193	0.9600
O2—C1—C10	114.03 (16)	H111—C11—H112	107.8
O2—C1—H11	108.7	C13—C12—C11	111.31 (15)
C10—C1—H11	108.7	C13—C12—H121	109.4
O2—C1—H12	108.7	C11—C12—H121	109.4
C10—C1—H12	108.7	C13—C12—H122	109.4
H11—C1—H12	107.6	C11—C12—H122	109.4
C3—O2—C1	117.04 (18)	H121—C12—H122	108.0
O3—C3—O2	117.9 (2)	C12—C13—C19	111.09 (18)
O3—C3—C4	123.4 (2)	C12—C13—C14	107.48 (15)
O2—C3—C4	118.41 (18)	C19—C13—C14	113.68 (16)
C5—C4—C3	122.5 (2)	C12—C13—C17	115.37 (16)
C5—C4—H4	118.8	C19—C13—C17	109.39 (16)
C3—C4—H4	118.8	C14—C13—C17	99.43 (15)
C4—C5—C6	121.96 (19)	C8—C14—C13	114.13 (14)
C4—C5—C10	120.42 (18)	C8—C14—C15	118.70 (17)
C6—C5—C10	117.50 (16)	C13—C14—C15	104.05 (17)
C5—C6—C7	112.98 (17)	C8—C14—H14	106.4
C5—C6—H61	109.0	C13—C14—H14	106.4
C7—C6—H61	109.0	C15—C14—H14	106.4
C5—C6—H62	109.0	C14—C15—C16	103.54 (18)
C7—C6—H62	109.0	C14—C15—H151	111.1
H61—C6—H62	107.8	C16—C15—H151	111.1
C6—C7—C8	111.90 (17)	C14—C15—H152	111.1
C6—C7—H71	109.2	C16—C15—H152	111.1
C8—C7—H71	109.2	H151—C15—H152	109.0
C6—C7—H72	109.2	C17—C16—C15	106.57 (17)
C8—C7—H72	109.2	C17—C16—H161	110.4
H71—C7—H72	107.9	C15—C16—H161	110.4
C14—C8—C7	112.15 (16)	C17—C16—H162	110.4
C14—C8—C9	108.67 (14)	C15—C16—H162	110.4
C7—C8—C9	109.27 (15)	H161—C16—H162	108.6
C14—C8—H8	108.9	O17—C17—C16	109.70 (18)
C7—C8—H8	108.9	O17—C17—C13	116.59 (18)
C9—C8—H8	108.9	C16—C17—C13	103.98 (17)
C11—C9—C8	113.83 (15)	O17—C17—H171	108.8
C11—C9—C10	112.85 (15)	C16—C17—H171	108.8
C8—C9—C10	111.65 (14)	C13—C17—H171	108.8
C11—C9—H9	105.9	C17—O17—H17	108.7 (19)
C8—C9—H9	105.9	C10—C18—H181	109.5
C10—C9—H9	105.9	C10—C18—H182	109.5
C5—C10—C1	108.56 (15)	H181—C18—H182	109.5
C5—C10—C18	108.58 (16)	C10—C18—H183	109.5
C1—C10—C18	109.38 (17)	H181—C18—H183	109.5
C5—C10—C9	109.04 (15)	H182—C18—H183	109.5
C1—C10—C9	108.15 (15)	C13—C19—H191	109.5
C18—C10—C9	113.04 (14)	C13—C19—H192	109.5
C12—C11—C9	113.11 (16)	H191—C19—H192	109.5
C12—C11—H111	109.0	C13—C19—H193	109.5
C9—C11—H111	109.0	H191—C19—H193	109.5
C12—C11—H112	109.0	H192—C19—H193	109.5
C9—C11—H112	109.0

(13) 6alpha-hydroxy-2-oxaandrost-4-ene-3,17-dione

Crystal data

C18H24O4	F(000) = 328
Mr = 304.37	Dx = 1.271 Mg m^−3
Monoclinic, P21	Melting point = 244–246 K
Hall symbol: P 2y1	Cu Kα radiation, λ = 1.54178 Å
a = 6.2214 (7) Å	Cell parameters from 43 reflections
b = 12.050 (1) Å	θ = 25–50°
c = 10.888 (1) Å	µ = 0.72 mm^−1
β = 103.07 (1)°	T = 293 K
V = 795.10 (13) Å^3	Plate, brown
Z = 2	0.40 × 0.40 × 0.20 mm

Data collection

KM-4 diffractometer	Rint = 0.031
Radiation source: fine-focus sealed tube	θmax = 70.1°, θmin = 4.2°
Graphite monochromator	h = −7→2
ω–2θ scans	k = −14→14
1624 measured reflections	l = −13→13
1596 independent reflections	2 standard reflections every 100 reflections
1458 reflections with I > 2σ(I)	intensity decay: less than 2

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	Riding
wR(F^2) = 0.105	Calculated w = 1/[σ^2(Fo^2) + (0.0677P)^2 + 0.099P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = −0.020
1512 reflections	Δρmax = 0.14 e Å^−3
228 parameters	Δρmin = −0.18 e Å^−3
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (30)

Special details

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 on F² for ALL reflections except for 2 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion 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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.2845 (6)	0.2776 (2)	0.2059 (3)	0.0608 (7)
H11	0.3663 (6)	0.2813 (2)	0.1400 (3)	0.077 (11)*
H12	0.1313 (6)	0.2631 (2)	0.1659 (3)	0.073 (10)*
O2	0.2987 (4)	0.3842 (2)	0.2683 (2)	0.0635 (5)
C3	0.2201 (4)	0.3901 (2)	0.3732 (3)	0.0545 (6)
O3	0.1886 (4)	0.4811 (2)	0.4138 (3)	0.0722 (6)
C4	0.1948 (4)	0.2869 (2)	0.4378 (3)	0.0496 (6)
H4	0.1184 (4)	0.2880 (2)	0.5020 (3)	0.058 (8)*
C5	0.2765 (3)	0.1911 (2)	0.4086 (2)	0.0394 (5)
C6	0.2953 (4)	0.0912 (2)	0.4931 (2)	0.0434 (5)
H61	0.4529 (4)	0.0798 (2)	0.5291 (2)	0.051 (8)*
O6	0.1942 (4)	0.1104 (2)	0.5954 (2)	0.0619 (6)
H6	0.080 (6)	0.061 (4)	0.589 (3)	0.072 (10)*
C7	0.2113 (5)	−0.0129 (2)	0.4182 (2)	0.0447 (6)
H71	0.0535 (5)	−0.0066 (2)	0.3849 (2)	0.051 (7)*
H72	0.2378 (5)	−0.0768 (2)	0.4737 (2)	0.051 (8)*
C8	0.3261 (4)	−0.0297 (2)	0.3098 (2)	0.0375 (5)
H8	0.4850 (4)	−0.0381 (2)	0.3441 (2)	0.047 (7)*
C9	0.2857 (4)	0.0724 (2)	0.2217 (2)	0.0405 (5)
H9	0.1253 (4)	0.0807 (2)	0.1948 (2)	0.044 (7)*
C10	0.3724 (4)	0.1813 (2)	0.2928 (2)	0.0411 (5)
C11	0.3701 (6)	0.0563 (3)	0.1003 (2)	0.0571 (7)
H111	0.3199 (6)	0.1180 (3)	0.0439 (2)	0.075 (10)*
H112	0.5301 (6)	0.0576 (3)	0.1215 (2)	0.077 (11)*
C12	0.2925 (5)	−0.0525 (3)	0.0309 (2)	0.0565 (7)
H121	0.1344 (5)	−0.0498 (3)	−0.0030 (2)	0.055 (8)*
H122	0.3641 (5)	−0.0620 (3)	−0.0388 (2)	0.068 (9)*
C13	0.3483 (4)	−0.1495 (2)	0.1208 (2)	0.0447 (6)
C14	0.2402 (4)	−0.1317 (2)	0.2326 (2)	0.0398 (5)
H14	0.0836 (4)	−0.1178 (2)	0.1962 (2)	0.065 (9)*
C15	0.2522 (5)	−0.2458 (2)	0.2960 (3)	0.0535 (6)
H151	0.3975 (5)	−0.2590 (2)	0.3492 (3)	0.078 (11)*
H152	0.1427 (5)	−0.2525 (2)	0.3464 (3)	0.067 (9)*
C16	0.2039 (6)	−0.3259 (3)	0.1841 (3)	0.0660 (8)
H161	0.2973 (6)	−0.3911 (3)	0.2018 (3)	0.100 (14)*
H162	0.0508 (6)	−0.3493 (3)	0.1660 (3)	0.086 (11)*
C17	0.2531 (4)	−0.2614 (3)	0.0736 (2)	0.0505 (6)
O17	0.2192 (3)	−0.2936 (2)	−0.0342 (2)	0.0667 (6)
C18	0.5999 (4)	−0.1692 (3)	0.1616 (3)	0.0628 (8)
H181	0.6708 (6)	−0.1031 (8)	0.200 (2)	0.094 (13)*
H182	0.6563 (8)	−0.187 (2)	0.0890 (5)	0.076 (10)*
H183	0.6289 (5)	−0.2294 (14)	0.2208 (19)	0.104 (15)*
C19	0.6254 (4)	0.1873 (3)	0.3332 (2)	0.0518 (6)
H191	0.6791 (5)	0.1267 (10)	0.3891 (16)	0.060 (9)*
H192	0.6683 (4)	0.2563 (8)	0.3758 (17)	0.081 (11)*
H193	0.6867 (4)	0.1825 (17)	0.2600 (3)	0.064 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.084 (2)	0.0416 (14)	0.0529 (14)	−0.0059 (14)	0.0084 (13)	0.0039 (12)
O2	0.0825 (13)	0.0383 (10)	0.0695 (12)	−0.0025 (10)	0.0167 (10)	0.0040 (9)
C3	0.0436 (12)	0.0410 (14)	0.077 (2)	0.0023 (11)	0.0109 (11)	−0.0024 (13)
O3	0.0672 (12)	0.0431 (11)	0.110 (2)	0.0065 (9)	0.0284 (12)	−0.0067 (12)
C4	0.0432 (12)	0.0445 (13)	0.0638 (14)	−0.0022 (10)	0.0177 (10)	−0.0057 (13)
C5	0.0339 (9)	0.0391 (11)	0.0453 (12)	−0.0057 (9)	0.0090 (8)	−0.0049 (10)
C6	0.0488 (12)	0.0418 (13)	0.0431 (11)	−0.0050 (10)	0.0174 (9)	−0.0044 (10)
O6	0.0818 (13)	0.0590 (12)	0.0556 (10)	−0.0205 (11)	0.0384 (10)	−0.0171 (9)
C7	0.0563 (13)	0.0390 (12)	0.0433 (12)	−0.0060 (10)	0.0209 (10)	−0.0011 (10)
C8	0.0374 (10)	0.0387 (11)	0.0371 (10)	−0.0008 (9)	0.0101 (8)	−0.0003 (9)
C9	0.0436 (11)	0.0390 (12)	0.0385 (11)	−0.0035 (10)	0.0084 (8)	−0.0009 (10)
C10	0.0438 (10)	0.0405 (12)	0.0399 (10)	−0.0053 (10)	0.0115 (8)	−0.0003 (10)
C11	0.085 (2)	0.0498 (15)	0.0411 (12)	−0.0125 (14)	0.0232 (12)	−0.0014 (12)
C12	0.075 (2)	0.058 (2)	0.0381 (11)	−0.0055 (14)	0.0155 (11)	−0.0047 (12)
C13	0.0400 (11)	0.052 (2)	0.0416 (11)	0.0018 (10)	0.0089 (9)	−0.0056 (11)
C14	0.0371 (9)	0.0406 (13)	0.0418 (11)	−0.0006 (9)	0.0093 (8)	−0.0009 (10)
C15	0.070 (2)	0.0402 (14)	0.0523 (13)	−0.0026 (12)	0.0172 (12)	0.0000 (11)
C16	0.086 (2)	0.045 (2)	0.067 (2)	−0.004 (2)	0.0175 (15)	−0.0071 (15)
C17	0.0457 (11)	0.0518 (14)	0.0520 (12)	0.0093 (11)	0.0068 (9)	−0.0102 (12)
O17	0.0730 (12)	0.0693 (15)	0.0542 (10)	0.0048 (10)	0.0070 (8)	−0.0235 (10)
C18	0.0408 (12)	0.087 (2)	0.063 (2)	0.0030 (14)	0.0170 (11)	−0.019 (2)
C19	0.0456 (12)	0.0581 (15)	0.0555 (13)	−0.0133 (12)	0.0196 (10)	−0.0064 (13)

Geometric parameters (Å, º)

C1—O2	1.446 (4)	C11—C12	1.536 (4)
C1—C10	1.519 (4)	C11—H111	0.97
C1—H11	0.97	C11—H112	0.97
C1—H12	0.97	C12—C13	1.513 (4)
O2—C3	1.342 (4)	C12—H121	0.97
C3—O3	1.215 (3)	C12—H122	0.97
C3—C4	1.454 (4)	C13—C17	1.515 (4)
C4—C5	1.328 (4)	C13—C14	1.532 (3)
C4—H4	0.93	C13—C18	1.546 (3)
C5—C6	1.503 (3)	C14—C15	1.532 (4)
C5—C10	1.517 (3)	C14—H14	0.98
C6—O6	1.417 (3)	C15—C16	1.530 (4)
C6—C7	1.522 (3)	C15—H151	0.97
C6—H61	0.98	C15—H152	0.97
O6—H6	0.92 (4)	C16—C17	1.520 (4)
C7—C8	1.525 (3)	C16—H161	0.97
C7—H71	0.97	C16—H162	0.97
C7—H72	0.97	C17—O17	1.209 (3)
C8—C14	1.516 (3)	C18—H181	0.96
C8—C9	1.545 (3)	C18—H182	0.96
C8—H8	0.98	C18—H183	0.96
C9—C11	1.541 (3)	C19—H191	0.96
C9—C10	1.557 (3)	C19—H192	0.96
C9—H9	0.98	C19—H193	0.96
C10—C19	1.537 (3)
O2—C1—C10	114.2 (2)	C9—C11—H111	108.86 (15)
O2—C1—H11	108.7 (2)	C12—C11—H112	108.9 (2)
C10—C1—H11	108.7 (2)	C9—C11—H112	108.86 (14)
O2—C1—H12	108.7 (2)	H111—C11—H112	107.7
C10—C1—H12	108.7 (2)	C13—C12—C11	109.9 (2)
H11—C1—H12	107.6	C13—C12—H121	109.68 (14)
C3—O2—C1	116.8 (2)	C11—C12—H121	109.7 (2)
O3—C3—O2	118.5 (3)	C13—C12—H122	109.69 (13)
O3—C3—C4	123.5 (3)	C11—C12—H122	109.69 (14)
O2—C3—C4	117.8 (2)	H121—C12—H122	108.2
C5—C4—C3	122.6 (2)	C12—C13—C17	116.9 (2)
C5—C4—H4	118.71 (14)	C12—C13—C14	109.2 (2)
C3—C4—H4	118.71 (15)	C17—C13—C14	100.7 (2)
C4—C5—C6	122.1 (2)	C12—C13—C18	111.9 (2)
C4—C5—C10	120.7 (2)	C17—C13—C18	104.7 (2)
C6—C5—C10	117.1 (2)	C14—C13—C18	113.0 (2)
O6—C6—C5	111.3 (2)	C8—C14—C13	113.0 (2)
O6—C6—C7	113.3 (2)	C8—C14—C15	120.1 (2)
C5—C6—C7	111.3 (2)	C13—C14—C15	104.3 (2)
O6—C6—H61	106.85 (13)	C8—C14—H14	106.16 (11)
C5—C6—H61	106.85 (11)	C13—C14—H14	106.16 (12)
C7—C6—H61	106.85 (14)	C15—C14—H14	106.16 (14)
C6—O6—H6	108 (2)	C16—C15—C14	103.1 (2)
C6—C7—C8	111.1 (2)	C16—C15—H151	111.1 (2)
C6—C7—H71	109.41 (13)	C14—C15—H151	111.15 (13)
C8—C7—H71	109.41 (13)	C16—C15—H152	111.1 (2)
C6—C7—H72	109.42 (13)	C14—C15—H152	111.15 (13)
C8—C7—H72	109.41 (13)	H151—C15—H152	109.1
H71—C7—H72	108.0	C17—C16—C15	105.6 (2)
C14—C8—C7	111.7 (2)	C17—C16—H161	110.6 (2)
C14—C8—C9	108.3 (2)	C15—C16—H161	110.6 (2)
C7—C8—C9	109.6 (2)	C17—C16—H162	110.6 (2)
C14—C8—H8	109.08 (11)	C15—C16—H162	110.6 (2)
C7—C8—H8	109.08 (13)	H161—C16—H162	108.8
C9—C8—H8	109.08 (11)	O17—C17—C13	125.8 (3)
C11—C9—C8	113.1 (2)	O17—C17—C16	125.6 (3)
C11—C9—C10	112.7 (2)	C13—C17—C16	108.7 (2)
C8—C9—C10	111.9 (2)	C13—C18—H181	109.5 (2)
C11—C9—H9	106.13 (14)	C13—C18—H182	109.47 (14)
C8—C9—H9	106.13 (11)	H181—C18—H182	109.5
C10—C9—H9	106.13 (12)	C13—C18—H183	109.5 (2)
C5—C10—C1	107.7 (2)	H181—C18—H183	109.5
C5—C10—C19	109.2 (2)	H182—C18—H183	109.5
C1—C10—C19	110.1 (2)	C10—C19—H191	109.47 (15)
C5—C10—C9	108.8 (2)	C10—C19—H192	109.47 (15)
C1—C10—C9	107.4 (2)	H191—C19—H192	109.5
C19—C10—C9	113.5 (2)	C10—C19—H193	109.47 (12)
C12—C11—C9	113.6 (2)	H191—C19—H193	109.5
C12—C11—H111	108.86 (15)	H192—C19—H193	109.5
C10—C1—O2—C3	−49.7 (4)	C8—C9—C10—C1	−168.8 (2)
C1—O2—C3—O3	−165.6 (3)	C11—C9—C10—C19	−59.6 (3)
C1—O2—C3—C4	19.4 (4)	C8—C9—C10—C19	69.2 (2)
O3—C3—C4—C5	−164.2 (3)	C8—C9—C11—C12	49.9 (3)
O2—C3—C4—C5	10.5 (4)	C10—C9—C11—C12	178.1 (2)
C3—C4—C5—C6	165.9 (2)	C9—C11—C12—C13	−52.8 (3)
C3—C4—C5—C10	−9.1 (4)	C11—C12—C13—C17	171.0 (2)
C4—C5—C6—O6	6.5 (3)	C11—C12—C13—C14	57.6 (3)
C10—C5—C6—O6	−178.4 (2)	C11—C12—C13—C18	−68.3 (3)
C4—C5—C6—C7	133.9 (2)	C7—C8—C14—C13	178.6 (2)
C10—C5—C6—C7	−51.0 (3)	C9—C8—C14—C13	57.8 (2)
O6—C6—C7—C8	−179.8 (2)	C7—C8—C14—C15	−57.6 (3)
C5—C6—C7—C8	53.9 (3)	C9—C8—C14—C15	−178.3 (2)
C6—C7—C8—C14	−178.7 (2)	C12—C13—C14—C8	−63.0 (2)
C6—C7—C8—C9	−58.7 (3)	C17—C13—C14—C8	173.4 (2)
C14—C8—C9—C11	−50.5 (2)	C18—C13—C14—C8	62.3 (3)
C7—C8—C9—C11	−172.5 (2)	C12—C13—C14—C15	164.9 (2)
C14—C8—C9—C10	−179.1 (2)	C17—C13—C14—C15	41.2 (2)
C7—C8—C9—C10	58.8 (2)	C18—C13—C14—C15	−69.9 (3)
C4—C5—C10—C1	−19.2 (3)	C8—C14—C15—C16	−166.9 (2)
C6—C5—C10—C1	165.6 (2)	C13—C14—C15—C16	−39.0 (3)
C4—C5—C10—C19	100.4 (3)	C14—C15—C16—C17	20.6 (3)
C6—C5—C10—C19	−74.8 (3)	C12—C13—C17—O17	32.7 (4)
C4—C5—C10—C9	−135.3 (2)	C14—C13—C17—O17	150.8 (3)
C6—C5—C10—C9	49.5 (2)	C18—C13—C17—O17	−91.8 (3)
O2—C1—C10—C5	47.1 (3)	C12—C13—C17—C16	−146.5 (2)
O2—C1—C10—C19	−71.8 (3)	C14—C13—C17—C16	−28.4 (3)
O2—C1—C10—C9	164.1 (2)	C18—C13—C17—C16	89.1 (3)
C11—C9—C10—C5	178.6 (2)	C15—C16—C17—O17	−174.1 (3)
C8—C9—C10—C5	−52.5 (2)	C15—C16—C17—C13	5.0 (3)
C11—C9—C10—C1	62.3 (3)

(14) 6-hydroxy-2-oxa-5beta-androstane-3,17-dione

Crystal data

C18H26O4	Dx = 1.244 Mg m^−3
Mr = 306.39	Melting point = 235–238 K
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 56 reflections
a = 6.335 (1) Å	θ = 16–42°
b = 9.482 (1) Å	µ = 0.70 mm^−1
c = 27.245 (6) Å	T = 293 K
V = 1636.6 (5) Å^3	Plate, colourless
Z = 4	0.3 × 0.2 × 0.1 mm
F(000) = 664

Data collection

KM-4 diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 65.1°, θmin = 3.2°
Graphite monochromator	h = 0→7
ω–2θ scans	k = 0→10
1586 measured reflections	l = 0→32
1586 independent reflections	2 standard reflections every 100 reflections
913 reflections with I > 2σ(I)	intensity decay: less than 2.3%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.034	w = 1/[σ^2(Fo^2) + (0.0573P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.104	(Δ/σ)max = 0.001
S = 0.98	Δρmax = 0.14 e Å^−3
1586 reflections	Δρmin = −0.13 e Å^−3
231 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0015 (4)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.0 (5)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	−0.1627 (7)	0.0346 (4)	0.16963 (13)	0.0607 (12)
H11	−0.2474	−0.0424	0.1824	0.049 (11)*
H12	−0.0888	−0.0002	0.1409	0.074 (13)*
O2	−0.0088 (4)	0.0724 (3)	0.20611 (10)	0.0678 (9)
C3	−0.0682 (8)	0.1548 (5)	0.24375 (15)	0.0629 (12)
O3	0.0597 (5)	0.1700 (4)	0.27636 (10)	0.0916 (11)
C4	−0.2735 (7)	0.2286 (5)	0.24298 (12)	0.0593 (11)
H41	−0.2452	0.3291	0.2434	0.12 (2)*
H42	−0.3463	0.2061	0.2733	0.066 (12)*
C5	−0.4261 (6)	0.1996 (4)	0.20056 (11)	0.0469 (9)
H51	−0.5180	0.1218	0.2107	0.060 (12)*
C6	−0.5674 (7)	0.3273 (4)	0.19073 (12)	0.0515 (10)
H61	−0.6776	0.2994	0.1674	0.062 (12)*
O6	−0.6667 (5)	0.3755 (3)	0.23476 (10)	0.0722 (10)
H6	−0.745 (11)	0.315 (6)	0.2501 (19)	0.14 (3)*
C7	−0.4470 (7)	0.4506 (4)	0.16920 (12)	0.0521 (10)
H71	−0.3497	0.4869	0.1936	0.057 (11)*
H72	−0.5456	0.5253	0.1611	0.074 (13)*
C8	−0.3240 (6)	0.4097 (4)	0.12334 (11)	0.0432 (9)
H81	−0.4254	0.3898	0.0971	0.044 (9)*
C9	−0.1868 (6)	0.2770 (4)	0.13117 (10)	0.0424 (9)
H91	−0.0796	0.3033	0.1554	0.044 (9)*
C10	−0.3097 (6)	0.1523 (4)	0.15371 (11)	0.0467 (10)
C11	−0.0656 (8)	0.2397 (4)	0.08390 (13)	0.0567 (11)
H111	0.0266	0.1602	0.0904	0.065 (12)*
H112	−0.1658	0.2111	0.0589	0.063 (12)*
C12	0.0664 (8)	0.3623 (4)	0.06433 (14)	0.0622 (11)
H121	0.1806	0.3819	0.0870	0.083 (15)*
H122	0.1280	0.3360	0.0330	0.085 (14)*
C13	−0.0660 (6)	0.4938 (4)	0.05778 (11)	0.0490 (9)
C14	−0.1800 (6)	0.5273 (4)	0.10631 (11)	0.0466 (10)
H141	−0.0682	0.5328	0.1311	0.043 (9)*
C15	−0.2553 (8)	0.6795 (4)	0.09900 (15)	0.0611 (12)
H151	−0.3783	0.6834	0.0778	0.068 (14)*
H152	−0.2885	0.7239	0.1301	0.080 (14)*
C16	−0.0637 (9)	0.7488 (5)	0.07470 (17)	0.0726 (13)
H161	−0.1081	0.8189	0.0509	0.115 (18)*
H162	0.0251	0.7939	0.0991	0.100 (17)*
C17	0.0528 (8)	0.6305 (5)	0.04984 (14)	0.0647 (12)
O17	0.2216 (6)	0.6411 (4)	0.02880 (12)	0.1031 (13)
C18	−0.4655 (7)	0.0859 (5)	0.11724 (14)	0.0656 (12)
H181	−0.5594	0.0238	0.1345	0.12 (2)*
H182	−0.3888	0.0335	0.0929	0.083 (14)*
H183	−0.5457	0.1590	0.1015	0.093 (17)*
C19	−0.2197 (9)	0.4808 (6)	0.01356 (12)	0.0744 (15)
H191	−0.3110	0.4011	0.0184	0.11 (2)*
H192	−0.1401	0.4681	−0.0161	0.13 (2)*
H193	−0.3030	0.5650	0.0111	0.11 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.075 (3)	0.052 (3)	0.055 (2)	0.008 (3)	0.009 (3)	0.007 (2)
O2	0.0600 (19)	0.080 (2)	0.0635 (17)	0.0082 (17)	−0.0039 (16)	0.0202 (16)
C3	0.065 (3)	0.071 (3)	0.052 (2)	−0.017 (3)	−0.008 (2)	0.025 (2)
O3	0.078 (2)	0.118 (3)	0.079 (2)	−0.016 (2)	−0.030 (2)	0.0286 (19)
C4	0.066 (3)	0.073 (3)	0.039 (2)	−0.007 (3)	−0.001 (2)	0.004 (2)
C5	0.050 (2)	0.051 (2)	0.0397 (18)	−0.008 (2)	0.0016 (19)	0.0017 (16)
C6	0.043 (2)	0.065 (3)	0.0462 (18)	0.000 (2)	0.011 (2)	−0.007 (2)
O6	0.076 (2)	0.076 (2)	0.0649 (17)	−0.0027 (19)	0.0332 (17)	−0.0112 (16)
C7	0.059 (3)	0.052 (2)	0.046 (2)	0.002 (3)	0.005 (2)	−0.0034 (18)
C8	0.046 (2)	0.048 (2)	0.0353 (17)	0.004 (2)	0.0032 (18)	−0.0050 (16)
C9	0.045 (2)	0.048 (2)	0.0339 (17)	0.007 (2)	−0.0005 (17)	−0.0036 (16)
C10	0.056 (2)	0.043 (2)	0.0403 (17)	−0.002 (2)	−0.002 (2)	−0.0047 (17)
C11	0.069 (3)	0.052 (3)	0.050 (2)	0.020 (3)	0.016 (2)	−0.0003 (19)
C12	0.067 (3)	0.070 (3)	0.050 (2)	0.013 (3)	0.022 (2)	0.009 (2)
C13	0.056 (2)	0.055 (2)	0.0363 (17)	0.004 (2)	0.006 (2)	0.0038 (17)
C14	0.055 (2)	0.051 (2)	0.0346 (17)	0.004 (2)	−0.0002 (19)	0.0008 (16)
C15	0.084 (3)	0.046 (2)	0.053 (2)	0.009 (3)	0.007 (3)	−0.0016 (19)
C16	0.096 (4)	0.055 (3)	0.067 (3)	−0.002 (3)	0.006 (3)	0.006 (2)
C17	0.077 (3)	0.065 (3)	0.051 (2)	−0.006 (3)	0.006 (3)	0.012 (2)
O17	0.091 (3)	0.101 (3)	0.117 (3)	−0.003 (2)	0.041 (2)	0.029 (2)
C18	0.080 (3)	0.061 (3)	0.055 (2)	−0.006 (3)	−0.006 (3)	−0.010 (2)
C19	0.105 (4)	0.078 (4)	0.040 (2)	0.014 (4)	−0.003 (2)	−0.002 (2)

Geometric parameters (Å, º)

C1—O2	1.438 (5)	C10—C18	1.535 (5)
C1—C10	1.517 (5)	C11—C12	1.528 (5)
C1—H11	0.9700	C11—H111	0.9700
C1—H12	0.9700	C11—H112	0.9700
O2—C3	1.343 (5)	C12—C13	1.513 (5)
C3—O3	1.211 (5)	C12—H121	0.9700
C3—C4	1.477 (6)	C12—H122	0.9700
C4—C5	1.532 (5)	C13—C17	1.515 (6)
C4—H41	0.9700	C13—C14	1.540 (4)
C4—H42	0.9700	C13—C19	1.554 (5)
C5—C6	1.529 (5)	C14—C15	1.533 (5)
C5—C10	1.541 (5)	C14—H141	0.9800
C5—H51	0.9800	C15—C16	1.531 (6)
C6—O6	1.429 (4)	C15—H151	0.9700
C6—C7	1.514 (5)	C15—H152	0.9700
C6—H61	0.9800	C16—C17	1.504 (6)
O6—H6	0.87 (6)	C16—H161	0.9700
C7—C8	1.523 (4)	C16—H162	0.9700
C7—H71	0.9700	C17—O17	1.218 (5)
C7—H72	0.9700	C18—H181	0.9600
C8—C14	1.514 (5)	C18—H182	0.9600
C8—C9	1.544 (5)	C18—H183	0.9600
C8—H81	0.9800	C19—H191	0.9600
C9—C11	1.541 (4)	C19—H192	0.9600
C9—C10	1.543 (5)	C19—H193	0.9600
C9—H91	0.9800
O2—C1—C10	115.5 (3)	C5—C10—C9	110.4 (3)
O2—C1—H11	108.4	C12—C11—C9	112.9 (3)
C10—C1—H11	108.4	C12—C11—H111	109.0
O2—C1—H12	108.4	C9—C11—H111	109.0
C10—C1—H12	108.4	C12—C11—H112	109.0
H11—C1—H12	107.5	C9—C11—H112	109.0
C3—O2—C1	118.9 (3)	H111—C11—H112	107.8
O3—C3—O2	116.2 (5)	C13—C12—C11	111.4 (4)
O3—C3—C4	122.9 (4)	C13—C12—H121	109.4
O2—C3—C4	120.8 (4)	C11—C12—H121	109.4
C3—C4—C5	118.8 (3)	C13—C12—H122	109.4
C3—C4—H41	107.6	C11—C12—H122	109.4
C5—C4—H41	107.6	H121—C12—H122	108.0
C3—C4—H42	107.6	C12—C13—C17	116.5 (4)
C5—C4—H42	107.6	C12—C13—C14	109.2 (3)
H41—C4—H42	107.0	C17—C13—C14	100.3 (3)
C6—C5—C4	111.1 (3)	C12—C13—C19	111.9 (4)
C6—C5—C10	111.5 (3)	C17—C13—C19	105.6 (3)
C4—C5—C10	112.0 (3)	C14—C13—C19	112.9 (3)
C6—C5—H51	107.3	C8—C14—C15	123.1 (3)
C4—C5—H51	107.3	C8—C14—C13	113.2 (3)
C10—C5—H51	107.3	C15—C14—C13	103.2 (3)
O6—C6—C7	107.5 (3)	C8—C14—H141	105.3
O6—C6—C5	111.3 (3)	C15—C14—H141	105.3
C7—C6—C5	112.6 (3)	C13—C14—H141	105.3
O6—C6—H61	108.4	C16—C15—C14	102.3 (3)
C7—C6—H61	108.4	C16—C15—H151	111.3
C5—C6—H61	108.4	C14—C15—H151	111.3
C6—O6—H6	116 (4)	C16—C15—H152	111.3
C6—C7—C8	112.3 (3)	C14—C15—H152	111.3
C6—C7—H71	109.2	H151—C15—H152	109.2
C8—C7—H71	109.2	C17—C16—C15	105.3 (4)
C6—C7—H72	109.2	C17—C16—H161	110.7
C8—C7—H72	109.2	C15—C16—H161	110.7
H71—C7—H72	107.9	C17—C16—H162	110.7
C14—C8—C7	111.8 (3)	C15—C16—H162	110.7
C14—C8—C9	107.7 (3)	H161—C16—H162	108.8
C7—C8—C9	112.5 (3)	O17—C17—C16	125.6 (5)
C14—C8—H81	108.2	O17—C17—C13	125.1 (4)
C7—C8—H81	108.2	C16—C17—C13	109.3 (4)
C9—C8—H81	108.2	C10—C18—H181	109.5
C11—C9—C10	114.1 (3)	C10—C18—H182	109.5
C11—C9—C8	110.6 (3)	H181—C18—H182	109.5
C10—C9—C8	113.3 (3)	C10—C18—H183	109.5
C11—C9—H91	106.0	H181—C18—H183	109.5
C10—C9—H91	106.0	H182—C18—H183	109.5
C8—C9—H91	106.0	C13—C19—H191	109.5
C1—C10—C18	106.1 (3)	C13—C19—H192	109.5
C1—C10—C5	105.7 (3)	H191—C19—H192	109.5
C18—C10—C5	110.4 (3)	C13—C19—H193	109.5
C1—C10—C9	111.6 (3)	H191—C19—H193	109.5
C18—C10—C9	112.4 (3)	H192—C19—H193	109.5

(15) 6,17-dihydroxy-2-oxaandrost-4-ene-3-one

Crystal data

C18H26O4	Dx = 1.275 Mg m^−3
Mr = 306.39	Melting point = 227–230 K
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 56 reflections
a = 9.3361 (7) Å	θ = 13–72°
b = 9.6261 (7) Å	µ = 0.71 mm^−1
c = 17.764 (2) Å	T = 293 K
V = 1596.5 (2) Å^3	Prism, white
Z = 4	0.5 × 0.4 × 0.2 mm
F(000) = 664

Data collection

KM-4 diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 70.1°, θmin = 5.0°
Graphite monochromator	h = 0→11
ω–2θ scans	k = 0→11
1746 measured reflections	l = 0→21
1746 independent reflections	2 standard reflections every 100 reflections
1634 reflections with I > 2σ(I)	intensity decay: less than 1%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	Riding
R[F^2 > 2σ(F^2)] = 0.031	Calculated w = 1/[σ^2(Fo^2) + (0.0538P)^2 + 0.2314P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.102	(Δ/σ)max = 0.042
S = 1.06	Δρmax = 0.17 e Å^−3
1741 reflections	Δρmin = −0.11 e Å^−3
234 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0007 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.06 (28)

Special details

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 on F² for ALL reflections except for 5 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion 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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.2964 (2)	0.8623 (2)	0.86551 (14)	0.0459 (5)
H11	0.2591 (2)	0.9448 (2)	0.89004 (14)	0.064 (8)*
H12	0.3032 (2)	0.8820 (2)	0.81207 (14)	0.054 (7)*
O2	0.19615 (14)	0.7488 (2)	0.87671 (10)	0.0522 (4)
C3	0.2404 (2)	0.6214 (2)	0.85772 (12)	0.0448 (5)
O3	0.1531 (2)	0.5281 (2)	0.85524 (11)	0.0643 (5)
C4	0.3931 (2)	0.5997 (2)	0.84450 (11)	0.0403 (4)
H41	0.4228 (2)	0.5180 (2)	0.82133 (11)	0.053 (7)*
C5	0.4916 (2)	0.6931 (2)	0.86450 (10)	0.0337 (4)
C6	0.6480 (2)	0.6589 (2)	0.86318 (13)	0.0406 (5)
H61	0.6774 (2)	0.6370 (2)	0.91479 (13)	0.035 (5)*
O6	0.6718 (2)	0.5394 (2)	0.81851 (12)	0.0636 (5)
H6O	0.753 (5)	0.490 (4)	0.848 (2)	0.108 (12)*
C7	0.7391 (2)	0.7799 (2)	0.83602 (13)	0.0416 (5)
H71	0.7225 (2)	0.7943 (2)	0.78268 (13)	0.046 (6)*
H72	0.8396 (2)	0.7574 (2)	0.84279 (13)	0.049 (6)*
C8	0.7050 (2)	0.9134 (2)	0.87846 (10)	0.0303 (4)
H81	0.7231 (2)	0.8992 (2)	0.93226 (10)	0.031 (5)*
C9	0.5460 (2)	0.9506 (2)	0.86688 (10)	0.0296 (4)
H91	0.5311 (2)	0.9562 (2)	0.81235 (10)	0.034 (5)*
C10	0.4458 (2)	0.8329 (2)	0.89578 (10)	0.0324 (4)
C11	0.5067 (2)	1.0936 (2)	0.89874 (13)	0.0433 (5)
H111	0.5080 (2)	1.0889 (2)	0.95328 (13)	0.060 (7)*
H112	0.4099 (2)	1.1166 (2)	0.88331 (13)	0.059 (7)*
C12	0.6082 (2)	1.2096 (2)	0.87294 (13)	0.0418 (5)
H121	0.5962 (2)	1.2249 (2)	0.81933 (13)	0.044 (6)*
H122	0.5840 (2)	1.2951 (2)	0.89881 (13)	0.051 (7)*
C13	0.7647 (2)	1.1720 (2)	0.88936 (10)	0.0330 (4)
C14	0.7962 (2)	1.0335 (2)	0.85058 (11)	0.0326 (4)
H141	0.7715 (2)	1.0464 (2)	0.79743 (11)	0.030 (5)*
C15	0.9602 (2)	1.0202 (2)	0.8536 (2)	0.0484 (5)
H151	0.9958 (2)	0.9673 (2)	0.8110 (2)	0.070 (8)*
H152	0.9907 (2)	0.9754 (2)	0.8998 (2)	0.056 (7)*
C16	1.0134 (2)	1.1722 (2)	0.8504 (2)	0.0513 (6)
H161	1.0723 (2)	1.1935 (2)	0.8939 (2)	0.074 (9)*
H162	1.0693 (2)	1.1881 (2)	0.8051 (2)	0.086 (10)*
C17	0.8778 (2)	1.2619 (2)	0.85001 (11)	0.0388 (4)
H171	0.8480 (2)	1.2761 (2)	0.79766 (11)	0.053 (7)*
O17	0.8934 (2)	1.39449 (15)	0.88491 (10)	0.0542 (4)
H17O	0.973 (3)	1.429 (3)	0.8692 (15)	0.054 (7)*
C18	0.7926 (3)	1.1699 (3)	0.97428 (12)	0.0525 (5)
H181	0.7265 (14)	1.1073 (15)	0.9981 (2)	0.097 (11)*
H182	0.7799 (19)	1.2616 (5)	0.9944 (2)	0.066 (7)*
H183	0.8889 (7)	1.1393 (18)	0.98360 (12)	0.083 (9)*
C19	0.4428 (3)	0.8221 (2)	0.98248 (11)	0.0505 (5)
H191	0.3802 (13)	0.7478 (10)	0.99723 (11)	0.044 (5)*
H192	0.4085 (15)	0.9079 (6)	1.00336 (12)	0.071 (8)*
H193	0.5377 (4)	0.8039 (15)	1.00078 (12)	0.077 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0265 (9)	0.0406 (10)	0.0705 (14)	−0.0075 (8)	0.0005 (10)	0.0023 (10)
O2	0.0274 (6)	0.0489 (8)	0.0802 (10)	−0.0116 (6)	0.0051 (7)	0.0000 (8)
C3	0.0392 (10)	0.0500 (11)	0.0452 (10)	−0.0164 (9)	−0.0017 (9)	−0.0001 (9)
O3	0.0499 (9)	0.0621 (10)	0.0810 (11)	−0.0315 (8)	0.0037 (9)	−0.0039 (9)
C4	0.0403 (9)	0.0357 (9)	0.0449 (10)	−0.0081 (9)	0.0004 (8)	−0.0023 (8)
C5	0.0335 (9)	0.0311 (8)	0.0364 (9)	−0.0044 (7)	−0.0009 (8)	0.0034 (7)
C6	0.0361 (10)	0.0257 (8)	0.0600 (12)	0.0008 (7)	−0.0065 (9)	−0.0008 (9)
O6	0.0516 (9)	0.0343 (7)	0.1048 (14)	0.0036 (7)	−0.0029 (10)	−0.0181 (9)
C7	0.0281 (9)	0.0326 (9)	0.0640 (12)	0.0006 (8)	0.0045 (9)	−0.0066 (9)
C8	0.0238 (8)	0.0265 (8)	0.0406 (8)	0.0002 (7)	−0.0004 (7)	−0.0003 (7)
C9	0.0237 (8)	0.0277 (8)	0.0373 (8)	−0.0011 (7)	0.0005 (7)	0.0007 (7)
C10	0.0266 (8)	0.0328 (9)	0.0379 (9)	−0.0037 (8)	0.0020 (7)	0.0004 (7)
C11	0.0276 (9)	0.0313 (10)	0.0708 (13)	−0.0004 (8)	0.0092 (9)	−0.0054 (9)
C12	0.0306 (9)	0.0280 (8)	0.0667 (13)	0.0000 (8)	0.0050 (9)	−0.0012 (9)
C13	0.0258 (8)	0.0284 (9)	0.0446 (9)	−0.0041 (7)	0.0023 (7)	−0.0022 (7)
C14	0.0243 (8)	0.0304 (8)	0.0432 (9)	0.0004 (7)	0.0024 (7)	0.0013 (8)
C15	0.0234 (9)	0.0375 (10)	0.084 (2)	−0.0022 (8)	0.0049 (10)	−0.0002 (11)
C16	0.0285 (9)	0.0425 (11)	0.083 (2)	−0.0055 (8)	0.0083 (11)	0.0006 (12)
C17	0.0300 (8)	0.0330 (8)	0.0533 (10)	−0.0060 (8)	0.0025 (8)	0.0004 (9)
O17	0.0407 (8)	0.0343 (7)	0.0876 (12)	−0.0137 (7)	0.0088 (8)	−0.0083 (7)
C18	0.0555 (14)	0.0566 (12)	0.0453 (10)	−0.0171 (11)	−0.0002 (10)	−0.0071 (10)
C19	0.0619 (14)	0.0487 (11)	0.0410 (10)	−0.0171 (11)	0.0110 (10)	−0.0008 (9)

Geometric parameters (Å, º)

C1—O2	1.453 (2)	C11—H111	0.97
C1—C10	1.521 (3)	C11—H112	0.97
C1—H11	0.97	C12—C13	1.533 (3)
C1—H12	0.97	C12—H121	0.97
O2—C3	1.338 (3)	C12—H122	0.97
C3—O3	1.213 (3)	C13—C14	1.529 (2)
C3—C4	1.460 (3)	C13—C18	1.531 (3)
C4—C5	1.334 (3)	C13—C17	1.533 (2)
C4—H41	0.93	C14—C15	1.537 (2)
C5—C6	1.497 (3)	C14—H141	0.98
C5—C10	1.518 (2)	C15—C16	1.546 (3)
C6—O6	1.415 (2)	C15—H151	0.97
C6—C7	1.521 (3)	C15—H152	0.97
C6—H61	0.98	C16—C17	1.533 (3)
O6—H6O	1.04 (4)	C16—H161	0.97
C7—C8	1.524 (2)	C16—H162	0.97
C7—H71	0.97	C17—O17	1.427 (2)
C7—H72	0.97	C17—H171	0.98
C8—C14	1.518 (2)	O17—H17O	0.86 (3)
C8—C9	1.541 (2)	C18—H181	0.96
C8—H81	0.98	C18—H182	0.96
C9—C11	1.533 (2)	C18—H183	0.96
C9—C10	1.556 (2)	C19—H191	0.96
C9—H91	0.98	C19—H192	0.96
C10—C19	1.544 (3)	C19—H193	0.96
C11—C12	1.535 (3)
O2—C1—C10	113.7 (2)	C12—C11—H112	108.92 (11)
O2—C1—H11	108.82 (11)	H111—C11—H112	107.7
C10—C1—H11	108.82 (11)	C13—C12—C11	111.1 (2)
O2—C1—H12	108.81 (12)	C13—C12—H121	109.41 (11)
C10—C1—H12	108.81 (11)	C11—C12—H121	109.42 (12)
H11—C1—H12	107.7	C13—C12—H122	109.42 (10)
C3—O2—C1	117.2 (2)	C11—C12—H122	109.41 (10)
O3—C3—O2	118.7 (2)	H121—C12—H122	108.0
O3—C3—C4	123.0 (2)	C14—C13—C18	113.5 (2)
O2—C3—C4	118.2 (2)	C14—C13—C12	107.67 (15)
C5—C4—C3	122.3 (2)	C18—C13—C12	110.7 (2)
C5—C4—H41	118.85 (12)	C14—C13—C17	98.85 (14)
C3—C4—H41	118.85 (11)	C18—C13—C17	109.9 (2)
C4—C5—C6	121.3 (2)	C12—C13—C17	115.9 (2)
C4—C5—C10	120.0 (2)	C8—C14—C13	114.13 (14)
C6—C5—C10	118.4 (2)	C8—C14—C15	118.9 (2)
O6—C6—C5	109.9 (2)	C13—C14—C15	104.4 (2)
O6—C6—C7	110.9 (2)	C8—C14—H141	106.16 (10)
C5—C6—C7	112.5 (2)	C13—C14—H141	106.16 (10)
O6—C6—H61	107.79 (12)	C15—C14—H141	106.16 (13)
C5—C6—H61	107.79 (12)	C14—C15—C16	103.9 (2)
C7—C6—H61	107.79 (12)	C14—C15—H151	110.98 (13)
C6—O6—H6O	102 (2)	C16—C15—H151	110.97 (13)
C6—C7—C8	111.9 (2)	C14—C15—H152	110.98 (13)
C6—C7—H71	109.24 (12)	C16—C15—H152	110.98 (14)
C8—C7—H71	109.25 (11)	H151—C15—H152	109.0
C6—C7—H72	109.24 (10)	C17—C16—C15	105.50 (15)
C8—C7—H72	109.24 (10)	C17—C16—H161	110.64 (12)
H71—C7—H72	107.9	C15—C16—H161	110.64 (14)
C14—C8—C7	111.32 (15)	C17—C16—H162	110.64 (12)
C14—C8—C9	108.67 (13)	C15—C16—H162	110.64 (13)
C7—C8—C9	109.32 (14)	H161—C16—H162	108.8
C14—C8—H81	109.17 (10)	O17—C17—C16	114.7 (2)
C7—C8—H81	109.17 (10)	O17—C17—C13	112.2 (2)
C9—C8—H81	109.17 (10)	C16—C17—C13	104.5 (2)
C11—C9—C8	112.93 (14)	O17—C17—H171	108.45 (11)
C11—C9—C10	112.81 (14)	C16—C17—H171	108.44 (13)
C8—C9—C10	111.50 (14)	C13—C17—H171	108.44 (10)
C11—C9—H91	106.34 (11)	C17—O17—H17O	107.3 (18)
C8—C9—H91	106.34 (10)	C13—C18—H181	109.47 (11)
C10—C9—H91	106.34 (9)	C13—C18—H182	109.47 (12)
C5—C10—C1	107.1 (2)	H181—C18—H182	109.5
C5—C10—C19	108.1 (2)	C13—C18—H183	109.47 (12)
C1—C10—C19	110.4 (2)	H181—C18—H183	109.5
C5—C10—C9	110.79 (14)	H182—C18—H183	109.5
C1—C10—C9	107.40 (15)	C10—C19—H191	109.47 (11)
C19—C10—C9	112.9 (2)	C10—C19—H192	109.47 (12)
C9—C11—C12	113.29 (15)	H191—C19—H192	109.5
C9—C11—H111	108.92 (11)	C10—C19—H193	109.47 (12)
C12—C11—H111	108.92 (12)	H191—C19—H193	109.5
C9—C11—H112	108.91 (10)	H192—C19—H193	109.5
C10—C1—O2—C3	−47.7 (3)	C8—C9—C10—C1	−166.7 (2)
C1—O2—C3—O3	−168.7 (2)	C11—C9—C10—C19	−57.0 (2)
C1—O2—C3—C4	14.2 (3)	C8—C9—C10—C19	71.4 (2)
O3—C3—C4—C5	−163.6 (2)	C8—C9—C11—C12	50.3 (2)
O2—C3—C4—C5	13.3 (3)	C10—C9—C11—C12	177.9 (2)
C3—C4—C5—C6	169.0 (2)	C9—C11—C12—C13	−53.3 (2)
C3—C4—C5—C10	−5.6 (3)	C11—C12—C13—C14	56.5 (2)
C4—C5—C6—O6	17.5 (3)	C11—C12—C13—C18	−68.1 (2)
C10—C5—C6—O6	−167.9 (2)	C11—C12—C13—C17	166.0 (2)
C4—C5—C6—C7	141.6 (2)	C7—C8—C14—C13	178.4 (2)
C10—C5—C6—C7	−43.7 (2)	C9—C8—C14—C13	58.0 (2)
O6—C6—C7—C8	174.6 (2)	C7—C8—C14—C15	−57.6 (2)
C5—C6—C7—C8	51.0 (2)	C9—C8—C14—C15	−178.0 (2)
C6—C7—C8—C14	−179.8 (2)	C18—C13—C14—C8	61.5 (2)
C6—C7—C8—C9	−59.7 (2)	C12—C13—C14—C8	−61.4 (2)
C14—C8—C9—C11	−50.6 (2)	C17—C13—C14—C8	177.76 (15)
C7—C8—C9—C11	−172.3 (2)	C18—C13—C14—C15	−70.0 (2)
C14—C8—C9—C10	−178.87 (14)	C12—C13—C14—C15	167.1 (2)
C7—C8—C9—C10	59.5 (2)	C17—C13—C14—C15	46.3 (2)
C4—C5—C10—C1	−25.3 (2)	C8—C14—C15—C16	−159.6 (2)
C6—C5—C10—C1	159.9 (2)	C13—C14—C15—C16	−31.0 (2)
C4—C5—C10—C19	93.7 (2)	C14—C15—C16—C17	2.9 (3)
C6—C5—C10—C19	−81.1 (2)	C15—C16—C17—O17	149.2 (2)
C4—C5—C10—C9	−142.2 (2)	C15—C16—C17—C13	26.0 (2)
C6—C5—C10—C9	43.1 (2)	C14—C13—C17—O17	−168.9 (2)
O2—C1—C10—C5	50.8 (2)	C18—C13—C17—O17	−49.9 (2)
O2—C1—C10—C19	−66.7 (2)	C12—C13—C17—O17	76.4 (2)
O2—C1—C10—C9	169.8 (2)	C14—C13—C17—C16	−44.1 (2)
C11—C9—C10—C5	−178.4 (2)	C18—C13—C17—C16	74.9 (2)
C8—C9—C10—C5	−50.0 (2)	C12—C13—C17—C16	−158.8 (2)
C11—C9—C10—C1	65.0 (2)

(22) 2-Oxa-4-androsten-3,17-dione and 2-Oxa-6beta-hydroxy-4-androsten-3,17-dione

Crystal data

0.72(C18H24O4)·0.28(C18H24O4)	F(000) = 328
Mr = 304.37	Dx = 1.271 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2y1	Cell parameters from 58 reflections
a = 6.2246 (7) Å	θ = 14.7–71.3°
b = 12.014 (1) Å	µ = 0.72 mm^−1
c = 10.915 (1) Å	T = 293 K
β = 103.09 (1)°	Cubic, light brown
V = 795.04 (13) Å^3	0.35 × 0.30 × 0.30 mm
Z = 2

Data collection

KM-4 diffractometer	Rint = 0.019
Radiation source: fine-focus sealed tube	θmax = 70.1°, θmin = 4.2°
Graphite monochromator	h = 0→7
ω–2θ scans	k = 0→14
1651 measured reflections	l = −13→12
1542 independent reflections	2 standard reflections every 100 reflections
1497 reflections with I > 2σ(I)	intensity decay: less than 2.9%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.032	Calculated w = 1/[σ^2(Fo^2) + (0.0542P)^2 + 0.0888P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.088	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.13 e Å^−3
1542 reflections	Δρmin = −0.12 e Å^−3
202 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0040 (8)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.0 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.2869 (5)	0.2785 (2)	0.2066 (2)	0.0620 (6)
H11	0.3697	0.2816	0.1413	0.072*
H12	0.1336	0.2651	0.1662	0.070*
O2	0.3038 (3)	0.38510 (13)	0.26960 (18)	0.0644 (5)
C3	0.2229 (4)	0.39165 (19)	0.3735 (2)	0.0558 (5)
O3	0.1922 (3)	0.48254 (15)	0.4136 (2)	0.0743 (6)
C4	0.1950 (3)	0.28815 (19)	0.4370 (2)	0.0502 (5)
H4	0.1185	0.2896	0.5010	0.078*
C5	0.2737 (3)	0.19166 (17)	0.40767 (18)	0.0413 (4)
C6	0.2868 (4)	0.09080 (17)	0.49156 (19)	0.0473 (5)
H61	0.4443	0.0787	0.5272	0.063*
O6	0.1926 (4)	0.1111 (2)	0.5940 (2)	0.0638 (9)	0.721 (7)
H6	0.096 (6)	0.068 (3)	0.5830 (7)	0.069*	0.721 (7)
C7	0.2060 (4)	−0.01367 (18)	0.4161 (2)	0.0470 (5)
H71	0.0485	−0.0079	0.3817	0.048*
H72	0.2320	−0.0779	0.4713	0.065*
C8	0.3237 (3)	−0.03010 (16)	0.30919 (17)	0.0388 (4)
H8	0.4822	−0.0388	0.3444	0.039*
C9	0.2854 (3)	0.07209 (18)	0.22164 (19)	0.0423 (4)
H9	0.1251	0.0805	0.1939	0.041*
C10	0.3712 (3)	0.18135 (17)	0.29337 (18)	0.0424 (4)
C11	0.3719 (5)	0.0562 (2)	0.1016 (2)	0.0610 (6)
H111	0.3238	0.1185	0.0456	0.081*
H112	0.5319	0.0568	0.1239	0.068*
C12	0.2937 (5)	−0.0523 (2)	0.0316 (2)	0.0593 (6)
H121	0.1358	−0.0490	−0.0027	0.081*
H122	0.3660	−0.0617	−0.0377	0.079*
C13	0.3474 (3)	−0.14999 (18)	0.12062 (19)	0.0467 (5)
C14	0.2376 (3)	−0.13258 (16)	0.23127 (18)	0.0412 (4)
H14	0.0814	−0.1181	0.1942	0.056*
C15	0.2468 (5)	−0.24719 (19)	0.2939 (2)	0.0578 (6)
H151	0.1363	−0.2538	0.3434	0.083*
H152	0.3913	−0.2613	0.3474	0.080*
C16	0.1982 (5)	−0.3268 (2)	0.1807 (2)	0.0700 (7)
H161	0.2894	−0.3930	0.1982	0.110*
H162	0.0445	−0.3491	0.1613	0.091*
C17	0.2517 (4)	−0.2622 (2)	0.0725 (2)	0.0525 (5)
O17	0.2187 (3)	−0.29409 (17)	−0.03526 (15)	0.0701 (5)
C18	0.5984 (3)	−0.1708 (3)	0.1623 (2)	0.0665 (7)
H181	0.6694	−0.1057	0.2037	0.114*
H182	0.6563	−0.1870	0.0899	0.063*
H183	0.6254	−0.2328	0.2192	0.113*
C19	0.6245 (3)	0.1859 (2)	0.3358 (2)	0.0528 (5)
H191	0.6754	0.1261	0.3934	0.074*
H192	0.6682	0.2557	0.3766	0.072*
H193	0.6879	0.1787	0.2638	0.072*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0882 (18)	0.0400 (12)	0.0543 (12)	−0.0065 (11)	0.0087 (12)	0.0005 (10)
O2	0.0866 (12)	0.0359 (8)	0.0709 (10)	−0.0039 (8)	0.0183 (9)	0.0046 (8)
C3	0.0491 (10)	0.0395 (12)	0.0769 (15)	0.0007 (9)	0.0107 (10)	−0.0028 (11)
O3	0.0765 (11)	0.0393 (9)	0.1103 (16)	0.0057 (8)	0.0281 (11)	−0.0072 (9)
C4	0.0468 (11)	0.0417 (11)	0.0646 (13)	−0.0007 (8)	0.0177 (9)	−0.0049 (10)
C5	0.0387 (8)	0.0371 (10)	0.0475 (10)	−0.0045 (8)	0.0084 (7)	−0.0036 (8)
C6	0.0615 (12)	0.0391 (11)	0.0452 (10)	−0.0025 (9)	0.0206 (9)	−0.0027 (9)
O6	0.0859 (17)	0.0559 (15)	0.0602 (14)	−0.0234 (12)	0.0385 (12)	−0.0170 (11)
C7	0.0609 (11)	0.0373 (10)	0.0477 (11)	−0.0052 (9)	0.0228 (9)	−0.0007 (9)
C8	0.0417 (9)	0.0362 (10)	0.0389 (9)	−0.0008 (7)	0.0097 (7)	−0.0003 (8)
C9	0.0467 (10)	0.0391 (10)	0.0404 (9)	−0.0046 (8)	0.0086 (7)	−0.0014 (8)
C10	0.0480 (9)	0.0368 (10)	0.0431 (9)	−0.0048 (8)	0.0119 (7)	0.0005 (9)
C11	0.0923 (17)	0.0502 (13)	0.0455 (11)	−0.0118 (13)	0.0260 (11)	−0.0007 (10)
C12	0.0829 (15)	0.0553 (14)	0.0408 (10)	−0.0067 (12)	0.0164 (9)	−0.0054 (10)
C13	0.0452 (10)	0.0510 (12)	0.0424 (10)	0.0010 (9)	0.0067 (8)	−0.0087 (9)
C14	0.0405 (8)	0.0385 (11)	0.0445 (10)	−0.0008 (7)	0.0092 (7)	−0.0019 (9)
C15	0.0793 (15)	0.0374 (12)	0.0579 (12)	−0.0014 (10)	0.0180 (11)	−0.0016 (10)
C16	0.0945 (18)	0.0412 (13)	0.0738 (16)	−0.0032 (13)	0.0181 (13)	−0.0070 (12)
C17	0.0484 (10)	0.0499 (12)	0.0554 (11)	0.0091 (9)	0.0037 (8)	−0.0107 (10)
O17	0.0773 (10)	0.0695 (13)	0.0588 (9)	0.0043 (9)	0.0056 (7)	−0.0259 (9)
C18	0.0457 (11)	0.0874 (19)	0.0681 (14)	0.0029 (12)	0.0167 (10)	−0.0218 (14)
C19	0.0491 (10)	0.0544 (12)	0.0584 (11)	−0.0132 (10)	0.0192 (9)	−0.0109 (11)

Geometric parameters (Å, º)

C1—O2	1.446 (3)	C11—C12	1.534 (3)
C1—C10	1.519 (3)	C11—H111	0.9700
C1—H11	0.9700	C11—H112	0.9700
C1—H12	0.9700	C12—C13	1.512 (3)
O2—C3	1.344 (3)	C12—H121	0.9700
C3—O3	1.207 (3)	C12—H122	0.9700
C3—C4	1.453 (3)	C13—C17	1.519 (3)
C4—C5	1.326 (3)	C13—C14	1.531 (3)
C4—H4	0.9300	C13—C18	1.545 (3)
C5—C6	1.510 (3)	C14—C15	1.532 (3)
C5—C10	1.511 (3)	C14—H14	0.9800
C6—O6	1.397 (3)	C15—C16	1.537 (3)
C6—C7	1.523 (3)	C15—H151	0.9700
C6—H61	0.9800	C15—H152	0.9700
O6—H6	0.7812	C16—C17	1.511 (4)
C7—C8	1.525 (2)	C16—H161	0.9700
C7—H71	0.9700	C16—H162	0.9700
C7—H72	0.9700	C17—O17	1.210 (3)
C8—C14	1.523 (3)	C18—H181	0.9600
C8—C9	1.541 (3)	C18—H182	0.9600
C8—H8	0.9800	C18—H183	0.9600
C9—C11	1.537 (3)	C19—H191	0.9600
C9—C10	1.559 (3)	C19—H192	0.9600
C9—H9	0.9800	C19—H193	0.9600
C10—C19	1.540 (3)
O2—C1—C10	113.99 (18)	C9—C11—H111	108.9
O2—C1—H11	108.8	C12—C11—H112	108.9
C10—C1—H11	108.8	C9—C11—H112	108.9
O2—C1—H12	108.8	H111—C11—H112	107.7
C10—C1—H12	108.8	C13—C12—C11	109.88 (17)
H11—C1—H12	107.6	C13—C12—H121	109.7
C3—O2—C1	116.89 (18)	C11—C12—H121	109.7
O3—C3—O2	118.6 (2)	C13—C12—H122	109.7
O3—C3—C4	123.8 (2)	C11—C12—H122	109.7
O2—C3—C4	117.43 (19)	H121—C12—H122	108.2
C5—C4—C3	122.86 (19)	C12—C13—C17	117.04 (17)
C5—C4—H4	118.6	C12—C13—C14	109.14 (17)
C3—C4—H4	118.6	C17—C13—C14	100.58 (17)
C4—C5—C6	121.83 (18)	C12—C13—C18	112.1 (2)
C4—C5—C10	120.70 (18)	C17—C13—C18	104.44 (18)
C6—C5—C10	117.29 (16)	C14—C13—C18	113.09 (16)
O6—C6—C5	111.78 (19)	C8—C14—C13	112.79 (15)
O6—C6—C7	115.46 (18)	C8—C14—C15	120.30 (16)
C5—C6—C7	111.57 (17)	C13—C14—C15	104.50 (17)
O6—C6—H61	105.7	C8—C14—H14	106.1
C5—C6—H61	105.7	C13—C14—H14	106.1
C7—C6—H61	105.7	C15—C14—H14	106.1
C6—O6—H6	102.2	C14—C15—C16	102.73 (18)
C6—C7—C8	111.33 (16)	C14—C15—H151	111.2
C6—C7—H71	109.4	C16—C15—H151	111.2
C8—C7—H71	109.4	C14—C15—H152	111.2
C6—C7—H72	109.4	C16—C15—H152	111.2
C8—C7—H72	109.4	H151—C15—H152	109.1
H71—C7—H72	108.0	C17—C16—C15	105.7 (2)
C14—C8—C7	111.26 (16)	C17—C16—H161	110.6
C14—C8—C9	108.20 (14)	C15—C16—H161	110.6
C7—C8—C9	109.74 (16)	C17—C16—H162	110.6
C14—C8—H8	109.2	C15—C16—H162	110.6
C7—C8—H8	109.2	H161—C16—H162	108.7
C9—C8—H8	109.2	O17—C17—C16	125.3 (2)
C11—C9—C8	113.24 (17)	O17—C17—C13	125.7 (2)
C11—C9—C10	112.72 (17)	C16—C17—C13	108.94 (18)
C8—C9—C10	111.84 (15)	C13—C18—H181	109.5
C11—C9—H9	106.1	C13—C18—H182	109.5
C8—C9—H9	106.1	H181—C18—H182	109.5
C10—C9—H9	106.1	C13—C18—H183	109.5
C5—C10—C1	107.75 (17)	H181—C18—H183	109.5
C5—C10—C19	108.92 (15)	H182—C18—H183	109.5
C1—C10—C19	110.22 (19)	C10—C19—H191	109.5
C5—C10—C9	109.12 (15)	C10—C19—H192	109.5
C1—C10—C9	107.63 (16)	H191—C19—H192	109.5
C19—C10—C9	113.06 (17)	C10—C19—H193	109.5
C12—C11—C9	113.45 (19)	H191—C19—H193	109.5
C12—C11—H111	108.9	H192—C19—H193	109.5