(8R,9S,13S,14S)-17-Butyl-16,17a-dioxo-17-aza-D-homoestra-1,3,5(10)-trien-3-ol

In the title compound, C₂₂H₂₉NO₃, a modified synthetic D-homo steroid, the cyclo­hexene ring adjacent to the aromatic ring adopts a half-chair conformation, while the cyclo­hexane ring has an ideal chair conformation. The heterocyclic ring adopts a 14β-sofa conformation. The butyl substituent is nearly planar, this plane lying almost perpendicular to the least-squares plane of the heterocyclic ring. Inter­molecular O—H...O hydrogen bonds link the mol­ecules into extended chains and the compound also exhibits some weak inter­molecular C—H...O inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 160 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.047
• wR factor = 0.122
• Data-to-parameter ratio = 8.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.16 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.91 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N17    -   C19     ..       5.76 su

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           25.02
           From the CIF: _reflns_number_total               1982
           Count of symmetry unique reflns         1985
           Completeness (_total/calc)             99.85%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1999); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

17-Butyl-16,17a-dioxo-17-aza-D-homoestra-1,3,5(10)-trien-3-ol

Crystal data

C22H29NO3	Dx = 1.230 Mg m^−3
Mr = 355.46	Melting point: 568 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1995 reflections
a = 6.2505 (2) Å	θ = 2.0–25.0°
b = 13.3718 (4) Å	µ = 0.08 mm^−1
c = 22.9703 (7) Å	T = 160 K
V = 1919.87 (10) Å^3	Prism, colourless
Z = 4	0.18 × 0.13 × 0.05 mm
F(000) = 768

Data collection

Nonius KappaCCD area-detector diffractometer	1601 reflections with I > 2σ(I)
Radiation source: Nonius FR590 sealed-tube generator	Rint = 0.069
Horizontally mounted graphite crystal monochromator	θmax = 25.0°, θmin = 2.3°
Detector resolution: 9 pixels mm^-1	h = −7→7
φ and ω scans with κ offsets	k = −15→15
20155 measured reflections	l = −27→27
1982 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: geom & difmap
R[F^2 > 2σ(F^2)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.122	w = 1/[σ^2(Fo^2) + (0.0677P)^2 + 0.1751P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
1979 reflections	Δρmax = 0.24 e Å^−3
241 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Absolute structure: Flack & Bernardinelli (2000)
Primary atom site location: structure-invariant direct methods

Special details

Experimental. Solvent used: Methanol Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.462 (2) Frames collected: 255 Seconds exposure per frame: 135 Degrees rotation per frame: 1.0 Crystal-Detector distance (mm): 35.0

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
O16	−0.1065 (4)	0.45481 (14)	0.16626 (9)	0.0475 (6)
O17A	0.4612 (3)	0.29720 (15)	0.08657 (8)	0.0412 (6)
O31	−0.3509 (4)	−0.37628 (16)	0.19240 (10)	0.0495 (7)
H31	−0.279 (6)	−0.422 (2)	0.1800 (14)	0.050 (11)*
C1	0.0490 (5)	−0.1902 (2)	0.14993 (12)	0.0358 (7)
H1	0.1836	−0.1872	0.1308	0.043*
C2	−0.0494 (5)	−0.2818 (2)	0.15617 (12)	0.0385 (8)
H2	0.0166	−0.3406	0.1414	0.046*
C3	−0.2440 (5)	−0.2875 (2)	0.18398 (12)	0.0347 (7)
C4	−0.3356 (5)	−0.2018 (2)	0.20562 (11)	0.0337 (7)
H4	−0.4693	−0.2060	0.2252	0.040*
C5	−0.2373 (5)	−0.10905 (19)	0.19960 (11)	0.0288 (7)
C6	−0.3479 (5)	−0.01832 (19)	0.22413 (13)	0.0359 (7)
H61	−0.3968	−0.0338	0.2641	0.043*
H62	−0.4763	−0.0041	0.2003	0.043*
C7	−0.2095 (5)	0.0749 (2)	0.22607 (12)	0.0344 (7)
H71	−0.1073	0.0699	0.2589	0.041*
H72	−0.3008	0.1343	0.2326	0.041*
C8	−0.0868 (5)	0.08689 (19)	0.16919 (11)	0.0291 (7)
H8	−0.1918	0.0839	0.1364	0.035*
C9	0.0696 (5)	−0.00104 (19)	0.16252 (11)	0.0308 (7)
H9	0.1773	0.0052	0.1945	0.037*
C10	−0.0417 (5)	−0.1018 (2)	0.17067 (11)	0.0307 (7)
C11	0.1921 (6)	0.0069 (2)	0.10519 (13)	0.0421 (8)
H111	0.0911	−0.0023	0.0724	0.051*
H112	0.2995	−0.0474	0.1033	0.051*
C12	0.3052 (5)	0.10757 (19)	0.09841 (13)	0.0385 (8)
H121	0.3710	0.1111	0.0593	0.046*
H122	0.4213	0.1124	0.1276	0.046*
C13	0.1523 (5)	0.19641 (19)	0.10620 (11)	0.0298 (6)
C14	0.0346 (4)	0.18645 (19)	0.16495 (11)	0.0288 (6)
H14	0.1462	0.1860	0.1961	0.035*
C15	−0.1060 (5)	0.27827 (19)	0.17533 (12)	0.0354 (7)
H151	−0.2436	0.2680	0.1548	0.043*
H152	−0.1378	0.2825	0.2175	0.043*
C16	−0.0147 (5)	0.3761 (2)	0.15624 (12)	0.0364 (7)
N17	0.1804 (4)	0.37790 (16)	0.12762 (9)	0.0356 (6)
C17A	0.2816 (5)	0.2916 (2)	0.10650 (11)	0.0328 (7)
C18	−0.0027 (5)	0.2053 (2)	0.05406 (12)	0.0420 (8)
H181	−0.0954	0.2636	0.0595	0.063*
H182	−0.0905	0.1447	0.0516	0.063*
H183	0.0797	0.2131	0.0180	0.063*
C19	0.2788 (6)	0.4744 (2)	0.11138 (13)	0.0469 (9)
H191	0.4357	0.4660	0.1079	0.056*
H192	0.2507	0.5243	0.1423	0.056*
C20	0.1890 (7)	0.5126 (2)	0.05363 (13)	0.0521 (9)
H201	0.2061	0.4600	0.0237	0.063*
H202	0.0340	0.5257	0.0582	0.063*
C21	0.2985 (7)	0.6078 (2)	0.03274 (14)	0.0640 (12)
H211	0.4506	0.5934	0.0242	0.077*
H212	0.2934	0.6587	0.0640	0.077*
C22	0.1906 (9)	0.6494 (3)	−0.02190 (18)	0.0913 (16)
H221	0.1964	0.5993	−0.0530	0.137*
H222	0.2654	0.7101	−0.0345	0.137*
H223	0.0410	0.6655	−0.0132	0.137*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O16	0.0525 (15)	0.0323 (12)	0.0577 (14)	0.0028 (11)	0.0100 (12)	−0.0045 (10)
O17A	0.0370 (14)	0.0431 (12)	0.0434 (12)	−0.0040 (11)	0.0033 (11)	0.0046 (9)
O31	0.0517 (16)	0.0308 (12)	0.0662 (15)	−0.0022 (12)	0.0152 (13)	−0.0008 (11)
C1	0.0336 (18)	0.0324 (15)	0.0413 (16)	0.0032 (14)	0.0086 (15)	0.0003 (12)
C2	0.046 (2)	0.0281 (15)	0.0410 (16)	0.0071 (14)	0.0078 (16)	0.0008 (12)
C3	0.0393 (19)	0.0296 (15)	0.0352 (16)	−0.0003 (14)	0.0016 (14)	0.0018 (12)
C4	0.0291 (17)	0.0363 (16)	0.0356 (15)	0.0020 (15)	0.0040 (14)	0.0034 (13)
C5	0.0283 (17)	0.0271 (15)	0.0311 (14)	0.0005 (13)	−0.0018 (13)	0.0018 (11)
C6	0.0339 (17)	0.0333 (15)	0.0405 (16)	0.0046 (14)	0.0084 (15)	0.0019 (12)
C7	0.0353 (18)	0.0302 (15)	0.0378 (15)	−0.0002 (14)	0.0080 (14)	−0.0021 (12)
C8	0.0287 (17)	0.0279 (14)	0.0308 (13)	0.0002 (12)	0.0005 (13)	−0.0008 (12)
C9	0.0267 (16)	0.0307 (15)	0.0351 (15)	0.0011 (13)	0.0037 (13)	−0.0005 (12)
C10	0.0305 (17)	0.0304 (14)	0.0312 (14)	0.0034 (13)	0.0021 (14)	0.0033 (12)
C11	0.044 (2)	0.0315 (15)	0.0505 (17)	0.0024 (15)	0.0166 (17)	−0.0037 (14)
C12	0.038 (2)	0.0346 (16)	0.0431 (16)	0.0005 (14)	0.0123 (15)	0.0012 (13)
C13	0.0304 (16)	0.0301 (14)	0.0289 (13)	0.0019 (14)	0.0024 (13)	−0.0006 (12)
C14	0.0249 (15)	0.0316 (14)	0.0300 (13)	0.0018 (12)	0.0013 (13)	−0.0014 (11)
C15	0.0370 (18)	0.0332 (15)	0.0360 (15)	0.0028 (14)	0.0027 (14)	−0.0022 (13)
C16	0.043 (2)	0.0320 (16)	0.0338 (15)	−0.0006 (15)	−0.0025 (15)	−0.0038 (12)
N17	0.0401 (16)	0.0293 (12)	0.0373 (13)	−0.0052 (12)	0.0018 (13)	−0.0007 (10)
C17A	0.0343 (19)	0.0380 (16)	0.0262 (14)	0.0005 (15)	−0.0036 (14)	0.0033 (12)
C18	0.0444 (19)	0.0491 (18)	0.0325 (14)	−0.0063 (17)	−0.0013 (15)	0.0006 (13)
C19	0.053 (2)	0.0405 (18)	0.0469 (18)	−0.0041 (16)	0.0081 (18)	−0.0061 (14)
C20	0.066 (3)	0.0400 (17)	0.0504 (18)	−0.0021 (18)	0.0098 (19)	−0.0001 (14)
C21	0.088 (3)	0.047 (2)	0.058 (2)	−0.004 (2)	0.024 (2)	0.0038 (17)
C22	0.116 (4)	0.076 (3)	0.081 (3)	0.005 (3)	0.025 (3)	0.032 (2)

Geometric parameters (Å, º)

O16—C16	1.220 (3)	C12—C13	1.535 (4)
O17A—C17A	1.215 (3)	C12—H121	0.9900
O31—C3	1.376 (3)	C12—H122	0.9900
O31—H31	0.81 (3)	C13—C17A	1.508 (4)
C1—C2	1.378 (4)	C13—C14	1.543 (4)
C1—C10	1.395 (4)	C13—C18	1.545 (4)
C1—H1	0.9500	C14—C15	1.529 (4)
C2—C3	1.376 (4)	C14—H14	1.0000
C2—H2	0.9500	C15—C16	1.494 (4)
C3—C4	1.374 (4)	C15—H151	0.9900
C4—C5	1.391 (4)	C15—H152	0.9900
C4—H4	0.9500	C16—N17	1.385 (4)
C5—C10	1.395 (4)	N17—C17A	1.403 (4)
C5—C6	1.506 (4)	N17—C19	1.478 (4)
C6—C7	1.518 (4)	C18—H181	0.9800
C6—H61	0.9900	C18—H182	0.9800
C6—H62	0.9900	C18—H183	0.9800
C7—C8	1.523 (4)	C19—C20	1.528 (5)
C7—H71	0.9900	C19—H191	0.9900
C7—H72	0.9900	C19—H192	0.9900
C8—C14	1.535 (4)	C20—C21	1.523 (5)
C8—C9	1.537 (4)	C20—H201	0.9900
C8—H8	1.0000	C20—H202	0.9900
C9—C11	1.527 (4)	C21—C22	1.529 (6)
C9—C10	1.528 (4)	C21—H211	0.9900
C9—H9	1.0000	C21—H212	0.9900
C11—C12	1.528 (4)	C22—H221	0.9800
C11—H111	0.9900	C22—H222	0.9800
C11—H112	0.9900	C22—H223	0.9800
C3—O31—H31	109 (2)	C17A—C13—C14	108.9 (2)
C2—C1—C10	122.4 (3)	C12—C13—C14	109.4 (2)
C2—C1—H1	118.8	C17A—C13—C18	106.0 (2)
C10—C1—H1	118.8	C12—C13—C18	111.0 (2)
C3—C2—C1	119.5 (3)	C14—C13—C18	112.7 (2)
C3—C2—H2	120.3	C15—C14—C8	113.7 (2)
C1—C2—H2	120.3	C15—C14—C13	110.0 (2)
C4—C3—C2	119.4 (3)	C8—C14—C13	111.5 (2)
C4—C3—O31	117.8 (3)	C15—C14—H14	107.1
C2—C3—O31	122.8 (3)	C8—C14—H14	107.1
C3—C4—C5	121.5 (3)	C13—C14—H14	107.1
C3—C4—H4	119.2	C16—C15—C14	116.0 (2)
C5—C4—H4	119.2	C16—C15—H151	108.3
C4—C5—C10	119.8 (2)	C14—C15—H151	108.3
C4—C5—C6	118.6 (2)	C16—C15—H152	108.3
C10—C5—C6	121.7 (2)	C14—C15—H152	108.3
C5—C6—C7	114.3 (2)	H151—C15—H152	107.4
C5—C6—H61	108.7	O16—C16—N17	119.3 (3)
C7—C6—H61	108.7	O16—C16—C15	121.3 (3)
C5—C6—H62	108.7	N17—C16—C15	119.4 (3)
C7—C6—H62	108.7	C16—N17—C17A	123.2 (2)
H61—C6—H62	107.6	C16—N17—C19	120.1 (2)
C6—C7—C8	110.4 (2)	C17A—N17—C19	116.3 (2)
C6—C7—H71	109.6	O17A—C17A—N17	119.7 (3)
C8—C7—H71	109.6	O17A—C17A—C13	123.1 (3)
C6—C7—H72	109.6	N17—C17A—C13	117.0 (2)
C8—C7—H72	109.6	C13—C18—H181	109.5
H71—C7—H72	108.1	C13—C18—H182	109.5
C7—C8—C14	113.2 (2)	H181—C18—H182	109.5
C7—C8—C9	109.0 (2)	C13—C18—H183	109.5
C14—C8—C9	110.0 (2)	H181—C18—H183	109.5
C7—C8—H8	108.2	H182—C18—H183	109.5
C14—C8—H8	108.2	N17—C19—C20	111.0 (3)
C9—C8—H8	108.2	N17—C19—H191	109.4
C11—C9—C10	113.3 (2)	C20—C19—H191	109.4
C11—C9—C8	110.6 (2)	N17—C19—H192	109.4
C10—C9—C8	111.9 (2)	C20—C19—H192	109.4
C11—C9—H9	106.9	H191—C19—H192	108.0
C10—C9—H9	106.9	C21—C20—C19	112.8 (3)
C8—C9—H9	106.9	C21—C20—H201	109.0
C5—C10—C1	117.4 (2)	C19—C20—H201	109.0
C5—C10—C9	121.3 (2)	C21—C20—H202	109.0
C1—C10—C9	121.4 (2)	C19—C20—H202	109.0
C9—C11—C12	112.4 (2)	H201—C20—H202	107.8
C9—C11—H111	109.1	C20—C21—C22	111.4 (4)
C12—C11—H111	109.1	C20—C21—H211	109.4
C9—C11—H112	109.1	C22—C21—H211	109.4
C12—C11—H112	109.1	C20—C21—H212	109.4
H111—C11—H112	107.9	C22—C21—H212	109.4
C11—C12—C13	112.4 (2)	H211—C21—H212	108.0
C11—C12—H121	109.1	C21—C22—H221	109.5
C13—C12—H121	109.1	C21—C22—H222	109.5
C11—C12—H122	109.1	H221—C22—H222	109.5
C13—C12—H122	109.1	C21—C22—H223	109.5
H121—C12—H122	107.8	H221—C22—H223	109.5
C17A—C13—C12	108.7 (2)	H222—C22—H223	109.5
C10—C1—C2—C3	−0.3 (4)	C7—C8—C14—C15	−53.8 (3)
C1—C2—C3—C4	−0.7 (4)	C9—C8—C14—C15	−176.0 (2)
C1—C2—C3—O31	−179.3 (3)	C7—C8—C14—C13	−178.8 (2)
C2—C3—C4—C5	0.6 (4)	C9—C8—C14—C13	59.0 (3)
O31—C3—C4—C5	179.3 (2)	C17A—C13—C14—C15	57.2 (3)
C3—C4—C5—C10	0.4 (4)	C12—C13—C14—C15	175.9 (2)
C3—C4—C5—C6	179.6 (3)	C18—C13—C14—C15	−60.1 (3)
C4—C5—C6—C7	168.5 (2)	C17A—C13—C14—C8	−175.7 (2)
C10—C5—C6—C7	−12.3 (4)	C12—C13—C14—C8	−57.0 (3)
C5—C6—C7—C8	44.4 (3)	C18—C13—C14—C8	67.0 (3)
C6—C7—C8—C14	172.7 (2)	C8—C14—C15—C16	−164.0 (2)
C6—C7—C8—C9	−64.5 (3)	C13—C14—C15—C16	−38.2 (3)
C7—C8—C9—C11	178.6 (2)	C14—C15—C16—O16	−174.6 (3)
C14—C8—C9—C11	−56.7 (3)	C14—C15—C16—N17	4.0 (4)
C7—C8—C9—C10	51.3 (3)	O16—C16—N17—C17A	−170.0 (3)
C14—C8—C9—C10	176.0 (2)	C15—C16—N17—C17A	11.3 (4)
C4—C5—C10—C1	−1.3 (4)	O16—C16—N17—C19	2.1 (4)
C6—C5—C10—C1	179.5 (3)	C15—C16—N17—C19	−176.6 (3)
C4—C5—C10—C9	179.2 (2)	C16—N17—C17A—O17A	−173.3 (2)
C6—C5—C10—C9	0.0 (4)	C19—N17—C17A—O17A	14.3 (4)
C2—C1—C10—C5	1.3 (4)	C16—N17—C17A—C13	10.8 (4)
C2—C1—C10—C9	−179.3 (3)	C19—N17—C17A—C13	−161.7 (3)
C11—C9—C10—C5	−145.9 (3)	C12—C13—C17A—O17A	19.9 (3)
C8—C9—C10—C5	−20.0 (3)	C14—C13—C17A—O17A	139.1 (3)
C11—C9—C10—C1	34.7 (4)	C18—C13—C17A—O17A	−99.5 (3)
C8—C9—C10—C1	160.5 (3)	C12—C13—C17A—N17	−164.3 (2)
C10—C9—C11—C12	−179.0 (3)	C14—C13—C17A—N17	−45.2 (3)
C8—C9—C11—C12	54.5 (3)	C18—C13—C17A—N17	76.3 (3)
C9—C11—C12—C13	−53.9 (3)	C16—N17—C19—C20	−83.9 (3)
C11—C12—C13—C17A	172.8 (2)	C17A—N17—C19—C20	88.7 (3)
C11—C12—C13—C14	54.0 (3)	N17—C19—C20—C21	−175.4 (3)
C11—C12—C13—C18	−71.0 (3)	C19—C20—C21—C22	−174.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O31—H31···O16^i	0.81 (3)	2.00 (3)	2.792 (3)	168 (3)
C15—H151···O17A^ii	0.99	2.45	3.397 (4)	159
C18—H183···O17A^iii	0.98	2.52	3.238 (3)	130

Symmetry codes: (i) x, y−1, z; (ii) x−1, y, z; (iii) x−1/2, −y+1/2, −z.