17-Allyl-16,17a-dioxo-17-aza-D-homoestra-1,3,5(10)-trien-3-yl acetate

In the title compound, C₂₃H₂₇NO₄, 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 and the heterocyclic ring has a sofa conformation. The plane of the allyl substituent lies almost perpendicular to the least-squares plane of the heterocyclic ring. The crystal structure contains a series of weak C—H...O intermolecular interactions.

Key indicators

• Single-crystal X-ray study
• T = 160 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.047
• wR factor = 0.128
• Data-to-parameter ratio = 10.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.62 Ratio
PLAT480_ALERT_4_C Long H...A H-Bond Reported H14    ..  CG1     ..       2.99 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           27.48
           From the CIF: _reflns_number_total               2596
           Count of symmetry unique reflns         2599
           Completeness (_total/calc)             99.88%
           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
   2 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
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 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: PLEASE PROVIDE; 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-allyl-16,17a-dioxo-17-aza-D-homoestra-1,3,5(10)-trien-3-yl acetate

Crystal data

C23H27NO4	F(000) = 816
Mr = 381.46	Dx = 1.270 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2614 reflections
a = 9.3546 (2) Å	θ = 2.0–27.5°
b = 10.7074 (2) Å	µ = 0.09 mm^−1
c = 19.9204 (5) Å	T = 160 K
V = 1995.30 (8) Å^3	Tablet, colourless
Z = 4	0.25 × 0.18 × 0.10 mm

Data collection

Nonius KappaCCD area-detector diffractometer	2063 reflections with I > 2σ(I)
Radiation source: Nonius FR590 sealed tube generator	Rint = 0.068
Horizontally mounted graphite crystal monochromator	θmax = 27.5°, θmin = 2.4°
Detector resolution: 9 pixels mm^-1	h = −12→12
φ and ω scans with κ offsets	k = −13→13
30780 measured reflections	l = −25→25
2596 independent reflections

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)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.128	w = 1/[σ^2(Fo^2) + (0.0731P)^2 + 0.1695P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.004
2591 reflections	Δρmax = 0.25 e Å^−3
256 parameters	Δρmin = −0.21 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.012 (3)

Special details

Experimental. Solvent used: methanol Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.435 (2) Frames collected: 247 Seconds exposure per frame: 90 Degrees rotation per frame: 1.8 Crystal-Detector distance (mm): 30.0

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	−0.1852 (2)	0.07213 (18)	0.51999 (10)	0.0566 (6)
O17A	0.0686 (2)	−0.12972 (16)	0.36185 (10)	0.0506 (5)
O31	0.38829 (19)	0.78490 (16)	0.20927 (8)	0.0391 (4)
O32	0.3554 (2)	0.7728 (2)	0.09810 (9)	0.0578 (6)
N17	−0.0626 (2)	−0.02694 (19)	0.43862 (10)	0.0354 (5)
C1	0.3033 (3)	0.4467 (2)	0.20939 (13)	0.0381 (6)
H1	0.3269	0.3723	0.1859	0.046*
C2	0.3636 (3)	0.5586 (2)	0.18849 (13)	0.0399 (6)
H2	0.4274	0.5610	0.1514	0.048*
C3	0.3290 (3)	0.6660 (2)	0.22273 (12)	0.0341 (6)
C4	0.2348 (3)	0.6631 (2)	0.27598 (12)	0.0333 (5)
H4	0.2116	0.7384	0.2987	0.040*
C5	0.1734 (3)	0.5508 (2)	0.29679 (12)	0.0328 (5)
C6	0.0723 (3)	0.5543 (2)	0.35577 (13)	0.0395 (6)
H61	0.0046	0.6245	0.3497	0.047*
H62	0.1278	0.5705	0.3972	0.047*
C7	−0.0117 (3)	0.4347 (2)	0.36457 (13)	0.0366 (6)
H71	−0.0869	0.4293	0.3297	0.044*
H72	−0.0587	0.4344	0.4091	0.044*
C8	0.0884 (3)	0.3226 (2)	0.35878 (11)	0.0284 (5)
H8	0.1722	0.3377	0.3889	0.034*
C9	0.1437 (3)	0.3156 (2)	0.28585 (12)	0.0326 (5)
H9	0.0591	0.2997	0.2564	0.039*
C10	0.2087 (3)	0.4396 (2)	0.26390 (11)	0.0319 (5)
C11	0.2452 (3)	0.2040 (2)	0.27792 (14)	0.0402 (6)
H111	0.2736	0.1966	0.2302	0.048*
H112	0.3327	0.2193	0.3046	0.048*
C12	0.1780 (3)	0.0823 (2)	0.30039 (13)	0.0378 (6)
H121	0.2497	0.0147	0.2968	0.045*
H122	0.0977	0.0616	0.2700	0.045*
C13	0.1221 (3)	0.0881 (2)	0.37327 (11)	0.0306 (5)
C14	0.0193 (3)	0.1990 (2)	0.37951 (11)	0.0285 (5)
H14	−0.0621	0.1834	0.3481	0.034*
C15	−0.0418 (3)	0.2020 (2)	0.45055 (11)	0.0351 (6)
H151	0.0348	0.2270	0.4821	0.042*
H152	−0.1176	0.2664	0.4526	0.042*
C16	−0.1030 (3)	0.0803 (2)	0.47322 (12)	0.0390 (6)
C17A	0.0420 (3)	−0.0311 (2)	0.38860 (13)	0.0354 (6)
C18	0.2485 (3)	0.0929 (2)	0.42361 (14)	0.0414 (6)
H181	0.2114	0.0905	0.4696	0.062*
H182	0.3027	0.1702	0.4169	0.062*
H183	0.3113	0.0210	0.4162	0.062*
C19	−0.1305 (3)	−0.1461 (3)	0.45737 (14)	0.0459 (7)
H191	−0.1481	−0.1962	0.4164	0.055*
H192	−0.2240	−0.1291	0.4788	0.055*
C20	−0.0389 (4)	−0.2194 (3)	0.50471 (16)	0.0585 (8)
H20	0.0561	−0.2372	0.4909	0.070*
C21	−0.0785 (5)	−0.2602 (3)	0.56264 (18)	0.0743 (10)
H211	−0.1727	−0.2444	0.5783	0.089*
H212	−0.0135	−0.3062	0.5897	0.089*
C31	0.3913 (3)	0.8318 (2)	0.14637 (13)	0.0384 (6)
C32	0.4437 (3)	0.9625 (3)	0.14636 (15)	0.0494 (7)
H321	0.5457	0.9635	0.1351	0.074*
H322	0.4297	0.9991	0.1910	0.074*
H323	0.3905	1.0111	0.1130	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O16	0.0725 (13)	0.0450 (11)	0.0523 (11)	0.0111 (11)	0.0310 (11)	0.0094 (9)
O17A	0.0623 (13)	0.0316 (9)	0.0580 (12)	−0.0033 (9)	0.0173 (11)	−0.0121 (9)
O31	0.0433 (10)	0.0384 (9)	0.0356 (9)	−0.0054 (8)	0.0024 (8)	0.0024 (8)
O32	0.0742 (15)	0.0606 (12)	0.0386 (11)	−0.0130 (12)	−0.0052 (10)	0.0030 (10)
N17	0.0381 (11)	0.0314 (10)	0.0366 (10)	−0.0012 (9)	0.0038 (9)	0.0003 (9)
C1	0.0408 (14)	0.0371 (13)	0.0365 (13)	−0.0007 (12)	0.0080 (11)	−0.0053 (11)
C2	0.0387 (14)	0.0441 (15)	0.0370 (13)	−0.0008 (12)	0.0096 (11)	−0.0012 (11)
C3	0.0328 (13)	0.0349 (12)	0.0347 (12)	−0.0031 (11)	−0.0017 (11)	0.0029 (11)
C4	0.0352 (13)	0.0349 (12)	0.0299 (12)	0.0012 (11)	−0.0017 (10)	0.0006 (10)
C5	0.0323 (12)	0.0350 (12)	0.0311 (12)	0.0020 (11)	−0.0009 (10)	0.0000 (10)
C6	0.0477 (15)	0.0313 (13)	0.0394 (13)	0.0038 (12)	0.0098 (12)	0.0000 (11)
C7	0.0404 (13)	0.0344 (13)	0.0351 (12)	0.0036 (11)	0.0096 (11)	0.0045 (11)
C8	0.0301 (11)	0.0307 (12)	0.0243 (11)	0.0020 (10)	0.0006 (9)	−0.0018 (9)
C9	0.0324 (13)	0.0356 (12)	0.0298 (12)	−0.0016 (11)	0.0018 (10)	−0.0050 (10)
C10	0.0275 (12)	0.0376 (13)	0.0307 (12)	−0.0019 (11)	0.0003 (9)	−0.0010 (10)
C11	0.0410 (14)	0.0360 (13)	0.0438 (14)	0.0014 (12)	0.0141 (12)	−0.0078 (12)
C12	0.0398 (14)	0.0339 (12)	0.0398 (13)	−0.0023 (11)	0.0114 (11)	−0.0114 (11)
C13	0.0309 (11)	0.0280 (11)	0.0328 (12)	0.0005 (10)	0.0019 (10)	−0.0049 (10)
C14	0.0290 (11)	0.0300 (12)	0.0265 (11)	0.0014 (10)	0.0000 (9)	−0.0020 (10)
C15	0.0419 (14)	0.0326 (12)	0.0309 (12)	0.0067 (11)	0.0075 (11)	0.0004 (10)
C16	0.0433 (14)	0.0403 (13)	0.0334 (13)	0.0055 (13)	0.0060 (11)	0.0036 (11)
C17A	0.0355 (13)	0.0343 (13)	0.0362 (12)	−0.0003 (11)	0.0030 (11)	−0.0034 (11)
C18	0.0369 (13)	0.0367 (13)	0.0506 (15)	0.0024 (12)	−0.0071 (12)	−0.0034 (12)
C19	0.0479 (16)	0.0411 (14)	0.0487 (15)	−0.0084 (13)	0.0049 (14)	0.0022 (13)
C20	0.067 (2)	0.0462 (17)	0.0627 (19)	−0.0030 (16)	0.0002 (16)	0.0071 (17)
C21	0.085 (2)	0.066 (2)	0.072 (2)	−0.008 (2)	−0.002 (2)	0.0180 (19)
C31	0.0312 (13)	0.0470 (15)	0.0369 (13)	0.0026 (11)	0.0023 (11)	0.0041 (12)
C32	0.0519 (16)	0.0480 (16)	0.0483 (16)	−0.0060 (14)	0.0049 (14)	0.0108 (13)

Geometric parameters (Å, º)

O16—C16	1.211 (3)	C9—H9	1.0000
O17A—C17A	1.209 (3)	C11—C12	1.514 (3)
O31—C31	1.350 (3)	C11—H111	0.9900
O31—C3	1.415 (3)	C11—H112	0.9900
O32—C31	1.199 (3)	C12—C13	1.544 (3)
N17—C16	1.391 (3)	C12—H121	0.9900
N17—C17A	1.397 (3)	C12—H122	0.9900
N17—C19	1.474 (3)	C13—C17A	1.512 (3)
C1—C2	1.389 (4)	C13—C14	1.532 (3)
C1—C10	1.403 (3)	C13—C18	1.552 (3)
C1—H1	0.9500	C14—C15	1.527 (3)
C2—C3	1.375 (4)	C14—H14	1.0000
C2—H2	0.9500	C15—C16	1.493 (4)
C3—C4	1.379 (3)	C15—H151	0.9900
C4—C5	1.396 (3)	C15—H152	0.9900
C4—H4	0.9500	C18—H181	0.9800
C5—C10	1.399 (3)	C18—H182	0.9800
C5—C6	1.509 (3)	C18—H183	0.9800
C6—C7	1.513 (3)	C19—C20	1.496 (4)
C6—H61	0.9900	C19—H191	0.9900
C6—H62	0.9900	C19—H192	0.9900
C7—C8	1.527 (3)	C20—C21	1.288 (5)
C7—H71	0.9900	C20—H20	0.9500
C7—H72	0.9900	C21—H211	0.9500
C8—C14	1.529 (3)	C21—H212	0.9500
C8—C9	1.544 (3)	C31—C32	1.482 (4)
C8—H8	1.0000	C32—H321	0.9800
C9—C10	1.524 (3)	C32—H322	0.9800
C9—C11	1.535 (3)	C32—H323	0.9800
C31—O31—C3	121.3 (2)	C11—C12—H122	109.1
C16—N17—C17A	124.7 (2)	C13—C12—H122	109.1
C16—N17—C19	118.15 (19)	H121—C12—H122	107.8
C17A—N17—C19	117.1 (2)	C17A—C13—C14	109.09 (18)
C2—C1—C10	122.4 (2)	C17A—C13—C12	108.90 (19)
C2—C1—H1	118.8	C14—C13—C12	108.65 (19)
C10—C1—H1	118.8	C17A—C13—C18	105.97 (19)
C3—C2—C1	118.5 (2)	C14—C13—C18	113.59 (19)
C3—C2—H2	120.8	C12—C13—C18	110.5 (2)
C1—C2—H2	120.8	C15—C14—C8	112.99 (18)
C2—C3—C4	120.9 (2)	C15—C14—C13	109.05 (19)
C2—C3—O31	124.5 (2)	C8—C14—C13	112.55 (18)
C4—C3—O31	114.6 (2)	C15—C14—H14	107.3
C3—C4—C5	120.7 (2)	C8—C14—H14	107.3
C3—C4—H4	119.7	C13—C14—H14	107.3
C5—C4—H4	119.7	C16—C15—C14	113.9 (2)
C4—C5—C10	119.8 (2)	C16—C15—H151	108.8
C4—C5—C6	117.9 (2)	C14—C15—H151	108.8
C10—C5—C6	122.3 (2)	C16—C15—H152	108.8
C5—C6—C7	113.2 (2)	C14—C15—H152	108.8
C5—C6—H61	108.9	H151—C15—H152	107.7
C7—C6—H61	108.9	O16—C16—N17	119.6 (2)
C5—C6—H62	108.9	O16—C16—C15	122.6 (2)
C7—C6—H62	108.9	N17—C16—C15	117.8 (2)
H61—C6—H62	107.7	O17A—C17A—N17	119.1 (2)
C6—C7—C8	109.8 (2)	O17A—C17A—C13	123.1 (2)
C6—C7—H71	109.7	N17—C17A—C13	117.7 (2)
C8—C7—H71	109.7	C13—C18—H181	109.5
C6—C7—H72	109.7	C13—C18—H182	109.5
C8—C7—H72	109.7	H181—C18—H182	109.5
H71—C7—H72	108.2	C13—C18—H183	109.5
C7—C8—C14	113.63 (19)	H181—C18—H183	109.5
C7—C8—C9	108.33 (18)	H182—C18—H183	109.5
C14—C8—C9	110.71 (18)	N17—C19—C20	111.5 (2)
C7—C8—H8	108.0	N17—C19—H191	109.3
C14—C8—H8	108.0	C20—C19—H191	109.3
C9—C8—H8	108.0	N17—C19—H192	109.3
C10—C9—C11	113.69 (19)	C20—C19—H192	109.3
C10—C9—C8	111.20 (18)	H191—C19—H192	108.0
C11—C9—C8	110.0 (2)	C21—C20—C19	125.3 (3)
C10—C9—H9	107.2	C21—C20—H20	117.4
C11—C9—H9	107.2	C19—C20—H20	117.4
C8—C9—H9	107.2	C20—C21—H211	120.0
C5—C10—C1	117.7 (2)	C20—C21—H212	120.0
C5—C10—C9	120.8 (2)	H211—C21—H212	120.0
C1—C10—C9	121.4 (2)	O32—C31—O31	122.8 (2)
C12—C11—C9	112.5 (2)	O32—C31—C32	126.2 (2)
C12—C11—H111	109.1	O31—C31—C32	111.0 (2)
C9—C11—H111	109.1	C31—C32—H321	109.5
C12—C11—H112	109.1	C31—C32—H322	109.5
C9—C11—H112	109.1	H321—C32—H322	109.5
H111—C11—H112	107.8	C31—C32—H323	109.5
C11—C12—C13	112.6 (2)	H321—C32—H323	109.5
C11—C12—H121	109.1	H322—C32—H323	109.5
C13—C12—H121	109.1
C10—C1—C2—C3	0.0 (4)	C7—C8—C14—C15	−55.9 (3)
C1—C2—C3—C4	−0.9 (4)	C9—C8—C14—C15	−178.07 (19)
C1—C2—C3—O31	176.4 (2)	C7—C8—C14—C13	−179.97 (19)
C31—O31—C3—C2	50.6 (3)	C9—C8—C14—C13	57.9 (2)
C31—O31—C3—C4	−131.9 (2)	C17A—C13—C14—C15	58.8 (2)
C2—C3—C4—C5	0.6 (4)	C12—C13—C14—C15	177.43 (19)
O31—C3—C4—C5	−177.0 (2)	C18—C13—C14—C15	−59.1 (3)
C3—C4—C5—C10	0.7 (4)	C17A—C13—C14—C8	−174.95 (19)
C3—C4—C5—C6	179.5 (2)	C12—C13—C14—C8	−56.4 (2)
C4—C5—C6—C7	167.6 (2)	C18—C13—C14—C8	67.1 (2)
C10—C5—C6—C7	−13.7 (4)	C8—C14—C15—C16	−177.0 (2)
C5—C6—C7—C8	46.4 (3)	C13—C14—C15—C16	−51.0 (3)
C6—C7—C8—C14	169.5 (2)	C17A—N17—C16—O16	−173.2 (2)
C6—C7—C8—C9	−67.0 (3)	C19—N17—C16—O16	4.5 (4)
C7—C8—C9—C10	53.1 (3)	C17A—N17—C16—C15	6.8 (4)
C14—C8—C9—C10	178.29 (19)	C19—N17—C16—C15	−175.5 (2)
C7—C8—C9—C11	179.91 (19)	C14—C15—C16—O16	−161.6 (2)
C14—C8—C9—C11	−54.9 (3)	C14—C15—C16—N17	18.4 (3)
C4—C5—C10—C1	−1.6 (4)	C16—N17—C17A—O17A	179.9 (2)
C6—C5—C10—C1	179.7 (2)	C19—N17—C17A—O17A	2.3 (4)
C4—C5—C10—C9	179.7 (2)	C16—N17—C17A—C13	3.1 (4)
C6—C5—C10—C9	1.0 (4)	C19—N17—C17A—C13	−174.5 (2)
C2—C1—C10—C5	1.2 (4)	C14—C13—C17A—O17A	146.9 (3)
C2—C1—C10—C9	179.9 (2)	C12—C13—C17A—O17A	28.5 (3)
C11—C9—C10—C5	−145.9 (2)	C18—C13—C17A—O17A	−90.4 (3)
C8—C9—C10—C5	−21.2 (3)	C14—C13—C17A—N17	−36.4 (3)
C11—C9—C10—C1	35.4 (3)	C12—C13—C17A—N17	−154.8 (2)
C8—C9—C10—C1	160.2 (2)	C18—C13—C17A—N17	86.2 (2)
C10—C9—C11—C12	179.7 (2)	C3—O31—C31—O32	−6.2 (4)
C8—C9—C11—C12	54.3 (3)	C3—O31—C31—C32	173.8 (2)
C9—C11—C12—C13	−55.4 (3)	C16—N17—C19—C20	−97.2 (3)
C11—C12—C13—C17A	173.5 (2)	C17A—N17—C19—C20	80.6 (3)
C11—C12—C13—C14	54.7 (3)	N17—C19—C20—C21	124.8 (3)
C11—C12—C13—C18	−70.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O17A^i	0.95	2.32	3.204 (3)	155
C8—H8···O16^ii	1.00	2.45	3.404 (3)	159
C15—H151···O32^iii	0.99	2.53	3.428 (3)	151
C15—H152···O32^iv	0.99	2.44	3.181 (3)	131
C14—H14···Cg1^iv	1.00	2.99	3.591 (3)	162

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