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

In the title compound, a modified synthetic D-homo steroid, C₂₄H₃₁NO₄, 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 butyl substituent is nearly planar, with this plane lying 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) = 0.005 Å
• R factor = 0.046
• wR factor = 0.124
• Data-to-parameter ratio = 8.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5

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           25.05
           From the CIF: _reflns_number_total               2164
           Count of symmetry unique reflns         2166
           Completeness (_total/calc)             99.91%
           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
   1 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
   0 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: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); 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-yl acetate

Crystal data

C24H31NO4	Dx = 1.237 Mg m^−3
Mr = 397.51	Melting point: 449 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2182 reflections
a = 9.7793 (4) Å	θ = 2.0–25.0°
b = 11.3997 (4) Å	µ = 0.08 mm^−1
c = 19.1470 (7) Å	T = 160 K
V = 2134.53 (14) Å^3	Needle, colourless
Z = 4	0.25 × 0.13 × 0.05 mm
F(000) = 856

Data collection

Nonius KappaCCD area-detector diffractometer	1675 reflections with I > 2s(I)
Radiation source: Nonius FR590 sealed tube generator	Rint = 0.074
Horizontally mounted graphite crystal monochromator	θmax = 25.1°, θmin = 2.7°
Detector resolution: 9 pixels mm^-1	h = −11→11
φ and ω scans with κ offsets	k = −12→13
22788 measured reflections	l = −22→22
2164 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.046	w = 1/[σ^2(Fo^2) + (0.0768P)^2 + 0.0087P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.124	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.18 e Å^−3
2159 reflections	Δρmin = −0.15 e Å^−3
266 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.014 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack & Bernardinelli (2000)
Secondary atom site location: difference Fourier map

Special details

Experimental. Solvent used: anhydrous ethylmethyl ketone Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.696 (2) Frames collected: 323 Seconds exposure per frame: 100 Degrees rotation per frame: 1.0 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	−0.1609 (3)	0.0914 (2)	0.51452 (12)	0.0778 (8)
O17A	0.0877 (3)	−0.07401 (19)	0.34344 (12)	0.0640 (7)
O31	0.3794 (2)	0.8050 (2)	0.21799 (10)	0.0543 (6)
O32	0.3289 (3)	0.8042 (3)	0.10407 (13)	0.0832 (8)
N17	−0.0477 (3)	0.0117 (2)	0.42397 (12)	0.0470 (7)
C1	0.3034 (3)	0.4880 (3)	0.20946 (16)	0.0532 (8)
H1	0.3277	0.4207	0.1830	0.064*
C2	0.3588 (3)	0.5954 (3)	0.19077 (16)	0.0543 (9)
H2	0.4199	0.6019	0.1524	0.065*
C3	0.3228 (3)	0.6923 (3)	0.22938 (15)	0.0480 (8)
C4	0.2338 (3)	0.6832 (3)	0.28426 (15)	0.0464 (7)
H4	0.2096	0.7514	0.3100	0.056*
C5	0.1780 (3)	0.5749 (3)	0.30298 (15)	0.0443 (7)
C6	0.0819 (4)	0.5697 (3)	0.36460 (15)	0.0521 (8)
H61	0.0172	0.6363	0.3617	0.062*
H62	0.1355	0.5788	0.4081	0.062*
C7	0.0012 (3)	0.4564 (2)	0.36848 (16)	0.0487 (8)
H71	−0.0700	0.4559	0.3317	0.058*
H72	−0.0447	0.4506	0.4144	0.058*
C8	0.0971 (3)	0.3516 (3)	0.35850 (14)	0.0413 (7)
H8	0.1761	0.3618	0.3911	0.050*
C9	0.1534 (3)	0.3549 (3)	0.28310 (14)	0.0470 (8)
H9	0.0740	0.3423	0.2510	0.056*
C10	0.2135 (3)	0.4743 (3)	0.26550 (14)	0.0464 (8)
C11	0.2520 (4)	0.2524 (3)	0.27181 (19)	0.0638 (10)
H111	0.2830	0.2523	0.2226	0.077*
H112	0.3334	0.2634	0.3018	0.077*
C12	0.1860 (4)	0.1344 (3)	0.28865 (18)	0.0591 (9)
H121	0.2545	0.0713	0.2827	0.071*
H122	0.1103	0.1197	0.2554	0.071*
C13	0.1302 (3)	0.1308 (3)	0.36337 (15)	0.0447 (7)
C14	0.0315 (3)	0.2333 (2)	0.37406 (14)	0.0403 (7)
H14	−0.0454	0.2227	0.3403	0.048*
C15	−0.0290 (4)	0.2252 (3)	0.44757 (15)	0.0501 (8)
H151	0.0428	0.2458	0.4819	0.060*
H152	−0.1033	0.2837	0.4520	0.060*
C16	−0.0846 (3)	0.1070 (3)	0.46517 (15)	0.0519 (8)
C17A	0.0558 (3)	0.0155 (3)	0.37384 (15)	0.0475 (8)
C18	0.2489 (3)	0.1303 (3)	0.41682 (18)	0.0621 (10)
H181	0.2128	0.1138	0.4635	0.093*
H182	0.2938	0.2072	0.4169	0.093*
H183	0.3154	0.0698	0.4039	0.093*
C19	−0.1117 (4)	−0.1022 (3)	0.43971 (16)	0.0546 (8)
H191	−0.1162	−0.1495	0.3964	0.066*
H192	−0.2064	−0.0890	0.4562	0.066*
C20	−0.0335 (3)	−0.1692 (3)	0.49455 (17)	0.0545 (8)
H201	−0.0105	−0.1150	0.5332	0.065*
H202	0.0535	−0.1969	0.4739	0.065*
C21	−0.1089 (4)	−0.2739 (3)	0.5245 (2)	0.0652 (9)
H211	−0.1975	−0.2472	0.5438	0.078*
H212	−0.1285	−0.3302	0.4864	0.078*
C22	−0.0295 (4)	−0.3356 (3)	0.5811 (2)	0.0838 (13)
H221	0.0455	−0.3804	0.5600	0.126*
H222	−0.0903	−0.3890	0.6064	0.126*
H223	0.0080	−0.2775	0.6135	0.126*
C31	0.3744 (3)	0.8546 (3)	0.15466 (17)	0.0572 (9)
C32	0.4346 (4)	0.9743 (3)	0.1549 (2)	0.0665 (10)
H321	0.5246	0.9723	0.1325	0.100*
H322	0.4445	1.0015	0.2032	0.100*
H323	0.3745	1.0280	0.1293	0.100*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O16	0.102 (2)	0.0566 (14)	0.0746 (16)	0.0206 (13)	0.0419 (16)	0.0129 (12)
O17A	0.0734 (16)	0.0478 (13)	0.0710 (14)	−0.0042 (12)	0.0134 (13)	−0.0252 (11)
O31	0.0586 (14)	0.0590 (13)	0.0454 (12)	−0.0051 (12)	0.0009 (11)	0.0042 (10)
O32	0.093 (2)	0.105 (2)	0.0518 (14)	−0.0111 (17)	−0.0125 (14)	0.0094 (14)
N17	0.0466 (16)	0.0484 (14)	0.0461 (14)	0.0035 (12)	0.0028 (12)	−0.0023 (12)
C1	0.053 (2)	0.058 (2)	0.0487 (17)	−0.0045 (17)	0.0117 (16)	−0.0143 (15)
C2	0.045 (2)	0.066 (2)	0.0523 (17)	−0.0072 (16)	0.0094 (16)	−0.0065 (16)
C3	0.0462 (19)	0.0527 (19)	0.0452 (16)	−0.0016 (15)	−0.0031 (14)	−0.0012 (15)
C4	0.0474 (18)	0.0493 (18)	0.0426 (16)	0.0045 (15)	−0.0017 (14)	−0.0035 (14)
C5	0.0410 (17)	0.0505 (18)	0.0413 (15)	0.0028 (15)	−0.0006 (14)	−0.0038 (14)
C6	0.062 (2)	0.0499 (17)	0.0439 (16)	0.0080 (17)	0.0097 (15)	−0.0026 (14)
C7	0.053 (2)	0.0484 (16)	0.0448 (16)	0.0105 (15)	0.0110 (15)	0.0031 (14)
C8	0.0388 (16)	0.0490 (16)	0.0361 (15)	0.0081 (14)	0.0000 (12)	−0.0065 (12)
C9	0.0465 (18)	0.0550 (19)	0.0395 (15)	−0.0065 (15)	0.0050 (13)	−0.0138 (14)
C10	0.0402 (18)	0.0573 (19)	0.0415 (15)	−0.0040 (15)	0.0018 (14)	−0.0108 (14)
C11	0.068 (2)	0.0530 (19)	0.070 (2)	−0.0051 (17)	0.0300 (18)	−0.0209 (18)
C12	0.062 (2)	0.0504 (19)	0.065 (2)	−0.0105 (17)	0.0235 (18)	−0.0243 (16)
C13	0.0420 (17)	0.0435 (16)	0.0487 (16)	0.0032 (14)	0.0011 (14)	−0.0146 (14)
C14	0.0375 (16)	0.0463 (17)	0.0370 (14)	0.0057 (13)	−0.0024 (12)	−0.0037 (12)
C15	0.061 (2)	0.0480 (17)	0.0413 (16)	0.0167 (15)	0.0082 (15)	0.0047 (13)
C16	0.059 (2)	0.0522 (18)	0.0443 (16)	0.0158 (16)	0.0078 (16)	0.0074 (15)
C17A	0.0432 (18)	0.0529 (19)	0.0466 (17)	0.0002 (15)	−0.0018 (14)	−0.0113 (15)
C18	0.049 (2)	0.0452 (18)	0.092 (2)	0.0109 (15)	−0.0178 (18)	−0.0130 (18)
C19	0.0481 (19)	0.0582 (19)	0.0575 (19)	−0.0032 (15)	0.0018 (16)	−0.0037 (15)
C20	0.0513 (18)	0.0491 (18)	0.063 (2)	−0.0012 (15)	−0.0057 (16)	−0.0043 (16)
C21	0.052 (2)	0.057 (2)	0.086 (2)	−0.0038 (16)	−0.0022 (19)	0.0064 (18)
C22	0.070 (2)	0.062 (2)	0.120 (4)	−0.0030 (19)	−0.009 (2)	0.032 (2)
C31	0.047 (2)	0.080 (2)	0.0451 (18)	0.0046 (18)	0.0023 (17)	0.0035 (18)
C32	0.073 (3)	0.064 (2)	0.063 (2)	0.0029 (19)	0.011 (2)	0.0122 (18)

Geometric parameters (Å, º)

O16—C16	1.217 (4)	C11—H112	0.9900
O17A—C17A	1.215 (3)	C12—C13	1.532 (4)
O31—C31	1.339 (4)	C12—H121	0.9900
O31—C3	1.416 (4)	C12—H122	0.9900
O32—C31	1.211 (4)	C13—C17A	1.516 (4)
N17—C16	1.390 (4)	C13—C14	1.529 (4)
N17—C17A	1.396 (4)	C13—C18	1.547 (4)
N17—C19	1.472 (4)	C14—C15	1.530 (4)
C1—C2	1.386 (4)	C14—H14	1.0000
C1—C10	1.396 (4)	C15—C16	1.492 (4)
C1—H1	0.9500	C15—H151	0.9900
C2—C3	1.375 (4)	C15—H152	0.9900
C2—H2	0.9500	C18—H181	0.9800
C3—C4	1.369 (4)	C18—H182	0.9800
C4—C5	1.396 (4)	C18—H183	0.9800
C4—H4	0.9500	C19—C20	1.507 (4)
C5—C10	1.398 (4)	C19—H191	0.9900
C5—C6	1.510 (4)	C19—H192	0.9900
C6—C7	1.514 (4)	C20—C21	1.515 (4)
C6—H61	0.9900	C20—H201	0.9900
C6—H62	0.9900	C20—H202	0.9900
C7—C8	1.530 (4)	C21—C22	1.507 (5)
C7—H71	0.9900	C21—H211	0.9900
C7—H72	0.9900	C21—H212	0.9900
C8—C14	1.523 (4)	C22—H221	0.9800
C8—C9	1.546 (4)	C22—H222	0.9800
C8—H8	1.0000	C22—H223	0.9800
C9—C10	1.520 (4)	C31—C32	1.486 (5)
C9—C11	1.531 (4)	C32—H321	0.9800
C9—H9	1.0000	C32—H322	0.9800
C11—C12	1.527 (4)	C32—H323	0.9800
C11—H111	0.9900
C31—O31—C3	120.6 (3)	C17A—C13—C18	105.6 (3)
C16—N17—C17A	123.7 (3)	C14—C13—C18	112.8 (2)
C16—N17—C19	117.6 (2)	C12—C13—C18	110.5 (3)
C17A—N17—C19	118.4 (2)	C8—C14—C13	112.7 (2)
C2—C1—C10	123.0 (3)	C8—C14—C15	113.3 (2)
C2—C1—H1	118.5	C13—C14—C15	108.8 (2)
C10—C1—H1	118.5	C8—C14—H14	107.3
C3—C2—C1	118.1 (3)	C13—C14—H14	107.3
C3—C2—H2	121.0	C15—C14—H14	107.3
C1—C2—H2	121.0	C16—C15—C14	113.8 (3)
C4—C3—C2	121.0 (3)	C16—C15—H151	108.8
C4—C3—O31	115.8 (3)	C14—C15—H151	108.8
C2—C3—O31	123.1 (3)	C16—C15—H152	108.8
C3—C4—C5	120.9 (3)	C14—C15—H152	108.8
C3—C4—H4	119.6	H151—C15—H152	107.7
C5—C4—H4	119.6	O16—C16—N17	119.1 (3)
C4—C5—C10	119.8 (3)	O16—C16—C15	122.0 (3)
C4—C5—C6	118.6 (3)	N17—C16—C15	118.9 (3)
C10—C5—C6	121.6 (3)	O17A—C17A—N17	119.3 (3)
C5—C6—C7	113.4 (2)	O17A—C17A—C13	122.8 (3)
C5—C6—H61	108.9	N17—C17A—C13	117.8 (2)
C7—C6—H61	108.9	C13—C18—H181	109.5
C5—C6—H62	108.9	C13—C18—H182	109.5
C7—C6—H62	108.9	H181—C18—H182	109.5
H61—C6—H62	107.7	C13—C18—H183	109.5
C6—C7—C8	109.9 (3)	H181—C18—H183	109.5
C6—C7—H71	109.7	H182—C18—H183	109.5
C8—C7—H71	109.7	N17—C19—C20	112.0 (3)
C6—C7—H72	109.7	N17—C19—H191	109.2
C8—C7—H72	109.7	C20—C19—H191	109.2
H71—C7—H72	108.2	N17—C19—H192	109.2
C14—C8—C7	114.2 (2)	C20—C19—H192	109.2
C14—C8—C9	110.7 (2)	H191—C19—H192	107.9
C7—C8—C9	108.4 (2)	C19—C20—C21	114.6 (3)
C14—C8—H8	107.8	C19—C20—H201	108.6
C7—C8—H8	107.8	C21—C20—H201	108.6
C9—C8—H8	107.8	C19—C20—H202	108.6
C10—C9—C11	114.1 (2)	C21—C20—H202	108.6
C10—C9—C8	111.5 (2)	H201—C20—H202	107.6
C11—C9—C8	109.7 (3)	C22—C21—C20	112.9 (3)
C10—C9—H9	107.0	C22—C21—H211	109.0
C11—C9—H9	107.0	C20—C21—H211	109.0
C8—C9—H9	107.0	C22—C21—H212	109.0
C1—C10—C5	117.3 (3)	C20—C21—H212	109.0
C1—C10—C9	121.0 (3)	H211—C21—H212	107.8
C5—C10—C9	121.7 (2)	C21—C22—H221	109.5
C12—C11—C9	112.1 (3)	C21—C22—H222	109.5
C12—C11—H111	109.2	H221—C22—H222	109.5
C9—C11—H111	109.2	C21—C22—H223	109.5
C12—C11—H112	109.2	H221—C22—H223	109.5
C9—C11—H112	109.2	H222—C22—H223	109.5
H111—C11—H112	107.9	O32—C31—O31	122.5 (3)
C11—C12—C13	111.8 (2)	O32—C31—C32	125.8 (3)
C11—C12—H121	109.3	O31—C31—C32	111.7 (3)
C13—C12—H121	109.3	C31—C32—H321	109.5
C11—C12—H122	109.3	C31—C32—H322	109.5
C13—C12—H122	109.3	H321—C32—H322	109.5
H121—C12—H122	107.9	C31—C32—H323	109.5
C17A—C13—C14	110.0 (2)	H321—C32—H323	109.5
C17A—C13—C12	108.5 (2)	H322—C32—H323	109.5
C14—C13—C12	109.2 (3)
C10—C1—C2—C3	−0.1 (5)	C7—C8—C14—C13	179.9 (2)
C1—C2—C3—C4	−0.6 (5)	C9—C8—C14—C13	57.2 (3)
C1—C2—C3—O31	175.9 (3)	C7—C8—C14—C15	−56.1 (3)
C31—O31—C3—C4	−128.5 (3)	C9—C8—C14—C15	−178.8 (2)
C31—O31—C3—C2	54.8 (4)	C17A—C13—C14—C8	−175.3 (2)
C2—C3—C4—C5	0.6 (5)	C12—C13—C14—C8	−56.4 (3)
O31—C3—C4—C5	−176.1 (3)	C18—C13—C14—C8	67.0 (3)
C3—C4—C5—C10	0.2 (5)	C17A—C13—C14—C15	58.1 (3)
C3—C4—C5—C6	179.2 (3)	C12—C13—C14—C15	177.1 (3)
C4—C5—C6—C7	165.3 (3)	C18—C13—C14—C15	−59.5 (3)
C10—C5—C6—C7	−15.8 (4)	C8—C14—C15—C16	−175.9 (3)
C5—C6—C7—C8	47.5 (4)	C13—C14—C15—C16	−49.8 (3)
C6—C7—C8—C14	169.8 (2)	C17A—N17—C16—O16	−168.9 (3)
C6—C7—C8—C9	−66.2 (3)	C19—N17—C16—O16	4.3 (4)
C14—C8—C9—C10	177.5 (2)	C17A—N17—C16—C15	11.0 (5)
C7—C8—C9—C10	51.5 (3)	C19—N17—C16—C15	−175.9 (3)
C14—C8—C9—C11	−55.1 (3)	C14—C15—C16—O16	−164.2 (3)
C7—C8—C9—C11	178.9 (2)	C14—C15—C16—N17	15.9 (4)
C2—C1—C10—C5	0.9 (5)	C16—N17—C17A—O17A	175.0 (3)
C2—C1—C10—C9	178.8 (3)	C19—N17—C17A—O17A	1.9 (4)
C4—C5—C10—C1	−0.9 (4)	C16—N17—C17A—C13	−0.9 (4)
C6—C5—C10—C1	−179.8 (3)	C19—N17—C17A—C13	−174.1 (3)
C4—C5—C10—C9	−178.8 (3)	C14—C13—C17A—O17A	149.7 (3)
C6—C5—C10—C9	2.3 (5)	C12—C13—C17A—O17A	30.3 (4)
C11—C9—C10—C1	36.5 (4)	C18—C13—C17A—O17A	−88.3 (3)
C8—C9—C10—C1	161.5 (3)	C14—C13—C17A—N17	−34.5 (3)
C11—C9—C10—C5	−145.7 (3)	C12—C13—C17A—N17	−153.9 (3)
C8—C9—C10—C5	−20.7 (4)	C18—C13—C17A—N17	87.6 (3)
C10—C9—C11—C12	−178.8 (3)	C16—N17—C19—C20	−87.2 (3)
C8—C9—C11—C12	55.3 (4)	C17A—N17—C19—C20	86.4 (3)
C9—C11—C12—C13	−56.4 (4)	N17—C19—C20—C21	167.3 (3)
C11—C12—C13—C17A	175.1 (3)	C19—C20—C21—C22	−177.8 (3)
C11—C12—C13—C14	55.2 (4)	C3—O31—C31—O32	−4.1 (5)
C11—C12—C13—C18	−69.5 (4)	C3—O31—C31—C32	177.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O17A^i	0.95	2.41	3.315 (4)	160
C8—H8···O16^ii	1.00	2.47	3.454 (4)	169
C9—H9···O17A^iii	1.00	2.59	3.476 (4)	148
C15—H152···O32^iv	0.99	2.46	3.223 (4)	133

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