17β-Ethynyl-17α-hydroxy­androsta-1,4-dien-3-one

In the title mol­ecule, C₂₁H₂₆O₂, two C=C bonds [1.327 (3) and 1.338 (3) Å] contribute to the planarity of ring A along with the carbonyl group. Rings B and C have regular chair conformations, and the five-membered ring D has an envelope conformation. In the crystal structure, inter­molecular O—H...·O hydrogen bonds link mol­ecules into chains running along the c axis.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.037
• wR factor = 0.099
• Data-to-parameter ratio = 10.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.52 Ratio

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           27.50
           From the CIF: _reflns_number_total               2266
           Count of symmetry unique reflns         2281
           Completeness (_total/calc)             99.34%
           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
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C8     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C9     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C10    = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C13    = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C14    = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C17    = .          R

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

   6 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

17β-Ethynyl-17α-hydroxyandrosta-1,4-dien-3-one

Crystal data

C21H26O2	F(000) = 672
Mr = 310.42	Dx = 1.195 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3961 reflections
a = 7.6330 (12) Å	θ = 2.2–25.6°
b = 9.9270 (16) Å	µ = 0.08 mm^−1
c = 22.766 (4) Å	T = 296 K
V = 1725.0 (5) Å^3	Prismatic, colourless
Z = 4	0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	2266 independent reflections
Radiation source: fine-focus sealed tube	1909 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
φ and ω scans	θmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→6
Tmin = 0.978, Tmax = 0.981	k = −12→12
11020 measured reflections	l = −29→28

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0521P)^2 + 0.1897P] where P = (Fo^2 + 2Fc^2)/3
2266 reflections	(Δ/σ)max < 0.001
214 parameters	Δρmax = 0.14 e Å^−3
1 restraint	Δρmin = −0.15 e Å^−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
O1	0.6274 (3)	0.47116 (19)	0.51210 (7)	0.0908 (7)
O2	0.8123 (2)	0.41262 (13)	0.12365 (6)	0.0588 (4)
H2X	0.831 (4)	0.441 (3)	0.0890 (8)	0.082 (9)*
C1	0.8652 (3)	0.2692 (2)	0.41128 (8)	0.0520 (5)
H1	0.9811	0.2463	0.4036	0.062*
C2	0.8345 (3)	0.3541 (2)	0.45511 (8)	0.0606 (6)
H2	0.9283	0.3884	0.4765	0.073*
C3	0.6577 (4)	0.3948 (2)	0.47044 (8)	0.0597 (6)
C4	0.5186 (3)	0.3404 (2)	0.43490 (8)	0.0523 (5)
H4	0.4041	0.3667	0.4430	0.063*
C5	0.5464 (3)	0.25391 (19)	0.39082 (7)	0.0416 (4)
C6	0.3995 (3)	0.2021 (3)	0.35403 (9)	0.0537 (5)
H6A	0.2903	0.2422	0.3671	0.064*
H6B	0.3902	0.1053	0.3589	0.064*
C7	0.4284 (3)	0.2350 (2)	0.28918 (8)	0.0503 (5)
H7A	0.3407	0.1885	0.2659	0.060*
H7B	0.4127	0.3310	0.2833	0.060*
C8	0.6100 (2)	0.19447 (18)	0.26764 (7)	0.0365 (4)
H8	0.6186	0.0960	0.2682	0.044*
C9	0.7535 (2)	0.25282 (18)	0.30779 (7)	0.0340 (4)
H9	0.7372	0.3507	0.3073	0.041*
C10	0.7275 (2)	0.20800 (18)	0.37358 (7)	0.0397 (4)
C11	0.9390 (2)	0.2276 (2)	0.28463 (7)	0.0429 (4)
H11A	0.9649	0.1321	0.2870	0.051*
H11B	1.0225	0.2749	0.3093	0.051*
C12	0.9606 (3)	0.2750 (2)	0.22076 (8)	0.0457 (4)
H12A	0.9489	0.3722	0.2190	0.055*
H12B	1.0767	0.2514	0.2068	0.055*
C13	0.8245 (3)	0.21041 (17)	0.18170 (7)	0.0389 (4)
C14	0.6409 (2)	0.24326 (19)	0.20510 (7)	0.0392 (4)
H14	0.6326	0.3417	0.2063	0.047*
C15	0.5193 (3)	0.1973 (3)	0.15594 (8)	0.0578 (6)
H15A	0.4122	0.2499	0.1556	0.069*
H15B	0.4896	0.1028	0.1603	0.069*
C16	0.6269 (4)	0.2214 (3)	0.09910 (9)	0.0638 (6)
H16A	0.6354	0.1389	0.0764	0.077*
H16B	0.5715	0.2898	0.0750	0.077*
C17	0.8097 (3)	0.26805 (19)	0.11865 (8)	0.0480 (5)
C18	0.8571 (3)	0.0579 (2)	0.17697 (9)	0.0536 (5)
H18A	0.9742	0.0423	0.1631	0.080*
H18B	0.7748	0.0192	0.1499	0.080*
H18C	0.8428	0.0172	0.2149	0.080*
C19	0.7428 (3)	0.0530 (2)	0.38110 (10)	0.0598 (6)
H19A	0.7185	0.0293	0.4212	0.090*
H19B	0.8593	0.0247	0.3711	0.090*
H19C	0.6602	0.0091	0.3557	0.090*
C20	0.9552 (4)	0.2267 (2)	0.08065 (9)	0.0618 (6)
C21	1.0783 (5)	0.1986 (3)	0.05247 (10)	0.0855 (10)
H21	1.1761	0.1762	0.0301	0.103*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.1400 (19)	0.0759 (12)	0.0564 (9)	−0.0123 (12)	0.0175 (11)	−0.0278 (9)
O2	0.0924 (12)	0.0385 (7)	0.0454 (7)	0.0103 (8)	0.0146 (8)	0.0095 (6)
C1	0.0529 (12)	0.0675 (13)	0.0357 (9)	−0.0028 (11)	−0.0077 (8)	0.0059 (9)
C2	0.0783 (16)	0.0666 (14)	0.0369 (10)	−0.0166 (13)	−0.0118 (10)	0.0025 (10)
C3	0.0949 (18)	0.0483 (11)	0.0359 (9)	−0.0088 (12)	0.0091 (11)	0.0002 (9)
C4	0.0642 (14)	0.0495 (11)	0.0431 (10)	0.0036 (10)	0.0144 (9)	0.0015 (9)
C5	0.0484 (10)	0.0409 (9)	0.0354 (8)	−0.0024 (9)	0.0082 (8)	0.0067 (8)
C6	0.0428 (11)	0.0658 (13)	0.0524 (11)	−0.0065 (10)	0.0092 (9)	−0.0005 (10)
C7	0.0382 (10)	0.0650 (13)	0.0475 (10)	−0.0008 (10)	−0.0011 (8)	−0.0033 (10)
C8	0.0386 (9)	0.0349 (9)	0.0359 (8)	−0.0022 (7)	−0.0015 (7)	−0.0017 (7)
C9	0.0380 (9)	0.0316 (8)	0.0324 (7)	−0.0001 (7)	−0.0009 (7)	0.0016 (6)
C10	0.0451 (10)	0.0406 (9)	0.0335 (8)	0.0011 (8)	0.0007 (7)	0.0034 (7)
C11	0.0366 (9)	0.0543 (11)	0.0378 (8)	0.0007 (9)	−0.0010 (7)	0.0009 (9)
C12	0.0437 (10)	0.0520 (11)	0.0414 (9)	−0.0022 (10)	0.0055 (8)	0.0021 (9)
C13	0.0500 (10)	0.0350 (8)	0.0317 (8)	0.0050 (8)	0.0031 (7)	0.0013 (7)
C14	0.0465 (10)	0.0364 (9)	0.0348 (8)	0.0019 (8)	−0.0037 (7)	−0.0002 (7)
C15	0.0609 (14)	0.0681 (15)	0.0443 (10)	−0.0013 (12)	−0.0133 (10)	−0.0022 (10)
C16	0.0865 (17)	0.0672 (14)	0.0378 (9)	0.0046 (13)	−0.0127 (11)	−0.0005 (10)
C17	0.0716 (13)	0.0387 (9)	0.0337 (8)	0.0081 (10)	0.0036 (9)	0.0014 (8)
C18	0.0771 (15)	0.0389 (10)	0.0449 (10)	0.0110 (10)	0.0077 (10)	0.0010 (8)
C19	0.0823 (16)	0.0466 (11)	0.0504 (11)	0.0107 (12)	0.0069 (11)	0.0122 (9)
C20	0.0992 (18)	0.0508 (12)	0.0353 (9)	0.0145 (13)	0.0126 (11)	0.0054 (9)
C21	0.123 (3)	0.0827 (18)	0.0511 (12)	0.0346 (18)	0.0324 (15)	0.0091 (12)

Geometric parameters (Å, º)

O1—C3	1.236 (3)	C11—C12	1.537 (2)
O2—C17	1.440 (2)	C11—H11A	0.9700
O2—H2X	0.849 (17)	C11—H11B	0.9700
C1—C2	1.327 (3)	C12—C13	1.510 (3)
C1—C10	1.487 (3)	C12—H12A	0.9700
C1—H1	0.9300	C12—H12B	0.9700
C2—C3	1.451 (4)	C13—C14	1.534 (3)
C2—H2	0.9300	C13—C18	1.538 (2)
C3—C4	1.440 (3)	C13—C17	1.549 (2)
C4—C5	1.338 (3)	C14—C15	1.524 (3)
C4—H4	0.9300	C14—H14	0.9800
C5—C6	1.491 (3)	C15—C16	1.552 (3)
C5—C10	1.507 (3)	C15—H15A	0.9700
C6—C7	1.528 (3)	C15—H15B	0.9700
C6—H6A	0.9700	C16—C17	1.536 (3)
C6—H6B	0.9700	C16—H16A	0.9700
C7—C8	1.524 (3)	C16—H16B	0.9700
C7—H7A	0.9700	C17—C20	1.466 (3)
C7—H7B	0.9700	C18—H18A	0.9599
C8—C14	1.522 (2)	C18—H18B	0.9599
C8—C9	1.540 (2)	C18—H18C	0.9599
C8—H8	0.9800	C19—H19A	0.9599
C9—C11	1.531 (2)	C19—H19B	0.9599
C9—C10	1.575 (2)	C19—H19C	0.9599
C9—H9	0.9800	C20—C21	1.172 (4)
C10—C19	1.553 (3)	C21—H21	0.9300
C17—O2—H2X	105 (2)	H11A—C11—H11B	107.9
C2—C1—C10	124.6 (2)	C13—C12—C11	110.71 (16)
C2—C1—H1	117.7	C13—C12—H12A	109.5
C10—C1—H1	117.7	C11—C12—H12A	109.5
C1—C2—C3	121.5 (2)	C13—C12—H12B	109.5
C1—C2—H2	119.3	C11—C12—H12B	109.5
C3—C2—H2	119.3	H12A—C12—H12B	108.1
O1—C3—C4	121.5 (2)	C12—C13—C14	109.49 (14)
O1—C3—C2	122.0 (2)	C12—C13—C18	110.31 (17)
C4—C3—C2	116.52 (18)	C14—C13—C18	112.44 (17)
C5—C4—C3	123.0 (2)	C12—C13—C17	116.03 (16)
C5—C4—H4	118.5	C14—C13—C17	100.19 (15)
C3—C4—H4	118.5	C18—C13—C17	108.09 (14)
C4—C5—C6	121.58 (19)	C8—C14—C15	119.81 (17)
C4—C5—C10	122.33 (18)	C8—C14—C13	113.49 (15)
C6—C5—C10	116.04 (15)	C15—C14—C13	103.74 (15)
C5—C6—C7	111.12 (17)	C8—C14—H14	106.3
C5—C6—H6A	109.4	C15—C14—H14	106.3
C7—C6—H6A	109.4	C13—C14—H14	106.3
C5—C6—H6B	109.4	C14—C15—C16	104.11 (18)
C7—C6—H6B	109.4	C14—C15—H15A	110.9
H6A—C6—H6B	108.0	C16—C15—H15A	110.9
C8—C7—C6	112.70 (17)	C14—C15—H15B	110.9
C8—C7—H7A	109.1	C16—C15—H15B	110.9
C6—C7—H7A	109.1	H15A—C15—H15B	109.0
C8—C7—H7B	109.1	C17—C16—C15	106.61 (16)
C6—C7—H7B	109.1	C17—C16—H16A	110.4
H7A—C7—H7B	107.8	C15—C16—H16A	110.4
C14—C8—C7	110.96 (15)	C17—C16—H16B	110.4
C14—C8—C9	108.99 (14)	C15—C16—H16B	110.4
C7—C8—C9	110.90 (14)	H16A—C16—H16B	108.6
C14—C8—H8	108.6	O2—C17—C20	108.37 (18)
C7—C8—H8	108.6	O2—C17—C16	109.62 (19)
C9—C8—H8	108.6	C20—C17—C16	115.62 (17)
C11—C9—C8	113.08 (13)	O2—C17—C13	107.10 (15)
C11—C9—C10	113.45 (14)	C20—C17—C13	112.86 (17)
C8—C9—C10	111.62 (14)	C16—C17—C13	102.89 (17)
C11—C9—H9	106.0	C13—C18—H18A	109.5
C8—C9—H9	106.0	C13—C18—H18B	109.5
C10—C9—H9	106.0	H18A—C18—H18B	109.5
C1—C10—C5	112.00 (15)	C13—C18—H18C	109.5
C1—C10—C19	106.71 (17)	H18A—C18—H18C	109.5
C5—C10—C19	109.89 (17)	H18B—C18—H18C	109.5
C1—C10—C9	110.14 (15)	C10—C19—H19A	109.5
C5—C10—C9	106.14 (14)	C10—C19—H19B	109.5
C19—C10—C9	112.04 (15)	H19A—C19—H19B	109.5
C9—C11—C12	112.02 (15)	C10—C19—H19C	109.5
C9—C11—H11A	109.2	H19A—C19—H19C	109.5
C12—C11—H11A	109.2	H19B—C19—H19C	109.5
C9—C11—H11B	109.2	C21—C20—C17	175.7 (3)
C12—C11—H11B	109.2	C20—C21—H21	180.0
C10—C1—C2—C3	0.4 (3)	C8—C9—C11—C12	52.7 (2)
C1—C2—C3—O1	178.1 (2)	C10—C9—C11—C12	−178.93 (15)
C1—C2—C3—C4	−1.3 (3)	C9—C11—C12—C13	−55.1 (2)
O1—C3—C4—C5	−177.6 (2)	C11—C12—C13—C14	57.1 (2)
C2—C3—C4—C5	1.8 (3)	C11—C12—C13—C18	−67.2 (2)
C3—C4—C5—C6	−178.58 (19)	C11—C12—C13—C17	169.49 (16)
C3—C4—C5—C10	−1.4 (3)	C7—C8—C14—C15	−59.1 (2)
C4—C5—C6—C7	122.1 (2)	C9—C8—C14—C15	178.53 (17)
C10—C5—C6—C7	−55.3 (2)	C7—C8—C14—C13	177.73 (15)
C5—C6—C7—C8	50.2 (3)	C9—C8—C14—C13	55.33 (19)
C6—C7—C8—C14	−173.50 (17)	C12—C13—C14—C8	−59.24 (19)
C6—C7—C8—C9	−52.2 (2)	C18—C13—C14—C8	63.8 (2)
C14—C8—C9—C11	−51.57 (19)	C17—C13—C14—C8	178.31 (14)
C7—C8—C9—C11	−174.01 (16)	C12—C13—C14—C15	169.13 (16)
C14—C8—C9—C10	179.07 (15)	C18—C13—C14—C15	−67.9 (2)
C7—C8—C9—C10	56.6 (2)	C17—C13—C14—C15	46.68 (18)
C2—C1—C10—C5	0.1 (3)	C8—C14—C15—C16	−159.86 (18)
C2—C1—C10—C19	−120.2 (2)	C13—C14—C15—C16	−32.0 (2)
C2—C1—C10—C9	117.9 (2)	C14—C15—C16—C17	4.8 (2)
C4—C5—C10—C1	0.4 (3)	C15—C16—C17—O2	−89.9 (2)
C6—C5—C10—C1	177.73 (17)	C15—C16—C17—C20	147.2 (2)
C4—C5—C10—C19	118.9 (2)	C15—C16—C17—C13	23.8 (2)
C6—C5—C10—C19	−63.8 (2)	C12—C13—C17—O2	−45.0 (2)
C4—C5—C10—C9	−119.79 (19)	C14—C13—C17—O2	72.7 (2)
C6—C5—C10—C9	57.5 (2)	C18—C13—C17—O2	−169.43 (19)
C11—C9—C10—C1	52.4 (2)	C12—C13—C17—C20	74.2 (2)
C8—C9—C10—C1	−178.44 (15)	C14—C13—C17—C20	−168.08 (17)
C11—C9—C10—C5	173.84 (15)	C18—C13—C17—C20	−50.3 (2)
C8—C9—C10—C5	−57.00 (18)	C12—C13—C17—C16	−160.49 (17)
C11—C9—C10—C19	−66.2 (2)	C14—C13—C17—C16	−42.77 (18)
C8—C9—C10—C19	63.0 (2)	C18—C13—C17—C16	75.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2X···O1^i	0.85 (2)	1.98 (2)	2.827 (2)	173 (3)

Symmetry code: (i) −x+3/2, −y+1, z−1/2.