17-Ethynyl-3,17α-dimethoxy-5β-estra-1,3,5(10)-triene

The title compound, C₂₂H₂₈O₂, was synthesized from 17α-ethynyl­estradiol in 86% yield. The X-ray structure determination shows that, in the steroid nucleus, one of the cyclo­hexane rings adopts a half-chair conformation and the other shows a chair conformation. The cyclo­pentane ring adopts an envelope conformation. In the crystal structure, symmetry-related mol­ecules exist as C—H...O hydrogen-bonded dimers.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.058
• wR factor = 0.151
• Data-to-parameter ratio = 10.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.98

Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.53 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           27.57
           From the CIF: _reflns_number_total               2221
           Count of symmetry unique reflns         2258
           Completeness (_total/calc)             98.36%
           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
   1 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 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
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

17-Ethynyl-3,17α-dimethyoxy-5β-estra-1,3,5(10)-triene

Crystal data

C22H28O2	F(000) = 704
Mr = 324.44	Dx = 1.196 Mg m^−3
Monoclinic, C2	Melting point: 387-388 K K
Hall symbol: C 2y	Mo Kα radiation, λ = 0.71073 Å
a = 12.340 (2) Å	Cell parameters from 4503 reflections
b = 6.8289 (13) Å	θ = 2.9–27.6°
c = 21.710 (4) Å	µ = 0.07 mm^−1
β = 100.037 (4)°	T = 293 K
V = 1801.4 (6) Å^3	Block, colourless
Z = 4	0.57 × 0.51 × 0.39 mm

Data collection

Siemens SMART CCD area-detector diffractometer	2221 independent reflections
Radiation source: fine-focus sealed tube	2141 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
Detector resolution: 8.33 pixels mm^-1	θmax = 27.6°, θmin = 2.9°
ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −7→8
Tmin = 0.959, Tmax = 0.972	l = −28→27
6003 measured reflections

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	w = 1/[σ^2(Fo^2) + (0.0874P)^2 + 0.3877P] where P = (Fo^2 + 2Fc^2)/3
2221 reflections	(Δ/σ)max < 0.001
216 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.23 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	1.07278 (18)	0.1921 (4)	0.43064 (9)	0.0533 (5)
O2	0.63488 (14)	0.5061 (4)	−0.03606 (8)	0.0481 (5)
C1	0.70259 (17)	0.5009 (4)	0.13210 (11)	0.0369 (5)
H1	0.6646	0.5002	0.1655	0.044*
C2	0.64337 (18)	0.5044 (5)	0.07211 (12)	0.0408 (5)
H2	0.5669	0.5056	0.0653	0.049*
C3	0.69928 (18)	0.5059 (4)	0.02198 (10)	0.0360 (5)
C4	0.81273 (19)	0.5081 (4)	0.03285 (11)	0.0367 (5)
H4	0.8501	0.5107	−0.0008	0.044*
C5	0.87201 (17)	0.5065 (4)	0.09336 (10)	0.0338 (5)
C6	0.99630 (18)	0.5103 (5)	0.10107 (11)	0.0431 (6)
H6A	1.0179	0.6130	0.0748	0.052*
H6B	1.0214	0.3866	0.0867	0.052*
C7	1.0527 (2)	0.5448 (5)	0.16791 (13)	0.0471 (7)
H7A	1.0471	0.6821	0.1784	0.057*
H7B	1.1301	0.5119	0.1722	0.057*
C8	0.99971 (18)	0.4203 (4)	0.21248 (11)	0.0349 (5)
H8	0.9978	0.2841	0.1981	0.042*
C9	0.88100 (17)	0.4899 (4)	0.21110 (10)	0.0345 (5)
H9	0.8853	0.6242	0.2272	0.041*
C10	0.81769 (16)	0.4984 (4)	0.14467 (10)	0.0324 (4)
C11	0.82461 (19)	0.3673 (5)	0.25512 (11)	0.0432 (6)
H11A	0.8166	0.2340	0.2396	0.052*
H11B	0.7515	0.4194	0.2553	0.052*
C12	0.8887 (2)	0.3654 (5)	0.32208 (11)	0.0448 (6)
H12A	0.8886	0.4958	0.3398	0.054*
H12B	0.8528	0.2779	0.3474	0.054*
C13	1.0067 (2)	0.2988 (4)	0.32385 (11)	0.0373 (5)
C14	1.05987 (19)	0.4277 (4)	0.27932 (11)	0.0380 (5)
H14	1.0549	0.5631	0.2935	0.046*
C15	1.1822 (2)	0.3706 (6)	0.29429 (13)	0.0513 (7)
H15A	1.2285	0.4787	0.2859	0.062*
H15B	1.1970	0.2584	0.2696	0.062*
C16	1.2023 (2)	0.3202 (6)	0.36451 (14)	0.0567 (8)
H16A	1.2542	0.4115	0.3878	0.068*
H16B	1.2317	0.1888	0.3713	0.068*
C17	1.0883 (2)	0.3355 (4)	0.38596 (12)	0.0433 (6)
C18	1.0083 (3)	0.0803 (5)	0.30757 (14)	0.0501 (7)
H18A	0.9695	0.0602	0.2657	0.075*
H18B	0.9733	0.0068	0.3363	0.075*
H18C	1.0831	0.0373	0.3105	0.075*
C19	1.0742 (3)	0.5336 (5)	0.40979 (13)	0.0564 (8)
C20	1.0653 (4)	0.6923 (7)	0.42686 (18)	0.0822 (13)
H20	1.0601	0.8228	0.4375	0.099*
C21	1.1435 (3)	0.2127 (7)	0.48961 (15)	0.0730 (11)
H21A	1.1312	0.1062	0.5164	0.110*
H21B	1.1281	0.3344	0.5085	0.110*
H21C	1.2188	0.2114	0.4836	0.110*
C22	0.6893 (2)	0.5038 (5)	−0.08813 (11)	0.0473 (6)
H22A	0.6359	0.5038	−0.1260	0.071*
H22B	0.7340	0.3883	−0.0867	0.071*
H22C	0.7351	0.6178	−0.0871	0.071*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0598 (11)	0.0543 (13)	0.0415 (10)	−0.0006 (10)	−0.0032 (8)	0.0092 (9)
O2	0.0412 (9)	0.0585 (12)	0.0419 (9)	−0.0001 (10)	−0.0006 (7)	0.0026 (10)
C1	0.0338 (10)	0.0397 (12)	0.0389 (11)	0.0007 (11)	0.0109 (8)	0.0026 (11)
C2	0.0307 (9)	0.0406 (12)	0.0501 (13)	0.0003 (12)	0.0049 (8)	0.0024 (12)
C3	0.0378 (10)	0.0322 (11)	0.0361 (11)	−0.0004 (11)	0.0010 (8)	0.0019 (11)
C4	0.0397 (11)	0.0352 (11)	0.0366 (10)	−0.0001 (11)	0.0102 (8)	0.0029 (11)
C5	0.0323 (10)	0.0290 (10)	0.0400 (11)	−0.0012 (10)	0.0061 (8)	0.0022 (11)
C6	0.0333 (10)	0.0566 (16)	0.0408 (12)	−0.0037 (13)	0.0102 (9)	0.0065 (13)
C7	0.0350 (11)	0.058 (2)	0.0484 (14)	−0.0126 (12)	0.0077 (10)	0.0057 (12)
C8	0.0309 (10)	0.0367 (12)	0.0366 (11)	−0.0026 (9)	0.0045 (8)	0.0017 (10)
C9	0.0330 (10)	0.0344 (12)	0.0365 (11)	−0.0012 (10)	0.0075 (8)	−0.0015 (10)
C10	0.0314 (9)	0.0288 (10)	0.0372 (10)	0.0003 (10)	0.0065 (8)	0.0009 (10)
C11	0.0335 (10)	0.0577 (17)	0.0396 (12)	−0.0021 (12)	0.0095 (9)	0.0074 (12)
C12	0.0398 (11)	0.0575 (17)	0.0377 (12)	0.0019 (12)	0.0082 (9)	0.0060 (12)
C13	0.0398 (11)	0.0377 (13)	0.0325 (11)	−0.0011 (10)	0.0016 (8)	0.0028 (10)
C14	0.0345 (10)	0.0397 (12)	0.0386 (12)	−0.0024 (10)	0.0034 (8)	0.0005 (10)
C15	0.0346 (11)	0.065 (2)	0.0521 (15)	−0.0007 (13)	0.0016 (10)	0.0059 (14)
C16	0.0414 (13)	0.064 (2)	0.0588 (17)	0.0031 (14)	−0.0069 (11)	0.0046 (16)
C17	0.0457 (13)	0.0419 (15)	0.0391 (12)	−0.0011 (11)	−0.0021 (10)	0.0025 (11)
C18	0.0604 (16)	0.0382 (13)	0.0485 (15)	−0.0035 (13)	0.0004 (12)	0.0021 (12)
C19	0.0653 (17)	0.056 (2)	0.0415 (14)	0.0007 (15)	−0.0092 (12)	−0.0009 (13)
C20	0.122 (3)	0.052 (2)	0.060 (2)	0.010 (2)	−0.018 (2)	−0.0132 (18)
C21	0.078 (2)	0.083 (3)	0.0498 (17)	−0.002 (2)	−0.0120 (15)	0.0176 (19)
C22	0.0559 (13)	0.0430 (13)	0.0401 (12)	0.0010 (14)	0.0001 (10)	0.0021 (13)

Geometric parameters (Å, º)

O1—C17	1.415 (3)	C11—H11B	0.97
O1—C21	1.425 (3)	C12—C13	1.519 (3)
O2—C3	1.368 (3)	C12—H12A	0.97
O2—C22	1.412 (3)	C12—H12B	0.97
C1—C2	1.378 (3)	C13—C18	1.534 (4)
C1—C10	1.399 (3)	C13—C14	1.537 (3)
C1—H1	0.93	C13—C17	1.556 (3)
C2—C3	1.386 (3)	C14—C15	1.538 (3)
C2—H2	0.93	C14—H14	0.98
C3—C4	1.379 (3)	C15—C16	1.540 (4)
C4—C5	1.388 (3)	C15—H15A	0.97
C4—H4	0.93	C15—H15B	0.97
C5—C10	1.398 (3)	C16—C17	1.561 (4)
C5—C6	1.514 (3)	C16—H16A	0.97
C6—C7	1.514 (3)	C16—H16B	0.97
C6—H6A	0.97	C17—C19	1.469 (5)
C6—H6B	0.97	C18—H18A	0.96
C7—C8	1.519 (3)	C18—H18B	0.96
C7—H7A	0.97	C18—H18C	0.96
C7—H7B	0.97	C19—C20	1.156 (6)
C8—C14	1.511 (3)	C20—H20	0.93
C8—C9	1.535 (3)	C21—H21A	0.96
C8—H8	0.98	C21—H21B	0.96
C9—C10	1.517 (3)	C21—H21C	0.96
C9—C11	1.527 (3)	C22—H22A	0.96
C9—H9	0.98	C22—H22B	0.96
C11—C12	1.529 (3)	C22—H22C	0.96
C11—H11A	0.97
C17—O1—C21	114.4 (3)	C13—C12—H12B	109.4
C3—O2—C22	117.15 (18)	C11—C12—H12B	109.4
C2—C1—C10	122.52 (19)	H12A—C12—H12B	108.0
C2—C1—H1	118.7	C12—C13—C18	109.6 (2)
C10—C1—H1	118.7	C12—C13—C14	109.0 (2)
C1—C2—C3	119.2 (2)	C18—C13—C14	112.8 (2)
C1—C2—H2	120.4	C12—C13—C17	116.5 (2)
C3—C2—H2	120.4	C18—C13—C17	108.9 (2)
O2—C3—C4	124.6 (2)	C14—C13—C17	99.8 (2)
O2—C3—C2	115.76 (19)	C8—C14—C13	113.14 (19)
C4—C3—C2	119.7 (2)	C8—C14—C15	119.6 (2)
C3—C4—C5	120.9 (2)	C13—C14—C15	103.5 (2)
C3—C4—H4	119.5	C8—C14—H14	106.6
C5—C4—H4	119.5	C13—C14—H14	106.6
C4—C5—C10	120.52 (19)	C15—C14—H14	106.6
C4—C5—C6	117.46 (18)	C14—C15—C16	104.4 (2)
C10—C5—C6	122.0 (2)	C14—C15—H15A	110.9
C5—C6—C7	113.32 (19)	C16—C15—H15A	110.9
C5—C6—H6A	108.9	C14—C15—H15B	110.9
C7—C6—H6A	108.9	C16—C15—H15B	110.9
C5—C6—H6B	108.9	H15A—C15—H15B	108.9
C7—C6—H6B	108.9	C15—C16—C17	106.4 (2)
H6A—C6—H6B	107.7	C15—C16—H16A	110.4
C6—C7—C8	110.3 (2)	C17—C16—H16A	110.4
C6—C7—H7A	109.6	C15—C16—H16B	110.4
C8—C7—H7A	109.6	C17—C16—H16B	110.4
C6—C7—H7B	109.6	H16A—C16—H16B	108.6
C8—C7—H7B	109.6	O1—C17—C19	111.0 (2)
H7A—C7—H7B	108.1	O1—C17—C13	109.8 (2)
C14—C8—C7	113.53 (19)	C19—C17—C13	110.8 (2)
C14—C8—C9	108.40 (18)	O1—C17—C16	113.3 (2)
C7—C8—C9	109.2 (2)	C19—C17—C16	109.5 (3)
C14—C8—H8	108.5	C13—C17—C16	102.2 (2)
C7—C8—H8	108.5	C13—C18—H18A	109.5
C9—C8—H8	108.5	C13—C18—H18B	109.5
C10—C9—C11	113.63 (18)	H18A—C18—H18B	109.5
C10—C9—C8	111.22 (17)	C13—C18—H18C	109.5
C11—C9—C8	110.8 (2)	H18A—C18—H18C	109.5
C10—C9—H9	106.9	H18B—C18—H18C	109.5
C11—C9—H9	106.9	C20—C19—C17	177.4 (4)
C8—C9—H9	106.9	C19—C20—H20	175.2
C5—C10—C1	117.1 (2)	O1—C21—H21A	109.5
C5—C10—C9	121.34 (18)	O1—C21—H21B	109.5
C1—C10—C9	121.54 (18)	H21A—C21—H21B	109.5
C9—C11—C12	112.5 (2)	O1—C21—H21C	109.5
C9—C11—H11A	109.1	H21A—C21—H21C	109.5
C12—C11—H11A	109.1	H21B—C21—H21C	109.5
C9—C11—H11B	109.1	O2—C22—H22A	109.5
C12—C11—H11B	109.1	O2—C22—H22B	109.5
H11A—C11—H11B	107.8	H22A—C22—H22B	109.5
C13—C12—C11	111.20 (19)	O2—C22—H22C	109.5
C13—C12—H12A	109.4	H22A—C22—H22C	109.5
C11—C12—H12A	109.4	H22B—C22—H22C	109.5
C10—C1—C2—C3	−0.1 (4)	C11—C12—C13—C18	−69.6 (3)
C22—O2—C3—C4	1.6 (4)	C11—C12—C13—C14	54.4 (3)
C22—O2—C3—C2	−178.8 (3)	C11—C12—C13—C17	166.2 (2)
C1—C2—C3—O2	179.0 (3)	C7—C8—C14—C13	−179.1 (2)
C1—C2—C3—C4	−1.4 (4)	C9—C8—C14—C13	59.3 (3)
O2—C3—C4—C5	−179.6 (2)	C7—C8—C14—C15	−56.8 (3)
C2—C3—C4—C5	0.8 (4)	C9—C8—C14—C15	−178.4 (3)
C3—C4—C5—C10	1.4 (4)	C12—C13—C14—C8	−58.8 (3)
C3—C4—C5—C6	−179.7 (3)	C18—C13—C14—C8	63.2 (3)
C4—C5—C6—C7	169.7 (2)	C17—C13—C14—C8	178.6 (2)
C10—C5—C6—C7	−11.4 (4)	C12—C13—C14—C15	170.3 (2)
C5—C6—C7—C8	44.3 (4)	C18—C13—C14—C15	−67.7 (3)
C6—C7—C8—C14	173.0 (2)	C17—C13—C14—C15	47.7 (3)
C6—C7—C8—C9	−65.9 (3)	C8—C14—C15—C16	−159.3 (3)
C14—C8—C9—C10	176.4 (2)	C13—C14—C15—C16	−32.4 (3)
C7—C8—C9—C10	52.3 (3)	C14—C15—C16—C17	4.1 (4)
C14—C8—C9—C11	−56.2 (3)	C21—O1—C17—C19	−57.0 (3)
C7—C8—C9—C11	179.7 (2)	C21—O1—C17—C13	−179.8 (3)
C4—C5—C10—C1	−2.8 (4)	C21—O1—C17—C16	66.7 (3)
C6—C5—C10—C1	178.3 (3)	C12—C13—C17—O1	78.4 (3)
C4—C5—C10—C9	178.0 (2)	C18—C13—C17—O1	−46.2 (3)
C6—C5—C10—C9	−0.9 (4)	C14—C13—C17—O1	−164.6 (2)
C2—C1—C10—C5	2.2 (4)	C12—C13—C17—C19	−44.5 (3)
C2—C1—C10—C9	−178.6 (2)	C18—C13—C17—C19	−169.1 (3)
C11—C9—C10—C5	−145.7 (3)	C14—C13—C17—C19	72.5 (3)
C8—C9—C10—C5	−19.8 (3)	C12—C13—C17—C16	−161.2 (3)
C11—C9—C10—C1	35.1 (4)	C18—C13—C17—C16	74.3 (3)
C8—C9—C10—C1	161.0 (3)	C14—C13—C17—C16	−44.1 (3)
C10—C9—C11—C12	−178.6 (2)	C15—C16—C17—O1	143.0 (3)
C8—C9—C11—C12	55.3 (3)	C15—C16—C17—C19	−92.5 (3)
C9—C11—C12—C13	−54.7 (3)	C15—C16—C17—C13	25.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2^i	0.93	2.46	3.386 (3)	174
C20—H20···O1^ii	0.93	2.53	3.415 (6)	159

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