In the steroidal nucleus of 16-[4-(3-chloropropoxy)-3-methoxybenzylidene]-17-oxoandrost-5-en-3
-ol, C
30H
29ClO
4, (I), the outer two six-membered rings are in chair conformations, while the five-membered ring and the central six-membered ring of the steroidal nucleus adopt half-chair and envelope conformations, respectively. In 16-[3-methoxy-4-(2-pyrrolidin-1-ylethoxy)benzylidene]-3
-pyrrolidinoandrost-5-en-17
-ol monohydrate, C
37H
54N
2O
3·H
2O, (II), one C atom of one of the outer six-membered rings of the steroid nucleus and the four C atoms of the ethoxypyrrolidine ring are disordered over two sites. The five-membered ring, and the central and one of the outer six-membered rings of the steroidal nucleus exhibit distorted half-chair, chair and envelope conformations, respectively. In (I), intermolecular O-H
O hydrogen bonds link the molecules into chains
via a co-operative O-H
O-H
O-H pattern. In (II), intermolecular O-H
O and O-H
N hydrogen bonds link the steroid and water molecules alternately into extended chains.
Supporting information
CCDC references: 231082; 231083
To a stirred suspension of 16-[3-methoxy-4-(2-pyrrolidin-1-ylethoxy)benzylidene]-3-pyrrolidino- 3,5-androstadien-17-one (0.5 g, 0.871 mmol) in methanol (75 ml), sodium borohydride (1.0 g) was added in small amounts over a period of 2 h at room temperature. Stirring was continued for a further 4 h. Excess solvent was removed under vacuum and the reaction mixture was poured into ice-cold water (100 ml). The precipitate obtained was filtered, washed with water, dried and crystallized from methanol-acetone (Ratio?) to afford (I) (institution code: DPJ-RG-1122; yield: 0.38 g, 75.54%; m.p. 469–472 K). To a solution of dehydroepiandrosterone (0.75 g, 2.60 mmol) in methanol (10 ml), sodium hydroxide pellets (1.5 g) were added and dissolved. 4-(3-chloro)-propoxy-3-methoxybenzaldehyde (1 g, 4.373 mmol) was added dropwise and stirred for 2 h. The completion of the reaction was monitored using thin-layer chromatography. Ice-cold water was added to the reaction mixture and the precipitate obtained was filtered, washed, dried and crystallized from acetone to afford (II) (institution code: DPJ-RG-1150; yield: 1.5 g, 86.7%; m.p. 483–485 K).
For compound (II), atom C4 on ring A of the steroid nucleus is disordered over two sites. The four ring C atoms of the ethoxypyrrolidine moiety are also disordered over two conformations and two sets of positions were defined for pyrrolidine ring atoms C31—C34. Constrained refinement of the site-occupation factors for the two disordered regions led to values of 0.788 (7) and 0.510 (13), respectively, for the major conformations. The chemically equivalent bonds involving the disordered C atoms were restrained to have similar lengths and the 1,3 distances within each conformation of the pyrrolidine ring were also restrained to be similar. Neighbouring disordered atoms within and between each conformation of the disordered region were also restrained to have similar atomic displacement parameters. The position of the hydroxy H atom in (I) was determined from a difference Fourier map and refined freely along with its isotropic displacement parameters. The positions of the water H atoms in (II) were also determined from a difference Fourier map and were refined along with their isotropic displacement parameters, while restraining the O—H bond length to 0.82 Å. The methyl H atoms in both compounds were constrained to an ideal geometry (C—H = 0.98 Å), with Uiso(H) = 1.5Ueq(C), but were allowed to rotate freely about the C—C bonds. All remaining H atoms were placed in geometrically idealized positions (C—H = 0.95–1.00 Å) and were constrained ride on their parent atoms. The presence of Cl in compound (I) permitted the determination of the absolute configuration of the molecule by refining the Flack parameter [−0.21 (7); Flack, 1983; Flack & Bernardinelli, 2000]. How many Friedel pairs? Due to the absence of any significant anomalous scatterers in (II), attempts to confirm the absolute structure by refinement of the Flack parameter in the presence of 3177 sets of Friedel equivalents led to an inconclusive value of 0.0 (8). Therefore, the Friedel pairs were merged before the final refinement and the absolute configuration was assigned to correspond with the known chiral centres in a precursor molecule, which remained unchanged during the synthesis of (II). Reflections 1 1 2, 0 1 2 and 1 1 1 in (I), and 0 2 1, 0 1 1 and 0 4 0 in (II), were partially obscured by the beam stop and were omitted.
For both compounds, 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).
(I) 16-[4-(3-chloropropoxy)-3-methoxybenzylidene]-17-oxoandrost-5-en-3
β-ol
top
Crystal data top
C30H39ClO4 | Dx = 1.266 Mg m−3 |
Mr = 499.09 | Melting point: 469 K |
Trigonal, R3 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: R 3 | Cell parameters from 19304 reflections |
a = 34.3749 (8) Å | θ = 2.0–27.5° |
c = 5.7585 (1) Å | µ = 0.18 mm−1 |
V = 5892.8 (2) Å3 | T = 160 K |
Z = 9 | Prism, colourless |
F(000) = 2412 | 0.30 × 0.12 × 0.10 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 5990 independent reflections |
Radiation source: Nonius FR591 sealed tube generator | 5077 reflections with I > 2σ(I) |
Horizontally mounted graphite crystal monochromator | Rint = 0.062 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 2.1° |
ϕ and ω scans with κ offsets | h = −44→41 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −44→44 |
Tmin = 0.909, Tmax = 0.984 | l = −7→7 |
29761 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.049 | w = 1/[σ2(Fo2) + (0.0672P)2 + 7.0766P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.127 | (Δ/σ)max < 0.001 |
S = 1.02 | Δρmax = 0.60 e Å−3 |
5987 reflections | Δρmin = −0.34 e Å−3 |
324 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.00078 (19) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack & Bernardinelli (2000) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.21 (7) |
Crystal data top
C30H39ClO4 | Z = 9 |
Mr = 499.09 | Mo Kα radiation |
Trigonal, R3 | µ = 0.18 mm−1 |
a = 34.3749 (8) Å | T = 160 K |
c = 5.7585 (1) Å | 0.30 × 0.12 × 0.10 mm |
V = 5892.8 (2) Å3 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 5990 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 5077 reflections with I > 2σ(I) |
Tmin = 0.909, Tmax = 0.984 | Rint = 0.062 |
29761 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.127 | Δρmax = 0.60 e Å−3 |
S = 1.02 | Δρmin = −0.34 e Å−3 |
5987 reflections | Absolute structure: Flack & Bernardinelli (2000) |
324 parameters | Absolute structure parameter: −0.21 (7) |
1 restraint | |
Special details top
Experimental. Solvent used: methnol-acetone mixture Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.464 (1) Frames collected: 222 Seconds exposure per frame: 120 Degrees rotation per frame: 2.0 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 (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | −0.06166 (3) | −0.00522 (3) | −0.34802 (14) | 0.0493 (2) | |
O3 | 0.34998 (6) | 0.03704 (6) | 0.4690 (3) | 0.0290 (4) | |
H3A | 0.3353 (9) | 0.0203 (9) | 0.377 (5) | 0.013 (7)* | |
O17 | 0.22766 (6) | 0.26738 (7) | 0.8851 (3) | 0.0358 (4) | |
O23 | −0.01387 (6) | 0.15520 (7) | 0.5467 (3) | 0.0382 (5) | |
O28 | −0.02007 (6) | 0.10901 (7) | 0.1773 (4) | 0.0400 (5) | |
C1 | 0.34027 (8) | 0.13116 (8) | 0.7416 (4) | 0.0241 (5) | |
H1A | 0.3624 | 0.1575 | 0.8319 | 0.029* | |
H1B | 0.3142 | 0.1131 | 0.8442 | 0.029* | |
C2 | 0.36165 (8) | 0.10263 (9) | 0.6755 (4) | 0.0260 (5) | |
H2A | 0.3898 | 0.1213 | 0.5878 | 0.031* | |
H2B | 0.3693 | 0.0918 | 0.8182 | 0.031* | |
C3 | 0.32981 (8) | 0.06328 (8) | 0.5301 (4) | 0.0248 (5) | |
H3 | 0.3018 | 0.0442 | 0.6214 | 0.030* | |
C4 | 0.31764 (9) | 0.07993 (8) | 0.3105 (4) | 0.0254 (5) | |
H4A | 0.3450 | 0.0977 | 0.2159 | 0.030* | |
H4B | 0.2961 | 0.0539 | 0.2167 | 0.030* | |
C5 | 0.29703 (8) | 0.10863 (8) | 0.3712 (4) | 0.0222 (5) | |
C6 | 0.25712 (8) | 0.09782 (8) | 0.2857 (4) | 0.0255 (5) | |
H6 | 0.2425 | 0.0718 | 0.1906 | 0.031* | |
C7 | 0.23348 (8) | 0.12370 (8) | 0.3282 (4) | 0.0265 (5) | |
H7A | 0.2076 | 0.1061 | 0.4325 | 0.032* | |
H7B | 0.2217 | 0.1278 | 0.1790 | 0.032* | |
C8 | 0.26414 (8) | 0.16971 (8) | 0.4371 (4) | 0.0200 (5) | |
H8 | 0.2837 | 0.1909 | 0.3133 | 0.024* | |
C9 | 0.29420 (8) | 0.16681 (8) | 0.6278 (4) | 0.0204 (4) | |
H9 | 0.2735 | 0.1446 | 0.7447 | 0.025* | |
C10 | 0.32422 (8) | 0.14817 (7) | 0.5334 (4) | 0.0199 (4) | |
C11 | 0.32102 (8) | 0.21191 (8) | 0.7566 (4) | 0.0240 (5) | |
H11A | 0.3438 | 0.2342 | 0.6496 | 0.029* | |
H11B | 0.3371 | 0.2078 | 0.8885 | 0.029* | |
C12 | 0.29172 (8) | 0.23087 (8) | 0.8496 (4) | 0.0243 (5) | |
H12A | 0.2716 | 0.2109 | 0.9729 | 0.029* | |
H12B | 0.3112 | 0.2609 | 0.9181 | 0.029* | |
C13 | 0.26382 (8) | 0.23446 (8) | 0.6540 (4) | 0.0214 (5) | |
C14 | 0.23609 (8) | 0.18781 (7) | 0.5438 (4) | 0.0212 (5) | |
H14 | 0.2196 | 0.1671 | 0.6756 | 0.025* | |
C15 | 0.19985 (8) | 0.19076 (8) | 0.4008 (4) | 0.0230 (5) | |
H15A | 0.2119 | 0.2061 | 0.2505 | 0.028* | |
H15B | 0.1736 | 0.1606 | 0.3721 | 0.028* | |
C16 | 0.18793 (8) | 0.21839 (8) | 0.5595 (4) | 0.0233 (5) | |
C17 | 0.22647 (8) | 0.24382 (8) | 0.7243 (4) | 0.0245 (5) | |
C18 | 0.29329 (8) | 0.27166 (8) | 0.4783 (4) | 0.0255 (5) | |
H18A | 0.3075 | 0.3009 | 0.5562 | 0.038* | |
H18B | 0.2745 | 0.2717 | 0.3502 | 0.038* | |
H18C | 0.3166 | 0.2660 | 0.4171 | 0.038* | |
C19 | 0.36533 (8) | 0.18453 (8) | 0.4001 (4) | 0.0274 (5) | |
H19A | 0.3811 | 0.1708 | 0.3250 | 0.041* | |
H19B | 0.3857 | 0.2078 | 0.5088 | 0.041* | |
H19C | 0.3553 | 0.1981 | 0.2818 | 0.041* | |
C20 | 0.14950 (8) | 0.21898 (8) | 0.5840 (4) | 0.0259 (5) | |
H20 | 0.1497 | 0.2388 | 0.6997 | 0.031* | |
C21 | 0.10732 (8) | 0.19336 (8) | 0.4574 (4) | 0.0261 (5) | |
C22 | 0.06748 (9) | 0.18875 (9) | 0.5571 (4) | 0.0284 (5) | |
H22 | 0.0695 | 0.2048 | 0.6952 | 0.034* | |
C23 | 0.02602 (8) | 0.16171 (9) | 0.4593 (4) | 0.0293 (5) | |
C24 | 0.02237 (9) | 0.13695 (9) | 0.2560 (5) | 0.0306 (6) | |
C25 | 0.06123 (9) | 0.14357 (9) | 0.1482 (4) | 0.0310 (6) | |
H25 | 0.0593 | 0.1288 | 0.0056 | 0.037* | |
C26 | 0.10314 (9) | 0.17170 (9) | 0.2474 (4) | 0.0287 (5) | |
H26 | 0.1294 | 0.1762 | 0.1696 | 0.034* | |
C27 | −0.01146 (10) | 0.18450 (11) | 0.7261 (5) | 0.0405 (7) | |
H27A | 0.0013 | 0.1789 | 0.8660 | 0.061* | |
H27B | −0.0417 | 0.1792 | 0.7603 | 0.061* | |
H27C | 0.0077 | 0.2157 | 0.6763 | 0.061* | |
C29 | −0.02468 (9) | 0.08087 (11) | −0.0190 (5) | 0.0388 (6) | |
H29A | −0.0118 | 0.0615 | 0.0178 | 0.047* | |
H29B | −0.0087 | 0.0996 | −0.1556 | 0.047* | |
C30 | −0.07440 (10) | 0.05247 (13) | −0.0691 (6) | 0.0527 (9) | |
H30A | −0.0883 | 0.0288 | 0.0510 | 0.063* | |
H30B | −0.0883 | 0.0716 | −0.0577 | 0.063* | |
C31 | −0.08459 (12) | 0.03056 (13) | −0.3051 (7) | 0.0545 (9) | |
H31A | −0.0725 | 0.0543 | −0.4256 | 0.065* | |
H31B | −0.1176 | 0.0128 | −0.3255 | 0.065* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0498 (5) | 0.0436 (4) | 0.0585 (5) | 0.0262 (4) | −0.0040 (4) | −0.0074 (3) |
O3 | 0.0324 (10) | 0.0271 (9) | 0.0341 (9) | 0.0199 (8) | −0.0076 (8) | −0.0053 (8) |
O17 | 0.0365 (10) | 0.0395 (11) | 0.0372 (10) | 0.0233 (9) | −0.0040 (8) | −0.0156 (8) |
O23 | 0.0255 (10) | 0.0541 (13) | 0.0387 (10) | 0.0227 (9) | −0.0008 (8) | −0.0096 (9) |
O28 | 0.0263 (10) | 0.0507 (12) | 0.0422 (11) | 0.0186 (9) | −0.0065 (8) | −0.0158 (9) |
C1 | 0.0279 (12) | 0.0280 (12) | 0.0195 (11) | 0.0163 (10) | −0.0044 (9) | −0.0016 (9) |
C2 | 0.0284 (12) | 0.0307 (13) | 0.0247 (11) | 0.0190 (11) | −0.0033 (9) | −0.0008 (9) |
C3 | 0.0246 (12) | 0.0244 (12) | 0.0289 (12) | 0.0149 (10) | −0.0023 (9) | 0.0013 (9) |
C4 | 0.0308 (13) | 0.0262 (12) | 0.0232 (11) | 0.0173 (11) | −0.0045 (9) | −0.0037 (9) |
C5 | 0.0282 (12) | 0.0208 (11) | 0.0184 (10) | 0.0128 (10) | −0.0019 (9) | −0.0005 (8) |
C6 | 0.0298 (13) | 0.0226 (12) | 0.0261 (11) | 0.0146 (10) | −0.0065 (9) | −0.0048 (9) |
C7 | 0.0252 (12) | 0.0240 (12) | 0.0308 (12) | 0.0127 (10) | −0.0089 (9) | −0.0075 (10) |
C8 | 0.0198 (11) | 0.0198 (11) | 0.0206 (10) | 0.0101 (9) | −0.0030 (8) | −0.0008 (8) |
C9 | 0.0225 (11) | 0.0219 (11) | 0.0191 (10) | 0.0128 (10) | −0.0023 (8) | −0.0002 (8) |
C10 | 0.0214 (11) | 0.0192 (11) | 0.0185 (10) | 0.0097 (9) | −0.0009 (8) | 0.0004 (8) |
C11 | 0.0246 (12) | 0.0251 (12) | 0.0246 (11) | 0.0140 (10) | −0.0077 (9) | −0.0052 (9) |
C12 | 0.0286 (12) | 0.0241 (12) | 0.0212 (11) | 0.0139 (10) | −0.0043 (9) | −0.0034 (9) |
C13 | 0.0237 (12) | 0.0192 (11) | 0.0215 (11) | 0.0109 (9) | 0.0001 (9) | −0.0012 (8) |
C14 | 0.0216 (11) | 0.0189 (11) | 0.0215 (10) | 0.0089 (9) | −0.0016 (8) | 0.0010 (8) |
C15 | 0.0211 (11) | 0.0254 (12) | 0.0244 (11) | 0.0129 (10) | −0.0029 (9) | −0.0010 (9) |
C16 | 0.0247 (12) | 0.0206 (11) | 0.0240 (11) | 0.0110 (10) | 0.0003 (9) | 0.0011 (9) |
C17 | 0.0267 (12) | 0.0225 (12) | 0.0251 (12) | 0.0130 (10) | 0.0007 (9) | 0.0007 (9) |
C18 | 0.0252 (12) | 0.0213 (12) | 0.0281 (12) | 0.0102 (10) | −0.0007 (9) | 0.0001 (9) |
C19 | 0.0246 (12) | 0.0274 (13) | 0.0288 (12) | 0.0120 (11) | 0.0019 (10) | 0.0015 (10) |
C20 | 0.0276 (12) | 0.0245 (12) | 0.0285 (12) | 0.0151 (10) | −0.0007 (10) | −0.0016 (9) |
C21 | 0.0270 (13) | 0.0267 (12) | 0.0293 (12) | 0.0169 (11) | −0.0001 (10) | 0.0036 (10) |
C22 | 0.0287 (13) | 0.0323 (13) | 0.0297 (12) | 0.0195 (11) | 0.0008 (10) | −0.0006 (10) |
C23 | 0.0246 (12) | 0.0375 (14) | 0.0318 (13) | 0.0200 (11) | 0.0014 (10) | 0.0003 (11) |
C24 | 0.0260 (13) | 0.0328 (14) | 0.0334 (13) | 0.0150 (11) | −0.0046 (10) | −0.0014 (10) |
C25 | 0.0272 (13) | 0.0388 (15) | 0.0287 (13) | 0.0178 (12) | −0.0023 (10) | −0.0034 (10) |
C26 | 0.0263 (12) | 0.0356 (14) | 0.0284 (12) | 0.0186 (11) | 0.0017 (10) | 0.0016 (10) |
C27 | 0.0358 (15) | 0.0527 (18) | 0.0419 (15) | 0.0288 (14) | 0.0038 (12) | −0.0058 (13) |
C29 | 0.0302 (14) | 0.0447 (17) | 0.0413 (15) | 0.0185 (13) | −0.0046 (12) | −0.0122 (13) |
C30 | 0.0304 (16) | 0.064 (2) | 0.061 (2) | 0.0218 (16) | −0.0073 (14) | −0.0238 (17) |
C31 | 0.050 (2) | 0.061 (2) | 0.064 (2) | 0.0370 (18) | −0.0215 (16) | −0.0246 (18) |
Geometric parameters (Å, º) top
Cl1—C31 | 1.779 (3) | C12—H12B | 0.9900 |
O3—C3 | 1.430 (3) | C13—C17 | 1.526 (3) |
O3—H3A | 0.76 (3) | C13—C14 | 1.534 (3) |
O17—C17 | 1.218 (3) | C13—C18 | 1.546 (3) |
O23—C23 | 1.370 (3) | C14—C15 | 1.538 (3) |
O23—C27 | 1.416 (3) | C14—H14 | 1.0000 |
O28—C24 | 1.362 (3) | C15—C16 | 1.514 (3) |
O28—C29 | 1.444 (3) | C15—H15A | 0.9900 |
C1—C2 | 1.539 (3) | C15—H15B | 0.9900 |
C1—C10 | 1.551 (3) | C16—C20 | 1.339 (3) |
C1—H1A | 0.9900 | C16—C17 | 1.504 (3) |
C1—H1B | 0.9900 | C18—H18A | 0.9800 |
C2—C3 | 1.499 (3) | C18—H18B | 0.9800 |
C2—H2A | 0.9900 | C18—H18C | 0.9800 |
C2—H2B | 0.9900 | C19—H19A | 0.9800 |
C3—C4 | 1.530 (3) | C19—H19B | 0.9800 |
C3—H3 | 1.0000 | C19—H19C | 0.9800 |
C4—C5 | 1.515 (3) | C20—C21 | 1.460 (3) |
C4—H4A | 0.9900 | C20—H20 | 0.9500 |
C4—H4B | 0.9900 | C21—C26 | 1.389 (4) |
C5—C6 | 1.324 (3) | C21—C22 | 1.419 (3) |
C5—C10 | 1.524 (3) | C22—C23 | 1.374 (4) |
C6—C7 | 1.495 (3) | C22—H22 | 0.9500 |
C6—H6 | 0.9500 | C23—C24 | 1.415 (4) |
C7—C8 | 1.529 (3) | C24—C25 | 1.385 (4) |
C7—H7A | 0.9900 | C25—C26 | 1.394 (4) |
C7—H7B | 0.9900 | C25—H25 | 0.9500 |
C8—C14 | 1.515 (3) | C26—H26 | 0.9500 |
C8—C9 | 1.545 (3) | C27—H27A | 0.9800 |
C8—H8 | 1.0000 | C27—H27B | 0.9800 |
C9—C11 | 1.541 (3) | C27—H27C | 0.9800 |
C9—C10 | 1.560 (3) | C29—C30 | 1.513 (4) |
C9—H9 | 1.0000 | C29—H29A | 0.9900 |
C10—C19 | 1.543 (3) | C29—H29B | 0.9900 |
C11—C12 | 1.544 (3) | C30—C31 | 1.507 (5) |
C11—H11A | 0.9900 | C30—H30A | 0.9900 |
C11—H11B | 0.9900 | C30—H30B | 0.9900 |
C12—C13 | 1.523 (3) | C31—H31A | 0.9900 |
C12—H12A | 0.9900 | C31—H31B | 0.9900 |
| | | |
C3—O3—H3A | 108 (2) | C8—C14—C13 | 113.99 (18) |
C23—O23—C27 | 117.0 (2) | C8—C14—C15 | 120.86 (19) |
C24—O28—C29 | 116.9 (2) | C13—C14—C15 | 104.66 (19) |
C2—C1—C10 | 114.97 (18) | C8—C14—H14 | 105.4 |
C2—C1—H1A | 108.5 | C13—C14—H14 | 105.4 |
C10—C1—H1A | 108.5 | C15—C14—H14 | 105.4 |
C2—C1—H1B | 108.5 | C16—C15—C14 | 101.56 (18) |
C10—C1—H1B | 108.5 | C16—C15—H15A | 111.5 |
H1A—C1—H1B | 107.5 | C14—C15—H15A | 111.5 |
C3—C2—C1 | 110.31 (19) | C16—C15—H15B | 111.5 |
C3—C2—H2A | 109.6 | C14—C15—H15B | 111.5 |
C1—C2—H2A | 109.6 | H15A—C15—H15B | 109.3 |
C3—C2—H2B | 109.6 | C20—C16—C17 | 120.9 (2) |
C1—C2—H2B | 109.6 | C20—C16—C15 | 130.6 (2) |
H2A—C2—H2B | 108.1 | C17—C16—C15 | 108.02 (19) |
O3—C3—C2 | 109.94 (19) | O17—C17—C16 | 126.4 (2) |
O3—C3—C4 | 110.0 (2) | O17—C17—C13 | 126.1 (2) |
C2—C3—C4 | 109.7 (2) | C16—C17—C13 | 107.44 (19) |
O3—C3—H3 | 109.1 | C13—C18—H18A | 109.5 |
C2—C3—H3 | 109.1 | C13—C18—H18B | 109.5 |
C4—C3—H3 | 109.1 | H18A—C18—H18B | 109.5 |
C5—C4—C3 | 110.92 (19) | C13—C18—H18C | 109.5 |
C5—C4—H4A | 109.5 | H18A—C18—H18C | 109.5 |
C3—C4—H4A | 109.5 | H18B—C18—H18C | 109.5 |
C5—C4—H4B | 109.5 | C10—C19—H19A | 109.5 |
C3—C4—H4B | 109.5 | C10—C19—H19B | 109.5 |
H4A—C4—H4B | 108.0 | H19A—C19—H19B | 109.5 |
C6—C5—C4 | 119.2 (2) | C10—C19—H19C | 109.5 |
C6—C5—C10 | 124.4 (2) | H19A—C19—H19C | 109.5 |
C4—C5—C10 | 116.36 (19) | H19B—C19—H19C | 109.5 |
C5—C6—C7 | 124.6 (2) | C16—C20—C21 | 128.9 (2) |
C5—C6—H6 | 117.7 | C16—C20—H20 | 115.5 |
C7—C6—H6 | 117.7 | C21—C20—H20 | 115.5 |
C6—C7—C8 | 112.6 (2) | C26—C21—C22 | 117.2 (2) |
C6—C7—H7A | 109.1 | C26—C21—C20 | 124.3 (2) |
C8—C7—H7A | 109.1 | C22—C21—C20 | 118.5 (2) |
C6—C7—H7B | 109.1 | C23—C22—C21 | 121.8 (2) |
C8—C7—H7B | 109.1 | C23—C22—H22 | 119.1 |
H7A—C7—H7B | 107.8 | C21—C22—H22 | 119.1 |
C14—C8—C7 | 109.88 (19) | O23—C23—C22 | 125.1 (2) |
C14—C8—C9 | 108.77 (17) | O23—C23—C24 | 115.2 (2) |
C7—C8—C9 | 111.24 (19) | C22—C23—C24 | 119.7 (2) |
C14—C8—H8 | 109.0 | O28—C24—C25 | 124.9 (2) |
C7—C8—H8 | 109.0 | O28—C24—C23 | 116.2 (2) |
C9—C8—H8 | 109.0 | C25—C24—C23 | 118.9 (2) |
C11—C9—C8 | 111.12 (18) | C24—C25—C26 | 120.5 (2) |
C11—C9—C10 | 113.27 (18) | C24—C25—H25 | 119.8 |
C8—C9—C10 | 112.32 (17) | C26—C25—H25 | 119.8 |
C11—C9—H9 | 106.5 | C21—C26—C25 | 121.5 (2) |
C8—C9—H9 | 106.5 | C21—C26—H26 | 119.2 |
C10—C9—H9 | 106.5 | C25—C26—H26 | 119.2 |
C5—C10—C19 | 108.81 (18) | O23—C27—H27A | 109.5 |
C5—C10—C1 | 108.22 (18) | O23—C27—H27B | 109.5 |
C19—C10—C1 | 109.60 (19) | H27A—C27—H27B | 109.5 |
C5—C10—C9 | 110.07 (18) | O23—C27—H27C | 109.5 |
C19—C10—C9 | 111.52 (18) | H27A—C27—H27C | 109.5 |
C1—C10—C9 | 108.56 (17) | H27B—C27—H27C | 109.5 |
C9—C11—C12 | 113.79 (19) | O28—C29—C30 | 107.0 (2) |
C9—C11—H11A | 108.8 | O28—C29—H29A | 110.3 |
C12—C11—H11A | 108.8 | C30—C29—H29A | 110.3 |
C9—C11—H11B | 108.8 | O28—C29—H29B | 110.3 |
C12—C11—H11B | 108.8 | C30—C29—H29B | 110.3 |
H11A—C11—H11B | 107.7 | H29A—C29—H29B | 108.6 |
C13—C12—C11 | 110.34 (18) | C31—C30—C29 | 113.5 (3) |
C13—C12—H12A | 109.6 | C31—C30—H30A | 108.9 |
C11—C12—H12A | 109.6 | C29—C30—H30A | 108.9 |
C13—C12—H12B | 109.6 | C31—C30—H30B | 108.9 |
C11—C12—H12B | 109.6 | C29—C30—H30B | 108.9 |
H12A—C12—H12B | 108.1 | H30A—C30—H30B | 107.7 |
C12—C13—C17 | 116.82 (19) | C30—C31—Cl1 | 113.5 (2) |
C12—C13—C14 | 107.98 (18) | C30—C31—H31A | 108.9 |
C17—C13—C14 | 100.45 (18) | Cl1—C31—H31A | 108.9 |
C12—C13—C18 | 111.84 (19) | C30—C31—H31B | 108.9 |
C17—C13—C18 | 105.76 (19) | Cl1—C31—H31B | 108.9 |
C14—C13—C18 | 113.66 (18) | H31A—C31—H31B | 107.7 |
| | | |
C10—C1—C2—C3 | −56.0 (3) | C18—C13—C14—C8 | 63.2 (3) |
C1—C2—C3—O3 | 179.85 (19) | C12—C13—C14—C15 | 164.34 (18) |
C1—C2—C3—C4 | 58.8 (3) | C17—C13—C14—C15 | 41.5 (2) |
O3—C3—C4—C5 | −178.87 (19) | C18—C13—C14—C15 | −71.0 (2) |
C2—C3—C4—C5 | −57.8 (3) | C8—C14—C15—C16 | −169.5 (2) |
C3—C4—C5—C6 | −124.9 (2) | C13—C14—C15—C16 | −39.2 (2) |
C3—C4—C5—C10 | 54.0 (3) | C14—C15—C16—C20 | −151.3 (3) |
C4—C5—C6—C7 | −178.8 (2) | C14—C15—C16—C17 | 21.2 (2) |
C10—C5—C6—C7 | 2.3 (4) | C20—C16—C17—O17 | −2.0 (4) |
C5—C6—C7—C8 | 12.5 (3) | C15—C16—C17—O17 | −175.4 (2) |
C6—C7—C8—C14 | −162.4 (2) | C20—C16—C17—C13 | 177.6 (2) |
C6—C7—C8—C9 | −41.9 (3) | C15—C16—C17—C13 | 4.3 (3) |
C14—C8—C9—C11 | −52.2 (2) | C12—C13—C17—O17 | 35.3 (3) |
C7—C8—C9—C11 | −173.4 (2) | C14—C13—C17—O17 | 151.8 (2) |
C14—C8—C9—C10 | 179.71 (18) | C18—C13—C17—O17 | −89.8 (3) |
C7—C8—C9—C10 | 58.6 (2) | C12—C13—C17—C16 | −144.3 (2) |
C6—C5—C10—C19 | −109.5 (3) | C14—C13—C17—C16 | −27.9 (2) |
C4—C5—C10—C19 | 71.6 (2) | C18—C13—C17—C16 | 90.5 (2) |
C6—C5—C10—C1 | 131.5 (2) | C17—C16—C20—C21 | −173.5 (2) |
C4—C5—C10—C1 | −47.4 (3) | C15—C16—C20—C21 | −1.9 (4) |
C6—C5—C10—C9 | 13.0 (3) | C16—C20—C21—C26 | −16.9 (4) |
C4—C5—C10—C9 | −165.90 (19) | C16—C20—C21—C22 | 160.8 (3) |
C2—C1—C10—C5 | 48.0 (3) | C26—C21—C22—C23 | 4.2 (4) |
C2—C1—C10—C19 | −70.6 (3) | C20—C21—C22—C23 | −173.8 (2) |
C2—C1—C10—C9 | 167.4 (2) | C27—O23—C23—C22 | 11.9 (4) |
C11—C9—C10—C5 | −169.45 (18) | C27—O23—C23—C24 | −169.9 (2) |
C8—C9—C10—C5 | −42.5 (2) | C21—C22—C23—O23 | 179.2 (2) |
C11—C9—C10—C19 | −48.6 (2) | C21—C22—C23—C24 | 1.2 (4) |
C8—C9—C10—C19 | 78.3 (2) | C29—O28—C24—C25 | 6.9 (4) |
C11—C9—C10—C1 | 72.3 (2) | C29—O28—C24—C23 | −175.3 (2) |
C8—C9—C10—C1 | −160.81 (18) | O23—C23—C24—O28 | −1.8 (4) |
C8—C9—C11—C12 | 52.1 (3) | C22—C23—C24—O28 | 176.4 (2) |
C10—C9—C11—C12 | 179.63 (18) | O23—C23—C24—C25 | 176.2 (2) |
C9—C11—C12—C13 | −54.5 (3) | C22—C23—C24—C25 | −5.6 (4) |
C11—C12—C13—C17 | 168.4 (2) | O28—C24—C25—C26 | −177.6 (2) |
C11—C12—C13—C14 | 56.2 (2) | C23—C24—C25—C26 | 4.6 (4) |
C11—C12—C13—C18 | −69.6 (2) | C22—C21—C26—C25 | −5.2 (4) |
C7—C8—C14—C13 | −178.88 (19) | C20—C21—C26—C25 | 172.6 (2) |
C9—C8—C14—C13 | 59.1 (2) | C24—C25—C26—C21 | 0.9 (4) |
C7—C8—C14—C15 | −52.8 (3) | C24—O28—C29—C30 | 178.6 (3) |
C9—C8—C14—C15 | −174.8 (2) | O28—C29—C30—C31 | 164.3 (3) |
C12—C13—C14—C8 | −61.5 (2) | C29—C30—C31—Cl1 | 58.9 (4) |
C17—C13—C14—C8 | 175.67 (18) | C19—C10—C13—C18 | 13.84 (18) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O3i | 0.76 (3) | 1.95 (3) | 2.710 (2) | 177 (3) |
Symmetry code: (i) −y+1/3, x−y−1/3, z−1/3. |
(II) 16-[3-methoxy-4-(2-pyrrolidin-1-ylethoxy)benzylidene]- 3
β-pyrrolidinoandrost-5-en-17
β-ol monohydrate
top
Crystal data top
C37H54N2O3·H2O | F(000) = 648 |
Mr = 592.86 | Dx = 1.185 Mg m−3 |
Monoclinic, P21 | Melting point: 483 K |
Hall symbol: P 2yb | Mo Kα radiation, λ = 0.71073 Å |
a = 6.4219 (1) Å | Cell parameters from 3313 reflections |
b = 32.4115 (5) Å | θ = 2.0–26.0° |
c = 8.0981 (1) Å | µ = 0.08 mm−1 |
β = 99.6510 (7)° | T = 160 K |
V = 1661.71 (4) Å3 | Prism, colourless |
Z = 2 | 0.28 × 0.18 × 0.15 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2865 reflections with I > 2σ(I) |
Radiation source: Nonius FR591 sealed tube generator | Rint = 0.052 |
Horizontally mounted graphite crystal monochromator | θmax = 26.0°, θmin = 2.6° |
Detector resolution: 9 pixels mm-1 | h = −7→7 |
ϕ and ω scans with κ offsets | k = −39→39 |
36139 measured reflections | l = −9→9 |
3302 independent reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.092 | w = 1/[σ2(Fo2) + (0.050P)2 + 0.1844P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
3299 reflections | Δρmax = 0.23 e Å−3 |
451 parameters | Δρmin = −0.22 e Å−3 |
120 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.017 (5) |
Crystal data top
C37H54N2O3·H2O | V = 1661.71 (4) Å3 |
Mr = 592.86 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.4219 (1) Å | µ = 0.08 mm−1 |
b = 32.4115 (5) Å | T = 160 K |
c = 8.0981 (1) Å | 0.28 × 0.18 × 0.15 mm |
β = 99.6510 (7)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2865 reflections with I > 2σ(I) |
36139 measured reflections | Rint = 0.052 |
3302 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 120 restraints |
wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.23 e Å−3 |
3299 reflections | Δρmin = −0.22 e Å−3 |
451 parameters | |
Special details top
Experimental. Solvent used: acetone Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.464 (1) Frames collected: 1976 Seconds exposure per frame: 91 Degrees rotation per frame: 0.76 Crystal-Detector distance (mm): 50.0 |
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 (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | −0.4812 (4) | 0.11425 (9) | 0.2016 (3) | 0.0411 (6) | |
H1A | −0.5098 | 0.1087 | 0.3160 | 0.049* | |
H1B | −0.5649 | 0.1388 | 0.1584 | 0.049* | |
C2 | −0.5581 (4) | 0.07741 (9) | 0.0906 (3) | 0.0436 (7) | |
H2A | −0.4861 | 0.0521 | 0.1391 | 0.052* | |
H2B | −0.7117 | 0.0738 | 0.0875 | 0.052* | |
C3 | −0.5150 (5) | 0.08320 (9) | −0.0859 (3) | 0.0473 (7) | |
H3A | −0.5895 | 0.1085 | −0.1359 | 0.057* | 0.788 (7) |
H3B | −0.6420 | 0.1006 | −0.1265 | 0.057* | 0.212 (7) |
C4A | −0.2713 (6) | 0.08913 (12) | −0.0720 (4) | 0.0441 (11) | 0.788 (7) |
H4A | −0.1983 | 0.0638 | −0.0246 | 0.053* | 0.788 (7) |
H4B | −0.2365 | 0.0934 | −0.1853 | 0.053* | 0.788 (7) |
C4B | −0.3505 (13) | 0.1154 (3) | −0.1141 (9) | 0.037 (3) | 0.212 (7) |
H4C | −0.2751 | 0.1053 | −0.2034 | 0.044* | 0.212 (7) |
H4D | −0.4246 | 0.1412 | −0.1546 | 0.044* | 0.212 (7) |
C5 | −0.1939 (4) | 0.12490 (8) | 0.0354 (3) | 0.0380 (6) | |
C6 | −0.0589 (5) | 0.15179 (9) | −0.0151 (3) | 0.0472 (7) | |
H6 | −0.0102 | 0.1463 | −0.1174 | 0.057* | |
C7 | 0.0195 (4) | 0.18975 (8) | 0.0791 (3) | 0.0350 (5) | |
H7A | −0.0685 | 0.2135 | 0.0333 | 0.042* | |
H7B | 0.1663 | 0.1952 | 0.0627 | 0.042* | |
C8 | 0.0142 (4) | 0.18601 (7) | 0.2657 (3) | 0.0312 (5) | |
H8 | 0.1309 | 0.1672 | 0.3171 | 0.037* | |
C9 | −0.1988 (4) | 0.16764 (7) | 0.2954 (3) | 0.0320 (5) | |
H9 | −0.3110 | 0.1865 | 0.2376 | 0.038* | |
C10 | −0.2450 (4) | 0.12454 (8) | 0.2131 (3) | 0.0340 (5) | |
C11 | −0.2203 (4) | 0.16805 (8) | 0.4822 (3) | 0.0362 (6) | |
H11A | −0.1243 | 0.1470 | 0.5418 | 0.043* | |
H11B | −0.3666 | 0.1601 | 0.4923 | 0.043* | |
C12 | −0.1696 (4) | 0.21018 (8) | 0.5693 (3) | 0.0341 (5) | |
H12A | −0.2787 | 0.2306 | 0.5228 | 0.041* | |
H12B | −0.1721 | 0.2074 | 0.6906 | 0.041* | |
C13 | 0.0473 (4) | 0.22550 (8) | 0.5432 (3) | 0.0310 (5) | |
C14 | 0.0437 (4) | 0.22780 (7) | 0.3529 (3) | 0.0303 (5) | |
H14 | −0.0838 | 0.2445 | 0.3066 | 0.036* | |
C15 | 0.2353 (4) | 0.25440 (7) | 0.3320 (3) | 0.0332 (5) | |
H15A | 0.3626 | 0.2372 | 0.3321 | 0.040* | |
H15B | 0.2077 | 0.2704 | 0.2265 | 0.040* | |
C16 | 0.2619 (4) | 0.28275 (7) | 0.4838 (3) | 0.0318 (5) | |
C17 | 0.0949 (4) | 0.27104 (8) | 0.5896 (3) | 0.0332 (5) | |
H17 | −0.0352 | 0.2877 | 0.5511 | 0.040* | |
O17 | 0.1562 (3) | 0.27666 (7) | 0.7643 (2) | 0.0426 (4) | |
H17A | 0.139 (5) | 0.3019 (12) | 0.786 (4) | 0.062 (11)* | |
C18 | 0.2270 (4) | 0.19869 (8) | 0.6355 (3) | 0.0373 (6) | |
H18A | 0.2285 | 0.2005 | 0.7565 | 0.056* | |
H18B | 0.3623 | 0.2085 | 0.6097 | 0.056* | |
H18C | 0.2050 | 0.1699 | 0.5993 | 0.056* | |
C19 | −0.1098 (5) | 0.09070 (8) | 0.3131 (4) | 0.0469 (7) | |
H19A | −0.1224 | 0.0650 | 0.2482 | 0.070* | |
H19B | −0.1594 | 0.0861 | 0.4197 | 0.070* | |
H19C | 0.0384 | 0.0994 | 0.3351 | 0.070* | |
C20 | 0.4024 (4) | 0.31267 (7) | 0.5286 (3) | 0.0336 (5) | |
H20 | 0.3888 | 0.3263 | 0.6302 | 0.040* | |
C21 | 0.5748 (4) | 0.32813 (7) | 0.4469 (3) | 0.0322 (5) | |
C22 | 0.6113 (4) | 0.31484 (7) | 0.2886 (3) | 0.0318 (5) | |
H22 | 0.5210 | 0.2947 | 0.2289 | 0.038* | |
C23 | 0.7762 (4) | 0.33061 (7) | 0.2191 (3) | 0.0318 (5) | |
C24 | 0.9123 (4) | 0.36041 (7) | 0.3045 (3) | 0.0333 (5) | |
C25 | 0.8775 (4) | 0.37374 (8) | 0.4601 (3) | 0.0374 (6) | |
H25 | 0.9679 | 0.3939 | 0.5197 | 0.045* | |
C26 | 0.7108 (4) | 0.35774 (8) | 0.5291 (3) | 0.0350 (6) | |
H26 | 0.6890 | 0.3673 | 0.6358 | 0.042* | |
O27 | 1.0729 (3) | 0.37382 (5) | 0.2248 (2) | 0.0371 (4) | |
C28 | 1.1991 (4) | 0.40731 (8) | 0.3026 (3) | 0.0400 (6) | |
H28A | 1.2599 | 0.3999 | 0.4193 | 0.048* | |
H28B | 1.1100 | 0.4321 | 0.3055 | 0.048* | |
C29 | 1.3735 (4) | 0.41640 (8) | 0.2055 (3) | 0.0392 (6) | |
H29A | 1.4526 | 0.4408 | 0.2560 | 0.047* | |
H29B | 1.4724 | 0.3927 | 0.2179 | 0.047* | |
O35 | 0.8209 (3) | 0.31898 (5) | 0.0657 (2) | 0.0393 (4) | |
C36 | 0.6711 (4) | 0.29305 (9) | −0.0370 (3) | 0.0436 (6) | |
H36A | 0.6596 | 0.2667 | 0.0201 | 0.065* | |
H36B | 0.7183 | 0.2881 | −0.1442 | 0.065* | |
H36C | 0.5329 | 0.3067 | −0.0571 | 0.065* | |
N37 | −0.5787 (3) | 0.04787 (7) | −0.1941 (3) | 0.0416 (5) | |
C38 | −0.8023 (5) | 0.03839 (10) | −0.2159 (4) | 0.0517 (7) | |
H38A | −0.8881 | 0.0636 | −0.2427 | 0.062* | |
H38B | −0.8389 | 0.0258 | −0.1131 | 0.062* | |
C39 | −0.8393 (5) | 0.00809 (10) | −0.3610 (4) | 0.0539 (7) | |
H39A | −0.9826 | 0.0115 | −0.4271 | 0.065* | |
H39B | −0.8223 | −0.0207 | −0.3202 | 0.065* | |
C40 | −0.6695 (5) | 0.01924 (9) | −0.4658 (4) | 0.0511 (7) | |
H40A | −0.5811 | −0.0050 | −0.4809 | 0.061* | |
H40B | −0.7344 | 0.0298 | −0.5773 | 0.061* | |
C41 | −0.5402 (6) | 0.05229 (12) | −0.3652 (4) | 0.0635 (9) | |
H41A | −0.3882 | 0.0486 | −0.3699 | 0.076* | |
H41B | −0.5842 | 0.0800 | −0.4095 | 0.076* | |
C31A | 1.1844 (18) | 0.4617 (3) | −0.0278 (11) | 0.064 (2) | 0.510 (13) |
H31A | 1.2430 | 0.4861 | 0.0373 | 0.077* | 0.510 (13) |
H31B | 1.0339 | 0.4585 | −0.0172 | 0.077* | 0.510 (13) |
C32A | 1.211 (2) | 0.4655 (3) | −0.2121 (9) | 0.069 (3) | 0.510 (13) |
H32A | 1.0936 | 0.4514 | −0.2863 | 0.083* | 0.510 (13) |
H32B | 1.2147 | 0.4948 | −0.2459 | 0.083* | 0.510 (13) |
C33A | 1.4219 (19) | 0.4441 (3) | −0.2191 (9) | 0.077 (2) | 0.510 (13) |
H33A | 1.5240 | 0.4640 | −0.2531 | 0.093* | 0.510 (13) |
H33B | 1.4022 | 0.4211 | −0.3007 | 0.093* | 0.510 (13) |
C34A | 1.5028 (10) | 0.4277 (4) | −0.0419 (11) | 0.060 (2) | 0.510 (13) |
H34A | 1.5725 | 0.4006 | −0.0455 | 0.072* | 0.510 (13) |
H34B | 1.6027 | 0.4473 | 0.0233 | 0.072* | 0.510 (13) |
N30 | 1.3057 (3) | 0.42420 (7) | 0.0287 (3) | 0.0452 (6) | |
C31B | 1.1416 (15) | 0.4567 (3) | 0.0084 (11) | 0.057 (2) | 0.490 (13) |
H31C | 1.1905 | 0.4813 | 0.0763 | 0.068* | 0.490 (13) |
H31D | 1.0095 | 0.4464 | 0.0418 | 0.068* | 0.490 (13) |
C32B | 1.1081 (18) | 0.4667 (3) | −0.1796 (10) | 0.071 (2) | 0.490 (13) |
H32C | 0.9949 | 0.4494 | −0.2427 | 0.086* | 0.490 (13) |
H32D | 1.0715 | 0.4962 | −0.1999 | 0.086* | 0.490 (13) |
C33B | 1.3228 (18) | 0.4567 (3) | −0.2288 (9) | 0.070 (3) | 0.490 (13) |
H33C | 1.3874 | 0.4820 | −0.2669 | 0.084* | 0.490 (13) |
H33D | 1.3059 | 0.4362 | −0.3208 | 0.084* | 0.490 (13) |
C34B | 1.4621 (12) | 0.4391 (4) | −0.0720 (11) | 0.064 (2) | 0.490 (13) |
H34C | 1.5514 | 0.4162 | −0.1012 | 0.077* | 0.490 (13) |
H34D | 1.5538 | 0.4607 | −0.0116 | 0.077* | 0.490 (13) |
O1W | 0.0923 (4) | 0.35589 (7) | 0.8658 (3) | 0.0610 (6) | |
H1W | 0.169 (6) | 0.3746 (11) | 0.924 (5) | 0.098 (14)* | |
H2W | 0.010 (6) | 0.3471 (12) | 0.935 (4) | 0.098 (15)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0412 (15) | 0.0476 (15) | 0.0378 (13) | −0.0062 (12) | 0.0164 (11) | −0.0051 (11) |
C2 | 0.0434 (16) | 0.0482 (16) | 0.0427 (15) | −0.0089 (12) | 0.0178 (12) | −0.0041 (12) |
C3 | 0.0608 (18) | 0.0465 (15) | 0.0382 (14) | −0.0161 (13) | 0.0184 (13) | −0.0068 (12) |
C4A | 0.048 (2) | 0.049 (2) | 0.0389 (19) | −0.0111 (17) | 0.0183 (16) | −0.0069 (16) |
C4B | 0.045 (6) | 0.025 (6) | 0.040 (6) | 0.017 (5) | 0.007 (5) | 0.003 (5) |
C5 | 0.0445 (15) | 0.0362 (13) | 0.0368 (13) | −0.0026 (11) | 0.0170 (11) | −0.0028 (11) |
C6 | 0.0634 (19) | 0.0514 (16) | 0.0304 (13) | −0.0179 (14) | 0.0178 (12) | −0.0058 (12) |
C7 | 0.0394 (14) | 0.0361 (13) | 0.0321 (13) | −0.0026 (11) | 0.0133 (10) | 0.0015 (10) |
C8 | 0.0315 (12) | 0.0338 (12) | 0.0299 (12) | 0.0023 (10) | 0.0092 (10) | 0.0036 (10) |
C9 | 0.0337 (13) | 0.0324 (12) | 0.0309 (12) | −0.0007 (10) | 0.0084 (10) | 0.0017 (10) |
C10 | 0.0366 (13) | 0.0338 (12) | 0.0336 (12) | −0.0013 (11) | 0.0114 (10) | 0.0016 (10) |
C11 | 0.0380 (14) | 0.0390 (13) | 0.0341 (13) | −0.0036 (11) | 0.0131 (11) | 0.0020 (10) |
C12 | 0.0355 (13) | 0.0387 (13) | 0.0300 (12) | −0.0006 (11) | 0.0110 (10) | 0.0011 (10) |
C13 | 0.0294 (12) | 0.0371 (12) | 0.0275 (11) | 0.0008 (10) | 0.0076 (9) | 0.0021 (10) |
C14 | 0.0296 (12) | 0.0329 (12) | 0.0292 (11) | 0.0002 (10) | 0.0074 (9) | 0.0033 (10) |
C15 | 0.0370 (13) | 0.0361 (13) | 0.0279 (12) | 0.0001 (11) | 0.0093 (10) | 0.0008 (10) |
C16 | 0.0303 (13) | 0.0356 (13) | 0.0299 (12) | 0.0018 (10) | 0.0062 (10) | 0.0012 (10) |
C17 | 0.0329 (13) | 0.0409 (13) | 0.0264 (11) | 0.0006 (10) | 0.0066 (10) | 0.0003 (10) |
O17 | 0.0489 (11) | 0.0517 (12) | 0.0281 (9) | −0.0046 (9) | 0.0089 (8) | −0.0051 (8) |
C18 | 0.0365 (14) | 0.0435 (14) | 0.0329 (12) | 0.0040 (11) | 0.0086 (10) | 0.0057 (11) |
C19 | 0.0522 (17) | 0.0344 (14) | 0.0540 (16) | 0.0006 (12) | 0.0087 (13) | 0.0042 (12) |
C20 | 0.0341 (13) | 0.0379 (13) | 0.0295 (11) | 0.0013 (11) | 0.0080 (10) | −0.0010 (10) |
C21 | 0.0310 (12) | 0.0340 (12) | 0.0314 (12) | 0.0033 (10) | 0.0044 (10) | 0.0012 (10) |
C22 | 0.0315 (12) | 0.0334 (12) | 0.0297 (12) | −0.0024 (10) | 0.0030 (10) | −0.0021 (10) |
C23 | 0.0355 (13) | 0.0328 (12) | 0.0276 (11) | 0.0001 (10) | 0.0063 (10) | −0.0030 (10) |
C24 | 0.0307 (13) | 0.0339 (12) | 0.0353 (13) | −0.0029 (10) | 0.0055 (10) | −0.0014 (10) |
C25 | 0.0378 (14) | 0.0395 (13) | 0.0348 (13) | −0.0031 (11) | 0.0060 (11) | −0.0072 (11) |
C26 | 0.0367 (14) | 0.0393 (13) | 0.0291 (12) | 0.0002 (11) | 0.0055 (10) | −0.0045 (10) |
O27 | 0.0345 (9) | 0.0420 (9) | 0.0360 (9) | −0.0100 (8) | 0.0093 (7) | −0.0052 (8) |
C28 | 0.0382 (14) | 0.0390 (14) | 0.0426 (14) | −0.0115 (11) | 0.0061 (12) | −0.0086 (11) |
C29 | 0.0360 (14) | 0.0412 (14) | 0.0405 (14) | −0.0075 (12) | 0.0070 (11) | −0.0024 (11) |
O35 | 0.0404 (10) | 0.0465 (10) | 0.0326 (9) | −0.0116 (8) | 0.0106 (7) | −0.0100 (8) |
C36 | 0.0477 (16) | 0.0504 (16) | 0.0318 (13) | −0.0090 (13) | 0.0038 (11) | −0.0097 (12) |
N37 | 0.0387 (12) | 0.0486 (13) | 0.0394 (12) | −0.0070 (10) | 0.0124 (9) | −0.0063 (10) |
C38 | 0.0414 (16) | 0.0587 (19) | 0.0557 (18) | −0.0085 (14) | 0.0100 (13) | −0.0086 (14) |
C39 | 0.0499 (17) | 0.0570 (18) | 0.0519 (17) | −0.0078 (15) | 0.0000 (13) | −0.0051 (14) |
C40 | 0.0585 (19) | 0.0520 (17) | 0.0419 (15) | −0.0007 (14) | 0.0056 (13) | −0.0061 (13) |
C41 | 0.074 (2) | 0.077 (2) | 0.0438 (16) | −0.0248 (18) | 0.0224 (15) | −0.0134 (16) |
C31A | 0.108 (5) | 0.032 (3) | 0.046 (4) | −0.001 (4) | −0.006 (4) | 0.016 (3) |
C32A | 0.109 (6) | 0.047 (3) | 0.048 (4) | −0.008 (5) | 0.001 (5) | 0.007 (3) |
C33A | 0.109 (5) | 0.071 (4) | 0.051 (3) | −0.004 (4) | 0.010 (4) | 0.018 (3) |
C34A | 0.088 (4) | 0.056 (5) | 0.037 (4) | −0.028 (3) | 0.012 (3) | 0.014 (3) |
N30 | 0.0581 (15) | 0.0384 (12) | 0.0387 (12) | −0.0108 (11) | 0.0067 (11) | 0.0000 (10) |
C31B | 0.098 (5) | 0.031 (3) | 0.034 (4) | −0.009 (4) | −0.007 (3) | 0.015 (3) |
C32B | 0.115 (6) | 0.049 (3) | 0.048 (4) | −0.014 (4) | 0.009 (4) | 0.015 (3) |
C33B | 0.104 (6) | 0.063 (5) | 0.042 (3) | −0.018 (5) | 0.009 (5) | 0.010 (3) |
C34B | 0.093 (5) | 0.067 (6) | 0.037 (4) | −0.040 (4) | 0.025 (4) | 0.008 (3) |
O1W | 0.0891 (17) | 0.0559 (13) | 0.0429 (11) | −0.0309 (12) | 0.0258 (11) | −0.0160 (10) |
Geometric parameters (Å, º) top
C1—C2 | 1.526 (4) | C22—C23 | 1.378 (3) |
C1—C10 | 1.541 (3) | C22—H22 | 0.9500 |
C1—H1A | 0.9900 | C23—O35 | 1.374 (3) |
C1—H1B | 0.9900 | C23—C24 | 1.404 (3) |
C2—C3 | 1.512 (3) | C24—O27 | 1.376 (3) |
C2—H2A | 0.9900 | C24—C25 | 1.385 (3) |
C2—H2B | 0.9900 | C25—C26 | 1.389 (3) |
C3—N37 | 1.458 (3) | C25—H25 | 0.9500 |
C3—C4B | 1.529 (6) | C26—H26 | 0.9500 |
C3—C4A | 1.562 (4) | O27—C28 | 1.436 (3) |
C3—H3A | 1.0000 | C28—C29 | 1.501 (4) |
C3—H3B | 1.0000 | C28—H28A | 0.9900 |
C4A—C5 | 1.484 (4) | C28—H28B | 0.9900 |
C4A—H4A | 0.9900 | C29—N30 | 1.447 (3) |
C4A—H4B | 0.9900 | C29—H29A | 0.9900 |
C4B—C5 | 1.471 (6) | C29—H29B | 0.9900 |
C4B—H4C | 0.9900 | O35—C36 | 1.433 (3) |
C4B—H4D | 0.9900 | C36—H36A | 0.9800 |
C5—C6 | 1.341 (4) | C36—H36B | 0.9800 |
C5—C10 | 1.528 (3) | C36—H36C | 0.9800 |
C6—C7 | 1.490 (4) | N37—C38 | 1.450 (4) |
C6—H6 | 0.9500 | N37—C41 | 1.455 (3) |
C7—C8 | 1.522 (3) | C38—C39 | 1.519 (4) |
C7—H7A | 0.9900 | C38—H38A | 0.9900 |
C7—H7B | 0.9900 | C38—H38B | 0.9900 |
C8—C14 | 1.524 (3) | C39—C40 | 1.533 (4) |
C8—C9 | 1.548 (3) | C39—H39A | 0.9900 |
C8—H8 | 1.0000 | C39—H39B | 0.9900 |
C9—C11 | 1.542 (3) | C40—C41 | 1.508 (4) |
C9—C10 | 1.555 (3) | C40—H40A | 0.9900 |
C9—H9 | 1.0000 | C40—H40B | 0.9900 |
C10—C19 | 1.542 (4) | C41—H41A | 0.9900 |
C11—C12 | 1.546 (3) | C41—H41B | 0.9900 |
C11—H11A | 0.9900 | C31A—N30 | 1.474 (4) |
C11—H11B | 0.9900 | C31A—C32A | 1.535 (5) |
C12—C13 | 1.526 (3) | C31A—H31A | 0.9900 |
C12—H12A | 0.9900 | C31A—H31B | 0.9900 |
C12—H12B | 0.9900 | C32A—C33A | 1.532 (5) |
C13—C18 | 1.535 (3) | C32A—H32A | 0.9900 |
C13—C14 | 1.539 (3) | C32A—H32B | 0.9900 |
C13—C17 | 1.541 (3) | C33A—C34A | 1.536 (5) |
C14—C15 | 1.535 (3) | C33A—H33A | 0.9900 |
C14—H14 | 1.0000 | C33A—H33B | 0.9900 |
C15—C16 | 1.521 (3) | C34A—N30 | 1.478 (4) |
C15—H15A | 0.9900 | C34A—H34A | 0.9900 |
C15—H15B | 0.9900 | C34A—H34B | 0.9900 |
C16—C20 | 1.333 (3) | N30—C34B | 1.478 (4) |
C16—C17 | 1.528 (3) | N30—C31B | 1.479 (4) |
C17—O17 | 1.415 (3) | C31B—C32B | 1.536 (5) |
C17—H17 | 1.0000 | C31B—H31C | 0.9900 |
O17—H17A | 0.85 (4) | C31B—H31D | 0.9900 |
C18—H18A | 0.9800 | C32B—C33B | 1.533 (5) |
C18—H18B | 0.9800 | C32B—H32C | 0.9900 |
C18—H18C | 0.9800 | C32B—H32D | 0.9900 |
C19—H19A | 0.9800 | C33B—C34B | 1.535 (5) |
C19—H19B | 0.9800 | C33B—H33C | 0.9900 |
C19—H19C | 0.9800 | C33B—H33D | 0.9900 |
C20—C21 | 1.470 (3) | C34B—H34C | 0.9900 |
C20—H20 | 0.9500 | C34B—H34D | 0.9900 |
C21—C26 | 1.390 (3) | O1W—H1W | 0.87 (2) |
C21—C22 | 1.408 (3) | O1W—H2W | 0.88 (2) |
| | | |
C2—C1—C10 | 115.0 (2) | C21—C20—H20 | 114.7 |
C2—C1—H1A | 108.5 | C26—C21—C22 | 117.4 (2) |
C10—C1—H1A | 108.5 | C26—C21—C20 | 118.7 (2) |
C2—C1—H1B | 108.5 | C22—C21—C20 | 123.9 (2) |
C10—C1—H1B | 108.5 | C23—C22—C21 | 121.0 (2) |
H1A—C1—H1B | 107.5 | C23—C22—H22 | 119.5 |
C3—C2—C1 | 111.6 (2) | C21—C22—H22 | 119.5 |
C3—C2—H2A | 109.3 | O35—C23—C22 | 124.0 (2) |
C1—C2—H2A | 109.3 | O35—C23—C24 | 115.3 (2) |
C3—C2—H2B | 109.3 | C22—C23—C24 | 120.7 (2) |
C1—C2—H2B | 109.3 | O27—C24—C25 | 125.2 (2) |
H2A—C2—H2B | 108.0 | O27—C24—C23 | 116.1 (2) |
N37—C3—C2 | 113.2 (2) | C25—C24—C23 | 118.7 (2) |
N37—C3—C4B | 125.2 (4) | C24—C25—C26 | 120.2 (2) |
C2—C3—C4B | 117.8 (4) | C24—C25—H25 | 119.9 |
N37—C3—C4A | 108.5 (2) | C26—C25—H25 | 119.9 |
C2—C3—C4A | 106.7 (2) | C25—C26—C21 | 122.0 (2) |
N37—C3—H3A | 109.5 | C25—C26—H26 | 119.0 |
C2—C3—H3A | 109.5 | C21—C26—H26 | 119.0 |
C4A—C3—H3A | 109.5 | C24—O27—C28 | 116.45 (18) |
N37—C3—H3B | 96.5 | O27—C28—C29 | 109.5 (2) |
C2—C3—H3B | 96.5 | O27—C28—H28A | 109.8 |
C4B—C3—H3B | 96.5 | C29—C28—H28A | 109.8 |
C5—C4A—C3 | 111.8 (3) | O27—C28—H28B | 109.8 |
C5—C4A—H4A | 109.3 | C29—C28—H28B | 109.8 |
C3—C4A—H4A | 109.3 | H28A—C28—H28B | 108.2 |
C5—C4A—H4B | 109.3 | N30—C29—C28 | 115.1 (2) |
C3—C4A—H4B | 109.3 | N30—C29—H29A | 108.5 |
H4A—C4A—H4B | 107.9 | C28—C29—H29A | 108.5 |
C5—C4B—C3 | 114.5 (4) | N30—C29—H29B | 108.5 |
C5—C4B—H4C | 108.6 | C28—C29—H29B | 108.5 |
C3—C4B—H4C | 108.6 | H29A—C29—H29B | 107.5 |
C5—C4B—H4D | 108.6 | C23—O35—C36 | 117.64 (18) |
C3—C4B—H4D | 108.6 | O35—C36—H36A | 109.5 |
H4C—C4B—H4D | 107.6 | O35—C36—H36B | 109.5 |
C6—C5—C4B | 105.8 (3) | H36A—C36—H36B | 109.5 |
C6—C5—C4A | 120.0 (2) | O35—C36—H36C | 109.5 |
C6—C5—C10 | 123.0 (2) | H36A—C36—H36C | 109.5 |
C4B—C5—C10 | 123.2 (4) | H36B—C36—H36C | 109.5 |
C4A—C5—C10 | 116.2 (2) | C38—N37—C41 | 103.2 (2) |
C5—C6—C7 | 124.1 (2) | C38—N37—C3 | 114.3 (2) |
C5—C6—H6 | 117.9 | C41—N37—C3 | 114.8 (2) |
C7—C6—H6 | 117.9 | N37—C38—C39 | 104.7 (2) |
C6—C7—C8 | 112.4 (2) | N37—C38—H38A | 110.8 |
C6—C7—H7A | 109.1 | C39—C38—H38A | 110.8 |
C8—C7—H7A | 109.1 | N37—C38—H38B | 110.8 |
C6—C7—H7B | 109.1 | C39—C38—H38B | 110.8 |
C8—C7—H7B | 109.1 | H38A—C38—H38B | 108.9 |
H7A—C7—H7B | 107.9 | C38—C39—C40 | 104.0 (2) |
C7—C8—C14 | 111.55 (18) | C38—C39—H39A | 111.0 |
C7—C8—C9 | 110.64 (19) | C40—C39—H39A | 111.0 |
C14—C8—C9 | 108.31 (18) | C38—C39—H39B | 111.0 |
C7—C8—H8 | 108.8 | C40—C39—H39B | 111.0 |
C14—C8—H8 | 108.8 | H39A—C39—H39B | 109.0 |
C9—C8—H8 | 108.8 | C41—C40—C39 | 104.3 (2) |
C11—C9—C8 | 112.09 (19) | C41—C40—H40A | 110.9 |
C11—C9—C10 | 112.76 (19) | C39—C40—H40A | 110.9 |
C8—C9—C10 | 112.89 (19) | C41—C40—H40B | 110.9 |
C11—C9—H9 | 106.1 | C39—C40—H40B | 110.9 |
C8—C9—H9 | 106.1 | H40A—C40—H40B | 108.9 |
C10—C9—H9 | 106.1 | N37—C41—C40 | 106.1 (2) |
C5—C10—C1 | 108.0 (2) | N37—C41—H41A | 110.5 |
C5—C10—C19 | 108.0 (2) | C40—C41—H41A | 110.5 |
C1—C10—C19 | 109.9 (2) | N37—C41—H41B | 110.5 |
C5—C10—C9 | 109.97 (19) | C40—C41—H41B | 110.5 |
C1—C10—C9 | 109.6 (2) | H41A—C41—H41B | 108.7 |
C19—C10—C9 | 111.3 (2) | N30—C31A—C32A | 103.3 (4) |
C9—C11—C12 | 114.10 (19) | N30—C31A—H31A | 111.1 |
C9—C11—H11A | 108.7 | C32A—C31A—H31A | 111.1 |
C12—C11—H11A | 108.7 | N30—C31A—H31B | 111.1 |
C9—C11—H11B | 108.7 | C32A—C31A—H31B | 111.1 |
C12—C11—H11B | 108.7 | H31A—C31A—H31B | 109.1 |
H11A—C11—H11B | 107.6 | C33A—C32A—C31A | 104.0 (5) |
C13—C12—C11 | 110.58 (19) | C33A—C32A—H32A | 111.0 |
C13—C12—H12A | 109.5 | C31A—C32A—H32A | 111.0 |
C11—C12—H12A | 109.5 | C33A—C32A—H32B | 111.0 |
C13—C12—H12B | 109.5 | C31A—C32A—H32B | 111.0 |
C11—C12—H12B | 109.5 | H32A—C32A—H32B | 109.0 |
H12A—C12—H12B | 108.1 | C32A—C33A—C34A | 106.5 (5) |
C12—C13—C18 | 112.2 (2) | C32A—C33A—H33A | 110.4 |
C12—C13—C14 | 107.07 (18) | C34A—C33A—H33A | 110.4 |
C18—C13—C14 | 113.51 (19) | C32A—C33A—H33B | 110.4 |
C12—C13—C17 | 115.2 (2) | C34A—C33A—H33B | 110.4 |
C18—C13—C17 | 108.71 (19) | H33A—C33A—H33B | 108.6 |
C14—C13—C17 | 99.61 (18) | N30—C34A—C33A | 102.2 (4) |
C8—C14—C15 | 119.17 (19) | N30—C34A—H34A | 111.3 |
C8—C14—C13 | 113.62 (19) | C33A—C34A—H34A | 111.3 |
C15—C14—C13 | 105.09 (18) | N30—C34A—H34B | 111.3 |
C8—C14—H14 | 106.0 | C33A—C34A—H34B | 111.3 |
C15—C14—H14 | 106.0 | H34A—C34A—H34B | 109.2 |
C13—C14—H14 | 106.0 | C29—N30—C31A | 120.5 (4) |
C16—C15—C14 | 103.49 (19) | C29—N30—C34B | 118.9 (4) |
C16—C15—H15A | 111.1 | C29—N30—C34A | 105.1 (4) |
C14—C15—H15A | 111.1 | C31A—N30—C34A | 105.0 (5) |
C16—C15—H15B | 111.1 | C29—N30—C31B | 109.0 (4) |
C14—C15—H15B | 111.1 | C34B—N30—C31B | 104.1 (5) |
H15A—C15—H15B | 109.0 | N30—C31B—C32B | 103.9 (4) |
C20—C16—C15 | 129.7 (2) | N30—C31B—H31C | 111.0 |
C20—C16—C17 | 122.3 (2) | C32B—C31B—H31C | 111.0 |
C15—C16—C17 | 108.00 (19) | N30—C31B—H31D | 111.0 |
O17—C17—C16 | 115.2 (2) | C32B—C31B—H31D | 111.0 |
O17—C17—C13 | 112.19 (19) | H31C—C31B—H31D | 109.0 |
C16—C17—C13 | 103.31 (18) | C33B—C32B—C31B | 103.3 (5) |
O17—C17—H17 | 108.6 | C33B—C32B—H32C | 111.1 |
C16—C17—H17 | 108.6 | C31B—C32B—H32C | 111.1 |
C13—C17—H17 | 108.6 | C33B—C32B—H32D | 111.1 |
C17—O17—H17A | 108 (2) | C31B—C32B—H32D | 111.1 |
C13—C18—H18A | 109.5 | H32C—C32B—H32D | 109.1 |
C13—C18—H18B | 109.5 | C32B—C33B—C34B | 106.8 (5) |
H18A—C18—H18B | 109.5 | C32B—C33B—H33C | 110.4 |
C13—C18—H18C | 109.5 | C34B—C33B—H33C | 110.4 |
H18A—C18—H18C | 109.5 | C32B—C33B—H33D | 110.4 |
H18B—C18—H18C | 109.5 | C34B—C33B—H33D | 110.4 |
C10—C19—H19A | 109.5 | H33C—C33B—H33D | 108.6 |
C10—C19—H19B | 109.5 | N30—C34B—C33B | 102.8 (4) |
H19A—C19—H19B | 109.5 | N30—C34B—H34C | 111.2 |
C10—C19—H19C | 109.5 | C33B—C34B—H34C | 111.2 |
H19A—C19—H19C | 109.5 | N30—C34B—H34D | 111.2 |
H19B—C19—H19C | 109.5 | C33B—C34B—H34D | 111.2 |
C16—C20—C21 | 130.7 (2) | H34C—C34B—H34D | 109.1 |
C16—C20—H20 | 114.7 | H1W—O1W—H2W | 103 (4) |
| | | |
C10—C1—C2—C3 | −56.9 (3) | C20—C16—C17—C13 | −153.8 (2) |
C1—C2—C3—N37 | 177.7 (2) | C15—C16—C17—C13 | 25.2 (2) |
C1—C2—C3—C4B | 18.5 (6) | C12—C13—C17—O17 | 79.6 (3) |
C1—C2—C3—C4A | 58.5 (3) | C18—C13—C17—O17 | −47.2 (3) |
N37—C3—C4A—C5 | 179.5 (3) | C14—C13—C17—O17 | −166.21 (19) |
C2—C3—C4A—C5 | −58.3 (3) | C12—C13—C17—C16 | −155.72 (18) |
C4B—C3—C4A—C5 | 55.6 (5) | C18—C13—C17—C16 | 77.4 (2) |
N37—C3—C4B—C5 | −132.8 (6) | C14—C13—C17—C16 | −41.6 (2) |
C2—C3—C4B—C5 | 23.7 (10) | C15—C16—C20—C21 | 0.4 (4) |
C4A—C3—C4B—C5 | −58.1 (5) | C17—C16—C20—C21 | 179.2 (2) |
C3—C4B—C5—C6 | 177.1 (6) | C16—C20—C21—C26 | −174.5 (2) |
C3—C4B—C5—C10 | −33.4 (10) | C16—C20—C21—C22 | 5.7 (4) |
C3—C4A—C5—C6 | −134.5 (3) | C26—C21—C22—C23 | 0.2 (3) |
C3—C4A—C5—C10 | 55.8 (4) | C20—C21—C22—C23 | −180.0 (2) |
C4B—C5—C6—C7 | 135.4 (5) | C21—C22—C23—O35 | 179.9 (2) |
C4A—C5—C6—C7 | 176.8 (3) | C21—C22—C23—C24 | 0.0 (4) |
C10—C5—C6—C7 | −14.2 (5) | O35—C23—C24—O27 | −0.5 (3) |
C5—C6—C7—C8 | 25.4 (4) | C22—C23—C24—O27 | 179.4 (2) |
C6—C7—C8—C14 | −166.4 (2) | O35—C23—C24—C25 | 180.0 (2) |
C6—C7—C8—C9 | −45.7 (3) | C22—C23—C24—C25 | −0.1 (4) |
C7—C8—C9—C11 | −173.4 (2) | O27—C24—C25—C26 | −179.5 (2) |
C14—C8—C9—C11 | −50.8 (3) | C23—C24—C25—C26 | 0.0 (4) |
C7—C8—C9—C10 | 58.0 (3) | C24—C25—C26—C21 | 0.2 (4) |
C14—C8—C9—C10 | −179.46 (18) | C22—C21—C26—C25 | −0.3 (3) |
C6—C5—C10—C1 | 142.7 (3) | C20—C21—C26—C25 | 179.9 (2) |
C4B—C5—C10—C1 | −1.8 (6) | C25—C24—O27—C28 | −6.8 (3) |
C4A—C5—C10—C1 | −48.0 (3) | C23—C24—O27—C28 | 173.7 (2) |
C6—C5—C10—C19 | −98.6 (3) | C24—O27—C28—C29 | 176.8 (2) |
C4B—C5—C10—C19 | 117.0 (5) | O27—C28—C29—N30 | 54.2 (3) |
C4A—C5—C10—C19 | 70.8 (3) | C22—C23—O35—C36 | 8.5 (3) |
C6—C5—C10—C9 | 23.1 (4) | C24—C23—O35—C36 | −171.6 (2) |
C4B—C5—C10—C9 | −121.4 (5) | C2—C3—N37—C38 | 60.9 (3) |
C4A—C5—C10—C9 | −167.5 (3) | C4B—C3—N37—C38 | −141.7 (5) |
C2—C1—C10—C5 | 47.7 (3) | C4A—C3—N37—C38 | 179.0 (3) |
C2—C1—C10—C19 | −69.9 (3) | C2—C3—N37—C41 | 179.9 (3) |
C2—C1—C10—C9 | 167.5 (2) | C4B—C3—N37—C41 | −22.7 (6) |
C11—C9—C10—C5 | −172.9 (2) | C4A—C3—N37—C41 | −62.0 (3) |
C8—C9—C10—C5 | −44.6 (3) | C41—N37—C38—C39 | 41.8 (3) |
C11—C9—C10—C1 | 68.5 (3) | C3—N37—C38—C39 | 167.2 (2) |
C8—C9—C10—C1 | −163.2 (2) | N37—C38—C39—C40 | −28.3 (3) |
C11—C9—C10—C19 | −53.2 (3) | C38—C39—C40—C41 | 4.4 (3) |
C8—C9—C10—C19 | 75.1 (2) | C38—N37—C41—C40 | −39.3 (3) |
C8—C9—C11—C12 | 49.7 (3) | C3—N37—C41—C40 | −164.3 (3) |
C10—C9—C11—C12 | 178.4 (2) | C39—C40—C41—N37 | 20.9 (3) |
C9—C11—C12—C13 | −53.3 (3) | N30—C31A—C32A—C33A | −27.1 (10) |
C11—C12—C13—C18 | −67.9 (2) | C31A—C32A—C33A—C34A | 2.1 (10) |
C11—C12—C13—C14 | 57.3 (2) | C32A—C33A—C34A—N30 | 23.4 (9) |
C11—C12—C13—C17 | 167.04 (19) | C28—C29—N30—C31A | 68.0 (7) |
C7—C8—C14—C15 | −53.3 (3) | C28—C29—N30—C34B | 171.5 (6) |
C9—C8—C14—C15 | −175.30 (19) | C28—C29—N30—C34A | −174.0 (5) |
C7—C8—C14—C13 | −178.00 (19) | C28—C29—N30—C31B | 52.6 (6) |
C9—C8—C14—C13 | 60.0 (2) | C32A—C31A—N30—C29 | 161.6 (5) |
C12—C13—C14—C8 | −63.7 (2) | C32A—C31A—N30—C34A | 43.5 (8) |
C18—C13—C14—C8 | 60.6 (3) | C33A—C34A—N30—C29 | −169.5 (5) |
C17—C13—C14—C8 | 175.99 (19) | C33A—C34A—N30—C31A | −41.4 (7) |
C12—C13—C14—C15 | 164.31 (19) | C29—N30—C31B—C32B | 171.6 (5) |
C18—C13—C14—C15 | −71.3 (3) | C34B—N30—C31B—C32B | 43.8 (7) |
C17—C13—C14—C15 | 44.0 (2) | N30—C31B—C32B—C33B | −28.2 (9) |
C8—C14—C15—C16 | −157.7 (2) | C31B—C32B—C33B—C34B | 3.4 (10) |
C13—C14—C15—C16 | −29.0 (2) | C29—N30—C34B—C33B | −162.2 (5) |
C14—C15—C16—C20 | −179.0 (2) | C31B—N30—C34B—C33B | −40.7 (8) |
C14—C15—C16—C17 | 2.1 (2) | C32B—C33B—C34B—N30 | 22.4 (10) |
C20—C16—C17—O17 | −31.1 (3) | C19—C10—C13—C18 | 11.34 (19) |
C15—C16—C17—O17 | 147.9 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O17—H17A···O1W | 0.85 (4) | 1.90 (4) | 2.748 (3) | 172 (3) |
O1W—H1W···N30i | 0.87 (2) | 1.95 (2) | 2.813 (3) | 169 (4) |
O1W—H2W···O35i | 0.88 (2) | 1.96 (2) | 2.835 (3) | 170 (4) |
O1W—H2W···O27i | 0.88 (2) | 2.47 (4) | 2.987 (3) | 118 (3) |
Symmetry code: (i) x−1, y, z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C30H39ClO4 | C37H54N2O3·H2O |
Mr | 499.09 | 592.86 |
Crystal system, space group | Trigonal, R3 | Monoclinic, P21 |
Temperature (K) | 160 | 160 |
a, b, c (Å) | 34.3749 (8), 34.3749 (8), 5.7585 (1) | 6.4219 (1), 32.4115 (5), 8.0981 (1) |
α, β, γ (°) | 90, 90, 120 | 90, 99.6510 (7), 90 |
V (Å3) | 5892.8 (2) | 1661.71 (4) |
Z | 9 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.18 | 0.08 |
Crystal size (mm) | 0.30 × 0.12 × 0.10 | 0.28 × 0.18 × 0.15 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) | – |
Tmin, Tmax | 0.909, 0.984 | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29761, 5990, 5077 | 36139, 3302, 2865 |
Rint | 0.062 | 0.052 |
(sin θ/λ)max (Å−1) | 0.649 | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.127, 1.02 | 0.037, 0.092, 1.04 |
No. of reflections | 5987 | 3299 |
No. of parameters | 324 | 451 |
No. of restraints | 1 | 120 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.60, −0.34 | 0.23, −0.22 |
Absolute structure | Flack & Bernardinelli (2000) | ? |
Absolute structure parameter | −0.21 (7) | ? |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O3i | 0.76 (3) | 1.95 (3) | 2.710 (2) | 177 (3) |
Symmetry code: (i) −y+1/3, x−y−1/3, z−1/3. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O17—H17A···O1W | 0.85 (4) | 1.90 (4) | 2.748 (3) | 172 (3) |
O1W—H1W···N30i | 0.87 (2) | 1.95 (2) | 2.813 (3) | 169 (4) |
O1W—H2W···O35i | 0.88 (2) | 1.96 (2) | 2.835 (3) | 170 (4) |
O1W—H2W···O27i | 0.88 (2) | 2.47 (4) | 2.987 (3) | 118 (3) |
Symmetry code: (i) x−1, y, z+1. |
It is well known that minor changes in the basic composition of steroids significantly alter their chemical and biological activities (Duax & Norton, 1975). The present crystallographic analyses of 16-[4-(3-chloropropoxy)-3-methoxybenzylidene]-17-oxoandrost-5-en-3β-ol, (I), and 16-[3-methoxy-4-(2-pyrrolidin-1-ylethoxy)benzylidene]- 3β-pyrrolidinoandrost-5-en-17β-ol monohydrate, (II), have been carried out to study the influence of different functionalities on the steroid skeleton, in particular substituents at the C3, C16 and C17 positions. This study extends ongoing investigations into a series of similar synthetic androstene derivatives (Thamotharan et al., 2002, and references therein; Hema et al., 2003). \sch
Compounds (I) and (II) are androstene steroid derivatives in which rings A, B and C are essentially rigid, whereas ring D has a flexible conformation with respect to the side chain. Both compounds have the normal 8β,9α,10β,13β,14α configuration and the B/C and C/D ring junctions have the trans configuration (Figs. 1 and 2). The crystals of (I) are enantiomerically pure and the absolute configuration of the molecule has been confirmed independently by the X-ray diffraction experiment. In (II), the absence of any significant anomalous scatterers in the compound prevented the determination of the absolute configuration and the enantiomer used in the refinement was assigned to correspond with the known chiral centres in a precursor molecule, which remained unchanged during the synthesis of (II).
In compound (I) (Fig. 1), rings A and C are in chair conformations, as shown by the Cremer & Pople (1975) puckering parameters [ring A: Q = 0.550 (3) Å, q2 = 0.078 (3) Å, q3 = 0.545 (3) Å, θ = 7.9 (3)° and ϕ2 = 107 (2)° for the atom sequence C1—C5/C10; ring C: Q = 0.577 (3) Å, q2 = 0.053 (3) Å, q3 = 0.575 (3) Å, θ = 5.2 (3)° and ϕ2 = 269 (3)° for the atom sequence C8/C9/C11—C14]. Thus, the presence of a hydroxy group at C3 has not disturbed the usual chair conformation of ring A of the steroid nucleus. The C3—O3 bond is oriented equatorially and (-)synclinal to the C3—C4 bond. In contrast, it lies (+)antiperiplanar to the C3—C4 bond in a related structure reported from our laboratory (Hema et al., 2003). In ring B, the C5═C6 (Csp2—Csp2) distance of 1.324 (3) Å confirms the localization of a double bond at this position. This double bond imposes a 8β,9α-half-chair conformation on ring B, with puckering parameters of Q = 0.468 (3) Å, q2 = 0.365 (3) Å, q3 = 0.292 (3) Å, θ = 51.5 (3)° and ϕ2 = 211.4 (4)° for the atom sequence C5—C10. Similar observations on the conformation of ring B in related structures have been reported by Caira et al. (1995), Hema et al. (2002), Vasuki et al. (2002) and Thamotharan et al. (2002). Ring D has a 14α-envelope conformation, with a pseudo-rotation angle of 12.4 (2)° and a maximum torsion angle of 42.5 (1)° (Rao et al., 1981) for the atom sequence C13—C17. Atom C14 is 0.142 (2) Å from the plane containing the four remaining atoms.
In compound (II) (Fig. 2), atom C4 in ring A of the steroid nucleus is disordered over two sites, so that ring A adopts two alternate conformations with the major conformation existing in 78.8 (7)% of the molecules. As seen from the puckering parameters, the major disordered component has a chair conformation [Q = 0.558 (3) Å, q2 = 0.087 (3) Å, q3 = 0.551 (3) Å, θ = 9.0 (3)° and ϕ2 = 113 (2)° for the atom sequence C1—C4A/C5/C10], while the minor disordered component has a boat conformation distorted towards that of a screw-boat [Q = 0.569 (5) Å, q2 = 0.556 (6) Å, q3 = 0.120 (5) Å, θ = 77.8 (5)° and ϕ2 = 8.8 (3)° for the atom sequence C1—C4B/C5/C10]. Ring B exhibits a slightly flattened half-chair conformation [Q = 0.454 (3) Å, q2 = 0.281 (3) Å, q3 = 0.356 (3) Å, θ = 38.3 (4)° and ϕ2 = 208.7 (6)° for the atom sequence C5—C10], while ring C adopts a chair conformation [Q = 0.581 (3) Å, q2 = 0.084 (3) Å, q3 = 0.574 (3) Å, θ = 8.7 (3)° and ϕ2 = 268.4 (18)° for the atom sequence C8/C9/C11—C14]. Ring D of the steroid exhibits an envelope conformation, as is evident from the pseudo-rotation angle of 345.0 (2)° and maximum torsion angle of 45.4 (1)° for the atom sequence C13—C17.
In (II), the four ring C atoms of the ethoxypyrrolidine ring are disordered over two almost equally occupied conformations. Both disordered components exhibit envelope conformations, as can be seen from the pseudo-rotation angles of 344.8 (8) and 346.8 (8)° and maximum torsion angles of 44.2 (6) and 44.3 (5)° for the atom sequences N30/C31A/C32A/C33A/C34A and N30/C31B/C32B/C33B/C34B, respectively. The pyrrolidine-ring substituent at C3 has an envelope conformation, with a pseudo-rotation angle of 348.0 (3)° and a maximum torsion angle of 42.7 (2)° for the atom sequence N37/C38—C41.
The C17—C16—C20—C21 torsion angles of −173.5 (2)° in (I) and 179.2 (2)° in (II) indicate that the benzylidene moiety has an E configuration with respect to the carbonyl or hydroxy substituted atom, C17. The chloropropoxy group in (I) projects in a planar zigzag fashion slightly away from the plane of the methoxybenzylidene ring [C25—C24—O28—C29 6.9 (4)°].
The pseudo-torsion angle C19—C10···C13—C18, which gives a quantitative measure of the molecular twist, is 13.84 (18) in (I) and 11.34 (19)° in (II). These values are comparable with those of related structures with bulky substitutions at C3 and C16 (Hema et al., 2002; Thamotharan et al., 2002). The C16—C20—C21—C22 torsion angles of 160.8 (3) in (I) and 5.7 (4)° in (II) indicate that the benzylidene moiety has been flipped by almost 180° about the C20—C21 bond in (II) with respect to its orientation in (I), thus bringing the methoxy group to the other side of the molecule. The A/B/C/D ring systems of both (I) and (II) could be superimposed on each other with a small r.m.s. deviation of the atoms of 0.084 Å.
In (I), the hydroxy substituent on atom C3 forms an intermolecular hydrogen bond with the hydroxy atom O3 of a symmetry-related molecule (Table 1). This interaction leads cooperatively to an O—H···O—H···O—H pattern, producing a chain which runs parallel to the [001] direction and has a graph-set motif of C(2) (Bernstein et al., 1995). As can be seen from Table 2, the hydroxy substituent on atom C17 in (II) forms an intermolecular O—H···O hydrogen bond with the O atom of the water molecule. In turn, the water molecule forms two intermolecular O—H···O and one intermolecular O—H···N hydrogen bonds with the methoxy, ethoxy and ethoxypyrrolidine O and N atoms, respectively, of a single adjacent steroid molecule. These three acceptor atoms form a pocket into which the water molecule is bound. The combination of all these interactions links the steroid and water molecules alternately into extended chains which run in the [101] direction. Binary graph-set motifs (Bernstein et al., 1995) of C22(11), C22(12) and C22(15) are present for the chain routes through acceptor atoms O37, O25 and N30, respectively. Ring motifs of R12(5), R22(7) and R22(10) are also formed by the various combinations of donor-acceptor interactions between the water molecule and the single acceptor steroid molecule.