Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010302866X/ga1026sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010302866X/ga1026Isup2.hkl |
CCDC reference: 233134
Compound (I) was prepared by hydrogenolysis of 3-o-benzyl-7-(5'-cyanopentyl)oestra-1,3,5(10),6-tetraen-3-ol-17-one (Pd/C, H2, MeOH; Thiemann et al., 2003). 3-o-Benzyl-7α-(5'-cyanopentyl)oestra-1,3,5(10),6-tetraen-3-ol-17-one was prepared from 3-o-benzyloestra-1,3,5(10),6-trien-3-ol-6,17-dione 17,17-[2''-(5'',5''-dimethyl-1'',3''-dioxane)] by a procedure analogous to that described for 3-o-methyloestra-1,3,5(10),6-trien-3-ol-6,17-dione 17,17-[2''-(5'',5''-dimethyl-1'',3''-dioxane)] (Inohae et al., 1999; Thiemann et al., 2002). The crystal used for the present X-ray structure analysis was obtained by recrystallization of (I) from dichloromethane/hexane (Ratio?).
The structure was solved by direct methods (Altomare et al., 1999) and expanded using Fourier techniques (Beurskens et al., 1999). The positional parameters of the H atoms were calculated geometrically (C—H = 0.95 and O—H = 0.82 Å) and refined using a riding model, with Uiso(H) set to 1.2Ueq(O, C). For geometric calculations, the program DIHED (Hitzer, Year?) was used. The ring-puckering analysis was carried out using PLATON (Spek, 2003).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Molecular Structure Corporation & Rigaku, 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CRYSTALS (Watkins et al., 1996); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: CrystalStructure.
C24H31NO2 | F(000) = 396.00 |
Mr = 365.51 | Dx = 1.188 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: P 2yb | Cell parameters from 9657 reflections |
a = 6.639 (3) Å | θ = 3.0–27.5° |
b = 13.530 (6) Å | µ = 0.07 mm−1 |
c = 11.910 (5) Å | T = 293 K |
β = 107.25 (3)° | Needle, colourless |
V = 1021.7 (7) Å3 | 0.50 × 0.20 × 0.12 mm |
Z = 2 |
Rigaku R-AXIS RAPID diffractometer | 2082 reflections with I > 2σ(I) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.034 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −8→8 |
Tmin = 0.982, Tmax = 0.991 | k = −17→17 |
20270 measured reflections | l = −15→15 |
2458 independent reflections |
Refinement on F2 | w = 1/[0.0003Fo2 + 1.0σ(Fo2)]/(4Fo2) |
R[F2 > 2σ(F2)] = 0.035 | (Δ/σ)max < 0.001 |
wR(F2) = 0.082 | Δρmax = 0.29 e Å−3 |
S = 1.04 | Δρmin = −0.25 e Å−3 |
2441 reflections | Extinction correction: Eq. 22 in Larson (1970) |
276 parameters | Extinction coefficient: 885 (45) |
H-atom parameters constrained |
C24H31NO2 | V = 1021.7 (7) Å3 |
Mr = 365.51 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.639 (3) Å | µ = 0.07 mm−1 |
b = 13.530 (6) Å | T = 293 K |
c = 11.910 (5) Å | 0.50 × 0.20 × 0.12 mm |
β = 107.25 (3)° |
Rigaku R-AXIS RAPID diffractometer | 2458 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2082 reflections with I > 2σ(I) |
Tmin = 0.982, Tmax = 0.991 | Rint = 0.034 |
20270 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 276 parameters |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.29 e Å−3 |
2441 reflections | Δρmin = −0.25 e Å−3 |
Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY |
Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
O1 | 0.0856 (3) | −0.0530 (1) | 0.4775 (1) | 0.0254 (4) | |
O2 | 1.0587 (3) | 0.1716 (1) | −0.0532 (2) | 0.0322 (5) | |
N1 | −0.1085 (3) | 0.7612 (2) | 0.3835 (2) | 0.0295 (6) | |
C1 | 0.4635 (3) | −0.0668 (2) | 0.3051 (2) | 0.0187 (5) | |
C2 | 0.3111 (4) | −0.0966 (2) | 0.3576 (2) | 0.0201 (5) | |
C3 | 0.2352 (4) | −0.0295 (2) | 0.4236 (2) | 0.0207 (6) | |
C4 | 0.3151 (4) | 0.0668 (2) | 0.4388 (2) | 0.0203 (5) | |
C5 | 0.4695 (4) | 0.0953 (2) | 0.3880 (2) | 0.0188 (5) | |
C6 | 0.5692 (4) | 0.1961 (2) | 0.4059 (2) | 0.0199 (5) | |
C7 | 0.5667 (3) | 0.2455 (2) | 0.2887 (2) | 0.0170 (5) | |
C8 | 0.5994 (3) | 0.1691 (2) | 0.1980 (2) | 0.0159 (5) | |
C9 | 0.6963 (3) | 0.0705 (2) | 0.2588 (2) | 0.0179 (5) | |
C10 | 0.5425 (3) | 0.0290 (2) | 0.3187 (2) | 0.0185 (5) | |
C11 | 0.7547 (4) | −0.0021 (2) | 0.1745 (2) | 0.0213 (5) | |
C12 | 0.8957 (4) | 0.0444 (2) | 0.1079 (2) | 0.0219 (6) | |
C13 | 0.7868 (3) | 0.1351 (2) | 0.0419 (2) | 0.0188 (5) | |
C14 | 0.7411 (3) | 0.2100 (2) | 0.1288 (2) | 0.0171 (5) | |
C15 | 0.6826 (4) | 0.3056 (2) | 0.0558 (2) | 0.0217 (6) | |
C16 | 0.8446 (4) | 0.3060 (2) | −0.0146 (2) | 0.0245 (6) | |
C17 | 0.9178 (4) | 0.1991 (2) | −0.0156 (2) | 0.0224 (6) | |
C18 | 0.5877 (4) | 0.1071 (2) | −0.0592 (2) | 0.0256 (6) | |
C19 | 0.3624 (3) | 0.3041 (2) | 0.2387 (2) | 0.0182 (5) | |
C20 | 0.3538 (4) | 0.4002 (2) | 0.3049 (2) | 0.0207 (5) | |
C21 | 0.1369 (3) | 0.4485 (2) | 0.2671 (2) | 0.0196 (5) | |
C22 | 0.1294 (3) | 0.5462 (2) | 0.3290 (2) | 0.0185 (5) | |
C23 | −0.0973 (3) | 0.5869 (2) | 0.2936 (2) | 0.0191 (5) | |
C24 | −0.1077 (4) | 0.6850 (2) | 0.3428 (2) | 0.0208 (5) | |
H1 | 0.5139 | −0.1127 | 0.2594 | 0.022 (1)* | |
H2 | 0.2593 | −0.1624 | 0.3484 | 0.023 (1)* | |
H3 | 0.2644 | 0.1129 | 0.4842 | 0.024 (1)* | |
H4 | 0.4928 | 0.2368 | 0.4439 | 0.023 (1)* | |
H5 | 0.7110 | 0.1902 | 0.4542 | 0.023 (1)* | |
H6 | 0.6808 | 0.2910 | 0.3049 | 0.020 (1)* | |
H7 | 0.4656 | 0.1546 | 0.1439 | 0.018 (1)* | |
H8 | 0.8221 | 0.0866 | 0.3189 | 0.021 (1)* | |
H9 | 0.8278 | −0.0565 | 0.2188 | 0.026 (1)* | |
H10 | 0.6287 | −0.0250 | 0.1192 | 0.026 (1)* | |
H11 | 1.0267 | 0.0634 | 0.1617 | 0.026 (1)* | |
H12 | 0.9198 | −0.0022 | 0.0536 | 0.026 (1)* | |
H13 | 0.8731 | 0.2230 | 0.1853 | 0.020 (1)* | |
H14 | 0.6984 | 0.3622 | 0.1049 | 0.026 (1)* | |
H15 | 0.5421 | 0.3027 | 0.0050 | 0.026 (1)* | |
H16 | 0.9606 | 0.3476 | 0.0223 | 0.029 (1)* | |
H17 | 0.7802 | 0.3282 | −0.0927 | 0.029 (1)* | |
H18 | 0.4977 | 0.0670 | −0.0295 | 0.030 (1)* | |
H19 | 0.5155 | 0.1659 | −0.0918 | 0.031 (1)* | |
H20 | 0.6271 | 0.0719 | −0.1185 | 0.031 (1)* | |
H21 | 0.0314 | −0.1064 | 0.4534 | 0.032 (1)* | |
H22 | 0.2473 | 0.2634 | 0.2415 | 0.022 (1)* | |
H23 | 0.3493 | 0.3206 | 0.1593 | 0.022 (1)* | |
H24 | 0.3887 | 0.3853 | 0.3864 | 0.025 (1)* | |
H25 | 0.4542 | 0.4454 | 0.2919 | 0.025 (1)* | |
H26 | 0.0382 | 0.4048 | 0.2845 | 0.023 (1)* | |
H27 | 0.0985 | 0.4596 | 0.1847 | 0.023 (1)* | |
H28 | 0.1774 | 0.5369 | 0.4117 | 0.022 (1)* | |
H29 | 0.2180 | 0.5925 | 0.3066 | 0.022 (1)* | |
H30 | −0.1830 | 0.5428 | 0.3216 | 0.023 (1)* | |
H31 | −0.1487 | 0.5906 | 0.2103 | 0.023 (1)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0302 (9) | 0.0229 (9) | 0.0267 (8) | −0.0049 (7) | 0.0141 (7) | −0.0033 (7) |
O2 | 0.0308 (9) | 0.039 (1) | 0.0328 (9) | −0.0012 (8) | 0.0189 (8) | −0.0046 (8) |
N1 | 0.026 (1) | 0.022 (1) | 0.043 (1) | 0.0027 (9) | 0.0138 (9) | 0.001 (1) |
C1 | 0.019 (1) | 0.017 (1) | 0.019 (1) | 0.0031 (8) | 0.0043 (8) | −0.0027 (9) |
C2 | 0.023 (1) | 0.016 (1) | 0.020 (1) | −0.0011 (9) | 0.0036 (9) | 0.0000 (9) |
C3 | 0.021 (1) | 0.024 (1) | 0.016 (1) | 0.0012 (9) | 0.0041 (9) | 0.0026 (9) |
C4 | 0.024 (1) | 0.021 (1) | 0.015 (1) | 0.0025 (9) | 0.0054 (8) | −0.0016 (9) |
C5 | 0.019 (1) | 0.017 (1) | 0.016 (1) | 0.0007 (9) | 0.0001 (8) | 0.0012 (9) |
C6 | 0.024 (1) | 0.018 (1) | 0.018 (1) | −0.0003 (9) | 0.0049 (9) | −0.0026 (9) |
C7 | 0.016 (1) | 0.016 (1) | 0.018 (1) | −0.0009 (8) | 0.0043 (8) | −0.0033 (9) |
C8 | 0.0146 (9) | 0.016 (1) | 0.0159 (9) | 0.0014 (8) | 0.0028 (8) | −0.0014 (8) |
C9 | 0.0154 (9) | 0.018 (1) | 0.019 (1) | 0.0014 (8) | 0.0034 (8) | 0.0008 (9) |
C10 | 0.017 (1) | 0.020 (1) | 0.016 (1) | 0.0018 (9) | 0.0006 (8) | 0.0010 (8) |
C11 | 0.022 (1) | 0.016 (1) | 0.026 (1) | 0.0032 (9) | 0.0079 (9) | −0.0013 (9) |
C12 | 0.021 (1) | 0.020 (1) | 0.025 (1) | 0.0028 (9) | 0.0086 (9) | −0.0037 (9) |
C13 | 0.017 (1) | 0.022 (1) | 0.019 (1) | −0.0003 (9) | 0.0064 (8) | −0.0039 (9) |
C14 | 0.0146 (9) | 0.018 (1) | 0.018 (1) | −0.0006 (8) | 0.0036 (8) | −0.0023 (9) |
C15 | 0.023 (1) | 0.020 (1) | 0.022 (1) | 0.0003 (9) | 0.0061 (9) | 0.0014 (9) |
C16 | 0.025 (1) | 0.028 (1) | 0.020 (1) | −0.002 (1) | 0.0063 (9) | 0.003 (1) |
C17 | 0.021 (1) | 0.030 (1) | 0.015 (1) | −0.004 (1) | 0.0030 (8) | −0.0017 (9) |
C18 | 0.023 (1) | 0.032 (1) | 0.022 (1) | −0.002 (1) | 0.0054 (9) | −0.006 (1) |
C19 | 0.018 (1) | 0.019 (1) | 0.018 (1) | 0.0018 (9) | 0.0053 (8) | −0.0021 (9) |
C20 | 0.020 (1) | 0.020 (1) | 0.023 (1) | 0.0020 (9) | 0.0060 (9) | −0.0024 (9) |
C21 | 0.018 (1) | 0.020 (1) | 0.020 (1) | 0.0002 (9) | 0.0045 (9) | −0.0028 (9) |
C22 | 0.018 (1) | 0.017 (1) | 0.021 (1) | 0.0019 (9) | 0.0060 (8) | −0.0014 (8) |
C23 | 0.018 (1) | 0.018 (1) | 0.021 (1) | 0.0019 (8) | 0.0058 (8) | 0.0003 (9) |
C24 | 0.017 (1) | 0.022 (1) | 0.025 (1) | 0.0021 (9) | 0.0088 (9) | 0.006 (1) |
O1—C3 | 1.371 (3) | C12—H12 | 0.950 |
O1—H21 | 0.820 | C13—C14 | 1.542 (3) |
O2—C17 | 1.209 (3) | C13—C17 | 1.526 (4) |
N1—C24 | 1.141 (3) | C13—C18 | 1.548 (3) |
C1—C2 | 1.396 (4) | C14—C15 | 1.542 (3) |
C1—C10 | 1.390 (3) | C14—H13 | 0.950 |
C1—H1 | 0.950 | C15—C16 | 1.548 (4) |
C2—C3 | 1.389 (4) | C15—H14 | 0.950 |
C2—H2 | 0.950 | C15—H15 | 0.950 |
C3—C4 | 1.398 (3) | C16—C17 | 1.527 (4) |
C4—C5 | 1.391 (4) | C16—H16 | 0.950 |
C4—H3 | 0.950 | C16—H17 | 0.950 |
C5—C6 | 1.503 (3) | C18—H18 | 0.950 |
C5—C10 | 1.399 (3) | C18—H19 | 0.950 |
C6—C7 | 1.543 (3) | C18—H20 | 0.950 |
C6—H4 | 0.950 | C19—C20 | 1.531 (3) |
C6—H5 | 0.950 | C19—H22 | 0.950 |
C7—C8 | 1.557 (3) | C19—H23 | 0.950 |
C7—C19 | 1.530 (3) | C20—C21 | 1.523 (3) |
C7—H6 | 0.950 | C20—H24 | 0.950 |
C8—C9 | 1.562 (3) | C20—H25 | 0.950 |
C8—C14 | 1.527 (3) | C21—C22 | 1.521 (3) |
C8—H7 | 0.950 | C21—H26 | 0.950 |
C9—C10 | 1.516 (4) | C21—H27 | 0.950 |
C9—C11 | 1.534 (3) | C22—C23 | 1.539 (3) |
C9—H8 | 0.950 | C22—H28 | 0.950 |
C11—C12 | 1.531 (4) | C22—H29 | 0.950 |
C11—H9 | 0.950 | C23—C24 | 1.461 (3) |
C11—H10 | 0.950 | C23—H30 | 0.950 |
C12—C13 | 1.519 (3) | C23—H31 | 0.950 |
C12—H11 | 0.950 | ||
O1···N1i | 2.894 (3) | C18···H17 | 3.324 |
O1···C2 | 2.429 (3) | C18···H25iii | 3.476 |
O1···C4 | 2.362 (3) | C18···H27iii | 3.521 |
O1···C9ii | 3.503 (2) | C18···H29iii | 3.554 |
O1···H2 | 2.634 | C18···H30xi | 3.572 |
O1···H3 | 2.529 | C18···H31xi | 2.945 |
O1···H8ii | 2.871 | C19···C5 | 3.300 (3) |
O1···H9ii | 3.05 | C19···C6 | 2.522 (3) |
O2···C12 | 3.007 (3) | C19···C8 | 2.550 (3) |
O2···C13 | 2.449 (3) | C19···C14 | 3.407 (3) |
O2···C14 | 3.482 (3) | C19···C15 | 3.466 (4) |
O2···C16 | 2.434 (3) | C19···C21 | 2.545 (3) |
O2···C18 | 3.227 (3) | C19···H4 | 2.509 |
O2···C22iii | 3.576 (3) | C19···H5 | 3.285 |
O2···C23iii | 3.165 (3) | C19···H6 | 2.033 |
O2···C24iii | 3.564 (3) | C19···H7 | 2.508 |
O2···H7iv | 3.017 | C19···H13ii | 3.307 |
O2···H11 | 3.01 | C19···H14 | 3.201 |
O2···H12 | 2.948 | C19···H15 | 3.338 |
O2···H13 | 3.485 | C19···H16ii | 3.167 |
O2···H15iv | 3.551 | C19···H24 | 2.037 |
O2···H16 | 2.692 | C19···H25 | 2.049 |
O2···H17 | 2.759 | C19···H26 | 2.736 |
O2···H18iv | 3.177 | C19···H27 | 2.692 |
O2···H19 | 3.498 | C20···C6 | 3.177 (3) |
O2···H19iv | 3.201 | C20···C7 | 2.565 (3) |
O2···H20 | 3.052 | C20···C22 | 2.541 (3) |
O2···H22iv | 3.581 | C20···H4 | 2.752 |
O2···H23iv | 3.361 | C20···H6 | 2.626 |
O2···H27iii | 3.286 | C20···H20ix | 3.242 |
O2···H29iii | 3.216 | C20···H22 | 2.044 |
O2···H31iii | 2.392 | C20···H23 | 2.034 |
N1···O1v | 2.894 (3) | C20···H26 | 2.038 |
N1···C1vi | 3.576 (3) | C20···H27 | 2.032 |
N1···C2v | 3.474 (3) | C20···H28 | 2.7 |
N1···C3v | 3.578 (3) | C20···H29 | 2.755 |
N1···C22 | 3.463 (3) | C20···H30iv | 3.586 |
N1···C23 | 2.601 (3) | C21···C19 | 2.545 (3) |
N1···H1vi | 3.03 | C21···C23 | 2.512 (3) |
N1···H2v | 2.795 | C21···H13ii | 3.509 |
N1···H9vi | 3.102 | C21···H14ii | 3.199 |
N1···H21v | 2.074 | C21···H16ii | 3.116 |
N1···H28 | 3.543 | C21···H20ix | 3.166 |
N1···H29 | 3.454 | C21···H22 | 2.652 |
N1···H30 | 3.051 | C21···H23 | 2.776 |
N1···H31 | 3.055 | C21···H24 | 2.034 |
C1···N1vii | 3.576 (3) | C21···H25 | 2.039 |
C1···C3 | 2.411 (4) | C21···H28 | 2.047 |
C1···C4 | 2.775 (3) | C21···H29 | 2.038 |
C1···C5 | 2.401 (3) | C21···H30 | 2.716 |
C1···C9 | 2.579 (3) | C21···H31 | 2.643 |
C1···C11 | 2.951 (4) | C22···O2ix | 3.576 (3) |
C1···H2 | 2.047 | C22···N1 | 3.463 (3) |
C1···H7 | 3.561 | C22···C20 | 2.541 (3) |
C1···H8 | 3.126 | C22···C24 | 2.487 (3) |
C1···H9 | 2.899 | C22···H20ix | 3.38 |
C1···H10 | 2.805 | C22···H24 | 2.734 |
C1···H11ii | 3.39 | C22···H25 | 2.697 |
C1···H17iii | 2.934 | C22···H26 | 2.029 |
C2···O1 | 2.429 (3) | C22···H27 | 2.039 |
C2···N1i | 3.474 (3) | C22···H30 | 2.05 |
C2···C4 | 2.409 (3) | C22···H31 | 2.054 |
C2···C5 | 2.784 (3) | C23···O2ix | 3.165 (3) |
C2···C10 | 2.425 (3) | C23···N1 | 2.601 (3) |
C2···H1 | 2.04 | C23···C21 | 2.512 (3) |
C2···H3 | 3.268 | C23···H18xii | 3.475 |
C2···H9ii | 3.19 | C23···H19xii | 3.267 |
C2···H11ii | 3.329 | C23···H20xii | 3.523 |
C2···H17iii | 3.197 | C23···H25ii | 3.535 |
C2···H21 | 2.455 | C23···H26 | 2.636 |
C3···N1i | 3.578 (3) | C23···H27 | 2.708 |
C3···C1 | 2.411 (4) | C23···H28 | 2.059 |
C3···C5 | 2.418 (3) | C23···H29 | 2.055 |
C3···C10 | 2.804 (4) | C24···O2ix | 3.564 (3) |
C3···H1 | 3.265 | C24···C22 | 2.487 (3) |
C3···H2 | 2.036 | C24···H2v | 3.179 |
C3···H3 | 2.046 | C24···H19xii | 3.397 |
C3···H8ii | 3.085 | C24···H21v | 3.135 |
C3···H9ii | 3.08 | C24···H28 | 2.711 |
C3···H11ii | 3.266 | C24···H29 | 2.643 |
C3···H21 | 1.823 | C24···H30 | 1.985 |
C4···O1 | 2.362 (3) | C24···H31 | 1.985 |
C4···C1 | 2.775 (3) | H1···N1vii | 3.03 |
C4···C2 | 2.409 (3) | H1···C2 | 2.04 |
C4···C6 | 2.541 (3) | H1···C3 | 3.265 |
C4···C10 | 2.422 (4) | H1···C5 | 3.259 |
C4···H2 | 3.267 | H1···C9 | 2.759 |
C4···H4 | 2.578 | H1···C10 | 2.032 |
C4···H5 | 3.073 | H1···C11 | 2.602 |
C4···H8ii | 3.171 | H1···C16iii | 3.355 |
C4···H11ii | 3.288 | H2···O1 | 2.634 |
C4···H21 | 3.044 | H2···N1i | 2.795 |
C4···H22 | 3.49 | H2···C1 | 2.047 |
C5···C1 | 2.401 (3) | H2···C3 | 2.036 |
C5···C2 | 2.784 (3) | H2···C4 | 3.267 |
C5···C3 | 2.418 (3) | H2···C10 | 3.281 |
C5···C7 | 2.529 (3) | H2···C24i | 3.179 |
C5···C8 | 2.832 (3) | H3···O1 | 2.529 |
C5···C9 | 2.475 (4) | H3···C2 | 3.268 |
C5···C19 | 3.300 (3) | H3···C3 | 2.046 |
C5···H1 | 3.259 | H3···C5 | 2.037 |
C5···H3 | 2.037 | H3···C6 | 2.712 |
C5···H4 | 2.018 | H3···C10 | 3.277 |
C5···H5 | 2.022 | H4···C4 | 2.578 |
C5···H6 | 3.283 | H4···C5 | 2.018 |
C5···H7 | 3.008 | H4···C7 | 2.052 |
C5···H8 | 2.705 | H4···C8 | 3.34 |
C5···H11ii | 3.376 | H4···C10 | 3.245 |
C5···H22 | 2.978 | H4···C19 | 2.509 |
C6···C4 | 2.541 (3) | H4···C20 | 2.752 |
C6···C7 | 1.543 (3) | H5···C4 | 3.073 |
C6···C8 | 2.569 (3) | H5···C5 | 2.022 |
C6···C9 | 2.748 (3) | H5···C7 | 2.06 |
C6···C10 | 2.473 (3) | H5···C8 | 2.933 |
C6···C19 | 2.522 (3) | H5···C9 | 2.814 |
C6···C20 | 3.177 (3) | H5···C10 | 2.747 |
C6···H3 | 2.712 | H5···C19 | 3.285 |
C6···H6 | 2.042 | H6···C5 | 3.283 |
C6···H7 | 3.041 | H6···C6 | 2.042 |
C6···H8 | 2.669 | H6···C8 | 2.056 |
C6···H22 | 2.598 | H6···C9 | 3.04 |
C6···H23 | 3.324 | H6···C14 | 2.501 |
C6···H24 | 2.806 | H6···C15 | 2.976 |
C7···C5 | 2.529 (3) | H6···C19 | 2.033 |
C7···C6 | 1.543 (3) | H6···C20 | 2.626 |
C7···C8 | 1.557 (3) | H7···O2ii | 3.017 |
C7···C9 | 2.580 (3) | H7···C1 | 3.561 |
C7···C10 | 2.961 (3) | H7···C5 | 3.008 |
C7···C14 | 2.551 (4) | H7···C6 | 3.041 |
C7···C15 | 3.196 (4) | H7···C7 | 2.061 |
C7···C20 | 2.565 (3) | H7···C9 | 2.067 |
C7···H4 | 2.052 | H7···C10 | 2.617 |
C7···H5 | 2.06 | H7···C11 | 2.811 |
C7···H7 | 2.061 | H7···C12 | 3.36 |
C7···H8 | 2.695 | H7···C13 | 2.763 |
C7···H13 | 2.69 | H7···C14 | 2.034 |
C7···H14 | 3.031 | H7···C15 | 2.871 |
C7···H15 | 3.423 | H7···C18 | 2.844 |
C7···H22 | 2.04 | H7···C19 | 2.508 |
C7···H23 | 2.042 | H8···O1iv | 2.871 |
C7···H24 | 2.672 | H8···C1 | 3.126 |
C7···H25 | 2.809 | H8···C3iv | 3.085 |
C8···C5 | 2.832 (3) | H8···C4iv | 3.171 |
C8···C6 | 2.569 (3) | H8···C5 | 2.705 |
C8···C7 | 1.557 (3) | H8···C6 | 2.669 |
C8···C9 | 1.562 (3) | H8···C7 | 2.695 |
C8···C10 | 2.474 (3) | H8···C8 | 2.059 |
C8···C11 | 2.584 (3) | H8···C10 | 2.013 |
C8···C12 | 3.020 (4) | H8···C11 | 2.035 |
C8···C13 | 2.566 (4) | H8···C12 | 2.758 |
C8···C15 | 2.672 (3) | H8···C13 | 3.303 |
C8···C18 | 3.155 (3) | H8···C14 | 2.735 |
C8···C19 | 2.550 (3) | H9···O1iv | 3.05 |
C8···H4 | 3.34 | H9···N1vii | 3.102 |
C8···H5 | 2.933 | H9···C1 | 2.899 |
C8···H6 | 2.056 | H9···C2iv | 3.19 |
C8···H8 | 2.059 | H9···C3iv | 3.08 |
C8···H9 | 3.384 | H9···C8 | 3.384 |
C8···H10 | 2.814 | H9···C9 | 2.046 |
C8···H11 | 3.317 | H9···C10 | 2.772 |
C8···H13 | 2.005 | H9···C12 | 2.04 |
C8···H14 | 2.987 | H9···C13 | 3.3 |
C8···H15 | 2.86 | H10···C1 | 2.805 |
C8···H18 | 2.935 | H10···C8 | 2.814 |
C8···H19 | 3.329 | H10···C9 | 2.047 |
C8···H22 | 2.843 | H10···C10 | 2.704 |
C8···H23 | 2.593 | H10···C12 | 2.046 |
C9···O1iv | 3.503 (2) | H10···C13 | 2.686 |
C9···C1 | 2.579 (3) | H10···C14 | 3.26 |
C9···C5 | 2.475 (4) | H10···C15iii | 3.364 |
C9···C6 | 2.748 (3) | H10···C18 | 2.728 |
C9···C7 | 2.580 (3) | H11···O2 | 3.01 |
C9···C8 | 1.562 (3) | H11···C1iv | 3.39 |
C9···C12 | 2.553 (4) | H11···C2iv | 3.329 |
C9···C13 | 2.953 (3) | H11···C3iv | 3.266 |
C9···C14 | 2.514 (3) | H11···C4iv | 3.288 |
C9···H1 | 2.759 | H11···C5iv | 3.376 |
C9···H5 | 2.814 | H11···C8 | 3.317 |
C9···H6 | 3.04 | H11···C9 | 2.768 |
C9···H7 | 2.067 | H11···C10iv | 3.412 |
C9···H9 | 2.046 | H11···C11 | 2.058 |
C9···H10 | 2.047 | H11···C13 | 2.041 |
C9···H11 | 2.768 | H11···C14 | 2.691 |
C9···H12 | 3.36 | H11···C17 | 2.729 |
C9···H13 | 2.648 | H11···C18 | 3.349 |
C9···H18 | 3.293 | H12···O2 | 2.948 |
C10···C2 | 2.425 (3) | H12···C9 | 3.36 |
C10···C3 | 2.804 (4) | H12···C11 | 2.052 |
C10···C4 | 2.422 (4) | H12···C13 | 2.044 |
C10···C6 | 2.473 (3) | H12···C14 | 3.329 |
C10···C7 | 2.961 (3) | H12···C16viii | 3.135 |
C10···C8 | 2.474 (3) | H12···C17 | 2.844 |
C10···C11 | 2.559 (4) | H12···C18 | 2.664 |
C10···H1 | 2.032 | H13···O2 | 3.485 |
C10···H2 | 3.281 | H13···C7 | 2.69 |
C10···H3 | 3.277 | H13···C8 | 2.005 |
C10···H4 | 3.245 | H13···C9 | 2.648 |
C10···H5 | 2.747 | H13···C11 | 3.139 |
C10···H7 | 2.617 | H13···C12 | 2.606 |
C10···H8 | 2.013 | H13···C13 | 2.02 |
C10···H9 | 2.772 | H13···C15 | 2.018 |
C10···H10 | 2.704 | H13···C16 | 2.588 |
C10···H11ii | 3.412 | H13···C17 | 2.517 |
C11···C1 | 2.951 (4) | H13···C18 | 3.355 |
C11···C8 | 2.584 (3) | H13···C19iv | 3.307 |
C11···C10 | 2.559 (4) | H13···C21iv | 3.509 |
C11···C13 | 2.487 (3) | H14···C7 | 3.031 |
C11···C14 | 2.918 (3) | H14···C8 | 2.987 |
C11···C18 | 3.055 (3) | H14···C13 | 3.257 |
C11···H1 | 2.602 | H14···C14 | 2.086 |
C11···H7 | 2.811 | H14···C16 | 2.089 |
C11···H8 | 2.035 | H14···C17 | 3.207 |
C11···H11 | 2.058 | H14···C19 | 3.201 |
C11···H12 | 2.052 | H14···C21iv | 3.199 |
C11···H13 | 3.139 | H15···O2ii | 3.551 |
C11···H15iii | 3.595 | H15···C7 | 3.423 |
C11···H18 | 2.688 | H15···C8 | 2.86 |
C11···H20 | 3.485 | H15···C11ix | 3.595 |
C11···H21iv | 3.575 | H15···C13 | 2.748 |
C12···O2 | 3.007 (3) | H15···C14 | 2.083 |
C12···C8 | 3.020 (4) | H15···C16 | 2.09 |
C12···C9 | 2.553 (4) | H15···C17 | 2.934 |
C12···C14 | 2.507 (3) | H15···C18 | 2.797 |
C12···C17 | 2.587 (4) | H15···C19 | 3.338 |
C12···C18 | 2.539 (3) | H16···O2 | 2.692 |
C12···H7 | 3.36 | H16···C12x | 3.359 |
C12···H8 | 2.758 | H16···C13 | 3.132 |
C12···H9 | 2.04 | H16···C14 | 2.88 |
C12···H10 | 2.046 | H16···C15 | 2.08 |
C12···H13 | 2.606 | H16···C17 | 2.061 |
C12···H16viii | 3.359 | H16···C19iv | 3.167 |
C12···H18 | 2.681 | H16···C21iv | 3.116 |
C12···H19 | 3.341 | H17···O2 | 2.759 |
C12···H20 | 2.781 | H17···C1ix | 2.934 |
C13···O2 | 2.449 (3) | H17···C2ix | 3.197 |
C13···C8 | 2.566 (4) | H17···C13 | 3.06 |
C13···C9 | 2.953 (3) | H17···C14 | 3.161 |
C13···C11 | 2.487 (3) | H17···C15 | 2.079 |
C13···C14 | 1.542 (3) | H17···C17 | 2.058 |
C13···C15 | 2.428 (3) | H17···C18 | 3.324 |
C13···C16 | 2.470 (3) | H18···O2ii | 3.177 |
C13···C18 | 1.548 (3) | H18···C8 | 2.935 |
C13···H7 | 2.763 | H18···C9 | 3.293 |
C13···H8 | 3.303 | H18···C11 | 2.688 |
C13···H9 | 3.3 | H18···C12 | 2.681 |
C13···H10 | 2.686 | H18···C13 | 2.07 |
C13···H11 | 2.041 | H18···C14 | 2.846 |
C13···H12 | 2.044 | H18···C15 | 3.496 |
C13···H13 | 2.02 | H18···C17 | 3.275 |
C13···H14 | 3.257 | H18···C23xi | 3.475 |
C13···H15 | 2.748 | H19···O2ii | 3.201 |
C13···H16 | 3.132 | H19···O2 | 3.498 |
C13···H17 | 3.06 | H19···C8 | 3.329 |
C13···H18 | 2.07 | H19···C12 | 3.341 |
C13···H19 | 2.062 | H19···C13 | 2.062 |
C13···H20 | 2.074 | H19···C14 | 2.677 |
C14···O2 | 3.482 (3) | H19···C15 | 2.595 |
C14···C7 | 2.551 (4) | H19···C16 | 2.832 |
C14···C9 | 2.514 (3) | H19···C17 | 2.592 |
C14···C11 | 2.918 (3) | H19···C23xi | 3.267 |
C14···C12 | 2.507 (3) | H19···C24xi | 3.397 |
C14···C13 | 1.542 (3) | H20···O2 | 3.052 |
C14···C15 | 1.542 (3) | H20···C11 | 3.485 |
C14···C16 | 2.403 (4) | H20···C12 | 2.781 |
C14···C17 | 2.356 (4) | H20···C13 | 2.074 |
C14···C18 | 2.577 (3) | H20···C14 | 3.379 |
C14···C19 | 3.407 (3) | H20···C16 | 3.548 |
C14···H6 | 2.501 | H20···C17 | 2.605 |
C14···H7 | 2.034 | H20···C20iii | 3.242 |
C14···H8 | 2.735 | H20···C21iii | 3.166 |
C14···H10 | 3.26 | H20···C22iii | 3.38 |
C14···H11 | 2.691 | H20···C23xi | 3.523 |
C14···H12 | 3.329 | H21···N1i | 2.074 |
C14···H14 | 2.086 | H21···C2 | 2.455 |
C14···H15 | 2.083 | H21···C3 | 1.823 |
C14···H16 | 2.88 | H21···C4 | 3.044 |
C14···H17 | 3.161 | H21···C11ii | 3.575 |
C14···H18 | 2.846 | H21···C24i | 3.135 |
C14···H19 | 2.677 | H22···O2ii | 3.581 |
C14···H20 | 3.379 | H22···C4 | 3.49 |
C14···H22iv | 3.308 | H22···C5 | 2.978 |
C14···H23 | 3.115 | H22···C6 | 2.598 |
C14···H26iv | 3.48 | H22···C7 | 2.04 |
C15···C7 | 3.196 (4) | H22···C8 | 2.843 |
C15···C8 | 2.672 (3) | H22···C14ii | 3.308 |
C15···C13 | 2.428 (3) | H22···C16ii | 3.456 |
C15···C14 | 1.542 (3) | H22···C17ii | 3.308 |
C15···C16 | 1.548 (4) | H22···C20 | 2.044 |
C15···C17 | 2.455 (4) | H22···C21 | 2.652 |
C15···C18 | 2.996 (3) | H23···O2ii | 3.361 |
C15···C19 | 3.466 (4) | H23···C6 | 3.324 |
C15···H6 | 2.976 | H23···C7 | 2.042 |
C15···H7 | 2.871 | H23···C8 | 2.593 |
C15···H10ix | 3.364 | H23···C14 | 3.115 |
C15···H13 | 2.018 | H23···C15 | 2.842 |
C15···H16 | 2.08 | H23···C16ii | 3.382 |
C15···H17 | 2.079 | H23···C17ii | 3.422 |
C15···H18 | 3.496 | H23···C20 | 2.034 |
C15···H19 | 2.595 | H23···C21 | 2.776 |
C15···H23 | 2.842 | H24···C6 | 2.806 |
C15···H26iv | 3.314 | H24···C7 | 2.672 |
C15···H27iv | 3.437 | H24···C19 | 2.037 |
C16···O2 | 2.434 (3) | H24···C21 | 2.034 |
C16···C13 | 2.470 (3) | H24···C22 | 2.734 |
C16···C14 | 2.403 (4) | H25···C7 | 2.809 |
C16···C15 | 1.548 (4) | H25···C18ix | 3.476 |
C16···C18 | 3.146 (4) | H25···C19 | 2.049 |
C16···H1ix | 3.355 | H25···C21 | 2.039 |
C16···H12x | 3.135 | H25···C22 | 2.697 |
C16···H13 | 2.588 | H25···C23iv | 3.535 |
C16···H14 | 2.089 | H26···C14ii | 3.48 |
C16···H15 | 2.09 | H26···C15ii | 3.314 |
C16···H19 | 2.832 | H26···C19 | 2.736 |
C16···H20 | 3.548 | H26···C20 | 2.038 |
C16···H22iv | 3.456 | H26···C22 | 2.029 |
C16···H23iv | 3.382 | H26···C23 | 2.636 |
C16···H27iv | 3.229 | H27···O2ix | 3.286 |
C17···C12 | 2.587 (4) | H27···C15ii | 3.437 |
C17···C14 | 2.356 (4) | H27···C16ii | 3.229 |
C17···C15 | 2.455 (4) | H27···C18ix | 3.521 |
C17···C18 | 2.439 (3) | H27···C19 | 2.692 |
C17···H11 | 2.729 | H27···C20 | 2.032 |
C17···H12 | 2.844 | H27···C22 | 2.039 |
C17···H13 | 2.517 | H27···C23 | 2.708 |
C17···H14 | 3.207 | H28···N1 | 3.543 |
C17···H15 | 2.934 | H28···C20 | 2.7 |
C17···H16 | 2.061 | H28···C21 | 2.047 |
C17···H17 | 2.058 | H28···C23 | 2.059 |
C17···H18 | 3.275 | H28···C24 | 2.711 |
C17···H19 | 2.592 | H29···O2ix | 3.216 |
C17···H20 | 2.605 | H29···N1 | 3.454 |
C17···H22iv | 3.308 | H29···C18ix | 3.554 |
C17···H23iv | 3.422 | H29···C20 | 2.755 |
C17···H31iii | 3.463 | H29···C21 | 2.038 |
C18···O2 | 3.227 (3) | H29···C23 | 2.055 |
C18···C8 | 3.155 (3) | H29···C24 | 2.643 |
C18···C11 | 3.055 (3) | H30···N1 | 3.051 |
C18···C12 | 2.539 (3) | H30···C18xii | 3.572 |
C18···C13 | 1.548 (3) | H30···C20ii | 3.586 |
C18···C14 | 2.577 (3) | H30···C21 | 2.716 |
C18···C15 | 2.996 (3) | H30···C22 | 2.05 |
C18···C16 | 3.146 (4) | H30···C24 | 1.985 |
C18···C17 | 2.439 (3) | H31···O2ix | 2.392 |
C18···H7 | 2.844 | H31···N1 | 3.055 |
C18···H10 | 2.728 | H31···C17ix | 3.463 |
C18···H11 | 3.349 | H31···C18xii | 2.945 |
C18···H12 | 2.664 | H31···C21 | 2.643 |
C18···H13 | 3.355 | H31···C22 | 2.054 |
C18···H15 | 2.797 | H31···C24 | 1.985 |
C3—O1—H21 | 110.1 | C18—C13—C12 | 111.7 (2) |
C2—C1—C10 | 121.0 (2) | C15—C14—H13 | 105.6 |
C2—C1—H1 | 119.6 | C15—C14—C8 | 121.1 (2) |
C10—C1—H1 | 119.4 | C15—C14—C13 | 103.9 (2) |
C3—C2—H2 | 119.8 | H13—C14—C8 | 105.8 |
C3—C2—C1 | 119.8 (2) | H13—C14—C13 | 105.8 |
H2—C2—C1 | 120.3 | C8—C14—C13 | 113.5 (2) |
C4—C3—O1 | 117.1 (2) | C16—C15—H14 | 111.2 |
C4—C3—C2 | 119.6 (2) | C16—C15—H15 | 111.3 |
O1—C3—C2 | 123.3 (2) | C16—C15—C14 | 102.1 (2) |
C5—C4—H3 | 119.8 | H14—C15—H15 | 109.5 |
C5—C4—C3 | 120.2 (2) | H14—C15—C14 | 111.5 |
H3—C4—C3 | 120.0 | H15—C15—C14 | 111.1 |
C6—C5—C10 | 116.8 (2) | C17—C16—H16 | 110.4 |
C6—C5—C4 | 122.7 (2) | C17—C16—H17 | 110.2 |
C10—C5—C4 | 120.5 (2) | C17—C16—C15 | 105.9 (2) |
C7—C6—H4 | 108.5 | H16—C16—H17 | 109.5 |
C7—C6—H5 | 109.1 | H16—C16—C15 | 110.5 |
C7—C6—C5 | 112.2 (2) | H17—C16—C15 | 110.4 |
H4—C6—H5 | 109.5 | O2—C17—C13 | 126.7 (2) |
H4—C6—C5 | 108.6 | O2—C17—C16 | 125.2 (2) |
H5—C6—C5 | 109.0 | C13—C17—C16 | 108.0 (2) |
C8—C7—C19 | 111.3 (2) | H18—C18—H19 | 109.5 |
C8—C7—H6 | 107.7 | H18—C18—H20 | 109.5 |
C8—C7—C6 | 112.0 (2) | H18—C18—C13 | 109.6 |
C19—C7—H6 | 107.8 | H19—C18—H20 | 109.5 |
C19—C7—C6 | 110.3 (2) | H19—C18—C13 | 108.9 |
H6—C7—C6 | 107.6 | H20—C18—C13 | 109.9 |
C9—C8—C14 | 109.0 (2) | C20—C19—H22 | 108.7 |
C9—C8—H7 | 108.2 | C20—C19—H23 | 107.8 |
C9—C8—C7 | 111.6 (2) | C20—C19—C7 | 113.8 (2) |
C14—C8—H7 | 108.1 | H22—C19—H23 | 109.5 |
C14—C8—C7 | 111.6 (2) | H22—C19—C7 | 108.4 |
H7—C8—C7 | 108.2 | H23—C19—C7 | 108.6 |
C10—C9—C11 | 114.0 (2) | C21—C20—H24 | 108.4 |
C10—C9—H8 | 107.2 | C21—C20—H25 | 108.9 |
C10—C9—C8 | 106.9 (2) | C21—C20—C19 | 112.9 (2) |
C11—C9—H8 | 107.7 | H24—C20—H25 | 109.5 |
C11—C9—C8 | 113.1 (2) | H24—C20—C19 | 108.1 |
H8—C9—C8 | 107.6 | H25—C20—C19 | 109.1 |
C1—C10—C5 | 118.8 (2) | C22—C21—H26 | 108.2 |
C1—C10—C9 | 125.0 (2) | C22—C21—H27 | 109.0 |
C5—C10—C9 | 116.1 (2) | C22—C21—C20 | 113.2 (2) |
C12—C11—H9 | 108.4 | H26—C21—H27 | 109.5 |
C12—C11—H10 | 108.8 | H26—C21—C20 | 108.7 |
C12—C11—C9 | 112.8 (2) | H27—C21—C20 | 108.3 |
H9—C11—H10 | 109.5 | C23—C22—H28 | 109.4 |
H9—C11—C9 | 108.6 | C23—C22—H29 | 109.0 |
H10—C11—C9 | 108.7 | C23—C22—C21 | 110.4 (2) |
C13—C12—H11 | 109.3 | H28—C22—H29 | 109.5 |
C13—C12—H12 | 109.5 | H28—C22—C21 | 109.7 |
C13—C12—C11 | 109.3 (2) | H29—C22—C21 | 109.0 |
H11—C12—H12 | 109.5 | C24—C23—H30 | 109.0 |
H11—C12—C11 | 109.9 | C24—C23—H31 | 109.0 |
H12—C12—C11 | 109.4 | C24—C23—C22 | 111.9 (2) |
C14—C13—C17 | 100.4 (2) | H30—C23—H31 | 109.5 |
C14—C13—C18 | 113.0 (2) | H30—C23—C22 | 108.6 |
C14—C13—C12 | 110.0 (2) | H31—C23—C22 | 108.9 |
C17—C13—C18 | 105.0 (2) | N1—C24—C23 | 177.6 (2) |
C17—C13—C12 | 116.3 (2) | ||
H21—O1—C3—C2 | −12.4 | H9—C11—C12—H12 | 63.3 |
H21—O1—C3—C4 | 168.7 | H10—C11—C12—C13 | 64.2 |
C10—C1—C2—C3 | 0.6 (3) | H10—C11—C12—H11 | −175.9 |
C10—C1—C2—H2 | −179.3 | H10—C11—C12—H12 | −55.7 |
H1—C1—C2—C3 | −179.3 | C11—C12—C13—C14 | 58.6 (2) |
H1—C1—C2—H2 | 0.8 | C11—C12—C13—C17 | 171.7 (2) |
C2—C1—C10—C5 | 1.2 (3) | C11—C12—C13—C18 | −67.8 (3) |
C2—C1—C10—C9 | −175.6 (2) | H11—C12—C13—C14 | −61.7 |
H1—C1—C10—C5 | −178.9 | H11—C12—C13—C17 | 51.5 |
H1—C1—C10—C9 | 4.3 | H11—C12—C13—C18 | 172.0 |
C1—C2—C3—O1 | 179.9 (2) | H12—C12—C13—C14 | 178.4 |
C1—C2—C3—C4 | −1.2 (3) | H12—C12—C13—C17 | −68.4 |
H2—C2—C3—O1 | −0.2 | H12—C12—C13—C18 | 52.1 |
H2—C2—C3—C4 | 178.7 | C12—C13—C14—C8 | −59.8 (2) |
O1—C3—C4—C5 | 179.0 (2) | C12—C13—C14—C15 | 166.8 (2) |
O1—C3—C4—H3 | −0.7 | C12—C13—C14—H13 | 55.8 |
C2—C3—C4—C5 | 0.1 (3) | C17—C13—C14—C8 | 177.1 (2) |
C2—C3—C4—H3 | −179.6 | C17—C13—C14—C15 | 43.7 (2) |
C3—C4—C5—C6 | −177.0 (2) | C17—C13—C14—H13 | −67.3 |
C3—C4—C5—C10 | 1.7 (3) | C18—C13—C14—C8 | 65.8 (2) |
H3—C4—C5—C6 | 2.8 | C18—C13—C14—C15 | −67.6 (2) |
H3—C4—C5—C10 | −178.6 | C18—C13—C14—H13 | −178.6 |
C4—C5—C6—C7 | −129.7 (2) | C12—C13—C17—O2 | 29.8 (3) |
C4—C5—C6—H4 | −9.8 | C12—C13—C17—C16 | −148.6 (2) |
C4—C5—C6—H5 | 109.3 | C14—C13—C17—O2 | 148.3 (2) |
C10—C5—C6—C7 | 51.6 (2) | C14—C13—C17—C16 | −30.0 (2) |
C10—C5—C6—H4 | 171.5 | C18—C13—C17—O2 | −94.3 (2) |
C10—C5—C6—H5 | −69.4 | C18—C13—C17—C16 | 87.4 (2) |
C4—C5—C10—C1 | −2.3 (3) | C12—C13—C18—H18 | 53.3 |
C4—C5—C10—C9 | 174.7 (2) | C12—C13—C18—H19 | 173.0 |
C6—C5—C10—C1 | 176.4 (2) | C12—C13—C18—H20 | −67.1 |
C6—C5—C10—C9 | −6.5 (3) | C14—C13—C18—H18 | −71.4 |
C5—C6—C7—C8 | −35.8 (2) | C14—C13—C18—H19 | 48.3 |
C5—C6—C7—C19 | 88.8 (2) | C14—C13—C18—H20 | 168.3 |
C5—C6—C7—H6 | −153.9 | C17—C13—C18—H18 | −179.8 |
H4—C6—C7—C8 | −155.7 | C17—C13—C18—H19 | −60.1 |
H4—C6—C7—C19 | −31.2 | C17—C13—C18—H20 | 59.8 |
H4—C6—C7—H6 | 86.1 | C8—C14—C15—C16 | −169.8 (2) |
H5—C6—C7—C8 | 85.1 | C8—C14—C15—H14 | 71.4 |
H5—C6—C7—C19 | −150.3 | C8—C14—C15—H15 | −51.0 |
H5—C6—C7—H6 | −33.1 | C13—C14—C15—C16 | −40.8 (2) |
C6—C7—C8—C9 | −18.2 (2) | C13—C14—C15—H14 | −159.7 |
C6—C7—C8—C14 | −140.4 (2) | C13—C14—C15—H15 | 77.9 |
C6—C7—C8—H7 | 100.8 | H13—C14—C15—C16 | 70.3 |
C19—C7—C8—C9 | −142.2 (2) | H13—C14—C15—H14 | −48.5 |
C19—C7—C8—C14 | 95.6 (2) | H13—C14—C15—H15 | −170.9 |
C19—C7—C8—H7 | −23.2 | C14—C15—C16—C17 | 21.5 (2) |
H6—C7—C8—C9 | 99.9 | C14—C15—C16—H16 | −98.1 |
H6—C7—C8—C14 | −22.3 | C14—C15—C16—H17 | 140.7 |
H6—C7—C8—H7 | −141.1 | H14—C15—C16—C17 | 140.5 |
C6—C7—C19—C20 | 73.3 (2) | H14—C15—C16—H16 | 20.9 |
C6—C7—C19—H22 | −47.8 | H14—C15—C16—H17 | −100.3 |
C6—C7—C19—H23 | −166.6 | H15—C15—C16—C17 | −97.2 |
C8—C7—C19—C20 | −161.8 (2) | H15—C15—C16—H16 | 143.3 |
C8—C7—C19—H22 | 77.2 | H15—C15—C16—H17 | 22.1 |
C8—C7—C19—H23 | −41.7 | C15—C16—C17—O2 | −172.9 (2) |
H6—C7—C19—C20 | −43.9 | C15—C16—C17—C13 | 5.5 (2) |
H6—C7—C19—H22 | −165.0 | H16—C16—C17—O2 | −53.3 |
H6—C7—C19—H23 | 76.2 | H16—C16—C17—C13 | 125.1 |
C7—C8—C9—C10 | 60.3 (2) | H17—C16—C17—O2 | 67.7 |
C7—C8—C9—C11 | −173.3 (2) | H17—C16—C17—C13 | −113.9 |
C7—C8—C9—H8 | −54.5 | C7—C19—C20—C21 | −170.5 (2) |
C14—C8—C9—C10 | −175.9 (2) | C7—C19—C20—H24 | −50.6 |
C14—C8—C9—C11 | −49.6 (2) | C7—C19—C20—H25 | 68.4 |
C14—C8—C9—H8 | 69.2 | H22—C19—C20—C21 | −49.6 |
H7—C8—C9—C10 | −58.6 | H22—C19—C20—H24 | 70.3 |
H7—C8—C9—C11 | 67.8 | H22—C19—C20—H25 | −170.7 |
H7—C8—C9—H8 | −173.4 | H23—C19—C20—C21 | 69.0 |
C7—C8—C14—C13 | 177.2 (2) | H23—C19—C20—H24 | −171.1 |
C7—C8—C14—C15 | −58.2 (2) | H23—C19—C20—H25 | −52.1 |
C7—C8—C14—H13 | 61.6 | C19—C20—C21—C22 | −177.6 (2) |
C9—C8—C14—C13 | 53.5 (2) | C19—C20—C21—H26 | 62.1 |
C9—C8—C14—C15 | 178.1 (2) | C19—C20—C21—H27 | −56.7 |
C9—C8—C14—H13 | −62.1 | H24—C20—C21—C22 | 62.7 |
H7—C8—C14—C13 | −63.9 | H24—C20—C21—H26 | −57.6 |
H7—C8—C14—C15 | 60.7 | H24—C20—C21—H27 | −176.4 |
H7—C8—C14—H13 | −179.5 | H25—C20—C21—C22 | −56.3 |
C8—C9—C10—C1 | 128.3 (2) | H25—C20—C21—H26 | −176.6 |
C8—C9—C10—C5 | −48.5 (2) | H25—C20—C21—H27 | 64.6 |
C11—C9—C10—C1 | 2.5 (3) | C20—C21—C22—C23 | −175.8 (2) |
C11—C9—C10—C5 | −174.3 (2) | C20—C21—C22—H28 | −55.2 |
H8—C9—C10—C1 | −116.5 | C20—C21—C22—H29 | 64.6 |
H8—C9—C10—C5 | 66.6 | H26—C21—C22—C23 | −55.2 |
C8—C9—C11—C12 | 52.8 (2) | H26—C21—C22—H28 | 65.4 |
C8—C9—C11—H9 | 173.0 | H26—C21—C22—H29 | −174.8 |
C8—C9—C11—H10 | −68.0 | H27—C21—C22—C23 | 63.7 |
C10—C9—C11—C12 | 175.3 (2) | H27—C21—C22—H28 | −175.7 |
C10—C9—C11—H9 | −64.5 | H27—C21—C22—H29 | −55.9 |
C10—C9—C11—H10 | 54.5 | C21—C22—C23—C24 | −174.8 (2) |
H8—C9—C11—C12 | −66.0 | C21—C22—C23—H30 | 64.9 |
H8—C9—C11—H9 | 54.2 | C21—C22—C23—H31 | −54.2 |
H8—C9—C11—H10 | 173.3 | H28—C22—C23—C24 | 64.4 |
C9—C11—C12—C13 | −56.5 (2) | H28—C22—C23—H30 | −55.9 |
C9—C11—C12—H11 | 63.4 | H28—C22—C23—H31 | −175.0 |
C9—C11—C12—H12 | −176.4 | H29—C22—C23—C24 | −55.2 |
H9—C11—C12—C13 | −176.8 | H29—C22—C23—H30 | −175.5 |
H9—C11—C12—H11 | −56.9 | H29—C22—C23—H31 | 65.4 |
Symmetry codes: (i) x, y−1, z; (ii) x−1, y, z; (iii) −x+1, y−1/2, −z; (iv) x+1, y, z; (v) x, y+1, z; (vi) x−1, y+1, z; (vii) x+1, y−1, z; (viii) −x+2, y−1/2, −z; (ix) −x+1, y+1/2, −z; (x) −x+2, y+1/2, −z; (xi) −x, y−1/2, −z; (xii) −x, y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C24H31NO2 |
Mr | 365.51 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 6.639 (3), 13.530 (6), 11.910 (5) |
β (°) | 107.25 (3) |
V (Å3) | 1021.7 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.50 × 0.20 × 0.12 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.982, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20270, 2458, 2082 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.082, 1.04 |
No. of reflections | 2441 |
No. of parameters | 276 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.25 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, CrystalStructure (Molecular Structure Corporation & Rigaku, 2003), SIR97 (Altomare et al., 1999), CRYSTALS (Watkins et al., 1996), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003), CrystalStructure.
O1—C3 | 1.371 (3) | C7—C8 | 1.557 (3) |
O2—C17 | 1.209 (3) | C7—C19 | 1.530 (3) |
N1—C24 | 1.141 (3) | C8—C9 | 1.562 (3) |
C6—C7 | 1.543 (3) | ||
C2—C1—C10 | 121.0 (2) | C9—C8—C7 | 111.6 (2) |
C8—C7—C6 | 112.0 (2) | C11—C9—C8 | 113.1 (2) |
C4—C5—C6—C7 | −129.7 (2) | C6—C7—C8—C14 | −140.4 (2) |
C10—C5—C6—C7 | 51.6 (2) | C7—C8—C9—C10 | 60.3 (2) |
C6—C7—C8—C9 | −18.2 (2) | C14—C8—C9—C10 | −175.9 (2) |
Recently, synthetic steroids have been proposed as radiodiagnostica (Katzenellenbogen, 1995; Melo e Silva et al., 2001; Wang et al., 2003), as well as potential drug delivery systems targeting oestrogen receptor positive breast cancer and other diseases associated with the oestrogen receptor ERα. Mandatory for the success of these compounds is a good binding affinity to the receptor. It has been determined that a C7 substituent, carrying a long chain with a polar terminus, often influences the binding affinity, where the commonly synthesized 7α-substituted oestrane-derived steroids have a much better binding affinity than the corresponding 7β-epimers. The authors have studied the binding affinity to the oestrogen receptor of C7-substituted oestra-1,3,5(10),6-tetraenes, i.e. compounds analogous to those described above, but with the C7 substituent branching off from an sp2-hybridized C atom (Inohae et al., 1999; Thiemann et al., 2002). It was deemed advantageous to prepare the 7β-substituted compounds in order to compare the binding affinity and in vivo biodistribution of a series of 7α- and 7β-substituted oestranes and of the corresponding 7-substituted oestra-1,3,5(10),6-tetraenes. The measurement of the X-ray crystal structure of the title compound, (I), was carried out in order to be able to better model the complex of a 7β-substituted steroidal ligand and the binding domain of the nuclear receptor, the X-ray crystal structure of which is known. \sch
The molecule of (I), with the atomic numbering scheme, is depicted in Fig. 1. Ring A shows a little distortion from planarity [average mean plane deviation 0.012 (2) Å], as is also evident in other oestrones and oestradiols for which X-ray structural analyses have been carried out. Ring C, with trans fusion to rings B and D, is fixed in a chair conformation. In oestra-1,3,5(10)-trienes, ring B, as a cyclohexen,e is known to be less rigid (Bucourt & Hainault, 1967). This is found in the three known polymorphs of oestrone [oestra-1,3,5(10)-trien-3-ol-17-one], where all three exhibit a slightly different conformation of ring B, although the α-H at C7 in each adopts an axial position (Busetta et al., 1973, and references cited therein). This situation holds true for derivatives of oestrone that are unsubstituted in ring B and for oestradiol [oestra-1,3,5(10)-trien-3,17β-diol], where both X-ray crystal structure analyses and calculations (Sebag et al., 2000) show that, again, the α-H at C7 (H6) takes an axial position.
The determining effect on the conformation of ring B in (I) is the 7β substituent, where potential interactions of the substituent with the C15α H atom (H14) and minor ones with the C5α and C5β H atoms (H5 and H4, respectively) force atom C7 and the C7β substituent upward, with a concomitant change in the C5—C7—C8—C9 dihedral angle to −18.2 (2)°. This compares with the range of −60.9 to −70.6° measured for different oestrane analogues of (I), such as for the polymorphs of oestrone, epioestradiol and oestradiol and as calculated for these molecules (Kubli-Garfias, 1998). Similarly, the C5—C5—C7—C8 dihedral angle here is −35.8 (2)°, compared with the range of 32.1–49.0° measured for the same oestrane analogues and as calculated (Kubli-Garfias, 1998). The C5—C5—C7—C19 dihedral angle is 88.8 (2)°; the equivalent C5—C5—C7—H7β dihedral angle in oestrone is 156.9 and 166.1° for the two crystal forms, respectively (Busetta et al., 1973). The intramolecular 1:4 contact distances H5···H6 (2.202 Å) and H4···H24 (2.169 Å) are short.
The conformation of ring B is between a boat and a twisted-boat conformation, as characterized by the Cremer & Pople (1975) puckering parameters, Q = 0.717 (3) Å, θ = 84.51 (21)° and ϕ = 227.8 (2)° [for a perfect boat conformation, θ = 90.0° and ϕ = k × 60°; for a perfect twisted-boat conformation, θ = 90.0° and ϕ = k × 60° + 30° (Boeyens, 1978)]. This is also in accordance with the relative signs of the endocyclic torsion angles within ring B [see Boeyens (1978)]. In contrast with most other oestrane derivatives, neither the α-H atom at C7 (H6) nor the β-H atom at C5 (H4) adopts an axial position. Importantly, this different conformation of ring B leads to a much larger tilt angle between ring D and the phenolic ring A than is known for oestra-1,3,5(10)-trienes; for (I), the angle between the two mean planes defined by the C atoms of rings A and D is 28.6 (1)°.
The C5—C7, C7—C8 and C8—C9 bond lengths in (I) (Table 1) are significantly longer than those reported for non-substituted oestrones (Busetta et al., 1973; Hejaz et al., 1999). The C5—C5 and C9—C10 bond lengths have comparable values or are a little shorter. In the crystal of (I), the C7 substituent lies above the mean plane defined by the steroidal skeleton (rings A, B, C and D, averaged over all 17 atoms of the framework), with a calculated distance from the plane of 3.862 Å for atom C24 and 3.798 Å for atom N1. The chiral centres at C7, C8, C9, C13 and C14 are S, R, S, S and S, respectively.
In the crystal, compound (I) packs as molecular chains along the b axis, bound by a strong O1—H21···N1i hydrogen bond [O1···N1i 2.894 (3) Å, H21···N1i 2.074 Å, O1—H21···N1i 177°; symmetry code: (i) x, y − 1, z] and a weaker C23—H31···O2ii interaction [C23···O2ii 3.165 (3) Å, H31···O2ii 2.392 Å, C23—H31···O2ii 138.2 Å; symmetry code: (ii) −x, 1/2 + y, −z], as shown in Fig. 2.