Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103029159/sk1692sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103029159/sk1692Isup2.hkl |
CCDC reference: 233142
A solution of 2'-p-fluorophenyl-17a-aza-D-homo-5-androsteno[17,16 − c]pyrazol-3β-ol (0.5 g, 1.186 mmol) in cyclohexanone (5 ml) and toluene (100 ml) was slowly distilled while aluminium isopropoxide (1 g) in toluene (10 ml) was added to remove moisture. Distillation was continued for 30 min. The reaction mixture was refluxed for 4 h and allowed to stand overnight. The solution was filtered, the filtrate was steam distilled and the residue obtained was crystallized from ethyl acetate to afford (I) (institution code DPJ-255) (yield 0.35 g, 70.42%; m.p. 499–501 K).
The positions of the amine H atoms were determined from a difference Fourier map and refined freely along with their isotropic displacement parameters. The methyl H atoms 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 to ride on their parent atoms. Due to the absence of any significant anomalous scatterers in (I), attempts to confirm the absolute structure by refinement of the Flack (1983) parameter in the presence of 5710 sets of Friedel equivalents led to an inconclusive value (Flack & Bernardinelli, 2000) of 0.2 (6). Therefore, the Friedel pairs were merged before the final refinement and the absolute configuration was assigned to correspond with that of the known chiral centres in a precursor molecule, which remained unchanged during the synthesis of (I). Reflections 003, 103, 012, 101, 110, 011, 002, 111, 102 and 101 were partially obscured by the beam stop and were omitted.
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, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).
C26H30FN3O | F(000) = 896 |
Mr = 419.53 | Dx = 1.301 Mg m−3 |
Monoclinic, P21 | Melting point: 499 K |
Hall symbol: P 2yb | Mo Kα radiation, λ = 0.71073 Å |
a = 13.5243 (2) Å | Cell parameters from 6708 reflections |
b = 7.3983 (1) Å | θ = 1.0–30.0° |
c = 21.8934 (3) Å | µ = 0.09 mm−1 |
β = 102.1562 (8)° | T = 160 K |
V = 2141.47 (5) Å3 | Prism, colourless |
Z = 4 | 0.30 × 0.28 × 0.15 mm |
Nonius KappaCCD area-detector diffractometer | 5595 reflections with I > 2σ(I) |
Radiation source: Nonius FR590 sealed tube generator | Rint = 0.055 |
Horizontally mounted graphite crystal monochromator | θmax = 30.0°, θmin = 1.5° |
Detector resolution: 9 pixels mm-1 | h = 0→19 |
ϕ and ω scans with κ offsets | k = 0→10 |
64206 measured reflections | l = −30→30 |
6714 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0503P)2 + 0.2257P] where P = (Fo2 + 2Fc2)/3 |
6704 reflections | (Δ/σ)max < 0.001 |
571 parameters | Δρmax = 0.23 e Å−3 |
1 restraint | Δρmin = −0.19 e Å−3 |
C26H30FN3O | V = 2141.47 (5) Å3 |
Mr = 419.53 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 13.5243 (2) Å | µ = 0.09 mm−1 |
b = 7.3983 (1) Å | T = 160 K |
c = 21.8934 (3) Å | 0.30 × 0.28 × 0.15 mm |
β = 102.1562 (8)° |
Nonius KappaCCD area-detector diffractometer | 5595 reflections with I > 2σ(I) |
64206 measured reflections | Rint = 0.055 |
6714 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 1 restraint |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.23 e Å−3 |
6704 reflections | Δρmin = −0.19 e Å−3 |
571 parameters |
Experimental. Solvent used: ethyl acetate Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.577 (1) Frames collected: 654 Seconds exposure per frame: 56 Degrees rotation per frame: 1.4 Crystal-Detector distance (mm): 33.00 |
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. |
x | y | z | Uiso*/Ueq | ||
F26A | 0.93563 (11) | 0.6916 (2) | 0.45681 (6) | 0.0608 (4) | |
O3A | 0.64070 (11) | 0.8096 (2) | −0.28067 (6) | 0.0440 (4) | |
N17A | 0.83048 (12) | 0.9618 (2) | 0.17080 (7) | 0.0274 (3) | |
H171 | 0.8706 (16) | 0.889 (3) | 0.1948 (9) | 0.030 (6)* | |
N20A | 0.83126 (12) | 1.1636 (2) | 0.25918 (7) | 0.0319 (4) | |
N21A | 0.82075 (13) | 1.3467 (2) | 0.26969 (8) | 0.0359 (4) | |
C1A | 0.77864 (14) | 0.7205 (3) | −0.12396 (8) | 0.0287 (4) | |
H11 | 0.8337 | 0.6385 | −0.1038 | 0.034* | |
H12 | 0.7154 | 0.6781 | −0.1127 | 0.034* | |
C2A | 0.76691 (15) | 0.7073 (3) | −0.19464 (8) | 0.0349 (4) | |
H21 | 0.8330 | 0.7312 | −0.2057 | 0.042* | |
H22 | 0.7458 | 0.5831 | −0.2084 | 0.042* | |
C3A | 0.69016 (14) | 0.8396 (3) | −0.22810 (8) | 0.0335 (4) | |
C4A | 0.68109 (14) | 1.0100 (3) | −0.19577 (8) | 0.0328 (4) | |
H41 | 0.6367 | 1.0996 | −0.2173 | 0.039* | |
C5A | 0.73176 (14) | 1.0472 (3) | −0.13751 (8) | 0.0287 (4) | |
C6A | 0.72597 (16) | 1.2325 (3) | −0.11010 (9) | 0.0345 (4) | |
H61 | 0.6680 | 1.2982 | −0.1357 | 0.041* | |
H62 | 0.7883 | 1.3001 | −0.1124 | 0.041* | |
C7A | 0.71387 (15) | 1.2292 (3) | −0.04201 (8) | 0.0328 (4) | |
H71 | 0.7205 | 1.3537 | −0.0251 | 0.039* | |
H72 | 0.6454 | 1.1849 | −0.0405 | 0.039* | |
C8A | 0.79300 (13) | 1.1077 (3) | −0.00106 (8) | 0.0260 (4) | |
H81 | 0.8614 | 1.1563 | −0.0026 | 0.031* | |
C9A | 0.78460 (13) | 0.9162 (2) | −0.02945 (8) | 0.0250 (4) | |
H91 | 0.7130 | 0.8772 | −0.0322 | 0.030* | |
C10A | 0.80224 (13) | 0.9129 (3) | −0.09776 (8) | 0.0266 (4) | |
C11A | 0.85062 (14) | 0.7776 (3) | 0.01259 (8) | 0.0294 (4) | |
H111 | 0.8344 | 0.6548 | −0.0046 | 0.035* | |
H112 | 0.9227 | 0.8019 | 0.0129 | 0.035* | |
C12A | 0.83405 (15) | 0.7846 (3) | 0.07924 (8) | 0.0281 (4) | |
H121 | 0.7634 | 0.7498 | 0.0794 | 0.034* | |
H122 | 0.8794 | 0.6963 | 0.1053 | 0.034* | |
C13A | 0.85460 (13) | 0.9724 (3) | 0.10753 (7) | 0.0250 (4) | |
C14A | 0.78224 (13) | 1.1097 (2) | 0.06784 (8) | 0.0256 (4) | |
H141 | 0.7117 | 1.0707 | 0.0684 | 0.031* | |
C15A | 0.79608 (14) | 1.3017 (3) | 0.09601 (8) | 0.0293 (4) | |
H151 | 0.8569 | 1.3585 | 0.0859 | 0.035* | |
H152 | 0.7367 | 1.3771 | 0.0778 | 0.035* | |
C16A | 0.80736 (14) | 1.2917 (3) | 0.16569 (9) | 0.0292 (4) | |
C17A | 0.82387 (14) | 1.1301 (3) | 0.19689 (8) | 0.0283 (4) | |
C18A | 0.96644 (13) | 1.0250 (3) | 0.11412 (9) | 0.0311 (4) | |
H181 | 0.9807 | 1.1343 | 0.1398 | 0.047* | |
H182 | 0.9803 | 1.0483 | 0.0727 | 0.047* | |
H183 | 1.0096 | 0.9260 | 0.1341 | 0.047* | |
C19A | 0.91197 (14) | 0.9679 (3) | −0.10031 (9) | 0.0329 (4) | |
H191 | 0.9208 | 0.9610 | −0.1435 | 0.049* | |
H192 | 0.9597 | 0.8857 | −0.0741 | 0.049* | |
H193 | 0.9247 | 1.0919 | −0.0849 | 0.049* | |
C22A | 0.80583 (15) | 1.4194 (3) | 0.21296 (9) | 0.0340 (4) | |
H221 | 0.7952 | 1.5450 | 0.2052 | 0.041* | |
C23A | 0.85678 (14) | 1.0425 (3) | 0.31009 (8) | 0.0301 (4) | |
C24A | 0.81643 (15) | 0.8700 (3) | 0.30567 (9) | 0.0346 (4) | |
H241 | 0.7697 | 0.8342 | 0.2690 | 0.042* | |
C25A | 0.84420 (16) | 0.7492 (3) | 0.35484 (9) | 0.0389 (5) | |
H251 | 0.8191 | 0.6288 | 0.3518 | 0.047* | |
C26A | 0.90889 (16) | 0.8090 (4) | 0.40784 (9) | 0.0410 (5) | |
C27A | 0.94871 (15) | 0.9799 (4) | 0.41414 (9) | 0.0416 (5) | |
H271 | 0.9929 | 1.0162 | 0.4519 | 0.050* | |
C28A | 0.92325 (14) | 1.0991 (3) | 0.36434 (9) | 0.0367 (5) | |
H281 | 0.9508 | 1.2177 | 0.3672 | 0.044* | |
F26B | 0.50302 (12) | 0.1489 (3) | 0.04360 (6) | 0.0726 (5) | |
O3B | 1.00431 (10) | 0.2061 (2) | 0.77531 (6) | 0.0409 (3) | |
N17B | 0.63298 (12) | 0.3303 (2) | 0.34312 (7) | 0.0275 (3) | |
H172 | 0.6866 (18) | 0.297 (4) | 0.3336 (10) | 0.042 (7)* | |
N20B | 0.57358 (12) | 0.5524 (2) | 0.26091 (7) | 0.0292 (3) | |
N21B | 0.54452 (12) | 0.7309 (2) | 0.25586 (7) | 0.0339 (4) | |
C1B | 0.85595 (15) | 0.0665 (3) | 0.62605 (8) | 0.0350 (4) | |
H13 | 0.8240 | −0.0471 | 0.6078 | 0.042* | |
H14 | 0.9131 | 0.0933 | 0.6057 | 0.042* | |
C2B | 0.89697 (17) | 0.0381 (3) | 0.69581 (9) | 0.0370 (5) | |
H23 | 0.8420 | −0.0070 | 0.7154 | 0.044* | |
H24 | 0.9510 | −0.0545 | 0.7019 | 0.044* | |
C3B | 0.93861 (14) | 0.2102 (3) | 0.72720 (8) | 0.0306 (4) | |
C4B | 0.89392 (15) | 0.3784 (3) | 0.70008 (8) | 0.0318 (4) | |
H42 | 0.9193 | 0.4886 | 0.7195 | 0.038* | |
C5B | 0.81865 (14) | 0.3871 (3) | 0.64901 (8) | 0.0277 (4) | |
C6B | 0.76515 (16) | 0.5618 (3) | 0.62932 (8) | 0.0355 (4) | |
H63 | 0.8061 | 0.6624 | 0.6512 | 0.043* | |
H64 | 0.6996 | 0.5615 | 0.6426 | 0.043* | |
C7B | 0.74563 (15) | 0.5966 (3) | 0.55868 (8) | 0.0303 (4) | |
H73 | 0.7017 | 0.7042 | 0.5486 | 0.036* | |
H74 | 0.8107 | 0.6229 | 0.5466 | 0.036* | |
C8B | 0.69525 (13) | 0.4355 (2) | 0.52090 (7) | 0.0247 (4) | |
H82 | 0.6276 | 0.4160 | 0.5314 | 0.030* | |
C9B | 0.76004 (13) | 0.2645 (2) | 0.54019 (8) | 0.0245 (3) | |
H92 | 0.8281 | 0.2905 | 0.5312 | 0.029* | |
C10B | 0.77796 (13) | 0.2208 (3) | 0.61146 (8) | 0.0269 (4) | |
C11B | 0.71825 (15) | 0.1016 (3) | 0.49992 (8) | 0.0305 (4) | |
H113 | 0.7649 | −0.0021 | 0.5109 | 0.037* | |
H114 | 0.6519 | 0.0670 | 0.5087 | 0.037* | |
C12B | 0.70572 (15) | 0.1435 (3) | 0.43066 (8) | 0.0308 (4) | |
H123 | 0.7728 | 0.1704 | 0.4215 | 0.037* | |
H124 | 0.6783 | 0.0356 | 0.4061 | 0.037* | |
C13B | 0.63550 (13) | 0.3030 (2) | 0.41053 (7) | 0.0250 (4) | |
C14B | 0.67903 (13) | 0.4701 (2) | 0.44983 (7) | 0.0240 (3) | |
H142 | 0.7473 | 0.4938 | 0.4407 | 0.029* | |
C15B | 0.61383 (15) | 0.6396 (3) | 0.42849 (8) | 0.0307 (4) | |
H153 | 0.5510 | 0.6345 | 0.4449 | 0.037* | |
H154 | 0.6516 | 0.7497 | 0.4452 | 0.037* | |
C16B | 0.58786 (14) | 0.6472 (3) | 0.35839 (8) | 0.0292 (4) | |
C17B | 0.60014 (13) | 0.5018 (3) | 0.32233 (8) | 0.0273 (4) | |
C18B | 0.52654 (13) | 0.2605 (3) | 0.41605 (8) | 0.0315 (4) | |
H184 | 0.4808 | 0.3531 | 0.3938 | 0.047* | |
H185 | 0.5225 | 0.2597 | 0.4602 | 0.047* | |
H186 | 0.5068 | 0.1418 | 0.3976 | 0.047* | |
C19B | 0.67893 (15) | 0.1657 (4) | 0.63078 (9) | 0.0405 (5) | |
H194 | 0.6913 | 0.1520 | 0.6763 | 0.061* | |
H195 | 0.6549 | 0.0507 | 0.6108 | 0.061* | |
H196 | 0.6276 | 0.2593 | 0.6175 | 0.061* | |
C22B | 0.55308 (14) | 0.7854 (3) | 0.31462 (8) | 0.0329 (4) | |
H222 | 0.5375 | 0.9043 | 0.3259 | 0.039* | |
C23B | 0.56032 (14) | 0.4450 (3) | 0.20570 (8) | 0.0317 (4) | |
C24B | 0.54753 (15) | 0.2598 (3) | 0.20783 (9) | 0.0367 (5) | |
H242 | 0.5513 | 0.2016 | 0.2469 | 0.044* | |
C25B | 0.52929 (16) | 0.1581 (4) | 0.15320 (9) | 0.0447 (5) | |
H252 | 0.5213 | 0.0307 | 0.1543 | 0.054* | |
C26B | 0.52323 (17) | 0.2470 (4) | 0.09777 (9) | 0.0479 (6) | |
C27B | 0.53627 (17) | 0.4288 (4) | 0.09393 (9) | 0.0493 (6) | |
H272 | 0.5321 | 0.4852 | 0.0545 | 0.059* | |
C28B | 0.55582 (16) | 0.5311 (4) | 0.14874 (9) | 0.0418 (5) | |
H282 | 0.5659 | 0.6580 | 0.1471 | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F26A | 0.0646 (9) | 0.0798 (11) | 0.0369 (7) | 0.0098 (8) | 0.0083 (6) | 0.0217 (7) |
O3A | 0.0476 (8) | 0.0563 (10) | 0.0251 (7) | 0.0006 (8) | 0.0005 (6) | −0.0034 (7) |
N17A | 0.0356 (8) | 0.0235 (8) | 0.0233 (7) | 0.0009 (7) | 0.0064 (6) | 0.0011 (6) |
N20A | 0.0389 (9) | 0.0310 (9) | 0.0265 (7) | 0.0008 (7) | 0.0081 (6) | −0.0062 (7) |
N21A | 0.0387 (9) | 0.0323 (9) | 0.0367 (9) | −0.0016 (7) | 0.0082 (7) | −0.0103 (8) |
C1A | 0.0357 (9) | 0.0252 (9) | 0.0246 (8) | 0.0010 (8) | 0.0051 (7) | −0.0001 (7) |
C2A | 0.0426 (11) | 0.0352 (11) | 0.0258 (8) | 0.0024 (9) | 0.0051 (7) | −0.0045 (8) |
C3A | 0.0350 (10) | 0.0410 (11) | 0.0242 (9) | −0.0044 (9) | 0.0057 (7) | 0.0019 (8) |
C4A | 0.0336 (9) | 0.0375 (11) | 0.0267 (9) | 0.0042 (8) | 0.0050 (7) | 0.0058 (8) |
C5A | 0.0301 (9) | 0.0288 (10) | 0.0280 (9) | 0.0016 (8) | 0.0079 (7) | 0.0057 (8) |
C6A | 0.0442 (11) | 0.0265 (10) | 0.0309 (9) | 0.0047 (8) | 0.0038 (8) | 0.0053 (8) |
C7A | 0.0386 (10) | 0.0290 (10) | 0.0294 (9) | 0.0068 (8) | 0.0039 (7) | 0.0004 (8) |
C8A | 0.0280 (8) | 0.0244 (9) | 0.0251 (8) | 0.0015 (7) | 0.0044 (6) | 0.0012 (7) |
C9A | 0.0278 (8) | 0.0231 (9) | 0.0237 (8) | −0.0005 (7) | 0.0044 (6) | 0.0004 (7) |
C10A | 0.0287 (9) | 0.0259 (9) | 0.0247 (8) | 0.0007 (7) | 0.0043 (7) | 0.0014 (7) |
C11A | 0.0397 (10) | 0.0230 (9) | 0.0245 (8) | 0.0045 (8) | 0.0044 (7) | −0.0006 (7) |
C12A | 0.0378 (9) | 0.0228 (9) | 0.0233 (8) | 0.0009 (8) | 0.0055 (7) | 0.0015 (7) |
C13A | 0.0296 (9) | 0.0234 (9) | 0.0219 (8) | −0.0002 (7) | 0.0048 (6) | −0.0003 (7) |
C14A | 0.0272 (8) | 0.0234 (9) | 0.0261 (8) | −0.0012 (7) | 0.0051 (7) | 0.0000 (7) |
C15A | 0.0343 (9) | 0.0236 (9) | 0.0297 (9) | 0.0004 (7) | 0.0061 (7) | −0.0013 (7) |
C16A | 0.0322 (9) | 0.0260 (9) | 0.0298 (9) | −0.0009 (8) | 0.0072 (7) | −0.0053 (7) |
C17A | 0.0279 (9) | 0.0316 (10) | 0.0262 (8) | −0.0021 (7) | 0.0074 (7) | −0.0034 (8) |
C18A | 0.0302 (9) | 0.0312 (10) | 0.0316 (9) | 0.0001 (8) | 0.0058 (7) | 0.0020 (8) |
C19A | 0.0313 (9) | 0.0355 (11) | 0.0326 (9) | 0.0010 (8) | 0.0084 (7) | 0.0021 (8) |
C22A | 0.0364 (10) | 0.0308 (11) | 0.0359 (10) | −0.0005 (8) | 0.0099 (8) | −0.0053 (8) |
C23A | 0.0306 (9) | 0.0368 (10) | 0.0240 (8) | 0.0015 (8) | 0.0083 (7) | −0.0050 (8) |
C24A | 0.0383 (10) | 0.0413 (12) | 0.0250 (9) | −0.0045 (9) | 0.0087 (7) | −0.0037 (8) |
C25A | 0.0432 (11) | 0.0423 (12) | 0.0340 (10) | −0.0015 (9) | 0.0145 (8) | 0.0034 (9) |
C26A | 0.0394 (11) | 0.0574 (15) | 0.0283 (10) | 0.0090 (10) | 0.0121 (8) | 0.0094 (10) |
C27A | 0.0342 (10) | 0.0634 (16) | 0.0268 (9) | 0.0054 (10) | 0.0052 (8) | −0.0056 (10) |
C28A | 0.0330 (10) | 0.0466 (13) | 0.0307 (9) | −0.0019 (9) | 0.0071 (8) | −0.0082 (9) |
F26B | 0.0783 (10) | 0.1054 (14) | 0.0295 (6) | 0.0167 (10) | 0.0010 (6) | −0.0274 (8) |
O3B | 0.0416 (8) | 0.0449 (9) | 0.0297 (7) | −0.0006 (7) | −0.0075 (6) | −0.0029 (6) |
N17B | 0.0329 (8) | 0.0303 (8) | 0.0194 (7) | 0.0051 (7) | 0.0056 (6) | −0.0021 (6) |
N20B | 0.0338 (8) | 0.0316 (9) | 0.0208 (7) | 0.0018 (7) | 0.0030 (6) | 0.0018 (6) |
N21B | 0.0389 (9) | 0.0321 (9) | 0.0284 (8) | −0.0017 (7) | 0.0016 (6) | 0.0052 (7) |
C1B | 0.0457 (11) | 0.0271 (10) | 0.0272 (9) | −0.0004 (9) | −0.0039 (8) | −0.0001 (8) |
C2B | 0.0453 (11) | 0.0320 (11) | 0.0283 (9) | −0.0023 (9) | −0.0045 (8) | 0.0039 (8) |
C3B | 0.0320 (9) | 0.0363 (11) | 0.0227 (8) | −0.0027 (8) | 0.0041 (7) | −0.0013 (8) |
C4B | 0.0375 (10) | 0.0324 (10) | 0.0238 (9) | −0.0052 (8) | 0.0029 (7) | −0.0043 (8) |
C5B | 0.0332 (9) | 0.0304 (10) | 0.0206 (8) | −0.0032 (8) | 0.0079 (7) | −0.0004 (7) |
C6B | 0.0499 (12) | 0.0322 (11) | 0.0220 (9) | 0.0023 (9) | 0.0022 (8) | −0.0046 (8) |
C7B | 0.0406 (10) | 0.0240 (9) | 0.0239 (8) | 0.0010 (8) | 0.0012 (7) | −0.0012 (7) |
C8B | 0.0293 (8) | 0.0252 (9) | 0.0195 (7) | −0.0019 (7) | 0.0048 (6) | −0.0018 (7) |
C9B | 0.0267 (8) | 0.0253 (9) | 0.0207 (8) | −0.0024 (7) | 0.0033 (6) | −0.0012 (7) |
C10B | 0.0302 (9) | 0.0277 (9) | 0.0214 (8) | −0.0053 (7) | 0.0022 (6) | 0.0013 (7) |
C11B | 0.0398 (10) | 0.0239 (9) | 0.0241 (8) | 0.0011 (8) | −0.0017 (7) | 0.0008 (7) |
C12B | 0.0392 (10) | 0.0272 (9) | 0.0238 (8) | 0.0049 (8) | 0.0013 (7) | −0.0031 (7) |
C13B | 0.0302 (9) | 0.0250 (9) | 0.0190 (8) | 0.0015 (7) | 0.0035 (6) | −0.0022 (7) |
C14B | 0.0291 (8) | 0.0236 (9) | 0.0186 (7) | −0.0010 (7) | 0.0034 (6) | −0.0012 (7) |
C15B | 0.0424 (10) | 0.0250 (9) | 0.0225 (8) | 0.0034 (8) | 0.0021 (7) | −0.0018 (7) |
C16B | 0.0336 (9) | 0.0285 (10) | 0.0238 (8) | −0.0009 (8) | 0.0022 (7) | −0.0005 (7) |
C17B | 0.0275 (8) | 0.0322 (10) | 0.0217 (8) | 0.0008 (7) | 0.0039 (6) | 0.0016 (7) |
C18B | 0.0317 (9) | 0.0340 (10) | 0.0274 (9) | −0.0031 (8) | 0.0032 (7) | −0.0007 (8) |
C19B | 0.0382 (10) | 0.0540 (14) | 0.0288 (9) | −0.0136 (10) | 0.0058 (8) | 0.0065 (10) |
C22B | 0.0395 (10) | 0.0269 (10) | 0.0296 (9) | 0.0005 (8) | 0.0010 (7) | 0.0020 (8) |
C23B | 0.0283 (9) | 0.0455 (12) | 0.0207 (8) | 0.0061 (8) | 0.0040 (7) | −0.0003 (8) |
C24B | 0.0378 (10) | 0.0470 (13) | 0.0244 (9) | 0.0002 (9) | 0.0045 (7) | −0.0055 (9) |
C25B | 0.0429 (11) | 0.0554 (14) | 0.0335 (10) | 0.0011 (11) | 0.0028 (8) | −0.0145 (10) |
C26B | 0.0418 (12) | 0.0766 (19) | 0.0233 (10) | 0.0143 (12) | 0.0018 (8) | −0.0139 (11) |
C27B | 0.0456 (12) | 0.080 (2) | 0.0213 (9) | 0.0200 (12) | 0.0056 (8) | 0.0041 (11) |
C28B | 0.0418 (11) | 0.0592 (15) | 0.0247 (9) | 0.0131 (11) | 0.0077 (8) | 0.0071 (10) |
F26A—C26A | 1.368 (2) | F26B—C26B | 1.368 (3) |
O3A—C3A | 1.224 (2) | O3B—C3B | 1.227 (2) |
N17A—C17A | 1.381 (3) | N17B—C17B | 1.389 (2) |
N17A—C13A | 1.491 (2) | N17B—C13B | 1.483 (2) |
N17A—H171 | 0.86 (2) | N17B—H172 | 0.83 (2) |
N20A—C17A | 1.369 (2) | N20B—C17B | 1.369 (2) |
N20A—N21A | 1.387 (3) | N20B—N21B | 1.376 (2) |
N20A—C23A | 1.415 (3) | N20B—C23B | 1.426 (2) |
N21A—C22A | 1.329 (3) | N21B—C22B | 1.330 (2) |
C1A—C2A | 1.525 (2) | C1B—C2B | 1.526 (3) |
C1A—C10A | 1.543 (3) | C1B—C10B | 1.542 (3) |
C1A—H11 | 0.9900 | C1B—H13 | 0.9900 |
C1A—H12 | 0.9900 | C1B—H14 | 0.9900 |
C2A—C3A | 1.501 (3) | C2B—C3B | 1.499 (3) |
C2A—H21 | 0.9900 | C2B—H23 | 0.9900 |
C2A—H22 | 0.9900 | C2B—H24 | 0.9900 |
C3A—C4A | 1.463 (3) | C3B—C4B | 1.454 (3) |
C4A—C5A | 1.343 (3) | C4B—C5B | 1.346 (3) |
C4A—H41 | 0.9500 | C4B—H42 | 0.9500 |
C5A—C6A | 1.505 (3) | C5B—C6B | 1.500 (3) |
C5A—C10A | 1.518 (2) | C5B—C10B | 1.517 (3) |
C6A—C7A | 1.534 (3) | C6B—C7B | 1.535 (2) |
C6A—H61 | 0.9900 | C6B—H63 | 0.9900 |
C6A—H62 | 0.9900 | C6B—H64 | 0.9900 |
C7A—C8A | 1.534 (2) | C7B—C8B | 1.527 (2) |
C7A—H71 | 0.9900 | C7B—H73 | 0.9900 |
C7A—H72 | 0.9900 | C7B—H74 | 0.9900 |
C8A—C9A | 1.542 (3) | C8B—C9B | 1.546 (2) |
C8A—C14A | 1.546 (2) | C8B—C14B | 1.546 (2) |
C8A—H81 | 1.0000 | C8B—H82 | 1.0000 |
C9A—C11A | 1.533 (2) | C9B—C11B | 1.530 (2) |
C9A—C10A | 1.564 (2) | C9B—C10B | 1.562 (2) |
C9A—H91 | 1.0000 | C9B—H92 | 1.0000 |
C10A—C19A | 1.551 (3) | C10B—C19B | 1.542 (3) |
C11A—C12A | 1.523 (2) | C11B—C12B | 1.522 (2) |
C11A—H111 | 0.9900 | C11B—H113 | 0.9900 |
C11A—H112 | 0.9900 | C11B—H114 | 0.9900 |
C12A—C13A | 1.522 (3) | C12B—C13B | 1.521 (3) |
C12A—H121 | 0.9900 | C12B—H123 | 0.9900 |
C12A—H122 | 0.9900 | C12B—H124 | 0.9900 |
C13A—C18A | 1.539 (2) | C13B—C18B | 1.536 (2) |
C13A—C14A | 1.545 (2) | C13B—C14B | 1.549 (2) |
C14A—C15A | 1.544 (3) | C14B—C15B | 1.547 (3) |
C14A—H141 | 1.0000 | C14B—H142 | 1.0000 |
C15A—C16A | 1.503 (2) | C15B—C16B | 1.502 (2) |
C15A—H151 | 0.9900 | C15B—H153 | 0.9900 |
C15A—H152 | 0.9900 | C15B—H154 | 0.9900 |
C16A—C17A | 1.372 (3) | C16B—C17B | 1.365 (3) |
C16A—C22A | 1.405 (3) | C16B—C22B | 1.412 (3) |
C18A—H181 | 0.9800 | C18B—H184 | 0.9800 |
C18A—H182 | 0.9800 | C18B—H185 | 0.9800 |
C18A—H183 | 0.9800 | C18B—H186 | 0.9800 |
C19A—H191 | 0.9800 | C19B—H194 | 0.9800 |
C19A—H192 | 0.9800 | C19B—H195 | 0.9800 |
C19A—H193 | 0.9800 | C19B—H196 | 0.9800 |
C22A—H221 | 0.9500 | C22B—H222 | 0.9500 |
C23A—C24A | 1.383 (3) | C23B—C24B | 1.383 (3) |
C23A—C28A | 1.394 (3) | C23B—C28B | 1.390 (3) |
C24A—C25A | 1.389 (3) | C24B—C25B | 1.390 (3) |
C24A—H241 | 0.9500 | C24B—H242 | 0.9500 |
C25A—C26A | 1.371 (3) | C25B—C26B | 1.367 (3) |
C25A—H251 | 0.9500 | C25B—H252 | 0.9500 |
C26A—C27A | 1.370 (4) | C26B—C27B | 1.361 (4) |
C27A—C28A | 1.388 (3) | C27B—C28B | 1.396 (3) |
C27A—H271 | 0.9500 | C27B—H272 | 0.9500 |
C28A—H281 | 0.9500 | C28B—H282 | 0.9500 |
C17A—N17A—C13A | 112.53 (15) | C17B—N17B—C13B | 112.88 (14) |
C17A—N17A—H171 | 113.6 (15) | C17B—N17B—H172 | 114.9 (18) |
C13A—N17A—H171 | 111.5 (14) | C13B—N17B—H172 | 111.8 (15) |
C17A—N20A—N21A | 110.68 (16) | C17B—N20B—N21B | 110.66 (16) |
C17A—N20A—C23A | 128.70 (17) | C17B—N20B—C23B | 129.84 (17) |
N21A—N20A—C23A | 120.30 (15) | N21B—N20B—C23B | 118.94 (15) |
C22A—N21A—N20A | 103.94 (16) | C22B—N21B—N20B | 104.35 (16) |
C2A—C1A—C10A | 113.93 (16) | C2B—C1B—C10B | 113.45 (17) |
C2A—C1A—H11 | 108.8 | C2B—C1B—H13 | 108.9 |
C10A—C1A—H11 | 108.8 | C10B—C1B—H13 | 108.9 |
C2A—C1A—H12 | 108.8 | C2B—C1B—H14 | 108.9 |
C10A—C1A—H12 | 108.8 | C10B—C1B—H14 | 108.9 |
H11—C1A—H12 | 107.7 | H13—C1B—H14 | 107.7 |
C3A—C2A—C1A | 111.53 (16) | C3B—C2B—C1B | 111.35 (17) |
C3A—C2A—H21 | 109.3 | C3B—C2B—H23 | 109.4 |
C1A—C2A—H21 | 109.3 | C1B—C2B—H23 | 109.4 |
C3A—C2A—H22 | 109.3 | C3B—C2B—H24 | 109.4 |
C1A—C2A—H22 | 109.3 | C1B—C2B—H24 | 109.4 |
H21—C2A—H22 | 108.0 | H23—C2B—H24 | 108.0 |
O3A—C3A—C4A | 121.75 (19) | O3B—C3B—C4B | 122.35 (18) |
O3A—C3A—C2A | 121.7 (2) | O3B—C3B—C2B | 120.44 (18) |
C4A—C3A—C2A | 116.47 (15) | C4B—C3B—C2B | 117.13 (14) |
C5A—C4A—C3A | 123.92 (18) | C5B—C4B—C3B | 123.81 (18) |
C5A—C4A—H41 | 118.0 | C5B—C4B—H42 | 118.1 |
C3A—C4A—H41 | 118.0 | C3B—C4B—H42 | 118.1 |
C4A—C5A—C6A | 120.43 (17) | C4B—C5B—C6B | 120.96 (17) |
C4A—C5A—C10A | 122.90 (18) | C4B—C5B—C10B | 122.44 (18) |
C6A—C5A—C10A | 116.54 (15) | C6B—C5B—C10B | 116.43 (14) |
C5A—C6A—C7A | 113.47 (15) | C5B—C6B—C7B | 113.87 (16) |
C5A—C6A—H61 | 108.9 | C5B—C6B—H63 | 108.8 |
C7A—C6A—H61 | 108.9 | C7B—C6B—H63 | 108.8 |
C5A—C6A—H62 | 108.9 | C5B—C6B—H64 | 108.8 |
C7A—C6A—H62 | 108.9 | C7B—C6B—H64 | 108.8 |
H61—C6A—H62 | 107.7 | H63—C6B—H64 | 107.7 |
C8A—C7A—C6A | 111.92 (15) | C8B—C7B—C6B | 112.15 (16) |
C8A—C7A—H71 | 109.2 | C8B—C7B—H73 | 109.2 |
C6A—C7A—H71 | 109.2 | C6B—C7B—H73 | 109.2 |
C8A—C7A—H72 | 109.2 | C8B—C7B—H74 | 109.2 |
C6A—C7A—H72 | 109.2 | C6B—C7B—H74 | 109.2 |
H71—C7A—H72 | 107.9 | H73—C7B—H74 | 107.9 |
C7A—C8A—C9A | 108.65 (14) | C7B—C8B—C9B | 109.16 (13) |
C7A—C8A—C14A | 111.55 (14) | C7B—C8B—C14B | 111.62 (14) |
C9A—C8A—C14A | 112.83 (14) | C9B—C8B—C14B | 111.25 (14) |
C7A—C8A—H81 | 107.9 | C7B—C8B—H82 | 108.2 |
C9A—C8A—H81 | 107.9 | C9B—C8B—H82 | 108.2 |
C14A—C8A—H81 | 107.9 | C14B—C8B—H82 | 108.2 |
C11A—C9A—C8A | 112.88 (13) | C11B—C9B—C8B | 111.58 (13) |
C11A—C9A—C10A | 112.13 (14) | C11B—C9B—C10B | 111.95 (15) |
C8A—C9A—C10A | 112.77 (14) | C8B—C9B—C10B | 113.71 (14) |
C11A—C9A—H91 | 106.1 | C11B—C9B—H92 | 106.3 |
C8A—C9A—H91 | 106.1 | C8B—C9B—H92 | 106.3 |
C10A—C9A—H91 | 106.1 | C10B—C9B—H92 | 106.3 |
C5A—C10A—C1A | 109.59 (14) | C5B—C10B—C1B | 109.51 (14) |
C5A—C10A—C19A | 107.30 (15) | C5B—C10B—C19B | 107.63 (16) |
C1A—C10A—C19A | 110.71 (16) | C1B—C10B—C19B | 110.07 (17) |
C5A—C10A—C9A | 109.51 (14) | C5B—C10B—C9B | 109.63 (15) |
C1A—C10A—C9A | 108.00 (14) | C1B—C10B—C9B | 108.40 (15) |
C19A—C10A—C9A | 111.72 (14) | C19B—C10B—C9B | 111.58 (14) |
C12A—C11A—C9A | 111.57 (15) | C12B—C11B—C9B | 111.37 (15) |
C12A—C11A—H111 | 109.3 | C12B—C11B—H113 | 109.4 |
C9A—C11A—H111 | 109.3 | C9B—C11B—H113 | 109.4 |
C12A—C11A—H112 | 109.3 | C12B—C11B—H114 | 109.4 |
C9A—C11A—H112 | 109.3 | C9B—C11B—H114 | 109.4 |
H111—C11A—H112 | 108.0 | H113—C11B—H114 | 108.0 |
C13A—C12A—C11A | 111.71 (15) | C13B—C12B—C11B | 112.23 (15) |
C13A—C12A—H121 | 109.3 | C13B—C12B—H123 | 109.2 |
C11A—C12A—H121 | 109.3 | C11B—C12B—H123 | 109.2 |
C13A—C12A—H122 | 109.3 | C13B—C12B—H124 | 109.2 |
C11A—C12A—H122 | 109.3 | C11B—C12B—H124 | 109.2 |
H121—C12A—H122 | 107.9 | H123—C12B—H124 | 107.9 |
N17A—C13A—C12A | 105.86 (14) | N17B—C13B—C12B | 106.02 (14) |
N17A—C13A—C18A | 109.22 (14) | N17B—C13B—C18B | 106.54 (13) |
C12A—C13A—C18A | 111.15 (16) | C12B—C13B—C18B | 111.66 (16) |
N17A—C13A—C14A | 108.69 (14) | N17B—C13B—C14B | 111.76 (14) |
C12A—C13A—C14A | 109.36 (13) | C12B—C13B—C14B | 108.49 (13) |
C18A—C13A—C14A | 112.32 (15) | C18B—C13B—C14B | 112.21 (14) |
C15A—C14A—C13A | 111.79 (14) | C8B—C14B—C15B | 112.89 (14) |
C15A—C14A—C8A | 111.73 (14) | C8B—C14B—C13B | 112.56 (14) |
C13A—C14A—C8A | 111.34 (14) | C15B—C14B—C13B | 110.67 (13) |
C15A—C14A—H141 | 107.2 | C8B—C14B—H142 | 106.8 |
C13A—C14A—H141 | 107.2 | C15B—C14B—H142 | 106.8 |
C8A—C14A—H141 | 107.2 | C13B—C14B—H142 | 106.8 |
C16A—C15A—C14A | 109.77 (15) | C16B—C15B—C14B | 109.57 (15) |
C16A—C15A—H151 | 109.7 | C16B—C15B—H153 | 109.8 |
C14A—C15A—H151 | 109.7 | C14B—C15B—H153 | 109.8 |
C16A—C15A—H152 | 109.7 | C16B—C15B—H154 | 109.8 |
C14A—C15A—H152 | 109.7 | C14B—C15B—H154 | 109.8 |
H151—C15A—H152 | 108.2 | H153—C15B—H154 | 108.2 |
C17A—C16A—C22A | 104.18 (16) | C17B—C16B—C22B | 103.98 (15) |
C17A—C16A—C15A | 121.30 (16) | C17B—C16B—C15B | 122.04 (17) |
C22A—C16A—C15A | 134.51 (19) | C22B—C16B—C15B | 133.92 (18) |
N20A—C17A—C16A | 108.00 (17) | C16B—C17B—N20B | 108.30 (16) |
N20A—C17A—N17A | 125.27 (17) | C16B—C17B—N17B | 126.87 (15) |
C16A—C17A—N17A | 126.72 (15) | N20B—C17B—N17B | 124.82 (16) |
C13A—C18A—H181 | 109.5 | C13B—C18B—H184 | 109.5 |
C13A—C18A—H182 | 109.5 | C13B—C18B—H185 | 109.5 |
H181—C18A—H182 | 109.5 | H184—C18B—H185 | 109.5 |
C13A—C18A—H183 | 109.5 | C13B—C18B—H186 | 109.5 |
H181—C18A—H183 | 109.5 | H184—C18B—H186 | 109.5 |
H182—C18A—H183 | 109.5 | H185—C18B—H186 | 109.5 |
C10A—C19A—H191 | 109.5 | C10B—C19B—H194 | 109.5 |
C10A—C19A—H192 | 109.5 | C10B—C19B—H195 | 109.5 |
H191—C19A—H192 | 109.5 | H194—C19B—H195 | 109.5 |
C10A—C19A—H193 | 109.5 | C10B—C19B—H196 | 109.5 |
H191—C19A—H193 | 109.5 | H194—C19B—H196 | 109.5 |
H192—C19A—H193 | 109.5 | H195—C19B—H196 | 109.5 |
N21A—C22A—C16A | 113.19 (19) | N21B—C22B—C16B | 112.70 (18) |
N21A—C22A—H221 | 123.4 | N21B—C22B—H222 | 123.7 |
C16A—C22A—H221 | 123.4 | C16B—C22B—H222 | 123.7 |
C24A—C23A—C28A | 120.71 (19) | C24B—C23B—C28B | 120.1 (2) |
C24A—C23A—N20A | 120.11 (17) | C24B—C23B—N20B | 121.18 (18) |
C28A—C23A—N20A | 119.18 (19) | C28B—C23B—N20B | 118.6 (2) |
C23A—C24A—C25A | 120.09 (18) | C23B—C24B—C25B | 120.5 (2) |
C23A—C24A—H241 | 120.0 | C23B—C24B—H242 | 119.7 |
C25A—C24A—H241 | 120.0 | C25B—C24B—H242 | 119.7 |
C26A—C25A—C24A | 117.9 (2) | C26B—C25B—C24B | 118.0 (3) |
C26A—C25A—H251 | 121.0 | C26B—C25B—H252 | 121.0 |
C24A—C25A—H251 | 121.0 | C24B—C25B—H252 | 121.0 |
F26A—C26A—C27A | 118.26 (19) | C27B—C26B—C25B | 123.1 (2) |
F26A—C26A—C25A | 118.4 (2) | C27B—C26B—F26B | 118.4 (2) |
C27A—C26A—C25A | 123.4 (2) | C25B—C26B—F26B | 118.6 (3) |
C26A—C27A—C28A | 118.68 (19) | C26B—C27B—C28B | 119.1 (2) |
C26A—C27A—H271 | 120.7 | C26B—C27B—H272 | 120.5 |
C28A—C27A—H271 | 120.7 | C28B—C27B—H272 | 120.5 |
C27A—C28A—C23A | 119.2 (2) | C23B—C28B—C27B | 119.1 (3) |
C27A—C28A—H281 | 120.4 | C23B—C28B—H282 | 120.4 |
C23A—C28A—H281 | 120.4 | C27B—C28B—H282 | 120.4 |
C17A—N20A—N21A—C22A | 0.8 (2) | C23B—N20B—N21B—C22B | 171.66 (16) |
C23A—N20A—N21A—C22A | 174.76 (16) | C10B—C1B—C2B—C3B | −53.8 (2) |
C10A—C1A—C2A—C3A | −53.9 (2) | C1B—C2B—C3B—O3B | −154.23 (19) |
C1A—C2A—C3A—O3A | −151.08 (19) | C1B—C2B—C3B—C4B | 29.0 (2) |
C1A—C2A—C3A—C4A | 31.8 (2) | O3B—C3B—C4B—C5B | −176.91 (19) |
O3A—C3A—C4A—C5A | 178.2 (2) | C2B—C3B—C4B—C5B | −0.2 (3) |
C2A—C3A—C4A—C5A | −4.6 (3) | C3B—C4B—C5B—C6B | 170.37 (18) |
C3A—C4A—C5A—C6A | 173.90 (17) | C3B—C4B—C5B—C10B | −4.8 (3) |
C3A—C4A—C5A—C10A | −1.9 (3) | C4B—C5B—C6B—C7B | 137.31 (19) |
C4A—C5A—C6A—C7A | 137.21 (18) | C10B—C5B—C6B—C7B | −47.3 (2) |
C10A—C5A—C6A—C7A | −46.7 (2) | C5B—C6B—C7B—C8B | 50.7 (2) |
C5A—C6A—C7A—C8A | 50.8 (2) | C6B—C7B—C8B—C9B | −54.8 (2) |
C6A—C7A—C8A—C9A | −56.7 (2) | C6B—C7B—C8B—C14B | −178.24 (15) |
C6A—C7A—C8A—C14A | 178.30 (15) | C7B—C8B—C9B—C11B | −175.07 (14) |
C7A—C8A—C9A—C11A | −172.29 (15) | C14B—C8B—C9B—C11B | −51.46 (19) |
C14A—C8A—C9A—C11A | −48.0 (2) | C7B—C8B—C9B—C10B | 57.14 (18) |
C7A—C8A—C9A—C10A | 59.36 (19) | C14B—C8B—C9B—C10B | −179.24 (14) |
C14A—C8A—C9A—C10A | −176.40 (14) | C4B—C5B—C10B—C1B | −19.2 (2) |
C4A—C5A—C10A—C1A | −18.8 (2) | C6B—C5B—C10B—C1B | 165.46 (16) |
C6A—C5A—C10A—C1A | 165.18 (16) | C4B—C5B—C10B—C19B | 100.4 (2) |
C4A—C5A—C10A—C19A | 101.4 (2) | C6B—C5B—C10B—C19B | −74.9 (2) |
C6A—C5A—C10A—C19A | −74.56 (19) | C4B—C5B—C10B—C9B | −138.01 (18) |
C4A—C5A—C10A—C9A | −137.13 (18) | C6B—C5B—C10B—C9B | 46.6 (2) |
C6A—C5A—C10A—C9A | 46.9 (2) | C2B—C1B—C10B—C5B | 48.1 (2) |
C2A—C1A—C10A—C5A | 46.4 (2) | C2B—C1B—C10B—C19B | −70.1 (2) |
C2A—C1A—C10A—C19A | −71.79 (19) | C2B—C1B—C10B—C9B | 167.65 (16) |
C2A—C1A—C10A—C9A | 165.60 (15) | C11B—C9B—C10B—C5B | −179.65 (15) |
C11A—C9A—C10A—C5A | 177.67 (15) | C8B—C9B—C10B—C5B | −52.05 (19) |
C8A—C9A—C10A—C5A | −53.58 (19) | C11B—C9B—C10B—C1B | 60.85 (19) |
C11A—C9A—C10A—C1A | 58.39 (19) | C8B—C9B—C10B—C1B | −171.55 (14) |
C8A—C9A—C10A—C1A | −172.87 (14) | C11B—C9B—C10B—C19B | −60.5 (2) |
C11A—C9A—C10A—C19A | −63.6 (2) | C8B—C9B—C10B—C19B | 67.1 (2) |
C8A—C9A—C10A—C19A | 65.15 (19) | C8B—C9B—C11B—C12B | 53.9 (2) |
C8A—C9A—C11A—C12A | 50.3 (2) | C10B—C9B—C11B—C12B | −177.40 (15) |
C10A—C9A—C11A—C12A | 178.99 (15) | C9B—C11B—C12B—C13B | −58.5 (2) |
C9A—C11A—C12A—C13A | −57.1 (2) | C17B—N17B—C13B—C12B | −160.30 (15) |
C17A—N17A—C13A—C12A | −166.57 (15) | C17B—N17B—C13B—C18B | 80.63 (18) |
C17A—N17A—C13A—C18A | 73.7 (2) | C17B—N17B—C13B—C14B | −42.3 (2) |
C17A—N17A—C13A—C14A | −49.2 (2) | C11B—C12B—C13B—N17B | 178.53 (15) |
C11A—C12A—C13A—N17A | 177.15 (14) | C11B—C12B—C13B—C18B | −65.83 (19) |
C11A—C12A—C13A—C18A | −64.36 (18) | C11B—C12B—C13B—C14B | 58.3 (2) |
C11A—C12A—C13A—C14A | 60.2 (2) | C7B—C8B—C14B—C15B | −58.2 (2) |
N17A—C13A—C14A—C15A | 62.20 (19) | C9B—C8B—C14B—C15B | 179.62 (14) |
C12A—C13A—C14A—C15A | 177.34 (15) | C7B—C8B—C14B—C13B | 175.64 (15) |
C18A—C13A—C14A—C15A | −58.77 (19) | C9B—C8B—C14B—C13B | 53.44 (18) |
N17A—C13A—C14A—C8A | −172.04 (14) | N17B—C13B—C14B—C8B | −172.58 (14) |
C12A—C13A—C14A—C8A | −56.91 (19) | C12B—C13B—C14B—C8B | −56.03 (19) |
C18A—C13A—C14A—C8A | 66.98 (18) | C18B—C13B—C14B—C8B | 67.81 (18) |
C7A—C8A—C14A—C15A | −60.1 (2) | N17B—C13B—C14B—C15B | 60.06 (19) |
C9A—C8A—C14A—C15A | 177.24 (14) | C12B—C13B—C14B—C15B | 176.60 (14) |
C7A—C8A—C14A—C13A | 174.10 (15) | C18B—C13B—C14B—C15B | −59.56 (19) |
C9A—C8A—C14A—C13A | 51.46 (19) | C8B—C14B—C15B—C16B | −171.07 (15) |
C13A—C14A—C15A—C16A | −42.4 (2) | C13B—C14B—C15B—C16B | −43.9 (2) |
C8A—C14A—C15A—C16A | −167.90 (14) | C14B—C15B—C16B—C17B | 14.7 (3) |
C14A—C15A—C16A—C17A | 12.5 (2) | C14B—C15B—C16B—C22B | −162.2 (2) |
C14A—C15A—C16A—C22A | −168.0 (2) | C22B—C16B—C17B—N20B | −0.2 (2) |
N21A—N20A—C17A—C16A | −0.6 (2) | C15B—C16B—C17B—N20B | −177.88 (17) |
C23A—N20A—C17A—C16A | −173.89 (18) | C22B—C16B—C17B—N17B | −179.72 (17) |
N21A—N20A—C17A—N17A | −179.65 (18) | C15B—C16B—C17B—N17B | 2.6 (3) |
C23A—N20A—C17A—N17A | 7.0 (3) | N21B—N20B—C17B—C16B | 0.5 (2) |
C22A—C16A—C17A—N20A | 0.1 (2) | C23B—N20B—C17B—C16B | −170.63 (18) |
C15A—C16A—C17A—N20A | 179.76 (16) | N21B—N20B—C17B—N17B | −179.97 (17) |
C22A—C16A—C17A—N17A | 179.16 (19) | C23B—N20B—C17B—N17B | 8.9 (3) |
C15A—C16A—C17A—N17A | −1.2 (3) | C13B—N17B—C17B—C16B | 11.7 (3) |
C13A—N17A—C17A—N20A | −160.51 (16) | C13B—N17B—C17B—N20B | −167.76 (16) |
C13A—N17A—C17A—C16A | 20.6 (3) | N20B—N21B—C22B—C16B | 0.4 (2) |
N20A—N21A—C22A—C16A | −0.7 (2) | C17B—C16B—C22B—N21B | −0.1 (2) |
C17A—C16A—C22A—N21A | 0.4 (2) | C15B—C16B—C22B—N21B | 177.10 (19) |
C15A—C16A—C22A—N21A | −179.17 (19) | C17B—N20B—C23B—C24B | 17.4 (3) |
C17A—N20A—C23A—C24A | −42.9 (3) | N21B—N20B—C23B—C24B | −153.09 (19) |
N21A—N20A—C23A—C24A | 144.39 (19) | C17B—N20B—C23B—C28B | −165.45 (18) |
C17A—N20A—C23A—C28A | 136.8 (2) | N21B—N20B—C23B—C28B | 24.0 (3) |
N21A—N20A—C23A—C28A | −35.9 (3) | C28B—C23B—C24B—C25B | −0.5 (3) |
C28A—C23A—C24A—C25A | −1.9 (3) | N20B—C23B—C24B—C25B | 176.54 (17) |
N20A—C23A—C24A—C25A | 177.79 (18) | C23B—C24B—C25B—C26B | −0.8 (3) |
C23A—C24A—C25A—C26A | 2.5 (3) | C24B—C25B—C26B—C27B | 1.4 (3) |
C24A—C25A—C26A—F26A | 179.17 (18) | C24B—C25B—C26B—F26B | −178.54 (18) |
C24A—C25A—C26A—C27A | −1.3 (3) | C25B—C26B—C27B—C28B | −0.6 (4) |
F26A—C26A—C27A—C28A | 179.01 (18) | F26B—C26B—C27B—C28B | 179.29 (17) |
C25A—C26A—C27A—C28A | −0.5 (3) | C24B—C23B—C28B—C27B | 1.3 (3) |
C26A—C27A—C28A—C23A | 1.2 (3) | N20B—C23B—C28B—C27B | −175.86 (18) |
C24A—C23A—C28A—C27A | 0.0 (3) | C26B—C27B—C28B—C23B | −0.7 (3) |
N20A—C23A—C28A—C27A | −179.64 (17) | C19A—C10A—C13A—C18A | −1.31 (15) |
C17B—N20B—N21B—C22B | −0.6 (2) | C19B—C10B—C13B—C18B | 1.88 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C24B—H242···N17B | 0.95 | 2.36 | 2.990 (2) | 123 |
N17A—H171···O3Bi | 0.86 (2) | 2.16 (2) | 2.975 (2) | 158.6 (19) |
N17B—H172···N21Aii | 0.83 (2) | 2.54 (2) | 3.281 (2) | 149 (2) |
C4A—H41···N21Biii | 0.95 | 2.61 | 3.467 (2) | 151 |
C27A—H271···F26Ai | 0.95 | 2.41 | 3.320 (2) | 161 |
C27B—H272···F26Biii | 0.95 | 2.42 | 3.365 (3) | 171 |
Symmetry codes: (i) −x+2, y+1/2, −z+1; (ii) x, y−1, z; (iii) −x+1, y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C26H30FN3O |
Mr | 419.53 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 160 |
a, b, c (Å) | 13.5243 (2), 7.3983 (1), 21.8934 (3) |
β (°) | 102.1562 (8) |
V (Å3) | 2141.47 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.30 × 0.28 × 0.15 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 64206, 6714, 5595 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.100, 1.02 |
No. of reflections | 6704 |
No. of parameters | 571 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.23, −0.19 |
Computer programs: COLLECT (Nonius, 2000), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97 and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
C24B—H242···N17B | 0.95 | 2.36 | 2.990 (2) | 123 |
N17A—H171···O3Bi | 0.86 (2) | 2.16 (2) | 2.975 (2) | 158.6 (19) |
N17B—H172···N21Aii | 0.83 (2) | 2.54 (2) | 3.281 (2) | 149 (2) |
C4A—H41···N21Biii | 0.95 | 2.61 | 3.467 (2) | 151 |
C27A—H271···F26Ai | 0.95 | 2.41 | 3.320 (2) | 161 |
C27B—H272···F26Biii | 0.95 | 2.42 | 3.365 (3) | 171 |
Symmetry codes: (i) −x+2, y+1/2, −z+1; (ii) x, y−1, z; (iii) −x+1, y+1/2, −z. |
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There has been considerable interest in the synthesis and biological activity of several heterocyclic steroids as extremely potent antiinflammatory agents (Gupta et al., 1996, and references therein). In the 17a-aza series, the presence of an α,β-unsaturated ketone produced compounds with good activity, while hydroxy and acetoxy derivatives were found to be inactive. The fusion of pyrazole ring systems at the 2,3- and 16,17-positions of azasteroids afforded compounds with enhanced antiinflammatory activity compared with standard drugs in the androstane series (Gupta et al., 1996). Crystal structure analyses have been carried out in order to study the influence of the fused pyrazole moiety on the steroid skeleton. The present study extends our ongoing investigation of a series of similar ring-A– or ring-D-modified steroids. In a previous paper, we reported two ring-A-modified steroids, namely 2'-(p-fluorophenyl)-4-azapyrazolo[4',3':2,3]-5α-androstan-17β-yl acetate and 2'-(p-fluorophenyl)-4-azapyrazolo[4',3':2,3]-5α-androstan-17β-ol (Thamotharan et al., 2003). In this paper, we report the crystal and molecular structure of a ring-D-modified steroid, namely 2'-(p-fluorophenyl)-17a-aza-D-homo-4-androsteno[17,16 − c]pyrazol-3-one, (I). \sch
The crystals of (I) are enantiomerically pure. However, due to the absence of any significant anomalous scatterers in the compound, the absolute configuration of the molecule has not been determined by the X-ray diffraction experiment. The enantiomer used in the refinement was assumed to correspond with the configuration of the known chiral centres in a precursor molecule, which remained unchanged during the synthesis of (I).
There are two symmetry-independent molecules, A and B, in the asymmetric unit of (I), and these are depicted in Fig. 1. The corresponding bond lengths and angles for the independent molecules agree well with each other. Excluding the atoms of the p-fluorophenyl group, the core skeletons of the two molecules have the same absolute configuration and almost identical conformations, with only very minor differences in the puckering of some rings. The unweighted r.m.s. fit of the remaining non-H atoms of molecule A with the corresponding atoms of molecule B is 0.12 Å. The main difference between the conformations of the two molecules is the orientation of the plane of the p-fluorophenyl ring in molecule B, which is tilted by approximately 63° with respect to its orientation in molecule A. The angle between the mean planes through the p-fluorophenyl ring (excluding the F atom) and the pyrazole ring is 38.85 (11)° for molecule A and −23.86 (11)° for molecule B. Another difference between the two symmetry-independent molecules is that the positions of the lone electron pair and the H atom on atom N17B in molecule B are reversed with respect to their positions on atom N17A in molecule A. This effective inversion of the configuration at this N atom also has consequences for the hydrogen-bonding interactions, as described below.
In both independent molecules, the methyl groups C18 and C19 lie in the expected β orientation, while the geometry at the B/C and C/D ring junctions is all-trans. The C4═C5 distances of 1.343 (3) and 1.346 (3) Å in molecules A and B, respectively, confirm the localization of the double bond at these positions.
The cyclohexenone ring A adopts a slightly distorted envelope conformation in both independent molecules, with the distortion being more severe and slightly towards a half-chair conformation in molecule A. Atoms C1A and C1B form the envelope flap in the respective molecules and the conformation of this ring is a consequence of the C4═C5 alkene bond. The puckering parameters (Cremer & Pople, 1975) for this ring in molecule A are Q = 0.436 (2) Å, q2 = 0.347 (2) Å, q3 = 0.265 (2) Å, θ = 52.7 (3)° and ϕ2 = 12.2 (4)° for the atom sequence C1A—C5A/C10A, while for molecule B, Q = 0.450 (2) Å, q2 = 0.371 (2) Å, q3 = 0.254 (2) Å, θ = 55.7 (3)° and ϕ2 = 8.2 (3)° for the atom sequence C1B—C5B/C10B.
The steroidal ring B exists in a slightly distorted chair conformation in both molecules, with puckering parameters for molecule A [molecule B in brackets] of Q = 0.543 (2) Å [0.529 (2) Å], q2 = 0.099 (2) Å [0.082 (2) Å], q3 = 0.534 (2) Å [0.522 (2) Å], θ = 10.6 (2)° [9.2 (2)°] and ϕ2 = 195.1 (12)° [192.7 (14)°] for the atom sequence C5A—C10A [C5B—C10B].
Ring C has a chair conformation in both molecules, although it is slightly more distorted in molecule A than in molecule B. The puckering parameters for molecule A [molecule B in brackets] are Q = 0.559 (2) Å [0.570 (2) Å], q2 = 0.077 (2) Å [0.041 (2) Å], q3 = 0.554 (2) Å [0.568 (2) Å], θ = 7.6 (2)° [3.9 (2)°] and ϕ2 = 218.0 (15)° [207 (3)°] for the atom sequence C8A/C9A/C11A—C14A [C8B/C9B/C11B—C14B]. The tetrahydropyridine ring D of the steroid nucleus adopts a half-chair conformation in both molecules A and B, twisted on C13A—C14A and C13B—C14B, respectively. The ring is considerably strained as a consequence of the presence of the fused planar pyrazole ring. The puckering parameters for ring D in molecule A [molecule B in brackets] are Q = 0.497 (2) Å [0.480 (2) Å], q2 = 0.379 (2) Å [0.377 (2) Å], q3 = 0.323 (2) Å [0.297 (2) Å], θ = 49.6 (2)° [51.8 (2)°] and ϕ2 = 83.5 (3)° [94.4 (3)°] for the atom sequence N17A/C13A—C17A [N17B/C13B—C17B].
The pseudo-torsion angles C19A—C10A···C13A—C18A [−1.31 (15)°] in molecule A and C19B—C10B···C13B—C18B [1.88 (17)°] in molecule B provide a quantitative measure of the twist about the length of the molecule and show that the molecules in (I) are not twisted to any significant degree and, with the exception of the tilted p-fluorphenyl group, that the entire molecule is quite flat. The values are comparable with those of related structures (Thamotharan et al., 2003).
In (I), atom C24B forms a weak intramolecular C—H···N interaction (Table 1) with atom N17B of molecule B, which leads to a loop with a graph-set motif of S(6) (Bernstein et al., 1995). Atoms C27A and C27B are involved in weak intermolecular C—H···F interactions with atoms F26A and F26B, respectively, of two different adjacent molecules, and each interaction links the A and B molecules independently into chains which have graph-set motifs of C(4) and run parallel to the y axis. Atoms N17A and N17B participate in intermolecular N—H···O or N—H···N hydrogen bonds with atoms O3B and N21A, respectively, of two different neighbouring molecules. These interactions serve to cross-link molecules A with B and act cooperatively to produce chains of alternating A and B molecules which have a graph-set motif of C22(16) and run parallel to the y axis. Atom C4A acts as donor for a weak intermolecular C—H···N interaction with atom N21B of an adjacent molecule.