The title compounds, C24H30N2O3, (I), and C24H34N2O3, (II), both contain an androstane backbone and a 2-methylimidazole-1-carboxylate moiety at the 17-position. Compound (I) contains two symmetry-independent molecules (denoted 1 and 2), while compound (II) contains just one molecule in the asymmetric unit. The C-C-O-C torsion angle that reflects the twisting of the 2-methylimidazole-1-carboxylate moiety from the mean steroid plane is 143.1 (2)° for molecule 1 of (I), 73.1 (3)° for molecule 2 of (I) and 86.63 (17)° for (II). The significance of this study lies in its observation of significant differences in both molecular conformation and supramolecular aggregation between the molecules of the title compounds. The solid-state conformations compared with those obtained theoretically from ab initio methods for the isolated molecules show large differences, especially in the orientation of the methylimidazole substituent.
Supporting information
CCDC references: 728208; 728209
Both compounds were synthesized as described previously (Moreira, Salvador
et al., 2008 or Moreira, Vasaitis et
al., 2008 ?). Compound (I) was crystallized from acetone by
slow evaporation. Compound (II) was crystallized from acetonitrile by slow
evaporation.
All H atoms were refined as riding on their parent atoms, with C—H =
0.93–0.98 Å, and with Uiso(H) = 1.2Ueq(C) or
1.5Ueq(methyl C). The absolute configuration was not determined from
the X-ray data but was known from the synthesis route. Friedel pairs were
merged before refinement.
For both compounds, data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
(I) 3-Oxoandrosta-4,6-dien-17
β-yl 2-methyl-1
H-imidazole-1-carboxylate
top
Crystal data top
C24H30N2O3 | F(000) = 1696 |
Mr = 394.50 | Dx = 1.256 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
a = 24.5935 (5) Å | Cell parameters from 7283 reflections |
b = 7.0351 (1) Å | θ = 2.5–21.0° |
c = 24.9875 (4) Å | µ = 0.08 mm−1 |
β = 105.1160 (11)° | T = 293 K |
V = 4173.69 (12) Å3 | Plate, colourless |
Z = 8 | 0.36 × 0.15 × 0.04 mm |
Data collection top
Bruker APEX CCD area-detector diffractometer | 5398 independent reflections |
Radiation source: fine-focus sealed tube | 3688 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
ϕ and ω scans | θmax = 28.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −32→32 |
Tmin = 0.906, Tmax = 0.997 | k = −9→9 |
45077 measured reflections | l = −32→32 |
Refinement top
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0502P)2 + 0.5036P] where P = (Fo2 + 2Fc2)/3 |
5398 reflections | (Δ/σ)max < 0.001 |
529 parameters | Δρmax = 0.13 e Å−3 |
1 restraint | Δρmin = −0.20 e Å−3 |
Crystal data top
C24H30N2O3 | V = 4173.69 (12) Å3 |
Mr = 394.50 | Z = 8 |
Monoclinic, C2 | Mo Kα radiation |
a = 24.5935 (5) Å | µ = 0.08 mm−1 |
b = 7.0351 (1) Å | T = 293 K |
c = 24.9875 (4) Å | 0.36 × 0.15 × 0.04 mm |
β = 105.1160 (11)° | |
Data collection top
Bruker APEX CCD area-detector diffractometer | 5398 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 3688 reflections with I > 2σ(I) |
Tmin = 0.906, Tmax = 0.997 | Rint = 0.052 |
45077 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 1 restraint |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.13 e Å−3 |
5398 reflections | Δρmin = −0.20 e Å−3 |
529 parameters | |
Special details top
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 | |
C1 | 0.67506 (13) | −0.0818 (5) | 0.47461 (11) | 0.0599 (8) | |
H1A | 0.6578 | −0.1923 | 0.4538 | 0.072* | |
H1B | 0.6956 | −0.0143 | 0.4522 | 0.072* | |
C2 | 0.71638 (14) | −0.1477 (5) | 0.52785 (12) | 0.0714 (10) | |
H2A | 0.6972 | −0.2334 | 0.5473 | 0.086* | |
H2B | 0.7467 | −0.2177 | 0.5187 | 0.086* | |
C3 | 0.74054 (13) | 0.0130 (5) | 0.56499 (11) | 0.0599 (8) | |
O1 | 0.78870 (9) | 0.0072 (4) | 0.59467 (8) | 0.0803 (8) | |
C4 | 0.70420 (12) | 0.1756 (5) | 0.56466 (10) | 0.0533 (7) | |
H4 | 0.7166 | 0.2707 | 0.5909 | 0.064* | |
C5 | 0.65355 (12) | 0.1957 (4) | 0.52836 (10) | 0.0440 (6) | |
C6 | 0.61938 (11) | 0.3635 (4) | 0.52950 (10) | 0.0481 (7) | |
H6 | 0.6305 | 0.4470 | 0.5592 | 0.058* | |
C7 | 0.57307 (12) | 0.4028 (4) | 0.48998 (10) | 0.0455 (6) | |
H7 | 0.5522 | 0.5091 | 0.4945 | 0.055* | |
C8 | 0.55243 (11) | 0.2865 (4) | 0.43871 (9) | 0.0399 (6) | |
H8 | 0.5216 | 0.2056 | 0.4434 | 0.048* | |
C9 | 0.60007 (11) | 0.1578 (4) | 0.43047 (9) | 0.0406 (6) | |
H9 | 0.6290 | 0.2434 | 0.4236 | 0.049* | |
C10 | 0.62846 (11) | 0.0485 (4) | 0.48459 (10) | 0.0435 (6) | |
C11 | 0.58070 (12) | 0.0355 (4) | 0.37815 (10) | 0.0515 (7) | |
H11A | 0.5523 | −0.0537 | 0.3831 | 0.062* | |
H11B | 0.6124 | −0.0371 | 0.3729 | 0.062* | |
C12 | 0.55622 (12) | 0.1565 (4) | 0.32623 (10) | 0.0507 (7) | |
H12A | 0.5859 | 0.2339 | 0.3184 | 0.061* | |
H12B | 0.5418 | 0.0735 | 0.2947 | 0.061* | |
C13 | 0.50900 (11) | 0.2848 (4) | 0.33405 (9) | 0.0417 (6) | |
C14 | 0.53085 (11) | 0.4068 (4) | 0.38653 (9) | 0.0406 (6) | |
H14 | 0.5633 | 0.4778 | 0.3812 | 0.049* | |
C15 | 0.48390 (12) | 0.5523 (4) | 0.38357 (10) | 0.0518 (7) | |
H15A | 0.4986 | 0.6681 | 0.4031 | 0.062* | |
H15B | 0.4548 | 0.5011 | 0.3992 | 0.062* | |
C16 | 0.46091 (14) | 0.5893 (4) | 0.32056 (11) | 0.0569 (8) | |
H16A | 0.4206 | 0.5676 | 0.3088 | 0.068* | |
H16B | 0.4686 | 0.7189 | 0.3115 | 0.068* | |
C17 | 0.49220 (12) | 0.4477 (4) | 0.29288 (10) | 0.0469 (7) | |
H17 | 0.5262 | 0.5079 | 0.2872 | 0.056* | |
C18 | 0.45672 (12) | 0.1660 (4) | 0.33553 (12) | 0.0550 (8) | |
H18A | 0.4272 | 0.2489 | 0.3400 | 0.082* | |
H18B | 0.4663 | 0.0785 | 0.3660 | 0.082* | |
H18C | 0.4441 | 0.0965 | 0.3015 | 0.082* | |
C19 | 0.58543 (13) | −0.0678 (4) | 0.50591 (12) | 0.0593 (8) | |
H19A | 0.6049 | −0.1439 | 0.5369 | 0.089* | |
H19B | 0.5646 | −0.1490 | 0.4768 | 0.089* | |
H19C | 0.5600 | 0.0169 | 0.5173 | 0.089* | |
O2 | 0.45513 (7) | 0.3927 (3) | 0.23914 (6) | 0.0492 (5) | |
C20 | 0.47925 (12) | 0.3664 (4) | 0.19823 (10) | 0.0460 (7) | |
O3 | 0.52863 (8) | 0.3654 (4) | 0.20117 (7) | 0.0650 (6) | |
N1 | 0.43759 (8) | 0.3413 (3) | 0.14802 (8) | 0.0409 (5) | |
C21 | 0.44604 (11) | 0.3181 (4) | 0.09593 (10) | 0.0472 (6) | |
C22 | 0.50168 (13) | 0.3150 (7) | 0.08342 (12) | 0.0786 (11) | |
H22A | 0.4971 | 0.2752 | 0.0458 | 0.118* | |
H22B | 0.5261 | 0.2279 | 0.1080 | 0.118* | |
H22C | 0.5178 | 0.4401 | 0.0884 | 0.118* | |
N2 | 0.39832 (10) | 0.3040 (4) | 0.05845 (8) | 0.0548 (6) | |
C23 | 0.35725 (12) | 0.3179 (5) | 0.08698 (11) | 0.0566 (7) | |
H23 | 0.3187 | 0.3124 | 0.0705 | 0.068* | |
C24 | 0.38017 (10) | 0.3402 (4) | 0.14131 (11) | 0.0481 (7) | |
H24A | 0.3613 | 0.3524 | 0.1689 | 0.058* | |
C25 | 0.30834 (14) | 0.2744 (4) | −0.24470 (11) | 0.0536 (7) | |
H25A | 0.3485 | 0.2501 | −0.2321 | 0.064* | |
H25B | 0.2903 | 0.2102 | −0.2195 | 0.064* | |
C26 | 0.28595 (14) | 0.1902 (4) | −0.30295 (11) | 0.0607 (8) | |
H26A | 0.3073 | 0.2415 | −0.3272 | 0.073* | |
H26B | 0.2912 | 0.0534 | −0.3012 | 0.073* | |
C27 | 0.22503 (15) | 0.2337 (5) | −0.32644 (11) | 0.0601 (9) | |
O4 | 0.19278 (11) | 0.1228 (4) | −0.35642 (9) | 0.0912 (8) | |
C28 | 0.20638 (12) | 0.4181 (4) | −0.31216 (10) | 0.0508 (7) | |
H28 | 0.1700 | 0.4565 | −0.3301 | 0.061* | |
C29 | 0.23814 (11) | 0.5365 (4) | −0.27492 (9) | 0.0410 (6) | |
C30 | 0.21623 (11) | 0.7195 (4) | −0.26304 (11) | 0.0458 (7) | |
H30 | 0.1835 | 0.7650 | −0.2874 | 0.055* | |
C31 | 0.24033 (10) | 0.8240 (4) | −0.21947 (10) | 0.0443 (6) | |
H31 | 0.2241 | 0.9405 | −0.2151 | 0.053* | |
C32 | 0.29242 (10) | 0.7650 (3) | −0.17661 (9) | 0.0368 (6) | |
H32 | 0.3246 | 0.8336 | −0.1836 | 0.044* | |
C33 | 0.30255 (10) | 0.5501 (4) | −0.18126 (9) | 0.0365 (6) | |
H33 | 0.2714 | 0.4865 | −0.1708 | 0.044* | |
C34 | 0.29809 (11) | 0.4895 (4) | −0.24217 (10) | 0.0392 (6) | |
C35 | 0.35634 (11) | 0.4871 (4) | −0.13862 (9) | 0.0445 (6) | |
H35A | 0.3886 | 0.5494 | −0.1465 | 0.053* | |
H35B | 0.3611 | 0.3510 | −0.1416 | 0.053* | |
C36 | 0.35392 (11) | 0.5364 (4) | −0.07941 (10) | 0.0455 (7) | |
H36A | 0.3238 | 0.4649 | −0.0703 | 0.055* | |
H36B | 0.3891 | 0.5001 | −0.0535 | 0.055* | |
C37 | 0.34384 (10) | 0.7489 (4) | −0.07362 (10) | 0.0373 (6) | |
C38 | 0.28982 (10) | 0.8076 (4) | −0.11761 (9) | 0.0370 (5) | |
H38 | 0.2595 | 0.7283 | −0.1109 | 0.044* | |
C39 | 0.27846 (12) | 1.0092 (4) | −0.10066 (10) | 0.0491 (7) | |
H39A | 0.2388 | 1.0407 | −0.1137 | 0.059* | |
H39B | 0.3002 | 1.1016 | −0.1152 | 0.059* | |
C40 | 0.29742 (12) | 1.0030 (4) | −0.03681 (10) | 0.0513 (7) | |
H40A | 0.3241 | 1.1040 | −0.0225 | 0.062* | |
H40B | 0.2654 | 1.0166 | −0.0213 | 0.062* | |
C41 | 0.32501 (10) | 0.8087 (4) | −0.02259 (9) | 0.0412 (6) | |
H41A | 0.2969 | 0.7182 | −0.0165 | 0.049* | |
C42 | 0.39582 (11) | 0.8651 (5) | −0.07702 (11) | 0.0522 (7) | |
H42A | 0.3897 | 0.9967 | −0.0704 | 0.078* | |
H42B | 0.4019 | 0.8509 | −0.1132 | 0.078* | |
H42C | 0.4283 | 0.8200 | −0.0496 | 0.078* | |
C43 | 0.34008 (11) | 0.5984 (4) | −0.26712 (10) | 0.0479 (7) | |
H43A | 0.3367 | 0.5548 | −0.3043 | 0.072* | |
H43B | 0.3777 | 0.5762 | −0.2450 | 0.072* | |
H43C | 0.3320 | 0.7320 | −0.2677 | 0.072* | |
O5 | 0.37301 (7) | 0.8122 (3) | 0.02642 (6) | 0.0449 (4) | |
C44 | 0.35960 (11) | 0.8305 (4) | 0.07410 (10) | 0.0408 (6) | |
O6 | 0.31303 (8) | 0.8408 (3) | 0.08028 (7) | 0.0559 (5) | |
N3 | 0.40849 (8) | 0.8364 (3) | 0.11802 (8) | 0.0401 (5) | |
C45 | 0.41188 (11) | 0.8512 (4) | 0.17415 (9) | 0.0424 (6) | |
C46 | 0.36256 (11) | 0.8561 (5) | 0.19779 (10) | 0.0604 (8) | |
H46A | 0.3753 | 0.8600 | 0.2375 | 0.091* | |
H46B | 0.3401 | 0.7444 | 0.1865 | 0.091* | |
H46C | 0.3404 | 0.9671 | 0.1846 | 0.091* | |
N4 | 0.46383 (10) | 0.8592 (4) | 0.20318 (9) | 0.0555 (6) | |
C47 | 0.49603 (12) | 0.8483 (5) | 0.16537 (11) | 0.0604 (8) | |
H47 | 0.5352 | 0.8511 | 0.1748 | 0.072* | |
C48 | 0.46369 (11) | 0.8332 (5) | 0.11395 (11) | 0.0520 (7) | |
H48 | 0.4756 | 0.8227 | 0.0817 | 0.062* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.067 (2) | 0.0626 (19) | 0.0455 (16) | 0.0133 (16) | 0.0068 (15) | −0.0047 (14) |
C2 | 0.076 (2) | 0.083 (2) | 0.0486 (16) | 0.030 (2) | 0.0037 (15) | 0.0012 (17) |
C3 | 0.056 (2) | 0.090 (2) | 0.0318 (14) | 0.0091 (18) | 0.0079 (14) | 0.0104 (16) |
O1 | 0.0592 (15) | 0.124 (2) | 0.0490 (12) | 0.0149 (15) | −0.0008 (11) | 0.0149 (14) |
C4 | 0.0545 (19) | 0.071 (2) | 0.0304 (14) | −0.0051 (16) | 0.0034 (13) | −0.0031 (13) |
C5 | 0.0510 (17) | 0.0498 (16) | 0.0311 (13) | −0.0049 (13) | 0.0108 (13) | 0.0010 (11) |
C6 | 0.0589 (18) | 0.0501 (16) | 0.0316 (13) | −0.0073 (15) | 0.0049 (12) | −0.0092 (12) |
C7 | 0.0582 (18) | 0.0424 (14) | 0.0345 (13) | −0.0021 (13) | 0.0098 (13) | −0.0059 (11) |
C8 | 0.0455 (15) | 0.0399 (13) | 0.0338 (12) | −0.0080 (12) | 0.0094 (11) | −0.0013 (11) |
C9 | 0.0473 (16) | 0.0426 (14) | 0.0312 (12) | −0.0027 (12) | 0.0090 (11) | −0.0031 (11) |
C10 | 0.0490 (16) | 0.0437 (15) | 0.0350 (13) | −0.0001 (13) | 0.0060 (11) | −0.0030 (11) |
C11 | 0.0567 (18) | 0.0521 (17) | 0.0402 (14) | 0.0057 (14) | 0.0026 (12) | −0.0093 (13) |
C12 | 0.0548 (18) | 0.0602 (18) | 0.0337 (14) | 0.0038 (15) | 0.0054 (12) | −0.0070 (13) |
C13 | 0.0460 (16) | 0.0476 (14) | 0.0277 (12) | −0.0073 (12) | 0.0028 (11) | −0.0051 (11) |
C14 | 0.0457 (15) | 0.0410 (14) | 0.0338 (13) | −0.0079 (12) | 0.0083 (11) | −0.0034 (11) |
C15 | 0.069 (2) | 0.0483 (16) | 0.0343 (13) | 0.0025 (15) | 0.0079 (13) | −0.0035 (12) |
C16 | 0.074 (2) | 0.0503 (16) | 0.0409 (15) | 0.0060 (15) | 0.0045 (14) | 0.0008 (13) |
C17 | 0.0506 (17) | 0.0556 (17) | 0.0302 (13) | −0.0108 (13) | 0.0026 (12) | 0.0006 (11) |
C18 | 0.058 (2) | 0.0518 (16) | 0.0498 (17) | −0.0143 (15) | 0.0050 (15) | −0.0033 (14) |
C19 | 0.069 (2) | 0.0501 (17) | 0.0532 (18) | −0.0125 (15) | 0.0065 (15) | 0.0044 (14) |
O2 | 0.0481 (11) | 0.0670 (12) | 0.0289 (9) | −0.0077 (10) | 0.0035 (8) | −0.0007 (9) |
C20 | 0.0465 (17) | 0.0538 (17) | 0.0336 (13) | −0.0071 (14) | 0.0031 (12) | 0.0027 (12) |
O3 | 0.0419 (12) | 0.1063 (18) | 0.0424 (10) | −0.0083 (13) | 0.0031 (9) | −0.0056 (12) |
N1 | 0.0398 (12) | 0.0482 (13) | 0.0316 (10) | −0.0054 (11) | 0.0038 (9) | −0.0013 (9) |
C21 | 0.0484 (17) | 0.0559 (16) | 0.0356 (13) | −0.0103 (14) | 0.0076 (12) | −0.0016 (13) |
C22 | 0.068 (2) | 0.126 (3) | 0.0455 (16) | −0.025 (2) | 0.0223 (15) | −0.014 (2) |
N2 | 0.0576 (15) | 0.0655 (15) | 0.0356 (12) | −0.0086 (13) | 0.0019 (11) | −0.0047 (11) |
C23 | 0.0460 (17) | 0.0659 (19) | 0.0516 (17) | 0.0011 (16) | 0.0015 (14) | −0.0074 (15) |
C24 | 0.0392 (16) | 0.0580 (17) | 0.0465 (15) | −0.0003 (14) | 0.0098 (12) | −0.0046 (14) |
C25 | 0.074 (2) | 0.0447 (16) | 0.0383 (14) | 0.0037 (15) | 0.0085 (14) | −0.0012 (12) |
C26 | 0.089 (2) | 0.0466 (16) | 0.0437 (16) | 0.0040 (16) | 0.0117 (16) | −0.0066 (13) |
C27 | 0.085 (2) | 0.0614 (19) | 0.0319 (15) | −0.0144 (18) | 0.0115 (15) | −0.0060 (14) |
O4 | 0.115 (2) | 0.0777 (17) | 0.0637 (14) | −0.0241 (16) | −0.0074 (14) | −0.0251 (13) |
C28 | 0.0484 (17) | 0.0680 (19) | 0.0321 (14) | −0.0080 (14) | 0.0035 (12) | −0.0012 (13) |
C29 | 0.0419 (15) | 0.0516 (16) | 0.0290 (12) | −0.0023 (13) | 0.0083 (11) | 0.0038 (11) |
C30 | 0.0378 (15) | 0.0580 (16) | 0.0372 (14) | 0.0020 (13) | 0.0017 (12) | 0.0060 (12) |
C31 | 0.0425 (15) | 0.0458 (14) | 0.0428 (14) | 0.0083 (13) | 0.0078 (11) | 0.0047 (12) |
C32 | 0.0352 (14) | 0.0402 (13) | 0.0339 (13) | −0.0021 (11) | 0.0068 (11) | 0.0011 (10) |
C33 | 0.0371 (14) | 0.0418 (14) | 0.0303 (12) | 0.0000 (11) | 0.0083 (10) | 0.0012 (10) |
C34 | 0.0422 (15) | 0.0436 (13) | 0.0303 (12) | 0.0025 (12) | 0.0069 (11) | 0.0010 (11) |
C35 | 0.0478 (16) | 0.0487 (15) | 0.0335 (13) | 0.0093 (13) | 0.0043 (11) | −0.0018 (12) |
C36 | 0.0459 (16) | 0.0550 (17) | 0.0330 (13) | 0.0102 (13) | 0.0056 (11) | 0.0042 (12) |
C37 | 0.0338 (14) | 0.0471 (14) | 0.0310 (12) | −0.0022 (11) | 0.0085 (11) | −0.0014 (10) |
C38 | 0.0352 (13) | 0.0402 (13) | 0.0348 (12) | −0.0006 (11) | 0.0081 (10) | −0.0028 (11) |
C39 | 0.0538 (18) | 0.0482 (15) | 0.0422 (14) | 0.0059 (13) | 0.0070 (12) | −0.0062 (13) |
C40 | 0.0479 (17) | 0.0577 (17) | 0.0463 (15) | 0.0062 (14) | 0.0089 (13) | −0.0145 (14) |
C41 | 0.0370 (14) | 0.0522 (15) | 0.0329 (12) | −0.0083 (12) | 0.0066 (11) | −0.0040 (11) |
C42 | 0.0409 (15) | 0.072 (2) | 0.0434 (14) | −0.0126 (15) | 0.0107 (12) | −0.0027 (14) |
C43 | 0.0479 (17) | 0.0572 (17) | 0.0393 (14) | 0.0014 (14) | 0.0127 (12) | 0.0011 (13) |
O5 | 0.0426 (10) | 0.0621 (11) | 0.0295 (8) | −0.0048 (9) | 0.0084 (7) | −0.0049 (8) |
C44 | 0.0451 (16) | 0.0423 (14) | 0.0350 (13) | −0.0057 (13) | 0.0105 (12) | −0.0035 (11) |
O6 | 0.0447 (11) | 0.0819 (15) | 0.0421 (10) | −0.0101 (11) | 0.0131 (8) | −0.0080 (10) |
N3 | 0.0403 (12) | 0.0475 (13) | 0.0329 (10) | −0.0021 (11) | 0.0104 (9) | −0.0024 (9) |
C45 | 0.0505 (16) | 0.0445 (15) | 0.0320 (12) | −0.0006 (13) | 0.0103 (12) | 0.0006 (11) |
C46 | 0.0585 (18) | 0.085 (2) | 0.0412 (15) | −0.0010 (18) | 0.0192 (13) | −0.0038 (16) |
N4 | 0.0514 (15) | 0.0719 (17) | 0.0398 (12) | −0.0015 (13) | 0.0056 (11) | 0.0028 (12) |
C47 | 0.0411 (16) | 0.088 (2) | 0.0497 (16) | −0.0005 (17) | 0.0074 (13) | 0.0043 (17) |
C48 | 0.0449 (16) | 0.070 (2) | 0.0435 (15) | 0.0022 (16) | 0.0163 (13) | 0.0014 (15) |
Geometric parameters (Å, º) top
C1—C2 | 1.521 (4) | C25—C26 | 1.535 (4) |
C1—C10 | 1.538 (4) | C25—C34 | 1.538 (4) |
C1—H1A | 0.9700 | C25—H25A | 0.9700 |
C1—H1B | 0.9700 | C25—H25B | 0.9700 |
C2—C3 | 1.485 (5) | C26—C27 | 1.491 (5) |
C2—H2A | 0.9700 | C26—H26A | 0.9700 |
C2—H2B | 0.9700 | C26—H26B | 0.9700 |
C3—O1 | 1.223 (3) | C27—O4 | 1.221 (4) |
C3—C4 | 1.450 (5) | C27—C28 | 1.451 (5) |
C4—C5 | 1.344 (4) | C28—C29 | 1.338 (4) |
C4—H4 | 0.9300 | C28—H28 | 0.9300 |
C5—C6 | 1.454 (4) | C29—C30 | 1.456 (4) |
C5—C10 | 1.516 (4) | C29—C34 | 1.524 (4) |
C6—C7 | 1.327 (3) | C30—C31 | 1.319 (4) |
C6—H6 | 0.9300 | C30—H30 | 0.9300 |
C7—C8 | 1.493 (3) | C31—C32 | 1.498 (3) |
C7—H7 | 0.9300 | C31—H31 | 0.9300 |
C8—C14 | 1.529 (3) | C32—C38 | 1.522 (3) |
C8—C9 | 1.536 (4) | C32—C33 | 1.541 (3) |
C8—H8 | 0.9800 | C32—H32 | 0.9800 |
C9—C11 | 1.534 (3) | C33—C35 | 1.532 (3) |
C9—C10 | 1.554 (3) | C33—C34 | 1.557 (3) |
C9—H9 | 0.9800 | C33—H33 | 0.9800 |
C10—C19 | 1.538 (4) | C34—C43 | 1.542 (4) |
C11—C12 | 1.537 (4) | C35—C36 | 1.536 (3) |
C11—H11A | 0.9700 | C35—H35A | 0.9700 |
C11—H11B | 0.9700 | C35—H35B | 0.9700 |
C12—C13 | 1.523 (4) | C36—C37 | 1.528 (4) |
C12—H12A | 0.9700 | C36—H36A | 0.9700 |
C12—H12B | 0.9700 | C36—H36B | 0.9700 |
C13—C17 | 1.523 (4) | C37—C41 | 1.525 (3) |
C13—C14 | 1.542 (3) | C37—C42 | 1.538 (4) |
C13—C18 | 1.542 (4) | C37—C38 | 1.544 (3) |
C14—C15 | 1.530 (4) | C38—C39 | 1.527 (4) |
C14—H14 | 0.9800 | C38—H38 | 0.9800 |
C15—C16 | 1.550 (4) | C39—C40 | 1.542 (4) |
C15—H15A | 0.9700 | C39—H39A | 0.9700 |
C15—H15B | 0.9700 | C39—H39B | 0.9700 |
C16—C17 | 1.530 (4) | C40—C41 | 1.526 (4) |
C16—H16A | 0.9700 | C40—H40A | 0.9700 |
C16—H16B | 0.9700 | C40—H40B | 0.9700 |
C17—O2 | 1.465 (3) | C41—O5 | 1.463 (3) |
C17—H17 | 0.9800 | C41—H41A | 0.9800 |
C18—H18A | 0.9600 | C42—H42A | 0.9600 |
C18—H18B | 0.9600 | C42—H42B | 0.9600 |
C18—H18C | 0.9600 | C42—H42C | 0.9600 |
C19—H19A | 0.9600 | C43—H43A | 0.9600 |
C19—H19B | 0.9600 | C43—H43B | 0.9600 |
C19—H19C | 0.9600 | C43—H43C | 0.9600 |
O2—C20 | 1.322 (3) | O5—C44 | 1.323 (3) |
C20—O3 | 1.197 (3) | C44—O6 | 1.197 (3) |
C20—N1 | 1.409 (3) | C44—N3 | 1.401 (3) |
N1—C24 | 1.378 (3) | N3—C45 | 1.387 (3) |
N1—C21 | 1.380 (3) | N3—C48 | 1.388 (3) |
C21—N2 | 1.300 (3) | C45—N4 | 1.295 (3) |
C21—C22 | 1.481 (4) | C45—C46 | 1.482 (3) |
C22—H22A | 0.9600 | C46—H46A | 0.9600 |
C22—H22B | 0.9600 | C46—H46B | 0.9600 |
C22—H22C | 0.9600 | C46—H46C | 0.9600 |
N2—C23 | 1.383 (4) | N4—C47 | 1.384 (3) |
C23—C24 | 1.336 (4) | C47—C48 | 1.327 (4) |
C23—H23 | 0.9300 | C47—H47 | 0.9300 |
C24—H24A | 0.9300 | C48—H48 | 0.9300 |
| | | |
C2—C1—C10 | 113.3 (2) | C26—C25—C34 | 113.4 (2) |
C2—C1—H1A | 108.9 | C26—C25—H25A | 108.9 |
C10—C1—H1A | 108.9 | C34—C25—H25A | 108.9 |
C2—C1—H1B | 108.9 | C26—C25—H25B | 108.9 |
C10—C1—H1B | 108.9 | C34—C25—H25B | 108.9 |
H1A—C1—H1B | 107.7 | H25A—C25—H25B | 107.7 |
C3—C2—C1 | 112.4 (3) | C27—C26—C25 | 111.7 (3) |
C3—C2—H2A | 109.1 | C27—C26—H26A | 109.3 |
C1—C2—H2A | 109.1 | C25—C26—H26A | 109.3 |
C3—C2—H2B | 109.1 | C27—C26—H26B | 109.3 |
C1—C2—H2B | 109.1 | C25—C26—H26B | 109.3 |
H2A—C2—H2B | 107.8 | H26A—C26—H26B | 108.0 |
O1—C3—C4 | 121.9 (3) | O4—C27—C28 | 121.7 (3) |
O1—C3—C2 | 121.3 (3) | O4—C27—C26 | 122.4 (3) |
C4—C3—C2 | 116.8 (2) | C28—C27—C26 | 115.9 (3) |
C5—C4—C3 | 123.3 (3) | C29—C28—C27 | 124.2 (3) |
C5—C4—H4 | 118.4 | C29—C28—H28 | 117.9 |
C3—C4—H4 | 118.4 | C27—C28—H28 | 117.9 |
C4—C5—C6 | 120.7 (2) | C28—C29—C30 | 120.8 (3) |
C4—C5—C10 | 123.1 (3) | C28—C29—C34 | 123.1 (3) |
C6—C5—C10 | 116.1 (2) | C30—C29—C34 | 116.1 (2) |
C7—C6—C5 | 122.9 (2) | C31—C30—C29 | 123.4 (3) |
C7—C6—H6 | 118.6 | C31—C30—H30 | 118.3 |
C5—C6—H6 | 118.6 | C29—C30—H30 | 118.3 |
C6—C7—C8 | 123.9 (3) | C30—C31—C32 | 123.5 (3) |
C6—C7—H7 | 118.0 | C30—C31—H31 | 118.3 |
C8—C7—H7 | 118.0 | C32—C31—H31 | 118.3 |
C7—C8—C14 | 113.1 (2) | C31—C32—C38 | 113.2 (2) |
C7—C8—C9 | 109.7 (2) | C31—C32—C33 | 110.0 (2) |
C14—C8—C9 | 108.63 (19) | C38—C32—C33 | 108.3 (2) |
C7—C8—H8 | 108.4 | C31—C32—H32 | 108.4 |
C14—C8—H8 | 108.4 | C38—C32—H32 | 108.4 |
C9—C8—H8 | 108.4 | C33—C32—H32 | 108.4 |
C11—C9—C8 | 111.5 (2) | C35—C33—C32 | 111.0 (2) |
C11—C9—C10 | 115.7 (2) | C35—C33—C34 | 115.4 (2) |
C8—C9—C10 | 111.12 (19) | C32—C33—C34 | 111.8 (2) |
C11—C9—H9 | 105.9 | C35—C33—H33 | 106.0 |
C8—C9—H9 | 105.9 | C32—C33—H33 | 106.0 |
C10—C9—H9 | 105.9 | C34—C33—H33 | 106.0 |
C5—C10—C1 | 110.1 (2) | C29—C34—C25 | 109.7 (2) |
C5—C10—C19 | 107.5 (2) | C29—C34—C43 | 109.3 (2) |
C1—C10—C19 | 110.4 (2) | C25—C34—C43 | 109.7 (2) |
C5—C10—C9 | 107.2 (2) | C29—C34—C33 | 106.1 (2) |
C1—C10—C9 | 109.8 (2) | C25—C34—C33 | 109.8 (2) |
C19—C10—C9 | 111.8 (2) | C43—C34—C33 | 112.0 (2) |
C9—C11—C12 | 112.0 (2) | C33—C35—C36 | 111.2 (2) |
C9—C11—H11A | 109.2 | C33—C35—H35A | 109.4 |
C12—C11—H11A | 109.2 | C36—C35—H35A | 109.4 |
C9—C11—H11B | 109.2 | C33—C35—H35B | 109.4 |
C12—C11—H11B | 109.2 | C36—C35—H35B | 109.4 |
H11A—C11—H11B | 107.9 | H35A—C35—H35B | 108.0 |
C13—C12—C11 | 111.3 (2) | C37—C36—C35 | 111.1 (2) |
C13—C12—H12A | 109.4 | C37—C36—H36A | 109.4 |
C11—C12—H12A | 109.4 | C35—C36—H36A | 109.4 |
C13—C12—H12B | 109.4 | C37—C36—H36B | 109.4 |
C11—C12—H12B | 109.4 | C35—C36—H36B | 109.4 |
H12A—C12—H12B | 108.0 | H36A—C36—H36B | 108.0 |
C12—C13—C17 | 116.2 (2) | C41—C37—C36 | 116.2 (2) |
C12—C13—C14 | 109.3 (2) | C41—C37—C42 | 109.7 (2) |
C17—C13—C14 | 97.4 (2) | C36—C37—C42 | 110.9 (2) |
C12—C13—C18 | 110.5 (2) | C41—C37—C38 | 97.41 (19) |
C17—C13—C18 | 110.1 (2) | C36—C37—C38 | 109.0 (2) |
C14—C13—C18 | 112.9 (2) | C42—C37—C38 | 113.1 (2) |
C8—C14—C15 | 120.1 (2) | C32—C38—C39 | 120.6 (2) |
C8—C14—C13 | 112.6 (2) | C32—C38—C37 | 113.03 (19) |
C15—C14—C13 | 103.9 (2) | C39—C38—C37 | 103.7 (2) |
C8—C14—H14 | 106.5 | C32—C38—H38 | 106.2 |
C15—C14—H14 | 106.5 | C39—C38—H38 | 106.2 |
C13—C14—H14 | 106.5 | C37—C38—H38 | 106.2 |
C14—C15—C16 | 103.4 (2) | C38—C39—C40 | 103.4 (2) |
C14—C15—H15A | 111.1 | C38—C39—H39A | 111.1 |
C16—C15—H15A | 111.1 | C40—C39—H39A | 111.1 |
C14—C15—H15B | 111.1 | C38—C39—H39B | 111.1 |
C16—C15—H15B | 111.1 | C40—C39—H39B | 111.1 |
H15A—C15—H15B | 109.0 | H39A—C39—H39B | 109.0 |
C17—C16—C15 | 104.9 (2) | C41—C40—C39 | 105.2 (2) |
C17—C16—H16A | 110.8 | C41—C40—H40A | 110.7 |
C15—C16—H16A | 110.8 | C39—C40—H40A | 110.7 |
C17—C16—H16B | 110.8 | C41—C40—H40B | 110.7 |
C15—C16—H16B | 110.8 | C39—C40—H40B | 110.7 |
H16A—C16—H16B | 108.9 | H40A—C40—H40B | 108.8 |
O2—C17—C13 | 114.5 (2) | O5—C41—C37 | 110.48 (19) |
O2—C17—C16 | 108.7 (2) | O5—C41—C40 | 113.1 (2) |
C13—C17—C16 | 105.3 (2) | C37—C41—C40 | 105.4 (2) |
O2—C17—H17 | 109.4 | O5—C41—H41A | 109.2 |
C13—C17—H17 | 109.4 | C37—C41—H41A | 109.2 |
C16—C17—H17 | 109.4 | C40—C41—H41A | 109.2 |
C13—C18—H18A | 109.5 | C37—C42—H42A | 109.5 |
C13—C18—H18B | 109.5 | C37—C42—H42B | 109.5 |
H18A—C18—H18B | 109.5 | H42A—C42—H42B | 109.5 |
C13—C18—H18C | 109.5 | C37—C42—H42C | 109.5 |
H18A—C18—H18C | 109.5 | H42A—C42—H42C | 109.5 |
H18B—C18—H18C | 109.5 | H42B—C42—H42C | 109.5 |
C10—C19—H19A | 109.5 | C34—C43—H43A | 109.5 |
C10—C19—H19B | 109.5 | C34—C43—H43B | 109.5 |
H19A—C19—H19B | 109.5 | H43A—C43—H43B | 109.5 |
C10—C19—H19C | 109.5 | C34—C43—H43C | 109.5 |
H19A—C19—H19C | 109.5 | H43A—C43—H43C | 109.5 |
H19B—C19—H19C | 109.5 | H43B—C43—H43C | 109.5 |
C20—O2—C17 | 116.6 (2) | C44—O5—C41 | 114.80 (19) |
O3—C20—O2 | 127.3 (2) | O6—C44—O5 | 126.4 (2) |
O3—C20—N1 | 123.0 (2) | O6—C44—N3 | 123.5 (2) |
O2—C20—N1 | 109.7 (2) | O5—C44—N3 | 110.1 (2) |
C24—N1—C21 | 106.6 (2) | C45—N3—C48 | 105.9 (2) |
C24—N1—C20 | 126.4 (2) | C45—N3—C44 | 127.4 (2) |
C21—N1—C20 | 127.0 (2) | C48—N3—C44 | 126.7 (2) |
N2—C21—N1 | 111.0 (2) | N4—C45—N3 | 111.1 (2) |
N2—C21—C22 | 123.8 (2) | N4—C45—C46 | 124.5 (2) |
N1—C21—C22 | 125.1 (2) | N3—C45—C46 | 124.4 (2) |
C21—C22—H22A | 109.5 | C45—C46—H46A | 109.5 |
C21—C22—H22B | 109.5 | C45—C46—H46B | 109.5 |
H22A—C22—H22B | 109.5 | H46A—C46—H46B | 109.5 |
C21—C22—H22C | 109.5 | C45—C46—H46C | 109.5 |
H22A—C22—H22C | 109.5 | H46A—C46—H46C | 109.5 |
H22B—C22—H22C | 109.5 | H46B—C46—H46C | 109.5 |
C21—N2—C23 | 105.5 (2) | C45—N4—C47 | 105.8 (2) |
C24—C23—N2 | 111.1 (2) | C48—C47—N4 | 111.1 (2) |
C24—C23—H23 | 124.4 | C48—C47—H47 | 124.4 |
N2—C23—H23 | 124.4 | N4—C47—H47 | 124.4 |
C23—C24—N1 | 105.8 (2) | C47—C48—N3 | 106.2 (2) |
C23—C24—H24A | 127.1 | C47—C48—H48 | 126.9 |
N1—C24—H24A | 127.1 | N3—C48—H48 | 126.9 |
| | | |
C10—C1—C2—C3 | −52.8 (4) | C34—C25—C26—C27 | −54.9 (4) |
C1—C2—C3—O1 | −147.1 (3) | C25—C26—C27—O4 | −145.5 (3) |
C1—C2—C3—C4 | 33.5 (4) | C25—C26—C27—C28 | 35.5 (3) |
O1—C3—C4—C5 | 172.4 (3) | O4—C27—C28—C29 | 172.4 (3) |
C2—C3—C4—C5 | −8.1 (4) | C26—C27—C28—C29 | −8.5 (4) |
C3—C4—C5—C6 | −179.0 (3) | C27—C28—C29—C30 | 179.9 (2) |
C3—C4—C5—C10 | 1.3 (4) | C27—C28—C29—C34 | −0.9 (4) |
C4—C5—C6—C7 | 170.2 (3) | C28—C29—C30—C31 | 165.4 (3) |
C10—C5—C6—C7 | −10.1 (4) | C34—C29—C30—C31 | −13.8 (4) |
C5—C6—C7—C8 | −3.4 (4) | C29—C30—C31—C32 | −1.2 (4) |
C6—C7—C8—C14 | −138.3 (3) | C30—C31—C32—C38 | −137.8 (3) |
C6—C7—C8—C9 | −16.9 (4) | C30—C31—C32—C33 | −16.5 (3) |
C7—C8—C9—C11 | 180.0 (2) | C31—C32—C33—C35 | 178.79 (19) |
C14—C8—C9—C11 | −55.9 (3) | C38—C32—C33—C35 | −57.0 (3) |
C7—C8—C9—C10 | 49.4 (3) | C31—C32—C33—C34 | 48.4 (3) |
C14—C8—C9—C10 | 173.5 (2) | C38—C32—C33—C34 | 172.62 (19) |
C4—C5—C10—C1 | −19.7 (4) | C28—C29—C34—C25 | −17.4 (3) |
C6—C5—C10—C1 | 160.5 (2) | C30—C29—C34—C25 | 161.9 (2) |
C4—C5—C10—C19 | 100.6 (3) | C28—C29—C34—C43 | 103.0 (3) |
C6—C5—C10—C19 | −79.2 (3) | C30—C29—C34—C43 | −77.7 (3) |
C4—C5—C10—C9 | −139.1 (3) | C28—C29—C34—C33 | −136.0 (3) |
C6—C5—C10—C9 | 41.1 (3) | C30—C29—C34—C33 | 43.3 (3) |
C2—C1—C10—C5 | 44.7 (4) | C26—C25—C34—C29 | 44.5 (3) |
C2—C1—C10—C19 | −73.8 (3) | C26—C25—C34—C43 | −75.7 (3) |
C2—C1—C10—C9 | 162.5 (3) | C26—C25—C34—C33 | 160.7 (2) |
C11—C9—C10—C5 | 170.0 (2) | C35—C33—C34—C29 | 170.6 (2) |
C8—C9—C10—C5 | −61.6 (3) | C32—C33—C34—C29 | −61.4 (3) |
C11—C9—C10—C1 | 50.4 (3) | C35—C33—C34—C25 | 52.1 (3) |
C8—C9—C10—C1 | 178.9 (2) | C32—C33—C34—C25 | −179.9 (2) |
C11—C9—C10—C19 | −72.4 (3) | C35—C33—C34—C43 | −70.2 (3) |
C8—C9—C10—C19 | 56.0 (3) | C32—C33—C34—C43 | 57.9 (3) |
C8—C9—C11—C12 | 55.0 (3) | C32—C33—C35—C36 | 57.2 (3) |
C10—C9—C11—C12 | −176.8 (2) | C34—C33—C35—C36 | −174.3 (2) |
C9—C11—C12—C13 | −54.6 (3) | C33—C35—C36—C37 | −56.6 (3) |
C11—C12—C13—C17 | 164.0 (2) | C35—C36—C37—C41 | 164.2 (2) |
C11—C12—C13—C14 | 55.1 (3) | C35—C36—C37—C42 | −69.6 (3) |
C11—C12—C13—C18 | −69.7 (3) | C35—C36—C37—C38 | 55.5 (3) |
C7—C8—C14—C15 | −56.5 (3) | C31—C32—C38—C39 | −55.9 (3) |
C9—C8—C14—C15 | −178.6 (2) | C33—C32—C38—C39 | −178.2 (2) |
C7—C8—C14—C13 | −179.3 (2) | C31—C32—C38—C37 | −179.3 (2) |
C9—C8—C14—C13 | 58.6 (3) | C33—C32—C38—C37 | 58.4 (3) |
C12—C13—C14—C8 | −58.7 (3) | C41—C37—C38—C32 | −179.1 (2) |
C17—C13—C14—C8 | −179.8 (2) | C36—C37—C38—C32 | −58.1 (3) |
C18—C13—C14—C8 | 64.7 (3) | C42—C37—C38—C32 | 65.7 (3) |
C12—C13—C14—C15 | 169.8 (2) | C41—C37—C38—C39 | 48.7 (2) |
C17—C13—C14—C15 | 48.7 (2) | C36—C37—C38—C39 | 169.7 (2) |
C18—C13—C14—C15 | −66.7 (3) | C42—C37—C38—C39 | −66.5 (3) |
C8—C14—C15—C16 | −161.2 (2) | C32—C38—C39—C40 | −163.0 (2) |
C13—C14—C15—C16 | −34.3 (3) | C37—C38—C39—C40 | −35.3 (3) |
C14—C15—C16—C17 | 5.7 (3) | C38—C39—C40—C41 | 7.2 (3) |
C12—C13—C17—O2 | 79.9 (3) | C36—C37—C41—O5 | 78.1 (3) |
C14—C13—C17—O2 | −164.3 (2) | C42—C37—C41—O5 | −48.7 (3) |
C18—C13—C17—O2 | −46.6 (3) | C38—C37—C41—O5 | −166.5 (2) |
C12—C13—C17—C16 | −160.8 (2) | C36—C37—C41—C40 | −159.4 (2) |
C14—C13—C17—C16 | −45.0 (3) | C42—C37—C41—C40 | 73.8 (3) |
C18—C13—C17—C16 | 72.7 (3) | C38—C37—C41—C40 | −44.0 (2) |
C15—C16—C17—O2 | 148.4 (2) | C39—C40—C41—O5 | 144.6 (2) |
C15—C16—C17—C13 | 25.2 (3) | C39—C40—C41—C37 | 23.7 (3) |
C13—C17—O2—C20 | −99.4 (3) | C37—C41—O5—C44 | −168.9 (2) |
C16—C17—O2—C20 | 143.1 (2) | C40—C41—O5—C44 | 73.1 (3) |
C17—O2—C20—O3 | 7.4 (4) | C41—O5—C44—O6 | 1.3 (4) |
C17—O2—C20—N1 | −171.7 (2) | C41—O5—C44—N3 | −178.7 (2) |
O3—C20—N1—C24 | 179.8 (3) | O6—C44—N3—C45 | 1.1 (4) |
O2—C20—N1—C24 | −1.1 (4) | O5—C44—N3—C45 | −178.8 (2) |
O3—C20—N1—C21 | −2.0 (5) | O6—C44—N3—C48 | −177.1 (3) |
O2—C20—N1—C21 | 177.1 (2) | O5—C44—N3—C48 | 2.9 (4) |
C24—N1—C21—N2 | 0.3 (3) | C48—N3—C45—N4 | 0.7 (3) |
C20—N1—C21—N2 | −178.2 (3) | C44—N3—C45—N4 | −177.8 (2) |
C24—N1—C21—C22 | 178.6 (3) | C48—N3—C45—C46 | −178.9 (3) |
C20—N1—C21—C22 | 0.1 (5) | C44—N3—C45—C46 | 2.5 (4) |
N1—C21—N2—C23 | −0.2 (3) | N3—C45—N4—C47 | −0.3 (3) |
C22—C21—N2—C23 | −178.5 (3) | C46—C45—N4—C47 | 179.3 (3) |
C21—N2—C23—C24 | 0.0 (4) | C45—N4—C47—C48 | −0.2 (4) |
N2—C23—C24—N1 | 0.2 (4) | N4—C47—C48—N3 | 0.6 (4) |
C21—N1—C24—C23 | −0.3 (3) | C45—N3—C48—C47 | −0.8 (3) |
C20—N1—C24—C23 | 178.2 (3) | C44—N3—C48—C47 | 177.8 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O4i | 0.93 | 2.58 | 3.468 (4) | 161 |
C43—H43A···O1ii | 0.96 | 2.51 | 3.415 (3) | 156 |
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x−1/2, y+1/2, z−1. |
(II) 3-oxo-5
α-androst-17
β-yl 2-methyl-1
H-imidazole-1-carboxylate
top
Crystal data top
C24H34N2O3 | Dx = 1.231 Mg m−3 |
Mr = 398.53 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 7266 reflections |
a = 6.5828 (2) Å | θ = 2.8–9.1° |
b = 12.3368 (5) Å | µ = 0.08 mm−1 |
c = 26.4702 (10) Å | T = 293 K |
V = 2149.66 (14) Å3 | Prism, colourless |
Z = 4 | 0.35 × 0.33 × 0.13 mm |
F(000) = 864 | |
Data collection top
Bruker APEX CCD area-detector diffractometer | 5844 independent reflections |
Radiation source: fine-focus sealed tube | 3709 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ϕ and ω scans | θmax = 36.4°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −10→10 |
Tmin = 0.963, Tmax = 0.990 | k = −20→20 |
65343 measured reflections | l = −43→44 |
Refinement top
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0787P)2 + 0.068P] where P = (Fo2 + 2Fc2)/3 |
5844 reflections | (Δ/σ)max < 0.001 |
265 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
Crystal data top
C24H34N2O3 | V = 2149.66 (14) Å3 |
Mr = 398.53 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.5828 (2) Å | µ = 0.08 mm−1 |
b = 12.3368 (5) Å | T = 293 K |
c = 26.4702 (10) Å | 0.35 × 0.33 × 0.13 mm |
Data collection top
Bruker APEX CCD area-detector diffractometer | 5844 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 3709 reflections with I > 2σ(I) |
Tmin = 0.963, Tmax = 0.990 | Rint = 0.043 |
65343 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.24 e Å−3 |
5844 reflections | Δρmin = −0.16 e Å−3 |
265 parameters | |
Special details top
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 | |
C1 | 0.6927 (3) | 0.36556 (17) | 0.06358 (6) | 0.0542 (4) | |
H1A | 0.5853 | 0.4183 | 0.0587 | 0.065* | |
H1B | 0.6315 | 0.3004 | 0.0773 | 0.065* | |
C2 | 0.7877 (3) | 0.3386 (2) | 0.01199 (7) | 0.0661 (5) | |
H2A | 0.8711 | 0.2742 | 0.0155 | 0.079* | |
H2B | 0.6798 | 0.3221 | −0.0118 | 0.079* | |
C3 | 0.9150 (3) | 0.42797 (19) | −0.00912 (6) | 0.0574 (4) | |
O1 | 0.9051 (3) | 0.45238 (18) | −0.05317 (5) | 0.0878 (6) | |
C4 | 1.0521 (3) | 0.48505 (18) | 0.02740 (6) | 0.0568 (4) | |
H4A | 1.0991 | 0.5521 | 0.0123 | 0.068* | |
H4B | 1.1700 | 0.4400 | 0.0339 | 0.068* | |
C5 | 0.9465 (2) | 0.51067 (13) | 0.07767 (5) | 0.0427 (3) | |
H5 | 0.8368 | 0.5617 | 0.0698 | 0.051* | |
C6 | 1.0890 (3) | 0.56926 (15) | 0.11358 (6) | 0.0525 (4) | |
H6A | 1.1439 | 0.6329 | 0.0969 | 0.063* | |
H6B | 1.2017 | 0.5219 | 0.1221 | 0.063* | |
C7 | 0.9812 (3) | 0.60347 (14) | 0.16173 (6) | 0.0509 (4) | |
H7A | 0.8836 | 0.6599 | 0.1538 | 0.061* | |
H7B | 1.0799 | 0.6336 | 0.1850 | 0.061* | |
C8 | 0.8707 (2) | 0.50910 (12) | 0.18743 (5) | 0.0384 (3) | |
H8 | 0.9725 | 0.4572 | 0.1995 | 0.046* | |
C9 | 0.7298 (2) | 0.45053 (12) | 0.14965 (5) | 0.0389 (3) | |
H9 | 0.6333 | 0.5053 | 0.1377 | 0.047* | |
C10 | 0.8449 (2) | 0.41053 (12) | 0.10200 (5) | 0.0394 (3) | |
C11 | 0.6013 (3) | 0.36189 (15) | 0.17507 (6) | 0.0556 (4) | |
H11A | 0.5035 | 0.3344 | 0.1508 | 0.067* | |
H11B | 0.6894 | 0.3023 | 0.1846 | 0.067* | |
C12 | 0.4873 (3) | 0.40188 (17) | 0.22213 (6) | 0.0560 (4) | |
H12A | 0.3849 | 0.4542 | 0.2122 | 0.067* | |
H12B | 0.4191 | 0.3413 | 0.2382 | 0.067* | |
C13 | 0.6330 (2) | 0.45403 (12) | 0.25950 (5) | 0.0410 (3) | |
C14 | 0.7452 (2) | 0.54683 (12) | 0.23240 (5) | 0.0399 (3) | |
H14 | 0.6392 | 0.5940 | 0.2185 | 0.048* | |
C15 | 0.8458 (3) | 0.61154 (17) | 0.27524 (6) | 0.0566 (4) | |
H15A | 0.8589 | 0.6874 | 0.2661 | 0.068* | |
H15B | 0.9794 | 0.5828 | 0.2830 | 0.068* | |
C16 | 0.7006 (3) | 0.59749 (16) | 0.32057 (6) | 0.0562 (4) | |
H16A | 0.7710 | 0.5658 | 0.3492 | 0.067* | |
H16B | 0.6435 | 0.6667 | 0.3307 | 0.067* | |
C17 | 0.5339 (2) | 0.52113 (13) | 0.30119 (5) | 0.0443 (3) | |
H17 | 0.4234 | 0.5643 | 0.2867 | 0.053* | |
C18 | 0.7786 (3) | 0.37114 (16) | 0.28266 (7) | 0.0607 (5) | |
H18A | 0.7019 | 0.3136 | 0.2979 | 0.091* | |
H18B | 0.8606 | 0.4058 | 0.3079 | 0.091* | |
H18C | 0.8646 | 0.3420 | 0.2567 | 0.091* | |
C19 | 1.0017 (3) | 0.32244 (15) | 0.11563 (7) | 0.0550 (4) | |
H19A | 0.9323 | 0.2587 | 0.1273 | 0.082* | |
H19B | 1.0896 | 0.3489 | 0.1418 | 0.082* | |
H19C | 1.0809 | 0.3049 | 0.0863 | 0.082* | |
O2 | 0.45134 (17) | 0.45028 (9) | 0.34049 (4) | 0.0472 (3) | |
C20 | 0.3007 (2) | 0.49158 (13) | 0.36725 (6) | 0.0450 (3) | |
O3 | 0.2285 (2) | 0.57953 (12) | 0.36235 (5) | 0.0703 (4) | |
N1 | 0.22526 (18) | 0.41767 (11) | 0.40297 (5) | 0.0431 (3) | |
C21 | 0.3021 (2) | 0.32076 (13) | 0.42121 (6) | 0.0447 (3) | |
C22 | 0.4980 (3) | 0.27103 (16) | 0.40548 (8) | 0.0627 (5) | |
H22A | 0.5258 | 0.2091 | 0.4263 | 0.094* | |
H22B | 0.6053 | 0.3231 | 0.4092 | 0.094* | |
H22C | 0.4892 | 0.2488 | 0.3708 | 0.094* | |
N2 | 0.1826 (2) | 0.28013 (13) | 0.45555 (6) | 0.0537 (3) | |
C23 | 0.0206 (3) | 0.35156 (17) | 0.45991 (7) | 0.0554 (4) | |
H23 | −0.0893 | 0.3421 | 0.4815 | 0.066* | |
C24 | 0.0445 (2) | 0.43571 (16) | 0.42877 (6) | 0.0538 (4) | |
H24 | −0.0424 | 0.4946 | 0.4251 | 0.065* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0480 (7) | 0.0706 (11) | 0.0439 (8) | −0.0188 (8) | 0.0028 (6) | −0.0106 (7) |
C2 | 0.0676 (10) | 0.0860 (14) | 0.0449 (8) | −0.0192 (11) | 0.0033 (8) | −0.0173 (9) |
C3 | 0.0477 (7) | 0.0854 (13) | 0.0390 (7) | −0.0025 (8) | 0.0047 (6) | −0.0035 (8) |
O1 | 0.0790 (9) | 0.1434 (16) | 0.0411 (6) | −0.0150 (12) | −0.0020 (7) | 0.0086 (8) |
C4 | 0.0514 (8) | 0.0771 (12) | 0.0419 (7) | −0.0131 (9) | 0.0059 (6) | 0.0055 (7) |
C5 | 0.0408 (6) | 0.0489 (7) | 0.0386 (6) | −0.0076 (6) | 0.0004 (5) | 0.0075 (6) |
C6 | 0.0500 (7) | 0.0590 (10) | 0.0484 (8) | −0.0232 (7) | 0.0042 (6) | 0.0037 (7) |
C7 | 0.0553 (8) | 0.0497 (8) | 0.0477 (8) | −0.0205 (7) | 0.0005 (6) | −0.0010 (6) |
C8 | 0.0364 (5) | 0.0408 (7) | 0.0379 (6) | −0.0068 (5) | −0.0011 (5) | 0.0020 (5) |
C9 | 0.0370 (5) | 0.0419 (7) | 0.0379 (6) | −0.0094 (5) | 0.0018 (5) | 0.0003 (5) |
C10 | 0.0386 (5) | 0.0429 (7) | 0.0367 (6) | −0.0080 (5) | 0.0008 (5) | 0.0008 (5) |
C11 | 0.0622 (9) | 0.0562 (9) | 0.0485 (8) | −0.0274 (8) | 0.0132 (7) | −0.0068 (7) |
C12 | 0.0536 (8) | 0.0669 (10) | 0.0476 (8) | −0.0229 (8) | 0.0127 (7) | −0.0043 (7) |
C13 | 0.0445 (6) | 0.0400 (7) | 0.0385 (6) | 0.0020 (6) | 0.0052 (5) | 0.0036 (5) |
C14 | 0.0424 (6) | 0.0389 (6) | 0.0383 (6) | −0.0021 (6) | −0.0020 (5) | 0.0013 (5) |
C15 | 0.0630 (9) | 0.0609 (10) | 0.0458 (8) | −0.0138 (8) | 0.0006 (7) | −0.0097 (7) |
C16 | 0.0713 (10) | 0.0531 (9) | 0.0442 (8) | 0.0000 (9) | 0.0042 (8) | −0.0069 (7) |
C17 | 0.0496 (7) | 0.0454 (7) | 0.0379 (6) | 0.0098 (6) | 0.0056 (5) | 0.0068 (5) |
C18 | 0.0720 (10) | 0.0541 (9) | 0.0560 (9) | 0.0234 (9) | 0.0162 (9) | 0.0151 (8) |
C19 | 0.0618 (9) | 0.0508 (9) | 0.0524 (8) | 0.0073 (8) | 0.0069 (7) | 0.0043 (7) |
O2 | 0.0533 (6) | 0.0469 (5) | 0.0413 (5) | 0.0138 (5) | 0.0109 (4) | 0.0085 (4) |
C20 | 0.0442 (7) | 0.0495 (8) | 0.0414 (6) | 0.0105 (6) | 0.0013 (5) | 0.0046 (6) |
O3 | 0.0721 (8) | 0.0633 (8) | 0.0754 (9) | 0.0332 (7) | 0.0260 (7) | 0.0229 (7) |
N1 | 0.0382 (5) | 0.0508 (7) | 0.0403 (5) | 0.0067 (5) | 0.0023 (5) | 0.0041 (5) |
C21 | 0.0439 (6) | 0.0452 (7) | 0.0449 (7) | 0.0026 (6) | −0.0013 (6) | 0.0035 (6) |
C22 | 0.0582 (9) | 0.0567 (10) | 0.0734 (11) | 0.0183 (8) | 0.0116 (9) | 0.0180 (9) |
N2 | 0.0517 (7) | 0.0560 (8) | 0.0533 (7) | −0.0033 (6) | 0.0014 (6) | 0.0089 (6) |
C23 | 0.0420 (7) | 0.0769 (12) | 0.0473 (8) | −0.0006 (8) | 0.0042 (6) | 0.0061 (8) |
C24 | 0.0410 (7) | 0.0715 (11) | 0.0489 (8) | 0.0127 (7) | 0.0055 (6) | 0.0065 (8) |
Geometric parameters (Å, º) top
C1—C10 | 1.532 (2) | C13—C17 | 1.526 (2) |
C1—C2 | 1.539 (2) | C13—C18 | 1.529 (2) |
C1—H1A | 0.9700 | C13—C14 | 1.539 (2) |
C1—H1B | 0.9700 | C14—C15 | 1.537 (2) |
C2—C3 | 1.493 (3) | C14—H14 | 0.9800 |
C2—H2A | 0.9700 | C15—C16 | 1.544 (3) |
C2—H2B | 0.9700 | C15—H15A | 0.9700 |
C3—O1 | 1.206 (2) | C15—H15B | 0.9700 |
C3—C4 | 1.498 (2) | C16—C17 | 1.535 (3) |
C4—C5 | 1.534 (2) | C16—H16A | 0.9700 |
C4—H4A | 0.9700 | C16—H16B | 0.9700 |
C4—H4B | 0.9700 | C17—O2 | 1.4633 (17) |
C5—C6 | 1.519 (2) | C17—H17 | 0.9800 |
C5—C10 | 1.546 (2) | C18—H18A | 0.9600 |
C5—H5 | 0.9800 | C18—H18B | 0.9600 |
C6—C7 | 1.519 (2) | C18—H18C | 0.9600 |
C6—H6A | 0.9700 | C19—H19A | 0.9600 |
C6—H6B | 0.9700 | C19—H19B | 0.9600 |
C7—C8 | 1.532 (2) | C19—H19C | 0.9600 |
C7—H7A | 0.9700 | O2—C20 | 1.3209 (18) |
C7—H7B | 0.9700 | C20—O3 | 1.192 (2) |
C8—C14 | 1.5220 (19) | C20—N1 | 1.404 (2) |
C8—C9 | 1.5434 (18) | N1—C21 | 1.385 (2) |
C8—H8 | 0.9800 | N1—C24 | 1.3896 (19) |
C9—C11 | 1.538 (2) | C21—N2 | 1.302 (2) |
C9—C10 | 1.5517 (19) | C21—C22 | 1.487 (2) |
C9—H9 | 0.9800 | C22—H22A | 0.9600 |
C10—C19 | 1.542 (2) | C22—H22B | 0.9600 |
C11—C12 | 1.536 (2) | C22—H22C | 0.9600 |
C11—H11A | 0.9700 | N2—C23 | 1.388 (2) |
C11—H11B | 0.9700 | C23—C24 | 1.335 (3) |
C12—C13 | 1.521 (2) | C23—H23 | 0.9300 |
C12—H12A | 0.9700 | C24—H24 | 0.9300 |
C12—H12B | 0.9700 | | |
| | | |
C10—C1—C2 | 113.69 (14) | C11—C12—H12B | 109.5 |
C10—C1—H1A | 108.8 | H12A—C12—H12B | 108.1 |
C2—C1—H1A | 108.8 | C12—C13—C17 | 115.46 (13) |
C10—C1—H1B | 108.8 | C12—C13—C18 | 111.90 (16) |
C2—C1—H1B | 108.8 | C17—C13—C18 | 109.93 (12) |
H1A—C1—H1B | 107.7 | C12—C13—C14 | 108.29 (11) |
C3—C2—C1 | 113.60 (16) | C17—C13—C14 | 97.97 (12) |
C3—C2—H2A | 108.8 | C18—C13—C14 | 112.56 (13) |
C1—C2—H2A | 108.8 | C8—C14—C15 | 120.14 (12) |
C3—C2—H2B | 108.8 | C8—C14—C13 | 113.40 (12) |
C1—C2—H2B | 108.8 | C15—C14—C13 | 104.43 (12) |
H2A—C2—H2B | 107.7 | C8—C14—H14 | 106.0 |
O1—C3—C2 | 121.06 (18) | C15—C14—H14 | 106.0 |
O1—C3—C4 | 122.60 (19) | C13—C14—H14 | 106.0 |
C2—C3—C4 | 116.34 (15) | C14—C15—C16 | 104.37 (14) |
C3—C4—C5 | 112.56 (13) | C14—C15—H15A | 110.9 |
C3—C4—H4A | 109.1 | C16—C15—H15A | 110.9 |
C5—C4—H4A | 109.1 | C14—C15—H15B | 110.9 |
C3—C4—H4B | 109.1 | C16—C15—H15B | 110.9 |
C5—C4—H4B | 109.1 | H15A—C15—H15B | 108.9 |
H4A—C4—H4B | 107.8 | C17—C16—C15 | 104.59 (12) |
C6—C5—C4 | 111.18 (12) | C17—C16—H16A | 110.8 |
C6—C5—C10 | 112.77 (12) | C15—C16—H16A | 110.8 |
C4—C5—C10 | 113.13 (14) | C17—C16—H16B | 110.8 |
C6—C5—H5 | 106.4 | C15—C16—H16B | 110.8 |
C4—C5—H5 | 106.4 | H16A—C16—H16B | 108.9 |
C10—C5—H5 | 106.4 | O2—C17—C13 | 110.42 (12) |
C5—C6—C7 | 111.63 (13) | O2—C17—C16 | 113.24 (12) |
C5—C6—H6A | 109.3 | C13—C17—C16 | 105.59 (13) |
C7—C6—H6A | 109.3 | O2—C17—H17 | 109.2 |
C5—C6—H6B | 109.3 | C13—C17—H17 | 109.2 |
C7—C6—H6B | 109.3 | C16—C17—H17 | 109.2 |
H6A—C6—H6B | 108.0 | C13—C18—H18A | 109.5 |
C6—C7—C8 | 112.55 (14) | C13—C18—H18B | 109.5 |
C6—C7—H7A | 109.1 | H18A—C18—H18B | 109.5 |
C8—C7—H7A | 109.1 | C13—C18—H18C | 109.5 |
C6—C7—H7B | 109.1 | H18A—C18—H18C | 109.5 |
C8—C7—H7B | 109.1 | H18B—C18—H18C | 109.5 |
H7A—C7—H7B | 107.8 | C10—C19—H19A | 109.5 |
C14—C8—C7 | 111.88 (13) | C10—C19—H19B | 109.5 |
C14—C8—C9 | 108.90 (11) | H19A—C19—H19B | 109.5 |
C7—C8—C9 | 110.69 (11) | C10—C19—H19C | 109.5 |
C14—C8—H8 | 108.4 | H19A—C19—H19C | 109.5 |
C7—C8—H8 | 108.4 | H19B—C19—H19C | 109.5 |
C9—C8—H8 | 108.4 | C20—O2—C17 | 115.44 (12) |
C11—C9—C8 | 112.32 (12) | O3—C20—O2 | 126.32 (15) |
C11—C9—C10 | 113.46 (12) | O3—C20—N1 | 121.56 (14) |
C8—C9—C10 | 112.47 (11) | O2—C20—N1 | 112.09 (13) |
C11—C9—H9 | 105.9 | C21—N1—C24 | 106.25 (13) |
C8—C9—H9 | 105.9 | C21—N1—C20 | 131.75 (13) |
C10—C9—H9 | 105.9 | C24—N1—C20 | 121.98 (14) |
C1—C10—C19 | 109.76 (14) | N2—C21—N1 | 110.77 (14) |
C1—C10—C5 | 107.22 (12) | N2—C21—C22 | 124.08 (15) |
C19—C10—C5 | 111.78 (12) | N1—C21—C22 | 125.11 (15) |
C1—C10—C9 | 109.60 (11) | C21—C22—H22A | 109.5 |
C19—C10—C9 | 111.15 (12) | C21—C22—H22B | 109.5 |
C5—C10—C9 | 107.21 (12) | H22A—C22—H22B | 109.5 |
C12—C11—C9 | 113.29 (14) | C21—C22—H22C | 109.5 |
C12—C11—H11A | 108.9 | H22A—C22—H22C | 109.5 |
C9—C11—H11A | 108.9 | H22B—C22—H22C | 109.5 |
C12—C11—H11B | 108.9 | C21—N2—C23 | 106.13 (14) |
C9—C11—H11B | 108.9 | C24—C23—N2 | 110.59 (15) |
H11A—C11—H11B | 107.7 | C24—C23—H23 | 124.7 |
C13—C12—C11 | 110.82 (13) | N2—C23—H23 | 124.7 |
C13—C12—H12A | 109.5 | C23—C24—N1 | 106.25 (15) |
C11—C12—H12A | 109.5 | C23—C24—H24 | 126.9 |
C13—C12—H12B | 109.5 | N1—C24—H24 | 126.9 |
| | | |
C10—C1—C2—C3 | −49.3 (2) | C9—C8—C14—C15 | −177.80 (14) |
C1—C2—C3—O1 | −137.2 (2) | C7—C8—C14—C13 | −179.55 (12) |
C1—C2—C3—C4 | 42.3 (3) | C9—C8—C14—C13 | 57.78 (15) |
O1—C3—C4—C5 | 135.6 (2) | C12—C13—C14—C8 | −61.15 (16) |
C2—C3—C4—C5 | −43.9 (3) | C17—C13—C14—C8 | 178.62 (12) |
C3—C4—C5—C6 | −179.53 (16) | C18—C13—C14—C8 | 63.10 (16) |
C3—C4—C5—C10 | 52.4 (2) | C12—C13—C14—C15 | 166.30 (14) |
C4—C5—C6—C7 | 175.19 (15) | C17—C13—C14—C15 | 46.07 (14) |
C10—C5—C6—C7 | −56.53 (19) | C18—C13—C14—C15 | −69.45 (17) |
C5—C6—C7—C8 | 52.86 (19) | C8—C14—C15—C16 | −159.56 (14) |
C6—C7—C8—C14 | −173.95 (13) | C13—C14—C15—C16 | −30.98 (18) |
C6—C7—C8—C9 | −52.30 (18) | C14—C15—C16—C17 | 2.86 (19) |
C14—C8—C9—C11 | −51.36 (17) | C12—C13—C17—O2 | 78.11 (16) |
C7—C8—C9—C11 | −174.74 (14) | C18—C13—C17—O2 | −49.63 (17) |
C14—C8—C9—C10 | 179.17 (12) | C14—C13—C17—O2 | −167.20 (12) |
C7—C8—C9—C10 | 55.79 (17) | C12—C13—C17—C16 | −159.15 (14) |
C2—C1—C10—C19 | −65.8 (2) | C18—C13—C17—C16 | 73.11 (16) |
C2—C1—C10—C5 | 55.8 (2) | C14—C13—C17—C16 | −44.46 (14) |
C2—C1—C10—C9 | 171.83 (16) | C15—C16—C17—O2 | 147.51 (14) |
C6—C5—C10—C1 | 175.14 (13) | C15—C16—C17—C13 | 26.58 (17) |
C4—C5—C10—C1 | −57.61 (17) | C13—C17—O2—C20 | −155.21 (13) |
C6—C5—C10—C19 | −64.52 (17) | C16—C17—O2—C20 | 86.63 (17) |
C4—C5—C10—C19 | 62.73 (17) | C17—O2—C20—O3 | −0.2 (3) |
C6—C5—C10—C9 | 57.52 (16) | C17—O2—C20—N1 | 178.00 (13) |
C4—C5—C10—C9 | −175.23 (12) | O3—C20—N1—C21 | −167.68 (17) |
C11—C9—C10—C1 | 57.80 (18) | O2—C20—N1—C21 | 14.0 (2) |
C8—C9—C10—C1 | −173.32 (13) | O3—C20—N1—C24 | 10.3 (3) |
C11—C9—C10—C19 | −63.71 (17) | O2—C20—N1—C24 | −168.00 (14) |
C8—C9—C10—C19 | 65.17 (16) | C24—N1—C21—N2 | −0.07 (19) |
C11—C9—C10—C5 | 173.86 (13) | C20—N1—C21—N2 | 178.18 (16) |
C8—C9—C10—C5 | −57.27 (15) | C24—N1—C21—C22 | −177.93 (17) |
C8—C9—C11—C12 | 51.2 (2) | C20—N1—C21—C22 | 0.3 (3) |
C10—C9—C11—C12 | −179.88 (14) | N1—C21—N2—C23 | 0.58 (19) |
C9—C11—C12—C13 | −54.1 (2) | C22—C21—N2—C23 | 178.47 (16) |
C11—C12—C13—C17 | 165.49 (14) | C21—N2—C23—C24 | −0.9 (2) |
C11—C12—C13—C18 | −67.76 (18) | N2—C23—C24—N1 | 0.9 (2) |
C11—C12—C13—C14 | 56.88 (19) | C21—N1—C24—C23 | −0.49 (19) |
C7—C8—C14—C15 | −55.13 (18) | C20—N1—C24—C23 | −178.96 (15) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19A···O3i | 0.96 | 2.47 | 3.408 (2) | 167 |
C24—H24···O1ii | 0.93 | 2.54 | 3.301 (2) | 139 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1/2, −y+1, z+1/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C24H30N2O3 | C24H34N2O3 |
Mr | 394.50 | 398.53 |
Crystal system, space group | Monoclinic, C2 | Orthorhombic, P212121 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 24.5935 (5), 7.0351 (1), 24.9875 (4) | 6.5828 (2), 12.3368 (5), 26.4702 (10) |
α, β, γ (°) | 90, 105.1160 (11), 90 | 90, 90, 90 |
V (Å3) | 4173.69 (12) | 2149.66 (14) |
Z | 8 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.08 |
Crystal size (mm) | 0.36 × 0.15 × 0.04 | 0.35 × 0.33 × 0.13 |
|
Data collection |
Diffractometer | Bruker APEX CCD area-detector diffractometer | Bruker APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.906, 0.997 | 0.963, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 45077, 5398, 3688 | 65343, 5844, 3709 |
Rint | 0.052 | 0.043 |
(sin θ/λ)max (Å−1) | 0.660 | 0.835 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.102, 1.01 | 0.046, 0.144, 1.01 |
No. of reflections | 5398 | 5844 |
No. of parameters | 529 | 265 |
No. of restraints | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.13, −0.20 | 0.24, −0.16 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O4i | 0.93 | 2.58 | 3.468 (4) | 161 |
C43—H43A···O1ii | 0.96 | 2.51 | 3.415 (3) | 156 |
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x−1/2, y+1/2, z−1. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19A···O3i | 0.96 | 2.47 | 3.408 (2) | 167 |
C24—H24···O1ii | 0.93 | 2.54 | 3.301 (2) | 139 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1/2, −y+1, z+1/2. |
Hormonal treatments for prostate cancer therapy are based on the Nobel Prize winning discovery by Huggins & Hodges (1941) that the growth and progression of prostate cancer cells depends on androgen levels in the body. Cytochrome 17α-hydroxylase-C17,20-lyase, CYP17, is one of the enzymes involved in androgen biosynthesis in the human body (Nakajin & Hall, 1981; Hall, 1991). Its inhibition has traditionally been recognized as an important strategy for prostate cancer treatment as a way of lowering androgen levels and thus preventing disease progression (Barrie & Jarman, 1996; Njar & Brodie, 1999; Hartmann et al., 2002; Moreira, Salvador et al., 2008). The present work is within a project of synthesizing and characterizing new steroidal compounds bearing heteroatom-containing moieties at C17 as potential inhibitors for C17 [CYP17 ?] and thus aiming to contribute to the field of prostate cancer treatment (Ramos Silva et al., 2008a,b; Moreira, Vasaitis et al., 2008; Moreira et al., 2007). Both title compounds, 3-oxoandrosta-4,6-dien-17β-yl 2-methyl-1H-imidazole-1-carboxylate, (I), and 3-oxo-5α-androst-17β-yl 2-methyl-1H-imidazole-1-carboxylate, (II), have previously been tested for biological activity and show very good affinity towards important receptors (Moreira, Vasaitis et al., 2008). We report here the molecular structures of (I) and (II) as determined by single-crystal X-ray analysis, and compare them with those of the free molecules as given by quantum mechanical ab initio calculations.
An ORTEPII (Johnson, 1976) plot of (I) is shown in Fig. 1 and a plot of (II) is shown in Fig. 2. The two compounds are very similar, both with a nearly planar methylimidazole carbamate moiety at the 17-position.
Compound (I) has two molecules in the asymmetric unit that differ in the orientation of the methylimidazole mean plane with respect to the steroid nucleus. In both molecules, the A/B ring junction is quasi-trans, whereas rings B/C and C/D are trans-fused. The five-membered ring D has an envelope conformation, with atom C13 at the flap position displaced by 0.738 (3) Å from the best plane of the other four C atoms for molecule 1 (atoms C1–C24) and by 0.733 (3) Å for molecule 2 (atoms C25–C46)]. The C16—C17—O2—C20 torsion angle is 143.1 (2) in molecule 1 and the corresponding angle is 73.1 (3)° in molecule 2, reflecting the large difference in the orientation of the methylimidazole plane for the two independent molecules. Rings A and B have half-chair conformations while ring C has a chair conformation, with endocyclic torsion-angle magnitudes in the range 54.6 (3)–58.7 (3)° for molecule 1 and 55.5 (3)–58.1 (3)° for molecule 2. The molecules are slightly convex towards the β side. The value of the pseudo torsion angle C19—C10···C13—C18 is -8.9 (3)° for molecule 1 and the corresponding angle in molecule 2 is -7.4 (3)°. The corresponding distances between terminal atoms C3 and C16 are 8.895 (5) and 8.838 (5) Å, respectively, for molecules 1 and 2. The molecules pack in stacks with the aromatic tail substituents interacting via π–π interactions. These stacks are further joined by C—H···O interactions to form layers (Fig. 3, Table 1).
Compound (II) crystallizes with just one independent molecule in the asymmetric unit. All six-membered rings are saturated and adjusted to chair conformations. They are all trans-fused. The five-membered ring D has an envelope conformation, with atom C13 at the flap position displaced by 0.7128 (14) Å from the best plane of the other four C atoms. The molecule is slightly convex towards the β side. The pseudo torsion angle C19—C10···C13—C18 is 1.1 (2)° and the distance between terminal atoms C3 and C16 is 9.084 (2) Å. The C16—C17—O2—C20 torsion angle is 86.63 (17)°. The molecular packing is influenced by a C—H···π interaction of type III, as described by Malone et al. (1997), with a C4···π distance of 3.670 (2) Å (Fig. 4); atom H4A is above the centre of the aromatic ring N1/C21/N2/C23/C24 but the C4—H4A bond points towards the ring edge. Further intermolecular C—H···O interactions join all the molecules into a three-dimensional network, reinforcing crystal cohesion (Table 2).
In order to check if the orientation of the 2-methylimidazole-1-carboxylate moiety is intrinsic to the free steroid molecule or rather due to intermolecular interactions, we have performed quantum mechanical calculations of the equilibrium geometries of the free molecules. These calculations were performed using the computer program GAMESS (Schmidt et al., 1993) starting with the solid-state conformations. A molecular-orbital Roothan Hartree–Fock method was used with an extended 6-31G(d,p) basis set. Tight conditions for convergence of both the self-consistent field cycles and the maximum density and energy gradients were imposed (10-5 atomic units). Before engaging in heavier calculations, we computed the energy of the molecule just by changing the orientation of the 2-methylimidazole-1-carboxylate moiety (changing the C16—C17—O2—C20 torsion angle in steps of 10°) without relaxing the molecular geometry. This preliminary calculation shows a global minimum near the conformation of molecule 2 in (I) and a local minimum near the conformation of molecule 1 in (I). Both geometries of molecules 1 and 2 were then relaxed. For molecules 1 and 2, the calculated geometries differ more significantly in the conformation of ring B and on the orientation of the methylimidazole mean plane. The geometry that corresponds to the local energy minimum of molecule 1 shows a ring B with an average torsion angle of 29.4° [observed mean value 36.05 (14)°]. The orientation of the methylimidazole plane converges to a C16—C17—O2—C20 torsion angle of 141.7°. The geometry that corresponds to the global energy minimum of molecule 2 shows a ring B with an average torsion angle of 29.4° [observed mean value 34.74 (13)°]. The orientation of the methylimidazole plane converges to a C16—C17—O2—C20 torsion angle of 81.4°. We can therefore conclude that supramolecular aggregation plays an important role in stabilizing the two observed geometries. The minimum energy for compound (II) is achieved with a C16—C17—O2—C20 torsion angle of 86.6°, equal to the experimental value. The remaining calculated structural features agree well with those determined experimentally.