The title compound, C
31H
32N
2O
7·0.25C
4H
8O
2, is a key intermediate in the synthesis of [
18F]fluorine-labelled thymidine (
18F-FLT), which is the most widely used molecular imaging probe for positron emission tomography (PET). The crystallographic asymmetric unit contains two independent thymine molecules plus one partially occupied site for an ethyl acetate molecule. The two independent thymine molecules show similar geometrical features, except that the dimethoxytrityl groups adopt different orientations with respect to the remainder of the molecule. Each thymine base adopts an
anti conformation with respect to the attached deoxyribose ring, and the deoxyribose rings show C3-
endo puckering. The conformation of the side chain at the C1 position of the deoxyribose ring is
gauche+. Intermolecular N—H
O and O—H
O hydrogen bonds link the molecules into one-dimensional chains.
Supporting information
CCDC reference: 914660
The title compound was synthesized according to the literature procedure of Yun
et al. (2003). The crude product was recrystallized from ethyl
acetate
(m.p. 349.8–350.3 K, literature 350 K). 1H NMR (400 MHz; DMSO-d6):
δ 7.29–6.84 (m, 14H, Ar—H and H-6), 3.85 (m, 1H, H-4'), 3.73 (s, 6H,
OCH3), 3.42 (m, 2H, H-5), 2.51 (m, 2H, H-2), 1.79 (s, 3H, 5-CH3). 13C
NMR (100 MHz, DMSO-d6): δ 85.2 (C-1'), 83.7 (CPh3), 80.3 (C-4'), 69.0
(C-3'), 60.1 (C-5'), 55.3 (OCH3), 41.4 (C-2'), 12.8 (CH3).
H atoms bound to C atoms were placed geometrically and refined using a riding
model, with C—H = 0.95–1.00 Å and Uiso(H) = 1.2 or
1.5Ueq(C). The methyl groups were allowed to rotate around their
local threefold axes. H atoms bound to N2, N2' and O2' were located in
difference Fourier maps and refined without restraint. Atom H2O could not be
treated in this way and so was placed geometrically and refined as riding,
with O—H = 0.84 Å and Uiso(H) = 1.2Ueq(O). The site
occupancy of the ethyl acetate molecule was constrained to 0.5 in order to
produce reasonable displacement parameters. The geometry of this molecule was
also restrained. The maxima in the final difference Fourier map are located
around the solvent molecule. In the absence of significant anomalous
scattering effects, Friedel pairs were merged as equivalent data. The absolute
structure is assigned on the basis of known chirality of thymidine used in the
chemical synthesis.
Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: SHELXTL97 (Sheldrick, 2008).
[5'-
O-[Bis(4-methoxyphenyl)(phenyl)methyl]-2'-deoxy-
β-
D-
threopentofuranosyl]thymine ethyl acetate 0.25-solvate
top
Crystal data top
C31H32N2O7·0.25C4H8O2 | F(000) = 1200 |
Mr = 566.61 | Dx = 1.218 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 10255 reflections |
a = 10.542 (2) Å | θ = 2.3–29.1° |
b = 17.931 (4) Å | µ = 0.09 mm−1 |
c = 17.136 (3) Å | T = 153 K |
β = 107.51 (3)° | Prism, colorless |
V = 3089.1 (11) Å3 | 0.54 × 0.32 × 0.25 mm |
Z = 4 | |
Data collection top
Rigaku AFC10/Saturn724+ diffractometer | 6327 reflections with I > 2σ(I) |
Radiation source: Rotating Anode | Rint = 0.038 |
Graphite monochromator | θmax = 27.5°, θmin = 2.3° |
Detector resolution: 28.5714 pixels mm-1 | h = −13→13 |
ϕ and ω scans | k = −23→19 |
24617 measured reflections | l = −22→22 |
7094 independent reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.056 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.151 | w = 1/[σ2(Fo2) + (0.0959P)2 + 0.869P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.001 |
7094 reflections | Δρmax = 0.79 e Å−3 |
790 parameters | Δρmin = −0.32 e Å−3 |
5 restraints | Absolute structure: In the absence of significant anomalous scattering effects,
Friedel pairs were merged as equivalent reflections. |
Primary atom site location: structure-invariant direct methods | |
Crystal data top
C31H32N2O7·0.25C4H8O2 | V = 3089.1 (11) Å3 |
Mr = 566.61 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.542 (2) Å | µ = 0.09 mm−1 |
b = 17.931 (4) Å | T = 153 K |
c = 17.136 (3) Å | 0.54 × 0.32 × 0.25 mm |
β = 107.51 (3)° | |
Data collection top
Rigaku AFC10/Saturn724+ diffractometer | 6327 reflections with I > 2σ(I) |
24617 measured reflections | Rint = 0.038 |
7094 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.056 | 5 restraints |
wR(F2) = 0.151 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.79 e Å−3 |
7094 reflections | Δρmin = −0.32 e Å−3 |
790 parameters | Absolute structure: In the absence of significant anomalous scattering effects,
Friedel pairs were merged as equivalent reflections. |
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 | Occ. (<1) |
O1 | −0.2151 (2) | 0.32719 (13) | 0.07146 (13) | 0.0218 (5) | |
O2 | −0.3666 (2) | 0.32102 (15) | 0.20273 (16) | 0.0301 (5) | |
H2O | −0.4499 | 0.3221 | 0.1903 | 0.036* | |
O4 | 0.0951 (2) | 0.23199 (14) | 0.20216 (15) | 0.0276 (5) | |
O3 | 0.3646 (2) | 0.38126 (18) | 0.11039 (18) | 0.0392 (7) | |
O5 | −0.2788 (2) | 0.48282 (13) | 0.03782 (13) | 0.0241 (5) | |
O6 | −0.3179 (3) | 0.44313 (19) | −0.32883 (17) | 0.0444 (7) | |
O7 | 0.0999 (3) | 0.75605 (18) | 0.14832 (18) | 0.0483 (8) | |
N1 | 0.0087 (3) | 0.34228 (16) | 0.14261 (17) | 0.0215 (6) | |
N2 | 0.2275 (3) | 0.31054 (17) | 0.15847 (18) | 0.0242 (6) | |
H2N | 0.298 (4) | 0.275 (2) | 0.180 (2) | 0.026 (10)* | |
C1 | −0.3396 (3) | 0.36087 (18) | 0.07274 (19) | 0.0201 (6) | |
H1 | −0.4112 | 0.3223 | 0.0553 | 0.024* | |
C2 | −0.3219 (3) | 0.38051 (19) | 0.1624 (2) | 0.0226 (6) | |
H2 | −0.3660 | 0.4288 | 0.1677 | 0.027* | |
C3 | −0.1723 (3) | 0.3848 (2) | 0.19975 (19) | 0.0230 (6) | |
H3A | −0.1455 | 0.3723 | 0.2587 | 0.028* | |
H3B | −0.1385 | 0.4350 | 0.1927 | 0.028* | |
C4 | −0.1227 (3) | 0.32666 (19) | 0.15144 (19) | 0.0204 (6) | |
H4 | −0.1224 | 0.2764 | 0.1769 | 0.025* | |
C8 | 0.1086 (3) | 0.29146 (19) | 0.17000 (19) | 0.0210 (6) | |
C5 | 0.0272 (3) | 0.40655 (19) | 0.1018 (2) | 0.0254 (7) | |
H5 | −0.0456 | 0.4399 | 0.0826 | 0.030* | |
C6 | 0.1424 (3) | 0.4238 (2) | 0.0883 (2) | 0.0292 (7) | |
C7 | 0.2540 (3) | 0.3730 (2) | 0.1176 (2) | 0.0284 (7) | |
C9 | 0.1611 (4) | 0.4934 (3) | 0.0439 (3) | 0.0441 (11) | |
H9A | 0.1675 | 0.4801 | −0.0103 | 0.053* | |
H9B | 0.2429 | 0.5187 | 0.0753 | 0.053* | |
H9C | 0.0850 | 0.5267 | 0.0377 | 0.053* | |
C10 | −0.3738 (3) | 0.42424 (19) | 0.0119 (2) | 0.0238 (7) | |
H10A | −0.3739 | 0.4061 | −0.0427 | 0.029* | |
H10B | −0.4639 | 0.4433 | 0.0074 | 0.029* | |
C11 | −0.3062 (3) | 0.54958 (19) | −0.0126 (2) | 0.0246 (7) | |
C12 | −0.4332 (4) | 0.58728 (19) | −0.0058 (2) | 0.0274 (7) | |
C13 | −0.5132 (4) | 0.6323 (2) | −0.0675 (3) | 0.0364 (9) | |
H13 | −0.4920 | 0.6381 | −0.1173 | 0.044* | |
C14 | −0.6222 (5) | 0.6685 (2) | −0.0574 (3) | 0.0465 (11) | |
H14 | −0.6771 | 0.6978 | −0.1006 | 0.056* | |
C15 | −0.6519 (5) | 0.6622 (3) | 0.0151 (4) | 0.0509 (12) | |
H15 | −0.7278 | 0.6868 | 0.0217 | 0.061* | |
C16 | −0.5721 (5) | 0.6204 (2) | 0.0782 (3) | 0.0458 (11) | |
H16 | −0.5913 | 0.6174 | 0.1289 | 0.055* | |
C17 | −0.4633 (4) | 0.5824 (2) | 0.0679 (2) | 0.0348 (8) | |
H17 | −0.4091 | 0.5529 | 0.1113 | 0.042* | |
C18 | −0.3099 (3) | 0.52775 (19) | −0.1004 (2) | 0.0240 (7) | |
C19 | −0.4273 (4) | 0.5060 (2) | −0.1590 (2) | 0.0275 (7) | |
H19 | −0.5094 | 0.5100 | −0.1470 | 0.033* | |
C20 | −0.4265 (4) | 0.4785 (2) | −0.2343 (2) | 0.0327 (8) | |
H20 | −0.5077 | 0.4642 | −0.2733 | 0.039* | |
C21 | −0.3083 (4) | 0.4719 (2) | −0.2531 (2) | 0.0303 (8) | |
C22 | −0.1906 (4) | 0.4939 (2) | −0.1965 (2) | 0.0310 (8) | |
H22 | −0.1092 | 0.4907 | −0.2093 | 0.037* | |
C23 | −0.1924 (4) | 0.5210 (2) | −0.1202 (2) | 0.0282 (7) | |
H23 | −0.1111 | 0.5351 | −0.0811 | 0.034* | |
C24 | −0.1951 (5) | 0.4262 (3) | −0.3457 (3) | 0.0541 (12) | |
H24A | −0.1475 | 0.4726 | −0.3483 | 0.065* | |
H24B | −0.2146 | 0.4000 | −0.3982 | 0.065* | |
H24C | −0.1399 | 0.3944 | −0.3021 | 0.065* | |
C25 | −0.1916 (4) | 0.60279 (19) | 0.0278 (2) | 0.0260 (7) | |
C26 | −0.1615 (4) | 0.6628 (2) | −0.0147 (2) | 0.0371 (9) | |
H26 | −0.2087 | 0.6688 | −0.0710 | 0.045* | |
C27 | −0.0645 (4) | 0.7142 (2) | 0.0231 (2) | 0.0388 (9) | |
H27 | −0.0448 | 0.7543 | −0.0076 | 0.047* | |
C28 | 0.0043 (4) | 0.7073 (2) | 0.1058 (2) | 0.0345 (8) | |
C29 | −0.0274 (4) | 0.6495 (2) | 0.1499 (2) | 0.0404 (9) | |
H29 | 0.0161 | 0.6455 | 0.2070 | 0.048* | |
C30 | −0.1222 (4) | 0.5976 (2) | 0.1111 (2) | 0.0340 (8) | |
H30 | −0.1408 | 0.5572 | 0.1419 | 0.041* | |
C31 | 0.1295 (5) | 0.8176 (3) | 0.1044 (3) | 0.0498 (11) | |
H31A | 0.1593 | 0.7993 | 0.0589 | 0.060* | |
H31B | 0.2001 | 0.8478 | 0.1411 | 0.060* | |
H31C | 0.0496 | 0.8482 | 0.0828 | 0.060* | |
O1' | 0.7264 (2) | 0.08358 (14) | 0.32231 (15) | 0.0271 (5) | |
O2' | 0.9396 (3) | 0.20564 (18) | 0.31128 (18) | 0.0397 (7) | |
H2'O | 1.024 (5) | 0.189 (3) | 0.310 (3) | 0.048 (14)* | |
O3' | 0.1955 (2) | 0.11553 (16) | 0.37975 (17) | 0.0343 (6) | |
O4' | 0.4300 (2) | 0.20799 (15) | 0.22002 (14) | 0.0263 (5) | |
O5' | 0.8659 (2) | 0.05605 (15) | 0.48853 (14) | 0.0274 (5) | |
O6' | 1.4497 (3) | −0.0349 (2) | 0.6915 (2) | 0.0564 (10) | |
O7' | 0.6227 (5) | 0.1702 (3) | 0.7502 (3) | 0.0826 (14) | |
N1' | 0.5462 (3) | 0.15000 (16) | 0.33837 (16) | 0.0220 (6) | |
N2' | 0.3184 (3) | 0.16005 (17) | 0.30231 (18) | 0.0232 (6) | |
H2'N | 0.253 (4) | 0.176 (2) | 0.274 (2) | 0.013 (9)* | |
C1' | 0.8694 (3) | 0.0862 (2) | 0.3544 (2) | 0.0256 (7) | |
H1' | 0.9075 | 0.0709 | 0.3099 | 0.031* | |
C2' | 0.9064 (3) | 0.1685 (2) | 0.3760 (2) | 0.0290 (8) | |
H2' | 0.9791 | 0.1732 | 0.4290 | 0.035* | |
C3' | 0.7779 (3) | 0.2028 (2) | 0.3811 (2) | 0.0259 (7) | |
H3'1 | 0.7718 | 0.2561 | 0.3655 | 0.031* | |
H3'2 | 0.7694 | 0.1979 | 0.4368 | 0.031* | |
C4' | 0.6731 (3) | 0.15678 (19) | 0.3196 (2) | 0.0229 (6) | |
H4' | 0.6568 | 0.1782 | 0.2635 | 0.028* | |
C5' | 0.5434 (3) | 0.1157 (2) | 0.4100 (2) | 0.0247 (7) | |
H5' | 0.6256 | 0.1007 | 0.4477 | 0.030* | |
C6' | 0.4316 (3) | 0.1022 (2) | 0.4298 (2) | 0.0274 (7) | |
C7' | 0.3057 (3) | 0.12454 (19) | 0.3711 (2) | 0.0249 (7) | |
C8' | 0.4313 (3) | 0.17471 (18) | 0.2828 (2) | 0.0220 (6) | |
C9' | 0.4293 (4) | 0.0644 (3) | 0.5067 (3) | 0.0413 (10) | |
H9'1 | 0.5206 | 0.0545 | 0.5407 | 0.050* | |
H9'2 | 0.3806 | 0.0172 | 0.4934 | 0.050* | |
H9'3 | 0.3850 | 0.0966 | 0.5367 | 0.050* | |
C10' | 0.9179 (4) | 0.0321 (2) | 0.4247 (2) | 0.0275 (7) | |
H10C | 0.8865 | −0.0189 | 0.4068 | 0.033* | |
H10D | 1.0163 | 0.0317 | 0.4444 | 0.033* | |
C11' | 0.8902 (3) | 0.0099 (2) | 0.5610 (2) | 0.0291 (8) | |
C12' | 0.8104 (4) | −0.0631 (2) | 0.5410 (2) | 0.0341 (8) | |
C13' | 0.8453 (4) | −0.1265 (3) | 0.5898 (3) | 0.0465 (11) | |
H13' | 0.9255 | −0.1262 | 0.6340 | 0.056* | |
C14' | 0.7669 (5) | −0.1896 (3) | 0.5759 (4) | 0.0620 (15) | |
H14' | 0.7935 | −0.2321 | 0.6100 | 0.074* | |
C15' | 0.6482 (5) | −0.1908 (3) | 0.5116 (4) | 0.0662 (16) | |
H15' | 0.5920 | −0.2334 | 0.5025 | 0.079* | |
C16' | 0.6136 (4) | −0.1287 (3) | 0.4610 (3) | 0.0502 (11) | |
H16' | 0.5347 | −0.1294 | 0.4159 | 0.060* | |
C17' | 0.6932 (4) | −0.0661 (2) | 0.4760 (2) | 0.0364 (9) | |
H17' | 0.6675 | −0.0240 | 0.4412 | 0.044* | |
C18' | 1.0409 (4) | −0.0040 (2) | 0.5970 (2) | 0.0318 (8) | |
C19' | 1.1023 (4) | −0.0619 (2) | 0.5687 (2) | 0.0352 (8) | |
H19' | 1.0496 | −0.0946 | 0.5283 | 0.042* | |
C20' | 1.2394 (4) | −0.0734 (3) | 0.5980 (3) | 0.0383 (9) | |
H20' | 1.2792 | −0.1131 | 0.5770 | 0.046* | |
C21' | 1.3161 (4) | −0.0272 (3) | 0.6570 (3) | 0.0426 (11) | |
C22' | 1.2572 (4) | 0.0323 (3) | 0.6849 (3) | 0.0425 (10) | |
H22' | 1.3109 | 0.0655 | 0.7244 | 0.051* | |
C23' | 1.1215 (4) | 0.0436 (3) | 0.6559 (2) | 0.0363 (9) | |
H23' | 1.0825 | 0.0841 | 0.6762 | 0.044* | |
C24' | 1.5121 (5) | −0.0974 (4) | 0.6669 (4) | 0.0663 (18) | |
H24D | 1.4763 | −0.1436 | 0.6825 | 0.080* | |
H24E | 1.6083 | −0.0953 | 0.6938 | 0.080* | |
H24F | 1.4946 | −0.0963 | 0.6074 | 0.080* | |
C25' | 0.8318 (4) | 0.0558 (3) | 0.6168 (2) | 0.0339 (8) | |
C26' | 0.7903 (5) | 0.0218 (3) | 0.6793 (3) | 0.0480 (11) | |
H26' | 0.8083 | −0.0296 | 0.6911 | 0.058* | |
C27' | 0.7247 (6) | 0.0618 (4) | 0.7231 (3) | 0.0582 (13) | |
H27' | 0.6989 | 0.0383 | 0.7656 | 0.070* | |
C28' | 0.6955 (5) | 0.1366 (3) | 0.7056 (3) | 0.0509 (12) | |
C29' | 0.7421 (5) | 0.1716 (3) | 0.6489 (3) | 0.0520 (12) | |
H29' | 0.7273 | 0.2234 | 0.6391 | 0.062* | |
C30' | 0.8113 (5) | 0.1310 (3) | 0.6057 (2) | 0.0445 (10) | |
H30' | 0.8452 | 0.1561 | 0.5674 | 0.053* | |
C31' | 0.5816 (9) | 0.2452 (5) | 0.7312 (4) | 0.094 (3) | |
H31D | 0.6571 | 0.2750 | 0.7269 | 0.112* | |
H31E | 0.5489 | 0.2656 | 0.7746 | 0.112* | |
H31F | 0.5103 | 0.2468 | 0.6791 | 0.112* | |
O15 | −0.2273 (8) | 0.7847 (6) | 0.2520 (7) | 0.084 (3) | 0.50 |
O16 | −0.0726 (15) | 0.8569 (8) | 0.3339 (12) | 0.155 (6) | 0.50 |
C63 | −0.2266 (16) | 0.8284 (16) | 0.1824 (12) | 0.155 (6) | 0.50 |
H63A | −0.1377 | 0.8267 | 0.1740 | 0.186* | 0.50 |
H63B | −0.2484 | 0.8810 | 0.1905 | 0.186* | 0.50 |
C64 | −0.3286 (10) | 0.7960 (6) | 0.1105 (7) | 0.059 (3) | 0.50 |
H64A | −0.3104 | 0.7428 | 0.1062 | 0.071* | 0.50 |
H64B | −0.3255 | 0.8217 | 0.0606 | 0.071* | 0.50 |
H64C | −0.4170 | 0.8021 | 0.1173 | 0.071* | 0.50 |
C65 | −0.1420 (14) | 0.8015 (9) | 0.3250 (8) | 0.140 (11) | 0.50 |
C66 | −0.128 (2) | 0.7486 (11) | 0.3939 (10) | 0.146 (10) | 0.50 |
H66A | −0.0357 | 0.7479 | 0.4288 | 0.175* | 0.50 |
H66B | −0.1543 | 0.6985 | 0.3721 | 0.175* | 0.50 |
H66C | −0.1860 | 0.7646 | 0.4262 | 0.175* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0175 (10) | 0.0245 (11) | 0.0224 (11) | −0.0002 (9) | 0.0046 (9) | −0.0009 (9) |
O2 | 0.0220 (11) | 0.0368 (14) | 0.0341 (13) | −0.0035 (11) | 0.0127 (10) | 0.0072 (11) |
O4 | 0.0183 (11) | 0.0297 (12) | 0.0365 (13) | 0.0040 (10) | 0.0108 (10) | 0.0108 (11) |
O3 | 0.0180 (12) | 0.0503 (17) | 0.0509 (16) | −0.0013 (12) | 0.0130 (11) | 0.0166 (14) |
O5 | 0.0272 (12) | 0.0192 (11) | 0.0220 (11) | −0.0017 (9) | 0.0015 (9) | 0.0031 (9) |
O6 | 0.0509 (18) | 0.0556 (19) | 0.0279 (13) | −0.0011 (15) | 0.0136 (13) | −0.0119 (13) |
O7 | 0.064 (2) | 0.0425 (17) | 0.0316 (14) | −0.0248 (15) | 0.0038 (13) | 0.0005 (13) |
N1 | 0.0152 (12) | 0.0240 (13) | 0.0257 (13) | 0.0010 (10) | 0.0067 (10) | 0.0052 (11) |
N2 | 0.0156 (12) | 0.0295 (14) | 0.0266 (14) | 0.0033 (12) | 0.0048 (11) | 0.0041 (11) |
C1 | 0.0151 (14) | 0.0203 (14) | 0.0234 (14) | 0.0006 (12) | 0.0038 (11) | 0.0003 (12) |
C2 | 0.0173 (14) | 0.0259 (16) | 0.0258 (15) | 0.0031 (13) | 0.0080 (12) | 0.0043 (13) |
C3 | 0.0192 (15) | 0.0296 (16) | 0.0199 (14) | −0.0016 (13) | 0.0055 (12) | 0.0003 (13) |
C4 | 0.0115 (13) | 0.0241 (15) | 0.0248 (15) | −0.0018 (12) | 0.0042 (11) | 0.0042 (12) |
C8 | 0.0188 (15) | 0.0256 (16) | 0.0191 (14) | 0.0041 (13) | 0.0063 (12) | 0.0018 (12) |
C5 | 0.0179 (15) | 0.0249 (16) | 0.0319 (17) | −0.0008 (13) | 0.0055 (13) | 0.0047 (13) |
C6 | 0.0204 (16) | 0.0334 (18) | 0.0321 (17) | −0.0016 (14) | 0.0054 (13) | 0.0095 (15) |
C7 | 0.0209 (16) | 0.0349 (18) | 0.0292 (17) | −0.0003 (14) | 0.0072 (13) | 0.0042 (14) |
C9 | 0.0244 (18) | 0.046 (2) | 0.062 (3) | −0.0028 (18) | 0.0135 (18) | 0.025 (2) |
C10 | 0.0228 (15) | 0.0220 (15) | 0.0234 (15) | 0.0000 (13) | 0.0025 (12) | 0.0016 (12) |
C11 | 0.0279 (16) | 0.0217 (15) | 0.0220 (15) | 0.0011 (13) | 0.0041 (13) | 0.0034 (12) |
C12 | 0.0339 (18) | 0.0191 (15) | 0.0307 (17) | 0.0004 (14) | 0.0118 (14) | 0.0020 (13) |
C13 | 0.041 (2) | 0.0261 (18) | 0.043 (2) | 0.0093 (17) | 0.0150 (18) | 0.0090 (16) |
C14 | 0.041 (2) | 0.030 (2) | 0.073 (3) | 0.0130 (18) | 0.024 (2) | 0.010 (2) |
C15 | 0.048 (3) | 0.033 (2) | 0.082 (4) | 0.008 (2) | 0.036 (3) | −0.003 (2) |
C16 | 0.054 (3) | 0.031 (2) | 0.064 (3) | −0.0059 (19) | 0.036 (2) | −0.008 (2) |
C17 | 0.046 (2) | 0.0277 (18) | 0.0365 (19) | −0.0022 (17) | 0.0208 (17) | −0.0014 (15) |
C18 | 0.0273 (17) | 0.0217 (15) | 0.0218 (15) | 0.0042 (13) | 0.0056 (13) | 0.0019 (12) |
C19 | 0.0248 (16) | 0.0312 (18) | 0.0245 (16) | 0.0040 (14) | 0.0045 (13) | 0.0017 (13) |
C20 | 0.0306 (19) | 0.039 (2) | 0.0242 (16) | −0.0026 (16) | 0.0017 (14) | −0.0024 (15) |
C21 | 0.041 (2) | 0.0265 (17) | 0.0232 (16) | 0.0011 (15) | 0.0090 (15) | −0.0016 (13) |
C22 | 0.0322 (19) | 0.0320 (18) | 0.0309 (17) | 0.0050 (15) | 0.0126 (15) | −0.0025 (15) |
C23 | 0.0249 (17) | 0.0326 (18) | 0.0254 (16) | 0.0016 (14) | 0.0049 (13) | −0.0004 (14) |
C24 | 0.070 (3) | 0.058 (3) | 0.044 (2) | 0.005 (3) | 0.031 (2) | −0.012 (2) |
C25 | 0.0301 (17) | 0.0219 (15) | 0.0243 (16) | −0.0013 (14) | 0.0057 (13) | 0.0015 (12) |
C26 | 0.051 (2) | 0.0319 (19) | 0.0242 (17) | −0.0094 (18) | 0.0048 (16) | 0.0017 (15) |
C27 | 0.051 (2) | 0.032 (2) | 0.0304 (18) | −0.0151 (18) | 0.0087 (17) | 0.0042 (16) |
C28 | 0.042 (2) | 0.0321 (18) | 0.0273 (17) | −0.0109 (17) | 0.0083 (16) | −0.0037 (15) |
C29 | 0.050 (2) | 0.041 (2) | 0.0245 (17) | −0.0100 (19) | 0.0022 (16) | 0.0009 (16) |
C30 | 0.046 (2) | 0.0270 (17) | 0.0259 (17) | −0.0103 (16) | 0.0053 (15) | 0.0045 (14) |
C31 | 0.066 (3) | 0.040 (2) | 0.043 (2) | −0.027 (2) | 0.014 (2) | −0.0032 (19) |
O1' | 0.0192 (11) | 0.0308 (13) | 0.0296 (12) | 0.0051 (10) | 0.0047 (9) | 0.0015 (10) |
O2' | 0.0298 (14) | 0.0503 (17) | 0.0455 (16) | 0.0008 (13) | 0.0211 (13) | 0.0188 (14) |
O3' | 0.0206 (12) | 0.0407 (15) | 0.0460 (15) | 0.0020 (11) | 0.0167 (11) | 0.0117 (12) |
O4' | 0.0224 (11) | 0.0348 (13) | 0.0224 (11) | 0.0085 (10) | 0.0078 (9) | 0.0092 (10) |
O5' | 0.0267 (12) | 0.0359 (13) | 0.0210 (11) | 0.0075 (11) | 0.0094 (9) | 0.0097 (10) |
O6' | 0.0225 (14) | 0.082 (3) | 0.062 (2) | 0.0028 (16) | 0.0080 (13) | 0.0292 (19) |
O7' | 0.098 (3) | 0.107 (4) | 0.057 (2) | 0.029 (3) | 0.046 (2) | 0.001 (2) |
N1' | 0.0160 (13) | 0.0287 (14) | 0.0220 (13) | 0.0032 (11) | 0.0066 (10) | 0.0060 (11) |
N2' | 0.0131 (13) | 0.0313 (15) | 0.0239 (13) | 0.0037 (12) | 0.0038 (11) | 0.0051 (12) |
C1' | 0.0163 (15) | 0.0386 (19) | 0.0226 (15) | 0.0065 (14) | 0.0068 (12) | 0.0072 (14) |
C2' | 0.0175 (15) | 0.043 (2) | 0.0251 (16) | −0.0008 (15) | 0.0046 (13) | 0.0101 (15) |
C3' | 0.0197 (16) | 0.0334 (17) | 0.0260 (16) | 0.0021 (14) | 0.0089 (13) | 0.0035 (14) |
C4' | 0.0185 (15) | 0.0266 (16) | 0.0259 (15) | 0.0044 (13) | 0.0101 (12) | 0.0058 (13) |
C5' | 0.0213 (16) | 0.0299 (17) | 0.0236 (15) | 0.0043 (13) | 0.0078 (13) | 0.0053 (13) |
C6' | 0.0225 (16) | 0.0316 (18) | 0.0288 (16) | 0.0024 (14) | 0.0089 (13) | 0.0097 (14) |
C7' | 0.0208 (16) | 0.0244 (16) | 0.0312 (17) | 0.0007 (13) | 0.0103 (13) | 0.0051 (13) |
C8' | 0.0188 (15) | 0.0224 (15) | 0.0233 (15) | 0.0003 (12) | 0.0043 (12) | 0.0006 (12) |
C9' | 0.032 (2) | 0.059 (3) | 0.038 (2) | 0.0031 (19) | 0.0184 (17) | 0.019 (2) |
C10' | 0.0278 (17) | 0.0347 (18) | 0.0216 (15) | 0.0124 (15) | 0.0098 (13) | 0.0074 (13) |
C11' | 0.0227 (16) | 0.039 (2) | 0.0231 (16) | 0.0016 (15) | 0.0038 (13) | 0.0127 (14) |
C12' | 0.0249 (17) | 0.042 (2) | 0.0346 (19) | 0.0053 (16) | 0.0081 (15) | 0.0133 (17) |
C13' | 0.030 (2) | 0.052 (3) | 0.050 (2) | 0.0005 (19) | 0.0014 (18) | 0.027 (2) |
C14' | 0.046 (3) | 0.051 (3) | 0.079 (4) | −0.004 (2) | 0.003 (2) | 0.032 (3) |
C15' | 0.044 (3) | 0.050 (3) | 0.096 (4) | −0.011 (2) | 0.008 (3) | 0.022 (3) |
C16' | 0.035 (2) | 0.045 (2) | 0.060 (3) | 0.000 (2) | −0.001 (2) | 0.008 (2) |
C17' | 0.0288 (18) | 0.036 (2) | 0.040 (2) | 0.0058 (16) | 0.0030 (16) | 0.0146 (17) |
C18' | 0.0259 (17) | 0.044 (2) | 0.0251 (16) | −0.0009 (16) | 0.0066 (14) | 0.0174 (15) |
C19' | 0.0284 (18) | 0.042 (2) | 0.0351 (19) | 0.0057 (16) | 0.0085 (15) | 0.0144 (17) |
C20' | 0.032 (2) | 0.043 (2) | 0.042 (2) | 0.0082 (18) | 0.0142 (17) | 0.0207 (18) |
C21' | 0.0230 (18) | 0.063 (3) | 0.041 (2) | 0.0021 (19) | 0.0096 (16) | 0.029 (2) |
C22' | 0.033 (2) | 0.054 (3) | 0.034 (2) | −0.0126 (19) | 0.0014 (16) | 0.0111 (19) |
C23' | 0.0282 (18) | 0.047 (2) | 0.0316 (18) | 0.0019 (17) | 0.0058 (15) | 0.0132 (17) |
C24' | 0.034 (2) | 0.094 (4) | 0.074 (4) | 0.020 (3) | 0.021 (2) | 0.047 (3) |
C25' | 0.0251 (17) | 0.056 (2) | 0.0198 (16) | 0.0034 (17) | 0.0057 (13) | 0.0060 (16) |
C26' | 0.053 (3) | 0.058 (3) | 0.037 (2) | 0.001 (2) | 0.019 (2) | 0.012 (2) |
C27' | 0.067 (3) | 0.079 (4) | 0.038 (2) | 0.006 (3) | 0.029 (2) | 0.008 (2) |
C28' | 0.048 (3) | 0.071 (3) | 0.039 (2) | 0.012 (2) | 0.023 (2) | 0.003 (2) |
C29' | 0.060 (3) | 0.060 (3) | 0.032 (2) | 0.013 (2) | 0.008 (2) | 0.006 (2) |
C30' | 0.048 (2) | 0.059 (3) | 0.0283 (19) | 0.012 (2) | 0.0136 (18) | 0.0023 (18) |
C31' | 0.120 (6) | 0.102 (6) | 0.061 (4) | 0.065 (5) | 0.031 (4) | 0.005 (4) |
O15 | 0.049 (4) | 0.094 (7) | 0.112 (8) | −0.006 (5) | 0.029 (5) | −0.032 (6) |
O16 | 0.121 (9) | 0.153 (11) | 0.229 (15) | −0.044 (8) | 0.110 (10) | −0.094 (11) |
C63 | 0.121 (9) | 0.153 (11) | 0.229 (15) | −0.044 (8) | 0.110 (10) | −0.094 (11) |
C64 | 0.046 (5) | 0.054 (6) | 0.084 (8) | 0.007 (5) | 0.027 (5) | 0.011 (6) |
C65 | 0.119 (16) | 0.112 (16) | 0.24 (3) | −0.051 (13) | 0.13 (2) | −0.086 (18) |
C66 | 0.16 (2) | 0.16 (2) | 0.101 (14) | 0.056 (17) | 0.015 (13) | −0.063 (15) |
Geometric parameters (Å, º) top
O1—C1 | 1.452 (4) | O5'—C11' | 1.450 (4) |
O1—C4 | 1.422 (4) | O6'—C21' | 1.361 (5) |
O2—C2 | 1.426 (4) | O6'—C24' | 1.427 (8) |
O2—H2O | 0.8400 | O7'—C28' | 1.374 (6) |
O4—C8 | 1.228 (4) | O7'—C31' | 1.420 (9) |
O3—C7 | 1.218 (4) | N1'—C8' | 1.370 (4) |
O5—C10 | 1.427 (4) | N1'—C5' | 1.382 (4) |
O5—C11 | 1.453 (4) | N1'—C4' | 1.471 (4) |
O6—C21 | 1.372 (4) | N2'—C8' | 1.355 (4) |
O6—C24 | 1.441 (6) | N2'—C7' | 1.382 (4) |
O7—C28 | 1.368 (5) | N2'—H2'N | 0.77 (4) |
O7—C31 | 1.424 (5) | C1'—C10' | 1.511 (4) |
N1—C8 | 1.364 (4) | C1'—C2' | 1.543 (5) |
N1—C5 | 1.392 (4) | C1'—H1' | 1.0000 |
N1—C4 | 1.466 (4) | C2'—C3' | 1.514 (5) |
N2—C8 | 1.370 (4) | C2'—H2' | 1.0000 |
N2—C7 | 1.393 (5) | C3'—C4' | 1.520 (5) |
N2—H2N | 0.96 (4) | C3'—H3'1 | 0.9900 |
C1—C10 | 1.511 (4) | C3'—H3'2 | 0.9900 |
C1—C2 | 1.531 (4) | C4'—H4' | 1.0000 |
C1—H1 | 1.0000 | C5'—C6' | 1.342 (5) |
C2—C3 | 1.515 (4) | C5'—H5' | 0.9500 |
C2—H2 | 1.0000 | C6'—C7' | 1.459 (5) |
C3—C4 | 1.518 (5) | C6'—C9' | 1.489 (5) |
C3—H3A | 0.9900 | C9'—H9'1 | 0.9800 |
C3—H3B | 0.9900 | C9'—H9'2 | 0.9800 |
C4—H4 | 1.0000 | C9'—H9'3 | 0.9800 |
C5—C6 | 1.340 (5) | C10'—H10C | 0.9900 |
C5—H5 | 0.9500 | C10'—H10D | 0.9900 |
C6—C7 | 1.453 (5) | C11'—C25' | 1.525 (6) |
C6—C9 | 1.505 (5) | C11'—C12' | 1.538 (6) |
C9—H9A | 0.9800 | C11'—C18' | 1.541 (5) |
C9—H9B | 0.9800 | C12'—C17' | 1.394 (5) |
C9—H9C | 0.9800 | C12'—C13' | 1.394 (5) |
C10—H10A | 0.9900 | C13'—C14' | 1.379 (7) |
C10—H10B | 0.9900 | C13'—H13' | 0.9500 |
C11—C25 | 1.532 (5) | C14'—C15' | 1.397 (7) |
C11—C12 | 1.535 (5) | C14'—H14' | 0.9500 |
C11—C18 | 1.543 (5) | C15'—C16' | 1.390 (7) |
C12—C13 | 1.394 (5) | C15'—H15' | 0.9500 |
C12—C17 | 1.395 (5) | C16'—C17' | 1.379 (6) |
C13—C14 | 1.375 (6) | C16'—H16' | 0.9500 |
C13—H13 | 0.9500 | C17'—H17' | 0.9500 |
C14—C15 | 1.375 (7) | C18'—C19' | 1.385 (6) |
C14—H14 | 0.9500 | C18'—C23' | 1.398 (6) |
C15—C16 | 1.375 (7) | C19'—C20' | 1.395 (5) |
C15—H15 | 0.9500 | C19'—H19' | 0.9500 |
C16—C17 | 1.391 (6) | C20'—C21' | 1.367 (7) |
C16—H16 | 0.9500 | C20'—H20' | 0.9500 |
C17—H17 | 0.9500 | C21'—C22' | 1.391 (7) |
C18—C23 | 1.385 (5) | C22'—C23' | 1.381 (6) |
C18—C19 | 1.395 (5) | C22'—H22' | 0.9500 |
C19—C20 | 1.383 (5) | C23'—H23' | 0.9500 |
C19—H19 | 0.9500 | C24'—H24D | 0.9800 |
C20—C21 | 1.383 (6) | C24'—H24E | 0.9800 |
C20—H20 | 0.9500 | C24'—H24F | 0.9800 |
C21—C22 | 1.383 (5) | C25'—C30' | 1.369 (7) |
C22—C23 | 1.400 (5) | C25'—C26' | 1.411 (6) |
C22—H22 | 0.9500 | C26'—C27' | 1.367 (7) |
C23—H23 | 0.9500 | C26'—H26' | 0.9500 |
C24—H24A | 0.9800 | C27'—C28' | 1.388 (8) |
C24—H24B | 0.9800 | C27'—H27' | 0.9500 |
C24—H24C | 0.9800 | C28'—C29' | 1.366 (7) |
C25—C26 | 1.389 (5) | C29'—C30' | 1.392 (7) |
C25—C30 | 1.397 (5) | C29'—H29' | 0.9500 |
C26—C27 | 1.384 (6) | C30'—H30' | 0.9500 |
C26—H26 | 0.9500 | C31'—H31D | 0.9800 |
C27—C28 | 1.388 (5) | C31'—H31E | 0.9800 |
C27—H27 | 0.9500 | C31'—H31F | 0.9800 |
C28—C29 | 1.382 (6) | O15—C65 | 1.338 (3) |
C29—C30 | 1.381 (5) | O15—C63 | 1.43 (3) |
C29—H29 | 0.9500 | O16—C65 | 1.216 (3) |
C30—H30 | 0.9500 | C63—C64 | 1.489 (3) |
C31—H31A | 0.9800 | C63—H63A | 0.9900 |
C31—H31B | 0.9800 | C63—H63B | 0.9900 |
C31—H31C | 0.9800 | C64—H64A | 0.9800 |
O1'—C1' | 1.442 (4) | C64—H64B | 0.9800 |
O1'—C4' | 1.423 (4) | C64—H64C | 0.9800 |
O2'—C2' | 1.424 (4) | C65—C66 | 1.486 (3) |
O2'—H2'O | 0.95 (5) | C66—H66A | 0.9800 |
O3'—C7' | 1.225 (4) | C66—H66B | 0.9800 |
O4'—C8' | 1.227 (4) | C66—H66C | 0.9800 |
O5'—C10' | 1.429 (4) | | |
| | | |
C4—O1—C1 | 110.4 (2) | O1'—C1'—C10' | 110.3 (3) |
C2—O2—H2O | 109.5 | O1'—C1'—C2' | 106.4 (3) |
C10—O5—C11 | 115.2 (2) | C10'—C1'—C2' | 115.0 (3) |
C21—O6—C24 | 117.0 (3) | O1'—C1'—H1' | 108.3 |
C28—O7—C31 | 117.2 (3) | C10'—C1'—H1' | 108.3 |
C8—N1—C5 | 121.1 (3) | C2'—C1'—H1' | 108.3 |
C8—N1—C4 | 119.5 (3) | O2'—C2'—C3' | 106.8 (3) |
C5—N1—C4 | 119.3 (3) | O2'—C2'—C1' | 111.3 (3) |
C8—N2—C7 | 127.1 (3) | C3'—C2'—C1' | 103.6 (3) |
C8—N2—H2N | 115 (2) | O2'—C2'—H2' | 111.6 |
C7—N2—H2N | 118 (2) | C3'—C2'—H2' | 111.6 |
O1—C1—C10 | 109.4 (3) | C1'—C2'—H2' | 111.6 |
O1—C1—C2 | 105.8 (2) | C2'—C3'—C4' | 102.5 (3) |
C10—C1—C2 | 116.8 (3) | C2'—C3'—H3'1 | 111.3 |
O1—C1—H1 | 108.2 | C4'—C3'—H3'1 | 111.3 |
C10—C1—H1 | 108.2 | C2'—C3'—H3'2 | 111.3 |
C2—C1—H1 | 108.2 | C4'—C3'—H3'2 | 111.3 |
O2—C2—C3 | 106.6 (3) | H3'1—C3'—H3'2 | 109.2 |
O2—C2—C1 | 110.8 (3) | O1'—C4'—N1' | 107.0 (3) |
C3—C2—C1 | 103.5 (3) | O1'—C4'—C3' | 106.3 (3) |
O2—C2—H2 | 111.8 | N1'—C4'—C3' | 114.3 (3) |
C3—C2—H2 | 111.8 | O1'—C4'—H4' | 109.7 |
C1—C2—H2 | 111.8 | N1'—C4'—H4' | 109.7 |
C2—C3—C4 | 102.7 (3) | C3'—C4'—H4' | 109.7 |
C2—C3—H3A | 111.2 | C6'—C5'—N1' | 124.1 (3) |
C4—C3—H3A | 111.2 | C6'—C5'—H5' | 118.0 |
C2—C3—H3B | 111.2 | N1'—C5'—H5' | 118.0 |
C4—C3—H3B | 111.2 | C5'—C6'—C7' | 117.5 (3) |
H3A—C3—H3B | 109.1 | C5'—C6'—C9' | 123.7 (3) |
O1—C4—N1 | 107.1 (2) | C7'—C6'—C9' | 118.7 (3) |
O1—C4—C3 | 105.8 (2) | O3'—C7'—N2' | 120.2 (3) |
N1—C4—C3 | 114.6 (3) | O3'—C7'—C6' | 125.4 (3) |
O1—C4—H4 | 109.7 | N2'—C7'—C6' | 114.4 (3) |
N1—C4—H4 | 109.7 | O4'—C8'—N2' | 122.1 (3) |
C3—C4—H4 | 109.7 | O4'—C8'—N1' | 122.7 (3) |
O4—C8—N1 | 123.6 (3) | N2'—C8'—N1' | 115.2 (3) |
O4—C8—N2 | 121.1 (3) | C6'—C9'—H9'1 | 109.5 |
N1—C8—N2 | 115.4 (3) | C6'—C9'—H9'2 | 109.5 |
C6—C5—N1 | 123.3 (3) | H9'1—C9'—H9'2 | 109.5 |
C6—C5—H5 | 118.3 | C6'—C9'—H9'3 | 109.5 |
N1—C5—H5 | 118.3 | H9'1—C9'—H9'3 | 109.5 |
C5—C6—C7 | 118.5 (3) | H9'2—C9'—H9'3 | 109.5 |
C5—C6—C9 | 122.8 (3) | O5'—C10'—C1' | 107.6 (3) |
C7—C6—C9 | 118.7 (3) | O5'—C10'—H10C | 110.2 |
O3—C7—N2 | 119.4 (3) | C1'—C10'—H10C | 110.2 |
O3—C7—C6 | 126.0 (3) | O5'—C10'—H10D | 110.2 |
N2—C7—C6 | 114.5 (3) | C1'—C10'—H10D | 110.2 |
C6—C9—H9A | 109.5 | H10C—C10'—H10D | 108.5 |
C6—C9—H9B | 109.5 | O5'—C11'—C25' | 103.2 (3) |
H9A—C9—H9B | 109.5 | O5'—C11'—C12' | 110.5 (3) |
C6—C9—H9C | 109.5 | C25'—C11'—C12' | 107.7 (3) |
H9A—C9—H9C | 109.5 | O5'—C11'—C18' | 109.3 (3) |
H9B—C9—H9C | 109.5 | C25'—C11'—C18' | 113.5 (3) |
O5—C10—C1 | 109.8 (3) | C12'—C11'—C18' | 112.4 (3) |
O5—C10—H10A | 109.7 | C17'—C12'—C13' | 117.3 (4) |
C1—C10—H10A | 109.7 | C17'—C12'—C11' | 120.4 (3) |
O5—C10—H10B | 109.7 | C13'—C12'—C11' | 122.1 (3) |
C1—C10—H10B | 109.7 | C14'—C13'—C12' | 121.9 (4) |
H10A—C10—H10B | 108.2 | C14'—C13'—H13' | 119.0 |
O5—C11—C25 | 104.8 (3) | C12'—C13'—H13' | 119.0 |
O5—C11—C12 | 109.9 (3) | C13'—C14'—C15' | 119.9 (4) |
C25—C11—C12 | 106.2 (3) | C13'—C14'—H14' | 120.1 |
O5—C11—C18 | 108.2 (3) | C15'—C14'—H14' | 120.1 |
C25—C11—C18 | 112.6 (3) | C16'—C15'—C14' | 118.9 (5) |
C12—C11—C18 | 114.7 (3) | C16'—C15'—H15' | 120.5 |
C13—C12—C17 | 118.2 (4) | C14'—C15'—H15' | 120.5 |
C13—C12—C11 | 122.7 (3) | C17'—C16'—C15' | 120.4 (4) |
C17—C12—C11 | 118.8 (3) | C17'—C16'—H16' | 119.8 |
C14—C13—C12 | 121.1 (4) | C15'—C16'—H16' | 119.8 |
C14—C13—H13 | 119.5 | C16'—C17'—C12' | 121.6 (4) |
C12—C13—H13 | 119.5 | C16'—C17'—H17' | 119.2 |
C15—C14—C13 | 120.1 (4) | C12'—C17'—H17' | 119.2 |
C15—C14—H14 | 120.0 | C19'—C18'—C23' | 117.6 (4) |
C13—C14—H14 | 120.0 | C19'—C18'—C11' | 121.0 (4) |
C14—C15—C16 | 120.2 (4) | C23'—C18'—C11' | 121.3 (4) |
C14—C15—H15 | 119.9 | C18'—C19'—C20' | 121.9 (4) |
C16—C15—H15 | 119.9 | C18'—C19'—H19' | 119.1 |
C15—C16—C17 | 120.0 (4) | C20'—C19'—H19' | 119.1 |
C15—C16—H16 | 120.0 | C21'—C20'—C19' | 119.6 (4) |
C17—C16—H16 | 120.0 | C21'—C20'—H20' | 120.2 |
C16—C17—C12 | 120.4 (4) | C19'—C20'—H20' | 120.2 |
C16—C17—H17 | 119.8 | O6'—C21'—C20' | 124.5 (5) |
C12—C17—H17 | 119.8 | O6'—C21'—C22' | 116.0 (4) |
C23—C18—C19 | 117.6 (3) | C20'—C21'—C22' | 119.6 (4) |
C23—C18—C11 | 119.9 (3) | C23'—C22'—C21' | 120.7 (4) |
C19—C18—C11 | 122.0 (3) | C23'—C22'—H22' | 119.7 |
C20—C19—C18 | 121.2 (3) | C21'—C22'—H22' | 119.7 |
C20—C19—H19 | 119.4 | C22'—C23'—C18' | 120.6 (4) |
C18—C19—H19 | 119.4 | C22'—C23'—H23' | 119.7 |
C21—C20—C19 | 120.5 (3) | C18'—C23'—H23' | 119.7 |
C21—C20—H20 | 119.8 | O6'—C24'—H24D | 109.5 |
C19—C20—H20 | 119.8 | O6'—C24'—H24E | 109.5 |
O6—C21—C22 | 124.5 (4) | H24D—C24'—H24E | 109.5 |
O6—C21—C20 | 116.0 (3) | O6'—C24'—H24F | 109.5 |
C22—C21—C20 | 119.6 (3) | H24D—C24'—H24F | 109.5 |
C21—C22—C23 | 119.5 (3) | H24E—C24'—H24F | 109.5 |
C21—C22—H22 | 120.2 | C30'—C25'—C26' | 117.3 (4) |
C23—C22—H22 | 120.2 | C30'—C25'—C11' | 121.4 (4) |
C18—C23—C22 | 121.6 (3) | C26'—C25'—C11' | 121.2 (4) |
C18—C23—H23 | 119.2 | C27'—C26'—C25' | 120.9 (5) |
C22—C23—H23 | 119.2 | C27'—C26'—H26' | 119.5 |
O6—C24—H24A | 109.5 | C25'—C26'—H26' | 119.5 |
O6—C24—H24B | 109.5 | C26'—C27'—C28' | 120.3 (5) |
H24A—C24—H24B | 109.5 | C26'—C27'—H27' | 119.8 |
O6—C24—H24C | 109.5 | C28'—C27'—H27' | 119.8 |
H24A—C24—H24C | 109.5 | C29'—C28'—O7' | 125.0 (5) |
H24B—C24—H24C | 109.5 | C29'—C28'—C27' | 119.5 (5) |
C26—C25—C30 | 117.1 (3) | O7'—C28'—C27' | 115.4 (5) |
C26—C25—C11 | 121.3 (3) | C28'—C29'—C30' | 119.8 (5) |
C30—C25—C11 | 121.3 (3) | C28'—C29'—H29' | 120.1 |
C27—C26—C25 | 121.6 (3) | C30'—C29'—H29' | 120.1 |
C27—C26—H26 | 119.2 | C25'—C30'—C29' | 121.8 (4) |
C25—C26—H26 | 119.2 | C25'—C30'—H30' | 119.1 |
C26—C27—C28 | 120.3 (4) | C29'—C30'—H30' | 119.1 |
C26—C27—H27 | 119.9 | O7'—C31'—H31D | 109.5 |
C28—C27—H27 | 119.9 | O7'—C31'—H31E | 109.5 |
O7—C28—C29 | 116.7 (3) | H31D—C31'—H31E | 109.5 |
O7—C28—C27 | 124.2 (4) | O7'—C31'—H31F | 109.5 |
C29—C28—C27 | 119.1 (4) | H31D—C31'—H31F | 109.5 |
C30—C29—C28 | 120.1 (3) | H31E—C31'—H31F | 109.5 |
C30—C29—H29 | 120.0 | C65—O15—C63 | 119.1 (11) |
C28—C29—H29 | 120.0 | O15—C63—C64 | 107.0 (16) |
C29—C30—C25 | 121.8 (3) | O15—C63—H63A | 110.3 |
C29—C30—H30 | 119.1 | C64—C63—H63A | 110.3 |
C25—C30—H30 | 119.1 | O15—C63—H63B | 110.3 |
O7—C31—H31A | 109.5 | C64—C63—H63B | 110.3 |
O7—C31—H31B | 109.5 | H63A—C63—H63B | 108.6 |
H31A—C31—H31B | 109.5 | C63—C64—H64A | 109.5 |
O7—C31—H31C | 109.5 | C63—C64—H64B | 109.5 |
H31A—C31—H31C | 109.5 | H64A—C64—H64B | 109.5 |
H31B—C31—H31C | 109.5 | C63—C64—H64C | 109.5 |
C4'—O1'—C1' | 109.9 (3) | H64A—C64—H64C | 109.5 |
C2'—O2'—H2'O | 109 (3) | H64B—C64—H64C | 109.5 |
C10'—O5'—C11' | 118.3 (3) | O16—C65—O15 | 120.7 (15) |
C21'—O6'—C24' | 117.3 (4) | O16—C65—C66 | 120.8 (16) |
C28'—O7'—C31' | 118.1 (5) | O15—C65—C66 | 118.5 (13) |
C8'—N1'—C5' | 120.7 (3) | C65—C66—H66A | 109.5 |
C8'—N1'—C4' | 119.6 (3) | C65—C66—H66B | 109.5 |
C5'—N1'—C4' | 119.7 (3) | H66A—C66—H66B | 109.5 |
C8'—N2'—C7' | 128.1 (3) | C65—C66—H66C | 109.5 |
C8'—N2'—H2'N | 117 (3) | H66A—C66—H66C | 109.5 |
C7'—N2'—H2'N | 115 (3) | H66B—C66—H66C | 109.5 |
| | | |
C4—O1—C1—C10 | 125.0 (3) | O1'—C1'—C2'—O2' | −95.8 (3) |
C4—O1—C1—C2 | −1.7 (3) | C10'—C1'—C2'—O2' | 141.8 (3) |
O1—C1—C2—O2 | −92.0 (3) | O1'—C1'—C2'—C3' | 18.7 (3) |
C10—C1—C2—O2 | 146.0 (3) | C10'—C1'—C2'—C3' | −103.7 (3) |
O1—C1—C2—C3 | 22.0 (3) | O2'—C2'—C3'—C4' | 86.9 (3) |
C10—C1—C2—C3 | −100.0 (3) | C1'—C2'—C3'—C4' | −30.8 (3) |
O2—C2—C3—C4 | 84.3 (3) | C1'—O1'—C4'—N1' | −144.8 (3) |
C1—C2—C3—C4 | −32.7 (3) | C1'—O1'—C4'—C3' | −22.2 (3) |
C1—O1—C4—N1 | −142.2 (3) | C8'—N1'—C4'—O1' | −121.5 (3) |
C1—O1—C4—C3 | −19.5 (3) | C5'—N1'—C4'—O1' | 55.5 (4) |
C8—N1—C4—O1 | −120.7 (3) | C8'—N1'—C4'—C3' | 121.1 (3) |
C5—N1—C4—O1 | 55.3 (4) | C5'—N1'—C4'—C3' | −61.9 (4) |
C8—N1—C4—C3 | 122.3 (3) | C2'—C3'—C4'—O1' | 33.2 (3) |
C5—N1—C4—C3 | −61.8 (4) | C2'—C3'—C4'—N1' | 151.0 (3) |
C2—C3—C4—O1 | 32.6 (3) | C8'—N1'—C5'—C6' | 1.9 (5) |
C2—C3—C4—N1 | 150.3 (3) | C4'—N1'—C5'—C6' | −175.1 (3) |
C5—N1—C8—O4 | −175.7 (3) | N1'—C5'—C6'—C7' | 0.7 (6) |
C4—N1—C8—O4 | 0.2 (5) | N1'—C5'—C6'—C9' | 179.3 (4) |
C5—N1—C8—N2 | 3.5 (4) | C8'—N2'—C7'—O3' | 180.0 (3) |
C4—N1—C8—N2 | 179.4 (3) | C8'—N2'—C7'—C6' | 1.4 (5) |
C7—N2—C8—O4 | 174.8 (3) | C5'—C6'—C7'—O3' | 179.3 (4) |
C7—N2—C8—N1 | −4.5 (5) | C9'—C6'—C7'—O3' | 0.7 (6) |
C8—N1—C5—C6 | −1.5 (5) | C5'—C6'—C7'—N2' | −2.2 (5) |
C4—N1—C5—C6 | −177.4 (3) | C9'—C6'—C7'—N2' | 179.1 (4) |
N1—C5—C6—C7 | 0.0 (6) | C7'—N2'—C8'—O4' | −178.8 (3) |
N1—C5—C6—C9 | 179.9 (4) | C7'—N2'—C8'—N1' | 1.0 (5) |
C8—N2—C7—O3 | −177.9 (3) | C5'—N1'—C8'—O4' | 177.1 (3) |
C8—N2—C7—C6 | 3.1 (5) | C4'—N1'—C8'—O4' | −5.9 (5) |
C5—C6—C7—O3 | −179.5 (4) | C5'—N1'—C8'—N2' | −2.7 (5) |
C9—C6—C7—O3 | 0.6 (6) | C4'—N1'—C8'—N2' | 174.3 (3) |
C5—C6—C7—N2 | −0.6 (5) | C11'—O5'—C10'—C1' | 175.5 (3) |
C9—C6—C7—N2 | 179.5 (4) | O1'—C1'—C10'—O5' | −63.3 (4) |
C11—O5—C10—C1 | −175.7 (3) | C2'—C1'—C10'—O5' | 57.0 (4) |
O1—C1—C10—O5 | −66.4 (3) | C10'—O5'—C11'—C25' | 175.3 (3) |
C2—C1—C10—O5 | 53.7 (4) | C10'—O5'—C11'—C12' | −69.9 (4) |
C10—O5—C11—C25 | 179.9 (3) | C10'—O5'—C11'—C18' | 54.3 (4) |
C10—O5—C11—C12 | 66.2 (3) | O5'—C11'—C12'—C17' | −26.2 (5) |
C10—O5—C11—C18 | −59.7 (4) | C25'—C11'—C12'—C17' | 85.8 (4) |
O5—C11—C12—C13 | −153.9 (3) | C18'—C11'—C12'—C17' | −148.5 (4) |
C25—C11—C12—C13 | 93.3 (4) | O5'—C11'—C12'—C13' | 159.0 (4) |
C18—C11—C12—C13 | −31.8 (5) | C25'—C11'—C12'—C13' | −89.0 (5) |
O5—C11—C12—C17 | 32.5 (4) | C18'—C11'—C12'—C13' | 36.6 (5) |
C25—C11—C12—C17 | −80.3 (4) | C17'—C12'—C13'—C14' | −1.0 (7) |
C18—C11—C12—C17 | 154.6 (3) | C11'—C12'—C13'—C14' | 174.0 (5) |
C17—C12—C13—C14 | −2.7 (6) | C12'—C13'—C14'—C15' | −0.4 (9) |
C11—C12—C13—C14 | −176.4 (4) | C13'—C14'—C15'—C16' | 2.0 (10) |
C12—C13—C14—C15 | 1.8 (7) | C14'—C15'—C16'—C17' | −2.1 (9) |
C13—C14—C15—C16 | 0.6 (7) | C15'—C16'—C17'—C12' | 0.7 (8) |
C14—C15—C16—C17 | −2.0 (7) | C13'—C12'—C17'—C16' | 0.9 (7) |
C15—C16—C17—C12 | 1.0 (6) | C11'—C12'—C17'—C16' | −174.2 (4) |
C13—C12—C17—C16 | 1.4 (6) | O5'—C11'—C18'—C19' | −85.6 (4) |
C11—C12—C17—C16 | 175.3 (4) | C25'—C11'—C18'—C19' | 159.9 (3) |
O5—C11—C18—C23 | −82.0 (4) | C12'—C11'—C18'—C19' | 37.5 (4) |
C25—C11—C18—C23 | 33.4 (4) | O5'—C11'—C18'—C23' | 90.7 (4) |
C12—C11—C18—C23 | 154.9 (3) | C25'—C11'—C18'—C23' | −23.8 (5) |
O5—C11—C18—C19 | 90.5 (4) | C12'—C11'—C18'—C23' | −146.2 (3) |
C25—C11—C18—C19 | −154.2 (3) | C23'—C18'—C19'—C20' | 0.7 (5) |
C12—C11—C18—C19 | −32.6 (5) | C11'—C18'—C19'—C20' | 177.1 (3) |
C23—C18—C19—C20 | 0.1 (5) | C18'—C19'—C20'—C21' | 0.8 (6) |
C11—C18—C19—C20 | −172.6 (3) | C24'—O6'—C21'—C20' | −3.0 (6) |
C18—C19—C20—C21 | 0.2 (6) | C24'—O6'—C21'—C22' | 177.2 (4) |
C24—O6—C21—C22 | 8.2 (6) | C19'—C20'—C21'—O6' | 177.8 (4) |
C24—O6—C21—C20 | −171.8 (4) | C19'—C20'—C21'—C22' | −2.3 (6) |
C19—C20—C21—O6 | 179.1 (4) | O6'—C21'—C22'—C23' | −177.8 (4) |
C19—C20—C21—C22 | −0.9 (6) | C20'—C21'—C22'—C23' | 2.4 (6) |
O6—C21—C22—C23 | −178.6 (4) | C21'—C22'—C23'—C18' | −0.9 (6) |
C20—C21—C22—C23 | 1.5 (6) | C19'—C18'—C23'—C22' | −0.6 (5) |
C19—C18—C23—C22 | 0.5 (5) | C11'—C18'—C23'—C22' | −177.1 (3) |
C11—C18—C23—C22 | 173.3 (3) | O5'—C11'—C25'—C30' | −20.2 (5) |
C21—C22—C23—C18 | −1.3 (6) | C12'—C11'—C25'—C30' | −137.1 (4) |
O5—C11—C25—C26 | 161.0 (3) | C18'—C11'—C25'—C30' | 97.9 (4) |
C12—C11—C25—C26 | −82.7 (4) | O5'—C11'—C25'—C26' | 156.4 (4) |
C18—C11—C25—C26 | 43.6 (5) | C12'—C11'—C25'—C26' | 39.5 (5) |
O5—C11—C25—C30 | −25.7 (5) | C18'—C11'—C25'—C26' | −85.4 (5) |
C12—C11—C25—C30 | 90.6 (4) | C30'—C25'—C26'—C27' | 4.1 (7) |
C18—C11—C25—C30 | −143.1 (3) | C11'—C25'—C26'—C27' | −172.7 (4) |
C30—C25—C26—C27 | 1.7 (6) | C25'—C26'—C27'—C28' | 1.2 (8) |
C11—C25—C26—C27 | 175.3 (4) | C31'—O7'—C28'—C29' | 6.2 (9) |
C25—C26—C27—C28 | −1.0 (7) | C31'—O7'—C28'—C27' | −175.6 (6) |
C31—O7—C28—C29 | −177.4 (4) | C26'—C27'—C28'—C29' | −5.2 (8) |
C31—O7—C28—C27 | 0.2 (7) | C26'—C27'—C28'—O7' | 176.5 (5) |
C26—C27—C28—O7 | −178.8 (4) | O7'—C28'—C29'—C30' | −178.0 (5) |
C26—C27—C28—C29 | −1.3 (7) | C27'—C28'—C29'—C30' | 3.9 (8) |
O7—C28—C29—C30 | −179.5 (4) | C26'—C25'—C30'—C29' | −5.5 (7) |
C27—C28—C29—C30 | 2.8 (7) | C11'—C25'—C30'—C29' | 171.3 (4) |
C28—C29—C30—C25 | −2.1 (7) | C28'—C29'—C30'—C25' | 1.6 (7) |
C26—C25—C30—C29 | −0.2 (6) | C65—O15—C63—C64 | 178.8 (13) |
C11—C25—C30—C29 | −173.7 (4) | C63—O15—C65—O16 | 6 (2) |
C4'—O1'—C1'—C10' | 127.4 (3) | C63—O15—C65—C66 | −170.2 (16) |
C4'—O1'—C1'—C2' | 2.1 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O4′ | 0.96 (4) | 1.81 (4) | 2.774 (4) | 180 (5) |
O2—H2O···O3i | 0.84 | 2.28 | 3.000 (4) | 144 |
O2—H2O···O4′i | 0.84 | 2.54 | 3.029 (4) | 119 |
N2′—H2′N···O4 | 0.77 (4) | 2.02 (4) | 2.778 (4) | 172 (4) |
O2′—H2′O···O3′ii | 0.95 (5) | 2.27 (5) | 3.060 (4) | 141 (4) |
O2′—H2′O···O4ii | 0.95 (5) | 2.33 (5) | 2.873 (4) | 116 (4) |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z. |
Experimental details
Crystal data |
Chemical formula | C31H32N2O7·0.25C4H8O2 |
Mr | 566.61 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 153 |
a, b, c (Å) | 10.542 (2), 17.931 (4), 17.136 (3) |
β (°) | 107.51 (3) |
V (Å3) | 3089.1 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.54 × 0.32 × 0.25 |
|
Data collection |
Diffractometer | Rigaku AFC10/Saturn724+ diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24617, 7094, 6327 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.151, 1.00 |
No. of reflections | 7094 |
No. of parameters | 790 |
No. of restraints | 5 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.79, −0.32 |
Absolute structure | In the absence of significant anomalous scattering effects,
Friedel pairs were merged as equivalent reflections. |
Selected geometric parameters (Å, º) topO1—C1 | 1.452 (4) | O1'—C1' | 1.442 (4) |
O1—C4 | 1.422 (4) | O1'—C4' | 1.423 (4) |
C1—C2 | 1.531 (4) | C1'—C2' | 1.543 (5) |
C2—C3 | 1.515 (4) | C2'—C3' | 1.514 (5) |
C3—C4 | 1.518 (5) | C3'—C4' | 1.520 (5) |
| | | |
C8—N1—C4—O1 | −120.7 (3) | C8'—N1'—C4'—O1' | −121.5 (3) |
C11—O5—C10—C1 | −175.7 (3) | C11'—O5'—C10'—C1' | 175.5 (3) |
O1—C1—C10—O5 | −66.4 (3) | O1'—C1'—C10'—O5' | −63.3 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O4' | 0.96 (4) | 1.81 (4) | 2.774 (4) | 180 (5) |
O2—H2O···O3i | 0.84 | 2.28 | 3.000 (4) | 144.00 |
O2—H2O···O4'i | 0.84 | 2.54 | 3.029 (4) | 119.00 |
N2'—H2'N···O4 | 0.77 (4) | 2.02 (4) | 2.778 (4) | 172 (4) |
O2'—H2'O···O3'ii | 0.95 (5) | 2.27 (5) | 3.060 (4) | 141 (4) |
O2'—H2'O···O4ii | 0.95 (5) | 2.33 (5) | 2.873 (4) | 116 (4) |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z. |
[18F]Fluorine-labeled thymidine (FLT) appears to be the most promising radiopharmaceutical because of its lack of in vivo degradation, metabolic trapping in proliferating cells, and the favorable half life for PET imaging (Troost et al., 2010; Agool et al., 2011). The title compound, (I), is one of the key intermediates in the chemical synthesis of 18F-FLT. It comprises thymidine protected at the 5'-O-position by reaction with dimethoxytrityl chloride in pyridine (Martin et al., 2002; Yun et al., 2003).
The crystal structure of (I) has two independent molecules in the asymmetric unit (molecules A and B; Fig. 1) and one ethyl acetate molecule with a site-occupancy factor of 0.50. The bond lengths and angles (Table 1) are similar to those reported for other deoxythymidine analogs (Young & Wilson, 1975; Sato, 1988; Jia et al., 1990a,b). The two molecules exhibit similar geometrical features, except that the dimethoxytrityl group adopts a different orientation with respect to the remainder of the molecule (Fig. 2). The conformation of the thymine ring with respect to the deoxyribose ring is anti, as inferred from the torsion angles about the glycosyl bond (C8—N1—C4—O1). The thymine ring (O3/O4/N1/N2/C5–C9) is essentially planar (average deviations from the mean plane of 0.019 and 0.015 Å for molecules A and B, respectively), and makes dihedral angles of 81.3 (1) and 80.1 (1)° with the mean plane through the attached deoxyribose ring (O1/C1–C4).
The C—C bonds within the deoxyribose rings (Table 1) have bond lengths in the range 1.514 (5)–1.543 (5) Å. The conformations of the rings are C3-endo, with atoms C3 and C3' displaced by 0.52 and 0.51 Å, respectively, from the mean plane constituted by the remaining four atoms of each deoxyribose ring. The puckering mode is described by the pseudorotation phase angle, P (Altona & Sundaralingam, 1972; Saenger, 1984). Here, P = 164.5 (3) and 158.2 (3)° for molecules A and B, respectively. The ring puckering amplitude τm= 34.7 (2) and 34.0 (2)°, which is in agreement with (τm) = 38±3° observed for nucleosides. Further insight into the distortions is obtained from the Cremer–Pople puckering parameters (Cremer & Pople, 1975): for molecule A, Q = 0.334 (4) Å and Φ = 76.1 (6)°; for molecule B, Q = 0.326 (4) Å and Φ = 70.3 (6)°.
The conformation about the C1—C10 and C1'—C10' bonds is gauche+ (g+), as seen from their torsion angles (Table 1). Although the g+ conformation is the most common for the side chain at C1 for cytidine and 2'-deoxycytidine nucleosides (Young & Wilson, 1975; Jia et al., 1990a; Audette et al., 1997, 1998), some 2'-deoxycytidine analogues display the trans conformation (Sato, 1988; Jia et al., 1990b; Napper et al., 1995). The torsion angles about the O5—C10 and O5'—C10' bonds (Table 1) show that the dimethoxytrityl group is in a staggered orientation, as in other trityl nucleoside structures (Capron et al., 1994). As shown in Fig. 2, the dimethyloxytrityl groups adopt different orientations in molecules A and B, related by rotation of the group around the C11—O5 or C11'—O5' bonds.
In the crystal structure, molecules A and B are linked into one-dimensional chains running parallel to the a axis by several intermolecular hydrogen bonds (Table 2 and Fig. 3). The thymine rings make an approximately centrosymmetric interaction through pairs of N2'—H2'N···O4 and N2—H2N···O4' hydrogen bonds. Neighbouring pairs of molecules are then linked by O—H···O hydrogen bonds from the exocyclic hydroxy group of the deoxyfuranose ring to the O atoms of the thymine groups. These interactions are bifurcated, viz. O2—H2O···O3i and O2'—H2'O···O3'ii, and O2—H2O···O4'i and O2'—H2'O···O4ii (symmetry codes are as in Table 2).