The title compound is a substituted 2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxole. The furanose ring adopts an envelope conformation, close to C 3-exo, as does the fused dioxolane ring. In the crystal, molecules are linked by weak C—H⋯O hydrogen bonds, forming zigzag chains along [010].
Keywords: crystal structure; 1,2,3-triazole; click chemistry; carbohydrate triazole conjugate; pseudo-nucleoside
Abstract
The title compound, C23H25N3O4, {systematic name: 1-benzyl-4-[(3aR,5R,6R,6aR)-6-benzyloxy-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-5-yl]-1H-1,2,3-triazole}, consists of a substituted 2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxole. The furanose ring adopts an envelope conformation close to C 3-exo, where the C atom substituted by the benzyloxy group is the flap. The fused dioxolane ring also adopts an envelope conformation, with the methylene C atom as the flap. In the crystal, molecules are linked by weak C—H⋯O hydrogen bonds, forming zigzag chains along [010].
Chemical context
The title compound, (1), was obtained in a one-pot multicomponent click reaction (Rostovtsev et al., 2002 ▸; Kumar et al., 2009 ▸) of alkyne (2), sodium azide, and benzyl bromide (3), in the presence of copper(II) sulfate and sodium ascorbate in THF solution at 323 K (Fig. 1 ▸). Similar C(4)-linked carbohydrate-1,2,3-triazole conjugates have been synthesized under different reaction conditions (Dururgkar et al., 2009 ▸; Kaliappan et al., 2009 ▸; Strakova et al., 2011 ▸). Many carbohydrate-triazole conjugates have been probed as glycosidase inhibitors (Rjabova et al., 2012 ▸), galectin inhibitors (Mackeviča et al., 2014 ▸), and antimicrobial agents (Jana et al., 2014 ▸; Reddy et al., 2014 ▸). Starting alkyne (2) and similar carbohydrate alkynes have been studied previously as precursors for triazole syntheses (Ciunik & Jarosz, 1998 ▸; Jarosz, 1988 ▸; Rjabovs et al., 2015 ▸; Strakova et al., 2011 ▸).
Figure 1.
Synthesis of the title compound (1).
Structural commentary
The title compound, Fig. 2 ▸, consists of a tetrahydrofuran core fused with a dioxolane ring, and substituted with benzyl and (1-benzyl)-1H-1,2,3-triazol-4-yl moieties. The furanose ring adopts an envelope conformation close to C 3-exo, where atom C3 deviates from the mean plane through atoms O1/C1/C2/C4 by 0.577 (4) Å. The fused dioxolane ring also adopts an envelope conformation, where atom C2 deviates from the mean plane through the four near planar atoms (O17/C18/O19/C1) by 0.364 (4) Å. The dihedral angle between the mean planes of the fragments of these rings is 69.3 (1)°.
Figure 2.
The molecular structure of compound (1), showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
Supramolecular features
In the crystal, weak C—H⋯O hydrogen bonds (Table 1 ▸) link the molecules, forming zigzag chains along the b-axis direction. There are no other significant intermolecular interactions present.
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C21—H21C⋯O19i | 0.96 | 2.53 | 3.285 (3) | 136 |
Symmetry code: (i) 
.
Database survey
A search of the Cambridge Structural Database (Version 5.36; Groom & Allen, 2014 ▸) for substituted 3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxoles gave 485 hits (excluding organometallics). Three of them are triazoles: (4R)-4-(2-allyl-2H-1,2,3-triazol-4-yl)-1,2-O-isopropylidene-l-threose (LOHTIM; Jenkinson et al., 2008 ▸) and 5-({5-[6-(benzyloxy)-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-5-yl]-1H-1,2,3-triazol-1-yl}methyl)-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-6-ol (DOPVAH01 and DOPVEL01, two stereoisomers; Kayet et al., 2014 ▸).
Synthesis and crystallization
The synthesis of the title compound is illustrated in Fig. 1 ▸. Sodium azide (98 mg, 1.5 mmol, 3 eq.) was added to a solution of alkyne (2) (140 mg, 0.5 mmol, 1 eq.) in THF (10 ml). The mixture was cooled to 273 K and benzyl bromide (3) (70 µl, 0.6 mmol, 1.2 eq.) was added. After 20 min solutions of copper(II) sulfate pentahydrate (12 mg, 10 mol%) in water (0.5 ml) and sodium ascorbate (20 mg, 20 mol%) in water (0.5 ml) were added and the resulting reaction mixture was warmed to 323 K. After 3 h the solvent was evaporated under reduced pressure, the residue was dissolved in EtOAc (20 ml). The organic layer was washed with a saturated aqueous solution of NaHCO3 (3 × 5 ml) and brine (3 × 5 ml), dried over Na2SO4, filtered and evaporated. The solid residue was purified by column chromatography on silica gel eluting with hexanes/EtOAc giving a white crystalline solid (yield: 132 mg, 65%; m.p. 430-431 K). Colourless plate-like crystals were obtained by slow evaporation of a dichloromethane solution at ambient temperature.
Spectroscopic data: IR (KBr, cm−1): 3125, 3085, 2985, 2895, 1495, 1455, 1385, 1370, 1230, 1145, 1100, 1075, 1040, 995. 1H NMR (CDCl3, 300 MHz): δ 7.37 (m, 4H), 7.28–7.16 (m, 6H), 5.83 (d, J = 3.6 Hz, 1H), 5.54 (d, AB syst., J = 14.8 Hz, 1H), 5.47 (d, AB syst., J = 14.8 Hz, 1H), 5.13 (d, J = 9.0 Hz, 1H), 4.64 (m, 2H), 4.55 (d, AB syst., J = 12.2 Hz, 1H), 4.25 (dd, J = 8.0, 4.0 Hz, 1H), 1.63 (s, 3H), 1.37 (s, 3H). 13C NMR (CDCl3, 75 MHz): 13C NMR (75 MHz, CDCl3) δ 145.12, 137.64, 134.54, 129.28, 128.96, 128.43, 128.27, 128.12, 127.98, 123.26, 113.14, 103.98, 81.43, 77.93, 72.59, 72.57, 54.31, 26.92, 26.54.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The C-bound H atoms were positioned geometrically and refined as riding on their parent atoms: C—H = 0.93–0.98Å with U iso(H) = 1.5U eq(C) for methyl H atoms and 1.2U eq(C) for other H atoms. Reflection (0,0,2) whose intensity was affected by the beam-stop was removed from the final refinement. In the final cycles of refinement, in the absence of significant anomalous scattering effects, Friedel pairs were merged and Δf′′ set to zero.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | C23H25N3O4 |
| M r | 407.46 |
| Crystal system, space group | Orthorhombic, P212121 |
| Temperature (K) | 173 |
| a, b, c (Å) | 9.5276 (2), 10.0030 (2), 21.9495 (7) |
| V (Å3) | 2091.89 (9) |
| Z | 4 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.09 |
| Crystal size (mm) | 0.31 × 0.17 × 0.12 |
| Data collection | |
| Diffractometer | Nonius KappaCCD |
| Absorption correction | – |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 5878, 3423, 1983 |
| R int | 0.070 |
| (sin θ/λ)max (Å−1) | 0.705 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.053, 0.106, 1.02 |
| No. of reflections | 3423 |
| No. of parameters | 273 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.19, −0.20 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015022434/su5245sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015022434/su5245Isup2.hkl
CCDC reference: 1438541
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
JSC ‘Olainfarm’ is acknowledged for the donation of diacetone-d-glucose and JSC ‘Grindeks’ is acknowledged for the donation of organic solvents.
supplementary crystallographic information
Crystal data
| C23H25N3O4 | Dx = 1.294 Mg m−3 |
| Mr = 407.46 | Mo Kα radiation, λ = 0.71073 Å |
| Orthorhombic, P212121 | Cell parameters from 11742 reflections |
| a = 9.5276 (2) Å | θ = 1.0–30.0° |
| b = 10.0030 (2) Å | µ = 0.09 mm−1 |
| c = 21.9495 (7) Å | T = 173 K |
| V = 2091.89 (9) Å3 | Plate, colourless |
| Z = 4 | 0.31 × 0.17 × 0.12 mm |
| F(000) = 864 |
Data collection
| Nonius KappaCCD diffractometer | 1983 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.070 |
| Graphite monochromator | θmax = 30.1°, θmin = 2.2° |
| φ and ω scan | h = −13→13 |
| 5878 measured reflections | k = −14→14 |
| 3423 independent reflections | l = −30→30 |
Refinement
| 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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.106 | H-atom parameters constrained |
| S = 1.02 | w = 1/[σ2(Fo2) + (0.0425P)2] where P = (Fo2 + 2Fc2)/3 |
| 3423 reflections | (Δ/σ)max < 0.001 |
| 273 parameters | Δρmax = 0.19 e Å−3 |
| 0 restraints | Δρmin = −0.20 e Å−3 |
Special details
| 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)
| x | y | z | Uiso*/Ueq | ||
| O1 | 1.16295 (19) | 0.88874 (17) | 0.19794 (8) | 0.0303 (4) | |
| C1 | 1.2698 (3) | 0.9325 (2) | 0.23846 (11) | 0.0257 (6) | |
| H1 | 1.2802 | 1.0299 | 0.2367 | 0.031* | |
| C2 | 1.2262 (3) | 0.8879 (2) | 0.30203 (12) | 0.0264 (6) | |
| H2 | 1.2484 | 0.9535 | 0.3338 | 0.032* | |
| C3 | 1.0704 (3) | 0.8622 (2) | 0.29521 (11) | 0.0249 (6) | |
| H3 | 1.0190 | 0.9468 | 0.2983 | 0.030* | |
| C4 | 1.0612 (3) | 0.8090 (2) | 0.23003 (11) | 0.0255 (6) | |
| H4 | 1.0914 | 0.7153 | 0.2295 | 0.031* | |
| C5 | 0.9254 (3) | 0.8207 (2) | 0.19804 (11) | 0.0247 (6) | |
| C6 | 0.8620 (3) | 0.9299 (3) | 0.17250 (11) | 0.0281 (7) | |
| H6 | 0.8943 | 1.0176 | 0.1724 | 0.034* | |
| N7 | 0.8440 (3) | 0.7120 (2) | 0.18755 (10) | 0.0330 (6) | |
| N8 | 0.7314 (3) | 0.7502 (2) | 0.15626 (10) | 0.0340 (6) | |
| N9 | 0.7435 (2) | 0.8834 (2) | 0.14768 (9) | 0.0281 (5) | |
| C10 | 0.6401 (3) | 0.9530 (3) | 0.11021 (12) | 0.0347 (7) | |
| H10A | 0.6524 | 1.0487 | 0.1150 | 0.042* | |
| H10B | 0.5466 | 0.9304 | 0.1243 | 0.042* | |
| C11 | 0.6530 (3) | 0.9172 (2) | 0.04351 (12) | 0.0278 (6) | |
| C12 | 0.7666 (4) | 0.9615 (3) | 0.00985 (13) | 0.0424 (8) | |
| H12 | 0.8340 | 1.0160 | 0.0278 | 0.051* | |
| C13 | 0.7797 (4) | 0.9242 (3) | −0.05091 (14) | 0.0509 (9) | |
| H13 | 0.8563 | 0.9536 | −0.0735 | 0.061* | |
| C14 | 0.6808 (4) | 0.8446 (3) | −0.07767 (14) | 0.0507 (9) | |
| H14 | 0.6908 | 0.8191 | −0.1182 | 0.061* | |
| C15 | 0.5672 (4) | 0.8026 (3) | −0.04496 (15) | 0.0511 (9) | |
| H15 | 0.4987 | 0.7502 | −0.0635 | 0.061* | |
| C16 | 0.5537 (3) | 0.8380 (3) | 0.01595 (14) | 0.0402 (8) | |
| H16 | 0.4770 | 0.8078 | 0.0382 | 0.048* | |
| O17 | 1.29867 (19) | 0.76405 (16) | 0.30941 (8) | 0.0286 (5) | |
| C18 | 1.4170 (3) | 0.7600 (2) | 0.26879 (11) | 0.0278 (6) | |
| O19 | 1.3983 (2) | 0.86916 (16) | 0.22727 (8) | 0.0308 (5) | |
| C20 | 1.5517 (3) | 0.7802 (3) | 0.30359 (13) | 0.0360 (7) | |
| H20A | 1.5477 | 0.8636 | 0.3252 | 0.054* | |
| H20B | 1.6292 | 0.7816 | 0.2757 | 0.054* | |
| H20C | 1.5639 | 0.7084 | 0.3321 | 0.054* | |
| C21 | 1.4123 (3) | 0.6299 (2) | 0.23368 (12) | 0.0364 (7) | |
| H21A | 1.4858 | 0.6291 | 0.2038 | 0.055* | |
| H21B | 1.3230 | 0.6216 | 0.2137 | 0.055* | |
| H21C | 1.4250 | 0.5564 | 0.2613 | 0.055* | |
| O3' | 1.0121 (2) | 0.76803 (16) | 0.33605 (8) | 0.0283 (4) | |
| C4' | 0.9967 (4) | 0.8185 (3) | 0.39562 (13) | 0.0497 (9) | |
| H4'1 | 0.9405 | 0.8992 | 0.3945 | 0.060* | |
| H4'2 | 1.0883 | 0.8413 | 0.4119 | 0.060* | |
| C5' | 0.9281 (3) | 0.7180 (2) | 0.43610 (12) | 0.0303 (7) | |
| C6' | 0.9439 (4) | 0.7281 (3) | 0.49853 (14) | 0.0446 (8) | |
| H6' | 0.9965 | 0.7976 | 0.5150 | 0.054* | |
| C7' | 0.8820 (4) | 0.6357 (3) | 0.53642 (13) | 0.0495 (9) | |
| H7' | 0.8924 | 0.6437 | 0.5784 | 0.059* | |
| C8' | 0.8054 (4) | 0.5322 (3) | 0.51301 (15) | 0.0500 (9) | |
| H8' | 0.7648 | 0.4692 | 0.5388 | 0.060* | |
| C9' | 0.7889 (4) | 0.5223 (3) | 0.45101 (15) | 0.0480 (9) | |
| H9' | 0.7360 | 0.4528 | 0.4348 | 0.058* | |
| C10' | 0.8498 (3) | 0.6139 (3) | 0.41277 (12) | 0.0360 (7) | |
| H10' | 0.8383 | 0.6058 | 0.3709 | 0.043* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0293 (11) | 0.0383 (10) | 0.0232 (9) | −0.0053 (9) | −0.0004 (9) | 0.0065 (8) |
| C1 | 0.0310 (17) | 0.0218 (14) | 0.0244 (14) | −0.0016 (13) | 0.0007 (13) | 0.0025 (11) |
| C2 | 0.0315 (16) | 0.0208 (13) | 0.0267 (14) | 0.0026 (12) | −0.0007 (13) | −0.0005 (11) |
| C3 | 0.0319 (16) | 0.0216 (12) | 0.0211 (13) | 0.0002 (13) | 0.0030 (13) | −0.0002 (10) |
| C4 | 0.0318 (17) | 0.0212 (13) | 0.0235 (13) | 0.0007 (13) | 0.0046 (13) | 0.0038 (10) |
| C5 | 0.0325 (16) | 0.0231 (12) | 0.0185 (13) | −0.0036 (13) | 0.0028 (13) | 0.0020 (11) |
| C6 | 0.0304 (17) | 0.0298 (14) | 0.0242 (14) | −0.0049 (13) | −0.0024 (13) | −0.0029 (11) |
| N7 | 0.0321 (14) | 0.0315 (13) | 0.0354 (14) | −0.0074 (12) | −0.0046 (12) | 0.0026 (10) |
| N8 | 0.0346 (14) | 0.0320 (13) | 0.0354 (13) | −0.0103 (12) | 0.0012 (12) | 0.0013 (11) |
| N9 | 0.0278 (14) | 0.0283 (13) | 0.0281 (12) | 0.0003 (11) | −0.0023 (11) | −0.0025 (10) |
| C10 | 0.0305 (17) | 0.0389 (15) | 0.0347 (16) | 0.0069 (15) | −0.0020 (14) | −0.0042 (13) |
| C11 | 0.0285 (16) | 0.0281 (14) | 0.0268 (14) | 0.0061 (13) | −0.0068 (13) | −0.0018 (12) |
| C12 | 0.042 (2) | 0.0478 (19) | 0.0371 (18) | −0.0066 (17) | −0.0070 (16) | −0.0003 (14) |
| C13 | 0.053 (2) | 0.061 (2) | 0.0384 (19) | 0.0017 (19) | 0.0041 (18) | 0.0066 (17) |
| C14 | 0.071 (3) | 0.053 (2) | 0.0280 (17) | 0.0107 (19) | −0.0061 (19) | −0.0054 (15) |
| C15 | 0.061 (3) | 0.0497 (18) | 0.043 (2) | −0.0042 (19) | −0.016 (2) | −0.0110 (15) |
| C16 | 0.0359 (19) | 0.0394 (17) | 0.0452 (19) | −0.0010 (15) | −0.0034 (17) | −0.0013 (14) |
| O17 | 0.0303 (11) | 0.0232 (9) | 0.0324 (10) | 0.0064 (8) | 0.0054 (9) | 0.0073 (8) |
| C18 | 0.0317 (16) | 0.0252 (13) | 0.0266 (14) | 0.0049 (13) | 0.0040 (13) | 0.0039 (11) |
| O19 | 0.0279 (11) | 0.0299 (9) | 0.0346 (10) | 0.0030 (9) | 0.0061 (9) | 0.0087 (8) |
| C20 | 0.0371 (18) | 0.0359 (16) | 0.0350 (16) | 0.0024 (14) | −0.0021 (15) | 0.0045 (13) |
| C21 | 0.0406 (19) | 0.0271 (14) | 0.0415 (17) | 0.0033 (15) | 0.0032 (16) | −0.0038 (12) |
| O3' | 0.0390 (11) | 0.0255 (9) | 0.0203 (9) | −0.0023 (9) | 0.0070 (8) | 0.0003 (8) |
| C4' | 0.080 (3) | 0.0394 (17) | 0.0298 (17) | −0.0144 (19) | 0.0176 (18) | −0.0088 (13) |
| C5' | 0.0356 (18) | 0.0296 (14) | 0.0258 (15) | −0.0002 (14) | 0.0070 (13) | −0.0038 (11) |
| C6' | 0.050 (2) | 0.0518 (19) | 0.0317 (17) | −0.0111 (18) | 0.0060 (16) | −0.0077 (14) |
| C7' | 0.060 (2) | 0.064 (2) | 0.0240 (16) | −0.003 (2) | 0.0109 (17) | 0.0030 (15) |
| C8' | 0.061 (3) | 0.0463 (19) | 0.043 (2) | −0.0046 (18) | 0.0200 (18) | 0.0107 (15) |
| C9' | 0.053 (2) | 0.0410 (17) | 0.050 (2) | −0.0119 (17) | 0.0146 (19) | −0.0063 (16) |
| C10' | 0.0406 (18) | 0.0404 (17) | 0.0270 (15) | −0.0024 (16) | 0.0031 (14) | −0.0011 (13) |
Geometric parameters (Å, º)
| O1—C1 | 1.421 (3) | C14—H14 | 0.9300 |
| O1—C4 | 1.439 (3) | C15—C16 | 1.389 (4) |
| C1—O19 | 1.400 (3) | C15—H15 | 0.9300 |
| C1—C2 | 1.523 (3) | C16—H16 | 0.9300 |
| C1—H1 | 0.9800 | O17—C18 | 1.438 (3) |
| C2—O17 | 1.428 (3) | C18—O19 | 1.433 (3) |
| C2—C3 | 1.514 (4) | C18—C20 | 1.507 (4) |
| C2—H2 | 0.9800 | C18—C21 | 1.513 (3) |
| C3—O3' | 1.414 (3) | C20—H20A | 0.9600 |
| C3—C4 | 1.529 (3) | C20—H20B | 0.9600 |
| C3—H3 | 0.9800 | C20—H20C | 0.9600 |
| C4—C5 | 1.477 (4) | C21—H21A | 0.9600 |
| C4—H4 | 0.9800 | C21—H21B | 0.9600 |
| C5—N7 | 1.355 (3) | C21—H21C | 0.9600 |
| C5—C6 | 1.369 (3) | O3'—C4' | 1.409 (3) |
| C6—N9 | 1.337 (3) | C4'—C5' | 1.492 (4) |
| C6—H6 | 0.9300 | C4'—H4'1 | 0.9700 |
| N7—N8 | 1.330 (3) | C4'—H4'2 | 0.9700 |
| N8—N9 | 1.351 (3) | C5'—C10' | 1.379 (4) |
| N9—C10 | 1.460 (3) | C5'—C6' | 1.382 (4) |
| C10—C11 | 1.513 (3) | C6'—C7' | 1.376 (4) |
| C10—H10A | 0.9700 | C6'—H6' | 0.9300 |
| C10—H10B | 0.9700 | C7'—C8' | 1.367 (4) |
| C11—C16 | 1.374 (4) | C7'—H7' | 0.9300 |
| C11—C12 | 1.383 (4) | C8'—C9' | 1.373 (4) |
| C12—C13 | 1.391 (4) | C8'—H8' | 0.9300 |
| C12—H12 | 0.9300 | C9'—C10' | 1.371 (4) |
| C13—C14 | 1.366 (4) | C9'—H9' | 0.9300 |
| C13—H13 | 0.9300 | C10'—H10' | 0.9300 |
| C14—C15 | 1.365 (5) | ||
| C1—O1—C4 | 110.29 (18) | C13—C14—H14 | 120.0 |
| O19—C1—O1 | 112.16 (19) | C14—C15—C16 | 120.0 (3) |
| O19—C1—C2 | 105.47 (19) | C14—C15—H15 | 120.0 |
| O1—C1—C2 | 106.7 (2) | C16—C15—H15 | 120.0 |
| O19—C1—H1 | 110.8 | C11—C16—C15 | 120.5 (3) |
| O1—C1—H1 | 110.8 | C11—C16—H16 | 119.8 |
| C2—C1—H1 | 110.8 | C15—C16—H16 | 119.8 |
| O17—C2—C3 | 109.7 (2) | C2—O17—C18 | 109.46 (17) |
| O17—C2—C1 | 103.1 (2) | O19—C18—O17 | 105.97 (19) |
| C3—C2—C1 | 103.1 (2) | O19—C18—C20 | 109.0 (2) |
| O17—C2—H2 | 113.3 | O17—C18—C20 | 110.5 (2) |
| C3—C2—H2 | 113.3 | O19—C18—C21 | 109.1 (2) |
| C1—C2—H2 | 113.3 | O17—C18—C21 | 108.4 (2) |
| O3'—C3—C2 | 115.8 (2) | C20—C18—C21 | 113.5 (2) |
| O3'—C3—C4 | 109.82 (19) | C1—O19—C18 | 110.00 (19) |
| C2—C3—C4 | 102.0 (2) | C18—C20—H20A | 109.5 |
| O3'—C3—H3 | 109.6 | C18—C20—H20B | 109.5 |
| C2—C3—H3 | 109.6 | H20A—C20—H20B | 109.5 |
| C4—C3—H3 | 109.6 | C18—C20—H20C | 109.5 |
| O1—C4—C5 | 108.25 (19) | H20A—C20—H20C | 109.5 |
| O1—C4—C3 | 103.10 (19) | H20B—C20—H20C | 109.5 |
| C5—C4—C3 | 117.9 (2) | C18—C21—H21A | 109.5 |
| O1—C4—H4 | 109.1 | C18—C21—H21B | 109.5 |
| C5—C4—H4 | 109.1 | H21A—C21—H21B | 109.5 |
| C3—C4—H4 | 109.1 | C18—C21—H21C | 109.5 |
| N7—C5—C6 | 108.5 (2) | H21A—C21—H21C | 109.5 |
| N7—C5—C4 | 121.3 (2) | H21B—C21—H21C | 109.5 |
| C6—C5—C4 | 130.2 (2) | C4'—O3'—C3 | 113.00 (19) |
| N9—C6—C5 | 105.2 (2) | O3'—C4'—C5' | 110.9 (2) |
| N9—C6—H6 | 127.4 | O3'—C4'—H4'1 | 109.5 |
| C5—C6—H6 | 127.4 | C5'—C4'—H4'1 | 109.5 |
| N8—N7—C5 | 108.6 (2) | O3'—C4'—H4'2 | 109.5 |
| N7—N8—N9 | 106.6 (2) | C5'—C4'—H4'2 | 109.5 |
| C6—N9—N8 | 111.0 (2) | H4'1—C4'—H4'2 | 108.0 |
| C6—N9—C10 | 129.3 (2) | C10'—C5'—C6' | 118.8 (3) |
| N8—N9—C10 | 119.5 (2) | C10'—C5'—C4' | 121.6 (2) |
| N9—C10—C11 | 112.1 (2) | C6'—C5'—C4' | 119.5 (3) |
| N9—C10—H10A | 109.2 | C7'—C6'—C5' | 120.2 (3) |
| C11—C10—H10A | 109.2 | C7'—C6'—H6' | 119.9 |
| N9—C10—H10B | 109.2 | C5'—C6'—H6' | 119.9 |
| C11—C10—H10B | 109.2 | C8'—C7'—C6' | 120.7 (3) |
| H10A—C10—H10B | 107.9 | C8'—C7'—H7' | 119.7 |
| C16—C11—C12 | 119.2 (3) | C6'—C7'—H7' | 119.7 |
| C16—C11—C10 | 120.5 (3) | C7'—C8'—C9' | 119.2 (3) |
| C12—C11—C10 | 120.3 (3) | C7'—C8'—H8' | 120.4 |
| C11—C12—C13 | 119.8 (3) | C9'—C8'—H8' | 120.4 |
| C11—C12—H12 | 120.1 | C10'—C9'—C8' | 120.7 (3) |
| C13—C12—H12 | 120.1 | C10'—C9'—H9' | 119.7 |
| C14—C13—C12 | 120.4 (3) | C8'—C9'—H9' | 119.7 |
| C14—C13—H13 | 119.8 | C9'—C10'—C5' | 120.4 (3) |
| C12—C13—H13 | 119.8 | C9'—C10'—H10' | 119.8 |
| C15—C14—C13 | 120.0 (3) | C5'—C10'—H10' | 119.8 |
| C15—C14—H14 | 120.0 | ||
| C4—O1—C1—O19 | 109.7 (2) | N9—C10—C11—C12 | −70.7 (3) |
| C4—O1—C1—C2 | −5.3 (3) | C16—C11—C12—C13 | −0.8 (4) |
| O19—C1—C2—O17 | −24.2 (2) | C10—C11—C12—C13 | 177.9 (3) |
| O1—C1—C2—O17 | 95.2 (2) | C11—C12—C13—C14 | 0.3 (5) |
| O19—C1—C2—C3 | −138.4 (2) | C12—C13—C14—C15 | 0.8 (5) |
| O1—C1—C2—C3 | −19.0 (3) | C13—C14—C15—C16 | −1.6 (5) |
| O17—C2—C3—O3' | 44.2 (3) | C12—C11—C16—C15 | 0.1 (4) |
| C1—C2—C3—O3' | 153.50 (19) | C10—C11—C16—C15 | −178.6 (3) |
| O17—C2—C3—C4 | −75.0 (2) | C14—C15—C16—C11 | 1.1 (5) |
| C1—C2—C3—C4 | 34.3 (2) | C3—C2—O17—C18 | 131.7 (2) |
| C1—O1—C4—C5 | 152.8 (2) | C1—C2—O17—C18 | 22.4 (2) |
| C1—O1—C4—C3 | 27.2 (3) | C2—O17—C18—O19 | −12.5 (2) |
| O3'—C3—C4—O1 | −161.15 (19) | C2—O17—C18—C20 | 105.5 (2) |
| C2—C3—C4—O1 | −37.8 (2) | C2—O17—C18—C21 | −129.5 (2) |
| O3'—C3—C4—C5 | 79.7 (3) | O1—C1—O19—C18 | −98.2 (2) |
| C2—C3—C4—C5 | −156.9 (2) | C2—C1—O19—C18 | 17.6 (3) |
| O1—C4—C5—N7 | 136.0 (2) | O17—C18—O19—C1 | −4.0 (3) |
| C3—C4—C5—N7 | −107.6 (3) | C20—C18—O19—C1 | −123.0 (2) |
| O1—C4—C5—C6 | −41.0 (4) | C21—C18—O19—C1 | 112.5 (2) |
| C3—C4—C5—C6 | 75.3 (3) | C2—C3—O3'—C4' | 74.5 (3) |
| N7—C5—C6—N9 | 0.4 (3) | C4—C3—O3'—C4' | −170.7 (3) |
| C4—C5—C6—N9 | 177.7 (2) | C3—O3'—C4'—C5' | 177.0 (2) |
| C6—C5—N7—N8 | −0.1 (3) | O3'—C4'—C5'—C10' | −20.4 (4) |
| C4—C5—N7—N8 | −177.7 (2) | O3'—C4'—C5'—C6' | 159.0 (3) |
| C5—N7—N8—N9 | −0.3 (3) | C10'—C5'—C6'—C7' | −0.2 (5) |
| C5—C6—N9—N8 | −0.5 (3) | C4'—C5'—C6'—C7' | −179.6 (3) |
| C5—C6—N9—C10 | −174.5 (2) | C5'—C6'—C7'—C8' | 0.6 (5) |
| N7—N8—N9—C6 | 0.5 (3) | C6'—C7'—C8'—C9' | −0.9 (5) |
| N7—N8—N9—C10 | 175.2 (2) | C7'—C8'—C9'—C10' | 0.8 (5) |
| C6—N9—C10—C11 | 103.7 (3) | C8'—C9'—C10'—C5' | −0.3 (5) |
| N8—N9—C10—C11 | −69.9 (3) | C6'—C5'—C10'—C9' | 0.0 (5) |
| N9—C10—C11—C16 | 108.0 (3) | C4'—C5'—C10'—C9' | 179.4 (3) |
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C21—H21C···O19i | 0.96 | 2.53 | 3.285 (3) | 136 |
Symmetry code: (i) −x+3, y−1/2, −z+1/2.
References
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015022434/su5245sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015022434/su5245Isup2.hkl
CCDC reference: 1438541
Additional supporting information: crystallographic information; 3D view; checkCIF report