The title compound consists of a substituted 2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxolane skeleton. The furanose ring adopts a conformation close to C 3-exo. Both dioxolane rings adopt envelope conformations with an O atom as the flap in each case. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, forming chains propagating along the b-axis direction.
Keywords: crystal structure, 3-aminomethyl diacetone-d-allose, imino sugar precursor, sugar amino acid precursor, hydrogen bonding.
Abstract
The title compound, C21H29NO7 (1) [systematic name: benzyl ({(3aR,5S,6R,6aR)-5-[(R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-6-yl}methyl)carbamate], consists of a substituted 2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxolane skeleton. The furanose ring adopts an envelope conformation close to C 3-exo, where the C atom substituted by the benzyl carbamate group is the flap. The fused dioxolane ring also adopts an envelope conformation, as does the terminal dioxolane ring, with in each case an O atom as the flap. In the crystal, molecules are linked by N—H⋯O and C–H⋯O hydrogen bonds, forming chains propagating along the b-axis direction.
Chemical context
The title compound, 3-C-(N-benzyloxycarbonyl)aminomethyl-3-deoxy-1,2:5,6-di-O-isopropylidene-α-d-allofuranose (1), was obtained as an intermediate in the syntheses of carbohydrate-based non-natural amino acids, so called sugar amino acids (Rjabovs et al., 2015 ▸), by hydrogenation and carbamate protection of either nitro (Lugiņina et al., 2013 ▸) or azido (Filichev & Pedersen, 2001 ▸; Rjabova et al., 2012 ▸) precursors (Fig. 1 ▸).
Figure 1.
Synthesis of the title compound.
The synthesis of sugar amino acids and their properties and applications have been reported on by Rjabovs et al. (2015 ▸), and reviewed by Rjabovs & Turks (2013 ▸) and Risseeuw et al. (2013 ▸). The title compound can be used as a precursor for the syntheses of imino sugars and 10-aza-C-nucleosides (Filichev & Pedersen, 2001 ▸). The syntheses and biological properties of imino sugars have been reviewed by López et al. (2012 ▸), while the syntheses and biological properties of aza-nucleosides have been reported on by Romeo et al. (2010 ▸) and Merino (2006 ▸).
Structural commentary
The title compound, Fig. 2 ▸, consists of a tetrahydrofuran core fused with a dioxolane ring and substituted with dioxolane and (N-benzyloxycarbonyl)aminomethyl moieties. The furanose ring adopts a conformation close to C 3-exo. On the other hand, the furanose ring may be viewed as an envelope, where atom C3 deviates from the mean plane through atoms O1/C1/C2/C4 by 0.567 (2) Å. The fused dioxolane ring also adopts an envelope conformation, where O14 deviates from the mean plane through the four near planar atoms (O12/C1/C2/C13) by 0.422 (2) Å. The dihedral angle between the planar fragments of these rings is 67.1 (1)°. The five-membered ring of the 2,2-dimethyl-1,3-dioxolan-4-yl group also adopts an envelope conformation, with atom O7 deviating from the mean plane through the four planar atoms (O9/C5/C6/C8) by 0.519 (1) Å.
Figure 2.
The molecular structure of compound (1), with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
Supramolecular features
In the crystal, molecules are linked by N—H⋯O and C–H⋯O hydrogen bonds, forming chains propagating along the b-axis direction (Fig. 3 ▸ and Table 1 ▸).
Figure 3.
The crystal packing of compound (1), viewed along the a axis. Hydrogen bonds are shown as dashed lines (see Table 1 ▸ for details). For clarity only H atoms involved in these interactions have been included.
Table 1. Hydrogen-bond geometry (, ).
| DHA | DH | HA | D A | DHA |
|---|---|---|---|---|
| N4H4O6i | 0.80(3) | 2.51(3) | 3.295(3) | 167(2) |
| C6H6BO9ii | 0.97 | 2.32 | 3.184(3) | 141 |
Symmetry codes: (i) 
; (ii) 
.
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 metal-organics). However, only two structures are 3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-6-ylmethylcarbamic acid derivatives, viz. (3R)-3′-ethyl-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-a-d-allofuranose-3,5′-oxazolidin)-2′-one (CIDVES; Turks et al., 2013 ▸), and (3R)-3′-phenylacetyl-1,2:5,6-di-O-isopropylidenespiro(3-deoxy-a-d-allofuranose-3,5′-oxazolidin)-2′-one (YIMBED; Turks et al., 2013 ▸).
Synthesis and crystallization
The two methods for the synthesis of compound (1) are illustrated in Fig. 1 ▸.
From compound (2): A mixture of nitromethyl compound (2) (5.00 g, 16.5 mmol, 1 equiv.) and 10% Pd/C (1.00 g) in MeOH (200 ml) was hydrogenated under 40 atm pressure at 313 K overnight (TLC control). The resulting reaction mixture was filtered through celite and the filtrate was evaporated under reduced pressure. The residue was dissolved in THF (60 ml) and a solution of K2CO3 (2.50 g, 18.1 mmol, 1.1 equiv.) in water (35 ml) was added. The resulting mixture was cooled to 273 K and N-(benzyloxycarbonyloxy)succinimide (4.50 g, 18.1 mmol, 1.1 equiv) was added portion-wise. The reaction mixture was stirred at 273 K for 4 h (TLC control). Solid K2CO3 (1 g) was added and the formed layers were separated. The organic phase was washed with saturated aqueous solution of NaHSO4 (50 ml) while the aqueous phase was extracted with a mixture of hexanes and CH2Cl2 (3 × 100 ml, 8:2 v/v). The combined organic phase was washed with brine (2 × 100 ml), dried over Na2SO4, filtered and evaporated under reduced pressure. Crude product (1) was obtained as a yellow oil (6.60 g, 98% crude) and used further without additional purification.
From compound (3): Through a mixture of azide (3) (14.86 g, 49.7 mmol, 1.0 equiv) and 10% Pd/C (1.45 g) in MeOH (150 ml) hydrogen flow was passed at ambient temperature and pressure for 1 h (TLC control). The reaction mixture was filtered through a celite pad and the filtrate was evaporated under reduced pressure. The residue was dissolved in anhydrous CH2Cl2 (200 ml) and triethylamine (8.5 ml, 61.0 mmol, 1.0 equiv) was added. The resulting solution was cooled to 273 K and benzyl chloroformate (7.0 ml, 60.5 mmol, 1.2 equiv) was added portion-wise. The reaction mixture was stirred under an argon atmosphere at ambient temperature overnight. The solvent was evaporated under reduced pressure and the residue was dissolved in EtOAc (100 ml). The resulting solution was washed with a saturated aqueous solution of NaHCO3 (3 × 20 ml) and brine (3 × 30 ml), dried over Na2SO4, filtered and evaporated. Column chromatography (hexanes/EtOAc 4:1 to 2:1 v/v) yielded product (1) (15.22 g, 75%) as a colourless oil that solidifies at low temperatures. R f = 0.6 (hexanes/EtOAc 1:1). 1H NMR (CDCl3, 300 MHz): 1.30, 1.34, 1.41, 1.50 (4s, 12H, 2 (H3C)2C), 2.13 [dq, J = 9.6, 4.9 Hz, 1H, H-C(3)], 3.52 [m, 2H, H2C(3′)], 3.77 [m, 1H, H-C(5)], 3.95 [m, 2H, H2C(6)], 4.11 [m, 1H, H-C(4]), 4.68 [t, J = 4.3 Hz, 1H, H-C(2)], 5.11 (s, AB syst., 2H, H2C-Ph), 5.67 (t, J = 6.0 Hz, 1H, HN), 5.75 [d, J = 3.8 Hz, 1H, H-C(1)], 7.35 (m, 5H, Ph). 13C NMR (CDCl3, 75 MHz): 25.2, 26.3, 26.5, 26.7, 38.0, 48.6, 66.5, 67.8, 77.3, 81.4, 82.0, 104.8, 109.8, 112.2, 128.0, 128.0, 128.5, 136.8, 156.4. HRMS: Calculated for C21H29NO7Na, [M + Na]+ 430.1842. Found: 430.1795.
X-ray quality single crystals were obtained by spontaneous crystallization of the title compound from the neat oily material at 277 K.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The H atom on the amino group was located in a difference Fourier map and freely refined. 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. Reflections (1,0,0) and (0,0,2), whose intensities were affected by the beam-stop, were removed from the final refinement.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | C21H29NO7 |
| M r | 407.45 |
| Crystal system, space group | Monoclinic, P21 |
| Temperature (K) | 173 |
| a, b, c () | 9.3235(3), 5.4118(1), 20.4381(7) |
| () | 96.748(1) |
| V (3) | 1024.10(5) |
| Z | 2 |
| Radiation type | Mo K |
| (mm1) | 0.10 |
| Crystal size (mm) | 0.32 0.31 0.20 |
| Data collection | |
| Diffractometer | Nonius KappaCCD |
| No. of measured, independent and observed [I > 2(I)] reflections | 5535, 3279, 2597 |
| R int | 0.034 |
| (sin /)max (1) | 0.705 |
| Refinement | |
| R[F 2 > 2(F 2)], wR(F 2), S | 0.045, 0.100, 1.03 |
| No. of reflections | 3279 |
| No. of parameters | 270 |
| No. of restraints | 1 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| max, min (e 3) | 0.23, 0.21 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015017582/su5210sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015017582/su5210Isup2.hkl
CCDC reference: 1425954
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
JSC ‘Olainfarm’ is acknowledged for the donation of diacetone—glucose. JSC ‘Grindeks’ is acknowledged for the donation of organic solvents.
supplementary crystallographic information
Crystal data
| C21H29NO7 | F(000) = 436 |
| Mr = 407.45 | Dx = 1.321 Mg m−3 |
| Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2yb | Cell parameters from 11906 reflections |
| a = 9.3235 (3) Å | θ = 1.0–30.0° |
| b = 5.4118 (1) Å | µ = 0.10 mm−1 |
| c = 20.4381 (7) Å | T = 173 K |
| β = 96.748 (1)° | Block, colourless |
| V = 1024.10 (5) Å3 | 0.32 × 0.31 × 0.20 mm |
| Z = 2 |
Data collection
| Nonius KappaCCD diffractometer | 2597 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.034 |
| Graphite monochromator | θmax = 30.1°, θmin = 2.3° |
| CCD scans | h = −13→13 |
| 5535 measured reflections | k = −7→6 |
| 3279 independent reflections | l = −28→28 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.044P)2 + 0.1203P] where P = (Fo2 + 2Fc2)/3 |
| 3279 reflections | (Δ/σ)max < 0.001 |
| 270 parameters | Δρmax = 0.23 e Å−3 |
| 1 restraint | Δρmin = −0.21 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 | 0.34514 (16) | 0.3163 (3) | 0.37758 (7) | 0.0315 (4) | |
| C1 | 0.2837 (2) | 0.3609 (4) | 0.31216 (10) | 0.0257 (4) | |
| H1 | 0.2922 | 0.5356 | 0.3006 | 0.031* | |
| C2 | 0.3645 (2) | 0.1973 (4) | 0.26790 (10) | 0.0236 (4) | |
| H2 | 0.3840 | 0.2807 | 0.2273 | 0.028* | |
| C3 | 0.5014 (2) | 0.1255 (4) | 0.31153 (9) | 0.0216 (4) | |
| H3 | 0.5695 | 0.2635 | 0.3118 | 0.026* | |
| C4 | 0.4468 (2) | 0.1149 (4) | 0.37946 (9) | 0.0219 (4) | |
| H4 | 0.3965 | −0.0419 | 0.3842 | 0.026* | |
| C5 | 0.5571 (2) | 0.1572 (4) | 0.43934 (10) | 0.0221 (4) | |
| H5 | 0.5063 | 0.1803 | 0.4782 | 0.027* | |
| C6 | 0.6694 (2) | −0.0473 (4) | 0.45328 (10) | 0.0239 (4) | |
| H6A | 0.6898 | −0.0777 | 0.5002 | 0.029* | |
| H6B | 0.6366 | −0.1997 | 0.4314 | 0.029* | |
| O7 | 0.79329 (15) | 0.0472 (3) | 0.42712 (7) | 0.0251 (3) | |
| C8 | 0.7920 (2) | 0.3060 (4) | 0.43977 (10) | 0.0234 (4) | |
| O9 | 0.64107 (15) | 0.3721 (3) | 0.43018 (7) | 0.0251 (3) | |
| C10 | 0.8696 (3) | 0.4342 (4) | 0.38914 (12) | 0.0326 (5) | |
| H10A | 0.8217 | 0.3997 | 0.3459 | 0.049* | |
| H10B | 0.9674 | 0.3758 | 0.3923 | 0.049* | |
| H10C | 0.8695 | 0.6092 | 0.3968 | 0.049* | |
| C11 | 0.8532 (2) | 0.3653 (4) | 0.51018 (11) | 0.0313 (5) | |
| H11A | 0.9549 | 0.3308 | 0.5161 | 0.047* | |
| H11B | 0.8057 | 0.2657 | 0.5400 | 0.047* | |
| H11C | 0.8376 | 0.5369 | 0.5190 | 0.047* | |
| O12 | 0.13924 (16) | 0.2825 (3) | 0.30147 (9) | 0.0356 (4) | |
| C13 | 0.1257 (2) | 0.0752 (4) | 0.25826 (11) | 0.0277 (5) | |
| O14 | 0.27047 (15) | −0.0114 (3) | 0.25586 (7) | 0.0282 (3) | |
| C15 | 0.0589 (3) | 0.1589 (6) | 0.19055 (13) | 0.0490 (7) | |
| H15A | 0.1160 | 0.2897 | 0.1752 | 0.074* | |
| H15B | −0.0375 | 0.2176 | 0.1932 | 0.074* | |
| H15C | 0.0558 | 0.0225 | 0.1604 | 0.074* | |
| C16 | 0.0396 (3) | −0.1209 (5) | 0.28758 (14) | 0.0411 (6) | |
| H16A | −0.0564 | −0.0612 | 0.2904 | 0.062* | |
| H16B | 0.0849 | −0.1617 | 0.3309 | 0.062* | |
| H16C | 0.0352 | −0.2656 | 0.2602 | 0.062* | |
| C3' | 0.5763 (2) | −0.1049 (4) | 0.29004 (10) | 0.0240 (4) | |
| H3'1 | 0.6569 | −0.1470 | 0.3226 | 0.029* | |
| H3'2 | 0.5093 | −0.2427 | 0.2863 | 0.029* | |
| N4' | 0.6281 (2) | −0.0585 (4) | 0.22661 (9) | 0.0279 (4) | |
| C5' | 0.6706 (2) | −0.2436 (4) | 0.18935 (10) | 0.0279 (5) | |
| O6' | 0.66529 (19) | −0.4616 (3) | 0.20170 (8) | 0.0363 (4) | |
| O7' | 0.71820 (19) | −0.1464 (3) | 0.13471 (8) | 0.0403 (4) | |
| C8' | 0.7650 (3) | −0.3172 (5) | 0.08682 (11) | 0.0418 (6) | |
| H8'1 | 0.7087 | −0.4682 | 0.0856 | 0.050* | |
| H8'2 | 0.8662 | −0.3584 | 0.0979 | 0.050* | |
| C1'' | 0.7418 (3) | −0.1870 (5) | 0.02154 (11) | 0.0355 (5) | |
| C2'' | 0.8230 (3) | 0.0185 (6) | 0.00934 (12) | 0.0444 (6) | |
| H2'' | 0.8968 | 0.0708 | 0.0409 | 0.053* | |
| C3'' | 0.7954 (3) | 0.1460 (6) | −0.04903 (14) | 0.0525 (7) | |
| H3'' | 0.8502 | 0.2845 | −0.0565 | 0.063* | |
| C4'' | 0.6868 (3) | 0.0694 (6) | −0.09655 (13) | 0.0520 (8) | |
| H4'' | 0.6679 | 0.1563 | −0.1359 | 0.062* | |
| C5'' | 0.6074 (3) | −0.1351 (7) | −0.08519 (13) | 0.0523 (8) | |
| H5'' | 0.5349 | −0.1882 | −0.1173 | 0.063* | |
| C6'' | 0.6334 (3) | −0.2644 (6) | −0.02641 (13) | 0.0454 (7) | |
| H6'' | 0.5783 | −0.4028 | −0.0191 | 0.055* | |
| H4' | 0.647 (3) | 0.080 (5) | 0.2161 (12) | 0.028 (7)* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0247 (8) | 0.0388 (9) | 0.0308 (8) | 0.0114 (7) | 0.0028 (6) | −0.0044 (7) |
| C1 | 0.0195 (10) | 0.0230 (9) | 0.0345 (11) | 0.0010 (8) | 0.0020 (8) | 0.0002 (9) |
| C2 | 0.0211 (10) | 0.0238 (10) | 0.0262 (10) | −0.0003 (8) | 0.0038 (8) | 0.0025 (8) |
| C3 | 0.0170 (9) | 0.0232 (9) | 0.0249 (10) | −0.0002 (8) | 0.0032 (7) | −0.0002 (8) |
| C4 | 0.0189 (9) | 0.0221 (10) | 0.0255 (10) | 0.0005 (7) | 0.0065 (8) | −0.0007 (8) |
| C5 | 0.0225 (10) | 0.0197 (9) | 0.0250 (10) | −0.0009 (9) | 0.0062 (8) | −0.0007 (8) |
| C6 | 0.0250 (11) | 0.0190 (9) | 0.0272 (10) | −0.0019 (8) | 0.0016 (8) | 0.0025 (8) |
| O7 | 0.0232 (7) | 0.0175 (6) | 0.0356 (8) | 0.0016 (6) | 0.0072 (6) | 0.0001 (6) |
| C8 | 0.0191 (10) | 0.0202 (9) | 0.0309 (11) | −0.0007 (8) | 0.0035 (8) | −0.0022 (8) |
| O9 | 0.0209 (7) | 0.0162 (6) | 0.0373 (8) | 0.0016 (6) | −0.0002 (6) | −0.0009 (6) |
| C10 | 0.0311 (12) | 0.0280 (11) | 0.0403 (13) | −0.0024 (10) | 0.0107 (9) | −0.0010 (10) |
| C11 | 0.0267 (11) | 0.0284 (10) | 0.0373 (12) | 0.0007 (9) | −0.0031 (9) | −0.0035 (10) |
| O12 | 0.0190 (7) | 0.0322 (9) | 0.0553 (10) | 0.0009 (7) | 0.0031 (7) | −0.0107 (8) |
| C13 | 0.0202 (10) | 0.0256 (10) | 0.0361 (12) | 0.0009 (8) | −0.0015 (8) | −0.0003 (9) |
| O14 | 0.0206 (7) | 0.0272 (8) | 0.0361 (8) | 0.0014 (6) | 0.0002 (6) | −0.0051 (6) |
| C15 | 0.0341 (13) | 0.0673 (18) | 0.0430 (15) | 0.0070 (15) | −0.0067 (11) | 0.0092 (14) |
| C16 | 0.0270 (12) | 0.0316 (12) | 0.0651 (17) | 0.0012 (10) | 0.0069 (11) | 0.0080 (12) |
| C3' | 0.0235 (10) | 0.0266 (10) | 0.0226 (10) | 0.0031 (8) | 0.0053 (8) | −0.0002 (8) |
| N4' | 0.0324 (10) | 0.0264 (9) | 0.0262 (9) | −0.0010 (8) | 0.0086 (7) | −0.0008 (8) |
| C5' | 0.0249 (11) | 0.0371 (12) | 0.0215 (10) | 0.0018 (9) | 0.0015 (8) | −0.0028 (9) |
| O6' | 0.0486 (11) | 0.0295 (8) | 0.0319 (9) | 0.0045 (8) | 0.0087 (7) | −0.0024 (7) |
| O7' | 0.0574 (11) | 0.0382 (9) | 0.0287 (8) | 0.0009 (9) | 0.0195 (7) | −0.0046 (7) |
| C8' | 0.0536 (15) | 0.0439 (14) | 0.0300 (12) | 0.0132 (13) | 0.0142 (11) | −0.0045 (11) |
| C1'' | 0.0417 (13) | 0.0390 (13) | 0.0274 (11) | 0.0092 (11) | 0.0106 (9) | −0.0045 (10) |
| C2'' | 0.0479 (15) | 0.0494 (15) | 0.0354 (14) | 0.0047 (13) | 0.0027 (11) | −0.0031 (12) |
| C3'' | 0.0637 (18) | 0.0468 (15) | 0.0491 (17) | 0.0009 (16) | 0.0156 (14) | 0.0045 (14) |
| C4'' | 0.0669 (19) | 0.0580 (19) | 0.0323 (14) | 0.0206 (16) | 0.0110 (13) | 0.0033 (13) |
| C5'' | 0.0498 (16) | 0.075 (2) | 0.0310 (13) | 0.0108 (17) | 0.0005 (11) | −0.0100 (14) |
| C6'' | 0.0480 (15) | 0.0546 (16) | 0.0352 (13) | 0.0027 (13) | 0.0111 (11) | −0.0086 (12) |
Geometric parameters (Å, º)
| O1—C1 | 1.412 (2) | C13—C16 | 1.498 (3) |
| O1—C4 | 1.442 (2) | C13—C15 | 1.519 (3) |
| C1—O12 | 1.404 (2) | C15—H15A | 0.9600 |
| C1—C2 | 1.526 (3) | C15—H15B | 0.9600 |
| C1—H1 | 0.9800 | C15—H15C | 0.9600 |
| C2—O14 | 1.433 (2) | C16—H16A | 0.9600 |
| C2—C3 | 1.519 (3) | C16—H16B | 0.9600 |
| C2—H2 | 0.9800 | C16—H16C | 0.9600 |
| C3—C3' | 1.519 (3) | C3'—N4' | 1.457 (3) |
| C3—C4 | 1.535 (3) | C3'—H3'1 | 0.9700 |
| C3—H3 | 0.9800 | C3'—H3'2 | 0.9700 |
| C4—C5 | 1.520 (3) | N4'—C5' | 1.346 (3) |
| C4—H4 | 0.9800 | N4'—H4' | 0.80 (3) |
| C5—O9 | 1.427 (2) | C5'—O6' | 1.209 (3) |
| C5—C6 | 1.527 (3) | C5'—O7' | 1.355 (3) |
| C5—H5 | 0.9800 | O7'—C8' | 1.450 (3) |
| C6—O7 | 1.424 (3) | C8'—C1'' | 1.502 (3) |
| C6—H6A | 0.9700 | C8'—H8'1 | 0.9700 |
| C6—H6B | 0.9700 | C8'—H8'2 | 0.9700 |
| O7—C8 | 1.424 (2) | C1''—C2'' | 1.384 (4) |
| C8—O9 | 1.443 (2) | C1''—C6'' | 1.387 (4) |
| C8—C10 | 1.501 (3) | C2''—C3'' | 1.376 (4) |
| C8—C11 | 1.519 (3) | C2''—H2'' | 0.9300 |
| C10—H10A | 0.9600 | C3''—C4'' | 1.382 (4) |
| C10—H10B | 0.9600 | C3''—H3'' | 0.9300 |
| C10—H10C | 0.9600 | C4''—C5'' | 1.367 (5) |
| C11—H11A | 0.9600 | C4''—H4'' | 0.9300 |
| C11—H11B | 0.9600 | C5''—C6'' | 1.387 (4) |
| C11—H11C | 0.9600 | C5''—H5'' | 0.9300 |
| O12—C13 | 1.424 (3) | C6''—H6'' | 0.9300 |
| C13—O14 | 1.435 (3) | ||
| C1—O1—C4 | 110.30 (15) | C1—O12—C13 | 110.36 (16) |
| O12—C1—O1 | 111.76 (17) | O12—C13—O14 | 105.28 (15) |
| O12—C1—C2 | 105.29 (17) | O12—C13—C16 | 108.82 (19) |
| O1—C1—C2 | 106.75 (16) | O14—C13—C16 | 109.43 (18) |
| O12—C1—H1 | 110.9 | O12—C13—C15 | 109.1 (2) |
| O1—C1—H1 | 110.9 | O14—C13—C15 | 110.69 (19) |
| C2—C1—H1 | 110.9 | C16—C13—C15 | 113.2 (2) |
| O14—C2—C3 | 110.74 (16) | C2—O14—C13 | 107.18 (15) |
| O14—C2—C1 | 102.96 (16) | C13—C15—H15A | 109.5 |
| C3—C2—C1 | 103.87 (16) | C13—C15—H15B | 109.5 |
| O14—C2—H2 | 112.8 | H15A—C15—H15B | 109.5 |
| C3—C2—H2 | 112.8 | C13—C15—H15C | 109.5 |
| C1—C2—H2 | 112.8 | H15A—C15—H15C | 109.5 |
| C2—C3—C3' | 115.04 (17) | H15B—C15—H15C | 109.5 |
| C2—C3—C4 | 101.29 (16) | C13—C16—H16A | 109.5 |
| C3'—C3—C4 | 116.30 (17) | C13—C16—H16B | 109.5 |
| C2—C3—H3 | 107.9 | H16A—C16—H16B | 109.5 |
| C3'—C3—H3 | 107.9 | C13—C16—H16C | 109.5 |
| C4—C3—H3 | 107.9 | H16A—C16—H16C | 109.5 |
| O1—C4—C5 | 106.73 (15) | H16B—C16—H16C | 109.5 |
| O1—C4—C3 | 103.54 (15) | N4'—C3'—C3 | 109.09 (17) |
| C5—C4—C3 | 117.26 (16) | N4'—C3'—H3'1 | 109.9 |
| O1—C4—H4 | 109.7 | C3—C3'—H3'1 | 109.9 |
| C5—C4—H4 | 109.7 | N4'—C3'—H3'2 | 109.9 |
| C3—C4—H4 | 109.7 | C3—C3'—H3'2 | 109.9 |
| O9—C5—C4 | 110.29 (16) | H3'1—C3'—H3'2 | 108.3 |
| O9—C5—C6 | 103.92 (14) | C5'—N4'—C3' | 121.7 (2) |
| C4—C5—C6 | 115.15 (17) | C5'—N4'—H4' | 116.9 (18) |
| O9—C5—H5 | 109.1 | C3'—N4'—H4' | 120.3 (18) |
| C4—C5—H5 | 109.1 | O6'—C5'—N4' | 125.9 (2) |
| C6—C5—H5 | 109.1 | O6'—C5'—O7' | 125.2 (2) |
| O7—C6—C5 | 103.79 (16) | N4'—C5'—O7' | 108.9 (2) |
| O7—C6—H6A | 111.0 | C5'—O7'—C8' | 117.5 (2) |
| C5—C6—H6A | 111.0 | O7'—C8'—C1'' | 106.1 (2) |
| O7—C6—H6B | 111.0 | O7'—C8'—H8'1 | 110.5 |
| C5—C6—H6B | 111.0 | C1''—C8'—H8'1 | 110.5 |
| H6A—C6—H6B | 109.0 | O7'—C8'—H8'2 | 110.5 |
| C6—O7—C8 | 105.08 (16) | C1''—C8'—H8'2 | 110.5 |
| O7—C8—O9 | 104.38 (16) | H8'1—C8'—H8'2 | 108.7 |
| O7—C8—C10 | 108.31 (18) | C2''—C1''—C6'' | 118.9 (2) |
| O9—C8—C10 | 109.48 (17) | C2''—C1''—C8' | 120.8 (2) |
| O7—C8—C11 | 111.69 (17) | C6''—C1''—C8' | 120.2 (3) |
| O9—C8—C11 | 109.16 (17) | C3''—C2''—C1'' | 120.6 (3) |
| C10—C8—C11 | 113.42 (18) | C3''—C2''—H2'' | 119.7 |
| C5—O9—C8 | 108.74 (14) | C1''—C2''—H2'' | 119.7 |
| C8—C10—H10A | 109.5 | C2''—C3''—C4'' | 120.4 (3) |
| C8—C10—H10B | 109.5 | C2''—C3''—H3'' | 119.8 |
| H10A—C10—H10B | 109.5 | C4''—C3''—H3'' | 119.8 |
| C8—C10—H10C | 109.5 | C5''—C4''—C3'' | 119.4 (3) |
| H10A—C10—H10C | 109.5 | C5''—C4''—H4'' | 120.3 |
| H10B—C10—H10C | 109.5 | C3''—C4''—H4'' | 120.3 |
| C8—C11—H11A | 109.5 | C4''—C5''—C6'' | 120.8 (3) |
| C8—C11—H11B | 109.5 | C4''—C5''—H5'' | 119.6 |
| H11A—C11—H11B | 109.5 | C6''—C5''—H5'' | 119.6 |
| C8—C11—H11C | 109.5 | C5''—C6''—C1'' | 119.9 (3) |
| H11A—C11—H11C | 109.5 | C5''—C6''—H6'' | 120.1 |
| H11B—C11—H11C | 109.5 | C1''—C6''—H6'' | 120.1 |
| C4—O1—C1—O12 | 107.54 (18) | C11—C8—O9—C5 | −95.99 (19) |
| C4—O1—C1—C2 | −7.1 (2) | O1—C1—O12—C13 | −111.56 (19) |
| O12—C1—C2—O14 | −20.6 (2) | C2—C1—O12—C13 | 4.0 (2) |
| O1—C1—C2—O14 | 98.33 (18) | C1—O12—C13—O14 | 14.4 (2) |
| O12—C1—C2—C3 | −136.12 (17) | C1—O12—C13—C16 | 131.58 (19) |
| O1—C1—C2—C3 | −17.2 (2) | C1—O12—C13—C15 | −104.5 (2) |
| O14—C2—C3—C3' | 49.2 (2) | C3—C2—O14—C13 | 140.31 (17) |
| C1—C2—C3—C3' | 159.10 (16) | C1—C2—O14—C13 | 29.82 (19) |
| O14—C2—C3—C4 | −77.1 (2) | O12—C13—O14—C2 | −28.1 (2) |
| C1—C2—C3—C4 | 32.8 (2) | C16—C13—O14—C2 | −144.9 (2) |
| C1—O1—C4—C5 | 152.58 (16) | C15—C13—O14—C2 | 89.6 (2) |
| C1—O1—C4—C3 | 28.2 (2) | C2—C3—C3'—N4' | 65.0 (2) |
| C2—C3—C4—O1 | −37.23 (19) | C4—C3—C3'—N4' | −176.82 (16) |
| C3'—C3—C4—O1 | −162.69 (16) | C3—C3'—N4'—C5' | −165.57 (19) |
| C2—C3—C4—C5 | −154.43 (17) | C3'—N4'—C5'—O6' | 3.5 (4) |
| C3'—C3—C4—C5 | 80.1 (2) | C3'—N4'—C5'—O7' | −177.68 (18) |
| O1—C4—C5—O9 | −67.04 (19) | O6'—C5'—O7'—C8' | 0.7 (3) |
| C3—C4—C5—O9 | 48.4 (2) | N4'—C5'—O7'—C8' | −178.11 (19) |
| O1—C4—C5—C6 | 175.77 (16) | C5'—O7'—C8'—C1'' | 153.0 (2) |
| C3—C4—C5—C6 | −68.8 (2) | O7'—C8'—C1''—C2'' | 67.3 (3) |
| O9—C5—C6—O7 | −20.8 (2) | O7'—C8'—C1''—C6'' | −109.6 (3) |
| C4—C5—C6—O7 | 99.97 (19) | C6''—C1''—C2''—C3'' | 0.9 (4) |
| C5—C6—O7—C8 | 35.75 (19) | C8'—C1''—C2''—C3'' | −176.1 (2) |
| C6—O7—C8—O9 | −37.11 (19) | C1''—C2''—C3''—C4'' | −0.5 (4) |
| C6—O7—C8—C10 | −153.69 (17) | C2''—C3''—C4''—C5'' | −0.3 (4) |
| C6—O7—C8—C11 | 80.7 (2) | C3''—C4''—C5''—C6'' | 0.7 (4) |
| C4—C5—O9—C8 | −125.60 (16) | C4''—C5''—C6''—C1'' | −0.3 (4) |
| C6—C5—O9—C8 | −1.7 (2) | C2''—C1''—C6''—C5'' | −0.5 (4) |
| O7—C8—O9—C5 | 23.5 (2) | C8'—C1''—C6''—C5'' | 176.5 (2) |
| C10—C8—O9—C5 | 139.31 (17) |
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4′—H4′···O6′i | 0.80 (3) | 2.51 (3) | 3.295 (3) | 167 (2) |
| C6—H6B···O9ii | 0.97 | 2.32 | 3.184 (3) | 141 |
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z.
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/S2056989015017582/su5210sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015017582/su5210Isup2.hkl
CCDC reference: 1425954
Additional supporting information: crystallographic information; 3D view; checkCIF report