research communications
O-isopropylidene-α-D-allofuranose
of 3-deoxy-3-nitromethyl-1,2;5,6-di-aInstitute of Technology of Organic Chemistry, Faculty of Materials Science and, Applied Chemistry, Riga Technical University, P. Valdena 3/7, Riga, LV-1048, Latvia, and bLatvian Institute of Organic Synthesis, Str. Aizkraukles 21, Riga, LV 1006, Latvia
*Correspondence e-mail: vitalijs.rjabovs@rtu.lv, d_stepanovs@osi.lv
The title compound, C13H21NO7 {systematic name: (3aR,5S,6R,6aR)-5-[(R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-6-(nitromethyl)tetrahydrofuro[2,3-d][1,3]dioxole}, consists of a substituted 2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxolane skeleton. The furanose ring A adopts a oT4 conformation. The fused dioxolane ring B and the substituent dioxolane ring C also have twisted conformations. There are no strong hydrogen bonds in the only weak C—H⋯O contacts are present, which link the molecules to form a three-dimensional structure.
Keywords: crystal structure; nitro carbohydrate; nitro sugar; C(3)-nitromethyl allose; allofuranose; C—H⋯O hydrogen bonding.
CCDC reference: 1451051
1. Chemical context
The title compound 1, has been used for the syntheses of isoxazoles (Lugiņina et al., 2013) and carbohydrate-based and amino acids (Rjabovs et al., 2015a). with amino groups are valuable synthetic precursors and are easily converted to spirocyclic carbohydrate derivatives (Turks et al., 2013), imino sugars (Filichev & Pedersen, 2001), nucleic acid mimetics (Rozners et al., 2003), and azido sugars (Mackeviča et al., 2014; Rjabova et al., 2012). The latter are widely used for the syntheses of triazoles (Uzuleņa et al., 2015; Grigorjeva et al., 2015) and THF-amino acids (sugar amino acids) (Rjabovs & Turks, 2013).
2. Structural commentary
The title compound 1, consists of a tetrahydrofuran core (ring A) fused with a dioxolane ring (B) and substituted with a dioxolane (ring C) and a nitromethyl group (Fig. 1). The of the furanose ring (A) based on the internal dihedral angles of the ring shows that its pseudorotational phase angle P = 70° (Altona & Sundaralingam, 1972; Taha et al., 2013). Thus, this ring adopts a conformation close to oT4, where O1 and C4 deviate by 0.214 (2) and −0.340 (3) Å, respectively, from the plane through atoms C1/C2/C3. Such a conformation of the furanose ring is rather unusual for 3-C-monosubstituted 3-deoxy-1,2-O-isopropylidene-α-D-allofuranoses. For example, previously reported structures (Rjabovs et al., 2014, 2015a,b) had conformations between 3E and 3T4. The fused dioxolane ring B also adopts a twisted conformation on bond C13—O12; these atoms deviate by −0.324 (4) and 0.224 (3) Å, respectively, from plane C1/C2/O14. The dihedral angle subtended by the mean planes of rings A and B is 63.7 (2)°. The five-membered ring of the 2,2-dimethyl-1,3-dioxolan-4-yl group, ring C, also adopts a twisted conformation, on bond C6—O7; these atoms deviate by 0.143 (4) and −0.381 (2) Å, respectively from plane C5/O9/C8.
3. Supramolecular features
In the crystal, molecules are linked via C—H⋯O hydrogen bonds, forming chains along [100]. The chains are linked via further C—H⋯O hydrogen bonds, forming a three-dimensional structure (Table 1 and Fig. 2).
4. Database survey
A search of the Cambridge Structural Database (Version 5.37; Groom & Allen, 2014) for S1 (Fig. 3) gave 137 hits, while a search for S2 (Fig. 3) gave only five hits. Amongst the latter compounds, four concern the structures with a hydroxyl and a nitromethyl group attached to atom C3 (BOGFOU: Turks et al., 2014; BOGFUA: Turks et al., 2014; CIDVO: Turks et al., 2013; USODEM: Zhang et al., 2011). They are crystallizing in space groups P212121, P32, C2 and P61, respectively. In the fifth compound (KATWIN; Lugiņina et al., 2012), the extra substituent at atom C3 is a methylthio group; it crystallizes in C2.
5. Synthesis and crystallization
The title compound 1, was synthesized by reduction of the nitro olefin 2 (Albrecht & Moffatt, 1970; Filichev et al., 2001; Lugiņina et al., 2012) with sodium borohydride in methanol solution, as illustrated in Fig. 4. NaBH4 (6.2 g, 163.9 mmol, 5.5 eq.) was added portion wise to a solution of 2 (9.1 g, 30.0 mmol, 1.0 eq.) in MeOH (200 ml) over 30 min at 273 K. After completion (monitored by TLC) the reaction mixture was acidified using 10% aqueous solution of AcOH to pH 6–7 and then evaporated to dryness. The residue was dissolved in EtOAc (90 ml), washed with brine (3 × 10 ml), dried over NaSO4, and evaporated. The product 1 was purified by on silica gel (Hexanes/EtOAc 3:1 → 2:1) giving a white crystalline solid (yield: 6.5 g, 72%; m.p. 355–356 K). Rf = 0.9 (hexanes/EtOAc 1:1). 1H NMR (CDCl3, 300 MHz): δ 5.84 (d, J = 3.7 Hz, 1H), 4.88–4.82 (m, 21H), 4.68 (dd, AB syst., J = 14.9 Hz, J = 10.4 Hz, 1H), 4.14 (dd, J = 8.0 Hz, J = 5.5 Hz, 1H), 4.02–3.92 (m, 2H), 3.65 (dd, J = 9.9 Hz, J = 8.4 Hz, 1H), 2.74 (tt, J = 10.1 Hz, J = 4.4 Hz, 1H), 1.52 (s, 3H), 1.40, (s, 3H), 1.33 (s, 3H), 1.32 (s, 3H). 13C-NMR (75 MHz, CDCl3): δ 112.6, 110.1, 105.4, 80.5, 79.0, 77.8, 70.8, 68.2, 46.6, 26.8, 26.7, 26.4, 25.1. X-ray quality single crystals were obtained by slow evaporation of a dichloromethane solution at ambient temperature.
6. Refinement
Crystal data, data collection and structure . The H atoms were included in calculated positions and refined as riding atoms: C—H = 0.96–0.98 Å with Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms. The is based on that of the starting material.
details are summarized in Table 2Supporting information
CCDC reference: 1451051
10.1107/S2056989016001845/su5270sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016001845/su5270Isup2.hkl
The title compound 1, has been used for the syntheses of isoxazoles (Lugiņina et al., 2013) and carbohydrate-based
and amino acids (Rjabovs et al., 2015a). with amino groups are valuable synthetic precursors and are easily converted to spirocyclic carbohydrate derivatives (Turks et al., 2013), imino sugars (Filichev & Pedersen, 2001), nucleic acid mimetics (Rozners et al., 2003), and azido sugars (Mackeviča et al., 2014; Rjabova et al., 2012). The latter are widely used for the syntheses of triazoles (Uzuleņa et al., 2015; Grigorjeva et al., 2015) and THF-amino acids (sugar amino acids) (Rjabovs & Turks, 2013).The title compound 1, consists of a tetrahydrofuran core (ring A) fused with a dioxolane ring (B) and substituted with a dioxolane (ring C) and a nitromethyl group (Fig. 1). The α-D-allofuranoses. For example, previously reported structures (Rjabovs et al., 2014, 2015a,b) had conformations between 3E and 3T4. The fused dioxolane ring B also adopts a twisted conformation on bond C13—O12; these atoms deviate by −0.324 (4) and 0.224 (3) Å, respectively, from plane C1/C2/O14. The dihedral angle subtended by the mean planes of rings A and B is 63.7 (2)°. The five-membered ring of the 2,2-dimethyl-1,3-dioxolan-4-yl group, ring C, also adopts a twisted conformation, on bond C6—O7; these atoms deviate by 0.143 (4) and −0.381 (2) Å, respectively from plane C5/O9/C8.
of the furanose ring (A) based on the internal dihedral angles of the ring shows that its pseudorotational phase angle P = 70° (Altona & Sundaralingam, 1972; Taha et al., 2013). Thus, this ring adopts a conformation close to oT4, where O1 and C4 deviate by 0.214 (2) and −0.340 (3) Å, respectively, from the plane through atoms C1/C2/C3. Such a conformation of the furanose ring is rather unusual for 3-C-monosubstituted 3-deoxy-1,2-O-isopropylidene-In the crystal, molecules are linked via C—H···O hydrogen bonds, forming chains along [100]. The chains are linked via further C—H···O hydrogen bonds, forming a three-dimensional structure (Table 1 and Fig. 2).
A search of the Cambridge Structural Database (Version 5.37; Groom & Allen, 2014) for
S1 (Fig. 3) gave 137 hits, while a search for S2 (Fig. 3) gave only five hits. Amongst the latter compounds, four concern the same structure with both a hydroxyl and a nitromethyl group on atom C3 (BOGFOU: Turks et al., 2014; BOGFUA: Turks et al., 2014; CIDVO: Turks et al., 2013; USODEM: Zhang et al., 2011). They are polymorphs crystallizing in space groups P212121, P32, C2 and P61, respectively. In the fifth compound (KATWIN; Lugiņina et al., 2012), the extra substituent on atom C3 is a methyl sulfanyl group; it crystallizes in C2.The title compound 1, was synthesized by reduction of the nitro olefin 2 (Albrecht & Moffatt, 1970; Filichev et al., 2001; Lugiņina et al., 2012) with sodium borohydride in methanol solution, as illustrated in Fig. 4. NaBH4 (6.2 g, 163.9 mmol, 5.5 eq.) was added portion wise to a solution of 2 (9.1 g, 30.0 mmol, 1.0 eq.) in MeOH (200 ml) over 30 min at 273 K. After completion (monitored by TLC) the reaction mixture was acidified using 10% aqueous solution of AcOH to pH 6–7 and then evaporated to dryness. The residue was dissolved in EtOAc (90 ml), washed with brine (3 × 10 ml), dried over NaSO4, and evaporated. The product 1 was purified by → 2:1) giving a white crystalline solid (yield: 6.5 g, 72%; m.p. 355–356 K). Rf = 0.9 (hexanes/EtOAc 1:1). 1H NMR (CDCl3, 300 MHz): δ 5.84 (d, J = 3.7 Hz, 1H), 4.88–4.82 (m, 21H), 4.68 (dd, AB syst., J = 14.9 Hz, J = 10.4 Hz, 1H), 4.14 (dd, J = 8.0 Hz, J = 5.5 Hz, 1H), 4.02–3.92 (m, 2H), 3.65 (dd, J = 9.9 Hz, J = 8.4 Hz, 1H), 2.74 (tt, J = 10.1 Hz, J = 4.4 Hz, 1H), 1.52 (s, 3H), 1.40, (s, 3H), 1.33 (s, 3H), 1.32 (s, 3H). 13C-NMR (75 MHz, CDCl3): δ 112.6, 110.1, 105.4, 80.5, 79.0, 77.8, 70.8, 68.2, 46.6, 26.8, 26.7, 26.4, 25.1. X-ray quality single crystals were obtained by slow evaporation of a dichloromethane solution at ambient temperature.
on silica gel (Hexanes/EtOAc 3:1The title compound 1, has been used for the syntheses of isoxazoles (Lugiņina et al., 2013) and carbohydrate-based
and amino acids (Rjabovs et al., 2015a). with amino groups are valuable synthetic precursors and are easily converted to spirocyclic carbohydrate derivatives (Turks et al., 2013), imino sugars (Filichev & Pedersen, 2001), nucleic acid mimetics (Rozners et al., 2003), and azido sugars (Mackeviča et al., 2014; Rjabova et al., 2012). The latter are widely used for the syntheses of triazoles (Uzuleņa et al., 2015; Grigorjeva et al., 2015) and THF-amino acids (sugar amino acids) (Rjabovs & Turks, 2013).The title compound 1, consists of a tetrahydrofuran core (ring A) fused with a dioxolane ring (B) and substituted with a dioxolane (ring C) and a nitromethyl group (Fig. 1). The α-D-allofuranoses. For example, previously reported structures (Rjabovs et al., 2014, 2015a,b) had conformations between 3E and 3T4. The fused dioxolane ring B also adopts a twisted conformation on bond C13—O12; these atoms deviate by −0.324 (4) and 0.224 (3) Å, respectively, from plane C1/C2/O14. The dihedral angle subtended by the mean planes of rings A and B is 63.7 (2)°. The five-membered ring of the 2,2-dimethyl-1,3-dioxolan-4-yl group, ring C, also adopts a twisted conformation, on bond C6—O7; these atoms deviate by 0.143 (4) and −0.381 (2) Å, respectively from plane C5/O9/C8.
of the furanose ring (A) based on the internal dihedral angles of the ring shows that its pseudorotational phase angle P = 70° (Altona & Sundaralingam, 1972; Taha et al., 2013). Thus, this ring adopts a conformation close to oT4, where O1 and C4 deviate by 0.214 (2) and −0.340 (3) Å, respectively, from the plane through atoms C1/C2/C3. Such a conformation of the furanose ring is rather unusual for 3-C-monosubstituted 3-deoxy-1,2-O-isopropylidene-In the crystal, molecules are linked via C—H···O hydrogen bonds, forming chains along [100]. The chains are linked via further C—H···O hydrogen bonds, forming a three-dimensional structure (Table 1 and Fig. 2).
A search of the Cambridge Structural Database (Version 5.37; Groom & Allen, 2014) for
S1 (Fig. 3) gave 137 hits, while a search for S2 (Fig. 3) gave only five hits. Amongst the latter compounds, four concern the same structure with both a hydroxyl and a nitromethyl group on atom C3 (BOGFOU: Turks et al., 2014; BOGFUA: Turks et al., 2014; CIDVO: Turks et al., 2013; USODEM: Zhang et al., 2011). They are polymorphs crystallizing in space groups P212121, P32, C2 and P61, respectively. In the fifth compound (KATWIN; Lugiņina et al., 2012), the extra substituent on atom C3 is a methyl sulfanyl group; it crystallizes in C2.The title compound 1, was synthesized by reduction of the nitro olefin 2 (Albrecht & Moffatt, 1970; Filichev et al., 2001; Lugiņina et al., 2012) with sodium borohydride in methanol solution, as illustrated in Fig. 4. NaBH4 (6.2 g, 163.9 mmol, 5.5 eq.) was added portion wise to a solution of 2 (9.1 g, 30.0 mmol, 1.0 eq.) in MeOH (200 ml) over 30 min at 273 K. After completion (monitored by TLC) the reaction mixture was acidified using 10% aqueous solution of AcOH to pH 6–7 and then evaporated to dryness. The residue was dissolved in EtOAc (90 ml), washed with brine (3 × 10 ml), dried over NaSO4, and evaporated. The product 1 was purified by → 2:1) giving a white crystalline solid (yield: 6.5 g, 72%; m.p. 355–356 K). Rf = 0.9 (hexanes/EtOAc 1:1). 1H NMR (CDCl3, 300 MHz): δ 5.84 (d, J = 3.7 Hz, 1H), 4.88–4.82 (m, 21H), 4.68 (dd, AB syst., J = 14.9 Hz, J = 10.4 Hz, 1H), 4.14 (dd, J = 8.0 Hz, J = 5.5 Hz, 1H), 4.02–3.92 (m, 2H), 3.65 (dd, J = 9.9 Hz, J = 8.4 Hz, 1H), 2.74 (tt, J = 10.1 Hz, J = 4.4 Hz, 1H), 1.52 (s, 3H), 1.40, (s, 3H), 1.33 (s, 3H), 1.32 (s, 3H). 13C-NMR (75 MHz, CDCl3): δ 112.6, 110.1, 105.4, 80.5, 79.0, 77.8, 70.8, 68.2, 46.6, 26.8, 26.7, 26.4, 25.1. X-ray quality single crystals were obtained by slow evaporation of a dichloromethane solution at ambient temperature.
on silica gel (Hexanes/EtOAc 3:1 detailsCrystal data, data collection and structure
details are summarized in Table 2. The H atoms were included in calculated positions and refined as riding atoms: C—H = 0.96–0.98 Å with Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms. The is based on that of the starting material.Data collection: KappaCCD Server Software (Nonius, 1997); cell
SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2011 (Burla et al., 2012); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).Fig. 1. The molecular structure of the title compound 1, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. A view along the b axis of the crystal packing of the title compound 1. Hydrogen bonds are shown as dashed lines (see Table 1) and H atoms not involved in these interactions have been omitted for clarity. | |
Fig. 3. Substructures used for the database survey. | |
Fig. 4. Synthesis of the title compound. |
C13H21NO7 | Dx = 1.341 Mg m−3 |
Mr = 303.31 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 26214 reflections |
a = 5.5044 (2) Å | θ = 1.0–30.0° |
b = 12.6144 (4) Å | µ = 0.11 mm−1 |
c = 21.6348 (9) Å | T = 173 K |
V = 1502.21 (10) Å3 | Needle, colourless |
Z = 4 | 0.26 × 0.08 × 0.06 mm |
F(000) = 648 |
Nonius KappaCCD diffractometer | 2316 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | θmax = 30.1°, θmin = 3.2° |
φ and ω scan | h = −7→7 |
4225 measured reflections | k = −17→17 |
4225 independent reflections | l = −30→30 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.065 | H-atom parameters constrained |
wR(F2) = 0.127 | w = 1/[σ2(Fo2) + (0.0367P)2 + 0.3523P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
4225 reflections | Δρmax = 0.20 e Å−3 |
194 parameters | Δρmin = −0.25 e Å−3 |
C13H21NO7 | V = 1502.21 (10) Å3 |
Mr = 303.31 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.5044 (2) Å | µ = 0.11 mm−1 |
b = 12.6144 (4) Å | T = 173 K |
c = 21.6348 (9) Å | 0.26 × 0.08 × 0.06 mm |
Nonius KappaCCD diffractometer | 4225 independent reflections |
4225 measured reflections | 2316 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.065 | 0 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.20 e Å−3 |
4225 reflections | Δρmin = −0.25 e Å−3 |
194 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.1756 (4) | 0.94348 (18) | 0.03395 (11) | 0.0372 (6) | |
C1 | 0.2580 (7) | 0.8418 (3) | 0.04912 (17) | 0.0368 (9) | |
H1 | 0.3478 | 0.8095 | 0.0148 | 0.044* | |
C2 | 0.4157 (6) | 0.8508 (3) | 0.10747 (17) | 0.0339 (8) | |
H2 | 0.5873 | 0.8361 | 0.0990 | 0.041* | |
C3 | 0.3744 (6) | 0.9665 (2) | 0.12881 (17) | 0.0306 (8) | |
H3 | 0.5155 | 1.0090 | 0.1166 | 0.037* | |
C4 | 0.1536 (6) | 1.0022 (2) | 0.09017 (16) | 0.0309 (8) | |
H4 | 0.0025 | 0.9832 | 0.1114 | 0.037* | |
C5 | 0.1502 (6) | 1.1182 (3) | 0.07239 (18) | 0.0360 (9) | |
H5 | 0.3020 | 1.1371 | 0.0514 | 0.043* | |
C6 | −0.0661 (6) | 1.1468 (3) | 0.03179 (19) | 0.0392 (9) | |
H6A | −0.0244 | 1.2023 | 0.0026 | 0.047* | |
H6B | −0.1248 | 1.0854 | 0.0093 | 0.047* | |
O7 | −0.2414 (4) | 1.18276 (17) | 0.07540 (12) | 0.0391 (6) | |
C8 | −0.1090 (6) | 1.2369 (3) | 0.12245 (19) | 0.0393 (9) | |
O9 | 0.1197 (4) | 1.18174 (19) | 0.12615 (13) | 0.0470 (7) | |
C10 | −0.0637 (8) | 1.3514 (3) | 0.1055 (2) | 0.0489 (11) | |
H10A | −0.2159 | 1.3882 | 0.1027 | 0.073* | |
H10B | 0.0184 | 1.3548 | 0.0664 | 0.073* | |
H10C | 0.0354 | 1.3840 | 0.1367 | 0.073* | |
C11 | −0.2428 (8) | 1.2243 (3) | 0.18262 (19) | 0.0554 (11) | |
H11A | −0.2530 | 1.1505 | 0.1930 | 0.083* | |
H11B | −0.4035 | 1.2530 | 0.1786 | 0.083* | |
H11C | −0.1572 | 1.2614 | 0.2147 | 0.083* | |
O12 | 0.0607 (5) | 0.77711 (19) | 0.06819 (12) | 0.0397 (6) | |
C13 | 0.1517 (6) | 0.7096 (3) | 0.11560 (17) | 0.0346 (9) | |
O14 | 0.3131 (4) | 0.77660 (18) | 0.14980 (11) | 0.0362 (6) | |
C15 | 0.2887 (8) | 0.6163 (3) | 0.08712 (19) | 0.0489 (11) | |
H15A | 0.3527 | 0.5723 | 0.1194 | 0.073* | |
H15B | 0.4198 | 0.6425 | 0.0621 | 0.073* | |
H15C | 0.1798 | 0.5756 | 0.0619 | 0.073* | |
C16 | −0.0501 (7) | 0.6743 (3) | 0.1567 (2) | 0.0484 (11) | |
H16A | −0.1272 | 0.7352 | 0.1748 | 0.073* | |
H16B | 0.0138 | 0.6299 | 0.1889 | 0.073* | |
H16C | −0.1670 | 0.6352 | 0.1330 | 0.073* | |
C3' | 0.3314 (6) | 0.9814 (3) | 0.19700 (17) | 0.0339 (8) | |
H3'1 | 0.2859 | 1.0546 | 0.2044 | 0.041* | |
H3'2 | 0.1959 | 0.9372 | 0.2095 | 0.041* | |
N4' | 0.5468 (6) | 0.9550 (2) | 0.23638 (16) | 0.0373 (7) | |
O5' | 0.7368 (4) | 0.9282 (2) | 0.21135 (13) | 0.0518 (8) | |
O6' | 0.5199 (5) | 0.9616 (3) | 0.29175 (14) | 0.0612 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0535 (15) | 0.0301 (13) | 0.0281 (14) | 0.0051 (11) | −0.0038 (12) | −0.0004 (12) |
C1 | 0.045 (2) | 0.0324 (19) | 0.033 (2) | 0.0065 (17) | 0.0013 (17) | −0.0011 (16) |
C2 | 0.0328 (19) | 0.0309 (18) | 0.038 (2) | 0.0052 (15) | 0.0025 (17) | 0.0038 (17) |
C3 | 0.0258 (17) | 0.0283 (19) | 0.038 (2) | −0.0020 (13) | −0.0002 (15) | −0.0018 (16) |
C4 | 0.0273 (17) | 0.0285 (18) | 0.037 (2) | −0.0028 (14) | −0.0016 (16) | −0.0007 (17) |
C5 | 0.0299 (18) | 0.0302 (19) | 0.048 (2) | 0.0000 (14) | −0.0025 (18) | 0.0015 (18) |
C6 | 0.038 (2) | 0.0311 (19) | 0.048 (2) | 0.0058 (16) | −0.0062 (18) | 0.0003 (19) |
O7 | 0.0308 (13) | 0.0349 (13) | 0.0517 (17) | −0.0016 (11) | −0.0035 (12) | −0.0014 (13) |
C8 | 0.038 (2) | 0.0284 (19) | 0.052 (3) | 0.0024 (15) | −0.0039 (18) | −0.0024 (18) |
O9 | 0.0418 (15) | 0.0345 (14) | 0.0646 (19) | 0.0089 (11) | −0.0173 (13) | −0.0132 (14) |
C10 | 0.055 (2) | 0.030 (2) | 0.062 (3) | −0.0002 (18) | 0.003 (2) | 0.003 (2) |
C11 | 0.068 (3) | 0.046 (2) | 0.052 (3) | −0.004 (2) | 0.002 (2) | 0.003 (2) |
O12 | 0.0432 (14) | 0.0323 (13) | 0.0436 (15) | −0.0020 (11) | −0.0114 (12) | 0.0004 (13) |
C13 | 0.040 (2) | 0.0257 (18) | 0.038 (2) | −0.0024 (15) | −0.0072 (17) | −0.0009 (16) |
O14 | 0.0408 (14) | 0.0327 (13) | 0.0352 (15) | −0.0045 (11) | −0.0058 (12) | 0.0045 (12) |
C15 | 0.065 (3) | 0.0281 (19) | 0.053 (3) | 0.0049 (18) | −0.004 (2) | −0.0008 (19) |
C16 | 0.045 (2) | 0.042 (2) | 0.059 (3) | −0.0028 (18) | 0.000 (2) | 0.006 (2) |
C3' | 0.0245 (17) | 0.038 (2) | 0.040 (2) | −0.0017 (15) | −0.0016 (16) | −0.0010 (17) |
N4' | 0.0387 (18) | 0.0316 (17) | 0.042 (2) | −0.0026 (14) | −0.0078 (16) | 0.0001 (16) |
O5' | 0.0312 (14) | 0.0693 (19) | 0.0548 (19) | 0.0061 (14) | −0.0057 (14) | 0.0012 (15) |
O6' | 0.0627 (19) | 0.085 (2) | 0.0355 (18) | 0.0003 (16) | −0.0099 (16) | −0.0045 (17) |
O1—C1 | 1.399 (4) | C8—C10 | 1.511 (5) |
O1—C4 | 1.429 (4) | C10—H10A | 0.9600 |
C1—O12 | 1.420 (4) | C10—H10B | 0.9600 |
C1—C2 | 1.537 (5) | C10—H10C | 0.9600 |
C1—H1 | 0.9800 | C11—H11A | 0.9600 |
C2—O14 | 1.427 (4) | C11—H11B | 0.9600 |
C2—C3 | 1.547 (5) | C11—H11C | 0.9600 |
C2—H2 | 0.9800 | O12—C13 | 1.424 (4) |
C3—C3' | 1.506 (5) | C13—O14 | 1.432 (4) |
C3—C4 | 1.542 (5) | C13—C16 | 1.491 (5) |
C3—H3 | 0.9800 | C13—C15 | 1.527 (5) |
C4—C5 | 1.514 (4) | C15—H15A | 0.9600 |
C4—H4 | 0.9800 | C15—H15B | 0.9600 |
C5—O9 | 1.422 (4) | C15—H15C | 0.9600 |
C5—C6 | 1.523 (5) | C16—H16A | 0.9600 |
C5—H5 | 0.9800 | C16—H16B | 0.9600 |
C6—O7 | 1.424 (4) | C16—H16C | 0.9600 |
C6—H6A | 0.9700 | C3'—N4' | 1.498 (4) |
C6—H6B | 0.9700 | C3'—H3'1 | 0.9700 |
O7—C8 | 1.426 (4) | C3'—H3'2 | 0.9700 |
C8—O9 | 1.441 (4) | N4'—O6' | 1.210 (4) |
C8—C11 | 1.504 (6) | N4'—O5' | 1.225 (4) |
C1—O1—C4 | 107.6 (2) | C11—C8—C10 | 113.0 (3) |
O1—C1—O12 | 110.3 (3) | C5—O9—C8 | 109.2 (3) |
O1—C1—C2 | 107.9 (3) | C8—C10—H10A | 109.5 |
O12—C1—C2 | 103.7 (3) | C8—C10—H10B | 109.5 |
O1—C1—H1 | 111.5 | H10A—C10—H10B | 109.5 |
O12—C1—H1 | 111.5 | C8—C10—H10C | 109.5 |
C2—C1—H1 | 111.5 | H10A—C10—H10C | 109.5 |
O14—C2—C1 | 104.8 (3) | H10B—C10—H10C | 109.5 |
O14—C2—C3 | 111.7 (3) | C8—C11—H11A | 109.5 |
C1—C2—C3 | 103.4 (3) | C8—C11—H11B | 109.5 |
O14—C2—H2 | 112.1 | H11A—C11—H11B | 109.5 |
C1—C2—H2 | 112.1 | C8—C11—H11C | 109.5 |
C3—C2—H2 | 112.1 | H11A—C11—H11C | 109.5 |
C3'—C3—C4 | 111.8 (3) | H11B—C11—H11C | 109.5 |
C3'—C3—C2 | 115.7 (3) | C1—O12—C13 | 106.5 (3) |
C4—C3—C2 | 103.3 (3) | O12—C13—O14 | 103.8 (2) |
C3'—C3—H3 | 108.6 | O12—C13—C16 | 110.2 (3) |
C4—C3—H3 | 108.6 | O14—C13—C16 | 109.3 (3) |
C2—C3—H3 | 108.6 | O12—C13—C15 | 110.1 (3) |
O1—C4—C5 | 106.6 (3) | O14—C13—C15 | 110.9 (3) |
O1—C4—C3 | 104.1 (3) | C16—C13—C15 | 112.2 (3) |
C5—C4—C3 | 115.5 (3) | C2—O14—C13 | 107.5 (2) |
O1—C4—H4 | 110.1 | C13—C15—H15A | 109.5 |
C5—C4—H4 | 110.1 | C13—C15—H15B | 109.5 |
C3—C4—H4 | 110.1 | H15A—C15—H15B | 109.5 |
O9—C5—C4 | 109.8 (3) | C13—C15—H15C | 109.5 |
O9—C5—C6 | 104.2 (3) | H15A—C15—H15C | 109.5 |
C4—C5—C6 | 112.7 (3) | H15B—C15—H15C | 109.5 |
O9—C5—H5 | 110.0 | C13—C16—H16A | 109.5 |
C4—C5—H5 | 110.0 | C13—C16—H16B | 109.5 |
C6—C5—H5 | 110.0 | H16A—C16—H16B | 109.5 |
O7—C6—C5 | 102.9 (3) | C13—C16—H16C | 109.5 |
O7—C6—H6A | 111.2 | H16A—C16—H16C | 109.5 |
C5—C6—H6A | 111.2 | H16B—C16—H16C | 109.5 |
O7—C6—H6B | 111.2 | N4'—C3'—C3 | 113.9 (3) |
C5—C6—H6B | 111.2 | N4'—C3'—H3'1 | 108.8 |
H6A—C6—H6B | 109.1 | C3—C3'—H3'1 | 108.8 |
C6—O7—C8 | 106.2 (2) | N4'—C3'—H3'2 | 108.8 |
O7—C8—O9 | 104.8 (3) | C3—C3'—H3'2 | 108.8 |
O7—C8—C11 | 108.5 (3) | H3'1—C3'—H3'2 | 107.7 |
O9—C8—C11 | 109.2 (3) | O6'—N4'—O5' | 124.1 (3) |
O7—C8—C10 | 111.7 (3) | O6'—N4'—C3' | 116.8 (3) |
O9—C8—C10 | 109.3 (3) | O5'—N4'—C3' | 119.1 (3) |
C4—O1—C1—O12 | 82.3 (3) | C6—O7—C8—O9 | −32.8 (3) |
C4—O1—C1—C2 | −30.3 (3) | C6—O7—C8—C11 | −149.3 (3) |
O1—C1—C2—O14 | 126.3 (3) | C6—O7—C8—C10 | 85.4 (3) |
O12—C1—C2—O14 | 9.3 (3) | C4—C5—O9—C8 | −115.4 (3) |
O1—C1—C2—C3 | 9.3 (4) | C6—C5—O9—C8 | 5.6 (4) |
O12—C1—C2—C3 | −107.7 (3) | O7—C8—O9—C5 | 16.0 (4) |
O14—C2—C3—C3' | 23.3 (4) | C11—C8—O9—C5 | 132.1 (3) |
C1—C2—C3—C3' | 135.5 (3) | C10—C8—O9—C5 | −103.8 (3) |
O14—C2—C3—C4 | −99.1 (3) | O1—C1—O12—C13 | −144.5 (3) |
C1—C2—C3—C4 | 13.1 (3) | C2—C1—O12—C13 | −29.2 (3) |
C1—O1—C4—C5 | 161.0 (3) | C1—O12—C13—O14 | 38.3 (3) |
C1—O1—C4—C3 | 38.5 (3) | C1—O12—C13—C16 | 155.2 (3) |
C3'—C3—C4—O1 | −155.8 (3) | C1—O12—C13—C15 | −80.4 (3) |
C2—C3—C4—O1 | −30.8 (3) | C1—C2—O14—C13 | 13.7 (3) |
C3'—C3—C4—C5 | 87.7 (4) | C3—C2—O14—C13 | 125.0 (3) |
C2—C3—C4—C5 | −147.3 (3) | O12—C13—O14—C2 | −31.8 (3) |
O1—C4—C5—O9 | 177.9 (3) | C16—C13—O14—C2 | −149.4 (3) |
C3—C4—C5—O9 | −67.0 (4) | C15—C13—O14—C2 | 86.4 (3) |
O1—C4—C5—C6 | 62.2 (4) | C4—C3—C3'—N4' | −176.0 (3) |
C3—C4—C5—C6 | 177.3 (3) | C2—C3—C3'—N4' | 66.2 (4) |
O9—C5—C6—O7 | −25.0 (3) | C3—C3'—N4'—O6' | −177.3 (3) |
C4—C5—C6—O7 | 94.0 (3) | C3—C3'—N4'—O5' | 2.6 (4) |
C5—C6—O7—C8 | 35.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3′—H3′2···O5′i | 0.97 | 2.53 | 3.355 (4) | 143 |
C1—H1···O12ii | 0.98 | 2.41 | 3.386 (5) | 178 |
C15—H15A···O6′iii | 0.96 | 2.48 | 3.433 (5) | 174 |
Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+3/2, −z; (iii) −x+1, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3'—H3'2···O5'i | 0.97 | 2.53 | 3.355 (4) | 143 |
C1—H1···O12ii | 0.98 | 2.41 | 3.386 (5) | 178 |
C15—H15A···O6'iii | 0.96 | 2.48 | 3.433 (5) | 174 |
Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+3/2, −z; (iii) −x+1, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C13H21NO7 |
Mr | 303.31 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 173 |
a, b, c (Å) | 5.5044 (2), 12.6144 (4), 21.6348 (9) |
V (Å3) | 1502.21 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.26 × 0.08 × 0.06 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4225, 4225, 2316 |
Rint | ? |
(sin θ/λ)max (Å−1) | 0.705 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.127, 1.01 |
No. of reflections | 4225 |
No. of parameters | 194 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.25 |
Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR2011 (Burla et al., 2012), SHELXL2014 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012), PLATON (Spek, 2009) and publCIF (Westrip, 2010).
Acknowledgements
JSC `Olainfarm' is acknowledged for the donation of diacetone-D-glucose. JSC 'Grindeks' is acknowledged for the donation of organic solvents.
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