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Acta Cryst. (2007). E63, o3484    [ doi:10.1107/S160053680703303X ]

3,4-Di-O-acetyl-2-azidodeoxy-1-O-nitro-[alpha]-L-fucose

D. C. McCutcheon, P. Norris and M. Zeller

Abstract top

The title compound, C10H14N4O8, crystallizes with two crystallographically independent molecules in the asymmetric unit, in an arrangement stabilized by a range of non-classical C-H...O hydrogen bonds. The crystals of the [alpha] anomer were selectively grown from a mixture of both 1-O-nitrates. The compound exhibits the expected 1C4 chair conformation, with the azide group in an equatorial and the nitrate in an axial position.

Comment top

Azidodeoxynitrates such as the tile compound serve as versatile intermediates in the preparation of a variety of aminosugar derivatives. 3,4-Di-O-acetyl-2-azidodeoxy-1-O-nitro-α-L-fucose (I) specifically was used as a precursor for the synthesis of L-fucosamine analogs, for example derivatives of the bacterial aminosugar N-acetyl-L-fucosamine (Anisuzzaman & Horton, 1987), as well as glycosyl phosphates through reaction with caesium dibenzyl phosphate (Illarionov et al., 1999).

(I) was prepared by the reaction of 3,4-di-O-acetyl-L-fucal (Figure 1, Hansen et al., 1999) with sodium azide and ceric ammonium nitrate in acetone leading to a mixture of 1-O-hydroxides and 1-O-nitrates with the 2-azidodeoxy-L-fucose configuration (Lehmann et al., 1979). The α and β 1-O-nitrates can be separated from the 1-O-hydroxides by column chromatography on silica gel, and from the mixture of the two nitrates the α-1-O-nitrate, namely 3,4-di-O-acetyl-2-azidodeoxy-1-O-nitro-α-L-fucose, was selectively crystallized by vapor diffusion of hexane into a solution of the nitrate mixture in ethyl acetate.

The title compound crystallizes in the orthorhombic chiral space group P212121 with two crystallographically independent molecules in the asymmetric part of the unit cell. The two independent molecules are chemically identical and both exhibit an almost perfect chair configuration (Figure 2). The rings adopt the 1C4 conformation with the azide groups at C2 in the expected equatorial and the nitrate at C1 in the axial position. The largest deviations between the two independent molecules is found for the azide and the two acetyl groups: the weighted r.m.s. deviation for an overlay of both molecules is 0.24 Å for all non-hydrogen atoms, but drops to only 0.08 Å when the N3 and OAc groups are omitted from the fit.

The observed arrangement seems to be stabilized by a range of C—H···O and also C—H···N hydrogen bonds. The most significant interactions with C···X distances below or close to the sum of the van der Waals radii (Vainshtein et al., 1982) are given in the hydrogen bonding table.

Related literature top

For related literature on the synthesis of the title compound, see: Hansen et al. (1999); Lehmann et al. (1979). For the use of the title compound in aminosugar synthesis, see: Anisuzzaman & Horton (1987); Illarionov et al. (1999).

For related literature, see: Herbstein (2000); Vainshtein et al. (1982).

Experimental top

Under a nitrogen atmosphere, ceric ammonium nitrate (10.84 g, 19.78 mmol) and sodium azide (1.35 g, 20.76 mmol) were placed in a flame-dried flask equipped with a magnetic stir bar and rubber septum. The reaction vessel was cooled to 258 K (-15 °C) using a dry ice ethylene glycol slush bath. 3,4-Di-O-acetyl-L-fucal (2.13 g, 9.94 mmol) was dissolved in freshly distilled acetone (50 ml) and transferred via cannula to the reaction vessel while maintaining 258 K. Overnight stirring and monitoring by TLC (3:1 petroleum ether-EtOAc) showed consumption of the starting material and the appearance of spots corresponding to the α- and β-anomers of 3,4-di-O-acetyl-2-azidodeoxy-1-O-nitro-L-fucose and the α- and β-anomers of 3,4-di-O-acetyl-2-azidodeoxy-L-fucose. The reaction mixture was diluted with diethyl ether (40 ml) and washed with H2O (3 × 20 ml). The organic layer was dried over MgSO4, filtered, and concentrated under reduced pressure. Column chromatography on silica gel (2:1 hexane-ethyl acetate as eluent) provided the mixture of the α- and β-anomers of 3,4-di-O-acetyl-2-azidodeoxy-1-O-nitro-L-fucose in 32% yield and that of 3,4-di-O-acetyl-2-azidodeoxy-α,β-L-fucose in 64% yield. Crystals of 3,4-di-O-acetyl-2-azidodeoxy-1-O-nitro-α-L-fucose suitable for X-ray analysis were obtained by vapor diffusion of hexane into a solution of the mixture of the nitrates in ethyl acetate.

Refinement top

Friedel pairs were merged prior to refinement and the absolute structure was assigned based on known stereocenters. All hydrogen atoms were placed in calculated positions and were isotropically refined using a riding model, with C—H = 0.97–1.00 Å and with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(C) for methyl H atoms. Methyl hydrogen atoms were allowed to rotate to best fit the observed electron density. The e.s.d. values of the cell parameters are taken from the software recognizing that the values are unreasonably small (Herbstein, 2000).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Synthesis of the title compound.
[Figure 2] Fig. 2. ORTEP presentation of one independent molecule of the title compound with the atom numbering scheme. Anisotropic displacement parameters are at the 50% level.
3,4-Di-O-acetyl-2-azidodeoxy-1-O-nitro-α-L-fucose top
Crystal data top
C10H14N4O8F(000) = 1328
Mr = 318.25Dx = 1.488 Mg m−3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 8591 reflections
a = 8.2169 (6) Åθ = 2.3–30.5°
b = 15.8825 (12) ŵ = 0.13 mm−1
c = 21.7738 (16) ÅT = 100 K
V = 2841.6 (4) Å3Block, colorless
Z = 80.52 × 0.50 × 0.36 mm
Data collection top
Bruker SMART APEX CCD
diffractometer		3960 independent reflections
Radiation source: fine-focus sealed tube3777 reflections with I > 2σ(I)
graphiteRint = 0.057
ω scansθmax = 28.3°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS in SAINT-Plus; Bruker, 2003)		h = −10→10
Tmin = 0.783, Tmax = 0.954k = −21→21
25826 measured reflectionsl = −28→28
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0432P)2 + 0.6271P]
where P = (Fo2 + 2Fc2)/3
3960 reflections(Δ/σ)max = 0.001
403 parametersΔρmax = 0.27 e Å−3
0 restraintsΔρmin = −0.18 e Å−3
Crystal data top
C10H14N4O8V = 2841.6 (4) Å3
Mr = 318.25Z = 8
Orthorhombic, P212121Mo Kα radiation
a = 8.2169 (6) ŵ = 0.13 mm−1
b = 15.8825 (12) ÅT = 100 K
c = 21.7738 (16) Å0.52 × 0.50 × 0.36 mm
Data collection top
Bruker SMART APEX CCD
diffractometer		3960 independent reflections
Absorption correction: multi-scan
(SADABS in SAINT-Plus; Bruker, 2003)		3777 reflections with I > 2σ(I)
Tmin = 0.783, Tmax = 0.954Rint = 0.057
25826 measured reflectionsθmax = 28.3°
Refinement top
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.084Δρmax = 0.27 e Å−3
S = 1.05Δρmin = −0.18 e Å−3
3960 reflectionsAbsolute structure: ?
403 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
C1A0.1519 (2)0.68931 (11)0.96074 (8)0.0173 (3)
H1A0.16970.69071.00620.021*
C2A0.3138 (2)0.70045 (11)0.92821 (8)0.0165 (3)
H2A0.36530.75450.94160.020*
C3A0.2871 (2)0.70192 (11)0.85901 (8)0.0160 (3)
H3A0.24450.64600.84520.019*
C4A0.1645 (2)0.77066 (11)0.84250 (8)0.0171 (3)
H4A0.13940.76790.79760.021*
C5A0.0083 (2)0.75793 (11)0.87924 (8)0.0178 (3)
H5A−0.04390.70430.86540.021*
C6A−0.1136 (2)0.82860 (12)0.87166 (9)0.0234 (4)
H6A1−0.07300.87920.89240.035*
H6A2−0.21780.81190.88980.035*
H6A3−0.12880.84050.82790.035*
C7A0.4653 (2)0.68822 (11)0.77365 (8)0.0180 (3)
C8A0.6392 (2)0.69823 (12)0.75485 (9)0.0233 (4)
H8A10.65330.67750.71280.035*
H8A20.70890.66590.78270.035*
H8A30.66940.75790.75670.035*
C9A0.3093 (3)0.89460 (12)0.81195 (9)0.0230 (4)
C10A0.3549 (3)0.98127 (13)0.83182 (10)0.0301 (5)
H10A0.25681.01610.83470.045*
H10B0.42971.00600.80180.045*
H10C0.40820.97870.87200.045*
C1B0.2547 (2)0.43484 (11)0.79007 (8)0.0180 (3)
H1B0.30180.43670.74770.022*
C2B0.3935 (2)0.43329 (11)0.83734 (8)0.0178 (3)
H2B0.46270.38260.82970.021*
C3B0.3204 (2)0.42703 (11)0.90164 (8)0.0163 (3)
H3B0.25210.47770.91050.020*
C4B0.2164 (2)0.34711 (11)0.90480 (8)0.0175 (3)
H4B0.16640.34150.94650.021*
C5B0.0837 (2)0.35172 (11)0.85600 (8)0.0178 (3)
H5B0.01020.40000.86600.021*
C6B−0.0187 (3)0.27262 (13)0.85109 (9)0.0251 (4)
H6B10.04900.22620.83610.038*
H6B2−0.10860.28230.82240.038*
H6B3−0.06240.25820.89160.038*
C7B0.4189 (2)0.44343 (11)1.00306 (8)0.0198 (4)
C8B0.5676 (3)0.43756 (15)1.04241 (10)0.0304 (4)
H8B10.53600.44011.08580.046*
H8B20.64070.48451.03290.046*
H8B30.62340.38421.03430.046*
C9B0.3866 (2)0.23554 (11)0.94182 (9)0.0204 (4)
C10B0.5124 (3)0.17257 (13)0.92196 (10)0.0274 (4)
H10D0.49290.11890.94280.041*
H10E0.62100.19340.93260.041*
H10F0.50540.16440.87740.041*
N1A−0.0035 (2)0.56522 (10)0.98752 (7)0.0216 (3)
N2A0.41780 (19)0.62882 (10)0.94692 (7)0.0184 (3)
N3A0.5655 (2)0.64117 (10)0.94132 (7)0.0206 (3)
N4A0.7021 (2)0.64433 (12)0.93857 (10)0.0313 (4)
N1B0.0763 (2)0.54341 (10)0.75172 (7)0.0226 (3)
N2B0.4937 (2)0.50950 (10)0.82922 (8)0.0209 (3)
N3B0.6420 (2)0.49697 (10)0.83443 (8)0.0230 (3)
N4B0.7785 (2)0.49429 (13)0.83732 (11)0.0374 (5)
O1A0.04098 (16)0.75143 (8)0.94464 (6)0.0181 (3)
O2A0.09418 (16)0.60611 (8)0.94303 (6)0.0188 (3)
O3A0.44471 (16)0.71616 (8)0.83227 (6)0.0181 (3)
O4A0.22958 (17)0.85305 (8)0.85736 (6)0.0191 (3)
O5A−0.0240 (2)0.59973 (10)1.03602 (7)0.0311 (3)
O6A−0.05346 (18)0.49872 (9)0.96954 (7)0.0280 (3)
O7A0.35749 (18)0.65942 (9)0.74306 (6)0.0237 (3)
O8A0.3355 (2)0.86470 (9)0.76178 (7)0.0311 (3)
O1B0.15313 (16)0.36579 (8)0.79517 (6)0.0189 (3)
O2B0.16796 (16)0.51307 (8)0.80211 (6)0.0194 (3)
O3B0.45529 (16)0.42301 (8)0.94370 (6)0.0191 (3)
O4B0.32046 (16)0.27581 (8)0.89237 (6)0.0180 (3)
O5B0.0821 (2)0.50576 (10)0.70412 (7)0.0371 (4)
O6B0.00131 (18)0.60629 (9)0.76422 (7)0.0265 (3)
O7B0.28545 (17)0.46294 (9)1.01992 (6)0.0228 (3)
O8B0.3492 (2)0.25016 (10)0.99387 (7)0.0291 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1A0.0205 (8)0.0149 (7)0.0164 (7)0.0001 (7)0.0012 (7)0.0008 (6)
C2A0.0171 (8)0.0150 (7)0.0172 (8)−0.0007 (6)0.0006 (6)0.0001 (6)
C3A0.0177 (8)0.0159 (7)0.0144 (7)−0.0017 (7)0.0033 (6)−0.0001 (6)
C4A0.0194 (8)0.0172 (8)0.0148 (8)−0.0010 (7)0.0007 (6)0.0003 (6)
C5A0.0184 (8)0.0185 (8)0.0164 (8)0.0013 (7)0.0003 (6)0.0011 (7)
C6A0.0231 (9)0.0234 (9)0.0237 (9)0.0048 (8)0.0011 (7)0.0028 (7)
C7A0.0216 (9)0.0152 (7)0.0172 (8)−0.0002 (7)0.0021 (6)0.0022 (6)
C8A0.0211 (9)0.0256 (9)0.0231 (9)−0.0024 (8)0.0039 (7)0.0001 (7)
C9A0.0281 (9)0.0195 (8)0.0215 (9)−0.0014 (8)0.0020 (7)0.0043 (7)
C10A0.0432 (12)0.0219 (9)0.0252 (10)−0.0069 (9)0.0032 (9)0.0023 (8)
C1B0.0206 (8)0.0161 (8)0.0175 (8)0.0020 (7)−0.0007 (7)0.0003 (6)
C2B0.0189 (8)0.0148 (7)0.0198 (8)0.0001 (7)−0.0006 (7)0.0010 (7)
C3B0.0158 (8)0.0161 (7)0.0169 (8)0.0012 (7)−0.0018 (6)0.0003 (6)
C4B0.0182 (8)0.0178 (8)0.0164 (8)0.0011 (7)−0.0005 (6)−0.0015 (6)
C5B0.0176 (8)0.0202 (8)0.0156 (8)−0.0003 (7)0.0000 (6)−0.0003 (7)
C6B0.0257 (10)0.0261 (9)0.0235 (9)−0.0068 (8)−0.0011 (8)0.0011 (8)
C7B0.0236 (9)0.0171 (8)0.0187 (8)−0.0035 (7)−0.0029 (7)0.0013 (7)
C8B0.0263 (10)0.0427 (12)0.0221 (9)−0.0012 (9)−0.0072 (8)−0.0013 (9)
C9B0.0224 (8)0.0167 (8)0.0220 (9)−0.0022 (7)−0.0041 (7)0.0030 (7)
C10B0.0314 (10)0.0229 (9)0.0278 (10)0.0079 (8)−0.0064 (8)0.0008 (8)
N1A0.0185 (7)0.0208 (7)0.0256 (8)0.0022 (6)0.0053 (6)0.0076 (7)
N2A0.0169 (7)0.0165 (7)0.0218 (7)−0.0007 (6)−0.0002 (6)0.0025 (6)
N3A0.0225 (8)0.0175 (7)0.0218 (7)0.0019 (6)0.0006 (6)0.0008 (6)
N4A0.0206 (8)0.0277 (9)0.0457 (11)0.0021 (7)0.0019 (8)0.0040 (8)
N1B0.0247 (8)0.0206 (7)0.0225 (8)0.0005 (7)−0.0058 (6)0.0022 (6)
N2B0.0186 (7)0.0180 (7)0.0262 (8)0.0002 (6)0.0008 (6)0.0016 (6)
N3B0.0228 (8)0.0204 (7)0.0257 (8)−0.0015 (7)−0.0011 (6)0.0011 (6)
N4B0.0219 (9)0.0304 (9)0.0600 (14)−0.0021 (8)−0.0063 (9)0.0018 (9)
O1A0.0210 (6)0.0177 (6)0.0157 (6)0.0033 (5)0.0010 (5)−0.0003 (5)
O2A0.0203 (6)0.0165 (6)0.0196 (6)−0.0020 (5)0.0047 (5)0.0015 (5)
O3A0.0174 (6)0.0191 (6)0.0178 (6)−0.0034 (5)0.0028 (5)0.0000 (5)
O4A0.0242 (6)0.0158 (6)0.0173 (6)−0.0021 (5)0.0019 (5)0.0013 (5)
O5A0.0384 (9)0.0290 (7)0.0259 (7)0.0035 (7)0.0150 (6)0.0057 (6)
O6A0.0230 (7)0.0210 (7)0.0400 (8)−0.0047 (6)0.0017 (6)0.0063 (6)
O7A0.0246 (7)0.0259 (7)0.0205 (6)−0.0027 (6)0.0020 (5)−0.0024 (5)
O8A0.0464 (9)0.0244 (7)0.0225 (7)−0.0026 (7)0.0091 (7)0.0026 (6)
O1B0.0229 (6)0.0174 (6)0.0162 (6)−0.0012 (5)0.0006 (5)−0.0002 (5)
O2B0.0234 (6)0.0170 (6)0.0179 (6)0.0033 (5)−0.0033 (5)0.0010 (5)
O3B0.0183 (6)0.0208 (6)0.0181 (6)0.0008 (5)−0.0033 (5)−0.0006 (5)
O4B0.0208 (6)0.0152 (5)0.0179 (6)0.0020 (5)−0.0022 (5)0.0003 (5)
O5B0.0551 (10)0.0321 (8)0.0242 (7)0.0103 (8)−0.0154 (7)−0.0057 (6)
O6B0.0235 (6)0.0224 (6)0.0337 (8)0.0047 (6)−0.0022 (6)0.0023 (6)
O7B0.0240 (7)0.0242 (7)0.0201 (6)−0.0010 (6)0.0010 (5)−0.0004 (5)
O8B0.0382 (8)0.0292 (7)0.0198 (7)0.0051 (7)−0.0022 (6)0.0040 (5)
Geometric parameters (Å, °) top
C1A—O1A1.388 (2)C2B—C3B1.527 (2)
C1A—O2A1.456 (2)C2B—H2B1.0000
C1A—C2A1.518 (2)C3B—O3B1.440 (2)
C1A—H1A1.0000C3B—C4B1.532 (2)
C2A—N2A1.480 (2)C3B—H3B1.0000
C2A—C3A1.523 (2)C4B—O4B1.445 (2)
C2A—H2A1.0000C4B—C5B1.524 (2)
C3A—O3A1.438 (2)C4B—H4B1.0000
C3A—C4A1.529 (2)C5B—O1B1.459 (2)
C3A—H3A1.0000C5B—C6B1.516 (3)
C4A—O4A1.450 (2)C5B—H5B1.0000
C4A—C5A1.526 (2)C6B—H6B10.9800
C4A—H4A1.0000C6B—H6B20.9800
C5A—O1A1.453 (2)C6B—H6B30.9800
C5A—C6A1.513 (3)C7B—O7B1.197 (2)
C5A—H5A1.0000C7B—O3B1.366 (2)
C6A—H6A10.9800C7B—C8B1.495 (3)
C6A—H6A20.9800C8B—H8B10.9800
C6A—H6A30.9800C8B—H8B20.9800
C7A—O7A1.199 (2)C8B—H8B30.9800
C7A—O3A1.362 (2)C9B—O8B1.197 (2)
C7A—C8A1.495 (3)C9B—O4B1.365 (2)
C8A—H8A10.9800C9B—C10B1.502 (3)
C8A—H8A20.9800C10B—H10D0.9800
C8A—H8A30.9800C10B—H10E0.9800
C9A—O8A1.210 (2)C10B—H10F0.9800
C9A—O4A1.357 (2)N1A—O6A1.199 (2)
C9A—C10A1.491 (3)N1A—O5A1.202 (2)
C10A—H10A0.9800N1A—O2A1.4158 (19)
C10A—H10B0.9800N2A—N3A1.236 (2)
C10A—H10C0.9800N3A—N4A1.125 (2)
C1B—O1B1.383 (2)N1B—O5B1.198 (2)
C1B—O2B1.456 (2)N1B—O6B1.204 (2)
C1B—C2B1.536 (2)N1B—O2B1.4156 (19)
C1B—H1B1.0000N2B—N3B1.240 (2)
C2B—N2B1.474 (2)N3B—N4B1.124 (3)
O1A—C1A—O2A111.38 (14)N2B—C2B—H2B108.9
O1A—C1A—C2A112.01 (14)C3B—C2B—H2B108.9
O2A—C1A—C2A105.52 (14)C1B—C2B—H2B108.9
O1A—C1A—H1A109.3O3B—C3B—C2B106.45 (14)
O2A—C1A—H1A109.3O3B—C3B—C4B111.37 (14)
C2A—C1A—H1A109.3C2B—C3B—C4B108.34 (14)
N2A—C2A—C1A106.74 (14)O3B—C3B—H3B110.2
N2A—C2A—C3A111.55 (14)C2B—C3B—H3B110.2
C1A—C2A—C3A109.69 (15)C4B—C3B—H3B110.2
N2A—C2A—H2A109.6O4B—C4B—C5B109.31 (14)
C1A—C2A—H2A109.6O4B—C4B—C3B108.11 (14)
C3A—C2A—H2A109.6C5B—C4B—C3B109.14 (14)
O3A—C3A—C2A105.84 (14)O4B—C4B—H4B110.1
O3A—C3A—C4A112.72 (13)C5B—C4B—H4B110.1
C2A—C3A—C4A109.80 (14)C3B—C4B—H4B110.1
O3A—C3A—H3A109.5O1B—C5B—C6B106.25 (14)
C2A—C3A—H3A109.5O1B—C5B—C4B111.12 (14)
C4A—C3A—H3A109.5C6B—C5B—C4B113.97 (15)
O4A—C4A—C5A108.24 (14)O1B—C5B—H5B108.5
O4A—C4A—C3A110.41 (14)C6B—C5B—H5B108.5
C5A—C4A—C3A109.66 (14)C4B—C5B—H5B108.5
O4A—C4A—H4A109.5C5B—C6B—H6B1109.5
C5A—C4A—H4A109.5C5B—C6B—H6B2109.5
C3A—C4A—H4A109.5H6B1—C6B—H6B2109.5
O1A—C5A—C6A106.39 (14)C5B—C6B—H6B3109.5
O1A—C5A—C4A111.57 (14)H6B1—C6B—H6B3109.5
C6A—C5A—C4A113.64 (15)H6B2—C6B—H6B3109.5
O1A—C5A—H5A108.4O7B—C7B—O3B123.52 (17)
C6A—C5A—H5A108.4O7B—C7B—C8B126.08 (18)
C4A—C5A—H5A108.4O3B—C7B—C8B110.40 (16)
C5A—C6A—H6A1109.5C7B—C8B—H8B1109.5
C5A—C6A—H6A2109.5C7B—C8B—H8B2109.5
H6A1—C6A—H6A2109.5H8B1—C8B—H8B2109.5
C5A—C6A—H6A3109.5C7B—C8B—H8B3109.5
H6A1—C6A—H6A3109.5H8B1—C8B—H8B3109.5
H6A2—C6A—H6A3109.5H8B2—C8B—H8B3109.5
O7A—C7A—O3A123.58 (17)O8B—C9B—O4B123.61 (18)
O7A—C7A—C8A126.49 (17)O8B—C9B—C10B125.35 (18)
O3A—C7A—C8A109.92 (16)O4B—C9B—C10B111.03 (16)
C7A—C8A—H8A1109.5C9B—C10B—H10D109.5
C7A—C8A—H8A2109.5C9B—C10B—H10E109.5
H8A1—C8A—H8A2109.5H10D—C10B—H10E109.5
C7A—C8A—H8A3109.5C9B—C10B—H10F109.5
H8A1—C8A—H8A3109.5H10D—C10B—H10F109.5
H8A2—C8A—H8A3109.5H10E—C10B—H10F109.5
O8A—C9A—O4A123.53 (18)O6A—N1A—O5A129.84 (17)
O8A—C9A—C10A125.42 (18)O6A—N1A—O2A112.01 (15)
O4A—C9A—C10A111.03 (16)O5A—N1A—O2A118.14 (16)
C9A—C10A—H10A109.5N3A—N2A—C2A114.70 (15)
C9A—C10A—H10B109.5N4A—N3A—N2A172.9 (2)
H10A—C10A—H10B109.5O5B—N1B—O6B129.07 (17)
C9A—C10A—H10C109.5O5B—N1B—O2B118.64 (15)
H10A—C10A—H10C109.5O6B—N1B—O2B112.29 (15)
H10B—C10A—H10C109.5N3B—N2B—C2B113.95 (16)
O1B—C1B—O2B111.51 (14)N4B—N3B—N2B172.6 (2)
O1B—C1B—C2B112.43 (14)C1A—O1A—C5A114.81 (13)
O2B—C1B—C2B104.85 (14)N1A—O2A—C1A114.81 (13)
O1B—C1B—H1B109.3C7A—O3A—C3A116.11 (14)
O2B—C1B—H1B109.3C9A—O4A—C4A117.02 (14)
C2B—C1B—H1B109.3C1B—O1B—C5B115.50 (13)
N2B—C2B—C3B112.53 (15)N1B—O2B—C1B114.29 (13)
N2B—C2B—C1B108.72 (14)C7B—O3B—C3B115.02 (14)
C3B—C2B—C1B108.86 (15)C9B—O4B—C4B117.08 (14)
O1A—C1A—C2A—N2A−177.50 (14)C3B—C2B—N2B—N3B99.33 (19)
O2A—C1A—C2A—N2A−56.15 (17)C1B—C2B—N2B—N3B−140.00 (17)
O1A—C1A—C2A—C3A−56.49 (19)O2A—C1A—O1A—C5A−61.11 (19)
O2A—C1A—C2A—C3A64.86 (16)C2A—C1A—O1A—C5A56.80 (19)
N2A—C2A—C3A—O3A−64.30 (17)C6A—C5A—O1A—C1A−179.81 (14)
C1A—C2A—C3A—O3A177.64 (13)C4A—C5A—O1A—C1A−55.36 (19)
N2A—C2A—C3A—C4A173.77 (14)O6A—N1A—O2A—C1A176.94 (15)
C1A—C2A—C3A—C4A55.71 (18)O5A—N1A—O2A—C1A−3.3 (2)
O3A—C3A—C4A—O4A−53.14 (18)O1A—C1A—O2A—N1A−88.22 (17)
C2A—C3A—C4A—O4A64.59 (18)C2A—C1A—O2A—N1A150.01 (14)
O3A—C3A—C4A—C5A−172.32 (14)O7A—C7A—O3A—C3A5.9 (2)
C2A—C3A—C4A—C5A−54.59 (19)C8A—C7A—O3A—C3A−173.41 (14)
O4A—C4A—C5A—O1A−67.51 (17)C2A—C3A—O3A—C7A155.22 (14)
C3A—C4A—C5A—O1A53.00 (19)C4A—C3A—O3A—C7A−84.75 (18)
O4A—C4A—C5A—C6A52.77 (19)O8A—C9A—O4A—C4A−4.0 (3)
C3A—C4A—C5A—C6A173.28 (15)C10A—C9A—O4A—C4A174.42 (16)
O1B—C1B—C2B—N2B−179.13 (14)C5A—C4A—O4A—C9A−147.08 (16)
O2B—C1B—C2B—N2B−57.80 (17)C3A—C4A—O4A—C9A92.88 (18)
O1B—C1B—C2B—C3B−56.22 (19)O2B—C1B—O1B—C5B−62.93 (18)
O2B—C1B—C2B—C3B65.10 (17)C2B—C1B—O1B—C5B54.51 (19)
N2B—C2B—C3B—O3B−61.27 (18)C6B—C5B—O1B—C1B−178.66 (15)
C1B—C2B—C3B—O3B178.14 (13)C4B—C5B—O1B—C1B−54.18 (19)
N2B—C2B—C3B—C4B178.85 (14)O5B—N1B—O2B—C1B−2.9 (2)
C1B—C2B—C3B—C4B58.26 (18)O6B—N1B—O2B—C1B177.26 (15)
O3B—C3B—C4B—O4B−56.78 (17)O1B—C1B—O2B—N1B−80.51 (17)
C2B—C3B—C4B—O4B59.97 (17)C2B—C1B—O2B—N1B157.57 (14)
O3B—C3B—C4B—C5B−175.58 (14)O7B—C7B—O3B—C3B0.4 (3)
C2B—C3B—C4B—C5B−58.83 (18)C8B—C7B—O3B—C3B−179.70 (15)
O4B—C4B—C5B—O1B−62.93 (18)C2B—C3B—O3B—C7B160.42 (14)
C3B—C4B—C5B—O1B55.12 (18)C4B—C3B—O3B—C7B−81.68 (18)
O4B—C4B—C5B—C6B57.07 (19)O8B—C9B—O4B—C4B8.5 (3)
C3B—C4B—C5B—C6B175.12 (15)C10B—C9B—O4B—C4B−170.63 (15)
C1A—C2A—N2A—N3A−157.79 (16)C5B—C4B—O4B—C9B−147.23 (15)
C3A—C2A—N2A—N3A82.4 (2)C3B—C4B—O4B—C9B94.07 (17)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C10A—H10C···O5Ai0.982.423.305 (3)150
C8A—H8A3···O1Bii0.982.523.344 (2)142
C5B—H5B···N4Biii1.002.503.403 (3)150
C4B—H4B···O8B1.002.332.706 (2)101
C3B—H3B···O2A1.002.523.515 (2)174
C3A—H3A···O2B1.002.403.390 (2)173
C2B—H2B···O4B1.002.472.838 (2)101
C2A—H2A···O5Ai1.002.543.529 (2)173
Symmetry codes: (i) x+1/2, −y+3/2, −z+2; (ii) −x+1, y+1/2, −z+3/2; (iii) x−1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C10A—H10C···O5Ai0.982.423.305 (3)150
C8A—H8A3···O1Bii0.982.523.344 (2)142
C5B—H5B···N4Biii1.002.503.403 (3)150
C4B—H4B···O8B1.002.332.706 (2)101
C3B—H3B···O2A1.002.523.515 (2)174
C3A—H3A···O2B1.002.403.390 (2)173
C2B—H2B···O4B1.002.472.838 (2)101
C2A—H2A···O5Ai1.002.543.529 (2)173
Symmetry codes: (i) x+1/2, −y+3/2, −z+2; (ii) −x+1, y+1/2, −z+3/2; (iii) x−1, y, z.
Acknowledgements top

Funding for this research came from the National Institutes of Health (grant R15 AI053112–01) and the diffractometer was funded by NSF grant 0087210, by Ohio Board of Regents grant CAP-491 and by YSU.

references
References top

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