3-O-Benzyl-6-O-benzoyl-1,2-O-isopropil­idene-5-C-nitro­methyl-a-d-glucofuran­ose

Pampín, B.; Valencia, L.; Estévez, J.C.; Estévez, R.J.

doi:10.1107/S1600536808043353

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Pages o332-o333

doi:10.1107/S1600536808043353

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3-O-Benzyl-6-O-benzoyl-1,2-O-isopropilidene-5-C-nitromethyl-a-D-glucofuranose

Begoña Pampín,^a Laura Valencia,^b Juan C. Estévez ^a ^* and Ramón J. Estévez ^a

^aDepartamento de Química Orgánica, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain, and ^bDepartamento de Química Inorgánica, Facultade de Química, Universidad de Vigo, 36310 Vigo, Pontevedra, Spain
^*Correspondence e-mail: ramon.estevez@usc.es

(Received 24 September 2008; accepted 19 December 2008; online 17 January 2009)

The title compound, C₂₄H₂₇NO₉, is one of the epimers of the Henry reaction of 3-O-benzyl-6-O-benzoyl-2-O-isopropylidene-a-D-glucofuran-5-one with nitromethane. The conformation of the five membered rings is as expected from the precursor compound and the molecule is folded with a dihedral angle of 51.4 (2)° between the aromatic rings. One O—H⋯O hydrogen bond and some intramolecular and intermolecular C—H⋯O interactions are observed in the structure.

Related literature

For the preparation of 3-O-benzyl-6-O-benzoyl-1,2-isopropylidene-a-D-xilo-hexofuran-5-one, the precursor of the title compound, and for the Henry reaction of the title compound with nitromethane, see: Yoshikawa et al. (1990 ). For background to nitrosugars as precursors of a wide range of natural and synthetic products, see: Chakraborty et al. (2002 ); Gruner et al. (2002 ); Lillelund et al. (2002 ); Ogawa & Morikawa (2005 ).

Experimental

Crystal data

C₂₄H₂₇NO₉
M_r = 473.47
Orthorhombic, P 2₁ 2₁ 2₁
a = 9.5080 (12) Å
b = 11.8190 (16) Å
c = 21.395 (3) Å
V = 2404.3 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 113 (2) K
0.47 × 0.29 × 0.13 mm

Data collection

Bruker SMART CCD 1000 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick 1996 ) T_min = 0.626, T_max = 0.982
4735 measured reflections
2692 independent reflections
1940 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.131
S = 1.10
2692 reflections
313 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O28—H28⋯O9	0.84 (2)	1.83 (3)	2.628 (4)	157 (5)
C4—H4⋯O31ⁱ	1.00	2.44	3.084 (5)	122
C5—H5⋯O28ⁱⁱ	1.00	2.45	3.189 (5)	130
C5—H5⋯O31ⁱⁱ	1.00	2.49	3.352 (5)	144
C18—H18A⋯O32	0.99	2.46	3.000 (6)	114
C24—H24⋯O1ⁱⁱⁱ	0.95	2.59	3.445 (5)	151
C26—H26⋯O8^iv	0.95	2.60	3.514 (5)	162
C29—H29A⋯O27^v	0.99	2.54	3.334 (5)	137
Symmetry codes: (i) x-1, y, z; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+{\script{1\over 2}}, -y, z+{\script{1\over 2}}]$ ; (iv) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536808043353/zl2144sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808043353/zl2144Isup2.hkl

checkCIF report

Comment top

Nitrosugars are very important organic compounds because of their use as precursors of a wide range of natural and synthetic products with relevant properties (Gruner et al., 2002) as aminopoliols (Lillelund et al., 2002, Ogawa et al., 2005), polihydroxilated amino acids (Chakraborty et al., 2002), etc. The title nitrosugar compound 2 (C₂₄H₂₇NO₉, Figure 1) is one of the epimers of the Henry reaction (Yoshikawa et al., 1990) of 3-O-benzyl-6-O-benzoyl-2-O-isopropilidene-a-D-glucofuran-5-one (1) (Yoshikawa et al., 1990) with nitromethane (See Figure 1). The molecular structure of the title compound is represented in Figure 2. Bond lengths and angles are within the expected values and confirm the bond orders giving in the Scheme. The compound crystallized in the orthorhombic space group P2₁2₁2₁ with only one molecule in the asymmetric unit. The molecule is folded with a dihedral angle between the aromatic rings of 51.4 (2)°. The conformation of the five membered rings is as expected from the precursor compound (1). Some intramolecular and intermolecular H bond interactions have been observed in the structure. The intramolecular O28—H28···O9 H bond interaction shows a distance H28···O9 of 2.628 (4) Å and an angle of 157 (5)°. No π—π-stacking interactions have been observed in the structure of the title compound.

Related literature top

For the preparation of 3-O-benzyl-6-O-benzoyl-1,2-isopropylidene-a-D-xilo-hexofuran-5-one, the precursor of the title compound, and for the Henry reaction of the title compound with nitrometane, see: Yoshikawa et al. (1990). For background to nitrosugars as precursors of a wide range of natural and synthetic products, see: Chakraborty et al. (2002); Gruner et al. (2002); Lillelund et al. (2002); Ogawa & Morikawa (2005).

Experimental top

3-O-Benzyl-6-O-benzoyl-1,2-O-isopropilidene-5-C-nitromethyl-a-D-glucofuranose (2) and 3-O-benzyl-6-O-benzoyl-1,2-O-isopropilidene-5-C-nitromethyl-b-L-Idofuranose (3).

KF.2H₂O (0.46 g, 4.90 mmol) and 18-crown-6 ether (0.82 g, 3.10 mmol) were added to a solution of 3-O-benzyl-6-O-benzoyl-1,2-isopropylidene-a-D-xilo-hexofuran-5-one (1) (1.19 g, 2.90 mmol) in acetonitrile (18 ml) and the resulting suspension was stirred at room temperature for 1 h. The reaction mixture was poured into ice water (50 ml) and extracted with ethyl acetate (3 m × 80 ml). The organic layers were then dried with anhydrous sodium sulfate, filtered and evaporated to give a residue wich was purificated by flash column chromatography (ethyl acetate/hexane 1:3) to give 3-O-benzyl-6-O-benzoyl-1,2-O-isopropilidene-5-C-nitromethyl-a-D-glucofuranose (2) (0.47 g, 34%) and 3-O-benzyl-6-O-benzoyl-1,2-O-isopropilidene-5-C-nitromethyl-b-L-Idofuranose (3) (0.36 g, 26%) as white solids that were crystallized from a mixture of ethylacetate and hexane.

3-O-Benzyl-6-O-benzoyl-1,2-O-isopropilidene-5-C-nitromethyl-a-D-glucofuranose (2): mp: 375–379 K. [a]_D²²-75.6° (c 1.00, CHCl₃). IR (NaCl, cm^-1): 3454 (OH); 2854–3064 (C_ArH); 1722 (CO); 1554, 1375 (NO₂). ¹H NMR (250 MHz, CDCl₃) δ 1.32 (s, 3H, CH₃); 1.46 (s, 3H, CH₃); 4.30 (d, 1H, J_3,4= 3.35 Hz, H-3); 4.38 (d, 1H, J_4,3= 3.35 Hz, H-4); 4.42–4.47 (m, 2H, CH₂NO₂); 4.54–4.60 (m, 2H, H-6 + H-6'); 4.66 (d, 1H, J_2,1= 3.65 Hz, H-2); 4.73 (d, 1H, J= 11.87 Hz, CHPh); 4.80 (s, 1H, OH); 4.91 (d, 1H, J = 11.87 Hz, CHPh); 6.02 (d, 1H, J_1,2 = 3.65 Hz, H-1); 7.31–7.61 (m, 8H, 8 × HPh); 7.98–8.01 (m, 2H, 2 × HPh). ¹³CNMR (62.8 MHz, CDCl₃) δ 26.17 (CH₃); 26.56 (CH₃); 65.34 (CH₂); 72.40 (CH₂); 73.05 (CH₂); 77.62 (CH); 77.76 (C); 81.38 (CH); 82.99 (CH); 104.53 (CH); 112.19 (C); 128.21 (2 × C_ArH); 128.45 (2 × C_ArH); 128.67(C_ArH); 128.79 (2 × Ar C_ArH); 129.06 (C_Ar); 129.54 (2 × C_ArH); 133.39 (C_ArH); 135.47 (C_Ar); 165.64 (CO). MS (CI) m/z 474 [(M+H)⁺, 1]; 105 (38); 91 [(PhCH₂)⁺, 81], 28 (100).

3-O-Benzyl-6-O-benzoyl-1,2-O-isopropilidene-5-C-nitromethyl-b-L-Idofuranose (3): mp: 382–384 K. [a]_D²²-38.0° (c 1.90, CHCl₃). IR (NaCl, cm^-1): 3454 (OH); 2854–3089 (C_ArH); 1722 (CO); 1554, 1375 (NO₂). ¹H NMR (250 MHz, CDCl₃) δ 1.33 (s, 3H, CH₃); 1.45 (s, 3H, CH₃); 4.27 (d, 1H, J_3,4 = 3.35 Hz, H-3); 4.31 (s, 1H, OH); 4.39 (1H, d, J_4,3= 3.35 Hz, H-4); 4.49–4.64 (m, 5H, H-6 + H-6' + CH₂NO₂ + CHPh); 4.69 (d, 1H, J_2,1 =3.35 Hz, H-2); 4.74 (d, 1H, J = 11.8 Hz, CHPh); 6.01 (d, 1H, J_1,2= 3.35 Hz, H-1); 7.33–7.60 (m, 8H, 8 × H—Ph); 7.96–8.01 (m, 2H, 2 × H—Ph).¹³CNMR (62.8 MHz, CDCl₃) δ 26.60 (CH₃); 27.09 (CH₃); 65.90 (CH₂); 72.52 (CH₂); 73.90 (C); 78.96 (CH₂); 79.20 (CH); 81.80 (CH); 82.70 (CH); 104.90 (CH); 112.70 (C); 128.90 (4 × C_ArH); 129.20 (2 × C_ArH); 129.30 (2 × C_ArH); 129.80 (C_Ar); 130.02 (C_ArH); 133.70 (C_ArH); 136.02 (C_Ar); 166.05 (CO). MS (CI) m/z105 (38); 91 [(PhCH₂)⁺, 86], 61 (100); 28 (87).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SHELXTL ((Sheldrick, 2008); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound (2), with atom labels and 50% probability displacement ellipsoids.
	Fig. 2. Chemical reaction scheme of the molecule (2).

(I) top

Crystal data top

C₂₄H₂₇NO₉	D_x = 1.308 Mg m⁻³
M_r = 473.47	Mo Kα radiation, λ = 0.71069 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 915 reflections
a = 9.5080 (12) Å	θ = 2.6–24.4°
b = 11.8190 (16) Å	µ = 0.10 mm⁻¹
c = 21.395 (3) Å	T = 113 K
V = 2404.3 (5) Å³	Prism, colourless
Z = 4	0.47 × 0.29 × 0.13 mm
F(000) = 1000

Data collection top

Bruker SMART CCD 1000 diffractometer	2692 independent reflections
Radiation source: fine-focus sealed tube	1940 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω scans	θ_max = 26.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick 1996)	h = −11→11
T_min = 0.626, T_max = 0.982	k = 0→14
4735 measured reflections	l = 0→26

Refinement top

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0583P)² + 1.021P] where P = (F_o² + 2F_c²)/3
2692 reflections	(Δ/σ)_max < 0.001
313 parameters	Δρ_max = 0.25 e Å⁻³
1 restraint	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₂₄H₂₇NO₉	V = 2404.3 (5) Å³
M_r = 473.47	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 9.5080 (12) Å	µ = 0.10 mm⁻¹
b = 11.8190 (16) Å	T = 113 K
c = 21.395 (3) Å	0.47 × 0.29 × 0.13 mm

Data collection top

Bruker SMART CCD 1000 diffractometer	2692 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick 1996)	1940 reflections with I > 2σ(I)
T_min = 0.626, T_max = 0.982	R_int = 0.037
4735 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	1 restraint
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.25 e Å⁻³
2692 reflections	Δρ_min = −0.30 e Å⁻³
313 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.1700 (3)	0.0030 (2)	0.56353 (12)	0.0391 (7)
C2	0.0591 (5)	0.0120 (3)	0.61034 (19)	0.0402 (11)
O3	0.0623 (3)	0.1268 (2)	0.62962 (11)	0.0348 (7)
C4	0.1148 (5)	0.1931 (3)	0.57862 (16)	0.0302 (9)
H4	0.0397	0.2228	0.5503	0.036*
C5	0.2170 (4)	0.1109 (3)	0.54653 (16)	0.0303 (9)
H5	0.2143	0.1206	0.5001	0.036*
C6	0.2093 (4)	0.2840 (3)	0.60556 (16)	0.0288 (9)
H6	0.1677	0.3197	0.6437	0.035*
C7	0.3420 (5)	0.2167 (3)	0.62059 (15)	0.0283 (9)
H7	0.3265	0.1746	0.6606	0.034*
O8	0.3531 (3)	0.1354 (2)	0.57021 (11)	0.0308 (6)
O9	0.2419 (3)	0.3664 (2)	0.55803 (10)	0.0315 (6)
C10	0.1342 (5)	0.4495 (3)	0.54682 (17)	0.0337 (10)
H10A	0.0461	0.4106	0.5347	0.040*
H10B	0.1632	0.4986	0.5116	0.040*
C11	0.1070 (5)	0.5218 (3)	0.60372 (16)	0.0308 (9)
C12	−0.0205 (5)	0.5153 (4)	0.63417 (18)	0.0382 (10)
H12	−0.0940	0.4699	0.6177	0.046*
C13	−0.0408 (6)	0.5759 (4)	0.6894 (2)	0.0477 (12)
H13	−0.1286	0.5716	0.7104	0.057*
C14	0.0640 (6)	0.6412 (4)	0.7134 (2)	0.0443 (11)
H14	0.0490	0.6816	0.7512	0.053*
C15	0.1910 (5)	0.6489 (3)	0.6834 (2)	0.0422 (11)
H15	0.2640	0.6942	0.7005	0.051*
C16	0.2130 (5)	0.5899 (3)	0.62766 (18)	0.0363 (10)
H16	0.3001	0.5965	0.6062	0.044*
C17	0.4799 (5)	0.2818 (3)	0.62561 (15)	0.0279 (9)
C18	0.4703 (5)	0.3727 (3)	0.67693 (15)	0.0318 (9)
H18A	0.5578	0.4182	0.6778	0.038*
H18B	0.3903	0.4240	0.6684	0.038*
O19	0.4505 (3)	0.3165 (2)	0.73631 (10)	0.0330 (7)
C20	0.4824 (5)	0.3802 (3)	0.78726 (16)	0.0307 (9)
C21	0.4595 (5)	0.3169 (3)	0.84646 (16)	0.0317 (9)
C22	0.3918 (6)	0.2137 (4)	0.8481 (2)	0.0571 (15)
H22	0.3611	0.1799	0.8102	0.069*
C23	0.3680 (7)	0.1590 (5)	0.9043 (2)	0.0663 (17)
H23	0.3222	0.0876	0.9051	0.080*
C24	0.4120 (6)	0.2096 (4)	0.95958 (18)	0.0497 (13)
H24	0.3915	0.1748	0.9985	0.060*
C25	0.4849 (5)	0.3097 (4)	0.95812 (17)	0.0416 (11)
H25	0.5193	0.3417	0.9959	0.050*
C26	0.5087 (5)	0.3643 (3)	0.90188 (16)	0.0369 (10)
H26	0.5584	0.4341	0.9011	0.044*
O27	0.5252 (4)	0.4754 (2)	0.78355 (11)	0.0436 (8)
O28	0.5152 (3)	0.3409 (2)	0.56949 (11)	0.0339 (7)
C29	0.5974 (4)	0.1972 (3)	0.63705 (18)	0.0324 (9)
H29A	0.5829	0.1593	0.6778	0.039*
H29B	0.5963	0.1386	0.6040	0.039*
N30	0.7345 (4)	0.2559 (3)	0.63692 (16)	0.0411 (9)
O31	0.8021 (3)	0.2601 (3)	0.58777 (14)	0.0529 (9)
O32	0.7732 (4)	0.3030 (3)	0.68513 (14)	0.0516 (9)
C33	0.0979 (8)	−0.0629 (4)	0.6645 (2)	0.0663 (17)
H33A	0.1894	−0.0396	0.6812	0.099*
H33B	0.1033	−0.1417	0.6504	0.099*
H33C	0.0264	−0.0563	0.6973	0.099*
C34	−0.0801 (5)	−0.0168 (4)	0.5813 (2)	0.0530 (13)
H34A	−0.1544	−0.0109	0.6129	0.080*
H34B	−0.0771	−0.0942	0.5649	0.080*
H34C	−0.0998	0.0360	0.5470	0.080*
H28	0.434 (3)	0.366 (4)	0.561 (2)	0.060 (17)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.046 (2)	0.0339 (14)	0.0374 (14)	−0.0003 (14)	0.0047 (14)	−0.0101 (12)
C2	0.048 (3)	0.034 (2)	0.039 (2)	−0.002 (2)	0.008 (2)	−0.0016 (18)
O3	0.0463 (19)	0.0312 (13)	0.0269 (12)	0.0023 (14)	0.0063 (13)	0.0019 (11)
C4	0.038 (3)	0.0319 (18)	0.0208 (17)	0.0002 (18)	0.0030 (17)	0.0013 (15)
C5	0.034 (3)	0.033 (2)	0.0232 (17)	−0.0006 (18)	−0.0012 (17)	−0.0028 (15)
C6	0.040 (3)	0.0282 (18)	0.0180 (16)	0.0042 (18)	0.0027 (16)	0.0009 (14)
C7	0.039 (3)	0.0308 (19)	0.0148 (16)	0.0034 (18)	0.0016 (16)	−0.0045 (13)
O8	0.0351 (18)	0.0345 (13)	0.0228 (12)	0.0046 (13)	−0.0043 (11)	−0.0092 (10)
O9	0.0398 (18)	0.0338 (13)	0.0208 (11)	0.0091 (13)	0.0017 (12)	0.0046 (10)
C10	0.039 (3)	0.036 (2)	0.0263 (18)	0.0090 (19)	−0.0026 (18)	0.0021 (15)
C11	0.035 (3)	0.0298 (19)	0.0282 (18)	0.0045 (18)	−0.0009 (18)	0.0070 (15)
C12	0.033 (3)	0.045 (2)	0.036 (2)	0.003 (2)	0.0000 (19)	0.0016 (18)
C13	0.040 (3)	0.062 (3)	0.040 (2)	0.011 (3)	0.011 (2)	0.001 (2)
C14	0.051 (3)	0.046 (2)	0.036 (2)	0.009 (2)	0.000 (2)	−0.0074 (19)
C15	0.054 (3)	0.031 (2)	0.041 (2)	0.003 (2)	−0.006 (2)	−0.0039 (18)
C16	0.041 (3)	0.0318 (19)	0.036 (2)	0.0028 (19)	0.0047 (19)	0.0073 (17)
C17	0.040 (3)	0.0274 (18)	0.0167 (15)	0.0017 (18)	−0.0014 (16)	0.0017 (13)
C18	0.043 (3)	0.034 (2)	0.0186 (16)	0.000 (2)	−0.0009 (17)	0.0042 (14)
O19	0.052 (2)	0.0317 (13)	0.0157 (11)	−0.0066 (14)	−0.0016 (12)	−0.0007 (10)
C20	0.038 (3)	0.032 (2)	0.0218 (16)	−0.0028 (19)	−0.0013 (17)	−0.0042 (14)
C21	0.038 (3)	0.037 (2)	0.0201 (16)	−0.0037 (19)	0.0004 (17)	−0.0006 (15)
C22	0.085 (4)	0.060 (3)	0.027 (2)	−0.034 (3)	−0.009 (2)	0.0057 (19)
C23	0.087 (5)	0.071 (3)	0.040 (2)	−0.043 (3)	−0.010 (3)	0.019 (2)
C24	0.057 (3)	0.068 (3)	0.024 (2)	−0.007 (3)	0.001 (2)	0.014 (2)
C25	0.057 (3)	0.048 (2)	0.0192 (17)	0.006 (2)	−0.0037 (19)	−0.0037 (16)
C26	0.051 (3)	0.0364 (19)	0.0231 (17)	0.000 (2)	−0.0005 (18)	−0.0038 (15)
O27	0.079 (2)	0.0289 (14)	0.0231 (12)	−0.0101 (16)	−0.0052 (14)	−0.0029 (10)
O28	0.040 (2)	0.0450 (16)	0.0169 (11)	0.0035 (14)	0.0009 (12)	0.0047 (11)
C29	0.029 (3)	0.038 (2)	0.0301 (19)	0.0012 (19)	−0.0031 (18)	0.0020 (16)
N30	0.042 (2)	0.047 (2)	0.0340 (18)	0.0058 (19)	−0.0066 (17)	0.0115 (16)
O31	0.039 (2)	0.079 (2)	0.0404 (17)	0.0084 (18)	0.0052 (15)	0.0129 (16)
O32	0.056 (2)	0.061 (2)	0.0387 (16)	−0.0149 (18)	−0.0148 (16)	0.0018 (15)
C33	0.107 (5)	0.042 (2)	0.050 (3)	0.010 (3)	0.009 (3)	0.011 (2)
C34	0.048 (3)	0.049 (3)	0.062 (3)	−0.011 (2)	0.009 (3)	−0.009 (2)

Geometric parameters (Å, º) top

O1—C5	1.400 (5)	C17—O28	1.429 (4)
O1—C2	1.458 (5)	C17—C29	1.519 (5)
C2—O3	1.419 (5)	C17—C18	1.539 (5)
C2—C34	1.502 (7)	C18—O19	1.446 (4)
C2—C33	1.505 (6)	C18—H18A	0.9900
O3—C4	1.433 (4)	C18—H18B	0.9900
C4—C6	1.515 (5)	O19—C20	1.359 (4)
C4—C5	1.536 (5)	C20—O27	1.199 (5)
C4—H4	1.0000	C20—C21	1.487 (5)
C5—O8	1.419 (5)	C21—C22	1.379 (6)
C5—H5	1.0000	C21—C26	1.393 (5)
C6—O9	1.442 (4)	C22—C23	1.385 (6)
C6—C7	1.526 (6)	C22—H22	0.9500
C6—H6	1.0000	C23—C24	1.391 (6)
C7—O8	1.448 (4)	C23—H23	0.9500
C7—C17	1.524 (6)	C24—C25	1.371 (6)
C7—H7	1.0000	C24—H24	0.9500
O9—C10	1.439 (5)	C25—C26	1.384 (5)
C10—C11	1.510 (5)	C25—H25	0.9500
C10—H10A	0.9900	C26—H26	0.9500
C10—H10B	0.9900	O28—H28	0.84 (2)
C11—C12	1.378 (6)	C29—N30	1.476 (6)
C11—C16	1.388 (6)	C29—H29A	0.9900
C12—C13	1.394 (6)	C29—H29B	0.9900
C12—H12	0.9500	N30—O32	1.228 (4)
C13—C14	1.361 (7)	N30—O31	1.233 (5)
C13—H13	0.9500	C33—H33A	0.9800
C14—C15	1.370 (7)	C33—H33B	0.9800
C14—H14	0.9500	C33—H33C	0.9800
C15—C16	1.398 (6)	C34—H34A	0.9800
C15—H15	0.9500	C34—H34B	0.9800
C16—H16	0.9500	C34—H34C	0.9800

C5—O1—C2	110.1 (3)	C15—C16—H16	120.1
O3—C2—O1	104.7 (3)	O28—C17—C29	106.5 (3)
O3—C2—C34	110.9 (4)	O28—C17—C7	112.9 (3)
O1—C2—C34	109.7 (3)	C29—C17—C7	108.2 (3)
O3—C2—C33	109.5 (4)	O28—C17—C18	105.8 (3)
O1—C2—C33	108.0 (4)	C29—C17—C18	112.8 (3)
C34—C2—C33	113.7 (4)	C7—C17—C18	110.6 (3)
C2—O3—C4	108.0 (3)	O19—C18—C17	108.3 (3)
O3—C4—C6	107.7 (3)	O19—C18—H18A	110.0
O3—C4—C5	102.4 (3)	C17—C18—H18A	110.0
C6—C4—C5	104.1 (3)	O19—C18—H18B	110.0
O3—C4—H4	113.8	C17—C18—H18B	110.0
C6—C4—H4	113.8	H18A—C18—H18B	108.4
C5—C4—H4	113.8	C20—O19—C18	114.9 (3)
O1—C5—O8	112.6 (3)	O27—C20—O19	122.9 (3)
O1—C5—C4	104.9 (3)	O27—C20—C21	125.3 (3)
O8—C5—C4	106.8 (3)	O19—C20—C21	111.8 (3)
O1—C5—H5	110.8	C22—C21—C26	119.5 (3)
O8—C5—H5	110.8	C22—C21—C20	122.3 (3)
C4—C5—H5	110.8	C26—C21—C20	118.2 (3)
O9—C6—C4	109.8 (3)	C21—C22—C23	120.8 (4)
O9—C6—C7	108.8 (3)	C21—C22—H22	119.6
C4—C6—C7	101.6 (3)	C23—C22—H22	119.6
O9—C6—H6	112.0	C22—C23—C24	119.2 (4)
C4—C6—H6	112.0	C22—C23—H23	120.4
C7—C6—H6	112.0	C24—C23—H23	120.4
O8—C7—C17	109.0 (3)	C25—C24—C23	120.3 (4)
O8—C7—C6	104.4 (3)	C25—C24—H24	119.9
C17—C7—C6	117.6 (3)	C23—C24—H24	119.9
O8—C7—H7	108.5	C24—C25—C26	120.3 (4)
C17—C7—H7	108.5	C24—C25—H25	119.8
C6—C7—H7	108.5	C26—C25—H25	119.8
C5—O8—C7	109.6 (3)	C25—C26—C21	119.8 (4)
C10—O9—C6	115.2 (3)	C25—C26—H26	120.1
O9—C10—C11	112.0 (3)	C21—C26—H26	120.1
O9—C10—H10A	109.2	C17—O28—H28	97 (4)
C11—C10—H10A	109.2	N30—C29—C17	109.9 (3)
O9—C10—H10B	109.2	N30—C29—H29A	109.7
C11—C10—H10B	109.2	C17—C29—H29A	109.7
H10A—C10—H10B	107.9	N30—C29—H29B	109.7
C12—C11—C16	119.8 (4)	C17—C29—H29B	109.7
C12—C11—C10	120.0 (4)	H29A—C29—H29B	108.2
C16—C11—C10	120.1 (4)	O32—N30—O31	122.8 (4)
C11—C12—C13	119.6 (4)	O32—N30—C29	118.4 (4)
C11—C12—H12	120.2	O31—N30—C29	118.7 (3)
C13—C12—H12	120.2	C2—C33—H33A	109.5
C14—C13—C12	120.7 (5)	C2—C33—H33B	109.5
C14—C13—H13	119.7	H33A—C33—H33B	109.5
C12—C13—H13	119.7	C2—C33—H33C	109.5
C13—C14—C15	120.4 (4)	H33A—C33—H33C	109.5
C13—C14—H14	119.8	H33B—C33—H33C	109.5
C15—C14—H14	119.8	C2—C34—H34A	109.5
C14—C15—C16	119.9 (4)	C2—C34—H34B	109.5
C14—C15—H15	120.1	H34A—C34—H34B	109.5
C16—C15—H15	120.1	C2—C34—H34C	109.5
C11—C16—C15	119.7 (4)	H34A—C34—H34C	109.5
C11—C16—H16	120.1	H34B—C34—H34C	109.5

C5—O1—C2—O3	−11.5 (4)	C12—C13—C14—C15	0.5 (7)
C5—O1—C2—C34	107.5 (4)	C13—C14—C15—C16	0.3 (7)
C5—O1—C2—C33	−128.2 (4)	C12—C11—C16—C15	1.9 (6)
O1—C2—O3—C4	27.8 (4)	C10—C11—C16—C15	−174.4 (3)
C34—C2—O3—C4	−90.4 (4)	C14—C15—C16—C11	−1.5 (6)
C33—C2—O3—C4	143.4 (4)	O8—C7—C17—O28	59.3 (4)
C2—O3—C4—C6	−141.4 (4)	C6—C7—C17—O28	−59.2 (4)
C2—O3—C4—C5	−32.0 (4)	O8—C7—C17—C29	−58.3 (4)
C2—O1—C5—O8	107.9 (3)	C6—C7—C17—C29	−176.8 (3)
C2—O1—C5—C4	−7.8 (4)	O8—C7—C17—C18	177.6 (3)
O3—C4—C5—O1	23.9 (4)	C6—C7—C17—C18	59.1 (4)
C6—C4—C5—O1	136.0 (3)	O28—C17—C18—O19	−173.6 (3)
O3—C4—C5—O8	−95.8 (3)	C29—C17—C18—O19	−57.5 (4)
C6—C4—C5—O8	16.3 (3)	C7—C17—C18—O19	63.8 (4)
O3—C4—C6—O9	−168.4 (3)	C17—C18—O19—C20	160.9 (3)
C5—C4—C6—O9	83.3 (3)	C18—O19—C20—O27	−0.8 (6)
O3—C4—C6—C7	76.5 (3)	C18—O19—C20—C21	−180.0 (4)
C5—C4—C6—C7	−31.8 (3)	O27—C20—C21—C22	170.7 (5)
O9—C6—C7—O8	−79.1 (3)	O19—C20—C21—C22	−10.1 (6)
C4—C6—C7—O8	36.6 (3)	O27—C20—C21—C26	−9.3 (7)
O9—C6—C7—C17	41.7 (4)	O19—C20—C21—C26	169.9 (4)
C4—C6—C7—C17	157.5 (3)	C26—C21—C22—C23	2.2 (8)
O1—C5—O8—C7	−107.4 (3)	C20—C21—C22—C23	−177.8 (5)
C4—C5—O8—C7	7.3 (4)	C21—C22—C23—C24	0.6 (10)
C17—C7—O8—C5	−154.4 (3)	C22—C23—C24—C25	−3.5 (9)
C6—C7—O8—C5	−27.9 (3)	C23—C24—C25—C26	3.5 (8)
C4—C6—O9—C10	80.2 (4)	C24—C25—C26—C21	−0.6 (7)
C7—C6—O9—C10	−169.4 (3)	C22—C21—C26—C25	−2.2 (7)
C6—O9—C10—C11	62.9 (4)	C20—C21—C26—C25	177.7 (4)
O9—C10—C11—C12	−113.6 (4)	O28—C17—C29—N30	53.6 (4)
O9—C10—C11—C16	62.6 (4)	C7—C17—C29—N30	175.3 (3)
C16—C11—C12—C13	−1.1 (6)	C18—C17—C29—N30	−62.1 (4)
C10—C11—C12—C13	175.2 (4)	C17—C29—N30—O32	82.8 (4)
C11—C12—C13—C14	−0.1 (6)	C17—C29—N30—O31	−93.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O28—H28···O9	0.84 (2)	1.83 (3)	2.628 (4)	157 (5)
C4—H4···O31ⁱ	1.00	2.44	3.084 (5)	122
C5—H5···O28ⁱⁱ	1.00	2.45	3.189 (5)	130
C5—H5···O31ⁱⁱ	1.00	2.49	3.352 (5)	144
C18—H18A···O32	0.99	2.46	3.000 (6)	114
C22—H22···O19	0.95	2.41	2.739 (5)	100
C24—H24···O1ⁱⁱⁱ	0.95	2.59	3.445 (5)	151
C26—H26···O8^iv	0.95	2.60	3.514 (5)	162
C29—H29A···O19	0.99	2.57	2.907 (5)	100
C29—H29A···O27^v	0.99	2.54	3.334 (5)	137
C29—H29B···O8	0.99	2.42	2.824 (5)	104

Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+1/2, −z+1; (iii) −x+1/2, −y, z+1/2; (iv) −x+1, y+1/2, −z+3/2; (v) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₂₄H₂₇NO₉
M_r	473.47
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	113
a, b, c (Å)	9.5080 (12), 11.8190 (16), 21.395 (3)
V (Å³)	2404.3 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.47 × 0.29 × 0.13

Data collection
Diffractometer	Bruker SMART CCD 1000 diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick 1996)
T_min, T_max	0.626, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	4735, 2692, 1940
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.131, 1.10
No. of reflections	2692
No. of parameters	313
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.30

Computer programs: SMART (Bruker, 1998), SHELXTL ((Sheldrick, 2008), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX publication routines (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O28—H28···O9	0.84 (2)	1.83 (3)	2.628 (4)	157 (5)
C4—H4···O31ⁱ	1.00	2.44	3.084 (5)	121.8
C5—H5···O28ⁱⁱ	1.00	2.45	3.189 (5)	130.1
C5—H5···O31ⁱⁱ	1.00	2.49	3.352 (5)	143.6
C18—H18A···O32	0.99	2.46	3.000 (6)	113.5
C22—H22···O19	0.95	2.41	2.739 (5)	99.7
C24—H24···O1ⁱⁱⁱ	0.95	2.59	3.445 (5)	150.5
C26—H26···O8^iv	0.95	2.60	3.514 (5)	162.1
C29—H29A···O19	0.99	2.57	2.907 (5)	99.8
C29—H29A···O27^v	0.99	2.54	3.334 (5)	136.8
C29—H29B···O8	0.99	2.42	2.824 (5)	103.6

Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+1/2, −z+1; (iii) −x+1/2, −y, z+1/2; (iv) −x+1, y+1/2, −z+3/2; (v) −x+1, y−1/2, −z+3/2.

Acknowledgements

We gratefully acknowledge the Spanish Education Ministry and the Xunta de Galicia for financial support. Intensity measurements were performed at the Unidade de Raios X. RIAIDT. University of Santiago de Compostela, Spain.

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bruker (1998). SMART and SAINT. Bruker AXS, Madison, Wisconsin, USA. Google Scholar
Chakraborty, T. K., Ghosh, S. & Jayaprkas, S. (2002). Curr. Med. Chem. 9, 421–435. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Gruner, S. A. W., Locardi, E., Lohof, E. & Kessler, H. (2002). Chem. Rev. 102, 491–514. Web of Science CrossRef PubMed CAS Google Scholar
Lillelund, V. H., Jensen, H. H., Liang, X. & Bols, M. (2002). Chem. Rev. 102, 515–553. Web of Science CrossRef PubMed CAS Google Scholar
Ogawa, S. & Morikawa, T. (2005). Eur. J. Org. Chem. 19, 4065–4072. Web of Science CrossRef Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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Volume 65| Part 2| February 2009| Pages o332-o333

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

3-O-Benzyl-6-O-benzoyl-1,2-O-isopropil­­idene-5-C-nitro­methyl-a-D-gluco­furan­ose

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

3-O-Benzyl-6-O-benzoyl-1,2-O-isopropilidene-5-C-nitromethyl-a-D-glucofuranose