3,6-Didehydro-5-hy-droxy-1,2-O-iso-propyl-idene-5-C-nitro-meth-yl-α-d-gluco-furan-ose.

The title compound, C(10)H(15)NO(7), consists of one methyl-enedi-oxy ring and two fused tetra-hydro-furan rings. The three fused rings exhibit cis arrangements at the ring junctions. One O atom of a tetra-hydro-furan ring and the H atoms bound to the neighboring C atoms are disordered over two orientations with site-occupancy factors of 0.69 (1) and 0.31 (1). intra-molecular O-H⋯O and C-H⋯O inter-actions stabilize the mol-ecular conformation. In the crystal structure, inter-molecular O-H⋯O and C-H⋯O inter-actions link the mol-ecules into a three-dimensional network.

Related literature

For the synthesis of aza­sugars, see: Choi et al. (1991 ▶); Kvaernø et al. (2001 ▶). For the Henry reaction used to obtain the title compound, see: Saito et al. (2002 ▶). For research on carbohydrates and aza­sugars, see: Liu et al. (2004 ▶); Ke et al. (2009 ▶); Zhang et al. (2011 ▶). For a similar structure, see: Zhang & Yang (2010 ▶).

Experimental

Crystal data

C10H15NO7

M = 261.23

Orthorhombic,

a = 5.63290 (13) Å

b = 8.36405 (15) Å

c = 25.4014 (5) Å

V = 1196.76 (4) Å3

Z = 4

Cu Kα radiation

μ = 1.07 mm−1

T = 291 K

0.24 × 0.22 × 0.20 mm

Data collection

Bruker SMART diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.783, T max = 0.814

7427 measured reflections

2249 independent reflections

2161 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.165

S = 1.08

2249 reflections

174 parameters

8 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.59 e Å−3

Δρmin = −0.43 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681102191X/zq2104sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681102191X/zq2104Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C10H15NO7	Dx = 1.450 Mg m−3
Mr = 261.23	Melting point = 392–394 K
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5453 reflections
a = 5.63290 (13) Å	θ = 3.5–70.0°
b = 8.36405 (15) Å	µ = 1.07 mm−1
c = 25.4014 (5) Å	T = 291 K
V = 1196.76 (4) Å3	Block, white
Z = 4	0.24 × 0.22 × 0.20 mm
F(000) = 552

Bruker SMART diffractometer	2249 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2161 reflections with I > 2σ(I)
graphite	Rint = 0.021
Detector resolution: 0 pixels mm-1	θmax = 70.2°, θmin = 3.5°
ω scans	h = −6→4
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −9→10
Tmin = 0.783, Tmax = 0.814	l = −29→30
7427 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.165	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.1069P)2 + 0.3286P] where P = (Fo2 + 2Fc2)/3
2249 reflections	(Δ/σ)max < 0.001
174 parameters	Δρmax = 0.59 e Å−3
8 restraints	Δρmin = −0.43 e Å−3

Experimental. Melting point: 119–121 °C; Rf = 0.67 (CHCl3/EtOAc, 7:3); 1H NMR (400 MHz, CDCl3) σ: 5.98 (d, J = 3.4 Hz, 1H), 4.81 (d, J = 4.3 Hz, 1H), 4.68 (d, J = 3.4 Hz, 1H), 4.60 (dd, J = 8.3, 4.0 Hz, 2H), 4.52 (d, J = 12.3 Hz, 1H), 3.83 (d, J = 10.0 Hz, 1H), 3.75 (d, J = 10.0 Hz, 1H), 3.36 (s, 1H), 1.51 (s, 3H), 1.36 (s, 3H); 13C NMR (100 MHz, CDCl3) σ: 113.60, 107.18, 85.35, 85.08, 83.80, 78.62, 78.42, 74.89, 27.49, 26.77.

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.8215 (5)	−0.0074 (2)	0.86303 (8)	0.0635 (6)
O2	0.5738 (5)	0.1567 (3)	0.81809 (9)	0.0693 (7)
O3	0.4254 (5)	0.4145 (8)	0.92867 (15)	0.0833 (16)	0.695 (10)
O3A	0.4631 (15)	0.3468 (10)	0.93694 (15)	0.0833 (16)	0.305 (10)
O4	0.8877 (4)	0.2199 (2)	0.91272 (11)	0.0726 (8)
O5	1.0074 (4)	0.4587 (3)	0.97889 (8)	0.0526 (5)
H5	1.070 (10)	0.374 (6)	0.966 (2)	0.113 (19)*
O6	1.1140 (5)	0.6590 (3)	0.86098 (10)	0.0729 (7)
O7	1.2025 (5)	0.7827 (3)	0.93199 (11)	0.0735 (7)
N1	1.0673 (5)	0.7059 (3)	0.90501 (9)	0.0487 (6)
C1	0.7251 (6)	0.1003 (3)	0.89903 (10)	0.0530 (7)
H1	0.6693	0.0440	0.9305	0.064*
C2	0.5231 (5)	0.1803 (4)	0.87177 (13)	0.0598 (8)
H2	0.3681	0.1375	0.8822	0.072*
C3	0.5524 (6)	0.3547 (5)	0.88496 (14)	0.0712 (11)
H3A	0.5120	0.4186	0.8539	0.085*	0.695 (10)
H3B	0.4794	0.4325	0.8611	0.085*	0.305 (10)
C4	0.8110 (5)	0.3724 (3)	0.89597 (11)	0.0450 (6)
H4	0.9001	0.4120	0.8655	0.054*
C5	0.8201 (4)	0.4884 (3)	0.94342 (9)	0.0378 (5)
C6	0.5819 (5)	0.4568 (4)	0.96985 (11)	0.0517 (6)
H6A	0.5953	0.3704	0.9952	0.062*	0.695 (10)
H6B	0.5259	0.5518	0.9879	0.062*	0.695 (10)
H6C	0.6048	0.4120	1.0047	0.062*	0.305 (10)
H6D	0.4915	0.5550	0.9730	0.062*	0.305 (10)
C7	0.7269 (6)	0.0235 (3)	0.81191 (10)	0.0488 (7)
C8	0.9245 (10)	0.0693 (8)	0.7760 (2)	0.1050 (16)
H8A	1.0428	−0.0133	0.7761	0.157*
H8B	0.9940	0.1677	0.7879	0.157*
H8C	0.8640	0.0830	0.7410	0.157*
C9	0.5948 (9)	−0.1217 (5)	0.79390 (18)	0.0830 (12)
H9A	0.4567	−0.1366	0.8155	0.125*
H9B	0.6958	−0.2138	0.7967	0.125*
H9C	0.5471	−0.1080	0.7579	0.125*
C10	0.8305 (5)	0.6646 (3)	0.92708 (11)	0.0437 (6)
H10A	0.7090	0.6856	0.9009	0.052*
H10B	0.7985	0.7315	0.9575	0.052*

	U11	U22	U33	U12	U13	U23
O1	0.0991 (17)	0.0435 (10)	0.0480 (10)	0.0213 (12)	−0.0142 (12)	−0.0086 (8)
O2	0.0906 (17)	0.0641 (13)	0.0533 (11)	0.0267 (12)	−0.0249 (12)	−0.0142 (10)
O3	0.0301 (13)	0.080 (4)	0.140 (3)	0.0168 (15)	0.0027 (14)	−0.075 (3)
O3A	0.0301 (13)	0.080 (4)	0.140 (3)	0.0168 (15)	0.0027 (14)	−0.075 (3)
O4	0.0591 (13)	0.0422 (10)	0.117 (2)	0.0172 (10)	−0.0355 (13)	−0.0200 (12)
O5	0.0480 (10)	0.0557 (12)	0.0542 (11)	0.0076 (9)	−0.0076 (9)	0.0032 (9)
O6	0.0897 (17)	0.0640 (14)	0.0650 (13)	−0.0128 (13)	0.0300 (13)	−0.0073 (11)
O7	0.0693 (13)	0.0674 (13)	0.0836 (16)	−0.0247 (13)	−0.0016 (13)	−0.0072 (12)
N1	0.0578 (14)	0.0353 (10)	0.0529 (12)	−0.0020 (10)	0.0079 (11)	0.0004 (9)
C1	0.084 (2)	0.0345 (12)	0.0409 (13)	−0.0002 (13)	−0.0035 (14)	−0.0024 (9)
C2	0.0429 (14)	0.0694 (19)	0.0670 (18)	−0.0064 (14)	−0.0001 (13)	−0.0269 (15)
C3	0.0604 (19)	0.073 (2)	0.080 (2)	0.0310 (17)	−0.0269 (17)	−0.0296 (18)
C4	0.0550 (15)	0.0337 (11)	0.0463 (13)	0.0003 (11)	0.0054 (12)	−0.0045 (10)
C5	0.0377 (11)	0.0358 (11)	0.0398 (11)	0.0029 (10)	0.0024 (10)	0.0019 (9)
C6	0.0494 (14)	0.0501 (15)	0.0556 (14)	−0.0030 (12)	0.0124 (12)	−0.0011 (12)
C7	0.0614 (16)	0.0471 (14)	0.0380 (12)	0.0021 (12)	−0.0008 (12)	−0.0023 (10)
C8	0.100 (3)	0.133 (4)	0.082 (3)	−0.014 (3)	0.033 (3)	0.005 (3)
C9	0.096 (3)	0.074 (2)	0.079 (2)	−0.011 (2)	−0.014 (2)	−0.0243 (19)
C10	0.0494 (13)	0.0330 (11)	0.0487 (12)	0.0056 (10)	0.0050 (12)	−0.0011 (10)

O1—C1	1.394 (3)	C3—H3A	0.9800
O1—C7	1.427 (3)	C3—H3B	0.9800
O2—C2	1.407 (4)	C4—C5	1.548 (3)
O2—C7	1.418 (4)	C4—H4	0.9800
O3—C3	1.412 (3)	C5—C6	1.524 (3)
O3—C6	1.413 (3)	C5—C10	1.532 (3)
O3A—C6	1.412 (3)	C6—H6A	0.9700
O3A—C3	1.414 (3)	C6—H6B	0.9700
O4—C1	1.400 (4)	C6—H6C	0.9700
O4—C4	1.413 (3)	C6—H6D	0.9700
O5—C5	1.409 (3)	C7—C8	1.488 (6)
O5—H5	0.86 (6)	C7—C9	1.497 (5)
O6—N1	1.214 (3)	C8—H8A	0.9600
O7—N1	1.209 (3)	C8—H8B	0.9600
N1—C10	1.487 (4)	C8—H8C	0.9600
C1—C2	1.490 (5)	C9—H9A	0.9600
C1—H1	0.9800	C9—H9B	0.9600
C2—C3	1.506 (5)	C9—H9C	0.9600
C2—H2	0.9800	C10—H10A	0.9700
C3—C4	1.491 (4)	C10—H10B	0.9700
C1—O1—C7	109.5 (2)	C6—C5—C4	101.8 (2)
C2—O2—C7	109.9 (2)	C10—C5—C4	113.1 (2)
C3—O3—C6	110.8 (2)	O3A—C6—C5	105.6 (3)
C6—O3A—C3	110.7 (3)	O3—C6—C5	105.5 (2)
C1—O4—C4	111.7 (2)	O3A—C6—H6A	86.8
C5—O5—H5	102 (4)	O3—C6—H6A	110.6
O7—N1—O6	123.9 (3)	C5—C6—H6A	110.6
O7—N1—C10	118.3 (2)	O3A—C6—H6B	131.3
O6—N1—C10	117.8 (2)	O3—C6—H6B	110.6
O1—C1—O4	111.7 (3)	C5—C6—H6B	110.6
O1—C1—C2	106.4 (2)	H6A—C6—H6B	108.8
O4—C1—C2	107.1 (2)	O3A—C6—H6C	110.6
O1—C1—H1	110.5	O3—C6—H6C	131.4
O4—C1—H1	110.5	C5—C6—H6C	110.6
C2—C1—H1	110.5	H6B—C6—H6C	85.9
O2—C2—C1	103.5 (2)	O3A—C6—H6D	110.6
O2—C2—C3	109.2 (3)	O3—C6—H6D	86.9
C1—C2—C3	104.4 (2)	C5—C6—H6D	110.6
O2—C2—H2	113.0	H6A—C6—H6D	128.1
C1—C2—H2	113.0	H6C—C6—H6D	108.7
C3—C2—H2	113.0	O2—C7—O1	105.6 (2)
O3—C3—C4	108.2 (2)	O2—C7—C8	108.7 (3)
O3A—C3—C4	100.2 (4)	O1—C7—C8	108.9 (3)
O3—C3—C2	117.5 (4)	O2—C7—C9	111.7 (3)
O3A—C3—C2	97.1 (4)	O1—C7—C9	108.5 (3)
C4—C3—C2	104.2 (2)	C8—C7—C9	113.2 (3)
O3—C3—H3A	108.9	C7—C8—H8A	109.5
O3A—C3—H3A	134.0	C7—C8—H8B	109.5
C4—C3—H3A	108.9	H8A—C8—H8B	109.5
C2—C3—H3A	108.9	C7—C8—H8C	109.5
O3—C3—H3B	92.3	H8A—C8—H8C	109.5
O3A—C3—H3B	117.4	H8B—C8—H8C	109.5
C4—C3—H3B	117.4	C7—C9—H9A	109.5
C2—C3—H3B	117.4	C7—C9—H9B	109.5
O4—C4—C3	105.4 (3)	H9A—C9—H9B	109.5
O4—C4—C5	108.7 (2)	C7—C9—H9C	109.5
C3—C4—C5	103.9 (2)	H9A—C9—H9C	109.5
O4—C4—H4	112.7	H9B—C9—H9C	109.5
C3—C4—H4	112.7	N1—C10—C5	111.1 (2)
C5—C4—H4	112.7	N1—C10—H10A	109.4
O5—C5—C6	110.3 (2)	C5—C10—H10A	109.4
O5—C5—C10	108.3 (2)	N1—C10—H10B	109.4
C6—C5—C10	108.7 (2)	C5—C10—H10B	109.4
O5—C5—C4	114.3 (2)	H10A—C10—H10B	108.0
C7—O1—C1—O4	−104.4 (3)	C2—C3—C4—C5	−140.4 (3)
C7—O1—C1—C2	12.2 (3)	O4—C4—C5—O5	34.3 (3)
C4—O4—C1—O1	115.3 (3)	C3—C4—C5—O5	146.2 (3)
C4—O4—C1—C2	−0.9 (4)	O4—C4—C5—C6	−84.7 (3)
C7—O2—C2—C1	22.4 (3)	C3—C4—C5—C6	27.2 (3)
C7—O2—C2—C3	133.2 (3)	O4—C4—C5—C10	158.9 (2)
O1—C1—C2—O2	−20.9 (3)	C3—C4—C5—C10	−89.2 (3)
O4—C1—C2—O2	98.6 (3)	C3—O3A—C6—O3	70.2 (3)
O1—C1—C2—C3	−135.2 (3)	C3—O3A—C6—C5	−23.2 (8)
O4—C1—C2—C3	−15.6 (3)	C3—O3—C6—O3A	−70.5 (3)
C6—O3—C3—O3A	70.3 (3)	C3—O3—C6—C5	23.6 (6)
C6—O3—C3—C4	−5.4 (6)	O5—C5—C6—O3A	−125.5 (5)
C6—O3—C3—C2	112.1 (4)	C10—C5—C6—O3A	115.9 (5)
C6—O3A—C3—O3	−70.3 (3)	C4—C5—C6—O3A	−3.8 (5)
C6—O3A—C3—C4	40.3 (8)	O5—C5—C6—O3	−152.7 (3)
C6—O3A—C3—C2	146.2 (7)	C10—C5—C6—O3	88.7 (4)
O2—C2—C3—O3	155.5 (3)	C4—C5—C6—O3	−31.0 (4)
C1—C2—C3—O3	−94.4 (4)	C2—O2—C7—O1	−15.6 (3)
O2—C2—C3—O3A	172.8 (5)	C2—O2—C7—C8	−132.3 (3)
C1—C2—C3—O3A	−77.1 (5)	C2—O2—C7—C9	102.1 (3)
O2—C2—C3—C4	−84.8 (3)	C1—O1—C7—O2	1.4 (3)
C1—C2—C3—C4	25.3 (4)	C1—O1—C7—C8	118.0 (4)
C1—O4—C4—C3	17.3 (3)	C1—O1—C7—C9	−118.4 (3)
C1—O4—C4—C5	128.2 (3)	O7—N1—C10—C5	−104.9 (3)
O3—C3—C4—O4	99.7 (4)	O6—N1—C10—C5	74.5 (3)
O3A—C3—C4—O4	74.0 (4)	O5—C5—C10—N1	55.5 (3)
C2—C3—C4—O4	−26.1 (3)	C6—C5—C10—N1	175.3 (2)
O3—C3—C4—C5	−14.6 (5)	C4—C5—C10—N1	−72.4 (3)
O3A—C3—C4—C5	−40.3 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O4	0.86 (6)	2.13 (6)	2.696 (3)	123 (5)
O5—H5···O3i	0.86 (6)	2.24 (6)	2.703 (3)	114 (4)
C1—H1···O5ii	0.98	2.48	3.371 (3)	152
C4—H4···O6	0.98	2.39	3.074 (4)	126

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O4	0.86 (6)	2.13 (6)	2.696 (3)	123 (5)
O5—H5⋯O3i	0.86 (6)	2.24 (6)	2.703 (3)	114 (4)
C1—H1⋯O5ii	0.98	2.48	3.371 (3)	152
C4—H4⋯O6	0.98	2.39	3.074 (4)	126

Symmetry codes: (i) ; (ii) .