Methyl 6-de-oxy-6-iodo-2,3-O-iso-propyl-idene-α-d-manno-pyran-oside.

In the title compound, C10H17IO5, the six-membered tetra-hydro-pyran ring and the five-membered 1,3-dioxolane ring adopt sofa and envelope conformations, respectively. In the crystal, O-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into layers nearly parallel to the bc plane.

Related literature

For carbohydrates which are important for the preparation of unsaturated aldehydes, see: Kleban et al. (2000 ▶); Dransfield et al. (1999 ▶); Greul et al. (2001 ▶). For conversions of unsaturated aldehydes to oximes, nitro­nes and nitrile oxides, see: Dransfield et al. (1999 ▶); Bernet & Vasella (1979 ▶); Greul et al. (2001 ▶); Gallos et al. (1999 ▶); Kleban et al. (2001 ▶). For the methods reported in the literature for the preparation of the title compound, see: Garegg & Samuelsson (1980 ▶); Bundle et al. (1988 ▶); Ichikawa et al. (2004 ▶). For the synthesis of methyl 2,3-O-iso­propyl­idene-α-d-manno­pyran­oside, see: Evans & Parrish (1977 ▶); Isobe et al. (1981 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C10H17IO5

M = 344.14

Monoclinic,

a = 8.3121 (8) Å

b = 10.3911 (10) Å

c = 8.3128 (8) Å

β = 118.639 (3)°

V = 630.15 (11) Å3

Z = 2

Mo Kα radiation

μ = 2.55 mm−1

T = 100 K

0.99 × 0.58 × 0.44 mm

Data collection

Bruker Kappa APEXII DUO diffractometer

Absorption correction: numerical (Blessing, 1995 ▶) T min = 0.187, T max = 0.401

13656 measured reflections

3827 independent reflections

3803 reflections with I > 2σ(I)

R int = 0.027

Standard reflections: 0

Refinement

R[F 2 > 2σ(F 2)] = 0.016

wR(F 2) = 0.043

S = 1.24

3827 reflections

153 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.86 e Å−3

Δρmin = −0.82 e Å−3

Absolute structure: Flack (1983 ▶), 1811 Friedel pairs

Absolute structure parameter: 0.003 (12)

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813022629/xu5727sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813022629/xu5727Isup2.hkl

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

C10H17IO5	F(000) = 340
Mr = 344.14	Dx = 1.814 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3798 reflections
a = 8.3121 (8) Å	θ = 2.8–30.5°
b = 10.3911 (10) Å	µ = 2.55 mm−1
c = 8.3128 (8) Å	T = 100 K
β = 118.639 (3)°	Prism, colourless
V = 630.15 (11) Å3	0.99 × 0.58 × 0.44 mm
Z = 2

Bruker Kappa APEXII DUO diffractometer	3827 independent reflections
Radiation source: fine-focus sealed tube	3803 reflections with I > 2σ(I)
Triumph monochromator	Rint = 0.027
φ and ω scans	θmax = 30.5°, θmin = 2.8°
Absorption correction: numerical (Blessing, 1995)	h = −11→11
Tmin = 0.187, Tmax = 0.401	k = −14→14
13656 measured reflections	l = −11→11

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.016	w = 1/[σ2(Fo2) + (0.0159P)2 + 0.0596P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.043	(Δ/σ)max = 0.001
S = 1.24	Δρmax = 0.86 e Å−3
3827 reflections	Δρmin = −0.82 e Å−3
153 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
3 restraints	Extinction coefficient: 0.0949 (17)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1811 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.003 (12)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
I1	0.388710 (12)	0.741920 (17)	0.435425 (11)	0.01675 (5)
O1	0.59121 (17)	0.64971 (12)	0.87699 (17)	0.0126 (2)
O2	0.91193 (19)	0.47140 (13)	0.78471 (18)	0.0150 (2)
H2A	0.998 (4)	0.426 (3)	0.855 (4)	0.045 (10)*
O3	0.76827 (18)	0.82125 (12)	1.0565 (2)	0.0143 (2)
O4	1.04540 (17)	0.44287 (13)	1.19016 (17)	0.0130 (2)
O5	0.80476 (18)	0.50343 (12)	1.23592 (19)	0.0143 (2)
C1	0.6958 (2)	0.62356 (15)	0.7844 (2)	0.0113 (3)
H1	0.7689	0.7009	0.7875	0.014*
C2	0.8224 (2)	0.51098 (16)	0.8849 (2)	0.0111 (3)
H2	0.7473	0.4379	0.8912	0.013*
C3	0.9584 (2)	0.55251 (16)	1.0784 (2)	0.0105 (3)
H3	1.0518	0.6125	1.0768	0.013*
C4	0.8628 (2)	0.61411 (15)	1.1762 (2)	0.0119 (3)
H4	0.9530	0.6646	1.2845	0.014*
C5	0.6980 (3)	0.69768 (17)	1.0559 (2)	0.0118 (3)
H5	0.6183	0.7038	1.1152	0.014*
C6	0.6277 (3)	0.91625 (18)	0.9709 (3)	0.0226 (4)
H6A	0.5518	0.8950	0.8409	0.034*
H6B	0.6839	1.0010	0.9823	0.034*
H6C	0.5510	0.9178	1.0309	0.034*
C7	0.5644 (3)	0.58663 (17)	0.5897 (3)	0.0158 (3)
H7A	0.4882	0.5136	0.5903	0.019*
H7B	0.6351	0.5574	0.5287	0.019*
C8	0.9482 (3)	0.40997 (16)	1.2897 (2)	0.0143 (3)
C9	0.8614 (3)	0.27863 (19)	1.2334 (3)	0.0220 (4)
H9A	0.7752	0.2655	1.2809	0.033*
H9B	0.9570	0.2124	1.2832	0.033*
H9C	0.7957	0.2727	1.0993	0.033*
C10	1.0810 (3)	0.4196 (2)	1.4915 (3)	0.0231 (4)
H10A	1.1313	0.5070	1.5203	0.035*
H10B	1.1809	0.3579	1.5237	0.035*
H10C	1.0172	0.4004	1.5618	0.035*

	U11	U22	U33	U12	U13	U23
I1	0.01472 (6)	0.01220 (5)	0.01494 (6)	0.00098 (5)	0.00036 (4)	0.00353 (5)
O1	0.0087 (5)	0.0137 (5)	0.0134 (6)	0.0003 (4)	0.0036 (5)	−0.0021 (4)
O2	0.0145 (6)	0.0201 (6)	0.0104 (6)	0.0058 (5)	0.0060 (5)	0.0004 (5)
O3	0.0097 (6)	0.0093 (5)	0.0215 (7)	−0.0009 (4)	0.0055 (5)	−0.0018 (4)
O4	0.0107 (6)	0.0189 (6)	0.0111 (6)	0.0046 (5)	0.0065 (5)	0.0047 (5)
C1	0.0102 (7)	0.0112 (6)	0.0108 (7)	0.0007 (5)	0.0037 (6)	−0.0009 (5)
C2	0.0096 (7)	0.0130 (6)	0.0099 (7)	0.0014 (6)	0.0042 (6)	0.0002 (5)
C3	0.0078 (7)	0.0132 (6)	0.0101 (7)	0.0008 (5)	0.0039 (6)	0.0009 (5)
C4	0.0113 (7)	0.0131 (7)	0.0118 (7)	0.0001 (6)	0.0061 (6)	−0.0006 (6)
C5	0.0102 (7)	0.0116 (6)	0.0125 (8)	−0.0010 (5)	0.0046 (7)	−0.0018 (5)
O5	0.0138 (6)	0.0148 (5)	0.0175 (6)	0.0041 (4)	0.0102 (5)	0.0048 (5)
C6	0.0155 (9)	0.0131 (8)	0.0329 (11)	0.0036 (6)	0.0065 (8)	0.0002 (7)
C7	0.0150 (8)	0.0134 (7)	0.0118 (8)	0.0023 (6)	0.0005 (7)	0.0008 (6)
C8	0.0146 (8)	0.0173 (7)	0.0147 (8)	0.0044 (6)	0.0100 (7)	0.0039 (6)
C9	0.0234 (10)	0.0161 (7)	0.0313 (11)	0.0018 (6)	0.0171 (9)	0.0045 (6)
C10	0.0239 (10)	0.0326 (10)	0.0132 (9)	0.0095 (8)	0.0093 (8)	0.0069 (7)

I1—C7	2.1414 (18)	C4—O5	1.425 (2)
O1—C1	1.4362 (19)	C4—C5	1.522 (3)
O1—C5	1.408 (2)	C4—H4	1.0000
O2—C2	1.4182 (18)	C5—H5	1.0000
O2—H2A	0.823 (16)	C6—H6A	0.9800
O3—C5	1.409 (2)	C6—H6B	0.9800
O3—C6	1.432 (2)	C6—H6C	0.9800
O4—C8	1.4480 (19)	C7—H7A	0.9900
O5—C8	1.433 (2)	C7—H7B	0.9900
C1—C2	1.527 (2)	C8—C9	1.509 (3)
C1—C7	1.505 (2)	C8—C10	1.506 (3)
C1—H1	1.0000	C9—H9A	0.9800
C2—C3	1.519 (2)	C9—H9B	0.9800
C2—H2	1.0000	C9—H9C	0.9800
C3—O4	1.428 (2)	C10—H10A	0.9800
C3—C4	1.524 (2)	C10—H10B	0.9800
C3—H3	1.0000	C10—H10C	0.9800
C5—O1—C1	113.31 (13)	O3—C5—H5	108.2
C2—O2—H2A	106 (3)	C4—C5—H5	108.2
C5—O3—C6	112.85 (13)	O3—C6—H6A	109.5
C3—O4—C8	108.25 (12)	O3—C6—H6B	109.5
C4—O5—C8	106.61 (12)	O3—C6—H6C	109.5
O1—C1—C2	106.69 (13)	H6A—C6—H6B	109.5
O1—C1—C7	108.12 (14)	H6A—C6—H6C	109.5
O1—C1—H1	110.5	H6B—C6—H6C	109.5
C2—C1—H1	110.5	I1—C7—H7A	109.0
C7—C1—C2	110.34 (13)	I1—C7—H7B	109.0
C7—C1—H1	110.5	C1—C7—I1	112.76 (11)
O2—C2—C1	108.61 (13)	C1—C7—H7A	109.0
O2—C2—C3	111.71 (13)	C1—C7—H7B	109.0
O2—C2—H2	109.1	H7A—C7—H7B	107.8
C1—C2—H2	109.1	O4—C8—C9	110.52 (14)
C3—C2—C1	109.25 (13)	O4—C8—C10	107.99 (15)
C3—C2—H2	109.1	O5—C8—O4	105.68 (13)
O4—C3—C2	110.49 (14)	O5—C8—C9	108.28 (16)
O4—C3—C4	102.62 (12)	O5—C8—C10	111.02 (14)
O4—C3—H3	110.6	C10—C8—C9	113.10 (16)
C2—C3—C4	111.72 (14)	C8—C9—H9A	109.5
C2—C3—H3	110.6	C8—C9—H9B	109.5
C4—C3—H3	110.6	C8—C9—H9C	109.5
O5—C4—C3	101.37 (12)	H9A—C9—H9B	109.5
O5—C4—C5	109.94 (14)	H9A—C9—H9C	109.5
O5—C4—H4	110.0	H9B—C9—H9C	109.5
C3—C4—H4	110.0	C8—C10—H10A	109.5
C5—C4—C3	115.09 (14)	C8—C10—H10B	109.5
C5—C4—H4	110.0	C8—C10—H10C	109.5
O1—C5—O3	112.13 (14)	H10A—C10—H10B	109.5
O1—C5—C4	113.92 (14)	H10A—C10—H10C	109.5
O1—C5—H5	108.2	H10B—C10—H10C	109.5
O3—C5—C4	106.06 (14)
C5—O1—C1—C2	67.22 (16)	C2—C1—C7—I1	−177.65 (10)
C5—O1—C1—C7	−174.10 (14)	O2—C2—C3—O4	−75.14 (16)
C1—O1—C5—O3	67.12 (17)	O2—C2—C3—C4	171.29 (13)
C1—O1—C5—C4	−53.35 (18)	C1—C2—C3—O4	164.67 (12)
C6—O3—C5—O1	63.69 (19)	C1—C2—C3—C4	51.10 (17)
C6—O3—C5—C4	−171.39 (15)	C2—C3—O4—C8	−95.94 (15)
C3—O4—C8—O5	−0.79 (18)	C4—C3—O4—C8	23.30 (17)
C3—O4—C8—C9	116.14 (17)	O4—C3—C4—O5	−37.10 (16)
C3—O4—C8—C10	−119.67 (15)	O4—C3—C4—C5	−155.67 (14)
C4—O5—C8—O4	−24.18 (18)	C2—C3—C4—O5	81.28 (16)
C4—O5—C8—C9	−142.61 (15)	C2—C3—C4—C5	−37.29 (19)
C4—O5—C8—C10	92.67 (16)	C3—C4—O5—C8	37.73 (17)
O1—C1—C2—O2	172.83 (13)	C5—C4—O5—C8	159.94 (14)
O1—C1—C2—C3	−65.09 (16)	O5—C4—C5—O1	−76.30 (17)
C7—C1—C2—O2	55.61 (18)	O5—C4—C5—O3	159.88 (12)
C7—C1—C2—C3	177.69 (13)	C3—C4—C5—O1	37.36 (19)
O1—C1—C7—I1	66.01 (15)	C3—C4—C5—O3	−86.45 (16)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O3i	0.82 (3)	2.03 (3)	2.807 (2)	157 (3)
C10—H10C···O2ii	0.98	2.51	3.390 (3)	149

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O3i	0.82 (3)	2.03 (3)	2.807 (2)	157 (3)
C10—H10C⋯O2ii	0.98	2.51	3.390 (3)	149

Symmetry codes: (i) ; (ii) .