An ortho-rhom-bic polymorph of 6-de-oxy-6-iodo-1,2:3,4-di-O-isopropyl-idene-α-d-galactopyran-oside.

The title compound, C(12)H(19)IO(5), is the ortho-rhom-bic polymorph of a previously reported monoclinic form [Krajewski et al. (1987 ▶). Bull. Pol. Acad. Sci. Chem.35, 91-102]. The dihedral angles between the six-membered ring and the two five-membered rings are 67.66 (14) and 71.79 (13)°, whereas the dihedral angle between the five-membered rings is 74.41 (12)°, indicating that all three rings are twisted from each other. The six-membered ring has a twist-boat conformation while both of the five-membered rings have envelope conformations. The crystal structure is stabilized by a network of C-H⋯O contacts linking the mol-ecules into a two-dimensional array parallel to the ab plane.

Related literature

For the monoclinic polymorph of the title compound, see: Krajewski et al. (1987 ▶). For the synthesis and biological evaluation of 6-substituted purines, see: Gambogi Braga et al. (2007 ▶). For halogenation reagent systems, see: Classon et al. (1988 ▶). For the synthesis of perosamine derivatives, see: Stevens et al. (1970 ▶). For the synthesis of labilose, see: Westwood et al. (1967 ▶). For ring conformations and ring puckering analysis, see: Boeyens (1978 ▶); Cremer & Pople (1975 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C12H19IO5

M = 370.17

Orthorhombic,

a = 7.3595 (1) Å

b = 11.5145 (2) Å

c = 16.9945 (2) Å

V = 1440.13 (4) Å3

Z = 4

Mo Kα radiation

μ = 2.23 mm−1

T = 100 K

0.17 × 0.11 × 0.11 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.703, T max = 0.785

27359 measured reflections

7509 independent reflections

6211 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.096

S = 1.07

7509 reflections

167 parameters

H-atom parameters constrained

Δρmax = 0.87 e Å−3

Δρmin = −1.24 e Å−3

Absolute structure: Flack (1983 ▶), 3286 Friedel pairs

Flack parameter: −0.020 (19)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029031/tk2509sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029031/tk2509Isup2.hkl

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

C12H19IO5	F(000) = 736
Mr = 370.17	Dx = 1.707 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6517 reflections
a = 7.3595 (1) Å	θ = 3.0–30.1°
b = 11.5145 (2) Å	µ = 2.23 mm−1
c = 16.9945 (2) Å	T = 100 K
V = 1440.13 (4) Å3	Block, colourless
Z = 4	0.17 × 0.11 × 0.11 mm

Bruker SMART APEXII CCD area-detector diffractometer	7509 independent reflections
Radiation source: fine-focus sealed tube	6211 reflections with I > 2σ(I)
graphite	Rint = 0.046
φ and ω scans	θmax = 37.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −12→12
Tmin = 0.703, Tmax = 0.785	k = −19→17
27359 measured reflections	l = −28→29

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035	H-atom parameters constrained
wR(F2) = 0.096	w = 1/[σ2(Fo2) + (0.0418P)2 + 0.1348P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.003
7509 reflections	Δρmax = 0.87 e Å−3
167 parameters	Δρmin = −1.24 e Å−3
0 restraints	Absolute structure: Flack (1983), 3286 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.020 (19)

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
I1	0.48767 (2)	−0.062287 (16)	0.585388 (10)	0.02322 (5)
O1	0.3941 (3)	0.30650 (19)	0.54871 (11)	0.0202 (4)
O2	0.4126 (2)	0.41053 (17)	0.66190 (11)	0.0174 (4)
O3	−0.0095 (3)	0.31453 (16)	0.74636 (10)	0.0169 (3)
O4	0.0869 (3)	0.13209 (18)	0.77122 (12)	0.0181 (4)
O5	0.2158 (2)	0.16776 (16)	0.61095 (11)	0.0162 (3)
C1	0.2269 (3)	0.2856 (2)	0.58845 (16)	0.0166 (4)
H1A	0.1256	0.3041	0.5532	0.020*
C2	0.4873 (3)	0.4031 (2)	0.58404 (14)	0.0167 (4)
C3	0.2281 (3)	0.3722 (2)	0.65788 (15)	0.0166 (4)
H3A	0.1476	0.4379	0.6466	0.020*
C4	0.1835 (3)	0.3209 (3)	0.73797 (15)	0.0167 (4)
H4A	0.2335	0.3710	0.7793	0.020*
C5	−0.0464 (3)	0.2160 (2)	0.79401 (15)	0.0165 (4)
C6	0.2485 (3)	0.1941 (2)	0.75132 (13)	0.0152 (5)
H6A	0.3359	0.1907	0.7948	0.018*
C7	0.3309 (3)	0.1412 (2)	0.67660 (15)	0.0165 (5)
H7A	0.4522	0.1737	0.6677	0.020*
C8	0.3433 (4)	0.0106 (3)	0.68407 (16)	0.0194 (5)
H8A	0.2220	−0.0221	0.6864	0.023*
H8B	0.4059	−0.0092	0.7325	0.023*
C9	0.4481 (4)	0.5139 (3)	0.53734 (17)	0.0235 (6)
H9A	0.3193	0.5267	0.5353	0.035*
H9B	0.4945	0.5057	0.4848	0.035*
H9C	0.5058	0.5787	0.5626	0.035*
C10	0.6874 (4)	0.3785 (3)	0.59115 (18)	0.0220 (5)
H10A	0.7049	0.3032	0.6142	0.033*
H10B	0.7430	0.4364	0.6240	0.033*
H10C	0.7421	0.3804	0.5399	0.033*
C11	−0.0254 (4)	0.2444 (3)	0.88146 (15)	0.0241 (5)
H11A	0.0946	0.2739	0.8910	0.036*
H11B	−0.0440	0.1753	0.9120	0.036*
H11C	−0.1136	0.3018	0.8963	0.036*
C12	−0.2321 (4)	0.1723 (3)	0.77260 (18)	0.0205 (5)
H12A	−0.2307	0.1435	0.7196	0.031*
H12B	−0.3183	0.2346	0.7766	0.031*
H12C	−0.2662	0.1109	0.8078	0.031*

	U11	U22	U33	U12	U13	U23
I1	0.02406 (8)	0.02602 (9)	0.01959 (7)	0.00713 (7)	0.00446 (7)	0.00100 (6)
O1	0.0212 (9)	0.0223 (10)	0.0170 (8)	−0.0053 (8)	0.0033 (7)	−0.0029 (8)
O2	0.0136 (7)	0.0220 (10)	0.0167 (8)	−0.0033 (6)	0.0016 (6)	−0.0022 (7)
O3	0.0124 (7)	0.0161 (7)	0.0222 (7)	−0.0003 (6)	0.0014 (6)	0.0023 (6)
O4	0.0133 (8)	0.0188 (9)	0.0223 (9)	0.0002 (6)	0.0036 (7)	0.0023 (7)
O5	0.0169 (8)	0.0149 (9)	0.0166 (7)	−0.0011 (6)	−0.0038 (6)	0.0004 (7)
C1	0.0177 (9)	0.0178 (12)	0.0143 (9)	−0.0010 (8)	−0.0028 (9)	−0.0001 (9)
C2	0.0173 (9)	0.0193 (10)	0.0134 (8)	−0.0026 (8)	0.0025 (11)	0.0023 (8)
C3	0.0145 (10)	0.0180 (12)	0.0172 (10)	−0.0018 (8)	0.0006 (8)	−0.0008 (9)
C4	0.0127 (9)	0.0207 (13)	0.0167 (10)	−0.0020 (8)	0.0012 (8)	−0.0009 (9)
C5	0.0150 (10)	0.0179 (12)	0.0166 (10)	0.0003 (8)	0.0014 (8)	0.0017 (8)
C6	0.0125 (9)	0.0197 (13)	0.0135 (10)	−0.0002 (8)	−0.0011 (7)	0.0007 (9)
C7	0.0127 (10)	0.0218 (13)	0.0149 (10)	−0.0004 (8)	−0.0003 (8)	0.0005 (9)
C8	0.0186 (11)	0.0227 (14)	0.0170 (11)	0.0044 (9)	0.0011 (9)	0.0041 (10)
C9	0.0251 (13)	0.0236 (14)	0.0218 (12)	−0.0012 (10)	0.0004 (10)	0.0054 (11)
C10	0.0175 (10)	0.0292 (15)	0.0193 (11)	0.0012 (9)	0.0031 (10)	0.0007 (11)
C11	0.0227 (13)	0.0313 (15)	0.0182 (10)	0.0003 (11)	0.0021 (10)	−0.0010 (10)
C12	0.0170 (11)	0.0200 (14)	0.0245 (13)	−0.0021 (9)	0.0014 (9)	0.0036 (11)

I1—C8	2.155 (3)	C5—C11	1.530 (4)
O1—C1	1.424 (3)	C6—C7	1.533 (4)
O1—C2	1.438 (3)	C6—H6A	0.9800
O2—C3	1.430 (3)	C7—C8	1.512 (4)
O2—C2	1.435 (3)	C7—H7A	0.9800
O3—C5	1.420 (3)	C8—H8A	0.9700
O3—C4	1.429 (3)	C8—H8B	0.9700
O4—C6	1.428 (3)	C9—H9A	0.9600
O4—C5	1.431 (3)	C9—H9B	0.9600
O5—C1	1.412 (3)	C9—H9C	0.9600
O5—C7	1.434 (3)	C10—H10A	0.9600
C1—C3	1.545 (4)	C10—H10B	0.9600
C1—H1A	0.9800	C10—H10C	0.9600
C2—C10	1.505 (4)	C11—H11A	0.9600
C2—C9	1.530 (4)	C11—H11B	0.9600
C3—C4	1.519 (4)	C11—H11C	0.9600
C3—H3A	0.9800	C12—H12A	0.9600
C4—C6	1.554 (4)	C12—H12B	0.9600
C4—H4A	0.9800	C12—H12C	0.9600
C5—C12	1.501 (4)
C1—O1—C2	110.17 (19)	C7—C6—H6A	110.4
C3—O2—C2	107.52 (19)	C4—C6—H6A	110.4
C5—O3—C4	106.8 (2)	O5—C7—C8	108.2 (2)
C6—O4—C5	107.3 (2)	O5—C7—C6	109.1 (2)
C1—O5—C7	112.42 (19)	C8—C7—C6	110.4 (2)
O5—C1—O1	109.9 (2)	O5—C7—H7A	109.7
O5—C1—C3	114.4 (2)	C8—C7—H7A	109.7
O1—C1—C3	104.4 (2)	C6—C7—H7A	109.7
O5—C1—H1A	109.3	C7—C8—I1	110.61 (18)
O1—C1—H1A	109.3	C7—C8—H8A	109.5
C3—C1—H1A	109.3	I1—C8—H8A	109.5
O2—C2—O1	104.41 (18)	C7—C8—H8B	109.5
O2—C2—C10	108.2 (2)	I1—C8—H8B	109.5
O1—C2—C10	110.8 (2)	H8A—C8—H8B	108.1
O2—C2—C9	110.8 (2)	C2—C9—H9A	109.5
O1—C2—C9	109.8 (2)	C2—C9—H9B	109.5
C10—C2—C9	112.5 (2)	H9A—C9—H9B	109.5
O2—C3—C4	106.4 (2)	C2—C9—H9C	109.5
O2—C3—C1	104.0 (2)	H9A—C9—H9C	109.5
C4—C3—C1	115.6 (2)	H9B—C9—H9C	109.5
O2—C3—H3A	110.2	C2—C10—H10A	109.5
C4—C3—H3A	110.2	C2—C10—H10B	109.5
C1—C3—H3A	110.2	H10A—C10—H10B	109.5
O3—C4—C3	108.9 (2)	C2—C10—H10C	109.5
O3—C4—C6	104.1 (2)	H10A—C10—H10C	109.5
C3—C4—C6	115.4 (2)	H10B—C10—H10C	109.5
O3—C4—H4A	109.4	C5—C11—H11A	109.5
C3—C4—H4A	109.4	C5—C11—H11B	109.5
C6—C4—H4A	109.4	H11A—C11—H11B	109.5
O3—C5—O4	104.70 (19)	C5—C11—H11C	109.5
O3—C5—C12	107.7 (2)	H11A—C11—H11C	109.5
O4—C5—C12	109.4 (2)	H11B—C11—H11C	109.5
O3—C5—C11	111.4 (2)	C5—C12—H12A	109.5
O4—C5—C11	109.8 (2)	C5—C12—H12B	109.5
C12—C5—C11	113.5 (2)	H12A—C12—H12B	109.5
O4—C6—C7	109.1 (2)	C5—C12—H12C	109.5
O4—C6—C4	104.4 (2)	H12A—C12—H12C	109.5
C7—C6—C4	112.0 (2)	H12B—C12—H12C	109.5
O4—C6—H6A	110.4

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O2i	0.97	2.42	3.377 (3)	169
C12—H12C···O2ii	0.96	2.60	3.477 (4)	152

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯O2i	0.97	2.42	3.377 (3)	169
C12—H12C⋯O2ii	0.96	2.60	3.477 (4)	152

Symmetry codes: (i) ; (ii) .