Crystal structure of 1,2,3,4-di-O-methyl-ene-α-d-galacto-pyran-ose.

The title compound, C8H12O6, was synthesized by de-acetyl-ation of 6-acetyl-1,2,3,4-di-O-methyl-ene-α-d-galactose with sodium methoxide. The central part of the mol-ecule consists of a six-membered C5O pyran-ose ring with a twist-boat conformation. Both fused dioxolane rings adopt an envelope conformation with C and O atoms as the flap. In the crystal, O-H⋯O and C-H⋯O hydrogen bonds are present between adjacent mol-ecules, generating a three-dimensional network.

Related literature

For the synthesis of 6-acetyl-1,2,3,4-di-O-methyl­ene-α-d-galactose, see: Bok et al. (1952 ▸). For the crystal structures of the α- and β-anomers of d-galactose, see: Sheldrick (1976 ▸). For the crystal structure of 6-O-cyano­methyl-1,2:3,4-di-O-iso­propyl­idene-α-d-galactose, see: Langer et al. (2005 ▸). For the crystal structure of 6-[bis­(eth­oxy­carbon­yl)meth­yl]-6-de­oxy-1,2;3,4-di-O-iso­propyl­idene-d-galacto­pyran­ose, see: Doboszewski et al. (2010 ▸). For the crystal structure of 1,2,3,5-di-O-methyl­ene-α-d-xylo­furan­ose see: Tiritiris et al. (2015a ▸).

Experimental

Crystal data

C8H12O6

M = 204.18

Orthorhombic,

a = 6.4876 (6) Å

b = 6.6364 (5) Å

c = 20.1224 (16) Å

V = 866.36 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.14 mm−1

T = 100 K

0.43 × 0.32 × 0.04 mm

Data collection

Bruker Kappa APEXII DUO diffractometer

Absorption correction: multi-scan (Blessing, 1995 ▸) T min = 0.705, T max = 0.746

10453 measured reflections

2680 independent reflections

2464 reflections with I > 2σ(I)

R int = 0.023

Standard reflections: 0

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.075

S = 1.06

2680 reflections

131 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.18 e Å−3

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: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▸); software used to prepare material for publication: SHELXL2014.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015021854/zl2651sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015021854/zl2651Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015021854/zl2651Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015021854/zl2651fig1.tif

The structure of the title compound with displacement ellipsoids at the 50% probability level.

Click here for additional data file.

ac . DOI: 10.1107/S2056989015021854/zl2651fig2.tif

O—H⋯O hydrogen bonds (black dashed lines) between adjacent mol­ecules in the crystal structure of the title compound (ac view).

Click here for additional data file.

ac . DOI: 10.1107/S2056989015021854/zl2651fig3.tif

C—H⋯O and O—H⋯O hydrogen bonds (black dashed lines) between adjacent mol­ecules in the crystal structure of the title compound (ac view).

CCDC reference: 1437272

Additional supporting information: crystallographic information; 3D view; checkCIF report

C8H12O6	Dx = 1.565 Mg m−3
Mr = 204.18	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 2468 reflections
a = 6.4876 (6) Å	θ = 2.0–30.7°
b = 6.6364 (5) Å	µ = 0.14 mm−1
c = 20.1224 (16) Å	T = 100 K
V = 866.36 (12) Å3	Plate, colorless
Z = 4	0.43 × 0.32 × 0.04 mm
F(000) = 432

Bruker Kappa APEXII DUO diffractometer	2680 independent reflections
Radiation source: fine-focus sealed tube	2464 reflections with I > 2σ(I)
Triumph monochromator	Rint = 0.023
φ scans, and ω scans	θmax = 30.7°, θmin = 2.0°
Absorption correction: multi-scan (Blessing, 1995)	h = −9→6
Tmin = 0.705, Tmax = 0.746	k = −9→8
10453 measured reflections	l = −28→25

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.044P)2 + 0.0725P] where P = (Fo2 + 2Fc2)/3
2680 reflections	(Δ/σ)max < 0.001
131 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

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
O1	0.34564 (16)	0.56520 (14)	0.10994 (5)	0.0131 (2)
C1	0.2020 (2)	0.4035 (2)	0.11836 (7)	0.0131 (3)
H1	0.2178	0.3452	0.1639	0.016*
O2	0.44408 (19)	0.15283 (16)	0.08328 (5)	0.0213 (2)
H12	0.479 (4)	0.093 (4)	0.0465 (13)	0.046 (7)*
C2	−0.0156 (2)	0.4835 (2)	0.11004 (6)	0.0144 (3)
H2	−0.1186	0.3778	0.1224	0.017*
O3	0.12624 (15)	0.64670 (16)	0.25197 (5)	0.0161 (2)
C3	−0.0551 (2)	0.6797 (2)	0.15012 (6)	0.0151 (3)
H3	−0.1768	0.6608	0.1800	0.018*
O4	0.45725 (16)	0.63594 (16)	0.21656 (5)	0.0173 (2)
C4	0.1274 (2)	0.7537 (2)	0.19020 (6)	0.0134 (3)
H4	0.1135	0.9015	0.1987	0.016*
O5	−0.04486 (17)	0.54598 (15)	0.04200 (5)	0.0173 (2)
C5	0.3420 (2)	0.70826 (19)	0.16104 (7)	0.0129 (2)
H5	0.4051	0.8365	0.1447	0.016*
O6	−0.10172 (18)	0.82816 (16)	0.10055 (5)	0.0209 (2)
C6	0.3323 (2)	0.6556 (2)	0.27434 (7)	0.0162 (3)
H6A	0.3608	0.5448	0.3060	0.019*
H6B	0.3596	0.7857	0.2968	0.019*
C7	−0.1757 (2)	0.7162 (2)	0.04575 (7)	0.0193 (3)
H7A	−0.1678	0.7967	0.0044	0.023*
H7B	−0.3206	0.6746	0.0530	0.023*
C8	0.2518 (3)	0.2439 (2)	0.06717 (7)	0.0179 (3)
H8A	0.1419	0.1405	0.0666	0.021*
H8B	0.2594	0.3057	0.0225	0.021*

	U11	U22	U33	U12	U13	U23
O1	0.0137 (5)	0.0135 (4)	0.0122 (4)	−0.0019 (4)	0.0031 (4)	−0.0021 (3)
C1	0.0159 (6)	0.0117 (5)	0.0117 (6)	−0.0017 (5)	0.0011 (5)	0.0002 (4)
O2	0.0284 (6)	0.0197 (5)	0.0156 (5)	0.0096 (5)	−0.0014 (5)	−0.0029 (4)
C2	0.0142 (6)	0.0171 (6)	0.0118 (6)	−0.0039 (5)	0.0002 (5)	0.0014 (5)
O3	0.0139 (5)	0.0230 (5)	0.0115 (4)	−0.0016 (4)	0.0002 (4)	0.0030 (4)
C3	0.0129 (6)	0.0206 (6)	0.0119 (6)	0.0025 (5)	0.0008 (5)	0.0006 (5)
O4	0.0127 (5)	0.0262 (5)	0.0131 (4)	0.0037 (4)	−0.0017 (4)	−0.0034 (4)
C4	0.0137 (6)	0.0151 (5)	0.0113 (6)	0.0026 (5)	0.0015 (5)	0.0003 (5)
O5	0.0174 (5)	0.0238 (5)	0.0105 (4)	0.0015 (4)	−0.0018 (4)	0.0003 (4)
C5	0.0134 (6)	0.0125 (5)	0.0129 (6)	−0.0007 (5)	0.0000 (5)	−0.0014 (4)
O6	0.0249 (6)	0.0220 (5)	0.0158 (5)	0.0072 (4)	−0.0051 (4)	0.0008 (4)
C6	0.0155 (6)	0.0203 (6)	0.0128 (6)	−0.0005 (5)	−0.0005 (5)	−0.0008 (5)
C7	0.0141 (7)	0.0295 (7)	0.0144 (6)	0.0036 (6)	−0.0020 (5)	0.0015 (5)
C8	0.0237 (8)	0.0145 (6)	0.0155 (7)	0.0020 (6)	−0.0025 (5)	−0.0022 (5)

O1—C5	1.3997 (16)	C3—H3	1.0000
O1—C1	1.4313 (16)	O4—C6	1.4233 (17)
C1—C8	1.5123 (19)	O4—C5	1.4275 (17)
C1—C2	1.518 (2)	C4—C5	1.5404 (19)
C1—H1	1.0000	C4—H4	1.0000
O2—C8	1.4237 (19)	O5—C7	1.4152 (18)
O2—H12	0.87 (3)	C5—H5	1.0000
C2—O5	1.4430 (16)	O6—C7	1.4136 (18)
C2—C3	1.553 (2)	C6—H6A	0.9900
C2—H2	1.0000	C6—H6B	0.9900
O3—C6	1.4120 (17)	C7—H7A	0.9900
O3—C4	1.4313 (16)	C7—H7B	0.9900
C3—O6	1.4342 (17)	C8—H8A	0.9900
C3—C4	1.5146 (19)	C8—H8B	0.9900
C5—O1—C1	114.24 (10)	C5—C4—H4	109.8
O1—C1—C8	107.79 (11)	C7—O5—C2	104.94 (10)
O1—C1—C2	109.29 (10)	O1—C5—O4	109.75 (10)
C8—C1—C2	111.62 (11)	O1—C5—C4	115.33 (11)
O1—C1—H1	109.4	O4—C5—C4	103.95 (11)
C8—C1—H1	109.4	O1—C5—H5	109.2
C2—C1—H1	109.4	O4—C5—H5	109.2
C8—O2—H12	103.1 (18)	C4—C5—H5	109.2
O5—C2—C1	109.12 (11)	C7—O6—C3	104.66 (11)
O5—C2—C3	103.29 (11)	O3—C6—O4	105.95 (10)
C1—C2—C3	112.93 (11)	O3—C6—H6A	110.5
O5—C2—H2	110.4	O4—C6—H6A	110.5
C1—C2—H2	110.4	O3—C6—H6B	110.5
C3—C2—H2	110.4	O4—C6—H6B	110.5
C6—O3—C4	104.54 (10)	H6A—C6—H6B	108.7
O6—C3—C4	108.21 (12)	O6—C7—O5	104.91 (11)
O6—C3—C2	104.46 (10)	O6—C7—H7A	110.8
C4—C3—C2	114.78 (12)	O5—C7—H7A	110.8
O6—C3—H3	109.7	O6—C7—H7B	110.8
C4—C3—H3	109.7	O5—C7—H7B	110.8
C2—C3—H3	109.7	H7A—C7—H7B	108.8
C6—O4—C5	108.07 (11)	O2—C8—C1	109.23 (11)
O3—C4—C3	107.31 (11)	O2—C8—H8A	109.8
O3—C4—C5	103.80 (11)	C1—C8—H8A	109.8
C3—C4—C5	116.12 (11)	O2—C8—H8B	109.8
O3—C4—H4	109.8	C1—C8—H8B	109.8
C3—C4—H4	109.8	H8A—C8—H8B	108.3
C5—O1—C1—C8	−169.46 (11)	C3—C2—O5—C7	−24.54 (13)
C5—O1—C1—C2	69.05 (13)	C1—O1—C5—O4	80.45 (13)
O1—C1—C2—O5	66.87 (13)	C1—O1—C5—C4	−36.51 (15)
C8—C1—C2—O5	−52.27 (14)	C6—O4—C5—O1	−129.34 (12)
O1—C1—C2—C3	−47.39 (14)	C6—O4—C5—C4	−5.45 (13)
C8—C1—C2—C3	−166.53 (11)	O3—C4—C5—O1	103.14 (12)
O5—C2—C3—O6	0.05 (14)	C3—C4—C5—O1	−14.36 (17)
C1—C2—C3—O6	117.79 (12)	O3—C4—C5—O4	−17.05 (13)
O5—C2—C3—C4	−118.27 (12)	C3—C4—C5—O4	−134.55 (12)
C1—C2—C3—C4	−0.54 (16)	C4—C3—O6—C7	147.17 (12)
C6—O3—C4—C3	156.74 (11)	C2—C3—O6—C7	24.45 (14)
C6—O3—C4—C5	33.27 (13)	C4—O3—C6—O4	−37.75 (14)
O6—C3—C4—O3	159.69 (11)	C5—O4—C6—O3	26.67 (14)
C2—C3—C4—O3	−84.12 (13)	C3—O6—C7—O5	−41.25 (14)
O6—C3—C4—C5	−84.77 (14)	C2—O5—C7—O6	41.43 (14)
C2—C3—C4—C5	31.42 (16)	O1—C1—C8—O2	68.75 (14)
C1—C2—O5—C7	−144.91 (11)	C2—C1—C8—O2	−171.22 (11)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H12···O5i	0.87 (3)	2.01 (3)	2.846 (2)	161
C3—H3···O4ii	1.00	2.49	3.447 (2)	160
C4—H4···O3iii	1.00	2.46	3.296 (2)	141
C5—H5···O2iv	1.00	2.45	3.405 (2)	160
C7—H7A···O1v	0.99	2.48	3.455 (2)	169
C7—H7B···O1ii	0.99	2.56	3.509 (2)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H12⋯O5i	0.87 (3)	2.01 (3)	2.846 (2)	161
C3—H3⋯O4ii	1.00	2.49	3.447 (2)	160
C4—H4⋯O3iii	1.00	2.46	3.296 (2)	141
C5—H5⋯O2iv	1.00	2.45	3.405 (2)	160
C7—H7A⋯O1v	0.99	2.48	3.455 (2)	169
C7—H7B⋯O1ii	0.99	2.56	3.509 (2)	162

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .