Crystal structure of β-d,l-allose.

The title compound, C6H12O6, a C-3 position epimer of glucose, was crystallized from an equimolar mixture of d- and l-allose. It was confirmed that d-allose (l-allose) formed β-pyran-ose with a (4) C 1 ((1) C 4) conformation in the crystal. In the crystal, molecules are linked by O-H⋯O hydrogen bond, forming a three-dimensional framework. The cell volume of the racemic β-d,l-allose is 739.36 (3) Å(3), which is about 10 Å(3) smaller than that of chiral β-d-allose [V = 751.0 (2) Å(3)].

Related literature

For the crystal structure of the chiral β-d-allose, see: Kroon-Batenburg et al. (1984 ▸). For the crystal structure of racemic d,l-arabinose, see: Longchambon et al. (1985 ▸) and of chiral l-arabinose, see: Takagi & Jeffrey (1977 ▸). For the synthesis of chiral d- or l-allose, see: Menavuvu et al. (2006 ▸); Morimoto et al. (2006 ▸, 2013 ▸); Shimonishi & Izumori (1996 ▸).

Experimental

Crystal data

C6H12O6

M = 180.16

Monoclinic,

a = 4.98211 (10) Å

b = 12.5624 (3) Å

c = 11.8156 (3) Å

β = 91.1262 (14)°

V = 739.36 (3) Å3

Z = 4

Cu Kα radiation

μ = 1.29 mm−1

T = 295 K

0.10 × 0.10 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▸) T min = 0.687, T max = 0.879

12963 measured reflections

1350 independent reflections

1232 reflections with F 2 > 2σ(F 2)

R int = 0.075

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.102

S = 1.07

1350 reflections

115 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.22 e Å−3

Data collection: RAPID-AUTO (Rigaku, 2009 ▸); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SIR2008 in Il Milione (Burla et al., 2007 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ▸); molecular graphics: CrystalStructure (Rigaku, 2010 ▸); software used to prepare material for publication: CrystalStructure.

Crystal structure: contains datablock(s) General, I. DOI: 10.1107/S2056989015000353/is5386sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015000353/is5386Isup2.hkl

Click here for additional data file.

ORTEP . DOI: 10.1107/S2056989015000353/is5386fig1.tif

ORTEP view of the title compound with the atom-labeling scheme. The thermal ellipsoids of all non-hydrogen atoms are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius.

Click here for additional data file.

a . DOI: 10.1107/S2056989015000353/is5386fig2.tif

Part of the crystal structure of the title compound with hydrogen-bonding network represented as light green dashed lines, viewed down the tilted a axis. The hydrogen atoms are omitted for clarity.

Click here for additional data file.

d et al. a . DOI: 10.1107/S2056989015000353/is5386fig3.tif

Part of the crystal structure of the chiral β-d-allose (Kroon-Batenburg et al., 1984) with hydrogen-bonding network represented as light blue dashed lines, viewed down the a axis. The hydrogen atoms are omitted for clarity.

CCDC reference: 1037204

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

C6H12O6	F(000) = 384.00
Mr = 180.16	Dx = 1.618 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54187 Å
Hall symbol: -P 2ybc	Cell parameters from 11709 reflections
a = 4.98211 (10) Å	θ = 3.5–68.2°
b = 12.5624 (3) Å	µ = 1.29 mm−1
c = 11.8156 (3) Å	T = 295 K
β = 91.1262 (14)°	Block, colorless
V = 739.36 (3) Å3	0.10 × 0.10 × 0.10 mm
Z = 4

Rigaku R-AXIS RAPID diffractometer	1232 reflections with F2 > 2σ(F2)
Detector resolution: 10.000 pixels mm-1	Rint = 0.075
ω scans	θmax = 68.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −6→6
Tmin = 0.687, Tmax = 0.879	k = −15→15
12963 measured reflections	l = −14→14
1350 independent reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037	H-atom parameters constrained
wR(F2) = 0.102	w = 1/[σ2(Fo2) + (0.0463P)2 + 0.3535P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
1350 reflections	Δρmax = 0.37 e Å−3
115 parameters	Δρmin = −0.22 e Å−3
0 restraints	Extinction correction: SHELXL2013 (Sheldrick, 2015)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0159 (15)
Secondary atom site location: difference Fourier map

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

	x	y	z	Uiso*/Ueq
O1	0.1621 (3)	0.79703 (8)	0.67894 (10)	0.0283 (3)
O2	0.1676 (3)	0.85269 (9)	0.91826 (9)	0.0311 (4)
O3	−0.0213 (2)	1.05723 (8)	0.88005 (9)	0.0244 (3)
O4	0.3426 (3)	1.21319 (8)	0.80258 (10)	0.0270 (3)
O5	0.2673 (2)	0.96785 (8)	0.63757 (8)	0.0219 (3)
O6	0.6115 (3)	1.14807 (9)	0.56175 (9)	0.0282 (3)
C1	0.1454 (3)	0.90015 (11)	0.71937 (12)	0.0211 (4)
C2	0.2848 (3)	0.91736 (11)	0.83377 (12)	0.0207 (4)
C3	0.2552 (3)	1.03366 (11)	0.86734 (12)	0.0195 (4)
C4	0.3680 (3)	1.10357 (11)	0.77418 (12)	0.0189 (4)
C5	0.2263 (3)	1.07910 (11)	0.66196 (12)	0.0197 (4)
C6	0.3259 (4)	1.14427 (12)	0.56431 (13)	0.0259 (4)
H1A	0.3191	0.7774	0.6812	0.0340*
H1B	−0.0442	0.9196	0.7254	0.0254*
H2A	0.2377	0.7936	0.9180	0.0373*
H2B	0.4758	0.8998	0.8280	0.0248*
H3A	−0.0440	1.0847	0.9421	0.0293*
H3B	0.3529	1.0470	0.9387	0.0234*
H4B	0.5592	1.0872	0.7668	0.0226*
H4A	0.1849	1.2268	0.8151	0.0324*
H5A	0.0336	1.0920	0.6699	0.0237*
H6A	0.6640	1.1146	0.5069	0.0339*
H6C	0.2577	1.1140	0.4939	0.0311*
H6B	0.2565	1.2162	0.5702	0.0311*

	U11	U22	U33	U12	U13	U23
O1	0.0289 (7)	0.0177 (6)	0.0386 (7)	−0.0020 (5)	0.0058 (5)	−0.0067 (5)
O2	0.0465 (8)	0.0190 (6)	0.0283 (6)	0.0071 (5)	0.0162 (5)	0.0067 (5)
O3	0.0230 (6)	0.0284 (6)	0.0222 (6)	0.0063 (5)	0.0066 (4)	−0.0025 (5)
O4	0.0271 (6)	0.0147 (6)	0.0393 (7)	−0.0005 (4)	0.0044 (5)	−0.0042 (5)
O5	0.0292 (7)	0.0174 (6)	0.0193 (6)	−0.0019 (4)	0.0049 (5)	−0.0011 (4)
O6	0.0303 (7)	0.0300 (7)	0.0247 (6)	−0.0063 (5)	0.0089 (5)	−0.0044 (5)
C1	0.0232 (8)	0.0154 (8)	0.0250 (8)	−0.0019 (6)	0.0047 (6)	−0.0016 (6)
C2	0.0233 (8)	0.0182 (8)	0.0207 (8)	0.0035 (6)	0.0054 (6)	0.0030 (6)
C3	0.0202 (8)	0.0195 (8)	0.0187 (7)	0.0025 (6)	−0.0005 (6)	−0.0010 (6)
C4	0.0187 (8)	0.0139 (7)	0.0240 (8)	0.0013 (6)	0.0013 (6)	−0.0023 (6)
C5	0.0199 (8)	0.0165 (8)	0.0229 (8)	0.0017 (6)	0.0022 (6)	0.0002 (6)
C6	0.0282 (9)	0.0251 (8)	0.0245 (8)	0.0008 (6)	0.0025 (6)	0.0052 (7)

O1—C1	1.3837 (18)	O1—H1A	0.820
O2—C2	1.4216 (19)	O2—H2A	0.820
O3—C3	1.4199 (18)	O3—H3A	0.820
O4—C4	1.4236 (18)	O4—H4A	0.820
O5—C1	1.4314 (18)	O6—H6A	0.820
O5—C5	1.4423 (18)	C1—H1B	0.980
O6—C6	1.425 (2)	C2—H2B	0.980
C1—C2	1.523 (2)	C3—H3B	0.980
C2—C3	1.522 (2)	C4—H4B	0.980
C3—C4	1.524 (2)	C5—H5A	0.980
C4—C5	1.521 (2)	C6—H6C	0.970
C5—C6	1.507 (2)	C6—H6B	0.970
C1—O5—C5	112.16 (11)	C6—O6—H6A	109.474
O1—C1—O5	107.10 (12)	O1—C1—H1B	108.857
O1—C1—C2	114.20 (12)	O5—C1—H1B	108.860
O5—C1—C2	108.84 (12)	C2—C1—H1B	108.859
O2—C2—C1	110.83 (12)	O2—C2—H2B	109.452
O2—C2—C3	108.80 (12)	C1—C2—H2B	109.449
C1—C2—C3	108.83 (12)	C3—C2—H2B	109.458
O3—C3—C2	109.09 (12)	O3—C3—H3B	109.847
O3—C3—C4	109.17 (12)	C2—C3—H3B	109.848
C2—C3—C4	109.02 (12)	C4—C3—H3B	109.842
O4—C4—C3	110.57 (12)	O4—C4—H4B	108.392
O4—C4—C5	111.04 (12)	C3—C4—H4B	108.388
C3—C4—C5	109.98 (12)	C5—C4—H4B	108.388
O5—C5—C4	107.75 (11)	O5—C5—H5A	108.775
O5—C5—C6	108.87 (12)	C4—C5—H5A	108.778
C4—C5—C6	113.79 (12)	C6—C5—H5A	108.780
O6—C6—C5	112.25 (13)	O6—C6—H6C	109.153
C1—O1—H1A	109.467	O6—C6—H6B	109.157
C2—O2—H2A	109.472	C5—C6—H6C	109.152
C3—O3—H3A	109.470	C5—C6—H6B	109.146
C4—O4—H4A	109.476	H6C—C6—H6B	107.880
C1—O5—C5—C4	63.92 (13)	C1—C2—C3—C4	−56.31 (14)
C1—O5—C5—C6	−172.24 (10)	O3—C3—C4—O4	60.68 (14)
C5—O5—C1—O1	171.24 (10)	O3—C3—C4—C5	−62.31 (13)
C5—O5—C1—C2	−64.83 (13)	C2—C3—C4—O4	179.76 (11)
O1—C1—C2—O2	−61.24 (16)	C2—C3—C4—C5	56.77 (14)
O1—C1—C2—C3	179.15 (11)	O4—C4—C5—O5	178.40 (10)
O5—C1—C2—O2	179.15 (10)	O4—C4—C5—C6	57.59 (15)
O5—C1—C2—C3	59.54 (14)	C3—C4—C5—O5	−58.88 (14)
O2—C2—C3—O3	−58.04 (14)	C3—C4—C5—C6	−179.69 (10)
O2—C2—C3—C4	−177.17 (10)	O5—C5—C6—O6	−74.12 (14)
C1—C2—C3—O3	62.82 (14)	C4—C5—C6—O6	46.06 (16)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4i	0.82	1.88	2.6884 (16)	171
O2—H2A···O6i	0.82	1.99	2.8044 (16)	172
O3—H3A···O2ii	0.82	1.94	2.7494 (16)	169
O4—H4A···O1iii	0.82	1.94	2.7384 (16)	163
O4—H4A···O3	0.82	2.49	2.8333 (15)	106
O6—H6A···O5iv	0.82	2.03	2.8439 (15)	171

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O1H1AO4i	0.82	1.88	2.6884(16)	171
O2H2AO6i	0.82	1.99	2.8044(16)	172
O3H3AO2ii	0.82	1.94	2.7494(16)	169
O4H4AO1iii	0.82	1.94	2.7384(16)	163
O6H6AO5iv	0.82	2.03	2.8439(15)	171

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