Crystal structure of 6-de-oxy-α-l-psico-furan-ose.

The title compound, C6H12O5, was crystallized from an aqueous solution of 6-de-oxy-l-psicose (6-de-oxy-l-allulose, (3S,4S,5S)-1,3,4,5-tetra-hydroxy-hexan-2-one), and the mol-ecule was confirmed as α-furan-ose with a (3) T 4 (or E 4) conformation, which is a predominant tautomer in solution. This five-membered furan-ose ring structure is the second example in the field of the 6-de-oxy-ketohexose family. The cell volume of the title compound [742.67 (7) Å(3), Z = 4 at room temperature] is only 1.4% smaller than that of β-d-psico-pyran-ose, C6H12O6 (753.056 Å(3), Z = 4 at room temperature).

Related literature

For the predominant tautomer, α-furan­ose, of 6-de­oxy-l-psicose in aqueous solution, see: Yoshihara et al. (2015 ▸). For the crystal structure of chiral β-d-psicose, see: Kwiecień et al. (2008 ▸); Fukada et al. (2010 ▸). For the crystal structure of racemic β-D,l-psicose, see: Ishii et al. (2015 ▸). For the synthesis of 6-de­oxy-l-psicose, see: Shompoosang et al. (2014 ▸). For the crystal structures of 6-de­oxy-α-l-sorbo­furan­ose and 6-de­oxy-α-d-sorbo­furan­ose, see: Swaminathan et al. (1979 ▸); Rao et al. (1981 ▸); Jones et al. (2006 ▸).

Experimental

Crystal data

C6H12O5

M = 164.16

Orthorhombic,

a = 5.7853 (3) Å

b = 8.9442 (5) Å

c = 14.3528 (8) Å

V = 742.69 (7) Å3

Z = 4

Cu Kα radiation

μ = 1.12 mm−1

T = 296 K

0.10 × 0.10 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▸) T min = 0.732, T max = 0.894

13299 measured reflections

1358 independent reflections

1330 reflections with F 2 > 2σ(F 2)

R int = 0.072

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.065

S = 1.08

1358 reflections

105 parameters

H-atom parameters constrained

Δρmax = 0.15 e Å−3

Δρmin = −0.14 e Å−3

Absolute structure: Flack x determined using 521 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons & Flack, 2004 ▸)

Absolute structure parameter: 0.03 (8)

Data collection: RAPID-AUTO (Rigaku, 2009 ▸); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: Il Milione (Burla et al., 2012 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ▸); molecular graphics: CrystalStructure (Rigaku, 2014 ▸); software used to prepare material for publication: CrystalStructure.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015022215/is5433sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015022215/is5433Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015022215/is5433Isup3.png

Click here for additional data file.

ORTEP . DOI: 10.1107/S2056989015022215/is5433fig1.tif

An 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/S2056989015022215/is5433fig2.tif

A packing diagram of the title compound viewed down the a-axis, showing the hydrogen-bonding network (green dashed lines).

CCDC reference: 1437931

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

C6H12O5	Dx = 1.468 Mg m−3
Mr = 164.16	Cu Kα radiation, λ = 1.54187 Å
Orthorhombic, P212121	Cell parameters from 7546 reflections
a = 5.7853 (3) Å	θ = 3.1–68.3°
b = 8.9442 (5) Å	µ = 1.12 mm−1
c = 14.3528 (8) Å	T = 296 K
V = 742.69 (7) Å3	Block, colorless
Z = 4	0.10 × 0.10 × 0.10 mm
F(000) = 352.00

Rigaku R-AXIS RAPID diffractometer	1330 reflections with F2 > 2σ(F2)
Detector resolution: 10.000 pixels mm-1	Rint = 0.072
ω scans	θmax = 68.2°, θmin = 5.8°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −6→6
Tmin = 0.732, Tmax = 0.894	k = −10→10
13299 measured reflections	l = −17→17
1358 independent reflections

Refinement on F2	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.027	w = 1/[σ2(Fo2) + (0.0207P)2 + 0.1732P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.065	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 0.15 e Å−3
1358 reflections	Δρmin = −0.14 e Å−3
105 parameters	Extinction correction: SHELXL
0 restraints	Extinction coefficient: 0.0144 (15)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack x determined using 521 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.03 (8)
Hydrogen site location: inferred from neighbouring sites

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

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	1.1489 (3)	0.60359 (18)	0.19568 (11)	0.0370 (4)
O2	0.5730 (3)	0.45936 (18)	0.23138 (13)	0.0419 (4)
O3	0.5171 (2)	0.68432 (15)	0.34295 (10)	0.0274 (3)
O4	0.8265 (3)	0.72675 (18)	0.47842 (10)	0.0371 (4)
O5	0.8957 (3)	0.41852 (14)	0.32155 (9)	0.0297 (4)
C1	0.9314 (4)	0.5411 (2)	0.17460 (13)	0.0299 (5)
C2	0.7827 (3)	0.5218 (2)	0.26045 (13)	0.0239 (4)
C3	0.7513 (3)	0.6680 (2)	0.31678 (13)	0.0217 (4)
C4	0.9029 (3)	0.6417 (2)	0.40186 (13)	0.0243 (4)
C5	0.8846 (4)	0.4748 (2)	0.41607 (13)	0.0288 (5)
C6	1.0749 (5)	0.4055 (3)	0.47269 (18)	0.0472 (6)
H1A	1.14196	0.69485	0.19094	0.0444*
H1C	0.95355	0.44456	0.14516	0.0359*
H1B	0.85181	0.60539	0.13061	0.0359*
H2A	0.46647	0.5151	0.24595	0.0503*
H3A	0.47011	0.76663	0.32637	0.0328*
H3B	0.80479	0.75478	0.28114	0.0261*
H4A	0.93817	0.75318	0.50951	0.0445*
H4B	1.06309	0.66817	0.38712	0.0291*
H5A	0.73436	0.45008	0.44361	0.0346*
H6A	1.0678	0.44263	0.53538	0.0566*
H6B	1.05675	0.29881	0.47311	0.0566*
H6C	1.22165	0.4308	0.44577	0.0566*

	U11	U22	U33	U12	U13	U23
O1	0.0306 (8)	0.0317 (8)	0.0486 (9)	0.0022 (7)	0.0045 (7)	0.0026 (7)
O2	0.0265 (8)	0.0310 (9)	0.0683 (11)	−0.0008 (7)	−0.0091 (7)	−0.0203 (8)
O3	0.0221 (7)	0.0249 (8)	0.0351 (7)	0.0048 (6)	−0.0004 (6)	0.0008 (6)
O4	0.0320 (8)	0.0467 (10)	0.0325 (8)	0.0046 (8)	−0.0052 (6)	−0.0198 (7)
O5	0.0448 (9)	0.0177 (7)	0.0266 (7)	0.0073 (6)	−0.0022 (7)	0.0004 (5)
C1	0.0384 (11)	0.0263 (11)	0.0249 (10)	0.0058 (9)	−0.0033 (8)	−0.0040 (8)
C2	0.0267 (11)	0.0170 (9)	0.0282 (9)	0.0018 (8)	−0.0066 (8)	−0.0025 (7)
C3	0.0223 (9)	0.0165 (9)	0.0262 (9)	0.0002 (8)	0.0014 (8)	−0.0022 (7)
C4	0.0231 (9)	0.0244 (11)	0.0253 (9)	0.0001 (9)	−0.0000 (8)	−0.0055 (8)
C5	0.0333 (11)	0.0283 (11)	0.0248 (9)	0.0004 (9)	−0.0008 (8)	0.0004 (8)
C6	0.0607 (16)	0.0405 (14)	0.0404 (12)	0.0144 (12)	−0.0125 (12)	0.0049 (10)

O1—C1	1.410 (3)	O2—H2A	0.820
O2—C2	1.399 (2)	O3—H3A	0.820
O3—C3	1.414 (2)	O4—H4A	0.820
O4—C4	1.408 (2)	C1—H1C	0.970
O5—C2	1.432 (2)	C1—H1B	0.970
O5—C5	1.448 (2)	C3—H3B	0.980
C1—C2	1.512 (3)	C4—H4B	0.980
C2—C3	1.548 (3)	C5—H5A	0.980
C3—C4	1.522 (3)	C6—H6A	0.960
C4—C5	1.510 (3)	C6—H6B	0.960
C5—C6	1.502 (3)	C6—H6C	0.960
O1—H1A	0.820
C2—O5—C5	109.24 (14)	O1—C1—H1C	109.164
O1—C1—C2	112.20 (16)	O1—C1—H1B	109.167
O2—C2—O5	108.73 (15)	C2—C1—H1C	109.166
O2—C2—C1	107.19 (16)	C2—C1—H1B	109.170
O2—C2—C3	113.01 (16)	H1C—C1—H1B	107.872
O5—C2—C1	108.26 (16)	O3—C3—H3B	111.067
O5—C2—C3	106.18 (14)	C2—C3—H3B	111.068
C1—C2—C3	113.31 (16)	C4—C3—H3B	111.066
O3—C3—C2	109.81 (15)	O4—C4—H4B	109.543
O3—C3—C4	110.80 (15)	C3—C4—H4B	109.538
C2—C3—C4	102.75 (15)	C5—C4—H4B	109.537
O4—C4—C3	111.22 (16)	O5—C5—H5A	109.822
O4—C4—C5	114.02 (16)	C4—C5—H5A	109.816
C3—C4—C5	102.76 (15)	C6—C5—H5A	109.811
O5—C5—C4	102.34 (14)	C5—C6—H6A	109.470
O5—C5—C6	109.33 (18)	C5—C6—H6B	109.472
C4—C5—C6	115.43 (18)	C5—C6—H6C	109.471
C1—O1—H1A	109.468	H6A—C6—H6B	109.472
C2—O2—H2A	109.470	H6A—C6—H6C	109.470
C3—O3—H3A	109.471	H6B—C6—H6C	109.473
C4—O4—H4A	109.477
C2—O5—C5—C4	−34.64 (18)	O5—C2—C3—C4	12.06 (17)
C2—O5—C5—C6	−157.50 (14)	C1—C2—C3—O3	135.42 (15)
C5—O5—C2—O2	−107.81 (16)	C1—C2—C3—C4	−106.65 (16)
C5—O5—C2—C1	136.05 (14)	O3—C3—C4—O4	−37.4 (2)
C5—O5—C2—C3	14.07 (18)	O3—C3—C4—C5	85.02 (16)
O1—C1—C2—O2	−179.95 (14)	C2—C3—C4—O4	−154.60 (14)
O1—C1—C2—O5	−62.8 (2)	C2—C3—C4—C5	−32.21 (16)
O1—C1—C2—C3	54.7 (2)	O4—C4—C5—O5	161.44 (14)
O2—C2—C3—O3	13.2 (2)	O4—C4—C5—C6	−79.9 (2)
O2—C2—C3—C4	131.17 (15)	C3—C4—C5—O5	40.95 (18)
O5—C2—C3—O3	−105.88 (16)	C3—C4—C5—C6	159.59 (14)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O5i	0.82	2.02	2.839 (2)	177
O2—H2A···O1ii	0.82	2.13	2.819 (2)	142
O2—H2A···O3	0.82	2.08	2.592 (2)	121
O3—H3A···O2iii	0.82	1.93	2.732 (2)	166
O4—H4A···O3iv	0.82	2.24	2.902 (2)	138
O4—H4A···O4iv	0.82	2.26	2.987 (2)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O5i	0.82	2.02	2.839 (2)	177
O2—H2A⋯O1ii	0.82	2.13	2.819 (2)	142
O2—H2A⋯O3	0.82	2.08	2.592 (2)	121
O3—H3A⋯O2iii	0.82	1.93	2.732 (2)	166
O4—H4A⋯O3iv	0.82	2.24	2.902 (2)	138
O4—H4A⋯O4iv	0.82	2.26	2.987 (2)	148

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