Crystal structure of β-d,l-fructose

Abstract

The title compound, C₆H₁₂O₆, was crystallized from an aqueous solution of equimolar mixture of d- and l-fructose (1,3,4,5,6-penta­hydroxy­hexan-2-one, arabino-hexulose or levu­lose), and it was confirmed that d-fructose (or l-fructose) formed β-pyran­ose with a ² C ₅ (or ⁵ C ₂) conformation. In the crystal, two O—H⋯O hydrogen bonds between the hy­droxy groups at the C-1 and C-3 positions, and at the C-4 and C-5 positions connect homochiral mol­ecules into a column along the a axis. The columns are linked by other O—H⋯O hydrogen bonds between d- and l-fructose mol­ecules, forming a three-dimensional network.

Related literature  

For crystal structures of chiral β-d-fructose, racemic β-d,l-allose and racemic β-d,l-psicose, see: Kanters et al. (1977 ▸); Ishii, Senoo et al. (2015 ▸); Ishii, Sakane et al. (2015 ▸), respectively. For the synthesis of chiral l-fructose, see: Itoh & Izumori (1996 ▸).

Experimental  

Crystal data  

• C₆H₁₂O₆

• M _r = 180.16

• Triclinic,

• a = 5.43124 (19) Å

• b = 7.2727 (3) Å

• c = 10.1342 (4) Å

• α = 69.120 (2)°

• β = 83.907 (2)°

• γ = 78.381 (2)°

• V = 366.09 (2) ų

• Z = 2

• Cu Kα radiation

• μ = 1.30 mm⁻¹

• T = 296 K

• 0.10 × 0.10 × 0.10 mm

Data collection  

• Rigaku R-AXIS RAPID diffractometer

• Absorption correction: multi-scan (ABSCOR; Rigaku, 1995 ▸) T _min = 0.729, T _max = 0.878

• 6710 measured reflections

• 1329 independent reflections

• 1211 reflections with F ² > 2.0σ(F ²)

• R _int = 0.079

Refinement  

• R[F ² > 2σ(F ²)] = 0.037

• wR(F ²) = 0.095

• S = 1.08

• 1329 reflections

• 115 parameters

• H-atom parameters constrained

• Δρ_max = 0.32 e Å⁻³

• Δρ_min = −0.23 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 2009 ▸); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SIR2011 (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.

Supplementary Material

CCDC reference: 1422317

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O1H1AO3i	0.82	2.28	2.9202(14)	135
O2H2AO1ii	0.82	1.93	2.7224(13)	161
O3H3AO4iii	0.82	1.96	2.7831(18)	177
O4H4AO5iv	0.82	2.01	2.7893(13)	158
O5H5AO4v	0.82	2.05	2.8431(12)	163

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

supplementary crystallographic information

S1. Comment

Fructose, especially in D-fructose, is one of the most famous, fundamental and important monosaccharides in sugar family, and has been under intense investigation. On the other hand, L-fructose is classified into a rare sugar, and hardly exists in nature. In this study we investigate to create a novel racemic single-crystal including these D- and L-fructoses together with the ratio of 1: 1. The space group is triclinic P1 (Z = 2), which is significantly different from our previous reports of the racemic β-D,L-allose (monoclinic P2₁/c, Z = 4; Ishii, Senoo et al., 2015) and psicose (orthorhombic Pna2₁, Z = 4; Ishii, Sakane et al., 2015). In the unit cell, the D- and L-molecules are located with the heterochiral hydrogen bonding networks (O3—H3A···O4). As shown in Fig. 2, two homochiral hydrogen bonding networks (O1—H1A···O3 and O4—H4A···O5) have also been observed along to the a-axis. Additional two heterochiral hydrogen bonds (O2—H2A···O1 and O5—H5A···O4) are also confirmed (Fig. 3).

S2. Experimental

D-Fructose was purchased from Wako Pure Chemical Industries. L-Fructose was prepared from L-psicose by enzymatic epimerization using D-tagatose 3-epimerase (Itoh & Izumori, 1996). D-Fructose and L-fructose were mixed in equal amount and dissolved in hot water to give a 70 wt% solution. And these samples were kept at room temperature. After one day, small single crystals were obtained in a hermetically sealed test tube.

S3. Refinement

H atoms bounded to methine-type C (H3B, H4B, H5B) and methylene-type C (H1B, H1C, H6A, H6B) were positioned geometrically with C—H = 0.98 and 0.97 Å, respectively, and refined using a riding model with U_iso(H) = 1.2U_eq(C). H atoms bounded to O (H1A, H2A, H3A, H4A, H5A) were positioned geometrically (O—H = 0.82 Å) and refined as riding with U_iso(H) = 1.2U_eq(O), allowing for free rotation of the OH groups.

Figures

Fig. 1.

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.

Fig. 2.

Part of the packing diagram of the title compound viewed down the c-axis, showing the hydrogen-bonding network (green solid lines).

Fig. 3.

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

Crystal data

C6H12O6	Z = 2
Mr = 180.16	F(000) = 192.00
Triclinic, P1	Dx = 1.634 Mg m−3
a = 5.43124 (19) Å	Cu Kα radiation, λ = 1.54187 Å
b = 7.2727 (3) Å	Cell parameters from 4534 reflections
c = 10.1342 (4) Å	θ = 4.7–68.4°
α = 69.120 (2)°	µ = 1.30 mm−1
β = 83.907 (2)°	T = 296 K
γ = 78.381 (2)°	Block, colorless
V = 366.09 (2) Å3	0.10 × 0.10 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	1211 reflections with F2 > 2.0σ(F2)
Detector resolution: 10.000 pixels mm-1	Rint = 0.079
ω scans	θmax = 68.2°, θmin = 4.7°
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995)	h = −6→6
Tmin = 0.729, Tmax = 0.878	k = −8→8
6710 measured reflections	l = −12→12
1329 independent reflections

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037	H-atom parameters constrained
wR(F2) = 0.095	w = 1/[σ2(Fo2) + (0.0374P)2 + 0.1404P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
1329 reflections	Δρmax = 0.32 e Å−3
115 parameters	Δρmin = −0.23 e Å−3
0 restraints	Extinction correction: SHELXL2013 (Sheldrick, 2015)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.125 (6)
Secondary atom site location: difference Fourier map

Special details

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).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	1.19555 (19)	0.09152 (15)	0.87814 (12)	0.0325 (3)
O2	0.66671 (18)	0.27440 (15)	0.92243 (11)	0.0287 (3)
O3	0.50386 (19)	0.33842 (16)	0.65941 (12)	0.0294 (3)
O4	0.34223 (18)	0.76120 (15)	0.58108 (11)	0.0264 (3)
O5	0.81908 (18)	0.84537 (14)	0.60893 (12)	0.0290 (3)
O6	0.96847 (17)	0.47716 (14)	0.82413 (11)	0.0223 (3)
C1	1.0136 (3)	0.1818 (2)	0.77318 (17)	0.0265 (4)
C2	0.8236 (2)	0.34747 (19)	0.80373 (15)	0.0195 (3)
C3	0.6557 (2)	0.46432 (19)	0.67791 (15)	0.0190 (3)
C4	0.4906 (3)	0.6455 (2)	0.70256 (15)	0.0200 (3)
C5	0.6558 (3)	0.77295 (19)	0.72899 (16)	0.0223 (3)
C6	0.8182 (3)	0.6457 (2)	0.85210 (16)	0.0254 (4)
H1A	1.30779	0.15812	0.86062	0.0390*
H1C	0.92594	0.08085	0.76811	0.0318*
H1B	1.0976	0.23653	0.68208	0.0318*
H2A	0.74136	0.16995	0.97716	0.0345*
H3A	0.55367	0.31042	0.58847	0.0353*
H3B	0.76216	0.5097	0.59244	0.0227*
H4A	0.19353	0.75392	0.60178	0.0317*
H4B	0.37832	0.60041	0.78545	0.0240*
H5A	0.74552	0.94902	0.55285	0.0348*
H5B	0.55062	0.8858	0.75058	0.0268*
H6A	0.92669	0.72507	0.86923	0.0305*
H6B	0.71231	0.59981	0.93633	0.0305*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0202 (6)	0.0153 (5)	0.0465 (8)	−0.0003 (4)	−0.0014 (5)	0.0066 (5)
O2	0.0251 (6)	0.0190 (5)	0.0265 (6)	0.0006 (4)	0.0037 (5)	0.0074 (4)
O3	0.0292 (6)	0.0280 (6)	0.0361 (7)	−0.0153 (5)	−0.0002 (5)	−0.0118 (5)
O4	0.0160 (5)	0.0236 (6)	0.0298 (6)	−0.0001 (4)	−0.0051 (4)	0.0019 (5)
O5	0.0208 (5)	0.0154 (5)	0.0385 (7)	−0.0035 (4)	−0.0014 (5)	0.0060 (5)
O6	0.0186 (5)	0.0164 (5)	0.0309 (6)	−0.0004 (4)	−0.0061 (4)	−0.0071 (4)
C1	0.0223 (7)	0.0144 (7)	0.0389 (9)	−0.0022 (6)	−0.0001 (6)	−0.0054 (6)
C2	0.0176 (7)	0.0123 (6)	0.0242 (8)	−0.0039 (5)	0.0003 (6)	−0.0007 (5)
C3	0.0177 (7)	0.0140 (7)	0.0233 (8)	−0.0070 (5)	−0.0006 (6)	−0.0020 (6)
C4	0.0158 (7)	0.0163 (7)	0.0213 (8)	−0.0018 (5)	−0.0019 (6)	0.0013 (6)
C5	0.0198 (7)	0.0131 (7)	0.0315 (9)	−0.0005 (5)	−0.0002 (6)	−0.0060 (6)
C6	0.0272 (8)	0.0199 (7)	0.0304 (8)	−0.0015 (6)	−0.0044 (6)	−0.0107 (6)

Geometric parameters (Å, º)

O1—C1	1.4153 (19)	O1—H1A	0.820
O2—C2	1.4017 (16)	O2—H2A	0.820
O3—C3	1.419 (2)	O3—H3A	0.820
O4—C4	1.4395 (16)	O4—H4A	0.820
O5—C5	1.4305 (17)	O5—H5A	0.820
O6—C2	1.423 (2)	C1—H1C	0.970
O6—C6	1.4298 (19)	C1—H1B	0.970
C1—C2	1.520 (2)	C3—H3B	0.980
C2—C3	1.5304 (19)	C4—H4B	0.980
C3—C4	1.521 (2)	C5—H5B	0.980
C4—C5	1.517 (2)	C6—H6A	0.970
C5—C6	1.5075 (19)	C6—H6B	0.970
C2—O6—C6	113.25 (10)	C4—O4—H4A	109.467
O1—C1—C2	111.97 (14)	C5—O5—H5A	109.473
O2—C2—O6	111.23 (13)	O1—C1—H1C	109.215
O2—C2—C1	112.44 (10)	O1—C1—H1B	109.220
O2—C2—C3	107.69 (10)	C2—C1—H1C	109.218
O6—C2—C1	105.55 (11)	C2—C1—H1B	109.221
O6—C2—C3	109.06 (10)	H1C—C1—H1B	107.907
C1—C2—C3	110.86 (13)	O3—C3—H3B	109.026
O3—C3—C2	109.62 (10)	C2—C3—H3B	109.028
O3—C3—C4	110.08 (11)	C4—C3—H3B	109.024
C2—C3—C4	110.04 (13)	O4—C4—H4B	109.255
O4—C4—C3	110.05 (13)	C3—C4—H4B	109.253
O4—C4—C5	109.74 (10)	C5—C4—H4B	109.254
C3—C4—C5	109.27 (11)	O5—C5—H5B	109.808
O5—C5—C4	110.97 (14)	C4—C5—H5B	109.810
O5—C5—C6	107.71 (11)	C6—C5—H5B	109.807
C4—C5—C6	108.69 (11)	O6—C6—H6A	109.512
O6—C6—C5	110.67 (14)	O6—C6—H6B	109.511
C1—O1—H1A	109.469	C5—C6—H6A	109.511
C2—O2—H2A	109.478	C5—C6—H6B	109.513
C3—O3—H3A	109.476	H6A—C6—H6B	108.082
C2—O6—C6—C5	−61.73 (13)	C1—C2—C3—C4	−172.62 (10)
C6—O6—C2—O2	−58.74 (12)	O3—C3—C4—O4	−62.10 (13)
C6—O6—C2—C1	179.03 (9)	O3—C3—C4—C5	177.33 (9)
C6—O6—C2—C3	59.88 (13)	C2—C3—C4—O4	176.97 (10)
O1—C1—C2—O2	−68.49 (15)	C2—C3—C4—C5	56.41 (12)
O1—C1—C2—O6	52.95 (13)	O4—C4—C5—O5	−58.98 (13)
O1—C1—C2—C3	170.90 (9)	O4—C4—C5—C6	−177.25 (10)
O2—C2—C3—O3	−57.21 (15)	C3—C4—C5—O5	61.77 (12)
O2—C2—C3—C4	63.99 (14)	C3—C4—C5—C6	−56.50 (14)
O6—C2—C3—O3	−178.02 (10)	O5—C5—C6—O6	−61.97 (15)
O6—C2—C3—C4	−56.82 (13)	C4—C5—C6—O6	58.34 (14)
C1—C2—C3—O3	66.18 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3i	0.82	2.28	2.9202 (14)	135
O2—H2A···O1	0.82	2.60	2.9721 (14)	110
O2—H2A···O1ii	0.82	1.93	2.7224 (13)	161
O3—H3A···O4iii	0.82	1.96	2.7831 (18)	177
O4—H4A···O5iv	0.82	2.01	2.7893 (13)	158
O5—H5A···O4v	0.82	2.05	2.8431 (12)	163

Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y, −z+2; (iii) −x+1, −y+1, −z+1; (iv) x−1, y, z; (v) −x+1, −y+2, −z+1.