Crystal structure of β-d,l-fructose

Ishii, T.; Senoo, T.; Yoshihara, A.; Fukada, K.; Sakane, G.

doi:10.1107/S2056989015016503

organic compounds

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ISSN: 2056-9890

Volume 71| Part 10| October 2015| Pages o719-o720

doi:10.1107/S2056989015016503

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Crystal structure of β-D,L-fructose

Tomohiko Ishii,^a ^* Tatsuya Senoo,^a Akihide Yoshihara,^b Kazuhiro Fukada ^c and Genta Sakane ^d

^aDepartment of Advanced Materials Science, Faculty of Engineering, Kagawa University, 2217-20 Hayashi-cho, Takamatsu, Kagawa 761-0396, Japan, ^bRare Sugar Research Center, Kagawa University, 2393 Ikenobe, Kagawa 761-0795, Japan, ^cDepartment of Applied Biological Science, Faculty of Agriculture, Kagawa University, 2393 Ikenobe, Kagawa 761-0795, Japan, and ^dDepartment of Chemistry, Faculty of Science, Okayama University of Science, 1-1 Ridaicho, Kita-ku, Okayama 700-0005, Japan
^*Correspondence e-mail: tishii@eng.kagawa-u.ac.jp

Edited by H. Ishida, Okayama University, Japan (Received 25 August 2015; accepted 4 September 2015; online 12 September 2015)

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 ²C₅ (or ⁵C₂) 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.

Keywords: crystal structure; hydrogen bonding; racemic compound; rare sugar.

CCDC reference: 1422317

1. 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 ).

2. Experimental

2.1. Crystal data

C₆H₁₂O₆
M_r = 180.16
Triclinic, $[P \overline 1]$
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) Å³
Z = 2
Cu Kα radiation
μ = 1.30 mm⁻¹
T = 296 K
0.10 × 0.10 × 0.10 mm

2.2. 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 F² > 2.0σ(F²)
R_int = 0.079

2.3. Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 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

Table 1
Hydrogen-bond geometry (Å, °)

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⋯O1ⁱⁱ	0.82	1.93	2.7224 (13)	161
O3—H3A⋯O4ⁱⁱⁱ	0.82	1.96	2.7831 (18)	177
O4—H4A⋯O5^iv	0.82	2.01	2.7893 (13)	158
O5—H5A⋯O4^v	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.

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.

Supporting information

CCDC reference: 1422317

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989015016503/is5416sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015016503/is5416Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015016503/is5416Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2009); cell refinement: RAPID-AUTO (Rigaku, 2009); data reduction: RAPID-AUTO (Rigaku, 2009); 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 (Rigaku, 2014).

Figures top

	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).

1,3,4,5,6-Pentahydroxyhexan-2-one top

Crystal data top

C₆H₁₂O₆	Z = 2
M_r = 180.16	F(000) = 192.00
Triclinic, P1	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0374P)² + 0.1404P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1329 reflections	Δρ_max = 0.32 e Å⁻³
115 parameters	Δρ_min = −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

Crystal data top

C₆H₁₂O₆	γ = 78.381 (2)°
M_r = 180.16	V = 366.09 (2) Å³
Triclinic, P1	Z = 2
a = 5.43124 (19) Å	Cu Kα radiation
b = 7.2727 (3) Å	µ = 1.30 mm⁻¹
c = 10.1342 (4) Å	T = 296 K
α = 69.120 (2)°	0.10 × 0.10 × 0.10 mm
β = 83.907 (2)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1329 independent reflections
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995)	1211 reflections with F² > 2.0σ(F²)
T_min = 0.729, T_max = 0.878	R_int = 0.079
6710 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.08	Δρ_max = 0.32 e Å⁻³
1329 reflections	Δρ_min = −0.23 e Å⁻³
115 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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) top

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···O5^iv	0.82	2.01	2.7893 (13)	158
O5—H5A···O4^v	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.

Hydrogen-bond geometry (Å, º) top

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···O5^iv	0.82	2.01	2.7893 (13)	158
O5—H5A···O4^v	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.

Acknowledgements

The authors are grateful to Grants-in-Aid for Rare Sugar Research of Kagawa University.

References

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