α-d-Tagatopyran­ose

Punzo, F.; Watkin, D.J.; Fleet, G.W.J.

doi:10.1107/S1600536809017656

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Pages o1393-o1394

doi:10.1107/S1600536809017656

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α-D-Tagatopyranose

Francesco Punzo,^a ^*‡ David J. Watkin ^b and George W. J. Fleet ^c

^aLAMSUN and CSGI at Dipartimento di Scienze Chimiche, Università degli Studi di Catania, Viale Andrea Doria 6, 95125, Catania, Italy, ^bUniversity of Oxford, Department of Chemical Crystallography, Chemistry Research Laboratory, Oxford OX1 3TA, England, and ^cUniversity of Oxford, Department of Organic Chemistry, Chemistry Research Laboratory, Oxford OX1 3TA, England
^*Correspondence e-mail: fpunzo@unict.it

(Received 7 April 2009; accepted 11 May 2009; online 23 May 2009)

The title compound, C₆H₁₂O₆, also known as D-Tagatose, occurs in its furanose and pyranose forms in solution, but only the α-pyranose form crystallizes out. In the crystal, the molecules form hydrogen bonded chains propagating in [100] linked by O—H⋯O interactions. Further O—H⋯O bonds cross-link the chains.

Related literature

For the D-tagatose market price, syntheses and applications, see: Angyal (1991 ); Beadle et al. (1992 ); Granstrom et al. (2004 ); Izumori (2002 ); Skytte (2002 ); Porwell (2007 ). For the potential of the title compound as a chiral building block, see: Soengas et al. (2005 ); Jones et al. (2007 , 2008 ); Yoshihara et al. (2008 ). For related crystallographic literature, see: Takagi et al. (1969 ); Görbitz (1999 ); Watkin et al. (2005 ); Kwiecien et al. (2008 ); Larson (1970 ).

Experimental

Crystal data

C₆H₁₂O₆
M_r = 180.16
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.2201 (1) Å
b = 6.5022 (1) Å
c = 17.6629 (4) Å
V = 714.36 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 190 K
0.50 × 0.30 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.96, T_max = 0.97
2343 measured reflections
1378 independent reflections
1351 reflections with I > 2.0σ(I)
R_int = 0.010

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.065
S = 0.96
1378 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O10ⁱ	0.81	2.02	2.8236 (14)	171
O9—H91⋯O1ⁱⁱ	0.83	1.90	2.7203 (14)	173
O12—H121⋯O4ⁱⁱⁱ	0.83	2.09	2.7875 (14)	142
O10—H101⋯O4^iv	0.81	2.10	2.8518 (14)	155
O1—H11⋯O6^v	0.81	1.96	2.7661 (14)	175
Symmetry codes: (i) x, y+1, z; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x+1, y-1, z; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (v) x-1, y, z.

Data collection: COLLECT (Nonius, 2001 ); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: CAMERON (Watkin et al., 1996 ); software used to prepare material for publication: CRYSTALS.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809017656/fl2248sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809017656/fl2248Isup2.hkl

checkCIF report

Comment top

Until recently D-tagatose was a rare and expensive hexose; the price in the 2007–2008 Aldrich catalogue was 331.00 pounds sterling for 5 g (Porwell, 2007). It is now available cheaply in large quantities [around 5 pounds sterling per kg] prepared by either chemical (Beadle et al., 1992) or biotechnological (Granstrom et al., 2004; Izumori, 2002) techniques, and it is widely investigated as a low calorie sweetener (Skytte, 2002); the potential of D-tagatose as a chiral building block is also beginning to be recognized (Soengas et al., 2005; Watkin et al., 2005; Jones et al., 2007; Jones et al., 2008; Yoshihara et al., 2008). The crystal structure of another hitherto rare diasteroisomeric ketohexose, D-psicose, has recently been published (Kwiecien et al., 2008). A previous α-D-tagatose structure solution (Takagi et al., 1969), did not report either three-dimensional coordinates or bond lengths and angles. Although in aqueous solution both furanose and pyranose forms are present, only the α-pyranose crystallizes out. The crystal structure of the title compound (Fig. 1) consists of a network of hydrogen-bonded chains running parallel to the a axis (Fig.2). Referring to Table 1, O4—H41···O10 is the only intramolecular hydrogen bond detected in the structure. O12—H121···O4 and O1—H11···O6 link the molecules into chains, and O9—H91···O1 and O10—H101···O4 stabilize the structure with inter-chain hydrogen bonds. O4 is involved as an acceptor in two hydrogen bonds and as a donor in an almost linear hydrogen bond - the latter by means of H41. The crystal structure shows three equatorial groups and two axial groups, one of which is an axial anomeric hydroxyl group; this would be expected to be the most thermodynamically stable pyranose anomer. The fairly high value of the anisotropic displacement of O12 - compared to the other C and O atoms - is probably due to thermal motion. It results also in a higher - compared to the other H atoms - isotropic displacement for H121 i.e. the hydrogen atom connected to the last atom of the flexible C7—C11—O12 chain.

Related literature top

For the D-tagatose market price, syntheses and applications, see: Angyal (1991); Beadle et al. (1992); Granstrom et al. (2004); Izumori (2002); Skytte (2002); Porwell (2007). For the potential of the title compound as a chiral building block, see: Soengas et al. (2005); Jones et al. (2007, 2008); Yoshihara et al. (2008). For related crystallographic literature, see: Takagi et al. (1969); Görbitz (1999); Watkin et al. (2005); Kwiecien et al. (2008); Larson (1970).

Experimental top

In aqueous solution the major form present is α-D-tagatopyranose (71%) (Fig.1) with 18% of the β-pyranose and small amount of the furanoses (Angyal, 1991). The title compound was recrystallized from a 1:10 mixture of water and acetone allowing the slow competetive evaporation of the solvents, after which, transparent prismatic crystals appeared.

Computing details top

Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).

Figures top

	Fig. 1. The title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitary radius.
	Fig. 2. Packing diagram of title compound viewed down the a axis. Hydrogen bonds are shown as dotted lines.
	Fig. 3. D-Tagatose and α-D-tagatopyranose.

α-D-Tagatopyranose top

Crystal data top

C₆H₁₂O₆	F(000) = 384
M_r = 180.16	D_x = 1.675 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1344 reflections
a = 6.2201 (1) Å	θ = 5–32°
b = 6.5022 (1) Å	µ = 0.15 mm⁻¹
c = 17.6629 (4) Å	T = 190 K
V = 714.36 (2) Å³	Prism, colourless
Z = 4	0.50 × 0.30 × 0.20 mm

Data collection top

Nonius KappaCCD diffractometer	1351 reflections with I > 2.0σ(I)
Graphite monochromator	R_int = 0.010
ω scans	θ_max = 31.5°, θ_min = 5.6°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −9→9
T_min = 0.96, T_max = 0.97	k = −9→9
2343 measured reflections	l = −25→25
1378 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.025	Method = Modified Sheldrick w = 1/[σ²(F²) + ( 0.04P)² + 0.18P], where P = (max(F_o²,0) + 2F_c²)/3
wR(F²) = 0.065	(Δ/σ)_max = 0.000109
S = 0.97	Δρ_max = 0.34 e Å⁻³
1378 reflections	Δρ_min = −0.20 e Å⁻³
110 parameters	Extinction correction: Larson (1970), Equation 22
0 restraints	Extinction coefficient: 260 (40)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₆H₁₂O₆	V = 714.36 (2) Å³
M_r = 180.16	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.2201 (1) Å	µ = 0.15 mm⁻¹
b = 6.5022 (1) Å	T = 190 K
c = 17.6629 (4) Å	0.50 × 0.30 × 0.20 mm

Data collection top

Nonius KappaCCD diffractometer	1378 independent reflections
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	1351 reflections with I > 2.0σ(I)
T_min = 0.96, T_max = 0.97	R_int = 0.010
2343 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.065	H-atom parameters constrained
S = 0.97	Δρ_max = 0.34 e Å⁻³
1378 reflections	Δρ_min = −0.20 e Å⁻³
110 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	−0.20580 (13)	0.34108 (12)	0.17994 (4)	0.0157
C2	−0.02883 (15)	0.29006 (15)	0.13171 (5)	0.0113
C3	0.10689 (16)	0.47890 (15)	0.11569 (5)	0.0118
O4	−0.02429 (12)	0.62640 (12)	0.07662 (4)	0.0150
C5	0.29501 (17)	0.41697 (16)	0.06531 (6)	0.0143
O6	0.42202 (12)	0.25811 (12)	0.09985 (4)	0.0139
C7	0.30499 (16)	0.07510 (15)	0.11774 (5)	0.0118
C8	0.11083 (16)	0.12491 (15)	0.16890 (5)	0.0118
O9	0.18387 (14)	0.19838 (12)	0.24031 (4)	0.0171
O10	0.22054 (13)	−0.01458 (12)	0.05105 (4)	0.0142
C11	0.46654 (17)	−0.06848 (16)	0.15537 (6)	0.0155
O12	0.61351 (15)	−0.12797 (16)	0.09805 (5)	0.0271
H21	−0.0851	0.2365	0.0849	0.0134*
H31	0.1585	0.5338	0.1629	0.0151*
H51	0.3943	0.5322	0.0579	0.0174*
H52	0.2364	0.3698	0.0173	0.0181*
H81	0.0263	0.0023	0.1724	0.0147*
H112	0.5375	−0.0021	0.1979	0.0193*
H111	0.3929	−0.1876	0.1738	0.0194*
H41	0.0463	0.7255	0.0642	0.0240*
H91	0.1860	0.0956	0.2678	0.0275*
H121	0.7044	−0.2120	0.1130	0.0413*
H101	0.3225	−0.0416	0.0248	0.0252*
H11	−0.3163	0.3242	0.1565	0.0238*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0103 (3)	0.0192 (4)	0.0177 (3)	−0.0009 (3)	0.0026 (3)	−0.0047 (3)
C2	0.0102 (4)	0.0120 (4)	0.0118 (4)	−0.0005 (4)	0.0005 (3)	−0.0019 (3)
C3	0.0107 (4)	0.0107 (4)	0.0141 (4)	0.0001 (3)	−0.0003 (3)	0.0004 (3)
O4	0.0131 (3)	0.0119 (3)	0.0201 (3)	0.0026 (3)	−0.0007 (3)	0.0027 (3)
C5	0.0125 (4)	0.0121 (4)	0.0183 (4)	0.0022 (4)	0.0034 (4)	0.0041 (3)
O6	0.0097 (3)	0.0111 (3)	0.0209 (3)	−0.0001 (3)	−0.0007 (3)	0.0036 (3)
C7	0.0112 (4)	0.0100 (4)	0.0143 (4)	−0.0003 (4)	−0.0007 (3)	0.0007 (3)
C8	0.0124 (4)	0.0107 (4)	0.0122 (4)	−0.0020 (4)	−0.0001 (3)	−0.0004 (3)
O9	0.0243 (4)	0.0154 (3)	0.0115 (3)	−0.0007 (3)	−0.0033 (3)	0.0001 (3)
O10	0.0138 (3)	0.0151 (3)	0.0137 (3)	0.0009 (3)	0.0005 (3)	−0.0030 (3)
C11	0.0136 (4)	0.0139 (4)	0.0191 (4)	0.0026 (4)	−0.0015 (4)	0.0033 (4)
O12	0.0213 (4)	0.0322 (5)	0.0280 (4)	0.0161 (4)	0.0044 (4)	0.0078 (4)

Geometric parameters (Å, º) top

O1—C2	1.4309 (12)	O6—C7	1.4303 (12)
O1—H11	0.810	C7—C8	1.5426 (14)
C2—C3	1.5167 (14)	C7—O10	1.4155 (12)
C2—C8	1.5294 (14)	C7—C11	1.5241 (14)
C2—H21	0.963	C8—O9	1.4232 (11)
C3—O4	1.4359 (12)	C8—H81	0.957
C3—C5	1.5241 (14)	O9—H91	0.826
C3—H31	0.963	O10—H101	0.805
O4—H41	0.810	C11—O12	1.4178 (14)
C5—O6	1.4364 (12)	C11—H112	0.973
C5—H51	0.980	C11—H111	0.957
C5—H52	0.972	O12—H121	0.829

C2—O1—H11	108.5	O6—C7—C8	110.68 (8)
O1—C2—C3	110.58 (8)	O6—C7—O10	110.35 (8)
O1—C2—C8	110.13 (8)	C8—C7—O10	106.46 (8)
C3—C2—C8	109.41 (8)	O6—C7—C11	105.69 (8)
O1—C2—H21	108.4	C8—C7—C11	112.92 (8)
C3—C2—H21	109.6	O10—C7—C11	110.81 (8)
C8—C2—H21	108.7	C7—C8—C2	109.91 (8)
C2—C3—O4	108.31 (8)	C7—C8—O9	109.85 (8)
C2—C3—C5	108.81 (8)	C2—C8—O9	109.04 (8)
O4—C3—C5	109.40 (8)	C7—C8—H81	107.0
C2—C3—H31	108.9	C2—C8—H81	107.5
O4—C3—H31	111.0	O9—C8—H81	113.5
C5—C3—H31	110.3	C8—O9—H91	104.7
C3—O4—H41	110.7	C7—O10—H101	106.1
C3—C5—O6	111.36 (8)	C7—C11—O12	106.31 (8)
C3—C5—H51	111.1	C7—C11—H112	111.4
O6—C5—H51	105.1	O12—C11—H112	112.4
C3—C5—H52	107.7	C7—C11—H111	109.2
O6—C5—H52	110.4	O12—C11—H111	109.3
H51—C5—H52	111.2	H112—C11—H111	108.3
C5—O6—C7	114.34 (8)	C11—O12—H121	113.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O10ⁱ	0.81	2.02	2.8236 (14)	171
O9—H91···O1ⁱⁱ	0.83	1.90	2.7203 (14)	173
O12—H121···O4ⁱⁱⁱ	0.83	2.09	2.7875 (14)	142
O10—H101···O4^iv	0.81	2.10	2.8518 (14)	155
O1—H11···O6^v	0.81	1.96	2.7661 (14)	175

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

Experimental details

Crystal data
Chemical formula	C₆H₁₂O₆
M_r	180.16
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	190
a, b, c (Å)	6.2201 (1), 6.5022 (1), 17.6629 (4)
V (Å³)	714.36 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.50 × 0.30 × 0.20

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.96, 0.97
No. of measured, independent and observed [I > 2.0σ(I)] reflections	2343, 1378, 1351
R_int	0.010
(sin θ/λ)_max (Å⁻¹)	0.735

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.065, 0.97
No. of reflections	1378
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.20

Computer programs: COLLECT (Nonius, 2001), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O10ⁱ	0.81	2.02	2.8236 (14)	171
O9—H91···O1ⁱⁱ	0.83	1.90	2.7203 (14)	173
O12—H121···O4ⁱⁱⁱ	0.83	2.09	2.7875 (14)	142
O10—H101···O4^iv	0.81	2.10	2.8518 (14)	155
O1—H11···O6^v	0.81	1.96	2.7661 (14)	175

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

Footnotes

‡Visiting Scientist at the Department of Chemical Crystallography Chemical Research Laboratory Mansfield Road Oxford OX1 3TA England.

Acknowledgements

Arla Foods generously provided a sample of D-tagatose, obtained as described (Beadle et al., 1992) from D-galactose, for crystallization.

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