Crystal structure of 1,2,3,5-di-O-methyl­ene-α-d-xylo­furan­ose

Tiritiris, I.; Tussetschläger, S.; Kantlehner, W.

doi:10.1107/S2056989015020022

organic compounds

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Volume 71| Part 11| November 2015| Page o889

https://doi.org/10.1107/S2056989015020022

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Crystal structure of 1,2,3,5-di-O-methylene-α-D-xylofuranose

Ioannis Tiritiris,^a Stefan Tussetschläger ^a and Willi Kantlehner ^a ^*

^aFakultät Chemie/Organische Chemie, Hochschule Aalen, Beethovenstrasse 1, D-73430 Aalen, Germany
^*Correspondence e-mail: willi.kantlehner@hs-aalen.de

Edited by M. Zeller, Youngstown State University, USA (Received 18 October 2015; accepted 22 October 2015; online 28 October 2015)

The title compound, C₇H₁₀O₅, was synthesized by reaction of D-xylose with paraformaldehyde. In the crystal, the central part of the molecule consists of a five-membered C₄O ring with an envelope conformation, with the methine C atom adjacent to the O atom being the flap. The protected O atoms of both cyclic acetal groups are oriented so that the four chiral C atoms of the furanose part show an R configuration. C—H⋯O hydrogen bonds are present between adjacent molecules, generating a three-dimensional network.

Keywords: crystal structure; acetalation; D-xylose; C—H⋯O hydrogen bonds.

CCDC reference: 1432701

1. Related literature

For the synthesis of 1,2,3,5-di-O-methylene-α-D-xylose, see: Schmidt & Nieswandt (1949 ). For the synthesis and characterization of chiral 1,3-dihydrobenzo[c]furan derivatives and their intermediates, see: Ewing et al. (2000 ).

2. Experimental

2.1. Crystal data

C₇H₁₀O₅
M_r = 174.15
Orthorhombic C 222₁
a = 8.5509 (11) Å
b = 8.6327 (11) Å
c = 20.057 (3) Å
V = 1480.6 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 100 K
0.53 × 0.16 × 0.13 mm

2.2. Data collection

Bruker Kappa APEXII DUO diffractometer
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.707, T_max = 0.744
12973 measured reflections
1858 independent reflections
1667 reflections with I > 2σ(I)
R_int = 0.048

2.3. Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.074
S = 1.05
1858 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.23 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
C1—H1⋯O3ⁱ	1.00	2.57	3.311 (2)	131
C3—H3B⋯O1ⁱⁱ	0.99	2.54	3.458 (2)	154
C4—H4⋯O4ⁱⁱ	1.00	2.46	3.406 (2)	157
C5—H5⋯O2ⁱⁱⁱ	1.00	2.41	3.385 (2)	166
C7—H7A⋯O3^iv	0.99	2.47	3.337 (2)	147
C7—H7B⋯O5^v	0.99	2.55	3.390 (2)	142
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) x, -y+1, -z; (iv) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (v) x, -y+2, -z.

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXL97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: SHELXL2014.

Supporting information

CCDC reference: 1432701

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989015020022/zl2650sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015020022/zl2650Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015020022/zl2650Isup3.cml

checkCIF report

Comment top

The synthesis of the protected sugar 1,2,3,5-di-O-methylene-α-D-xylofuranose has been well known for many years (Schmidt & Nieswandt, 1949), its crystal structure, however, remained undetermined. According to the structure analysis, which we would like to now report, the central part of the molecule consists of a five-membered C₄O ring, which is build by the carbon atoms C1, C4, C5 and C6 and show an envelope conformation (Fig. 1). The protected oxygen atoms of both cyclic acetal groups are oriented in a way so that the four chiral carbon atoms of the furanose part exhibit R-configuration. Compounds with similar structures have been obtained as intermediates by using 1,2-O-isopropylidene-α-D-xylofuranose as a protecting group to synthesize chiral 1,3-dihydrobenzo[c]furan derivatives (Ewing et al., 2000). In the crystal structure of the title compound, C—H···O hydrogen bonds between adjacent molecules are present [d(H···O) = 2.41–2.57 Å] (Table 1), generating a three-dimensional network (Fig. 2).

Related literature top

For the synthesis of 1,2,3,5-di-O-methylene-α-D-xylose, see: Schmidt & Nieswandt, 1949. For the synthesis and characterization of chiral 1,3-dihydrobenzo[c]furan derivatives and their intermediates see: Ewing et al., 2000.

Experimental top

According to the literature (Schmidt & Nieswandt, 1949) a mixture of 7.5 g (50 mmol) D-xylose and 10.0 g (333 mmol) paraformaldehyde were heated to 373 K. After treating the mixture with 20 g (204 mmol) of concentrated phosphoric acid (85%) and subsequent cooling to room temperature, the mixture has been extracted five times with chloroform. The combined extracts were washed and dried over sodium sulfate. After evaporation of the solvent, the crude product was destilled under reduced presure using a 20 cm Vigreux column. The fraction at 363 K (0.1 mbar) contained 3.4 g (39%) of the title compound. Single crystals were obtained by recystallization from petroleum ether and colorless needles were formed suitable for X-ray analysis.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures top

	Fig. 1. The structure of the title compound with displacement ellipsoids at the 50% probability level.
	Fig. 2. C—H···O hydrogen bonds (black dashed lines) between adjacent molecules in the crystal structure of the title compound (bc view).

1,2,3,5-di-O-Methylene-α-D-xylofuranose top

Crystal data top

C₇H₁₀O₅	D_x = 1.563 Mg m⁻³
M_r = 174.15	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, C222₁	Cell parameters from 1667 reflections
a = 8.5509 (11) Å	θ = 2.0–28.4°
b = 8.6327 (11) Å	µ = 0.14 mm⁻¹
c = 20.057 (3) Å	T = 100 K
V = 1480.6 (3) Å³	Needle, colorless
Z = 8	0.53 × 0.16 × 0.13 mm
F(000) = 736

Data collection top

Bruker Kappa APEXII DUO diffractometer	1858 independent reflections
Radiation source: fine-focus sealed tube	1667 reflections with I > 2σ(I)
Triumph monochromator	R_int = 0.048
φ scans, and ω scans	θ_max = 28.4°, θ_min = 2.0°
Absorption correction: multi-scan (Blessing, 1995)	h = −11→9
T_min = 0.707, T_max = 0.744	k = −11→11
12973 measured reflections	l = −26→26

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.074	w = 1/[σ²(F_o²) + (0.0335P)² + 0.5951P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1858 reflections	Δρ_max = 0.23 e Å⁻³
110 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0061 (7)

Crystal data top

C₇H₁₀O₅	V = 1480.6 (3) Å³
M_r = 174.15	Z = 8
Orthorhombic, C222₁	Mo Kα radiation
a = 8.5509 (11) Å	µ = 0.14 mm⁻¹
b = 8.6327 (11) Å	T = 100 K
c = 20.057 (3) Å	0.53 × 0.16 × 0.13 mm

Data collection top

Bruker Kappa APEXII DUO diffractometer	1858 independent reflections
Absorption correction: multi-scan (Blessing, 1995)	1667 reflections with I > 2σ(I)
T_min = 0.707, T_max = 0.744	R_int = 0.048
12973 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 1.05	Δρ_max = 0.23 e Å⁻³
1858 reflections	Δρ_min = −0.20 e Å⁻³
110 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
O1	0.35776 (16)	0.73794 (16)	0.15438 (7)	0.0209 (3)
C1	0.2196 (2)	0.6569 (2)	0.17647 (10)	0.0183 (4)
H1	0.1430	0.7322	0.1957	0.022*
O2	0.23608 (16)	0.44818 (15)	0.09492 (7)	0.0200 (3)
C2	0.2642 (3)	0.5386 (3)	0.22854 (11)	0.0250 (5)
H2A	0.3352	0.5874	0.2614	0.030*
H2B	0.1689	0.5051	0.2526	0.030*
O3	0.33921 (17)	0.40599 (17)	0.20058 (7)	0.0224 (3)
C3	0.2474 (2)	0.3445 (2)	0.14901 (11)	0.0229 (4)
H3A	0.1413	0.3217	0.1662	0.027*
H3B	0.2941	0.2459	0.1335	0.027*
O4	0.28366 (16)	0.95180 (15)	0.08815 (8)	0.0229 (3)
C4	0.1535 (2)	0.5865 (2)	0.11288 (10)	0.0175 (4)
H4	0.0381	0.5689	0.1160	0.021*
O5	0.07534 (18)	0.81726 (16)	0.04937 (8)	0.0239 (4)
C5	0.1948 (2)	0.7043 (2)	0.05959 (10)	0.0185 (4)
H5	0.2246	0.6526	0.0168	0.022*
C6	0.3328 (2)	0.7957 (2)	0.08923 (10)	0.0186 (4)
H6	0.4287	0.7817	0.0613	0.022*
C7	0.1181 (2)	0.9509 (2)	0.08583 (11)	0.0213 (4)
H7A	0.0741	0.9467	0.1314	0.026*
H7B	0.0788	1.0454	0.0634	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0202 (5)	0.0228 (5)	0.0195 (5)	−0.0066 (4)	−0.0026 (4)	0.0012 (4)
C1	0.0181 (7)	0.0197 (7)	0.0172 (7)	−0.0015 (6)	0.0024 (6)	−0.0010 (6)
O2	0.0258 (5)	0.0129 (5)	0.0213 (5)	0.0043 (4)	−0.0029 (4)	−0.0014 (4)
C2	0.0290 (8)	0.0283 (8)	0.0176 (7)	−0.0006 (7)	0.0028 (6)	0.0026 (6)
O3	0.0213 (5)	0.0241 (5)	0.0217 (5)	0.0026 (4)	−0.0023 (4)	0.0048 (5)
C3	0.0236 (8)	0.0181 (7)	0.0268 (8)	−0.0009 (6)	−0.0026 (6)	0.0042 (6)
O4	0.0200 (5)	0.0141 (5)	0.0347 (6)	−0.0002 (4)	0.0032 (5)	−0.0002 (5)
C4	0.0171 (6)	0.0139 (7)	0.0214 (7)	0.0012 (6)	−0.0024 (6)	−0.0014 (6)
O5	0.0275 (6)	0.0145 (5)	0.0297 (6)	0.0034 (4)	−0.0094 (5)	−0.0004 (5)
C5	0.0245 (7)	0.0149 (7)	0.0162 (7)	0.0041 (6)	−0.0023 (6)	−0.0026 (5)
C6	0.0190 (7)	0.0164 (7)	0.0205 (7)	0.0024 (5)	0.0046 (6)	0.0005 (6)
C7	0.0220 (7)	0.0153 (7)	0.0267 (8)	0.0002 (5)	0.0004 (6)	−0.0015 (7)

Geometric parameters (Å, º) top

O1—C6	1.4147 (18)	C3—H3B	0.9900
O1—C1	1.4429 (17)	O4—C6	1.4119 (17)
C1—C2	1.509 (2)	O4—C7	1.4164 (18)
C1—C4	1.522 (2)	C4—C5	1.517 (2)
C1—H1	1.0000	C4—H4	1.0000
O2—C3	1.4099 (19)	O5—C7	1.4139 (18)
O2—C4	1.4333 (16)	O5—C5	1.4269 (17)
C2—O3	1.4272 (19)	C5—C6	1.539 (2)
C2—H2A	0.9900	C5—H5	1.0000
C2—H2B	0.9900	C6—H6	1.0000
O3—C3	1.4029 (18)	C7—H7A	0.9900
C3—H3A	0.9900	C7—H7B	0.9900

C6—O1—C1	109.33 (11)	C5—C4—C1	103.67 (11)
O1—C1—C2	109.50 (12)	O2—C4—H4	112.0
O1—C1—C4	103.92 (11)	C5—C4—H4	112.0
C2—C1—C4	113.81 (12)	C1—C4—H4	112.0
O1—C1—H1	109.8	C7—O5—C5	107.35 (11)
C2—C1—H1	109.8	O5—C5—C4	113.12 (13)
C4—C1—H1	109.8	O5—C5—C6	104.72 (10)
C3—O2—C4	111.67 (11)	C4—C5—C6	104.48 (12)
O3—C2—C1	112.60 (12)	O5—C5—H5	111.4
O3—C2—H2A	109.1	C4—C5—H5	111.4
C1—C2—H2A	109.1	C6—C5—H5	111.4
O3—C2—H2B	109.1	O4—C6—O1	113.30 (12)
C1—C2—H2B	109.1	O4—C6—C5	104.77 (11)
H2A—C2—H2B	107.8	O1—C6—C5	106.97 (11)
C3—O3—C2	109.98 (12)	O4—C6—H6	110.5
O3—C3—O2	111.43 (12)	O1—C6—H6	110.5
O3—C3—H3A	109.3	C5—C6—H6	110.5
O2—C3—H3A	109.3	O5—C7—O4	106.26 (12)
O3—C3—H3B	109.3	O5—C7—H7A	110.5
O2—C3—H3B	109.3	O4—C7—H7A	110.5
H3A—C3—H3B	108.0	O5—C7—H7B	110.5
C6—O4—C7	107.02 (11)	O4—C7—H7B	110.5
O2—C4—C5	105.46 (11)	H7A—C7—H7B	108.7
O2—C4—C1	111.11 (12)

C6—O1—C1—C2	154.82 (12)	O2—C4—C5—O5	151.81 (11)
C6—O1—C1—C4	32.88 (14)	C1—C4—C5—O5	−91.33 (14)
O1—C1—C2—O3	−74.81 (15)	O2—C4—C5—C6	−94.88 (12)
C4—C1—C2—O3	40.99 (18)	C1—C4—C5—C6	21.97 (14)
C1—C2—O3—C3	−52.63 (16)	C7—O4—C6—O1	−94.14 (14)
C2—O3—C3—O2	65.51 (15)	C7—O4—C6—C5	22.11 (15)
C4—O2—C3—O3	−65.43 (15)	C1—O1—C6—O4	96.17 (13)
C3—O2—C4—C5	162.32 (12)	C1—O1—C6—C5	−18.77 (14)
C3—O2—C4—C1	50.63 (15)	O5—C5—C6—O4	−4.41 (15)
O1—C1—C4—O2	79.61 (13)	C4—C5—C6—O4	−123.57 (12)
C2—C1—C4—O2	−39.42 (17)	O5—C5—C6—O1	116.12 (12)
O1—C1—C4—C5	−33.22 (14)	C4—C5—C6—O1	−3.04 (14)
C2—C1—C4—C5	−152.25 (13)	C5—O5—C7—O4	29.22 (16)
C7—O5—C5—C4	98.23 (14)	C6—O4—C7—O5	−32.32 (17)
C7—O5—C5—C6	−14.93 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O3ⁱ	1.00	2.57	3.311 (2)	131
C3—H3B···O1ⁱⁱ	0.99	2.54	3.458 (2)	154
C4—H4···O4ⁱⁱ	1.00	2.46	3.406 (2)	157
C5—H5···O2ⁱⁱⁱ	1.00	2.41	3.385 (2)	166
C7—H7A···O3^iv	0.99	2.47	3.337 (2)	147
C7—H7B···O5^v	0.99	2.55	3.390 (2)	142

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O3ⁱ	1.00	2.57	3.311 (2)	131
C3—H3B···O1ⁱⁱ	0.99	2.54	3.458 (2)	154
C4—H4···O4ⁱⁱ	1.00	2.46	3.406 (2)	157
C5—H5···O2ⁱⁱⁱ	1.00	2.41	3.385 (2)	166
C7—H7A···O3^iv	0.99	2.47	3.337 (2)	147
C7—H7B···O5^v	0.99	2.55	3.390 (2)	142

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

Acknowledgements

The authors thank Dr W. Frey (Institut für Organische Chemie, Universität Stuttgart) for measuring the diffraction data.

References

Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ewing, D. F., Len, C., Mackenzie, G., Ronco, G. & Villa, P. (2000). Tetrahedron Asymmetry, 11, 4995–5002. CSD CrossRef CAS Google Scholar
Schmidt, O. Th. & Nieswandt, G. (1949). Chem. Ber. 1, 1–7. CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar