Hydrogen-bonded sheets of R₂²(10) and R₄⁴(24) rings in 1-de­oxy-1-morpholino-D-fructopyran­ose

In the title compound, C₁₀H₁₉NO₆, both rings adopt almost perfect chair conformations and their mutual orientation is influenced by an intra­molecular O—H...N hydrogen bond. The mol­ecules are linked by three independent O—H...O hydrogen bonds into sheets containing equal numbers of R₂²(10) and R₄⁴(24) rings.

S1. Comment

As a possible intermediate for the synthesis of azasugars from glucose, we have prepared 1-deoxy-1-morpholino-D-fructopyranose, (I), by the reaction of D-glucose with morpholine, utilizing an Amadori rearrangement of the initially formed N-D-glucosylmorpholine (Hodge & Rist, 1953).

In (I), the sugar component has the pyranose form (Fig. 1), and the two independent rings both adopt almost perfect chair conformations. The ring puckering angles θ (Cremer & Pople, 1975) are 177.3 (2)° for the atom sequence O1—C2—C3—C4—C5—C6 and 1.4 (2)° for the atom sequence O11—C12—C13—-N14—C15—C16; the ideal values for a chair conformer are (180n)°, where n represents zero or an integer. In the pyranose ring, the substituent atoms O2 and O5 both occupy axial sites but all other non-H substituents adopt equatorial sites. The mutual orientation of the two independent rings appears to be influenced, and possibly controlled, by the presence of an intramolecular O—H···N hydrogen bond (Table 1). The coordination at the morpholine N atom is markedly pyramidal with a sum of bond angles of 333.6 (2)°; the bond distances and the remaining bond angles show no unexpected features.

The overall conformation adopted by (I) is very similar to those found for three close analogues retrieved from the Cambridge Structural Database (Allen, 2002). In each of EDEVUU, (II), where the amine component in the synthesis is dibenzylamine (Hou et al., 2001), ZIVTON, (III), where the amine component is 4-toluidine (Gomez de Anderez et al., 1996), and the zwitterionic YUXCUP, (IV), where the amine component is glycine (Mossine et al., 1995), the hydroxy groups corresponding to O2 and O5 in (I) occupy axial sites. There is an intramolecular O—H···N hydrogen bond in (II) exactly analogous to that in (I), while in (IV) the two intramolecular hydrogen bonds are both of N—H···O type; the H atoms bonded to N and O atoms in (II) could not be located.

Each of the other three hydroxyl groups acts as a donor in intermolecular hydrogen bonds, all with O atoms as acceptors (Table 1), leading to the formation of a hydrogen-bonded supramolecular structure which is two-dimensional. Since the only symmetry operations available are translations, the formation of the supramolecular structure is very readily analysed in terms of two simple one-dimensional substructures. In the first of these substructures, atoms O3 and O4 in the molecule at (x, y, z) act as hydrogen-bond donors, respectively, to atoms O1 and O5, both in the molecule at (x, 1 + y, z), so generating a C(5)C(5)[R₂²(10)] chain of rings (Bernstein et al., 1995) running parallel to the [010] direction (Fig. 2). In the second substructure, atom O5 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the morpholine atom O11 in the molecule at (1 + x, 1 + y, 1 + z), so generating a simple C(11) chain running parallel to the [111] direction (Fig. 2). The combination of the [010] and [111] chains generates a sheet lying parallel to (101) and containing alternating ribbons of antidromic (Steiner, 2002) R₂²(10) and antidromic R₄⁴(24) rings, both running parallel to the [010] direction (Fig. 2). There are no significant direction-specific interactions between adjacent sheets.

The two-dimensional hydrogen-bonded supramolecular structure found here for (I) may be contrasted with the one- and three-dimensional structures found in (II) and (IV), respectively. In (II), the combination of three intermolecular O—H···O hydrogen bonds generates a complex chain of rings (Hou et al., 2001), while in (IV), a combination of four intermolecular O—H···O hydrogen bonds and two intermolecular N—H···O hydrogen bonds links the molecules into a single three-dimensional framework structure (Mossine et al., 1995). Although the H atoms bonded to the N and O atoms in (II) were not located (Gomez de Anderez et al., 1996), the close intermolecular contacts involving N and O atoms suggest that the hydrogen-bonded supramolecular structure is probably two-dimensional. Hence, modest changes in the nature of the amino component can readily alter the dimensionality of the hydrogen-bonded structure.

Related literature

For related literature, see: Allen (2002); Bernstein et al. (1995); Cremer & Pople (1975); Gomez de Anderez, Gil, Helliwell & Mata Segreda (1996); Hodge & Rist (1953); Hou et al. (2001); Mossine et al. (1995); Steiner (2002).

S2. Experimental

A sample of compound (I) was prepared according to the published procedure (Hodge & Rist, 1953). Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in methanol [m.p. 419–421 K; literature m.p. (Hodge & Rist, 1953) 418–419 K].

S3. Refinement

Crystals of compound (I) are triclinic: space group P1 was selected and confirmed by the structure analysis. The labelling of the C atoms in the sugar component follows the conventional labelling for the glucose starting material. All H atoms were located in difference maps and then treated as riding atoms: the H atoms bonded to C atoms were placed in geometrically idealized positions, with C—H distances of 0.99 Å (CH₂) or 1.00 Å (CH), and with U_iso(H) = 1.2U_eq(C); H atoms bonded to O atoms were permitted to ride at the positions deduced from the difference maps, with U_iso(H) = 1.5U_eq(O), giving O—H distances in the range 0.86–0.93 Å. The only restraints were those required by the space group to fix the origin. In the absence of significant resonant scattering, the Friedel-equivalent reflections were merged and the absolute configuration was set by reference to the known absolute configuration of the starting material D-glucose.

Computing details

Data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: Sir2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. A molecule of (I), showing the atom-labelling scheme and the intramolecular hydrogen bond. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded sheet of R2^2(10) and R4^4(24) rings. For the sake of clarity, H atoms bonded to C atoms have been omitted.

1-deoxy-1-morpholino-D-fructopyranose

Crystal data

C10H19NO6	Z = 1
Mr = 249.26	F(000) = 134
Triclinic, P1	Dx = 1.477 Mg m^−3
Hall symbol: P 1	Melting point: 420 K
a = 5.2767 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 5.5375 (5) Å	Cell parameters from 1279 reflections
c = 10.2809 (13) Å	θ = 3.9–27.5°
α = 104.598 (10)°	µ = 0.12 mm^−1
β = 90.393 (12)°	T = 120 K
γ = 104.834 (10)°	Plate, colourless
V = 280.19 (6) Å^3	0.52 × 0.27 × 0.06 mm

Data collection

Bruker–Nonius KappaCCD diffractometer	1279 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1163 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ϕ & ω scans	θmax = 27.5°, θmin = 3.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −6→6
Tmin = 0.979, Tmax = 0.993	k = −6→7
7471 measured reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.075	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0351P)^2 + 0.0939P] where P = (Fo^2 + 2Fc^2)/3
1279 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.29 e Å^−3
3 restraints	Δρmin = −0.23 e Å^−3

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

	x	y	z	Uiso*/Ueq
C1	0.8058 (4)	0.5379 (4)	0.4170 (2)	0.0129 (4)
O1	0.6404 (3)	0.4344 (3)	0.61585 (15)	0.0123 (3)
O2	0.4747 (3)	0.7179 (3)	0.52752 (17)	0.0143 (3)
O3	0.9703 (3)	1.0861 (3)	0.58303 (16)	0.0160 (4)
O4	0.9784 (3)	1.1528 (3)	0.87384 (17)	0.0170 (4)
O5	0.9330 (3)	0.6445 (3)	0.87697 (18)	0.0175 (4)
O11	0.3306 (3)	−0.0073 (3)	0.08231 (17)	0.0177 (4)
N14	0.5902 (4)	0.3908 (4)	0.31449 (19)	0.0133 (4)
C2	0.7003 (4)	0.6418 (4)	0.5512 (2)	0.0116 (5)
C3	0.9004 (5)	0.8760 (4)	0.6437 (2)	0.0122 (4)
C4	0.7911 (4)	0.9523 (4)	0.7804 (2)	0.0128 (5)
C5	0.7099 (5)	0.7228 (4)	0.8417 (2)	0.0141 (5)
C6	0.5232 (4)	0.4989 (4)	0.7411 (2)	0.0137 (5)
C12	0.2641 (5)	−0.0188 (5)	0.2152 (2)	0.0175 (5)
C13	0.4932 (5)	0.1186 (4)	0.3194 (2)	0.0164 (5)
C15	0.6631 (5)	0.3968 (4)	0.1777 (2)	0.0157 (5)
C16	0.4290 (5)	0.2562 (5)	0.0778 (2)	0.0178 (5)
H1A	0.9161	0.6841	0.3866	0.016*
H1B	0.9174	0.4248	0.4287	0.016*
H2	0.3923	0.6026	0.4499	0.022*
H3	0.8297	1.1600	0.5928	0.024*
H4	0.9955	1.3009	0.8587	0.026*
H5	1.0355	0.7735	0.9443	0.026*
H3A	1.0631	0.8221	0.6580	0.015*
H4A	0.6330	1.0148	0.7681	0.015*
H5A	0.6175	0.7736	0.9247	0.017*
H6A	0.4773	0.3462	0.7785	0.016*
H6B	0.3591	0.5460	0.7251	0.016*
H12A	0.2032	−0.2024	0.2171	0.021*
H12B	0.1171	0.0610	0.2387	0.021*
H13A	0.4366	0.1119	0.4103	0.020*
H13B	0.6361	0.0313	0.3010	0.020*
H15A	0.8080	0.3134	0.1553	0.019*
H15B	0.7256	0.5786	0.1729	0.019*
H16A	0.2882	0.3458	0.0979	0.021*
H16B	0.4804	0.2608	−0.0141	0.021*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0154 (8)	0.0102 (8)	0.0103 (8)	0.0026 (6)	0.0029 (6)	0.0018 (6)
O2	0.0118 (8)	0.0166 (8)	0.0150 (8)	0.0056 (6)	−0.0012 (6)	0.0032 (6)
O3	0.0165 (8)	0.0126 (8)	0.0195 (9)	0.0020 (6)	0.0019 (7)	0.0074 (7)
O4	0.0239 (9)	0.0085 (7)	0.0153 (8)	0.0017 (7)	−0.0062 (7)	−0.0002 (6)
O5	0.0222 (9)	0.0129 (8)	0.0166 (8)	0.0057 (7)	−0.0074 (7)	0.0014 (6)
O11	0.0203 (9)	0.0150 (8)	0.0134 (8)	0.0008 (7)	0.0002 (7)	−0.0002 (6)
N14	0.0125 (9)	0.0134 (10)	0.0110 (9)	−0.0008 (7)	0.0000 (7)	0.0025 (7)
C1	0.0124 (11)	0.0133 (10)	0.0114 (11)	0.0009 (9)	0.0019 (8)	0.0027 (8)
C2	0.0097 (11)	0.0106 (10)	0.0138 (11)	0.0009 (8)	−0.0006 (9)	0.0038 (9)
C3	0.0136 (11)	0.0116 (10)	0.0119 (10)	0.0040 (8)	0.0008 (8)	0.0030 (8)
C4	0.0149 (11)	0.0102 (10)	0.0132 (11)	0.0040 (9)	−0.0013 (9)	0.0023 (9)
C5	0.0194 (12)	0.0121 (11)	0.0111 (11)	0.0066 (9)	0.0018 (9)	0.0014 (9)
C6	0.0155 (11)	0.0120 (11)	0.0139 (11)	0.0029 (9)	0.0031 (9)	0.0049 (9)
C12	0.0159 (12)	0.0166 (12)	0.0158 (12)	−0.0001 (10)	0.0014 (9)	0.0015 (9)
C13	0.0183 (12)	0.0129 (11)	0.0152 (11)	−0.0007 (9)	−0.0008 (9)	0.0037 (9)
C15	0.0163 (12)	0.0177 (11)	0.0114 (11)	0.0014 (9)	0.0013 (9)	0.0040 (9)
C16	0.0185 (12)	0.0198 (12)	0.0130 (11)	0.0029 (9)	−0.0014 (9)	0.0027 (9)

Geometric parameters (Å, º)

O1—C6	1.436 (3)	C4—C5	1.524 (3)
O1—C2	1.436 (3)	C4—H4A	1.00
O2—C2	1.399 (3)	C5—C6	1.514 (3)
O2—H2	0.9112	C5—H5A	1.00
O3—C3	1.424 (3)	C6—H6A	0.99
O3—H3	0.9295	C6—H6B	0.99
O4—C4	1.421 (3)	C12—C13	1.513 (3)
O4—H4	0.8553	C12—H12A	0.99
O5—C5	1.428 (3)	C12—H12B	0.99
O5—H5	0.9108	C13—H13A	0.99
O11—C12	1.425 (3)	C13—H13B	0.99
O11—C16	1.431 (3)	C15—C16	1.508 (3)
N14—C1	1.464 (3)	C15—H15A	0.99
N14—C15	1.467 (3)	C15—H15B	0.99
N14—C13	1.476 (3)	C16—H16A	0.99
C2—C1	1.523 (3)	C16—H16B	0.99
C2—C3	1.537 (3)	C1—H1A	0.99
C3—C4	1.525 (3)	C1—H1B	0.99
C3—H3A	1.00
C6—O1—C2	113.03 (16)	C5—C6—H6A	109.5
C2—O2—H2	105.2	O1—C6—H6B	109.5
C3—O3—H3	105.5	C5—C6—H6B	109.5
C4—O4—H4	112.3	H6A—C6—H6B	108.1
C5—O5—H5	109.1	O11—C12—C13	112.51 (19)
C12—O11—C16	110.28 (17)	O11—C12—H12A	109.1
C1—N14—C15	112.40 (18)	C13—C12—H12A	109.1
C1—N14—C13	112.23 (17)	O11—C12—H12B	109.1
C15—N14—C13	108.98 (17)	C13—C12—H12B	109.1
O2—C2—O1	111.04 (18)	H12A—C12—H12B	107.8
O2—C2—C1	109.26 (19)	N14—C13—C12	109.47 (19)
O1—C2—C1	106.57 (17)	N14—C13—H13A	109.8
O2—C2—C3	108.22 (17)	C12—C13—H13A	109.8
O1—C2—C3	109.06 (16)	N14—C13—H13B	109.8
C1—C2—C3	112.71 (17)	C12—C13—H13B	109.8
O3—C3—C4	112.13 (17)	H13A—C13—H13B	108.2
O3—C3—C2	111.32 (17)	N14—C15—C16	109.92 (18)
C4—C3—C2	109.58 (17)	N14—C15—H15A	109.7
O3—C3—H3A	107.9	C16—C15—H15A	109.7
C4—C3—H3A	107.9	N14—C15—H15B	109.7
C2—C3—H3A	107.9	C16—C15—H15B	109.7
O4—C4—C5	107.62 (17)	H15A—C15—H15B	108.2
O4—C4—C3	111.81 (18)	O11—C16—C15	111.57 (19)
C5—C4—C3	111.30 (17)	O11—C16—H16A	109.3
O4—C4—H4A	108.7	C15—C16—H16A	109.3
C5—C4—H4A	108.7	O11—C16—H16B	109.3
C3—C4—H4A	108.7	C15—C16—H16B	109.3
O5—C5—C6	109.49 (18)	H16A—C16—H16B	108.0
O5—C5—C4	111.32 (19)	N14—C1—C2	110.89 (18)
C6—C5—C4	109.14 (18)	N14—C1—H1A	109.5
O5—C5—H5A	109.0	C2—C1—H1A	109.5
C6—C5—H5A	109.0	N14—C1—H1B	109.5
C4—C5—H5A	109.0	C2—C1—H1B	109.5
O1—C6—C5	110.79 (18)	H1A—C1—H1B	108.0
O1—C6—H6A	109.5
C6—O1—C2—O2	−57.6 (2)	C2—O1—C6—C5	−62.2 (2)
C6—O1—C2—C1	−176.47 (17)	O5—C5—C6—O1	−66.0 (2)
C6—O1—C2—C3	61.6 (2)	C4—C5—C6—O1	56.1 (2)
O2—C2—C3—O3	−60.2 (2)	C16—O11—C12—C13	−56.5 (2)
O1—C2—C3—O3	178.93 (18)	C1—N14—C13—C12	177.65 (19)
C1—C2—C3—O3	60.8 (2)	C15—N14—C13—C12	−57.2 (2)
O2—C2—C3—C4	64.4 (2)	O11—C12—C13—N14	57.2 (3)
O1—C2—C3—C4	−56.5 (2)	C1—N14—C15—C16	−176.57 (19)
C1—C2—C3—C4	−174.60 (18)	C13—N14—C15—C16	58.4 (2)
O3—C3—C4—O4	−61.3 (2)	C12—O11—C16—C15	56.9 (2)
C2—C3—C4—O4	174.58 (17)	N14—C15—C16—O11	−58.8 (2)
O3—C3—C4—C5	178.32 (18)	C15—N14—C1—C2	151.84 (18)
C2—C3—C4—C5	54.2 (2)	C13—N14—C1—C2	−84.9 (2)
O4—C4—C5—O5	−55.4 (2)	O2—C2—C1—N14	−37.5 (2)
C3—C4—C5—O5	67.4 (2)	O1—C2—C1—N14	82.6 (2)
O4—C4—C5—C6	−176.42 (18)	C3—C2—C1—N14	−157.81 (18)
C3—C4—C5—C6	−53.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N14	0.91	2.06	2.652 (3)	122
O3—H3···O1^i	0.93	1.99	2.874 (2)	158
O4—H4···O5^i	0.86	1.98	2.785 (2)	158
O5—H5···O11^ii	0.91	2.01	2.897 (2)	164

Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z+1.