2,2-Di-C-meth­oxy-1,4:3,6-dianhydro­mannitol

The title compound, C₈H₁₄O₅, is a 1,4:3,6-dianhydro-D-fructose derivative. Its structure consists of two fused tetra­hydro­furan rings with a cis ring junction, giving a V-shaped mol­ecule with an angle between the two rings of 129.9°. Inter­molecular O—H...O hydrogen bonds help stabilize the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.051
• wR factor = 0.138
• Data-to-parameter ratio = 6.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.95

Alert level C
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       6.74
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.10 Ratio
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          6

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.00
           From the CIF: _reflns_number_total                829
           Count of symmetry unique reflns          869
           Completeness (_total/calc)             95.40%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C5     = .          R
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Sugar derivatives are an important class of compounds having a broad spectrum of applications in the chemical, biochemical, medicinal(Chang et al., 2001), and pharmaceutical fields (Stutz, 1999), Here we report the structure of a novel Sugar derivative.

The molecular structure of title compound is shown in Fig.1. Torsion angle C(2)—C(3)—C(4)—C(5) is -129.9°.Intermolecular O3–H···O4 hydrogen bonds links the molecules into chains along the a axis.

Related literature

Bioactivity of sugar derivatives: Stutz (1999); Chang et al. (2001).

S2. Experimental

1,4:3,6-dianhydro-D-fructose, having three known chiral centers, was dissolved in MeOH. Catalytic amount of H₂SO₄ was added and the mixture was stirred at room temperature for 4 h,and evaporated under reduced pressure to dryness. The residue was recrystallization from MeOH,to give title compound as a colorless crystal.

S3. Refinement

The absolute configuration could not be determined from the experimental data, therefore, the Friedel equivalents were merged before refinement. The absolute configuration was set from the starting material of known configurataion.

Computing details

Data collection: R-AXIS (Molecular Structure Corporation, 1993); cell refinement: R-AXIS; data reduction: R-AXIS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN (Molecular Structure Corporation, 1993); software used to prepare material for publication: TEXSAN.

Figures

	Fig. 1. The molecular structure of I, with 30% probability displacement ellipsoids and hydrogen atoms shown as spheres of arbitrary radii
	Fig. 2. The Molecular stacking of title compound along the a axis showing the intermolecular hydrogen bonds.

2,2-Di-C-methoxy-1,4:3,6-dianhydromannitol

Crystal data

C8H14O5	F(000) = 204
Mr = 190.19	Dx = 1.398 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 6.4996 (13) Å	Cell parameters from 389 reflections
b = 6.3375 (13) Å	θ = 2–25.1°
c = 10.983 (2) Å	µ = 0.12 mm^−1
β = 93.07 (3)°	T = 291 K
V = 451.77 (16) Å^3	Prism, colorless
Z = 2	0.20 × 0.18 × 0.17 mm

Data collection

Rigaku R-AXIS-IV diffractometer	772 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.045
Graphite monochromator	θmax = 25.0°, θmin = 1.9°
Detector resolution: 0 pixels mm^-1	h = 0→7
Oscillation frames scans	k = −7→7
1418 measured reflections	l = −13→13
829 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.138	w = 1/[σ^2(Fo^2) + (0.0956P)^2 + 0.0821P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
829 reflections	Δρmax = 0.20 e Å^−3
123 parameters	Δρmin = −0.23 e Å^−3
1 restraint	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.32 (5)

Special details

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.

Because the absolute configuration was established by the structure determination of a compound containing a chiral reference molecule of known absolute configuration, we have merged the Friedels in the refinement.

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

	x	y	z	Uiso*/Ueq
O1	0.0086 (5)	0.4646 (6)	0.1232 (3)	0.0643 (9)
O2	0.1615 (4)	0.4646 (6)	0.4086 (2)	0.0658 (9)
O3	−0.2707 (5)	0.2344 (7)	0.2434 (4)	0.0799 (11)
O4	0.4505 (4)	0.6120 (5)	0.1554 (2)	0.0534 (8)
O5	0.3034 (4)	0.8296 (5)	0.2983 (3)	0.0526 (8)
C1	0.0757 (7)	0.6726 (7)	0.1524 (4)	0.0559 (11)
H1A	−0.0253	0.7449	0.1992	0.067*
H1B	0.0954	0.7526	0.0786	0.067*
C2	0.2786 (6)	0.6500 (6)	0.2271 (3)	0.0453 (9)
C3	0.2496 (6)	0.4386 (7)	0.2940 (4)	0.0481 (10)
H3A	0.3798	0.3607	0.3029	0.058*
C4	0.0928 (6)	0.3198 (7)	0.2124 (3)	0.0543 (10)
H4A	0.1568	0.1992	0.1733	0.065*
C5	−0.0701 (6)	0.2466 (7)	0.2976 (4)	0.0543 (10)
H5A	−0.0308	0.1077	0.3304	0.065*
C6	−0.0468 (6)	0.4083 (9)	0.3988 (4)	0.0647 (13)
H6A	−0.1315	0.5311	0.3794	0.078*
H6B	−0.0887	0.3488	0.4750	0.078*
C7	0.5017 (8)	0.7814 (8)	0.0763 (4)	0.0684 (13)
H7A	0.6192	0.7426	0.0319	0.103*
H7B	0.5333	0.9054	0.1239	0.103*
H7C	0.3868	0.8098	0.0201	0.103*
C8	0.4823 (6)	0.8327 (9)	0.3786 (4)	0.0630 (12)
H8A	0.4872	0.9629	0.4233	0.095*
H8B	0.6028	0.8208	0.3322	0.095*
H8C	0.4777	0.7166	0.4344	0.095*
H3E	−0.298 (15)	0.36 (2)	0.204 (8)	0.18 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0798 (19)	0.0572 (19)	0.0542 (15)	−0.0192 (16)	−0.0124 (13)	0.0022 (16)
O2	0.0693 (17)	0.078 (2)	0.0499 (14)	−0.0169 (18)	0.0038 (12)	0.0008 (17)
O3	0.0611 (18)	0.074 (2)	0.103 (3)	−0.0198 (18)	−0.0077 (16)	0.016 (2)
O4	0.0644 (17)	0.0408 (15)	0.0562 (14)	−0.0050 (13)	0.0141 (12)	0.0020 (14)
O5	0.0541 (15)	0.0410 (15)	0.0622 (16)	0.0028 (14)	−0.0034 (12)	−0.0060 (15)
C1	0.061 (2)	0.045 (3)	0.060 (2)	−0.0047 (19)	−0.0137 (18)	0.010 (2)
C2	0.049 (2)	0.042 (2)	0.0446 (18)	0.0019 (16)	−0.0024 (15)	0.0011 (18)
C3	0.0427 (17)	0.044 (2)	0.057 (2)	0.0065 (17)	0.0017 (15)	0.011 (2)
C4	0.068 (2)	0.036 (2)	0.060 (2)	−0.0005 (19)	0.0112 (19)	−0.006 (2)
C5	0.057 (2)	0.042 (2)	0.064 (2)	−0.0064 (18)	0.0012 (17)	0.008 (2)
C6	0.064 (3)	0.065 (3)	0.067 (3)	−0.001 (2)	0.018 (2)	0.005 (2)
C7	0.091 (3)	0.052 (3)	0.063 (2)	−0.015 (2)	0.014 (2)	0.009 (2)
C8	0.062 (2)	0.062 (3)	0.064 (2)	−0.012 (2)	−0.0107 (18)	−0.007 (3)

Geometric parameters (Å, º)

O1—C1	1.420 (6)	C3—C4	1.521 (6)
O1—C4	1.429 (5)	C3—H3A	0.9800
O2—C6	1.399 (5)	C4—C5	1.522 (6)
O2—C3	1.419 (5)	C4—H4A	0.9800
O3—C5	1.406 (5)	C5—C6	1.514 (7)
O3—H3E	0.91 (14)	C5—H5A	0.9800
O4—C2	1.422 (5)	C6—H6A	0.9700
O4—C7	1.431 (5)	C6—H6B	0.9700
O5—C2	1.385 (5)	C7—H7A	0.9600
O5—C8	1.421 (4)	C7—H7B	0.9600
C1—C2	1.523 (5)	C7—H7C	0.9600
C1—H1A	0.9700	C8—H8A	0.9600
C1—H1B	0.9700	C8—H8B	0.9600
C2—C3	1.545 (6)	C8—H8C	0.9600
C1—O1—C4	109.9 (3)	C3—C4—H4A	110.9
C6—O2—C3	109.7 (3)	C5—C4—H4A	110.9
C5—O3—H3E	108 (7)	O3—C5—C6	113.7 (4)
C2—O4—C7	115.1 (3)	O3—C5—C4	114.6 (3)
C2—O5—C8	115.4 (3)	C6—C5—C4	101.5 (3)
O1—C1—C2	106.3 (3)	O3—C5—H5A	108.9
O1—C1—H1A	110.5	C6—C5—H5A	108.9
C2—C1—H1A	110.5	C4—C5—H5A	108.9
O1—C1—H1B	110.5	O2—C6—C5	106.7 (4)
C2—C1—H1B	110.5	O2—C6—H6A	110.4
H1A—C1—H1B	108.7	C5—C6—H6A	110.4
O5—C2—O4	112.4 (3)	O2—C6—H6B	110.4
O5—C2—C1	107.4 (3)	C5—C6—H6B	110.4
O4—C2—C1	113.7 (3)	H6A—C6—H6B	108.6
O5—C2—C3	117.2 (3)	O4—C7—H7A	109.5
O4—C2—C3	103.6 (3)	O4—C7—H7B	109.5
C1—C2—C3	102.3 (3)	H7A—C7—H7B	109.5
O2—C3—C4	106.9 (3)	O4—C7—H7C	109.5
O2—C3—C2	112.7 (3)	H7A—C7—H7C	109.5
C4—C3—C2	104.1 (3)	H7B—C7—H7C	109.5
O2—C3—H3A	110.9	O5—C8—H8A	109.5
C4—C3—H3A	110.9	O5—C8—H8B	109.5
C2—C3—H3A	110.9	H8A—C8—H8B	109.5
O1—C4—C3	107.8 (3)	O5—C8—H8C	109.5
O1—C4—C5	111.3 (3)	H8A—C8—H8C	109.5
C3—C4—C5	104.7 (3)	H8B—C8—H8C	109.5
O1—C4—H4A	110.9
C4—O1—C1—C2	25.6 (4)	O4—C2—C3—C4	−93.3 (3)
C8—O5—C2—O4	−56.7 (4)	C1—C2—C3—C4	25.1 (4)
C8—O5—C2—C1	177.6 (3)	C1—O1—C4—C3	−8.7 (4)
C8—O5—C2—C3	63.2 (4)	C1—O1—C4—C5	105.6 (4)
C7—O4—C2—O5	−56.8 (4)	O2—C3—C4—O1	108.3 (4)
C7—O4—C2—C1	65.4 (4)	C2—C3—C4—O1	−11.2 (4)
C7—O4—C2—C3	175.7 (3)	O2—C3—C4—C5	−10.4 (4)
O1—C1—C2—O5	−155.2 (3)	C2—C3—C4—C5	−129.9 (3)
O1—C1—C2—O4	79.9 (4)	O1—C4—C5—O3	32.0 (5)
O1—C1—C2—C3	−31.2 (4)	C3—C4—C5—O3	148.3 (4)
C6—O2—C3—C4	−10.7 (5)	O1—C4—C5—C6	−91.0 (4)
C6—O2—C3—C2	103.1 (4)	C3—C4—C5—C6	25.3 (4)
O5—C2—C3—O2	26.8 (4)	C3—O2—C6—C5	27.8 (5)
O4—C2—C3—O2	151.2 (3)	O3—C5—C6—O2	−156.3 (4)
C1—C2—C3—O2	−90.3 (4)	C4—C5—C6—O2	−32.7 (5)
O5—C2—C3—C4	142.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3E···O4^i	0.91 (14)	2.33 (13)	3.123 (6)	145 (9)

Symmetry code: (i) x−1, y, z.