2,6-Anhydro-1-de­oxy-3,4-O-isopropyl­idene-3-C-methyl-β-D-ribo-hex-2-ulofuran­ose

The relative configuration of the title compound, C₁₀H₁₆O₄, was firmly established by X-ray crystallographic analysis. The absolute configuration was determined by the use of 2-C-methyl-D-ribono-1,4-lactone as the starting material.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.031
• wR factor = 0.074
• Data-to-parameter ratio = 10.8

checkCIF/PLATON results

No syntax errors found



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           27.45
           From the CIF: _reflns_number_total               1370
           Count of symmetry unique reflns         1398
           Completeness (_total/calc)             98.00%
           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 C1     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C5     = .          R

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

   4 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
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

For background information see the previous paper (Curran et al., 2007). The crystal structure of the title compound (Fig. 1) exists as alternating layers of molecules running parallel to the ab-face (Fig.2). There is no hydrogen bonding.

Related literature

For related literature see: Curran et al. (2007); Jones et al. (2007); Hotchkiss et al. (2006).

S2. Experimental

Treatment of 1-deoxy-3-C-methyl-D-psicose 2 (Jones et al. in preparation) derived from 2-C-methyl-D-ribono-1,4-lactone 1 (Hotchkiss et al., 2006), with sodium cyanide, gave a mixture of 2,6-anhydro derivative 3 and lactone 4 (Curran et al. 2007) (Fig. 3). X-ray analysis firmly established the structure of the title compound as the 2,6-anhydro furanose 3. m.p. 321–326 K; [α]_D²² -47.0 (c, 1.0 in acetone).

S3. Refinement

In the absence of significant anomalous scattering, Friedel pairs were merged and the absolute configuration was assigned from the starting material.

The H atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H in the range 0.93–0.98, O—H = 0.82 Å) and U_iso(H) (in the range 1.2–1.5 times U_eq of the parent atom), after which the positions were refined with riding constraints.

Computing details

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.

Figures

	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 of the title compound projected along the b-axis.
	Fig. 3. The reaction scheme.

2,6-Anhydro-1-deoxy-3,4-O-isopropylidene-3-C-methyl-β-D– ribo-hex-2-ulofuranose

Crystal data

C10H16O4	F(000) = 432
Mr = 200.23	Dx = 1.277 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1321 reflections
a = 6.6307 (2) Å	θ = 5–27°
b = 11.1029 (4) Å	µ = 0.10 mm^−1
c = 14.1409 (5) Å	T = 150 K
V = 1041.05 (6) Å^3	Plate, colourless
Z = 4	0.60 × 0.50 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer	1160 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
ω scans	θmax = 27.5°, θmin = 5.3°
Absorption correction: multi-scan DENZO/SCALEPACK (Otwinowski & Minor, 1997)	h = −8→8
Tmin = 0.95, Tmax = 1.00	k = −14→14
6557 measured reflections	l = −18→18
1370 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.074	w = 1/[σ^2(F^2) + (0.03P)^2 + 0.18P], where P = [max(Fo^2,0) + 2Fc^2]/3
S = 0.93	(Δ/σ)max = 0.000171
1370 reflections	Δρmax = 0.24 e Å^−3
127 parameters	Δρmin = −0.19 e Å^−3
0 restraints

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

	x	y	z	Uiso*/Ueq
C1	0.3568 (2)	0.21011 (14)	0.20100 (10)	0.0212
C2	0.4422 (2)	0.31928 (14)	0.14619 (10)	0.0217
O3	0.56240 (17)	0.37828 (10)	0.21534 (8)	0.0263
C4	0.6883 (2)	0.27622 (15)	0.23612 (11)	0.0272
C5	0.5351 (2)	0.18346 (15)	0.26887 (10)	0.0245
O6	0.46475 (18)	0.21350 (13)	0.36068 (7)	0.0352
C7	0.2509 (3)	0.22921 (16)	0.35888 (11)	0.0270
O8	0.19903 (16)	0.25108 (11)	0.26189 (7)	0.0283
C9	0.1985 (3)	0.34073 (17)	0.41531 (13)	0.0403
C10	0.1483 (3)	0.11679 (18)	0.39421 (13)	0.0396
C11	0.7600 (3)	0.24199 (19)	0.13709 (12)	0.0353
O12	0.58629 (17)	0.27261 (11)	0.07985 (8)	0.0317
C13	0.2974 (3)	0.40276 (16)	0.09881 (12)	0.0305
C14	0.2857 (3)	0.10662 (15)	0.13904 (12)	0.0308
H41	0.8009	0.2937	0.2816	0.0355*
H51	0.5810	0.0978	0.2636	0.0310*
H91	0.0522	0.3542	0.4084	0.0621*
H92	0.2310	0.3255	0.4825	0.0614*
H93	0.2804	0.4099	0.3910	0.0617*
H101	0.0017	0.1299	0.3883	0.0594*
H102	0.1804	0.1039	0.4613	0.0595*
H103	0.1903	0.0467	0.3550	0.0594*
H111	0.7881	0.1541	0.1327	0.0480*
H112	0.8841	0.2875	0.1191	0.0473*
H131	0.3743	0.4706	0.0698	0.0479*
H132	0.1972	0.4328	0.1459	0.0487*
H133	0.2281	0.3599	0.0465	0.0489*
H141	0.2242	0.0438	0.1796	0.0485*
H142	0.4037	0.0743	0.1055	0.0487*
H143	0.1825	0.1383	0.0923	0.0481*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0180 (7)	0.0224 (8)	0.0231 (7)	0.0020 (7)	−0.0018 (6)	−0.0006 (7)
C2	0.0217 (7)	0.0228 (8)	0.0207 (7)	0.0003 (7)	−0.0004 (7)	−0.0020 (6)
O3	0.0255 (6)	0.0219 (5)	0.0316 (6)	−0.0021 (5)	−0.0053 (5)	−0.0018 (5)
C4	0.0185 (7)	0.0304 (9)	0.0326 (8)	0.0012 (8)	−0.0031 (7)	0.0014 (8)
C5	0.0219 (8)	0.0267 (8)	0.0248 (7)	0.0014 (8)	−0.0033 (7)	0.0028 (7)
O6	0.0274 (6)	0.0560 (8)	0.0221 (5)	0.0010 (7)	−0.0034 (5)	0.0044 (6)
C7	0.0257 (8)	0.0348 (10)	0.0204 (7)	−0.0004 (8)	−0.0008 (6)	0.0021 (7)
O8	0.0205 (5)	0.0431 (7)	0.0214 (5)	0.0029 (6)	0.0011 (5)	0.0025 (5)
C9	0.0467 (12)	0.0394 (10)	0.0347 (9)	0.0016 (10)	−0.0041 (9)	−0.0070 (8)
C10	0.0441 (11)	0.0375 (10)	0.0372 (9)	−0.0035 (10)	0.0063 (9)	0.0071 (9)
C11	0.0221 (8)	0.0443 (11)	0.0394 (10)	0.0043 (9)	0.0037 (8)	0.0026 (9)
O12	0.0273 (6)	0.0415 (7)	0.0262 (5)	0.0031 (6)	0.0057 (5)	0.0001 (6)
C13	0.0350 (10)	0.0261 (8)	0.0304 (8)	0.0022 (9)	−0.0060 (8)	0.0045 (7)
C14	0.0323 (9)	0.0254 (8)	0.0348 (9)	−0.0029 (8)	−0.0085 (8)	−0.0010 (8)

Geometric parameters (Å, º)

C1—C2	1.546 (2)	C7—C10	1.507 (3)
C1—C5	1.551 (2)	C9—H91	0.986
C1—O8	1.4293 (18)	C9—H92	0.988
C1—C14	1.520 (2)	C9—H93	1.001
C2—O3	1.4214 (18)	C10—H101	0.986
C2—O12	1.4357 (18)	C10—H102	0.983
C2—C13	1.493 (2)	C10—H103	0.995
O3—C4	1.438 (2)	C11—O12	1.448 (2)
C4—C5	1.519 (2)	C11—H111	0.995
C4—C11	1.527 (2)	C11—H112	0.998
C4—H41	1.004	C13—H131	0.998
C5—O6	1.4193 (19)	C13—H132	0.999
C5—H51	1.001	C13—H133	0.993
O6—C7	1.429 (2)	C14—H141	0.991
C7—O8	1.4348 (18)	C14—H142	0.983
C7—C9	1.514 (2)	C14—H143	1.014
C2—C1—C5	100.40 (12)	C7—O8—C1	110.27 (12)
C2—C1—O8	108.70 (12)	C7—C9—H91	107.3
C5—C1—O8	104.24 (11)	C7—C9—H92	108.4
C2—C1—C14	114.66 (13)	H91—C9—H92	109.6
C5—C1—C14	116.67 (13)	C7—C9—H93	108.8
O8—C1—C14	111.16 (13)	H91—C9—H93	112.5
C1—C2—O3	102.81 (11)	H92—C9—H93	110.0
C1—C2—O12	106.76 (12)	C7—C10—H101	107.1
O3—C2—O12	104.05 (12)	C7—C10—H102	110.0
C1—C2—C13	118.43 (14)	H101—C10—H102	108.4
O3—C2—C13	112.53 (13)	C7—C10—H103	109.6
O12—C2—C13	111.02 (13)	H101—C10—H103	110.2
C2—O3—C4	95.90 (11)	H102—C10—H103	111.4
O3—C4—C5	102.05 (13)	C4—C11—O12	101.92 (12)
O3—C4—C11	100.93 (13)	C4—C11—H111	111.1
C5—C4—C11	108.61 (15)	O12—C11—H111	110.1
O3—C4—H41	114.2	C4—C11—H112	111.4
C5—C4—H41	115.7	O12—C11—H112	113.2
C11—C4—H41	113.8	H111—C11—H112	109.0
C1—C5—C4	101.05 (12)	C11—O12—C2	104.40 (11)
C1—C5—O6	105.70 (12)	C2—C13—H131	108.9
C4—C5—O6	109.83 (14)	C2—C13—H132	109.6
C1—C5—H51	111.5	H131—C13—H132	111.3
C4—C5—H51	114.7	C2—C13—H133	109.5
O6—C5—H51	113.0	H131—C13—H133	107.0
C5—O6—C7	109.79 (12)	H132—C13—H133	110.5
O6—C7—O8	106.00 (12)	C1—C14—H141	109.1
O6—C7—C9	108.58 (16)	C1—C14—H142	107.9
O8—C7—C9	108.08 (14)	H141—C14—H142	110.5
O6—C7—C10	109.95 (16)	C1—C14—H143	108.8
O8—C7—C10	110.41 (14)	H141—C14—H143	110.0
C9—C7—C10	113.52 (15)	H142—C14—H143	110.5