3,4-O-Carbonyl-1,2:5,6-di-O-isopropyl­idene-D-mannitol

The title compound, C₁₃H₂₀O₇, the carbonate of a partially protected sugar alcohol, was obtained accidentally in the attempted preparation of an orthocarbonate thereof. The five-membered 1,3-dioxolane rings adopt twist and envelope conformations.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.045
• wR factor = 0.114
• Data-to-parameter ratio = 10.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5

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           27.49
           From the CIF: _reflns_number_total               1858
           Count of symmetry unique reflns         1866
           Completeness (_total/calc)             99.57%
           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 C2     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3     = .          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
   1 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
   1 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

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S1. Comment

The title compound, C₁₃H₂₀O₇, the carbonate of a partially protected sugar alcohol, 1,2:5,6-di-O-isopropylidene-D-mannitol, was obtained accidentally on the attempted preparation of an orthocarbonate thereof.

The molecular structure is shown in Fig. 1. The 5-membered 1,3-dioxolane ring O1–C1–C2–O2–C12 adopts a twist conformation on O1—C1 (Q₂ = 0.324 (3) Å, φ₂ = 16.7 (6)°), whereas O5–C5–C6–O6–C22 (Q₂ = 0.302 (3) Å, φ₂ = 319.3 (6)°) shows an envelope conformation on C22. The dioxolane ring O3–C3–C4–O4–C10, which contains the carbonate group, is twisted on C3—C4 (Q₂ = 0.165 (3) Å, φ₂ = 57.8 (11)°). Ring puckering parameters (Cremer & Pople, 1975) were calculated with PLATON (Spek, 2003).

The molecular packing is shown in Fig. 2.

Related literature

For related literature, see: Hough et al. (1962); Baker & Sachdev (1963); Mues & Buysch (1990). For analysis tools, see: Cremer & Pople (1975); Flack (1983).

S2. Experimental

The title compound was obtained accidentally as the sole product on the attempted preparation of an orthocarbonate by the reaction of dichlorodiphenoxymethane, (PhO)₂CCl₂, with 1,2:5,6-di-O-isopropylidene-D-mannitol in analogy to a literature procedure (Mues & Buysch, 1990). The crude product was recrystallized from boiling ethyl acetate.

S3. Refinement

All H atoms were located in a difference map and refined as riding on their parent atoms. One common isotropic displacement parameter for all H atoms was refined to U_iso(H) = 0.059 (2) Ų.

Due to the absence of significant anomalous scattering the absolute structure factor (Flack, 1983), which is 2.9 with an estimated standard deviation of 1.8 for the unmerged data set, is meaningless. Thus, Friedel opposites (1329 pairs) have been merged. The absolute structure has been assigned to match the known sterochemistry of the starting material 1,2:5,6-di-O-isopropylidene-D-mannitol.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Computing details

Data collection: COLLECT (Nonius, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of (I), with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level) for non-H atoms.
	Fig. 2. The packing of (I), viewed along [100]. H atoms omitted for clarity.

3,4-O-Carbonyl-1,2:5,6-di-O-isopropylidene-D-mannitol

Crystal data

C13H20O7	F(000) = 616
Mr = 288.29	Dx = 1.367 (1) Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 13166 reflections
a = 6.0863 (3) Å	θ = 3.1–27.5°
b = 11.6958 (4) Å	µ = 0.11 mm^−1
c = 19.6816 (8) Å	T = 200 K
V = 1401.02 (10) Å^3	Needle, colourless
Z = 4	0.16 × 0.04 × 0.04 mm

Data collection

Nonius KappaCCD area-detector diffractometer	1153 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.059
MONTEL, graded multilayered X-ray optics monochromator	θmax = 27.5°, θmin = 3.5°
Detector resolution: 9 pixels mm^-1	h = −7→7
φ and ω scans	k = −15→15
3191 measured reflections	l = −25→25
1858 independent reflections

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)] = 0.045	Hydrogen site location: difference Fourier map
wR(F^2) = 0.114	Only H-atom displacement parameters refined
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0615P)^2] where P = (Fo^2 + 2Fc^2)/3
1858 reflections	(Δ/σ)max < 0.001
186 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

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 > 2σ(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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.3167 (4)	0.4262 (2)	0.04204 (11)	0.0471 (6)
O2	0.0435 (4)	0.4772 (2)	0.11497 (10)	0.0442 (6)
O3	0.4588 (4)	0.52808 (19)	0.24498 (11)	0.0447 (6)
O4	0.2177 (4)	0.64536 (16)	0.29075 (10)	0.0392 (6)
O5	0.1688 (4)	0.43473 (18)	0.35795 (10)	0.0410 (6)
O6	−0.0359 (4)	0.28634 (17)	0.32210 (11)	0.0440 (6)
O10	0.5768 (5)	0.6762 (2)	0.30616 (13)	0.0634 (8)
C1	0.4190 (6)	0.4462 (3)	0.10539 (15)	0.0433 (8)
H11	0.5558	0.4911	0.0998	0.059 (2)*
H12	0.4537	0.3735	0.1288	0.059 (2)*
C2	0.2473 (6)	0.5135 (2)	0.14394 (14)	0.0361 (8)
H2	0.2686	0.5972	0.1360	0.059 (2)*
C3	0.2486 (5)	0.4882 (2)	0.22009 (15)	0.0370 (8)
H3	0.2329	0.4042	0.2282	0.059 (2)*
C4	0.0853 (5)	0.5539 (3)	0.26282 (14)	0.0342 (7)
H4	−0.0350	0.5856	0.2338	0.059 (2)*
C5	−0.0096 (6)	0.4859 (2)	0.32170 (15)	0.0389 (8)
H5	−0.0949	0.5374	0.3525	0.059 (2)*
C6	−0.1529 (6)	0.3852 (3)	0.29908 (17)	0.0461 (9)
H61	−0.3003	0.3893	0.3202	0.059 (2)*
H62	−0.1696	0.3842	0.2491	0.059 (2)*
C10	0.4302 (6)	0.6218 (3)	0.28301 (16)	0.0420 (8)
C11	−0.0367 (7)	0.4552 (3)	−0.00416 (16)	0.0527 (10)
H111	0.0049	0.4136	−0.0454	0.059 (2)*
H112	−0.0033	0.5366	−0.0099	0.059 (2)*
H113	−0.1944	0.4456	0.0041	0.059 (2)*
C12	0.0902 (6)	0.4089 (3)	0.05523 (15)	0.0400 (8)
C13	0.0364 (7)	0.2857 (3)	0.0715 (2)	0.0542 (10)
H131	0.1349	0.2582	0.1073	0.059 (2)*
H132	0.0554	0.2389	0.0307	0.059 (2)*
H133	−0.1162	0.2803	0.0871	0.059 (2)*
C21	0.3026 (7)	0.2459 (3)	0.37563 (17)	0.0499 (9)
H211	0.4105	0.2747	0.4084	0.059 (2)*
H212	0.3679	0.2451	0.3301	0.059 (2)*
H213	0.2590	0.1681	0.3883	0.059 (2)*
C22	0.1052 (6)	0.3218 (3)	0.37579 (15)	0.0370 (8)
C23	−0.0157 (7)	0.3221 (3)	0.44255 (17)	0.0547 (10)
H231	0.0792	0.3541	0.4780	0.059 (2)*
H232	−0.0564	0.2437	0.4547	0.059 (2)*
H233	−0.1488	0.3688	0.4384	0.059 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0490 (16)	0.0524 (14)	0.0398 (12)	0.0003 (13)	0.0080 (12)	−0.0053 (11)
O2	0.0397 (14)	0.0545 (14)	0.0383 (12)	0.0032 (12)	0.0004 (11)	−0.0122 (11)
O3	0.0407 (15)	0.0514 (14)	0.0421 (12)	0.0062 (12)	−0.0042 (11)	−0.0051 (11)
O4	0.0464 (15)	0.0292 (11)	0.0420 (12)	−0.0005 (10)	0.0015 (11)	−0.0011 (10)
O5	0.0485 (15)	0.0343 (10)	0.0403 (11)	−0.0035 (11)	−0.0062 (12)	0.0049 (9)
O6	0.0522 (16)	0.0317 (11)	0.0482 (13)	−0.0018 (11)	−0.0116 (12)	0.0008 (10)
O10	0.0551 (18)	0.0756 (17)	0.0595 (16)	−0.0169 (17)	−0.0102 (15)	−0.0074 (14)
C1	0.041 (2)	0.0480 (19)	0.0414 (17)	−0.0007 (18)	0.0032 (17)	−0.0082 (16)
C2	0.040 (2)	0.0349 (15)	0.0335 (15)	−0.0019 (16)	0.0010 (15)	−0.0020 (13)
C3	0.042 (2)	0.0303 (14)	0.0391 (16)	0.0002 (15)	−0.0035 (15)	−0.0001 (13)
C4	0.0383 (19)	0.0305 (15)	0.0337 (15)	0.0013 (15)	−0.0015 (15)	0.0024 (13)
C5	0.045 (2)	0.0350 (16)	0.0369 (16)	0.0025 (16)	0.0006 (15)	0.0012 (14)
C6	0.045 (2)	0.0381 (16)	0.056 (2)	−0.0002 (16)	−0.0038 (18)	0.0109 (16)
C10	0.046 (2)	0.0435 (18)	0.0367 (17)	−0.0026 (19)	−0.0040 (18)	0.0036 (16)
C11	0.062 (3)	0.057 (2)	0.0394 (17)	0.002 (2)	−0.0045 (19)	0.0043 (16)
C12	0.043 (2)	0.0441 (19)	0.0327 (16)	0.0011 (17)	0.0027 (16)	−0.0075 (13)
C13	0.060 (3)	0.0416 (18)	0.061 (2)	−0.0052 (19)	−0.008 (2)	−0.0011 (17)
C21	0.055 (2)	0.0486 (18)	0.0464 (18)	0.0096 (19)	−0.0025 (19)	0.0013 (17)
C22	0.045 (2)	0.0330 (15)	0.0333 (16)	−0.0022 (16)	−0.0008 (15)	0.0006 (13)
C23	0.064 (3)	0.057 (2)	0.043 (2)	−0.002 (2)	0.0130 (19)	0.0072 (16)

Geometric parameters (Å, º)

O1—C1	1.413 (4)	C4—H4	1.0000
O1—C12	1.417 (4)	C5—C6	1.531 (4)
O2—C2	1.429 (4)	C5—H5	1.0000
O2—C12	1.449 (4)	C6—H61	0.9900
O3—C10	1.339 (4)	C6—H62	0.9900
O3—C3	1.447 (4)	C11—C12	1.502 (5)
O4—C10	1.331 (4)	C11—H111	0.9800
O4—C4	1.448 (4)	C11—H112	0.9800
O5—C22	1.420 (4)	C11—H113	0.9800
O5—C5	1.430 (4)	C12—C13	1.512 (5)
O6—C22	1.424 (4)	C13—H131	0.9800
O6—C6	1.431 (4)	C13—H132	0.9800
O10—C10	1.187 (4)	C13—H133	0.9800
C1—C2	1.512 (4)	C21—C22	1.494 (5)
C1—H11	0.9900	C21—H211	0.9800
C1—H12	0.9900	C21—H212	0.9800
C2—C3	1.528 (4)	C21—H213	0.9800
C2—H2	1.0000	C22—C23	1.506 (5)
C3—C4	1.512 (4)	C23—H231	0.9800
C3—H3	1.0000	C23—H232	0.9800
C4—C5	1.520 (4)	C23—H233	0.9800
C1—O1—C12	106.9 (2)	H61—C6—H62	108.9
C2—O2—C12	108.5 (2)	O10—C10—O4	125.2 (3)
C10—O3—C3	109.8 (3)	O10—C10—O3	123.8 (4)
C10—O4—C4	110.2 (2)	O4—C10—O3	111.1 (3)
C22—O5—C5	107.8 (2)	C12—C11—H111	109.5
C22—O6—C6	107.4 (2)	C12—C11—H112	109.5
O1—C1—C2	103.0 (3)	H111—C11—H112	109.5
O1—C1—H11	111.2	C12—C11—H113	109.5
C2—C1—H11	111.2	H111—C11—H113	109.5
O1—C1—H12	111.2	H112—C11—H113	109.5
C2—C1—H12	111.2	O1—C12—O2	105.1 (3)
H11—C1—H12	109.1	O1—C12—C11	107.8 (3)
O2—C2—C1	104.2 (2)	O2—C12—C11	109.4 (3)
O2—C2—C3	109.8 (2)	O1—C12—C13	112.7 (3)
C1—C2—C3	112.8 (3)	O2—C12—C13	108.1 (3)
O2—C2—H2	110.0	C11—C12—C13	113.4 (3)
C1—C2—H2	110.0	C12—C13—H131	109.5
C3—C2—H2	110.0	C12—C13—H132	109.5
O3—C3—C4	103.2 (2)	H131—C13—H132	109.5
O3—C3—C2	105.9 (2)	C12—C13—H133	109.5
C4—C3—C2	116.3 (3)	H131—C13—H133	109.5
O3—C3—H3	110.3	H132—C13—H133	109.5
C4—C3—H3	110.3	C22—C21—H211	109.5
C2—C3—H3	110.3	C22—C21—H212	109.5
O4—C4—C3	102.7 (3)	H211—C21—H212	109.5
O4—C4—C5	108.0 (2)	C22—C21—H213	109.5
C3—C4—C5	114.1 (3)	H211—C21—H213	109.5
O4—C4—H4	110.6	H212—C21—H213	109.5
C3—C4—H4	110.6	O5—C22—O6	104.6 (2)
C5—C4—H4	110.6	O5—C22—C21	109.5 (3)
O5—C5—C4	108.1 (3)	O6—C22—C21	108.1 (2)
O5—C5—C6	104.8 (2)	O5—C22—C23	110.3 (2)
C4—C5—C6	113.4 (3)	O6—C22—C23	110.7 (3)
O5—C5—H5	110.1	C21—C22—C23	113.4 (3)
C4—C5—H5	110.1	C22—C23—H231	109.5
C6—C5—H5	110.1	C22—C23—H232	109.5
O6—C6—C5	104.2 (2)	H231—C23—H232	109.5
O6—C6—H61	110.9	C22—C23—H233	109.5
C5—C6—H61	110.9	H231—C23—H233	109.5
O6—C6—H62	110.9	H232—C23—H233	109.5
C5—C6—H62	110.9
C12—O1—C1—C2	−35.9 (3)	O4—C4—C5—C6	−179.6 (2)
C12—O2—C2—C1	−9.5 (3)	C3—C4—C5—C6	−66.0 (4)
C12—O2—C2—C3	−130.6 (2)	C22—O6—C6—C5	22.0 (3)
O1—C1—C2—O2	27.4 (3)	O5—C5—C6—O6	−2.6 (3)
O1—C1—C2—C3	146.5 (3)	C4—C5—C6—O6	115.1 (3)
C10—O3—C3—C4	−13.6 (3)	C4—O4—C10—O10	−173.1 (3)
C10—O3—C3—C2	109.1 (3)	C4—O4—C10—O3	7.3 (3)
O2—C2—C3—O3	−179.7 (2)	C3—O3—C10—O10	−175.1 (3)
C1—C2—C3—O3	64.6 (3)	C3—O3—C10—O4	4.6 (3)
O2—C2—C3—C4	−65.6 (3)	C1—O1—C12—O2	30.4 (3)
C1—C2—C3—C4	178.6 (3)	C1—O1—C12—C11	147.0 (3)
C10—O4—C4—C3	−15.2 (3)	C1—O1—C12—C13	−87.0 (3)
C10—O4—C4—C5	105.7 (3)	C2—O2—C12—O1	−11.9 (3)
O3—C3—C4—O4	16.7 (3)	C2—O2—C12—C11	−127.5 (3)
C2—C3—C4—O4	−98.9 (3)	C2—O2—C12—C13	108.6 (3)
O3—C3—C4—C5	−99.9 (3)	C5—O5—C22—O6	31.8 (3)
C2—C3—C4—C5	144.5 (3)	C5—O5—C22—C21	147.4 (3)
C22—O5—C5—C4	−139.1 (2)	C5—O5—C22—C23	−87.3 (3)
C22—O5—C5—C6	−17.8 (3)	C6—O6—C22—O5	−33.6 (3)
O4—C4—C5—O5	−63.8 (3)	C6—O6—C22—C21	−150.1 (3)
C3—C4—C5—O5	49.7 (3)	C6—O6—C22—C23	85.2 (3)