p-Tolyl 2,3-an­hydro-5,6-O-iso­propyl­idene-1-thio-β-D-gulo­furan­oside

In the title compound, C₁₆H₂₀O₄S, the epoxide ring is trans to the p-tolyl group and cis to the dioxolane moiety. The furan­ose ring adopts a conformation in which the furan­ose and epoxide O atoms are on the same face of the mol­ecule (E_O) and the p-tolyl group adopts the conformation favored by the exo-anomeric effect, gauche to the ring O atom and anti to the ring C atom.

Key indicators

• Single-crystal X-ray study
• T = 193 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.033
• wR factor = 0.079
• Data-to-parameter ratio = 16.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.61 mm

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           26.39
           From the CIF: _reflns_number_total               3202
           Count of symmetry unique reflns         1841
           Completeness (_total/calc)            173.93%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1361
           Fraction of Friedel pairs measured     0.739
           Are heavy atom types Z>Si present          yes

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

   0 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

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Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: SHELXTL (Bruker, 1997a); software used to prepare material for publication: SHELXTL.

p-tolyl 2,3-anhydro-5,6-O-isopropylidene-1-thio-β-D-talofuranoside

Crystal data

C16H20O4S	Dx = 1.307 Mg m^−3
Mr = 308.38	Melting point: 349 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5599 reflections
a = 9.1248 (7) Å	θ = 2.2–25.8°
b = 12.0366 (10) Å	µ = 0.22 mm^−1
c = 14.2666 (11) Å	T = 193 K
V = 1566.9 (2) Å^3	Rod, colourless
Z = 4	0.61 × 0.11 × 0.10 mm
F(000) = 656

Data collection

Bruker PLATFORM/SMART 1000 CCD area-detector diffractometer	3202 independent reflections
Radiation source: fine-focus sealed tube	2780 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
Detector resolution: 8.192 pixels mm^-1	θmax = 26.4°, θmin = 2.2°
ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −15→14
Tmin = 0.878, Tmax = 0.978	l = −17→17
12110 measured 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)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + (0.0376P)^2 + 0.2041P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
3202 reflections	Δρmax = 0.23 e Å^−3
191 parameters	Δρmin = −0.13 e Å^−3
0 restraints	Absolute structure: Flack (1983), 1359 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (7)

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.

Hydrogen atoms were generated in idealized positions (according to the sp² or sp³ geometries of their parent carbon atoms), and then refined using a riding model with fixed C—H distances (C—H = 0.95–1.00 Å) and with U_iso(H) = 1.2U_eq(C).

Data for compound (I) were collected at 193 K on a Bruker PLATFORM diffractometer equipped with a SMART 1000 CCD area detector. The structure of (I) was solved through use of the direct methods program SHELXS97 (Sheldrick, 1990).

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

	x	y	z	Uiso*/Ueq
S	0.66025 (5)	0.04196 (5)	0.31980 (3)	0.05176 (15)
O1	0.46045 (13)	−0.08484 (11)	0.22885 (8)	0.0442 (3)
O2	0.30951 (14)	0.07865 (13)	0.15432 (9)	0.0540 (4)
O5	0.49340 (14)	−0.16044 (12)	−0.01461 (9)	0.0540 (4)
O6	0.26305 (13)	−0.09677 (12)	−0.03577 (9)	0.0507 (3)
C1	0.47463 (19)	0.01728 (16)	0.27763 (13)	0.0438 (4)
H1	0.4032	0.0208	0.3307	0.053*
C2	0.4400 (2)	0.10482 (18)	0.20598 (13)	0.0483 (5)
H2	0.4718	0.1836	0.2151	0.058*
C3	0.44962 (18)	0.05148 (17)	0.11441 (13)	0.0434 (4)
H3	0.4877	0.0933	0.0590	0.052*
C4	0.49636 (19)	−0.06644 (15)	0.13180 (12)	0.0400 (4)
H4	0.6052	−0.0711	0.1245	0.048*
C5	0.4270 (2)	−0.15966 (17)	0.07556 (14)	0.0483 (5)
H5	0.4451	−0.2323	0.1075	0.058*
C6	0.2637 (2)	−0.1467 (2)	0.05546 (15)	0.0587 (6)
H6A	0.2135	−0.2196	0.0549	0.070*
H6B	0.2161	−0.0978	0.1023	0.070*
C7	0.38294 (19)	−0.14459 (16)	−0.08429 (14)	0.0439 (4)
C8	0.3410 (3)	−0.2552 (2)	−0.12746 (17)	0.0682 (6)
H8A	0.3068	−0.3057	−0.0782	0.082*
H8B	0.4265	−0.2876	−0.1588	0.082*
H8C	0.2624	−0.2439	−0.1733	0.082*
C9	0.4389 (2)	−0.0632 (2)	−0.15481 (15)	0.0571 (5)
H9A	0.4617	0.0072	−0.1235	0.069*
H9B	0.3639	−0.0506	−0.2028	0.069*
H9C	0.5277	−0.0928	−0.1843	0.069*
C10	0.66366 (17)	−0.04972 (16)	0.41675 (12)	0.0417 (4)
C11	0.5884 (2)	−0.02508 (18)	0.49798 (13)	0.0530 (5)
H11	0.5312	0.0408	0.5012	0.064*
C12	0.5951 (2)	−0.0948 (2)	0.57448 (15)	0.0606 (6)
H12	0.5416	−0.0763	0.6294	0.073*
C13	0.6773 (2)	−0.19034 (17)	0.57321 (16)	0.0550 (5)
C14	0.7529 (2)	−0.21488 (18)	0.49205 (19)	0.0620 (6)
H14	0.8112	−0.2802	0.4896	0.074*
C15	0.7459 (2)	−0.14616 (19)	0.41369 (16)	0.0570 (6)
H15	0.7975	−0.1655	0.3582	0.068*
C16	0.6843 (3)	−0.2655 (2)	0.65783 (19)	0.0822 (8)
H16A	0.7504	−0.3278	0.6449	0.099*
H16B	0.5860	−0.2940	0.6717	0.099*
H16C	0.7209	−0.2235	0.7118	0.099*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0406 (2)	0.0637 (3)	0.0509 (3)	−0.0113 (2)	−0.0010 (2)	−0.0017 (3)
O1	0.0429 (7)	0.0457 (8)	0.0439 (7)	−0.0061 (6)	−0.0064 (6)	0.0099 (6)
O2	0.0426 (7)	0.0660 (9)	0.0534 (8)	0.0132 (6)	0.0030 (6)	0.0137 (7)
O5	0.0415 (7)	0.0668 (10)	0.0538 (8)	0.0134 (7)	−0.0152 (6)	−0.0082 (7)
O6	0.0310 (6)	0.0677 (9)	0.0534 (8)	−0.0004 (6)	−0.0033 (6)	0.0080 (7)
C1	0.0335 (9)	0.0518 (12)	0.0461 (10)	−0.0020 (8)	0.0017 (8)	0.0030 (9)
C2	0.0460 (10)	0.0480 (12)	0.0511 (11)	0.0044 (9)	0.0060 (8)	0.0048 (9)
C3	0.0383 (9)	0.0459 (11)	0.0460 (9)	−0.0012 (8)	0.0065 (8)	0.0092 (9)
C4	0.0324 (8)	0.0436 (10)	0.0441 (9)	−0.0018 (7)	−0.0021 (7)	0.0055 (8)
C5	0.0503 (11)	0.0433 (11)	0.0511 (11)	−0.0056 (8)	−0.0105 (9)	0.0070 (9)
C6	0.0448 (11)	0.0795 (16)	0.0519 (12)	−0.0207 (11)	−0.0061 (9)	0.0048 (11)
C7	0.0343 (9)	0.0486 (11)	0.0488 (10)	0.0003 (8)	−0.0080 (8)	−0.0011 (9)
C8	0.0705 (15)	0.0608 (14)	0.0732 (15)	−0.0080 (12)	−0.0221 (13)	−0.0043 (12)
C9	0.0414 (10)	0.0704 (14)	0.0595 (12)	−0.0033 (10)	−0.0006 (9)	0.0037 (11)
C10	0.0340 (8)	0.0448 (10)	0.0462 (9)	−0.0027 (8)	−0.0073 (8)	−0.0106 (8)
C11	0.0547 (11)	0.0537 (13)	0.0507 (11)	0.0183 (10)	−0.0032 (9)	−0.0063 (10)
C12	0.0691 (13)	0.0665 (15)	0.0462 (11)	0.0127 (12)	−0.0027 (10)	−0.0025 (11)
C13	0.0571 (12)	0.0432 (11)	0.0646 (13)	−0.0058 (9)	−0.0261 (11)	−0.0057 (10)
C14	0.0594 (14)	0.0394 (12)	0.0871 (17)	0.0096 (10)	−0.0260 (12)	−0.0160 (12)
C15	0.0474 (11)	0.0594 (13)	0.0643 (13)	0.0061 (10)	−0.0019 (10)	−0.0248 (12)
C16	0.101 (2)	0.0581 (14)	0.0875 (18)	−0.0106 (14)	−0.0409 (16)	0.0123 (13)

Geometric parameters (Å, º)

S—C10	1.7697 (19)	C7—C9	1.494 (3)
S—C1	1.8217 (18)	C7—C8	1.517 (3)
O1—C1	1.419 (2)	C8—H8A	0.9800
O1—C4	1.440 (2)	C8—H8B	0.9800
O2—C2	1.435 (2)	C8—H8C	0.9800
O2—C3	1.437 (2)	C9—H9A	0.9800
O5—C5	1.422 (3)	C9—H9B	0.9800
O5—C7	1.428 (2)	C9—H9C	0.9800
O6—C7	1.417 (2)	C10—C11	1.379 (3)
O6—C6	1.433 (2)	C10—C15	1.383 (3)
C1—C2	1.502 (3)	C11—C12	1.378 (3)
C1—H1	1.0000	C11—H11	0.9500
C2—C3	1.458 (3)	C12—C13	1.373 (3)
C2—H2	1.0000	C12—H12	0.9500
C3—C4	1.503 (3)	C13—C14	1.380 (3)
C3—H3	1.0000	C13—C16	1.510 (3)
C4—C5	1.518 (3)	C14—C15	1.392 (3)
C4—H4	1.0000	C14—H14	0.9500
C5—C6	1.525 (3)	C15—H15	0.9500
C5—H5	1.0000	C16—H16A	0.9800
C6—H6A	0.9900	C16—H16B	0.9800
C6—H6B	0.9900	C16—H16C	0.9800
C10—S—C1	99.95 (8)	O6—C7—C9	109.05 (16)
C1—O1—C4	108.52 (13)	O5—C7—C9	108.36 (15)
C2—O2—C3	61.02 (11)	O6—C7—C8	111.11 (17)
C5—O5—C7	109.14 (14)	O5—C7—C8	110.09 (16)
C7—O6—C6	105.68 (15)	C9—C7—C8	112.88 (18)
O1—C1—C2	104.76 (14)	C7—C8—H8A	109.5
O1—C1—S	112.84 (12)	C7—C8—H8B	109.5
C2—C1—S	107.83 (13)	H8A—C8—H8B	109.5
O1—C1—H1	110.4	C7—C8—H8C	109.5
C2—C1—H1	110.4	H8A—C8—H8C	109.5
S—C1—H1	110.4	H8B—C8—H8C	109.5
O2—C2—C3	59.56 (11)	C7—C9—H9A	109.5
O2—C2—C1	111.74 (16)	C7—C9—H9B	109.5
C3—C2—C1	106.75 (16)	H9A—C9—H9B	109.5
O2—C2—H2	121.0	C7—C9—H9C	109.5
C3—C2—H2	121.0	H9A—C9—H9C	109.5
C1—C2—H2	121.0	H9B—C9—H9C	109.5
O2—C3—C2	59.41 (11)	C11—C10—C15	118.50 (19)
O2—C3—C4	113.70 (15)	C11—C10—S	120.92 (15)
C2—C3—C4	106.56 (15)	C15—C10—S	120.55 (15)
O2—C3—H3	120.5	C12—C11—C10	120.80 (18)
C2—C3—H3	120.5	C12—C11—H11	119.6
C4—C3—H3	120.5	C10—C11—H11	119.6
O1—C4—C3	103.86 (15)	C13—C12—C11	121.6 (2)
O1—C4—C5	107.44 (14)	C13—C12—H12	119.2
C3—C4—C5	119.51 (15)	C11—C12—H12	119.2
O1—C4—H4	108.5	C12—C13—C14	117.6 (2)
C3—C4—H4	108.5	C12—C13—C16	120.9 (2)
C5—C4—H4	108.5	C14—C13—C16	121.4 (2)
O5—C5—C4	107.78 (15)	C13—C14—C15	121.56 (19)
O5—C5—C6	104.29 (15)	C13—C14—H14	119.2
C4—C5—C6	115.52 (18)	C15—C14—H14	119.2
O5—C5—H5	109.7	C10—C15—C14	119.9 (2)
C4—C5—H5	109.7	C10—C15—H15	120.0
C6—C5—H5	109.7	C14—C15—H15	120.0
O6—C6—C5	102.58 (15)	C13—C16—H16A	109.5
O6—C6—H6A	111.3	C13—C16—H16B	109.5
C5—C6—H6A	111.3	H16A—C16—H16B	109.5
O6—C6—H6B	111.3	C13—C16—H16C	109.5
C5—C6—H6B	111.3	H16A—C16—H16C	109.5
H6A—C6—H6B	109.2	H16B—C16—H16C	109.5
O6—C7—O5	105.02 (14)
C4—O1—C1—C2	29.82 (17)	O1—C4—C5—C6	79.6 (2)
C4—O1—C1—S	−87.21 (14)	C3—C4—C5—C6	−38.2 (2)
C10—S—C1—O1	−75.82 (13)	C7—O6—C6—C5	35.7 (2)
C10—S—C1—C2	168.97 (13)	O5—C5—C6—O6	−23.0 (2)
C3—O2—C2—C1	−97.22 (17)	C4—C5—C6—O6	95.1 (2)
O1—C1—C2—O2	47.03 (18)	C6—O6—C7—O5	−35.10 (19)
S—C1—C2—O2	167.45 (12)	C6—O6—C7—C9	−151.05 (16)
O1—C1—C2—C3	−16.26 (18)	C6—O6—C7—C8	83.90 (19)
S—C1—C2—C3	104.17 (15)	C5—O5—C7—O6	19.8 (2)
C2—O2—C3—C4	95.86 (17)	C5—O5—C7—C9	136.19 (17)
C1—C2—C3—O2	105.77 (16)	C5—O5—C7—C8	−99.92 (19)
O2—C2—C3—C4	−108.14 (15)	C1—S—C10—C11	−73.55 (16)
C1—C2—C3—C4	−2.37 (19)	C1—S—C10—C15	108.51 (16)
C1—O1—C4—C3	−31.17 (16)	C15—C10—C11—C12	0.1 (3)
C1—O1—C4—C5	−158.71 (14)	S—C10—C11—C12	−177.84 (16)
O2—C3—C4—O1	−43.52 (18)	C10—C11—C12—C13	0.5 (3)
C2—C3—C4—O1	19.79 (18)	C11—C12—C13—C14	−0.4 (3)
O2—C3—C4—C5	76.1 (2)	C11—C12—C13—C16	179.6 (2)
C2—C3—C4—C5	139.41 (17)	C12—C13—C14—C15	−0.5 (3)
C7—O5—C5—C4	−121.00 (16)	C16—C13—C14—C15	179.5 (2)
C7—O5—C5—C6	2.3 (2)	C11—C10—C15—C14	−1.0 (3)
O1—C4—C5—O5	−164.23 (14)	S—C10—C15—C14	177.02 (15)
C3—C4—C5—O5	78.0 (2)	C13—C14—C15—C10	1.2 (3)