3-De­oxy-1,2-O-isopropyl­idene-3-C-methyl-5-O-(p-tolyl­sulfon­yl)-D-ribofuran­ose

In the title compound [alternative name: (2,2,6R-trimethyl­tetra­hydro­furo[2R,3R-d][1,3]dioxol-5S-yl)methyl 4-methyl­benzene­sulfonate], C₁₆H₂₂O₆S, the ribo-pento­furan­ose ring is in the T (twisted) conformation, with atom C3 exo and atom C4 endo. The isopropyl­idene ring is in an envelope conformation. The crystal structure is stabilized by means of van der Waals inter­actions and weak C—H...O inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.036
• wR factor = 0.105
• Data-to-parameter ratio = 9.9

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......       0.93

Alert level C
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.61 mm
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C9
PLAT850_ALERT_2_C Check Flack Parameter Exact Value 0.00 and su ..       0.02

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           69.19
           From the CIF: _reflns_number_total               2113
           Count of symmetry unique reflns         1849
           Completeness (_total/calc)            114.28%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       264
           Fraction of Friedel pairs measured     0.143
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
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 C3     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4     = .          S

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

   6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 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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Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: PLATON (Spek, 2003).

3-Deoxy-1,2-O-isopropylidene-3-C-methyl-5-O-(p-tolylsulfonyl)-D-ribofuranose

Crystal data

C16H22O6S	F(000) = 728
Mr = 342.40	Dx = 1.327 Mg m^−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 40 reflections
a = 7.7521 (3) Å	θ = 11.2–27.9°
b = 11.6202 (4) Å	µ = 1.93 mm^−1
c = 19.0242 (11) Å	T = 293 K
V = 1713.72 (13) Å^3	Prism, colourless
Z = 4	0.61 × 0.40 × 0.27 mm

Data collection

Siemens P4 four-circle diffractometer	2049 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.041
Graphite monochromator	θmax = 69.2°, θmin = 4.5°
ω/2θ scans	h = −1→9
Absorption correction: ψ scan [(North et al., 1968) and XEMP (Siemens, 1989)]	k = −1→14
Tmin = 0.441, Tmax = 0.595	l = −23→1
2295 measured reflections	3 standard reflections every 100 reflections
2113 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.036	w = 1/[σ^2(Fo^2) + (0.0618P)^2 + 0.1932P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.105	(Δ/σ)max = 0.010
S = 1.11	Δρmax = 0.15 e Å^−3
2113 reflections	Δρmin = −0.26 e Å^−3
213 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0202 (11)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), with 210 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.00 (2)

Special details

Experimental. Spectroscopic analysis: ¹H NMR (300 MHz, CDCl₃, δ, p.p.m.): 7.88 (d, J = 8.2 Hz, 2H, aromatic), 7.34 (d, J = 8.2 Hz, 2H, aromatic), 5.69 (d, J₁₂ = 3.5 Hz, 1H, H1), 4.52 (t, J₁₂ = J₂₃ = 4.1 Hz, 1H, H2), 4.23 (dd, J₄₅ = 2.5 Hz, J_55' = 11.1 Hz, 1H, H5), 4.07 (dd, J_5'4 = 3.9 Hz, J_5'5 = 11.1 Hz, 1H, H5'), 3.86 (dt, J₄₃ = 10.3 Hz, J₄₅ = J_45' = 3.2 Hz, 1H, H4), 2.45 (s, 3H, Me), 2.02 (dq, J₃₂ = 4.5 Hz, J₃₄ = 10.0 Hz, J_3-Me = 7.5 Hz, 1H, H3), 1.46 and 1.31 (two s, 3H each, isopropylidene), 1.03 (d, J_Me-3 = 6.8 Hz, 3H, Me); ¹³C NMR (75 MHz, CDCl₃, δ, p.p.m.): 144;91, 132.77, 129.84, 128.01, 111.72, 104.80, 82.50, 79.88, 68.50, 39.19, 26.71, 26.26, 21.65, 9.03. Exact mass calculated for C₁₆H₂₂O₆S + Na = 365.10295; found: 365.10166.

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 > 2/s(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
S1	0.42629 (8)	−0.00694 (6)	0.33590 (4)	0.0671 (2)
O1	0.8129 (3)	0.01976 (15)	0.16962 (9)	0.0685 (5)
O2	1.0693 (2)	0.22847 (15)	0.16694 (9)	0.0639 (5)
O3	1.0198 (4)	0.08386 (19)	0.09107 (11)	0.0939 (8)
O4	0.5597 (2)	0.00956 (18)	0.27433 (9)	0.0666 (5)
O5	0.4676 (3)	−0.10802 (17)	0.37455 (12)	0.0816 (6)
O6	0.2628 (3)	0.0008 (2)	0.30245 (12)	0.0854 (6)
C1	0.8602 (4)	0.1073 (2)	0.12240 (13)	0.0685 (7)
H1	0.7708	0.1183	0.0866	0.086*
C2	0.8867 (4)	0.2171 (2)	0.16474 (14)	0.0585 (6)
H2	0.8299	0.2840	0.1435	0.073*
C3	0.8162 (3)	0.1885 (2)	0.23695 (12)	0.0567 (6)
H3	0.6913	0.2015	0.2364	0.071*
C4	0.8480 (3)	0.0597 (2)	0.24002 (12)	0.0572 (6)
H4	0.9702	0.0464	0.2505	0.072*
C9	1.1400 (4)	0.1721 (2)	0.10741 (13)	0.0656 (7)
C6	1.1576 (5)	0.2531 (3)	0.04608 (15)	0.0854 (9)
H6A	1.0486	0.2896	0.0372	0.128*
H6B	1.1928	0.2108	0.0052	0.128*
H6C	1.2425	0.3106	0.0568	0.128*
C7	1.3105 (6)	0.1211 (4)	0.1286 (2)	0.1035 (12)
H7A	1.3856	0.1811	0.1450	0.155*
H7B	1.3620	0.0836	0.0888	0.155*
H7C	1.2929	0.0661	0.1655	0.155*
C8	0.8928 (5)	0.2566 (3)	0.29772 (15)	0.0758 (8)
H8A	0.8377	0.2342	0.3408	0.114*
H8B	0.8747	0.3374	0.2899	0.114*
H8C	1.0143	0.2414	0.3008	0.114*
C5	0.7413 (3)	−0.0092 (3)	0.29010 (14)	0.0636 (6)
H5A	0.7689	−0.0903	0.2855	0.080*
H5B	0.7657	0.0142	0.3380	0.080*
C10	0.4585 (3)	0.1132 (2)	0.38916 (14)	0.0622 (6)
C11	0.4272 (4)	0.2231 (2)	0.36226 (15)	0.0721 (7)
H11	0.3931	0.2322	0.3157	0.090*
C12	0.4467 (4)	0.3171 (3)	0.40457 (16)	0.0768 (8)
H12	0.4266	0.3902	0.3863	0.096*
C13	0.4965 (4)	0.3054 (3)	0.47488 (17)	0.0766 (8)
C14	0.5257 (5)	0.1965 (3)	0.50053 (15)	0.0798 (9)
H14	0.5579	0.1876	0.5473	0.100*
C15	0.5087 (4)	0.1004 (3)	0.45895 (15)	0.0724 (7)
H15	0.5306	0.0276	0.4773	0.091*
C16	0.5154 (6)	0.4090 (4)	0.5218 (2)	0.1023 (11)
H16A	0.6036	0.4585	0.5034	0.153*
H16B	0.5466	0.3845	0.5683	0.153*
H16C	0.4080	0.4500	0.5236	0.153*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0557 (3)	0.0705 (4)	0.0750 (4)	−0.0104 (4)	−0.0045 (3)	0.0200 (3)
O1	0.0837 (12)	0.0600 (9)	0.0618 (9)	−0.0184 (11)	−0.0003 (9)	−0.0067 (8)
O2	0.0637 (10)	0.0628 (10)	0.0651 (9)	−0.0054 (10)	0.0058 (9)	−0.0150 (8)
O3	0.1247 (19)	0.0782 (13)	0.0788 (12)	−0.0336 (15)	0.0377 (13)	−0.0294 (10)
O4	0.0588 (9)	0.0776 (11)	0.0633 (9)	−0.0103 (11)	−0.0057 (7)	0.0124 (9)
O5	0.0870 (15)	0.0681 (11)	0.0898 (13)	−0.0094 (12)	−0.0004 (12)	0.0238 (10)
O6	0.0573 (10)	0.1015 (14)	0.0975 (13)	−0.0157 (12)	−0.0141 (10)	0.0153 (14)
C1	0.0816 (18)	0.0692 (15)	0.0546 (12)	−0.0143 (17)	−0.0091 (13)	0.0015 (12)
C2	0.0618 (14)	0.0515 (12)	0.0621 (12)	0.0032 (13)	0.0004 (12)	0.0019 (11)
C3	0.0539 (12)	0.0553 (12)	0.0610 (12)	−0.0007 (13)	0.0006 (11)	−0.0033 (10)
C4	0.0565 (12)	0.0558 (12)	0.0594 (12)	−0.0009 (13)	−0.0033 (11)	0.0016 (10)
C9	0.0801 (18)	0.0610 (13)	0.0558 (12)	−0.0013 (16)	0.0102 (13)	−0.0043 (11)
C6	0.091 (2)	0.098 (2)	0.0675 (15)	−0.010 (2)	−0.0007 (16)	0.0165 (16)
C7	0.105 (3)	0.114 (3)	0.092 (2)	0.037 (3)	0.021 (2)	0.014 (2)
C8	0.084 (2)	0.0727 (16)	0.0703 (14)	−0.0110 (18)	0.0078 (16)	−0.0183 (13)
C5	0.0611 (13)	0.0634 (14)	0.0664 (13)	0.0031 (14)	−0.0038 (11)	0.0100 (12)
C10	0.0490 (12)	0.0721 (15)	0.0654 (13)	0.0021 (14)	−0.0015 (11)	0.0169 (12)
C11	0.0709 (16)	0.0765 (17)	0.0690 (14)	0.0060 (17)	−0.0050 (14)	0.0220 (13)
C12	0.0770 (19)	0.0709 (16)	0.0826 (17)	0.0112 (18)	0.0048 (16)	0.0167 (14)
C13	0.0631 (15)	0.088 (2)	0.0792 (16)	0.0028 (17)	0.0069 (15)	0.0033 (15)
C14	0.079 (2)	0.095 (2)	0.0655 (14)	0.011 (2)	−0.0014 (15)	0.0121 (14)
C15	0.0681 (16)	0.0790 (17)	0.0702 (14)	0.0058 (17)	−0.0020 (14)	0.0262 (13)
C16	0.102 (3)	0.100 (2)	0.105 (2)	0.002 (3)	0.010 (2)	−0.011 (2)

Geometric parameters (Å, º)

S1—O6	1.421 (2)	C6—H6C	0.9600
S1—O5	1.422 (2)	C7—H7A	0.9600
S1—O4	1.5740 (19)	C7—H7B	0.9600
S1—C10	1.743 (3)	C7—H7C	0.9600
O1—C1	1.406 (3)	C8—H8A	0.9600
O1—C4	1.443 (3)	C8—H8B	0.9600
O2—C9	1.418 (3)	C8—H8C	0.9600
O2—C2	1.423 (3)	C5—H5A	0.9700
O3—C1	1.400 (4)	C5—H5B	0.9700
O3—C9	1.420 (4)	C10—C15	1.392 (4)
O4—C5	1.456 (3)	C10—C11	1.397 (4)
C1—C2	1.523 (3)	C11—C12	1.366 (4)
C1—H1	0.9800	C11—H11	0.9300
C2—C3	1.515 (3)	C12—C13	1.399 (4)
C2—H2	0.9800	C12—H12	0.9300
C3—C4	1.518 (3)	C13—C14	1.375 (5)
C3—C8	1.522 (4)	C13—C16	1.506 (5)
C3—H3	0.9800	C14—C15	1.375 (5)
C4—C5	1.495 (4)	C14—H14	0.9300
C4—H4	0.9800	C15—H15	0.9300
C9—C7	1.504 (5)	C16—H16A	0.9600
C9—C6	1.505 (4)	C16—H16B	0.9600
C6—H6A	0.9600	C16—H16C	0.9600
C6—H6B	0.9600
O6—S1—O5	119.00 (15)	H6A—C6—H6C	109.5
O6—S1—O4	104.18 (12)	H6B—C6—H6C	109.5
O5—S1—O4	109.71 (13)	C9—C7—H7A	109.5
O6—S1—C10	109.70 (15)	C9—C7—H7B	109.5
O5—S1—C10	109.19 (13)	H7A—C7—H7B	109.5
O4—S1—C10	103.94 (12)	C9—C7—H7C	109.5
C1—O1—C4	108.12 (18)	H7A—C7—H7C	109.5
C9—O2—C2	108.5 (2)	H7B—C7—H7C	109.5
C1—O3—C9	110.2 (2)	C3—C8—H8A	109.5
C5—O4—S1	117.62 (15)	C3—C8—H8B	109.5
O3—C1—O1	111.2 (2)	H8A—C8—H8B	109.5
O3—C1—C2	105.6 (2)	C3—C8—H8C	109.5
O1—C1—C2	107.67 (19)	H8A—C8—H8C	109.5
O3—C1—H1	110.7	H8B—C8—H8C	109.5
O1—C1—H1	110.7	O4—C5—C4	108.9 (2)
C2—C1—H1	110.7	O4—C5—H5A	109.9
O2—C2—C3	110.6 (2)	C4—C5—H5A	109.9
O2—C2—C1	103.2 (2)	O4—C5—H5B	109.9
C3—C2—C1	104.29 (19)	C4—C5—H5B	109.9
O2—C2—H2	112.7	H5A—C5—H5B	108.3
C3—C2—H2	112.7	C15—C10—C11	119.7 (3)
C1—C2—H2	112.7	C15—C10—S1	120.6 (2)
C2—C3—C4	101.1 (2)	C11—C10—S1	119.6 (2)
C2—C3—C8	115.7 (2)	C12—C11—C10	119.8 (3)
C4—C3—C8	114.9 (2)	C12—C11—H11	120.1
C2—C3—H3	108.2	C10—C11—H11	120.1
C4—C3—H3	108.2	C11—C12—C13	121.1 (3)
C8—C3—H3	108.2	C11—C12—H12	119.5
O1—C4—C5	108.3 (2)	C13—C12—H12	119.5
O1—C4—C3	104.52 (19)	C14—C13—C12	118.3 (3)
C5—C4—C3	117.6 (2)	C14—C13—C16	120.6 (3)
O1—C4—H4	108.7	C12—C13—C16	121.0 (3)
C5—C4—H4	108.7	C15—C14—C13	121.8 (3)
C3—C4—H4	108.7	C15—C14—H14	119.1
O2—C9—O3	104.8 (2)	C13—C14—H14	119.1
O2—C9—C7	107.9 (3)	C14—C15—C10	119.3 (3)
O3—C9—C7	110.5 (3)	C14—C15—H15	120.4
O2—C9—C6	111.4 (2)	C10—C15—H15	120.4
O3—C9—C6	110.0 (2)	C13—C16—H16A	109.5
C7—C9—C6	112.0 (3)	C13—C16—H16B	109.5
C9—C6—H6A	109.5	H16A—C16—H16B	109.5
C9—C6—H6B	109.5	C13—C16—H16C	109.5
H6A—C6—H6B	109.5	H16A—C16—H16C	109.5
C9—C6—H6C	109.5	H16B—C16—H16C	109.5
O5—S1—O4—C5	−43.6 (2)	O1—C1—C2—C3	−10.8 (3)
O6—S1—O4—C5	−172.0 (2)	O1—C1—C2—O2	104.9 (2)
C10—S1—O4—C5	73.1 (2)	O3—C1—C2—O2	−14.0 (2)
O4—S1—C10—C11	62.6 (2)	O3—C1—C2—C3	−129.7 (2)
O4—S1—C10—C15	−119.9 (2)	O2—C2—C3—C4	−81.3 (2)
O5—S1—C10—C11	179.6 (2)	C1—C2—C3—C8	153.8 (2)
O5—S1—C10—C15	−2.9 (3)	O2—C2—C3—C8	43.5 (3)
O6—S1—C10—C11	−48.4 (3)	C1—C2—C3—C4	29.0 (2)
O6—S1—C10—C15	129.2 (2)	C2—C3—C4—O1	−37.8 (2)
C4—O1—C1—O3	101.6 (2)	C8—C3—C4—O1	−163.1 (2)
C4—O1—C1—C2	−13.6 (3)	C8—C3—C4—C5	76.8 (3)
C1—O1—C4—C3	32.8 (3)	C2—C3—C4—C5	−157.9 (2)
C1—O1—C4—C5	158.9 (2)	C3—C4—C5—O4	56.5 (3)
C9—O2—C2—C1	26.0 (2)	O1—C4—C5—O4	−61.6 (3)
C9—O2—C2—C3	137.08 (19)	S1—C10—C15—C14	−177.1 (3)
C2—O2—C9—O3	−28.2 (2)	C15—C10—C11—C12	0.2 (4)
C2—O2—C9—C6	90.6 (3)	S1—C10—C11—C12	177.8 (2)
C2—O2—C9—C7	−146.1 (3)	C11—C10—C15—C14	0.4 (4)
C9—O3—C1—O1	−119.3 (2)	C10—C11—C12—C13	−0.5 (5)
C9—O3—C1—C2	−2.8 (3)	C11—C12—C13—C14	0.1 (5)
C1—O3—C9—O2	18.7 (3)	C11—C12—C13—C16	−179.1 (3)
C1—O3—C9—C6	−101.1 (3)	C16—C13—C14—C15	179.7 (3)
C1—O3—C9—C7	134.7 (3)	C12—C13—C14—C15	0.6 (5)
S1—O4—C5—C4	−153.96 (18)	C13—C14—C15—C10	−0.8 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O4	0.98	2.56	2.964 (3)	105
C4—H4···O6^i	0.98	2.53	3.496 (3)	168
C15—H15···O5	0.93	2.56	2.923 (4)	104
C15—H15···O3^ii	0.93	2.55	3.309 (4)	139

Symmetry codes: (i) x+1, y, z; (ii) −x+3/2, −y, z+1/2.