1-O-p-Toluene­sulfonyl-2,3:4,5-di-O-iso­propyl­idene-L-arabitol

In the title compound, C₁₈H₂₆SO₇, the absolute configuration was confirmed as S at all three chiral centres. Molecules are linked by three C—H...O contacts.

Key indicators

• Single-crystal X-ray study
• T = 143 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.040
• wR factor = 0.100
• Data-to-parameter ratio = 17.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.53
         From the CIF: _reflns_number_total               4154
         Count of symmetry unique reflns         2311
         Completeness (_total/calc)            179.75%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      1843
         Fraction of Friedel pairs measured     0.797
         Are heavy atom types Z>Si present          yes
          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.

---

S1. Comment

The title compound, (I), is a representative of a class of compounds important in the synthesis of polyhydroxyalkyl derivatives (Holy, 1978, 1982).

The molecule of (I) is shown in Fig. 1. The absolute configuration is confirmed as S at all three chiral centres C2, C3 and C4.

The conformation of the five-membered ring C2/C3/C10/O8/C9 is approximately twist (local diad through O9 and the midpoint of C3—O8) and that of C4/C5/C13/O6/C7 is approximately envelope (local mirror though C4 and the midpoint of C13—O6).

Molecules are linked by three C—H···O contacts that may be regarded as weak hydrogen bonds (Table 2); one, H4···O17, is much shorter than the others. The two contacts with purely translational symmetry operators link the molecules to form layers parallel to the xz plane at y ≈ 1/4, 3/4 (Fig. 2).

S2. Experimental

The title compound was synthesized starting from L-arabitol, as described by Holy (1982). Single crystals arose when the mother liquor was left undisturbed.

S3. Refinement

Methyl H atoms were identified in difference syntheses, idealized and then refined using rigid methyl groups (C—H = 0.98 Å and H—C—H = 109.5°) allowed to rotate but not tip. Other H atoms were included using a riding model, with C—H = 0.95 (sp²), 0.99 (methylene) or 1.00 Å (methine). The absolute configuration was based on 1849 Friedel pairs.

Computing details

Data collection: DIF4 (Stoe & Cie, 1992); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecule of the title compound, (I), in the crystal. Ellipsoids represent 50% probability levels. H-atom radii are arbitrary.
	Fig. 2. Packing diagram of (I), projected parallel to the y axis. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonds have been omitted.

1-O-p-toluenesulfonyl-2,3:4,5-di-O-isopropylidene-L-arabitol

Crystal data

C18H26O7S	F(000) = 412
Mr = 386.45	Dx = 1.333 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.9957 (10) Å	Cell parameters from 52 reflections
b = 14.527 (3) Å	θ = 10–11.5°
c = 8.3194 (14) Å	µ = 0.20 mm^−1
β = 94.93 (2)°	T = 143 K
V = 962.8 (3) Å^3	Plate, colourless
Z = 2	0.7 × 0.5 × 0.15 mm

Data collection

Stoe DIF4 diffractometer	Rint = 0.018
Radiation source: fine-focus sealed tube	θmax = 27.5°, θmin = 3.4°
Graphite monochromator	h = −10→10
ω/θ scans	k = −16→18
4605 measured reflections	l = −10→10
4154 independent reflections	3 standard reflections every 60 min
3891 reflections with I > 2σ(I)	intensity decay: 1.3%

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)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.0531P)^2 + 0.2455P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
4154 reflections	Δρmax = 0.23 e Å^−3
240 parameters	Δρmin = −0.24 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (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.

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

	x	y	z	Uiso*/Ueq
C1	0.5207 (3)	0.79000 (15)	0.8035 (2)	0.0253 (4)
H1A	0.4795	0.8518	0.8311	0.030*
H1B	0.6448	0.7921	0.8082	0.030*
C2	0.4661 (3)	0.72006 (14)	0.9213 (2)	0.0221 (4)
H2	0.5010	0.7409	1.0337	0.026*
C3	0.2790 (2)	0.69517 (15)	0.9078 (2)	0.0225 (4)
H3	0.2320	0.7001	0.7928	0.027*
C4	0.1752 (3)	0.75241 (15)	1.0132 (3)	0.0242 (4)
H4	0.2187	0.7469	1.1292	0.029*
C5	−0.0122 (3)	0.73407 (18)	0.9925 (3)	0.0321 (5)
H5A	−0.0475	0.7133	0.8814	0.039*
H5B	−0.0446	0.6869	1.0698	0.039*
O6	−0.0839 (2)	0.82085 (13)	1.0249 (2)	0.0417 (5)
O7	0.18521 (19)	0.84537 (11)	0.9597 (2)	0.0312 (4)
O8	0.27746 (19)	0.60195 (11)	0.9579 (2)	0.0341 (4)
O9	0.54235 (18)	0.63342 (11)	0.89318 (19)	0.0259 (3)
C10	0.4464 (3)	0.56617 (16)	0.9697 (3)	0.0262 (4)
C11	0.4485 (3)	0.47753 (16)	0.8754 (3)	0.0314 (5)
H11A	0.5621	0.4516	0.8859	0.038*
H11B	0.4146	0.4898	0.7614	0.038*
H11C	0.3702	0.4336	0.9177	0.038*
C12	0.5090 (3)	0.55630 (19)	1.1451 (3)	0.0354 (5)
H12A	0.5070	0.6165	1.1980	0.042*
H12B	0.6242	0.5326	1.1533	0.042*
H12C	0.4366	0.5134	1.1978	0.042*
C13	0.0348 (3)	0.89175 (17)	0.9939 (3)	0.0298 (5)
C14	0.0641 (3)	0.9499 (2)	1.1433 (3)	0.0405 (6)
H14A	0.1401	1.0007	1.1227	0.049*
H14B	0.1144	0.9121	1.2323	0.049*
H14C	−0.0432	0.9749	1.1722	0.049*
C15	−0.0257 (4)	0.9470 (2)	0.8470 (3)	0.0431 (6)
H15A	−0.0577	0.9052	0.7571	0.052*
H15B	0.0643	0.9878	0.8176	0.052*
H15C	−0.1232	0.9839	0.8708	0.052*
O16	0.45175 (19)	0.76403 (11)	0.64149 (17)	0.0258 (3)
O17	0.4286 (2)	0.78277 (13)	0.35815 (19)	0.0368 (4)
O18	0.5789 (2)	0.90040 (12)	0.5278 (2)	0.0339 (4)
S19	0.53854 (6)	0.80636 (4)	0.49578 (6)	0.02601 (12)
C20	0.7248 (3)	0.74269 (16)	0.4949 (2)	0.0257 (4)
C21	0.7229 (3)	0.64848 (17)	0.5190 (3)	0.0323 (5)
H21	0.6218	0.6180	0.5398	0.039*
C22	0.8708 (3)	0.59911 (18)	0.5123 (3)	0.0342 (5)
H22	0.8701	0.5343	0.5279	0.041*
C23	1.0205 (3)	0.64290 (18)	0.4831 (3)	0.0313 (5)
C24	1.0180 (3)	0.73729 (19)	0.4593 (3)	0.0354 (5)
H24	1.1190	0.7680	0.4392	0.042*
C25	0.8718 (3)	0.78791 (17)	0.4642 (3)	0.0333 (5)
H25	0.8721	0.8525	0.4468	0.040*
C26	1.1808 (3)	0.5895 (2)	0.4795 (3)	0.0410 (6)
H26A	1.2607	0.6096	0.5684	0.049*
H26B	1.2287	0.6003	0.3766	0.049*
H26C	1.1576	0.5237	0.4911	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0284 (10)	0.0224 (12)	0.0251 (9)	−0.0039 (8)	0.0022 (8)	−0.0008 (8)
C2	0.0236 (10)	0.0197 (11)	0.0230 (9)	0.0017 (7)	0.0023 (7)	−0.0019 (7)
C3	0.0218 (9)	0.0179 (10)	0.0281 (10)	0.0011 (7)	0.0038 (7)	−0.0009 (8)
C4	0.0260 (10)	0.0208 (11)	0.0261 (10)	0.0035 (8)	0.0043 (8)	−0.0007 (8)
C5	0.0274 (11)	0.0277 (13)	0.0422 (13)	0.0005 (9)	0.0090 (9)	−0.0028 (10)
O6	0.0269 (8)	0.0303 (11)	0.0697 (12)	0.0045 (7)	0.0147 (8)	−0.0025 (8)
O7	0.0262 (8)	0.0199 (8)	0.0488 (10)	0.0040 (6)	0.0105 (7)	−0.0018 (7)
O8	0.0258 (8)	0.0178 (8)	0.0601 (11)	0.0023 (6)	0.0125 (7)	0.0028 (7)
O9	0.0252 (7)	0.0193 (8)	0.0341 (8)	0.0033 (6)	0.0082 (6)	0.0009 (6)
C10	0.0254 (10)	0.0198 (11)	0.0339 (11)	0.0018 (8)	0.0062 (8)	−0.0002 (8)
C11	0.0349 (12)	0.0215 (12)	0.0382 (12)	0.0035 (9)	0.0048 (9)	−0.0040 (9)
C12	0.0456 (14)	0.0276 (12)	0.0331 (12)	−0.0016 (10)	0.0048 (10)	0.0029 (10)
C13	0.0263 (12)	0.0241 (12)	0.0400 (13)	0.0059 (9)	0.0080 (9)	−0.0017 (9)
C14	0.0381 (13)	0.0435 (16)	0.0400 (14)	0.0095 (11)	0.0040 (10)	−0.0089 (11)
C15	0.0439 (15)	0.0460 (17)	0.0391 (14)	0.0131 (12)	0.0016 (11)	0.0020 (11)
O16	0.0252 (7)	0.0282 (8)	0.0242 (7)	−0.0054 (6)	0.0036 (6)	−0.0007 (6)
O17	0.0335 (8)	0.0485 (12)	0.0280 (8)	0.0004 (7)	0.0001 (6)	0.0055 (7)
O18	0.0353 (8)	0.0256 (9)	0.0417 (9)	0.0003 (7)	0.0084 (7)	0.0057 (7)
S19	0.0257 (2)	0.0269 (3)	0.0256 (2)	−0.0007 (2)	0.00322 (17)	0.0038 (2)
C20	0.0251 (10)	0.0282 (12)	0.0239 (10)	0.0015 (8)	0.0035 (7)	−0.0010 (8)
C21	0.0304 (11)	0.0288 (13)	0.0383 (12)	−0.0034 (9)	0.0059 (9)	0.0039 (9)
C22	0.0397 (12)	0.0257 (12)	0.0369 (12)	0.0040 (9)	0.0030 (10)	0.0006 (10)
C23	0.0312 (11)	0.0352 (14)	0.0270 (11)	0.0032 (10)	0.0004 (8)	−0.0079 (9)
C24	0.0274 (11)	0.0362 (14)	0.0435 (13)	−0.0037 (10)	0.0081 (9)	−0.0040 (11)
C25	0.0316 (11)	0.0303 (15)	0.0389 (12)	−0.0038 (9)	0.0086 (9)	0.0001 (9)
C26	0.0368 (13)	0.0363 (15)	0.0493 (15)	0.0066 (11)	0.0003 (11)	−0.0126 (11)

Geometric parameters (Å, º)

C1—O16	1.461 (2)	C12—H12C	0.9800
C1—C2	1.502 (3)	C13—C14	1.505 (3)
C1—H1A	0.9900	C13—C15	1.507 (3)
C1—H1B	0.9900	C14—H14A	0.9800
C2—O9	1.427 (2)	C14—H14B	0.9800
C2—C3	1.533 (3)	C14—H14C	0.9800
C2—H2	1.0000	C15—H15A	0.9800
C3—O8	1.417 (3)	C15—H15B	0.9800
C3—C4	1.508 (3)	C15—H15C	0.9800
C3—H3	1.0000	O16—S19	1.5728 (15)
C4—O7	1.426 (3)	O17—S19	1.4243 (17)
C4—C5	1.517 (3)	O18—S19	1.4237 (19)
C4—H4	1.0000	S19—C20	1.754 (2)
C5—O6	1.420 (3)	C20—C21	1.384 (3)
C5—H5A	0.9900	C20—C25	1.389 (3)
C5—H5B	0.9900	C21—C22	1.389 (3)
O6—C13	1.439 (3)	C21—H21	0.9500
O7—C13	1.428 (3)	C22—C23	1.395 (4)
O8—C10	1.443 (3)	C22—H22	0.9500
O9—C10	1.425 (3)	C23—C24	1.385 (4)
C10—C12	1.508 (3)	C23—C26	1.501 (3)
C10—C11	1.509 (3)	C24—C25	1.384 (3)
C11—H11A	0.9800	C24—H24	0.9500
C11—H11B	0.9800	C25—H25	0.9500
C11—H11C	0.9800	C26—H26A	0.9800
C12—H12A	0.9800	C26—H26B	0.9800
C12—H12B	0.9800	C26—H26C	0.9800
O16—C1—C2	108.63 (16)	H12B—C12—H12C	109.5
O16—C1—H1A	110.0	O7—C13—O6	106.13 (18)
C2—C1—H1A	110.0	O7—C13—C14	110.81 (19)
O16—C1—H1B	110.0	O6—C13—C14	108.2 (2)
C2—C1—H1B	110.0	O7—C13—C15	107.91 (19)
H1A—C1—H1B	108.3	O6—C13—C15	110.8 (2)
O9—C2—C1	109.73 (17)	C14—C13—C15	112.8 (2)
O9—C2—C3	102.01 (16)	C13—C14—H14A	109.5
C1—C2—C3	116.63 (17)	C13—C14—H14B	109.5
O9—C2—H2	109.4	H14A—C14—H14B	109.5
C1—C2—H2	109.4	C13—C14—H14C	109.5
C3—C2—H2	109.4	H14A—C14—H14C	109.5
O8—C3—C4	109.70 (17)	H14B—C14—H14C	109.5
O8—C3—C2	103.71 (16)	C13—C15—H15A	109.5
C4—C3—C2	114.18 (17)	C13—C15—H15B	109.5
O8—C3—H3	109.7	H15A—C15—H15B	109.5
C4—C3—H3	109.7	C13—C15—H15C	109.5
C2—C3—H3	109.7	H15A—C15—H15C	109.5
O7—C4—C3	107.00 (17)	H15B—C15—H15C	109.5
O7—C4—C5	102.24 (18)	C1—O16—S19	116.98 (12)
C3—C4—C5	115.13 (19)	O18—S19—O17	119.73 (11)
O7—C4—H4	110.7	O18—S19—O16	109.80 (10)
C3—C4—H4	110.7	O17—S19—O16	104.05 (9)
C5—C4—H4	110.7	O18—S19—C20	109.15 (11)
O6—C5—C4	103.50 (19)	O17—S19—C20	109.60 (11)
O6—C5—H5A	111.1	O16—S19—C20	103.19 (9)
C4—C5—H5A	111.1	C21—C20—C25	121.0 (2)
O6—C5—H5B	111.1	C21—C20—S19	120.07 (17)
C4—C5—H5B	111.1	C25—C20—S19	118.93 (18)
H5A—C5—H5B	109.0	C20—C21—C22	119.0 (2)
C5—O6—C13	108.55 (17)	C20—C21—H21	120.5
C4—O7—C13	108.30 (17)	C22—C21—H21	120.5
C3—O8—C10	109.42 (16)	C21—C22—C23	121.2 (2)
C10—O9—C2	106.11 (16)	C21—C22—H22	119.4
O9—C10—O8	105.03 (17)	C23—C22—H22	119.4
O9—C10—C12	110.51 (18)	C24—C23—C22	118.3 (2)
O8—C10—C12	109.35 (19)	C24—C23—C26	120.7 (2)
O9—C10—C11	108.81 (18)	C22—C23—C26	121.0 (3)
O8—C10—C11	108.91 (18)	C25—C24—C23	121.6 (2)
C12—C10—C11	113.8 (2)	C25—C24—H24	119.2
C10—C11—H11A	109.5	C23—C24—H24	119.2
C10—C11—H11B	109.5	C24—C25—C20	118.9 (2)
H11A—C11—H11B	109.5	C24—C25—H25	120.5
C10—C11—H11C	109.5	C20—C25—H25	120.5
H11A—C11—H11C	109.5	C23—C26—H26A	109.5
H11B—C11—H11C	109.5	C23—C26—H26B	109.5
C10—C12—H12A	109.5	H26A—C26—H26B	109.5
C10—C12—H12B	109.5	C23—C26—H26C	109.5
H12A—C12—H12B	109.5	H26A—C26—H26C	109.5
C10—C12—H12C	109.5	H26B—C26—H26C	109.5
H12A—C12—H12C	109.5
O16—C1—C2—O9	66.6 (2)	C4—O7—C13—C14	101.1 (2)
O16—C1—C2—C3	−48.7 (2)	C4—O7—C13—C15	−134.9 (2)
O9—C2—C3—O8	29.19 (19)	C5—O6—C13—O7	−6.2 (2)
C1—C2—C3—O8	148.71 (18)	C5—O6—C13—C14	−125.2 (2)
O9—C2—C3—C4	148.52 (17)	C5—O6—C13—C15	110.7 (2)
C1—C2—C3—C4	−92.0 (2)	C2—C1—O16—S19	−160.18 (14)
O8—C3—C4—O7	178.56 (17)	C1—O16—S19—O18	−40.71 (17)
C2—C3—C4—O7	62.7 (2)	C1—O16—S19—O17	−170.00 (16)
O8—C3—C4—C5	−68.6 (2)	C1—O16—S19—C20	75.55 (17)
C2—C3—C4—C5	175.52 (19)	O18—S19—C20—C21	158.93 (18)
O7—C4—C5—O6	−33.0 (2)	O17—S19—C20—C21	−68.2 (2)
C3—C4—C5—O6	−148.65 (19)	O16—S19—C20—C21	42.2 (2)
C4—C5—O6—C13	24.3 (2)	O18—S19—C20—C25	−23.2 (2)
C3—C4—O7—C13	151.62 (17)	O17—S19—C20—C25	109.67 (19)
C5—C4—O7—C13	30.2 (2)	O16—S19—C20—C25	−139.96 (18)
C4—C3—O8—C10	−133.01 (18)	C25—C20—C21—C22	0.1 (3)
C2—C3—O8—C10	−10.7 (2)	S19—C20—C21—C22	177.84 (18)
C1—C2—O9—C10	−161.76 (16)	C20—C21—C22—C23	0.5 (4)
C3—C2—O9—C10	−37.49 (19)	C21—C22—C23—C24	−0.5 (4)
C2—O9—C10—O8	31.7 (2)	C21—C22—C23—C26	178.7 (2)
C2—O9—C10—C12	−86.1 (2)	C22—C23—C24—C25	0.0 (4)
C2—O9—C10—C11	148.19 (18)	C26—C23—C24—C25	−179.2 (2)
C3—O8—C10—O9	−12.0 (2)	C23—C24—C25—C20	0.5 (4)
C3—O8—C10—C12	106.6 (2)	C21—C20—C25—C24	−0.5 (3)
C3—O8—C10—C11	−128.42 (19)	S19—C20—C25—C24	−178.35 (18)
C4—O7—C13—O6	−16.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O17^i	1.00	2.48	3.396 (3)	152
C15—H15C···O8^ii	0.98	2.61	3.509 (3)	153
C24—H24···O17^iii	0.95	2.63	3.521 (3)	156

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