Dipolar S=O...C=O and C-H...O inter­actions in the mol­ecular organization of 4,6-di-O-acetyl-2-O-tosyl-myo-inositol 1,3,5-orthoesters

In the absence of conventional hydrogen bonding, the mol­ecules of 4,6-di-O-acetyl-2-O-tosyl-myo-inositol 1,3,5-orthoformate, C₁₈H₂₀O₁₀S, (I), and 4,6-di-O-acetyl-2-O-tosyl-myo-inositol 1,3,5-orthobenzoate, C₂₄H₂₄O₁₀S, (II), are associated via C-H...O inter­actions. Mol­ecules of (II) are additionally linked via dipolar S=O...C=O contacts. It is inter­esting to note that the sulfonyl O atom involved in the dipolar S=O...C=O contacts does not take part in any other inter­action, indicating the competitive nature of this contact relative to the weak hydrogen-bonding inter­actions.

S1. Comment

Non-covalent intermolecular interactions play a vital role in the specificity associated with molecular recognition in chemical and complex biological processes (Glusker, 1998). This necessitates an understanding of the various types and strengths of non-covalent interactions that bind molecules in crystal structures. These studies are significant because of their application in crystal engineering, supramolecular chemistry, and the design of functional materials and drugs (Desiraju & Steiner, 1999). For instance, the importance of dipolar interactions such as C═O···C═O and C—F···C═O has been recognized in the conformational stabilization of proteins (Maccallum et al., 1995) and in structure-based drug design (Hof & Diedrich, 2004). We have previously reported (Manoj et al., 2006) the significance of dipolar S═O···C═O contacts between the diastereomers of camphorsulfonate derivatives of myo-inositol for the formation of solvent-inclusion crystals. The title compounds, (I) and (II), were synthesized to explore the activity of S═O···C═O interactions in sulfonylated myo-inositol derivatives containing sulfonyl and acyl groups. Sulfonylated myo-inositol orthoesters are key intermediates (Sureshan et al., 2003) for the synthesis of biologically important phosphorylated inositols, which play a significant role in cellular signal transduction (Potter & Lampe, 1995).

Crystallization of (I) and (II) from common organic solvents resulted in triclinic and monoclinic crystals, respectively. The molecules adopt similar conformations (Figs. 1 and 2) in both compounds, although the orthoester H atom in (I) is substituted by a phenyl group in (II). The regioisomers [racemic 2,4-di-O-acetyl-6-O-tosyl-myo-inositol orthoformate and its orthoacetate analogue] produce conformational polymorphs with different orientations of the tosyl group about the O—S bond (Manoj et al., 2009).

Molecules of (I) and (II) associate centrosymmetrically in their crystal structures to form dimers, via different non-covalent interactions involving sulfonyl O atoms. In compound (I), sulfonyl atom O8 is engaged in the formation of bifurcated C—H···O interactions with atoms H9^iv and H16B^iv(Fig. 3, Table 1); whereas in (II), the sulfonyl atom O7 is involved in a dipolar S═O···C═O contact with carbonyl atom C23ⁱ, and atom O8 makes a short C—H···O contact with inositol ring atom H1ⁱ across the inversion centre (Fig. 4, Table 2). In these S═O···C═O contacts, the S═O group is perpendicular to the C═O group (Manoj et al., 2007) and the geometric parameters [O7···C23ⁱ = 3.194 (3) Å, O7···C23═ O10ⁱ = 84.4 (2)° and S1═O7···C23ⁱ =147.9 (2)°; symmetry code: (i) -x + 2, -y + 2, -z + 1] indicate that the interaction motif is of Type I (Allen et al., 1998). It is worthy of note that the sulfonyl atom O7 involved in the S═O···C═O contacts (Manoj et al., 2007) does not take part in any other weak interaction. We have previously observed that S═O···C═O contacts are complementary to C—H···O interactions in camphorsulfonyl derivatives of myo-inositol orthoformate (Manoj et al., 2006).

The organization of the dimers (Figs. 3 and 4) in (I) and (II) is observed to be similar [in the bc plane in (I) and the ac plane in (II)]. The dimers translate to form chains via weak van der Waals contacts along the direction of the b axis in (I) (Fig. 5), and along the c axis in (II) (Fig. 6). These chains form a layered arrangement in the bc plane in (I) with four weak hydrogen-bonding interactions, namely C4—H4···O5ⁱⁱ, C7—H7···O9ⁱⁱ, C16—H16A···O10^vi and C18—H18A···O9^vi, whereas in (II) the chains are linked by a C5—H5···O10ⁱⁱ interaction (see Table 1 and 2 for symmetry codes).

These molecular layers are packed in the third dimension by translation of the dimers via C—H···O interactions (see supplementary material for figures): C1—H1···O9ⁱ and C16—H16B···O8^iv contacts in (I) (Table 1) and C22—H22C···O10ⁱⁱⁱ and C24—H24B···O9^iv contacts in (II) (Table 2), without leaving voids either for solvent inclusion or for conformational flexibility. In conclusion, the molecular association via S═O···C═O contacts observed in (II) is of considerable interest and could have relevance in the binding of sulfa [sulfur?] drugs to their receptor proteins. Further work on the theoretical energy calculation of dipolar associations and their packing motifs is underway.

S2. Experimental

The preparation of (I) was carried out as follows. 2-O-Tosyl-myo-inositol 1,3,5-orthoformate (0.172 g, 0.5 mmol; Sureshan et al., 2003) and acetic anhydride (0.2 ml, 2.10 mmol) were dissolved in pyridine (6 ml) and the mixture stirred at room temperature for 8 h. The solvent was evaporated from the reaction mixture under reduced pressure and the residue worked up with ethyl acetate. The product was purified by flash column chromatography to obtain 2-O-tosyl-4,6-di-O-acetyl-myo-inositol 1,3,5-orthoformate, (I), as a colourless solid (yield 0.205 g, 96%; m.p. 448–449 K). IR (CHCl₃, ν, cm^-1): 1751; ¹H NMR (200 MHz, CDCl₃, δ): 2.09 (s, 6H, MeCO), 2.47 (s, 3H, ArMe), 4.25–4.31 (m, 2H, Ins H), 4.52–4.58 (m, 1H, Ins H), 4.94–4.98 (m, 1H, Ins H), 5.46 (t, J = 3.9 Hz, 2H, Ins H), 5.52 (d, 1H, J = 1.5 Hz, O₃CH), 7.34–7.42 (m, 2H, ArH), 7.82–7.89 (m, 2H, ArH); ¹³C NMR (50 MHz, CDCl₃, δ): 20.5, 21.6, 65.8, 67.5, 68.8, 69.1, 71.8, 102.7, 127.7, 129.9, 133.3, 145.5, 168.7. Analysis, calculated for C₁₈H₂₀O₁₀S: C 50.47, H 4.71%; found: C 50.23, H 4.55%.

The preparation of (II) was carried out as follows. A mixture of myo-inositol 1,3,5-orthobenzoate (0.266 g, 1 mmol; Murali et al., 2007), tosyl chloride (0.200 g, 1.05 mmol) and pyridine (8 ml) was heated at 353 K for 48 h. The reaction mixture was concentrated under reduced pressure and the residue worked up as usual. The product was purified by column chromatography to obtain 2-O-tosyl-myo-inositol 1,3,5-orthobenzoate (yield 0.264 g, 63%; m.p. 429–430 K). The 2-O-tosyl derivative (0.211 g, 0.5 mmol) and acetic anhydride (0.2 ml, 4 mmol) were dissolved in pyridine (6 ml) and the mixture stirred at room temperature for 8 h. The solvent was evaporated from the reaction mixture under reduced pressure and the residue worked up as usual. The product was purified by flash column chromatography to obtain the diacetate, (II) as a colourless solid (yield 0.459 g, 91%; m.p. 461–462 K). IR (CHCl₃, ν, cm^-1): 1755; ¹H NMR (200 MHz, CDCl₃, δ): 2.11 (s, 6H, MeCO), 2.46 (s, 3H, ArMe), 4.43–4.50 (m, 2H, Ins H), 4.65–4.73 (m, 1H, Ins H), 5.01 (t, J = 1.9 Hz, 1H, Ins H), 5.58 (m, 2H, Ins H), 7.31–7.41 (m, 5H, ArH), 7.54–7.62 (m, 2H, ArH), 7.82–7.90 (m, 2H, ArH); ¹³C NMR (50 MHz, CDCl₃, δ): 20.6, 21.6, 66.8, 67.7, 68.2, 70.5, 107.8, 125.3, 127.7, 128.0, 129.8, 129.9, 133.6, 135.8, 145.4, 168.8. Analysis, calculated for C₂₄H₂₄O₁₀S: C 57.14, H 4.79%; found: C 57.23, H 4.97%.

Crystallization was carried out by the slow evaporation of a solution of (I) or (II) in organic solvents such as acetonitrile, chloroform, dichloromethane, ethyl acetate and nitromethane at ambient temperature.

S3. Refinement

All the H atoms were placed in idealized positions (C—H = 0.98 Å for atom H7 and inositol ring H atoms, C—H = 0.93 Å for phenyl H atoms and C—H = 0.96 Å for methyl H atoms) and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). In compound (I), the anisotropic displacement parameters for carbonyl atom O10 were too large, which indicates orientational disorder. However, a reasonable model was obtained by splitting the acetyl group into two components (C18—C17═O10 and C18'—C17'═O10'), with the sum of the site-occupancy factors for the disordered atoms constrained to unity. The geometry of the disordered acetyl group restrained to be the same using SAME and FLAT commands in SHELXL97 (Sheldrick, 2008). The structure was finally refined anisotropically using SIMU restraints in SHELXL97 (Sheldrick, 2008) with final occupancy values for the two components being 0.587 (13) and 0.413 (13), respectively.

Computing details

For both compounds, data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2009).

Figures

	Fig. 1. A view of (I), with the atom-numbering scheme and the disordered atoms with prime labelling. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The dimer in the crystal structure of (I) [symmetry code: (iv) -x+2, -y+1, -z+1.]
	Fig. 4. The dimer in crystal structure of (II) [symmetry code: (i) -x+2, -y+2, -z+1.]
	Fig. 5. The molecular organization of the dimers (shown in Fig. 3) in the structure of (I) [symmetry codes: (ii) -x+ 1, -y, -z; (vi) -x+1, -y+1, -z].
	Fig. 6. The molecular organization of the dimers (shown in Fig. 4) in the structure of (II) [symmetry codes: (ii) -x+1, -y+2, -z+1].

(I) 4,6-di-O-acetyl-2-O-tosyl-myo-inositol 1,3,5-orthoformate

Crystal data

C18H20O10S	Z = 2
Mr = 428.40	F(000) = 448
Triclinic, P1	Dx = 1.436 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5756 (6) Å	Cell parameters from 4544 reflections
b = 11.0381 (8) Å	θ = 2.4–28.2°
c = 11.2005 (8) Å	µ = 0.22 mm^−1
α = 100.426 (1)°	T = 298 K
β = 103.123 (1)°	Plate, colourless
γ = 99.660 (1)°	0.49 × 0.29 × 0.13 mm
V = 991.04 (12) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3581 independent reflections
Radiation source: fine-focus sealed tube	3179 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
ω and ϕ Scan scans	θmax = 25.3°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −10→10
Tmin = 0.901, Tmax = 0.972	k = −13→13
9864 measured reflections	l = −13→13

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.061P)^2 + 0.3245P] where P = (Fo^2 + 2Fc^2)/3
3581 reflections	(Δ/σ)max = 0.003
294 parameters	Δρmax = 0.41 e Å^−3
29 restraints	Δρmin = −0.22 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
S1	1.13187 (6)	0.28646 (5)	0.50072 (5)	0.05192 (17)
O1	0.97168 (16)	0.11776 (13)	0.08998 (14)	0.0576 (4)
O2	1.06658 (15)	0.20864 (12)	0.35854 (12)	0.0506 (3)
O3	0.79359 (16)	0.01944 (12)	0.18764 (13)	0.0532 (3)
O4	0.60749 (14)	0.28741 (13)	0.24659 (12)	0.0510 (3)
O5	0.69156 (16)	0.06411 (13)	−0.00552 (12)	0.0546 (4)
O6	0.82034 (19)	0.40686 (13)	0.11872 (13)	0.0607 (4)
O7	1.27275 (18)	0.24053 (16)	0.54906 (16)	0.0727 (5)
O8	1.14713 (18)	0.41723 (13)	0.50277 (15)	0.0644 (4)
O9	0.34999 (18)	0.25258 (16)	0.13177 (17)	0.0786 (5)
C1	0.9644 (2)	0.24132 (18)	0.15071 (18)	0.0493 (4)
H1	1.0686	0.3005	0.1629	0.059*
C2	0.9272 (2)	0.23932 (17)	0.27681 (16)	0.0425 (4)
H2	0.9097	0.3216	0.3145	0.051*
C3	0.7741 (2)	0.13669 (17)	0.25463 (17)	0.0446 (4)
H3	0.7535	0.1274	0.3354	0.054*
C4	0.6280 (2)	0.17260 (17)	0.17381 (17)	0.0448 (4)
H4	0.5294	0.1061	0.1575	0.054*
C5	0.6666 (2)	0.18537 (18)	0.04987 (17)	0.0481 (4)
H5	0.5744	0.2066	−0.0058	0.058*
C6	0.8256 (2)	0.27979 (18)	0.06432 (18)	0.0511 (5)
H6	0.8471	0.2764	−0.0184	0.061*
C7	0.8237 (2)	0.03049 (19)	0.0718 (2)	0.0551 (5)
H7	0.8347	−0.0521	0.0291	0.066*
C8	0.9742 (2)	0.23742 (17)	0.56804 (17)	0.0471 (4)
C9	0.8484 (3)	0.30170 (18)	0.56673 (19)	0.0545 (5)
H9	0.8536	0.3763	0.5389	0.065*
C10	0.7159 (3)	0.2540 (2)	0.6070 (2)	0.0608 (5)
H10	0.6308	0.2966	0.6051	0.073*
C11	0.7066 (3)	0.1438 (2)	0.65035 (19)	0.0598 (5)
C12	0.8367 (3)	0.0842 (2)	0.6551 (2)	0.0657 (6)
H12	0.8340	0.0119	0.6869	0.079*
C13	0.9696 (3)	0.12861 (19)	0.6141 (2)	0.0585 (5)
H13	1.0552	0.0865	0.6171	0.070*
C14	0.5575 (4)	0.0897 (3)	0.6879 (3)	0.0916 (9)
H14A	0.4776	0.0355	0.6153	0.137*
H14B	0.5116	0.1570	0.7228	0.137*
H14C	0.5876	0.0419	0.7498	0.137*
C15	0.4592 (2)	0.31450 (19)	0.21942 (19)	0.0505 (5)
C16	0.4525 (3)	0.4309 (2)	0.3063 (2)	0.0685 (6)
H16A	0.3805	0.4753	0.2615	0.103*
H16B	0.5605	0.4840	0.3390	0.103*
H16C	0.4122	0.4089	0.3745	0.103*
O10	0.6925 (14)	0.4293 (5)	−0.0650 (5)	0.122 (3)	0.581 (15)
C17	0.7656 (7)	0.4774 (8)	0.0455 (5)	0.098 (3)	0.581 (15)
C18	0.8025 (17)	0.6142 (10)	0.1121 (10)	0.093 (3)	0.581 (15)
H18A	0.7772	0.6642	0.0515	0.140*	0.581 (15)
H18B	0.9167	0.6406	0.1564	0.140*	0.581 (15)
H18C	0.7373	0.6251	0.1708	0.140*	0.581 (15)
O10'	0.818 (2)	0.4636 (8)	−0.0634 (8)	0.120 (3)	0.419 (15)
C17'	0.8016 (10)	0.4872 (12)	0.0435 (6)	0.094 (3)	0.419 (15)
C18'	0.760 (3)	0.6030 (17)	0.1115 (17)	0.110 (5)	0.419 (15)
H18D	0.6430	0.5927	0.0927	0.165*	0.419 (15)
H18E	0.8060	0.6755	0.0845	0.165*	0.419 (15)
H18F	0.8045	0.6148	0.2006	0.165*	0.419 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0382 (3)	0.0502 (3)	0.0571 (3)	0.0071 (2)	−0.0047 (2)	0.0106 (2)
O1	0.0397 (7)	0.0609 (8)	0.0677 (9)	0.0097 (6)	0.0195 (6)	−0.0020 (7)
O2	0.0359 (6)	0.0552 (8)	0.0561 (8)	0.0159 (6)	0.0025 (6)	0.0082 (6)
O3	0.0461 (7)	0.0450 (7)	0.0663 (9)	0.0104 (6)	0.0136 (6)	0.0082 (6)
O4	0.0331 (6)	0.0564 (8)	0.0532 (7)	0.0108 (5)	0.0054 (5)	−0.0063 (6)
O5	0.0454 (7)	0.0554 (8)	0.0516 (8)	0.0098 (6)	0.0069 (6)	−0.0080 (6)
O6	0.0805 (10)	0.0515 (8)	0.0451 (7)	0.0104 (7)	0.0092 (7)	0.0117 (6)
O7	0.0439 (8)	0.0856 (11)	0.0788 (11)	0.0181 (7)	−0.0079 (7)	0.0213 (9)
O8	0.0553 (8)	0.0471 (8)	0.0759 (10)	−0.0026 (6)	0.0001 (7)	0.0115 (7)
O9	0.0441 (8)	0.0726 (10)	0.0934 (12)	0.0172 (7)	−0.0087 (8)	−0.0160 (9)
C1	0.0366 (9)	0.0525 (11)	0.0539 (11)	0.0027 (8)	0.0131 (8)	0.0053 (8)
C2	0.0305 (8)	0.0466 (10)	0.0463 (10)	0.0093 (7)	0.0033 (7)	0.0081 (8)
C3	0.0357 (9)	0.0472 (10)	0.0483 (10)	0.0075 (7)	0.0097 (7)	0.0074 (8)
C4	0.0315 (8)	0.0469 (10)	0.0486 (10)	0.0067 (7)	0.0061 (7)	−0.0002 (8)
C5	0.0410 (10)	0.0523 (11)	0.0430 (10)	0.0120 (8)	0.0025 (8)	0.0001 (8)
C6	0.0550 (11)	0.0531 (11)	0.0416 (10)	0.0086 (9)	0.0111 (8)	0.0068 (8)
C7	0.0416 (10)	0.0510 (11)	0.0654 (13)	0.0105 (8)	0.0126 (9)	−0.0038 (9)
C8	0.0501 (10)	0.0396 (9)	0.0436 (10)	0.0106 (8)	−0.0013 (8)	0.0058 (8)
C9	0.0669 (13)	0.0435 (10)	0.0556 (11)	0.0211 (9)	0.0117 (10)	0.0149 (9)
C10	0.0672 (14)	0.0666 (13)	0.0586 (12)	0.0302 (11)	0.0198 (10)	0.0210 (10)
C11	0.0676 (13)	0.0660 (13)	0.0451 (11)	0.0149 (11)	0.0103 (9)	0.0165 (9)
C12	0.0815 (16)	0.0521 (12)	0.0656 (13)	0.0170 (11)	0.0121 (12)	0.0264 (10)
C13	0.0645 (13)	0.0486 (11)	0.0628 (12)	0.0227 (10)	0.0070 (10)	0.0163 (9)
C14	0.0839 (19)	0.123 (2)	0.0818 (18)	0.0182 (17)	0.0295 (15)	0.0524 (17)
C15	0.0342 (9)	0.0528 (11)	0.0588 (11)	0.0084 (8)	0.0091 (8)	0.0039 (9)
C16	0.0511 (12)	0.0678 (14)	0.0770 (15)	0.0194 (10)	0.0132 (11)	−0.0090 (11)
O10	0.195 (7)	0.084 (3)	0.055 (2)	0.033 (4)	−0.031 (3)	0.0132 (18)
C17	0.156 (5)	0.069 (4)	0.054 (4)	0.033 (4)	−0.014 (3)	0.018 (3)
C18	0.146 (6)	0.059 (4)	0.067 (4)	0.024 (4)	0.006 (4)	0.021 (3)
O10'	0.216 (9)	0.086 (4)	0.077 (4)	0.038 (5)	0.059 (5)	0.033 (3)
C17'	0.169 (7)	0.068 (5)	0.059 (5)	0.036 (5)	0.043 (5)	0.021 (4)
C18'	0.170 (10)	0.064 (7)	0.081 (7)	0.029 (7)	0.005 (7)	0.011 (5)

Geometric parameters (Å, º)

S1—O7	1.4204 (14)	C7—H7	0.9800
S1—O8	1.4228 (15)	C8—C9	1.386 (3)
S1—O2	1.5894 (14)	C8—C13	1.388 (3)
S1—C8	1.748 (2)	C9—C10	1.375 (3)
O1—C7	1.408 (2)	C9—H9	0.9300
O1—C1	1.428 (2)	C10—C11	1.386 (3)
O2—C2	1.4602 (19)	C10—H10	0.9300
O3—C7	1.401 (3)	C11—C12	1.383 (3)
O3—C3	1.430 (2)	C11—C14	1.500 (3)
O4—C15	1.336 (2)	C12—C13	1.372 (3)
O4—C4	1.438 (2)	C12—H12	0.9300
O5—C7	1.408 (2)	C13—H13	0.9300
O5—C5	1.442 (2)	C14—H14A	0.9600
O6—C17'	1.334 (12)	C14—H14B	0.9600
O6—C17	1.295 (8)	C14—H14C	0.9600
O6—C6	1.437 (2)	C15—C16	1.483 (3)
O9—C15	1.197 (2)	C16—H16A	0.9600
C1—C2	1.520 (3)	C16—H16B	0.9600
C1—C6	1.526 (3)	C16—H16C	0.9600
C1—H1	0.9800	O10—C17	1.226 (4)
C2—C3	1.523 (2)	C17—C18	1.504 (6)
C2—H2	0.9800	C18—H18A	0.9600
C3—C4	1.526 (2)	C18—H18B	0.9600
C3—H3	0.9800	C18—H18C	0.9600
C4—C5	1.523 (3)	O10'—C17'	1.222 (5)
C4—H4	0.9800	C17'—C18'	1.506 (6)
C5—C6	1.527 (3)	C18'—H18D	0.9600
C5—H5	0.9800	C18'—H18E	0.9600
C6—H6	0.9800	C18'—H18F	0.9600
O7—S1—O8	119.80 (9)	O3—C7—O5	111.00 (15)
O7—S1—O2	103.66 (9)	O1—C7—O5	111.09 (17)
O8—S1—O2	108.71 (8)	O3—C7—H7	108.0
O7—S1—C8	110.63 (10)	O1—C7—H7	108.0
O8—S1—C8	109.05 (9)	O5—C7—H7	108.0
O2—S1—C8	103.66 (8)	C9—C8—C13	120.4 (2)
C7—O1—C1	111.31 (13)	C9—C8—S1	119.92 (15)
C2—O2—S1	118.36 (11)	C13—C8—S1	119.52 (16)
C7—O3—C3	110.97 (14)	C10—C9—C8	119.34 (18)
C15—O4—C4	117.37 (13)	C10—C9—H9	120.3
C7—O5—C5	111.85 (13)	C8—C9—H9	120.3
C17'—O6—C6	118.4 (4)	C9—C10—C11	121.3 (2)
C17—O6—C6	119.2 (3)	C9—C10—H10	119.4
O1—C1—C2	110.12 (16)	C11—C10—H10	119.4
O1—C1—C6	106.78 (15)	C12—C11—C10	118.1 (2)
C2—C1—C6	109.61 (15)	C12—C11—C14	121.3 (2)
O1—C1—H1	110.1	C10—C11—C14	120.6 (2)
C2—C1—H1	110.1	C13—C12—C11	121.89 (19)
C6—C1—H1	110.1	C13—C12—H12	119.1
O2—C2—C1	107.81 (14)	C11—C12—H12	119.1
O2—C2—C3	109.64 (14)	C12—C13—C8	118.91 (19)
C1—C2—C3	108.09 (15)	C12—C13—H13	120.5
O2—C2—H2	110.4	C8—C13—H13	120.5
C1—C2—H2	110.4	C11—C14—H14A	109.5
C3—C2—H2	110.4	C11—C14—H14B	109.5
O3—C3—C2	110.26 (14)	H14A—C14—H14B	109.5
O3—C3—C4	107.71 (14)	C11—C14—H14C	109.5
C2—C3—C4	109.14 (15)	H14A—C14—H14C	109.5
O3—C3—H3	109.9	H14B—C14—H14C	109.5
C2—C3—H3	109.9	O9—C15—O4	122.26 (18)
C4—C3—H3	109.9	O9—C15—C16	125.96 (18)
O4—C4—C5	114.16 (16)	O4—C15—C16	111.72 (16)
O4—C4—C3	106.09 (13)	C15—C16—H16A	109.5
C5—C4—C3	107.57 (14)	C15—C16—H16B	109.5
O4—C4—H4	109.6	H16A—C16—H16B	109.5
C5—C4—H4	109.6	C15—C16—H16C	109.5
C3—C4—H4	109.6	H16A—C16—H16C	109.5
O5—C5—C4	106.03 (15)	H16B—C16—H16C	109.5
O5—C5—C6	105.65 (14)	O10—C17—O6	119.5 (7)
C4—C5—C6	114.32 (15)	O10—C17—C18	127.8 (5)
O5—C5—H5	110.2	O6—C17—C18	112.7 (6)
C4—C5—H5	110.2	O10'—C17'—O6	122.0 (10)
C6—C5—H5	110.2	O10'—C17'—C18'	128.6 (8)
O6—C6—C1	108.51 (15)	O6—C17'—C18'	109.4 (10)
O6—C6—C5	112.60 (16)	C17'—C18'—H18D	109.5
C1—C6—C5	107.81 (16)	C17'—C18'—H18E	109.5
O6—C6—H6	109.3	H18D—C18'—H18E	109.5
C1—C6—H6	109.3	C17'—C18'—H18F	109.5
C5—C6—H6	109.3	H18D—C18'—H18F	109.5
O3—C7—O1	110.69 (16)	H18E—C18'—H18F	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O9^i	0.98	2.64	3.344 (2)	129
C4—H4···O5^ii	0.98	2.49	3.370 (2)	149
C7—H7···O1^iii	0.98	2.47	3.221 (2)	133
C7—H7···O9^ii	0.98	2.60	3.391 (2)	138
C9—H9···O8^iv	0.93	2.41	3.329 (2)	171
C14—H14C···O5^v	0.96	2.63	3.443 (3)	142
C16—H16B···O8^iv	0.96	2.64	3.551 (3)	158
C16—H16A···O10^vi	0.96	2.60	3.444 (5)	146
C18—H18A···O9^vi	0.96	2.50	3.437 (15)	165

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

(II) 4,6-di-O-acetyl-2-O-tosyl-myo-inositol 1,3,5-orthobenzoate

Crystal data

C24H24O10S	F(000) = 1056
Mr = 504.49	Dx = 1.408 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2021 reflections
a = 12.3019 (14) Å	θ = 2.4–23.5°
b = 8.2155 (10) Å	µ = 0.19 mm^−1
c = 23.551 (3) Å	T = 298 K
β = 91.306 (2)°	Plate, colourless
V = 2379.6 (5) Å^3	0.59 × 0.17 × 0.07 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	4179 independent reflections
Radiation source: fine-focus sealed tube	3082 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ω and ϕ Scan scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −14→14
Tmin = 0.878, Tmax = 0.987	k = −9→9
11497 measured reflections	l = −28→13

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.123	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0516P)^2 + 0.5157P] where P = (Fo^2 + 2Fc^2)/3
4179 reflections	(Δ/σ)max = 0.001
319 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.22 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 > 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
S1	1.05937 (5)	0.80750 (9)	0.42697 (3)	0.0474 (2)
O1	0.75779 (14)	1.0810 (2)	0.38702 (7)	0.0427 (5)
O2	0.95453 (13)	0.8953 (2)	0.40129 (8)	0.0463 (5)
O3	0.77092 (13)	0.8699 (2)	0.32292 (7)	0.0425 (5)
O4	0.71253 (14)	0.5626 (2)	0.42790 (8)	0.0457 (5)
O5	0.60405 (13)	0.9342 (2)	0.36040 (7)	0.0424 (5)
O6	0.68432 (15)	0.8176 (2)	0.50513 (7)	0.0481 (5)
O7	1.14579 (15)	0.9079 (3)	0.40986 (10)	0.0670 (6)
O8	1.04358 (15)	0.7776 (2)	0.48563 (8)	0.0566 (5)
O9	0.54279 (19)	0.4688 (3)	0.42545 (12)	0.0833 (8)
O10	0.59918 (18)	1.0043 (3)	0.55677 (9)	0.0658 (6)
C1	0.7787 (2)	0.9762 (3)	0.43500 (11)	0.0407 (6)
H1	0.8160	1.0373	0.4654	0.049*
C2	0.84816 (18)	0.8332 (3)	0.41742 (11)	0.0379 (6)
H2	0.8563	0.7556	0.4488	0.045*
C3	0.79287 (19)	0.7526 (3)	0.36670 (11)	0.0387 (6)
H3	0.8396	0.6663	0.3521	0.046*
C4	0.68538 (19)	0.6803 (3)	0.38507 (11)	0.0403 (6)
H4	0.6484	0.6273	0.3527	0.048*
C5	0.6164 (2)	0.8209 (3)	0.40672 (11)	0.0413 (6)
H5	0.5451	0.7806	0.4180	0.050*
C6	0.6694 (2)	0.9163 (3)	0.45521 (11)	0.0403 (6)
H6	0.6237	1.0101	0.4642	0.048*
C7	0.7039 (2)	0.9977 (3)	0.34273 (11)	0.0426 (7)
C8	0.6801 (2)	1.1128 (4)	0.29430 (12)	0.0477 (7)
C9	0.6224 (2)	1.0555 (5)	0.24735 (13)	0.0670 (9)
H9	0.5991	0.9479	0.2465	0.080*
C10	0.5991 (3)	1.1565 (5)	0.20171 (14)	0.0774 (11)
H10	0.5607	1.1168	0.1702	0.093*
C11	0.6330 (3)	1.3165 (5)	0.20314 (16)	0.0771 (11)
H11	0.6167	1.3854	0.1728	0.092*
C12	0.6909 (3)	1.3736 (4)	0.24933 (15)	0.0739 (10)
H12	0.7141	1.4813	0.2501	0.089*
C13	0.7153 (3)	1.2718 (4)	0.29505 (14)	0.0640 (9)
H13	0.7553	1.3111	0.3261	0.077*
C14	1.0618 (2)	0.6210 (3)	0.39130 (12)	0.0431 (7)
C15	1.1103 (2)	0.6111 (4)	0.33899 (13)	0.0598 (8)
H15	1.1451	0.7011	0.3238	0.072*
C16	1.1064 (3)	0.4657 (5)	0.30982 (14)	0.0663 (9)
H16	1.1398	0.4588	0.2749	0.080*
C17	1.0547 (2)	0.3304 (4)	0.33060 (13)	0.0564 (8)
C18	1.0074 (2)	0.3440 (4)	0.38323 (13)	0.0569 (8)
H18	0.9723	0.2542	0.3984	0.068*
C19	1.0110 (2)	0.4865 (4)	0.41344 (12)	0.0498 (7)
H19	0.9793	0.4924	0.4488	0.060*
C20	1.0508 (3)	0.1744 (5)	0.29811 (15)	0.0878 (12)
H20A	1.0738	0.1934	0.2600	0.132*
H20B	0.9778	0.1331	0.2973	0.132*
H20C	1.0983	0.0965	0.3162	0.132*
C21	0.6319 (2)	0.4665 (3)	0.44671 (14)	0.0529 (8)
C22	0.6694 (3)	0.3677 (4)	0.49552 (16)	0.0740 (10)
H22A	0.6733	0.4346	0.5289	0.111*
H22B	0.7400	0.3240	0.4881	0.111*
H22C	0.6192	0.2801	0.5013	0.111*
C23	0.6467 (2)	0.8789 (4)	0.55424 (11)	0.0428 (7)
C24	0.6735 (3)	0.7698 (4)	0.60291 (12)	0.0612 (8)
H24A	0.7446	0.7242	0.5982	0.092*
H24B	0.6209	0.6837	0.6043	0.092*
H24C	0.6724	0.8310	0.6376	0.092*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0324 (4)	0.0550 (5)	0.0542 (5)	−0.0079 (3)	−0.0100 (3)	0.0083 (4)
O1	0.0460 (10)	0.0438 (11)	0.0380 (10)	−0.0023 (8)	−0.0051 (9)	0.0019 (8)
O2	0.0344 (10)	0.0501 (11)	0.0540 (12)	−0.0062 (8)	−0.0045 (9)	0.0140 (9)
O3	0.0382 (10)	0.0537 (12)	0.0355 (10)	0.0051 (8)	0.0017 (8)	−0.0014 (9)
O4	0.0388 (10)	0.0372 (10)	0.0610 (13)	−0.0033 (8)	0.0004 (9)	0.0015 (9)
O5	0.0316 (10)	0.0563 (12)	0.0392 (11)	0.0025 (8)	−0.0013 (8)	0.0035 (9)
O6	0.0591 (12)	0.0481 (11)	0.0372 (11)	0.0088 (9)	0.0052 (9)	−0.0005 (9)
O7	0.0382 (11)	0.0683 (14)	0.0939 (17)	−0.0179 (10)	−0.0076 (11)	0.0133 (12)
O8	0.0592 (12)	0.0673 (14)	0.0425 (12)	−0.0038 (10)	−0.0157 (10)	0.0024 (10)
O9	0.0530 (14)	0.0842 (18)	0.112 (2)	−0.0235 (12)	−0.0063 (14)	0.0136 (15)
O10	0.0695 (14)	0.0797 (16)	0.0487 (13)	0.0277 (12)	0.0116 (11)	−0.0025 (11)
C1	0.0471 (16)	0.0410 (15)	0.0337 (15)	−0.0008 (12)	−0.0055 (12)	−0.0027 (12)
C2	0.0289 (13)	0.0443 (16)	0.0403 (15)	−0.0053 (11)	0.0001 (11)	0.0041 (12)
C3	0.0329 (14)	0.0437 (15)	0.0394 (16)	0.0044 (12)	0.0005 (12)	−0.0023 (12)
C4	0.0358 (14)	0.0450 (16)	0.0400 (15)	−0.0030 (12)	−0.0036 (12)	−0.0059 (13)
C5	0.0326 (14)	0.0486 (17)	0.0427 (16)	0.0001 (12)	0.0040 (12)	0.0003 (13)
C6	0.0452 (15)	0.0416 (15)	0.0341 (15)	0.0082 (12)	0.0020 (13)	0.0009 (12)
C7	0.0368 (15)	0.0519 (17)	0.0390 (16)	0.0018 (13)	−0.0008 (13)	−0.0021 (13)
C8	0.0395 (15)	0.062 (2)	0.0419 (17)	0.0064 (14)	0.0018 (13)	0.0071 (14)
C9	0.0534 (19)	0.087 (3)	0.060 (2)	−0.0036 (17)	−0.0134 (17)	0.0147 (19)
C10	0.057 (2)	0.116 (3)	0.059 (2)	0.004 (2)	−0.0200 (17)	0.023 (2)
C11	0.061 (2)	0.105 (3)	0.065 (2)	0.022 (2)	0.0015 (19)	0.035 (2)
C12	0.086 (3)	0.068 (2)	0.067 (2)	0.0110 (19)	0.009 (2)	0.025 (2)
C13	0.071 (2)	0.066 (2)	0.055 (2)	0.0048 (17)	−0.0003 (17)	0.0055 (17)
C14	0.0305 (14)	0.0551 (18)	0.0434 (16)	0.0002 (12)	−0.0040 (12)	0.0108 (14)
C15	0.0536 (19)	0.068 (2)	0.058 (2)	−0.0047 (16)	0.0135 (16)	0.0143 (17)
C16	0.066 (2)	0.090 (3)	0.0440 (19)	0.0112 (19)	0.0164 (16)	0.0064 (19)
C17	0.0581 (19)	0.064 (2)	0.0464 (18)	0.0054 (16)	−0.0025 (15)	0.0027 (16)
C18	0.0621 (19)	0.056 (2)	0.0524 (19)	−0.0061 (15)	0.0058 (16)	0.0074 (16)
C19	0.0528 (17)	0.0573 (19)	0.0394 (17)	−0.0033 (14)	0.0052 (14)	0.0088 (14)
C20	0.109 (3)	0.089 (3)	0.066 (2)	0.005 (2)	0.003 (2)	−0.016 (2)
C21	0.0476 (18)	0.0401 (17)	0.071 (2)	−0.0023 (14)	0.0117 (17)	−0.0057 (15)
C22	0.078 (2)	0.0488 (19)	0.096 (3)	0.0047 (17)	0.018 (2)	0.0147 (19)
C23	0.0329 (14)	0.0549 (18)	0.0406 (17)	−0.0052 (13)	0.0017 (12)	−0.0033 (14)
C24	0.070 (2)	0.068 (2)	0.0456 (18)	−0.0076 (16)	−0.0019 (16)	0.0070 (16)

Geometric parameters (Å, º)

S1—O7	1.412 (2)	C9—C10	1.383 (4)
S1—O8	1.421 (2)	C9—H9	0.9300
S1—O2	1.5853 (18)	C10—C11	1.379 (5)
S1—C14	1.748 (3)	C10—H10	0.9300
O1—C7	1.401 (3)	C11—C12	1.369 (5)
O1—C1	1.439 (3)	C11—H11	0.9300
O2—C2	1.463 (3)	C12—C13	1.391 (4)
O3—C7	1.420 (3)	C12—H12	0.9300
O3—C3	1.432 (3)	C13—H13	0.9300
O4—C21	1.351 (3)	C14—C19	1.378 (4)
O4—C4	1.432 (3)	C14—C15	1.384 (4)
O5—C7	1.407 (3)	C15—C16	1.378 (4)
O5—C5	1.440 (3)	C15—H15	0.9300
O6—C23	1.353 (3)	C16—C17	1.376 (4)
O6—C6	1.437 (3)	C16—H16	0.9300
O9—C21	1.195 (3)	C17—C18	1.386 (4)
O10—C23	1.186 (3)	C17—C20	1.493 (4)
C1—C2	1.516 (4)	C18—C19	1.370 (4)
C1—C6	1.518 (4)	C18—H18	0.9300
C1—H1	0.9800	C19—H19	0.9300
C2—C3	1.514 (3)	C20—H20A	0.9600
C2—H2	0.9800	C20—H20B	0.9600
C3—C4	1.521 (3)	C20—H20C	0.9600
C3—H3	0.9800	C21—C22	1.472 (4)
C4—C5	1.527 (4)	C22—H22A	0.9600
C4—H4	0.9800	C22—H22B	0.9600
C5—C6	1.520 (4)	C22—H22C	0.9600
C5—H5	0.9800	C23—C24	1.486 (4)
C6—H6	0.9800	C24—H24A	0.9600
C7—C8	1.505 (4)	C24—H24B	0.9600
C8—C13	1.376 (4)	C24—H24C	0.9600
C8—C9	1.383 (4)
O7—S1—O8	119.95 (13)	C8—C9—C10	120.7 (3)
O7—S1—O2	103.69 (11)	C8—C9—H9	119.6
O8—S1—O2	108.76 (11)	C10—C9—H9	119.6
O7—S1—C14	110.73 (14)	C11—C10—C9	119.7 (3)
O8—S1—C14	108.65 (13)	C11—C10—H10	120.2
O2—S1—C14	103.77 (11)	C9—C10—H10	120.2
C7—O1—C1	111.43 (19)	C12—C11—C10	119.8 (3)
C2—O2—S1	117.87 (15)	C12—C11—H11	120.1
C7—O3—C3	111.24 (19)	C10—C11—H11	120.1
C21—O4—C4	117.7 (2)	C11—C12—C13	120.5 (4)
C7—O5—C5	112.73 (18)	C11—C12—H12	119.7
C23—O6—C6	116.7 (2)	C13—C12—H12	119.7
O1—C1—C2	109.9 (2)	C8—C13—C12	119.9 (3)
O1—C1—C6	107.2 (2)	C8—C13—H13	120.0
C2—C1—C6	110.1 (2)	C12—C13—H13	120.0
O1—C1—H1	109.9	C19—C14—C15	119.9 (3)
C2—C1—H1	109.9	C19—C14—S1	120.6 (2)
C6—C1—H1	109.9	C15—C14—S1	119.5 (2)
O2—C2—C3	109.6 (2)	C16—C15—C14	118.9 (3)
O2—C2—C1	108.3 (2)	C16—C15—H15	120.5
C3—C2—C1	108.0 (2)	C14—C15—H15	120.5
O2—C2—H2	110.3	C17—C16—C15	122.3 (3)
C3—C2—H2	110.3	C17—C16—H16	118.9
C1—C2—H2	110.3	C15—C16—H16	118.9
O3—C3—C2	110.3 (2)	C16—C17—C18	117.4 (3)
O3—C3—C4	108.45 (19)	C16—C17—C20	121.4 (3)
C2—C3—C4	108.9 (2)	C18—C17—C20	121.2 (3)
O3—C3—H3	109.7	C19—C18—C17	121.6 (3)
C2—C3—H3	109.7	C19—C18—H18	119.2
C4—C3—H3	109.7	C17—C18—H18	119.2
O4—C4—C3	105.89 (19)	C18—C19—C14	119.9 (3)
O4—C4—C5	113.5 (2)	C18—C19—H19	120.1
C3—C4—C5	107.0 (2)	C14—C19—H19	120.1
O4—C4—H4	110.1	C17—C20—H20A	109.5
C3—C4—H4	110.1	C17—C20—H20B	109.5
C5—C4—H4	110.1	H20A—C20—H20B	109.5
O5—C5—C6	105.8 (2)	C17—C20—H20C	109.5
O5—C5—C4	106.6 (2)	H20A—C20—H20C	109.5
C6—C5—C4	114.1 (2)	H20B—C20—H20C	109.5
O5—C5—H5	110.1	O9—C21—O4	121.8 (3)
C6—C5—H5	110.1	O9—C21—C22	127.2 (3)
C4—C5—H5	110.1	O4—C21—C22	111.0 (3)
O6—C6—C1	110.0 (2)	C21—C22—H22A	109.5
O6—C6—C5	111.6 (2)	C21—C22—H22B	109.5
C1—C6—C5	107.4 (2)	H22A—C22—H22B	109.5
O6—C6—H6	109.2	C21—C22—H22C	109.5
C1—C6—H6	109.2	H22A—C22—H22C	109.5
C5—C6—H6	109.2	H22B—C22—H22C	109.5
O1—C7—O5	111.2 (2)	O10—C23—O6	123.0 (3)
O1—C7—O3	109.73 (19)	O10—C23—C24	125.9 (3)
O5—C7—O3	109.9 (2)	O6—C23—C24	111.1 (3)
O1—C7—C8	109.8 (2)	C23—C24—H24A	109.5
O5—C7—C8	107.5 (2)	C23—C24—H24B	109.5
O3—C7—C8	108.7 (2)	H24A—C24—H24B	109.5
C13—C8—C9	119.3 (3)	C23—C24—H24C	109.5
C13—C8—C7	122.0 (3)	H24A—C24—H24C	109.5
C9—C8—C7	118.7 (3)	H24B—C24—H24C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O8^i	0.98	2.56	3.490 (3)	159
C5—H5···O10^ii	0.98	2.58	3.153 (3)	117
C22—H22C···O10^iii	0.96	2.63	3.435 (4)	142
C24—H24B···O9^iv	0.96	2.46	3.360 (4)	156

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