Structural implications of C-H•••S contacts in organophosphorus compounds.: Studies of 1,6-anhydro-2-O-tosyl-4-S-(5,5-dimethyl-2-thioxa-1,3,2-dioxaphosphorinan-2-yl)-β-D-glucopyranose by X-ray and solid-state NMR methods

1,6-Anhydro-2-O-tosyl-4-S-(5,5-dimethyl-2-thioxa-1,3,2-dioxaphosphorian-2-yl)-beta-D-glucopyranose (1, C18H25O8PS3), crystallized from polar and/or nonpolar solvents, forms different modifications in the solid phase. Crystal structures of 1 (obtained from a methanol solution) and its 2-propanol solvate (1a) were established by X-ray structure analysis at low temperature. One-component crystal 1 is orthorhombic, space group P2(1)2(1)2(1), with a = 7.483(4) Angstrom, b = 11.156 (6) Angstrom, c = 27.11(2) Angstrom, V = 2263 (2) Angstrom(3), Z = 4, and D-c = 1.457 g cm(-3). Refinement of 275 parameters using 2661 observed reflections (I > 2 sigma(I)) converged at R(F) = 0.0372. The crystal of 1a is an inclusion structure containing molecules of 1 and 2-propanol in the ratio 1/1; crystals are triclinic, space group P1, with a = 9.637(6)Angstrom, b = 9.709(6) Angstrom, c = 8.865(8) Angstrom, alpha = 110.27(5)degrees beta = 106.33(5)degrees, gamma = 108.70(6)degrees, V = 661.3(8) Angstrom(3), Z = 1, and D-c = 1.398 g cm(-3). Full-matrix least-squares refinement of 307 parameters using 2478 observed reflections gave final R(F) = 0.0349. Intermolecular hydrogen bonds (O-H ... O, C-H ... O; in 1; O-H ... O, O-H ... S in 1a) are present along with the C-H ... S=P intermolecular interactions. A search of Cambridge Structural Database shows that such contacts are not unusual for organothiophosphoryl compounds. The solid-state structures were studied by the NMR spectroscopy. The analysis of the P-31 chemical shift parameters enabled the correlation of the delta(33) principal element of chemical shift tensor and span (Omega) with C-H ... S=P. contact. The presence of toluene-d(s) in the crystal lattice of inclusion complex Ib was confirmed by H-2 NMR spectroscopy.