Sulfur compounds. 158. Structure and electron density of solid dimethoxysulfane, (CH3O)2S

Abstract

9243(6) Liu, Y.; Zhang, Q. L.; Tittel, F. K.; Curl, R. F.; Smalley, R. E. J.(7) Ramen, M.; Heimbrook, C. A.; Schwartz, G. P.; Bondybey, V. E. (41) Hurley, M. M.; Pacia, L. F.; Christiansen, P. A.; Ross, R. B.; Ermler, W. C. J. Chem. Phys. 1986,84, 6840. LaJohn, L. A.; Christiansen, P. A,; Ross, R. B.; Atashroo, T.; Ermler, W. C. J. Chem. Phys. 1987, 87, 2812. Ross, R. B.; Powers, J. M.; Atashroo, T.; Ermler, W. C.; LaJohn, L. A.; Christiansen, P. A.High-resolution X-ray data were collected at a low temperature (1 10 (1) K) to determine the crystal and molecular structure and the deformation electron density (DED) of CH30SOCH3. Crystal data: a = 9.156 (S), b = 7.451 (6), c = 6.593 (3) A, Pbcn (centric), Z = 4. The molecules are in special positions of C2 symmetry with bond lengths SO = 1.6212 (7), CO = 1.4444 (6), and CH = 1.067 (7) A (av), bond angles OS0 = 104.78 (5)", COS = 115.76 (2)O, OCH = 108.3O (av), and torsional angle COS0 = 81.75 ( 2 ) ' . The OCH, units deviate considerably from C3, symmetry. The deformation electron density is analyzed in terms of static (SDD) and dynamic deformation density (DDD) calculated from the fitted multipolepopulations and X-X Fourier synthesis. The r lone pairs at S and 0 are clearly discernible in these maps but there is no indication of any anomeric effect. The torsional angle of 82O at the S-0 bonds must therefore be the result of the lone pair interaction only. The molecules form layers with the OS0 units in parallel planes and the methyl groups separating these planes from each other. There are no intermolecular contacts shorter than the van der Waals distances, but the sulfur atoms are coordinated by two nonbonded oxygen atoms of neighboring molecules from the same plane resulting in a 2 + 2 coordination of local symmetry C, .

Sulfur compounds. Part 173. Structure and Electron Density of Solid Dimethoxydisulfane, (CH3O)2S2

“…The average S-0 bond length of2 (1.658-(4) A) is slightly longer than that of 1 (1.621(1) A), but still in the range of other S-O bonds originating from two-coordinated sulfur. 4 The S-S bond length of disulfanes is a function of various substituent properties82 and, in particular, depends on their electronegativity, as the data in Table 8 demonstrate. The value of 1.972(1) A observed for 2 fits the expectations from the group electronegativity of CH30-, which has been estimated as 2.5-3.1 on the Pauling scale.…”

σ-Hole interactions in small-molecule compounds containing divalent sulfur groupsR1—S—R2

“…All calculations were performed on the model systems using F 2 S, Cl 2 S and Br 2 S as donors of -hole and NH 3 , HCN and (CH 3 ) 2 O as acceptors of -hole, as well as the following molecules derived from CSD entries and highlighted in Fig. 1: (FOC,CN)S (from CSD entry AMOREA; Ramos et al, 2010), (CH 3 O) 2 S (from CSD entry KUYRIF; Buschmann et al, 1992), (Cl,(CH 3 ) 2 N)S (from CSD entry VAMPEF; Mitzel, 2003), methionine (from CSD entry FITLID; Dalhus & Gö rbitz, 1999) and (CN) 2 S (from CSD entry GOJZUC; Ilyukhin et al, 2014). The r S +r O (3.32 Å ), r S +r N (3.35 Å ), r S +r Cl (3.55 Å ) and r S +r S (3.60 Å ) sums of van der Waals radii were used to calculate Á using, respectively, the van der Waals radii values of 1.80 Å , 1.52 Å , 1.55 Å and 1.75 Å for the S, O, N and Cl atoms (Bondi, 1964).…”

Gas-Phase Structure and Vibrational Spectra of Dimethoxydisulfane, (CH3O)2S2

“…The camera pressure did not exceed 3 x 10-3 Pa during the experiment. The exposure times were [4][5][6][7][8] 0022-3654/95/2099-8987$09.00/0 © 1995 American Chemical Society s/nm'F igure 2. Experimental (•) and calculated (-) molecular scattering intensities and differences for (CH30)2S2.…”