The geometry of the charge transfer complex (CH3)3N,SO2 in the solid state

Abstract

The crystal structure of the charge transfer complex (CH,),N,SO, is reported.ALTHOUGH there have been numerous investigations of the crystal structure of charge transfer (CT) complexes,f there

Partially Bonded Molecules from the Solid State to the Stratosphere

“…26 Both molecules have the structure expected for a donor-acceptor complex, with the nitrogen lone pair directed toward the sulfur and the dative bond nearly perpendicular to the SO 2 plane. The TMA and DMA species have gas phase bond lengths of 2.260(30) and 2.335(30) Å, respectively, which qualify as intermediate, while that in the TMA adduct shortens to 2.046(4) Å 25,27 in the solid. The contraction of a partially formed bond upon crystallization is familiar, but what is interesting here is that, unlike the BF 3 and SO 3 complexes, the formation of crystalline TMA-SO 2 does not drive the N-S bond fully to completion (i.e., to the 1.74 Å sum of covalent bond radii).…”

“…The N-S bond length is 2.003(12) Å, which is 0.332(42) Å shorter than that in the gas phase, 26 yet almost identical to that of the TMA adduct in the solid state. 25,27 The take-home lesson is that while crystallization drives the bonds toward completion in all cases we have examined, it need not drive them to completion. For H 3 N-SO 3 and BF 3 adducts, the bonds are essentially complete in the solid, but in the SO 2 systems, their formation has stopped about 0.25 Å before the expected N-S single bond length is realized.…”

Mercury(I) chemistry. Part II. Reactions of the mercurous ion with some ligands having the heavier Group VA or VIA elements as donor atoms

“…Our data for PPh, in SO, suggest that the PPh, is coordinated to the SO,, the sulfur presumably acting as an acceptor as it does in various SO, (amine) complexes (ref. 13 (Table 1) shows the presence of a coordinated phosphine in the mercury-containing solution. The signals due to C,, C2,6, and C3,5, in Fig.…”

Charge‐Transfer Complexes between the Sulfur Molecules SO2, S2O, S3, SONH, and SOCl2 and the Amine Donors NH3 and NMe3 – A Theoretical Study

“…[5] Subsequently, this compound has been extensively studied by X-ray crystallography of single crystals, [6,7] microwave spectroscopy in the vapor phase, [7] UV/Vis spectroscopy in solution, [8] vapor density measurements, [9] and ab initio MO calculations. [3,[10][11][12] The most recent and most sophisticated theoretical study applying the MP2/6-31G* level of theory predicted S-N distances of 235.9 pm for 2 and 270.7 pm for SO 2 ·2NMe 3 (2a).…”