The crystal structures of NSF3 and (NSF2N(CH3)CH2–)2: How short is the ‘Crystallographic’ NS triple bond?

Thiazyl Trifluoride (NSF3) Adducts and Imidodifluorosulfate (F2OSN-) Derivatives of Hg(OTeF5)2

“…The S–F (1.489(6)–1.516(7) Å) bond lengths are comparable to those of [M­(NSF 3 ) 4 ]­[AsF 6 ] 2 (Mn, 1.501(5)–1.511(4) Å; Zn, 1.423(9)–1.515(5) Å), , [Re­(CO) 5 NSF 3 ]­[AsF 6 ] (1.499(10) Å), and [CpFe­(CO) 2 ­NSF 3 ]­[AsF 6 ] (1.512(3)–1.519(3) Å) . The shorter S–F bond lengths of adducted NSF 3 relative to those of free NSF 3 (1.531(1)–1.534(2) Å) are consistent with adduct formation . The N–S bond lengths (1.398(5) Å) are also comparable to those of [M­(NSF 3 ) 4 ]­[AsF 6 ] 2 (Mn, 1.357(6)–1.373(5) Å; Zn, 1.350(7)–1.387(6) Å), [Re­(CO) 5 ­NSF 3 ]­[AsF 6 ] (1.384(14) Å), [CpFe­(CO) 2 ­NSF 3 ]­[AsF 6 ] (1.376(3) Å), and free NSF 3 (1.400(3) Å).…”

“…An even more severely bent angle occurs in [F 3 19 The shorter S−F bond lengths of adducted NSF 3 relative to those of free NSF 3 (1.531(1)−1.534(2) Å) are consistent with adduct formation. 10 The N−S bond lengths (1.398 (5) …”

“…19 The shorter S−F bond lengths of adducted NSF 3 relative to those of free NSF 3 (1.531(1)−1.534(2) Å) are consistent with adduct formation. 10 The N−S bond lengths (1.398( 5 a The atom labeling scheme corresponds to that used in Figure 3. See Table S3 for a complete list of geometrical parameters.…”

“…Thiazyl trifluoride, NSF 3 , has been of importance as a synthetic precursor and in the development of sulfur–nitrogen–fluorine chemistry. − The distorted tetrahedral geometry of NSF 3 has been thoroughly studied by 19 F NMR, IR, − Raman, microwave spectroscopy, and by low-temperature single-crystal X-ray diffraction . The reactivity of NSF 3 may be categorized into three reaction types: (1) addition to the π-system of the NS bond, (2) nucleophilic attack at the positively charged and coordinatively unsaturated sulfur­(VI) atom, and (3) donation of the nitrogen electron lone pair to a Lewis acidic center.…”

CH3N=SF2=NCH3: Structural, Conformational, and Configurational Properties in the Gaseous and in the Condensed Phases

“…The molecular structure of 1 is shown in Figure 1 and the geometric parameters are listed in Table 1 together with the calculated values. Table 2 compares experimental bond lengths and bond angles of CH 3 –N=SF 2 =N–CH 3 ( 1 ) with the data of CH 3 –N=S=N–CH 3 ( 2 )10 (exchange of the two fluorine atoms at sulfur by a lone pair, change in the oxidation state), CH 3 –N=S(O)F 2 ( 3 ),41 and O 2 SF 2 ( 4 )42 (stepwise exchange of the imino group by oxygen), and the isomer N≡SF 2 –N(CH 3 ) 2 ( 5 )43 (exchange of two double bonds by a triple and a single bond).…”