Syntheses and X-ray structural analyses of [(C₆H₅)₄As][Sn(EC₆H₅)₃], E = S and Se

Abstract

Stannous chloride, in solutions containing at least three mole equivalents of NaEC6H5, E = S and Se, forms triligated anions which crystallize readily as the tetraphenylarsonium salts, [(C6H5)4As[Sn(SC6H5)3], 1, and [(C6H5)4As][Sn(SeC6H5)3], 2. The crystals so formed are isomorphous, and their structures have been determined by single crystal X-ray diffractometry techniques. The salts crystallize in the monoclinic space group P21/c, with four formula units in unit cells of dimensions a = 10.760(1), b = 17.515(2), c = 20.247(3) Å, β = 104.71(1)° for 1, and a = 10.885(2), b = 17.587(2), c = 20.612(2) Å, β = 105.47(1)°, for 2. The structures have been refined by full-matrix least-squares techniques on F to agreement factors R = 0.024 (4780 observations with Fo > 3σ(Fo)) for 1, and R = 0.030 (3442 observations with Fo > 3σ(Fo)) for 2. The discrete [Sn(EC6H5)3]− anions are isostructural; the three S or Se atoms form the base of a triangular pyramid whose apex is occupied by the Sn atom. Two Sn—S distances in 1 are 2.532(1) and the third 2.552(1) Å, while in 2 the Sn—Se distances are 2.649(1), 2.650(1), and 2.671(1) Å. Angles at the Sn atom are 89.91(3), 90.55(3), and 96.73(3)° in 1, and 88.74(3), 89.72(3), and 97.27(3)° in 2. In both anions all three phenyl groups adopt a propeller-like conformation and are disposed in equatorial positions above the basal plane of chalcogen atoms. These salts represent the first thiolato- and sele-nolatostannates(II) to be characterized structurally. Tin-119 nmr spectra confirm that the [Sn(EC6H5)3]− ions are the same anionic Sn(II) species recently prepared insitu in solution.

Solvothermal Syntheses of Two New Thiostannates and an In‐Situ Energy Dispersive X‐ray Scattering Study of Their Formation

“…Interestingly, Sn(3) is surrounded by only three S atoms to form a trigonal pyramidal SnS 3 unit. This geometry is an indication for Sn(II) and the bond valence calculations confirm this assignment as well as the mixed-valent character of (DBNH) 2 [43] and C 42 H 35 PSnS 3 . [44] In these compounds the Sn-S bond lengths are in the range of 2.532(10) to 2.765(2) Å and the S-Sn-S angles scatter from 83.59 (2) (Fig.…”

“…The Sn–S bond lengths in the SnS 3 pyramid are 2.5059(13), 2.5335(16) and 2.5511(17) Å (average Sn–S distance: 2.5302 Å), with the corresponding angles being 88.02(4), 88.62(4) and 102.39(6)°. The existence of Sn in a trigonal pyramidal environment is quite rare, but some examples of compounds in which this occurs are Ottemannite [Sn(SnS 3 )],41 C 25 H 27 NO 3 SnS 3 ,42 C 42 H 35 AsSnS 3 ,43 and C 42 H 35 PSnS 3 44. In these compounds the Sn–S bond lengths range from 2.532(10) to 2.765(2) Å, and the S–Sn–S angles scatter from 83.59(2) to 96.87(3)°.…”

1‐D‐Tin(II) Phenylchalcogenolato Complexes ∞1[Sn(EPh)2] (E = S, Se, Te) – Synthesis, Structures, Quantum Chemical Studies and Thermal Behaviour

“…Two of the Sn–Se distances [Sn(1)–Se(1): 266.87(8), Sn(1)–Se(2): 267.57(7), Sn(2)–Se(3): 268.32(7), Sn(2)–Se(4): 267.37(8) pm] are distinctly smaller than the “secondary” Sn–Se contacts [Sn(1)–Se(3) 291.45(7), Sn(2)–Se(2) 298.02(7), Sn(1)′–Se(4) 321.80(7), Sn(2)–Se(1)′ 310.73(7) pm]. The shorter Sn–Se distances are similar to those found in AsPh 4 [Sn(SePh) 3 ] (264.9–267.0 pm)21 and [Yb(C 4 H 8 O) 6 ][Sn(SePh) 3 ] 2 (262.9–268.5) 22. Therefore the crystal structure of 2 consists of Sn(SePh) 2 units [Se–Sn–Se angles: Se(1)–Sn(1)–Se(2) 88.15(3), Se(4)–Sn(2)–Se(3) 82.37(3)] which are linked by four additional weaker selenium to tin donor‐acceptor bonds in order to form one dimensional chains.…”

Heteroleptic Organostannylenes and an Organoplumbylene Bearing Phosphorus‐Containing Pincer‐Type Ligands – Structural Variations and Insights into the Configurational Stability

“…The Sn–Br distance of 2.6286(3) Å ( 4 ) is shorter than the corresponding distance in intramolecularly N→Sn coordinated [Sn{CH(SiMe 3 )C 9 H 6 N‐8}Br] (2.679(1) Å),8 whereas the Sn–I distance of 2.8544(3) ( 5 ) Å is longer than the corresponding distance reported for [Sn(I){C 6 H 3 ‐2,6‐Trip 2 }] (2.766(2) Å)1l with the tin atom of the latter being two‐coordinate. The Sn(1)–S(1) bond length in compound 6 of 2.512(1) Å resembles the corresponding Sn–S distances of 2.532–2.552 Å in the trithiophenolato stannates [Ph 4 E][Sn(SPh) 3 ] (E = P,16 As17a).…”