Short Sn Research Articles

Transition metal–tin ordering in SrPtSn, SrAuSn and BaAuSn and 119Sn Mössbauer spectroscopy of CaPdSn, CaPtSn and SrAuSn

Abstract Pure samples of CaPdSn, CaPtSn, SrPtSn, SrAuSn and BaAuSn can be prepared by reacting the elements in glassy carbon crucibles or in sealed tantalum tubes in a water-cooled sample chamber of a high-frequency furnace. The stannides have been investigated by X-ray diffraction on powders. Single crystal data yielded: TiNiSi type, Pnma , a =764.16(7), b =470.74(4), c =799.64(7) pm, wR 2 =0.0622, 469 F 2 values, 20 variables for SrPtSn, and CaCuGe type, Pnma , a =2341.4(3), b =481.80(5), c =826.7(1) pm, wR 2 =0.1368, 1136 F 2 values, 56 variables for SrAuSn. The platinum (gold) and tin atoms form two-dimensional layers of puckered Pt 3 Sn 3 and Au 3 Sn 3 hexagons with short PtSn (276 and 278 pm) and AuSn (279–286 pm) intralayer distances. These condensed two-dimensionally infinite nets are interconnected to each other via PtSn contacts (279 pm) in SrPtSn. In SrAuSn very weak interlayer AuSn (312 pm) and AuAu (340 pm) contacts occur, but stronger SnSn (304 pm) interactions. The SrAuSn structure is a superstructure of SrPtSn resulting from an isomorphic transition of index 3 from Pnma to Pnma . The KHg 2 type subcell of BaAuSn was determined from Guinier powder data: Imma , a =493.5(1), b =817.2(1), c =844.5(1) pm. 119 Sn Mossbauer spectra of TiNiSi type CaPdSn and CaPtSn show a single signal at 77 K at isomer shifts of δ =1.964(5) and 1.857(4) mm s −1 , respectively, subject to quadrupole splitting of ΔE Q =0.94(3) and 0.89(1) mm s −1 . SrAuSn shows two superimposed signals in a ratio of 2:1 at 77 K: δ 1 =2.03(5), δ 2 =2.12(5) mm s −1 , ΔE Q1 =0.9(1) and ΔE Q2 =0.6(2) mm s −1 .

Organotin unsymmetric dithiocarbamates: synthesis, formation and characterisation of tin(II) sulfide films by atmospheric pressure chemical vapour deposition

A series of tin unsymmetric dithiocarbamate complexes have been made from metathesis reaction of [CH 3(C 4H 9)NSC 2]Li and R n SnCl 4− n ; [R n Sn(S 2CN(C 4H 9)CH 3) 4− n ] [ n=3, R=Me ( 1), Bu ( 2), Ph ( 3); n=2, R=Me ( 4), Bu ( 5), Ph ( 6); n=1, R=Me ( 7), Bu ( 8), Ph ( 9)]. The complexes were characterised by microanalysis, 13C, 1H and 119Sn NMR, Mössbauer and, in the case of 3, by X-ray diffraction, which revealed one short SnS [2.4631(9) Å] and one long SnS interaction [3.084(1) Å] indicative of a weakly chelating dithiocarbamate ligand. Atmospheric pressure chemical vapour deposition using 1 and 8 with H 2S at 350–550 °C produced SnS and Sn 2S 3 films on glass substrates. The tin sulfides were analysed by Raman, EDAX, SEM and band gap measurements. Growth rates were of the order of 150 nm min −1.

A 1:1 adduct between dimethyltin dibromide andN-methylpyrrolidinone (NMP)

The title compound, di­bromo­di­methyl(N-methyl­pyrrolidin-2-one-O)­tin(IV), [SnBr2(CH3)2(C5H9NO)], exhibits pentacoordination of the Sn atom, with long and short Sn—Br bonds [2.6737 (4) and 2.5256 (4) A, respectively]. The distorted trigonal–bipyramidal coordination polyhedron has two methyl groups and one Br atom in the equatorial plane, the second Br atom and the N-methyl­pyrrolidinone (NMP) ligand occupying the apical positions.

Stable heterocyclic (Schiff base) divalent Group 14 element species (M=Ge, Sn, Pb)

Abstract The synthesis and characterization of new stable divalent germanium, tin and lead homoleptic species L2M [L2=2,2′-N,N′-bis(salicylidene)ethylenediamine, M=Ge (1), Sn (2), Pb (3); (R,R)-(−)-N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine, M=Ge (4), Sn (5), Pb (6) and N-methyl-2,2′-imino-bis(8-hydroxyquinoline), M=Ge (7), Sn (8)] are described. Compounds 1–8 were obtained in good yields by alcoholysis of the MN bonds of the divalent precursors [(Me3Si)2N]2M by diols with bis(salicylidene)diamine and 2,2′-imino-bis-quinoline structures. They have been isolated as solids at ambient temperature and are monomeric. NMR, IR and UV spectra are suggestive of N⋯M intramolecular coordination. The chemistry of 1–8 is illustrated through their reactions with iodine and 1,2-benzoquinones. The X-ray structure of the L2Sn-quinone adduct reveals a distorted octahedral coordination geometry around tin with remarkably short SnN distances. Various RCHO insertion reactions into the MO bonds of 1–8 and MO cleavage reactions with organic acids and acyl halides are also described; they provide a convenient procedure for the generation of new heteroleptic divalent species.

Synthesis, Structure, and Thermolysis Mechanism of S-Alkoxythiazynes

Abstract S-Alkoxy-S,S-diarylthiazynes were prepared by two methods: the alkaline hydrolysis of S,S-diaryl-N-halosulfilimines in aqueous alcohols and the reaction of S,S-diaryl-S-fluorothiazynes with sodium alkoxides. The structure of S,S-diphenyl-S-propoxythiazyne was determined by an X-ray crystallographic analysis, which showed a short SN bond length of 1.441(3) Å. The thermolysis of S-alkoxythiazynes gave elimination products, which were identified as the corresponding carbonyl compounds and N-unsubstituted S,S-diarylsulfilimines. Kinetic experiments for the thermolysis of the S-alkoxy-S,S-diarylthiazynes were carried out. The first-order kinetic behavior, a large kinetic isotope effect (kH/kD = 6.1) using S,S-diphenyl-S-[1,1-2H2]propoxythiazyne, a negative activation entropy (ΔS‡ = −30 J K−1mol−1), and a negative Hammett ρ-value (ρ = −0.35) on the phenyl group were obtained, suggesting that the reaction proceeds via a concerted five-membered cyclic transition state. A deviation from the ideal concerted transition state is discussed in comparison with that for sulfoxides.

8-Methylaminoquinolinium Salts of Tetrachlorodimethylstannate(IV) and Tetrachlorodiphenylstannate(IV)

The title compounds, (C10H11N2)2[SnCl4(CH3)2] and (C10H11N2)2[SnCl4(C6H5)2], have been prepared from the reaction of 8-methylaminoquinoline with diorganotin dichlorides. In the methyl compound, the Sn atom is coordinated to two methyl groups, which are trans with respect to each other [Sn—C 2.102 (5) and 2.103 (4) A], and to four Cl atoms [Sn—Cl 2.442 (1), 2.461 (1), 2.894 (1) and 3.098 (1) A]. The two long Sn—Cl bonds are trans to the short ones and their Cl atoms are hydrogen bonded to the N—H groups of the 8-methylaminoquinolinium cations. The Sn—CH3 bonds are bent away from the short Sn—Cl bonds so that the CH3—Sn—CH3 angle is 155.7 (2)°. A correlation between the C—Sn—C angle and the Sn—Cl bond lengths was observed. The anion of the phenyl compound is close to being octahedral and has exact twofold symmetry; the phenyl groups are trans with respect to each other [Sn—C 2.143 (2) A] and Sn—Cl distances are in the range 2.497 (1)–2.672 (1) A. Two Cl atoms are hydrogen bonded to N—H groups of the cations.

Arylsulfurdiimides: a new class of sulfur–nitrogen anion

N-Aryl-N′-trimethylsulfurdiimides (aryl = 2,6-F2C6H3, 2-FC6H4) react with TASF to give quantitatively the corresponding TAS salts with the ArNSN– anions (2a, 2b), isoelectronic with arylthionylimides 3; because of the short terminal SN bond the anions should be regarded as thiazylamide rather than sulfurdiimide anions.

DFT- and post-HF-study on structure and electronic excitation of acyclic and cyclic sulfur diimides

A series of representative organic acyclic and cyclic sulfur diimides were studied by Hartree–Fock-plus-correlation ab initio quantum chemistry and by density functional theory using Becke's three-parameter functional along with the LYP functional. The widely used formula representation –NSN– for these compounds suggests octet expansion of sulfur. This is not confirmed by theory. Although d-polarization functions significantly improve the numerical results, sulfur d-orbitals are hardly occupied. The calculated electronic charge distribution derived by population analysis and by the atoms-in-molecules topological theory favors charge separation resulting in a more or less ylidic structure with –NS+–N−– and –N−=S+–N– resonance contributors. This structure does not exclude relatively short SN bond lengths. The characteristics of the bonds in the parent structures is preserved in some non-Kekule-type NSN heterocyles. Strong SN bond charge separations of organyl sulfur diimides are accompanied by short SN bond distances and narrow S0/T1 and S0/S1 energy gaps. The experimentally well known naphtho[1,8-cd][1,2,6]thiadiazine and the unknown 3,4-dimethylene-1,2,5-thiadiazole belong to this series. The calculations confirm that 1,2,3-thiadiazole is the diaza analog of thiophene rather than the vinylene-bridged sulfur diimide, while more complex heterocycles such as benzo[1,2-c;4,5-c′]bis[1,2,5]thiadiazole take an intermediate position between classical and non-classical structures. Two closely related minimum structures are defined on the DFT Born–Oppenheimer energy surface of naphtho[1,8-cd;4,5-c′d′]bis[1,2,6]thiadiazine, but so far only one compound is experimentally known. The lowest energy structure is the quinoid form corresponding to the experimentally known compound. © 1997 John Wiley & Sons, Ltd.

DFT- and post-HF-study on structure and electronic excitation of acyclic and cyclic sulfur diimides

A series of representative organic acyclic and cyclic sulfur diimides were studied by Hartree–Fock-plus-correlation ab initio quantum chemistry and by density functional theory using Becke's three-parameter functional along with the LYP functional. The widely used formula representation –NSN– for these compounds suggests octet expansion of sulfur. This is not confirmed by theory. Although d-polarization functions significantly improve the numerical results, sulfur d-orbitals are hardly occupied. The calculated electronic charge distribution derived by population analysis and by the atoms-in-molecules topological theory favors charge separation resulting in a more or less ylidic structure with –NS+–N−– and –N−=S+–N– resonance contributors. This structure does not exclude relatively short SN bond lengths. The characteristics of the bonds in the parent structures is preserved in some non-Kekulé-type NSN heterocyles. Strong SN bond charge separations of organyl sulfur diimides are accompanied by short SN bond distances and narrow S0/T1 and S0/S1 energy gaps. The experimentally well known naphtho[1,8-cd][1,2,6]thiadiazine and the unknown 3,4-dimethylene-1,2,5-thiadiazole belong to this series. The calculations confirm that 1,2,3-thiadiazole is the diaza analog of thiophene rather than the vinylene-bridged sulfur diimide, while more complex heterocycles such as benzo[1,2-c;4,5-c′]bis[1,2,5]thiadiazole take an intermediate position between classical and non-classical structures. Two closely related minimum structures are defined on the DFT Born–Oppenheimer energy surface of naphtho[1,8-cd;4,5-c′d′]bis[1,2,6]thiadiazine, but so far only one compound is experimentally known. The lowest energy structure is the quinoid form corresponding to the experimentally known compound. © 1997 John Wiley & Sons, Ltd.

{N-(1-Adamantyl)[(pentafluoro-2-propenyl)thio]-amino}(fluoro)bis[2,4,6-tris(trifluoromethyl)phenyl]tin at 153K

The synthesis and structure of the title composed (adamantane is tricyclo[3.3.1.1 3,7 ]decane), [SnF(C 9 H 2 F 9 ) 2 {(C 3 F 5 S)(C 10 H 15 )N}], (1), are reported. (1) crystallizes as a monomer with short Sn...F interactions

X-ray and NMR study of the structure of the organotin carbohydrate: 6-Deoxy-1,2- O-isopropylidene-6-(triphenylstannyl)- α-D-glucofuranose

The crystal and molecular structure of the title compound has been determined by X-ray crystallography, 1H NMR and 13C NMR spectroscopy. In the crystals of the chiral carbohydrate the hydroxyl groups are held together by intramolecular H bonding, and there is an intermolecular link between one hydroxyl hydrogen atom and an oxygen of the isopropylidene ring. The tin atom is in a tetrahedral environment and the shortest Sn … O separation is 3.354(5) Å, an interaction that appeats to have no effect on the stereochemistry of the metal. The 1H NMR spectrum shows long-range splitting of a methylene proton by a hydroxyl hydrogen.

Zwei Extreme in der Zinnchemie: Ein nichtbindender Sn–Sn‐Abstand von 285 pm und eine 119Sn‐NMR‐Verschiebung δ = 3301 in metallorganischen Derivaten von Sn(0)

Two Extremes in Tin Chemistry: A Non‐bonding Sn–Sn Distance of 285 pm and a 119Sn‐NMR Shift δ = 3301 in Organome‐tallic Derivatives of Sn(0)The reaction of Na[{Cp'(CO)2Mn}2H] with SnCl2, which produces the inidene compound [Cp'(CO)2Mn\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ {\rm C}\ddot - {\rm C} $\end{document}Sn(Cl)\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ {\rm C}\ddot - {\rm C} $\end{document}Mn‐(CO)2Cp']− under standard workup procedures, results in the formation of [{Cp'(CO)2MnSn}2{μ2‐Mn(CO)2Cp'}2{μ2‐Cl}]− (1) when quenched with unpolar solvents. While, formally, 1 contains tin in its oxidation state zero, it may be conceived as composed of an Sn2−2 entity, which is linearly end‐on coordinated to two Cp'(CO)2Mn 16‐electron species; in addition the tin centers are bridged by two μ2‐Mn(CO)2Cp' moieties and a μ2‐Cl function. The resulting connectivity Sn2{μ2‐Mn(CO)2Cp'}2{μ2‐Cl} thus corresponds to a [1.1.1]propellane scaffolding. While there is no obvious need for a tin‐tin bond in this propellane‐type cage, a short Sn–Sn contact of only 285 pm is observed. While the 119Sn‐NMR signal of 1 could not be recorded, the peculiar bonding in this type of compounds is generally mirrored in their unconventional 119Sn‐NMR shift whereever signals can be observed: it is found that [{Cp*(CO)2Mn}3(μ3‐Sn)], which contains trigonally planar‐coordinated μ3‐Sn as a naked ligand atom, has its 119Sn‐NMR resonance at δ = 3301 well beyond the known range of 119Sn‐NMR shifts. This finding is interpreted in terms of a relatively week Snpπ‐Mndπ π bonding which leads to low‐energy unoccupied molecular orbitals as the prerequisit for a large paramagnetic contribution to the NMR shift.

THE FIRST COMPLETE CRYSTAL STRUCTURE OF A STANNATRANE. TRIMERIC METHYL(2,2′,2″-NITRILOTRIETHOXY)STANNANE HEXAHYDRATE

Abstract An X-ray analysis of the 1-methylstannatrane hexahydrate [MeSn(OCH2CH2)3N]3 . 6H2O (4) revealed a trimeric formulation. It crystallizes in the monoclinic space group C2/c (Z = 4) with a = 9.206 (3) Å, b = 13.774 (5) Å, c = 26.581 (4) Å, and β = 93.33 (2)°. The structure refined to R = 0.074 and R w = 0.086. The trimeric unit is disordered about a twofold axis, which passes through the central Sn atom. The geometry around this central atom closely approximates a pentagonal bipyramid. The two crystallographically equivalent end tin atoms have distorted-octahedral geometries. Strong association of the three monomeric methylstannatrane units formally leading to the trimer is suggested by the short Sn‒O bond lengths involved. These have values of 2.11 (1) and 2.21 (1) Å, as compared to corresponding values within the monomers of 2.17 (1) and 2.23 (1) Å, respectively. The solid-state structure agrees with solution NMR data suggesting its retention in solution. The trimeric unit is indicated in solution as is the presence of three nonequivalent tin centers. The structure of 4 is compared with other seven-coordinated tin compounds. The six water molecules of 4 appear hydrogen bonded to each other, forming hexagonal rings that contain inversion centers. Additional hydrogen bonding binds the rings to adjacent molecules of 4.

Synthesis and structure of Ir 4Sn 3(CO) 6{CH(SiMe 3) 2} 5O 3; a heterometallic ‘raft’ with sail hoisted!

Heterometallic raft clusters have been obtained previously for a variety of metals but none for tin and iridium, and more significantly none to date have had metal groups bonded above the raft plane. We report a hexametallic Ir 4Sn 2 raft to which a third tin group is attached by a single short IrSn bond and three IrOSn bridges.

Tris(chlorodimethylstannyl)amine, a Molecule with a Planar Sn3N Skeleton Stabilized by Intramolecular Sn‐Cl‐Sn Bridges

Nearly D3h symmetry, a planar Sn3N framework, almost symmetrical SnClSn bridges and extremely short SnN bonds-these are the features of the skeleton of (ClMe2Sn)3N 1. This unusual structure has been characterized by NMR spectroscopy, quantum chemical calculations, and X-ray structural analysis. No indications of SnN (dp)π bond participation were found.

REACTION OF 1,3-DI-TERT-BUTYL-2,2-DIMETHYL-4,4-DICHLORO-1,3,2,4λ4-DIAZASILASTANNETIDINE WITH SILVER TRIFLUOROMETHANESULFONATE. THE CRYSTAL STRUCTURE OF POLYMERIC 1,3-DI-TERT-BUTYL-2,4-DIMETHYL-2,4-DITRIFLUOROMETHANESULFONATE-1,3,2,4λ5-DIAZASILASTANNETIDINE

Abstract When 1,3-di-tert-butyl-2,2-dimethyl-4,4-dichloro-1,3,2,λ2-diazasilastannetidine (1) is allowed to react with the chloride abstracting reagent AgCF3SO3 the chlorides are displaced by triflates forming 2. At the same time a rearrangement in the molecule takes place, one of the methyl groups on silicon migrating to tin in exchange of a triflate. In the solid the new compound 2 is a coordination polymer with trigonal bi-pyramidal tin centers, which exhibit quite unusual short Sn—N bonds in the axial plane (2.005 A) [X-ray structure determination, space group P2/l/n, a = 10.199(6)A, b = 13.532(9)A, c = 17.641(9)A, β = 99.13(9)°, Z = 4].

REACTION OF 1,3-DI-TERT-BUTYL-2,2-DIMETHYL-4,4-DICHLORO-1,3,2,4λ4-DIAZASILASTANNETIDINE WITH SILVER TRIFLUOROMETHANESULFONATE. THE CRYSTAL STRUCTURE OF POLYMERIC 1,3-DI-TERT-BUTYL-2,4-DIMETHYL-2,4-DITRIFLUOROMETHANESULFONATE-1,3,2,4λ5-DIAZASILASTANNETIDINE

Abstract When 1,3-di-tert-butyl-2,2-dimethyl-4,4-dichloro-1,3,2,λ2-diazasilastannetidine (1) is allowed to react with the chloride abstracting reagent AgCF3SO3 the chlorides are displaced by triflates forming 2. At the same time a rearrangement in the molecule takes place, one of the methyl groups on silicon migrating to tin in exchange of a triflate. In the solid the new compound 2 is a coordination polymer with trigonal bi-pyramidal tin centers, which exhibit quite unusual short Sn—N bonds in the axial plane (2.005 Å) [X-ray structure determination, space group P2/l/n, a = 10.199(6)Å, b = 13.532(9)Å, c = 17.641(9)Å, β = 99.13(9)°, Z = 4].

Synthesis and crystal structure of [1,2-benzenedithiolate-(2—)- S, S′]bis{methyl-1,3-dithia-benzo[ c]-2-stannolanyl}, [(CH 3Sn) 2(C 6H 4S 2) 3

The reaction of sodium 1,2-benzenedithiolate with methyltin trichloride in water gives the benzenedithiolate of methyltin(IV) as a yellow precipitate. The structure of this compound has been determined by single-crystal X-ray diffractometry. The molecule consists of two benzol[ c]1,2,3-dithia-stannolanyl moieties held together by a bridging benzene-1,2-dithiolate ligand. The geometry about the tin could be described as distorted tetrahedral, even if in view of the short intramolecular Sn⋯S contacts the structure is better regarded as involving pentacoordinate tin in a distorted trigonal bypyramid.

ChemInform Abstract: THE FIRST COMPLETE CRYSTAL STRUCTURE OF A STANNATRANE. TRIMERIC METHYL(2,2′,2“‐NITRILOTRIETHOXY)STANNANE HEXAHYDRATE

Abstract An X-ray analysis of the 1-methylstannatrane hexahydrate [MeSn(OCH2CH2)3N]3 . 6H2O (4) revealed a trimeric formulation. It crystallizes in the monoclinic space group C2/c (Z = 4) with a = 9.206 (3) A, b = 13.774 (5) A, c = 26.581 (4) A, and β = 93.33 (2)°. The structure refined to R = 0.074 and R w = 0.086. The trimeric unit is disordered about a twofold axis, which passes through the central Sn atom. The geometry around this central atom closely approximates a pentagonal bipyramid. The two crystallographically equivalent end tin atoms have distorted-octahedral geometries. Strong association of the three monomeric methylstannatrane units formally leading to the trimer is suggested by the short Sn[sbnd]O bond lengths involved. These have values of 2.11 (1) and 2.21 (1) A, as compared to corresponding values within the monomers of 2.17 (1) and 2.23 (1) A, respectively. The solid-state structure agrees with solution NMR data suggesting its retention in solution. The trimeric unit is indicated in sol...

Crystal and molecular structure of tris(hexaamminerhodium(III)) tetrakis(trichlorostannato(II))(tetrachlorostannato(II)rhodate(I) hexachlorostannate(II) tetrahydrate

The crystal and molecular structure of the title compound, [Rh(NH 3) 6] 3[Rh(SnCl 3) 4(SnCl 4)] [SnCl 6] · 4H 2O, has been determined by the single-crystal X-ray diffraction method. The compound crystallizes in the monoclinic system, space group P2 n with a = 16.581(2), b = 11.010(4), c = 16.024(2)Å, β = 90.76(1), and two molecules per unit cell. The structure was solved by Patterson's method and refined by the least-squares technique to give a final R factor of 0.031. The three cations, [Rh(NH 3) 6] 3+, are a regular octahedron with an average RhN bond length of 2.07 Å. The rhodium anion, [Rh(SnCl 3) 4(SnCl 4)] 5−, is a trigonal bipyramid with the two axial RhSn bonds, 2.493 Å in length, and the three equatorial bonds, 2.546, 2.540, and 2.540 Å. One of the three tin atoms in the equatorial trigonal plane forms a distorted trigonal bipyramid with two short SnCl bonds 2.384 Å in length and two long bonds, 2.733 Å. The other four tin atoms have a distorted tetrahedral arrangement with an average SnCl bond length of 2.42 Å. The tin anion, [SnCl 6] 4−, which is not coordinated to rhodium, forms extremely long SnCl bonds of 2.763, 2.800, and 2.893 Å in a distorted octahedral arrangement.