Structural Study of Alkaline 1‐Phenyl‐1H‐1, 2, 3, 4‐tetrazole‐5‐thiolate Salts: An Example of Periodicity in Alkaline Cations

Abstract

The alkaline 1-phenyl-1H-1, 2, 3, 4-tetrazole-5-thiolate salts, M[C 6 H 5 N 4 CS] (M ϭ Li (1), Na (2), K (3), Rb (4) and Cs (5)) were obtained and characterized by means of mass spectrometry (FAB ϩ ) and NMR ( 1 H; 13 C) spectroscopy. The structures of Na (2), K (3), Rb (4) and Cs (5) compounds were determined by Xray diffraction methods. The ligand shows a rich variety of coordination patterns with the alkaline cations. The formation of a four- (1), Na (2), K (3), Rb (4) und Cs (5)) wurden hergestellt und durch Massenspektrometrie (FAB ϩ ) und NMR-Spektroskopie ( 1 H, 13 C) charakterisiert. Die Strukturen von 2, 3, 4 und 5 wurden röntgenographisch ermittelt. Die Ligandionen zeigen eine reichhaltige Variation des Koordinationsverhal-1627 membered ring MSCN in the compounds with heavier alkali cations (K, Rb and Cs) is shown. In all the cations the coordination number around it increases with the ionic radius. Compounds with Cs ϩ and Rb ϩ exhibited the formation of Cs-C and Rb-C interactions with the phenyl group. Keywords: Alkali metals; Phenylthiotetrazol; Crystal structure. tens mit den Alkalimetallionen. In den Verbindungen mit den Kationen K ϩ , Rb ϩ und Cs ϩ liegen viergliedrige Ringe MSCN vor. Die Koordinationszahl an den Kationen steigt mit der Größe des Ionenradius an. Die Verbindungen mit Rb ϩ und Cs ϩ weisen Rb···Cund Cs···C-Kontakte mit der Phenylgruppe auf. Strukturuntersuchungen an Alkali-1-Phenyl-1H-1,2,3,4-tetrazol-5-thiolat-Salzen: Ein Beispiel der Periodizität von Alkalimetallionen

Metal derivatives of tetrazoles

“…332 The coordination number of the cations increases from 5 to 8 following an increase in the ionic radius on passing from Na + to Cs + . In K + , Rb + and Cs + complexes, four-membered MSCN rings are formed upon bidentate coordination of the ligand by the S and N(4) atoms, while in Rb + and Cs + compounds, Rb_C and Cs_C contacts with the carbon atom of the phenyl group were also found.…”

Crystal structure of potassium 1-methyl-1H-1,2,3,4-tetrazole-5-thiolate, C2H3N4SK

“…The coordination behavior is quite different from that of sodium 1-phenyl-1H-1,2,3,4-tetrazole-5-thiolate monohydrate [Na(C 6 H 5 N 4 CS) 2 ·H 2 O] 2 , which is a 2D polymer. Cesium 1-methyl-1H-1,2,3,4-tetrazole-5-thiolate and cesium 1-phenyl-1H-1,2,3,4-tetrazole-5-thiolate were quite different in respect to their structures and coordination behavior [10,12]. To get deeper insight into coordination behavior of 1-methyl-1H-1,2,3,4-tetrazole-5-thiono anion, herein we report the crystal structure of potassium 1-methyl-1H-1,2,3,4-tetrazole-5-thiolate.…”

“…Early research mainly focused on their transition metal complexes and it was found that the ligand anion tends to coordinate through the exocyclic S atom [1][2][3][4][5][6][7][8][9]. It was not until 2004 that a crystallographic investigation on alkaline 1-phenyl-1H-1,2,3,4-tetrazole-5-thiolate compounds had been addressed [10]. It was found that in case of alkaline 1-phenyl-1H-1,2,3,4-tetrazole-5-thiolate, the ligand coordinates through both the exocyclic S atom and the N atoms.…”

Azide Chemistry – An Inorganic Perspective, Part II[‡][3+2]‐Cycloaddition Reactions of Metal Azides and Related Systems

“…XI), [402] a coordination mode which will be taken for granted in salts like [H 2 B{(κN 4 )-MeN 4 C=S} 2 ] -, [403] in accord with Pearson's hard/soft concept. Note that in the structures of alkali metal complexes (M{SCN 4 Ph}, [404] [M(18-crown-6)]{SCN 4 Me}, [405] ) four-membered MSCN rings have been found, i.e. we are dealing with a bidentate coordination of the ligand via the S and N 4 atoms according to types IX + X.…”