Crystal structure of indium(III) dithizonate

Abstract

The crystal structure of indium(rr1) dithizonate, [In( Hdz)J, has been determined by single-crystal X-ray diffraction methods at 295(1) K, and refined by least squares to a conventional residual of 0.043 for 3 081 ' observed ' reflections. Crystals are triclinic, space group P7, with a = 18.469( 6), b = 14.928(7), c = 7.570(4) A, a = 80.31 (4), f3 = 86.58(4), y = 75.48(4)", and Z = 2. The asymmetric unit of the structure is the mononuclear [In( Hdz),] molecule ; the indium atom is trigonally bipyramidal, five co-ordinated, one ligand being unidentate and co-ordinated equatorially through the sulphur [In-S 2.468(3) A], while the other two are bidentate (N,S), spanning axial and equatorial positions. The axial In-N distances are 2.372(6) and 2.334(6) A, while the associated equatorial In-S distances are 2.477(3) and 2.467(3) A.

(1,5-Diphenylthiocarbazonato-κS)trimethyltin(IV)

“…The structure revealed distorted tetrahedral coordination geometry around tin, with S-Sn-C bond angles 110.5 (4)°, 105.0 (4)° and 98.0 (9)°. Contrary to most bidentate metaldithizonate complexes, but with the exception of one ligand in In(HDz) 3 (Harrowfield et al, 1983) and in an osmium carbonyl cluster compound (Kong & Wong, 1999), coordination of dithizone to trimethyltin(IV) was found to be monodentate, through the sulfur atom alone. The dithizonate ligand clearly illustrates a high degree of planarity, with the ligand backbone being linear, comparable to that of uncoordinated dithizone (Herbstein & Schwotzer, 1984).…”

“…For structural aspects of dithizone and its oxidation products and observed solvatochromism and concentratochromism, see: Von Eschwege et al (2011a). For related ligand and complex structures, see: Harrowfield et al (1983); Kong & Wong (1999); Herbstein & Schwotzer (1984); Fernandes et al (2002); Von Eschwege et al (2008); Laing et al (1971). For electrochemical studies of dithizone and its Hg complex, see: Von Eschwege & Swarts (2010); Von Eschwege et al (2011b).…”

Coordination compounds of indium. Part 43. Indium(III) derivatives of benzenethiol, and the crystal structure of tetraphenylphosphonium bromotris(benzenethiolato)- indate(III), Ph4P[BrIn(SPh)3]

“…This caveat is strengthened by more recent results (25) for the compound In(dithi~onate)~, in which the local geometry at the metal is trigonal bipyramidal, with two bidentate and one monodentate ligand giving a InS2N2S1 kernel. In this compound the In-S bond lengths are 2.477(3), 2.467(3), and 2.468(3), close to the distances found in the present work.…”

A ruthenium complex with 1,5-diphenyl-3-thiocarbazone (dithizone) as monodentate ligands: bis(2,2′-bipyridyl-κ2N,N′)bis(dithizonato-κS)ruthenium(II)

“…Unlike the trans±cis structure of S-methyldithizone (Preuss & Gieren, 1975), which contains a ®ve-membered hydrogen-bonded ring, the structure of (I) is trans±trans about the N atoms, with no hydrogen bonding to the H atom attached to atom N2. This structure is similar to that of a monodentate Hdtz À ligand in an indium complex (Harrow®eld et al, 1983b), a bridging monodentate Hdtz À ligand in an osmium cluster (Kong & Wong, 1999) and the iodine adduct of dithizone (Herbstein & Acta Crystallographica Section C A view of the title ruthenium complex, with displacement ellipsoids drawn at the 30% probability level. Schwotzer, 1982Schwotzer, , 1984.…”

“…1 and Table 1). Other examples of monodentate binding of dithizone have involved a main group metal (Harrow®eld et al, 1983b) and bridging ligands (Kong & Wong, 1999).…”