- Structural investigations and thermal behaviour of mercury(II) sulfito complexes
-
The crystal structures of (NH4)[HgSO3Cl] (1) and of (NH4)2[Hg(SO3)2] (2) were determined from single crystal diffractometer data sets. 1: 22°C, Pnma, Z = 4, a = 15.430(3), b = 5.525(1), c = 6.679(1) A, R(F) = 0.0256, R W(F2) = 0.0642 (all 1056 unique reflections). 2: -108°C, P212121, Z = 4, a = 6.2240(4), b = 9.3908(6), c = 13.6110(8) A, R(F) = 0.0179, Rw(F2) = 0.0493 (all 2699 unique reflections). The structure of 1 contains bent Cl-Hg-SO3 entities (site symmetry m; d(Hg-Cl) = 2.3403(13) A, d(Hg-S) = 2.3636(12) A, ∠(Cl-Hg-S) = 164.51(5)°, d(S-O) 2×1.458(3) A, 1.468(4) A, d?(S-O) = 1.461 A) linked to undulated ribbons parallel to the 6-axis by intermolecular secondary bonds SO...Hg (d(O...Hg) = 2×2.595(3) A). These ribbons in turn aggregate to layers around the bc-plane. The layers are stacked along the a-axis with interlayer distances of a/2. The structure of 2 is made up of O 3S-Hg-SO3 moieties (d(Hg-S) = 2.3935(7), 2.3935(8) A; ∠.(Hg-S-Hg) = 174.41(3)°; d(S-O) = 1.474 A), that are linked to ribbons parallel to the a axis by coordination of Hg to three remote O atoms (2.801(4) ∠ d(Hg-O) > 2.844(3) A). Adjacent ribbons are joined together by an additional Hg-O contact of 2.733(3) A, leading to a three-dimensional anionic framework. Both crystal structures are stabilised by disordered NH4+ cations, placed between the anionic layers or in the vacancies of the framework, via moderate hydrogen bonding interactions N-H...O with donor-acceptor distances ranging from 2.8 to 3.2 A. 1 and 2 were further characterised by thermal analysis (TG, DSC). They start to decompose at temperatures above 130°C.
- Weil, Matthias,Breitinger, Dietrich K.,Liehr, Guenther,Zuerbig, Juergen
-
-
Read Online
- SYNTHESIS AND PROPERTIES OF COVALENT TRI- AND TETRAVALENT VANADIUM
-
Reactions of VCl3*3THF with RMgX (R = Ph, CH2SiMe3, C6F5) in various ratios have been studied.The stable compounds R3V*THF (R = CH2SiMe3, C6F5) were obtained.The chemical properties of R3V*THF, R4V*2L (R = CH2Ph, L = Et2O; R = C6F5, L = THF) and (Me3SiCH2)4V were investigated.Cleavage of the vanadium-carbonium ?-bond occurs in reactions with H2O, HCl and HgCl2.The insertion of carbon dioxide into the vanadium-carbon ?-bond was investigated.A scheme for the derivatives of tri- and tetravalent vanadium is proposed.Oxidative addition to (C6F5)3V*THF by Ph3CCl and VCl3*3THF was also studied.
- Razuvaev, G.A.,Latyaeva, V.N.,Vyshinskaya, L.I.,Drobotenko, V.V.
-
p. 169 - 182
(2007/10/02)
-