Synthesis, characterisation and study of mercury(II) chloride complexes with triphenylphosphine and heterocyclic thiones. The crystal structures of [(benzothiazole-2-thionato)(benzothiazole-2-thione)(
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- 作者：Hadjikakou ; S.K. ; Kubicki ; M.
- 关键词：Mercury(II) complexes ; Triphenylphosphine ; Benzothiazole-2-thione ; pyrimidine-2-thione ; Crystal structures
- 刊名：Polyhedron
- 出版年：2000
- 出版时间：October 30, 2000
- 年：2000
- 卷：19
- 期：20-21
- 页码：2231-2236
- 全文大小：112 K
文摘
Direct reaction of mercury(II) chloride with triphenylphosphine (PPh3) and benzothiazole-2-thione (bzthtH) in the molar ratio of 1:1:2 results in the formation of the [Hg(PPh3)(bzthztH)(bzthzt)Cl] (1) (bzthzt=the anion of benzothiazole-2-thione) while the reaction of mercury(II) chloride with triphenylphosphine (PPh3) and pyrimidine-2-thione (pmtH) in the molar ratio of 1:1:1 gives [Hg2Cl2(PPh3)2(pmt)2] (2) (pmt=the anion of pyrimidine-2-thione). The complexes have been characterised by their elemental analyses, melting points and their FTIR, far-IR spectroscopic data. The crystal structure of complex 1 which has been determined by single-crystal X-ray crystallography at r.t. reveals that the molecule is monomeric with tetrahedral geometry around the metal ion. A benzothiazole-2-thione molecule and a benzothiazole-2-thionato anion are coordinated, via sulfur atoms, to the mercury(II) ion [Hg
S(2A)=2.726(2) and HgS(2)=2.419(2) Å]. A triphenylphosphine molecule is also coordinated through a phosphorus atom to the metal ion [HgP=2.453(2) Å] while the tetrahedral geometry around the mercury is completed by a chlorine atom [HgCl=2.633(2) Å]. The complex is covalent in the solid state. The crystal structure of complex 2 which has also been established by single-crystal X-ray crystallography at 100(1) K shows that the molecule is binuclear and consists of two different moieties with tetrahedral geometry around each mercury(II) ion. One moiety consists of a mercury(II) ion with two phosphorus atoms from phosphine ligands and two bridging chlorine atoms, while the other consists of a mercury(II) ion and two sulfur atoms of pyrimidine-2-thionato ligands. The entire complex is covalent in the solid state. The two Hg(2)S(42) bond lengths are 2.3513(11) Å while the two Hg(1)P(1) bond lengths are 2.4826(9) Å. The two parts of the molecule are linked to each other by two chlorine atoms with Hg(1)Cl(1) and Hg(2)Cl(1) bond distances of 2.5310(10) and 3.0472(10) Å, respectively.
S(2A)=2.726(2) and HgS(2)=2.419(2) Å]. A triphenylphosphine molecule is also coordinated through a phosphorus atom to the metal ion [HgP=2.453(2) Å] while the tetrahedral geometry around the mercury is completed by a chlorine atom [HgCl=2.633(2) Å]. The complex is covalent in the solid state. The crystal structure of complex 2 which has also been established by single-crystal X-ray crystallography at 100(1) K shows that the molecule is binuclear and consists of two different moieties with tetrahedral geometry around each mercury(II) ion. One moiety consists of a mercury(II) ion with two phosphorus atoms from phosphine ligands and two bridging chlorine atoms, while the other consists of a mercury(II) ion and two sulfur atoms of pyrimidine-2-thionato ligands. The entire complex is covalent in the solid state. The two Hg(2)S(42) bond lengths are 2.3513(11) Å while the two Hg(1)P(1) bond lengths are 2.4826(9) Å. The two parts of the molecule are linked to each other by two chlorine atoms with Hg(1)Cl(1) and Hg(2)Cl(1) bond distances of 2.5310(10) and 3.0472(10) Å, respectively.