Synthetic and single-crystal X-ray diffraction studies of CH2I2 and aryl iodide complexes of silver carboxylates and β-diketonates

The silver(I) iodocarbon complexes [{Ag-2(O2CCF3)(2)(CH2I2)(2)}(n)] 1, [{Ag-2(O2CCF3)(2)(1,2-I2C6H4)(2)}(n)] 2, [{Ag-2(O2CCF3)(2)(1, 4-I2C6H4)(2)}(n)] 3, [{Ag-2(O2CCF3)(2)(IC6H5)}(n)] 4, [{Ag-4(O2CCF3)(4)(H2O)(2)(p-IC6H4Me)(2)}(n)] 5, [{Ag-2(O2CCF3)(2)(1,2-I2C6H4}(n)] 6, [{Ag-2(O2CCCl3)(2)(HO2CCCl3)(1,2-I2C6H4)}(n)] 7, [{Ag-2(O2CCCl3)(2)(HO2CCCl3)(IC6H5)}(n)] 8, [{Ag-4(hfacac)(4)(p-IC6H4Me)(2)] 10 (hfacac = 1,1,1,5,5,5-hexafluoroaceylacetonate) and [Ag-4(hfacac)(4)(1,2-I2C6H4)(3)] 11 have been prepared and structurally characterized by single-crystal X-ray diffraction. The silver carboxylate complexes all contain carboxylate-bridged Ag-2(carboxylate-O,O')(2) dimers (Ag-O 2.22-2.40 Angstrom) with the intradimer Ag ... Ag distance varying in the range 2.9106(12) to 3.1527(14) Angstrom which are the values observed for the alternating dimer units Ag-2(O2CCF3)(2)(H2O)(2) and Ag-2(O2CCF3)(2) observed in 5. In the complexes 1-3 the silver trifluoroacetate dimers are linked by I,I'-bridging I2R ligands with one 'short' Ag-I bond (2.94-3.05 Angstrom) and one 'long' Ag-I bond (3.13-3.14 Angstrom) per silver. In 4, 7 and 8 the Ag-2(carboxylate-O,O')(2) dimers are extended into a chain polymer via Ag2O2 rings formed by co-ordination of each silver to an oxygen atom (Ag-O 2.33-2.51 A) from an adjacent dimer. The 1,2-I2C6H4 forms an I,I' bridge across the two silver atoms of the dimer unit in 7 [Ag-I 2.918(1) and 3.024(1) Angstrom]. Complex 8 contains an acute angle bridging IC6H5 [Ag-I 2.927(2) and 2.970(2) Angstrom, Ag-I-Ag 61.4(1)degrees], whilst in 4 the IC6H5 is semibridging [Ag-I 2.853(1) and 3.309(1) 8]. In complex 5 the two structurally different dimer units are bridged in a wide-angle fashion by p-IC6H4Me [Ag-I 2.9200(9) and 2.9333(8) Angstrom, Ag-I-Ag 144.53(3)degrees]. Complex 6 contains eight-atom Ag-2(O2CCF3-O,O')(2) rings linked to six-atom Ag-2(O2CCF3-O,O')(O2CCF3-O,O) rings which are interlinked to give an alternating 8646 ring chain polymer with I,I'-bridging 1,2-I2C6H4 across the two silvers of the six-atom rings [Ag-I 2.722(2) and 2.980(2) Angstrom]. The hfacac complex 10 contains a tetranuclear unit in which the hfacac ligands both chelate and bridge whilst the p-iodo-toluenes each bridge two silvers via eta(1)-iodocarbon and eta(2)-aryl co-ordination. Complex 11 is a tetranuclear unit in which three hfacac ligands both chelate and bridge whilst the fourth hfacac ligand bridges two silvers and forms a monodentate interaction with a third silver in a mu-O, eta(1)-O' mode. One 1,2-I2C6H4 ligand forms a monodentate interaction with a silver atom [Ag-I 3.064(3) Angstrom] whilst the other two 1,2-I2C6H4 molecules function as highly unsymmetrical bidentate ligands [Ag-I 2.691(2), 3.350(2) and 2.719(2) and 3.228(2) Angstrom]. The Ag-I-C bond angles vary from 85.9(4)degrees in 11 to 108.70(12)degrees in 3.