One-dimensional polymeric chlorocadmate(II) systems of N-methylpiperazinium and N,N′-dimethylpiperazinium compounds: synthesis, structural and thermal properties |
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Authors: | Anna Bonamartini Corradi Maria Rita Cramarossa Monica Saladini Luigi Pietro Battaglia Jolanda Giusti |
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Institution: | a Dipartimento di Chimica, Università degli Studi di Modena, 41100, Modena, Italy b Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Università degli Studi di Parma, 43100, Parma, Italy c Dipartimento di Chimica, Università degli Studi di Firenze, 50100, Florence, Italy |
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Abstract: | The chlorocadmate(II) systems of (H2me2pipz)Cd2Cl6(H2O)2] (1) and (H2mepipz)2Cd3Cl10(H2O)] (2) (L = me2pipz = N,N′-dimethylpiperazine; L′ = mepipz = N-methylpiperazine) were prepared and their structural and thermal properties investigated. Compound 1 is monoclinic, space group P21/c, A = 7.664(1), B = 7.472(4), C = 15.347(1) Å, β = 99.468(7)°, Z = 2, R = 0.024. The crystal structure consists of organic cations and infinite one-dimensional chains of CdCl3(H2O)]n3? anions. Each Cd atom is octahedrally surrounded by bridged and terminal chlorine atoms and by a water molecule, which is in trans position with respect to the terminal chlorine atom. Inter- and intrachain hydrogen bond interactions between the terminal chlorine atoms and the water molecules contribute to the crystal packing. Compound 2 is orthorhombic, space group Cmc21, A = 15.286(3), B = 13.354(3), C = 13.154(3) Å, R = 0.023. The crystal structure consists of organic dications and infinite chains of Cd2Cl6(CdCl4H2O]n4? units running along the 001] axis. Each unit is formed of regularly alternate six-coordinated Cd atoms, one of them linking one pentacoordinated Cd atom which completes its coordination througha water molecule. A strong hydrogen bond interaction involving the organic dication and the inorganic chain contributes to the crystal packing. Differential hydrogen bond interaction involving the organic dication and the inorganic chain contributes to the crystal packing. Differential scanning calorimetry measurements did not show the presence of any structural phase transitions. The structures are compared with those of (H2pipz)Cd2Cl6(H2O)2] (3), (H2mepipz)Cd2Cl6(H2O)2]·H2O (4) and (H2mepipz)Cd2Cl6] (5) (L = pipz = piperazine, L′ = mepipz = N-ethylpiperazine). |
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Keywords: | Crystal structures Cadmium complexes Chlorocadmate complexes Polymeric complexes Monodimensional chain complexes |
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