THE FIRST AQUA PENTAFLUORO MANGANATES(III) : SYNTHESES AND STRUCTURES

For the first time aqua pentafluoro manganate(III) compounds with different organic N-cations have been prepared and their crystal structures have been determined: N,N′-DMenH2[MnF5(H2O)] · H2O 1 (N,N′-DMen = N,N′-Dimethylethylenediamine), space group P21/c, a = 916.0, b = 1004.8, c = 1247.9 pm, β = 106.03°, R = 0.035; NMpipzH2 · [MnF5(H2O)] · H2O 2 (NMpipz = N-Methylpiperazine), space group P21/n, a = 757.7, b = 1261.9, c = 1197.1 pm, β = 105.09°, R = 0.027; N,N′-DMpipzH2[MnF5(H2O)] · 2 HF 3 (N,N′-DMpipz = N,N′-Dimethylpiperazine), space group P1, a = 677.1, b = 863.9, c = 1187.7 pm, α = 79.18°, β = 81.63° γ = 67.62°, R = 0.026; and N,N-DMenH2[MnF5(H2O)] · 1/2 HF 4 (N,N-DMen = N,N-Dimethylethylenediamine), space group P1, a = 859.3, b = 1086.5, c = 1092.0 pm, α = 86.96°, β = 78.52° γ = 89.01°, R = 0.035. In all compounds the [MnF5(H2O)]2– octahedra are connected via H-bonds forming 3 D and 2 D network arrangements. The anions are strongly elongated by the Jahn-Teller effect. The FTIR spectra are presented. Die ersten Aquapentafluormanganate(III) – Synthese und Struktur Erstmalig gelang es, Aquapentafluoromanganate(III) mit verschiedenen N-haltigen Kationen darzustellen. Die Kristallstrukturen von vier neuen Verbindungen sind bestimmt worden: N,N′-DMenH2[MnF5(H2O)] · H2O 1 (N,N′-DMen = N,N′-Dimethylethylendiamin), Raumgruppe P21/c, a = 916,0, b = 1004,8, c = 1247,9 pm, β = 106,03°, R = 0,035; NMpipzH2[MnF5(H2O)] · H2O 2 (NMpipz = N-Methylpiperazin), Raumgruppe P21/n, a = 757,7, b = 1261,9, c = 1197,1 pm, β = 105,09°, R = 0,027; N,N′-DMpipzH2 · [MnF5(H2O)] · 2 HF 3 (N,N′-DMpipz = N,N′-Dimethylpiperazin), Raumgruppe P1, a = 677,1, b = 863,9, c = 1187,7 pm, α = 79,18°, β = 81,63° γ = 67,62°, R = 0,026; and N,N-DMenH2[MnF5(H2O)] · 1/2 HF 4 (N,N-DMen = N,N-Dimethylethylendiamin), Raumgruppe P1, a = 859,3, b = 1086,5, c = 1092,0 pm, α = 86,96°, β = 78,52° γ = 89,01°, R = 0,035. In allen Verbindungen erfolgt eine Verknupfung der [MnF5(H2O)]2– Oktaeder uber 3 D- bzw. 2 D-Wasserstoff-Brucken-Netze in unterschiedlicher Weise. Die Anionen sind durch den Jahn-Teller-Effekt stark gestreckt. Die FTIR Spektren der Verbindungen werden dargestellt.