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Abstract
The three title compounds were prepared from copper or copper(I) oxide and alkaline earth metals in sodium fluxes under medium nitrogen pressures and structurally characterized. Ba[CuN] crystallizes monoclinic in C 2/c (No. 15), with Z=12, a=14.462(2) Å, b=5.5700(8) Å, c=9.478(1) Å, β=102.960(2)°. The structure contains infinite chains ∞ 1[CuN 2/2 2−], which are kinked alternately at the first and then the second nitrogen atom. Ba 16[(CuN) 8][Cu 2N 3][Cu 3N 4] crystallizes monoclinic in P2 1/c (No. 14), with Z=1, a=9.5611(4) Å, b=7.2731(2) Å, c=13.5225(5) Å, β=93.115(2)°. It is build from infinite helical chains ∞ 1[CuN 2/2 2−] separated by discrete linear [Cu 2N 3] 7− and Z-shaped [Cu 3N 4] 9− ions. Ca 4Ba[CuN 2] 2 crystallizes tetragonal in P 4/ncc (No. 130), with Z=4, a=8.2366(4) Å, c=12.5731(6) Å. In this compound the nitridocuprate ions are broken down to isolated linear units [CuN 2] 5−.
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