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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[CuN2/22−], which are kinked alternately at the first and then the second nitrogen atom. Ba16[(CuN)8][Cu2N3][Cu3N4] crystallizes monoclinic in P21/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[CuN2/22−] separated by discrete linear [Cu2N3]7− and Z-shaped [Cu3N4]9− ions. Ca4Ba[CuN2]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 [CuN2]5−.
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Niewa et al. (1998) studied this question.
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