structure structure (solids and liquids) D 2000 43 -012 X-Ray and Raman Investigations on Cyanides of Mono-and Divalent Metals and Synthesis, Crystal Structure and Raman Spectrum of Tl 5 (CO 3 ) 2 (CN). -Pseudobinary cyanides of mono-and divalent metals are synthesized and characterized by XRD and Raman spectroscopy. Compound (IV) is an intermediate in the reaction path from TlCN to Tl 2 CO 3 . As revealed by single crystal XRD, (IV) crystallizes in the space group Cmca with Z = 4. (VIa) crystallizes in the space group Pn3m with Z = 2, Hg(CN) 2 in the space group I42d with Z = 8, and AgCN in space group R3m with Z = 3.

Binary and ternary alkaline earth metal nitrides compounds have been synthesized and characterized by the means of X-ray structure analysis. By the reaction of the alkaline earth metals Be, Mg, and Ca with dry nitrogen, we obtained crystalline material of Be 3 N 2 (1), Mg 3 N 2 (2), and Ca 3 N 2 (3), respectively. For these three compounds we could confirm the cubic anti bixbyite structure (Ia3 (#206); 1: a = 814.92(1) pm; 2: 997.26(6) pm and 3: a = 1147.86(2) pm). By reacting 1 : 2 : 1 mixtures of Ae (Ae = Ca, Sr) : Mg : NaN 3 we synthesized the ternary nitrides CaMg 2 N 2 (4) and SrMg 2 N 2 (5). We confirmed the structural data obtained by Rietveld-analysis of X-ray powder diffraction data for 4 and found 5 to be isotypic (anti-C±M 2 O 3 structure, trigonal, P 3ml (#164); 4: a = 354.77(5) pm, c = 609.60(12) pm; 4: a = 362.20(5), c = 635.90(13) pm). The indexing of the powder diffractogram of ªCa 3 Mg 3 N 4 º and refining the lattice parameters (hexagonal, a = 352.9(2) and c = 607.5(5) pm) suggest its identity with 4. The black ªlow-temperature phase of Ca 3 N 2 º has been synthesized and and the X-ray powder diffractogram has been recorded. The reactions of this phase are also described. The yellow ªhigh-temperature phase of Ca 3 N 2 º was found to be Ca 4 N 2 (CN 2 ).

No abstract

Red‐orange, transparent single crystals of EuCN2 (Pnma (62), a = 1232.41(9), b = 395.26(3) and c = 539.43(4) pm, Z = 4) are obtained by the reaction of EuN, C and NaN3 in arc‐welded Ta ampoules at 1300 K. The first ternary rare earth metal cyanamide is isotypic to α‐SrCN2 and shows the characteristic frequencies for the CN22— unit in the optical spectra (νs = 1244; νas = 1969 and 2087; δ = 655 / 666 cm—1).

The crystal structures of LiN3*H2O (P63/mcm (No. 193), Z = 6; 924.01(13); 560.06(7) pm); NH4N3 (Pmna (No. 53), Z =4; a=889.78(18), b=380,67(8), c=867.35(17) pm); Ca(N3)2 (Fddd (No. 70), Z = 8; a=595.4(2), b=1103.6(5), c=1133.1(6) pm), Sr(N3)2 (Fddd (No. 70), Z =8; a= 612.02(9), b = 1154.60(18), c = 1182.62(15) pm); Ba(N3)2 (P21/m (No. 11), Z = 2; a = 544.8(1), b = 439.9(1), c = 961.3(2) pm, β = 99.64(3)°) and TlN3 (I4/mcm (No. 140), Z = 2; 618.96(9); 732.71(15) pm) have been either determined for the first time or redetermined by X-ray diffraction on single crystals. The afore mentioned compounds, AN3 (A = Na, K, Rb, Cs), M(N3)2 · 2.5 H2O (M = Mg, Zn) and the cyanamides Li2CN2, CdCN2 and CuCN2 were investigated by Raman and IR spectroscopy (KBr technique). Structural features and spectroscopic data of azides and cyanamides from this work and from literature are listed and compared.