Synthesis of alkaline earth diazenides M(AE)N2 (M(AE) = Ca, Sr, Ba) by controlled thermal decomposition of azides under high pressure

The alkaline earth diazenides M(AE)N(2) with M(AE) = Ca, Sr and Ba were synthesized by a novel synthetic approach, namely, a controlled decomposition of the corresponding azides in a multianvil press at high-pressure/high-temperature conditions. The crystal structure of hitherto unknown calcium diazenide (space group I4/mmm (no. 139), a = 3.5747(6) ?, c = 5.9844(9) ?, Z = 2, wR(p) = 0.078) was solved and refined on the basis of powder X-ray diffraction data as well as that of SrN(2) and BaN(2). Accordingly, CaN(2) is isotypic with SrN(2) (space group I4/mmm (no. 139), a = 3.8054(2) ?, c = 6.8961(4) ?, Z = 2, wR(p) = 0.057) and the corresponding alkaline earth acetylenides (M(AE)C(2)) crystallizing in a tetragonally distorted NaCl structure type. In accordance with literature data, BaN(2) adopts a more distorted structure in space group C2/c (no. 15) with a = 7.1608(4) ?, b = 4.3776(3) ?, c = 7.2188(4) ?, β = 104.9679(33)°, Z = 4 and wR(p) = 0.049). The N-N bond lengths of 1.202(4) ? in CaN(2) (SrN(2) 1.239(4) ?, BaN(2) 1.23(2) ?) correspond well with a double-bonded dinitrogen unit confirming a diazenide ion [N(2)](2-). Temperature-dependent in situ powder X-ray diffractometry of the three alkaline earth diazenides resulted in formation of the corresponding subnitrides M(AE(2))N (M(AE) = Ca, Sr, Ba) at higher temperatures. FTIR spectroscopy revealed a band at about 1380 cm(-1) assigned to the N-N stretching vibration of the diazenide unit. Electronic structure calculations support the metallic character of alkaline earth diazenides.