The alkaline earth diazenides MAEN2 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 highpressure/high-temperature conditions. The crystal structure of hitherto unknown calcium diazenide (space group I4/mmm (no. 139), a = 3.5747(6) angstrom, c = 5.9844(9) angstrom, z = 2, wR(p) = 0.078) was solved and refined on the basis of powder X-ray diffraction data as well as that of SrN2 and BaN2. Accordingly, CaN2 is isotypic with SrN2 (space group I4/mmm (no. 139), a = 3.8054(2) angstrom, c = 6.8961(4) angstrom, Z = 2, wR(p), = 0.057) and the corresponding alkaline earth acetylenides (MAEC2) crystallizing in a tetragonally distorted NaCl structure type. In accordance with literature data, BaN2 adopts a more distorted structure in space group C2/c (no. 15) with a = 7.1608(4) angstrom, b = 4.3776(3) angstrom, c = 7.2188(4) angstrom, beta = 104.9679(33)degrees, Z = 4 and wRp = 0.049). The N-N bond lengths of 1.202(4) angstrom in CaN2 (SrN2 1.239(4) angstrom, BaN2 1.23(2) angstrom) 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 MAE2N (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.