Synthesis and thermal stability of perovskite alkali metal strontium borohydrides

Three new perovskite-type bimetallic alkali metal strontium borohydride compounds, alpha-MSr(BH4)(3) (M = K, Rb, Cs), have been synthesized and investigated by in situ synchrotron radiation powder X-ray diffraction, thermal analysis combined with mass spectrometry and Sievert's measurements. The bimetallic borohydrides were synthesized via an addition reaction between Sr(BH4)(2) and MBH4 (M = K, Rb, Cs) by mechanochemical treatment. The Sr(BH4)(2)-NaBH4 system, which was treated in a similar manner, did not undergo reaction. All three alpha-MSr(BH4)(3) compounds crystallize in the orthorhombic crystal system at room temperature: KSr(BH4)(3) (P2(1)cn), a = 7.8967(6), b = 8.2953(7), and c = 11.508(1) angstrom (V = 753.82(12) angstrom(3)). RbSr(BH4)(3) (Pbn2(1)), a = 8.0835(3), b = 8.3341(4), and c = 11.6600(5) angstrom (V = 785.52(6) angstrom(3)). CsSr(BH4)(3) (P22(1)2(1)), a = 8.2068(9), b = 8.1793(9), and c = 6.0761(4) angstrom (V = 407.87(7) angstrom(3)). All three compounds are perovskite-type 3D framework structures built from distorted [Sr(BH4)(6)] octahedra. High-temperature polymorphs are identified to form at 258, 220 and 150 degrees C for MSr(BH4)(3), M = K, Rb and Cs, respectively. The new compounds are thermally stable and decompose at T > 360 degrees C into SrB6, SrH2 and MBH4 (M = K, Rb, Cs).