Neutron Powder Diffraction with natSm: Crystal Structures and Magnetism of a Binary Samarium Deuteride and a Ternary Samarium Magnesium Deuteride

Binary SmH3 (trigonal, a=656.7(3), c=680.1(3) pm, Pc1, Z=6), ternary SmMg2H7 (tetragonal, a=626.47(6), c=937.2(2) pm, P41212, Z=4) and the corresponding deuterides SmD3 (a=653.9(1)m, c=676.7(2) pm) and SmMg2D7 (a=624.10(1), c=934.81(2) pm) have been prepared by hydrogenation (deuteration) of elemental samarium and the Laves phase SmMg2, respectively, and investigated by X-ray and neutron powder diffraction and SQUID and vibration magnetometry. The problem of the enormous neutron absorption of the natural isotopic mixture (natSm) is circumvented by carefully choosing the neutron wavelength (≈50 pm) and the use of double-walled cylindrical sample holders and a high-intensity neutron diffractometer (D4c at ILL). SmD3 crystallises with a tysonite-type structure and has three independently ordered deuterium atom sites with trigonal-planar, trigonal-pyramidal and tetrahedral metal environments and SmD bond lengths in the range 220(1)–258(1) pm (average: 235 pm). SmMg2D7 is a new deuteride that crystallises with an LaMg2D7-type structure. It displays four fully occupied deuterium sites having triangular and tetrahedral metal environments and SmD bond lengths in the range 227.6(5)–246.8(8) pm (average: 239 pm). These are the first samarium–deuterium bond lengths to be reported. Both deuterides are paramagnetic down to 2 K (SmD3: μeff=0.63(1) μB,θp≈−4 K; SmMg2D7: μeff=0.57(2) μB, θp≈−4 K). Their crystal structures and chemical and physical properties suggest mainly ionic bonding according to the limiting ionic formulae Sm3+(H−)3 and Sm3+(Mg2+)2(H−)7.