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The crystal structures of Ba(OD)Cl and Ba(OD)Br have been determined by neutron powder diffraction at 295 K and 1.5 K and Rietveld refinement methods { R  I  = 9.3, 8.2 [Ba(OD)Cl], 5.7, and 4.9% [Ba(OD)Br]}, that of Ba(OH)Cl by single-crystal X-ray diffraction at 295 K ( R  = 4.1% for 1260 reflections). They are isostructural to laurionite Pb(OH)Cl {space group  Pnma ,  Z  = 4,  a  = 738.97(3),  b  = 443.69(3), and  c  = 913.90(5) pm [Ba(OH)Cl],  a  = 738.07(4),  b  = 447.62(2) and  c  = 897.93(5) pm [Ba(OD)Cl] and  a  = 759.65(2),  b  = 438.77(1), and  c  = 1030.22(2) pm [Ba(OD)Br] at 295 K}. Whereas hydrogen bonds are not present in the bromide, in the case of Ba(OH)Cl weak hydrogen bonds to adjacent Cl −  ions are formed which are strengthened on going down to lower temperatures due to reorientation of the OH −  ions from trifurcated H-bonds to nearly linear ones. The hydrogen bonds of Ba(OD)Cl have been established to be stronger than those of Ba(OH)Cl. This becomes apparent by both the smaller cell volume [296.65(4) pm 3  instead of 299.6(1) pm 3 ] and the different transition temperature (170 K–300 K instead of 100 K–180 K).

Bestimmung der Strukturen von Ba(OH)Cl, Ba(OD)Cl und Ba(OD)Br durch Röntgeneinkristall- und Neutronenpulver-Messungen