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The lattice parameters extracted from Lebail analysis of neutron powder diffraction data collected between 2 and 300 K have been used to calculate the temperature evolution of the thermal expansion tensor for hopeite, Zn 3 (PO 4 ) 2 ·2H 2 O, Pnma, Z = 4 with a = 10.6065(4) Å, b = 18.2977(4) Å, c = 5.0257(2) Å at 275 K. The a lattice parameter shows a negative thermal expansion, the b lattice parameter appears to saturate at 275 K while the c lattice parameter has a more typical positive thermal expansion. At 275 K, the magnitudes of the thermal expansion coeficients are α a  = -1.1(4) × 10 -5  K -1 , α b  = 2.4(9) × 10 -6  K -1  and α c  = 3.6(2) × 10 -5  K -1 . Under the conditions of these experiments, hopeite begins to dehydrate to the dihydrate between 300 and 325 K, and between 480 and 500 K the monohydrate is formed. The thermal expansion of the dihydrate has been calculated between 335 and 480 and at 480 K the magnitudes of the thermal expansion coeficients are α a  = 1(2) × 10 -5  K.1, α b  = 4(1) × 10 -6  K -1 , α c  = 4(2) × 10 -5  K -1 , α β = 1(1) × 10 -5  K -1 , and α V  = 2(2) × 10 -5  K -1 . The thermal expansion of hopeite is described in terms of its crystal structure and possible dehydration mechanisms for the α and β modifications of hopeite are discussed.

Thermal expansion of deuterated hopeite, Zn 3 (PO 4 ) 2 ·4D 2 O