To study the temperature-dependent structural changes and to analyze the crystal chemical behavior of the halogens as a function of temperature, a crystal of the recently discovered mineral mutnovskite, ideally Pb
2AsS
3(I,Cl,Br), has been investigated by X-ray single-crystal diffraction methods at 300 and 110 K. At room temperature (RT) mutnovskite was confirmed to possess a centrosymmetric structure-type, space group
Pnma, while at low temperature (110 K) it adopts a non-centrosymmetric orthorhombic structure-type, space group
Pnm2
1, with
a=11.5394(9) Å,
b=6.6732(5) Å,
c=9.3454(7) Å,
V=719.64(9) Å
3 and
Z=2. Mutnovskite reconverts to the centrosymmetric-type upon returning to RT thus indicating that the phase transition is completely reversible in character. The refinement of the LT-structure leads to a residual factor
R=0.0336 for 1827 independent observed reflections [
Fo>4
σ(
Fo)] and 80 variables. The crystal structure of cooled mutnovskite is topologically identical to that observed at RT and the slight structural changes occurring during the phase transition
Pnma→
Pnm2
1 are mainly restricted to the coordination polyhedra around Pb. The structure solution revealed that I and Cl are ordered into two specific sites. Indeed, the unique mixed (I,Cl) position in the RT-structure (Wyckoff position 4
c) transforms into two 2
a Wyckoff positions in the LT-structure hosting I and Cl, respectively.
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