CsPbP(IF3)2 crystallizes in the tetragonal P4/mmm space group. Cs(1) is bonded to eight equivalent F(2) atoms to form CsF8 hexagonal bipyramids that share edges with four equivalent Cs(1)F8 hexagonal bipyramids and edges with four equivalent P(1)F6 octahedra. Pb(1) is bonded to four equivalent I(1) and two equivalent F(1) atoms to form distorted PbI4F2 octahedra that share corners with two equivalent P(1)F6 octahedra and corners with four equivalent Pb(1)I4F2 octahedra. The corner-sharing octahedra are not tilted. P(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form PF6 octahedra that share corners with two equivalent Pb(1)I4F2 octahedra and edges with four equivalent Cs(1)F8 hexagonal bipyramids. The corner-sharing octahedra are not tilted. I(1) is bonded in a linear geometry to two equivalent Pb(1) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to one Pb(1) and one P(1) atom. In the second F site, F(2) is bonded in a single-bond geometry to two equivalent Cs(1) and one P(1) atom.
CsPbP(IF3)2 crystallizes in the tetragonal P4/mmm space group. Cs(1) is bonded to eight equivalent F(2) atoms to form CsF8 hexagonal bipyramids that share edges with four equivalent Cs(1)F8 hexagonal bipyramids and edges with four equivalent P(1)F6 octahedra. All Cs(1)-F(2) bond lengths are 3.49 Å. Pb(1) is bonded to four equivalent I(1) and two equivalent F(1) atoms to form distorted PbI4F2 octahedra that share corners with two equivalent P(1)F6 octahedra and corners with four equivalent Pb(1)I4F2 octahedra. The corner-sharing octahedra are not tilted. All Pb(1)-I(1) bond lengths are 3.15 Å. Both Pb(1)-F(1) bond lengths are 2.65 Å. P(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form PF6 octahedra that share corners with two equivalent Pb(1)I4F2 octahedra and edges with four equivalent Cs(1)F8 hexagonal bipyramids. The corner-sharing octahedra are not tilted. Both P(1)-F(1) bond lengths are 1.65 Å. All P(1)-F(2) bond lengths are 1.64 Å. I(1) is bonded in a linear geometry to two equivalent Pb(1) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to one Pb(1) and one P(1) atom. In the second F site, F(2) is bonded in a single-bond geometry to two equivalent Cs(1) and one P(1) atom.