CsPbBr3 crystallizes in the orthorhombic Pnma space group. Cs(1) is bonded in a 9-coordinate geometry to two equivalent Br(1), three equivalent Br(3), and four equivalent Br(2) atoms. Pb(1) is bonded to one Br(2), two equivalent Br(3), and three equivalent Br(1) atoms to form edge-sharing PbBr6 octahedra. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded to two equivalent Cs(1) and three equivalent Pb(1) atoms to form BrCs2Pb3 trigonal bipyramids that share corners with three equivalent Br(2)Cs4Pb square pyramids, corners with four equivalent Br(1)Cs2Pb3 trigonal bipyramids, corners with six equivalent Br(3)Cs3Pb2 trigonal bipyramids, edges with four equivalent Br(2)Cs4Pb square pyramids, edges with two equivalent Br(1)Cs2Pb3 trigonal bipyramids, and edges with three equivalent Br(3)Cs3Pb2 trigonal bipyramids. In the second Br site, Br(2) is bonded to four equivalent Cs(1) and one Pb(1) atom to form distorted BrCs4Pb square pyramids that share corners with four equivalent Br(2)Cs4Pb square pyramids, corners with three equivalent Br(1)Cs2Pb3 trigonal bipyramids, corners with six equivalent Br(3)Cs3Pb2 trigonal bipyramids, edges with four equivalent Br(2)Cs4Pb square pyramids, edges with four equivalent Br(1)Cs2Pb3 trigonal bipyramids, and edges with four equivalent Br(3)Cs3Pb2 trigonal bipyramids. In the third Br site, Br(3) is bonded to three equivalent Cs(1) and two equivalent Pb(1) atoms to form distorted BrCs3Pb2 trigonal bipyramids that share corners with six equivalent Br(2)Cs4Pb square pyramids, corners with six equivalent Br(1)Cs2Pb3 trigonal bipyramids, edges with four equivalent Br(2)Cs4Pb square pyramids, edges with three equivalent Br(1)Cs2Pb3 trigonal bipyramids, and edges with four equivalent Br(3)Cs3Pb2 trigonal bipyramids.
CsPbBr3 crystallizes in the orthorhombic Pnma space group. Cs(1) is bonded in a 9-coordinate geometry to two equivalent Br(1), three equivalent Br(3), and four equivalent Br(2) atoms. There is one shorter (3.83 Å) and one longer (3.91 Å) Cs(1)-Br(1) bond length. There are two shorter (3.78 Å) and one longer (3.83 Å) Cs(1)-Br(3) bond length. All Cs(1)-Br(2) bond lengths are 3.70 Å. Pb(1) is bonded to one Br(2), two equivalent Br(3), and three equivalent Br(1) atoms to form edge-sharing PbBr6 octahedra. The Pb(1)-Br(2) bond length is 2.87 Å. Both Pb(1)-Br(3) bond lengths are 3.05 Å. There are two shorter (3.10 Å) and one longer (3.25 Å) Pb(1)-Br(1) bond length. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded to two equivalent Cs(1) and three equivalent Pb(1) atoms to form BrCs2Pb3 trigonal bipyramids that share corners with three equivalent Br(2)Cs4Pb square pyramids, corners with four equivalent Br(1)Cs2Pb3 trigonal bipyramids, corners with six equivalent Br(3)Cs3Pb2 trigonal bipyramids, edges with four equivalent Br(2)Cs4Pb square pyramids, edges with two equivalent Br(1)Cs2Pb3 trigonal bipyramids, and edges with three equivalent Br(3)Cs3Pb2 trigonal bipyramids. In the second Br site, Br(2) is bonded to four equivalent Cs(1) and one Pb(1) atom to form distorted BrCs4Pb square pyramids that share corners with four equivalent Br(2)Cs4Pb square pyramids, corners with three equivalent Br(1)Cs2Pb3 trigonal bipyramids, corners with six equivalent Br(3)Cs3Pb2 trigonal bipyramids, edges with four equivalent Br(2)Cs4Pb square pyramids, edges with four equivalent Br(1)Cs2Pb3 trigonal bipyramids, and edges with four equivalent Br(3)Cs3Pb2 trigonal bipyramids. In the third Br site, Br(3) is bonded to three equivalent Cs(1) and two equivalent Pb(1) atoms to form distorted BrCs3Pb2 trigonal bipyramids that share corners with six equivalent Br(2)Cs4Pb square pyramids, corners with six equivalent Br(1)Cs2Pb3 trigonal bipyramids, edges with four equivalent Br(2)Cs4Pb square pyramids, edges with three equivalent Br(1)Cs2Pb3 trigonal bipyramids, and edges with four equivalent Br(3)Cs3Pb2 trigonal bipyramids.