KPbOBr3 crystallizes in the orthorhombic Cmc2_1 space group. K(1) is bonded in a 2-coordinate geometry to two equivalent O(1), one Br(3), and two equivalent Br(1) atoms. Pb(1) is bonded to one Br(2), two equivalent Br(1), and three equivalent Br(3) atoms to form a mixture of corner and edge-sharing PbBr6 octahedra. The corner-sharing octahedral tilt angles are 49°. O(1) is bonded in a trigonal planar geometry to two equivalent K(1) and one Br(2) atom. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded to two equivalent K(1) and two equivalent Pb(1) atoms to form distorted BrK2Pb2 tetrahedra that share corners with four equivalent Br(1)K2Pb2 tetrahedra, corners with six equivalent Br(3)KPb3 trigonal pyramids, and  an edgeedge with one Br(3)KPb3 trigonal pyramid. In the second Br site, Br(2) is bonded in a distorted single-bond geometry to one Pb(1) and one O(1) atom. In the third Br site, Br(3) is bonded to one K(1) and three equivalent Pb(1) atoms to form BrKPb3 trigonal pyramids that share corners with six equivalent Br(1)K2Pb2 tetrahedra, corners with six equivalent Br(3)KPb3 trigonal pyramids, and  an edgeedge with one Br(1)K2Pb2 tetrahedra.
KPbOBr3 crystallizes in the orthorhombic Cmc2_1 space group. K(1) is bonded in a 2-coordinate geometry to two equivalent O(1), one Br(3), and two equivalent Br(1) atoms. Both K(1)-O(1) bond lengths are 2.57 Å. The K(1)-Br(3) bond length is 3.81 Å. There is one shorter (3.29 Å) and one longer (3.75 Å) K(1)-Br(1) bond length. Pb(1) is bonded to one Br(2), two equivalent Br(1), and three equivalent Br(3) atoms to form a mixture of corner and edge-sharing PbBr6 octahedra. The corner-sharing octahedral tilt angles are 49°. The Pb(1)-Br(2) bond length is 3.06 Å. Both Pb(1)-Br(1) bond lengths are 3.02 Å. There are two shorter (3.16 Å) and one longer (3.17 Å) Pb(1)-Br(3) bond length. O(1) is bonded in a trigonal planar geometry to two equivalent K(1) and one Br(2) atom. The O(1)-Br(2) bond length is 1.81 Å. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded to two equivalent K(1) and two equivalent Pb(1) atoms to form distorted BrK2Pb2 tetrahedra that share corners with four equivalent Br(1)K2Pb2 tetrahedra, corners with six equivalent Br(3)KPb3 trigonal pyramids, and  an edgeedge with one Br(3)KPb3 trigonal pyramid. In the second Br site, Br(2) is bonded in a distorted single-bond geometry to one Pb(1) and one O(1) atom. In the third Br site, Br(3) is bonded to one K(1) and three equivalent Pb(1) atoms to form BrKPb3 trigonal pyramids that share corners with six equivalent Br(1)K2Pb2 tetrahedra, corners with six equivalent Br(3)KPb3 trigonal pyramids, and  an edgeedge with one Br(1)K2Pb2 tetrahedra.