KCaBr3 crystallizes in the monoclinic P2_1/m space group. K(1) is bonded in a 8-coordinate geometry to two equivalent Br(2) and six equivalent Br(1) atoms. Ca(1) is bonded to two equivalent Br(2) and four equivalent Br(1) atoms to form a mixture of corner and edge-sharing CaBr6 octahedra. The corner-sharing octahedral tilt angles are 42°. There are two inequivalent Br sites. In the first Br site, Br(2) is bonded to two equivalent K(1) and two equivalent Ca(1) atoms to form distorted BrK2Ca2 tetrahedra that share corners with four equivalent Br(2)K2Ca2 tetrahedra, corners with eight equivalent Br(1)K3Ca2 trigonal bipyramids, and edges with six equivalent Br(1)K3Ca2 trigonal bipyramids. In the second Br site, Br(1) is bonded to three equivalent K(1) and two equivalent Ca(1) atoms to form distorted BrK3Ca2 trigonal bipyramids that share corners with four equivalent Br(2)K2Ca2 tetrahedra, corners with nine equivalent Br(1)K3Ca2 trigonal bipyramids, edges with three equivalent Br(2)K2Ca2 tetrahedra, and edges with six equivalent Br(1)K3Ca2 trigonal bipyramids.
KCaBr3 crystallizes in the monoclinic P2_1/m space group. K(1) is bonded in a 8-coordinate geometry to two equivalent Br(2) and six equivalent Br(1) atoms. Both K(1)-Br(2) bond lengths are 3.26 Å. There are four shorter (3.42 Å) and two longer (3.66 Å) K(1)-Br(1) bond lengths. Ca(1) is bonded to two equivalent Br(2) and four equivalent Br(1) atoms to form a mixture of corner and edge-sharing CaBr6 octahedra. The corner-sharing octahedral tilt angles are 42°. Both Ca(1)-Br(2) bond lengths are 2.88 Å. All Ca(1)-Br(1) bond lengths are 2.92 Å. There are two inequivalent Br sites. In the first Br site, Br(2) is bonded to two equivalent K(1) and two equivalent Ca(1) atoms to form distorted BrK2Ca2 tetrahedra that share corners with four equivalent Br(2)K2Ca2 tetrahedra, corners with eight equivalent Br(1)K3Ca2 trigonal bipyramids, and edges with six equivalent Br(1)K3Ca2 trigonal bipyramids. In the second Br site, Br(1) is bonded to three equivalent K(1) and two equivalent Ca(1) atoms to form distorted BrK3Ca2 trigonal bipyramids that share corners with four equivalent Br(2)K2Ca2 tetrahedra, corners with nine equivalent Br(1)K3Ca2 trigonal bipyramids, edges with three equivalent Br(2)K2Ca2 tetrahedra, and edges with six equivalent Br(1)K3Ca2 trigonal bipyramids.