KSnBr3 crystallizes in the orthorhombic Pnma space group. K(1) is bonded in a 9-coordinate geometry to two equivalent Br(2), three equivalent Br(1), and four equivalent Br(3) atoms. Sn(1) is bonded to one Br(3), two equivalent Br(1), and two equivalent Br(2) atoms to form edge-sharing SnBr5 square pyramids. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded to three equivalent K(1) and two equivalent Sn(1) atoms to form distorted BrK3Sn2 trigonal bipyramids that share corners with eight equivalent Br(2)K2Sn2 tetrahedra,  an edgeedge with one Br(2)K2Sn2 tetrahedra, and edges with four equivalent Br(1)K3Sn2 trigonal bipyramids. In the second Br site, Br(2) is bonded to two equivalent K(1) and two equivalent Sn(1) atoms to form BrK2Sn2 tetrahedra that share corners with four equivalent Br(2)K2Sn2 tetrahedra, corners with eight equivalent Br(1)K3Sn2 trigonal bipyramids, and  an edgeedge with one Br(1)K3Sn2 trigonal bipyramid. In the third Br site, Br(3) is bonded in a 5-coordinate geometry to four equivalent K(1) and one Sn(1) atom.
KSnBr3 crystallizes in the orthorhombic Pnma space group. K(1) is bonded in a 9-coordinate geometry to two equivalent Br(2), three equivalent Br(1), and four equivalent Br(3) atoms. There is one shorter (3.39 Å) and one longer (3.40 Å) K(1)-Br(2) bond length. There are two shorter (3.50 Å) and one longer (3.69 Å) K(1)-Br(1) bond length. There are two shorter (3.42 Å) and two longer (3.80 Å) K(1)-Br(3) bond lengths. Sn(1) is bonded to one Br(3), two equivalent Br(1), and two equivalent Br(2) atoms to form edge-sharing SnBr5 square pyramids. The Sn(1)-Br(3) bond length is 2.68 Å. Both Sn(1)-Br(1) bond lengths are 3.03 Å. Both Sn(1)-Br(2) bond lengths are 2.99 Å. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded to three equivalent K(1) and two equivalent Sn(1) atoms to form distorted BrK3Sn2 trigonal bipyramids that share corners with eight equivalent Br(2)K2Sn2 tetrahedra,  an edgeedge with one Br(2)K2Sn2 tetrahedra, and edges with four equivalent Br(1)K3Sn2 trigonal bipyramids. In the second Br site, Br(2) is bonded to two equivalent K(1) and two equivalent Sn(1) atoms to form BrK2Sn2 tetrahedra that share corners with four equivalent Br(2)K2Sn2 tetrahedra, corners with eight equivalent Br(1)K3Sn2 trigonal bipyramids, and  an edgeedge with one Br(1)K3Sn2 trigonal bipyramid. In the third Br site, Br(3) is bonded in a 5-coordinate geometry to four equivalent K(1) and one Sn(1) atom.