CaSb2O4 is Spinel-like structured and crystallizes in the trigonal P3m1 space group. There are six inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(9) and three equivalent O(1) atoms to form CaO4 tetrahedra that share corners with three equivalent Ca(5)O6 octahedra, corners with three equivalent Sb(5)O6 octahedra, and corners with six equivalent Sb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-68°. In the second Ca site, Ca(2) is bonded to one O(2) and three equivalent O(3) atoms to form CaO4 tetrahedra that share corners with three equivalent Ca(3)O6 octahedra, corners with three equivalent Sb(1)O6 octahedra, and corners with six equivalent Sb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-67°. In the third Ca site, Ca(3) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form CaO6 octahedra that share corners with three equivalent Ca(2)O4 tetrahedra, corners with three equivalent Sb(4)O4 tetrahedra, edges with three equivalent Sb(1)O6 octahedra, and edges with three equivalent Sb(2)O6 octahedra. In the fourth Ca site, Ca(4) is bonded to one O(5) and three equivalent O(7) atoms to form CaO4 tetrahedra that share corners with three equivalent Sb(2)O6 octahedra, corners with three equivalent Sb(3)O6 octahedra, and corners with six equivalent Sb(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-69°. In the fifth Ca site, Ca(5) is bonded to three equivalent O(1) and three equivalent O(11) atoms to form CaO6 octahedra that share corners with three equivalent Ca(1)O4 tetrahedra, corners with three equivalent Sb(6)O4 tetrahedra, edges with three equivalent Sb(1)O6 octahedra, and edges with three equivalent Sb(5)O6 octahedra. In the sixth Ca site, Ca(6) is bonded to one O(12) and three equivalent O(8) atoms to form CaO4 tetrahedra that share corners with three equivalent Sb(3)O6 octahedra, corners with three equivalent Sb(5)O6 octahedra, and corners with six equivalent Sb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-61°. There are six inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one O(2), one O(6), two equivalent O(1), and two equivalent O(4) atoms to form SbO6 octahedra that share  a cornercorner with one Ca(2)O4 tetrahedra,  a cornercorner with one Sb(6)O4 tetrahedra, corners with two equivalent Ca(1)O4 tetrahedra, corners with two equivalent Sb(4)O4 tetrahedra,  an edgeedge with one Ca(3)O6 octahedra,  an edgeedge with one Ca(5)O6 octahedra, and edges with four equivalent Sb(1)O6 octahedra. In the second Sb site, Sb(2) is bonded to one O(10), one O(5), two equivalent O(3), and two equivalent O(8) atoms to form SbO6 octahedra that share  a cornercorner with one Ca(4)O4 tetrahedra,  a cornercorner with one Sb(4)O4 tetrahedra, corners with two equivalent Ca(2)O4 tetrahedra, corners with two equivalent Ca(6)O4 tetrahedra,  an edgeedge with one Ca(3)O6 octahedra,  an edgeedge with one Sb(3)O6 octahedra, and edges with four equivalent Sb(2)O6 octahedra. In the third Sb site, Sb(3) is bonded to three equivalent O(7) and three equivalent O(8) atoms to form distorted SbO6 octahedra that share corners with three equivalent Ca(4)O4 tetrahedra, corners with three equivalent Ca(6)O4 tetrahedra, edges with three equivalent Sb(2)O6 octahedra, and edges with three equivalent Sb(5)O6 octahedra. In the fourth Sb site, Sb(4) is bonded to one O(10) and three equivalent O(4) atoms to form SbO4 tetrahedra that share corners with three equivalent Ca(3)O6 octahedra, corners with three equivalent Sb(2)O6 octahedra, and corners with six equivalent Sb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-57°. In the fifth Sb site, Sb(5) is bonded to one O(12), one O(9), two equivalent O(11), and two equivalent O(7) atoms to form SbO6 octahedra that share  a cornercorner with one Ca(1)O4 tetrahedra,  a cornercorner with one Ca(6)O4 tetrahedra, corners with two equivalent Ca(4)O4 tetrahedra, corners with two equivalent Sb(6)O4 tetrahedra,  an edgeedge with one Ca(5)O6 octahedra,  an edgeedge with one Sb(3)O6 octahedra, and edges with four equivalent Sb(5)O6 octahedra. In the sixth Sb site, Sb(6) is bonded to one O(6) and three equivalent O(11) atoms to form SbO4 tetrahedra that share corners with three equivalent Ca(5)O6 octahedra, corners with three equivalent Sb(1)O6 octahedra, and corners with six equivalent Sb(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-58°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one Ca(5), and two equivalent Sb(1) atoms to form distorted OCa2Sb2 trigonal pyramids that share corners with two equivalent O(1)Ca2Sb2 trigonal pyramids,  an edgeedge with one O(2)CaSb3 trigonal pyramid, and edges with two equivalent O(1)Ca2Sb2 trigonal pyramids. In the second O site, O(2) is bonded to one Ca(2) and three equivalent Sb(1) atoms to form a mixture of distorted corner and edge-sharing OCaSb3 trigonal pyramids. In the third O site, O(3) is bonded to one Ca(2), one Ca(3), and two equivalent Sb(2) atoms to form distorted OCa2Sb2 trigonal pyramids that share  a cornercorner with one O(2)CaSb3 trigonal pyramid, corners with two equivalent O(3)Ca2Sb2 trigonal pyramids,  an edgeedge with one O(5)CaSb3 trigonal pyramid, and edges with two equivalent O(3)Ca2Sb2 trigonal pyramids. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Ca(3), one Sb(4), and two equivalent Sb(1) atoms. In the fifth O site, O(5) is bonded to one Ca(4) and three equivalent Sb(2) atoms to form distorted edge-sharing OCaSb3 trigonal pyramids. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Sb(6) and three equivalent Sb(1) atoms. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Ca(4), one Sb(3), and two equivalent Sb(5) atoms. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Ca(6), one Sb(3), and two equivalent Sb(2) atoms. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Ca(1) and three equivalent Sb(5) atoms. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Sb(4) and three equivalent Sb(2) atoms. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Ca(5), one Sb(6), and two equivalent Sb(5) atoms. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Ca(6) and three equivalent Sb(5) atoms.
CaSb2O4 is Spinel-like structured and crystallizes in the trigonal P3m1 space group. There are six inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(9) and three equivalent O(1) atoms to form CaO4 tetrahedra that share corners with three equivalent Ca(5)O6 octahedra, corners with three equivalent Sb(5)O6 octahedra, and corners with six equivalent Sb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-68°. The Ca(1)-O(9) bond length is 2.36 Å. All Ca(1)-O(1) bond lengths are 2.40 Å. In the second Ca site, Ca(2) is bonded to one O(2) and three equivalent O(3) atoms to form CaO4 tetrahedra that share corners with three equivalent Ca(3)O6 octahedra, corners with three equivalent Sb(1)O6 octahedra, and corners with six equivalent Sb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-67°. The Ca(2)-O(2) bond length is 2.42 Å. All Ca(2)-O(3) bond lengths are 2.36 Å. In the third Ca site, Ca(3) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form CaO6 octahedra that share corners with three equivalent Ca(2)O4 tetrahedra, corners with three equivalent Sb(4)O4 tetrahedra, edges with three equivalent Sb(1)O6 octahedra, and edges with three equivalent Sb(2)O6 octahedra. All Ca(3)-O(3) bond lengths are 2.48 Å. All Ca(3)-O(4) bond lengths are 2.35 Å. In the fourth Ca site, Ca(4) is bonded to one O(5) and three equivalent O(7) atoms to form CaO4 tetrahedra that share corners with three equivalent Sb(2)O6 octahedra, corners with three equivalent Sb(3)O6 octahedra, and corners with six equivalent Sb(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-69°. The Ca(4)-O(5) bond length is 2.56 Å. All Ca(4)-O(7) bond lengths are 2.27 Å. In the fifth Ca site, Ca(5) is bonded to three equivalent O(1) and three equivalent O(11) atoms to form CaO6 octahedra that share corners with three equivalent Ca(1)O4 tetrahedra, corners with three equivalent Sb(6)O4 tetrahedra, edges with three equivalent Sb(1)O6 octahedra, and edges with three equivalent Sb(5)O6 octahedra. All Ca(5)-O(1) bond lengths are 2.46 Å. All Ca(5)-O(11) bond lengths are 2.33 Å. In the sixth Ca site, Ca(6) is bonded to one O(12) and three equivalent O(8) atoms to form CaO4 tetrahedra that share corners with three equivalent Sb(3)O6 octahedra, corners with three equivalent Sb(5)O6 octahedra, and corners with six equivalent Sb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-61°. The Ca(6)-O(12) bond length is 2.20 Å. All Ca(6)-O(8) bond lengths are 2.28 Å. There are six inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one O(2), one O(6), two equivalent O(1), and two equivalent O(4) atoms to form SbO6 octahedra that share  a cornercorner with one Ca(2)O4 tetrahedra,  a cornercorner with one Sb(6)O4 tetrahedra, corners with two equivalent Ca(1)O4 tetrahedra, corners with two equivalent Sb(4)O4 tetrahedra,  an edgeedge with one Ca(3)O6 octahedra,  an edgeedge with one Ca(5)O6 octahedra, and edges with four equivalent Sb(1)O6 octahedra. The Sb(1)-O(2) bond length is 2.29 Å. The Sb(1)-O(6) bond length is 2.50 Å. Both Sb(1)-O(1) bond lengths are 2.19 Å. Both Sb(1)-O(4) bond lengths are 2.53 Å. In the second Sb site, Sb(2) is bonded to one O(10), one O(5), two equivalent O(3), and two equivalent O(8) atoms to form SbO6 octahedra that share  a cornercorner with one Ca(4)O4 tetrahedra,  a cornercorner with one Sb(4)O4 tetrahedra, corners with two equivalent Ca(2)O4 tetrahedra, corners with two equivalent Ca(6)O4 tetrahedra,  an edgeedge with one Ca(3)O6 octahedra,  an edgeedge with one Sb(3)O6 octahedra, and edges with four equivalent Sb(2)O6 octahedra. The Sb(2)-O(10) bond length is 2.45 Å. The Sb(2)-O(5) bond length is 2.29 Å. Both Sb(2)-O(3) bond lengths are 2.22 Å. Both Sb(2)-O(8) bond lengths are 2.52 Å. In the third Sb site, Sb(3) is bonded to three equivalent O(7) and three equivalent O(8) atoms to form distorted SbO6 octahedra that share corners with three equivalent Ca(4)O4 tetrahedra, corners with three equivalent Ca(6)O4 tetrahedra, edges with three equivalent Sb(2)O6 octahedra, and edges with three equivalent Sb(5)O6 octahedra. All Sb(3)-O(7) bond lengths are 2.68 Å. All Sb(3)-O(8) bond lengths are 2.13 Å. In the fourth Sb site, Sb(4) is bonded to one O(10) and three equivalent O(4) atoms to form SbO4 tetrahedra that share corners with three equivalent Ca(3)O6 octahedra, corners with three equivalent Sb(2)O6 octahedra, and corners with six equivalent Sb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-57°. The Sb(4)-O(10) bond length is 2.17 Å. All Sb(4)-O(4) bond lengths are 2.12 Å. In the fifth Sb site, Sb(5) is bonded to one O(12), one O(9), two equivalent O(11), and two equivalent O(7) atoms to form SbO6 octahedra that share  a cornercorner with one Ca(1)O4 tetrahedra,  a cornercorner with one Ca(6)O4 tetrahedra, corners with two equivalent Ca(4)O4 tetrahedra, corners with two equivalent Sb(6)O4 tetrahedra,  an edgeedge with one Ca(5)O6 octahedra,  an edgeedge with one Sb(3)O6 octahedra, and edges with four equivalent Sb(5)O6 octahedra. The Sb(5)-O(12) bond length is 2.41 Å. The Sb(5)-O(9) bond length is 2.34 Å. Both Sb(5)-O(11) bond lengths are 2.48 Å. Both Sb(5)-O(7) bond lengths are 2.24 Å. In the sixth Sb site, Sb(6) is bonded to one O(6) and three equivalent O(11) atoms to form SbO4 tetrahedra that share corners with three equivalent Ca(5)O6 octahedra, corners with three equivalent Sb(1)O6 octahedra, and corners with six equivalent Sb(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-58°. The Sb(6)-O(6) bond length is 2.14 Å. All Sb(6)-O(11) bond lengths are 2.14 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one Ca(5), and two equivalent Sb(1) atoms to form distorted OCa2Sb2 trigonal pyramids that share corners with two equivalent O(1)Ca2Sb2 trigonal pyramids,  an edgeedge with one O(2)CaSb3 trigonal pyramid, and edges with two equivalent O(1)Ca2Sb2 trigonal pyramids. In the second O site, O(2) is bonded to one Ca(2) and three equivalent Sb(1) atoms to form a mixture of distorted corner and edge-sharing OCaSb3 trigonal pyramids. In the third O site, O(3) is bonded to one Ca(2), one Ca(3), and two equivalent Sb(2) atoms to form distorted OCa2Sb2 trigonal pyramids that share  a cornercorner with one O(2)CaSb3 trigonal pyramid, corners with two equivalent O(3)Ca2Sb2 trigonal pyramids,  an edgeedge with one O(5)CaSb3 trigonal pyramid, and edges with two equivalent O(3)Ca2Sb2 trigonal pyramids. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Ca(3), one Sb(4), and two equivalent Sb(1) atoms. In the fifth O site, O(5) is bonded to one Ca(4) and three equivalent Sb(2) atoms to form distorted edge-sharing OCaSb3 trigonal pyramids. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Sb(6) and three equivalent Sb(1) atoms. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Ca(4), one Sb(3), and two equivalent Sb(5) atoms. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Ca(6), one Sb(3), and two equivalent Sb(2) atoms. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Ca(1) and three equivalent Sb(5) atoms. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Sb(4) and three equivalent Sb(2) atoms. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Ca(5), one Sb(6), and two equivalent Sb(5) atoms. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Ca(6) and three equivalent Sb(5) atoms.