CaSb2O4 is Ilmenite-like structured and crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form distorted CaO6 pentagonal pyramids that share edges with four equivalent Sb(2)O6 octahedra. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(3) atoms. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), and two equivalent O(3) atoms. In the second Sb site, Sb(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form SbO6 octahedra that share edges with two equivalent Sb(2)O6 octahedra and edges with two equivalent Ca(1)O6 pentagonal pyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Sb(1), and two equivalent Sb(2) atoms. In the second O site, O(2) is bonded to one Ca(2), one Sb(1), and two equivalent Sb(2) atoms to form OCaSb3 trigonal pyramids that share corners with three equivalent O(2)CaSb3 trigonal pyramids, corners with six equivalent O(3)Ca2Sb2 trigonal pyramids, and edges with two equivalent O(3)Ca2Sb2 trigonal pyramids. In the third O site, O(3) is bonded to one Ca(1), one Ca(2), one Sb(1), and one Sb(2) atom to form distorted OCa2Sb2 trigonal pyramids that share corners with three equivalent O(2)CaSb3 trigonal pyramids, corners with four equivalent O(3)Ca2Sb2 trigonal pyramids,  an edgeedge with one O(2)CaSb3 trigonal pyramid, and edges with two equivalent O(3)Ca2Sb2 trigonal pyramids.
CaSb2O4 is Ilmenite-like structured and crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form distorted CaO6 pentagonal pyramids that share edges with four equivalent Sb(2)O6 octahedra. Both Ca(1)-O(1) bond lengths are 2.32 Å. All Ca(1)-O(3) bond lengths are 2.38 Å. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(3) atoms. Both Ca(2)-O(2) bond lengths are 2.48 Å. All Ca(2)-O(3) bond lengths are 2.76 Å. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), and two equivalent O(3) atoms. The Sb(1)-O(1) bond length is 2.17 Å. The Sb(1)-O(2) bond length is 2.51 Å. Both Sb(1)-O(3) bond lengths are 2.04 Å. In the second Sb site, Sb(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form SbO6 octahedra that share edges with two equivalent Sb(2)O6 octahedra and edges with two equivalent Ca(1)O6 pentagonal pyramids. Both Sb(2)-O(1) bond lengths are 2.40 Å. Both Sb(2)-O(2) bond lengths are 2.31 Å. Both Sb(2)-O(3) bond lengths are 2.48 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Sb(1), and two equivalent Sb(2) atoms. In the second O site, O(2) is bonded to one Ca(2), one Sb(1), and two equivalent Sb(2) atoms to form OCaSb3 trigonal pyramids that share corners with three equivalent O(2)CaSb3 trigonal pyramids, corners with six equivalent O(3)Ca2Sb2 trigonal pyramids, and edges with two equivalent O(3)Ca2Sb2 trigonal pyramids. In the third O site, O(3) is bonded to one Ca(1), one Ca(2), one Sb(1), and one Sb(2) atom to form distorted OCa2Sb2 trigonal pyramids that share corners with three equivalent O(2)CaSb3 trigonal pyramids, corners with four equivalent O(3)Ca2Sb2 trigonal pyramids,  an edgeedge with one O(2)CaSb3 trigonal pyramid, and edges with two equivalent O(3)Ca2Sb2 trigonal pyramids.