CaSb2O4 crystallizes in the triclinic P1 space group. There are six inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(1), one O(17), one O(21), one O(3), and one O(4) atom to form distorted corner-sharing CaO5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 49-74°. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to one O(11), one O(18), one O(5), one O(6), one O(8), and one O(9) atom. In the third Ca site, Ca(3) is bonded to one O(1), one O(10), one O(12), one O(2), one O(3), and one O(8) atom to form distorted corner-sharing CaO6 octahedra. In the fourth Ca site, Ca(4) is bonded to one O(13), one O(14), one O(15), one O(16), one O(19), and one O(20) atom to form distorted edge-sharing CaO6 pentagonal pyramids. In the fifth Ca site, Ca(5) is bonded in a 4-coordinate geometry to one O(15), one O(20), one O(5), and one O(9) atom. In the sixth Ca site, Ca(6) is bonded to one O(13), one O(16), one O(17), one O(22), one O(23), and one O(24) atom to form distorted CaO6 octahedra that share  a cornercorner with one Ca(1)O5 trigonal bipyramid and  an edgeedge with one Ca(4)O6 pentagonal pyramid. There are twelve inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a distorted rectangular see-saw-like geometry to one O(10), one O(12), one O(4), and one O(6) atom. In the second Sb site, Sb(2) is bonded in a distorted T-shaped geometry to one O(11), one O(2), and one O(5) atom. In the third Sb site, Sb(3) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(21), one O(3), and one O(4) atom. In the fourth Sb site, Sb(4) is bonded in a 5-coordinate geometry to one O(10), one O(2), one O(3), one O(6), and one O(8) atom. In the fifth Sb site, Sb(5) is bonded in a distorted T-shaped geometry to one O(14), one O(20), and one O(7) atom. In the sixth Sb site, Sb(6) is bonded in a distorted trigonal non-coplanar geometry to one O(13), one O(16), and one O(7) atom. In the seventh Sb site, Sb(7) is bonded in a distorted T-shaped geometry to one O(11), one O(18), and one O(9) atom. In the eighth Sb site, Sb(8) is bonded in a 3-coordinate geometry to one O(19), one O(23), and one O(24) atom. In the ninth Sb site, Sb(9) is bonded in a distorted T-shaped geometry to one O(12), one O(18), and one O(8) atom. In the tenth Sb site, Sb(10) is bonded in a rectangular see-saw-like geometry to one O(16), one O(17), one O(19), and one O(22) atom. In the eleventh Sb site, Sb(11) is bonded in a distorted T-shaped geometry to one O(14), one O(15), and one O(23) atom. In the twelfth Sb site, Sb(12) is bonded in a distorted trigonal non-coplanar geometry to one O(21), one O(22), and one O(24) atom. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ca(3), and one Sb(3) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(3), one Sb(2), and one Sb(4) atom. In the third O site, O(3) is bonded to one Ca(1), one Ca(3), one Sb(3), and one Sb(4) atom to form corner-sharing OCa2Sb2 trigonal pyramids. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ca(1), one Sb(1), and one Sb(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Ca(2), one Ca(5), and one Sb(2) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Ca(2), one Sb(1), and one Sb(4) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Sb(5) and one Sb(6) atom. In the eighth O site, O(8) is bonded to one Ca(2), one Ca(3), one Sb(4), and one Sb(9) atom to form distorted corner-sharing OCa2Sb2 trigonal pyramids. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Ca(2), one Ca(5), and one Sb(7) atom. In the tenth O site, O(10) is bonded in a trigonal non-coplanar geometry to one Ca(3), one Sb(1), and one Sb(4) atom. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one Ca(2), one Sb(2), and one Sb(7) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Ca(3), one Sb(1), and one Sb(9) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Ca(4), one Ca(6), and one Sb(6) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Ca(4), one Sb(11), and one Sb(5) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one Ca(4), one Ca(5), and one Sb(11) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal pyramidal geometry to one Ca(4), one Ca(6), one Sb(10), and one Sb(6) atom. In the seventeenth O site, O(17) is bonded in a distorted T-shaped geometry to one Ca(1), one Ca(6), and one Sb(10) atom. In the eighteenth O site, O(18) is bonded in a distorted trigonal non-coplanar geometry to one Ca(2), one Sb(7), and one Sb(9) atom. In the nineteenth O site, O(19) is bonded in a trigonal non-coplanar geometry to one Ca(4), one Sb(10), and one Sb(8) atom. In the twentieth O site, O(20) is bonded in a distorted T-shaped geometry to one Ca(4), one Ca(5), and one Sb(5) atom. In the twenty-first O site, O(21) is bonded in a distorted bent 120 degrees geometry to one Ca(1), one Sb(12), and one Sb(3) atom. In the twenty-second O site, O(22) is bonded in a trigonal planar geometry to one Ca(6), one Sb(10), and one Sb(12) atom. In the twenty-third O site, O(23) is bonded in a distorted trigonal planar geometry to one Ca(6), one Sb(11), and one Sb(8) atom. In the twenty-fourth O site, O(24) is bonded in a distorted trigonal non-coplanar geometry to one Ca(6), one Sb(12), and one Sb(8) atom.
CaSb2O4 crystallizes in the triclinic P1 space group. There are six inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(1), one O(17), one O(21), one O(3), and one O(4) atom to form distorted corner-sharing CaO5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 49-74°. The Ca(1)-O(1) bond length is 2.41 Å. The Ca(1)-O(17) bond length is 2.35 Å. The Ca(1)-O(21) bond length is 2.35 Å. The Ca(1)-O(3) bond length is 2.45 Å. The Ca(1)-O(4) bond length is 2.76 Å. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to one O(11), one O(18), one O(5), one O(6), one O(8), and one O(9) atom. The Ca(2)-O(11) bond length is 2.37 Å. The Ca(2)-O(18) bond length is 2.74 Å. The Ca(2)-O(5) bond length is 2.31 Å. The Ca(2)-O(6) bond length is 2.31 Å. The Ca(2)-O(8) bond length is 2.52 Å. The Ca(2)-O(9) bond length is 2.44 Å. In the third Ca site, Ca(3) is bonded to one O(1), one O(10), one O(12), one O(2), one O(3), and one O(8) atom to form distorted corner-sharing CaO6 octahedra. The Ca(3)-O(1) bond length is 2.39 Å. The Ca(3)-O(10) bond length is 2.40 Å. The Ca(3)-O(12) bond length is 2.42 Å. The Ca(3)-O(2) bond length is 2.33 Å. The Ca(3)-O(3) bond length is 2.47 Å. The Ca(3)-O(8) bond length is 2.36 Å. In the fourth Ca site, Ca(4) is bonded to one O(13), one O(14), one O(15), one O(16), one O(19), and one O(20) atom to form distorted edge-sharing CaO6 pentagonal pyramids. The Ca(4)-O(13) bond length is 2.33 Å. The Ca(4)-O(14) bond length is 2.47 Å. The Ca(4)-O(15) bond length is 2.39 Å. The Ca(4)-O(16) bond length is 2.46 Å. The Ca(4)-O(19) bond length is 2.39 Å. The Ca(4)-O(20) bond length is 2.39 Å. In the fifth Ca site, Ca(5) is bonded in a 4-coordinate geometry to one O(15), one O(20), one O(5), and one O(9) atom. The Ca(5)-O(15) bond length is 2.26 Å. The Ca(5)-O(20) bond length is 2.24 Å. The Ca(5)-O(5) bond length is 2.26 Å. The Ca(5)-O(9) bond length is 2.23 Å. In the sixth Ca site, Ca(6) is bonded to one O(13), one O(16), one O(17), one O(22), one O(23), and one O(24) atom to form distorted CaO6 octahedra that share  a cornercorner with one Ca(1)O5 trigonal bipyramid and  an edgeedge with one Ca(4)O6 pentagonal pyramid. The Ca(6)-O(13) bond length is 2.41 Å. The Ca(6)-O(16) bond length is 2.51 Å. The Ca(6)-O(17) bond length is 2.36 Å. The Ca(6)-O(22) bond length is 2.34 Å. The Ca(6)-O(23) bond length is 2.51 Å. The Ca(6)-O(24) bond length is 2.51 Å. There are twelve inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a distorted rectangular see-saw-like geometry to one O(10), one O(12), one O(4), and one O(6) atom. The Sb(1)-O(10) bond length is 2.03 Å. The Sb(1)-O(12) bond length is 2.08 Å. The Sb(1)-O(4) bond length is 2.13 Å. The Sb(1)-O(6) bond length is 2.40 Å. In the second Sb site, Sb(2) is bonded in a distorted T-shaped geometry to one O(11), one O(2), and one O(5) atom. The Sb(2)-O(11) bond length is 2.06 Å. The Sb(2)-O(2) bond length is 1.95 Å. The Sb(2)-O(5) bond length is 1.96 Å. In the third Sb site, Sb(3) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(21), one O(3), and one O(4) atom. The Sb(3)-O(1) bond length is 1.98 Å. The Sb(3)-O(21) bond length is 2.68 Å. The Sb(3)-O(3) bond length is 2.07 Å. The Sb(3)-O(4) bond length is 2.12 Å. In the fourth Sb site, Sb(4) is bonded in a 5-coordinate geometry to one O(10), one O(2), one O(3), one O(6), and one O(8) atom. The Sb(4)-O(10) bond length is 2.08 Å. The Sb(4)-O(2) bond length is 2.54 Å. The Sb(4)-O(3) bond length is 2.32 Å. The Sb(4)-O(6) bond length is 1.97 Å. The Sb(4)-O(8) bond length is 2.41 Å. In the fifth Sb site, Sb(5) is bonded in a distorted T-shaped geometry to one O(14), one O(20), and one O(7) atom. The Sb(5)-O(14) bond length is 2.03 Å. The Sb(5)-O(20) bond length is 1.93 Å. The Sb(5)-O(7) bond length is 1.98 Å. In the sixth Sb site, Sb(6) is bonded in a distorted trigonal non-coplanar geometry to one O(13), one O(16), and one O(7) atom. The Sb(6)-O(13) bond length is 1.98 Å. The Sb(6)-O(16) bond length is 2.02 Å. The Sb(6)-O(7) bond length is 2.06 Å. In the seventh Sb site, Sb(7) is bonded in a distorted T-shaped geometry to one O(11), one O(18), and one O(9) atom. The Sb(7)-O(11) bond length is 2.00 Å. The Sb(7)-O(18) bond length is 2.03 Å. The Sb(7)-O(9) bond length is 1.92 Å. In the eighth Sb site, Sb(8) is bonded in a 3-coordinate geometry to one O(19), one O(23), and one O(24) atom. The Sb(8)-O(19) bond length is 2.02 Å. The Sb(8)-O(23) bond length is 2.07 Å. The Sb(8)-O(24) bond length is 2.07 Å. In the ninth Sb site, Sb(9) is bonded in a distorted T-shaped geometry to one O(12), one O(18), and one O(8) atom. The Sb(9)-O(12) bond length is 2.02 Å. The Sb(9)-O(18) bond length is 2.07 Å. The Sb(9)-O(8) bond length is 1.98 Å. In the tenth Sb site, Sb(10) is bonded in a rectangular see-saw-like geometry to one O(16), one O(17), one O(19), and one O(22) atom. The Sb(10)-O(16) bond length is 2.26 Å. The Sb(10)-O(17) bond length is 1.99 Å. The Sb(10)-O(19) bond length is 2.04 Å. The Sb(10)-O(22) bond length is 2.20 Å. In the eleventh Sb site, Sb(11) is bonded in a distorted T-shaped geometry to one O(14), one O(15), and one O(23) atom. The Sb(11)-O(14) bond length is 2.03 Å. The Sb(11)-O(15) bond length is 1.93 Å. The Sb(11)-O(23) bond length is 2.03 Å. In the twelfth Sb site, Sb(12) is bonded in a distorted trigonal non-coplanar geometry to one O(21), one O(22), and one O(24) atom. The Sb(12)-O(21) bond length is 1.95 Å. The Sb(12)-O(22) bond length is 2.02 Å. The Sb(12)-O(24) bond length is 2.14 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ca(3), and one Sb(3) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(3), one Sb(2), and one Sb(4) atom. In the third O site, O(3) is bonded to one Ca(1), one Ca(3), one Sb(3), and one Sb(4) atom to form corner-sharing OCa2Sb2 trigonal pyramids. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ca(1), one Sb(1), and one Sb(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Ca(2), one Ca(5), and one Sb(2) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Ca(2), one Sb(1), and one Sb(4) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Sb(5) and one Sb(6) atom. In the eighth O site, O(8) is bonded to one Ca(2), one Ca(3), one Sb(4), and one Sb(9) atom to form distorted corner-sharing OCa2Sb2 trigonal pyramids. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Ca(2), one Ca(5), and one Sb(7) atom. In the tenth O site, O(10) is bonded in a trigonal non-coplanar geometry to one Ca(3), one Sb(1), and one Sb(4) atom. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one Ca(2), one Sb(2), and one Sb(7) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Ca(3), one Sb(1), and one Sb(9) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Ca(4), one Ca(6), and one Sb(6) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Ca(4), one Sb(11), and one Sb(5) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one Ca(4), one Ca(5), and one Sb(11) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal pyramidal geometry to one Ca(4), one Ca(6), one Sb(10), and one Sb(6) atom. In the seventeenth O site, O(17) is bonded in a distorted T-shaped geometry to one Ca(1), one Ca(6), and one Sb(10) atom. In the eighteenth O site, O(18) is bonded in a distorted trigonal non-coplanar geometry to one Ca(2), one Sb(7), and one Sb(9) atom. In the nineteenth O site, O(19) is bonded in a trigonal non-coplanar geometry to one Ca(4), one Sb(10), and one Sb(8) atom. In the twentieth O site, O(20) is bonded in a distorted T-shaped geometry to one Ca(4), one Ca(5), and one Sb(5) atom. In the twenty-first O site, O(21) is bonded in a distorted bent 120 degrees geometry to one Ca(1), one Sb(12), and one Sb(3) atom. In the twenty-second O site, O(22) is bonded in a trigonal planar geometry to one Ca(6), one Sb(10), and one Sb(12) atom. In the twenty-third O site, O(23) is bonded in a distorted trigonal planar geometry to one Ca(6), one Sb(11), and one Sb(8) atom. In the twenty-fourth O site, O(24) is bonded in a distorted trigonal non-coplanar geometry to one Ca(6), one Sb(12), and one Sb(8) atom.