CaTl4(NiO3)4 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 6-coordinate geometry to one O(10), one O(2), one O(5), one O(7), one O(8), and one O(9) atom. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(10), one O(2), one O(5), one O(6), and one O(7) atom to form distorted corner-sharing NiO5 square pyramids. The corner-sharing octahedral tilt angles are 39°. In the second Ni site, Ni(2) is bonded to one O(1), one O(12), one O(3), one O(4), one O(6), and one O(8) atom to form corner-sharing NiO6 octahedra. In the third Ni site, Ni(3) is bonded to one O(1), one O(11), one O(12), one O(3), and one O(4) atom to form corner-sharing NiO5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 22-45°. In the fourth Ni site, Ni(4) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(2), one O(5), one O(7), and one O(9) atom. There are four inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(2), one O(4), one O(5), and one O(6) atom. In the second Tl site, Tl(2) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(3), one O(4), one O(8), and one O(9) atom. In the third Tl site, Tl(3) is bonded in a distorted pentagonal planar geometry to one O(12), one O(3), one O(7), one O(8), and one O(9) atom. In the fourth Tl site, Tl(4) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(2), one O(4), one O(5), and one O(6) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Ni(2), one Ni(3), one Tl(1), and one Tl(4) atom to form distorted OTl2Ni2 tetrahedra that share  a cornercorner with one O(11)Tl2Ni2 tetrahedra, corners with two equivalent O(5)CaTl2Ni2 trigonal bipyramids, corners with two equivalent O(12)Tl2Ni2 trigonal pyramids, edges with two equivalent O(4)Tl3Ni2 square pyramids,  an edgeedge with one O(11)Tl2Ni2 tetrahedra, and  an edgeedge with one O(2)CaTl2Ni2 trigonal bipyramid. In the second O site, O(2) is bonded to one Ca(1), one Ni(1), one Ni(4), one Tl(1), and one Tl(4) atom to form distorted OCaTl2Ni2 trigonal bipyramids that share corners with two equivalent O(4)Tl3Ni2 square pyramids,  a cornercorner with one O(11)Tl2Ni2 tetrahedra, corners with three equivalent O(10)CaTlNi2 trigonal pyramids,  an edgeedge with one O(1)Tl2Ni2 tetrahedra,  an edgeedge with one O(11)Tl2Ni2 tetrahedra,  an edgeedge with one O(5)CaTl2Ni2 trigonal bipyramid, and  a faceface with one O(5)CaTl2Ni2 trigonal bipyramid. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Ni(2), one Ni(3), one Tl(2), and one Tl(3) atom. In the fourth O site, O(4) is bonded to one Ni(2), one Ni(3), one Tl(1), one Tl(2), and one Tl(4) atom to form distorted OTl3Ni2 square pyramids that share corners with three equivalent O(11)Tl2Ni2 tetrahedra, corners with two equivalent O(2)CaTl2Ni2 trigonal bipyramids,  a cornercorner with one O(10)CaTlNi2 trigonal pyramid,  a cornercorner with one O(12)Tl2Ni2 trigonal pyramid, edges with two equivalent O(1)Tl2Ni2 tetrahedra,  an edgeedge with one O(5)CaTl2Ni2 trigonal bipyramid, and  an edgeedge with one O(12)Tl2Ni2 trigonal pyramid. In the fifth O site, O(5) is bonded to one Ca(1), one Ni(1), one Ni(4), one Tl(1), and one Tl(4) atom to form distorted OCaTl2Ni2 trigonal bipyramids that share corners with two equivalent O(1)Tl2Ni2 tetrahedra, corners with three equivalent O(11)Tl2Ni2 tetrahedra,  a cornercorner with one O(10)CaTlNi2 trigonal pyramid,  an edgeedge with one O(4)Tl3Ni2 square pyramid,  an edgeedge with one O(2)CaTl2Ni2 trigonal bipyramid,  an edgeedge with one O(10)CaTlNi2 trigonal pyramid, and  a faceface with one O(2)CaTl2Ni2 trigonal bipyramid. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Ni(1), one Ni(2), one Tl(1), and one Tl(4) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Ca(1), one Ni(1), one Ni(4), and one Tl(3) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Ni(2), one Tl(2), and one Tl(3) atom. In the ninth O site, O(9) is bonded in a distorted see-saw-like geometry to one Ca(1), one Ni(4), one Tl(2), and one Tl(3) atom. In the tenth O site, O(10) is bonded to one Ca(1), one Ni(1), one Ni(4), and one Tl(2) atom to form distorted OCaTlNi2 trigonal pyramids that share  a cornercorner with one O(4)Tl3Ni2 square pyramid,  a cornercorner with one O(11)Tl2Ni2 tetrahedra,  a cornercorner with one O(5)CaTl2Ni2 trigonal bipyramid, corners with three equivalent O(2)CaTl2Ni2 trigonal bipyramids,  a cornercorner with one O(12)Tl2Ni2 trigonal pyramid, and  an edgeedge with one O(5)CaTl2Ni2 trigonal bipyramid. In the eleventh O site, O(11) is bonded to one Ni(3), one Ni(4), one Tl(1), and one Tl(4) atom to form distorted OTl2Ni2 tetrahedra that share corners with three equivalent O(4)Tl3Ni2 square pyramids,  a cornercorner with one O(1)Tl2Ni2 tetrahedra,  a cornercorner with one O(2)CaTl2Ni2 trigonal bipyramid, corners with three equivalent O(5)CaTl2Ni2 trigonal bipyramids,  a cornercorner with one O(10)CaTlNi2 trigonal pyramid,  a cornercorner with one O(12)Tl2Ni2 trigonal pyramid,  an edgeedge with one O(1)Tl2Ni2 tetrahedra, and  an edgeedge with one O(2)CaTl2Ni2 trigonal bipyramid. In the twelfth O site, O(12) is bonded to one Ni(2), one Ni(3), one Tl(2), and one Tl(3) atom to form distorted OTl2Ni2 trigonal pyramids that share  a cornercorner with one O(4)Tl3Ni2 square pyramid,  a cornercorner with one O(11)Tl2Ni2 tetrahedra, corners with two equivalent O(1)Tl2Ni2 tetrahedra,  a cornercorner with one O(10)CaTlNi2 trigonal pyramid, and  an edgeedge with one O(4)Tl3Ni2 square pyramid.
CaTl4(NiO3)4 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 6-coordinate geometry to one O(10), one O(2), one O(5), one O(7), one O(8), and one O(9) atom. The Ca(1)-O(10) bond length is 2.26 Å. The Ca(1)-O(2) bond length is 2.29 Å. The Ca(1)-O(5) bond length is 2.46 Å. The Ca(1)-O(7) bond length is 2.25 Å. The Ca(1)-O(8) bond length is 2.27 Å. The Ca(1)-O(9) bond length is 2.38 Å. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(10), one O(2), one O(5), one O(6), and one O(7) atom to form distorted corner-sharing NiO5 square pyramids. The corner-sharing octahedral tilt angles are 39°. The Ni(1)-O(10) bond length is 1.93 Å. The Ni(1)-O(2) bond length is 1.97 Å. The Ni(1)-O(5) bond length is 2.05 Å. The Ni(1)-O(6) bond length is 2.06 Å. The Ni(1)-O(7) bond length is 1.91 Å. In the second Ni site, Ni(2) is bonded to one O(1), one O(12), one O(3), one O(4), one O(6), and one O(8) atom to form corner-sharing NiO6 octahedra. The Ni(2)-O(1) bond length is 2.01 Å. The Ni(2)-O(12) bond length is 2.10 Å. The Ni(2)-O(3) bond length is 2.17 Å. The Ni(2)-O(4) bond length is 2.27 Å. The Ni(2)-O(6) bond length is 2.05 Å. The Ni(2)-O(8) bond length is 2.02 Å. In the third Ni site, Ni(3) is bonded to one O(1), one O(11), one O(12), one O(3), and one O(4) atom to form corner-sharing NiO5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 22-45°. The Ni(3)-O(1) bond length is 1.93 Å. The Ni(3)-O(11) bond length is 2.05 Å. The Ni(3)-O(12) bond length is 1.99 Å. The Ni(3)-O(3) bond length is 2.01 Å. The Ni(3)-O(4) bond length is 2.03 Å. In the fourth Ni site, Ni(4) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(2), one O(5), one O(7), and one O(9) atom. The Ni(4)-O(10) bond length is 1.98 Å. The Ni(4)-O(11) bond length is 2.07 Å. The Ni(4)-O(2) bond length is 2.09 Å. The Ni(4)-O(5) bond length is 2.12 Å. The Ni(4)-O(7) bond length is 2.49 Å. The Ni(4)-O(9) bond length is 2.07 Å. There are four inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(2), one O(4), one O(5), and one O(6) atom. The Tl(1)-O(1) bond length is 2.25 Å. The Tl(1)-O(11) bond length is 2.14 Å. The Tl(1)-O(2) bond length is 2.51 Å. The Tl(1)-O(4) bond length is 2.56 Å. The Tl(1)-O(5) bond length is 2.20 Å. The Tl(1)-O(6) bond length is 2.64 Å. In the second Tl site, Tl(2) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(3), one O(4), one O(8), and one O(9) atom. The Tl(2)-O(10) bond length is 2.56 Å. The Tl(2)-O(12) bond length is 2.24 Å. The Tl(2)-O(3) bond length is 2.30 Å. The Tl(2)-O(4) bond length is 2.38 Å. The Tl(2)-O(8) bond length is 2.28 Å. The Tl(2)-O(9) bond length is 2.24 Å. In the third Tl site, Tl(3) is bonded in a distorted pentagonal planar geometry to one O(12), one O(3), one O(7), one O(8), and one O(9) atom. The Tl(3)-O(12) bond length is 2.22 Å. The Tl(3)-O(3) bond length is 2.34 Å. The Tl(3)-O(7) bond length is 2.29 Å. The Tl(3)-O(8) bond length is 2.42 Å. The Tl(3)-O(9) bond length is 2.21 Å. In the fourth Tl site, Tl(4) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(2), one O(4), one O(5), and one O(6) atom. The Tl(4)-O(1) bond length is 2.40 Å. The Tl(4)-O(11) bond length is 2.43 Å. The Tl(4)-O(2) bond length is 2.29 Å. The Tl(4)-O(4) bond length is 2.26 Å. The Tl(4)-O(5) bond length is 2.47 Å. The Tl(4)-O(6) bond length is 2.20 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Ni(2), one Ni(3), one Tl(1), and one Tl(4) atom to form distorted OTl2Ni2 tetrahedra that share  a cornercorner with one O(11)Tl2Ni2 tetrahedra, corners with two equivalent O(5)CaTl2Ni2 trigonal bipyramids, corners with two equivalent O(12)Tl2Ni2 trigonal pyramids, edges with two equivalent O(4)Tl3Ni2 square pyramids,  an edgeedge with one O(11)Tl2Ni2 tetrahedra, and  an edgeedge with one O(2)CaTl2Ni2 trigonal bipyramid. In the second O site, O(2) is bonded to one Ca(1), one Ni(1), one Ni(4), one Tl(1), and one Tl(4) atom to form distorted OCaTl2Ni2 trigonal bipyramids that share corners with two equivalent O(4)Tl3Ni2 square pyramids,  a cornercorner with one O(11)Tl2Ni2 tetrahedra, corners with three equivalent O(10)CaTlNi2 trigonal pyramids,  an edgeedge with one O(1)Tl2Ni2 tetrahedra,  an edgeedge with one O(11)Tl2Ni2 tetrahedra,  an edgeedge with one O(5)CaTl2Ni2 trigonal bipyramid, and  a faceface with one O(5)CaTl2Ni2 trigonal bipyramid. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Ni(2), one Ni(3), one Tl(2), and one Tl(3) atom. In the fourth O site, O(4) is bonded to one Ni(2), one Ni(3), one Tl(1), one Tl(2), and one Tl(4) atom to form distorted OTl3Ni2 square pyramids that share corners with three equivalent O(11)Tl2Ni2 tetrahedra, corners with two equivalent O(2)CaTl2Ni2 trigonal bipyramids,  a cornercorner with one O(10)CaTlNi2 trigonal pyramid,  a cornercorner with one O(12)Tl2Ni2 trigonal pyramid, edges with two equivalent O(1)Tl2Ni2 tetrahedra,  an edgeedge with one O(5)CaTl2Ni2 trigonal bipyramid, and  an edgeedge with one O(12)Tl2Ni2 trigonal pyramid. In the fifth O site, O(5) is bonded to one Ca(1), one Ni(1), one Ni(4), one Tl(1), and one Tl(4) atom to form distorted OCaTl2Ni2 trigonal bipyramids that share corners with two equivalent O(1)Tl2Ni2 tetrahedra, corners with three equivalent O(11)Tl2Ni2 tetrahedra,  a cornercorner with one O(10)CaTlNi2 trigonal pyramid,  an edgeedge with one O(4)Tl3Ni2 square pyramid,  an edgeedge with one O(2)CaTl2Ni2 trigonal bipyramid,  an edgeedge with one O(10)CaTlNi2 trigonal pyramid, and  a faceface with one O(2)CaTl2Ni2 trigonal bipyramid. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Ni(1), one Ni(2), one Tl(1), and one Tl(4) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Ca(1), one Ni(1), one Ni(4), and one Tl(3) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Ni(2), one Tl(2), and one Tl(3) atom. In the ninth O site, O(9) is bonded in a distorted see-saw-like geometry to one Ca(1), one Ni(4), one Tl(2), and one Tl(3) atom. In the tenth O site, O(10) is bonded to one Ca(1), one Ni(1), one Ni(4), and one Tl(2) atom to form distorted OCaTlNi2 trigonal pyramids that share  a cornercorner with one O(4)Tl3Ni2 square pyramid,  a cornercorner with one O(11)Tl2Ni2 tetrahedra,  a cornercorner with one O(5)CaTl2Ni2 trigonal bipyramid, corners with three equivalent O(2)CaTl2Ni2 trigonal bipyramids,  a cornercorner with one O(12)Tl2Ni2 trigonal pyramid, and  an edgeedge with one O(5)CaTl2Ni2 trigonal bipyramid. In the eleventh O site, O(11) is bonded to one Ni(3), one Ni(4), one Tl(1), and one Tl(4) atom to form distorted OTl2Ni2 tetrahedra that share corners with three equivalent O(4)Tl3Ni2 square pyramids,  a cornercorner with one O(1)Tl2Ni2 tetrahedra,  a cornercorner with one O(2)CaTl2Ni2 trigonal bipyramid, corners with three equivalent O(5)CaTl2Ni2 trigonal bipyramids,  a cornercorner with one O(10)CaTlNi2 trigonal pyramid,  a cornercorner with one O(12)Tl2Ni2 trigonal pyramid,  an edgeedge with one O(1)Tl2Ni2 tetrahedra, and  an edgeedge with one O(2)CaTl2Ni2 trigonal bipyramid. In the twelfth O site, O(12) is bonded to one Ni(2), one Ni(3), one Tl(2), and one Tl(3) atom to form distorted OTl2Ni2 trigonal pyramids that share  a cornercorner with one O(4)Tl3Ni2 square pyramid,  a cornercorner with one O(11)Tl2Ni2 tetrahedra, corners with two equivalent O(1)Tl2Ni2 tetrahedra,  a cornercorner with one O(10)CaTlNi2 trigonal pyramid, and  an edgeedge with one O(4)Tl3Ni2 square pyramid.