CaTl4(NiO3)4 crystallizes in the triclinic P1 space group. Ca(1) is bonded to one O(11), one O(12), one O(3), one O(4), and one O(6) atom to form distorted CaO5 trigonal bipyramids that share  a cornercorner with one Ni(4)O6 octahedra,  a cornercorner with one Ni(1)O5 trigonal bipyramid,  a cornercorner with one Ni(2)O5 trigonal bipyramid,  a cornercorner with one Tl(2)O5 trigonal bipyramid, and  an edgeedge with one Ni(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 65°. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(10), one O(2), one O(6), one O(7), and one O(8) atom to form distorted NiO5 trigonal bipyramids that share corners with three equivalent Ni(4)O6 octahedra,  a cornercorner with one Ca(1)O5 trigonal bipyramid,  a cornercorner with one Ni(2)O5 trigonal bipyramid, and corners with two equivalent Tl(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 33-47°. In the second Ni site, Ni(2) is bonded to one O(1), one O(12), one O(3), one O(4), and one O(8) atom to form NiO5 trigonal bipyramids that share  a cornercorner with one Ca(1)O5 trigonal bipyramid,  a cornercorner with one Ni(1)O5 trigonal bipyramid, corners with two equivalent Tl(2)O5 trigonal bipyramids, and  an edgeedge with one Ca(1)O5 trigonal bipyramid. In the third Ni site, Ni(3) is bonded in a distorted see-saw-like geometry to one O(1), one O(12), one O(3), and one O(9) atom. In the fourth Ni site, Ni(4) is bonded to one O(10), one O(11), one O(2), one O(5), one O(7), and one O(9) atom to form NiO6 octahedra that share  a cornercorner with one Ca(1)O5 trigonal bipyramid,  a cornercorner with one Tl(2)O5 trigonal bipyramid, corners with three equivalent Ni(1)O5 trigonal bipyramids, and  an edgeedge with one Tl(2)O5 trigonal bipyramid. There are four inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 6-coordinate geometry to one O(10), 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 to one O(3), one O(5), one O(7), one O(8), and one O(9) atom to form distorted TlO5 trigonal bipyramids that share  a cornercorner with one Ni(4)O6 octahedra,  a cornercorner with one Ca(1)O5 trigonal bipyramid, corners with two equivalent Ni(1)O5 trigonal bipyramids, corners with two equivalent Ni(2)O5 trigonal bipyramids, and  an edgeedge with one Ni(4)O6 octahedra. The corner-sharing octahedral tilt angles are 70°. In the third Tl site, Tl(3) is bonded in a 7-coordinate geometry to one O(1), one O(10), 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 in a 4-coordinate geometry to one Ni(2), one Ni(3), one Tl(3), and one Tl(4) atom. In the second O site, O(2) is bonded to one Ni(1), one Ni(4), one Tl(1), and one Tl(4) atom to form OTl2Ni2 tetrahedra that share  a cornercorner with one O(9)Tl2Ni2 tetrahedra, corners with two equivalent O(7)Tl2Ni2 tetrahedra, and corners with two equivalent O(4)CaTl2Ni trigonal pyramids. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Ca(1), 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 Ca(1), one Ni(2), one Tl(1), and one Tl(4) atom to form corner-sharing OCaTl2Ni trigonal pyramids. In the fifth O site, O(5) is bonded in a distorted see-saw-like geometry to one Ni(4), one Tl(1), one Tl(2), and one Tl(4) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Ni(1), one Tl(1), and one Tl(4) atom. In the seventh O site, O(7) is bonded to one Ni(1), one Ni(4), one Tl(2), and one Tl(3) atom to form corner-sharing OTl2Ni2 tetrahedra. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Ni(1), one Ni(2), one Tl(2), and one Tl(3) atom. In the ninth O site, O(9) is bonded to one Ni(3), one Ni(4), one Tl(2), and one Tl(3) atom to form corner-sharing OTl2Ni2 tetrahedra. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Ni(1), one Ni(4), one Tl(1), and one Tl(3) atom. In the eleventh O site, O(11) is bonded in a see-saw-like geometry to one Ca(1), one Ni(4), one Tl(1), and one Tl(4) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Ni(2), one Ni(3), and one Tl(3) atom.
CaTl4(NiO3)4 crystallizes in the triclinic P1 space group. Ca(1) is bonded to one O(11), one O(12), one O(3), one O(4), and one O(6) atom to form distorted CaO5 trigonal bipyramids that share  a cornercorner with one Ni(4)O6 octahedra,  a cornercorner with one Ni(1)O5 trigonal bipyramid,  a cornercorner with one Ni(2)O5 trigonal bipyramid,  a cornercorner with one Tl(2)O5 trigonal bipyramid, and  an edgeedge with one Ni(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 65°. The Ca(1)-O(11) bond length is 2.28 Å. The Ca(1)-O(12) bond length is 2.58 Å. The Ca(1)-O(3) bond length is 2.34 Å. The Ca(1)-O(4) bond length is 2.29 Å. The Ca(1)-O(6) bond length is 2.32 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(6), one O(7), and one O(8) atom to form distorted NiO5 trigonal bipyramids that share corners with three equivalent Ni(4)O6 octahedra,  a cornercorner with one Ca(1)O5 trigonal bipyramid,  a cornercorner with one Ni(2)O5 trigonal bipyramid, and corners with two equivalent Tl(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 33-47°. The Ni(1)-O(10) bond length is 1.89 Å. The Ni(1)-O(2) bond length is 1.95 Å. The Ni(1)-O(6) bond length is 1.95 Å. The Ni(1)-O(7) bond length is 2.13 Å. The Ni(1)-O(8) bond length is 1.94 Å. In the second Ni site, Ni(2) is bonded to one O(1), one O(12), one O(3), one O(4), and one O(8) atom to form NiO5 trigonal bipyramids that share  a cornercorner with one Ca(1)O5 trigonal bipyramid,  a cornercorner with one Ni(1)O5 trigonal bipyramid, corners with two equivalent Tl(2)O5 trigonal bipyramids, and  an edgeedge with one Ca(1)O5 trigonal bipyramid. The Ni(2)-O(1) bond length is 1.93 Å. The Ni(2)-O(12) bond length is 1.94 Å. The Ni(2)-O(3) bond length is 2.17 Å. The Ni(2)-O(4) bond length is 1.88 Å. The Ni(2)-O(8) bond length is 2.00 Å. In the third Ni site, Ni(3) is bonded in a distorted see-saw-like geometry to one O(1), one O(12), one O(3), and one O(9) atom. The Ni(3)-O(1) bond length is 1.94 Å. The Ni(3)-O(12) bond length is 1.97 Å. The Ni(3)-O(3) bond length is 1.97 Å. The Ni(3)-O(9) bond length is 1.95 Å. In the fourth Ni site, Ni(4) is bonded to one O(10), one O(11), one O(2), one O(5), one O(7), and one O(9) atom to form NiO6 octahedra that share  a cornercorner with one Ca(1)O5 trigonal bipyramid,  a cornercorner with one Tl(2)O5 trigonal bipyramid, corners with three equivalent Ni(1)O5 trigonal bipyramids, and  an edgeedge with one Tl(2)O5 trigonal bipyramid. The Ni(4)-O(10) bond length is 1.99 Å. The Ni(4)-O(11) bond length is 2.15 Å. The Ni(4)-O(2) bond length is 2.01 Å. The Ni(4)-O(5) bond length is 2.12 Å. The Ni(4)-O(7) bond length is 2.12 Å. The Ni(4)-O(9) bond length is 2.27 Å. There are four inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(2), one O(4), one O(5), and one O(6) atom. The Tl(1)-O(10) bond length is 2.45 Å. The Tl(1)-O(11) bond length is 2.25 Å. The Tl(1)-O(2) bond length is 2.18 Å. The Tl(1)-O(4) bond length is 2.46 Å. The Tl(1)-O(5) bond length is 2.32 Å. The Tl(1)-O(6) bond length is 2.33 Å. In the second Tl site, Tl(2) is bonded to one O(3), one O(5), one O(7), one O(8), and one O(9) atom to form distorted TlO5 trigonal bipyramids that share  a cornercorner with one Ni(4)O6 octahedra,  a cornercorner with one Ca(1)O5 trigonal bipyramid, corners with two equivalent Ni(1)O5 trigonal bipyramids, corners with two equivalent Ni(2)O5 trigonal bipyramids, and  an edgeedge with one Ni(4)O6 octahedra. The corner-sharing octahedral tilt angles are 70°. The Tl(2)-O(3) bond length is 2.33 Å. The Tl(2)-O(5) bond length is 2.36 Å. The Tl(2)-O(7) bond length is 2.17 Å. The Tl(2)-O(8) bond length is 2.33 Å. The Tl(2)-O(9) bond length is 2.22 Å. In the third Tl site, Tl(3) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(12), one O(3), one O(7), one O(8), and one O(9) atom. The Tl(3)-O(1) bond length is 2.61 Å. The Tl(3)-O(10) bond length is 2.37 Å. The Tl(3)-O(12) bond length is 2.32 Å. The Tl(3)-O(3) bond length is 2.59 Å. The Tl(3)-O(7) bond length is 2.31 Å. The Tl(3)-O(8) bond length is 2.49 Å. The Tl(3)-O(9) bond length is 2.23 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 2.31 Å. The Tl(4)-O(11) bond length is 2.28 Å. The Tl(4)-O(2) bond length is 2.27 Å. The Tl(4)-O(4) bond length is 2.36 Å. The Tl(4)-O(5) bond length is 2.32 Å. The Tl(4)-O(6) bond length is 2.46 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Ni(2), one Ni(3), one Tl(3), and one Tl(4) atom. In the second O site, O(2) is bonded to one Ni(1), one Ni(4), one Tl(1), and one Tl(4) atom to form OTl2Ni2 tetrahedra that share  a cornercorner with one O(9)Tl2Ni2 tetrahedra, corners with two equivalent O(7)Tl2Ni2 tetrahedra, and corners with two equivalent O(4)CaTl2Ni trigonal pyramids. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Ca(1), 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 Ca(1), one Ni(2), one Tl(1), and one Tl(4) atom to form corner-sharing OCaTl2Ni trigonal pyramids. In the fifth O site, O(5) is bonded in a distorted see-saw-like geometry to one Ni(4), one Tl(1), one Tl(2), and one Tl(4) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Ni(1), one Tl(1), and one Tl(4) atom. In the seventh O site, O(7) is bonded to one Ni(1), one Ni(4), one Tl(2), and one Tl(3) atom to form corner-sharing OTl2Ni2 tetrahedra. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Ni(1), one Ni(2), one Tl(2), and one Tl(3) atom. In the ninth O site, O(9) is bonded to one Ni(3), one Ni(4), one Tl(2), and one Tl(3) atom to form corner-sharing OTl2Ni2 tetrahedra. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Ni(1), one Ni(4), one Tl(1), and one Tl(3) atom. In the eleventh O site, O(11) is bonded in a see-saw-like geometry to one Ca(1), one Ni(4), one Tl(1), and one Tl(4) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Ni(2), one Ni(3), and one Tl(3) atom.