Ni5(SeO3)4Cl2 crystallizes in the triclinic P-1 space group. There are five inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(3), one O(5), one O(7), one O(8), one O(9), and one Cl(2) atom to form distorted NiClO5 octahedra that share  a cornercorner with one Ni(3)ClO5 octahedra,  a cornercorner with one Ni(4)O6 octahedra,  an edgeedge with one Ni(5)ClO5 octahedra, and  a faceface with one Ni(2)Cl2O4 octahedra. The corner-sharing octahedral tilt angles range from 49-54°. In the second Ni site, Ni(2) is bonded to one O(10), one O(5), one O(6), one O(9), one Cl(1), and one Cl(2) atom to form distorted NiCl2O4 octahedra that share  a cornercorner with one Ni(3)ClO5 octahedra,  a cornercorner with one Ni(4)O6 octahedra, corners with two equivalent Ni(5)ClO5 octahedra, and  a faceface with one Ni(1)ClO5 octahedra. The corner-sharing octahedral tilt angles range from 34-68°. In the third Ni site, Ni(3) is bonded to one O(11), one O(3), one O(4), two equivalent O(2), and one Cl(1) atom to form NiClO5 octahedra that share  a cornercorner with one Ni(2)Cl2O4 octahedra,  a cornercorner with one Ni(1)ClO5 octahedra,  a cornercorner with one Ni(5)ClO5 octahedra,  a cornercorner with one Ni(4)O6 octahedra, and  an edgeedge with one Ni(3)ClO5 octahedra. The corner-sharing octahedral tilt angles range from 48-68°. In the fourth Ni site, Ni(4) is bonded to one O(1), one O(4), one O(6), one O(8), and two equivalent O(12) atoms to form NiO6 octahedra that share  a cornercorner with one Ni(2)Cl2O4 octahedra,  a cornercorner with one Ni(1)ClO5 octahedra,  a cornercorner with one Ni(3)ClO5 octahedra,  an edgeedge with one Ni(4)O6 octahedra, and edges with two equivalent Ni(5)ClO5 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. In the fifth Ni site, Ni(5) is bonded to one O(1), one O(10), one O(11), one O(12), one O(8), and one Cl(2) atom to form distorted NiClO5 octahedra that share  a cornercorner with one Ni(3)ClO5 octahedra, corners with two equivalent Ni(2)Cl2O4 octahedra,  an edgeedge with one Ni(1)ClO5 octahedra, and edges with two equivalent Ni(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-52°. There are four inequivalent Se sites. In the first Se site, Se(1) is bonded in a trigonal non-coplanar geometry to one O(12), one O(2), and one O(7) atom. In the second Se site, Se(2) is bonded in a trigonal non-coplanar geometry to one O(1), one O(4), and one O(9) atom. In the third Se site, Se(3) is bonded in a trigonal non-coplanar geometry to one O(11), one O(3), and one O(5) atom. In the fourth Se site, Se(4) is bonded in a distorted T-shaped geometry to one O(10), one O(6), and one O(8) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Ni(4), one Ni(5), and one Se(2) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to two equivalent Ni(3) and one Se(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Ni(1), one Ni(3), and one Se(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Ni(3), one Ni(4), and one Se(2) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Ni(1), one Ni(2), and one Se(3) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Ni(2), one Ni(4), and one Se(4) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Ni(1) and one Se(1) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Ni(1), one Ni(4), one Ni(5), and one Se(4) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Ni(1), one Ni(2), and one Se(2) atom. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one Ni(2), one Ni(5), and one Se(4) atom. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one Ni(3), one Ni(5), and one Se(3) atom. In the twelfth O site, O(12) is bonded to one Ni(5), two equivalent Ni(4), and one Se(1) atom to form distorted edge-sharing ONi3Se trigonal pyramids. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a water-like geometry to one Ni(2) and one Ni(3) atom. In the second Cl site, Cl(2) is bonded in a distorted T-shaped geometry to one Ni(1), one Ni(2), and one Ni(5) atom.
Ni5(SeO3)4Cl2 crystallizes in the triclinic P-1 space group. There are five inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(3), one O(5), one O(7), one O(8), one O(9), and one Cl(2) atom to form distorted NiClO5 octahedra that share  a cornercorner with one Ni(3)ClO5 octahedra,  a cornercorner with one Ni(4)O6 octahedra,  an edgeedge with one Ni(5)ClO5 octahedra, and  a faceface with one Ni(2)Cl2O4 octahedra. The corner-sharing octahedral tilt angles range from 49-54°. The Ni(1)-O(3) bond length is 2.06 Å. The Ni(1)-O(5) bond length is 2.12 Å. The Ni(1)-O(7) bond length is 2.02 Å. The Ni(1)-O(8) bond length is 2.06 Å. The Ni(1)-O(9) bond length is 2.05 Å. The Ni(1)-Cl(2) bond length is 2.70 Å. In the second Ni site, Ni(2) is bonded to one O(10), one O(5), one O(6), one O(9), one Cl(1), and one Cl(2) atom to form distorted NiCl2O4 octahedra that share  a cornercorner with one Ni(3)ClO5 octahedra,  a cornercorner with one Ni(4)O6 octahedra, corners with two equivalent Ni(5)ClO5 octahedra, and  a faceface with one Ni(1)ClO5 octahedra. The corner-sharing octahedral tilt angles range from 34-68°. The Ni(2)-O(10) bond length is 2.06 Å. The Ni(2)-O(5) bond length is 2.09 Å. The Ni(2)-O(6) bond length is 2.09 Å. The Ni(2)-O(9) bond length is 2.10 Å. The Ni(2)-Cl(1) bond length is 2.35 Å. The Ni(2)-Cl(2) bond length is 2.52 Å. In the third Ni site, Ni(3) is bonded to one O(11), one O(3), one O(4), two equivalent O(2), and one Cl(1) atom to form NiClO5 octahedra that share  a cornercorner with one Ni(2)Cl2O4 octahedra,  a cornercorner with one Ni(1)ClO5 octahedra,  a cornercorner with one Ni(5)ClO5 octahedra,  a cornercorner with one Ni(4)O6 octahedra, and  an edgeedge with one Ni(3)ClO5 octahedra. The corner-sharing octahedral tilt angles range from 48-68°. The Ni(3)-O(11) bond length is 2.14 Å. The Ni(3)-O(3) bond length is 2.16 Å. The Ni(3)-O(4) bond length is 2.02 Å. There is one shorter (2.08 Å) and one longer (2.11 Å) Ni(3)-O(2) bond length. The Ni(3)-Cl(1) bond length is 2.41 Å. In the fourth Ni site, Ni(4) is bonded to one O(1), one O(4), one O(6), one O(8), and two equivalent O(12) atoms to form NiO6 octahedra that share  a cornercorner with one Ni(2)Cl2O4 octahedra,  a cornercorner with one Ni(1)ClO5 octahedra,  a cornercorner with one Ni(3)ClO5 octahedra,  an edgeedge with one Ni(4)O6 octahedra, and edges with two equivalent Ni(5)ClO5 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. The Ni(4)-O(1) bond length is 2.05 Å. The Ni(4)-O(4) bond length is 2.08 Å. The Ni(4)-O(6) bond length is 2.14 Å. The Ni(4)-O(8) bond length is 2.06 Å. There is one shorter (2.07 Å) and one longer (2.14 Å) Ni(4)-O(12) bond length. In the fifth Ni site, Ni(5) is bonded to one O(1), one O(10), one O(11), one O(12), one O(8), and one Cl(2) atom to form distorted NiClO5 octahedra that share  a cornercorner with one Ni(3)ClO5 octahedra, corners with two equivalent Ni(2)Cl2O4 octahedra,  an edgeedge with one Ni(1)ClO5 octahedra, and edges with two equivalent Ni(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-52°. The Ni(5)-O(1) bond length is 2.09 Å. The Ni(5)-O(10) bond length is 2.07 Å. The Ni(5)-O(11) bond length is 2.05 Å. The Ni(5)-O(12) bond length is 2.18 Å. The Ni(5)-O(8) bond length is 2.31 Å. The Ni(5)-Cl(2) bond length is 2.41 Å. There are four inequivalent Se sites. In the first Se site, Se(1) is bonded in a trigonal non-coplanar geometry to one O(12), one O(2), and one O(7) atom. The Se(1)-O(12) bond length is 1.83 Å. The Se(1)-O(2) bond length is 1.74 Å. The Se(1)-O(7) bond length is 1.68 Å. In the second Se site, Se(2) is bonded in a trigonal non-coplanar geometry to one O(1), one O(4), and one O(9) atom. The Se(2)-O(1) bond length is 1.76 Å. The Se(2)-O(4) bond length is 1.74 Å. The Se(2)-O(9) bond length is 1.74 Å. In the third Se site, Se(3) is bonded in a trigonal non-coplanar geometry to one O(11), one O(3), and one O(5) atom. The Se(3)-O(11) bond length is 1.75 Å. The Se(3)-O(3) bond length is 1.73 Å. The Se(3)-O(5) bond length is 1.72 Å. In the fourth Se site, Se(4) is bonded in a distorted T-shaped geometry to one O(10), one O(6), and one O(8) atom. The Se(4)-O(10) bond length is 1.72 Å. The Se(4)-O(6) bond length is 1.73 Å. The Se(4)-O(8) bond length is 1.78 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Ni(4), one Ni(5), and one Se(2) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to two equivalent Ni(3) and one Se(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Ni(1), one Ni(3), and one Se(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Ni(3), one Ni(4), and one Se(2) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Ni(1), one Ni(2), and one Se(3) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Ni(2), one Ni(4), and one Se(4) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Ni(1) and one Se(1) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Ni(1), one Ni(4), one Ni(5), and one Se(4) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Ni(1), one Ni(2), and one Se(2) atom. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one Ni(2), one Ni(5), and one Se(4) atom. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one Ni(3), one Ni(5), and one Se(3) atom. In the twelfth O site, O(12) is bonded to one Ni(5), two equivalent Ni(4), and one Se(1) atom to form distorted edge-sharing ONi3Se trigonal pyramids. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a water-like geometry to one Ni(2) and one Ni(3) atom. In the second Cl site, Cl(2) is bonded in a distorted T-shaped geometry to one Ni(1), one Ni(2), and one Ni(5) atom.