BaCaV2Ni3(HO5)2 crystallizes in the triclinic P1 space group. Ba(1) is bonded in a 8-coordinate geometry to one H(1), one O(2), one O(3), one O(4), one O(6), one O(7), and two equivalent O(8) atoms. Ca(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(5), one O(7), and one O(8) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(5), and one O(8) atom to form VO4 tetrahedra that share corners with two equivalent Ni(1)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra, and corners with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-66°. In the second V site, V(2) is bonded to one O(3), one O(4), one O(6), and one O(7) atom to form VO4 tetrahedra that share corners with two equivalent Ni(1)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra, and corners with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-62°. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(10), one O(2), one O(3), one O(4), and one O(9) atom to form NiO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. In the second Ni site, Ni(2) is bonded to one O(1), one O(10), one O(3), one O(5), one O(6), and one O(9) atom to form NiO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. In the third Ni site, Ni(3) is bonded to one O(10), one O(2), one O(4), one O(5), one O(6), and one O(9) atom to form NiO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one Ba(1) and one O(9) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(10) atom. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Ca(1), one V(1), one Ni(1), and one Ni(2) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Ba(1), one Ca(1), one V(1), one Ni(1), and one Ni(3) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Ba(1), one V(2), one Ni(1), and one Ni(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Ba(1), one V(2), one Ni(1), and one Ni(3) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Ca(1), one V(1), one Ni(2), and one Ni(3) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Ba(1), one V(2), one Ni(2), and one Ni(3) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ba(1), one Ca(1), and one V(2) atom. In the eighth O site, O(8) is bonded in a 2-coordinate geometry to two equivalent Ba(1), one Ca(1), and one V(1) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Ni(1), one Ni(2), one Ni(3), and one H(1) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to one Ni(1), one Ni(2), one Ni(3), and one H(2) atom.
BaCaV2Ni3(HO5)2 crystallizes in the triclinic P1 space group. Ba(1) is bonded in a 8-coordinate geometry to one H(1), one O(2), one O(3), one O(4), one O(6), one O(7), and two equivalent O(8) atoms. The Ba(1)-H(1) bond length is 2.74 Å. The Ba(1)-O(2) bond length is 3.06 Å. The Ba(1)-O(3) bond length is 2.58 Å. The Ba(1)-O(4) bond length is 2.67 Å. The Ba(1)-O(6) bond length is 2.74 Å. The Ba(1)-O(7) bond length is 2.61 Å. There is one shorter (2.94 Å) and one longer (3.14 Å) Ba(1)-O(8) bond length. Ca(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(5), one O(7), and one O(8) atom. The Ca(1)-O(1) bond length is 2.18 Å. The Ca(1)-O(2) bond length is 2.43 Å. The Ca(1)-O(5) bond length is 2.33 Å. The Ca(1)-O(7) bond length is 2.35 Å. The Ca(1)-O(8) bond length is 2.32 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(5), and one O(8) atom to form VO4 tetrahedra that share corners with two equivalent Ni(1)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra, and corners with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-66°. The V(1)-O(1) bond length is 1.87 Å. The V(1)-O(2) bond length is 1.86 Å. The V(1)-O(5) bond length is 1.86 Å. The V(1)-O(8) bond length is 1.82 Å. In the second V site, V(2) is bonded to one O(3), one O(4), one O(6), and one O(7) atom to form VO4 tetrahedra that share corners with two equivalent Ni(1)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra, and corners with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-62°. The V(2)-O(3) bond length is 1.86 Å. The V(2)-O(4) bond length is 1.84 Å. The V(2)-O(6) bond length is 1.84 Å. The V(2)-O(7) bond length is 1.84 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(10), one O(2), one O(3), one O(4), and one O(9) atom to form NiO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The Ni(1)-O(1) bond length is 2.11 Å. The Ni(1)-O(10) bond length is 2.01 Å. The Ni(1)-O(2) bond length is 2.31 Å. The Ni(1)-O(3) bond length is 2.06 Å. The Ni(1)-O(4) bond length is 2.10 Å. The Ni(1)-O(9) bond length is 2.02 Å. In the second Ni site, Ni(2) is bonded to one O(1), one O(10), one O(3), one O(5), one O(6), and one O(9) atom to form NiO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The Ni(2)-O(1) bond length is 2.08 Å. The Ni(2)-O(10) bond length is 2.01 Å. The Ni(2)-O(3) bond length is 2.07 Å. The Ni(2)-O(5) bond length is 2.21 Å. The Ni(2)-O(6) bond length is 2.16 Å. The Ni(2)-O(9) bond length is 2.04 Å. In the third Ni site, Ni(3) is bonded to one O(10), one O(2), one O(4), one O(5), one O(6), and one O(9) atom to form NiO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. The Ni(3)-O(10) bond length is 2.03 Å. The Ni(3)-O(2) bond length is 2.40 Å. The Ni(3)-O(4) bond length is 2.10 Å. The Ni(3)-O(5) bond length is 2.10 Å. The Ni(3)-O(6) bond length is 2.14 Å. The Ni(3)-O(9) bond length is 2.10 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one Ba(1) and one O(9) atom. The H(1)-O(9) bond length is 0.98 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(10) atom. The H(2)-O(10) bond length is 0.99 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Ca(1), one V(1), one Ni(1), and one Ni(2) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Ba(1), one Ca(1), one V(1), one Ni(1), and one Ni(3) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Ba(1), one V(2), one Ni(1), and one Ni(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Ba(1), one V(2), one Ni(1), and one Ni(3) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Ca(1), one V(1), one Ni(2), and one Ni(3) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Ba(1), one V(2), one Ni(2), and one Ni(3) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ba(1), one Ca(1), and one V(2) atom. In the eighth O site, O(8) is bonded in a 2-coordinate geometry to two equivalent Ba(1), one Ca(1), and one V(1) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Ni(1), one Ni(2), one Ni(3), and one H(1) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to one Ni(1), one Ni(2), one Ni(3), and one H(2) atom.