Ca4Ni20H crystallizes in the orthorhombic Cmm2 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 1-coordinate geometry to two equivalent Ni(1), two equivalent Ni(3), two equivalent Ni(8), four equivalent Ni(6), four equivalent Ni(7), and one H(1) atom. In the second Ca site, Ca(2) is bonded in a 18-coordinate geometry to one Ni(2), one Ni(3), four equivalent Ni(1), four equivalent Ni(5), four equivalent Ni(6), and four equivalent Ni(7) atoms. There are eight inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 9-coordinate geometry to one Ca(1), two equivalent Ca(2), two equivalent Ni(5), two equivalent Ni(6), and two equivalent Ni(7) atoms. In the second Ni site, Ni(2) is bonded in a single-bond geometry to one Ca(2), four equivalent Ni(7), and one H(1) atom. In the third Ni site, Ni(3) is bonded in a 9-coordinate geometry to one Ca(2), two equivalent Ca(1), two equivalent Ni(8), and four equivalent Ni(6) atoms. In the fourth Ni site, Ni(4) is bonded in a distorted single-bond geometry to four equivalent Ni(7) and two equivalent H(1) atoms. In the fifth Ni site, Ni(5) is bonded to four equivalent Ca(2), two equivalent Ni(6), two equivalent Ni(7), and four equivalent Ni(1) atoms to form a mixture of edge, corner, and face-sharing NiCa4Ni8 cuboctahedra. In the sixth Ni site, Ni(6) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Ni(5), one Ni(6), one Ni(7), one Ni(8), two equivalent Ni(1), and two equivalent Ni(3) atoms to form a mixture of edge, corner, and face-sharing NiCa4Ni8 cuboctahedra. In the seventh Ni site, Ni(7) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Ni(4), one Ni(5), one Ni(6), one Ni(7), two equivalent Ni(1), and two equivalent Ni(2) atoms to form a mixture of edge, corner, and face-sharing NiCa4Ni8 cuboctahedra. In the eighth Ni site, Ni(8) is bonded to four equivalent Ca(1), four equivalent Ni(3), and four equivalent Ni(6) atoms to form a mixture of edge, corner, and face-sharing NiCa4Ni8 cuboctahedra. H(1) is bonded in a 6-coordinate geometry to two equivalent Ca(1), two equivalent Ni(2), and two equivalent Ni(4) atoms.
Ca4Ni20H crystallizes in the orthorhombic Cmm2 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 1-coordinate geometry to two equivalent Ni(1), two equivalent Ni(3), two equivalent Ni(8), four equivalent Ni(6), four equivalent Ni(7), and one H(1) atom. Both Ca(1)-Ni(1) bond lengths are 2.87 Å. Both Ca(1)-Ni(3) bond lengths are 2.84 Å. There is one shorter (3.13 Å) and one longer (3.14 Å) Ca(1)-Ni(8) bond length. There are two shorter (3.14 Å) and two longer (3.15 Å) Ca(1)-Ni(6) bond lengths. All Ca(1)-Ni(7) bond lengths are 3.17 Å. The Ca(1)-H(1) bond length is 2.44 Å. In the second Ca site, Ca(2) is bonded in a 18-coordinate geometry to one Ni(2), one Ni(3), four equivalent Ni(1), four equivalent Ni(5), four equivalent Ni(6), and four equivalent Ni(7) atoms. The Ca(2)-Ni(2) bond length is 2.79 Å. The Ca(2)-Ni(3) bond length is 2.82 Å. There are two shorter (2.81 Å) and two longer (2.86 Å) Ca(2)-Ni(1) bond lengths. All Ca(2)-Ni(5) bond lengths are 3.12 Å. All Ca(2)-Ni(6) bond lengths are 3.11 Å. All Ca(2)-Ni(7) bond lengths are 3.16 Å. There are eight inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 9-coordinate geometry to one Ca(1), two equivalent Ca(2), two equivalent Ni(5), two equivalent Ni(6), and two equivalent Ni(7) atoms. Both Ni(1)-Ni(5) bond lengths are 2.42 Å. Both Ni(1)-Ni(6) bond lengths are 2.41 Å. There is one shorter (2.38 Å) and one longer (2.39 Å) Ni(1)-Ni(7) bond length. In the second Ni site, Ni(2) is bonded in a single-bond geometry to one Ca(2), four equivalent Ni(7), and one H(1) atom. There are two shorter (2.37 Å) and two longer (2.38 Å) Ni(2)-Ni(7) bond lengths. The Ni(2)-H(1) bond length is 1.61 Å. In the third Ni site, Ni(3) is bonded in a 9-coordinate geometry to one Ca(2), two equivalent Ca(1), two equivalent Ni(8), and four equivalent Ni(6) atoms. Both Ni(3)-Ni(8) bond lengths are 2.40 Å. All Ni(3)-Ni(6) bond lengths are 2.41 Å. In the fourth Ni site, Ni(4) is bonded in a distorted single-bond geometry to four equivalent Ni(7) and two equivalent H(1) atoms. All Ni(4)-Ni(7) bond lengths are 2.51 Å. There is one shorter (1.66 Å) and one longer (2.23 Å) Ni(4)-H(1) bond length. In the fifth Ni site, Ni(5) is bonded to four equivalent Ca(2), two equivalent Ni(6), two equivalent Ni(7), and four equivalent Ni(1) atoms to form a mixture of edge, corner, and face-sharing NiCa4Ni8 cuboctahedra. Both Ni(5)-Ni(6) bond lengths are 2.48 Å. Both Ni(5)-Ni(7) bond lengths are 2.44 Å. In the sixth Ni site, Ni(6) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Ni(5), one Ni(6), one Ni(7), one Ni(8), two equivalent Ni(1), and two equivalent Ni(3) atoms to form a mixture of edge, corner, and face-sharing NiCa4Ni8 cuboctahedra. The Ni(6)-Ni(6) bond length is 2.45 Å. The Ni(6)-Ni(7) bond length is 2.44 Å. The Ni(6)-Ni(8) bond length is 2.47 Å. In the seventh Ni site, Ni(7) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Ni(4), one Ni(5), one Ni(6), one Ni(7), two equivalent Ni(1), and two equivalent Ni(2) atoms to form a mixture of edge, corner, and face-sharing NiCa4Ni8 cuboctahedra. The Ni(7)-Ni(7) bond length is 2.44 Å. In the eighth Ni site, Ni(8) is bonded to four equivalent Ca(1), four equivalent Ni(3), and four equivalent Ni(6) atoms to form a mixture of edge, corner, and face-sharing NiCa4Ni8 cuboctahedra. H(1) is bonded in a 6-coordinate geometry to two equivalent Ca(1), two equivalent Ni(2), and two equivalent Ni(4) atoms.