Ca2Ni10H crystallizes in the orthorhombic Cmm2 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Ni(1), four equivalent Ni(3), four equivalent Ni(6), and two equivalent H(1) atoms. In the second Ca site, Ca(2) is bonded in a 18-coordinate geometry to two equivalent Ni(2), two equivalent Ni(5), four equivalent Ni(3), four equivalent Ni(6), and six equivalent Ni(4) atoms. There are six inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a distorted single-bond geometry to one Ca(1), two equivalent Ni(3), two equivalent Ni(6), and one H(1) atom. In the second Ni site, Ni(2) is bonded in a single-bond geometry to two equivalent Ca(2), two equivalent Ni(4), four equivalent Ni(3), and one H(1) atom. In the third Ni site, Ni(3) is bonded to two equivalent Ca(1), two equivalent Ca(2), two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(3), and two equivalent Ni(4) atoms to form NiCa4Ni8 cuboctahedra that share corners with four equivalent Ni(3)Ca4Ni8 cuboctahedra, corners with eight equivalent Ni(6)Ca4Ni8 cuboctahedra, corners with two equivalent H(1)Ca2Ni4 octahedra, edges with two equivalent Ni(3)Ca4Ni8 cuboctahedra, edges with four equivalent Ni(6)Ca4Ni8 cuboctahedra, faces with two equivalent Ni(6)Ca4Ni8 cuboctahedra, faces with four equivalent Ni(3)Ca4Ni8 cuboctahedra, and faces with two equivalent H(1)Ca2Ni4 octahedra. The corner-sharing octahedral tilt angles are 70°. In the fourth Ni site, Ni(4) is bonded in a 9-coordinate geometry to three equivalent Ca(2), one Ni(2), one Ni(5), two equivalent Ni(3), and two equivalent Ni(6) atoms. In the fifth Ni site, Ni(5) is bonded in a distorted single-bond geometry to two equivalent Ca(2), two equivalent Ni(4), four equivalent Ni(6), and one H(1) atom. In the sixth Ni site, Ni(6) is bonded to two equivalent Ca(1), two equivalent Ca(2), two equivalent Ni(1), two equivalent Ni(4), two equivalent Ni(5), and two equivalent Ni(6) atoms to form NiCa4Ni8 cuboctahedra that share corners with four equivalent Ni(6)Ca4Ni8 cuboctahedra, corners with eight equivalent Ni(3)Ca4Ni8 cuboctahedra, corners with two equivalent H(1)Ca2Ni4 octahedra, edges with two equivalent Ni(6)Ca4Ni8 cuboctahedra, edges with four equivalent Ni(3)Ca4Ni8 cuboctahedra, faces with two equivalent Ni(3)Ca4Ni8 cuboctahedra, faces with four equivalent Ni(6)Ca4Ni8 cuboctahedra, and faces with two equivalent H(1)Ca2Ni4 octahedra. The corner-sharing octahedral tilt angles are 64°. H(1) is bonded to two equivalent Ca(1), one Ni(2), one Ni(5), and two equivalent Ni(1) atoms to form distorted HCa2Ni4 octahedra that share corners with four equivalent Ni(3)Ca4Ni8 cuboctahedra, corners with four equivalent Ni(6)Ca4Ni8 cuboctahedra, corners with two equivalent H(1)Ca2Ni4 octahedra, faces with four equivalent Ni(3)Ca4Ni8 cuboctahedra, and faces with four equivalent Ni(6)Ca4Ni8 cuboctahedra. The corner-sharing octahedral tilt angles are 9°.
Ca2Ni10H crystallizes in the orthorhombic Cmm2 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Ni(1), four equivalent Ni(3), four equivalent Ni(6), and two equivalent H(1) atoms. Both Ca(1)-Ni(1) bond lengths are 2.76 Å. All Ca(1)-Ni(3) bond lengths are 3.21 Å. All Ca(1)-Ni(6) bond lengths are 3.21 Å. Both Ca(1)-H(1) bond lengths are 2.48 Å. In the second Ca site, Ca(2) is bonded in a 18-coordinate geometry to two equivalent Ni(2), two equivalent Ni(5), four equivalent Ni(3), four equivalent Ni(6), and six equivalent Ni(4) atoms. Both Ca(2)-Ni(2) bond lengths are 3.17 Å. Both Ca(2)-Ni(5) bond lengths are 3.17 Å. All Ca(2)-Ni(3) bond lengths are 3.16 Å. All Ca(2)-Ni(6) bond lengths are 3.16 Å. There are four shorter (2.84 Å) and two longer (2.98 Å) Ca(2)-Ni(4) bond lengths. There are six inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a distorted single-bond geometry to one Ca(1), two equivalent Ni(3), two equivalent Ni(6), and one H(1) atom. Both Ni(1)-Ni(3) bond lengths are 2.43 Å. Both Ni(1)-Ni(6) bond lengths are 2.41 Å. The Ni(1)-H(1) bond length is 1.63 Å. In the second Ni site, Ni(2) is bonded in a single-bond geometry to two equivalent Ca(2), two equivalent Ni(4), four equivalent Ni(3), and one H(1) atom. Both Ni(2)-Ni(4) bond lengths are 2.42 Å. All Ni(2)-Ni(3) bond lengths are 2.51 Å. The Ni(2)-H(1) bond length is 1.74 Å. In the third Ni site, Ni(3) is bonded to two equivalent Ca(1), two equivalent Ca(2), two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(3), and two equivalent Ni(4) atoms to form NiCa4Ni8 cuboctahedra that share corners with four equivalent Ni(3)Ca4Ni8 cuboctahedra, corners with eight equivalent Ni(6)Ca4Ni8 cuboctahedra, corners with two equivalent H(1)Ca2Ni4 octahedra, edges with two equivalent Ni(3)Ca4Ni8 cuboctahedra, edges with four equivalent Ni(6)Ca4Ni8 cuboctahedra, faces with two equivalent Ni(6)Ca4Ni8 cuboctahedra, faces with four equivalent Ni(3)Ca4Ni8 cuboctahedra, and faces with two equivalent H(1)Ca2Ni4 octahedra. The corner-sharing octahedral tilt angles are 70°. Both Ni(3)-Ni(3) bond lengths are 2.47 Å. Both Ni(3)-Ni(4) bond lengths are 2.41 Å. In the fourth Ni site, Ni(4) is bonded in a 9-coordinate geometry to three equivalent Ca(2), one Ni(2), one Ni(5), two equivalent Ni(3), and two equivalent Ni(6) atoms. The Ni(4)-Ni(5) bond length is 2.43 Å. Both Ni(4)-Ni(6) bond lengths are 2.41 Å. In the fifth Ni site, Ni(5) is bonded in a distorted single-bond geometry to two equivalent Ca(2), two equivalent Ni(4), four equivalent Ni(6), and one H(1) atom. All Ni(5)-Ni(6) bond lengths are 2.52 Å. The Ni(5)-H(1) bond length is 2.11 Å. In the sixth Ni site, Ni(6) is bonded to two equivalent Ca(1), two equivalent Ca(2), two equivalent Ni(1), two equivalent Ni(4), two equivalent Ni(5), and two equivalent Ni(6) atoms to form NiCa4Ni8 cuboctahedra that share corners with four equivalent Ni(6)Ca4Ni8 cuboctahedra, corners with eight equivalent Ni(3)Ca4Ni8 cuboctahedra, corners with two equivalent H(1)Ca2Ni4 octahedra, edges with two equivalent Ni(6)Ca4Ni8 cuboctahedra, edges with four equivalent Ni(3)Ca4Ni8 cuboctahedra, faces with two equivalent Ni(3)Ca4Ni8 cuboctahedra, faces with four equivalent Ni(6)Ca4Ni8 cuboctahedra, and faces with two equivalent H(1)Ca2Ni4 octahedra. The corner-sharing octahedral tilt angles are 64°. Both Ni(6)-Ni(6) bond lengths are 2.47 Å. H(1) is bonded to two equivalent Ca(1), one Ni(2), one Ni(5), and two equivalent Ni(1) atoms to form distorted HCa2Ni4 octahedra that share corners with four equivalent Ni(3)Ca4Ni8 cuboctahedra, corners with four equivalent Ni(6)Ca4Ni8 cuboctahedra, corners with two equivalent H(1)Ca2Ni4 octahedra, faces with four equivalent Ni(3)Ca4Ni8 cuboctahedra, and faces with four equivalent Ni(6)Ca4Ni8 cuboctahedra. The corner-sharing octahedral tilt angles are 9°.