Ca3Ni3N5 crystallizes in the triclinic P-1 space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 4-coordinate geometry to one N(1), one N(3), one N(4), and two equivalent N(2) atoms. In the second Ca site, Ca(2) is bonded in a 5-coordinate geometry to one N(3), one N(4), two equivalent N(1), and two equivalent N(5) atoms. In the third Ca site, Ca(3) is bonded in a 5-coordinate geometry to one N(1), one N(2), one N(4), and two equivalent N(3) atoms. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one N(1), one N(5), and two equivalent N(3) atoms to form a mixture of edge and corner-sharing NiN4 tetrahedra. In the second Ni site, Ni(2) is bonded to one N(1), one N(2), and two equivalent N(4) atoms to form a mixture of distorted edge and corner-sharing NiN4 tetrahedra. In the third Ni site, Ni(3) is bonded to one N(1), one N(2), one N(4), and one N(5) atom to form a mixture of edge and corner-sharing NiN4 tetrahedra. There are five inequivalent N sites. In the first N site, N(1) is bonded in a 7-coordinate geometry to one Ca(1), one Ca(3), two equivalent Ca(2), one Ni(1), one Ni(2), and one Ni(3) atom. In the second N site, N(2) is bonded in a 5-coordinate geometry to one Ca(3), two equivalent Ca(1), one Ni(2), and one Ni(3) atom. In the third N site, N(3) is bonded to one Ca(1), one Ca(2), two equivalent Ca(3), and two equivalent Ni(1) atoms to form edge-sharing NCa4Ni2 octahedra. In the fourth N site, N(4) is bonded in a 6-coordinate geometry to one Ca(1), one Ca(2), one Ca(3), one Ni(3), and two equivalent Ni(2) atoms. In the fifth N site, N(5) is bonded in a 4-coordinate geometry to two equivalent Ca(2), one Ni(1), and one Ni(3) atom.
Ca3Ni3N5 crystallizes in the triclinic P-1 space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 4-coordinate geometry to one N(1), one N(3), one N(4), and two equivalent N(2) atoms. The Ca(1)-N(1) bond length is 2.94 Å. The Ca(1)-N(3) bond length is 2.43 Å. The Ca(1)-N(4) bond length is 2.48 Å. There is one shorter (2.33 Å) and one longer (2.52 Å) Ca(1)-N(2) bond length. In the second Ca site, Ca(2) is bonded in a 5-coordinate geometry to one N(3), one N(4), two equivalent N(1), and two equivalent N(5) atoms. The Ca(2)-N(3) bond length is 2.43 Å. The Ca(2)-N(4) bond length is 2.45 Å. There is one shorter (2.54 Å) and one longer (2.91 Å) Ca(2)-N(1) bond length. There is one shorter (2.39 Å) and one longer (2.49 Å) Ca(2)-N(5) bond length. In the third Ca site, Ca(3) is bonded in a 5-coordinate geometry to one N(1), one N(2), one N(4), and two equivalent N(3) atoms. The Ca(3)-N(1) bond length is 2.51 Å. The Ca(3)-N(2) bond length is 2.42 Å. The Ca(3)-N(4) bond length is 2.57 Å. There is one shorter (2.34 Å) and one longer (2.57 Å) Ca(3)-N(3) bond length. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one N(1), one N(5), and two equivalent N(3) atoms to form a mixture of edge and corner-sharing NiN4 tetrahedra. The Ni(1)-N(1) bond length is 1.86 Å. The Ni(1)-N(5) bond length is 1.82 Å. There is one shorter (1.90 Å) and one longer (1.92 Å) Ni(1)-N(3) bond length. In the second Ni site, Ni(2) is bonded to one N(1), one N(2), and two equivalent N(4) atoms to form a mixture of distorted edge and corner-sharing NiN4 tetrahedra. The Ni(2)-N(1) bond length is 1.91 Å. The Ni(2)-N(2) bond length is 1.88 Å. There is one shorter (1.88 Å) and one longer (1.98 Å) Ni(2)-N(4) bond length. In the third Ni site, Ni(3) is bonded to one N(1), one N(2), one N(4), and one N(5) atom to form a mixture of edge and corner-sharing NiN4 tetrahedra. The Ni(3)-N(1) bond length is 1.89 Å. The Ni(3)-N(2) bond length is 1.94 Å. The Ni(3)-N(4) bond length is 1.93 Å. The Ni(3)-N(5) bond length is 1.87 Å. There are five inequivalent N sites. In the first N site, N(1) is bonded in a 7-coordinate geometry to one Ca(1), one Ca(3), two equivalent Ca(2), one Ni(1), one Ni(2), and one Ni(3) atom. In the second N site, N(2) is bonded in a 5-coordinate geometry to one Ca(3), two equivalent Ca(1), one Ni(2), and one Ni(3) atom. In the third N site, N(3) is bonded to one Ca(1), one Ca(2), two equivalent Ca(3), and two equivalent Ni(1) atoms to form edge-sharing NCa4Ni2 octahedra. In the fourth N site, N(4) is bonded in a 6-coordinate geometry to one Ca(1), one Ca(2), one Ca(3), one Ni(3), and two equivalent Ni(2) atoms. In the fifth N site, N(5) is bonded in a 4-coordinate geometry to two equivalent Ca(2), one Ni(1), and one Ni(3) atom.