Ca4IrN4 crystallizes in the triclinic P-1 space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 5-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 distorted see-saw-like geometry to two equivalent N(2) and two equivalent N(3) atoms. In the third Ca site, Ca(3) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form distorted edge-sharing CaN5 trigonal bipyramids. In the fourth Ca site, Ca(4) is bonded in a 5-coordinate geometry to one N(2), one N(3), one N(4), and two equivalent N(1) atoms. Ir(1) is bonded in a distorted see-saw-like geometry to one N(1), one N(2), one N(3), and one N(4) atom. There are four inequivalent N sites. In the first N site, N(1) is bonded to one Ca(1), two equivalent Ca(3), two equivalent Ca(4), and one Ir(1) atom to form a mixture of edge, face, and corner-sharing NCa5Ir octahedra. The corner-sharing octahedral tilt angles range from 11-67°. In the second N site, N(2) is bonded to one Ca(4), two equivalent Ca(1), two equivalent Ca(2), and one Ir(1) atom to form a mixture of distorted edge, face, and corner-sharing NCa5Ir octahedra. The corner-sharing octahedral tilt angles range from 28-67°. In the third N site, N(3) is bonded to one Ca(1), one Ca(3), one Ca(4), two equivalent Ca(2), and one Ir(1) atom to form a mixture of edge, face, and corner-sharing NCa5Ir octahedra. The corner-sharing octahedral tilt angles range from 11-61°. In the fourth N site, N(4) is bonded in a 5-coordinate geometry to one Ca(1), one Ca(4), two equivalent Ca(3), and one Ir(1) atom.
Ca4IrN4 crystallizes in the triclinic P-1 space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 5-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 2.37 Å. The Ca(1)-N(3) bond length is 2.39 Å. The Ca(1)-N(4) bond length is 2.43 Å. There is one shorter (2.50 Å) and one longer (2.75 Å) Ca(1)-N(2) bond length. In the second Ca site, Ca(2) is bonded in a distorted see-saw-like geometry to two equivalent N(2) and two equivalent N(3) atoms. There is one shorter (2.37 Å) and one longer (2.51 Å) Ca(2)-N(2) bond length. There is one shorter (2.46 Å) and one longer (2.48 Å) Ca(2)-N(3) bond length. In the third Ca site, Ca(3) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form distorted edge-sharing CaN5 trigonal bipyramids. The Ca(3)-N(3) bond length is 2.38 Å. There is one shorter (2.37 Å) and one longer (2.40 Å) Ca(3)-N(1) bond length. There is one shorter (2.56 Å) and one longer (2.70 Å) Ca(3)-N(4) bond length. In the fourth Ca site, Ca(4) is bonded in a 5-coordinate geometry to one N(2), one N(3), one N(4), and two equivalent N(1) atoms. The Ca(4)-N(2) bond length is 2.47 Å. The Ca(4)-N(3) bond length is 2.42 Å. The Ca(4)-N(4) bond length is 2.53 Å. There is one shorter (2.54 Å) and one longer (2.55 Å) Ca(4)-N(1) bond length. Ir(1) is bonded in a distorted see-saw-like geometry to one N(1), one N(2), one N(3), and one N(4) atom. The Ir(1)-N(1) bond length is 2.08 Å. The Ir(1)-N(2) bond length is 1.99 Å. The Ir(1)-N(3) bond length is 2.06 Å. The Ir(1)-N(4) bond length is 1.92 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded to one Ca(1), two equivalent Ca(3), two equivalent Ca(4), and one Ir(1) atom to form a mixture of edge, face, and corner-sharing NCa5Ir octahedra. The corner-sharing octahedral tilt angles range from 11-67°. In the second N site, N(2) is bonded to one Ca(4), two equivalent Ca(1), two equivalent Ca(2), and one Ir(1) atom to form a mixture of distorted edge, face, and corner-sharing NCa5Ir octahedra. The corner-sharing octahedral tilt angles range from 28-67°. In the third N site, N(3) is bonded to one Ca(1), one Ca(3), one Ca(4), two equivalent Ca(2), and one Ir(1) atom to form a mixture of edge, face, and corner-sharing NCa5Ir octahedra. The corner-sharing octahedral tilt angles range from 11-61°. In the fourth N site, N(4) is bonded in a 5-coordinate geometry to one Ca(1), one Ca(4), two equivalent Ca(3), and one Ir(1) atom.