Ca4ReN4 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 distorted rectangular see-saw-like geometry to one N(1), one N(2), one N(3), and one N(4) atom. 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 square pyramids. In the fourth Ca site, Ca(4) is bonded in a 6-coordinate geometry to one N(2), one N(3), two equivalent N(1), and two equivalent N(4) atoms. Re(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 Re(1) atom to form a mixture of distorted corner and edge-sharing NCa5Re octahedra. The corner-sharing octahedral tilt angles range from 11-19°. In the second N site, N(2) is bonded in a 5-coordinate geometry to one Ca(1), one Ca(4), two equivalent Ca(2), and one Re(1) atom. 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 Re(1) atom to form a mixture of corner and edge-sharing NCa5Re octahedra. The corner-sharing octahedral tilt angles range from 11-19°. In the fourth N site, N(4) is bonded in a 6-coordinate geometry to one Ca(1), two equivalent Ca(3), two equivalent Ca(4), and one Re(1) atom.
Ca4ReN4 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 distorted rectangular see-saw-like geometry to one N(1), one N(2), one N(3), and one N(4) atom. The Ca(1)-N(1) bond length is 2.47 Å. The Ca(1)-N(2) bond length is 2.61 Å. The Ca(1)-N(3) bond length is 2.40 Å. The Ca(1)-N(4) bond length is 2.45 Å. 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 (2.46 Å) and one longer (2.49 Å) Ca(2)-N(2) bond length. There is one shorter (2.42 Å) and one longer (2.46 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 square pyramids. The Ca(3)-N(3) bond length is 2.37 Å. There is one shorter (2.43 Å) and one longer (2.48 Å) Ca(3)-N(1) bond length. There is one shorter (2.57 Å) and one longer (2.60 Å) Ca(3)-N(4) bond length. In the fourth Ca site, Ca(4) is bonded in a 6-coordinate geometry to one N(2), one N(3), two equivalent N(1), and two equivalent N(4) atoms. The Ca(4)-N(2) bond length is 2.59 Å. The Ca(4)-N(3) bond length is 2.36 Å. There is one shorter (2.58 Å) and one longer (2.61 Å) Ca(4)-N(1) bond length. There is one shorter (2.50 Å) and one longer (2.89 Å) Ca(4)-N(4) bond length. Re(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 Re(1)-N(1) bond length is 1.94 Å. The Re(1)-N(2) bond length is 1.92 Å. The Re(1)-N(3) bond length is 2.09 Å. The Re(1)-N(4) bond length is 1.91 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 Re(1) atom to form a mixture of distorted corner and edge-sharing NCa5Re octahedra. The corner-sharing octahedral tilt angles range from 11-19°. In the second N site, N(2) is bonded in a 5-coordinate geometry to one Ca(1), one Ca(4), two equivalent Ca(2), and one Re(1) atom. 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 Re(1) atom to form a mixture of corner and edge-sharing NCa5Re octahedra. The corner-sharing octahedral tilt angles range from 11-19°. In the fourth N site, N(4) is bonded in a 6-coordinate geometry to one Ca(1), two equivalent Ca(3), two equivalent Ca(4), and one Re(1) atom.