Ca4PbN4 crystallizes in the triclinic P-1 space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(1), one N(2), one N(3), and one N(4) atom to form distorted CaN4 trigonal pyramids that share  a cornercorner with one Ca(3)N5 square pyramid, corners with three equivalent Ca(4)N5 square pyramids, corners with four equivalent Pb(1)N4 tetrahedra,  an edgeedge with one Ca(4)N5 square pyramid, and edges with two equivalent Ca(3)N5 square pyramids. In the second Ca site, Ca(2) is bonded in a 4-coordinate 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 CaN5 square pyramids that share corners with three equivalent Ca(4)N5 square pyramids, corners with three equivalent Pb(1)N4 tetrahedra,  a cornercorner with one Ca(1)N4 trigonal pyramid, edges with two equivalent Ca(3)N5 square pyramids, edges with three equivalent Ca(4)N5 square pyramids,  an edgeedge with one Pb(1)N4 tetrahedra, and edges with two equivalent Ca(1)N4 trigonal pyramids. In the fourth Ca site, Ca(4) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form CaN5 square pyramids that share corners with three equivalent Ca(3)N5 square pyramids,  a cornercorner with one Pb(1)N4 tetrahedra, corners with three equivalent Ca(1)N4 trigonal pyramids, edges with two equivalent Ca(4)N5 square pyramids, edges with three equivalent Ca(3)N5 square pyramids, edges with two equivalent Pb(1)N4 tetrahedra, and  an edgeedge with one Ca(1)N4 trigonal pyramid. Pb(1) is bonded to one N(1), one N(2), one N(3), and one N(4) atom to form distorted PbN4 tetrahedra that share  a cornercorner with one Ca(4)N5 square pyramid, corners with three equivalent Ca(3)N5 square pyramids, corners with four equivalent Ca(1)N4 trigonal pyramids,  an edgeedge with one Ca(3)N5 square pyramid, and edges with two equivalent Ca(4)N5 square pyramids. 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 Pb(1) atom to form NCa5Pb octahedra that share corners with two equivalent N(3)Ca5Pb octahedra, corners with two equivalent N(4)Ca5Pb octahedra, corners with two equivalent N(2)Ca3Pb tetrahedra, edges with two equivalent N(1)Ca5Pb octahedra, edges with two equivalent N(3)Ca5Pb octahedra, and edges with four equivalent N(4)Ca5Pb octahedra. The corner-sharing octahedral tilt angles range from 6-13°. In the second N site, N(2) is bonded to one Ca(1), two equivalent Ca(2), and one Pb(1) atom to form NCa3Pb tetrahedra that share corners with two equivalent N(1)Ca5Pb octahedra, corners with two equivalent N(4)Ca5Pb octahedra, corners with six equivalent N(3)Ca5Pb octahedra, and  an edgeedge with one N(2)Ca3Pb tetrahedra. The corner-sharing octahedral tilt angles range from 51-67°. 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 Pb(1) atom to form NCa5Pb octahedra that share corners with two equivalent N(1)Ca5Pb octahedra, corners with six equivalent N(2)Ca3Pb tetrahedra,  an edgeedge with one N(3)Ca5Pb octahedra, edges with two equivalent N(1)Ca5Pb octahedra, and edges with three equivalent N(4)Ca5Pb octahedra. The corner-sharing octahedral tilt angles range from 6-9°. In the fourth N site, N(4) is bonded to one Ca(1), two equivalent Ca(3), two equivalent Ca(4), and one Pb(1) atom to form NCa5Pb octahedra that share corners with two equivalent N(1)Ca5Pb octahedra, corners with two equivalent N(2)Ca3Pb tetrahedra, edges with two equivalent N(4)Ca5Pb octahedra, edges with three equivalent N(3)Ca5Pb octahedra, and edges with four equivalent N(1)Ca5Pb octahedra. The corner-sharing octahedral tilt angles range from 8-13°.
Ca4PbN4 crystallizes in the triclinic P-1 space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(1), one N(2), one N(3), and one N(4) atom to form distorted CaN4 trigonal pyramids that share  a cornercorner with one Ca(3)N5 square pyramid, corners with three equivalent Ca(4)N5 square pyramids, corners with four equivalent Pb(1)N4 tetrahedra,  an edgeedge with one Ca(4)N5 square pyramid, and edges with two equivalent Ca(3)N5 square pyramids. The Ca(1)-N(1) bond length is 2.45 Å. The Ca(1)-N(2) bond length is 2.42 Å. The Ca(1)-N(3) bond length is 2.34 Å. The Ca(1)-N(4) bond length is 2.42 Å. In the second Ca site, Ca(2) is bonded in a 4-coordinate geometry to two equivalent N(2) and two equivalent N(3) atoms. Both Ca(2)-N(2) bond lengths are 2.38 Å. There is one shorter (2.48 Å) and one longer (2.49 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 CaN5 square pyramids that share corners with three equivalent Ca(4)N5 square pyramids, corners with three equivalent Pb(1)N4 tetrahedra,  a cornercorner with one Ca(1)N4 trigonal pyramid, edges with two equivalent Ca(3)N5 square pyramids, edges with three equivalent Ca(4)N5 square pyramids,  an edgeedge with one Pb(1)N4 tetrahedra, and edges with two equivalent Ca(1)N4 trigonal pyramids. The Ca(3)-N(3) bond length is 2.57 Å. There is one shorter (2.43 Å) and one longer (2.52 Å) Ca(3)-N(1) bond length. There is one shorter (2.37 Å) and one longer (2.64 Å) Ca(3)-N(4) bond length. In the fourth Ca site, Ca(4) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form CaN5 square pyramids that share corners with three equivalent Ca(3)N5 square pyramids,  a cornercorner with one Pb(1)N4 tetrahedra, corners with three equivalent Ca(1)N4 trigonal pyramids, edges with two equivalent Ca(4)N5 square pyramids, edges with three equivalent Ca(3)N5 square pyramids, edges with two equivalent Pb(1)N4 tetrahedra, and  an edgeedge with one Ca(1)N4 trigonal pyramid. The Ca(4)-N(3) bond length is 2.55 Å. Both Ca(4)-N(1) bond lengths are 2.54 Å. There is one shorter (2.43 Å) and one longer (2.60 Å) Ca(4)-N(4) bond length. Pb(1) is bonded to one N(1), one N(2), one N(3), and one N(4) atom to form distorted PbN4 tetrahedra that share  a cornercorner with one Ca(4)N5 square pyramid, corners with three equivalent Ca(3)N5 square pyramids, corners with four equivalent Ca(1)N4 trigonal pyramids,  an edgeedge with one Ca(3)N5 square pyramid, and edges with two equivalent Ca(4)N5 square pyramids. The Pb(1)-N(1) bond length is 2.28 Å. The Pb(1)-N(2) bond length is 2.17 Å. The Pb(1)-N(3) bond length is 2.28 Å. The Pb(1)-N(4) bond length is 2.27 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 Pb(1) atom to form NCa5Pb octahedra that share corners with two equivalent N(3)Ca5Pb octahedra, corners with two equivalent N(4)Ca5Pb octahedra, corners with two equivalent N(2)Ca3Pb tetrahedra, edges with two equivalent N(1)Ca5Pb octahedra, edges with two equivalent N(3)Ca5Pb octahedra, and edges with four equivalent N(4)Ca5Pb octahedra. The corner-sharing octahedral tilt angles range from 6-13°. In the second N site, N(2) is bonded to one Ca(1), two equivalent Ca(2), and one Pb(1) atom to form NCa3Pb tetrahedra that share corners with two equivalent N(1)Ca5Pb octahedra, corners with two equivalent N(4)Ca5Pb octahedra, corners with six equivalent N(3)Ca5Pb octahedra, and  an edgeedge with one N(2)Ca3Pb tetrahedra. The corner-sharing octahedral tilt angles range from 51-67°. 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 Pb(1) atom to form NCa5Pb octahedra that share corners with two equivalent N(1)Ca5Pb octahedra, corners with six equivalent N(2)Ca3Pb tetrahedra,  an edgeedge with one N(3)Ca5Pb octahedra, edges with two equivalent N(1)Ca5Pb octahedra, and edges with three equivalent N(4)Ca5Pb octahedra. The corner-sharing octahedral tilt angles range from 6-9°. In the fourth N site, N(4) is bonded to one Ca(1), two equivalent Ca(3), two equivalent Ca(4), and one Pb(1) atom to form NCa5Pb octahedra that share corners with two equivalent N(1)Ca5Pb octahedra, corners with two equivalent N(2)Ca3Pb tetrahedra, edges with two equivalent N(4)Ca5Pb octahedra, edges with three equivalent N(3)Ca5Pb octahedra, and edges with four equivalent N(1)Ca5Pb octahedra. The corner-sharing octahedral tilt angles range from 8-13°.