Ca3Ga3N5 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 4-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 6-coordinate geometry to one N(1), one N(2), one N(4), one N(5), and two equivalent N(3) atoms. There are three inequivalent Ga sites. In the first Ga site, Ga(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 GaN4 tetrahedra. In the second Ga site, Ga(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 GaN4 tetrahedra. In the third Ga site, Ga(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 GaN4 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 Ga(1), one Ga(2), and one Ga(3) atom. In the second N site, N(2) is bonded to one Ca(3), two equivalent Ca(1), one Ga(2), and one Ga(3) atom to form distorted NCa3Ga2 trigonal bipyramids that share corners with four equivalent N(3)Ca4Ga2 octahedra and  an edgeedge with one N(2)Ca3Ga2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 40-71°. In the third N site, N(3) is bonded to one Ca(1), one Ca(2), two equivalent Ca(3), and two equivalent Ga(1) atoms to form distorted NCa4Ga2 octahedra that share corners with four equivalent N(2)Ca3Ga2 trigonal bipyramids and edges with two equivalent N(3)Ca4Ga2 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 Ga(3), and two equivalent Ga(2) atoms. In the fifth N site, N(5) is bonded in a 5-coordinate geometry to one Ca(3), two equivalent Ca(2), one Ga(1), and one Ga(3) atom.
Ca3Ga3N5 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 2.98 Å. The Ca(1)-N(3) bond length is 2.42 Å. The Ca(1)-N(4) bond length is 2.51 Å. There is one shorter (2.35 Å) and one longer (2.50 Å) Ca(1)-N(2) bond length. In the second Ca site, Ca(2) is bonded in a 4-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 2.45 Å. The Ca(2)-N(4) bond length is 2.53 Å. There is one shorter (2.82 Å) and one longer (3.07 Å) Ca(2)-N(1) bond length. There is one shorter (2.33 Å) and one longer (2.56 Å) Ca(2)-N(5) bond length. In the third Ca site, Ca(3) is bonded in a 6-coordinate geometry to one N(1), one N(2), one N(4), one N(5), and two equivalent N(3) atoms. The Ca(3)-N(1) bond length is 2.63 Å. The Ca(3)-N(2) bond length is 2.48 Å. The Ca(3)-N(4) bond length is 3.00 Å. The Ca(3)-N(5) bond length is 2.77 Å. There is one shorter (2.41 Å) and one longer (2.73 Å) Ca(3)-N(3) bond length. There are three inequivalent Ga sites. In the first Ga site, Ga(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 GaN4 tetrahedra. The Ga(1)-N(1) bond length is 1.95 Å. The Ga(1)-N(5) bond length is 1.92 Å. There is one shorter (2.00 Å) and one longer (2.04 Å) Ga(1)-N(3) bond length. In the second Ga site, Ga(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 GaN4 tetrahedra. The Ga(2)-N(1) bond length is 1.97 Å. The Ga(2)-N(2) bond length is 1.95 Å. There is one shorter (1.96 Å) and one longer (2.04 Å) Ga(2)-N(4) bond length. In the third Ga site, Ga(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 GaN4 tetrahedra. The Ga(3)-N(1) bond length is 1.99 Å. The Ga(3)-N(2) bond length is 2.03 Å. The Ga(3)-N(4) bond length is 2.01 Å. The Ga(3)-N(5) bond length is 1.93 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 Ga(1), one Ga(2), and one Ga(3) atom. In the second N site, N(2) is bonded to one Ca(3), two equivalent Ca(1), one Ga(2), and one Ga(3) atom to form distorted NCa3Ga2 trigonal bipyramids that share corners with four equivalent N(3)Ca4Ga2 octahedra and  an edgeedge with one N(2)Ca3Ga2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 40-71°. In the third N site, N(3) is bonded to one Ca(1), one Ca(2), two equivalent Ca(3), and two equivalent Ga(1) atoms to form distorted NCa4Ga2 octahedra that share corners with four equivalent N(2)Ca3Ga2 trigonal bipyramids and edges with two equivalent N(3)Ca4Ga2 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 Ga(3), and two equivalent Ga(2) atoms. In the fifth N site, N(5) is bonded in a 5-coordinate geometry to one Ca(3), two equivalent Ca(2), one Ga(1), and one Ga(3) atom.