Ca4RuN4 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 6-coordinate geometry to one Ru(1), one N(1), two equivalent N(2), and two equivalent N(3) atoms. In the second Ca site, Ca(2) is bonded in a 9-coordinate geometry to two equivalent N(1), two equivalent N(2), two equivalent N(4), and three equivalent N(3) atoms. In the third Ca site, Ca(3) is bonded in a 5-coordinate geometry to three equivalent Ru(1), one N(2), and one N(4) atom. In the fourth Ca site, Ca(4) is bonded in a 3-coordinate geometry to one N(2) and two equivalent N(1) atoms. Ru(1) is bonded in a 1-coordinate geometry to one Ca(1), three equivalent Ca(3), and one N(4) atom. There are four inequivalent N sites. In the first N site, N(4) is bonded in a 3-coordinate geometry to one Ca(3), two equivalent Ca(2), one Ru(1), and one N(1) atom. In the second N site, N(1) is bonded to one Ca(1), two equivalent Ca(2), two equivalent Ca(4), and one N(4) atom to form a mixture of edge and corner-sharing NCa5N octahedra. The corner-sharing octahedral tilt angles are 8°. In the third N site, N(2) is bonded in a 7-coordinate geometry to one Ca(3), one Ca(4), two equivalent Ca(1), two equivalent Ca(2), and one N(3) atom. In the fourth N site, N(3) is bonded to two equivalent Ca(1), three equivalent Ca(2), and one N(2) atom to form a mixture of edge and corner-sharing NCa5N octahedra. The corner-sharing octahedral tilt angles are 8°.
Ca4RuN4 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 6-coordinate geometry to one Ru(1), one N(1), two equivalent N(2), and two equivalent N(3) atoms. The Ca(1)-Ru(1) bond length is 2.88 Å. The Ca(1)-N(1) bond length is 2.35 Å. Both Ca(1)-N(2) bond lengths are 2.63 Å. Both Ca(1)-N(3) bond lengths are 2.42 Å. In the second Ca site, Ca(2) is bonded in a 9-coordinate geometry to two equivalent N(1), two equivalent N(2), two equivalent N(4), and three equivalent N(3) atoms. Both Ca(2)-N(1) bond lengths are 2.55 Å. Both Ca(2)-N(2) bond lengths are 2.77 Å. Both Ca(2)-N(4) bond lengths are 2.66 Å. There is one shorter (2.31 Å) and two longer (2.45 Å) Ca(2)-N(3) bond lengths. In the third Ca site, Ca(3) is bonded in a 5-coordinate geometry to three equivalent Ru(1), one N(2), and one N(4) atom. There is one shorter (2.92 Å) and two longer (3.03 Å) Ca(3)-Ru(1) bond lengths. The Ca(3)-N(2) bond length is 2.68 Å. The Ca(3)-N(4) bond length is 2.48 Å. In the fourth Ca site, Ca(4) is bonded in a 3-coordinate geometry to one N(2) and two equivalent N(1) atoms. The Ca(4)-N(2) bond length is 2.44 Å. Both Ca(4)-N(1) bond lengths are 2.48 Å. Ru(1) is bonded in a 1-coordinate geometry to one Ca(1), three equivalent Ca(3), and one N(4) atom. The Ru(1)-N(4) bond length is 1.92 Å. There are four inequivalent N sites. In the first N site, N(4) is bonded in a 3-coordinate geometry to one Ca(3), two equivalent Ca(2), one Ru(1), and one N(1) atom. The N(4)-N(1) bond length is 1.32 Å. In the second N site, N(1) is bonded to one Ca(1), two equivalent Ca(2), two equivalent Ca(4), and one N(4) atom to form a mixture of edge and corner-sharing NCa5N octahedra. The corner-sharing octahedral tilt angles are 8°. In the third N site, N(2) is bonded in a 7-coordinate geometry to one Ca(3), one Ca(4), two equivalent Ca(1), two equivalent Ca(2), and one N(3) atom. The N(2)-N(3) bond length is 1.36 Å. In the fourth N site, N(3) is bonded to two equivalent Ca(1), three equivalent Ca(2), and one N(2) atom to form a mixture of edge and corner-sharing NCa5N octahedra. The corner-sharing octahedral tilt angles are 8°.