Ca2PN3 crystallizes in the orthorhombic Cmce space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent N(1), two equivalent N(2), and three equivalent N(3) atoms to form distorted CaN7 pentagonal bipyramids that share corners with four equivalent Ca(1)N7 pentagonal bipyramids,  a cornercorner with one P(1)N4 tetrahedra, edges with three equivalent Ca(1)N7 pentagonal bipyramids, and edges with four equivalent P(1)N4 tetrahedra. In the second Ca site, Ca(2) is bonded in a 5-coordinate geometry to two equivalent N(3) and three equivalent N(2) atoms. P(1) is bonded to one N(2), one N(3), and two equivalent N(1) atoms to form PN4 tetrahedra that share  a cornercorner with one Ca(1)N7 pentagonal bipyramid, corners with two equivalent P(1)N4 tetrahedra, and edges with four equivalent Ca(1)N7 pentagonal bipyramids. There are three inequivalent N sites. In the first N site, N(1) is bonded in a 4-coordinate geometry to two equivalent Ca(1) and two equivalent P(1) atoms. In the second N site, N(2) is bonded to two equivalent Ca(1), three equivalent Ca(2), and one P(1) atom to form a mixture of distorted corner and edge-sharing NCa5P octahedra. The corner-sharing octahedral tilt angles range from 16-56°. In the third N site, N(3) is bonded to two equivalent Ca(2), three equivalent Ca(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing NCa5P octahedra. The corner-sharing octahedral tilt angles range from 15-56°.
Ca2PN3 crystallizes in the orthorhombic Cmce space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent N(1), two equivalent N(2), and three equivalent N(3) atoms to form distorted CaN7 pentagonal bipyramids that share corners with four equivalent Ca(1)N7 pentagonal bipyramids,  a cornercorner with one P(1)N4 tetrahedra, edges with three equivalent Ca(1)N7 pentagonal bipyramids, and edges with four equivalent P(1)N4 tetrahedra. Both Ca(1)-N(1) bond lengths are 2.49 Å. There is one shorter (2.46 Å) and one longer (2.47 Å) Ca(1)-N(2) bond length. There is one shorter (2.52 Å) and two longer (2.62 Å) Ca(1)-N(3) bond lengths. In the second Ca site, Ca(2) is bonded in a 5-coordinate geometry to two equivalent N(3) and three equivalent N(2) atoms. There is one shorter (2.43 Å) and one longer (2.45 Å) Ca(2)-N(3) bond length. There is one shorter (2.48 Å) and two longer (2.62 Å) Ca(2)-N(2) bond lengths. P(1) is bonded to one N(2), one N(3), and two equivalent N(1) atoms to form PN4 tetrahedra that share  a cornercorner with one Ca(1)N7 pentagonal bipyramid, corners with two equivalent P(1)N4 tetrahedra, and edges with four equivalent Ca(1)N7 pentagonal bipyramids. The P(1)-N(2) bond length is 1.63 Å. The P(1)-N(3) bond length is 1.62 Å. Both P(1)-N(1) bond lengths are 1.67 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a 4-coordinate geometry to two equivalent Ca(1) and two equivalent P(1) atoms. In the second N site, N(2) is bonded to two equivalent Ca(1), three equivalent Ca(2), and one P(1) atom to form a mixture of distorted corner and edge-sharing NCa5P octahedra. The corner-sharing octahedral tilt angles range from 16-56°. In the third N site, N(3) is bonded to two equivalent Ca(2), three equivalent Ca(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing NCa5P octahedra. The corner-sharing octahedral tilt angles range from 15-56°.