DOE OSTI2020
AlP3(NCl3)3 is beta Np structured and crystallizes in the orthorhombic Pmn2_1 space group. The structure is zero-dimensional and consists of four AlP3(NCl3)3 clusters. In two of the AlP3(NCl3)3 clusters, Al3+ is bonded to one N3- and three Cl1- atoms to form AlNCl3 tetrahedra that share corners with two equivalent PN2Cl2 tetrahedra. The Al–N bond length is 2.02 Å. There are one shorter (2.13 Å) and two longer (2.14 Å) Al–Cl bond lengths. There are two inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to two equivalent N3- and two Cl1- atoms to form corner-sharing PN2Cl2 tetrahedra. Both P–N bond lengths are 1.59 Å. There are one shorter (1.99 Å) and one longer (2.02 Å) P–Cl bond lengths. In the second P5+ site, P5+ is bonded to two N3- and two Cl1- atoms to form PN2Cl2 tetrahedra that share a cornercorner with one AlNCl3 tetrahedra and corners with two PN2Cl2 tetrahedra. There is one shorter (1.58 Å) and one longer (1.67 Å) P–N bond length. There is one shorter (1.98 Å) and one longer (2.01 Å) P–Cl bond length. There are two inequivalent N3- sites. In the first N3- site, N3- is bonded in a bent 120 degrees geometry to two P5+ atoms. In the second N3- site, N3- is bonded in a trigonal planar geometry to one Al3+ and two equivalent P5+ atoms. There are six inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ atom. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ atom. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ atom. In the fourth Cl1- site, Cl1- is bonded in a single-bond geometry to one Al3+ atom. In the fifth Cl1- site, Cl1- is bonded in a single-bond geometry to one Al3+ atom. In the sixth Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ atom. In two of the AlP3(NCl3)3 clusters, Al3+ is bonded to one N3- and three Cl1- atoms to form AlNCl3 tetrahedra that share corners with two equivalent PN2Cl2 tetrahedra. The Al–N bond length is 2.03 Å. There are two shorter (2.13 Å) and one longer (2.14 Å) Al–Cl bond lengths. There are two inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to two equivalent N3- and two Cl1- atoms to form corner-sharing PN2Cl2 tetrahedra. Both P–N bond lengths are 1.59 Å. Both P–Cl bond lengths are 2.01 Å. In the second P5+ site, P5+ is bonded to two N3- and two Cl1- atoms to form PN2Cl2 tetrahedra that share a cornercorner with one AlNCl3 tetrahedra and corners with two PN2Cl2 tetrahedra. There is one shorter (1.58 Å) and one longer (1.67 Å) P–N bond length. There is one shorter (1.99 Å) and one longer (2.00 Å) P–Cl bond length. There are two inequivalent N3- sites. In the first N3- site, N3- is bonded in a trigonal planar geometry to one Al3+ and two equivalent P5+ atoms. In the second N3- site, N3- is bonded in a bent 120 degrees geometry to two P5+ atoms. There are six inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ atom. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ atom. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one Al3+ atom. In the fourth Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ atom. In the fifth Cl1- site, Cl1- is bonded in a single-bond geometry to one P5+ atom. In the sixth Cl1- site, Cl1- is bonded in a single-bond geometry to one Al3+ atom.