Two Hitherto Unknown Lithium Holmium(III) Ortho ‐Thiophosphates(V): Li 9 Ho 2 [PS 4 ] 5 and Li 15 Ho 7 [PS 4 ] 12

Abstract The two hitherto unknown lithium holmium(III) o rtho ‐thiophosphates(V) Li 9 Ho 2 [PS 4 ] 5 and Li 15 Ho 7 [PS 4 ] 12 crystallize in the monoclinic space group C 2/ c with the lattice parameters a =1489.43(9) pm, b =979.84(6) pm, c =2051.68(12) pm, β =96.221(3)° for Li 9 Ho 2 [PS 4 ] 5 ( Z =4) and a =2826.73(16) pm, b =1003.25(6) pm, c =3361.46(19) pm, β =113.992(3)° for Li 15 Ho 7 [PS 4 ] 12 ( Z =5). While Li 9 Ho 2 [PS 4 ] 5 extends the Li 9 RE 2 [PS 4 ] 5 series, Li 15 Ho 7 [PS 4 ] 12 can be regarded as a cation‐distribution variant of the Li 6 RE 3 [PS 4 ] 5 series ( Z =12). Both structures feature characteristic [HoS 8 ] 13− polyhedra ( d (Ho 3+ −S 2− )=275–314 pm) and [PS 4 ] 3− tetrahedra ( d (P 5+ −S 2− )=202–207 pm), but Li 15 Ho 7 [PS 4 ] 12 exhibits one Ho 3+ position, which is mixed occupied with Li + and settles with C.N.=6+2. The coordination numbers of all other Li + cations range from four to six in both new compounds with Li + −S 2− distances from 238 to 317 pm.