The two hitherto unknown lithium holmium(III) ortho-thiophosphates(V) Li9Ho2[PS4]5 and Li15Ho7[PS4]12 crystallize in the monoclinic space group C2/c with lattice parameters a=1489.43(9) pm, b=979.84(6) c=2051.68(12) ?=96.221(3)° for (Z=4) a=2826.73(16) b=1003.25(6) c=3361.46(19) ?=113.992(3)° (Z=5). While extends Li9RE2[PS4]5 series, can be regarded as a cation-distribution variant of Li6RE3[PS...