Three new chalcogenophosphates, 1D-KInP 2 Se 6 ( I ), 1D-NaCrP 2 S 6 ( II ) and 3D-NaCrP 2 S 6 ( III ), have been synthesized and their structure determined from single crystal diffraction analysis. ( I ) and ( II ) crystallize in the monoclinic system (space group P2 1 /n, No. 14) with cell parameters a =7.5112(11), b =6.4861(5), c =22.789(2) A and β =98.912(16)° ( V =1096.9(2) A 3 ), Z =4 and R / Rw ( F 2 )=0.0234/0.0387 (for 900 observed reflections and 92 refined parameters) for ( I ) and a =7.0279(5), b =5.8797(2), c =21.2578(14) A and β =92.110(3)° ( V =877.82(9) A 3 ), Z =4 and R / Rw ( F 2 )=0.0572/0.1151 (for 1455 observed reflections and 92 refined parameters) for ( II ). Both materials exhibit 1 / ∞ [MP 2 Q 6 ] − chains built upon [MQ 6 ] octahedra (M=In, Cr; Q=Se, S) sharing edges to define 1 / ∞ [MQ 4 ] 5− zigzag fibers which are capped by tetradentate ethane-like [P 2 Q 6 ] groups. ( III ) crystallizes in the orthorhombic system (space group Fdd2, No. 43) with cell parameters a =10.9742(7), b =7.9828(6), c =20.8590(19) A ( V =1827.3(4) A 3 ), Z =8 and R / Rw =0.0184/0.0378 (for 967 observed reflections and 47 refined parameters), and displays a three-dimensional framework arrangement. Its structure is similar to that of TiP 2 S 6 where titanium atoms are substituted for the chromium, the sodium atoms being inserted in the empty tunnels to ensure the charge balance. The exfoliation properties of 1D-NaCrP 2 S 6 in polar solvents are reported.