The new compounds (\mathrm{NaCuTiS}{3}) and (\mathrm{NaCuZr}{3}(Q=\mathrm{S}, \mathrm{Se}, \mathrm{Te})) have been synthesized through reaction of the elements with a (\mathrm{Na}{2} Q{n}) flux. The compounds (\mathrm{NaCuTiS}{3}, \mathrm{NaCuZrSe}{3}), and (\mathrm{NaCuZrTe}{3}) crystallize in space group (D{2 h}^{16})-Pnma of the orthorhombic system with four formula units in cells of dimensions (a=12.738(10) . b=3.554(3), c=9.529(8) \AA) for (\mathrm{NaCuTiS}{3} ; a=13.392(5), b=3.833(1), c=10.250(4)) (\AA ฬ) for (\mathrm{NaCuZrSe}{3} ; a=14.34(4), b=4.06(1), c=10.93(3) \AA \AA) for (\mathrm{NaCuZrTe}{3}(T=113 \mathrm{~K}) . \mathrm{NaCuZrS}{3}) crystallizes in space group (D_{2 k}^{17} \mathrm{Cmcm}) of the orthorhombic system with four formula units in a cell of dimensions (a=3.688(1), b=12.838(5), c=9.726(3) \AA). The structures of all four compounds have been determined by single-crystal X-ray methods. The structures are composed of ({ }{2}^{2}\left[\mathrm{Cu} M Q{3}^{-}\right](M=) Ti, (Q=\mathrm{S} ; M=\mathrm{Zr}, Q=\mathrm{S}, \mathrm{Se}, \mathrm{Te}) ) layers separated by (\mathrm{Na}^{+})cations. The (\mathrm{Cu}) atoms are letrahedrally coordinated and the (M) atoms are octahedrally coordinated. (\mathrm{NaCuZrS}{3}) is isostructural with the recently reported series of compounds (\mathrm{KCuZr}{3}(Q=\mathrm{S}, \mathrm{Se}, \mathrm{Te}) . \mathrm{NaCuTiS}{ }{3}, \mathrm{NaCuZrSe}{3}), and (\mathrm{NaCuZrTe}{3}) represent a new structure type with the ({ }{x}^{2}\left[\mathrm{CuMQ} Q_{3}^{-}\right])layer being composed of alternating pairs of (\mathrm{Cu}{4}) Ietrathedrat and (M Q{4}) octahedrat in the ([001]) direction. The (\mathrm{Na}^{\prime}) cations are coordinated by seven chalcogen atoms in a monocapped trigonal prismatic arrangement. () 1993 Academic Press, Inc.