Two novel copper selenite chlorides, K[Cu3O](SeO3)2Cl (I) and Na2[Cu7O2](SeO3)4Cl4 (II), have been synthesized by the CVT method. Their crystal structures have been solved by direct methods and refined by least-squares techniques. I is triclinic, space group Pforumla, a = 7.6821(5), b = 8.1179(5), c = 8.7836(6) Å, α = 113.193(3), β = 108.735(4), γ = 98.245(4)°, V = 453.32(5) Å3, R1 = 0.0481 for 1210 unique reflections with F ≥ 4σ(F); II is triclinic, space group Pforumla, a = 7.4362(6), b = 8.3361(7), c = 9.1343(11) Å, α = 110.277(6), β = 106.212(6), γ = 105.158(4)°, V = 467.94(8) Å3, R1 = 0.0265 for 2498 unique reflections with F ≥ 4σ(F). The structures of I and II can be described in terms of dimers of copper oxocentred tetrahedra. In I, two (OCu4)6+ tetrahedra share a common Cu···Cu edge to form the [O2Cu6]8+ dimer, whereas the structure of II is based upon two (OCu4)6+ tetrahedra linked together by one common Cu atom resulting in the formation of the [O2Cu7]10+ dimer. A comparison with related minerals and inorganic compounds is given.

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