Reactions of 18-crown-6(18-C-6) with Na2[M(mnt)2][M=Cu, Ni; mnt=1, 2- dicanoethene-1, 2-dithiolate, C2S2(CN)^2^-~2] were studied and the novel complexes {[Na(18-C-6)][Na(18-C-6)(H2O)]}[Cu(mnt)2](1) and [Na (18-C-6)(H2O)]2[Ni(mnt)2].(18-C-6)(2) were characterized by elemental analysis, IR and X-ray diffraction analysis. 1 and 2 belong to triclinic, space group P1 with cell dimensions: 1, a=1.22697(19) nm, b=1.22780(19) nm, c=1.5665(3) nm, α=95.083(3)°, β=101.534(3)°, Υ =91.007(3)°, V=2.3016(6) nm^3, Z=2, Dcalcd=1.350 g/cm^3, F(000)=976, R1=0.0726, wR2=0.1843 and 2, a=1.11620(17) nm, b=1.22054(18) nm, c=1. 27939(18) nm, α=111.647(2)°, β=29.792(3)°, Υ=103.201(2)°, V=2. 5461(4) nm^3, Z=1, Dcalcd=1.304 g/cm^3, F(000)=642, R1=0.0459, wR2=0. 1003. 1 Displays a one-dimensional chain of [Na(18-C-6)]^+ complex cations and [Cu(mnt)2]^2^- complex anion bridged by Na-N interactions. The complex cation [Na-(18-C-6)(H2O)]^+ serves as a balancing charge in crystal. In 2. two [Na(18-C-6)(H2O)]^+ complex cations and a [Ni (mnt)2]^2^- complex anion form a stable neutral complex through Na-N binding.

Key words: CROWN ETHER, CRYSTAL STRUCTURE, COPPER COMPLEX, NICKEL COMPLEX, BUTANENITRILE P