Supra molecular assembly and structural transformation of d10-metal complexes containing (aza-15-crown-5)dithiocarbamate

The reaction of potassium (aza-15-crown-5)dithiocarbamate (KO4NCS2) and (Me2S)AuCl gave the dinuclear complex [Au(O4NCS2)](2), which underwent structuraL transformation upon heating to rearrange into the hexanudear complex [Au(O4NCS2)](6). Under similar reaction conditions, KO4NCS2 reacted with AgNO3 or [Cu(CH3CN)(4)] (2) to give the 1-D coordination polymer [Ag(O4NCS2)](n) (1) and the tetranudear compLex [Cu(O4NCS2)](4) (2), respectively. It is noted that upon heating a similar structural transformation process occurs from tetranudear complex 2 to the octanudear complex [Cu(O4NCS2)](8) (2'), connected by a weak Cu center dot center dot center dot S contact of 2.846 angstrom, and it has been isolated and corroborated by powder and single-crystal X-ray diffraction studies as well Moreover, a variety of MO4NCS2 salts (M = Li+, Na+, K+ and Rb+) were used to react with AgNO3 to construct a series of coordination architectures: [LiAg(O4NCS2)(2)(rH(2)O)(0.5)](2) (3), {Na[Ag(O4NCS2)(2)])(n), (4), {K[Ag(O4NCS2)(2)])(n) (5) and {Rb[Ag(O4NCS2)(2)])(n) (6). The smallest Li+ ion only coordinates with four oxygen atoms from the same azacrown ether ring and one H2O molecule, Leading to a 1-D hydrogen-bonded chain with another azacrown ether ring for complex 3. The Larger Na+ ion coordinates with seven oxygen atoms from two different crown ether rings, Leading to a 1-D chain for complex 4. However, the Largest K+ and Rb+ ions constitute a 1-D framework, except that each metal ion coordinates with eight oxygen atoms from two different crown ether rings, featuring a 1-D helical chain for complexes 5 and 6. Hence, the different sizes of alkaline metal ions exert a dramatic effect on the structuraL motifs of complexes 3-6. Remarkably, the dithiocarbamate moieties adopt mu(2)-bridging ([Au(O4NCS2)](2) and [Au(O4NCS2)](6)), mu(3)- and mu(4)-bridging (1-2) and cheLate forms (3-6) in the structuraL backbones.

Automated summary

The reaction of potassium (aza-15-crown-5)dithiocarbamate with Au, Ag, and Cu metals was studied, resulting in different coordination systems, and the size of alkaline metal ions has a significant impact on the structures.