Crystal Engineering with the New Linker Tolanedisulfonic Acid (H2 TDS): Helical Chains in Zn(TDS)(DMA)3 , Linear Chains in Zn(TDS)(NMP)3 , and Complex Anions in [HDMA]2 [Zn(TDS)2 (DMA)3 ](DMA)2.

Abstract

Reaction of 4,4'-tolanedisulfonic acid, H2 TDS, with zinc hydroxide in dimethylacetamide, DMA, under solvothermal conditions led to the coordination polymer Zn(TDS)(DMA)3 (I). In the crystal structure [trigonal, P32 21, Z=3, a=1175.0(1) pm, c=1949.5(1) pm, R1 ; wR2 (Io > 2σ(Io ))=0.0393; 0.0921] the disulfonate anions linked the Zn(2+) ions into helical chains according to ∞ (1) [Zn(DMA)3/1 (TDS)2/2 ] (I) causing the chirality of the compound. By using higher concentrations of H2 TDS in the starting mixture the compound [HDMA]2 [Zn(TDS)2 (DMA)3 ](DMA)2 (II) was formed. The structure [monoclinic, Cc, Z=4, a=1201.5(1) pm, b=1996.0(1) pm, c=2749.2(2) pm, β=101.897(2)°, R1 ; wR2 (Io > 2σ(Io ))=0.0699; 0.2017] displayed the complex anion [Zn(TDS)2 (DMA)3 ](2-) which was a perfect cut-off of the helical chain in I. Charge compensation was achieved by protonated DMA molecules. If N-methylpyrrolidone, NMP, was chosen as a solvent, the sulfonate Zn(TDS)(NMP)3 (III) [monoclinic, I2/a, Z=4, a=1575.7(1) pm, b=1077.3(1) pm, c=1870.0(1) pm, β=101.189(9)°, R1 ; wR2 (Io > 2σ(Io ))=0.0563; 0.1320] was obtained. Similarly to the findings for I, the formation of chains according to ∞ (1) [Zn(NMP)3/1 (TDS)2/2 ] was observed. However, due to the more bulky NMP molecules these chains were no longer helical but straight instead.