Crystal Engineering with the New Linker Tolanedisulfonic Acid (H2TDS): 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 |
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| Authors: | Christina Zitzer Dr Thomas W T Muesmann Prof Jens Christoffers Prof Mathias S Wickleder |
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| Institution: | 1. Carl von Ossietzky University of Oldenburg, Institute of Chemistry, Oldenburg, Germany;2. (+49)?4417983352 |
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| Abstract: | Reaction of 4,4′‐tolanedisulfonic acid, H2TDS, with zinc hydroxide in dimethylacetamide, DMA, under solvothermal conditions led to the coordination polymer Zn(TDS)(DMA)3 ( I ). In the crystal structure trigonal, P3221, 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 Zn2+ ions into helical chains according to ∞1Zn(DMA)3/1(TDS)2/2] ( I ) causing the chirality of the compound. By using higher concentrations of H2TDS in the starting mixture the compound HDMA]2Zn(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 ∞1Zn(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. |
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| Keywords: | coordination polymers helical structure solvothermal synthesis thermal analysis tolanedisulfonic acid |
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