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Crystal Engineering with the New Linker Tolanedisulfonic Acid (H 2 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
Author(s) -
Zitzer Christina,
Muesmann Thomas W. T.,
Christoffers Jens,
Wickleder Mathias S.
Publication year - 2015
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201403392
Subject(s) - monoclinic crystal system , crystallography , chemistry , zinc , protonation , crystal structure , zinc hydroxide , ion , organic chemistry
Abstract Reaction of 4,4′‐tolanedisulfonic acid, H 2 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, P 3 2 21, Z =3, a =1175.0(1) pm, c =1949.5(1) pm, R 1 ; w R 2 ( I o > 2σ( I o ))=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 H 2 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)°, R 1 ; w R 2 ( I o > 2σ( I o ))=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, I 2 /a, Z =4, a =1575.7(1) pm, b =1077.3(1) pm, c =1870.0(1) pm, β =101.189(9)°, R 1 ; w R 2 ( I o > 2σ( I o ))=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.