535993-83-0Relevant academic research and scientific papers
The influence of functional group orientation on the structure of zinc 1,1,4-trimethylthiosemicarbazide dicarboxylates: Probing the limits of crystal engineering strategies
Burrows, Andrew D.,Harrington, Ross W.,Mahon, Mary F.,Teat, Simon J.
, p. 766 - 776 (2003)
The reaction of [Zn(tmtsc)2](NO3)2 [tmtsc = 1,1,4-trimethyl-thiosemicarbazide, MeNHC(S)NHNMe2] with a range of sodium dicarboxylates has been shown to lie on the borderline between commonly used crystal engineering strategies. The products exhibit a wide range of structural diversity with the main driving force being the relative orientation of the carboxylate groups. Thus, fumarate leads to the hydrogen-bonded aggregate [Zn(tmtsc)2(OH2)][fumarate] (2) in which cations and anions are linked by hydrogen bond donor-donor acceptor-acceptor (DD:AA) interactions, whereas isophthalate and (+)-camphorate lead to coordination polymers [Zn(tmtsc)(μ-isophthalate)] (3a) and [Zn (tmtsc)(μ-camphorate)] (4) with the metal centres linked by bridging dicarboxylate ligands. In the case of isophthalate, a hydrated product [Zn(tmtsc)(μ-isophthalate)]·H2O (3b) was also characterised, although microanalysis and powder X-ray diffraction revealed this to be a minor product. Incorporation of water was shown to lead to a change in carboxylate coordination mode from η1 in 3a to η2 in 3b. Use of terephthalate leads to the compound [(Zn(tmtsc)(OH2)}2(μ-terephthalate)]- [terephthalate]·2H2O (5), in which half of the terephthalates bridge metal centres, to form dimers, and the remainder link the dimeric cations through DD:AA hydrogen bond interactions. Homophthalate leads to discrete dimers [Zn(tmtsc)(μ-homophthalate)]2 (6), whereas acetylenedicarboxylate yields the unexpected compound [Zn(tmtsc)2(OH2)][O2CCH= CC(O)N(Me)C(=NNMe2)S]2·H2O (7) in which the dicarboxylate has reacted with tmtsc to give a 2-hydrazono-4-oxo-1,3-thiazolidineacetate, which is subsequently trapped in the solid state by DD:AA hydrogen bonding interactions with [Zn(tmtsc)2(OH2)]2+. All products were characterised by single crystal X-ray crystallography, and the representational nature of these crystal structures to the bulk materials was confirmed by microanalysis and powder diffraction. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
