The Influence of Functional Group Orientation on the Structure of Zinc 1,1,4‐Trimethylthiosemicarbazide Dicarboxylates: Probing the Limits of Crystal Engineering Strategies
The Influence of Functional Group Orientation on the Structure of Zinc 1,1,4‐Trimethylthiosemicarbazide Dicarboxylates: Probing the Limits of Crystal Engineering Strategies
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DOI：
10.1002/ejic.200390106
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发表时间：
2003-02
影响因子：
2.3
通讯作者：
A. Burrows;R. Harrington;M. Mahon;S. Teat
中科院分区：
文献类型：
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作者：
A. Burrows;R. Harrington;M. Mahon;S. Teat
[Zn（tmtsc）（2）]（NO3）（2）[tmtsc = 1，1，4-三甲基氨基硫脲，MeNHC（S）NHNMe 2]与一系列二羧酸钠的反应已被证明位于常用晶体工程策略之间的边界。产物表现出广泛的结构多样性，主要驱动力是羧酸酯基团的相对取向。因此，富马酸盐导致氢键聚集体[Zn（tmtsc）（2）（OH 2）][富马酸盐]（2），其中阳离子和阴离子通过氢键供体-供体-受体（DD：AA）相互作用连接，而反丁烯二酸盐和（+）-反丁烯二酸盐导致配位聚合物[Zn（tmtsc）（μ-反丁烯二酸盐）]（3a）和[Zn（tmtsc）（μ-反丁烯二酸盐）]（4），其中金属中心通过桥接二羧酸盐配体连接。在锌酸盐的情况下，还表征了水合产物[Zn（tmtsc）（μ-锌酸盐）]·H2O（3b），尽管微量分析和粉末X射线衍射显示这是次要产物。水的引入导致羧酸盐配位模式从3a中的eta（1）改变为3b中的112。使用对苯二甲酸酯导致化合物[{Zn（tmtsc）（OH 2）}（2）（μ-对苯二甲酸酯）]-[对苯二甲酸酯]·2 H（2）O（5），其中一半的对苯二甲酸酯桥接金属中心以形成二聚体，并且其余的通过DD：AA氢键相互作用连接二聚阳离子。高邻苯二甲酸酯导致离散的二聚体[Zn（tmtsc）]（μ-高邻苯二甲酸酯）12（6），而乙炔二羧酸酯产生意外的化合物[Zn（tmtsc）（2）（OH 2）][O 2 CCH = CC（O）N（Me）C（= NNMe 2）S]（2）·H 2 O（7），其中二羧酸酯与tmtsc反应得到2-亚肼基-4-氧代1，3-噻唑烷乙酸酯，其随后通过DDAA与[Zn（tMtSO（2）（OH 2）]（2+）的氢键相互作用而被捕获在固态中。所有产品的特征在于单晶X射线晶体学，并通过微量分析和粉末衍射证实了这些晶体结构的代表性性质的散装材料。(C)Wiley-VCH Verlag GmbH & Co. KGaA，69451魏因海姆，德国，2003.
The reaction of [Zn(tmtsc)(2)](NO3)(2) [tmtsc = 1,1,4-trimethylthiosemicarbazide, 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)(mu-isophthalate)] (3a) and [Zn(tmtsc)(mu-camphorate)] (4) with the metal centres linked by bridging dicarboxylate ligands. In the case of isophthalate, a hydrated product [Zn(tmtsc)(mu-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 eta(1) in 3a to 112 in 3b. Use of terephthalate leads to the compound [{Zn(tmtsc)(OH2)}(2)(mu-terephthalate)]-[terephthalate].2H(2)O (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)(mu-homophthalate)12 (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-oxo1,3-thiazolidineacetate, which is subsequently trapped in the solid state by DDAA hydrogen bonding interactions with [Zn(tMtSO(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. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.