Abstract Coordination complexes of iron(III), cobalt(II) and zinc(II) with the ligand N′-{[1-(pyridin-2-yl)ethylidene]amino}pyridine-2-carboximidamide (pmhpa) have been synthesised and were structurally characterized by elemental analysis, mass spectrometry, X-ray diffraction and infrared spectroscopy. The mononuclear iron(III) complex, [Fe(pmhap)2][FeCl4], (1), adopts the orthorhombic non-centric space group P212121. The iron is present in an octahedral environment in the ion [Fe(pmhap)2]+. The crystallographically-determined formula of the cobalt(II) complex (2) is [Co2(pmhap)2Cl3]2[CoCl4].4MeOH. The compound crystallizes in the non-centric space group P 4 21c with a single cobalt ion in the asymmetric unit. The complex is dinuclear, with two cobalt ions bridged by chloride and the two nitrogen atoms of N=N of the pmhap ligand. The zinc(II) complex; [Zn2(pmhpa)3](NO3)4.2.75MeOH (3) crystallizes in the cubic space group Pa 3 with disordered methanol molecules present. This is dinuclear with the two zinc atoms being bridged by three N=N links from the ligand to form a threefold symmetric rotor. Infrared spectroscopy confirms that coordination occurs through the azide bridge. Measurements of magnetic susceptibility for the iron(III) and cobalt(II) complexes show that they are paramagnetic between 5 and 300 K. Mossbauer spectroscopic data supports the structure of the iron(III) complex being composed of an octahedral and a tetrahedral iron atom.

中文翻译：

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具有羧酰亚胺配体的铁（III）、钴（II）和锌（II）配位化合物：合成、结构和性质

摘要 已经合成了铁（III）、钴（II）和锌（II）与配体 N'-{[1-(pyridin-2-yl)ethylidene]amino}pyridine-2-carboximidamide (pmhpa) 的配位配合物并通过元素分析、质谱、X射线衍射和红外光谱对其进行了结构表征。单核铁 (III) 配合物 [Fe(pmhap)2][FeCl4], (1) 采用正交非中心空间群 P212121。铁以离子 [Fe(pmhap)2]+ 的形式存在于八面体环境中。钴 (II) 配合物 (2) 的晶体学确定式为 [Co2(pmhap)2Cl3]2[CoCl4].4MeOH。该化合物在非中心空间群 P 4 21c 中结晶，在不对称单元中具有单个钴离子。该复合物是双核的，两个钴离子被氯离子和 pmhap 配体的 N=N 的两个氮原子桥接。锌（II）络合物；[Zn2(pmhpa)3](NO3)4.2.75MeOH (3) 在立方空间群 Pa 3 中结晶，同时存在无序的甲醇分子。这是双核的，两个锌原子通过来自配体的三个 N=N 链接桥接形成三重对称转子。红外光谱证实通过叠氮化物桥发生配位。铁 (III) 和钴 (II) 配合物的磁化率测量表明它们在 5 到 300 K 之间是顺磁性的。穆斯堡尔光谱数据支持铁 (III) 配合物的结构由八面体和四面体铁原子组成. 这是双核的，两个锌原子通过来自配体的三个 N=N 链接桥接形成三重对称转子。红外光谱证实通过叠氮化物桥发生配位。铁 (III) 和钴 (II) 配合物的磁化率测量表明它们在 5 到 300 K 之间是顺磁性的。穆斯堡尔光谱数据支持铁 (III) 配合物的结构由八面体和四面体铁原子组成. 这是双核的，两个锌原子通过来自配体的三个 N=N 链接桥接形成三重对称转子。红外光谱证实通过叠氮化物桥发生配位。铁 (III) 和钴 (II) 配合物的磁化率测量表明它们在 5 到 300 K 之间是顺磁性的。穆斯堡尔光谱数据支持铁 (III) 配合物的结构由八面体和四面体铁原子组成.