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首页> 外文期刊>Acta crystallographica. Section C, Structural chemistry. >Phase-transformation-induced twinning of an iron(III) calix[4]pyrrolidine complex
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Phase-transformation-induced twinning of an iron(III) calix[4]pyrrolidine complex

机译：相变诱导的铁（III）杯[4]吡咯烷配合物孪生

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摘要

The title compound, tetrachlorido-1κCl;2κ3 Cl-(2,2,7,7,12,12,17,17-octamethyl-21,22,23,24-tetraazapentacyclo[16.2.1.1 3,6.18,11.113,16]tetracosane- 1κ4 N,N',N'',N''')-μ2-oxido-diiron(III), [Fe 2Cl4O(C28H52N4)], undergoes a slow phase transformation at ca 173 K from monoclinic space group P21, denoted form (I), to the maximal non-isomorphic subgroup, triclinic space group P , denoted form (II), which is accompanied by nonmerohedral twinning [twin fractions of 0.693 (4) and 0.307 (4)]. The transformation was found to be reversible, as on raising the temperature the crystal reverted to monoclinic form (I). In the asymmetric unit of form (I), Z' = 1, while in form (II), Z' = 2, with a very small reduction (ca 1.8%) in the unit-cell volume. The two independent molecules (A and B) in form (II) are related by a pseudo-twofold screw axis along the b axis. The molecular overlay of molecule A on molecule B has an r.m.s. deviation of 0.353 ?, with the largest distance between two equivalent atoms being 1.202 ?. The reaction of calix[4]pyrrolidine, the fully reduced form of meso-octamethylporphyrinogen, with FeCl3 gave a red-brown solid that was recrystallized from ethanol in air, resulting in the formation of the title compound. In both forms, (I) and (II), the Fe III atoms are coordinated to the macrocyclic ligand and have distorted octahedral FeN4OCl coordination spheres. These Fe III atoms lie out of the mean plane of the four N atoms, displaced towards the O atom of the [OFeCl3] unit by 0.2265 (5) ? in form (I), and by 0.2210 (14) and 0.2089 (14) ?, respectively, in the two independent molecules (A and B) of form (II). The geometry of the [OFeCl 3] units are similar, with each FeIII atom having a tetrahedral coordination sphere. The NH H atoms are directed below the planes of the macrocycles and are hydrogen bonded to the coordinated Cl- ions. There are also intramolecular C-H?Cl hydrogen bonds present in both (I) and (II). In form (I), there are no significant intermolecular interactions present. In form (II), the individual molecules are arranged in alternate layers parallel to the ac plane. The B molecules are linked by a C-H?Cl hydrogen bond, forming chains along [100].
机译：标题化合物tetrachlorido-1κCl;2κ3Cl-（2,2,7,7,12,12,17,17-八甲基-21,22,23,24-四氮杂五环[16.2.1.1 3,6.18,11.113,16 ]四氢呋喃-1κ4N，N'，N''，N'''）-μ2-氧化二铁（III），[Fe 2Cl4O（C28H52N4）]在单斜空间群P21处于173 K处经历缓慢的相变/ n，以形式（I）表示，到最大非同构亚组三斜空间群P，以形式（II）表示，并伴有非面体孪晶[孪生分数0.693（4）和0.307（4）]。发现该转变是可逆的，因为在升高温度时晶体恢复为单斜晶形式（I）。在形式（I）的不对称单位中，Z'= 1，而在形式（II）中，Z'= 2，单位细胞体积的减小非常小（约1.8％）。形式（II）中的两个独立分子（A和B）通过沿b轴的假双螺旋轴关联。分子A在分子B上的分子重叠度为r.m.s.偏差为0.353 ?，两个等效原子之间的最大距离为1.202?。杯[4]吡咯烷，内消旋八甲基卟啉原的完全还原形式，与FeCl 3反应，得到红棕色固体，其在空气中从乙醇中重结晶，从而形成标题化合物。在两种形式（I）和（II）中，Fe III原子与大环配体配位并且具有扭曲的八面体FeN4OCl配位球。这些Fe III原子位于四个N原子的平均平面之外，朝[OFeCl3]单元的O原子偏移0.2265（5）？在形式（I）的两个独立分子（A和B）中，分别以形式（I）的α，β，α和β分别为0.2210（14）和0.2089（14）Ω。 [OFeCl 3]单元的几何形状相似，每个FeIII原子均具有四面体配位球。 NH H原子指向大环平面以下，并氢键合到配位的Cl-离子上。在（Ⅰ）和（Ⅱ）中也都存在分子内的C-H 2 Cl氢键。在形式（I）中，不存在明显的分子间相互作用。在形式（II）中，各个分子布置在平行于ac平面的交替层中。 B分子通过C-H2Cl氢键连接，沿着[100]形成链。

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