An Unusual Near-Eclipsed Porphyrin Ring Orientation in Two Crystalline Forms of (.mu.-Oxo)bis[(octaethylporphinato)iron(III)]. Structural and Molecular Mechanics Studies
An Unusual Near-Eclipsed Porphyrin Ring Orientation in Two Crystalline Forms of (.mu.-Oxo)bis[(octaethylporphinato)iron(III)]. Structural and Molecular Mechanics Studies
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(μ-氧代)双[(八乙基卟啉)铁(III)]的两种晶型中不寻常的近失卟啉环取向。
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发表时间：
1995
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通讯作者：
W. Scheidt
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作者：
B. Cheng;J. Hobbs;P. Debrunner;J. Erlebacher;J. Shelnutt;W. Scheidt
({mu}-oxo)bis[(八乙基卟啉)铁(III)]、[Fe(OEP)]{sub 2}O (C{sub 72}H{sub 88}Fe{sub 2}N{sub 8}O) 的两种多晶型物的结构已通过使用区域探测器收集的数据进行 X 射线结构分析来确定。两种[Fe(OEP)]{sub 2}O多晶型物（三斜晶型和单斜晶型）显示出很强的结构相似性。八个 Fe-N{sub p} 键距的平均值在三斜晶型中为 2.077(3) {埃}，在单斜晶型中为 2.080(5) {埃}。铁(III)原子从平均卟啉核的平均位移在三斜晶型中为0.50埃，在单斜晶型中为0.54埃。两种晶型的分子最重要的结构特征是近乎重叠的分子内卟啉环取向：三斜晶型中的平均N-Fe-Fe{prime}-N{prime}二面角为17.0(10){°}，单斜晶型中为16.8(6){°}。进行了分子力学计算以探索环间取向；这些表明外围乙基相互作用导致近乎重叠的方向。晶体数据：三斜晶型，a = 11.561(5) {埃}，b = 12.299(8) {埃}，c = 23.341(16) {埃}，{alpha} = 82.56(3){度}，{beta} = 81.94(7){度}，{gamma} = 79.18(1){度}，空间群 P1，V = 3210(5) {Angstrom}{sup 3}，Z = 2,8931 个观测数据，R{sub 1} = 0.050，R{sub 2} = 0.056；单斜更多 » 形式，a = 18.433(13) {Angstrom}，b = 15.104(6) {Angstrom}，c = 23.489(6) {Angstrom}，{beta} = 97.82(1){ Degrees}，空间群 P2{sub 1}/c，V = 6479(9) {Angstrom} {sup 3}，Z = 4,6169 个观测数据，R{sub 1} = 0.054，R{sub 2} = 0.060。« 更少
The structures of two polymorphs of ({mu}-oxo)bis[(octaethylporphinato)iron(III)], [Fe(OEP)]{sub 2}O (C{sub 72}H{sub 88}Fe{sub 2}N{sub 8}O), have been determined by X-ray structure analyses using data collected with an area detector. The two [Fe(OEP)]{sub 2}O polymorphs (a triclinic and a monoclinic form) show strong structural similarities. The eight Fe-N{sub p} bond distances have average values of 2.077(3) {Angstrom} in the triclinic form and 2.080(5) {Angstrom} in the monoclinic form. The average displacements of the iron(III) atom from the mean porphinato core are 0.50 {Angstrom} in the triclinic form and 0.54 {Angstrom} in the monoclinic form. The most important structural feature of the molecule in the two crystal forms is the near-eclipsed intramolecular porphyrin ring orientation: the average N-Fe-Fe{prime}-N{prime} dihedral angles are 17.0(10){degrees} in the triclinic form and 16.8(6){degrees} in the monoclinic form. Molecular mechanics calculations have been carried out to explore the inter-ring orientation; these suggest that peripheral ethyl group interactions lead to the near-eclipsed orientation. Crystal data: triclinic form, a = 11.561(5) {Angstrom}, b = 12.299(8) {Angstrom}, c = 23.341(16) {Angstrom}, {alpha} = 82.56(3){degrees}, {beta} = 81.94(7){degrees}, {gamma} = 79.18(1){degrees}, space group P1, V = 3210(5) {Angstrom}{sup 3}, Z = 2,8931 observed data, R{sub 1} = 0.050, R{sub 2} = 0.056; monoclinicmore » form, a = 18.433(13) {Angstrom}, b = 15.104(6) {Angstrom}, c = 23.489(6) {Angstrom}, {beta} = 97.82(1){degrees}, space group P2{sub 1}/c, V = 6479(9) {Angstrom} {sup 3},Z = 4,6169 observed data, R{sub 1} = 0.054, R{sub 2} = 0.060.« less