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首页> 外文期刊>Acta Crystallographica Section E: Crystallographic Communications >Crystal structure and redox potentials of the tppz-bridged {RuCl(bpy)}+ dimer
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Crystal structure and redox potentials of the tppz-bridged {RuCl(bpy)}+ dimer

机译：tppz桥接{RuCl（bpy）} +二聚体的晶体结构和氧化还原电势

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We report the structural and electrochemical characterization of the binuclear complex [μ-(C24H16N6){RuCl(C10H8N2)}2](PF6)2, which contains the bis-tridentate bridging ligand 2,3,5,6-tetra­kis­(pyridin-2-yl)pyrazine (tppz), the monodentate ligand Cl−, and the bidentate ligand 2,2′-bi­pyridine (bpy) {systematic name: μ-2,3,5,6-tetra­kis­(pyridin-2-yl)pyrazine-bis­[(2,2′-bi­pyridine)­chlorido­ru­thenium(II)] bis­(hexa­fluorido­phosphate)}. The complete [(bpy)(Cl)Ru(tppz)Ru(Cl)(bpy)]2+ dication is generated by crystallographic twofold symmetry; the tppz bridging ligand has a significantly twisted conformation, with an average angle of 42.4° between the mean planes of adjacent pyridyl rings. The metal-coordinated chloride ligands are in a trans configuration relative to each other across the {Ru(tppz)Ru} unit. The RuII ion exhibits a distorted octa­hedral geometry due to the restricted bite angle [160.6 (3)°] of the tppz ligand. For bpy, the bond lengths of the Ru—N bonds are 2.053 (8) and 2.090 (8) Å, with the shorter bond being opposite to Ru—Cl. For the tridentate tppz, the Ru—N distances involving the outer N atoms trans to each other are 2.069 (8) and 2.072 (9) Å, whereas the Ru—N bond involving the central N atom has the much shorter length of 1.939 (7) Å as a result of the geometric constraints and stronger π-acceptor ability of the pyrazine-centered bridge. The Ru—Cl distance is 2.407 (3) Å and the intra­molecular distance between Ru centers is 6.579 (4) Å. In the crystal, weak C—H⋯Cl and C—H⋯F inter­actions consolidate the packing.
机译：我们报告了双核复合物[μ-（C24H16N6）{RuCl（C10H8N2）} 2]（PF6）2的结构和电化学表征，该复合物包含双三齿桥联配体2,3,5,6-四（吡啶- 2-基）吡嗪（tppz），单齿配体Cl-和双齿配体2,2'-联吡啶（bpy）（系统名称：μ-2,3,5,6-四（吡啶-2-基）吡嗪-双[（2,2'-联吡啶）氯钌（II）]双（六氟磷酸）}。完整的[（bpy）（Cl）Ru（tppz）Ru（Cl）（bpy）] 2+指示是通过晶体学对称性产生的; tppz桥联配体具有明显的扭曲构象，相邻吡啶环的平均平面之间的平均角度为42.4°。金属配位的氯化物配体在{Ru（tppz）Ru}单元上相对于彼此呈反式构型。由于tppz配体的限制咬合角[160.6°（3）°]，RuII离子呈现出扭曲的八面体几何形状。对于bpy，Ru-N键的键长为2.053（8）和2.090（8）Å，较短的键与Ru-Cl相反。对于三齿tppz，涉及到外部N原子相互转移的Ru-N距离为2.069（8）和2.072（9）Å，而涉及中心N原子的Ru-N键的长度短得多，为1.939（ 7）由于吡嗪中心桥的几何约束和更强的π受体能力而导致Ru-Cl距离为2.407（3）Å，Ru中心之间的分子内距离为6.579（4）Å。在晶体中，弱的C–H⋯Cl和C–H⋯F相互作用会巩固堆积。

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