Miecznikowski John R, Jasinski Jerry P, Ostrowski Tyler J, Landy Kendra R, Bonitatibus Sheila C, Smolinsky Allison N, Bertolotti Natalia R
Department of Chemistry and Biochemistry, Fairfield University, 1073 North Benson Road, Fairfield, CT 06824, USA.
Department of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435, USA.
Acta Crystallogr E Crystallogr Commun. 2020 Oct 16;76(Pt 11):1757-1761. doi: 10.1107/S2056989020013547. eCollection 2020 Nov 1.
The structure of the title compound, [CoCl(CHNS)(HO)], at 173 K has monoclinic (2/) symmetry. We report here the synthesis, single-crystal structure, electrospray mass spectrum and NMR spectroscopy of a new six-coordinate cobalt(II) pincer complex. The pincer ligand, in this complex, which is novel, coordinates three nitro-gen atoms (two triazole and one pyridine). The ligand is ambidentate and can coordinate three nitro-gen atoms or two sulfur and one nitro-gen atoms. The cobalt(II) metal center has pseudo-octa-hedral geometry and based on the single-crystal structure, the pincer ligand coordinates in a meridional fashion with the metal and adjacent six-membered ring ligands all in a similar plane and forming two slightly distorted boat configurations. The other two coordinated monodentate ligands are one water mol-ecule and two chloride ions with four cobalt(II) complexes in the unit cell. The asymmetric unit of the complex is comprised of half the pyridine ring and water mol-ecule with the Co atom at the center of the pincer situated about a twofold axis. The Co-N, Co-O, and Co-Cl bond lengths are consistent with single bonds. In the crystal, the complex forms a three-centre bifurcated weak hydrogen-bonding inter-action with a chlorine ion, forming one inter-molecular inter-action with the pincer group and a water mol-ecule and a second intra-molecular inter-action with a C-H group within the pincer group. Crystal packing is also highlighted with (6)>< infinite chains forming along [001] supported by (8)>> ring motifs, forming a three-dimensional supra-molecular network structure. While some stacking of the pyridine rings in the unit cell is observed, there are no relevant π-π inter-actions in the crystal packing. The H and C{H} NMR spectra of the complex are consistent with a plane of symmetry being present. The electrospray mass spectrum, which was collected in positive ion mode, showed the loss of one water mol-ecule and one chloride ligand from the complex. In the future, we plan to screen this cobalt(II) complex for electrocatalysis reactivity.
标题化合物[CoCl(CHNS)(HO)]在173 K时具有单斜（2/）对称性。我们在此报告一种新型六配位钴（II）钳形配合物的合成、单晶结构、电喷雾质谱和核磁共振光谱。在这种配合物中，新型的钳形配体配位三个氮原子（两个三唑和一个吡啶）。该配体是两可配体，可以配位三个氮原子或两个硫和一个氮原子。钴（II）金属中心具有假八面体几何构型，基于单晶结构，钳形配体以子午线方式与金属配位，相邻的六元环配体都在同一平面内，形成两个略有扭曲的船型构型。另外两个配位的单齿配体是一个水分子和两个氯离子，晶胞中有四个钴（II）配合物。配合物的不对称单元由半个吡啶环和水分子组成，钳形结构中心的Co原子位于一个二重轴上。Co-N、Co-O和Co-Cl键长与单键一致。在晶体中，该配合物与一个氯离子形成三中心分叉弱氢键相互作用，与钳形基团和一个水分子形成一种分子间相互作用，与钳形基团内的一个C-H基团形成第二种分子内相互作用。晶体堆积也很突出，沿着[001]方向形成(6)><无限链，由(8)>>环基序支撑，形成三维超分子网络结构。虽然在晶胞中观察到吡啶环有一些堆积，但在晶体堆积中没有相关的π-π相互作用。该配合物的H和C{H}核磁共振光谱与存在对称平面一致。在正离子模式下收集的电喷雾质谱显示该配合物失去了一个水分子和一个氯配体。未来，我们计划筛选这种钴（II）配合物的电催化反应活性。
