Albert Daniel R, Gau Michael, Rajaseelan Edward
Department of Chemistry Millersville University,Millersville PA 17551 USA.
Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104, USA.
IUCrdata. 2025 Jul 8;10(Pt 7):x250598. doi: 10.1107/S241431462500598X. eCollection 2025 Jul.
The structure of the title compound, [Rh(NO)(NO)(CHP)] or [Rh(NO)(NO)(ONO)(PPh)], has been determined by single-crystal X-ray diffraction. A previous report of the title compound showed it crystallized in a monoclinic space group [Rajaseelan (1999 ▸). , 63-66; refcode SASTOW in the CSD]. However, it was unable to be refined because of severe disorder. In this study, two distinct crystals of the title compound were found showing the compound to be polymorphic. One of the crystals was unable to be resolved but was found to be in a monoclinic space group, as in the previously reported study. The other crystal was able to be refined and crystallizes in the triclinic space group 1. The refined structure consists of two discrete monomeric mol-ecules per unit cell. The mol-ecular geometry around rhodium is that of a distorted square pyramid, with nitro-gen of the nitro ligand, oxygen of the nitrito ligand and phospho-rus atoms of the phosphane ligands lying in the basal plane and the nitro-gen atom of the bent nitrosyl occupying the apical position. The nitrosyl ligand exhibits positional disorder whereas the nitro and nitrito ligands show disorder across coordination sites with the disorder modelled in a 0.91:0.09 ratio. Both intra-molecular C-H ⋯O (nitro and nitrito) and inter-molecular C-H ⋯N (nitrito) inter-actions are observed. There are no hydrogen-bonding inter-actions with the N or O atoms of the nitrosyl ligand.
标题化合物[Rh(NO)(NO)(CHP)]或[Rh(NO)(NO)(ONO)(PPh)]的结构已通过单晶X射线衍射确定。之前关于该标题化合物的报告显示它结晶于单斜空间群[Rajaseelan (1999 ▸). , 63 - 66; CSD中的参考代码SASTOW]。然而，由于严重的无序性，它无法被精修。在本研究中，发现了该标题化合物的两种不同晶体，表明该化合物具有多晶型性。其中一种晶体无法解析，但发现其处于单斜空间群，与之前报道的研究一致。另一种晶体能够被精修，结晶于三斜空间群1。精修后的结构在每个晶胞中由两个离散的单体分子组成。铑周围的分子几何形状为扭曲的四方锥，硝基配体的氮、亚硝酸根配体的氧和膦配体的磷原子位于基面，弯曲的亚硝酰基的氮原子占据顶端位置。亚硝酰基配体表现出位置无序，而硝基和亚硝酸根配体在配位位点上表现出无序，无序比例建模为0.91:0.09。观察到分子内的C - H⋯O（硝基和亚硝酸根）和分子间的C - H⋯N（亚硝酸根）相互作用。与亚硝酰基配体的N或O原子没有氢键相互作用。
