Daniel R. Albert , Michael Gau , Edward Rajaseelan
{"title":"(亚硝酸盐-κ或)(的-κ(N) (nitrosyl -κ(N)之二- (tri-phenylphosphane -κP) rhodium (III)。","authors":"Daniel R. Albert , Michael Gau , Edward Rajaseelan","doi":"10.1107/S241431462500598X","DOIUrl":null,"url":null,"abstract":"<div><div>The title Rh<sup>III</sup> complex is a rare example of a mononuclear compound gathering nitrito, nitro and nitrosyl ligands.</div></div><div><div>The structure of the title compound, [Rh(NO)(NO<sub>2</sub>)<sub>2</sub>(C<sub>18</sub>H<sub>15</sub>P)<sub>2</sub>] or [Rh(NO)(NO<sub>2</sub>)(ONO)(PPh<sub>3</sub>)<sub>2</sub>], 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 <em>et al.</em> (1999<span><span>#</span></span>). <em>J. PA. Acad. Sci.</em><strong>73</strong>, 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 <em>P</em>1. The refined structure consists of two discrete monomeric molecules per unit cell. The molecular geometry around rhodium is that of a distorted square pyramid, with nitrogen of the nitro ligand, oxygen of the nitrito ligand and phosphorus atoms of the phosphane ligands lying in the basal plane and the nitrogen 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 intramolecular C—H ⋯O (nitro and nitrito) and intermolecular C—H ⋯N (nitrito) interactions are observed. There are no hydrogen-bonding interactions with the N or O atoms of the nitrosyl ligand.<blockquote><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (325KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div></blockquote></div></div>","PeriodicalId":94324,"journal":{"name":"IUCrData","volume":"10 7","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"(Nitrito-κO)(nitro-κN)(nitrosyl-κN)bis(triphenylphosphane-κP)rhodium(III)\",\"authors\":\"Daniel R. Albert , Michael Gau , Edward Rajaseelan\",\"doi\":\"10.1107/S241431462500598X\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The title Rh<sup>III</sup> complex is a rare example of a mononuclear compound gathering nitrito, nitro and nitrosyl ligands.</div></div><div><div>The structure of the title compound, [Rh(NO)(NO<sub>2</sub>)<sub>2</sub>(C<sub>18</sub>H<sub>15</sub>P)<sub>2</sub>] or [Rh(NO)(NO<sub>2</sub>)(ONO)(PPh<sub>3</sub>)<sub>2</sub>], 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 <em>et al.</em> (1999<span><span>#</span></span>). <em>J. PA. Acad. Sci.</em><strong>73</strong>, 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 <em>P</em>1. The refined structure consists of two discrete monomeric molecules per unit cell. The molecular geometry around rhodium is that of a distorted square pyramid, with nitrogen of the nitro ligand, oxygen of the nitrito ligand and phosphorus atoms of the phosphane ligands lying in the basal plane and the nitrogen 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 intramolecular C—H ⋯O (nitro and nitrito) and intermolecular C—H ⋯N (nitrito) interactions are observed. 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引用次数: 0
摘要
用单晶x射线衍射测定了标题化合物[Rh(NO)(NO2)2(C18H15P)2]或[Rh(NO)(NO2)(ONO)(PPh3)2]的结构。标题化合物的先前报道表明它在单斜空间群中结晶[Rajaseelan et al.（1999▸）]。j . PA。自然科学学报，23 (2)；在CSD中重新编码SASTOW]。然而，由于严重的混乱，它无法被提炼。在这项研究中，标题化合物的两个不同的晶体被发现，表明该化合物是多态的。其中一个晶体无法被分解，但被发现在单斜空间群中，就像之前报道的研究一样。另一个晶体能够被细化并在三斜空间群P1中结晶。精细化的结构由每个细胞两个离散的单体分子组成。铑周围的分子几何形状是一个扭曲的方形金字塔，其中硝基配体的氮原子、亚硝基配体的氧原子和磷化配体的磷原子位于基面上，弯曲的亚硝基的氮原子位于顶端位置。亚硝基配体表现出位置无序性，而硝基配体和亚硝基配体在配位位点上表现出无序性，无序性的模型比例为0.91:0.09。观察到分子内C-H⋯O（硝基和亚硝基）和分子间C-H⋯N（亚硝基）相互作用。与亚硝基配体的N或O原子没有氢键相互作用。
The title RhIII complex is a rare example of a mononuclear compound gathering nitrito, nitro and nitrosyl ligands.
The structure of the title compound, [Rh(NO)(NO2)2(C18H15P)2] or [Rh(NO)(NO2)(ONO)(PPh3)2], 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 et al. (1999#). J. PA. Acad. Sci.73, 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 P1. The refined structure consists of two discrete monomeric molecules per unit cell. The molecular geometry around rhodium is that of a distorted square pyramid, with nitrogen of the nitro ligand, oxygen of the nitrito ligand and phosphorus atoms of the phosphane ligands lying in the basal plane and the nitrogen 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 intramolecular C—H ⋯O (nitro and nitrito) and intermolecular C—H ⋯N (nitrito) interactions are observed. There are no hydrogen-bonding interactions with the N or O atoms of the nitrosyl ligand.
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