Crystal structure of neodymium(III) formate, Nd(HCO2)3

Abstract

Source of materialBiphenyl-3,3',4,4'-tetracarboxylic acid (0.033 g, 0.1 mmol), Nd(NO 3 ) 3 · 6H 2 O(0.0876 g, 0.2 mmol), NaOH (0.4 mmol, 0.016 g), DMF (N,N-dimethylformamide; 1m L), H 2 O( 6m L), and HNO 3 (0.5 mL, 0.75 MinH2O) were added respectively to a15 mL Teflon-lined steel autoclave, which was sealed and heated to 443K for 3d ays and then cooled to room temperature. Perfect pink block crystals were collected. Chemical analysis -found: C, 12.85 %; H, 1.12 %; calculated for C 3H3NdO6:C,12.90 %, H, 1.08 %. The synthesis of the title compound is out of the expectation of our original purpose. The ligand in the complex is af ormate, which was not directly introduced as one of the starting reaction materials. The starting materials biphenyl-3,3',4,4'-tetracarboxylic acid do not take part in the coordination. The synthetic procedure involves DMF and H 2 Oassolvents, and we think the formate group comes from DMF. Similar situation also occurred in other systems [1][2][3], and it has long been known that DMF can be hydrolyzed to formate and DMA (dimethylamine) and that the rate of this process increases at high temperature and pressure [4]. DiscussionThe title crystal structure, is isotypic with numerous lanthanide formates, like those of La, Ce, Tb and Tm [5]. Unit cell data have been reported previously for [Nd(HCO 2 ) 3 ] n [6], although the compound was described in that case as afractional hydrate and atomic coordinates were not determined. The title compound is a 3D neutral framework composed of Nd(III) ions and formate anions in a1:3ratio. The asymmetric unit contains 1/3 neodymium(III) cation and one formate HCO 2 − anion. The Nd ion lies on asite of 3m symmetry and is coordinated by nine Oatoms from nine HCO 2 − anions, which lie on mirror planes. The coordinating oxygen atoms of the formate ligand differ with respect to their linkage. O1 forms m 2-bridges between neighbouring neodymium centres, while O2 is monocoordinating. Each Catom makes three C−O−Nd linkages through one m 2-bridging Oatom (O1) and one m 1 -bound Oatom (O2). Three Nd ions and three HCO 2− anions are connected, forming six-membered rings, which are connected by further HCO 2− anions, generating a3Dframework. The distance between adjacent Nd ions is 4.0588(8) Å.

Water-Free Neodymium 2,6-Naphthalenedicarboxylates Coordination Complexes and Their Application as Catalysts for Isoprene Polymerization

“…41,42,51−56 The structure of the neodymium formate was recently redetermined from singlecrystal analysis in a rhombohedral symmetry. 41,42 It is based on the connection of infinite ribbons of tricapped trigonal prismatic polyhedra NdO 9 , linked to each other via the formate groups, which adopt the bidentate bridging mode μ 3 -η 2 :η 1 (Figure 3). The linkage of the NdO 9 polyhedra occurs through trigonal faces with three μ 3 -oxo species.…”

“…Only the mixed formate-naphthalenedicarboxylate phase has no coordinated water. During our investigations, a fourth phase, consisting of an anhydrous neodymium formate network, Nd(form) 3 ( 4 ), also has been prepared. The crystal structures of the compounds 1 , 2 , and 3 have been analyzed by means of single-crystal X-ray diffraction.…”

Insight into the Structural and Emissive Behavior of a Three‐Dimensional Americium(III) Formate Coordination Polymer

“…The initial report is limited to powder X-ray diffraction data which revealed that the structure was isomorphous with several analogous lanthanide formates as well as one uranium formate complex. [4,[44][45][46][47][48][49][50][51][52][53][54][55] No optical or other spectroscopic properties were reported, and no further work has been published for this foundational complex. Therefore, we recognize the importance of completing the record with respect to the synthesis and interpretation of spectroscopic signatures.…”

“…Only a single instance of americium formate has been reported to date, by Weigel and Meer in 1967, [4] which was synthesized via the dissolution of americium hydroxide in concentrated formic acid. The initial report is limited to powder X‐ray diffraction data which revealed that the structure was isomorphous with several analogous lanthanide formates as well as one uranium formate complex [4,44–55] . No optical or other spectroscopic properties were reported, and no further work has been published for this foundational complex.…”