Uranyl Coordination Compounds with Alkaline Earth Metals and Crotonate Ligands

Abstract

Crystal structures of three new uranyl compounds were solved using single crystal X‐ray diffraction and studied using FTIR spectroscopy. Although the syntheses conditions were very similar differing only in the alkaline earth metal (Mg, Ca or Sr), the resulting structures are different, containing, respectively, mono‐, tri‐ and hexanuclear metal‐containing building units. This fact proves the profound crystal‐chemical role of secondary metal atoms on the formation of crystal structures. Parameters of alkaline earth metal cations in the three newly synthesized compounds as well as in the earlier reported Ba‐containing analog are discussed in detail using Voronoi–Dirichlet polyhedra and the method of intersecting spheres. Differences in packing of building units in the four mentioned compounds, as well as inter‐ and intramolecular noncovalent interactions in their structures are reported. The results of analysis are consistent with the stereoatomic model of crystal structures.

New Polymorphic Structures of Uranyl Butyrate and Crotonate

“…Crystal structures of uranyl carboxylates with s-, p-, or d-block metals may be constructed either of separated s-, p-or d-block metal cations/aqua cations and uranyl based anions, for example [29] Tl-…”

“…Crystal structures of uranyl carboxylates with s ‐, p ‐, or d ‐block metals may be constructed either of separated s ‐, p ‐ or d ‐block metal cations/aqua cations and uranyl based anions, for example [Mg(H 2 O) 6 ][UO 2 (C 3 H 5 COO) 3 ] 2 ⋅ H 2 O {XOSGIY}, [29] Tl[UO 2 (C 2 H 5 COO) 3 ] {RIKBAO}, [30] [Co(H 2 O) 6 ][UO 2 (CH 2 C(CH 3 )COO) 3 ] 2 ⋅ 8H 2 O {GENBIO}, [31] or of heteronuclear (molecular or extended) species, for example {Ca(H 2 O) 3 [UO 2 (C 3 H 5 COO) 3 ] 2 } ⋅ 1.5H 2 O {XOSGOE}, [29] {PbUO 2 (CH 2 C(CH 3 )COO) 4 } {XOLDEK}, [32] [Zn(H 2 O) 4 (C 2 H 5 OH) 2 ]{Ag[UO 2 (CH 3 COO) 3 ] 3 } {GIKTAW} [33] . By reaction of α‐uranyl crotonate with crotonic acid at presence of MgCO 3 or UO 3 with butyric acid at presence of CoCO 3 in water/ethanol mixture yellow precipitates were obtained.…”