Castiñeiras Campos, AlfonsoFernández Hermida, NuriaFrontera, AntonioGarcía Santos, María IsabelGómez Rodríguez, Lourdes2025-11-052025-11-052025-09-12Donmez, M., Sekerci, M., Adiguzel, R., Oğuz, E., Türkan, F., Yildiko, U., & Colak, N. (2025). Reactivity of acetylbarbituric thiosemicarbazone derivatives with silver(I) nitrate and the influence of substituents at nitrogen atom 4N on the bonding and nuclearity of the resulting silver(I) complexes. ACS Omega, 10 (37), 1109–1127. https://doi.org/10.1021/acsomega.5c055392470-1343https://hdl.handle.net/10347/43569The reactions of silver(I) nitrate with N-substituted thiosemicarbazones derived from 5-acetylbarbituric acid (H2Acb4R, R = NH2, NHCH3, N(CH3)2, piperidine (Pip), or hexamethylenimine (hexim) in the presence of triphenylphosphine and triethylamine form a series of silver(I) complexes with various structural motifs and different coordination geometries at the metal, with the composition [Ag(PPh3)2(HAcb4NH2)] (1), [Ag(PPh3)3(HAcb4NH2)]·EtOH·H2O (2), Ag(PPh3)(H2Acb4NHM)(NO3)·2H2O (3), [Ag(PPh3)3(HAcb4NHM)]·2EtOH (4), Ag(PPh3)(H2Acb4NHM)2(NO3)·3H2O (5), [Ag(PPh3)3(HAcb4NDM)]·3EtOH (6), [Ag(PPh3)3(HAcb4NDM)]·2DMSO·H2O (7), [Ag(PPh3)(HAcb4Pip)]3·4.5H2O (8) and [Ag(PPh3)3(HAcb4Hexim)]·3EtOH·3H2O (9), and {[Ag(H2O)14](NO3)}n, [Ag(PPh3)4](NO3)·EtOH, [AgCl(PPh3)]4 as byproducts. In many cases, polycrystalline samples of these compounds were characterized using elemental analysis, FT-IR, UV–Visible, 1H, 13C{1H} and 31P{1H} NMR spectroscopy, FAB-MS, and single-crystal X-ray crystallography. The spectroscopic properties and structures of these compounds, except 1, 3, and 5, are discussed. Various hydrogen-bonding interactions, such as N–H···O, O–H···O, C–H···O, and π–π stacking interactions, contribute to the crystal packing. The influence of these weak interactions has been addressed with the help of Hirshfeld surface analyses and further analyzed using DFT calculations and Bader’s theory of atoms-in-molecules.Las reacciones del nitrato de plata (I) con tiosemicarbazonas sustituidas en N derivadas del ácido 5-acetilbarbitúrico (H2Acb4R, R = NH2, NHCH3, N(CH3)2, piperidina (Pip) o hexametilenimina (hexim) en presencia de trifenilfosfina y trietilamina forman una serie de complejos de plata (I) con diversos motivos estructurales y diferentes geometrías de coordinación en el metal, con la composición [Ag ( P P h 3 ) 2 ( H A c b 4 N H 2 ) ] ( 1 ), [ A g - (PPh3)3(HAcb4NH2)]·EtOH·H2O (2), Ag(PPh3)(H2Acb4NHM)(NO3)· 2H2 O (3), [Ag(PPh3 )3 (HAcb4NHM)]·2EtOH (4), Ag(PPh3 )- (H2Acb4NHM)2(NO3)·3H2O (5), [Ag(PPh3)3(HAcb4NDM)]·3EtOH (6), [Ag(PPh3)3(HAcb4NDM)]·2DMSO·H2O (7), [Ag(PPh3)(HAcb4Pip)]3· 4,5H2O (8) y [Ag(PPh3)3(HAcb4Hexim)]·3EtOH·3H2O (9), y {[Ag- (H2O)14](NO3)}n, [Ag(PPh3)4](NO3)·EtOH, [AgCl(PPh3)]4 como subproductos. En muchos casos, las muestras policristalinas de estos compuestos se caracterizaron mediante análisis elemental, FT-IR, UV-Visible, espectroscopia de RMN 1H, 13C{1H} y 31P{1H}, FAB-MS y cristalografía de rayos X de cristal único. Se discuten las propiedades espectroscópicas y las estructuras de estos compuestos, excepto 1, 3 y 5. Varias interacciones de enlaces de hidrógeno, como N−H···O, O−H···O, C−H···O e interacciones de apilamiento π−π, contribuyen al empaquetamiento cristalino. La influencia de estas interacciones débiles se ha abordado con la ayuda de análisis de superficie de Hirshfeld y se ha analizado más a fondo utilizando cálculos DFT y la teoría de Bader de átomos en moléculas.engThis article is licensed under CC-BY 4.0Crystal structureCrystalsLigandsMathematical methodsMetalsjournal article10.1021/acsomega.5c05539open access