0000000001303212
AUTHOR
María Hernández-molina
Crystal growth and structural remarks on malonate-based lanthanide coordination polymers
The synthesis, structural characterization and thermal study of new coordination polymers (CPs) of formula [Ln2(mal)3(H2O)5]·2H2O [Ln = Ho (1·2H2O), Tb (1a), Dy (1b), Er (1c) and Yb (1d); mal = malonate], [Ln2(mal)3(H2O)6] [Ln = Sm (2) and Ce (2a)], [Ce2(mal)3(H2O)6]·2H2O (3·2H2O) and [Ce2(mal)3(H2O)3]·2H2O (4·2H2O) are presented. Complexes 1–4 have been also characterized by single crystal X-ray diffraction. The structure of 2 was previously reported (Elsegood, M. R. J., Husain, S., Private Communication, 2014) and it is very close to that of 3. In the light of these results and those previously reported in the literature for malonate-containing lanthanide(III) complexes, a detailed overvi…
Malonate-based copper(II) coordination compounds: Ferromagnetic coupling controlled by dicarboxylates
Studies on structural and magnetic properties of polynuclear transition metal complexes, aimed at understanding the structural and chemical factors governing electronic exchange coupling mediated by multiatom bridging ligands, are of continuing interest to design new molecular materials exhibiting unusual magnetic, optical and electrical properties, bound to their molecular nature. Looking at potentially flexible bridging ligands, the malonate group seems a suitable candidate. The occurrence of two carboxylate groups in the 1,3 positions allows this ligand to adopt simultaneously chelating bidentate and different carboxylato bridging modes (syn–syn, anti–anti and syn–anti trough one or two …
Malonic acid: A multi-modal bridging ligand for new architectures and properties on molecule-based magnets
Abstract In this work, we show how the design of one-, two- and three-dimensional materials can strongly benefit from the use of crystal engineering techniques, which can give rise to structures of different shapes, and how these differences can give rise to different properties. We will focus on the networks constructed by assembling malonate ligands and metal centres. The idea of using malonate (dianion of propanedioic acid, H 2 mal) is that they can give rise to different coordination modes with the metal ions bind. Extended magnetic networks of dimensionalities 1 (1D), 2 (2D) and 3 (3D) can be chemically constructed from malonato-bridged metallic complexes. These coordination polymers b…
Crystal structure and magnetic properties of the single-μ-chloro copper(II) chain [Cu(bipy)Cl2] (bipy = 2,2′-bipyridine)
Abstract The crystal and molecular structure of the copper(II) chain [Cu(bipy)Cl2] (1) (bipy = 2,2′-bipyridine) has been determined by X-ray diffraction methods. The crystal structure of 1 consists of neutral single chloro-bridged copper(II) chains with alternating short and long Cu–Cl distances through a screw axis parallel to a. The copper surrounding is best described as distorted square pyramidal, the equatorial plane being built by the two nitrogen atoms of the chelating bipy and two chlorine atoms (one terminal and the other bridging), whereas the apical position is filled by the bridging chlorine atom from the symmetry-related adjacent unit. The equatorial Cu–Cl bonds (2.291(3) and 2…
Generation of lanthanide coordination polymers with dicarboxylate ligands: synthesis, structure, thermal decomposition and magnetic properties of the two-dimensional triaquatris(malonato)dipraseodymium(III) dihydrate {[Pr2(C3H2O4)3(H2O)3]·2H2O}
The malonate complex of formula [Pr2(C3H2O4)3(H2O)3]·2H2O (1) was prepared and his crystal structure determined by X-ray diffraction methods. 1 crystallizes in the monoclinic space group P21, Z = 4, with unit cell parameters a = 7.631(2), b = 12.899(4), c = 8.923(2) A and β = 101.11(3)°. 1 is a polymer which grows in the (110) plane. The hydrogen bond stabilizes the crystal structure forming a three-dimensional network. The two non-equivalent praseodymium(III) ions have different environments. Finally, the thermal behaviour and magnetic properties were investigated.
Synthesis, crystal structure and magnetic properties of the three-dimensional compound [Na2Ni(mal)2(H2O)6]n (H2mal=malonic acid)
Abstract A new three-dimensional nickel–sodium compound of formula [Na 2 Ni(mal) 2 (H 2 O) 6 ] n (H 2 mal=malonic acid) was prepared and its structure was determined by X-ray diffraction methods. Four malonate–oxygen atoms and two trans -(Ni) or cis -(Na) coordinated water molecules build distorted octahedral surroundings around the metal atoms. The malonate group exhibits bidentate (Ni) and tetrakis-monodentate (Na) coordination modes. The structure can be described as corrugated sheets of malonato-containing Ni(II) and Na(I) cations which grow in the (101) plane, each sheet being linked to the adjacent one in the [101] direction through bis(μ-aqua)disodium(I) units. Within each corrugated…
Geometric isomeric pairs: synthesis, structure, thermal decomposition and magnetic properties of cis- and trans-[Cr(mal)(bpy)(H2O)2][NO3]·xH2O (H2mal=malonic acid, bpy=2,2′-bipyridine)
Abstract Procedures are given for the preparation and isolation of cis-[Cr(mal)(bpy)(H2O)2][NO3]·3H2O (I) and trans-[Cr(mal)(bpy)(H2O)2][NO3]·H2O (II) (H2mal=malonic acid, bpy=2,2′-bipyridine). The single crystals X-ray structure of cis-compound reveals that the cations and anions as well as cations between cations are linked into hydrogen-bonded chains. Unfortunately, little structural information is available for the trans compound II (only isotropic cation refinement), nevertheless, from this result is observed that there also exists a hydrogen-bonded network between anion units. Thermal analysis and magnetic behaviour for both compounds were studied.
1,2,4,5‐Benzenetetracarboxylic Acid and 4,4′‐Bipyridine as Ligands in Designing Low‐Dimensional Coordination Polymers
The combined use of 1,2,4,5-benzenetetracarboxylic acid (H4bta) and 4,4′-bipyridine (bpy) as ligands with MnII and CoII ions afforded two polymeric compounds with the formulae [Mn(Hbta)(Hbpy)(H2O)2] (1) and [H2bpy][Co(bta)(bpy)(H2O)2] (2). 1 and 2 were prepared under hydrothermal conditions (145 °C, 3 h) and characterized by elemental analysis, IR spectroscopy, TG-DTA analysis and single-crystal X-ray diffraction methods. 1 exhibits a novel double chain structure growing along the b axis where the manganese atoms are linked by tris-monodentate Hbta3− ligands. The values of the manganese···manganese intrachain separations are 7.627(2) A [Mn(1)···Mn(1c); c = −x + 1/2, y − 1/2, −z] and 9.274(4…
The flexibility of molecular components as a suitable tool in designing extended magnetic systems
In this work we show how the design of n-dimensional magnetic compounds (nD with n = 1–3) can strongly benefit from the use crystal engineering techniques, which can give rive to structures of different shapes with different properties. We focus on the networks built by assembling the malonato-bridged tetranuclear copper(II) units Cu4(mal)4 (mal2− is the dianion of propanedioic acid, H2mal) through the potentially bridging 2,4′-bipyridine (2,4′-bpy), 4,4′-bipyridine (4,4′-bpy) and pyrazine (pyz). The magneto-structural study of the complexes of formula [Cu4(mal)4(2,4′-bpy)4(H2O)4]·8H2O (1), [Cu4(mal)4(H2O)4(4,4′-bpy)2] (2) (this compound was the subject of a previous report but it is includ…
Synthesis, crystal structure and magnetic properties of the malonato-bridged bimetallic chain [Mn(II)Cu(II)(mal)2(H2O)4]·2H2O
Abstract The first malonato-bridged bimetallic chain of formula [MnCu(mal)2(H2O)4]·2H2O (1) (H2mal=malonic acid) was prepared and its structure determined by X-ray diffraction methods. Each copper atom in 1 is in a square planar environment formed by four malonate-oxygens from two malonate ligands. The manganese atom is six-coordinated with four water molecules and two cis-coordinated malonate-oxygens from two malonate groups building a distorted octahedral surrounding. The malonate group acts simultaneously as bidentate and monodentate ligand towards copper and manganese atoms respectively, leading to a bimetallic chain. Two structurally different carboxylato-bridges exhibiting an anti–syn…
Structural versatility of the malonate ligand as a tool for crystal engineering in the design of molecular magnets
The synthesis of ferro- and ferri-magnetic systems with a tunable Tc and three-dimensional (3-D) ordering from molecular precursors implying transition metal ions is one of the active branches of molecular inorganic chemistry. The nature of the interactions between the transition metal ions (or transition metal ions and radicals) is not so easy to grasp by synthetic chemists working in this field since it may be either electrostatic (orbital) or magnetic (mainly dipolar). Therefore, the systems fulfilling the necessary requirements to present the expected magnetic properties are not so easy to design on paper and realize in the beaker. In this work we show how the design of one-, two- and t…
Crystal structures and magnetic properties of two- and three-dimensional malonato-bridged manganese(ii) complexes
Two new manganese(II) compounds of formula [Mn(mal)(H2O)(2,4′-bpy)]n (1) and [Mn2(mal)2(H2O)2(4,4′-bpy)]n (2) (2,4′-bpy = 2,4′-bipyridine, 4,4′-bpy = 4,4′-bipyridine and H2mal = malonic acid) have been prepared and structurally characterized by X-ray crystallography. Their structures are made up of two- (1) and three-dimensional (2) arrangements of manganese atoms linked by carboxylate-malonate groups in the anti–syn bridging mode (1 and 2) and bis(monodentate) 4,4′-bpy (2). The 2,4′-bpy group in 1 acts as a monodentate ligand. Each manganese atom in 1 and 2 is six-coordinated with four carboxylate-oxygens in the equatorial plane and a nitrogen atom and a water molecule in the axial positio…
Synthesis, crystal structure and magnetic properties of two-dimensional malonato-bridged cobalt(ii) and nickel(ii) compounds
Two isostructural malonato-bridged complexes of formula {[M(H2O)2][M(mal)2(H2O)2]}n [M = Co(II) (1), Ni(II) (2); H2mal = malonic acid] have been synthesised and characterized by X-ray diffraction. Their structure consists of corrugated layers of trans-diaquabismalonatemetalate(II) and trans-diaquametal(II) units bridged by carboxylate–malonate groups in the anti–syn conformation. Two crystallographycally independent metal atoms occur in 1 and 2. The malonate anion acts simultaneously as a bidentate and bis-monodentate ligand. Variable-temperature (1.9–295 K) magnetic susceptibility measurements indicate the occurrence of weak antiferro- (1) and ferromagnetic (2) interactions between the cob…
CCDC 294297: Experimental Crystal Structure Determination
Related Article: Fernando S. Delgado, Pablo Lorenzo-Luís, Jorge Pasán, Laura Cañadillas-Delgado, Oscar Fabelo, María Hernández-Molina, Antonio D. Lozano-Gorrín, Francesc Lloret, Miguel Julve, Catalina Ruiz-Pérez|2016|CrystEngComm|18|7831|doi:10.1039/C6CE01360K
CCDC 294298: Experimental Crystal Structure Determination
Related Article: Fernando S. Delgado, Pablo Lorenzo-Luís, Jorge Pasán, Laura Cañadillas-Delgado, Oscar Fabelo, María Hernández-Molina, Antonio D. Lozano-Gorrín, Francesc Lloret, Miguel Julve, Catalina Ruiz-Pérez|2016|CrystEngComm|18|7831|doi:10.1039/C6CE01360K
CCDC 1475076: Experimental Crystal Structure Determination
Related Article: Fernando S. Delgado, Pablo Lorenzo-Luís, Jorge Pasán, Laura Cañadillas-Delgado, Oscar Fabelo, María Hernández-Molina, Antonio D. Lozano-Gorrín, Francesc Lloret, Miguel Julve, Catalina Ruiz-Pérez|2016|CrystEngComm|18|7831|doi:10.1039/C6CE01360K
CCDC 294299: Experimental Crystal Structure Determination
Related Article: Fernando S. Delgado, Pablo Lorenzo-Luís, Jorge Pasán, Laura Cañadillas-Delgado, Oscar Fabelo, María Hernández-Molina, Antonio D. Lozano-Gorrín, Francesc Lloret, Miguel Julve, Catalina Ruiz-Pérez|2016|CrystEngComm|18|7831|doi:10.1039/C6CE01360K