Glutarate Anions Research Articles

Synthesis, structure, thermal and magnetic properties of new tetranuclear copper(II) complex supported by multidentate ligand and glutarate functionality

A new tetranuclear Cu(II) complex, [Cu(H2O)4][Cu4(cpdp)2(glut)]Cl2·6H2O (1) was successfully constructed by utilization of carboxylate-based multidentate ligand N,N'-bis[2-carboxybenzomethyl]-N,N'-bis[2-pyridylmethyl]-1,3-diaminopropan-2-ol (H3cpdp), in combination with glutarate (glut) and Cu(II) ions, and characterized systematically. Originally, the symmetrical flexible ligand cpdp3− is capable to bind two Cu(II) ions, leaving behind accessible binding sites for further coordination of exogenous glutarate anion which facilitates the assembly of two ligand-bound Cu(II) pairs. In MeOH/H2O, the reaction of CuCl2·2H2O with H3cpdp and sodium glutarate in the presence of NaOH results in the formation of 1. Complex 1 was characterized by different analytical techniques, including single crystal X-ray structure investigation. Analysis of single crystal X-ray structure shows that 1 is a self-assembled tetranuclear copper complex in which two dinuclear [Cu2(cpdp)]+ species are exclusively bridged by one glutarate functionality through μ4:η1:η1:η1:η1 manner, acting as a coligand. Thermoanalytical methods (TGA/DTA) were used to examine the thermal stability and it was observed that 1 is stable up to ∼190°C. Variable temperature (2-300 K) magnetic susceptibility studies show the weak antiferromagnetic interactions among the copper centers with the value of magnetic exchange coupling constant (J) of -0.5 cm−1.

The conglomerate crystal formation of methoxetamine salts in the presence of some organic achiral anions: a theoretical approach

ABSTRACT Density functional theory (DFT) calculations were made to investigate the interaction between enantiomers of methoxetamine (R & S) and achiral organic reagents, such as oxalate, succinate, fumarate, maleate, glutarate, adipate, pimelate, and suberate anions. The obtained results indicate that the oxalate and maleate anions have a greater ability to form conglomerate crystal of methoxetamine in the gas phase and in solution with chloroform, ethanol, and water. Results of the energy analysis reveal that, in comparison to gas phase and chloroform, the Gibbs energy, enthalpy, and internal thermal energy become more positive in the presence of water and ethanol solvents, confirming the negative effect of solvent polarity on enantiomer separation. It should also be noted that the presence of carbon-chain lengths greater than 3 atoms in organic reagents is not suitable for enantiomer separation and conglomerate crystal formation. .

Synthesis and Structure of New Glutarate-Containing U(VI), Np(V), and Pu(VI) Compounds

The structures of three new glutarate-containing compounds have been characterized. These compounds are (CN3H6)2[(UO2)2(C5H6O4)3] · 4H2O (I), (CN3H6)4[(NpO2)2(C5H6O4)3] · 12H2O (II), and [PuO2(C5H6O4)(H2O)] (III), where C5H6O$$_{4}^{{2 - }}$$ are glutarate anions and CN3H$$_{6}^{ + }$$ are guanidium cations. It was established that the structures of crystals I and II contain [(AnO2)2(C5H6O4)3]z– layers (An = U(VI) or Np(V) and z = 2 or 4, respectively), which can be described by the A2Q$$_{3}^{{02}}$$ crystallochemical formula, where A is UO$$_{2}^{{2 + }}$$ or NpO$$_{2}^{ + }$$ and Q02 are glutarate ions. The structure of crystal III contains two interpenetrating [PuO2(C5H6O4)(H2O)] frameworks and can be described by the AQ21M1 crystallochemical formula, where A = PuO$$_{2}^{{2 + }}$$, Q21 = C5H6O$$_{4}^{{2 - }}$$, and М1 = H2O. The influence of topological isomerism on the structures of the glutarate-containing complexes belonging to the A2Q023 and AQ21M1 crystallochemical groups was discussed.

The effect of organic cations on the structure of uranyl glutarate complexes

Two novel uranyl glutarate coordination polymers were characterized by single crystal X-ray diffraction and IR spectroscopy. The structure of the first compound with [N(CH3)3(CH2C6H5)]2[(UO2)2(C5H6O4)3]·H2O (1) composition (where C5H6O42− = C3H6(COO−)2 = glt2− are glutarate anions) contains [(UO2)2(glt)3]2− chains with A2Q023 crystallochemical formula (CCF) (A = UO22+, Q02 = C5H6O42−). The second structure with [N(C2H5)4]2[(UO2)3(C5H6O4)4(H2O)2]·2H2O (2) composition contains another type of chains with [(UO2)3(glt)4(H2O)2]2− composition and A3Q024M12 (A = UO22+, Q02 = glt2−, M1 = H2O) CCF. 1D uranyl glutarate complexes in 1 and 2 differ in UO22+:glt2− ratio leading to the different topology. While [(UO2)2(glt)3]2− chains in 1 have a simple “ladder” topology common for uranyl dicarboxylates structures, in 2 [(UO2)3(glt)4(H2O)2]2− units have additional spacing due to the presence of extra uranium atom with different coordination. The topological difference is described in terms of coordination sequences. The analysis of non-covalent interactions in 1 and 2 was done in topos-Intermol program package and the small contribution of π-staking was revealed in 1.

Mg, Ca and Ba glutaratouranylates – Synthesis and structure

Three novel uranyl coordination polymers were synthesized and structurally characterized by single crystal X-ray diffraction – [Mg(H2O)6][UO2(glt)(Hglt)]2·6H2O (1), [Ca(H2O)4][UO2(glt)(Hglt)]2·4H2O (2) and [Ba(H2O)5][UO2(glt)(Hglt)]2·2H2O (3), where glt = C5H6O42− (glutarate) and Hglt = C5H7O4− (hydroglutarate) anions. The structures of compounds 1–3 contain 1D [UO2(glt)(Hglt)]− units that belong to the AQ02B01 (A = UO22+, Q02 = glt, B01 = Hglt) crystallochemical group. The different roles of alkaline earth R2+ cations in the structures and the flexibility of the glutarate anions account for the structural distinctions of 1–3. The diverse ways for the connection between the R2+ ions and the [UO2(glt)(Hglt)]− chains, the water content and the geometry of the uranyl-glutarate units present the main structural features of the new complexes. A comparative analysis based on Pauling's second rule of 1–3 and alkali glutaratouranylates has allowed an explanation of their structural dissimilarity.

Structure of glutarate-containing uranyl coordination polymers with organic amides

Three new uranyl complexes [UO2(C5H6O4)(Meur)] (I), [UO2(C5H6O4)(Aa)] (II), and [(UO2)2(C5H6O4)2(Tmur)2(H2O)] • H2O (III), where C5H6O4 2− is glutarate anion, Meur is methylcarmamide, Aa is acetamide, and Tmur is tetramethylcarbamide, have been synthesized and characterized by X-ray diffraction. 1D uranyl-glutarate complexes have been found in the structures of all compounds; in I and II their composition is [UO2(C5H6O4)(L)] and crystallographic formula is AQ21M1 (where A = UO2 2+, Q21 = C5H6O4 2-, and M1 = L = Meur or Aa). In crystals III, chain complexes have the composition [(UO2)2(C5H6O4)2(Tmur)2(H2O)] and crystallographic formula A2Q2 02M3 1 (where A = UO2 2+, Q02 = C5H4O6 2-, and M1 = Tmur or H2O). All compounds were characterized by IR spectroscopy. Structural features of all known complexes of uranyl glutarate with neutral ligands have been discussed.

Preorganized Fluorescent Receptor for the Preferential Binding of the Glutarate Anion

A carbazolo[1,2‐a]carbazole‐2,11‐dicarboxamide has been synthesized and studied as a dicarboxylate anion receptor. The preorganized structure of this ligand affords a size‐selective response when a homologous series of dicarboxylates are analyzed. The structural correlation between the receptor and the different dianions was confirmed by 1H NMR studies, and different binding modes were also studied by X‐ray crystal structure analysis. The fluorescent properties of the carbazolocarbazole unit give a ratiometric response for those anions that have the best size fit. During the recognition process, the selective signaling of the glutarate anion results in a switch in the fluorescence color between the free and bound species. The detection of glutarate metabolites is important for the diagnosis of glutaric aciduria.

Crystal structures of new uranyl glutarate coordination polymers (NH4)2[(UO2)2(glt)3]·nH2O (n = 3 or 6) and R[UO2(glt)(Hglt)]·H2O (R = Na, K, Rb or Cs)

Six novel uranyl compounds with glutarate anions, (NH4)2[(UO2)2(glt)3]·6H2O (1), (NH4)2[(UO2)2(glt)3]·3H2O (2) and R[UO2(glt)(Hglt)]·H2O, where R=Na (3), K (4), Rb (5) or Cs (6), were synthesized and characterized by single crystal X-ray diffraction. The uranyl cations in 1 and 2 form complexes with an A2Q023 crystallochemical formula, whereas the uranyl complexes in 3–6 correspond to an AQ02B01 crystallochemical formula (A=UO22+, Q02=glt2−, B01=Hglt−). The structures of 1 and 2 are 2D coordination polymers. In 3–6, the main structural units are [UO2(glt)(Hglt)]− chains united by hydrogen bonds into sheets (3 and 4) or interpenetrating frameworks (5 and 6). The crystal structures of more than 30 uranyl compounds with anions of glutaric, thiodiglycolic, iminodiacetic and oxidiacetic acids were used to analyze the coordination abilities of dicarboxylate anions with uranium.

Structural similarities and diversity in a series of crystalline solids composed of 2-aminopyridines and glutaric acid

A solvent co-crystallization of three 2-aminopyridine derivatives, 2-aminopyridine (AP), 2-amino-6-methylpyridine (AMP), and 2,6-diaminopyridine (DAP) with the odd-membered propane-1,3-dicarboxylic acid (C5H12O4 = GAH2, glutaric acid) resulted in six ionic crystalline products, (HAP)(GAH) (1), (HAMP)(GAH) (2, 3), (HDAP)(GAH) (4), (HDAP)2(GA) (5), and (HDAP)2(DAP)(GA)(EtOH) (6, EtOH = ethanol). New compounds were characterized by single-crystal and powder X-ray diffraction, melting points, and IR spectra. The proton transfer to the pyridine nitrogen atom in all compounds and the location of H-atom in the carboxylic group in the hydrogen glutarate anion in binary adducts 1–4 was determined reliably from the low-temperature X-ray experiments. All compounds adopt the recurring R22(8) 2-aminopyridine–carboxylic acid heteromeric supramolecular synthon. The aggregation of hydrogen glutarate anions in the C(8) chain motifs in 1–4 occurs via the homomeric COOH···COO− robust pattern. Adducts 2 and 3 represent conformational polymorphs; adducts 4, 5 and 6 reveal the diversity in the components’ forms (ionic and neutral), acid–base ratios (1:1, 1:2, and 1:3), and hydrogen-bonding systems. This work demonstrates the variety of forms of glutaric acid in the H-bonded adducts.

Structural and vibrational spectral investigations of melaminium glutarate monohydrate by FTIR, FT-Raman and DFT methods

Melaminium glutarate monohydrate has been synthesised and FTIR and FT-Raman spectral investigations are carried out. The molecular geometry and vibrational frequencies of melaminium glutarate monohydrate in the ground state have been determined by using B3LYP method with 6-31++G**, 6-31++G and cc-pVDZ basis sets. The stability of the system, inter molecular hydrogen bonding and the electron donor–acceptor interactions of the complex have been investigated by using natural bonding orbital analysis. It reveals that the NH⋯O and OH⋯O intermolecular interactions significantly influence crystal packing of this molecular complex. The glutarate anion forms hydrogen bonds to the melaminium cation as the proton donor of the type NH⋯O with a distance (N⋯O)=2.51Å. It is also linked by other hydrogen bonds to the water molecule of the type OH⋯O with (O⋯O)=2.82Å and to the amino (NH2) group of melaminium cation of the type NH⋯O with (N⋯O)=2.82Å as the proton acceptor. The electrostatic potential of the complex is in the range +1.892e×10−2 to −1.892e×10−2. The limits of total electron density of the complex is +6.679e×10−2 to −6.679e×10−2.

Syntheses, crystal structures, and magnetic properties of four one-dimensional metal–nitroxide coordination polymers linked by flexible dicarboxylate anions

Four new one-dimensional coordination polymers [Co(IM4Py)2(adi)(H2O)2] n , [Zn(IM4Py)2(adi)(H2O)2] n , [Cd(IM4Py)2(adi)(H2O)2] n , and [Ni(IM4Py)2(glu)(H2O)2] n (IM4Py = 2-(4′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl, adi = adipate anion and glu = glutarate anion) were synthesized and structurally characterized. The single-crystal X-ray analyses indicate that all four complexes crystallize in neutral one-dimensional chains in which the nitroxide–metal–nitroxide units are bridged by the flexible dicarboxylate anions. The adipate anions adopt the anti/gauche/anti and anti/anti/anti conformations in the Co(II), Zn(II), and Cd(II) complexes, while the glutarate anions only possess the anti/anti conformation in the Ni(II) complex. The magnetic properties of the Co(II) and Ni(II) complexes show the occurrence of weak antiferromagnetic interactions between the metal atoms and the nitroxide radicals.

Synthesis, crystal structures and properties of three glutarato and adipato bridged manganese(II) coordination polymers under ambient conditions

Three Mn(II) polymers Mn(H2O)4(C5H6O4) 1, [Mn(H2O)2(C5H6O4)]·H2O 2 and Mn(H2O)(C6H8O4) 3 were synthesized (H2(C5H6O4) = glutaric acid, H2(C6H8O4) = adipic acid) under mild ambient conditions. The [Mn(H2O)2]2+ units in 2 are interlinked by the glutarate anions with a η4μ3 bridging mode to form 2D (4·82) topological networks, which are stacked via interlayer hydrogen bonds into a 3D (43·65·82)(47·63) topological net. Compound 3 crystallizes in the acentric space group P21 and exhibits significant ferroelectricity (remnant polarization Pr = 0.371 nC cm−2, coercive field Ec = 0.028 kV cm−1, saturation of the spontaneous polarization Ps = 0.972 nC cm−2). The adjacent MnO6 octahedrons in 3 are one atom-shared to generate the Mn2O11 bi-octahedron, leading into 1D metal oxide chains. The resulting chains are interconnected by the η5μ5 adipate anions to form new 2D (48·62) networks, which are held together via strong interlayer hydrogen bonds into 3D α-Po topological supra-molecular architecture. The temperature-dependent magnetic susceptibility data of 1–3 shows overall anti-ferromagnetic interactions between the metal ions bridged by the carboxylate groups.

Synthesis and crystal structures of two new Zn(II) coordination polymers with 4,4′-dipyridyl disulfide and dicarboxylate acid

The title compounds, Zn(C5H6O4)(Dpds) · 5H2O (I) and Zn(C6H8O4)(Dpds) (II) (C5H8O4 = glutaric acid, Dpds = 4,4′-dipyridyl disulfide, and C6H10O4 = adipic acid), are two-dimensional metal-organic coordination polymers. In I, the tetrahedra coordinated Zn atoms are bridged by glutarate anions and Dpds ligand to form a 2D layer parallel to (001) plane, which are connected by the 1D water tape notated as T4(2)5(2) to build up 3D supramolecular architecture. In II, both Dpds ligands and adipate anions act as bidentate bridges, connecting the Zn(II) centers in a tetrahedral coordination geometry into a two-dimensional (4,4) layer. Each layer polycatenates adjacent layers, exhibiting the rare combination of 2D → 2D parallels interpenetration.

Syntheses, Crystal Structures, and Magnetic Properties of Three 1D Chain Metal–Nitroxide Complexes Bridged by ­Flexible Dicarboxylate Anions

AbstractThree new one‐dimensional (1D) chain metal–nitroxide complexes {[Cu(NIT4Py)2(suc)(H2O)]·3H2O}n (1), {[Cd(NIT4Py)2(suc)(H2O)]·[Cd(NIT4Py)2(suc)(H2O)2]·3H2O}n (2), and {[Zn(NIT4Py)(glu)(H2O)]·H2O}n (3) [NIT4Py = 2‐(4′‐pyridyl)‐4, 4, 5, 5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide, suc = succinate anion and glu = glutarate anion] were synthesized and structurally characterized. Single‐crystal X‐ray analyses indicate that the three complexes crystallize in neutral 1D chains in which the metal‐nitroxide units are linked by flexible dicarboxylate anions. The succinate anions only adopt trans configuration in complexes 1 and 2, whereas the glutarate anion has gauche/anti conformation in complex 3. Magnetic measurements show that complex 1 exhibits weak antiferromagnetic interactions between the copper ions and the nitroxides.

2,3-Diaminopyridinium 4-carboxybutanoate

In the title mol­ecular salt, C5H8N3 +·C5H7O4 −, the 2,3-diamino­pyridine mol­ecule is protonated at the pyridine N atom. The cation is essentially planar, with a maximum deviation of 0.015 (2) Å, and the anion adopts an extended conformation. In the crystal, the hydrogen glutarate (4-carb­oxy­butano­ate) anions are self-assembled through O—H⋯O hydrogen bonds, forming chains. The cations are connected to the anion chains via N—H⋯O hydrogen bonds, forming a three-dimensional network. The crystal structure also features aromatic π–π inter­actions between the pyridinium cations, with a centroid–centroid distance of 3.4464 (10) Å.

Aquaglutarato(2,4,6-tri-2-pyridyl-1,3,5-triazine)nickel(II) trihydrate

In the title compound, [Ni(C5H6O4)(C18H12N6)(H2O)2]·3H2O, the NiII atom shows a distorted octa­hedral coordination by three N atoms of the tridentate chelating ligand and three O atoms of two aqua ligands and an O atom of one carboxylate group of the glutarate anion. Mol­ecules are self-assembled via inter­molecular O—H⋯O and O—H⋯N hydrogen-bonding inter­actions and π–π stacking inter­actions [centroid–centroid distance = 3.836 (3) Å] into a supra­molecular network.

Poly[[tetraaquadi-μ4-glutarato-μ2-terephthalato-dineodymium(III)] heptadecahydrate

The title compound, [Nd(2)(C(5)H(6)O(4))(2)(C(8)H(4)O(4))(H(2)O)(4)]·17H(2)O, obtained via hydrothermal reaction of Nd(2)O(3) with glutaric acid and terephthalic acid, assembles as a three-dimensional open framework with ten-coordinate Nd-O polyhedra. The asymmetric part of the unit cell contains half a glutarate anion, a quarter of a terephthalate dianion, half an Nd(III) cation, one coordinated water molecule and 4.25 solvent water molecules. Each [NdO(10)] coordination polyhedron is comprised of six O atoms originating from four glutarate anions, two others from a terephthalate carboxylate group, which coordinates in a bidentate fashion, and two from water molecules. The Nd-O distances range from 2.4184 (18) to 2.7463 (18) Å. The coordination polyhedra are interconnected by the glutarate anions, extending as a two-dimensional layer throughout the bc plane. Individual two-dimensional layers are interlinked via terephthalate anions along the a axis. This arrangement results in rectangular-shaped cavities with interstices of approximately 3.5 × 6 × 6.5 Å (approximately 140 Å(3)), which are occupied by water molecules. The Nd(III) cations, terephthalate anions, glutarate anions and one of the interstitial water molecules are located on special crystallographic positions. The Nd-terephthalate-Nd units are located across twofold rotation axes parallel to [100], with the Nd(III) cations located directly on these axes. In addition, the terephthalate anion is bisected by a crystallographic mirror plane perpendicular to that axis, thus creating an inversion centre in the middle of the aromatic ring. The glutarate ligand is bisected by a crystallographic mirror plane perpendicular to (001). One of the solvent water molecules lies on a site of 2/m symmetry, and the symmetry-imposed disorder of its H atoms extends to the H atoms of the other four solvent water molecules, which are disordered over two equally occupied and mutually exclusive sets of positions.

2-Amino-5-chloropyridinium 4-carboxybutanoate

In the title salt, C5H6ClN2 +·C5H7O4 −, the 2-amino-5-chloro­pyridinium cation is essentially planar, with a maximum deviation of 0.010 (3) Å. In the crystal structure, the protonated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxyl­ate O atoms of the anion via a pair of N—H⋯O hydrogen bonds, forming an R 2 2(8) ring motif. The ion pairs are further connected via O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, forming a layer parallel to the bc plane. In the layer, the hydrogen glutarate anions self-assemble via O—H⋯O hydrogen bonds, forming a supra­molecular chain along the c axis. Furthermore, the cations and anions are stacked down along the a axis, forming a three-dimensional network.

2-Amino-5-bromopyridinium 4-carboxybutanoate

In the title salt, C5H6BrN2 +·C5H7O4 −, the 2-amino-5-bromo­pyridinium cation is essentially planar, with a maximum deviation of 0.005 (3) Å. In the crystal structure, the proton­ated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxyl­ate O atoms of the anion via a pair of N—H⋯O hydrogen bonds, forming an R 2 2(8) ring motif. The ion pairs are further connected via O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, forming a two-dimensional network parallel to the bc plane. In the network, the hydrogen glutarate (4-carb­oxy­butano­ate) anions self-assemble through O—H⋯O hydrogen bonds, forming a supra­molecular chain along the c axis.

Influence of dicarboxylic acids on self-assembly process: Syntheses and structural characterization of new Ag(I) complexes derived from mixed ligands

Using the principle of crystal engineering, three new silver metal–organic coordination polymers, [Ag 2(L1) 2(L2)]·2H 2O ( 1), [Ag 2(L1) 2(L3)]·H 2O ( 2), [Ag 2(L1) 2(L4)]·2H 2O ( 3) (L1 = 2-aminopyrimidine, L2 = oxalate anion, L3 = glutarate anion and L4 = 1,4-naphthalenedicarboxylate anion) have been synthesized by solution phase reactions of silver nitrate with various dicarboxylic acids and cooperative heterocyclic 2-aminopyrimidine ligand under the ammoniacal conditions. All the complexes have been characterized by elemental analyses, IR spectra and X-ray diffraction. In complex 1, L1 ligands are coordinated to Ag(I) metal centers in rare tridentate fashions, forming one-dimensional (1-D) ladder-like structure, which is interlinked by L2 anions to generate 2-D pleated molecular sheet. Complex 2 displays an interesting two-dimensional (2-D) tongue-and-groove structure containing a new kind of “T-shaped” unit. Meanwhile, each of 2-D bilayers is interlocked by four adjacent identical motifs to form three-dimensional (3-D) 5-fold interpenetrating conformation with weak Ag···Ag interactions. In complex 3, L1 ligands are coordinated to the Ag(I) ions to form 1-D polymeric chain. And L4 anions, acting as bridging linkers through corresponding μ 2-carboxylates, link a pair of Ag(I) atoms from adjacent chains to yield 3-D supramolecular network. The structures of complexes 1– 3 which span from 2-D to 3-D networks suggest that dicarboxylate anions play important role in the formation of such coordination architectures.