An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Three discrete tetranuclear coordination compounds with formulae (H3O)(+)[M-4(HL)(3)(H2O)(6)](-)center dot xH(2)O where M = Ni(II), HL = HcbtZol(3-) (1a), M = Ni(II)/Co(II), HL = HcptZol(3-) (2a/2b) and x = 13.8, 16.8 or 10.5 for 1a, 2a and 2b, respectively, (H(4)cbtZol = 1-hydroxy-2-[1-(1H-imidazol-1-yl)cyclobutyl]ethylidene-1,1-diphosphonic acid, H(4)cptZol = 1-hydroxy-2-[1-(1H-imidazol-1-yl)cyclopentyl]ethylidene-1,1-diphosphonic acid) were hydrothermally prepared and characterized by single crystal X-ray diffraction, IR, UV-Vis-NIR, thermal analysis and magnetic studies. All the compounds crystallize in the trigonal R (3) over bar space group and show a propeller-shaped {M(1)(II)M2(3)(II)O(6)} cores with M cations arranged into trigonal pyramid, in which the M1 ion is located in the apex while three peripheral M2 ions occupy the vertices of a triangle base. Both M1 and M2 are six-coordinate with M1 coordination octahedron slightly contracted along the 3-fold axis towards trigonal antiprism and peripheral M2 octahedrons slightly rotated towards trigonal prism. Discrete [M-4(HL)(3)(H2O)(6)](-) coordination units are assembled by O-H center dot center dot center dot O interactions involving hydroxyl O atom and coordinated water molecules as proton donors. Multiple lattice water molecules additionally stabilize the crystal structure through O-H center dot center dot center dot O interactions. All the compounds reveal thermal stability up to ca. 90 degrees C above which lattice water starts to be released. The architecture of [M-4(HL)(3)(H2O)(6)](-) cores remains intact up to ca. 130-140 degrees C. Qualitative analysis of potential paths of magnetic interactions in tetranuclear cores suggests ferromagnetic exchange with antiferromagnetic admixture.

Two novel isomorphous Co(II) and Zn(II) complexes of 5-nitroorotate have been synthesized and characterized by a single crystal X-ray diffraction, FT-IR, Raman and UV-Vis-NIR spectroscopy as well as thermal analysis. Both tetraaqua(5-nitroorotato)cobalt(II), [Co(5-NO2HOr)(H2O)4] (1) and tetraaqua(5-nitroorotato)zinc(II), [Zn(5-NO2HOr)(H2O)4] (2) crystallize in the orthorhombic system (space group Pca21). Each metal ion is chelated by the carboxylate oxygen (O1) and the deprotonated nitrogen (N1) atoms of the 5-nitroorotate ligand. Four water molecules complete the distorted octahedral coordination sphere around the metal center with an elongated axial M‒O bonds. The pattern of hydrogen bonding in the crystals of (1) and (2) is somewhat different than that reported for similar metal-orotate complexes. Weak C‒O···π and N‒O···π intermolecular interactions promote the crystal cohesion. Theoretical studies were performed using the DFT/B3LYP method and a detailed interpretation of the vibrational spectra has been made on the basis of the calculated potential energy distribution (PED). The electronic spectra and photoluminescent properties of (1), (2) and K(5-NO2H2Or) (3) were investigated. Temperature and field-dependent magnetic studies of (1) revealed the existence of a weak antiferromagnetic exchange coupling transmitted by medium-strong O‒H···O intermolecular hydrogen bonds. In addition, (1), (2) and (3) were studied in vitro for their activity against selected Gram-positive (S. aureus) and two Gram-negative (E. coli, P. aeruginosa) bacteria and one yeast (C. albicans).

The problem in formation of 3,5-diiodo-L-tyrosinato (L-I2Tyr) various metal ion complexes as a crystals is generated by the low solubility of iodo-L-tyrosinato derivatives (as ligands) in pure aqueous solution. However, two inorganic–organic hybrid l-I2Tyr copper(II) complexes i.e. [CuCl(L-I2TyrOH)(phen)]∙2H2O (1) and [Cu(l-I2TyrOH)(H2O)(phen)](NO3) (2) with l-I2TyrOH were isolated in acid aqueous/methanol medium. In crystals 1 and 2, the monomeric distorted square planar pyramidal copper(II) coordination is stabilized by weak intramolecular π···π stacking, copper(II)···π and π···I non-covalent interactions. The connection of adjacent 2D layers into 3D supramolecular network is realised by weak π···π contacts in 1, while in 2 the 3D architecture is stabilized by weak CH···π interaction as well as π···π contacts. The complexes are also characterized by infrared and Raman spectroscopies (FT-IR, FT-Raman), X- and Q-band electron paramagnetic resonance spectroscopy (EPR), electronic spectroscopy (NIR-Vis-UV), magnetic method, and theoretical calculation.

The ternary Cu(II)/amino-acid/diamine systems have large positive logK values than binary Cu/amino systems, suggesting stabilization due to the effective stacking interaction between aromatic diamine and the aromatic side group of the amino acid. Thus, a hybrid 3,5-diiodo-L-tyrosinato copper(II) complex with an aromatic diamine, of formula [Cu(L-I2TyrO-)(H2O)(phen)]center dot 2H2O (1) was characterized in depth by using X-ray, TG/DTG, DSC, FTIR, Raman, Q-band EPR, NIR-Vis-UV, magnetic methods and the theoretical calculations. The crystal structure is stabilized by weak pi center dot center dot center dot pi stacking, metal center dot center dot center dot pi and intraand intermolecular pi center dot center dot center dot I non-covalent interactions. The computed interaction energies of Cg(1)center dot center dot center dot Cg(2), Cg(3)center dot center dot center dot I and Cg(1)center dot center dot center dot Cu ranging from 0.69 kcal/mol--2.20 kcal/ mol. The weak interactions shift the bands assigned as nu(C-I) to higher frequency in the FT-IR spectrum. The g tensor is axial with g|| (2.239) > g perpendicular to (2.057) indicating that the unpaired electron residues in the dx2-y2 orbital. The exchange pathway occurs in the zig-zag chain with d(Cu center dot center dot center dot Cu) = 9.429 angstrom.

1D Co(ii)/Ni(ii) coordination polymers with alternating antiferromagnetic–ferromagnetic exchange interactions between metal centers propagated through double (–O–P–O–)2 bridges.

Complex of formula [Cu(L-Arg)(phen)Cl)Cl center dot 2H(2)O (1) was synthesized in crystalline form (triclinic crystal system, P1 (No. 1) space group with a = 9.376(1) angstrom, b = 10.415(1) angstrom, c = 12.209(2) angstrom and Z = 2). The relations between the crystal structure, DFT calculations, spectroscopic properties (FT-IR, FT-Raman, NIR-Vis-UV, EPR) as well as the parameters of magnetic data were investigated. The square pyramidal geometry around copper (II) cations is very slightly distorted toward bipyramid geometry. The DFT-calculated interaction energies (AE) for the L-Arg zwitterion and phen ligands are -135.31 and -54.17 kcal mol(-1), respectively. The g tensor diagonal components obey the relationship g(parallel to) > g(perpendicular to) (g(perpendicular to) = 2.063, g(parallel to) = 2.23) which suggested the pure d(x2-y2) ground state orbital. Analysis of the crystal structure shows two possible magnetic exchange pathways: the neighboring [Cu(L-Arg)(phen)Cl](+) cations are linked in dimeric units by the N-H center dot center dot center dot Cl type hydrogen bonds, and almost parallel phenanthroline molecules provide pi-pi stacking interaction between the dimers. Analysis of the magnetic data, using an alternating ferro- and antiferromagnetic chain model for S = 1/2 spins, reveals the existence of weak antiferromagnetic coupling within the dimers (J(AF) = -0.23 cm(-1)) and weak ferromagnetic interaction between dimers (J(F) = 0.11 cm(-1)).

We synthesized an l-arginine complex with the formula [Cu(l-Arg)(2)(NCS)](NCS)H2O (1) (l-Arg = l-arginine). Two cis-chelated l-arginine zwitterions form the basal plane, while the weakly N-bonded isothiocyanate is located at the apex of the distorted square pyramidal structure (=0.143). The non-coordinated NCS- anions held layers together in a 3-D supramolecular network. The crystal structure, spectroscopic (FT-IR, Raman, NIR-Vis-UV, EPR) and magnetic properties of 1 have been compared with [Cu(l-Arg)(NCS)(2)] (2). For 1, two absorptions are observed for (C=N) stretching vibrations, corresponding to NCS- ions N-bonded to the central Cu(II) (2077cm(-1)) and in the lattice (2057cm(-1)). In 2 a single band is observed at 2102cm(-1), indicating equivalent NCS- ions in the structure. The EPR spectra of complexes show anisotropic signal with g(perpendicular to) and g(||) 2.062, 2.235 (1), and 2.08, 2.225 (2) characteristic for cis-N2O2 and N3O donor sets in the xy plane, respectively. The unpaired electron mainly occupies the d(x2-y2) orbital, also confirmed by the single envelope of d-d bands at ca. 16,000cm(-1) for 1 and 16,500cm(-1) for 2. The magnetic properties ofcompounds are characteristic of a very weak antiferromagnetic interaction with J=-0.055cm(-1) and J=-0.096cm(-1) for 1 and 2, respectively. [GRAPHICS] .

Two novel derivatives of zoledronic acid (1-hydroxy-2-[1-(1H-imidazol-1-yl)cyclobutyl] ethylidene-1,1-diphosphonic acid (H(4)cbtZol) and 1-hydroxy-2-[1-(1H-imidazol-1-yl)cyclopentyl] ethylidene-1,1-diphosphonic acid (H(4)cptZol)) were synthesized, crystallized from water solutions as H(4)cbtZol center dot H2O (1) and H(4)cptZol center dot 4H(2)O (2), and characterized by single-crystal X-ray diffraction. The reactions of H(4)cbtZol and H(4)cptZol with acetate or sulphate Co(II) salts, carried out under hydrothermal conditions, afforded Co-3(HcbtZol)(2)(H2O)(6)center dot 6H(2)O (1a), being isomorphous with recently reported Co(II)/Ni(II) complexes based on HdmtZol(3-) and HcppZol(3-) anions, and Co-3(HcptZol)(2)(H2O)(4)center dot 2H(2)O (2a). Both 1a and 2a were characterized by means of X-ray crystallography, IR and NIR-Vis-UV spectroscopic methods. Furthermore, their thermal stabilities and magnetic properties were compared. Compounds 1a and 2a comprise 1D polymeric chains with crystallographically and spectroscopically distinct six-coordinated Co1 and Co2 centers, which differ in architectures. In 1a, the chains feature alternately arranged [Co2(HcbtZol)(H2O)(2)](2) and {Co1O(6)} units. The chains of 2a are constructed from dinuclear [Co2(HcptZol)(H2O)(2)](2) units built up from symmetry related edge-sharing {Co2O(6)} octahedrons, extended by corner-sharing {Co1O(6)} octahedrons, which results in higher rigidity imposed on trinuclear units and shorter Co2 center dot center dot center dot Co2 and Co1 center dot center dot center dot Co2 distances as compared to 1a. The crystal field parameters D-q, D-s, D-t and B of 798 cm(-1), 450 cm-(1), -75 cm(-1) and 857 cm(-1) for 1a and 644 cm(-1), 509 cm(-1), -146 cm(-1) and 902 cm(-1) for 2a revealed that the {Co2O(6)} octahedron of 2a exhibits a larger tetragonal distortion as compared to 1a, despite the nearly identical values of the tetragonality T parameter (1.07 for 2a and 1.06 for 1a). These differences are reflected in the thermal and magnetic behaviors of 1a and 2a. In particular, compound 2a is more stable than 1a, retaining thermal stability up to 208 degrees C. On the other hand, its dehydration is a one-stage process, accompanied by simultaneous destruction of its 1D architecture and immediate elimination and decomposition of ligands. The analysis of magnetic properties revealed the existence of competing interactions, with the predominant participation of antiferromagnetic interactions in 1a (spin-3/2 Heisenberg trimer chain) and ferromagnetic interactions in 2a (spin-1/2 Ising diamond chain).

The reaction of alpha,alpha-dimethyl substituted derivative of zoledronic acid with Ni(II) afforded 1D coordination polymer, Ni-3(HL)(2)(H2O)(6)center dot 6H(2)O (1). The title compound possess crystallographically and spectroscopically distinct Ni1 and Ni2 centers characterized by tetragonality distortion parameter T = 0.97 and 1.04, respectively, and is isomorphous with recently reported Co-3(HL)(2)(H2O)(6)center dot 6H(2)O complexes based on a,ot-dimethyl and cyclopropyl substituted zoledronate derivatives. Detailed analysis of thermal stability of 1 revealed that partly dehydrated [Ni-3(HL)(2)(H2O)(3)] still retains its architecture and structural integrity of coordinated ligands. Exploring supramolecular interactions that build up the crystal of 1 and related Co(II) complexes allowed a conclusion that distinct dehydration pathways observed for each compound may be correlated with subtle differences in 3D crystals packing. Ni-2(P2O7) salt was identified as the major final product of thermolysis of 1. xThe magnetic properties of 1 analyzed in term of a spin-1 Heisenberg Ni2Ni1Ni2 trimer chains model revealed antiferromagnetic Nil center dot center dot center dot Ni2 interactions within the trimers (J(1) = -7.32 cm(-1)) and ferromagnetic Ni2 center dot center dot center dot Ni2 intertrimers coupling (Theta(W) = 1.72 K). Furthermore, different values of the axial zfs D parameters and the g-factors were assigned to the Ni1 and Ni2 centers. (C) 2017 Elsevier Ltd. All rights reserved.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

While metal organic frameworks (MOFs) or, more generally, coordination polymers (CPs) built using linkers possessing two different functional groups are known very well in the literature, the effect of a third functional group on the physicochemical properties of those materials is weakly recognized. To study this issue we designed an aminocarboxy-phosphonic ligand, 3-amino-5-(dihydroxyphosphoryl)benzoic acid (H(3)APB), which is an amino derivative of meta-phosphonobenzoic acid. By self-assembly with a copper(II) source, we obtained the three-dimensional CP {[Cu-3(APB)(2)(H2O)(6)].6H(2)O}(n), 1, featuring rare binodal 4,5-connected tcs topology. By comparison with previously known representatives of that topology, we put forward a hypothesis that CPs of rare topologies, such as tcs, are obtained when polytopic, differentially substituted ligands are used. The structure of 1 is layered, but not in the manner typical for "traditional" metal phosphonates and carboxyphosphonates, and it was found to be flexible; structural flexibility has been demonstrated by dehydration hydration experiments. The structural changes were probed with the use of PXRD and IR methods. We have also shown that the copper(II) aminocarboxyphosphonate 1 presented herein has moderate capability for degradation of methylene blue, rhodamine B, and acridine orange in oxidizing conditions; however, the rate of dye degradation is greatly enhanced under visible light irradiation. Analysis of magnetic properties revealed that 1 is a spin-frustrated system with a diamond-chain arrangement of copper(II) ions. The Magnetic data were fitted using the isotropic Heisenberg as well as Ising models. Both models consistently indicate that magnetic exchange paths are both antiferromagnetic and ferromagnetic, with dominating participation of the former interaction.

Two novel α,α-disubstituted derivatives of zoledronic acid, namely 1-hydroxy-2-(1H-imidazol-1-yl)-2-methylpropylidene-1,1-diphosphonic acid (H4L1) and 1-hydroxy-2-[1-(1H-imidazol-1-yl)cyclopropyl]ethylidene-1,1-diphosphonic acid (H4L2) were synthesized and structurally characterized by single-crystal X-ray diffraction. The reaction of cobalt acetate with H4L1 and H4L2 carried out under hydrothermal conditions afforded two isomorphous Co3(HL1)2(H2O)6·6H2O (1a) and Co3(HL2)2(H2O)6·6H2O (2a) complexes. Both compounds are characterized by means of X-ray crystallography, IR and NIR-Vis-UV spectroscopic methods. Furthermore, their magnetic properties and thermal stabilities are reported. The crystals of 1a and 2a feature infinite 1D polymeric chains built from alternately arranged dinuclear [Co2(HL1/HL2)(H2O)2]2 units and {Co1O6} octahedra running along the [1[combining macron]10] crystallographic direction. In both compounds, crystallographically distinct Co1 and Co2 atoms are six-coordinated. As is reflected in T values (T - index of tetragonality), the coordination environment of Co1 generates a slightly elongated octahedron (T = 0.94), whereas a slightly compressed octahedron (T = 1.06 for 1a and 1.05 for 2a) is formed around Co2. An assumption that the d-d type absorption is mainly attributed to the inversion related Co2 centers, whose population is two times higher than that of Co1, afforded a good correlation between calculated transition energies and experimental NIR-Vis-UV spectra. The magnetic susceptibility measurements analyzed in terms of a spin-3/2 Heisenberg trimer chain revealed that Co1Co2 interactions within the trimer are antiferromagnetic whereas Co2Co2 intertrimer interactions are ferromagnetic.

The reaction of L-arginine and oxalate ions with copper(II) salts yields a new complex with formula of [Cu(L-Arg)(2)(H2O)]center dot C2O4 center dot 6H(2)O (1) (where L-Arg = L-arginine). Single crystals of I were synthesized by crystallization from aqueous solution. The complex properties were characterized by X-ray diffraction, spectroscopy (FT-IR, FT-Raman, NIR-Vis-IJV and EPR) as well as thermal and magnetic methods. The square pyramidal (SP) geometry around Cu(II) ions in [Cu(L-Arg)(2)(H2O)](2+) cation complex is formed by two cis-chelated L-arginine zwitterions and a water molecule coordinated in the apex of square pyramid. The trigonality distortion of SP geometry is relatively small, tau = 0.0087. The solid state EPR spectrum showed broad hyperfine splitting with g(perpendicular to)= 2.061 at 77 K. The copper centres distanced at 7.558(5) angstrom are joined in a single zig-zag structure via a chain based on the combination of Cu-O(5)-H(29)center dot center dot center dot O(2)-C1-O1-Cu hydrogen bonds along the b axis (d (O2 center dot center dot center dot O5) = 2.812 angstrom). Taking into account the structural features, the magnetic susceptibility data were best-fitted, giving the exchange parameter J = -0.16 cm(-1). Complex 1 is thermally stable up to 66 degrees C, where it was observed to lose the crystallization water molecules with an 11.7% mass loss (calc. 11.5%). (C) 2016 Elsevier B.V. All rights reserved.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

A novel 1D polymeric copper(ii) complex of formula {[Cu(l-Arg)2(μ-4,4′-bpy)]Cl2·3H2O∞} was synthesized and characterized using X-ray diffraction, FT-IR, Raman, electron paramagnetic resonance and NIR-vis-UV spectroscopy, and its microbiological properties were analyzed.

The 4,4′-bpy molecules are weakly bonded with nickel(ii) ions in 1Dl-tyrosinato coordination polymer.

Three novel isomorphous coordination polymers with a general formula [M(HO3P-C5H4N-PO3H)(2)(H2O)(2)](n) [M-II = Co (1), Zn (2) and Cd (3)] have been synthesized and characterized by powder and single-crystal X-ray diffraction, vibrational spectroscopy (IR and Raman) and simultaneous thermal analysis (TG-DTA-MS). Crystal structure analyses of compounds 1-3 have revealed that both phosphonate groups of (pyridin-1-ium-3,5-diyl)diphosphonate ligands serve to extend the metal cations into a strongly undulated grid structure parallel to the (101) plane. The adjacent monolayers are held together via multiple hydrogen bonds and offset face-to-face pi-pi interactions. The interlayer interaction energy values, estimated using the CRYSTAL code, have revealed that the stabilization energies of compounds 1-3 are quite similar, where 1 is least and 3 most advantageous. Computational studies have been further related to the results of thermal analyses. In the case of compound 1, which has unpaired electrons at the metal centre, the investigation has been supplemented by magnetic measurements. The magnetic properties of 1 (1.7-300 K) have been analyzed assuming that any possible exchange interactions are very weak. The obtained best-fit parameters are: Delta (axial splitting of T-4(1g) term) = -478 cm(-1), lambda (spin-orbit coupling) = -103 cm(-1), alpha (orbital reduction factor) = 1.38, and zJ' (mean-field exchange parameter) = -0.11 cm(-1). The negative value of Delta implies that the ground state is the orbital doublet, which cannot be treated within the spin-Hamiltonian approach.