RESUMO

The title mononuclear CoII complex, [Co(C5H7N6)2(C14H8O5)2(H2O)2]·2H2O, has been synthesized and its crystal structure determined by X-ray diffraction. The complex crystallizes in the triclinic space group P-1, with one formula unit per cell (Z = 1 and Z' = 1/2). It consists of a mononuclear unit with the CoII ion on an inversion centre coordinated by two 2,6-diamino-7H-purin-1-ium cations, two 4,4'-oxydibenzoate anions (in a nonbridging κO-monodentate coordination mode, which is less common for the anion in its CoII complexes) and two water molecules, defining an octahedral environment around the metal atom. There is a rich assortment of nonbonding interactions, among which a strong N+-H...O- bridge, with a short N...O distance of 2.5272 (18) Å, stands out, with the H atom ostensibly displaced away from its expected position at the donor side, towards the acceptor. The complex molecules assemble into a three-dimensional hydrogen-bonded network. A variable-temperature magnetic study between 2 and 300 K reveals an orbital contribution to the magnetic moment and a weak antiferromagnetic interaction between CoII centres as the temperature decreases. The model leads to the following values: A (crystal field strength) = 1.81, λ (spin-orbit coupling) = -59.9 cm-1, g (Landé factor) = 2.58 and zJ (exchange coupling) = -0.5 cm-1.

RESUMO

Three isotypic rare earth complexes, catena-poly[[aquabis(but-2-enoato-κ(2)O,O')yttrium(III)]-bis(µ-but-2-enoato)-κ(3)O,O':O;κ(3)O:O,O'-[aquabis(but-2-enoato-κ(2)O,O')yttrium(III)]-µ-4,4'-(ethane-1,2-diyl)dipyridine-κ(2)N:N'], [Y2(C4H5O2)6(C12H12N2)(H2O)2], the gadolinium(III) analogue, [Gd2(C4H5O2)6(C12H12N2)(H2O)2], and the gadolinium(III) analogue with a 4,4'-(ethene-1,2-diyl)dipyridine bridging ligand, [Gd2(C4H5O2)6(C12H10N2)(H2O)2], are one-dimensional coordination polymers made up of centrosymmetric dinuclear [M(but-2-enoato)3(H2O)]2 units (M = rare earth), further bridged by centrosymmetric 4,4'-(ethane-1,2-diyl)dipyridine or 4,4'-(ethene-1,2-diyl)dipyridine spacers into sets of chains parallel to the [201̄] direction. There are intra-chain and inter-chain hydrogen bonds in the structures, the former providing cohesion of the linear arrays and the latter promoting the formation of broad planes parallel to (010).

RESUMO

The asymmetric unit of the title compound, C8H9NO2·H2O consists of an isolated 4-(ammonio-meth-yl)benzoate zwitterion derived from 4-amino-methyl-benzoic acid through the migration of the acidic proton, together with a water molecule of crystallization that is disordered over three sites with occupancy ratios (0.50:0.35:0.15). In the crystal structure, N-H⋯O hydrogen bonds together with π-π stacking of the benzene rings [centroid-centroid distance = 3.8602 (18) Å] result in a strongly linked, compact three-dimensional structure.

RESUMO

4,4'-(Disulfanediyl)dibutanoic acid (dtba) and 4,4'-bipyridine (4,4'-bpy) crystallize in an 1:1 ratio, leading to the title co-crystal with composition C8H14O4S2·C10H8N2. A distinctive feature of the crystal structure is the geometry of the dtba moiety, which appears to be stretched [with a 9.98 (1) Šspan between outermost carbons] and acts as an hydrogen-bonding connector, forming linear chains along [-211] with the 4,4'-bpy moiety by way of O-H⋯N hydrogen bonds and C-H⋯O interactions. The influence of the mol-ecular shape on the hydrogen-bonding pattern is analysed by comparing the title compound and two other 4,4'-bpy co-crystals with closely related mol-ecules of similar formulation but different geometry, showing the way in which this correlates with the packing arrangement.

RESUMO

Two new Ni(II) complexes involving the ancillary ligand bis[(pyridin-2-yl)methyl]amine (bpma) and two different carboxylate ligands, i.e. homophthalate [hph; systematic name: 2-(2-carboxylatophenyl)acetate] and benzene-1,2,4,5-tetracarboxylate (btc), namely catena-poly[[aqua{bis[(pyridin-2-yl)methyl]amine-κ(3)N,N',N''}nickel(II)]-µ-2-(2-carboxylatophenyl)aceteto-κ(2)O:O'], [Ni(C9H6O4)(C12H13N3)(H2O)]n, and (µ-benzene-1,2,4,5-tetracarboxylato-κ(4)O(1),O(2):O(4),O(5))bis(aqua{bis[(pyridin-2-yl)methyl]amine-κ(3)N,N',N''}nickel(II)) bis(triaqua{bis[(pyridin-2-yl)methyl]amine-κ(3)N,N',N''}nickel(II)) benzene-1,2,4,5-tetracarboxylate hexahydrate, [Ni2(C10H2O8)(C12H13N3)2(H2O)2]·[Ni(C12H13N3)(H2O)3]2(C10H2O8)·6H2O, (II), are presented. Compound (I) is a one-dimensional polymer with hph acting as a bridging ligand and with the chains linked by weak C-H···O interactions. The structure of compound (II) is much more complex, with two independent Ni(II) centres having different environments, one of them as part of centrosymmetric [Ni(bpma)(H2O)]2(btc) dinuclear complexes and the other in mononuclear [Ni(bpma)(H2O)3](2+) cations which (in a 2:1 ratio) provide charge balance for btc(4-) anions. A profuse hydrogen-bonding scheme, where both coordinated and crystal water molecules play a crucial role, provides the supramolecular linkage of the different groups.

RESUMO

The title mononuclear complex, [Nd(C5H3N2O3)3(H2O)3]·3H2O, consists of an Nd(III) cation, three 2,4-dioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate ligands and three aqua ligands forming the neutral complex molecule, and three solvent water molecules. The pyrimidinecarboxylate ligands act in a chelating manner, via carboxylate and keto O atoms. The NdO9 coordination polyhedron is in the form of a distorted monocapped square antiprism. The availability of numerous hydrogen-bonding donors and acceptors results in a very dense hydrogen-bonding network, the immediate effect of which is an unusually large packing index.

Assuntos

RESUMO

Poly[[tetraaquadi-µ4-citrato-tetrakis(2,6-diaminopurine)tetracobalt(II)] 6.35-hydrate], {[Co4(C6H4O7)2(C5H6N6)4(H2O)4]·6.35H2O}n, presents three different types of Co(II) cations in the asymmetric unit, two of them lying on symmetry elements (one on an inversion centre and the other on a twofold axis). The main fragment is further composed of one fully deprotonated citrate (cit) tetraanion, two 2,6-diaminopurine (dap) molecules and two aqua ligands. The structure is completed by a mixture of fully occupied and disordered solvent water molecules. The two independent dap ligands are neutral and the cit tetraanion provides for charge balance, compensating the 4+ cationic charge. There are two well defined coordination geometries in the structure. The simplest is mononuclear, with the Co(II) cation arranged in a regular centrosymmetric octahedral array, coordinated by two aqua ligands, two dap ligands and two O atoms from the ß-carboxylate groups of the bridging cit tetraanions. The second, more complex, group is trinuclear, bisected by a twofold axis, with the metal centres coordinated by two cit tetraanions through their α- and ß-carboxylate and α-hydroxy groups, and by two dap ligands bridging through one of their pyridine and one of their imidazole N atoms. The resulting coordination geometry around each metal centre is distorted octahedral. Both groups are linked alternately to each other, defining parallel chains along [201], laterally interleaved and well connected via hydrogen bonding to form a strongly coupled three-dimensional network. The compound presents a novel µ4-κ(5)O:O,O':O',O'',O''':O'''' mode of coordination of the cit tetraanion.

RESUMO

The title compound, C(9)H(8)N(2), presents two almost identical independent molecules in the asymmetric unit, both of them exhibiting an extremely planar isoquinoline core (maximum r.m.s. deviation = 0.014 Å). The most significant deviation is found in the -NH(2) groups, which present a noticeable pyramidalization around the N atom, a feature also present in related structures containing the molecule as a ligand. The supramolecular structure is based on pairs of parallel hydrogen-bonded chains formed by just one molecular type each, defined by the strongest hydrogen bonds in the structure, which are of the N-H···N type. These parallel chains are linked into pairs (or strips) via weaker C-H···N hydrogen bonds. Related strips generated by the c-glide plane define two families running along [110] and [110], giving rise to an interesting system of interwoven chains stabilized by a number of weaker contacts of the C-H···π type.

RESUMO

The title ionic compound, (C(7)H(8)N(3))(2)[Ho(2)(C(4)H(5)O(2))(8)], is constructed from two almost identical independent centrosymmetric anionic dimers balanced by two independent 2-amino-1H-benzimidazol-3-ium (Habim(+)) cations. The asymmetric part of each dimer is made up of one Ho(III) cation and four crotonate (crot or but-2-enoate) anions, two of them acting in a simple η(2)-chelating mode and the remaining two acting in two different µ(2):η(2) fashions, viz. purely bridging and bridging-chelating. Symmetry-related Ho(III) cations are linked by two Ho-O-Ho and two Ho-O-C-O-Ho bridges which lead to rather short intracationic Ho···Ho distances [3.8418 (3) and 3.8246 (3) Å]. In addition to the obvious Coulombic interactions linking the cations and anions, the isolated [Ho(2)(crot)(8)](2-) and Habim(+) ions are linked by a number of N-H···O hydrogen bonds, in which all N-H groups of the cation are involved as donors and all (simple chelating) crot O atoms are involved as acceptors. These interactions result in compact two-dimensional structures parallel to (110), which are linked to each other by weaker π-π contacts between Habim(+) benzene groups.

Assuntos

RESUMO

The asymmetric unit of the title compound, {[La(C(4)H(5)O(2))(3)(H(2)O)(2)]·C(5)H(5)N(5)·H(2)O}(n), consists of an La(III) cation, three crotonate (but-2-enoate) anions and two coordinated water molecules forming the neutral complex, completed by an external adenine molecule and one hydration water molecule. The LaO(10) coordination polyhedra, connected through the sharing of a single edge, form isolated chains running along the [100] direction. These one-dimensional structures are characterized by two different centrosymmetric La(2)O(2) loops, with La...La distances of 4.5394 (6) and 4.5036 (6) Å. The unbound adenine and water solvent molecules form a highly planar hydrogen-bonded array parallel to (110) (r.m.s. deviation from the mean plane < 0.10 Å) which intersects the isolated La-crotonate chains in a slanted fashion to form an extremely connected hydrogen-bonded three-dimensional structure.

RESUMO

The asymmetric unit of the title dimeric compounds, [Ln(2)(C(4)H(5)O(2))(6)(H(2)O)(4)]·C(5)H(5)N(5)·7H(2)O, with Ln = Dy, (I), and Sm, (II), consists of an Ln(III) cation, three crotonate (but-2-enoate) anions and two coordinated water molecules forming the neutral complex, cocrystallized with half of an external adenine molecule and 3.5 water molecules. The metal complex has crystallographic inversion symmetry. The LnO(9) coordination polyhedra are connected through the sharing of a single edge to form isolated dimeric units, with Ln...Ln separations of 4.1766 (12) Å for (I) and 4.2340 (12) Å for (II). The unbound adenine molecule and one of the solvent water molecules are disordered around an inversion centre into two overlapping, equally populated, units. The structure is sustained by a complex hydrogen-bonding scheme involving all possible O-H and N-H groups as donors, and crotonate and water O and adenine N atoms as acceptors. The system is compared with recently published related compounds.

RESUMO

In the title polymeric compound, [Cu(C(9)H(6)O(4))(C(3)H(4)N(2))(2)](n), the copper(II) cation occupies an N(2)O(3) coordination sphere defined by two 1H-imidazole (imid) ligands in trans positions and three carboxylate O atoms from three different 2-(carboxylatomethyl)benzoate (hpt(2-)) dianions. The geometry is that of a square pyramid with one of the O atoms at the apex, bridging neighbouring metal centres into an [-ON(2)CuO(2)CuN(2)O-] dinuclear unit. These units are in turn connected by hpt anions into a reticular mesh topologically characterized by two types of loops, viz. a four-membered Cu(2)O(2) diamond motif and a 32-membered Cu(4)O(8)C(20) ring. The imid groups do not take part in the formation of the two-dimensional structure, but take part in the N-H···O interactions. These arise only within individual planes, interplanar interactions being only of the van der Waals type.

Assuntos

RESUMO

The title polymeric compound, {(C(13)H(16)N(2))[Co(C(10)H(3)O(8))(C(13)H(14)N(2))(H(2)O)(2)](2)·5H(2)O}(n), is an ionic structure comprising an anionic two-dimensional mesh characterized by a {[Co(Hbtc)(bpp)(H(2)O)(2)](-)}(2) motif [Hbtc is 5-carboxybenzene-1,2,4-tricarboxylate and bpp is 1,3-bis(4-pyridyl)propane], with interspersed 4,4'-(propane-1,3-diyl)dipyridinium cations, denoted (H(2)bpp)(2+), and water molecules providing the charge balance and structure stabilization. The reticular mesh consists of two independent types of [Co(H(2)O)(2)](2+) cationic nodes (lying on inversion centres), interconnected in the [101] direction by two independent sets of neutral bridging bpp ligands, both types of ligands being split by non-equivalent twofold axes. One set is formed by genuinely symmetric moieties, while those in the second set are only symmetric by disorder in the central propane bridge. These chains contain only one type of Co(II) centre and one type of bpp ligand; the metal cations therein are laterally bridged by Hbtc anions, thus forming transverse chains of alternating types of Co(II) cations. The elemental motif of the resulting grid is a highly distorted parallelogram, with metal-metal distances of 13.5242 (14) Å in the bpp direction and 9.105 (2) Å in the Hbtc direction, and a large internal angle of 138.42 (18)°. These two-dimensional structures have a profusion of hydrogen-bonding interactions with each other, either directly (with the aqua molecules as donors and the Hbtc anions as acceptors) or mediated by the unbound (H(2)bpp)(2+) cations and water molecules of hydration. These interactions generate a very complex hydrogen-bonding scheme involving all of the available N-H and O-H groups and which links these two-dimensional grids into a three-dimensional network.

Assuntos

RESUMO

The title compound, [Co(C(5)H(7)N(6))(2)(H(2)O)(4)](C(10)H(2)O(8))·4H(2)O, is an ionic structure comprising a [Co(Hdap)(2)(H(2)O)(4)](4+) cation (dap is 2,6-diaminopurine) in a general position, two benzene-1,2,4,5-tetracarboxylate (btc(4-)) anions straddling two different inversion centres and four solvent water molecules. The structure presents a remarkable degree of pseudosymmetry, with the Co(II) cation lying almost exactly on a noncrystallographic pseudo-inversion centre. The overall spatial arrangement can be described in terms of cationic and anionic chains running along the [111] direction and linked into a three-dimensional network by a very complex hydrogen-bonding scheme in which all the available N-H and O-H groups take part.

RESUMO

The two isomorphous title compounds, [M(C(5)H(7)N(6))(2)(C(9)H(6)O(4))(2)(H(2)O)(2)]·4H(2)O or M(2+)(Hdap(+))(2)(hpt(2-))(2)(H(2)O)(2)·4H(2)O {where dap is 2,6-diaminopurine, H(2)hpt is homophthalic acid [2-(2-carboxyphenyl)acetic acid] and M is Ni(II) or Co(II)}, consist of neutral M(2+)(Hdap(+))(2)(hpt(2-))(2)(H(2)O)(2) monomers, where the M(II) cation lies on an inversion centre and its MN(2)O(4) octahedral environment is defined by one N atom (from Hdap(+)), two O atoms (from one hpt(2-) dianion and one water molecule) and their inversion images. The structures are unusual in that the Hdap(+) cation occurs in an uncommon protonated state (as 2,6-diamino-7H-purin-1-ium) and both ligands bind in an unprecedented monodentate fashion. The existence of a large number of donors and acceptors for hydrogen bonding, together with π-π interactions, leads to a rather complex three-dimensional structure.

Assuntos

RESUMO

The structure of the ionic title compound, (C(5)H(7)N(6))(2)[Nd(2)(C(5)O(5))(4)(H(2)O)(8)], consists of anionic dimers built around an inversion centre and is made up of an Nd(III) cation, two croconate (croco) dianions and four water molecules (plus their inversion images), with two noncoordinated symmetry-related 2,6-diamino-1H-purin-3-ium (Hdap(+)) cations providing charge balance. Each Nd(III) atom is bound to nine O atoms from four water and three croco units. The coordination polyhedron has the form of a rather regular monocapped square antiprism. The croconate anions are regular and the Hdap(+) cation presents a unique, thus far unreported, protonation state. The abundance of hydrogen-bonding donors and acceptors gives rise to a complex packing scheme consisting of dimers interlinked along the three crystallographic directions and defining anionic `cages' where the unbound Hdap(+) cations lodge, linking to the mainframe via (N-H)(Hdap)···O(water/croco) and (O-H)(water)···N(Hdap) interactions.

Assuntos

RESUMO

Two structures presenting an uncomplexed 2,6-diaminopurine (dap) group are reported, namely 2,6-diamino-9H-purine monohydrate, C(5)H(6)N(6)·H(2)O, (I), and bis(2,6-diamino-9H-purin-1-ium) 2-(2-carboxylatophenyl)acetate heptahydrate, 2C(5)H(7)N(6)(+)·C(9)H(6)O(4)(2-)·7H(2)O, (II). Both structures are rather featureless from a molecular point of view, but present instead an outstanding hydrogen-bonding scheme. In compound (I), this is achieved through a rather simple independent unit content (one neutral dap and one water molecule) and takes the form of two-dimensional layers tightly connected by strong hydrogen bonds, and interlinked by much weaker hydrogen bonds and π-π interactions. In compound (II), the fundamental building blocks are more complex, consisting of two independent 2,6-diamino-9H-purin-1-ium (Hdap(+)) cations, one homophthalate [2-(2-carboxylatophenyl)acetate] dianion and seven solvent water molecules. The large number of hydrogen-bond donors and acceptors produces 26 independent interactions, leading to an extended and complicated network of hydrogen bonds in a packing organization characterized by the stacking of interleaved anionic and cationic planar arrays. These structural characteristics are compared with those of similar compounds in the literature.

RESUMO

When excess uronic acid over Cr(VI) is used, the oxidation of D-glucuronic acid (Glucur) by Cr(VI) yields D-glucaric acid (Glucar) and Cr(III) as final products. The redox reaction involves the formation of intermediate Cr(IV) and Cr(V) species, with Cr(VI) and Cr(V) reacting with Glucur at comparable rates. The rate of disappearance of Cr(VI), and Cr(V) increases with [H(+)] and [substrate]. The experimental results indicated that Cr(IV) is a very reactive intermediate since its disappearance rate is much faster than Cr(VI)/Cr(V) and decreases when [H(+)] rises. Even at high [H(+)] Cr(IV) intermediate was involved in fast steps and does not accumulate in the reaction. Kinetic studies show that the redox reaction between Glucur and Cr(VI) proceeds through a mechanism combining one- and two-electron pathways for the reduction of intermediate Cr(IV) by the organic substrate: Cr(VI) --> Cr(IV) --> Cr(II) and Cr(VI) --> Cr(IV) --> Cr(III). The mechanism is supported by the observation of free radicals, CrO(2)(2+) (superoxoCr(III) ion) and Cr(V) as reaction intermediates. The EPR spectra show that five-co-ordinate oxo-Cr(V) bischelates are formed at pH < or = 4 with the uronic acid bound to Cr(V) through the carboxylate and the alpha-OH group of the furanose form. Five-co-ordinated oxo-Cr(V) monochelates are observed as minor species in addition to the major five-co-ordinated oxo-Cr(V) bischelates. At pH 7.5 the EPR spectra show the formation of a Cr(V) complex where the cis-diol groups of Glucur participate in the bonding to Cr(V). In vitro, our studies on the chemistry of Cr(V) complexes can provide information on the nature of the species that are likely to be stabilized in vivo. In particular, the EPR pattern of Glucur-Cr(V) species can be used as a finger print to identify Cr(V) complexes formed in biological systems.

Assuntos

RESUMO

The title isomorphous compounds, tetra-mu-but-2-enoato-bis[diaqua(but-2-enoato)dysprosium(III)]-2,6-diaminopurine (1/2), [Dy(2)(C(4)H(5)O(2))(6)(H(2)O)(4)].2C(5)H(6)N(6), and tetra-mu-but-2-enoato-bis[diaqua(but-2-enoato)holmium(III)]-2,6-diaminopurine (1/2), [Ho(2)(C(4)H(5)O(2))(6)(H(2)O)(4)].2C(5)H(6)N(6), consist of [Ln(crot)(3)(H(2)O)(2)](2) dimers (crot is crotonate or but-2-enoate; Ln is the lanthanide cation), built up around inversion centres and completed by 2,6-diaminopurine molecules. The lanthanide cation is coordinated by three chelating crotonate units and two water molecules. One of the chelating carboxylate groups acts also in a bridging mode sharing one O atom with both cations and the final result is a pair of DyO(9) tricapped prismatic polyhedra linked to each other through a central (Dy-O)(2) loop. A feature of the structures is the existence of a complex intermolecular interaction scheme involving two sets of tightly interlinked non-intersecting one-dimensional structures, one of them formed by the [Dy(crot)(3)(H(2)O)(2)](2) dimers (running along [100] and linked by O-H...O hydrogen bonds) and the second formed by 2,6-diaminopurine molecules (evolving along [010] linked by N-H...N hydrogen bonds).

Assuntos

RESUMO

catena-Poly[[tetraaquabis(1H-pyrazole-kappaN(2))nickel(II)] [[diaquabis(1H-pyrazole-kappaN(2))nickel(II)]-mu-benzene-1,2,4,5-tetracarboxylato-kappa(2)O(1):O(4)] tetrahydrate], {[Ni(C(3)H(4)N(2))(2)(H(2)O)(4)][Ni(C(10)H(2)O(8))(C(3)H(4)N(2))(2)(H(2)O)(2)].4H(2)O}(n), (I), and poly[[(mu(4)-benzene-1,2,4,5-tetracarboxylato-kappa(4)O(1):O(2):O(4):O(5))octakis(1H-pyrazole-kappaN(2))dicobalt(II)] tetrahydrate], {[Co(2)(C(10)H(2)O(8))(C(3)H(4)N(2))(8)].4H(2)O}(n), (II), are polymeric compounds crystallizing in the space group P1, with two independent metallic cations and one benzene-1,2,4,5-tetracarboxylate (btc) anion, each lying on symmetry centres. Individual coordination polyhedra are regular and the main differences are in the way the btc anion binds [mu(2) in (I) and mu(4) in (II)], promoting a 'chain-like' one-dimensional structure in (I) and a 'sieve-like' two-dimensional motif in (II).

Assuntos