Aqua(oxydiacetato‐κ3O,O′,O′′)(pyridine‐3‐carboxamide‐κN1)copper(II) sesquihydrate

In the monomeric title compound, [Cu(C₄H₄O₅)(C₆H₆N₂O)(H₂O)]·1.5H₂O, the Cu^II cation is bound in a square‐pyramidal coordination to a tridentate oxydiacetate (ODA) ligand, a monodentate pyridine‐3‐carboxamide (p3ca) ligand and one aqua ligand, where the two organic ligands form the basal plane and the water O atom occupies the unique apical site. The ODA ligand presents a slight out‐of‐plane puckering in its central ether O atom, while the p3ca ligand is essentially planar. The availability of efficient donors and acceptors for hydrogen bonding results in the formation of strongly linked hydrogen‐bonded bilayers parallel to (101), with an interplanar distance of 3.18 (1) Å and a stacking separation between the bilayers of 3.10 (1) Å, both of them governed by extended π–π interactions. The disordered nature of the solvent water molecules around inversion centres is discussed. The monoaqua compound is compared with the octahedral diaqua analogue, [Cu(C₄H₄O₅)(C₆H₆N₂O)(H₂O)₂], reported recently [Perec & Baggio (2009). Acta Cryst. C 65 , m296–m298].     

Diaqua(oxydiacetato‐κ3O,O′,O′′)(pyridine‐3‐carboxamide‐κN1)copper(II)

In the mononuclear title compound, [Cu(C₄H₄O₅)(C₆H₆N₂O)(H₂O)₂], the Cu^II centre is bound to a chelating oxydiacetate ligand, a monodentate pyridine‐3‐carboxamide unit and two water molecules, defining an octahedral coordination where the first two ligands form the equatorial plane and the last two occupy the apical sites. The planar oxydiacetate ligand is slightly disordered at its central ether O atom. The availability of efficient donors and acceptors for hydrogen bonding results in a complex interaction scheme where each monomer links to six similar units to define a well connected three‐dimensional structure. A comparison is made with related structures in the literature, and the reasons for their differences are discussed.     

(2,2′‐Biquinoline‐κ2N,N′)bis(nitrato‐κ2O,O′)copper(II)

In the title monomer, [Cu(NO₃)₂(C₁₈H₁₂N₂)], the six‐coordinated Cu^II atom lies on a twofold axis which bisects one of the ligands (a chelating biquinoline) and duplicates the remaining ligand, a chelating nitrate. The latter binds in a very asymmetric way, consistent with a Jahn–Teller distortion in the coordination polyhedron which, due to the triple chelation, is extremely distorted and difficult to describe in terms of any regular model.     

(Acetato‐κO)aqua(1H‐imidazole‐κN3)(picolinato‐κ2N,O)copper(II) 0.87‐hydrate: a Z′> 1 structure

The crystal structure of the title compound, [Cu(C₆H₄NO₂)(C₂H₃O₂)(C₃H₄N₂)(H₂O)]·0.87H₂O, has a square‐pyramidal‐coordinated Cu^II centre (the imidazole is trans to the picolinate N atom, the acetate is trans to the picolinate –CO₂ group and the aqua ligand is in a Jahn–Teller‐elongated apical position) and has two symmetry‐independent molecules in the unit cell (Z′ = 2), which are connected through complementary imidazole–picolinate N—H...O hydrogen bonding. The two partially occupied solvent water molecules are each disordered over two positions. The disordered solvent water molecules, together with pseudosymmetry elements, support the notion that a crystal structure with multiple identical chemical formula units in the structural asymmetric unit (Z′ > 1) can represent a crystal `on the way', that is, a kinetic intermediate form which has not yet reached its thermodynamic minimum. Neighbouring molecules form π–π stacks between their imidazole and picolinate N‐heterocycles, with centroid–centroid distances in the range 3.582 (2)–3.764 (2) Å.     

catena‐Poly[[bis(1H‐benzimidazole‐κN3)(salicylato‐κO)copper(II)]‐μ‐salicylato‐O,O′:O′′]

The title compound, [Cu(C₇H₅O₃)₂(C₇H₆N₂)₂]_n, is a one‐dimensional polymeric complex bridged by salicyl­ate anions. The Cu^II atom is surrounded by three salicyl­ate and two benz­imidazole ligands, with a tetragonally elongated octahedral coordination geometry. The Cu—O bond distances in the axial directions are 2.6092 (16) and 2.6834 (17) Å. π–π stacking interactions exist between the benz­imidazole rings of neighboring polymeric complex chains.     

Poly[(N,N‐dimethylformamide‐κO)(μ3‐4,4′‐ethylenedibenzoato‐κ5O,O′:O′:O′′,O′′′)(pyrazino[2,3‐f][1,10]phenanthroline‐κ2N8,N9)lead(II)]

In the title Pb^II coordination polymer, [Pb(C₁₆H₁₀O₄)(C₁₄H₈N₄)(C₃H₇NO)]_n, each Pb^II atom is eight‐coordinated by two chelating N atoms from one pyrazino[2,3‐f][1,10]phenanthroline (L) ligand, one dimethylformamide (DMF) O atom and five carboxylate O atoms from three different 4,4′‐ethylenedibenzoate (eedb) ligands. The eedb dianions bridge neighbouring Pb^II centres through four typical Pb—O bonds and one longer Pb—O interaction to form a two‐dimensional structure. The C atoms from the L and eedb ligands form C—H...O hydrogen bonds with the O atoms of eedb and DMF ligands, which further stabilize the structure. The title compound is the first Pb^II coordination polymer incorporating the L ligand.     

Aqua(dipicolinato‐κ3O,N,O′)(1H‐imidazole‐κN3)(1,10‐phenanthroline‐N,N′)manganese(II)

In the title compound, [Mn(C₇H₃NO₄)(C₃H₄N₂)(C₁₂H₈N₂)(H₂O)], the Mn^II centre is surrounded by one bidentate phenanthroline ligand [Mn—N = 2.383 (3) and 2.421 (3) Å], one tridentate dipicolinate ligand [Mn—N = 2.300 (3) Å, and Mn—O = 2.300 (2) and 2.357 (2) Å], one monodentate imidazole ligand [Mn—N = 2.238 (3) Å] and one water molecule [Mn—O = 2.157 (3) Å]. It displays a distorted pentagonal‐bipyramidal geometry, with neighbouring angles within the equatorial plane ranging from 68.05 (9) to 77.48 (10)°. Intermolecular O—H...O hydrogen bonds link the molecules into infinite chains. The chains are crosslinked by hydrogen bonds involving the carboxyl O atoms of the dipicolinate ligand and the protonated imidazole N atom, leading to an infinite two‐dimensional network sheet packing mode. The complete solid‐state structure can be described as a three‐dimensional supramolecular framework, stabilized by these intermolecular hydrogen‐bonding interactions and π–π stacking interactions involving the phenanthroline rings.     

A novel titanium–μ‐O–zirconium complex: bis(μ‐methyliminodiethanolato‐1κ3O,N,O′;1:2κ2O)(methyliminodiethanolato‐2κ3O,N,O′)dipropanolato‐1κO,2κO‐titanium(IV)zirconium(IV)

The title compound, [TiZr(C₅H₁₁NO₂)₃(C₃H₇O)₂], contains three methyl­imino­diethano­late ligands, two in different μ‐oxo bridging coordination modes and one bound only to the Ti atom. The Ti and Zr atoms have distorted octahedral and pentagonal–bipyramidal coordinations, respectively, which share edges. As well as some conformational disorder in the carbon chains, there is chemical disorder at one Ti site, with a mix of n‐ and isopropanolate ligands.     

Dibromido(dimethyl sulfoxide‐κO)(1,10‐phenanthroline‐κ2N,N′)copper(II)

The solvent effect on the molecular structures of copper(II) complexes produced from the reaction between CuBr₂ and 1,10‐phenanthroline is evident. The momomeric title compound, [CuBr₂(C₁₂H₈N₂)(C₂H₆OS)], which consists of discrete units, is produced from this reaction in dimethyl sulfoxide (DMSO), whereas a polymeric copper(II) compound is known to be produced from the same reaction in the poor coordinating solvent ethanol. The geometry around the copper(II) ion in the title compound is best described as trigonal–bipyramidal distorted square‐based pyramidal, with a τ value of 0.37. The two phenanthroline N atoms, the DMSO O atom and one of the Br atoms occupy the four basal positions, while the second Br atom occupies the axial position. The magnetic susceptibility data also indicate that the title compound is monomeric, but there is still a weak antiferromagnetic interaction between paramagnetic copper(II) centers via the intermolecular `Cu—Br...Br—Cu' contact pathway.     

(N‐{[4‐(1,3‐Benzothiazol‐2‐yl)anilino]carbonylmethyl‐κO}iminodiacetato‐κ3O,N,O′)(1,10‐phenanthroline‐κ2N,N′)cobalt(II) pentahydrate

The title compound, [Co(C₁₉H₁₅N₃O₅S)(C₁₂H₈N₂)]·5H₂O, has a moderately distorted octahedral coordination environment composed of two N atoms of a 1,10‐phenanthroline ligand and one N and three O atoms of an N‐{[4‐(1,3‐benzothiazol‐2‐yl)anilino]carbonylmethyl}iminodiacetate (ZL‐5²⁻) ligand. The ring systems of the phenanthroline and ZL‐5²⁻ ligands are coplanar and the complexes pack in layers parallel to the ab plane with the rings of adjacent complexes facing one another. The layers stack along the c axis and are linked by hydrogen bonds involving the five water solvent molecules in the asymmetric unit and O atoms of the acetate groups of the ZL‐5²⁻ ligand. This is believed to be the first crystal structure of a complex of a 2‐(4‐aminophenyl)benzothiazole ligand.     

Chlorido[N,N′‐dibenzyl‐N′′‐(trichloroacetyl)phosphoramidato‐κ2O,O′](1,10‐phenanthroline‐κ2N,N′)copper(II)

In the title complex, [Cu(C₁₆H₁₆Cl₃N₃O₂P)Cl(C₁₂H₈N₂)], the Cu^II cation presents a square‐pyramidal environment, where the CuO₂N₂ base is formed by two O atoms from carbonyl and phosphoryl groups, and by two N atoms from a 1,10‐phenanthroline molecule. A coordinated Cl atom occupies the apex. N—H...Cl hydrogen bonds link the molecules into one‐dimensional chains. The trichloromethyl group is rotationally disordered over two positions, with occupancies of 0.747 (7) and 0.253 (7).     

catena‐Poly­[[aqua(2,2′‐bi­pyridine‐κ2N,N′)­manganese(II)]‐μ‐terephthalato‐κ3O,O′:O′′]

The title complex, [Mn(C₈H₄O₄)(C₁₀H₈N₂)(H₂O)]_n, takes the form of a zigzag chain, with the terephthalate dianion (tp) acting as a tridentate ligand. The Mn^II center is surrounded by two tp ligands, one water mol­ecule and one 2,2′‐bi­pyridine (bipy) ligand and exhibits a severely distorted octahedral coordination environment, with cis angles ranging from 57.31 (8) to 123.97 (11)°. The complete solid‐state structure can be described as a three‐dimensional supramolecular framework stabilized by hydrogen‐bonding interactions involving the coordinated water mol­ecule and the carboxy O atoms of the tp ligands, and by π–π stacking interactions involving the bipy rings and the benzene ring of the tp ligand.     

Bis(4,4′‐bi­pyridine‐κN)­bis­(hydrogen phthalato)‐κ2O,O′;κO‐zinc(II)

The title compound, [Zn(C₈H₅O₄)₂(C₁₀H₈N₂)₂], was obtained by the hydro­thermal reaction of ZnSO₄·7H₂O with phthalic acid (H₂pht) and 4,4′‐bi­pyridine (4,4′‐bipy). Crystallographic analysis shows that it has a one‐dimensional double‐chain structure via hydrogen‐bonding interactions. Each Zn^II atom, adopting a distorted tetrahedral geometry, is coordinated by two N atoms from two 4,4′‐bipy ligands, with Zn—N distances of 2.054 (4) and 2.104 (4) Å, and by two O atoms from symmetry‐related Hpht⁻ ligands, with Zn—O distances of 1.921 (4) and 2.019 (4) Å.     

Bis(2‐chloro‐5‐methylpyridine‐κN)bis(nitrato‐κ2O,O′)copper(II)

In the molecule of the title compound, [Cu(NO₃)₂(C₆H₆ClN)₂], the Cu atom lies on an inversion centre and is six‐coordinated by two pyridine N atoms and four nitrate O atoms in trans positions. The nitrate acts as an unsymmetrical bidentate ligand. The coordination geometry is octahedral, with the Cu—N and the two Cu—O distances being 1.9939 (16), 2.0246 (16) and 2.4866 (19) Å, respectively. There are five types of C—H⋯O hydrogen bonds. Two of these generate two‐dimensional molecular networks in the direction of the a axis, and the others connect adjacent molecular networks.     

mer‐Bis(1,4‐dibenzoylthiosemicarbazidato‐κ3O,N,O′)cobalt(II)

The title complex, [Co(C₁₅H₁₂N₃O₂S)₂], consists of an octahedrally coordinated Co^II ion, with two crystallographically independent 1,4‐dibenzoylthiosemicarbazidate ligands in a tridentate mer coordination [Co—O = 2.064 (3)–2.132 (3) Å and Co—N = 2.037 (3)–2.043 (3) Å]. There are intermolecular N—H...S hydrogen bonds involving one ligand and strong π–π stacking interactions involving the other ligand, resulting in a three‐dimensional supramolecular framework. The hydrogen bonds and π–π interactions, as well as different intramolecular aryl–benzamide H—C...H(—N) distances, give rise to a difference in conformation between the two ligands.     

μ2‐Acetato‐κ2O:O′‐tris(μ2‐ferrocenecarboxylato‐κ2O:O′)bis[(N,N‐dimethylformamide‐κO)copper(II)]

The title compound, [Cu₂Fe₃(C₅H₅)₃(C₂H₃O₂)(C₆H₄O₂)₃(C₃H₇NO)₂], belongs to the classic dimeric paddle‐wheel structure type. It is an unusual example in that it contains two different carboxylate groups, viz. ferrocenecarboxylate and acetate. With three ferrocenecarboxylate groups and only one acetate group bridging the two Cu centres, a noncentrosymmetric molecular arrangement results.     

Dibromo(pyridoxal semicarbazone‐κ3N1,O3,O3′)copper(II)

The title compound, di­bromo(3‐hydroxy‐5‐hydroxy­methyl‐2‐methyl‐4‐pyridine­carbox­aldehyde semicarbazone‐κ³N¹,O³,O^3′)copper(II), [CuBr₂(C₉H₁₂N₄O₃)], consists of discrete complex units with the tridentate pyridoxal semicarbazone ligand as a zwitterion in an almost planar configuration. The Cu^II ions are in a distorted square‐pyramidal coordination, with the equatorial Br atom at a distance of 2.4017 (6) Å and the apical Br atom at a distance of 2.6860 (6) Å.     

(2,2′‐Di­amino‐4,4′‐bi‐1,3‐thia­zole‐κ2N3,N3′)(oxy­diacetato‐κ3O,O′,O′′)­copper(II) monohydrate

The title compound, [Cu(C₄H₄O₅)(C₆H₆N₄S₂)]·H₂O, displays a square‐pyramidal coordination geometry. The tridentate oxy­di­acetate dianion chelates the Cu^II atom in the facial mode. The large difference [0.487 (4) Å] between the longest Cu—O distance in the basal plane and that in the apical direction correlates with the small displacement of the Cu^II atom [0.0576 (13) Å] from the basal plane towards the apex of the square pyramid. The intermolecular hydrogen‐bonding network results in a closely overlapped arrangement of the coordination basal plane and the thia­zole ring of a neighboring mol­ecule.     

Bis(1‐ferrocenylbutane‐1,3‐dionato‐κ2O,O′)copper(II) and bis­(1,3‐diferrocenylpropane‐1,3‐dionato‐κ2O,O′)­copper(II)

The title compounds, [CuFe₂(C₅H₅)₂(C₉H₈O₂)₂], (I), and [CuFe₄(C₅H₅)₄(C₁₃H₉O₂)₂], (II), are four‐coordinate square‐planar copper(II) complexes with two bidentate 1‐ferrocenylbutane‐1,3‐dionate or 1,3‐diferrocenylpropane‐1,3‐dionate ligands, respectively. The copper ion in (I) lies on an inversion centre, with one‐half of the mol­ecule in the asymmetric unit, while in (II), there are two independent half mol­ecules in the asymmetric unit, with the copper ions also situated on inversion centres. The ferrocene substituents in (I) are in an anti arrangement. The mol­ecules assemble in the crystal structure in layers with ferrocene groups at the surface. The pairs of ferrocene substituents on each ligand in complex (II) are syn and these adopt an anti arrangement with respect to the pair on the other diketonate ligand. As found in (I), complexes assemble in a layered structure with ferrocene‐coated surfaces.     

Bis(2,6‐diamino‐1H‐purin‐3‐ium) di‐μ‐croconato‐κ3O,O′:O′′;κ3O:O′,O′′‐bis[tetraaqua(croconato‐κ2O,O′)neodymium(III)]

The structure of the ionic title compound, (C₅H₇N₆)₂[Nd₂(C₅O₅)₄(H₂O)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.