catena‐Poly­[[chloro(1,10‐phenanthroline‐κ2N,N′)copper(II)]‐μ‐imidazolato‐κ2N:N′]

In the polymeric title compound, [Cu(im)Cl(phen)]_n, where im is the imidazolate anion (C₃H₃N₂) and phen is 1,10‐phenanthroline (C₁₂H₈N₂), each Cu^II ion is five‐coordinated by four basal N atoms (two from two different im anions and two from one phen ligand) and one axial Cl atom, in a distorted square‐pyramidal coordination geometry. Moreover, each im anion bridges two identical {CuCl(phen)}⁺ cations through its two N atoms, resulting in a one‐dimensional zigzag chain along the crystallographic a axis. In addition, pairs of adjacent chains are staggered by π–π interactions, generating a two‐dimensional layer, and neighbouring layers are further linked by two different kinds of C—H⋯Cl interactions, producing a three‐dimensional network.     

Bis(1,10‐phenanthroline‐κ2N,N′)(squarato‐κO)copper(II) trihydrate

The title mononuclear [Cu(sq)(phen)₂]·3H₂O complex [sq is squarate (C₄O₄) and phen is 1,10‐phenanthroline (C₁₂H₈N₂)] has been synthesized and the structure consists of a neutral mononuclear [Cu(sq)(phen)₂] unit and three solvate water mol­ecules. The Cu^II ion has distorted square‐pyramidal coordination geometry, comprised of one carboxyl­ate O atom from a monodentate squarate ligand and four N atoms from two chelating phen ligands. An extensive three‐dimensional network of OW—H⋯O/OW hydrogen bonds, face‐to‐face π–­π interactions between the 1,10‐phenanthroline aromatic rings and a weak π–ring interaction are responsible for crystal stabilization.     

(1,3‐Dimethylimidazolidine‐2‐selone‐κSe)bis(1,10‐phenanthroline‐κ2N,N′)copper(II) bis(perchlorate) and bis(2,2′‐bipyridyl‐κ2N,N′)(imidazolidine‐2‐thione‐κS)copper(II) bis(perchlorate)

In the first title salt, [Cu(C₁₂H₈N₂)₂(C₅H₁₀N₂Se)](ClO₄)₂, the Cu^II centre occupies a distorted trigonal–bipyramidal environment defined by four N donors from two 1,10‐phenanthroline (phen) ligands and by the Se donor of a 1,3‐dimethylimidazolidine‐2‐selone ligand, with the equatorial plane defined by the Se and by two N donors from different phen ligands and the axial sites occupied by the two remaining N donors, one from each phen ligand. The Cu—N distances span the range 1.980 (10)–2.114 (11) Å and the Cu—Se distance is 2.491 (3) Å. Intermolecular π–π contacts between imidazolidine rings and the central rings of phen ligands generate chains of cations. In the second salt, [Cu(C₁₀H₈N₂)₂(C₃H₆N₂S)](ClO₄)₂, the Cu^II centre occupies a similar distorted trigonal–bipyramidal environment comprising four N donors from two 2,2′‐bipyridyl (bipy) ligands and an S donor from an imidazolidine‐2‐thione ligand. The equatorial plane is defined by the S donor and two N donors from different bipy ligands. The Cu—N distances span the range 1.984 (6)–2.069 (7) Å and the Cu—S distance is 2.366 (3) Å. Intermolecular π–π contacts between imidazolidine and pyridyl rings form chains of cations. A major difference between the two structures is due to the presence in the second complex of two N—H...O hydrogen bonds linking the imidazolidine N—H hydrogen‐bond donors to perchlorate O‐atom acceptors.     

(2‐Aminopyrimidine‐κN1)aqua(pyridine‐2,6‐dicarboxylato‐κ3O2,N,O6)copper(II): X‐ray and DFT calculated structure

In the title compound, [Cu(C₇H₃N₂O₄)(C₄H₅N₂)(H₂O)], (I), pyridine‐2,6‐dicarboxylate (pydc²⁻), 2‐aminopyrimidine and aqua ligands coordinate the Cu^II centre through two N atoms, two carboxylate O atoms and one water O atom, respectively, to give a nominally distorted square‐pyramidal coordination geometry, a common arrangement for copper complexes containing the pydc²⁻ ligand. Because of the presence of Cu...X_bridged contacts (X = N or O) between adjacent molecules in the crystal structures of (I) and three analogous previously reported compounds, and the corresponding uncertainty about the effective coordination number of the Cu^II centre, density functional theory (DFT) calculations were used to elucidate the degree of covalency in these contacts. The calculated Wiberg and Mayer bond‐order indices reveal that the Cu...O contact can be considered as a coordination bond, whereas the amine group forming a Cu...N contact is not an effective participant in the coordination environment.     

catena‐Poly[[(1,10‐phenanthroline‐κ2N,N′)copper(II)]‐μ‐(dihydrogen benzene‐1,2,4,5‐tetracarboxylato)‐κ2O1:O4]

In the title compound, [Cu(C₁₀H₄O₈)(C₁₂H₈N₂)]_n, the Cu^II cation has a four‐coordination environment completed by two N atoms from one 1,10‐phenanthroline (phen) ligand and two O atoms belonging to two di­hydrogen benzene‐1,2,4,5‐­tetra­carboxyl­ate anions (H₂TCB²⁻). There is a twofold axis passing through the Cu^II cation and the centre of the phen ligand. The [Cu(phen)]²⁺ moieties are bridged by H₂TCB²⁻ anions to form an infinite one‐dimensional coordination polymer with a zigzag chain structure along the c axis. A double‐chain structure is formed by hydrogen bonds between adjacent zigzag chains. Furthermore, there are π–π stacking inter­actions between the phen ligands, with an average distance of 3.64 Å, resulting in a two‐dimensional network structure.     

catena‐Poly[[[aqua(ethylenediamine‐κ2N,N′)(nitrato‐κO)copper(II)]‐μ‐4,4′‐dithiodipyridine‐κ2N:N′] nitrate monohydrate]

The title compound, {[Cu(NO₃)(C₂H₄N₂)(C₁₀H₈N₂S₂)(H₂O)]NO₃·H₂O}_n, is composed of a one‐dimensional linear coordination polymer involving cis‐protected copper(II) ions and a 4,4′‐dithiodipyridine bridging ligand. The polymeric chains run along the c‐axis direction. N—H...O and O—H...O hydrogen bonds involving the coordinating amine groups, nitrate ions and water molecules, as well as cocrystallized noncoordinating nitrate ions and water molecules, generate a three‐dimensional structure.     

Acetato(N‐phenylpyridine‐2‐carboxamidato‐κ2N,N)(N‐phenylpyridine‐2‐carboxamide‐κ2N1,O)copper(II)

The title complex, [Cu(C₁₂H₉N₂O)(C₂H₃O₂)(C₁₂H₁₀N₂O)], is a neutral Cu^II complex with a primary N₃O₂ coordination sphere. The Cu centre coordinates to both a deprotonated and a neutral molecule of N‐phenylpyridine‐2‐carboxamide and also to an acetate anion. The coordination around the metal centre is asymmetric, the deprotonated ligand providing two N donor atoms [Cu—N = 1.995 (2) and 2.013 (2) Å] and the neutral ligand providing one N and one O donor atom to the coordination environment [Cu—N = 2.042 (2) Å and Cu—O = 2.2557 (19) Å], the fifth donor being an O atom of the acetate ion [Cu—O = 1.9534 (19) Å]. The remaining O atom from the acetate ion can be considered as a weak donor atom [Cu—O = 2.789 (2) Å], conferring to the Cu complex an asymmetric octahedral geometry. The crystal structure is stabilized by intermolecular N—H...O, C—H...O and C—H...π interactions.     

Aqua­chloro(1,10‐phenanthroline‐κ2N,N′)(p‐toluenesulfonato‐κO)copper(II)

In the title compound, [CuCl(C₇H₇O₃S)(C₁₂H₈N₂)(H₂O)], the central Cu atom is coordinated by a water mol­ecule, a chloride ion, an O‐monodentate p‐toluene­sulfonate anion and an N,N′‐bidentate 1,10‐phenanthroline ligand. The copper environment is best described as a slightly distorted square pyramid, with bond distances Cu—Cl 2.2282 (9) Å, Cu—OW 1.984 (3) Å, and Cu—N 2.006 (3) and 2.028 (3) Å; the apical Cu—O distance is 2.281 (2) Å. In the supramolecular structure, π–π‐stacking stabilization is observed, and classical and non‐classical hydrogen bonds also play an important role.     

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).     

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.     

Polymeric aqua­(nitrato‐κ2O,O′)(1,10‐phenanthroline‐κ2N,N′)(2,3‐pyrazine­di­carboxyl­ato‐κ2N,O)­europium(III) monohydrate

In polymeric {[Eu(pzdc)(NO₃)(phen)(H₂O)]·H₂O}_n [pzdc is 2,3‐pyrazine­di­carboxyl­ate (C₆H₂O₄) and phen is 1,10‐phenanthroline (C₁₂H₈N₂)], each europium(III) ion is coordinated by seven O atoms (from three pzdc anions, a nitrate anion and a water mol­ecule) and the two N atoms of the phen ligand, resulting in a nine‐coordinated europium(III) center with a distorted monocapped square‐antiprismatic coordination polyhedron. Four pzdc anions bridge four europium(III) ions, forming a parallelogram unit, the four vertices of which are occupied by the four pzdc anions. Moreover, each parallelogram unit links six other adjacent parallelogram units, forming a two‐dimensional network with disordered lattice water mol­ecules.     

A bicapped trigonal–prismatic lead complex: catena‐poly[[[aqua­bis(1,10‐phenanthroline‐κ2N,N′)lead(II)]‐μ‐squarato‐κO1:κ2O2,O3] dihydrate]

The asymmetric unit of the title compound, {[Pb(C₄O₄)(C₁₂H₈N₂)₂(H₂O)]·2H₂O}_n, contains one squarate dianion, two phenanthroline (phen) ligands and one aqua ligand all coordinated to Pb, and two solvent water mol­ecules. The eight‐coordinate Pb metal ion displays a distorted bicapped trigonal–prismatic coordination environment, defined by three squarate O atoms, four N atoms from two chelating phen ligands and one O atom from the coordinated water mol­ecule. The crystal structure contains chains of squarate‐1,2,3‐bridged Pb^II ions running in the [010] direction. These polymeric chains are linked to one another via offset face‐to‐face π–π inter­actions between the phen ligands, which lead to a two‐dimensional network extending along the (001) plane. The crystal structure is also stabilized by O—H⋯O inter­molecular hydrogen‐bond inter­actions, forming a three‐dimensional network.     

The double‐stranded ladder‐like structure of poly[[bis(μ2‐acetato‐κ2O:O′)bis(acetato‐κO)bis(μ‐4,4′‐bipyridine‐κ2N:N′)dicopper(II)] 4‐nitrophenol disolvate tetrahydrate]

The reaction of 4,4′‐bipyridine with copper acetate in the presence of 4‐nitrophenol led to the formation of the title compound, {[Cu(CH₃COO)₂(C₁₀H₈N₂)]·C₆H₅NO₃·2H₂O}_n. The complex forms a double‐stranded ladder‐like coordination polymer extending along the b axis. The double‐stranded polymers are separated by 4‐nitrophenol and water solvent molecules. The two Cu^II centres of the centrosymmetric Cu₂O₂ ladder rungs have square‐pyramidal coordination environments, which are formed by two acetate O atoms and two 4,4′‐bipyridine N atoms in the basal plane and another acetate O atom at the apex. The ladder‐like double strands are separated from each other by one unit‐cell length along the c axis, and are connected by the water and 4‐nitrophenol molecules through a series of O—H...O and C—H...O hydrogen‐bonding interactions and two unique intermolecular π–π interactions.     

Poly­[[[(1,10‐phenanthroline‐κ2N,N′)­zinc(II)]‐μ3‐5‐hydroxy­isophthalato‐κ4O,O′:O′′:O′′′] monohydrate]

In the title compound, {[Zn(C₈H₄O₅)(C₁₂H₈N₂)]·H₂O}_n or {[Zn(OH‐BDC)(phen)]·H₂O}_n (where OH‐H₂BDC is 5‐hydroxy­isophthalic acid and phen is 1,10‐phenanthroline), the Zn atoms are coordinated by two N atoms from the phen ligands and by four O atoms from hydroxy­isophthalate ligands in a highly distorted octahedral geometry, with Zn—O distances in the range 2.042 (4)–2.085 (5) Å and Zn—N distances of 2.133 (5) and 2.137 (5) Å. The {[Zn(OH‐BDC)(phen)]·H₂O}_n infinite zigzag polymer forms a helical chain of [Zn₂(OH‐BDC)₂]_n units. Face‐to‐face π–π interactions (3.60–3.75 Å) occur between two phen rings belonging to the same helical chain. Consolidation of the packing structure is achieved by O—H⋯O hydrogen‐bonding interactions between the carboxyl­ate O atoms, the hydroxyl group and the water mol­ecule, forming two‐dimensional sheets.     

Bis­(acetone‐κO)­bis(N,N′‐di­methyl­ethyl­enedi­amine‐κ2N,N′)copper(II) diperchlorate

The title compound, [Cu(C₄H₁₂N₂)₂(C₃H₆O)₂](ClO₄)₂, is the first structurally characterized Cu^II complex having acetone as axial ligands. The complex adopts an elongated octahedral trans‐[CuN₄O₂] coordination geometry, with the Cu atom having 222 site symmetry. The axial Cu—O(acetone) and in‐plane Cu—N bond lengths are 2.507 (5) and 2.041 (3) Å, respectively.     

{μ‐N,N′‐Bis[3‐(dimethyl­amino)prop­yl]­oxamidato(2–)‐κ6N,N′,O′:N′′,N′′′,O}­bis­[(1H‐imidazole‐κN3)(methanol‐κO)copper(II)] bis­(perchlorate)

The structure of the title compound, [Cu₂(C₁₂H₂₄N₄O₂)(C₃H₄N₂)₂(CH₄O)₂](ClO₄)₂ or [Cu₂(dmoxpn)(HIm)₂(CH₃OH)₂](ClO₄)₂, where dmoxpn is the dianion of N,N′‐bis­[3‐(dimethyl­amino)prop­yl]oxamide and HIm is imidazole, consists of a centrosymmetric trans‐oxamidate‐bridged copper(II) binuclear cation, having an inversion centre at the mid‐point of the central C—C bond, and two perchlorate anions. The Cu^II atom has square‐pyramidal coordination geometry involving two N atoms and an O atom from the dmoxpn ligand, an N atom from an imidazole ring, and an O atom from a methanol mol­ecule. The crystal structure is stabilized by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds and imidazole π–π stacking inter­actions to form a three‐dimensional supra­molecular array.     

Di­aqua­bis(1,10‐phenanthroline‐κ2N,N′)­manganese(II) thiodiglycolate bis(1,10‐phenanthroline‐κ2N,N′)(thiodiglycolato‐κ2O,O′)­manganese(II) tridecahydrate

The title compound, [Mn(C₁₂H₈N₂)₂(H₂O)₂](C₄H₄O₄S)·[Mn(C₄H₄O₄S)(C₁₂H₈N₂)₂]·13H₂O, contains one dianion of thio­diglycolic acid (tdga²⁻) and two independent man­ganese(II) moieties, viz. [Mn(phen)₂(H₂O)₂]²⁺ and [Mn(tdga)(phen)₂], where phen is 1,10‐phenanthroline. The Mn^II atoms are octahedrally coordinated by four N atoms of two bidentate phen ligands [Mn—N = 2.240 (2)–2.3222 (19) Å] and either two water O atoms or two tdga carboxyl O atoms [Mn—O = 2.1214 (17)–2.1512 (17) Å]. The tdga ligand chelates as an O,O′‐bidentate ligand, forming an eight‐membered ring with one Mn atom. The free tdga²⁻ dianion is hydrogen bonded to an [Mn(phen)₂(H₂O)₂]²⁺ ion, with O⋯O distances of 2.606 (2) and 2.649 (2) Å. The crystal structure is further stabilized by an extensive network of hydrogen bonds involving 13 water mol­ecules.     

μ‐Acetato‐1:2κ2O:O′‐diacetato‐1κ2O,O′;2κO‐bis(di‐2‐pyridylamine)‐1κ2N,N′;2κ2N,N′‐isothiocyanato‐2κN‐dicopper(II)

In the title dinuclear acetate‐bridged complex, [Cu₂(C₂H₃O₂)₃(NCS)(C₁₀H₉N₃)₂], the two Cu atoms are five‐coordinated, with a basal plane consisting of two N atoms of a di‐2‐pyridylamine (dpyam) ligand and two O atoms of two different acetate ligands. The axial positions of these Cu atoms are coordinated to N and O atoms from thio­cyanate and acetate mol­ecules, respectively, leading to a distorted square‐pyramidal geometry with τ values of 0.30 and 0.22. Both Cu^II ions are linked by an acetate group in the equatorial–equatorial positions and have syn–anti bridging configurations. Hydrogen‐bond inter­actions between the amine H atom and the coordinated and uncoordinated O atoms of the acetate anions generate an infinite one‐dimensional chain.     

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].     

catena‐Poly[[(1,10‐phenanthroline‐κ2N,N′)manganese(II)]‐di‐μ‐salicylato‐κ4O:O′]

In the title polymeric complex, [Mn(C₇H₅O₃)₂(C₁₂H₈N₂)]_n, the Mn^II atom is located on a twofold axis and displays a distorted octa­hedral coordination geometry, formed by four salicylate anions and one 1,10‐phenanthroline (phen) mol­ecule. The salicylate anions doubly bridge the Mn^II atoms to form one‐dimensional polymeric chains. A comparison of Mn—O bond distances with the corresponding Mn—O—C angles suggests a significant electrostatic content in the Mn—O bonds. A face‐to‐face distance of 3.352 (7) Å between neighbouring parallel phen planes indicates π–π stacking inter­actions between polymeric chains.