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.     

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.     

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.     

Diaquabis(2,5‐dihydroxybenzoato‐κO)bis(1,10‐phenanthroline‐κ2N,N′)strontium(II) bis(1,10‐phenanthroline) tetrahydrate

The title compound, [Sr(C₇H₅O₄)₂(C₁₂H₈N₂)₂(H₂O)₂]·2C₁₂H₈N₂·4H₂O, consists of an Sr^II complex, uncoordinated phenanthroline (phen) molecules and solvent water molecules. The Sr^II ion is located on a twofold axis and is coordinated by two phen ligands, two dihydroxybenzoate anions and two water molecules in a distorted tetragonal antiprismatic geometry. Partially overlapped arrangements exist between parallel coordinated and parallel uncoordinated phen rings; the face‐to‐face separations between the former (coordinated) and the latter (uncoordinated) rings are 3.436 (13) and 3.550 (14) Å, respectively. This difference suggests the effect of metal coordination on π–π stacking between phen rings.     

(Hexafluorosilicato‐κ2F,F′)bis(1,10‐phenanthroline‐κ2N,N′)zinc(II) methanol monosolvate

The title compound, [Zn(SiF₆)(C₁₂H₈N₂)₂]·CH₃OH, contains a neutral heteroleptic tris‐chelate Zn^II complex, viz. [Zn(SiF₆)(phen)₂] (phen is 1,10‐phenanthroline), exhibiting approximate molecular C₂ point‐group symmetry. The Zn^II cation adopts a severely distorted octahedral coordination. As far as can be ascertained, the title complex represents the first structurally characterized example of a Zn^II complex bearing a bidentate‐bound hexafluorosilicate ligand. A density functional theory study of the isolated [Zn(SiF₆)(phen)₂] complex was undertaken to reveal the influence of crystal packing on the molecular structure of the complex. In the crystal structure, the methanol solvent molecule forms a hydrogen bond to one F atom of the hexafluorosilicate ligand. The hydrogen‐bonded assemblies so formed are tightly packed in the crystal, as indicated by a high packing coefficient (74.1%).     

Tris(1,10‐phenanthroline‐κ2N,N′)cadmium(II) bis(perchlorate) 3.5‐hydrate: a water chain stabilized by perchlorate anions

The title compound, [Cd(C₁₂H₈N₂)₃](ClO₄)₂·3.5H₂O, contains a cross‐shaped one‐dimensional channel along the c axis which encapsulates an ordered water chain. This water chain features a centrosymmetric cyclic water hexamer unit with a chair‐like conformation. Neighbouring hexamers are linked by bridging water molecules. The host perchlorate anions recognize and stabilize the guest water chain via three kinds of hydrogen‐bond patterns, leading to the formation of a complex one‐dimensional {[(H₂O)₇(ClO₄)₄]⁴⁻}_n anionic chain. One perchlorate acts as a single hydrogen‐bond acceptor dangling on the chain, the second perchlorate on the chain serves as a double hydrogen‐bond acceptor for only one water molecule to form an R₂²(6) ring, where both entities lie on a twofold axis, while the third perchlorate, which also lies on a twofold axis, accepts two hydrogen bonds from two equivalent water molecules and is involved in the construction of an R₆⁵(14) ring.     

Two polymorphs of bis(1,10‐phenanthroline‐κ2N,N′)copper(I) iodide

The title complex, [Cu(C₁₂H₈N₂)₂]I, (I), has been crystallized in two polymorphic forms, both containing four‐coordinate copper. Both forms are orthorhombic, with form (Ia) crystallizing in the primitive space group Pban and form (Ib) in the c‐centred space group Ccca. In (Ia), the complex cation and the I⁻ anion both have 222 crystallographic symmetry, and in (Ib), the complex cation has approximate 222 symmetry, with the I⁻ counter‐ion distributed over three special positions.     

Tetra­aqua(1,10‐phenanthroline‐κ2N,N′)­manganese(II) sulfate dihydrate

The title compound, [Mn(C₁₂H₈N₂)(H₂O)₄]SO₄·2H₂O, was obtained unexpectedly as a by‐product from the reaction of sodium maleate, 1,10‐phenanthroline (phen) and manganese sulfate tetrahydrate. The Mn atom is coordinated by the two N atoms of the phen ligand and four water O atoms in a highly distorted octahedral geometry, with Mn—O distances in the range 2.155 (2)–2.203 (2) Å and Mn—N distances of 2.254 (2) and 2.272 (3) Å. Extensive hydrogen‐bonding interactions involving the water mol­ecules and sulfate anions, and stacking interactions involving the phen rings, are observed in the crystal structure.     

Aqua­bis(2‐nitro­benzoato‐κO)(1,10‐phenanthroline‐κ2N,N′)­zinc(II)

The title compound, [Zn(C₇H₄NO₄)₂(C₁₂H₈N₂)(H₂O)], has been synthesized. X‐Ray analysis reveals that it is a neutral zinc(II) mononuclear carboxyl­ate complex based on mixed N‐ and O‐donor ligands. The Zn atom is five‐coordinate in a distorted trigonal–bipyramidal coordination environment involving two O atoms of two monodentate 2‐nitro­benzoate mol­ecules, two N atoms of a 1,10‐phenanthroline mol­ecule and one O atom of a water mol­ecule. The axial positions are occupied by a carboxyl­ate O atom from the 2‐nitro­benzoate ligand and an N atom from the 1,10‐phenanthroline ligand [N—Zn—O = 167.66 (9)°].     

Tris(2,2′‐bioxazoline‐κ2N,N′)copper(II) diperchlorate and tris(2,2′‐bioxazoline‐κ2N,N′)­nickel(II) diperchlorate

In the two isomorphous title compounds, viz. tris­[2,2′‐bi(4,5‐di­hydro‐1,3‐oxazole)‐κ²N,N′]copper(II) diperchlorate, [Cu(C₆H₈N₂O₂)₃](ClO₄)₂, (I), and tris­[2,2′‐bi(4,5‐di­hydro‐1,3‐oxazole)‐κ²N,N′]­nickel(II) diperchlorate, [Ni(C₆H₈N₂O₂)₃](ClO₄)₂, (II), the M^II ions each have a distorted octahedral coordination geometry formed via six N atoms from three 2,2′‐bioxazoline ligands. For each ligand, the two five‐membered rings are nearly coplanar. It is noteworthy that the Jahn–Teller effect is stronger in (I) than in (II). The three‐dimensional supramolecular structures of (I) and (II) are formed via weak hydrogen‐bonding interactions between O atoms from per­chlorate anions and H atoms from 2,2′‐bioxazoline ligands.     

(2,2′‐Bi­pyridine‐κ2N,N′)(dichromato‐κO)copper(II)

The title compound, [Cu(Cr₂O₇)(C₁₀H₈N₂)₂], a new mixed‐metal molecular compound, contains isolated molecular units, each comprised of one Cu^II atom coordinated to two 2,2′‐bi­pyridine ligands and also to an oxy­gen vertex of a dichromate anion. The Cu^II atom has an approximate trigonal–bipyramidal geometry, which is consistent with previous studies. Both enantiomers of the chiral complex mol­ecule are present and are related by inversion centers. In a reported pyridine analogue, achiral [Cu(Cr₂O₇)(pyridine)₄] chains pack in the non‐centrosymmetric space group Pna2₁. Differences in the organic ligands influence the chirality and dimensionality of the Cu—Cr₂O₇ bonding.     

Bis(2,2′‐bi­pyridine‐κ2N,N′)(1,10‐phen­anthroline‐κ2N,N′)­ruthenium(II) tetra­cyano­platinate(II)

In the title compound, [Ru(C₁₀H₈N₂)₂(C₁₂H₈N₂)][Pt(CN)₄], cations and anions alternate along the a axis to afford a one‐dimensional network. The one‐dimensional character arises from the π–π stacking as well as from the electrostatic interactions formed between the phen (1,10‐phenanthroline) and [Pt(CN)₄]²⁻ units. Two adjacent one‐dimensional chains form further stacks based on the π–π stacking interactions between the phen moieties, where the interplanar spacing is 3.50 (1) Å.     

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.     

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.     

(Croconato‐κ2O,O′)bis­(1,10‐phenanthroline‐κ2N,N′)cobalt(II), and the nickel(II) and copper(II) analogues

The title complexes, [M(C₅O₅)(C₁₂H₈N₂)₂], with M = Co^II, Ni^II and Cu^II, all lie across twofold rotation axes, around which two 1,10‐phenanthroline ligands are arranged in a chiral propeller manner. The Co^II and Ni^II complexes are isostructural, with octa­hedral coordination geometry, while the local geometry of the Cu^II complex is severely distorted from octa­hedral.     

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).     

Tris(acetyl­acetonato‐κ2O,O′)(1,10‐phenanthroline‐κ2N,N′)erbium(III)

The title compound, [Er(C₅H₇O₂)₃(C₁₂H₈N₂)], is a mixed‐ligand metal–organic precursor for chemical vapour deposition, with the Er atom being eight‐coordinate. The coordination polyhedron, described as a distorted square anti­prism, is formed by three bidentate (chelating) acetyl­acetonate residues and a phenanthroline ligand in the apical positions. Mol­ecular assembly via C—H⋯O hydrogen bonds generates a sheet structure in the ac plane. Weak co‐operative C—H⋯π inter­actions form mol­ecular dimers and contribute to the stability of the inter­sheet packing. The supra­molecular assembly contains voids which form hydro­phobic porous channels, surrounded by a cluster of dimers.     

(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.     

{μ‐N,N′‐Bis[2‐(dimethylamino)ethyl]oxamidato(2–)‐κ6N,N′,O′:N′′,N′′′,O}bis[(2,2′‐bipyridine‐κ2N,N′)copper(II)] bis(perchlorate)

In the crystal structure of the title complex, [Cu₂(C₁₀H₂₀N₄O₂)(C₁₀H₈N₂)₂](ClO₄)₂, the deprotonated dmaeoxd²⁻ ligand {H₂dmaeoxd is N,N′‐bis[2‐(dimethylamino)ethyl]oxamide} occupies an inversion centre at the mid‐point of the central C—C bond and is thus in a trans conformation. The two Cu^II atoms are located in slightly distorted square‐based pyramidal environments. The binuclear units interact with each other viaπ–π interactions to form a one‐dimensional chain extending in the c direction.     

(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.