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.     

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.     

(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%).     

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.     

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.     

cis‐Dichloridobis(1,10‐phenanthroline‐5,6‐diol‐κ2N,N′)manganese(II): a supramolecular chain formed via O—H...Cl bonds and aromatic stacking

The title compound, [MnCl₂(C₁₂H₈N₂O₂)₂], displays a novel supramolecular chain formed by intermolecular O—H...Cl hydrogen bonds and aromatic stacking. The molecule has crystallographically imposed twofold symmetry with the Mn^II atom on the twofold axis. In the 1,10‐phenanthroline‐5,6‐diol ligand, each H atom of the two hydroxy groups is oriented towards the other hydroxy O atom. Both hydroxy groups form intermolecular O—H...Cl hydrogen bonds with a single Cl atom of an adjacent molecule. These hydrogen bonds connect the molecules via operation of the molecular twofold axis and the centre of inversion of the crystal lattice, forming a doubly‐bridged one‐dimensional structure with Mn atoms as the nodes. Strong aromatic π‐stacking between two antiparallel neighbouring 1,10‐phenanthroline‐5,6‐diol ligands also helps to stabilize the chain.     

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).     

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.     

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)°].     

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.     

Bis(isoquinoline‐1‐carboxylato‐κ2O,N)(1,10‐phenanthroline‐κ2N,N′)zinc(II) dimethylformamide sesqui­solvate

The asymmetric unit of the title compound, [Zn(C₁₀H₆NO₂)₂(C₁₂H₈N₂)]·1.5C₃H₇NO, contains one monomeric zinc com­plex and 1.5 disordered di­methyl­form­amide solvate mol­ecules. The Zn atom is coordinated to one 1,10‐phenanthroline ligand and to two iso­quinoline­carboxyl­ate anions (IQC^?) via their N and O atoms. The complex exhibits a distorted octahedral geometry around the Zn^II atom, with the apical positions occupied by the O atoms of the IQC^? ligands. The Zn atom lies 0.049 (1) Å out of the basal plane. The crystal packing is characterized by several hydrogen bonds.     

Aqua­(5,6‐di­methyl‐1,10‐phenanthroline‐N,N′)­(glycolato‐O,O′)­copper(II) nitrate

The title compound, [Cu(C₂H₃O₃)(C₁₄H₁₂N₂)(H₂O)]NO₃, is the first example of a mixed copper glycolate compound with a di­imine ligand. The copper(II) compound lies in a slightly distorted square‐pyramidal coordination environment with one water mol­ecule coordinated in the apical position. The glycolate ligand binds to the Cu atom as a chelate through a carboxyl­ate and the α‐OH O atom which, together with the N atoms of the substituted phenanthroline, constitute the base of the pyramid.     

Tetra­aqua(3,4,7,8‐tetra­methyl‐1,10‐phenanthroline‐κ2N,N′)­zinc(II) thio­sulfate

In the title complex of zinc(II) with 3,4,7,8‐tetra­methyl‐1,10‐phenanthroline (tmph), viz. [Zn(C₁₆H₁₆N₂)(H₂O)₄](S₂O₃), the metal atom has a monomeric octahedral ZnN₂O₄ complex environment comprising two N‐atom donors from the tmph group and four aqua O‐atom donors. The complex cation is connected to four thio­sulfate anions through a compact hydrogen‐bonding network involving all coordinated aqua H‐atom donors and all the outer acceptors (O and S) of the anion.     

Tris(1,10‐phenanthroline‐N,N′)­iron(II) di­thio­cyanate tri­hydrate

The title mononuclear iron(II) complex, [Fe(C₁₂H₈N₂)₃](NCS)₂·3H₂O, has a slightly distorted octa­hedral coordination. One of the thio­cyanate ions and one of the water mol­ecules of crystallization show positional disorder.     

(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.     

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.     

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.     

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.     

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.     

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.