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)°].     

Tetrakis(μ‐benzoato‐κ2O:O)bis{[4‐(dimethylamino)pyridine‐κN1]copper(II)}

The title compound, [Cu₂(C₇H₅O₂)₄(C₇H₁₀N₂)₂], is a crystallographically centrosymmetric binuclear complex, with Cu atoms [Cu...Cu = 2.6982 (4) Å] bridged by four benzoate ligands. Each of the Cu atoms in this bunuclear copper(II) acetate hydrate analogue is present in an approximately square‐pyramidal environment, with four O atoms in a plane and the pyridine N atom at the apical site. Selected geometric parameters are compared with values for related tetrabenzoate complexes of copper(II).     

(4‐Bromo‐2‐formyl­phenolato)­perchlorato­(1,10‐phenanthroline)­copper(II)

In the title copper(II) compound, [Cu(C₇H₄BrO₂)(ClO₄)(C₁₂H₈N₂)], the Cu atom is five‐coordinated in a distorted square‐pyramidal geometry by the N‐ and O‐donors of 4‐bromo‐2‐formyl­phenolate, 1,10‐phenanthroline and perchlorate. Pairs of complexes are linked together by Cu⋯O(phenolate) and π–π stacking inter­actions between 4‐bromo‐2‐formyl­phenolate and 1,10‐phenanthroline. Along the crystallographic a axis, the dimers are linked by hydrogen bonds between a perchlorate O atom and a 4‐bromo‐2‐formyl­phenolate H atom, and by further π–π stacking inter­actions. Hydrogen bonding between the Br atom and a 1,10‐phenanthroline H atom takes place between the stacks of dimers.     

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.     

Dichlorobis(pyridine‐κN)bis(3,3,3‐trifluoropropyl‐κC1)tin(IV)

In the title compound, [Sn(C₃H₄F₃)₂Cl₂(C₅H₅N)₂], the Sn atom lies on an inversion centre and is octahedrally coordinated by two Cl atoms, two tri­fluoro­propyl groups and two N atoms in an all‐trans configuration. The electronegative tri­fluoro­propyl groups increase the electrophilic properties of the Sn atom, and the Sn—Cl and Sn—N bonds are shortened in comparison with those reported for analogous compounds.     

(Benzoyl­acetonato)­chloro(1,10‐phen­anthroline)copper(II)

The crystal structure of the title compound, chloro(1,10‐phenanthroline‐N,N′)(1‐phenyl‐1,3‐butane­dion­ato‐O,O′)copper(II), [CuCl(C₁₀H₉O₂)(C₁₂H₈N₂)], has been determined. The Cu^II ion displays a distorted square‐pyramidal coordination, being linked to the two O atoms of the benzoyl­acetonate ligand and the two N atoms of the 1,10‐phenanthroline ligand in the basal plane, and the Cl atom in the apical site. TheCu—N, Cu—O and Cu—Cl bond lengths are 2.043 (2)/2.025 (2), 1.914 (2)/1.941 (2) and 2.485 (1) Å, respectively.     

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.     

Low‐dimensional compounds containing cyano groups. XVI. (Dicyanamido‐κN1)bis(1,10‐phenanthroline‐κ2N,N′)copper(II) tetrafluoridoborate

The title compound, [Cu{N(CN)₂}(C₁₂H₈N₂)₂]BF₄, was prepared as part of our study of the shape of coordination polyhedra in five‐coordinated copper(II) complexes. Single‐crystal X‐ray analysis reveals that the structure consists of [Cu{N(CN)₂}(phen)₂]⁺ cations (phen is 1,10‐phenanthroline) and BF₄⁻ anions. The Cu centre is five‐coordinated in a distorted trigonal bipyramidal manner by four N atoms of two phen ligands and one N atom of a dicyanamide anion, which is coordinated in the equatorial plane at a distance of 1.996 (2) Å. The two axial Cu—N_phen distances have similar values [average 1.994 (6) Å] and are shorter than the two equatorial Cu—N_phen bonds [average 2.09 (6) Å]. This work demonstrates the effect of ligand rigidity on the shape of coordination polyhedra in five‐coordinated copper(II) complexes.     

Di­bromo(N,N′‐di‐2‐pyridyl­amine‐κ2N,N′)­palladium(II)

The palladium center of the title compound, [PdBr₂(C₁₀H₉N₃)], has a slightly distorted square‐planar conformation, with the Pd atom bonded to the two pyridine N atoms of the di‐2‐pyridyl­amine moiety and to two Br atoms. The Pd—Br and Pd—N bond lengths are 2.4168 (6)/2.4201 (5) and 2.036 (3)/2.042 (3) Å, respectively.     

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.     

Poly[μ2‐chloro‐μ2‐1,4‐oxathiane‐κ2S:S‐copper(I)]

The title complex, [CuCl(C₄H₈OS)]_n, contains infinite spiral (CuS)_n chains linked by bridging Cl atoms into layers. The Cl atoms do not form polymeric fragments with Cu^I, but combine into isolated centrosymmetric Cu₂Cl₂ units. The compound is non‐isomorphous with the Br‐containing analogue, which contains Cu₈S₈ rings linked by Br atoms into chains. The O atom of the 1,4‐oxathiane mol­ecule does not realize its coordination abilities in the known copper(I)–halide complexes, while in copper(II)–halide complexes, oxathiane is coordinated via the S and O atoms. This falls into a pattern of the preferred inter­actions, viz. weak acid (Cu^I atom) with weak base (S atom) and harder acid (Cu^II atom) with harder base (O atom).     

[Bis(3,5‐dimethylpyrazol‐1‐yl‐κN2)dithioacetato‐κS](triphenylphosphine‐κP)copper(I)

In the title compound, [Cu(C₁₂H₁₅N₄S₂)(C₁₈H₁₅P)], the copper(I) center is tetrahedrally coordinated by one S atom and two N atoms from one bis(3,5‐dimethylpyrazol‐1‐yl)dithioacetate ligand and one P atom from a triphenylphosphine ligand. In the crystal structure, adjacent pyrazole rings are involved in weak π–π interactions, thereby forming a one‐dimensional zigzag chain running along the b axis.     

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.     

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.     

(2,2′‐Biquinoline‐κ2N,N′)dichloropalladium(II), ‐copper(II) and ‐zinc(II)

In the three title complexes, namely (2,2′‐biquinoline‐κ²N,N′)dichloro­palladium(II), [PdCl₂(C₁₈H₁₂N₂)], (I), and the corresponding copper(II), [CuCl₂(C₁₈H₁₂N₂)], (II), and zinc(II) complexes, [ZnCl₂(C₁₈H₁₂N₂)], (III), each metal atom is four‐coordinate and bonded by two N atoms of a 2,2′‐biquinoline molecule and two Cl atoms. The Pd^II atom has a distorted cis‐square‐planar coordination geometry, whereas the Cu^II and Zn^II atoms both have a distorted tetra­hedral geometry. The dihedral angles between the N—M—N and Cl—M—Cl planes are 14.53 (13), 65.42 (15) and 85.19 (9)° for (I), (II) and (III), respectively. The structure of (II) has twofold imposed symmetry.     

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.     

Bis(μ‐4‐chloro­benzoato‐κ2O:O)bis[(2‐aminopyridine‐κN)silver(I)]

The title compound, [Ag₂(C₇H₄ClO₂)₂(C₅H₆N₂)₂], lies about an inversion centre and the Ag atom is three‐coordinated by two O atoms and one N atom from three different ligands. The 4‐chloro­benzoate anion acts as a monodonor ligand, bridging two inversion‐related Ag atoms of the compound into a dimer. There are weak intermolecular N—H⋯O hydrogen bonds in the structure.     

Bis(2‐amino­pyridine‐κN1)(benzoato‐κO)silver(I)

In the title compound, [Ag(C₇H₅O₂)(C₅H₆N₂)₂], the Ag^I atom is tricoordinated by two independent pyridine N atoms and one benzoate O atom in a nearly planar geometry. An intramolecular N—H⃛O hydrogen bond forms an S(8) graph ring. The packing is built from molecular layers stabilized by two types of N—H⃛O hydrogen bond. Intermolecular Ag⃛N and intramolecular Ag⃛O contacts were also observed, together with three weak intermolecular C—H⃛π interactions.     

(4‐Aminopyridine‐κN1)(phthalocyaninato‐κ4N)zinc(II) tetrahydrofuran disolvate

The title compound, [Zn(C₃₂H₁₆N₈)(C₅H₆N₂)]·2C₄H₈O, consists of one (phthalocyaninato)zinc (ZnPc) unit, a coordinated 4‐aminopyridine (4‐ap) molecule and two tetrahydrofuran (THF) solvent molecules. The central Zn atom is (4+1)‐coordinated by four isoindole N atoms of the Pc core and by the pyridine N atom of 4‐aminopyridine. The Zn atom is displaced by 0.4464 (8) Å from the isoindole N₄ plane towards the pyridine N atom. The crystal structure is stabilized by intermolecular amine–phthalocyaninate N—H...N hydrogen bonds and π–π interactions between the aggregated Pc rings, which form molecular layers, and by weak van der Waals interactions between the layers. As well as hindering the aggregation of ZnPc molecules by occupying an axial position, the amino group will add new interactions which will favor applications of ZnPc, for example, as a sensitizer of photodynamic therapy.     

Aqua(dipicolinato‐κ3O2,N,O6)(1,10‐phenanthroline‐κ2N,N′)manganese(II) monohydrate

In the title compound [systematic name: aqua(1,10‐phenanthroline‐κ²N,N′)(pyridine‐2,6‐di­carboxyl­ato‐κ³O²,N,O⁶)manganese(II) monohydrate, [Mn(C₇H₃NO₄)(C₁₂H₈N₂)(H₂O)]·H₂O, the manganese(II) centre is surrounded by one bidentate phenanthroline ligand [Mn—N = 2.248 (3) and 2.278 (3) Å], one tridentate dipicolinate ligand [Mn—N = 2.179 (3) Å, and Mn—O = 2.237 (2) and 2.266 (2) Å] and one water mol­ecule [Mn—O = 2.117 (3) Å], and it exhibits a strongly distorted octahedral geometry, with trans angles ranging from 144.12 (9) to 158.88 (11)°. Extensive intermolecular hydrogen‐bonding interactions involving coordinated and uncoordinated water mol­ecules and the carboxyl O atoms of the dipicolinate ligand, as well as a stacking interaction involving the phenanthroline rings, are observed in the crystal structure.