Aquachloro[N,N′‐ethylenebis(salicylideneiminato)]manganese(III)

The title compound, aqua­chloro{2,2′‐[1,2‐ethanediyl­bis­(nitrilo­methyl­idyne)]­diphenolato‐κ⁴O,N,N′,O′}manganese(III),[MnCl(C₁₆H₁₄N₂O₂)(H₂O)], is a neutral manganese(III) complex with a pseudo‐octahedral metal centre. The equatorial plane comprises the four donor atoms of the tetradentate Schiff base ligand [Mn—O 1.886 (4) and 1.893 (4) Å, and Mn—N 1.978 (5) and 1.982 (5) Å], with a water mol­ecule [Mn—O 2.383 (4) Å] and a Cl^? ligand [Mn—Cl 2.4680 (16) Å] completing the coordination sphere. The distorted geometry is highlighted by the marked displacement of the Mn^III ion out of the least‐squares plane of the four Schiff base donor atoms by 0.165 (2) Å. These monomeric Mn^III centres are then linked into a polymeric array via hydrogen bonds between the coordinated water mol­ecule and the phenolic O‐atom donors of an adjacent Mn^III centre [O—H?O 2.789 (5) and 2.881 (5) Å].     

Chloro{2,2′‐[(1S,2S)‐1,2‐di­phenyl‐1,2‐ethanediyl­bis­(nitrilo­methyl­idyne)]­diphenolato‐κ4O,N,N′,O′}(ethanol‐κO)­manganese(III)

The crystal structure of the title compound, [MnCl(C₂₈H₂₂N₂O₂)(C₂H₆O)], has been determined at 173 (2) K in the non‐centrosymmetric space group P2₁2₁2₁. The asymmetric unit contains two molecular units. An intermolecular O—H⋯Cl hydrogen bond is formed between the OH group of an ethanol mol­ecule coordinated to the Mn atom and the coordinated Cl⁻ anion, and so polymeric chains of Mn‐containing fragments are formed [O—H⋯Cl = 3.1281 (16) and 3.1282 (15) Å]. The Mn atoms have a pseudo‐octahedral coordination sphere, with the four donor atoms of the Schiff base forming an equatorial plane [Mn—O distances are 1.8740 (13), 1.8717 (13), 1.8749 (13) and 1.8823 (13) Å, and Mn—N distances are 1.9868 (15), 1.9910 (14), 1.9828 (15) and 1.9979 (14) Å]. The axial positions are occupied by an ethanol mol­ecule [Mn—O distances of 2.3069 (15) and 2.3130 (15) Å] and a Cl⁻ ligand [Mn—Cl distances of 2.5732 (6) and 2.5509 (6) Å].     

trans‐[N,N′‐Bis­(salicyl­idene)­cyclo­hexane‐1,2‐diaminato]­nickel(II)–chloro­form (1/1)

In the title complex, trans‐{2,2′‐[cyclo­hexane‐1,2‐diyl­bis­(ni­t­rilo­methyl­idyne)]­di­phenol­ato‐κ⁴O,N,N′,O′}­nickel(II)–chloro­form (1/1), [Ni(C₂₀H₂₀N₂O₂)]·CHCl₃, the Ni atom has a square‐planar geometry, slightly tetrahedrally distorted. The Ni—N and Ni—O bonding distances are within the expected ranges for Ni–Schiff base derivatives. The di­imine bridge has a gauche conformation with the cyclo­hexyl ring almost coplanar with the NiN₂O₂ plane. The complex mol­ecules pack in dimers with an Ni?Ni distance of 3.59 (1) Å and form a three‐dimensional structure displaying a herring‐bone configuration. Channels are occupied by solvent mol­ecules, which are involved in C—H?O hydrogen bonds with the ligand O atoms.     

The layered structure of poly­[[di‐μ‐chloro‐bis­[chloro(2‐ethyl­tetrazole‐κN4)copper(II)]]‐di‐μ‐2‐ethyl­tetrazole‐κ2N1:N4]

In the polymeric title complex, [CuCl₂(C₃H₆N₄)₂]_n, there are two ligands in the asymmetric unit. The Cu atom adopts an elongated octahedral geometry, with two 2‐ethyl­tetrazole ligands [Cu—N = 2.0037 (16) and 2.0136 (16) Å] and two Cl atoms [Cu—Cl = 2.2595 (6) and 2.2796 (6) Å] in equatorial positions. A Cl atom and a symmetry‐related 2‐ethyl­tetrazole mol­ecule [Cu—Cl = 2.8845 (8) Å and Cu—N = 2.851 (2) Å] lie in the axial positions of the octahedron. One of the two 2‐­ethyltetrazole ligands of the asymmetric unit exhibits bidentate binding to two Cu atoms through two N atoms of the tetrazole ring, whereas the other ligand is coordinated in a monodentate fashion via one tetrazole N atom. The Cu‐atom octahedra form dimer entities by sharing edges with equatorial and axial Cl atoms. The dimers are linked together through the 2‐ethyl­tetrazole ligands to form one‐dimensional polymeric zigzag chains extending along the b axis. The chains are connected into infinite layers parallel to the (10) plane via the 2‐ethyl­tetrazole ligands.     

catena‐Poly­[[bis­(quinoxaline‐κN)cobalt(II)]‐di‐μ‐dicyan­amido‐κ2N1:N5] and catena‐poly­[[bis(quinoxaline‐κN)copper(II)]‐di‐μ‐dicyan­amido‐κ2N1:N5]

Two new complexes, [Co(C₂N₃)₂(C₈H₆N₂)₂], (I), and [Cu(C₂N₃)₂(C₈H₆N₂)₂], (II), are reported. They are essentially isomorphous. Complex (I) displays distorted octahedral geometry, with the Co atom coordinated by four dicyan­amide nitrile N atoms [Co—N = 2.098 (3) and 2.104 (3) Å] in the basal plane, along with two monodentate quinoxaline N atoms [Co—N = 2.257 (2) Å] in the apical positions. In complex (II), the Cu atom is surrounded by four dicyan­amide nitrile N atoms [Cu—N = 2.003 (3) and 2.005 (3) Å] in the equatorial plane and two monodentate quinoxaline N atoms [Cu—N = 2.479 (3) Å] in the axial sites, to form a distorted tetragonal–bipyramidal geometry. The metal atoms reside on twofold axes of rotation. Neighbouring metal atoms are connected via double dicyan­amide bridges to form one‐dimensional infinite chains. Adjacent chains are then linked by π–π stacking interactions of the quinoxaline mol­ecules, resulting in the formation of a three‐dimensional structure.     

{2,2′‐[1,1′‐(4‐Aza­heptane‐1,7‐diyl­dinitrilo)diethyl­idyne]­diphenolato}­copper(II)

The quinquedentate ligand 2,2′‐[1,1′‐(4‐aza­heptane‐1,7‐diyl­dinitrilo)diethyl­idyne]diphenol in the title compound, [Cu(C₂₂H₂₇N₃O₂)], furnishes an N₃O₂ donor set, which results in a distorted square‐pyramidal coordination; the two O and two imine N atoms lie in the basal plane, while the secondary amine N atom of the ligand occupies the axial position. The axial Cu—N bond is 0.33 Å longer than the average of the equatorial bonds, and the O atoms are trans. The symmetry of the mol­ecule is lowered by the twist–boat and chair conformations adopted by the two CuNN chelate rings. The complex contains two intra­molecular C—H⋯O inter­actions, and two mol­ecules of the complex are linked into a dimer by means of moderate N—H⋯O hydrogen bonds. Spectroscopic evidence supports the presence of hydrogen bonds.     

Bis­[1,3‐bis(2‐methyl­tetrazol‐5‐yl‐κN4)­triazenido‐κN2]­nickel(II)

The title compound, [Ni(BMTT)₂], where BMTT is 1,3‐bis(2‐methyl­tetrazol‐5‐yl)­triazenide (C₄H₆N₁₁), presents a molecular complex with tridentate ligands. The tridentate mode of the ligand is realised through the central N atom of the triazene group and two N atoms of the two tetrazole rings. The [Ni(BMTT)₂] mol­ecule is the meridional isomer, with crystallographic symmetry in space group P4₂/n. The nickel centre has a distorted octahedral environment, with two axial Ni—N bonds of 2.041 (2) Å and four equatorial Ni—N bonds of 2.0739 (14) Å. The mol­ecules are linked together by van der Waals interactions only.     

Dichloro­[(1E,1′E)‐1,1′‐(pyridine‐2,6‐di­yl)diethanone bis­(O‐methyloxime)‐κ3N1,N2,N6]cobalt(II)

In the title compound, [CoCl₂(C₁₁H₁₅N₃O₂)], the Co^II ion is five‐coordinated in a strongly distorted square‐pyramidal arrangement, with one of the two Cl atoms located in the apical position, and the other Cl atom and the three N‐donor atoms of the tridentate methyloxime ligand located in the basal plane. The non‐H atoms, except for the Cl atoms, lie on a mirror plane. The two equatorial Co—N_oxime distances are almost equal (mean 2.253 Å) and are substanti­ally longer than the equatorial Co—N_pyridine bond [2.0390 (19) Å]. The structure is stabilized by intra‐ and inter­molecular C—H⋯Cl contacts, which involve one of the methyl C atoms belonging to the methyloxime groups.     

(2‐Methyl­quinolin‐8‐olato)­iron(III) and ‐copper(II) complexes

The crystal structures of tris(2‐methyl­quinolin‐8‐olato‐N,O)­iron(III), [Fe­(C₁₀­H₈­NO)₃], (I), and aqua­bis(2‐methyl­quinolin‐8‐olato‐N,O)­copper(II), [Cu­(C₁₀­H₈NO)₂­(H₂O)], (II), have been determined. Compound (I) has a distorted octahedral configuration, in which the central Fe atom is coordinated by three N atoms and three O atoms from three 2‐methylquinolin‐8‐olate ligands. The three Fe—O bond distances are in the range 1.934 (2)–1.947 (2) Å, while the three Fe—N bond distances range from 2.204 (2) to 2.405 (2) Å. In compound (II), the central Cu^II atom and H₂O group lie on the crystallographic twofold axis and the coordination geometry of the Cu^II atom is close to trigonal bipyramidal, with the three O atoms in the basal plane and the two N atoms in apical positions. The Cu—N bond length is 2.018 (5) Å. The Cu—O bond length in the basal positions is 1.991 (4) Å, while the Cu—O bond length in the apical position is 2.273 (6) Å. There is an intermolecular OW—H?O hydrogen bond which links the mol­ecules into a linear chain along the b axis.     

(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.     

trans‐Di­aqua­bis(5‐carboxy‐1H‐imidazole‐4‐carboxyl­ato‐κ2N3,O4)­cobalt(II) 4,4′‐bi­pyridine solvate

In the title compound, [Co(C₅H₃N₂O₄)₂(H₂O)₂]·C₁₀H₈N₂, the Co atom is trans‐coordinated by two pairs of N and O atoms from two monoanionic 4,5‐di­carboxy­imidazole ligands, and by two O atoms from two coordinated water mol­ecules, in a distorted octahedral geometry. The 4,4′‐bi­pyridine solvent molecule is not involved in coordination but is linked by an N—H⋯N hydrogen bond to the neutral [Co(C₅H₃N₂O₄)₂(H₂O)₂] mol­ecule. Both mol­ecules are located on inversion centers. The crystal packing is stabilized by N—H⋯N and O—H⋯O hydrogen bonds, which produce a three‐dimensional hydrogen‐bonded network. Offset π–π stacking interactions between the pyridine rings of adjacent 4,4′‐bi­pyridine molecules were observed, with a face‐to‐face distance of 3.345 (1) Å.     

[N,N′‐Bis(5‐bromo­salicyl­idene)‐1,3‐di­amino­propane]­nickel(II) and [N,N′‐­bis(5‐chloro­salicyl­idene)‐1,3‐­di­amino­propane]copper(II)

The title compounds, {4,4′‐di­bromo‐2,2′‐[1,3‐propane­diyl­bis(nitrilo­methyl­idyne‐N)]­diphenolato‐O,O′}nickel(II), [Ni(C₁₇­H₁₄­Br₂­N₂O₂)], and {4,4′‐di­chloro‐2,2′‐[1,3‐pro­pane­diyl­bis­(ni­trilo­methyl­idyne‐N)]­di­phen­ol­ato‐O,O′}­copper(II), [Cu­(C₁₇­H₁₄­Cl₂­N₂O₂)], lie on crystallographic twofold axes. In both structures, the metal coordination sphere is a tetrahedrally distorted square plane formed by the four‐coordinate N₂O₂ donor set of the Schiff base imine–phenol ligands. In the Ni compound, the Ni—O and Ni—N distances are 1.908 (3) and 1.959 (4) Å, respectively, while in the Cu compound, the Cu—O and Cu—N distances are 1.907 (2) and 1.960 (2) Å, respectively. The two Schiff base moieties, which themselves are nearly planar, are inclined at an angle of 29.26 (7)° for the Ni compound and 29.26 (5)° for the Cu compound.     

trans‐Diaquabis(1H‐imidazole‐4,5‐di­carboxyl­ate‐κ2N3,O4)­manganese(II)

In the title compound, [Mn(C₅H₃N₂O₄)₂(H₂O)₂], the Mn^II atom lies on an inversion centre, is trans‐coordinated by two N,O‐bidentate 1H‐imidazole‐4,5‐di­carboxyl­ate monoanionic ligands [Mn—O = 2.202 (3) Å and Mn—N = 2.201 (4) Å] and two water mol­ecules [Mn—O = 2.197 (4) Å], and exhibits a distorted octahedral geometry, with adjacent cis angles of 76.45 (13), 86.09 (13) and 89.20 (13)°. The complete solid‐state structure can be described as a three‐dimensional supramol­ecular framework, stabilized by extensive hydrogen‐bonding interactions involving the coordinated water mol­ecules, the carboxy O atoms and the protonated imidazole N atoms of the imidazole‐4,5‐di­carboxyl­ate ligands.     

A complex containing both five‐ and six‐coordinate [bis(5‐bromosalicyli­dene)benzene‐1,2‐diimine]chloro­iron(III)

The title compound, aqua­chloro{4,4′‐di­bromo‐2,2′‐[o‐phenylenebis­(nitrilo­methyl­idyne)]­diphenolato‐O,N,N′,O′}iron(III)–chloro{4,4′‐di­bromo‐2,2′‐[o‐phenyl­enebis­(nitrilomethyli‐dyne)]diphenolato‐O,N,N′,O′}iron(III)–di­methyl­form­amide (1/1/1), [FeCl(C₂₀H₁₂Br₂N₂O₂)][FeCl(C₂₀H₁₂Br₂N₂O₂)(H₂O)]·C₃H₇NO, contains one independent five‐coordinate [FeCl(C₂₀H₁₂Br₂N₂O₂)] monomer, one six‐coordinate [FeCl(C₂₀H₁₂Br₂N₂O₂)(H₂O)] monomer and a non‐coordinating di­methyl­form­amide solvent mol­ecule in the asymmetric unit. In the five‐coordinate monomer, the Fe atom shows distorted square‐pyramidal geometry, with the N and O atoms of the ligand at the base and the Cl atom at the apex of the pyramid. In the six‐coordinate monomer, the Fe atom is in a distorted octahedral geometry and coordinated by the donor atoms of the tetrafunctional ligand in the horizontal plane, and the coordination sphere is completed by the O atom of the water mol­ecule and the Cl atom at the axial positions. The title compound contains intermolecular O—H?O hydrogen bonds. Apart from these hydrogen bonds, there are also intermolecular C—H?Cl and C—H?O contacts.     

Aquachlorobis[4,4,5,5‐tetramethyl‐2‐(2‐pyridyl)‐4,5‐dihydro‐1H‐imidazol‐1‐oxyl 3‐oxide‐κ2O1,N2]nickel(II) nitrate methanol disolvate monohydrate

The title complex, [NiCl(C₁₂H₁₆N₃O₂)₂(H₂O)]NO₃·2CH₄O·H₂O, was obtained from a methano­lic solution of Ni(NO₃)₂·6H₂O, 2‐pyridyl nitro­nyl nitro­xide (2‐NITpy) and (NEt₄)₂[CoCl₄]. The equatorial coordination sites of the octahedral Ni^II centre are occupied by two chelating radical ligands, with the axial positions occupied by the Cl^? and water ligands. The H₂O—Ni—Cl axis of the complex lies along a crystallographic twofold axis, so that only half the cation is present in the asymmetric unit. The Ni—Cl bond length [2.3614 (17) Å] is significantly shorter than distances typical of octahedral Ni^II centres [2.441 (5) Å]. However, with only one nitrate anion per formula unit, the oxidation state of the metal must be assigned as Ni^II. The 2‐NITpy ligands bend away from the equatorial plane, forming a hydro­phobic region around the Cl atoms. Conversely, the ligated water mol­ecule forms moderately strong hydrogen bonds with the disordered methanol solvent mol­ecules, which in turn form interactions with the water of crystallization and the disordered nitrate anion. These interactions combine to give hydro­philic regions throughout the crystal structure.     

Di‐μ‐aqua‐bis­[(N‐salicyl­idene‐β‐alaninato‐κ3O,N,O′)copper(II)] urea disolvate

Crystals of the title compound, [Cu₂(C₁₀H₉NO₃)₂(H₂O)₂]·2CH₄N₂O, consist of two (N‐salicyl­idene‐β‐alaninato‐κ³O,N,O′)copper(II) coordination units bridged by two water moieties to form a dimer residing on a crystallographic inversion center, along with two uncoordinated urea mol­ecules. The Cu^II atom has square‐pyramidal coordination, with three donor atoms of the tridentate Schiff base and an O atom of the bridging aqua ligand in the basal plane. The axial position is occupied by the second bridging water ligand at a distance of 2.5941 (18) Å. Hydro­gen bonds between mol­ecules of urea and the neighboring dimer units lead to the formation of a two‐dimensional grid of mol­ecules parallel to [101]. The superposition of the normals of the pyramidal base planes in the direction [100] indicates possible π–π interactions between the neighboring units.     

Dichloro­(O‐ethyl 3‐methyl­pyridine‐2‐carboximidic acid‐κ2N,N′)copper(II)

In the title compound, [CuCl₂(C₉H₁₂N₂O)], the Cu^II atom is coordinated by two Cl⁻ anions and two N atoms of one O‐ethyl 3‐methyl­pyridine‐2‐carboximidic acid mol­ecule in a slightly distorted square‐planar geometry, with Cu—N distances of 2.0483 (17) and 1.9404 (18) Å, and Cu—Cl distances of 2.2805 (10) and 2.2275 (14) Å. In addition, each Cu^II atom is connected by one Cl⁻ anion and the Cu^II atom from a neighbouring mol­ecule, with Cu⋯Cl and Cu⋯Cu distances of 2.9098 (13) and 3.4022 (12) Å, respectively, and, therefore, a centrosymmetric dimer is formed. Adjacent mol­ecular dimers are connected by π–π stacking inter­actions between pyridine rings to form a zigzag mol­ecular chain. The mol­ecular chains are also enforced by N—H⋯Cl and C—H⋯Cl inter­actions.     

{4‐Bromo‐2‐[2‐(5‐bromo‐2‐oxido­benzyl­idene­amino­methyl)­phenyl­imino­methyl]­phenolato‐κ4O,N,N′,O′}nickel(II)

In the title complex, [Ni(C₂₁H₁₄Br₂N₂O₂)], the Ni^II atom is coordinated by the two imine N and two phenolate O atoms of the Schiff base ligand in a tetrahedrally distorted square‐planar geometry. The Ni—N and Ni—O distances are within the ranges expected for Ni–Schiff base derivatives. Intermolecular C—H⋯O hydrogen bonds link the mol­ecules into centrosymmetric dimers, forming (12) (A) and (10) (B) rings. These dimers combine to form a supramolecular ABAB… aggregate which propagates along the [100] direction.     

Aqua(2,2′‐di­amino‐4,4′‐bi‐1,3‐thia­zole‐κ2N,N′)(imino­diacetato‐κ3O,N,O′)­chromium(III) chloride mono­hydrate

Crystals of the title compound, [Cr(C₄H₅NO₄)(C₆H₆N₄S₂)(H₂O)]Cl·H₂O, consist of Cr^III complex cations, Cl⁻ counter‐ions and lattice water mol­ecules. The complex cation assumes an octahedral coordination geometry, formed by a tridentate imino­di­acetate dianion (IDA), a di­amino­bi­thia­zole (DABT) mol­ecule and a water mol­ecule. The planar DABT group chelates the Cr^III ion with normal Cr—N distances [2.0574 (17) and 2.0598 (17) Å], but the DABT mol­ecule is inclined to the coordination plane by a dihedral angle of 17.23 (7)°. In the monodentate carboxylate groups of the IDA ion, the coordinated C—O bonds [1.288 (3) and 1.284 (3) Å] are much longer than the uncoordinated C—O bonds [1.222 (3) and 1.225 (3) Å].     

catena‐Poly­[[tetrakis(2‐allyl­tetrazole‐κN4)‐tetra‐μ‐chloro‐tricopper(II)]‐di‐μ‐chloro]

In the crystal structure of the title compound, [Cu₃Cl₆(C₄H₆N₄)₄]_n, there are three Cu atoms, six Cl atoms and four 2‐allyl­tetrazole ligands in the asymmetric unit. The polyhedron of one Cu atom adopts a flattened octahedral geometry, with two 2‐allyl­tetrazole ligands in the axial positions [Cu—N4 = 1.990 (2) and 1.991 (2) Å] and four Cl atoms in the equatorial positions [Cu—Cl = 2.4331 (9)–2.5426 (9) Å]. The polyhedra of the other two Cu atoms have a square‐pyramidal geometry, with three basal sites occupied by Cl atoms [Cu—Cl = 2.2487 (9)–2.3163 (8) and 2.2569 (9)–2.3034 (9) Å] and one basal site occupied by a 2‐allyl­tetrazole ligand [Cu—N4 = 2.028 (2) and 2.013 (2) Å]. A Cl atom lies in the apical position of either pyramid [Cu—Cl = 2.8360 (10) and 2.8046 (9) Å]. The possibility of including the tetrazole N3 atoms in the coordination sphere of the two Cu atoms is discussed. Neighbouring copper polyhedra share their edges with Cl atoms to form one‐dimensional polymeric chains running along the a axis.