(Acetonitrile){2,6‐bis[1‐(2,4,6‐trimethylphenylimino)ethyl]pyridine}dichloridoruthenium(II) dichloromethane solvate

In the title compound, [RuCl₂(C₂H₃N)(C₂₇H₃₁N₃)]·CH₂Cl₂, the Ru^II ion is six‐coordinated in a distorted octahedral arrangement, with the two Cl atoms located in the apical positions, and the pyridine (py) N atom, the two imino N atoms and the acetonitrile N atom located in the basal plane. The two equatorial Ru—N_imino distances are almost equal (mean 2.087 Å) and are substantially longer than the equatorial Ru—N_py bond [1.921 (4) Å]. It is observed that the N_imino—M—N_py angle for the five‐membered chelate rings of pyridine‐2,6‐diimine complexes is inversely related to the magnitude of the M—N_py bond. The title structure is stabilized by intra‐ and intermolecular C—H...Cl hydrogen bonds, as well as by van der Waals interactions.     

(2,6‐Bis{1‐[4‐(dimethylamino)phenylimino]ethyl}pyridine)dichlorido(triphenylphosphine‐κP)ruthenium(II): a zigzag chain of fused centrosymmetric R22(12) rings

The title compound, [RuCl₂(C₂₅H₂₉N₅)(C₁₈H₁₅P)], a transfer hydrogenation catalyst, is supported by an N,N′,N′′‐tridentate pyridine‐bridged ligand and triphenylphosphine. The Ru^II centre is six‐coordinated in a distorted octahedral arrangement, with the two Cl atoms located in the axial positions, and the pyridine (py) N atom, the two imino N atoms and the triphenylphosphine P atom located in the equatorial plane. The two equatorial Ru—N_imino distances (mean 2.093 Å) are substantially longer than the equatorial Ru—N_py bond [1.954 (4) Å]. It is observed that the N_imino—M—N_py bond angle for the five‐membered chelate rings of 2,6‐bis(imino)pyridine‐based complexes is inversely related to the magnitude of the M—N_py bond. The title structure is stabilized by intra‐ and intermolecular C—H...Cl hydrogen bonds, as well as by intramolecular π–π stacking interactions between the aromatic rings belonging to the triphenylphosphine ligand and the dimethylaminophenyl fragment. The intermolecular hydrogen bonds form an R₂²(12) ring and a zigzag chain of fused centrosymmetric rings running parallel to the [100] direction.     

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

In the title compound, [CuCl₂(C₁₁H₁₅N₃O₂)], the Cu^II ion is five‐coordinated in a strongly distorted trigonal–bipyramidal arrangement, with the two methyl­oxime N atoms located in the apical positions, and the pyridine N and the Cl atoms located in the basal plane. The two axial Cu—N distances are almost equal (mean 2.098 Å) and are substantially longer than the equatorial Cu—N bond [1.9757 (15) Å]. It is observed that the N(oxime)—M—N(pyridine) bond angle for five‐membered chelate rings of 2,6‐diacetyl­pyridine dioxime complexes is inversely related to the magnitude of the M—N(pyridine) bond. The structure is stabilized by intra‐ and inter­molecular C—H⋯Cl hydrogen bonds which involve the methyl H atoms, except for one of the two acetyl­methyl groups.     

(Nitro‐κN)[2‐(phenyldiazenyl‐κN2)pyridine‐κN](2,2′:6′,2′′‐terpyridine‐κ3N)ruthenium(II) tetrafluoroborate

The Ru—N bond distances in the title complex, [Ru(NO₂)(C₁₁H₉N₃)(C₁₅H₁₁N₃)]BF₄ or [Ru(NO₂)(tpy)(azpy)]BF₄, [tpy is 2,2′:6′,2′′‐ter­pyridine and azpy is 2‐(phenyl­azo)­pyridine], are Ru—N_py 2.063 (4), Ru—N_azo 2.036 (4), Ru—N_nitro 2.066 (3) Å, and Ru—N_tpy 2.082 (4), 1.982 (3) and 2.074 (4) Å. The azo N atom is trans to the nitro group. The azo N=N bond length is 1.265 (5) Å, which is the shortest found in such complexes to date. This indicates a multiple bond between Ru and the N atom of the nitro group, and π‐­backbonding [dπ(Ru) π*(azo)] is decreased.     

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.     

Bis(2,2′‐bipyridine)(dicyanamido)­copper(II) tetrafluoroborate

In the title compound, [Cu(C₂N₃)(C₁₀H₈N₂)₂]BF₄, the Cu^II atom shows distorted trigonal‐bipyramidal geometry, with the dicyan­amido ligand in the equatorial plane. The two out‐of‐plane Cu—N bond lengths to bi­pyridine are 2.006 (3) and 1.998 (3) Å, whereas the in‐plane Cu—N distances are 2.142 (3) and 2.043 (3) Å to the bi­pyridine, and 2.015 (3) Å to the dicyan­amide.     

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.     

{2,2′‐[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.     

Pentacarbonyl(4‐phenylpyridine)­tungsten(0) and pentacarbonyl(2‐phenylpyridine)chromium(0)

In penta­carbonyl(4‐phenyl­pyridine)­tungsten(0), [W­(C₁₁H₉N)(CO)₅], the mol­ecules have mm site symmetry and the pyridine ligand, with m symmetry, is completely planar. In penta­carbonyl(2‐phenyl­pyridine)­chromium(0), [Cr(C₁₁­H₉N)(CO)₅], the mol­ecules are in general positions and the phenyl and pyridine rings of the ligand are twisted by 67.7 (3)° with respect to one another by rotation about the C—C bond joining them. In both compounds, the axial M—C_carbonyl bond trans to the M—N_ligand bond is significantly shorter than the equatorial M—C_carbonyl bonds.     

Tris[N‐(4‐fluorophenyl)pyridine‐2‐carboxamidato‐κ2N,N′]cobalt(III) trihydrate: a novel meridional complex

The title complex, [Co(C₁₂H₈FN₂O)₃]·3H₂O, has been synthesized for the first time. The complex comprises three bidentate ligands containing the pyridine‐2‐carbox­amide stem. The distorted octahedral coordination around the Co atom is formed via the pyridine (py) N atom and the deprotonated amide N atom of each ligand, with the three pyridine rings in a meridional arrangement. For each ligand, the pyridine ring and the carbonyl group are nearly coplanar, with torsion angles in the range 0.4 (3)–4.8 (4)°. The Co—N_py distances [1.9258 (16)–1.9656 (17) Å] are shorter than the corresponding Co—N_amide distances [1.9372 (17)–1.9873 (15) Å]. In addition, the Co—N_py distances are closely related to the magnitudes of the chelate angles, a shorter Co—N_py distance corresponding to a larger angle. Five intermolecular hydrogen bonds, involving carbonyl O atoms of the ligands and lattice water mol­ecules, lead to the formation of a mesh structure.     

5‐n‐Butylpyridine‐2‐carboxylate–copper(II) and –iron(III) complexes

In trans‐bis(5‐n‐butyl­pyridine‐2‐carboxyl­ato‐κ²N,O)­bis­(methanol‐κO)copper(II), [Cu(C₁₀H₁₂NO₂)₂(CH₄O)₂], the Cu atom lies on a centre of symmetry and has a distorted octahedral coordination. The Cu—O(methanol) bond length in the axial direction is 2.596 (3) Å, which is much longer than the Cu—­O(carboxylate) and Cu—N distances in the equatorial plane [1.952 (2) and 1.977 (2) Å, respectively]. In mer‐tris(5‐n‐bu­tyl­pyridine‐2‐carboxyl­ato‐κ²N,O)­iron(III), [Fe(C₁₀H₁₂NO₂)₃], the Fe atom also has a distorted octahedral geometry, with Fe—O and Fe—N bond‐length ranges of 1.949 (4)–1.970 (4) and 2.116 (5)–2.161 (5) Å, respectively. Both crystals are stabilized by stacking interactions of the 5‐n‐butyl­pyridine‐2‐carboxyl­ate ligand, although hydrogen bonds also contribute to the stabilization of the copper(II) complex.     

Bis{μ‐2‐[(2,3‐dichloro­phenyl)­amino]­benzoato‐κO}di‐μ2‐ethoxo‐octa­methyl­di‐μ3‐oxo‐tetra­tin(IV)

The title compound, [Sn₄(CH₃)₈(C₁₃H₈Cl₂NO₂)₂(C₂H₅O)₂O₂], is a centrosymmetric dimer, with three linearly fused four‐membered Sn—O—Sn—O rings. The coordination poly­hedron of the Sn atom bonded to the carboxyl­ate can be described as trigonal–bipyramidal distorted toward square‐pyramidal. That of the second Sn atom is similar, but the distortion towards square‐pyramidal geometry is greater. The Sn—O and Sn—C distances are 2.020 (2)–2.226 (2) and 2.096 (4)–2.114 (4) Å, respectively. The benzene rings of the 2‐[(2,3‐dichloro­phenyl)­amino]benzoate ligand subtend an angle of 50.49 (17)°; the conformation of the ligand is stabilized by intra­molecular N—H⋯Cl and N—H⋯O hydrogen bonds. The structure is assembled viaπ–π stacking inter­actions to form chains parallel to [10].     

(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.     

trans‐Di­chloro­tetrakis(4‐methylpyrimidine‐N1)­ruthenium(II)

The title compound, trans‐[Ru^IICl₂(N¹‐mepym)₄] (mepym is 4‐methylpyrimidine, C₅H₆N₂), obtained from the reaction of trans,cis,cis‐[Ru^IICl₂(N¹‐mepym)₂(SbPh₃)₂] (Ph is phenyl) with excess mepym in ethanol, has fourfold crystallographic symmetry and has the four pyrimidine bases coordinated through N¹ and arranged in a propeller‐like orientation. The Ru—N and Ru—Cl bond distances are 2.082 (2) and 2.400 (4) Å, respectively. The methyl group, and the N³ and Cl atoms are involved in intermolecular C—H?N and C—­H?Cl hydrogen‐bond interactions.     

catena‐Poly­[[(di‐2‐pyridyl­amine)­silver(I)]‐μ‐nicotinato] and catena‐poly­[[(di‐2‐pyridyl­amine)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato]

In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐nico­tinato‐κ²N:O], [Ag(C₆H₄NO₂)(C₁₀H₉N₃)]_n, the Ag^I atom is tetracoordinated by two N atoms from the di‐2‐pyridyl­amine (BPA) ligand [Ag—N = 2.3785 (18) and 2.3298 (18) Å] and by one N atom and one carboxyl­ate O atom from nicotinate ligands [Ag—N = 2.2827 (15) Å and Ag—O = 2.3636 (14) Å]. Bridging by nicotinate N and O atoms generates a polymeric chain structure, which extends along [100]. The carboxyl O atom not bonded to the Ag atom takes part in an intrachain C—H⋯O hydrogen bond, further stabilizing the chain. Pairs of chains are linked by N—H⋯O hydrogen bonds to generate ribbons. There are no π–π interactions in this complex. In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato‐κ²O¹:O²], [Ag(C₇H₅O₄)(C₁₀H₉N₃)]_n, the Ag^I atom has a distorted tetrahedral coordination, with three strong bonds to two pyridine N atoms from the BPA ligand [Ag—N = 2.286 (5) and 2.320 (5) Å] and to one carboxyl­ate O atom from the 2,6‐di­hydroxy­benzoate ligand [Ag—O = 2.222 (4) Å]; the fourth, weaker, Ag‐atom coordination is to one of the phenol O atoms [Ag⋯O = 2.703 (4) Å] of an adjacent moiety, and this interaction generates a polymeric chain along [100]. Pairs of chains are linked about inversion centers by N—H⋯O hydrogen bonds to form ribbons, within which there are π–π interactions. The ribbons are linked about inversion centers by pairs of C—H⋯O hydrogen bonds and additional π–π interactions between inversion‐related pairs of 2,6‐di­hydroxy­benzoate ligands to generate a three‐dimensional network.     

catena‐Poly­[[[cis‐bis(1‐phenyl­tetra­zole‐κN4)copper(II)]‐di‐μ‐chloro] hemi(1‐phenyl­tetrazole)]

The title compound, {[CuCl₂(PhTz)₂]·0.5PhTz}_n (PhTz is 1‐­phenyl­tetrazole, C₇H₆N₄), has a polymeric structure, with uncoordinated disordered PhTz mol­ecules in the cavities. The coordination polyhedron of the Cu atom is a highly elongated octahedron. The equatorial positions are occupied by two Cl atoms [Cu—Cl = 2.2687 (9) and 2.2803 (7) Å] and two N atoms of the PhTz ligands [Cu—N = 2.0131 (19) and 2.0317 (18) Å]. The more distant axial positions are occupied by two Cl atoms [Cu—Cl = 3.0307 (12) and 2.8768 (11) Å] that lie in the equatorial planes of two neighbouring Cu octahedra. The [CuCl₂(PhTz)₂] units are linked by Cu—Cl bridges into infinite chains extending parallel to the a axis. The chains are linked into two‐dimensional networks by intermolecular C—H⋯N interactions between the phenyl and tetrazole fragments, and by face‐to‐face π–π interactions between symmetry‐related phenyl rings. These two‐dimensional networks, which lie parallel to the ac plane, are connected by intermolecular π–π stacking interactions between phenyl rings, thus forming a three‐dimensional network.     

2‐Amino‐5‐methyl­pyridinium (2‐amino‐5‐methyl­pyridine)trichloro­zincate(II)

The title compound, (C₆H₉N₂)[ZnCl₃(C₆H₈N₂)], consists of one 2‐amino‐5‐methyl­pyridinium cation and one (2‐amino‐5‐methyl­pyridine)trichloro­zincate(II) anion, which are held together by N—H·Cl hydrogen bonds and π–π inter­actions. The cation and the pyridine ligand show similar geometric features, except for the N—C bond lengths. Mol­ecules of the title compound are connected by N—H·Cl hydrogen bonds to form chiral chains; these chains are associated further by C—H·Cl hydrogen bonds to form layers, which are in turn linked by π–π inter­actions.     

(η6‐Hexamethylbenzene)(mesidine)­ditriflatoruthenium(II)

The crystal structure of the title complex, (η⁶‐hexamethylbenzene)bis(trifluoromethanesulfonato‐O)(2,4,6‐trimethylanil­ine‐N)ruthenium(II), [Ru(CF₃O₃S)₂(C₁₂H₁₈)(C₉H₁₃N)], is described. The complex has the classic three‐legged piano‐stool structure with a planar arene 1.667 Å from the metal, two monodentate O‐bound tri­fluoro­methane­sulfonate ligands [Ru—O 2.169 (2) and 2.174 (2) Å] and one N‐bound mesidine ligand [Ru—N 2.198 (2) Å]. The Ru—N distance is relatively long and the average Ru—O distance is relatively short when compared with previously characterized Ru^II complexes.     

{2‐[(3‐Amino­propyl)­amino­propyl­imino­methyl]­imidazol­ato‐N,N′,N′′,N′′′}­(methanol‐O)­copper(II) per­chlorate

In the title compound, [Cu(C₁₀H₁₈N₅)(CH₄O)]ClO₄, four N atoms from the deprotonated ligand derived from bis(3‐amino­propyl)­amine and 2‐imidazole­carbox­aldehyde are coordinated to the Cu atom. The four N atoms occupy equatorial positions with Cu—N bond distances ranging from 1.998 (2) to 2.046 (3) Å. The methanol O atom occupies one axial position with a Cu—O bond distance of 2.295 (2) Å.     

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.