(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.     

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.     

{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.     

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.     

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.     

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

The title polymeric compound, [CuCl₂(C₅H₁₀N₄)₂]_n, is the first structurally characterized complex with a bulky 1‐alkyl­tetrazole ligand. The coordination polyhedron of the Cu atom is an elongated octahedron. The equatorial positions of the octahedron are occupied by the two Cl atoms, with Cu—Cl distances of 2.2920 (8) and 2.2796 (9) Å, and by the two N‐4 atoms of the tetrazole ligands, with Cu—N distances of 2.023 (2) and 2.039 (2) Å. Two symmetry‐related Cl atoms occupy the axial positions, at distances of 2.8244 (8) and 3.0174 (8) Å from the Cu atom. The [CuCl₂(C₅H₁₀N₄)₂] units form infinite chains extended along the b axis, linked together only by van der Waals interactions. The skeleton of each chain consists of Cu and Cl atoms.     

[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.     

Bis(4,4′‐bi­pyridine‐κN)­bis­(hydrogen phthalato)‐κ2O,O′;κO‐zinc(II)

The title compound, [Zn(C₈H₅O₄)₂(C₁₀H₈N₂)₂], was obtained by the hydro­thermal reaction of ZnSO₄·7H₂O with phthalic acid (H₂pht) and 4,4′‐bi­pyridine (4,4′‐bipy). Crystallographic analysis shows that it has a one‐dimensional double‐chain structure via hydrogen‐bonding interactions. Each Zn^II atom, adopting a distorted tetrahedral geometry, is coordinated by two N atoms from two 4,4′‐bipy ligands, with Zn—N distances of 2.054 (4) and 2.104 (4) Å, and by two O atoms from symmetry‐related Hpht⁻ ligands, with Zn—O distances of 1.921 (4) and 2.019 (4) Å.     

Poly[[aqua­tetra­imidazole­di‐μ‐phthalato‐dicopper(II)] monohydrate]

The title complex, {[Cu₂(C₈H₄O₄)₂(C₃H₄N₂)₄(H₂O)]·H₂O}_n, is a three‐dimensional polymer formed through bridging by phthalate dianions of two different Cu^II cations and a network of O(N)—H⋯O hydrogen bonds. The Cu—O and Cu—N inter­action distances are in the ranges 2.0020 (16)–2.4835 (17) and 1.968 (2)–1.9855 (19) Å, respectively. The structure is composed of alternating polymer chains parallel to the c axis, with a shortest Cu⋯Cu distance of 6.3000 (5) Å.     

Bis(μ‐succinato‐O,O′:O′′,O′′′)bis[bis(2‐amino‐1,3‐benzothiazole‐N3)copper(II)]

In the title dimeric complex, [Cu₂(C₄H₄O₄)₂(C₇H₆N₂S)₄], which possesses a centre of symmetry, the Cu atoms are enclosed in a 14‐membered ring. They adopt a distorted square‐bipyramidal (4+2) coordination. The four closest donor atoms are two N atoms of 2‐amino­benzo­thiazole ligands and two O atoms of the succinate carboxylate groups. They form a square‐planar cis arrangement, with an average Cu—N distance of 2.003 (3) Å and Cu—O distances of 1.949 (3) and 1.965 (3) Å. Two longer Cu—O bonds of 2.709 (3) and 2.613 (3) Å involving the remaining O atoms of the carboxylate groups complete the sixfold coordination of the Cu atoms. The H atoms of each amino group of the 2‐amino­benzo­thiazole molecules form intra‐ and inter­molecular N—H?O hydrogen bonds. A nearly perpendicular inter­molecular C—H?Cg interaction (Cg is the centroid of the imidazole ring) is observed. The intramolecular Cu?Cu distance is 6.384 (2) Å.     

catena‐Poly[[[tetrakis(1‐methylimidazole‐κN3)copper(II)]‐μ2‐sulfato‐κ2O:O′] acetonitrile hemisolvate sesquihydrate]

The title compound, [Cu(C₄H₈N₂)₄]SO₄·0.5CH₃CN·1.5H₂O, consists of a double chain wherein the Cu centres are octahedrally coordinated by four 1‐methyl­imidazole ligands in the equatorial plane and by two axial sulfate ions which act as bridges between the Cu centres. The Cu—N bond lengths lie between 1.9929 (14) and 2.0226 (14) Å, but the Cu—O bond distances are longer, with values between 2.3496 (13) and 2.8276 (14) Å. The water mol­ecules participate in the formation of a network of hydrogen bonds of significance in maintaining the connectivity of the structure.     

Di‐μ‐methoxo‐bis({N,N′‐bis­[2‐(3,5‐di­methyl­pyrazol‐1‐yl)­ethyl]­amine‐κ3N}copper(II)) bis­(hexa­fluoro­phosphate)

The title compound, [Cu₂(C₁₄H₂₃N₅)₂(CH₃O)₂](PF₆)₂, has a doubly methoxo‐bridged centrosymmetric copper dimer cation involving two tridentate bis­(pyrazolyl)­amine ligands. The geometry of each Cu^II atom is a distorted square pyramid with two N atoms of the pyrazole in bis­[2‐(3,5‐di­methyl‐1‐pyrazolyl)­ethyl]­amine (bpea) and two μ₂‐bridging O atoms of the methoxo ligands forming the basal plane, and the amine N atom occupying the axial position. In the bridging plane, the Cu—O bond lengths are 1.940 (4) and 1.942 (4) Å, and the bond angles for O—Cu—O and Cu—O—Cu are 76.1 (2) and 103.9 (2)°, respectively. The Cu?Cu distance is 3.058 (1) Å. The central four‐membered ring lies on an inversion centre.     

Poly­[[bis­(pyridine‐κN)copper(II)]‐μ3‐5‐hydroxy­isophthalato‐κ3O:O′:O′′]

In the title compound, [Cu(C₈H₄O₅)(C₅H₅N)₂]_n or [Cu(OH‐BDC)(py)₂]_n (where OH‐H₂BDC is 5‐hydroxy­isophthalic acid and py is pyridine), the Cu atoms are coordinated by two N atoms from the pyridine ligands and by three O atoms from hydroxy­isophthalate ligands in a highly distorted triangular bipyramidal environment, with Cu—O distances in the range 1.941 (4)–2.225 (5) Å and Cu—N distances of 2.014 (6) and 2.046 (6) Å. The [Cu(OH‐BDC)]_n two‐dimensional network is built up from interlocking 22‐, 15‐ and eight‐membered rings via sharing of Cu atoms and O—H⋯O hydrogen bonds. Consolidation of the packing structure is achieved by edge‐ or point‐to‐face C—H⋯π interactions and offset or slipped π–π stacking interactions.     

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].     

[2,2′‐(1,3,5,8,10,12‐Hexaazacyclotetradecane‐3,10‐diyl)diethanol‐κ4N1,N5,N8,N12]bis(thiocyanato‐κS)copper(II)

In the crystal structure of the title compound, [Cu(NCS)₂(C₁₂H₃₀N₆O₂)], the Cu atom lies on an inversion centre and has an elongated octahedral coordination, with Cu—N distances of 2.004 (2) and 2.015 (2) Å, and a Cu—S distance of 2.9696 (10) Å. The 2,2′‐ethanol chains are axially oriented. The mol­ecules are linked to form a three‐dimensional network via O—H?N, N—H?O and N—H?S hydrogen bonds.     

Bis[1,1‐di­methyl­biguanide(1–)‐κ2N2,N5]copper(II) monohydrate

The crystal structure of the title compound, [Cu(C₄H₁₀N₅)₂]·H₂O, contains two independent copper N,N‐di­methyl­biguanide complex units, each with square‐planar coordination of the Cu atom by four N atoms. The two complexes have different symmetry, with one Cu atom lying on an inversion centre and the other on a twofold rotation axis. The Cu—N bond lengths are 1.923 (2) and 1.950 (2) Å in the centrosymmetric complex, and 1.928 (2) and 1.938 (2) Å in the non‐centrosymmetric complex. The crystal structure is stabilized by N—H⋯O, O—H⋯N and N—H⋯N hydrogen bonds; each water mol­ecule forms four hydrogen bonds involving three different Cu complexes.     

catena‐Poly[[[bis(μ‐4,5‐dihydrothiazole‐2‐thiolato)‐tetrahedro‐tetracopper(I)]‐di‐μ‐4,5‐dihydrothiazole‐2‐thiolato] dihydrate]

The title compound, {[Cu₄(C₃H₄NS₂)₄]·2H₂O}_n, was produced by diffusing a solution of 2‐mercapto­thia­zoline in tetra­hydro­furan into a solution of CuCl in CH₃CN at room temperature. The structure is characterized by self‐assembled one‐dimensional chains that are condensed from butterfly‐like [Cu(C₃H₄NS₂)]₄ tetrameric units via double S‐bridging at opposite ends. The Cu—Cu distances within the Cu₄ butterfly cluster are in the range 2.7103 (10)–2.9764 (10) Å, while the shortest Cu?Cu intercluster distance is 3.468 (1) Å, much longer than the sum of the van der Waals radii.     

μ‐(4,4′‐Bi­pyri­dine)‐N:N′‐bis[bis‐(pyrrol­idine­dithio­car­boxyl­ato‐S,S′)zinc(II)]

The title compound, [Zn₂(C₅H₈NS₂)₄(C₁₀H₈N₂)], consists of two bis(pyrrol­idine­dithio­carboxylato)­zinc molecules bridged by a 4,4′‐bi­pyridine molecule, and has a 222 symmetry. Each Zn atom forms a five‐coordinate pseudo‐square‐based pyramidal arrangement, with four Zn—S interactions and one Zn—N interaction; the Zn—N distance is 2.085 (3) Å and the Zn—S distances are in the range 2.3319 (8)–2.6290 (9) Å.     

2‐(4‐Bromophenyl)‐1,2‐dihydropyrimido[1,2‐a]benzimidazol‐4(3H)‐one and 4‐(4‐methylphenyl)‐3,4‐dihydropyrimido[1,2‐a]benzimidazol‐2(1H)‐one form hydrogen‐bonded base‐paired dimers

The title compounds, 2‐(4‐bromo­phenyl)‐1,2‐di­hydro­pyrimido­[1,2‐a]­benzimidazol‐4‐(3H)‐one, C₁₆H₁₂Br­N₃O, (IVa), and 4‐(4‐methylphenyl)‐3,4‐dihydropyrimido[1,2‐a]benzimidazol‐2‐(1H)‐one, C₁₇H₁₅N₃O, (Vb), both form R(8) centrosymmetric dimers via N—H?N hydrogen bonds. The N?N distance is 2.943 (3) Å for (IVa) and 2.8481 (16) Å for (Vb), with the corresponding N—H?N angles being 129 and 167°, respectively. However, in other respects, the supra­molecular structures of the two compounds differ. Both compounds contain different C—H?π interactions, in which the C—H?π(centroid) distances are 2.59 and 2.47 Å for (IVa) and (Vb), respectively (the latter being a short distance), with C—H?π(centroid) angles of 158 and 159°, respectively. The supramolecular structures also differ, with a short Br?O distance of 3.117 (2) Å in bromo derivative (IVa), and a C—H?O interaction with a C?O distance of 3.2561 (19) Å and a C—H?O angle of 127° in tolyl system (Vb). The di­hydro­pyrimido part of (Vb) is disordered, with a ratio of the major and minor components of 0.9:0.1. The disorder consists of two non‐interchangeable envelope conformers, each with an equatorial tolyl group and an axial methine H atom.     

Two‐dimensional square‐grid frameworks formed by self‐associating copper(II) complexes with 1‐(3‐pyridyl)‐ and 1‐(4‐pyridyl)‐substituted butane‐1,3‐diones

In bis­[1‐(3‐pyridyl)butane‐1,3‐dionato]copper(II) (the Cu atom occupies a centre of inversion), [Cu(C₉H₈NO₂)₂], (I), and bis­[1‐(4‐pyridyl)butane‐1,3‐dionato]copper(II) methanol solvate, [Cu(C₉H₈NO₂)₂]·CH₃OH, (II), the O,O′‐chelating diketonate ligands support square‐planar coordination of the metal ions [Cu—O = 1.948 (1)–1.965 (1) Å]. Weaker Cu⋯N inter­actions [2.405 (2)–2.499 (2) Å], at both axial sides, occur between symmetry‐related bis­(1‐pyridylbutane‐1,3‐dion­ato)copper(II) mol­ecules. This causes their self‐organization into two‐dimensional square‐grid frameworks, with uniform [6.48 Å for (I)] or alternating [4.72 and 6.66 Å for (II)] inter­layer separations. Guest methanol mol­ecules in (II) reside between the distal layers and form weak hydrogen bonds to coordinated O atoms [O⋯O = 3.018 (4) Å].