Bis­(dicyan­amido)(diethyl­enetri­amine‐κ3N)copper(II) and (dicyan­amido)(tri­ethyl­enetetr­amine‐κ4N)copper(II) dicyan­amide

Two new complexes, [Cu(C₂N₃)₂(dien)] (dien is diethyl­ene­tri­amine, C₄H₁₃N₃), (I), and [Cu(C₂N₃)(trien)](C₂N₃) (trien is triethyl­ene­tetr­amine, C₆H₁₈N₄), (II), have been characterized by single‐crystal X‐ray diffraction. Both complexes display a distorted tetragonal–pyramidal geometry. In (I), the Cu atom is coordinated in the basal plane by three diethyl­ene­tri­amine N atoms [Cu—N = 2.000 (2), 2.004 (2) and 2.025 (2) Å] and one terminal N atom [Cu—N = 1.974 (2) Å] from one monodentate dicyan­amide group, and in the apical position by one terminal N atom [Cu—N = 2.280 (2) Å] from the other monodentate dicyan­amide group. In (II), the Cu atom is surrounded by four triethyl­ene­tetr­amine N atoms [Cu—N = 2.012 (2), 2.014 (2), 2.019 (2) and 2.031 (2) Å in the basal plane] and a terminal N atom [Cu—N = 2.130 (2) Å in the apical site] from one monodentate dicyan­amide group. The other dicyan­amide anion is not directly coordinated to the metal atom. In both (I) and (II), hydro­gen‐bond interactions between the uncoordinated terminal N atoms of two dicyan­amide ions and the amine H atoms lead to the formation of three‐dimensional networks.     

Low‐dimensional compounds containing cyano groups. II. catena‐Poly[[(2,2′‐bipyridine‐κ2N:N′)(dicyanamido‐κN)copper(II)]‐μ‐dicyanamido‐κ2N:N′]

The crystal structure of the title compound, [Cu(C₂N₃)₂(C₁₀H₈N₂)]_n, is formed by neutral zigzag chains of the [–NC–N–CN–Cu{(bpy)N(CN)₂}–NC–N–CN–] type run­ning along the c axis (bpy is 2,2′‐bi­pyridine). The Cu atoms in the chains are pentacoordinated in the form of a distorted tetragonal pyramid, with a CuN₅ chromophore. The coordination sites are occupied by two N atoms of one bpy mol­ecule in the basal plane [Cu—N 2.018 (4) and 2.025 (2) Å] and by three terminal N atoms of two dicyan­amide ligands. One of the dicyan­amide ligands is coordinated in a monodentate fashion through a nitrile N atom in the basal plane [Cu—N 1.963 (4) Å]. The second acts as an end‐to‐end bridging ligand to a neighbouring Cu atom and is coordinated by one nitrile N atom in the basal plane [Cu—N 2.001 (2) Å], while the second nitrile N atom occupies the apical position [Cu—N 2.159 (2) Å] and originates from the bridge connecting another Cu atom. The shortest intrachain Cu?Cu distance is 8.212 (1) Å, as a consequence of the large bridging ligand, whereas the minimum interchain distance between Cu atoms is only 5.77 (7) Å, because of the interdigitation of the chains.     

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

The title compound, [Cu(C₂N₃)(C₁₂H₈N₂)₂]ClO₄, represents a relatively rare class of compounds with dicyan­amide coordinated in a monodentate manner. The structure is formed by the [Cu{N(CN)₂}(phen)₂]⁺ complex cation (phen is 1,10‐phenanthroline) and an uncoordinated ClO₄⁻ anion. The Cu atom is five‐coordinate, with a slightly distorted trigonal–bipyramidal environment. The dicyan­amide ligand is coordinated through one nitrile N atom in the equatorial plane, at a distance of 2.033 (6) Å from the metal. The two axial Cu—N distances are similar [mean 1.999 (4) Å] and are substantially shorter than the remaining two equatorial Cu—N bonds [mean 2.087 (1) Å].     

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.     

Bis­[bis­(pyrimidin‐2‐yl‐κN)­amine](dicyan­amido‐κN1)(tri­fluoro­methanesulfonato‐κO)copper(II) ethanol hemisolvate forms a hydrogen‐bonded chain

In the crystal structure of [Cu(CF₃SO₃)(C₂N₃)(C₈H₇N₅)₂]·0.5C₂H₆O, the Cu^II atom adopts a distorted octahedral geometry, with the basal plane formed by two N atoms of one dipyrimidinyl­amine ligand, one N atom of the second pyrimidine ligand and a nitrile N atom of the dicyan­amide anion [Cu—N = 1.972 (2)–2.021 (2) Å]. The apical positions are occupied by an N atom of the second ligand [Cu—N = 2.208 (2) Å], and an O atom of the tri­fluoro­methane­sulfonate anion [Cu—O = 2.747 (2) Å] at a semi‐coordination distance. Pairs of inversion‐related N—H⋯N hydrogen bonds of the so‐called Watson–Crick type, augmented by two C—H⋯N contacts, link adjacent complexes into an infinite one‐dimensional chain running in the [101] direction.     

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.     

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.     

(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.     

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.     

[N,N′‐Bis(3‐aminopropyl)ethylenediamine‐κ4N,N′,N′′,N′′′](trithiocyanurato‐κ2N,S)zinc(II) ethanol solvate

In the crystal structure of the title compound, [N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine‐κ⁴N,N′,N′′,N′′′][1,3,5‐triazine‐2,4,6(1H,3H,5H)‐tri­thionato(2−)‐κ²N,S]­zinc(II) ethanol sol­vate, [Zn(C₈H₂₂N₄)₂(C₃HN₃S₃)]·C₂H₆O, the Zn^II atom is octa­hedrally coordinated by four N atoms [Zn—N = 2.104 (2)–2.203 (2) Å] of a tetradentate N‐donor N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine (bapen) ligand and by two S and N atoms [Zn—S = 2.5700 (7) Å and Zn—N = 2.313 (2) Å] of a tri­thio­cyanurate(2−) (ttcH²⁻) dianion bonded as a bidentate ligand in a cis configuration. The crystal structure of the compound is stabilized by a network of hydrogen bonds.     

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.     

Acetato(N‐phenylpyridine‐2‐carboxamidato‐κ2N,N)(N‐phenylpyridine‐2‐carboxamide‐κ2N1,O)copper(II)

The title complex, [Cu(C₁₂H₉N₂O)(C₂H₃O₂)(C₁₂H₁₀N₂O)], is a neutral Cu^II complex with a primary N₃O₂ coordination sphere. The Cu centre coordinates to both a deprotonated and a neutral molecule of N‐phenylpyridine‐2‐carboxamide and also to an acetate anion. The coordination around the metal centre is asymmetric, the deprotonated ligand providing two N donor atoms [Cu—N = 1.995 (2) and 2.013 (2) Å] and the neutral ligand providing one N and one O donor atom to the coordination environment [Cu—N = 2.042 (2) Å and Cu—O = 2.2557 (19) Å], the fifth donor being an O atom of the acetate ion [Cu—O = 1.9534 (19) Å]. The remaining O atom from the acetate ion can be considered as a weak donor atom [Cu—O = 2.789 (2) Å], conferring to the Cu complex an asymmetric octahedral geometry. The crystal structure is stabilized by intermolecular N—H...O, C—H...O and C—H...π interactions.     

Bis(3‐amino­pyridine‐κN)(4,4′‐di­methyl‐2,2′‐bipyridine‐κ2N,N′)(per­chlorato‐κO)copper(II) per­chlorate

The title compound, [Cu(ClO₄)(C₅H₆N₂)₂(C₁₂H₁₂N₂)]ClO₄, was prepared by in situ partial ligand substitution between 3‐amino­pyridine and 4,4′‐dimethyl‐2,2′‐bipyridine at room temperature. The central copper(II) ion is five‐coordinated by one bidentate 4,4′‐dimethyl‐2,2′‐bipyridine mol­ecule, two monodentate pyridine‐coordinated 3‐amino­pyridine mol­ecules and one apical O atom from the perchlorate counter‐ion. Inter­molecular N—H⋯O and C—H⋯O hydrogen‐bonding inter­actions form a hydrogen‐bond‐sustained network.     

(2,2′‐Bi­pyridine‐κ2N)­bis­[N‐(2‐pyridyl‐κN)‐p‐toluene­sulfon­amido‐κN]zinc(II)

The structure of the title compound, [Zn(C₁₂­H₁₁­N₂­O₂S)₂(C₁₀H₈N₂)], consists of monomeric mol­ecules in which the central ZnN₂N′N′′ unit has a distorted tetrahedral geometry, with bond lengths ranging from 2.020 (3) to 2.109 (3) Å. The anionic ligands are potential bidentate donors and thus there are two secondary Zn—N interactions. The shorter of these is 2.317 (3) Å and completes at the Zn atom an irregular five‐coordinated geometry, which can be described as a square pyramid showing 30% distortion towards the trigonal bipyramid; the other Zn—N contact is much longer at 2.549 (3) Å.     

The CoIII—C bond in (1‐thia‐4,7‐diazacyclodecyl‐κ3N4,N7,C10)(1,4,7‐triazacyclononane‐κ3N1,N4,N7)cobalt(III) dithionate hydrate

In the title compound, [Co(C₆H₁₅N₃)(C₇H₁₅N₂S)]S₂O₆·H₂O, the Co—C bond distance is 1.9930 (13) Å, which is shorter than for related compounds with the linear 1,6‐di­amino‐3‐thia­hexan‐4‐ide anion in place of the macrocyclic 1‐thia‐4,7‐diazacyclo­decan‐8‐ide anion. The coordinated carbanion produces an elongation of 0.102 (7) Å of the Co—N bond to the 1,4,7‐tri­aza­cyclo­nonane N atom in the trans position. This relatively small trans influence is presumably a result of the tri­amine ligand forming strong bonds to the Co^III atom.     

Low‐dimensional compounds containing cyano groups. I. catena‐Poly[[[dicyanoargentato(I)‐κN]bis(4‐methylpyridine‐κN)copper(II)]‐μ‐dicyanoargentato(I)‐κ2N:N′]

The structure of the title compound, [Cu(C₆H₇N)₂{Ag(CN)₂}₂]_n, is made up of neutral zigzag chains of [–NC–Ag–CN–Cu(4‐Mepy)₂{Ag(CN)₂}–NC–Ag–CN–] (4‐Mepy is 4‐methyl­pyridine). Neighbouring chains are linked by weak argentophilic interactions, with Ag?Ag distances of 3.2322 (12) Å. The Cu atom, which lies on a twofold rotation axis, is pentacoordinated by one monodentate Ag(CN)₂^? anion [Cu—N 1.985 (3) Å], the atoms of which lie on the same rotation axis, and by bridging di­cyano­argentate anions [2 × Cu—N 2.0827 (19) Å], with Ag atoms on inversion centres. The coordination polyhedron is completed by two 4‐Mepy mol­ecules [2 × Cu—N 2.038 (2) Å], which occupy the axial positions of a distorted trigonal bipyramid.     

(2,2′‐Bipyridyl‐κ2N,N′)­bis­(salicyl­ato‐κ2O,O′)­zinc(II)

The asymmetric unit of the title compound, [Zn(C₇H₅O₃)₂(C₁₀H₈N₂)], contains one monomeric zinc complex. The Zn atom is coordinated to one 2,2′‐bipyridyl ligand via both N atoms and to two salicyl­ate anions (Hsal⁻) in a bidentate chelating manner involving carboxyl­ate O‐atom coordination. The complex exhibits a distorted octahedral geometry about the Zn^II atom, with the `apical' positions occupied by one of the two N atoms of the bipyridyl ligand and an O atom from one Hsal<sup>−</sup> ligand; the Zn atom is 0.168 (1) Å out of the `basal' plane. Two intramolecular six‐membered hydrogen‐bonded rings are present, generated from interactions between the carboxyl and hydroxyl groups of the salicyl­ate ligands. The crystal packing is governed by weak C—H⋯O and C—H⋯π interactions.     

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.     

(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.     

catena‐Poly[[aqua­(2,2′‐bipyridine‐κ2N,N′)cadmium(II)]‐μ‐4‐carboxyl­atophenoxy­acetato‐κ3O:O4,O4′]

In the title compound, [Cd(C₉H₆O₅)(C₁₀H₈N₂)(H₂O)]_n, the Cd^II atom is coordinated in a distorted octa­hedral fashion by two carboxyl­ate groups (one in a monodentate and one in a bidentate fashion) from two 4‐carboxyl­ato­phenoxy­acetate anions, two N atoms from a 2,2′‐bipyridine ligand and one aqua ligand. The structure is a helix with a long pitch of 16.441 (5) Å. A three‐dimensional supra­molecular network is further constructed through π–π stacking and hydrogen‐bonding inter­actions between the helices.