Aqua(n‐hexyl)[3,3′‐(propane‐1,3‐diyldinitrilo)­bis­(butan‐2‐one) dioximato‐­κ4N]cobalt(III) perchlorate

The title compound, [Co(C₆H₁₃)(C₁₁H₁₉N₄O₂)(H₂O)]ClO₄, is in the general class of coenzyme B₁₂ models which contain a ClO₄ anion and a [Co(C₆H₁₃)(C₁₁H₁₉N₄O₂)(H₂O)]⁺ cation. In the cation, the Co atom has a distorted octahedral coordination, with the n‐hexyl and H₂O ligands in axial positions. The crystal data reveal some degree of flexibility in the Costa‐type system, which is similar to the coenzyme B₁₂.     

trans‐(4‐Amino‐2,2,6,6‐tetramethyl­piperidine‐N4)bis(pentane‐2,4‐dion­ato‐O,O′)(triphenylphosphine‐P)cobalt(III) hexafluorophosphate dichloromethane solvate

The complex cation in the title compound, [Co(C₅H₇O₂)₂(C₉H₂₀N₂)(C₁₈H₁₅P)]PF₆·CH₂Cl₂, is the first example of a Co^III complex in which a trans configuration for the coordinated monodentate phosphine and amine ligands has been confirmed by X‐ray analysis. Owing to the large steric bulkiness of the axial PPh₃ ligands influencing the interaction with the equatorial acetyl­acetonate ligands, the acetyl­acetonate planes bend away considerably from the PPh₃ ligands.     

cis,cis,cis‐(Acetato‐O,O′)­bis­[1,2‐bis­(di­phenyl­phosphino)­ethane‐P,P′]­ruthenium(II) hexa­fluoro­phosphate di­methanol solvate

In the cation of the title complex, cis,cis,cis‐[Ru(η²‐O₂CMe)(dppe)₂]PF₆·2MeOH [dppe is 1,2‐bis­(di­phenyl­phosphino)­ethane, C₂₆H₂₄P₂], the Ru atom is in a pseudo‐octahedral coordination environment with two chelating dppe ligands and one chelating acetate ligand. Intra‐phosphine and intra‐acetate bond lengths and angles are unexceptional. Deviations from idealized octahedral coordination angles at ruthenium [O—Ru—O 59.43 (8)° and P—Ru—P 103.19 (2)°] presumably derive from constraints imposed by the chelate rings. The Ru—P distances for the mutually trans P‐donor atoms [2.3785 (6) Å] are significantly longer than those for the Ru—P linkages trans to the acetate ligand [2.3074 (6) Å]. The Ru1, C1 and C2 atoms lie on a twofold axis, and atom P3 of the anion lies on an inversion centre.     

(Tetra­hydro­furan)­potassium mer‐trans‐tris­(carbazolyl)­di­chloro(tetra­hydro­furan)­zirconate

In the title compound, [K(C₄H₈O)][ZrCl₂(C₁₂H₈N)₃(C₄H₈O)], the Zr atom is pseudo‐octahedral, with two Cl ligands in trans positions. There is extensive interaction between the potassium cation and two of the aromatic carbazolyl ligands in η⁶ [C⃛K = 3.167 (3)–3.331 (3) Å] and η² [C⃛K = 3.147 (3)–3.268 (2) Å] fashions.     

Bis­(aceto­nitrile‐N)(o‐benzoquinone di­imine‐N,N′)‐trans‐bis­(tri­phenyl­phosphine‐P)­ruthenium(II) bis(hexa­fluoro­phosphate) methanol solvate

The title complex, [Ru(C₂H₃N)₂(C₆H₆N₂)(C₁₈H₁₅P)₂](PF₆)₂.CH₄O, is the third of a series of ruthenium complexes containing two tri­phenyl­phosphine groups in a trans arrangement, o‐benzoquinone di­imine and two other non‐redox active ligands to been characterized. The effect of electron donor–acceptor properties of the two non‐redox active ligands does not change the quinone arrangement for the o‐benzoquinone di­imine ligand, as can be seen from the bond distances of the quinone ring. The asymmetric unit contains half a mol­ecule of complex cation (on a twofold rotation axis), one hexa­fluoro­phosphate anion and half a mol­ecule of methanol in a general position close to a twofold rotation axis.     

[N‐(Carboxyl­ato­methyl)­aspartato(3–)](ethyl­enedi­amine)­cobalt(III) trihydrate

The mononuclear title complex, [Co(C₆H₆NO₆)(C₂H₈N₂)]·3H₂O, contains an octahedrally coordinated Co^III atom. The N‐(carboxy­methyl)­aspartate moiety is coordinated as a tetradentate ligand, providing an OONO‐donor set and forming two trans five‐membered chelate rings and one six‐membered chelate ring. A seven‐membered chelate ring is also formed, which consists of part of the six‐membered chelate ring and part of one of the five‐membered chelate rings. The crystal structure of the complex is stabilized by hydrogen bonds with three water mol­ecules.     

{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.     

Cyano­cobalt(III) complexes of penta‐ and tetra­dentate‐coordinated macrocyclic hexa­amines

The pendent‐arm macrocyclic hexa­amine trans‐6,13‐dimethyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐6,13‐diamine (L) may coordinate in tetra‐, penta‐ or hexa­dentate modes, depending on the metal ion and the synthetic procedure. We report here the crystal structures of two pseudo‐octa­hedral cobalt(III) complexes of L, namely sodium trans‐cyano­(trans‐6,13‐dimethyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐6,13‐diamine)cobalt(III) triperchlorate, Na[Co(CN)(C₁₃H₃₀N₆)](ClO₄)₃ or Na{trans‐[CoL(CN)]}(ClO₄)₃, (I), where L is coordinated as a penta­dentate ligand, and trans‐dicyano­(trans‐6,13‐dimethyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐6,13‐diamine)cobalt(III) trans‐dicyano­(trans‐6,13‐dimethyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐6,13‐diaminium)cobalt(III) tetra­perchlorate tetra­hydrate, [Co(CN)₂(C₁₄H₃₂N₆)][Co(CN)₂(C₁₄H₃₀N₆)](ClO₄)₄·4H₂O or trans‐[CoL(CN)₂]trans‐[Co(H₂L)(CN)₂](ClO₄)₄·4H₂O, (II), where the ligand binds in a tetra­dentate mode, with the remaining coordination sites being filled by C‐­bound cyano ligands. In (I), the secondary amine Co—N bond lengths lie within the range 1.944 (3)–1.969 (3) Å, while the trans influence of the cyano ligand lengthens the Co—N bond length of the coordinated primary amine [Co—N = 1.986 (3) Å]. The Co—CN bond length is 1.899 (3) Å. The complex cations in (II) are each located on centres of symmetry. The Co—N bond lengths in both cations are somewhat longer than in (I) and span a narrow range [1.972 (3)–1.982 (3) Å]. The two independent Co—CN bond lengths are similar [1.918 (4) and 1.926 (4) Å] but significantly longer than in the structure of (I), again a consequence of the trans influence of each cyano ligand.     

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].     

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.     

Potassium bis­(carbonato‐O,O′)(ethylenedi­amine‐N,N′)­cobaltate(III) monohydrate at 173 K

The title salt, K[Co(C₂H₈N₂)(CO₃)₂]·H₂O, consists of a distorted octahedral cobalt complex anion and a seven‐coordinate potassium cation. Both metal atoms have crystallographic twofold symmetry, one C₂ axis passing through the Co atom and C—C bond, and another along a short K—O (water) bond of 2.600 Å (corrected for libration). The carbonate is bidentate to both cobalt and potassium and the water forms a hydrogen bond to a carbonate O atom.     

(Azido‐κN)bis­(di‐2‐pyridylamine)­copper(II) hexa­fluoro­phosphate and (azido‐κN)bis­(di‐2‐pyridylamine)­copper(II) chloride tetra­hydrate

The two new title complexes, [Cu(N₃)(dpyam)₂]PF₆ (dpyam is di‐2‐pyridylamine, C₁₀H₁₁N₃), (I), and [Cu(N₃)(dpyam)₂]Cl·4H₂O, (II), respectively, have been characterized by single‐crystal X‐ray diffraction. Both complexes display a distorted square‐pyramidal geometry. Each Cu atom is coordinated in the basal plane by three dpyam N atoms and one azide N atom in equatorial positions, and by another N atom from the dpyam group in the apical position. In complex (I), the one‐dimensional supra­molecular architecture is assembled via hydrogen‐bonding inter­actions between the amine N atom and terminal azide N atoms and the F atoms of the PF₆⁻ anion. For complex (II), hydrogen‐bonding inter­actions between the amine N atom, the Cl⁻ anion and water O atoms result in a two‐dimensional lattice.     

Cobalt(II) and nickel(II) complexes of isoquinoline‐1‐carboxylate

trans‐Di­aqua­bis­(iso­quinoline‐1‐carboxyl­ato‐κ²N,O)­cobalt(II) dihydrate, [Co(C₁₀H₆NO₂)₂(H₂O)₂]·2H₂O, and trans‐di­aqua­bis­(iso­quinoline‐1‐carboxyl­ato‐κ²N,O)­nickel(II) dihydrate, [Ni(C₁₀H₆NO₂)₂(H₂O)₂]·2H₂O, contain the same isoquinoline ligand, with both metal atoms residing on a centre of symmetry and having the same distorted octahedral coordination. In the former complex, the Co—O(water) bond length in the axial direction is 2.167 (2) Å, which is longer than the Co—O(carboxylate) and Co—N bond lengths in the equatorial plane [2.055 (2) and 2.096 (2) Å, respectively]. In the latter complex, the corresponding bond lengths for Ni—O(water), Ni—O(carboxylate) and Ni—N are 2.127 (2), 2.036 (2) and 2.039 (3) Å, respectively. Both crystals are stabilized by similar stacking interactions of the ligand, and also by hydrogen bonds between the hydrate and coordinated water molecules.     

Bis­(pyridine­carboxyl­ato‐O,N)­(pyri­dine­carboxyl­ic acid‐O,N)­manganese(III) hy­drox­ide

The title complex, [Mn(C₅H₄NCO₂)₂(C₅H₄NCOOH)]OH, consists of a cation and a hydro­xide ion. The Mn atom is coordinated by three N atoms and three O atoms from three pyridine­carboxyl­ate ligands, and has a distorted octahedral geometry, with Mn—N distances ranging from 2.157 (1) to 2.233 (1) Å and Mn—O distances from 1.910 (1) to 1.927 (4) Å. One ligand is protonated as the acid form. This forms one of two independent hydrogen bonds, to the anion.     

catena‐Poly­[[bis(pentane‐2,4‐dionato‐κ2O,O′)­cobalt(II)]‐μ‐4,4′‐methylene­dianiline‐κ2N:N′]

In the title compound, [Co(C₅H₇O₂)₂(C₁₃H₁₄N₂)]_n or [Co(acac)₂(dadpm)]_n, where acac is acetyl­acetonate and dadpm is 4,4′‐methylenedianiline, the Co atom is on a centre of symmetry and is octahedrally coordinated by four O atoms from two acac anions and by two N atoms from two dadpm ligands. Each dadpm ligand, which has a twofold axis passing through its methyl­ene C atom, bridges two Co atoms to form a spiral polymeric chain. Neighbouring chains connect via hydrogen bonds to form a two‐dimensional network.     

Bis­(acetato‐O)­tetrakis­(imidazole‐N3)­nickel(II)

In the title compound, [Ni(C₂H₃O)₂(C₃H₄N₂)₄], the Ni atom is coordinated centrosymmetrically by four N and two O atoms in an octahedral coordination [Ni—N = 1.986 (3) and 2.054 (3) Å; Ni—O = 2.697 (3) Å]. The O atoms of the acetate anions form hydrogen bonds to adjacent imidazole moieties, with the free O atom forming a somewhat shorter bond [N?O = 2.679 (3) and 2.870 (4) Å]. The hydrogen bonds give rise to a two‐dimensional layer structure.     

Aqua­(phthalocyaninato)­magnesium

The title compound, [Mg(C₃₂H₁₆N₈)(H₂O)], crystallizes with two MgPc(H₂O) mol­ecules (Pc is phthalocyaninate) in the asymmetric unit. The geometries of the two mol­ecules are very similar, with the Mg atoms each 4+1‐coordinated by four iso­indole N atoms at the base and by the O atom of the water mol­ecule. The Mg atoms are displaced by 0.447 (1) and 0.468 (1) Å from the basal coordination planes towards the water O atoms. O—H?N hydrogen bonds form dimers stacked along the b axis in a herring‐bone fashion.     

Methanol[1‐(methoxymethanimidoyl)‐2‐(pyridin‐2‐ylmethyl)guanidine]bis(perchlorato)copper(II)

The title complex, [Cu(ClO₄)₂(C₉H₁₃N₅O)(CH₃OH)], was synthesized from a methanolysis reaction of N‐(methylpyridin‐2‐yl)cyanoguanidine (L³) and copper(II) perchlorate hexahydrate in a 1:1 molar ratio. The Cu^II ion is six‐coordinated by an N₃O₃ donor set which confers a highly distorted and asymmetric octahedral geometry. Three N‐donor atoms from the chelating 1‐(methoxymethanimidoyl)‐2‐(pyridin‐2‐ylmethyl)guanidine (L^3m) ligand and one O atom from the methanol molecule define the equatorial plane, with two perchlorate O atoms in the apical sites, one of which has a long Cu—O bond of 2.9074 (19) Å. The dihedral angle between the five‐ and six‐membered chelate rings is 8.21 (8)°. Two molecules are associated into a dimeric unit by intermolecular N—H...O(perchlorate) hydrogen bonds. Additionally, the weakly coordinated perchlorate anions also link adjacent [Cu(ClO₄)₂(L^3m)(CH₃OH)] dimers by hydrogen‐bonding interactions, resulting in a two‐dimensional layer in the (100) plane. Further C—H...O hydrogen bonds link the two‐dimensional layers along [100] to generate a three‐dimensional network.     

Coordination behaviour and two‐dimensional‐network formation in poly[[μ‐aqua‐diaqua(μ5‐propane‐1,3‐diyldinitrilotetraacetato)dilithium(I)cobalt(II)] dihydrate]: the first example of an MII–1,3‐pdta complex with a monovalent metal counter‐ion

The title compound, {[CoLi₂(C₁₁H₁₄N₂O₈)(H₂O)₃]·2H₂O}_n, constitutes the first example of a salt of the [M^II(1,3‐pdta)]²⁻ complex (1,3‐pdta is propane‐1,3‐diyldinitrilotetraacetate) with a monopositive cation as counter‐ion. Insertion of the Li⁺ cation could only be achieved through application of the ion‐exchange column technique which, however, appeared unsuccessful with other alkali metals and the ammonium cation. The structure contains two tetrahedrally coordinated Li⁺ cations, an octahedral [Co(1,3‐pdta)]²⁻ anion and five water molecules, two of which are uncoordinated, and is built of two‐dimensional layers extending parallel to the (010) lattice plane, the constituents of which are connected by the coordinate bonds. O—H_water...O hydrogen bonds operate both within and between these layers. The crystal investigated belongs to the enantiomeric space group P2₁ with only one (Λ) of two possible optical isomers of the [Co(1,3‐pdta)]²⁻ complex. A possible cause of enantiomer separation during crystallization might be the rigidification and polarization of the [M(1,3‐pdta)]²⁻ core, resulting from direct coordination of Li⁺ cations to three out of four carboxylate groups constituting the 1,3‐pdta ligand. The structure of (I) differs considerably from those of the other [M^II(1,3‐pdta)]²⁻ complexes, in which the charge compensation is realized by means of divalent hexaaqua complex cations. This finding demonstrates a significant structure‐determining role of the counter‐ions.     

μ‐1,2‐Bis(4‐pyridyl)ethene‐κ2N:N′‐bis(tetraaqua­{4‐[2‐(4‐pyridinio)­ethenyl]pyridine‐κN}cobalt(II)) hexaaqua­cobalt(II) tetrakis(sulfate) octahydrate

The title compound, [Co₂(C₁₂H₁₁N₂)₂(C₁₂H₁₀N₂)(H₂O)₈][Co(H₂O)₆](SO₄)₄·8H₂O, consists of bis(4‐pyridyl)ethenedicobalt(II) cations, hexaaqua­cobalt cations, sulfate anions and water solvent molecules that are linked by hydrogen bonds into a network structure. In the hexaaquacobalt cation, the six water molecules are coordinated in an octahedral geometry to the Co atom, which lies on an inversion centre. The other cation is a 1,2‐bis(4‐pyridyl)ethene‐bridged centrosymmetric dimer, consisting of protonated 1,2‐bis(4‐pyridyl)­ethene cations, a bridging 1,2‐bis(4‐pyridyl)ethene ligand and tetraaqua­cobalt cations. Each Co atom is six‐coordinated by four water molecules and two N atoms from a protonated 1,2‐bis(4‐pyridyl)ethene cation and the bridging 1,2‐bis(4‐pyridyl)­ethene ligand, and the geometry around each Co atom is octahedral.