A dimeric cobalt(II)–suberate complex with 3‐amino­pyridine

The title complex, μ‐octane‐1,8‐dioato‐bis[bis(3‐aminopyridine)chloro(methanol)cobalt(II)], [Co₂(C₈H₁₂O₄)Cl₂(C₅H₆N₂)₄(CH₄O)₂], is located on a crystallographic centre of inversion. The coordination around each of the Co centres is distorted octa­hedral, involving two N, three O and one Cl atom. Discrete dimers are connected in a three‐dimensional arrangement through N—H⋯O, N—H⋯Cl and O—H⋯O hydrogen‐bond inter­actions.     

trans‐Cyano(6‐methyl‐1,4,8,11‐tetraazacyclotetradecan‐6‐amine)cobalt(III) bis(perchlorate) hydrate and trans‐hydroxo(6‐methyl‐1,4,8,11‐tetraazacyclotetradecan‐6‐amine)cobalt(III) bis(perchlorate)

The crystal structures of a pair of closely related macrocyclic cyano‐ and hydroxopenta­amine­cobalt(III) complexes, as their perchlorate salts, are reported. Although the two complexes, [Co(CN)(C₁₁H₂₇N₅)](ClO₄)₂·H₂O and [Co(OH)(C₁₁H₂₇N₅)](ClO₄)₂, exhibit similar conformations, significant differences in the Co—N bond lengths arise from the influence of the sixth ligand (cyano as opposed to hydroxo). The ensuing hydrogen‐bonding patterns are also distinctly different. Disorder in the perchlorate anions was clearly resolved and this was rationalized on the basis of distinct hydrogen‐bonding motifs involving the anion O atoms and the N—H and O—H donors.     

cis‐Tetra­carbonyl­[(4‐fluoro­phenyl)di­phenyl­phosphine‐P](piperidine‐N)molybdenum(0)

The title mol­ecule, [Mo{P(C₆H₅)₂(C₆H₄F)}(HNC₅H₁₀)(CO)₄] or [Mo(C₁₈H₁₄FP)(C₅H₁₁N)(CO)₄], has irregular octahedral geometry about the Mo atom. The mol­ecules form a complicated hydrogen‐bonded network comprising C—H?O, C—H?F and C—H?π hydrogen bonds and π–π interactions. The C—H?π and π–π interactions form chains containing C—H?π/π–π dimers linked via C—H?π interactions and the chains are linked into a three‐dimensional network via C—H?O and C—H?F hydrogen bonds.     

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.     

Constructor graph description of the hydrogen‐bonding supramolecular assembly in two ionic compounds: 2‐(pyrazol‐1‐yl)ethylammonium chloride and diaquadichloridobis(2‐hydroxyethylammonium)cobalt(II) dichloride

Covalent bond tables are used to generate hydrogen‐bond pattern designator symbols for the crystallographically characterized title compounds. 2‐(Pyrazol‐1‐yl)ethylammonium chloride, C₅H₁₀N₃⁺·Cl⁻, (I), has three unique, strong, charge‐assisted hydrogen bonds of the types N—H...Cl and N—H...N that form unary through ternary levels of graph‐set interactions. Diaquadichloridobis(2‐hydroxyethylammonium)cobalt(II) dichloride, [CoCl₂(C₂H₈NO)₂(H₂O)₂]Cl₂, (II), forms five unique charge‐assisted hydrogen bonds of the types O—H...Cl and N—H...Cl. These form graph‐set patterns up to the quinary level. The Co complex in (II) resides at a crystallographic inversion center; thus the number of hydrogen bonds to consider doubles due to their G‐equivalence, and the handling of such a case is demonstrated.     

Optisch aktive übergangsmetall-komplexe : XVIII. Über die reaktion von C5H5Co(CO)(C3F7)j mit isonitrilen

In the reaction of C₅H₅Co(CO)(C₃F₇)I with isonitriles in the molár ratio $\text{1}\text{1}$ the brown complexes C₅H₅Co(CNR)(C₃F₇)I are formed. The fluorine atoms of the α-CF₂ groups are diastereotopic because of the asymmetric center at the Co atom. With (—)-α-phenylethylisonitrile a pair of diastereoisomers is obtained which could not be separated.C₅H₅Co(CO)(C₃F₇)I and C₅H₅Co(CNR)(C₃F₇)I react with excess isonitrile with the formation of benzene soluble, yellow salts [C₅H₅Co(CNR)₂(C₃F₇)]⁺I^?, which can be transformed into the corresponding PF^?₆ salts. The new compounds were characterised by C, H, N, Co analyses, molecular weight determinations, IR, ¹H NMR, ¹⁹F NMR, ¹³C NMR, ESCA and mass spectra.     

The mononuclear cobalt(II) complex CoII(DMBDIZ)2(NCS)2, where DMBDIZ is 2,6‐di­methyl­benzo[1,2‐d:4,5‐d′]­di­imidazole

In the title mononuclear cobalt complex, bis(2,6‐di­methyl‐1H,7H‐benzo­[1,2‐d:4,5‐d′]­di­imidazole‐κN³)­bis­(thio­cyanato‐κN)cobalt(II), [Co^II(NCS)₂(DMBDIZ)₂] or [Co(NCS)₂(C₁₀H₁₀N₄)₂], the cobalt(II) ion is coordinated to four N atoms, from two thio­cyanate anions and two DMBDIZ ligands, in a distorted tetrahedral geometry. In the DMBDIZ ligand, the two imine N atoms are positioned cis with respect to one another. The crystal packing of the complex is dominated by both hydrogen bonding, involving two N—H?N and two N—H?S interactions, and aromatic π–π stacking.     

mer‐Diaquabis(1H‐imidazole‐κN3)[orotato(2–)]cobalt(II)

In the title complex, mer‐diaqua[2,6‐dioxo‐1,2,3,6‐tetrahydropyrimidine‐4‐carboxylato(2−)]bis(1H‐imidazole‐κN³)cobalt(II), [Co(C₅H₂N₂O₄)(C₃H₄N₂)₂(H₂O)₂], the Co^II ion is coordinated by a deprotonated N atom and the carboxylate O atom of the orotate ligand, two imidazole N atoms and two aqua ligands in a distorted octahedral geometry. The title complex exists as discrete doubly hydrogen‐bonded dimers, and a three‐dimensional network of O—H...O and N—H...O hydrogen bonds and weak π–π interactions is responsible for crystal stabilization.     

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.     

The protonation of Co(C5Me4Et)(C2H4)2

Reversible protonation of the bis-ethylene complex, Co(C₅Me₄Et)(C₂H₄)₂ yields [Co(C₅Me₄Et)(C₂H₄)₂H][BF₄], which readily exchanges its hydridic and olefinic protons stereospecifically at low temperatures; subsequent protonation at room temperature yields cobalt(III) complexes, C₂H₄ and C₂H₆.     

Diacetatobis(2‐amino­benzothia­zole‐κN)cobalt(II)

The title complex, [Co(C₂H₃O₂)₂(C₇H₆N₂S)₂], contains a Co centre with a slightly distorted tetra­hedral coordination geometry, involving two acetate ligands and two N atoms from the thia­zole moiety [Co—O = 2.0025 (14) and 1.9953 (16) Å, and Co—N = 2.0524 (18) and 2.0568 (18) Å]. The inter­planar angle between the two benzothia­zole moieties is 77.86 (3)°. The amine groups, acting as donors, participate in intra‐ and inter­molecular N—H⋯O hydrogen bonds, with N⋯O distances in the range 2.806 (2)–2.857 (2) Å.     

trans‐Diaquabis(nicotinamide‐κN)bis(salicylato‐κO)cobalt(II)

The title compound, [Co(C₇H₅O₃)₂(C₆H₆N₂O)₂(H₂O)₂], forms a three‐dimensional hydrogen‐bonded supramolecular structure. The Co^II ion is in an octahedral coordination environment comprising two pyridyl N atoms, two carboxylate O atoms and two O atoms from water molecules. Intermolecular N—H...O and O—H...O hydrogen bonds produce R₂²(8), R₂²(12) and R₂²(14) rings, which lead to two‐dimensional chains. An extensive three‐dimensional supramolecular network of C—H...O, N—H...O and O—H...O hydrogen bonds and C—H...π interactions is responsible for crystal structure stabilization. This study is an example of the construction of a supramolecular assembly based on hydrogen bonds in mixed‐ligand metal complexes.     

catena‐Poly[[[N,N′‐bis­(salicyl­idene)propane‐1,3‐diaminato]cobalt(III)]‐μ‐azido] and catena‐poly[[[N,N′‐bis(salicyl­idene)propane‐1,3‐diaminato]cobalt(III)]‐μ‐thio­cyanato]

The two title complexes, catena‐poly[[{2,2′‐[1,3‐propane­diylbis(nitrilo­methyl­idyne)]diphenolato}cobalt(III)]‐μ‐azido], [Co(C₁₇H₁₆N₂O₂)(N₃)]_n, (I), and catena‐poly[[{2,2′‐[1,3‐propane­diylbis(nitrilo­methyl­idyne)]diphenolato}cobalt(III)]‐μ‐thio­cyanato], [Co(C₁₇H₁₆N₂O₂)(NCS)]_n, (II), are isomorphous polynuclear cobalt(III) compounds. In both structures, the Co^III atom is six‐coordinated in an octa­hedral configuration by two N atoms and two O atoms of one Schiff base, and two terminal N or S atoms from two bridging ligands. The [N,N′‐bis­(salicyl­idene)propane‐1,3‐diaminato]cobalt(III) moieties are linked by the bridging ligands, viz. azide in (I) and thio­cyanate in (II), giving zigzag polymeric chains with backbones of the type [–Co—N—N—N—Co]_n in (I) or [–Co—N—C—S—Co]_n in (II) running along the c axis.     

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.     

Derivate des borabenzols: XVI. (Borinato)(cyclobutadien)cobalt-komplexe mit tetramethyl- und tetraphenylcyclobutadien-liganden. Synthese,elektrophile aromatische substitution und ringgliedsubstitution am borinato-liganden

The preparation of (borinato)(cyclobutadiene)cobalt complexes from the reactions of Co(C₅H₅BR)(1,5-C₈H₁₂) with acetylenes C₂R′₂ and of [C₄(CH₃)₄]Co(CO)₂I with Tl(C₅H₅BR) (R,R′ = CH₃, C₆H₅) is described.In electrophilic substitution reactions Co(C₅H₅BCH₃)[C₄(CH₃)₄] (IVa) is more reactive than ferrocene. CF₃CO₂D effects H/D-exchange in the α-position of the borabenzene ring within a few minutes at ambient temperature and in the γ-position within less than four hours Friedel-Crafts acetylation with CH₃COCl/AsCl₃ in CH₂Cl₂ affords the 2-acetyl and the 2,6-diacetyl derivative of IVa. With the more active catalyst AlCl₃, ring-member substitution is effected to give cations [Co(arene)C₄(CH₃)₄]⁺ (arene = C₆H₅CH₃, 2-CH₃C₆H₄COCH₃). Vilsmeier formylation gives the 2-formyl derivative of IVa. The acyl derivatives Co(2-R¹CO-6-R²C₅H₃BCH₃)[C₄(CH₃)₄] (R¹ = CH₃, R² = H, CH₃CO and R¹ = R² = H) transform to the corresponding cations [Co(ortho-R¹R²C₆H₄)C₄(CH₃)₄]⁺ in superacidic media. The mechanistic relationship between acylation and ring-member substitution is discussed in detail.     

Diaquabis(4‐fluorobenzoato‐κO)bis(nicotinamide‐κN)cobalt(II)

The title compound, [Co(C₇H₄FO₂)₂(C₆H₆N₂O)₂(H₂O)₂], is a three‐dimensional hydrogen‐bonded supramolecular complex. The Co^II ion resides on a centre of symmetry and is in an octahedral coordination environment comprising two pyridyl N atoms, two carboxylate O atoms and two O atoms from water molecules. Intermolecular N—H...O and O—H...O hydrogen bonds produce R₃²(6), R₂²(12) and R₂²(16) rings, which lead to two‐dimensional chains. An extensive three‐dimensional network of C—H...F, N—H...O and O—H...O hydrogen bonds and π–π interactions are responsible for crystal stabilization.     

A new trinuclear cobalt(II) complex: deca­aqua-1κ3O,2κ4O,3κ3O-bis­(benzene-1,3,5-tricarboxyl­ato)-1κO,3κO-di-μ-4,4′-bipyridine-1:2κ2N:N′;2:3κ2N:N′-di-4,4′-bipyridine-1κN,3κN-tricobalt(II) 4,4′-bipyridine solvate octa­hydrate

The principal building units in the title compound, [Co₃(C₉H₃O₆)₂(C₁₀H₈N₂)₄(H₂O)₁₀]·C₁₀H₈N₂·8H₂O, are the linear centrosymmetric tricobalt(II) complex mol­ecules resulting from two square-pyramidal [Co(btc)(bpy)(H₂O)₃]⁻ entities (bpy is 4,4′-bipyridine and btc is the benzene-1,3,5-tricarboxyl­ate trianion) bridged by one trans-[Co(bpy)₂(H₂O)₄]²⁺ unit. The trinuclear complex mol­ecules are assembled into infinite chains through inter­molecular O—H⋯N hydrogen bonds and π–π stacking inter­actions between adjacent monodentate bpy ligands. The chains and uncoordinated bpy mol­ecules are further assembled into two-dimensional open layers, which are stacked in a staggered manner to give a three-dimensional supra­molecular architecture with the solvent water mol­ecules in the cavities.     

Clemizoledichlorocobalt(II)

The structure of di­chloro­[1‐(p‐chloro­benzyl)‐2‐(1‐pyrrol­idinyl­methyl‐N)‐1,3‐benz­imidazole‐N³]­cobalt(II), [Co­Cl₂(C₁₉­H₂₀ClN₃)], contains a mol­ecule of clemizole bound in a bidentate manner to cobalt through its imidazole and pyrrolidinyl N atoms, with significantly different Co—N distances of 1.976 (5) and 2.126 (5) Å, respectively. The geometry around cobalt is distorted tetrahedral, with significantly different Co—Cl distances of 2.217 (2) and 2.233 (2) Å, and the pyrrolidinyl ring is disordered.     

Two Fe3(μ3‐S)2(CO)8 clusters with terminal N‐heterocyclic carbenes

The title compounds with terminal N‐heterocyclic carbenes, namely octacarbonyl(imidazolidinylidene‐κC²)di‐μ₃‐sulfido‐triiron(II)(2 Fe—Fe), [Fe₃(C₃H₆N₂)(μ₃‐S)₂(CO)₈], (I), and octacarbonyl(1‐methylimidazo[1,5‐a]pyridin‐3‐ylidene‐κC³)di‐μ₃‐sulfido‐triiron(II)(2 Fe—Fe), [Fe₃(C₈H₈N₂)(μ₃‐S)₂(CO)₈], (II), have been synthesized. Each compound contains two Fe—Fe bonds and two S atoms above and below a triiron triangle. One of the eight carbonyl ligands deviates significantly from linearity. In (I), dimers generated by an N—H...S hydrogen bond are linked into [001] double chains by a second N—H...S hydrogen bond. These chains are packed by a C—H...O hydrogen bond to yield [101] sheets. In (II), dimers generated by an N—H...S hydrogen bond are linked by C—H...O hydrogen bonds to form [111] double chains.     

Hydrogen‐bonded chains in three cis‐dichloridoplatinum(II) complexes bearing piperidine and amine ligands

The crystal structures of cis‐dichlorido(ethylamine‐κN)(piperidine‐κN)platinum(II), [PtCl₂(C₂H₇N)(C₅H₁₁N)], (I), cis‐dichlorido(3‐methoxyaniline‐κN)(piperidine‐κN)platinum(II), [PtCl₂(C₅H₁₁N)(C₇H₉NO)], (II), and cis‐dichlorido(piperidine‐κN)(quinoline‐κN)platinum(II), [PtCl₂(C₅H₁₁N)(C₉H₇N)], (III), have been determined at 100 K in order to verify the influence of the nonpiperidine ligand on the geometry and crystal packing. The crystal packing is characterized by N—H...Cl hydrogen bonding, resulting in the formation of chains of molecules connected in a head‐to‐tail fashion. Hydrogen‐bonding interactions play a major role in the packing of (I), where the chains further aggregate into planes, but less so in the case of (II) and (III), where π–π stacking interactions are of greater importance.