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.     

catena‐Poly[[diaqua­bis(5‐carboxy­pentan­oato‐κO)cobalt(II)]‐μ‐1,2‐di‐4‐pyridylethane‐κ2N:N′]

The title compound, [Co(C₆H₉O₄)₂(C₁₂H₁₂N₂)(H₂O)₂]_n, crystallizes in the space group P. The Co atom is on a center of symmetry and the 1,2‐di‐4‐pyridylethane (bpe) ligand also sits across a crystallographic inversion center. The Co atom is octa­hedrally coordinated by two aqua ligands, two carboxyl­ate O atoms and two pyridyl N atoms, and is bridged by the anti‐bpe ligands to generate one‐dimensional {[Co(Hadip)₂(H₂O)₂](bpe)_2/2} chains (Hadip is 5‐carboxypentanoate), which are further inter­linked by O—H⋯O and C—H⋯O hydrogen bonds into two‐dimensional layers.     

[N‐(2‐Hydroxy­ethyl)ethyl­enediamine‐κ3N,N′,O]‐cis‐bis(isothio­cyanato‐κN)copper(II)

In the novel transition metal isothio­cyanate complex of N‐(2‐hydroxy­ethyl)ethyl­enediamine (hydet‐en) with copper, [Cu(NCS)₂(C₄H₁₂N₂O)], the Cu atom lies in a distorted square‐pyramidal environment, coordinated by four N atoms in the basal plane and an apical O atom. The hydet‐en ligand is N,N,O‐tridentate, in contrast to the disposition in previously studied complexes, while the isothio­cyanate ions act as N‐atom donor ligands. The monomeric units are linked to one another by hydrogen bonds.     

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.     

Poly[[diaquabis[μ2‐2‐(4‐pyridinio)propane‐1,3‐dionato‐κ2O:O′]cobalt(II)] dinitrate]

The title compound, {[Co(C₈H₇NO₂)₂(H₂O)₂](NO₃)₂}_n, is the first d‐metal ion complex involving bidentate bridging of a β‐dialdehyde group. The Co²⁺ ion is situated on an inversion centre and adopts an octahedral coordination with four equatorial aldehyde O atoms [Co—O = 2.0910 (14) and 2.1083 (14) Å] and two axial aqua ligands [Co—O = 2.0631 (13) Å]. The title compound has a two‐dimensional square‐grid framework structure supported by propane‐1,3‐dionate O:O′‐bridges between the metal ions. The organic ligand itself possesses a zwitterionic structure, involving conjugated anionic propane‐1,3‐dionate and cationic pyridinium fragments. Hydrogen bonding between coordinated water molecules, the pyridinium NH group and the nitrate anions [O...O = 2.749 (2) and 2.766 (3) Å, and N...O = 2.864 (3) Å] is essential for the crystal packing.     

trans‐Diaquabis(3‐hydroxybenzoato‐κO1)bis(nicotinamide‐κN1)copper(II)

The title compound, [Cu(C₇H₅O₃)₂(C₆H₆N₂O)₂(H₂O)₂], is a two‐dimensional hydrogen‐bonded supramolecular complex. The Cu^II ion resides on a centre of symmetry and is in an octahedral coordination environment comprising two pyridine 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(4), R₂²(8) and R₂²(15) rings which lead to one‐dimensional polymeric chains. An extensive two‐dimensional network of N—H...O and O—H...O hydrogen bonds and C—H...π interactions are responsible for crystal stabilization.     

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.     

Bis(μ‐diphenyl­phosphinato‐κ2O:O′)bis­[aqua­(diphenyl­phosphinato‐κO)bis­(pyridine‐κN)cobalt(II)]

In the centrosymmetric title compound, [Co₂(C₁₂H₁₀O₂P)₄(C₅H₅N)₄(H₂O)₂], each approximately octa­hedral Co atom features two trans‐coordinated pyridine mol­ecules, one water mol­ecule, a terminally coordinated monodentate diphenyl­phosphinate ligand, and two bidentate diphenyl­phosphinate ligands that bridge the two Co atoms across a centre of inversion to form a dimeric binuclear complex. The discrete mol­ecules are linked by double hydrogen bonds between the terminally coordinated diphenyl­phosphinate ligand and the water mol­ecule to form a continuous chain along the crystallographic b axis.     

Di‐μ‐formato‐1κ2O:2κ2O′‐di‐μ‐pyridin‐2‐olato‐1κO:2κN;1κN:2κO‐bis­[(2‐pyridone‐κO)copper(II)] acetonitrile 1.02‐solvate

In the title compound, [Cu₂(CHO₂)₂(C₅H₄NO)₂(C₅H₅NO)₂]·1.02CH₃CN, the dimeric unit is centrosymmetric, with two bidentate pyridin‐2‐olate and two bidentate formate syn–syn bridges, and two apical 2‐pyridone ligands coordinated through the O atoms. The N atom from the apical 2‐pyridone ligand is a donor of a hydrogen bond to the O atom of the bridging pyridinolate ligand of the same complex. The coordination polyhedron of the Cu atom is a distorted square pyramid.     

catena‐Poly[tris(ethylenediamine‐κ2N,N′)nickel(II) [[trithiocyanato‐κ3N‐sodium(I)]‐μ‐aqua‐κ2O:O]]

The title complex, {[Ni(C₂H₈N₂)₃][Na(NCS)₃(H₂O)]}_n, con­sists of discrete [Ni(en)₃]²⁺ dications (en is ethyl­enedi­amine) and polymeric [(H₂O)_0.5Na(NCS)₃(H₂O)_0.5]_n^2n? anions. The compound crystallizes in space group Pc1. The Ni^II atom lies on a threefold axis and has a distorted octahedral coordination geometry. The Na⁺ cation also lies on a site with imposed crystallographic threefold symmetry and is coordinated by the thio­cyanate N atoms (the thio­cyanates are in general posi­tions), by one water mol­ecule with crystallographically imposed 32 symmetry and by a second water mol­ecule with crystallographically imposed symmetry. The unique Na atom thus has trigonal–bipyramidal coordination. The O atoms of the water mol­ecules bridge the Na⁺ cations to form one‐dimensional polymeric chains in the crystal structure. The [Ni(en)₃]²⁺ dications are distributed around and between the chains and are linked to them via N—H?S hydrogen bonds.     

A new coordination mode of 6‐methylnicotinic acid in trans‐tetraaquabis(6‐methylpyridine‐3‐carboxylato‐κO)cobalt(II) tetrahydrate

The title compound, [Co(C₇H₆NO₂)₂(H₂O)₄]·4H₂O, contains a Co^II ion lying on a crystallographic inversion centre. The Co^II ion is octahedrally coordinated by two 6‐methylpyridine‐3‐carboxylate ligands in axial positions [Co—O = 2.0621 (9) Å] and by four water molecules in the equatorial plane [Co—O = 2.1169 (9) and 2.1223 (11) Å]. There are also four uncoordinated water molecules. The 6‐methylpyridine‐3‐carboxylate ligands are bound to the Co^II ion in a monodentate manner through a carboxylate O atom. There is one strong intramolecular O—H...O hydrogen bond, and six strong intermolecular hydrogen bonds of type O—H...O and one of type O—H...N in the packing, resulting in a complex three‐dimensional supramolecular structure.     

Poly­[[di­aqua­cobalt(II)]‐di‐μ‐4‐cyano­benzoato‐κ4O:O′]

The title compound, [Co(C₈H₄NO₂)₂(H₂O)₂]_n, which was obtained by the reaction of CoCl₂·6H₂O with 4‐cyano­benzoic acid, is the first two‐dimensional 4‐cyano­benzoate cobalt(II) polymer. The Co atom lies on a centre of symmetry and its coordination polyhedron is a slightly distorted octahedron, defined by two water and four carboxyl­ate O atoms. The 4‐cyano­benzoate (cba) anion is bridging in a syn‐skew coordination mode, which ensures a two‐dimensional architecture with the building block Co₄(cba)₄.     

Polymorphism of the dinuclear CoIII–Schiff base complex [Co2(o‐van‐en)3]·4CH3CN (o‐van‐en is a salen‐type ligand)

Reactions of Co(OH)₂ with the Schiff base bis(2‐hydroxy‐3‐methoxybenzylidene)ethylenediamine, denoted H₂(o‐van‐en), under different conditions yielded the previously reported complex aqua[bis(3‐methoxy‐2‐oxidobenzylidene)ethylenediamine]cobalt(II), [Co(C₁₈H₁₈N₂O₄)(H₂O)], 1 , under anaerobic conditions and two polymorphs of [μ‐bis(3‐methoxy‐2‐oxidobenzylidene)ethylenediamine]bis{[bis(3‐methoxy‐2‐oxidobenzylidene)ethylenediamine]cobalt(III)} acetonitrile tetrasolvate, [Co₂(C₁₈H₁₈N₂O₄)₃]·4CH₃CN, i.e. monoclinic 2 and triclinic 3 , in the presence of air. Both novel polymorphs were chemically and spectroscopically characterized. Their crystal structures are built up of centrosymmetric dinuclear [Co₂(o‐van‐en)₃] complex molecules, in which each Co^III atom is coordinated by one tetradentate dianionic o‐van‐en ligand in an uncommon bent fashion. The pseudo‐octahedral coordination of the Co^III atom is completed by one phenolate O and one amidic N atom of the same arm of the bridging o‐van‐en ligand. In addition, the asymmetric units of both polymorphs contain two acetonitrile solvent molecules. The polymorphs differ in the packing orders of the dinuclear [Co₂(o‐van‐en)₃] complex molecules, i.e. alternating ABABAB in 2 and AAA in 3 . In addition, differences in the conformations, the positions of the acetonitrile solvent molecules and the pattern of intermolecular interactions were observed. Hirshfeld surface analysis permits a qualitative inspection of the differences in the intermolecular space in the two polymorphs. A knowledge‐based study employing Full Interaction Maps was used to elucidate possible reasons for the polymorphism.     

A three‐dimensional framework in 2,2′‐biimidazolium bis(2,2′‐biimidazole‐κ2N,N′)bis(biphenyl‐2,4′‐dicarboxylato‐κO)manganese(II) hexahydrate

In the title salt, (C₆H₈N₄)[Mn(C₁₄H₈O₄)₂(C₆H₆N₄)₂]·6H₂O, the Mn^II atom lies on an inversion centre and is coordinated by four N atoms from two 2,2′‐biimidazole (biim) ligands and two O atoms from two biphenyl‐2,4′‐dicarboxylate (bpdc) anions to give a slightly distorted octahedral coordination, while the cation lies about another inversion centre. Adjacent [Mn(bpdc)₂(biim)₂]²⁻ anions are linked via two pairs of N—H...O hydrogen bonds, leading to an infinite chain along the [100] direction. The protonated [H₂biim]²⁺ moiety acts as a charge‐compensating cation and space‐filling structural subunit. It bridges two [Mn(bpdc)₂(biim)₂]²⁻ anions through two pairs of N—H...O hydrogen bonds, constructing two R₂²(9) rings, leading to a zigzag chain in the [2] direction, which gives rise to a ruffled set of [H₂biim]²⁺[Mn(bpdc)₂(biim)₂]²⁻ moieties in the [01] plane. The water molecules give rise to a chain structure in which O—H...O hydrogen bonds generate a chain of alternating four‐ and six‐membered water–oxygen R₄²(8) and R₆⁶(12) rings, each lying about independent inversion centres giving rise to a chain along the [100] direction. Within the water chain, the (H₂O)₆ water rings are hydrogen bonded to two O atoms from two [Mn(bpdc)₂(biim)₂]²⁻ anions, giving rise to a three‐dimensional framework.     

Di‐μ‐hydroxo‐bis­[aqua(1,10‐phenanthroline‐κ2N,N′)copper(II)] trans‐bis(2‐{[(E)‐5‐formyl‐2‐oxido‐κO‐benzyl­idene]­amino‐κN}ethanesulfonato(2–))copper(II) hexahydrate

The title compound, [Cu₂(OH)₂(C₁₂H₈N₂)₂(H₂O)₂][Cu(C₁₀H₉NO₅S)₂]·6H₂O, is comprised of a copper‐centred complex cation and a copper‐centred complex anion; the cation lies about an inversion centre and in the anion the Cu atom lies on an inversion centre. In the doubly charged bridged dicopper cation, each Cu centre has distorted square‐pyramidal geometry. In the square‐planar dianion, two sulfonate ligands are trans coordinated to the Cu atom via a deprotonated hydroxyl O atom and an imine N atom, forming two six‐membered chelate rings. The structure is stabilized by an extensive hydrogen‐bond system and aromatic‐ring stacking interactions.     

Tetraaquabis(2,6‐diamine‐7H‐purine‐κN9)cobalt(II) benzene‐1,2,4,5‐tetracarboxylate tetrahydrate

The title compound, [Co(C₅H₇N₆)₂(H₂O)₄](C₁₀H₂O₈)·4H₂O, is an ionic structure comprising a [Co(Hdap)₂(H₂O)₄]⁴⁺ cation (dap is 2,6‐diaminopurine) in a general position, two benzene‐1,2,4,5‐tetracarboxylate (btc⁴⁻) anions straddling two different inversion centres and four solvent water molecules. The structure presents a remarkable degree of pseudosymmetry, with the Co^II cation lying almost exactly on a noncrystallographic pseudo‐inversion centre. The overall spatial arrangement can be described in terms of cationic and anionic chains running along the [111] direction and linked into a three‐dimensional network by a very complex hydrogen‐bonding scheme in which all the available N—H and O—H groups take part.     

Tetraaqua‐1κO,2κ3O‐(μ‐2,4‐dinitrophenolato‐1κ2O1,O2:2κO1)(2,4‐dinitrophenolato‐1κ2O1,O2)dilithium(I): a dinuclear lithium(I) complex

The title complex, [Li₂(C₆H₃N₂O₅)₂(H₂O)₄], contains two kinds of Li atoms, viz. five‐coordinated and four‐coordinated. The five‐coordinated Li ion has a tetragonal–pyramidal geometry, with a water molecule in the apical position and four O atoms from two 2,4‐dinitrophenolate (2,4‐DNP) ligands in the basal plane. The four‐coordinated Li ion has a tetrahedral geometry, with three water molecules and one phenolate O atom of a 2,4‐DNP ligand. The Li ions are bridged by a phenolate O atom, giving the complex a dinuclear structure. The crystal packing is stabilized by O—H...O hydrogen‐bonding interactions involving the water molecules and nitro O atoms.     

catena‐Poly[[[aqua[3‐(2‐pyridylsulfanyl)propionato N‐oxide‐κO1]copper(II)]‐μ‐[3‐(2‐pyridylsulfanyl)propionato N‐oxide‐κ3O3:O1,O1′] dihydrate]

In the title complex, {[Cu(C₈H₈NO₃S)₂(H₂O)]·2H₂O}_n, the Cu^II cation has a distorted square‐pyramidal coordination environment consisting of five O atoms, one from a water molecule, one from an N—O group and the other three from the carboxylate groups of two 3‐(2‐pyridylsulfanyl)propionate N‐oxide anions. The aqua[3‐(2‐pyridylsulfanyl)propionato N‐oxide]copper(II) moieties are bridged by 3‐(2‐pyridylsulfanyl)propionate N‐oxide anions to form an infinite three‐dimensional coordination polymer with a zigzag chain structure. The crystal structure is stabilized by hydrogen bonds.     

Two isomorphous ZnII/CoII complexes with tri‐tert‐butoxysilanethiol and histamine,and (4‐hydroxymethyl‐1H‐imidazole‐κN)bis(tri‐tert‐butoxysilanethiolato‐κ2O,S)zinc(II)

The complexes [2‐(1H‐imidazol‐4‐yl‐κN³)ethylamine‐κN]bis(tri‐tert‐butoxysilanethiolato‐κS)cobalt(II), [Co(C₁₂H₂₇O₃SSi)₂(C₅H₉N₃)], and [2‐(1H‐imidazol‐4‐yl‐κN³)ethylamine‐κN]bis(tri‐tert‐butoxysilanethiolato‐κS)zinc(II), [Zn(C₁₂H₂₇O₃SSi)₂(C₅H₉N₃)], are isomorphous. The central Zn^II/Co^II ions are surrounded by two S atoms from the tri‐tert‐butoxysilanethiolate ligand and by two N atoms from the chelating histamine ligand in a distorted tetrahedral geometry, with two intramolecular N—H...O hydrogen‐bonding interactions between the histamine NH₂ groups and tert‐butoxy O atoms. Molecules of the complexes are joined into dimers via two intermolecular bifurcated N—H...(S,O) hydrogen bonds. The Zn^II atom in [(1H‐imidazol‐4‐yl‐κN³)methanol]bis(tri‐tert‐butoxysilanethiolato‐κ²O,S)zinc(II), [Zn(C₁₂H₂₇O₃SSi)₂(C₄H₆N₂O)], is five‐coordinated by two O and two S atoms from the O,S‐chelating silanethiolate ligand and by one N atom from (1H‐imidazol‐4‐yl)methanol; the hydroxy group forms an intramolecular hydrogen bond with sulfur. Molecules of this complex pack as zigzag chains linked by N—H...O hydrogen bonds. These structures provide reference details for cysteine‐ and histidine‐ligated metal centers in proteins.     

Two two‐dimensional hydrogen‐bonded coordination networks: bis(3‐carboxybenzoato‐κO)bis(4‐methyl‐1H‐imidazole‐κN3)copper(II) and bis(3‐methylbenzoato‐κN)bis(4‐methyl‐1H‐imidazole‐κN3)copper(II) monohydrate

The title two‐dimensional hydrogen‐bonded coordination compounds, [Cu(C₈H₅O₄)₂(C₄H₆N₂)₂], (I), and [Cu(C₈H₇O₂)₂(C₄H₆N₂)₂]·H₂O, (II), have been synthesized and structurally characterized. The molecule of complex (I) lies across an inversion centre, and the Cu²⁺ ion is coordinated by two N atoms from two 4‐methyl‐1H‐imidazole (4‐MeIM) molecules and two O atoms from two 3‐carboxybenzoate (HBDC⁻) anions in a square‐planar geometry. Adjacent molecules are linked through intermolecular N—H...O and O—H...O hydrogen bonds into a two‐dimensional sheet with (4,4) topology. In the asymmetric part of the unit cell of (II) there are two symmetry‐independent molecules, in which each Cu²⁺ ion is also coordinated by two N atoms from two 4‐MeIM molecules and two O atoms from two 3‐methylbenzoate (3‐MeBC⁻) anions in a square‐planar coordination. Two neutral complex molecules are held together via N—H...O(carboxylate) hydrogen bonds to generate a dimeric pair, which is further linked via discrete water molecules into a two‐dimensional network with the Schläfli symbol (4³)₂(4⁶,6⁶,8³). In both compounds, as well as the strong intermolecular hydrogen bonds, π–π interactions also stabilize the crystal stacking.