Bis(2‐amino­pyridine‐κN1)(benzoato‐κO)silver(I)

In the title compound, [Ag(C₇H₅O₂)(C₅H₆N₂)₂], the Ag^I atom is tricoordinated by two independent pyridine N atoms and one benzoate O atom in a nearly planar geometry. An intramolecular N—H⃛O hydrogen bond forms an S(8) graph ring. The packing is built from molecular layers stabilized by two types of N—H⃛O hydrogen bond. Intermolecular Ag⃛N and intramolecular Ag⃛O contacts were also observed, together with three weak intermolecular C—H⃛π interactions.     

catena‐Poly­[[(benzoato‐κO)silver(I)]‐μ‐2‐amino­pyrimidine‐κ2N1:N3]

The title complex, [Ag(C₇H₅O₂)(C₄H₅N₃)]_n, is a polymer based on a mononuclear silver(I)‐centered fragment. The Ag^I atom is trigonally coordinated by two N atoms from two 2‐­amino­pyrimidine ligands and one O atom from one benzoate anion, giving zigzag polymeric chains with an [–Ag—N—C—N–]_n backbone running along the a axis. It is proposed that intermolecular hydrogen bonding drives the formation of the chain polymer.     

Di‐μ‐acesulfamato‐κ3N,O:O;κ3O:N,O‐bis[(acesulfamato‐κ2N,O)bis(3‐methylpyridine)cadmium(II)]

In the structure of the title compound, [Cd₂(C₄H₄NO₄S)₂(C₆H₇N)₂], the dinuclear Cd^II complex is located on a twofold axis with two Cd²⁺ ions bridged by two oxide O atoms. Each Cd²⁺ ion is additionally coordinated in an equatorial plane by two N and three O atoms of the acesulfamate ligands and axially by two N atoms of the 3‐methylpyridine ligands, resulting in a distorted pentagonal bipyramidal coordination. We present here an example of a supramolecular assembly based on hydrogen bonds in a mixed‐ligand metal complex; intermolecular C—H...O hydrogen bonds give rise to R₄⁴(40) rings, which lead to one‐dimensional chains.     

Two novel silver(I) coordination polymers: poly[(μ2‐2‐aminopyrimidine‐κ2N1:N3)bis(μ3‐thiocyanato‐κ3S:S:S)disilver(I)] and poly[(2‐amino‐4,6‐dimethylpyrimidine‐κN)(μ3‐thiocyanato‐κ3N:S:S)silver(I)]

2‐Aminopyrimidine (L1) and 2‐amino‐4,6‐dimethylpyrimidine (L2) have been used to create the two novel title complexes, [Ag₂(NCS)₂(C₄H₅N₃)]_n, (I), and [Ag(NCS)(C₆H₉N₃)]_n, (II). The structures of complexes (I) and (II) are mainly directed by the steric properties of the ligands. In (I), the L1 ligand is bisected by a twofold rotation axis running through the amine N atom and opposite C atoms of the pyrimidine ring. The thiocyanate anion adopts the rare μ₃‐κ³S coordination mode to link three tetrahedrally coordinated Ag^I ions into a two‐dimensional honeycomb‐like 6³ net. The L1 ligands further extend the two‐dimensional sheet to form a three‐dimensional framework by bridging Ag^I ions in adjacent layers. In (II), with three formula units in the asymmetric unit, the L2 ligand bonds to a single Ag^I ion in a monodentate fashion, while the thiocyanate anions adopt a μ₃‐κ¹N,κ²S coordination mode to link the AgL2 subunits to form two‐dimensional sheets. These layers are linked by N—H...N hydrogen bonds between the noncoordinated amino H atoms and both thiocyanate and pyrimidine N atoms.     

Tetrakis(μ‐benzoato‐κ2O:O)bis{[4‐(dimethylamino)pyridine‐κN1]copper(II)}

The title compound, [Cu₂(C₇H₅O₂)₄(C₇H₁₀N₂)₂], is a crystallographically centrosymmetric binuclear complex, with Cu atoms [Cu...Cu = 2.6982 (4) Å] bridged by four benzoate ligands. Each of the Cu atoms in this bunuclear copper(II) acetate hydrate analogue is present in an approximately square‐pyramidal environment, with four O atoms in a plane and the pyridine N atom at the apical site. Selected geometric parameters are compared with values for related tetrabenzoate complexes of copper(II).     

Poly[[μ3‐2‐(carboxylatomethyl)benzoato‐κ3O1:O2:O2]bis(1H‐imidazole‐κN3)copper(II)]

In the title polymeric compound, [Cu(C₉H₆O₄)(C₃H₄N₂)₂]_n, the copper(II) cation occupies an N₂O₃ coordination sphere defined by two 1H‐imidazole (imid) ligands in trans positions and three carboxylate O atoms from three different 2‐(carboxylatomethyl)benzoate (hpt²⁻) dianions. The geometry is that of a square pyramid with one of the O atoms at the apex, bridging neighbouring metal centres into an [–ON₂CuO₂CuN₂O–] dinuclear unit. These units are in turn connected by hpt anions into a reticular mesh topologically characterized by two types of loops, viz. a four‐membered Cu₂O₂ diamond motif and a 32‐membered Cu₄O₈C₂₀ ring. The imid groups do not take part in the formation of the two‐dimensional structure, but take part in the N—H...O interactions. These arise only within individual planes, interplanar interactions being only of the van der Waals type.     

Tetra‐μ‐acetato‐κ2O:O′‐bis[(4‐phenylpyridine‐κN)copper(II)]

The title compound, [Cu₂(C₂H₃O₂)₄(C₁₁H₉N)₂] or [Cu₂(MeCO₂)₄(phpy)₂] (phpy is 4‐phenyl­pyridine), consists of centrosymmetric dimers in which the Cu^II atoms display a square‐pyramidal CuO₄N coordination, with four acetate O atoms in the basal plane [Cu—O 1.975 (3)–1.987 (3) Å] and the phpy N atom in the apical position [Cu—N 2.150 (3) Å]. The Cu atoms are 2.654 (1) Å apart and are bridged by four acetate groups. The discrete dimers are extended into a three‐dimensional supramolecular array through intermolecular π–π‐stacking interactions.     

catena‐Poly[[silver(I)‐μ‐[9,10‐bis(1H‐benzimidazol‐1‐ylmethyl)anthracene]‐κ2N3:N3′] bis(nitrato‐κO)silver(I)]

Yellow needle‐shaped crystals of the title compound, {[Ag(C₃₀H₂₂N₄)][Ag(NO₃)₂]}_n, were obtained by the reaction of AgNO₃ and 9,10‐bis(benzimidazol‐1‐ylmethyl)anthracene (L) in a 2:1 ratio. The asymmetric unit consists of two Ag^I cations, one half L ligand and one nitrate anion. One Ag^I cation occupies a crystallographic inversion centre and links two N‐atom donors of two distinct L ligands to form an infinite one‐dimensional coordination polymer. The second Ag^I cation lies on a crystallographic twofold axis and is coordinated by two O‐atom donors of two nitrate anions to form an [Ag(NO₃)₂]⁻ counter‐ion. The polymeric chains are linked into a supramolecular framework via weak Ag...O [3.124 (5) Å] and Ag...π (2.982 Å) interactions (π is the centroid of an outer anthracene benzene ring). The π interactions contain two short Ag...C contacts [2.727 (6) and 2.765 (6) Å], which can be considered to define Ag–η²‐anthracene bonding interactions. In comparison with a previously reported binuclear Ag^I complex [Du, Hu, Zhang, Zeng & Bu (2008). CrystEngComm, 10 , 1866–1874], this new one‐dimensional coordination polymer was obtained by changing the metal–ligand ratio during the synthesis.     

μ2‐Acetato‐κ2O:O′‐tris(μ2‐ferrocenecarboxylato‐κ2O:O′)bis[(N,N‐dimethylformamide‐κO)copper(II)]

The title compound, [Cu₂Fe₃(C₅H₅)₃(C₂H₃O₂)(C₆H₄O₂)₃(C₃H₇NO)₂], belongs to the classic dimeric paddle‐wheel structure type. It is an unusual example in that it contains two different carboxylate groups, viz. ferrocenecarboxylate and acetate. With three ferrocenecarboxylate groups and only one acetate group bridging the two Cu centres, a noncentrosymmetric molecular arrangement results.     

The coordination polymer poly[(μ3‐3‐aminocarbonylpyrazine‐2‐carboxylato‐κ3N1:O2:O2′)silver(I)]

The title compound, [Ag(C₆H₄N₃O₃)]_n or [Ag(pyzca)]_n (where pyzca is 3‐aminocarbonylpyrazine‐2‐carboxylate), (I), was obtained by silver‐catalysed partial hydrolysis of pyrazine‐2,3‐dicarbonitrile in aqueous solution. The compound has a distorted trigonal–planar coordination geometry around the Ag^I ion, with each ligand bridging three Ag^I ions to form a one‐dimensional strand of molecules parallel to the b axis. An extensive hydrogen‐bond pattern connects these strands to form a three‐dimensional network of mog topology.     

Poly[bis[μ2‐3‐(pyridin‐4‐yl)benzoato‐κ3N:O,O′]lead(II)]

In the title compound, [Pb(C₁₂H₈NO₂)₂]_n, the Pb atom sits on a crystallographic C₂ axis and is six‐coordinate, ligated by two chelating carboxylate groups from two 3‐(pyridin‐4‐yl)benzoate (L) ligands and by two N atoms from another two ligands. Each ligand bridges two Pb^II centres, extending the structure into a corrugated two‐dimensional (4,4) net. The ligand L is conformationally chiral, with a torsion angle of 27.9 (12)° between the planes of its two rings. The torsion angle has the same sense throughout the structure, so that the extended two‐dimensional polymer is homochiral. Investigation of the thermal stability shows that the network is stable up to 613 K. In the absence of any stereoselective factor in the preparation of the compound, the enantiomeric purity of the crystal studied, based only on the torsional conformation of the ligand, implies that the bulk sample is a racemic conglomerate.     

A novel dinuclear bismuth(III) coordination compound: bis(μ‐pyridine‐2,6‐dicarboxylato)‐κ4O2,N,O6:O6′;κ4O2:O2′,N,O6‐bis[(azido‐κN)(1,10‐phenanthroline‐κ2N,N′)bismuth(III)] tetrahydrate

A novel dinuclear bismuth(III) coordination compound, [Bi₂(C₇H₃NO₄)₂(N₃)₂(C₁₂H₈N₂)₂]·4H₂O, has been synthesized by an ionothermal method and characterized by elemental analysis, energy‐dispersive X‐ray spectroscopy, IR, X‐ray photoelectron spectroscopy and single‐crystal X‐ray diffraction. The molecular structure consists of one centrosymmetric dinuclear neutral fragment and four water molecules. Within the dinuclear fragment, each Bi^III centre is seven‐coordinated by three O atoms and four N atoms. The coordination geometry of each Bi^III atom is distorted pentagonal–bipyramidal (BiO₃N₄), with one azide N atom and one bridging carboxylate O atom located in axial positions. The carboxylate O atoms and water molecules are assembled via O—H...O hydrogen bonds, resulting in the formation of a three‐dimensional supramolecular structure. Two types of π–π stacking interactions are found, with centroid‐to‐centroid distances of 3.461 (4) and 3.641 (4) Å.     

Poly[(μ2‐aqua‐κ2O:O)(μ3‐azido‐κ3N1:N1:N3)(μ2‐isonicotinato‐κ2O:O′)lead(II)]

In the title compound, [Pb(C₆H₄NO₂)(N₃)(H₂O)]_n, the Pb ion is seven‐coordinated by three N atoms from three azide ligands, two O atoms from two isonicotinate (inic) ligands and two O atoms from two coordinated water molecules, forming a distorted monocapped triangular prismatic coordination geometry. Each azide ligand bridges three Pb^II ions in a μ_1,1,3 coordination mode to form a two‐dimensional three‐connected 6³ topology network extending in the bc plane. The carboxylate group of the inic unit and the aqua ligand act as coligands to bridge Pb^II ions. Adjacent two‐dimensional layers are connected by hydrogen‐bonding interactions between the isonicotinate N atom and the water molecule, resulting in an extended three‐dimensional network. The title complex is the first reported coordination polymer involving a p‐block metal, an azide and a carboxylate.     

Bis[(μ‐cyclopentylamino‐N:N)dimethyl­aluminium(III)]

Reaction of AlMe₃ with NH₂(C₅H₉) caused the evolution of methane and produced the dimeric species bis(μ‐cyclo­pentyl­amino‐N:N)bis[dimethylaluminium(III)], [Al(CH₃)₂‐(C₅H₁₀N)]₂, which was found to adopt a cis configuration of cyclopentyl groups about a bent AlNAlN ring (which has twofold crystallographic symmetry) instead of the more common trans arrangement.     

catena‐Poly[[bis(acetonitrile‐κN)manganese(II)]‐bis(μ‐trifluoromethanesulfonato‐κ2O:O′)]

The title compound, [Mn(CF₃SO₃)₂(CH₃CN)₂]_n, has an Mn^II cation on an inversion centre in an octahedral environment. The trifluoromethanesulfonate anions act as bridging ligands and form a one‐dimensional coordination polymer in the direction of the a axis. The F atoms of the trifluoromethanesulfonate anions form layers parallel to the ab plane, but despite short intermolecular distances, no stabilizing F...F interactions are detected. The Mn—N and C—C bonds of the acetonitrile ligand are analyzed according to the Hirshfeld rigid‐bond test. Renninger effects in the reflection data are considered, explored and discussed.     

Bis(2‐amino‐2‐thiazolinium) tetra‐μ‐formato‐κ8O:O′‐bis[(formato‐κO)copper(II)]

In the title dimeric compound, (C₃H₇N₂S)₂[Cu₂(CHO₂)₆], each Cu^II atom has a square‐pyramidal coordination, with the nonbridging formate ion at the apical position. The complex anion is located on a crystallographic inversion centre, with a Cu...Cu separation of 2.6566 (4) Å. 2‐Amino‐2‐thiazolinium cations connect complex anions via hydrogen bonds to form a ribbon running along the a axis.     

Bis[μ‐1,2‐bis(2‐pyridyl)ethyne‐κ2N:N′]bis[aquadinitratocadmium(II)]

Two twisted 1,2‐bis(2‐pyridyl)­ethyne ligands bridge two Cd²⁺ centers in the C₂‐symmetric title complex, [Cd₂(NO₃)₄(μ‐C₁₂H₈N₂)₂(H₂O)₂]. The bridging ligands arch across one another creating a `zigzag loop' molecular geometry. Two nitrate ions and a water mol­ecule complete the irregular seven‐coordinate Cd‐atom environment. The dihedral angles between the equivalent pyridyl ring planes of the two independent ligands are 67.2 (1)°. O_water—H⃛O_nitrate hydrogen bonding creates two‐dimensional layers parallel to the ab plane.     

Bis[μ‐4‐(ethylammoniomethyl)‐3,5‐dimethylpyrazolato‐κ2N1:N2]bis[(η4‐1,5‐cyclooctadiene)rhodium(I)] dichloride dichloromethane methanol solvate

In the title compound, [Rh₂(C₈H₁₅N₃)₂(C₈H₁₂)₂]Cl₂·CH₂Cl₂·CH₃OH, the dinuclear Rh^I complex has C₂ symmetry and the two pyrazolato ligands act as μ‐bridges. The coordination of each Rh^I cation is completed by one cyclo­octa­diene (COD) ligand. It is shown that the average Rh—C(COD) distance is linearly dependent on the Rh—N(pyrazole) distance in this type of compound, and this is ascribed to the steric hindrance produced by the packing.     

catena‐Poly[[[(iminodiacetato‐κO)silver(I)]‐μ3‐2‐aminopyrimidine‐κ3N1:N2:N3] monohydrate]: a one‐dimensional silver(I) coordination polymer with mixed ligands

The title compound, {[Ag(C₄H₆NO₄)(C₄H₅N₃)]·H₂O}_n, was synthesized by the reaction of silver(I) nitrate with 2‐aminopyrimidine and iminodiacetic acid. X‐ray analysis reveals that the crystal structure contains a one‐dimensional ladder‐like Ag^I coordination polymer and that N—H...O and O—H...O hydrogen bonding results in a three‐dimensional network. The Ag^I centre is four‐coordinated by three N atoms from three different 2‐aminopyrimidine ligands and one O atom from one iminodiacetate ligand. Comparison of the structural features with previous findings suggests that the existence of a second ligand plays an important role in the construction of such polymer frameworks.