catena‐Poly[[bis(nicotinamide‐κN1)copper(I)]‐μ‐thiocyanato‐κ2N:S]

The Cu^I cations in the title compound, [Cu(NCS)(C₆H₆N₂O)₂]_n, are coordinated by N atoms from each of two mirror‐related nicotin­amide ligands, as well as by one N atom of one thio­cyanate ligand and one S atom of a symmetry‐related thio­cyanate ligand, within a slightly distorted tetrahedron. The Cu^I cations and the thio­cyanate anions are located on a crystallographic mirror plane and the nicotin­amide ligands occupy general positions. The Cu^I cations are connected by the thio­cyanate anions to form chains in the direction of the crystallographic a axis. These chains are connected by hydrogen bonds between the amide H atoms and the O atoms of adjacent nicotin­amide ligands, to give a three‐dimensional structure.     

catena‐Poly[[bis[pentaaquaerbium(III)]‐μ‐benzenehexacarboxylato] tetrahydrate]

The title compound is composed of one‐dimensional polymeric {[Er₂(C₁₂O₁₂)(H₂O)₁₀]·4H₂O}_n chains containing Er in a slightly distorted antiprismatic eightfold coordination. The benzene­hexa­carboxyl­ate ion is located about an inversion centre. Water mol­ecules of crystallization, linked by hydrogen bonding to water mol­ecules of the rare earth coordination spheres or the carboxyl­ate groups of the organic ligands, fill the space generated by the packing of the separated chains.     

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.     

catena‐Poly­[[bis­(thio­cyanato‐κN)cadmium(II)]‐di‐μ‐thio­urea‐κ4S:S]

The Cd^II ion in the title complex, [Cd(SCN)₂{SC(NH₂)₂}₂]_∞, is situated at a centre of symmetry, and is bound to two N atoms belonging to thio­cyanate groups and to four S atoms of bridging thio­urea ligands. The structure consists of infinite chains of slightly distorted edge‐shared Cd‐centred octahedra. The bridging S atoms of two thio­urea ligands comprise the common edge. Some thermal properties are described.     

catena‐Poly[[di‐μ‐chloro‐bis[(triphenylphosphine)silver(I)]]‐μ‐2‐aminopyrimidine‐κ2N1:N3]

In the title supramolecular complex, [Ag₂Cl₂(C₄H₅N₃)(C₁₈H₁₅P)₂]_n, a one‐dimensional chain is formed by dimeric {Ag₂Cl₂(PPh₃)₂} units bridged by 2‐amino­pyrimidine moieties. The Ag atoms are four‐coordinate, with an AgCl₂NP core. A crystallographic inversion centre is located in the centre of the Ag₂Cl₂ chelate ring, while the crystallographic twofold axis bisects the 2‐amino­pyrimidine ligand.     

catena‐Poly[[diaquamanganese(II)]‐di‐μ‐1,1,3,3‐tetracyano‐2‐ethoxypropenido‐κ4N1:N3]

The crystal structure of the title compound, [Mn(C₉H₅N₄O)₂(H₂O)₂], conventionally denoted Mn(EtO‐TCA)₂(H₂O)₂, where EtO‐TCA is 2‐ethoxy‐1,1,3,3‐tetra­cyano­propenide, is described. The EtO‐TCA anions bridge Mn^II centers through one of the nitrile N atoms of each of their two di­cyano­methanide groups, thus forming dibridged chains along ab. These chains are linked into two‐dimensional sheets through hydrogen bonding. The seven‐atom bridge, which results in a long Mn⃛Mn intrachain interaction [9.0044 (4) Å], as well as the large interchain separations [8.3288 (4) and 8.5220 (4) Å] prohibit long‐range magnetic ordering down to temperatures as low as 1.55 K.     

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.     

catena‐Poly[[bis(cis‐1‐tert‐butyltetrazole‐κN4)copper(II)]‐di‐μ‐chloro]

The title polymeric compound, [CuCl₂(C₅H₁₀N₄)₂]_n, is the first structurally characterized complex with a bulky 1‐alkyl­tetrazole ligand. The coordination polyhedron of the Cu atom is an elongated octahedron. The equatorial positions of the octahedron are occupied by the two Cl atoms, with Cu—Cl distances of 2.2920 (8) and 2.2796 (9) Å, and by the two N‐4 atoms of the tetrazole ligands, with Cu—N distances of 2.023 (2) and 2.039 (2) Å. Two symmetry‐related Cl atoms occupy the axial positions, at distances of 2.8244 (8) and 3.0174 (8) Å from the Cu atom. The [CuCl₂(C₅H₁₀N₄)₂] units form infinite chains extended along the b axis, linked together only by van der Waals interactions. The skeleton of each chain consists of Cu and Cl atoms.     

catena‐Poly[[aqua­bis(1H‐benzimidazole‐κN3)manganese(II)]‐μ‐adipato]

In the title polymeric complex, [Mn(C₆H₈O₄)(C₇H₆N₂)₂(H₂O)]_n, the Mn^II atom is surrounded by two adipate dianions, two benzimidazole mol­ecules and one coordinated water mol­ecule. The Mn atoms and coordinated water mol­ecule are located on a twofold axis, and the bridging adipate ligand is located on an inversion center. The adipate dianions bridge neighboring Mn^II atoms to form polymeric chains. Each Mn^II atom is seven‐coordinate, the longest Mn—O bond length being 2.5356 (16) Å.     

catena‐Poly[[bis(μ‐2‐sulfonatobenzoato)bis[triaquagadolinium(III)]]‐μ‐oxalato]

The asymmetric unit of the title coordination polymer, [Gd₂(C₇H₄O₅S)₂(C₂O₄)(H₂O)₆]_n or [Gd(2‐SB)(ox)_0.5(H₂O)₃]_2n (2‐SB is 2‐sulfonatobenzoate and ox is oxalate), (I), consists of one Gd^III ion, one 2‐SB anion, three coordinated water molecules and one half of an ox ligand. The ox ligand is located on a crystallographic inversion centre. The Gd^III centre shows a distorted tricapped trigonal–prismatic coordination formed by nine O atoms from two 2‐SB anions, one ox ligand and three coordinated water molecules. The carboxylate and sulfonate groups of the 2‐SB anions adopt μ₂‐η¹:η² and μ₁‐η⁰:η⁰:η¹ coordination modes to link two Gd^III ions, generating a centrosymmetric binuclear [Gd₂(2‐SB)₂(H₂O)₆]²⁻ subunit. The ox ligand acts as a bridge, linking the binuclear [Gd₂(2‐SB)₂(H₂O)₆]²⁻ subunits into a one‐dimensional chain structure parallel to the b axis. Furthermore, extensive O—H...O hydrogen bonds connect the chains into a three‐dimensional supramolecular architecture.     

An unusual chain cadmium(II) coordination polymer: catena‐poly[[(2,2′‐bipyridyl‐κ2N,N′)cadmium(II)]‐di‐μ‐chlorido‐[(2,2′‐bipyridyl‐κ2N,N′)cadmium(II)]‐di‐μ‐thiocyanato‐κ2N:S;κ2S:N]

The title complex, [CdCl(NCS)(C₁₀H₈N₂)]_n, represents an unusual Cd^II coordination polymer constructed by two types of anionic bridges and 2,2′‐bipyridyl (bipy) terminal ligands. These two types of bridges are arranged around inversion centers. The distorted octahedral coordination of the Cd^II center is provided by two chloride ions, one N‐ and one S‐donor atom from two thiocyanate ions, and a pair of N atoms from the chelating bipy ligand. Interestingly, adjacent Cd^II ions are interconnected alternately by paired chloride [Cd...Cd = 3.916 (1) Å] and thiocyanate bridges [Cd...Cd = 5.936 (1) Å] to generate an infinite one‐dimensional coordination chain. Furthermore, weak interchain C—H...S interactions between the bipy components and thiocyanate ions lead to the formation of a layered supramolecular structure.     

catena‐Poly[[bis[aqua­(1,10‐phenanthroline)lead(II)]‐di‐μ3‐5‐carboxy‐3‐sulfonatobenzoato] dihydrate]

In the centrosymmetric title polymer, catena‐poly[[bis[aqua­(1,10‐phenanthroline‐κ²N,N′)lead(II)]‐di‐μ₃‐5‐carboxy‐3‐sulfonatobenzoato‐1:2:1′κ⁴O³:O¹,O^1′:O¹;2′:1:2κ⁴O¹:O¹,O^1′:O³] dihydrate], {[Pb(C₈H₄O₇S)(C₁₂H₈N₂)(H₂O)]·H₂O}_n, each seven‐coordinate lead(II) ion is bound by five O atoms from one water molecule and three 5‐sulfoisophthalate (sip) anions, and by two N atoms from a 1,10‐phenanthroline (phen) ligand. The sip sulfonate group is monodentate. One O atom of the sip carboxyl­ate group is chelated to one Pb²⁺ cation, with the other also bridging an adjacent Pb²⁺ cation. The carboxyl group is uncoordinated. This unusual coordination results in a chain structure along the b axis, which is linked by strong intermolecular hydrogen bonds into a three‐dimensional network.     

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.     

catena‐Poly[[dinitratocadmium(II)]bis[μ‐bis(2‐methyl‐1H‐imidazol‐1‐yl)methane‐κ2N3:N3′]]

The title compound, [Cd(NO₃)₂(C₉H₁₂N₄)₂]_n, has a one‐dimensional double‐bridged chain polymer structure with a 16‐membered macrometallacyclic tetragonal structural motif. The Cd^II ion occupies a crystallographic inversion centre and is coordinated by four equatorial N atoms from four distinct bis(2‐methylimidazol‐1‐yl)methane ligands and two apical nitrate O atoms to form a slightly distorted octahedral coordination geometry.     

catena‐Poly[[aqua­(3,4,7,8‐tetra­methyl‐1,10‐phenanthroline‐κ2N,N′)cadmium(II)]‐μ3‐thio­sulfato‐κ3S:S:O]

The title compound, [Cd(S₂O₃)(C₁₆H₁₆N₂)(H₂O)]_n, presents a polymeric one‐dimensional structure running along the P2₁/c glide direction, with elementary units defined by six‐coordinate Cd^II atoms bonded to three symmetry‐related thio­sulfate groups, a bidentate tetra­methyl­phenanthroline ligand and one aqua ligand. The bridging thio­sulfates bind metal centers through two different sequences, viz. Cd—S—Cd′ and Cd′—S′—S′—O′—Cd, defining a closed six‐membered ring. Individual chains are held together viaπ–π inter­actions to generate two‐dimensional networks parallel to the (100) plane. These, in turn, are connected by much weaker van der Waals inter­actions.     

Poly[[bis(dimethyl sulfoxide‐κO)tris(thiocyanato‐κN)­manganese(II)]‐μ‐thio­cyanato‐κ2N:S‐mercury(II)]

In the title complex, [MnHg(SCN)₄(C₂H₆SO)₂]_n, each Hg atom is tetrahedrally coordinated to four S atoms of the SCN ions, while each Mn atom is octahedrally coordinated to four N atoms of the SCN ions and two O atoms of the di­methyl sulfoxide mol­ecules which occupy the trans positions. Each pair of Hg and Mn atoms is bridged by one SCN ion. Two Mn atoms, two Hg atoms and four SCN ions make a 16‐membered ring which organises into a two‐dimensional network. The di­methyl sulfoxide ligands are extended perpendicular to the plane on both sides.     

Poly[[aquabis(μ2‐isonicotinato‐κ3N:O,O′)cadmium(II)] 1,4‐di‐3‐pyridyl‐2,3‐diaza‐1,3‐butadiene hemisolvate]

The title compound, {[Cd(C₆H₄NO₂)₂(H₂O)]·0.5C₁₂H₁₀N₄}_n, presents an intricate three‐dimensional network with cavities traversing it in three orthogonal directions, where the (disordered) guest molecules lodge. The compound is a member of a series of coordination polymers presenting the same main host framework but with guests of variable size and geometry, to which the flexible skeleton seems to adapt. The disorder in the structure is explained in terms of an apparently well defined specificity in the position/orientation of the guest molecules, as determined by the main framework.     

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.     

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.     

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.