catena‐Poly[[(1,10‐phenanthroline‐κ2N,N′)manganese(II)]‐di‐μ‐salicylato‐κ4O:O′]

In the title polymeric complex, [Mn(C₇H₅O₃)₂(C₁₂H₈N₂)]_n, the Mn^II atom is located on a twofold axis and displays a distorted octa­hedral coordination geometry, formed by four salicylate anions and one 1,10‐phenanthroline (phen) mol­ecule. The salicylate anions doubly bridge the Mn^II atoms to form one‐dimensional polymeric chains. A comparison of Mn—O bond distances with the corresponding Mn—O—C angles suggests a significant electrostatic content in the Mn—O bonds. A face‐to‐face distance of 3.352 (7) Å between neighbouring parallel phen planes indicates π–π stacking inter­actions between polymeric chains.     

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.     

catena‐Poly[[nickel(II)‐μ2‐[1,3‐bis(imidazol‐1‐ylmethyl)benzene‐κ2N3:N3′]‐μ2‐(5‐carboxybenzene‐1,3‐dicarboxylato‐κ4O1,O1′:O3,O3′)] 0.41‐hydrate]

The title compound, {[Ni(C₉H₄O₆)(C₁₄H₁₄N₄)]·0.41H₂O}_n, exhibits a three‐dimensional hydrogen‐bonded supramolecular framework. The Ni^II cation is six‐coordinated in a distorted triangular prism defined by two N atoms from two 1,3‐bis(imidazol‐l‐ylmethyl)benzene (bix) ligands and four O atoms from two 5‐carboxybenzene‐1,3‐dicarboxylate (HBTC) dianions. The bix molecules and HBTC dianions both act as bidentate ligands, linking the Ni^II cations to form a one‐dimensional coordination polymer. A two‐dimensional wave‐like net is constructed by O—H...O hydrogen bonds linking adjacent chains. Partially occupied solvent water molecules fill the cavities and link these layers to form a three‐dimensional supramolecular structure via O—H...O hydrogen bonds. The title compound was also characterized by powder X‐ray diffraction and thermogravimetric analysis.     

Poly[(μ4‐adamantane‐1,3‐dicarboxylato‐κ5O1:O1′:O3,O3′:O3′)(μ3‐adamantane‐1,3‐dicarboxylato‐κ5O1,O1′:O3,O3′:O3′)dimagnesium]: a layered coordination polymer

The title compound, [Mg₂(C₁₂H₁₄O₄)₂]_n, is the first example of an s‐block metal adamantanedicarboxylate coordination polymer. The asymmetric unit comprises two crystallographically unique Mg^II centers and two adamantane‐1,3‐dicarboxylate ligands. The compound is constructed from a combination of chains of corner‐sharing magnesium‐centered polyhedra, parallel to the a axis, connected by organic linkers to form a layered polymer. The two Mg^II centers are present in distorted tetrahedral and octahedral coordination environments derived from carboxylate O atoms. Tetrahedrally coordinated Mg^II centers have been reported in organometallic compounds, but this is the first time that such coordination has been observed in a magnesium‐based coordination polymer. The bond valance sums of the two Mg^II centers are 2.05 and 2.11 valence units, matching well with the expected value of 2.     

catena‐Poly[[diaquabis(2‐chloronicotinato‐κ2O,O′)cadmium(II)]‐μ‐2‐chloronicotinato‐κ3O,O′:N]

In the title neutral coordination polymer, [Cd(C₆H₃ClNO₂)₂(H₂O)₂]_n, each Cd^II ion is coordinated by one N and four O atoms from three 2‐chloro­nicotinate ligands and by two aqua ligands, defining a distorted monocapped octahedral coordination geometry. Adjacent Cd atoms are linked by the pyridyl N atom and the bidentate carboxyl­ate functional group of a 2‐­chloro­nicotinate ligand, forming a one‐dimensional infinite chain along the b axis. The Cd⋯Cd distance is 8.112 (3) Å. These chains are linked by O—H⋯O and O—H⋯N hydrogen bonds into a three‐dimensional network structure.     

catena‐Poly[[[(oxamide dioxime‐κ2N,N′)copper(II)]‐μ‐l‐tartrato‐κ4O1,O2:O3,O4] tetrahydrate]: a chiral nanochannel framework hosting solvent water molecules

The crystal structure of the title compound, {[Cu(C₄H₄O₆)(C₂H₆N₄O₂)]·4H₂O}_n, contains the central Cu^II cation in a distorted octahedral coordination, symmetrically chelated by the two imine N atoms of a neutral oxamide dioxime (H₂oxado) ligand [Cu—N = 1.9829 (16) Å] and unsymmetrically bis‐chelated by two halves of the l ‐(+)‐tartrate(2−) (tart) ligands, each half being linked to the Cu^II cation via the deprotonated carboxylate group and protonated hydroxy group [Cu—O = 1.9356 (14) and 2.4674 (13) Å, respectively]. The extended asymmetric unit is defined by twofold axes, one passing through the Cu^II cation and the centre of the oxamide dioxime (H₂oxado) ligand and the another two (symmetry related) bisecting the central C—C bonds of the tartrate ions. The structure is chiral, consisting of enantiomeric linear‐chain polymers oriented along [001], with virtual monomeric {Cu(tart_0.5)₂(H₂oxado)} repeat units and with the chains interleaved face‐to‐face into `twin pillars'. Nanochannels exist, running parallel to the c axis and bisecting a and b, which host `double strings' of solvent water molecules. Extensive hydrogen bonding (O—H...O and N—H...O) between the chains and solvent water molecules, together with extended π–σ interactions, consolidate the bulk crystal structure.     

catena‐Poly[[[aqua(ethylenediamine‐κ2N,N′)(nitrato‐κO)copper(II)]‐μ‐4,4′‐dithiodipyridine‐κ2N:N′] nitrate monohydrate]

The title compound, {[Cu(NO₃)(C₂H₄N₂)(C₁₀H₈N₂S₂)(H₂O)]NO₃·H₂O}_n, is composed of a one‐dimensional linear coordination polymer involving cis‐protected copper(II) ions and a 4,4′‐dithiodipyridine bridging ligand. The polymeric chains run along the c‐axis direction. N—H...O and O—H...O hydrogen bonds involving the coordinating amine groups, nitrate ions and water molecules, as well as cocrystallized noncoordinating nitrate ions and water molecules, generate a three‐dimensional structure.     

catena‐Poly[[(acetato‐κ2O,O′)triaquabarium(II)]‐μ3‐acetato‐κ4O:O,O′:O′]

The present form of barium acetate, formulated as [Ba(C₂H₃O₂)₂(H₂O)₃]_n, is the largest reported hydrate of the salt and this leads to a distinct structural behaviour setting it apart from the rest of the family. The compound is a linear polymer with a nine‐coordinate Ba(O_aqua)₃(O_acetate)₆ monomer unit. The non‐H part of the structure is ordered according to C2/m symmetry, while the disordered water H atoms only abide by this symmetry in a statistical sense. Each molecule is halved by a mirror plane bisecting the Ba centre, one water molecule and one acetate ligand, while containing the other acetate ligand. The chains are interconnected by a disordered water–water/acetate O—H...O hydrogen‐bonding network involving all water H atoms. The structure and stability of this phase are compared with the other known acetates of barium which differ in the degree of hydration.     

Polymeric diaqua(μ2‐2,2′‐bipyrimidinyl‐κ4N1,N1′:N3,N3′)‐di‐μ3‐hydroxy‐bis(μ5‐benzene‐1,3,5‐tricarboxylato‐κ5O1:O2:O3:O3:O5)tetracobalt(II) dihydrate

The structure of the title compound, [Co₄(C₉H₃O₆)₂(OH)₂(C₈H₆N₄)(H₂O)₂]·2H₂O, contains three separate species, namely the μ₅‐bridging C₉H₃O₆^3? anion, the doubly chelating and therefore μ₂‐bridging C₈H₆N₄ ligand (bi­pyrimidine, BPM), and the dihydrated di­aqua­di­hydroxy tetranuclear cationic cluster, [Co₄(OH^?)₂(H₂O)₂]⁶⁺·2H₂O, which lies on a crystallographic centre of symmetry, as does the BPM ligand with, in this case, the centre of symmetry coincident with the midpoint of the C—C bond joining the six‐membered rings. Within the cation cluster, the Co atoms of one pair are five‐coordinate and those of the other six‐coordinate.     

catena‐Poly[[μ‐hexa­nedioato‐1κO1:2κO6‐bis­[aqua­(5‐carboxy­penta­noato‐κO)copper(II)]]‐di‐μ‐4,4′‐bipyridine‐1κN:1′κN′;2κN:2′κN′]

In the title compound, [Cu₂(C₆H₈O₄)(C₆H₉O₄)₂(C₁₀H₈N₂)₂(H₂O)₂]_n, the square‐pyramidally coordinated Cu atoms are bridged by both 4,4‐bipyridine and adipate ligands into ladder‐­like chains, with exo‐orientated 5‐carboxypentan­oate ligands pendant from both side rails. Half of the adipate ligand is related to the other half by inversion symmetry. Inter­chain O—H⋯O hydrogen bonds from the aqua ligands to the carbonyl O atoms of the 5‐carboxy­penta­noate ligands are responsible for the formation of two‐dimensional grid‐like (4,4)‐networks, which complete a twofold inter­penetration.     

Bis(di‐2‐pyridylamine‐κ2N2,N2′)(nitrato‐κ2O,O′)nickel(II) nitrate

<!?tpct=26.8pt>In the ionic title compound, [Ni(NO₃)(C₁₀H₉N₃)₂]NO₃, the central Ni^II atom exhibits cis‐NiN₄O₂ octahedral coordination with three chelating ligands, viz. one nitrate anion and two di‐2‐pyridylamine (dpya) molecules. A second nitrate group acts as a counter‐ion. The complex cations and the nitrate anions are also linked by N—H...O hydrogen bonds. The compound was prepared in two different reproducible ways: direct synthesis from Ni(NO₃)₂ and dpya yielded systematically twinned crystals (the twinning law is discussed), while single crystals were obtained unexpectedly from the Ni(NO₃)₂/dpya/maleic acid/NaOH system.     

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[[(1,10‐phenanthroline‐κ2N,N′)copper(II)]‐μ‐(dihydrogen benzene‐1,2,4,5‐tetracarboxylato)‐κ2O1:O4]

In the title compound, [Cu(C₁₀H₄O₈)(C₁₂H₈N₂)]_n, the Cu^II cation has a four‐coordination environment completed by two N atoms from one 1,10‐phenanthroline (phen) ligand and two O atoms belonging to two di­hydrogen benzene‐1,2,4,5‐­tetra­carboxyl­ate anions (H₂TCB²⁻). There is a twofold axis passing through the Cu^II cation and the centre of the phen ligand. The [Cu(phen)]²⁺ moieties are bridged by H₂TCB²⁻ anions to form an infinite one‐dimensional coordination polymer with a zigzag chain structure along the c axis. A double‐chain structure is formed by hydrogen bonds between adjacent zigzag chains. Furthermore, there are π–π stacking inter­actions between the phen ligands, with an average distance of 3.64 Å, resulting in a two‐dimensional network structure.     

Poly[aqua[μ2‐1,4‐bis(imidazol‐1‐ylmethyl)benzene‐κ2N3:N3′](μ2‐5‐hydroxybenzene‐1,3‐dicarboxylato‐κ4O1,O1′:O3,O3′)cadmium(II)], a twofold interpenetrated CdSO4‐like metal–organic polymer

In the title cadmium(II) complex, [Cd(C₈H₄O₅)(C₁₄H₁₄N₄)(H₂O)]_n, the 5‐hydroxybenzene‐1,3‐dicarboxylate (5‐OH‐1,3‐bdc) and 1,4‐bis(imidazol‐1‐ylmethyl)benzene (1,4,‐bix) ligands bridge water‐coordinated Cd^II atoms to generate a three‐dimensional network. Two carboxylate groups from different ligands function as O,O′‐chelates, while two imidazole N atoms from different ligands coordinate in a monodentate fashion, and one water molecule completes the seven‐coordinate pentagonal bipyramid around the Cd^II atom, in which the N atoms occupy the axial sites and the O atoms occupy the equatorial sites. The overall architecture is a twofold interpenetrated CdSO₄‐type framework. The two crystallographically equivalent frameworks are linked by O—H...O hydrogen bonds between the water, hydroxy and carboxylate groups.     

catena‐Poly[[dicyanamido(5,5′‐dimethyl‐2,2′‐bipyridine‐κ2N,N′)copper(II)]‐μ‐dicyanamido‐κ2N1:N5]

In the crystal structure of the title compound, [Cu(C₂N₃)₂(C₁₂H₁₂N₂)]_n, the Cu^II atom adopts a distorted square‐pyramidal geometry, the basal plane of which is formed by two N atoms of the bi­pyridine ligand, one N atom of a bidentate dicyan­amide anion and one N atom of a monodentate dicyan­amide anion [Cu—N = 1.9760 (15)–2.0157 (15) Å]. The apical position is occupied by an N atom of a bidentate dicyan­amide anion, located 2.2468 (16) Å from the Cu atom, thus forming a one‐dimensional polymeric chain.     

catena‐Poly[[(2,2′‐biimidazole‐κ2N,N′)chloro­copper(II)]‐μ‐chloro]

In the polymeric title compound, [CuCl₂(C₆H₆N₄)]_n, each Cu^II ion is five‐coordinated by four basal atoms (two N atoms from a 2,2′‐biimidazole mol­ecule and two Cl⁻ anions) and one axial Cl⁻ anion, in a distorted square‐pyramidal coordination geometry. Cl⁻ anions bridge the {Cu(C₆H₆N₄)Cl} units into one‐dimensional linear chains, which are reinforced by π–π inter­actions. Adjacent linear chains are linked by N—H⋯Cl hydrogen bonds, resulting in a grid layer. The hydrogen‐bonding pattern can be described in graph‐set notation as C(9)R(9)R(14). This study extends our knowledge of the multifunctional properties of the 2,2′‐biimidazole ligand and of the coordination stereochemistry of copper(II).     

catena‐Poly[[[triaquazinc(II)]‐μ‐2‐nitroterephthalato‐κO1:κ2O4,O4′] monohydrate]

The title complex, {[Zn(C₈H₃NO₆)(H₂O)₃]·H₂O}_n, has a one‐dimensional chain structure. The two carboxylate groups of the dianionic 2‐nitroterephthalate ligand adopt mono‐ and bidentate chelating modes. The Zn atom shows distorted octahedral coordination, bonded to three O atoms from two carboxylate groups and three O atoms of three non‐equivalent coordinated water molecules. The one‐dimensional chains are aggregated into two‐dimensional layers through inter‐chain hydrogen bonding. The whole three‐dimensional structure is further stabilized by inter‐layer hydrogen bonds.     

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.     

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.     

Poly[[[μ‐1,1′‐(butane‐1,4‐diyl)diimidazole‐κ2N:N′](μ‐cyclohexane‐1,4‐dicarboxylato‐κ4O1,O1′:O4,O4′)cadmium(II)] hemihydrate]: a parallel interpenetrating two‐dimensional (4,4) network

In the title coordination compound, {[Cd(C₈H₁₀O₄)(C₁₀H₁₄N₄)]·0.5H₂O}_n, the 1,1′‐(butane‐1,4‐diyl)diimidazole ligand and the cyclohexane‐1,4‐dicarboxylate dianion both function in a bridging mode to link adjacent cadmium(II) centers into a two‐dimensional four‐connected (4,4) network. The networks are parallel to the (001) plane. Two (4,4) networks are interpenetrated in an unusual parallel mode. The compound is the first two‐dimensional parallel interpenetrating (4,4) network structure based on a flexible dicarboxylate and a long bidentate N‐donor ligand. The interpenetrating nets are further consolidated by water–carboxylate O—H...O hydrogen bonds.