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.     

Poly[[cobalt(II)‐di‐μ3‐3,5‐diamino­benzoato‐κ3N:N′:O] monohydrate]

In the title compound, {[Co(C₇H₇N₂O₂)₂]·H₂O}_n, the Co^II atom lies on an inversion centre and has octahedral geometry, defined by two O atoms in axial positions and four N atoms in equatorial sites from six different 3,5‐diamino­benzoate ligands. Each 3,5‐diamino­benzoate anion acts as a μ₃‐bridging ligand, linking three adjacent Co^II ions through one O atom and two N atoms to form a three‐dimensional coordination polymer.     

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[[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[[diiodo­zinc(II)]‐μ‐4,4′‐bipyridine‐κ2N:N′]

The title compound, [ZnI₂(bipy)]_n (bipy is 4,4′‐bipyridine, C₁₀H₈N₂), has been prepared by the hydro­thermal reaction of ZnI₂ and bipy at 433 K. Each Zn atom is coordinated by two N atoms from two different bipy ligands and by two I atoms in a distorted tetra­hedral geometry, with Zn—N distances ranging from 2.068 (7) to 2.101 (8) Å and Zn—I distances ranging from 2.5471 (13) to 2.5673 (13) Å. The mol­ecular structure features a zigzag polymeric chain. Face‐to‐face π–π stacking inter­actions between adjacent bipy ligands stabilize the structure.     

catena‐Poly[[[diaqua­bis(pyridine‐4‐carboxamide‐κN)copper(II)]‐μ2‐squarato‐κO1:O3] dihydrate]

The asymmetric unit of the title compound, {[Cu(C₄O₄)(C₆H₆N₂O)₂(H₂O)₂]·2H₂O}_n, consists of one pyridine‐4‐carbox­amide (isonicotinamide or ina) ligand, one‐half of a squarate dianion, a coordinated aqua ligand and a solvent water mol­ecule. Both the Cu^II and the squarate ions are located on inversion centers. The Cu^II ions are octa­hedrally surrounded by four O atoms of two water mol­ecules and two squarate anions, and by two N atoms of the isonicotinamide ligands. The crystal structure contains chains of squarate‐1,3‐bridged Cu^II ions. These chains are held together by N—H⋯O and O—H⋯O inter­molecular hydrogen‐bond inter­actions, forming an extensive three‐dimensional network.     

Poly[[tetraaquabis(μ2‐2‐nitroterephthalato‐κ3O1:O4,O4′)(μ2‐piperazine‐κ3N:N′)dicadmium(II)] dihydrate]

In the title complex, {[Cd₂(C₈H₃NO₆)₂(C₄H₁₀N₂)(H₂O)₄]·2H₂O}_n, the Cd^II atoms show distorted octahedral coordination. The two carboxylate groups of the dianionic 2‐nitroterephthalate ligand adopt monodentate and 1,2‐bridging modes. The piperazine molecule is in a chair conformation and lies on a crystallographic inversion centre. The Cd^II atoms are connected via three O atoms from two carboxylate groups and two N atoms from piperazine molecules to form a two‐dimensional macro‐ring layer structure. These layers are further aggregated to form a three‐dimensional structure via rich intra‐ and interlayer hydrogen‐bonding networks. This study illustrates that, by using the labile Cd^II salt and a combination of 2‐nitroterephthalate and piperazine as ligands, it is possible to generate interesting metal–organic frameworks with rich intra‐ and interlayer O—H...O hydrogen‐bonding networks.     

catena‐Poly[[diaquazinc(II)]‐μ‐4,4′‐sulfonyldibenzoato‐κ2O:O′]

The title compound, [Zn(C₁₄H₈O₆S)(H₂O)₂]_n, is the first reported metal complex of the 4,4′‐sulfonyldibenzoate anion. The structure comprises zigzag chains of alternating [Zn(H₂O)₂]²⁺ and sulfonyldibenzoate units, the central Zn and S atoms of which lie on crystallographic twofold axes. The Zn^II centre occupies a strongly distorted tetrahedral environment [O—Zn—O = 83.30 (7)–136.19 (8)°], coordinated by the two water O atoms [Zn—O = 1.986 (2) Å] and one O atom from each of two carboxylate groups [Zn—O = 1.9942 (19) Å], with much longer contacts to the other O atoms of these carboxylates [Zn—O = 2.528 (2) Å]. Hydrogen bonds between carboxylate O atoms and coordinated water molecules in adjacent chains lead to the formation of a three‐dimensional network structure.     

Poly[[diaqua­cadmium(II)]‐μ4‐[N‐(phosphonato­methyl)ammonio]acetato]

The title compound, [Cd(C₃H₆NO₅P)(H₂O)₂]_n, is a three‐dimensional polymeric complex. The asymmetric unit contains one Cd atom, one N‐(phosphono­methyl)glycine zwitterion [(O⁻)₂OPCH₂NH₂⁺CH₂COO⁻] and two water mol­ecules. The coordination geometry is a distorted CdO₆ octa­hedron. Each N‐(phosphono­methyl)glycine ligand bridges four adjacent water‐coordinated Cd cations through three phospho­nate O atoms and one carboxyl­ate O atom, like a regular PO₄³⁻ group in zeolite‐type frameworks. One‐dimensional zigzag (–O—P—C—N—C—C—O—Cd–)_n chains along the [101] direction are linked to one another via Cd—O—P bridges and form a three‐dimensional network motif with three types of channel systems. The variety of O—H⋯O and N—H⋯O hydrogen bonds is likely to be responsible for stabilizing the three‐dimensional network structure and preventing guest mol­ecules from entering into the channels.     

catena‐Poly[[aqua­(2,2′‐bipyridine‐κ2N,N′)cadmium(II)]‐μ‐4‐carboxyl­atophenoxy­acetato‐κ3O:O4,O4′]

In the title compound, [Cd(C₉H₆O₅)(C₁₀H₈N₂)(H₂O)]_n, the Cd^II atom is coordinated in a distorted octa­hedral fashion by two carboxyl­ate groups (one in a monodentate and one in a bidentate fashion) from two 4‐carboxyl­ato­phenoxy­acetate anions, two N atoms from a 2,2′‐bipyridine ligand and one aqua ligand. The structure is a helix with a long pitch of 16.441 (5) Å. A three‐dimensional supra­molecular network is further constructed through π–π stacking and hydrogen‐bonding inter­actions between the helices.     

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(1H‐benzimidazole‐κN3)(salicylato‐κO)copper(II)]‐μ‐salicylato‐O,O′:O′′]

The title compound, [Cu(C₇H₅O₃)₂(C₇H₆N₂)₂]_n, is a one‐dimensional polymeric complex bridged by salicyl­ate anions. The Cu^II atom is surrounded by three salicyl­ate and two benz­imidazole ligands, with a tetragonally elongated octahedral coordination geometry. The Cu—O bond distances in the axial directions are 2.6092 (16) and 2.6834 (17) Å. π–π stacking interactions exist between the benz­imidazole rings of neighboring polymeric complex chains.     

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[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.     

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[[[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[[bis(acetylacetonato‐κ2O,O′)cobalt(II)]‐μ‐1,3‐di‐4‐pyridylpropane‐κ2N:N′]: a one‐dimensional coordination polymer capable of forming clathrates with prochiral aldehydes

The title compound, [Co(C₅H₇O₂)₂(C₁₃H₁₄N₂)]_n, forms a coordination polymer in which the Co^II centre is located on an inversion centre and the 1,3‐di‐4‐pyridylpropane ligand is located on a twofold axis. The polymeric chains are parallel and are held together by weak intermolecular C—H...O interactions. The complex is intended as a possible host for prochiral aldehydes and ketones, and one clathrate was isolated with p‐tolylaldehyde.     

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[[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.     

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.