A novel three‐dimensional copper(I) cyanide coordination polymer constructed from various bridging ligands: synthesis,crystal structure and characterization

The cyanide ligand can act as a strong σ‐donor and an effective π‐electron acceptor that exhibits versatile bridging abilities, such as terminal, μ₂‐C:N, μ₃‐C:C:N and μ₄‐C:C:N:N modes. These ligands play a key role in the formation of various copper(I) cyanide systems, including one‐dimensional (1D) chains, two‐dimensional (2D) layers and three‐dimensional (3D) frameworks. According to the literature, numerous coordination polymers based on terminal, μ₂‐C:N and μ₃‐C,C,N bridging modes have been documented so far. However, systems based on the μ₄‐C:C:N:N bridging mode are relatively rare. In this work, a novel cyanide‐bridged 3D Cu^I coordination framework, namely poly[(μ₂‐2,2′‐biimidazole‐κ²N³:N^3′)(μ₄‐cyanido‐κ⁴C:C:N:N)(μ₂‐cyanido‐κ²C:N)dicopper(I)], [Cu₂(CN)₂(C₆H₆N₄)]_n, (I), was synthesized hydrothermally by reaction of environmentally friendly K₃[Fe(CN)₆], CuCl₂·2H₂O and 2,2′‐biimidazole (H₂biim). It should be noted that cyanide ligands may act as reducing agents to reduce Cu^II to Cu^I under hydrothermal conditions. Compound (I) contains diverse types of bridging ligands, such as μ₄‐C:C:N:N‐cyanide, μ₂‐C:N‐cyanide and μ₂‐biimidazole. Interestingly, the [Cu₂] dimers are bridged by rare μ₄‐C:C:N:N‐mode cyanide ligands giving rise to the first example of a 1D dimeric {[Cu₂(μ₄‐C:C:N:N)]ⁿ⁺}_n infinite chain. Furthermore, adjacent dimer‐based chains are linked by μ₂‐C:N bridging cyanide ligands, generating a neutral 2D wave‐like (4,4) layer structure. Finally, the 2D layers are joined together via bidentate bridging H₂biim to create a 3D cuprous cyanide network. This arrangement leads to a systematic variation in dimensionality from 1D chain→2D sheet→3D framework by different types of bridging ligands. Compound (I) was further characterized by thermal analysis, solid‐state UV–Vis diffuse‐reflectance and photoluminescence studies. The solid‐state UV–Vis diffuse‐reflectance spectra show that compound (I) is a wide‐gap semiconductor with band gaps of 3.18 eV. The photoluminescence study shows a strong blue–green photoluminescence at room temperature, which may be associated with metal‐to‐ligand charge transfer.     

A two‐dimensional cadmium(II) polymer based on nicotinic acid and thiocyanate ligands

A cadmium–thiocyanate complex, poly[[bis(nicotinic acid‐κN)di‐μ‐thiocyanato‐κ²N:S;κ²S:N‐cadmium(II)] monohydrate], {[Cd(NCS)₂(C₆H₅NO₂)₂]·H₂O}_n, was synthesized by the reaction of nicotinic acid, cadmium nitrate tetrahydrate and potassium thiocyanide in aqueous solution. In the crystal structure, each Cd^II cation is in a distorted octahedral coordination environment, coordinated by the N and S atoms of nicotinic acid and thiocyanate ligands. Neighbouring Cd^II cations are linked together by thiocyanate bridges to form a two‐dimensional network. Hydrogen‐bond interactions between the uncoordinated solvent water molecules and the organic ligands result in the formation of the three‐dimensional supramolecular network.     

A novel three‐dimensional AgI coordination polymer based on mixed naphthalene‐1,5‐disulfonate and aminoacetate ligands

The three‐dimensional coordination polymer poly[[bis(μ₃‐2‐aminoacetato)di‐μ‐aqua‐μ₃‐(naphthalene‐1,5‐disulfonato)‐hexasilver(I)] dihydrate], {[Ag₆(C₁₀H₆O₆S₂)(C₂H₄NO₂)₄(H₂O)₂]·2H₂O}_n, based on mixed naphthalene‐1,5‐disulfonate (L1) and 2‐aminoacetate (L2) ligands, contains two Ag^I centres (Ag1 and Ag4) in general positions, and another two (Ag2 and Ag3) on inversion centres. Ag1 is five‐coordinated by three O atoms from one L1 anion, one L2 anion and one water molecule, one N atom from one L2 anion and one Ag^I cation in a distorted trigonal–bipyramidal coordination geometry. Ag2 is surrounded by four O atoms from two L2 anions and two water molecules, and two Ag^I cations in a slightly octahedral coordination geometry. Ag3 is four‐coordinated by two O atoms from two L2 anions and two Ag^I cations in a slightly distorted square geometry, while Ag4 is also four‐coordinated by two O atoms from one L1 and one L2 ligand, one N atom from another L2 anion, and one Ag^I cation, exhibiting a distorted tetrahedral coordination geometry. In the crystal structure, there are two one‐dimensional chains nearly perpendicular to one another (interchain angle = 87.0°). The chains are connected by water molecules to give a two‐dimensional layer, and the layers are further bridged by L1 anions to generate a novel three‐dimensional framework. Moreover, hydrogen‐bonding interactions consolidate the network.     

A novel three‐dimensional coordination polymer constructed from pyrazine and copper(I): poly[[copper(I)‐di‐μ2‐pyrazine‐κ4N:N′] 3,5‐dicarboxybenzenesulfonate monohydrate]

In the title metal–organic framework complex, {[Cu(C₄H₄N₂)₂](C₈H₅O₇S)·H₂O}_n or {[Cu^I(pyz)₂](H₂SIP)·H₂O}_n (pyz is pyrazine and H₃SIP is 5‐sulfoisophthalic acid or 3,5‐dicarboxybenzenesulfonic acid), the asymmetric unit is composed of one copper(I) center, one whole pyrazine ligand, two half pyrazine ligands lying about inversion centres, one H₂SIP⁻ anion and one lattice water molecule, wherein each Cu^I atom is in a slightly distorted tetrahedral coordination environment completed by four pyrazine N atoms, with the Cu—N bond lengths in the range 2.017 (3)–2.061 (3) Å. The structure features a three‐dimensional diamondoid network with one‐dimensional channels occupied by H₂SIP⁻ anions and lattice water molecules. Interestingly, the guest–water hydrogen‐bonded network is also a diamondoid network, which interpenetrates the metal–pyrazine network.     

A novel three-dimensional coordination polymer constructed with mixed-valence dimeric copper(I,II) units

A novel three-dimensional coordination polymer with a mixed-valence localized copper(I,II) dimeric unit, [Cu2(4-pya)3]n (4-pya = 4-pyridinecarboxylate), was hydrothermally synthesized via a simultaneous in-situa redox and hydrolysis reaction of Cu(II) and 4-cyanopyridine and crystallographically characterized to be a twofold interpenetrated three-dimensional coordination network with a cubic [Cu16(4-pya)12] building unit.     

A one‐dimensional CdII coordination polymer constructed from 4‐(dimethylamino)pyridinium‐1‐acetate ligands and thiocyanate coordination bridges

A new cadmium–thiocyanate complex, namely catena‐poly[1‐carboxymethyl‐4‐(dimethylamino)pyridinium [cadmium(II)‐tri‐μ‐thiocyanato‐κ⁴N:S;κ²S:N] [[[4‐(dimethylamino)pyridinium‐1‐acetate‐κ²O,O′]cadmium(II)]‐di‐μ‐thiocyanato‐κ²N:S;κ²S:N]], {(C₉H₁₃N₂O₂)[Cd(NCS)₃][Cd(NCS)₂(C₉H₁₂N₂O₂)]}_n, was synthesized by the reaction of 4‐(dimethylamino)pyridinium‐1‐acetate, cadmium nitrate tetrahydrate and potassium thiocyanide in aqueous solution. In the crystal structure, two types of Cd^II atoms are observed in distorted octahedral coordination environments. One type of Cd^II atom is coordinated by two O atoms from the carboxylate group of the 4‐(dimethylamino)pyridinium‐1‐acetate ligand and by two N atoms and two S atoms from four different thiocyanate ligands, while the second type of Cd^II atom is coordinated by three N atoms and three S atoms from six different thiocyanate ligands. Neighbouring Cd^II atoms are linked by thiocyanate bridges to form a one‐dimensional zigzag chain and a one‐dimensional coordination polymer. Hydrogen‐bond interactions are involved in the formation of the supramolecular network.     

A novel two‐dimensional zinc(II) coordination polymer with 6‐mercaptonicotinic acid

The novel title Zn^II coordination polymer, poly[bis(μ‐6‐thioxo‐1,6‐dihydropyridine‐3‐carboxylato‐κ²S:O)zinc(II)], [Zn(C₆H₄NO₂S)₂]_n, consists of two crystallographically independent zinc centers and two 6‐mercaptonicotinate (Hmna⁻) ligands. Each Zn^II atom is four‐coordinated and lies at the center of a distorted tetrahedral ZnS₂O₂ coordination polyhedron, bridged by four Hmna⁻ ligands to form a two‐dimensional (4,4)‐network. Each Hmna⁻ ion acts as a bridging bidentate ligand, coordinating to two Zn^II atoms through the S atom and a carboxyl O atom. The metal centers reside on twofold rotation axes. The coordination mode of the S atoms and N—H...O hydrogen‐bonding interactions between the protonated N atoms and the uncoordinated carboxyl O atoms give the extended structure a wavelike form.     

A novel one‐dimensional zigzag coordination polymer of copper(II) with di­methyl­glyoxime

A novel metal‐organic based polymeric complex, namely catena‐poly­[[bis(μ₄‐di­methyl­glyoximato)­bis(μ₂‐di­methyl­gly­oxi­mato)­bis­(di­methyl­glyoxime)­tetracopper(II)] diperchlorate dihydrate], {[Cu₄(dmg)₂(Hdmg)₂(H₂dmg)₂](ClO₄)₂·2H₂O}_∞ (H₂dmg is di­methyl­glyoxime, C₂H₈N₂O₂), has been synthesized and characterized by single‐crystal X‐ray diffraction methods. The complex is a one‐dimensional zigzag chain coordination polymer, in which the tetranuclear repeat unit is a centrosymmetric Cu₄ moiety coordinated to di­methyl­glyoxime ligands only. These units are linked by double Cu—O—Cu bridges in a centrosymmetric rectangular ­junction.     

A two‐dimensional layered CdII coordination polymer with a three‐dimensional supramolecular architecture incorporating mixed multidentate N‐ and O‐donor ligands

The combination of N‐heterocyclic and multicarboxylate ligands is a good choice for the construction of metal–organic frameworks. In the title coordination polymer, poly[bis{μ₂‐1‐[(1H‐benzimidazol‐2‐yl)methyl]‐1H‐tetrazole‐κ²N³:N⁴}(μ₄‐butanedioato‐κ⁴O¹:O^1′:O⁴:O^4′)(μ₂‐butanedioato‐κ²O¹:O⁴)dicadmium], [Cd(C₄H₄O₄)(C₉H₈N₆)]_n, each Cd^II ion exhibits an irregular octahedral CdO₄N₂ coordination geometry and is coordinated by four O atoms from three carboxylate groups of three succinate (butanedioate) ligands and two N atoms from two 1‐[(1H‐benzimidazol‐2‐yl)methyl]‐1H‐tetrazole (bimt) ligands. Cd^II ions are connected by two kinds of crystallographically independent succinate ligands to generate a two‐dimensional layered structure with bimt ligands located on each side of the layer. Adjacent layers are further connected by hydrogen bonding, leading to a three‐dimensional supramolecular architecture in the solid state. Thermogravimetric analysis of the title polymer shows that it is stable up to 529 K and then loses weight from 529 to 918 K, corresponding to the decomposition of the bimt ligands and succinate groups. The polymer exhibits a strong fluorescence emission in the solid state at room temperature.     

A one‐dimensional copper coordination polymer containing both dicyan­amide and 1,10‐phenanthroline ligands

The crystal structure of catena‐poly­[[[acetato(1,10‐phenanthroline‐κ²N,N′)copper(II)]‐μ‐dicyan­amido‐κ²N¹:N⁵] trihydrate], {[Cu(C₂H₃O₂)(C₂N₃)(C₁₂H₈N₂)]·3H₂O}_n, consists of a zigzag chain formed by the polymer [Cu(CH₃COO)(dca)(phen)]_n (phen is 1,10‐phenanthroline and dca is dicyan­amide), with three water mol­ecules per repeat unit of the polymer. The Cu^II atom has a slightly distorted square‐pyramidal coordination environment consisting of two N atoms of the phen ligand, two nitrile N atoms of different dca ligands, one of them axial, and one O atom of the acetate anion. The compound forms a one‐dimensional chain using dca as an end‐to‐end bridging ligand. Non‐covalent interactions, π–π stacking and hydrogen bonding mediate the bundling of the polymer chains into a three‐dimensional structure, with the water mol­ecules playing an important role in the hydrogen bonding.     

A three‐dimensional coordination polymer of 3‐(3,5‐dicarboxybenzyloxy)benzoic acid with zinc

The synthesis is reported of the tricarboxylic acid 3‐(3,5‐dicarboxybenzyloxy)benzoic acid (H₃L) and the product of its reaction under solvothermal conditions with Zn^II cations, namely poly[[μ₆‐3‐(3,5‐dicarboxylatobenzyloxy)benzoato](dimethylformamide)‐μ₃‐hydroxido‐dizinc(II)], [Zn₂(C₁₆H₉O₇)(OH)(C₃H₇NO)]_n, the formation of which is associated with complete deprotonation of H₃L. Its crystal structure consists of a single‐framework coordination polymer of the organic L³⁻ ligand with Zn^II cations in a 1:2 ratio, with additional hydroxide and dimethylformamide (DMF) ligands coordinated to the Zn^II centres. The Zn^II cations are characterized by coordination numbers of 5 and 6, being bridged to each other by hydroxide ligands. In the polymeric framework, the carboxylate‐ and hydroxy‐bridged Zn^II cations are arranged in coordination‐tessellated columns, which propagate along the a axis of the crystal structure, and each L³⁻ ligand links to seven different Zn^II centres via Zn—O bonds of two different columns. The coordination framework, composed of [Zn₂(L)(OH)(DMF)]_n units, forms an open architecture, the channel voids within it being filled by the zinc‐coordinating DMF ligands. This report provides the first structural evidence for the formation of coordination polymers with H₃L via multiple metal–ligand bonds through its carboxylate groups.<!?tpb=21.5pt>     

A novel three‐dimensional copper(II) coordination polymer with 1,4‐bis(1,2,4‐triazol‐1‐ylmeth­yl)benzene and thio­cyanate

In the title complex, poly[copper(II)‐di‐μ₂‐thio­cyanato‐μ₂‐1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene], [Cu(NCS)₂(C₁₂H₁₂N₆)]_n, the Cu^II atom lies on an inversion centre in a tetra­gonally distorted octa­hedral environment. Four N atoms from thio­cyanate and 1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene (bbtz) ligands fill the equatorial positions, and S atoms from symmetry‐related thio­cyanate ligands fill the axial positions. The benzene ring of the bbtz ligand lies about an inversion centre. Single thio­cyanate bridges link the Cu^II atoms into two‐dimensional sheets containing an unprecedented 16‐membered [Cu₄(μ‐NCS‐N:S)₄] ring. The bbtz ligands further link the two‐dimensional sheets into a three‐dimensional network.     

Green conversion of a three‐dimensional organometallic coordination polymer to a three‐dimensional organometallic supramolecular polymer upon mechanochemical 2‐aminopyridine addition

Green conversion of three‐dimensional organometallic [Ag₂(μ₆‐tp)]_n ( 1 ) coordination polymer (CP) nanosheets, prepared by sonochemical procedure, to three‐dimensional organometallic [Ag₂(μ₄‐tp)(apy)₂]_n ( 2 ) (where H₂tp = terephthalic acid and apy = 2‐aminopyridine) CP nanoparticles has been observed upon solid‐state mechanochemical reaction of compound 1 with 2‐aminopyridine. The AgO₃ Ag ···C₆ coordination sphere of silver ion in 1 changed to NO₂ Ag ···C coordination sphere in 2 during this mechanochemical addition. These samples were characterized by infrared spectroscopy, thermogravimetric and differential thermal analyses, X‐ray powder diffraction and scanning electron microscopy.     

A new two‐dimensional anionic cadmium(II) polymer constructed through thiocyanate coordination bridges

A new cadmium–thiocyanate complex, poly[4‐(dimethylamino)pyridin‐1‐ium [di‐μ‐thiocyanato‐κ²N:S;κ²S:N‐thiocyanato‐κN‐cadmium(II)]], {(C₇H₁₁N₂)[Cd(NCS)₃]}_n, was synthesized by the reaction of cadmium thiocyanate and 4‐(dimethylamino)pyridine hydrochloride in aqueous solution. In the crystal structure, each Cd^II ion is square‐pyramidally coordinated by three N and two S atoms from five different thiocyanate ligands, four of which are bridging. The thiocyanate ligands play different roles in the build up of the structure; one role results in the formation of [Cd₂(NCS)₂] building blocks, while the other links the building blocks and cations via N—H...S hydrogen bonds. The N—H...S hydrogen bonds and weak π–π stacking interactions are involved in the formation of both a two‐dimensional network structure and the supramolecular network.     

A two‐dimensional anionic CdII polymer constructed through dicyanamide coordination bridges

In the search for potential ferroelectric materials, molecular‐based one‐, two‐ and three‐dimensional cadmium(II) organic–inorganic compounds have been of interest as they often display solid–solid phase transitions induced by a variation in temperature. A new cadmium dicyanamide complex, poly[4‐dimethylamino‐1‐ethylpyridin‐1‐ium [tri‐μ‐dicyanamido‐κ⁶N¹:N⁵‐cadmium(II)]], {(C₉H₁₅N₂)[Cd(C₂N₃)₃]}_n, was synthesized by the reaction of 4‐dimethylamino‐1‐ethylpyridin‐1‐ium bromide, cadmium nitrate tetrahydrate and sodium dicyanamide in aqueous solution. In the crystal structure, each Cd^II cation is octahedrally coordinated by six terminal N atoms from six anionic dicyanamide (dca) ligands. Neighbouring Cd^II cations are linked together by dicyanamide bridges to form a two‐dimensional coordination polymer. The organic cations are not involved in the formation of the supramolecular network.     

A coordination polymer consisting of two different one‐dimensional copper(II) chains

The title compound, catena‐poly[[[diaqua(methanol‐κO)copper(II)]‐μ‐N‐(4‐methylpyrimidin‐2‐yl‐κN¹)pyrazin‐2‐amine‐κ²N¹:N⁴] [[aqua(aqua/methanol‐κO)(perchlorato‐κO)copper(II)]‐μ‐N‐(4‐methylpyrimidin‐2‐yl‐κN¹)pyrazin‐2‐amine‐κ²N¹:N⁴] tris(perchlorate) methanol monosolvate 1.419‐hydrate], {[Cu(C₉H₉N₅)(CH₃OH)(H₂O)₂][Cu(C₉H₉N₅)(ClO₄)(CH₃OH)_0.581(H₂O)_1.419](ClO₄)₃·CH₃OH·1.419H₂O}_n, is a one‐dimensional straight‐chain polymer of N‐(4‐methylpyrimidin‐2‐yl)pyrazin‐2‐amine (L) with Cu(ClO₄)₂. The complex consists of two crystallographically independent one‐dimensional chains in which the Cu^II atoms exhibit two different octahedral coordination geometries. The L ligand coordinates to two Cu^II centres in a tridentate manner, with the pyrazine ring acting as a bridge linking the Cu^II coordination units and building an infinite one‐dimensional chain. Extensive hydrogen bonding among perchlorate anions, water molecules and L ligands results in three‐dimensional networks.     

A novel one‐dimensional coordination polymer with Cd2+ and diethylenetriaminepentaacetic acid

catena‐Poly­[[[bis­[di­aqua(4,4′‐bi­pyridine)­cadmium(II)]‐bis­[μ‐(N′′‐carboxy­methyl­diethyl­enetri­amine‐N,N,N′,N′′‐tetra­ace­ta­to)­cadmium(II)]]‐μ‐4,4′‐bi­pyridine] tetradecahydrate], [Cd₄­(C₁₄H₁₉N₃O₁₀)₂(C₁₀H₈N₂)₃(H₂O)₄]·14H₂O or [Cd₄(HD­TPA)₂(BPY)₃(H₂O)₄]·14H₂O, where BPY is 4,4′‐bi­pyridine and HDTPA^4? is N′′‐carboxy­methyl­diethyl­enetri­amine‐N,N,N′,N′′‐tetra­acetate, consists of a one‐dimensional coordination polymer formed from a secondary building unit which comprises four Cd centres. The chain structure of the title compound was obtained by the use of a multidentate organic ligand, N,N,N′,N′′,N′′‐diethyl­enetri­amine­penta­acetic acid (H₅DTPA), which forms multiple chelate rings with the Cd metal centres. An extended network is formed via hydrogen bonds.     

A three‐dimensional cadmium(II) coordination polymer with unequal homochiral double‐stranded concentric helical chains

A homochiral helical three‐dimensional coordination polymer, poly[[(μ₂‐acetato‐κ³O,O′:O)(hydroxido‐κO)(μ₄‐5‐nicotinamido‐1H‐1,2,3,4‐tetrazol‐1‐ido‐κ⁵N¹,O:N²:N⁴:N⁵)(μ₃‐5‐nicotinamido‐1H‐1,2,3,4‐tetrazol‐1‐ido‐κ⁴N¹,O:N²:N⁴:N⁵)dicadmium(II)] 0.75‐hydrate], {[Cd₂(C₇H₅N₆O)₂(CH₃COO)(OH)]·0.75H₂O}_n, was synthesized by the reaction of cadmium acetate, N‐(1H‐tetrazol‐5‐yl)isonicotinamide (H‐NTIA), ethanol and H₂O under hydrothermal conditions. The asymmetric unit contains two crystallographically independent Cd^II cations, two deprotonated 5‐nicotinamido‐1H‐1,2,3,4‐tetrazol‐1‐ide (NTIA⁻) ligands, one acetate anion, one hydroxide anion and three independent partially occupied water sites. The two Cd^II cations, with six‐coordinated octahedral and seven‐coordinated pentagonal bipyramidal geometries are located on general sites. The tetrazole group of one symmetry‐independent NTIA⁻ ligand links one of the independent Cd^II cations into 6₁ helical chains, while the other NTIA⁻ ligand links the other independent Cd^II cations into similar but unequal 6₁ helical chains. These chains, with a pitch of 24.937 (5) Å, intertwine into a double‐stranded helix. Each of the double‐stranded 6₁ helices is further connected to six adjacent helical chains through an acetate μ₂‐O atom and the tetrazole group of the NTIA⁻ ligand into a three‐dimensional framework. The helical channel is occupied by the isonicotinamide groups of NTIA⁻ ligands and two helices are connected to each other through the pyridine N and carbonyl O atoms of isonicotinamide groups. In addition, N—H...O and O—H...N hydrogen bonds exist in the complex.     

A new three‐dimensional silver(I) coordination framework with a diamondoid topology constructed from 2‐(pyridin‐4‐yl)‐1H‐imidazole‐4,5‐dicarboxylic acid

The title compound, poly[[μ₄‐5‐carboxy‐4‐carboxylato‐2‐(pyridin‐4‐yl)‐1H‐imidazol‐1‐ido]disilver(I)], [Ag₂(C₁₀H₅N₃O₄)]_n, was synthesized by reacting silver nitrate with 2‐(pyridin‐4‐yl)‐1H‐imidazole‐4,5‐dicarboxylic acid (H₃PyIDC) under hydrothermal conditions. The asymmetric unit contains two crystallographically independent Ag^I cations and one unique HPyIDC²⁻ anion. Both Ag^I cations are three‐coordinated in distorted T‐shaped coordination geometries. One Ag^I cation is coordinated by one N and two O atoms from two HPyIDC²⁻ anions, while the other is bonded to one O and two N atoms from two HPyIDC²⁻ anions. It is interesting to note that the HPyIDC²⁻ group acts as a μ₄‐bridging ligand to link the Ag^I cations into a three‐dimensional framework, which can be simplified as a diamondoid topology. The thermal stability and photoluminescent properties of the title compound have also been studied.     

A three‐dimensional (3D) manganese (II) coordination polymer: Synthesis,structure and catalytic activities

A new Mn (II)‐containing coordination polymer, [Mn₆(Ipa)₆(ad)?6H₂O] ( 1 ; Ipa = isophthalate ligand; ad = adenine), was synthesized by reacting hydrated manganese nitrate with isophthalic acid and adenine under solvothermal reaction conditions. Polymer 1 was characterized using single‐crystal X‐ray diffraction analysis and other techniques such as Fourier transform infrared spectroscopy, elemental analyses and powder X‐ray diffraction. The solid‐state structure of 1 confirmed the formation of a three‐dimensional framework structure based on Mn₆ secondary building units. Phase purity of bulk 1 and its thermal stability were investigated. Polymer 1 was evaluated for its performance as a heterogeneous catalyst for the Henry (nitroaldol) reaction of nitromethane with several aldehydes. The recyclability of 1 and heterogeneity of the reaction were also explored. A plausible mechanism for such reaction is proposed. To the best of our knowledge, polymer 1 represents the first example of a Mn (II)‐ and adenine‐containing coordination polymer as well as the first example of a Mn (II)‐containing coordination polymer that has been employed for the Henry reaction.