Bis(μ‐5‐carboxybenzene‐1,3‐dicarboxylato‐κ2O1:O3)bis[(2,2′‐bi‐1H‐imidazole‐κ2N3,N3′)zinc]

The title compound, [Zn₂(C₉H₄O₆)₂(C₆H₆N₄)₂], consists of two Zn^II ions, two 5‐carboxybenzene‐1,3‐dicarboxylate (Hbtc²⁻) dianions and two 2,2′‐bi‐1H‐imidazole (bimz) molecules. The Zn^II centre is coordinated by two carboxylate O atoms from two Hbtc²⁻ ligands and by two imidazole N atoms of a bimz ligand, in a distorted tetrahedral coordination geometry. Two neighbouring Zn^II ions are bridged by a pair of Hbtc²⁻ ligands, forming a discrete binuclear [Zn₂(Hbtc)₂(bimz)₂] structure lying across an inversion centre. Hydrogen bonds between carboxyl H atoms and carboxylate O atoms and between imidazole H atoms and carboxylate O atoms link the binuclear units. These binuclear units are further extended into a three‐dimensional supramolecular structure through extensive O—H...O and N—H...O hydrogen bonds. Moreover, the three‐dimensional nature of the crystal packing is reinforced by the π–π stacking. The title compound exhibits photoluminescence in the solid state, with an emission maximum at 415 nm.     

Poly[μ8‐4,4′‐bipyridine‐2,2′,6,6′‐tetracarboxylato‐dilead(II)]

The Pb^II cation in the title compound, [Pb₂(C₁₄H₄N₂O₈)]_n, is seven‐coordinated by one N atom and six O atoms from four 4,4′‐bipyridine‐2,2′,6,6′‐tetracarboxylate (BPTCA⁴⁻) ligands. The geometric centre of the BPTCA⁴⁻ anion lies on an inversion centre. Each pyridine‐2,6‐dicarboxylate moiety of the BPTCA⁴⁻ ligand links four Pb^II cations via its pyridyl N atom and two carboxylate groups to form two‐dimensional sheets. The centrosymmetric BPTCA⁴⁻ ligand then acts as a linker between the sheets, which results in a three‐dimensional metal–organic framework.     

Poly[[diaqua‐μ‐4,4′‐bipyridine‐dinitratodi‐μ‐l‐tyrosinato‐dicopper(II)]: a chiral two‐dimensional coordination polymer

The title compound, [Cu₂(C₉H₁₀NO₃)₂(NO₃)₂(C₁₀H₈N₂)(H₂O)₂]_n, contains Cu^II atoms and l ‐tyrosinate (l ‐tyr) and 4,4′‐bipyridine (4,4′‐bipy) ligands in a 2:2:1 ratio. Each Cu atom is coordinated by one amino N atom and two carboxylate O atoms from two l ‐tyr ligands, one N atom from a 4,4′‐bipy ligand, a monodentate nitrate ion and a water molecule in an elongated octahedral geometry. Adjacent Cu atoms are bridged by the bidentate carboxylate groups into a chain. These chains are further linked by the bridging 4,4′‐bipy ligands, forming an undulated chiral two‐dimensional sheet. O—H...O and N—H...O hydrogen bonds connect the sheets in the [100] direction. This study offers useful information for the engineering of chiral coordination polymers with amino acids and 4,4′‐bipy ligands by considering the ratios of the metal ion and organic components.     

A one‐dimensional zinc(II) coordination polymer incorporating [1,1′‐biphenyl]‐4,4′‐dicarboxylate and N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide ligands

In the title compound, catena‐poly[[[N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide]chloridozinc(II)]‐μ‐[1,1′‐biphenyl]‐4,4′‐dicarboxylato‐[[N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide]chloridozinc(II)]‐μ‐[N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide]], [Zn₂(C₁₄H₈O₄)Cl₂(C₂₆H₂₂N₄O₂)₃]_n, the Zn^II centre is four‐coordinate and approximately tetrahedral, bonding to one carboxylate O atom from a bidentate bridging dianionic [1,1′‐biphenyl]‐4,4′‐dicarboxylate ligand, to two pyridine N atoms from two N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide ligands and to one chloride ligand. The pyridyl ligands exhibit bidentate bridging and monodentate terminal coordination modes. The bidentate bridging pyridyl ligand and the bridging [1,1′‐biphenyl]‐4,4′‐dicarboxylate ligand both lie on special positions, with inversion centres at the mid‐points of their central C—C bonds. These bridging groups link the Zn^II centres into a one‐dimensional tape structure that propagates along the crystallographic b direction. The tapes are interlinked into a two‐dimensional layer in the ab plane through N—H...O hydrogen bonds between the monodentate ligands. In addition, the thermal stability and solid‐state photoluminescence properties of the title compound are reported.     

A three‐dimensional ZnII coordination framework: poly[[μ2‐(E)‐1,2‐bis(pyridin‐4‐yl)ethene][μ4‐(E)‐2,2′‐(diazene‐1,2‐diyl)dibenzoato][μ2‐(E)‐2,2′‐(diazene‐1,2‐diyl)dibenzoato]dizinc(II)]

In the title coordination polymer, [Zn₂(C₁₄H₈N₂O₄)₂(C₁₂H₁₀N₂)]_n, the asymmetric unit contains one Zn^II cation, two halves of 2,2′‐(diazene‐1,2‐diyl)dibenzoate anions (denoted L²⁻) and half of a 1,2‐bis(pyridin‐4‐yl)ethene ligand (denoted bpe). The three ligands lie across crystallographic inversion centres. Each Zn^II centre is four‐coordinated by three O atoms of bridging carboxylate groups from three L²⁻ ligands and by one N atom from a bpe ligand, forming a tetrahedral coordination geometry. Two Zn^II atoms are bridged by two carboxylate groups of L²⁻ ligands, generating a [Zn₂(CO₂)₂] ring. Each loop serves as a fourfold node, which links its four equivalent nodes via the sharing of four L²⁻ ligands to form a two‐dimensional [Zn₂L₄]_n net. These nets are separated by bpe ligands acting as spacers, producing a three‐dimensional framework with a 4⁶6⁴ topology. Powder X‐ray diffraction and solid‐state photoluminescence were also measured.     

A novel parallel interpenetrating two‐dimensional (4,4) network: poly[[μ2‐1,4‐bis(imidazol‐1‐ylmethyl)benzene](μ2‐naphthalene‐1,4‐dicarboxylato)zinc(II)]

In the title coordination compound, [Zn(C₁₂H₆O₄)(C₁₄H₁₄N₄)]_n, the two Zn^II centers exhibit different coordination environments. One Zn^II center is four‐coordinated in a distorted tetrahedral environment surrounded by two carboxylate O atoms from two different naphthalene‐1,4‐dicarboxylate (1,4‐ndc) anions and two N atoms from two distinct 1,4‐bis(imidazol‐1‐ylmethyl)benzene (1,4‐bix) ligands. The coordination of the second Zn^II center comprises two N atoms from two different 1,4‐bix ligands and three carboxylate O atoms from two different 1,4‐ndc ligands in a highly distorted square‐pyramidal environment. The 1,4‐bix ligand and the 1,4‐ndc anion link adjacent Zn^II centers into a two‐dimensional four‐connected (4,4) network. The two (4,4) networks are interpenetrated in a parallel mode.     

A three‐dimensional cadmium(II) coordination polymer: poly[[[μ‐4,4′‐(propane‐1,3‐diyl)dipyridine‐κ2N:N](μ‐3,3′‐thiodipropionato‐κ3O,O′:O)cadmium(II)] monohydrate]

In the title coordination polymer, {[Cd(C₆H₈O₄S)(C₁₃H₁₄N₂)]·H₂O}_n, the Cd^II atom displays a distorted octahedral coordination, formed by three carboxylate O atoms and one S atom from three different 3,3′‐thiodipropionate ligands, and two N atoms from two different 4,4′‐(propane‐1,3‐diyl)dipyridine ligands. The Cd^II centres are bridged through carboxylate O atoms of 3,3′‐thiodipropionate ligands and through N atoms of 4,4′‐(propane‐1,3‐diyl)dipyridine ligands to form two different one‐dimensional chains, which intersect to form a two‐dimensional layer. These two‐dimensional layers are linked by S atoms of 3,3′‐thiodipropionate ligands from adjacent layers to form a three‐dimensional network.     

Bis(μ‐benzene‐1,2‐dicarboxylato)bis{aqua[2‐(2‐chloro‐6‐fluorophenyl)‐1H‐imidazo[4,5‐f][1,10]phenanthroline]cadmium(II)} and its zinc(II) analogue

In the isomorphous title compounds, [Cd₂(C₈H₄O₄)₂(C₁₉H₁₀ClFN₄)₂(H₂O)₂] and [Zn₂(C₈H₄O₄)₂(C₁₉H₁₀ClFN₄)₂(H₂O)₂], the Cd^II centre is seven‐coordinated by two N atoms from one [2‐(2‐chloro‐6‐fluorophenyl)‐1H‐imidazo[4,5‐f][1,10]phenanthroline (L) ligand, one water O atom and four carboxylate O atoms from two different benzene‐1,2‐dicarboxylate (1,2‐bdc) ligands in a distorted pentagonal–bipyramidal coordination, while the Zn^II centre is six‐coordinated by two N atoms from one L ligand, one water O atom and three carboxylate O atoms from two different 1,2‐bdc ligands in a distorted octahedral coordination. Each pair of adjacent metal centres is bridged by two 1,2‐bdc ligands to form a dimeric structure. In the dimer, each L ligand coordinates one metal centre. The dimer is centrosymmetric, with a crystallographic inversion centre midway between the two metal centres. The aromatic interactions lead the dimers to form a two‐dimensional supramolecular architecture. Finally, O—H...O and N—H...O hydrogen bonds reinforce the two‐dimensional structures of the two compounds.     

Poly[[trans‐diaquabis(μ2‐biphenyl‐2,2′‐dicarboxylato)bis(μ2‐4,4′‐bipyridine)dicobalt(II)] biphenyl‐2,2′‐dicarboxylic acid disolvate]

In the title compound, {[Co₂(C₁₄H₈O₄)₂(C₁₀H₈N₂)₂(H₂O)₂]·2C₁₄H₁₀O₄}_n, each Co^II ion is six‐coordinate in a slightly distorted octahedral geometry. Both Co^II ions are located on twofold axes. One is surrounded by two O atoms from two biphenyl‐2,2′‐dicarboxylate (dpa) dianions, two N atoms from two 4,4′‐bipyridine (bpy) ligands and two water molecules, while the second is surrounded by four O atoms from two dpa dianions and two N atoms from two bpy ligands. The coordinated dpa dianion functions as a κ³‐bridge between the two Co^II ions. One carboxylate group of a dpa dianion bridges two adjacent Co^II ions, and one O atom of the other carboxylate group also chelates to a Co^II ion. The Co^II ions are bridged by dpa dianions and bpy ligands to form a chiral sheet. There are several strong intermolecular hydrogen bonds between the H₂dpa solvent molecule and the chiral sheet, which result in a sandwich structure.     

A one‐dimensional coordination polymer with a three‐dimensional supramolecular framework: catena‐poly[[[(3,4,7,8‐tetramethyl‐1,10‐phenanthroline)cadmium(II)]‐μ3‐4,4′‐sulfonyldibenzoato] trihydrate]

In the title mixed‐ligand metal–organic polymeric compound, {[Cd(C₁₄H₈O₆S)(C₁₆H₁₆N₂)]·3H₂O}_n, the asymmetric unit contains a crystallographically unique Cd^II atom, one doubly deprotonated 4,4′‐sulfonyldibenzoic acid (H₂SDBA) ligand, one 3,4,7,8‐tetramethyl‐1,10‐phenanthroline (TMPHEN) molecule and three solvent water molecules. Each Cd^II centre is six‐coordinated by two O atoms from a chelating carboxylate group of a SDBA²⁻ ligand, two O atoms from monodentate carboxylate groups of two different SDBA²⁻ ligands and two N atoms from a chelating TMPHEN ligand. There are two coordination patterns for the carboxylate groups of the SDBA²⁻ ligand, with one in a μ₁‐η¹:η¹ chelating mode and the other in a μ₂‐η¹:η¹ bis‐monodentate mode. Single‐crystal X‐ray diffraction analysis revealed that the title compound is a one‐dimensional double‐chain polymer containing 28‐membered rings based on the [Cd₂(CO₂)₂] rhomboid subunit. More interestingly, a chair‐shaped water hexamer cluster is observed in the compound.     

Poly[bis(μ4‐benzene‐1,2‐dicarboxylato)di‐μ3‐isonicotinato‐dilanthanum(III)]

In the title compound, [La₂(C₈H₄O₄)₂(C₆H₄NO₂)₂]_n, there are two crystallographically independent La centres, both nine‐coordinated in tricapped trigonal prismatic coordination geometries by eight carboxylate O atoms and one pyridyl N atom. The La centres are linked by the carboxylate groups of isonicotinate (IN⁻) and benzene‐1,2‐dicarboxylate (BDC²⁻) ligands to form La–carboxylate chains, which are further expanded into a three‐dimensional framework with nanometre‐sized channels by La—N bonds. In the construction of the resultant architecture, in tricapped trigonal prismatic coordination geometries by eight carboxylate O atoms and one pyridyl N atom, while the BDC ligands link to four different cations each, displaying penta‐ and heptadentate chelating–bridging modes, respectively.     

A two‐dimensional manganese(II) coordination polymer: poly­[[di­aqua­manganese(II)]‐μ‐4,4‐bi­pyridine‐κ2N:N′‐μ‐(p‐phenyl­ene­dioxy­diacetato)‐κ2O:O′]

In the title two‐dimensional coordination polymer, [Mn(1,4‐BDOA)(4,4‐bipy)(H₂O)₂]_n [1,4‐BDOA²⁻ is the p‐phenyl­ene­dioxy­di­acetate dianion (C₁₀H₈O₆) and 4,4‐bipy is 4,4‐bi­pyridine (C₁₀H₈N₂)], each Mn^II atom displays octahedral coordination by two O atoms of the 1,4‐BDOA²⁻ groups, two N atoms of the 4,4‐bipy ligands and two solvent water mol­ecules. The Mn^II atom, 4,4‐bipy ligand and 1,4‐BDOA²⁻ group occupy different inversion centres. Adjacent Mn^II atoms are bridged by 1,4‐BDOA²⁻ groups and 4,4‐bipy ligands, forming a two‐dimensional network with Mn⋯Mn separations of 11.592 (2) and 11.699 (2) Å. Hydro­gen bonds from a water O—H group link the layers in the third dimension.     

A novel cadmium(II) coordination polymer with biphenyl‐3,3′,4,4′‐tetra­carboxylic acid and 4,4′‐bipyridine

A novel cadmium(II) coordination polymer, poly[[[bis­(4,4′‐bipyridine)cadmium(II)]‐μ₃‐4,4′‐dicarboxy­biphenyl‐3,3′‐di­carboxyl­ato] 0.35‐hydrate], {[Cd(C₁₆H₈O₈)(C₁₀H₈N₂)₂]·0.35H₂O}_n, was obtained by reaction of Cd(CH₃COO)₂·3H₂O, 4,4′‐bipyridine (4,4′‐bpy) and biphenyl‐3,3′,4,4′‐tetra­car­boxylic acid (H₄L) under hydro­thermal conditions. Each Cd^II atom lies at the centre of a distorted octa­hedron, coordinated by four O atoms from three H₂L²⁻ ligands and N atoms from two monodentate 4,4′‐bpy ligands. Each H₂L²⁻ ligand coordinates to three Cd^II atoms through two carboxyl­ate groups, one acting as a bridging bidentate ligand and the other in a chelating bidentate fashion. Two Cd atoms, two H₂L²⁻ anions and four 4,4′‐bpy ligands form a ring dimer node, which links into an extended broad zonal one‐dimensional chain along the c axis.     

Poly[aqua(μ2‐benzene‐1,4‐dicarboxylato)(μ2‐4,4′‐bipyridine N,N′‐dioxide)cadmium(II)], a threefold interpenetrating diamond net

In the title compound, [Cd(C₈H₄O₄)(C₁₀H₈N₂O₂)(H₂O)]_n, (I), each Cd^II atom is seven‐coordinated in a distorted monocapped trigonal prismatic coordination geometry, surrounded by four carboxylate O atoms from two different benzene‐1,4‐dicarboxylate (1,4‐bdc) anions, two O atoms from two distinct 4,4′‐bipyridine N,N′‐dioxide (bpdo) ligands and one water O atom. The Cd^II atom and the water O atom are on a twofold rotation axis. The bpdo and 1,4‐bdc ligands are on centers of inversion. Each crystallographically unique Cd^II center is bridged by the 1,4‐bdc dianions and bpdo ligands to give a three‐dimensional diamond framework containing large adamantanoid cages. Three identical such nets are interlocked with each other, thus directly leading to the formation of a threefold interpenetrated three‐dimensional diamond architecture. To the best of our knowledge, (I) is the first example of a threefold interpenetrating diamond net based on both bpdo and carboxylate ligands. There are strong linear O—H...O hydrogen bonds between the water molecules and carboxylate O atoms within different diamond nets. Each diamond net is hydrogen bonded to its two neighbors through these hydrogen bonds, which further consolidates the threefold interpenetrating diamond framework.     

Two‐dimensional ZnII and one‐dimensional CoII coordination polymers based on benzene‐1,4‐dicarboxylate and pyridine ligands

Coordination polymers constructed from metal ions and organic ligands have attracted considerable attention owing to their diverse structural topologies and potential applications. Ligands containing carboxylate groups are among the most extensively studied because of their versatile coordination modes. Reactions of benzene‐1,4‐dicarboxylic acid (H₂BDC) and pyridine (py) with Zn^II or Co^II yielded two new coordination polymers, namely, poly[(μ₄‐benzene‐1,4‐dicarboxylato‐κ⁴O:O′:O′′:O′′′)(pyridine‐κN)zinc(II)], [Zn(C₈H₄O₂)(C₅H₅N)]_n, (I), and catena‐poly[aqua(μ₃‐benzene‐1,4‐dicarboxylato‐κ³O:O′:O′′)bis(pyridine‐κN)cobalt(II)], [Co(C₈H₄O₂)(C₅H₅N)₂(H₂O)]_n, (II). In compound (I), the Zn^II cation is five‐coordinated by four carboxylate O atoms from four BDC²⁻ ligands and one pyridine N atom in a distorted square‐pyramidal coordination geometry. Four carboxylate groups bridge two Zn^II ions to form centrosymmetric paddle‐wheel‐like Zn₂(μ₂‐COO)₄ units, which are linked by the benzene rings of the BDC²⁻ ligands to generate a two‐dimensional layered structure. The two‐dimensional layer is extended into a three‐dimensional supramolecular structure with the help of π–π stacking interactions between the aromatic rings. Compound (II) has a one‐dimensional double‐chain structure based on Co₂(μ₂‐COO)₂ units. The Co^II cations are bridged by BDC²⁻ ligands and are octahedrally coordinated by three carboxylate O atoms from three BDC²⁻ ligands, one water O atom and two pyridine N atoms. Interchain O—H…O hydrogen‐bonding interactions link these chains to form a three‐dimensional supramolecular architecture.     

A two‐dimensional coordination polymer containing a two‐dimensional zinc–carboxylate layer constructed from helical chains: poly[(μ4‐benzene‐1,2‐dicarboxylato)zinc(II)]

The title compound, [Zn(C₈H₄O₄)]_n, consists of one Zn^II cation and one benzene‐1,2‐dicarboxylate dianion (BDC²⁻) as the building unit. The Zn^II cation is four‐coordinated by four carboxylate O atoms from four dianionic BDC²⁻ ligands in a distorted tetrahedral geometry. The Zn^II cations are linked by the BDC²⁻ ligands to generate a structure featuring two‐dimensional zinc–carboxylate layers containing left‐ and right‐handed helical chains. The two‐dimensional layers are stacked along the a direction. The thermal stability of the title compound has been studied.     

A novel 8‐carboxyindeno[1,2‐b]quinoxalin‐11‐one thio­semi­carbazone zinc(II) Schiff base complex

In the novel title binuclear zinc(II) Schiff base complex, bis­(μ‐11‐thio­semicarbazonoindeno[1,2‐b]quinoxaline‐8‐carboxylato)bis­[(dimethyl sulfoxide)zinc(II)] dimethyl sulfoxide tri­solvate, [Zn₂(C₁₇H₉N₅O₂S)₂(C₂H₆OS)₂]·3C₂H₆OS, each Zn^II atom is five‐coordinated and situated in a distorted square‐pyramidal environment, coordinated by two L²⁻ ligands and one dimethyl sulfoxide mol­ecule. Each L²⁻ ligand, which coordinates to two Zn^II atoms, has two parts. One part, acting in a tridentate chelating mode, coordinates to one Zn^II atom through two N atoms and one S atom, while another part coordinates to another Zn^II atom through a monodentate carboxylate group. The whole complex has a dimeric structure. The coordination mode of the nearly planar L²⁻ ligand is quite different from the most common mode for Schiff bases.     

A novel two‐dimensional cobalt(II) complex composed of one‐dimensional twisted pair‐like chains: poly[[tetraaquabis(μ3‐pyridine‐2,5‐dicarboxylato‐κ4N,O2:O5:O5′)dicobalt(II)] dihydrate]

A novel neutral polymer, {[Co₂(C₇H₃NO₄)₂(H₂O)₄]·2H₂O}_n, was hydrothermally synthesized using pyridine‐2,5‐dicarboxylate (2,5‐PDC²⁻) as the organic linker. It features a two‐dimensional layer structure constructed from one‐dimensional {[Co(2,5‐PDC)₂]²⁻}_n chains interlinked by [Co(H₂O)₄]⁺ units. The two Co^II cations occupy special positions, sitting on inversion centres. Each 2,5‐PDC²⁻ anion chelates to one Co^II cation via the pyridine N atom and an O atom of the adjacent carboxylate group, and links to two other Co^II cations in a bridging mode via the O atoms of the other carboxylate group. In this way, the 2,5‐PDC²⁻ ligand connects three neighbouring Co^II centres to form a two‐dimensional network. The two‐dimensional undulating layers are linked by extensive hydrogen bonds to form a three‐dimensional supramolecular structure, with the uncoordinated solvent molecules occupying the interlamellar region.     

A two‐dimensional cadmium(II) coordination polymer based on 5‐(pyridin‐4‐yl)isophthalic acid: poly[[tetraaquabis[μ3‐5‐(pyridin‐4‐yl)isophthalato]dicadmium(II)] pentahydrate]

The title Cd^II compound, {[Cd₂(C₁₃H₇NO₄)₂(H₂O)₄]·5H₂O}_n, was synthesized by the hydrothermal reaction of Cd(NO₃)₂·4H₂O and 5‐(pyridin‐4‐yl)isophthalic acid (H₂L). The asymmetric unit contains two crystallographically independent Cd^II cations, two deprotonated L²⁻ ligands, four coordinated water molecules and five isolated water molecules. One of the Cd^II cations adopts a six‐coordinate octahedral coordination geometry involving three O atoms from one bidentate chelating and one monodentate carboxylate group of two different L²⁻ ligands, one N atom of another L²⁻ ligand and two coordinated water molecules. The second Cd^II cation adopts a seven‐coordinate pentagonal–bipyramidal coordination geometry involving four O atoms from two bidentate chelating carboxylate groups of two different L²⁻ ligands, one N atom of another L²⁻ ligand and two coordinated water molecules. Each L²⁻ ligand bridges three Cd^II cations and, likewise, each Cd^II cation connects to three L²⁻ ligands, giving rise to a two‐dimensional graphite‐like 6³ layer structure. These two‐dimensional layers are further linked by O—H...O hydrogen‐bonding interactions to form a three‐dimensional supramolecular architecture. The photoluminescence properties of the title compound were also investigated.     

A twofold interpenetrating three‐dimensional zinc–organic framework built from naphthalene‐1,4‐dicarboxylate and 4,4′‐bipyridine ligands

A novel three‐dimensional Zn^II complex, poly[[(μ₂‐4,4′‐bipyridine)(μ₄‐naphthalene‐1,4‐dicarboxylato)(μ₂‐naphthalene‐1,4‐dicarboxylato)dizinc(II)] dimethylformamide monosolvate monohydrate], {[Zn₂(C₁₂H₆O₄)₂(C₁₀H₈N₂)]·2C₃H₇NO·H₂O)}_n, has been prepared by the solvothermal assembly of Zn(NO₃)·6H₂O, naphthalene‐1,4‐dicarboxylic acid and 4,4′‐bipyridine. The two crystallographically independent Zn atoms adopt the same four‐coordinated tetrahedral geometry (ZnO₃N) by bonding to three O atoms from three different naphthalene‐1,4‐dicarboxylate (1,4‐ndc) ligands and one N atom from a 4,4′‐bipyridine (bpy) ligand. The supramolecular secondary building unit (SBU) is a distorted paddle‐wheel‐like {Zn₂(COO)₂N₂O₂} unit and these units are linked by 1,4‐ndc ligands within the layer to form a two‐dimensional net parallel to the ab plane, which is further connected by bpy ligands to form the three‐dimensional framework. The single net leaves voids that are filled by mutual interpenetration of an independent equivalent framework in a twofold interpenetrating architecture. The title compound is stable up to 673 K. Excitation and luminescence data observed at room temperature show that it emits bright‐blue fluorescence.