Synthesis and Chloride Affinity of Sterically Demanding Ditopic Lithium Bis(pyrazol‐1‐yl)borates

The synthesis and full characterization of the sterically demanding ditopic lithium bis(pyrazol‐1‐yl)borates Li₂[p‐C₆H₄(B(Ph)pz^R₂)₂] is reported (pz^R = 3‐phenylpyrazol‐1‐yl ( 3 ^Ph), 3‐t‐butylpyrazol‐1‐yl ( 3 ^tBu)). Compound 3 ^Ph crystallizes from THF as THF‐adduct 3 ^Ph(THF)₄ which features a straight conformation with a long Li···Li distance of 12.68(1) Å. Compound 3 ^tBu was found to function as efficient and selective scavenger of chloride ions. In the presence of LiCl it forms anionic complexes [ 3 ^tBuCl]⁻ with a central Li‐Cl‐Li core (Li···Li = 3.75(1) Å).     

[Bis(3,5‐dimethylpyrazol‐1‐yl‐κN2)hydro(pyrazol‐1‐yl‐κN2)borato][(3,5‐dimethylpyrazol‐1‐yl‐κN2)dihydro(pyrazol‐1‐yl‐κN2)borato]nickel(II)

The title compound, [Ni(C₈H₁₂BN₄)(C₁₃H₁₈BN₆)] or Bp′Tp′Ni^II, where Bp′ is (3,5‐dimethylpyrazol‐1‐yl)dihydro(pyrazol‐1‐yl)borate and Tp′ is bis(3,5‐dimethylpyrazol‐1‐yl)hydro(pyrazol‐1‐yl)borate, contains a divalent Ni^II centre bound by the chelating N atoms of the polysubstituted pyrazolylborate ligands. It is shown to lack a strong agostic B—H...Ni interaction, implying that the sixth coordination site is unoccupied in the solid state. This square‐pyramidal complex is the only known crystal structure where the Ni^II centre is pentacoordinated while bonded exclusively to pyrazolyl units. This is of interest with respect to electrochemical and catalytic properties.     

[2,5‐Bis(2,2′‐bipyridyl‐6‐yl)‐3,4‐diazahexa‐2,4‐diene]dichloridomanganese(II): from a mononuclear compound to a three‐dimensional supramolecular framework through C—H...Cl hydrogen bonds and π–π stacking interactions

The title compound, [MnCl₂(C₂₄H₂₀N₆)], has been synthesized and characterized based on the multifunctional ligand 2,5‐bis(2,2′‐bipyridyl‐6‐yl)‐3,4‐diazahexa‐2,4‐diene (L). The Mn^II centre is five‐coordinate with an approximately square‐pyramidal geometry. The L ligand acts as a tridendate chelating ligand. The mononuclear molecules are bridged into a one‐dimensional chain by two C—H...Cl hydrogen bonds. These chains are assembled into a two‐dimensional layer through π–π stacking interactions between adjacent uncoordinated bipyridyl groups. Furthermore, a three‐dimensional supramolecular framework is attained through π–π stacking interactions between adjacent coordinated bipyridyl groups.     

Polymeric [dihydrobis(pyrazol‐1‐yl)borato]potassium(I) and three dihydrobis(pyrazol‐1‐yl)borate–magnesium(I) compounds obtained by disproportionation of the Grignard reagent

Reaction of the Grignard reagent with polydentate nitrogen‐donor ligands yields new species with rare magnesium coordination and possible catalytic activity. In the first of the title compounds, poly[[μ₄‐dihydrobis(pyrazol‐1‐yl)borato‐κ²N,N′]potassium(I)], [K(C₆H₈BN₄)]_n, (I), polymeric chains form a two‐dimensional network in the [100] plane. Each potassium ion is coordinated by four N atoms of pyrazolyl ligands, while weak (μ‐BH)...K⁺ interactions additionally stabilize the structure. The K and B atoms both lie on a mirror plane. In three new structures obtained by disproportionation of the Grignard reagent, each Mg atom is bound to a κ²N,N′‐type ligand, forming the basal plane, and tetrahydrofuran molecules occupy the axial positions. Di‐μ‐chlorido‐bis[dihydridobis(pyrazol‐1‐yl)borato]tris(tetrahydrofuran)dimagnesium(II), [Mg₂(C₆H₈BN₄)₂Cl₂(C₄H₈O)₃], (II), adopts a dimeric structure with μ‐Cl—Mg interactions. One of the Mg atoms has an octahedral coordination, while the other has a distorted square‐pyramidal environment. However, in the bis‐chelate compounds bis[dihydridobis(pyrazol‐1‐yl)borato‐κ²N,N′](tetrahydrofuran‐κO)magnesium(II), [Mg(C₆H₈BN₄)₂(C₄H₈O)], (III), and bis[dihydridobis(pyrazol‐1‐yl)borato‐κ²N,N′]bis(tetrahydrofuran‐κO)magnesium(II), [Mg(C₆H₈BN₄)₂(C₄H₈O)₂], (IV), the Mg atoms have square‐pyramidal and octahedral environments, respectively. The Mg atom in (IV) lies on an inversion centre.     

In situ synthesis of mononuclear copper(II) complexes of the new tridentate ligand bis[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methyl]amine

Two mononuclear copper complexes, {bis[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl‐κN²)methyl]amine‐κN}(3,5‐dimethyl‐1H‐pyrazole‐κN²)(perchlorato‐κO)copper(II) perchlorate, [Cu(ClO₄)(C₅H₈N₂)(C₁₂H₁₉N₅)]ClO₄, (I), and {bis[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl‐κN²)methyl]amine‐κN}bis(3,5‐dimethyl‐1H‐pyrazole‐κN²)copper(II) bis(hexafluoridophosphate), [Cu(C₅H₈N₂)₂(C₁₂H₁₉N₅)](PF₆)₂, (II), have been synthesized by the reactions of different copper salts with the tripodal ligand tris[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methyl]amine (TDPA) in acetone–water solutions at room temperature. Single‐crystal X‐ray diffraction analysis revealed that they contain the new tridentate ligand bis[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methyl]amine (BDPA), which cannot be obtained by normal organic reactions and has thus been captured in the solid state by in situ synthesis. The coordination of the Cu^II ion is distorted square pyramidal in (I) and distorted trigonal bipyramidal in (II). The new in situ generated tridentate BDPA ligand can act as a meridional or facial ligand during the process of coordination. The crystal structures of these two compounds are stabilized by classical hydrogen bonding as well as intricate nonclassical hydrogen‐bond interactions.     

Carbonyl­[di­hydro­bis­(pyrazol‐1‐yl‐κN2)­borato]­hydrido­bis­(tri‐p‐tolyl­phosphine‐κP)­ruthenium(II)

The title compound, [RuH(C₆H₈BN₄)(C₂₁H₂₁P)₂(CO)], possesses two trans‐disposed tri‐p‐tolyl­phosphines in axial positions and the remaining ligands in equatorial positions. The overall geometry of the Ru^II ion is a distorted octahedral structure. The P—Ru—P axis deviates from linearity by about 13°. This distortion arises mainly from the steric congestion between the bulky phosphine moieties and the tetrahedral di­hydro­bis­(pyrazol‐1‐yl)­borate ligands.     

A one‐dimensional coordination polymer formed from the reaction of 1,1‐diphenyl‐3,3′‐[(1R,2R)‐cyclohexane‐1,2‐diylbis(azanediyl)]dibut‐2‐en‐1‐one with MnCl2·4H2O

In the title coordination polymer, catena‐poly[[dichloridomanganese(II)]‐μ‐1,1‐diphenyl‐3,3′‐[(1R,2R)‐cyclohexane‐1,2‐diylbis(azaniumylylidene)]dibut‐1‐en‐1‐olate‐κ²O:O′], [MnCl₂(C₂₆H₃₀N₂)]_n, synthesized by the reaction of the chiral Schiff base ligand 1,1‐diphenyl‐3,3′‐[(1R,2R)‐cyclohexane‐1,2‐diylbis(azanediyl)]dibut‐2‐en‐1‐one (L) with MnCl₂·4H₂O, the asymmetric unit contains one crystallographically unique Mn^II ion, one unique spacer ligand, L, and two chloride ions. Each Mn^II ion is four‐coordinated in a distorted tetrahedral coordination environment by two O atoms from two L ligands and by two chloride ligands. The Mn^II ions are bridged by L ligands to form a one‐dimensional chain structure along the a axis. The chloride ligands are monodentate (terminal). The ligand is in the zwitterionic enol form and displays intramolecular ionic N⁺—H...O⁻ hydrogen bonding and π–π interactions between pairs of phenyl rings which strengthen the chains.     

Bis[bis­(3‐phenyl­pyrazol‐1‐yl)­(pyrazol‐1‐yl)­methane]­copper(II) bis­(per­chlor­ate) acetonitrile disolvate

The title copper(II) complex, [Cu(C₂₂H₁₈N₆)₂](ClO₄)₂·2C₂H₃N, comprises two neutral substituted tris­(pyrazol‐1‐yl)­methane ligands bonded to a central Cu^II ion, which is positioned on a crystallographic inversion center. Six Cu—N bonds are arranged in a distorted octa­hedral fashion. The unsubstituted pyrazole rings on each ligand are oriented trans with respect to each other, inter­digitated with the two 3‐phenyl­pyrazole rings of the other ligand.     

Binuclear and chain‐structure zinc(II) complexes constructed from 3,4‐dimethoxy‐trans‐cinnamic acid and N‐donor coligands 4‐(1H‐pyrazol‐3‐yl)pyridine and 4,4′‐bipyridine

3,4‐Dimethoxy‐trans‐cinnamic acid (Dmca) reacts with zinc sulfate in the presence of 4‐(1H‐pyrazol‐3‐yl)pyridine (L₁) or 4,4′‐bipyridine (L₂) under hydrothermal conditions to afford two mixed‐ligand coordination complexes, namely tetrakis(μ‐3,4‐dimethoxy‐trans‐cinnamato‐κ²O:O′)bis[[4‐(1H‐pyrazol‐3‐yl)pyridine]zinc(II)] heptahydrate, [Zn₂(C₁₁H₁₁O₄)₄(C₈H₇N₃)₂]·7H₂O or [Zn₂(Dmca)₄(L₁)₂]·7H₂O, (I), and catena‐poly[[bis(3,4‐dimethoxy‐trans‐cinnamato‐κO)zinc(II)]‐μ‐4,4′‐bipyridine‐κ²N:N′], [Zn(C₁₁H₁₁O₄)₂(C₁₀H₈N₂)]_n or [Zn(Dmca)₂(L₂)]_n, (II). The Zn^II centres in the two compounds display different coordination polyhedra. In complex (I), the Zn^II cation is five‐coordinated with a pseudo‐square‐pyramidal geometry, while in complex (II) the Zn^II cation sits on a twofold axis and adopts a distorted tetrahedral coordination environment. Complex (I) features a centrosymmetric binuclear paddle‐wheel‐like structure, while complex (II) shows a chain structure. This study emphasizes the significant effect of the coordination mode of both carboxylate‐group and N‐donor coligands on the formation of complex structures.     

Two nickel(II) bis[(pyridin‐2‐yl)methyl]amine complexes with homophthalic and benzene‐1,2,4,5‐tetracarboxylic acids

Two new Ni^II complexes involving the ancillary ligand bis[(pyridin‐2‐yl)methyl]amine (bpma) and two different carboxylate ligands, i.e. homophthalate [hph; systematic name: 2‐(2‐carboxylatophenyl)acetate] and benzene‐1,2,4,5‐tetracarboxylate (btc), namely catena‐poly[[aqua{bis[(pyridin‐2‐yl)methyl]amine‐κ³N,N′,N′′}nickel(II)]‐μ‐2‐(2‐carboxylatophenyl)aceteto‐κ²O:O′], [Ni(C₉H₆O₄)(C₁₂H₁₃N₃)(H₂O)]_n, and (μ‐benzene‐1,2,4,5‐tetracarboxylato‐κ⁴O¹,O²:O⁴,O⁵)bis(aqua{bis[(pyridin‐2‐yl)methyl]amine‐κ³N,N′,N′′}nickel(II)) bis(triaqua{bis[(pyridin‐2‐yl)methyl]amine‐κ³N,N′,N′′}nickel(II)) benzene‐1,2,4,5‐tetracarboxylate hexahydrate, [Ni₂(C₁₀H₂O₈)(C₁₂H₁₃N₃)₂(H₂O)₂]·[Ni(C₁₂H₁₃N₃)(H₂O)₃]₂(C₁₀H₂O₈)·6H₂O, (II), are presented. Compound (I) is a one‐dimensional polymer with hph acting as a bridging ligand and with the chains linked by weak C—H...O interactions. The structure of compound (II) is much more complex, with two independent Ni^II centres having different environments, one of them as part of centrosymmetric [Ni(bpma)(H₂O)]₂(btc) dinuclear complexes and the other in mononuclear [Ni(bpma)(H₂O)₃]²⁺ cations which (in a 2:1 ratio) provide charge balance for btc⁴⁻ anions. A profuse hydrogen‐bonding scheme, where both coordinated and crystal water molecules play a crucial role, provides the supramolecular linkage of the different groups.     

Controllable assembly of a three‐dimensional metal–organic supramolecular framework displaying hydrogen‐bonding and π–π stacking interactions

The complex poly[[aqua(μ₂‐phthalato‐κ²O¹:O²){μ₃‐2‐[3‐(pyridin‐2‐yl)‐1H‐pyrazol‐1‐yl]acetato‐κ⁴N²,N³:O:O′}{μ₂‐2‐[3‐(pyridin‐2‐yl)‐1H‐pyrazol‐1‐yl]acetato‐κ³N²,N³:O}dizinc(II)] dihydrate], {[Zn₂(C₁₀H₈N₃O₂)₂(C₈H₄O₄)(H₂O)]·2H₂O}_n, has been prepared by solvothermal reaction of 2‐[3‐(pyridin‐2‐yl)‐1H‐pyrazol‐1‐yl]acetonitrile (PPAN) with zinc(II). Under hydrothermal conditions, PPAN is hydrolyzed to 2‐[3‐(pyridin‐2‐yl)‐1H‐pyrazol‐1‐yl]acetate (PPAA⁻). The structure determination reveals that the complex is a one‐dimensional double chain containing cationic [Zn₄(PPAA)₄]⁴⁺ structural units, which are further extended by bridging phthalate ligands. The one‐dimensional chains are extended into a three‐dimensional supramolecular architecture via hydrogen‐bonding and π–π stacking interactions.     

A two‐dimensional zinc(II) coordination polymer created via in situ ligand synthesis involving C—N bond formation

The novel Zn^II coordination polymer poly[{μ₄‐2‐[3‐(pyridin‐2‐yl)‐1H‐pyrazol‐3‐yl]butanedioato}zinc(II)], [Zn(C₁₂H₉N₃O₄)]_n, has been synthesized hydrothermally and structurally characterized. The results demonstrate that the complex shows two‐dimensional neutral wave‐like layers. The complex was prepared by the conjugate addition reaction of 2‐(1H‐pyrazol‐3‐yl)pyridine to cis‐fumaric acid in the presence of Zn(OAc)₂·2H₂O (OAc is acetate) at 413 K.     

Synthesis,crystal structures and magnetic and electrochemiluminescence properties of three manganese(II) complexes

Three novel complexes, namely, penta‐μ‐acetato‐bis(μ₂‐2‐{[2‐(6‐chloropyridin‐2‐yl)hydrazinylidene]methyl}‐6‐methoxyphenolato)‐μ‐formato‐tetramanganese(II), [Mn₄(C₁₃H₁₁ClN₃O₂)₂(C₂H₃O₂)_5.168(CHO₂)_0.832], 1 , hexa‐μ₂‐acetato‐bis(μ₂‐2‐{[2‐(6‐bromopyridin‐2‐yl)hydrazinylidene]methyl}‐6‐methoxyphenolato)tetramanganese(II), [Mn₄(C₁₃H₁₁BrN₃O₂)₂(C₂H₃O₂)₆], 2 , and catena‐poly[[μ₂‐acetato‐acetatoaqua(μ₂‐2‐{[2‐(6‐chloropyridin‐2‐yl)hydrazinylidene]methyl}‐6‐methoxyphenolato)dimanganese(II)]‐μ₂‐acetato], [Mn₂(C₁₃H₁₁ClN₃O₂)(C₂H₃O₂)₃(H₂O)]_n, 3 , have been synthesized using solvothermal methods. Complexes 1 – 3 were characterized by IR spectroscopy, elemental analysis and single‐crystal X‐ray diffraction. Complexes 1 and 2 are tetranuclear manganese clusters, while complex 3 has a one‐dimensional network based on tetranuclear Mn₄(L¹)₂(CH₃COO)₆(H₂O)₂ building units (L¹ is 2‐{[2‐(6‐chloropyridin‐2‐yl)hydrazinylidene]methyl}‐6‐methoxyphenolate). Magnetic studies reveal that complexes 1 – 3 display dominant antiferromagnetic interactions between Mn^II ions through μ₂‐O bridges. In addition, 1 – 3 also display favourable electrochemiluminescence (ECL) properties.     

catena‐Poly[[di‐μ2‐aqua‐hexaaquabis(μ3‐4‐oxidopyridine‐2,6‐dicarboxylato)trimanganese(II)] trihydrate]: a new one‐dimensional coordination polymer based on a trinuclear MnII complex of chelidamic acid

4‐Hydroxypyridine‐2,6‐dicarboxylic acid (chelidamic acid, hypydc_[H]H₂) reacts with MnCl₂·2H₂O in the presence of piperazine in water to afford the title complex, {[Mn₃(C₇H₂NO₅)₂(H₂O)₈]·3H₂O}_n or {[Mn₃(hypydc)₂(H₂O)₈]·3H₂O}_n. This compound is a one‐dimensional coordination polymer, with the twofold symmetric repeat unit containing three metal centres. Two different coordination geometries are observed for the two independent Mn^II metal centres, viz. a distorted pentagonal bipyramid and a distorted octahedron. The 4‐oxidopyridine‐2,6‐dicarboxylate anions and two of the water molecules act as bridging ligands. The zigzag‐like geometry of the coordination polymer is stabilized by hydrogen bonds. O—H...O and C—H...O hydrogen bonds and water clusters consolidate the three‐dimensional network structure.     

An iron(III) complex salt containing pyrazole as both ligand and counter‐ion: bis(1H‐pyrazol‐2‐ium) pentacyanido(1H‐pyrazole‐κN2)ferrate(III)

The title compound, (C₃H₅N₂)₂[Fe(CN)₅(C₃H₄N₂)], is composed of a mononuclear [Fe(CN)₅(pyrazole)]²⁻ dianion and two 1H‐pyrazol‐2‐ium cations. A three‐dimensional supramolecular network is formed through a rich scheme of N—H...N hydrogen bonds and C—H...π interactions among the cations and anions.     

A three‐dimensional cyanide‐bridged heterometallic coordination polymer: poly[[diacetonitrilediaqua[μ2‐3,6‐bis(pyridin‐2‐yl)‐1,2,4,5‐tetrazine‐κ4N1,N6:N3,N4]tetra‐μ‐cyanido‐tetracyanidodimanganese(II)molybdate(IV)] dihydrate]

A metal coordination polymer, {[Mn₂Mo(CN)₈(C₁₂H₈N₆)(CH₃CN)₂(H₂O)₂]·2H₂O}_n, has been synthesized by the reaction of Mn(ClO₄)₂·6H₂O with 3,6‐bis(pyridin‐2‐yl)‐1,2,4,5‐tetrazine (bptz) and (Bu₃N)₃[Mo(CN)₈] at room temperature. The polymer was characterized by IR spectroscopy, elemental analysis and X‐ray diffraction, and the magnetic properties were also investigated. The X‐ray diffraction analysis reveals that the compound is a new three‐dimensional coordination polymer with a PtS‐type network. Magnetic investigation shows antiferromagnetic coupling between adjacent Mn²⁺ cations.     

Two new cadmium(II) coordination polymers based on bis(1,2,4‐triazol‐1‐yl)alkane ligands and pyrazine‐2,3‐dicarboxylic acid

Assemblies of pyrazine‐2,3‐dicarboxylic acid and Cd^II in the presence of bis(1,2,4‐triazol‐1‐yl)butane or bis(1,2,4‐triazol‐1‐yl)ethane under ambient conditions yielded two new coordination polymers, namely poly[[tetraaqua[μ₂‐1,4‐bis(1,2,4‐triazol‐1‐yl)butane‐κ²N⁴:N^4′]bis(μ₂‐pyrazine‐2,3‐dicarboxylato‐κ³N¹,O²:O³)dicadmium(II)] dihydrate], {[Cd₂(C₆H₂N₂O₄)₂(C₈H₁₂N₆)(H₂O)₄]·2H₂O}_n, (I), and poly[[diaqua[μ₂‐1,2‐bis(1,2,4‐triazol‐1‐yl)ethane‐κ²N⁴:N^4′]bis(μ₃‐pyrazine‐2,3‐dicarboxylato‐κ⁴N¹,O²:O³:O^3′)dicadmium(II)] dihydrate], {[Cd₂(C₆H₂N₂O₄)₂(C₆H₈N₆)(H₂O)₂]·2H₂O}_n, (II). Complex (I) displays an interesting two‐dimensional wave‐like structure and forms a distinct extended three‐dimensional supramolecular structure with the help of O—H...N and O—H...O hydrogen bonds. Complex (II) has a three‐dimensional framework structure in which hydrogen bonds of the O—H...N and O—H...O types are found.     

Synthesis and crystal structures of some bis(3‐methyl‐1H‐indol‐2‐yl)(salicyl)methanes

Four 2,2′‐bisindolylmethanes (BIMs), a useful class of polyindolyl species joined to a central carbon, were synthesized using salicylaldehyde derivatives and simple acid catalysis; these are 2‐[bis(3‐methyl‐1H‐indol‐2‐yl)methyl]‐6‐methylphenol, (IIa), 2‐[bis(3‐methyl‐1H‐indol‐2‐yl)methyl]‐4,6‐dichlorophenol, (IIb), 2‐[bis(3‐methyl‐1H‐indol‐2‐yl)methyl]‐4‐nitrophenol, (IIc), and 2‐[bis(3‐methyl‐1H‐indol‐2‐yl)methyl]‐4,6‐di‐tert‐butylphenol, (IId). BIMs (IIa) and (IIb) were characterized crystallographically as the dimethyl sulfoxide (DMSO) disolvates, i.e. C₂₆H₂₄N₂O·2C₂H₆OS and C₂₅H₂₀Cl₂N₂O·2C₂H₆OS, respectively. Both form strikingly similar one‐dimensional hydrogen‐bonding chain motifs with the DMSO solvent molecules. BIM (IIa) packs into double layers of chains whose orientations alternate every double layer, while (IIb) forms more simply packed chains along the a axis. BIM (IIa) has a remarkably long c axis.     

Unusual Coordination Modes of Tris(pyrazol‐1‐yl)borates: Synthesis and Solid State Structures of Sodium[(dimethylamino)tris(pyrazol‐1‐yl)borate], Potassium[(dimethylamino)tris(pyrazol‐1‐yl)borate], and Potassium[phenyltris(pyrazol‐1‐yl)borate]

We report the optimized syntheses and the solid state structures of the alkali metal tris(pyrazol‐1‐yl)borates M[Me₂NBpz₃] (M = Na⁺ ( 1 ), K⁺ ( 2 ); pz = pyrazol‐1‐yl) and K[PhBpz₃] ( 3 ). Even though 1 and 2 consist of polymeric chains in the solid state, it is possible to identify subunits where the [Me₂NBpz₃]^? ion acts as tridentate ligand towards Na⁺ and K⁺ and binds via two of its pyrazolyl rings and its dimethylamino nitrogen atom (κ³N_pz,N_pz,N_NMe). In 3 , the ligand [PhBpz₃]^? employs two pyrazolyl donors and the π‐face of its phenyl substituent for potassium coordination (κ³N,N,C).     

A novel two‐dimensional MnII coordination polymer with 1,2‐bis­(imidazol‐1‐yl)­ethane

In the crystal structure of the title complex, poly­[[di­azido­manganese(II)]‐di‐μ‐1,2‐bis­(imidazol‐1‐yl)­ethane‐κ⁴N³:N^3′], [Mn(N₃)₂(C₈H₁₀N₄)₂]_n or [Mn(N₃)₂(bim)₂]_n, where bim is 1,2‐­bis(imidazol‐1‐yl)­ethane, each Mn^II atom is six‐coordinated in a distorted octahedral coordination environment to four N atoms from four bim ligands and two N atoms from two azide ligands. The Mn^II atoms, which lie on inversion centres, are bridged by four bim ligands to form a two‐dimensional (4,4)‐network. The azide ligands are monodentate (terminal).