Synthesis of 5‐Aryl‐3‐(methylsulfanyl)‐1H‐pyrazoles via Three‐Component Reaction of 1,1‐Bis(methylsulfanyl)‐2‐nitroethene,Aromatic Aldehydes,and Hydrazine

An efficient approach for the preparation of functionalized 5‐aryl‐3‐(methylsulfanyl)‐1H‐pyrazoles 2 is described. This three‐component reaction between benzaldehydes 1 , NH₂NH₂?H₂O, and 1,1‐bis(methylsulfanyl)‐2‐nitroethene proceeds in EtOH under reflux conditions in good‐to‐excellent yields. The structures of 2 were corroborated spectroscopically (IR, ¹H‐ and ¹³C‐NMR, and EI‐MS). A plausible mechanism for this type of reaction is proposed (Scheme 2).     

Palladium‐catalyzed cyclization of β‐bromo‐α,β‐unsaturated ketones with arylhydrazines leading to 3‐substituted 1‐aryl‐1 H‐pyrazoles

β‐Bromo‐α,β‐unsaturated ketones are condensed with arylhydrazines to form hydrazones, which are in situ intramolecularly cyclized into 3‐substituted 1‐aryl‐1 H‐pyrazoles under a catalytic system of Pd(OAc)₂/1,3‐bis(diphenylhosphino)propane (dppp)/NaO^tBu. Copyright © 2012 John Wiley & Sons, Ltd.     

Investigation of Some Functionalization Reactions of 4‐Benzoyl‐5‐phenyl‐1‐(4‐methoxyphenyl)‐1H‐pyrazole‐3‐carbonyl Chloride and Their Antimicrobial Activity

The 1H‐pyrazole‐3‐carboxylic acid 1 was converted via reactions of its acid chloride 3 with various asymmetrical disubstituted urea and alcohol derivatives into the corresponding novel 4‐benzoyl‐N‐(N′,N′‐dialkylcarbamyl)‐1‐(4‐methoxyphenyl)‐5‐phenyl‐1H‐pyrazole‐3‐carboxamide 4a , b and alkyl 4‐benzoyl‐1‐(4‐methoxyphenyl)‐5‐phenyl‐1H‐pyrazole‐3‐carboxylate 7a‐c , respectively, in good yields (57%‐78%). Friedel‐Crafts reactions of 3 with aromatic compouns for 15 min.‐2 h led to the formation of the 4‐3‐diaroyl‐1‐(4‐hydroxyphenyl)‐5‐phenyl‐1H‐pyrazoles 9a‐c , 4‐benzoyl‐1‐(4‐methoxyphenyl)‐3‐aroyl‐5‐phenyl‐1H‐pyrazoles 10a , b and than from the acylation reactions of 9a‐c were obtained the 3,4‐diaroyl‐1‐(4‐acyloxyphenyl)‐5‐phenyl‐1H‐pyrazoles 13a‐d . The structures of all new synthesized compounds were established by NMR experiments such as ¹H, and ¹³C, as well as 2D COSY and IR spectroscopic data, and elemental analyses. All the compounds were evaluated for their antimicrobial activities (agar diffusion method) against eight bacteria and two yeasts.     

1,3‐Dipolar Cycloadditions of Ethyl 2‐Diazo‐3,3,3‐trifluoropropanoate to Alkynes and [1,5] Sigmatropic Rearrangements of the Resulting 3H‐Pyrazoles: Synthesis of Mono‐, Bis‐ and Tris(trifluoromethyl)‐Substituted Pyrazoles

The 1,3‐dipolar cycloadditions of ethyl 2‐diazo‐3,3,3‐trifluoropropanoate with electron‐rich and electron‐deficient alkynes, as well as the van Alphen? Hüttel rearrangements of the resulting 3H‐pyrazoles were investigated. These reactions led to a series of CF₃‐substituted pyrazoles in good overall yields. Phenyl‐ and diphenylacetylene proved to be unreactive, but, at high temperature, the diazoalkane and phenylacetylene furnished a cyclopropene derivative. As expected, the 1,3‐dipolar cycloaddition to the ynamine occurred much faster than those to electron‐deficient alkynes. With one exception, all cycloadditions proceeded with excellent regioselectivities. The [1,5] sigmatropic rearrangement of the primary 3H‐pyrazoles provided products with shifted acyl groups; products resulting from the migration of a CF₃ group were not detected. In agreement with literature reports, this rearrangement occurs faster with 3H‐pyrazoles bearing electron‐withdrawing substituents.     

Synthesis,Crystal Structures,and Fungicidal Activity of Novel 1,5‐Diaryl‐3‐(glucopyranosyloxy)‐1H‐pyrazoles

Five novel pyrazole‐coupled glucosides, 1,5‐diaryl‐1H‐pyrazol‐3‐yl 2,3,4,6‐tetra‐O‐acetyl‐β‐D ‐glucopyranosides 5a – 5e , were synthesized by the phase‐transfer catalytic reaction of 1,5‐diaryl‐1H‐pyrazol‐3‐ols 4a – 4e with acetobromo‐α‐D ‐glucose in H₂O/CHCl₃ under alkaline conditions, using Bu₄N⁺Br^? as catalyst. Then, glucosides 5a – 5c were deacetylated in a solution of Na₂CO₃/MeOH to yield the 1,5‐diaryl‐3‐(β‐D ‐glucopyranosyloxy)‐1H‐pyrazoles 6a – 6c . Their structures were characterized by ¹H,¹H‐COSY, ¹H‐, ¹³C‐, and ¹⁹F‐NMR spectroscopy, as well as elemental analysis. The structures of 5d and 6c were also determined by single‐crystal X‐ray diffraction analysis. A preliminary in vitro bioassay indicated that compounds 4e and 5d exhibited excellent‐to‐medium fungicidal activity against Sclerotinia sclerotiorum at the dosage of 10 μg/ml.     

Reactions of Methyl Diazoacetate with (E)‐ and (Z)‐1,2‐Bis(trifluoromethyl)ethene‐1,2‐dicarbonitrile: Novel and Unanticipated Pathways

The cycloadditions of methyl diazoacetate to 2,3‐bis(trifluoromethyl)fumaronitrile ((E)‐ BTE ) and 2,3‐bis(trifluoromethyl)maleonitrile ((Z)‐ BTE ) furnish the 4,5‐dihydro‐1H‐pyrazoles 13 . The retention of dipolarophile configuration proceeds for (E)‐ BTE with > 99.93% and for (Z)‐ BTE with > 99.8% (CDCl₃, 25°), suggesting concertedness. Base catalysis (1,4‐diazabicyclo[2.2.2]octane (DABCO), proton sponge) converts the cycloadducts, trans‐ 13 and cis‐ 13 , to a 94 : 6 equilibrium mixture (CDCl₃, r.t.); the first step is N‐deprotonation, since reaction with methyl fluorosulfonate affords the 4,5‐dihydro‐1‐methyl‐1H‐pyrazoles. Competing with the cis/trans isomerization of 13 is the formation of a bis(dehydrofluoro) dimer (two diastereoisomers), the structure of which was elucidated by IR, ¹⁹F‐NMR, and ¹³C‐NMR spectroscopy. The reaction slows when DABCO is bound by HF, but F^? as base keeps the conversion to 22 going and binds HF. The diazo group in 22 suggests a common intermediate for cis/trans isomerization of 13 and conversion to 22 : reversible ring opening of N‐deprotonated 13 provides 18 , a derivative of methyl diazoacetate with a carbanionic substituent. Mechanistic comparison with the reaction of diazomethane and dimethyl 2,3‐dicyanofumarate, a related tetra‐acceptor‐ethylene, brings to light unanticipated divergencies.     

Characterization of 4,5‐Dihydro‐1H‐Pyrazole Derivatives by 13C NMR Spectroscopy

The ¹³ C NMR resonances of 19 1‐acyl‐3‐(2‐nitro‐5‐substitutedphenyl)‐4,5‐dihydro‐1H‐pyrazoles, and 19 1‐acyl‐3‐(2‐amino‐5‐substituted)‐4,5‐dihydro‐1H‐pyrazoles, were completely assigned using the concerted application of one‐ and two‐dimensional NMR experiments (DEPT, gs‐HSQC and gs‐HMBC). Copyright © 2012 John Wiley & Sons, Ltd.     

Directing/Protecting‐Group‐Free Synthesis of Tetraaryl‐Substituted Pyrazoles through Four Direct Arylations on an Unsubstituted Pyrazole Scaffold

A directing/protecting‐group‐free synthesis of 1,3,4,5‐tetraaryl‐substituted pyrazoles was achieved through four transition metal‐catalyzed direct arylations. Various pyrazoles with four different aryl rings were obtained using readily available reagents from an unsubstituted pyrazole. Two aryl‐substituted pyrazoles showed intense violet fluorescence, high quantum yields (Φ_f=0.68, 0.64), and large Stokes shifts (19000, 15200 cm^?1).     

Microwave‐assisted Synthesis of Novel 3,4‐Bis‐chalcone‐N‐arylpyrazoles and Their Anti‐inflammatory Activity

A series of 3,4‐bis‐chalcone‐N‐arylpyrazoles 3a‐h was prepared conveniently from diacetyl pyrazoles 2a,b . All reactions were carried out under conventional thermal heating and/or microwave irradiation. The structure of the latter functionally pyrazoles was confirmed under the bases of their IR, mass, ¹H NMR and ¹³C NMR. The X‐ray diffraction of compound 3e not only confirmed the chemical structure of 3a‐h , but also showed the E configuration of their chalcone moieties. Treatment of compound 3e with phenyl hydrazine in presence of acetic acid afforded the tri‐pyrazle 4 . The anti‐inflammatory activity of the newly synthesized compounds was investigated. Some of these compounds showed a moderate activity when compared with indomethacin as a reference drug. The combination between chalcone and pyrazole moieties revealed a variable effect in anti‐inflammatory activity.     

One‐Pot Synthesis of Functionalized 3‐Aryl‐1‐phenyl‐1H‐pyrazoles from Hydrazonoyl Chlorides and Acetylenic Esters in the Presence of Ph3P

The zwitterionic 1 : 1 intermediates generated by addition of Ph₃P to acetylenic esters is trapped by 1‐[(aryl)chloromethylene]‐2‐phenylhydrazines (=N‐phenylarenecarbohydrazonoyl chlorides) to yield functionalized 3‐aryl‐1‐phenyl‐1H‐pyrazoles in good yields.     

A two‐dimensional cadmium(II) coordination polymer constructed from 4‐carboxy‐1‐(4‐carboxylatobenzyl)‐2‐propyl‐1H‐imidazole‐5‐carboxylate and 1‐(4‐carboxylatobenzyl)‐2‐propyl‐1H‐imidazole‐4‐carboxylate ligands

Crystals of poly[[aqua[μ₃‐4‐carboxy‐1‐(4‐carboxylatobenzyl)‐2‐propyl‐1H‐imidazole‐5‐carboxylato‐κ⁵O¹O^1′:N³,O⁴:O⁵][μ₄‐1‐(4‐carboxylatobenzyl)‐2‐propyl‐1H‐imidazole‐4‐carboxylato‐κ⁷N³,O⁴:O⁴,O^4′:O¹,O^1′:O¹]cadmium(II)] monohydrate], {[Cd₂(C₁₅H₁₄N₂O₄)(C₁₆H₁₄N₂O₆)(H₂O)]·H₂O}_n or {[Cd₂(Hcpimda)(cpima)(H₂O)]·H₂O}_n, (I), were obtained from 1‐(4‐carboxybenzyl)‐2‐propyl‐1H‐imidazole‐4,5‐dicarboxylic acid (H₃cpimda) and cadmium(II) chloride under hydrothermal conditions. The structure indicates that in‐situ decarboxylation of H₃cpimda occurred during the synthesis process. The asymmetric unit consists of two Cd²⁺ centres, one 4‐carboxy‐1‐(4‐carboxylatobenzyl)‐2‐propyl‐1H‐imidazole‐5‐carboxylate (Hcpimda²⁻) anion, one 1‐(4‐carboxylatobenzyl)‐2‐propyl‐1H‐imidazole‐4‐carboxylate (cpima²⁻) anion, one coordinated water molecule and one lattice water molecule. One Cd²⁺ centre, i.e. Cd1, is hexacoordinated and displays a slightly distorted octahedral CdN₂O₄ geometry. The other Cd centre, i.e. Cd2, is coordinated by seven O atoms originating from one Hcpimda²⁻ ligand and three cpima²⁻ ligands. This Cd²⁺ centre can be described as having a distorted capped octahedral coordination geometry. Two carboxylate groups of the benzoate moieties of two cpima²⁻ ligands bridge between Cd2 centres to generate [Cd₂O₂] units, which are further linked by two cpima²⁻ ligands to produce one‐dimensional (1D) infinite chains based around large 26‐membered rings. Meanwhile, adjacent Cd1 centres are linked by Hcpimda²⁻ ligands to generate 1D zigzag chains. The two types of chains are linked through a μ₂‐η² bidentate bridging mode from an O atom of an imidazole carboxylate unit of cpima²⁻ to give a two‐dimensional (2D) coordination polymer. The simplified 2D net structure can be described as a 3,6‐coordinated net which has a (4³)₂(4⁶.6⁶.8³) topology. Furthermore, the FT–IR spectroscopic properties, photoluminescence properties, powder X‐ray diffraction (PXRD) pattern and thermogravimetric behaviour of the polymer have been investigated.     

2, 4‐Dimethylpenta‐1, 3‐dien‐ und 2, 4‐Dimethylpentadienyl‐Komplexe des Rhodiums und Iridiums

2, 4‐Dimethylpenta‐1, 3‐diene and 2, 4‐Dimethylpentadienyl Complexes of Rhodium and Iridium The complexes [(η⁴‐C₇H₁₂)RhCl]₂ ( 1 ) (C₇H₁₂ = 2, 4‐dimethylpenta‐1, 3‐diene) and [(η⁴‐C₇H₁₂)₂IrCl] ( 2 ) were obtained by interaction of C₇H₁₂ with [(η²‐C₂H₄)₂RhCl]₂ and [(η²‐cyclooctene)₂IrCl]₂, respectively. The reaction of 1 or 2 with CpTl (Cp = η⁵‐C₅H₅) yields the compounds [CpM(η⁴‐C₇H₁₂)] ( 3a : M = Rh; 3b : M = Ir). The hydride abstraction at the pentadiene ligand of 3a , b with Ph₃CBF₄ proceeds differently depending on the solvent. In acetone or THF the “half‐open” metallocenium complexes [CpM(η⁵‐C₇H₁₁)]BF₄ ( 4a : M = Rh; 4b : M = Ir) are obtained exclusively. In dichloromethane mixtures are produced which additionally contain the species [(η⁵‐C₇H₁₁)M(η⁵‐C₅H₄CPh₃)]BF₄ ( 5a : M = Rh; 5b : M = Ir) formed by electrophilic substitution at the Cp ring, as well as the η³‐2, 4‐dimethylpentenyl compound [(η³‐C₇H₁₃)Rh{η⁵‐C₅H₃(CPh₃)₂}]BF₄ ( 6 ). By interaction of 2, 4‐dimethylpentadienyl potassium with 1 or 2 the complexes [(η⁴‐C₇H₁₂)M(η⁵‐C₇H₁₁)] ( 7a : M = Rh; 7b : M = Ir) are generated which show dynamic behaviour in solution; however, attempts to synthesize the “open” metallocenium cations [(η⁵‐C₇H₁₁)₂M]⁺ by hydride abstraction from 7a , b failed. The new compounds were characterized by elemental analysis and spectroscopically, 4b and 5a also by X‐ray structure analysis.     

A Simple Synthesis of 5‐(2‐Aminophenyl)‐1H‐pyrazoles

A four‐step synthesis of 1‐substituted 5‐(2‐aminophenyl)‐1H‐pyrazoles 5 as a novel type of histamine analogs and versatile building blocks for further transformations was developed. The synthesis starts from commercially available 2‐nitroacetophenone ( 12 ), which is converted into the enamino ketone 13 as the key intermediate. Cyclization of the key intermediate 13 with monosubstituted hydrazines 14a – 14l afforded the 5‐(2‐nitrophenyl)‐1H‐pyrazoles 17a – 17l . Finally, catalytic hydrogenation of the nitro compounds 17a, 17c – 17e , and 17g – 17j furnished the title compounds 5a, 5c – 5e , and 5g – 5j , respectively, in good yields. As demonstrated by some further transformations, additional functionalization of compounds 17 and 5 is feasible, either by electrophilic substitution at C(4) of the pyrazole ring, or at the NH₂ group.     

Syntheses,Structures, and Photophysical Properties of Two Coordination Polymers Based on 2,3‐Dioxo‐1,2,3,4‐tetrahydroquinoxaline‐6‐carboxylic Acid

Two complexes based on the ligand 1,4‐dihydro‐2,3‐quinoxalinedione, namely [Mn(H₂L)₂(H₂O)₂]_n ( 1 ) and {[Zn₂(H₂L)₂(tz)₂] · 5H₂O}_n ( 2 ) (H₃L = 2,3‐dioxo‐1,2,3,4‐tetrahydroquinoxaline‐6‐carboxylic acid, Htz = 1,2,4‐triazole) were hydrothermally synthesized and characterized by elemental analyses, IR spectroscopy, as well as single‐crystal and powder X‐ray diffraction. Complex 1 exhibited a 1D comb‐like chain formed by H₂L^– anions linking Mn^II ions, whereas complex 2 was a 2D layer‐like structure with square‐shaped windows and outstretched arms built by combination of H₂L^– and tz^– ligands with Zn^II ions. The adjacent chains or layers connected with each other by intermolecular hydrogen bonding and π–π stacking to further extend to a 3D supermolecular framework. In addition, the thermal stabilities, luminescence properties, and optical energy gap of 1 and 2 were investigated in detail.     

Synthesis of 2‐Aryl‐5‐oxo‐4‐[2‐(phenylmethylidene)hydrazino]‐2,5‐dihydro‐1H‐pyrrole‐3‐carboxylates by the Reaction between Hydrazones,Acetylenedicarboxylates, and 1‐Aryl‐N,N′‐bis(arylmethylidene)methanediamines

An efficient approach for the preparation of functionalized 2‐aryl‐2,5‐dihydro‐5‐oxo‐4‐[2‐(phenylmethylidene)hydrazino]‐1H‐pyrroles is described. The four‐component reaction between aldehydes, NH₂NH₂?H₂O, dialkyl acetylenedicarboxylates, and 1‐aryl‐N,N′‐bis(arylmethylidene)methanediamines proceeds in EtOH under reflux in good‐to‐excellent yields (Scheme 1). The structures of 4 were corroborated spectroscopically (IR, ¹H‐ and ¹³C‐NMR, and EI‐MS, and, in the case of 4f , by X‐ray crystallography). A plausible mechanism for this type of reaction is proposed (Scheme 2).     

Synthesis of [3,3′(4H,4′H)‐Bi‐2H‐1,3‐oxazine]‐4,4′‐diones and Their Hydrolysis

The [3,3′(4H,4′H)‐bi‐2H‐1,3‐oxazine]‐4,4′‐diones 3a – 3i were obtained by [2+4] cycloaddition reactions of furan‐2,3‐diones 1a – 1c with aromatic aldazines 2a – 2d (Scheme 1). So, new derivatives of bi‐2H‐1,3‐oxazines and their hydrolysis products, 3,5‐diaryl‐1H‐pyrazoles 4a – 4c (Scheme 3), which are potential biologically active compounds, were synthesized for the first time.     

A twofold interpenetrating three‐dimensional CdII coordination framework: poly[[μ2‐1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene](μ3‐5‐nitrobenzene‐1,3‐dicarboxylato)cadmium(II)]

A twofold interpenetrating three‐dimensional Cd^II coordination framework, [Cd(C₈H₃NO₆)(C₁₄H₁₄N₄)]_n, has been prepared and characterized by IR spectroscopy, elemental analysis, thermal analysis and single‐crystal X‐ray diffraction. The asymmetric unit consists of a divalent Cd^II atom, one 1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene (1,3‐BMIB) ligand and one fully deprotonated 5‐nitrobenzene‐1,3‐dicarboxylate (NO₂‐BDC²⁻) ligand. The coordination sphere of the Cd^II atom consists of five O‐donor atoms from three different NO₂‐BDC²⁻ ligands and two imidazole N‐donor atoms from two different 1,3‐BMIB ligands, forming a distorted {CdN₂O₅} pentagonal bipyramid. The NO₂‐BDC ligand links three Cd^II atoms via a μ₁‐η¹:η¹ chelating mode and a μ₂‐η²:η¹ bridging mode. The title compound is a twofold interpenetrating 3,5‐connected network with the {4².6⁵.8³}{4².6} topology. In addition, the compound exhibits fluorescence emissions in the solid state at room temperature.     

Syntheses,Structures, Electrochemistry,and Electrocatalysis of Three Copper(II) Coordination Polymers constructed from 5‐[4‐(1H‐Imidazol‐1‐yl)phenyl]‐1H‐tetrazole

Three coordination polymers (CPs) based on the 5‐[4‐(1H‐imidazol‐1‐yl)phenyl]‐1H‐tetrazole ( HL ) ligand, namely, [Cu(μ₂‐ L )(μ₄‐pbda)(H₂O)] ( 1 ), [Cu₂(μ‐Hbtc)(H₂btc)(μ₃‐OH)(μ₄‐ HL )] ( 2 ) and [Cu₅(μ₃‐ L )(μ₄‐ L )(μ₃‐ip)(μ₃‐OH)(H₂O)₂] · 2H₂O ( 3 ) (H₂pbda = 1,4‐benzenedicarboxylic acid, H₃btc = 1,3,5‐benzenetricarboxylic acid, H₂ip = isophthalic acid) were hydrothermally synthesized and structurally characterized. Complex 1 represents “weave”‐type 2D layers consisting of wave‐like 1D chains and 1D straight chains, which are further connected by hydrogen bonds to form a 3D supramolecular structure. Complex 2 exhibits a uninodal (4)‐connected 2D layer with a point symbol of {4⁴ · 6²}, in which the L ligand can be described as μ₅‐bridging and the H₂btc^– ions display multiple kinds of coordination modes to connect Cu^II ions into 1D “H”‐type Cu‐H₂btc chains. In complex 3 , 2D Cu‐ L layers with two kinds of grids and 1D “stair”‐type Cu‐ip chains link each other to construct a 3D {4¹² · 6³} framework, which contains the pentanuclear subunits. Deprotonated degree and coordination modes of carboxylate ligands may consequentially influence the coordination patterns of main ligands and the final structures of complexes 1 – 3 . Furthermore, electrochemical behaviors and electrocatalytic activities of the title complexes were analyzed at room temperature, suggesting practical applications in areas of electrocatalytic reduction toward nitrite and hydrogen dioxide in aqueous solutions, respectively.     

A 2D Metal‐Organic Framework Based on 9‐(Pyridin‐4‐yl)‐9H‐carbazole‐3,6‐dicarboxylic Acid: Synthesis,Structure and Properties

A metal‐organic framework (MOF ) formulated as [Cd₂(μ₃‐L)₂(DMF )₄]•H₂O ( CdL ) [H₂L =9‐(pyridin‐4‐yl)‐ 9H ‐carbazole‐3,6‐dicarboxylic acid, DMF =N ,N ‐dimethylformamide] was synthesized under solvothermal condition. Crystal structural analysis reveals that CdL features the layered 2D framework with L^{2 −} ligands as 3‐connected nodes. The compound CdL emits blue‐violet light with the narrow emission peak and the emission maximum at 414 nm upon excitation at the maximum excitation wavelength of 340 nm. The compound CdL has a similar emission spectrum curve to the free H₂L ligand that indicates the emission of compound CdL should be originated from the coordinated L^{2 −} ligands.     

A three‐dimensional cadmium coordination polymer based on 1,4‐bis(1,2,4‐triazol‐1‐yl)but‐2‐ene and benzene‐1,3,5‐tricarboxylic acid

The Cd^II three‐dimensional coordination poly[[[μ₄‐1,4‐bis(1,2,4‐triazol‐1‐yl)but‐2‐ene]bis(μ₃‐5‐carboxybenzene‐1,3‐dicarboxylato)dicadmium(II)] dihydrate], {[Cd₂(C₉H₄O₆)₂(C₈H₁₀N₆)]·2H₂O}_n , (I), has been synthesized by the hydrothermal reaction of Cd(NO₃)₂·4H₂O, benzene‐1,3,5‐tricarboxylic acid (1,3,5‐H₃BTC) and 1,4‐bis(1,2,4‐triazol‐1‐yl)but‐2‐ene (1,4‐btbe). The IR spectrum suggests the presence of protonated carboxylic acid, deprotonated carboxylate and triazolyl groups. The purity of the bulk sample was confirmed by elemental analysis and X‐ray powder diffraction. Single‐crystal X‐ray diffraction analysis reveals that the Cd^II ions adopt a five‐coordinated distorted trigonal–bipyramidal geometry, coordinated by three O atoms from three different 1,3,5‐HBTC²⁻ ligands and two N atoms from two different 1,4‐btbe ligands; the latter are situated on centres of inversion. The Cd^II centres are bridged by 1,3,5‐HBTC²⁻ and 1,4‐btbe ligands into an overall three‐dimensional framework. When the Cd^II centres and the tetradentate 1,4‐btbe ligands are regarded as nodes, the three‐dimensional topology can be simplified as a binodal 4,6‐connected network. Thermogravimetric analysis confirms the presence of lattice water in (I). Photoluminescence studies imply that the emission of (I) may be ascribed to intraligand fluorescence.