Synthesis,Characterization of a Novel 1,2,4‐Thiotriazine Derivative (CAMTTO), and Copper(I) and Silver(I) Complexes thereof (CAMTTO = {(4‐[(4‐Chlorobenzylidene)‐amino]‐6‐methyl‐3‐thioxo‐[1,2,4]‐triazin‐3,4‐dihydro(2H)‐5‐one)}

The reaction of 4‐amino‐6‐methyl‐1,2,4‐triazin‐thione‐5‐one (H₂AMTTO, 1 ) with 4‐chlorobenzaldhyde led to the corresponding iminic compound {(4‐[(4‐chloro‐benzylidene)‐amino]‐6‐methyl‐3‐thioxo[1,2,4]‐triazin‐3,4‐dihydro(2H)‐5‐one), CAMTTO ( 2 ). Treatment of 2 with copper(I) chloride in chloroform gave the dimeric complex [{(CAMTTO)₂CuCl}₂]·2CHCl₃ ( 3 ). Treatment of 2 with copper(I) chloride and silver(I) nitrate in the presence of the co‐ligand triphenylphophane gave the complexes [(CAMTTO)CuCl(PPh₃)₂] ( 4 ) and [(CAMTTO)Ag(PPh₃)₂]NO₃·2CHCl₃ ( 5 ). All compounds have been characterized by elemental analyses, ¹H NMR spectroscopy, IR spectroscopy, and partly by mass spectrometry and X‐ray diffraction studies. In addition 4 and 5 have been characterized by ³¹P{¹H} NMR spectroscopy. Crystal data for 2 at ?80 °C: monoclinic, space group P2₁/c, a = 1370.3(1), b = 767.8(1), c = 1268.7(1) pm, β = 107.12(1)°, Z = 4, R₁ = 0.0379; for 3 at ?80 °C: monoclinic, space group P2₁/c, a = 1442.6(2), b = 878.8(1), c = 2558.7(3) pm, β = 95.31(1)°, Z = 2, R₁ = 0.0746; for 4 at ?80 °C: triclinic, space group , a = 1287.9(1), b = 1291.7(1), c = 1359.5(1) pm, α = 90.44(1)°, β = 94.81(1)°, γ = 107.54(1)°, Z = 2, R₁ = 0.0359 and for 5 at ?80 °C: triclinic, space group , a = 1060.5(1), b = 1578.2(2), c = 1689.6(2) pm, α = 87.70(1)°, β = 86.66(1)°, γ = 76.84(1)°, Z = 2, R₁ = 0.0487.     

Syntheses and Crystal Structures of Copper(II) and Silver Complexes with 5‐Methyl‐1‐(4‐Methylphenyl)‐1,2,3‐Triazol‐4‐Carboxylic Acid

Two novel complexes [Cu L ₂(MeOH)] ( 1 )and [Ag₂ L (H L )₂(MeOH)] ( 2 ) ( L = 5‐methyl‐1‐(4‐methylphenyl)‐1,2,3‐triazol‐4‐carboxylic acid) were synthesized and characterized by elemental analysis, IR and X‐ray diffraction. Complex 1 is a mononuclear structure; the molecules were assembled into an infinite 2–D supramolecular by the C–H···O weak interactions. Complex 2 is a centrosymmetric dinuclear structure with bis(unidentate) carboxylato co‐ordination mode, and the molecules were assembled into 2–D layers by C–H···O and O–H···O weak interactions.     

Copper(II)‐Catalyzed Synthesis of N‐Substituted‐3‐amino‐4‐cyano‐isoquinoline‐1(2H)‐ones by the Reaction of N‐Substituted‐2‐iodobenzamides with Malononitrile

A novel Cu(OAc)₂·H₂O catalyzed coupling reaction of N‐substituted‐2‐iodobenzamides with malononitrile to afford N‐substituted‐3‐amino‐4‐cyano‐isoquinoline‐1(2H)‐ones is described. The reaction proceeded in DMSO at 90°C for 5 h in nitrogen without external ligands.     

Electronic spectra and first‐order hyperpolarizability of 4‐(dicyanomethylene)‐2,6‐bis‐ (2′‐thiophene‐vinyl)‐pyran derivatives

On the basis of the ZINDO program, we have designed a program to calculate the first‐order hyperpolarizability β_ijk and β_μ according to the sum‐over‐states (SOS) expression. The first‐order hyperpolarizability of 4‐(dicyanomethylene)‐2,6‐bis‐(2′‐thiophene‐vinyl)‐pyran derivatives were studied. The calculated results were that the 4‐(dicyanomethylene)‐2,6‐bis‐(2′‐thiophene‐vinyl)‐pyran derivatives exhibit good nonlinearity with their β₀ values, which are slightly less than that of the corresponding 2,6‐bis‐styryl‐4‐(dicyanomethylene)‐pyran derivatives. It does not agree with the auxiliary donor–acceptor effects theory. The 4‐(dicyanomethylene)‐2,6‐bis‐(2′‐thiophene‐vinyl)‐pyran derivatives, having two low‐lying electronic excited states that contribute to the molecular hyperpolarizability in an additive manner, are good candidates as chromophores due to their high nonlinearities and good thermal stability. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 82: 65–72, 2001     

Synthesis,Characterization and Crystal Structure of the Dimeric Silver(I) Complex containing 4‐Amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione

The reaction of 4‐amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione (AMTT, 1 ) with AgNO₃ and triphenylphosphane in a molar ratio 1:1:2 in ethanol led to the dimeric complex {[Ag(AMTT)(PPh₃)₂]NO₃}₂·4EtOH ( 2 ). 2 was characterized by elemental analyses, IR, ³¹P NMR spectroscopy as well as single crystal X‐ray diffraction. Crystal data for 2 at ?80 °C: space group with a = 1265.5(2), b = 1300.9(2), c = 1509.5(2) pm, α = 83.77(2)°, β = 79.22(2)°, γ = 62.89(2)°, Z = 2, R₁ = 0.0330.     

Mononuclear Co(III), Ni(II) and Cu(II) complexes of 2‐(2,4‐dichlorobenzamido)‐N'‐(3,5‐di‐tert‐butyl‐2‐hydroxybenzylidene)benzohydrazide: Structural insight and biological assay

A series of mononuclear metal complexes of Co(III), Ni(II) and Cu(II) with 2‐(2,4‐dichlorobenzamido)‐N′‐(3,5‐di‐tert‐butyl‐2‐hydroxybenzylidene)benzohydrazide ( LH ₃ ) have been synthesized and characterized using various physico‐chemical, spectroscopic and single crystal X‐ray diffraction techniques. Structural studies of [Co( LH )( LH ₂ )]·H₂O ( 4 ) revealed the presence of both amido and imidol tautomeric forms of LH ₃ , resulting in a distorted octahedral geometry around the Co(III) ion. [Ni( LH )(H₂O)]·H₂O ( 5 ) and [Cu( LH )(H₂O)]·H₂O ( 6 ) are isomorphous structures and crystallize in the monoclinic P2₁/c space group. The crystal structures of 4 , 5 and 6 are stabilized by hydrogen bonds formed by the enclathrated water molecules, C‐H···π and π···π interactions. Complexes along with the ligand ( LH ₃ ) were screened for their in vivo anti‐inflammatory activity (carrageenan‐induced rat paw edema method) and in vitro antioxidant activity (DPPH free radical scavenging assay). Metal complexes have shown significant anti‐inflammatory and antioxidant potential.     

Embryotoxicity studies of tri‐n‐butyltin(IV) complexes of 5‐[(E)‐2‐(aryl)‐1‐diazenyl]‐2‐hydroxybenzoic acid and 2‐[(E)‐2‐(3‐formyl‐4‐hydroxyphenyl)‐1‐diazenyl] benzoic acid on sea urchin development

The toxicity studies of free 5‐[(E)‐2‐(aryl)‐1‐diazenyl]‐2‐hydroxybenzoic acid and 2‐[(E)‐2‐(3‐formyl‐4‐hydroxyphenyl)‐1‐diazenyl]benzoic acid and their tri‐n‐butyltin(IV) complexes were evaluated by using sea urchin early developmental stages as recommended model organisms for toxicity tests. The novel complexes, as the parent tri‐n‐butyltin(IV) chloride (TBTCl), caused mitosis block and induced high embryonic mortality in sea urchin. Copyright © 2005 John Wiley & Sons, Ltd.     

Novel 5‐Methyl‐2‐[(un)substituted phenyl]‐4‐{4,5‐dihydro‐ 3‐[(un)substituted phenyl]‐5‐(1,2,3,4‐tetrahydroisoquinoline‐2‐yl)pyrazol‐1‐yl}‐oxazole Derivatives: Synthesis and Anticancer Activity

Eleven novel 5‐methyl‐2‐[(un)substituted phenyl]‐4‐{4,5‐dihydro‐3‐[(un)substituted phenyl]‐5‐(1,2,3,4‐tetrahydroisoquinoline‐2‐yl)pyrazol‐1‐yl}‐oxazole derivatives were synthesized and characterized by elemental analysis, ESI‐MS, ¹H NMR and ¹³C NMR. All of the compounds have been screened for their antiproliferative activities against PC‐3 cell (human prostate cancer) and A431 cell (human epidermoid carcinoma cancer) lines in vitro. The results revealed that compounds 4g , 4j and 4k exhibited the strong inhibitory activities against the PC‐3 cell lines (with IC₅₀ values of 2.8±0.11, 3.1±0.10 and 3.0±0.06 μg/mL, respectively).     

Synthesis and properties of ortho‐linked aromatic polyimides based on 1,2‐bis(4‐aminophenoxy)‐4‐tert‐butylbenzene

A bis(ether amine) containing the ortho‐substituted phenylene unit and pendant tert‐butyl group, 1,2‐bis(4‐aminophenoxy)‐4‐tert‐butylbenzene, was synthesized and used as a monomer to prepare polyimides with six commercial dianhydrides via a conventional two‐stage procedure. The intermediate poly(amic acid)s had inherent viscosities of 0.78–1.44 dL/g, and most of them could be thermally converted into transparent, flexible, and tough polyimide films. The inherent viscosities of the resulting polyimides were in the range of 0.46–0.87 dL/g. All polyimides were noncrystalline, and most of them showed excellent solubility in polar organic solvents. The glass‐transition temperatures of these polyimides were in the range of 222–259 °C in differential scanning calorimetry and 212–282 °C in thermomechanicl analysis. These polyimides showed no appreciable decomposition up to 500 °C in thermogravimetric analysis in air or nitrogen. A comparative study of the properties with the corresponding polyimides without pendant tert‐butyl groups derived from 1,2‐bis(4‐aminophenoxy)benzene is also presented. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1551–1559, 2000     

Synthesis,one‐ and two‐photon properties of poly[9,10‐bis(3,4‐bis(2‐ethylhexyl‐oxy)phenyl)‐2,6‐anthracenevinylene‐alt‐N‐octyl‐3,6‐/2,7‐carbazolevinylene]

The synthesis, one‐ and two‐photon absorption (TPA) and emission properties of two novel 2,6‐anthracenevinylene‐based copolymers, poly[9,10‐bis(3,4‐bis(2‐ethylhexyloxy)phenyl)‐2,6‐anthracenevinylene‐alt‐N‐octyl‐3,6‐carbazolevinyl‐ene] ( P1 ) and poly[9,10‐bis(3,4‐bis(2‐ethylhexyloxy)phenyl)‐2,6‐anthracenevinyl‐ene‐alt‐N‐octyl‐2,7‐carbazolevinylene] ( P2 ) were reported. The as‐synthesized polymers have the number‐average molecular weights of 1.56 × 10⁴ for P1 and 1.85 × 10⁴ g mol^?1 for P2 and are readily soluble in common organic solvents. They emit strong bluish‐green one‐ and two‐photon excitation fluorescence in dilute toluene solution (? _P1 = 0.85, ? _P2 = 0.78, λ_em( P1 ) = 491 nm, λ_em( P2 ) = 483 nm). The maximal TPA cross‐sections of P1 and P2 measured by the two‐photon‐induced fluorescence method using femtosecond laser pulses in toluene are 840 and 490 GM per repeating unit, respectively, which are obviously larger than that (210 GM) of poly[9,10‐bis‐(3,4‐bis(2‐ethylhexyloxy) phenyl)‐2,6‐anthracenevinylene], indicating that the poly(2,6‐anthracenevinylene) derivatives with large TPA cross‐sections can be obtained by inserting electron‐donating moieties into the polymer backbone. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 463–470, 2010     

Synthesis,Spectroscopic, and X‐Ray Diffraction Studies of cis‐Dichlorobis(4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl3 H‐pyrazol‐3‐onato) Tin(IV)

Reaction between an aqueous ethanol solution of tin(II) chloride and that of 4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl‐3 H‐pyrazol‐3‐one in the presence of O₂ gave the compound cis‐dichlorobis(4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl‐3 H‐pyrazol‐3‐onato) tin(IV) [(C₂₆H₂₆N₄O₄)SnCl₂]. The compound has a six‐coordinated Sn^IV centre in a distorted octahedral configuration with two chloro ligands in cis position. The tin atom is also at a pseudo two‐fold axis of inversion for both the ligand anions and the two cis‐chloro ligands. The orange compound crystallizes in the triclinic space group P 1 with unit cell dimensions, a = 8.741(3) Å, b = 12.325(7) Å, c = 13.922(7) Å; α = 71.59(4), β = 79.39(3), γ = 75.18(4); Z = 2 and D_x = 1.575 g cm^–3. The important bond distances in the chelate ring are Sn–O [2.041 to 2.103 Å], Sn–Cl [2.347 to 2.351 Å], C–O [1.261 to 1.289 Å] and C–C [1.401 Å] the bond angles are O–Sn–O 82.6 to 87.7° and Cl–Sn–Cl 97.59°. The UV, IR, ¹H NMR and ¹¹⁹Sn Mössbauer spectral data of the compound are reported and discussed.     

Formation of 2‐(Phenylsulfonyl)resorcinols (=2‐(Phenylsulfonyl)benzene‐1,3‐diols) from Symmetrically Substituted Maleic Anhydrides (=Furan‐2,5‐diones)

Treatment of symmetrically substituted maleic anhydrides (=furan‐2,5‐diones) 6 with lithium (phenylsulfonyl)methanide, followed by methylation of the adduct with MeI/K₂CO₃ in acetone, give the corresponding 4,5‐disubstituted 2‐methyl‐2‐(phenylsulfonyl)cyclopent‐4‐ene‐1,3‐diones 8 (Scheme 3). Reaction of the latter with lithium (phenylsulfonyl)methanide in THF (?78°) and then with 4 mol‐equiv. BuLi (?5° to r.t.) leads to 5,6‐disubstituted 4‐methyl‐2‐(phenylsulfonyl)benzene‐1,3‐diols 9 (Scheme 4).     

Structural Diversity in the Self‐assembly of Cd(II) Complexes Containing 2,6‐Dimethyl‐3,5‐dicyano‐4‐(4‐pyridyl)‐1,4‐dihydropyridine

The syntheses, structures and properties of the complexes [CdBr₂( L )₂·4H₂O]_n [ L = 2,6‐dimethyl‐3,5‐dicyano‐4‐(4‐pyridyl)‐1,4‐dihydropyridine], 1 and [Cd(SCN)₂( L )₂(H₂O)]_n, 2 , are reported. In polymeric complexes 1 — 2 , the L ligands bridge the metal centers through the pyrimidyl and cyano nitrogen atoms forming 1‐D double‐stranded chain and zigzag chain, respectively. The L ligands in complex 1 act as κ1, κ1‐bidentate bridging ligand, whereas the L ligands in complex 2 act as κ1‐monodentae and κ1, κ1‐bidentate bridging ligand. The molecules of these complexes are interlinked through various weak interactions that form the packed structure. All the complexes exhibit emissions which may be tentatively assigned as intraligand (IL) π→π* transitions.     

Highly Selective and Sensitive Copper(II) Membrane Sensors Based on 6‐Methyl‐4‐(1‐phenylmethylidene)amino‐3‐thioxo‐1,2,4‐triazin‐5‐one as a New Neutral Ionophore

A new Cu(II) ion‐selective PVC membrane sensor based on 6‐methyl‐4‐(1‐phenylmethylidene)amino‐3‐thioxo‐1,2,4‐triazin‐5‐one (MATTO) as an excellent sensing material was developed. The electrode exhibits a Nernstian slope of 29.2±0.4 mV per decade over a very wide concentration range between 1.0×10^?1 and 1.0×10^?6 M, with a detection limit of 4.8×10^?7 M (30.5 ng/mL). The sensor possesses the advantages of short conditioning time, fast response time (<10 s), and especially, very good selectivity towards transition and heavy metal, and some mono, di and trivalent cations. The proposed electrode was successfully applied to the determination of copper in wastewater of copper electroplating samples and as an indicator electrode in potentiometric titration of Cu(II) ions with EDTA.     

Dihalodimethyltin(IV) complexes of 2‐(pyrazol‐1‐ylmethyl)pyridine

Reaction of dichloro‐ and dibromodimethyltin(IV) with 2‐(pyrazol‐1‐ylmethyl)pyridine (PMP) afforded [SnMe₂Cl₂(PMP)] and [SnMe₂Br₂(PMP)] respectively. The new complexes were characterized by elemental analysis and mass spectrometry and by IR, Raman and NMR (¹H, ¹³C) spectroscopies. Structural studies by X‐ray diffraction techniques show that the compounds consist of discrete units with the tin atom octahedrally coordinated to the carbon atoms of the two methyl groups in a trans disposition (Sn? C = 2.097(5), 2.120(5) Å and 2.110(6), 2.121(6) Å in the chloro and in the bromo compounds respectively), two cis halogen atoms (Sn? Cl = 2.4908(16), 2.5447(17) Å; Sn? Br = 2.6875(11), 2.7464(9) Å) and the two donor atoms of the ligand (Sn? N = 2.407(4), 2.471(4) Å and 2.360(5), 2.455(5) Å). In both cases, the Sn? N(pyridine) bond length is markedly longer than the Sn? N(pyrazole) distance. Copyright © 2003 John Wiley & Sons, Ltd.     

Assembly of Three 2D Metal‐Organic Frameworks (MOFs) Derived from Flexible Ligands, 1,4‐bis(3‐pyridyl)‐2,3‐diaza‐1,3‐butadiene (3‐bpd) and/or 1,2‐bis(4‐pyridyl)ethane (dpe)

Three coordination polymers, {[Cd(3‐bpd)₂(NCS)₂]×C₂H₅OH}_n ( 1 ), {[Cd(3‐bpd)(dpe)(NO₃)₂]×(3‐bpd)}₂ ( 2 ), {[Cd(dpe)₂(NCS)₂]×3‐bpd×2H₂O}_n ( 3 ) (3‐bpd = 1,4‐bis(3‐pyridyl)‐2,3‐diaza‐1,3‐butadiene; dpe = 1,2‐bis(4‐pyridyl)ethane), were prepared and structurally characterized by a single‐crystal X‐ray diffraction method. In compound 1 , each Cd(II) ion is six‐coordinate bonded to six nitrogen atoms from four 3‐bpd and two NCS^? ligands. The 3‐bpd acts as a bridging ligand connecting the Cd(II) ion to generate a 2D layered metal‐organic framework (MOF) by using a rhomboidal‐grid as the basic building units with the 4⁴ topology. In compound 2 , the Cd(II) ion is also six‐coordinate bonded to four nitrogen atoms of two 3‐bpd, two dpe and two oxygen atoms of two NO₃^? ligands. The 3‐bpd and dpe ligands both adopt bis‐monodentate coordination mode connecting the Cd(II) ions to generate a 2D layered MOF by using a rectangle‐grid as the basic building units with the 4⁴ topology. In compound 3 , two crystallographically independent Cd(II) ions are both coordinated by four nitrogen atoms of dpe ligands in the basal plane and two nitrogen atom of NCS^? in the axial sites. The dpe acts as a bridging ligand to connect the Cd(II) ions forming a 2D interpenetrating MOFs by using a square‐grid as the basic unit with the 4⁴ topology. All of their 2D layered MOFs in compounds 1 ‐ 3 are then arranged in a parallel non‐interpenetrating ABAB—packing manner in 1 and 2 , and mutually interpenetrating manner in 3 , respectively, to extend their 3D supramolecular architectures with their 1D pores intercalated with solvent (ethanol in 1 or H₂O in 3 ) or free 3‐bpd molecules in 2 and 3 , respectively. The photoluminescence measurements of 1 ‐ 3 reveal that the emission is tentatively assigned to originate from π‐π* transition for 1 and 2 and probably due to ligand‐center luminescence for compounds 3 , respectively.     

1,2‐Dithioquadratato‐ und 1,2‐Dithiooxalatoindate(III)

Indium(III) chloride forms in water with potassium 1,2‐dithiooxalate (dto) and potassium 1,2‐dithiosquarate (dtsq) stable coordination compounds. Due to the higher bridging ability of the 1,2‐dithiooxalate ligand in all cases only thiooxalate bridged binuclear complexes were found. From 1,2‐dithioquadratate with an identical donor atom set mononuclear trischelates could be isolated. Five crystalline complexes, (BzlMe₃N)₄[(dto)₂In(dto)In(dto)₂] ( 1 ), (BzlPh₃P)₄[(dto)₂In(dto)In(dto)₂] ( 2 ), (BzlMe₃N)₃[In(dtsq)₃] ( 3 ), (Bu₄N)₃[In(dtsq)₃] ( 4 ) and (Ph₄P)[In(dtsq)₂(DMF)₂] ( 5 ), have been isolated and characterized by X‐ray analyses. Due to the type of the complex and the cations involved these compounds crystallize in different space groups with the following parameters: 1 , monoclinic in P2₁/c with a = 14.4035(5) Å, b = 10.8141(5) Å, c = 23.3698(9) Å, β = 124.664(2)°, and Z = 2; 2 , triclinic in P with a = 11.3872(7) Å, b = 13.6669(9) Å, c = 17.4296(10) Å, α = 88.883(5)°, β = 96.763(1)°, γ = 74.587(5)°, and Z = 1; 3 , hexagonal in R3 with a = 20.6501(16) Å, b = 20.6501(16) Å, c = 19.0706(13) Å and Z = 6; 4 , monoclinic in P2₁/c with a = 22.7650(15) Å, b = 20.4656(10) Å, c = 14.4770(9) Å, β = 101.095(5)°, and Z = 4; 5 , triclinic in P with a = 9.2227(6) Å, b = 15.3876(9) Å, c = 15.5298(9) Å, α = 110.526(1)°, β = 100.138(1)°, γ = 101.003(1)°, and Z = 2.     

Investigation of the Reaction of Gold(III) with 2‐[2‐(4‐Dimethylamino‐Phenyl)‐Vinyl]‐1,3,3‐Trimethyl‐3H‐Indolium. Application for Determination of Gold

A new, simple, rapid, sensitive, efficient and low‐cost spectrophotometric procedure for the determination of gold was developed. The method is based on the reaction of [AuCl₄]^? with 2‐[2‐(4‐dimethylaminophenyl)‐vinyl]‐1,3,3‐trimethyl‐3H‐indolium reagent to form a colored ion associate extractable by various organic solvents. The molar absorptivity of the ion associates is in the range (5.7–9.2) × 10⁴ L mol^?1 cm^?1 depending on the extractant. Butyl acetate was chosen as the extractant. The optimum reaction conditions were established: pH 2–4, concentration of the dye reagent (0.8–1.5) × 10^?4 mol L^?1. The determination of gold is not hindered even by a 1000‐fold concentration of Ni and Co; a 500‐fold concentration of Pb and Zn; a 100‐fold concentration of Bi, Cu, Cd, Pt, Rh and Ru; or a 20‐fold concentration of Ag. The established method was applied to the determination of gold in model samples and enriched polymetallic ores.     

Grid‐like Cobalt(II) Layered Complex with an Unprecedented Double 1,2‐Bis(1,2,4‐triazole‐1‐yl)methane Bridges

A novel two‐dimensional cobalt complex, [Co(btrm)₂(dca)]ClO₄ ( 1 , btrm = 1,2‐bis(1,2,4‐triazole‐1‐yl)methane, dca = dicyanamide), was synthesized and characterized. X‐ray diffraction analyses reveal that the title complex crystallizes in the monoclinic space group C2/m with a = 29.507(13)Å, b = 17.804(8) Å, c = 14.709(7) Å, β = 119.916(7)°, Z = 12, and R₁ = 0.0784, wR₂ = 0.2041. The cobalt atom involves a six‐coordinated CoN₆ environment, with a distorted octahedral coordination. Two btrm ligands connect the Co^II atoms with the exodentate nitrogen atoms on the 4‐position of triazole rings to form a sixteen‐membered rhombic grid. The unprecedented double btrm bridges and μ_1,5‐dca bridge connect the cobalt atoms to form a two‐dimensional grid‐like layered structure. The spectroscopic and magnetic properties have also been investigated.     

Anion Effects on the Formation of Silver(I) Complexes with the Flexible Ligand 4,4′‐Bis(1,2,4‐triazol‐1‐ylmethyl)biphenyl

The reaction of 4,4′‐bis(1,2,4‐triazol‐1‐ylmethyl)biphenyl (btmb) with silver(I) salts of BF₄^–, NO₃^– and N₃^– led to the formation of four new silver(I) coordination polymers {[Ag(btmb)]BF₄}_n ( 1 ), {[Ag₂(btmb)₃](NO₃)₂(H₂O)₅}_n ( 2 ), [Ag₂(btmb)(N₃)₂]_n ( 3 ), and [Ag(btmb)(N₃)]_n ( 4 ). Their coordination number varies from 2 (in 1 ) to 3 (in 2 ), 4 (in 3 ), and 5 (in 4 ). Different from the single chain structure of 1 , complex 2 displays a 1D ladder‐like double chain framework, whereas complex 3 exhibits a 2D layered architecture. Complex 4 has the same anion as complex 3 but shows a different metal‐to‐ligand ratio and a 1D double‐zigzag chain structure. Both 3 and 4 have Ag ··· Ag argentophilic interactions. The ligand btmb adopts both cis or trans configuration in the studied complexes. A trans‐ or cis‐btmb ligand link silver ions with Ag ··· Ag distances of ≈?18 and 13 Å, respectively. BF₄^– and NO₃^– are non‐coordinating anions in 1 and 2 . N₃^– is the bridging anion in 3 (1,3‐bridging fashion) and 4 (1,1‐bridging fashion). These findings suggest that the coordination numbers around the Ag^I ion correlate to the coordination abilities of anions and the btmb to silver ratio. In addition, the influence of anions on thermal stability were also investigated. This work is a good example that nicely supports the less explored field of anion‐dependent structures of complexes with non‐pyridyl ligands.