Hydroxo‐bridged Tetranuclear CuII Complexes: {[Cu(bpy)(OH)]4Cl2}Cl2 · 6 H2O and {[Cu(phen)(OH)]4(H2O)2}]Cl4 · 4 H2O

The blue tetranuclear Cu^II complexes {[Cu(bpy)(OH)]₄Cl₂}Cl₂ · 6 H₂O ( 1 ) and {[Cu(phen)(OH)]₄(H₂O)₂}Cl₄ · 4 H₂O ( 2 ) were synthesized and characterized by single crystal X‐ray diffraction. ( 1 ): P 1 (no. 2), a = 9.240(1) Å, b = 10.366(2) Å, c = 12.973(2) Å, α = 85.76(1)°, β = 75.94(1)°, γ = 72.94(1)°, V = 1152.2(4) ų, Z = 1; ( 2 ): P 1 (no. 2), a = 9.770(3) Å, b = 10.118(3) Å, c = 14.258(4) Å, α = 83.72(2)°, β = 70.31(1)°, γ = 70.63(1)°, V = 1252.0(9) ų, Z = 1. The building units are centrosymmetric tetranuclear {[Cu(bpy)(OH)]₄Cl₂}²⁺ and {[Cu(phen)(OH)]₄(H₂O)₂}⁴⁺ complex cations formed by condensation of four elongated square pyramids CuN₂(OH)₂L^ap with the apical ligands L^ap = Cl, H₂O, OH. The resulting [Cu₄(μ₂‐OH)₂(μ₃‐OH)₂] core has the shape of a zigzag band of three Cu₂(OH)₂ squares. The cations exhibit intramolecular and intermolecular π‐π stacking interactions and the latter form 2D layers with the non‐bonded Cl^– anions and H₂O molecules in between (bond lengths: Cu–N = 1.995–2.038 Å; Cu–O = 1.927–1.982 Å; Cu–Cl^ap = 2.563; Cu–O^ap(OH) = 2.334–2.369 Å; Cu–O^ap(H₂O) = 2.256 Å). The Cu…Cu distances of about 2.93 Å do not indicate direct interactions, but the strongly reduced magnetic moment of about 2.74 B.M. corresponds with only two unpaired electrons per formula unit of 1 (1.37 B.M./Cu) and obviously results from intramolecular spin couplings (χ_m(T‐θ) = 0.933 cm³ · mol^–1 · K with θ = –0.7 K).     

Konformation und Vernetzung von (CuCN)6‐Ringen in polymeren Cyanocupraten(I) [Cu2(CN)3—] (n = 2, 3)

Conformation and Cross Linking of (CuCN)₆‐Rings in Polymeric Cyanocuprates(I) equation/tex2gif-stack-8.gif [Cu₂(CN)₃^—] (n = 2, 3) The alkaline‐tricyano‐dicuprates(I) Rbequation/tex2gif-stack-9.gif[Cu₂(CN)₃] · H₂O ( 1 ) and Csequation/tex2gif-stack-10.gif[Cu₂(CN)₃] · H₂O ( 2 ) were synthesized by hydrothermal reaction of CuCN and RbCN or CsCN. The dialkylammonium‐tricyano‐dicuprates(I) [NH₂(Me)₂]equation/tex2gif-stack-11.gif[Cu₂(CN)₃] ( 3 ), [NH₂(iPr)₂]equation/tex2gif-stack-12.gif[Cu₂(CN)₃] ( 4 ), [NH₂(Pr)₂]equation/tex2gif-stack-13.gif[Cu₂(CN)₃] ( 5 ) and [NH₂(secBu)₂]equation/tex2gif-stack-14.gif[Cu₂(CN)₃] ( 6 ) were obtained by the reaction of dimethylamine, diisopropylamine, dipropylamine or di‐sec‐butylamine with CuCN and NaCN in the presence of formic acid. The crystal structures of these compounds are built up by (CuCN)₆‐rings with varying conformations, which are connected to layers ( 1 ) or three‐dimensional zeolite type cyanocuprate(I) frameworks, depending on the size and shape of the cations ( 2 to 6 ). Crystal structure data: 1 , monoclinic, P2₁/c, a = 12.021(3)Å, b = 8.396(2)Å, c = 7.483(2)Å, β = 95.853(5)°, V = 751.4(3)ų, Z = 4, d_c = 2.728 gcm^—1, R₁ = 0.036; 2 , orthorhombic, Pbca, a = 8.760(2)Å, b = 6.781(2)Å, c = 27.113(5)Å, V = 1610.5(5)ų, Z = 8, d_c = 2.937 gcm^—1, R₁ = 0.028; 3 , orthorhombic, Pna2₁, a = 13.504(3)Å, b = 7.445(2)Å, c = 8.206(2)Å, V = 825.0(3)ų, Z = 4, d_c = 2.023 gcm^—1, R₁ = 0.022; 4 , orthorhombic, Pbca, a = 12.848(6)Å, b = 13.370(7)Å, c = 13.967(7)Å, V = 2399(2)ų, Z = 8, d_c = 1.702 gcm^—1, R₁ = 0.022; 5 , monoclinic, P2₁/n, a = 8.079(3)Å, b = 14.550(5)Å, c = 11.012(4)Å, β = 99.282(8)°, V = 1277.6(8)ų, Z = 4, d_c = 1.598 gcm^—1, R₁ = 0.039; 6 , monoclinic, P2₁/c, a = 16.215(4)Å, b = 13.977(4)Å, c = 14.176(4)Å, β = 114.555(5)°, V = 2922(2)ų, Z = 8, d_c = 1.525 gcm^—1, R₁ = 0.070.     

Synthesis,Crystal Structure,and Magnetic Properties of (2,2′‐dipyridylamine)(X−) Copper(II) Complexes (X−: Cyanate,Dicyanamide, Acetate,Thiocyanato)

The synthesis, structure, and magnetic properties of four 2,2′‐dipyridylamine ligand (abbreviated as Hdpa) containing copper(II) complexes. There is one binuclear compound, which is [Cu₂(μ_1,1‐NCO)₂(NCO)₂(Hdpa)₂] ( 1 ), and three mononuclear compounds, which are [Cu{N(CN)₂}₂(Hdpa)₂] ( 2 ), [Cu(CH₃CO₂)(Hdpa)₂·N(CN)₂] ( 3 ), and [Cu(NCS)(Acac)] ( 4 ). Compounds 1 and 4 crystallize in the monoclinic system, space group P2(1)/c and Z = 4, with a = 8.2465(6) Å, b = 9.3059(7) Å, c = 16.0817(12) Å, β = 91.090(1)°, and V = 1233.90(16) ų for 1 and a = 7.6766(6) Å, b = 21.888(3) Å, c = 10.4678(12) Å, β = 90.301(2)°, and V= 1758.8(4) ų for 4 . Compounds 2 and 3 crystallize in the triclinic system, space group P‐1 and Z = 1, with a = 8.1140(3) Å, b = 8.2470(3) Å, c = 9.3120(4) Å, β = 102.2370(10)°, and V = 592.63(4) ų for 2 and a = 7.4780(2) Å, b = 12.5700(3) Å, c = 13.0450(3) Å, β = 96.351(2)°, and V = 1211.17(5) ų for 3 . Complex ( 1 ), the magnetic data was fitted by the Bleaney‐Bowers equation (1). A very good fit was derived with J = 23.96, Θ = ?1.5 (g = 1.97). Complex ( 1 ) shows the ferromagnetism. Complexes ( 2 ), ( 3 ) and ( 4 ) of have the it is the typical paramagnetic behavior of unpaired electrons. Under a low temperature around 25 K, complexes ( 2 ) and ( 3 ) show weak ferromagnetic behavior. They are the cause of hydrogen bonds.     

Hydrothermal Synthesis and Structures of Two New Molybdenum Phosphate Compounds based on Keggin Cluster Units

Two new molybdenum phosphate complexes, [Cu₂(phen)₄(μ‐Cl)][PMo₁₂O₄₀]·H₂O (phen = 1,10‐phenanthroline) ( 1 ) and (Hbpy)[Cu^I(bpy)]₂[PMo^V₂Mo^VI₁₀O₃₉] (bpy = 4,4′‐bipyridine) ( 2 ), have been prepared under mild hydrothermal conditions and structurally characterized by single‐crystal X‐ray diffraction. Compounds 1 and 2 crystallize in triclinic system, space group , with a = 12.5458(7) Å, b = 13.4486(8) Å, c = 21.2406(12) Å, α = 99.7020(10)°, β = 94.2320(10)°, γ = 95.0890(10)°, V = 3504.2(3) ų and Z = 2 for 1 , and a = 10.7871(6) Å, b = 10.9016(6) Å, c = 12.7897(7) Å, α = 96.8500(10)°, β = 110.0850(10)°, γ = 103.5800(10)°, V = 1339.74(13) ų and Z = 1 for 2 . Compound 1 contains a [Cu₂(phen)₄(μ‐Cl)]³⁺ cation in which two similar [Cu(phen)₂] units are bridged by one chlorine atom. Compound 2 contains one‐dimensional straight chain of Keggin polyoxoanions [PMo^V₂Mo^VI₁₀O₃₉]_n^3? and two linear cationic chains of [Cu^I(bpy)]_nⁿ⁺. The molecular packing shows a two‐dimensional network, which is formed by the cross of the linear Keggin anions and Cu‐bpy cations.     

Inorganic−Organic Hybrid Polymers via Hydrothermal Syntheses: Tetraaquahexakis(pyrazine‐2‐carboxylato)pentacopper(4+) Hexacosaoxooctamolybdate(4−) Polymer ({[Cu5(pzca)6(H2O)4][Mo8O26]}n; pzca=Pyrazine‐2‐carboxylate) and Dicopperdecaoxo(pyrazine)trimolybdenum Polymer ([Mo3Cu2O10(pz)]n; pz=pyrazine)

Hydrothermal reactions of MoO₃, CuO, and pyrazine‐2‐carboxylic acid (Hpzca) resulted in two polymeric complexes, {[Cu₅(pzca)₆(H₂O)₄][Mo₈O₂₆]}_n ( 1 ; pzca=pyrazine‐2‐carboxylate) and [Mo₃Cu₂O₁₀(pz)]_n ( 2 ; pz=pyrazine). The former crystallized in the monoclinic space group P2₁/c with a=10.805(3) Å, b=13.061(5) Å, c=13.337(10) Å, β=90.20(4)°, V=2729(2) ų, and Z=2. The later crystallized in the orthorhombic space group Pnma with a=12.385(2) Å, b=7.6044(9) Å, c=12.7880(14) Å, V=1204.4(2) ų, and Z=4. X‐Ray diffraction analysis revealed that 1 possesses a two‐dimensional wave‐like structure, formed from a zigzag one‐dimensional chain, and 2 is a three‐dimensional network structure formed from a one‐dimensional chain and a pz bridging ligand. The temperature‐dependent magnetic behavior of 1 was studied.     

Molecular and Low‐dimensional Coordination Compounds of Copper(II) and 3, 5‐Dimethylpyrazole — Synthesis,Crystal Structure,and Properties

Three 3, 5‐dimethylpyrazole (pz*) copper(II) complexes, [Cu(pz*)₄(H₂O)](ClO₄)₂ ( 1 ), [Cu(pz*)₂(NCS)₂]·H₂O ( 2 ), and [Cu(pz*)₂(OOCCH=CHCOO)(H₂O)]·1.5H₂O ( 3 ), have been synthesized and characterized with single crystal X‐ray structure analysis. 1 crystallizes in the tetragonal space group, 14/m, with a = 14.027 (3) Å, c = 16.301 (5) Å, and Z = 4. 2 crystallizes in the monoclinic space group, P2₁/c, with a = 8.008 (3) Å, b = 27.139 (9) Å, c = 8.934 (3) Å, β = 106.345 (6)°, and Z = 4. 3 crystallizes in the triclinic space group, P1¯, with a = 7.291 (9) Å, b = 10.891 (13) Å, c = 11.822 (14) Å, α = 80.90 (2)°, β = 79.73(2)°, γ = 70.60(2)°, and Z = 2. In 1 , one water molecule and four pz* ligands are coordinated to Cu^II. Two [Cu(pz*)₄(H₂O)]²⁺ units are connected to ClO₄^— via hydrogen bonds. One lattice water molecule is found in the unit cell of 2 , which forms an one‐dimensional chain via intermolecular hydrogen bonds with the N‐H atom of pz*. In 3 , the oxygen atom of the coordinated water molecule is connected with two C=O groups of two neighbouring maleic acid molecules to form a linear parallelogram structure. Another C=O group of maleic acid forms a hydrogen bond with the N‐H atom of pz* to create a two‐dimensional structure. The spectroscopic and bond properties are also discussed.     

Hydrothermal Synthesis of Two Mixed‐Valence Copper Complexes with Mixed Ligands

Hydrothermal reactions of copper salts with fumaric acid, 1, 10‐phenanthroline or 2, 2‐bipyridine in basic aqueous solution gave rise to two mixed‐valence copper complexes [Cu₄(ophen)₄(fum)] ( 1 ) and [Cu₄(obipy)₄(fum)]·6H₂O ( 2 ) (fum = fumarate dianion, Hophen = 2‐hydroxy‐1, 10‐phenanthroline and Hobpy = 6‐hydroxy‐2, 2′‐bipyridine), which were characterized by single crystal X‐ray analysis. [Cu₄(ophen)₄(fum)] (1) crystallizes in the monoclinic space group P2₁/n, with a = 10.4749(8), b = 13.4210(9), c = 15.1090(10)Å, β = 103.811(3)° Z = 2; [Cu₄(obipy)₄(fum)]·6H₂O ( 2 ) has the triclinic space group P1¯, with a = 10.1302(11), b = 10.4406(12), c = 11.4450(13)Å, α = 84.384(2)°, β = 79.064(2)°, g = 67.734(2)° and Z = 1. The fumaric acid ligand acts as a multi‐dentate bridging ligand in both compounds, 1 and 2 , to link copper atoms into dumbbell structure. During the reactions, 1, 10‐phenanthroline and 2, 2′‐bipyridine ligands are all hydroxylated into ophen and obipy, which provide useful structural evidence for the study on the Gillard mechanism.     

Syntheses and Crystal Structures of Three Polymeric Silver(I) Terephthalate Complexes with Organic N‐Donor Ligands: [Ag(pren)]2(tp)·2H2O, [Ag(en)][Ag(μ2‐tp)]·H2O,and [Ag2(μ4‐tp)(apy)2]

Three polymeric silver(I) complexes with terephthalate anions as counterions or ligands, [Ag(pren)]₂(tp)·2H₂O ( 1 ), [Ag(en)][Ag(μ₂‐tp)]·H₂O ( 2 ), and [Ag₂(μ₄‐tp)(apy)₂] ( 3 ) (where pren = 1, 2‐propylenediamine, tp =terephthalate dianion, en = ethylenediamine, and apy = 2‐aminopyridine) were synthesized and characterized by X‐ray single crystal analysis and infrared spectroscopy. 1 crystallizes in the monoclinic space group P2₁1/c with a = 11.3221(5), b = 7.1522(3), c = 14.8128(5)Å, V = 1015.77(7)ų, β = 122.132(2), and Z = 2. 2 crystallizes in the orthorhombic space group Pnma with a = 9.6144(6), b = 11.3465(7), c = 11.4810(7)Å, V = 1252.5(1)ų, and Z = 4. 3 crystallizes in the monoclinic space group P2₁/n with a = 8.2003(5), b = 5.8869(4), c = 18.3769(11)Å, β = 92.593(1), V = 886.2(1)ų, and Z = 4. Terephthalate dianions are not coordinated to the metal atoms in 1 , but act as a μ₂‐bridging ligand in 2 and as a μ₄‐bridging ligand in 3 .     

A New Octadecanuclear Copper(II)‐Lanthanide(III) Cluster Complex: Synthesis and Structural Characterization of [Cu12Nd6(OH)24(betaine)16(NO3)3(H2O)10](NO3)[PF6]14·5H2O

The new octadecanuclear Cu‐Ln complex, [Cu₁₂Nd₆(OH)₂₄(betaine)₁₆(NO₃)₃(H₂O)₁₀](NO₃)[PF₆]₁₄·5H₂O, was synthesized, which crystallizes in triclinic P1¯ space group, a = 18.649(6)Å, b = 20.363(7)Å, c = 19.865(7)Å, α = 116.61(2)°, β = 91.99(2)°, γ = 117.93(2)°, V = 5666(3)ų. Its crystal structure features a [Cu₁₂Nd₆(OH)₂₄(betaine)₁₆(NO₃)₃(H₂O)₁₀]¹⁵⁺ core of pseudocubic O_h symmetry, with the six Nd ions positioned at the vertices of a regular octahedron and the twelve Cu ions located at the midpoints of the twelve octahedral edges. The Cu‐Nd metal framework may be viewed as a cuboctahedron, which is interconnected by twenty‐four μ₃‐OH bridges that are each linked to one Nd ion and two Cu ions. In the centre of metal polyhedron, there is an encapsulated NO₃^— anion that exhibits a multi‐ coordinating mode.     

Binuclear Copper(II) Complexes with Robsori-Type Ligands. Synthesis,characterization, crystal structure,and magnetic properties

Three binuclear copper(II) complexes, [Cu₂(μ-L)(μ-N₃)](ClO₄)2′ 1-5 EtOH (1), [Cu₂(μ-L)(μ-MeO)(ClO₄)]-ClO₄ - EtOH ( 2 ) and [Cu₂(μ-L)(μ-C₃H₃N₂)](ClO₄)₂ · 2H₂O, ( 3 ) where L is the pentadentale bridging ligand derived from 5-(tert-butyl)-2-hydroxybenzene-1, 3-dicarbaldehyde bis(benzoylhydrazone) ( HL ) were synthesized and characterized. The crystal-structure determination of complex 2 provided the following crystal data: monoclinic, space group P2₁}/a, a = 11.412(2), b = 24.509(4), c = 14.833(4) Å, β = 104.41(2)°, K = 4018(3) ų, Z = 4. The structure shows that the Cu^II ions are bridged by the endogenous phenolato O-atom and by an exogenous bridge CH₃O^?. The analysis of variable-temperature magnetic susceptibility data (4-300 K.) indicates that there is an antiferromagnetic interaction between the Cu^II ions in these complexes with an exchange parameter (2J) of ?119.1 cm^?1 for complex 1 and ?361.8 cm^?1 for complex 3 . The effect of some exogenous bridging ligands on magnetic coupling for this type of complex is suggested.     

Complex Formation of 2, 6‐Bis‐(2′‐hydroxyphenyl)pyridine with AlIII,FeIII and CuII

Complex formation of 2, 6‐bis(2′‐hydroxyphenyl)pyridine (H₂Lⁱ) with Fe³⁺ and Cu²⁺ was investigated in a H₂O/DMSO medium (mole fraction x_DMSO = 0.2) by potentiometric and spectrophotometric methods. The pK_a values of [H₃Lⁱ]⁺ are 2.25, 10.51 and 14.0 (25 °C, 0.1 M KCl). The formation constants of [Fe^III(Lⁱ)]⁺ and [Cu^II(Lⁱ)] (25 °C, 0.1 M KCl) are log β₁ = 21.5 for Fe³⁺ and log β₁ = 18.5 for Cu²⁺. The crystal structures of [Al(Lⁱ)₂Na(EtOH)₃], [Fe(Lⁱ)₂Na(EtOH)₃], and [Cu(Lⁱ)(py)]₂ were investigated by single‐crystal X‐ray diffraction analyses. The Fe^III and the Al^III compound are isotypic and crystallize in the monoclinic space group P2₁/n. Al‐compound (215 K): a = 12.599(3) Å, b = 16.653(3) Å, c = 17.525(4) Å, β = 100.27(3)°, Z = 4 for C₄₀H₄₀AlN₂NaO₇; Fe‐compound (293 K): a = 12.753(3) Å, b = 16.715(3) Å, c = 17.493(3) Å, β = 99.68(3)°, Z = 4 for C₄₀H₄₀FeN₂NaO₇. Both compounds contain a homoleptic, anionic bis‐complex [M(Lⁱ)₂]^‐ of approximate D₂ symmetry. The Cu compound crystallized as an uncharged, dinuclear and centrosymmetric [Cu(Lⁱ)(py)]₂ complex in the monoclinic space group P2₁/n with (293 K) a = 13.386(3) Å, b = 9.368(2) Å, c = 14.656(3) Å, β = 100.65(3)°, Z = 2 for C₄₄H₃₂Cu₂N₄O₄. The structural properties and in particular the possible influence of the ligand geometry on the stability of the metal complexes is discussed.     

Mesityl‐phenolato‐vanadium(III)‐Komplexe: Synthese,Struktur und Verhalten

Mesityl‐vanadium(III)‐phenolate Complexes: Synthesis, Structure, and Reactivity Protolysis reactions of [VMes₃(THF)] with ortho‐substituted phenols (2‐iso‐propyl‐(H–IPP), 2‐tert‐butyl(H–TBP), 2,4,6‐trimethylphenol (HOMes) and 2,2′biphenol (H₂–Biphen) yield the partially and fully phenolate substituted complexes [VMes(OAr)₂(THF)₂] (OAr = IPP ( 1 ), TBP ( 2 )), [VMes₂(OMes)(THF)] ( 4 ), [V(OAr)₃(THF)₂] (OAr = TBP ( 3 ), OMes ( 5 )), and [V₂(Biphen)₃(THF)₄] ( 6 ). Treatment of 6 with Li₂Biphen(Et₂O)₄ results in formation of [{Li(OEt₂)}₃V(Biphen)₃] ( 7 ) and with MesLi complexes [{Li(THF)₂}₂VMes(Biphen)₂] · THF ( 8 ) and [{Li(DME)}VMes₂(Biphen)] ( 9 ) are formed. Reacting [VCl₃(THF)₃] with LiOMes in 1 : 1 to 1 : 4 ratios yields the componds [VCl_3–n(OMes)_n(THF)₂] (n = 1 ( 5 b ), 2 ( 5 a ), 3 ( 5 )) and [{Li(DME)₂}V(OMes)₄] ( 5 c ), the latter showing thermochromism due to a complexation/decomplexation equilibrium of the solvated cation. The mixed ligand mesityl phenolate complexes [{Li(DME)_n}{VMes₂(OAr)₂}] (OAr = IPP ( 10 ), TBP ( 11 ), OMes ( 12 ) (n = 2 or 3) and [{Li(DME)₂}{VMes(OMes)₃}] ( 15 ) are obtained by reaction of 1 , 2 , 5 a and 5 with MesLi. With [{Li(DME)₂(THF)}{VMes₃(IPP)}] ( 13 ) a ligand exchange product of 10 was isolated. Addition of LiOMes to [VMes₃(THF)] forming [Li(THF)₄][VMes₃(OMes)] ( 14 ) completes the series of [Li(solv.)_x][VMes_4–n(OMes)_n] (n = 1 to 4) complexes which have been oxidised to their corresponding neutral [VMes_4–n(OMes)_n] derivatives 16 to 19 by reaction with p‐chloranile. They were investigated by epr spectroscopy. The molecular structures of 1 , 3 , 5 , 5 a , 5 a – Br , 7 , 10 and 13 have been determined by X‐ray analysis. In 1 (monoclinic, C2/c, a = 29.566(3) Å, b = 14.562(2) Å, c = 15.313(1) Å, β = 100.21(1)°, Z = 8), 3 (orthorhombic, Pbcn, a = 28.119(5) Å, b = 14.549(3) Å, c = 17.784(4) Å, β = 90.00°, Z = 8), ( 5 ) (triclinic, P1, a = 8.868(1) Å, b = 14.520(3) Å, c = 14.664(3) Å, α = 111.44(1)°, β = 96.33(1)°, γ = 102.86(1)°, Z = 2), 5 a (monoclinic, P2₁/c, a = 20.451(2) Å, b = 8.198(1) Å, c = 15.790(2) Å, β = 103.38(1)°, Z = 4) and 5 a – Br (monoclinic, P2₁/c, a = 21.264(3) Å, b = 8.242(4) Å, c = 15.950(2) Å, β = 109.14(1)°, Z = 4) the vanadium atoms are coordinated trigonal bipyramidal with the THF molecules in the axial positions. The central atom in 7 (trigonal, P3c1, a = 20.500(3) Å, b = 20.500(3) Å, c = 18.658(4) Å, Z = 6) has an octahedral environment. The three Li(OEt₂)⁺ fragments are bound bridging the biphenolate ligands. The structures of 10 (monoclinic, P2₁/c, a = 16.894(3) Å, b = 12.181(2) Å, c = 25.180(3) Å, β = 91.52(1)°, Z = 4) and 13 (orthorhombic, Pna2₁, a = 16.152(4) Å, b = 17.293(6) Å, c = 16.530(7) Å, Z = 4) are characterised by separated ions with tetrahedrally coordinated vanadate(III) anions and the lithium cations being the centres of octahedral and trigonal bipyramidal solvent environments, respectively.     

[CoIICuI2(Im)4];∞: A Layered Bimetallic Imidazolate Polymer,the First Hybridized Cobalt(II) Imidazolate

A 2D grid‐shaped bimetallic imidazolate polymer [Co^IICu^I₂(Im)₄]_;∞ ( 1 ) was solvothermally synthesized and characterized with single crystal X‐ray analysis: tetragonal space group P 2₁/c (No.114), a = b = 10.9513(15) Å, c = 6.3063(13) Å, V = 756.3(2) ų. This is the first cobalt(II) imidazolate polymer hybridized with other transition metals.     

Influence of the Counterions on the Structures of Ternary Zn/Sn/Se Anions: Synthesis and Properties of [Rb10(H2O)14.5][Zn4(μ4‐Se)2(SnSe4)4] and [Ba5(H2O)32][Zn5Sn(μ3‐Se)4(SnSe4)4]

Reactions of rubidium or barium salts of the ortho‐selenostannate anion, [Rb₄(H₂O)₄][SnSe₄] ( 1 ) or [Ba₂(H₂O)₅][SnSe₄] ( 2 ) with Zn(OAc)₂ or ZnCl₂ in aqueous solution yielded two novel compounds with different ternary Zn/Sn/Se anions, [Rb₁₀(H₂O)_14.5][Zn₄(μ₄‐Se)₂(SnSe₄)₄] ( 3 ) and [Ba₅(H₂O)₃₂][Zn₅Sn(μ₃‐Se)₄(SnSe₄)₄] ( 4 ). 1 – 4 have been determined by means of single crystal X‐ray diffraction: 1 : triclinic space group lattice dimensions at 203 K: a = 8.2582(17) Å, b = 10.634(2) Å, c = 10.922(2) Å, α = 110.16(3)°, β = 91.74(3)°, γ = 97.86(3)°, V = 888.8(3) ų; R₁ [I > 2σ(I)] = 0.0669; wR₂ = 0.1619; 2 : orthorhombic space group Pnma; lattice dimensions at 203 K: a = 17.828(4) Å, b = 11.101(2) Å, c = 6.7784(14) Å, V = 1341.5(5) ų; R₁ [I > 2σ(I)] = 0.0561; wR₂ = 0.1523; 3 : triclinic space group ; lattice dimension at 203 K: a = 17.431(4) Å, b = 17.459(4) Å, c = 22.730(5) Å, α = 105.82(3)°, β = 99.17(3)°, γ = 90.06(3)°, V = 6563.1(2) ų; R₁ [I > 2σ(I)] = 0.0822; wR₂ = 0.1782; 4 : monoclinic space group P2₁/c; lattice dimensions at 203 K: a = 25.231(5) Å, b = 24.776(5) Å, c = 25.396(5) Å, β = 106.59(3)°, V = 15215.0(5) ų; R₁ [I > 2σ(I)] = 0.0767; wR₂ = 0.1734. The results serve to underline the crucial role of the counterion for the type of ternary anion to be observed in the crystal. Whereas Rb⁺(aq) stabilizes a P1‐type Zn/Sn/Se supertetrahedron in 3 like K⁺, the Ba²⁺(aq) ions better fit to an anionic T3‐type Zn/Sn/Se cluster arrangement as do Na⁺ ions. It is possible to estimate a radius:charge ratio for the stabilization of the two structural motifs.     

Synthesis and Crystal Structure of [Cu2(H2O)2(phen)2(OH)2][Cu2(phen)2(OH)2(CO3)2] · 10 H2O with phen = 1,10‐phenanthroline

The blue copper complex [Cu₂(H₂O)₂(phen)₂(OH)₂][Cu₂(phen)₂(OH)₂(CO₃)₂] · 10 H₂O, which was prepared by reaction of 1,10‐phenanthroline monohydrate, CuCl₂ · 2 H₂O and Na₂CO₃ in the presence of succinic acid in CH3OH/H₂O at pH = 13.0, crystallized in the triclinic space group P1 (no. 2) with cell dimensions: a = 9.515(1) Å, b = 12.039(1) Å, c = 12.412(2) Å, α = 70.16(1)°, β = 85.45(1)°, γ = 81.85(1)°, V = 1323.2(2) ų, Z = 1. The crystal structure consists of dinuclear [Cu₂(H₂O)₂(phen)₂(OH)₂]²⁺ complex cations, dinuclear [Cu₂(phen)₂(OH)₂(CO₃)₂]^2– complex anions and hydrogen bonded H₂O molecules. In both the centrosymmetric dinuclear cation and anion, the Cu atoms are coordinated by two N atoms of one phen ligand, three O atoms of two μ‐OH groups and respectively one H₂O molecule or one CO₃^2– anion to complete distorted [CuN₂O₃] square‐pyramids with the H₂O molecule or the CO₃^2– anion at the apical position (equatorial d(Cu–O) = 1.939–1.961 Å, d(Cu–N) = 2.026–2.051 Å and axial d(Cu–O) = 2.194, 2.252 Å). Two adjacent [CuN₂O₃] square pyramids are condensed via two μ‐OH groups. Through the interionic hydrogen bonds, the dinuclear cations and anions are linked into 1D chains with parallel phen ligands on both sides. Interdigitation of phen ligands of neighboring 1D chains generated 2D layers, between which the hydrogen bonded water molecules are sandwiched.     

Two Novel CuII Phenanthroline Adipato Complexes with π‐π Stacking Interactions: [Cu(phen)2(C6H8O4)] · 4.5 H2O and [(Cu2(phen)2Cl2)(C6H8O4)] · 4 H2O

The blue copper complex compounds [Cu(phen)₂(C₆H₈O₄)] · 4.5 H₂O ( 1 ) and [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)] · 4 H₂O ( 2 ) were synthesized from CuCl₂, 1,10‐phenanthroline (phen) and adipic acid in CH₃OH/H₂O solutions. [Cu(phen)₂‐ (C₆H₈O₄)] complexes and hydrogen bonded H₂O molecules form the crystal structure of ( 1 ) (P1 (no. 2), a = 10.086(2) Å, b = 11.470(2) Å, c = 16.523(3) Å, α = 99.80(1)°, β = 115.13(1)°, γ = 115.13(1)°, V = 1617.5(5) ų, Z = 2). The Cu atoms are square‐pyramidally coordinated by four N atoms of the phen ligands and one O atom of the adipate anion (d(Cu–O) = 1.989 Å, d(Cu–N) = 2.032–2.040 Å, axial d(Cu–N) = 2.235 Å). π‐π stacking interactions between phen ligands are responsible for the formation of supramolecular assemblies of [Cu(phen)₂(C₆H₈O₄)] complex molecules into 1 D chains along [111]. The crystal structure of ( 2 ) shows polymeric [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)_2/2] chains (P1 (no. 2), a = 7.013(1) Å, b = 10.376(1) Å, c = 11.372(3) Å, α = 73.64(1)°, β = 78.15(2)°, γ = 81.44(1)°, V = 773.5(2) ų, Z = 1). The Cu atoms are fivefold coordinated by two Cl atoms, two N atoms of phen ligands and one O atom of the adipate anion, forming [CuCl₂N₂O] square pyramids with an axial Cl atom (d(Cu–O) = 1.958 Å, d(Cu–N) = 2.017–2.033 Å, d(Cu–Cl) = 2.281 Å; axial d(Cu–Cl) = 2.724 Å). Two square pyramids are condensed via the common Cl–Cl edge to centrosymmetric [Cu₂Cl₂N₄O₂] dimers, which are connected via the adipate anions to form the [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)_2/2] chains. The supramolecular 3 D network results from π‐π stacking interactions between the chains. H₂O molecules are located in tunnels.     

Syntheses and Crystal Structures of Two Metal Succinates Modified by Bipyridines

Two new metal succinates modified by rigid bipyridines, Cd(4, 4′‐bpy)(C₄H₄O₄)·1/4H₂O ( 1 ) and Cu(2, 2′‐bpy)(C₄H₄O₄)_0.5(NO₃)(H₂O) ( 2 ) (bpy = bipyridine), have been synthesized by hydrothermal reactions and structurally determined. Complex 1 crystallizes in the orthorhombic space group Cmca with the cell parameters a = 11.696(2), b = 15.554(2), c = 15.874(3) Å, α = β = γ = 90.00°, V = 2888(3) ų, Z = 8. Complex 2 crystallizes in the triclinic space group with a = 7.077(1), b = 9.838(2), c = 10.461(2) Å, α = 71.941(3)°, β = 73.078(3)°, γ = 74.502(3)°, V = 649.8(2) ų, Z = 2. In complex 1 , a 2‐D network was formed by Cd‐succinato bonding. The 2‐D networks are pillared by 4, 4′‐bpy ligands, forming a 3‐D grid framework. The 2‐fold interpenetration of the resulting 3‐D frameworks completes the molecular structure. In complex 2 , the Cu^II atom adopts a distorted octahedral in which the Cu^II atoms are bridged by two H₂O molecules into an infinite zigzag chain, [Cu₂(H₂O)₂(C₄H₄O₄)]_n. The neighboring chains are further linked by π‐π stacking interactions into a 2‐D network, and the interlayer hydrogen bonds lead to the final 3‐D crystal structure.     

Palladium(II) Complexes with the Mixed‐Donor Ligand CH3S‐(CH2)3‐PPh2 Crystal Structures of [PdCl2{CH3S‐(CH2)3‐PPh2}n](n = 1, 2)

The phosphorus‐sulfur ligand 1‐(methylthio)‐3‐(diphenylphosphino)‐propane (S‐P3) has been synthesized and characterized by ¹H NMR and ¹³C NMR. Reactions of S‐P3 with [PdCl₂(PhCN)₂] afforded the complexes [PdCl₂(S‐P3)] ( I ) and [PdCl₂(S‐P3)₂] ( II ), in which S‐P3 acts as a bidentate and monodentate ligand, respectively. Compound I crystallizes in monoclinic space group P2₁/n (No. 14) with cell dimensions: a = 8.589(3), b = 15.051(3), c = 17.100(3)Å, β = 102.91(2)°, V = 2154.7(9)ų, Z = 4. Likewise, compound II crystallizes in monoclinic space group P2₁/n (No. 14) with a = 9.993(5), b = 8.613(4), c = 18.721(5)Å, β = 90.18(3)°, V = 1611.3(12)ų, Z = 2. Compound II has a trans square planar configuration with only the P‐site of the ligand bonded to the palladium atom.     

Hydrothermal Synthesis and X‐ray Crystal Structure of Four Inorganic‐Organic Hybrid Compounds in Vanadium /Copper Iodate Family

Four inorganic‐organic hybrid compounds with the formulae (1,10‐phen)(VO₂)(IO₃) ( 1 ), (2,2′‐bipy)(VO₂)(IO₃) ( 2 ), [Cu₃(2,2′‐bipy)₃Cl₃(IO₃)₂]·I_1.5 ( 3 ), and [Cu(2,2′‐bipy)(H₂O)(IO₃)₂]· (H₂O)₂ ( 4 ) are hydrothermally synthesized at 120 °C for 6 d and characterized by single‐crystal X‐ray diffraction. The use of two different bidentate organodiamine ligands 1,10‐phen and 2,2′‐bipy in the V/I/O system gives rise to compounds 1 and 2 , which crystallize in a monoclinic system with the space group C2/c, a = 17.8131(6) Å, b = 15.0470(7) Å, c = 12.9902(4) Å, β = 133.095(2)°, V = 2542.49(17) ų for 1 and space group P2₁/c, a = 13.3095(5) Å, b = 15.0993(8) Å, c = 13.0454(4) Å, β = 116.971(2)°, V = 2335.88(17) ų for 2 . The use of the bidentate organodiamine ligand 2,2′‐bipy in the Cu/I/O system gives rise to the variety in the structure of products 3 and 4 , which crystallize in a triclinic system with the same space group . a = 8.5143(2) Å, b = 10.4908(3) Å, c = 22.8420(6) Å, α = 93.769(10)°, β = 91.723(10)°, γ = 112.111(10)°, V = 1882.83(9) ų for 3 and a = 6.731(6) Å, b = 10.110(4) Å, c = 12.899(6) Å, α = 106.00(5)°, β = 95.45(4)°, γ = 107.69(6)°, V = 788.4(9) ų for 4 . The solid‐state structures of the compounds 1 and 2 have chains with repeat units of alternative corner sharing of [VO₄N₂] octahedra and [IO₃] pyramids. Compound 3 is a chain containing [IO₃] pyramids and [VO₄N] square pyramids and compound 4 consists of Cu(2,2′‐bipy)²⁺ linked by one water molecule and two [IO₃] pyramids. The thermal stabilities of the compounds are investigated.     

Hydrothermal Synthesis,Structure, and Optical Properties of Two Nanosized Ln26@CO3 (Ln=Dy and Tb) Cluster‐Based Lanthanide–Transition‐Metal–Organic Frameworks (Ln MOFs)

Two Ln₂₆@CO₃ (Ln=Dy and Tb) cluster‐based lanthanide–transition‐metal–organic frameworks (Ln MOFs) formulated as [Dy₂₆Cu₃(Nic)₂₄(CH₃COO)₈(CO₃)₁₁(OH)₂₆(H₂O)₁₄]Cl ? 3 H₂O ( 1 ; HNic=nicotinic acid) and [Tb₂₆NaAg₃(Nic)₂₇(CH₃COO)₆(CO₃)₁₁(OH)₂₆Cl(H₂O)₁₅] ? 7.5 H₂O ( 2 ) have been successfully synthesized by hydrothermal methods and characterized by IR, thermogravimetric analysis (TGA), elemental analysis, and single X‐ray diffraction. Compound 1 crystallizes in the monoclinic space group Cc with a=35.775(12) Å, b=33.346(11) Å, c=24.424(8) Å, β=93.993(5)°, V=29065(16) ų, whereas 2 crystallizes in the triclinic space group P with a=20.4929(19) Å, b=24.671(2) Å, c=29.727(3) Å, α=81.9990(10)°, β=88.0830(10)°, γ=89.9940(10)°, V=14875(2) ų. Structural analysis indicates the framework of 1 is a 3D perovskite‐like structure constructed out of CO₃@Dy₂₆ building units and Cu⁺ centers by means of nicotinic acid ligand bridging. In 2 , however, nanosized CO₃@Tb₂₆ units and [Ag₃Cl]²⁺ centers are connected by Nic^? bridges to give rise to a 2D structure. It is worth mentioning that this kind of 4d–4f cluster‐based MOF is quite rare as most of the reported analogous compounds are 3d–4f ones. Additionally, the solid‐state emission spectra of pure compound 2 at room temperature suggest an efficient energy transfer from the ligand Nic^? to Tb³⁺ ions, which we called the “antenna effect”. Compound 2 shows a good two‐photon absorption (TPA) with a TPA coefficient of 0.06947 cm GM^?1 (1 GM=10^?50 cm⁴ s photon^?1), which indicates that compound 2 might be a good choice for third‐order nonlinear optical materials.