Synthesis of the One-dimensional Compound (Ph4P)[In(P2Se6)] in a Ph4P+-Containing Selenophosphate Flux,and Structure of [In(P2Se6)2]5– – a Discrete Molecular Fragment of the [In(P2Se6)]nn– Chain

The reaction of one equivalent of In with a molten flux of (Ph₄P)₂Se₅ and P₂Se₅ (1 : 2), at 250 °C gave the (Ph₄P)[In(P₂Se₆)] ( I ). Stoichiometric elemental synthesis at 750 °C produced the Cs₅In(P₂Se₆)₂ ( II ). The thin, yellow crystals of ( I ), and the irregular, dark orange crystals of ( II ), appear to be air- and water-stable. Compound ( I ) crystallizes in the monoclinic space group C2/c (no. 15) and at 23 °C: a = 23.127(7) Å, b = 6.564(1) Å, c = 19.083(3) Å, β = 97.42(2)°, V = 2873(1) ų, Z = 4, final R/R_w = 4.4/5.2%. Compound ( II ) crystallizes in the tetragonal space group P4₂/m (no. 84) and at 23 °C: a = b = 13.886(1) Å, c = 7.597(2) Å, V = 1464.9(3) ų, Z = 2, final R/R_w = 3.9/5.1%. Compound ( I ) contains infinite [In(P₂Se₆)]_n^n– with a structure related to that of K₂FeP₂Se₆. Compound ( II ) contains the discrete [In(P₂Se₆)₂]^5– which can be viewed as a fragment of the [In(P₂Se₆)]_n^n– chain.     

Synthesis,Crystal Structure,and Vibrational Spectroscopy of the Alkali Diselenates A2Se2O7 (A = Li – Cs)

The reaction of alkali carbonates and selenium acid yielded the “pyroanions” [Se₂O₇]^2– containing alkali diselenates. By varying the alkali carbonates we were able to synthesize and determinate the crystal structures of the whole row from Li to Cs. Li₂Se₂O₇ crystallizes isotypic to Li₂S₂O₇ [Pnma, Z = 4, a = 13.815(3), b = 8.452(2) c = 5.0585(10) Å]. The structure of Na₂Se₂O₇ [P$\bar{1}$ , Z = 2, a = 6.9896(14), b = 6.9938(14), c = 7.0829(14) Å, α = 83.32(3), β = 64.56(3), γ = 83.18(3)°] is isotypic to Ag₂S₂O₇. A₂Se₂O₇ (A = K, Rb) [A = K: C2/c, Z = 4, a = 12.851(3), b = 7.5677(15), c = 7.5677(15) Å, β = 93.35(3)°; A = Rb: C2/c, Z = 4, a = 13.118(3), b = 7.7963(16), c = 7.7811(16) Å, β = 94.03(3)°] are isotypic to K₂S₂O₇. The crystal structure of Cs₂Se₂O₇ [P$\bar{1}$ , Z = 10, a = 7.7271(3), b = 16.2408(8), c = 18.4427(8) Å, α = 89.685(2), β = 89.193(2), γ = 76.251(2)°] seems to be isotypic to the averaged room‐temperature modification of Cs₂S₂O₇. With exception of the caesium compound all diselenate anions show an ecliptic arrangement and can be therefore classified as dichromate‐like structures. In Cs₂Se₂O₇ most of the [Se₂O₇]^2– units have a staggered alignment. The transition between both orientations can be explained by the increase of the cations size. Additionally the vibrational spectra of A₂Se₂O₇ with A = Li – Cs are discussed as well as the resulting bond forces.     

Synthesis,Crystal Structure and Properties of [Mn(hdpa)2(N(CN)2)2] and [Co(hdpa)2(N(CN)2)2] (hdpa = 2, 2'‐Dipyridylamine)

Two new transition metal(II) complexes [M(hdpa)₂(N(CN)₂)₂] (M = Mn ( 1 ), Co ( 2 ); hdpa = 2, 2'‐dipyridylamine) have been prepared and characterized structurally and magnetically. Both compounds crystallize in the monoclinic space group C2/c. 1 and 2 are isotypic with the unit cell parameters a = 8.634(9), b = 13.541(14), c = 21.99(2) Å, β = 94.806(18)°, and V = 2562(5) ų for 1 , a = 8.617(3) Å, b = 13.629(5)Å, c = 21.598(8)Å, β = 94.593(6)°, and V = 2528.4(15)ų for 2 , and Z = 4 for both. According to X‐ray crystallographic studies, each metal(II) ion was six‐coordinated with four nitrogen atoms from two bidentate hdpa ligand and two nitrogen atoms from two N(CN)^— anions to form slightly distorted octahedrons. Adjacent complex molecules are connected by hydrogen bonds or π···π interactions to form three‐dimensional network. The IR and UV spectroscopy were measured and the magnetic behaviors were investigated.     

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.     

Syntheses and crystal structure studies of two compounds of quinolones

Two complexes with enoxacin and ciprofloxacin were synthesized and the crystal structures are reported. Compound 1, [Cu(H-Eno) · Cl₂] · 3H₂O (H-Eno = Enoxacin), crystallizes in the triclinic system, space group P 1, with lattice parameters a = 8.7731(12) Å, b = 9.4976(14) Å, c = 13.2033(19) Å, α = 86.319(7)°, β = 71.912(7)°, γ = 80.604(7)°, V = 1031.6(3) ų, Z = 2, D _c = 1.625 mgm^?3. 2, [Mn(Cip)₂] · 2H₂O (Cip = mono-anion of ciprofloxacin), crystallizes in the monoclinic, space group P2(1)/c, with lattice parameters a = 5.85690(10), b = 21.9490(6), c = 13.4443(3) Å, β = 100.9700(10)°, V = 1696.72(7) ų, Z = 2, D _c = 1.459 mgm^?3.     

Three Crystal Structures,One Chemical Formula – Barium Dihydrogen‐hypodiphosphate(IV)‐dihydrate,BaH2P2O6·2H2O

Three polymorphs of barium dihydrogen‐hypodiphosphate(IV)‐dihydrate, BaH₂P₂O₆ · 2H₂O ( A , B and C ), were obtained and structurally characterized by single‐crystal X‐ray diffraction. A crystallizes in the monoclinic space group P2₁/n (no. 14) with a = 7.459(1) Å, b = 8.066(1) Å, c = 12.460(2) Å, β = 91.27(1) ° and Z = 4. B crystallizes in the monoclinic space group C2/c (no. 15) with a = 11.049(8) Å, b = 6.486(3) Å, c = 10.956(6) Å, β = 106.89(5) ° and Z = 4. C crystallizes in the orthorhombic space group C222₁ (no. 20) with a = 9.193(3) Å, b = 6.199(2) Å, c = 12.888(4) Å and Z = 4. Discrete [H₂P₂O₆]^2– units, barium cations and water molecules, held together by intermolecular hydrogen bonds of the type O–H ··· O, build up the structures of the three polymorphs. The phase purity of A and C was verified by powder diffraction measurements.     

Synthesis and Structural Characterization of the Helical Coordination Polymers [Co(phen)(oba)(H2O)2] and [Cd3(phen)3(oba)2(Hoba)2(H2O)2] (phen = 1, 10‐phenanthroline; oba = 4, 4′‐oxybis(benzoate)

Two coordination polymers, [Co(phen)(oba)(H₂O)₂] ( 1 ) and [Cd₃(phen)₃(oba)₂(Hoba)₂(H₂O)₂] ( 2 ) (oba = 4, 4′‐oxybis(benzoate), phen = 1, 10‐phenanthroline) have been synthesized under hydrothermal conditions. Complex 1 crystallizes in monoclinic, P2₁/n, a = 7.543(6), b = 33.05(2), c = 9.902(5)Å, β = 103.69(2)°, V = 2398(3)ų, Z = 4; 2 in monoclinic, P2/n, a = 15.11(1), b = 10.069(8), c = 28.02(2)Å, β = 101.83(1)°, V = 4174(5)ų, Z = 2. X‐ray single‐crystal diffraction investigations shows that the complexes 1 and 2 consist of helical chains, which are further assembled into layers and networks via supramolecular interactions such as π—π stacking interactions and hydrogen bonds, respectively. The results indicate that the coordination environment is one of the most important factors for assembly of single‐stranded helical chains into double‐stranded helical chains via supramolecular interactions.     

Alkoxo‐Verbindungen des dreiwertigen Eisen: Synthese und Charakterisierung von [Fe2(OtBu)6], [Fe2Cl2(OtBu)4], [Fe2Cl4(OtBu)2] und [N(nBu)4]2[Fe6OCl6(OMe)12]

Alkoxo Compounds of Iron(III): Syntheses and Characterization of [Fe₂(OtBu)₆], [Fe₂Cl₂(OtBu)₄], [Fe₂Cl₄(OtBu)₂] and [N(nBu)₄]₂[Fe₆OCl₆(OMe)₁₂] The reaction of iron(III)chloride in diethylether with sodium tert‐butylat yielded the homoleptic dimeric tert‐‐butoxide Fe₂(OtBu)₆ ( 1 ). The chloro‐derivatives [Fe₂Cl₂(OtBu)₄] ( 2 ), and [Fe₂Cl₄(OtBu)₂] ( 3 ) could be synthesized by ligand exchange between 1 and iron(III)chloride. Each of the molecules 1 , 2 , and 3 consists of two edge‐sharing tetrahedrons, with two tert‐butoxo‐groups as μ₂‐bridging ligands. For the synthesis of the alkoxides 1 , 2 , and 3 diethylether plays an important role. In the first step the dietherate of iron(III)chloride FeCl₃(OEt₂)₂ ( 4 ) is formed. The reaction of iron(III)chloride with tetrabutylammonium methoxide in methanol results in the formation of a tetrabutylammonium methoxo‐chloro‐oxo‐hexairon cluster [N(nBu)₄]₂[Fe₆OCl₆(OMe)₁₂] ( 5 ). Crystal structure data: 1 , triclinic, P1¯, a = 9.882(2) Å, b = 10.523(2) Å, c = 15.972(3) Å, α = 73.986(4)°, β = 88.713(4)°, γ = 87.145(4)°, V = 1594.4(5) ų, Z = 2, d_c = 1.146 gcm^—1, R₁ = 0.044; 2 , monoclinic, P2₁/n, a = 11.134(2) Å, b = 10.141(2) Å, c = 12.152(2) Å und β = 114.157(3)°, V = 1251.8(4) ų, Z = 2, d_c = 1.377 gcm^—1, R₁ = 0.0581; 3 , monoclinic, P2₁/n, a = 6.527(2) Å, b = 11.744(2) Å, c = 10.623(2), β = 96.644(3)°, V = 808.8(2) ų, Z = 2, d_c = 1.641 gcm^—1, R₁ = 0.0174; 4 , orthorhombic, Iba2, a = 23.266(5) Å, b = 9.541(2) Å, c = 12.867(3) Å, V = 2856(2) ų, Z = 8, d_c = 1.444 gcm^—1, R₁ = 0.0208; 5 , trigonal, P3₁, a = 13.945(2) Å, c = 30.011(6) Å, V = 5054(2) ų, Z = 6, d_c = 1.401 gcm^—1; R_c = 0.0494.     

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.     

Syntheses and Crystal Structures of the Novel Ternary Thioborates Na3BS3, K3BS3, and Rb3BS3

The orthothioborates Na₃BS₃, K₃BS₃ and Rb₃BS₃ were prepared from the metal sulfides, amorphous boron and sulfur in solid state reactions at temperatures between 923 and 973 K. In a systematic study on the structural cation influence on this type of ternary compounds, the crystal structures were determined by single crystal X‐ray diffraction experiments. Na₃BS₃ crystallizes in the monoclinic space group C2/c (No. 15) with a = 11.853(14) Å, b = 6.664(10) Å, c = 8.406(10) Å, β = 118.18(2)° and Z = 4. K₃BS₃ and Rb₃BS₃ are monoclinic, space group P2₁/c (No. 14) with a = 10.061(3) Å, b = 6.210(2) Å, c = 12.538(3) Å, β = 112.97(2) and a = 10.215(3) Å, b = 6.407(1) Å, c = 13.069(6) Å, β = 103.64(5)°, Z = 4. The potassium and rubidium compounds are not isotypic. All three compounds contain isolated [BS₃]^3– anions with boron in a trigonal‐planar coordination. The sodium cations in Na₃BS₃ are located between layers of orthothioborate anions, in the case of K₃BS₃ and Rb₃BS₃ stacks of [BS₃]^3– entities are connected via the corresponding cations. X‐ray powder patterns were measured and compared to calculated ones obtained from single crystal X‐ray structure determinations.     

Alkoholyse von [Fe2(OtBu)6] als einfacher Weg zu neuen Eisen(III)‐Alkoxo‐Verbindungen: Synthesen und Kristallstrukturen von [Fe2(OtAmyl)6], [Fe5OCl(OiPr)12], [Fe5O(OiPr)13], [Fe5O(OiBu)13], [Fe5O(OCH2CF3)13], [Fe5O(OnPr)13] und [Fe9O3(OnPr)21] · iPrOH

Alcoholysis of [Fe₂(O^tBu)₆] as a Simple Route to New Iron(III)‐Alkoxo Compounds: Synthesis and Crystal Structures of [Fe₂(O^tAmyl)₆], [Fe₅OCl(OⁱPr)₁₂], [Fe₅O(OⁱPr)₁₃], [Fe₅O(OⁱBu)₁₃], [Fe₅O(OCH₂CF₃)₁₃], [Fe₅O(OⁿPr)₁₃], and [Fe₉O₃(OⁿPr)₂₁] · ⁿPrOH New alkoxo‐iron compounds can be synthesized easily by alcoholysis of [Fe₂(O^tBu)₆] ( 1 ). Due to different bulkyness of the alcohols used, three different structure types are formed: [Fe₂(OR)₆], [Fe₅O(OR)₁₃] and [Fe₉O₃(OR)₂₁] · ROH. We report synthesis and crystal structures of the compounds [Fe₅OCl(OⁱPr)₁₂] ( 2 ), [Fe₂(O^tAmyl)₆] ( 3 ), [Fe₅O(OⁱPr)₁₃] ( 4 ), [Fe₅O(OⁱBu)₁₃] ( 5 ), [Fe₅O(OCH₂CF₃)₁₃] ( 6 ), [Fe₉O₃(OⁿPr)₂₁] · ⁿPrOH ( 7 ) and [Fe₅O(OⁿPr)₁₃] ( 8 ). Crystallographic Data: 2 , tetragonal, P 4/n, a = 16.070(5) Å, c = 9.831(5) Å, V = 2539(2) ų, Z = 2, d_c = 1.360 gcm^?3, R₁ = 0.0636; 3 , monoclinic, P 2₁/c, a = 10.591(5) Å, b = 10.654(4) Å, c = 16.740(7) Å, β = 104.87(2)°, V = 1826(2) ų, Z = 2, d_c = 1.154 gcm^?3, R₁ = 0.0756; 4 , triclinic, , a = 20.640(3) Å, b = 21.383(3) Å, c = 21.537(3) Å, α = 82.37(1)°, β = 73.15(1)°, γ = 61.75(1)°, V = 8013(2) ų, Z = 6, d_c = 1.322 gcm^?3, R₁ = 0.0412; 5 , tetragonal, P 4cc, a = 13.612(5) Å, c = 36.853(5) Å, V = 6828(4) ų, Z = 4, d_c = 1.079 gcm^?3, R₁ = 0.0609; 6 , triclinic, , a = 12.039(2) Å, b = 12.673(3) Å, c = 19.600(4) Å, α = 93.60(1)°, β = 97.02(1)°, γ = 117.83(1)°, V = 2600(2) ų, Z = 2, d_c = 2.022 gcm^?3, R₁ = 0.0585; 7 , triclinic, , a = 12.989(3) Å, b = 16.750(4) Å, c = 21.644(5) Å, α = 84.69(1)°, β = 86.20(1)°, γ = 77.68(1)°, V = 4576(2) ų, Z = 2, d_c = 1.344 gcm^?3, R₁ = 0.0778; 8 , triclinic, , a = 12.597(5) Å, b = 12.764(5) Å, c = 16.727(7) Å, α = 91.94(1)°, β = 95.61(1)°, γ = 93.24(2)°, V = 2670(2) ų, Z = 2, d_c = 1.323 gcm^?3, R₁ = 0.0594.     

Three Copper(II) Coordination Polymers Constructed by Both Rigid and Flexible Ligands

Three new Copper(II) polymers coordinated by both rigid and flexible ligands, [Cu(bpy)(C₅H₆O₄)]_n ( 1 ), [Cu(bpy)(C₆H₈O₄)]_n ( 2 ), and [Cu₂(bpy)₂(C₆H₈O₄)₂]_n ( 3 ) (bpy = 4,4′‐bipyridine), have been hydrothermally synthesized and structurally characterized. Complex 1 features a box‐like bilayer motif of (4, 4) net. It crystallizes in triclinic space group with cell parameters: a = 8.1395(6) Å, b = 9.43 12(8) Å, c = 10.5473(8) Å, α = 112.1830(1)°, β = 92.423(2)°, γ = 104.752(2)°, V = 716.31(1) ų, Z = 2. Complex 2 crystallizes in triclinic space group with a = 8.8652(4) Å, b = 8.9429(4) Å, c = 10.6390(4) Å, α = 89.520(2)°, β = 69.123(2)°, γ = 75.2440(1)°, V = 758.92(6) ų, Z = 2. Complex 3 crystallizes in monoclinic space group Cc with a = 11.1521(1) Å, b = 15.3961(1) Å, c = 17.7419(1) Å, β = 105.715(3)°, V = 2932.4(5) ų, Z = 4. Complexes 2 and 3 are isomeric with different coordination modes of adipato ligand. Both of them possess the two‐fold interpenetrated 3‐D pcu topological net.     

Crystal structure,electronic structure and electrical conductivity of the antimony selenide BaLaSb2Se6

BaLaSb₂S₆ and BaLaSb₂Se₆ were prepared by heating the elements in the stoichiometric ratio under exclusion of air at 850 °C. Both chalcogenides adopt the KThSb₆Se₆ structure type, crystallizing in the space group P2₁/c (Z = 4) with a = 4.324(3) Å, b = 14.7057(16) Å, c = 15.910(2) Å, β = 92.741(3)°, Z = 4 for the sulfide and a = 4.4173(3) Å, b = 15.333(1) Å, c = 16.816(1) Å, β = 92.545(2)°, Z = 4 for the selenide. The structure of BaLaSb₂Se₆ is composed of ribbons of distorted SbSe₆ octahedra and Se₂^2? pairs. Electronic structure calculations show that the selenide is a semiconductor, in accord with the electrical conductivity measurement.     

Synthesis,Crystal Structures,and Characterization of Two 3d‐3d Heterometallic Coordination Frameworks: [ZnCo(Hcit)Cl] and [ZnCo(Hcit)Br]

Reactions between CoO, ZnCl₂ (or ZnBr₂), and molten citric acid (Hcit) led to the formation of two 3d‐3d heterometallic coordination frameworks: [ZnCo(Hcit)Cl] ( 1 ) and [ZnCo(Hcit)Br] ( 2 ). X‐ray structure analyses show that both compounds 1 and 2 crystallize in the monoclinic space group P2₁/n [ 1 : a = 5.8699(5) Å, b = 17.7963(13) Å, c = 9.2152(8) Å, β = 106.806(4) °, Z = 4, V = 921.53(13) Å³; 2 : a = 5.909(3) Å, b = 17.798(8) Å, c = 9.302(5) Å, β = 106.374(7) °, Z = 4, V = 938.6(8) Å³]. The structures of the two compounds are almost the same except for the terminal halogen ligand. Both of them are 3D frameworks based on citric acid bridging ligands and a 1D backbone chain built of corner‐shared {CoO₆} and {ZnO₃Cl} polyhedra. Photoluminescence and thermal stabilities of the compounds were studied.     

Adipato‐Bridged Mixed Ligand catena Complexes: ${_{\infty}^1}${[M(phen)(H2O)]L2/2} with M = NiII,CuII, ZnII; H2L = Adipic Acid

Three adipato bridged mixed ligand catena complexes {[M(phen)(H₂O)]‐(C₆H₈O₄)_2/2} with M = Ni^II ( 1 ), Cu^II ( 2 ), Zn^II ( 3 ) were synthesized. Structure determination based on X‐ray diffraction shows that they crystallize isostructurally in the monoclinic space group C2/c (no. 15) with cell dimensions of: 1 a = 22.451(4)Å, b = 9.041(1)Å, c = 17.440(2)Å, β = 103.41(1)°, U = 3443.4(9)ų, Z = 8; 2 a = 22.479(2)Å, b = 9.067(1)Å, c = 17.494(3)Å, β = 103.67(1)°, U = 3464.6(8)ų, Z = 8; 3 a = 22.635(3)Å, b = 9.052(1)Å, c = 17.571(3)Å, β = 103.24(1)°, U = 3504.5(9)ų, Z = 8. The crystal structure consists of 1D {[M(phen)(H₂O)]‐(C₆H₈O₄)_2/2} zigzag chains, in which the metal atoms are all octahedrally coordinated by two N atoms of one phen ligands and four O atoms of one H₂O molecule and two adipato ligands. The zigzag chains are held together by interchain π‐π stacking interactions and interchain hydrogen bonds.     

Synthesis and Characterization of the Rubidium Thiophosphate Rb6(PS5)(P2S10) and the Rubidium Silver Thiophosphates Rb2AgPS4, RbAg5(PS4)2 and Rb3Ag9(PS4)4

The metal thiophosphates Rb₂AgPS₄ ( 2 ), RbAg₅(PS₄)₂ ( 3 ), and Rb₃Ag₉(PS₄)₄ ( 4 ) were synthesized by stoichiometric reactions, whereas Rb₆(PS₅)(P₂S₁₀) ( 1 ) was prepared with excess amount of sulfur. The compounds crystallize as follows: 1 monoclinic, P2₁/c (no. 14), a = 17.0123(7) Å, b = 6.9102(2) Å, c = 23.179(1) Å, β = 94.399(4)°; 2 triclinic, P$\bar{1}$ (no. 2), a = 6.600(1) Å, b = 6.856(1) Å, c = 10.943(3) Å, α = 95.150(2)°, β = 107.338(2)°, γ = 111.383(2)°; 3 orthorhombic, Pbca (no. 61), a = 12.607(1) Å, b = 12.612(1) Å, c = 17.759(2) Å; 4 orthorhombic, Pbcm (no. 57), a = 6.3481(2) Å, b = 12.5782(4) Å, c = 35.975(1) Å. The crystal structures contain discrete units, chains, and 3D polyanionic frameworks composed of PS₄ tetrahedral units arranged and connected in different manner. Compounds 1 – 3 melt congruently, whereas incongruent melting behavior was observed for compound 4 . 1 – 4 are semiconductors with bandgaps between 2.3 and 2.6 eV and thermally stable up to 450 °C in an inert atmosphere.     

Synthesis,Crystal Structure,and Characterization of three New Letrozole Complexes

Three new letrozole complexes {[Cu(Le)₄Cl₂] · (H₂O)} ( 1 ), {[Ni(Le)₄Cl₂] · (H₂O)}( 2 ) and {[Co(Le)₄Cl₂] · (H₂O)} ( 3 ) (Le = letrozole = 1‐[bis(4‐cyanophenyl)methyl]‐1, 2, 4‐triazole) were obtained from self‐assembly of CuCl₂, NiCl₂ · 6H₂O, and CoCl₂ · 6H₂O with medicine letrozole. All compounds were characterized by IR spectroscopy, elemental, single‐crystal as well as powder X‐ray diffraction, and thermogravimetric analyses. The analyses of the structures indicate that all crystals belong to monoclinic system, space group C2/c, for complex 1 with crystal data a = 34.501(18) Å, b = 12.724(7) Å, c = 16.116(9) Å, β = 114.958(7) °, V = 6414(6) Å ³, Z = 4, F(000) = 2660, R₁ = 0.0668, wR₂ = 0.1574; for complex 2 , a = 34.769(6) Å, b = 12.7267(18) Å, c = 16.046(2) Å, β = 115.281(3) °, V = 6420.1(16) Å ³, Z = 4, F(000) = 2656, R₁ = 0.0510, wR₂ = 0.0896; for complex 3 , a = 35.063(8) Å,b = 12.658(3) Å, c = 16.056(4) Å, β = 115.387(3) °, V = 6438(2) ų, Z = 4, F(000) = 2652, R₁ = 0.0528, wR₂ = 0.1205. The local arrangements around central metal atoms (Cu^II, Ni^II, and Co^II) can be best described as distorted octahedra which are constructed by two chlorine atoms and four monodentate nitrogen atoms from different letrozole ligands. XRD results of 1 – 3 show that all peaks displayed in the measured patterns at room temperature closely match those in the simulated patterns generated from single‐crystal diffraction data, indicating single phases of 1 – 3 were formed.     

Bridging chlorides and hydroxides: syntheses and crystal structures of binuclear and tetranuclear NiII complexes derived from a reduced Schiff-base ligand 2-(2-pyridylmethylamino)ethanesulfonic acid

Two complexes, [Ni(pmt)(Cl)] (1) and [Ni₄(pmt)₄(OH)₄]·8H₂O (2) [Hpmt = 2-(2-pyridylmethylamino)ethanesulfonic acid], were synthesized by different experimental methods in methanol-water mixed solution. Compound 1 crystallizes in triclinic, space group P?1 with unit cell parameters: a = 8.315(2) Å, b = 8.383(2) Å, c = 9.128(2) Å, α = 103.654(2)°, β = 98.125(2)°, γ = 113.154(2)°, V = 548.6(2) ų, Z = 2. A pair of chlorides is μ ₂-bridges linking two Ni^II atoms in forming binuclear complex 1. The coordination environment at Ni^II is distorted square-pyramidal geometry. Compound (2) belongs to monoclinic, space group C2/c, with a = 16.5168(15) Å, b = 18.3718(17) Å, c = 17.5473(16) Å, α = γ = 90°, β = 93.3820(10)°, V = 5315.3(8) ų, Z = 4. Four hydroxides are μ ₃-bridges joining four Ni^II atoms to generate a cubic framework as a tetranuclear complex. The configuration at each Ni^II is distorted octahedral. Both π–π stacking of pyridine rings and intermolecular hydrogen bonds stabilize the solid state structures for 1 and 2.     

Synthesis and structure determination of MIL-10: A monodimensional metallodiphosphonate formulated MIVO{O3P-CH2-PO3}(NH4)2 (M = Ti,V)

In the view of synthesizing microporous composite compounds, the ternary systems NH₄VO₃: alkyldiphosphonic acid:H₂O were hydrothermally investigated. Using the methylendiphosphonic acid, the mixture corresponding to the molar ratio 1:0.3:500 heated three days at 200 °C, leads to small platelets whose structure was determined by single crystal X-ray diffraction. Their symmetry is orthorhombic (space group Pnma (n° 62)) with lattice parameters: a = 7.3182(1) Å, b = 16.5633(1) Å, c = 7.5225(2) Å, V = 911.83(4) ų, Z = 4. The compound labelled MIL-10, is formulated V^IVO{O₃P-CH₂-PO₃}(NH₄)₂, and shows a monodimensional structure characterized by the presence of polyhedral chains between which ammonium cations are located. The isostructural titanium compound was also hydrothermally synthesized. Its structure was solved from single crystal data; its symmetry is orthorhombic (space group Cmcm (n° 63)) with lattice parameters: a = 16.462(1) Å, b = 7.7671(6) Å, c = 7.2830(6) Å, V = 931.2(1) ų, Z = 4.