Crystal Structure of the Octahedral Cs4[Re6S8Br6] · 2H2O Cluster Complex

The octahedral Cs₄[Re₆S₈Br₆] cluster complex was obtained by the hightemperature (850°) reaction of stoichiometric amounts of elemental substances (metallic rhenium, sulfur, bromine) in molten CsBr. Crystal hydrate of Cs₄[Re₆S₈Br₆]· 2H₂O composition was isolated by recrystallization from an aqueous HBr solution. The crystal structure of the hydrate was determined by means of singlecrystal Xray structural analysis. The compound crystallizes in the hexagonal system with space group P6₃/mcm and unit cell parameters a = 9.762(1), c = 18.763(2), V_cell = 1548.5(3)³, Z = 2, d _calc = 5.192 g/cm³.     

Two binuclear complexes containing the enrofloxacinate anion: Cd2(C19H21N3O3F)4(H2O)2 · 4H2O and Pb2(C19H21N3O3F)4 · 4H2O

The syntheses and crystal structures of the closely related but non-isostructural Cd₂(C₁₉H₂₁N₃O₃F)₄(H₂O)₂?·?4H₂O (1) and Pb₂(C₁₉H₂₁N₃O₃F)₄?·?4H₂O (2) are described, where C₁₉H₂₁N₃O₃F^? is enrofloxacinate (enro). Both compounds contain centrosymmetric, binuclear, neutral complexes incorporating a central diamond-shaped M₂O₂ (M?=?Cd, Pb) structural unit. The Cd²⁺ coordination polyhedron in 1 is a CdO₆ trigonal prism, including one coordinated water. The Pb²⁺ coordination polyhedron in 2 can be described as a very distorted square-based PbO₅ pyramid, although two additional short Pb?···?O (<3.1?Å) contacts are also present. In the crystal of the cadmium complex, O–H?···?O hydrogen bonds lead to a layered structure. In the lead compound, O–H?···?O and O–H?···?N interactions lead to chains in the crystal. Crystal data: 1: C₇₆H₉₆Cd₂F₄N₁₂O₁₈, M _r?=?1766.45, triclinic, P 1, a?=?12.185(2)?Å, b?=?12.306(3)?Å, c?=?14.826(3)?Å, α?=?68.15(3)°, β?=?70.28(3)°, γ?=?86.11(3)°, V?=?1938.2(7)?ų, Z?=?1, T?=?298 K, R(F)?=?0.030, wR(F ²)?=?0.079. 2: C₇₆H₈₈F₄N₁₂O₁₆Pb₂, M _r?=?1920.00, triclinic, P 1, a?=?12.0283(4)?Å, b?=?12.7465(4)?Å, c?=?13.0585(4)?Å, α?=?83.751(1)°, β?=?74.635(1)°, γ?=?81.502(1)°, V?=?1904.3(1)?ų, Z?=?1, T?=?298?K, R(F)?=?0.021, wR(F ²)?=?0.049.     

23-Electron Re6 metal clusters: syntheses and crystal structures of (Ph4P)3[Re6S8(CN)6], (Ph4P)2(H)[Re6Se8(CN)6]·8H2O,and (Et4N)2(H)[Re6Te8(CN)6]·2H2O

The cluster anions [Re₆X₈(CN)₆]^34– (X = S, Se, or Te) containing 23 cluster valence electrons in the Re₆ octahedron were synthesized and isolated as salts with organic cations. The crystal structures of the (Ph₄P)₃[Re₆S₈(CN)₆], (Ph₄P)₂(H)[Re₆Se₈(CN)₆]·8H₂O, and (Et₄N)₂(H)[Re₆Te₈(CN)₆]·2H₂O clusters were solved by X-ray diffraction analysis. Removal of one electron has virtually no effect on the geometry and interatomic distances in the cluster anion but leads to a substantial change in the electronic spectrum and to an increase in stretching vibration frequencies _CN compared to those of the [Re₆X₈(CN)₆]^4– anions.     

Synthesis and Structural Characterization of a Novel Coordination Polymer [Cd(C4H2O4)(C3H4N2)3]n·2nH2O

At room temperature, a new three-dimensional organic-inorganic coordination polymer [Cd(C4H2O4)(C3H4N2)3]n·2nH2O was synthesized by the reaction of Cd(CH3COO)2(2H2O, imidazole and fumaric acid. It was characterized by EA, IR, TG-DTA and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 8.980(3), b = 15.803(5), c = 13.415(4) (A), α = γ = 90.00°, β = 98.450(5)°, F(000) = 936, Mr = 466.73, Z = 4, V = 1883.0(10) (A)3, Dc = 1.646 g/cm3, μ(MoKα) = 1.201 mm-1, S = 1.041, the final R = 0.0237 and wR = 0.0469. The crystal structure shows that the cadmium has a distorted octahedral environment with three carboxyl oxygen donors and three imidazole nitrogen donors. Each cadmium atom is linked by a fumatate as bridging ligand to afford a one-dimensional framework, and then an infinite threedimensional supramolecular network is formed through hydrogen bonding interactions.     

Crystal Structure of [(C2H5)4N]4Cu7Cl14O2: A Cu14Cl28O4 8− Cluster

The synthesis and crystal structure of a novel copper(ll) halide cluster, (Et₄N)₈Cu₁₄Cl₂₈O₄, is reported. The cluster anion Cu₁₄Cl₂₈O₄ ^8? can be Viewed as being formed by the dimerization of two Cu₇Cl₁₄O₂ ^4? fragments. The hypothetical precursor anion of this latter cluster, Cu₇Cl₁₅O₂ ^5? in tum can be viewed as being formed from. the known parent Cu₇Cl₁₄O₂ ^4? cluster anions by fusion of pairs across a common CuCI₃ face. The fusion and dimenzation processes cause substantial distortion of the trigonal bipyramidal coordmation geometry of the copper(II) ions in the parent cluster. For three of the copper(II) ions this Yields a 4+1 geometry distinct from either trigonal blpyramldal or square pyramidal. The dimerization of the two Cu₇ clusters forces a severe distortion upon one additional copper(II) ion, this time towards a tetrahedral geometry. The implications of these distortions for the catalytic properties reactivities and magnetic behaviour of the parent complex are discussed.     

Two zincophosphite frameworks templated by 1,4-diaminobenzene: syntheses and structures of C6N2H10·Zn(HPO3)2 and (C6N2H8)0.5·ZnHPO3

The solution-mediated syntheses and single crystal structures of C₆N₂H₁₀·Zn(HPO₃)₂ (I) and (C₆N₂H₈)_0.5·ZnHPO₃ (II) are reported. Slight variation of the synthesis conditions led to two quite different phases. I contains infinite chains of ZnO₄ and HPO₃ groups with the protonated organic moiety acting as a template and interacting with the chains by NH⋯O hydrogen bonds and possible CH⋯O interactions. In II, the neutral 1,4-diamino benzene molecule bonds to Zn (as a ligand) and an unusual composite, “pillared”, structure results, with the organic species bridging 6³ polyhedral sheets, although NH⋯O bonds are also present. Similarities and differences to other zinc phosphites and phosphates are briefly discussed for I and II. Crystal data: C₆N₂H₁₀·Zn(HPO₃)₂, M_r=335.48, monoclinic, C2/c (No. 15), a=17.2471 (14) Å, b=9.0720 (8) Å, c=7.6529 (6) Å, β=103.752 (2)°, V=1163.09 (7) Å³, Z=4, R(F)=0.038, wR(F²)=0.084. (C₆N₂H₈)_0.5·ZnHPO₃, M_r=199.42, orthorhombic, Pbca (No. 61), a=8.0314 (16) Å, b=8.1299 (16) Å, c=18.830 (4) Å, V=1229.5 (4) Å³, Z=8, R(F)=0.026, wR(F²)=0.055.     

Coordination behavior of 1,4-diallylpiperazinium and 1-allyloxybenzotriazole toward silver(I) in the crystalline π-complexes [Ag2(C4H8N2(C3H5)2(H+)2)(H2O)2(NO3)2](NO3)2 and [Ag(C6H4N3(OC3H5)(NO3))]

Reactions of a solution of AgNO₃ in aqueous methanol with solutions of 1,4-diallylpiperazine (acidified with HNO₃ to pH = 4) and 1-allyloxybenzotriazole in ethanol gave the crystalline silver(I) π-complexes [Ag₂(C₄H₈N₂(C₃H₅)₂(H⁺)₂)(H₂O)₂(NO₃)₂](NO₃)₂ (I) and [Ag(C₆H₄N₃(OC₃H₅)(NO₃))] (II). Their crystal structures were determined by X-ray diffraction. Crystals of complexes I and II are monoclinic, space group P2₁/c; for I: a = 7.053(3)Å, b = 9.389(3)Å, c = 15.488(4)Å, β = 91.60°, V = 1025.3(6)ų, Z = 4; for II: a = 10.650(4)Å, b = 15.062(5)Å, c = 7.412(4)Å, β = 104.20(3)°, V = 1152.6(8)ų, Z = 4. In both structures, the organic components act as bidentate ligands forming with AgNO₃ 34- and 14-membered topological rings, respectively. In complex I, the nearly tetrahedral environment of the Ag(I) atom is made up of the olefinic C=C bond, the O atoms of the nitrate anions, and the water molecule. 1-Allyloxybenzotriazole in structure II causes the deformation of the coordination polyhedron of Ag into a trigonal pyramid via inclusion of the ligand N atom in its coordination sphere. The topological units of the complexes form infinite polymer layers linked by anionic NO ₃ ^? bridges. In structure I, these layers are united through a system of hydrogen bonds into a three-dimensional framework.     

Synthesis and Characterization of Two New Compounds: N(C2H4NH3)3(H2TO4)(HTO4)·2H2O (T = P,As)

The synthesis and structures of two new compounds with the general formula N(C₂H₄NH₃)₃(H₂TO₄)(HTO₄)·2H₂O (T = P, As) are reported. They crystallize with triclinic unit cells and are isotropic. We determined the structure of phosphate salt. The following unit cell parameters were found: a = 9.886(4), b = 9.308(2), c = 10.140(3) Å, α = 109.38(2), β = 108.83(3), γ = 74.40(3)°, V = 819.2(5) ų, and ρ_cal. = 1.537 g · cm^?3. The crystal structure was solved with a final R = 0.042 for 3748 with I > 3σ I). The space group is P-1 and Z = 2. The atomic arrangement can be described as a three-dimensional network of hydrogen bonds made up from H_nPO₄ ^3?n (n = 1, 2) anions and H ₂ O molecules between which are trapped the tris(2-ammoniumethyl)amine cations. Solid-state ¹³C and ³¹P MAS-NMR spectroscopies are in agreement with X-ray structure. Ab initio calculations allow the attribution of the phosphorus signals to the independent crystallographic sites.     

[Cu(C8H4F3O2S)2(C12H8N2)]·C3H6O的合成及其晶体结构

标题配合物 [Cu(C8H4 F3O2 S) 2 (C12 H8N2 ) ]·C3H6 O属于三斜晶系 ,空间群为P1,并测得如下晶胞参数a =10 .5 77(3) ,b =15 .72 2 (4) ,c =10 .133(2 ) ,α =94 .5 3(2 ) ,β =10 0 .81(2 ) ,γ =96 .18(2 )° ,V =16 37.0 3 3,Z =2 ,Mr =74 4.18,Dx =1.5 1× 10 6 g·m- 3,F(0 0 0 ) =5 2 6 ,μ =8 2 4cm- 1,最终偏差因子为R =0 .0 83,Rw=0 .0 74。Cu(II)与 2个 4 ,4 ,4 三氟 1 (2 噻吩基 )丁二酮 1,3中的四个氧原子和菲咯啉中的两个氮原子 ,组成了一个畸变的八面体构型。     

Synthesis and Structure of anti-Configuration Complex [Cu(tssb)2]·2[(H3O)Cl]·4H2O

The title complex [Cu(tssb)2]·2[(H3O)Cl]·4H2O (C18H34Cl2CuN2O14S2) (tssb = taurine salicylaldehyde Schiff base) has been synthesized by the reaction of taurine salicylaldehyde Schiff base (tssb) and copper acetate in water-ethanol. Its single-crystal structure was determined by X-ray diffraction method. The crystal structure belongs to triclinic, space group P with a = 0.7407(1), b = 1.3329(3), c = 1.5736(3)nm, α = 103.800(4), β = 95.030(4), γ = 104.416(4)°, Mr = 701.06, V = 1.4433(5) nm3, Z = 2, Dc = 1.613 g/cm3, μ = 1.153 mm-1 and F(000) = 726. The compound is an infinitely expanding three-dimensional network connected with hydrogen bonds. The Cu(Ⅱ) atom is coordinated by two nitrogen and two oxygen atoms to form a distorted planar coordination compound which adopts anti-configuration because two sulfonic acid groups are positioned diagonally on a plane.     

Construction of a 3D Co(Ⅱ) Framework Based on Two Types of V-shaped Bidentate Ligands

A three-dimensional(3D) coordination polymer {[Co(bdc)(dpb)]·H2O}n(1) was prepared by solvothermal reaction of 1,3-dipyridyl benzene(dpb) with deprotonated 1,3-benzenedicarboxylate(H2bdc), and was characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group C2/c with a = 15.478(6), b = 12.865(5), c = 24.091(10) ?, β = 95.599(5)°, V = 4774(3) ?3, C24H18CoN2O5, Mr = 473.34, Dc = 1.267 g/cm3, F(000) = 1864.0, μ = 0.748 mm-1 and Z = 8. Each Co(II) ion links three bdc2- anions to form an infinitely 1D ladder-shaped chain containing binuclear [(COO)Co]2 cluster, and dpb links adjacent 1D chains to form a 3D pcu framework. In addition, the UV-vis of 1 was also studied.     

Synthesis and Crystal Structure of (C6N3H18)2Ti4O4(C2O4)7·4H2O

The title compound (C6N3H18)2Ti4O4(C2O4)7(4H2O 1 (C13H22N3O18Ti2, Mr = 604.14) was synthesized by the reaction of Ti(SO4)2, H2C2O4(2H2O and N-(2-ammonioethyl)- piperazinium (AEPP) in aqueous solution. The single-crystal X-ray analysis has revealed that 1 crystallizes in the triclinic system, space group Pī with a = 9.1437(6), b = 11.4991(10), c = 11.6975(8)A, α = 96.2915(18), β = 107.998(3), γ = 104.276(4)°, V = 1110.35(14)A3, Z = 2, Dc = 1.807 g/cm3, F(000) = 618, μ = 0.815 mm－1, the final R = 0.0463 and wR = 0.1264 for 3718 observed reflections with I > 2σ(I). X-ray crystal-structure analysis suggests that compound 1 consists of [Ti4O4(C2O4)7]6－ anion and two protonated N-(2-ammonioethyl)piperazinium cations. The anions are linked into an infinite chain through Ti4O4(C2O4)8 by sharing the oxalates as bridging ligands.     

Molar heat capacity and thermodynamic properties of crystalline Eu(C2H5O2N)2Cl3·3H2O

A complex of europium hydrochloric acid coordinated with 2-aminoacetic acid (C₂H₅O₂N), Eu(C₂H₅O₂N)₂Cl₃·3H₂O was synthesized and characterized by IR and elements analysis. The heat capacities of the complex was measured with an automatic adiabatic calorimeter, and the thermodynamic functions [H _T ? H _298.15] and [S _T ? S _298.15] were derived in the temperature range from 80 to 340 K with temperature interval of 5 K. Thermal decomposition behavior of the complex in nitrogen atmosphere was studied by thermogravimetric (TG) analysis and differential scan calorimeter (DSC).     

Investigation of Copper Halide:Hydrothermal Syntheses and Characterization of CuBr2(C12H8N2) and Cu3Br3(C12H8N2)2

The reaction of CuBr₂ with 1,10‐phen‐H₂O (1,10‐phen = 1,10‐phenanthroline) gave two compounds: CuBr₂(C₁₂H₈N₂) and Cu₃Br₃(C₁₂H₈N₂)₂. Their structures have been characterized by single‐crystal X‐ray diffraction analysis, elemental analyses, thermogravimetric analyses (TGA) and measurement of variable temperature magnetic susceptibility. Crystal data for CuBr₂(C₁₂‐H₈N₂): monoclinic, space group P2₁/n, a = 0.9977(3) nm, b = 0.65138(14) nm, c = 1.8207(4) nm, β = 91.624(18)°, V = 1.1828(5) nm³, Z = 2. Crystal data for Cu₃Br₃(C₁₂H₈N₂)₂: monoclinic, space group C2/c, a = 1.00167(11) nm, b = 1.4523(4) nm, c = 1.6295(3) nm, β = 94.386(14)°, V = 2.3635(8) nm³, Z = 3.     

Syntheses and structures of two new M6Li8(N3)a6 cluster-unit based compounds: Cs4Re6S8(N3)6·H2O and Na2Mo6Br8(N3)6·2H2O

The two new cluster compounds, Cs₄Re₆S₈(N₃)₆·H₂O (1) and Na₂Mo₆Br₈(N₃)₆·2H₂O (2), have been prepared via solution chemistry route, starting from the Cs₄Re₆S₈Br₆CsBr and Mo₆Br₁₂ precursors synthesized by solid state chemistry techniques, and structurally characterized (crystal data: Cs₄Re₆S₈(N₃)₆·H₂O (1): Orthorhombic, space group Pnam, a=10.0651(1) Å, b=15.8856(2) Å, c=20.1714(3) Å, V=3225.2(7) Å³, Z=4, d_calc=4.48 g cm⁻³, μ=27.43 mm⁻¹; Na₂Mo₆Br₈(N₃)₆·2H₂O (2): Orthorhombic, space group Ibam, a=11.5643(3) Å, b=14.3959(5) Å, c=17.0340(7) Å, V=2835.8(2) ų, Z=4, d_calc=3.63 g cm⁻³, μ=13.91 mm⁻¹). Their structures revealed that in both cases, the M₆Lⁱ₈ cluster core remains unchanged in the starting and final compounds whereas the bromine apical ligands (Br^a) are substituted by N₃ azide groups leading to M₆Lⁱ₈(N₃)^a₆ cluster unit. The new Cs₄Re₆S₈(N₃)₆·H₂O is the first example of a compound containing an octahedral rhenium cluster coordinated to azide groups.     

A spectrochemical study of quinoxaline-2,3-dithiol C8H6N2S2 and its monobasic salts M·C8H5N2S2, oxidation product (C8H5N2S2)2 and the related compound (C8H4N2S)2

The new quinoxaline-2,3-dithioderivative (C₈H₅N₂S₂)₂, (HQS₂)₂, was prepared by oxidation of quinoxaline-2,3-dithiol, H₂QS₂, with iodine or oxygen. These substances and the compound (C₈H₄N₂S)₂, Q₂S₂, have different and characteristic electronic spectra in DMF solution; in the presence of air H₂QS₂ 10⁻⁴ M in DMF is transformed within 14 hr into (HQS₂)₂ and this, after 72 hr, into a new stable not isolated compound. (HQS₂)₂, H₂QS₂ and its salts M·HQS₂ (M = K, (CH₃)₂NH₂) do not show any ν(SH) band in the region 2500–2600 cm⁻¹ but show, like 2,3-dihydroxy-quinoxaline, a ν(NH) band at 3125–3150 cm⁻¹ and a NH-vibration band at 730–750 cm⁻¹ which are absent in quinoxaline, 2,3-dimethyl- and 2,3-dichloroquinoxaline and in Q₂S₂. It may be assigned the constitution of quinoxaline-2,3-dithione to H₂QS₂, bis(quinoxaline)-2,2′-di-sulphide-3,3′-dithione to (HQS₂)₂ and bis(quinoxaline)-2,2′-3,3′-dithioether to Q₂S₂. The i.r. spectra of these quinoxaline-2,3-dithioderivatives are compared with those of quinoxaline and its 2,3-disubstituted derivatives and some tentative assignments are given for their ν(NCS) asym., ν(NCS) sym., ν(CS) and δ(NCS) modes.     

Cupro(I)-π-complexes with 1-allyloxybenzotriazole: Synthesis and crystal structure of CuBF4 · 2C6H4N3(OC3H5) · H2O and CuCF3COO · C6H4N3(OC3H5)

The crystals of copper(I) π-complexes CuBF₄ · 2C₆H₄N₃(OC₃H₅) · H₂O (I) and CuCF₃COO · C₆H₄N₃(OC₃H₅) (II) were obtained by alternating-current electrosynthesis and studied by X-ray diffraction: I, space group P2₁/n, a = 10.226(8), b = 13.233(10), c = 16.30(1) Å, β = 98.13(1)°, V = 2249(2) ų, Z = 4, R = 0.0705, 577 reflections; I, space group P $ P\bar 1 The crystals of copper(I) π-complexes CuBF₄ · 2C₆H₄N₃(OC₃H₅) · H₂O (I) and CuCF₃COO · C₆H₄N₃(OC₃H₅) (II) were obtained by alternating-current electrosynthesis and studied by X-ray diffraction: I, space group P2₁/n, a = 10.226(8), b = 13.233(10), c = 16.30(1) ?, β = 98.13(1)°, V = 2249(2) ?³, Z = 4, R = 0.0705, 577 reflections; I, space group P , a = 8.8625(7), b = 9.0647(4), c = 9.1650(5) ?, α = 68.37(2)°, β = 85.31(3)°, γ = 69.86(2)°, V = 646(4) ?³, Z = 2, R = 0.1354, 2669 reflections. In compound I, the tetrahedrally distorted trigonal pyramidal environment of the copper atom comprises two nitrogen atoms of two organic molecules (L), the C=C bond of another L molecule, and the O atom of the water molecule. Due to the bridging function of L molecule, infinite chains [Cu · 2C₆H₄N₃(OC₃H₅) · H₂O] _n are formed in the structure along the y axis. The chains are, in turn, assembled into layers through strong O-H…F hydrogen bonds involving both hydrogen atoms of the water molecule and fluorine atoms of the BF₄⁻ anion. In compound II, two bridging oxygen atoms of two trifluoroacetate anions and two copper atoms form a centrosymmetric dimer. The nitrogen atom of the benzotriazole ring of one molecule L and the C=C double bond of the allyl group of the other molecule L complete the distorted coordination tetrahedron of the metal atom. Owing to the bridging function of the L molecule, the [CuCF₃COO · C₆H₄N₃(OC₃H₅)]₂ dimers are connected to form infinite double chains associated in a three-dimensional framework by only weak interactions. The replacement of the covalently bonded trifluoroacetate anion by an outer-sphere tetrafluoroborate ion opens up the possibility for metal atom binding to three L molecules simultaneously. Original Russian Text ? E.A. Goreshnik, M.G. Mys’kiv, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 11, pp. 826–830.     

Syntheses and Structures of Two New Coordination Polymers:[Cu(C14H9O4)(C14H10O4)(C12H12N2)2] and [Ag(C14H9O4)(C13H14N2)]·0.5 H2O

Under hydrothermal conditions, two new ribbon-like structures, [Cu(C14H9O4)-analysis revealed that these structures were constructed by mixed ligands. The coordination polymer forms the basic architecture while the weak interactions extend the framework into a secondary structure. The whole structures of them are governed by collaboration of the strong and weak interactions. Compound 1 crystallizes in monoclinic, space group C2/c with a = 17.0485(3), b =1 1.0558(3), c = 22.7623(4) A, β = 102.465(1)°, V = 4189.2(2) A3, Z = 4, Mr = 915.44, Dc = 1.451g/mL, F(000) = 1900 andμ(MoKα) = 0.587 cm-1. The final R and wR are 0.0030 and 0.1022,respectively for 3037 observed reflections with I ＞ 2σ(I). Compound 2 crystallizes in monoclinic,space group P21/c with a = 11.5963(4), b = 11.7004(5), c = 17.1254(5) A,β = 95.620(1)°, V =2312.4(1) A3, Z = 4, Mr = 556.35, Dc = 1.598 g/mL, F(000) = 1132 andμ(MoKα) = 0.912 cm-1The final R and wR are 0.0431 and 0.1050, respectively for 2629 observed reflections with I ＞ 2σ(I).     

Architecture of framework copper(I) halide π-complexes with N-allyl-N,N,N′,N′-tetramethyl-ethylenediaminium and N,N′-diallyl-N,N,N′,N′-tetramethylethylenediaminium: Synthesis and crystal structure of [{C2H4N2(H+)×(CH3)4(C3H5)} Cu4Cl6] and [{C2H4N2(CH3)4(C3H5)2}0.5Cu2Cl1.67Br1.33]

N,N,N??,N??-tetramethylethylenediamine is obtained by the reaction of ethylenediamine with formaldehyde and formic acid (the Eschweiler-Clarke reaction) and then alkylated with allyl chloride (or bromide) in a ratio of 1:1 or 1:2 to obtain N-allyl-N,N,N??,N??-tetramethylethylenediaminium and N,N??-diallyl-N,N,N??,N??-tetramethylethylenediaminium bromide respectively. [{C₂H₄N₂(H⁺)(CH₃)₄(C₃H₅)}Cu₄Cl₆] (1) and [{C₂H₄N₂(CH₃)₄(C₃H₅)2}_0.5Cu₂Cl_1.67Br_1.33] (2) ??-complexes are obtained from alcohol solutions containing an ethylenediamine derivative and copper(II) chloride by ac-electrochemical synthesis on copper wire electrodes. An XRD study of the complexes is carried out. The crystals are monoclinic; 1: P2₁/n space group, a = 9.0081(6) ?, b = 12.5608(7) ?, c = 16.8610(10) ?, ?? = 102.061(3)°, V = 1865.7(2) ?³, Z = 4; 2: C2/c space group, a = 14.462(2) ?, b = 12.519(1) ?, c = 12.762(2) ?, ?? = 107.861(5)°, V = 2199.1(4) ?³, Z = 8. The structure of 1 consists of infinite copper halide networks with four crystallographically independent copper atoms, one of which coordinates the double bond of the allyl group of the ligand. The [C₂H₄N₂(H)(CH₃)₄(C₃H₅)]²⁺ cations are attached above and below the plane of the network. The individual fragments are bonded via an extensive system of (N)H??Cl and (C)H??Cl hydrogen bonds. The structure of 2 contains a three-dimensional copper halide framework whose cavities contain the [C₂H₄N₂(CH₃)₄(C₃H₅)₂]²⁺ cations that are ??-coordinated with copper(I) atoms. In both structures, the Cu(I) atom that coordinates the C=C bond has a trigonal-pyramidal coordination environment consisting of the double C=C bond of the corresponding ligand and three halogen atoms. The other Cu(I) atoms have a tetrahedral environment consisting solely of halogen atoms. The Cu-(C=C) distance is 1.958(1) ?, (1) and 1.974(1) ? (2).     

Hydrothermal Synthesis, Crystal Structure and Fluorescent Property of a Novel Mo(Ⅴ) Phosphate [Zn(Mov6P4O31H10)2(C4H14N3)2]·2C4H13N3·8H2O

A new molybdenum phosphate [Zn(Mov6P4O31H10)2(C4H14N3)2]·2C4H13N3·8H2O 1 (C4H13N3 = diethylenetriamine) has been synthesized under hydrothermal condition. Single-crystal X-ray diffraction reveals that compound 1 crystallizes in the monoclinic, space group P21/n, a =13.1679(3), b = 22.1240(6), c = 13.6146(3) (A), β = 103.4847(7)°, V = 3856.95(16) (A)3,C16H90N12O70P8ZnMo12, Mr = 3035.41, Z = 2, Dc = 2.614 g/cm3, μ = 2.483 mm-1, F(000) = 2968, S = 1.014, the final R = 0.0196 and wR = 0.0506 for 7486 observed reflections (I ＞ 2σ(Ⅰ)). Compound 1 consists of two identical rings of six edge-sharing MoO6 octahedra interconnected by one ZnO6 octahedron, whereas the PO4 tetrahedra which share their apices with the MoO6 octahedra are only located on one side of each Mo6 ring. The 2-charge of polyanion [Zn(Mov6P4O31H10)2]2- unit is compensated in the crystal by two mono-protonated diethylenetriamines (C4H14N3)+. By hydrogen bonding interactions the polyanion of compound 1 is interconnected to form pseudo three dimensional molybdophosphate. Other characterizations by elemental analyses, IR spectrum and fluorescent spectrum are also described.