The crystal structure and magnetic properties of a new ferrimagnetic semiconductor: Ca21Mn4Sb18

Single crystals of the new transition metal Zintl phase, Ca(21)Mn(4)Sb(18), were prepared by high temperature melt synthesis. The crystal structure was determined by single crystal X-ray diffraction to be monoclinic in the space group C2/c. Crystal information was obtained at 90 K, and unit cell parameters were determined (a = 17.100(2) A, b = 17.073(2) A, c = 16.857(2) A, beta = 92.999(2) degrees, Z = 2, R1 = 0.0540, wR2 = 0.1437). The structure can be described as containing 4 discreet units per formula unit: 1 linear [Mn(4)Sb(10)](22-) anion, 2 dumbbell-shaped [Sb(2)](4-) anions, 4 individual Sb(3-) anions, and 21 Ca(2+) cations. The [Mn(4)Sb(10)](22-) anion contains four edge-shared MnSb(4) tetrahedra with distances between Mn ions of 3.388(4) A, 2.782(4) A, and 2.760(4) A. Electron counting suggests that the Mn are 2+. Temperature dependent magnetization shows a ferromagnetic-like transition temperature at approximately 52 K which is suppressed with increasing magnetic field. The paramagnetic regime is best fit to a ferrimagnetic model, providing a total effective moment of 4.04(2) mu(B), significantly less than that expected for 4 Mn(2+) ions (11.8 mu(B)). Temperature dependent resistivity shows that this compound is a semiconductor with an activation energy of 0.159(2) eV (100-300 K).     

New calcium germanium nitrides: Ca2GeN2, Ca4GeN4, and Ca5Ge2N6

We report three new calcium germanium nitrides synthesized as crystals from the elements in sealed niobium tubes at 760 degrees C using liquid sodium as a growth medium. Black Ca2GeN2 is isostructural with the previously reported strontium analogue. It is tetragonal P4(2)/mbc (no. 135) with a = 11.2004(8) A, c = 5.0482(6) A, and Z = 8. It contains GeN2(4-) units which have 18 valence electrons, and consequently are bent, like the isoelectronic molecule SO2. In contrast, clear, orange Ca4GeN4 with fully oxidized germanium contains isolated GeN4(8-) tetrahedra and is monoclinic P2(1)/c (no. 14) with a = 9.2823(8) A, b = 6.0429(5) A, c = 11.1612(9) A, beta = 116.498(6) degrees, and Z = 4. Clear, colorless Ca5Ge2N6, also with fully oxidized germanium, contains infinite chains, 1 infinity[GeN2N2/2(5-)], of corner-sharing tetrahedra similar to those found in pyroxenes. However, the precise structure of this latter phase has not yet been determined because of twinning problems.     

Eu10Mn6Sb13: a new ternary rare-Earth transition-metal Zintl phase

A new transition-metal-containing Zintl compound, Eu(10)Mn(6)Sb(13), was prepared by a high-temperature Sn-flux synthesis. The structure was determined by single-crystal X-ray diffraction. Eu(10)Mn(6)Sb(13) crystallizes in the monoclinic space group C2/m with a = 15.1791(6) A, b = 19.1919(7) A, c = 12.2679(4) A, beta = 108.078(1)*, Z = 4 (R1 = 0.0410, wR2 = 0.0920), and T = 90(2) K. The structure of Eu(10)Mn(6)Sb(13) is composed of double layers of Mn-centered tetrahedra separated by Eu(2+) cations. The double layers are composed of edge- and corner-sharing Mn-centered tetrahedra which form cavities occupied by Eu(2+) cations and [Sb(2)](4-) dumbbells. Linear [Sb(3)](5-) trimers bridging two tetrahedra across the cavity are also present. Bulk susceptibility data indicate paramagnetic behavior with a ferromagnetic component present below 60 K. Temperature-dependent electrical resistivity measurements show semiconducting behavior above 60 K (E(a)() = 0.115(2) eV), a large and unusually sharp maximum in the resistivity at approximately 40 K, and metallic behavior below 40 K. (151)Eu M?ssbauer spectra confirm that the europium is divalent with an average isomer shift of -11.2(1) mm/s at 100 K; the spectra obtained below 40 K reveal magnetic ordering of six of the seven europium sublattices and, at 4.2 K, complete ordering of the seven europium sublattices.     

Luminescence detection of transition and heavy metals by inversion of excited states: synthesis, spectroscopy, and X-ray crystallography of Ca, Mn, Pb, and Zn complexes of 1,8-anthraquinone-18-crown-5

A lumophore composed of anthraquinone attached to a macrocyclic polyether ring containing an intraannular carbonyl is capable of selectively detecting Pb(2+)() ion in solution using an alternative photophysical detection mechanism. Of the various methods available for detection of ions in solution, a mechanism involving inversion of excited states has not been previously employed for the detection of transition and heavy metals. In this mechanism, nonradiative n-pi transitions are replaced by radiative pi-pi transitions upon complexation by a suitable guest cation. Optimum fluorescence enhancement is achieved using cations of high charge, large cations that form long bonds within the host, and cations which do not coordinate solvent or the counteranion, all of which are necessary for inversion of excited states to occur. Photophysical properties and binding constants of this new class of luminescence sensors are provided, as well as the X-ray crystallographic results for Pb(2+), Mn(2+), and Zn(2+) complexes of 1,8-oxybis(ethylene-oxyethyleneoxy)anthracene-9,10-dione (1), referred to as 1,8-anthraquinone-18-crown-5. ([1.Pb](ClO(4))(2) (2) (monoclinic, P21/n, a = 8.0303(6) A, b = 25.976(2) A, c = 12.1616(9) A, beta = 94.956(1) degrees , Z = 4, 4980 reflections [I > or = 2sigma(I)], R1 = 0.0266, wR2, 0.0500, 173(2) K). [1.Mn(H(2)O)(NCCH(3))](ClO(4))(2) (5) (monoclinic, P21/c, a = 10.132(2) A, b = 11.8030(4) A, c = 23.999(7) A, beta = 95.75(2) degrees , Z = 4, 3000 reflections [I > or = 2sigma(I)], R1 = 0.0488, wR2, 0.0938, 203(2) K). [1.Zn(H(2)O)(NCCH(3))](ClO(4))(2) (6) (monoclinic, P21/c, a = 10.177(10) A, b = 11.977(6) A, c = 24.166(4) A, beta = 95.83(4) degrees , Z = 4, 3061 reflections [I > or = 2sigma(I)], R1 = 0.0673, wR2, 0.1729, 295(2) K).).     

Probing the limits of the Zintl concept: structure and bonding in rare-earth and alkaline-earth zinc-antimonides Yb9Zn4+xSb9 and Ca9Zn4.5Sb9

A new transition metal Zintl phase, Yb(9)Zn(4+x)Sb(9), was prepared by high-temperature flux syntheses as large single crystals, or by direct fusion of the corresponding elements in polycrystalline form. Its crystal structure was determined by single-crystal X-ray diffraction. Its Ca-counterpart, hitherto known as Ca(9)Zn(4)Sb(9), and the presence of nonstoichiometry in it were also studied. Yb(9)Zn(4+x)Sb(9) was found to exist in a narrow homogeneity range, as suggested from the crystallographic data at 90(3) K (orthorhombic, space group Pbam (No. 55), Z = 2): (1) a = 21.677(2) A, b = 12.3223(10) A, c = 4.5259(4) A, R1 = 3.09%, wR2 = 7.18% for Yb(9)Zn(4.23(2))Sb(9); (2) a = 21.706(2) A, b = 12.3381(13) A, c = 4.5297(5) A, R1 = 2.98%, wR2 = 5.63% for Yb(9)Zn(4.380(12))Sb(9); and (3) a = 21.700(2) A, b = 12.3400(9) A, c = 4.5339(4) A, R1 = 2.75%, wR2 = 5.65% for Yb(9)Zn(4.384(14))Sb(9). The isostructural Ca(9)Zn(4.478(8))Sb(9) has unit cell parameters a = 21.830(2) A, b = 12.4476(9) A, and c = 4.5414(3) A (R1 = 3.33%, wR2 = 5.83%). The structure type in which these compounds crystallize is related to the Ca(9)Mn(4)Bi(9) type, and can be considered an interstitially stabilized variant. Formal electron count suggests that the Yb or Ca cations are in the +2 oxidation state. This is supported by the virtually temperature-independent magnetization for Yb(9)Zn(4.5)Sb(9). Electrical resistivity data show that Yb(9)Zn(4.5)Sb(9) and Ca(9)Zn(4.5)Sb(9) are poor metals with room-temperature resistivity of 10.2 and 19.6 mOmega.cm, respectively.     

三维无机-有机杂化微孔化合物Mn3(BTC)2(DMF)4的合成与结构

传统的沸石和分子筛微孔晶体材料是指以硅酸盐、硅铝酸盐、磷铝酸盐和无机金属磷酸盐为骨架的晶体材料．近年来,利用刚性和热稳定性较好的有机分子(如芳香多酸和多碱)和金属离子作为结构单元制备出了新型的无机一有机杂化微孔晶体材料．这类晶体材料能够在去除孔道中的溶剂分     

Syntheses and Crystal Structures of(H_3O)(C_3H_5N_2)[Mn(OH)_6Mo_6O_(18)]·3.5H_2O and (H_3O)_3[Co(OH)_6Mo_6O_(18)]·7H_2O

1 INTRODUCTION Polyoxometalates, a rich and remarkable classof inorganic cluster system[1], exhibit diverse appli-cation possibilities due to their topological and elec-tronic properties, ranging from their well-known roleas reagents in analytical, b…     

Syntheses and Crystal Structures of (H3O)(C3H5N2)[Mn(OH)6 Mo6O18]·3.5H2O and (H3O)3[Co(OH)6Mo6O18]·7H2O

The crystals of the title compounds (H3O)(C3H5N2)[Mn(OH)6Mo6O18]·3.5H2O 1 and (H3O)3[Co(OH)6Mo6O18]·7H2O 2 have been prepared and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group C2/c with a = 21.5018(9), b = 10.9331(5), c = 11.8667(5)A,β = 95.3570(10)o, V = 2777.5(2)A3, Z = 4, Dc = 2.802 g/cm3, Mr = 1171.80,μ(MoKα) = 3.173 mm-1, F(000) = 223, the final R = 0.0458 and wR = 0.1041 for 2093 observed reflections (I>2σ(I)); Compound 2 crystallizes in monoclinic, space group P21/c with a = 11.4042(12), b = 10.9481(11), c = 11.6722(12)A, β= 99.948(2)o, V = 1435.4(3)A3, Z = 2, Dc = 2.794 g/cm3, Mr = 1207.80,μ(MoKα) = 3.223 mm-1, F(000) = 1160, the final R = 0.0544 and wR = 0.1066 for 1906 observed reflections (I > 2σ(I)). Both compounds 1 and 2 adopt the Anderson structure, in which the anion is of centrosymmetry and formed by six octahedral edge-sharing MoO6 units surrounding the central MO6 (M = Mn or Co) octahedron.     

X-ray crystal structures of alpha-KrF(2),[KrF][MF(6)](M=As,Sb,Bi),[Kr(2)F(3)][SbF(6).KrF(2), [Ke(2)F(3)2[SbF(6)]2.KrF(2), and [Kr(2)F(3)][AsF(6)].[KrF][AsF(6)]; synthesis and characterization of [Kr(2)F(3)][PF(6).nKrF(2); and theoretical studies of KrF(2), KrF+, Kr(2)F(3)+, and the [KrF][MF(6)](M=P,As,Sb,Bi) ion pairs

The crystal structures of alpha-KrF(2) and salts containing the KrF(+) and Kr(2)F(3)(+) cations have been investigated for the first time using low-temperature single-crystal X-ray diffraction. The low-temperature alpha-phase of KrF(2) crystallizes in the tetragonal space group I4/mmm with a = 4.1790(6) A, c = 6.489(1) A, Z = 2, V = 113.32(3) A(3), R(1) = 0.0231, and wR(2) = 0.0534 at -125 degrees C. The [KrF][MF(6)] (M = As, Sb, Bi) salts are isomorphous and isostructural and crystallize in the monoclinic space group P2(1)/c with Z = 4. The unit cell parameters are as follows: beta-[KrF][AsF(6)], a = 5.1753(2) A, b = 10.2019(7) A, c = 10.5763(8) A, beta = 95.298(2) degrees, V = 556.02(6) A(3), R(1) = 0.0265, and wR(2) = 0.0652 at -120 degrees C; [KrF][SbF(6)], a = 5.2922(6) A, b = 10.444(1) A, c = 10.796(1) A, beta = 94.693(4) degrees, V = 594.73(1) A(3), R(1) = 0.0266, wR(2) = 0.0526 at -113 degrees C; [KrF][BiF(6)], a = 5.336(1) A, b = 10.513(2) A, c = 11.046(2) A, beta = 94.79(3) degrees, V = 617.6(2) A(3), R(1) = 0.0344, and wR(2) = 0.0912 at -130 degrees C. The Kr(2)F(3)(+) cation was investigated in [Kr(2)F(3)][SbF(6)].KrF(2), [Kr(2)F(3)](2)[SbF(6)](2).KrF(2), and [Kr(2)F(3)][AsF(6)].[KrF][AsF(6)]. [Kr(2)F(3)](2)[SbF(6)](2).KrF(2) crystallizes in the monoclinic P2(1)/c space group with Z = 4 and a = 8.042(2) A, b = 30.815(6) A, c = 8.137(2) A, beta = 111.945(2) degrees, V = 1870.1(7) A(3), R(1) = 0.0376, and wR(2) = 0.0742 at -125 degrees C. [Kr(2)F(3)][SbF(6)].KrF(2) crystallizes in the triclinic P1 space group with Z = 2 and a = 8.032(3) A, b = 8.559(4) A, c = 8.948(4) A, alpha = 69.659(9) degrees, beta = 63.75(1) degrees, gamma = 82.60(1) degrees, V = 517.1(4) A(3), R(1) = 0.0402, and wR(2) = 0.1039 at -113 degrees C. [Kr(2)F(3)][AsF(6)].[KrF][AsF(6)] crystallizes in the monoclinic space group P2(1)/c with Z = 4 and a = 6.247(1) A, b = 24.705(4) A, c = 8.8616(6) A, beta = 90.304(6) degrees, V = 1367.6(3) A(3), R(1) = 0.0471 and wR(2) = 0.0958 at -120 degrees C. The terminal Kr-F bond lengths of KrF(+) and Kr(2)F(3)(+) are very similar, exhibiting no crystallographically significant variation in the structures investigated (range, 1.765(3)-1.774(6) A and 1.780(7)-1.805(5) A, respectively). The Kr-F bridge bond lengths are significantly longer, with values ranging from 2.089(6) to 2.140(3) A in the KrF(+) salts and from 2.027(5) to 2.065(4) A in the Kr(2)F(3)(+) salts. The Kr-F bond lengths of KrF(2) in [Kr(2)F(3)][SbF(6)].KrF(2) and [Kr(2)F(3)](2)[SbF(6)](2).KrF(2) range from 1.868(4) to 1.888(4) A and are similar to those observed in alpha-KrF(2) (1.894(5) A). The synthesis and Raman spectrum of the new salt, [Kr(2)F(3)][PF(6)].nKrF(2), are also reported. Electron structure calculations at the Hartree-Fock and local density-functional theory levels were used to calculate the gas-phase geometries, charges, Mayer bond orders, and Mayer valencies of KrF(+), KrF(2), Kr(2)F(3)(+), and the ion pairs, [KrF][MF(6)] (M = P, As, Sb, Bi), and to assign their experimental vibrational frequencies.     

Two new one-dimensional compounds with end-to-end dicyanamide as a bridging ligand: syntheses and structural characterization of trans-[Mn(4-bzpy)2(N(CN)2)2]n and cis-[Mn(Bpy)(N(CN)2)2]n, (4-bzpy = 4-benzoylpyridine; bpy = 2,2'-bipyridyl)

Two new one-dimensional compounds, trans-[Mn(4-bzpy)2(N(CN)2)2]n (1) and cis-[Mn(bpy)(N(CN)2)2]n (2), have been synthesized and studied from a magnetic point of view (4-bzpy = 4-benzoylpyridine; bpy = 2,2'-bipyridyl). The crystal structures of 1 and 2 have been solved. Compound 1 crystallizes in the monoclinic system, P2(1)/n group, a = 6.374(2) A, b = 7.584(2) A, c = 26.766(5) A, beta = 91.87 degrees, and Z = 2, whereas compound 2 crystallizes in the monoclinic system, C2/c group, a = 6.707(2) A, b = 17.188(5) A, c = 13.096(5) A, beta = 90.54 degrees, and Z = 4. The two compounds consist of chains with double mu 1,5-dicyanamide bridges between neighboring manganese(II) atoms. The weak antiferromagnetic coupling found for the two compounds (J = -0.3 cm-1 for 1 and -0.4 cm-1 for 2) has been studied by MO analysis, and the superexchange pathway through the mu 1,5-(NCNCN-) bridge has been compared with the shorter mu 1,3-(NNN-).     

Syntheses and Crystal Structures of Two Complexes with 3-（3-Pyridyl）acrylic Acid

1 INTRODUCTION A recent feature in the development and progress of chemical research is the concern for molecular assemblies, ensembles, and all of structural aggre- gates[1]. The self-assembly of transition metal ions and N-containing organic ligands has been proven a popular approach for the construction of supramo- lecular architecture[2～7]. 3-(3-Pyridyl)acrylic acid is an excellent ligand, not only due to its prolific coor- dination sites but also to its potential hydrogen bon- ding…     

Bimetallic cyanide-bridged complexes based on the photochromic nitroprusside anion and paramagnetic metal complexes. Syntheses, structures, and physical characterization of the coordination compounds [Ni(en)2]4[Fe(CN)5NO]2[Fe(CN)6]x5H2O, [Ni(en)2][Fe(CN)5NO]x3H2O, [Mn(3-MeOsalen)(H2O)]2[Fe(CN)5NO], and [Mn(5-Brsalen)]2[Fe(CN)5NO

The synthesis, crystal structure, and physical characterization of the coordination compounds [Ni(en)2]4[Fe(CN)5NO]2[Fe(CN)6]x5H2O (1), [Ni(en)2][Fe(CN)5NO]x3H2O (2), [Mn(3-MeOsalen)(H2O)]2[Fe(CN)5NO] (3), and [Mn(5-Brsalen)]2[Fe(CN)5NO] (4) are presented. 1 crystallizes in the monoclinic space group P2(1)/n (a = 7.407(4) A, b = 28.963(6) A, c = 14.744(5) A, alpha = 90 degrees, beta = 103.26(4) degrees, gamma = 90 degrees, Z = 2). Its structure consists of branched linear chains formed by cis-[Ni(en)2]2+ cations and ferrocyanide and nitroprusside anions. The presence of two kinds of iron(II) sites has been demonstrated by M?ssbauer spectroscopy. 2 crystallizes in the monoclinic space group P2(1)/c (a = 11.076(3) A, b = 10.983(2) A, c = 17.018(5) A, alpha = 90 degrees, beta = 107.25(2) degrees, gamma = 90 degrees, Z = 4). Its structure consists of zigzag chains formed by an alternated array of cis-[Ni(en)2]2+ cations and nitroprusside anions. 3 crystallizes in the triclinic space group P1 (a = 8.896(5) A, b = 10.430(5) A, c = 12.699(5) A, alpha = 71.110(5) degrees, beta = 79.990(5) degrees, gamma = 89.470(5) degrees, Z = 1). Its structure comprises neutral trinuclear bimetallic complexes in which a central [Fe(CN)5NO]2- anion is linked to two [Mn(3-MeOsalen)]+ cations. 4 crystallizes in the tetragonal space group P4/ncc (a = 13.630(5) A, c = 21.420(8) A, Z = 4). Its structure shows an extended 2D neutral network formed by cyclic octameric [-Mn-NC-Fe-CN-]4 units. The magnetic properties of these compounds indicate the presence of quasi-isolated paramagnetic Ni2+ and Mn3+. Irradiated samples of the four compounds have been studied by differential scanning calorimetry to detect the existence of the long-lived metastable states of nitroprusside.     

Trinuclear thiocyanate-bridged compounds of the type [ML]2[Mn(NCS)4](ClO4)2 (where M = Cu(II), Ni(II); L = N-dl-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)

The complexes of general formula [ML]2[Mn(NCS)4](ClO4)2 (where M = Cu(II), Ni(II); L = N-dl-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene) were obtained and the crystal structures of both heteronuclear compounds were determined at 173 K. Complex [CuL]2[Mn(NCS)4](ClO4)2 (1) crystallizes in a monoclinic space group, C2/c, with a = 41.297(9) A, b = 7.571(2) A, c = 16.417(4) A, beta = 96.97(15) degrees, Z = 8, whereas complex [NiL]2[Mn(NCS)4](ClO4)2.H2O (2) crystallizes in a monoclinic space group, P2/c, with a = 21.018(5) A, b = 7.627(2) A, c = 16.295(4) A, beta = 104.47(1) degrees, Z = 4. The magnetic behaviour of (1) and (2) has been investigated over the temperature range 1.8-300 K. Complex (1) displays ferromagnetic coupling inside the trinuclear core of CuMnCu and compound (2) behaves like a mononuclear Mn(II) system. The magnetic properties of the second compound (2) with a similar trinuclear structure shows that Ni(II) ions have a diamagnetic character and a rather weak zero-field splitting at the central Mn(II) ion occurs. Finally, the magnitudes of the Cu(II)-M(II) interactions with M = Ni and Mn have been compared and qualitatively justified.     

Sulfosalts with alkaline earth metals. Centrosymmetric vs acentric interplay in Ba3Sb4.66S10 and Ba2.62Pb1.38Sb4S10 based on the Ba/Pb/Sb ratio. Phases related to arsenosulfide minerals of the rathite group and the novel polysulfide Sr6Sb6S17

The new compounds, Sr6Sb6S17, Ba2.62Pb1.38Sb4S10, and Ba3Sb4.66S10 were prepared by the molten polychalcogenide salt method. Sr6Sb6S17 crystallizes in the orthorhombic space group P2(1)2(1)2(1) with a = 8.2871(9) A, b = 15.352(2) A, c = 22.873(3) A, and Z = 4. This compound presents a new structure type composed of [Sb3S7]5- units and trisulfide groups, (S3)2-, held together by Sr2+ ions. The [Sb3S7]5- fragment is formed from three corner-sharing SbS3 trigonal pyramids. The trisulfide groups are separated from the [Sb3S7]5- unit and embedded between the Sr2+ ions. Ba3Sb4.66S10 and Ba2.62Pb1.38Sb4S10 are not isostructural but are closely related to the known mineral sulfosalts of the rathite group. Ba3Sb4.67S10 is monoclinic P2(1)/c with a = 8.955(2) A, b = 8.225(2) A, c = 26.756(5) A, beta = 100.29(3) degrees, and Z = 4. Ba2.62Pb1.38Sb4S10 is monoclinic P2(1) with a = 8.8402(2) A, b = 8.2038(2) A, c = 26.7623(6) A, beta = 99.488(1) degrees, and Z = 4. The Sb atoms are stabilized in SbS3 trigonal pyramids that share corners to build ribbonlike slabs, which are stitched by Ba/Pb atoms to form layers perpendicular to the c-axis. These materials are semiconductors and show optical band gaps of 2.10, 2.14, and 1.64 eV for Sr6Sb6S17, Ba3Sb4.66S10, and Ba2.62Pb1.38Sb4S10, respectively. Raman spectroscopic characterization is reported. Sr6Sb6S17, Ba3Sb4.66S10, and Ba2.62Pb1.38Sb4S10 melt congruently at 729, 770, and 749 degrees C, respectively.     

二维层状水合酸式硫酸铈H3O[Ce(SO4)2·(H2O)3]·H2O的水热合成与结构表征

镧系金属硫酸盐由于在稀土分离等方面具有重要的应用而受到广泛关注。但是，因其适于结构测定的单晶相对难以得到，迄今，关于稀土硫酸盐的结构报道仍然较少，且主要局限于水合硫酸盐和三元硫酸盐．近几年中，基于硫酸根与磷酸根在结构上的相似性，借鉴在水热／溶剂热体系中采用有机胺作模板剂大量合成具有空旷骨架结构的微孔磷酸盐的成功经验，以有机胺为模板剂合成具有空旷骨架结构的镧系金属硫酸盐的工作也已见诸报道．在这些化合物中，由于硫酸根配位方式的多样性和稀土元素配位数和配位构型的可调变性，展现出了一些有趣的结构特征．     

Synthesis and Structure of Bis（indene—1,2,3—trione 2—oximato）bis （aqua）Mn（Ⅱ）：Mn（C9H4NO3）2（H2O）2

1 INTRODUCTION The interest in the complexes of transition metals with ligands ketoxime[1, 2] as potential models for metal binding sites in ferroverdin[3, 4] has prompted the investigation on the structures and the overall coordination geometry of the metal centers in these complexes. Oxime derivatives are interesting ligands since the ketoximes are found to chelate transition metals through the N (oxime) and O (ketone) atoms[5, 6]. However, monodentate coordination via only one O or …     

Syntheses, crystal structures and characterizations of two new quaternary thioborates: PbMBS4 (M = Sb, Bi)

Two new quaternary thioborates, PbSbBS(4) and PbBiBS(4), have been synthesized from solid-state reaction methods at temperatures from 1073 to 1123 K in evacuated sealed quartz tubes. The crystal structures have been determined by means of single crystal X-ray diffraction and they both crystallize in the P2(1)/m space group of the monoclinic system with a = 5.9532(18) ?, b = 6.2031(13) ?, c = 9.250(3) ?, β = 108.200(16)°, Z = 2 for PbSbBS(4) and a = 5.971(10) ?, b = 6.273(9) ?, c = 9.132(15) ?, β = 107.75(2)°, Z = 2 for PbBiBS(4), respectively. The two compounds are isostructural and both constructed with the infinite one-dimensional [MBS(4)](2-) (M = Sb or Bi) chains as building blocks, which are composed of [BS(3)](3-) trigonal plane units with [MS(3)](3-) (M = Sb or Bi) trigonal pyramids connected alternatively through corner-sharing along the crystallographic b axis. Two adjacent [MBS(4)](2-) chains are further bridged by the intermediate Pb(2+) cations, forming a novel S-shaped Pb-[MBS(4)] dimeric chain structure. In addition, first-principles electronic structure calculations based on the density functional theory (DFT) were performed on compound PbSbBS(4), indicating that the compound belongs to direct semiconductor with a band gap of 1.803 eV, which is in good agreement with the experimental value estimated from the UV-Vis diffuse reflectance spectroscopy.     

[Cu（en）_2]_2[Cu（en）_2（H_2O）][PW_（11.5）Cu_（0.5）O_（40）]·OH·3H_2O的水热合成及结构表征

利用水热合成法制备了基于Keggin结构阴离子的1D链状化合物[Cu（en）2]2[Cu（en）2（H2O）][PW11.5Cu0.5O40].OH.3H2O,并经红外、紫外和X射线单晶衍射等手段进行了表征.标题化合物属于单斜晶系,P21/c空间群,晶胞参数：a=1.266 25（10）,b=2.145 45（19）,c=2.455 95（18）nm,β=114.919（3）,V=6.050 9（8）nm3,Z=4,R1=0.068 1,wR2=0.146 8.     

hree Inorganic-organic Composite Polyoxotungstates:Syntheses, Characterization and Structures of [Cu(2,2'-bpy)2]5[α-PW11.5Cu0.5O40]·2H2O,[Co(2,2'-bpy)2(N3)2]4H3[α-PW12O40]·3H2O and [Cu(2,2'-bpy)2(4,4'-bpy)]2[α-GeW12O40]·4H2O

Three new inorganic-organic composite polyoxotungstates [Cu(2,2'- bpy)2]5[α- PW11.5Cu0.5O40]·2H2O 1, [Co(2,2'-bp3)2(N3)2]4H3[α-PW12O40]·3H2O 2 and [Cu(2,2'-bpy)2(4,4'- bpy)]2[α-GeW12O40].4H2O 3 (2,2'-bpy = 2,2'-bipyridine, 4,4'-bpy = 4,4'-bipyridine) have been hydrothermally synthesized and structurally characterized. 1 crystallizes in the orthorhombie space group Pna21 with α = 27.847(3), b = 21.597(2), c = 20.1179(19) A, V = 12099(2) A3, Z = 4, GOF= 1.038, R = 0.0427 and wR = 0.1035; 2 belongs to the triclinic space group P1 with a= 12.31150(10), b = 16.1954(4), c = 19.36290(10) A, α = 99.366(11), β=105.168(8),γ = 111.836(8)°, V = 3309.98(9) A3, Z = 1, GOF = 1.024, R = 0.0739 and wR = 0.2216; and 3 crystallizes in the monoclinic space group P21/n with a = 12.858(4), b = 20.943(6), c = 15.598(5) A, β = 102.338(5)°, V = 4103(2) A3, Z = 2, GOF = 1.026, R = 0.0557 and wR = 0.1316. The common structural features of 1～3 are that their molecular structures all consist of a saturated a-Keggin polyoxoanion and several discrete metal-organic moieties. Intriguingly, 2 and 3 are composed of metal-organic coordination moieties with two mixed ligands.     

pH-Dependent Assembly of Hybrid Materials Based on Molybdates and Copper/imidazole Complexes

Three novel inorganic-organic hybrid materials, [Cu（imi）2（H2O）（MoO4）]n 1, [Cuz（imi）3（MoO4）E]n.nH2O 2 and [Cu3（imi）2（OH）2（MoO4）2]n 3 （imi = imidazole）, were synthesized and characterized by X-ray single-crystal structure determination. 1 crystallizes in orthorhombic, space group Pca21 with a = 13.382（4）, b = 8.527（2）, c = 9.622（3）A, V = 1098.0（5） A^3 Z = 4, C6H10CuMoN4O5, Mr = 377.66, Dc = 2.285 g/cm^3, F（000） = 740,μ（MoKa） = 3.095 mm^-1, the final R = 0.0256 and wR = 0.0722 for 1896 observed reflections with I 〉 2σ（I）. 2 crystallizes in monoclinic, space group P2t/c with a= 11.170（2）, b = 7.8244（15）, c = 22.631（4）A, β = 115.790（7）°, V = 1780.9（6）A^3 Z = 4, C9H14Cu2Mo2N6O9, Mr = 669.24, Dc= 2.496 g/cm^3, F（000）=1295,μ（MoKa） = 3.792 mm^-1, the final R = 0.0225 and wR = 0.0615 for 3838 observed reflections with I 〉 2σ（I）. 3 crystallizes in monoclinic, space group P21/c with a = 5.5599（19）, b = 23.771（8）, c = 7.3044（18）A , β = 129.356（16）°, V = 746.5（4）A^3, Z = 2, C6H10Cu3Mo2N4O10, Mr = 680.71, Dc = 3.029 g/cm^3, F（000） = 650,μ（MoKa） = 5.900 mm^-1, the final R = 0.0215 and wR = 0.0524 for 1620 observed reflections with I 〉 2σ（I）.