Hydrolysis studies on bismuth nitrate: synthesis and crystallization of four novel polynuclear basic bismuth nitrates

Hydrolysis of Bi(NO(3))(3) in aqueous solution gave crystals of the novel compounds [Bi(6)O(4)(OH)(4)(NO(3))(5)(H(2)O)](NO(3)) (1) and [Bi(6)O(4)(OH)(4)(NO(3))(6)(H(2)O)(2)]·H(2)O (2) among the series of hexanuclear bismuth oxido nitrates. Compounds 1 and 2 both crystallize in the monoclinic space group P2(1)/n but show significant differences in their lattice parameters: 1, a = 9.2516(6) ?, b = 13.4298(9) ?, c = 17.8471(14) ?, β = 94.531(6)°, V = 2210.5(3) ?(3); 2, a = 9.0149(3) ?, b = 16.9298(4) ?, c = 15.6864(4) ?, β = 90.129(3)°, V = 2394.06(12) ?(3). Variation of the conditions for partial hydrolysis of Bi(NO(3))(3) gave bismuth oxido nitrates of even higher nuclearity, [{Bi(38)O(45)(NO(3))(24)(DMSO)(26)}·4DMSO][{Bi(38)O(45)(NO(3))(24)(DMSO)(24)}·4DMSO] (3) and [{Bi(38)O(45)(NO(3))(24)(DMSO)(26)}·2DMSO][{Bi(38)O(45)(NO(3))(24)(DMSO)(24)}·0.5DMSO] (5), upon crystallization from DMSO. Bismuth oxido clusters 3 and 5 crystallize in the triclinic space group P1? both with two crystallographically independent molecules in the asymmetric unit. The following lattice parameters are observed: 3, a = 20.3804(10) ?, b = 20.3871(9) ?, c = 34.9715(15) ?, α = 76.657(4)°, β = 73.479(4)°, γ = 60.228(5)°, V = 12021.7(9) ?(3); 5, a = 20.0329(4) ?, b = 20.0601(4) ?, c = 34.3532(6) ?, α = 90.196(1)°, β = 91.344(2)°, γ = 119.370(2)°, V = 12025.8(4) ?(3). Differences in the number of DMSO molecules (coordinated and noncoordinated) and ligand (nitrate, DMSO) coordination modes are observed.     

Synthesis, characterization and magnetic properties of four new organically templated metal sulfates [C5H14N2][M(II)(H2O)6](SO4)2, (M(II) = Mn, Fe, Co, Ni)

A series of novel organically templated metal sulfates, [C(5)H(14)N(2)][M(II)(H(2)O)(6)](SO(4))(2) with (M(II) = Mn (1), Fe (2), Co (3) and Ni (4)), have been successfully synthesized by slow evaporation and characterized by single-crystal X-ray diffraction as well as with infrared spectroscopy, thermogravimetric analysis and magnetic measurements. All compounds were prepared using a racemic source of the 2-methylpiperazine and they crystallized in the monoclinic systems, P2(1)/n for (1, 3) and P2(1)/c for (2,4). Crystal data are as follows: [C(5)H(14)N(2)][Mn(H(2)O)(6)](SO(4))(2), a = 6.6385(10) ?, b = 11.0448(2) ?, c = 12.6418(2) ?, β = 101.903(10)°, V = 906.98(3) ?(3), Z = 2; [C(5)H(14)N(2)][Fe(H(2)O)(6)](SO(4))(2), a = 10.9273(2) ?, b = 7.8620(10) ?, c = 11.7845(3) ?, β = 116.733(10)°, V = 904.20(3) ?(3), Z = 2; [C(5)H(14)N(2)][Co(H(2)O)(6)](SO(4))(2), a = 6.5710(2) ?, b = 10.9078(3) ?, c = 12.5518(3) ?, β = 101.547(2)°, V = 881.44(4) ?(3), Z = 2; [C(5)H(14)N(2)][Ni(H(2)O)(6)](SO(4))(2), a = 10.8328(2) ?, b = 7.8443(10) ?, c = 11.6790(2) ?, β = 116.826(10)°, V = 885.63(2) ?(3), Z = 2. The three-dimensional structure networks for these compounds consist of isolated [M(II)(H(2)O)(6)](2+) and [C(5)H(14)N(2)](2+) cations and (SO(4))(2-) anions linked by hydrogen-bonds only. The use of racemic 2-methylpiperazine results in crystallographic disorder of the amines and creation of inversion centers. The magnetic measurements indicate that the Mn complex (1) is paramagnetic, while compounds 2, 3 and 4, (M(II) = Fe, Co, Ni respectively) exhibit single ion anisotropy.     

Hydrothermal synthesis and crystal structure of two new hydrated alkaline earth metal borates Sr3B6O11(OH)2 and Ba3B6O11(OH)2

Two new hydrated borates Sr(3)B(6)O(11)(OH)(2) (1) and Ba(3)B(6)O(11)(OH)(2) (2) were hydrothermally synthesized. Their structures were determined by single-crystal X-ray diffraction and further characterized by IR, powder XRD, and DSC/TGA. Compound 1 crystallizes in the triclinic space group P-1 with unit cell parameters of a = 6.6275(13) ?, b = 6.6706(13) ?, c = 11.393(2) ?, α = 91.06(3)°, β = 94.50(3)°, and γ = 93.12(3)°, while compound 2 crystallizes in the noncentrosymmetric monoclinic space group Pc with a = 6.958(14) ?, b = 7.024(14) ?, c = 11.346(2) ?, and β = 90.10(3)°. In spite of the differences in symmetry and packing of the borate chains, both structures consist of the same fundamental building block (FBB) of a [B(6)O(11)(OH)(2)](-6) unit and three unique alkaline earth metal atoms.     

Spectroscopic and magnetic properties of a series of μ-cyano bridged bimetallic compounds of the type M(II)-NC-Fe(III) (M = Mn, Co, and Zn) using the building block [Fe(III)(CN)5imidazole]2-

In this contribution, we describe the preparation and single-crystal X-ray diffraction of a new building block for bimetallic solid state materials. X-ray diffraction data of these complexes indicate that (PPh(4))(2)[Fe(CN)(5)imidazole]·2H(2)O crystallizes in the triclinic space group P1 with a = 9.8108(15) ?, b = 11.1655(17) ?, c = 23.848(4) ?, α = 87.219(2)°, β = 85.573(2)°, γ = 70.729(2)°, and Z = 2, while its precursor Na(3)[Fe(CN)(5)(en)]·5H(2)O crystallizes in the monoclinic space group P2(1)/n with a = 8.3607(7) ?, b = 11.1624(9) ?, c = 17.4233(14) ?, β = 90.1293(9)°, and Z = 4. Spectroscopic and magnetic properties of a series of bimetallic materials were obtained by reaction of the complex [Fe(CN)(5)imidazole](2-) with hydrated transition metal ions [M(H(2)O)(n)](2+) (M = Mn, Co, Zn; n = 4 or 6). The new bimetallic materials obtained are [Co(H(2)O)(2)][Fe(CN)(5)imidazole]·2H(2)O (1), [Mn(CH(3)OH)(2)][Fe(CN)(5)imidazole] (2), Zn[Fe(CN)(5)imidazole]·H(2)O (3), and [Mn(bpy)][Fe(CN)(5)imidazole].H(2)O (4). All of the complexes crystallize in the orthorhombic system. X-ray single-crystal analysis of the compounds identified the Imma space group with a = 7.3558(10) ?, b = 14.627(2) ?, c = 14.909(2) ?, and Z = 4 for 1; the P2(1)2(1)2(1) space group with a = 7.385(5) ?, b = 13.767(9) ?, c = 14.895(10) ?, and Z = 4 for 2; the Pnma space group with a = 13.783(2) ?, b = 7.167(11) ?, c = 12.599(2) ?, and Z = 4 for 3; and the Pnma space group with a = 13.192(3) ?, b = 7.224(16) ?, c = 22.294(5) ?, and Z = 4 for 4. The structures of 1, 2, and 4 consist of two-dimensional network layers containing, as the repeating unit, a cyclic tetramer [M(2)Fe(2)(CN)(4)] (M = Mn, Co). H bonding between the layers in the structure of 1 results in a quasi-three-dimensional network. The structure of 3 was found to be three-dimensional, where all of the cyano ligands are involved in bridging between the metal centers. The bridging character of the cyano is confirmed spectroscopically. The magnetic properties have been investigated for all of the bimetallic systems. Compound 1 shows ferromagnetic behavior with an ordering temperature at 25 K, which is higher than the corresponding Prussian Blue analogue Co(x)[Fe(CN)(6)](y)?·zH(2)O. Compound 2 shows weak ferromagnetic behavior and an interlayer antiferromagnetic character, while 3, as expected, shows paramagnetic character due to the diamagnetic character of Zn(2+). Compound 4 shows antiferromagnetic behavior.     

Occurence of an octanuclear motif of uranyl isophthalate with cation-cation interactions through edge-sharing connection mode

An uranyl isophthalate has been hydrothermally synthesized at 200 °C for 24 h, from a mixture of uranyl nitrate, isophthalic acid, and hydrazine in water. It was characterized by single-crystal analysis [triclinic, P ?1, a = 7.3934(3) ?, b = 13.3296(5) ?, c = 15.4432(5) ?, α = 111.865(2)°, β = 90.637(2)°, γ = 104.867(2)°, V = 1355.49(9) ?(3)] and different spectroscopic techniques (Raman, IR-ATR, UV-visible). The 3D structure of the phase (UO(2))(8)O(2)(OH)(4)(H(2)O)(4)(1,3-bdc)(4)·4H(2)O (1,3-bdc = 1,3-benzenedicarboxylate) reveals octanuclear units based on the association of 7-fold coordinated uranyl cations (pentagonal bipyramid) involving a rare case of cation-cation interaction together with edge-sharing polyhedral connection mode. UV-visible absorption spectroscopy confirmed that uranium was only involved in the structure as uranyl forms (excluding the presence of tetravalent or pentavalent uranium). Additionally, μ-Raman and IR-ATR experiments allowed assigning four uranyl contributions to the four types of uranyl entities in the structure, in agreement with the XRD analysis.     

H(x)TeV9O28]((5-x)-) (x=1 and 2): vanadotellurates with decavanadate structure

Two new vanadotellurates, [HTeV(9)O(28)](4-) and [H(2)TeV(9)O(28)](3-) have been synthesized and structurally characterized as tetra-n-butylammonium (TBA) salts: TBA(4)[HTeV(9)O(28)]·2CH(3)CN [triclinic, space group P ?1, a = 16.7102(6) ?, b = 17.4680(7) ?, c = 17.9634(7) ?, α = 74.412(1)°, β = 67.494(1)°, γ = 74.160(2)°, Z = 2] and TBA(3)[H(2)TeV(9)O(28)] [monoclinic, space group P2(1)/c, a = 13.0013(5) ?, b = 19.157(1) ?, c = 28.453(1) ?, β = 97.222(2)°, Z = 4]. The results of the structural analyses indicate that the four O atoms that bridge two V atoms on the Te side are the most basic ones in the structure. The results of density-functional theory (DFT) calculations support this view.     

Metal-centered deltahedral Zintl ions: synthesis of [Ni@Sn9]4- by direct extraction from intermetallic precursors and of the vertex-fused dimer [{Ni@Sn8(μ-Ge)(1/2)}2]4-

Ni-centered deltahedral Sn(9) clusters with a charge of 4-, i.e., [Ni@Sn(9)](4-), were extracted in ethylenediamine in high yield directly from intermetallic precursors with the nominal composition "K(4)Sn(9)Ni(3)". The new endohedral clusters were crystallized and structurally characterized in K[K(18-crown-6)](3)[Ni@Sn(9)]·3benzene (1a, triclinic, P1?, a = 10.2754(5) ?, b = 19.5442(9) ?, and c = 20.5576(13) ?, α = 73.927(3)°, β = 79.838(4)°, and γ = 84.389(3)°, V = 3899.6(4) ?(3), Z = 2) and K[K(2,2,2-crypt)](3)[Ni@Sn(9)] (1b, triclinic, P1, a = 15.8028(8) ?, b = 16.21350(9) ?, and c = 20.1760(12) ?, α = 98.71040(10)°, β = 104.4690(10)°, and γ = 118.3890(10)°, V = 4181.5(4) ?(3), Z = 2). The alternative method of a post-synthetic insertion of a Ni atom in empty Sn(9) clusters by a reaction with Ni(cod)(2) predominantly produces the more-oxidized clusters with a charge of 3-, i.e., the recently reported [Ni@Sn(9)](3-). Nonetheless, using substoichiometric amounts of 18-crown-6 as a cation sequestering agent, we also have been able to isolate the 4- clusters as a minor phase from such reactions. They were structurally characterized in K[K(en)][K(18-crown-6)](2)[Ni@Sn(9)]·0.5en (2, monoclinic, P2(1)/n, a = 10.4153(5) ?, b = 25.6788(11) ?, and c = 20.6630(9) ?, β = 102.530(2)°, V = 5394.7(4) ?(3), Z = 2). The ability of the Ni-centered clusters to exist with both 3- and 4- charges parallels the same ability of the empty clusters and is very promising for similarly rich chemistry involving electron transfer and flexible "oxidation states". We also report the synthesis and characterization of the endohedral heteroatomic dimer [{Ni@Sn(8)(μ-Ge)(1/2)}(2)](4-) composed of two [Ni@(Sn(8)Ge)]-clusters fused at the Ge-vertex. The dimer was synthesized by reacting an ethylenediamine solution of a ternary precursor with the nominal composition "K(4)Ge(4.5)Sn(4.5)", which is known to produce heteroatomic Ge(9-x)Sn(x) clusters, with Ni(cod)(2). It is isostructural with the reported [{Ni@Sn(8)(μ-Sn)(1/2)}(2)](4-) and is structurally characterized in [K-(2,2,2-crypt)](4)[{Ni@Sn(8)(μ-Ge)(1/2)}(2)]·2en (3, monoclinic, C2/c, a = 30.636(2) ?, b = 16.5548(12) ?, and c = 28.872(2) ?, β = 121.2140(10)°, V = 12523.5(15) ?(3), Z = 4).     

Synthesis and structure of QD-6: a novel aluminoborate constructed from unprecedented [B@Al6O24] and polyborate clusters

A novel aluminoborate (NH(4))(6)[C(5)NH(12)](6)[Al(12)B(65)O(105)(OH)(33)]·(H(2)O)(15) (QD-6), has been synthesized under mild hydrothermal conditions and characterized by IR, elemental analysis, TGA, powder and single-crystal X-ray diffractions. This compound crystallizes in the rhombohedral space group R3 (No. 148) with the lattice constants a = 23.7421(2) ?, c = 24.7699(3) ?, V = 12091.9(2) ?(3), and Z = 3. QD-6 consists of two unprecedented aluminoborate clusters, [Al(6)B(34)O(54)(OH)(18)](6-) and [Al(6)B(31)O(51)(OH)(15)](6-), which are built from the same hexagon-like [B@Al(6)O(24)] clusters and [B(11)O(17)(OH)(6)] or [B(10)O(16)(OH)(5)] polyborates.     

Unprecedented lanthanide-containing coordination polymers constructed from hexanuclear molecular building blocks: {[Ln6O(OH)8](NO3)2(bdc)(Hbdc)2·2NO3·H)bdc}∞

Reactions in acetonitrile between 1,4-benzene-dicarboxylic acid (C(8)H(6)O(4)) and a hexanuclear complex of lanthanide [Ln(6)O(OH)(8)(NO(3))(6)·2NO(3)] with Ln = Y or Tb lead to 1D-coordination polymers with the general chemical formula {[Ln(6)O(OH)(8)](NO(3))(2)(bdc)(Hbdc)(2)·2NO(3)·H(2)bdc}(∞) where H(2)bdc stands for 1,4-benzene-dicarboxylic acid (or terephthalic acid). These two compounds are isostructural. The crystal structure has been solved on the basis of the X-ray powder diffraction diagram of the Y-containing compound. This compound crystallizes in the triclinic system, space group P1 (no. 2) with a = 10.4956(6) ?, b = 11.529(2) ?, c = 12.357(2) ?, α = 86.869(9)°, β = 114.272(6)°, γ = 71.624(7)°, V = 1264.02 ?(3), and Z = 2. The crystal structure can be described as the juxtaposition of linear chains of hexanuclear entities linked to each other by terephthalate ligands. Two additional partially protonated terephthalate ligands spreading laterally to the chain are bound to each hexanuclear entity. Another diprotonated terephthalic ligand and two nitrate ions ensuring the electroneutrality of the crystal structure lie in the interchain space. These two compounds are thermally stable until 200 °C. Thanks to a so-called antenna effect, the Tb-containing compound, despite short intermetallic distances, exhibits a strong luminescence under UV irradiation.     

Ionothermal syntheses and characterizations of new open-framework metal borophosphates

Three new open-framework metal borophosphates, [Na(6)Co(3)B(2)P(5)O(21)Cl]·H(2)O (JIS-4), K(5)Mn(2)B(2)P(5)O(19)(OH)(2) (JIS-5), (NH(4))(8)[Co(2)B(4)P(8)O(30)(OH)(4)] (JIS-6), have been prepared under ionothermal conditions using ionic liquid 1-ethyl-3-methylimidazolium ([Emim]Br) as the solvent. They are the first examples of metalloborophosphate prepared by the ionothermal method. Their structures are determined by single-crystal X-ray diffraction. The 3-D open framework of JIS-4 is made of CoO(5)Cl octahedra, CoO(5) square pyramids, and PO(4) and BO(4) tetrahedra forming 12-ring channels along the [010] direction. It is noted that JIS-4 is the first 3-D open-framework structure in the family of borophosphate with the B/P ratio of 2/5, which features a borophosphate cluster anionic partial structure. Such cluster anionic partial structures connect with MnO(6) octahedra and MnO(5) trigonal bipyramids resulting in the formation of the 2-D layer structure of JIS-5 with the same B/P ratio as JIS-4. The 2-D layer structure of JIS-6 belongs to the largest family of borophosphate with a B/P ratio of 1/2 which features a unique 1-D chain anionic partial structure. Crystal data for JIS-4, orthorhombic, Pnma, a = 14.0638(8) ?, b = 9.8813(7) ?, c = 14.0008(10) ?, V = 1945.7(2) ?(3), and Z = 2; for JIS-5, monoclinic, P2(1)/n, a = 14.4939(3) ?, b = 9.2539(3) ?, c = 14.8031(4) ?, β = 101.4600(10)°, V = 1945.88(9) ?(3), and Z = 4. For JIS-6, triclinic, P1, a = 9.6928(3) ?, b = 9.8747(3) ?, c = 10.0125(2) ?, α = 62.057(2)°, β = 82.456(2)°, γ = 76.095(2)°, V = 821.60(4) ?(3), and Z = 1.     

Extreme differences in oxidation states: synthesis and structural analysis of the germanide oxometallates A10[Ge9]2[WO4] as well as A(10+x)[Ge9]2[W(1–x)Nb(x)O4] with A = K and Rb containing [Ge9]4- polyanions

Semitransparent dark-red or ruby-red moisture- and air-sensitive single crystals of A(10+x)[Ge(9)](2)[W(1-x)Nb(x)O(4)] (A = K, Rb; x = 0, 0.35) were obtained by high-temperature solid-state reactions. The crystal structure of the compounds was determined by single-crystal X-ray diffraction experiments. They crystallize in a new structure type (P2(1)/c, Z = 4) with a = 13.908(1) ?, b = 15.909(1) ?, c = 17.383(1) ?, and β = 90.050(6)° for K(10.35(1))[Ge(9)](2)[W(0.65(1))Nb(0.35(1))O(4)]; a = 14.361(3) ?, b = 16.356(3) ?, c = 17.839(4) ?, and β = 90.01(3)° for Rb(10.35(1))[Ge(9)](2)[W(0.65(1))Nb(0.35(1))O(4)]; a = 13.8979(2) ?, b = 15.5390(3) ?, c = 17.4007(3) ?, and β = 90.188(1)° for K(10)[Ge(9)](2)WO(4); and a = 14.3230(7) ?, b = 15.9060(9) ?, c = 17.8634(9) ?, and β = 90.078(4)° for Rb(10)[Ge(9)](2)WO(4). The compounds contain discrete Ge(9)(4-) Wade's nido clusters and WO(4)(2-) (or NbO(4)(3-)) anions, which are packed according to a hierarchical atom-to-cluster replacement of the Al(2)Cu prototype and are separated by K and Rb cations, respectively. The alkali metal atoms occupy the corresponding tetrahedral sites of the Al(2)Cu prototype. The amount of the alkali metal atoms on these diamagnetic compounds corresponds directly to the amount of W substituted by Nb. Thus, the transition metals W and Nb appear with oxidation numbers +6 and +5, respectively, in the vicinity of a [Ge(9)](4-) polyanion. The crystals of the mixed salts were further characterized by Raman spectroscopy. The Raman data are in good agreement with the results from the X-ray structural analyses.     

Synthesis and characterization of thorium(IV) sulfates

Three Th(IV) sulfates, two new and one previously reported, have been synthesized from aqueous solution. In all of the compounds, the sulfate anions coordinate the Th(4+) metal center(s) in a monodentate manner with Th-S distances of 3.7-3.8 ?. Th(SO(4))(2)(H(2)O)(7)·2(H(2)O) (1; P2(1)/m, a = 7.224(1) ?, b = 12.151(1) ?, c = 7.989(1) ?, ss =98.289(2)°) and Th(4)(SO(4))(7)(H(2)O)(7)(OH)(2)·H(2)O (2; Pnma, a = 18.139(2) ?, b = 11.173(1) ?, c = 14.391(2) ?) each contain 9-coordinate monomeric (1,2) and dimeric (2) Th(IV) cations in monocapped square antiprism geometry. Alternatively, Th(OH)(2)SO(4) (3; Pnma, a = 11.684(1) ?, b = 6.047(1) ?, c = 7.047(1) ?) is built from chains of hydroxo-bridged, 8-coordinate Th(4+) centers. Whereas 1 adopts a molecular structure, 2 and 3 both exhibit 3D architectures. Differences in the dimensionality and the topology of 1-3 are manifested in the local coordination environment about the Th(IV) centers, the formation of oligomeric Th(4+) species, and the extended connectivity of the sulfate ligands. Herein, we report the syntheses and characterization of 1-3 as well as the atomic correlations of 1 in solution, as determined by high-energy X-ray scattering (HEXS).     

Investigation of the crystal structure of a basic bismuth(III) nitrate with the composition [Bi6O4(OH)4](0.54(1))[Bi6O5(OH)3](0.46(1))(NO3)(5.54(1))

A basic bismuth(III) nitrate with the composition [Bi(6)O(4)(OH)(4)](0.5)[Bi(6)O(5)(OH)(3)](0.5)(NO(3))(5.5) formed in a slow crystal growth mode has an ordered crystal structure with the monoclinic space group P2(1) and lattice parameters a = 15.850(3), b = 14.986(3), c = 18.230(4) ?, β = 107.329(17)° and volume V = 4133.6 ?(3) (Henry et al. 2003). In a very fast crystal growth mode the complex ions disorder in another P2(1) cell with slightly different lattice parameters a = 15.8404(1), b = 15.1982(1), c = 18.3122(1) ?, β = 106.829(1)° and V = 4219.8 ?(3). This cell can be related to two smaller cells: a monoclinic C2/m cell with a = 13.7161(1), b = 15.1943(1), c = 10.2399(1) ?, β = 98.586(1)° and V = 2110.1 ?(3) and a trigonal R3 cell with a = 15.18650(6), c = 15.8416(1) ? (hexagonal setting) and V = 3164.1 ?(3). These smaller cells correspond to average structures and hence the X-ray data do not account for the difference in the structures of the two different complex ions. However, when analysing neutron powder diffraction data, it is possible to distinguish between the two complex ions using a trigonal R3 cell with a = 15.1865(1) and c = 15.8416(1) ? (hexagonal setting). In a Rietveld type structure model refinement with a total of 28 atom sites (4 Bi, 3 N, 15 O and 6 H), the composition of this sample is determined to be [Bi(6)O(4)(OH)(4)](0.54(1))[Bi(6)O(5)(OH)(3)](0.46(1))(NO(3))(5.54(1)).     

Aluminosilicate relatives: Chalcogenoaluminogermanates Rb(3)(AlQ(2))(3)(GeQ(2))(7) (Q = S, Se)

The new compounds Rb(3)(AlQ(2))(3)(GeQ(2))(7) [Q = S (1), Se (2)] feature the 3D anionic open framework [(AlQ(2))(3)(GeQ(2))(7)](3-) in which aluminum and germanium share tetrahedral coordination sites. Rb ions are located in channels formed by the connection of 8, 10, and 16 (Ge/Al)S(4) tetrahedra. The isostructural sulfur and selenium derivatives crystallize in the space group P2(1)/c. 1: a = 6.7537(3) ?, b = 37.7825(19) ?, c = 6.7515(3) ?, and β = 90.655(4)°. 2: a = 7.0580(5) ?, b = 39.419(2) ?, c = 7.0412(4) ?, β = 90.360(5)°, and Z = 2 at 190(2) K. The band gaps of the congruently melting chalcogenogermanates are 3.1 eV (1) and 2.4 eV (2).     

The unprecedented preparation of dinuclear zinc(II) complexes from 4-halido-2-[(3-cyclohexylaminopropylimino)methyl]phenol

Three new centrosymmetric trinuclear nickel(II) and manganese(II) complexes, Ni[Ni(CH(3)COO)(CPA)](2) (1), Ni[Ni(CH(3)COO)(BPA)](2) (2), Mn[Mn(CH(3)COO)(BPA)](2) (3), where H(2)CPA = N,N'-bis(5-chlorosalicylidene)-1,3-propanediamine, H(2)BPA = N,N'-bis(5-bromosalicylidene)-1,3-propanediamine, and two new centrosymmetric dinuclear zinc(II) complexes, [Zn(2)(CMP)(2)] (4) and [Zn(2)(BMP)(2)] (5), where H(2)CMP = 4-chloro-2-{[3-(5-chloro-2-hydroxybenzyl)aminopropylimino]methyl}phenol, and H(2)BMP = 4-bromo-2-{[3-(5-bromo-2-hydroxybenzyl)aminopropylimino]methyl}phenol, have been prepared from the Schiff bases derived from 5-halido-substituted salicylaldehydes with N-hexylpropane-1,3-diamine under solvothermal conditions. The complexes have been characterised by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction studies. The complexes 1, 2, and 3 crystallise in the monoclinic space group P2(1)/c with cell dimensions a = 9.347(1), b = 11.507(2), c = 18.539(2) ?, β = 93.774(2)°, Z = 2 (for 1), a = 9.111(4), b = 12.089(6), c = 18.724(8) ?, β = 92.117(7)°, Z = 2 (for 2), and a = 11.328(2), b = 22.468(5), c = 8.270(2) ?, β = 93.74(3)°, Z = 2 (for 3), while complexes 4 and 5 crystallise in the triclinic space group P1, with cell dimensions a = 7.483(1), b = 9.990(2), c = 12.155(2) ?, α = 75.27(3), β = 85.00(3), γ = 73.82(3)°, Z = 1 (for 4), and a = 7.008(1), b = 10.081(2), c = 13.095(3) ?, α = 100.62(3), β = 95.51(3), γ = 104.03(3)°, Z = 1 (for 5). It is interesting that the mono-Schiff bases 4-chloro-2-[(3-cyclohexylaminopropylimino)methyl]phenol (HCCP) and 4-bromo-2-[(3-cyclohexylaminopropylimino)methyl]phenol (HBCP) used to prepare the nickel(II) and manganese(II) complexes were transferred to bis-Schiff bases H(2)CPA and H(2)BPA in the complexes 1, 2, and 3, while the mono-Schiff bases HCCP and HBCP used to prepare the zinc(II) complexes were transferred to novel ligands H(2)CMP and H(2)BMP, bearing the unexpected, newly formed carbon-nitrogen single bond.     

A C2-symmetric antimonato polyoxovanadate cluster [V16Sb4O42(H2O)](8-) derived from the {V18O42} archetype

The new antimonato polyoxovanadate [V(IV)(16)Sb(III)(4)O(42)(H(2)O)](8-) cluster (1a) is the main structural motif of the solvothermally obtained compound {(trenH(2))Zn(tren)}(2)[V(16)Sb(4)O(42)(H(2)O)]·xH(2)O (x = 6-10) (1) (tren = tris(2-aminoethyl)amine). The C(2)-symmetric cluster structure is closely related to the {V(18)O(42)} archetype. 1 crystallizes in the monoclinic space group C2/c with a = 30.7070(19) ?, b = 13.9512(5) ?, c = 23.1435(14) ?, β = 128.076(6)°, and V = 7804.8(7) ?(3). The orientation of the [Sb(III)(2)O(5)](4-) groups in each cluster leads to intermolecular Sb···O contacts and the formation of channels between the clusters. [Zn(tren)(trenH(2))] complexes with trigonal bipyramidal coordination environments are located between the [V(16)Sb(4)O(42)(H(2)O)](8-) anions, and form a three dimensional network with them via strong N-H···O hydrogen bonds. Up to 250 °C crystal water molecules are emitted, which are reversibly incorporated in humid air.     

New ionic crystals of oppositely charged cluster ions and their characterization

By reacting Keggin-type polyoxometalate cluster anions H(2)W(12)O(40)(6)(-) (metatungstate) or Co(II)W(12)O(40)(6)(-) (tungstocobaltate) with the large aluminum cluster polycation [Al(30)O(8)(OH)(56)(H(2)O)(26)](18+), Keggin ion based molecular ionic compounds [delta-Al(13)O(4)(OH)(24)(H(2)O)(12)][XW(12)O(40)](OH).nH(2)O (X = H(2) (1) and Co (2); n congruent with 20) and [W(2)Al(28)O(18)(OH)(48)(H(2)O)(24)][H(2)W(12)O(40)](2).55H(2)O (3) were obtained. The polygon-shaped cluster ions are packed alternately through intercluster hydrogen bonds as well as electrostatic interactions, leaving large pores, which result from the packing of large clusters. The clusters are arranged in square pyramidal geometries, showing face-to-face interactions between them. The isolation of metastable [delta-Al(13)O(4)(OH)(24)(H(2)O)(12)](7+) and the formation of a new transition metal substituted aluminum heteropolycation [W(2)Al(28)O(18)(OH)(48)(H(2)O)(24)](12+) in 1-3 result from the slow fragmentation and recombination of Al(30) in the presence of suitable counter cluster anions with similar shape and charge.     

Systematic investigation of zinc aminoalkylphosphonates: influence of the alkyl chain lengths on the structure formation

With the high-throughput (HT) methodology, the bifunctional aminoalkylphosphonic acids (AAPA) linker molecules 2-aminoethyl- (AEPA), 3-aminopropyl- (APPA), and 4-aminobutylphosphonic acid (ABPA) [HO(3)P-C(n)H(2n)-NH(2) (n = 2-4)] and zinc nitrate were used to synthesize new metal phosphonates in order to investigate the influence of the alkyl chain length on the structure formation. The systematic investigations led to one known (ZnO(3)PC(2)H(4)NH(2)) and six new compounds: one using AEPA, three using APPA, and two using ABPA. The crystal structures of five compounds were determined by single crystal X-ray diffraction, using X-ray powder diffraction (XRPD) data as well as structure modeling employing force field methods. For compound 1, Zn(O(3)P-C(2)H(4)-NH(3))(NO(3))(H(2)O) (monoclinic, Cc, a = 4.799(1) ?, b = 29.342(6) ?, c = 5.631(1) ?, β = 91.59(3)°, V = 792.7(3) ?(3), Z = 4), and compound 2, Zn(2)(OH)(O(3)P-C(3)H(6)-NH(3))(NO(3)) (monoclinic, P2/c, a = 12.158(2) ?, b = 5.0315(10) ?, c = 13.952(3) ?, β = 113.23(3)°, V = 784.3(3) ?(3), Z = 2), the structures were determined using single crystal X-ray diffraction data. The crystal structures of [Zn(O(3)P-C(3)H(6)-NH(2))]·H(2)O (3) (monoclinic, P2(1)/c, a = 9.094(2) ?, b = 5.0118(7) ?, c = 16.067(4) ?, β = 90.38(2)°, V = 732.3(2) ?(3), Z = 4) and Zn(O(3)P-C(4)H(8)-NH(2)) (5) (monoclinic, P2(1)/c, a = 8.570(7) ?, b = 8.378(4) ?, c = 9.902(6) ?, β = 90.94(5)°, V = 710.9(8) ?(3), Z = 4) were determined using XRPD data. The structural model for compound 6, Zn(O(3)P-C(4)H(8)-NH(3))(NO(3))(H(2)O), was established using lattice parameters from XRPD data and following crystal structure modeling employing force field methods. The structures depend strongly on the alkyl chain length n. For n = 2 and 4 isoreticular compounds are observed, while n = 3 leads to new structures. Larger amounts of all compounds were obtained employing scale-up syntheses in a conventional oven as well as in a microwave reactor system. In addition, in situ energy dispersive X-ray diffraction (EDXRD) experiments at 130 °C were performed at beamline F3 at HASYLAB, DESY, Hamburg, to investigate the formation of compounds 2 and 3 as well as the phase transformation of 2 into 3 upon addition of NaOH. All compounds were characterized in detail using X-ray powder diffraction, IR/Raman spectroscopy, and thermogravimetric and elemental analysis.     

A new organic-inorganic hybrid layered molybdenum(V) cobalt phosphate constructed from [H24(Mo16O32)Co16(PO4)24(OH)4(C5H4N)2(H2O)6](4-) wheels and 4,4'-bipyridine linkers

A new layered molybdenum cobalt phosphate, Na(2)[Co(H(2)O)(6)][(Mo(16)O(32))Co(16)(PO(4))(4) (HPO(4))(16)(H(2)PO(4))(4)(OH)(4)(C(10)H(8)N(2))(4)(C(5)H(4)N)(2)(H(2)O)(6)]·4H(2)O (1), has been hydrothermally synthesized and structurally characterized. 1 crystallizes in the monoclinic space group P2(1)/n with a = 15.6825(18) ?, b = 39.503(4) ?, c = 17.2763(17) ?, β = 93.791(2)°, V = 10679.4(18) ?(3), and Z = 2. A polyoxoanion of 1 exhibits an unusual organic-inorganic hybrid wheel-type cluster, in which two pyridine ligands link to the surface Co(II) atoms of a [H(24)(Mo(16)O(32))Co(16)(PO(4))(24)(OH)(4)(H(2)O)(6)] (namely, {Mo(16)Co(16)P(24)}) wheel via the Co-N bonds. Furthermore, each {Mo(16)Co(16)P(24)} wheel is connected to four adjacent wheels by four pairs of 4,4'-bipyridine linkers, forming a 2D layered network. The susceptibility measurement shows the existence of dominant antiferromagnetic interactions in 1.     

The series of molecular conductors and superconductors ET4[AFe(C2O4)3]·PhX (ET = bis(ethylenedithio)tetrathiafulvalene; (C2O4)2- = oxalate; A+ = H3O+, K+; X = F, Cl, Br, and I): influence of the halobenzene guest molecules on the crystal structure and superconducting properties

An extensive series of radical salts formed by the organic donor bis(ethylenedithio)tetrathiafulvalene (ET), the paramagnetic tris(oxalato)ferrate(III) anion [Fe(C(2)O(4))(3)](3-), and halobenzene guest molecules has been synthesized and characterized. The change of the halogen atom in this series has allowed the study of the effect of the size and charge polarization on the crystal structures and physical properties while keeping the geometry of the guest molecule. The general formula of the salts is ET(4)[A(I)Fe(C(2)O(4))(3)]·G with A/G = H(3)O(+)/PhF (1); H(3)O(+)/PhCl (2); H(3)O(+)/PhBr (3), and K(+)/PhI (4), (crystal data at room temperature: (1) monoclinic, space group C2/c with a = 10.3123(2) ?, b = 20.0205(3) ?, c = 35.2732(4) ?, β = 92.511(2)°, V = 7275.4(2) ?(3), Z = 4; (2) monoclinic, space group C2/c with a = 10.2899(4) ?, b = 20.026(10) ?, c = 35.411(10) ?, β = 92.974°, V = 7287(4) ?(3), Z = 4; (3) monoclinic, space group C2/c with a = 10.2875(3) ?, b = 20.0546(15) ?, c = 35.513(2) ?, β = 93.238(5)°, V = 7315.0(7) ?(3), Z = 4; (4) monoclinic, space group C2/c with a = 10.2260(2) ?, b = 19.9234(2) ?, c = 35.9064(6) ?, β = 93.3664(6)°, V = 7302.83(18) ?(3), Z = 4). The crystal structures at 120 K evidence that compounds 1-3 undergo a structural transition to a lower symmetry phase when the temperature is lowered (crystal data at 120 K: (1) triclinic, space group P1 with a = 10.2595(3) ?, b = 11.1403(3) ?, c = 34.9516(9) ?, α = 89.149(2)°, β = 86.762(2)°, γ = 62.578(3)°, V = 3539.96(19) ?(3), Z = 2; (2) triclinic, space group P1 with a = 10.25276(14) ?, b = 11.15081(13) ?, c = 35.1363(5) ?, α = 89.0829(10)°, β = 86.5203(11)°, γ = 62.6678(13)°, V = 3561.65(8) ?(3), Z = 2; (3) triclinic, space group P1 with a = 10.25554(17) ?, b = 11.16966(18) ?, c = 35.1997(5) ?, α = 62.7251(16)°, β = 86.3083(12)°, γ = 62.7251(16)°, V = 3575.99(10) ?(3), Z = 2; (4) monoclinic, space group C2/c with a = 10.1637(3) ?, b = 19.7251(6) ?, c = 35.6405(11) ?, β = 93.895(3)°, V = 7128.7(4) ?(3), Z = 4). A detailed crystallographic study shows a change in the symmetry of the crystal for compound 3 at about 200 K. This structural transition arises from the partial ordering of some ethylene groups in the ET molecules and involves a slight movement of the halobenzene guest molecules (which occupy hexagonal cavities in the anionic layers) toward one of the adjacent organic layers, giving rise to two nonequivalent organic layers at 120 K (compared to only one at room temperature). The structural transition at about 200 K is also observed in the electrical properties of 1-3 and in the magnetic properties of 1. The direct current (dc) conductivity shows metallic behavior in salts 1-3 with superconducting transitions at about 4.0 and 1.0 K in salts 3 and 1, respectively. Salt 4 shows a semiconductor behavior in the temperature range 300-50 K with an activation energy of 64 meV. The magnetic measurements confirm the presence of high spin S = 5/2 [Fe(C(2)O(4))(3)](3-) isolated monomers together with a Pauli paramagnetism, typical of metals, in compounds 1-3. The magnetic properties can be very well reproduced in the whole temperature range with a simple model of isolated S = 5/2 ions with a zero field splitting plus a temperature independent paramagnetism (Nα) with the following parameters: g = 1.965, |D| = 0.31 cm(-1), and Nα = 1.5 × 10(-3) emu mol(-1) for 1, g = 2.024, |D| = 0.65 cm(-1), and Nα = 1.4 × 10(-3) emu mol(-1) for 2, and g = 2.001, |D| = 0.52 cm(-1), and Nα = 1.5 × 10(-3) emu mol(-1) for 3.