ASb2(SO4)2(PO4) (A = H3O+, K,Rb): Layered Structure Containing Ordered Sulfate and Phosphate Anions

Three compounds ASb₂(SO₄)₂(PO₄) (A = H₃O⁺, K, Rb) were obtained from the reactions of Sb₂O₃, A₂CO₃ (A = Li, Rb) or K₂SO₄ and NH₄H₂PO₄ in H₂SO₄ (98 %) at 220–250 °C. Their structures were determined by single‐crystal X‐ray diffraction. All compounds crystallize in the triclinic space group P$\bar{1}$ (no.2) and are isostructural. The crystal structures consist of two‐dimensional ²_∞[Sb₂(SO₄)₂(PO₄)]^– anionic layers and alkali cations, which are located between anionic layers. The anionic layers are composed of [SbO₄] ψ‐trigonal bipyramids, [SbO₅] ψ octahedra, [SO₄] tetrahedra, and [PO₄] tetrahedra. All compounds are characterized by solid state UV/Vis/NIR diffuse reflectance spectra, FT‐IR spectroscopy, and Raman spectroscopy.     

Synthesis,crystal structure and studies on the interaction with albumin of a new silver(I) complex based on 2‐(4‐nitrobenzenesulfonamido)benzoic acid

In the present work, the two‐dimensional (2D) polymer poly[[μ₄‐2‐(4‐nitrobenzenesulfonamido)benzoato‐κ⁴O¹:O¹:O^1′:N⁶]silver(I)] (AgL), [Ag(C₁₃H₉N₂O₆S)]_n, was obtained from 2‐(4‐nitrobenzenesulfonamido)benzoic acid (HL), C₁₃H₁₀N₂O₆S. FT–IR, ¹H and ¹³C{¹H} NMR spectroscopic analyses were used to characterize both compounds. The crystal structures of HL and AgL were determined by single‐crystal X‐ray diffraction. In the structure of HL, O—H…O hydrogen bonds between neighbouring molecules result in the formation of dimers, while the silver(I) complex shows polymerization associated with the O atoms of three distinct deprotonated ligands (L^?). Thus, the structure of the Ag complex can be considered as a coordination polymer consisting of a one‐dimensional linear chain, constructed by carboxylate bridging groups, running parallel to the b axis. Neighbouring polymeric chains are further bridged by Ag—C monohapto contacts, resulting in a 2D framework. Fingerprint analysis of the Hirshfeld surfaces show that O…H/H…O hydrogen bonds are responsible for the most significant contacts in the crystal packing of HL and AgL, followed by the H…H and O…C/C…O interactions. The Ag…Ag, Ag…O/O…Ag and Ag…C/C…Ag interactions in the Hirshfeld surface represent 12.1% of the total interactions in the crystal packing. Studies of the interactions of the compounds with human serum albumin (HSA) indicated that both HL and AgL interact with HSA.     

Homologous Silver Bismuth Chalcogenide Halides (N,x)P. III. The (4, x)P, (5, x)P,and (7, x)P Structure Families of Modular Compounds with Tunable Composition and Structure

The crystal structures of six members of the homologous series with general formula [BiQX]₂[Ag_xBi_1?xQ_2?2xX_2x?1]_N+1 (Q = S, Se; X = Cl, Br; 1/2 ≤ x ≤ 1) and N = 4, 5, or 7 were determined by single‐crystal X‐ray diffraction. The series are characterized by the parameters N and x and are denoted ^{(N, x)}P. Ag₃Bi₄S₆Cl₃ (x = 0.60) (I) , Ag_3.5Bi_3.5S₅Br₄ (x = 0.70) (II) and Ag_3.65Bi_3.35Se_4.70Br_4.30 (x = 0.73) (III) belong to ^{(4, x})P series Ag_5xBi_7?5xQ_12?10xX_10x?3 and adopt the AgBi₆S₉ structure type. The ^{(5, x)}P compound Ag_3.66Bi_4.34S_6.68Br_3.32 (IV) , which corresponds to x = 0.61 in Ag_6xBi_8?6xS_14?12xBr_12x?4, crystallizes isostructurally to AgBi₃S₅. The compounds Ag_4.56Bi_5.44Se_8.88Br_3.12 (x = 0.57) (V) and Ag_5.14Bi_4.86S_7.76Br_4.24 (x = 0.64) (VI) , which are members of ^{(7, x)}P series Ag_8xBi_10?8xQ_18?16xBr_16x?6, adopt the Ag₃Bi₇S₁₂ structure type. In the monoclinic crystal structures (space group C2/m) two kinds of layered modules alternate along [001]. Modules of type A uniformly consist of paired rods of face‐sharing monocapped trigonal prisms around Bi atoms with octahedra around mixed occupied metal positions (M = Ag/Bi) between them. Modules of type B are composed of [MZ₆] octahedra, which are arranged in NaCl‐type fragments of thickness N. All structures exhibit Ag/Bi disorder in octahedrally coordinated metal positions as well as Q/X mixed occupation of some anion positions. Corresponding to their black color, all compounds are narrow‐gap semiconductors (E_g = 0.35 eV for (II) ). General characteristics of the entire class of ^{(N, x)}P compounds are gathered in a catalogue.     

Potassium thiocyanate argentates: K3[Ag(SCN)4], K4[Ag2(SCN)6] and K[Ag(SCN)2]

The anions of the title compounds contain [Ag(SCN)₄] units, with the S atoms coordinating to Ag⁺ in a tetrahedral arrangement. Whereas in the isolated anions of tripotassium tetra­thio­cyanatoargentate(I), K₃[Ag(SCN)₄], (I), all SCN^? groups are bonded as terminal ligands, in tetrapotassium di‐μ‐thio­cyanato‐S:S‐bis­[dithio­cyanato­argentate(I)], K₄[Ag₂(SCN)₆], (II), two AgS₄ tetrahedra share one common edge. In poly[potassium [argentate(I)‐di‐μ‐thio­cyanato‐S:S]], K[Ag(SCN)₂], (III), edge‐ and vertex‐sharing of AgS₄ tetrahedra results in infinite [Ag(SCN)₂]^? layers.     

Synthese und Kristallstruktur von Hydrogensulfaten einwertiger Metalle – Ag(H3O)(HSO4)2, Ag2(HSO4)2(H2SO4), AgHSO4 und Hg2(HSO4)2

Synthesis and Crystal Structure of Metal(I) Hydrogen Sulfates – Ag(H₃O)(HSO₄)₂, Ag₂(HSO₄)₂(H₂SO₄), AgHSO₄, and Hg₂(HSO₄)₂ Hydrogen sulfates Ag(H₃O)(HSO₄)₂, Ag₂(HSO₄)₂ · (H₂SO₄), and AgHSO₄ have been synthesized from Ag₂SO₄ and sulfuric acid. Hg₂(HSO₄)₂ was obtained from metallic mercury and 96% sulfuric acid as starting materials. The compounds were characterized by X‐ray single crystal structure determination. Ag(H₃O)(HSO₄)₂ belongs to the structure type of Na(H₃O)(HSO₄). The silver atom is coordinated by 6 + 2 oxygen atoms. In the structure, there are dimers and chains of hydrogen bonded HSO₄^– tetrahedra. Dimers and chains are connected by the H₃O⁺ ion to form a three dimensional hydrogen network. Ag₂(HSO₄)₂(H₂SO₄) crystallizes isotypic to Na₂(HSO₄)₂(H₂SO₄). The coordination number of silver is 6 + 1. The structure of Ag₂(HSO₄)₂(H₂SO₄) is characterized by hydrogen bonded trimers of HSO₄^– tetrahedra, which are further connected to chains. For the recently published structure of AgHSO₄ the hydrogen bonding system was discussed. There are tetrameres and chains, connected by bifurcated hydrogen bonds. The structure of Hg₂(HSO₄)₂ contains Hg₂²⁺ cations with Hg–Hg distance of 2.509 Å. Every mercury atom is coordinated by one oxygen atom at shorter distance (2.18 Å) and three ones at longer distances (2.57 to 3.08 Å). The HSO₄^– tetrahedra form zigzag chains by hydrogen bonds.     

Synthese und Kristallstruktur von K2(HSO4)(H2PO4), K4(HSO4)3(H2PO4) und Na(HSO4)(H3PO4)

Synthesis and Crystal Structure of K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄), and Na(HSO₄)(H₃PO₄) Mixed hydrogen sulfate phosphates K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄) and Na(HSO₄)(H₃PO₄) were synthesized and characterized by X‐ray single crystal analysis. In case of K₂(HSO₄)(H₂PO₄) neutron powder diffraction was used additionally. For this compound an unknown supercell was found. According to X‐ray crystal structure analysis, the compounds have the following crystal data: K₂(HSO₄)(H₂PO₄) (T = 298 K), monoclinic, space group P 2₁/c, a = 11.150(4) Å, b = 7.371(2) Å, c = 9.436(3) Å, β = 92.29(3)°, V = 774.9(4) ų, Z = 4, R₁ = 0.039; K₄(HSO₄)₃(H₂PO₄) (T = 298 K), triclinic, space group P 1, a = 7.217(8) Å, b = 7.521(9) Å, c = 7.574(8) Å, α = 71.52(1)°, β = 88.28(1)°, γ = 86.20(1)°, V = 389.1(8)ų, Z = 1, R₁ = 0.031; Na(HSO₄)(H₃PO₄) (T = 298 K), monoclinic, space group P 2₁, a = 5.449(1) Å, b = 6.832(1) Å, c = 8.718(2) Å, β = 95.88(3)°, V = 322.8(1) ų, Z = 2, R₁ = 0,032. The metal atoms are coordinated by 8 or 9 oxygen atoms. The structure of K₂(HSO₄)(H₂PO₄) is characterized by hydrogen bonded chains of mixed H_nS/PO₄^– tetrahedra. In the structure of K₄(HSO₄)₃(H₂PO₄), there are dimers of H_nS/PO₄^– tetrahedra, which are further connected to chains. Additional HSO₄^– tetrahedra are linked to these chains. In the structure of Na(HSO₄)(H₃PO₄) the HSO₄^– tetrahedra and H₃PO₄ molecules form layers by hydrogen bonds.     

Neue Thiophosphate: Die Verbindungen Li6Ln3(PS4)5 (Ln: Y,Gd, Dy,Yb, Lu) und Ag3Y(PS4)2

New Thiophosphates: The Compounds Li₆Ln₃(PS₄)₅ (Ln: Y, Gd, Dy, Yb, Lu) and Ag₃Y(PS₄)₂ The new thiophosphates Li₆Ln₃(PS₄)₅ (Ln: Y, Gd, Dy, Yb, Lu) were synthesized by heating mixtures of Ln, P, S, and Li₂S₄ at 900 °C (100 h) and they were investigated by single crystal X‐ray methods. The compounds with Ln = Y (a = 28.390(2), b = 10.068(1), c = 33.715(2) Å, β = 113.85(1)°), Gd (a = 28.327(2), b = 10.074(1), c = 33.822(2) Å, β = 114.297(7)°), Dy (a = 28.124(6), b = 10.003(2), c = 33.486(7) Å, β = 113.89(3)°), Yb (a = 28.178(3), b = 9.977(1), c = 33.392(4) Å, β = 113.65(1)°), and Lu (a = 28.169(6), b = 10.002(2), c = 33.432(7) Å, β = 113.54(3)°) are isotypic and crystallize in a new structure type (C2/c; Z = 12). Main feature are PS₄ tetrahedra isolated from each other surrounding the Ln and Li atoms via their S atoms. The coordination number of the five crystallographically independent Ln atoms is eight, but the polyhedra are quite different and they are interlinked to larger units extending in [010]. The environment of the Li atoms is irregular and formed by five to six S atoms. The crystal structure is compared with that of Li₉Ln₂(PS₄)₅ (Ln: Nd, Gd). For the synthesis of Ag₃Y(PS₄)₂ (a = 16.874(3), b = 9.190(2), c = 9.312(2) Å, β = 123.17(3)°) a mixture of Y, P, S, and Ag₂S was heated to 700 °C (50 h). The thiophosphate crystallizes in a new structure type (C2/c; Z = 4) composed of isolated PS₄ tetrahedra. The two crystallographically independent Ag atoms are surrounded by four S atoms in the shape of distorted tetrahedra. The Ag(1)S₄ polyhedra are cornershared to strands running along [001], which are linked together via Ag(2)S₄ tetrahedra. The environment of the Y atoms is composed of eight S atoms each building distorted square antiprisms. These polyhedra are connected with each other via common edges to a strand running along [001].     

Counter‐anion role in the formation of two supramolecular complexes: [Ag2(DPP)2](ClO4)2·CH3CN and [Ag2(DPP)2(NO3)2] {DPP is N‐[(diphenylphosphanyl)methyl]pyridin‐4‐amine}

The title compounds, bis{μ‐N‐[(diphenylphosphanyl)methyl]pyridin‐4‐amine‐κ²N¹:P}disilver bis(perchlorate) acetonitrile monosolvate, [Ag₂(C₁₈H₁₇N₂P)₂](ClO₄)₂·CH₃CN, (1), and bis{μ‐N‐[(diphenylphosphanyl)methyl]pyridin‐4‐amine‐κ²N¹:P}bis[(nitrato‐κ²O,O)silver], [Ag₂(C₁₈H₁₇N₂P)₂(NO₃)₂], (2), each contain disilver macrocyclic [Ag₂(C₁₈H₁₇N₂P)₂]²⁺ cations lying about inversion centres. The cations are constructed by two N‐[(diphenylphosphanyl)methyl]pyridin‐4‐amine (DPP) ligands linking two Ag⁺ cations in a head‐to‐tail fashion. In (1), the unique Ag⁺ cation has a near‐linear coordination geometry consisting of one pyridine N atom and one P atom from two different DPP ligands. Two ClO₄⁻ anions doubly bridge two metallomacrocycles through Ag...O and N—H...O weak interactions to form a chain extending in the c direction. The half‐occupancy acetonitrile molecule lies with its methyl C atom on a twofold axis and makes a weak N...Ag contact. In (2), there are two independent [Ag(C₁₈H₁₇N₂P)]⁺ cations. The nitrate anions weakly chelate to each Ag⁺ cation, leading to each Ag⁺ cation having a distorted tetrahedral coordination geometry consisting of one pyridine N atom and one P atom from two different DPP ligands, and two chelating nitrate O atoms. Each dinuclear [Ag₂(C₁₈H₁₇N₂P)₂(NO₃)₂] molecule acts as a four‐node to bridge four adjacent equivalent molecules through N—H...O interactions, forming a two‐dimensional sheet parallel to the bc plane. Each sheet contains dinuclear molecules involving just Ag1 or Ag2 and these two types of sheet are stacked in an alternating fashion. The sheets containing Ag1 all lie near x = , , etc, while those containing Ag2 all lie near x = 0, 1, 2 etc. Thus, the two independent sheets are arranged in an alternating sequence at x = 0, , 1, etc. These two different supramolecular structures result from the different geometric conformations of the templating anions which direct the self‐assembly of the cations and anions.     

Structural Characterization of Some Coinage Metal(I) Thiosulfate Complexes, $\rm M^{1}_{a}M\rm ^{2}_{b}(X_{c}) (S_{2}O_{3})_{d}(\cdot eS)$ (M1 = Group 1 Cation,X = Univalent Anion,M2 = CuI,AgI, S = Solvent)

Building on previous single crystal X‐ray structure determinations for the group 1 salts of complex thiosulfate/univalent coinage metal anions previously defined for (NH₄)₉AgCl₂(S₂O₃)₄, NaAgS₂O₃·H₂O and Na₄[Cu(NH₃)₄][Cu(S₂O₃)₂]·NH₃, a wide variety of similar salts, of the form , M¹ = group 1 metal cation, M² = univalent coinage metal cation (Cu, Ag), (X = univalent anion), most previously known, but some not, have been isolated and subjected to similar determinations. These have defined further members of the isotypic, tetragonal series, for M¹ = NH₄, M² = Cu, Ag, X = NO₃, Cl, Br, I, together with the K/Cu/NO₃ complex, all containing the complex anion [M²(SSO₃)₄]^7? with M² in an environment of symmetry, Cu, Ag‐S typically ca. 2.37, 2.58Å, with quasi‐tetrahedral S‐M‐S angular environments. Further salts of the form , n = 1‐3, have also been defined: For n = 3, M² = Cu, M¹/x = K/2.25 or 1 5/6, NH₄/6, (and also for the (NH₄)₄Na/4H₂O·MeOH adduct) the arrays take the form with distorted trigonal planar CuS₃ coordination environments, Cu‐S distances being typically 2.21Å, S‐Cu‐S ranging between 105.31(4)–129.77(4)°; the silver counterparts take the form for M¹ = K, NH₄. For n = 2, adducts have only been defined for M² = Ag, the anions of the M¹ = Na, K adducts being dimeric and polymeric respectively: Na₆[(O₃SS)₂Ag(μ‐SSO₃)₂Ag(SSO₃)]·3H₂O, K₃[Ag(μ‐SSO₃)₂]_(∞|∞)·H₂O; a polymeric copper(I) counterpart of the latter is found in Na₅Cu(NO₃)₂(S₂O₃)₂ ≡ 2NaNO₃·Na₃[Cu(μ‐SSO₃)₂]_(∞|∞). For n = 1, NaAgS₂O₃, the an‐ and mono‐ hydrates, exhibit a two‐dimensional polymeric complex anion in both forms but with different contributing motifs. (NH₄)₁₃Ag₃(S₂O₃)₈·2H₂O takes the form (NH₄)₁₃[{(O₃SS)₃Ag(μ‐SSO₃)}₂Ag], a linearly coordinated central silver atom linking a pair of peripheral [Ag(SSO₃)₄]^7? entities. In Na₆[(O₃SS)Ag(μ‐SSO₃)₂Ag(SSO₃)]·3H₂O, the binuclear anions present as Ag₂S₄ sheets, the associated oxygen atoms being disposed to one side, thus sandwiching layers of sodium ions; the remarkable complex Na₅[Ag₃(S₂O₃)₄]_(∞|∞)·H₂O is a variant, in which one sodium atom is transformed into silver, linking the binuclear species into a one‐dimensional polymer. In (NH₄)₈[Cu₂(S₂O₃)₅]·2H₂O a binuclear anion of the form [(O₃SS)₂Cu(μ‐S.SO₃)Cu(SSO₃)₂]^8? is found; the complex (NH₄)₁₁Cu(S₂O₃)₆ is 2(NH₄)₂(S₂O₃)·(NH₄)₇[Cu(SSO₃)₄]. A novel new hydrate of sodium thiosulfate is described, 4Na₄S₂O₃·5H₂O, largely describable as sheets of the salt, shrouded in water molecules to either side, together with a redetermination of the structure of 3K₂S₂O₃·H₂O.     

Ag4Bi2O5 — ein neues Silberbismutat(III)

Ag₄Bi₂O₅ — A Novel Silverbismuthate(III) Yellow single crystals of Ag₄Bi₂O₅ have been obtained for the first time by solid state reaction of Ag₂O and Bi₂O₃ applying an oxygen pressure of 10 MPa at a temperature of 473 K. According to the results of a single crystal structure determination (Pnna, a = 1428.3(2), b = 569.2(1), c = 877.7(1) pm, Z = 4, 1544 diffractometer data, R₁ = 0.050, wR² = 0.094) the anionic partial structure of Ag₄Bi₂O₅ consists of chains of corner and edge sharing BiO₄-units. The silveratoms form a network of threedimensionally connected trigonal bipyramides with Ag? Ag-contacts between 285 and 323 pm.     

Ag9I3(SeO4)2(IO3)2 – Synthesis,Crystal Structure,and Ionic Conductivity

Ag₉I₃(SeO₄)₂(IO₃)₂ was obtained for the first time by reacting a stoichiometric mixture of Ag₂O, AgI and SeO₂ at elevated oxygen pressure (255 MPa) and at a temperature of 500 °C. Ag₉I₃(SeO₄)₂(IO₃)₂ was characterized by X‐ray powder diffraction, differential scanning calorimetry, impedance spectroscopy and single crystal structure analysis. The crystal structure was solved by direct methods (I23, Z = 8, a = 12.9584(6) Å, V = 2175.9(2) ų and R₁ = 2.70 %). The crystal structure consists of isolated SeO₄ tetrahedra and trigonal IO₃ pyramids separated by Ag⁺ and I^– ions. Each four of the SeO₄^2– and IO₃^– anions aggregate, forming a novel supramolecular building block, showing a hetero‐cubane like structure. According to the results of impedance measurements, Ag₉I₃(SeO₄)₂(IO₃)₂ is a good silver ion conductor. The compound shows an abrupt increase in the ionic conductivity in the temperature range of 115 to 147 °C, and has a silver ion conductivity of 7.1 × 10^–5 Ω^–1 cm^–1 at 25 °C. The activation energy for silver ion conduction is 0.45 eV, in the temperature range from 25 to 115°.     

Synthesis and Crystal Structure of a Two-dimensional Silver（Ⅰ）-Iron（Ⅲ） Heteronuclear Coordination Polymer： {[Ag4Fe2（SCN）12（H2O）2] [（inaH）2（H2O）2]}n

The 2‐D heteronuclear coordination polymer {[Ag₄Fe2(SCN)₁₂(H₂O)₂] (inaH)₂(H₂O)₂}_n (1) (inaH is the abbreviation of protonated isonicotinic acid) with chemical formula C₂₄Ag₄Fe₂N₁₄O₈S₁₂ has been synthesized and characterized by single crystal X‐ray diffraction, elemental analysis and IR spectroscopy. The Ag₂S₂ rings connect two kinds of octahedral geometries of Fe(III) ions, [Fe(NCS)₆]^3– and Fe(H₂O)₂(NCS)₄]^? units with bridging thiocyanate ions leading to 2‐D [Ag₄Fe₂(SCN)₁₂(H₂O)₂^2– anion framework. Four kinds of rings including the unprecedented thirty‐two membered Ag₄Fe₄(SCN)₈ rings share comers or edges in the 2‐D anion layer structure. All thiocyanates coordinate to the metal ions according to the HSAB principle with N atoms binding to the Fe(III) ions and with S atoms binding to Ag(I) ions. Pronoated ina cations stabilize the layer structure as counter ions and hydrogen bonds were formed within the pronoated in a cations dimer and between the dimers and the lattice waters. Crystal data: M_r= 1560.44, triclinic, P1, a=0.76082(1) nm, b=0.9234 nm, c= 1.85611(4) nm, a= 103.0170(10)°, β=93.7780(10)°, y=97.4080(10)°, V= 1.25385(3) nm³, Z=1, μ(Mo Kα)=2.650 mm^?1, D_c,=2.067 g · cm^?3, F(000)=758, R₁=0.0412. wR₂=0.1003.     

Darstellung,Ramanspektren und Kristallstrukturen von V2O3(SO4)2, K[VO(SO4)2] und NH4[VO(SO4)2]

Preparation, Raman Spectra, and Crystal Structures of V₂O₃(SO₄)₂, K[VO(SO₄)₂], and NH₄[VO(SO₄)₂] The oxo-sulfato-vanadates(V) V₂O₃(SO₄)₂, K[VO(SO₄)₂], and NH₄[VO(SO₄)₂] have been prepared as crystals suitable for X-ray structure determination. In all structures sulfate acts as an unidentate ligand only toward a single vanadium atom. The structure of V₂O₃(SO₄)₂ consists of a threedimensional network of pairs of cornershared VO₆ octahedra with one terminal oxygen atom each, and SO₄ tetrahedra. All oxygen atoms of the sulfate ions are coordinated. NH₄[VO(SO₄)₂] and K[VO(SO₄)₂] are isostructural. VO₆ octahedra with one terminal oxygen atom and pairs of sulfate tetrahedra form infinite chains by corner sharing. The chains are weakly interlinked to layers. The sulfate ions are distorted towards planar SO₃ molecules and single oxygen atoms attached to vanadium. This structural detail gives an explanation for the mechanism of the reversible reaction K[VO(SO₄)₂] ? K[VO₂(SO₄)] + SO₃ at 400°C. Raman spectra of the compounds have been recorded and interpreted with respect to their structures. Crystal data: V₂O₃(SO₄)₂, monoclinic, space group P2₁/a, a = 947.2(4), b = 891.3(3), c? 989.1(4) pm, β = 104.56(3)°, Z = 4, 878 unique data, R(R_w) = 0.039(0,033); K[VO(SO₄)₂], orthorhombic, space group P2₁2₁2₁, a = 495.3(2), b = 869.6(9), c = 1 627(1)pm, Z = 4, 642 unique data, R(R_w) = 0,11(0,10); NH₄[VO(SO₄)₂], orthorhombic, space group P2₁2₁2₁, a = 495.3(1), b = 870.0(2), c = 1 676.7(4)pm, Z = 4, 768 unique data, R(R_w) = 0.088(0.083).     

Two silver(I) complexes with bis(benzimidazole)‐2‐oxopropane ligands: Syntheses,crystal structures and DNA binding studies

Two Ag(I) complexes, [Ag₂(bobb)₂]⋅(NO₃)₂ ( 1 ) and [Ag₂(crotonate)₂(aobb)]_n ( 2 ) (bobb =1,3‐bis(1‐benzylbenzimidazol‐2‐yl)‐2‐oxapropane; aobb =1,3‐bis(1‐allylbenzimidazol‐2‐yl)‐2‐oxopropane), have been synthesized and characterized using elemental analysis, electrical conductivities, infrared and UV–visible spectral measurements and single‐crystal X‐ray diffraction. Complex 1 is binuclear and three‐coordinated by two N atoms from two bobb ligands, while complex 2 is a unique metal organic compound with diamond‐like multinuclear Ag centers with each Ag bridged by two aobb ligands and two crotonate ions to form one‐dimensional single polymer chain structures and extended into two‐dimensional frameworks through π–π and intermolecular C─H⋅⋅⋅O hydrogen bonds. The adjacent Ag(I) centers are bridged by allyl from aobb which is not only a σ‐bonding ligand, but also a π‐acid ligand. The DNA binding modes of complexes 1 and 2 were investigated using electronic absorption titration, fluorescence spectra and viscosity measurements. The results suggest that the two complexes bind to DNA via an intercalative mode, and their binding affinity for DNA follows the order 2  >  1 . This is due to the chelating effects which can enhance the planar functionality of the metal complexes.     

Neue Phosphido-verbrückte Mehrkernkomplexe des Ag,Cd und Zn Die Kristallstrukturen von [Ag4(PPh2)4(PMe3)4], [Ag6(PPh2)6(PtBu3)2] und [M4Cl4(PPh2)4(PnPr3)2] (M = Zn,Cd)

New Phosphido-bridged Multinuclear Complexes of Ag, Cd and Zn. The Crystal Structures of [Ag₄(PPh₂)₄(PMe₃)₄], [Ag₆(PPh₂)₆(P^tBu₃)₂] and [M₄Cl₄(PPh₂)₄(PⁿPr₃)₂] (M = Zn, Cd) AgCl reacts with Ph₂PSiMe₃ in the presence of a tertiary Phosphine PMe₃ or P^tBu₃ to form the multinuclear complexes [Ag₄(PPh₂)₄(PMe₃)₄] ( 1 ) and [Ag₆(PPh₂)₆(P^tBu₃)₂] ( 2 ). In analogy to that MCl₂ reacts with Ph₂PSiMe₃ in the presence of PⁿPr₃ to form the two multinuclear complexes [M₄Cl₄(PPh₂)₄(PⁿPr₃)₂] (M = Zn ( 3 ), Cd ( 4 )). The structures were characterized by X-ray single crystal structure analysis ( 1 : space group Pna2₁ (Nr. 33), Z = 4, a = 1 313.8(11) pm, b = 1 511.1(6) pm, c = 4 126.0(18) pm, 2 : space group P–1 (Nr. 2), Z = 2, a = 1 559.0(4) pm, b = 1 885.9(7) pm, c = 2 112.4(8) pm, α = 104.93(3)°, β = 94.48(3)°, γ = 104.41(3)°; 3 : space group C2/c (Nr. 15), Z = 4, a = 2 228.6(6) pm, b = 1 847.6(6) pm, c = 1 827.3(6) pm, β = 110.86(2); 4 : space group C2/c (Nr. 15), Z = 4, a = 1 894.2(9) pm, b = 1 867.9(7) pm, c = 2 264.8(6) pm, β = 111.77(3)°). 3 and 4 may be considered as intermediates on the route towards polymeric [M(PPh₂)₂]_n (M = Zn, Cd).     

Synthesis,Structural Characterization,and Cation Transport of Tripotassium Pentabismuth Arsenate K3Bi5(AsO4)6

During the exploration of the K₂O-Bi₂O ₃ -As₂O₅ system, single crystals of a new arsenate of trivalent bismuth, K₃Bi₅(AsO₄) ₆, were isolated by solid state reaction at 600°C. The title compound crystallizes in the monoclinic system, space group C2/c (N°15) with a = 18.257(2) Å, b = 7.260(1) Å, c = 20.130(4) Å, β = 119.86(1)°, and Z = 4. Its structure consists of a three-dimensional framework made up of AsO₄ tetrahedra and BiO₆ and BiO₇ polyhedra sharing edges and corners, delimiting cavities wherein K⁺ ions reside. This compound exhibits a potassium ion conductivity but with rather low conductivity value.     

K3FeSe3 und K3Fe2Se4, zwei neue Verbindungen im System K/Fe/Se

K₃FeSe₃ and K₃Fe₂Se₄, Two New Compounds in the System K/Fe/Se The two selenides K₃FeSe₃ and K₃Fe₂Se₄ were synthesised by fusion reactions of potassium carbonate with iron and selenium in a stream of hydrogen charged with selenium at 695 °C and 710–730 °C, respectively. The crystal structures were determined by single‐crystal X‐ray diffractometer data. The atomic arrangement of K₃FeSe₃ is characterised by edge sharing [Fe₂Se₆] double tetrahedra separated by potassium ions (space group P2₁/c, Z = 4). The characteristic structural unit of the mixed‐valent compound K₃Fe₂Se₄ is a zig‐zag chain of edge‐sharing, iron‐centred selenium tetrahedra, again separated by potassium ions (space group Pnma, Z = 4).     

The first silver bismuth borate,AgBi2B5O11

The first silver bismuth borate, AgBi₂B₅O₁₁ (silver dibismuth pentaborate), has been prepared via glass crystallization in the Ag₂O–Bi₂O₃–B₂O₃ system and characterized by single‐crystal X‐ray diffraction. Its structure is derived from that of centrosymmetric Bi₃B₅O₁₂ by ordered substitution of one Bi³⁺ ion for Ag⁺, which results in the disappearance of the mirror plane and inversion centre. Second harmonic generation (SHG) measurements confirm the acentric crystal structure. It is formed by [Bi₂B₅O₁₁]_∞ layers stretched along c and comprised of vertex‐sharing B₅O₁₀ and BiO₃ groups which incorporate the Ag⁺ cations. The new compound was characterized by thermal analysis, high‐temperature powder X‐ray diffraction, and vibrational and UV–Vis–NIR (near infrared) spectroscopy. Its thermal expansion is strongly anisotropic due to the presence of rigid B₅O₁₀ groups aligned in a parallel manner. The minimal value is observed along their axis [parallel to c, α_c = 3.1 (1) × 10^?6 K^?1], while maximal values are observed in the ab plane [α_a = 20.4 (2) and α_b = 7.8 (2) × 10^?6 K^?1]. Upon heating, AgBi₂B₅O₁₁ starts to decay above 684 K due to partial reduction of silver; incongruent melting is observed at 861 K. According to density functional theory (DFT) band‐structure calculations, the new compound is a semiconductor with an indirect energy gap of 3.57 eV, which agrees with the experimental data (absorption onset at 380 nm).     

Potassium gallium hydrogenphosphate fluoride,K2Ga[H(HPO4)2]F2

Hydrothermally synthesized dipotassium gallium {hydrogen bis[hydrogenphosphate(V)]} difluoride, K₂Ga[H(HPO₄)₂]F₂, is isotypic with K₂Fe[H(HPO₄)₂]F₂. The main features of the structure are ([Ga{H(HPO₄)₂}F₂]²⁻)_n columns consisting of centrosymmetric Ga(F₂O₄) octahedra [average Ga—O = 1.966 (3) Å and Ga—F = 1.9076 (6) Å] stacked above two HPO₄ tetrahedra [average P—O = 1.54 (2) Å] sharing two O‐atom vertices. The charge‐balancing seven‐coordinate K⁺ cations [average K—O,F = 2.76 (2) Å] lie in the intercolumn space, stabilizing a three‐dimensional structure. Strong [O...O = 2.4184 (11) Å] and medium [O...F = 2.6151 (10) Å] hydrogen bonds further reinforce the connections between adjacent columns.     

Synthesis,Crystal Structure,and Characterization of a New Metal Borophosphate: PbII4{Co2[B(OH)2P2O8](PO4)2}Cl

A new metal borophosphate Pb^II₄{Co₂[B(OH)₂P₂O₈](PO₄)₂}Cl ( 1 ), containing both Pb²⁺ cations and Cl^– anions, was hydrothermally synthesized and characterized by powder X‐ray diffraction, ICP, TG/DTA, and FTIR spectroscopic analyses. The crystal structure determination from single‐crystal X‐ray diffraction reveals that compound 1 crystallizes in the trigonal space group R c (No. 167), a = 9.7513(7) Å, c = 91.060(13) Å, V = 7498.7(13) Å³ and Z = 18. Its structure features a new cobalt borophosphate layer {Co₂[B(OH)₂P₂O₈](PO₄)₂}^7– built up from CoO₅ square pyramids, [B(OH)₂P₂O₈]^5– borophosphate trimers and PO₄ tetrahedra. Extra‐framework Pb²⁺ and Cl^– ions are located at the vacancy of layers to achieve the charge neutrality of the framework. Magnetic measurements indicate that antiferromagnetic interactions exist between Co²⁺ ions with a negative Weiss constant of –20.3 K.