The crystal structure of hexathallium(I) hexatellurodigermanate(III), Tl6[Ge2Te6]

The new compound Tl₆[Ge₂Te₆] was prepared by thermal synthesis from the elements. The material is triclinic, space group $\text{P}\text{1}$, with a = 9.471(2), b = 9.714(2), c = 10.389(2) Å, α = 89.39(1), β = 97.27(1), γ = 100.79(1)°, and Z = 2. The crystal structure was determined from single-crystal intensity data measured by means of an automated four-circle diffractometer and refined to an R value of 0.053 for 1831 observed reflections. Tl₆[Ge₂Te₆] is characterized by Ge₂Te₆ units with GeGe bonds which are linked into a three-dimensional structure by Tl atoms coordinated to essentially six Te atoms. The most important mean distances are $\text{d}\text{GeGe}\text{) = 2.456}$ Å, $\text{d}\text{(}\text{GeTe}\text{) = 2.573}$ Å, and $\text{d}\text{(}\text{TlTe}\text{) = 3.515}$Å. The lone 6s electron pairs of the thallium(I) atoms exhibit significant stereochemical activity. Tl₆[Ge₂Te₆] represents a new structure type.     

Crystal structure of [Cs2Na(H2O)2(C23H16O3)(C23H15O3)3]

The crystal structure of a double salt of sodium and cesium with 2-diphenylacetyl-1,3-indandione of the composition [Cs₂Na(H₂O)₂(C₂₃H₁₆O₃)(C₂₃H₁₅O₃)₃] (I) was studied by X-ray crystallography. The crystals of I are monoclinic, Z = 2, space group P2₁/n, a = 10.212(2) ?, b = 23.479(5) ?, c = 15.638(3) ?, β = 98.30(03)°. The compound contains [Cs₂NaO₁₀] trimers, in which the central Na atom shares two edges with two Cs atoms through deprotonated bridging ligands. The trimers are connected to adjacent trimers by paired C-H...O contacts to form layers. The layers form an infinite open framework via hydrogen bonds between the oxygen atoms of keto groups of noncoordinated indandione moieties and water molecules that enter the cesium coordination sphere in trimers of the adjacent layers.     

New Selenidogermanates with Transition-Metal Complexes as Counterions: Solvothermal Synthesis, Crystal Structures, and Properties of [Mn(en)3]2Ge2Se6 and [Fe(dien)2]2Ge2Se6

Summary. New selenidogermanates [Mn(en)₃]₂Ge₂Se₆ (en = ethylenediamine) and [Fe(dien)₂]₂Ge₂Se₆ (dien= diethylenetriamine) were synthesized by the reaction of germanium dioxide, elemental selenium, and transition metal chlorides in respectively en and dien. Both compounds crystallize in the monoclinic space group P2₁/n with two formula units in the unit cell, and consist of discrete [Ge₂Se₆]⁴⁻ anions with transition metal complex cations as counter ions. The [Ge₂Se₆]⁴⁻ anion is formed by two GeSe₄ tetrahedra sharing a common edge to form a planar Ge₂Se₂ four-membered ring. The [Mn(en)₃]²⁺ and [Ni(dien)₂]²⁺ complex cations are in distorted octahedral geometry. In both selenidogermanates extensive N–H···Se hydrogen bonding contacts lead to 3-dimensional network structures. The band gaps of 2.36 and 2.25 eV were derived from optical absorption spectra. Thermogravimetric analysis shows that the first compound decomposes in two steps under the nitrogen stream, while the second exhibits a one-step decomposition process.     

Synthesis and structure of [Ph3MeP]3[Sb3I12]·Me2C=O, [Ph3MeP]3[Sb2I9], [Ph3MeP]2[SbI5], and [Ph3MeP]3[Sb3I12] antimony complexes

Complexes [Ph₃MeP]₃[Sb₃I₁₂]Me₂C=O (I), [Ph₃MeP]₃[Sb₂I₉] (II), and [Ph₃MeP]₂[SbI₅] (III) were obtained via the reaction of triphenylphosphonium iodide with antimony triiodide in acetone in 1:1, 3:2 and 2:1 molar ratios. Reaction of the complex III with antimony triiodide (1:1) affords [Ph₃MeP]₃[Sb₃I₁₂] (IV). The structure of the obtained complexes was confirmed by X-ray analysis.     

Crystal and molecular structure of (NH4)2[UO2(NO3)4] and [(NH4)(18C6)]2[UO2(NO3)4]

Single crystals of diammonium tetranitratouranylate (NH₄)₂[UO₂(NO₃)₄] (I) and a new diammonium tetranitratouranylate complex with 18-crown-6 [(NH₄)(18C6)]₂[UO₂(NO₃)₄] (II) have been synthesized by the reaction of diaquadinitratouranyl tetrahydrate with ammonium nitrate in a nitric acid solution and the reaction of the same reagents with 18C6 in an ethanol solution, respectively. The X-ray diffraction analysis of compounds I and II has been performed. Crystals of compounds I and II are monoclinic, Z = 2, space group P2₁/n, a = 6.4075(5) ?, b = 7.7851(7) ?, c = 12.4461(12) ?, β = 101.239(1)°, V = 608. 94(9) ?³ for compound I and a = 10.542(9) ?, b = 8.590(8) ?, c = 22.5019(19) ?, β = 101.632(1)°, V = 2058.3(3) ?³ for compound II. The [UO₂(NO₃)₄]²⁻ complex anion in compounds I and II contains two monodentate and two bidentate cyclic nitrato groups, and the coordination number of uranyl is 6. The 18C6 molecule in the structure of compound II has the classic crown conformation and combined with the ammonium ion by three hydrogen bonds. Compounds I and II formed by electrostatic attraction forces between counterions are stabilized by (NH₄⁺)NH...O(NO₃⁻) interionic hydrogen bonds.     

Heterometallic clusters with the {MoNbI8} core: The synthesis and crystal structures of (Ph4P)2[Mo5NbI8Cl6] and (4-MePyH)5[Mo5NbI8Cl6]Cl2

Heterometallic chloride complexes [Mo₅NbI₈Cl₆] ⁿ⁻ (n = 2, 3) are synthesized. The crystal structures of their salts are determined: for (Ph₄P)₂[Mo₅NbI₈Cl₆] (I), triclinic crystal system, spacegroup P [`1]\bar 1, a = 10.9886(6), b = 11.4604(5), c = 13.4343(7) ?, α = 66.124(2), β = 86.892(2), γ = 86.490(2)°, Z = 1, V = 1543.35(13) ?³; and for (4-MePyH)₅[Mo₅NbI₈Cl₆]Cl₂ (II), monoclinic crystal system, space group C2/m, a = 16.4937(4), b = 14.7335(3), c = 11.6534(3) ?, β = 99.8750(10)°, Z = 2, V = 2789.94(11) ? The geometric parameters of compounds I and II and the conditions for the formation of the complexes with the charges −2 and −3 are discussed.     

Structure and properties of double complex salts [Co(NH3)6][Fe(CN)6] and [Co(NH3)6]2[Cu(C2O4)2]3

Double complex salts (DCSs) [Co(NH₃)₆][Fe(CN)₆] (I) and [Co(NH₃)₆]₂[Cu(C₂O₄)₂]₃ (II) and complex [Co(NH₃)₆]₂(C₂O₄)₃·4H₂O (III) are synthesized and investigated by single crystal XRD, crystal optics, and elemental analysis. The crystalline phases of I, II, and III (R-3, P2₁/c, and Pnnm space groups respectively) have the following crystallographic characteristics: a = 10.9804(2) ?, b = 10.9804(2) ?, c = 10.8224(3) ?, V = 1130.03(4) ?³, Z = 3, d _x = 1.65 g/cm³ (I); a = 9.6370(2) ?, b = 10.2452(2) ?, c = 13.2108(3) ?, V = 1932.90(9) ?³, Z = 2, d _x= 1.97 g/cm³ (II), and a = 11.7658(3) ?, b = 11.7254(3) ?, c = 14.1913(4) ?, V = 1304.34(5) ?³, Z = 2, d _x = 1.68 g/cm³ (III). This paper investigates the products of DCS thermolysis in a hydrogen atmosphere: the intermetallic compound CoFe with the bcc parameter a = 2.852 ? for I and a heterogeneous mixture of Co and Cu in the decomposition of II. The coordinated CN⁻ and C₂O₄²⁻ groups then turn into NH₃, hydrocarbons, and CO₂. The dominant hydrocarbon is methane.     

Crystal structure of cadmium iodide complexes with acetamide and propaneamide [Cd(CH3CONH2)6][Cd2I6] and [Cd(C2H5CONH2)6][Cd2I6]

The complexes of CdI₂ with acetamide (AA) and propaneamide (PrA) of the composition [Cd(AA)₆][Cd₂I₆] (I) and [Cd(PrA)₆][Cd₂I₆] (II) were synthesized and studied by X-ray diffraction. Isostructural crystals I and II are triclinic: a = 7.285(3) and 8.066(6), b = 11.266(4) and 11.649(3), c = 11.554(3) and 12.063(2) ?, α = 100.96(2)° and 102.74(2)°, β = 91.59(2)° and 91.73(4)°, γ = 100.76(3)° and 101.05(4)°, V = 912.5 and 1081.9 ?³, respectively; space group , Z = 1. Original Russian Text ? I.A. Zamilatskov, E.V. Savinkina, D.V. Al’bov, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 6, pp. 407–410.     

The Cu(I) thiocyanate complexes with N-allylquinolinium: Synthesis and crystal structures of [C9H7NC3H5]Cu(SCN)2 and [C9H7NC3H5]Cu2(SCN)3

The crystals of [C₉H₇NC₃H₅]Cu(SCN)₂ (I) and [C₉H₇NC₃H₅]Cu₂(SCN)₃ (II) were obtained in the reaction of N-allylquinolinium bromide with CuSCN and NH₄SCN in a methanol solution. The crystals of I are triclinic: space group P , Z = 2, a = 8.619(2), b = 8.755(2), c = 10.463(3) ?, α = 77.18(3), β = 69.95(3), γ = 79.38(3)°, V = 718.1(3) ?³. The crystals of II are opthorhombic: space group P2₁2₁2₁, Z = 4, a = 5.744(2), b = 16.799(4), c = 17.980(5), V = 1735.9(9) ?³. The structure of compound I is built of infinite linear {Cu(SCN)₂⁻}_∞ anions and the N-allylquinolinium cations bonded additionally by relatively weak hydrogen contacts C-H...S. The [C₉H₇NC₃H₅]⁺ cations are located between the corrugated layers of the {Cu₂(SCN)₃⁻}_∞ anions in compound II. As in the case of the previously studied copper(I) halide complexes, the C=C bond of the allyl group in the N-allylquinolinium cation of complexes I, II does not interact with Cu(I). Original Russian Text ? A.V. Pavlyuk, V. Kinzhybalo, T. Lis, M.G. Mys’kiv, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 10, pp. 764–769.     

Syntheses, crystal structures and spectroscopic properties of Ag2Nb[P2S6][S2] and KAg2[PS4]

Ag₂Nb[P₂S₆][S₂] (1) was obtained from the direct solid state reaction of Ag, Nb, P₂S₅ and S at 500 °C. KAg₂[PS₄] (2) was prepared from the reaction of K₂S₃, Ag, Nd, P₂S₅ and extra S powder at 700 °C. Compound 1 crystallizes in the orthorhombic space group Pnma with a=12.2188(11), b=26.3725(16), c=6.7517(4) Å, V=2175.7(3) Å³, Z=8. Compound 2 crystallizes in the non-centrosymmetric tetragonal space group with lattice parameters a=6.6471(7), c=8.1693(11) Å, V=360.95(7) Å³, Z=2. The structure of Ag₂Nb[P₂S₆][S₂] (1) consists of [Nb₂S₁₂], [P₂S₆] and new found puckered [Ag₂S₄] chains which are along [001] direction. The Nb atoms are located at the center of distorted bicapped trigonal prisms. Two prisms share square face of two [S₂²⁻] to form one [Nb₂S₁₂] unit, in which Nb-Nb bond is formed. The [Nb₂S₁₂] units share all S²⁻ corners with ethane-like [P₂S₆] units to form 14-membered rings. The novel puckered [Ag₂S₄] chains are composed of distorted [AgS₄] tetrahedra and [AgS₃] triangles that share corners with each other. These chains are connected with [P₂S₆] units and [Nb₂S₁₂] units to form three-dimensional frame work. The structural skeleton of 2 is built up from [AgS₄] and [PS₄] tetrahedra linked by corner-sharing. The three-dimensional anionic framework contains orthogonal, intersecting tunnels directed along [100] and [010]. This compound possesses a compressed chalcopyrite-like structure. The structure is compressed along [001] and results from eight coordination sphere for K⁺. Both compounds are characterized with UV/vis diffuse reflectance spectroscopy and compound 1 with IR and Raman spectra.     

Syntheses, crystal structures and spectroscopic properties of KEu[AsS4], K3Dy[AsS4]2 and Rb4Nd0.67[AsS4]2

Three rare earth compounds, KEu[AsS₄] (1), K₃Dy[AsS₄]₂ (2), and Rb₄Nd_0.67[AsS₄]₂ (3) have been synthesized employing the molten flux method. The reactions of A₂S₃ (A = K, Rb), Ln (Ln = Eu, Dy, Nd), As₂S₃, S were accomplished at 600 °C for 96 h in evacuated fused silica ampoules. Crystal data for these compounds are: 1, monoclinic, space group P2₁/m (no. 11), a = 6.7276(7) Å, b = 6.7190(5) Å, c = 8.6947(9) Å, β = 107.287(12)°, Z = 2; 2, monoclinic, space group C2/c (no. 15), a = 10.3381(7) Å, b = 18.7439(12) Å, c = 8.8185(6) Å, β = 117.060(7)°, Z = 4; 3, orthorhombic, space group Ibam (no. 72), a = 18.7333(15) Å, b = 9.1461(5) Å, c = 10.2060(6) Å, Z = 4. 1 is a two-dimensional structure with ²_∞[Eu(AsS₄)]⁻ layers separated by potassium cations. Within each layer, distorted bicapped trigonal [EuS₈] prisms are linked through distorted [AsS₄]³⁻ tetrahedra. Each Eu²⁺ cation is coordinated by two [AsS₄]³⁻ units by edge-sharing and bonded to further two [AsS₄]³⁻ units by corner-sharing. Compound 2 contains a one-dimensional structure with ¹_∞[Dy(AsS₄)₂]³⁻ chains separated by potassium cations. Within each chain, distorted bicapped trigonal prisms of [DyS₈] are linked by slightly distorted [AsS₄]³⁻ tetrahedra. Each Dy³⁺ ion is surrounded by four [AsS₄]³⁻ moieties in an edge-sharing fashion. For compound 3 also a one-dimensional structure with ¹_∞[Nd₀.₆₇(AsS₄)₂]⁴⁻ chains is observed. But the Nd position is only partially occupied and overall every third Nd atom is missing along the chain. This cuts the infinite chains into short dimers containing two bridging [As₄]³⁻ units and four terminal [AsS₄]³⁻ groups. 1 is characterized with UV/vis diffuse reflectance spectroscopy, IR, and Raman spectra.     

Hydrothermal synthesis and crystal structure of lithium scandium orthophosphate Li2Sc[H(PO4)2]. The Li2MIII[H(PO4)2] family (MIII = Fe, Sc, In)

Conditions of the hydrothermal synthesis of scandium hydrogen orthophosphate Li₂Sc[H(PO₄)₂] (I) have been studied and the range of its monomineral crystallization have been determined. The existence of bound hydrogen in the structure has been confirmed by IR spectroscopy. The crystals of I are monoclinic: a = 4.857(1) ?, b = 8.198(2) ?, c = 7.664(2) ?, β = 104.097(5)°, space group P2₁/n, Z = 2. The structure was solved by direct methods and refined by full-matrix least-squares calculation in the anisotropic approximation for all non-hydrogen atoms, R _obs = 0.0215, R _wall = 0.0335 (705 reflections with I > 3σ(I)). The basis of the structure is a mixed anionic para-framework {Sc[H(PO₄)₂]}_3∞²⁻, composed of vertex-sharing ScO₆ octahedra and PO₄ tetrahedra. The structural unit of the para-framework is the microblock [ScP₆O₂₄] with symmetry $ \bar 1 $ \bar 1 . The microblocks are condensed in columns running in the [100] direction to form through channels filled with Li⁺ cations (CN = 5). A model with splitting of the hydrogen atom position implying the formation of a strong asymmetric nonlinear H-bond has been suggested and considered. The compound is stable to 400°C. The results of studying compound I are presented together with the data on the Fe- and In-containing Li₂M^III[H(PO₄)₂] analogues.     

Na12Ge17: A Compound with the Zintl Anions [Ge4]4— and [Ge9]4— — Synthesis,Crystal Structure,and Raman Spectrum

Na₁₂Ge₁₇ is prepared from the elements at 1025 K in sealed niobium ampoules. The crystal structure reinvestigation reveals a doubling of the unit cell (space group:P2₁/c; a = 22.117(3)Å, b = 12.803(3)Å, c = 41.557(6)Å, β = 91.31(2)°, Z = 16; Pearson code: mP464), furthermore, weak superstructure reflections indicate an even larger C‐centred monoclinic cell. The characteristic structural units are the isolated cluster anions [Ge₉]^4— and [Ge₄]^4— in ratio 1:2, respectively. The crystal structure represents a hierarchical cluster replacement structure of the hexagonal Laves phase MgZn₂ in which the Mg and Zn atoms are replaced by the Ge₉ and Ge₄ units, respectively. The Raman spectrum of Na₁₂Ge₁₇ exhibits the characteristic breathing modes of the constituent cluster anions at ν = 274 cm^—1 ([Ge₉]^4—) and ν = 222 cm^—1 ([Ge₄]^4—) which may be used for identification of these clusters in solid phases and in solutions. Raman spectra further prove that Na₁₂Ge₁₇ is partial soluble both in ethylenediamine and liquid ammonia. The solution and the solid extract contain solely [Ge₉]^4—. The remaining insoluble residue is Na₄Ge₄. By heating the solvate Na₄Ge₉(NH₃)_n releases NH₃ and decomposes irreversibly at 742 K, yielding Na₁₂Ge₁₇ and Ge.     

Synthesis and X-ray diffraction study of R[UO2(CH3COO)3] (R = H3O+ or NH(C2H5) 3+ )

Single crystals of (H₃O)[UO₂(CH₃COO)₃] (I) and (NH(C₂H₅)₃)[UO₂(CH₃COO)₃] (II) are synthesized, and their structures are studied by X-ray crystallography. Compound I crystallizes in the tetragonal crystal system with the unit cell parameters a = 13.70640(10) ?, c = 27.5258(5) ?, V = 5171.14(11) ?³, space group I4₁/a, Z = 16, R = 0.0238. The crystals of compound II are orthorhombic with the parameters a = 13.3685(3) ?, b = 10.6990(3) ?, c = 12.2616(3) ?, V = 1753.77(8) ?³, space group Pna2₁, Z = 4, R = 0.0228. The uranium-containing structural units of crystals I and II are [UO₂(CH₃COO)₃]⁻ island mononuclear groups belonging to the A B₃⁰¹(A = UO₂²⁺, B⁰¹ = CH₃COO⁻) crystal-chemical group of uranyl complexes. [UO₂(CH₃COO)₃]⁻ complexes are linked into a three-dimensional framework by electrostatic interactions with the outer-sphere cations and by hydrogen bonds involving the hydrogen atoms of hydroxonium (I) or triethylammonium (II) with the oxygen atoms of the acetato groups.     

Hydrothermal synthesis and structural characterization of a new 3D chiral coordination polymer [Cd2(C4H4O6)2]n

A new chiral coordination polymer [Cd₂(C₄H₄O₆)₂] _n (I) has been synthesized and characterized by elemental analysis, IR, and X-ray single-crystal diffraction. The X-ray diffraction analysis reveals that I crystallizes in the orthorhombic system, space group P2₁2₁2₁. The adjacent Cd(1) and Cd(2) centers are linked by one tartrate ligand through tridentate coordination to form a dimer. The dimer is further connected to the other dimer via tartrate ligands to construct an infinite three-dimensional (3D) coordination polymer. The unit cell parameters for I: a = 7.4984(17), b = 7.9106(18), c = 19.560(4) ?, V = 1160.2(5) ?³, Z = 4.     

Synthesis and characterization of the [Cu(Cin2bda)2]ClO4 and [Cu(Ncin2bda)2]ClO4 complexes: Crystal structure of [Cu(Ncin2bda)2]ClO4

Two copper(I) complexes [Cu(Cin₂bda)₂]ClO₄ (I) and [Cu(Ncin₂bda)₂]ClO₄ (II) have been prepared by the reaction of the ligands N²,N²′-bis(3-phenylallylidene)biphenyl-2,2′-diamine (L¹) and N²,N²′-bis[3-(2-nitrophenyl)allylidene]biphenyl-2,2′-diamine (L²) and copper(I) salt. These compounds were characterized by CHN analyses, ¹H NMR, IR, and UV-Vis spectroscopy. The C=N stretching frequency in the copper(I) complexes shows a shift to a lower frequency relative to the free ligand due to the coordination of the nitrogen atoms. The crystal and molecular structure of II was determined by X-ray single-crystal crystallography. The coordination polyhedron about the copper(I) center in the complex is best described as a distorted tetrahedron. A quasireversible redox behavior was observed for complexes I and II. The article is published in the original.     

Diversity of Strontium Nitridogermanates(IV): Novel Sr4[GeN4], Sr8Ge2[GeN4], and Sr17Ge2[GeN3]2[GeN4]2

Single crystals of three new strontium nitridogermanates(IV) were grown in sealed niobium ampules from sodium flux. Dark red Sr₄[GeN₄] crystallizes in space group P2₁/c with a = 9.7923(2) Å, b = 6.3990(1) Å, c = 11.6924(3) Å and β = 115.966(1)°. Black Sr₈Ge₂[GeN₄] contains Ge^4– anions coexisting with [Ge^IVN₄]^8– tetrahedra and adopts space group Cc with a = 10.1117(4) Å, b = 17.1073(7) Å, c = 10.0473(4) Å and β = 115.966(1)°. Black Sr₁₇Ge₆N₁₄ features the same anions alongside trigonal planar [Ge^IVN₃]^5– units. It crystallizes in P1 with a = 7.5392(1) Å, b = 9.7502(2) Å, c = 11.6761(2) Å, α = 103.308(1)°, β = 94.651(1)° and γ = 110.248(1)°.     

Crystal and molecular structure and properties of [Ni(4-NH2Py)2(iso-Bu2PS2)2] and [Co(4-NH2Py)(iso-Bu2PS2)2]

The interaction of the Co(iso-Bu₂PS₂)₂ chelate with 4-NH₂Py afforded a paramagnetic complex [Co(4-NH₂Py)(iso-Bu₂PS₂)₂] (μ_eff = 4.53 BM). Single crystals of [Ni(4-NH₂Py)₂(iso-Bu₂PS₂)₂] (I) and [Co(4-NH₂Py)(iso-Bu₂PS₂)₂] (II) were grown and used for X-ray diffraction investigation (X8 APEX diffractometer, MoK _α radiation). Crystals I are monoclinic with unit cell parameters a = 12.5336(5) Å, b = 9.4356(4) Å, c = 16.4095(6) Å; β = 111.351(1)°; V = 1807.4(1) ų; Z = 2, ρ = 1.223 g/cm³, space group P2₁/n. Crystals II are triclinic with unit cell parameters a = 8.7572(4) Å, b = 9.6934(6) Å, c = 18.665(1) Å; α = 79.374(2)°, β = 87.049(2)°, γ = 75.640(2)°; V = 1508.6(1) ų; Z = 2, ρ = 1.259 g/cm³; space group . The structures of I and II are formed by isolated mononuclear molecules. The coordination unit is NiN₂S₄ (octahedron) in I and CoNS₄ (tetragonal pyramid) in II. The 4-NH₂Py molecule is coordinated through the N atom of the heterocycle. Electronic spectroscopy data for II agree with the symmetry of the NS₄ polyhedron found by X-ray diffraction (XRD) analysis. The noncoordinated amine groups link the complex molecules via N-H...S hydrogen bonds. __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 6, pp.1072–1080, November–December, 2005. Original Russian Text Copyright ? 2005 by T. E. Kokina, L. A. Glinskaya, E. A. Sankova, R. F. Klevtsova, and S. V. Larionov     

Hydrothermal synthesis, crystal structure, and magnetic properties of a novel organo-templated iron(III) borophosphate: (C3H12N2)Fe 6(H2O)4[B4P8O32(OH)8]

The organo-templated iron(III) borophosphate (C₃H₁₂N₂)Fe^III ₆(H₂O)₄[B₄P₈O₃₂(OH)₈] was prepared under mild hydrothermal conditions (at 443 K) and the crystal structure was determined from single crystal X-ray data at 295 K (monoclinic, P2₁/c (No. 14), a=5.014(2) Å, b=9.309(2) Å, c=20.923(7) Å, β=110.29(2)°, V=915.9(5) Å³, Z=2, R1=0.049, wR2=0.107 for all data, 2234 observed reflections with I>2σ(I)). The title compound contains a complex inorganic framework of borophosphate trimers [BP₂O₈(OH)₂]⁵⁻ together with FeO₄(OH)(H₂O)- and FeO₄(OH)₂-octahedra forming channels with ten-membered ring apertures in which the diaminopropane cations are located. The magnetization measurements confirm the Fe(III)-state and show an antiferromagnetic ordering at T_N≈14.0(1) K.     

Enhancing the Variability of [Ge9] Cluster Chemistry through Phosphine Functionalization

The synthetic approach towards molecules that contain Ge atoms with oxidation state 0, and which are exclusively connected to other Ge atoms, is explored by using anionic clusters extracted from binary solids. Besides providing a novel variable method for the introduction of alkenyl moieties to [Ge₉] cluster compounds, this work expands the spectrum of mixed-functionalized [Ge₉] cluster anions, which are suitable for the straightforward synthesis of zwitterionic compounds upon coordination to metal cations. In detail, the synthesis of a series of mixed-functionalized [Ge₉] clusters is reported, including [Ge₉{Si(TMS)₃}₃PRR^I] (R=tBu, R^I=(CH₂)₃CH=CH₂; 2 ) and [Ge₉{Si(TMS)₃}₂PRR^I]⁻ (R and R^I: alkyl, alkenyl, aryl, aminoalkyl; 3 a to 11 a , TMS: (trimethyl)silyl). In 2 and 3 a , pentenyl functionalization of the [Ge₉] clusters was achieved by reaction of the novel chlorophosphine tBu{(CH₂)₃CH=CH₂}PCl ( 1 ) with silylated [Ge₉] clusters. Furthermore, the reactivity of the cluster anions 3 a to 11 a towards NHC^DippMCl (NHC^Dipp=1,3-di(2,6-diisopropylphenyl)imidazolylidine; M=Cu, Ag) showed a dependency on the steric demand of the phosphine either zwitterions ( 3 -MNHC^Dipp to 7 -MNHC^Dipp) featuring P–M interactions are formed, or Ge–M coordination ( 8 -MNHC^Dipp to 11 -MNHC^Dipp) occurs. For M=Ag, the formation of zwitterionic complexes was unequivocally proven by NMR investigations showing ¹J(³¹P-¹⁰⁷Ag/¹⁰⁹Ag) spin-spin coupling.