Two new borates containing the first examples of large isolated polyborate anions: chain [B7O9(OH)5]2- and ring [B14O20(OH)6]4-

Two novel hydrated borates were synthesized under mild solvothermal conditions. One is hydrated rubidium borate, Rb2B7O9(OH)5, which contains the first example of the isolated chain heptaborate anion, [B7O9(OH)5]2-. The other is hydrated diethylenetriamine borate, [(C4H15N3)]2[B14O20(OH)6], which contains the first example of the largest isolated ring tetradecaborate anion, [B14O20(OH)6]4-.     

Effects of water uptake on the inherently oxygen-deficient compounds Ln26O27 square(BO3)8 (Ln=La, Nd)

The inherently oxygen-deficient compounds Ln26O27 square(BO3)8 (Ln=La, Nd) react with water vapor leading to Ln26O26(OH)2(BO3)8 phases, and this reaction is reversible. The crystal structure of Nd26O27 square(BO3)8 has been determined from single-crystal data (space group P with a=6.7643(10) A, b=12.663(2) A, c=14.271(2) A, alpha=90.553(8) degrees, beta=99.778(10) degrees, and gamma=90.511(9) degrees). It is a triclinic distorted version of the monoclinic structure of La26O27 square(BO3)8. The Ln26O26(OH)2(BO3)8 phases both crystallize in the monoclinic system (space group P21/c with a=6.7445(4) A, b=12.6177(9) A, c=14.4947(10) A, and beta=100.168(7) degrees for Nd26O26(OH)2(BO3)8 and a=6.9130(15) A, b=12.896(3) A, c=14.792(4) A, beta=99.698(16) degrees for La26O26(OH)2(BO3)8), and their crystal structure has been determined from single-crystal data, showing that the hydroxyl groups are localized mainly on one of the oxygen sites at room temperature (RT). For the Nd phases, the change in crystal system can result from two different phenomena depending on the atmosphere, either a phase transformation corresponding to a water uptake under wet conditions (triclinic Nd26O27 square(BO3)8 at RT-->monoclinic Nd26O26(OH)2(BO3)8) or a phase transition at approximately 300 degrees C for the anhydrous phase under dry conditions (triclinic Nd26O27 square(BO3)8 at RT-->monoclinic Nd26O27 square(BO3)8 at T>300 degrees C). For Nd26O26(OH)2(BO3)8, the conductivity measured under wet conditions at 300 degrees C is sigma300 degrees C approximately 0.5x10(-5) S cm(-1). Due to the dehydration process, the proton contribution to the total conductivity of the Nd phase is no longer observed above 500 degrees C whereas it was still clearly visible at 600 degrees C for the La phase.     

Influence of hydrogen bonding on the assembly of six-membered vanadium borophosphate cluster anions: synthesis and structures of (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12](6)10H2O, (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12](6)17H2O, and (NH4)3(C4H14N2)4 5[Sr(H2O)5]2[Sr(H2O)4][V2P2BO12]6 10H2O

Three new strontium vanadium borophosphate compounds, (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12]6 10H2O (Sr-VBPO1) (1), (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12]6 17H2O (Sr-VBPO2) (2), and (NH4)3(C4H14N2)4.5[Sr(H2O)5]2[Sr(H2O)4][V2P2BO12]6 10H2O (Sr-VBPO3) (3) have been synthesized by interdiffusion methods in the presence of diprotonated ethylenediamine, 1,3-diaminopropane, and 1,4-diaminobutane. Compound 1 has a chain structure, whereas 2 and 3 have layered structures with different arrangements of [(NH4) [symbol: see text] [V2P2BO12]6] cluster anions within the layers. Crystal data: (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12]6 10H2O, monoclinic, space group C2/c (no. 15), a = 21.552(1) A, b = 27.694(2) A, c = 20.552(1) A, beta = 113.650(1) degrees, Z = 4; (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12]6 17H2O, monoclinic, space group I2/m (no. 12), a = 15.7618(9) A, b = 16.4821(9) A, c = 21.112(1) A, beta = 107.473(1) degrees, Z = 2; (NH4)3(C4H14N2)4.5[Sr(H2O)5]2[Sr(H2O)4] [V2P2BO12]6 10H2O, monoclinic, space group C2/c (no. 15), a = 39.364(2) A, b = 14.0924(7) A, c = 25.342(1) A, beta = 121.259(1) degrees, Z = 4. The differences in the three structures arise from the different steric requirements of the amines that lead to different amine-cluster hydrogen bonds.     

Polyoxometalate Derivatives with Multiple Organic Groups. 2. Synthesis and Structures of Tris(organotin) alpha, beta-Keggin Tungstosilicates

Eight tris(organotin)-substituted Keggin tungstosilicate heteropolyanions have been synthesized and characterized by elemental analysis, infrared and M?ssbauer spectroscopy, multinuclear NMR, and X-ray crystallography. The new anions contain alpha- or beta-SiW(9)O(34)(10)(-) moieties and are of two structural types, [(RSn)(3)(SiW(9)O(37))](7)(-) (R, isomer: Ph, alpha-, 1; n-Bu, alpha-, 2; Ph, beta-, 3; n-Bu, beta-, 4) and [(RSnOH)(3)(SiW(9)O(34))(2)](14)(-) (Ph, alpha-, 5; n-Bu, alpha-, 6; Ph, beta-, 7; n-Bu, beta-, 8). Crystals of Cs(4)H(3)[(PhSn)(3)(SiW(9)O(37))].8H(2)O (anion 3) are monoclinic, space group C2/c, with lattice constants a = 48.91(2) ?, b = 12.111(3) ?, c = 20.334(9) ?, beta = 102.30 degrees, and Z = 8. The anion has nominal C(3)(v)() symmetry and has a structure with three corner-shared WO(6) octahedra of the beta-Keggin anion replaced by three PhSnO(5) groups. Crystals of Cs(9)H(5)[(BuSnOH)(3)(SiW(9)O(34))(2)].36H(2)O (anion 6) are tetragonal, space group P&fourmacr;2(1)m, with lattice constants a = b = 29.005(4) ?, c = 13.412(4) ?, and Z = 4. The anion has the anticipated D(3)(h)() symmetry and contains three BuSnOH groups sandwiched between A,alpha-SiW(9)O(34)(10)(-) anions.     

Templated heptaborate and pentaborate salts of cyclo-alkylammonium cations: structural and thermal properties

The synthesis and characterization of a series of cyclo-alkylammonium pentaborate salts {[cyclo-C(n)H(2n-1)NR(3)][B(5)O(6)(OH)(4)] (R = H, n = 3, 5-7 (1-4); R = Me, n = 6 (5))} are reported. Compounds 1, 2 and 5 have been further characterized by single-crystal XRD studies. Attempted recrystallization of 3 and 4 yielded small crops of the unexpected heptaborate salts, [cyclo-C(6)H(11)NH(3)](2)[B(7)O(9)(OH)(5)]·3H(2)O·B(OH)(3) (6) and [cyclo-C(7)H(13)NH(3)](2)[B(7)O(9)(OH)(5)]·2H(2)O·2B(OH)(3) (7) which were also characterized crystallographically. All compounds show extensive supramolecular H-bonded anionic lattices templated by the cations. H-bond interactions are described in detail. TGA-DSC analysis of the pentaborates 1-5 showed that they thermally decomposed in air at 800 °C to 2.5B(2)O(3), in a 2 step process involving dehydration (<250 °C) and oxidative decomposition (250-600 °C). BET analysis of materials derived from the pentaborates had internal porosities of <1 m(2) g(-1).     

Novel mixed-valence heteropolyoxometalates: a molybdenum diphosphonate anion [MoV7MoVIO16(O3PPhPO3H)4]3- and its one- and two-dimensional assemblies

A novel mixed-valence polyoxomolybdenum anion, [Mo(V)(7)Mo(VI)O(16)(O(3)PPhPO(3)H)(4)](3)(-), was synthesized hydrothermally from molybdenum oxide, molybdenum metal, boric and phosphoric acids, 1,2-phenyldiphosphonic acid, and imidazole (ImH) and was structurally characterized as an imidazolium salt (orthorhombic, Aba2; a = 16.674(4), b = 17.238(1), and c = 24.81(2) A). One- and two-dimensional structures of this anion and additional molybdenum diphosphonate linkers were assembled as well. They were structurally characterized as their pyridinium (pyH) salts (pyH)(4)[[Mo(V)(7)Mo(VI)O(16)(O(3)PPhPO(3))(2)(O(3)PPhPO(3)H)(2)][Mo(2)O(4)(OH)(HO(3)PPhPO(3)H)]].5H(2)O (monoclinic, P2(1)/c; a = 20.8506(9), b = 22.866(1), and c = 21.1403(9) A; beta = 118.7087(8) degrees ) and (pyH)(3)[[Mo(V)(7)Mo(VI)O(16)(O(3)PPhPO(3))(4)][Mo(2)O(2)(OH)(2)(HO(3)PPhPO(3)H)]].3H(2)O (orthorhombic, Pca2(1); a = 19.057(1), b = 20.402(2), and c = 20.660(2) A). The compounds were also characterized by IR spectroscopy and magnetic measurements.     

Synthesis and structural characterization of 0D vanadium borophosphate [Co(en)(3)](2)[V(3)P(3)BO(19)][H(2)PO(4)].4H(2)O and 1D vanadium oxides [Co(en)(3)][V(3)O(9)].H(2)O and [Co(dien)(2)][V(3)O(9)].H(2)O templated by cobalt complexes: cooperative organization of the complexes and the inorganic networks

A 0D vanadium borophosphate [Co(en)(3)](2)[V(3)P(3)BO(19)][H(2)PO(4)].4H(2)O (1) and two 1D vanadium oxides [Co(en)(3)][V(3)O(9)].H(2)O (2) and [Co(dien)(2)][V(3)O(9)].H(2)O (3) have been synthesized hydrothermally from the reaction mixture of V(2)O(5)-H(3)PO(4)-H(3)BO(3)-CoCl(2)-R-H(2)O at 110 degrees C (R: en or dien). The complex cations Co(en)(3)(3+) and Co(dien)(2)(3+) are cooperatively organized in the reaction medium to play a structure-directing role in the formation of the inorganic clusters and chains. The structures are determined by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, ICP, and TG analyses. The structure of 1 contains isolated [V(3)P(3)BO(19)](5)(-) cluster anions, H(2)PO(4)(-) anions, racemic Co(en)(3)(3+) cations, and H(2)O molecules, which form a complex H-bond network. 2 and 3 both contain chains of corner-sharing VO(4) tetrahedra running along the 2(1) screw axis. The complex cations located in the interchain region interact with the chains through H-bonds. 2 is crystallized in an enantiomorphic space group and only one enantiomer of Co(en)(3)(3+) is involved in the structure. Crystal data: 1, monoclinic, C2/c, a = 32.8492(14) A, b = 11.9601(3) A, c = 22.6001(7) A, beta = 108.9630(8) degrees, Z = 8; 2, orthorhombic, P2(1)2(1)2(1), a = 8.1587(16) A, b = 12.675(3) A, c = 18.046(4) A, Z = 4; 3, monoclinic, P2(1)/c, a = 16.1663(10) A, b = 8.7028(3) A, c = 13.9773(5) A, beta = 103.1340(18) degrees, Z = 4.     

2-（1,3-Diphenylpropen-1,3-diolato）-1,3,2-（5-formylbenzo）dioxaborol： A ＇Whole-molecule Disorder＇ Crystal Structure

The boron atom in C22H15BO5 is O,O’-chelated by the anions in a tetrahedral geometry, with the planar five-and six-membered chelate rings being orthogonal to each other. The molecule lies on a two-fold rotation axis. The molecule is disordered with respect to another molecule in a 93:7 ratio; the treatment of the ‘whole-molecule disorder’ by employing a large number of restraints is described. Crystal data: C22H15BO5, monoclinic C2/c, a = 17.1804(5), b = 12.9409(4), c = 9.8842(3) , β = 124.832(2)o, V = 1803.82(9) 3 at –173 K.     

A study of the sequential acid-catalyzed hydroxylation of dodecahydro-closo-dodecaborate(2-)

The closo-[B12H12-n(OH)n]2- (n = 1-4) ions have been synthesized by the reaction of cesium dodecahydro-closo-dodecaborate(2-), Cs21, with aqueous sulfuric acid. Variation of the reaction temperature, time, and acid concentration results in the stepwise introduction of from one to four hydroxyl groups. Each individual hydroxylation step proceeds regioselectively, affording only one isomer per step. Further substitution of the hydroxylated cluster preferentially takes place at a B-H vertex meta to a B-OH vertex. The closo-[B12H12-n(OH)n]2- (n = 1-4) species, designated 2-5, respectively, are characterized by one- and two-dimensional 11B NMR spectroscopy, IR spectroscopy, and high-resolution fast atom bombardment (FAB) mass spectrometry. A rationale that qualitatively explains the influence of the hydroxyl group on the chemical shifts of the individual boron vertices is developed. Furthermore, the solid state structures of closo-[B12H11(OH)]2-, 2, and closo-1,7-[B12H10(OH)2]2-,3, are determined by X-ray diffraction. Crystallographic data are as follows: For [MePPh3](2)2, monoclinic, space group P2(1)/n, a = 890.1(5) pm, b = 1814(1) pm, c = 1270.5(7) pm, beta = 101.66(2) degrees, Z = 2, R = 0.055; for [MePPh3](2)3, monoclinic, space group P2(1)/n, a = 887.6(4) pm, b = 1847.2(8) pm, c = 1271.1(5) pm, beta = 101.17(1) degrees, Z = 2, R = 0.065. In addition, synthetic routes to O-derivatized species of the anions 2-5 such as closo-[B12H11(OTiCpCl2)]2-, 7, closo-1,7-[B12H10(OTiCpCl2)2]2-, 8, closo-1,7,9-[B12H9(OTiCpCl2)3]2-, 9, closo-[B12H11(OCONHPh)]2-, 10, and closo-1,7-[B12H10(OSO2Me)2]2-, 11, are described. The crystal structures of 7 and 11 are determined by single-crystal X-ray diffraction. Crystallographic data are as follows: For [MePPh3](2)7, monoclinic, space group Cc, a = 2530.5(2) pm, b = 1653.3(1) pm, c = 1281.3(1) pm, beta = 118.79(2) degrees, Z = 4, R = 0.085; for [HPy](2)11, monoclinic, space group P2(1)/n, a = 1550.9(8) pm, b = 993.1(5) pm, c = 1726.5(9) pm, beta = 112.36(2) degrees, Z = 4, R = 0.061.     

含水杨醛缩对硝基苯甲酰腙的钒酰配合物和钴配合物的合成和晶体结构

本文合成了含水杨醛缩对硝基苯甲酰腙(简写为H2L)的钒酰配合物VOL(CH3OH)(CH3O)(1,C16H16N3O7V,Mr=413.26)和钴配合物[CoL(C5H5N)3]NO3C5H5N(2,C34H29N8O7Co,Mr=720.58)。配合物1属单斜晶系,空间群为P21/c,a=7.3253(3),b=18.8237(9),c=12.9014(5)?b=91.672(1),V=1778.2(1)3,Z=4,F(000)=848,m(MoKa)=0.603mm1,R=0.0470,wR=0.1312。配合物2属单斜晶系,空间群为P21/c,a=11.4196(8),b=17.157(1),c=17.081(1)?b=96.8233(9),V=3323.0(4)3,Z=4,F(000)=1488,m(MoKa)=0.578mm1,R=0.0455,wR=0.1311。在配合物1中,钒(V)原子由周围的酰氧基原子、配体L2的3个配位原子,去质子化甲醇的甲氧基原子和配位甲醇的氧原子配位,形成畸变的VO(ONO)(O)(O)八面体配位构型。晶体内每2个分子间通过氢键作用缔合成中心对称的分子对,OH…N氢键键长为2.861(4)?键角163.20。晶体中存在着弱p-p共轭作用。在配合物2中,钴(Ⅲ)原子由1个L2的3个配位原子和3个配位吡啶分子的3个氮原子配位,呈N4O2八面体配位构型。     

New framework connectivity patterns in templated networks: the creatinine zinc phosphites C4N3OH7.ZnHPO3, C4N3OH7.Zn(H2O)HPO3, and (C4N3OH7)2.ZnHPO3.H2O

The syntheses, crystal structures, and properties of C(4)N(3)OH(7).ZnHPO(3), C(4)N(3)OH(7).Zn(H(2)O)HPO(3), and (C(4)N(3)OH(7))(2).ZnHPO(3).H(2)O are reported. These new creatinine zinc phosphites are built up from networks of vertex-sharing HPO(3) pseudopyramids and various types of ZnO(2)N(2), ZnO(3)N, and ZnO(2)N(H(2)O) tetrahedra, resulting in extended structures of different dimensionalities (as sheets, clusters, and chains, respectively). They demonstrate the structural effect of incorporating "terminal" (nonnetworking) Zn-N and Zn-OH(2) moieties into zinc centers. Crystal data: C(4)N(3)OH(7).ZnHPO(3), triclinic, P1 (No. 2), a = 8.9351(4) A, b = 9.5011(4) A, c = 9.9806(4) A, alpha = 87.451(1) degrees, beta = 85.686(1) degrees, gamma = 89.551(1) degrees, Z = 4; C(4)N(3)OH(7).Zn(H(2)O)HPO(3), monoclinic, P2(1)/c (No. 14), a = 10.1198(7) A, b = 7.2996(5) A, c = 13.7421(9) A, beta = 107.522(1) degrees, Z = 4; (C(4)N(3)OH(7))(2).ZnHPO(3).H(2)O, triclinic, P1 (No. 2), a = 10.7289(6) A, b = 10.9051(6)A, c = 13.9881(8) A, alpha = 89.508(1) degrees, beta = 74.995(1) degrees, gamma = 74.932(1) degrees, Z = 4.     

Effects of large halides on the structures of lanthanide(III) and plutonium(III) borates

Reactions of LnBr(3) or LnOI with molten boric acid result in formation of Ln[B(5)O(8)(OH)(H(2)O)(2)Br] (Ln = La-Pr), Nd(4)[B(18)O(25)(OH)(13)Br(3)], or Ln[B(5)O(8)(OH)(H(2)O)(2)I] (Ln = La-Nd). Reaction of PuOI with molten boric acid yields Pu[B(7)O(11)(OH)(H(2)O)(2)I]. The Ln(III) and Pu(III) centers in these compounds are found as nine-coordinate hula-hoop or 10-coordinate capped triangular cupola geometries where there are six approximately coplanar oxygen donors provided by triangular holes in the polyborate sheets. The borate sheets are connected into three-dimensional networks by additional BO(3) triangles and/or BO(4) tetrahedra that are roughly perpendicular to the layers. The room-temperature absorption spectrum of single crystals of Pu[B(7)O(11)(OH)(H(2)O)(2)I] shows characteristic f-f transitions for Pu(III) that are essentially indistinguishable from Pu(III) in other compounds with alternative ligands and different coordination environments.     

Protonation and methylation of an Anderson-type polyoxoanion [IMo6O24]5-

A series of protonated and methylated Anderson-type molybdoperiodates as well as the unprotonated [IMo6O24]5- have been synthesized and structurally characterized as tetra-n-butylammonium salts: [(n-C4H9)4N]5[IMo6O24] [monoclinic, space group C2/c, a = 33.6101(3) A, b = 15.2575(1) A, c = 24.0294(2) A, beta = 126.9569(3) degrees , Z = 4], [(n-C4H9)4N]4[IMo6O23(OH)] [monoclinic, space group P21/c, a = 9.5587(1) A, b = 24.1364(2) A, c = 18.2788(2) A, beta = 90.1562(5) degrees , Z = 2], [(n-C4H9)4N]3[IMo6O22(OH)2].2DMF [monoclinic, space group P21/a, a = 17.6105(4) A, b = 15.5432(5) A, c = 29.3316(9) A, beta = 91.475(3) degrees , Z = 4], [(n-C4H9)4N]4[IMo6O23(OMe)].3H2O [orthorhombic, space group Pbca, a = 17.0679(4) A, b = 25.6998(6) A, c = 20.7428(4) A, Z = 4], [(n-C4H9)4N]3[IMo6O22(OMe)2] [monoclinic, space group P21/n, a = 10.4009(1) A, b = 14.6658(3) A, c = 23.5395(4) A, beta = 100.324(1) degrees , Z = 2]. In all of these compounds, the [IMo6O24]5- anion is protonated or methylated selectively at O atoms shared by two Mo atoms. The results have also revealed that the protonated Anderson-type molybdoperiodates readily react with methanol in a very selective manner, while the unprotonated [IMo6O24]5- anion does not react with methanol under similar conditions.     

Exploratory Investigation of New SHG Materials Based on Galloborates

Three new galloborates, namely, GaB(5)O(8)(OH)(2)(en)(2)·H(2)O (1), LiGa(OH)(BO(3))(H(2)O) (2), and Rb(2)Ga(B(5)O(10))(H(2)O)(4) (3), have been synthesized by hydrothermal reactions. Compound 1 is the first example of a galloborate that contains an organic component. It crystallizes in space group P2(1)/c, and its crystal structure exhibits an infinite zigzag chain consisting of [B(5)O(8)(OH)(2)](3-) anions and GaO(2)N(4) octahedra interconnected via corner sharing. Compound 2 crystallizes in space group P31c with a layered structure composed of GaO(4), LiO(4), and BO(3) building units. Compound 3 belongs to chiral space group C222(1); the basic building blocks of the structure are the [B(5)O(10)](5-) cluster anion and GaO(4) tetrahedron, which are interconnected to form a three-dimensional network with tunnels of Ga2B6 eight-membered rings (8-MRs) which are filled by Rb(+) cations and lattice water molecules. Interestingly, Rb(2)Ga(B(5)O(10))(H(2)O)(4) displays a moderate second-harmonic generation (SHG) response comparable to that of KH(2)PO(4) (KDP), and it is phase matchable. Band structure and optical property calculations for Rb(2)Ga(B(5)O(10))(H(2)O)(4) based on DFT methods were also performed.     

Pentanuclear homoleptic M(5)L(6) (M = Mn(II), Co(II), Zn(II)) complexes formed by strict self-assembly

A series of trigonal bipyramidal pentanuclear complexes involving the alkoxo-diazine ligands poap and p3oap, containing the M(5)[mu-O](6) core is described, which form by a strict self-assembly process. [Co(5)(poap-H)(6)](ClO(4))(4).3H(2)O (1), [Mn(5)(poap-H)(6)](ClO(4))(4).3.5CH(3)OH.H(2)O (2), [Mn(5)(p3oap-H)(6)](ClO(4))(4).CH(3)CH(2)OH.3H(2)O (3), and [Zn(5)(poap-H)(6)](ClO(4))(4).2.5H(2)O (4) are homoleptic pentanuclear complexes, where there is an exact match between the coordination requirements of the five metal ions in the cluster, and the available coordination pockets in the polytopic ligand. [Zn(4)(poap)(poap-H)(3)(H(2)O)(4)] (NO(3))(5).1.5H(2)O (5) is a square [2 x 2] grid with a Zn(4)[mu-O](4) core, and appears to result from the presence of NO(3), which is thought to be a competing ligand in the self-assembly. X-ray structures are reported for 1, 4, and 5. 1 crystallized in the monoclinic system, space group P2(1)/n with a = 13.385(1) A, b = 25.797(2) A, c = 28.513(3) A, beta = 98.704(2) degrees, and Z = 4. 4 crystallized in the triclinic system, space group P1 with a = 13.0897(9) A, b = 18.889(1) A, c = 20.506(2) A, alpha = 87.116(1) degrees, beta = 74.280(2) degrees, gamma = 75.809(2) degrees, and Z = 2. 5 crystallized in the monoclinic system, space group P2(1)/n with a = 14.8222(7) A, b = 21.408(1) A, c = 21.6197(9) A, beta = 90.698(1) degrees, and Z = 4. Compounds 1-3 exhibit intramolecular antiferromagnetic coupling.     

(C4N3H15)[(BO2)2(GeO2)4]: the first organically templated 3D borogermanate showing 1D 12-rings, large channels, and a novel zeolite-type framework topology constructed from Ge8O24 and B2O7 cluster units

The first organically templated 3D borogermanate with a novel zeolite-type topology, (C4N3H15)[(BO2)2(GeO2)4] FJ-17, has been solvothermally synthesized and characterized by IR spectroscopy, powder X-ray diffraction (PXRD), TGA, and single-crystal X-ray diffraction. The compound crystallized in the monoclinic space group P2(1)/c with a = 6.967(1) A, b = 10.500(1) A, c = 20.501(1) A, beta = 90.500(3) degrees , V = 1499.68(8) A3, and Z = 4. The framework topology of this compound is the previously unknown topology with the vertex symbols 3.4.3.9.3.8(2) (vertex 1), 3.8.3.4.6(2).9(2) (vertex 2), 3.8(2).4.6(2).6(2).8 (vertex 3), 4.8.4.8.8(3).12 (vertex 4), 4.8.4.8.8(2).12 (vertex 5), and 3.8.4.6(2).6.8(2) (vertex 6). The structure is constructed from Ge8O24 and B2O7 clusters. The Ge8O24 cluster contains eight GeO4 tetrahedra that share vertices; the B2O7 unit is composed of two BO4 tetrahedra sharing a vertex. The cyclic Ge8O24 clusters connect to each other through vertices to form a 2D layer with 8,12-nets. The adjacent layers are further linked by the dimeric B2O7 cluster units, resulting in a 3D framework with 12- and 8-ring channels along the a and b axes, respectively. In addition, there is a unique B2GeO9 3-ring in the structure.     

Synthesis of ortho- and meta-Re(I)-metallocarboranes in water

A series of metallocarboranes of the types rac-[M(CO)3(eta(5)-7-R-7,8-C2B9H11)]-, rac-[M(CO)3(eta(5)-7-R-8-R'-7,8-C2B9H11)]-, and rac-[M(CO)3(eta(5)-7-R-7,9-C2B9H11)]- (M=Re) were prepared by reacting [NEt4]2[Re(CO)3Br3] or [Re(CO)3(OH2)3]Br with the corresponding carboranes in the presence of aqueous solutions of either alkali metal or tetraalkylammonium fluoride salts. Carborane derivatives that were investigated included those containing pyridine, amino, carboxylic acid, carbohydrate, and aryl substituents. During the course of the research, it was discovered that Re metallocarboranes can be prepared directly from the respective closo-clusters under similar reaction conditions used with nido-carboranes. Reaction yields ranged from modest to excellent depending on the carborane isomer and the nature of the cage substituent(s). A crystal structure of an amine-substituted Re metallocarborane was obtained where the complex crystallized in the orthorhombic space group P2(1)2(1)2(1) with a=8.982(2) A, b=11.563(3) A, c=16.811(4) A, alpha=beta=gamma=90 degrees, V=1746.1(7) A3, Z=4, and R1=0.0684.     

Synthesis and characterization of [Mo(7)O(16)(O(3)PCH(2)PO(3))(3)]:(8-) a mixed-valent polyoxomolybdenum diphosphonate anion with octahedrally and tetrahedrally coordinated molybdenum

Two new compounds containing the title diphosphono-polyoxometalate anion and diprotonated ethylenediamine (enH(2)) or piperazine (ppzH(2)) countercations have been hydrothermally synthesized and structurally characterized ((enH(2))(4)[Mo(7)O(16)(O(3)PCH(2)PO(3))(3)].7H(2)O, triclinic, P(-)1, Z = 2, a = 10.3455(7) A, b = 13.136(1) A, and c = 20.216(3) A, alpha = 93.247(6) degrees, beta = 96.434(6) degrees, and gamma = 111.900(6) degrees; (ppzH(2))(4)[Mo(7)O(16)(O(3)PCH(2)PO(3))(3)].8H(2)O, triclinic, P(-)1, Z = 2, a = 13.255(2) A, b = 13.638(2) A, and c = 16.874(4) A, alpha = 93.20(2) degrees, beta = 101.27(2) degrees, and gamma = 105.87(1) degrees). The anion is a ring of three pairs of edge-sharing octahedra of Mo(V)O(6) (with Mo(V)-Mo(V) bonds) that share corners with each other. The diphosphonate groups connect the pairs at the periphery. The ring is "capped" by a tetrahedron of Mo(VI)O(4). According to magnetic measurements, the compounds are diamagnetic.     

C(4)N(3)OH(7).Zn(H2O)HPO4, a neutral zincophosphate cluster

C(4)N(3)OH(7).Zn(H(2)O)HPO(4), built up from 4-rings of ZnO(2)(H(2)O)N and HPO(4) tetrahedra, is the first neutral, molecular, zincophosphate cluster. The unit-cell packing involves numerous O-H...O and N-H...O hydrogen bonds and pi...pi stacking interactions. Crystal data: C(4)N(3)OH(7).Zn(H(2)O)HPO(4), M(r) = 292.49, triclinic, P1 (No. 2), a = 9.2956(5) A, b = 11.2077(6) A, c = 19.8319(12) A, alpha = 80.314(1) degrees, beta = 78.829(1) degrees, gamma = 89.241(1) degrees, V = 1997.7(2) A(3), Z = 4.     

Coordination chemistry of a novel tetramacrocyclic ligand derived from 1,4,7-triazacyclononane: synthesis,structure, and properties of nickel(II) and copper(II) complexes

A new polynucleating ligand, 1,2,4,5-tetrakis(1,4,7-triazacyclonon-1-ylmethyl)benzene (Ldur), has been prepared and characterized as its dodecahydrobromide salt. Addition of base to an aqueous solution of this salt and 4 molar equivalents (m.e.) of a Ni(II) salt produces a mixture of bi- and trinuclear complexes, which can be separated by cation-exchange chromatography (CEC) and crystallized as [Ni2Ldur](ClO4)(4).2H2O (1) and [Ni3Ldur(H2O)6](ClO4)(6).9H2O (2). The "full capacity" tetranuclear complex, [Ni4Ldur(H2O)12](ClO4)(8).8H2O (3), is obtained by slow addition of Ldur to a refluxing aqueous solution of excess Ni2+ ions, followed by CEC purification. Treatment of Ldur with 4 m.e. of a copper(II) salt produces exclusively the tetranuclear complex, [Cu4Ldur(H2O)8](ClO4)(8).9H2O (4), while reaction with only 2 m.e. of Cu2+ ions yields the binuclear complex, [Cu2Ldur](ClO4)(4).4H2O (5). The X-ray structures of complexes 1,2,4, and [Cu2Ldur](ClO4)(4).3H2O (5') have been determined; all are monoclinic, P2(1)/c: for 1, a = 9.497(3) A, b = 13.665(5) A, c = 19.355(6) A, beta = 100.57(2) degrees, V = 2469(1) A3, and Z = 2; for 2, a = 22.883(7) A, b = 15.131(6) A, c = 20.298(8) A, beta = 97.20(3) degrees, V = 6973(4) A3, and Z = 4; for 4, a = 16.713(7) A, b = 16.714(6) A, c = 14.775(11) A, beta = 108.24(5) degrees, V = 3920(4) A3, and Z = 2; and for 5', a = 9.5705(1) A, b = 13.0646(1) A, c = 20.1298(2) A, beta = 103.1618(8) degrees, V = 2450.81(4) A3, and Z = 2. The metal centers in 1 and 5' lie in distorted octahedral environments, each facially coordinated by two of the triamine rings of Ldur, the cation in each case being centrosymmetric. In 2, one of the nickel(II) centers is similarly sandwiched by two triamine rings, while the other two nickel(II) centers are each coordinated by a single triamine ring from the ligand, with their distorted octahedral coordination spheres each being completed by three water molecules. In 4, the four triamine rings of Ldur bind to separate copper(II) centers, with two water molecules occupying the remaining two sites of the distorted square pyramidal (SP) coordination spheres, the cation again being centrosymmetric.