Synthesis, structure, and bonding of open-shell Sr3In5: an unusual electron deficiency in an indium network, beyond the Zintl boundary.

The new title compound has been synthesized and characterized by physical property measurements and electronic structure calculations. The results ratify the highly uncommon deficiency of one electron that has been long speculated for its Ca3Ga5-type structure on the basis of the simple Zintl electron counting formalism. In the Sr3In5 structure (Cmcm), 4- and 2-bonded indium atoms in a 4:1 ratio form a three-dimensional classical network that encapsulates strontium atoms in its narrow channels. The electrical conductivity of the compound shows typical metallic behavior. The detailed electronic structure analysis suggests that the electron hole is mainly localized on a nonbonding p-orbital on the 2-bonded indium atoms, and that these orbitals, stacked in a sigma-type way along avector (4.97 A), interact only weakly with each other to form highly one-dimensional bands.     

Synthesis and Structure of Ba(2)Sn(3)Sb(6), a Zintl Phase Containing Channels and Chains

The new Zintl phase dibarium tritin hexaantimonide, Ba(2)Sn(3)Sb(6) has been synthesized, and its structure has been determined by single-crystal X-ray diffraction methods. It crystallizes in the orthorhombic space group -Pnma with a = 13.351(1) ?, b = 4.4100(5) ?, c = 24.449(3) ?, and Z = 4 (T = -50 degrees C). The structure of Ba(2)Sn(3)Sb(6) comprises large channels [010] defined by 30-membered rings constructed from an anionic framework. This framework is built up from Sn-centered trigonal pyramids and tetrahedra, as well as zigzag chains of Sb atoms. Within the channels reside the Ba(2+) cations and additional isolated zigzag Sb-Sb chains. The simultaneous presence of Sn trigonal pyramids and tetrahedra implies that Ba(2)Sn(3)Sb(6) is a mixed-valence compound whose oxidation state notation can be best represented as (Ba(2+))(2)[(Sn(II))(2)(Sn(IV))(Sb(-)(III))(3)(Sb(-)(I))](2)(-)[(Sb(-)(I))(2)](2)(-).     

Metal-biradical chains from a high-spin ligand and bis(hexafluoroacetylacetonato)copper(II)

The synthesis, X-ray crystal structure, and magnetic studies of a rare example of organic/inorganic spin hybrid clusters extended in infinite ladder-type chain [Cu(C5F6HO2)2]7(C35H35N5O4)2 ([Cu(hfac)2]7(pyacbisNN)2, 2) formed by the reaction of a high spin nitronylnitroxide biradical C35H35N5O4 (pyacbisNN, 1) and bis(hexafluroacetylacetonate)copper(II) = Cu(hfac)2 are described. Single-crystal X-ray structure analysis revealed the triclinic P1 space group of 2 with the following parameters: a = 10.6191(4) A, b = 19.6384(7) A, c = 21.941(9) A, alpha = 107.111(7) degrees, beta = 95.107(8) degrees, gamma = 94.208(0) degrees , Z = 2. Each repeating unit in 2 carries a centrosymmetric cyclic six spin and a linear five spin cluster with four different copper coordination environments having octahedral and square planar geometries. These clusters are interconnected to form infinite chains which are running along the crystallographic b axis. The magnetic measurements show nearly paramagnetic behavior with very small variations over a large temperature range. The magnetic properties are thus result of complex competitions of many weak ferro- and antiferromagnetic interactions, which appear as small deviations from quite linear mu(eff) vs T dependence at low temperature. At high temperature (300-14 K), antiferromagnetic behavior dominates a little, while at very low temperature (14-2 K), a small increase of mu(eff) was observed. The magnetic susceptibility data are described by the Curie-Weiss law [chi = C/(T - theta)] with the optimal parameters C = 4.32 +/- 0.01 emuK/mol and theta = - 0.6 +/- 0.3 K, where C is the Curie constant and theta is the Weiss temperature.     

Three novel phases in the Sm-Co-Ga system. Syntheses, crystal and electronic structures, and electrical and magnetic properties

This paper presents the synthesis, identification, and characterization of three novel phases in the ternary system Sm-Co-Ga: SmCoGa5 (tP7, HoCoGa5 type, tetragonal P4/mmm, Z = 1, a = 4.2419(3) A, and c = 6.8559(5) A), Sm4Co3Ga16 (tP23, tetragonal P4/mmm, Z = 1, a = 6.0620(5) A, and c = 11.1495(9) A), and SmCoGa4 (oC24, YNiAl4 type, orthorhombic Cmcm, Z = 4, a = 4.1246(6) A, b = 15.608(2) A, and c = 6.4556(9) A). The structure of SmCoGa5 was obtained from a multiphase X-ray powder Rietveld refinement whereas the crystal structures of the other two phases were determined from single-crystal X-ray analysis. Electronic structures were calculated for all phases by first-principles DFT methods. The atomic arrangements and bonding are discussed on the basis of the partial anionic networks involving Co and Ga atoms, and a strong structural correlation is observed between SmCoGa5 and Sm4Co3Ga16. The latter, which displays paramagnetic behavior, has a resistivity of 4.2 microOmega.cm at 3 K and undergoes a superconducting transition at 2.8 K.     

Synthesis, structure, and bonding of A5Cd2Tl11, A = Cs, Rb. Naked pentagonal antiprismatic columns centered by cadmium

A new anionic thallium cluster chain 1 infinity[Cd2Tl11(5-)] has been discovered in the A-Cd-Tl systems for A = Cs, Rb. The compounds are synthesized by direct fusion of the elements at 700 degrees C and equilibration of the quenched product at 200 degrees C for 1 month. The thallides crystallize in the orthorhombic space group Amm2, Z = 2, a = 56107(7) and 55999(6) A, b = 18090(3) and 17603(3) A, c = 13203(3) and 12896(2) A for A = Cs and Rb, respectively, and contain chains of face-sharing pentagonal Tl10 antiprisms embedded in a matrix of alkali metal cations. Cadmium atoms occupy the center of the antiprisms and donate electrons to the anionic chain. Additional four-bonded Tl atoms on one side of the chain make the structure acentric. The compounds are diamagnetic (chi 296 = -08, -40 (x 10(-4) emu/mol, respectively) and metallic (10-20 mu omega cm at 275 K), and the indirect band gap energy of both compounds is close to zero according to extended Hückel calculations on the isolated chain.     

Cr[(H3N-(CH2)2-PO3)(Cl)(H2O)]: X-ray single-crystal structure and magnetism of a polar organic-inorganic hybrid chromium(II) organophosphonate

Cr[(H(3)N-(CH(2))(2)-PO(3))(Cl)(H(2)O)], a rare example of a polar organic-inorganic hybrid material containing Cr(2+), was prepared from CrCl(2), 2-aminoethylphosphonic acid, and urea in water and isolated as light-blue crystals. It crystallizes in the noncentrosymmetric monoclinic space group P2(1), with a = 5.249(1) A, b = 14.133(3) A, c = 5.275(1) A, and beta = 105.55(2) degrees. The inorganic layer of the hybrid network is formed by Cr(II) five-coordinated by three oxygen atoms from the phosphonates and one from the water molecule in a square pyramidal unit, whose apical position is occupied by the Cl(-) ion. Hydrogen bonds are established between the coordinating water molecule and the oxygen atoms of adjacent phosphonate ligands. The inorganic network is interspersed by ethylammonium groups, and the terminal ammonium moiety is linked to the apical Cl(-) ions through hydrogen bonds. Electrostatic interactions as well as hydrogen bonds and the coordinated chlorine atoms ensure the cohesion of the 3D structure. The lattice is polar (lack of inversion center), and this fact determines the magnetic behavior of the compound at low temperatures. The magnetic susceptibility data in the temperature range from 300 to 50 K show Curie-Weiss behavior, with C = 2.716 cm(3) K mol(-1) and the Weiss constant theta = -2.2 K. The corresponding effective magnetic moment of 4.7 mu(B) compares well with the expected value for Cr(2+) in d(4) high-spin configuration. A slight decrease of the chiT product versus T observed at temperatures below 50 K indicates nearest-neighbor antiferromagnetic exchange interactions. On cooling below T = 6 K, the magnetic susceptibility increases sharply up to a maximum at ca. 5 K and then decreases again. Below T = 6 K, hysteresis loops taken at different temperatures show that Cr[(H(3)N-(CH(2))(2)-PO(3))(Cl)(H(2)O)] behaves as a weak ferromagnet with the critical temperature T(N) at 5.5 K. The spin canting is responsible of the long-range magnetic ordering. The values of the coercive field, H(c), and of remnant magnetization, M(r), obtained from the hysteresis loop at T = 4.5 K (the lowest measured temperature) are 30 Oe and 0.08 mu(B), respectively.     

Phase stabilization through electronic tuning: electron-poorer alkali-metal-indium compounds with unprecedented In/Li clusters

Three alkali-metal-indium compounds K34In(92.30)Li(12.70) (I), K14Na20In(91.82)Li(13.18) (II), and K14Na20In(96.30) (III) (all Rm) have been synthesized and characterized by structural and physical property measurements and electronic structure calculations. Novel mixed In/Li anionic icosahedra and fused icosahedra form in I and II. All three contain In28 as the first triply fused In icosahedra, which are further linked into (In28)In(In28) sandwich adducts in compounds I and II and (In28)In2(In28) in III. Stabilization of these electron-poorer phases through electronic tuning occurs via two different structural (redox) perturbations, either by substitution of certain indium atoms in the clusters by electron-poorer lithium atoms or by the introduction of defects and disorder in the fused cluster (III). The preferential occurrence of either substitutions or defect formation in the clusters is consistent with extended Huckel band calculation results for both the ideal pure indium phase and the Li-substituted equivalent. Model (ideal) and experimental EF values (based on stoichiometries) fall around a pseudogap in DOS. All three compounds are metallic according to both EHTB band calculations and measured resistivities. The cations (A = K, Na) in all the three structures generate A136 clathrate-IotaIotatype networks with remarkably specific and transferable cation dispositions around the two types of anionic cluster units.     

Ca6Cu2Sn7: novel 3D open framework with unusual Sn4 tetramers

The new ternary polar intermetallic phase, Ca6Cu2Sn7, has been synthesized by the solid-state reaction of the stoichiometric mixture of the pure elements in welded Ta tubes at high temperature. Its structure was established by single-crystal X-ray diffraction studies. Ca6Cu2Sn7 crystallizes in the monoclinic space group C2/m (No. 12) with cell parameters of a=14.257(7), b=4.564(2), and c=12.376(7) A, beta=93.979(6) degrees, V=803.3(7) A3, and Z=2. The structure of Ca6Cu2Sn7 belongs to a new structure type and features a 3D anionic open-framework composed of [Cu2Sn3] layers interconnected by unusual Sn4 tetramers, forming large tunnels along the b axis which are composed of Cu4Sn12 16-membered rings. The calcium atoms are located in these large tunnels. Ca6Cu2Sn7 is metallic and exhibits temperature-independent paramagnetism.     

BaIrIn4 and Ba2Ir4In13: two In-rich polar intermetallic structures with different augmented prismatic environments about the cations

The title phases were synthesized via high-temperature reactions of the elements in welded Ta tubes and characterized by single-crystal X-ray diffraction methods and band calculations. BaIrIn4 adopts the LaCoAl4-type structure: Pmma, Z = 2, a = 8.642(2), b = 4.396(1), and c = 7.906(2) A. Ba2Ir4In13 exhibits a new structure type: Cmc2(1), Z = 4, a = 4.4856(9), b = 29.052(6), and c = 13.687(3) A. BaIrIn4 is constructed from a single basic unit, a Ba-centered pentagonal prism of indium on which two adjacent and the opposed rectangular faces are capped by In and Ir, respectively. The three capping atoms are coplanar with Ba and represent the only augmentation of the pentagonal prism. The relatively large proportions of Ba:Ir, In, and of In:Ir lead to the condensation of homoatomic pentagonal prisms into zigzag chains through the sharing of the two uncapped faces. The cation proportion is much lower in Ba2Ir4In13, and Ba atoms are surrounded by a more anionic Ir/In network without any condensation between prisms. This and the greater Ir proportion lead to a network of formal augmented pentagonal Ba@Ir5In15 and hexagonal Ba@Ir7In15 prisms with overall 5-10-5 and 6-10-6 arrangements of parallel planar rings, respectively, although most Ir is not well bound to the prisms. The latter prism, with alternating Ir/In atoms in the basal faces, is novel for Ae-T-In phases (Ae = alkaline-earth metal, T = Co, Rh, Ir). Band structure calculation results (linear-muffin-tin-orbital method in the atomic sphere approximation) emphasize the greater overlap populations (approximately strengths) of the Ir-In bonds and confirm expectations that both compounds are metallic. The Ir 5d bands are narrower and lie higher in energy than those for Au in analogous phases.     

Planar versus puckered nets in the polar intermetallic series EuGaTt (Tt = Si, Ge, Sn)

The ternary polar intermetallic compounds EuGaTt (Tt = Si, Ge, Sn) have been synthesized and characterized experimentally, as well as theoretically. EuGaSi crystallizes in the hexagonal AlB(2)-type structure (space group P6/mmm, Z = 1, Pearson symbol hP3) with randomly distributed Ga and Si atoms on the graphite-type planes: a = 4.1687(6) A, c = 4.5543(9) A. On the other hand, EuGaGe and EuGaSn adopt the hexagonal YPtAs-type structure (space group P6(3)/mmc, Z = 4, Pearson symbol hP12): a = 4.2646(6) A and c = 18.041(5) A for EuGaGe; a = 4.5243(5) A and c = 18.067(3) A for EuGaSn. The three crystal structures contain formally [GaTt](2-) polyanionic 3-bonded, hexagonal networks, which change from planar to puckered and exhibit a significant decrease in interlayer Ga-Ga distances as the size of Tt increases. Magnetic susceptibility measurements of this series of compounds show Curie-Weiss behavior above 86(5), 95(5), and 116(5) K with magnetic moments of 7.93, 7.97, and 7.99 mu(B) for EuGaSi, EuGaGe, and EuGaSn, respectively, indicating a 4f(7) electronic configuration (Eu(2+)) for Eu atoms. X-ray absorption spectra (XAS) are also consistent with these magnetic properties. Electronic structure calculations supplemented by a crystal orbital Hamilton population (COHP) analysis identifies the synergy between atomic sizes, from both Eu and Tt atoms, and the orbital contributions from Eu toward influencing the structural features of EuGaTt. A multicentered interaction between planes of Eu atoms and the [GaTt](2-) layers rather than through-space Ga-Ga bonding is seen in ELF distributions.     

Crystal Structure and Magnetic Behavior of [(C(2)H(5))(4)N](2)Cu(5)Cl(12). A Novel Two-Dimensional Copper(II) Halide Network Derived from the CuCl(2) Structure

A new chlorocuprate(II), [(C(2)H(5))(4)N](2)Cu(5)Cl(12), was prepared by reaction of CuCl(2).2H(2)O and (C(2)H(5))(4)NCl in 1,1,2-trichloroethane-ethanol followed by water-ethanol evaporation. The crystal structure, solved by single-crystal X-ray diffraction at room temperature, was found to be triclinic, space group P&onemacr;, with cell parameters a = 8.9123(9) ?, b = 11.0690(8) ?, c = 11.2211(9) ?, alpha = 118.766(6) degrees beta = 109.041(8) degrees, gamma = 97.465(7) degrees, and Z = 1, and consists of a two-dimensional network of [(Cu(5)Cl(12))(2)(-)](infinity) parallel to the a, b plane, alternating with layers of the organic cations along c. The anionic sheets are built up by aggregation of infinite zigzag chains of alternating tetranuclear and mononuclear subsequences. This structure can be related to the anhydrous CuCl(2) structure by systematic removal of (Cu(2)Cl(6))(2+) fragments. The magnetic susceptibility of this compound can be described by a simple model, suggested by the structural data, that considers independent contributions of linear tetramers, with antiferromagnetically coupled pairs of copper atoms (J(1)/k = -64(2) K), and almost magnetically isolated Cu(II) centers, that obey a Curie-Weiss law with a Θ = -2.7(8) K.     

Synthesis and characterization of f-element iodate architectures with variable dimensionality, alpha- and beta-Am(IO3)3

Two americium(III) iodates, beta-Am(IO3)3 (I) and alpha-Am(IO3)3 (II), have been prepared from the aqueous reactions of Am(III) with KIO(4) at 180 degrees C and have been characterized by single-crystal X-ray diffraction, diffuse reflectance, and Raman spectroscopy. The alpha-form is consistent with the known structure type I of anhydrous lanthanide iodates. It consists of a three-dimensional network of pyramidal iodate groups bridging [AmO8] polyhedra where each of the americium ions are coordinated to eight iodate ligands. The beta-form reveals a novel architecture that is unknown within the f-element iodate series. beta-Am(IO3)3 exhibits a two-dimensional layered structure with nine-coordinate Am(III) atoms. Three crystallographically unique pyramidal iodate anions link the Am atoms into corrugated sheets that interact with one another through intermolecular IO3-...IO3- interactions forming dimeric I2O10 units. One of these anions utilizes all three O atoms to simultaneously bridge three Am atoms. The other two iodate ligands bridge only two Am atoms and have one terminal O atom. In contrast to alpha-Am(IO3)3, where the [IO3] ligands are solely corner-sharing with [AmO8] polyhedra, a complex arrangement of corner- and edge-sharing mu2- and mu3-[IO3] pyramids can be found in beta-Am(IO3)3. Crystallographic data: I, monoclinic, space group P2(1)/n, a = 8.871(3) A, b = 5.933(2) A, c = 15.315(4) A, beta = 96.948(4) degrees , V = 800.1(4) A(3), Z = 4; II, monoclinic, space group P2(1)/c, a = 7.243(2) A, b = 8.538(3) A, c = 13.513(5) A, beta = 100.123(6) degrees , V = 822.7(5) A(3), Z = 4.     

Structure and magnetism of a spin ladder system: (C5H9NH3)2CuBr4

The crystal structure of bis(cyclopentylammonium)tetrabromocuprate(II) has been determined at room temperature and at -70 degrees C. The room temperature structure is orthorhombic, space group Pn2(1)a, with a = 12.092(6) A, b = 8.134(4) A, and c = 18.698(10) A. The low temperature structure is also orthorhombic, space group Pna2(1), with a = 24.111(5) A, b = 8.089(2) A, and c = 18.448(4) A. DSC studies reveal the presence of a weak endotherm at -13 degrees C. The structures of the two phases are very similar, differing only in the relative orientations of the cyclopentyl rings of the organic cations and slight displacements of the anionic tetrahedra. The CuBr(4)(2)(-) anions in the low temperature phase are arranged to define a spin ladder system through Cu-Br.Br-Cu two-halide exchange pathways. Magnetic susceptibility data have been analyzed and yield antiferromagnetic exchange strengths 2J(rail)/k = -11.6 K and 2J(rung)/k = -5.5 K with a singlet-triplet gap energy Delta/k(B) = 2.3 K. This is the first report of a spin ladder with a stronger interaction along the axis of the ladder than along the rungs.     

High-pressure synthesis and transport properties of a new binary germanide, SrGe6-delta (delta congruent with 0.5), with a cagelike structure

A new germanide, SrGe6-delta (delta congruent with 0.5), was synthesized by the reaction of Sr and Ge mixtures under a pressure of 5 GPa at 1200 degrees C. It crystallized in the orthorhombic space group Cmcm (No. 63) with a = 4.0981(6) A, b = 11.159(1) A, c = 12.6825(8) A, V = 580.0(1) A3, and Z = 4. SrGe6-delta is composed of a Ge covalent network having a cagelike structure and Sr atoms situated in the cages. Each Ge atom is coordinated by four neighboring Ge atoms. The coordination polyhedra are fairly distorted from an ideal tetrahedron, and the Ge network contains vacancies and disordering. The resistivity shows metallic behavior down to 2 K, and the positive thermoelectric power indicates the dominant carriers to be holes.     

Construction of hydrogen-bonded and coordination-bonded networks of cobalt(II) with pyromellitate: synthesis,structures, and magnetic properties

Synthesis (hydrothermal and metathesis), characterization (UV-vis, IR, TG/DTA), single-crystal X-ray structures, and magnetic properties of three cobalt(II)-pyromellitate complexes, purple [Co(2)(pm)](n) (1), red [Co(2)(pm)(H(2)O)(4)](n) x 2nH(2)O (2), and pink [Co(H(2)O)(6)](H(2)pm) (3) (H(4)pm = pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid)), are described. 1 consists of one-dimensional chains of edge-sharing CoO(6) octahedra that are connected into layers via O-C-O bridges. The layers are held together by the pyromellitate (pm(4-)) backbone to give a three-dimensional structure, each ligand participating in an unprecedented 12 coordination bonds (Co-O) to 10 cobalt atoms. 2 consists of a three-dimensional coordination network possessing cavities in which unbound water molecules reside. This highly symmetric network comprises eight coordinate bonds (Co-O) between oxygen atoms of pm(4-) to six trans-Co(H(2)O)(2). 3 possesses a hydrogen-bonded sandwich structure associating layers of [Co(H(2)O)(6)](2+) and planar H(2)pm(2-). The IR spectra, reflecting the different coordination modes and charges of the pyromellitate, are presented and discussed. The magnetic properties of 1 indicate complex behavior with three ground states (collinear and canted antiferromagnetism and field-induced ferromagnetism). Above the Néel temperature (T(N)) of 16 K it displays paramagnetism with short-range ferromagnetic interactions (Theta = +16.4 K, mu(eff) = 4.90 mu(B) per Co). Below T(N) a weak spontaneous magnetization is observed at 12.8 K in low applied fields (H < 100 Oe). At higher fields (H > 1000 Oe) metamagnetic behavior is observed. Two types of hysteresis loops are observed; one centered about zero field and the second about the metamagnetic critical field. The critical field and the hysteresis width increase as the temperature is lowered. The heat capacity data suggest that 1 has a 2D or 3D magnetic lattice, and the derived magnetic entropy data confirm an anisotropic s(eff) = 1/2 for the cobalt(II) ion. Magnetic susceptibility data indicate that 2 and 3 are paramagnets.     

Formation of anionic σ-aryl complexes of platinum (IV) in the reaction of H2PtCl6 with aromatic compounds. The crystal and molecular structures of platinum (IV) complexes of naphthalene and ortho-nitrotoluene

The crystal and molecular structures of anionic platinum(IV) complexes of naphthalene (I) and ortho-nitrotoluene (II) have been determined by X-ray diffraction. The structures of both complexes are similar. The platinum atom is octahedrally coordinated with four chlorine atoms occupying the equatorial positions and σ-bonded aryl and neutral ammonia ligands situated in the axial positions.     

SrAu4In4 and Sr4Au9In13: polar intermetallic structures with cations in augmented hexagonal prismatic environments

The title compounds were synthesized via high-temperature reactions of the elements in welded Ta tubes and characterized by single-crystal X-ray diffraction analyses and band structure calculations. SrAu(3.76(2))In(4.24) crystallizes in the YCo5In3 structure type with two of eight network sites occupied by mixtures of Au and In: Pnma, Z = 4, a = 13.946(7), b = 4.458(2), c = 12.921(6) A. Its phase breadth appears to be small. Sr4Au9In 13 exhibits a new structure type, P_6 m2, Z = 1, a = 12.701(2), c = 4.4350(9) A. The Sr atoms in both compounds center hexagonal prisms of nominally alternating In and Au atoms and also have nine augmenting (outer) Au + In atoms around their waists so as to define 21-vertex Sr@Au9M4In8 (M = Au/In) and Sr@Au9In12 polyhedra, respectively. The relatively larger Sr content in the second phase also leads to condensation of some of the ideal building units into trefoil-like cages with edge-shared six-member rings. One overall driving force for the formation of these structures can be viewed as the need for each Sr cation to have as many close neighbors as possible in the more anionic Au-In network. The results also depend on the cation size as well as on the flexibility of the anionic network and an efficient intercluster condensation mode as all clusters are shared. Band structure calculations (LMTO-ASA) emphasize the greater strengths (overlap populations) of the Au-In bonds and confirm expectations that both compounds are metallic.     

Binding of phosphate with a simple hexaaza polyammonium macrocycle

A mixture of dihydrogen phosphate and phosphoric acid has been crystallized with a hexaprotonated 26-membered polyammonium macrocycle, 1,4,7,14,17,20-hexaazacyclohexacosane, as the counterion. The complex crystallizes in the monoclinic space group P2(1)/c with unit cell parameters of a = 10.006(2) A, b = 12.525(1) A, c = 19.210(2) A, beta = 102.91(1) degrees, and V = 2346.6(5) A3. The hexaprotonated macrocycle is located on a crystallographic center of inversion and is surrounded by eight phosphate anions. Six of the phosphates are dihydrogen phosphates (H2PO4-), and the other two are neutral phosphoric acid molecules. Intricate hydrogen-bonding networks, involving the anionic and neutral phosphates and the protonated macrocycle, dominate the crystal lattice. Potentiometric studies using NaCl as the supporting electrolyte indicate high formation constants for the triprotonated macrocycle, H3L3+, with PO4(3-) at pH approximately 9.5 (log K = 4.55(4)), for the tetraprotonated macrocycle, H4L4+, with monohydrogen phosphate, HPO4(2-), at pH approximately 8.0 (log K = 6.01(3)), and for ditopic complexes with H5L5+ and H6L6+ and dihydrogen phosphate, H2PO4-, at pH approximately 4.0 (log K = 6.16(6)) and pH approximately 2.5 (log K = 6.44(5)), respectively. The ditopic behavior in the simple polyazamacrocycle receptor is a somewhat unusual occurrence, as is the finding of phosphoric acid species in the crystal structure.     

Polynuclear palladium complexes with 3,5-dimethylpyrazolate exhibiting three different coordination modes

The characterisation of dinuclear pyrazolato-bridged Pd(II) complexes, [(Pd(mu-dmpz)Cl(Hdmpz))2] (1) and [(Pd(mu-dmpz)(dmpz)(Hdmpz))2] (2) (Hdmpz=dimethylpyrazole), has been carried out. An X-ray study of compound 2 reveals the existence of intramolecular N-H...N hydrogen bonds between neighbouring dmpz groups. Compound 2 has been deprotonated and both acidic hydrogen atoms substituted by two metal atoms of Cu(I), Ag(I) or Au(I) to give the tetranuclear compounds [Pd2M2(mu(2)-dmpz-kappaN,N')6] (M=Cu, Ag, Au). The structure of these compounds resembles a box with a small cavity inside. There are also three pi-electron-rich clefts between each of the three pairs of azolato rings, capable of further complexation. The reactions of [Pd2M2(mu(2)-dmpz-kappaN,N')6] (M=Cu, Ag, Au) with AgClO4 render compounds of the type [(Pd2M2(mu(2)-dmpz-kappaN,N')2(-)(mu(3)-dmpz-kappaN,N',C4)4Ag2(mu(2)-O2ClO2))2] (M=Cu, Ag, Au). The X-ray structures of crystals obtained from a solution of compounds [(Pd2M2(mu(2)-dmpz-kappaN,N')2(mu(3)-dmpz-kappaN,N',C4)4Ag2(mu(2)-O(2)ClO2))2] (M=Ag, Au) in acetone reveals a [(Pd2M2(mu(2)-dmpz-kappaN,N')2(mu(3)-dmpz-kappaN,N',C4)4Ag(OCMe2)(OClO3)Ag(mu(2)-O2ClO2))2] stoichiometry, indicating that only two of the three pi-electron-rich clefts have been used to accommodate Ag+ ions. Each of the silver atoms are located in between two 3,5-dmpz rings and are eta(1)-bonded to the C4 atom of each group.