Synthesis and characterization of the silver maleonitrilediselenolates and silver maleonitriledithiolates [K([2.2.2]-cryptand)]4[Ag4(Se2C2(CN)2)4], [Na([2.2.2]-cryptand)]4[Ag4(S2C2(CN)2)4].0.33MeCN, [NBu4]4[Ag4(S2C2(CN)2)4], [K([2.2.2]-cryptand)]3[Ag(Se2C2(CN)2)2].2MeCN, and [Na([2.2.2]-cryptand)]3[Ag(S2C2(CN)2)2

Reaction of AgBF(4), KNH(2), K(2)Se, Se, and [2.2.2]-cryptand in acetonitrile yields [K([2.2.2]-cryptand)](4)[Ag(4)(Se(2)C(2)(CN)(2))(4)] (1). In the unit cell of 1 there are four [K([2.2.2]-cryptand)](+) units and a tetrahedral Ag(4) anionic core coordinated in mu(1)-Se, mu(2)-Se fashion by each of four mns ligands (mns = maleonitrilediselenolate, [Se(2)C(2)(CN)(2)](2)(-)). Reaction of AgNO(3), Na(2)(mnt) (mnt = maleonitriledithiolate, [S(2)C(2)(CN)(2)](2)(-)), and [2.2.2]-cryptand in acetonitrile yields [Na([2.2.2]-cryptand)](4)[Ag(4)(mnt)(4)].0.33MeCN (2). The Ag(4) anion of 2 is analogous to that in 1. Reaction of AgNO(3), Na(2)(mnt), and [NBu(4)]Br in acetonitrile yields [NBu(4)](4)[Ag(4)(mnt)(4)] (3). The anion of 3 also comprises an Ag(4) core coordinated by four mnt ligands, but the Ag(4) core is diamond-shaped rather than tetrahedral. Reaction of [K([2.2.2]-cryptand)](3)[Ag(mns)(Se(6))] with KNH(2) and [2.2.2]-cryptand in acetonitrile yields [K([2.2.2]-cryptand)](3)[Ag(mns)(2)].2MeCN (4). The anion of 4 comprises an Ag center coordinated by two mns ligands in a tetrahedral arrangement. Reaction of AgNO(3), 2 equiv of Na(2)(mnt), and [2.2.2]-cryptand in acetonitrile yields [Na([2.2.2]-cryptand)](3)[Ag(mnt)(2)] (5). The anion of 5 is analogous to that of 4. Electronic absorption and infrared spectra of each complex show behavior characteristic of metal-maleonitriledichalcogenates. Crystal data (153 K): 1, P2/n, Z = 2, a = 18.362(2) A, b = 16.500(1) A, c = 19.673(2) A, beta = 94.67(1) degrees, V = 5941(1) A(3); 2, P4, Z = 4, a= 27.039(4) A, c = 15.358(3) A, V = 11229(3) A(3); 3, P2(1)/c, Z = 6, a = 15.689(3) A, b = 51.924(11) A, c = 17.393(4) A, beta = 93.51(1) degrees, V = 14142(5) A(3); 4, P2(1)/c, Z = 4, a = 13.997(1) A, b = 21.866(2) A, c = 28.281(2) A, beta = 97.72(1) degrees, V = 8578(1) A(3); 5, P2/n, Z = 2, a = 11.547(2) A, b = 11.766(2) A, c = 27.774(6) A, beta = 91.85(3) degrees, V = 3772(1) A(3).     

Structural influences of organonitrogen ligands on vanadium oxide solids. Hydrothermal syntheses and structures of the terpyridine vanadates [V2O4(terpy)2]3[V10O28], [VO2(terpy)][V4O10], and [V9O22(terpy)3

Hydrothermal reactions of the V2O5/2,2':6':2"-terpyridine/ZnO/H2O system under a variety of conditions yielded the organic-inorganic hybrid materials [V2O4(terpy)2]3[V10O28].2H2O (VOXI-10), [VO2(terpy)][V4O10] (VOXI-11), and [V9O22(terpy)3] (VOXI-12). The structure of VOXI-10 consists of discrete binuclear cations [V2O4(terpy)2]2+ and one-dimensional chains [V10O28]6-, constructed of cyclic [V4O12]4- clusters linked through (VO4) tetrahedra. In contrast, the structure of VOXI-11 exhibits discrete mononuclear cations [VO2(terpy)]1+ and a two-dimensional vanadium oxide network, [V4O10]1-. The structure of the oxide layer is constructed from ribbons of edge-sharing square pyramids; adjacent ribbons are connected through corner-sharing interactions into the two-dimensional architecture. VOXI-12 is also a network structure; however, in this case the terpy ligand is incorporated into the two-dimensional oxide network whose unique structure is constructed from cyclic [V6O18]6- clusters and linear (V3O5(terpy)3) moieties of corner-sharing vanadium octahedra. The rings form chains through corner-sharing linkages; adjacent chains are connected through the trinuclear units. Crystal data: VOXI-10, C90H70N18O42V16, triclinic P1, a = 12.2071(7) A, b = 13.8855(8) A, 16.9832(10) A, alpha = 69.584(1) degrees, beta = 71.204(1) degrees, gamma = 84.640(1) degrees, Z = 1; VOXI-11, C15H11N3O12V5, monoclinic, P2(1)/n, a = 7.7771(1) A, b = 10.3595(2) A, c = 25.715(4) A, beta = 92.286(1) degrees, Z = 4; VOXI-12, C45H33N9O22V9, monoclinic C2/c, a = 23.774(2) A, b = 9.4309(6) A, c = 25.380(2) A, beta = 112.047(1) degrees, Z = 4.     

Cs3AgAs4Se8 and CsAgAs2Se4: selenoarsenates with infinite 1 infinity[AsSe2]- chains in different Ag+ coordination environments

Two quaternary silver selenoarsenates Cs3AgAs4Se8 (I) and CsAgAs2Se4 (II) have been discovered by methanothermal reaction of Li3AsSe3 with AgBF4 in the presence of the respective alkali metal sources Cs2CO3 and CsCl. Orange crystals of Cs3AgAs4Se8 (I) were formed after reaction at 120 degrees C for 72 h, whereas red CsAgAs2Se4 (II) was obtained under slightly different conditions at 140 degrees C for 70 h. Both compounds possess novel two-dimensional (2D) polyanions consisting of infinite 1 infinity[AsSe2]- chains that are interconnected by Ag+ ions in different coordination patterns. In I, a double layer of 1 infinity[AsSe2]- chains is bridged by distorted trigonal planar coordinated Ag+ atoms to form a 2 infinity[AgAs4Se8]3- layer with a thickness of about 11.3 A. The nonbonding Ag...Ag distances are about 4.220 A, and large cavities within the layers accommodate for three of the four crystallographic Cs+ cations. The double amount of Ag+ atoms per AsSe2 chain unit in II leads to simple layers 2 infinity[AgAs2Se4]- [=[Ag2As4Se8]2-] in which the Ag+ atoms are arranged in rows between the 1 infinity[AsSe2]- chains, with alternating Ag...Ag distances of 3.053(3) and 3.488(3) A. Hereby the 1 infinity[AsSe2]- polyanions show a disorder within the central (-As-Seb)- chain (b = bridging), while the positions of the terminal Se atoms (Set) remain unaffected. The thermal, optical, and spectroscopic properties of the compounds are reported. Both I and II melt with decomposition and are wide band gap semiconductors with values of 2.07 and 1.79 eV, respectively. Raman spectroscopic data show typical band patterns expected for infinite [AsSe2]- chains. Crystal Data: Cs3AgAs4Se8 (I), monoclinic, C2/c, a = 25.212(2) A, b = 8.0748(7) A, c = 22.803(2) A, beta = 116.272(2) degrees, Z = 8; CsAgAs2Se4 (II), monoclinic, P2(1)/n, a = 10.9211(1) A, b = 6.5188(2) A, c = 13.7553(3) A, beta = 108.956(1) degrees, Z = 4.     

Gold(I) and silver(I) mixed-metal trinuclear complexes: dimeric products from the reaction of gold(I) carbeniates or benzylimidazolates with silver(I) 3,5-diphenylpyrazolate

Trinuclear mixed-metal gold-silver compounds are obtained by the reaction of gold(I) carbeniate [Au(mu-C(OEt)=NC6H4-p-CH3)]3, TR(carb), or gold(I) imidazolate [Au-mu-C,N-1-benzyl-2-imidazolate]3, TR(bzim), with silver(I) pyrazolate [Ag(mu-3,5-Ph2pz)]3. The crystalline products are mixed-ligand, mixed-metal dimeric products [Au(carb)Ag2(mu-3,5-Ph2pz)2], [Au2(carb)2Ag(mu-3,5-Ph2pz)].CH2Cl2, [Au(bzim)2Ag2(mu-3,5-Ph2pz)], and [Au2(bzim)2Ag(mu-3,5-Ph2pz)]. They have been characterized by elemental analysis and 1H NMR and mass spectrometry. The X-ray structure of [Au(carb)Ag2(mu-3,5-Ph2pz)2] shows it to be a dimer with two Ag...Au contacts between the trinuclear units of 3.083(2) and 3.310(2) A and with average intramolecular Ag...Ag and Au...Ag distances of approximately 3.3 and 3.2 A, respectively. The structure of [Au2(carb)2Ag(mu-3,5-Ph2pz)].CH2Cl2 is a dimer with one intermolecular Au...Au attraction of 3.3354(10) A and a short Ag...Au distance of approximately 3.42 A and intramolecular Ag...Au and Au...Au contacts of approximately 3.2 and approximately 3.3 A, respectively. Packing diagrams of both complexes show that the dimeric units are independent, similar to their parent molecules. The dimers of trinuclear [Au(carb)Ag2(mu-3,5-Ph2pz)2] and [Au2(carb)2Ag(mu-3,5-Ph2pz)].CH2Cl2 crystallize in the triclinic space group P (Z = 2), a = 9.688(3) A, b = 15.542(4) A, c = 23.689(6) A, alpha = 82.560(5) degrees , beta = 87.887(6) degrees , gamma = 78.060(5) degrees , and the orthorhombic space group Pca2(1) (Z = 4), a = 29.644(4) A, b = 7.4582(10) A, c = 30.473(4) A, respectively. The structure of [Au(bzim)Ag2(mu-3,5-Ph2pz)2] is a dimer with two metallophilic Ag...Au interactions of 3.14 A. The complex crystallizes in the monoclinic space group C2/c (Z = 4), a = 26.368(5) A, b = 15.672(3) A, c = 17.010(3) A, beta = 102.206(3) degrees .     

Heteroatomic deltahedral clusters of main-group elements: synthesis and structure of the Zintl ions [In4Bi5]3-, [InBi3]2-, and [GaBi3]2-

Reported are the first heteroatomic deltahedral Zintl ions made of elements differing by more than one group, indium or gallium and bismuth. Nine-atom clusters [In4Bi5]3- are characterized in two different compounds, (Na-crypt)3[In4Bi5] (4, P2(1)/n, a = 23.572(6) A, b = 15.042(4) A, c = 24.071(4) A, beta = 106.00(3) degrees, Z = 4) and (K-crypt)6[In4Bi5][In4Bi5].1.5en.0.5tol (5, P2(1)/c, a = 28.532(2) A, b = 23.707(2) A, c = 28.021(2) A, beta = 93.274(4) degrees, Z = 4). Tetrahedra of [InBi3]2- or [GaBi3]2- are found in (K-crypt)2[InBi3].en (1, P2(1), a = 12.347(4) A, b = 20.884(4) A, c = 12.619(7) A, beta = 119.02(4) degrees, Z = 2) and in the isostructural (Rb-crypt)2[InBi3].en (2, a = 12.403(8) A, b = 20.99(1) A, c = 12.617(9) A, beta = 118.83(4) degrees) and (K-crypt)2[GaBi3].en (3, a = 12.324(5) A, b = 20.890(8) A, c = 12.629(5) A, beta = 118.91(3) degrees). All compounds are crystallized from ethylenediamine/crypt solutions of precursors with nominal composition "A5E2Bi4" where A = Na, K, or Rb and E = Ga or In. The cluster in 4 is a well-ordered monocapped square antiprism with the four indium atoms occupying the five-bonded positions. Compound 5 contains two independent [In4Bi5]3- clusters; one is the same as the cluster in 4, while the other is a tricapped trigonal prism with two elongated prismatic edges. All compounds are EPR-silent and therefore diamagnetic.     

Bimetallic cyanide-bridged complexes based on the photochromic nitroprusside anion and paramagnetic metal complexes. Syntheses, structures, and physical characterization of the coordination compounds [Ni(en)2]4[Fe(CN)5NO]2[Fe(CN)6]x5H2O, [Ni(en)2][Fe(CN)5NO]x3H2O, [Mn(3-MeOsalen)(H2O)]2[Fe(CN)5NO], and [Mn(5-Brsalen)]2[Fe(CN)5NO

The synthesis, crystal structure, and physical characterization of the coordination compounds [Ni(en)2]4[Fe(CN)5NO]2[Fe(CN)6]x5H2O (1), [Ni(en)2][Fe(CN)5NO]x3H2O (2), [Mn(3-MeOsalen)(H2O)]2[Fe(CN)5NO] (3), and [Mn(5-Brsalen)]2[Fe(CN)5NO] (4) are presented. 1 crystallizes in the monoclinic space group P2(1)/n (a = 7.407(4) A, b = 28.963(6) A, c = 14.744(5) A, alpha = 90 degrees, beta = 103.26(4) degrees, gamma = 90 degrees, Z = 2). Its structure consists of branched linear chains formed by cis-[Ni(en)2]2+ cations and ferrocyanide and nitroprusside anions. The presence of two kinds of iron(II) sites has been demonstrated by M?ssbauer spectroscopy. 2 crystallizes in the monoclinic space group P2(1)/c (a = 11.076(3) A, b = 10.983(2) A, c = 17.018(5) A, alpha = 90 degrees, beta = 107.25(2) degrees, gamma = 90 degrees, Z = 4). Its structure consists of zigzag chains formed by an alternated array of cis-[Ni(en)2]2+ cations and nitroprusside anions. 3 crystallizes in the triclinic space group P1 (a = 8.896(5) A, b = 10.430(5) A, c = 12.699(5) A, alpha = 71.110(5) degrees, beta = 79.990(5) degrees, gamma = 89.470(5) degrees, Z = 1). Its structure comprises neutral trinuclear bimetallic complexes in which a central [Fe(CN)5NO]2- anion is linked to two [Mn(3-MeOsalen)]+ cations. 4 crystallizes in the tetragonal space group P4/ncc (a = 13.630(5) A, c = 21.420(8) A, Z = 4). Its structure shows an extended 2D neutral network formed by cyclic octameric [-Mn-NC-Fe-CN-]4 units. The magnetic properties of these compounds indicate the presence of quasi-isolated paramagnetic Ni2+ and Mn3+. Irradiated samples of the four compounds have been studied by differential scanning calorimetry to detect the existence of the long-lived metastable states of nitroprusside.     

Organometallic coordination polymers generated from bent Bis(acetylenylphenyl)oxadiazole ligands and Ag(I) salts

Two new bent oxadiazole bridging benzoacetylene ligands 2,5-bis(4-ethynylphenyl)-1,3,4-oxadiazole (L9) and 2,5-bis(3-ethynylphenyl)-1,3,4-oxadiazole (L10) were synthesized. The coordination chemistry of them with various inorganic Ag(I) salts has been investigated. Seven new coordination polymers were prepared by solution reactions and fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. [Ag2(L9)](SO3CF3)2 (1) (triclinic, P; a =10.292(4), b = 10.794(4), c = 11.399(5) A; alpha = 98.894(5), beta = 102.360(6), gamma = 90.319(5) degrees ; Z = 2), [Ag(L9)]SbF6 (2) (orthorhombic, Cmca; a = 19.059(9), b = 12.922(6), c = 15.609(7) A; Z = 8), [Ag(L9)]BF4 (3) (orthorhombic, Cmca; a = 19.128(3), b = 12.6042(18), c = 28.003(4) A; Z = 16), [Ag(L9)]ClO4 (4) (monoclinic, P2(1)/c; a = 8.5153(16), b = 19.722(4), c = 10.320(2) A; beta = 105.307(3) degrees ; Z = 4), [Ag(L10)]SO3CF3 (5) (triclinic, P; a = 9.0605(13), b = 10.4956(15), c = 10.8085(16) A; alpha = 101.666(2), beta = 109.269(2), gamma = 100.944(2) degrees ; Z = 2), [Ag(L10)(H2O)(0.5)]BF4.0.5H2O (6) (monoclinic, C2/m; a = 32.180(6), b = 17.027(3), c = 8.1453(15) A; beta = 102.541(3) degrees ; Z = 8), and {[Ag2(L10)2(H2O)](ClO4)2}.o-xylene (7) (monoclinic, P2(1)/c; a = 8.1460(10), b = 17.326(2), c = 30.345(4) A; beta = 97.71 degrees ; Z = 4) were obtained by the combination of L9 and L10 with various Ag(I) salts in a benzene/methylene chloride mixed solvent system. In addition, the luminescent and electrical conductive properties of these new compounds were investigated.     

A hydrothermal investigation of the 1/2V2O5-H2C2O4/H3PO4/NH4OH system: synthesis and structures of (NH4)VOPO(4).1.5H2O, (NH4)0.5VOPO(4).1.5H2O, (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2](2).3H2O, and (NH4)2[VO(HPO4)]2(C2O4).5H2O

The 1/2V2O5-H2C2O4/H3PO4/NH4OH system was investigated using hydrothermal techniques. Four new phases, (NH4)VOPO(4).1.5H2O (1), (NH4)0.5VOPO(4).1.5H2O (2), (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2]2.3H2O (3), and (NH4)2[VO(HPO4)]2(C2O4).H2O (4), have been prepared and structurally characterized. Compounds 1 and 2 have layered structures closely related to VOPO(4).2H2O and A0.5VOPO4.yH2O (A = mono- or divalent metals), whereas 3 has a 3D open-framework structure. Compound 4 has a layered structure and contains both oxalate and phosphate anions coordinated to vanadium cations. Crystal data: (NH4)VOPO(4).1.5H2O, tetragonal (I), space group I4/mmm (No. 139), a = 6.3160(5) A, c = 13.540(2) A, Z = 4; (NH4)0.5VOPO(4).1.5H2O, monoclinic, space group P2(1)/m (No. 11), a = 6.9669(6) A, b = 17.663(2) A, c = 8.9304(8) A, beta = 105.347(1) degrees, Z = 8; (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2]2.3H2O, triclinic, space group P1 (No. 2), a = 10.2523(9) A, b = 12.263(1) A, c = 12.362(1) A, alpha = 69.041(2) degrees, beta = 65.653(2) degrees, gamma = 87.789(2) degrees, Z = 2; (NH4)2[VO(HPO4)]2(C2O4).5H2O, monoclinic (C), space group C2/m (No. 12), a = 17.735(2) A, b = 6.4180(6) A, c = 22.839(2) A, beta = 102.017(2) degrees, Z = 6.     

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.     

Synthese und Struktur von Silber(II)-tetrafluoroaurat(III) Ag[AuF4]2

Synthesis and Structure of Silver(II) Tetrafluoroaurate(III) Ag[AuF₄]₂ Intensive green single crystals of Ag[AuF₄]₂ can be obtained by heating up micro crystalline Ag[AuF₄]₂ in autoclaves (p(F₂) ～ 200 bar, T ～ 400°C, t ～ 14 d). It crystallizes monoclinic, space group P2₁/n ? C; (No. 14) with a = 522.3(1), b = 1101.3(3), c = 550.5(2) pm, β = 94.98(3), Z = 2 and is isotypic with Pd[AuF₄]₂.     

Syntheses, structures, and spectroscopic properties of K9Nd[PS4]4, K3Nd[PS4]2, Cs3Nd[PS4]2, and K3Nd3[PS4]4

Four new quaternary alkali neodymium thiophosphates K 9Nd[PS 4] 4 ( 1), K 3Nd[PS 4] 2 ( 2), Cs 3Nd[PS 4] 2 ( 3), and K 3Nd 3[PS 4] 4 ( 4) were synthesized by reacting Nd with in situ formed fluxes of K 2S 3 or Cs 2S 3, P 2S 5 and S in appropriate molar ratios at 973 K. Their crystal structures are determined by single crystal X-ray diffraction. Crystal data: 1: space group C2/ c, a = 20.1894(16), b = 9.7679(5), c = 17.4930(15) A, beta = 115.66(1) degrees , and Z = 4; 2: space group P2 1/ c, a = 9.1799(7), b = 16.8797(12), c = 9.4828(7) A, beta = 90.20(1) degrees , and Z = 4; 3: space group P2 1/ n, a = 15.3641(13), b = 6.8865(4), c = 15.3902(13) A, beta = 99.19(1) degrees , and Z = 4; 4: space group C2/ c, a = 16.1496(14), b = 11.6357(7), c = 14.6784(11) A, beta = 90.40(1) degrees , and Z = 4. The structure of 1 is composed of one-dimensional (1) infinity{Nd[PS 4] 4} (9-) chains and charge balancing K (+) ions. Within the chains, eight-coordinated Nd (3+) ions, which are mixed with K (+) ions, are connected by [PS 4] (3-) tetrahedra. The crystal structures of 2 and 3 are characterized by anionic chains (1) infinity{Nd[PS 4] 2} (3-) being separated by K (+) or Cs (+) ions. Along each chain the Nd (3+) ions are bridged by [PS 4] (3-) anions. The difference between the structures of 2 and 3 is that in 2 the Nd (3+) ions are coordinated by four edge-sharing [PS 4] (3-) tetrahedra while in 3 each Nd (3+) ion is surrounded by one corner-sharing, one face-sharing, and two edge-sharing [PS 4] (3-) tetrahedra. The structure of 4 is a three-dimensional network with K (+) cations residing in tunnels running along [110] and [110]. The {Nd(1)S 8} polyhedra share common edges with four [PS 4] tetrahedra forming one-dimensional chains (1) infinity{Nd[PS 4] 2} (3-) running along [110] and [110]. The chains are linked by {Nd(2)S 8} polyhedra yielding the final three-dimensional network (3) infinity{Nd[PS 4] 2} (3-). The internal vibrations of both crystallographically independent [PS 4] (3-) anions of 2- 4 have been assigned in the range 200-650 cm (-1) by comparison of their corresponding far/mid infrared and Raman spectra (lambda exc = 488 nm) on account of locally imposed C 1 symmetry. In the Fourier-transform-Raman spectrum (lambda exc = 1064 nm) of 2- 4, very similar well-resolved electronic Raman (ER) transitions from the electronic Nd (3+) ground-state to two levels of the (4)I 9/2 ground manifold and to the six levels of the (4)I 11/2 manifold have been determined. Resonant Raman excitation via a B-term mechanism involving the (4)I 15/2 and (4)F 3/2 intermediate states may account for the significant intensity enhancement of the ER transitions with respect to the symmetric P-S stretching vibration nu 1. Broad absorptions in the UV/vis/NIR diffuse reflectance spectrum at 293 K in the range 5000-25000 cm (-1) of 2- 4 are attributed to spin-allowed excited quartet states [ (4)(I < F < S < G < D)] and spin-forbidden doublet states [ (2)(H < G < K < D < P)] of Nd (3+). A luminescense spectrum of 3 obtained at 15 K by excitation with 454.5 nm shows multiplets of narrow lines that reproduce the Nd (3+) absorptions. Sharp and intense luminescence lines are produced instead by excitation with 514.5 nm. Lines at 18681 ( (4)G 7/2), 16692 ( (4)G 5/2), 14489 ( (4)F 9/2), and 13186 cm (-1) ( (4)F 7/2) coincide with the corresponding absorptions. Hypersensitive (4)G 5/2 is split by 42 cm (-1). The most intense multiplet at about 16500 cm (-1) is assigned to the transition from (4)G 5/2 to the Stark levels of the ground manifold (4)I 9/2.     

New metalloligands [M(SC[O]Ph)(4)](-): synthesis and characterization of polymeric [A(MeCN)(x)[M(SC[O]Ph)(4)]] compounds (A = Li,Na and K; M = Ga and In; x = 0-2)

Exploiting the ability of the [M(SC[O]Ph)(4)](-) anion to behave like an anionic metalloligand, we have synthesized [Li[Ga(SC[O]Ph)(4)]] (1), [Li[In(SC[O]Ph)(4)]] (2), [Na[Ga(SC[O]Ph)(4)]] (3), [Na(MeCN)[In(SC[O]Ph)(4)]] (4), [K[Ga(SC[O]Ph)(4)]] (5), and [K(MeCN)(2)[In(SC[O]Ph)(4)]] (6) by reacting MX(3) and PhC[O]S(-)A(+) (M = Ga(III) and In(III); X = Cl(-) and NO(3)(-); and A = Li(I), Na(I), and K(I)) in the molar ratio 1:4. The structures of 2, 4, and 6 determined by X-ray crystallography indicate that they have a one-dimensional coordination polymeric structure, and structural variations may be attributed to the change in the alkali metal ion from Li(I) to Na(I) to K(I). Crystal data for 2 x 0.5MeCN x 0.25H(2)O: monoclinic space group C2/c, a = 24.5766(8) A, b = 13.2758(5) A, c = 19.9983(8) A, beta = 108.426(1) degrees, Z = 8, and V = 6190.4(4) A(3). Crystal data for 4: monoclinic space group P2(1)/c, a = 10.5774(7) A, b = 21.9723(15) A, c = 14.4196(10) A, beta = 110.121(1) degrees, Z = 4, and V = 3146.7(4) A(3). Crystal data for 6: monoclinic space group P2(1)/c, a = 12.307(3) A, b = 13.672(3) A, c = 20.575(4) A, beta = 92.356(4) degrees, Z = 4, and V = 3458.8(12) A(3). The thermal decomposition of these compounds indicated the formation of the corresponding AMS(2) materials.     

Synthesis and structure of coordination polymers of Ag(I) with isomeric (aminomethyl)pyridines. Formation of a novel circular helicate and 2-D networks via Ag...Ag contacts and coordination shell expansion under anion control

Reaction between Ag(I) salts and the three isomers of (aminomethyl)pyridines, viz., 2-amp, 3-amp, and 4-amp, lead to either discrete or polymeric (1-D and 2-D) structures influenced by anions and closed shell Ag.Ag contacts. Characterization data for Ag(2-amp)BF(4) (1) follow: monoclinic, space group C2/c, with a = 16.788(2) A, b = 11.5719(6) A, c = 11.3864(7) A, beta = 123.671(8) degrees, and Z = 8. For Ag(2)(2-amp)(3)(PF(6))(2) (2): monoclinic, space group P2(1)/a, with a = 10.029(7) A, b = 20.291(12) A, c = 13.907(6) A, beta = 95.38(5) degrees, and Z = 4. For Ag(2)(3-amp)(3)(PF(6))(2) (4): triclinic, space group P1, with a = 10.4482(7) A, b = 11.1468(9) A, c = 12.2720(11) A, alpha = 81.018(7) degrees, beta = 80.668(6) degrees, gamma = 80.977(6) degrees, and Z = 2. For Ag(4-amp)BF(4).0.75CH(3)CN (5): orthorhombic, space group C222(1), with a = 9.272(2) A, b = 16.164(12) A, c = 27.851(2) A, and Z = 8. For Ag(4-amp)PF(6) (6): monoclinic, space group P2(1)/m, with a = 5.2089(7) A, b = 14.3950(17) A, c = 7.0149(14) A, beta = 96.538(14) degrees, and Z = 2. While Ag(I) is 2-coordinate in 1, 5 and 6, it shows 3-coordination in 2 and 4. Compound 1 consists of a 1-D polymeric cation chain with interchain Ag...Ag contacts and the anions sitting on the edges of the chains. The dication in 2 is held in the form of a circular helicate by closed shell Ag...Ag interactions. Compound 4 generates a 2-D network with channels big enough to accommodate the anions. Compound 5 is a 2-D chiral network of chains connected by Ag...Ag contacts. Compound 6 shows a simple 1-D chain structure with an alternating arrangement of cationic chains and anions.     

Architectural isomerism in the three-dimensional polymeric spin crossover system [Fe(pmd)2[Ag(CN)2]2]: synthesis, structure, magnetic properties, and calorimetric studies

Two coordination polymers formulated [Fe(pmd)2[Ag(CN)2]2] (pmd = pyrimidine) have been synthesized and characterized. Both polymers, considered to be architectural isomers, display different crystal structures and magnetic properties. Isomer 1 crystallizes in the monoclinic C2/c space group with a = 6.9750(8) angstroms, b = 16.1700(9) angstroms, c = 14.2020(8) angstroms, beta = 97.954(2) degrees, V = 1586.37(14) angstroms3, and Z = 4. The crystal structure of isomer 2 has been studied at 250 and 150 K. At both temperatures, 2 displays the orthorhombic Pccn space group with a = 15.7700(2) [14.8950(2)] angstroms, b = 8.2980(4) [8.1580(4)] angstroms, c = 13.4180(6) [13.3480(5)] angstroms, V = 1755.87(14) [1621.96(10)] angstroms3, and Z = 4 for 250 [150] K. The iron(II) ions define distorted octahedral [FeN6] chromophores in both isomers. The equatorial positions are occupied by four [Ag(CN)2]- bridging ligands, which connect the defining layers of two iron(II) ions. Isomer 1 has two crystallographically distinct [Ag(CN)2]- groups; one is essentially linear, while the other is severely distorted [C(5)-Ag(2)-C(5i)] = 138.8(5) degrees. This fact facilitates the parallel interpenetration of two layers, which in addition show short Ag(1)....Ag(2) interactions (distance Ag(1)....Ag(2) = 2.9972(10) angstroms). Isomer 2 shows only one type of Ag atom, which is slightly bent [C-Ag-C = 161.54(12) degrees], and as a consequence, the layers defined are not interpenetrated. In both cases, the axial positions are occupied by the pmd ligands which interact with the Ag atoms of adjacent layers defining a 3D coordination polymer. Compound 1 is high spin in the whole range of temperatures, while 2 undergoes a cooperative high-spin <--> low-spin effect centered at ca. 184 K with a hysteresis loop ca. 5 K wide. The experimental enthalpy and entropy variations were 11.5 +/- 0.4 kJ mol(-1) and 64 +/- 3 J K(-1) mol(-1). Consistency between the experimental thermodynamic data and the magnetic data was checked in the frame of regular solution theory.     

Synthesis and characterization of new coordination polymers generated from bent bis(cyanophenyl)oxadiazole ligands and Ag(I) salts

Two new bent bis(cyanophenyl)oxadiazole ligands, 2,5-bis(4-cyanophenyl)-1,3,4-oxadiazole (L7) and 2,5-bis(3-cyanophenyl)-1,3,4-oxadiazole (L8), were synthesized. The coordination chemistry of these ligands with various Ag(I) salts has been investigated. Seven new coordination polymers, namely, {[Ag(L7)(H2O)]ClO4}n) (1) (triclinic, P1, a = 9.342(4) A, b = 9.889(4) A, c = 10.512(4) A, alpha = 68.978(6) degrees, beta = 78.217(6) degrees, gamma = 81.851(7) degrees, Z = 2), {[Ag(L7)]SO3CF3}n (2) (monoclinic, P2(1)/n, a = 7.559(2) A, b = 23.739(6) A, c = 10.426(3) A, beta = 108.071(4) degrees, Z = 4), {[Ag(L8)]BF4 x 0.5(C6H6) x H2O}n (3) (triclinic, P1, a = 7.498(3) A, b = 10.649(4) A, c = 13.673(5) A, alpha = 98.602(5) degrees, beta = 100.004(5) degrees, gamma =110.232(5) degrees, Z = 2), {[Ag(L8)SbF6] x H2O}n (4) (triclinic, P1, a = 8.2621(9) A, b = 10.6127(12) A, c = 13.3685(15) A, alpha = 98.012(2) degrees, beta = 106.259(2) degrees, gamma = 112.362(2) degrees, Z = 2), {[Ag2(L8)2(SO3CF3)] x H2O}n (5) (triclinic, P1, a = 10.713(4) A, b = 13.449(5) A, c = 15.423(5) A, alpha = 65.908(5) degrees, beta = 74.231(5) degrees, gamma = 83.255(5) degrees, Z = 2), {[Ag2(L8)(C6H6)(ClO4)] x ClO4}n (6) (monoclinic, P2(1)/n, a = 6.9681(17) A, b = 20.627(5) A, c = 17.437(4) A, beta = 95.880(4) degrees, Z = 4), and {[Ag2(L8)(H2PO4)2]}n (7) (triclinic, P1, a = 7.956(2) A, b = 9.938(3) A, c = 14.242(4) A, alpha = 106.191(4) degrees, beta = 97.322(4) degrees, gamma = 107.392(4) degrees, Z = 1), were obtained by the combination of L7 and L8 with Ag(I) salts in a benzene/methylene chloride mixed-solvent system and fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. In addition, the luminescence and electrical conductance properties of compounds 1-6 and the host-guest chemistry of compound 3 were investigated.     

CRYSTAL STRUCTURES OF [Bu4N]2[M2Ag3（ μ3—S）2（μ—S）4S2Et2dtc]（M=W,Mo）

<正> The title compounds were prepared from the reation of (NH4)2MS4 (M=W,Mo),AgNO3,NadtcEt2 and Et4NBr in CH3CN-H2O solution. The isomorphous compounds [Bu4N]2[W2Ag3S8Et2du] ( I ) and [Bu4N]2[Mo2Ag3S8Et2dtc] (Ⅱ) crystallize in triclinic space qroup Pi with the following crystal parameters:α=13. 043(4),b = 21. 640(6),c=10. 757(6)A ,α=95. 09(5),β = 91. 90(4),γ = 98. 57(3)°,Z = 2,V = 2987A3,Dc=1. 76g/cm3 for I 5;a= 12. 989(2) ,b=21. 574 (9) ,c= 10. 7/1(1) A .α= 95. 06(7), β=91. 61(4), γ=98. 52(2)°, Z = 2,V = 2961 A3.Dc= 1. 58g/cm3 for Ⅱ . The final R and Rw values are 0. 061 and 0. 072 for Ⅰ ,and 0. 062 and 0. 076 for Ⅱ The M2Ag3 (M = W, Mo) unit in anion M2Ag3S8Et2dtc forms a five-membered ring.     

Yttrium calix[4]arene complexes. Silylation and silylamine elimination reactions on model oxo surfaces

The synthesis and the spectroscopic and structural characterization of lower-rim-silylated and rare-earth-metalated calix[4]arenes are presented. Hexamethyldisilazane, HN(SiMe3)2, reacted in a selective manner with [p-tert-buttylcalix[4]arene]H4 (1) in refluxing mesitylene to give the 1,3-silylated product [p-tert-butylcalix[4]arene(SiMe3)2]H2 (2) in high yield. The molecular structure of compound 2, as revealed by X-ray crystallography, shows the pinched cone conformation of the calixarene bowl, featuring hydrogen bonding between the phenylsilyl ether and phenolic oxygen atoms (O...O, 2.838 A). From the reaction of the sterically more crowded tetraphenyldimethyldisilazane, HN(SiMePh2)2, only starting material could be recovered. In contrast, tetramethyldisilazane, HN(SiHMe2)2, afforded the tetrakis-silylated product [p-tert-butylcalix[4]arene(SiHMe2)4] (3) in hexane solution at ambient temperature. A single-crystal X-ray diffraction study of compound 3 established the 1,2-alternate conformation, which is also present in solution, as indicated by 1H NMR spectroscopy. The yttrium complex Y[N(SiHMe2)2]3(THF)2 (4) exchanged all of its silylamide ligands when treated with an equimolar amount of 1 in toluene at ambient temperature to yield compound 5, as indicated by IR and NMR spectroscopy. The molecular structure of 5 revealed a centrosymmetric dimer of composition [Y(p-tert-butylcalix[4]arene(SiHMe2)(THF)]2. Three of the deprotonated phenolic oxygen atoms of the calixarene bowl bind to the metal center, two as terminal ligands and one in a bridging mode, while the fourth undergoes in situ silylation (nu(SiH) 2127 cm-1). The distorted-trigonal-bipyramidal coordination geometry is completed by a THF molecule. Bis-silylated 2 reacted with 4 to form the heteroleptic complex (Y[p-tert-butylcalix[4]arene(SiMe3)2][N(SiHMe2)2]) (6). Crystal data: C50H72O4Si2 (2), triclinic, P1, a = 12.8914(3) A, b = 14.9270(5) A, c = 15.1652(4) A, alpha = 77.293(2) degrees, beta = 65.019(2) degrees, gamma = 72.234(2) degrees, Z = 2; C52H80O4Si4 (3), triclinic, P1, a = 10.1774(2) A, b = 14.1680(2) A, c = 18.7206(2) A, alpha = 95.8195(8) degrees, beta = 95.5294(8) degrees, gamma = 98.1098(7) degrees, Z = 2; C100H132O10Si2Y2, 2(C6H6) (5), triclinic, P1, a = 13.2625(4) A, b = 14.5894(3) A, c = 17.0458(5) A, alpha = 65.0986(14) degrees, beta = 77.8786(8) degrees, gamma = 85.5125(13) degrees, Z = 1.     

Trimerization of alkali dicyanamides M[N(CN)2] and formation of tricyanomelaminates M3[C6N9] (M = K, Rb) in the melt: crystal structure determination of three polymorphs of K[N(CN)2], two of Rb[N(CN)2], and one of K3[C6N9] and Rb3[C6N9] from X-ray powder diffractometry

The alkali dicyanamides M[N(CN)2] (M=K, Rb) were synthesized through ion exchange, and the corresponding tricyanomelaminates M3[C6N9] were obtained by heating the respective dicyanamides. The thermal behavior of the dicyanamides and their reaction to form the tricyanomelaminates were investigated by temperature-dependent X-ray powder diffractometry and thermoanalytical measurements. Potassium dicyanamide K[N(CN)2] was found to undergo four phase transitions: At 136 degrees C the low-temperature modification alpha-K[N(CN)2] transforms to beta-K[N(CN)2], and at 187degrees C the latter transforms to the high-temperature modification gamma-K[N(CN)2], which melts at 232 degrees C. Above 310 degrees C the dicyanamide ions [N(CN)2]- trimerize and the resulting tricyanomelaminate K3[C6N9] solidifies. Two modifications of rubidium dicyanamide have been identified: Even at -25 degrees C, the a form slowly transforms to beta-Rb[N(CN)2] within weeks. Rb[N(CN)2] has a melting point of 190 degrees C. Above 260 degrees C the dicyanamide ions [N(CN)2]- of the rubidium salt trimerize in the melt and the tricyanomelaminate Rb3[C6N9] solidifies. The crystal structures of all phases were determined by powder diffraction methods and were refined by the Rietveld method. alpha-K[N(CN)2] (Pbcm, a = 836.52(1), b = 46.90(1), c =7 21.27(1) pm, Z = 4), gamma-K[N(CN)2] (Pnma, a = 855.40(3), b = 387.80(1), 1252.73(4) pm, Z = 4), and Rb[N(CN)2] (C2/c, a = 1381.56(2), b = 1000.02(1), c = 1443.28(2) pm, 116.8963(6) degrees, Z = 16) represent new structure types. The crystal structure of beta-K[N(CN)2] (P2(1/n), a = -726.92(1), b 1596.34(2), c = 387.037(5) pm, 111.8782(6) degrees, Z = 4) is similar but not isotypic to the structure of alpha Na[N(CN)2]. alpha-Rb[N(CN)2] (Pbcm, a = 856.09(1), b = 661.711(7), c = 765.067(9) pm, Z = 4) is isotypic with alpha-K[N(CN)2]. The alkali dicyanamides contain the bent planar anion [N(CN)2]- of approximate symmetry C2, (average bond lengths: C-N(bridge) 133, C-N(term) 113 pm; average angles N-C-N 170 degrees, C-N-C 120 degrees). K3[C6N9] (P2(1/c), a = 373.82(1), b = 1192.48(5), c = 2500.4(1) pm, beta = 101.406(3) degrees, Z = 4) and Rb,[C6N9] (P2(1/c), a = 389.93(2), b = 1226.06(6), c = 2547.5(1) pm, 98.741(5) degrees, Z=4) are isotypic and they contain the planar cyclic anion [C6N9]3-. Although structurally related, Na3[C6N9] is not isotypic with the tricyanomelaminates M3[C6N9] (M = K, Rb).     

STRUCTURE STUDIES OF [Et_4N]_4[Cu_8(i-mnt)_6] (i-mnt=S_2C=C(CN)_2) AND [Me_4N]_4[Cu_5Ag_3(i-mnt)_6]·H_2O

<正> [Me4N]6[Ag6(i-mnt)6].H2O(1),[Et4N]4[Cu8(i-mnt)6](2) and [Me4N]4-[Cu5Ag3(i-mnt)6].H2O(3)(i-mnt=S2C=C(CN)2) were synthesized. The crystal and molecular structure of the complex 1 was reported by us.The structure of the complex 2 was determined from single crystal X-ray diffraction data. [Et4N]4[Cu8(i-mnt)s] 2, Mr=1870.46, monoclinic, P21/n, a=14.724(6), b = 17.228(3), c=15.59(1)A,β= 100.75(7)°,V=3886.3A3;Z = 2,Dc= 1.598 g/cm3. Complex 3 has been characterized by ICP elemental analyses and IR spectrum.     

Oxidative addition of small molecules to a dinuclear Au(I) amidinate complex, Au2[(2,6-Me2Ph)2N2CH]2. Syntheses and characterization of Au(II) amidinate complexes including one which possesses Au(II)-oxygen bonds

The dinuclear Au(I) amidinate complex Au2(2,6-Me2Ph-form)2 (1) is isolated in quantitative yield by the reaction of (THT)AuCl and the potassium salt of 2,6-Me2Ph-form in a 1:1 stoichiometric ratio. Various reagents such as Cl2, Br2, I2, CH3I, and benzoyl peroxide add to the dinuclear Au(I)amidinate complex Au2(2,6-Me2Ph-form)2 to form oxidative-addition Au(II) metal-metal-bonded complexes 2, 3, 4, 5, and 6. The Au(II) amidinate complexes are stable as solids at room temperature. The structures of the dinuclear Au2(2,6-Me2Ph-form)2 and the Au(II) oxidative-addition products Au2(2,6-Me2Ph-form)2X2, X=Cl, Br, I, are reported. Crystalline products with an equal amount of oxidized and unoxidized complexes in the same unit cell, [Au2(2,6-Me2Ph-form)2X2][Au2(2,6-Me2Ph-form)2], X=Cl, 2m, or Br, 3m, are isolated and their structures are presented. The structure of [Au2(2,6-Me2Ph-form)2X2][Au2(2,6-Me2Ph-form)2], X=Cl has a Au(II)-Au(II) distance slightly longer, 0.05A, than that observed in the fully oxidized product Au2(2,6-Me2-form)2Cl2, 2. The gold-gold distance in the dinuclear complex decreases upon oxidative addition with halogens from 2.7 to 2.5 A, similar to observations made with the Au(I) dithiolates and ylides. The oxidative addition of benzoyl peroxide leads to the isolation of the first stable dinuclear Au(II) nitrogen complex possessing Au-O bonds, Au2(2,6-Me2Ph-form)2(PhCOO)2, 6, with the shortest Au-Au distance known for Au(II) amidinate complexes, 2.48 A. The structure consists of unidentate benzoate units linked through oxygen to the Au(II) centers. The replacement of the bromide in 3 by chloride, and the benzoate groups in 6 by chloride or bromide also occurs readily. The unit cell dimensions are, for 1, a=7.354(6) A, b=9.661(7) A, c=11.421(10) A, alpha=81.74(5) degrees, beta=71.23(5) degrees, and gamma=86.07(9) degrees (space group P, Z=1), for 2.1.5C6H12, a=11.012(2) A, b=18.464(4) A, c=19.467(4) A, alpha=90 degrees, beta=94.86(3) degrees, and gamma=90 degrees (space group P21/c, Z=4), for 2m.ClCH2CH2Cl, a=16.597(3) A, b=10.606(2) A, c=19.809(3) A, alpha=90 degrees, beta=94.155(6) degrees, and gamma=90 degrees (space group P21/n, Z=2), for 3m, a=16.967(3) A, b=10.783(2) A, c=20.060(4) A, alpha=90 degrees, beta=93.77(3) degrees, and gamma=90 degrees (space group P21/n, Z=2), for 4.THF, a=8.0611(12) A, b=10.956(16) A, c=11.352(17) A, alpha=84.815(2) degrees, beta=78.352(2) degrees, and gamma=88.577(2) degrees (space group P, Z=1), for 5, a=16.688 A, b=10.672(4) A, c=19.953(7) A, alpha=90.00 (6) degrees, beta=94.565(7) degrees, and gamma=90.00 degrees (space group P21/n, Z=4), for 6.0.5C7H8, a=11.160(3) A, b=12.112(3) A, c=12.364(3) A, alpha=115.168(4) degrees, beta=161.112(4) degrees, and gamma=106.253(5) degrees (space group P, Z=1).