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.     

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.     

Coordination polymers and hybrid networks of different dimensionalities formed by metal sulfites

In our effort to explore the use of the sulfite ion to design hybrid and open-framework materials, we have been able to prepare, under hydrothermal conditions, zero-dimensional [Zn(C12H8N2)(SO3)].2H2O, I (a = 7.5737(5) A, b = 10.3969(6) A, c = 10.3986(6) A, alpha = 64.172(1) degrees , beta = 69.395(1) degrees , gamma = 79.333(1) degrees , Z = 2, and space group P), one-dimensional [Zn2(C12H8N2)(SO3)2(H2O)], II (a = 8.0247(3) A, b = 9.4962(3) A, c = 10.2740(2) A, alpha = 81.070(1) degrees , beta = 80.438(1) degrees , gamma = 75.66(5) degrees , Z = 2, and space group P), two-dimensional [Zn2(C10H8N2)(SO3)2].H2O, III (a = 16.6062(1) A, b = 4.7935(1) A, c = 19.2721(5) A, beta = 100.674(2) degrees , Z = 4, and space group C2/c), and three-dimensional [Zn4(C6H12N2)(SO3)4(H2O)4], IV (a = 11.0793(3) A, c = 8.8246(3) A, Z = 2, and space group P42nm), of which the last three are coordination polymers. A hybrid open-framework sulfite-sulfate of the composition [C2H10N2][Nd(SO3)(SO4)(H2O)]2, V (a = 9.0880(3) A, b = 6.9429(2) A, c = 13.0805(5) A, beta = 91.551(2) degrees , Z = 2, and space group P21/c), with a layered structure containing metal-oxygen-metal bonds has also been described.     

New amine-templated zinc phosphates with a temperature-induced increase of structural dimensionality

Three new amine-templated zinc phosphates, [C4N2H14][Zn(HPO4)2].H2O, AU-I, [C4N2H14][Zn2(H(0.5)PO4)2(H2PO4)], AU-II, and [C4N2H14][Zn5(H2O)(PO4)4], AU-III, are prepared by hydrothermal synthesis using an organic amine, N,N'-dimethylethylendiamine CH3NHCH2CH2NHCH3, as structure-directing agent. The three materials are prepared from the same reaction mixture, 1Zn(CH3CO2)2:3.05H3PO4:2.25CH3NHCH2CH2NHCH3:138H2O (pH = 5.1), AU-I at RT, AU-II at 60 degrees C, and AU-III at 170 degrees C. The materials are built from corner-sharing ZnO4 and PO4 tetrahedra forming chains, layers, or framework structures for AU-I to III, respectively, and are linked together by hydrogen bonds via the diprotonated amine ions. The complete hydrogen-bond scheme is resolved for these new compounds and reveals some interesting phenomena, for example, a hydrogen shared between two phosphate groups in AU-II, thereby forming H(0.5)PO4 groups. Furthermore, the water molecules are different; that is, in AU-I they act as hydrogen-bond donor and acceptor, whereas they act as ligand in AU-III with coordination to Zn. The structures of the compounds are determined by single-crystal X-ray diffraction analysis. AU-I, [C4N2H14][Zn(HPO4)2].H2O, crystallizes in the triclinic space group P-1, a = 8.215(2), b = 8.810(3), c = 8.861(3) A, alpha = 88.001(4) degrees , beta = 89.818(5) degrees , and gamma = 89.773(5) degrees , Z = 2. AU-II, [C4N2H14][Zn2(H(0.5)PO4)2(H2PO4)], is monoclinic, P2/n, a = 11.7877(4), b = 5.2093(2), c = 12.2031(4) A, beta = 98.198(1) degrees , Z = 2. AU-III, [C4N2H14][Zn5(H2O)(PO4)4], crystallizes in the orthorhombic space group Pna2(1) with lattice parameters, a = 20.723(2), b = 5.2095(6), c = 17.874(2) A, Z = 4. The phase stability investigated by systematic hydrothermal synthesis is presented, and the materials are further characterized by 31P solid-state MAS NMR, for example, by determination of 31P chemical shift anisotropies for AU-III, while the thermal behavior is investigated by thermogravimetry (TG).     

Synthesis,structural and spectroscopic properties of two new ethylenediamine-templated gallophosphate-oxalate layered materials

Two new layered gallophosphate-oxalate materials have been prepared hydrothermally using ethylenediamine and oxalic acid as structure-directing agents. The compounds (C2N2H10)2[Ga2(C2O4)2(HPO4)3].H2O 1 and (C2N2H10)3- [Ga4(C2O4)4(HPO4)4(H2PO4)2] 2 are closely related, consisting of anionic double chains built of alternating paris of GaO6 and HPO4 polyhedra. These double chains are linked via bridging HPO4 or H2PO4 tetrahedra to form corrugated layers containing eight-membered rings. The oxalate group acts as a bidentate ligand to each of the GaO6 octahedron. The corrugated layers are held together by strong to weak hydrogen-bonding interactions between oxalate groups, water and diprotonated ethylenediamine molecules, and the framework components. The compounds were characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and infrared and Raman spectroscopy. Crystal data for 1: monoclinic, space group P21/C (No. 14), a = 6.355(1) A, b = 39.362(8) A, c = 9.249(2) A, beta = 106.7(1) degrees, Z = 2. Crystal data for 2: triclinic, space group P1 (No. 2), a = 8.730(1) A, b = 11.575(1) A, c = 11.696(1) A, alpha = 115.12(1) degree, beta = 90.07(1) degree, gamma = 111.23(1) degree, Z = 2.     

Preparation, characterization, and X-ray crystal structures of helical and syndiotactic zinc-based coordination polymers

The reactions of (facac)2Zn.2H2O (facac = 1,1,1,5,5,5-hexafluoroacetylacetonate) with 2,5-bis(4-ethynylpyridyl)furan (1) and 1,2-bis(4-ethynylpyridyl)benzene (2) yield, upon crystallization, coordination polymers. The former polymer, ((facac)2Zn.1)n, has an isotactic, helical structure in the solid state [monoclinic space group P2(1)/n; a = 11.0374(3) A, b = 24.2179(10) A, c = 14.3970(4) A, beta = 92.880(2) degrees; Z = 4]. The latter polymer, ((facac)2Zn.2)n, adopts a syndiotactic structure in the solid state [monoclinic space group P2(1)/n; a = 9.1344(1) A, b = 21.7985(5) A, c = 16.0322(4) A, beta = 99.6680(11) degrees; Z = 4]. The solution structures of the corresponding oligomers have been studied by low-temperature 1H and 19F NMR spectroscopy. Chiral polymers were prepared using the fragment [(+)-tfc]2Zn ((+)-tfc = 3-((trifluoromethyl)hydroxymethylene)-(+)-camphorate). A linear, zigzag structure was found for ([(+)-tfc]2Zn.1)n [triclinic space group P1; a = 7.4833(2) A, b = 14.1563(5) A, c = 21.21230(5) A, alpha = 78.4440(15) degrees, beta = 81.5644(15) degrees, gamma = 76.4976(13) degrees; Z = 1]. Reaction with tris(4-pyridyl)methanol (3) yielded a homochiral, helical polymer, ([(+)-tfc]2Zn.3)n [monoclinic space group C2; a = 25.0633(12) A, b = 11.8768(7) A, c = 17.1205(9) A, alpha = 90 degrees, beta = 117.954(3) degrees, gamma = 90 degrees; Z = 4].     

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.     

Novel examples of high-dimensional mixed-valence copper cyanide complexes

The first examples of high-dimensional mixed-valence homometallic cyano-bridged copper complexes were synthesized and characterized: net-structured [Cu(CN)(4){Cu(cyclam)}(1.5)](2)(n)()(H(2)O)(5)(n) (1), ladder-type double-chain-structured [Cu(CN)(2){Cu(CN)(2)Cu(cyclam)}](n)()(H(2)O)(n) (2), layer-structured [{Cu(CN)(2)}(2)Cu(cycalm)](n) (3), and hydrogen-bond-based 2-D [Cu(CN)(3)Cu(cyclam)](n)()(CH(3)OH)(n) (4) (cyclam = 1,4,8,11-tetraazacyclotetradecane). (1) Crystallizes in triclinic space group P with a = 8.3589(11) A, b = 13.478(2) A, c = 14.828(2) A, alpha = 66.895(2) degrees , beta = 77.916(3) degrees , gamma = 85.939(3) degrees , and Z = 1; (2) crystallizes in triclinic space group P with a = 8.2305(12) A, b = 9.8861(15) A, c = 13.219(2) A, alpha = 84.863(3) degrees , beta = 75.744(3) degrees , gamma = 89.818(3) degrees , and Z = 2; 3 crystallizes in monoclinic space group P2(1)/c with a = 6.830(2) A, b = 8.482(2) A, c = 17.306(4) A, beta = 98.144(4) degrees , and Z = 2; 4 crystallizes in triclinic space group P with a = 9.470(1) A, b = 10.034(1) A, c = 12.064(1) A, alpha = 67.325(2), beta = 75.593(2), gamma = 70.672(2), and Z = 2. The coordination sphere of Cu(I) sites in the complexes shows diverse structures: tetrahedral [CuC(4)] for (1), tetrahedral [CuC(3)N] and triangular [CuC(2)N] for (2), triangular [CuC(2)N] for (3), and triangular [CuC(3)] for 4. In particular, (1) constitutes the first example of a structurally characterized system containing a bridging tetrahedral [Cu(CN)(4)](3)(-) unit. The diverse structural nature of these complexes is governed by the capping amines and the content of water in the reaction media. The magnetic interactions are negligible in these mixed-valence complexes.     

Three-dimensional open-framework cobalt(II) phosphates by novel routes

Two new three-dimensional open-framework cobalt phosphates, [C2N2H10]2[Co4(PO4)4]H2O, I, and [C4N3H16]3-[Co6(PO4)5(HPO4)3]H2O, II, have been prepared by the reaction of amine phosphates with Co2+ salts. I could also be prepared by the reaction of the cobalt tris amine complex with H3PO4. The crystal data for I and II are as follows: phosphate I, orthorhombic, space group P2(1)2(1)2(1) (no. 19), a = 10.277 (1) A, b = 10.302 (1) A, c = 18.836 (1) A, V = 1994.2 (2) A3, Z = 4; phosphate II, monoclinic, space group P2(1)/c (No. 14), a = 31.950 (1) A, b = 8.360 (1) A, c = 15.920 (1) A, beta = 96.6 (1) degrees V = 4223.4 (2) A3, Z = 4. The structures of both I and II are constructed from alternating CoO4 and PO4 tetrahedra. The connectivity leads to the formation of eight-membered channels in all the crystallographic directions resembling the aluminosilicate zeolite, merlinoite in the case of I and to a rather large, one-dimensional 16-membered channel in II. Strong hydrogen-bond interactions involving the amine and framework oxygen are present in both I and II.     

Synthesis and characterization of diverse coordination polymers. Linear and zigzag chains involving their structural transformation via intermolecular hydrogen-bonded, interpenetrating ladders polycatenane, and noninterpenetrating square grid from long, rigid N,N'-bidentate ligands: 1,4-bis[(x-pyridyl)ethynyl]benzene (x = 3 and 4)

The long, rigid ligands 1,4-bis[(3-pyridyl)ethynyl]benzene (L1) and 1,4-bis[(4-pyridyl)ethynyl]benzene (L2) were used in the synthesis of 10 new organic-inorganic coordination frameworks, each of them adopting different structural motifs. Synthesis, single-crystal X-ray structure determination, and spectroscopic and thermogravimetric analyses are presented. The reactions between M(NO3)2 x xH2O; M = Cd(II), Cu(II), and Co(II); x = 3-6 and Cu(hfac)2 x H2O [hfac = bis(hexafluoroacetylacetonato)] with L1 afforded the following one-dimensional zigzag chain structures: [Cd(C20H12N2)0.5(NO3)(CH3OH)]n (1, monoclinic, C2/c; a = 7.586(1) A, b = 23.222(1) A, c = 13.572(1) A, beta = 92.824(1), Z = 4); [{Cu(C20H12N2)(NO3)2(CH3OH)} x CH3OH]n (2, orthorhombic, P2(1)2(1)2(1); a = 8.589(1) A, b = 15.766(1) A, c = 17.501(1) A, Z = 4); [Co(C20H12N2)2(NO3)2(H2O)2] (5, triclinic, P1; a = 7.493(1) A, b = 8.948(1) A, c = 14.854(1) A, alpha = 100.427(1), beta = 97.324(1), gamma = 110.901(1), Z = 1); [Cu(C20H12N2)(hfac)2]n (4, monoclinic, C2/c, a = 18.828(1) A, b = 14.671(1) A, c = 13.427(1) A, beta = 90.447(1) degrees, Z = 4). Moreover, the minority phase compound formed from Cu(NO3)2 x 3H2O and L1 yielded a metallocyclic chain structure, [Cu(C20H12N2)(NO3)]n (3, triclinic, P; a = 8.728(1) A, b = 10.018(1) A, c = 11.893(1) A, alpha = 109.991(1), beta = 97.109(1), gamma = 115.542(1), Z = 1). In addition to the dinuclear coordination complex 5, all other polymeric structures (1-4) from L1 are composed of interpenetrating 2D and 3D cross-linked zigzag chains via hydrogen-bonding interactions. The reactions between M(NO3)2 x xH2O; M = Cd(II), Cu(II), and Co(II); x = 3-6 and Cu(hfac)2 x H2O [hfac = bis(hexafluoroacetylacetonato)] and L2 were dependent on the nature of the metal center and resulted in the formation of four different interpenetrating and noninterpenetrating compounds (6-10): [Co(C20H12N2)1.5(NO3)2]n (6, triclinic, P; a = 14.172(1) A, b = 15.795(1) A, c = 18.072(1) A, alpha = 115.380(1), beta = 101.319(1), gamma = 93.427(2), Z = 4), which consists of T-shaped building blocks assembled into three-dimensional interpenetrating polycatenated ladders; [Cd(C20H12N2)2(NO3)2]n (7, monoclinic, I2/a; a = 11.371(1) A, b = 20.311(2) A, c = 15.240(2) A, beta = 100.201(2) degrees, Z = 4), which adopts a two-dimensional noninterpenetrating square-grid motif; [Cu(C20H12N2)(hfac)2]n (8, monoclinic, I2/a; a = 11.371(1) A, b = 20.311(2) A, c = 15.240(2) A, beta = 100.201(2) degrees, Z = 4), composed of three sets of distinct one-dimensional linear chains; [Cu(C20H12N2)(EtOH)(NO3)2] [Cu(C20H12N2)1.5(NO3)2] x 2EtOH (9, triclinic, P; a = 12.248(2) A, b = 13.711(3) A, c = 18.257(4) A, alpha = 108.078(4) degrees, beta = 97.890(4) degrees, gamma = 103.139(5) degrees, Z = 2) and [Cu(C20H12N2)(MeOH)(NO3)2] [Cu(C20H12N2)1.5(NO3)2] x 2MeOH (10, triclinic, P; a = 12.136(1) A, b = 13.738(2) A, c = 17.563(3) A, alpha = 107.663(3) degrees, beta = 94.805(4) degrees, gamma = 104.021(4) degrees, Z = 2). Both 9 and 10 stack into infinite interpenetrating ladders through bundles of infinite chains and are described in our preliminary communication.     

Hydro/solvothermal synthesis and structures of new zinc phosphates of varying dimensionality

Hydro/solvothermal reactions of ZnO, HCl, H(3)PO(4), 1,4-diazacycleheptane (homopiperazine), and H(2)O under a variety of conditions yielded three new organic-inorganic hybrid materials, [C(5)N(2)H(14)][Zn(HPO(4))(2)].xH(2)O (x = approximately 0.46), I, [C(5)N(2)H(14)][Zn(3)(H(2)O)(PO(4))(2)(HPO(4))], II, and [C(5)N(2)H(14)][Zn(2)(HPO(4))(3)].H(2)O, III. While I has a one-dimensional structure, II possesses a two-dimensional layered structure, and III has a three-dimensional structure closely related to the ABW zeolitic architecture. All the compounds consist of vertex linking of ZnO(4), PO(4), and HPO(4) tetrahedral units. The fundamental building unit, single four-membered ring (S4R), is present in all the cases, and the observed differences in their structures result from variations in the connectivity between the S4R units. Thus I has a corner-shared S4R forming an infinite one-dimensional chain, II has two corner-shared chains fused through a 3-coordinated oxygen atom forming a strip and a layer with eight-membered apertures, and III has S4R units connected via oxygen atoms to give rise to channels bound by eight T atoms (T = Zn, P) in all crystallographic directions. Crystal data: I, monoclinic, space group = P2(1)/n (No. 14), a = 8.6053(3) A, b = 13.7129(5) A, c = 10.8184(4) A, beta = 97.946(1) degrees, V = 1264.35(8) A(3), Z = 4; II, monoclinic, space group = P2(1)/c (No. 14), a = 11.1029(1) A, b = 17.5531(4) A, c = 8.2651(2) A, beta = 97.922(2) degrees, V = 1595.42(5) A(3), Z = 4; III, monoclinic, space group = P2(1) (No. 4), a = 8.0310(2) A, b = 10.2475(3) A, c = 10.570(3) A, beta = 109.651(1) degrees, V = 819.24(3) A(3), Z = 2.     

Copper(I) complexes, copper(I)/O(2) reactivity, and copper(II) complex adducts, with a series of tetradentate tripyridylalkylamine tripodal ligands

Copper(I) and copper(II) complexes possessing a series of related ligands with pyridyl-containing donors have been investigated. The ligands are tris(2-pyridylmethyl)amine (tmpa), bis[(2-pyridyl)methyl]-2-(2-pyridyl)ethylamine (pmea), bis[2-(2-pyridyl)ethyl]-(2-pyridyl)methylamine (pmap), and tris[2-(2-pyridyl)ethyl]amine (tepa). The crystal structures of the protonated ligand H(tepa)ClO(4), the copper(I) complexes [Cu(pmea)]PF(6) (1b-PF(6)), [Cu(pmap)]PF(6) (1c-PF(6)), and copper(II) complexes [Cu(pmea)Cl]ClO(4).H(2)O (2b-ClO(4).H(2)O), [Cu(pmap)Cl]ClO(4).H(2)O (2c-ClO(4).H(2)O), [Cu(pmap)Cl]ClO(4) (2c-ClO(4)), and [Cu(pmea)F](2)(PF(6))(2) (3b-PF(6)) were determined. Crystal data: H(tepa)ClO(4), formula C(21)H(25)ClN(4)O(4), triclinic space group P1, Z = 2, a = 10.386(2) A, b = 10.723(2) A, c = 11.663(2) A, alpha = 108.77(3) degrees, beta = 113.81(3) degrees, gamma = 90.39(3) degrees; 1b-PF(6), formula C(19)H(20)CuF(6)N(4)P, orthorhombic space group Pbca, Z = 8, a = 14.413(3) A, b = 16.043(3) A, c = 18.288(4) A, alpha = beta = gamma = 90 degrees; (1c-PF(6)), formula C(20)H(22)CuF(6)N(4)P, orthorhombic space group Pbca, Z = 8, a = 13.306(3) A, b = 16.936(3) A, c = 19.163(4) A, alpha = beta = gamma = 90 degrees; 2b-ClO(4).H(2)O, formula C(19)H(22)Cl(2)CuN(4)O(5), triclinic space group P1, Z = 4, a = 11.967(2) A, b = 12.445(3) A, c = 15.668(3) A, alpha = 84.65(3) degrees, beta = 68.57(3) degrees, gamma = 87.33(3) degrees; 2c-ClO(4).H(2)O, formula C(20)H(24)Cl(2)CuN(4)O(5), monoclinic space group P2(1)/c, Z = 4, a = 11.2927(5) A, b = 13.2389(4) A, c = 15.0939(8) A, alpha = gamma = 90 degrees, beta = 97.397(2) degrees; 2c-ClO(4), formula C(20)H(22)Cl(2)CuN(4)O(4), monoclinic space group P2(1)/c, Z = 4, a = 8.7682(4) A, b = 18.4968(10) A, c = 13.2575(8) A, alpha = gamma = 90 degrees, beta = 94.219(4) degrees; 3b-PF(6), formula [C(19)H(20)CuF(7)N(4)P](2), monoclinic space group P2(1)/n, Z = 2, a = 11.620(5) A, b = 12.752(5) A, c = 15.424(6) A, alpha = gamma = 90 degrees, beta = 109.56(3) degrees. The oxidation of the copper(I) complexes with dioxygen was studied. [Cu(tmpa)(CH(3)CN)](+) (1a) reacts with dioxygen to form a dinuclear peroxo complex that is stable at low temperatures. In contrast, only a very labile peroxo complex was observed spectroscopically when 1b was reacted with dioxygen at low temperatures using stopped-flow kinetic techniques. No dioxygen adduct was detected spectroscopically during the oxidation of 1c, and 1d was found to be unreactive toward dioxygen. Reaction of dioxygen with 1a-PF(6), 1b-PF(6), and 1c-PF(6) at ambient temperatures leads to fluoride-bridged dinuclear copper(II) complexes as products. All copper(II) complexes were characterized by UV-vis, EPR, and electrochemical measurements. The results manifest the dramatic effects of ligand variations and particularly chelate ring size on structure and reactivity.     

Complementarity and countercomplementarity in polynuclear copper(II) complexes with R2NCH2CH(OH)CH2NR2 (R = H, CH3): crystal structures and magnetic study

The syntheses, structural characterization and magnetic behavior of five new copper(II) polynuclear compounds with formulae [Cu4(mu2-CH3COO)2(mu-bdmap)2(micro(1,5)-dca)2(dca)2(H2O)2] 1, [Cu2(mu2-CH3COO)(mu-bdap)(mu(1,1,5)-dca)(mu(1,3)-dca)]n 2, [Cu4(mu2-CH3COO)2(mu-bdmap)2(mu(1,1)-NCS)2(NCS)2] 3, [Cu2(mu2-CH3COO)(mu-bdap)(NCS)2] 4 and [Cu2(mu(1,3)-N3)(mu-bdmap)(N3)2]n 5 in which bdmapH is 1,3-bis(dimethylamino)-2-propanol, bdapH is 1,3-bis(amino)-2-propanol and dca is the anionic dicyanamide ligand, are reported herein. Tetranuclear complex 1 crystallizes in the monoclinic system, space group P2(1)/n, with unit cell parameters a = 8.284(8), b = 21.52(1), c = 11.432(3) A, beta = 105.19(2) degrees , Z = 2. Bi-dimensional complex 2 crystallizes in the triclinic system, space group P1, with unit cell parameters a = 8.184(5), b = 8.792(2), c = 10.887(2) A, alpha = 75.65(2), beta = 76.55(3), gamma = 74.36(3) degrees , Z = 2. Tetranuclear complex 3 crystallizes in the triclinic system, space group P1, with unit cell parameters a = 8.455(4), b = 9.114(9), c = 12.744(8) A, alpha = 104.62(8), beta = 99.86(6), gamma = 106.10(8) degrees, Z = 1. Dinuclear complex 4 crystallizes in the triclinic system, space group P1, with unit cell parameters a = 8.15(1), b = 8.18(2), c = 11.44(1) A, alpha = 69.39(2), beta = 80.36(2), gamma = 80.37(2) degrees , Z = 2. One-dimensional complex 5 crystallizes in the orthorhombic system, space group P2(1)2(1)2(1), with unit cell parameters a = 20.45(4), b = 11.36(3), c = 6.43(1) A, Z = 4. The magnetic behavior of all the complexes has been checked giving a bulk antiferromagnetic coupling in all the cases with |J| values in the range 109-144 cm(-1) for 1-4. Compound 5 is diamagnetic in the 2-300 K range of temperatures. The found J values 1-5 for can be justified from the structural data taking into account the orbital countercomplementarity for 1-4 and the orbital complementarity for 5.     

Syntheses and structures of two low-dimensional beryllium phosphate compounds: [C5H14N2]2[Be3(HPO4)5].H2O and [C6H18N2]0.5[Be2(PO4)(HPO4)OH].0.5H2O

The first two low-dimensional beryllium phosphates, [C5H14N2]2[Be3(HPO4)5].H2O (BePO-CJ29) and [C6H18N2]0.5[Be2(PO4)(HPO4)OH].0.5 H2O (BePO-CJ30), have been successfully synthesized under mild hydrothermal/solvothermal conditions. BePO-CJ29 is built up from strict alternation of BeO4 and HPO4 tetrahedra forming a unique one-dimensional double chains with 12-ring apertures. There are pseudo-10-ring apertures enclosed by two double chains through H-bonds. BePO-CJ29 can also be viewed as a pseudo 2-D layered structure stabilized by strong H-bonds. The diprotonated 2-methylpiperazium cations are located at three positions (i.e., inside the 12-ring aperture, inside the pseudo-10-ring aperture, and in the interlayer of the inorganic pseudo-layers. BePO-CJ30 is constructed by the alternation of Be-centered tetrahedra (including BeO4 and HBeO4) and P-centered tetrahedra (including PO4 and HPO4) resulting in a two-dimensional layered structure parallel to the (0 1 1) direction. The complex layer is composed of coupled 4.8 net sheets. The diprotonated 1,6-hexandiamine cations and water molecules reside in the interlayer regions and interact with the inorganic layers through H-bonds. Crystal data are as follows: [C5H14N2]2[Be3(HPO4)5].H2O (BePO-CJ29), triclinic, P1 (No. 2), a = 8.1000(9) A, b = 8.4841(14) A, c = 19.665(2) A, alpha = 89.683(10) degrees, beta = 78.182(8) degrees, gamma = 87.932(9) degrees, V = 1321.9(3) A3, Z = 2, R1 = 0.0523 (I > 2sigma(I)), and wR2 = 0.1643 (all data); [C6H18N2]0.5[Be2(PO4)(HPO4)OH].0.5 H2O (BePO-CJ30), orthorhombic, Pccn (No. 56), a = 26.01(4) A, b = 8.431(12) A, c = 9.598(13) A, V = 2105(5) A3, Z = 8, R1 = 0.0833 (I > 2sigma(I)), and wR2 = 0.2278 (all data).     

Zinc diphosphonates templated by organic amines: syntheses and characterizations of [NH3(CH2)2NH3]Zn(hedpH2)2*2H2O and [NH3(CH2)nNH3(CH2)nNH3]Zn2(hedpH)2*2H2O (n=4,5,6) (hedp=1-hydroxyethylidenediphophonate)

Four new zinc diphosphonate compounds with formulas [NH(3)(CH(2))(2)NH(3)]Zn(hedpH(2))(2).2H(2)O, 1, [NH(3)(CH(2))(n)()NH(3)]Zn(2)(hedpH)(2).2H(2)O, (n = 4, 2; n = 5, 3; n = 6, 4) (hedp = 1-hydroxyethylidenediphosphonate) have been synthesized under hydrothermal conditions at 110 degrees C and in the presence of alkylenediamines NH(2)(CH(2))(n)()NH(2) (n = 2, 4, 5, 6). Crystallographic data for 1: monoclinic, space group C2/c, a = 24.7422(15), b = 5.2889(2), c = 16.0338(2) A, beta = 117.903(1) degrees, V = 1856.17(18) A(3), Z = 4; 2: monoclinic, space group P2(1)/n, a = 5.4970(3), b = 12.1041(6), c = 16.2814(12) A, beta = 98.619(5) degrees, V = 1071.07(11) A(3), Z = 2; 3: monoclinic, space group P2(1)/n, a = 5.5251(2), b = 12.5968(3), c = 16.1705(5) A, beta = 99.182(1) degrees, V = 1111.02(6) A(3), Z = 2; 4: triclinic, space group P-1, a = 5.4785(2), b = 14.1940(5), c = 16.0682(6) A, alpha = 81.982(2) degrees, beta = 89.435(2) degrees, gamma = 79.679(2) degrees, V = 1217.11(8) A(3), Z = 2. In compound 1, two of the phosphonate oxygens are protonated. The metal ions are bridged by the hedpH(2)(2-) groups through three of the remaining four phosphonate oxygens, forming a one-dimensional infinite chain. The protonated ethylenediamines locate between the chains in the lattice. In compounds 2-4, only one phosphonate oxygen is protonated. Compounds 2 and 3 have a similar three-dimensional open-network structure composed of [Zn(2)(hedpH)(2)](n) double chains with strong hydrogen bonding interactions between them, thus generating channels along the [100] direction. The protonated diamines and water molecules reside in the channels. Compound 4 contains two types of [Zn(2)(hedpH)(2)](n) double chains which are held together by strong hydrogen bonds, forming a two-dimensional network. The interlayer spaces are occupied by the [NH(3)(CH(2))(6)NH(3)](2+) cations and water molecules. The significant difference between structures 2-4 is also featured by the coordination geometries of the zinc atoms. The geometries of those in 2 can be described as distorted octahedral, and those in 3 as distorted square pyramidal. In 4, two independent zinc atoms are found, each with a distorted octahedral and a tetrahedral geometry, respectively.     

Octanuclear zinc(II) and cobalt(II) clusters produced by cooperative tetrameric assembling of oxime chelate ligands

We have synthesized an octanuclear zinc(II) cluster [L4Zn8(H2O)3] by the complexation of 3-hydroxysalamo (H4L) with zinc(II) acetate. The complex crystallizes in the triclinic system, space group P, with unit cell parameters a = 18.233(10) A, b = 20.518(11) A, c = 21.366(11) A, alpha = 98.7557(2) degrees, beta = 99.191(11) degrees, gamma = 108.309(10) degrees, and Z = 4. The crystallographic analysis revealed the S4 symmetrical assembling of four ligands and that the tetrameric complex has three water molecules in an unsymmetrical fashion. Spectroscopic analysis of the complex strongly suggests that the octanuclear cluster also exists in solution and maintains a conformation similar to that in the crystal structure, although exchange of the coordinating water molecules presumably takes place. In addition, the formation process of the octanuclear complex is highly cooperative. A high coordinating ability of the [(salamo)Zn] unit as well as the catecholato2- moieties probably stabilizes the octanuclear assembly and makes the complexation process cooperative. The corresponding octanuclear cobalt(II) cluster [L4Co8(EtOH)3] was prepared in a similar manner. Complex [L4Co8(H2O)2X] (X = H2O or EtOH) was obtained by the recrystallization from chloroform/hexane. The complex crystallizes in the triclinic system, space group P, with unit cell parameters a = 15.2359(10) A, b = 16.9625(12) A, c = 18.9325(13) A, alpha = 101.9710(10) degrees, beta = 105.5410(10) degrees, gamma = 97.1290(10) degrees, and Z = 2. Temperature dependence of magnetic susceptibility showed a continuous decrease in the chi(M)T value with decreasing temperature, suggesting antiferromagnetic interaction among cobalt(II) ions. The magnetic susceptibility above 40 K obeys the Curie-Weiss law with a Weiss constant theta of -39 K and a Curie constant C of 19.7 cm(3) K mol(-1).     

A chain of changes: influence of noncovalent interactions on the one-dimensional structures of nickel(II) dicarboxylate coordination polymers with chelating aromatic amine ligands

Five one-dimensional coordination polymers, Ni(BDC)(1,10-phen) (1), Ni(BDC)(2,2'-bipy).0.75H(2)BDC (2), Ni(BDC)(1,10-phen)(H(2)O) (3), Ni(BDC)(1,10-phen)(H(2)O).0.5H(2)BDC (4) and Ni(BDC)(2,2'-bipy)(H(2)O) (5) [where BDC = 1,4-benzenedicarboxylate, 2,2-bipy = 2,2'-bipyridine, and 1,10-phen = 1,10-phenanthroline] that have the same topology but markedly different geometry and packing of the chains have been synthesized by hydrothermal reactions. The results of variations of synthesis conditions and substitutions of 1,10-phenanthroline with 2,2'-bipyridine indicate that incorporation of the coordinating water molecule, which affects the degree of bending of the chain, is primarily influenced by the amine ligand size, suggesting a substantial structural role of aromatic-aromatic interactions and amine ligand steric effects. The incorporation of the guest H(2)BDC molecules was found to be favored by lower pH conditions. Crystal data: 1, monoclinic, space group P2(1)/n, a = 9.5589(6) A, b = 12.6776(8) A, c = 13.5121(9) A, beta = 95.437(1) degrees, Z = 4; 2, monoclinic, space group P2(1)/c, a = 20.532(3) A, b = 21.505(3) A, c = 18.872(3) A, beta = 93.86(1) degrees, Z = 16; 3, triclinic, space group P1, a = 8.618(3) A, b = 10.058(4) A, c = 11.353(4) A, alpha = 115.31(1) degrees, beta = 92.33(1) degrees, gamma = 94.03(1) degrees, Z = 2; 4, triclinic, space group P1, a = 9.7682(12) A, b = 10.6490(13) A, c = 11.2468(14) A, alpha = 76.685(2) degrees, beta = 65.309(2) degrees, gamma = 85.612(2) degrees, Z = 2; 5, monoclinic, space group P2(1)/c, a = 13.9683(9) A, b = 17.4489(11) A, c = 13.7737(9) A, beta = 99.12(1) degrees, Z = 8.     

Nickel(II) and zinc(II) dibenzoylmethanates: molecular and crystal structure, polymorphism, and guest- or temperature-induced oligomerization

Four forms of nickel(II) and two of zinc(II) dibenzoylmethanates have been isolated and characterized with powder and single-crystal X-ray diffraction analyses, differential scanning calorimetry, magnetic susceptibility measurements, and solid-state 13C cross-polarization/magic angle spinning NMR. Nickel dibenzoylmethanate, Ni(DBM)2 (DBM = PhCOCHCOPh-), forms three polymorphic forms (light-green, brown, and green) and a fourth clathrate form with guest benzene included. The light-green polymorph is metastable. Substituted benzenes induce recrystallization of the polymorph into a stable brown form (C30H22NiO4; a = 26.502(3) A, b = 5.774(1) A, c = 16.456(2) A, beta = 116.03(1) degrees; monoclinic, C2/c; Z = 4). Unlike the other forms, the brown form is diamagnetic and is comprised of monomers of the low-spin [Ni(DBM)2] complex. The Ni(II) is chelated by two DBM ligands in a square planar environment by four donor oxygen atoms. When heated, the brown form transforms to a green form which is stable above 202 degrees C (C90H66Ni3O12; a = 13.819(2) A, b = 16.252(2) A, c = 17.358(2) A, beta = 108.28(1) degrees; monoclinic, P2(1)/n; Z = 2). This polymorph is formed by van der Waals packing of trimers [Ni3(DBM)6] containing linear Ni3 clusters with an Ni-Ni distance of 2.81 A. The cluster is surrounded by six DBM ligands, providing a distorted octahedral environment about each Ni by six oxygen atoms. Benzene stabilizes the trimeric structure at room temperature, forming a [Ni3(DBM)6].2(benzene) inclusion compound (Ni-Ni distance of 2.83 A) with guest benzene molecules located in channels (C90H66Ni3O12 + 2(C6H6); a = 17.670(2) A, b = 20.945(3) A, c=11.209(2) A, beta = 102.57(1) degrees; monoclinic, P2(1)/c; Z = 2). Zinc dibenzoylmethanate has been prepared in two polymorphic forms. The monomeric form contains [Zn(DBM)2] molecules with the zinc center in a distorted tetrahedral environment of four oxygens from the two chelated DBMs (C30H22O4Zn; a = 10.288(2) A, b = 10.716(2) A, c = 12.243(2) A, alpha = 89.19(1) degrees, beta = 75.39(1) degrees, gamma = 64.18(1) degrees; triclinic, P1; Z = 2). Another, dimeric form contains [Zn2(DBM)4] species, with two zinc atoms separated by a distance of 3.14 A and each zinc coordinated by five oxygen atoms (C60H44O8Zn2; a = 25.792(3) A, b = 7.274(1) A, c = 24.307(2) A, beta = 90.58(1) degrees; monoclinic, C2/c; Z = 4). The polymorphic variety of the title complexes and the peculiarities of the Ni(II) and Zn(II) coordination environments are discussed in the context of using the complexes as precursors for new metal complex hosts.     

Lanthanide chalcogenolate complexes: synthesis and crystal structures of the isoleptic series [Sm(TpMe,Me)2ER] (E = O, S, Se, Te; TpMe,Me = tris-3,5-dimethylpyrazolylborate)

A series of lanthanide complexes containing a chalcogenolate ligand supported by two TpMe,Me (tris-3,5-dimethylpyrazolylborate) groups has been prepared and crystallized and provides direct comparisons of bonding to hard and soft ligands at lanthanide centers. Reaction of [Sm(TpMe,Me)2Cl] with NaOR (R = Ph, Ph-Bu(t)) gives [Sm(TpMe,Me)2OR] (1a and 1b, respectively) in good yields. Reductive cleavage of dichalcogenides by samarium(II) was used to prepare the heavier congeners. Complexes of the type [Sm(TpMe,Me)2ER] for E = S, R = Ph (2a), E = S, R = Ph-4-Me (2b), E = S, R = CH2Ph (2c), E = Se, R = Ph (3a), E = Se, R = Ph-4-Bu(t) (3b), E = Se, R = CH2Ph (3c), and E = Te, R = Ph (4) have been prepared together with the corresponding complexes with TpMe,Me,4-Et as ancillary. The X-ray crystal structures of 1b, 2b, 3a, 3b, and 4 have been determined. The crystal of 1b (C40H57B2N12OSm.C7H8) was monoclinic, P2(1)/c, a = 10.6845(6) A, b = 18.5573(11) A, c = 24.4075(14) A, beta = 91.616(2) degrees, Z = 4. The crystal of 2b (C37H51B2N12SSm) was monoclinic, P2(1)/n, a = 15.0154(9) A, b = 13.1853(8) A, c = 21.1254(13) A, beta = 108.628(2) degrees, Z = 4. The crystal of 3a (C36H49B2N12SeSm.C7H8) was triclinic, P1, a = 10.7819(6) A, b = 19.3011(10) A, c = 23.0235(12) A, alpha = 79.443(2) degrees, beta = 77.428(2) degrees, gamma = 89.827(2) degrees, Z = 4. The crystal of 3b (C40H57B2N12SeSm) was triclinic, P1, a = 10.1801(6) A, b = 10.2622(6) A, c = 23.4367(14) A, alpha = 88.313(2) degrees, beta = 86.268(2) degrees, gamma = 62.503(2) degrees, Z = 2. The crystal of 4 (C36H49B2N12TeSm.C7H8) was monoclinic, P2(1)/c, a = 18.7440(10) A, b = 10.3892(6) A, c = 23.8351(13) A, beta = 94.854(2) degrees, Z = 4. The compounds form an isoleptic series of seven-coordinate complexes with terminal chalcogenolate ligands. Examination of 1b and other crystallographically characterized lanthanide alkoxides suggests that there is little correlation between bond angle and bond length. The structures of 3a and 3b, however, contain molecules in which one of the pyrazolylborate ligands undergoes a major distortion arising from twisting around a B-N bond so as to give an effectively eight-coordinate complex with pi-stacking of the phenyl group with one pyrazolyl ring. These distortions shed light on the fluxionality of these systems.     

From metallacyclophanes to 1-D coordination polymers: role of anions in self-assembly processes of copper(II) and 2,5-bis(3-pyridyl)-1,3,4-oxadiazole

The reaction of various CuII salts with 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (L) in CH3CN-H2O medium affords different complexes, the solid structures of which are controlled only by the choice of the counteranions. Reaction of Cu-(ClO4)2.6H2O or Cu(NO3)2.3H2O and L yields the novel bimetallic macrocyclic complex [Cu2L2(H2O)6](ClO4)4(H2O)4 (1) [monoclinic, space group P21/m, a = 8.745(5) A, b = 16.179(10) A, c = 14.930(8) A, beta = 93.253(10) degrees, Z = 2] or [CuL(NO3)2]2(CH3CN)2 (2) [triclinic, space group P1, a = 7.863(3) A, b = 8.679(3) A, c = 13.375(5) A, alpha = 74.121(5) degrees, beta = 78.407(6) degrees, gamma = 86.307(6) degrees, Z = 1]. However, with the replacement of CuII perchlorate or nitrate salts with CuSO4.5H2O or Cu(OAc)2.H2O in the above reaction, two different one-dimensional (1-D) coordination polymers [[Cu2L2(H2O)6(SO4)2](H2O)6]n (3) [triclinic, space group P1, a = 7.078(3) A, b = 11.565(4) A, c = 12.561(5) A, alpha = 109.511(6) degrees, beta = 105.265(6) degrees, gamma = 94.042(6) degrees, Z = 1] or [[Cu2L(mu-OAc)4]]n (4) [monoclinic, space group C2/c, a = 20.007(7) A, b = 7.506(2) A, c = 16.062(5) A, beta = 108.912(5) degrees, Z = 4] were obtained. These results unequivocally indicate that the nature of the counteranions, which play different roles in each complex, is the key factor governing the structural topologies of them. The magnetic properties of these CuII complexes have been investigated by variable-temperature magnetic susceptibility and magnetization measurements, and the magneto-structural correlation has been analyzed in detail.