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

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

A novel group of alkaline earth metal amides: syntheses and characterization of M[N(2,6-(i)Pr(2)C(6)H(3))(SiMe(3))](2)(THF)(2) (M = Mg,Ca, Sr,Ba) and the linear,two-coordinate Mg[N(2,6-(i)Pr(2)C(6)H(3))(SiMe(3))](2)

Novel alkaline earth metal aryl-substituted silylamides were prepared using alkane (Mg) and salt elimination reactions (Mg, Ca, Sr, and Ba). The salt elimination regime involved the treatment of the alkaline earth metal iodides with 2 equiv of the respective potassium amide KNDiip(SiMe(3)), (Diip = 2,6-i-Pr(2)C(6)H(3)). The organomagnesium source for the alkane elimination was ((n)()Bu/(s)()Bu)(2)Mg. All compounds were characterized using (1)H, (13)C NMR, and IR spectroscopy, in addition to X-ray crystallography (except Mg[NDiip(SiMe(3))](2)THF(2)). Crystal data with Mo Kalpha (lambda = 0.710 73 A) are as follows: Mg[NDiip(SiMe(3))](2), 1, a = 9.4687(6) A, b = 9.6818(6) A, c = 17.9296(1) A, alpha = 96.487(1) degrees, beta = 94.537(1) degrees, gamma = 89.222(1) degrees, V = 1608.8(2) A(3), Z = 2 (two independent molecules), triclinic, space group P(-)1, R1 (all data) = 0.0508; (n)()BuMg[NDiip(SiMe(3))]THF(2), 2, a = 9.5413(1) A, b = 16.493(2) A, c = 9.8218(1) A, beta = 108.149(2) degrees, V = 1468.7(4) A(3), Z = 2, monoclinic, space group P2(1), R1(all data) = 0.1232; Ca[NDiip(SiMe(3))](2)THF(2), 4, a = 9.7074(1) A, b = 20.9466(4) A, c = 21.6242(3) A, alpha = 73.573(1) degrees, beta = 78.632(1) degrees, gamma = 89.621(1) degrees, V = 4129.1(1) A(3), Z = 4 (two independent molecules), triclinic, space group P(-)1, R1 (all data) = 0.0902; Sr[NDiip(SiMe(3))](2)THF(2), 5, a = 20.5874(5) A, b = 9.8785(2) A, c = 20.8522(5) A, beta = 102.035(2) degrees, V = 4147.6(2) A(3), Z = 4 (two independent molecules), monoclinic, space group P2/n, R1 (all data) = 0.0756; Ba[NDiip(SiMe(3))](2)THF(2), 6, a = 20.5476(2) A, b = 10.0353(2) A, c = 20.9020(4) A, beta = 101.657(1) degrees, V = 4221.0(1) A(3), Z = 4 (two independent molecules), monoclinic, space group P2/n, R1 (all data) = 0.0573.     

Modulating the reduction potential of mononuclear cobalt(II) complexes via selective deprotonation of tris[(2-benzimidazolyl)methyl]amine

Remote site deprotonation of the coordinated tripodal ligand, tris((2-benzimidazolyl)methyl)amine, was examined using electronic spectroscopy and electrochemistry techniques. The solid-state structures [CoH(3)1(tba)(NCS)]+ and [CoH(2)1(tba)(NCS)] are reported. These complexes crystallized in the triclinic space group P1 [a = 13.3043(2) A, b = 13.8019(2) A, c = 14.1322(2) A, alpha = 63.6670(10) degrees, beta = 68.0590(10) degrees, gamma = 81.8960 degrees; Z = 2] and the monoclinic space group P2(1)/n [a = 15.3530(9) A, b = 11.0645(6) A, c = 19.1319(10) A, beta = 105.6750(10) degrees; Z = 4], respectively. Preliminary results suggest that selective and reversible deprotonation of coordinated benzimidazolyl ligands can tune the reduction potential of several isostructural cobalt(II) complexes.     

Reactions and reactivity of Co-bpdc coordination polymers (bpdc = 4,4'-biphenyldicarboxylate)

By choosing a suitable metal center, ligand, and solvents, we have revealed several structural transformations involving a polymer precursor. infinity 1[Co(bpdc)(H2O)2].H2O (1) was prepared by reaction of Na2bpdc and Co(NO3)2 in aqueous solution. Immersing 1 in pyridine/water solutions of (2:1) and (8:1) ratios yielded a second one-dimensional structure infinity 1[Co(bpdc)(py)2(H2O)2].2py (2) and a two-dimensional structure infinity 2[Co(bpdc)(py)2].H2O (3), respectively. After heating 1 under N2 to remove all water within the structure, the compound Co(bpdc) (IR) was obtained. When IR was immersed in solutions of pyridine/water (5:4) and in pure pyridine (in air), a third one-dimensional structure of infinity 1[Co(bpdc)(py)2(H2O)2].2py.H2O (4) and 3, respectively, were obtained. Compounds 2-4 easily transformed to 1 when immersed in water. Crystal data for 1: monoclinic, space group C2/c with a = 6.950(1), b = 31.585(6), and c = 6.226(1) A, beta = 95.84(3) degrees, Z = 4. Crystal data for 2: triclinic, space group P1 with a = 9.646(2), b = 10.352(2), and c = 17.031(3) A, alpha = 79.02(3) degrees, beta = 86.88(3) degrees, gamma = 77.16(3) degrees, Z = 2. Crystal data for 3: triclinic, space group P1 with a = 9.137(2), b = 10.480(2), and c = 12.254(2) A, alpha = 102.10(3) degrees, beta = 100.80(3) degrees, gamma = 99.43(3) degrees, Z = 2. Crystal data for 4: orthorhombic, space group Pbcn with a = 13.468(3), b = 16.652 (3), and c = 14.977(3) A, Z = 4.     

Synthesis of monohalogeno derivatives of closo-[B9H9]2-. Crystal structures of (Ph4P)2[1-XB9H8].CH3CN (X = Cl, Br, I)

By reaction of Na2[B9H9] with the appropriate N-halogenosuccinimide, the monohalogenated anion [1-XB9H8]2- (X = Cl, Br, or I) is formed. The X-ray diffraction analyses performed on single crystals of (Ph4P)2[1-XB9H8].CH3CN (X = Cl, Br, I) reveal that the tricapped trigonal prismatic geometry of the cluster is retained after substitution in the 1-position. Crystallographic data are as follows for (Ph4P)2[1-XB9H8].CH3CN. X = Cl, Br: monoclinic, space group P2(1), a = 10.7 A, b = 32.9 A, c = 13.8 A, beta = 96 degrees, Z = 4, R1 = 0.038 and R1 = 0.036, respectively. X = I: monoclinic, space group P2(1)/n, a = 10.5 A, b = 13.6 A, c = 33.4 A, beta = 94 degrees, Z = 4, R1 = 0.094. The compounds have been characterized by vibrational and 11B NMR spectroscopy as well.     

An additional structural and electrical study of polymeric haloplumbates(II) with heterocyclic diprotonated amines

The crystal structures of three polymeric bidimensional piperazinium, N,N'-dimethylpiperazinium, and N-benzylpiperazinium hydrate haloplumbates(II) and one polymeric monodimensional N,N'-dimethylpiperazinium hydrate haloplumbate(II) were determined by means of X-ray analysis. The (pipzH2)[PbCl4] salt is monoclinic, space group P2(1)/c, with a = 5.778(2) A, b = 22.612(26) A, c = 9.061(4) A, beta = 95.37(6) degrees, Z = 4; (me2pipzH2)[PbBr4] crystallizes in the monoclinic P2(1) space group with a = 6.101(3) A, b = 18.822(12) A, c = 6.229(2) A, beta = 98.62(4) degrees, Z = 2; the crystals of (me2pipzH2)2[Pb3I10].4H2O are monoclinic, space group P2(1)/c, a = 19.054(4) A, b = 12.239(3) A, c = 18.273(4) A, beta = 93.42(12) degrees, Z = 4; (benzpipzH2)3[Pb2Br10].2H2O crystallizes in the monoclinic P2(1)/c space group with a = 22.380(22) A, b = 9.304(15) A, c = 24.577(25) A, beta = 94.28(11) degrees, Z = 2. Different model type structures, such as one-dimensional linear chain, ribbonlike, and perovskite-like, were observed, and factors governing these structural arrangements are pointed out. The compounds were also investigated by means of thermal and electrical measurements, and correlations between electrical properties and crystal structures were noted.     

Formation of one-, two-, and three-dimensional open-framework zinc phosphates in the presence of a tetramine

Five new open-framework zinc phosphates, encompassing the entire hierarchy of open-framework structures, have been synthesized hydrothermally in the presence of triethylenetetramine. The structures include one-dimensional ladders, two-dimensional layers, and three-dimensional structures as well as a zinc phosphate where the amine acts as a ligand. [C6N4H22]0.5[Zn(HPO4)2] (I): monoclinic, space group P2(1)/c (no. 14), a = 5.2677(1) A, b = 13.3025(1) A, c = 14.7833(1) A, beta = 96.049 degrees, Z = 4. [C6N4H22]0.5[Zn2(HPO4)3] (II): triclinic, space group P1 (no. 2), a = 7.515(1) A, b = 8.2553(1) A, c = 12.911(1) A, alpha = 98.654(1) degrees, beta = 101.274(1) degrees, gamma = 115.791(1) degrees, Z = 2. [C6N4H22]0.5[Zn2P2O8] (III): triclinic, space group P1 (no. 2), a = 8.064(1) A, b = 8.457(1) A, c = 9.023(1) A, alpha = 111.9(1) degrees, beta = 108.0(1) degrees, gamma = 103.6(1) degrees, Z = 2. [C6N4H22]0.5[Zn3(PO4)2(HPO4)] (IV): triclinic, space group P1 (no. 2), a = 5.218(1) A, b = 8.780(1) A, c = 16.081(1) A, alpha = 89.3(1) degrees, beta = 83.5(1) degrees, gamma = 74.3(1) degrees, Z = 2. [C6N4H20]0.5[Zn4P4O16] (V): monoclinic, space group P2(1)/c (no. 14), a = 9.219(1) A, b = 15.239(1) A, c = 10.227(1) A, beta = 105.2(1), Z = 4. The structure of I is composed of ZnO4 and HPO4 tetrahedra, which are edge-shared to form four-membered rings, which, in turn, form a one-dimensional chain (ladder). In II, these ladders are fused into a layer. The structures of III and IV comprise networks of ZnO4 and PO4 tetrahedra forming three-dimensional architectures. In V, the amine molecule coordinates to the Zn and acts as a pillar supporting the zinc phosphate layers, which possess infinite Zn-O-Zn linkages. The 16-membered one-dimensional channel in IV and the ZnO3N pillar, along with infinite Zn-O-Zn linkages in V, are novel features. The structure of the open-framework zinc phosphates is found to depend sensitively on the relative concentrations of the amine and phosphoric acid, with high concentrations of the latter favoring structures with lower dimensions.     

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.     

Structural and Electrochemical Comparison of Copper(II) Complexes with Tripodal Ligands

A series of copper(II) complexes with tripodal polypyridylmethylamine ligands, such as tris(2-pyridylmethyl)amine (tpa), ((6-methyl-2-pyridyl)methyl)bis(2-pyridylmethyl)amine (Me(1)tpa), bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine (Me(2)tpa), and tris((6-methyl-2-pyridyl)methyl)amine (Me(3)tpa), have been synthesized and characterized by X-ray crystallography. [Cu(H(2)O)(tpa)](ClO(4))(2) (1) crystallized in the monoclinic system, space group P2(1)/a, with a = 15.029(7) ?, b = 9.268(2) ?, c = 17.948(5) ?, beta = 113.80(3) degrees, and Z = 4 (R = 0.061, R(w) = 0.059). [CuCl(Me(1)tpa)]ClO(4) (2) crystallized in the triclinic system, space group P&onemacr;, with a = 13.617(4) ?, b = 14.532(4) ?, c = 12.357(4) ?, alpha = 106.01(3) degrees, beta = 111.96(2) degrees, gamma = 71.61(2) degrees, and Z = 4 (R = 0.054, R(w) = 0.037). [CuCl(Me(2)tpa)]ClO(4) (3) crystallized in the monoclinic system, space group P2(1)/n, with a = 19.650(4) ?, b = 13.528(4) ?, c = 8.55(1) ?, beta = 101.51(5) degrees, and Z = 4 (R = 0.071, R(w) = 0.050). [CuCl(Me(3)tpa)][CuCl(2)(Me(3)tpa)]ClO(4) (4) crystallized in the monoclinic system, space group P2(1)/a, with a = 15.698(6) ?, b = 14.687(7) ?, c = 19.475(4) ?, beta = 97.13(2) degrees, and Z = 4 (R = 0.054, R(w) = 0.038). All the Cu atoms of 1-4 have pentacoordinate geometries with three pyridyl and one tertiary amino nitrogen atoms, and a chloride or aqua oxygen atom. Nitrite ion coordinated to the Cu(II) center of Me(1)tpa, Me(2)tpa, and Me(3)tpa complexes with only oxygen atom to form nitrito adducts. The cyclic voltammograms of [Cu(H(2)O)(Me(n)()tpa)](2+) (n = 0, 1, 2, and 3) in the presence of NO(2)(-) in H(2)O (pH 7.0) revealed that the catalytic activity for the reduction of NO(2)(-) increases in the order Me(3)tpa < Me(2)tpa < Me(1)tpa < tpa complexes.     

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.     

Mixed-metal uranium(VI) iodates: hydrothermal syntheses,structures, and reactivity of Rb[UO(2)(CrO(4))(IO(3))(H(2)O)], A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K,Rb, Cs), and K(2)[UO(2)(MoO(4))(IO(3))(2)

The reactions of the molecular transition metal iodates A[CrO(3)(IO(3))] (A = K, Rb, Cs) with UO(3) under mild hydrothermal conditions provide access to four new, one-dimensional, uranyl chromatoiodates, Rb[UO(2)(CrO(4))(IO(3))(H(2)O)] (1) and A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K (2), Rb (3), Cs (4)). Under basic conditions, MoO(3), UO(3), and KIO(4) can be reacted to form K(2)[UO(2)(MoO(4))(IO(3))(2)] (5), which is isostructural with 2 and 3. The structure of 1 consists of one-dimensional[UO(2)(CrO(4))(IO(3))(H(2)O)](-) ribbons that contain uranyl moieties bound by bridging chromate and iodate anions as well as a terminal water molecule to create [UO(7)] pentagonal bipyramidal environments around the U(VI) centers. These ribbons are separated from one another by Rb(+) cations. When the iodate content is increased in the hydrothermal reactions, the terminal water molecule is replaced by a monodentate iodate anion to yield 2-4. These ribbons can be further modified by replacing tetrahedral chromate anions with MoO(4)(2)(-) anions to yield isostructural, one-dimensional [UO(2)(MoO(4))(IO(3))(2)](2)(-) ribbons. Crystallographic data: 1, triclinic, space group P(-)1, a = 7.3133(5) A, b = 8.0561(6) A, c = 8.4870(6) A, alpha = 88.740(1) degrees, beta = 87.075(1) degrees, gamma = 71.672(1) degrees, Z = 2; 2, monoclinic, space group P2(1)/c, a = 11.1337(5) A, b = 7.2884(4) A, c = 15.5661(7) A, beta = 107.977(1) degrees, Z = 4; 3, monoclinic, space group P2(1)/c, a = 11.3463(6) A, b = 7.3263(4) A, c = 15.9332(8) A, beta = 108.173(1) degrees, Z = 4; 4, monoclinic, space group P2(1)/n, a = 7.3929(5) A, b = 8.1346(6) A, c = 22.126(2) A, beta = 90.647(1) degrees, Z = 4; 5, monoclinic, space group P2(1)/c, a = 11.3717(6) A, b = 7.2903(4) A, c = 15.7122(8) A, beta = 108.167(1) degrees, Z = 4.     

Structurally reinforced tetraazamacrocyclic complexes

The reaction between alkyl or aryl aldehydes and macrocyclic ligands with pendant amine groups produced imidazolidine-containing bi- or tricyclic ligands. The copper complexes of three of these ligands were structurally characterized: [CuL3Cl].3H2O (triclinic, P1, a = 10.041(2) A, b = 10.172(1) A, c = 11.202(1) A, alpha = 92.07(1) degrees, beta = 96.76(2) degrees, gamma = 92.99(1) degrees, Z = 2), [Cu(H2L4)Cl]Cl.2H2O (monoclinic, P2(1)/n, a = 15.159(5) A, b = 10.645(1) A, c = 19.094(6) A, beta = 93.78(1) degrees, Z = 4), [CuL5].2H2O.NaNO3 (monoclinic, P2(1)/n, a = 10.649(8) A, b = 7.261(2) A, c = 15.25(1) A, beta = 94.77(4) degrees, Z = 2). The conformational rigidity and stereochemical activity of these macrocycles and their complexes are discussed in comparison with close analogues.     

A convergent synthetic approach using sterically demanding aryldipyrrylmethanes for tuning the pocket sizes of cofacial bisporphyrins

Meso substitution opposite to the spacer provides a convenient approach for tuning the pocket sizes of pillared cofacial bisporphyrins. The synthesis and coordination chemistry of xanthene and dibenzofuran anchored platforms structurally modified with 2,6-dimethoxyaryl groups are described. Comparative structural analysis of xanthene derivatives confirms the ability of the trans-aryl groups to adjust the vertical dimension of the cofacial cleft: 7 (C(97)H(106)Cl(4)N(8)O(5)), monoclinic, space group P2(1)/c, a = 28.8353(12) A, b = 17.1139(7) A, c = 17.5978(7) A, beta = 98.826(1) degrees, Z = 4; 8 (C(101)H(123)Cl(2)N(8)O(11.5)Zn(2)), monoclinic, space group P2(1)/n, a = 14.5517(6) A, b = 22.9226(10) A, c = 28.5155(13) A, beta = 90.312(14) degrees, Z = 4; 12 (C(99)H(102)Cl(14)N(8)O(5)Mn(2)), monoclinic, space group P2/c, a = 19.5891(3) A, b = 15.0741(2) A, c = 33.2019(6) A, beta = 91.947(10) degrees, Z = 4. The convenience and versatility of this synthetic method offers intriguing opportunities to specifically tailor the binding pockets of cofacial bisporphyrins for the study of small-molecule activation within a proton-coupled electron transfer framework.     

New d0 transition metal iodates: synthesis, structure, and characterization of BaTi(IO3)6, LaTiO(IO3)5, Ba2VO2(IO3)4.(IO3), K2MoO2(IO3)4, and BaMoO2(IO3)4.H2O

Five new d0 transition metal iodates, BaTi(IO3)6, LaTiO(IO3)5, Ba2VO2(IO3)4.(IO3), K2MoO2(IO3)4, and BaMoO2(IO3)4.H2O, have been synthesized by hydrothermal methods using Ba(OH)2.8H2O, La2O3, K2CO3, TiO2, V2O5, MoO3, and HIO3 as reagents. The structures of these compounds were determined by single-crystal X-ray diffraction. All of the reported materials have zero-dimensional or pseudo-one-dimensional crystal structures composed of MO6 (M = Ti4+, V5+, or Mo6+) octahedra connected to IO3 polyhedra. Infrared and Raman spectroscopy, thermogravimetric analysis, and UV-vis diffuse reflectance spectroscopy are also presented. Crystal data: BaTi(IO3)6, trigonal, space group R-3 (No. 148), with a = b = 11.4711(10) A, c = 11.1465(17) A, V = 1270.2(2) A3, and Z = 3; LaTiO(IO3)5, monoclinic, space group P2(1)/n (No. 14), with a = 7.4798(10) A, b = 18.065(2) A, c = 10.4843(14) A, beta = 91.742(2) degrees , V = 1416.0(3) A3, and Z = 4; Ba2VO2(IO3)4.(IO3), monoclinic, space group P2(1)/c (No. 14), with a = 7.5012(9) A, b = 33.032(4) A, c = 7.2150(9) A, beta = 116.612(2) degrees , V = 1598.3(3) A3, and Z = 4; K2MoO2(IO3)4, monoclinic, space group C2/c (No. 15), with a = 12.959(2) A, b = 6.0793(9) A, c = 17.748(3) A, beta = 102.410(4) degrees , V = 1365.5(4) A3, and Z = 4; BaMoO2(IO3)4.H(2)O, monoclinic, space group P2(1)/n (No. 14), with a = 13.3368(17) A, b = 5.6846(7) A, c = 18.405(2) A, beta = 103.636(2) degrees , V = 1356.0(3) A3, and Z = 4.     

Pseudo-polyrotaxane and beta-sheet layer-based three-dimensional coordination polymers constructed with silver salts and flexible pyridyl-type ligands

A fascinating 3D pseudo-polyrotaxane architecture with 1D polymeric [Ag(bpp)](n) chains penetrating 2D (6,3) [Ag(2)(bpp)(2)(ox)](n) sheets and a 3D coordination network constructed with 2D infinite [Ag(ppa)](n) beta-sheetlike layers pillared by ox ligands (bpp = 1,3-bis(4-pyridyl)propane; ppa = N-(4-pyridinylmethyl)-4-pyridinecarboxamide; ox = oxalate) have been prepared by utilizing flexible pyridyl-type ligands and have been crystallographically characterized. Crystal data for 1: monoclinic, space group C2/c, a = 7.619(2) A, b = 19.781(4) A, c = 26.799(5) A, beta = 94.720(10) degrees, U = 4025.2(15) A(3), and Z = 4. Crystal data for 2: monoclinic, space group C2/c, a = 28.947(8) A, b = 8.617(3) A, c = 16.307(6) A, beta =121.07(1) degrees, U = 3484(2) A(3), and Z = 4.     

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.     

Synthesis and Characterization of Water-Soluble 1,2-Bis(bis(hydroxyalkyl)phosphino)ethane Ligands and Their Nickel(II), Ruthenium(III), and Rhodium(I) Complexes

The syntheses of the water-soluble, chelating phosphines 1,2-bis(bis(hydroxybutyl)phosphino)ethane (1, n = 3; DHBuPE) and 1,2-bis(bis(hydroxypentyl)phosphino)ethane (1, n = 4; DHPePE) are reported. These ligands (and, in general, other 1,2-bis(bis(hydroxyalkyl)phosphino)ethane ligands) can be used to impart water solubility to metal complexes. As examples of this, the [Ni(DHPrPE)(2)Cl]Cl (2), [Rh(DHPrPE)(2)][Cl] (3), and [Ru(DHBuPE)(2)Cl(2)][Cl] (4) complexes were synthesized; they are indeed soluble in water (>0.5 M). Crystals of DHPrPE (1, n = 2) are monoclinic, space group P2(1)/c, with a = 9.5935(8) ?, b = 9.353(2) ?, c = 10.655(2) ?, alpha = 90 degrees, beta = 100.03(1) degrees, gamma = 90, V = 941.5(5) ?(3), R = 0.051, and Z = 2. Crystals of [Ni(DHPrPE)(2)Cl]Cl (2) are monoclinic, space group I2, with a = 15.951(3) ?, b = 11.454(2) ?, c = 20.843(3) ?, alpha = 90 degrees, beta = 91.24(2) degrees, gamma = 90 degrees, V = 3807(2) ?(3), R = 0.062, and Z = 4. Crystals of [Rh(DHPrPE)(2)][Cl] (3) are triclinic, space group P&onemacr;, with a = 13.900(2) ?, b = 15.378(2) ?, c = 18.058(2) ?, alpha = 87.71(1) degrees, beta = 75.03(1) degrees, gamma = 85.24(1), V = 3715(2) ?(3), R = 0.044, and Z = 4. Crystals of [Ru(DHBuPE)(2)Cl(2)][Cl] (4) are monoclinic, space group C2/c, with a = 14.310(2) ?, b = 21.630(2) ?, c = 15.459(3) ?, alpha = 90 degrees, beta = 99.83(1) degrees, gamma = 90, V = 4715(1) ?(3), R = 0.056, and Z = 4.     

Two versatile N,N'-bipyridine-type ligands for preparing organic-inorganic coordination polymers: new cobalt- and nickel-containing framework materials

The Schiff base ligands 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene (L1, monoclinic, P2(1)/c, a = 3.856(1) A, b = 11.032(2) A, c = 12.738(3) A, beta = 92.21(3) degrees, Z = 2) and 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene (L2, monoclinic, P2(1)/c, a = 10.885(2) A, b = 4.613(1) A, c = 14.978(3) A, beta = 92.827(4) degrees, Z = 2) were used in the synthesis of four new organic-inorganic coordination polymers, each of them adopting a different structural motif. Synthesis, X-ray structural determinations, and spectroscopic and thermogravimetric analyses are presented. The reaction between Co(NO(3))(2).6H(2)O and L1 afforded a two-dimensional noninterpenetrating brick-wall structure, [Co(C(12)N(4)H(10))(1.5)(NO(3))(2)(H(2)O)(CH(2)Cl(2))(2)](n)() (1, triclinic, P1; a = 10.242(7) A, b = 10.802(7) A, c = 15.100(1) A, alpha = 70.031(1), beta = 75.168(11), gamma = 76.155(11), Z = 2), while Ni(NO(3))(2).6H(2)O combined with L1 yielded an interpenetrating three-dimensional rhombus-grid polymer, [Ni(C(12)N(4)H(10))(2)(NO(3))(2)(OC(4)H(8))(1.66)(H(2)O)(0.33)](n) (2, monoclinic, C2/c; a = 20.815(8) A, b = 23.427(8) A, c = 17.291(6) A, beta = 116.148(6), Z = 8). The reaction of Co(NO(3))(2).6H(2)O and L2 was found to be solvent-sensitive and resulted in the formation of two different noninterpenetrating compounds: [Co(C(14)N(4)H(14))(2)(NO(3))(2)(C(6)H(6))(1.5)](n)() (3, monoclinic, C2/c; a = 22.760(2) A, b = 21.010(3) A, c = 25.521(2) A, beta = 97.151(2), Z = 8), which adopts a two-dimensional square-grid motif formed by propeller-type modules, and [Co(C(14)N(4)H(14))(1.5)(NO(3))(2)(CH(2)Cl(2))(2)](n)() (4, monoclinic, P2(1)/n; a = 14.432(2) A, b = 14.543(8) A, c = 15.448(4) A, beta = 96.968(0), Z = 4), consisting of T-shaped building blocks assembled into a one-dimensional ladder-type structure. These four coordination polymers all exhibit impressive thermal stability. Thermogravimetric studies showed that after complete removal of the solvents, the frameworks are stable to temperatures between 234 degrees C and 260 degrees C.     

Hydrothermal synthesis,structures, and magnetic properties of three novel 5-aminoisophthalic acid ligand bridged transition metal cation polymers

Three novel 5-aminoisophthalic acid (AIP) bridged polymers [Co(C(8)NH(5)O(4))(H(2)O)](n)() (1), [Ni(C(8)NH(5)O(4))(H(2)O)(2)](n)() (2), and [Zn(C(8)NH(5)O(4))(H(2)O)](n)() (3) were synthesized by hydrothermal reactions and characterized by IR, Raman, elemental analysis, ESR, and magnetic measurements. X-ray single-crystal analyses were carried out for [Co(C(8)NH(5)O(4))(H(2)O)](n)() (1), which crystallizes in the triclinic system, space group P1 macro, with a = 6.477(1) A, b = 7.130(1) A, c = 9.826(2) A, alpha = 108.9(1) degrees, beta = 93.97(3) degrees, gamma = 98.82(3) degrees, and Z = 2; for [Ni(C(8)NH(5)O(4))(H(2)O)(2)](n)() (2), in the triclinic system, space group P1 macro, a = 6.425(1) A, b = 8.115(2) A, c = 10.146(2) A, alpha = 113.09(3)(o), beta = 99.64(3)(o), gamma = 98.90(3)(o), and Z = 2; and for [Zn(C(8)NH(5)O(4))(H(2)O)](n)() (3), in the monoclinic system, space group P2(1)/n, a = 9.044(1) A, b = 8.264(1) A, c = 11.646(1) A, beta = 100.77(1) degrees, and Z = 4. The single X-ray diffraction studies reveal that 1 consists of an infinite honeycomb layer formed by four crystallographically independent motifs packed alternatively together; 2 consists of an infinite neutral railroad-like linear polymer, and 3 consists of infinite layers of alternating four-coordinated Zn(II) cations and AIP ligands. Finally, they are all packed into beautiful three-dimensional frameworks through complicated hydrogen bonding. Antiferromagnetic and ferromagnetic behaviors were observed for 1 and 2 from the magnetic measurements.     

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

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