Syntheses and magneto-structural study of several polynuclear copper(II) complexes derived from 1,3-Bis(dimethylamino)-2-propanolato

The syntheses, structural characterization, and magnetic behavior of the three new polynuclear copper(II) complexes with formulas [Cu(4)(eta(2):mu-CH(3)COO)(2)(mu-OH)(2)(mu-OH(2))(mu-bdmap)(2)](ClO(4))(2).H(2)O (1), [Cu(8)(NCO)(2)(eta(1):mu-NCO)(4)(mu-OH)(2)(mu(3)-OH)(2)(mu-OH(2))(3)(mu-bdmap)(4)](ClO(4))(2)x2H(2)O (2), and [Cu(9)(eta(1):mu-NCO)(8)(mu(3)-OH)(4)(OH(2))(2)(mu-bdmap)(4)](ClO(4))(2).4H(2)O (3), in which bdmapH is 1,3-bis(dimethylamino)-2-propanol, are reported. Tetranuclear complex 1 crystallizes in the triclinic system, space group P, with unit cell parameters a = 12.160(1) A, b = 13.051(1) A, c = 13.235(1) A, alpha = 110.745(1) degrees , beta = 109.683(1) degrees , gamma = 97.014(1), and Z = 2. Octanuclear complex 2 crystallizes in the monoclinic system, space group C2/c, with unit cell parameters a = 26.609(1) A, b = 14.496(1) A, c = 16.652(1) A, beta = 97.814(1) degrees , and Z = 4, and nonanuclear complex 3 crystallizes in the monoclinic system, space group C2/c, with unit cell parameters a = 24.104(1) A, b = 13.542(1) A, c = 24.355(1) A, beta = 109.98(1) degrees , and Z = 4. The magnetic behavior of the three complexes has been checked showing strong antiferromagnetic coupling in all the cases.     

Novel acetate binding modes in [Na2Cu(CH3COO)4(H2O)].H2O

A new copper(II) acetate, [Na(2)Cu(CH(3)COO)(4)(H(2)O)].H(2)O (1), has been crystallized from an aqueous solution containing sodium acetate and copper(II) acetate monohydrate in a 4:1 ratio and the structure determined by X-ray crystallography. 1 crystallizes in the monoclinic space group P2(1)/c, with a = 16.638(3) A, b = 11.781(2) A, c = 15.668(3) A, beta = 90.11(3) degrees, V = 3071.0(11) A(3), and Z = 4. In the asymmetric unit, sodium ions bridge two crystallographically unique square planar [Cu(CH(3)COO)(4)](2-) units to their symmetry-generated neighbors to form corrugated 2D sheets of Na(2)Cu(CH(3)COO)(4), which are held together by H-bonding interactions involving the waters of crystallization. In contrast, the structures of known sodium copper acetates are better described as 3D frameworks. The metal centers are bridged by a number of acetates in novel coordination modes. The square planar Cu(II) geometry generated by oxygen atoms from four different acetates is an unexpected feature given the weak ligand field provided by the acetate ligands.     

Synthesis and structural characterization of trinuclear Cu(II)-pyrazolato complexes containing mu(3)-OH, mu(3)-O, and mu(3)-Cl ligands. Magnetic susceptibility study of [PPN](2)[(mu(3)-O)Cu(3)(mu-pz)(3)Cl(3)

The nine-membered [-Cu(II)-N-N-](3) ring of trimeric copper-pyrazolato complexes provides a sturdy framework on which water is twice deprotonated in consecutive steps, forming mu(3)-OH and mu(3)-O species. In the presence of excess chlorides the mu(3)-O(H) ligand is replaced by two mu(3)-Cl ions. The interconversion of mu(3)-OH and mu(3)-O and the exchange of mu(3)-O(H) and mu(3)-Cl are reversible, and the three species involved have been structurally characterized: [PPN][Cu(3)(mu(3)-OH)(mu-pz)(3)Cl(3)(thf)].CH(2)Cl(2) (1a), monoclinic P2(1)/n, a = 10.055(2) A, b = 35.428(5) A, c = 15.153(2) A, beta = 93.802(3) degrees, V = 5386(1) A(3), Z = 4; [Bu(4)N][Cu(3)(mu(3)-OH)(mu-pz)(3)Cl(3)] (1b), triclinic P-1, a = 9.135(2) A, b = 13.631(2) A, c = 14.510(2) A, alpha = 67.393(2) degrees, beta = 87.979(2) degrees, gamma = 80.268(3) degrees, V = 1643.2(4) A(3), Z = 2; [PPN](2)[Cu(3)(mu(3)-O)(mu-pz)(3)Cl(3)] (2), monoclinic P2/c, a = 12.807(2) A, b = 13.093(2) A, c = 23.139(4) A, beta = 105.391(3) degrees, V = 3741(1) A(3), Z = 2; [PPN](2)[Cu(3)(mu(3)-Cl)(2)(mu-pz)(3)Cl(3)].0.75H(2)O.0.5CH(2)Cl(2) (3a), triclinic P-1, a = 14.042(2) A, b = 23.978(4) A, c = 25.195(4) A, alpha = 76.796(3) degrees, beta = 79.506(3) degrees, gamma = 77.629(3) degrees, V = 7988(2) A(3), Z = 4; [Bu(4)N](2)[Cu(3)(mu(3)-Cl)(2)(mu-pz)(3)Cl(3)] (3b), monoclinic C2/c, a = 17.220(2) A, b = 15.606(2) A, c = 20.133(2) A, beta = 103.057(2) degrees, V = 5270(1) A(3), Z = 4; [Et(3)NH][Cu(3)(mu(3)-OH)(mu-pz)(3)Cl(3)(pzH)] (4), triclinic P-1, a = 11.498(2) A, b = 11.499(2) A, c = 12.186(2) A, alpha = 66.475(3) degrees, beta = 64.279(3) degrees, gamma = 80.183(3) degrees, V = 1331.0(5) A(3), Z = 2. Magnetic susceptibility measurements show that the three copper centers of 2 are strongly antiferromagnetically coupled with J(Cu-Cu) = -500 cm(-1).     

Sandwich-type germanotungstates: structure and magnetic properties of the dimeric polyoxoanions [M4(H2O)2(GeW9O34)2]12 - (M = Mn2+, Cu2+, Zn2+, Cd2+)

The novel dimeric germanotungstates [M(4)(H(2)O)(2)(GeW(9)O(34))(2)](12)(-) (M = Mn(2+), Cu(2+), Zn(2+), Cd(2+)) have been synthesized and characterized by IR spectroscopy, elemental analysis, magnetic measurements, and (183)W-NMR spectroscopy. X-ray single-crystal analyses were carried out on Na(12)[Mn(4)(H(2)O)(2)(GeW(9)O(34))(2)].38H(2)O (Na(12)()-1), which crystallizes in the monoclinic system, space group P2(1)/n, with a = 13.0419(8) A, b = 17.8422(10) A, c = 21.1626(12) A, beta = 93.3120(10) degrees, and Z = 2; Na(11)Cs(2)[Cu(4)(H(2)O)(2)(GeW(9)O(34))(2)]Cl.31H(2)O (Na(11)()Cs-2) crystallizes in the triclinic system, space group P, with a = 12.2338(17) A, b = 12.3833(17) A, c = 15.449(2) A, alpha = 100.041(2) degrees, beta = 97.034(2) degrees, gamma = 101.153(2) degrees, and Z = 1; Na(12)[Zn(4)(H(2)O)(2)(GeW(9)O(34))(2)].32H(2)O (Na(12)()-3) crystallizes in the triclinic system, space group P, with a = 11.589(3) A, b = 12.811(3) A, c = 17.221(4) A, alpha = 97.828(6) degrees, beta = 106.169(6) degrees, gamma = 112.113(5) degrees, and Z = 1; Na(12)[Cd(4)(H(2)O)(2)(GeW(9)O(34))(2)].32.2H(2)O (Na(12)()-4) crystallizes also in the triclinic system, space group P, with a = 11.6923(17) A, b = 12.8464(18) A, c = 17.616(2) A, alpha = 98.149(3) degrees, beta = 105.677(3) degrees, gamma = 112.233(2) degrees, and Z = 1. The polyanions consist of two lacunary B-alpha-[GeW(9)O(34)](10)(-) Keggin moieties linked via a rhomblike M(4)O(16) (M = Mn, Cu, Zn, Cd) group leading to a sandwich-type structure. (183)W-NMR studies of the diamagnetic Zn and Cd derivatives indicate that the solid-state polyoxoanion structures are preserved in solution. EPR measurements on Na(12)()-1 at frequencies up to 188 GHz and temperatures down to 4 K yield a single, exchange-narrowed peak, at g(iso) = 1.9949, typical of Mn systems, and an upper limit of |D| = 20.0 mT; its magnetization studies still await further theoretical treatment. Detailed EPR studies on Na(11)()Cs-2 over temperatures down to 2 K and variable frequencies yield g( parallel ) = 2.4303 and g( perpendicular ) = 2.0567 and A( parallel ) = 4.4 mT (delocalized over the Cu(4) framework), with |D| = 12.1 mT. Magnetization studies in addition yield the exchange parameters J(1) = -11 and J(2) = -82 cm(-)(1), in agreement with the EPR studies.     

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.     

Long-range ferromagnetic ordering in two-dimensional coordination polymers Co[N(CN)2]2(L) [L = pyrazine dioxide (pzdo) and 2-methyl pyrazine dioxide (mpdo)] with dual mu- and mu3-[N(CN)2] bridges

Two novel coordination polymers of Co(II) with dicyanamide (dca) were obtained by the addition of ancillary ligands of pyrazine dioxide (pzdo) and 2-methyl pyrazine dioxide (mpdo) into the Co-dca binary system, respectively. Co[N(CN)(2)](2)(pzdo) (1) crystallizes in the orthorhombic space group of Pnnm (No. 58) with a = 9.4699(5) A, b = 14.9984(3) A, c = 7.4313(7) A, and Z = 4, while Co[N(CN)(2)](2)(mpdo) (2) is in the monoclinic space group C2 (No. 5) with a = 16.5391(4) A, b = 9.6065(2) A, c = 7.5001(2) A, beta = 105.779(1) degrees, and Z = 4. Both complexes contain similar two-dimensional triangular Co-dca layers, which offer rare examples of mixed 1,5-mu- and mu(3)-dca bridging coordination polymers with long-range ferromagnetic ordering below ca. 2.5 K.     

Synthesis, crystal structures, and magnetism of cobalt coordination polymers based on dicyanamide and pyrazine-dioxide derivatives

Three coordination polymers of Co(II) with dicyanamide (dca) were obtained by adding coligands of 2,5-dimethylpyrazine-dioxide (2,5-dmpdo), 2,3,5-trimethylpyrazine-dioxide (2,3,5-tmpdo), or 2,3,5,6-tetramethylpyrazine-dioxide (2,3,5,6-tmpdo) to the binary system of Co-dca. Co2(dca)(4)(2,5-dmpdo)2 (1) crystallizes in the triclinic space group P with a=7.4962(2), b=9.0364(2), c = 10.4783(4) A, alpha = 72.567(1), beta = 72.557(1), gamma = 68.814(2) degrees , V = 616.61(3) A(3), Z = 1, and R1 = 0.0345. [Co3(dca)6(H2O)4].2(2,3,5-tmpdo) (2) is in the monoclinic space group C2/c with a = 29.477(1), b = 7.3735(2), c = 17.4631(7) A, beta = 93.652(1) degrees , V = 3787.9(2) A(3), Z = 4, and R1 = 0.0532. [Co(dca)2(H2O)2].2(2,3,5,6-tmpdo) (3) is in the monoclinic space group P2(1)/c with a = 9.4739(3), b = 11.3876(3), c = 12.1778(3) A, beta = 98.967(1) degrees , V = 1297.74(6) A(3), Z = 4, and R1 = 0.0481. 1 contains an unusual (4,4) Co-dca layer, representing a rare example of metal-dca coordination polymers with mixing 1,3-mu(2)- and 1,5-mu2-dca bridges. The Co-dca (4, 4) layers are connected by 2,5-dmpdo to give an alpha-Po-type network, which displays antiferromagnetic ordering below 10.8 K. 2 is a unique 3D framework composed of 2D twinned 1,5-mu2-dca bridged layers, which are connected by Co-H2O-Co linkages. The noncoordinated 2,3,5-tmpdo units and the coordination water molecules form hydrogen-bonded chains that thread the framework. 3 has alternating stacks of usual Co-dca (4, 4) layers through 1,5-mu2-dca bridges and organic layers of noncoordinated 2,3,5,6-tmpdo. Weak antiferromagnetic and weak ferromagnetic coupling was observed in 2 and 3, respectively.     

2D copper(II) complex built from N-methyl-1,3-diamino-2-propanolate and azide ligands: structure, magnetic, and DFT studies

The synthesis, structural characterization, and magnetic behavior of a new 2D copper(II) compound with formula {[Cu2(mu-O2CMe)(mu-MedapO)(mu1,1-N3)2]n (CH3OH)n} 1, in which MedapOH is N-methyl-1,3-diamino-2-propanol is reported herein. 1 crystallizes in the triclinic system, space group P1, with unit cell parameters a = 6.688(5) A, b = 10.591(6) A, c = 12.100(7) A, alpha = 113.01(3) degrees, beta = 105.08(4) degrees, gamma = 93.93(3) degrees, Z = 2. The structure of 1 consists of neutral alternate 1D chains formed by the sequence of [Cu(1)-(mu1,1-N3)2-Cu(1)-(MedapO/acetate)-Cu(2)-(mu1,1-N3)2-Cu2)]. Each dinuclear [Cu(1)-Cu(2)] unit interacts with similar dinuclear units of neighbor chains in basis to large Cu-N(azido) distances to give a 2D arrangement. The magnetic behavior of 1 has been checked giving a net ferromagnetic coupling. The fit of the chiM versus T data as dinuclear compound affords a J value of 53.0 cm(-1) as a consequence of the orbital countercomplementarity phenomenon. The exchange pathways have been justified by density functional calculations.     

Macrocyclic copper(II) and zinc(II) complexes incorporating phosphate esters

Slow evaporation of solutions prepared by adding either Cu(ClO(4))(2).6H(2)O or Zn(ClO(4))(2).6H(2)O to solutions containing appropriate proportions of Me(3)tacn (1,4,7-trimethyl-1,4,7-triazacyclononane) and sodium phenyl phosphate (Na(2)PhOPO(3)) gave dark blue crystals of [Cu(3)(Me(3)tacn)(3)(PhOPO(3))(2)](ClO(4))(2).(1)/(2)H(2)O (1) and colorless crystals of [Zn(2)(Me(3)tacn)(2)(H(2)O)(4)(PhOPO(3))](ClO(4))(2).H(2)O (2), respectively. Blue crystals of [Cu(tacn)(2)](BNPP)(2) (3) formed in an aqueous solution of [Cu(tacn)Cl(2)], bis(p-nitrophenyl phosphate) (BNPP), and HEPES buffer (pH 7.4). Compound 1 crystallizes in the triclinic space group P1 (No. 2) with a = 9.8053(2) A, b = 12.9068(2) A, c = 22.1132(2) A, alpha = 98.636(1) degrees, beta = 99.546(1) degrees, gamma = 101.1733(8) degrees, and Z = 2 and exhibits trinuclear Cu(II) clusters in which square pyramidal metal centers are capped by two phosphate esters located above and below the plane of the metal centers. The trinuclear cluster is asymmetric having Cu...Cu distances of 4.14, 4.55, and 5.04 A. Compound 2 crystallizes in the monoclinic space group P2(1)/c (No. 14) with a = 13.6248(2) A, b = 11.6002(2) A, c = 25.9681(4) A, beta = 102.0072(9) degrees, and Z = 4 and contains a dinuclear Zn(II) complex formed by linking two units of [Zn(Me(3)tacn)(OH(2))(2)](2+) by a single phosphate ester. Compound 3 crystallizes in the monoclinic space group C2/c (No. 15) with a = 24.7105(5) A, b = 12.8627(3) A, c = 14.0079(3) A, beta = 106.600(1) degrees, and Z = 4 and consists of mononuclear [Cu(tacn)(2)](2+) cations whose charge is balanced by the BNPP(-) anions.     

Copper(II) complexes of a series of alkoxy diazine ligands: mononuclear, dinuclear, and tetranuclear examples with structural, magnetic, and DFT studies

Picolyl hydrazide ligands have two potentially bridging functional groups (micro-O, micro-N-N) and consequently can exist in different coordination conformers, both of which form spin-coupled polynuclear coordination complexes, with quite different magnetic properties. The complex [Cu(2)(POAP-H)Br(3)(H(2)O)] (1) involves a micro-N-N bridge (Cu-N-N-Cu 150.6 degrees ) and exhibits quite strong antiferromagnetic coupling (-2J = 246(1) cm(-)(1)). [Cu(2)(PZOAPZ-H)Br(3)(H(2)O)(2)] (2) has two Cu(II) centers bridged by an alkoxide group with a very large Cu-O-Cu angle of 141.7 degrees but unexpectedly exhibits quite weak antiferromagnetic exchange (-2J = 91.5 cm(-)(1)). This is much weaker than anticipated, despite direct overlap of the copper magnetic orbitals. Density functional calculations have been carried out on compound 2, yielding a similar singlet-triplet splitting energy. Structural details are reported for [Cu(2)(POAP-H)Br(3)(H(2)O)] (1), [Cu(2)(PZOAPZ-H)Br(3)(H(2)O)(2)] (2), [Cu(2)(PAOPF-2H)Br(2)(DMSO)(H(2)O)].H(2)O (3), [Cu(4)(POMP-H))(4)](NO(3))(4).2H(2)O (4), and PPOCCO (5) (a picolyl hydrazide ligand with a terminal oxime group) and its mononuclear complexes [Cu(PPOCCO-H)(NO(3))] (6) and [Cu(PPOCCO-H)Cl] (7). Compound 1 (C(12)H(13)Br(3)Cu(2)N(5)O(4)) crystallizes in the monoclinic system, space group P2(1)/c, with a = 15.1465(3) A, b = 18.1848(12) A, c = 6.8557(5) A, beta = 92.751(4) degrees, and Z = 4. Compound 2 (C(10)H(13)Br(3)Cu(2)N(7)O(4)) crystallizes in the triclinic system, space group P, with a = 9.14130(1) A, b = 10.4723(1) A, c = 10.9411(1) A, alpha = 100.769(1), beta = 106.271(1) degrees, gamma = 103.447(1) degrees, and Z = 2. Compound 3 (C(23)H(22)Br(2)Cu(2)N(7)O(5.5)S) crystallizes in the monoclinic system, space group P2(1)/c, with a = 12.406(2) A, b = 22.157(3) A, c = 10.704(2) A, beta = 106.21(1) degrees, and Z = 4. Compound 4(C(52)H(48)Cu(4)N(20)O(18)) crystallizes in the monoclinic system, space group P2(1)/n, with a = 14.4439(6) A, b = 12.8079(5) A, c = 16.4240(7) A, beta = 105.199(1) degrees, and Z = 4. Compound 5 (C(15)H(14)N(4)O(2)) crystallizes in the orthorhombic system, space group Pna2(1), with a = 7.834(3) A, b = 11.797(4) A, c = 15.281(3) A, and Z = 4. Compound 6(C(15)H(13)CuN(5)O(5)) crystallizes in the monoclinic system, space group P2(1)/c, with a = 8.2818(9) A, b = 17.886(2) A, c = 10.828(1) A, beta = 92.734(2) degrees, and Z = 4. Compound 7 (C(15)H(13)CuClN(4)O(2)) crystallizes in the orthorhombic system, space group Pna2(1), with a = 7.9487(6) A, b = 14.3336(10) A, c = 13.0014(9) A, and Z = 4. Density functional calculations on PPOCCO are examined in relation to the anti-eclipsed conformational change that occurs on coordination to copper(II).     

Synthesis, structures, and magnetic properties of tri- and dinuclear copper(II)-gadolinium(III) complexes of linear oligooxime ligands

We have designed and synthesized a new Cu2Gd heterotrinuclear complex, [LCu2Gd(OAc)3] (1), where H4L is a bis(salen)-type tetraoxime ligand useful in the synthesis of discrete (3d)2(4f) complexes. Complex 1 crystallizes in the triclinic system, space group P1, with unit cell parameters a = 12.442(4) A, b = 13.397(3) A, c = 13.966(4) A, alpha = 77.052(8) degrees, beta = 88.656(10) degrees, gamma = 77.761(8) degrees, and Z = 2. In the crystal structure of 1, Cu-Gd distances are 3.3-3.5 A, whereas the two Cu atoms are separated by 6.08 A. The corresponding dinuclear CuGd complexes, 2 and 3, with mono(salen)-type chelate 3-MeOsalamo were also synthesized. Complex 2 crystallizes in the monoclinic system, space group P2(1)/c, with unit cell parameters a = 13.869(8) A, b = 13.688(7) A, c = 18.728(10) A, beta = 92.861(8) degrees, and Z = 4, and complex 3 crystallizes in the triclinic system, space group P1, with unit cell parameters a = 12.319(4) A, b = 13.989(4) A, c = 16.774(5) A, alpha = 64.699(14) degrees, beta = 66.672(13) degrees, gamma = 76.891(17) degrees, and Z = 4. Interaction between Cu(II) and Gd(III) in the dinuclear complexes 2 and 3 is ferromagnetic (J = 4.5 and 7.6 cm(-1), respectively, using spin Hamiltonian H = -JS(Cu) x S(Gd)) as observed in the previously prepared [LCuGdX3] complexes, where L is a salen-type chelate. Magnetic data for the Cu2Gd trinuclear complex can be reasonably interpreted with the use of a spin Hamiltonian H = -J(CuGd)S(Cu1) x S(Gd) - J(CuGd)S(Cu2) x S(Gd) - J(CuCu)S(Cu1) x S(Cu2) with J(CuGd) = 5.0 cm(-1) and J(CuCu) = 0 cm(-1). The S = 9/2 ground state resulted from the ferromagnetic interaction among the Cu(II)-Gd(III)-Cu(II) triad was also supported by the saturation magnetization at 1.8 K.     

Two-dimensional coordination polymers of copper(II) with oxalate: lattice water control of structure

Three oxalate copper(II) complexes, [Cu(bipy)(C(2)O(4))(H(2)O)].2H(2)O (1), [Cu(nphen)(C(2)O(4))(H(2)O)].2H(2)O (2), and [Cu(phen)(C(2)O(4))(H(2)O)].H(2)O (3) (bipy = 2,2'-bipyridine, nphen = 5-nitro-1,10-phenanthroline and phen = 1,10-phenanthroline), have been synthesized and their crystal structures have been determined. Compound 1 crystallizes in the triclinic space group P1 with a = 7.2554(10) A, b = 10.5712(14) A, c = 10.8178(15) A, alpha = 62.086(2) degrees, beta = 77.478(3) degrees, gamma = 81.773(3) degrees, and Z = 2. Compound 2 crystallizes in the triclinic space group P1 with a = 9.582(2) A, b = 10.086(2) A, c = 10.592(2) A, alpha = 64.18(3) degrees, beta = 79.47(3) degrees, gamma = 60.06(3) degrees, and Z = 2. Compound 3 crystallizes in the monoclinic space group P2(1)/n with a = 8.4655(7) A, b = 9.7057(8) A, c = 17.4572(14) A; beta = 103.865(2) degrees, and Z = 4. The crystal structures of all complexes consist of neutral [Cu(L)(C(2)O(4))(H(2)O)] (L = bipy, nphen, and phen) units and one or two lattice water molecules in the unit cell. Each copper atom in 1, 2, and 3 involves a five-coordinate CuN(2)O(2)O' environment, with a distorted square-pyramidal structure. In 1 and 2, two lattice water molecules are around each unit of [CuL(C(2)O(4))(H(2)O)] (L = bipy and nphen) and form two-dimensional networks. Only one lattice water molecule is found in the unit cell of 3 and the two-dimensional structure is different from 1 and 2. The extended three-dimensional structure is formed through pi-pi interactions between layers. The influences of hydrogen bonds and the sizes and Lewis basicity of ligands to the structures were discussed.     

Homologous series of redox-active, dinuclear cations [M(2)(O(2)CCH(3))(2)(pynp)(2)](2+) (M = Mo, Ru, Rh) with the bridging ligand 2-(2-pyridyl)-1,8-naphthyridine (pynp)

A homologous series of dinuclear compounds with the bridging ligand 2-(2-pyridyl)-1,8-naphthyridine (pynp) has been prepared and characterized by X-ray crystallographic and spectroscopic methods. [Mo(2)(O(2)CCH(3))(2)(pynp)(2)][BF(4)](2) x 3CH(3)CN (1) crystallizes in the monoclinic space group P2(1)/c with a = 15.134(5) A, b = 14.301(6) A, c = 19.990(6) A, beta = 108.06(2) degrees, V = 4113(3) A(3), and Z = 4. [Ru(2)(O(2)CCH(3))(2)(pynp)(2)][PF(6)](2) x 2CH(3)OH (2) crystallizes in the monoclinic space group C2/c with a = 14.2228(7) A, b = 20.3204(9) A, c = 14.1022(7) A, beta = 95.144(1) degrees, V = 4059.3(3) A(3), and Z = 4. [Rh(2)(O(2)CCH(3))(2)(pynp)(2)][BF(4)](2) x C(7)H(8) (3) crystallizes in the monoclinic space group C2/c with a = 13.409(2) A, b = 21.670(3) A, c = 13.726(2) A, beta = 94.865(2) degrees, V = 3973.9(8) A(3), and Z = 4. A minor product, [Rh(2)(O(2)CCH(3))(2)(pynp)(2)(CH(3)CN)(2)][BF(4)][PF(6)] x 2CH(3)CN (4), was isolated from the mother liquor after crystals of 3 had been harvested; this compound crystallizes in the triclinic space group, P1 with a = 12.535(3) A, b = 13.116(3) A, c = 13.785(3) A, alpha = 82.52(3) degrees, beta = 77.70(3) degrees, gamma = 85.76(3) degrees, V = 2193.0(8) A(3), and Z = 2. Compounds 1-3 constitute a convenient series for probing the influence of the electronic configuration on the extent of mixing of the M-M orbitals with the pi system of the pynp ligand. Single point energy calculations performed on 1-3 at the B3LYP level of theory lend insight into the bonding in these compounds and allow for correlations to be made with electronic spectral data. Although purely qualitative in nature, the values for normalized change in orbital energies (NCOE) of the frontier orbitals before and after reduction are in agreement with the observed differences in reduction potentials as determined by cyclic voltammetry.     

A novel hexanuclear mixed oxidation state Cu(II)(4)Cu(I)(2) cluster complex exhibiting weak ferromagnetic exchange

The complex [(PAH)(4)Cu(II)(4)Cu(I)(2)Br(10)] (1) (PAH = picolinamide hydrazone) containing a Cu(II)(4)Cu(I)(2) hexanuclear cluster, with two well-separated Cu(II)(2) dinuclear centers, results from a redox reaction involving a hydrolytically unstable ligand, salicilyl picolinamide hydrazone, and CuBr(2) in aqueous acetonitrile. The Cu(II) centers are axially bridged via long bromine contacts, leading to ferromagnetic exchange (2J = 4.04 cm(-)(1)). Density functional calculations have been carried out, giving a comparable singlet-triplet splitting energy. 1 crystallizes in the triclinic system, space group Ponemacr;, with a = 9.253(3) A, b = 18.159(3) A, c = 7.199(5) A, alpha = 91.31(3) degrees, beta = 107.35(4) degrees, gamma = 104.22(2) degrees, and Z = 2.     

Synthesis and characterization of the complexes of pentane-2,4-dione with nickel(II) and cobalt(III): [Ni(acac)2].0.5CH3OH and [Co(acac)2NO3].2H2O (acac = pentane-2,4-dione)

Two mononuclear complexes, [Ni(acac)2].0.5CH3OH (1) and[Co(acac)2NO3].2H2O (2) (acac = pentane-2,4-dione), have been synthesized and characterized by single crystal X-ray analysis. Complex 1 crystallizes in the monoclinic space group P2(1)/c with a = 9.295(4), b = 11.450(5), c = 12.974(6) A, V = 1379.1(11) A(3),beta = 92.854(7), and Z = 4. Complex 2 crystallizes in the triclinic space group P(-1) with a= 8.153(9), b = 9.925(11), c = 10.355(12), V = 746.3(15) A(3), alpha = 70.530(16), beta =71.154(15), gamma = 80.698(16) and Z = 2. Complex 1 has a one-dimensional chain-like structure, which is extended by weak hydrogen contacts, while complex 2 shows a three-dimensional network structure.     

Crystal Structures of a Family of New Copper(I) Cyanide Complexes of Thiourea and Substituted Thioureas

The syntheses and crystal structures of the first cyanide, sulfur mixed ligand copper(I) complexes are reported. The first complex of the family was discovered when (CuCN)(3)(C(6)H(12)N(4))(2) (1) (C(6)H(12)N(4) = hexamethylenetetramine) was treated with aqueous thiourea. The sulfur ligands include thiourea (tu), 1,3-dimethyl-2-thiourea (dmtu), 1,3-diethyl-2-thiourea (detu), 1,1,3,3-tetramethyl-2-thiourea (tmtu), and 2-imidazolidinethione (N,N'-ethylenethiourea, etu). Synthesis was effected by adding the ligand to a solution of CuCN in aqueous sodium thiosulfate. Complex 2, (CuCN)(2)(tu)(3)(H(2)O), crystallizes in the triclinic space group P&onemacr;with unit cell dimensions a = 7.696(5) ?, b = 9.346(2) ?, c = 10.772(2) ?, alpha = 106.53(2) degrees, beta = 91.11(4) degrees, gamma = 98.42(3) degrees, and Z = 2. Complex 3, (CuCN)(3)(dmtu)(2), crystallizes in the monoclinic space group Cc with unit cell dimensions a = 10.082(3) ?, b = 14.984(5) ?, c = 11.413(3) ?, beta = 104.50(2) degrees, and Z = 4. Complex 4, (CuCN)(2)(detu)(H(2)O), crystallizes in the monoclinic space group P2(1)/n with unit cell dimensions a = 7.969(5) ?, b = 11.559(4) ?, c = 13.736(5) ?, beta = 100.48(4) degrees, and Z = 4. Complex 5, (CuCN)(tmtu) (polymorph a), crystallizes in the orthorhombic space group P2(1)2(1)2(1) with unit cell dimensions a = 8.653(1) ?, b = 9.426(1) ?, c = 11.620(3) ?, and Z = 4. Complex 6, (CuCN)(tmtu) (polymorph b), which has the same connectivity as 5, crystallizes in the triclinic space group P&onemacr; with unit cell dimensions a = 9.660(4) ?, b = 14.202(4) ?, c = 16.03(1) ?, alpha = 101.68(5) degrees, beta = 107.08(6) degrees, gamma = 70.07(2) degrees, and Z = 8. The difference between the polymorphs is that 5 has a zig-zag chain with a repeat unit of two while 6 has a 4-fold helix. Complex 7, (CuCN)(2)(etu), crystallizes in the monoclinic space group P2(1)( )()with unit cell dimensions a = 3.994(2) ?, b = 13.886(3) ?, c = 7.556(1) ?, beta = 97.07(2) degrees, and Z = 2.     

Synthesis and characterization of six new quaternary actinide thiophosphate compounds: Cs(8)U(5)(P(3)S(10))(2)(PS(4))(6)(,) K(10)Th(3)(P(2)S(7))(4)(PS(4))(2), and A(5)An(PS(4))(3), (A = K, Rb, Cs; An = U, Th)

Six new actinide metal thiophosphates have been synthesized by the reactive flux method and characterized by single-crystal X-ray diffraction: Cs(8)U(5)(P(3)S(10))(2)(PS(4))(6) (I), K(10)Th(3)(P(2)S(7))(4)(PS(4))(2) (II), K(5)U(PS(4))(3) (III), K(5)Th(PS(4))(3) (IV), Rb(5)Th(PS(4))(3) (V), and Cs(5)Th(PS(4))(3) (VI). Compound I crystallizes in the monoclinic space group P2(1)/c with a = 33.2897(1) A, b = 14.9295(1) A, c = 17.3528(2) A, beta = 115.478(1) degrees, Z = 8. Compound II crystallizes in the monoclinic space group C2/c with a = 32.8085(6) A, b = 9.0482(2) A, c = 27.2972(3) A, beta = 125.720(1) degrees, Z = 8. Compound III crystallizes in the monoclinic space group P2(1)/c with a = 14.6132(1) A, b = 17.0884(2) A, c = 9.7082(2) A, beta = 108.63(1) degrees, Z = 4. Compound IV crystallizes in the monoclinic space group P2(1)/n with a = 9.7436(1) A, b = 11.3894(2) A, c = 20.0163(3) A, beta = 90.041(1) degrees, Z = 4, as a pseudo-merohedrally twinned cell. Compound V crystallizes in the monoclinic space group P2(1)/c with a = 13.197(4) A, b = 9.997(4) A, c = 18.189(7) A, beta = 100.77(1) degrees, Z = 4. Compound VI crystallizes in the monoclinic space group P2(1)/c with a = 13.5624(1) A, b = 10.3007(1) A, c = 18.6738(1) A, beta = 100.670(1) degrees, Z = 4. Optical band-gap measurements by diffuse reflectance show that compounds I and III contain tetravalent uranium as part of an extended electronic system. Thorium-containing compounds are large-gap materials. Raman spectroscopy on single crystals displays the vibrational characteristics expected for [PS(4)](3)(-), [P(2)S(7)](4-), and the new [P(3)S(10)](5)(-) building blocks. This new thiophosphate building block has not been observed except in the structure of the uranium-containing compound Cs(8)U(5)(P(3)S(10))(2)(PS(4))(6).     

Linear Trinuclear Pt.Mo-Mo Complexes [Mo(2)PtX(2)(pyphos)(2)(O(2)CR)(2)](2) (X = Cl, Br, I; R = CH(3), C(CH(3))(3); pyphos = 6-(Diphenylphosphino)-2-pyridonate) with an Axial Interaction between the Quadruply Bonded Mo(2) Moiety and the Platinum Atom

An example of a direct axial interaction of a platinum(II) atom with a Mo(2) core through a uniquely designed tridentate ligand 6-(diphenylphosphino)-2-pyridonate (abbreviated as pyphos) is described. Treatment of PtX(2)(pyphosH)(2) (2a, X = Cl; 2b, X = Br; 2c, X = I) with a 1:1 mixture of Mo(2)(O(2)CCH(3))(4) and [Mo(2)(O(2)CCH(3))(2)(NCCH(3))(6)](2+) (3a) in dichloromethane afforded the linear trinuclear complexes [Mo(2)PtX(2)(pyphos)(2)(O(2)CCH(3))(2)](2) (4a, X = Cl; 4b, X = Br; 4c, X = I). The reaction of [Mo(2)(O(2)CCMe(3))(2)(NCCH(3))(4)](2+) (3b) with 2a-c in dichloromethane afforded the corresponding pivalato complexes [Mo(2)PtX(2)(pyphos)(2)(O(2)CCMe(3))(2)](2) (5a, X = Cl; 5b, X = Br; 5c, X = I), whose bonding nature is discussed on the basis of the data from Raman and electronic spectra as well as cyclic voltammograms. The linear trinuclear structures in 4b and 5a-c were confirmed by NMR studies and X-ray analyses: 4b, monoclinic, space group C2/c, a = 34.733(4) ?, b = 17.81(1) ?, c = 22.530(5) ?, beta = 124.444(8) degrees, V = 11498(5) ?(3), Z = 8, R = 0.060 for 8659 reflections with I > 3sigma(I) and 588 parameters; 5a, triclinic, space group P&onemacr;, a = 13.541(3) ?, b = 17.029(3) ?, c = 12.896(3) ?, alpha = 101.20(2) degrees, beta = 117.00(1) degrees, gamma = 85.47(2) degrees, V = 2599(1) ?(3), Z = 2, R = 0.050 for 8148 reflections with I > 3sigma(I) and 604 parameters; 5b, triclinic, space group P&onemacr;, a = 12.211(2) ?, b = 20.859(3) ?, c = 10.478(2) ?, alpha = 98.88(1) degrees, beta = 112.55(2) degrees, gamma = 84.56(1) degrees, V = 2433.3(8) ?(3), Z = 2, R = 0.042 for 8935 reflections with I > 3sigma(I) and 560 parameters; 5c, monoclinic, space group P2(1)/n, a = 13.359(4) ?, b = 19.686(3) ?, c = 20.392(4) ?, beta = 107.92(2) degrees, V = 5101(2) ?(3), Z = 4, R = 0.039 for 8432 reflections with I > 3sigma(I) and 560 parameters.     

Cyano-bridged homometallic 1-D and bimetallic 2-D assemblies: synthesis,structures, and magnetic properties of [Ni(baepn)(CN)]n(ClO4)n and [Ni(baepn)]2n[Fe(CN)(6)]n(H2O)8n

Cyano-bridged homometallic complex [Ni(baepn)(CN)](n)(ClO(4))(n)(1) and bimetallic complex [Ni(baepn)](2)(n)[Fe(CN)(6)](n)(H(2)O)(8)(n)(2) [baepn = N,N'-bis(2-aminoethyl)-1,3-propanediamine] were synthesized and characterized. 1 crystallizes in the monoclinic space group P2(1)/n with a = 9.560(3) A, b = 10.700(3) A, c = 14.138(9) A, beta = 90.18(6) degrees, and Z = 4; 2 crystallizes in the monoclinic space group P2(1)/c with a = 8.951(2) A, b = 13.672(3) A, c = 14.392(3) A, beta = 98.906(4) degrees, and Z = 4. The complex 1 has one-dimensional structure whose chain vector runs along the b axis with baepn ligands and perchlorate anions alternately arranged up and down in the c direction. The antiferromagnetic nature of 1 was explained in terms of the infinite chain model and Haldane gap, giving g = 2.33, J = -29.4 cm(-1), and the magnitude of Haldane gap E(g) = 5.22 K. The complex 2 that constitutes the first example of 2-D bimetallic assembly of Ni(II) ion and ferrocyanide anion is composed of the neutral layers based on the [Ni(4)Fe(4)] square grid spanning in the bc plane. For 2, the analysis with the Curie-Weiss law in 2-300 K range results in THETA = 0.200 K and the magnetism was explained in terms of the ability of ferrocyanide in the -Ni-NC-Fe-CN-Ni unit to promote ferromagnetic Ni-Ni interaction.     

三维银配位聚合物[Ag3(IN)2(CF3COO)]的水热合成与晶体结构

本文在水热条件下, 通过4-氰基吡啶发生原位水解得到异烟酸, 将其与AgCF3CO2作用合成了新型银配位聚合物, 并通过元素分析和X射线单晶衍射分析等手段对其结构进行了表征.