C–H···F Hydrogen-Bonded Assembly of Ni(II) and Cu(II) Complexes Generate 3D Supramolecular Frameworks

Abstract  Syntheses and X-ray structural characterizations of two new complexes [Ni(imi)₆](pfbz)₂ (1) and Cu(imi)₂(pfbz)₂ (2) (imi = imidazole, pfbz = pentafluorobenzoate) are reported. The first complex crystallizes in the triclinic space group P-1 with the crystal cell parameters a = 9.180(2) ?, b = 9.742(3) ?, c = 11.466(3) ?, α = 76.947(18)°, β = 80.629(18)°, γ = 78.043(19)°, V = 970.0(4) ?³ and Z = 1. The second complex crystallizes in the triclinic space group P-1 with the crystal cell parameters a = 7.3250(12) ?, b = 7.6685(10) ?, c = 10.888(4) ?, α = 92.80(2)°, β = 101.92(2)°, γ = 115.038(12)°, V = 535.7(2) ?³ and Z = 1. Examination of the structures shows that both complexes form three-dimensional hydrogen bonded networks in which C–H···F hydrogen bonds play significant roles. Index Abstract   C–H···F Hydrogen-Bonded Assembly of Ni(II) and Cu(II) Complexes Generate 3D Supramolecular Frameworks Chun-Hua Ge, Xiao-Yan Zhang, Fang Yu, Ya-Nan Guo, Xiang-Dong Zhang* and Qi-Tao Liu C–H···F interactions link simple complexes to form intricate three-dimensional supramolecular networks.      

Bis(2,2′-biimidazoline)bis(isothiocyanato)Metal(II) compounds. Synthesis,characterization and lattice hydrogen bonding for Metal = Mn(II) and Ni(II)

The synthesis, characterization and X-ray structures of two compounds with the general formula trans-M(biz)₂(NCS)₂ (in which biz = 2,2′-biimidazoline and M = Mn(II) for compound 1 and Ni(II) for compound 2) are reported. Both compounds crystallize in the triclinic space group P-1 with a = 8.393(5), b = 8.946(5), c = 7.659(5) Å, α = 104.440(5), β = 106.880(5), γ = 66.180(5)^∘, V = 497.7(5) ų, Z = 1 for compound 1 and a = 8.155(2), b = 8.8190(10), c = 7.480(2) Å, α = 102.259(15), β = 106.135(13), γ = 67.706(14)^∘, V = 474.7(2) ų, Z = 1 for compound 2.Both metal ions show octahedral coordination with the four nitrogen atoms of two biz ligands in the equatorial plane and the two nitrogen atoms of two isothiocyanate anions in the axial positions. The M–N≡C angles are 166.5(2) and 167.7(2) for compounds 1 and 2, respectively. These values are in the usually obtained range for trans-isothiocyanate coordinated compounds. The sulfur atom of each isothiocyanate anion acts as acceptor for the hydrogen bond with the NH group of the biz ligands. In the IR spectrum the vibrations of the thiocyanate anion are observed at 2090 and 776 cm⁻¹ for compound 1 and at 2108 and 778 cm⁻¹ for compound 2, and these values are typical for linear-bond isothiocyanate complexes of transition metals.     

Structural comparisons between Cu(II) and Ni(II) diaza-coupled quasi-aromatic α-amineoxime complexes

Reaction of NioylH and CuoylH with the diazonium salt of sulfanilic acid quantitatively produces diaza complexes by coupling at the C-12 position. X-ray structural study: [Nioyl–N=N–C₆H₄SO₃H]·H₂O; C₁₉H₂₈O₆N₆S₁Ni₁ M _r = 527.23, monoclinic P2₁/c, a = 12.752(3), b = 10.795(3), c = 16.609(3) Å, = 92.46(3)°, V = 2284.2(9) ų, Z = 4, D _x = 1.533(2) mg m^–3 [Cuoyl–N=N–C₆H₄SO₃H]· HCl ·3H₂O; C₁₉H₃₃O₈N₆S₁Cu₁Cl₁, M _r = 604.56, triclinic, , a = 8.4019(8), b = 11.2266(99), c = 14.9370(20) Å, = 84.264(7), = 75.309(8), = 73.024(8)°, V = 1303.0(2) ų, Z = 2, D _x = 1.541(2) mg m^–3. The complexes were isolated from about 0.2 M HCl and had different formulas due to differing protonation. The sulfonic acid proton resides on the diaza nitrogen attached to the C₆H₄ ring and with the copper(II) analogue, protonation also occurs on the intramolecular hydrogen-bond oxygen. Bond distance and angle comparisons are made and related to potential electron delocalization between aromatic rings.     

Syntheses and Crystal Structures of Two New Cadmium(II) and Nickel(II) Complexes with 1,4-Phenylenediacetate and 2,2′-Bipyridyl-Like Ligands

Abstract  

Two new complexes, namely [Cd(PDA)_0.5(2,2′-bpy)Cl](H₂PDA) (1) and [Ni(PDA)(phen)(H₂O)]₂ (2) (H₂PDA = 1,4-phenylenediacetic acid, 2,2′-bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline), have been synthesized and characterized by elemental analysis, IR spectra and X-ray crystal diffraction. Single-crystal X-ray diffraction analysis shows that complex 1 crystallizes in the triclinic space group P-1 with unit cell dimensions a = 8.760 (4) ?, b = 11.190 (5) ?, c = 13.917 (7) ?, α = 110.383 (5)°, β = 101.736 (5)°, γ = 100.612 (5)°, V = 1202.8 (10) ?³, Z = 2, R ₁ = 0.0314 and wR ₂ = 0.0898. Complex 2 crystallizes in the monoclinic space group P2(1)/n with unit cell dimensions a = 9.911 (3) ?, b = 17.924 (6) ?, c = 10.638 (4) ?, β = 94.998 (5)°, V = 1882.7 (11) ?³, Z = 2, R ₁ = 0.0397 and wR ₂ = 0.1150. In complex 1, Cd(II) ions are alternately bridged by PDA ligands and chloride ions into 1D chains and the PDA ligands display trans-configuration. Complex 2 is a dimer and two Ni(II) ions are linked by two PDA ligands with cis-configuration, resulting in a cyclic structure. In spite of these differences, both in complexes 1 and 2 there are π–π stacking interactions and hydrogen bonding to make them 3D supramolecular frameworks.     

Synthesis, spectral, and single crystal X-ray structural studies on (2,2′-bipyridyl)bis(dimethyldithiocarbamato) zinc(II) and (1,10-phenanthroline) bis(dimethyldithiocarbamato)zinc(II)

Synthesis, spectral, and single crystal X-ray structural studies on (2,2-bipyridyl)bis (dimethyldithiocarbamato)zinc(II) (1) and (l,10-phenanthroline)bis(dimethyldithiocarbamato)zinc(II) (2) complexes are reported in this paper. The complex (1) crystallizes in the orthorhombic lattice, space group Pcca, a = 18.456(3), b = 6.529(2), and c = 17.092(2) Å. The complex (2) crystallizes in the monoclinic space group C2/c, a = 13.372(2), b = 13.850(2), c = 24.680(3) Å, and = 102.71(4)°. IR spectra of the complexes (1) and (2) show the thioureide (C-N) bands at 1489 and 1510 cm^–1, respectively, which are lower than the value observed for the parent bisdithiocarbamate. Reduction in the thioureide stretching frequency is due to the increase in coordination around the zinc ion and the resultant increase in electron density. Thermal studies indicate that the 1,10-phenanthroline adduct is marginally more stable than the other complex. X-ray crystal structures of the two adducts show them to be octahedrally coordinated and monomeric in nature. The Zn-S distances are longer than those observed in the parent bisdithiocarbamate. The thioureide C-N bond distances in (1) and in (2) indicate the partial double bond character. The most important structural changes as a result of the adduct formation are observed in the Zn-S bond distances and S-Zn-S bond angles, in terms of very significant increases in Zn-S bond distances and reductions in S-Zn-S angles, compared to the parent bisdithiocarbamate. The observed changes are indicative of a strong steric force in operation in the adducts rather than electronic effects.     

The X-ray crystal structures of bis(l-α-alaninehydroxamato)nickel(II) and bis(l-α-alaninehydroxamato)copper(II)

The structure of twol--alaninehydroxamato (-Alaha) complexes of Ni(II) and Cu(II) have been determined by single-crystal X-ray diffraction methods. The crystals of Ni(-Alaha)₂·2H₂O (I) are monoclinic witha=12.267(4),b=4.798(2),c=10.017(4)Å,=95.48(3)°,Z=2, and space groupP2₁. The crystals of Cu(-Alaha)₂·2H₂O (II) are monoclinic witha=5.073(2),b=11.463(3),c=20.198(5) Å,Z=4 and space groupP2₁2₁2₁. The values of the final residualsR for Ni(-Alaha)₂·2H₂O and Cu(-Alaha)₂·2H₂O are 0.06 and 0.03, respectively. The molecular structures of Ni(-Alaha)₂ and Cu(-Alaha)₂ consist of a square planar and a pentanuclear piramidal, respectively, with the-alaninehydroxamato, (CH₃CH₂(NH₂)CONOH^–), ligands coordinating to metal ion via the N(amino) and the hydroxamic N^– donors.     

Synthesis and Structure of bis(β-Diketiminate) Chromium(II) Complexes

Abstract  

The new ligand 2,4-N,N′-bis(napthylamino)-pent-2-ene (L^napth) (1) has been synthesized and crystallizes in space group P2₁2₁2₁ with crystal cell parameters a = 8.196(3) ?, b = 9.119(3) ?, c = 25.746(10) ?, V = 1924.3(12) ?³ and Z = 4. The complexes bis[2,4-pentane-N,N′-bis(napthyl)ketiminato] chromium(II) (2), bis[2,4-pentane-N,N′-bis(isopropylphenyl)ketiminato] chromium(II) (3), and bis[2,4-pentane-N,N′-bis(tertbutylphenyl)ketiminato] chromium(II) (4) were synthesized and structurally characterized. Complex 2, the first complex reported with a bis(napthyl) β-diketiminate ligand, crystallizes in space group P − 1 with crystal cell parameters a = 12.0824(15) ?, b = 12.2462(16) ?, c = 14.8975(19) ?, α = 87.035(2)°, β = 80.615(2)°, γ = 62.756(2)°, V = 1932.9(4) ?³ and Z = 2. Complex 3 crystallizes in space group P2₁/n with crystal cell parameters a = 13.088(3) ?, b = 22.222(5) ?, c = 14.206(3) ?, β = 102.310(4)°, V = 4036.6(17) ?³ and Z = 4. Complex 4 crystallizes in space group P2₁/n with crystal cell parameters a = 20.831(6) ?, b = 11.575(4) ?, c = 21.373(7) ?, β = 107.241(5)°, V = 4922(3) ?³ and Z = 4. The degree of twist between the ligand planes is dependent on the steric bulk of the ligand.     

Complexes in the Ni2+-imidazole-RN(CH2COO−)2 systems. The crystal structures of tris(imidazole)iminodiacetatonickel(II) monohydrate, hexa(imidazole)nickel(II) bis(N-methyliminodiacetato)nickelate(II) hexahydrate, and tetra(aqua)bis(imidazole)nickel(II) bis(N-benzyliminodiacetato)nickelate(II)

Crystals of different compositions, namely, [Ni(Ida)(Im)₃] ? H₂O (I), [Ni(Im)₆][Ni(Mida)₂] ? 6H₂O (II), and [Ni(Im)₂(H₂O)₄][Ni(Bida)₂] (III), have been precipitated from aqueous solutions of the Ni²⁺-Lig ^2?-Im systems, where Lig ^2? is Ida, Mida, and Bida, respectively. The crystal structures of I–III are determined by X-ray diffraction analysis (R = 0.0307, 0.0348, and 0.0302 for 3061, 4706, and 2882 reflections, respectively). Crystals I are built of monomeric mixed-ligand complexes and molecules of crystallization water, which are interlinked by hydrogen bonds into a three-dimensional framework. In II and III, the ligands Lig ^2? and Im form charged complexes separately. In II, the cationic and anionic layers of the complexes alternate along the c-axis. Numerous hydrogen bonds involving molecules of crystallization water link the layers into a three-dimensional framework. In III, the cationic and anionic complexes, which serve as proton donors and acceptors, respectively, are bound into layers parallel to the xy plane.     

Structure,magnetic and IR studies of copper(II) diphenylphosphate dihydrate,Cu(DPhP)2·(H2O)2

The title compound has been synthesized, and characterized by means of X-ray, magnetic, and IR-spectroscopic measurements.The crystals of Cu(DPhP)₂(H₂O)₂(DPhP=diphenylphosphate) are monoclinic, space groupI2/c witha=24.126(6),b=8.510(2),c=12.333(3) Å,=90.73(5)° andZ=4. The structure was solved by the heavy-atom technique, and refined by full-matrix least-squares calculations to a finalR of 0.040 for 1494 reflections.The complex is centrosymmetric, and the Cu atom at a center of symmetry is four-fold coordinated with two oxygen atoms from two phosphate groups and two water molecules. The coordination about the Cu atom is square-planar, with Cu-O and Cu-O(W) distances 1.926(3) and 1.912(3) Å, respectively.The O(2) phosphate oxygen is an acceptor of two H bonds; one of them is an intramolecular O(W)-H(2)O(2) of 2.714(4) Å, and the other is an intermolecularO(W)-H(1)O(2ⁱ) of 2.667(4) Å. Their presence is also deduced from the IR spectrum of this compound at 3250 and 3000 cm^–1, respectively.The calculated magnetic moment value of 1.92 B.M. corresponds to that of the monomeric copper(II) complexes including those of some alkyl phosphates.     

Synthesis and crystal structure of Nd(III)–Zn(II) complex

A novel heteronuclear complex, [NdZn₂L₆(NO ₃)(phen)₂] (HL = -methylacrylic acid, phen = 1,10-phenanthroline), was synthesized and characterized by elemental analysis, infrared absorption spectra (IR) and its molecular structure was also determined by X-ray structure analysis. The title complex contains a discrete trinuclear ZnNdZn molecule bridged by carboxylate groups between Zn and Nd ions and crystallizes in space group P¯1 with the cell dimensions: a = 13.601(3) Å, b = 16.859(2) Å, c = 12.575(2) Å, = 110.09(1), = 112.21(1), = 81.10(2).     

Crystal Structures and Properties of Bis(2-Aminopyrimidine-N-)-Bis(Thiocyanato-N)Zinc(II) and Catena-[2-Aminopyrimidine-N- (μ-Thiocynanto-S,N)(Thiocyanato-S)Cadmium(II)]

Abstract  

Complexes [Zn(NCS)₂(2-AMP)₂] (2-AMP = 2-aminopyrimidine) 1 and [Cd(SCN)₂(2-AMP)₂]_n 2 are prepared and characterized by X-ray crystallographic methods. 1 crystallizes in the monoclinic, space group C2/c, with a = 13.5761(14), b = 8.3330(10), c = 13.5962(15) ?, β = 99.5450(10)°, V = 1516.8(3) ?³, Z = 4. In 1, the zinc atom is coordinated by four N atoms from two AMP and two NCS⁻. 2 crystallizes in the monoclinic, space group C2/c, with a = 9.7259(11), b = 19.332(2), c = 8.2149(9) ?, β = 99.817(2)°, V = 1522.0(3) ?³, Z = 4. Complex 2 is made up of 1D chains along a-axis. Each Cd is attached to four NCS⁻ bridges and two pendant 2-AMP ligands.     

Novel Assembly of a Cyanide-Bridged Copper(II)–Nickel(II) Binuclear Complex with a Copper(II) Macrocyclic Ligand

Abstract  

A mononuclear fragment [Cu(L)Cl]ClO₄ (1) and a cyano-bridged Cu^II–Ni^II binuclear complex [CuL][Ni(CN)₄]·0.25H₂O (2) (L = 1,3,6,8,11,14-hexaazatricyclo[12.2.1.18,11]-octadecane), have been prepared and characterized. X-ray single crystal analyses indicate that the both complexes crystallize in the monoclinic crystalline system. The complex of 1 in P1n1 space group with unit cell constants a = 6.1176(6) ?, b = 11.9147(10) ?, c = 12.2041(12) ?, β = 98.816(5)° and 2 in the P2₁/n space group with unit cell constants a = 8.1419(13) ?, b = 14.695(2) ?, c = 16.863(3) ?, β = 98.375(2)° have been revealed. The complex 2 assumes a binuclear structure in which the nickel(II) ion is in a square planar environment and the copper(II) is in a square-prism geometry environment.     

Crystal and molecular structure of aquabis(2,2′-bipyridine)nitratomanganese(II) nitrate monohydrate

A new monomeric manganese(II) nitrate complex with 2,2-bipyridine (bpy), [Mn(bpy)₂(NO₃)(H₂O)](NO₃)·H₂O, has been prepared and characterized by X-ray crystallography. The complex crystallizes in the triclinic space group witha=9.721(3),b=14.691(5),c=8.578(3) Å, =106.79(3), =96.05(3), =82.55(3)°,V=1159.9 ų andZ=2. The structure comprises discrete cation [Mn(bpy)₂(NO₃)(H₂O)]⁺ in which the metal atom is coordinated by a pair of bidentate bpy ligands [Mn–N=2.261(4)–2.299(4) Å], a unidentate nitrato [Mn–O=2.284(4) Å] and aqua [Mn–O=2.160(3) Å] ligands in a highly distorted octahedral arrangement.     

Crystal and molecular structure of aqua(2,2′-bipyridine)bis(betaine)copper(II) perchlorate monohydrate

A new monomeric copper(II) complex with 2,2-bipyridine (bpy) and betaine (bet), [Cu(byy)(bet)₂(H₂O)](ClO₄)₂ · H₂O, has been prepared and characterized by X-ray crystallography. The complex crystallizes in the triclinic space groupP-1 witha=8.859(2),b=11.191(2),c=14.850(3) Å, =91.41(1), =97.19(1), =91.97(1)°,V=1459.2(7) ų, andZ=2. The structure comprises discrete cations [Cu(bpy)(bet)₂(H₂O)]²⁺ in which the metal atom is coordinated in a distorted square-pyramidal environment by two oxygen atoms from a pair of monodentate carboxylato ligands [Cu–O=1.950(2) Å] and two nitrogen atoms of a bidentate bpy ligand [Cu–N=1.997(3)–2.005(3) Å] on the basal plane, and one aqua [Cu–O=2.267(3) Å] ligand at the apical position.     

Phenylmercury(II) dithiophosphates. Crystal structure of (O,O′-diethyldithiophosphate) phenylmercury(II)

The phenylmercury(II) derivatives PhHgS₂P(OR)₂ (R=C₂H₅, C₆H₁₁ and C₆H₅) have been synthesized. (O,O-diethyldithiophosphate) phenylmercury(II), C₁₀H₁₅HgO₂PS₂, crystallizes in the monoclinic space groupP2₁/c (n° 14) witha=7.330(5),b=18.085(2),c=11.552(4)Å,=105.96(5)°,V=1472.3(6)ų,Z=4,D=2.088 g.cm^–3. The mercury atom is coordinated to the phenyl carbon atom and to a ligand sulphur atom in an almost linear arrangement (C-Hg-S angle, 176.0(2)°. The ligand is almost monodentate, its second sulphur atom only being involved in a weak secondary intermolecular bond.IR and Raman studies of the other two compounds suggest the same coordination scheme. Positive ion FAB and¹³C,³¹P and¹⁹⁹Hg NMR spectra are also discussed.     

Crystal structures of bis(cyanido)bis(N,N′-diethylthiourea-κS) mercury(II) and bis(cyanido)bis(N,N′-dipropylthiourea-κS) mercury(II)

Two mercury(II) complexes containing cyanide and, N,N′-diethylthiourea (detu) and N,N′-dipropylthiourea (dprtu) ligands, [(detu)₂Hg(CN)₂] (1) and [(dprtu)₂Hg(CN)₂] (2), respectively, have been prepared and characterized by X-ray crystallography. In the both complexes Hg atom lies on a 2-fold rotation axis, and is coordinated to the sulfur atoms of two thiourea ligands and to two cyanide carbon atoms. Both have a distorted tetrahedral environment with bond angles about the Hg atoms in the range of 93.41(4)°–146.75(19)°. In the crystal structures symmetry related molecules are linked via N-H-N hydrogen bonds resulting in the formation of a two-dimensional network in 1, while in 2 a double stranded one-dimensional chain is formed.     

Crystal and molecular structure of the photocatalyst tris(2,2′-bipyrazine)ruthenium(II) hexafluorophosphate

The X-ray structure determination of the complex tris(2,2-bipyrazine)ruthenium(II) hexafluorophosphate, [Ru(C₈N₄H₆)₃](PF₆)₂, has shown that the compound crystallizes in the monoclinic space group P2₁/c witha=13.459(5),b=23.486(8),c=17.913(10) Å,=139.85(1)°, andZ=4. Each asymmetric unit also contains one dimethylformamide and one water molecule. Least-squares refinement led to an R factor of 0.074 based on 3463 reflections for which I>2(I). The [Ru(C₈N₄H₆)₃]²⁺ cation has no crystallographic symmetry, but the requirements for point symmetry 32 are nearly met. The six Ru-N bond lengths agree within experimental error and have an average length of 2.05(1) Å.     

Crystal and molecular structure of β-resorcylidene aminoguanidine copper(II) complex

The tridentate Schiff base, -resorcylidene aminoguanidine (RAG)1 was synthesized from 2,4-dihydroxybenzaldehyde and aminoguanidine and complexed with copper(II) to form a copper(II)--resorcylidene aminoguanidine (Cu-RAG)2 complex. X-ray diffraction analysis of compound2 (orthorhombic, Pnma,a=11.674(1);b=6.7198(7);c=17.836(2) ) revealed a square-planar copper(II) cation with a tridentate·ligand bound through two nitrogen atoms (N1 and N3) of the aminoguanidine moiety and an oxygen (O1) of the monodeprotonated dihydroxybenzaldehyde function. The remaining coordination site was occupied by chloride and the structure was rigidly planar as demanded by the restrictions of the crystallographic space group. The unit cell contents exhibited an extended sheet-like structure constructed via hydrogen bonds both intermolecularly and involving two water molecules (O3 and O4) also restricted by the same mirror symmetry. The remaining water (O5) provided for interlayer hydrogen bonding.     

Crystal structure and magnetic properties of bis(2,2′-bipyridine) azido copper(II) perchlorate

The title compound has been synthesized and its crystal structure has been solved at room temperature. It crystallizes in the triclinic system, space groupP, witha=7.853(1) Å,b=10.177(1) Å,c=13.651(4) Å,=74.57(1)°,=88.49(1)°, =80.675(4)°, andZ=2. The structure consists of isolated [Cu(bipy)₂N₃]⁺ cations (bipy=2,2-bipyridine) and perchlorate anions. The metallic cation environment has a distorted trigonal-bipyramidal geometry. The EPR spectrum is rhombic, which indicates that the distortion with respect to the perfect trigonal bipyramid is sufficiently pronounced to mixz ²- andx ²–y ²-type orbitals in the ground state. The temperature dependence of the molar magnetic susceptibility has been investigated in the 300-2.2 K temperature range.     

Crystal and molecular structure,and infrared study of bis(2,2′-bipyridine) [N-(toluene-p-sulfonyl)glycinato-NO] cadmium(II) complex and related compounds

A series of complexes of formula [M(II)(bpy)₂(ArSO₂-N-aminoacidato-NO)]·3H₂O [bpy=2,2-bipyridine, M(II)=Zn(II), ArSO₂-N-aminoacidato-NO=N(toluene-p-sulfonyl)- and N(benzenesulfonyl)-glycinate-NO dianion, hereafter abbreviated as tsgly-NO and bsgly-NO, respectively, M(II)=Cd(II), ArSO₂-N-aminoacidato-NO=tsgly-NO] was separated and investigated by spectroscopic and X-ray methods. The crystal structure of [Cd(bpy)₂(tsgly-NO)]·3H₂O was determined. The compound crystallizes in the monoclinic space groupP2/n,Z=4,a=15.427(4),b=13.580(2),c=15.546(4)Å, =110.97(3),R=0.041,R _w =0.043. The structure consists of monomeric, approximately octahedral [Cd(bpy)₂(tsgly-NO)] units with a N₅O donor atom set, which gives rise to three almost orthogonal five-membered chelate rings. The IR spectra suggest similar environments for all the complexes.