Structural Modulation in Lanthanide Tetracyanoplatinates Incorporating Terpyridine: Synthesis and Structures of Four Distinct One-Dimensional Variants

Abstract  

The synthesis of four different lanthanide tetracyanoplatinates all incorporating 2,2′:6′,2″-terpyridine have been carried out in acetonitrile/water mixtures by reaction of an appropriate Ln³⁺ salt with 2,2′:6′,2″-terpyridine and potassium tetracyanoplatinate. The use of different Ln³⁺ salts as reactants results in the isolation of {La(tpy)(H₂O)₃}₂[Pt(CN)₄]₃·2CH₃CN·2H₂O (La-1) space group P[`1] P\bar{1} , a = 9.3862(15) ?, b = 12.186(1) ?, c = 13.493(1) ?, α = 88.082(7)°, β = 80.22(1)°, γ = 74.88(1)°, {Pr(tpy)(H<sub>2</sub>O)<sub>3</sub>}<sub>2</sub>[Pt(CN)<sub>4</sub>]<sub>3</sub>·2H<sub>2</sub>O (Pr-2) space group P[`1] P\bar{1} , a = 9.2458(15) ?, b = 10.8068(9) ?, c = 13.6178(14) ?, α = 84.554(8)°, β = 74.905(10)°, γ = 79.490(9)°, Ho(tpy)(H₂O)₂(NO₃)[Pt(CN)₄] · CH₃CN (Ho-3) space group P2₁/c, a = 12.867(1) ?, b = 15.1046(15) ?, c = 13.651(4) ?, β = 105.39(1)°, or Yb(tpy)(H₂O)₂(NO₃)[Pt(CN)₄]·0.5CH₃CN·1.5H₂O (Yb-4) space group Pbcn, a = 13.226(7) ?, b = 15.870(2) ?, c = 24.276(3) ? under quite similar reaction conditions. All four of these compounds have been isolated as single crystals and X-ray diffraction has been used to investigate their structural features. None of these compounds are isostructural with one another, but all contain one-dimensional, polymeric structures that contain tris chelation of the Ln³⁺ cations by terpyridine and bridging of the Ln³⁺ ions by tetracyanoplatinate. La-1 and Pr-2 contain both cis- and trans-bridging of Ln³⁺ cations by tetracyanoplatinate resulting in double chains with a ladder-type structure. Ho-3 and Yb-4 are similar in that they contain chelation of Ln³⁺ by both terpyridine and a nitrate anion and both structure types only contain cis-bridging by tetracyanoplatinate. All four structures contain Pt–Pt interactions in the form of dimeric units.     

Synthesis and Crystal Structure of a Pure Inorganic Network Based Tetra-Sodium Capped Sandwich-Type Polyanion

Abstract  

The synthesis and single-crystal structure of a Na-salt compound Na₁₀[Co₄(OH₂)₂(AsW₉O₃₄)₂]·32H₂O (1) was reported. Compound 1 crystallizes in triclinic system, space group P−1, with the lattice parameters: a = 11.6040(10) ?, b = 12.9361(13) ?, c = 17.396(2) ?, α = 97.4120(10)°, β = 106.8590(10)°, γ = 111.867(2)° and Z = 1. Compound 1 consists of a pure inorganic network based on tetra-sodium capped sandwich-type anionic clusters [Co₄(OH₂)₂(AsW₉O₃₄)₂]¹⁰⁻ bridged through Na–OH₂ subunits. The thermogravimetric and electrochemistry measurements had also been studied.     

Synthesis and Crystal Structures of Dioxomolybdenum(VI) Complexes with ONS-Donor Ligands

Abstract  

Three dioxomolybdenum complexes namely dioxo(5-chlorosalicylaldehyde thiosemicarbazonato) dimethylsulfoxide molybdenum(VI) (C1), dioxo(5-chlorosalicylaldehyde 2-ethylthiosemicarbazonato) dimethylsulfoxide molybdenum(VI) (C2) and dioxo(5-chlorosalicylaldehyde N-phenylthiosemicarbazonato) dimethylsulfoxide molybdenum(VI) (C3) were prepared. The compounds all crystallize in the triclinic space group P-1 with a = 7.3184(3) ?, b = 7.5035(3) ?, c = 14.9713(6) ?, α = 85.005(2)°, β = 85.616(2)°, γ = 66.987(2)° for C1, a = 8.2339(1) ?, b = 10.1739(1) ?, c = 10.4017(1) ?, α = 78.486(1)°, β = 89.312(1)°, γ = 81.730(1)° for C2, a = 7.0591(1) ?, b = 9.5603(1) ?, c = 14.5762(2) ?, α = 76.280(1)°, β = 81.351(1)°, γ = 81.985(1)° for C3. In general, the overall geometry of these complexes can be regarded as a distorted octahedron with the tridentate thiosemicarbazonato ligands (L²⁻) bonded to the MoO₂ ²⁺ core, with the imine nitrogen, phenoxyl oxygen, sulfur atom and one of the terminal oxygen atoms of the dioxomolybdenum occupying the equatorial position. The sixth coordination site is occupied by the dimethylsulfoxide (DMSO) solvent molecules. The adjacent molecules of C1 are linked by N–H···N intermolecular hydrogen bonding, forming polymeric chains that run parallel to the bc plane. On the other hand, C2 is a discrete molecule while the molecules of C3 associate via weak N–H···O hydrogen bonding interaction to form a polymeric chain that runs along the a-axis.     

Synthesis and Crystal Structure of a 3D Er(III) Coordination Polymer Based on Tripodal Flexible Ligand

Abstract  

Solvothermal reaction of Er(NO₃)₃·6H₂O and tri(2-carboxyethyl)isocyanurate (H₃tci) in DMF/H₂O (DMF = dimethylformamide) medium leads to the generation of one new 3D coordination polymer, [Er(tci)(H₂O)] DMF·2H₂O (1), which was characterized by the elemental analysis, IR spectroscopy and single crystal X-ray diffraction. X-ray diffraction analysis reveals that 1 crystallizes in triclinic space group P-1, features an interesting 3D coordination framework constructed from the flexible tridentate ligand H₃tci. Unit cell parameters for 1: a = 7.853(2) ?, b = 12.186(3) ?, c = 13.222(2) ?, α = 112.156(14)°, β = 105.457(15)°, γ = 91.541(18)° and Z = 2.     

Crystal Structure and Photoluminescent Properties of Two Cadmium(II) Complexes with Orotic Acid

Abstract  

Assembly of orotic acid (2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylic acid, H₃dtpc) and Cd(OAc)₂·2H₂O gave rise to two complexes [Cd₂(H₂dtpc)₂(H₂O)₆] (I) and [Cd(H₂dtpc)(bpy)(H₂O)]_n (II) (bpy = 2,2′-bipyridine). Complex (I) and (II) have been characterized by X-ray single crystal diffraction, IR, PXRD, TGA and fluorescence spectra. Structural analyses reveal that (I) is a binuclear structure, and complex (II) possesses a one-dimensional infinite zig-zag chain architecture and the chains are further assembled into 2D supramolecular network by strong hydrogen bonding interactions. Crystal data for (I): Monoclinic, space group P2(1)/n, a = 9.3221(19) ?, b = 6.6315(13) ?, c = 15.322(3) ?, β = 102.31(3)°, V = 925.4(3) ?³, Z = 4, R1 = 0.0269, and wR2 = 0.0604; for (II): Monoclinic, space group P2(1)/c, a = 9.9880(2) ?, b = 14.5085(2) ?, c = 11.6957(2) ?, β = 107.976(2)°, V = 1612.10(5) ?³, Z = 4, R1 = 0.0234 and wR2 = 0.0554.     

Synthesis and Crystal Structure of γ-Type Octamolybdates Coordinated by Alanines

Abstract  

The acidification of aqueous solutions containing Na₂MoO₄·2H₂O and KCl in the presence of alanine ligand gives an octamolybdate coordinated by two alanine ligands, K₄[Mo₈O₂₆(CH₃CH(NH₃)CO₂)₂]·4H₂O (1), which crystallizes with triclinic symmetry in the space group P[`1] P\overline{1} , the cell parameters being a = 9.0622(10) ?, b = 9.9652(11) ?, c = 10.6322(12) ?, α = 90.021(2)°, β = 100.656(2)°, γ = 106.271 (2)°, V = 904.42(17) ?³, Z = 1, D _c  = 2.920 g cm⁻³ and final R indices (I > 2σ(I)) R ₁ = 0.0257, wR ₂ = 0.0682, S = 1.115. The alanine ligands are coordinated via their carboxylate–oxygen as a monodentate ligand to γ-[Mo₈O₂₆]⁴⁻ anion.     

Crystal Structure Studies of Two Regioisomers of Bromo-4-Aryloxymethylcoumarins

Abstract  

The 4-(2-bromo-4-methyl-phenoxymethyl)-6-methylcoumarin (1) have been synthesized from bromination of corresponding 4-aryloxymethyl coumarin, which is a regioisomer of 4-(2-bromo-4-methyl-phenoxymethyl)-7-methylcoumarin (2) (CCDC-695895). The compound 1 crystallizes with triclinic space group P-1, a = 8.0943(3) ?, b = 9.3502(3) ?, c = 10.1476(4) ?, α = 90.234(2)°, β = 94.065(2)°, γ = 95.106(2)°, Z = 2 and compound 2 crystallizes with monoclinic space group P2₁/n, a = 8.465(5) ?, b = 13.649(5) ?, c = 13.304(5) ?, α = 90.000(5)°, β = 90.740(5)°, γ = 90.000(5)°, Z = 4. Both the compounds are planar with variation in their intermolecular hydrogen bonds between C–H···O and C–H···π.     

Characterization of Molecular Complexes of 1,4-Naphthoquinone Derivatives

Abstract  

The structures of sulphur atom tethered quinone containing flexible carboxylic acid (3-methyl-1,4-dioxo-1,4-dihydronaphthalen-2-ylsulfanyl)acetic acid (1) and its molecular complex with 4,4′-bipyridine (3) are determined. The compound 1 crystallizes in P-1 (triclinic, a = 7.5378(6) ?, b = 7.6413(7) ?, c = 10.3101(9) ?; α = 89.779 (7)°, β = 81.042 (5)°, γ = 89.101(7)°) and the molecular complex 3 crystallises in P2(1)/n (monoclinic, a = 9.3383(7) ?, b = 3.970(3) ?, c = 42.130(3) ?, β = 91.056(5)°) space groups, respectively. The R₂²(8) type hydrogen bonding between dicarboxylic acid groups present in the parent compound 1 is lost on interaction with 4, 4′-bipyridine; in the molecular complex 3 R₂²(7) type of O···H–C and O–H···N interactions are present between the pyridine rings and carboxylic acid groups. The molecular complex (4) derived from 3-carboxymethylsulfanyl-1,4-dihydroxynaphthalen-2-yl-sulfanyl) acetic acid (2) with triphenylphosphine oxide in 1:2 ratio, crystallises in C2/c space group have monoclinic, a = 26.0494(13) ?, b = 10.5402(5) ?, c = 17.1023(8) ?, β = 108.719 (5)°). The triphenylphosphine oxide molecules are preferentially held by O–H···O interactions between carboxylic acid and P=O bond.     

A Facile Synthesis and Crystallographic Analysis of Seven Trityl Phosphorus Compounds and Two Nickel(II) Phosphine Side-Products

Abstract  The syntheses and X-ray analyses of triphenylmethyl (trityl=Tr) phosphorus compounds are reported and the structural similarities, differences and ³¹P chemical shifts compared. A series of seven trityl-substituted phosphorus-containing compounds have been characterized by single crystal X-ray diffraction. Ph₃CPPh₂, 1, a bulky P(III) compound crystallizes in the triclinic space group , a = 7.5624(6) ?, b = 9.5470(8) ?, c = 16.9722(14) ?, α = 83.4720(10)°, β = 80.541(2)°, γ = 68.1580(10)°, the borane complex of 1, 2, Ph₃CPPh₂(BH₃) crystallizes as monoclinic colorless crystals, P2₁/c, a = 10.0972(12) ?, b = 9.6955(12) ?, c = 25.197(3) ?, β = 90.258(2)°. The analogous methyl substituted, 3, Ph₃CPMe₂(BH₃) is monoclinic, C₂/c, a = 15.628(3) ?, b = 12.770(3) ?, c = 18.406(4) ?, β = 103.968(3)°. Compounds 4–7 are trityl substituted P(V) compounds: Ph₃CP(Ph)(O)(OH), 4, crystallizes in the triclinic space group , a = 8.9847(18) ?, b = 9.7443(19) ?, c = 12.786(3) ?, α = 72.045(3)°, β = 72.031(3)°, γ = 78.769(3)°. Esterification of 4 affords TrCP(O)(Ph)OBn 5, space group, P2₁/c, a = 7.9196(5) ?, b = 31.701(2) ?, c = 19.8062(13) ?, β = 99.7750(10)°. A phosphonate diester was also characterized, Ph₃CP(O)(OEt)₂, 6, triclinic, , a = 7.9521(17) ?, b = 9.2205(19) ?, c = 14.471(3) ?, α = 85.906(4)°, β = 83.031(4)°, γ = 68.283(4)°. Treatment of the trityl H-phosphinic acid, Ph₃CPO₂H_2, with elemental selenium yields yellow crystals of 7, [Ph₃CP(O)(OH)Se]_2, P2₁/c, a = 9.0603(4) ?, b = 22.3652(11) ?, c = 16.9134(7) ?, β = 107.035(2)°. In our efforts to isolate a nickel-phosphine complex, two Ni(II) complexes were crystallographically analyzed, [Ni(OP(H)Ph₂)₆]₂BF₄ ⁻ 8 and 9. Complex 8 with an uncoordinated BF₄ ⁻ ion crystallizes as yellow orthorhombic crystals, Pbca, a = 18.8247(12) ?, b = 18.5518(12) ?, c = 21.0976(14) ?, while crystals of 9 are trigonal, , a = b = 13.1545(12) ?, c = 68.461(9) ?. Graphical Abstract  The syntheses and X-ray analyses of triphenylmethyl (trityl=Tr) phosphorus compounds are reported and the structural similarities, differences and ³¹P chemical shifts compared.      

Synthesis,Crystal Structure and IR Spectra of Complexes of Mn(II) by Indole-2-Carboxylic or Isoquinoline-1-Carboxylic Acids and 1,10-Phenanthroline

Abstract  

Two ternary complexes of manganese(II) indole-2-carboxylate (2-IC⁻) or isoquinolinecarboxylate (IQC⁻) with 1,10-phenanthroline (phen) in methanol or in dimethylacetamide (DMA) were synthesized and studied by X-ray diffraction and IR spectra. [Mn(C₉H₆NO₂)₂(C₁₂H₈N₂)₂]·CH₄O (1) crystallizes in the triclinic space group P-1 with cell parameters of a = 10.548(2) ?, b = 14.168(3) ?, c = 14.580(3) ?, α = 62.35(2)°, β = 69.16(2)°, γ = 78.61(2)°, V = 1802.4(6) ?³ and Z = 2; [Mn(C₁₀H₆NO₂)₂(C₁₂H₈N₂)].C₄H₉NO (2) crystallizes in the monoclinic space group P2₁/a with cell parameters of a = 15.304(5) ?, b = 12.871(5) ?, c = 17.421(5) ?, β = 114.39(1), V = 3125(2) ?³ and Z = 4. In 1, Mn is six-coordinate by two bidentate phen ligands and two 2-IC⁻ ligands and exhibits a very distorted octahedral geometry. This complex is solvated by methanol involved in hydrogen bonding. In 2, Mn atom is surrounded by one bidentate phen ligand and two bidentate IQC⁻ ligands. The complex exhibits a distorted octahedral geometry around the Mn^II atom. The crystal structure is completed by a disordered DMA solvate molecule. The IR spectra of both compounds are slightly different in the range 4000–2400 cm⁻¹ which may be attributed to hydrogen bond lack in 2.     

Synthesis and Crystal Structure of a Novel Double-Chain Coordination Polymer [Zn<Subscript>2</Subscript>(bipy)<Subscript>2</Subscript>(btec)(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>]<Subscript>n</Subscript> (bipy = 2,2′-bipyridine; btec = 1,2,4,5-benzenetetracarboxylate)

Abstract  A novel aromatic polycarboxylate polymer, [Zn₂(bipy)₂(btec)(H₂O)₂]_n (1), has been synthesized and structurally characterized by the single crystal X-ray diffraction. Compound 1 belongs to the triclinic crystal system, space group P-1; a = 7.7449(6) ?, b = 8.9286(8) ?, c = 10.7422(8) ?, α = 80.95(1)°, β = 70.21(1)°, γ = 78.14(1)°, V = 680.93(10) ?³, Z = 2. The coordination geometry of Zn(II) atom is distorted trigonal bipyramidal with two nitrogen atoms of one 2,2′-bipy group, two oxygen atoms from two different btec ligands, and one water. The 16-membered rings are alternately arranged forming an infinite 1-D double-chain structure. A 3-D network was constructed by interlayer C···H–O, O···H–O hydrogen bonds and π–π stacking interactions. Compound 1 exhibits fluorescence at room temperature in the solid state. Graphical Abstract  A 1-D double-chain aromatic polycarboxylate polymer, [Zn₂(bipy)₂(btec)(H₂O)₂]_n (1), has been synthesized and structurally characterized by the single crystal X-ray diffraction. A 3-D network was constructed by intermolecular C···H–O, O···H–O hydrogen bonds and π–π stacking interactions. Compound 1 exhibits fluorescence at room temperature in the solid state.      

Synthesis and Structural Characterization of Substituted Salicylate Titanocene Complexes: Three Supramolecular Frameworks Determined by Weak Interactions

Abstract  Based on the reaction between Cp₂TiCl₂ and substituted salicylic acids in the presence of β-cyclodextrin polymer (β-CDP), three four-coordinated titanocene complexes [(η⁵-C₅H₅)₂Ti(S,O′)(OCC₆H₄)·(C₆H₆)_0.5] (1), [(η⁵-C₅H₅)₂Ti{(O,O′)(3,5-Cl₂-OCC₆H₂)}] (2) and [(η⁵-C₅H₅)₂Ti{(O,O′)(3,5-(NO₂)₂-OCC₆H₂)}] (3) were synthesized in high yields and their crystal structures have been determined by single-crystal X-ray diffraction. The structure of 1 has a Monoclinic space group P2₁/c with a = 8.313(3) ?, b = 9.960(4) ?, c = 22.330(8) ?, β = 111.856(11)° and Z = 4. The structure of 2 has a Monoclinic space group P2₁/c with a = 8.0577(13) ?, b = 8.9022(14) ?, c = 21.977(4) ?, β = 96.298(3)° and Z = 4. The structure of 3 has a Triclinic space group P-1 with a = 8.1687(11) ?, b = 8.3027(11) ?, c = 12.7164(17) ?, α = 102.930(2)°, β = 100.479(2)°, γ = 95.458(2)° and Z = 2. Each of the complexes exhibits a three-dimensional framework constructed through weak interactions, which are hydrogen bonding, π–π stacking and C–H···π interactions. It was found that the variation of the substituted salicylate ligands affect the weak interactions as well as the specific framework structure that forms. Graphical Abstract  Three four-coordinated titanocene complexes [(η⁵-C₅H₅)₂Ti(S,O′)(OCC₆H₄)·(C₆H₆)_0.5] (1), [(η⁵-C₅H₅)₂Ti{(O,O′)(3,5-Cl₂-OCC₆H₂)}] (2) and [(η⁵-C₅H₅)₂Ti{(O,O′)(3,5-(NO₂)₂-OCC₆H₂)}] (3) were synthesized in high yields, each of the complexes exhibits a three-dimensional framework constructed through weak interactions. It was found that simple variation of the substituted salicylate ligands affect the weak interactions as well as the specific framework structure that forms. .     

Preparation, Crystal Structure and Spectroscopic Properties of Dimeric [Zn(2-bromobenzoato)2(phenazone)]2 and Monomeric [Zn(2-bromobenzoato)2(thiourea)2]·2H2O

Abstract  

The binuclear zinc complex bis(2-bromobenzoato-O)-bis(μ ₂ -2-bromobenzoato-O,O′)-bis(phenazone-O)-dizinc(II) (I) and the mononuclear dihydrate bis(2-bromobenzoato-O)-bis(thiourea-S)-zinc(II) (II) have been synthesized and characterized by means of elemental analysis and spectroscopic methods (IR, ¹H and ¹³C NMR, EDS). The solid state structures of both compounds were determined by single-crystal X-ray diffractometry. Compound [Zn(2-BrC₆H₄COO)₂(phen)]₂ (phen—phenazone) (I) crystallized as a dimeric compound with a triclinic lattice (space group P − 1), where both zinc atoms, interconnected by two carboxylate groups, possess a distorted tetrahedral coordination environment. The crystallographic data of complex I: a = 9.9410(3) ?, b = 10.7309(3) ?, c = 12.9237(4) ?, α = 93.6004(17)°, β = 92.5898(11)°, γ = 116.2192(16)°, V = 1230.26(6) ?³, Z = 1. Complex [Zn(2-BrC₆H₄COO)₂(tu)₂]·2H₂O (tu—thiourea) (II) crystallized with an orthorhombic lattice (space group Aba2) as a monomeric compound, where the coordination environment of the central zinc atom is a distorted tetrahedron. The crystallographic data of complex II are: a = 9.8595(3) ?, b = 19.7052(5) ?, c = 12.5908(3) ?, V = 2446.18(11) ?³, Z = 4. The modes of the carboxylate binding were assigned from the IR spectra using the magnitude of the separation between the carboxylate stretches (Δ), which correlated well with the crystal structures. The computed theoretical IR spectrum agreed well with the experimental data.     

Synthesis,Characterization and Fluorescent Property of Two Mixed Ligand Coordination Polymers Constructed from 4-Cyclohexene-1,2-dicarboxylate and Nitrogen-Containing Ligands

Abstract  

Two new coordination polymers [Cd(1,2′-cy)(btx)_0.5H₂O]_n 1 and {[Ni(1,2-cy)(2,2′-bipy)(H₂O)₂]·3H₂O}_n 2 (1,2′-cy=4-cyclohexene-1,2-dicarboxylate, btx=1,4-bis(triazol-1-ylmethyl)benzene, 2,2′-bipy=2,2′-bipyridine) had been synthesized. Their structures were characterized by elemental analysis, IR, TG and X-ray single-crystal diffraction analysis. Crystal data for complex 1: Triclinic, space group P-1, a = 6.4303(13) ?, b = 10.399(2) ?, c = 11.713(2), α = 83.04(3)°, β = 81.87(3)°, γ = 83.84(3)°, and Z = 2. For complex 2: Orthorhombic, space group Pbcn, a = 15.613(3) ?, b = 13.970(3) ?, c = 21.290(4) ?, and Z = 4. Complex 1 exhibits an interesting two-dimensional wavelike covalent layer structure. When Ni salt was replaced by Cd salt, and reacts with 1,2′-cy and 2,2′-bipy, one-dimensional chain-like complex 2 was obtained. Furthermore, the fluorescent property of complex 1 was reported.     

Synthesis and Crystal Structures of Two Binuclear Lanthanide [Ln = Pr,Dy] Complexes with 4-Quinolineacarboxylate

Abstract  

The reaction of the organic ligand, 4-quinolineacarboxylate (L) with Pr(ClO₄)₃·6H₂O and Dy(ClO₄)₃·6H₂O, leads to the formation of two novel complexes [Pr₂(L)₆(H₂O)₄]2H₂O 1 and [Dy₂(L)₆(H₂O)₄]2H₂O 2, which have been characterized by elemental analysis, IR and single-crystal X-ray diffraction analysis (monoclinic system, space group P2(1)/n, with a = 11.805(2), b = 16.645(3), c = 15.367(3) ?, β = 106.78(3)°, V = 2891.1(10) ?³, Z = 4 for 1, monoclinic system, space group P2(1)/n, with a = 11.629(2), b = 16.478(3), c = 5.336(3) ?, β = 105.83°, V = 2827.4(10) ?³, Z = 4). The two isostructure complexes are binuclear and possess an inversion center which is at the midpoint of the linkage of two symmetrical La(III) centers. In two complexes, each metal center adopts nine-coordinated mode coordinated by nine O atoms from two H₂O molecules and three carboxyls of three ligands, and L displays three different coordination modes. Hydrogen bonds join the binuclear complexes into 3D networks.     

Structures and Characterization of [Zn(n-chlorosalicylato)2(N-methylnicotinamide)2(H2O)2] (n?=?4 or 5) Ligand Isomers

Abstract  

Two ligand isomers [Zn{4-ClC₆H₃-2-(OH)COO}₂(Menia)₂(H₂O)₂] (I) and [Zn{5-ClC₆H₃-2-(OH)COO}₂(Menia)₂(H₂O)₂] (II) (Menia = N-methylnicotinamide) were prepared and characterized by elemental analysis, IR spectroscopy and thermal analysis. The X-ray crystal structures of complexes (I) and (II) were determined. Compound (I) crystallizes in the triclinic space group P[`1] P\bar{1} with a = 8.105(1) ?, b = 10.036(2) ?, c = 10.545(2) ?, α = 109.088(9)°, β = 91.416(8)°, γ = 102.757(9)°, V = 786.2(2) ?<sup>3</sup>, Z = 1. Compound (II) crystallizes in the triclinic space group P[`1] P\bar{1} . Its cell parameters are: a = 8.133(1) ?, b = 10.119(2) ?, c = 10.428(1) ?, α = 66.44(1)°, β = 74.32(1)°, γ = 80.16(1)°, V = 755.5(2) ?³, Z = 1. The molecular structure of both isomers is monomeric. Each Zn(II) atom is hexacoordinated by three pairs of unidentate ligands in trans-positions (ZnO₄N₂). The 5-Clsal complex is somewhat less distorted than 4-Clsal complex (Cl-sal = chlorosalicylate). The structural data are compared with those found in similar [Zn(RCOO)₂(NL)₂(H₂O)₂].     

Synthesis and Crystal Structures of the Coordination Polymers Pb(PYTAC)<Subscript>2</Subscript> and Pb<Subscript>2</Subscript>(PYTAC)<Subscript>3</Subscript>(NO<Subscript>3</Subscript>) (PYTAC = 2-(pyridin-4-yl)thiazole-5-carboxylate)

Abstract  

Two lead coordination compounds, Pb(PYTAC)₂ (1), and Pb(PYTAC)₂(NO₃) (2), were grown as single crystals via hydrothermal synthesis (PYTAC = 2-(4-pyridyl) thiazole-4-carboxylate). Both compounds have been identified via single crystal X-ray diffraction. Coordination polymer 1 crystallizes in a triclinic space group P-1 (a = 5.5097(4) ?, b = 7.2822(5) ?, c = 11.3134(8) ?, α = 103.5580(10)°, β = 99.4330(10)°, γ = 97.1050(10)°), and forms 2-D layers parallel to the crystallographic (ac) plane. Coordination polymer 2 crystallizes in a triclinic space group P-1 (a = 9.8102(5) ?, b = 10.5972(6) ?, c = 14.8076(8) ?, α = 91.9350(10)°, β = 100.8050(10)°, γ = 103.1350(10)°), and forms an infinite 1-D chains along the a axis.     

Syntheses and Crystal Structures of Two CuII Coordination Isomers [Cu(pmt)2] · 4H2O (1) and {[Cu(pmt)2] · 2H2O} n (2)

Abstract  A pair of Cu^II coordination isomers [Cu(pmt)₂] · 4H₂O (1) and {[Cu(pmt)₂] · 2H₂O} _n (2) [Hpmt = 2-(2-pyridylmethylamino) ethanesulfonic acid] have been prepared by reaction of the same proportion CuCl₂ · 2H₂O and Hpmt but with different experimental methods in water–methanol mixed solution, and were characterized by X-ray diffraction, elemental analysis, IR spectrum. X-ray analysis indicates that complex (1) is a mononuclear complex in which two deprotonated pmt ligands coordinate in a facial tridentate arrangement about the Cu^II atom. While complex (2) is a coordination polymer, in which four N atoms of pmt ligands coordinate to one Cu^II atom but its sulfonate O atoms bond to adjacent Cu^II atom. Thus 12-membered rings (–Cu–N–C–C–S–O–)₂ are obtained between two neighbouring Cu^II atoms and they connect one another to form this new polymer. Crystal data: [Cu(pmt)₂] · 4H₂O (1), Mr = 566.10, monoclinic, P2 ₁/c, a = 9.1950(8) ?, b = 11.5093(10) ?, c = 11.2304(10) ?, β  = 105.5550(10)°, Z = 2, V = 1144.96(17) ?³, R ₁  = 0.0407, wR ₂  = 0.1242 [I > 2σ (I)]; {[Cu(pmt)₂] · 2H₂O} _n (2), Mr = 530.07, triclinic, P-1, a = 7.6165(19) ?, b = 8.806(2) ?, c = 9.592(4) ?, α = 104.933(4)°, β = 106.732(4)°, γ = 109.503(3)°, Z = 1, V = 534.2(3) ?³, R ₁ = 0.0470, wR ₂ = 0.1082 [I > 2σ(I)]. Index Abstract  A pair of Cu^II coordination isomers [Cu(pmt)₂] · 4H₂O (1) and {[Cu(pmt)₂] · 2H₂O} _n (2) [Hpmt = 2-(2-pyridylmethylamino) ethanesulfonic acid] have been prepared by reaction of the same proportion CuCl₂ · 2H₂O and Hpmt but with different experimental methods in water–methanol mixed solution.      

Synthesis, Structure and Characterization of Two 1D Chain-like Cadmium Terephthalate Complexes: [Cd(tp)(H2O)3]?·?4H2O and [Ph4P][Cd(tp)0.5Cl2]?·?H2O

Abstract  Two new compounds, [Cd(tp)(H₂O)₃] · 4H₂O (1) and [Ph₄P][Cd (tp)_0.5Cl₂] · H₂O (2) (tp = terephthalate, [Ph₄P] = tetraphenylphosphonium), are metal-polycarboxylate coordination polymers prepared by similar hydrothermal synthesis techniques. Both compounds crystallize in the 1D chain-like architectures. 1 (C₈H₁₈CdO₁₁) is orthorhombic Pcca, Z = 4 (a = 7.3018(1) ?, b = 9.9975(3) ?, c = 19.9695(5) ?, V = 1457.77(6) ?³). 2 (C₂₈H₂₄CdCl₂O₃P) is triclinic P−1, Z = 2 (a = 9.5028(4) ?, b = 12.3130(5) ?, c = 12.7343(6) ?, α = 68.380(1)°, β = 73.723(1)°, γ = 89.624(1)°, V = 1321.8(1) ?³). Transition metal cadmium centers bridged by rigid linear tp ligands give rise to a 1D infinite zigzag chain polymer for 1 and a simple 1D infinite stepped chain polymer for 2. 1 presents an interesting plywood-like packing network while 2 shows a simple parallel rod-like stacking network. An intense fluorescent emission at 412 nm (λ_exc = 338 nm) for 1 in the solid state at room temperature is observed. Index Abstract  Polymeric compounds [Cd(tp)(H₂O)₃] · 4H₂O (1) and [Ph₄P][Cd (tp)_0.5Cl₂] · H₂O (2) crystallize in two remarkable 1D chain-like architectures prepared by similar hydrothermal synthesis techniques, showing an interesting plywood-like packing network in 1 and a simple parallel rod-like stacking network in 2, respectively. An intense fluorescent emission at 412 nm (λ_exc = 338 nm) for 1 in the solid state at room temperature is observed.      

Solvothermal Synthesis and Crystal Structure of a 18-Membered Macrocycle Schiff Base Dinuclear Copper(II) Complex: Cu2(NO3)4(APTY)4 (APTY = 1,5-dimethyl-2-phenyl-4-{[(1E)-pyridine-4-ylmethylene]amino}-1,2-dihydro-3H-pyrazol-3-one)

Abstract  A new 18-membered macrocycle Schiff base dinuclear copper(II) complex: Cu₂(NO₃)₄(APTY)₄ (1) (APTY = 1,5-dimethyl-2-phenyl-4-{[(1E)-pyridine-4-ylmethylene]amino}-1,2-dihydro-3H-pyrazol-3-one), has been successfully synthesized by solvothermal treatment of Cu(NO₃)₂ · 6H₂O with APTY. Compound 1 crystallizes in the triclinic space group P-1 with cell parameters: a = 10.556(2) ?, b = 12.075(2) ?, c = 15.230(3) ?, α = 74.75(3), β = 81.50(3), γ = 70.60(3)°, V = 1762.7(6) ?³, R1 = 0.0493, wR2 = 0.1400, Z = 1, D _calc = 1.455 g/cm³, F(000) = 798, S = 1.009. In the compound molecules, each of the six-coordinated Cu^II atoms are bridged by APTY ligands into 18-membered macrocycle, and each the Cu²⁺ atoms exhibits a significantly distorted octahedral geometry. The crystal packing is stabilized by C–H···O hydrogen-bonding interactions into a three-dimensional supramolecular framework. Index Abstract  A new 18-membered macrocycle Schiff base dinuclear copper(II) complex: Cu₂(NO₃)₄(APTY)₄ (1), has been successfully synthesized by solvothermal treatment (APTY = 1,5-dimethyl-2-phenyl-4-{[(1E)-pyridine-4-ylmethylene]amino}-1,2-dihydro-3H-pyrazol-3-one). The six-coordinated Cu²⁺ atom exhibit significantly distorted octahedral geometry. The crystal packing is stabilized by C–H···O hydrogen-bonding interactions into a three-dimensional supramolecular framework.