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.     

Reactivity of [Re2(CO)8(MeCN)2] With 1-vinylimidazole: X-ray Structures of [Re2(CO)8{η1-NC3H3N(CH=CH2)}2] and [ReCl2(CO)2{η1-NC3H3N(CH=CH2)}2]

Abstract  Treatment of [Re₂(CO)₈(MeCN)₂] with excess 1-vinylimidazole in refluxing benzene gives three new compounds [Re₂(CO)₉{η ¹-NC₃H₃N(CH=CH₂)}] (1), [Re₂(CO)₈{η ¹-NC₃H₃N(CH=CH₂)}₂] (2) and [ReCl₂(CO)₂{η ¹-NC₃H₃N(CH=CH₂)}₂] (3) in 11, 32 and 2% yields, respectively. The solid-state structures of complexes 2 and 3 have been determined by single crystal X-ray diffraction studies. Compound 2 crystallizes in the monoclinic space group C2/c, with lattice parameters a = 13.8378(5) ?, b = 11.8909(5) ?, c = 14.4591(6) ?, β = 116.6470(10)°, Z = 4 and V = 2131.99(15) ?³. Compound 3 crystallizes in the monoclinic space group C2/c, with lattice parameters a = 10.1028(3) ?, b = 13.5640(5) ?, c = 12.5398(4) ?, β = 109.637(2)°, Z = 4 and V = 1618.4(9) ?³. The disubstituted dinuclear compound 2 contains two 1-vinylimidazole ligands coordinated through the imino nitrogen atoms at the equatorial sites, whereas the mononuclear compound 3 contains two carbonyl ligands, two N coordinated η ¹-1-vinylimidazole ligands and two terminal Cl ligands. Graphical Abstract  Two dinuclear complesxes [Re₂(CO)₉{η ¹-NC₃H₃N(CH=CH₂)}] (1) and [Re₂(CO)₈{η ¹-NC₃H₃N(CH=CH₂)}₂] (2) and the mononuclear [ReCl₂(CO)₂{η ¹-NC₃H₃N(CH=CH₂)}₂] (3) were obtained from the reaction of [Re₂(CO)₈(MeCN)₂] with excess 1-vinylimidazole at 80 °C. The X-ray structrures of 2 and 3 are described.      

Crystal and Molecular Structures of C6H5CH2SOCH2CONHCH2C6H5 and C6H5SOCH2CON(iC3H7)2

Abstract  The crystal structures for two of the ligands C₆H₅CH₂SOCH₂CONHCH₂C₆H₅ (1) and C₆H₅SOCH₂CON(ⁱC₃H₇)₂ (2) have been determined by X-ray diffraction. These compounds crystallize in orthorhombic system with space groups and cell parameters, Pca21(no. 29), a = 8.4600(5) ?, b = 5.3534(5) ?, c = 32.136(2) ?, V = 1455.42(15) ?³ and Pna21(no. 33) a = 17.5563(11) ?, b = 5.7902(4) ?, c = 14.2866(9) ?, V = 1452.30(16) ?³, respectively. These molecules are stabilized in solid state by various intra and intermolecular hydrogen bonding interactions to give polymeric structures. The reported IR spectra of these compounds in solid state could be explained on the basis of the observed intermolecular hydrogen bonding interactions. Index Abstract  The title compounds C₆H₅CH₂SOCH₂CONHCH₂C₆H₅ (1) and C₆H₅SOCH₂CON(ⁱC₃H₇)₂ (2) were prepared by the oxidation of corresponding sulfides with H₂O₂/SeO₂ in methanol and their structures were determined. The structures show that the SO and CO groups are having “anti” configuration in 1 and “syn” configuration in 2. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synthesis and Molecular Structure of Sulfur Containing Cobalt Compounds

Abstract  

The reaction of cobalt (II) chloride hexahydrate and N-tert-butyl-2-thioimidazole (tm^t-Bu) yielded products [k²-(tm^t-Bu)₂]CoCl₂ (1) and [(tm^t-Bu)₂Co₂(μ-tm^t-Bu)₂Cl₂]·CH₃CN (2) at different reaction time. The single crystal X-ray diffraction analysis was carried out for 1 and 2 {Bruker Kappa Apex-II CCD diffractometer, MoK_α radiation}. Crystal data for 1: orthorhombic P212121 unit cell a = 8.195(6) ?, b = 13.778(10) ?, c = 17.354(11) ? and V = 1960(2) ?³ whereas the compound 2 crystallizes in monoclinic system P21/c with unit cell a = 10.069(7) ?, b = 11.181(7) ?, c = 18.156 ?, β = 95.322(4)° and V = 2035.4(2) ?³. The complex 1 contains one dimensional chain running along the a-axis and the complex 2 contains one dimensional chain running along the b-axis due to existence of different types of intermolecular interaction. The change in structure of the product is directly related to the reaction time i.e. reaction for lesser time produces mononuclear product and for longer time produces binuclear compound.     

Synthesis and Crystal Structures of Anionic Gallium(II) and Gallium(III) Heterocyclic Compounds Derived from a Gallium(I) N-Heterocyclic Carbene Analogue

Abstract  

The addition of the N–H bond of the formamidine, ArN(H)C=NAr (Ar = C₆H₃Pr₂ⁱ-2,6), to the gallium(I) center of [K(tmeda)][:Ga(Ar-DAB)] (Ar-DAB={(Ar)NC(H)}₂) yields K[(Ar-DAB)Ga^III(H){N(Ar)C=NAr}] 1. The crystal structure of this and two other related anionic compounds, [K(18-crown-6)][(Ar-DAB)Ga^III{N(H)N=Fl}{(H)Fl}] (Fl = fluorendiyl) 2 and [K(OEt₂)₃][(Ar-DAB)Ga^II(CH₂Ph)Ga^II(Ar-DAB)] 3, have been determined. The cell parameters of the compounds are 1: P2₁/c, a = 20.2350(9), b = 14.1760(7), c = 19.6441(10), β = 111.307(1); 2: P2₁/c, a = 13.115(3), b = 21.799(4), c = 22.646(5), β = 90.20(3); 3: P2₁/n, a = 16.783(3), b = 21.635(4), c = 19.814(4), β = 92.34(3). The crystal structures of all complexes exhibit distorted tetrahedral gallium centers, and interactions between anion aryl substituents and the potassium cations.     

Synthesis and Structural Characterization of [2-(2-1H-Imidazoly)-1H-imidazolium nitrate] and [2-(2-1H-Imidazoly)-2H-imidazolium phthalyl glycinate] Based on the 2,2′-bi-1H-Imidazole Molecule

Abstract  

Two new compounds (H₃biim)(NO₃)(1) and (H₄biim)(phthgly)₂ (2) (H₂biim=biimidazole; Hphthgly=N-phthaloylglycine) have been synthesized and characterized by luminescence and single crystal X-ray diffraction study. Compound 1 crystallizes in the monoclinic space group C2/c, where a = 14.8078(15), b = 5.9233(6), c = 20.028(2) ?, β = 92.7910(10)°, V = 1754.6(3) ?³ and Z = 8. Compound 2 crystallizes in the monoclinic space group P2(1)/n, where a = 15.3775(14), b = 5.3200(6), c = 6.4689(18)?, β = 115.418(2)° V = 1216.9(2)?³ and Z = 4. In 1, the N–H groups of H₃biim⁺ and the oxygen atoms of NO₃ ⁻ are linked by hydrogen bonds leading to H₃biim⁺(N,N)–R₂²(10) and N–H···O interactions forming infinite 1D helical chains along the b-axis. Compound 2 consists of a planar diprotonated biimidazole moiety and two phthgly anions which connect to the dication by hydrogen bonds phthgly⁻(O,O)–R₂²(9).     

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,Crystal Structure and Magnetic Property of a One-Dimensional Samarium(III) Coordination Polymer

Abstract  

A novel samarium(III) polymer, [Sm₂(C₆H₅COO)₆(CH₃OH)₃]·CH₃OH (1) has been synthesized and characterized by single crystal X-ray diffraction and magnetic measurements. Polymer 1 crystallizes in monoclinic space group P2(1)/c, with a = 15.1247(6), b = 18.3351(7), c = 21.1266(6) ?, β = 126.830(2)°, V = 4689.4(3) ?³, and Z = 4. Single crystal X-ray analysis reveals a chain-like structure of 1 consisted of alternating eight- and nine-coordinate Sm(III) ions bridged by benzoate ligands in different coordination modes. A treatment of the variable-temperature magnetic susceptibility using an expression deduced from free-ion approximation and molecular field theory suggests the existence of a weak antiferromagnetic coupling between the samarium ions.     

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.     

Absence of Platinophilic Interactions in a Series of Tetracyanoplatinates Incorporating Cyclic Amines

Abstract  

Three novel compounds have been synthesized and structurally characterized: [1,10-Hphen]₂Pt(CN)₄·2H₂O (1a) space group P2₁/n, a = 8.73070(17) ?, b = 15.4609(2) ?, c = 9.82661(19) ?, β = 103.252(2)°; [2,2′-Hbipy]₂Pt(CN)₄·2H₂O (1b) space group P2₁/n, a = 7.0859(14) ?, b = 12.940(2) ?, c = 13.7486(19) ?, β = 100.708(16)°; K₂[Pt(CN)₄]·2phen (phen = 1,10-phenanthroline) (2) space group P2₁/c, a = 8.1393(4) ?, b = 20.4050(9) ?, c = 8.4085(4) ?, β = 105.284°. All three structures contain isolated [Pt(CN)₄]²⁻ ions and they all illustrate the absence of Pt⋯Pt interactions due to the presence of bulky cyclic amines or ammoniums. The structures of 1a and 1b contain large organic cations, 2,2′-bipyridinium and 1,10-phenanthrolinium, respectively while compound 2 contains neutral 1,10-phenanthroline molecules co-crystallized between the potassium tetracyanoplatinate framework.     

Structural Studies of Electron Deficient Titanacyclobutanes

Abstract  

Two 16 electron titanacyclobutanes of the formula Ti(C₅H₄R)₂(μ₂-CH₂)₂C(CH₃)(i-C₃H₇) (R=H, CH₃) have been prepared from the reaction of Ti(C₅H₅)₂(μ₂-CH₂)(μ₂-Cl)Al(CH₃)₂ or Ti(C₅H₄CH₃)₂(μ₂-CH₂)(μ₂-Cl)Al(CH₃)₂ with H₂C=C(CH₃)(i-C₃H₇). Structural parameters, most notably lengthened C–C bonds in the titanacyclobutane ring, for both complexes reveal the expected presence of (C–C)→Ti agostic interactions. The complexes are isomorphous, crystallizing in the monoclinic space group Cc. For Ti(C₅H₅)₂(μ₂-CH₂)₂C(CH₃)(i-C₃H₇), a = 11.3459(3) ?, b = 16.2108(4) ?, c = 8.1646(2) ?, β = 105.5276(16)°, V = 1446.87(6)°, D_calc = 1.268 at 150(1) K. For Ti(C₅H₄CH₃)₂(μ₂-CH₂)₂C(CH₃)(i-C₃H₇), a = 12.6591(2) ?, b = 16.2795(4) ?, c = 8.2462(2) ?, β = 107.2421(14)°, V = 1623.04(6) ?³, D_calc = 1.245 at 150(1) K.     

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].     

The Zolmitriptan-Pyridine (1:1) and Zolmitriptan-Propiophenone (3:2) Inclusion Complex

Abstract  

The crystal structures of zolmitriptan with pyridine (I) and propiophenone (II) solvates have been determined by single crystal X-ray diffraction studies. Compound (I) crystallizes in the orthorhombic space group P2₁2₁2₁ with a = 8.5610(5) ?, b = 12.2709(7) ?, c = 19.6201(12) ?, V = 2061.1(2) ?³, and Z = 4, while compound (II) crystallizes in the monoclinic space group P2₁ with a = 15.085(1) ?, b = 19.656(12) ?, c = 21.0860(13) ?, β = 92.068(1)°, V = 6248(4) ?³ and Z = 4. The asymmetric unit of (I), C₁₆H₂₁N₃O₂·C₅H₅N, contains one zolmitriptan molecule and one pyridine solvate, while the asymmetric unit of (II), 3(C₁₆H₂₁N₃O₂)·2(C₉H₁₀O) comprises six zolmitriptan molecules and four propiophenone solvates. In both structures, the N–H···N hydrogen bonds, form an infinite helical chain and generate a C(11)-type motif in (I) and a D₂²(13)-type motif in (II). Both the complexes have layer structures, the layers being constructed from rings (cavity) of four zolmitriptan molecules, hydrogen bonded through N–H···N and N–H···O bonds, where the pyridine (I) and propiophenone (II) solvates are included in an R₄⁴(33) ring.     

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.     

Solvothermal and Reflux Syntheses,Crystal Structure and Properties of Lanthanide-Thiophenedicarboxylate-Based Metal-Organic Frameworks

Abstract  

Two new lanthanide thiophenedicarboxylate-based metal-organic frameworks with the formulas La₂(2,5-TDC)₃(DMF)₂H₂O DMF (1) and Gd₂(2,5-TDC)₃(DMF)₂H₂O (2) (2,5-TDC = 2,5-thiophenedicarboxylic acid; DMF = N,N′-dimethylformamide), have been synthesized by two different methods (solvothermal and reflux). The synthesis of these materials from metal nitrate hydrates with 2,5-TDC as the organic linker in DMF/n-propanol afforded two rigid non-interpenetrating frameworks with coordinated solvent molecules (DMF and H₂O) occupying the channels. Compound (1) crystallizes in an orthorhombic space group Pna2₁ with Z = 4, a = 17.434(4) ?, b = 11.227(3) ?, c = 17.980(4) ? and V = 3,519.0(15) ?³. Compound (2) crystallizes in a monoclinic P2₁/n space group with Z = 4, a = 17.5387(17) ?, b = 10.8038(11) ?, c = 17.7283(18) ?, β = 104.793(2) and V = 3,247.9(6) ?³. Powder X-ray diffraction, thermogravimetric analysis and infrared spectroscopy of (1) and (2) are presented.     

Molecular Structures of RN(H)Py (R?=?2,4,6-Me3C6H2, 2,6-Et2C6H3, Ph3C), and the Copper Complex [Cu{(2,4,6-Me3C6H2)N(H)Py}2]BF4

Abstract  The molecular structures of RN(H)Py [R = 2,4,6-Me₃C₆H₂ (1), 2,6-Et₂C₆H₃ (2), -CPh₃ (3)] have been determined along with the copper(I) complex [Cu{(2,4,6-Me₃C₆H₂)N(H)Py}₂]BF₄ (4). Each of the amines exists as a hydrogen-bonded head-to-tail dimer. Compound 3 has four independent molecules in the asymmetric unit as a consequence of changes in the relative orientation of the pyridyl and phenyl rings. The copper in 4 is two-coordinate with the conformation of the aryl rings being dominated by inter-cation packing. Crystal data: 1 space group P2₁/c, a = 14.047(3), b = 7.154(1), c = 13.890(3) ?, β = 116.45(3)°; V = 1,249.7(4) ?³, Z = 4, R = 0.0547, wR ₂ = 0.1397; 2 space group P2₁/n, a = 13.035(3), b = 8.120(1), c = 13.562(3) ?, β = 111.87(3)°; V = 1,345.2(5) ?³, Z = 4, R = 0.0669, wR ₂ = 0.1512; 3 space group P2₁/c, a = 26.729(5), b = 17.008(3), c = 18.903(4) ?, β = 92.42(3)°; V = 8,586(3) ?³, Z = 8, R = 0.0911, wR ₂ = 0.163; 4 space group P2₁/c, a = 9.149(1), b = 15.901(3), c = 19.703(4) ?, β = 102.89(3)°; V = 2,794(1) ?³, Z = 4, R = 0.0504, wR ₂ = 0.1291. Graphical Abstract  The hydrogen-bonded head-to-tail dimer structures of RN(H)Py [R = 2,4,6-Me₃C₆H₂, 2,6-Et₂C₆H₃, -CPh₃] have been determined along with the two-coordinate copper complex [Cu{(2,4,6-Me₃C₆H₂)N(H)Py}₂]BF₄      

Unusual Co-Crystallization of both Monomeric and Dimeric Forms of Cu[PhN(py)quin]Cl<Subscript>2</Subscript>

Abstract  

The aryl functionalized diquinolyl amine MesN(quin)₂ (1) and the pyridyl-quinolyl amine (2,6-iPr₂C₆H₃)N(py)quin (2) have been prepared via palladium catalyzed cross-coupling of substituted anilines with 2-chloroquinoline. The HBF₄ acid salts of (2,6-ⁱPr₂C₆H₃)N(quin)₂ (3) and MesN(py)quin (4), as well as the copper complex [Cu{PhN(py)quin}Cl₂] (5) have been prepared in order to probe the effect that ligand coordination has on its geometry. The molecular structures of each have been determined by X-ray crystallography. The free ligands 1 and 2 crystallize in three-bladed propellar conformations, having smaller degrees of “pitch” between the two heterocycles than either has with the aryl “blade”, allowing for greater heterocycle π-system overlap with the amine lone pair. Acid confinement of similar ligands in 3 and 4 results in forced coplanarity of the two heterocycles, which coordinate the HBF₄ proton in an asymmetric fashion. The copper complex 5 crystallizes with both monomeric and dimeric forms present in the asymmetric unit. Crystal data: (1) Space group P2₁/c, a = 14.058(3), b = 12.202(2), c = 12.831(3) ?, β = 104.61(3)°, V = 2129.8(8) ?³, Z = 4, R = 0.0596, wR₂ = 0.1453. (2) Space group P2₁/c, a = 22.250(4), b = 8.628(2), c = 23.031(5) ?, β = 92.88(3)°, V = 4370(2) ?³, Z = 8, R = 0.0514, wR₂ = 0.1323. (3) Space group Pbca, a = 13.886(3), b = 18.016(4), c = 21.347(4) ?, V = 5340(2) ?³, Z = 8, R = 0.0722, wR₂ = 0.1635. (4) Space group P2₁/c, a = 10.629(2), b = 18.489(4), c = 10.907(2) ?, β = 92.88(3), V = 2140.6(7) ?³, Z = 4, R = 0.0551, wR₂ = 0.1531. (5) Space group \text P[`1]{\text P}\bar{1}, a = 9.706(2), b = 11.325(2), c = 17.322(4) ?, α = 98.28(3), β = 94.85(3), γ = 91.83(3)°, V = 1875.6(7) ?³, Z = 1, R = 0.0481, wR₂ = 0.0946.     

Cross Coupling of Substituted Anilines with Quinoline: Synthesis and Structural Characterization of HN(py)quin,PhN(py)quin,MesN(py)quin,and [PhN(py)(H-quin)]BF<Subscript>4</Subscript>

Abstract  

The molecular structure of (2,6-ⁱPr₂C₆H₃)N(quin)₂ (1) and both the methanol and toluene solvates of its copper complex [Cu{(2,6-ⁱPr₂C₆H₃)N(quin)₂}₂]BF₄, 2·MeOH and 2.2(C₆H₅Me), respectively, have been determined. The quinolyl rings in 1 adopt anti-syn (C_Ar–N–C–N_quin) conformation as a result of π–π stacking. The cation in 2·MeOH crystallizes on a C₂ axis, while the cation in 2·2(C₆H₅Me) is crystallographically independent. As a result of intramolecular π–π stacking there are significant changes within the coordination geometry about the copper centers between the two solvates, suggesting that the coordination around copper is supple. Crystal data: 1 group P2₁/c, a = 8.614(1), b = 16.137(3), c = 17.601(4) ?, β = 93.32(3)°, V = 2,442.5(9) ?³, Z = 4, R = 0.0544, wR ₂ = 0.1340. 2·MeOH group P3₂21, a = 13.254(1), b = 13.254(1), c = 27.214(5) ?, V = 4,140(1) ?³, Z = 3, R = 0.0392, wR ₂ = 0.0917. 2.2(C₆H₅Me) group P1, a = 11.677(2), b = 16.261(3), c = 17.077(3) ?, α = 93.63(3), β = 97.30(3), γ = 96.26(3)°, V = 3,187(1) ?³, Z = 4, R = 0.0526, wR ₂ = 0.1221.     

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. .     

Synthesis, Spectroscopic Studies and X-ray Crystal Structures of New Pyrazoline and Pyrazole Derivatives

Abstract  

The synthesis and characterization of some pyrazoline compounds of 1,3-diketones with hydrazine derivatives, namely, 1-(S-benzyldithiocarbazate)-3-methyl-5-phenyl-5-hydroxypyrazoline (1); 1-(2-thiophenecarboxylic)-3-methyl-5-phenyl-5-hydroxypyrazoline (2); 1-(2-thiophenecarboxylic)-3,5-dimethyl-5-hydroxypyrazoline (3); 1-(S-benzyldithiocarbazato)-3-methyl-5-phenylpyrazole (4); 1-(2-thiophenecarboxylic)-3-methyl-5-phenylpyrazole (5) and 1-(S-benzyldithiocarbazate)-3,5-dimethylpyrazole (6) are reported. Studies by IR, (¹H, ¹³C)-NMR spectroscopies and single crystal X-ray diffraction revealed that compounds (1)_, (2) and (3) are formed as pyrazoline, whereas (4) and (5) are formed as pyrazole derivatives only under acidic conditions. Compound (1) crystallizes in orthorhombic P2₁2₁2₁, a = 6.38960(10) ?, b = 12.9176(3) ?, c = 21.2552(5) ?, (2) crystallizes in monoclinic, P2₁/n, a = 11.3617(2) ?, b = 8.4988(2) ?, c = 92.8900(10) ? and β = 92.8900(5)°, (3) crystallizes in monoclinic, C2/c, a = 15.9500(5) ?, b = 9.3766(3) ?, c = 16.6910(5) ? and β = 113.825(2)°, (4) crystallizes in monoclinic, P2₁/c, a = 15.228(4) ?, b = 5.5714(13) ?, c = 19.956(5) ? and β = 91.575(7)° and (6) crystallizes in orthorhombic, P2₁2₁2₁, a = 5.3920(2) ?, b = 11.2074(5) ?, c = 21.885(1) ?. The (3) derivative represents the first pyrazoline compound prepared from 2,4-pentanedione and characterized crystallographically.