Cl Weak Interactions Research Articles

Synthesis and complexation behavior of 3,4-bis(chloromercurio)2,5-dimethylthiophene

Synthesis of a new bidentate Lewis acid 3,4-bis(chloromercurio)2,5-dimethylthiophene (1) has been reported which is not accessible using other methods. Crystallization of compound 1 from a tetrahydrofuran (THF) and dimethyl sulfoxide (DMSO) results Lewis acid-nucleophile (Lewis base) adduct in 1:2 ratio such as C6H6SHg2Cl2•2THF (2) & C6H6SHg2Cl2•2DMSO (3) respectively. The bifunctional Lewis acid on crystallization with Et4NCl resulted in the formation of compound 4 {[(C6H6SHg2Cl2)3Cl2][Et4N]2}, which is a unique 3:2 adduct of compound 1 with chloride anion. Compounds 1–4 have been characterized by NMR, elemental analysis, and X-ray crystallography. The solid state structures of compounds 1–4 reveals the existence of Hg•••Cl, CH•••Cl weak interactions which lead to the formation of 1D, 2D and 3D supramolecular structures.

Synthesis, crystal structure, and magnetic characterization of chiral Schiff-base manganese(III) complex containing cocrystallized crown ether molecule

A chiral Schiff-base Mn(III) compound containing cocrystallized crown ether {Mn[(R,R)-Salcy]·(H2O)2}2(ClO4)2·18-Crown-6 (I), where (R,R)-Salcy = (R,R)-N, N′-(1,2-cyclohexanediylethylene)bis(salicylideneiminato) dianion, has been synthesized by the reaction of {Mn[(R,R)-Salcy](H2O)2}ClO4 with 18-crown-6 ether and K4[Mo(CN)8]. X-ray diffraction analysis revealed that the cationic mononuclear Mn(III) Schiff-base compounds were self-complementary via intermolecular O-H⋯O H-bond formed by coordinated aqua ligand of one molecule and phenolic oxygen atoms of the neighboring molecule, giving supramolecular dimeric structure. The H-bond between O atoms of the cocrystallized crown molecule and that of the mentioned above dimer supported formation of one-dimensional supramolecular chain structure which can be linked to two-dimensional supramolecular network based on intermolecular O-H⋯Cl weak interactions. Our study of its magnetic properties revealed weak antiferromagnetic coupling between the adjacent Mn(III) ions.

Temperature-triggered reversible dielectric and nonlinear optical switch based on the one-dimensional organic-inorganic hybrid phase transition compound [C6H11NH3]2CdCl4.

The one-dimensional organic-inorganic hybrid compound bis(cyclohexylammonium) tetrachlorocadmate(II) (1), in which the adjacent infinite [CdCl4]n(-) chains are connected to each other though Cd···Cl weak interactions to form perovskite-type layers of corner-sharing CdCl6 octahedra separated by cyclohexylammonium cation bilayers, was synthesized. It undergoes two successive structural phase transitions, at 215 and 367 K, which were confirmed by systematic characterizations including differential scanning calorimetry (DSC) measurements, variable-temperature structural analyses, and dielectric and second harmonic generation (SHG) measurements. A precise structural analysis discloses that the phase transition at 215 K is induced by the disorder-order transition of cyclohexylammonium cations, while the phase transition at 367 K derives from changes in the relative location of Cd atoms. Emphatically, both the dielectric constant and SHG intensity of 1 show a striking change between low and high states at around 367 K, which reveals that 1 might be considered as a potential dielectric and nonlinear optical (NLO) switch with high-temperature response characterization, excellent reversibility, and obvious change of states.

Syntheses, Crystal Structures, and Properties of Two New Ion-Pair Compounds Based Upon bis(1,2,5-thiadiazole-3, 4-dithiolate)nickelate Anion and Substituted Benzyltriphenylphosphium Cations

Two new ion-pair compounds based on [Ni(tdas)2]2− (tdas = 1,2,5-thiadiazole-3,4-dithiolate) anion with substituted benzyl triphenylphosphium cation, [2ClBzTPP]2[Ni(tdas)2](1) and [4ClBzTPP]2[Ni(tdas)2](2), have been prepared and characterized by UV, IR, ESI-MS, molar conductivity, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analyses indicate that 1 crystallizes in the triclinic space group P–1, while 2 crystallizes in the monoclinic space group P21/n. Some intramolecular contacts such as C−H···Cl, C−H···S, C−H···N or S···Cl weak interactions observed in 1 and 2 consolidate the crystal packing and generate a 3D network structure.

New Co(II) Metal–Organic Coordination Polymers with 9,10-Bis(triazol-1-ylmethyl)anthracene (L): Synthesis and Crystal Structures

Single crystals of L [L = 9,10-bis(triazol-1-ylmethyl)anthracene] and a new Co(II) metal coordination polymers with ligand L, [Co(L)2Cl2]∞ were synthesized and characterized by elemental analyses, IR spectroscopy and single-crystal X-ray diffraction. Complex 1 has one-dimensional (1-D) chain structure, and was further linked into infinite three-dimensional (3-D) supramolecular sheets by inter-chain C–H···Cl weak interactions. In 1, the Co(II) ion is four-coordinated to two nitrogen atoms of two distinct L ligand and two chlorine atoms to form a distorted tetrahedral geometry, L adopts a trans-gauche conformation with the shortest N···N distance between the two N donors. Ligand 9,10-bis(triazol-1-ylmethyl)anthracene (L) and a new Co(II) metal coordination polymers [Co(L)2Cl2]∞ were synthesized. Complex [Co(L)2Cl2]∞ has one-dimensional (1-D) chain structure, and was further linked into infinite three-dimensional (3-D) supramolecular sheets by inter-chain C–H···Cl weak interactions. In [Co(L)2Cl2]∞, L adopts a trans-gauche conformation with the shortest N···N distance between the two N donors.

Supramolecular structure of enaminones in solid-state

The crystalline structure of four enaminones [R 1C(O)CH C(Me)NR 2R 3, where R 1 = CCl 3, R 2 = H, R 3 = Bn ( 1); R 1 = CHCl 2, R 2 = H, R 3 = Bn ( 2); R 1 = CCl 3, R 2, R 3 = (CH 2) 4 ( 3); R 1 = CHCl 2, R 2 , R 3 = (CH 2) 2 O (CH 2) 2 ( 4)] were determined by X-ray diffraction. It was found that compounds 1– 4 adopted the enaminone tautomeric form. Compounds 1 and 2 displayed intramolecular hydrogen bonds (2.658 ⩽ d (N⋯O) ⩾ 2.726), which are associated with the presence of resonance-assisted hydrogen bonds (RABHs). The bond length data implicated that π-delocalization in 3 and 4 was reduced in comparison to 1 and 2 and this can be interpreted as some gain of the aromatic character in the chelate form. In addition, it was shown that the crystal packing of these enaminones is governed by C H⋯O, C H⋯Cl, Cl⋯Cl weak interactions and these interactions presents interatomic distances in accordance with the reported van der Waals radii of the atoms involved. The energy of these intermolecular interactions was calculated as a difference in energy between the complex on the one hand and the sum of isolated monomers on the other. The energetic contributions of each interaction to the stability of the crystalline packing were determined, firstly for each interaction independently and secondly, for all interactions simultaneously. The additive effect was verified by the fact that the sum of all individual energetic contributions resulted in the same stability as that found when the energetic contribution of all interactions was calculated simultaneously.

Synthesis, spectroscopic and crystal structure investigation of [Cu(bzsmp) 2Cl 2];{bzsmp = 2-benzylsulfanyl-5-(2-methoxyphenyl)-1,3,4-oxadiazole}: cyclization of N 2-[bis(benzylsulfanyl)methylene]-2-methoxybenzohydrazide to 2-benzylsulfanyl-5-(2-methoxyphenyl)-1,3,4 -oxadiazole during complexation

The ligand N 2-[bis(benzylsulfanyl)methylene]-2-methoxybenzohydrazide (N 2-bmbh) ( 1) on reaction with CuCl 2.2H 2O yielded the mononuclear complex [Cu(bzsmp) 2Cl 2] ( 2) (2-benzylsulfanyl-5-(2-methoxyphenyl)-1,3,4-oxadiazole, bzsmp). Complex 2 has been characterized by analytical, spectroscopic and X-ray data. X-ray study of 2 reveals that the cyclized ligand 2-benzylsulfanyl-5-(2-methoxyphenyl)-1,3,4-oxadiazole (bzsmp) acts as neutral bidentate ligand to form six membered chelate ring and the presence of C–H⋯π (face to edge) and C–H⋯S and two type of C–H⋯Cl weak interactions.

Metal Coordination Architectures of 2,3‐Bis(triazol‐1‐ylmethyl)quinoxaline: Effect of Metal Ion and Counterion on Complex Structures

AbstractA series of complexes, [ZnLCl2]2 (1), [ZnL2(NO3)2]∞ (2), [MnL2(NO3)2]∞ (3), {[ZnL2(H2O)2](ClO4)2(CH3COCH3)2}∞ (4), {[MnL2(H2O)2](ClO4)2(CH3COCH3)2}∞ (5), {[CdL2(H2O)2]‐(ClO4)2(H2O)6}∞ (6), and {[AgL](ClO4)(H2O)1.5}∞ (7), based on the flexible ligand 2,3‐bis(triazol‐1‐ylmethyl)quinoxaline (L) were synthesized and characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses, and single‐crystal X‐ray diffraction. Complex 1 is a dinuclear macrocyclic molecular, which is further linked into a 1D supramolecular chain by intermolecular C–H···Cl weak interactions. The metal centers in 2 and 3 coordinate two NO3– anions, and the flexible ligand bridges M(NO3)2 [M = ZnII or MnII] units to form 1D chain structures. Complexes 4, 5, and 6 show a 2D network structure with (4,4) topology. As expected, complex 7 has a 1D strand chain structure that is different than other MII complexes (4, 5, and 6) with the same ligand. These chains are further extended into a 2D supramolecular network by O···Ag···O weak interactions. In all these complexes, the ligand bridges in a similar mode; however, the complexes have different structures ranging from a dinuclear structure to a 2D network mainly due to the differences in the coordination geometries of the metal centers and counterions. These results reveal that the coordination geometry of metal ions and the coordinating abilities of the counterions play important roles in defining the overall structure of metal–organic frameworks. In addition, the fluorescent properties of complexes 1, 2, 4, 6, 7, and ligand L and the EPR spectra of complex 5 were also investigated. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Crystal Structure and Surface Photovoltage Properties of MnII Coordination Supramolecules

AbstractThree MnII coordination supramolecular complexes [Mn(pdc)(H2O)]n 1, {[Mn(pdc) (phen)(H2O)]·3H2O}n 2, and {[Mn(cyan)2(H2O)4]·2HCl·2(Hcyan)} 3 (H2pdc = pyridine‐2,3‐dicarboxylic acid, Hcyan = cyanuric acid, phen = 1,10‐phenanthroline) were hydrothermally synthesized and their structures determined by single‐crystal X‐ray diffraction. The pdc group in complex 1 bridges the MnII ions to form an infinite 3D structure. In complex 2, the MnII ion is bridged to a 1D infinite chain by pdc groups and the chain is further connected to a 2D structure by hydrogen bonds. The 3D structure of complex 3 is formed by hydrogen bonds and O···Cl weak interactions. Surface photovoltage spectroscopy (SPS) of complexes 1–3 indicate that they all possess positive SPV response in the range of 300–800 nm and show p‐type semiconductor characteristic. The intensities of the SPV responses are obviously different, and this can mainly be attributed to the differences in their structures. Field‐induced surface photovoltage spectroscopy (FISPS) of complexes 1–3 confirms their p‐type semiconductor characteristic.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Synthesis and single crystal structural investigations on quaternary salts of tellurated alkylamine derivatives

Tellurated alkylamine derivatives 4 - CH 3 OC 6 H 4 Te ( CH 2 ) 2 NH 3 + Cl - ( 1 ) , 4 - CH 3 OC 6 H 4 Te ( Cl 2 ) ( CH 2 ) 3 NH 3 + Cl - ( 2 ) , Cl 2 Te ( ( CH 2 ) 2 NH 3 + Cl - ) 2 ( 3 ) and Cl 2 Te ( ( CH 2 ) 3 NH 3 + Cl - ) 2 ( 4 ) have been synthesized by reacting appropriate organic halides with the nucleophile 4-CH 3OC 6H 4Te − or Te 2− generated in situ by borohydride reduction of (4-CH 3OC 6H 4Te) 2 or Te powder followed by reaction with HCl of appropriate concentration. The zwitterionic species [ − Cl 4 Te ( CH 2 ) 3 NH 3 + ] was generated when single crystals of 2 were grown in methanol at 0 °C. Complexes 1– 4 exhibit characteristic 1H NMR spectra. The single crystal structures of 1– 4 and 2a have been determined. In the crystals of 1, C–H⋯π distances have been found to be 3.31(7)–3.59(5) Å. In both 2 and 2a, weak Te⋯Cl interactions (3.54(2) –3.62(2) Å) are observed. The C–H⋯π distance in the crystal of 2 is 3.19(0) Å. In 2a and 3, water hydrogen bonds connect the water molecules with the end NH 3 + groups from different molecules. In the case of 3, Te⋯Cl weak interactions involving the Cl − ions connect together two such chains. The geometry of Te in 1 is V shaped. In 2 and 3 it is pseudo trigonal bipyramidal, and in 2a, it is square pyramidal. However, in the latter case it becomes distorted octahedral due to weak Te⋯Cl secondary interactions. The geometry about Te in 4 is distorted octahedral due to weak Te⋯Cl interactions involving Cl − ions. However, there are no intermolecular Te⋯Cl interactions.