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In this article, we present the syntheses, crystal structures, vibrational spectra, optical and antibacterial properties of two new organic-inorganic hybrids, [Py(CH2)3TPP][CoCl4]·H2O (1) and [Py(CH2)3TPP][CuCl4] (2), where [Py(CH2)3TPP]2+ was 1-(1′-pyridyl-propyl)-3-triphenyl phosphonium. Two hybrids were crystallized in the monoclinic space group P21/n. The hybrids consisted of a [Py(CH2)3TPP]2+ cation and a tetrahedral [CoCl4]2−/[CuCl4]2− anion, where the crystal structure was stabilized by C−H···Cl, O−H···Cl, and C−H···O hydrogen bonds due to the presence of a water molecule in 1, and the crystal structure of 2 was stabilized by C−H···Cl hydrogen bonds. Experimental vibrational bands (IR and Raman) have been discussed and assigned. The intermolecular energy, the energy gap between HOMO and LUMO orbitals, as well as the first hyperpolarizabilities were predicted based on DFT calculations. The low energy gaps (1.26 eV for 1 and 1.20 eV for 2) were responsible for the charge transfer interactions that eventually occur between the cation and anion. The first hyperpolarizabilities (βtot) of 1 and 2 were 82 and 237 times as high as that of the standard KDP crystal, respectively, indicating that the as-prepared hybrids were excellent materials for NLO applications. Furthermore, it was found that both salts exhibit good bactericidal activity against Escherichia coli and Staphylococcus aureus. [ABSTRACT FROM AUTHOR]

A new tetrachlorocobalt(II) salt, [QlH]2[CoCl4]·2H2O(1) ([QlH]+= quinolinium), has been prepared and characterized by elemental analysis, IR, UV-Vis, ESI-MS, single-crystal X-ray diffraction, and magnetic susceptibility. Compound 1 crystallizes in the monoclinic space groupC2/cwith cell dimensionsa= 11.848(2) Å,b= 10.069(1) Å,c= 18.494(2) Å,β= 101.35(1) Å,V= 2163.3(4) Å3,Z= 4. The unit cell contains two [QlH]+cations, one [CoCl4]2–anion and two water molecules. The [QlH]+cations stack and form a 1D column through p···π and π···π interactions. The water molecules are linked to the anions through O-H···Cl hydrogen bonds to form two-dimensional molecular networks. The cations and [CoCl4]2–anions are linked through N-H···O and C-H···O hydrogen bonds and give further rise to a 3D hydrogen-bonding network structure. Magnetic susceptibility measurement in the temperature range 2–300 K shows that 1 exhibits a weak antiferromagnetic coupling behavior withθ= –2.90 K. [ABSTRACT FROM PUBLISHER]

Two new ion-pair complexes, based on [Ni(i-mnt)2]2–(i-mnt = isomaleonitriledithiolate) anion, [Bz-4-MePy]2[Ni(i-mnt)2]([Bz-4- MePy]+= 1-benzyl-4′-methylpyridinium) (1) and [Bz-4-MeQl]2[Ni(i-mnt)2]([Bz-4-MeQl]+= 1-benzyl-4′-methylquinolinium) (2), were obtained and characterized. The most obvious structure feature of 1 and 2 is that the [Ni(i-mnt)2]2–anions form a 1D chain through C···N or C···C short interactions between the i-mnt ligands, and the [Bz-4-MeQl]+cations of 2 form a 2D structure through the π···π stacking interactions between the aromatic rings. The C–H···N and C–H···Ni hydrogen bonds observed in the anions and cations consolidate the stacking of the molecules and give rise to a 3D network structure. [ABSTRACT FROM PUBLISHER]

Two new salts, [BzPid][Ni(mnt)] ( 1) and [4-NOBzPid][Ni(mnt)] ( 2) ([BzPid] = 1-benzylpiperidinium and [4-NOBzPid] = 1-(4′-nitrobenzyl)piperidinium, mnt = maleonitriledithiolate), were synthesized and characterized. The [Ni(mnt)] anions of 1 and 2 form the stepwise structure through short N···N interactions. In 1, there exists weak N-H···N, C-H···N, and C-H···Ni hydrogen bonds, while some weak interactions such as π···π, short O···O interaction, C-H···O and C-H···N hydrogen bonds are found in 2. These weak interactions play important roles in the stacking of the molecular and result in the forming of a 3D structure. Graphical Abstract: The [Ni(mnt)] anions of two new salts [BzPid][Ni(mnt)]( 1) and [4-NOBzPid][Ni(mnt)2]( 2) form the stepwise structure through short N···N interactions, and some weak interactions such as N-H···N, C-H···N, C−H···O, C-H···Ni hydrogen bonds and π···π and O···O interactions result in the forming of a 3D structure[Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Two hybrid materials, [4RBzTPP]2[Co(NCS)4] (NCS− = isothiocyanate, [4RBzTPP]+ = 4-R-benzyltriphenylphosphinium, R = F(1), Br(2)), have been prepared and characterized by elemental analyses, IR, UV spectra, X-ray diffraction, and magnetic susceptibility measurements. The Co(II) ions of the [Co(NCS)4]2− anions in 1 form a 1D chain through S···S interactions with the distance of 3.508 Å, while the anions and the [4BrBzTPP]+ cations formed an alternate chain by p···π, C-H···Co weak interaction and C-H···Br hydrogen bond in 2. Magnetic susceptibility measurement in the temperature range 2–300 K shows that both 1 and 2 exhibit a weak antiferromagnetic coupling property. [ABSTRACT FROM PUBLISHER]

Two new salts based on [Ni(tdas)] (tdas = 1,2,5-thiadiazole-3,4-dithiolate) anion, [Bz4EtPy][Ni(tdas)] ( 1) and [4ClBz4EtPy][Ni(tdas)] ( 2), have been prepared by reaction of Natdas, NiCl·6HO, and [Bz4EtPy]Br ([Bz4EtPy] = 1-benzyl-4-ethylpyridinium) or [4ClBz4EtPy]Br ([4ClBz4EtPy] = 1-(4′-chlorobenzyl)-4-ethylpyridinium), and characterized by elemental analyses, UV, IR, MS spectrum, molar conductivity and single crystal X-ray diffraction. Single-crystal X-ray diffraction analyses indicate that the two salts crystallize in a triclinic system with space group P−1. The unit cell contains two [Bz4EtPy]/[4ClBz4EtPy] and one [Ni(tdas)] anion in which the anion exhibits a quasi-planar structure. The crystals of 1 and 2 are stabilized through C-H···S and C-H···Ni hydrogen bonds, π···π stacking interactions and S···Cl short interactions. Graphical Abstract: In two new salts based on [Ni(tdas)] (tdas = 1,2,5-thiadiazole-3,4-dithiolate) anion, [Bz4EtPy][Ni(tdas)] ( 1) and [4ClBz4EtPy][Ni(tdas)] ( 2), the unit cell contains two cations and one [Ni(tdas)] anion, and C-H···S and C-H···Ni hydrogen bonds, π···π stacking interactions and S···Cl short interactions are founded.[Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Two new salts, [1-NaMe-2-NH2Py]2[Ni(mnt)2] (1) and [1-NaMe-2-NH2Py]2[Ni(i-mnt)2] (2) ([1-NaMe-2-NH2Py]+ = 1-(1'-naphthylmethyl)-2-aminopyridinium, mnt2- = maleonitriledithiolate, and i-mnt2- = iso-maleonitriledithiolate), have been obtained and characterized by elemental analyses, infrared (IR), ultraviolet (UV), mass spectroscopy (MS), molar conductivities, and single-crystal x-ray diffraction. The results have shown that the change of the ligand from mnt to i-mnt results in differences in the crystal system, space group, weak interactions, and the stacking mode of the cations and anions. The effects of weak interactions such as C--H···N, N-H···N, or C--H···Ni hydrogen bonds and p···π, π···π, and C--H···π stacking interactions generate a three-dimensional (3D) network structure. [ABSTRACT FROM AUTHOR]

Two tetrachlorocuprate(II) salts with substituted benzyl pyridinium, [BzPy]2[CuCl4](1) and [Bz-4-NH2Py]2[CuCl4](2) ([BzPy]+ = 1-benzylpyridinium; [Bz-4-NH2Py]+ = 1-benzyl-4'-aminopyridinium), were synthesized and characterized. The two salts comprise a [CuCl4]2- anion and two [BzPy]+ or [Bz-4-NH2Py]+ cations. The [CuCl4]2- anion exhibits a very distorted tetrahedral and square-planar coordination geometry for 1 and 2, respectively. The C-H···Cl, N-H···Cl and C-H···Cu weak hydrogen bonds between the anion and cation found in the crystal play important roles in the stacking and stabilization of the two salts. The experimental results indicated that the two salts show good antibacterial activities for colibacillus, aurococcus, and bacillus subtilus. [ABSTRACT FROM AUTHOR]

Two new Ni(II) complexes, [4RBzTPP]2[Ni(i-mnt)2] (i-mnt = isomaleonitriledithiolate, [4RBzTPP]+ = 1-(4'-R-benzyl)triphenylphosphinium; R = Br(1) and CN(2)), were obtained in the crystalline form by the reaction of K2(i-mnt), NiCl2·6H2O and 1-(4'-R-benzyl)-triphenylphosphinium bromide in H2O. Both complexes crystallize in the triclinic system and the central Ni(II) ion has a distorted square planar coordination. Some weak hydrogen bonds, such as C-H···S, C-H···N, or C-H···Ni, observed between the [Ni(i-mnt)2]2- anion and the cation, play important roles in the stacking of the molecules, and give rise to a 3D network structure. [ABSTRACT FROM AUTHOR]

Two new salts, [NO2BrBzPy]2[M(mnt)2] ([NO2BrBzPy]+= 1-(2'-bromo-4'-nitrobenzyl)pyridinium; mnt2-= maleonitriledithiolate; M = Ni(1), Pd(2)) have been prepared and characterized by elemental analyses, IR, UV, ESI-MS spectra, TG, and single-crystal X-ray diffraction. The results reveal that when the metal ion is changed from Ni(II) to Pd(II), the crystal system, and the dihedral angles between the phenyl and pyridine rings and the C-C-N reference plane of the cation, and the stacking modes of the anions and the cations are evidently different. Some weak interactions such as C-H···Br, C-H···O, C-H···N and C-H···S hydrogen bonds, p[image omitted] or [image omitted] stacking interactions in 1 and 2 play important roles in the molecular stacking and generate a 2D structure. [ABSTRACT FROM AUTHOR]

A new ion-pair complex, [BzTPP]2[Ni(i-mnt)2](1) (i-mnt2- = iso-maleonitriledithiolate, [BzTPP]+ = benzyltriphenylphosphinium) was synthesized and characterized by elemental analysis, IR, UV, EI-MS spectra and single crystal X-ray diffraction. The single-crystal structural analysis shows that 1 crystallizes in the triclinic space group P-1, with a = 9.466(1) Å, b = 10.196(1)Å, c = 29.252(3)Å, α = 99.28(1)ˆ, β = 93.96(1)ˆ, γ = 106.34(1)ˆ, V = 2654.3(4)Å3, Z = 2. The Ni(II) ions of the [Ni(i-mnt)2]2 - anion adopted a square-planar coordination geometry. Four weak C─H...N hydrogen bonds between the anions and the cations observed in the crystal give further rise to a 3D structure. [ABSTRACT FROM AUTHOR]

Complexes [Ni(H 2 O) 6 (ML) 2 ]· n H 2 O (M = Cu, Ni; L = Schiff base derived from glycylglycine and salicylaldehyde, C 11 H 9 N 2 O 4 ) were synthesized and characterized. The [Ni(H 2 O) 6 (CuL) 2 ]·10H 2 O complex 1 crystallized in the space group , with a = 7.217(1), b = 11.674(1), c = 12.678(1) Å, α = 66.56(1), β = 76.60(1), γ = 80.46(1)°, and Z = 1. The [Ni(H 2 O) 6 (NiL) 2 ]·2H 2 O complex 2 crystallized in the group P 2(1)/ c , with a = 10.564(2), b = 20.246(4), c = 6.965(2) Å, β = 103.14(1)°, and Z = 2. Hydrogen bonding involving [ML] - , Ni(H 2 O) 6 2+ and molecular water forms a three-dimensional (3D) supermolecule. The determination of variable-temperature magnetic susceptibilities indicates an antiferromagnetic interaction between the metallic atoms of 1 , and a corresponding ferromagnetic interaction for 2 . [ABSTRACT FROM AUTHOR]

The title complex, (C25H21NO2P)2[Ni(C4N2S2)2]·2H2O or (NO2BzTPP)2 [Ni(mnt)2]·2H2O [where NO2BzTPP is (4-nitro­benz­yl)tripenylphosphinium and mnt is maleonitrile­dithiol­ate], is reported. The Ni atom lies on a centre of symmetry. The square-planar NiII ion of the anion is coordinated by four S atoms of the two mnt2− ligands. The benzene rings in the [NO2BzTPP]+ cation are twisted with respect to the plane of the P—C—C chain. Weak C—H⋯Ni inter­actions between the anion and cation and C—H⋯π, π–π and C—H⋯O inter­actions between cations are observed in the crystal structure. [ABSTRACT FROM AUTHOR]

The self-assembly of [Zn(NCS) 4 ] 2− (NCS − = isothiocyanate) anion and substituted benzyl triphenylphosphonium cations [4RBzTPP] + (R = H( 1 ), NO 2 ( 2 ); BzTPP = benzyl triphenylphosphonium) results in the forming of two new molecular solids, [BzTPP] 2 [Zn(NCS) 4 ] ( 1 ) and [4NO 2 BzTPP] 2 [Zn(NCS) 4 ] ( 2 ), which have been characterized by elemental analyses, UV, IR, ESI-MS and single-crystal X-ray diffraction. The Zn(II) ion of the [Zn(NCS) 4 ] 2− anion both 1 and 2 has a distorted tetrahedral environment with four N atoms of four NCS − anions. The anions form a 1D chain through S⋯S interactions with the distances of 3.470 Å for 1 and 4.067 Å for 2 , while the combination of the C H⋯S and C H⋯O hydrogen bonds as well as p⋯π interaction in 2 make the cations form a 1D column. The title molecular solids show fluorescence emission in the solid state at room temperature. [ABSTRACT FROM AUTHOR]

Abstract: The preparation, crystal structures and magnetic properties of two novel salts, [DiBzPid][Ni(mnt)2](1) and [DiBzPid]2[Cu(mnt)2](2), where [DiBzPid]+ = N,N′-dibenzylpiperidinium and mnt2− =maleonitriledithiolate, are investigated. The Ni(III) ions of 1 form a 1D zigzag alternating chain in a [Ni(mnt)2]− column through intermolecular π⋯π stacking interaction, short C⋯S and C⋯N interactions between the adjacent anions, while the cations(C) and anions(A) of 2 stack into a 1D alternating ⋯CCACCACC⋯ column via C–H⋯N, C–H⋯π hydrogen bonds and π⋯π stacking interactions. Magnetic susceptibility measurements in the temperature range 2–300K show that 1 exhibits a spin-gap transition around 150K with Δ/kb =429.94K, while 2 shows a very weakly ferromagnetic coupling behavior with θ =1.18×10−2 K. [Copyright &y& Elsevier]

Abstract: The preparation, crystal structures and magnetic properties of two complexes containing bis(maleonitriledithiolate)nickel(III)/copper(II) anion, [4BrBzTPP][Ni(mnt)2] (1) and [4BrBzTPP]2[Cu(mnt)2] (2) ([4BrBzTPP]+ =1-(4′-bromobenzyl)triphenylphosphinium) are report here. The crystals of two complexes belong to the triclinic system with space group P-1. The [Ni(mnt)2]− anions form a stepwise stack for 1 through weak π···π stacking interactions, short C···S interactions between the neighboring anions, while the [Cu(mnt)2]2− anions and the [4BrBzTPP]+ cations in 2 are linked through Ch name="pdbond" />S, Ch name="pdbond" />N and Ch name="pdbond" />Cu hydrogen bonds. The difference of the stacking mode and the weak interactions in 1 and 2 results in the difference of the magnetic properties: complex 1 exhibits an activated magnetic behavior in the high-temperature range together with a Curie tail at lower temperature range, while 2 shows a ferromagnetic exchange interaction with θ =25.65K. [Copyright &y& Elsevier]

Abstract: The self-assembly of [Co(NCS)4]2− anion and substituted benzyltriphenylphosphonium cations [4RBzTPP]+ (R=H(1), NO2(2)) results in the forming of two new hybrid materials, [BzTPP]2[Co(NCS)4](1) and [4NO2BzTPP]2[Co(NCS)4](2). The Co(II) ions of the [Co(NCS)4]2− anions in 1 form a 1D chain through S⋯S interactions with the S⋯S distance of 3.458Å, while the C–H⋯S, C–H⋯O hydrogen bond and p⋯π interaction were found in 2. Magnetic susceptibility measurement in the temperature range 2–300K shows that 1 exhibits a magnetic coupling interaction from ferromagnetic to antiferromagnetic around 30K as the temperature is lowered, while 2 shows weak antiferromagnetic coupling behavior. [ABSTRACT FROM AUTHOR]

Abstract: Syntheses, crystal structures and magnetic properties of two salts, [FBzTPP][Ni(mnt)2](1) and [FBzTPP]2[Cu(mnt)2](2) ([FBzTPP]+ =1-(4′-fluorobenzyl)triphenylphosphinium, mnt2− =maleonitriledithiolate), are investigated. In 1, the anions and cations stack into well-segregated columns, and the Ni(III) ions form a 1D alternating chain in a [Ni(mnt)2]− column through intermolecular Ni⋯S and π⋯π interactions with the Ni⋯Ni distances of 3.939, 4.057 and 4.101Å, and the C–H⋯N hydrogen bonds are found between the [Ni(mnt)2]− anion and the neighboring [FBzTPP]+ cation. The [Cu(mnt)2]2− anions in 2 do not form a column and no weak interactions exist between the anions duo to isolation of the [FBzTPP]+ cations, while C–H⋯F and C–H⋯S hydrogen bonds were found in 2. Magnetic susceptibility measurements in the temperature range 2–300K show that 1 exhibits a spin–gap transition around 46K, and antiferromagnetic interaction (θ =−49.0K) in the high-temperature phase (HT) and spin gap (Δ/kb =88.2K) in the low-temperature phase (LT), while 2 shows a very weak antiferromagnetic coupling behavior with θ =−1.33×10−2 K. [ABSTRACT FROM AUTHOR]

Abstract: Three new ion-pair complexes, [4RBzDMAP]2[Cu(mnt)2] (mnt2− =maleonitriledithiolate; [4RBzDMAP]+ =1-(4′-R-benzyl)-4-dimethylaminopyridinium, R=F(1), Cl(2) and Br(3)) were synthesized and characterized by elemental analyses, IR, UV, single crystal X-ray diffraction and magnetic measurements. The [Cu(mnt)2]2− anions and the cations stack alternately and form a 1D column via C–H···S, C–H···π or C–H···Cu interactions for 1 and 2. While the cations stack into a column though π···π or C–H···π interactions between pyridine and phenyl rings for 1 and 3. The change of the molecular topology of the counteraction when the 4-substituted group in the benzyl ring have been changed from F or Cl to Br atom, results in the difference in the crystal system, space group and the stacking mode of the cations and anions of 1, 2 and 3. Some weak hydrogen bonds between the adjacent columns further generate a 3D network structure. It is interesting that 1 and 2 exhibits antiferromagnetic coupling with θ =−2.372K and θ =−14.732K, while 3 shows weak ferromagnetic coupling feature with θ =0.381K. [ABSTRACT FROM AUTHOR]

A novel coordination polymer [Ba(H2O)4(CuL)2]n (where L=Schiff base derived from 5-bromosalicylaldehyde and glycylglycine) has been synthesized and characterized by X-ray crystallography. The structure reveals the formation of one-dimensional chains, which are assembled further into two-dimensional network by hydrogen bonds between the coordinated water molecules. [Copyright &y& Elsevier]