Lin-Liang Yu

Synthesis, Weak Hydrogen Bonds and 3D Crystal Structure of a New Iso-maleonitriledithiolate Nickel Ion-pair Complex

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.

Two New Salts Based on Bis(nitriledithiolate)nickelate Anion with Substituted 2-Aminopyridinium: Syntheses, Crystal Structures, and Properties

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.

3D network structure and magnetic behaviour of a new Ni(III) maleonitriledithiolate complex with C–H • • • π and π • • • π interactions using 4-dimethylaminopyridinium cation

A new ion-pair complex, [DMAPH][Ni(mnt)2] ([DMAPH]+ = 4-dimethylaminopyridinium and mnt2− = maleonitriledithiolate), was prepared and characterized by elemental analysis, IR spectra, electrospray mass spectra and X-ray single-crystal diffraction. In the solid state, the anions and [DMAPH]+ cations are alternately stacked and form 1D column via π ··· π and C–H ··· π interactions between the anion and neighboring [DMAPH]+ cations. The anion–anion C ··· N interactions, and the anion–cation hydrogen bonds between adjacent columns further generate a 3D network structure. The variable temperature magnetic susceptibility measurement in the temperature range 1.8–300 K shows that the complex exhibits an antiferromagnetic behavior with a Neel temperature (T N) of 7.0 K.

Two New Salts Based on Bis(1,2,5-thiadiazole-3,4-dithiolate)nickelate Anion with Benzylpyridinium Derivatives: Syntheses, Crystal Structures and Properties

Two new salts based on [Ni(tdas) 2 ] 2 − (tdas 2 − = 1, 2, 5-thiadiazole-3,4-dithiolate) anion with substituted benzylpyridinium cation, [BzPy][Ni(tdas) 2 ] (1) and [NO 2 BzPy] 2 [Ni(tdas) 2 ] (2), have been prepared by reaction of Na 2 tdas, NiCl 2 .6H 2 O, and 1-Rbenzylpyrid-inium bromide [RBzPyBr, R = H(1), NO 2 (2)]. Single-crystal X-ray diffraction analyses indicate that the two salts crystallize in a monoclinic system with space group C 2/c, but the stacking modes of the anions and the cations are different. Some intra-molecular contacts such as p· · · π, π · · · π, or C−H · · · N weak interactions in 1 and 2 play important roles in the molecular stacking and generate a 2D structure. In addition, IR, UV, MS, molar conductivities and effect on crystal structures 1 and 2 are successively described.

An Ionic Pair Complex Containing Bis(maleonitriledithiolato)palladium(II) Anion and Substituted 4-Dimethylaminopyridinium: Synthesis, Weak Interactions and 3D Network Structure

An ionic pair complex, [FClBzDMAP]2[Pd(mnt)2] (1) , ([FClBzDMAP]+ = [1-(4′-fluoro-2′-chlorobenzyl)-4-dimetylamino pyridinium, mnt2− = maleonitriledithiolate), was synthesized and characterized by elemental analyses, IR, UV-vis spectra, molar conductivities and single crystal diffraction. The crystal belongs to the triclinic system, space group P-1 with cell constants a = 8.3472(8) Å, b = 9.3988(9) Å, c = 13.5875(14) Å, α = 76.676(1)°, β = 86.036(1)°, γ = 71.182(1)°, Z = 1. It is interesting that the [FClBzDMAP]+ cations (C) and the [Pd(mnt)2]2− anions (A) in 1 stack into a 1D alternating CC-A-CC-A-CC column along ab direction, while the cations form a 1D column along bc direction. Some weak interactions such as p … π, π … π, Cl … S, and C─ H … N interactions in the crystal play important roles in the self-assembly process and give rise to a 3D network structure.

Synthesis, Crystal Structure, Weak Interactions, Spectra and Magnetic Behavior of a New Ion-pair Complex Containing Bis(maleonitriledithiolato)nickel(III) Monoanion and Substituted Isoquinolinium Cation

A new ion-pair complex, [BrClBzIQl][Ni(mnt)2](1) ([BrClBzIQl]+ = 1-(2′ -chloro-4′ -bromobenzyl)isoquinolinium, and mnt2− = maleonitriledithiolate) has been prepared and characterized by elemental analyses, IR, MS spectra, single crystal X-ray diffraction and magnetic susceptibility. The crystals are monoclinic space group, C c, a = 9.249(3) Å, b = 18.312(5) Å, c = 32.062(9) Å, β = 90.92(1)°, V = 5430(3) Å3, Z = 4. The Ni(III) ions of 1 form a dimer with Ni…Ni distance being 4.332 Å through short Ni…S and S…S interactions. The weak anion-cation πvπ stacking interactions, C─H…N hydrogen bonds and short Ni…N interactions further generate a 3D network structure. Magnetic susceptibility measurement in the temperature range 2–300 K shows that 1 exhibits antiferromagnetic behavior with g = 2.02, J = −373.3 cm−1.

Syntheses, Crystal Structures and Antibacterial Properties of Bis(1-benzyl-4′-R-pyridinium)tetrabromocuprate(II) [R = NH2 or N(CH3)2]

Two tetrabromocuprate(II) salts with benzyl substituted pyridinium, [Bz-4-NH2Py]2[CuBr4] (1) and [Bz-4-N(CH3)2Py]2- [CuBr4] (2) ([Bz-4-NH2Py]+ = (1-benzyl-4′-aminopyridinium), [Bz-4-N(CH3)2Py]+ = 1-benzyl-4′-dimethylaminopyridinium) were crystallized from methanol and diluted in HBr solution. Compound 1 crystallizes in the orthorhombic Pna21, with 2 in the monoclinic P21/n. Two salts are composed of one tetrahedral [CuBr4]2− anion and two tortuous [Bz-4-NH2Py]+/[Bz-4-N(CH3)2Py]+ cations. The [CuBr4]2− anions in 1 form a linear chain, while the combination of C-H···π, C-H···Br, C-H···N weak hydrogen bonds and π···π interactions results in the forming of a 3D network structure of 1 and 2. The two salts show good antibacterial activities for E. coli and S. aureus.

Syntheses, Crystal Structures, Weak Interactions, and Properties of Two Salts Containing Bis(maleonitriledithiolato)nickel/Palladium(II) Anion and Disubstituted Benzylpyridinium

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 or stacking interactions in 1 and 2 play important roles in the molecular stacking and generate a 2D structure.

Synthesis, Complicated Weak Interactions, and Network Structure of a New Salt Containing Bis(iso-maleonitriledithiolato)nickel(II) Anion and Substituted Dipyridinium

A new salt, [EtdiPy][Ni(i-mnt)2](1) (i-mnt = iso-maleonitriledithiolate, [EtdiPy]2+= 1,1′-ethylene-2,2′-dipyridinium) has been synthesized and characterized by elemental analysis, IR, UV-Vis, EI-MS spectra, and single crystal X-ray diffraction. It is interesting that the [Ni(i-mnt)2]2− anions containing Ni(1) atom form a 1D chain by the π···π stacking interactions between the CN groups, while the anions containing Ni(2) atom form a ring structure through the S···N short interactions. The weak p···π and π···π stacking interactions, as well as C‒H···N and C‒H···S hydrogen bonds between the anions and the cations observed in the crystal, give further rise to a complicated network structure.

A Hybrid Organic-Inorganic Salt Containing Bis(maleonitriledithiolate)copper(II) Anion and Substituted 4-Dimethylaminopyridinium: Synthesis, Crystal Structure, and Magnetic Property

A new hybrid organic-inorganic salt, [4CNBzDMAP]2 [Cu(mnt)2] (mnt2−= maleonitriledithiolate; [4CNBzDMAP]+= 1-(4′-cyanobenzyl)-4-dimethylaminopyridinium) was synthesized and characterized by elemental analyses, IR, UV, molar conductivity , single crystal X-ray diffraction and magnetic measurement. The crystal belongs to the triclinic system, space group P-1 with cell constants a = 7.0785(9) Å, b = 11.3432(14) Å, c = 13.1406(16) Å, α = 71.784(1)°, β = 81.772(1)°, γ = 82.663(1)°, Z = 1. The structure was solved by direct methods and refined to R1= 0.0343 (wR2= 0.1186). The [Cu(mnt)2]2 − anions and the [4CNBzDMAP]+ cations in 1 stack alternately and form a 1D column via π · · · π stacking interactions. Weak C−H═ N hydrogen bonds between [Cu(mnt)2]2 − anions and [4CNBzDMAP]+ cations of the adjacent columns further generate a 3D network structure. The magnetic susceptibility of 1 measured in the temperature range 2.0−310 K shows weak antiferromagnetic coupling feature with θ = −0.0775 K.