Chun-Lin Ni

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.

Syntheses, weak interactions, and 3-D network structures of two salts based on [Ni(i-mnt)2]2− (i-mnt2−=iso-maleonitriled-ithiolate) anion with substituted pyridinium cation

Two new salts, [2-NaMePy]2[Ni(i-mnt)2] (1) and [2-NaMe-4-MePy]2[Ni(i-mnt)2] (2) ([2-NaMePy]+ = 1-(2′-naphthylmethyl)pyridinium, [2-NaMe-4-MePy]+ = 1-(2′-naphthylmethyl)-4-methylpyridinium and i-mnt2− = iso-maleonitriledithiolate), have been prepared and characterized by elemental analyses, UV, IR, molar conductivity, and single crystal X-ray diffraction. The anions in 1 form a 1-D chain through short C ··· N interactions between the anions, while the cations in 2 stack a 1-D column via C–H ··· π and π ··· π stacking interactions between the cations. The effect of weak intramolecular interactions such as C–H ··· N, C–H ··· S, C–H ··· Ni hydrogen bonds, and π ··· π stacking interactions between the cations and the anions further generate a 3-D network structure. The change of the molecular topology of the countercation when the 4-substituted group in the pyridine ring is changed from H atom to CH3 group results in different crystal system, space group, and the stacking mode of the cations and anions of 1 and 2.

Syntheses, Crystal Structures, and Magnetic Properties of Two Hybrid Materials Self-Assembly from Tetra(isothiocyanate)cobalt(II) Anion and Substituted Benzyl Triphenylphosphinium

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.

Synthesis, crystal structure, and magnetic properties of a salt containing [Cu2Cl7]3− and 4-nitrobenzyl-4′-dimethylaminopyridinium

A new salt, [NO2BzDMAP]3[Cu2Cl7] · H2O (1), has been synthesized, where [NO2BzDMAP]+ is 1-(4′-nitrobenzyl)-4-dimethylaminopyridinium. Herein, the synthesis, spectral and structural characterization, and magnetic behavior of 1 are reported. It is orthorhombic, with space group Pca21, and a = 26.639(2) Å, b = 9.638(1) Å, and c = 20.011(2) Å with V = 5137.5(7) Å3 for Z = 4. The anion shows a chloride-bridged binuclear structure with Cu ··· Cu distance of 3.872 Å; the two Cu(II) ions have a tetrahedral geometry. The cations stack through p ··· π and π ··· π interactions, and a complicated hydrogen-bonding network structure is formed through C–H ··· Cl and C–H ··· O hydrogen bonds. The variable temperature magnetic susceptibility measurements reveal that 1 exhibits strong antiferromagnetic interaction with J = −193.0 cm−1.

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.

Two Novel Ion-Pair Complexes Based on Bis(isomaleonitriledithiolate)nickelate Anion and Substituted Triphenylphosphinium: Syntheses, Weak Interactions, and 3D Structures

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.

Complicated Weak Interactions and 3D Structure of a New Ion-pair Maleonitriledithiolate Nickel(II) Complex

A new ion-pair complex, bis[1-(4 ′ -nitrobenzyl)-3-cyanopyridinium]-bis(maleonitrile-dithiolate)nickelate(II)(1) ([NO 2 BzCNPy] 2 [Ni(mnt) 2 ]), was synthesized and characterized by elemental analyses, IR, MS spectra and single crystal diffraction. The crystal belongs to the triclinic system, space group P-1 with cell constants a = 9.452(1) Å, b = 10.395(2) Å, c = 11.117(2) Å, α = 96.56(1)°, β = 113.94(1)°, γ = 112.68(1)°, Z = 1. The structure was solved by direct methods and refined to R1 = 0.0415 (wR 2 = 0.0771). The structure analysis reveals that the weak C… N, C-H… π, C-H… O, C-H… N interactions and π… π stacking interactios in the crystal play important roles in the self-assembly process and give rise to a 3D network structure.

Syntheses, Crystal Structures, and Magnetic Properties of Two Meta-Substituted Benzyl Triphenylphosphinium Tetra(isothiocyanate)cobaltate(II) Complexes

Two new complexes of tetra(isothiocyanate)cobalt(II) dianion and meta-substituted benzyl triphenylphosphinium, [3BrBzTPP]2[Co(NCS)4] (1) and [3CNBzTPP]2[Co(NCS)4] (2) ([3BrBzTPP]+ = 1-(3′-bromobenzyltriphenylphosphonium and [3CNBzTPP]+ = 1-(3′-cyanobenzyltriphenylphosphonium), were prepared and characterized by elemental analysis, FT–IR, UV-vis spectra, ESI-MS, and single-crystal X-ray diffraction method. Both 1 and 2 crystallize in monoclinic P2(1)/c, and the Co(II) ion of the [Co(NCS)4]2− anion shows a distorted tetrahedral coordination geometry. The C-H···S hydrogen bonds and p···π interaction found in 1 and 2 consolidate the stacking of the crystal. Magnetic susceptibility measurement in the temperature range 2–300 K shows that 1 and 2 exhibit a weak antiferromagnetic coupling behavior.

Two New Ion-Pair Complexes Based on Bis(iso-maleonitriledithiolate)nickelate(II) Anion and Substituted Pyridinium/Quinolinium: Syntheses, Weak Interactions, and 3D Structures

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.

Complicated weak interactions in a hybrid material containing tetra(isothiocyanate)cobalt(II) and 1,1′-ethylene-2,2′-dipyridinium: synthesis, crystal structure, and magnetic properties

A new inorganic–organic hybrid material, [EtdiPy][Co(NCS)4] (1) ([EtdiPy]2+ = 1,1′-ethylene-2,2′-dipyridinium), was synthesized and characterized by elemental analysis, IR spectrum, UV-Vis spectrum, ESI-MS, and single-crystal X-ray diffraction. Compound 1 is monoclinic, space group P21/n, with a = 21.691(5) Å, b = 8.639(2) Å, c = 21.748(5) Å, β = 90.124(3)°, V = 4075.1(16) Å3, D c = 1.550 g cm−3, Z = 8, F(000) = 1928, and R 1 = 0.0435. The C–H···S hydrogen bond, short S···C, S···N interactions, p···π, and π···π interactions observed in the solid state of 1 give a 3-D structure. Magnetic measurements from 2 to 300 K have shown weak antiferromagnetic exchange with θ = −0.892 K in 1.