Hong-Rong Zuo

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.

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.

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.

Syntheses, crystal structures, magnetic properties and theoretical analysis of two new molecular solids based on Ni(mnt)− 2

Two new molecular solids, [1-(2′-Cl-4′-Rbenzyl)pyridinium][bis(maleonitriledithiolato)nickel] [abbreviated as ([ClRBzPy][Ni(mnt)2]), R = Br(1), I(2)], have been prepared and characterized. The Ni(III) ions form a 1-D zigzag alternating chain within a column through Ni ··· S, S … S, or π … π stacking interactions in 1 and a tetramer in 2. The variable temperature magnetic susceptibilities of 1 and 2 in the temperature range 1.8–300 K have been interpreted in terms of a simple dimer model approximation (H = −2JSASB ), revealing strong antiferromagnetic interactions with the fitting value g = 1.98 and J = −231.5 cm−1 for 1, g = 1.96 and J = −245.3 cm−1 for 2.

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, 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.

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.