Jin-Fang Liu

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 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.

Synthesis, Characterization, Weak Interactions, and 3D Crystal Structures of Two New Salts Based on Bis(1,2,5-thiadiazole-3,4-dithiolate)nickelate Anion with 4-Substituted Benzyl 4-Ethylpyridinium Derivatives

Two new salts based on [Ni(tdas)2]2− (tdas2− = 1, 2, 5-thiadiazole-3,4-dithiolate), [4FBz-4EtPy]2[Ni(tdas)2](1) and [4BrBz-4EtPy]2[Ni(tdas)2] (2), have been prepared by reaction of Na2tdas, NiCl2.6H2O, and [4RBz-4EtPy]Br([4RBz-4EtPy]+ = 4-R-benzyl-4′-ethylpyridinium, R = F(1), Br(2)), and characterized by elemental analysis, IR, UV-Vis, EI-MS spectra, and single-crystal X-ray diffraction. Two salts crystallize in different systems with the different stacking modes of the anions and the cations. The [4FBz-4EtPy]+ cations in 1 form a 1D chain through C−H···F hydrogen bonds, while the [Ni(tdas)2]2− anions form a 1D chain in 2 through intermolecular short S···S interactions. Some other intra-molecular contacts such as C−H···S, C−H···N, C–H···Ni, π···π, S···N, and S···Br weak interactions in 1 and 2 play an important role in the stacking of the molecules and give further rise to a network 3D structure.

Synthesis, Structure, and Magnetic Properties of a New Bis(maleonitriledithiolate)nickelate(III) Anion Salt Containing 1-(2′-Chlorobenzyl)-2-aminopyridinium

A new salt, [2ClBz2NH2Py][Ni(mnt)2](1), ([2ClBz2NH2Py]+ = 1-(2´-chlorobenzyl)-2-aminopyridinium, mnt2− = maleonitril-edithiolate), was prepared and characterized structurally by means of CHN elemental analyses, IR, MS spectra and single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic space group C2/c with lattice contents a = 24.947(2) Å, b = 12.658(1) Å, c = 15.045(2) Å, β = 97.41(1)°, V = 4711.0(8) Å3, and Z = 8. The Ni(III) ions of 1 form a 1D spiral zigzag non-uniform magnetic chain within a [Ni(mnt)2]− column with the Ni···Ni distances of 3.971 and 4.386 Å, whereas two neighboring [2ClBz2NH2Py]+ cations from a dimer by the short Cl···Cl interaction with a distance of 3.585 Å. The cations and anions are linked by N···π, S···π interactions and C-H···N, C-H···S hydrogen bonds. Magnetic susceptibility measurements in the temperature range 2–300 K show that the salt shows characteristic of spin-gap with Δ/kb = 789.1 K.

Syntheses, Crystal Structures, Weak Interactions, and Magnetic Properties of Two Bis(maleonitriledithiolate)copper(II) Salts with Substituted Benzyl 1-Methylimidazolium

In two new bis(maleonitriledithiolate)copper(II) salts, [Bz-1-MeIm]2[Cu(mnt)2] (1) and [4-NO2Bz-1-MeIm]2[Cu(mnt)2] (2) ([Bz-1-MeIm]+ = Bz-1-MeMz = 1-methyl-3-benzylimidazolium; [4-NO2Bz-1-MeIm]+ = 1-methyl-3-(4′-nitrobenzyl)imidazolium), 1 crystallizes in the triclinic system with space group P-1, whereas 2 crystallizes in the monoclinic system with space group P21/c. The cations and anions stack alternately into a column by π···π and C‒H···π interactions, and the C‒H···N and C‒H···O hydrogen bonds consolidate the crystal packing and give further rise to a 3D network structure. Magnetic susceptibility measurements show that 1 displays strong antiferromagnetic interaction with θ = –255.98 K, whereas 2 shows weak ferromagnetic coupling with θ = 0.527 K.

Crystal structure of bis(iso-maleonitril-edithiolate)nickel(II) benzylpiperidinium

Bis(iso-maleonitriledithiolate)nickel(II) benzylpiperidinium, [BzPid]2[Ni(i-mnt)2] (1) is prepared and characterized by elemental analyses, UV, IR, molar conductivity, and single crystal X-ray diffraction. It is found that 1 crystallizes in the monoclinic space group P21/n with a = 9.551(1) Å, b = 16.520(2) Å, c = 11.004(1) Å, β = 96.60(1)°, V = 1724.6(3) Å3, Z = 2. Consolidate the stacking of the molecules The electrostatic interaction between [Ni(i-mnt)2]2− anions and [BzPid]+ cations consolidates the stacking of the molecules.

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.