1-(2-Fluoro­benz­yl)quinolinium bis­(2-sulfanylidene-1,3-dithiole-4,5-dithiol­ato-κ2 S,S′)nickelate(III)

Wen-Wen Shan; Peng Zhang; Xi-Ying Hu

doi:10.1107/S1600536811014899

. 2011 Apr 29;67(Pt 5):m634. doi: 10.1107/S1600536811014899

1-(2-Fluorobenzyl)quinolinium bis(2-sulfanylidene-1,3-dithiole-4,5-dithiolato-κ² S,S′)nickelate(III)

Wen-Wen Shan ^a, Peng Zhang ^a, Xi-Ying Hu ^a,^*

PMCID: PMC3089345 PMID: 21754342

Abstract

The crystal structure of the title compound, (C₁₆H₁₃FN)[Ni(C₃S₅)₂], consists of Ni^III complex anions and 1-(2-fluorobenzyl)quinolinium (fbq) cations. In the complex anion, the Ni^III cation is chelated by two 2-sulfanylidene-1,3-dithiole-4,5-dithiolate (dmit) dianions in a distorted square-planar geometry; the two dmit mean planes are twisted with respect to each other at a dihedral angle of 8.44 (3)°. In the fbq cation, the dihedral angle between the benzene ring and the quinoline ring system is 80.57 (14)°. The centroid–centroid distance of 3.860 (5) Å between benzene rings indicates π–π stacking between adjacent fbq cations. The distance of 3.4958 (18) Å between the S atom and the centroid of the pyridine ring suggests the existence of a lone-pair–aromatic interaction between the anion and the cation. A short S⋯S contact [3.387 (2) Å] is also observed in the crystal structure.

Related literature

For the potential applications of bis(dithiolate)–metal complexes, see: Cassoux (1999 ▶). For the lone-pair–aromatic interaction, see: Egli & Sarkhel (2007 ▶). For the oxidation of Ni^II compounds, see: Cassoux et al. (1991 ▶). For the synthesis, see: Wang et al. (1998 ▶).

Experimental

Crystal data

(C₁₆H₁₃FN)[Ni(C₃S₅)₂]
M _r = 689.64
Triclinic,
a = 8.740 (3) Å
b = 12.464 (4) Å
c = 12.464 (4) Å
α = 76.103 (4)°
β = 81.491 (6)°
γ = 81.491 (6)°
V = 1294.7 (8) Å³
Z = 2
Mo Kα radiation
μ = 1.58 mm⁻¹
T = 296 K
0.20 × 0.20 × 0.16 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.743, T _max = 0.786
6461 measured reflections
4475 independent reflections
2981 reflections with I > 2σ(I)
R _int = 0.054

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.082
S = 0.99
4475 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811014899/xu5187sup1.cif

e-67-0m634-sup1.cif^{(22.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811014899/xu5187Isup2.hkl

e-67-0m634-Isup2.hkl^{(219.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Ni1—S4	2.1529 (14)
Ni1—S5	2.1534 (15)
Ni1—S6	2.1502 (14)
Ni1—S7	2.1595 (14)

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Acknowledgments

This work was supported financially by the Natural Science Foundation of Henan Province (grant No. 2010 A140009) and the International Technology Cooperation Project of the Science and Technology Department of Henan Province of China (grant No. 104300510044).

supplementary crystallographic information

Comment

The bis(dithiolate)-metal complexes and their analogues with interesting structures and/or potential applications such as conducting/magnetic or non-linear optical (NLO) materials have been reported in recent years (Cassoux, 1999). We report herein the crystal structure of the title bis-dithiolate-metal complex.

In this compound, the Ni^II cations of NiCl₂.6H₂O have been oxidized to Ni^III cation by I₂ (Cassoux et al., 1991), the Ni^III cation is coordinated with two dmit^II anions. As shown in Fig. 1, the asymmetric unit of the title compound contains one [Ni^III(dmit)₂]^- anion and one [Fbzql]⁺ cation. Each Ni^III ion is coordinated by four S atoms from two dmit ligands to complete a square-planar geometry, with Ni—S bond lengths ranging from 2.1502 (14) to 2.1595 (14) Å. Some of the [Ni^III(dmit)₂]^- anions are parallel and coplanar arrangements with the shortest S···S distance of 3.387 (2) Å (S3—S8ⁱ) [symmetry code: (i) x, y, -1 + z], indicating the existence of the S···S interactions. Adjacent [Ni^III(dmit)₂]^- anions are associated together through such S···S interactions result in a one-dimensional ribbon structure running along the c-axis. Two neighbouring anion ribbons are parallel each other and linked together through S6···S8ⁱⁱ [symmetry code: (ii) 1 - x, -y, 2 - z] interactions forming a double-chain which is further connected to other four anion double-chains through S···S contacts [S2···S2ⁱⁱⁱ: 3.519 (3) Å, S9···S9^iv: 3.568 (2) Å [symmetry codes: (iii) -x, -y, 1 - z; (iv) 1 - x, 1 - y, 2 - z] along four orientations to form a three-dimensional supramolecular structure with large channels, as depicted in Fig 2.

Two [Fbzql]⁺ cations are associated together through face-to-face π···π interactions between two phenyl rings from different 2-fluorobenzyl groups (inter-centeriod distance: 3.8501 (9) Å) to form a bi-molecular unit, which expended to a one-dimensional structure running along the c-axis through another π···π interaction involving adjacent quinoline groups from different bi-molecular units with the shortest interface distance of 3.407 (4) Å.

The voids of the three-dimensional anion supramolecular structure are filled with the cation chains, as shown in Fig 3. Electrostatic attraction between the anions and cations play an important role in the stabilization of the whole structure. Additional investigation of this structure indicates that different noncovalent interactions can be detected between the two kinds of ions. The quinoline group of the [Fbzql]⁺ cation and neighbouring anion planes are parallel and associated together through lp···π (Egli & Sarkhel, 2007) interactions between one terminal sulfur atom of [Ni^III(dmit)₂]^- anion and the pyridine ring of the quinoline group [S9^v-centroid distance 3.4958 (18) Å, symmetry codes: (v) 1 - x, 1 - y, 1 - z]. In addition, the distance between the benzene ring of the quinoline group from [Fbzql]⁺ cation and the terminal π system of adjacent [Ni^III(dmit)₂]^- anion is about 3.8294 (13) Å, indicating the existence of face-to-face π···π interaction which stabilizes the three-dimensional structure.

Experimental

4,5-Bis(thiobenzoyl)-1,3-dithiole-2-thione (812 mg, 2.0 mmol; Wang et al., 1998) was suspended in dry methanol (20 ml) and sodium (92 mg, 4.0 mmol) was added under a nitrogen atmosphere at room temperature to give a bright-red solution. NiCl₂.6H₂O (238 mg, 1 mmol) was then added, followed successively by I₂ (127 mg, 0.5 mmol) and a solution of N-(2-fluorobenzyl)quinolinium chloride (274 mg, 1 mmol) in methanol at an interval of approximately 20 min. The solution was stirred for a further 30 min and the resulting solid collected by filtration. Single crystals of the title compound were obtained by evaporation of a dilute acetone solution over two weeks at room temperature.