Bis[(2-chloro-4-fluoro­benz­yl)triphenyl­phospho­nium] bis­(1,2,5-thia­diazole-3,4-dithiol­ato)nickelate(II)

Zhou-Hua Zeng; Shui-Bin Yang

doi:10.1107/S1600536812003625

. 2012 Feb 4;68(Pt 3):m239–m240. doi: 10.1107/S1600536812003625

Bis[(2-chloro-4-fluorobenzyl)triphenylphosphonium] bis(1,2,5-thiadiazole-3,4-dithiolato)nickelate(II)

Zhou-Hua Zeng ^a, Shui-Bin Yang ^a,^*

PMCID: PMC3297212 PMID: 22412402

Abstract

The title ion-pair complex, (C₂₅H₂₀ClFP)₂[Ni(C₂N₂S₃)₂], was obtained by the direct reaction of (4-F,2-ClBzTPP)⁺·Br⁻ [4-F,2-ClBzTPP⁺ is (2-chloro-4-fluorobenzyl)triphenylphosphonium], NiCl₂·6H₂O and Na₂tdas (tdas²⁻ is 1,2,5-thiadiazole-3,4-dithiolate) in methanol. The asymmetric unit of the title structure comprises one (4-F,2-ClBzTPP)⁺ cation and half of an [Ni(tdas)₂]²⁻ complex anion, with the Ni^II ion situated on a center of symmetry, leading to a slightly distorted square-planar coordination of the latter. In the cation, the tetrahedral angles around the P atom are nearly undistorted. In the crystal, the cations and anions are linked by C—H⋯S, C—H⋯N and C—H⋯Cl hydrogen bonds.

Related literature

For background to complexes containing the [Ni(maleonitriledithiolate)₂]²⁻ anion, see: Chen et al. (2010 ▶); Hou et al. (2008 ▶); Ni et al. (2005 ▶); Ren et al. (2002 ▶); Robertson & Cronin (2002 ▶); Xie et al. (2002 ▶); Zhou et al. (2011 ▶). For details of other square-planar Ni(1,2,5-thiadiazole-3,4-dithiolate)₂ complexes, see: Awaga et al. (1994 ▶); Yamochi et al. (2001 ▶); Okuno et al. (2003 ▶); Ni et al. (2004 ▶); Zuo et al. (2009 ▶).

Experimental

Crystal data

(C₂₅H₂₀ClFP)₂[Ni(C₂N₂S₃)₂]
M _r = 1166.81
Triclinic,
a = 9.4447 (11) Å
b = 12.1385 (15) Å
c = 13.1309 (16) Å
α = 71.447 (1)°
β = 83.601 (2)°
γ = 68.691 (2)°
V = 1329.6 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 291 K
0.19 × 0.15 × 0.11 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.861, T _max = 0.916
9694 measured reflections
4652 independent reflections
3807 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.118
S = 1.00
4652 reflections
322 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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 datablock(s) I, global. DOI: 10.1107/S1600536812003625/wm2587sup1.cif

e-68-0m239-sup1.cif^{(20.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812003625/wm2587Isup2.hkl

e-68-0m239-Isup2.hkl^{(227.9KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Ni1—S1	2.1842 (9)
Ni1—S2	2.1966 (9)

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S1ⁱ—Ni1—S2	86.82 (3)
S1—Ni1—S2	93.18 (3)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯S1ⁱⁱ	0.97	2.71	3.635 (4)	160
C9—H9B⋯Cl1	0.97	2.66	3.129 (4)	110
C24—H24⋯N2ⁱⁱⁱ	0.93	2.61	3.401 (7)	143

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Symmetry codes: (ii) Inline graphic ; (iii) .

Acknowledgments

The authors thank the Department of Education of Hubei Province (grant No. D20082705) for financial support.

supplementary crystallographic information

Comment

Transition metal complexes of bis(1,2-ditholene) and derivatives thereof have been extensively studied due to their potential applications in molecular materials showing superconducting, magnetic or optical properties (Robertson & Cronin, 2002; Ni et al., 2005; Ren et al., 2002). In recent years, much attention has been paid to the study of ion-pair complexes containing the [Ni(mnt)₂]^n- (mnt is maleonitriledithiolate, n is 1 or 2) anion that possesses spin bistability with potential application as a molecular switch, in data storage or in displays (Chen et al., 2010; Hou et al., 2008; Xie et al., 2002; Zhou et al., 2011), while there is only few information available on complexes containing the [M(tdas)₂]^n- (tdas is 1,2,5-thiadiazole-3,4-dithiolate, n is 1 or 2; M is a transition metal) anion (Awaga et al., 1994; Yamochi et al., 2001; Okuno et al., 2003). Substantial efforts have been devoted for finding more suitable counter cations to tune the stacking in the crystal structures containing [M(tdas)₂]^n- anions and also to obtain materials with interesting properties (Ni et al., 2004; Zuo et al., 2009). Substituted benzyl triphenylphosphonium as a cation has been proved to be suitable for this purpose. In this article we report on the preparation and crystal structure of the new ion-pair complex, [4-F,2-ClBzTPP]₂[Ni(tdas)₂] (I).

The molecular structure of (I) is shown in Fig. 1. There are one (2-chloro-4-fluorobenzyl)triphenylphosphonium and half of an [Ni(tdas)₂]^2- anion in the asymmetric unit of (I). The nickel(II) ion of the complex [Ni(tdas)₂]^2- anion is situated on a center of symmetry within a slightly distorted square-planar coordination. The Ni1—S1 and Ni1—S2 bond lengths are 2.1842 (9) Å and 2.1966 (9) Å, and the S1—Ni1—S2 bond angle within the five-membered metalla ring is 93.18 (3)°, similar to those observed for other structures with an [Ni(tdas)₂]^2- anion (Okuno et al., 2003; Zuo et al., 2009). In the cation, the deviations of the F and Cl atoms from the C3—C8 benzene ring are 0.082 (2)Å and -0.029 (2) Å, respectively.

C—H···S, C—H···N and C—H···Cl hydrogen bonds between the anion and cation consolidate the crystal packing (Fig. 2, Table 2).

Experimental

The title ion-pair complex was prepared by the direct reaction of 1:2:2 mol equiv. of NiCl₂^.6H₂O, Na₂tdas and (2-chloro-4-fluorobenzyl)triphenylphosphonium bromide in methanol. A brown product was obtained and purified through recrystallization from a mixed solution of methanol and water (yield: 86%). Brown block-sheped single crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent at room temperature within 3 weeks.