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

Zeng, Z.-H.; Yang, S.-B.

doi:10.1107/S1600536812003625

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages m239-m240

doi:10.1107/S1600536812003625

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

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

^aCollege of Chemical Engineering, Huanggang Normal University, Huangzhou 438000, People's Republic of China
^*Correspondence e-mail: yangsb168@126.com

(Received 18 January 2012; accepted 27 January 2012; online 4 February 2012)

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, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.042
wR(F²) = 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

Table 1
Selected geometric parameters (Å, °)

Ni1—S1	2.1842 (9)
Ni1—S2	2.1966 (9)

S1ⁱ—Ni1—S2	86.82 (3)
S1—Ni1—S2	93.18 (3)
Symmetry code: (i) -x+1, -y+1, -z.

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
Symmetry codes: (ii) x, y, z+1; (iii) x+1, y, z.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812003625/wm2587sup1.cif

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

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and atoms displayed with displacement ellipsoids at the 30% probability level for all non-H atoms. The non-labelled atoms are generated by the inversion symmetry operation: -x + 1, -y + 1, -z.
	Fig. 2. The crystal packing of (I), viewed approximately down the a axis, showing the network of molecules connected by non-classical hydrogen bonds (dashed lines).

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

Crystal data top

(C₂₅H₂₀ClFP)₂[Ni(C₂N₂S₃)₂]	Z = 1
M_r = 1166.81	F(000) = 598
Triclinic, P1	D_x = 1.457 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4447 (11) Å	Cell parameters from 3884 reflections
b = 12.1385 (15) Å	θ = 2.3–26.0°
c = 13.1309 (16) Å	µ = 0.81 mm⁻¹
α = 71.447 (1)°	T = 291 K
β = 83.601 (2)°	Block, brown
γ = 68.691 (2)°	0.19 × 0.15 × 0.11 mm
V = 1329.6 (3) Å³

Data collection top

Bruker SMART CCD diffractometer	4652 independent reflections
Radiation source: fine-focus sealed tube	3807 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −11→10
T_min = 0.861, T_max = 0.916	k = −14→14
9694 measured reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0368P)² + 1.988P] where P = (F_o² + 2F_c²)/3
4652 reflections	(Δ/σ)_max < 0.001
322 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

(C₂₅H₂₀ClFP)₂[Ni(C₂N₂S₃)₂]	γ = 68.691 (2)°
M_r = 1166.81	V = 1329.6 (3) Å³
Triclinic, P1	Z = 1
a = 9.4447 (11) Å	Mo Kα radiation
b = 12.1385 (15) Å	µ = 0.81 mm⁻¹
c = 13.1309 (16) Å	T = 291 K
α = 71.447 (1)°	0.19 × 0.15 × 0.11 mm
β = 83.601 (2)°

Data collection top

Bruker SMART CCD diffractometer	4652 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	3807 reflections with I > 2σ(I)
T_min = 0.861, T_max = 0.916	R_int = 0.033
9694 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.00	Δρ_max = 0.54 e Å⁻³
4652 reflections	Δρ_min = −0.39 e Å⁻³
322 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ni1	0.5000	0.5000	0.0000	0.03811 (17)
S1	0.58693 (12)	0.34739 (9)	−0.07028 (7)	0.0552 (3)
S2	0.42586 (13)	0.38755 (9)	0.14777 (8)	0.0618 (3)
S3	0.49400 (15)	0.04337 (10)	0.12386 (9)	0.0728 (3)
Cl1	0.70371 (13)	0.46088 (10)	0.42942 (8)	0.0685 (3)
F1	0.5385 (4)	0.1177 (3)	0.4145 (3)	0.1061 (10)
N1	0.5634 (4)	0.1203 (3)	0.0147 (3)	0.0644 (9)
N2	0.4341 (4)	0.1508 (3)	0.1854 (3)	0.0654 (9)
P1	0.95727 (10)	0.22890 (8)	0.69433 (7)	0.0408 (2)
C1	0.5392 (4)	0.2291 (3)	0.0242 (3)	0.0459 (8)
C2	0.4655 (4)	0.2480 (3)	0.1213 (3)	0.0475 (8)
C3	0.6640 (4)	0.3250 (3)	0.4940 (3)	0.0505 (8)
C4	0.6126 (5)	0.2753 (4)	0.4295 (3)	0.0632 (11)
H4	0.5992	0.3136	0.3559	0.076*
C5	0.5826 (5)	0.1690 (4)	0.4779 (4)	0.0684 (11)
C6	0.5948 (5)	0.1121 (4)	0.5864 (4)	0.0680 (11)
H6	0.5686	0.0418	0.6172	0.082*
C7	0.6469 (4)	0.1618 (4)	0.6486 (3)	0.0544 (9)
H7	0.6565	0.1236	0.7224	0.065*
C8	0.6859 (4)	0.2682 (3)	0.6042 (3)	0.0436 (8)
C9	0.7547 (4)	0.3131 (3)	0.6737 (3)	0.0456 (8)
H9A	0.7042	0.3038	0.7429	0.055*
H9B	0.7376	0.4006	0.6404	0.055*
C10	0.8961 (5)	0.0449 (4)	0.8608 (3)	0.0588 (10)
H10	0.8138	0.1087	0.8753	0.071*
C11	0.9250 (6)	−0.0750 (4)	0.9244 (3)	0.0738 (12)
H11	0.8615	−0.0925	0.9819	0.089*
C12	1.0475 (6)	−0.1698 (5)	0.9035 (4)	0.0797 (14)
H12	1.0651	−0.2511	0.9461	0.096*
C13	1.1436 (5)	−0.1448 (4)	0.8202 (4)	0.0717 (12)
H13	1.2272	−0.2089	0.8075	0.086*
C14	1.1167 (4)	−0.0246 (3)	0.7551 (3)	0.0553 (9)
H14	1.1824	−0.0076	0.6990	0.066*
C15	0.9911 (4)	0.0703 (3)	0.7741 (3)	0.0454 (8)
C16	0.9476 (5)	0.3957 (4)	0.8019 (3)	0.0583 (10)
H16	0.8426	0.4258	0.7933	0.070*
C17	1.0149 (6)	0.4456 (5)	0.8554 (4)	0.0757 (13)
H17	0.9553	0.5092	0.8832	0.091*
C18	1.1704 (6)	0.4007 (5)	0.8674 (4)	0.0777 (13)
H18	1.2152	0.4347	0.9032	0.093*
C19	1.2600 (5)	0.3067 (5)	0.8274 (4)	0.0760 (13)
H19	1.3650	0.2777	0.8352	0.091*
C20	1.1938 (5)	0.2558 (4)	0.7757 (3)	0.0673 (11)
H20	1.2540	0.1904	0.7501	0.081*
C21	1.0368 (4)	0.3015 (3)	0.7614 (3)	0.0475 (8)
C22	1.1227 (4)	0.3129 (3)	0.5183 (3)	0.0559 (9)
H22	1.1355	0.3625	0.5553	0.067*
C23	1.1813 (5)	0.3194 (4)	0.4163 (4)	0.0721 (12)
H23	1.2353	0.3724	0.3855	0.087*
C24	1.1614 (5)	0.2499 (5)	0.3607 (4)	0.0773 (14)
H24	1.2011	0.2559	0.2919	0.093*
C25	1.0820 (5)	0.1692 (4)	0.4052 (3)	0.0663 (11)
H25	1.0678	0.1221	0.3662	0.080*
C26	1.0242 (4)	0.1596 (3)	0.5083 (3)	0.0524 (9)
H26	0.9721	0.1052	0.5394	0.063*
C27	1.0450 (4)	0.2327 (3)	0.5651 (3)	0.0439 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0364 (3)	0.0470 (4)	0.0314 (3)	−0.0127 (3)	0.0052 (2)	−0.0163 (2)
S1	0.0713 (6)	0.0579 (6)	0.0441 (5)	−0.0277 (5)	0.0236 (4)	−0.0269 (4)
S2	0.0861 (7)	0.0503 (5)	0.0480 (5)	−0.0237 (5)	0.0288 (5)	−0.0230 (4)
S3	0.0978 (9)	0.0573 (6)	0.0710 (7)	−0.0355 (6)	0.0188 (6)	−0.0257 (5)
Cl1	0.0798 (7)	0.0599 (6)	0.0587 (6)	−0.0315 (5)	−0.0064 (5)	0.0020 (5)
F1	0.123 (3)	0.127 (3)	0.108 (2)	−0.064 (2)	−0.0197 (19)	−0.056 (2)
N1	0.085 (2)	0.055 (2)	0.061 (2)	−0.0268 (18)	0.0149 (17)	−0.0296 (16)
N2	0.082 (2)	0.057 (2)	0.059 (2)	−0.0284 (18)	0.0207 (17)	−0.0200 (16)
P1	0.0422 (5)	0.0435 (5)	0.0385 (4)	−0.0172 (4)	0.0047 (4)	−0.0137 (4)
C1	0.0465 (19)	0.048 (2)	0.0452 (19)	−0.0146 (16)	0.0030 (15)	−0.0204 (16)
C2	0.0447 (19)	0.054 (2)	0.0430 (18)	−0.0168 (16)	0.0083 (15)	−0.0157 (16)
C3	0.046 (2)	0.054 (2)	0.050 (2)	−0.0155 (17)	0.0012 (16)	−0.0157 (17)
C4	0.058 (2)	0.079 (3)	0.052 (2)	−0.019 (2)	−0.0064 (18)	−0.022 (2)
C5	0.063 (3)	0.081 (3)	0.077 (3)	−0.029 (2)	−0.010 (2)	−0.036 (3)
C6	0.066 (3)	0.067 (3)	0.083 (3)	−0.037 (2)	−0.003 (2)	−0.021 (2)
C7	0.050 (2)	0.061 (2)	0.054 (2)	−0.0263 (18)	0.0026 (17)	−0.0123 (18)
C8	0.0367 (17)	0.0486 (19)	0.0444 (18)	−0.0121 (15)	0.0041 (14)	−0.0168 (15)
C9	0.0443 (19)	0.050 (2)	0.0436 (18)	−0.0154 (16)	0.0045 (15)	−0.0182 (16)
C10	0.059 (2)	0.069 (3)	0.044 (2)	−0.024 (2)	0.0023 (17)	−0.0088 (18)
C11	0.083 (3)	0.078 (3)	0.052 (2)	−0.040 (3)	−0.002 (2)	0.006 (2)
C12	0.098 (4)	0.063 (3)	0.068 (3)	−0.037 (3)	−0.025 (3)	0.011 (2)
C13	0.075 (3)	0.056 (3)	0.073 (3)	−0.013 (2)	−0.019 (2)	−0.010 (2)
C14	0.053 (2)	0.054 (2)	0.056 (2)	−0.0165 (18)	−0.0012 (17)	−0.0143 (18)
C15	0.0471 (19)	0.052 (2)	0.0387 (17)	−0.0216 (16)	−0.0003 (15)	−0.0098 (15)
C16	0.059 (2)	0.064 (2)	0.060 (2)	−0.022 (2)	0.0012 (18)	−0.029 (2)
C17	0.083 (3)	0.083 (3)	0.077 (3)	−0.032 (3)	−0.001 (2)	−0.041 (3)
C18	0.094 (4)	0.091 (3)	0.068 (3)	−0.050 (3)	−0.013 (3)	−0.025 (3)
C19	0.066 (3)	0.088 (3)	0.081 (3)	−0.029 (3)	−0.018 (2)	−0.027 (3)
C20	0.054 (2)	0.074 (3)	0.074 (3)	−0.015 (2)	−0.012 (2)	−0.027 (2)
C21	0.052 (2)	0.052 (2)	0.0408 (18)	−0.0230 (17)	−0.0022 (15)	−0.0108 (15)
C22	0.060 (2)	0.051 (2)	0.058 (2)	−0.0253 (19)	0.0099 (18)	−0.0135 (18)
C23	0.072 (3)	0.073 (3)	0.068 (3)	−0.038 (2)	0.025 (2)	−0.011 (2)
C24	0.075 (3)	0.085 (3)	0.055 (2)	−0.020 (3)	0.029 (2)	−0.016 (2)
C25	0.071 (3)	0.072 (3)	0.053 (2)	−0.016 (2)	0.013 (2)	−0.030 (2)
C26	0.054 (2)	0.057 (2)	0.048 (2)	−0.0209 (18)	0.0103 (16)	−0.0185 (17)
C27	0.0429 (18)	0.0435 (19)	0.0437 (18)	−0.0155 (15)	0.0081 (14)	−0.0132 (15)

Geometric parameters (Å, º) top

Ni1—S1ⁱ	2.1842 (9)	C10—H10	0.9300
Ni1—S1	2.1842 (9)	C11—C12	1.379 (7)
Ni1—S2ⁱ	2.1966 (9)	C11—H11	0.9300
Ni1—S2	2.1966 (9)	C12—C13	1.371 (7)
S1—C1	1.736 (4)	C12—H12	0.9300
S2—C2	1.737 (4)	C13—C14	1.381 (6)
S3—N2	1.644 (3)	C13—H13	0.9300
S3—N1	1.655 (3)	C14—C15	1.386 (5)
Cl1—C3	1.752 (4)	C14—H14	0.9300
F1—C5	1.361 (5)	C16—C21	1.373 (5)
N1—C1	1.300 (4)	C16—C17	1.384 (5)
N2—C2	1.324 (5)	C16—H16	0.9300
P1—C27	1.798 (3)	C17—C18	1.376 (7)
P1—C21	1.799 (3)	C17—H17	0.9300
P1—C15	1.802 (4)	C18—C19	1.370 (7)
P1—C9	1.816 (3)	C18—H18	0.9300
C1—C2	1.427 (5)	C19—C20	1.368 (6)
C3—C8	1.393 (5)	C19—H19	0.9300
C3—C4	1.394 (5)	C20—C21	1.394 (5)
C4—C5	1.361 (6)	C20—H20	0.9300
C4—H4	0.9300	C22—C27	1.379 (5)
C5—C6	1.368 (6)	C22—C23	1.380 (6)
C6—C7	1.375 (5)	C22—H22	0.9300
C6—H6	0.9300	C23—C24	1.349 (6)
C7—C8	1.401 (5)	C23—H23	0.9300
C7—H7	0.9300	C24—C25	1.391 (6)
C8—C9	1.503 (5)	C24—H24	0.9300
C9—H9A	0.9700	C25—C26	1.388 (5)
C9—H9B	0.9700	C25—H25	0.9300
C10—C11	1.371 (6)	C26—C27	1.400 (5)
C10—C15	1.395 (5)	C26—H26	0.9300

S1ⁱ—Ni1—S1	180.00 (4)	C10—C11—H11	119.8
S1ⁱ—Ni1—S2ⁱ	93.18 (3)	C12—C11—H11	119.8
S1—Ni1—S2ⁱ	86.82 (3)	C13—C12—C11	120.3 (4)
S1ⁱ—Ni1—S2	86.82 (3)	C13—C12—H12	119.9
S1—Ni1—S2	93.18 (3)	C11—C12—H12	119.9
S2ⁱ—Ni1—S2	180.00 (8)	C12—C13—C14	120.3 (4)
C1—S1—Ni1	103.26 (11)	C12—C13—H13	119.8
C2—S2—Ni1	102.65 (12)	C14—C13—H13	119.8
N2—S3—N1	98.37 (16)	C13—C14—C15	119.4 (4)
C1—N1—S3	106.9 (3)	C13—C14—H14	120.3
C2—N2—S3	106.6 (3)	C15—C14—H14	120.3
C27—P1—C21	109.46 (16)	C14—C15—C10	120.0 (3)
C27—P1—C15	109.54 (16)	C14—C15—P1	120.6 (3)
C21—P1—C15	109.54 (16)	C10—C15—P1	119.2 (3)
C27—P1—C9	108.25 (16)	C21—C16—C17	119.6 (4)
C21—P1—C9	109.81 (16)	C21—C16—H16	120.2
C15—P1—C9	110.22 (16)	C17—C16—H16	120.2
N1—C1—C2	114.5 (3)	C18—C17—C16	119.8 (4)
N1—C1—S1	125.5 (3)	C18—C17—H17	120.1
C2—C1—S1	120.1 (3)	C16—C17—H17	120.1
N2—C2—C1	113.6 (3)	C19—C18—C17	120.9 (4)
N2—C2—S2	125.7 (3)	C19—C18—H18	119.6
C1—C2—S2	120.7 (3)	C17—C18—H18	119.6
C8—C3—C4	121.8 (4)	C20—C19—C18	119.5 (4)
C8—C3—Cl1	121.3 (3)	C20—C19—H19	120.2
C4—C3—Cl1	116.8 (3)	C18—C19—H19	120.2
C5—C4—C3	117.8 (4)	C19—C20—C21	120.3 (4)
C5—C4—H4	121.1	C19—C20—H20	119.8
C3—C4—H4	121.1	C21—C20—H20	119.8
F1—C5—C4	117.8 (4)	C16—C21—C20	119.8 (4)
F1—C5—C6	119.0 (4)	C16—C21—P1	122.2 (3)
C4—C5—C6	123.2 (4)	C20—C21—P1	117.9 (3)
C5—C6—C7	118.1 (4)	C27—C22—C23	119.8 (4)
C5—C6—H6	120.9	C27—C22—H22	120.1
C7—C6—H6	120.9	C23—C22—H22	120.1
C6—C7—C8	122.0 (4)	C24—C23—C22	120.9 (4)
C6—C7—H7	119.0	C24—C23—H23	119.6
C8—C7—H7	119.0	C22—C23—H23	119.6
C3—C8—C7	116.9 (3)	C23—C24—C25	120.7 (4)
C3—C8—C9	122.8 (3)	C23—C24—H24	119.7
C7—C8—C9	120.2 (3)	C25—C24—H24	119.7
C8—C9—P1	112.3 (2)	C26—C25—C24	119.4 (4)
C8—C9—H9A	109.2	C26—C25—H25	120.3
P1—C9—H9A	109.2	C24—C25—H25	120.3
C8—C9—H9B	109.2	C25—C26—C27	119.4 (4)
P1—C9—H9B	109.2	C25—C26—H26	120.3
H9A—C9—H9B	107.9	C27—C26—H26	120.3
C11—C10—C15	119.5 (4)	C22—C27—C26	119.8 (3)
C11—C10—H10	120.3	C22—C27—P1	120.8 (3)
C15—C10—H10	120.3	C26—C27—P1	119.2 (3)
C10—C11—C12	120.4 (4)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (ii) x, y, z+1; (iii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	(C₂₅H₂₀ClFP)₂[Ni(C₂N₂S₃)₂]
M_r	1166.81
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	9.4447 (11), 12.1385 (15), 13.1309 (16)
α, β, γ (°)	71.447 (1), 83.601 (2), 68.691 (2)
V (Å³)	1329.6 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.81
Crystal size (mm)	0.19 × 0.15 × 0.11

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.861, 0.916
No. of measured, independent and observed [I > 2σ(I)] reflections	9694, 4652, 3807
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.118, 1.00
No. of reflections	4652
No. of parameters	322
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.39

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Ni1—S1	2.1842 (9)	Ni1—S2	2.1966 (9)

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

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···S1ⁱⁱ	0.970	2.710	3.635 (4)	160.0
C9—H9B···Cl1	0.970	2.660	3.129 (4)	110.0
C24—H24···N2ⁱⁱⁱ	0.930	2.610	3.401 (7)	143.0

Symmetry codes: (ii) x, y, z+1; (iii) x+1, y, z.

Acknowledgements

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

References

Awaga, K., Okuno, T., Maruyama, Y., Kobayashi, A., Kobayashi, H., Schenk, S. & Underhill, A. E. (1994). Inorg. Chem. 33, 5598–5600. CSD CrossRef CAS Web of Science Google Scholar
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Volume 68| Part 3| March 2012| Pages m239-m240

doi:10.1107/S1600536812003625

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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