1-(2-Fluoro­benz­yl)quinolinium bis­(2-sulfanylidene-1,3-dithiole-4,5-dithiol­ato-κ2S,S′)nickelate(III)

Shan, W.-W.; Zhang, P.; Hu, X.-Y.

doi:10.1107/S1600536811014899

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page m634

doi:10.1107/S1600536811014899

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1-(2-Fluorobenzyl)quinolinium bis(2-sulfanylidene-1,3-dithiole-4,5-dithiolato-κ²S,S′)nickelate(III)

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

^aInstitute of Environmental and Municipal Engineering, North China University of Water Conservancy and Electric Power, Zhengzhou 450011, People's Republic of China
^*Correspondence e-mail: hbsyhxy@163.com

(Received 3 April 2011; accepted 20 April 2011; online 29 April 2011)

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, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.052
wR(F²) = 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

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)

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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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 cation and anion in [Fbzql][Ni(dmit)₂], showing the atom-labelling scheme, with thermal ellipsoids drawn at the 50% probability level. Hydrogen atoms have been omitted for clarity.
	Fig. 2. Three-dimensional supramolecular structure of [Ni(dmit)₂]^- anions through S···S contacts. Dashed lines indicate S···S interactions.
	Fig. 3. Packing of [Fbzql][Ni(dmit)₂] viewed along c-axis

1-(2-Fluorobenzyl)quinolinium bis(2-sulfanylidene-1,3-dithiole-4,5-dithiolato-κ²S,S')nickelate(III) top

Crystal data top

(C₁₆H₁₃FN)[Ni(C₃S₅)₂]	Z = 2
M_r = 689.64	F(000) = 698
Triclinic, P1	D_x = 1.769 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.740 (3) Å	Cell parameters from 717 reflections
b = 12.464 (4) Å	θ = 2.7–25.1°
c = 12.464 (4) Å	µ = 1.58 mm⁻¹
α = 76.103 (4)°	T = 296 K
β = 81.491 (6)°	Needle, green
γ = 81.491 (6)°	0.20 × 0.20 × 0.16 mm
V = 1294.7 (8) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4475 independent reflections
Radiation source: fine-focus sealed tube	2981 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
T_min = 0.743, T_max = 0.786	k = −12→14
6461 measured reflections	l = −11→14

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.P)²] where P = (F_o² + 2F_c²)/3
4475 reflections	(Δ/σ)_max < 0.001
316 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

(C₁₆H₁₃FN)[Ni(C₃S₅)₂]	γ = 81.491 (6)°
M_r = 689.64	V = 1294.7 (8) Å³
Triclinic, P1	Z = 2
a = 8.740 (3) Å	Mo Kα radiation
b = 12.464 (4) Å	µ = 1.58 mm⁻¹
c = 12.464 (4) Å	T = 296 K
α = 76.103 (4)°	0.20 × 0.20 × 0.16 mm
β = 81.491 (6)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4475 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2981 reflections with I > 2σ(I)
T_min = 0.743, T_max = 0.786	R_int = 0.054
6461 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.082	H-atom parameters constrained
S = 0.99	Δρ_max = 0.47 e Å⁻³
4475 reflections	Δρ_min = −0.38 e Å⁻³
316 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	0.41132 (7)	0.16680 (5)	0.73700 (5)	0.03802 (18)
C1	0.2375 (6)	0.0349 (4)	0.3914 (4)	0.0535 (14)
C2	0.2836 (5)	0.0542 (3)	0.5856 (4)	0.0366 (12)
C3	0.3561 (5)	0.1355 (4)	0.5140 (4)	0.0381 (12)
C4	0.4629 (5)	0.1971 (3)	0.9616 (3)	0.0342 (11)
C5	0.5169 (5)	0.2876 (3)	0.8906 (4)	0.0374 (12)
C6	0.5638 (6)	0.3042 (4)	1.0876 (4)	0.0468 (13)
C7	0.1790 (7)	0.5439 (5)	0.3914 (5)	0.0612 (16)
C8	0.2756 (8)	0.5221 (5)	0.4752 (7)	0.084 (2)
H8	0.3592	0.4662	0.4795	0.101*
C9	0.2400 (10)	0.5875 (8)	0.5504 (7)	0.107 (3)
H9	0.3006	0.5753	0.6085	0.129*
C10	0.1210 (13)	0.6688 (7)	0.5439 (6)	0.112 (4)
H10	0.1007	0.7125	0.5964	0.134*
C11	0.0294 (9)	0.6875 (5)	0.4600 (6)	0.084 (2)
H11	−0.0533	0.7440	0.4562	0.101*
C12	0.0566 (6)	0.6248 (4)	0.3814 (4)	0.0469 (13)
C13	−0.0480 (6)	0.6391 (5)	0.2939 (4)	0.0741 (19)
H13A	−0.0599	0.5660	0.2839	0.089*
H13B	−0.1499	0.6721	0.3202	0.089*
C14	0.0848 (6)	0.7917 (4)	0.1797 (4)	0.0537 (14)
H14	0.1111	0.8031	0.2454	0.064*
C15	0.1308 (6)	0.8628 (4)	0.0803 (5)	0.0567 (15)
H15	0.1856	0.9217	0.0791	0.068*
C16	0.0947 (6)	0.8449 (4)	−0.0148 (4)	0.0556 (15)
H16	0.1262	0.8916	−0.0822	0.067*
C17	0.0105 (6)	0.7573 (4)	−0.0143 (4)	0.0487 (13)
C18	−0.0288 (7)	0.7402 (5)	−0.1135 (5)	0.0735 (18)
H18	0.0038	0.7850	−0.1818	0.088*
C19	−0.1159 (8)	0.6565 (6)	−0.1074 (6)	0.087 (2)
H19	−0.1426	0.6438	−0.1724	0.104*
C20	−0.1649 (7)	0.5905 (5)	−0.0067 (7)	0.0769 (19)
H20	−0.2242	0.5341	−0.0056	0.092*
C21	−0.1301 (6)	0.6045 (4)	0.0913 (5)	0.0622 (16)
H21	−0.1652	0.5590	0.1585	0.075*
C22	−0.0391 (6)	0.6897 (4)	0.0882 (5)	0.0489 (14)
F1	0.2101 (5)	0.4827 (3)	0.3141 (3)	0.1095 (14)
N1	0.0047 (5)	0.7081 (3)	0.1846 (3)	0.0464 (11)
S1	0.1815 (2)	−0.00195 (13)	0.28683 (12)	0.0827 (6)
S2	0.19521 (17)	−0.03013 (11)	0.52769 (11)	0.0559 (4)
S3	0.34297 (17)	0.14623 (11)	0.37414 (10)	0.0568 (4)
S4	0.28115 (17)	0.03673 (10)	0.72632 (10)	0.0500 (4)
S5	0.45265 (16)	0.22330 (10)	0.55899 (10)	0.0477 (4)
S6	0.38493 (15)	0.10156 (9)	0.91397 (9)	0.0429 (3)
S7	0.51306 (16)	0.31011 (10)	0.75026 (10)	0.0476 (4)
S8	0.48219 (16)	0.18258 (10)	1.10106 (10)	0.0458 (3)
S9	0.58815 (16)	0.37899 (10)	0.95174 (10)	0.0491 (4)
S10	0.6115 (2)	0.34431 (13)	1.19276 (12)	0.0728 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0479 (4)	0.0404 (3)	0.0299 (3)	−0.0144 (3)	−0.0087 (3)	−0.0077 (3)
C1	0.067 (4)	0.054 (3)	0.047 (3)	−0.004 (3)	−0.017 (3)	−0.023 (3)
C2	0.039 (3)	0.043 (3)	0.034 (3)	−0.007 (2)	−0.010 (2)	−0.014 (2)
C3	0.039 (3)	0.044 (3)	0.033 (3)	−0.008 (2)	−0.005 (2)	−0.011 (2)
C4	0.038 (3)	0.039 (3)	0.026 (3)	−0.005 (2)	−0.008 (2)	−0.005 (2)
C5	0.047 (3)	0.037 (3)	0.033 (3)	−0.010 (2)	−0.008 (2)	−0.011 (2)
C6	0.053 (3)	0.045 (3)	0.050 (3)	−0.005 (3)	−0.011 (3)	−0.021 (3)
C7	0.061 (4)	0.051 (4)	0.063 (4)	−0.015 (3)	0.004 (3)	0.001 (3)
C8	0.059 (5)	0.070 (5)	0.097 (6)	−0.011 (4)	−0.007 (4)	0.032 (4)
C9	0.123 (8)	0.128 (8)	0.072 (6)	−0.092 (7)	−0.027 (6)	0.029 (6)
C10	0.207 (12)	0.083 (6)	0.057 (5)	−0.079 (6)	0.012 (6)	−0.017 (5)
C11	0.114 (6)	0.064 (4)	0.064 (5)	−0.011 (4)	0.010 (4)	−0.007 (4)
C12	0.044 (3)	0.045 (3)	0.043 (3)	−0.013 (3)	0.000 (3)	0.008 (3)
C13	0.054 (4)	0.092 (4)	0.066 (4)	−0.035 (4)	−0.009 (3)	0.017 (3)
C14	0.059 (4)	0.052 (3)	0.051 (4)	−0.014 (3)	−0.003 (3)	−0.011 (3)
C15	0.064 (4)	0.045 (3)	0.060 (4)	−0.018 (3)	0.009 (3)	−0.013 (3)
C16	0.067 (4)	0.042 (3)	0.049 (4)	0.002 (3)	0.002 (3)	−0.002 (3)
C17	0.050 (3)	0.043 (3)	0.051 (4)	−0.001 (3)	−0.005 (3)	−0.008 (3)
C18	0.074 (5)	0.088 (5)	0.060 (4)	0.010 (4)	−0.019 (4)	−0.024 (4)
C19	0.079 (5)	0.106 (6)	0.092 (6)	0.024 (4)	−0.043 (5)	−0.056 (5)
C20	0.059 (4)	0.074 (4)	0.118 (6)	−0.005 (4)	−0.027 (4)	−0.052 (5)
C21	0.043 (4)	0.056 (4)	0.094 (5)	−0.008 (3)	−0.012 (3)	−0.024 (3)
C22	0.038 (3)	0.041 (3)	0.069 (4)	0.000 (3)	−0.011 (3)	−0.014 (3)
F1	0.135 (4)	0.070 (2)	0.118 (3)	−0.015 (2)	0.028 (3)	−0.034 (2)
N1	0.042 (3)	0.045 (2)	0.050 (3)	−0.015 (2)	−0.004 (2)	−0.001 (2)
S1	0.1301 (16)	0.0845 (11)	0.0519 (10)	−0.0306 (11)	−0.0308 (10)	−0.0277 (9)
S2	0.0773 (11)	0.0535 (8)	0.0478 (8)	−0.0257 (8)	−0.0199 (8)	−0.0137 (7)
S3	0.0775 (11)	0.0685 (9)	0.0306 (7)	−0.0251 (8)	−0.0035 (7)	−0.0149 (7)
S4	0.0716 (10)	0.0506 (8)	0.0327 (7)	−0.0289 (7)	−0.0140 (7)	−0.0010 (6)
S5	0.0626 (9)	0.0536 (8)	0.0320 (7)	−0.0263 (7)	−0.0031 (7)	−0.0088 (6)
S6	0.0614 (9)	0.0398 (7)	0.0322 (7)	−0.0198 (7)	−0.0112 (6)	−0.0050 (6)
S7	0.0675 (10)	0.0465 (7)	0.0334 (7)	−0.0260 (7)	−0.0087 (7)	−0.0047 (6)
S8	0.0609 (9)	0.0488 (8)	0.0315 (7)	−0.0120 (7)	−0.0095 (6)	−0.0106 (6)
S9	0.0645 (10)	0.0471 (8)	0.0446 (8)	−0.0213 (7)	−0.0110 (7)	−0.0161 (6)
S10	0.0957 (13)	0.0880 (11)	0.0528 (10)	−0.0297 (10)	−0.0184 (9)	−0.0335 (9)

Geometric parameters (Å, º) top

Ni1—S4	2.1529 (14)	C10—C11	1.366 (10)
Ni1—S5	2.1534 (15)	C10—H10	0.9300
Ni1—S6	2.1502 (14)	C11—C12	1.368 (7)
Ni1—S7	2.1595 (14)	C11—H11	0.9300
C1—S1	1.641 (5)	C12—C13	1.487 (7)
C1—S2	1.709 (5)	C13—N1	1.475 (6)
C1—S3	1.731 (5)	C13—H13A	0.9700
C2—C3	1.347 (6)	C13—H13B	0.9700
C2—S4	1.713 (4)	C14—N1	1.324 (5)
C2—S2	1.729 (4)	C14—C15	1.383 (6)
C3—S5	1.712 (4)	C14—H14	0.9300
C3—S3	1.735 (4)	C15—C16	1.346 (7)
C4—C5	1.354 (5)	C15—H15	0.9300
C4—S6	1.713 (4)	C16—C17	1.403 (6)
C4—S8	1.734 (4)	C16—H16	0.9300
C5—S7	1.708 (4)	C17—C22	1.399 (6)
C5—S9	1.742 (4)	C17—C18	1.403 (7)
C6—S10	1.637 (5)	C18—C19	1.362 (8)
C6—S9	1.725 (5)	C18—H18	0.9300
C6—S8	1.732 (4)	C19—C20	1.372 (8)
C7—F1	1.341 (6)	C19—H19	0.9300
C7—C12	1.355 (7)	C20—C21	1.357 (8)
C7—C8	1.390 (8)	C20—H20	0.9300
C8—C9	1.359 (9)	C21—C22	1.408 (6)
C8—H8	0.9300	C21—H21	0.9300
C9—C10	1.337 (10)	C22—N1	1.393 (6)
C9—H9	0.9300

S6—Ni1—S4	86.54 (5)	N1—C13—H13A	108.4
S6—Ni1—S5	175.79 (6)	C12—C13—H13A	108.4
S4—Ni1—S5	93.15 (5)	N1—C13—H13B	108.4
S6—Ni1—S7	93.24 (5)	C12—C13—H13B	108.4
S4—Ni1—S7	172.57 (6)	H13A—C13—H13B	107.5
S5—Ni1—S7	87.61 (5)	N1—C14—C15	122.3 (5)
S1—C1—S2	123.9 (3)	N1—C14—H14	118.8
S1—C1—S3	122.9 (3)	C15—C14—H14	118.8
S2—C1—S3	113.2 (3)	C16—C15—C14	118.6 (5)
C3—C2—S4	120.8 (4)	C16—C15—H15	120.7
C3—C2—S2	116.6 (3)	C14—C15—H15	120.7
S4—C2—S2	122.6 (3)	C15—C16—C17	121.4 (5)
C2—C3—S5	121.8 (4)	C15—C16—H16	119.3
C2—C3—S3	115.6 (4)	C17—C16—H16	119.3
S5—C3—S3	122.5 (3)	C22—C17—C16	118.4 (5)
C5—C4—S6	121.0 (3)	C22—C17—C18	120.5 (5)
C5—C4—S8	116.3 (3)	C16—C17—C18	121.1 (5)
S6—C4—S8	122.7 (2)	C19—C18—C17	118.4 (6)
C4—C5—S7	121.6 (3)	C19—C18—H18	120.8
C4—C5—S9	115.7 (3)	C17—C18—H18	120.8
S7—C5—S9	122.7 (2)	C18—C19—C20	121.0 (6)
S10—C6—S9	123.7 (3)	C18—C19—H19	119.5
S10—C6—S8	123.5 (3)	C20—C19—H19	119.5
S9—C6—S8	112.8 (3)	C21—C20—C19	122.5 (6)
F1—C7—C12	117.6 (6)	C21—C20—H20	118.7
F1—C7—C8	118.2 (6)	C19—C20—H20	118.7
C12—C7—C8	124.2 (6)	C20—C21—C22	118.1 (6)
C9—C8—C7	115.7 (7)	C20—C21—H21	121.0
C9—C8—H8	122.1	C22—C21—H21	121.0
C7—C8—H8	122.1	C17—C22—N1	118.7 (5)
C10—C9—C8	122.4 (9)	C17—C22—C21	119.5 (5)
C10—C9—H9	118.8	N1—C22—C21	121.8 (5)
C8—C9—H9	118.8	C14—N1—C22	120.5 (4)
C9—C10—C11	119.9 (9)	C14—N1—C13	119.6 (4)
C9—C10—H10	120.1	C22—N1—C13	119.8 (4)
C11—C10—H10	120.1	C1—S2—C2	97.4 (2)
C12—C11—C10	121.4 (7)	C1—S3—C3	97.1 (2)
C12—C11—H11	119.3	C2—S4—Ni1	102.32 (15)
C10—C11—H11	119.3	C3—S5—Ni1	101.87 (15)
C7—C12—C11	116.4 (6)	C4—S6—Ni1	102.21 (14)
C7—C12—C13	121.4 (6)	C5—S7—Ni1	101.89 (14)
C11—C12—C13	122.1 (6)	C6—S8—C4	97.5 (2)
N1—C13—C12	115.4 (4)	C6—S9—C5	97.6 (2)

S4—C2—C3—S5	1.4 (6)	C17—C22—N1—C14	3.5 (7)
S2—C2—C3—S5	−178.4 (2)	C21—C22—N1—C14	−177.2 (4)
S4—C2—C3—S3	−177.8 (3)	C17—C22—N1—C13	179.1 (4)
S2—C2—C3—S3	2.4 (5)	C21—C22—N1—C13	−1.6 (7)
S6—C4—C5—S7	−1.0 (6)	C12—C13—N1—C14	−32.3 (7)
S8—C4—C5—S7	177.3 (3)	C12—C13—N1—C22	152.0 (5)
S6—C4—C5—S9	178.4 (2)	S1—C1—S2—C2	−178.3 (4)
S8—C4—C5—S9	−3.2 (5)	S3—C1—S2—C2	0.5 (3)
F1—C7—C8—C9	179.2 (5)	C3—C2—S2—C1	−1.7 (4)
C12—C7—C8—C9	0.4 (9)	S4—C2—S2—C1	178.4 (3)
C7—C8—C9—C10	−0.8 (10)	S1—C1—S3—C3	179.3 (4)
C8—C9—C10—C11	0.7 (12)	S2—C1—S3—C3	0.5 (3)
C9—C10—C11—C12	−0.2 (11)	C2—C3—S3—C1	−1.7 (4)
F1—C7—C12—C11	−178.7 (5)	S5—C3—S3—C1	179.1 (3)
C8—C7—C12—C11	0.0 (8)	C3—C2—S4—Ni1	−0.2 (4)
F1—C7—C12—C13	5.2 (7)	S2—C2—S4—Ni1	179.6 (2)
C8—C7—C12—C13	−176.1 (5)	S6—Ni1—S4—C2	−176.51 (17)
C10—C11—C12—C7	−0.1 (8)	S5—Ni1—S4—C2	−0.72 (17)
C10—C11—C12—C13	175.9 (5)	C2—C3—S5—Ni1	−1.8 (4)
C7—C12—C13—N1	−85.7 (6)	S3—C3—S5—Ni1	177.4 (3)
C11—C12—C13—N1	98.5 (6)	S4—Ni1—S5—C3	1.26 (17)
N1—C14—C15—C16	−1.1 (8)	S7—Ni1—S5—C3	−171.34 (17)
C14—C15—C16—C17	0.8 (8)	C5—C4—S6—Ni1	1.8 (4)
C15—C16—C17—C22	1.5 (8)	S8—C4—S6—Ni1	−176.5 (2)
C15—C16—C17—C18	179.0 (5)	S4—Ni1—S6—C4	−174.04 (16)
C22—C17—C18—C19	0.0 (8)	S7—Ni1—S6—C4	−1.47 (16)
C16—C17—C18—C19	−177.5 (5)	C4—C5—S7—Ni1	−0.3 (4)
C17—C18—C19—C20	0.3 (9)	S9—C5—S7—Ni1	−179.7 (3)
C18—C19—C20—C21	0.0 (10)	S6—Ni1—S7—C5	1.07 (17)
C19—C20—C21—C22	−0.5 (9)	S5—Ni1—S7—C5	−174.79 (17)
C16—C17—C22—N1	−3.6 (7)	S10—C6—S8—C4	179.3 (3)
C18—C17—C22—N1	178.9 (5)	S9—C6—S8—C4	−0.3 (3)
C16—C17—C22—C21	177.0 (5)	C5—C4—S8—C6	2.1 (4)
C18—C17—C22—C21	−0.5 (8)	S6—C4—S8—C6	−179.6 (3)
C20—C21—C22—C17	0.7 (8)	S10—C6—S9—C5	179.4 (3)
C20—C21—C22—N1	−178.6 (5)	S8—C6—S9—C5	−1.1 (3)
C15—C14—N1—C22	−1.1 (7)	C4—C5—S9—C6	2.6 (4)
C15—C14—N1—C13	−176.7 (5)	S7—C5—S9—C6	−177.9 (3)

Experimental details

Crystal data
Chemical formula	(C₁₆H₁₃FN)[Ni(C₃S₅)₂]
M_r	689.64
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.740 (3), 12.464 (4), 12.464 (4)
α, β, γ (°)	76.103 (4), 81.491 (6), 81.491 (6)
V (Å³)	1294.7 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.58
Crystal size (mm)	0.20 × 0.20 × 0.16

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.743, 0.786
No. of measured, independent and observed [I > 2σ(I)] reflections	6461, 4475, 2981
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.082, 0.99
No. of reflections	4475
No. of parameters	316
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.38

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

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

Acknowledgements

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).

References

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