1-(2-Fluoro­benzyl­ideneamino)pyridinium bis­(1,2-dicyano­ethene-1,2-dithiol­ato)nickelate(II)

Zhang, H.; Zhou, Q.; Hu, F.; Xu, H.; Chang, G.

doi:10.1107/S1600536809015360

metal-organic compounds

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Volume 65| Part 5| May 2009| Page m599

doi:10.1107/S1600536809015360

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1-(2-Fluorobenzylideneamino)pyridinium bis(1,2-dicyanoethene-1,2-dithiolato)nickelate(II)

Hui Zhang,^a ^* Quan Zhou,^a Fengkai Hu,^a Han Xu ^a and Guanru Chang ^a

^aDepartment of Chemistry, Huangshan University, Huangshang 245001, People's Republic of China
^*Correspondence e-mail: xuanfang.1984@163.com

(Received 14 April 2009; accepted 24 April 2009; online 30 April 2009)

In the title complex, (C₁₂H₁₀FN₂)₂[Ni(C₄N₂S₂)₂], the anion lies on an inversion center with the Ni^II ion coordinated by four S atoms in a slightly distorted square-planar environment. In the unique cation, the dihedral angle between the benzene and pyridine rings is 7.1 (2) Å.

Related literature

For metal–[dithiolene]₂ complexes, see: Ni et al. (2004 , 2005 ); Nishijo et al. (2000 ); Ren et al. (2004 ); Robertson & Cronin (2002 ).

Experimental

Crystal data

(C₁₂H₁₀FN₂)₂[Ni(C₄N₂S₂)₂]
M_r = 741.51
Triclinic, $[P \overline 1]$
a = 7.9248 (13) Å
b = 9.1774 (15) Å
c = 11.1526 (18) Å
α = 88.326 (3)°
β = 77.202 (4)°
γ = 85.448 (4)°
V = 788.4 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.93 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.732, T_max = 0.809
4282 measured reflections
3030 independent reflections
1785 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.094
S = 0.76
3030 reflections
214 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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 global, I. DOI: 10.1107/S1600536809015360/lh2806sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809015360/lh2806Isup2.hkl

checkCIF report

Comment top

Molecular solids based on transition metal dithiolene complexes have attracted intense interest in recent years, not only owing to the fundamental research of magnetic interactions and magneto-structural correlations but also to the development of new functional molecule-based materials (Robertson & Cronin (2002). Much work has been performed on molecular solids based on M[dithiolene]₂ complexes owing to their application as building blocks in molecular-based materials showing magnetic, superconducting, and optical properties (Nishijo et al., 2000; Ni et al., 2005). Herein we report the crystal structure of the title compound (I).

The molecular structure of (I) is illustrated in Fig. 1. The asymmetric unit contains one half [Ni(mnt)₂]^2- (mnt = maleonitriledithiolato) dianion and one o-fluorbenzylidene-1-aminopyrazine cation, the formula unit being generated by an inversion center. In the [Ni(mnt)₂]^2- cation the bond lengths and angles are in good agreement with related [Ni(mnt)₂]^2- compounds (Ni et al., 2004; Ren et al., 2004)

Related literature top

For metal–[dithiolene]₂ complexes, see: Ni et al. (2004, 2005); Nishijo et al. (2000); Ren et al. (2004); Robertson & Cronin (2002).

Experimental top

Disodium maleonitriledithiolate (456 mg, 2.5 mmol) and nickel chloride hexahydrate (297 mg, 1.25 mmol) were mixed under stirring in water (20 mL) at room temperature. A solution of o-fluorbenzylidene-1-aminopyridinium bromide(665 mg, 2.5 mmol) in methanol (10 mL) was added to the mixture, and the red precipitate that was immediately formed was filtered off, and washed with methanol. The crude product was recrystallized in acetone (20 mL) to give red block crystals. Anal. Calcd. for C32 H20 F2 N8 Ni S4: C, 51.83; H, 2.72; N, 15.11%. Found: C, 51.96; H, 2.93; N, 15.03%.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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), showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level. Only the symmetry unique anion is shown. Symmetry code (A): -x, -y+1, -z.

1-(2-Fluorobenzylideneamino)pyridinium bis(1,2-dicyanoethene-1,2-dithiolato)nickelate(II) top

Crystal data top

(C₁₂H₁₀FN₂)₂[Ni(C₄N₂S₂)₂]	V = 788.4 (2) Å³
M_r = 741.51	Z = 1
Triclinic, P1	F(000) = 378
Hall symbol: -P 1	D_x = 1.562 Mg m⁻³
a = 7.9248 (13) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.1774 (15) Å	θ = 1.9–26.0°
c = 11.1526 (18) Å	µ = 0.93 mm⁻¹
α = 88.326 (3)°	T = 293 K
β = 77.202 (4)°	Block, red
γ = 85.448 (4)°	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3030 independent reflections
Radiation source: fine-focus sealed tube	1785 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→9
T_min = 0.732, T_max = 0.809	k = −11→11
4282 measured reflections	l = −13→12

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) = 0.094	H-atom parameters constrained
S = 0.76	w = 1/[σ²(F_o²) + (0.0323P)²] where P = (F_o² + 2F_c²)/3
3030 reflections	(Δ/σ)_max = 0.004
214 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

(C₁₂H₁₀FN₂)₂[Ni(C₄N₂S₂)₂]	γ = 85.448 (4)°
M_r = 741.51	V = 788.4 (2) Å³
Triclinic, P1	Z = 1
a = 7.9248 (13) Å	Mo Kα radiation
b = 9.1774 (15) Å	µ = 0.93 mm⁻¹
c = 11.1526 (18) Å	T = 293 K
α = 88.326 (3)°	0.30 × 0.20 × 0.20 mm
β = 77.202 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3030 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1785 reflections with I > 2σ(I)
T_min = 0.732, T_max = 0.809	R_int = 0.038
4282 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 0.76	Δρ_max = 0.31 e Å⁻³
3030 reflections	Δρ_min = −0.24 e Å⁻³
214 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
F1	0.5021 (3)	0.3555 (2)	−0.1896 (2)	0.0724 (7)
N7	0.7362 (4)	0.1871 (3)	0.1593 (3)	0.0528 (8)
N8	0.7118 (5)	0.1192 (3)	0.0532 (3)	0.0646 (10)
C21	0.5600 (5)	0.2153 (4)	−0.2199 (4)	0.0561 (11)
C22	0.5388 (6)	0.1628 (5)	−0.3283 (4)	0.0735 (13)
H22A	0.4832	0.2200	−0.3804	0.088*
C23	0.6029 (6)	0.0220 (5)	−0.3571 (4)	0.0797 (14)
H23A	0.5949	−0.0156	−0.4320	0.096*
C24	0.6779 (6)	−0.0643 (5)	−0.2792 (4)	0.0742 (14)
H24A	0.7179	−0.1602	−0.3001	0.089*
C25	0.6944 (5)	−0.0094 (4)	−0.1700 (4)	0.0609 (11)
H25A	0.7452	−0.0686	−0.1166	0.073*
C26	0.6362 (5)	0.1333 (4)	−0.1381 (3)	0.0484 (10)
C27	0.6580 (5)	0.1978 (4)	−0.0257 (4)	0.0531 (10)
H27A	0.6319	0.2974	−0.0126	0.064*
C28	0.8296 (6)	0.1020 (4)	0.2236 (4)	0.0616 (12)
H28A	0.8723	0.0089	0.1956	0.074*
C29	0.8626 (6)	0.1496 (4)	0.3287 (4)	0.0704 (13)
H29A	0.9291	0.0905	0.3725	0.085*
C30	0.7965 (5)	0.2868 (4)	0.3703 (4)	0.0622 (12)
H30A	0.8182	0.3215	0.4425	0.075*
C31	0.6997 (6)	0.3708 (4)	0.3049 (4)	0.0667 (13)
H31A	0.6533	0.4632	0.3326	0.080*
C32	0.6708 (6)	0.3200 (4)	0.1996 (4)	0.0700 (13)
H32A	0.6048	0.3780	0.1546	0.084*
Ni1	0.0000	0.5000	0.0000	0.0484 (2)
S1	0.17387 (15)	0.40603 (10)	0.11191 (9)	0.0589 (3)
S2	−0.08272 (14)	0.68427 (10)	0.12200 (9)	0.0585 (3)
N1	0.2744 (5)	0.4501 (4)	0.4175 (3)	0.0771 (12)
N2	−0.0466 (5)	0.8166 (4)	0.4231 (3)	0.0776 (12)
C1	−0.0194 (5)	0.7374 (4)	0.3440 (4)	0.0571 (11)
C2	0.0169 (5)	0.6389 (4)	0.2423 (3)	0.0490 (10)
C3	0.1256 (5)	0.5188 (4)	0.2397 (3)	0.0501 (10)
C4	0.2087 (6)	0.4806 (4)	0.3384 (4)	0.0553 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0756 (18)	0.0615 (15)	0.0818 (18)	0.0122 (13)	−0.0271 (14)	−0.0013 (13)
N7	0.063 (2)	0.0415 (18)	0.054 (2)	0.0031 (17)	−0.0156 (18)	−0.0038 (16)
N8	0.088 (3)	0.050 (2)	0.062 (2)	0.0107 (19)	−0.033 (2)	−0.0115 (18)
C21	0.049 (3)	0.057 (3)	0.061 (3)	−0.001 (2)	−0.010 (2)	−0.006 (2)
C22	0.076 (4)	0.084 (3)	0.067 (3)	−0.005 (3)	−0.031 (3)	0.004 (3)
C23	0.089 (4)	0.091 (4)	0.066 (3)	−0.004 (3)	−0.027 (3)	−0.023 (3)
C24	0.090 (4)	0.062 (3)	0.072 (3)	0.006 (3)	−0.022 (3)	−0.021 (3)
C25	0.070 (3)	0.049 (2)	0.068 (3)	0.003 (2)	−0.026 (2)	−0.006 (2)
C26	0.048 (3)	0.050 (2)	0.048 (2)	−0.006 (2)	−0.010 (2)	−0.0039 (19)
C27	0.053 (3)	0.044 (2)	0.061 (3)	0.003 (2)	−0.011 (2)	−0.007 (2)
C28	0.078 (3)	0.046 (2)	0.062 (3)	0.010 (2)	−0.024 (2)	−0.001 (2)
C29	0.091 (4)	0.058 (3)	0.068 (3)	0.013 (3)	−0.036 (3)	−0.005 (2)
C30	0.072 (3)	0.064 (3)	0.053 (3)	−0.001 (2)	−0.020 (2)	−0.009 (2)
C31	0.089 (4)	0.050 (3)	0.060 (3)	0.014 (2)	−0.019 (3)	−0.016 (2)
C32	0.095 (4)	0.053 (3)	0.066 (3)	0.026 (2)	−0.035 (3)	−0.012 (2)
Ni1	0.0527 (5)	0.0408 (4)	0.0520 (5)	0.0016 (3)	−0.0130 (4)	−0.0090 (3)
S1	0.0704 (8)	0.0504 (6)	0.0575 (7)	0.0119 (5)	−0.0214 (6)	−0.0151 (5)
S2	0.0655 (8)	0.0496 (6)	0.0631 (7)	0.0100 (5)	−0.0230 (6)	−0.0163 (5)
N1	0.100 (3)	0.068 (2)	0.068 (3)	0.008 (2)	−0.032 (2)	−0.010 (2)
N2	0.109 (3)	0.061 (2)	0.066 (3)	0.007 (2)	−0.028 (2)	−0.0186 (19)
C1	0.064 (3)	0.051 (3)	0.058 (3)	−0.002 (2)	−0.018 (2)	0.000 (2)
C2	0.050 (3)	0.039 (2)	0.056 (3)	−0.0034 (19)	−0.008 (2)	−0.0112 (19)
C3	0.057 (3)	0.043 (2)	0.051 (3)	0.000 (2)	−0.013 (2)	−0.0091 (19)
C4	0.068 (3)	0.042 (2)	0.055 (3)	0.001 (2)	−0.011 (2)	−0.011 (2)

Geometric parameters (Å, º) top

F1—C21	1.358 (4)	C29—C30	1.378 (5)
N7—C28	1.335 (4)	C29—H29A	0.9300
N7—C32	1.337 (4)	C30—C31	1.355 (5)
N7—N8	1.410 (4)	C30—H30A	0.9300
N8—C27	1.249 (4)	C31—C32	1.348 (5)
C21—C22	1.364 (5)	C31—H31A	0.9300
C21—C26	1.377 (5)	C32—H32A	0.9300
C22—C23	1.371 (5)	Ni1—S2ⁱ	2.1689 (10)
C22—H22A	0.9300	Ni1—S2	2.1689 (9)
C23—C24	1.360 (5)	Ni1—S1ⁱ	2.1703 (10)
C23—H23A	0.9300	Ni1—S1	2.1703 (10)
C24—C25	1.369 (4)	S1—C3	1.741 (3)
C24—H24A	0.9300	S2—C2	1.726 (4)
C25—C26	1.382 (5)	N1—C4	1.138 (4)
C25—H25A	0.9300	N2—C1	1.132 (4)
C26—C27	1.451 (4)	C1—C2	1.436 (5)
C27—H27A	0.9300	C2—C3	1.341 (5)
C28—C29	1.348 (5)	C3—C4	1.424 (5)
C28—H28A	0.9300

C28—N7—C32	120.4 (3)	C28—C29—C30	119.2 (4)
C28—N7—N8	113.1 (3)	C28—C29—H29A	120.4
C32—N7—N8	126.4 (3)	C30—C29—H29A	120.4
C27—N8—N7	118.0 (3)	C31—C30—C29	119.3 (4)
F1—C21—C22	118.7 (4)	C31—C30—H30A	120.3
F1—C21—C26	117.7 (3)	C29—C30—H30A	120.3
C22—C21—C26	123.5 (4)	C32—C31—C30	119.8 (4)
C21—C22—C23	117.0 (4)	C32—C31—H31A	120.1
C21—C22—H22A	121.5	C30—C31—H31A	120.1
C23—C22—H22A	121.5	N7—C32—C31	120.6 (4)
C24—C23—C22	121.9 (4)	N7—C32—H32A	119.7
C24—C23—H23A	119.1	C31—C32—H32A	119.7
C22—C23—H23A	119.1	S2ⁱ—Ni1—S2	180.0
C23—C24—C25	119.7 (4)	S2ⁱ—Ni1—S1ⁱ	92.10 (4)
C23—C24—H24A	120.1	S2—Ni1—S1ⁱ	87.90 (4)
C25—C24—H24A	120.1	S2ⁱ—Ni1—S1	87.90 (4)
C24—C25—C26	120.7 (4)	S2—Ni1—S1	92.10 (4)
C24—C25—H25A	119.7	S1ⁱ—Ni1—S1	180.00 (4)
C26—C25—H25A	119.7	C3—S1—Ni1	102.69 (14)
C21—C26—C25	117.1 (4)	C2—S2—Ni1	102.72 (13)
C21—C26—C27	120.4 (4)	N2—C1—C2	178.9 (5)
C25—C26—C27	122.5 (4)	C3—C2—C1	121.6 (4)
N8—C27—C26	119.8 (3)	C3—C2—S2	121.5 (3)
N8—C27—H27A	120.1	C1—C2—S2	116.9 (3)
C26—C27—H27A	120.1	C2—C3—C4	121.9 (3)
N7—C28—C29	120.7 (4)	C2—C3—S1	120.3 (3)
N7—C28—H28A	119.7	C4—C3—S1	117.7 (3)
C29—C28—H28A	119.7	N1—C4—C3	179.7 (5)

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	(C₁₂H₁₀FN₂)₂[Ni(C₄N₂S₂)₂]
M_r	741.51
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.9248 (13), 9.1774 (15), 11.1526 (18)
α, β, γ (°)	88.326 (3), 77.202 (4), 85.448 (4)
V (Å³)	788.4 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.93
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.732, 0.809
No. of measured, independent and observed [I > 2σ(I)] reflections	4282, 3030, 1785
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.094, 0.76
No. of reflections	3030
No. of parameters	214
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.24

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank the Natural Science Foundation of High Learning Institutions of Abhui Province, China, for financial support (grant No. KJ2009B275Z).

References

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ni, C. L., Dang, D. B. & Song, Y. (2004). Chem. Phys. Lett. 396, 353–358. Web of Science CSD CrossRef CAS Google Scholar
Ni, Z. P., Ren, X. M. & Ma, J. (2005). J. Am. Chem. Soc. 127, 14330–14338. Web of Science CrossRef PubMed CAS Google Scholar
Nishijo, J., Ogura, E., Yamaura, J. & Miyazaki, A. (2000). Solid State Commun. 116, 661–664. Web of Science CSD CrossRef CAS Google Scholar
Ren, X. M., Okudera, H. & Kremer, R. K. (2004). Inorg. Chem. 43, 2569–2576. Web of Science CSD CrossRef PubMed CAS Google Scholar
Robertson, N. & Cronin, L. (2002). Coord. Chem. Rev. 227, 93–127. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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