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Acta Cryst. (2007). E63, m3084    [ doi:10.1107/S160053680705814X ]

Bis[1-(4-fluorobenzyl)pyridinium] bis(2,2-dicyanoethene-1,1-dithiolato-[kappa]2S,S')nickelate(II)

A.-Q. Zhou and C.-L. Ni

Abstract top

A new ion-pair complex, (C12H11FN)2[Ni(C4N2S2)2] or (FBzPy)2[Ni(imnt)2], where FBzPy is 1-(4-fluorobenzyl)pyridinium and imnt is 2,2-dicyanoethene-1,1-dithiolate, was obtained by the direct reaction of NiCl2, K2(imnt) and (FBzPy)+Br- in H2O. The asymmetric unit contains a [FBzPy]+ cation and one half of the Ni[imnt]22- anion. The NiII ion lies on an inversion centre and adopts a square-planar configuration. In the [FBzPy]+ cation, the benzene and pyridinium rings make a dihedral angle of 77.2 (3)°. In the crystal structure, C-H...N hydrogen bonds and [pi]-[pi] interactions [3.450 (3) Å] between ethenyl groups of the Ni[imnt]22- anion and the pyridinium ring of the cation generate a three-dimensional network.

Comment top

2,2-Dicyanoethene-1,1-dithiolate (imnt) or 1,2-dicyanoethene-1,2-dithiolate (mnt) transition metal complexes have attracted cosiderable interest in molecular materials research (Liu et al., 1996; Robertson & Cronin, 2002; Ni et al., 2007; Ren et al., 2002; Nishijo et al., 2003; Xie et al., 2002; Canadell, 1999). Our studies have been focused on the design, preparation, and investigation of some new salts that based on the molecular architecture of Ni(imnt)22− anions because the topology and the size of the counterions used with Ni(imnt)22− anion play an important role in tuning the stacks of anions and cations (Liu et al., 1996; Liu et al., 2006; Feng et al., 2007).

The asymmetric unit of the title compound consists of one [FBzPy]+ cation and one-half of Ni(imnt)2 anion located on an inversion center; the NiII ion lies on an inversion centre. The NiS4 core exhibits a square-planar configuration, with Ni—S distances of 2.2058 (5) and 2.2133 (5) Å. The S1—Ni1—S2 bond angle within the four-membered ring (Ni1/S1/C1/S2) is 78.80 (2)°. Atoms N1 and N2 of the –C≡N groups deviate from the Ni1/S1/C1/S2 plane by 0.607 (3) Å and 0.174 (3) Å, respectively. The [FBzPy]+ cation adopts a conformation where both the benzene and pyridinium rings are twisted with respect to the N3/C11/C10 reference plane with dihedral angles of 97.7 (2)° and 95.6 (3)°, respectively. The benzene and pyridinium rings make a dihedral angle of 77.2 (3)°. The F atom deviates from the benzene plane by 0.024 (3) Å.

In the crystal structure, C—H···N type hydrogen bonds (Table 1) and π-π interactions are observed between cations and anions. The π-π interaction is observed between ethenyl groups of the Ni(imnt)22− anion and the N3i/C12i—C16i [symmetry code: (i) x, −1 + y, z] ring of the cation, with the distance between atom C2 and the centroid of the ring being 3.492 (3) Å. The above interactions generate a three-dimensional network structure (Fig 2).

Related literature top

For related Ni(imnt)22− complexes, see: Liu et al. (1996, 2006); Feng et al. (2007). For related literature, see: Canadell (1999); Ni et al. (2007); Nishijo et al. (2003); Ren et al. (2002); Robertson & Cronin (2002); Xie et al. (2002).

Experimental top

The title compound was prepared by the direct reaction of NiCl2·6H2O (0.24 g, 1 mmol), K2(imnt)·H2O (0.48 g, 2 mmol) and (FBzPy)+Br− (0.54 g, 2 mmol) in H2O (50 ml). Brown crystals were obtained by slow evaporation of a CH3CN solution at room temperature over two weeks.

Refinement top

H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined using a riding model, with Uiso = 1.2 Ueq(parent atom).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The cation and anion of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms have been omitted for clarity. Unlabelled atoms are related to the labelled atoms by the symmetry operation (2 − x, −y, 1 − z).
[Figure 2] Fig. 2. The crystal packing of the title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines.
Bis[1-(4-fluorobenzyl)pyridinium] bis(2,2-dicyanoethene-1,1-dithiolato-κ2S,S')nickelate(II) top
Crystal data top
(C12H11FN)2[Ni(C4N2S2)2]Z = 1
Mr = 715.51F000 = 366
Triclinic, P1Dx = 1.537 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 7.085 (1) ÅCell parameters from 3505 reflections
b = 9.048 (1) Åθ = 2.4–29.5º
c = 13.182 (1) ŵ = 0.94 mm−1
α = 71.68 (1)ºT = 291 (2) K
β = 74.93 (1)ºBlock, brown
γ = 82.11 (1)º0.30 × 0.25 × 0.20 mm
V = 773.19 (15) Å3
Data collection top
Bruker SMART APEX CCD
diffractometer		2695 independent reflections
Radiation source: fine-focus sealed tube2568 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.009
T = 291(2) Kθmax = 25.0º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −8→6
Tmin = 0.766, Tmax = 0.836k = −10→10
4185 measured reflectionsl = −15→11
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.071  w = 1/[σ2(Fo2) + (0.045P)2 + 0.1686P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
2695 reflectionsΔρmax = 0.19 e Å−3
205 parametersΔρmin = −0.25 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
(C12H11FN)2[Ni(C4N2S2)2]γ = 82.11 (1)º
Mr = 715.51V = 773.19 (15) Å3
Triclinic, P1Z = 1
a = 7.085 (1) ÅMo Kα
b = 9.048 (1) ŵ = 0.94 mm−1
c = 13.182 (1) ÅT = 291 (2) K
α = 71.68 (1)º0.30 × 0.25 × 0.20 mm
β = 74.93 (1)º
Data collection top
Bruker SMART APEX CCD
diffractometer		2695 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		2568 reflections with I > 2σ(I)
Tmin = 0.766, Tmax = 0.836Rint = 0.009
4185 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.025205 parameters
wR(F2) = 0.071H-atom parameters constrained
S = 1.03Δρmax = 0.19 e Å−3
2695 reflectionsΔρmin = −0.25 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni11.00000.00000.50000.03971 (11)
S10.87140 (6)−0.02721 (5)0.67579 (3)0.04361 (12)
S20.86668 (7)0.23756 (5)0.49460 (3)0.04755 (13)
N10.7048 (3)0.1351 (2)0.91290 (14)0.0747 (5)
N20.6279 (3)0.54849 (19)0.63808 (14)0.0611 (4)
N30.33540 (19)0.96970 (15)0.76440 (11)0.0391 (3)
F1−0.34351 (17)0.52632 (13)0.90040 (10)0.0665 (3)
C10.8128 (2)0.17017 (19)0.63538 (12)0.0376 (3)
C20.7406 (2)0.25975 (19)0.70595 (13)0.0398 (3)
C30.7188 (3)0.1919 (2)0.82093 (14)0.0479 (4)
C40.6808 (2)0.4202 (2)0.66752 (13)0.0440 (4)
C50.1503 (3)0.64193 (18)0.78041 (13)0.0442 (4)
H50.25370.63110.72250.053*
C6−0.0245 (3)0.57681 (19)0.79671 (14)0.0472 (4)
H6−0.04060.52340.75000.057*
C7−0.1730 (3)0.59274 (19)0.88309 (14)0.0474 (4)
C8−0.1575 (3)0.6725 (2)0.95277 (14)0.0516 (4)
H8−0.26190.68241.01040.062*
C90.0174 (3)0.7379 (2)0.93532 (13)0.0486 (4)
H90.03100.79260.98180.058*
C100.1731 (2)0.72308 (17)0.84929 (12)0.0398 (3)
C110.3599 (3)0.8020 (2)0.82662 (15)0.0469 (4)
H11A0.39240.79360.89540.056*
H11B0.46630.75100.78430.056*
C120.2810 (3)1.0763 (2)0.81891 (15)0.0493 (4)
H120.26631.04650.89470.059*
C130.2468 (3)1.2291 (2)0.76345 (17)0.0586 (5)
H130.20761.30290.80170.070*
C140.2701 (3)1.2737 (2)0.65203 (17)0.0556 (5)
H140.24821.37770.61400.067*
C150.3260 (3)1.1639 (2)0.59723 (15)0.0551 (5)
H150.34261.19200.52140.066*
C160.3573 (3)1.0107 (2)0.65574 (14)0.0510 (4)
H160.39410.93490.61910.061*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.04242 (18)0.04293 (18)0.02804 (16)0.00353 (12)−0.00639 (12)−0.00631 (12)
S10.0494 (2)0.0426 (2)0.0298 (2)0.00407 (17)−0.00642 (16)−0.00304 (16)
S20.0599 (3)0.0461 (2)0.0271 (2)0.00719 (19)−0.00731 (18)−0.00378 (17)
N10.1176 (16)0.0689 (11)0.0361 (9)−0.0076 (11)−0.0206 (9)−0.0101 (8)
N20.0720 (11)0.0493 (10)0.0542 (10)0.0051 (8)−0.0146 (8)−0.0078 (7)
N30.0380 (7)0.0403 (7)0.0360 (7)0.0011 (5)−0.0115 (5)−0.0062 (6)
F10.0581 (7)0.0592 (7)0.0736 (8)−0.0097 (5)−0.0123 (5)−0.0073 (6)
C10.0335 (7)0.0442 (8)0.0311 (8)−0.0003 (6)−0.0091 (6)−0.0048 (6)
C20.0410 (8)0.0451 (9)0.0301 (8)0.0003 (7)−0.0100 (6)−0.0062 (7)
C30.0599 (10)0.0487 (9)0.0353 (9)−0.0026 (8)−0.0115 (8)−0.0123 (7)
C40.0454 (9)0.0506 (11)0.0350 (8)−0.0019 (8)−0.0084 (7)−0.0120 (7)
C50.0521 (9)0.0384 (8)0.0366 (8)0.0107 (7)−0.0087 (7)−0.0101 (7)
C60.0591 (10)0.0372 (8)0.0454 (9)0.0052 (7)−0.0166 (8)−0.0119 (7)
C70.0506 (9)0.0356 (8)0.0463 (10)0.0012 (7)−0.0135 (8)0.0018 (7)
C80.0563 (10)0.0501 (10)0.0354 (9)0.0035 (8)0.0000 (7)−0.0058 (7)
C90.0647 (11)0.0454 (9)0.0327 (8)0.0038 (8)−0.0096 (7)−0.0116 (7)
C100.0494 (9)0.0317 (7)0.0328 (8)0.0068 (6)−0.0136 (7)−0.0022 (6)
C110.0509 (10)0.0424 (9)0.0454 (9)0.0089 (7)−0.0191 (8)−0.0081 (7)
C120.0597 (11)0.0470 (10)0.0401 (9)−0.0018 (8)−0.0135 (8)−0.0103 (8)
C130.0717 (13)0.0427 (10)0.0593 (12)0.0000 (9)−0.0156 (10)−0.0129 (9)
C140.0527 (10)0.0438 (10)0.0616 (12)−0.0072 (8)−0.0185 (9)0.0031 (9)
C150.0567 (11)0.0613 (11)0.0378 (9)−0.0132 (9)−0.0116 (8)0.0033 (8)
C160.0557 (10)0.0561 (10)0.0381 (9)−0.0030 (8)−0.0068 (8)−0.0128 (8)
Geometric parameters (Å, °) top
Ni1—S1i2.2058 (5)C6—H60.93
Ni1—S12.2058 (4)C7—C81.366 (3)
Ni1—S22.2133 (5)C8—C91.380 (3)
Ni1—S2i2.2133 (5)C8—H80.93
S1—C11.7201 (17)C9—C101.387 (2)
S2—C11.7163 (15)C9—H90.93
N1—C31.142 (2)C10—C111.507 (2)
N2—C41.145 (2)C11—H11A0.97
N3—C161.334 (2)C11—H11B0.97
N3—C121.336 (2)C12—C131.368 (3)
N3—C111.491 (2)C12—H120.93
F1—C71.357 (2)C13—C141.366 (3)
C1—C21.377 (2)C13—H130.93
C2—C31.420 (2)C14—C151.364 (3)
C2—C41.423 (2)C14—H140.93
C5—C61.382 (2)C15—C161.378 (3)
C5—C101.385 (2)C15—H150.93
C5—H50.93C16—H160.93
C6—C71.365 (3)
S1i—Ni1—S1180C7—C8—H8120.9
S1i—Ni1—S2101.201 (18)C9—C8—H8120.9
S1—Ni1—S278.799 (19)C8—C9—C10120.87 (16)
S1i—Ni1—S2i78.799 (18)C8—C9—H9119.6
S1—Ni1—S2i101.201 (18)C10—C9—H9119.6
S2—Ni1—S2i180C5—C10—C9118.90 (16)
C1—S1—Ni185.66 (5)C5—C10—C11120.24 (15)
C1—S2—Ni185.51 (6)C9—C10—C11120.76 (15)
C16—N3—C12120.66 (15)N3—C11—C10109.83 (13)
C16—N3—C11119.73 (15)N3—C11—H11A109.7
C12—N3—C11119.50 (14)C10—C11—H11A109.7
C2—C1—S2125.81 (13)N3—C11—H11B109.7
C2—C1—S1124.73 (12)C10—C11—H11B109.7
S2—C1—S1109.42 (9)H11A—C11—H11B108.2
C1—C2—C3120.24 (15)N3—C12—C13120.07 (17)
C1—C2—C4121.83 (14)N3—C12—H12120.0
C3—C2—C4117.91 (15)C13—C12—H12120.0
N1—C3—C2178.5 (2)C14—C13—C12120.18 (19)
N2—C4—C2178.26 (19)C14—C13—H13119.9
C6—C5—C10120.72 (16)C12—C13—H13119.9
C6—C5—H5119.6C15—C14—C13119.22 (17)
C10—C5—H5119.6C15—C14—H14120.4
C7—C6—C5118.37 (16)C13—C14—H14120.4
C7—C6—H6120.8C14—C15—C16119.12 (17)
C5—C6—H6120.8C14—C15—H15120.4
F1—C7—C6118.43 (17)C16—C15—H15120.4
F1—C7—C8118.65 (16)N3—C16—C15120.75 (18)
C6—C7—C8122.93 (17)N3—C16—H16119.6
C7—C8—C9118.20 (16)C15—C16—H16119.6
Symmetry codes: (i) −x+2, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C12—H12···N1ii0.932.593.471 (3)157
C15—H15···N2iii0.932.603.337 (3)136
Symmetry codes: (ii) −x+1, −y+1, −z+2; (iii) −x+1, −y+2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C12—H12···N1i0.932.593.471 (3)157
C15—H15···N2ii0.932.603.337 (3)136
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+2, −z+1.
Acknowledgements top

The authors thank the Science and Technology Project (grant No. 2007B011000008) from Guangdong Science and Technology Department and the President's Science Foundation of South China Agricultural University (grant No. 2005 K092) for financial support.

references
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