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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 π–π 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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680705814X/ci2509sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680705814X/ci2509Isup2.hkl
Contains datablock I

CCDC reference: 672708

Key indicators

  • Single-crystal X-ray study
  • T = 291 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.025
  • wR factor = 0.071
  • Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Ni1 - S2 .. 11.08 su
Alert level C PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 100 Ang. PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 1000 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 6 PLAT230_ALERT_2_C Hirshfeld Test Diff for C2 - C4 .. 5.71 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni1 - S1 .. 9.84 su PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C2 - C3 ... 1.42 Ang. PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C2 - C4 ... 1.42 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1 (2) 2.15
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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 –CN 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 = 715.51F(000) = 366
Triclinic, P1Dx = 1.537 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.085 (1) ÅCell parameters from 3505 reflections
b = 9.048 (1) Åθ = 2.4–29.5°
c = 13.182 (1) ŵ = 0.94 mm1
α = 71.68 (1)°T = 291 K
β = 74.93 (1)°Block, brown
γ = 82.11 (1)°0.30 × 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)
Graphite monochromatorRint = 0.009
ϕ and ω scansθmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
h = 86
Tmin = 0.766, Tmax = 0.836k = 1010
4185 measured reflectionsl = 1511
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.045P)2 + 0.1686P]
where P = (Fo2 + 2Fc2)/3
2695 reflections(Δ/σ)max = 0.001
205 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
(C12H11FN)2[Ni(C4N2S2)2]γ = 82.11 (1)°
Mr = 715.51V = 773.19 (15) Å3
Triclinic, P1Z = 1
a = 7.085 (1) ÅMo Kα radiation
b = 9.048 (1) ŵ = 0.94 mm1
c = 13.182 (1) ÅT = 291 K
α = 71.68 (1)°0.30 × 0.25 × 0.20 mm
β = 74.93 (1)°
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)] = 0.0250 restraints
wR(F2) = 0.071H-atom parameters constrained
S = 1.03Δρmax = 0.19 e Å3
2695 reflectionsΔρmin = 0.26 e Å3
205 parameters
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)
F10.34351 (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*
C60.0245 (3)0.57681 (19)0.79671 (14)0.0472 (4)
H60.04060.52340.75000.057*
C70.1730 (3)0.59274 (19)0.88309 (14)0.0474 (4)
C80.1575 (3)0.6725 (2)0.95277 (14)0.0516 (4)
H80.26190.68241.01040.062*
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, º) 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 code: (i) x+2, y, z+1.
Hydrogen-bond geometry (Å, º) 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.

Experimental details

Crystal data
Chemical formula(C12H11FN)2[Ni(C4N2S2)2]
Mr715.51
Crystal system, space groupTriclinic, P1
Temperature (K)291
a, b, c (Å)7.085 (1), 9.048 (1), 13.182 (1)
α, β, γ (°)71.68 (1), 74.93 (1), 82.11 (1)
V3)773.19 (15)
Z1
Radiation typeMo Kα
µ (mm1)0.94
Crystal size (mm)0.30 × 0.25 × 0.20
Data collection
DiffractometerBruker SMART APEX CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2004)
Tmin, Tmax0.766, 0.836
No. of measured, independent and
observed [I > 2σ(I)] reflections
4185, 2695, 2568
Rint0.009
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.071, 1.03
No. of reflections2695
No. of parameters205
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.26

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Bruker, 2000), SHELXTL.

Hydrogen-bond geometry (Å, º) 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.
 

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