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In the title compound, (C12H10Br2N)2[Ni(C4N2S2)2], the NiII atom of the anion lies on an inversion centre and exhibits a square-planar coordination geometry. The benzene and pyridine rings of the cation make a dihedral angle of 74.6 (3)°. The cations (C1 and C2) and anions (A) are arranged in a …C1C2AC1C2AC1C2… pattern along the [\overline{1}10] direction and are linked by C—H...S hydrogen bonds and π–π stacking inter­actions involving the benzene ring [centroid–centroid separation = 3.778 (3) Å].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807056620/ci2505sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807056620/ci2505Isup2.hkl
Contains datablock I

CCDC reference: 672650

Key indicators

  • Single-crystal X-ray study
  • T = 291 K
  • Mean [sigma](C-C) = 0.009 Å
  • R factor = 0.055
  • wR factor = 0.117
  • Data-to-parameter ratio = 15.5

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 9 PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C1 - C2 ... 1.49 Ang. PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C3 - C4 ... 1.42 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1 (3) 2.82
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 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

Recently, some substituted benzylpyridinium cations have been introduced into the Ni(mnt)2 system (mnt is maleonitriledithiolate) in order to obtain some Ni(mnt)2-based molecular solids showing unusual magnetic properties (Ni et al., 2005; Xie et al., 2002; Ren et al., 2002). We report here the crystal structure of the title compound, in which 1-(3,5-dibromobenzyl)pyridinium functions as a counterion of Ni(mnt)2 anion.

As shown in Fig.1, the asymmetric unit of the title compound consists of one C12H10Br2N+ cation and one-half of a [Ni(C4N2S2)2]2- anion. The NiII ion lies on an inversion centre and exhibits a square-planar coordination geometry. The CN groups of the [Ni(mnt)2]2- unit are slightly tipped out of the C1/S1/Ni1/S2i/C3i plane, and the deviations from the plane are -0.116 (6) Å for N1 and 0.009 (6) Å for N2i [symmetry code: (i) 1 - x, 2 - y, 1 - z]. The benzene and pyridine rings of the C12H10Br2N+ unit form a dihedral angle of 74.6 (3)°. Atoms Br1 and Br2 deviate from the plane of the benzene ring by 0.038 (1) and 0.077 (1) Å, respectively.

Two C12H10Br2N+ units are linked to a [Ni(C4N2S2)2]2- unit through C16—H16···S1 hydrogen bonds (Table 1). The adjacent hydrogen-bonded units are cross-linked via weak π-π interactions between the benzene ring of the cation at (x, y, z) and (2 - x, 1 - y, 1 - z), with a centroid-centroid separation of 3.778 (3) Å. The cations and anions involved in the above interactions are arranged alternately along the [1 1 0] direction (Fig. 2).

Related literature top

For related literature, see: Liu & Ni (2006a,b); Ni et al. (2005); Ren et al. (2002); Xie et al. (2002).

Experimental top

The title compound was prepared by the direct reaction of NiCl2.6H2O (0.24 g, 1.0 mmol), disodium maleonitriledithiolate (0.37 g, 2.0 mmol) and 1-(3,5-dibromobenzyl)pyridinium bromide (0.85 g, 2.1 mmol) in water (50 ml). Red block-shaped single crystals were obtained by slow evaporation of a CH3CN-i-PrOH (1:1) solution at room temperature over three weeks.

Refinement top

All H atoms were placed in geometrically calculated positions (C—H = 0.93–0.97 Å) and treated as riding, with Uiso = 1.2 Ueq(parent atom).

Computing details top

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

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. Unlabelled atoms are related to the labelled atoms by the symmetry operation (1 - x, 2 - y, 1 - z).
[Figure 2] Fig. 2. The packing of the title compound, showing a column of anions and cations.
Bis[1-(3,5-dibromobenzyl)pyridinium] bis(1,2-dicyanoethene-1,2-dithiolato-κ2S,S')nickelate(II) top
Crystal data top
(C12H10Br2N)2[Ni(C4N2S2)2]Z = 1
Mr = 995.13F(000) = 486
Triclinic, P1Dx = 1.913 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.843 (3) ÅCell parameters from 904 reflections
b = 9.415 (3) Åθ = 2.7–27.9°
c = 10.861 (4) ŵ = 5.46 mm1
α = 77.701 (5)°T = 291 K
β = 78.427 (6)°Block, red
γ = 84.221 (5)°0.35 × 0.30 × 0.21 mm
V = 864.0 (5) Å3
Data collection top
Bruker SMART APEX CCD
diffractometer
3309 independent reflections
Radiation source: fine-focus sealed tube2482 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
ϕ and ω scansθmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
h = 510
Tmin = 0.165, Tmax = 0.323k = 1111
4584 measured reflectionsl = 1313
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)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.06P)2 + 0.99P]
where P = (Fo2 + 2Fc2)/3
3309 reflections(Δ/σ)max = 0.001
214 parametersΔρmax = 0.59 e Å3
0 restraintsΔρmin = 0.96 e Å3
Crystal data top
(C12H10Br2N)2[Ni(C4N2S2)2]γ = 84.221 (5)°
Mr = 995.13V = 864.0 (5) Å3
Triclinic, P1Z = 1
a = 8.843 (3) ÅMo Kα radiation
b = 9.415 (3) ŵ = 5.46 mm1
c = 10.861 (4) ÅT = 291 K
α = 77.701 (5)°0.35 × 0.30 × 0.21 mm
β = 78.427 (6)°
Data collection top
Bruker SMART APEX CCD
diffractometer
3309 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
2482 reflections with I > 2σ(I)
Tmin = 0.165, Tmax = 0.323Rint = 0.033
4584 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.117H-atom parameters constrained
S = 0.99Δρmax = 0.59 e Å3
3309 reflectionsΔρmin = 0.96 e Å3
214 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br11.36658 (7)0.41523 (7)0.40770 (6)0.03356 (18)
Br20.95637 (7)0.72824 (8)0.73580 (6)0.04073 (19)
C10.4467 (7)0.8563 (6)0.7832 (6)0.0340 (13)
C20.3762 (8)0.7687 (7)0.9091 (6)0.0384 (15)
C30.4290 (7)1.0569 (7)0.2308 (6)0.0323 (13)
C40.3562 (7)1.0604 (7)0.1245 (6)0.0349 (13)
C51.0417 (7)0.7617 (7)0.3449 (6)0.0317 (13)
C61.1611 (7)0.6488 (6)0.3263 (5)0.0298 (12)
H61.20190.63030.24500.036*
C71.2118 (7)0.5708 (7)0.4307 (6)0.0397 (15)
C81.1544 (7)0.5909 (7)0.5510 (5)0.0340 (13)
H81.18900.53200.62140.041*
C91.0407 (7)0.7037 (7)0.5658 (6)0.0339 (13)
C100.9816 (7)0.7898 (7)0.4667 (6)0.0358 (14)
H100.90520.86340.47970.043*
C110.9801 (7)0.8528 (6)0.2317 (5)0.0330 (13)
H11A1.06440.87740.16000.040*
H11B0.92900.94260.25360.040*
C120.9136 (8)0.6867 (7)0.1004 (6)0.0404 (15)
H121.01340.69120.05260.048*
C130.8089 (7)0.6021 (7)0.0802 (6)0.0362 (14)
H130.84140.53650.02580.043*
C140.6588 (7)0.6107 (6)0.1371 (6)0.0335 (13)
H140.58800.55710.11650.040*
C150.6095 (7)0.7000 (7)0.2271 (6)0.0361 (14)
H150.50770.70510.27020.043*
C160.7215 (7)0.7806 (6)0.2484 (6)0.0356 (14)
H160.69310.84720.30230.043*
N10.3176 (7)0.7000 (6)0.9957 (5)0.0456 (14)
N20.2845 (6)1.0553 (6)0.0475 (5)0.0373 (12)
N30.8642 (6)0.7645 (6)0.1946 (4)0.0350 (12)
Ni10.50001.00000.50000.0337 (3)
S10.34573 (18)0.87197 (16)0.65724 (15)0.0358 (4)
S20.35180 (18)0.96071 (17)0.37648 (15)0.0367 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0360 (3)0.0317 (3)0.0297 (3)0.0000 (2)0.0024 (2)0.0077 (2)
Br20.0298 (3)0.0566 (4)0.0336 (3)0.0010 (3)0.0058 (2)0.0158 (3)
C10.037 (3)0.023 (3)0.043 (3)0.008 (2)0.010 (3)0.004 (2)
C20.038 (3)0.030 (3)0.040 (3)0.008 (3)0.010 (3)0.005 (3)
C30.029 (3)0.033 (3)0.035 (3)0.013 (3)0.001 (2)0.010 (2)
C40.031 (3)0.029 (3)0.046 (3)0.007 (2)0.003 (3)0.013 (3)
C50.026 (3)0.037 (3)0.034 (3)0.007 (2)0.005 (2)0.019 (3)
C60.030 (3)0.028 (3)0.027 (3)0.010 (2)0.005 (2)0.001 (2)
C70.028 (3)0.043 (4)0.048 (4)0.011 (3)0.001 (3)0.012 (3)
C80.035 (3)0.037 (3)0.026 (3)0.018 (3)0.005 (2)0.000 (2)
C90.037 (3)0.035 (3)0.031 (3)0.007 (3)0.008 (3)0.006 (2)
C100.033 (3)0.031 (3)0.040 (3)0.001 (3)0.001 (3)0.007 (3)
C110.036 (3)0.028 (3)0.029 (3)0.002 (3)0.000 (2)0.000 (2)
C120.049 (4)0.041 (3)0.029 (3)0.003 (3)0.018 (3)0.006 (3)
C130.033 (3)0.044 (4)0.029 (3)0.010 (3)0.012 (3)0.002 (3)
C140.034 (3)0.024 (3)0.047 (3)0.004 (2)0.022 (3)0.001 (3)
C150.032 (3)0.035 (3)0.038 (3)0.005 (3)0.003 (3)0.006 (3)
C160.035 (3)0.028 (3)0.038 (3)0.007 (3)0.000 (3)0.002 (3)
N10.044 (3)0.045 (3)0.042 (3)0.026 (3)0.003 (3)0.010 (3)
N20.036 (3)0.039 (3)0.031 (3)0.007 (2)0.006 (2)0.009 (2)
N30.032 (3)0.034 (3)0.031 (3)0.023 (2)0.006 (2)0.000 (2)
Ni10.0298 (6)0.0282 (5)0.0365 (6)0.0150 (4)0.0035 (4)0.0020 (4)
S10.0322 (8)0.0298 (7)0.0382 (8)0.0141 (6)0.0039 (6)0.0009 (6)
S20.0331 (8)0.0325 (8)0.0396 (8)0.0079 (6)0.0034 (6)0.0026 (6)
Geometric parameters (Å, º) top
Br1—C71.923 (7)C10—H100.93
Br2—C91.901 (6)C11—N31.543 (9)
C1—C3i1.400 (8)C11—H11A0.97
C1—C21.490 (8)C11—H11B0.97
C1—S11.751 (7)C12—C131.359 (10)
C2—N11.088 (8)C12—N31.360 (8)
C3—C1i1.400 (8)C12—H120.93
C3—C41.424 (9)C13—C141.349 (9)
C3—S21.694 (6)C13—H130.93
C4—N21.158 (8)C14—C151.400 (9)
C5—C101.393 (8)C14—H140.93
C5—C61.437 (8)C15—C161.388 (9)
C5—C111.507 (9)C15—H150.93
C6—C71.344 (9)C16—N31.288 (7)
C6—H60.93C16—H160.93
C7—C81.350 (9)Ni1—S2i2.1607 (18)
C8—C91.399 (9)Ni1—S22.1607 (18)
C8—H80.93Ni1—S1i2.1795 (16)
C9—C101.363 (9)Ni1—S12.1795 (16)
C3i—C1—C2122.6 (6)C5—C11—H11B110.0
C3i—C1—S1120.0 (5)N3—C11—H11B110.0
C2—C1—S1116.4 (5)H11A—C11—H11B108.4
N1—C2—C1174.1 (8)C13—C12—N3116.2 (6)
C1i—C3—C4119.8 (5)C13—C12—H12121.9
C1i—C3—S2120.8 (5)N3—C12—H12121.9
C4—C3—S2119.1 (4)C14—C13—C12121.7 (6)
N2—C4—C3172.6 (6)C14—C13—H13119.2
C10—C5—C6121.1 (6)C12—C13—H13119.2
C10—C5—C11118.8 (5)C13—C14—C15120.1 (6)
C6—C5—C11120.1 (5)C13—C14—H14119.9
C7—C6—C5117.6 (5)C15—C14—H14119.9
C7—C6—H6121.2C16—C15—C14116.2 (6)
C5—C6—H6121.2C16—C15—H15121.9
C6—C7—C8123.6 (6)C14—C15—H15121.9
C6—C7—Br1118.0 (5)N3—C16—C15121.0 (6)
C8—C7—Br1118.3 (5)N3—C16—H16119.5
C7—C8—C9117.5 (6)C15—C16—H16119.5
C7—C8—H8121.3C16—N3—C12123.8 (6)
C9—C8—H8121.3C16—N3—C11116.5 (5)
C10—C9—C8123.8 (6)C12—N3—C11119.4 (5)
C10—C9—Br2118.9 (5)S2i—Ni1—S2180
C8—C9—Br2117.3 (4)S2i—Ni1—S1i86.58 (6)
C9—C10—C5116.4 (6)S2—Ni1—S1i93.42 (6)
C9—C10—H10121.8S2i—Ni1—S193.42 (6)
C5—C10—H10121.8S2—Ni1—S186.58 (6)
C5—C11—N3108.5 (5)S1i—Ni1—S1180
C5—C11—H11A110.0C1—S1—Ni1101.1 (2)
N3—C11—H11A110.0C3—S2—Ni1103.4 (2)
Symmetry code: (i) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C16—H16···S1i0.932.753.591 (5)151
Symmetry code: (i) x+1, y+2, z+1.

Experimental details

Crystal data
Chemical formula(C12H10Br2N)2[Ni(C4N2S2)2]
Mr995.13
Crystal system, space groupTriclinic, P1
Temperature (K)291
a, b, c (Å)8.843 (3), 9.415 (3), 10.861 (4)
α, β, γ (°)77.701 (5), 78.427 (6), 84.221 (5)
V3)864.0 (5)
Z1
Radiation typeMo Kα
µ (mm1)5.46
Crystal size (mm)0.35 × 0.30 × 0.21
Data collection
DiffractometerBruker SMART APEX CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2004)
Tmin, Tmax0.165, 0.323
No. of measured, independent and
observed [I > 2σ(I)] reflections
4584, 3309, 2482
Rint0.033
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.117, 0.99
No. of reflections3309
No. of parameters214
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.59, 0.96

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

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C16—H16···S1i0.9302.753.591 (5)151
Symmetry code: (i) x+1, y+2, z+1.
 

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