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Acta Cryst. (2007). E63, m2030    [ doi:10.1107/S1600536807031157 ]

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

J.-R. Zhou, Y. Hou and C.-L. Ni

Abstract top

The asymmetric unit of the title ion-pair complex, (C7H11N2)2[Ni(C4N2S2)2] or (DMAPH)2[Ni(mnt)2] [where DMAPH is 4-(dimethylamino)pyridinium and mnt is maleonitriledithiolate], consists of one cation and one half-anion, the NiII atom lying on a crystallographic centre of symmetry. The metal is coordinated by four S atoms of two mnt2- ligands in a square-planar geometry. The [Ni(mnt)2]2- anions (A) and DMAPH+ cations (C) are stacked in an ACCA arrangement to form one-dimensional columns along the a axis, with a centroid-centroid separation between the pyridine rings of 4.032 (4) Å. The columns are linked by intermolecular N-H...N hydrogen bonds, resulting in a two-dimensional network.

Comment top

The syntheses, crystal structures and properties of maleonitriledithiolate (mnt2-) transition metal complexes have received much attention in many areas such as non-linear optics and magnetic and conducting materials [Robertson & Cronin, 2002]. The introduction of some organic cations was recognized to be a powerful strategy to tune the stacking pattern of the Ni(mnt)2 dianion in order to obtain molecular materials with unusual magnetic properties.

The asymmetric unit of the title compound consists of one DMAPH+ cation (DMAPH is 4-dimethylaminopyridinium) and one half-anion of formula Ni(mnt)22- (mnt is 1,2-dicyanoethylene-1,2-dithiolate or maleonitriledithiolate). The nickel(II) metal, which lies on a crystallographic centre of symmetry, is coordinated by four S atoms from two mnt ligands in a square planar geometry (Fig. 1). The five-membered chelating ring is essentially planar (maximum displacement 0.019 (2) Å for atom C2). The conformations of anion and cation are similar to those observed in the corresponding copper(II) complex (Zhou & Ren, 2006). The Ni(mnt)2 anions (A) and DMAPH+ cations (C) are stacked in a ACCA arrangement to form one-dimensional columns along the a axis, with a centroid···centroid separation between the pyridine rings of 4.032 (4) Å. The columns are linked by intermolecular N—H···N hydrogen bonds (Table 1) resulting in a two-dimensional network (Fig. 2).

Related literature top

For general background, see: Robertson & Cronin (2002). For a related structure, see: (Zhou & Ren, 2006).

Experimental top

The title compound was prepared by the direct reaction of NiCl2.6H2O (1 mmol, 0.24 g), Na2mnt (2 mmol, 0.37 g) and 4-dimethylaminopyridinium chloride (2 mmol, 0.32 g) in water (60 ml). Red block-shaped single crystals were obtained by slow evaporation of a CH3CN solution at room temperature for about two weeks.

Refinement top

The pyridinium H atom was located in a difference Fourier map and refined freely. All other H atoms were placed in geometrically calculated positions with C—H = 0.93–0.96 Å, and refined using the riding atom approximation, with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(C) for the methyl groups.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 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 molecular structure of the title compound, with atom-labelling scheme and 30% probability displacement ellipsoids. H atoms are omitted for clarity. Atoms labelled with the suffix A are generated by the symmetry operator (-x, -y, -z).
[Figure 2] Fig. 2. A perspective view of the crystal packing of the title compound viewed along the a axis. H atoms are omitted for clarity.
Bis[4-(dimethylamino)pyridinium] bis(1,2-dicyanoethylene-1,2-dithiolato-κ2S,S')nickelate(II) top
Crystal data top
(C7H11N2)2[Ni(C4N2S2)2]F(000) = 604
Mr = 585.43Dx = 1.523 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4341 reflections
a = 14.1631 (12) Åθ = 2.7–29.3°
b = 6.5833 (6) ŵ = 1.12 mm−1
c = 15.0751 (13) ÅT = 291 K
β = 114.771 (1)°Block, red
V = 1276.27 (19) Å30.46 × 0.40 × 0.15 mm
Z = 2
Data collection top
Bruker SMART APEX CCD
diffractometer		3075 independent reflections
Radiation source: fine-focus sealed tube2744 reflections with I > 2σ(I)
graphiteRint = 0.015
φ and ω scansθmax = 28.0°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −10→18
Tmin = 0.628, Tmax = 0.851k = −8→8
8238 measured reflectionsl = −19→15
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)] = 0.028H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.079 w = 1/[σ2(Fo2) + (0.0471P)2 + 0.1627P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
3075 reflectionsΔρmax = 0.37 e Å−3
167 parametersΔρmin = −0.24 e Å−3
0 restraintsExtinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0060 (8)
Crystal data top
(C7H11N2)2[Ni(C4N2S2)2]V = 1276.27 (19) Å3
Mr = 585.43Z = 2
Monoclinic, P21/cMo Kα radiation
a = 14.1631 (12) ŵ = 1.12 mm−1
b = 6.5833 (6) ÅT = 291 K
c = 15.0751 (13) Å0.46 × 0.40 × 0.15 mm
β = 114.771 (1)°
Data collection top
Bruker SMART APEX CCD
diffractometer		3075 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		2744 reflections with I > 2σ(I)
Tmin = 0.628, Tmax = 0.851Rint = 0.015
8238 measured reflectionsθmax = 28.0°
Refinement top
R[F2 > 2σ(F2)] = 0.028H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.079Δρmax = 0.37 e Å−3
S = 1.08Δρmin = −0.24 e Å−3
3075 reflectionsAbsolute structure: ?
167 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.00000.00000.00000.03144 (10)
S10.09496 (3)0.27334 (6)0.03137 (3)0.04174 (12)
S20.11660 (3)−0.16103 (6)0.12276 (3)0.04267 (12)
C10.20511 (11)0.2056 (2)0.13333 (11)0.0355 (3)
C20.21416 (12)0.0182 (2)0.17392 (11)0.0360 (3)
C30.30409 (13)−0.0369 (2)0.25921 (12)0.0423 (4)
C40.28715 (12)0.3503 (2)0.17446 (12)0.0418 (3)
N10.35347 (13)0.4638 (2)0.20822 (13)0.0602 (4)
N20.37520 (13)−0.0796 (3)0.32811 (12)0.0621 (4)
C50.57111 (14)0.1127 (3)−0.10347 (14)0.0569 (5)
H50.53270.1986−0.15500.068*
C60.66305 (13)0.1782 (3)−0.03421 (13)0.0484 (4)
H60.68660.3081−0.03850.058*
C70.72351 (12)0.0507 (2)0.04465 (11)0.0382 (3)
C80.68034 (14)−0.1433 (3)0.04575 (14)0.0486 (4)
H80.7159−0.23380.09610.058*
C90.58738 (15)−0.1975 (3)−0.02630 (16)0.0572 (5)
H90.5602−0.3252−0.02440.069*
C100.88001 (16)−0.0288 (3)0.18988 (14)0.0552 (5)
H10A0.8451−0.06430.23020.083*
H10B0.94470.03680.22900.083*
H10C0.8932−0.14950.16120.083*
C110.85807 (15)0.3081 (3)0.11201 (15)0.0578 (5)
H11A0.89420.30570.07050.087*
H11B0.90560.34470.17710.087*
H11C0.80280.40600.08760.087*
H40.472 (2)−0.107 (4)−0.1457 (19)0.094 (9)*
N30.81502 (10)0.1083 (2)0.11314 (10)0.0425 (3)
N40.53422 (12)−0.0721 (3)−0.09962 (13)0.0596 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.02752 (15)0.03259 (15)0.03065 (15)−0.00072 (9)0.00868 (11)0.00233 (9)
S10.0343 (2)0.0353 (2)0.0432 (2)−0.00337 (14)0.00413 (16)0.00727 (15)
S20.0382 (2)0.0373 (2)0.0404 (2)−0.00338 (15)0.00455 (16)0.00841 (15)
C10.0302 (7)0.0374 (7)0.0356 (7)0.0001 (6)0.0104 (6)−0.0025 (6)
C20.0303 (7)0.0400 (8)0.0336 (7)0.0018 (5)0.0093 (6)−0.0005 (5)
C30.0384 (8)0.0399 (7)0.0416 (9)0.0033 (6)0.0099 (7)−0.0001 (6)
C40.0357 (8)0.0403 (8)0.0417 (8)0.0008 (6)0.0085 (6)0.0020 (6)
N10.0455 (9)0.0502 (8)0.0626 (10)−0.0107 (7)0.0007 (7)0.0012 (7)
N20.0491 (9)0.0626 (10)0.0536 (9)0.0113 (8)0.0008 (7)0.0056 (8)
C50.0447 (9)0.0711 (13)0.0450 (9)0.0119 (9)0.0092 (8)0.0012 (8)
C60.0460 (9)0.0480 (9)0.0476 (9)0.0029 (7)0.0162 (7)0.0034 (7)
C70.0358 (8)0.0428 (7)0.0380 (8)−0.0001 (6)0.0174 (6)−0.0031 (6)
C80.0459 (9)0.0437 (8)0.0549 (10)−0.0032 (7)0.0198 (8)−0.0002 (7)
C90.0496 (10)0.0505 (10)0.0726 (13)−0.0114 (8)0.0267 (10)−0.0149 (9)
C100.0484 (10)0.0668 (12)0.0411 (9)0.0072 (8)0.0095 (8)0.0001 (8)
C110.0544 (11)0.0585 (11)0.0591 (11)−0.0190 (9)0.0224 (9)−0.0131 (9)
N30.0368 (7)0.0470 (7)0.0401 (7)−0.0027 (6)0.0126 (5)−0.0033 (6)
N40.0366 (8)0.0743 (11)0.0589 (10)−0.0031 (8)0.0113 (7)−0.0196 (9)
Geometric parameters (Å, °) top
Ni1—S22.1714 (4)C7—N31.330 (2)
Ni1—S2i2.1714 (4)C7—C81.419 (2)
Ni1—S12.1766 (4)C8—C91.357 (3)
Ni1—S1i2.1766 (4)C8—H80.9300
S1—C11.7278 (15)C9—N41.332 (3)
S2—C21.7330 (15)C9—H90.9300
C1—C21.359 (2)C10—N31.452 (2)
C1—C41.428 (2)C10—H10A0.9600
C2—C31.426 (2)C10—H10B0.9600
C3—N21.138 (2)C10—H10C0.9600
C4—N11.140 (2)C11—N31.453 (2)
C5—N41.335 (3)C11—H11A0.9600
C5—C61.354 (3)C11—H11B0.9600
C5—H50.9300C11—H11C0.9600
C6—C71.414 (2)N4—H40.89 (3)
C6—H60.9300
S2—Ni1—S2i180.00 (4)C9—C8—C7120.37 (17)
S2—Ni1—S192.200 (14)C9—C8—H8119.8
S2i—Ni1—S187.800 (14)C7—C8—H8119.8
S2—Ni1—S1i87.800 (14)N4—C9—C8121.51 (18)
S2i—Ni1—S1i92.200 (14)N4—C9—H9119.2
S1—Ni1—S1i180.00 (2)C8—C9—H9119.2
C1—S1—Ni1103.03 (5)N3—C10—H10A109.5
C2—S2—Ni1103.11 (5)N3—C10—H10B109.5
C2—C1—C4120.26 (13)H10A—C10—H10B109.5
C2—C1—S1120.95 (12)N3—C10—H10C109.5
C4—C1—S1118.78 (11)H10A—C10—H10C109.5
C1—C2—C3121.12 (14)H10B—C10—H10C109.5
C1—C2—S2120.69 (12)N3—C11—H11A109.5
C3—C2—S2118.19 (11)N3—C11—H11B109.5
N2—C3—C2179.0 (2)H11A—C11—H11B109.5
N1—C4—C1179.03 (19)N3—C11—H11C109.5
N4—C5—C6121.62 (18)H11A—C11—H11C109.5
N4—C5—H5119.2H11B—C11—H11C109.5
C6—C5—H5119.2C7—N3—C10121.84 (15)
C5—C6—C7120.49 (18)C7—N3—C11121.77 (15)
C5—C6—H6119.8C10—N3—C11116.30 (15)
C7—C6—H6119.8C9—N4—C5120.39 (16)
N3—C7—C6122.23 (15)C9—N4—H4120.9 (18)
N3—C7—C8122.16 (16)C5—N4—H4118.6 (18)
C6—C7—C8115.61 (15)
S2—Ni1—S1—C1−0.14 (5)N4—C5—C6—C70.4 (3)
S2i—Ni1—S1—C1179.86 (5)C5—C6—C7—N3178.82 (16)
S1—Ni1—S2—C20.74 (6)C5—C6—C7—C8−0.9 (3)
S1i—Ni1—S2—C2−179.26 (6)N3—C7—C8—C9−179.04 (17)
Ni1—S1—C1—C2−0.76 (14)C6—C7—C8—C90.7 (3)
Ni1—S1—C1—C4179.09 (11)C7—C8—C9—N40.1 (3)
C4—C1—C2—C31.4 (2)C6—C7—N3—C10−175.46 (16)
S1—C1—C2—C3−178.76 (13)C8—C7—N3—C104.3 (3)
C4—C1—C2—S2−178.27 (12)C6—C7—N3—C111.0 (2)
S1—C1—C2—S21.57 (19)C8—C7—N3—C11−179.29 (16)
Ni1—S2—C2—C1−1.46 (14)C8—C9—N4—C5−0.7 (3)
Ni1—S2—C2—C3178.86 (12)C6—C5—N4—C90.4 (3)
Symmetry codes: (i) −x, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4···N1ii0.89 (3)2.34 (3)3.040 (2)135 (2)
Symmetry codes: (ii) x, −y+1/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4···N1i0.89 (3)2.34 (3)3.040 (2)135 (2)
Symmetry codes: (i) x, −y+1/2, z−1/2.
Acknowledgements top

The authors thank the President's Science Foundation of South China Agricultural University (No. 2005 K092) for financial support.

references
References top

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Robertson, N. & Cronin, L. (2002). Coord. Chem. Rev. 227, 93–127.

Sheldrick, G. M. (2000). SHELXTL. Version 5.0. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.

Zhou, H. & Ren, X.-M. (2006). Acta Cryst. E62, m1119–m1121.