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Acta Cryst. (2007). E63, m1762    [ doi:10.1107/S1600536807025251 ]

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

C.-W. Feng, X.-R. Li, Y. Hou and C.-L. Ni

Abstract top

A new ion-pair complex, (C14H17N2)2[Ni(C4N2S2)2] or (BzDMAP)2[Ni(i-mnt)2], where BzDMAP is 1-benzyl-4-(dimethylamino)pyridinium and i-mnt is 2,2-dicyanoethylene-1,1-dithiolate, has been prepared. The [Ni(i-mnt)2]2- anion, which is located on an inversion center, exhibits a planar structure. The crystal packing is governed by short C-H...N and C-H...S contacts between anions and cations and by [pi]-[pi] stacking interactions between the phenyl groups of the cations (the centroid-centroid distance is 3.802 Å; symmetry code: -x + 2, -y + 2, -z).

Comment top

As shown in Fig.1 the asymmetric unit of the title compound consists of one [BzDMAP]+ cation and one-half of Ni(i-mnt)2 anion located on an inversion center. The nickel(II) ion is coordinated by four S atoms from two i-mnt ligands and the complex anion Ni(i-mnt)2 is in square planar configuration. The [BzDMAP]+ cation adopts a conformation where both the phenyl ring and the pyridine rings are twisted with respect to the C10\C11\N3 reference plane with the dihedral angles of 86.4 (3) and 89.7 (3)°, respectively.

Molecules are linked by C—H···N and C—H···S hydrogen bonds between anions and cations and π···π stacking interaction between cations (Fig. 2).

Related literature top

For the i-mnt complex of square-planar geometry with substituted pyridinium as counter-ion, see: Liu et al. (2006).

Experimental top

The title compound was prepared by the direct reaction of NiCl2.6H2O, K2(i-mnt)and (BzDMAP)Br in methanol. The brown block single crystals were obtained by slow evaporation of a CH3CN solution at room temperature for about two weeks.

Refinement top

All H atoms were placed in geometrically calculated positions (C—H = 0.93–0.97 Å) and refined as riding on their parent atoms with Uiso = 1.2 Ueq(C)

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 molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. The packing of the title compound viewed down the c axis. Hydrogen atoms have been omitted for clarity.
Bis[1-benzyl-4-(dimethylamino)pyridinium] bis(2,2-dicyanoethylene-1,1-dithiolato-κ2S,S')nickelate(II) top
Crystal data top
(C14H17N2)2[Ni(C4N2S2)2]Z = 1
Mr = 765.66F(000) = 398
Triclinic, P1Dx = 1.377 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.0456 (12) ÅCell parameters from 2430 reflections
b = 9.6829 (15) Åθ = 2.3–26.9°
c = 13.202 (2) ŵ = 0.79 mm−1
α = 76.134 (2)°T = 291 K
β = 78.312 (2)°Block, brown
γ = 68.834 (2)°0.38 × 0.22 × 0.20 mm
V = 923.5 (2) Å3
Data collection top
Bruker SMART APEX CCD
diffractometer		3180 independent reflections
Radiation source: fine-focus sealed tube2431 reflections with I > 2σ(I)
graphiteRint = 0.019
φ and ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −5→9
Tmin = 0.798, Tmax = 0.858k = −11→11
4642 measured reflectionsl = −14→15
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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.08P)2]
where P = (Fo2 + 2Fc2)/3
3180 reflections(Δ/σ)max = 0.001
225 parametersΔρmax = 0.40 e Å−3
0 restraintsΔρmin = −0.21 e Å−3
Crystal data top
(C14H17N2)2[Ni(C4N2S2)2]γ = 68.834 (2)°
Mr = 765.66V = 923.5 (2) Å3
Triclinic, P1Z = 1
a = 8.0456 (12) ÅMo Kα radiation
b = 9.6829 (15) ŵ = 0.79 mm−1
c = 13.202 (2) ÅT = 291 K
α = 76.134 (2)°0.38 × 0.22 × 0.20 mm
β = 78.312 (2)°
Data collection top
Bruker SMART APEX CCD
diffractometer		3180 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		2431 reflections with I > 2σ(I)
Tmin = 0.798, Tmax = 0.858Rint = 0.019
4642 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.128Δρmax = 0.40 e Å−3
S = 1.07Δρmin = −0.21 e Å−3
3180 reflectionsAbsolute structure: ?
225 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.50000.00000.50000.0519 (2)
S10.37050 (10)0.05129 (8)0.35743 (6)0.0583 (2)
S20.63405 (10)0.15279 (9)0.39411 (6)0.0613 (2)
N10.2591 (4)0.2793 (3)0.0912 (2)0.0764 (8)
N20.6676 (5)0.4409 (4)0.1454 (2)0.0951 (10)
N30.8270 (3)0.6225 (3)0.25242 (19)0.0604 (6)
N40.8293 (3)0.3522 (3)0.5458 (2)0.0673 (7)
C10.4950 (3)0.1708 (3)0.3041 (2)0.0499 (6)
C20.4823 (4)0.2637 (3)0.2104 (2)0.0525 (7)
C30.3600 (4)0.2714 (3)0.1435 (2)0.0566 (7)
C40.5878 (4)0.3613 (3)0.1738 (2)0.0634 (8)
C51.1483 (5)0.7158 (4)0.0913 (2)0.0750 (9)
H51.17620.62170.07390.090*
C61.2810 (5)0.7788 (5)0.0786 (3)0.0907 (11)
H61.39800.72710.05270.109*
C71.2422 (6)0.9167 (5)0.1037 (3)0.0901 (11)
H71.33280.95820.09580.108*
C81.0716 (6)0.9932 (4)0.1402 (3)0.0893 (11)
H81.04481.08810.15600.107*
C90.9375 (5)0.9307 (4)0.1541 (3)0.0746 (9)
H90.82100.98310.18020.089*
C100.9749 (4)0.7903 (3)0.1295 (2)0.0611 (7)
C110.8306 (5)0.7209 (4)0.1471 (2)0.0785 (10)
H11A0.71510.79980.14160.094*
H11B0.85140.66190.09310.094*
C120.9269 (4)0.4776 (4)0.2663 (2)0.0625 (8)
H120.99520.43790.20770.075*
C130.9340 (4)0.3853 (3)0.3610 (2)0.0616 (7)
H131.00740.28510.36660.074*
C140.8300 (4)0.4407 (3)0.4516 (2)0.0564 (7)
C150.7280 (4)0.5943 (4)0.4341 (2)0.0678 (8)
H150.65740.63830.49050.081*
C160.7305 (4)0.6790 (4)0.3371 (3)0.0709 (8)
H160.66250.78070.32860.085*
C170.7161 (5)0.4124 (5)0.6370 (3)0.0962 (12)
H17A0.74330.49770.64480.144*
H17B0.73850.33620.69910.144*
H17C0.59200.44280.62730.144*
C180.9379 (5)0.1947 (4)0.5619 (3)0.0876 (10)
H18A0.90620.14390.51840.131*
H18B0.91700.15000.63440.131*
H18C1.06260.18570.54350.131*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0539 (3)0.0459 (3)0.0456 (3)−0.0108 (2)−0.0076 (2)0.0030 (2)
S10.0626 (5)0.0545 (4)0.0535 (5)−0.0221 (4)−0.0120 (3)0.0065 (3)
S20.0632 (5)0.0658 (5)0.0522 (5)−0.0248 (4)−0.0151 (3)0.0064 (3)
N10.089 (2)0.090 (2)0.0581 (17)−0.0432 (17)−0.0213 (15)0.0035 (14)
N20.132 (3)0.105 (2)0.072 (2)−0.080 (2)−0.0298 (18)0.0162 (17)
N30.0685 (15)0.0629 (16)0.0529 (15)−0.0263 (13)−0.0175 (11)−0.0009 (12)
N40.0744 (17)0.0784 (18)0.0507 (15)−0.0310 (15)−0.0118 (12)−0.0019 (13)
C10.0479 (15)0.0435 (14)0.0522 (16)−0.0072 (12)−0.0036 (11)−0.0120 (13)
C20.0577 (16)0.0528 (16)0.0461 (16)−0.0195 (13)−0.0048 (12)−0.0065 (13)
C30.0696 (19)0.0539 (17)0.0424 (16)−0.0255 (15)−0.0019 (14)0.0022 (13)
C40.081 (2)0.0644 (19)0.0468 (17)−0.0340 (18)−0.0112 (14)0.0042 (14)
C50.102 (3)0.0560 (18)0.0533 (19)−0.0225 (19)0.0051 (17)−0.0027 (15)
C60.086 (3)0.093 (3)0.061 (2)−0.018 (2)0.0101 (18)0.010 (2)
C70.101 (3)0.096 (3)0.074 (3)−0.051 (3)−0.011 (2)0.011 (2)
C80.123 (3)0.072 (2)0.079 (3)−0.044 (2)−0.015 (2)−0.007 (2)
C90.079 (2)0.061 (2)0.067 (2)−0.0103 (17)−0.0073 (16)−0.0047 (16)
C100.079 (2)0.0591 (18)0.0398 (15)−0.0207 (16)−0.0159 (13)0.0036 (13)
C110.099 (3)0.085 (2)0.058 (2)−0.037 (2)−0.0327 (17)0.0049 (17)
C120.0691 (19)0.0636 (19)0.0571 (19)−0.0233 (16)−0.0019 (14)−0.0182 (15)
C130.0631 (18)0.0534 (17)0.0622 (19)−0.0143 (14)−0.0066 (14)−0.0082 (15)
C140.0563 (16)0.0635 (18)0.0546 (18)−0.0243 (14)−0.0109 (13)−0.0099 (14)
C150.071 (2)0.066 (2)0.059 (2)−0.0138 (16)−0.0022 (15)−0.0158 (16)
C160.071 (2)0.0573 (19)0.075 (2)−0.0087 (16)−0.0132 (16)−0.0118 (17)
C170.108 (3)0.132 (4)0.051 (2)−0.050 (3)−0.0025 (19)−0.012 (2)
C180.106 (3)0.075 (2)0.078 (2)−0.033 (2)−0.030 (2)0.0153 (19)
Geometric parameters (Å, °) top
Ni1—S1i2.2019 (8)C7—H70.9300
Ni1—S12.2019 (8)C8—C91.379 (5)
Ni1—S2i2.2037 (8)C8—H80.9300
Ni1—S22.2037 (8)C9—C101.385 (4)
S1—C11.732 (3)C9—H90.9300
S2—C11.730 (3)C10—C111.495 (4)
N1—C31.140 (4)C11—H11A0.9700
N2—C41.126 (4)C11—H11B0.9700
N3—C121.330 (4)C12—C131.350 (4)
N3—C161.337 (4)C12—H120.9300
N3—C111.487 (4)C13—C141.413 (4)
N4—C141.331 (4)C13—H130.9300
N4—C181.446 (4)C14—C151.404 (4)
N4—C171.459 (4)C15—C161.346 (4)
C1—C21.342 (4)C15—H150.9300
C2—C31.421 (4)C16—H160.9300
C2—C41.429 (4)C17—H17A0.9600
C5—C101.372 (4)C17—H17B0.9600
C5—C61.375 (5)C17—H17C0.9600
C5—H50.9300C18—H18A0.9600
C6—C71.364 (5)C18—H18B0.9600
C6—H60.9300C18—H18C0.9600
C7—C81.354 (5)
S1i—Ni1—S1180.0C5—C10—C9118.3 (3)
S1i—Ni1—S2i78.96 (3)C5—C10—C11121.2 (3)
S1—Ni1—S2i101.04 (3)C9—C10—C11120.5 (3)
S1i—Ni1—S2101.04 (3)N3—C11—C10111.0 (2)
S1—Ni1—S278.96 (3)N3—C11—H11A109.4
S2i—Ni1—S2180.00 (3)C10—C11—H11A109.4
C1—S1—Ni186.41 (10)N3—C11—H11B109.4
C1—S2—Ni186.40 (10)C10—C11—H11B109.4
C12—N3—C16118.0 (3)H11A—C11—H11B108.0
C12—N3—C11121.1 (3)N3—C12—C13123.3 (3)
C16—N3—C11120.8 (3)N3—C12—H12118.3
C14—N4—C18122.0 (3)C13—C12—H12118.3
C14—N4—C17120.3 (3)C12—C13—C14120.1 (3)
C18—N4—C17117.7 (3)C12—C13—H13120.0
C2—C1—S2126.1 (2)C14—C13—H13120.0
C2—C1—S1125.8 (2)N4—C14—C15123.2 (3)
S2—C1—S1108.02 (16)N4—C14—C13121.9 (3)
C1—C2—C3121.3 (3)C15—C14—C13115.0 (3)
C1—C2—C4121.9 (3)C16—C15—C14121.1 (3)
C3—C2—C4116.8 (3)C16—C15—H15119.4
N1—C3—C2178.6 (3)C14—C15—H15119.4
N2—C4—C2178.4 (4)N3—C16—C15122.5 (3)
C10—C5—C6120.6 (3)N3—C16—H16118.7
C10—C5—H5119.7C15—C16—H16118.7
C6—C5—H5119.7N4—C17—H17A109.5
C7—C6—C5120.4 (4)N4—C17—H17B109.5
C7—C6—H6119.8H17A—C17—H17B109.5
C5—C6—H6119.8N4—C17—H17C109.5
C8—C7—C6120.0 (4)H17A—C17—H17C109.5
C8—C7—H7120.0H17B—C17—H17C109.5
C6—C7—H7120.0N4—C18—H18A109.5
C7—C8—C9120.2 (4)N4—C18—H18B109.5
C7—C8—H8119.9H18A—C18—H18B109.5
C9—C8—H8119.9N4—C18—H18C109.5
C8—C9—C10120.5 (3)H18A—C18—H18C109.5
C8—C9—H9119.7H18B—C18—H18C109.5
C10—C9—H9119.7
Symmetry codes: (i) −x+1, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C11—H11B···N1ii0.972.623.368 (4)134
C12—H12···N1iii0.932.593.477 (4)161
C16—H16···S1iv0.932.863.750 (4)160
Symmetry codes: (ii) −x+1, −y+1, −z; (iii) x+1, y, z; (iv) x, y+1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C11—H11B···N1i0.972.623.368 (4)134
C12—H12···N1ii0.932.593.477 (4)161
C16—H16···S1iii0.932.863.750 (4)160
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x+1, y, z; (iii) x, y+1, z.
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 (2000). SHELXTL. Version 5.0. Bruker AXS Inc., Madison, Wisconsin, USA.

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

Liu, M.-G., Li, X.-Y., Lin, L.-F. & Ni, C.-L. (2006). Acta Cryst. E62, m2919–m2921.

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