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Acta Cryst. (2013). E69, m59    [ doi:10.1107/S1600536812050623 ]

Bis(4,4'-sulfanediyldipyridinium) tetrachloridonickelate(II) dichloride

J. Werner, I. Jess and C. Näther

Abstract top

In the title compound, (C10H10N2S)2[NiCl4]Cl2, the Ni2+ cation is tetrahedrally coordinated by four chloride anions. Two 4,4'-sulfanediyldipyridinium cations and two non-coordinating chloride anions are connected via N-H...Cl hydrogen-bonding interactions into 20-membered rings, in the middle of which are situated the [NiCl4]2- complex anions. These rings are stacked in the b-axis direction. The Ni2+ cation is located on a twofold rotation axis, whereas the chloride anions and the 4,4'-sulfanediyldipyridinium cations occupy general positions.

Comment top

The title compound was prepared within a project on the synthesis and properties of transition metal thiocyanato coordination polymers (Boeckmann & Näther, 2010, 2011; Wöhlert et al., 2011). During our attempts to prepare a one-dimensional coordination polymer based on 4-chloropyridine as a co-ligand, crystals of the title compound, (C10H10N2S+)2[NiCl4]Cl2 (I), have been obtained accidentally and were characterized by single crystal X-ray diffraction.

In the crystal structure of (I) the Ni2+ cation is coordinated by four chloride anions within a slightly distorted tetrahedral coordination environment. The complex [NiCl4]2- anions are surrounded by two 4,4'-sulfanediyldipyridinium cations and two chloride counter-anions (Fig. 1 and Table 1). Intermolecular N—H···Cl hydrogen bonding is found between the 4,4'-sulfanediyldipyridinium cations and the non-coordinating chloride anions, which leads to the formation of 20-membered rings (Fig. 2 and Table 2). These rings are stacked in the direction of the b axis.

The dihedral angle between the pyridine rings in the cations amounts to 52.57 (7) °. The corresponding bond lengths and angles are comparable to those in the neutral 4,4'-thiodipyridine molecule. Slight differences are found with respect to the dihedral angle between the pyridine rings which amounts to 65.4° in the neutral molecule (Vaganova et al., 2004).

Related literature top

For background information on this project, see: Boeckmann & Näther (2010, 2011); Wöhlert et al. (2011). For the crystal structure of 4,4'-thiodipyridine, see: Vaganova et al. (2004).

Experimental top

Barium thiocyanate trihydrate and 4-chloropyridine hydrochloride were purchased from Alfa Aesar, Ni(SO4)2.6H2O was obtained from Merck. Ni(NCS)2 was prepared by stirring Ba(NCS)2.3H2O (17.5 g, 56.9 mmol) and NiSO4.6H2O (15.0 g, 57 mmol) in water (500 mL). The white residue of BaSO4 was filtered off and the solution evaporated using a rotary evaporator. The homogeneity of the product was investigated by X-ray powder diffraction. The title compound was prepared by the reaction of 26.2 mg Ni(NCS)2 (0.15 mmol) and 97.5 mg 4-chloropyridine hydrochloride (0.60 mmol) in 1.5 mL ethanol at 354 K in a closed 10 mL glas culture tube. After one day blue needles of the title compound were obtained. The formation of 4,4'-thiodipyridine starting from 4-chloropyridine in an SCN--containing environment and the presence of free Cl- and complex [NiCl4]2- anions seem to be a result of cleavage reactions of both the 4-chloropyridine and SCN- anions. However, the exact mechanism is unclear.

Refinement top

The aromatic H atoms (C- and N-bound) were located in a difference map but were positioned with idealized geometries and were refined isotropically with Uiso(H) = 1.2.Ueq(C,N) using a riding model approximation with C—H = 0.95 Å and N—H = 0.88 Å.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry code: i = -x+1, y, -z+3/2.]
[Figure 2] Fig. 2. Crystal structure of the title compound in a view along the b-axis. N—H···Cl hydrogen bonding is shown as dashed lines.
Bis(4,4'-sulfanediyldipyridinium) tetrachloridonickelate(II) dichloride top
Crystal data top
(C10H10N2S)2[NiCl4]Cl2F(000) = 1320
Mr = 651.93Dx = 1.588 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 10707 reflections
a = 19.0497 (9) Åθ = 2.3–27.9°
b = 8.0534 (5) ŵ = 1.47 mm1
c = 17.7883 (11) ÅT = 200 K
β = 92.368 (6)°Needle, blue
V = 2726.7 (3) Å30.32 × 0.13 × 0.07 mm
Z = 4
Data collection top
Stoe IPDS-1
diffractometer
3162 independent reflections
Radiation source: fine-focus sealed tube2308 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.062
Phi scansθmax = 27.9°, θmin = 2.3°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
h = 2322
Tmin = 0.789, Tmax = 0.899k = 1010
10707 measured reflectionsl = 2323
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)] = 0.037H-atom parameters constrained
wR(F2) = 0.084 w = 1/[σ2(Fo2) + (0.0463P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.001
3162 reflectionsΔρmax = 0.47 e Å3
151 parametersΔρmin = 0.43 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0013 (3)
Crystal data top
(C10H10N2S)2[NiCl4]Cl2V = 2726.7 (3) Å3
Mr = 651.93Z = 4
Monoclinic, C2/cMo Kα radiation
a = 19.0497 (9) ŵ = 1.47 mm1
b = 8.0534 (5) ÅT = 200 K
c = 17.7883 (11) Å0.32 × 0.13 × 0.07 mm
β = 92.368 (6)°
Data collection top
Stoe IPDS-1
diffractometer
3162 independent reflections
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
2308 reflections with I > 2σ(I)
Tmin = 0.789, Tmax = 0.899Rint = 0.062
10707 measured reflectionsθmax = 27.9°
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.084Δρmax = 0.47 e Å3
S = 0.99Δρmin = 0.43 e Å3
3162 reflectionsAbsolute structure: ?
151 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.50000.66427 (5)0.75000.02527 (13)
Cl10.59273 (4)0.81985 (9)0.71816 (4)0.0465 (2)
Cl20.55194 (4)0.49082 (8)0.83619 (3)0.03563 (17)
Cl30.75812 (4)0.08791 (10)0.90585 (4)0.04236 (19)
N10.73877 (13)0.1738 (3)0.73764 (14)0.0425 (6)
H1N10.76370.15820.77980.051*
C10.76591 (16)0.1281 (4)0.67229 (18)0.0424 (7)
H10.81210.08390.67180.051*
C20.72674 (14)0.1451 (3)0.60598 (16)0.0366 (6)
H20.74440.10730.55980.044*
C30.66077 (14)0.2189 (3)0.60792 (14)0.0305 (5)
C40.63496 (14)0.2699 (3)0.67604 (14)0.0319 (5)
H40.59050.32270.67790.038*
C50.67510 (14)0.2424 (3)0.74071 (15)0.0351 (6)
H50.65750.27240.78800.042*
S10.61640 (4)0.26112 (10)0.52047 (4)0.03808 (18)
N20.38935 (13)0.1530 (3)0.55137 (14)0.0394 (5)
H1N20.34430.13510.55700.047*
C60.40903 (15)0.2520 (4)0.49540 (15)0.0383 (6)
H60.37460.29860.46150.046*
C70.47845 (14)0.2859 (3)0.48701 (14)0.0313 (5)
H70.49260.35730.44790.038*
C80.52829 (13)0.2148 (3)0.53643 (13)0.0262 (5)
C90.50641 (14)0.1074 (3)0.59261 (14)0.0284 (5)
H90.53980.05410.62570.034*
C100.43635 (15)0.0807 (3)0.59898 (15)0.0357 (6)
H100.42060.01000.63760.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0281 (3)0.0202 (2)0.0271 (2)0.0000.00296 (16)0.000
Cl10.0355 (4)0.0461 (4)0.0574 (4)0.0070 (3)0.0039 (3)0.0256 (3)
Cl20.0370 (4)0.0359 (3)0.0341 (3)0.0052 (3)0.0038 (2)0.0137 (3)
Cl30.0275 (4)0.0549 (4)0.0440 (4)0.0065 (3)0.0057 (3)0.0111 (3)
N10.0347 (15)0.0451 (13)0.0462 (14)0.0034 (11)0.0153 (10)0.0021 (11)
C10.0290 (17)0.0392 (16)0.0586 (19)0.0058 (11)0.0034 (12)0.0004 (13)
C20.0266 (15)0.0371 (15)0.0462 (15)0.0021 (11)0.0050 (10)0.0019 (12)
C30.0248 (14)0.0302 (12)0.0365 (13)0.0030 (9)0.0002 (9)0.0021 (10)
C40.0256 (14)0.0339 (13)0.0359 (13)0.0016 (10)0.0006 (9)0.0040 (10)
C50.0351 (16)0.0326 (13)0.0372 (14)0.0001 (11)0.0035 (10)0.0023 (11)
S10.0278 (4)0.0548 (4)0.0316 (3)0.0045 (3)0.0014 (2)0.0041 (3)
N20.0240 (13)0.0422 (13)0.0520 (14)0.0035 (10)0.0005 (9)0.0154 (11)
C60.0339 (16)0.0375 (14)0.0421 (15)0.0076 (12)0.0139 (11)0.0110 (12)
C70.0360 (16)0.0305 (13)0.0269 (12)0.0033 (10)0.0051 (9)0.0018 (9)
C80.0265 (13)0.0239 (11)0.0280 (11)0.0017 (9)0.0005 (9)0.0082 (9)
C90.0282 (14)0.0236 (11)0.0330 (12)0.0000 (9)0.0039 (9)0.0021 (9)
C100.0384 (17)0.0292 (13)0.0397 (14)0.0060 (11)0.0038 (11)0.0047 (11)
Geometric parameters (Å, º) top
Ni1—Cl12.2569 (7)C4—H40.9500
Ni1—Cl1i2.2569 (7)C5—H50.9500
Ni1—Cl2i2.2706 (7)S1—C81.754 (3)
Ni1—Cl22.2706 (6)N2—C101.340 (4)
N1—C51.336 (4)N2—C61.341 (4)
N1—C11.343 (4)N2—H1N20.8800
N1—H1N10.8800C6—C71.365 (4)
C1—C21.376 (4)C6—H60.9500
C1—H10.9500C7—C81.391 (3)
C2—C31.392 (4)C7—H70.9500
C2—H20.9500C8—C91.398 (3)
C3—C41.389 (4)C9—C101.361 (4)
C3—S11.772 (3)C9—H90.9500
C4—C51.373 (4)C10—H100.9500
Cl1—Ni1—Cl1i112.56 (5)N1—C5—H5119.7
Cl1—Ni1—Cl2i119.73 (3)C4—C5—H5119.7
Cl1i—Ni1—Cl2i100.79 (2)C8—S1—C3104.00 (12)
Cl1—Ni1—Cl2100.79 (2)C10—N2—C6121.9 (3)
Cl1i—Ni1—Cl2119.73 (3)C10—N2—H1N2119.1
Cl2i—Ni1—Cl2104.07 (4)C6—N2—H1N2119.1
C5—N1—C1122.1 (2)N2—C6—C7120.1 (2)
C5—N1—H1N1119.0N2—C6—H6119.9
C1—N1—H1N1119.0C7—C6—H6119.9
N1—C1—C2120.0 (3)C6—C7—C8119.2 (3)
N1—C1—H1120.0C6—C7—H7120.4
C2—C1—H1120.0C8—C7—H7120.4
C1—C2—C3118.7 (3)C7—C8—C9119.4 (2)
C1—C2—H2120.7C7—C8—S1116.3 (2)
C3—C2—H2120.7C9—C8—S1124.26 (19)
C4—C3—C2120.0 (2)C10—C9—C8118.6 (2)
C4—C3—S1122.4 (2)C10—C9—H9120.7
C2—C3—S1117.3 (2)C8—C9—H9120.7
C5—C4—C3118.6 (3)N2—C10—C9120.7 (3)
C5—C4—H4120.7N2—C10—H10119.7
C3—C4—H4120.7C9—C10—H10119.7
N1—C5—C4120.5 (3)
Symmetry code: (i) x+1, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H1N2···Cl3i0.882.122.987 (3)168
N1—H1N1···Cl30.882.323.078 (3)144
Symmetry code: (i) x+1, y, z+3/2.
Selected bond lengths (Å) top
Ni1—Cl12.2569 (7)Ni1—Cl22.2706 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H1N2···Cl3i0.882.122.987 (3)168.3
N1—H1N1···Cl30.882.323.078 (3)144.4
Symmetry code: (i) x+1, y, z+3/2.
Acknowledgements top

We gratefully acknowledge financial support by the DFG (project No. NA 720/3–1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

references
References top

Boeckmann, J. & Näther, C. (2010). Dalton Trans. 39, 11019–11026.

Boeckmann, J. & Näther, C. (2011). Chem. Commun. 47, 7104–7106.

Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.

Vaganova, E., Wachtel, E., Rozenberg, H., Khodorkovsky, V., Leitus, V., Shimon, L., Reich, S. & Yitzchaik, S. (2004). Chem. Mater. 16, 3976–3979.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.

Wöhlert, S., Boeckmann, J., Wriedt, M. & Näther, C. (2011). Angew. Chem. Int. Ed. 50, 6920–6923.