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accessPoly[bis(acetonitrile-κN)di-μ-thiocyanato-κ2N,S;κ2S,N-nickel(II)]
aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Strasse 2, 24098 Kiel, Germany
*Correspondence e-mail: swoehlert@ac.uni-kiel.de
In the title compound, [Ni(NCS)2(CH3CN)2]n, the NiII cation is coordinated by two N-bonded and two S-bonded thiocyanate anions, as well as two acetonitrile molecules in an octahedral NiN4S2 coordination mode. The comprises one nickel cation, two thiocyanate anions and two actonitrile molecules. In the crystal, the NiII cations are connected by bridging thiocyanate anions into a three-dimensional coordination network.
Related literature
For background of this work see: Boeckmann & Näther (2010![[Boeckmann, J. & Näther, C. (2010). Dalton Trans. pp. 11019-11026.]](../../../../../../logos/arrows/e_arr.gif "Boeckmann, J. & Näther, C. (2010). Dalton Trans. pp. 11019-11026.")
); Wriedt et al. (2009a,b).
![[Scheme 1]](im2264scheme1.gif)
Experimental
Crystal data
|
Data collection: X-AREA (Stoe & Cie, 2008); cell X-AREA; data reduction: X-AREA; 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, 1999); software used to prepare material for publication: XCIF in SHELXTL.
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536811004132/im2264sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536811004132/im2264Isup2.hkl
Ni(NCS)2 was obtained from Alfa Aesar and trans-1,2-bis(4-pyridyl)-ethylene (bpe) was obtained from Sigma Aldrich. All chemicals were used without further purification. 0.6 mmol (104.7 mg) Ni(NCS)2 and 0.15 mmol (28.2 mg) bpe were reacted with 1 ml acetonitrile in a closed test-tube at 120°C for three days. On cooling blue block-shaped single crystals of the title compound were obtained in a mixture with a unknown phase. It must be noted, that the reaction without bpe does not lead to the formation of the title compound.
H atoms were positioned with idealized geometry, allowed to rotate but not to tip and were refined isotropically with Uiso(H) = 1.5Ueq(C) and C—H distances of 0.96 Å using a riding model. The was determined on the basis of 1127 Friedel pairs.
Data collection: X-AREA (Stoe & Cie, 2008); cell 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, 1999); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008).
![[Figure 1]](./im2264fig1thm.gif) | Fig. 1. Crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 30 % probability level. Symmetry codes: i = x-1/2, -y+3/2, -z+1; ii = -x, y-1/2, -z+3/2. |
![[Figure 2]](./im2264fig2thm.gif) | Fig. 2. Crystal structure of the title compound approximately viewed along the crystallographic b-axis. |
| [Ni(NCS)2(C2H3N)2] | F(000) = 520 |
| Mr = 256.98 | Dx = 1.710 Mg m−3 |
| Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2ac 2ab | Cell parameters from 11157 reflections |
| a = 9.0666 (4) Å | θ = 2.8–29.2° |
| b = 9.1215 (3) Å | µ = 2.32 mm−1 |
| c = 12.0696 (6) Å | T = 293 K |
| V = 998.17 (7) Å3 | Block, blue |
| Z = 4 | 0.11 × 0.09 × 0.06 mm |
| Stoe IPDS-2 diffractometer | 2694 independent reflections |
| Radiation source: fine-focus sealed tube | 2479 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.023 |
| ω scans | θmax = 29.2°, θmin = 2.8° |
| Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008) | h = −12→10 |
| Tmin = 0.683, Tmax = 0.772 | k = −12→12 |
| 11157 measured reflections | l = −16→16 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
| wR(F2) = 0.051 | w = 1/[σ2(Fo2) + (0.0221P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.29 | (Δ/σ)max = 0.001 |
| 2694 reflections | Δρmax = 0.29 e Å−3 |
| 120 parameters | Δρmin = −0.28 e Å−3 |
| 0 restraints | Absolute structure: Flack (1983), 1127 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.003 (13) |
| [Ni(NCS)2(C2H3N)2] | V = 998.17 (7) Å3 |
| Mr = 256.98 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα radiation |
| a = 9.0666 (4) Å | µ = 2.32 mm−1 |
| b = 9.1215 (3) Å | T = 293 K |
| c = 12.0696 (6) Å | 0.11 × 0.09 × 0.06 mm |
| Stoe IPDS-2 diffractometer | 2694 independent reflections |
| Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008) | 2479 reflections with I > 2σ(I) |
| Tmin = 0.683, Tmax = 0.772 | Rint = 0.023 |
| 11157 measured reflections |
| R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
| wR(F2) = 0.051 | Δρmax = 0.29 e Å−3 |
| S = 1.29 | Δρmin = −0.28 e Å−3 |
| 2694 reflections | Absolute structure: Flack (1983), 1127 Friedel pairs |
| 120 parameters | Absolute structure parameter: −0.003 (13) |
| 0 restraints |
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. |
| x | y | z | Uiso*/Ueq | ||
| Ni1 | −0.10172 (3) | 0.83322 (3) | 0.62898 (2) | 0.02615 (6) | |
| N1 | −0.0070 (2) | 1.0335 (2) | 0.63730 (18) | 0.0388 (4) | |
| C1 | 0.0391 (2) | 1.1504 (3) | 0.64845 (15) | 0.0307 (4) | |
| S1 | 0.10459 (8) | 1.31745 (6) | 0.66142 (4) | 0.03781 (12) | |
| N2 | 0.0983 (2) | 0.7362 (2) | 0.61691 (15) | 0.0356 (4) | |
| C2 | 0.2172 (2) | 0.6972 (2) | 0.60194 (15) | 0.0283 (4) | |
| S2 | 0.38867 (6) | 0.64753 (7) | 0.58006 (4) | 0.03776 (13) | |
| N3 | −0.2036 (2) | 0.6293 (2) | 0.62176 (17) | 0.0341 (4) | |
| C3 | −0.2491 (2) | 0.5139 (3) | 0.6242 (2) | 0.0335 (4) | |
| C4 | −0.3109 (3) | 0.3669 (3) | 0.6278 (3) | 0.0468 (6) | |
| H4A | −0.4134 | 0.3723 | 0.6472 | 0.070* | |
| H4B | −0.2593 | 0.3098 | 0.6823 | 0.070* | |
| H4C | −0.3007 | 0.3215 | 0.5565 | 0.070* | |
| N4 | −0.3065 (2) | 0.9326 (2) | 0.63801 (17) | 0.0365 (4) | |
| C5 | −0.4170 (2) | 0.9893 (2) | 0.63197 (19) | 0.0344 (4) | |
| C6 | −0.5579 (3) | 1.0633 (3) | 0.6230 (3) | 0.0452 (5) | |
| H6A | −0.5743 | 1.1215 | 0.6881 | 0.068* | |
| H6B | −0.6351 | 0.9920 | 0.6161 | 0.068* | |
| H6C | −0.5575 | 1.1256 | 0.5589 | 0.068* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ni1 | 0.02348 (10) | 0.02426 (11) | 0.03072 (11) | −0.00044 (11) | −0.00046 (11) | −0.00142 (9) |
| N1 | 0.0458 (11) | 0.0336 (10) | 0.0371 (9) | −0.0091 (8) | −0.0039 (10) | −0.0018 (9) |
| C1 | 0.0340 (9) | 0.0322 (11) | 0.0258 (9) | −0.0008 (9) | −0.0008 (7) | 0.0003 (8) |
| S1 | 0.0523 (3) | 0.0278 (3) | 0.0333 (2) | −0.0104 (3) | −0.0001 (2) | 0.00087 (19) |
| N2 | 0.0288 (7) | 0.0434 (9) | 0.0346 (9) | 0.0041 (9) | 0.0021 (10) | −0.0025 (7) |
| C2 | 0.0318 (9) | 0.0280 (10) | 0.0252 (8) | −0.0010 (8) | −0.0010 (7) | −0.0013 (7) |
| S2 | 0.0262 (2) | 0.0527 (3) | 0.0343 (2) | 0.0089 (3) | 0.0010 (2) | 0.0033 (2) |
| N3 | 0.0339 (8) | 0.0314 (10) | 0.0369 (9) | −0.0033 (7) | 0.0016 (9) | −0.0011 (9) |
| C3 | 0.0351 (9) | 0.0332 (11) | 0.0322 (9) | −0.0013 (8) | −0.0007 (9) | 0.0025 (9) |
| C4 | 0.0585 (15) | 0.0327 (12) | 0.0492 (13) | −0.0105 (11) | −0.0028 (14) | −0.0001 (12) |
| N4 | 0.0334 (9) | 0.0379 (10) | 0.0382 (9) | 0.0053 (8) | −0.0016 (9) | −0.0003 (9) |
| C5 | 0.0333 (10) | 0.0368 (10) | 0.0332 (9) | −0.0002 (9) | 0.0007 (10) | −0.0034 (9) |
| C6 | 0.0326 (10) | 0.0485 (13) | 0.0547 (14) | 0.0061 (10) | 0.0018 (12) | −0.0008 (13) |
| Ni1—N1 | 2.0210 (19) | S2—Ni1iv | 2.5305 (6) |
| Ni1—N2 | 2.0231 (18) | N3—C3 | 1.131 (3) |
| Ni1—N4 | 2.0685 (19) | C3—C4 | 1.454 (3) |
| Ni1—N3 | 2.0782 (18) | C4—H4A | 0.9600 |
| Ni1—S2i | 2.5305 (6) | C4—H4B | 0.9600 |
| Ni1—S1ii | 2.5341 (6) | C4—H4C | 0.9600 |
| N1—C1 | 1.154 (3) | N4—C5 | 1.130 (3) |
| C1—S1 | 1.643 (2) | C5—C6 | 1.449 (3) |
| S1—Ni1iii | 2.5341 (6) | C6—H6A | 0.9600 |
| N2—C2 | 1.149 (3) | C6—H6B | 0.9600 |
| C2—S2 | 1.641 (2) | C6—H6C | 0.9600 |
| N1—Ni1—N2 | 91.02 (8) | N2—C2—S2 | 178.0 (2) |
| N1—Ni1—N4 | 89.02 (8) | C2—S2—Ni1iv | 100.02 (7) |
| N2—Ni1—N4 | 178.89 (9) | C3—N3—Ni1 | 173.7 (2) |
| N1—Ni1—N3 | 178.69 (9) | N3—C3—C4 | 178.7 (3) |
| N2—Ni1—N3 | 90.23 (8) | C3—C4—H4A | 109.5 |
| N4—Ni1—N3 | 89.73 (8) | C3—C4—H4B | 109.5 |
| N1—Ni1—S2i | 90.09 (6) | H4A—C4—H4B | 109.5 |
| N2—Ni1—S2i | 89.40 (5) | C3—C4—H4C | 109.5 |
| N4—Ni1—S2i | 89.50 (6) | H4A—C4—H4C | 109.5 |
| N3—Ni1—S2i | 90.29 (6) | H4B—C4—H4C | 109.5 |
| N1—Ni1—S1ii | 90.35 (6) | C5—N4—Ni1 | 173.2 (2) |
| N2—Ni1—S1ii | 93.23 (6) | N4—C5—C6 | 179.2 (3) |
| N4—Ni1—S1ii | 87.88 (6) | C5—C6—H6A | 109.5 |
| N3—Ni1—S1ii | 89.22 (6) | C5—C6—H6B | 109.5 |
| S2i—Ni1—S1ii | 177.34 (2) | H6A—C6—H6B | 109.5 |
| C1—N1—Ni1 | 174.6 (2) | C5—C6—H6C | 109.5 |
| N1—C1—S1 | 178.77 (19) | H6A—C6—H6C | 109.5 |
| C1—S1—Ni1iii | 98.29 (7) | H6B—C6—H6C | 109.5 |
| C2—N2—Ni1 | 170.90 (18) |
| Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) −x, y−1/2, −z+3/2; (iii) −x, y+1/2, −z+3/2; (iv) x+1/2, −y+3/2, −z+1. |
Experimental details
| Crystal data | |
| Chemical formula | [Ni(NCS)2(C2H3N)2] |
| Mr | 256.98 |
| Crystal system, space group | Orthorhombic, P212121 |
| Temperature (K) | 293 |
| a, b, c (Å) | 9.0666 (4), 9.1215 (3), 12.0696 (6) |
| V (Å3) | 998.17 (7) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 2.32 |
| Crystal size (mm) | 0.11 × 0.09 × 0.06 |
| Data collection | |
| Diffractometer | Stoe IPDS2 diffractometer |
| Absorption correction | Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008) |
| Tmin, Tmax | 0.683, 0.772 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 11157, 2694, 2479 |
| Rint | 0.023 |
| (sin θ/λ)max (Å−1) | 0.686 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.051, 1.29 |
| No. of reflections | 2694 |
| No. of parameters | 120 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.29, −0.28 |
| Absolute structure | Flack (1983), 1127 Friedel pairs |
| Absolute structure parameter | −0.003 (13) |
Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), XCIF in SHELXTL (Sheldrick, 2008).
Acknowledgements
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
Boeckmann, J. & Näther, C. (2010). Dalton Trans. pp. 11019–11026. Web of Science CSD CrossRef CAS PubMed Google Scholar
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Wriedt, M., Jess, J. & Näther, C. (2009b). Eur. J. Inorg. Chem. pp. 1406–1413. Web of Science CSD CrossRef Google Scholar
Wriedt, M., Sellmer, S. & Näther, C. (2009a). Dalton Trans. pp. 7975–7984. Web of Science CSD CrossRef Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
In recent work, we have shown that thermal decomposition reactions are an elegant route for discovering and synthesising new ligand-deficient coordination polymers with attractive magnetic properties (Boeckmann & Näther, 2010; Wriedt et al., 2009a, 2009b). In our investigation on the syntheses, structures and properties of such compounds based on paramagnetic transition metals, pseudo-halides and N-donor ligands, we have reacted nickel(II) thiocyanate and trans-1,2-bis(4-pyridyl)-ethylene in acteonitrile. In this reaction single crystals of the title compound were obtained accidentally in a mixture with an unknown phase. To identify the reaction product the compound was investigated by single crystal X-ray diffraction.
In the crystal structure of the title compound, each nickel(II) cation is coordinated by four bridging thiocyanato anions and by two acetonitrile molecules (Fig. 1). The NiN4S2 octahedron is slightly distorted with two long Ni—SCN distances of 2.5305 (6) Å and 2.5341 (6) Å as well as two short Ni—NCS distances of 2.021 (2) Å and 2.023 (2) Å. The angles around the metal atom range from 87.88 (6) ° to 93.23 (6) ° and 178° (Tab. 1).
The nickel cations are linked by the thiocyanato anions into chains, that are further connected into a three-dimensional network (Fig. 2). The shortest intramolecular Ni···Ni distance amounts to 5.7052 (4) Å and the shortest intermolecular Ni···Ni distance amounts to 9.0666 (4) Å.