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accesscatena-Poly[[dipyridinenickel(II)]-trans-di-μ-chlorido] from powder data
aUniversity of Frankfurt, Institute of Inorganic and Analytical Chemistry, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main, Germany, and bMersin Universitesi, Ciftlikkoy Kampusu Fen-Edebiyat Fakultesi Kimya Bolumu, Mersin, Turkey
*Correspondence e-mail: fink@chemie.uni-frankfurt.de
The asymetric unit of the title compound, [NiCl2(C5H5N)2]n, contains two NiII ions located on different twofold rotational axes, two chloride anions and two pyridine rings in general positions. Each NiII ion is coordinated by two pyridine rings, which form dihedral angles of 33.0 (2) and 11.0 (2)° for the two centers, and four chloride anions in a distorted octahedral geometry. The chloride anions bridge NiII ions related by translation along the short b axes into two crystallographically independent polymeric chains.
Related literature
For the preparation of related compounds, see: Liptay et al. (1986![[Liptay, G., Wadsten, T. & Borbély-Kuszmann, A. (1986). J. Therm. Anal. 31, 845-852.]](../../../../../../logos/arrows/e_arr.gif "Liptay, G., Wadsten, T. & Borbély-Kuszmann, A. (1986). J. Therm. Anal. 31, 845-852.")
). For related polymeric chains of octahedrally coordinated transition metal ions, see: Hu et al. (2003) and McConnell & Nuttall (1978). For the isostructural compound [CoCl2(C5H5N)2] with a detailed discussion of the pseudo-orthorhombic symmetry, see: Dunitz (1957). For details of the indexing algorithm, see: Boultif & Louër (1991). For details of see: Young (1993).
![[Scheme 1]](cv2682scheme1.gif)
Experimental
Crystal data
|
Data collection: WinXPOW (Stoe & Cie, 2004); cell DASH (David et al., 2004); data reduction: WinXPOW (Stoe & Cie, 2004); program(s) used to solve structure: DASH; program(s) used to refine structure: TOPAS (Coelho, 2007); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2009).
Supporting information
contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810001820/cv2682sup1.cif
Rietveld powder data: contains datablock I. DOI: https://doi.org/10.1107/S1600536810001820/cv2682Isup2.rtv
Indexing with DICVOL (Boultif & Louër, 1991) led to two possible unit cells, a monoclinic and an orthorhombic one. The Pawley fit calculates nearly identical profile χ2 values for both cells. The structure solution was carried out using simulated annealing with DASH (David et al., 2004) and a modified molecular structure model based on [CoCl2(C5H5N)2] (Dunitz, 1957). The structure solution was tried in both crystal systems: monoclinic in P2/c with a = 19.24 Å, b = 3.63 Å, c = 17.35 Å, β = 116.82 ° and Z = 4 and several orthorhombic space groups with C-centered cells with a = 17.35 Å, b = 34.34 Å, c = 3.63 Å and Z = 8. As for [CoCl2(C5H5N)2] (Dunitz, 1957) the structure solution was succesful only for the monoclinic cell. The was carried out using TOPAS (Coelho, 2007) with Chebychev polynomial background correction and the pyridine rings restrained to be flat. Thermal parameters of non-hydrogen atoms were combined refined, except Ni. Thermal parameters of hydrogen atoms were constrained to those of the non-hydrogen atoms. The smooth difference curve (Fig. 2) shows that the structure is correct.
The title compound (I) was prepared by thermal decomposition of [NiCl2(C5H5N)4]. The product, [NiCl2(C5H5N)2], is isotypic with trans-[CoCl2(C5H5N)2] (Dunitz, 1957). The of the title compound was determined to P2/c with a = 19.24 Å, b= 3.63 Å, c = 17.35 Å, β = 116.82 ° and Z = 4. The four nickel atoms are located on two special positions (the twofold axes; Wyckoff positions 2e and 2f). Each nickel atom is coordinated by four chlorine atoms in the equatorial plane and two nitrogen atoms of the pyridine rings in axial positions. This leads to two different distorted coordination octahedra which are connected by edge sharing via bridging Cl atoms to build up two different one-dimensional chains. The distance between neighboured nickel atoms in each chain is equal to the lattice parameter b= 3.63 Å. An orthorhombic found by DICVOL (Boultif & Louër, 1991), is related to the pseudo-orthorhombic cell for the isostructural compound trans-[CoCl2(C5H5N)2], which was discussed by Dunitz (1957). Similar as for the last compound, we found that the structure solution and in orthorhombic symmetry does not lead to satisfying results.
For the preparation of related compounds, see: Liptay et al. (1986). For related polymeric chains of octahedrally coordinated transition metal ions, see: Hu et al. (2003) and McConnell et al. (1978). For the isostructural compound [CoCl2(C5H5N)2] with a detailed discussion of the pseudo-orthorhombic symmetry, see: Dunitz (1957). For details of the indexing algorithm, see: Boultif & Louër (1991). For details of see: Young (1993).
Data collection: WINXPOW (Stoe & Cie, 2004); cell DASH (David et al., 2004); data reduction: WINXPOW (Stoe & Cie, 2004; program(s) used to solve structure: DASH (David et al., 2004); program(s) used to refine structure: TOPAS (Coelho, 2007); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2009).
![[Figure 1]](./cv2682fig1thm.gif) | Fig. 1. A portion of the crystal structure of (I) showing the atomic numbering of independent atoms and 50% probability displacement spheres. |
![[Figure 2]](./cv2682fig2thm.gif) | Fig. 2. Experimental (black) and calculated (red) powder profiles of (I) with difference plot (blue). |
| [NiCl2(C5H5N)2] | F(000) = 584.0 |
| Mr = 287.79 | Dx = 1.770 Mg m−3 |
| Monoclinic, P2/c | Cu Kα1 radiation, λ = 1.54056 Å |
| Hall symbol: -P 2yc | µ = 6.85 mm−1 |
| a = 19.2483 (4) Å | T = 298 K |
| b = 3.62535 (4) Å | Particle morphology: no specific habit |
| c = 17.3504 (2) Å | light green |
| β = 116.883 (2)° | cylinder, 12 × 0.5 mm |
| V = 1079.91 (3) Å3 | Specimen preparation: Prepared at 400 K |
| Z = 4 |
| Stoe Stadi-P diffractometer | Data collection mode: transmission |
| Radiation source: X-ray tube | Scan method: step |
| Primary focussing, Ge 111 monochromator | 2θmin = 2°, 2θmax = 110°, 2θstep = 0.01° |
| Specimen mounting: Specimen was sealed in a 0.5 mm diameter borosilicate glass capillary |
| Least-squares matrix: full with fixed elements per cycle | 126 parameters |
| Rp = 0.024 | 61 restraints |
| Rwp = 0.032 | 3 constraints |
| Rexp = 0.028 | H-atom parameters constrained |
| RBragg = 0.009 | Weighting scheme based on measured s.u.'s w = 1/σ(Yobs)2 |
| 10599 data points | (Δ/σ)max = 0.001 |
| Excluded region(s): none | Background function: Chebychev polynomial |
| Profile function: modified Thompson–Cox–Hastings pseudo-Voigt (Young, 1993) | Preferred orientation correction: none |
| [NiCl2(C5H5N)2] | V = 1079.91 (3) Å3 |
| Mr = 287.79 | Z = 4 |
| Monoclinic, P2/c | Cu Kα1 radiation, λ = 1.54056 Å |
| a = 19.2483 (4) Å | µ = 6.85 mm−1 |
| b = 3.62535 (4) Å | T = 298 K |
| c = 17.3504 (2) Å | cylinder, 12 × 0.5 mm |
| β = 116.883 (2)° |
| Stoe Stadi-P diffractometer | Scan method: step |
| Specimen mounting: Specimen was sealed in a 0.5 mm diameter borosilicate glass capillary | 2θmin = 2°, 2θmax = 110°, 2θstep = 0.01° |
| Data collection mode: transmission |
| Rp = 0.024 | 10599 data points |
| Rwp = 0.032 | 126 parameters |
| Rexp = 0.028 | 61 restraints |
| RBragg = 0.009 | H-atom parameters constrained |
| x | y | z | Uiso*/Ueq | ||
| N1 | 0.08340 (13) | 0.5786 (4) | 0.19907 (14) | 0.01963 (5)* | |
| Ni1 | 0 | 0.5639 (4) | 0.25 | 0.02118 (10)* | |
| C11 | 0.15787 (11) | 0.4942 (5) | 0.25223 (11) | 0.01963 (5)* | |
| C15 | 0.06141 (11) | 0.6731 (5) | 0.11471 (12) | 0.01963 (5)* | |
| Cl1 | −0.07443 (14) | 1.0643 (6) | 0.14865 (16) | 0.01963 (5)* | |
| H11 | 0.1719 (7) | 0.428 (3) | 0.3113 (6) | 0.02356 (6)* | |
| C12 | 0.21450 (11) | 0.5012 (4) | 0.22198 (12) | 0.01963 (5)* | |
| C14 | 0.11707 (11) | 0.6807 (5) | 0.08359 (12) | 0.01963 (5)* | |
| H15 | 0.0088 (6) | 0.737 (4) | 0.0767 (7) | 0.02356 (6)* | |
| H12 | 0.2662 (6) | 0.443 (3) | 0.2583 (7) | 0.02356 (6)* | |
| C13 | 0.19366 (11) | 0.5934 (5) | 0.13910 (12) | 0.01963 (5)* | |
| H14 | 0.1030 (5) | 0.740 (4) | 0.0275 (7) | 0.02356 (6)* | |
| H13 | 0.2309 (6) | 0.599 (4) | 0.1200 (7) | 0.02356 (6)* | |
| N2 | 0.58174 (12) | 0.1488 (4) | 0.37857 (14) | 0.01963 (5)* | |
| Ni2 | 0.5 | 0.1713 (5) | 0.25 | 0.01780 (10)* | |
| C21 | 0.55807 (11) | 0.1700 (5) | 0.44079 (12) | 0.01963 (5)* | |
| C25 | 0.65861 (11) | 0.1073 (5) | 0.39945 (12) | 0.01963 (5)* | |
| Cl2 | 0.42724 (14) | 0.6650 (5) | 0.27908 (17) | 0.01963 (5)* | |
| H21 | 0.5032 (6) | 0.202 (4) | 0.4254 (6) | 0.02356 (6)* | |
| C22 | 0.61220 (10) | 0.1492 (5) | 0.52776 (12) | 0.01963 (5)* | |
| C24 | 0.71442 (11) | 0.0859 (5) | 0.48673 (12) | 0.01963 (5)* | |
| H25 | 0.6734 (6) | 0.098 (4) | 0.3546 (7) | 0.02356 (6)* | |
| H22 | 0.5945 (6) | 0.162 (4) | 0.5697 (7) | 0.02356 (6)* | |
| C23 | 0.68985 (11) | 0.1072 (5) | 0.55017 (12) | 0.01963 (5)* | |
| H24 | 0.7656 (6) | 0.057 (4) | 0.5017 (7) | 0.02356 (6)* | |
| H23 | 0.7259 (6) | 0.097 (4) | 0.6068 (7) | 0.02356 (6)* |
| Ni1—Cl1 | 2.481 (2) | C12—C13 | 1.349 (3) |
| Ni2—Cl2 | 2.461 (3) | C14—C13 | 1.385 (2) |
| N1—Ni1 | 2.155 (3) | C14—H14 | 0.91 (1) |
| N1—C11 | 1.343 (2) | C13—H13 | 0.92 (1) |
| N1—C15 | 1.371 (3) | C21—H21 | 0.97 (1) |
| N2—Ni2 | 2.070 (2) | C21—C22 | 1.395 (2) |
| N2—C21 | 1.350 (4) | C25—C24 | 1.408 (2) |
| N2—C25 | 1.363 (3) | C25—H25 | 0.94 (1) |
| C11—H11 | 0.96 (1) | C22—H22 | 0.93 (1) |
| C11—C12 | 1.408 (3) | C22—C23 | 1.372 (3) |
| C15—C14 | 1.401 (4) | C24—C23 | 1.383 (4) |
| C15—H15 | 0.954 (9) | C24—H24 | 0.90 (1) |
| C12—H12 | 0.93 (1) | C23—H23 | 0.912 (9) |
| Ni1—N1—C15 | 121.1 (2) | C11—C12—H12 | 121.0 (7) |
| Ni1—Cl1—Ni1 | 93.8 (1) | C11—C12—C13 | 119.7 (2) |
| Ni1—N1—C11 | 118.3 (2) | C11—N1—C15 | 120.6 (2) |
| Ni2—N2—C21 | 119.5 (2) | C12—C13—C14 | 120.3 (2) |
| Ni2—N2—C25 | 119.7 (2) | C12—C13—H13 | 119.2 (7) |
| Ni2—Cl2—Ni2 | 94.0 (1) | C13—C14—H14 | 120.4 (7) |
| N1—Ni1—Cl1 | 89.4 (1) | C14—C15—H15 | 119.1 (7) |
| N1—Ni1—N1 | 177.1 (1) | C14—C13—H13 | 120.3 (7) |
| N1—C11—C12 | 120.4 (2) | C15—C14—C13 | 119.0 (2) |
| N1—C15—C14 | 119.7 (2) | C15—C14—H14 | 120.5 (7) |
| N1—C15—H15 | 121.2 (7) | C21—N2—C25 | 120.8 (2) |
| N1—C11—H11 | 119.0 (7) | C21—C22—H22 | 118.9 (8) |
| N2—C21—H21 | 120.3 (7) | C21—C22—C23 | 119.84 (19) |
| N2—C21—C22 | 120.3 (2) | C22—C23—C24 | 120.1 (2) |
| N2—C25—C24 | 120.0 (2) | C22—C23—H23 | 120.7 (8) |
| N2—C25—H25 | 118.8 (8) | C23—C24—H24 | 120.6 (8) |
| N2—Ni2—Cl2 | 91.9 (1) | C23—C24—H24 | 120.6 (8) |
| N2—Ni2—N2 | 175.5 (1) | C24—C25—H25 | 120.5 (8) |
| Cl1—Ni1—Cl1 | 86.1 (1) | C24—C23—H23 | 119.2 (8) |
| Cl1—Ni1—Cl1 | 179.9 (1) | C25—C24—C23 | 118.9 (2) |
| Cl1—Ni1—Cl1 | 93.8 (1) | C25—C24—H24 | 120.8 (8) |
| Cl1—Ni1—Cl1 | 86.2 (1) | H11—C11—C12 | 119.7 (7) |
| Cl2—Ni2—Cl2 | 86.7 (1) | H12—C12—C13 | 119.3 (7) |
| Cl2—Ni2—Cl2 | 179.3 (1) | H22—C22—C23 | 121.3 (8) |
| Cl2—Ni2—Cl2 | 94.0 (1) | H21—C21—C22 | 119.1 (7) |
| Cl2—Ni2—Cl2 | 85.3 (1) |
Experimental details
| Crystal data | |
| Chemical formula | [NiCl2(C5H5N)2] |
| Mr | 287.79 |
| Crystal system, space group | Monoclinic, P2/c |
| Temperature (K) | 298 |
| a, b, c (Å) | 19.2483 (4), 3.62535 (4), 17.3504 (2) |
| β (°) | 116.883 (2) |
| V (Å3) | 1079.91 (3) |
| Z | 4 |
| Radiation type | Cu Kα1, λ = 1.54056 Å |
| µ (mm−1) | 6.85 |
| Specimen shape, size (mm) | Cylinder, 12 × 0.5 |
| Data collection | |
| Diffractometer | Stoe Stadi-P |
| Specimen mounting | Specimen was sealed in a 0.5 mm diameter borosilicate glass capillary |
| Data collection mode | Transmission |
| Scan method | Step |
| 2θ values (°) | 2θmin = 2 2θmax = 110 2θstep = 0.01 |
| Refinement | |
| R factors and goodness of fit | Rp = 0.024, Rwp = 0.032, Rexp = 0.028, RBragg = 0.009, χ2 = 1.357 |
| No. of parameters | 126 |
| No. of restraints | 61 |
| H-atom treatment | H-atom parameters constrained |
Computer programs: WINXPOW (Stoe & Cie, 2004), DASH (David et al., 2004), WINXPOW (Stoe & Cie, 2004, DASH (David et al., 2004), TOPAS (Coelho, 2007), Mercury (Macrae et al., 2006), PLATON (Spek, 2009).
Acknowledgements
The authors thank Sonja Hammer, Jürgen Glinnemann and Martin U. Schmidt for helpful discussions.
References
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David, W. I. F., Shankland, K., Van de Streek, J., Pidcock, E. & Motherwell, S. (2004). DASH. Cambridge Crystallographic Data Centre, Cambridge, England Google Scholar
Dunitz, J. D. (1957). Acta Cryst. 10, 307–313. CSD CrossRef CAS IUCr Journals Google Scholar
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Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
The title compound (I) was prepared by thermal decomposition of [NiCl2(C5H5N)4]. The product, [NiCl2(C5H5N)2], is isotypic with trans-[CoCl2(C5H5N)2] (Dunitz, 1957). The space group of the title compound was determined to P2/c with a = 19.24 Å, b= 3.63 Å, c = 17.35 Å, β = 116.82 ° and Z = 4. The four nickel atoms are located on two special positions (the twofold axes; Wyckoff positions 2e and 2f). Each nickel atom is coordinated by four chlorine atoms in the equatorial plane and two nitrogen atoms of the pyridine rings in axial positions. This leads to two different distorted coordination octahedra which are connected by edge sharing via bridging Cl atoms to build up two different one-dimensional chains. The distance between neighboured nickel atoms in each chain is equal to the lattice parameter b= 3.63 Å. An orthorhombic unit cell, found by DICVOL (Boultif & Louër, 1991), is related to the pseudo-orthorhombic cell for the isostructural compound trans-[CoCl2(C5H5N)2], which was discussed by Dunitz (1957). Similar as for the last compound, we found that the structure solution and refinement in orthorhombic symmetry does not lead to satisfying results.