The crystal structure of the title compound consists of discrete octahedral complexes that are linked by intermolecular O—H⋯S, C—H⋯Cl, C—H⋯S and C—H⋯Cl hydrogen bonding.
Keywords: crystal structure, discrete metal complex, nickel(II) thiocyanate, 2-chloropyridine, hydrogen bonding
Abstract
The asymmetric unit of the title compound, [Ni(NCS)2(C5H4ClN)2(H2O)2], consists of one nickel(II) cation that is located on a center of inversion and one thiocyanate anion, one water molecule and one 2-chloropyridine ligand all occupying general positions. The NiII cation is octahedrally coordinated by two terminal N-bound thiocyanato ligands, two aqua ligands and two N-bound 2-chloropyridine ligands into discrete complexes. Individual complexes are linked by intermolecular O—H⋯S and O—H⋯Cl hydrogen-bonding interactions into a layered network extending parallel to the bc plane. Weak interactions of types C—H⋯S and C—H⋯Cl consolidate the crystal packing.
Chemical context
The synthesis of materials with interesting cooperative magnetic properties is still a major field in coordination chemistry (Zhang et al., 2011 ▸). One feasible strategy for the preparation of such compounds is to link paramagnetic cations with small anionic ligands such as, for example, thiocyanate anions to enable a magnetic exchange between the cations (Palion-Gazda et al., 2015 ▸; Massoud et al., 2013 ▸). In this regard, our group has reported on a number of coordination polymers with bridging thiocyanato ligands. Dependent on the metal cation and the neutral co-ligand, they show different magnetic phenomena including a slow relaxation of the magnetization, which is indicative for single-chain magnetism (Werner et al., 2014 ▸, 2015a ▸,b ▸,c ▸). In the context of this research, discrete complexes are likewise of interest because such compounds can be transformed into the desired polymeric systems by thermal decomposition (Näther et al., 2013 ▸). In view of our systematic studies, we became interested into compounds based on 2-chloropyridine as co-ligand, for which only two different polymorphs were found for representatives containing Zn or Co (Wöhlert et al., 2013 ▸). In a more recent study, investigations were also carried out for Ni that led to the title compound being characterized by single crystal X-ray diffraction. Unfortunately, no single-phase crystalline powder could be synthesized, which prevented further investigations of its physical properties.
Structural commentary
The asymmetric unit of the title compound, [Ni(NCS)2(C5H4NCl)2(H2O)2], consists of one NiII cation, one thiocyanate anion, one water molecule and one neutral 2-chloropyridine co-ligand. The cation is located on a center of inversion whereas all ligands are located on general positions. The NiII cation is coordinated by two terminal N-bound inorganic anionic ligands, two water molecules and two 2-chloropyridine ligands that are coordinated via the pyridine N atom in an all-trans configuration (Fig. 1 ▸). As expected, and in agreement with values reported in literature (Đaković et al., 2008 ▸; Werner et al., 2015b
▸), the Ni—N bond lengths to the thiocyanato ligands are significantly shorter[2.018 (3) Å] than to the pyridine N atom of the neutral 2-chloropyridine ligand [2.208 (3) Å].
Figure 1.
View of a discrete complex with labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry code: (i) −x + 
, −y + 
, -z.+1.]
Supramolecular features
In the crystal, discrete complexes are linked by pairs of intermolecular O—H⋯S hydrogen bonds between one of the two water H atoms and the thiocyanato S atoms of a neighboring complex into centrosymmetric dimers that are further connected into chains along the b axis (Fig. 2 ▸, Table 1 ▸). Neighbouring complexes are additionally linked in the same direction by pairs of C—H⋯Cl hydrogen bonds between the chloro substituent of one complex and one pyridine H atom of a neighbouring complex (Fig. 2 ▸, Table 1 ▸). These chains are further linked by O—H⋯S hydrogen bonding between the second water H atom of one complex and a thiocyanato S atom of a neighbouring complex into layers parallel to the bc plane (Fig. 3 ▸, Table 1 ▸). Within these layers, weak C—H⋯Cl hydrogen bonding is present (Table 1 ▸). Weak intramolecular O—H⋯Cl interactions are also observed (Figs. 2 ▸ and 3 ▸, Table 1 ▸).
Figure 2.
View of the hydrogen-bonded chain that elongates along the b axis. Hydrogen bonds are shown as dashed lines.
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C11—H21⋯S1i | 0.95 | 2.99 | 3.904 (4) | 162 |
| C13—H23⋯S1ii | 0.95 | 2.99 | 3.796 (4) | 143 |
| C14—H24⋯Cl1iii | 0.95 | 2.96 | 3.796 (4) | 147 |
| O1—H1O1⋯S1iv | 0.82 | 2.39 | 3.175 (2) | 160 |
| O1—H2O1⋯S1v | 0.82 | 2.53 | 3.239 (2) | 145 |
| O1—H2O1⋯Cl1vi | 0.82 | 2.75 | 3.180 (3) | 115 |
Symmetry codes: (i) 
; (ii) 
; (iii) 
; (iv) 
; (v) 
; (vi) 
.
Figure 3.
Crystal structure of the title compound showing the hydrogen-bonded layers with hydrogen bonds shown as dashed lines.
Database survey
To the best of our knowledge, there are only four coordination compounds containing thiocyanato and 2-chloropyridine ligands deposited in the Cambridge Structure Database (Version 5.37, last update 2015; Groom et al., 2016 ▸). The structures consist of tetrahedrally coordinated metal cations (Co and Zn) where each metal cation is surrounded by two 2-chloropyridine ligands as well as two thiocyanate anions (Wöhlert et al., 2013 ▸). A general search for coordination compounds with 2-chloropyridine ligands resulted in 16 structures including the aforementioned ones. Two examples relate to a Pd compound, similar to the Co and Zn ones, however with the PdII cation in a square-planar conformation coordinated by two 2-chloropyridine ligands as well as two azide anions (Beck et al., 2001 ▸) as well as a Cu compound with a square-pyramidal coordinated metal cation surrounded by two 2-chloropyridine ligands, one water ligand and two chloride anions (Jin et al., 2005 ▸).
Synthesis and crystallization
Ba(NCS)2·3H2O, Ni(SO4)·6H2O and 2-chloropyridine were purchased from Alfa Aesar. Ni(NCS)2 was synthesized by stirring 17.5 g Ba(NCS)2·3H2O (57 mmol) with 15.0 g Ni(SO4)·6H2O (57 mmol) in 500 ml water. The green residue was filtered off and the filtrate was dried using a rotary evaporator. The homogeneity was checked by X-ray powder diffraction and elemental analysis. Crystals of the title compound suitable for single crystal X-ray diffraction were obtained by the reaction of 26.2 mg Ni(NCS)2 (0.15 mmol) with 56.0 µl 2-chloropyridine (0.6 mmol) in ethanol (1.0 ml) after a few days.
Refinement
Crystal data, data collection, and structure refinement details are summarized in Table 2 ▸. The CH H atoms were positioned with idealized geometry and were refined in a riding model with U iso(H) = 1.2U eq(C). The OH H atoms were located in a difference map, and their bond lengths constrained to 0.82 Å, with U iso(H) = 1.5U eq(O).
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | [Ni(NCS)2(C5H4ClN)2(H2O)2] |
| M r | 437.99 |
| Crystal system, space group | Monoclinic, C2/c |
| Temperature (K) | 200 |
| a, b, c (Å) | 19.5045 (15), 7.5486 (5), 14.9387 (11) |
| β (°) | 125.560 (7) |
| V (Å3) | 1789.3 (3) |
| Z | 4 |
| Radiation type | Mo Kα |
| μ (mm−1) | 1.63 |
| Crystal size (mm) | 0.14 × 0.09 × 0.06 |
| Data collection | |
| Diffractometer | STOE IPDS1 |
| Absorption correction | Numerical (X-RED32 and X-SHAPE; Stoe, 2008 ▸) |
| T min, T max | 0.796, 0.881 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 7195, 1568, 1321 |
| R int | 0.086 |
| (sin θ/λ)max (Å−1) | 0.596 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.049, 0.123, 1.03 |
| No. of reflections | 1568 |
| No. of parameters | 107 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.87, −0.87 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016015218/wm5326sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016015218/wm5326Isup2.hkl
CCDC reference: 1506903
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
This project was supported by the Deutsche Forschungsgemeinschaft (Project No. NA 720/5–1) and the State of Schleswig-Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.
supplementary crystallographic information
Crystal data
| [Ni(NCS)2(C5H4ClN)2(H2O)2] | F(000) = 888 |
| Mr = 437.99 | Dx = 1.626 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 19.5045 (15) Å | Cell parameters from 7195 reflections |
| b = 7.5486 (5) Å | θ = 2.8–25.1° |
| c = 14.9387 (11) Å | µ = 1.63 mm−1 |
| β = 125.560 (7)° | T = 200 K |
| V = 1789.3 (3) Å3 | Block, blue |
| Z = 4 | 0.14 × 0.09 × 0.06 mm |
Data collection
| STOE IPDS-1 diffractometer | 1321 reflections with I > 2σ(I) |
| Phi scans | Rint = 0.086 |
| Absorption correction: numerical (X-Red and X-Shape; Stoe, 2008) | θmax = 25.1°, θmin = 2.8° |
| Tmin = 0.796, Tmax = 0.881 | h = −23→23 |
| 7195 measured reflections | k = −8→8 |
| 1568 independent reflections | l = −17→17 |
Refinement
| Refinement on F2 | Hydrogen site location: mixed |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.049 | w = 1/[σ2(Fo2) + (0.0887P)2] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.123 | (Δ/σ)max < 0.001 |
| S = 1.03 | Δρmax = 0.87 e Å−3 |
| 1568 reflections | Δρmin = −0.87 e Å−3 |
| 107 parameters | Extinction correction: SHELXL-2014/7 (Sheldrick 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 restraints | Extinction coefficient: 0.0046 (11) |
Special details
| 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| Ni1 | 0.2500 | 0.7500 | 0.5000 | 0.0294 (3) | |
| N1 | 0.2189 (2) | 0.5551 (4) | 0.3900 (2) | 0.0374 (7) | |
| C1 | 0.2063 (2) | 0.4433 (4) | 0.3291 (3) | 0.0307 (7) | |
| S1 | 0.18836 (7) | 0.28294 (11) | 0.24339 (8) | 0.0404 (3) | |
| N10 | 0.1155 (2) | 0.7772 (4) | 0.4334 (3) | 0.0360 (7) | |
| C10 | 0.0670 (2) | 0.9202 (4) | 0.4075 (3) | 0.0367 (8) | |
| C11 | −0.0154 (3) | 0.9163 (6) | 0.3732 (3) | 0.0500 (10) | |
| H21 | −0.0466 | 1.0227 | 0.3568 | 0.060* | |
| C12 | −0.0520 (3) | 0.7528 (6) | 0.3630 (4) | 0.0586 (12) | |
| H22 | −0.1088 | 0.7447 | 0.3395 | 0.070* | |
| C13 | −0.0039 (3) | 0.6027 (6) | 0.3879 (4) | 0.0520 (10) | |
| H23 | −0.0271 | 0.4888 | 0.3814 | 0.062* | |
| C14 | 0.0780 (3) | 0.6201 (5) | 0.4222 (3) | 0.0425 (8) | |
| H24 | 0.1104 | 0.5153 | 0.4391 | 0.051* | |
| Cl1 | 0.11007 (7) | 1.12552 (11) | 0.41519 (9) | 0.0523 (4) | |
| O1 | 0.26098 (19) | 0.5775 (3) | 0.6135 (2) | 0.0506 (8) | |
| H1O1 | 0.2506 | 0.5933 | 0.6588 | 0.076* | |
| H2O1 | 0.2750 | 0.4730 | 0.6262 | 0.076* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ni1 | 0.0383 (4) | 0.0205 (4) | 0.0375 (4) | 0.0053 (2) | 0.0267 (3) | 0.0031 (2) |
| N1 | 0.0443 (18) | 0.0298 (14) | 0.0434 (17) | 0.0060 (11) | 0.0285 (15) | −0.0008 (12) |
| C1 | 0.0350 (18) | 0.0247 (15) | 0.0417 (19) | 0.0052 (12) | 0.0276 (17) | 0.0077 (13) |
| S1 | 0.0613 (7) | 0.0251 (4) | 0.0505 (6) | −0.0030 (3) | 0.0415 (5) | −0.0032 (3) |
| N10 | 0.0388 (17) | 0.0317 (14) | 0.0423 (17) | 0.0040 (11) | 0.0264 (15) | 0.0018 (11) |
| C10 | 0.036 (2) | 0.0375 (17) | 0.0383 (19) | 0.0087 (14) | 0.0225 (17) | 0.0037 (14) |
| C11 | 0.036 (2) | 0.064 (2) | 0.043 (2) | 0.0151 (18) | 0.019 (2) | 0.0064 (18) |
| C12 | 0.034 (2) | 0.087 (4) | 0.050 (3) | −0.0007 (19) | 0.022 (2) | −0.004 (2) |
| C13 | 0.042 (2) | 0.057 (2) | 0.054 (3) | −0.0120 (19) | 0.026 (2) | −0.0078 (19) |
| C14 | 0.042 (2) | 0.0371 (18) | 0.051 (2) | −0.0066 (14) | 0.029 (2) | −0.0054 (15) |
| Cl1 | 0.0574 (7) | 0.0308 (5) | 0.0770 (8) | 0.0163 (4) | 0.0438 (6) | 0.0128 (4) |
| O1 | 0.079 (2) | 0.0367 (13) | 0.0661 (18) | 0.0270 (13) | 0.0597 (18) | 0.0243 (12) |
Geometric parameters (Å, º)
| Ni1—N1i | 2.018 (3) | C10—Cl1 | 1.734 (4) |
| Ni1—N1 | 2.018 (3) | C11—C12 | 1.389 (6) |
| Ni1—O1 | 2.048 (2) | C11—H21 | 0.9500 |
| Ni1—O1i | 2.048 (2) | C12—C13 | 1.377 (6) |
| Ni1—N10 | 2.208 (3) | C12—H22 | 0.9500 |
| Ni1—N10i | 2.208 (3) | C13—C14 | 1.372 (6) |
| N1—C1 | 1.158 (4) | C13—H23 | 0.9500 |
| C1—S1 | 1.645 (3) | C14—H24 | 0.9500 |
| N10—C10 | 1.336 (4) | O1—H1O1 | 0.8198 |
| N10—C14 | 1.352 (4) | O1—H2O1 | 0.8201 |
| C10—C11 | 1.375 (6) | ||
| N1i—Ni1—N1 | 180.0 | C14—N10—Ni1 | 112.9 (2) |
| N1i—Ni1—O1 | 87.27 (12) | N10—C10—C11 | 124.6 (4) |
| N1—Ni1—O1 | 92.73 (12) | N10—C10—Cl1 | 117.9 (3) |
| N1i—Ni1—O1i | 92.73 (12) | C11—C10—Cl1 | 117.4 (3) |
| N1—Ni1—O1i | 87.27 (12) | C10—C11—C12 | 118.3 (4) |
| O1—Ni1—O1i | 180.0 | C10—C11—H21 | 120.8 |
| N1i—Ni1—N10 | 90.88 (11) | C12—C11—H21 | 120.8 |
| N1—Ni1—N10 | 89.12 (11) | C13—C12—C11 | 118.4 (4) |
| O1—Ni1—N10 | 87.55 (11) | C13—C12—H22 | 120.8 |
| O1i—Ni1—N10 | 92.45 (11) | C11—C12—H22 | 120.8 |
| N1i—Ni1—N10i | 89.11 (11) | C14—C13—C12 | 119.0 (4) |
| N1—Ni1—N10i | 90.88 (11) | C14—C13—H23 | 120.5 |
| O1—Ni1—N10i | 92.45 (11) | C12—C13—H23 | 120.5 |
| O1i—Ni1—N10i | 87.55 (11) | N10—C14—C13 | 124.0 (4) |
| N10—Ni1—N10i | 180.0 | N10—C14—H24 | 118.0 |
| C1—N1—Ni1 | 175.7 (3) | C13—C14—H24 | 118.0 |
| N1—C1—S1 | 179.4 (3) | Ni1—O1—H1O1 | 129.3 |
| C10—N10—C14 | 115.6 (3) | Ni1—O1—H2O1 | 131.5 |
| C10—N10—Ni1 | 131.4 (2) | H1O1—O1—H2O1 | 99.1 |
Symmetry code: (i) −x+1/2, −y+3/2, −z+1.
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C11—H21···S1ii | 0.95 | 2.99 | 3.904 (4) | 162 |
| C13—H23···S1iii | 0.95 | 2.99 | 3.796 (4) | 143 |
| C14—H24···Cl1iv | 0.95 | 2.96 | 3.796 (4) | 147 |
| O1—H1O1···S1v | 0.82 | 2.39 | 3.175 (2) | 160 |
| O1—H2O1···S1vi | 0.82 | 2.53 | 3.239 (2) | 145 |
| O1—H2O1···Cl1i | 0.82 | 2.75 | 3.180 (3) | 115 |
Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x, y+1, −z+1/2; (iii) −x, y, −z+1/2; (iv) x, y−1, z; (v) x, −y+1, z+1/2; (vi) −x+1/2, −y+1/2, −z+1.
References
- Beck, W., Fehlhammer, W. P., Feldl, K., Klapötke, T. M., Kramer, G., Mayer, P., Piotrowski, H., Pöllmann, P., Ponikwar, W., Schütt, T., Schuierer, E. & Vogt, M. (2001). Z. Anorg. Allg. Chem. 627, 1751–1758.
- Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
- Đaković, M., Popović, Z. & Smrečki-Lolić, N. (2008). J. Mol. Struct. 888, 394–400.
- Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. [DOI] [PMC free article] [PubMed]
- Jin, Z.-M., Li, Z.-G., Tu, B., Shen, Z.-L. & Hu, M.-L. (2005). Acta Cryst. E61, m2566–m2567.
- Massoud, S. S., Guilbeau, A. E., Luong, H. T., Vicente, R., Albering, J. H., Fischer, R. C. & Mautner, F. A. (2013). Polyhedron, 54, 26–33.
- Näther, C., Wöhlert, S., Boeckmann, J., Wriedt, M. & Jess, I. (2013). Z. Anorg. Allg. Chem. 639, 2696–2714.
- Palion-Gazda, J., Machura, B., Lloret, F. & Julve, M. (2015). Cryst. Growth Des. 15, 2380–2388.
- Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
- Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.
- Stoe (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.
- Werner, J., Rams, M., Tomkowicz, Z. & Näther, C. (2014). Dalton Trans. 43, 17333–17342. [DOI] [PubMed]
- Werner, J., Rams, M., Tomkowicz, Z., Runčevski, T., Dinnebier, R. E., Suckert, S. & Näther, C. (2015a). Inorg. Chem. 54, 2893–2901. [DOI] [PubMed]
- Werner, J., Runčevski, T., Dinnebier, R. E., Ebbinghaus, S. G., Suckert, S. & Näther, C. (2015b). Eur. J. Inorg. Chem. 2015, 3236–3245.
- Werner, J., Tomkowicz, Z., Rams, M., Ebbinghaus, S. G., Neumann, T. & Näther, C. (2015c). Dalton Trans. 44, 14149–14158. [DOI] [PubMed]
- Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
- Wöhlert, S., Jess, I., Englert, U. & Näther, C. (2013). CrystEngComm, 15, 5326–5336.
- Zhang, S.-Y., Zhang, Z.-J., Shi, W., Zhao, B., Cheng, P., Liao, D.-Z. & Yan, S.-P. (2011). Dalton Trans. 40, 7993–8002. [DOI] [PubMed]
Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016015218/wm5326sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016015218/wm5326Isup2.hkl
CCDC reference: 1506903
Additional supporting information: crystallographic information; 3D view; checkCIF report