PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actae2this articlesearchopen accesssubmitActa Crystallographica Section E: Crystallographic CommunicationsActa Crystallographica Section E: Crystallographic Communications
 
Acta Crystallogr E Crystallogr Commun. 2017 March 1; 73(Pt 3): 365–368.
Published online 2017 February 14. doi:  10.1107/S2056989017002201
PMCID: PMC5347055

Crystal structure of bis­(aceto­nitrile-κN)bis­(4-benzoyl­pyridine-κN)bis­(thio­cyanato-κN)cobalt(II)

Abstract

The crystal structure of the title compound, [Co(NCS)2(C2H3N)2(C12H9NO)2], consists of cobalt(II) cations that are octa­hedrally coordinated by the N atoms of two terminal thio­cyanate anions, two aceto­nitrile mol­ecules and two 4-benzoyl­pyridine ligands. The discrete complexes are located on centres of inversion. They are connected by weak inter­molecular C—H(...)O and C—H(...)S hydrogen-bonding inter­actions between one of the pyridine H atoms and the carbonyl O atom, and between one of the methyl H atoms of the aceto­nitrile mol­ecule and the thio­cyanate S atoms into layers parallel to (101). No pronounced inter­molecular inter­actions are observed between these layers.

Keywords: crystal structure, discrete complex, cobalt(II) thio­cyanate, 4-benzoyl­pyridine, hydrogen bonding

Chemical context  

In recent times, the synthesis of materials exhibiting cooperative magnetic properties has still been a topic of major inter­est in coordination chemistry (Zhang et al., 2011  ). A good approach for the preparation of such compounds is the use of small anionic ligands such as e.g. thio­cyanate anions to link paramagnetic cations, enabling a magnetic exchange between the cations (Palion-Gazda et al., 2015  ; Massoud et al., 2013  ). During the last few years, our group has reported on a number of coordination polymers with thio­cyanato ligands that show different magnetic phenomena, including a slow relaxation of the magnetization (Werner et al., 2014  , 2015a  ,b  ,c  ,d  ). In the course of this project, we became inter­ested in compounds based on 4-benzoyl­pyridine, for which at that time only three thio­cyanato compounds had been reported (Drew et al., 1985  ; Soliman et al., 2014  ; Bai et al., 2011  ). During these investigations, we obtained a compound with composition [Co(NCS)2(4-benzoyl­pyridine)2] in which the CoII cations are linked by pairs of anionic ligands into chains. In contrast to all other such chain compounds where all ligands are always trans-coordinating, in this compound a cis-coordination of the N and the S atoms of the thio­cyanate anions was observed (Rams et al., 2017  ). Therefore, we assumed that this compound might be metastable and that a second modification with the usual trans-coordination could be prepared by thermal annealing of precursors with terminal N-bonded thio­cyanate anions. In this context, it is noted that there are many examples where different modifications or isomers have been obtained by this alternative route (Werner et al., 2015a  ,c  ; Suckert et al., 2016  ). In the course of these studies, crystals of the title compound, [Co(NCS)2(C2H3N)2(C12H9NO)2], were obtained and characterized by single crystal X-ray diffraction. Unfortunately, no pure crystalline powder could be obtained, which prevented further investigations of the thermal properties of this compound.

An external file that holds a picture, illustration, etc.
Object name is e-73-00365-scheme1.jpg

Structural commentary  

The asymmetric unit of the title compound consists of one cobalt(II) cation, one thio­cyanato anion, one aceto­nitrile mol­ecule and one neutral 4-benzoyl­pyridine ligand. The cobalt(II) cation is located on a center of inversion while the thio­cyanato anion, the aceto­nitrile mol­ecule and the 4-benzoyl­pyridine ligand are located in general positions. The CoII cation is octa­hedrally coordinated by the N atoms of two terminal anionic ligands, two aceto­nitrile mol­ecules and two 4-benzoyl­pyridine ligands (Fig. 1  ). As expected, the Co—N bond lengths to the thio­cyanate anions are significantly shorter [2.0520 (15) Å] than those to the pyridine N atom of the neutral 4-benzoyl­pyridine ligand [2.1831 (13) Å]. All bond lengths are in agreement with values reported in the literature (Drew et al., 1985  ; Soliman et al., 2014  ). The 4-benzoyl­pyridine ligand is not planar; the dihedral angle between the phenyl and pyridine rings is 55.37 (8)°. This is in agreement with values retrieved from the literature, which vary between 40.4 and 74.3° (Escuer et al., 2000  , 2004  ).

Figure 1
View of a discrete complex of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) −x + 1, −y, −z + 1.]

Supra­molecular features  

In the crystal structure of the title compound, the discrete complexes are linked by inter­molecular C—H(...)O hydrogen bonds between one of the pyridine ring H atoms and the oxygen atom of the 4-benzoyl­pyridine ligand of a neighboring complex into dimers, which are further connected into chains (Fig. 2  , Table 1  ). These chains are further linked into layers parallel to (101) by centrosymmetric pairs of inter­molecular C—H(...)S hydrogen bonds between one of the aceto­nitrile hydrogen atoms and the neighbouring thio­cyanato S atom (Fig. 3  , Table 1  ). Pronounced inter­molecular inter­actions are not observed between these layers.

Figure 2
View of the hydrogen-bonded layers extending parallel to (101). Hydrogen bonds are shown as dashed lines.
Figure 3
Part of the crystal structure of the title compound, showing the hydrogen-bonded layers. Hydrogen bonds are shown as dashed lines.
Table 1
Hydrogen-bond geometry (Å, °)

Database survey  

To the best of our knowledge, there are only three coordination compounds with thio­cyanato ligands and with 4-benzoyl­pyridine reported in the Cambridge Structural Database (Version 5.38, last update 2016; Groom et al., 2016  ). In two of these structures, CoII or NiII cations are octa­hedrally coordinated by four 4-benzoyl­pyridine ligands and two thio­cyanate anions (Drew et al., 1985  ; Soliman et al., 2014  ). In the third compound, CuII cations are coordinated in a square-planar mode by two 4-benzoyl­pyridine ligands and two thio­cyanate anions (Bai et al., 2011  ). A general search for coord­ination compounds with 4-benzoyl­pyridine resulted in 22 structures including the aforementioned ones. One of these compounds consists of MnII cations that are octa­hedrally coordinated by two 4-benzoyl­pyridine ligands as well as by four μ 1,3-bridging azido ligands and linked into chains by the anionic ligands (Mautner et al., 2015  ).

Synthesis and crystallization  

Co(NCS)2 and 4-benzoyl­pyridine were purchased from Alfa Aesar. Crystals of the title compound suitable for single crystal X-ray diffraction were obtained by the reaction of 26.3 mg Co(NCS)2 (0.15 mmol) with 55.0 mg 4-benzoyl­pyridine (0.3 mmol) in aceto­nitrile (1.5 ml) after a few days.

Refinement  

Crystal data, data collection and structure refinement details are summarized in Table 2  . The C-bound H atoms were positioned with idealized geometry and were refined with fixed isotropic displacement parameters U iso(H) = 1.2U eq(C) for aromatic and U iso(H) = 1.5 U eq(C) for methyl H atoms using a riding model. The methyl H atoms were allowed to rotate but not to tip.

Table 2
Experimental details

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017002201/wm5365sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017002201/wm5365Isup2.hkl

CCDC reference: 1532114

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

supplementary crystallographic information

Crystal data

[Co(NCS)2(C2H3N)2(C12H9NO)2]F(000) = 642
Mr = 623.60Dx = 1.357 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 10.0304 (6) ÅCell parameters from 17991 reflections
b = 8.3355 (4) Åθ = 2.7–27.1°
c = 18.2581 (12) ŵ = 0.74 mm1
β = 90.547 (8)°T = 200 K
V = 1526.46 (15) Å3Block, purple
Z = 20.16 × 0.08 × 0.02 mm

Data collection

Stoe IPDS-1 diffractometer2895 reflections with I > 2σ(I)
phi scansRint = 0.032
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008)θmax = 27.1°, θmin = 2.7°
Tmin = 0.897, Tmax = 0.964h = −12→12
17991 measured reflectionsk = −10→10
3347 independent reflectionsl = −23→23

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.036w = 1/[σ2(Fo2) + (0.0604P)2 + 0.5217P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.096(Δ/σ)max < 0.001
S = 1.04Δρmax = 0.46 e Å3
3347 reflectionsΔρmin = −0.69 e Å3
189 parametersExtinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.030 (3)

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)

xyzUiso*/Ueq
Co10.50000.00000.50000.02109 (12)
N10.65155 (15)0.11822 (18)0.55359 (9)0.0322 (3)
C10.71187 (17)0.2142 (2)0.58531 (10)0.0313 (4)
S10.79948 (6)0.34828 (9)0.62877 (5)0.0698 (3)
N20.49639 (16)−0.17253 (18)0.58858 (8)0.0311 (3)
C20.50846 (19)−0.2619 (2)0.63506 (10)0.0317 (4)
C30.5267 (3)−0.3769 (3)0.69412 (13)0.0514 (6)
H3A0.5739−0.47140.67570.077*
H3B0.4395−0.40930.71280.077*
H3C0.5791−0.32760.73370.077*
N110.35979 (14)0.15671 (16)0.55624 (7)0.0234 (3)
C110.37171 (18)0.1751 (2)0.62899 (9)0.0281 (4)
H110.43860.11590.65430.034*
C120.29053 (18)0.2770 (2)0.66876 (9)0.0283 (4)
H120.30090.28530.72040.034*
C130.19360 (17)0.36697 (18)0.63229 (9)0.0240 (3)
C140.18049 (17)0.3477 (2)0.55676 (9)0.0266 (3)
H140.11530.40650.52990.032*
C150.26444 (17)0.2409 (2)0.52146 (9)0.0262 (3)
H150.25380.22670.47010.031*
C160.10657 (17)0.4749 (2)0.67758 (9)0.0253 (3)
C170.06203 (16)0.63359 (18)0.64974 (9)0.0238 (3)
C180.13193 (17)0.7173 (2)0.59627 (10)0.0296 (4)
H180.20590.66870.57290.036*
C190.0930 (2)0.8723 (2)0.57732 (12)0.0390 (4)
H190.14170.93000.54160.047*
C20−0.0159 (2)0.9428 (2)0.61001 (12)0.0396 (5)
H20−0.04191.04840.59660.048*
C21−0.08743 (19)0.8590 (2)0.66259 (11)0.0361 (4)
H21−0.16310.90700.68450.043*
C22−0.04865 (17)0.7059 (2)0.68300 (10)0.0293 (4)
H22−0.09680.64970.71950.035*
O110.07747 (15)0.43077 (16)0.73898 (7)0.0373 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Co10.02286 (18)0.01851 (17)0.02185 (17)0.00227 (11)−0.00268 (11)−0.00305 (10)
N10.0281 (7)0.0316 (8)0.0370 (8)−0.0008 (6)−0.0050 (6)−0.0088 (6)
C10.0233 (8)0.0312 (9)0.0393 (9)0.0064 (7)−0.0022 (7)−0.0102 (7)
S10.0407 (3)0.0604 (4)0.1081 (6)−0.0008 (3)−0.0150 (3)−0.0554 (4)
N20.0377 (8)0.0274 (7)0.0281 (7)0.0052 (6)0.0022 (6)0.0011 (6)
C20.0358 (9)0.0264 (8)0.0330 (9)0.0051 (7)0.0027 (7)−0.0012 (7)
C30.0766 (17)0.0344 (11)0.0432 (11)0.0146 (10)0.0073 (11)0.0130 (9)
N110.0255 (7)0.0208 (6)0.0239 (6)0.0034 (5)−0.0014 (5)−0.0021 (5)
C110.0338 (9)0.0275 (8)0.0230 (8)0.0076 (7)−0.0034 (7)0.0008 (6)
C120.0371 (9)0.0287 (8)0.0192 (7)0.0064 (7)−0.0013 (6)−0.0004 (6)
C130.0280 (8)0.0210 (7)0.0232 (7)0.0014 (6)0.0001 (6)−0.0010 (6)
C140.0279 (8)0.0277 (8)0.0240 (8)0.0078 (6)−0.0048 (6)−0.0031 (6)
C150.0292 (8)0.0281 (8)0.0211 (7)0.0053 (6)−0.0048 (6)−0.0044 (6)
C160.0283 (8)0.0241 (7)0.0235 (7)−0.0008 (6)0.0000 (6)−0.0058 (6)
C170.0229 (8)0.0223 (7)0.0262 (8)0.0002 (6)−0.0023 (6)−0.0068 (6)
C180.0278 (8)0.0250 (8)0.0361 (9)0.0009 (6)0.0023 (7)−0.0016 (7)
C190.0414 (11)0.0280 (9)0.0477 (11)0.0002 (8)0.0017 (9)0.0040 (8)
C200.0456 (11)0.0236 (8)0.0495 (11)0.0083 (8)−0.0084 (9)−0.0052 (8)
C210.0304 (9)0.0328 (9)0.0450 (11)0.0082 (7)−0.0051 (8)−0.0162 (8)
C220.0265 (8)0.0308 (8)0.0305 (8)0.0003 (7)0.0008 (7)−0.0108 (7)
O110.0517 (8)0.0352 (7)0.0254 (6)0.0055 (6)0.0083 (6)−0.0005 (5)

Geometric parameters (Å, º)

Co1—N1i2.0520 (15)C13—C141.393 (2)
Co1—N12.0520 (15)C13—C161.506 (2)
Co1—N22.1647 (15)C14—C151.388 (2)
Co1—N2i2.1648 (15)C14—H140.9500
Co1—N11i2.1831 (13)C15—H150.9500
Co1—N112.1831 (13)C16—O111.218 (2)
N1—C11.155 (2)C16—C171.485 (2)
C1—S11.6244 (18)C17—C181.394 (2)
N2—C21.135 (2)C17—C221.406 (2)
C2—C31.453 (3)C18—C191.392 (3)
C3—H3A0.9800C18—H180.9500
C3—H3B0.9800C19—C201.380 (3)
C3—H3C0.9800C19—H190.9500
N11—C151.341 (2)C20—C211.392 (3)
N11—C111.341 (2)C20—H200.9500
C11—C121.386 (2)C21—C221.384 (3)
C11—H110.9500C21—H210.9500
C12—C131.392 (2)C22—H220.9500
C12—H120.9500
N1i—Co1—N1180.0C11—C12—H12120.3
N1i—Co1—N291.13 (6)C13—C12—H12120.3
N1—Co1—N288.88 (6)C12—C13—C14118.03 (15)
N1i—Co1—N2i88.87 (6)C12—C13—C16117.70 (14)
N1—Co1—N2i91.13 (6)C14—C13—C16124.24 (15)
N2—Co1—N2i180.0C15—C14—C13118.79 (15)
N1i—Co1—N11i88.05 (6)C15—C14—H14120.6
N1—Co1—N11i91.95 (6)C13—C14—H14120.6
N2—Co1—N11i88.24 (5)N11—C15—C14123.27 (15)
N2i—Co1—N11i91.76 (5)N11—C15—H15118.4
N1i—Co1—N1191.95 (6)C14—C15—H15118.4
N1—Co1—N1188.05 (6)O11—C16—C17120.68 (15)
N2—Co1—N1191.76 (5)O11—C16—C13118.05 (15)
N2i—Co1—N1188.24 (5)C17—C16—C13121.22 (14)
N11i—Co1—N11180.00 (5)C18—C17—C22119.48 (16)
C1—N1—Co1162.48 (14)C18—C17—C16122.27 (15)
N1—C1—S1178.75 (18)C22—C17—C16118.06 (15)
C2—N2—Co1172.91 (16)C19—C18—C17119.76 (17)
N2—C2—C3178.8 (2)C19—C18—H18120.1
C2—C3—H3A109.5C17—C18—H18120.1
C2—C3—H3B109.5C20—C19—C18120.58 (19)
H3A—C3—H3B109.5C20—C19—H19119.7
C2—C3—H3C109.5C18—C19—H19119.7
H3A—C3—H3C109.5C19—C20—C21119.97 (18)
H3B—C3—H3C109.5C19—C20—H20120.0
C15—N11—C11117.74 (14)C21—C20—H20120.0
C15—N11—Co1123.36 (11)C22—C21—C20120.19 (17)
C11—N11—Co1118.85 (11)C22—C21—H21119.9
N11—C11—C12122.79 (15)C20—C21—H21119.9
N11—C11—H11118.6C21—C22—C17120.00 (17)
C12—C11—H11118.6C21—C22—H22120.0
C11—C12—C13119.35 (15)C17—C22—H22120.0

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···AD—HH···AD···AD—H···A
C3—H3A···S1ii0.982.853.771 (3)156
C11—H11···O11iii0.952.493.193 (2)131

Symmetry codes: (ii) x, y−1, z; (iii) −x+1/2, y−1/2, −z+3/2.

References

  • Bai, Y., Zheng, G.-S., Dang, D.-B., Zheng, Y.-N. & Ma, P.-T. (2011). Spectrochim. Acta Part A, 79, 1338–1344. [PubMed]
  • Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
  • Drew, M. G. B., Gray, N. I., Cabral, M. F. & Cabral, J. deO. (1985). Acta Cryst. C41, 1434–1437.
  • Escuer, A., Mautner, F. A., Sanz, N. & Vicente, R. (2000). Inorg. Chem. 39, 1668–1673. [PubMed]
  • Escuer, A., Sanz, N., Mautner, F. A. & Vicente, R. (2004). Eur. J. Inorg. Chem. pp. 309–316.
  • Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. [PMC free article] [PubMed]
  • 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.
  • Mautner, F. A., Berger, C., Scherzer, M., Fischer, R. C., Maxwell, L., Ruiz, E. & Vicente, R. (2015). Dalton Trans. 44, 18632–18642. [PubMed]
  • Palion-Gazda, J., Machura, B., Lloret, F. & Julve, M. (2015). Cryst. Growth Des. 15, 2380–2388.
  • Rams, M., Tomkowicz, Z., Böhme, M., Plass, W., Suckert, S., Werner, J., Jess, I. & Näther, C. (2017). Phys. Chem. Chem. Phys. 19, 3232–3243. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. [PMC free article] [PubMed]
  • Soliman, S. M., Elzawy, Z. B., Abu-Youssef, M. A. M., Albering, J., Gatterer, K., Öhrström, L. & Kettle, S. F. A. (2014). Acta Cryst. B70, 115–125. [PubMed]
  • Stoe (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.
  • Suckert, S., Rams, M., Böhme, M., Germann, L. S., Dinnebier, R. E., Plass, W., Werner, J. & Näther, C. (2016). Dalton Trans. 45, 18190–18201. [PubMed]
  • Werner, J., Rams, M., Tomkowicz, Z. & Näther, C. (2014). Dalton Trans. 43, 17333–17342. [PubMed]
  • Werner, J., Rams, M., Tomkowicz, Z., Runčevski, T., Dinnebier, R. E., Suckert, S. & Näther, C. (2015a). Inorg. Chem. 54, 2893–2901. [PubMed]
  • Werner, J., Runčevski, T., Dinnebier, R. E., Ebbinghaus, S. G., Suckert, S. & Näther, C. (2015c). Eur. J. Inorg. Chem. 2015, 3236–3245.
  • Werner, J., Tomkowicz, Z., Rams, M., Ebbinghaus, S. G., Neumann, T. & Näther, C. (2015d). Dalton Trans. 44, 14149–14158. [PubMed]
  • Werner, J., Tomkowicz, Z., Reinert, T. & Näther, C. (2015b). Eur. J. Inorg. Chem. pp. 3066–3075.
  • Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
  • Zhang, S.-Y., Zhang, Z.-J., Shi, W., Zhao, B., Cheng, P., Liao, D.-Z. & Yan, S.-P. (2011). Dalton Trans. 40, 7993–8002. [PubMed]

Articles from Acta Crystallographica Section E: Crystallographic Communications are provided here courtesy of International Union of Crystallography