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COMMUNICATIONS
ISSN: 2056-9890
Volume 81| Part 5| May 2025| Pages 420-424
https://doi.org/10.1107/S2056989025003469

Synthesis, crystal structure and thermal properties of di­aqua­bis­­(4-methyl­pyridine-κN)bis­­(thio­cyanato-κN)cobalt(II)

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Christian Näthera* and Jan Boeckmanna

aInstitut für Anorganische Chemie, Universität Kiel, Germany
*Correspondence e-mail: [email protected]

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 19 March 2025; accepted 17 April 2025; online 24 April 2025)

The reaction of Co(NCS)2 and 4-methyl­pyridine (C6H7N) in water leads to the formation of light-blue single crystals of the title compound, [Co(NCS)2(C6H7N)2(H2O)2]. The asymmetric unit consists of one CoII cation (site symmetry 1) as well as one thio­cyanate anion, one 4-methyl­pyridine coligand and one water mol­ecule in general positions to generate trans-CoN4O2 octa­hedra. In the crystal, the complexes are linked by O—H⋯S hydrogen bonds into a layered network. Powder X-ray diffraction (PXRD) shows that a pure sample has been obtained. Upon heating, the title compound loses its water mol­ecules and transforms into Co(NCS)2(C6H7N)2, which is already reported in the literature.

CCDC reference: 2444751

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1. Chemical context

The synthesis of new coordination compounds is still an important field in inorganic chemistry. In most cases, they are prepared in solution but there are synthetic alternatives such as mol­ecular milling (Braga et al., 2005[Braga, D., Curzi, M., Grepioni, F. & Polito, M. (2005). Chem. Commun. pp. 2915-2917.], 2006[Braga, D., Giaffreda, S. L., Grepioni, F., Pettersen, A., Maini, L., Curzi, M. & Polito, M. (2006). Dalton Trans. pp. 1249-1263.]; James et al., 2012[James, S. L., Adams, C. J., Bolm, C., Braga, D., Collier, P., Friščić, T., Grepioni, F., Harris, K. D. M., Hyett, G., Jones, W., Krebs, A., Mack, J., Maini, L., Orpen, A. G., Parkin, I. P., Shearouse, W. C., Steed, J. W. & Waddell, D. (2012). Chem. Soc. Rev. 41, 413-447.]; Do & Friščić, 2017[Do, J. L. & Friščić, T. (2017). ACS Cent. Sci. 3, 13-19.]; Stolar et al., 2017[Stolar, T., Batzdorf, L., Lukin, S., Žilić, D., Motillo, C., Friščić, T., Emmerling, F., Halasz, I. & Užarević, K. (2017). Inorg. Chem. 56, 6599-6608.]) or reactions in melts (Müller-Buschbaum, 2005[Müller-Buschbaum, K. (2005). Z. Anorg. Allg. Chem. 631, 811-828.]; Höller & Müller-Buschbaum, 2008[Höller, C. J. & Müller-Buschbaum, K. (2008). Inorg. Chem. 47, 10141-10149.]; Zurawski et al., 2012[Zurawski, A., Rybak, J. C., Meyer, L. V., Matthes, P. R., Stepanenko, V., Dannenbauer, N., Würthner, F. & Müller-Buschbaum, K. (2012). Dalton Trans. 41, 4067-4078.]). We have also developed a new route, which is based on thermal ligand removal, that in the beginning was used for the preparation of new transition-metal halide compounds (Näther et al., 2001[Näther, C., Jess, I. & Greve, J. (2001). Polyhedron, 20, 1017-1022.], 2002[Näther, C., Greve, J. & Jess, I. (2002). Solid State Sci. 4, 813-820.]). Later, this method was used for the synthesis of transition-metal thio- and seleno­cyanate coordination compounds, which were of inter­est not only because of their versatile structural behavior but also because of their promising magnetic properties. Following this route, discrete complexes with the composition M(NCS)2(L)4 (M = Mn, Fe, Co, Ni and L = neutral N-donor coligand) are heated in a thermobalance, which mostly leads to a stepwise removal of the coligands and the transformation into new compounds with the composition M(NCS)2(L)2, in which the metal cations are linked into chains or layers (Werner et al., 2015[Werner, J., Rams, M., Tomkowicz, Z., Runčevski, T., Dinnebier, R. E., Suckert, S. & Näther, C. (2015). Inorg. Chem. 54, 2893-2901.]; Neumann et al., 2018[Neumann, T., Ceglarska, M., Germann, L. S., Rams, M., Dinnebier, R. E., Suckert, S., Jess, I. & Näther, C. (2018). Inorg. Chem. 57, 3305-3314.]; Jochim et al., 2020a[Jochim, A., Lohmiller, T., Rams, M., Böhme, M., Ceglarska, M., Schnegg, A., Plass, W. & Näther, C. (2020a). Inorg. Chem. 59, 8971-8982.]). In this context, Co(NCS)2 compounds with chain structures are of special inter­est, because they can show one-dimensional or three-dimensional ferromagnetic ordering (Mautner et al., 2018[Mautner, F. E., Traber, M., Fischer, R. C., Torvisco, A., Reichmann, K., Speed, S., Vicente, R. & Massoud, S. S. (2018). Polyhedron, 154, 436-442.]; Rams et al., 2017[Rams, M., Böhme, M., Kataev, V., Krupskaya, Y., Büchner, B., Plass, W., Neumann, T., Tomkowicz, Z. & Näther, C. (2017). Phys. Chem. Chem. Phys. 19, 24534-24544.], 2020[Rams, M., Jochim, A., Böhme, M., Lohmiller, T., Ceglarska, M., Rams, M. M., Schnegg, A., Plass, W. & Näther, C. (2020). Chem. Eur. J. 26, 2837-2851.]; Jochim et al., 2020b[Jochim, A., Lohmiller, T., Rams, M., Böhme, M., Ceglarska, M., Schnegg, A., Plass, W. & Näther, C. (2020b). Inorg. Chem. 59, 8971-8982.]).

However, in some cases the thermogravimetric curves are not well resolved and the isolation of a pure inter­mediate phase is difficult or even impossible to achieve. In such cases, the usage of precursors, consisting of simple solvato complexes with the composition M(NCS)2(L1)2(L2)2 (L1 = monocoordinating neutral N-donor coligand, L2 = e.g., H2O, MeOH, EtOH, MeCN) is of advantage. If they are heated, the solvent is lost in the beginning in a well-resolved step and the desired inter­mediate phase is obtained pure (Näther et al., 2013[Näther, C., Wöhlert, S., Boeckmann, J., Wriedt, M. & Jess, I. (2013). Z. Anorg. Allg. Chem. 639, 2696-2714.]). In this context, we have reported on two isomers of Co(NCS)2(4-chloro­pyridine)2 in which the metal cations are octa­hedrally coordinated and linked by pairs of thio­cyanate anions into chains (Böhme et al., 2020[Böhme, M., Jochim, A., Rams, M., Lohmiller, T., Suckert, S., Schnegg, A., Plass, W. & Näther, C. (2020). Inorg. Chem. 59, 5325-5338.]). In the triclinic isomer, an all-trans configuration is observed, leading to the formation of linear chains, whereas in the monoclinic isomer an alternating all-trans and cis–cis–trans configurations are observed, which results in the formation of corrugated chains. The monoclinic form is obtained from solution, whereas the triclinic form can be obtained by thermal decomposition of the precursor complex Co(NCS)2(4-chloro­pyridine)2(H2O)2. Solvent-mediated conversion experiments reveal that the monoclinic form with corrugated chains is thermodynamically stable at room-temperature.

[Scheme 1]

In a continuation of this work, we reported the synthesis and crystal structure of the analogous compound Co(NCS)2(4-methyl­pyridine)2 in which the chlorine atom is replaced by a methyl group (Näther & Boeckmann, 2025[Näther, C. & Boeckmann, J. (2025). Acta Cryst. E81, 58-62.]). Based on the chloro–methyl exchange rule (Desiraju & Sarma, 1986[Desiraju, G. R. & Sarma, J. A. (1986). Proc. - Indian Acad. Sci. Chem. Sci. 96, 599-605.]), we expected the formation of a similar crystal structure that might be isotypic to one of the two forms of Co(NCS)2(4-chloro­pyridine)2. A single-crystal structure determination of the 4-methyl­pyridine compound proved that it is isotypic to the monoclinic form of Co(NCS)2(4-chloro­pyridine)2 that consists of corrugated chains. Based on the results obtained for the 4-chloro­pyridine ligands, it was of inter­est if an isomer with linear chains can be prepared by thermal decomposition of a suitable precursor with the composition Co(NCS)2(4-chloro­pyridine)2(H2O)2, which is not reported in the literature.

2. Structural commentary

The asymmetric unit of the title compound, Co(NCS)2(C6H7N)2(H2O)2 (C6H7N = 4-methyl­pyridine) is built up of one cobalt cation located on a crystallographic inversion centre as well as one thio­cyanate anion, one 4-methyl­pyridine ligand and one water mol­ecule that occupy general positions (Fig. 1[link]). The Co cation is therefore sixfold coordinated in a trans-CoN4O2 geometry by two terminal N-bonded thio­cyanate anions, two 4-methyl­pyridine ligands and two water mol­ecules (Fig. 1[link]). The bonding angles around the Co centers deviate from the ideal values, which means that the octa­hedra are slightly distorted (Table 1[link]).

Table 1
Selected geometric parameters (Å, °)

Co1—N1 2.090 (3) Co1—N11 2.162 (2)
Co1—O1 2.105 (2)    
       
N1i—Co1—O1 86.81 (10) O1—Co1—N11i 88.16 (9)
N1—Co1—O1 93.19 (10) O1—Co1—N11 91.84 (9)
N1i—Co1—N11 90.12 (10) C1—N1—Co1 163.9 (3)
N1—Co1—N11 89.88 (10)    
Symmetry code: (i) Mathematical equation.
[Figure 1]
Figure 1
The mol­ecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. Symmetry code: (i) −x + 1, −y, −z.

It is noted that the title compound is isotypic to Fe(NCS)2(4-methyl­pyridine)2(H2O)2 (Cambridge Structural Database refcode VUCCEE; Neumann et al., 2020a[Neumann, T., Gallo, G., Jess, I., Dinnebier, R. E. & Näther, C. (2020a). CrystEngComm, 22, 184-194.]) and Mn(NCS)2(4-methyl­pyridine)2(H2O)2 (VUJYAD; Neumann et al., 2020b[Neumann, T., Gallo, G., Dinnebier, R. E. & Näther, C. (2020b). Z. Anorg. Allge Chem. 646, 88-94.]) reported in the literature. That the chloro-methyl-exchange is also valid for these compounds is shown by the fact that the title compound is also isotypic to Ni(NCS)2(4-chloro­pyridine)2(H2O)2 (GIQQEF; Jochim et al., 2018[Jochim, A., Rams, M., Neumann, T., Wellm, C., Reinsch, H., Wójtowicz, G. M. & Näther, C. (2018). Eur. J. Inorg. Chem. 4779-4789.]) and Co(NCS)2(4-chloro­pyridine)2(H2O)2 (UHUVEB; Böhme et al., 2020[Böhme, M., Jochim, A., Rams, M., Lohmiller, T., Suckert, S., Schnegg, A., Plass, W. & Näther, C. (2020). Inorg. Chem. 59, 5325-5338.]).

3. Supra­molecular features

In the extended structure of the title compound, the complexes are linked by O—H⋯S hydrogen bonds into layers that lie parallel to the bc-plane (Fig. 2[link]). The O—H⋯S bond angles are close to linear, which indicates that these are relatively strong inter­actions (Table 2[link]). Between the layers, no pronounced directional inter­actions are observed (Fig. 3[link]).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O1—H1A⋯S1ii 0.96 (4) 2.35 (4) 3.234 (3) 153 (3)
O1—H1B⋯S1iii 0.93 (5) 2.35 (5) 3.252 (2) 164 (5)
C12—H12⋯S1iv 0.95 2.91 3.833 (3) 164
Symmetry codes: (ii) Mathematical equation; (iii) Mathematical equation; (iv) Mathematical equation.
[Figure 2]
Figure 2
Crystal structure of the title compound in a view along the a-axis direction. O—H⋯S hydrogen bonds are shown as dashed lines.
[Figure 3]
Figure 3
Crystal structure of the title compound in a view along the c-axis direction. O—H⋯S hydrogen bonding is shown as dashed lines.

4. Thermal properties

Comparison of the experimental powder pattern of the residue obtained in the synthesis with that calculated for the title compound shows that a pure crystalline phase has been obtained (Fig. 4[link]).

[Figure 4]
Figure 4
Experimental (top) and calculated (bottom) PXRD patterns for the title compound.

The thermal properties of the title compound were investigated by differential thermoanalysis coupled to thermogravimetry (DTA–TG). Upon heating, one mass loss is observed in the TG curve accompanied with an endothermic event in the DTA curve at 88°C (Fig. 5[link]). On further heating, the sample mass decreases continuously with a further poorly resolved mas-losss step, which is apparent in the DTG curve and which is accompanied with a second endothermic event in the DTA curve. The experimental mass loss in the first step of 9.2% is in good agreement with that calculated for the removal of the two water mol­ecules (9.1%). Comparison of the experimental powder pattern of the residue obtained after the first mass loss shows that the monoclinic form with linear chains of Co(NCS)2(4-methyl­pyridine)2 (Näther & Boeckmann, 2025[Näther, C. & Boeckmann, J. (2025). Acta Cryst. E81, 58-62.]) has formed, which can also be obtained from solution (Fig. 6[link]). This is in contrast to the observations made for the corresponding 4-chloro­pyridine compound (see Chemical context) and indicates that with 4-methyl­pyridine only one isomer might be accessible.

[Figure 5]
Figure 5
DTG, TG and DTA curves for the title compound. The mass loss is given in % and the peak temperature in °C.
[Figure 6]
Figure 6
Experimental PXRD pattern of the residue obtained after the first mass loss in a TG measurement of the title compound (top) and the powder pattern for Co(NCS)2(4-methyl­pyridine)2 calculated from single-crystal data (bottom, Näther & Boeckmann, 2025[Näther, C. & Boeckmann, J. (2025). Acta Cryst. E81, 58-62.]).

5. Database survey

According to a search in the CSD (version 5.43, last update December 2024; Groom et al., 2016[Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171-179.]) using CONQUEST (Bruno et al., 2002[Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389-397.]), some compounds containing Co(NCS)2 and 4-methyl­pyridine have already been reported in the literature. These include a discrete complex with the composition CoNCS(4-methyl­pyridine)3 with p-xylene solvate mol­ecules (QQQGKJ; Solaculu et al., 1974[Solaculu, I., Sandulescu, D. & Dragulescu, C. (1974). Rev. Roum. Chim. 19, 415-417.]), but because no atomic coordinates are given and no charge balance is achieved, the existence of this compound is questionable. There is also a compound with the composition Co(NCS)2(4-methyl­pyridine)2-bis­(p-toluidine)2, which should consists of chains, but even for this structure no atomic coordinates are reported (Refcode: CECDAP; Micu-Semeniuc et al., 1983[Micu-Semeniuc, R., Hila, E., Dobos-Roman, G. & Ghergari, L. (1983). Rev. Roum. Chim. 28, 471-475.]).

All of the remaining hits describe discrete complexes with the composition Co(NCS)2(4-methyl­pyridine)4, which forms clathrates with 4-methyl­pyridine (XIHHEB; Harris et al., 2001[Harris, J. D., Eckles, W. E., Hepp, A. F., Duraj, S. A., Fanwick, P. E., Richardson, J. & Gordon, E. M. (2001). Mater. Des. 22, 625-634.] and XIHHEB01; Harris et al., 2003[Harris, J. D., Eckles, W. E., Hepp, A. F., Duraj, S. A., Hehemann, D. G., Fanwick, P. E. & Richardson, J. (2003). NASA Technical Reports, 211890.]), nitro­benzene (ZZZUXU; Belitskus et al., 1963[Belitskus, D., Jeffrey, G. A., McMullan, R. K. & Stephenson, N. C. (1963). Inorg. Chem. 2, 873-875.]), p-toluidine (CECCOC; Micu-Semeniuc et al., 1983[Micu-Semeniuc, R., Hila, E., Dobos-Roman, G. & Ghergari, L. (1983). Rev. Roum. Chim. 28, 471-475.]), nitro­ethane (ZZZUXY; Belitskus et al., 1963[Belitskus, D., Jeffrey, G. A., McMullan, R. K. & Stephenson, N. C. (1963). Inorg. Chem. 2, 873-875.]) and benzene (ZZZUYI; Belitskus et al., 1963[Belitskus, D., Jeffrey, G. A., McMullan, R. K. & Stephenson, N. C. (1963). Inorg. Chem. 2, 873-875.]). With one exception (XIHHEB), no atomic coordinates are presented for any of these compounds. The crystal structure of the complex Co(NCS)2(4-methyl­pyridine)4 is also found, but the unit-cell parameters are almost identical to that of several of the clathrates mentioned above, indicating that a potential solvent was not located (VERNUC; Harris et al., 2003[Harris, J. D., Eckles, W. E., Hepp, A. F., Duraj, S. A., Hehemann, D. G., Fanwick, P. E. & Richardson, J. (2003). NASA Technical Reports, 211890.]).

6. Synthesis and crystallization

Co(NCS)2 (350.2 mg, 2.06 mmol, Alfa Aesar) and 4-methyl­pyridine (100 µl, 1.03 mmol, Fluka) were stirred together in 3 ml of water at room temperature in a snap cap vial for 3 d. Single crystals were prepared by the same method in the absence of stirring.

Powder X-ray diffraction measurements were performed using a Stoe STADI P transmission powder diffractometer with Cu Kα1 radiation (λ = 1.540598 Å), a Johann-type Ge(111) monochromator and a MYTHEN 1K detector from Dectris. Thermogravimetry and differential thermoanalysis (TG–DTA) measurements were performed in a dynamic nitro­gen atmosphere in Al2O3 crucibles with a heating rate of 4°C min−1 using a STA-PT 1000 thermobalance from Linseis. The TG–DTA instrument was calibrated using standard reference materials.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. The C-bound hydrogen atoms were positioned with idealized geometry (methyl H atoms allowed to rotate and not to tip) and were refined with Uiso(H) = 1.2Ueq(C) (1.5 for methyl H atoms) using a riding model. The O-bound H atoms were located in a difference map and their positions and Uiso values were freely refined. The crystal chosen for data collection was twinned and therefore a twin refinement using data in HKLF-5 format was used leading to a BASF factor of 0.173 (3) for the minor twin component.

Table 3
Experimental details

Crystal data
Chemical formula [Co(NCS)2(C6H7N)2(H2O)2]
Mr 397.37
Crystal system, space group Monoclinic, P21/c
Temperature (K) 200
a, b, c (Å) 10.1901 (6), 12.2379 (10), 7.6165 (9)
β (°) 103.379 (10)
V (Å3) 924.04 (15)
Z 2
Radiation type Mo Kα
μ (mm−1) 1.17
Crystal size (mm) 0.30 × 0.22 × 0.21
 
Data collection
Diffractometer Stoe IPDS2
Absorption correction Numerical (X-SHAPE and X-RED32; Stoe, 2008[Stoe (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.])
Tmin, Tmax 0.793, 0.813
No. of measured, independent and observed [I > 2σ(I)] reflections 2179, 2179, 1822
Rint ?
(sin θ/λ)max (Å−1) 0.662
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.143, 1.04
No. of reflections 2179
No. of parameters 117
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 1.23, −0.56
Computer programs: X-AREA (Stoe, 2008[Stoe (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.]), SHELXT (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]), SHELXL (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]), DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]), XP in SHELXTL-PC (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information

CCDC reference: 2444751

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025003469/hb8129sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025003469/hb8129Isup2.hkl

checkCIF report


Computing details top

Diaquabis(4-methylpyridine-κN)bis(thiocyanato-κN)cobalt(II) top
Crystal data top
[Co(NCS)2(C6H7N)2(H2O)2]F(000) = 410
Mr = 397.37Dx = 1.428 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 10.1901 (6) ÅCell parameters from 5888 reflections
b = 12.2379 (10) Åθ = 2.6–28.1°
c = 7.6165 (9) ŵ = 1.17 mm−1
β = 103.379 (10)°T = 200 K
V = 924.04 (15) Å3Block, light blue
Z = 20.30 × 0.22 × 0.21 mm
Data collection top
Stoe IPDS-2
diffractometer		1822 reflections with I > 2σ(I)
ω scansθmax = 28.1°, θmin = 2.6°
Absorption correction: numerical
(X-Shape and X-Red32; Stoe, 2008)		h = −13→13
Tmin = 0.793, Tmax = 0.813k = −16→16
2179 measured reflectionsl = 0→9
2179 independent reflections
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.047 w = 1/[σ2(Fo2) + (0.1088P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.143(Δ/σ)max < 0.001
S = 1.04Δρmax = 1.23 e Å−3
2179 reflectionsΔρmin = −0.56 e Å−3
117 parametersExtinction correction: SHELXL2016/6 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.044 (9)
Primary atom site location: dual
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. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co10.5000000.0000000.0000000.0221 (2)
N10.5788 (3)−0.0691 (2)0.2534 (4)0.0319 (6)
C10.6496 (3)−0.1080 (2)0.3783 (4)0.0227 (6)
S10.75122 (7)−0.16385 (6)0.55520 (11)0.0295 (2)
O10.3604 (2)0.09689 (18)0.0952 (4)0.0357 (5)
H1A0.351 (4)0.100 (3)0.218 (6)0.032 (10)*
H1B0.333 (5)0.161 (4)0.032 (7)0.061 (14)*
N110.6515 (2)0.12690 (18)0.0581 (4)0.0262 (5)
C110.7790 (3)0.1036 (2)0.1405 (5)0.0327 (7)
H110.8030340.0292410.1649390.039*
C120.8776 (3)0.1823 (3)0.1920 (5)0.0352 (7)
H120.9669850.1612950.2493290.042*
C130.8462 (3)0.2924 (2)0.1600 (5)0.0326 (7)
C140.7142 (3)0.3165 (2)0.0721 (5)0.0326 (7)
H140.6876920.3901050.0449340.039*
C150.6213 (3)0.2326 (2)0.0241 (5)0.0294 (6)
H150.5315930.251015−0.0360860.035*
C160.9504 (4)0.3801 (3)0.2155 (7)0.0495 (10)
H16A0.9160530.4491220.1572880.074*
H16B1.0329960.3594510.1786400.074*
H16C0.9702680.3890820.3468780.074*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0262 (3)0.0165 (3)0.0219 (3)0.00175 (17)0.0019 (2)0.00247 (18)
N10.0395 (13)0.0261 (11)0.0262 (13)−0.0018 (10)−0.0002 (11)0.0060 (10)
C10.0284 (12)0.0190 (11)0.0211 (13)−0.0054 (9)0.0068 (10)−0.0017 (10)
S10.0286 (4)0.0301 (4)0.0255 (4)−0.0001 (3)−0.0025 (3)0.0029 (3)
O10.0472 (13)0.0261 (10)0.0374 (14)0.0112 (9)0.0171 (11)0.0031 (9)
N110.0259 (11)0.0191 (10)0.0314 (13)0.0022 (8)0.0024 (10)0.0020 (9)
C110.0273 (14)0.0238 (13)0.0430 (19)0.0030 (11)−0.0001 (13)0.0049 (12)
C120.0247 (13)0.0330 (15)0.0435 (19)0.0000 (12)−0.0011 (12)0.0037 (14)
C130.0332 (15)0.0275 (14)0.0400 (18)−0.0062 (12)0.0140 (13)−0.0024 (12)
C140.0343 (14)0.0200 (12)0.0437 (19)−0.0007 (11)0.0094 (13)0.0022 (12)
C150.0252 (12)0.0221 (12)0.0399 (17)0.0035 (10)0.0055 (12)0.0049 (12)
C160.0386 (18)0.0418 (19)0.065 (3)−0.0149 (15)0.0063 (17)−0.0028 (18)
Geometric parameters (Å, º) top
Co1—N12.090 (3)C11—H110.9500
Co1—N1i2.090 (3)C11—C121.381 (4)
Co1—O1i2.105 (2)C12—H120.9500
Co1—O12.105 (2)C12—C131.393 (4)
Co1—N11i2.162 (2)C13—C141.387 (4)
Co1—N112.162 (2)C13—C161.501 (4)
N1—C11.155 (4)C14—H140.9500
C1—S11.646 (3)C14—C151.387 (4)
O1—H1A0.96 (4)C15—H150.9500
O1—H1B0.93 (5)C16—H16A0.9800
N11—C111.337 (4)C16—H16B0.9800
N11—C151.341 (3)C16—H16C0.9800
N1—Co1—N1i180.0C15—N11—Co1122.18 (19)
N1i—Co1—O186.81 (10)N11—C11—H11118.3
N1i—Co1—O1i93.19 (10)N11—C11—C12123.3 (3)
N1—Co1—O193.19 (10)C12—C11—H11118.3
N1—Co1—O1i86.81 (10)C11—C12—H12119.9
N1i—Co1—N11i89.88 (10)C11—C12—C13120.1 (3)
N1i—Co1—N1190.12 (10)C13—C12—H12119.9
N1—Co1—N1189.88 (10)C12—C13—C16121.6 (3)
N1—Co1—N11i90.12 (10)C14—C13—C12116.6 (3)
O1—Co1—O1i180.0C14—C13—C16121.9 (3)
O1—Co1—N11i88.16 (9)C13—C14—H14120.1
O1i—Co1—N1188.16 (9)C15—C14—C13119.8 (3)
O1—Co1—N1191.84 (9)C15—C14—H14120.1
O1i—Co1—N11i91.84 (9)N11—C15—C14123.4 (3)
N11i—Co1—N11180.00 (9)N11—C15—H15118.3
C1—N1—Co1163.9 (3)C14—C15—H15118.3
N1—C1—S1179.5 (3)C13—C16—H16A109.5
Co1—O1—H1A126 (2)C13—C16—H16B109.5
Co1—O1—H1B116 (3)C13—C16—H16C109.5
H1A—O1—H1B113 (4)H16A—C16—H16B109.5
C11—N11—Co1120.91 (18)H16A—C16—H16C109.5
C11—N11—C15116.8 (2)H16B—C16—H16C109.5
Co1—N11—C11—C12−175.4 (3)C11—C12—C13—C16179.5 (4)
Co1—N11—C15—C14175.0 (3)C12—C13—C14—C151.1 (5)
N11—C11—C12—C130.5 (6)C13—C14—C15—N110.1 (6)
C11—N11—C15—C14−0.9 (5)C15—N11—C11—C120.6 (5)
C11—C12—C13—C14−1.4 (5)C16—C13—C14—C15−179.7 (4)
Symmetry code: (i) −x+1, −y, −z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···S1ii0.96 (4)2.35 (4)3.234 (3)153 (3)
O1—H1B···S1iii0.93 (5)2.35 (5)3.252 (2)164 (5)
C12—H12···S1iv0.952.913.833 (3)164
Symmetry codes: (ii) −x+1, −y, −z+1; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+2, −y, −z+1.
 

Acknowledgements

This work was supported by the State of Schleswig-Holstein.

References

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Volume 81| Part 5| May 2025| Pages 420-424
https://doi.org/10.1107/S2056989025003469
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