Synthesis, crystal structure and thermal properties of bis­(1,3-di­cyclo­hexyl­thio­urea-κS)bis(iso­thiocyanato-κN)cobalt(II)

Krebs, C.; Jess, I.; Näther, C.

doi:10.1107/S205698902101327X

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ISSN: 2056-9890

Volume 78| Part 1| January 2022| Pages 71-75

https://doi.org/10.1107/S205698902101327X

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Synthesis, crystal structure and thermal properties of bis(1,3-dicyclohexylthiourea-κS)bis(isothiocyanato-κN)cobalt(II)

Christoph Krebs,^a ^* Inke Jess ^a and Christian Näther ^a

^aInstitute of Inorganic Chemistry, University of Kiel, Max-Eyth.-Str. 2, 24118 Kiel, Germany
^*Correspondence e-mail: ckrebs@ac.uni-kiel.de

Edited by O. Blacque, University of Zürich, Switzerland (Received 5 November 2021; accepted 14 December 2021; online 1 January 2022)

Crystals of the title compound, [Co(NCS)₂(C₁₃H₂₄N₂S)₂], were obtained by the reaction of Co(NCS)₂ with 1,3-dicyclohexylthiourea in ethanol. Its crystal structure consists of discrete complexes that are located on twofold rotation axes, in which the Co^II cations are tetrahedrally coordinated by two terminal N-bonded thiocyanate anions and two 1,3-dicyclohexylthiourea ligands. These complexes are linked via intermolecular N—H⋯S and C—H⋯S hydrogen bonding into chains, which elongate in the b-axis direction. These chains are closely packed in a pseudo-hexagonal manner. The CN stretching vibration of the thiocyanate anions located at 2038 cm⁻¹ is in agreement with only terminal bonded anionic ligands linked to metal cations in a tetrahedral coordination. TG–DTA measurements prove the decomposition of the compound at about 227°C. DSC measurements reveal a small endothermic signal before decomposition at about 174°C, which might correspond to melting.

Keywords: crystal structure; cobalt(II)thiocyanate; 1,3-dicyclohexylthiourea; thermal properties.

CCDC reference: 2128608

1. Chemical context

Coordination polymers based on Co(NCS)₂ have been investigated for several years because they can show interesting magnetic properties due to the large magnetic anisotropy of Co^II. This is the reason why we and others are especially interested in this class of compounds. In most cases, the Co^II cations are octahedrally coordinated and linked by pairs of thiocyanate anions into chains, even if a few compounds with single thiocyanate bridges have been reported (Palion-Gazda et al., 2015 ). If the Co cations are all-trans or cis–cis–trans coordinated with the thiocyanate anions in the trans-position, the chains are linear and frequently show antiferromagnetic or ferromagnetic behavior or a slow relaxation of the magnetization indicative of single-chain magnetism (Wang et al., 2005 ; Shurda et al., 2013 ; Wöhlert et al., 2014 ; Jin et al., 2007 ; Prananto et al., 2017 ; Mautner et al., 2018 ; Rams et al., 2020 ; Jochim et al., 2020a ). In the case where the Co centers are cis–cis–trans coordinated with the thiocyanate anions in the cis-position, the chains are corrugated and the magnetic exchange is suppressed (Shi et al., 2007 ; Böhme et al., 2020 ). In some cases Co(NCS)₂ layers are observed, in which the Co cations are linked by single and double thiocyanate bridges or by single anionic ligands exclusively (Suckert et al., 2016 ; Werner et al., 2015a ). These compounds usually show ferromagnetic behavior with low critical temperatures, which can be tuned by mixed crystal formation with Ni^II cations (Wellm et al., 2018 , 2020 ; Neumann et al., 2018a ).

In the case where monocoordinating co-ligands are used and the chains are linear, these compounds have the general composition Co(NCS)₂(L)₂ (L = co-ligand) but for this composition a second structure exists, in which the Co cations are tetrahedrally coordinated and in this case, no cooperative magnetic exchange interactions can be observed. The reason why, dependent on the nature of the co-ligand, chains or complexes are formed is not clear. First of all, one can assume that the cobalt cations would prefer a tetrahedral coordination with bulky co-ligands because of steric crowding. On the other hand, we observed that strong N-donor co-ligands such as, for example, 4-(dimethylamino)pyridine would lead to the formation of tetrahedral complexes (Neumann et al., 2018b ), whereas weaker donors such as 4-(4-chlorobenzyl)pyridine (Werner et al., 2015b ) or 4-(3-phenylpropyl)pyridine (Werner et al., 2014 ; Ceglarska et al., 2021 ) lead to the formation of chains. In the case of intermediate donor ligands like 4-methoxypyridine, both isomers can be obtained, chains and discrete complexes (Mautner et al., 2018; Rams et al., 2020).

In the course of our systematic work, we became interested in S-donor co-ligands and with thiourea we obtained a compound with the desired chain structure showing antiferromagnetic ordering but no slow relaxation of the magnetization (Jochim et al., 2020a). In further work, we obtained two compounds with 1,3-dimethylthiourea (and 1,1,3,3-tetramethylthiourea) but in this case, tetrahedral discrete complexes were obtained (Jochim et al., 2020b ,c ). To investigate the influence of the co-ligand in more detail we used 1,3-dicyclohexylthiourea as the co-ligand and we obtained crystals of the title compound, which were characterized by single crystal X-ray diffraction, which proves the formation of a discrete complex even with this ligand. Investigations using X-ray powder diffraction show that the title compound was obtained as a pure phase (Fig. 1). The CN stretching vibration is observed at 2038 cm⁻¹, which is typical for thiocyanates that are only terminal bonded to metal cations in a tetrahedral coordination (Fig. S1). Measurements using simultaneously differential thermoanalysis (DTA) and thermogravimetry reveal the decomposition of the title compound starting at about 227°C, which is accompanied with an endothermic event in the DTA curve (Fig. S2). The experimental mass loss of 37.7% is in a reasonable agreement with that calculated for the removal of one 1,3-dicyclohexylthiourea ligand of 36.6%. The mass loss in the second step is higher than expected for the removal of the second 1,3-dicyclohexylthiourea ligand, but in this temperature region the thiocyanate anions also decompose. Additional measurements using differential scanning calorimetry show a small endothermic event before the compound decomposes (Fig. S3). To check if this event corresponds to some transition, the residue formed after the endothermic signal (see point `x′ in Fig. S3) was isolated and investigated by XRPD measurements, which shows that the powder pattern is identical to that of the pristine material but of lower crystallinity (Fig. S4).

Figure 1
Experimental (top) and calculated powder pattern (bottom) of the title compound measured with Cu Kα radiation.

2. Structural commentary

The asymmetric unit of the title compound consists of one Co^II cation that is located on a twofold rotation axis, one thiocyanate anion and one 1,3-dicyclohexylthiourea ligand that occupies general positions. The Co^II cations are fourfold coordinated by two terminal N-bonded thiocyanate anions and two sulfur atoms of 1,3-dicyclohexylthiourea ligands each (Fig. 2). The Co—N and Co—S distances are comparable to that observed in other Co(NCS)₂ compounds with thiourea derivatives (Table 1, Jochim et al., 2020a,b). The bond angles deviate from the ideal values, revealing that the tetrahedra are slightly distorted (see supporting information). Both hexane rings of the 1,3-dimethylthiourea ligand are in a chair conformation (Figs. 2 and 3). There are two symmetry-equivalent intramolecular N—H⋯N hydrogen bonds between the amino H atom of the 1,3-dicyclohexylthiourea ligand and the N atoms of the thiocyanate anions (Table 2 and Fig. 3). The N—H⋯N angle is close to linearity, indicating that this is a relatively strong interaction (Table 2).

Table 1
Selected geometric parameters (Å, °)

Co1—N1	1.9516 (16)	Co1—S11	2.3130 (5)

N1—Co1—N1ⁱ	113.00 (10)	N1—Co1—S11	106.00 (5)
N1—Co1—S11ⁱ	109.67 (5)
Symmetry code: (i) $[-x+1, y, -z+{\script{3\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11⋯N1	0.88	2.33	3.169 (2)	160
C12—H12⋯S1ⁱⁱ	1.00	2.93	3.774 (2)	143
N12—H12A⋯S1ⁱⁱ	0.88	2.84	3.6770 (16)	159
C19—H19B⋯S11	0.99	3.00	3.529 (2)	114
Symmetry code: (ii) .

Figure 2
Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level. [Symmetry code: (i) −x + 1, y, −z + $[{3\over 2}]$ .]

Figure 3
View of the discrete complex with intramolecular N—H⋯N hydrogen bonding shown as dashed lines.

3. Supramolecular features

In the crystal structure of the title compound the discrete complexes are linked into chains by two intermolecular N—H⋯S hydrogen bonds related by the twofold rotation axis between the N—H H atoms and the thiocyanate S atom of a neighboring complex (Fig. 4, Table 2). The discrete complexes are additionally linked by two symmetry-equivalent C—H⋯S hydrogen bonds, which might correspond to a weak interaction (Fig. 4, Table 2). These chains elongate along the b-axis direction and each chain is surrounded by six neighboring chains in a pseudo-hexagonal manner (Fig. 5).

Figure 4
Crystal structure of the title compound with a view of a chain formed by intermolecular N—H⋯S and C—H⋯S hydrogen bonding (dashed lines).

Figure 5
Crystal structure of the title compound with a view in the direction of the crystallographic b-axis, showing the arrangement of the chains. Intermolecular N—H⋯S and C—H⋯S hydrogen bonding is shown as dashed lines.

4. Database survey

There are only ten crystal structures with this ligand reported in the Cambridge Structural Database (CSD version 5.42, last update November 2020; Groom et al., 2016 ). The most important for us is bis(1,3-dicyclohexylthiourea)bis(isothiocyanato)zinc(II), which is isotypic to the title compound (refcode: TINBIC; Jia et al., 2007 ). These authors also reported the structure of hexakis(1,3-dicyclohexylthiourea)lead(II)bis(isothiocyanate) ethanol solvate, which consists of discrete complexes, in which the Pb^II cations are octahedrally coordinated by six 1,3-dicyclohexylthiourea ligands (refcode: TINBUO; Jia et al., 2007). In that paper, the crystal structure of bis(1,3-dicyclohexylthiourea)dichlorocobalt(II) is also reported (refcode: TINBEY). The crystal structures of chlorobis(1,3-dicyclohexylthiourea)copper(I), of bromobis(1,3-dicyclohexylthiourea)copper(I) (refcodes: WODVER and WODVIV; Jia et al., 2008 ) and of chloro-tris(1,3-dicyclohexylthiourea)tellurium(II) chloride (refcode: OCAWUK; Husebye et al., 2001 ) also consist of discrete complexes. The crystal structure of 1,3-dicyclohexylthiourea was reported by Ramnathan et al. (1996 ) (refcode: ZIVGUG).

There are also several crystal structures with Co(NCS)₂ reported, in which the Co^II cations are tetrahedrally coordinated by two terminal N-bonded thiocyanate anions and two N-donor co-ligands, for example two polymorphic modifications of bis(4-dimethylaminopyridine)bis(isothiocyanato)cobalt(II) (refcode: GIQPEE; Neumann et al., 2018a; Krebs et al., 2021 ), bis(4-vinylpyridine)di(isothiocyanato)cobalt(II) (refcode: BOZJUW; Foxman & Mazurek, 1982 ), bis(2-chloropyridine)bis(isothiocyanato)cobalt(II), bis(2-bromopyridine)bis(isothiocyanato)cobalt(II), bis(2-methylpyridine)bis(isothiocyanato)cobalt(II) (refcodes: DEYDUI, DEYFIY and DEYGAR; Wöhlert et al., 2013 ) and bis(4-methoxypyridine)bis(isothiocyanato)cobalt(II) (refcode: KIJQAY; Mautner et al., 2018).

Two structures have already been reported with thiourea derivatives and Co(NCS)₂, viz. bis(1,3-dimethylthiourea)bis(isothiocyanato)cobalt(II) (refcode: QUSZAI; Jochim et al., 2020b) and bis(1,1,3,3-tetramethylthiourea)bis(isothiocyanato)cobalt(II) (refcode: WUQTIO; Jochim et al., 2020c).

5. Synthesis and crystallization

Synthesis

Co(NCS)₂ was purchased from Merck. 1,3-Dicyclohexylthiourea was purchased from Alfa Aesar. All chemicals were used without further purification. Blue-colored single crystals suitable for single-crystal X-ray analysis were obtained after storage of 0.25 mmol Co(NCS)₂ (43.8 mg) and 0.50 mmol 1,3-dicyclohexylthiourea (120.2 mg) in 2.0 ml ethanol at 333 K over night.

Experimental details

The data collection for single crystal structure analysis was performed using an XtaLAB Synergy, Dualflex, HyPix diffractometer from Rigaku with Cu-Kα radiation.

The IR spectrum was measured using an ATI Mattson Genesis Series FTIR Spectrometer, control software: WINFIRST, from ATI Mattson.

The PXRD measurement was performed with Cu Kα₁ radiation (λ = 1.540598 Å) using a Stoe Transmission Powder Diffraction System (STADI P) equipped with a MYTHEN 1K detector and a Johansson-type Ge(111) monochromator.

Thermogravimetry and differential thermoanalysis (TG–DTA) measurements were performed in a dynamic nitrogen atmosphere in Al₂O₃ crucibles using a STA-PT 1000 thermobalance from Linseis. The instrument was calibrated using standard reference materials.

The DSC experiments were performed using a DSC 1 star system with STARe Excellence software from Mettler-Toledo AG under dynamic nitrogen flow in Al pans.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All non-hydrogen atoms were refined anisotropically. The C-bound H atoms were positioned with idealized geometry and were refined isotropically with U_iso(H) = 1.2 U_eq(C) using a riding model.

Table 3
Experimental details

Crystal data
Chemical formula	[Co(NCS)₂(C₁₃H₂₄N₂S)₂]
M_r	655.89
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	24.0667 (4), 8.8282 (1), 18.8910 (3)
β (°)	125.619 (2)
V (Å³)	3262.76 (11)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	6.73
Crystal size (mm)	0.15 × 0.08 × 0.03

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction.]$ )
T_min, T_max	0.704, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	20399, 3503, 3462
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.096, 1.05
No. of reflections	3503
No. of parameters	177
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.36
Computer programs: CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction.]$ ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2016/6 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 1999 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2128608

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698902101327X/zq2269sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902101327X/zq2269Isup2.hkl

Figure S1. IR spectrum of the title compound. Given is the value of the CN stretching vibration. DOI: https://doi.org/10.1107/S205698902101327X/zq2269sup3.png

Figure S2. DTG (top) TG (mid) and DTA curve of the title compound measured with 4C/min. Given is the mass loss in % and the peak temperature. DOI: https://doi.org/10.1107/S205698902101327X/zq2269sup4.png

Figure S3. DSC curve of the title compound measured with 4C/min. x denotes the point where the residue was isolated. DOI: https://doi.org/10.1107/S205698902101327X/zq2269sup5.png

Figure S4. Experimental XRPD pattern measured with Cu Kalpha radiation of the residue formed after the first weak endothermic signal in a DSC measurement (top) and XRPD pattern of the title compound calculated from single crystal data (bottom). DOI: https://doi.org/10.1107/S205698902101327X/zq2269sup6.png

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2021); cell refinement: CrysAlis PRO (Rigaku OD, 2021); data reduction: CrysAlis PRO (Rigaku OD, 2021); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(1,3-dicyclohexylthiourea-κS)bis(isothiocyanato-κN)cobalt(II) top

Crystal data top

[Co(NCS)₂(C₁₃H₂₄N₂S)₂]	F(000) = 1396
M_r = 655.89	D_x = 1.335 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
a = 24.0667 (4) Å	Cell parameters from 13904 reflections
b = 8.8282 (1) Å	θ = 2.9–78.5°
c = 18.8910 (3) Å	µ = 6.73 mm⁻¹
β = 125.619 (2)°	T = 100 K
V = 3262.76 (11) Å³	Block, intense blue
Z = 4	0.15 × 0.08 × 0.03 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	3503 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	3462 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.025
Detector resolution: 10.0000 pixels mm^-1	θ_max = 80.0°, θ_min = 4.5°
ω scans	h = −30→30
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2021)	k = −11→10
T_min = 0.704, T_max = 1.000	l = −20→24
20399 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.096	w = 1/[σ²(F_o²) + (0.054P)² + 5.0479P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3503 reflections	Δρ_max = 0.65 e Å⁻³
177 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co1	0.500000	0.91248 (4)	0.750000	0.02073 (12)
N1	0.57874 (8)	1.03449 (18)	0.78063 (11)	0.0283 (3)
C1	0.62890 (10)	1.1041 (2)	0.82549 (13)	0.0241 (4)
S1	0.69885 (2)	1.19936 (6)	0.88857 (3)	0.02946 (13)
S11	0.53579 (2)	0.76716 (5)	0.87146 (3)	0.02478 (12)
C11	0.59547 (9)	0.6489 (2)	0.87525 (12)	0.0221 (3)
N11	0.63300 (8)	0.70206 (18)	0.84996 (11)	0.0257 (3)
H11	0.628830	0.799458	0.837934	0.031*
C12	0.68063 (9)	0.6182 (2)	0.83960 (13)	0.0250 (4)
H12	0.664260	0.511209	0.823464	0.030*
C13	0.67862 (11)	0.6900 (3)	0.76500 (14)	0.0377 (5)
H13A	0.691074	0.798367	0.777936	0.045*
H13B	0.631610	0.683568	0.710954	0.045*
C14	0.72780 (12)	0.6107 (3)	0.75124 (15)	0.0433 (6)
H14A	0.712524	0.504987	0.732404	0.052*
H14B	0.727319	0.662885	0.704507	0.052*
C15	0.80009 (11)	0.6105 (3)	0.83419 (15)	0.0342 (5)
H15A	0.817213	0.715832	0.849578	0.041*
H15B	0.830355	0.553156	0.824289	0.041*
C16	0.80239 (10)	0.5391 (2)	0.90921 (14)	0.0297 (4)
H16A	0.849393	0.546680	0.963165	0.036*
H16B	0.790582	0.430304	0.896754	0.036*
C17	0.75272 (10)	0.6167 (2)	0.92332 (13)	0.0276 (4)
H17A	0.752748	0.562352	0.969193	0.033*
H17B	0.767965	0.721974	0.943308	0.033*
N12	0.60327 (7)	0.50735 (18)	0.90351 (10)	0.0224 (3)
H12A	0.635837	0.452301	0.908415	0.027*
C18	0.56066 (9)	0.4371 (2)	0.92713 (12)	0.0212 (3)
H18	0.550070	0.515812	0.955748	0.025*
C19	0.49330 (9)	0.3789 (2)	0.84687 (12)	0.0244 (4)
H19A	0.502584	0.301113	0.817278	0.029*
H19B	0.468264	0.463403	0.805576	0.029*
C20	0.44955 (10)	0.3106 (2)	0.87343 (13)	0.0262 (4)
H20A	0.437460	0.390552	0.898999	0.031*
H20B	0.406622	0.270325	0.821191	0.031*
C21	0.48772 (10)	0.1834 (2)	0.93957 (13)	0.0281 (4)
H21A	0.495221	0.098353	0.911865	0.034*
H21B	0.459693	0.145614	0.958672	0.034*
C22	0.55656 (10)	0.2392 (2)	1.01863 (12)	0.0256 (4)
H22A	0.581609	0.153099	1.058555	0.031*
H22B	0.548684	0.315490	1.050304	0.031*
C23	0.60031 (10)	0.3096 (2)	0.99230 (13)	0.0264 (4)
H23A	0.643242	0.349894	1.044513	0.032*
H23B	0.612306	0.231184	0.965832	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0151 (2)	0.0140 (2)	0.0277 (2)	0.000	0.00945 (17)	0.000
N1	0.0226 (8)	0.0191 (8)	0.0361 (9)	−0.0028 (6)	0.0130 (7)	0.0022 (7)
C1	0.0240 (9)	0.0176 (8)	0.0317 (9)	0.0029 (7)	0.0167 (8)	0.0038 (7)
S1	0.0212 (2)	0.0271 (2)	0.0354 (2)	−0.00593 (17)	0.0138 (2)	−0.00315 (18)
S11	0.0221 (2)	0.0209 (2)	0.0337 (2)	0.00480 (16)	0.01759 (19)	0.00516 (17)
C11	0.0167 (8)	0.0214 (9)	0.0251 (8)	0.0010 (7)	0.0105 (7)	0.0026 (7)
N11	0.0209 (7)	0.0206 (8)	0.0381 (9)	0.0044 (6)	0.0186 (7)	0.0086 (6)
C12	0.0182 (8)	0.0251 (9)	0.0329 (9)	0.0022 (7)	0.0156 (8)	0.0053 (8)
C13	0.0241 (10)	0.0537 (14)	0.0336 (10)	0.0071 (9)	0.0157 (9)	0.0142 (10)
C14	0.0342 (12)	0.0667 (17)	0.0342 (11)	0.0050 (11)	0.0229 (10)	0.0070 (11)
C15	0.0251 (10)	0.0360 (11)	0.0479 (12)	0.0000 (8)	0.0250 (10)	0.0022 (9)
C16	0.0199 (9)	0.0290 (10)	0.0376 (10)	0.0010 (8)	0.0154 (8)	−0.0003 (8)
C17	0.0234 (9)	0.0285 (9)	0.0292 (9)	0.0023 (7)	0.0144 (8)	0.0011 (8)
N12	0.0177 (7)	0.0215 (7)	0.0298 (7)	0.0023 (6)	0.0148 (6)	0.0042 (6)
C18	0.0186 (8)	0.0197 (8)	0.0261 (9)	0.0001 (7)	0.0134 (7)	0.0027 (7)
C19	0.0221 (9)	0.0261 (9)	0.0242 (8)	−0.0031 (7)	0.0129 (7)	−0.0002 (7)
C20	0.0227 (9)	0.0275 (10)	0.0290 (9)	−0.0066 (7)	0.0155 (8)	−0.0030 (7)
C21	0.0324 (10)	0.0239 (9)	0.0344 (10)	−0.0052 (8)	0.0232 (9)	−0.0014 (8)
C22	0.0280 (9)	0.0238 (9)	0.0288 (9)	0.0040 (7)	0.0188 (8)	0.0066 (7)
C23	0.0220 (9)	0.0255 (9)	0.0310 (9)	0.0044 (7)	0.0151 (8)	0.0086 (7)

Geometric parameters (Å, º) top

Co1—N1	1.9516 (16)	C16—H16B	0.9900
Co1—N1ⁱ	1.9517 (16)	C16—C17	1.530 (3)
Co1—S11	2.3130 (5)	C17—H17A	0.9900
Co1—S11ⁱ	2.3131 (5)	C17—H17B	0.9900
N1—C1	1.167 (3)	N12—H12A	0.8800
C1—S1	1.620 (2)	N12—C18	1.472 (2)
S11—C11	1.7431 (18)	C18—H18	1.0000
C11—N11	1.330 (2)	C18—C19	1.526 (2)
C11—N12	1.328 (2)	C18—C23	1.525 (2)
N11—H11	0.8800	C19—H19A	0.9900
N11—C12	1.470 (2)	C19—H19B	0.9900
C12—H12	1.0000	C19—C20	1.529 (2)
C12—C13	1.520 (3)	C20—H20A	0.9900
C12—C17	1.522 (3)	C20—H20B	0.9900
C13—H13A	0.9900	C20—C21	1.526 (3)
C13—H13B	0.9900	C21—H21A	0.9900
C13—C14	1.522 (3)	C21—H21B	0.9900
C14—H14A	0.9900	C21—C22	1.528 (3)
C14—H14B	0.9900	C22—H22A	0.9900
C14—C15	1.519 (3)	C22—H22B	0.9900
C15—H15A	0.9900	C22—C23	1.534 (3)
C15—H15B	0.9900	C23—H23A	0.9900
C15—C16	1.522 (3)	C23—H23B	0.9900
C16—H16A	0.9900

N1—Co1—N1ⁱ	113.00 (10)	C12—C17—C16	110.88 (16)
N1—Co1—S11ⁱ	109.67 (5)	C12—C17—H17A	109.5
N1—Co1—S11	106.00 (5)	C12—C17—H17B	109.5
N1ⁱ—Co1—S11ⁱ	106.00 (5)	C16—C17—H17A	109.5
N1ⁱ—Co1—S11	109.67 (5)	C16—C17—H17B	109.5
S11—Co1—S11ⁱ	112.63 (3)	H17A—C17—H17B	108.1
C1—N1—Co1	157.11 (17)	C11—N12—H12A	118.1
N1—C1—S1	179.39 (19)	C11—N12—C18	123.87 (15)
C11—S11—Co1	101.24 (6)	C18—N12—H12A	118.1
N11—C11—S11	119.32 (14)	N12—C18—H18	108.3
N12—C11—S11	120.02 (13)	N12—C18—C19	111.41 (15)
N12—C11—N11	120.67 (16)	N12—C18—C23	109.67 (14)
C11—N11—H11	116.0	C19—C18—H18	108.3
C11—N11—C12	127.98 (16)	C23—C18—H18	108.3
C12—N11—H11	116.0	C23—C18—C19	110.89 (16)
N11—C12—H12	108.5	C18—C19—H19A	109.7
N11—C12—C13	107.87 (16)	C18—C19—H19B	109.7
N11—C12—C17	111.80 (16)	C18—C19—C20	110.05 (15)
C13—C12—H12	108.5	H19A—C19—H19B	108.2
C13—C12—C17	111.64 (16)	C20—C19—H19A	109.7
C17—C12—H12	108.5	C20—C19—H19B	109.7
C12—C13—H13A	109.4	C19—C20—H20A	109.4
C12—C13—H13B	109.4	C19—C20—H20B	109.4
C12—C13—C14	111.01 (18)	H20A—C20—H20B	108.0
H13A—C13—H13B	108.0	C21—C20—C19	110.96 (16)
C14—C13—H13A	109.4	C21—C20—H20A	109.4
C14—C13—H13B	109.4	C21—C20—H20B	109.4
C13—C14—H14A	109.4	C20—C21—H21A	109.5
C13—C14—H14B	109.4	C20—C21—H21B	109.5
H14A—C14—H14B	108.0	C20—C21—C22	110.86 (16)
C15—C14—C13	111.2 (2)	H21A—C21—H21B	108.1
C15—C14—H14A	109.4	C22—C21—H21A	109.5
C15—C14—H14B	109.4	C22—C21—H21B	109.5
C14—C15—H15A	109.4	C21—C22—H22A	109.2
C14—C15—H15B	109.4	C21—C22—H22B	109.2
C14—C15—C16	111.08 (17)	C21—C22—C23	111.83 (16)
H15A—C15—H15B	108.0	H22A—C22—H22B	107.9
C16—C15—H15A	109.4	C23—C22—H22A	109.2
C16—C15—H15B	109.4	C23—C22—H22B	109.2
C15—C16—H16A	109.3	C18—C23—C22	109.63 (15)
C15—C16—H16B	109.3	C18—C23—H23A	109.7
C15—C16—C17	111.61 (17)	C18—C23—H23B	109.7
H16A—C16—H16B	108.0	C22—C23—H23A	109.7
C17—C16—H16A	109.3	C22—C23—H23B	109.7
C17—C16—H16B	109.3	H23A—C23—H23B	108.2

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···N1	0.88	2.33	3.169 (2)	160
C12—H12···S1ⁱⁱ	1.00	2.93	3.774 (2)	143
N12—H12A···S1ⁱⁱ	0.88	2.84	3.6770 (16)	159
C19—H19B···S11	0.99	3.00	3.529 (2)	114

Symmetry code: (ii) x, y−1, z.

Acknowledgements

Financial support by the State of Schleswig-Holstein and the Deutsche Forschungsgemeinschaft is gratefully acknowledged.

Funding information

Funding for this research was provided by: Deutsche Forschungsgemeinschaft (grant No. NA720/5-2).

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