Synthesis, crystal structure and properties of poly[(μ-2-methyl­pyridine N-oxide-κ2O:O)bis­(μ-thio­cyanato-κ2N:S)cobalt(II)]

Näther, C.; Jess, I.

doi:10.1107/S2056989023010721

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ISSN: 2056-9890

Volume 80| Part 1| January 2024| Pages 67-71

https://doi.org/10.1107/S2056989023010721

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Synthesis, crystal structure and properties of poly[(μ-2-methylpyridine N-oxide-κ²O:O)bis(μ-thiocyanato-κ²N:S)cobalt(II)]

Christian Näther ^a ^* and Inke Jess ^a

^aInstitut für Anorganische Chemie, Universität Kiel, Max-Eyth.-Strasse 2, 24118 Kiel, Germany
^*Correspondence e-mail: cnaether@ac.uni-kiel.de

Edited by S. Parkin, University of Kentucky, USA (Received 6 December 2023; accepted 14 December 2023; online 1 January 2024)

The title compound, [Co(NCS)₂(C₆H₇NO)]_n or Co(NCS)₂(2-methylpyridine N-oxide), was prepared by the reaction of Co(NCS)₂ and 2-methylpyridine N-oxide in methanol. All crystals obtained by this procedure show reticular pseudo-merohedric twinning, but after recrystallization, one crystal was found that had a minor component with only a very few overlapping reflections. The asymmetric unit consists of one Co^II cation, two thiocyanate anions and one 2-methylpyridine N-oxide coligand in general positions. The Co^II cations are octahedrally coordinated by two O-bonding 2-methylpyridine N-oxide ligands, as well as two S- and two N-bonding thiocyanate anions, and are connected via μ-1,3(N,S)-bridging thiocyanate anions into chains that are linked by μ-1,1(O,O) bridging coligands into layers. No pronounced directional intermolecular interactions are observed between the layers. The 2-methylpyridine coligand is disordered over two orientations and was refined using a split model with restraints. Powder X-ray diffraction (PXRD) indicates that a pure sample was obtained and IR spectroscopy confirms that bridging thiocyanate anions are present. Thermogravimetry and differential thermoanalysis (TG-DTA) shows one poorly resolved mass loss in the TG curve that is accompanied by an exothermic and an endothermic signal in the DTA curve, which indicate the decomposition of the 2-methylpyridine N-oxide coligands.

Keywords: synthesis; crystal structure; layered structure; IR spectrum; thermal properties.

CCDC reference: 2314409

1. Chemical context

Investigations on the synthesis, structures and properties of coordination compounds is still an active field in coordination chemistry because of their versatile structural behavior and their diverse physical properties. Based on simple considerations concerning the coordination behavior of the cations, the anions and the additional coligands, their structures can be influenced to some extent. In this regard, coordination polymers are of special interest, because mono-, di- and tri-periodic networks can be generated, which can show, for example, cooperative magnetic phenomena, non-linear optical properties or conductivity (Yue & Gao, 2019 ; Ferrando-Soria et al., 2017 ; Wang et al., 2012 ; Coronado et al., 2000 ). In this context, numerous compounds based on small-sized anions such as, for example, cyanide, azide or carboxylate have been reported in recent years (Nowicka et al., 2012 ; Yue & Gao, 2019; Ohba & Ōkawa, 2000 ; Zhou et al., 2012 ).

In our own research, we are focused on the synthesis, structures and properties of transition-metal thiocyanate coordination polymers, for which predominantly chain and layered compounds are observed (Näther et al., 2013 ). In most chain compounds, the metal cations are linked by pairs of μ-1,3-bridging thiocyanate anions and the geometry of the chain – linear or corrugated – depends on the actual metal coordination, e.g. all-trans or cis–cis–trans (Jochim et al., 2018 ; Rams et al., 2020 ; Böhme et al., 2020 ). For layered compounds, two different motifs are mainly observed in which the metal cations are linked by only single bridging anionic ligands (Werner et al., 2015a ) or in which two metal cations are connected by pairs of thiocyanate anions into dinuclear units that are further linked into layers by single μ-1,3-bridging anionic ligands (Werner et al., 2015b ). Compared to this, thiocyanate compounds with more condensed networks are rare (Neumann et al., 2018 ).

In recent work, we mainly focused on monocoordinating coligands that in nearly all cases consist of pyridine derivatives, but it is noted that chain or layered thiocyanate networks can be further connected if bridging coligands such as pyrazine or bipyridine derivatives are used (Real et al., 1991 ; Adams et al., 2010 ).

Another class of interesting ligands are represented by pyridine N-oxide ligands, for which many structures are reported. In nearly all compounds, these ligands show two different coordination modes, which include the terminal N-coordination or the μ-1,1(O,O)-bridging mode, where the latter mode is of interest for the synthesis of compounds with more condensed networks. We therefore became interested in this class of ligands. Within this project, we tried to prepare compounds based on Co(NCS)₂, which is of interest for our project. We used 2-methylpyridine as the ligand, for which only three compounds with Mn, Cd and Zn are reported (see Database survey). Within this work, we reacted Co(NCS)₂ with 2-methylpyridine in methanol, which led to the formation of violet-colored, block-like crystals, which were characterized by single-crystal X-ray diffraction. This proved that a coordination polymer with the composition Co(NCS)₂(2-methylpyridine N-oxide) was obtained that is isotypic to its Cd and Mn analogs already reported in the literature (Mautner et al., 2016 and 2018 ).

2. Structural commentary

The asymmetric unit of the title compound, Co(NCS)₂(2-methylpyridine N-oxide), consists of one cobalt cation, one 2-methylpyridine N-oxide coligand as well as of two thiocyanate anions, all of them located in general positions (Fig. 1). The 2-methylpyridine coligand is disordered over two orientations and was refined using a split model with restraints (see Refinement). The Co^II cations are sixfold coordinated by two O atoms of two symmetry-equivalent μ-1,1(O,O)-bridging 2-methylpyridine N-oxide coligands, as well as by two N and two S atoms of four μ-1,3(N,S)-bridging thiocyanate anions (Fig. 1). The two N-bonding thiocyanate anions are in trans-positions, whereas the two S-bonding anions as well as the two O atoms of the coligands are in cis-positions (Figs. 1 and 2). The bond distances correspond to standard values and from the bonding angles it is obvious that the Co^II cations are in a slightly distorted octahedral coordination (Table 1). The Co^II cations are linked by pairs of thiocyanate anions that are located on centers of inversion into chains that proceed along the [110] direction (Figs. 2 and 3). Because of the cis–cis–trans-coordination, these chains are corrugated with a dihedral angle of 108.52 (3)° between the two neighbouring Co(NCS)₂Co planes. These chains are further linked into layers by planar four-membered centrosymmetric Co₂O₂ rings, built up of two cobalt cations and two μ-1,1(O,O)-bridging O atoms of the 2-methylpyridine N-oxide coligands. The layers are parallel to the ab-plane (Fig. 3 and S1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯S1ⁱ	0.95	2.81	3.491 (3)	129
C14—H14⋯S2ⁱⁱ	0.95	2.82	3.514 (3)	131
C16—H16A⋯N1	0.98	2.63	3.484 (4)	145
Symmetry codes: (i) ; (ii) .

Figure 1
Crystal structure of the title compound showing the Co coordination with labeling and displacement ellipsoids drawn at the 50% probability level. Symmetry codes: (i) −x + 1, −y + 2, −z + 1; (ii) −x, −y + 1, −z + 1; (iii) −x + 1, −y + 1, −z + 1. For clarity, the disorder of the 2-methylpyridine N-oxide coligand is shown with full and open bonds for only one ligand.

Figure 2
Crystal structure of the title compound, showing the connection of the Co cations. The C—H hydrogen atoms as well as the disorder of the 2-methylpyridine N-oxide coligand are omitted for clarity.

Figure 3
Crystal structure of the title compound with view along the crystallographic c-axis direction of a part of a layer. The disorder of the 2-methylpyridine coligand is not shown.

3. Supramolecular features

In the crystal structure of the title compound, the layers are stacked in the c-axis direction and are separated by the 2-methylpyridine N-oxide coligands (Fig. S1). There are no pronounced directional intermolecular interactions between the layers. There are two interlayer C—H⋯S and one intralayer C—H⋯N contacts with large distances and angles far from linearity that should correspond to only very weak interactions (Table 1).

4. Database survey

Searching for structures built up of a transition-metal thiocyanate and 2-methylpyridine N-oxide using the Cambridge Structural Database (CSD version 5.43, last update November 2021; Groom et al., 2016 ) and ConQuest (Bruno et al., 2002) reveals that only three structures have been published. They include M(NCS)₂(2-methylpyridine N-oxide with M = Mn, Cd that are isotypic to the title compound [Refcodes: KESRUY (Mautner et al., 2018) and UKILIL (Mautner et al., 2016)]. There is one additional compound with the composition Zn(NCS)₂(2-methylpyridine N-oxide)₂(H₂O) that is built up of discrete complexes, in which the Zn cations are fivefold coordinated by two terminal N-bonding anionic ligands, two O-bonding 2-methylpyridine N-oxide coligands and one water molecule (Refcode: UKIMEI; Mautner et al., 2016).

If the search is extended to compounds with Co(NCS)₂ and the other methylpyridine N-oxide isomers, no hits for 3-methylpyridine N-oxide are observed, whereas two structures were found for 4-methylpyridine N-oxide. The crystal structure of Co(NCS)₂(4-methylpyridine N-oxide) is very similar to that of the title compound, because the Co^II cations are linked by pairs of thiocyanate anions into chains that are connected into layers by μ-1,1(O,O)-bridging O atoms of the 4-methylpyridine ligands (Refcode: MEQKOJ; Zhang et al., 2006 ). In contrast to the title compound, the N-coordinating thiocyanate anions are in cis-positions, whereas the S-bonding anionic ligands are in a trans-configuration. In the second compound, Co(NCS)₂(4-methylpyridine N-oxide)(MeOH), the Co^II cations are octahedrally coordinated by one terminal N-bonding and two bridging thiocyanate anions, one methanol molecule and two μ-1,1(O,O)-bridging O atoms of the 4-methylpyridine ligands (Shi et al., 2006 ). Each of the two Co^II cations are linked by pairs of anionic ligands into dinuclear units, which are further connected via two μ-1,1(O,O)-bridging 4-methylpyridine ligands into chains.

5. Physical characterization

Comparison of the experimental X-ray powder pattern with that calculated from single-crystal data proves that a pure crystalline phase has been obtained that is of poor crystallinity (Fig. 4). In the IR spectrum, the CN stretching vibration is observed at 2107 and 2160 cm⁻¹, in agreement with the presence of only μ-1,3-bridging thiocyanate anions (Fig. S2). The occurrence of two different bands might be traced back to the fact that two crystallographically independent thiocyanate anions are present.

Figure 4
Experimental (top) and calculated X-ray powder pattern (bottom) for the title compound.

The thermal properties of the title compound were investigated by thermogravimetry (TG) and differential thermoanalysis (DTA). Upon heating, decomposition starts at about 240°C, followed by a continuous mass loss that is not finished until 450°C (Fig. S3). From the first derivative of the TG curve (DTG curve), it is indicated that this mass loss consists of two different steps, which cannot be resolved even at lower heating rates. The mass loss is accompanied by a small exothermic signal, followed by an endothermic signal, which points to the decomposition of the coligands, as observed in previous work (Näther & Jess, 2023 ).

6. Synthesis and crystallization

Synthesis

Co(NCS)₂ (99%) was purchased from Sigma Aldrich and 2-methylpyridine N-oxide (96%) from Aldrich. Single crystals were prepared by reacting 0.5 mmol of Co(NCS)₂ (87.1 mg), with 0.25 mmol of 2-methylpyridine N-oxide (27.3) mg in 1 mL of methanol. Within 3 days, violet-colored crystals were obtained that all showed reticular pseudo-merohedric twinning. A nearly single crystal was found in a recrystallized batch. A microcrystalline powder was obtained using the same amount of reactants under continuous stirring.

Experimental details

The data collection was performed using an XtaLAB Synergy, Dualflex, HyPix diffractometer from Rigaku with Cu Kα radiation. The PXRD measurements were performed with a Stoe Transmission Powder Diffraction System (STADI P) with a MYTHEN 1K detector, a Johansson-type Ge(111) monochromator and Cu Kα₁ radiation (λ = 1.540598 Å). The IR spectrum was measured using an ATI Mattson Genesis Series FTIR Spectrometer. Thermogravimetry and differential thermoanalysis (TG-DTA) was performed in a dynamic nitrogen atmosphere in Al₂O₃ crucibles using an STA-PT 1000 thermobalance from Linseis. The instrument was calibrated using standard reference materials.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. In the beginning, it was noted that all crystals investigated consisted of reticular pseudo-merohedric twins, giving the impression of a very large unit cell axis. For these crystals, about 26% of the reflections overlap (Fig. S4). Several of these twins were measured, which always revealed the same kind of twinning. For these crystals only poor reliability factors were obtained, even if a twin refinement using data in HKLF-5 format were used. After recrystallization from methanol, however, one crystal was found that consisted of two intergrown individuals and in this case less than 2% of the reflections overlapped if a measurement at large detector distances was performed (Fig. S5). A two-component refinement with data in HKLF-5 format led to comparable reliability factors and, therefore, the data presented here originate from a refinement neglecting the smaller component.

Table 2
Experimental details

Crystal data
Chemical formula	[Co(NCS)₂(C₆H₇NO)]
M_r	284.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.67386 (11), 7.66462 (9), 18.8755 (2)
β (°)	97.4258 (12)
V (Å³)	1100.89 (2)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	15.58
Crystal size (mm)	0.16 × 0.12 × 0.10

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.392, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	16436, 2355, 2337
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.637

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.066, 1.17
No. of reflections	2355
No. of parameters	202
No. of restraints	108
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.48
Computer programs: CrysAlis PRO (Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2014/5 (Sheldrick, 2015b ), SHELXL2016/6 (Sheldrick, 2015a ), DIAMOND (Brandenburg & Putz, 1999 ) and publCIF (Westrip, 2010 ).

The C-bound H atoms were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined isotropically with U_iso(H) = 1.2 U_eq(C) (1.5 for methyl H atoms) using a riding model. The 2-methylpyridine coligand is disordered over two orientations and was refined using a split model with SADI and RIGU as restraints. Refinement of the occupancy led to a value of 0.841 (4) for N11 to C16.

Supporting information

CCDC reference: 2314409

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989023010721/pk2699sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023010721/pk2699Isup2.hkl

Figure S1. Crystal structure of the title compound with view of the arrangement of the layers along the crystallographic a-axis direction. DOI: https://doi.org/10.1107/S2056989023010721/pk2699sup3.png

Figure S2. IR spectrum of the title compound. Given are the values of the CN stretching vibration of the thiocyanate anions. DOI: https://doi.org/10.1107/S2056989023010721/pk2699sup4.png

Figure S3. TG, DTA and DTG curve of the title compound. DOI: https://doi.org/10.1107/S2056989023010721/pk2699sup5.png

Figure S4. Reciprocal space plot of a crystal of the title compound showing the partial merohedral twinning, which is common for most crystals. Reflections of the second indiviual are indicated in turquoise. DOI: https://doi.org/10.1107/S2056989023010721/pk2699sup6.png

Figure S5. Reciprocal space plot of the crystal of the title compound used for the structure determination. Reflections of the second indiviual are indicated in turquoise. DOI: https://doi.org/10.1107/S2056989023010721/pk2699sup7.png

checkCIF report

Computing details top

Poly[(µ-2-methylpyridine N-oxide-κ²O:O)bis(µ-thiocyanato-κ²N:S)cobalt(II)] top

Crystal data top

[Co(NCS)₂(C₆H₇NO)]	F(000) = 572
M_r = 284.22	D_x = 1.715 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 7.67386 (11) Å	Cell parameters from 12043 reflections
b = 7.66462 (9) Å	θ = 4.7–78.3°
c = 18.8755 (2) Å	µ = 15.58 mm⁻¹
β = 97.4258 (12)°	T = 100 K
V = 1100.89 (2) Å³	Block, violet
Z = 4	0.16 × 0.12 × 0.10 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	2355 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2337 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.023
Detector resolution: 10.0000 pixels mm^-1	θ_max = 79.1°, θ_min = 4.7°
ω scans	h = −9→7
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2023)	k = −9→9
T_min = 0.392, T_max = 1.000	l = −23→23
16436 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.029	w = 1/[σ²(F_o²) + (0.0149P)² + 1.9175P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.066	(Δ/σ)_max = 0.001
S = 1.17	Δρ_max = 0.37 e Å⁻³
2355 reflections	Δρ_min = −0.48 e Å⁻³
202 parameters	Extinction correction: SHELXL2016/6 (Sheldrick, 2015a), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
108 restraints	Extinction coefficient: 0.00044 (8)

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	Occ. (<1)
Co1	0.34308 (4)	0.65702 (5)	0.50034 (2)	0.01618 (11)
N1	0.4776 (3)	0.8322 (3)	0.44534 (11)	0.0208 (4)
C1	0.5616 (3)	0.9467 (3)	0.42847 (12)	0.0178 (4)
S1	0.68342 (7)	1.10993 (7)	0.40518 (3)	0.02297 (14)
N2	0.1858 (2)	0.5034 (3)	0.55502 (11)	0.0197 (4)
C2	0.0761 (3)	0.4137 (3)	0.57123 (12)	0.0173 (4)
S2	−0.07968 (7)	0.28422 (7)	0.59360 (3)	0.02083 (14)
O11	0.4258 (2)	0.4442 (2)	0.44114 (9)	0.0216 (3)
N11	0.3245 (4)	0.3636 (4)	0.38733 (13)	0.0169 (5)	0.841 (4)
C11	0.3369 (3)	0.4046 (4)	0.31808 (14)	0.0191 (5)	0.841 (4)
C12	0.2263 (4)	0.3189 (4)	0.26500 (18)	0.0216 (6)	0.841 (4)
H12	0.230783	0.346504	0.216205	0.026*	0.841 (4)
C13	0.1095 (4)	0.1932 (4)	0.28298 (16)	0.0233 (6)	0.841 (4)
H13	0.034696	0.134137	0.246672	0.028*	0.841 (4)
C14	0.1026 (4)	0.1545 (4)	0.35428 (15)	0.0210 (5)	0.841 (4)
H14	0.023386	0.068607	0.367329	0.025*	0.841 (4)
C15	0.2116 (4)	0.2416 (4)	0.40574 (16)	0.0182 (5)	0.841 (4)
H15	0.207596	0.216017	0.454751	0.022*	0.841 (4)
C16	0.4679 (4)	0.5389 (4)	0.30386 (18)	0.0292 (7)	0.841 (4)
H16A	0.440560	0.649386	0.326122	0.044*	0.841 (4)
H16B	0.463728	0.555500	0.252188	0.044*	0.841 (4)
H16C	0.585805	0.500344	0.323906	0.044*	0.841 (4)
N11'	0.3614 (17)	0.3997 (17)	0.3791 (6)	0.012 (2)	0.159 (4)
C11'	0.2342 (16)	0.2832 (16)	0.3592 (6)	0.016 (2)	0.159 (4)
C12'	0.1856 (19)	0.2643 (19)	0.2851 (7)	0.018 (3)	0.159 (4)
H12'	0.095521	0.184123	0.267840	0.021*	0.159 (4)
C13'	0.2677 (19)	0.361 (2)	0.2368 (8)	0.024 (2)	0.159 (4)
H13'	0.233256	0.348303	0.186914	0.029*	0.159 (4)
C14'	0.4001 (18)	0.4778 (18)	0.2616 (7)	0.022 (2)	0.159 (4)
H14'	0.457737	0.544852	0.229290	0.026*	0.159 (4)
C15'	0.4451 (18)	0.4935 (19)	0.3330 (7)	0.021 (2)	0.159 (4)
H15'	0.536599	0.571321	0.350960	0.025*	0.159 (4)
C16'	0.157 (2)	0.1870 (19)	0.4155 (8)	0.018 (3)	0.159 (4)
H16D	0.066740	0.106925	0.393423	0.027*	0.159 (4)
H16E	0.249770	0.120445	0.444436	0.027*	0.159 (4)
H16F	0.104815	0.269982	0.446106	0.027*	0.159 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01039 (17)	0.01187 (18)	0.0253 (2)	−0.00181 (13)	−0.00148 (13)	0.00080 (14)
N1	0.0176 (9)	0.0175 (10)	0.0271 (10)	−0.0046 (8)	0.0021 (8)	−0.0025 (8)
C1	0.0133 (10)	0.0160 (11)	0.0233 (11)	0.0019 (9)	−0.0001 (8)	−0.0030 (9)
S1	0.0194 (3)	0.0162 (3)	0.0350 (3)	−0.0040 (2)	0.0102 (2)	−0.0005 (2)
N2	0.0141 (9)	0.0164 (9)	0.0272 (10)	−0.0039 (7)	−0.0029 (7)	0.0035 (8)
C2	0.0148 (10)	0.0139 (10)	0.0214 (11)	0.0020 (8)	−0.0041 (8)	0.0020 (8)
S2	0.0137 (2)	0.0181 (3)	0.0295 (3)	−0.0029 (2)	−0.0020 (2)	0.0083 (2)
O11	0.0142 (7)	0.0193 (8)	0.0286 (9)	0.0002 (6)	−0.0078 (6)	−0.0075 (7)
N11	0.0143 (11)	0.0141 (11)	0.0215 (8)	0.0003 (8)	−0.0010 (6)	−0.0005 (6)
C11	0.0174 (9)	0.0171 (10)	0.0218 (8)	−0.0020 (8)	−0.0008 (6)	−0.0001 (6)
C12	0.0192 (10)	0.0194 (11)	0.0247 (9)	−0.0016 (9)	−0.0025 (8)	−0.0021 (8)
C13	0.0198 (11)	0.0204 (12)	0.0285 (9)	−0.0022 (9)	−0.0022 (7)	−0.0010 (7)
C14	0.0169 (10)	0.0162 (11)	0.0287 (9)	0.0004 (8)	−0.0018 (6)	−0.0011 (7)
C15	0.0141 (9)	0.0138 (10)	0.0260 (9)	0.0009 (8)	0.0001 (7)	0.0003 (7)
C16	0.0287 (12)	0.0295 (13)	0.0283 (15)	−0.0132 (11)	0.0000 (11)	0.0021 (11)
N11'	0.007 (4)	0.004 (4)	0.024 (3)	0.003 (3)	−0.001 (2)	0.003 (2)
C11'	0.011 (4)	0.009 (4)	0.027 (3)	−0.001 (3)	−0.001 (2)	0.001 (2)
C12'	0.013 (5)	0.013 (5)	0.026 (3)	−0.008 (4)	0.000 (2)	0.002 (2)
C13'	0.020 (4)	0.022 (5)	0.031 (3)	−0.012 (3)	0.002 (3)	0.006 (3)
C14'	0.018 (4)	0.018 (5)	0.029 (3)	−0.009 (3)	0.001 (3)	0.008 (3)
C15'	0.016 (4)	0.017 (5)	0.029 (3)	−0.004 (4)	0.001 (2)	0.007 (3)
C16'	0.014 (5)	0.011 (5)	0.029 (3)	−0.001 (4)	0.001 (3)	0.003 (3)

Geometric parameters (Å, º) top

Co1—N1	2.055 (2)	C14—H14	0.9500
Co1—S1ⁱ	2.5507 (7)	C14—C15	1.371 (4)
Co1—N2	2.057 (2)	C15—H15	0.9500
Co1—S2ⁱⁱ	2.5507 (6)	C16—H16A	0.9800
Co1—O11ⁱⁱⁱ	2.1126 (16)	C16—H16B	0.9800
Co1—O11	2.1200 (17)	C16—H16C	0.9800
N1—C1	1.158 (3)	N11'—C11'	1.340 (13)
C1—S1	1.654 (2)	N11'—C15'	1.354 (14)
N2—C2	1.158 (3)	C11'—C12'	1.408 (14)
C2—S2	1.650 (2)	C11'—C16'	1.478 (14)
O11—N11	1.346 (3)	C12'—H12'	0.9500
O11—N11'	1.258 (11)	C12'—C13'	1.389 (14)
N11—C11	1.359 (4)	C13'—H13'	0.9500
N11—C15	1.351 (4)	C13'—C14'	1.387 (14)
C11—C12	1.391 (4)	C14'—H14'	0.9500
C11—C16	1.488 (4)	C14'—C15'	1.351 (15)
C12—H12	0.9500	C15'—H15'	0.9500
C12—C13	1.387 (5)	C16'—H16D	0.9800
C13—H13	0.9500	C16'—H16E	0.9800
C13—C14	1.386 (4)	C16'—H16F	0.9800

N1—Co1—S1ⁱ	89.21 (6)	C13—C14—H14	120.4
N1—Co1—N2	173.32 (8)	C15—C14—C13	119.2 (3)
N1—Co1—S2ⁱⁱ	86.46 (6)	C15—C14—H14	120.4
N1—Co1—O11ⁱⁱⁱ	93.52 (7)	N11—C15—C14	120.5 (3)
N1—Co1—O11	91.85 (7)	N11—C15—H15	119.7
S1ⁱ—Co1—S2ⁱⁱ	103.58 (2)	C14—C15—H15	119.7
N2—Co1—S1ⁱ	86.86 (6)	C11—C16—H16A	109.5
N2—Co1—S2ⁱⁱ	89.22 (5)	C11—C16—H16B	109.5
N2—Co1—O11	93.38 (7)	C11—C16—H16C	109.5
N2—Co1—O11ⁱⁱⁱ	91.99 (7)	H16A—C16—H16B	109.5
O11ⁱⁱⁱ—Co1—S1ⁱ	91.66 (5)	H16A—C16—H16C	109.5
O11—Co1—S1ⁱ	164.49 (5)	H16B—C16—H16C	109.5
O11—Co1—S2ⁱⁱ	91.93 (4)	O11—N11'—C11'	128.8 (10)
O11ⁱⁱⁱ—Co1—S2ⁱⁱ	164.76 (5)	O11—N11'—C15'	107.0 (9)
O11ⁱⁱⁱ—Co1—O11	72.83 (7)	C11'—N11'—C15'	124.2 (11)
C1—N1—Co1	165.51 (19)	N11'—C11'—C12'	115.9 (11)
N1—C1—S1	179.3 (2)	N11'—C11'—C16'	118.3 (11)
C1—S1—Co1ⁱ	104.18 (8)	C12'—C11'—C16'	125.8 (11)
C2—N2—Co1	165.02 (18)	C11'—C12'—H12'	119.6
N2—C2—S2	179.3 (2)	C13'—C12'—C11'	120.8 (13)
C2—S2—Co1ⁱⁱ	104.54 (8)	C13'—C12'—H12'	119.6
Co1ⁱⁱⁱ—O11—Co1	107.17 (7)	C12'—C13'—H13'	120.1
N11—O11—Co1	124.58 (16)	C14'—C13'—C12'	119.8 (13)
N11—O11—Co1ⁱⁱⁱ	126.14 (16)	C14'—C13'—H13'	120.1
N11'—O11—Co1	126.2 (7)	C13'—C14'—H14'	120.8
O11—N11—C11	120.9 (2)	C15'—C14'—C13'	118.4 (12)
O11—N11—C15	116.8 (2)	C15'—C14'—H14'	120.8
C15—N11—C11	122.3 (3)	N11'—C15'—H15'	119.6
N11—C11—C12	118.1 (3)	C14'—C15'—N11'	120.8 (12)
N11—C11—C16	117.8 (2)	C14'—C15'—H15'	119.6
C12—C11—C16	124.1 (3)	C11'—C16'—H16D	109.5
C11—C12—H12	119.8	C11'—C16'—H16E	109.5
C13—C12—C11	120.3 (3)	C11'—C16'—H16F	109.5
C13—C12—H12	119.8	H16D—C16'—H16E	109.5
C12—C13—H13	120.2	H16D—C16'—H16F	109.5
C14—C13—C12	119.5 (3)	H16E—C16'—H16F	109.5
C14—C13—H13	120.2

Co1—O11—N11—C11	98.2 (3)	C11—N11—C15—C14	−0.6 (5)
Co1ⁱⁱⁱ—O11—N11—C11	−100.5 (3)	C11—C12—C13—C14	0.5 (4)
Co1—O11—N11—C15	−81.8 (3)	C12—C13—C14—C15	0.1 (4)
Co1ⁱⁱⁱ—O11—N11—C15	79.5 (3)	C13—C14—C15—N11	−0.1 (4)
Co1ⁱⁱⁱ—O11—N11'—C11'	95.9 (16)	C15—N11—C11—C12	1.2 (5)
Co1—O11—N11'—C11'	−93.1 (16)	C15—N11—C11—C16	−179.0 (3)
Co1ⁱⁱⁱ—O11—N11'—C15'	−84.3 (12)	C16—C11—C12—C13	179.0 (3)
Co1—O11—N11'—C15'	86.8 (12)	N11'—C11'—C12'—C13'	0 (2)
O11—N11—C11—C12	−178.8 (3)	C11'—N11'—C15'—C14'	2 (3)
O11—N11—C11—C16	1.0 (4)	C11'—C12'—C13'—C14'	0 (2)
O11—N11—C15—C14	179.4 (2)	C12'—C13'—C14'—C15'	0 (2)
O11—N11'—C11'—C12'	178.2 (13)	C13'—C14'—C15'—N11'	−1 (2)
O11—N11'—C11'—C16'	−2 (2)	C15'—N11'—C11'—C12'	−2 (2)
O11—N11'—C15'—C14'	−177.9 (13)	C15'—N11'—C11'—C16'	178.5 (16)
N11—C11—C12—C13	−1.1 (4)	C16'—C11'—C12'—C13'	−179.7 (15)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···S1^iv	0.95	2.81	3.491 (3)	129
C14—H14···S2^v	0.95	2.82	3.514 (3)	131
C16—H16A···N1	0.98	2.63	3.484 (4)	145

Symmetry codes: (iv) x−1, y−1, z; (v) −x, −y, −z+1.

Acknowledgements

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

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