Synthesis, crystal structure and properties of catena-poly[[bis­(4-methyl­pyridine-κN)cobalt(II)]-di-μ-thio­cyanato-κ2N:S;κ2S:N], which shows a rare coordination geometry

Näther, C.; Boeckmann, J.

doi:10.1107/S2056989024012003

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Volume 81| Part 1| January 2025| Pages 58-62

https://doi.org/10.1107/S2056989024012003

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Synthesis, crystal structure and properties of catena-poly[[bis(4-methylpyridine-κN)cobalt(II)]-di-μ-thiocyanato-κ²N:S;κ²S:N], which shows a rare coordination geometry

Christian Näther ^a ^* and Jan Boeckmann ^a

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

Edited by Y. Ozawa, University of Hyogo, Japan (Received 11 November 2024; accepted 11 December 2024; online 1 January 2025)

Reaction of Co(NCS)₂ with 4-methylpyridine in water leads to the formation of single crystals of the title compound, [Co(NCS)₂(C₆H₇N)₂]_n. The asymmetric unit consists of two crystallographically independent thiocyanate anions and two crystallographically independent 4-methylpyridine coligands in general positions, as well as of two different Co^II cations, of which one is located on a twofold rotational axis, whereas the second occupies a center of inversion. The methyl H atoms in both 4-methylpyridine ligands are disordered and were refined using a split model. Both Co^II cations are octahedrally coordinated by two N- and two S-bonded thiocyanate anions and two 4-methylpyridine coligands and are linked by pairs of 1,3-bridging anionic ligands into chains. Within these chains the cations show an alternating all-trans and cis–cis–trans configuration, which leads to the formation of corrugated chains. Powder X-ray diffraction proves that a pure crystalline phase has been obtained and the values of the CN stretching vibrations of the anionic ligands observed in the IR and the Raman spectra are in agreement with the presence of bridging anionic ligands.

Keywords: synthesis; crystal structure; coordination polymer; chain structure; spectroscopic properties; cobalt thiocyanate; 4-methylpyridine.

CCDC reference: 2409370

1. Chemical context

For a long time, our interest has focused on the synthesis and crystal structure of transition-metal thiocyanate coordination compounds based on Mn^II, Fe^II, Co^II and Ni^II, because they show a large structural variability, which can partly be traced back to the versatile coordination behavior of this anionic ligand (Näther et al., 2013 ). In nearly all cases these cations are in an octahedral coordination, even though with cobalt several compounds with a tetrahedral coordination are also known. Within this project we are especially interested in compounds in which the metal cations are linked into chains or layers, because such compounds show versatile magnetic behavior (Neumann et al., 2018 ; Suckert et al., 2016 ). This is especially the case for compounds based on cobalt, which can show 1D or 3D ferromagnetic ordering (Mautner et al., 2018 ; Jochim et al., 2020 ; Rams et al., 2017a , 2020 ).

In most cases, chain compounds are observed in which the metal cations are in an octahedral all-trans coordination, leading to the formation of linear chains. Linear chains are also observed for a cis–cis–trans-coordination if the neutral coligands are in trans-positions, which is the case, for example, in M(NCS)₂(4-benzoylpyridine)₂ with M = Co, Ni [refcodes ODEYII (Rams et al., 2017b ) and GIQQUV (Jochim et al., 2018 )] or in Co(NCS)₂(2,3-dimethylpyrazine-1,4-dioxide) (PEVZOG; Shi et al., 2007 ). Corrugated chains are observed if the two bridging S-bonded thiocyanate anions are in an trans-position like in Mn(NCS)₂(4-nitropyridine N-oxide (SINKUW; Shi et al., 2006a ) or in Ni(NCS)₂(2,2′-bipyridine (GIQREG; Jochim et al., 2018). If the two bridging N-bonded thiocanate anions are in a trans-position like in Ni(NCS)₂[1-(2-aminoethyl)pyrrolidine-N,N′) (ABOBIC; Maji et al., 2001 ) corrugated chains are also observed, Finally, in Ni(NCS)₂(4-methylpyridine N-oxide [PEDSUN (Shi et al., 2006b ) and PEDSUN0 (Marsh, 2009 )] an all-cis configuration is observed that also leads to the formation of corrugated chains.

In this context it is noted that we have reported on Co and Ni compounds with the composition Ni(NCS)₂(4-chloropyridine)₂ (UHUVIF and UHUVIF01; Jochim et al., 2018 and Co(NCS)₂(4-chloropyridine)₂ (GIQQIJ and GIQQIJ01; Böhme et al., 2020 ) for each of which two isomers exist. In one of these isomers the metal cations are in an all-trans configuration, whereas in the second isomer that is thermodynamically stable at room temperature, an alternating all-trans and cis–cis–trans configuration is observed. Based on these results, we tried to prepare compounds with Ni(NCS)₂ and 4-methylpyridine as ligand for which, because of the chloro–methyl exchange rule (Desiraju & Sarma, 1986 ), similar structures can be expected, but only one isomer with the composition Ni(NCS)₂(4-methylpyridine)₂ was obtained, which is isotypic to the stable isomer of Ni(NCS)₂(4-chloropyridine)₂ with an alternating all-trans and cis–cis–trans configuration (Näther & Mangelsen, 2024 ).

In the course of our systematic work we became interested in Co(NCS)₂ compounds with 4-methylpyridine as coligand, to check which of the two isomers might form and if this compound is isotypic to the corresponding Ni compound. It is noted that some of such compounds are already reported with this ligand. Most of them consist of solvates of discrete complexes but one chain compound is reported, for which no atomic coordinates are presented (see Database survey).

2. Structural commentary

The asymmetric unit of the title compound, Co(NCS)₂(C₆H₇N)₂, is built up of two crystallographically independent thiocyanate anions and two crystallographically independent 4-methylpyridine coligands in general positions, as well as of two crystallographically independent Co^II cations, of which one is located on a twofold rotational axis whereas the second occupies a center of inversion (Figs. 1 and 2). The methyl H atoms in both 4-methylpyridine ligands are disordered and were refined in two different orientations. Both Co^II cations are octahedrally coordinated by two 4-methylpyridine ligands and two N- and two S-bonding thiocyanate anions (Figs. 1 and 2). One of the Co^II cations (Co1) shows a cis–cis–trans configuration with the thiocyanate N atoms in a trans position and the pyridine N atom as well as the thiocyanate S atom in cis positions (Fig. 2). The second crystallographically independent Co^II cation (Co2) shows an all-trans configuration (Fig. 2). For the Co^II cation that shows a cis–cis–trans configuration, the Co—N distances to the 4-methylpyridine ligands are slightly shorter compared to the cation in the cis–cis–trans configuration (Table 1). Moreover, from the bond lengths and angles it is obvious that the octahedra are slightly distorted. The metal cations are linked by pairs of μ-1,3-bridging thiocyanate anions into chains that, because of the alternating all-trans and cis–cis–trans configurations, are corrugated (Fig. 3). It is noted that the title compound is isotypic to the corresponding compound with Ni(NCS)₂ (Näther & Mangelsen, 2024) and to the isomer that is thermodynamically stable at room temperature of Ni(NCS)₂(4-chloropyridine)₂, which proves that the chloro–methyl exchange rule is valid in this case. From our synthetic work there is no hint of the existence of a second isomer of the title compound as observed for the corresponding 4-chloropyridine compound. Finally, it is noted that the title compound with an alternating all-trans and cis–cis–trans configuration shows a very rare Co coordination.

Table 1
Selected geometric parameters (Å, °)

Co1—N1	2.0699 (16)	Co2—S1	2.5752 (4)
Co1—S2	2.6138 (6)	Co2—N2	2.0585 (16)
Co1—N11	2.1437 (16)	Co2—N21	2.1768 (16)

N1ⁱ—Co1—N1	174.16 (10)	N2—Co2—S1	93.94 (4)
N1ⁱ—Co1—S2	82.53 (5)	N2ⁱⁱ—Co2—S1	86.06 (5)
N1—Co1—S2	93.32 (5)	N2—Co2—N2ⁱⁱ	180.00 (10)
N1ⁱ—Co1—N11	93.35 (6)	N2—Co2—N21ⁱⁱ	90.54 (6)
N1—Co1—N11	90.80 (6)	N2—Co2—N21	89.46 (6)
S2ⁱ—Co1—S2	89.82 (3)	N21—Co2—S1	90.10 (4)
N11—Co1—S2	90.71 (4)	N21ⁱⁱ—Co2—S1ⁱⁱ	90.09 (4)
N11ⁱ—Co1—S2	173.33 (4)	N21ⁱⁱ—Co2—S1	89.90 (4)
N11—Co1—N11ⁱ	89.54 (8)	N21—Co2—N21ⁱⁱ	180.0
S1—Co2—S1ⁱⁱ	180.0
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Figure 1
Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level. Symmetry codes: (i) −x + 1, y, −z + $[{1\over 2}]$ ; (ii) −x + $[{3\over 2}]$ , −y + $[{1\over 2}]$ , −z + 1. The disorder of the methyl H atoms is shown with full and open bonds.

Figure 2
Crystal structure of the title compound with view of a part of a chain with labeling of the Co^II cations and showing the actual metal configuration. For clarity the disorder of the methyl H atoms is not shown.

Figure 3
Crystal structure of the title compound in a view along [101]. For clarity the disorder of the methyl H atoms is not shown.

3. Supramolecular features

In the crystal structure of the title compound, the chains elongate along [101] with each chain surrounded by six neighboring chains (Fig. 3). There are no significant intermolecular C—H⋯N or C—H⋯S contacts and there are also no hints of any π–π stacking interactions (Table 2).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15⋯N1	0.94	2.67	3.131 (3)	111

4. Database survey

A search in the CSD (version 5.43, last update December 2024; Groom et al., 2016 ) using CONQUEST (Bruno et al., 2002 ) for compounds based on Co(NCS)₂ and 4-methylpyridine revealed that some such compounds are already reported. This includes a compound with the composition Co(NCS)₂(4-methylpyridine)4·p-xylene in which the Co cations are tetrahedrally coordinated by only one N-bonding thiocyanate anion and three 4-methylpyridine ligands and which crystallizes with additional p-xylene solvate molecules (Refcode: QQQGKJ; Solaculu et al., 1974 ). However, no atomic coordinates are given and no charge balance is achieved, which means that the existence of this compound is questionable. There is also one compound with the composition Co(NCS)₂(4-methylpyridine)₂bis(p-toluidine)₂ reported for which also no atomic coordinates are given (Refcode: CECDAP; Micu-Semeniuc et al., 1983 ). Surprisingly, the unit-cell parameters are very similar and the crystal system identical to that of compounds built up of octahedral discrete complexes with additional solvate molecules (see below).

All remaining compounds consists of discrete complexes with the composition Co(NCS)₂(4-methylpyridine)₄ that crystallize as clathrates with p-toluidine (Refcode CECCOC; Micu-Semeniuc et al., 1983), 4-methylpyridine [Refcodes: XIHHEB (Harris et al., 2001 ) and XIHHEB01 (Harris et al., 2003 )] and nitrobenzene (Refcode ZZZUXU), nitroethane (Refcode: ZZZUXY) and benzene solvate (Refcode: ZZZUYI; Belitskus et al., 1963 ). However, only for one of these compounds (XIHHEB) are atomic coordinates available. Finally, the crystal structure of the pure complex Co(NCS)₂(4-methylpyridine)₄ is also reported but the unit-cell parameters are identical to that of several clathrates, which indicates that the solvent was not located (Refcode: VERNUC; Harris et al., 2003).

5. Additional investigations

Powder X-ray diffraction measurements prove that the title compound has been obtained as a pure phase (Fig. 4). In the IR and Raman spectrum the CN stretching vibration is observed at 2108 and 2095 cm⁻¹ (IR) and at 2100 cm⁻¹ (Raman), which confirms the presence of μ-1,3-bridging thiocyanate anions (Fig. 5). To determine whether the title compound can be transformed into a discrete aqua complex with the composition Co(NCS)₂(4-methylpyridine)₂(H₂O)₂, which exists for the corresponding compound with 4-chloropyridine (Böhme et al., 2020), a sample of the title compound was stored for 2 d in a humid atmosphere, but no changes were observed (Fig. 6).

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

Figure 5
IR (top) and Raman (bottom) spectra of the title compound. The CN stretching vibration of the thiocyanate anions is given.

Figure 6
Experimental X-ray powder pattern of a sample of the title compound stored for 2 d in a humid atmosphere (top) and the calculated powder pattern (bottom).

6. Synthesis and crystallization

Synthesis

4-Methylpyridine and Co(NCS)₂ were obtained from Sigma-Aldrich. The title compound was prepared by the reaction of Co(NCS)₂ (350.2 mg, 2.06 mmol) and 4-methylpyridine (100 µL, 1.03 mmol) in 3 mL of water. The reaction mixture was stirred for 2 d at 393 K in a closed glass tube. C₁₄H₁₄CoN₄S₂ (361.34): calculated C 46.53, H 3.91, N 15.50, S 17.75; found C 46.2, H 3.7, N 15.3, S 17.4. Single crystals were prepared by the same method without stirring. The purity was proven by powder X-ray diffraction (see Fig. 4). An IR and a Raman spectrum of the title compound can be seen in Fig. 5.

Experimental details

Elemental analysis was performed with a vario MICRO cube from Elementar Analysensysteme GmbH. IR spectra were recorded at room temperature on a Bruker Vertex70 FT-IR spectrometer using a broadband spectral range extension VERTEX FM for full mid and far IR. Raman spectra were recorded on a Bruker RAM II FT-Raman spectrometer using a liquid nitrogen cooled, highly sensitive Ge detector, 1064 nm radiation and 3 cm⁻¹ resolution. X-ray powder diffraction experiments 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.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The hydrogen atoms were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined with U_iso(H) = 1.2U_eq(C) (1.5 for methyl H atoms) using a riding model. The methyl H atoms in both crystallographically independent 4-methylpyridine ligands are disordered and were refined in two orientations rotated by 60°.

Table 3
Experimental details

Crystal data
Chemical formula	[Co(NCS)₂(C₆H₇N)₂]
M_r	361.34
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	220
a, b, c (Å)	20.1106 (12), 9.2112 (4), 19.2309 (12)
β (°)	116.353 (6)
V (Å³)	3192.2 (3)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	1.33
Crystal size (mm)	0.19 × 0.15 × 0.12

Data collection
Diffractometer	Stoe IPDS2
Absorption correction	Numerical (X-RED and X-SHAPE; Stoe, 2008 )
T_min, T_max	0.685, 0.763
No. of measured, independent and observed [I > 2σ(I)] reflections	18094, 3840, 3249
R_int	0.030

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.095, 1.04
No. of reflections	3840
No. of parameters	195
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.44
Computer programs: X-AREA (Stoe, 2008), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 1999 ), XP in SHELXTL (Sheldrick, 2008 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2409370

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024012003/ox2010sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024012003/ox2010Isup2.hkl

checkCIF report

Computing details top

catena-Poly[[bis(4-methylpyridine-κN)cobalt(II)]-di-µ-thiocyanato-κ²N:S;κ²S:N] top

Crystal data top

[Co(NCS)₂(C₆H₇N)₂]	F(000) = 1480
M_r = 361.34	D_x = 1.504 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.1106 (12) Å	Cell parameters from 18094 reflections
b = 9.2112 (4) Å	θ = 2.4–28.0°
c = 19.2309 (12) Å	µ = 1.33 mm⁻¹
β = 116.353 (6)°	T = 220 K
V = 3192.2 (3) Å³	Block, violet
Z = 8	0.19 × 0.15 × 0.12 mm

Data collection top

Stoe IPDS-2 diffractometer	3249 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω scans	θ_max = 28.0°, θ_min = 2.4°
Absorption correction: numerical (X-Red and X-Shape; Stoe, 2008)	h = −26→26
T_min = 0.685, T_max = 0.763	k = −12→12
18094 measured reflections	l = −25→25
3840 independent 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)] = 0.035	w = 1/[σ²(F_o²) + (0.0668P)² + 0.3181P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.095	(Δ/σ)_max = 0.001
S = 1.04	Δρ_max = 0.54 e Å⁻³
3840 reflections	Δρ_min = −0.44 e Å⁻³
195 parameters	Extinction correction: SHELXL-2016/6 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0057 (5)

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	0.500000	0.49107 (4)	0.250000	0.02383 (11)
Co2	0.750000	0.250000	0.500000	0.02301 (11)
S1	0.66193 (2)	0.42603 (6)	0.52245 (2)	0.02860 (13)
C1	0.59987 (9)	0.4576 (2)	0.43277 (10)	0.0227 (3)
N1	0.55673 (9)	0.47963 (18)	0.36976 (9)	0.0282 (3)
S2	0.58146 (3)	0.29010 (6)	0.22966 (3)	0.03552 (15)
C2	0.64772 (10)	0.2750 (2)	0.31844 (10)	0.0241 (3)
N2	0.69410 (9)	0.26457 (19)	0.38096 (9)	0.0289 (3)
N11	0.57409 (8)	0.65628 (18)	0.24774 (9)	0.0272 (3)
C11	0.59645 (10)	0.6656 (2)	0.19205 (11)	0.0295 (4)
H11	0.577925	0.597731	0.151360	0.035*
C12	0.64542 (11)	0.7701 (2)	0.19119 (11)	0.0307 (4)
H12	0.658799	0.772892	0.150181	0.037*
C13	0.67484 (10)	0.8707 (2)	0.25094 (11)	0.0293 (4)
C14	0.65122 (12)	0.8613 (2)	0.30850 (13)	0.0375 (5)
H14	0.669143	0.927491	0.349996	0.045*
C15	0.60160 (12)	0.7551 (2)	0.30501 (12)	0.0358 (5)
H15	0.586236	0.751641	0.344562	0.043*
C16	0.72997 (13)	0.9827 (3)	0.25418 (15)	0.0423 (5)
H16A	0.719681	1.011652	0.201869	0.063*	0.3193
H16B	0.779623	0.942496	0.280015	0.063*	0.3193
H16C	0.726370	1.066719	0.282752	0.063*	0.3193
H16D	0.764102	1.002260	0.307889	0.063*	0.6807
H16E	0.704159	1.071415	0.229743	0.063*	0.6807
H16F	0.757413	0.947192	0.227005	0.063*	0.6807
N21	0.67949 (8)	0.06822 (18)	0.49669 (9)	0.0280 (3)
C21	0.70667 (11)	−0.0423 (2)	0.54644 (12)	0.0348 (4)
H21	0.758041	−0.045551	0.578635	0.042*
C22	0.66266 (12)	−0.1523 (2)	0.55279 (13)	0.0374 (4)
H22	0.684392	−0.227674	0.588788	0.045*
C23	0.58650 (11)	−0.1515 (2)	0.50608 (12)	0.0306 (4)
C24	0.55912 (11)	−0.0391 (2)	0.45241 (12)	0.0333 (4)
H24	0.508301	−0.035451	0.417935	0.040*
C25	0.60634 (10)	0.0673 (2)	0.44959 (11)	0.0304 (4)
H25	0.586322	0.142359	0.413022	0.036*
C26	0.53661 (13)	−0.2648 (2)	0.51418 (14)	0.0404 (5)
H26A	0.485301	−0.234544	0.485588	0.061*	0.6344
H26B	0.548454	−0.276466	0.568562	0.061*	0.6344
H26C	0.543875	−0.356370	0.493626	0.061*	0.6344
H26D	0.566452	−0.343709	0.546263	0.061*	0.3656
H26E	0.503299	−0.301788	0.463289	0.061*	0.3656
H26F	0.507879	−0.221883	0.538224	0.061*	0.3656

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01963 (17)	0.0287 (2)	0.01631 (17)	0.000	0.00182 (13)	0.000
Co2	0.01948 (17)	0.0281 (2)	0.01689 (17)	0.00358 (12)	0.00393 (13)	0.00223 (13)
S1	0.0267 (2)	0.0373 (3)	0.0161 (2)	0.00936 (18)	0.00425 (17)	0.00090 (17)
C1	0.0198 (7)	0.0243 (8)	0.0228 (8)	0.0022 (6)	0.0083 (6)	−0.0016 (7)
N1	0.0247 (7)	0.0350 (9)	0.0190 (7)	0.0046 (6)	0.0044 (6)	−0.0003 (6)
S2	0.0337 (3)	0.0424 (3)	0.0187 (2)	0.0092 (2)	0.00094 (19)	−0.00481 (19)
C2	0.0243 (8)	0.0255 (9)	0.0229 (8)	0.0033 (6)	0.0109 (7)	0.0013 (7)
N2	0.0274 (7)	0.0356 (9)	0.0202 (7)	0.0072 (6)	0.0075 (6)	0.0015 (6)
N11	0.0232 (7)	0.0311 (8)	0.0246 (7)	−0.0022 (6)	0.0082 (6)	−0.0051 (6)
C11	0.0295 (8)	0.0335 (10)	0.0230 (8)	−0.0015 (7)	0.0093 (7)	−0.0077 (8)
C12	0.0329 (9)	0.0344 (10)	0.0285 (9)	−0.0002 (8)	0.0170 (8)	−0.0036 (8)
C13	0.0252 (8)	0.0294 (10)	0.0328 (9)	−0.0006 (7)	0.0125 (7)	−0.0041 (8)
C14	0.0426 (11)	0.0395 (12)	0.0343 (10)	−0.0130 (9)	0.0205 (9)	−0.0160 (9)
C15	0.0428 (11)	0.0392 (11)	0.0317 (10)	−0.0107 (9)	0.0224 (9)	−0.0133 (9)
C16	0.0437 (12)	0.0404 (12)	0.0498 (13)	−0.0125 (9)	0.0271 (11)	−0.0095 (10)
N21	0.0245 (7)	0.0297 (9)	0.0272 (8)	0.0017 (6)	0.0092 (6)	0.0005 (6)
C21	0.0287 (9)	0.0331 (10)	0.0347 (10)	0.0013 (8)	0.0069 (8)	0.0033 (9)
C22	0.0380 (10)	0.0312 (11)	0.0363 (10)	0.0011 (8)	0.0106 (9)	0.0057 (9)
C23	0.0343 (9)	0.0289 (9)	0.0329 (9)	−0.0008 (8)	0.0187 (8)	−0.0064 (8)
C24	0.0256 (8)	0.0385 (11)	0.0350 (10)	0.0006 (8)	0.0126 (8)	−0.0046 (9)
C25	0.0260 (8)	0.0340 (10)	0.0288 (9)	0.0049 (7)	0.0101 (7)	0.0022 (8)
C26	0.0438 (11)	0.0358 (11)	0.0477 (12)	−0.0072 (9)	0.0260 (10)	−0.0082 (10)

Geometric parameters (Å, º) top

Co1—N1ⁱ	2.0699 (16)	C14—C15	1.377 (3)
Co1—N1	2.0699 (16)	C15—H15	0.9400
Co1—S2ⁱ	2.6138 (6)	C16—H16A	0.9700
Co1—S2	2.6138 (6)	C16—H16B	0.9700
Co1—N11	2.1437 (16)	C16—H16C	0.9700
Co1—N11ⁱ	2.1437 (16)	C16—H16D	0.9700
Co2—S1	2.5752 (4)	C16—H16E	0.9700
Co2—S1ⁱⁱ	2.5753 (4)	C16—H16F	0.9700
Co2—N2	2.0585 (16)	N21—C21	1.336 (3)
Co2—N2ⁱⁱ	2.0585 (16)	N21—C25	1.342 (2)
Co2—N21	2.1768 (16)	C21—H21	0.9400
Co2—N21ⁱⁱ	2.1768 (16)	C21—C22	1.386 (3)
S1—C1	1.6448 (18)	C22—H22	0.9400
C1—N1	1.153 (2)	C22—C23	1.390 (3)
S2—C2	1.6401 (18)	C23—C24	1.392 (3)
C2—N2	1.153 (2)	C23—C26	1.503 (3)
N11—C11	1.336 (2)	C24—H24	0.9400
N11—C15	1.344 (2)	C24—C25	1.382 (3)
C11—H11	0.9400	C25—H25	0.9400
C11—C12	1.382 (3)	C26—H26A	0.9700
C12—H12	0.9400	C26—H26B	0.9700
C12—C13	1.388 (3)	C26—H26C	0.9700
C13—C14	1.387 (3)	C26—H26D	0.9700
C13—C16	1.495 (3)	C26—H26E	0.9700
C14—H14	0.9400	C26—H26F	0.9700

N1ⁱ—Co1—N1	174.16 (10)	C13—C16—H16D	109.5
N1ⁱ—Co1—S2	82.53 (5)	C13—C16—H16E	109.5
N1—Co1—S2	93.32 (5)	C13—C16—H16F	109.5
N1ⁱ—Co1—S2ⁱ	93.32 (5)	H16A—C16—H16B	109.5
N1—Co1—S2ⁱ	82.53 (5)	H16A—C16—H16C	109.5
N1ⁱ—Co1—N11	93.35 (6)	H16A—C16—H16D	141.1
N1ⁱ—Co1—N11ⁱ	90.80 (6)	H16A—C16—H16E	56.3
N1—Co1—N11	90.80 (6)	H16A—C16—H16F	56.3
N1—Co1—N11ⁱ	93.34 (6)	H16B—C16—H16C	109.5
S2ⁱ—Co1—S2	89.82 (3)	H16B—C16—H16D	56.3
N11—Co1—S2	90.71 (4)	H16B—C16—H16E	141.1
N11ⁱ—Co1—S2	173.33 (4)	H16B—C16—H16F	56.3
N11—Co1—S2ⁱ	173.33 (4)	H16C—C16—H16D	56.3
N11ⁱ—Co1—S2ⁱ	90.71 (4)	H16C—C16—H16E	56.3
N11—Co1—N11ⁱ	89.54 (8)	H16C—C16—H16F	141.1
S1—Co2—S1ⁱⁱ	180.0	H16D—C16—H16E	109.5
N2—Co2—S1	93.94 (4)	H16D—C16—H16F	109.5
N2ⁱⁱ—Co2—S1ⁱⁱ	93.94 (4)	H16E—C16—H16F	109.5
N2ⁱⁱ—Co2—S1	86.06 (5)	C21—N21—Co2	120.72 (13)
N2—Co2—S1ⁱⁱ	86.06 (4)	C21—N21—C25	117.11 (18)
N2—Co2—N2ⁱⁱ	180.00 (10)	C25—N21—Co2	121.95 (14)
N2—Co2—N21ⁱⁱ	90.54 (6)	N21—C21—H21	118.5
N2—Co2—N21	89.46 (6)	N21—C21—C22	123.07 (19)
N2ⁱⁱ—Co2—N21	90.54 (6)	C22—C21—H21	118.5
N2ⁱⁱ—Co2—N21ⁱⁱ	89.46 (7)	C21—C22—H22	119.9
N21—Co2—S1	90.10 (4)	C21—C22—C23	120.2 (2)
N21ⁱⁱ—Co2—S1ⁱⁱ	90.09 (4)	C23—C22—H22	119.9
N21ⁱⁱ—Co2—S1	89.90 (4)	C22—C23—C24	116.29 (18)
N21—Co2—S1ⁱⁱ	89.91 (4)	C22—C23—C26	121.6 (2)
N21—Co2—N21ⁱⁱ	180.0	C24—C23—C26	122.07 (19)
C1—S1—Co2	101.18 (6)	C23—C24—H24	119.9
N1—C1—S1	179.55 (16)	C25—C24—C23	120.27 (18)
C1—N1—Co1	164.70 (14)	C25—C24—H24	119.9
C2—S2—Co1	100.25 (6)	N21—C25—C24	122.98 (19)
N2—C2—S2	179.70 (18)	N21—C25—H25	118.5
C2—N2—Co2	162.72 (14)	C24—C25—H25	118.5
C11—N11—Co1	123.13 (13)	C23—C26—H26A	109.5
C11—N11—C15	116.78 (17)	C23—C26—H26B	109.5
C15—N11—Co1	120.08 (13)	C23—C26—H26C	109.5
N11—C11—H11	118.3	C23—C26—H26D	109.5
N11—C11—C12	123.36 (17)	C23—C26—H26E	109.5
C12—C11—H11	118.3	C23—C26—H26F	109.5
C11—C12—H12	120.0	H26A—C26—H26B	109.5
C11—C12—C13	119.95 (17)	H26A—C26—H26C	109.5
C13—C12—H12	120.0	H26A—C26—H26D	141.1
C12—C13—C16	122.08 (17)	H26A—C26—H26E	56.3
C14—C13—C12	116.57 (18)	H26A—C26—H26F	56.3
C14—C13—C16	121.35 (18)	H26B—C26—H26C	109.5
C13—C14—H14	119.9	H26B—C26—H26D	56.3
C15—C14—C13	120.20 (18)	H26B—C26—H26E	141.1
C15—C14—H14	119.9	H26B—C26—H26F	56.3
N11—C15—C14	123.12 (17)	H26C—C26—H26D	56.3
N11—C15—H15	118.4	H26C—C26—H26E	56.3
C14—C15—H15	118.4	H26C—C26—H26F	141.1
C13—C16—H16A	109.5	H26D—C26—H26E	109.5
C13—C16—H16B	109.5	H26D—C26—H26F	109.5
C13—C16—H16C	109.5	H26E—C26—H26F	109.5

Co1—N11—C11—C12	−178.58 (15)	C15—N11—C11—C12	0.0 (3)
Co1—N11—C15—C14	177.88 (18)	C16—C13—C14—C15	−178.6 (2)
Co2—N21—C21—C22	172.50 (17)	N21—C21—C22—C23	0.2 (3)
Co2—N21—C25—C24	−172.73 (15)	C21—N21—C25—C24	2.0 (3)
N11—C11—C12—C13	1.0 (3)	C21—C22—C23—C24	2.2 (3)
C11—N11—C15—C14	−0.8 (3)	C21—C22—C23—C26	−176.8 (2)
C11—C12—C13—C14	−1.3 (3)	C22—C23—C24—C25	−2.5 (3)
C11—C12—C13—C16	177.9 (2)	C23—C24—C25—N21	0.4 (3)
C12—C13—C14—C15	0.6 (3)	C25—N21—C21—C22	−2.3 (3)
C13—C14—C15—N11	0.5 (4)	C26—C23—C24—C25	176.55 (18)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···N1	0.94	2.67	3.131 (3)	111

Acknowledgements

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

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