Synthesis and crystal structure of poly[ethanol(μ-4-methyl­pyridine N-oxide)di-μ-thio­cyanato-cobalt(II)]

Näther, C.; Jess, I.

doi:10.1107/S2056989024009058

research communications

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ISSN: 2056-9890

Volume 80| Part 10| October 2024| Pages 1029-1033

https://doi.org/10.1107/S2056989024009058

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Synthesis and crystal structure of poly[ethanol(μ-4-methylpyridine N-oxide)di-μ-thiocyanato-cobalt(II)]

Christian Näther ^a ^* and Inke Jess ^a

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

Edited by S. Parkin, University of Kentucky, USA (Received 4 September 2024; accepted 16 September 2024; online 20 September 2024)

Reaction of 4-methylpyridine N-oxide and Co(NCS)₂ in ethanol as solvent accidentally leads to the formation of single crystals of Co(NCS)₂(4-methylpyridine N-oxide)(ethanol) or [Co(NCS)₂(C₆H₇NO)(C₂H₆O)]_n. The asymmetric unit of the title compound consists of one Co^II cation, two crystallographically independent thiocyanate anions, one 4-methylpyridine N-oxide coligand and one ethanol molecule on general positions. The cobalt cations are sixfold coordinated by one terminal and two bridging thiocyanate anions, two bridging 4-methylpyridine N-oxide coligands and one ethanol molecule, with a slightly distorted octahedral geometry. The cobalt cations are linked by single μ-1,3(N,S)-bridging thiocyanate anions into corrugated chains, that are further connected into layers by pairs of μ-1,1(O,O)-bridging 4-methylpyridine N-oxide coligands. The layers are parallel to the bc plane and are separated by the methyl groups of the 4-methylpyridine N-oxide coligands. Within the layers, intralayer hydrogen bonding is observed.

Keywords: synthesis; crystal structure; cobalt thiocyanate; coordination polymer; layered network; 4-methylpyridine N-oxide.

CCDC reference: 2384436

1. Chemical context

Coordination polymers based on transition-metal thiocyanate coordination polymers are characterized by a pronounced structural variability, which can partly be traced back to the variety of coordination modes of this anionic ligand. This includes mainly the terminal coordination, the μ-1,3(N,S) and the μ-1,3,3(N,S,S) bridging modes. With μ-1,3(N,S) bridging anionic ligands and octahedrally coordinated metal cations the majority of compounds consist of M(NCS)₂ chains, in which the metal centers are connected by pairs of thiocyanate anions. In most cases an all-trans coordination is found, which leads to the formation of linear chains (Rams et al., 2017a , 2020 ; Mautner et al., 2018a ,b ). Linear chains are also observed if the co-ligands are in trans-positions and the thiocyanate N and S atoms are in cis-positions (Rams et al., 2017b ). For the other or cis–cis–trans and the all-cis coordination, corrugated chains are observed (Maji et al., 2001 ; Marsh, 2009 ; Shi et al., 2006a , 2007a ; Böhme et al., 2020 ). In contrast, chain compounds in which the metal cations are linked by single μ-1,3-bridging thiocyanate anions are rarer (Palion-Gazda et al., 2015 ; Neumann et al., 2018 ).

We have been interested in transition-metal thiocyanates for a long time, with special focus on Co(NCS)₂ chain compounds with pyridine derivatives as coligands (Rams et al., 2017a,b, 2020; Böhme et al., 2022 ). Later we also used pyridine N-oxide derivatives as coligands, because they can additionally connect metal cations via the μ-1,1(O,O) bridging mode. In this regard we became interested in 4-methylpyridine N-oxide as coligand. With this ligand, two compounds with the composition Co(NCS)₂(4-methylpyridine-N-oxide) (Zhang et al., 2006a ) and Co(NCS)₂(4-methylpyridine N-oxide)(methanol) (Shi et al., 2006a) were reported in the literature. In the first compound, the cobalt cations are octahedrally coordinated by two N- and two S-bonding thiocyanate anions and two bridging 4-methylpyridine N-oxide coligands and are connected by pairs of bridging anionic ligands into corrugated chains, which are further connected into layers by the 4-methylpyridine N-oxide coligands. In the second compound, the cobalt cations are octahedrally coordinated by one terminal and two bridging thiocyanate anions, two bridging 4-methylpyridine N-oxide coligands and one methanol molecule. The metal cations are linked by alternating pairs of μ-1,3-bridging thiocyanate anions and μ-1,1(O,O) bridging 4-methylpyridine N-oxide coligands into chains. In the course of our investigations we have synthesized two discrete complexes with the composition Co(NCS)₂(4-methylpyridine N-oxide)₃ and Co(NCS)₂(4-methylpyridine N-oxide)₄ that show a trigonal–bipyramidal or an octahedral coordination (Näther & Jess, 2024a ). The first complex can easily be synthesized from methanol, but in some of these batches an additional 4-methylpyridine N-oxide compound was detected. Later we have found that a compound with the composition Co₂(NCS)₄(4-methylpyridine N-oxide)₄(methanol)₂ was obtained as a by-phase, in which the Co^II cations are linked by pairs of μ-1,1-bridging 4-methylpyridine N-oxide coligands into centrosymmetric dinuclear units (Näther & Jess, 2024b ).

Some of the 4-pyridine N-oxide compounds mentioned above can also be prepared in ethanol as solvent. However, in some of these batches traces of an additional product were detected by X-ray powder diffraction and therefore a large number of crystallization experiments were performed. In one of these batches crystals suitable for single-crystal X-ray diffraction were accidentally obtained, which proved that a compound with the composition Co(NCS)₂(4-methylpyridine N-oxide)(ethanol) had formed.

2. Structural commentary

The asymmetric unit of the title compound, Co(NCS)₂(4-methylpyridine N-oxide)(ethanol), is built up of one cobalt cation, two crystallographically independent thiocyanate anions, one ethanol and one 4-methylpyridine N-oxide coligand that are located in general positions. The Co cations are sixfold coordinated by one terminal N-bonded and two μ-1,3(N,S)-bridging thiocyanate anions, one ethanol molecule and two μ-1,1(O,O)-bridging 4-methylpyridine N-oxide coligands (Fig. 1). The bridging thiocyanate anions and the 4-methylpyridine N-oxide coligands are each in cis-positions. The Co—N bond length to the terminal anions is slightly shorter than that to the bridging anionic ligands (Table 1). The bond angles deviate from ideal values, which shows that a distorted octahedral coordination is present (Table 1). The Co^II cations are linked by single μ-1,3(N,S)-bridging thiocyanate anions into corrugated chains that proceed along the crystallographic c-axis direction (Fig. 2). The chains are linked by two μ-1,1(O,O)-bridging 4-methylpyridine N-oxide coligands into layers via four-membered Co₂O₂ rings (Fig. 3). These layers consist of large rings built up of six Co^II cations, four bridging thiocyanate anions and two bridging 4-methylpyridine N-oxide coligands (Fig. 3). Within these rings, each of the two Co^II cations are linked by pairs of μ-1,1(O,O)-bridging 4-methylpyridine N-oxide coligands into dinuclear units that are further connected by single μ-1,3-bridging thiocyanate anions (Fig. 3).

Table 1
Selected geometric parameters (Å, °)

Co1—N1	2.0472 (13)	Co1—O11	2.0971 (10)
Co1—N2	2.0569 (12)	Co1—O11ⁱⁱ	2.1594 (10)
Co1—S2ⁱ	2.5171 (4)	Co1—O21	2.1559 (10)

N1—Co1—N2	110.80 (5)	N2—Co1—O21	86.53 (5)
N1—Co1—S2ⁱ	90.75 (4)	O11—Co1—S2ⁱ	98.02 (3)
N1—Co1—O11ⁱⁱ	160.49 (5)	O11ⁱⁱ—Co1—S2ⁱ	95.96 (3)
N1—Co1—O11	89.92 (4)	O11—Co1—O11ⁱⁱ	71.03 (4)
N1—Co1—O21	82.55 (5)	O11—Co1—O21	92.89 (4)
N2—Co1—S2ⁱ	85.67 (4)	O21—Co1—S2ⁱ	167.20 (3)
N2—Co1—O11ⁱⁱ	88.01 (4)	O21—Co1—O11ⁱⁱ	93.90 (4)
N2—Co1—O11	158.96 (5)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) .

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

Figure 2
Crystal structure of the title compound with view of a Co(NCS)₂ chain.

Figure 3
Crystal structure of the title compound with view along the crystallographic a-axis, showing the layered network. For the 4-methylpyridine N-oxide coligands, only the O atoms are shown.

Even though the overall composition of the title compound is very similar to that of Co(NCS)₂(4-methylpyridine N-oxide)(methanol), which has already been reported in the literature, their crystal structures are completely different. In the compound with methanol, the Co^II cations are linked by alternating pairs of μ-1,3-bridging thiocyanate anions and μ-1,1(O,O)-bridging 4-methylpyridine N-oxide coligands into chains (Shi et al., 2006a). However, layered thiocyanate networks that also consist of condensed rings are known from compounds with pyridine derivatives as coligands. In, for example, M(NCS)₂(ethylisonicotinate)₂ with M = Co, Ni (Suckert et al., 2016 ), both metal cations are linked by pairs of μ-1,3-bridging anions into dinuclear units that, as in the title compound, are further connected by single μ-1,3-bridging anionic ligands into layers.

3. Supramolecular features

In the crystal structure of the title compound, the layers are parallel to the bc plane and are separated by the methyl groups of the 4-methylpyridine N-oxide coligands (Fig. 3). Therefore, no significant intermolecular interactions are observed between the layers (Table 2). However, intralayer C—H⋯S and O—H⋯S hydrogen bonding is present with C—H⋯S and O—H⋯S angles close to linearity (Table 2 and Fig. 4).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯S2ⁱⁱⁱ	0.95	2.95	3.4900 (15)	118
C11—H11⋯O21	0.95	2.57	3.2004 (18)	124
C12—H12⋯S1^iv	0.95	2.96	3.8544 (16)	157
O21—H21⋯S1^v	0.82 (2)	2.53 (2)	3.3028 (11)	159 (2)
C22—H22C⋯S2^vi	0.98	2.93	3.7185 (18)	138
Symmetry codes: (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) ; (v) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vi) .

Figure 4
Crystal structure of the title compound with view along the crystallographic b-axis, showing the arrangement of the layers. Intralayer hydrogen bonding is shown as dashed lines.

4. Database survey

As mentioned above, two compounds based on Co(NCS)₂ and 4-methylpyridine N-oxide are already reported in the CSD (version 5.43, last update March 2023; Groom et al., 2016 ). These include Co(NCS)₂(4-methylpyridine N-oxide) (Refcode: MEQKOJ, Zhang et al., 2006a) and Co(NCS)₂(4-methylpyridineN-oxide)(methanol) (Refcode: REKBUF, Shi et al., 2006a). Two discrete complexes with the composition Co(NCS)₂(4-methylpyridine N-oxide)₃ and Co(NCS)₂(4-methylpyridine N-oxide)₄ (Näther & Jess, 2024a) as well as one chain compound with the composition Co₂(NCS)₄(4-methylpyridine N-oxide)₄(methanol)₂ (Näther & Jess, 2024b) are also reported.

Additionally, several other M(NCS)₂ compounds with 4-methylpyridine N-oxide are also listed in the CSD. These include M(NCS)₂(4-methylpyridine N-oxide) with M = Ni, Cd) (Refcodes: PEDSUN, Shi et al., 2006b ; PEDSUN01, Marsh, 2009; TEQKAC, Shi et al., 2006c ). With copper(II), a compound with the composition Cu(NCS)₂(4-methylpyridine N-oxide) is reported in which the Cu^II cations are octahedrally coordinated and linked into chains by pairs of bridging thiocyanate anions, which are further connected into double chains via Cu₂S₂ rings (Refcode TEBTAW, Shi et al., 2006d ). With Ni^II and Mn^II, two discrete aqua complexes with the composition M(NCS)₂(4-methylpyridine N-oxide)₂(H₂O)₂ (M = Ni, Shi et al., 2006a and M = Mn, Mautner et al., 2018a,b) are also reported. Three isotypic compounds with the composition M(NCS)₂)(acetato)₂(H₂O)₃(4-methylpyridine N-oxide) with M = Sm, Eu, Gd) are also known (Refcodes: GIHBUV, Zhang & Shi, 2007 ; PIJBIU and PIJBOA, Shi et al., 2007a).

Some Co(NCS)₂ compounds with other pyridine N-oxide derivatives are also known. These include Co(NCS)₂(pyridine N-oxide)₂(H₂O)₂ and Co(NCS)₂(3-hydroxypyridine N-oxide)₂(H₂O)₂, which consist of discrete octahedral complexes (Refcodes: FONBIU, Shi et al., 2005 ; IDOYEG, Shi et al., 2006e ). They also include Co(NCS)₂(4-methoxypyridine N-oxide), which is isotypic to its 4-methylpyridine analog (Refcode TERRAK, Zhang et al., 2006b ) and Co(NCS)₂(4-nitropyridine N-oxide) (Shi et al., 2007b ). Finally, we have also reported some Co(NCS)₂ compounds with pyridine N-oxide derivatives, including Co(NCS)₂(3-cyanopyridine N-oxide)₄ (Näther & Jess, 2023 ), Co(NCS)₂(2-methylpyridine N-oxide) (Näther & Jess, 2024c ), and Co(NCS)₂(2-methylpyridine N-oxide)₃ (Näther & Jess, 2024d ).

5. Synthesis and crystallization

Co(NCS)₂ (99%) was purchased from Sigma Aldrich and 4-methylpyridine N-oxide (97%) from Thermo Scientific.

Synthesis:

Crystals of the title compound were accidentally obtained by the reaction of 0.5 mmol (87 mg) Co(SCN)₂ and 0.5 mmol (54 mg) of 4-methylpyridine N-oxide in 1 mL of ethanol. The reaction mixture was stored overnight, which led to the formation of a violet-colored crystalline precipitate. X-ray powder diffraction measurements prove that the majority of the sample consists of the known discrete complex Co(NCS)₂(4-methylpyridine N-oxide)₃ (Näther & Jess, 2024a) and that only traces of the title compound are present.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The C—H hydrogen atoms were positioned with idealized geometry (methyl H atoms allowed to rotate and not to tip) and were refined with U_iso(H) = 1.2U_eq(C) (1.5 for methyl H atoms) using a riding model.

Table 3
Experimental details

Crystal data
Chemical formula	[Co(NCS)₂(C₆H₇NO)(C₂H₆O)]
M_r	330.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	11.67627 (7), 11.61861 (6), 10.60662 (7)
β (°)	107.5929 (7)
V (Å³)	1371.62 (2)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	12.65
Crystal size (mm)	0.15 × 0.12 × 0.10 × 0.08 (radius)

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	0.453, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	23514, 2937, 2909
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.058, 1.05
No. of reflections	2937
No. of parameters	170
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.29
Computer programs: CrysAlis PRO (Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2016/6 (Sheldrick, 2015b ), DIAMOND (Brandenburg, 1999 ) and XP in SHELXTL-PC (Sheldrick, 2008 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2384436

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024009058/pk2710sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024009058/pk2710Isup2.hkl

checkCIF report

Computing details top

Poly[ethanol(µ-4-methylpyridine N-oxide)di-µ-thiocyanato-cobalt(II)] top

Crystal data top

[Co(NCS)₂(C₆H₇NO)(C₂H₆O)]	F(000) = 676
M_r = 330.28	D_x = 1.599 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 11.67627 (7) Å	Cell parameters from 19460 reflections
b = 11.61861 (6) Å	θ = 4.0–79.9°
c = 10.60662 (7) Å	µ = 12.65 mm⁻¹
β = 107.5929 (7)°	T = 100 K
V = 1371.62 (2) Å³	Block, pink
Z = 4	0.15 × 0.12 × 0.10 × 0.08 (radius) mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	2937 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2909 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.022
Detector resolution: 10.0000 pixels mm^-1	θ_max = 80.4°, θ_min = 4.0°
ω scans	h = −14→13
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2023)	k = −14→14
T_min = 0.453, T_max = 1.000	l = −11→13
23514 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.022	w = 1/[σ²(F_o²) + (0.0303P)² + 0.9886P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.058	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 0.35 e Å⁻³
2937 reflections	Δρ_min = −0.29 e Å⁻³
170 parameters	Extinction correction: SHELXL2016/6 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.00084 (11)
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.

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

	x	y	z	U_iso*/U_eq
Co1	0.56402 (2)	0.37657 (2)	0.58362 (2)	0.01116 (8)
N1	0.70562 (11)	0.28747 (11)	0.55557 (12)	0.0163 (3)
C1	0.77833 (13)	0.25258 (12)	0.51159 (14)	0.0156 (3)
S1	0.88296 (3)	0.20182 (3)	0.45220 (4)	0.02192 (10)
N2	0.51802 (11)	0.31162 (11)	0.74214 (12)	0.0155 (2)
C2	0.47782 (13)	0.29336 (12)	0.82748 (14)	0.0143 (3)
S2	0.41839 (3)	0.26862 (3)	0.94760 (3)	0.01787 (9)
O11	0.56699 (9)	0.48910 (9)	0.43004 (10)	0.0133 (2)
N11	0.66546 (11)	0.50302 (10)	0.38914 (12)	0.0123 (2)
C11	0.76069 (13)	0.56068 (13)	0.46681 (14)	0.0164 (3)
H11	0.759449	0.589098	0.550371	0.020*
C12	0.86013 (13)	0.57840 (13)	0.42474 (15)	0.0179 (3)
H12	0.927076	0.619664	0.479306	0.021*
C13	0.86310 (13)	0.53621 (13)	0.30276 (15)	0.0175 (3)
C14	0.76325 (14)	0.47485 (13)	0.22755 (15)	0.0182 (3)
H14	0.762990	0.443743	0.144637	0.022*
C15	0.66507 (13)	0.45867 (13)	0.27160 (14)	0.0164 (3)
H15	0.597523	0.416577	0.219592	0.020*
C16	0.96938 (15)	0.55720 (18)	0.25409 (17)	0.0289 (4)
H16A	0.984966	0.488350	0.208476	0.043*
H16B	1.040050	0.574519	0.329344	0.043*
H16C	0.952495	0.622453	0.192663	0.043*
O21	0.70560 (9)	0.46801 (9)	0.72670 (10)	0.0153 (2)
H21	0.7507 (19)	0.4167 (18)	0.764 (2)	0.036 (6)*
C21	0.68639 (13)	0.54339 (13)	0.82663 (15)	0.0173 (3)
H21A	0.671358	0.496901	0.898243	0.021*
H21B	0.614811	0.591950	0.787326	0.021*
C22	0.79487 (16)	0.61910 (14)	0.88314 (18)	0.0248 (4)
H22A	0.808629	0.666175	0.812428	0.037*
H22B	0.865522	0.570888	0.922494	0.037*
H22C	0.780882	0.669390	0.951198	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01275 (12)	0.01291 (13)	0.00940 (12)	0.00043 (8)	0.00570 (9)	0.00058 (8)
N1	0.0177 (6)	0.0179 (6)	0.0145 (6)	0.0026 (5)	0.0067 (5)	0.0004 (5)
C1	0.0164 (7)	0.0152 (7)	0.0144 (6)	−0.0010 (5)	0.0033 (5)	−0.0004 (5)
S1	0.01501 (17)	0.0262 (2)	0.0272 (2)	−0.00084 (14)	0.01044 (14)	−0.00874 (15)
N2	0.0178 (6)	0.0167 (6)	0.0136 (6)	0.0006 (5)	0.0070 (5)	0.0013 (5)
C2	0.0151 (6)	0.0137 (6)	0.0135 (6)	0.0023 (5)	0.0033 (5)	0.0004 (5)
S2	0.02135 (18)	0.02055 (18)	0.01625 (17)	0.00594 (13)	0.01250 (14)	0.00563 (13)
O11	0.0125 (5)	0.0164 (5)	0.0145 (5)	0.0014 (4)	0.0092 (4)	0.0033 (4)
N11	0.0127 (5)	0.0132 (5)	0.0130 (5)	0.0007 (4)	0.0067 (4)	0.0018 (4)
C11	0.0170 (7)	0.0187 (7)	0.0139 (6)	0.0007 (6)	0.0051 (5)	−0.0004 (5)
C12	0.0149 (7)	0.0213 (7)	0.0181 (7)	−0.0022 (6)	0.0060 (5)	−0.0009 (6)
C13	0.0162 (7)	0.0206 (7)	0.0181 (7)	0.0010 (6)	0.0087 (6)	0.0031 (6)
C14	0.0206 (7)	0.0212 (7)	0.0152 (7)	0.0013 (6)	0.0092 (6)	−0.0008 (6)
C15	0.0183 (7)	0.0173 (7)	0.0145 (6)	−0.0017 (6)	0.0063 (5)	−0.0021 (5)
C16	0.0216 (8)	0.0459 (11)	0.0242 (8)	−0.0054 (7)	0.0143 (7)	−0.0012 (7)
O21	0.0154 (5)	0.0180 (5)	0.0130 (5)	0.0007 (4)	0.0052 (4)	−0.0017 (4)
C21	0.0169 (7)	0.0196 (7)	0.0165 (7)	0.0011 (6)	0.0067 (6)	−0.0039 (6)
C22	0.0225 (8)	0.0266 (9)	0.0263 (8)	−0.0042 (6)	0.0088 (7)	−0.0098 (6)

Geometric parameters (Å, º) top

Co1—N1	2.0472 (13)	C13—C14	1.393 (2)
Co1—N2	2.0569 (12)	C13—C16	1.501 (2)
Co1—S2ⁱ	2.5171 (4)	C14—H14	0.9500
Co1—O11	2.0971 (10)	C14—C15	1.375 (2)
Co1—O11ⁱⁱ	2.1594 (10)	C15—H15	0.9500
Co1—O21	2.1559 (10)	C16—H16A	0.9800
N1—C1	1.158 (2)	C16—H16B	0.9800
C1—S1	1.6438 (15)	C16—H16C	0.9800
N2—C2	1.158 (2)	O21—H21	0.815 (16)
C2—S2	1.6498 (15)	O21—C21	1.4437 (17)
O11—N11	1.3557 (15)	C21—H21A	0.9900
N11—C11	1.3454 (19)	C21—H21B	0.9900
N11—C15	1.3477 (18)	C21—C22	1.509 (2)
C11—H11	0.9500	C22—H22A	0.9800
C11—C12	1.379 (2)	C22—H22B	0.9800
C12—H12	0.9500	C22—H22C	0.9800
C12—C13	1.394 (2)

N1—Co1—N2	110.80 (5)	C13—C12—H12	119.8
N1—Co1—S2ⁱ	90.75 (4)	C12—C13—C16	121.15 (14)
N1—Co1—O11ⁱⁱ	160.49 (5)	C14—C13—C12	117.39 (14)
N1—Co1—O11	89.92 (4)	C14—C13—C16	121.46 (14)
N1—Co1—O21	82.55 (5)	C13—C14—H14	119.5
N2—Co1—S2ⁱ	85.67 (4)	C15—C14—C13	120.97 (14)
N2—Co1—O11ⁱⁱ	88.01 (4)	C15—C14—H14	119.5
N2—Co1—O11	158.96 (5)	N11—C15—C14	119.46 (14)
N2—Co1—O21	86.53 (5)	N11—C15—H15	120.3
O11—Co1—S2ⁱ	98.02 (3)	C14—C15—H15	120.3
O11ⁱⁱ—Co1—S2ⁱ	95.96 (3)	C13—C16—H16A	109.5
O11—Co1—O11ⁱⁱ	71.03 (4)	C13—C16—H16B	109.5
O11—Co1—O21	92.89 (4)	C13—C16—H16C	109.5
O21—Co1—S2ⁱ	167.20 (3)	H16A—C16—H16B	109.5
O21—Co1—O11ⁱⁱ	93.90 (4)	H16A—C16—H16C	109.5
C1—N1—Co1	163.29 (12)	H16B—C16—H16C	109.5
N1—C1—S1	178.79 (14)	Co1—O21—H21	103.2 (17)
C2—N2—Co1	166.81 (12)	C21—O21—Co1	124.02 (9)
N2—C2—S2	178.99 (14)	C21—O21—H21	107.9 (17)
C2—S2—Co1ⁱⁱⁱ	100.98 (5)	O21—C21—H21A	109.6
Co1—O11—Co1ⁱⁱ	108.96 (4)	O21—C21—H21B	109.6
N11—O11—Co1	122.53 (8)	O21—C21—C22	110.31 (12)
N11—O11—Co1ⁱⁱ	122.99 (8)	H21A—C21—H21B	108.1
C11—N11—O11	119.16 (12)	C22—C21—H21A	109.6
C11—N11—C15	121.87 (12)	C22—C21—H21B	109.6
C15—N11—O11	118.97 (12)	C21—C22—H22A	109.5
N11—C11—H11	120.1	C21—C22—H22B	109.5
N11—C11—C12	119.79 (13)	C21—C22—H22C	109.5
C12—C11—H11	120.1	H22A—C22—H22B	109.5
C11—C12—H12	119.8	H22A—C22—H22C	109.5
C11—C12—C13	120.49 (14)	H22B—C22—H22C	109.5

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···S2^iv	0.95	2.95	3.4900 (15)	118
C11—H11···O21	0.95	2.57	3.2004 (18)	124
C12—H12···S1^v	0.95	2.96	3.8544 (16)	157
O21—H21···S1ⁱⁱⁱ	0.82 (2)	2.53 (2)	3.3028 (11)	159 (2)
C22—H22C···S2^vi	0.98	2.93	3.7185 (18)	138

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

Acknowledgements

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

References

Böhme, M., Jochim, A., Rams, M., Lohmiller, T., Suckert, S., Schnegg, A., Plass, W. & Näther, C. (2020). Inorg. Chem. 59, 5325–5338. Web of Science PubMed Google Scholar
Böhme, M., Rams, M., Krebs, C., Mangelsen, S., Jess, I., Plass, W. & Näther, C. (2022). Inorg. Chem. 61, 16841–16855. Web of Science PubMed Google Scholar
Brandenburg, K. & Putz, H. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Maji, T. K., Laskar, I. R., Mostafa, G., Welch, A. J., Mukherjee, P. S. & Chaudhuri, N. E. (2001). Polyhedron, 20, 651–655. Web of Science CSD CrossRef CAS Google Scholar
Marsh, R. E. (2009). Acta Cryst. B65, 782–783. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Mautner, F. E., Berger, C., Fischer, R. C., Massoud, S. S. & Vicente, R. (2018a). Polyhedron, 141, 17–24. Web of Science CSD CrossRef CAS Google Scholar
Mautner, F. E., Traber, M., Fischer, R. C., Torvisco, A., Reichmann, K., Speed, S., Vicente, R. & Massound, S. S. (2018b). Polyhedron, 154, 436–442. CSD CrossRef CAS Google Scholar
Näther, C. & Jess, I. (2023). Acta Cryst. E79, 302–307. Web of Science CSD CrossRef IUCr Journals Google Scholar
Näther, C. & Jess, I. (2024a). Acta Cryst. E80, 174–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Näther, C. & Jess, I. (2024b). Acta Cryst. E80, 481–485. CSD CrossRef IUCr Journals Google Scholar
Näther, C. & Jess, I. (2024c). Acta Cryst. E80, 67–71. CSD CrossRef IUCr Journals Google Scholar
Näther, C. & Jess, I. (2024d). Acta Cryst. E80, 463–467. CSD CrossRef IUCr Journals Google Scholar
Neumann, T., Ceglarska, M., Rams, M., Germann, L. Z., Dinnebier, R. E., Suckert, S., Jess, I. & Näther, C. (2018). Inorg. Chem. 57, 3305–3314. CSD CrossRef CAS PubMed Google Scholar
Palion-Gazda, J., Machura, B., Lloret, F. & Julve, M. (2015). Cryst. Growth Des. 56, 2380–2388. Google Scholar
Rams, M., Böhme, M., Kataev, V., Krupskaya, Y., Büchner, B., Plass, W., Neumann, T., Tomkowicz, Z. & Näther, C. (2017a). Phys. Chem. Chem. Phys. 19, 24534–24544. Web of Science CrossRef CAS PubMed Google Scholar
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. Web of Science CSD CrossRef CAS PubMed Google Scholar
Rams, M., Tomkowicz, Z., Böhme, M., Plass, W., Suckert, S., Werner, J., Jess, I. & Näther, C. (2017b). Phys. Chem. Chem. Phys. 19, 3232–3243. Web of Science CSD CrossRef CAS PubMed Google Scholar
Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shi, J. M., Chen, J. N., Wu, C. J. & Ma, J. P. (2007b). J. Coord. Chem. 60, 2009–2013. Web of Science CSD CrossRef CAS Google Scholar
Shi, J. M., Li, W. N., Zhang, F. X., Zhang, X. & Liu, L. D. (2007a). Chin. J. Struct. Chem. 26, 118–121. CAS Google Scholar
Shi, J. M., Liu, Z., Lu, J. J. & Liu, L. D. (2005). Acta Cryst. E61, m1133–m1134. Web of Science CSD CrossRef IUCr Journals Google Scholar
Shi, J. M., Liu, Z., Wu, C. J., Xu, H. Y. & Liu, L. D. (2006c). J. Coord. Chem. 59, 1883–1889. Web of Science CSD CrossRef CAS Google Scholar
Shi, J. M., Sun, Y. M., Liu, Z. & Liu, L. D. (2006b). Chem. Phys. Lett. 418, 84–89. Web of Science CSD CrossRef CAS Google Scholar
Shi, J. M., Sun, Y. M., Liu, Z., Liu, L. D., Shi, W. & Cheng, P. (2006d). Dalton Trans. 376–380.pp. CSD CrossRef Google Scholar
Shi, J.-M., Xu, H.-Y. & Liu, L.-D. (2006e). Acta Cryst. E62, m1577–m1578. Web of Science CSD CrossRef IUCr Journals Google Scholar
Shi, J. M. L., Liu, Z., Sun, Y. M., Yi, L. & Liu, L. D. (2006a). Chem. Phys. 325, 237–242. Web of Science CSD CrossRef CAS Google Scholar
Suckert, S., Rams, M., Böhme, M., Germann, L. S., Dinnebier, R. E., Plass, W., Werner, J. & Näther, C. (2016). Dalton Trans. 45, 18190–18201. Web of Science CSD CrossRef CAS PubMed Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, S.-G., Li, W.-N. & Shi, J.-M. (2006a). Acta Cryst. E62, m3506–m3608. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhang, S.-G., Li, W.-N. & Shi, J.-M. (2006b). Acta Cryst. E62, m3398–m3400. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhang, S.-G. & Shi, J.-M. (2007). Acta Cryst. E63, m1775–m1776. Web of Science CSD CrossRef IUCr Journals Google Scholar

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