Crystal structure of bis­(N,N′-di­methyl­thio­urea-κS)bis­(thio­cyanato-κN)cobalt(II)

Jochim, A.; Radulovic, R.; Jess, I.; Näther, C.

doi:10.1107/S2056989020011111

research communications

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ISSN: 2056-9890

Volume 76| Part 9| September 2020| Pages 1476-1481

https://doi.org/10.1107/S2056989020011111

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Crystal structure of bis(N,N′-dimethylthiourea-κS)bis(thiocyanato-κN)cobalt(II)

Aleksej Jochim,^a ^* Rastko Radulovic,^a Inke Jess ^a and Christian Näther ^a

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

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 10 August 2020; accepted 12 August 2020; online 18 August 2020)

During systematic investigations on the synthesis of coordination polymers with Co(NCS)₂ involving different thiourea derivatives as coligands, crystals of the title compound Co(NCS)₂(N,N′-dimethylthiourea)₂, or [Co(C₃H₈N₂S)₂(NCS)₂], were obtained. These crystals were non-merohedric twins and therefore, a twin refinement using data in HKLF-5 format was performed. In the crystal structure of this compound, the Co^II cations are coordinated by two N-terminally bonded thiocyanate anions as well as two S-bonding N,N′-dimethylthiourea molecules, forming two crystallographically independent discrete complexes each with a strongly distorted tetrahedral geometry. An intricate network of intermolecular N—H⋯S and C—H⋯S hydrogen bonds can be found between the complexes. The thermogravimetric curve of the title compound shows two discrete steps in which all coligand molecules have been emitted, which is also accompanied by partial decomposition of the cobalt thiocyanate. If the measurement is stopped after the first mass loss, only broad reflections of CoS can be found in the XRPD pattern of the residue, which proves that this compound decomposes completely upon heating. However, at lower temperatures an endothermic signal can be found in the DTA and DSC curve, which corresponds to melting, as proven by thermomicroscopy.

Keywords: crystal structure; cobalt thiocyanate; N,N′-dimethylthiourea; discrete complexes; thermal properties.

CCDC reference: 2023019

1. Chemical context

Investigations on the synthesis, crystal structures and magnetic properties of coordination polymers based on transition-metal thiocyanates have become of increasing interest in recent years, which is due to the high structural diversity of the thiocyanate anion and its ability to mediate reasonable magnetic exchange. Although many different transition-metal thiocyanate coordination compounds are known, our main interests focus on first-row transition-metal thiocyanate compounds with the general composition M(NCS)₂(L)₂ in which paramagnetic metal cations M are connected by pairs of μ-1,3 bridging thiocyanate anions into chains, while the remaining coordination sites are occupied by neutral coligands L, forming an octahedral coordination polyhedron. In most of these compounds, linear chains are formed in which all ligands are trans (Prananto et al., 2017 ; Werner et al., 2015a ; Mautner et al., 2018 ; Rams et al., 2020 ; Jin et al., 2007 ), but other isomers are also possible. This includes compounds in which either the N-bonding thiocyanates, the S-bonding thiocyanates or the coligands are trans, while the other ligands are cis. These motifs are found, for example, in [M(NCS)₂(4-benzylpyridine)₂]_n (M = Mn, Ni, Cd) (Suckert et al., 2015 ; Jochim et al., 2018 ; Neumann et al., 2018a ), [M(NCS)₂(4-nitropyridine N-oxide)₂]_n (M = Mn, Co, Cd) (Shi et al., 2006 , 2007 ; Mautner et al., 2016 ) and [M(NCS)₂(4-benzoylpyridine)₂]_n (M = Co, Ni) (Rams et al., 2017 ; Jochim et al., 2018), in which different cis–cis–trans configurations can be found around the metal centers. The last possible isomer, in which all ligands are cis, is not found for the composition M(NCS)₂(L)₂, although it was observed in more ligand-deficient compounds of composition Co(NCS)₂(L), with L representing either 4-methylpyridine N-oxide or 4-methoxypyridine N-oxide (Zhang et al., 2006a ,b ).

In those cases in which either only the N-bonding or the S-bonding thiocyanate are cis, corrugated chains are formed instead of linear ones, which is also the case if all ligands are cis. Furthermore, in some compounds a mixture of these configurations can be found, as in [M(NCS)₂(4-chloropyridine)₂]_n (M = Co, Ni, Cd) (Böhme et al., 2020 ; Jochim et al., 2018; Goher et al., 2003 ) or the high-temperature modification of [Ni(NCS)₂(4-aminopyridine)₂]_n (Neumann et al., 2018b ), in which an alternating arrangement of all-trans and cis–cis–trans-coordinated metal cations is present.

For some compounds of composition M(NCS)₂(L)₂ a completely different structure is observed, in which the metal cations are connected into layers of different topologies by the thiocyanate anions. Only one topology is known for cobalt compounds of this composition, in which every two cobalt cations are connected by a pair of μ-1,3-bridging thiocyanate anions, forming dimers, which are connected to four adjacent dimers by single μ-1,3-bridging thiocyanate anions (Wöhlert & Näther, 2013 ; Suckert et al., 2016 , 2017 ; Werner et al., 2015b ). Nevertheless, with other metal cations different layer topologies are known in which, for example, trimers are formed instead of dimers, which are connected by single μ-1,3-thiocyanate bridges (Kozísková et al., 1990 ; Kabešová et al., 1990 ) or in which each metal cation is directly connected to four neighboring metal cations by single μ-1,3-thiocyanate bridges (McElearney et al., 1979 ; Werner et al., 2015c ; Đaković et al., 2010 ). Although it is not clear by which parameters the formation of either chains or layers is promoted, a third isomer of composition Co(NCS)₂(L)₂ exists in which the thiocyanate anions are N-terminally coordinated, forming discrete tetrahedral complexes (Prananto et al., 2017; Neumann et al., 2018c ; Hannachi et al., 2019 ). In most of these compounds, electron-rich coligands are found, which might indicate that this type of compound is formed when a strong donor is used as coligand.

Most of the aforementioned compounds contain N-donor coligands, but in the course of our systematic work we became interested in the influence of S-donor coligands based on thiourea derivatives on the magnetic properties of Co(NCS)₂ chain compounds, in which the metal cations are linked by pairs of μ-1,3-bridging thiocyanate anions. With nickel, two compounds with the composition Ni(NCS)₂(ethylenethiourea)₂ (Nardelli et al., 1966 ) and Ni(NCS)₂(thioacetamide)₂ (Capacchi et al., 1968 ) are known. We prepared the corresponding cobalt compound with ethylenethiourea, which is isotypic to the nickel analogue (Jochim et al., 2020a ). Only one additional polymeric compound with the composition [Co(NCS)₂(thiourea)₂]_n is known, in which the cobalt cations are connected by the sulfur atoms of the coligands, while the thiocyanate anions are N-terminally coordinated (Rajarajan et al., 2012 ; Muthu et al., 2015 ). In further work we prepared Co(NCS)₂(tetramethylthiourea)₂, which surprisingly consists of discrete tetrahedral complexes (Jochim et al., 2020b ).

To further investigate this structural behavior, we used N,N′-dimethylthiourea as coligand, which is between thiourea and tetramethylthiourea considering the substitution with methyl groups, and during these investigations the title compound was obtained. Its IR spectrum shows that the C—N stretching vibration is found at 2064 cm⁻¹, which is indicative of N-terminally bonded thiocyanate anions, pointing to the formation of a tetrahedral complex, as proven by single crystal X-ray diffraction (see Fig. S1 in the supporting information). Although the experimental XRPD pattern is very similar to that calculated for the title compound, some additional reflections are found, indicating some contamination (Fig. S2). This is surprising, because all samples were prepared in different ways and using a different ratio of Co(NCS)₂ and dimethylthiourea leads to an identical XRPD pattern. In the thermogravimetry curve (Fig. S3), two mass losses of 37.2% and 26.3% are observed, which in total is more than expected for the emission of both coligand molecules (54.3%), indicating the decomposition of the thiocyanate anions. This was proven by PXRD of the residue isolated after the first mass loss, which is mostly amorphous but which contains a small amount of crystalline CoS (Fig. S4). At low temperatures, an additional endothermic event can be found in the differential thermoanalysis curve, which is not accompanied by a mass change of the sample. This event corresponds to melting of the sample and is not reversible upon cooling, which was shown by differential scanning calorimetry (Fig. S5) and thermomicroscopy (Fig. S6).

2. Structural commentary

The asymmetric unit of the title compound contains two crystallographically independent complexes built up of two thiocyanate anions and two N,N′-dimethylthiourea molecules in general positions as well as one cobalt(II) cation, which is situated on a twofold rotational axis in both crystallographically independent complexes. Both metal cations are coordinated by two N-bonding thiocyanate anions and two S-bonding N,N′-dimethylthiourea molecules, forming strongly distorted tetrahedra (Fig. 1), which becomes obvious from the tetrahedral angle variance σ_θ〈tet〉² = 73.2 (Co1) or 73.3 (Co2) and the mean tetrahedral quadratic elongation 〈λ_tet〉 = 1.030 (Co1, Co2) (Robinson et al., 1971 ). However, all bond lengths and angles are comparable to those reported for similar compounds in the literature (Neumann et al. 2018c). Both N,N′-dimethylthiourea molecules are nearly planar with C_Me—N—C—N torsion angles of 177.7 (3) and −0.5 (4)° for the complex containing Co1 and 178.9 (3) and −1.2 (4)° for that containing Co2. Both N,N′-dimethylthiourea planes within each complex are slightly tilted relative to each other, leading to an angle of 9.51 (10)° between the normal vectors of the N,N′-dimethylthiourea planes in the complex containing Co1, while the corresponding angle for the complex containing Co2 is 13.52 (8)°. Similar values are observed for the corresponding angles between the N,N′-dimethylthiourea planes of different crystallographically independent complexes.

Figure 1
View of the two crystallographically independent molecules in the asymmetric unit of the title compound with atom labeling and displacement ellipsoids drawn at the 50% probability level. Symmetry codes: (i) −x + 1, y, −z + $[3\over2]$ ; (ii) −x, y, −z + $[1\over2]$ .

3. Supramolecular features

The discrete complexes are connected via relatively weak N—H⋯S_NCS hydrogen bonds (Table 1), forming chains along the [101] direction in which the two crystallographically independent discrete complexes alternate. For both complexes, either only the thiocyanate anions (Co1) or the N,N′-dimethylthiourea molecules (Co2) are involved in the formation of this structure. Two neighboring chains are connected into double chains by pairs of additional N—H⋯S_NCS hydrogen bonds involving only the complexes containing Co1 (Fig. 2). In a similar way, chains built up of an alternating sequence of complexes containing either Co1 or Co2 are formed, which run along the a-axis direction, but in this case, in the complexes containing Co1, only the N,N′-dimethylthiourea molecules participate in the N—H⋯S_NCS hydrogen bonds, while in the complex containing Co2, only the thiocyanate anions are involved. Within these chains, additional C—H⋯S hydrogen bonds between the N,N′-dimethylthiourea molecules of adjacent complexes can be found (Fig. 3). The two types of chain are connected via C—H⋯S hydrogen bonds between the N,N′-dimethylthiourea molecules, forming layers parallel to the ac plane (Fig. 4), which are further connected into a three-dimensional network by additional N—H⋯S_NCS hydrogen bonds.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11⋯S1ⁱ	0.88	2.65	3.341 (2)	136
N12—H12⋯N1	0.88	2.69	3.282 (3)	126
N12—H12⋯S2ⁱⁱ	0.88	2.88	3.582 (2)	138
C13—H13B⋯S21ⁱⁱⁱ	0.98	2.80	3.578 (3)	137
N21—H21⋯S1	0.88	2.61	3.372 (2)	146
C22—H22A⋯S2^iv	0.98	3.01	3.591 (3)	120
C22—H22A⋯S21ⁱⁱⁱ	0.98	3.02	3.752 (4)	132
N22—H22⋯S2^v	0.88	2.79	3.486 (3)	137
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (iii) -x, -y+1, -z+1; (iv) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (v) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Figure 2
Crystal structure of the title compound with a view of the chains that extend along [101]. Intermolecular N—H⋯S hydrogen bonding is shown as dashed lines.

Figure 3
Crystal structure of the title compound with a view of the chains that extend along the a-axis direction. Intermolecular N—H⋯S and C—H⋯S hydrogen bonds are shown as dashed lines.

Figure 4
Crystal structure of the title compound with a view perpendicular to the layers parallel to the crystallographic ac plane. Intermolecular N—H⋯S and C—H⋯S hydrogen bonds are shown as dashed lines.

4. Database survey

In the Cambridge Structure Database (Version 5.41, last update November 2019; Groom et al., 2016 ), only one transition-metal thiocyanate compound with N,N′-dimethylthiourea is reported, which has the composition Cu(NCS)(N,N′-dimethylthiourea)[propane-1,3-diylbis(diphenylphosphine)] (Wattanakanjana et al., 2015 ). In this compound, the Cu^I cations are tetrahedrally coordinated by one thiocyanate anion, one N,N′-dimethylthiourea molecule and one propane-1,3-diylbis(diphenylphosphine) molecule, with both phosphines coordinating to the metal center. In total, only 49 compounds containing a transition-metal cation and N,N′-dimethylthiourea are known, none of which contains cobalt. In fact, 28 of these compounds involve more chalcophilic second or third row transition-metal cations, while nearly half of the remaining compounds contain copper.

Considering compounds that contain cobalt thiocyanate, over one thousand compounds are found, most of which show either an octahedral or a tetrahedral coordination geometry with the octahedral coordination geometry being the most common. Nevertheless, approximately 200 compounds with tetrahedral coordination geometry are known, making it the second most common coordination geometry for cobalt thiocyanate compounds.

5. Synthesis and crystallization

General

N,N′-dimethylthiourea was purchased from Sigma Aldrich, while Co(NCS)₂ was purchased from Alfa Aesar. All chemicals were used without further purification.

Synthesis

Single crystals were obtained by reacting Co(NCS)₂ (0.15 mmol, 26.3 mg) with N,N′-dimethylthiourea (0.3 mmol, 31.3 mg) in 0.4 mL of water. After approximately one week, deep-blue crystals were obtained, which were suitable for single crystal analysis. The same procedure was used to obtain powder samples using a higher amount of Co(NCS)₂ (1.00 mmol, 175.1 mg), N,N′-dimethylthiourea (2.0 mmol, 208.4 mg) and water (0.75 mL). The resulting crystals were ground into powder. In some cases, no crystallization of the mixture occurred, which was prevented by storing the reaction mixture at 281 K. Elemental analysis calculated for C₈H₁₆N₆CoS₄ (383.45 g/mol) C 25.06%, H 4.21%, N 21.92%, S 33.45%, found: C 24.79%, H 4.34%, N 21.75%, S 32.16%.

Experimental details

Elemental analysis was performed using a EURO EA elemental analyzer fabricated by EURO VECTOR Instruments.

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.

DTA–TG measurements were performed in a dynamic nitrogen atmosphere (100 sccm) in Al₂O₃ crucibles using a STA-PT 1600 thermobalance from Linseis. The instrument was calibrated using standard reference materials.

The DSC measurements were performed with a DSC 1 Star System with STARe Excellence Software from Mettler–Toledo AG. The instrument was calibrated using standard reference materials.

Thermomicroscopic measurements were performed using an FP82 hot stage from Mettler and a BX60 microscope from Olympus, using the analysis software package from Mettler.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All non-hydrogen atoms were refined anisotropically. The C—H H atoms were positioned with idealized geometry and refined isotropically with U_iso(H) = 1.5U_eq(C), allowing them to rotate, but not to tip. The N—H H atoms were located in the difference map, their bond lengths were set to ideal values and finally they were refined using a riding model [U_iso(H) = 1.2U_eq(N)]. As the crystal studied was twinned by non-merohedry, a twin refinement using data in HKLF 5 format was performed. The corresponding files were generated by PLATON (Spek 2020 ).

Table 2
Experimental details

Crystal data
Chemical formula	[Co(C₃H₈N₂S)₂(NCS)₂]
M_r	383.44
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	16.8070 (8), 14.4212 (6), 15.5669 (9)
β (°)	118.744 (4)
V (Å³)	3308.1 (3)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	1.54
Crystal size (mm)	0.10 × 0.08 × 0.07

Data collection
Diffractometer	Stoe IPDS2
No. of measured, independent and observed [I > 2σ(I)] reflections	3218, 3218, 2767
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.105, 1.07
No. of reflections	3218
No. of parameters	178
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.40
Computer programs: X-AREA and XP (Stoe & Cie, 2002 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ), DIAMOND (Brandenburg & Putz, 1999 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2023019

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020011111/tx2032sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020011111/tx2032Isup2.hkl

Figure S1. IR spectrum of the title compound. Given is the value of the CN stretching vibration of the thiocyanate anions. DOI: https://doi.org/10.1107/S2056989020011111/tx2032sup3.tif

Figure S2. Experimental (top) and calculated (bottom) PXRD pattern of the title compound measured with Cu-radiation. DOI: https://doi.org/10.1107/S2056989020011111/tx2032sup4.tif

Figure S3. DTG, TG and DTA curve of the title compound measured with 4C/min. in a nitrogen atmosphere. DOI: https://doi.org/10.1107/S2056989020011111/tx2032sup5.tif

Figure S4. XRPD pattern of the residue obtained after the first mass loss (top) together with the calculated pattern for CoS. DOI: https://doi.org/10.1107/S2056989020011111/tx2032sup6.tif

Figure S5. DSC heating and cooling curve of the title compound until the first endothermic event using a heating rate of 4C/min. under a nitrogen atmosphere. DOI: https://doi.org/10.1107/S2056989020011111/tx2032sup7.tif

Figure S6. Thermomicroscopic images of the title compound at different temperatures when heated in air with 10 C/min. DOI: https://doi.org/10.1107/S2056989020011111/tx2032sup8.tif

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-AREA (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: XP (Sheldrick, 2008) and DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(N,N'-dimethylthiourea-κS)bis(thiocyanato-κN)cobalt(II) top

Crystal data top

[Co(C₃H₈N₂S)₂(NCS)₂]	F(000) = 1576
M_r = 383.44	D_x = 1.540 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.8070 (8) Å	Cell parameters from 3218 reflections
b = 14.4212 (6) Å	θ = 2.0–26.0°
c = 15.5669 (9) Å	µ = 1.54 mm⁻¹
β = 118.744 (4)°	T = 200 K
V = 3308.1 (3) Å³	Block, blue
Z = 8	0.10 × 0.08 × 0.07 mm

Data collection top

Stoe IPDS-2 diffractometer	θ_max = 26.0°, θ_min = 2.0°
ω scans	h = −20→19
3218 measured reflections	k = −17→17
3218 independent reflections	l = −2→19
2767 reflections with I > 2σ(I)

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.105	w = 1/[σ²(F_o²) + (0.0632P)² + 1.3645P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
3218 reflections	Δρ_max = 0.72 e Å⁻³
178 parameters	Δρ_min = −0.40 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component twin.

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

	x	y	z	U_iso*/U_eq
Co1	0.500000	0.35611 (3)	0.750000	0.04070 (15)
Co2	0.000000	0.64084 (3)	0.250000	0.04322 (15)
N1	0.38555 (14)	0.28706 (15)	0.69242 (15)	0.0454 (5)
C1	0.30981 (16)	0.26507 (16)	0.65171 (17)	0.0399 (5)
S1	0.20412 (4)	0.23531 (6)	0.59318 (5)	0.0602 (2)
N2	0.11433 (14)	0.70960 (15)	0.30776 (16)	0.0488 (5)
C2	0.19017 (16)	0.73153 (16)	0.34319 (17)	0.0414 (5)
S2	0.29563 (4)	0.76089 (6)	0.39174 (6)	0.0609 (2)
S11	0.52044 (4)	0.43897 (5)	0.88607 (5)	0.05212 (19)
C11	0.41958 (16)	0.49900 (16)	0.84464 (17)	0.0404 (5)
N11	0.41916 (14)	0.58993 (14)	0.85125 (16)	0.0464 (5)
H11	0.366818	0.618316	0.831086	0.056*
C12	0.5004 (2)	0.64714 (19)	0.8938 (3)	0.0603 (7)
H12A	0.539073	0.629383	0.962335	0.090*
H12B	0.483201	0.712509	0.890419	0.090*
H12C	0.533658	0.638091	0.857165	0.090*
N12	0.34179 (14)	0.45328 (15)	0.80762 (17)	0.0525 (5)
H12	0.346693	0.392461	0.809838	0.063*
C13	0.25300 (16)	0.4945 (2)	0.7730 (2)	0.0596 (7)
H13A	0.247660	0.518724	0.828810	0.089*
H13B	0.206126	0.447472	0.738940	0.089*
H13C	0.245126	0.545309	0.727713	0.089*
S21	−0.01638 (5)	0.55786 (6)	0.36690 (6)	0.0628 (2)
C21	0.08297 (16)	0.49509 (18)	0.42795 (17)	0.0448 (5)
N21	0.08038 (14)	0.40531 (15)	0.43729 (16)	0.0494 (5)
H21	0.131208	0.377325	0.478147	0.059*
C22	−0.0021 (2)	0.3505 (2)	0.3986 (3)	0.0710 (9)
H22A	−0.037573	0.369132	0.430511	0.107*
H22B	0.013644	0.284667	0.411331	0.107*
H22C	−0.037934	0.360733	0.327816	0.107*
N22	0.16179 (14)	0.53884 (16)	0.46741 (18)	0.0562 (6)
H22	0.158916	0.599750	0.468078	0.067*
C23	0.24956 (16)	0.4953 (2)	0.5241 (2)	0.0584 (7)
H23A	0.254623	0.471054	0.585312	0.088*
H23B	0.297563	0.541035	0.538953	0.088*
H23C	0.255899	0.444206	0.486232	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0279 (2)	0.0390 (3)	0.0494 (3)	0.000	0.0138 (2)	0.000
Co2	0.0258 (2)	0.0420 (3)	0.0532 (3)	0.000	0.0121 (2)	0.000
N1	0.0382 (11)	0.0428 (11)	0.0500 (11)	−0.0038 (9)	0.0171 (9)	0.0013 (9)
C1	0.0369 (12)	0.0355 (11)	0.0441 (11)	−0.0007 (9)	0.0169 (10)	0.0046 (9)
S1	0.0349 (4)	0.0658 (5)	0.0642 (4)	−0.0127 (3)	0.0112 (3)	0.0176 (3)
N2	0.0359 (11)	0.0480 (12)	0.0564 (12)	−0.0041 (9)	0.0173 (9)	−0.0074 (9)
C2	0.0343 (12)	0.0383 (12)	0.0472 (12)	−0.0009 (9)	0.0162 (10)	−0.0027 (10)
S2	0.0338 (4)	0.0657 (5)	0.0756 (5)	−0.0133 (3)	0.0202 (3)	−0.0155 (4)
S11	0.0319 (3)	0.0517 (4)	0.0584 (4)	0.0053 (3)	0.0103 (3)	−0.0126 (3)
C11	0.0342 (12)	0.0430 (13)	0.0427 (11)	−0.0007 (9)	0.0174 (10)	−0.0042 (9)
N11	0.0359 (10)	0.0408 (11)	0.0594 (12)	0.0012 (8)	0.0204 (9)	0.0004 (9)
C12	0.0480 (16)	0.0447 (15)	0.0811 (19)	−0.0081 (12)	0.0252 (14)	0.0004 (13)
N12	0.0337 (11)	0.0430 (11)	0.0722 (14)	−0.0023 (9)	0.0185 (10)	−0.0081 (10)
C13	0.0315 (15)	0.065 (2)	0.0759 (18)	0.0008 (11)	0.0205 (13)	−0.0055 (14)
S21	0.0330 (3)	0.0697 (5)	0.0821 (5)	0.0105 (3)	0.0248 (3)	0.0292 (4)
C21	0.0336 (12)	0.0530 (15)	0.0435 (12)	−0.0003 (10)	0.0152 (10)	0.0039 (10)
N21	0.0381 (11)	0.0438 (12)	0.0560 (12)	−0.0009 (9)	0.0145 (10)	−0.0041 (9)
C22	0.0503 (18)	0.0550 (18)	0.094 (2)	−0.0149 (14)	0.0233 (16)	−0.0172 (16)
N22	0.0337 (11)	0.0455 (12)	0.0771 (15)	0.0016 (9)	0.0169 (11)	0.0117 (11)
C23	0.0309 (15)	0.061 (2)	0.0665 (16)	0.0046 (11)	0.0103 (12)	0.0036 (13)

Geometric parameters (Å, º) top

Co1—N1ⁱ	1.959 (2)	C2—S2	1.614 (2)
Co1—N1	1.959 (2)	S11—C11	1.728 (2)
Co1—S11	2.3093 (7)	C11—N11	1.316 (3)
Co1—S11ⁱ	2.3093 (7)	C11—N12	1.323 (3)
Co2—N2ⁱⁱ	1.955 (2)	N11—C12	1.454 (4)
Co2—N2	1.955 (2)	N12—C13	1.448 (3)
Co2—S21	2.3024 (8)	S21—C21	1.728 (3)
Co2—S21ⁱⁱ	2.3024 (8)	C21—N21	1.306 (3)
N1—C1	1.161 (3)	C21—N22	1.322 (3)
C1—S1	1.616 (2)	N21—C22	1.451 (4)
N2—C2	1.163 (3)	N22—C23	1.448 (3)

N1ⁱ—Co1—N1	118.89 (13)	C2—N2—Co2	165.2 (2)
N1ⁱ—Co1—S11	99.39 (6)	N2—C2—S2	179.3 (2)
N1—Co1—S11	111.28 (6)	C11—S11—Co1	103.32 (8)
N1ⁱ—Co1—S11ⁱ	111.28 (6)	N11—C11—N12	119.3 (2)
N1—Co1—S11ⁱ	99.39 (6)	N11—C11—S11	120.75 (18)
S11—Co1—S11ⁱ	117.68 (4)	N12—C11—S11	119.95 (18)
N2ⁱⁱ—Co2—N2	119.05 (13)	C11—N11—C12	124.2 (2)
N2ⁱⁱ—Co2—S21	99.35 (7)	C11—N12—C13	125.6 (2)
N2—Co2—S21	111.39 (7)	C21—S21—Co2	104.82 (8)
N2ⁱⁱ—Co2—S21ⁱⁱ	111.39 (7)	N21—C21—N22	120.1 (2)
N2—Co2—S21ⁱⁱ	99.35 (7)	N21—C21—S21	120.37 (18)
S21—Co2—S21ⁱⁱ	117.37 (5)	N22—C21—S21	119.5 (2)
C1—N1—Co1	165.2 (2)	C21—N21—C22	124.8 (2)
N1—C1—S1	178.9 (2)	C21—N22—C23	125.1 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···S1ⁱⁱⁱ	0.88	2.65	3.341 (2)	136
N12—H12···N1	0.88	2.69	3.282 (3)	126
N12—H12···S2^iv	0.88	2.88	3.582 (2)	138
C13—H13B···S21^v	0.98	2.80	3.578 (3)	137
N21—H21···S1	0.88	2.61	3.372 (2)	146
C22—H22A···S2^vi	0.98	3.01	3.591 (3)	120
C22—H22A···S21^v	0.98	3.02	3.752 (4)	132
N22—H22···S2^vii	0.88	2.79	3.486 (3)	137

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

Acknowledgements

We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

Funding information

This project was supported by the Deutsche Forschungsgemeinschaft (project No. NA 720/5–2) and the State of Schleswig-Holstein.

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