Synthesis, crystal structure and stability of a new isomer of bis­(ethyl­ene­thio­urea)di­thio­cyanatocobalt(II)

Näther, C.; Jochim, A.

doi:10.1107/S2056989026007383

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ISSN: 2056-9890

Volume 82| Part 8| August 2026| Pages 968-973

https://doi.org/10.1107/S2056989026007383

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Synthesis, crystal structure and stability of a new isomer of bis(ethylenethiourea)dithiocyanatocobalt(II)

Christian Näther ^a ^* and Aleksej Jochim ^a

^aInstitut für Anorganische Chemie, Universität Kiel, Max-Eyth.-Str. 2, 24118 Kiel, Germany
^*Correspondence e-mail: [email protected]

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 24 June 2026; accepted 17 July 2026; online 23 July 2026)

The title compound, bis(imidazolidine-2-thione-κS)dithiocyanatocobalt(II), [Co(NCS)₂(C₃H₆N₂S)₂], was prepared by the reaction of cobalt thiocyanate with ethylenethiourea in ethanol solution. The asymmetric unit (space group P2₁/c) consists of one cobalt cation, as well as two crystallographically independent thiocyanate anions and two ethylenethiourea ligands, all of them located in general positions. The metal cations are tetrahedrally coordinated by two N-bonding anionic ligands and two ethylenethiourea ligands into discrete complexes. These complexes are linked by N—H⋯S hydrogen bonds into layers. The IR spectrum is in agreement with the presence of a tetrahedral coordination with N-bonding thiocyanate anions and measurements using X-ray powder diffraction indicate that a pure crystalline phase has been obtained. The title compound represents a new isomer of Co(NCS)₂(C₃H₆N₂S)₂, which was already reported in the literature in space group P1 [Mautner et al., (2018 ). Polyhedron 154, 436–442]. In contrast to the title compound, in the triclinic isomer the cobalt cations are octahedrally coordinated and linked into chains by μ-1,3-bridging thiocyanate anions. Solvent-mediated conversion experiments starting from a mixture of both isomers show that the title complex is the thermodynamically stable form at room temperature.

Keywords: synthesis; crystal structure; isomerism; thermodynamic stability; cobalt thiocyanate; ethylenethiourea.

CCDC reference: 2574161

1. Chemical context

Polymorphism and isomerism are widespread phenomena in coordination chemistry (Braga & Grepioni, 2000 ; Barnett et al., 2002 ; Moulton & Zaworotko, 2001 ). Different polymorphs or isomers are frequently found in, for example, coordination compounds based on transition-metal thiocyanates with N-donor coligands, which might be traced back to the fact that this class of compounds shows a large structural variability, which originates in part from the different coordination modes of this anionic ligand but also from the fact that some transition-metal cations show variability in their coordination numbers (Krebs et al., 2021a ; Wellm et al., 2020 ; Böhme et al., 2020 ; Neumann et al., 2018 ).

For many years, we and others have been especially interested in cobalt thiocyanate and selenocyanate compounds with the general composition Co(NCX)₂(L)₂ (X = S, Se and L = N-donor coligand) because some of them show interesting magnetic properties such as single-chain magnet (SCM) behavior (Wöhlert et al., 2012 , 2013 ). This is the case in compounds in which the cobalt cations are octahedrally coordinated by two N- and two S-bonding thiocyanate anions and two N-donor coligands and linked into chains by μ-1,3-bridging thiocyanate anions. Such a coordination represents an MA₂B₂C₂ system for which five isomers exist, namely one all-trans, three different cis–cis–trans and one all-cis isomer. We found that for SCM behavior to be observed in compounds with linear chains, an all-trans coordination or a cis–cis–trans coordination with the coligands in trans-positions is needed (Böhme et al., 2020). The other isomers lead to the formation of corrugated chains, for which the magnetic exchange is suppressed (Böhme et al., 2020). There are a few additional compounds with this composition in which Co(NCS)₂ layers are observed and that show ferromagnetic ordering at low temperatures (Suckert et al., 2016 ).

In the beginning, we focused on pyridine derivatives as coligands, for which the majority of compounds consist of linear chains. However, in the course of our systematic work we also used 4-dimethylaminopyridine as coligand, but in contrast to all other ligands investigated before, discrete tetrahedral complexes were obtained, which crystallize in different isomeric or polymorphic modifications and which represent an isomer of the compounds mentioned above (Näther et al., 2018 ; Krebs et al., 2021b ). Such complexes are of less interest for our project because no SCM behavior can be observed. The reason why for some ligands chains and for some others discrete complexes are observed is still unknown.

In 2018, Mautner and coworkers reported on the synthesis, structure and properties of Co(NCS)₂(4-methoxypyridine)₂, which shows linear chains and SCM behavior (Mautner et al., 2018; Rams et al., 2020 ). However, under slightly different reaction conditions they were also able to prepare a second isomer with this composition that consists of discrete complexes. Unfortunately it was not determined which of the two isomers is thermodynamically stable at a given temperature.

Some time later, we became interested in such compounds with coligands other than pyridine derivatives, to study the influence of the coligand on the structural and magnetic behavior. With ethylenethiourea, we obtained a compound with the composition Co(NCS)₂(ethylenethiourea)₂ (CSD refcode ZZZFAI01, space group P $[\overline{1}]$ ; Böhme et al., 2020) in which the cations are octahedrally coordinated with an all-trans coordination and linked into linear chains by the anionic ligands (Fig. 1). Recently we tried to synthesize this compound again for additional investigations, but instead of the known chain isomer, the title compound was obtained and we now describe its crystal structure and thermodynamic stability using solvent-mediated conversion experiments.

Figure 1
View of apart of a chain in the known isomer of Co(NCS)₂(ethylenethiourea)₂.

2. Structural commentary

The asymmetric unit of the title compound, Co(NCS)₂(C₃H₆N₂S)₂ (C₃H₆N₂S = ethylenethiourea), which crystallizes in space group P2₁/c, consists of one crystallographically independent cobalt cation, two independent thiocyanat anions and two independent ethylenethiourea ligands with all atoms lying on general positions. The metal cations are fourfold coordinated (Table 1) by two N-bonding thiocyanate anions and two ethylenethiourea ligands in a slightly distorted tetrahedral environment (Fig. 2). The C11 ethylenethiourea ring is an envelope with atom C12 as the flap whereas the C21 ring is twisted about the C22—C23 bond. Therefore, this structure is completely different from that of the known isomer of Co(NCS)₂(ethylenethiourea) already reported in the literature, which consists of octahedrally cobalt cations that are linked into chains via pairs of μ-1,3-bridging thiocyanato anions (Fig. 1).

Table 1
Selected geometric parameters (Å, °)

Co1—N1	1.9446 (15)	Co1—S11	2.3111 (5)
Co1—N2	1.9544 (16)	Co1—S21	2.3120 (5)

N1—Co1—N2	110.32 (7)	S11—Co1—S21	113.076 (19)
N1—Co1—S11	114.80 (5)	C1—N1—Co1	167.80 (15)
N2—Co1—S11	102.29 (5)	C2—N2—Co1	171.01 (15)
N1—Co1—S21	100.61 (5)	C11—S11—Co1	102.33 (6)
N2—Co1—S21	116.30 (5)	C21—S21—Co1	110.89 (6)

Figure 2
Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level.

Even if cobalt thiocyanate compounds with an octahedral coordination and bridging anionic ligands represent the majority of structures, compounds with a tetrahedral coordination are also reported. These include, for example, Co(NCS)₂(4-N,N′-dimethylaminopyridine)₂, which crystallizes in different polymorphic modifications [Neumann et al., 2018 (refcode GIQPEE); Krebs et al., 2021b (GIQPEE01 and GIQPEE02)] as well as Co(NCS)₂(3-aminopyridine (ANUMII; Mautner et al., 2021 ), Co(NCS)₂(4-aminopyridine)₂ (UGUWEA; Sugiyama et al., 2015 ) Co(NCS)₂(4-vinylpyridine)₂ (BOZJUW; Foxman & Mazurek, 1982 ) and Co(NCS)₂(3-methylpyridine)₂ (EYARIG; Boeckmann et al., 2011 ).

3. Supramolecular features

In the extended structure of the title compound, a number of N—H⋯S interactions are observed (Table 2), with some of them at relatively short H⋯S distances and N—H⋯S angles close to linearity, indicating hydrogen bonding rather than incidental contacts (Table 2). This leads to the formation of chains, which propagate in the crystallographic a-axis direction (Fig. 3). These chains are further connected into layers that lie parallel to the bc plane (Fig. 4). Additional N—H⋯S interactions are found between the layers, but at long distances and angles far from 180°.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11⋯S2ⁱ	0.88	2.57	3.3693 (16)	152
N12—H12⋯S11ⁱⁱ	0.88	2.95	3.5571 (17)	128
N12—H12⋯S21ⁱⁱⁱ	0.88	2.97	3.4542 (15)	116
C12—H12A⋯S21ⁱⁱⁱ	0.99	2.91	3.4371 (19)	114
C13—H13B⋯S1ⁱⁱⁱ	0.99	2.95	3.816 (2)	147
N21—H21⋯S11^iv	0.88	2.74	3.5823 (16)	161
N22—H22⋯S2^v	0.88	2.83	3.3560 (16)	120
N22—H22⋯S11	0.88	2.73	3.5346 (15)	152
C22—H22A⋯S2ⁱ	0.99	2.96	3.800 (2)	143
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 3
View onto a layer in the crystal structure of the title compound. Intermolecular N—H⋯S hydrogen bonding is shown as dashed lines.

Figure 4
Crystal structure of the title compound in a view along the crystallographic a-axis direction. Intermolecular N—H⋯S hydrogen bonding is shown as dashed lines.

4. Physical characterization

The IR spectrum reveals that the CN stretching vibration of the thiocyanate anions occurs at 2056 cm⁻¹, in agreement with the presence of tetrahedral coordination (Fig. 5). The bands between 3000 and 3500 cm⁻¹ can be assigned to the N—H stretching vibration with this group involved in intermolecular hydrogen bonding.

Figure 5
IR spectrum of the title compound. The value of the CN stretching vibration of the thiocyanate anions is given.

Comparison of the experiment X-ray powder pattern with that calculated using single crystal data reveal that a pure sample has been obtained (Fig. 6).

Figure 6
Experimental (top) and calculated (bottom)X-ray powder patterns of the title compound.

To investigate which of the two modifications of Co(NCS)₂(C₃H₆N₂S)₂ is the thermodynamically stable form at room temperature, solvent-mediated conversion experiments were performed. In this experiment, a mixture of the two isomers with excess of solid was stirred in ethanol at room temperature and these residues were investigated by X-ray powder diffraction after one and four days (Fig. 7). This shows that the reflections of the chain isomer disappear completely, which proves that the title compound represents the thermodynamically stable isomer at room temperature, where the chain isomer is metastable.

Figure 7
Calculated X-ray powder pattern of the chain isomer (A) and the title compound (B) as well as experimental pattern of a mixture of both isomers (C) and after stirring this mixture in ethanol for 1 d (D) and 4 d (E).

5. Database survey

First of all it may be mentioned that beside the chain isomer of Co(NCS)₂(C₃H₆N₂S)₂ (CSD refcode ZZZFAI01; Jochim et al., 2020a ), another compound with same composition is reported in the Cambridge Structural Database [CSD Version 5.43, update of May 2026 (Groom et al., 2016 ), search with CONQUEST (Bruno et al., 2002 )] for which only unit-cell parameters are reported (ZZZFAI; Nardelli & Chierici, 1958 ). According to the entry in the CSD, this compound should consist of discrete complexes but the unit-cell parameters are very similar to the chain isomer of this compound. Moreover, it is stated that this form crystallizes in the triclinic system with Z = 1, in which space group P $[\overline{1}]$ is impossible. The same authors also reported unit-cell parameters for the corresponding Mn and Zn compounds. The unit-cell parameters for the Mn compound (ZZZEZA; Nardelli & Chierici, 1958) are also very similar to those of the chain isomer, whereas the Zn compound is isotypic to the title complex (ZZZDUE; Nardelli & Chierici, 1958). Later, Nardelli and co-workers reported the crystal structure of Ni(NCS)₂(C₃H₆N₂S)₂ (ESUNSC10; Nardelli et al., 1966 ), which consists of chains and is isotypic to the chain isomer of the corresponding Co compound. The crystal structure of the Cd compound is also published and consists of chains, but is not isotypic to the Co and Ni compounds (ETCDTH; Calvaca et al., 1960 ).

Finally, there are some compounds with Co(NCS)₂ and other thiourea derivatives as ligand reported in the CSD, including Co(NCS)₂(tetramethylthiourea)₂ (WUQTIO; Jochim et al., 2020b ), Co(NCS)₂(N,N′-dimethylthiourea)₂ (QUSZAI; Jochim et al., 2020c ) and Co(NCS)₂(1,3-dicyclohexylthiourea)₂ (LAMPUO; Krebs et al., 2022 ). All of these compounds consist of discrete complexes with a tetrahedral coordination. However, in Co(NCS)₂(thiourea)₂, the cobalt cations are linked by pairs of μ-1,3-bridging thiocyanate into chains (LEHQAS; Rajarajan et al., 2012 ).

6. Synthesis and crystallization

Cobalt thiocyanate and ethylenethiourea were purchased from Sigma-Aldrich. 87.6 mg (0.50 mmol) of Co(NCS)₂ and 102.4 mg (1.0 mmol) of ethylenethiourea were stirred in 3 ml of ethanol for 3 d. Then, 3 ml of n-heptane were added and stirred for another 10 min. The precipitate was filtered off, leading to a microcrystalline powder of the title compound. As the solvent slowly evaporated from the filtrate, blue block-shaped crystals suitable for single crystal X-ray diffraction were obtained.

The chain isomer of Co(NCS)₂(C₃H₆N₂S)₂ used for the solvent-mediated conversion experiments was prepared according to literature procedures (Jochim et al., 2020a).

The IR spectroscopic measurements were performed with an ATI Mattson Genesis Series FTIR Spectrometer, control software: WINFIRST, from ATI Mattson in ATR mode. The PXRD measurements were 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.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3.The C-bound hydrogen atoms were positioned with idealized geometry and were refined isotropically with U_iso(H) = 1.2 U_eq(C) using a riding model. The N-bound hydrogen atoms were located in difference maps, their bond lengths set to ideal values and finally they were refined isotropically with U_iso(H) = 1.2 U_eq(N) using a riding model.

Table 3
Experimental details

Crystal data
Chemical formula	[Co(NCS)₂(C₃H₆N₂S)₂]
M_r	379.41
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	170
a, b, c (Å)	7.7636 (2), 9.1388 (3), 21.9230 (5)
β (°)	96.552 (2)
V (Å³)	1545.28 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.65
Crystal size (mm)	0.18 × 0.11 × 0.08

Data collection
Diffractometer	Stoe IPDS2
Absorption correction	Numerical (X-SHAPE and X-RED 32; Stoe, 2008 )
T_min, T_max	0.638, 0.798
No. of measured, independent and observed [I > 2σ(I)] reflections	21701, 3351, 3080
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.062, 1.08
No. of reflections	3351
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.23
Computer programs: X-AREA and X-RED (Stoe, 2008), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), DIAMOND (Brandenburg, 1999 ), XP in SHELXTL-PC (Sheldrick, 2008 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2574161

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989026007383/hb8234sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989026007383/hb8234Isup2.hkl

checkCIF report

Computing details top

Bis(imidazolidine-2-thione-κS)dithiocyanatocobalt(II) top

Crystal data top

[Co(NCS)₂(C₃H₆N₂S)₂]	F(000) = 772
M_r = 379.41	D_x = 1.631 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.7636 (2) Å	Cell parameters from 8000 reflections
b = 9.1388 (3) Å	θ = 10.0–25.0°
c = 21.9230 (5) Å	µ = 1.65 mm⁻¹
β = 96.552 (2)°	T = 170 K
V = 1545.28 (7) Å³	Block, blue
Z = 4	0.18 × 0.11 × 0.08 mm

Data collection top

Stoe IPDS-2 diffractometer	3080 reflections with I > 2σ(I)
ω scans	R_int = 0.022
Absorption correction: numerical (X-Shape and X-Red 32; Stoe, 2008)	θ_max = 27.0°, θ_min = 1.9°
T_min = 0.638, T_max = 0.798	h = −9→9
21701 measured reflections	k = −11→11
3351 independent reflections	l = −28→28

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.025	H-atom parameters constrained
wR(F²) = 0.062	w = 1/[σ²(F_o²) + (0.031P)² + 0.5882P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
3351 reflections	Δρ_max = 0.30 e Å⁻³
172 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints

Special details top

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

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

	x	y	z	U_iso*/U_eq
Co1	0.21856 (3)	0.34622 (2)	0.40792 (2)	0.03252 (8)
N1	0.2712 (2)	0.27718 (18)	0.49188 (7)	0.0412 (3)
C1	0.3166 (2)	0.2152 (2)	0.53726 (8)	0.0372 (4)
S1	0.37618 (8)	0.12604 (6)	0.59973 (2)	0.05231 (14)
N2	0.1156 (2)	0.18903 (18)	0.35535 (7)	0.0413 (3)
C2	0.0766 (2)	0.08932 (19)	0.32363 (7)	0.0336 (3)
S2	0.02460 (6)	−0.05075 (5)	0.27987 (2)	0.03993 (11)
S11	0.00832 (5)	0.52604 (5)	0.39459 (2)	0.03687 (11)
C11	0.1030 (2)	0.66747 (18)	0.43786 (7)	0.0321 (3)
N11	0.0839 (2)	0.80539 (18)	0.42222 (7)	0.0437 (4)
H11	0.029316	0.832996	0.386690	0.052*
N12	0.2017 (2)	0.65511 (16)	0.49075 (7)	0.0410 (3)
H12	0.213882	0.575491	0.513402	0.049*
C12	0.2443 (3)	0.7985 (2)	0.51792 (9)	0.0440 (4)
H12A	0.369897	0.807233	0.531493	0.053*
H12B	0.178507	0.817590	0.553222	0.053*
C13	0.1886 (3)	0.9017 (2)	0.46461 (9)	0.0436 (4)
H13A	0.119347	0.984540	0.477760	0.052*
H13B	0.289889	0.940337	0.446111	0.052*
S21	0.48883 (6)	0.42711 (5)	0.38813 (2)	0.03941 (11)
C21	0.4724 (2)	0.53905 (18)	0.32552 (7)	0.0311 (3)
N21	0.60888 (19)	0.57669 (18)	0.29779 (7)	0.0393 (3)
H21	0.717127	0.559478	0.312620	0.047*
N22	0.33055 (18)	0.59910 (18)	0.29709 (7)	0.0375 (3)
H22	0.229503	0.573146	0.308204	0.045*
C22	0.3662 (2)	0.6770 (2)	0.24139 (9)	0.0457 (4)
H22A	0.311627	0.775101	0.238903	0.055*
H22B	0.325286	0.620757	0.203928	0.055*
C23	0.5628 (2)	0.6878 (3)	0.25054 (9)	0.0476 (5)
H23A	0.613416	0.664837	0.212208	0.057*
H23B	0.601404	0.786424	0.264968	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.03490 (13)	0.03183 (12)	0.03132 (12)	−0.00233 (9)	0.00588 (9)	0.00202 (8)
N1	0.0486 (9)	0.0421 (8)	0.0333 (7)	−0.0018 (7)	0.0065 (6)	0.0033 (6)
C1	0.0409 (9)	0.0361 (9)	0.0356 (9)	−0.0001 (7)	0.0084 (7)	−0.0041 (7)
S1	0.0693 (3)	0.0490 (3)	0.0373 (2)	0.0069 (2)	0.0002 (2)	0.0068 (2)
N2	0.0449 (9)	0.0403 (8)	0.0390 (8)	−0.0043 (7)	0.0061 (6)	0.0006 (7)
C2	0.0322 (8)	0.0377 (9)	0.0313 (8)	0.0002 (7)	0.0048 (6)	0.0058 (7)
S2	0.0456 (2)	0.0387 (2)	0.0345 (2)	0.00118 (18)	0.00043 (17)	−0.00220 (17)
S11	0.0325 (2)	0.0404 (2)	0.0370 (2)	0.00086 (17)	0.00088 (16)	0.00048 (17)
C11	0.0289 (8)	0.0362 (8)	0.0318 (8)	0.0033 (6)	0.0070 (6)	0.0063 (6)
N11	0.0472 (9)	0.0384 (8)	0.0429 (8)	−0.0003 (7)	−0.0057 (7)	0.0120 (7)
N12	0.0519 (9)	0.0335 (8)	0.0355 (8)	0.0029 (7)	−0.0048 (6)	0.0055 (6)
C12	0.0503 (11)	0.0363 (9)	0.0436 (10)	0.0002 (8)	−0.0031 (8)	−0.0005 (8)
C13	0.0460 (10)	0.0342 (9)	0.0498 (10)	0.0016 (8)	0.0021 (8)	0.0028 (8)
S21	0.0319 (2)	0.0459 (2)	0.0396 (2)	−0.00271 (17)	0.00027 (16)	0.01317 (18)
C21	0.0307 (8)	0.0317 (8)	0.0309 (8)	−0.0011 (6)	0.0034 (6)	−0.0025 (6)
N21	0.0280 (7)	0.0483 (9)	0.0426 (8)	0.0028 (6)	0.0085 (6)	0.0102 (7)
N22	0.0280 (7)	0.0475 (8)	0.0376 (7)	0.0007 (6)	0.0065 (6)	0.0111 (6)
C22	0.0388 (10)	0.0556 (12)	0.0437 (10)	0.0054 (8)	0.0096 (8)	0.0184 (9)
C23	0.0401 (10)	0.0595 (12)	0.0447 (10)	0.0002 (9)	0.0110 (8)	0.0180 (9)

Geometric parameters (Å, º) top

Co1—N1	1.9446 (15)	C12—H12A	0.9900
Co1—N2	1.9544 (16)	C12—H12B	0.9900
Co1—S11	2.3111 (5)	C13—H13A	0.9900
Co1—S21	2.3120 (5)	C13—H13B	0.9900
N1—C1	1.164 (2)	S21—C21	1.7050 (17)
C1—S1	1.6153 (18)	C21—N22	1.321 (2)
N2—C2	1.165 (2)	C21—N21	1.326 (2)
C2—S2	1.6228 (18)	N21—C23	1.466 (2)
S11—C11	1.7182 (18)	N21—H21	0.8800
C11—N11	1.310 (2)	N22—C22	1.467 (2)
C11—N12	1.320 (2)	N22—H22	0.8801
N11—C13	1.459 (2)	C22—C23	1.520 (3)
N11—H11	0.8800	C22—H22A	0.9900
N12—C12	1.462 (2)	C22—H22B	0.9900
N12—H12	0.8799	C23—H23A	0.9900
C12—C13	1.526 (3)	C23—H23B	0.9900

N1—Co1—N2	110.32 (7)	N11—C13—H13A	111.4
N1—Co1—S11	114.80 (5)	C12—C13—H13A	111.4
N2—Co1—S11	102.29 (5)	N11—C13—H13B	111.4
N1—Co1—S21	100.61 (5)	C12—C13—H13B	111.4
N2—Co1—S21	116.30 (5)	H13A—C13—H13B	109.3
S11—Co1—S21	113.076 (19)	C21—S21—Co1	110.89 (6)
C1—N1—Co1	167.80 (15)	N22—C21—N21	110.04 (15)
N1—C1—S1	178.59 (18)	N22—C21—S21	127.65 (13)
C2—N2—Co1	171.01 (15)	N21—C21—S21	122.30 (13)
N2—C2—S2	179.20 (17)	C21—N21—C23	111.12 (15)
C11—S11—Co1	102.33 (6)	C21—N21—H21	124.3
N11—C11—N12	110.46 (16)	C23—N21—H21	122.1
N11—C11—S11	123.40 (13)	C21—N22—C22	111.61 (14)
N12—C11—S11	126.14 (13)	C21—N22—H22	118.6
C11—N11—C13	112.06 (15)	C22—N22—H22	128.3
C11—N11—H11	122.4	N22—C22—C23	101.74 (14)
C13—N11—H11	124.6	N22—C22—H22A	111.4
C11—N12—C12	111.27 (15)	C23—C22—H22A	111.4
C11—N12—H12	125.5	N22—C22—H22B	111.4
C12—N12—H12	120.4	C23—C22—H22B	111.4
N12—C12—C13	102.19 (15)	H22A—C22—H22B	109.3
N12—C12—H12A	111.3	N21—C23—C22	102.05 (14)
C13—C12—H12A	111.3	N21—C23—H23A	111.4
N12—C12—H12B	111.3	C22—C23—H23A	111.4
C13—C12—H12B	111.3	N21—C23—H23B	111.4
H12A—C12—H12B	109.2	C22—C23—H23B	111.4
N11—C13—C12	101.73 (15)	H23A—C23—H23B	109.2

Co1—S11—C11—N11	143.67 (14)	Co1—S21—C21—N22	12.57 (18)
Co1—S11—C11—N12	−37.17 (16)	Co1—S21—C21—N21	−166.68 (13)
N12—C11—N11—C13	5.1 (2)	N22—C21—N21—C23	7.9 (2)
S11—C11—N11—C13	−175.63 (13)	S21—C21—N21—C23	−172.69 (14)
N11—C11—N12—C12	5.5 (2)	N21—C21—N22—C22	4.9 (2)
S11—C11—N12—C12	−173.74 (14)	S21—C21—N22—C22	−174.42 (14)
C11—N12—C12—C13	−12.9 (2)	C21—N22—C22—C23	−14.7 (2)
C11—N11—C13—C12	−12.6 (2)	C21—N21—C23—C22	−16.5 (2)
N12—C12—C13—N11	14.3 (2)	N22—C22—C23—N21	17.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···S2ⁱ	0.88	2.57	3.3693 (16)	152
N12—H12···S11ⁱⁱ	0.88	2.95	3.5571 (17)	128
N12—H12···S21ⁱⁱⁱ	0.88	2.97	3.4542 (15)	116
C12—H12A···S21ⁱⁱⁱ	0.99	2.91	3.4371 (19)	114
C13—H13B···S1ⁱⁱⁱ	0.99	2.95	3.816 (2)	147
N21—H21···S11^iv	0.88	2.74	3.5823 (16)	161
N22—H22···S2^v	0.88	2.83	3.3560 (16)	120
N22—H22···S11	0.88	2.73	3.5346 (15)	152
C22—H22A···S2ⁱ	0.99	2.96	3.800 (2)	143

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

Acknowledgements

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

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