research communications
κS)bis(thiocyanato-κN)cobalt(II)
of bis(tetramethylthiourea-aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth Str. 2, D-24118 Kiel, Germany
*Correspondence e-mail: ajochim@ac.uni-kiel.de
In the course of systematic investigations on the synthesis of Co(NCS)2 coordination compounds with different thiourea ligands, the title compound, [Co(NCS)2(C5H12N2S)2], was obtained. In this compound the CoII cations are coordinated by two crystallographically independent N-bonded thiocyanate anions and two tetramethylthiourea ligands into discrete complexes that are located in general positions and show a strongly distorted tetrahedral geometry. Intermolecular C—H⋯S hydrogen bonds of different strength can be observed between the discrete complexes, which are connected by pairs of hydrogen bonds into zigzag-like chains that elongate in the b-axis direction. These chains are additionally linked by strong C—H⋯S hydrogen bonds along the a-axis direction, resulting in the formation of layers that are parallel to the ab plane. There is also one weak intramolecular C—H⋯S hydrogen bond between two neighbouring thiourea ligands within the complexes. Comparison of the experimental PXRD pattern with that calculated from the single-crystal data prove that a pure phase has been obtained. Thermoanalytical investigations reveal that this compound melts at 364 K and decomposes upon further heating.
Keywords: crystal structure; cobalt thiocyanate; tetramethylthiourea; discrete complexes; thermal properties.
CCDC reference: 2018676
1. Chemical context
The thiocyanate anion is a very versatile ligand, which can coordinate in many different ways to metal cations, leading to compounds with a variety of coordination networks (Buckingham, 1994; Haasnoot et al., 1984; Barnett et al., 2002; Bhowmik et al., 2010; Abedi et al., 2016). This ligand is also able to mediate reasonable magnetic exchange (Palion-Gazda et al., 2015), which is one reason why we have been interested in transition-metal thiocyanate coordination compounds for many years. In this context, we are especially interested in compounds of the general composition [M(NCS)2(L)2]n, in which paramagnetic first-row transition-metal cations M such as MnII, FeII, CoII or NiII are octahedrally coordinated by two N- and two S-bonding thiocyanate anions and two coligands L that usually consist of pyridine derivatives. Depending on the nature of the coligand, the metal cations are connected into chains by pairs of μ-1,3 coordinating anionic ligands (Mautner et al., 2018; Prananto et al., 2017; Shurdha et al., 2013; Jin et al., 2007; Böhme et al., 2020), or they are linked into layers with different layer topologies (Werner et al., 2015a; Neumann et al., 2018a; Suckert et al., 2016). The chain compounds show either ferromagnetism (Neumann et al., 2019), antiferromagnetism (Jochim et al., 2020) or they represent antiferromagnetic phases of single-chain magnets (Mautner et al., 2018; Rams et al., 2017, 2020; Werner et al., 2015b), whereas the layer compounds are in most cases (Suckert et al., 2016). For this composition a third structure type is known, in which the metal cations are tetrahedrally coordinated, forming discrete complexes with only N-terminally bonded thiocyanate anions (Neumann et al., 2018b). For some coligands, at least two of the three isomers can be obtained. With 4-acetylpyridine as coligand, for example, the chain as well as the layer isomer can be prepared, with the latter representing the thermodynamically stable form at room temperature (Werner et al., 2015a). If 4-methoxypyridine is used as coligand, the chain isomer as well as the tetrahedral discrete complex can be obtained, and in this case the chain compound is thermodynamically stable at room temperature (Mautner et al., 2018; Rams et al., 2020). Finally, different polymorphic modifications can also be obtained for discrete complexes (Neumann et al., 2018b).
However, in all previous work we exclusively used N-donor coligands for the synthesis of Co(NCS)2 thiocyanate coordination polymers, and to investigate the influence of the coligand on the structure and the magnetic behaviour, we became interested in donor ligands that can coordinate via a sulfur atom, including thiourea derivatives. With thiourea, the of one Co(NCS)2 coordination compound has already been already reported, and in this case the Co cations are linked by pairs of thiourea sulfur atoms, whereas the thiocyanate anions are only terminally N-bonded (Rajarajan et al., 2012). Independent of this, we used ethylenethiourea as coligand and obtained a compound with the composition [Co(NCS)2(ethylenethiourea)2]n. Single-crystal proves that, in this case, the CoII cations are connected by pairs of thiocyanate ligands into chains, which corresponds exactly to the desired structure (Jochim et al., 2020). In contrast to the analogous compounds with N-donor coligands, this compound shows antiferromagnetic ordering but no relaxations of single chains. To investigate this in more detail, we used tetramethylthiourea as coligand and obtained crystals of the title compound Co(NCS)2(tetramethylthiourea)2. Surprisingly, this compound consists of discrete complexes, in which the CoII cations are tetrahedrally coordinated, which is also reflected in its IR spectra, where the C—N stretching vibration of the thiocyanate anion is observed at 2048 cm−1 (see Fig. S1 in the supporting information). The powder diffraction pattern reveals that a pure product has been obtained (Fig. S2). The thermogravimetric (TG) curve shows that all tetramethylthiourea ligands are emitted in one step (theoretical mass loss: 60.2%), which is accompanied by an exothermic peak in the differential thermoanalysis (DTA) curve (Fig. S3). However, two endothermic peaks are observed at low temperatures where the sample mass does not change. To investigate this phenomenon in more detail, measurements using (DSC) were performed, which prove that the first endothermic signal is reversible with some hysteresis, pointing to some (Fig. S4), which could explain why no changes in the PXRD pattern are observed after cooling. The second endothermic peak is irreversible, but thermomicroscopic measurements prove that this event corresponds to melting, which means that upon cooling no crystallization is observed (Figs. S5 and S6).
2. Structural commentary
The II cation in general positions (Fig. 1). The CoII cations are coordinated by two N-bonded thiocyanate anions and two tetramethylthiourea molecules into discrete complexes, with bonds lengths and angles similar to those reported in the literature (Table 1). The coordination polyhedra around the CoII cations can be described as strongly distorted tetrahedra (Table 1), which is also obvious from the tetrahedral angle variance σθ〈tet〉2 = 81.0 and the mean tetrahedral quadratic elongation 〈λtet〉 = 1.036 (Robinson et al., 1971). The C—N bond lengths between the thioketone C and the amino groups are significantly shorter than those between the amino groups and the methyl C atoms, which points to some degree of double-bond character of the former. This is expected as thioketones are subject to thioketone–enthiole similar to the found for regular which is also supported by the fact that the CNMe2 groups are planar with angles close to 120° (Devillanova, 2007). The NMe2 groups of the same coligand are twisted against each other with angles of 45.74 (9) and 46.32 (8)° for the two crystallographically independent tetramethylthiourea coligands.
of the title compound contains two crystallographically independent tetramethylthiourea molecules, two thiocyanate anions and one Co
|
3. Supramolecular features
As can be seen in Table 2, two sets of hydrogen bonds can be found for which the D—H⋯A angles are either relatively near to 180° (174.0 and 166.2°) or far from 180° (142.8 and 140.8°), which is indicative for strong or relatively weak hydrogen bonds, respectively. Although nearly all of these hydrogen bonds are intermolecular bonds between the thiocyanate sulfur and a C—H hydrogen atom from an adjacent complex, in one case relatively weak intramolecular hydrogen C—H⋯S bonding between two different tetramethylthiourea molecules of the same discrete complex is found. Each complex is connected to two different neighbouring complexes by pairs of C—H⋯SNCS hydrogen bonds between the tetramethylthiourea coligands and the thiocyanate anions. This leads to the formation of zigzag-like chains along the b-axis direction (Fig. 2), which are further connected by additional single C—H⋯SNCS hydrogen bonds into layers that are parallel to the ab plane (Fig. 3). These layers are stacked along the c-axis direction with no pronounced intermolecular interactions between them (Fig. 4).
4. Database survey
In the Cambridge Structural Database (Version 5.41, last update November 2019; Groom et al., 2016) only 72 compounds containing transition-metal cations and tetramethylthiourea are reported, but none of them contains thiocyanate anions. This search also reveals that no tetrahedral Co(NCS)2 compounds with other thiourea derivatives are known, but one chain compound with the composition [Co(NCS)2(thiourea)2]n has been reported (Rajarajan et al., 2012). However, several structures built up of discrete tetrahedral complexes with cobalt thiocyanate and a variety of N-containing ligands are reported in the CCDC. These include, for example, bis(3-methylpyridine)diisothiocyanatocobalt(II) (Böckmann et al. 2011) and bis(quinoline)diisothiocyanatocobalt(II) (Mirčeva & Golič, 1990). It is noted that, in several cases, pyridine or imidazole derivatives are used that have large substituents adjacent to the coordinating N atoms, which might enforce the formation of a tetrahedral complex for steric reasons.
5. Synthesis and crystallization
General
Co(NCS)2 and tetramethylthiourea were purchased from Sigma Aldrich and were used without further purification.
Synthesis
A suspension of Co(NCS)2 (0.50 mmol, 87.5 mg) and tetramethylthiourea (1.00 mmol, 132.23 mg) in 0.75 mL water was stored at 281 K. After a few days, deep-blue-coloured crystals were obtained, which were filtered off, and ground into powder or used for single-crystal It is noted that no crystalline product could be obtained from an analogous reaction at room temperature. Elemental analysis calculated for C12H24N6CoS4 (439.56 g mol−1) C 32.79, H 5.50, N 19.12%, S 29.18, found: C 32.37, H 5.38, N 18.75, S 28.64.
Experimental details
Elemental analysis was performed using an EURO EA elemental analyser 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 a hot-stage FP82 from Mettler and a BX60 microscope from Olympus, using the software analysis package from Mettler.
6. Refinement
Crystal data, data collection and structure . All non-hydrogen atoms were refined anisotropically. The C—H atoms were positioned with idealized geometry (allowed to rotate but not to tip) and refined isotropically with Uiso(H) = 1.5Ueq(C).
details are summarized in Table 3Supporting information
CCDC reference: 2018676
https://doi.org/10.1107/S205698902001021X/tx2029sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902001021X/tx2029Isup2.hkl
Figure S1. IR spectrum of the title compound. DOI: https://doi.org/10.1107/S205698902001021X/tx2029sup3.tif
Figure S2. Experimental (top) and calculated (bottom) PXRD pattern of the title compound measured with Cu-radiation. DOI: https://doi.org/10.1107/S205698902001021X/tx2029sup4.tif
Figure S3. DTG, TG and DTA curve of the title compound measured at a rate of 4 degrees C/min. in a nitrogen atmosphere. DOI: https://doi.org/10.1107/S205698902001021X/tx2029sup5.tif
Figure S4. DSC heating and cooling curve of the title compound until the first endothermic event using a heating rate of 4 degrees C/min. under nitrogen atmosphere. DOI: https://doi.org/10.1107/S205698902001021X/tx2029sup6.tif
Figure S5. DSC heating and cooling curve of the title compound until the second endothermic event using a heating rate of 4 degrees C/min. under nitrogen atmosphere. DOI: https://doi.org/10.1107/S205698902001021X/tx2029sup7.tif
Figure S6. Thermomicroscopic images of the title compound at different temperatures when heated in air with 10 degrees C/min. DOI: https://doi.org/10.1107/S205698902001021X/tx2029sup8.tif
Data collection: X-AREA (Stoe & Cie, 2002); cell
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).[Co(NCS)2(C5H12N2S)2] | F(000) = 916 |
Mr = 439.54 | Dx = 1.422 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.3288 (13) Å | Cell parameters from 14562 reflections |
b = 11.2140 (8) Å | θ = 2.4–27.0° |
c = 13.8579 (13) Å | µ = 1.25 mm−1 |
β = 97.667 (8)° | T = 200 K |
V = 2052.8 (3) Å3 | Block, blue |
Z = 4 | 0.19 × 0.15 × 0.10 mm |
Stoe IPDS-2 diffractometer | 3826 reflections with I > 2σ(I) |
ω scans | Rint = 0.044 |
Absorption correction: numerical (X-Red and X-Shape; Stoe & Cie, 2002) | θmax = 27.0°, θmin = 2.4° |
Tmin = 0.644, Tmax = 0.805 | h = −15→16 |
14562 measured reflections | k = −13→14 |
4409 independent reflections | l = −17→17 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.031 | w = 1/[σ2(Fo2) + (0.0593P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.084 | (Δ/σ)max = 0.001 |
S = 1.02 | Δρmax = 0.33 e Å−3 |
4409 reflections | Δρmin = −0.39 e Å−3 |
217 parameters | Extinction correction: SHELXL2018/3 (Sheldrick 2018), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0092 (16) |
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. |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.31466 (2) | 0.44406 (2) | 0.18631 (2) | 0.03623 (10) | |
N1 | 0.26892 (14) | 0.28853 (15) | 0.13540 (11) | 0.0473 (4) | |
C1 | 0.22426 (14) | 0.20050 (17) | 0.11758 (12) | 0.0400 (4) | |
S1 | 0.16309 (4) | 0.07801 (5) | 0.09170 (4) | 0.05239 (14) | |
N2 | 0.23001 (14) | 0.56237 (15) | 0.11124 (12) | 0.0476 (4) | |
C2 | 0.18324 (14) | 0.63196 (16) | 0.06226 (12) | 0.0389 (4) | |
S2 | 0.11944 (5) | 0.73069 (6) | −0.00388 (4) | 0.05992 (16) | |
S11 | 0.31339 (4) | 0.42243 (5) | 0.35233 (3) | 0.04323 (13) | |
C11 | 0.20254 (13) | 0.33900 (15) | 0.34598 (11) | 0.0346 (3) | |
N11 | 0.11381 (12) | 0.39071 (14) | 0.31533 (11) | 0.0410 (3) | |
C12 | 0.09967 (18) | 0.51955 (19) | 0.32179 (17) | 0.0551 (5) | |
H12A | 0.150522 | 0.552429 | 0.372410 | 0.083* | |
H12B | 0.031805 | 0.536217 | 0.338259 | 0.083* | |
H12C | 0.107221 | 0.556414 | 0.259049 | 0.083* | |
C13 | 0.02995 (16) | 0.3274 (2) | 0.25917 (16) | 0.0580 (5) | |
H13A | 0.053452 | 0.249499 | 0.239227 | 0.087* | |
H13B | 0.004558 | 0.374051 | 0.201245 | 0.087* | |
H13C | −0.024519 | 0.316034 | 0.299316 | 0.087* | |
N12 | 0.20637 (12) | 0.22456 (14) | 0.37071 (10) | 0.0392 (3) | |
C14 | 0.12200 (18) | 0.1612 (2) | 0.40544 (16) | 0.0538 (5) | |
H14A | 0.071235 | 0.218979 | 0.420747 | 0.081* | |
H14B | 0.147061 | 0.115724 | 0.464096 | 0.081* | |
H14C | 0.091237 | 0.106630 | 0.354706 | 0.081* | |
C15 | 0.29981 (18) | 0.1561 (2) | 0.37811 (16) | 0.0561 (5) | |
H15A | 0.345116 | 0.191657 | 0.335874 | 0.084* | |
H15B | 0.284447 | 0.073696 | 0.357751 | 0.084* | |
H15C | 0.332793 | 0.156901 | 0.445679 | 0.084* | |
S21 | 0.47009 (4) | 0.51223 (5) | 0.15128 (3) | 0.04435 (13) | |
C21 | 0.56218 (13) | 0.43472 (14) | 0.22564 (11) | 0.0333 (3) | |
N21 | 0.57661 (12) | 0.45344 (13) | 0.32191 (10) | 0.0369 (3) | |
C22 | 0.54437 (16) | 0.56303 (18) | 0.36544 (14) | 0.0463 (4) | |
H22A | 0.540529 | 0.627600 | 0.317434 | 0.069* | |
H22B | 0.593316 | 0.584178 | 0.422032 | 0.069* | |
H22C | 0.477595 | 0.550936 | 0.386096 | 0.069* | |
C23 | 0.60727 (17) | 0.3590 (2) | 0.39199 (12) | 0.0507 (5) | |
H23A | 0.610361 | 0.283021 | 0.357553 | 0.076* | |
H23B | 0.557930 | 0.352888 | 0.438242 | 0.076* | |
H23C | 0.674128 | 0.377561 | 0.427288 | 0.076* | |
N22 | 0.62202 (12) | 0.35804 (13) | 0.18656 (9) | 0.0384 (3) | |
C24 | 0.72499 (16) | 0.3301 (2) | 0.23060 (14) | 0.0509 (5) | |
H24A | 0.745874 | 0.386147 | 0.283738 | 0.076* | |
H24B | 0.771017 | 0.336746 | 0.181307 | 0.076* | |
H24C | 0.727201 | 0.248577 | 0.256314 | 0.076* | |
C25 | 0.59760 (19) | 0.3148 (2) | 0.08646 (13) | 0.0536 (5) | |
H25A | 0.523941 | 0.309911 | 0.069608 | 0.080* | |
H25B | 0.627351 | 0.235605 | 0.080900 | 0.080* | |
H25C | 0.625178 | 0.370024 | 0.041890 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.03421 (15) | 0.03936 (14) | 0.03465 (14) | 0.00045 (9) | 0.00284 (9) | 0.00153 (8) |
N1 | 0.0544 (10) | 0.0439 (9) | 0.0433 (8) | −0.0005 (7) | 0.0056 (7) | −0.0033 (6) |
C1 | 0.0435 (10) | 0.0433 (9) | 0.0341 (8) | 0.0064 (8) | 0.0078 (7) | 0.0016 (6) |
S1 | 0.0532 (3) | 0.0467 (3) | 0.0576 (3) | −0.0074 (2) | 0.0087 (2) | −0.0008 (2) |
N2 | 0.0442 (9) | 0.0477 (9) | 0.0489 (9) | 0.0033 (7) | −0.0017 (7) | 0.0035 (7) |
C2 | 0.0350 (9) | 0.0444 (9) | 0.0374 (8) | −0.0011 (7) | 0.0049 (6) | −0.0005 (7) |
S2 | 0.0516 (3) | 0.0689 (4) | 0.0587 (3) | 0.0139 (3) | 0.0055 (2) | 0.0237 (3) |
S11 | 0.0358 (3) | 0.0584 (3) | 0.0352 (2) | −0.00976 (19) | 0.00353 (16) | −0.00086 (17) |
C11 | 0.0327 (8) | 0.0426 (8) | 0.0288 (6) | 0.0009 (7) | 0.0053 (6) | −0.0055 (6) |
N11 | 0.0335 (8) | 0.0444 (8) | 0.0446 (7) | 0.0057 (6) | 0.0036 (6) | −0.0023 (6) |
C12 | 0.0537 (13) | 0.0477 (11) | 0.0659 (12) | 0.0154 (9) | 0.0155 (10) | 0.0021 (9) |
C13 | 0.0371 (11) | 0.0755 (15) | 0.0574 (11) | 0.0002 (10) | −0.0080 (8) | −0.0021 (10) |
N12 | 0.0382 (8) | 0.0401 (8) | 0.0395 (7) | 0.0033 (6) | 0.0056 (6) | −0.0009 (6) |
C14 | 0.0545 (13) | 0.0496 (11) | 0.0571 (11) | −0.0128 (9) | 0.0068 (9) | 0.0030 (9) |
C15 | 0.0566 (13) | 0.0549 (12) | 0.0573 (11) | 0.0209 (10) | 0.0096 (9) | 0.0043 (9) |
S21 | 0.0363 (3) | 0.0573 (3) | 0.0390 (2) | −0.00071 (19) | 0.00352 (16) | 0.01763 (18) |
C21 | 0.0341 (9) | 0.0352 (8) | 0.0307 (7) | −0.0069 (6) | 0.0048 (6) | 0.0035 (6) |
N21 | 0.0404 (8) | 0.0407 (7) | 0.0295 (6) | 0.0014 (6) | 0.0049 (5) | 0.0007 (5) |
C22 | 0.0430 (11) | 0.0498 (10) | 0.0477 (9) | −0.0052 (8) | 0.0118 (8) | −0.0134 (8) |
C23 | 0.0588 (13) | 0.0611 (12) | 0.0320 (8) | 0.0063 (10) | 0.0048 (7) | 0.0106 (8) |
N22 | 0.0468 (9) | 0.0381 (7) | 0.0303 (6) | −0.0006 (6) | 0.0055 (5) | −0.0012 (5) |
C24 | 0.0517 (12) | 0.0556 (11) | 0.0458 (9) | 0.0138 (9) | 0.0083 (8) | 0.0007 (8) |
C25 | 0.0690 (14) | 0.0571 (11) | 0.0355 (9) | −0.0105 (10) | 0.0107 (8) | −0.0100 (8) |
Co1—N1 | 1.9484 (17) | N11—C13 | 1.459 (3) |
Co1—N2 | 1.9499 (17) | N11—C12 | 1.461 (3) |
Co1—S11 | 2.3157 (5) | N12—C15 | 1.455 (3) |
Co1—S21 | 2.3196 (6) | N12—C14 | 1.465 (3) |
N1—C1 | 1.162 (3) | S21—C21 | 1.7282 (17) |
C1—S1 | 1.613 (2) | C21—N22 | 1.336 (2) |
N2—C2 | 1.160 (2) | C21—N21 | 1.339 (2) |
C2—S2 | 1.6066 (18) | N21—C23 | 1.458 (2) |
S11—C11 | 1.7411 (18) | N21—C22 | 1.459 (2) |
C11—N12 | 1.327 (2) | N22—C24 | 1.460 (3) |
C11—N11 | 1.335 (2) | N22—C25 | 1.464 (2) |
N1—Co1—N2 | 106.56 (7) | C11—N11—C12 | 121.74 (17) |
N1—Co1—S11 | 102.86 (5) | C13—N11—C12 | 114.72 (17) |
N2—Co1—S11 | 121.40 (5) | C11—N12—C15 | 122.09 (17) |
N1—Co1—S21 | 117.66 (5) | C11—N12—C14 | 123.28 (16) |
N2—Co1—S21 | 97.67 (6) | C15—N12—C14 | 114.12 (17) |
S11—Co1—S21 | 111.564 (19) | C21—S21—Co1 | 107.02 (6) |
C1—N1—Co1 | 164.57 (16) | N22—C21—N21 | 119.39 (15) |
N1—C1—S1 | 179.27 (18) | N22—C21—S21 | 119.81 (12) |
C2—N2—Co1 | 175.96 (17) | N21—C21—S21 | 120.76 (13) |
N2—C2—S2 | 178.70 (18) | C21—N21—C23 | 122.68 (15) |
C11—S11—Co1 | 97.16 (5) | C21—N21—C22 | 122.21 (15) |
N12—C11—N11 | 120.27 (16) | C23—N21—C22 | 114.11 (15) |
N12—C11—S11 | 120.22 (13) | C21—N22—C24 | 123.21 (14) |
N11—C11—S11 | 119.51 (14) | C21—N22—C25 | 121.86 (16) |
C11—N11—C13 | 122.80 (17) | C24—N22—C25 | 113.75 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12B···S1i | 0.98 | 2.93 | 3.906 (2) | 174 |
C14—H14A···S2ii | 0.98 | 2.93 | 3.741 (2) | 141 |
C22—H22C···S11 | 0.98 | 2.61 | 3.442 (2) | 143 |
C24—H24A···S1iii | 0.98 | 2.92 | 3.878 (2) | 166 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) −x+1, y+1/2, −z+1/2. |
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.
References
Abedi, M., Kirschbaum, K., Shamkhali, A. N., Brue, C. R. & Khandar, A. A. (2016). Polyhedron, 109, 176–181. CSD CrossRef CAS Google Scholar
Barnett, S. A., Blake, A. J., Champness, N. R. & Wilson, C. (2002). Chem. Commun. pp. 1640–1641. CSD CrossRef Google Scholar
Bhowmik, P., Chattopadhyay, S., Drew, M. G. B., Diaz, C. & Ghosh, A. (2010). Polyhedron, 29, 2637–2642. CSD CrossRef CAS Google Scholar
Böckmann, J., Reimer, B. & Näther, C. (2011). Z. Naturforsch. B: Chem. Sci. 66, 819–827. Google Scholar
Böhme, M., Jochim, A., Rams, M., Lohmiller, T., Suckert, S., Schnegg, A., Plass, W. & Näther, C. (2020). Inorg. Chem. 59, 5325–5338. PubMed Google Scholar
Brandenburg, K. & Putz, H. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Buckingham, S. (1994). Coord. Chem. Rev. 135–136, 587–621. CrossRef Google Scholar
Devillanova, F. A. (2007). Editor. Handbook of Chalcogen Chemistry: New Perspectives in Sulfur, Selenium and Tellurium, 1st ed., pp. 107–108. Cambridge: Royal Society of Chemistry. 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
Haasnoot, J. G., Driessen, W. L. & Reedijk, J. (1984). Inorg. Chem. 23, 2803–2807. CSD CrossRef CAS Web of Science Google Scholar
Jin, Y., Che, Y. X. & Zheng, J. M. (2007). J. Coord. Chem. 60, 2067–2074. CSD CrossRef CAS Google Scholar
Jochim, A., Lohmiller, T., Rams, M., Böhme, M., Ceglarska, M., Schnegg, A., Plass, W. & Näther, C. (2020). Inorg. Chem. 59, 8971–8982. CSD CrossRef CAS PubMed Google Scholar
Mautner, F. A., Traber, M., Fischer, R. C., Torvisco, A., Reichmann, K., Speed, S., Vicente, R. & Massoud, S. S. (2018). Polyhedron, 154, 436–442. Web of Science CSD CrossRef CAS Google Scholar
Mirčeva, A. & Golič, L. (1990). Acta Cryst. C46, 1001–1003. CSD CrossRef Web of Science IUCr Journals Google Scholar
Neumann, T., Jess, I., Pielnhofer, F. & Näther, C. (2018b). Eur. J. Inorg. Chem. pp. 4972–4981. CSD CrossRef Google Scholar
Neumann, T., Rams, M., Tomkowicz, Z., Jess, I. & Näther, C. (2019). Chem. Commun. 55, 2652–2655. Web of Science CSD CrossRef CAS Google Scholar
Neumann, T., Rams, M., Wellm, C. & Näther, C. (2018a). Cryst. Growth Des. 18, 6020–6027. Web of Science CrossRef CAS Google Scholar
Palion-Gazda, J., Machura, B., Lloret, F. & Julve, M. (2015). Inorg. Chem. 56, 2380–2388. Google Scholar
Prananto, Y. P., Urbatsch, A., Moubaraki, B., Murray, K. S., Turner, D. R., Deacon, G. B. & Batten, S. R. (2017). Aust. J. Chem. 70, 516–528. Web of Science CSD CrossRef CAS Google Scholar
Rajarajan, K., Sendil Kumar, K., Ramesh, V., Shihabuddeen, V. & Murugavel, S. (2012). Acta Cryst. E68, m1125–m1126. CSD CrossRef IUCr Journals 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. CSD CrossRef CAS PubMed Google Scholar
Rams, M., Tomkowicz, Z., Böhme, M., Plass, W., Suckert, S., Werner, J., Jess, I. & Näther, C. (2017). Phys. Chem. Chem. Phys. 19, 3232–3243. Web of Science CSD CrossRef CAS PubMed Google Scholar
Robinson, K., Gibbs, G. V. & Ribbe, P. H. (1971). Science, 172, 567–570. CrossRef PubMed CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shurdha, E., Moore, C. E., Rheingold, A. L., Lapidus, S. H., Stephens, P. W., Arif, A. M. & Miller, J. S. (2013). Inorg. Chem. 52, 10583–10594. Web of Science CSD CrossRef CAS PubMed Google Scholar
Stoe & Cie (2002). X-AREA, X-RED and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Suckert, S., Rams, M., Böhme, M., Germann, L. S., Dinnebier, R., Plass, W., Werner, J. & Näther, C. (2016). Dalton Trans. 45, 18190–18201. CSD CrossRef CAS PubMed Google Scholar
Werner, J., Rams, M., Tomkowicz, Z., Runčevski, T., Dinnebier, R. E., Suckert, S. & Näther, C. (2015a). Inorg. Chem. 54, 2893–2901. Web of Science CSD CrossRef CAS PubMed Google Scholar
Werner, S., Tomkowicz, Z., Rams, M., Ebbinghaus, S. G., Neumann, T. & Näther, C. (2015b). Dalton Trans. 44, 14149–14158. 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
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.