Synthesis, crystal structure and properties of catena-poly[[[bis­(3-methyl­pyridine-κN)nickel(II)]-di-μ-1,3-thio­cyanato] aceto­nitrile monosolvate]

Näther, C.; Jess, I.; Krebs, C.

doi:10.1107/S2056989022009598

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ISSN: 2056-9890

Volume 78| Part 11| November 2022| Pages 1097-1102

https://doi.org/10.1107/S2056989022009598

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Synthesis, crystal structure and properties of catena-poly[[[bis(3-methylpyridine-κN)nickel(II)]-di-μ-1,3-thiocyanato] acetonitrile monosolvate]

Christian Näther,^a ^* Inke Jess ^a and Christoph Krebs ^a

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

Edited by J. Reibenspies, Texas A & M University, USA (Received 7 September 2022; accepted 29 September 2022; online 6 October 2022)

In the crystal structure of the title compound, {[Ni(NCS)₂(C₆H₇N)₂]·CH₃CN}_n, the Ni^II cation is octahedrally coordinated by two N-bonding and two S-bonding thiocyanate anions, as well as two 3-methylpyridine coligands, with the thiocyanate S atoms and the 3-methylpyridine N atoms in cis-positions. The metal cations are linked by pairs of thiocyanate anions into chains that, because of the cis–cis–trans coordination, are corrugated. These chains are arranged in such a way that channels are formed in which disordered acetonitrile solvate molecules are located. This overall structural motif is very similar to that observed in Ni(NCS)₂[4-(boc-amino)pyridine]₂·CH₃CN reported in the literature. At room temperature, the title compound loses its solvent molecules within a few hours, leading to a crystalline phase that is structurally related to that of the pristine material. If the ansolvate is stored in an acetonitrile atmosphere, the solvate is formed again. Single-crystal X-ray analysis at room-temperature proves that the crystals decompose immediately, presumably because of the loss of solvent molecules, and from the reciprocal space plots it is obvious that this reaction, in contrast to that in Ni(NCS)₂[4-(boc-amino)pyridine]₂·CH₃CN, does not proceed via a topotactic reaction.

Keywords: crystal structure; solvate; nickel thiocyanate; solvent removal.

CCDC reference: 2210399

1. Chemical context

Over the past several years, we and others have been interested in the synthesis and crystal structures of coordination polymers based on transition-metal cations and thiocyanate anions. For this anionic ligand, two major coordination modes are known, which include terminal coordination and the μ-1,3-bridging mode. The latter mode is of special interest if magnetic coordination polymers are to be prepared, because thiocyanate anions can mediate reasonable magnetic exchange (Palion-Gazda et al., 2015 ; Mekuimemba et al., 2018 ; Böhme & Plass, 2019 ; Rams et al., 2020 ). In the majority of such compounds, the metal cations are octahedrally coordinated by each of two trans thiocyanate S and N atoms as well as two N atoms of neutral coligands that mostly consist of pyridine derivatives. The metal cations are linked by pairs of anionic ligands into chains that, because of the all-trans coordination, are linear (Shurdha et al., 2013 ; Prananto et al., 2017 ; Mautner, Traber et al., 2018 ; Jochim et al., 2020a ,b ).

For octahedrally coordinated metal cations, however, five different isomers exist, which include the all-trans, all-cis and three cis–cis–trans coordinations. For compounds based on thiocyanate anions, the all-trans coordination is the most common, the all-cis coordination is unknown and the cis–cis–trans-coordination is very rare. It is noted that the latter coordination leads to the formation of linear chains if the coligands are in the trans-position (Werner et al., 2014 , 2015a ,b ), whereas corrugated chains are observed if they are in the cis-position (Böhme et al., 2020 ; Suckert et al., 2017 ).

In this context, we have reported on a compound with the composition Ni(NCS)₂[4-(boc-amino)pyridine]₂·CH₃CN in which the Ni^II cations are octahedrally coordinated by four μ-1,3-bridging thiocyanate anions as well as two 4-(boc-amino)pyridine ligands (Suckert et al., 2017). The coligands and the S-bonding thiocyanate anions are in cis-positions, whereas the two N-bonding anionic ligands are trans, leading to the formation of corrugated chains (Fig. 1: top). These chains are interconnected by strong N—H⋯O hydrogen bonding into layers that are packed in such a way that channels are formed in which disordered acetonitrile solvate molecules are located (Fig. 1: bottom). The acetonitrile molecules can be removed under vacuum and reincorporated via the gas phase without any loss in crystallinity. More importantly, single-crystal structure analysis of one crystal showed that the solvent removal is accompanied by a change in symmetry from primitive to C-centered. If this crystal is stored in an acetonitrile atmosphere, the solvent is reincorporated and the reflections violating the C-centering are observed again. Images of reciprocal space at different acetonitrile contents look like that of a single crystal, but the mosaic spread increases during formation of the ansolvate and reformation of the solvate, which proves that these reactions proceed via a topotactic reaction (Suckert et al., 2017).

Figure 1
Crystal structure of dithiocyanatobis[4-(boc-amino)pyridine]nickel(II) acetonitrile solvate retrieved from the literature showing a view of the chains with intermolecular N—H⋯O hydrogen bonding indicated by dashed lines (top) and with a view along the crystallographic c-axis (bottom).

In the course of our systematic work we became interested in Ni(NCS)₂ compounds based on 3-methylpyridine (3-picoline) as coligand. Many compounds have been reported with this ligand, but with nickel only discrete complexes with a terminal coordination are known and most of these compounds consist of solvates (see Database survey). An Ni(NCS)₂ compound with 3-methylpyridine that shows a bridging coordination of the anionic ligands does not exist.

However, in the course of our systematic investigations we accidentally obtained crystals of a further crystalline phase with the composition Ni(NCS)₂(3-methylpyridine)₂·acetonitrile. Single-crystal structure analysis shows that a network has formed, which is very similar to that observed in Ni(NCS)₂[4-(boc-amino)pyridine]₂·acetonitrile mentioned above. That both compounds are structurally related is already obvious from their similar unit-cell parameters, but also from the crystal symmetry (see Structural commentary). X-ray powder diffraction proves the formation of a pure crystalline phase (Fig. S1 in the supporting information). In the IR spectrum, the CN-stretching vibration of the thiocyanate anion is observed at 2109 cm⁻¹, in agreement with the presence of μ-1,3-bridging thiocyanate anions and that of the acetonitrile solvate molecules at 2164 cm⁻¹, proving the presence of acetonitrile (Fig. S2). In view of these results, we investigated whether the acetonitrile solvate molecules can be removed from the title compound and if this proceeds via a topotactic reaction as observed in Ni(NCS)₂[4-(boc-amino)pyridine]₂·CH₃CN mentioned above (Suckert et al., 2017). Experiments using X-ray powder diffraction show that the crystals have already decomposed at room temperature because of the loss of the solvate molecules, leading to the formation of a crystalline phase. The IR spectrum is very similar to that of the pristine phase but the CN-stretching vibration of the acetonitrile ligands have disappeared, proving that the ansolvate has formed (Fig. S3). The X-ray powder pattern of the ansolvate obtained by storing the title compound for 24 h at room temperature is very similar to that of the pristine material, which indicates that both structures must be strongly related (Fig. S4). In particular, the first three intense reflections are shifted to higher Bragg angles, which is in agreement with a decrease of the unit-cell volume. If the ansolvate is stored for 3 d in a desiccator in an acetonitrile atmosphere, the powder pattern is identical to that calculated for the title compound, which proves that this process is reversible. We also tried to determine the crystal structure of the title compound at room temperature, but during the measurement the crystal started to decompose and no reasonable data were obtained. However, the lattice parameters were determined from indexing the reflections and used for the calculation of the powder patterns. Moreover, from the reciprocal space plots of this data set, it is obvious that the mosaic spread strongly increases, which would be in agreement with a topotactic reaction, but the diffraction pattern does not look like that of a single crystal, as was the case for Ni(NCS)₂[4-(boc-amino)pyridine]₂·CH₃CN mentioned above (Suckert et al., 2017).

2. Structural commentary

The asymmetric unit of the title compound consists of one Ni^II cation, two thiocyanate anions, two 3-methylpyridine ligands and one acetonitrile molecule, all of them located in general positions (Fig. 2). The Ni cations are octahedrally coordinated by two 3-methylpyridine coligands and two N- as well two S-bonding thiocyanate anions in a cis–cis–trans coordination with the thiocyanate S atoms and the 3-methylpyridine N atoms in cis-positions. The Ni—N and Ni—S bond lengths correspond to those in similar compounds (Table 1). From the bonding angles, it is obvious that the octahedra are slightly distorted (Table 1). This is also obvious from the values of the octahedral angle variance and the mean octahedral quadratic elongation calculated by the method of Robinson et al. (1971 ), which amount to 12.7996 and 1.0190.

Table 1
Selected geometric parameters (Å, °)

Ni1—N1	2.0285 (11)	Ni1—S1ⁱⁱ	2.5508 (4)
Ni1—N1ⁱ	2.0286 (11)	Ni1—N11	2.0836 (11)

N1—Ni1—N1ⁱ	175.54 (6)	S1ⁱⁱⁱ—Ni1—S1ⁱⁱ	87.022 (18)
N1—Ni1—S1ⁱⁱ	83.43 (3)	N11—Ni1—S1ⁱⁱⁱ	173.74 (3)
N1—Ni1—S1ⁱⁱⁱ	93.32 (3)	N11—Ni1—S1ⁱⁱ	89.87 (3)
N1—Ni1—N11	91.71 (4)	N11—Ni1—N11ⁱ	93.73 (6)
N1—Ni1—N11ⁱ	91.34 (4)
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y, z+{\script{1\over 2}}]$ ; (iii) .

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

The metal cations are linked by pairs of anionic ligands into chains that are corrugated because of the cis-coordination of the 3-methylpyridine ligands (Fig. 3).

Figure 3
Crystal structure of the title compound with view of part of a chain showing the Ni coordination along the crystallographic a-axis.

3. Supramolecular features

In the crystal structure of the title compound, the chains proceed in the direction of the crystallographic c-axis and are arranged in such a way that cavities are formed, in which disordered acetonitrile molecules are embedded (Figs. 4 and 5). This arrangement is very similar to that observed in Ni(NCS)₂[4-(boc-amino)pyridine]₂·CH₃CN already reported in the literature (please compare Fig. 1 with Figs. 4 and 5, Suckert et al., 2017). That this structure is structurally related to that of the title compound is also indicated by comparing their unit-cell parameters and their space groups. Ni(NCS)₂[4-(boc-amino)pyridine]₂·CH₃CN crystallizes in space group P2₁/n with a = 26.5715 (7) Å, b = 11.4534 (4) Å, c = 9.8286 (2) Å and β = 94.982 (2)°, whereas the corresponding ansolvate crystallizes in space group C2/c with a = 26.7251 (8) Å, b = 11.3245 (5) Å, c = 9.8036 (3) Å and β = 94.922 (2)°. For a better comparison of the crystal structure of the title compound with that of Ni(NCS)₂[4-(boc-amino)pyridine]₂·CH₃CN already reported in the literature, the unit-cell parameters of the title compound must be given for the unconventional setting I2/c, leading to values of a = 16.3513 (1) Å, b = 11.7493 (1) Å, c = 9.7383 (1) Å and β = 94.9271 (1)°. The much larger value of the a-axis in the 4-(boc-amino)pyridine compound originates from the much larger size of this neutral coligand, separating the Ni(NCS)₂ chains more effectively.

Figure 4
Crystal structure of the title compound with view along the crystallographic a-axis.

Figure 5
Crystal structure of the title compound with view along the crystallographic c-axis.

Finally, it is noted that there are no pronounced intermolecular hydrogen bonds in the title compound, except for one C—H⋯N contact that is much too long for any significant interaction [C22—H22A⋯N21(1 − x, y, $[{1\over 2}]$ − z), H⋯N = 1.61 Å, C⋯N = 2.57 (2) Å, C—H⋯N = 162°]. This is in contrast to Ni(NCS)₂[4-(boc-amino)pyridine]₂·CH₃CN where the chains are linked by strong N—H⋯O hydrogen bonding, which might be the reason why this compound is much more stable than the title compound.

4. Database survey

A search in the Cambridge Structure Database (CSD, version 5.43, last update November 2021; Groom et al., 2016 ) for transition-metal thiocyanate compounds with 3-methylpyridine as coligand leads to several hits. There are a couple of known compounds containing nickel, all of which are discrete complexes of the composition Ni(NCS)₂(3-methylpyridine)₄ that contain additional solvate molecules such as one molecule per complex of a mixture of dibromo and dichloromethane, of 2,2-dichloropropane and of dichloromethane, as well as two molecules of dichloromethane and trichloromethane (LAYLAY, LAYLEC, LAYLUS, LAYLIG and LAYLOM; Pang et al., 1992 ). Moreover, crystal structures of the mono-trichloromethane (CIVJEW and CIFJEW01; Nassimbeni et al., 1984 , 1986 ) and monotetrachloromethane solvate (JICMIR; Pang et al., 1990 ) have also been reported. In Ni(NCS)₂(3-methylpyridine)₂(H₂O)₂, two of the coligands are substituted by aqua ligands and no solvate molecules are present (MEGCEH; Tan et al., 2006 ).

In the discrete copper complex Cu(NCS)₂(3-methylpyridine)₂ (ABOTET; Handy et al., 2017 ) the metal center is fourfold and in Cu(NCS)₂(3-methylpyridine)₃ (VEPBAT; Kabešová & Kožíšková, 1989 ) fivefold coordinated. Also one more copper compound with the composition Cu(NCS)(3-methylpyridine)₂ (CUHBEM; Healy et al., 1984 ) has been reported in which the cations are tetrahedrally coordinated by two coligands and also two thiocyanate anions, linking them into chains. Some compounds with Co(NCS)₂ and 3-methylpyridine can also be found in the CSD. All are discrete complexes, but Co(NCS)₂(3-methylpyridine)₂ (EYARIG; Boeckmann et al., 2011 ) has a tetrahedral coordination around the metal center compared to the octahedral complexes Co(NCS)₂(3-methylpyridine)₄ (EYAROM and EYAROM01; Boeckmann et al., 2011 and Małecki et al., 2012 ) and Co(NCS)₂(3-methylpyridine)₂(H₂O)₂ (EYAREC; Boeckmann et al., 2011).

With zinc and cadmium, just one compound could be found each, viz. the discrete tedrahedral complex Zn(NCS)₂(3-methylpyridine)₂ (ETUSAO; Boeckmann & Näther, 2011 ) and Cd(NCS)₂(3-methylpyridine)₂ (FIYGUP; Taniguchi et al., 1987 ) with octahedrally coordinated cations that are linked into chains by the thiocyanate anions. Although not yet included in this CSD version, an octahedral iron complex is known, with the cations coordinated by two thiocyanate anions and four 3-methylpyridine ligands (Ceglarska et al., 2022 ), which was reported analogously also as an isotypic complex with manganese in the same publication. Otherwise, only one more manganese compound is reported, which however contains 3-methylpyridine-N-oxide coligands and consists of a chain structure (KESSAF; Mautner, Berger et al., 2018 ). There are also two compounds with a mixed-metal composition, on the one hand with catena-[tetrakis(thiocyanato)bis(3-methylpyridine)manganesemercury] (NAQYOW; Małecki, 2017a ) and on the other hand with catena-[tetrakis(μ-thiocyanato)bis(3-methylpyridine)mercuryzinc] (QAMSIJ; Małecki, 2017b ).

5. Synthesis and crystallization

Synthesis

Ni(NCS)₂ was purchased from Santa Cruz Biotechnology and 3-methylpyridine was purchased from Alfa Aesar. Acetonitrile, which was used as the solvent, was dried over CaH₂ before use.

Ni(NCS)₂(3-methylpyridine)₂·acetonitrile: The reaction mixture containing 0.25 mmol of Ni(NCS)₂ (43.7 mg) and 0.25 mmol of 3-methylpyridine (24.3 µl) in 1.5 mL of acetonitrile was stored for 2 days at room temperature, resulting in light-green crystals suitable for single-crystal X-ray diffraction measurements.

Experimental details

The data collection for single-crystal structure analysis was performed using an XtaLAB Synergy, Dualflex, HyPix diffractometer from Rigaku with Cu Kα radiation. The PXRD measurements were performed with a Stoe Transmission Powder Diffraction System (STADI P) that is equipped with a MYTHEN 1K detector and a Johansson-type Ge(111) monochromator using Cu Kα₁ radiation (λ = 1.540598 Å). The IR spectra were measured using an ATI Mattson Genesis Series FTIR Spectrometer, control software: WINFIRST, from ATI Mattson. The instruments were calibrated using standard reference materials.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All non-hydrogen atoms were refined anisotropically. The C-bound H atoms were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined isotropically with U_iso(H) = 1.2U_eq(C) (1.5 for methyl H atoms) using a riding model. The acetonitrile solvate molecules are disordered within the channels around a center of inversion, which is located in the middle of two acetonitrile N atoms that show an N—N distance of 1.151 Å. Therefore, they were refined with an sof of 0.5, leading to reasonable anisotropic displacement parameters. The situation is similar to that in Ni(NCS)₂[4-(boc-amino)pyridine]₂·acetonitrile mentioned above.

Table 2
Experimental details

Crystal data
Chemical formula	[Ni(NCS)₂(C₆H₇N)₂]·C₂H₃N
M_r	402.17
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	18.2934 (9), 11.7472 (4), 9.7341 (5)
β (°)	117.043 (6)
V (Å³)	1863.11 (17)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	3.65
Crystal size (mm)	0.15 × 0.15 × 0.03

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction.]$ )
T_min, T_max	0.705, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11840, 1966, 1955
R_int	0.015

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.066, 1.07
No. of reflections	1966
No. of parameters	125
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.37
Computer programs: CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction.]$ ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2016/6 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 1999 ) and publCIF (Westrip, 2010 ).

It is noted that some additional reflections are observed, leading to a doubling of the unit cell and change from C-centered to primitive. The relation between the sub-cell and the super cell is obvious if the super cell [a = 16.3542 (5) Å, b = 23.4916 (8) Å, c = 9.7358 (3) Å and β = 94.977 (3)°, space group P2₁/c] is compared with the sub-cell in space group I2/a instead of C2/c [a = 9.7383 (1) Å, b = 11.7493 (1) Å, c = 16.3513 (1) Å and β = 94.927 (1)°]. However, only very few reflections were observed and their intensity is close to zero (Fig. S5). Nevertheless, the structure can easily be refined in space group P2₁/c, leading to two crystallographically independent Ni^II cations and two unique acetonitrile ligands, but a closer look reveals that even in the super cell the solvate molecules are disordered. Therefore, the very few and weak additional reflections were neglected.

Supporting information

CCDC reference: 2210399

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022009598/jy2022sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022009598/jy2022Isup2.hkl

Experimental (top) and calculated (bottom) X-ray powder pattern of the title compound. DOI: https://doi.org/10.1107/S2056989022009598/jy2022sup3.png

IR spectra of the title compound. The values of the CN stretching vibration of the thiocyanate anions and of the acetonitrile molecules are given. DOI: https://doi.org/10.1107/S2056989022009598/jy2022sup4.png

IR spectra of the title compound after 2h in air atmosphere. The value of the CN stretching vibration is given. DOI: https://doi.org/10.1107/S2056989022009598/jy2022sup5.png

Experimental X-ray powder pattern of the title compound stored for 24h in air atmosphere (top), of the ansolvate stored for 5d in an acetonitrile atmosphere (mid) and the calculated powder pattern (bottom). DOI: https://doi.org/10.1107/S2056989022009598/jy2022sup6.png

View of the reciprocal space in c* direction of a crystal of the title compound measured at room-temperature. DOI: https://doi.org/10.1107/S2056989022009598/jy2022sup7.png

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2021); cell refinement: CrysAlis PRO (Rigaku OD, 2021); data reduction: CrysAlis PRO (Rigaku OD, 2021); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

catena-Poly[[[bis(3-methylpyridine-κN)nickel(II)]-di-µ-1,3-thiocyanato] acetonitrile monosolvate] top

Crystal data top

[Ni(NCS)₂(C₆H₇N)₂]·C₂H₃N	F(000) = 832
M_r = 402.17	D_x = 1.434 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
a = 18.2934 (9) Å	Cell parameters from 9752 reflections
b = 11.7472 (4) Å	θ = 4.6–77.2°
c = 9.7341 (5) Å	µ = 3.65 mm⁻¹
β = 117.043 (6)°	T = 100 K
V = 1863.11 (17) Å³	Plate, light green
Z = 4	0.15 × 0.15 × 0.03 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	1966 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	1955 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.015
Detector resolution: 10.0000 pixels mm^-1	θ_max = 77.7°, θ_min = 4.6°
ω scans	h = −23→21
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2021)	k = −13→14
T_min = 0.705, T_max = 1.000	l = −10→12
11840 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.024	H-atom parameters constrained
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.0356P)² + 1.9913P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
1966 reflections	Δρ_max = 0.27 e Å⁻³
125 parameters	Δρ_min = −0.37 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	Occ. (<1)
Ni1	0.500000	0.11950 (2)	0.250000	0.01509 (10)
N1	0.54965 (7)	0.11278 (9)	0.10148 (12)	0.0185 (2)
C1	0.57231 (7)	0.08251 (10)	0.01406 (14)	0.0165 (2)
S1	0.60344 (2)	0.03798 (3)	−0.11091 (4)	0.01977 (10)
N11	0.58540 (6)	0.24076 (9)	0.38595 (12)	0.0181 (2)
C11	0.62454 (8)	0.22828 (11)	0.53994 (15)	0.0204 (3)
H11	0.607248	0.168907	0.584775	0.025*
C12	0.68901 (8)	0.29758 (12)	0.63729 (16)	0.0244 (3)
C13	0.71270 (9)	0.38429 (13)	0.56974 (18)	0.0297 (3)
H13	0.756660	0.433386	0.631780	0.036*
C14	0.67207 (10)	0.39913 (13)	0.41148 (19)	0.0309 (3)
H14	0.687354	0.458893	0.363972	0.037*
C15	0.60876 (9)	0.32557 (12)	0.32326 (16)	0.0240 (3)
H15	0.581066	0.335802	0.214608	0.029*
C16	0.73170 (9)	0.27472 (15)	0.80794 (17)	0.0336 (3)
H16A	0.696992	0.226009	0.835783	0.050*
H16B	0.741856	0.346916	0.864123	0.050*
H16C	0.784063	0.236346	0.835127	0.050*
N21	0.4958 (3)	0.5343 (3)	0.0380 (4)	0.0525 (8)	0.5
C21	0.4990 (2)	0.5882 (3)	0.1369 (4)	0.0366 (7)	0.5
C22	0.4981 (19)	0.6557 (4)	0.238 (3)	0.059 (3)	0.5
H22A	0.511446	0.613590	0.333381	0.089*	0.5
H22B	0.443345	0.689575	0.200183	0.089*	0.5
H22C	0.538683	0.716083	0.258413	0.089*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01446 (16)	0.01706 (17)	0.01370 (16)	0.000	0.00635 (12)	0.000
N1	0.0176 (5)	0.0201 (5)	0.0177 (5)	−0.0016 (4)	0.0080 (4)	−0.0005 (4)
C1	0.0134 (5)	0.0164 (6)	0.0163 (6)	−0.0017 (4)	0.0039 (4)	0.0010 (4)
S1	0.01886 (16)	0.02257 (18)	0.02138 (17)	−0.00378 (11)	0.01220 (13)	−0.00468 (11)
N11	0.0172 (5)	0.0192 (5)	0.0184 (5)	−0.0010 (4)	0.0084 (4)	−0.0021 (4)
C11	0.0190 (6)	0.0237 (6)	0.0189 (6)	−0.0030 (5)	0.0087 (5)	−0.0027 (5)
C12	0.0199 (6)	0.0288 (7)	0.0245 (6)	−0.0049 (5)	0.0101 (5)	−0.0068 (5)
C13	0.0275 (7)	0.0305 (8)	0.0324 (8)	−0.0124 (6)	0.0148 (6)	−0.0105 (6)
C14	0.0358 (8)	0.0268 (7)	0.0348 (8)	−0.0101 (6)	0.0203 (7)	−0.0018 (6)
C15	0.0271 (6)	0.0223 (6)	0.0245 (6)	−0.0022 (5)	0.0135 (5)	−0.0006 (5)
C16	0.0284 (7)	0.0454 (9)	0.0219 (7)	−0.0141 (7)	0.0070 (6)	−0.0098 (6)
N21	0.071 (2)	0.0457 (19)	0.0431 (19)	−0.0022 (17)	0.0280 (17)	0.0091 (14)
C21	0.0440 (19)	0.0299 (16)	0.0381 (18)	0.0031 (14)	0.0206 (15)	0.0091 (15)
C22	0.080 (3)	0.0398 (18)	0.075 (7)	−0.004 (6)	0.050 (4)	0.017 (6)

Geometric parameters (Å, º) top

Ni1—N1	2.0285 (11)	C13—H13	0.9500
Ni1—N1ⁱ	2.0286 (11)	C13—C14	1.384 (2)
Ni1—S1ⁱⁱ	2.5508 (4)	C14—H14	0.9500
Ni1—S1ⁱⁱⁱ	2.5508 (4)	C14—C15	1.386 (2)
Ni1—N11ⁱ	2.0836 (11)	C15—H15	0.9500
Ni1—N11	2.0836 (11)	C16—H16A	0.9800
N1—C1	1.1590 (17)	C16—H16B	0.9800
C1—S1	1.6456 (13)	C16—H16C	0.9800
N11—C11	1.3435 (16)	N21—C21	1.132 (5)
N11—C15	1.3360 (17)	C21—C22	1.270 (19)
C11—H11	0.9500	C22—H22A	0.9800
C11—C12	1.3912 (18)	C22—H22B	0.9800
C12—C13	1.384 (2)	C22—H22C	0.9800
C12—C16	1.504 (2)

N1—Ni1—N1ⁱ	175.54 (6)	C13—C12—C11	117.29 (13)
N1—Ni1—S1ⁱⁱⁱ	83.43 (3)	C13—C12—C16	122.58 (13)
N1ⁱ—Ni1—S1ⁱⁱⁱ	93.32 (3)	C12—C13—H13	120.1
N1—Ni1—S1ⁱⁱ	93.32 (3)	C14—C13—C12	119.72 (13)
N1ⁱ—Ni1—S1ⁱⁱ	83.43 (3)	C14—C13—H13	120.1
N1—Ni1—N11	91.71 (4)	C13—C14—H14	120.5
N1—Ni1—N11ⁱ	91.34 (4)	C13—C14—C15	119.06 (13)
N1ⁱ—Ni1—N11	91.34 (4)	C15—C14—H14	120.5
N1ⁱ—Ni1—N11ⁱ	91.71 (4)	N11—C15—C14	122.18 (13)
S1ⁱⁱ—Ni1—S1ⁱⁱⁱ	87.022 (18)	N11—C15—H15	118.9
N11ⁱ—Ni1—S1ⁱⁱⁱ	173.74 (3)	C14—C15—H15	118.9
N11—Ni1—S1ⁱⁱ	173.74 (3)	C12—C16—H16A	109.5
N11ⁱ—Ni1—S1ⁱⁱ	89.87 (3)	C12—C16—H16B	109.5
N11—Ni1—S1ⁱⁱⁱ	89.87 (3)	C12—C16—H16C	109.5
N11—Ni1—N11ⁱ	93.73 (6)	H16A—C16—H16B	109.5
C1—N1—Ni1	163.89 (10)	H16A—C16—H16C	109.5
N1—C1—S1	179.13 (12)	H16B—C16—H16C	109.5
C1—S1—Ni1ⁱⁱ	101.56 (4)	N21—C21—C22	174.4 (12)
C11—N11—Ni1	119.96 (9)	C21—C22—H22A	109.5
C15—N11—Ni1	121.53 (9)	C21—C22—H22B	109.5
C15—N11—C11	118.17 (11)	C21—C22—H22C	109.5
N11—C11—H11	118.2	H22A—C22—H22B	109.5
N11—C11—C12	123.56 (12)	H22A—C22—H22C	109.5
C12—C11—H11	118.2	H22B—C22—H22C	109.5
C11—C12—C16	120.10 (13)

Ni1—N11—C11—C12	172.20 (10)	C11—C12—C13—C14	0.4 (2)
Ni1—N11—C15—C14	−172.51 (11)	C12—C13—C14—C15	−0.8 (2)
N11—C11—C12—C13	0.6 (2)	C13—C14—C15—N11	0.2 (2)
N11—C11—C12—C16	−177.52 (13)	C15—N11—C11—C12	−1.20 (19)
C11—N11—C15—C14	0.8 (2)	C16—C12—C13—C14	178.47 (15)

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

Acknowledgements

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

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