research communications
Synthesis, κN)bis(thiocyanato-κN)nickel(II)
and thermal properties of tetrakis(3-methylpyridine-aInstitut für Anorganische Chemie, Universität Kiel, Max-Eyth.-Str. 2, 24118 Kiel, Germany
*Correspondence e-mail: cnaether@ac.uni-kiel.de
Reaction of Ni(NCS)2 with 3-methylpyridine in water leads to the formation of crystals of the title compound, [Ni(NCS)2(C6H7N)4]. All of them are of poor quality and non-merohedrally twinned but a using data in HKLF-5 format leads to a reasonable structure model and reliability factors. The of the title compound consists of discrete complexes, in which the nickel cations are sixfold coordinated by two terminal N-bonded thiocyanate anions and four 3-methylpyridine ligands within slightly distorted octahedra. One of the 3-methylpyridine ligands is disordered and was refined using a split model. The discrete complexes are arranged into layers. X-ray powder diffraction proves that pure samples have been obtained, and in the IR spectrum, the CN stretching vibration is observed at 2072 cm−1, in agreement with the presence of only terminally coordinated thiocyanate anions. Comparing the calculated powder pattern with those of the residues obtained by solvent removal from several solvates already reported in the literature proves that, in each case, this crystalline phase is formed. Assessing the crystal structures of the solvates in comparison with that of the ansolvate reveals some similarities.
Keywords: synthesis; crystal structure; IR spectra; thermal properties.
CCDC reference: 2222139
1. Chemical context
Thiocyanate anions are versatile ligands that can coordinate in many different ways to metal cations. The most common coordination is the terminal mode, in which these anionic ligands are only connected via the N or S atom, while the latter is only rarely observed. For several reasons, the μ-1,3 bridging coordination is more interesting and can lead to the formation of chains or layers (Näther et al., 2013). There are also a few compounds with more condensed thiocyanate networks that can form if these anionic ligands take up, for example, the μ-1,3,3 (N,S,S) bridging mode (Näther et al., 2013).
We have been interested in this class of compounds for several years targeting, for example, compounds that show interesting magnetic properties (Suckert et al., 2016; Werner et al., 2014, 2015a,b). In most cases, the neutral coligands used by us and others comprise pyridine derivatives and many such compounds have been reported in the literature (Mautner et al., 2018; Böhme et al., 2020; Rams et al., 2020). If less chalcophilic metal cations such as MnII, FeII, CoII or NiII are used, compounds with the composition M(NCS)2(L)4 (M = Mn, Fe, Co, Ni and L = pyridine derivative) are frequently obtained, in which the metal cations are octahedrally coordinated by two terminal N-bonded thiocyanate anions and four coligands. Many of them have already been reported in the literature. If such compounds are heated, in several cases two of the coligands are removed, leading to a transformation to coligand-deficient compounds, in which the metal cations are linked by the anionic ligands and this is the reason why we are also interested in such discrete complexes (Näther et al., 2013).
Throughout these investigations, we became interested in Ni compounds with 3-methylpyridine as coligand for which some complexes have already been reported in the literature. However, all of these compounds consist of octahedral discrete complexes and the majority forms solvates with the composition Ni(NCS)2(3-methylpyridine)4·X with X = bis(trichloromethane) (LAYLOM; Pang et al., 1992), which crystallizes in P, bis(dichloromethane) (LAYLIG; Pang et al., 1992), which crystallizes in C2/c, mono-tetrachloromethane, mono-dibromo-dichloromethane, mono-dichloromethane and mono-2,2-dichloropropane (JICMIR, LAYLAY, LAYLUS and LAYLEC; Pang et al., 1990, 1992) as well as mono-trichloromethane (CIVJEW and CIFJEW01; Nassimbeni et al., 1984, 1986), all of which crystallize in the orthorhombic Fddd. Surprisingly, for unknown reasons, the of the ansolvate is unknown. What is common to all of the solvates mentioned above is the fact that they contain non-polar solvents, which cannot coordinate to metal cations. We used solvents with donor atoms able to coordinate when attempting to prepare compounds with the composition Ni(NCS)2(3-methylpyridine)2(solvent)2. Upon heating, these should lose their two solvent molecules, transforming into compounds with a bridging coordination. Surprisingly, even in this case, octahedral complexes with the composition Ni(NCS)2(3-methylpyridine)4·X (X = acetonitrile, ethanol, diethyl ether) were obtained (Krebs et al., 2022). We have found that these solvates are unstable and have lost their solvents already at room temperature. X-ray powder diffraction (XRPD) proves that, independent of the of the precursor, the same crystalline phase is always obtained (Fig. 1) which, according to IR spectroscopic data, bears only terminal N-bonded anionic ligands. Unfortunately no single crystals were obtained by this procedure, which means that the of the ansolvate remained unknown. Starting from these observations, we tried to prepare crystals of the ansolvate using a variety of solvents and we eventually obtained crystals with the desired composition from H2O. The CN stretching vibration of the anions in the crystals is observed at 2072 cm−1, indicating the presence of terminal thiocyanate anions (Fig. S1). Single crystal X-ray diffraction proves that the hitherto missing ansolvate has formed and XRPD investigations reveal the formation of a phase-pure sample (Fig. S2). Comparison of the experimental powder pattern obtained by solvent removal from the acetonitrile, ethanol and diethyl ether solvates with that calculated for the ansolvate proves that all of these crystalline phases are identical (Fig. 1). TG-DTA measurements show that the title compound decomposes in three steps, which are all accompanied by an endothermic event in the DTA curve (Fig. S3). The calculated mass loss per coligand amounts to 17.0%, which means that the first step (33.3%) is in reasonable agreement with the loss of two ligands and the second (15.7%) and third (14.9%) step with the loss of one ligand each, indicating the formation of additional compounds.
2. Structural commentary
The 2(3-methylpyridine)4, consists of one NiII cation, two thiocyanate anions and four 3-methylpyridine coligands that occupy general positions. One of the 3-methylpyridine coligands is disordered and was refined using a split model (Fig. 2). In the of the title compound, the nickel cations are sixfold coordinated by two terminal N-bonded thiocyanate anions and four 3-methylpyridine coligands and from the bond lengths and angles it is obvious that the octahedra are slightly distorted (Table 1). This can also be seen from the octahedral angle variance (with a value of 11.2355°2) and the mean octahedral quadratic elongation (with a value of 1.0042) determined by the method of Robinson et al. (1971).
of the title compound, Ni(NCS)
|
3. Supramolecular features
In the ab plane (Fig. 3: top). These layers are separated from neighbouring layers by pairs of 3-methylpyridine ligands that show a butterfly-like arrangement. There are no indications for π–π stacking or intermolecular hydrogen bonding. There are only C—H⋯N and C—H⋯S contacts, but from the distances and angles it is obvious that these are not significant interactions. The arrangement of the complexes in the title compound is similar to that in the solvates Ni(NCS)2(3-methylpyridine)4·ethanol and the isotypic compound Ni(NCS)2(3-methylpyridine)4·acetonitrile (Krebs et al., 2022), indicating some structural relationship (Fig. 3). However, the third solvate, Ni(NCS)2(3-methylpyridine)4·diethyl ether (Krebs et al., 2022) is not isotypic to the ethanol and acetonitrile solvates, yet also transforms into the title compound upon solvent removal. Even in this compound, a similar arrangement of the complexes is formed, which strongly suggests that the same crystalline ansolvate phase is particularly stable.
of the title compound, the discrete complexes are arranged into layers that are located in the4. Database survey
Some compounds with 3-methylpyridine as coligand and transition-metal thiocyanates other than Ni(NCS)2 (see Chemical context) were found in the CSD (version 5.43, last update November 2021; Groom et al., 2016) using ConQuest (Bruno et al., 2002). They include discrete complexes with Co(NCS)2 with an octahedral coordination around the metal center such as 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) and a tedrahedral coordination as in Co(NCS)2(3-methylpyridine)2 (EYARIG; Boeckmann et al., 2011). Some Cu(NCS)2 compounds are also known from the literature. These are the tetrahedrally coordinated compound Cu(NCS)(3-methylpyridine)2 where thiocyanate anions link the copper cations into chains (CUHBEM; Healy et al., 1984), Cu(NCS)2(3-methylpyridine)3 with a fivefold trigonal–bipyramidal-like coordination (VEPBAT; Kabešová & Kožíšková, 1989), and Cu(NCS)2(3-methylpyridine)2 where the metal center is square planar and coordinated by two thiocyanate anions and two 3-methylpyridine coligands (ABOTET; Handy et al., 2017). Additionally, two isotypic iron and manganese complexes with the composition M(NCS)2(3-methylpyridine)4 (M = Fe, Mn) are reported (Ceglarska et al., 2022). With Cd(NCS)2, only the octahedral complex Cd(NCS)2(3-methylpyridine)2 is known, in which the cadmium cations are bridged into chains by thiocyanate anions (FIYGUP; Taniguchi et al., 1987). There is also one zinc complex with the composition Zn(NCS)2(3-methylpyridine)2 (ETUSAO; Boeckmann & Näther, 2011), where the metal centers are tetrahedrally coordinated. Finally, the two non-heterometallic complexes catena-[tetrakis(thiocyanato)bis(3-methylpyridine)manganesemercury] (NAQYOW; Małecki, 2017a) and catena-[tetrakis(μ-thiocyanato)bis(3-methylpyridine)mercuryzinc (QAMSIJ; Małecki, 2017b) are also known.
5. Synthesis and crystallization
Synthesis
Ni(NCS)2 was purchased from Santa Cruz Biotechnology. 3-Methylpyridine (also known as 3-picoline) was purchased from Alfa Aesar.
Ni(NCS)2(3-methylpyridine)4: 0.25mmol Ni(SCN)2 (43.7 mg) and 2.5 mmol 3-methylpyridine (243 µl) where added to 1.5 mL deionized H2O and stored under hydrothermal conditions for 2 d at 403 K. As a result, light-blue single crystals were obtained.
Experimental details
The data collection for single Kα radiation.
analysis was performed using an XtaLAB Synergy, Dualflex, HyPix diffractometer from Rigaku with CuThe XRPD measurements were performed with a Stoe Transmission Powder Diffraction System (STADI P) 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.
Thermogravimetry and differential thermoanalysis (TG-DTA) measurements were performed in a dynamic nitrogen atmosphere in Al2O3 crucibles using a STA-PT 1000 thermobalance from Linseis. The instrument was calibrated using standard reference materials.
6. Refinement
All crystals are of poor quality and merohedrally twinned with at least two componenents that are difficult to separate as is obvious from a view along the b* direction (Fig. S4). Therefore, a twin using data in HKLF-5 format was performed, leading to a BASF parameter of 0.457 (5). using anisotropic displacement parameters leads to relatively large components of the anisotropic displacement parameters, indicating static or dynamic disordering. For one of the four crystallographically independent 3-methylpyridine coligands, the disorder was resolved and this ligand was refined using a split model with restraints. 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 Uiso(H) = 1.5Ueq(C) for methyl H atoms and with Uiso(H) = 1.2 Ueq(C) for all other H atoms using a riding model. Crystal data, data collection and structure details are summarized in Table 2.
Supporting information
CCDC reference: 2222139
https://doi.org/10.1107/S2056989022011379/yz2025sup1.cif
contains datablock I. DOI:IR spectrum of the title compound. The value of the CN stretching vibration of the thiocyanate anions is given. DOI: https://doi.org/10.1107/S2056989022011379/yz2025sup3.png
Experimental (top) and calculated XRPD pattern (bottom) of the title compound. DOI: https://doi.org/10.1107/S2056989022011379/yz2025sup4.png
DTG (top) TG (mid) and DTA curve (bottom) of the title compound measured with 8C/min. The mass loss in % and the peak temperatures are given. DOI: https://doi.org/10.1107/S2056989022011379/yz2025sup5.png
View of the diffraction pattern of the crystal of the title compound along the b* direction. The two twin components are indicated in black and blue. DOI: https://doi.org/10.1107/S2056989022011379/yz2025sup6.png
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022011379/yz2025Isup7.hkl
Data collection: CrysAlis PRO (Rigaku OD, 2021); cell
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).[Ni(NCS)2(C6H7N)4] | Dx = 1.281 Mg m−3 |
Mr = 547.37 | Cu Kα radiation, λ = 1.54184 Å |
Orthorhombic, Pbca | Cell parameters from 11586 reflections |
a = 14.2012 (4) Å | θ = 3.4–77.9° |
b = 15.2704 (4) Å | µ = 2.55 mm−1 |
c = 26.1738 (6) Å | T = 100 K |
V = 5676.0 (3) Å3 | Block, light blue |
Z = 8 | 0.15 × 0.1 × 0.1 mm |
F(000) = 2288 |
XtaLAB Synergy, Dualflex, HyPix diffractometer | 6767 measured reflections |
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source | 6767 independent reflections |
Mirror monochromator | 5975 reflections with I > 2σ(I) |
Detector resolution: 10.0000 pixels mm-1 | θmax = 68.3°, θmin = 3.4° |
ω scans | h = −15→17 |
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2021) | k = −17→18 |
Tmin = 0.814, Tmax = 1.000 | l = −31→31 |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.072 | H-atom parameters constrained |
wR(F2) = 0.203 | w = 1/[σ2(Fo2) + (0.0864P)2 + 8.6753P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
6767 reflections | Δρmax = 0.74 e Å−3 |
386 parameters | Δρmin = −0.61 e Å−3 |
15 restraints |
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 two-component twin. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.51000 (5) | 0.76369 (4) | 0.61618 (2) | 0.0493 (2) | |
N1 | 0.4176 (3) | 0.8666 (3) | 0.62644 (15) | 0.0654 (9) | |
C1 | 0.3581 (3) | 0.9147 (3) | 0.63485 (14) | 0.0595 (10) | |
S1 | 0.27254 (11) | 0.98387 (12) | 0.64613 (6) | 0.0992 (6) | |
N2 | 0.6035 (3) | 0.6638 (2) | 0.60680 (13) | 0.0647 (10) | |
C2 | 0.6745 (4) | 0.6257 (3) | 0.60497 (15) | 0.0683 (14) | |
S2 | 0.77540 (12) | 0.57472 (10) | 0.60158 (6) | 0.0984 (6) | |
N11 | 0.4125 (2) | 0.7018 (2) | 0.56639 (11) | 0.0510 (8) | |
C11 | 0.4102 (3) | 0.6152 (3) | 0.56289 (14) | 0.0546 (10) | |
H11 | 0.437953 | 0.582251 | 0.589725 | 0.065* | |
C12 | 0.3696 (3) | 0.5693 (3) | 0.52235 (15) | 0.0575 (10) | |
C13 | 0.3294 (3) | 0.6190 (3) | 0.48387 (15) | 0.0623 (11) | |
H13 | 0.302533 | 0.591038 | 0.454903 | 0.075* | |
C14 | 0.3283 (3) | 0.7090 (3) | 0.48761 (15) | 0.0627 (11) | |
H14 | 0.299610 | 0.743464 | 0.461734 | 0.075* | |
C15 | 0.3698 (3) | 0.7485 (3) | 0.52963 (15) | 0.0550 (9) | |
H15 | 0.367899 | 0.810485 | 0.532513 | 0.066* | |
C16 | 0.3721 (4) | 0.4712 (3) | 0.52121 (19) | 0.0778 (14) | |
H16A | 0.422808 | 0.450120 | 0.543429 | 0.117* | |
H16B | 0.383374 | 0.451212 | 0.486156 | 0.117* | |
H16C | 0.311698 | 0.448037 | 0.533300 | 0.117* | |
N21 | 0.5673 (2) | 0.8250 (2) | 0.55058 (12) | 0.0503 (7) | |
C21 | 0.5828 (3) | 0.7784 (3) | 0.50761 (15) | 0.0570 (10) | |
H21 | 0.577635 | 0.716422 | 0.509351 | 0.068* | |
C22 | 0.6058 (3) | 0.8161 (4) | 0.46099 (17) | 0.0750 (15) | |
C23 | 0.6157 (4) | 0.9059 (5) | 0.4605 (3) | 0.098 (2) | |
H23 | 0.631190 | 0.934897 | 0.429489 | 0.117* | |
C24 | 0.6034 (4) | 0.9536 (4) | 0.5041 (3) | 0.0869 (17) | |
H24 | 0.611759 | 1.015283 | 0.503588 | 0.104* | |
C25 | 0.5787 (3) | 0.9119 (3) | 0.5489 (2) | 0.0654 (12) | |
H25 | 0.569678 | 0.945459 | 0.579052 | 0.079* | |
C26 | 0.6213 (4) | 0.7585 (5) | 0.41446 (19) | 0.102 (2) | |
H26A | 0.673140 | 0.717732 | 0.421148 | 0.153* | |
H26B | 0.636960 | 0.795217 | 0.384962 | 0.153* | |
H26C | 0.563707 | 0.725337 | 0.407245 | 0.153* | |
N31 | 0.6110 (3) | 0.8264 (2) | 0.66364 (12) | 0.0526 (8) | |
C31 | 0.7026 (3) | 0.8279 (3) | 0.65102 (15) | 0.0560 (9) | |
H31 | 0.720195 | 0.803220 | 0.619100 | 0.067* | |
C32 | 0.7734 (3) | 0.8631 (3) | 0.68143 (17) | 0.0636 (11) | |
C33 | 0.7455 (4) | 0.8989 (3) | 0.72751 (18) | 0.0705 (12) | |
H33 | 0.790971 | 0.923652 | 0.749867 | 0.085* | |
C34 | 0.6519 (4) | 0.8988 (3) | 0.74102 (17) | 0.0686 (12) | |
H34 | 0.632489 | 0.923237 | 0.772691 | 0.082* | |
C35 | 0.5854 (3) | 0.8623 (3) | 0.70773 (16) | 0.0602 (10) | |
H35 | 0.520662 | 0.863337 | 0.716855 | 0.072* | |
C36 | 0.8747 (4) | 0.8623 (5) | 0.6636 (2) | 0.0935 (18) | |
H36A | 0.884808 | 0.812250 | 0.640852 | 0.140* | |
H36B | 0.916506 | 0.857366 | 0.693291 | 0.140* | |
H36C | 0.888383 | 0.916723 | 0.645267 | 0.140* | |
N41 | 0.4324 (8) | 0.7054 (7) | 0.6801 (3) | 0.038 (2) | 0.508 (9) |
C41 | 0.4817 (8) | 0.6676 (6) | 0.7171 (3) | 0.047 (2) | 0.508 (9) |
H41 | 0.548178 | 0.663650 | 0.713665 | 0.056* | 0.508 (9) |
C42 | 0.4391 (10) | 0.6336 (8) | 0.7607 (5) | 0.060 (4) | 0.508 (9) |
C43 | 0.3410 (8) | 0.6417 (6) | 0.7648 (4) | 0.058 (3) | 0.508 (9) |
H43 | 0.309505 | 0.619128 | 0.794012 | 0.070* | 0.508 (9) |
C44 | 0.2899 (8) | 0.6821 (6) | 0.7267 (3) | 0.055 (2) | 0.508 (9) |
H44 | 0.223478 | 0.688128 | 0.729071 | 0.066* | 0.508 (9) |
C45 | 0.3393 (8) | 0.7135 (6) | 0.6849 (3) | 0.044 (2) | 0.508 (9) |
H45 | 0.305316 | 0.742056 | 0.658496 | 0.053* | 0.508 (9) |
C46 | 0.4967 (7) | 0.5905 (8) | 0.8022 (4) | 0.077 (3) | 0.508 (9) |
H46A | 0.553891 | 0.565381 | 0.787301 | 0.115* | 0.508 (9) |
H46B | 0.459517 | 0.544001 | 0.818299 | 0.115* | 0.508 (9) |
H46C | 0.513938 | 0.634263 | 0.827964 | 0.115* | 0.508 (9) |
N41A | 0.4738 (7) | 0.6913 (7) | 0.6803 (4) | 0.045 (3) | 0.492 (9) |
C41A | 0.3824 (10) | 0.6897 (7) | 0.6936 (4) | 0.044 (2) | 0.492 (9) |
H41A | 0.339204 | 0.717790 | 0.671248 | 0.053* | 0.492 (9) |
C42A | 0.3452 (8) | 0.6500 (6) | 0.7378 (4) | 0.052 (3) | 0.492 (9) |
C43A | 0.4107 (10) | 0.6097 (8) | 0.7696 (5) | 0.060 (4) | 0.492 (9) |
H43A | 0.390213 | 0.583224 | 0.800541 | 0.072* | 0.492 (9) |
C44A | 0.5050 (8) | 0.6076 (7) | 0.7569 (3) | 0.061 (2) | 0.492 (9) |
H44A | 0.549538 | 0.579352 | 0.778394 | 0.073* | 0.492 (9) |
C45A | 0.5335 (8) | 0.6479 (6) | 0.7114 (3) | 0.048 (2) | 0.492 (9) |
H45A | 0.598007 | 0.644640 | 0.702042 | 0.058* | 0.492 (9) |
C46A | 0.2399 (7) | 0.6515 (7) | 0.7488 (4) | 0.067 (3) | 0.492 (9) |
H46D | 0.211614 | 0.703204 | 0.732851 | 0.101* | 0.492 (9) |
H46E | 0.229632 | 0.653656 | 0.785833 | 0.101* | 0.492 (9) |
H46F | 0.210660 | 0.598466 | 0.734885 | 0.101* | 0.492 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0694 (5) | 0.0412 (4) | 0.0372 (4) | −0.0156 (3) | −0.0019 (3) | −0.0012 (2) |
N1 | 0.060 (2) | 0.070 (2) | 0.066 (2) | −0.0123 (19) | 0.0107 (17) | −0.0036 (19) |
C1 | 0.066 (3) | 0.071 (3) | 0.0416 (19) | −0.008 (2) | 0.0102 (17) | 0.0098 (18) |
S1 | 0.1028 (10) | 0.1118 (12) | 0.0831 (9) | 0.0356 (9) | 0.0467 (8) | 0.0492 (8) |
N2 | 0.098 (3) | 0.0470 (19) | 0.0487 (18) | −0.003 (2) | −0.0278 (18) | −0.0025 (15) |
C2 | 0.119 (4) | 0.041 (2) | 0.045 (2) | 0.004 (3) | −0.040 (2) | −0.0070 (17) |
S2 | 0.1265 (12) | 0.0774 (9) | 0.0913 (9) | 0.0348 (8) | −0.0594 (9) | −0.0317 (7) |
N11 | 0.0614 (19) | 0.0553 (19) | 0.0365 (14) | −0.0197 (15) | 0.0011 (12) | 0.0000 (13) |
C11 | 0.069 (2) | 0.058 (2) | 0.0371 (17) | −0.0218 (19) | 0.0012 (16) | −0.0019 (16) |
C12 | 0.059 (2) | 0.066 (3) | 0.0469 (19) | −0.019 (2) | 0.0017 (16) | −0.0111 (18) |
C13 | 0.058 (2) | 0.082 (3) | 0.047 (2) | −0.022 (2) | −0.0059 (17) | −0.010 (2) |
C14 | 0.054 (2) | 0.084 (3) | 0.049 (2) | −0.015 (2) | −0.0061 (17) | 0.005 (2) |
C15 | 0.052 (2) | 0.064 (2) | 0.049 (2) | −0.0147 (19) | 0.0028 (16) | 0.0041 (18) |
C16 | 0.090 (3) | 0.075 (3) | 0.069 (3) | −0.020 (3) | −0.012 (2) | −0.024 (2) |
N21 | 0.0485 (16) | 0.0506 (18) | 0.0518 (17) | −0.0086 (14) | −0.0036 (13) | 0.0102 (14) |
C21 | 0.053 (2) | 0.072 (3) | 0.046 (2) | −0.0062 (19) | −0.0031 (16) | 0.0132 (19) |
C22 | 0.052 (2) | 0.118 (5) | 0.055 (2) | −0.007 (3) | 0.0010 (18) | 0.031 (3) |
C23 | 0.063 (3) | 0.132 (6) | 0.098 (4) | −0.004 (3) | 0.008 (3) | 0.073 (4) |
C24 | 0.065 (3) | 0.076 (3) | 0.121 (5) | −0.005 (3) | 0.002 (3) | 0.048 (3) |
C25 | 0.050 (2) | 0.058 (3) | 0.088 (3) | −0.0111 (19) | −0.003 (2) | 0.025 (2) |
C26 | 0.090 (4) | 0.169 (7) | 0.047 (3) | −0.003 (4) | 0.008 (2) | 0.021 (3) |
N31 | 0.074 (2) | 0.0369 (16) | 0.0472 (16) | −0.0094 (15) | −0.0043 (15) | −0.0048 (13) |
C31 | 0.074 (3) | 0.045 (2) | 0.049 (2) | −0.0072 (19) | −0.0067 (18) | −0.0036 (16) |
C32 | 0.068 (3) | 0.058 (3) | 0.065 (2) | −0.004 (2) | −0.017 (2) | −0.003 (2) |
C33 | 0.083 (3) | 0.060 (3) | 0.068 (3) | −0.011 (2) | −0.021 (2) | −0.016 (2) |
C34 | 0.092 (3) | 0.054 (2) | 0.060 (2) | −0.007 (2) | −0.012 (2) | −0.020 (2) |
C35 | 0.080 (3) | 0.047 (2) | 0.054 (2) | −0.010 (2) | −0.0031 (19) | −0.0122 (17) |
C36 | 0.075 (3) | 0.118 (5) | 0.087 (4) | −0.002 (3) | −0.018 (3) | −0.014 (4) |
N41 | 0.031 (6) | 0.052 (5) | 0.032 (3) | −0.015 (5) | 0.006 (4) | −0.004 (3) |
C41 | 0.059 (6) | 0.039 (4) | 0.042 (5) | −0.001 (4) | −0.008 (4) | 0.001 (3) |
C42 | 0.086 (10) | 0.044 (6) | 0.050 (7) | −0.016 (6) | −0.015 (6) | 0.014 (4) |
C43 | 0.087 (8) | 0.044 (5) | 0.044 (5) | −0.013 (5) | 0.006 (5) | 0.000 (4) |
C44 | 0.052 (5) | 0.053 (5) | 0.060 (5) | −0.008 (4) | 0.008 (4) | −0.001 (4) |
C45 | 0.056 (6) | 0.040 (5) | 0.037 (4) | −0.010 (4) | −0.002 (4) | −0.005 (3) |
C46 | 0.083 (7) | 0.086 (7) | 0.062 (6) | −0.008 (5) | −0.012 (4) | 0.026 (5) |
N41A | 0.033 (5) | 0.050 (5) | 0.051 (5) | −0.017 (4) | 0.007 (5) | −0.016 (4) |
C41A | 0.049 (8) | 0.044 (5) | 0.039 (5) | −0.002 (5) | 0.001 (5) | −0.008 (4) |
C42A | 0.074 (7) | 0.041 (5) | 0.042 (5) | −0.012 (5) | 0.019 (6) | −0.012 (4) |
C43A | 0.092 (10) | 0.044 (7) | 0.043 (5) | −0.005 (6) | 0.021 (5) | −0.001 (5) |
C44A | 0.079 (7) | 0.057 (6) | 0.047 (5) | 0.001 (5) | −0.002 (4) | 0.005 (4) |
C45A | 0.055 (6) | 0.050 (5) | 0.040 (4) | −0.003 (4) | 0.002 (4) | −0.004 (3) |
C46A | 0.069 (6) | 0.065 (6) | 0.067 (5) | −0.005 (5) | 0.031 (5) | 0.000 (5) |
Ni1—N1 | 2.064 (4) | C31—H31 | 0.9500 |
Ni1—N2 | 2.037 (4) | C31—C32 | 1.391 (6) |
Ni1—N11 | 2.124 (3) | C32—C33 | 1.383 (7) |
Ni1—N21 | 2.118 (3) | C32—C36 | 1.511 (7) |
Ni1—N31 | 2.126 (3) | C33—H33 | 0.9500 |
Ni1—N41 | 2.193 (10) | C33—C34 | 1.375 (7) |
Ni1—N41A | 2.075 (11) | C34—H34 | 0.9500 |
N1—C1 | 1.142 (6) | C34—C35 | 1.400 (6) |
C1—S1 | 1.637 (5) | C35—H35 | 0.9500 |
N2—C2 | 1.165 (6) | C36—H36A | 0.9800 |
C2—S2 | 1.633 (6) | C36—H36B | 0.9800 |
N11—C11 | 1.326 (5) | C36—H36C | 0.9800 |
N11—C15 | 1.342 (5) | N41—C41 | 1.326 (12) |
C11—H11 | 0.9500 | N41—C45 | 1.333 (11) |
C11—C12 | 1.396 (5) | C41—H41 | 0.9500 |
C12—C13 | 1.384 (6) | C41—C42 | 1.394 (14) |
C12—C16 | 1.499 (7) | C42—C43 | 1.403 (14) |
C13—H13 | 0.9500 | C42—C46 | 1.510 (13) |
C13—C14 | 1.378 (7) | C43—H43 | 0.9500 |
C14—H14 | 0.9500 | C43—C44 | 1.378 (13) |
C14—C15 | 1.386 (6) | C44—H44 | 0.9500 |
C15—H15 | 0.9500 | C44—C45 | 1.385 (12) |
C16—H16A | 0.9800 | C45—H45 | 0.9500 |
C16—H16B | 0.9800 | C46—H46A | 0.9800 |
C16—H16C | 0.9800 | C46—H46B | 0.9800 |
N21—C21 | 1.349 (5) | C46—H46C | 0.9800 |
N21—C25 | 1.337 (6) | N41A—C41A | 1.343 (12) |
C21—H21 | 0.9500 | N41A—C45A | 1.349 (13) |
C21—C22 | 1.388 (6) | C41A—H41A | 0.9500 |
C22—C23 | 1.379 (9) | C41A—C42A | 1.410 (14) |
C22—C26 | 1.518 (9) | C42A—C43A | 1.392 (15) |
C23—H23 | 0.9500 | C42A—C46A | 1.524 (13) |
C23—C24 | 1.365 (10) | C43A—H43A | 0.9500 |
C24—H24 | 0.9500 | C43A—C44A | 1.381 (14) |
C24—C25 | 1.380 (7) | C44A—H44A | 0.9500 |
C25—H25 | 0.9500 | C44A—C45A | 1.398 (11) |
C26—H26A | 0.9800 | C45A—H45A | 0.9500 |
C26—H26B | 0.9800 | C46A—H46D | 0.9800 |
C26—H26C | 0.9800 | C46A—H46E | 0.9800 |
N31—C31 | 1.342 (6) | C46A—H46F | 0.9800 |
N31—C35 | 1.329 (5) | ||
N1—Ni1—N11 | 90.23 (15) | C31—N31—Ni1 | 121.2 (3) |
N1—Ni1—N21 | 90.76 (14) | C35—N31—Ni1 | 120.6 (3) |
N1—Ni1—N31 | 90.57 (14) | C35—N31—C31 | 118.2 (4) |
N1—Ni1—N41 | 83.7 (3) | N31—C31—H31 | 117.7 |
N1—Ni1—N41A | 98.2 (3) | N31—C31—C32 | 124.5 (4) |
N2—Ni1—N1 | 178.73 (15) | C32—C31—H31 | 117.7 |
N2—Ni1—N11 | 91.01 (14) | C31—C32—C36 | 120.6 (4) |
N2—Ni1—N21 | 89.04 (14) | C33—C32—C31 | 116.4 (4) |
N2—Ni1—N31 | 88.17 (14) | C33—C32—C36 | 123.0 (4) |
N2—Ni1—N41 | 96.6 (3) | C32—C33—H33 | 120.0 |
N2—Ni1—N41A | 82.0 (3) | C34—C33—C32 | 120.1 (4) |
N11—Ni1—N31 | 177.86 (12) | C34—C33—H33 | 120.0 |
N11—Ni1—N41 | 87.7 (3) | C33—C34—H34 | 120.3 |
N21—Ni1—N11 | 87.12 (12) | C33—C34—C35 | 119.5 (4) |
N21—Ni1—N31 | 90.89 (12) | C35—C34—H34 | 120.3 |
N21—Ni1—N41 | 172.4 (3) | N31—C35—C34 | 121.3 (5) |
N31—Ni1—N41 | 94.4 (3) | N31—C35—H35 | 119.3 |
N41A—Ni1—N11 | 95.6 (3) | C34—C35—H35 | 119.3 |
N41A—Ni1—N21 | 170.6 (3) | C32—C36—H36A | 109.5 |
N41A—Ni1—N31 | 86.2 (3) | C32—C36—H36B | 109.5 |
C1—N1—Ni1 | 170.3 (4) | C32—C36—H36C | 109.5 |
N1—C1—S1 | 179.3 (4) | H36A—C36—H36B | 109.5 |
C2—N2—Ni1 | 160.5 (3) | H36A—C36—H36C | 109.5 |
N2—C2—S2 | 178.4 (5) | H36B—C36—H36C | 109.5 |
C11—N11—Ni1 | 120.2 (3) | C41—N41—Ni1 | 117.8 (7) |
C11—N11—C15 | 118.0 (3) | C41—N41—C45 | 119.7 (9) |
C15—N11—Ni1 | 119.9 (3) | C45—N41—Ni1 | 122.2 (6) |
N11—C11—H11 | 117.8 | N41—C41—H41 | 119.0 |
N11—C11—C12 | 124.3 (4) | N41—C41—C42 | 122.0 (10) |
C12—C11—H11 | 117.8 | C42—C41—H41 | 119.0 |
C11—C12—C16 | 120.5 (4) | C41—C42—C43 | 117.4 (9) |
C13—C12—C11 | 116.6 (4) | C41—C42—C46 | 121.1 (11) |
C13—C12—C16 | 122.9 (4) | C43—C42—C46 | 121.4 (10) |
C12—C13—H13 | 120.0 | C42—C43—H43 | 119.8 |
C14—C13—C12 | 120.0 (4) | C44—C43—C42 | 120.5 (10) |
C14—C13—H13 | 120.0 | C44—C43—H43 | 119.8 |
C13—C14—H14 | 120.5 | C43—C44—H44 | 121.3 |
C13—C14—C15 | 119.1 (4) | C43—C44—C45 | 117.4 (11) |
C15—C14—H14 | 120.5 | C45—C44—H44 | 121.3 |
N11—C15—C14 | 122.0 (4) | N41—C45—C44 | 123.0 (10) |
N11—C15—H15 | 119.0 | N41—C45—H45 | 118.5 |
C14—C15—H15 | 119.0 | C44—C45—H45 | 118.5 |
C12—C16—H16A | 109.5 | C42—C46—H46A | 109.5 |
C12—C16—H16B | 109.5 | C42—C46—H46B | 109.5 |
C12—C16—H16C | 109.5 | C42—C46—H46C | 109.5 |
H16A—C16—H16B | 109.5 | H46A—C46—H46B | 109.5 |
H16A—C16—H16C | 109.5 | H46A—C46—H46C | 109.5 |
H16B—C16—H16C | 109.5 | H46B—C46—H46C | 109.5 |
C21—N21—Ni1 | 120.3 (3) | C41A—N41A—Ni1 | 117.3 (7) |
C25—N21—Ni1 | 120.8 (3) | C41A—N41A—C45A | 116.2 (10) |
C25—N21—C21 | 118.4 (4) | C45A—N41A—Ni1 | 126.5 (7) |
N21—C21—H21 | 118.2 | N41A—C41A—H41A | 117.2 |
N21—C21—C22 | 123.5 (5) | N41A—C41A—C42A | 125.6 (11) |
C22—C21—H21 | 118.2 | C42A—C41A—H41A | 117.2 |
C21—C22—C26 | 119.9 (5) | C41A—C42A—C46A | 121.1 (12) |
C23—C22—C21 | 116.4 (5) | C43A—C42A—C41A | 115.6 (10) |
C23—C22—C26 | 123.6 (5) | C43A—C42A—C46A | 123.3 (10) |
C22—C23—H23 | 119.7 | C42A—C43A—H43A | 119.6 |
C24—C23—C22 | 120.6 (5) | C44A—C43A—C42A | 120.9 (10) |
C24—C23—H23 | 119.7 | C44A—C43A—H43A | 119.6 |
C23—C24—H24 | 120.1 | C43A—C44A—H44A | 120.8 |
C23—C24—C25 | 119.8 (5) | C43A—C44A—C45A | 118.4 (10) |
C25—C24—H24 | 120.1 | C45A—C44A—H44A | 120.8 |
N21—C25—C24 | 121.1 (5) | N41A—C45A—C44A | 123.2 (10) |
N21—C25—H25 | 119.4 | N41A—C45A—H45A | 118.4 |
C24—C25—H25 | 119.4 | C44A—C45A—H45A | 118.4 |
C22—C26—H26A | 109.5 | C42A—C46A—H46D | 109.5 |
C22—C26—H26B | 109.5 | C42A—C46A—H46E | 109.5 |
C22—C26—H26C | 109.5 | C42A—C46A—H46F | 109.5 |
H26A—C26—H26B | 109.5 | H46D—C46A—H46E | 109.5 |
H26A—C26—H26C | 109.5 | H46D—C46A—H46F | 109.5 |
H26B—C26—H26C | 109.5 | H46E—C46A—H46F | 109.5 |
Acknowledgements
This work was supported by the state of Schleswig-Holstein.
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