The crystal structures of the title compounds consist of discrete octahedral complexes that are arranged in such a way that cavities are formed in which the solvate molecules are located.
Keywords: nickel(II)thiocyanate, 3-methylpyridine, clathrates, crystal structure
Abstract
The reaction of nickel(II)thiocyanate with 3-methylpyridine (3-picoline; C6H7N) in different solvents leads to the formation of crystals of bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)nickel(II) as the ethanol disolvate, [Ni(NCS)2(C6H7N)4]·2C2H5OH (1), the acetonitrile disolvate, [Ni(NCS)2(C6H7N)4]·2CH3CN (2), and the diethyl ether monosolvate, [Ni(NCS)2(C6H7N)4]·C4H10O (3). The crystal structures of these compounds consist of NiII cations coordinated by two N-bonded thiocyanate anions and four 3-methylpyridine ligands to generate NiN6 octahedra with the thiocyanate groups in a trans orientation. In compounds 1 and 2 these complexes are located on centers of inversion, whereas in compound 3, they occupy general positions. In the crystal structures, the complexes are packed in such a way that cavities are formed in which the solvent molecules are located. Compounds 1 and 2 are isotypic, which is not the case for compound 3. In compounds 1 and 2 the solvate molecules are disordered, whereas they are fully ordered in compound 3. Disorder is also observed for one of the 3-methylpyridine ligands in compound 2. Powder X-ray diffraction and IR measurements show that at room temperature all compounds decompose almost immediately into the same phase, as a result of the loss of the solvent molecules.
1. Chemical context
The synthesis and structural characterization of new compounds is still an important topic in coordination chemistry, because some of them might have the potential for future applications such as magnetic behavior. In this context, coordination compounds in which the cations are linked by small-sized anionic ligands into networks of different dimensionality are of special interest. Therefore, many compounds based on, for example, cyanide or azide ligands have been reported in the literature. Magnetic exchange can also be mediated by thiocyanate anions and this is one reason why we and others have been interested in this class of compounds for many years (Mautner et al., 2018 ▸, Rams et al., 2020 ▸, Böhme et al., 2020 ▸). Regarding this, compounds are of interest in which the paramagnetic metal cations are linked by thiocyanate anions into chains or layers (Werner et al., 2014 ▸, 2015a
▸,b
▸; Suckert et al., 2016 ▸). In contrast to azides or cyanides, the synthesis of thiocyanates with bridging coordination is more difficult to achieve, because metal cations such as MnII, FeII, CoII and NiII are less chalcophilic and therefore prefer a terminal N coordination. Nevertheless, a large number of compounds with μ-1,3-bridging thiocyanate anions have been reported in recent years (Mautner et al., 2018 ▸ and Werner et al., 2015a
▸,b
▸).
In our own investigations, we are particularly interested in the influence of the neutral co-ligand on the chemical reactivity, the crystal structure and the magnetic properties of thiocyanate coordination polymers of 3d metal cations. In most cases, we used pyridine derivatives that are substituted in the 4-position as co-ligands, but recently we also became interested in such ligands where the substitutent is located in the 3-position, including 3-methylpyridine (also called 3-picoline), C6H7N. With Co(NCS)2, two discrete complexes with the composition Co(NCS)2(C6H7N)4 (refcodes EYAROM and EYAROM01; Boeckmann et al., 2011 ▸ and Małecki et al., 2012 ▸) and Co(NCS)2(C6H7N)2(H2O)2 (EYAREC; Boeckmann et al., 2011 ▸) are deposited in the Cambridge Structural Database, in which the cobalt cations are octahedrally coordinated by two terminal N-bonded thiocyanate anions and four 3-methylpyridine in the former compound and two 3-methylpyridine and two water ligands in the latter. Upon heating, these complexes lose half of their co-ligands and transform into Co(NCS)2(C6H7N)2 (EYARIG; Boeckmann et al., 2011 ▸) before a decomposition into Co(NCS)2 is observed. Surprisingly, in contrast to most other compounds with pyridine derivatives substituted in the 4-position where chains or layers are formed, in this compound the CoII cations are tetrahedrally coordinated by two terminal N-bonded thiocyanate anions and two 3-methylpyridine co-ligands, forming discrete complexes.
Most compounds with 3-methylpyridine as co-ligand are reported with Ni(NCS)2, but surprisingly in none of them are the NiII cations linked by the thiocyanate anions. This includes, for example, Ni(NCS)2(C6H7N)2(H2O)2 (MEGCEH; Tan et al., 2006 ▸), which is isotypic to its cobalt analog. Moreover, a number of compounds consist of discrete complexes with the general composition Ni(NCS)2(C6H7N)4 in which the NiII cations are octahedrally coordinated by two terminal N-bonded thiocyanate anions as well as by four 3-methylpyridine co-ligands. In all of these compounds, the discrete complexes are packed in such a way that cavities are formed, in which additional solvate molecules are embedded. Altogether, three different structure types are observed. The mono-dichloromethane (Laylus, Pang et al., 1992 ▸), mono-trichloromethane (CIVJEW and CIFJEW01; Nassimbeni et al., 1984 ▸, 1986 ▸), mono-tetrachloromethane, mono-dibromodichloromethane and mono-2,2-dichloropropane clathrates (JICMIR, LAYLAY and LAYLEC; Pang et al., 1990 ▸, 1992 ▸) crystallize in the orthorhombic space group Fddd. If two molecules of trichloromethane are incorporated, the clathrate crystallizes with triclinic symmetry in space group P
(LAYLOM; Pang et al., 1992 ▸) and the bis(dichloromethane) clathrate crystallizes in the monoclinic space group C2/c (LAYLIG; Pang et al., 1992 ▸). It is noted that the two latter unit cells are crystallographically unrelated. The formation of these clathrates for such simple nickel complexes is surprising because this is not observed in practically all other complexes with Ni(NCS)2 and pyridine derivatives as co-ligands. However, it might be traced back to the fact that all of these solvents are non-polar and cannot coordinate to NiII cations to form, for example, solvato octahedral complexes with the composition Ni(NCS)2(C6H7N)2(L)2 (L = co-ligand).
Based on these assumptions, we tried to prepare additional compounds based on Ni(NCS)2 and 3-methylpyridine as co-ligand, for which we used diethyl ether, ethanol and acetonitrile as solvents. All of them can coordinate to NiII cations, which might lead to solvato complexes that afterwards might be transformed into the desired compounds with a bridging coordination by thermal decomposition. On the other hand, they are not very strong donor ligands, which means that compounds with a bridging coordination of the anionic ligands might form directly. With all three solvents, suitable crystals were obtained, which were characterized by single-crystal X-ray diffraction. Structure analysis reveals that even in this case, clathrates with the composition Ni(NCS)2(C6H7N)4 · 2 ethanol (1), Ni(NCS)2(C6H7N)4 · 2 acetonitrile (2) and Ni(NCS)2(C6H7N)4 · diethyl ether (3) have formed, which crystallize in two different structure types, with compounds 1 and 2 isotypic to the bis(dichloromethane) clathrate reported by Pang et al. (1992 ▸). Unfortunately, all of these compounds lose their solvents almost immediately at room temperature and X-ray powder diffraction shows that the same crystalline phase is obtained (Fig. S1 in the supporting information). In their IR spectra, the CN stretching vibration is observed at 2074 cm−1, indicating that the anionic ligands are still terminally N-bonded (Fig. S2). Therefore, one can assume that a solvent-free compound with the composition Ni(NCS)2(C6H7N)4 has formed, that still consists of discrete complexes and for which the crystal structure is unknown.
2. Structural commentary
The asymmetric units of Ni(NCS)2(C6H7N)4 · 2 ethanol (1) and Ni(NCS)2(C6H7N)4 · 2 acetonitrile (2) consist of half of an NiII cation that is located on a center of inversion, one thiocyanate anion and two 3-methylpyridine ligands as well as one ethanol (1) and one acetonitrile (2) solvate molecules in general positions (Figs. 1 ▸ and 2 ▸). The asymmetric unit in Ni(NCS)2(C6H7N)4 · diethyl ether (3) consists of one NiII cation, two thiocyanate anions, four 3-methylpyridine ligands and one diethyl ether solvate molecule that occupy general positions (Fig. 3 ▸). In compounds 1 and 2, the solvate molecules are disordered and were refined using a split model (see Refinement), whereas in compound 3 they are fully ordered. The ethanol and acetonitrile solvates 1 and 2 crystallize in the monoclinic C-centered space group C2/c and are isotypic to the bis(dichloromethane) clathrate reported by Pang et al. (1992 ▸). Compound 3 crystallizes in space group P21/n and its structure type is different from that of the solvates of Ni(NCS)2(C6H7N)4 already reported in the literature (see Chemical Context).
Figure 1.
The molecular structure of compound 1 with labeling and displacement ellipsoids drawn at the 50% probability level. Symmetry code: (A) −x + 1, y, −z +
.
Figure 2.
The molecular structure of compound 2 with labeling and displacement ellipsoids drawn at the 50% probability level. Symmetry code: (A) −x + 1, y, −z +
.
Figure 3.
The molecular structure of compound 3 with labeling and displacement ellipsoids drawn at the 50% probability level.
In all three compounds the nickel(II) cations are octahedrally coordinated by two terminal N-bonded thiocyanate anions and four 3-methylpyridine co-ligands, forming discrete complexes. In compound 1 and 2 the discrete complexes are located on centers of inversion, whereas in compound 3 the complexes are located in general positions. The Ni—N bond lengths are comparable in all three compounds (Tables 1 ▸–3 ▸ ▸) and from the bonding angles, it is obvious that all octahedra are slightly distorted (see supporting information). This is reflected in the octahedral angle variance and the mean octahedral quadratic elongation calculated by the method of Robinson et al. (1971 ▸), which amount to 0.0857°2 and 1.0004, respectively, for compound 1, 0.3299°2 and 1.0006 for compound 2 and 1.0694°2 and 1.0010 for compound 3.
Table 1. Selected bond lengths (Å) for 1 .
| Ni1—N1 | 2.0597 (13) | Ni1—N21 | 2.1200 (11) |
| Ni1—N11 | 2.1196 (12) |
Table 2. Selected bond lengths (Å) for 2 .
| Ni1—N1 | 2.0528 (16) | Ni1—N21 | 2.1224 (13) |
| Ni1—N11 | 2.1235 (14) |
Table 3. Selected bond lengths (Å) for 3 .
| Ni1—N1 | 2.0517 (11) | Ni1—N21 | 2.1266 (10) |
| Ni1—N2 | 2.0552 (11) | Ni1—N31 | 2.1523 (11) |
| Ni1—N11 | 2.1358 (10) | Ni1—N41 | 2.1291 (11) |
3. Supramolecular features
In the crystal structures, the Ni(NCS)2(C6H7N)4 complexes are packed in such a way that cavities are formed, in which the solvate molecules are embedded (Figs. 4 ▸ and 5 ▸). In compound 1, both ethanol molecules are linked to the complex by O—H⋯S hydrogen bonding between the hydroxyl hydrogen atom of the ethanol molecule and the thiocyanate S atom (Fig. 4 ▸). The H⋯S distance amounts to 2.464 (4) Å and the O—H⋯S angle to 172 (2)°, which indicates that this is a strong interaction (Table 4 ▸). There is one additional intermolecular contact between a pyridine H atom and the ethanol O atom, but the distance and geometry of this contact shows that this should be only a very weak interaction (Table 4 ▸). In the isotypic compound 2, no pronounced intermolecular interactions are observed and the packing seems to be dominated by van der Waals interactions. This is similar in the diethyl ether solvate 3, where the complexes are arranged in stacks along the c-axis direction (Fig. 5 ▸). For all compounds, the void spaces occupied by the solvate molecules were calculated, leading to values of 221 Å3 (6.5% of the unit-cell volume) for 1, 162 Å3 (4.8%) for 2 and 165 Å3 (5.1%) for 3. The higher value for compound 1 might be traced back to the intermolecular hydrogen bonding.
Figure 4.
Crystal structure of compound 1 as a representative with view along the crystallographic b-axis and intermolecular O—H⋯S hydrogen bonds shown as dashed lines.
Figure 5.
Crystal structure of compound 3 with view along the crystallographic c-axis.
Table 4. Hydrogen-bond geometry (Å, °) for 1 .
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C15—H15⋯O31i | 0.95 | 2.61 | 3.373 (2) | 138 |
| O31—H31⋯S1 | 0.88 (4) | 2.46 (4) | 3.3379 (17) | 172 (2) |
Symmetry code: (i)
.
4. Database survey
Several thiocyanate compounds with transition metal cations and 3-methylpyridine as co-ligand are reported in the Cambridge Structure Database CSD (version 5.43, last update November 2021; Groom et al., 2016 ▸), including the Co and Ni compounds mentioned above.
With Cd(NCS)2, one compound with the composition Cd(NCS)2(C6H7N)2 (FIYGUP; Taniguchi et al., 1987 ▸) is reported, in which the CdII cations are octahedrally coordinated and linked by pairs of thiocyanate anions into chains. With copper, discrete complexes with the composition Cu(NCS)2(C6H7N)2 (ABOTET; Handy et al., 2017 ▸) and Cu(NCS)2(C6H7N)3 (VEPBAT; Kabešová & Kožíšková, 1989 ▸) are reported. There is also one chain compound with the composition Cu(NCS)2(C6H7N)2 (CUHBEM; Healy et al., 1984 ▸), in which the copper cations are tetrahedrally coordinated. With Zn(NCS)2, the discrete complex Zn(NCS)2(C6H7N)2 with a tetrahedral structure is found (ETUSAO; Boeckmann & Näther, 2011 ▸), which is isotypic to Co(NCS)2(C6H7N)2. With MnII and FeII, two discrete complexes with the composition M(NCS)2(C6H7N)4 (M = Mn, Fe) are reported (Ceglarska et al., 2022 ▸). Additionally there is also a mixed-metal compound with manganese and mercury with the composition catena-[tetrakis(thiocyanato)bis(3-methylpyridine)manganese-mercury] (NAQYOW; Małecki, 2017 ▸).
5. Synthesis and crystallization
Synthesis
3-Methylpyridine was purchased from Alfa Aesar. Ni(NCS)2 was purchased from Santa Cruz Biotechnology. Acetonitrile was dried over CaH2 and ethanol over sodium before use.
Ni(NCS)2(C6H7N)4 · 2 ethanol (1): 0.25 mmol Ni(NCS)2 (43.7 mg) and 2.5 mmol 3-methylpyridine (243 µl) were added to 1.5 ml of ethanol and stored under hydrothermal conditions at 403 K to form light-purple single crystals.
Ni(NCS)2(C6H7N)4 · 2 acetonitrile (2): To synthesize single crystals suitable for single-crystal X-ray analysis, 0.25 mmol of Ni(NCS)2 (43.7 mg) and 2.5 mmol of 3-methylpyridine (243 µl) were combined in a snap-cap vial and 1.5 ml of acetonitrile were added. After two days at room temperature, light-purple blocks were obtained.
Ni(NCS)2(C6H7N)4 · diethylether (3): In a mixture of diethyl ether and H2O, 0.25 mmol of Ni(NCS)2 (43.7 mg) and 2.5 mmol of 3-methylpyridine (243 µl) were added. Single crystals in the form of light-purple blocks were obtained after heating the reaction mixture to 353 K and storing it at this temperature for two days.
6. Refinement
Crystal data, data collection and structure refinement details are summarized in Table 5 ▸. 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) = 1.2 U eq(C) (1.5 for methyl H atoms) using a riding model.
Table 5. Experimental details.
| 1 | 2 | 3 | |
|---|---|---|---|
| Crystal data | |||
| Chemical formula | [Ni(NCS)2(C6H7N)4]·2C2H6O | [Ni(NCS)2(C6H7N)4]·2C2H3N | [Ni(NCS)2(C6H7N)4]·C4H10O |
| M r | 639.51 | 629.48 | 621.49 |
| Crystal system, space group | Monoclinic, C2/c | Monoclinic, C2/c | Monoclinic, P21/n |
| Temperature (K) | 100 | 100 | 100 |
| a, b, c (Å) | 18.5763 (1), 11.6179 (1), 15.8998 (1) | 18.7990 (1), 11.3033 (1), 15.8639 (1) | 10.2275 (10), 25.0468 (1), 12.7180 (1) |
| β (°) | 97.448 (1) | 96.825 (1) | 94.600 (1) |
| V (Å3) | 3402.51 (4) | 3347.04 (4) | 3247.4 (3) |
| Z | 4 | 4 | 4 |
| Radiation type | Cu Kα | Cu Kα | Cu Kα |
| μ (mm−1) | 2.24 | 2.25 | 2.31 |
| Crystal size (mm) | 0.2 × 0.1 × 0.05 | 0.25 × 0.15 × 0.05 | 0.2 × 0.2 × 0.15 |
| Data collection | |||
| Diffractometer | XtaLAB Synergy, Dualflex, HyPix | XtaLAB Synergy, Dualflex, HyPix | XtaLAB Synergy, Dualflex, HyPix |
| Absorption correction | Multi-scan (CrysAlis PRO; Rigaku OD, 2021 ▸) | Multi-scan (CrysAlis PRO; Rigaku OD, 2021 ▸) | Multi-scan (CrysAlis PRO; Rigaku OD, 2021 ▸) |
| T min, T max | 0.857, 1.000 | 0.746, 1.000 | 0.933, 1.000 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 36997, 3672, 3589 | 35196, 3605, 3462 | 56224, 6974, 6907 |
| R int | 0.018 | 0.021 | 0.020 |
| (sin θ/λ)max (Å−1) | 0.638 | 0.638 | 0.638 |
| Refinement | |||
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.036, 0.098, 1.09 | 0.046, 0.153, 1.07 | 0.029, 0.076, 1.03 |
| No. of reflections | 3672 | 3605 | 6974 |
| No. of parameters | 213 | 264 | 368 |
| No. of restraints | 1 | 82 | 0 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.44, −0.38 | 0.80, −0.46 | 0.54, −0.32 |
Supplementary Material
Crystal structure: contains datablock(s) 1, 2, 3, global. DOI: 10.1107/S2056989022008891/hb8036sup1.cif
Structure factors: contains datablock(s) 1. DOI: 10.1107/S2056989022008891/hb80361sup2.hkl
Structure factors: contains datablock(s) 2. DOI: 10.1107/S2056989022008891/hb80362sup3.hkl
Structure factors: contains datablock(s) 3. DOI: 10.1107/S2056989022008891/hb80363sup4.hkl
Experimental X-ray powder patterns of the residues obtained by storing the compounds 1 (A), 2 (B) and 3 (C) for one hour at room-temperature. DOI: 10.1107/S2056989022008891/hb8036sup5.png
IR spectra of the residues obtained by storing the compounds 1 (A), 2 (B) and 3 (C) for one hour at room-temperature. The value of the CN stretching vibrations is given. DOI: 10.1107/S2056989022008891/hb8036sup6.png
Additional supporting information: crystallographic information; 3D view; checkCIF report
supplementary crystallographic information
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) ethanol disolvate (1) . Crystal data
| [Ni(NCS)2(C6H7N)4]·2C2H6O | F(000) = 1352 |
| Mr = 639.51 | Dx = 1.248 Mg m−3 |
| Monoclinic, C2/c | Cu Kα radiation, λ = 1.54184 Å |
| a = 18.5763 (1) Å | Cell parameters from 28027 reflections |
| b = 11.6179 (1) Å | θ = 4.5–79.4° |
| c = 15.8998 (1) Å | µ = 2.24 mm−1 |
| β = 97.448 (1)° | T = 100 K |
| V = 3402.51 (4) Å3 | Block, light purple |
| Z = 4 | 0.2 × 0.1 × 0.05 mm |
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) ethanol disolvate (1) . Data collection
| XtaLAB Synergy, Dualflex, HyPix diffractometer | 3672 independent reflections |
| Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source | 3589 reflections with I > 2σ(I) |
| Mirror monochromator | Rint = 0.018 |
| Detector resolution: 10.0000 pixels mm-1 | θmax = 79.7°, θmin = 4.5° |
| ω scans | h = −23→21 |
| Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2021) | k = −14→14 |
| Tmin = 0.857, Tmax = 1.000 | l = −19→20 |
| 36997 measured reflections |
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) ethanol disolvate (1) . Refinement
| Refinement on F2 | Hydrogen site location: mixed |
| Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
| R[F2 > 2σ(F2)] = 0.036 | w = 1/[σ2(Fo2) + (0.0454P)2 + 3.9194P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.098 | (Δ/σ)max = 0.001 |
| S = 1.09 | Δρmax = 0.44 e Å−3 |
| 3672 reflections | Δρmin = −0.38 e Å−3 |
| 213 parameters | Extinction correction: SHELXL-2016/6 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 1 restraint | Extinction coefficient: 0.00015 (4) |
| Primary atom site location: dual |
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) ethanol disolvate (1) . Special details
| 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. |
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) ethanol disolvate (1) . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Ni1 | 0.500000 | 0.25420 (2) | 0.750000 | 0.01790 (12) | |
| N1 | 0.42011 (7) | 0.25422 (10) | 0.82854 (8) | 0.0245 (3) | |
| C1 | 0.36585 (8) | 0.25217 (11) | 0.85683 (9) | 0.0221 (3) | |
| S1 | 0.28878 (2) | 0.24794 (3) | 0.89699 (2) | 0.03098 (12) | |
| N11 | 0.55731 (6) | 0.38324 (10) | 0.82555 (7) | 0.0245 (2) | |
| C11 | 0.52238 (9) | 0.47165 (12) | 0.85584 (9) | 0.0288 (3) | |
| H11 | 0.470896 | 0.473317 | 0.844620 | 0.035* | |
| C12 | 0.55721 (10) | 0.56143 (14) | 0.90293 (11) | 0.0398 (4) | |
| C13 | 0.63193 (12) | 0.5568 (2) | 0.91929 (16) | 0.0632 (7) | |
| H13 | 0.657909 | 0.615808 | 0.951651 | 0.076* | |
| C14 | 0.66863 (11) | 0.4666 (2) | 0.88857 (16) | 0.0678 (7) | |
| H14 | 0.720101 | 0.462974 | 0.899044 | 0.081* | |
| C15 | 0.62980 (9) | 0.38109 (16) | 0.84226 (11) | 0.0393 (4) | |
| H15 | 0.655461 | 0.318635 | 0.821579 | 0.047* | |
| C16 | 0.51427 (13) | 0.65865 (17) | 0.93377 (14) | 0.0536 (5) | |
| H16A | 0.506739 | 0.718348 | 0.889971 | 0.080* | |
| H16B | 0.540910 | 0.691251 | 0.985543 | 0.080* | |
| H16C | 0.467130 | 0.629800 | 0.945930 | 0.080* | |
| N21 | 0.44290 (6) | 0.12465 (10) | 0.67471 (7) | 0.0212 (2) | |
| C21 | 0.43798 (7) | 0.12692 (12) | 0.58975 (8) | 0.0220 (3) | |
| H21 | 0.460160 | 0.189164 | 0.564102 | 0.026* | |
| C22 | 0.40237 (7) | 0.04368 (12) | 0.53708 (8) | 0.0248 (3) | |
| C23 | 0.37036 (9) | −0.04668 (14) | 0.57566 (10) | 0.0329 (3) | |
| H23 | 0.345507 | −0.105716 | 0.542233 | 0.039* | |
| C24 | 0.37492 (10) | −0.05012 (15) | 0.66333 (10) | 0.0381 (4) | |
| H24 | 0.353266 | −0.111351 | 0.690695 | 0.046* | |
| C25 | 0.41140 (8) | 0.03678 (13) | 0.71022 (9) | 0.0294 (3) | |
| H25 | 0.414269 | 0.034090 | 0.770276 | 0.035* | |
| C26 | 0.39962 (9) | 0.05215 (14) | 0.44214 (9) | 0.0323 (3) | |
| H26A | 0.361753 | 0.106922 | 0.419902 | 0.048* | |
| H26B | 0.388635 | −0.023684 | 0.416676 | 0.048* | |
| H26C | 0.446699 | 0.078720 | 0.428104 | 0.048* | |
| O31 | 0.21100 (8) | 0.26594 (14) | 0.69605 (11) | 0.0553 (4) | |
| H31 | 0.2297 (17) | 0.253 (2) | 0.749 (2) | 0.081 (10)* | |
| C31 | 0.2139 (2) | 0.1760 (4) | 0.6416 (3) | 0.0422 (8) | 0.5 |
| H31A | 0.263961 | 0.165811 | 0.627965 | 0.051* | 0.5 |
| H31B | 0.181366 | 0.190337 | 0.588223 | 0.051* | 0.5 |
| C32 | 0.1896 (3) | 0.0696 (4) | 0.6854 (4) | 0.0599 (13) | 0.5 |
| H32A | 0.224565 | 0.052494 | 0.735440 | 0.090* | 0.5 |
| H32B | 0.187016 | 0.004215 | 0.646123 | 0.090* | 0.5 |
| H32C | 0.141655 | 0.083178 | 0.702817 | 0.090* | 0.5 |
| C31' | 0.2032 (3) | 0.1313 (6) | 0.6797 (3) | 0.0653 (13) | 0.5 |
| H31C | 0.244289 | 0.088968 | 0.711492 | 0.078* | 0.5 |
| H31D | 0.157185 | 0.101977 | 0.696669 | 0.078* | 0.5 |
| C32' | 0.2038 (3) | 0.1196 (5) | 0.5860 (3) | 0.0780 (16) | 0.5 |
| H32D | 0.162597 | 0.161779 | 0.555935 | 0.117* | 0.5 |
| H32E | 0.200058 | 0.038053 | 0.570215 | 0.117* | 0.5 |
| H32F | 0.249214 | 0.151212 | 0.570516 | 0.117* | 0.5 |
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) ethanol disolvate (1) . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ni1 | 0.01946 (19) | 0.01906 (18) | 0.01550 (18) | 0.000 | 0.00346 (12) | 0.000 |
| N1 | 0.0232 (6) | 0.0273 (6) | 0.0235 (6) | 0.0014 (4) | 0.0054 (5) | 0.0020 (4) |
| C1 | 0.0271 (7) | 0.0214 (6) | 0.0178 (6) | 0.0030 (5) | 0.0024 (5) | 0.0015 (4) |
| S1 | 0.0215 (2) | 0.0433 (2) | 0.0295 (2) | 0.00391 (13) | 0.00857 (15) | 0.00623 (14) |
| N11 | 0.0283 (6) | 0.0239 (6) | 0.0218 (5) | −0.0037 (5) | 0.0046 (4) | −0.0031 (4) |
| C11 | 0.0368 (8) | 0.0249 (7) | 0.0257 (7) | −0.0014 (6) | 0.0079 (6) | −0.0026 (5) |
| C12 | 0.0528 (10) | 0.0317 (8) | 0.0383 (8) | −0.0107 (7) | 0.0190 (7) | −0.0116 (7) |
| C13 | 0.0501 (11) | 0.0683 (14) | 0.0754 (15) | −0.0315 (10) | 0.0244 (10) | −0.0458 (12) |
| C14 | 0.0319 (9) | 0.0880 (17) | 0.0852 (16) | −0.0214 (10) | 0.0138 (10) | −0.0533 (14) |
| C15 | 0.0272 (7) | 0.0477 (10) | 0.0435 (9) | −0.0073 (7) | 0.0067 (7) | −0.0188 (8) |
| C16 | 0.0740 (14) | 0.0356 (9) | 0.0547 (11) | −0.0057 (9) | 0.0221 (10) | −0.0198 (8) |
| N21 | 0.0231 (5) | 0.0233 (5) | 0.0172 (5) | −0.0032 (4) | 0.0031 (4) | −0.0004 (4) |
| C21 | 0.0230 (6) | 0.0247 (6) | 0.0184 (6) | −0.0016 (5) | 0.0034 (5) | 0.0015 (5) |
| C22 | 0.0242 (6) | 0.0297 (7) | 0.0202 (6) | −0.0010 (5) | 0.0019 (5) | −0.0022 (5) |
| C23 | 0.0371 (8) | 0.0324 (8) | 0.0290 (7) | −0.0132 (6) | 0.0034 (6) | −0.0058 (6) |
| C24 | 0.0504 (10) | 0.0354 (8) | 0.0295 (8) | −0.0206 (7) | 0.0091 (7) | 0.0001 (6) |
| C25 | 0.0379 (8) | 0.0315 (7) | 0.0195 (6) | −0.0102 (6) | 0.0057 (6) | 0.0019 (5) |
| C26 | 0.0393 (8) | 0.0371 (8) | 0.0197 (7) | −0.0045 (6) | 0.0014 (6) | −0.0043 (6) |
| O31 | 0.0430 (8) | 0.0768 (11) | 0.0444 (8) | 0.0050 (7) | −0.0006 (6) | −0.0149 (7) |
| C31 | 0.0380 (19) | 0.048 (2) | 0.041 (2) | −0.0017 (16) | 0.0067 (16) | −0.0083 (19) |
| C32 | 0.052 (3) | 0.041 (2) | 0.089 (4) | −0.016 (2) | 0.018 (2) | −0.013 (3) |
| C31' | 0.075 (4) | 0.068 (4) | 0.050 (3) | −0.007 (3) | −0.006 (3) | 0.001 (3) |
| C32' | 0.093 (4) | 0.077 (3) | 0.058 (3) | 0.021 (3) | −0.010 (3) | −0.020 (3) |
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) ethanol disolvate (1) . Geometric parameters (Å, º)
| Ni1—N1i | 2.0596 (13) | C22—C23 | 1.388 (2) |
| Ni1—N1 | 2.0597 (13) | C22—C26 | 1.5070 (19) |
| Ni1—N11i | 2.1195 (12) | C23—H23 | 0.9500 |
| Ni1—N11 | 2.1196 (12) | C23—C24 | 1.386 (2) |
| Ni1—N21 | 2.1200 (11) | C24—H24 | 0.9500 |
| Ni1—N21i | 2.1200 (11) | C24—C25 | 1.380 (2) |
| N1—C1 | 1.156 (2) | C25—H25 | 0.9500 |
| C1—S1 | 1.6423 (15) | C26—H26A | 0.9800 |
| N11—C11 | 1.3375 (19) | C26—H26B | 0.9800 |
| N11—C15 | 1.339 (2) | C26—H26C | 0.9800 |
| C11—H11 | 0.9500 | O31—H31 | 0.88 (4) |
| C11—C12 | 1.393 (2) | O31—C31 | 1.362 (4) |
| C12—C13 | 1.380 (3) | O31—C31' | 1.589 (7) |
| C12—C16 | 1.501 (2) | C31—H31A | 0.9900 |
| C13—H13 | 0.9500 | C31—H31B | 0.9900 |
| C13—C14 | 1.375 (3) | C31—C32 | 1.515 (6) |
| C14—H14 | 0.9500 | C32—H32A | 0.9800 |
| C14—C15 | 1.382 (2) | C32—H32B | 0.9800 |
| C15—H15 | 0.9500 | C32—H32C | 0.9800 |
| C16—H16A | 0.9800 | C31'—H31C | 0.9900 |
| C16—H16B | 0.9800 | C31'—H31D | 0.9900 |
| C16—H16C | 0.9800 | C31'—C32' | 1.498 (7) |
| N21—C21 | 1.3423 (16) | C32'—H32D | 0.9800 |
| N21—C25 | 1.3376 (17) | C32'—H32E | 0.9800 |
| C21—H21 | 0.9500 | C32'—H32F | 0.9800 |
| C21—C22 | 1.3894 (19) | ||
| N1i—Ni1—N1 | 179.98 (6) | C22—C21—H21 | 118.0 |
| N1—Ni1—N11 | 90.27 (5) | C21—C22—C26 | 120.66 (13) |
| N1i—Ni1—N11 | 89.72 (5) | C23—C22—C21 | 117.25 (12) |
| N1—Ni1—N11i | 89.72 (5) | C23—C22—C26 | 122.09 (13) |
| N1i—Ni1—N11i | 90.27 (5) | C22—C23—H23 | 120.2 |
| N1—Ni1—N21i | 90.27 (4) | C24—C23—C22 | 119.50 (14) |
| N1i—Ni1—N21i | 89.74 (5) | C24—C23—H23 | 120.2 |
| N1i—Ni1—N21 | 90.27 (4) | C23—C24—H24 | 120.5 |
| N1—Ni1—N21 | 89.74 (5) | C25—C24—C23 | 118.95 (14) |
| N11i—Ni1—N11 | 89.96 (7) | C25—C24—H24 | 120.5 |
| N11i—Ni1—N21 | 90.25 (5) | N21—C25—C24 | 122.79 (13) |
| N11—Ni1—N21i | 90.25 (5) | N21—C25—H25 | 118.6 |
| N11—Ni1—N21 | 179.79 (5) | C24—C25—H25 | 118.6 |
| N11i—Ni1—N21i | 179.79 (5) | C22—C26—H26A | 109.5 |
| N21i—Ni1—N21 | 89.53 (6) | C22—C26—H26B | 109.5 |
| C1—N1—Ni1 | 165.69 (12) | C22—C26—H26C | 109.5 |
| N1—C1—S1 | 179.47 (12) | H26A—C26—H26B | 109.5 |
| C11—N11—Ni1 | 121.04 (10) | H26A—C26—H26C | 109.5 |
| C11—N11—C15 | 117.74 (13) | H26B—C26—H26C | 109.5 |
| C15—N11—Ni1 | 121.18 (10) | C31—O31—H31 | 116.0 (18) |
| N11—C11—H11 | 118.1 | C31'—O31—H31 | 90.7 (18) |
| N11—C11—C12 | 123.72 (15) | O31—C31—H31A | 110.3 |
| C12—C11—H11 | 118.1 | O31—C31—H31B | 110.3 |
| C11—C12—C16 | 120.62 (17) | O31—C31—C32 | 107.2 (4) |
| C13—C12—C11 | 117.27 (16) | H31A—C31—H31B | 108.5 |
| C13—C12—C16 | 122.11 (17) | C32—C31—H31A | 110.3 |
| C12—C13—H13 | 120.1 | C32—C31—H31B | 110.3 |
| C14—C13—C12 | 119.71 (17) | C31—C32—H32A | 109.5 |
| C14—C13—H13 | 120.1 | C31—C32—H32B | 109.5 |
| C13—C14—H14 | 120.4 | C31—C32—H32C | 109.5 |
| C13—C14—C15 | 119.27 (18) | H32A—C32—H32B | 109.5 |
| C15—C14—H14 | 120.4 | H32A—C32—H32C | 109.5 |
| N11—C15—C14 | 122.30 (17) | H32B—C32—H32C | 109.5 |
| N11—C15—H15 | 118.9 | O31—C31'—H31C | 111.0 |
| C14—C15—H15 | 118.9 | O31—C31'—H31D | 111.0 |
| C12—C16—H16A | 109.5 | H31C—C31'—H31D | 109.0 |
| C12—C16—H16B | 109.5 | C32'—C31'—O31 | 103.9 (5) |
| C12—C16—H16C | 109.5 | C32'—C31'—H31C | 111.0 |
| H16A—C16—H16B | 109.5 | C32'—C31'—H31D | 111.0 |
| H16A—C16—H16C | 109.5 | C31'—C32'—H32D | 109.5 |
| H16B—C16—H16C | 109.5 | C31'—C32'—H32E | 109.5 |
| C21—N21—Ni1 | 121.21 (9) | C31'—C32'—H32F | 109.5 |
| C25—N21—Ni1 | 121.18 (9) | H32D—C32'—H32E | 109.5 |
| C25—N21—C21 | 117.61 (12) | H32D—C32'—H32F | 109.5 |
| N21—C21—H21 | 118.0 | H32E—C32'—H32F | 109.5 |
| N21—C21—C22 | 123.90 (12) |
Symmetry code: (i) −x+1, y, −z+3/2.
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) ethanol disolvate (1) . Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C15—H15···O31i | 0.95 | 2.61 | 3.373 (2) | 138 |
| O31—H31···S1 | 0.88 (4) | 2.46 (4) | 3.3379 (17) | 172 (2) |
Symmetry code: (i) −x+1, y, −z+3/2.
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) acetonitrile disolvate (2) . Crystal data
| [Ni(NCS)2(C6H7N)4]·2C2H3N | F(000) = 1320 |
| Mr = 629.48 | Dx = 1.249 Mg m−3 |
| Monoclinic, C2/c | Cu Kα radiation, λ = 1.54184 Å |
| a = 18.7990 (1) Å | Cell parameters from 26840 reflections |
| b = 11.3033 (1) Å | θ = 4.5–79.2° |
| c = 15.8639 (1) Å | µ = 2.25 mm−1 |
| β = 96.825 (1)° | T = 100 K |
| V = 3347.04 (4) Å3 | Block, light purple |
| Z = 4 | 0.25 × 0.15 × 0.05 mm |
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) acetonitrile disolvate (2) . Data collection
| XtaLAB Synergy, Dualflex, HyPix diffractometer | 3605 independent reflections |
| Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source | 3462 reflections with I > 2σ(I) |
| Mirror monochromator | Rint = 0.021 |
| Detector resolution: 10.0000 pixels mm-1 | θmax = 79.7°, θmin = 4.6° |
| ω scans | h = −23→21 |
| Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2021) | k = −13→14 |
| Tmin = 0.746, Tmax = 1.000 | l = −20→19 |
| 35196 measured reflections |
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) acetonitrile disolvate (2) . Refinement
| Refinement on F2 | Primary atom site location: dual |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
| wR(F2) = 0.153 | w = 1/[σ2(Fo2) + (0.0965P)2 + 2.692P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.07 | (Δ/σ)max = 0.001 |
| 3605 reflections | Δρmax = 0.80 e Å−3 |
| 264 parameters | Δρmin = −0.46 e Å−3 |
| 82 restraints |
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) acetonitrile disolvate (2) . Special details
| 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. |
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) acetonitrile disolvate (2) . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Ni1 | 0.500000 | 0.24890 (3) | 0.750000 | 0.02595 (17) | |
| N1 | 0.42021 (9) | 0.24892 (10) | 0.82781 (11) | 0.0345 (4) | |
| C1 | 0.36511 (10) | 0.24794 (11) | 0.85346 (11) | 0.0284 (4) | |
| S1 | 0.28727 (2) | 0.24611 (4) | 0.88985 (3) | 0.04010 (18) | |
| N11 | 0.55665 (7) | 0.38053 (12) | 0.82637 (9) | 0.0330 (3) | |
| C11 | 0.52259 (10) | 0.47154 (15) | 0.85750 (11) | 0.0386 (4) | |
| H11 | 0.472097 | 0.476613 | 0.843833 | 0.046* | |
| C12 | 0.55697 (12) | 0.55942 (17) | 0.90889 (13) | 0.0503 (5) | |
| C13 | 0.63026 (13) | 0.5497 (2) | 0.92937 (16) | 0.0608 (6) | |
| H13 | 0.655637 | 0.607165 | 0.964830 | 0.073* | |
| C14 | 0.66640 (11) | 0.4564 (2) | 0.89825 (16) | 0.0612 (6) | |
| H14 | 0.716769 | 0.448707 | 0.911946 | 0.073* | |
| C15 | 0.62794 (9) | 0.37415 (17) | 0.84660 (12) | 0.0449 (4) | |
| H15 | 0.653079 | 0.310505 | 0.824553 | 0.054* | |
| C16 | 0.51514 (16) | 0.6613 (2) | 0.93882 (19) | 0.0760 (8) | |
| H16A | 0.509929 | 0.722969 | 0.895090 | 0.114* | |
| H16B | 0.540591 | 0.693673 | 0.991274 | 0.114* | |
| H16C | 0.467636 | 0.633742 | 0.949620 | 0.114* | |
| N21 | 0.44432 (7) | 0.11538 (12) | 0.67464 (8) | 0.0310 (3) | |
| C21 | 0.43764 (9) | 0.12022 (14) | 0.58979 (10) | 0.0337 (3) | |
| H21 | 0.460555 | 0.183760 | 0.564569 | 0.040* | 0.757 (5) |
| H21A | 0.452665 | 0.188327 | 0.561597 | 0.040* | 0.243 (5) |
| C22 | 0.4005 (3) | 0.0410 (5) | 0.5368 (4) | 0.0347 (12) | 0.757 (5) |
| C23 | 0.3683 (3) | −0.0535 (4) | 0.5741 (3) | 0.0400 (9) | 0.757 (5) |
| H23 | 0.343460 | −0.112681 | 0.539724 | 0.048* | 0.757 (5) |
| C24 | 0.3730 (2) | −0.0603 (3) | 0.6615 (2) | 0.0453 (8) | 0.757 (5) |
| H24 | 0.350897 | −0.123617 | 0.687939 | 0.054* | 0.757 (5) |
| C25 | 0.4100 (2) | 0.0254 (5) | 0.7095 (4) | 0.0380 (11) | 0.757 (5) |
| H25 | 0.411687 | 0.021686 | 0.769528 | 0.046* | 0.757 (5) |
| C26 | 0.39812 (15) | 0.0533 (2) | 0.44197 (14) | 0.0466 (7) | 0.757 (5) |
| H26A | 0.368378 | 0.121456 | 0.422608 | 0.070* | 0.757 (5) |
| H26B | 0.377644 | −0.018657 | 0.414374 | 0.070* | 0.757 (5) |
| H26C | 0.446794 | 0.064930 | 0.427212 | 0.070* | 0.757 (5) |
| C22' | 0.4062 (13) | 0.017 (2) | 0.5403 (11) | 0.042 (4) | 0.243 (5) |
| H22' | 0.398402 | 0.020171 | 0.480103 | 0.051* | 0.243 (5) |
| C23' | 0.3890 (8) | −0.0810 (15) | 0.5813 (11) | 0.048 (3) | 0.243 (5) |
| H23' | 0.367339 | −0.146067 | 0.550209 | 0.058* | 0.243 (5) |
| C24' | 0.4025 (5) | −0.0869 (9) | 0.6675 (6) | 0.0368 (19) | 0.243 (5) |
| C25' | 0.4322 (6) | 0.0147 (15) | 0.7115 (12) | 0.027 (2) | 0.243 (5) |
| H25' | 0.444086 | 0.009232 | 0.771277 | 0.033* | 0.243 (5) |
| C26' | 0.3910 (5) | −0.1978 (8) | 0.7179 (5) | 0.054 (2) | 0.243 (5) |
| H26D | 0.349846 | −0.241696 | 0.689851 | 0.081* | 0.243 (5) |
| H26E | 0.381743 | −0.175834 | 0.775373 | 0.081* | 0.243 (5) |
| H26F | 0.433910 | −0.247524 | 0.721077 | 0.081* | 0.243 (5) |
| N31 | 0.3955 (6) | 0.6917 (11) | 0.7911 (7) | 0.164 (3) | 0.5 |
| C31 | 0.3454 (6) | 0.6475 (8) | 0.8069 (6) | 0.126 (2) | 0.5 |
| C32 | 0.2775 (8) | 0.5919 (12) | 0.8173 (13) | 0.160 (5) | 0.5 |
| H32A | 0.241992 | 0.613118 | 0.769401 | 0.239* | 0.5 |
| H32B | 0.261097 | 0.619130 | 0.870340 | 0.239* | 0.5 |
| H32C | 0.283598 | 0.505767 | 0.819183 | 0.239* | 0.5 |
| N31' | 0.2788 (5) | 0.7116 (10) | 0.9198 (8) | 0.163 (3) | 0.5 |
| C31' | 0.2854 (4) | 0.6431 (8) | 0.8677 (8) | 0.113 (2) | 0.5 |
| C32' | 0.2937 (5) | 0.5588 (9) | 0.8067 (11) | 0.122 (3) | 0.5 |
| H32D | 0.328828 | 0.586604 | 0.770166 | 0.182* | 0.5 |
| H32E | 0.247670 | 0.545062 | 0.772217 | 0.182* | 0.5 |
| H32F | 0.310663 | 0.484778 | 0.834360 | 0.182* | 0.5 |
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) acetonitrile disolvate (2) . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ni1 | 0.0266 (3) | 0.0241 (3) | 0.0272 (3) | 0.000 | 0.00339 (17) | 0.000 |
| N1 | 0.0328 (8) | 0.0347 (8) | 0.0367 (8) | −0.0004 (4) | 0.0076 (6) | 0.0012 (5) |
| C1 | 0.0336 (8) | 0.0257 (8) | 0.0254 (8) | 0.0016 (5) | 0.0009 (6) | 0.0006 (4) |
| S1 | 0.0297 (3) | 0.0488 (3) | 0.0431 (3) | 0.00236 (14) | 0.0093 (2) | 0.00200 (15) |
| N11 | 0.0360 (7) | 0.0286 (6) | 0.0346 (7) | −0.0035 (5) | 0.0044 (5) | −0.0037 (5) |
| C11 | 0.0452 (9) | 0.0324 (8) | 0.0395 (8) | −0.0026 (7) | 0.0099 (7) | −0.0057 (6) |
| C12 | 0.0649 (12) | 0.0391 (9) | 0.0491 (10) | −0.0099 (8) | 0.0166 (9) | −0.0137 (8) |
| C13 | 0.0609 (13) | 0.0601 (13) | 0.0611 (13) | −0.0223 (11) | 0.0067 (10) | −0.0259 (11) |
| C14 | 0.0425 (10) | 0.0660 (14) | 0.0729 (14) | −0.0132 (9) | −0.0023 (9) | −0.0211 (11) |
| C15 | 0.0364 (8) | 0.0431 (9) | 0.0538 (10) | −0.0042 (7) | 0.0001 (7) | −0.0112 (8) |
| C16 | 0.0889 (19) | 0.0580 (14) | 0.0850 (18) | −0.0064 (12) | 0.0269 (15) | −0.0332 (13) |
| N21 | 0.0352 (7) | 0.0295 (6) | 0.0276 (6) | −0.0048 (5) | 0.0008 (5) | 0.0009 (5) |
| C21 | 0.0393 (8) | 0.0330 (8) | 0.0288 (7) | −0.0021 (6) | 0.0038 (6) | 0.0018 (6) |
| C22 | 0.0409 (18) | 0.031 (2) | 0.0324 (18) | −0.0011 (17) | 0.0058 (14) | 0.0012 (12) |
| C23 | 0.046 (2) | 0.037 (2) | 0.0369 (16) | −0.0138 (16) | 0.0011 (16) | −0.0052 (13) |
| C24 | 0.054 (2) | 0.0409 (17) | 0.0411 (14) | −0.0197 (15) | 0.0044 (15) | 0.0019 (12) |
| C25 | 0.041 (3) | 0.0412 (18) | 0.0315 (15) | −0.014 (2) | 0.001 (2) | 0.0053 (12) |
| C26 | 0.0616 (15) | 0.0482 (14) | 0.0294 (11) | −0.0122 (11) | 0.0032 (10) | −0.0058 (9) |
| C22' | 0.064 (8) | 0.037 (7) | 0.019 (4) | 0.014 (5) | −0.020 (4) | −0.012 (4) |
| C23' | 0.053 (8) | 0.042 (6) | 0.045 (4) | 0.000 (5) | −0.012 (5) | −0.009 (4) |
| C24' | 0.034 (5) | 0.036 (4) | 0.038 (3) | −0.004 (3) | −0.004 (3) | −0.004 (3) |
| C25' | 0.021 (6) | 0.030 (4) | 0.029 (4) | −0.006 (4) | −0.008 (4) | −0.002 (3) |
| C26' | 0.063 (5) | 0.045 (4) | 0.050 (4) | −0.025 (4) | −0.010 (4) | 0.001 (3) |
| N31 | 0.188 (4) | 0.153 (7) | 0.146 (7) | 0.007 (4) | 0.003 (4) | 0.067 (6) |
| C31 | 0.178 (4) | 0.098 (5) | 0.096 (5) | 0.025 (3) | −0.002 (4) | 0.040 (4) |
| C32 | 0.172 (5) | 0.099 (9) | 0.202 (14) | 0.038 (4) | 0.000 (5) | 0.092 (9) |
| N31' | 0.128 (7) | 0.131 (5) | 0.221 (5) | 0.049 (5) | −0.016 (4) | 0.031 (4) |
| C31' | 0.051 (3) | 0.087 (4) | 0.197 (5) | 0.011 (3) | −0.001 (4) | 0.062 (3) |
| C32' | 0.100 (5) | 0.077 (4) | 0.184 (5) | 0.025 (4) | 0.000 (4) | 0.076 (3) |
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) acetonitrile disolvate (2) . Geometric parameters (Å, º)
| Ni1—N1i | 2.0528 (16) | C22—C26 | 1.506 (6) |
| Ni1—N1 | 2.0528 (16) | C23—H23 | 0.9500 |
| Ni1—N11 | 2.1235 (14) | C23—C24 | 1.381 (5) |
| Ni1—N11i | 2.1235 (13) | C24—H24 | 0.9500 |
| Ni1—N21 | 2.1224 (13) | C24—C25 | 1.370 (7) |
| Ni1—N21i | 2.1224 (13) | C25—H25 | 0.9500 |
| N1—C1 | 1.157 (3) | C26—H26A | 0.9800 |
| C1—S1 | 1.6358 (19) | C26—H26B | 0.9800 |
| N11—C11 | 1.337 (2) | C26—H26C | 0.9800 |
| N11—C15 | 1.342 (2) | C22'—H22' | 0.9500 |
| C11—H11 | 0.9500 | C22'—C23' | 1.34 (2) |
| C11—C12 | 1.394 (2) | C23'—H23' | 0.9500 |
| C12—C13 | 1.382 (3) | C23'—C24' | 1.363 (19) |
| C12—C16 | 1.503 (3) | C24'—C25' | 1.423 (19) |
| C13—H13 | 0.9500 | C24'—C26' | 1.516 (13) |
| C13—C14 | 1.377 (3) | C25'—H25' | 0.9500 |
| C14—H14 | 0.9500 | C26'—H26D | 0.9800 |
| C14—C15 | 1.385 (3) | C26'—H26E | 0.9800 |
| C15—H15 | 0.9500 | C26'—H26F | 0.9800 |
| C16—H16A | 0.9800 | N31—C31 | 1.121 (11) |
| C16—H16B | 0.9800 | C31—C32 | 1.449 (14) |
| C16—H16C | 0.9800 | C32—H32A | 0.9800 |
| N21—C21 | 1.3381 (19) | C32—H32B | 0.9800 |
| N21—C25 | 1.357 (6) | C32—H32C | 0.9800 |
| N21—C25' | 1.312 (19) | N31'—C31' | 1.151 (12) |
| C21—H21 | 0.9500 | C31'—C32' | 1.381 (15) |
| C21—H21A | 0.9500 | C32'—H32D | 0.9800 |
| C21—C22 | 1.363 (6) | C32'—H32E | 0.9800 |
| C21—C22' | 1.490 (19) | C32'—H32F | 0.9800 |
| C22—C23 | 1.394 (6) | ||
| N1i—Ni1—N1 | 179.99 (7) | C22'—C21—H21A | 120.6 |
| N1i—Ni1—N11i | 90.55 (6) | C21—C22—C23 | 117.3 (4) |
| N1—Ni1—N11i | 89.44 (6) | C21—C22—C26 | 120.5 (3) |
| N1—Ni1—N11 | 90.55 (6) | C23—C22—C26 | 122.1 (5) |
| N1i—Ni1—N11 | 89.44 (6) | C22—C23—H23 | 120.3 |
| N1i—Ni1—N21 | 90.46 (6) | C24—C23—C22 | 119.3 (4) |
| N1—Ni1—N21 | 89.55 (6) | C24—C23—H23 | 120.3 |
| N1—Ni1—N21i | 90.46 (6) | C23—C24—H24 | 120.4 |
| N1i—Ni1—N21i | 89.55 (6) | C25—C24—C23 | 119.1 (4) |
| N11—Ni1—N11i | 91.03 (8) | C25—C24—H24 | 120.4 |
| N21i—Ni1—N11 | 89.80 (6) | N21—C25—C24 | 122.5 (5) |
| N21i—Ni1—N11i | 179.16 (5) | N21—C25—H25 | 118.7 |
| N21—Ni1—N11i | 89.80 (6) | C24—C25—H25 | 118.7 |
| N21—Ni1—N11 | 179.16 (5) | C22—C26—H26A | 109.5 |
| N21—Ni1—N21i | 89.36 (7) | C22—C26—H26B | 109.5 |
| C1—N1—Ni1 | 163.77 (15) | C22—C26—H26C | 109.5 |
| N1—C1—S1 | 179.81 (16) | H26A—C26—H26B | 109.5 |
| C11—N11—Ni1 | 121.35 (11) | H26A—C26—H26C | 109.5 |
| C11—N11—C15 | 117.48 (15) | H26B—C26—H26C | 109.5 |
| C15—N11—Ni1 | 121.16 (11) | C21—C22'—H22' | 120.2 |
| N11—C11—H11 | 118.1 | C23'—C22'—C21 | 119.6 (14) |
| N11—C11—C12 | 123.73 (17) | C23'—C22'—H22' | 120.2 |
| C12—C11—H11 | 118.1 | C22'—C23'—H23' | 120.0 |
| C11—C12—C16 | 120.5 (2) | C22'—C23'—C24' | 120.0 (15) |
| C13—C12—C11 | 117.42 (18) | C24'—C23'—H23' | 120.0 |
| C13—C12—C16 | 122.1 (2) | C23'—C24'—C25' | 117.9 (13) |
| C12—C13—H13 | 120.1 | C23'—C24'—C26' | 123.3 (10) |
| C14—C13—C12 | 119.83 (19) | C25'—C24'—C26' | 118.7 (11) |
| C14—C13—H13 | 120.1 | N21—C25'—C24' | 124.1 (15) |
| C13—C14—H14 | 120.6 | N21—C25'—H25' | 118.0 |
| C13—C14—C15 | 118.7 (2) | C24'—C25'—H25' | 118.0 |
| C15—C14—H14 | 120.6 | C24'—C26'—H26D | 109.5 |
| N11—C15—C14 | 122.78 (18) | C24'—C26'—H26E | 109.5 |
| N11—C15—H15 | 118.6 | C24'—C26'—H26F | 109.5 |
| C14—C15—H15 | 118.6 | H26D—C26'—H26E | 109.5 |
| C12—C16—H16A | 109.5 | H26D—C26'—H26F | 109.5 |
| C12—C16—H16B | 109.5 | H26E—C26'—H26F | 109.5 |
| C12—C16—H16C | 109.5 | N31—C31—C32 | 173.6 (12) |
| H16A—C16—H16B | 109.5 | C31—C32—H32A | 109.5 |
| H16A—C16—H16C | 109.5 | C31—C32—H32B | 109.5 |
| H16B—C16—H16C | 109.5 | C31—C32—H32C | 109.5 |
| C21—N21—Ni1 | 121.24 (10) | H32A—C32—H32B | 109.5 |
| C21—N21—C25 | 116.6 (3) | H32A—C32—H32C | 109.5 |
| C25—N21—Ni1 | 122.0 (3) | H32B—C32—H32C | 109.5 |
| C25'—N21—Ni1 | 117.8 (8) | N31'—C31'—C32' | 178.5 (12) |
| C25'—N21—C21 | 118.9 (8) | C31'—C32'—H32D | 109.5 |
| N21—C21—H21 | 117.5 | C31'—C32'—H32E | 109.5 |
| N21—C21—H21A | 120.6 | C31'—C32'—H32F | 109.5 |
| N21—C21—C22 | 125.0 (2) | H32D—C32'—H32E | 109.5 |
| N21—C21—C22' | 118.8 (8) | H32D—C32'—H32F | 109.5 |
| C22—C21—H21 | 117.5 | H32E—C32'—H32F | 109.5 |
Symmetry code: (i) −x+1, y, −z+3/2.
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) acetonitrile disolvate (2) . Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C25′—H25′···N21i | 0.95 | 2.48 | 2.991 (15) | 114 |
| C32—H32A···S1ii | 0.98 | 2.93 | 3.791 (17) | 147 |
| C32′—H32F···S1 | 0.98 | 2.89 | 3.779 (10) | 152 |
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1/2, y+1/2, −z+3/2.
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) diethyl ether monosolvate (3) . Crystal data
| [Ni(NCS)2(C6H7N)4]·C4H10O | F(000) = 1312 |
| Mr = 621.49 | Dx = 1.271 Mg m−3 |
| Monoclinic, P21/n | Cu Kα radiation, λ = 1.54184 Å |
| a = 10.2275 (10) Å | Cell parameters from 43692 reflections |
| b = 25.0468 (1) Å | θ = 3.5–79.0° |
| c = 12.7180 (1) Å | µ = 2.31 mm−1 |
| β = 94.600 (1)° | T = 100 K |
| V = 3247.4 (3) Å3 | Block, light purple |
| Z = 4 | 0.2 × 0.2 × 0.15 mm |
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) diethyl ether monosolvate (3) . Data collection
| XtaLAB Synergy, Dualflex, HyPix diffractometer | 6974 independent reflections |
| Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source | 6907 reflections with I > 2σ(I) |
| Mirror monochromator | Rint = 0.020 |
| Detector resolution: 10.0000 pixels mm-1 | θmax = 79.6°, θmin = 3.5° |
| ω scans | h = −12→13 |
| Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2021) | k = −31→30 |
| Tmin = 0.933, Tmax = 1.000 | l = −15→16 |
| 56224 measured reflections |
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) diethyl ether monosolvate (3) . Refinement
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.029 | w = 1/[σ2(Fo2) + (0.0356P)2 + 1.9652P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.076 | (Δ/σ)max = 0.002 |
| S = 1.03 | Δρmax = 0.54 e Å−3 |
| 6974 reflections | Δρmin = −0.32 e Å−3 |
| 368 parameters | Extinction correction: SHELXL-2016/6 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 restraints | Extinction coefficient: 0.00020 (4) |
| Primary atom site location: dual |
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) diethyl ether monosolvate (3) . Special details
| 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. |
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) diethyl ether monosolvate (3) . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| Ni1 | 0.24076 (2) | 0.61197 (2) | 0.27926 (2) | 0.01630 (7) | |
| N1 | 0.24400 (11) | 0.60562 (4) | 0.44028 (9) | 0.0217 (2) | |
| C1 | 0.24082 (12) | 0.62304 (5) | 0.52491 (10) | 0.0188 (2) | |
| S1 | 0.23850 (4) | 0.64887 (2) | 0.64199 (3) | 0.03244 (9) | |
| N2 | 0.23270 (11) | 0.61727 (4) | 0.11760 (9) | 0.0209 (2) | |
| C2 | 0.26680 (12) | 0.62259 (5) | 0.03386 (10) | 0.0195 (2) | |
| S2 | 0.31719 (4) | 0.63063 (2) | −0.08404 (3) | 0.02805 (9) | |
| N11 | 0.11637 (10) | 0.54346 (4) | 0.26359 (8) | 0.0182 (2) | |
| C11 | 0.12071 (12) | 0.51046 (5) | 0.18089 (10) | 0.0195 (2) | |
| H11 | 0.180894 | 0.518406 | 0.129934 | 0.023* | |
| C12 | 0.04240 (12) | 0.46529 (5) | 0.16522 (10) | 0.0212 (2) | |
| C13 | −0.04471 (13) | 0.45407 (5) | 0.24070 (11) | 0.0252 (3) | |
| H13 | −0.100594 | 0.423786 | 0.233060 | 0.030* | |
| C14 | −0.04931 (13) | 0.48748 (6) | 0.32726 (11) | 0.0259 (3) | |
| H14 | −0.107695 | 0.480129 | 0.379882 | 0.031* | |
| C15 | 0.03222 (12) | 0.53170 (5) | 0.33612 (10) | 0.0218 (2) | |
| H15 | 0.028503 | 0.554484 | 0.395516 | 0.026* | |
| C16 | 0.05390 (14) | 0.42992 (6) | 0.07075 (11) | 0.0286 (3) | |
| H16A | 0.090667 | 0.450425 | 0.014493 | 0.043* | |
| H16B | −0.033150 | 0.416564 | 0.045699 | 0.043* | |
| H16C | 0.111655 | 0.399722 | 0.090543 | 0.043* | |
| N21 | 0.40489 (10) | 0.55986 (4) | 0.27878 (8) | 0.0181 (2) | |
| C21 | 0.48770 (12) | 0.56126 (5) | 0.20234 (10) | 0.0209 (2) | |
| H21 | 0.479956 | 0.589974 | 0.153433 | 0.025* | |
| C22 | 0.58430 (13) | 0.52316 (5) | 0.19038 (11) | 0.0249 (3) | |
| C23 | 0.59499 (13) | 0.48144 (5) | 0.26294 (11) | 0.0251 (3) | |
| H23 | 0.658347 | 0.454105 | 0.256871 | 0.030* | |
| C24 | 0.51244 (13) | 0.48016 (5) | 0.34399 (11) | 0.0240 (3) | |
| H24 | 0.519758 | 0.452469 | 0.395165 | 0.029* | |
| C25 | 0.41891 (12) | 0.51993 (5) | 0.34931 (10) | 0.0208 (2) | |
| H25 | 0.362470 | 0.518900 | 0.405078 | 0.025* | |
| C26 | 0.67263 (16) | 0.52747 (7) | 0.10169 (14) | 0.0393 (4) | |
| H26A | 0.632509 | 0.551229 | 0.046997 | 0.059* | |
| H26B | 0.685163 | 0.492004 | 0.071558 | 0.059* | |
| H26C | 0.757741 | 0.541995 | 0.128735 | 0.059* | |
| N31 | 0.36520 (10) | 0.68134 (4) | 0.29236 (8) | 0.0190 (2) | |
| C31 | 0.44241 (12) | 0.69197 (5) | 0.38051 (10) | 0.0206 (2) | |
| H31 | 0.445853 | 0.666502 | 0.436028 | 0.025* | |
| C32 | 0.51760 (12) | 0.73812 (5) | 0.39515 (10) | 0.0220 (3) | |
| C33 | 0.51474 (13) | 0.77437 (5) | 0.31195 (11) | 0.0240 (3) | |
| H33 | 0.565253 | 0.806207 | 0.318239 | 0.029* | |
| C34 | 0.43767 (14) | 0.76355 (5) | 0.22017 (11) | 0.0262 (3) | |
| H34 | 0.435711 | 0.787548 | 0.162214 | 0.031* | |
| C35 | 0.36329 (13) | 0.71725 (5) | 0.21377 (11) | 0.0238 (3) | |
| H35 | 0.308631 | 0.710622 | 0.151170 | 0.029* | |
| C36 | 0.59863 (15) | 0.74773 (6) | 0.49744 (12) | 0.0310 (3) | |
| H36A | 0.567883 | 0.780167 | 0.530802 | 0.046* | |
| H36B | 0.690902 | 0.752064 | 0.483540 | 0.046* | |
| H36C | 0.589876 | 0.717217 | 0.544596 | 0.046* | |
| N41 | 0.07440 (10) | 0.66297 (4) | 0.28090 (9) | 0.0202 (2) | |
| C41 | −0.02476 (13) | 0.65985 (5) | 0.20552 (11) | 0.0228 (3) | |
| H41 | −0.020280 | 0.633303 | 0.152574 | 0.027* | |
| C42 | −0.13370 (13) | 0.69318 (6) | 0.20032 (12) | 0.0277 (3) | |
| C43 | −0.13848 (14) | 0.73168 (5) | 0.27870 (12) | 0.0291 (3) | |
| H43 | −0.211005 | 0.755405 | 0.278184 | 0.035* | |
| C44 | −0.03766 (15) | 0.73536 (5) | 0.35720 (12) | 0.0291 (3) | |
| H44 | −0.040057 | 0.761438 | 0.411257 | 0.035* | |
| C45 | 0.06728 (14) | 0.70034 (5) | 0.35589 (11) | 0.0252 (3) | |
| H45 | 0.136618 | 0.702897 | 0.410014 | 0.030* | |
| C46 | −0.24086 (16) | 0.68799 (8) | 0.11234 (16) | 0.0458 (4) | |
| H46A | −0.215254 | 0.661426 | 0.061268 | 0.069* | |
| H46B | −0.254755 | 0.722555 | 0.077099 | 0.069* | |
| H46C | −0.322232 | 0.676613 | 0.141465 | 0.069* | |
| O1 | 0.69662 (10) | 0.62578 (4) | 0.59182 (9) | 0.0317 (2) | |
| C51 | 0.73601 (16) | 0.60727 (7) | 0.41488 (14) | 0.0366 (3) | |
| H51A | 0.795731 | 0.589524 | 0.369494 | 0.055* | |
| H51B | 0.732205 | 0.645494 | 0.398425 | 0.055* | |
| H51C | 0.648145 | 0.591754 | 0.402625 | 0.055* | |
| C52 | 0.78480 (15) | 0.59971 (6) | 0.52804 (14) | 0.0347 (3) | |
| H52A | 0.789405 | 0.561178 | 0.545302 | 0.042* | |
| H52B | 0.873782 | 0.615096 | 0.541081 | 0.042* | |
| C53 | 0.72920 (16) | 0.61857 (6) | 0.70157 (13) | 0.0343 (3) | |
| H53A | 0.820988 | 0.629759 | 0.720164 | 0.041* | |
| H53B | 0.720701 | 0.580448 | 0.720396 | 0.041* | |
| C54 | 0.63737 (18) | 0.65180 (8) | 0.76094 (14) | 0.0444 (4) | |
| H54A | 0.546535 | 0.642006 | 0.738825 | 0.067* | |
| H54B | 0.651052 | 0.689678 | 0.745921 | 0.067* | |
| H54C | 0.654630 | 0.645388 | 0.836800 | 0.067* |
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) diethyl ether monosolvate (3) . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ni1 | 0.01686 (11) | 0.01632 (11) | 0.01561 (11) | 0.00084 (7) | 0.00063 (8) | −0.00079 (7) |
| N1 | 0.0249 (5) | 0.0217 (5) | 0.0185 (5) | 0.0001 (4) | 0.0018 (4) | −0.0013 (4) |
| C1 | 0.0193 (6) | 0.0166 (5) | 0.0206 (6) | −0.0011 (4) | 0.0021 (4) | 0.0029 (4) |
| S1 | 0.0513 (2) | 0.02888 (18) | 0.01775 (16) | 0.00010 (15) | 0.00635 (14) | −0.00430 (12) |
| N2 | 0.0198 (5) | 0.0204 (5) | 0.0223 (6) | 0.0006 (4) | 0.0008 (4) | 0.0006 (4) |
| C2 | 0.0214 (6) | 0.0145 (5) | 0.0216 (6) | 0.0021 (4) | −0.0046 (5) | −0.0029 (4) |
| S2 | 0.03759 (19) | 0.02713 (17) | 0.02051 (16) | −0.00213 (13) | 0.00901 (13) | 0.00014 (12) |
| N11 | 0.0171 (5) | 0.0177 (5) | 0.0196 (5) | 0.0011 (4) | 0.0002 (4) | 0.0001 (4) |
| C11 | 0.0187 (5) | 0.0204 (6) | 0.0192 (6) | 0.0007 (4) | 0.0006 (4) | 0.0002 (5) |
| C12 | 0.0197 (6) | 0.0201 (6) | 0.0232 (6) | 0.0009 (5) | −0.0027 (5) | −0.0010 (5) |
| C13 | 0.0203 (6) | 0.0228 (6) | 0.0323 (7) | −0.0033 (5) | 0.0007 (5) | −0.0002 (5) |
| C14 | 0.0209 (6) | 0.0282 (7) | 0.0294 (7) | −0.0023 (5) | 0.0064 (5) | 0.0006 (5) |
| C15 | 0.0189 (6) | 0.0237 (6) | 0.0229 (6) | 0.0012 (5) | 0.0029 (5) | −0.0014 (5) |
| C16 | 0.0313 (7) | 0.0265 (7) | 0.0276 (7) | −0.0049 (5) | 0.0005 (5) | −0.0061 (5) |
| N21 | 0.0165 (5) | 0.0175 (5) | 0.0199 (5) | 0.0002 (4) | −0.0003 (4) | −0.0010 (4) |
| C21 | 0.0190 (6) | 0.0207 (6) | 0.0230 (6) | 0.0003 (5) | 0.0015 (5) | 0.0016 (5) |
| C22 | 0.0220 (6) | 0.0244 (6) | 0.0287 (7) | 0.0018 (5) | 0.0056 (5) | 0.0001 (5) |
| C23 | 0.0218 (6) | 0.0211 (6) | 0.0326 (7) | 0.0038 (5) | 0.0024 (5) | −0.0010 (5) |
| C24 | 0.0247 (6) | 0.0196 (6) | 0.0275 (7) | 0.0009 (5) | −0.0006 (5) | 0.0031 (5) |
| C25 | 0.0205 (6) | 0.0203 (6) | 0.0215 (6) | −0.0003 (5) | 0.0012 (5) | 0.0010 (5) |
| C26 | 0.0373 (8) | 0.0393 (9) | 0.0441 (9) | 0.0125 (7) | 0.0206 (7) | 0.0100 (7) |
| N31 | 0.0191 (5) | 0.0164 (5) | 0.0212 (5) | 0.0008 (4) | 0.0008 (4) | −0.0007 (4) |
| C31 | 0.0202 (6) | 0.0200 (6) | 0.0215 (6) | 0.0005 (5) | 0.0003 (5) | 0.0002 (5) |
| C32 | 0.0206 (6) | 0.0206 (6) | 0.0245 (6) | 0.0004 (5) | 0.0001 (5) | −0.0030 (5) |
| C33 | 0.0240 (6) | 0.0172 (6) | 0.0310 (7) | −0.0012 (5) | 0.0031 (5) | −0.0014 (5) |
| C34 | 0.0318 (7) | 0.0193 (6) | 0.0272 (7) | −0.0006 (5) | 0.0002 (5) | 0.0038 (5) |
| C35 | 0.0266 (6) | 0.0203 (6) | 0.0236 (6) | 0.0007 (5) | −0.0026 (5) | 0.0014 (5) |
| C36 | 0.0350 (7) | 0.0260 (7) | 0.0302 (7) | −0.0064 (6) | −0.0077 (6) | −0.0020 (6) |
| N41 | 0.0201 (5) | 0.0185 (5) | 0.0223 (5) | 0.0022 (4) | 0.0033 (4) | 0.0007 (4) |
| C41 | 0.0216 (6) | 0.0209 (6) | 0.0259 (6) | 0.0013 (5) | 0.0021 (5) | 0.0005 (5) |
| C42 | 0.0215 (6) | 0.0251 (7) | 0.0363 (8) | 0.0030 (5) | 0.0013 (5) | 0.0052 (6) |
| C43 | 0.0257 (7) | 0.0221 (6) | 0.0407 (8) | 0.0076 (5) | 0.0092 (6) | 0.0059 (6) |
| C44 | 0.0344 (7) | 0.0207 (6) | 0.0333 (7) | 0.0062 (5) | 0.0088 (6) | −0.0009 (5) |
| C45 | 0.0287 (7) | 0.0208 (6) | 0.0260 (7) | 0.0036 (5) | 0.0027 (5) | −0.0012 (5) |
| C46 | 0.0300 (8) | 0.0435 (9) | 0.0607 (11) | 0.0116 (7) | −0.0155 (8) | −0.0055 (8) |
| O1 | 0.0290 (5) | 0.0293 (5) | 0.0369 (6) | 0.0067 (4) | 0.0030 (4) | 0.0052 (4) |
| C51 | 0.0323 (8) | 0.0337 (8) | 0.0445 (9) | 0.0039 (6) | 0.0078 (7) | −0.0041 (7) |
| C52 | 0.0259 (7) | 0.0278 (7) | 0.0502 (9) | 0.0042 (6) | 0.0026 (6) | −0.0010 (7) |
| C53 | 0.0341 (8) | 0.0298 (7) | 0.0380 (8) | −0.0031 (6) | −0.0044 (6) | 0.0070 (6) |
| C54 | 0.0454 (10) | 0.0504 (10) | 0.0375 (9) | −0.0008 (8) | 0.0045 (7) | 0.0028 (8) |
Bis(isothiocyanato-κN)tetrakis(3-methylpyridine-κN)\ nickel(II) diethyl ether monosolvate (3) . Geometric parameters (Å, º)
| Ni1—N1 | 2.0517 (11) | C31—H31 | 0.9500 |
| Ni1—N2 | 2.0552 (11) | C31—C32 | 1.3926 (18) |
| Ni1—N11 | 2.1358 (10) | C32—C33 | 1.3928 (19) |
| Ni1—N21 | 2.1266 (10) | C32—C36 | 1.5047 (18) |
| Ni1—N31 | 2.1523 (11) | C33—H33 | 0.9500 |
| Ni1—N41 | 2.1291 (11) | C33—C34 | 1.382 (2) |
| N1—C1 | 1.1643 (17) | C34—H34 | 0.9500 |
| C1—S1 | 1.6254 (13) | C34—C35 | 1.3858 (19) |
| N2—C2 | 1.1546 (18) | C35—H35 | 0.9500 |
| C2—S2 | 1.6366 (13) | C36—H36A | 0.9800 |
| N11—C11 | 1.3413 (16) | C36—H36B | 0.9800 |
| N11—C15 | 1.3437 (16) | C36—H36C | 0.9800 |
| C11—H11 | 0.9500 | N41—C41 | 1.3409 (17) |
| C11—C12 | 1.3912 (17) | N41—C45 | 1.3423 (17) |
| C12—C13 | 1.3898 (19) | C41—H41 | 0.9500 |
| C12—C16 | 1.5050 (18) | C41—C42 | 1.3894 (18) |
| C13—H13 | 0.9500 | C42—C43 | 1.391 (2) |
| C13—C14 | 1.387 (2) | C42—C46 | 1.508 (2) |
| C14—H14 | 0.9500 | C43—H43 | 0.9500 |
| C14—C15 | 1.3855 (18) | C43—C44 | 1.380 (2) |
| C15—H15 | 0.9500 | C44—H44 | 0.9500 |
| C16—H16A | 0.9800 | C44—C45 | 1.3872 (19) |
| C16—H16B | 0.9800 | C45—H45 | 0.9500 |
| C16—H16C | 0.9800 | C46—H46A | 0.9800 |
| N21—C21 | 1.3400 (16) | C46—H46B | 0.9800 |
| N21—C25 | 1.3436 (16) | C46—H46C | 0.9800 |
| C21—H21 | 0.9500 | O1—C52 | 1.4195 (19) |
| C21—C22 | 1.3907 (18) | O1—C53 | 1.4202 (19) |
| C22—C23 | 1.3927 (19) | C51—H51A | 0.9800 |
| C22—C26 | 1.5045 (19) | C51—H51B | 0.9800 |
| C23—H23 | 0.9500 | C51—H51C | 0.9800 |
| C23—C24 | 1.3841 (19) | C51—C52 | 1.497 (2) |
| C24—H24 | 0.9500 | C52—H52A | 0.9900 |
| C24—C25 | 1.3864 (18) | C52—H52B | 0.9900 |
| C25—H25 | 0.9500 | C53—H53A | 0.9900 |
| C26—H26A | 0.9800 | C53—H53B | 0.9900 |
| C26—H26B | 0.9800 | C53—C54 | 1.503 (2) |
| C26—H26C | 0.9800 | C54—H54A | 0.9800 |
| N31—C31 | 1.3452 (16) | C54—H54B | 0.9800 |
| N31—C35 | 1.3437 (17) | C54—H54C | 0.9800 |
| N1—Ni1—N2 | 178.45 (4) | N31—C31—H31 | 118.1 |
| N1—Ni1—N11 | 89.58 (4) | N31—C31—C32 | 123.82 (12) |
| N1—Ni1—N21 | 90.33 (4) | C32—C31—H31 | 118.1 |
| N1—Ni1—N31 | 91.33 (4) | C31—C32—C33 | 117.51 (12) |
| N1—Ni1—N41 | 89.18 (4) | C31—C32—C36 | 120.55 (12) |
| N2—Ni1—N11 | 89.02 (4) | C33—C32—C36 | 121.94 (12) |
| N2—Ni1—N21 | 90.29 (4) | C32—C33—H33 | 120.3 |
| N2—Ni1—N31 | 90.07 (4) | C34—C33—C32 | 119.32 (12) |
| N2—Ni1—N41 | 90.18 (4) | C34—C33—H33 | 120.3 |
| N11—Ni1—N31 | 179.05 (4) | C33—C34—H34 | 120.4 |
| N21—Ni1—N11 | 88.35 (4) | C33—C34—C35 | 119.14 (13) |
| N21—Ni1—N31 | 91.93 (4) | C35—C34—H34 | 120.4 |
| N21—Ni1—N41 | 178.94 (4) | N31—C35—C34 | 122.78 (12) |
| N41—Ni1—N11 | 90.72 (4) | N31—C35—H35 | 118.6 |
| N41—Ni1—N31 | 89.02 (4) | C34—C35—H35 | 118.6 |
| C1—N1—Ni1 | 153.43 (10) | C32—C36—H36A | 109.5 |
| N1—C1—S1 | 178.36 (12) | C32—C36—H36B | 109.5 |
| C2—N2—Ni1 | 159.93 (10) | C32—C36—H36C | 109.5 |
| N2—C2—S2 | 179.10 (13) | H36A—C36—H36B | 109.5 |
| C11—N11—Ni1 | 120.75 (8) | H36A—C36—H36C | 109.5 |
| C11—N11—C15 | 117.80 (11) | H36B—C36—H36C | 109.5 |
| C15—N11—Ni1 | 121.44 (8) | C41—N41—Ni1 | 121.14 (9) |
| N11—C11—H11 | 118.0 | C41—N41—C45 | 117.88 (11) |
| N11—C11—C12 | 123.96 (12) | C45—N41—Ni1 | 120.95 (9) |
| C12—C11—H11 | 118.0 | N41—C41—H41 | 118.1 |
| C11—C12—C16 | 120.81 (12) | N41—C41—C42 | 123.82 (13) |
| C13—C12—C11 | 117.33 (12) | C42—C41—H41 | 118.1 |
| C13—C12—C16 | 121.86 (12) | C41—C42—C43 | 117.17 (13) |
| C12—C13—H13 | 120.3 | C41—C42—C46 | 121.06 (14) |
| C14—C13—C12 | 119.39 (12) | C43—C42—C46 | 121.76 (13) |
| C14—C13—H13 | 120.3 | C42—C43—H43 | 120.1 |
| C13—C14—H14 | 120.4 | C44—C43—C42 | 119.85 (13) |
| C15—C14—C13 | 119.24 (12) | C44—C43—H43 | 120.1 |
| C15—C14—H14 | 120.4 | C43—C44—H44 | 120.6 |
| N11—C15—C14 | 122.27 (12) | C43—C44—C45 | 118.89 (13) |
| N11—C15—H15 | 118.9 | C45—C44—H44 | 120.6 |
| C14—C15—H15 | 118.9 | N41—C45—C44 | 122.38 (13) |
| C12—C16—H16A | 109.5 | N41—C45—H45 | 118.8 |
| C12—C16—H16B | 109.5 | C44—C45—H45 | 118.8 |
| C12—C16—H16C | 109.5 | C42—C46—H46A | 109.5 |
| H16A—C16—H16B | 109.5 | C42—C46—H46B | 109.5 |
| H16A—C16—H16C | 109.5 | C42—C46—H46C | 109.5 |
| H16B—C16—H16C | 109.5 | H46A—C46—H46B | 109.5 |
| C21—N21—Ni1 | 122.07 (8) | H46A—C46—H46C | 109.5 |
| C21—N21—C25 | 117.64 (11) | H46B—C46—H46C | 109.5 |
| C25—N21—Ni1 | 119.80 (8) | C52—O1—C53 | 113.17 (12) |
| N21—C21—H21 | 118.1 | H51A—C51—H51B | 109.5 |
| N21—C21—C22 | 123.87 (12) | H51A—C51—H51C | 109.5 |
| C22—C21—H21 | 118.1 | H51B—C51—H51C | 109.5 |
| C21—C22—C23 | 117.46 (12) | C52—C51—H51A | 109.5 |
| C21—C22—C26 | 120.49 (13) | C52—C51—H51B | 109.5 |
| C23—C22—C26 | 122.06 (12) | C52—C51—H51C | 109.5 |
| C22—C23—H23 | 120.3 | O1—C52—C51 | 108.25 (12) |
| C24—C23—C22 | 119.38 (12) | O1—C52—H52A | 110.0 |
| C24—C23—H23 | 120.3 | O1—C52—H52B | 110.0 |
| C23—C24—H24 | 120.5 | C51—C52—H52A | 110.0 |
| C23—C24—C25 | 118.96 (12) | C51—C52—H52B | 110.0 |
| C25—C24—H24 | 120.5 | H52A—C52—H52B | 108.4 |
| N21—C25—C24 | 122.64 (12) | O1—C53—H53A | 110.0 |
| N21—C25—H25 | 118.7 | O1—C53—H53B | 110.0 |
| C24—C25—H25 | 118.7 | O1—C53—C54 | 108.46 (13) |
| C22—C26—H26A | 109.5 | H53A—C53—H53B | 108.4 |
| C22—C26—H26B | 109.5 | C54—C53—H53A | 110.0 |
| C22—C26—H26C | 109.5 | C54—C53—H53B | 110.0 |
| H26A—C26—H26B | 109.5 | C53—C54—H54A | 109.5 |
| H26A—C26—H26C | 109.5 | C53—C54—H54B | 109.5 |
| H26B—C26—H26C | 109.5 | C53—C54—H54C | 109.5 |
| C31—N31—Ni1 | 121.89 (8) | H54A—C54—H54B | 109.5 |
| C35—N31—Ni1 | 120.64 (9) | H54A—C54—H54C | 109.5 |
| C35—N31—C31 | 117.39 (11) | H54B—C54—H54C | 109.5 |
| Ni1—N11—C11—C12 | −179.71 (9) | C23—C24—C25—N21 | 0.0 (2) |
| Ni1—N11—C15—C14 | 179.93 (10) | C25—N21—C21—C22 | 1.80 (19) |
| Ni1—N21—C21—C22 | −170.21 (10) | C26—C22—C23—C24 | 178.84 (14) |
| Ni1—N21—C25—C24 | 170.56 (10) | N31—C31—C32—C33 | −1.89 (19) |
| Ni1—N31—C31—C32 | −175.46 (9) | N31—C31—C32—C36 | 178.29 (12) |
| Ni1—N31—C35—C34 | 177.39 (10) | C31—N31—C35—C34 | 0.66 (19) |
| Ni1—N41—C41—C42 | −177.75 (10) | C31—C32—C33—C34 | 0.66 (19) |
| Ni1—N41—C45—C44 | 177.81 (10) | C32—C33—C34—C35 | 1.1 (2) |
| N11—C11—C12—C13 | −0.29 (19) | C33—C34—C35—N31 | −1.8 (2) |
| N11—C11—C12—C16 | −179.46 (12) | C35—N31—C31—C32 | 1.23 (19) |
| C11—N11—C15—C14 | −0.57 (18) | C36—C32—C33—C34 | −179.52 (13) |
| C11—C12—C13—C14 | −0.44 (19) | N41—C41—C42—C43 | −0.1 (2) |
| C12—C13—C14—C15 | 0.6 (2) | N41—C41—C42—C46 | 179.09 (14) |
| C13—C14—C15—N11 | −0.1 (2) | C41—N41—C45—C44 | −0.3 (2) |
| C15—N11—C11—C12 | 0.79 (18) | C41—C42—C43—C44 | −0.2 (2) |
| C16—C12—C13—C14 | 178.71 (13) | C42—C43—C44—C45 | 0.2 (2) |
| N21—C21—C22—C23 | −0.3 (2) | C43—C44—C45—N41 | 0.0 (2) |
| N21—C21—C22—C26 | 179.49 (14) | C45—N41—C41—C42 | 0.4 (2) |
| C21—N21—C25—C24 | −1.63 (18) | C46—C42—C43—C44 | −179.38 (15) |
| C21—C22—C23—C24 | −1.4 (2) | C52—O1—C53—C54 | 174.86 (13) |
| C22—C23—C24—C25 | 1.5 (2) | C53—O1—C52—C51 | 176.55 (12) |
Funding Statement
Financial support by the State of Schleswig-Holstein and the Deutsche Forschungsgemeinschaft is gratefully acknowledged.
References
- Boeckmann, J. & Näther, C. (2011). Acta Cryst. E67, m994. [DOI] [PMC free article] [PubMed]
- Boeckmann, J., Reimer, B. & Näther, C. (2011). Z. Naturforsch. Teil B, 66, 819–827.
- Böhme, M., Jochim, A., Rams, M., Lohmiller, T., Suckert, S., Schnegg, A., Plass, W. & Näther, C. (2020). Inorg. Chem. 59, 5325–5338. [DOI] [PubMed]
- Brandenburg, K. & Putz, H. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
- Ceglarska, M., Krebs, C. & Näther, C. (2022). Acta Cryst. E78, 755–760. [DOI] [PMC free article] [PubMed]
- Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. [DOI] [PMC free article] [PubMed]
- Handy, J. V., Ayala, G. & Pike, R. D. (2017). Inorg. Chim. Acta, 456, 64–75.
- Healy, P. C., Pakawatchai, C., Papasergio, R. I., Patrick, V. A. & White, A. H. (1984). Inorg. Chem. 23, 3769–3776.
- Kabešová, M. & Kožíšková, Z. (1989). Collect. Czech. Chem. Commun. 54, 1800–1807.
- Małecki, J. G. (2017). CSD Communication (refcode NAQYOW). CCDC, Cambridge, England.
- Małecki, J. G., Bałanda, M., Groń, T. & Kruszyński, R. (2012). Struct. Chem. 23, 1219–1232.
- Mautner, F. A., Traber, M., Fischer, R. C., Torvisco, A., Reichmann, K., Speed, S., Vicente, R. & Massoud, S. S. (2018). Polyhedron, 154, 436–442.
- Nassimbeni, L. R., Bond, D. R., Moore, M. & Papanicolaou, S. (1984). Acta Cryst. A40, C111.
- Nassimbeni, L. R., Papanicolaou, S. & Moore, M. H. (1986). J. Inclusion Phenom. 4, 31–42.
- Pang, L., Lucken, E. A. C. & Bernardinelli, G. (1990). J. Am. Chem. Soc. 112, 8754–8764.
- Pang, L., Lucken, E. A. C. & Bernardinelli, G. (1992). J. Incl Phenom. Macrocycl Chem. 13, 63–76.
- 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. [DOI] [PMC free article] [PubMed]
- Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.
- Robinson, K., Gibbs, G. V. & Ribbe, P. H. (1971). Science, 172, 567–570. [DOI] [PubMed]
- Sheldrick, G. M. (2015a). Acta Cryst. C71, 3–8.
- Sheldrick, G. M. (2015b). Acta Cryst. A71, 3–8.
- Suckert, S., Rams, M., Böhme, M., Germann, L., Dinnebier, R. E., Plass, W., Werner, J. & Näther, C. (2016). Dalton Trans. 45, 18190–18201. [DOI] [PubMed]
- Tan, X.-N., Che, Y.-X. & Zheng, J.-M. (2006). Jiegou Huaxue, 25, 358.
- Taniguchi, M., Sugita, Y. & Ouchi, A. (1987). Bull. Chem. Soc. Jpn, 60, 1321–1326.
- Werner, J., Rams, M., Tomkowicz, Z. & Näther, C. (2014). Dalton Trans. 43, 17333–17342. [DOI] [PubMed]
- Werner, J., Runčevski, T., Dinnebier, R., Ebbinghaus, S. G., Suckert, S. & Näther, C. (2015a). Eur. J. Inorg. Chem. pp. 3236–3245.
- Werner, J., Tomkowicz, Z., Rams, M., Ebbinghaus, S. G., Neumann, T. & Näther, C. (2015b). Dalton Trans. 44, 14149–14158. [DOI] [PubMed]
- Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) 1, 2, 3, global. DOI: 10.1107/S2056989022008891/hb8036sup1.cif
Structure factors: contains datablock(s) 1. DOI: 10.1107/S2056989022008891/hb80361sup2.hkl
Structure factors: contains datablock(s) 2. DOI: 10.1107/S2056989022008891/hb80362sup3.hkl
Structure factors: contains datablock(s) 3. DOI: 10.1107/S2056989022008891/hb80363sup4.hkl
Experimental X-ray powder patterns of the residues obtained by storing the compounds 1 (A), 2 (B) and 3 (C) for one hour at room-temperature. DOI: 10.1107/S2056989022008891/hb8036sup5.png
IR spectra of the residues obtained by storing the compounds 1 (A), 2 (B) and 3 (C) for one hour at room-temperature. The value of the CN stretching vibrations is given. DOI: 10.1107/S2056989022008891/hb8036sup6.png
Additional supporting information: crystallographic information; 3D view; checkCIF report