research communications
Bis[1,2-bis(4-tert-butylphenyl)ethylene-1,2-dithiolato(1−)]nickel(II) pentane 0.25-solvate
aDepartment of Chemistry, Tulane University, 6400 Freret Street, New Orleans, Louisiana 70118-5698, USA
*Correspondence e-mail: donahue@tulane.edu
The title compound, [Ni(C22H26S2)2], 1, is a square-planar D2h-symmetric compound that occurs on a general position in non-centrosymmetric tetragonal P41212 (No. 92) with ¼ eq of n-pentane (C5H12) as co-crystallite. Intraligand bond lengths show the dithiolene ligands to be in their half-oxidized radical monoanionic form. Intermolecular tBu-C—H⋯arenecentroid and tBu-C—H⋯NiS2C2 centroid close contacts guide the packing arrangement for 1.
Keywords: crystal structure; dithiolene; nickel; electron-withdrawing; electron-donating.
CCDC reference: 2239611
1. Chemical context
Group 10 metallodithiolene complexes have elicited considerable and sustained interest because their optical and solid-state properties are well suited for such important applications as reversibly bleaching dyes in neodymium YAG lasers (Mueller-Westerhoff et al., 1991), as robust dyes for optical data storage (Nakazumi et al., 1992), as non-linear optical devices (Deplano et al., 2010) and as conducting (Robertson & Cronin, 2002; Kato, 2004; Ouahab, 1998) or magnetic materials (Robertson & Cronin, 2002; Ouahab, 1998; Faulmann & Cassoux, 2003). Among the ligand type generally, those with aryl (Ar) substituents enjoy the advantages of straightforward synthesis from readily accessible benzoin or benzil precursors and of qualitatively predictable effect upon redox potentials and absorption spectra. Our own interest in complexes featuring such ligands has been motivated by their potential to host, by means of appropriately set dithiolene radicals, coherent quantum states for application in quantum computing and data storage (McGuire et al., 2018). With the aim of broadening the window of redox potentials for the [Ar2C2S22–] − e− → [Ar2C2S.S−] oxidation, thereby creating the possibility for completely resolving and separately observing these oxidation processes in mixed dithiolene complexes of the form [(Ar2C2S2)M(tpbz)M(S2C2Ar'2)] (tpbz = 1,2,4,5-tetrakis(diphenylphosphino)benzene; Ar ≠ Ar'), we have undertaken the synthesis and electrochemical characterization of a variety of [Ni(S2C2Ar2)2] complexes with either electron-withdrawing or electron-donating ring substituents. In the course of this effort, crystalline samples of [Ni(S2C2(C6H4-4-tBu)2)2] that were suited for crystallography were obtained. Herein, the details of this structure are described.
The 4,4′-di-tert-butylbenzoin that serves as a dithiolene ligand precursor is prepared from the corresponding benzaldehyde by a 1,4-dimethyl-1,2,4-triazolium iodide-mediated coupling reaction (Myles et al., 2013). Following a procedure originally disclosed by Schrauzer (Schrauzer & Mayweg, 1965a) and well vetted by others, benzoins and benzils are subject equally well to transformation to dithiolene thiophosphoryl (Schrauzer & Mayweg, 1965b; Arumugam et al., 2007) upon treatment with P4S10 in refluxing dioxane. Without the necessity of their being isolated and purified, the introduction of a Ni2+ salt to these dithiolene thiophosphoryl intermediates leads to the metal bis(dithiolene) complex as a charge-neutral species that precipitates from the reaction mixture. Execution of Schrauzer's protocol using 4,4′-di-tert-butylbenzoin produces [Ni(S2C2(C6H4-4-tBu)2)2], 1, in a yield of 32%. The bis(4-tert-butylphenyl)-substituted dithiolene ligand has been used in the preparation and structural characterization of homoleptic Au3+ (Kokatam et al., 2007), Pd2+ (Kokatam et al., 2007), and Pt2+ complexes (Pap, et al., 2007), but its Ni2+ compound, although investigated spectroscopically (Men et al., 2008), has not been the subject of a crystallographic study.
2. Structural commentary
Compound 1 (Fig. 1) crystallizes in the non-centrosymmetric tetragonal P41212 (No. 92) with ¼ eq of n-pentane (C5H12) and features a c axis much longer [65.014 (4) Å] than its other cell dimensions [11.7187 (4) Å]. The intraligand bond lengths (S—C ≃ 1.71 Å, C—Cchelate ≃ 1.37 Å) are indicative of the radical monoanionic redox state for the dithiolene ligand [Fig. 2(b)]. The bond lengths presented in Fig. 2 are taken from well-defined nickel bis(dithiolene) complexes in which both ligands are fully reduced (Lim et al., 2001), half-oxidized (Lim et al., 2001), and fully oxidized (Bigoli et al., 2001). The angles at which the arene rings meet the central NiS4C4 mean plane range quite narrowly [41.7 (1)–53.5 (1)°].
3. Supramolecular features
For 1, the appreciably longer molecular axis that bisects the dithiolene C—Cchelate bonds and the non-planarity/non-orthogonality of the arene rings relative to the NiS4C4 core are features that support the occurrence of P41212, as seen with similarly elongated molecules bearing a twisted character [cf., for example, ACAGAN (Dowd & Stevens, 2004); BALWAO (Trzeciak-Karlikowska et al., 2011); CANCIH (Lin et al., 2021)]. Simple translations relate one molecule of 1 to another along the a- and b-axis directions (Fig. 3, left), while in the direction of the c axis, replication of 1 arises by movement along 21 axes that are coincident with the c edges of the cell (Fig. 3, right) and by 41 axes positioned parallel to the c axis at the middle of the ac and bc faces. Multiple intermolecular tBu-C—H⋯arenecentroid and tBu-C—H⋯NiS2C2centroid close contacts appear to play a decisive role in determining the packing symmetry patterns (Fig. 4). The most important of these interactions, as gauged by physical proximity, is the C22—H22A⋯Ni2S3S4C3C4centroid contact (2.78 Å).
4. Database survey
Table 1 summarizes selected data pertinent to a set of structurally characterized Group 10 and 11 bis(dithiolene) complexes that are symmetrically substituted with the same arene rings, which now includes three complete series for Group 10 (Ar = Ph, MeO-4-C6H4, tBu-4-C6H4). The database entries included in this tabular survey are NIDPDS01 (Megnamisi-Belombe & Nuber, 1989), NIDPDS03 (Miao et al., 2011), GOLRAA (Sheu & Lee, 1999), BUGDUC (Dessy et al., 1982), SICWOR (Arumugam et al., 2007), SONPUI (Chandrasekaran et al., 2014), SOPMOB (Chandrasekaran et al., 2014), ECEKAA (Miao et al., 2011), DATTUR (Koehne et al., 2022), JUHJUR (Nakazumi et al., 1992), TEYSEW (Kokatam et al., 2007), TIDBEO (Pap et al., 2007), and TEYSAS (Kokatam et al., 2007). Constancy of and unit-cell dimensions is found only for the Ar = Ph series, primarily owing to the absence versus presence of co-crystallized solvent in the other series. However, [Au(S2C2(C6H4-4-tBu)2)2]·CH2Cl2 crystallizes in P41212 with parameters nearly identical to those of 1·0.25(C5H12). Nickel–sulfur bond lengths generally assemble tightly at 2.12 Å. Although the resolution for its structure is somewhat more coarse, [Au(S2C2(C6H4-4-tBu)2)2] differs from the Group 10 metal complexes in having, effectively, its dithiolene ligand set halfway between redox states a and b in Fig. 2 such that the Au3+ ion is paired with three anionic ligand charges arising from one fully reduced dithiolate ligand and one half-oxidized monoanionic ligand. Consequently, its S—C and C—Cchelate bond lengths are longer and shorter, respectively, than those in its Group 10 counterparts. Conspicuous among the φ values for these compounds is the relatively large ≃ 66° angle observed for one unique Ph group in the [M(S2C2Ph2)2] (M = Ni, Pd, Pt) series, which has its origin in specific intermolecular phenyl C—H⋯arenecentroid interactions that are not pertinent to 1.
5. Synthesis and crystallization
[Ni(S2C2(C6H4-4-tBu)2)2], 1. A mixture of 4,4′-di-tert-butylbenzoin (0.350 g, 1.1 mmol) and P4S10 (0.355 g, 0.8 mmol) and dioxane (30 ml) in an oven-dried 100 ml three-neck flask was refluxed at 378 K for 12 h under N2 with continuous stirring. The reaction mixture was cooled to ambient temperature and then gravity filtered through paper in the open air into a 100 ml Schlenk flask. Nickel(II) dichloride hexahydrate (0.120 g, 0.5 mmol) dissolved in 1 ml of H2O was added to the filtrate, and reflux under N2 was recommenced and continued for 12 h with constant stirring. After being cooled to ambient temperature, the solid precipitate that formed was collected by vacuum filtration and then washed with CH3OH followed by Et2O. Yield: 0.135 g, 0.176 mmol, 32%. 1H NMR (δ, CDCl3): 7.33 (pseudo quartet, 16 H, aromatic C–H), 1.32 (s, 36 H, tBu). Analysis calculated for C44H52S4Ni: C, 68.83; H, 6.83; S, 16.70. Found: C, 68.71; H, 6.80; S, 16.63. This analysis was performed upon crystalline 1 grown by vapor diffusion of MeOH into a toluene solution, which produced crystals without interstitial solvent.
Vapor-diffusion methods were effective in generating crystals of diffraction quality. Crystals grown without interstitial solvent were complicated by significant non-merohedral n-pentane vapor into a THF solution of 1 produced crystalline 1·0.25(C5H12) that was not subject to this problem or otherwise necessitating special treatment.
However, introduction of6. Refinement
Crystal data, data collection and structure . The tert-butyl groups defined by C11–C14 and C41–C44 were disordered and treated with independent, floating site occupancy variables that identified 54:46 and 52:48 optimal partitioning, respectively, for the two groups. Hydrogen atoms were added in calculated positions and refined with isotropic displacement parameters that were approximately 1.2 times (for aromatic C—H) or 1.5 times (for –CH3) those of the carbon atoms to which they were attached. The C—H distances assumed were 0.95 and 0.98 Å for the aromatic C—H and –CH3 types of hydrogen atoms, respectively.
details are summarized in Table 2
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Supporting information
CCDC reference: 2239611
https://doi.org/10.1107/S205698902300097X/jy2027sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902300097X/jy2027Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S205698902300097X/jy2027sup3.txt
Data collection: APEX4 (Bruker, 2021); cell
SAINT (Bruker, 2021); data reduction: SAINT (Bruker, 2021); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Ni(C22H26S2)2]·0.25C5H12 | Dx = 1.169 Mg m−3 |
Mr = 785.84 | Cu Kα radiation, λ = 1.54178 Å |
Tetragonal, P41212 | Cell parameters from 9381 reflections |
a = 11.7187 (4) Å | θ = 4.0–72.6° |
c = 65.014 (4) Å | µ = 2.58 mm−1 |
V = 8928.2 (8) Å3 | T = 150 K |
Z = 8 | Column, black |
F(000) = 3348 | 0.21 × 0.11 × 0.05 mm |
Bruker D8 VENTURE PHOTON 3 CPAD diffractometer | 8886 independent reflections |
Radiation source: INCOATEC IµS micro—-focus source | 8592 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.072 |
Detector resolution: 7.3910 pixels mm-1 | θmax = 72.7°, θmin = 4.0° |
φ and ω scans | h = −14→14 |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | k = −14→14 |
Tmin = 0.77, Tmax = 0.88 | l = −80→80 |
203444 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.138 | w = 1/[σ2(Fo2) + (0.0951P)2 + 5.7915P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.003 |
8886 reflections | Δρmax = 1.57 e Å−3 |
497 parameters | Δρmin = −0.40 e Å−3 |
27 restraints | Absolute structure: Refined as an inversion twin. |
Primary atom site location: dual | Absolute structure parameter: 0.03 (2) |
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 2-component inversion twin. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.11325 (6) | 0.50471 (6) | 0.66096 (2) | 0.02572 (18) | |
S1 | 0.16585 (8) | 0.54152 (9) | 0.63052 (2) | 0.0270 (2) | |
S2 | 0.26404 (8) | 0.40913 (9) | 0.66631 (2) | 0.0284 (2) | |
S3 | −0.03961 (8) | 0.59838 (8) | 0.65575 (2) | 0.0264 (2) | |
S4 | 0.06448 (9) | 0.46883 (9) | 0.69166 (2) | 0.0318 (2) | |
C1 | 0.2970 (3) | 0.4783 (3) | 0.62760 (6) | 0.0252 (7) | |
C2 | 0.3415 (3) | 0.4174 (3) | 0.64413 (6) | 0.0253 (7) | |
C3 | −0.1135 (3) | 0.5915 (3) | 0.67829 (6) | 0.0269 (8) | |
C4 | −0.0659 (3) | 0.5317 (3) | 0.69492 (6) | 0.0295 (8) | |
C5 | 0.3489 (3) | 0.4871 (3) | 0.60685 (6) | 0.0244 (7) | |
C6 | 0.3989 (3) | 0.3928 (4) | 0.59745 (6) | 0.0277 (8) | |
H6 | 0.408370 | 0.323934 | 0.604960 | 0.033* | |
C7 | 0.4348 (3) | 0.3990 (4) | 0.57716 (6) | 0.0300 (8) | |
H7 | 0.467590 | 0.333322 | 0.570971 | 0.036* | |
C8 | 0.4244 (3) | 0.4987 (4) | 0.56554 (6) | 0.0303 (8) | |
C9 | 0.3773 (4) | 0.5935 (4) | 0.57528 (6) | 0.0308 (8) | |
H9 | 0.370156 | 0.662995 | 0.567872 | 0.037* | |
C10 | 0.3406 (3) | 0.5888 (4) | 0.59557 (6) | 0.0271 (8) | |
H10 | 0.309538 | 0.655085 | 0.601869 | 0.032* | |
C11 | 0.4587 (4) | 0.5019 (5) | 0.54280 (7) | 0.0394 (10) | |
C12A | 0.3892 (19) | 0.4182 (18) | 0.5312 (2) | 0.074 (7) | 0.461 (19) |
H12A | 0.421610 | 0.407950 | 0.517424 | 0.111* | 0.461 (19) |
H12B | 0.310697 | 0.446374 | 0.530004 | 0.111* | 0.461 (19) |
H12C | 0.389198 | 0.344980 | 0.538470 | 0.111* | 0.461 (19) |
C13A | 0.4460 (16) | 0.6250 (14) | 0.53373 (19) | 0.058 (4) | 0.461 (19) |
H13A | 0.487709 | 0.629958 | 0.520695 | 0.087* | 0.461 (19) |
H13B | 0.477300 | 0.680560 | 0.543481 | 0.087* | 0.461 (19) |
H13C | 0.365115 | 0.641493 | 0.531339 | 0.087* | 0.461 (19) |
C14A | 0.5838 (13) | 0.4692 (18) | 0.54094 (19) | 0.068 (6) | 0.461 (19) |
H14A | 0.593129 | 0.414042 | 0.529742 | 0.102* | 0.461 (19) |
H14B | 0.609666 | 0.435055 | 0.553881 | 0.102* | 0.461 (19) |
H14C | 0.629133 | 0.537554 | 0.537998 | 0.102* | 0.461 (19) |
C12B | 0.3464 (13) | 0.500 (2) | 0.5301 (2) | 0.086 (6) | 0.539 (19) |
H12D | 0.311742 | 0.576312 | 0.530291 | 0.129* | 0.539 (19) |
H12E | 0.293295 | 0.444965 | 0.536151 | 0.129* | 0.539 (19) |
H12F | 0.363294 | 0.478302 | 0.515887 | 0.129* | 0.539 (19) |
C13B | 0.530 (2) | 0.6003 (19) | 0.5382 (2) | 0.106 (10) | 0.539 (19) |
H13D | 0.492102 | 0.669788 | 0.543104 | 0.158* | 0.539 (19) |
H13E | 0.541539 | 0.605513 | 0.523298 | 0.158* | 0.539 (19) |
H13F | 0.603756 | 0.591920 | 0.545073 | 0.158* | 0.539 (19) |
C14B | 0.510 (2) | 0.3851 (15) | 0.5356 (2) | 0.097 (8) | 0.539 (19) |
H14D | 0.536602 | 0.391757 | 0.521379 | 0.146* | 0.539 (19) |
H14E | 0.451461 | 0.325667 | 0.536495 | 0.146* | 0.539 (19) |
H14F | 0.574518 | 0.364714 | 0.544519 | 0.146* | 0.539 (19) |
C15 | 0.4557 (3) | 0.3629 (3) | 0.64462 (6) | 0.0247 (7) | |
C16 | 0.4669 (3) | 0.2503 (3) | 0.65136 (6) | 0.0257 (7) | |
H16 | 0.400958 | 0.207967 | 0.655083 | 0.031* | |
C17 | 0.5738 (3) | 0.1998 (3) | 0.65265 (6) | 0.0267 (7) | |
H17 | 0.579397 | 0.122266 | 0.656774 | 0.032* | |
C18 | 0.6728 (3) | 0.2598 (3) | 0.64807 (6) | 0.0254 (7) | |
C19 | 0.6602 (3) | 0.3733 (4) | 0.64133 (7) | 0.0329 (9) | |
H19 | 0.726089 | 0.416447 | 0.637899 | 0.039* | |
C20 | 0.5537 (3) | 0.4231 (4) | 0.63961 (7) | 0.0331 (9) | |
H20 | 0.547600 | 0.499669 | 0.634928 | 0.040* | |
C21 | 0.7914 (3) | 0.2093 (3) | 0.65087 (6) | 0.0289 (8) | |
C22 | 0.8510 (4) | 0.2736 (4) | 0.66836 (8) | 0.0411 (10) | |
H22A | 0.856736 | 0.354653 | 0.664813 | 0.062* | |
H22B | 0.927732 | 0.242173 | 0.670390 | 0.062* | |
H22C | 0.806794 | 0.265018 | 0.681056 | 0.062* | |
C23 | 0.7887 (4) | 0.0820 (4) | 0.65608 (8) | 0.0383 (10) | |
H23A | 0.753235 | 0.071129 | 0.669589 | 0.057* | |
H23B | 0.866802 | 0.052053 | 0.656359 | 0.057* | |
H23C | 0.744385 | 0.041142 | 0.645628 | 0.057* | |
C24 | 0.8616 (4) | 0.2242 (5) | 0.63087 (9) | 0.0492 (13) | |
H24A | 0.816219 | 0.198526 | 0.619089 | 0.074* | |
H24B | 0.931582 | 0.178616 | 0.631763 | 0.074* | |
H24C | 0.881503 | 0.304810 | 0.629110 | 0.074* | |
C25 | −0.2282 (3) | 0.6431 (3) | 0.67841 (6) | 0.0267 (8) | |
C26 | −0.3229 (4) | 0.5781 (4) | 0.68385 (9) | 0.0425 (11) | |
H26 | −0.313031 | 0.501166 | 0.688097 | 0.051* | |
C27 | −0.4317 (4) | 0.6248 (4) | 0.68311 (9) | 0.0453 (12) | |
H27 | −0.495056 | 0.578704 | 0.686895 | 0.054* | |
C28 | −0.4510 (3) | 0.7372 (4) | 0.67700 (6) | 0.0291 (8) | |
C29 | −0.3557 (4) | 0.8014 (4) | 0.67168 (7) | 0.0319 (8) | |
H29 | −0.365326 | 0.878569 | 0.667577 | 0.038* | |
C30 | −0.2463 (4) | 0.7548 (4) | 0.67226 (7) | 0.0319 (9) | |
H30 | −0.182968 | 0.800535 | 0.668360 | 0.038* | |
C31 | −0.5721 (4) | 0.7830 (4) | 0.67471 (7) | 0.0347 (9) | |
C32 | −0.5777 (5) | 0.9115 (5) | 0.67685 (13) | 0.0668 (19) | |
H32A | −0.542830 | 0.934267 | 0.689922 | 0.100* | |
H32B | −0.657541 | 0.936162 | 0.676570 | 0.100* | |
H32C | −0.536216 | 0.947115 | 0.665444 | 0.100* | |
C33 | −0.6538 (5) | 0.7297 (6) | 0.69042 (11) | 0.0655 (18) | |
H33A | −0.620952 | 0.736244 | 0.704226 | 0.098* | |
H33B | −0.665624 | 0.649050 | 0.687078 | 0.098* | |
H33C | −0.727136 | 0.769902 | 0.689986 | 0.098* | |
C34 | −0.6154 (5) | 0.7513 (6) | 0.65312 (9) | 0.0584 (15) | |
H34A | −0.698181 | 0.762907 | 0.652457 | 0.088* | |
H34B | −0.597801 | 0.671104 | 0.650284 | 0.088* | |
H34C | −0.577955 | 0.799788 | 0.642861 | 0.088* | |
C35 | −0.1179 (4) | 0.5215 (4) | 0.71562 (6) | 0.0331 (8) | |
C36 | −0.1179 (5) | 0.4183 (4) | 0.72576 (7) | 0.0448 (11) | |
H36 | −0.088892 | 0.352356 | 0.719052 | 0.054* | |
C37 | −0.1602 (5) | 0.4093 (5) | 0.74586 (7) | 0.0480 (12) | |
H37 | −0.159235 | 0.337265 | 0.752549 | 0.058* | |
C38 | −0.2035 (5) | 0.5031 (5) | 0.75617 (7) | 0.0464 (12) | |
C39 | −0.2077 (6) | 0.6049 (5) | 0.74547 (8) | 0.0572 (15) | |
H39 | −0.239496 | 0.669983 | 0.752028 | 0.069* | |
C40 | −0.1672 (5) | 0.6156 (4) | 0.72546 (8) | 0.0494 (13) | |
H40 | −0.173016 | 0.686603 | 0.718481 | 0.059* | |
C41 | −0.2483 (5) | 0.4953 (5) | 0.77823 (7) | 0.0585 (16) | |
C42A | −0.1891 (16) | 0.3937 (11) | 0.78986 (19) | 0.051 (4)* | 0.48 (3) |
H42A | −0.218619 | 0.389213 | 0.803941 | 0.077* | 0.48 (3) |
H42B | −0.106439 | 0.406361 | 0.790249 | 0.077* | 0.48 (3) |
H42C | −0.205229 | 0.322032 | 0.782647 | 0.077* | 0.48 (3) |
C43A | −0.227 (2) | 0.6045 (12) | 0.7902 (2) | 0.059 (4)* | 0.48 (3) |
H43A | −0.267924 | 0.667602 | 0.783673 | 0.089* | 0.48 (3) |
H43B | −0.144626 | 0.621226 | 0.790162 | 0.089* | 0.48 (3) |
H43C | −0.253082 | 0.595077 | 0.804358 | 0.089* | 0.48 (3) |
C44A | −0.3728 (12) | 0.465 (3) | 0.7777 (3) | 0.083 (6)* | 0.48 (3) |
H44A | −0.402360 | 0.461900 | 0.791837 | 0.124* | 0.48 (3) |
H44B | −0.382656 | 0.390692 | 0.771135 | 0.124* | 0.48 (3) |
H44C | −0.414595 | 0.523307 | 0.769961 | 0.124* | 0.48 (3) |
C42B | −0.2387 (19) | 0.3819 (9) | 0.7882 (2) | 0.061 (4)* | 0.52 (3) |
H42D | −0.284956 | 0.326412 | 0.780606 | 0.092* | 0.52 (3) |
H42E | −0.266099 | 0.386955 | 0.802407 | 0.092* | 0.52 (3) |
H42F | −0.158737 | 0.357487 | 0.788152 | 0.092* | 0.52 (3) |
C43B | −0.1921 (14) | 0.5929 (10) | 0.79087 (17) | 0.044 (3)* | 0.52 (3) |
H43D | −0.210581 | 0.583221 | 0.805470 | 0.066* | 0.52 (3) |
H43E | −0.221200 | 0.666640 | 0.786075 | 0.066* | 0.52 (3) |
H43F | −0.109150 | 0.590326 | 0.789038 | 0.066* | 0.52 (3) |
C44B | −0.3796 (9) | 0.5117 (18) | 0.7777 (2) | 0.064 (4)* | 0.52 (3) |
H44D | −0.414406 | 0.449483 | 0.769802 | 0.096* | 0.52 (3) |
H44E | −0.397658 | 0.584817 | 0.771121 | 0.096* | 0.52 (3) |
H44F | −0.409572 | 0.511207 | 0.791743 | 0.096* | 0.52 (3) |
C45 | −0.6695 (19) | 0.6695 (19) | 0.750000 | 0.104 (9)* | 0.5 |
H45A | −0.625613 | 0.640961 | 0.738040 | 0.125* | 0.25 |
H45B | −0.640954 | 0.625607 | 0.761958 | 0.125* | 0.25 |
C46 | −0.621 (2) | 0.796 (2) | 0.7537 (4) | 0.126 (8)* | 0.5 |
H46A | −0.665818 | 0.849448 | 0.745177 | 0.152* | 0.5 |
H46B | −0.633358 | 0.816350 | 0.768245 | 0.152* | 0.5 |
C47 | −0.497 (2) | 0.814 (2) | 0.7489 (4) | 0.138 (9)* | 0.5 |
H47A | −0.476819 | 0.893635 | 0.751644 | 0.208* | 0.5 |
H47B | −0.450667 | 0.763562 | 0.757474 | 0.208* | 0.5 |
H47C | −0.483233 | 0.796770 | 0.734331 | 0.208* | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0209 (3) | 0.0316 (4) | 0.0247 (3) | 0.0036 (2) | 0.0032 (2) | 0.0019 (3) |
S1 | 0.0211 (4) | 0.0343 (5) | 0.0257 (4) | 0.0055 (3) | 0.0021 (3) | 0.0047 (4) |
S2 | 0.0234 (4) | 0.0357 (5) | 0.0263 (4) | 0.0056 (4) | 0.0023 (3) | 0.0051 (4) |
S3 | 0.0229 (4) | 0.0314 (5) | 0.0249 (4) | 0.0042 (3) | 0.0037 (3) | 0.0034 (3) |
S4 | 0.0290 (5) | 0.0412 (5) | 0.0252 (4) | 0.0091 (4) | 0.0026 (3) | 0.0044 (4) |
C1 | 0.0194 (16) | 0.0253 (17) | 0.0309 (18) | −0.0014 (14) | 0.0005 (14) | −0.0002 (15) |
C2 | 0.0218 (17) | 0.0276 (18) | 0.0266 (17) | −0.0019 (14) | 0.0007 (14) | −0.0009 (15) |
C3 | 0.0256 (18) | 0.0277 (19) | 0.0275 (18) | −0.0003 (15) | 0.0060 (15) | −0.0006 (15) |
C4 | 0.0286 (18) | 0.0312 (19) | 0.0287 (18) | 0.0025 (16) | 0.0030 (15) | 0.0009 (15) |
C5 | 0.0164 (15) | 0.0282 (19) | 0.0286 (17) | −0.0003 (13) | −0.0017 (13) | 0.0029 (15) |
C6 | 0.0214 (17) | 0.0296 (19) | 0.0320 (19) | 0.0018 (15) | 0.0000 (15) | 0.0013 (15) |
C7 | 0.0244 (18) | 0.034 (2) | 0.032 (2) | 0.0011 (15) | 0.0011 (15) | −0.0030 (16) |
C8 | 0.0217 (18) | 0.042 (2) | 0.0275 (19) | −0.0056 (16) | 0.0012 (15) | −0.0005 (17) |
C9 | 0.0264 (19) | 0.035 (2) | 0.031 (2) | −0.0045 (16) | −0.0010 (15) | 0.0049 (16) |
C10 | 0.0215 (17) | 0.0301 (19) | 0.0295 (19) | −0.0002 (15) | −0.0007 (14) | 0.0033 (16) |
C11 | 0.041 (2) | 0.052 (3) | 0.0252 (19) | −0.005 (2) | 0.0031 (18) | −0.0001 (19) |
C12A | 0.095 (15) | 0.097 (14) | 0.029 (6) | −0.052 (12) | 0.006 (7) | −0.005 (7) |
C13A | 0.072 (10) | 0.074 (9) | 0.028 (5) | 0.007 (8) | 0.012 (6) | 0.019 (5) |
C14A | 0.061 (8) | 0.111 (15) | 0.032 (6) | 0.024 (9) | 0.031 (6) | 0.017 (7) |
C12B | 0.064 (8) | 0.16 (2) | 0.037 (6) | 0.010 (10) | −0.011 (5) | −0.001 (9) |
C13B | 0.133 (19) | 0.132 (17) | 0.052 (8) | −0.075 (16) | 0.049 (11) | −0.023 (9) |
C14B | 0.16 (2) | 0.083 (11) | 0.052 (7) | 0.056 (13) | 0.039 (10) | −0.007 (7) |
C15 | 0.0208 (17) | 0.0276 (18) | 0.0257 (17) | 0.0022 (14) | −0.0011 (14) | 0.0024 (14) |
C16 | 0.0232 (17) | 0.0265 (18) | 0.0274 (17) | −0.0030 (14) | −0.0003 (14) | −0.0008 (15) |
C17 | 0.0266 (18) | 0.0231 (17) | 0.0304 (18) | −0.0003 (14) | −0.0009 (15) | 0.0011 (15) |
C18 | 0.0214 (17) | 0.0282 (19) | 0.0266 (17) | 0.0034 (15) | −0.0009 (14) | 0.0000 (14) |
C19 | 0.0205 (18) | 0.031 (2) | 0.048 (2) | 0.0012 (15) | 0.0031 (17) | 0.0103 (18) |
C20 | 0.0236 (19) | 0.0287 (19) | 0.047 (2) | 0.0016 (16) | 0.0011 (17) | 0.0137 (18) |
C21 | 0.0240 (18) | 0.030 (2) | 0.033 (2) | 0.0049 (15) | 0.0013 (15) | 0.0011 (16) |
C22 | 0.026 (2) | 0.042 (2) | 0.055 (3) | 0.0059 (18) | −0.0105 (19) | −0.004 (2) |
C23 | 0.030 (2) | 0.030 (2) | 0.055 (3) | 0.0086 (17) | −0.0027 (19) | 0.0017 (19) |
C24 | 0.035 (2) | 0.060 (3) | 0.053 (3) | 0.017 (2) | 0.017 (2) | 0.011 (2) |
C25 | 0.0255 (19) | 0.0282 (19) | 0.0264 (17) | 0.0009 (15) | 0.0043 (14) | −0.0009 (15) |
C26 | 0.030 (2) | 0.032 (2) | 0.066 (3) | 0.0067 (18) | 0.016 (2) | 0.013 (2) |
C27 | 0.028 (2) | 0.030 (2) | 0.078 (4) | 0.0019 (17) | 0.019 (2) | 0.013 (2) |
C28 | 0.0240 (18) | 0.030 (2) | 0.0337 (19) | 0.0036 (15) | 0.0044 (15) | −0.0020 (16) |
C29 | 0.027 (2) | 0.0261 (19) | 0.042 (2) | 0.0004 (15) | 0.0012 (17) | 0.0051 (17) |
C30 | 0.027 (2) | 0.030 (2) | 0.039 (2) | −0.0010 (16) | 0.0019 (16) | 0.0042 (17) |
C31 | 0.029 (2) | 0.031 (2) | 0.045 (2) | 0.0054 (16) | 0.0057 (17) | 0.0025 (17) |
C32 | 0.034 (3) | 0.034 (3) | 0.133 (6) | 0.013 (2) | −0.009 (3) | −0.015 (3) |
C33 | 0.033 (3) | 0.078 (4) | 0.086 (4) | 0.019 (3) | 0.025 (3) | 0.022 (4) |
C34 | 0.036 (3) | 0.077 (4) | 0.062 (3) | 0.023 (3) | −0.009 (2) | −0.018 (3) |
C35 | 0.032 (2) | 0.039 (2) | 0.0279 (19) | 0.0029 (17) | 0.0062 (16) | 0.0016 (16) |
C36 | 0.062 (3) | 0.039 (2) | 0.034 (2) | 0.009 (2) | 0.014 (2) | 0.0048 (19) |
C37 | 0.070 (4) | 0.042 (3) | 0.031 (2) | 0.003 (2) | 0.013 (2) | 0.007 (2) |
C38 | 0.063 (3) | 0.047 (3) | 0.029 (2) | −0.006 (2) | 0.013 (2) | 0.000 (2) |
C39 | 0.085 (4) | 0.046 (3) | 0.041 (3) | 0.006 (3) | 0.024 (3) | −0.008 (2) |
C40 | 0.075 (4) | 0.038 (2) | 0.036 (2) | 0.008 (2) | 0.019 (2) | 0.006 (2) |
C41 | 0.087 (4) | 0.056 (3) | 0.032 (2) | −0.011 (3) | 0.023 (3) | −0.002 (2) |
Ni1—S1 | 2.1174 (11) | C24—H24B | 0.9800 |
Ni1—S4 | 2.1185 (11) | C24—H24C | 0.9800 |
Ni1—S2 | 2.1207 (11) | C25—C30 | 1.386 (6) |
Ni1—S3 | 2.1281 (11) | C25—C26 | 1.392 (6) |
S1—C1 | 1.716 (4) | C26—C27 | 1.389 (6) |
S2—C2 | 1.707 (4) | C26—H26 | 0.9500 |
S3—C3 | 1.704 (4) | C27—C28 | 1.394 (6) |
S4—C4 | 1.710 (4) | C27—H27 | 0.9500 |
C1—C2 | 1.392 (5) | C28—C29 | 1.390 (6) |
C1—C5 | 1.484 (5) | C28—C31 | 1.525 (6) |
C2—C15 | 1.483 (5) | C29—C30 | 1.394 (6) |
C3—C4 | 1.404 (6) | C29—H29 | 0.9500 |
C3—C25 | 1.473 (5) | C30—H30 | 0.9500 |
C4—C35 | 1.482 (5) | C31—C32 | 1.513 (7) |
C5—C6 | 1.392 (6) | C31—C33 | 1.533 (7) |
C5—C10 | 1.402 (5) | C31—C34 | 1.538 (7) |
C6—C7 | 1.386 (6) | C32—H32A | 0.9800 |
C6—H6 | 0.9500 | C32—H32B | 0.9800 |
C7—C8 | 1.396 (6) | C32—H32C | 0.9800 |
C7—H7 | 0.9500 | C33—H33A | 0.9800 |
C8—C9 | 1.393 (6) | C33—H33B | 0.9800 |
C8—C11 | 1.532 (5) | C33—H33C | 0.9800 |
C9—C10 | 1.389 (6) | C34—H34A | 0.9800 |
C9—H9 | 0.9500 | C34—H34B | 0.9800 |
C10—H10 | 0.9500 | C34—H34C | 0.9800 |
C11—C13B | 1.455 (16) | C35—C36 | 1.378 (7) |
C11—C12A | 1.481 (15) | C35—C40 | 1.400 (7) |
C11—C14A | 1.520 (14) | C36—C37 | 1.402 (6) |
C11—C12B | 1.553 (14) | C36—H36 | 0.9500 |
C11—C13A | 1.566 (15) | C37—C38 | 1.384 (8) |
C11—C14B | 1.567 (14) | C37—H37 | 0.9500 |
C12A—H12A | 0.9800 | C38—C39 | 1.382 (8) |
C12A—H12B | 0.9800 | C38—C41 | 1.530 (6) |
C12A—H12C | 0.9800 | C39—C40 | 1.391 (7) |
C13A—H13A | 0.9800 | C39—H39 | 0.9500 |
C13A—H13B | 0.9800 | C40—H40 | 0.9500 |
C13A—H13C | 0.9800 | C41—C42B | 1.482 (10) |
C14A—H14A | 0.9800 | C41—C44A | 1.501 (12) |
C14A—H14B | 0.9800 | C41—C43A | 1.518 (11) |
C14A—H14C | 0.9800 | C41—C44B | 1.551 (11) |
C12B—H12D | 0.9800 | C41—C43B | 1.554 (10) |
C12B—H12E | 0.9800 | C41—C42A | 1.572 (10) |
C12B—H12F | 0.9800 | C42A—H42A | 0.9800 |
C13B—H13D | 0.9800 | C42A—H42B | 0.9800 |
C13B—H13E | 0.9800 | C42A—H42C | 0.9800 |
C13B—H13F | 0.9800 | C43A—H43A | 0.9800 |
C14B—H14D | 0.9800 | C43A—H43B | 0.9800 |
C14B—H14E | 0.9800 | C43A—H43C | 0.9800 |
C14B—H14F | 0.9800 | C44A—H44A | 0.9800 |
C15—C20 | 1.387 (6) | C44A—H44B | 0.9800 |
C15—C16 | 1.397 (5) | C44A—H44C | 0.9800 |
C16—C17 | 1.388 (6) | C42B—H42D | 0.9800 |
C16—H16 | 0.9500 | C42B—H42E | 0.9800 |
C17—C18 | 1.389 (6) | C42B—H42F | 0.9800 |
C17—H17 | 0.9500 | C43B—H43D | 0.9800 |
C18—C19 | 1.409 (6) | C43B—H43E | 0.9800 |
C18—C21 | 1.521 (5) | C43B—H43F | 0.9800 |
C19—C20 | 1.382 (6) | C44B—H44D | 0.9800 |
C19—H19 | 0.9500 | C44B—H44E | 0.9800 |
C20—H20 | 0.9500 | C44B—H44F | 0.9800 |
C21—C23 | 1.530 (6) | C45—C46i | 1.61 (3) |
C21—C22 | 1.533 (6) | C45—C46 | 1.61 (3) |
C21—C24 | 1.548 (6) | C45—H45A | 0.9900 |
C22—H22A | 0.9800 | C45—H45B | 0.9900 |
C22—H22B | 0.9800 | C46—C47 | 1.49 (3) |
C22—H22C | 0.9800 | C46—H46A | 0.9900 |
C23—H23A | 0.9800 | C46—H46B | 0.9900 |
C23—H23B | 0.9800 | C47—H47A | 0.9800 |
C23—H23C | 0.9800 | C47—H47B | 0.9800 |
C24—H24A | 0.9800 | C47—H47C | 0.9800 |
S1—Ni1—S4 | 178.67 (5) | H24A—C24—H24C | 109.5 |
S1—Ni1—S2 | 91.05 (4) | H24B—C24—H24C | 109.5 |
S4—Ni1—S2 | 88.02 (4) | C30—C25—C26 | 117.9 (4) |
S1—Ni1—S3 | 89.49 (4) | C30—C25—C3 | 121.7 (4) |
S4—Ni1—S3 | 91.45 (4) | C26—C25—C3 | 120.3 (4) |
S2—Ni1—S3 | 179.10 (6) | C27—C26—C25 | 120.6 (4) |
C1—S1—Ni1 | 106.01 (14) | C27—C26—H26 | 119.7 |
C2—S2—Ni1 | 105.95 (14) | C25—C26—H26 | 119.7 |
C3—S3—Ni1 | 105.44 (14) | C26—C27—C28 | 122.1 (4) |
C4—S4—Ni1 | 105.80 (14) | C26—C27—H27 | 119.0 |
C2—C1—C5 | 125.8 (3) | C28—C27—H27 | 119.0 |
C2—C1—S1 | 118.2 (3) | C29—C28—C27 | 116.9 (4) |
C5—C1—S1 | 115.9 (3) | C29—C28—C31 | 122.2 (4) |
C1—C2—C15 | 125.2 (3) | C27—C28—C31 | 120.7 (4) |
C1—C2—S2 | 118.8 (3) | C28—C29—C30 | 121.4 (4) |
C15—C2—S2 | 115.9 (3) | C28—C29—H29 | 119.3 |
C4—C3—C25 | 124.3 (4) | C30—C29—H29 | 119.3 |
C4—C3—S3 | 119.0 (3) | C25—C30—C29 | 121.3 (4) |
C25—C3—S3 | 116.6 (3) | C25—C30—H30 | 119.4 |
C3—C4—C35 | 125.2 (4) | C29—C30—H30 | 119.4 |
C3—C4—S4 | 118.3 (3) | C32—C31—C28 | 112.4 (4) |
C35—C4—S4 | 116.4 (3) | C32—C31—C33 | 108.5 (5) |
C6—C5—C10 | 118.3 (4) | C28—C31—C33 | 111.9 (4) |
C6—C5—C1 | 121.1 (4) | C32—C31—C34 | 108.0 (5) |
C10—C5—C1 | 120.4 (4) | C28—C31—C34 | 108.2 (4) |
C7—C6—C5 | 120.2 (4) | C33—C31—C34 | 107.7 (5) |
C7—C6—H6 | 119.9 | C31—C32—H32A | 109.5 |
C5—C6—H6 | 119.9 | C31—C32—H32B | 109.5 |
C6—C7—C8 | 122.2 (4) | H32A—C32—H32B | 109.5 |
C6—C7—H7 | 118.9 | C31—C32—H32C | 109.5 |
C8—C7—H7 | 118.9 | H32A—C32—H32C | 109.5 |
C9—C8—C7 | 117.1 (4) | H32B—C32—H32C | 109.5 |
C9—C8—C11 | 121.5 (4) | C31—C33—H33A | 109.5 |
C7—C8—C11 | 121.3 (4) | C31—C33—H33B | 109.5 |
C10—C9—C8 | 121.6 (4) | H33A—C33—H33B | 109.5 |
C10—C9—H9 | 119.2 | C31—C33—H33C | 109.5 |
C8—C9—H9 | 119.2 | H33A—C33—H33C | 109.5 |
C9—C10—C5 | 120.6 (4) | H33B—C33—H33C | 109.5 |
C9—C10—H10 | 119.7 | C31—C34—H34A | 109.5 |
C5—C10—H10 | 119.7 | C31—C34—H34B | 109.5 |
C12A—C11—C14A | 108.9 (12) | H34A—C34—H34B | 109.5 |
C13B—C11—C8 | 111.6 (7) | C31—C34—H34C | 109.5 |
C12A—C11—C8 | 109.3 (6) | H34A—C34—H34C | 109.5 |
C14A—C11—C8 | 108.9 (6) | H34B—C34—H34C | 109.5 |
C13B—C11—C12B | 112.7 (13) | C36—C35—C40 | 118.2 (4) |
C8—C11—C12B | 106.9 (6) | C36—C35—C4 | 120.3 (4) |
C12A—C11—C13A | 111.5 (11) | C40—C35—C4 | 121.4 (4) |
C14A—C11—C13A | 107.1 (10) | C35—C36—C37 | 120.8 (5) |
C8—C11—C13A | 111.2 (6) | C35—C36—H36 | 119.6 |
C13B—C11—C14B | 114.3 (12) | C37—C36—H36 | 119.6 |
C8—C11—C14B | 111.5 (6) | C38—C37—C36 | 121.5 (5) |
C12B—C11—C14B | 99.0 (12) | C38—C37—H37 | 119.3 |
C11—C12A—H12A | 109.5 | C36—C37—H37 | 119.3 |
C11—C12A—H12B | 109.5 | C39—C38—C37 | 117.0 (4) |
H12A—C12A—H12B | 109.5 | C39—C38—C41 | 120.8 (5) |
C11—C12A—H12C | 109.5 | C37—C38—C41 | 122.2 (5) |
H12A—C12A—H12C | 109.5 | C38—C39—C40 | 122.5 (5) |
H12B—C12A—H12C | 109.5 | C38—C39—H39 | 118.8 |
C11—C13A—H13A | 109.5 | C40—C39—H39 | 118.8 |
C11—C13A—H13B | 109.5 | C39—C40—C35 | 119.8 (5) |
H13A—C13A—H13B | 109.5 | C39—C40—H40 | 120.1 |
C11—C13A—H13C | 109.5 | C35—C40—H40 | 120.1 |
H13A—C13A—H13C | 109.5 | C44A—C41—C43A | 111.8 (12) |
H13B—C13A—H13C | 109.5 | C42B—C41—C38 | 115.9 (7) |
C11—C14A—H14A | 109.5 | C44A—C41—C38 | 109.1 (9) |
C11—C14A—H14B | 109.5 | C43A—C41—C38 | 111.8 (8) |
H14A—C14A—H14B | 109.5 | C42B—C41—C44B | 101.3 (9) |
C11—C14A—H14C | 109.5 | C38—C41—C44B | 108.1 (7) |
H14A—C14A—H14C | 109.5 | C42B—C41—C43B | 113.4 (8) |
H14B—C14A—H14C | 109.5 | C38—C41—C43B | 107.8 (6) |
C11—C12B—H12D | 109.5 | C44B—C41—C43B | 110.0 (9) |
C11—C12B—H12E | 109.5 | C44A—C41—C42A | 105.1 (11) |
H12D—C12B—H12E | 109.5 | C43A—C41—C42A | 108.6 (9) |
C11—C12B—H12F | 109.5 | C38—C41—C42A | 110.2 (7) |
H12D—C12B—H12F | 109.5 | C41—C42A—H42A | 109.5 |
H12E—C12B—H12F | 109.5 | C41—C42A—H42B | 109.5 |
C11—C13B—H13D | 109.5 | H42A—C42A—H42B | 109.5 |
C11—C13B—H13E | 109.5 | C41—C42A—H42C | 109.5 |
H13D—C13B—H13E | 109.5 | H42A—C42A—H42C | 109.5 |
C11—C13B—H13F | 109.5 | H42B—C42A—H42C | 109.5 |
H13D—C13B—H13F | 109.5 | C41—C43A—H43A | 109.5 |
H13E—C13B—H13F | 109.5 | C41—C43A—H43B | 109.5 |
C11—C14B—H14D | 109.5 | H43A—C43A—H43B | 109.5 |
C11—C14B—H14E | 109.5 | C41—C43A—H43C | 109.5 |
H14D—C14B—H14E | 109.5 | H43A—C43A—H43C | 109.5 |
C11—C14B—H14F | 109.5 | H43B—C43A—H43C | 109.5 |
H14D—C14B—H14F | 109.5 | C41—C44A—H44A | 109.5 |
H14E—C14B—H14F | 109.5 | C41—C44A—H44B | 109.5 |
C20—C15—C16 | 118.5 (4) | H44A—C44A—H44B | 109.5 |
C20—C15—C2 | 121.5 (3) | C41—C44A—H44C | 109.5 |
C16—C15—C2 | 119.9 (4) | H44A—C44A—H44C | 109.5 |
C17—C16—C15 | 120.4 (4) | H44B—C44A—H44C | 109.5 |
C17—C16—H16 | 119.8 | C41—C42B—H42D | 109.5 |
C15—C16—H16 | 119.8 | C41—C42B—H42E | 109.5 |
C16—C17—C18 | 121.7 (4) | H42D—C42B—H42E | 109.5 |
C16—C17—H17 | 119.1 | C41—C42B—H42F | 109.5 |
C18—C17—H17 | 119.1 | H42D—C42B—H42F | 109.5 |
C17—C18—C19 | 117.1 (4) | H42E—C42B—H42F | 109.5 |
C17—C18—C21 | 122.7 (4) | C41—C43B—H43D | 109.5 |
C19—C18—C21 | 120.1 (4) | C41—C43B—H43E | 109.5 |
C20—C19—C18 | 121.3 (4) | H43D—C43B—H43E | 109.5 |
C20—C19—H19 | 119.3 | C41—C43B—H43F | 109.5 |
C18—C19—H19 | 119.3 | H43D—C43B—H43F | 109.5 |
C19—C20—C15 | 120.9 (4) | H43E—C43B—H43F | 109.5 |
C19—C20—H20 | 119.6 | C41—C44B—H44D | 109.5 |
C15—C20—H20 | 119.6 | C41—C44B—H44E | 109.5 |
C18—C21—C23 | 112.8 (3) | H44D—C44B—H44E | 109.5 |
C18—C21—C22 | 108.3 (3) | C41—C44B—H44F | 109.5 |
C23—C21—C22 | 109.0 (4) | H44D—C44B—H44F | 109.5 |
C18—C21—C24 | 109.9 (3) | H44E—C44B—H44F | 109.5 |
C23—C21—C24 | 107.9 (4) | C46i—C45—C46 | 133 (3) |
C22—C21—C24 | 109.0 (4) | C46i—C45—H45A | 104.0 |
C21—C22—H22A | 109.5 | C46—C45—H45A | 104.0 |
C21—C22—H22B | 109.5 | C46i—C45—H45B | 104.0 |
H22A—C22—H22B | 109.5 | C46—C45—H45B | 104.0 |
C21—C22—H22C | 109.5 | H45A—C45—H45B | 105.5 |
H22A—C22—H22C | 109.5 | C47—C46—C45 | 116 (2) |
H22B—C22—H22C | 109.5 | C47—C46—H46A | 108.2 |
C21—C23—H23A | 109.5 | C45—C46—H46A | 108.2 |
C21—C23—H23B | 109.5 | C47—C46—H46B | 108.2 |
H23A—C23—H23B | 109.5 | C45—C46—H46B | 108.2 |
C21—C23—H23C | 109.5 | H46A—C46—H46B | 107.3 |
H23A—C23—H23C | 109.5 | C46—C47—H47A | 109.5 |
H23B—C23—H23C | 109.5 | C46—C47—H47B | 109.5 |
C21—C24—H24A | 109.5 | H47A—C47—H47B | 109.5 |
C21—C24—H24B | 109.5 | C46—C47—H47C | 109.5 |
H24A—C24—H24B | 109.5 | H47A—C47—H47C | 109.5 |
C21—C24—H24C | 109.5 | H47B—C47—H47C | 109.5 |
Symmetry code: (i) −y, −x, −z+3/2. |
φ represents the angles between the MS4C4 MS4C4 mean plane and the aryl C6 planes. Values of φ that were refined in SHELXL carry an uncertainty. All other values of φ were evaluated using Mercury 3.7. |
Ar, M | Space group | M—S | S—C | C—Cchelate | φ | Refcode |
Ph, Ni2+ | P1 | 2.120, 2.127 | 1.701 (4), 1.695 (4) | 1.424 | 50.64, 44.79 | NIDPDS01a |
2.125, 2.125 | 1.718 (4), 1.702 (4) | 1.404 | 53.06, 34.75 | |||
Ph, Ni2+ | P21/n | 2.1209 (6) | 1.7152 (17) | 1.388 (2) | 34.20 | NIDPDS03b |
2.1226 (7) | 1.7035 (17) | 65.77 | ||||
Ph, Pd2+ | P21/n | 2.2502, 2.2496 | 1.696 (2), 1.712 (2) | 1.399 (3) | 35.83, 66.40 | GOLRAAc |
Ph, Pt2+ | P21/n | 2.2443, 2.2460 | 1.6978, 1.7161 | 1.3965 | 35.87, 66.68 | BUGDUCd |
MeO-p-C6H4, Ni2+ | P1 | 2.1221 (6) | 1.7169 (19) | 29.40 | SICWORe | |
2.1218 (6) | 1.7029 (19) | 1.393 (3) | 53.00 | |||
2.1341 (5) | 1.7171 (19) | 1.391 (3) | 41.61 | |||
2.1182 (6) | 1.7100 (19) | 39.91 | ||||
MeO-p-C6H4, Pd2+ | P1 | 2.2535 (18) | 1.699 (6) | 40.24 | SONPUIf | |
2.2566 (18) | 1.715 (6) | 1.417 (9) | 43.57 | |||
2.2706 (18) | 1.711 (6) | 1.411 (9) | 30.22 | |||
2.2505 (18) | 1.708 (6) | 51.76 | ||||
MeO-p-C6H4, Pt2+ | P1 | 2.240 (2), 2.243 (2) | 1.696 (9), 1.710 (7) | 1.402 (12) | 40.83, 42.04 | SOPMOBf |
2.245 (3), 2.249 (3) | 1.712 (8), 1.709 (9) | 1.391 (12) | 45.82, 38.35 | |||
MeO-p-C6H4, Ni2+ | P1 | 2.104 (3), 2.108 (3) | 1.689 (5), 1.699 (5) | 1.394 (6) | 40.41, 43.96 | ECEKAAb |
2.103 (3), 2.106 (3) | 1.682 (5), 1.698 (5) | 1.386 (6) | 54.91, 35.28 | |||
Cl-p-C6H4, Ni2+ | P1 | 2.1277 (7) | 1.706 (2) | 35.39 (9) | DATTURg | |
2.1192 (6) | 1.704 (2) | 1.399 (3) | 54.34 (5) | |||
2.1207 (7) | 1.706 (2) | 1.391 (3) | 40.05 (6) | |||
2.1261 (6) | 1.713 (2) | 42.99 (7) | ||||
3,5-(MeO)2-4-BuO-C6H2, Ni2+ | P21/n | 2.112 | 1.67 (1) | 45.55 | JUHJURh | |
2.123 | 1.69 (2) | 1.39 (2) | 48.73 | |||
tBu-p-C6H4, Ni2+, 1 | P41212 | 2.1175 (11) | 1.717 (4) | 41.7 (1) | This work | |
2.1206 (12) | 1.705 (4) | 1.393 (6) | 53.5 (1) | |||
2.1280 (11) | 1.705 (4) | 1.403 (6) | 53.4 (1) | |||
2.1185 (11) | 1.709 (4) | 44.5 (2) | ||||
tBu-p-C6H4, Pd2+ | Pna21 | 2.2503 (10) | 44.16 | TEYSEWi | ||
2.2443 (10) | 1.707 (4) | 1.393 (5) | 49.40 | |||
2.2667 (10) | 1.712 (4) | 51.77 | ||||
2.2440 (10) | 51.38 | |||||
tBu-p-C6H4, Pt2+ | Pna21 | 2.243 (2), 2.242 (2) | 1.728 (9), 1.729 (8) | 1.381 (12) | 48.37, 44.80 | TIDBEOj |
2.259 (2), 2.243 (2) | 1.709 (10), 1.685 (9) | 1.404 (13) | 52.30, 52.63 | |||
tBu-p-C6H4, Au3+ | P41212 | 2.284 (5), 2.288 (5) | 1.74 (2), 1.745 (18) | 1.38 (2) | 41.16, 56.21 | TEYSASi |
2.290 (5), 2.303 (5) | 1.751 (19). 1.76 (2) | 1.33 (2) | 47.30, 54.24 |
Notes: (a) Megnamisi-Belombe & Nuber (1989); (b) Miao et al. (2011); (c) Sheu & Lee (1999); (d) Dessy et al. (1982); (e) Arumugam et al. (2007); (f) Chandrasekaran et al. (2014); (g) Koehne et al. (2022); (h) Nakazumi et al. (1992); (i) Kotakam et al. (2007); (j) Pap et al. (2007). |
Acknowledgements
Tulane University is acknowledged for its ongoing assistance with operational costs for the X-ray diffraction facility.
Funding information
Funding for this research was provided by: National Science Foundation, Directorate for Mathematical and Physical Sciences (award No. MRI: 1228232; grant No. CHE: 1836589).
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