research communications
κ2N,N′)(1,3-thiazole-2-thiolato-κ2S2,N)nickel(II) hexafluoridophosphate 1,4-dioxane sesquisolvate
of bis(1,10-phenanthroline-aDepartment of Chemistry, Faculty of Science, Fukuoka University, 8-19-1 Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan
*Correspondence e-mail: thama@fukuoka-u.ac.jp
The title salt, [Ni(C3H2NS2)(C12H8N2)2]PF6·1.5C4H8O2, was the unexpected product on making an attempt to prepare an [Ni(2-mercaptothiazolate)(1,10-phenanthroline)]+ complex by reaction of [NiCl2(1,10-phenanthroline)] with 2-mercaptothiazolate. In the resulting complex, the 2-mercaptothiazolate anion acts as a chelating ligand, which coordinates to the NiII ion with the thiazolyl N and thiolate S atoms. In the crystal, π–π stacking interactions between the coordinating 1,10-phenanthroline molecules of adjacent complexes result in a zigzag chain running parallel to the c axis. Weak C—H⋯X (X = O, F) hydrogen-bonding interactions between the chains and 1,4-dioxane solvent molecules and PF6− counter-anions lead to the formation of sheets parallel to the ac plane.
Keywords: crystal structure; 2-mercaptothiazolate; π–π stacking; hydrogen bonding; nickel(II) complex.
CCDC reference: 1539577
1. Chemical context
2-Mercaptothiazolate (tzS) has three types of atoms available for coordination, namely the thiazolyl N, the thiazolyl S, and the thiolate S atom. Hence the tzS ligand is able to show different coordination modes. The anionic tzS ligand and its protonated neutral form are generally used as bridging ligands [μ2-tzS-κ(N, thiolate S)] or as monodentate ligands [κ(thiolate S)] (Raper et al., 1989, 1990a) whereas transition metal complexes with tzS in a bidentate coordination mode are rare (Raper et al., 1989), although a number of transition metal complexes with 2-mercaptobenzothiazolate as a bidentate ligand exist (Raper et al., 1990b; Ballester et al., 1994; Khan et al., 2010).
In a project intended to prepare the square-planar [Ni(tzS)(phen)]+ cation involving tzS as a bidentate ligand by reaction of [NiCl2(phen)] (phen is 1,10-phenanthroline) with 2-mercaptothiazolate, we obtained the unexpected title dioxane solvate compound [Ni(tzS)(phen)2](PF6)·1.5(1,4-dioxane) in which the tzS ligand acts after all as a bidentate ligand.
2. Structural commentary
The title salt consists of a complex cation [Ni(tzS)(phen)2]+, one PF6− counter-anion, and 1.5 1,4-dioxane solvent molecules of crystallization (one located about a centre of inversion), as shown in Fig. 1. The nickel(II) atom exhibits a considerably distorted octahedral N5S coordination environment, which is constructed from one bidentate tzS and two bidentate phen ligands whereby the tzS ligand chelates to the NiII atom through the thiazolyl N and thiolate S atoms. Selected bond lengths and angles are gathered in Table 1. These values are very similar to that of related Ni complexes with bidentate 2-mercaptobenzothiazolate ligands (Raper et al., 1990b; Ballester et al., 1994; Khan et al., 2010). The narrow bite angle involving the tzS ligand (Table 1) is due to formation of a four-membered chelate ring. The averaged Ni—N(phen) distances and bite angles are 2.08 Å and 80.2°, which are typical values for Ni–phen complexes (Bouzaid et al., 2012).
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3. Supramolecular features
In the crystal, π–π stacking interactions between phen ligands of adjacent [Ni(tzS)(phen)2]+ exist (Fig. 2). The interactions result in zigzag chains parallel to the c axis. The distances between the centroids of the rings are 3.8528 (11) for Cg6⋯Cg9ii and Cg9⋯Cg6ii, and 3.6126 (10) Å for Cg8⋯Cg10iii and Cg10⋯Cg8iii, respectively [Cg6, Cg9, Cg8, and Cg10 are the centroids of the N3/C14/C10–C13, C7–C10/C14/C15, N5/C26/C22–C25 and C19–C22/C26/C27 rings, respectively; symmetry codes: (ii) 2 − x, 1 − y, 1 − z; (iii) 2 − x, 1 − y, −z]. Such chains in turn are linked by weak C—H⋯X (X = O, F) hydrogen-bonding interactions involving the PF6− counter-anion and 1,4-dioxane solvent molecules, which results in the formation of a sheet structure parallel to the ac plane (Fig. 3, Table 2).
4. Database survey
A search in the Cambridge Structural Database (Groom et al., 2016) reveals four reports of Ni complexes with bidentate 2-mercaptobenzothiazolate ligands. One is a square-planar complex (Banerji et al., 1982), the others being octahedral complexes. Two of them consist of two 2-mercaptobenzothiazole ligands and another bidentate ligand (Ballester et al., 1994; Khan et al., 2010) whereas the third is a tris-2-mercaptobenzothiazolate complex (Raper et al., 1990b). In the case of a tzS-Ni complex, one μ2-tzS-κ(N, thiolate S)-Ni2 complex is reported (Raper et al., 1989).
5. Synthesis and crystallization
The title compound was synthesized using [NiCl2(phen)], prepared by a literature protocol (Yakhvarov et al., 2007). A mixture of 2-mercaptothiazole (8.07 × 10 −4 mol) and one equivalent of Et3N in methanol (10 ml) was added slowly to a solution of [NiCl2(phen)] (8.07 × 10 −4 mol) in methanol (20 ml). After stirring overnight, the colour of the solution turned from blue to brown–yellow. 10 equivalents of NH4PF6 were added to the solution, resulting in a pale-brown–yellow precipitate. The precipitate was filtered off and dried in vacuo. The crude product containing excess NH4PF6 was purified by recrystallization using 1,4-dioxane vapor diffusion into an acetonitrile solution of the crude product. The title complex was isolated as brown block-like crystals [yield 365 mg, 40.6% (based on Ni)].
6. Refinement
Crystal data, data collection and structure . H atoms were placed in calculated positions and refined as riding, with phenyl C—H = 0.95 Å and methylene C—H = 0.99 Å, both with Uiso(H) = 1.2Ueq(C).
details are summarized in Table 3
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Supporting information
CCDC reference: 1539577
https://doi.org/10.1107/S205698901700456X/wm5374sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901700456X/wm5374Isup2.hkl
Data collection: CrystalClear (Molecular Structure Corporation & Rigaku , 2001); cell
CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2006) and Yadokari-XG (Kabuto et al., 2009; Wakita, 2001); software used to prepare material for publication: Yadokari-XG (Kabuto et al., 2009; Wakita, 2001), PLATON (Spek, 2009) and publCIF (Westrip, 2010).[Ni(C3H2NS2)(C12H8N2)2]PF6·1.5C4H8O2 | Z = 2 |
Mr = 812.42 | F(000) = 832 |
Triclinic, P1 | Dx = 1.636 Mg m−3 |
a = 9.1800 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.1460 (2) Å | Cell parameters from 17089 reflections |
c = 14.9005 (3) Å | θ = 2.7–31.3° |
α = 88.490 (2)° | µ = 0.84 mm−1 |
β = 89.166 (2)° | T = 110 K |
γ = 83.278 (2)° | Block, pale brown |
V = 1649.31 (6) Å3 | 0.27 × 0.24 × 0.16 mm |
Rigaku Saturn 724+ CCD area-detector diffractometer | 8109 reflections with I > 2σ(I) |
ω scans | Rint = 0.037 |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015) | θmax = 31.1°, θmin = 2.6° |
Tmin = 0.942, Tmax = 1.000 | h = −13→12 |
30580 measured reflections | k = −17→17 |
9593 independent reflections | l = −21→21 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0353P)2 + 1.5145P] where P = (Fo2 + 2Fc2)/3 |
9593 reflections | (Δ/σ)max = 0.001 |
460 parameters | Δρmax = 1.07 e Å−3 |
0 restraints | Δρmin = −0.55 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.73044 (2) | 0.61812 (2) | 0.24062 (2) | 0.01241 (6) | |
S1 | 0.53398 (5) | 0.58427 (4) | 0.12496 (3) | 0.02027 (10) | |
S2 | 0.27542 (5) | 0.74630 (4) | 0.20072 (3) | 0.02077 (10) | |
N1 | 0.53418 (17) | 0.71330 (13) | 0.26332 (10) | 0.0156 (3) | |
N2 | 0.67416 (17) | 0.49693 (12) | 0.33146 (10) | 0.0149 (3) | |
N3 | 0.83585 (16) | 0.66322 (12) | 0.35503 (10) | 0.0141 (3) | |
N4 | 0.80703 (16) | 0.73517 (12) | 0.15381 (10) | 0.0135 (3) | |
N5 | 0.91276 (17) | 0.52383 (12) | 0.18870 (10) | 0.0145 (3) | |
C1 | 0.4540 (2) | 0.68055 (15) | 0.19814 (12) | 0.0168 (3) | |
C2 | 0.4575 (2) | 0.79119 (15) | 0.31651 (12) | 0.0163 (3) | |
H1 | 0.500491 | 0.823032 | 0.365735 | 0.020* | |
C3 | 0.3158 (2) | 0.81894 (16) | 0.29321 (13) | 0.0200 (4) | |
H2 | 0.248221 | 0.870981 | 0.323482 | 0.024* | |
C4 | 0.5919 (2) | 0.41613 (15) | 0.31850 (13) | 0.0193 (4) | |
H3 | 0.556632 | 0.407017 | 0.259865 | 0.023* | |
C5 | 0.5550 (2) | 0.34380 (16) | 0.38736 (14) | 0.0233 (4) | |
H4 | 0.496199 | 0.286649 | 0.375371 | 0.028* | |
C6 | 0.6045 (2) | 0.35620 (16) | 0.47238 (14) | 0.0235 (4) | |
H5 | 0.579898 | 0.307848 | 0.519931 | 0.028* | |
C7 | 0.6921 (2) | 0.44098 (16) | 0.48883 (12) | 0.0191 (4) | |
C8 | 0.7474 (2) | 0.46125 (17) | 0.57547 (13) | 0.0249 (4) | |
H6 | 0.726221 | 0.415078 | 0.625286 | 0.030* | |
C9 | 0.8292 (2) | 0.54520 (18) | 0.58738 (13) | 0.0254 (4) | |
H7 | 0.864927 | 0.556815 | 0.645483 | 0.030* | |
C10 | 0.8632 (2) | 0.61703 (16) | 0.51402 (12) | 0.0191 (4) | |
C11 | 0.9467 (2) | 0.70618 (17) | 0.52245 (14) | 0.0239 (4) | |
H8 | 0.984806 | 0.721607 | 0.579105 | 0.029* | |
C12 | 0.9726 (2) | 0.77056 (16) | 0.44835 (14) | 0.0222 (4) | |
H9 | 1.029589 | 0.830557 | 0.453062 | 0.027* | |
C13 | 0.9142 (2) | 0.74704 (15) | 0.36545 (13) | 0.0178 (4) | |
H10 | 0.931415 | 0.792980 | 0.314734 | 0.021* | |
C14 | 0.8106 (2) | 0.59880 (15) | 0.42826 (12) | 0.0151 (3) | |
C15 | 0.7239 (2) | 0.50946 (15) | 0.41569 (12) | 0.0156 (3) | |
C16 | 0.7508 (2) | 0.83886 (15) | 0.13609 (12) | 0.0169 (3) | |
H11 | 0.667891 | 0.869149 | 0.169923 | 0.020* | |
C17 | 0.8085 (2) | 0.90583 (15) | 0.06957 (13) | 0.0194 (4) | |
H12 | 0.764610 | 0.979628 | 0.058505 | 0.023* | |
C18 | 0.9287 (2) | 0.86359 (15) | 0.02080 (12) | 0.0179 (4) | |
H13 | 0.968495 | 0.907501 | −0.024998 | 0.021* | |
C19 | 0.9929 (2) | 0.75454 (15) | 0.03913 (12) | 0.0152 (3) | |
C20 | 1.1203 (2) | 0.70379 (16) | −0.00691 (12) | 0.0190 (4) | |
H14 | 1.163820 | 0.744055 | −0.053612 | 0.023* | |
C21 | 1.1801 (2) | 0.59931 (16) | 0.01492 (12) | 0.0193 (4) | |
H15 | 1.266761 | 0.568516 | −0.015128 | 0.023* | |
C22 | 1.1142 (2) | 0.53469 (15) | 0.08271 (12) | 0.0161 (3) | |
C23 | 1.1700 (2) | 0.42569 (16) | 0.10745 (13) | 0.0202 (4) | |
H16 | 1.258641 | 0.392175 | 0.081252 | 0.024* | |
C24 | 1.0956 (2) | 0.36811 (16) | 0.16959 (13) | 0.0210 (4) | |
H17 | 1.131644 | 0.294102 | 0.186555 | 0.025* | |
C25 | 0.9656 (2) | 0.41942 (15) | 0.20793 (12) | 0.0178 (4) | |
H18 | 0.913046 | 0.377820 | 0.249434 | 0.021* | |
C26 | 0.98624 (19) | 0.58098 (14) | 0.12670 (11) | 0.0140 (3) | |
C27 | 0.92727 (19) | 0.69317 (14) | 0.10620 (11) | 0.0134 (3) | |
P1 | −0.06216 (5) | 1.07671 (4) | 0.28379 (3) | 0.01764 (10) | |
F1 | 0.08571 (15) | 1.13260 (13) | 0.29517 (10) | 0.0407 (4) | |
F2 | −0.07497 (16) | 1.12468 (12) | 0.18336 (8) | 0.0367 (3) | |
F3 | −0.20929 (14) | 1.02145 (11) | 0.27239 (9) | 0.0330 (3) | |
F4 | −0.04921 (18) | 1.02975 (13) | 0.38455 (9) | 0.0462 (4) | |
F5 | −0.15412 (16) | 1.18707 (11) | 0.31890 (10) | 0.0372 (3) | |
F6 | 0.02958 (15) | 0.96652 (11) | 0.24816 (11) | 0.0407 (4) | |
O1 | 0.46687 (16) | 0.11530 (11) | 0.48337 (10) | 0.0246 (3) | |
C28 | 0.6101 (2) | 0.05903 (18) | 0.46710 (15) | 0.0275 (4) | |
H19 | 0.684348 | 0.110335 | 0.476684 | 0.033* | |
H20 | 0.618213 | 0.035696 | 0.403887 | 0.033* | |
C29 | 0.3598 (2) | 0.04078 (17) | 0.47172 (15) | 0.0267 (4) | |
H21 | 0.361853 | 0.017159 | 0.408583 | 0.032* | |
H22 | 0.260907 | 0.079038 | 0.484938 | 0.032* | |
O2 | 0.43879 (16) | 0.25330 (12) | 0.19127 (10) | 0.0258 (3) | |
C30 | 0.4199 (2) | 0.14818 (19) | 0.23091 (14) | 0.0279 (5) | |
H23 | 0.345190 | 0.157520 | 0.279569 | 0.034* | |
H24 | 0.513406 | 0.114588 | 0.257485 | 0.034* | |
C31 | 0.3720 (3) | 0.07302 (19) | 0.16157 (16) | 0.0343 (5) | |
H25 | 0.358712 | 0.000165 | 0.189903 | 0.041* | |
H26 | 0.276598 | 0.105373 | 0.136657 | 0.041* | |
O3 | 0.4778 (2) | 0.05827 (13) | 0.09123 (12) | 0.0406 (4) | |
C32 | 0.5003 (3) | 0.16329 (19) | 0.05165 (15) | 0.0298 (5) | |
H27 | 0.408580 | 0.197032 | 0.023020 | 0.036* | |
H28 | 0.577340 | 0.152711 | 0.004431 | 0.036* | |
C33 | 0.5455 (2) | 0.23982 (19) | 0.12063 (15) | 0.0275 (4) | |
H29 | 0.641539 | 0.209207 | 0.145690 | 0.033* | |
H30 | 0.556615 | 0.312911 | 0.092026 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.01357 (11) | 0.01267 (11) | 0.01108 (11) | −0.00176 (8) | −0.00075 (8) | −0.00039 (8) |
S1 | 0.0239 (2) | 0.0193 (2) | 0.0174 (2) | −0.00050 (18) | −0.00023 (18) | −0.00451 (17) |
S2 | 0.0155 (2) | 0.0246 (2) | 0.0219 (2) | −0.00020 (18) | −0.00392 (17) | −0.00288 (18) |
N1 | 0.0160 (7) | 0.0166 (7) | 0.0140 (7) | −0.0014 (6) | −0.0003 (6) | 0.0004 (6) |
N2 | 0.0158 (7) | 0.0137 (7) | 0.0152 (7) | −0.0014 (6) | 0.0007 (6) | −0.0004 (5) |
N3 | 0.0132 (7) | 0.0137 (7) | 0.0153 (7) | −0.0006 (5) | −0.0018 (5) | −0.0015 (5) |
N4 | 0.0142 (7) | 0.0141 (7) | 0.0124 (7) | −0.0018 (5) | −0.0019 (5) | −0.0006 (5) |
N5 | 0.0165 (7) | 0.0136 (7) | 0.0133 (7) | −0.0016 (6) | −0.0016 (6) | −0.0008 (5) |
C1 | 0.0178 (9) | 0.0165 (8) | 0.0159 (8) | −0.0009 (7) | −0.0001 (7) | −0.0001 (7) |
C2 | 0.0208 (9) | 0.0152 (8) | 0.0134 (8) | −0.0041 (7) | 0.0001 (7) | 0.0006 (6) |
C3 | 0.0205 (9) | 0.0201 (9) | 0.0189 (9) | 0.0001 (7) | 0.0019 (7) | −0.0026 (7) |
C4 | 0.0216 (9) | 0.0160 (9) | 0.0209 (9) | −0.0044 (7) | −0.0007 (7) | −0.0009 (7) |
C5 | 0.0263 (10) | 0.0153 (9) | 0.0288 (10) | −0.0055 (8) | 0.0045 (8) | 0.0001 (7) |
C6 | 0.0289 (11) | 0.0147 (9) | 0.0257 (10) | −0.0004 (8) | 0.0080 (8) | 0.0060 (7) |
C7 | 0.0217 (9) | 0.0177 (9) | 0.0163 (8) | 0.0039 (7) | 0.0030 (7) | 0.0028 (7) |
C8 | 0.0312 (11) | 0.0260 (10) | 0.0155 (9) | 0.0032 (8) | 0.0018 (8) | 0.0054 (7) |
C9 | 0.0310 (11) | 0.0309 (11) | 0.0126 (8) | 0.0042 (9) | −0.0036 (8) | −0.0005 (8) |
C10 | 0.0192 (9) | 0.0211 (9) | 0.0155 (8) | 0.0050 (7) | −0.0034 (7) | −0.0032 (7) |
C11 | 0.0233 (10) | 0.0272 (10) | 0.0206 (9) | 0.0021 (8) | −0.0081 (8) | −0.0086 (8) |
C12 | 0.0196 (9) | 0.0196 (9) | 0.0278 (10) | −0.0021 (7) | −0.0057 (8) | −0.0074 (8) |
C13 | 0.0174 (9) | 0.0151 (8) | 0.0209 (9) | −0.0014 (7) | −0.0016 (7) | −0.0021 (7) |
C14 | 0.0158 (8) | 0.0149 (8) | 0.0136 (8) | 0.0032 (6) | −0.0009 (6) | −0.0022 (6) |
C15 | 0.0171 (9) | 0.0137 (8) | 0.0153 (8) | 0.0005 (7) | 0.0008 (7) | −0.0003 (6) |
C16 | 0.0172 (9) | 0.0146 (8) | 0.0184 (8) | 0.0005 (7) | −0.0003 (7) | −0.0016 (7) |
C17 | 0.0234 (10) | 0.0142 (8) | 0.0203 (9) | −0.0009 (7) | −0.0023 (7) | 0.0020 (7) |
C18 | 0.0219 (9) | 0.0174 (9) | 0.0151 (8) | −0.0052 (7) | −0.0009 (7) | 0.0022 (7) |
C19 | 0.0161 (8) | 0.0177 (8) | 0.0125 (8) | −0.0039 (7) | −0.0023 (6) | −0.0008 (6) |
C20 | 0.0180 (9) | 0.0244 (9) | 0.0152 (8) | −0.0046 (7) | 0.0023 (7) | −0.0005 (7) |
C21 | 0.0164 (9) | 0.0240 (9) | 0.0173 (9) | −0.0013 (7) | 0.0023 (7) | −0.0043 (7) |
C22 | 0.0162 (8) | 0.0175 (8) | 0.0148 (8) | −0.0011 (7) | −0.0020 (7) | −0.0031 (6) |
C23 | 0.0173 (9) | 0.0194 (9) | 0.0229 (9) | 0.0036 (7) | −0.0021 (7) | −0.0061 (7) |
C24 | 0.0235 (10) | 0.0151 (8) | 0.0233 (9) | 0.0030 (7) | −0.0049 (8) | −0.0014 (7) |
C25 | 0.0213 (9) | 0.0154 (8) | 0.0168 (8) | −0.0019 (7) | −0.0039 (7) | −0.0005 (7) |
C26 | 0.0138 (8) | 0.0142 (8) | 0.0138 (8) | −0.0005 (6) | −0.0032 (6) | −0.0017 (6) |
C27 | 0.0143 (8) | 0.0142 (8) | 0.0119 (7) | −0.0019 (6) | −0.0032 (6) | −0.0010 (6) |
P1 | 0.0179 (2) | 0.0176 (2) | 0.0175 (2) | −0.00266 (18) | −0.00070 (18) | 0.00178 (17) |
F1 | 0.0282 (7) | 0.0550 (9) | 0.0433 (8) | −0.0218 (7) | 0.0021 (6) | −0.0075 (7) |
F2 | 0.0479 (9) | 0.0412 (8) | 0.0197 (6) | −0.0024 (7) | −0.0003 (6) | 0.0089 (6) |
F3 | 0.0254 (7) | 0.0397 (8) | 0.0370 (7) | −0.0140 (6) | 0.0059 (5) | −0.0143 (6) |
F4 | 0.0601 (10) | 0.0546 (10) | 0.0254 (7) | −0.0157 (8) | −0.0099 (7) | 0.0166 (7) |
F5 | 0.0406 (8) | 0.0258 (7) | 0.0450 (8) | −0.0014 (6) | 0.0112 (6) | −0.0130 (6) |
F6 | 0.0302 (7) | 0.0273 (7) | 0.0615 (10) | 0.0095 (6) | 0.0039 (7) | −0.0039 (7) |
O1 | 0.0298 (8) | 0.0153 (7) | 0.0285 (8) | −0.0022 (6) | 0.0013 (6) | −0.0007 (6) |
C28 | 0.0279 (11) | 0.0232 (10) | 0.0314 (11) | −0.0048 (8) | 0.0076 (9) | 0.0008 (8) |
C29 | 0.0253 (11) | 0.0221 (10) | 0.0325 (11) | −0.0013 (8) | −0.0005 (9) | −0.0006 (8) |
O2 | 0.0232 (7) | 0.0280 (8) | 0.0265 (7) | −0.0036 (6) | 0.0015 (6) | −0.0043 (6) |
C30 | 0.0207 (10) | 0.0383 (12) | 0.0241 (10) | −0.0018 (9) | −0.0007 (8) | 0.0059 (9) |
C31 | 0.0444 (14) | 0.0247 (11) | 0.0345 (12) | −0.0083 (10) | 0.0017 (10) | 0.0040 (9) |
O3 | 0.0588 (12) | 0.0220 (8) | 0.0392 (10) | 0.0015 (8) | 0.0122 (8) | −0.0051 (7) |
C32 | 0.0342 (12) | 0.0316 (12) | 0.0231 (10) | −0.0022 (9) | 0.0043 (9) | −0.0001 (9) |
C33 | 0.0198 (10) | 0.0352 (12) | 0.0279 (11) | −0.0059 (9) | 0.0011 (8) | 0.0020 (9) |
Ni1—N1 | 2.0524 (16) | C17—H12 | 0.9500 |
Ni1—N5 | 2.0668 (15) | C18—C19 | 1.407 (3) |
Ni1—N4 | 2.0735 (15) | C18—H13 | 0.9500 |
Ni1—N2 | 2.0780 (15) | C19—C27 | 1.402 (2) |
Ni1—N3 | 2.0890 (15) | C19—C20 | 1.432 (3) |
Ni1—S1 | 2.5871 (5) | C20—C21 | 1.355 (3) |
S1—C1 | 1.7143 (19) | C20—H14 | 0.9500 |
S2—C3 | 1.724 (2) | C21—C22 | 1.433 (3) |
S2—C1 | 1.7377 (19) | C21—H15 | 0.9500 |
N1—C1 | 1.324 (2) | C22—C26 | 1.403 (2) |
N1—C2 | 1.373 (2) | C22—C23 | 1.404 (3) |
N2—C4 | 1.326 (2) | C23—C24 | 1.368 (3) |
N2—C15 | 1.360 (2) | C23—H16 | 0.9500 |
N3—C13 | 1.327 (2) | C24—C25 | 1.401 (3) |
N3—C14 | 1.359 (2) | C24—H17 | 0.9500 |
N4—C16 | 1.325 (2) | C25—H18 | 0.9500 |
N4—C27 | 1.359 (2) | C26—C27 | 1.433 (2) |
N5—C25 | 1.329 (2) | P1—F3 | 1.5901 (13) |
N5—C26 | 1.359 (2) | P1—F2 | 1.5925 (13) |
C2—C3 | 1.353 (3) | P1—F4 | 1.5929 (14) |
C2—H1 | 0.9500 | P1—F5 | 1.5944 (14) |
C3—H2 | 0.9500 | P1—F6 | 1.5946 (14) |
C4—C5 | 1.397 (3) | P1—F1 | 1.6002 (14) |
C4—H3 | 0.9500 | O1—C29 | 1.427 (2) |
C5—C6 | 1.370 (3) | O1—C28 | 1.430 (3) |
C5—H4 | 0.9500 | C28—C29i | 1.499 (3) |
C6—C7 | 1.407 (3) | C28—H19 | 0.9900 |
C6—H5 | 0.9500 | C28—H20 | 0.9900 |
C7—C15 | 1.402 (2) | C29—H21 | 0.9900 |
C7—C8 | 1.431 (3) | C29—H22 | 0.9900 |
C8—C9 | 1.352 (3) | O2—C30 | 1.421 (3) |
C8—H6 | 0.9500 | O2—C33 | 1.427 (3) |
C9—C10 | 1.434 (3) | C30—C31 | 1.500 (3) |
C9—H7 | 0.9500 | C30—H23 | 0.9900 |
C10—C14 | 1.405 (2) | C30—H24 | 0.9900 |
C10—C11 | 1.407 (3) | C31—O3 | 1.419 (3) |
C11—C12 | 1.370 (3) | C31—H25 | 0.9900 |
C11—H8 | 0.9500 | C31—H26 | 0.9900 |
C12—C13 | 1.403 (3) | O3—C32 | 1.427 (3) |
C12—H9 | 0.9500 | C32—C33 | 1.498 (3) |
C13—H10 | 0.9500 | C32—H27 | 0.9900 |
C14—C15 | 1.436 (2) | C32—H28 | 0.9900 |
C16—C17 | 1.403 (3) | C33—H29 | 0.9900 |
C16—H11 | 0.9500 | C33—H30 | 0.9900 |
C17—C18 | 1.369 (3) | ||
N1—Ni1—N5 | 167.32 (6) | C17—C18—H13 | 120.3 |
N1—Ni1—N4 | 93.43 (6) | C19—C18—H13 | 120.3 |
N5—Ni1—N4 | 80.54 (6) | C27—C19—C18 | 117.60 (17) |
N1—Ni1—N2 | 91.11 (6) | C27—C19—C20 | 118.87 (17) |
N5—Ni1—N2 | 95.58 (6) | C18—C19—C20 | 123.53 (17) |
N4—Ni1—N2 | 174.56 (6) | C21—C20—C19 | 121.19 (17) |
N1—Ni1—N3 | 96.71 (6) | C21—C20—H14 | 119.4 |
N5—Ni1—N3 | 95.07 (6) | C19—C20—H14 | 119.4 |
N4—Ni1—N3 | 96.57 (6) | C20—C21—C22 | 120.89 (17) |
N2—Ni1—N3 | 79.90 (6) | C20—C21—H15 | 119.6 |
N1—Ni1—S1 | 67.71 (4) | C22—C21—H15 | 119.6 |
N5—Ni1—S1 | 100.94 (4) | C26—C22—C23 | 117.41 (17) |
N4—Ni1—S1 | 89.91 (4) | C26—C22—C21 | 119.09 (17) |
N2—Ni1—S1 | 94.59 (4) | C23—C22—C21 | 123.49 (17) |
N3—Ni1—S1 | 163.53 (4) | C24—C23—C22 | 119.49 (18) |
C1—S1—Ni1 | 72.66 (6) | C24—C23—H16 | 120.3 |
C3—S2—C1 | 90.25 (9) | C22—C23—H16 | 120.3 |
C1—N1—C2 | 112.89 (16) | C23—C24—C25 | 119.32 (18) |
C1—N1—Ni1 | 100.84 (12) | C23—C24—H17 | 120.3 |
C2—N1—Ni1 | 146.25 (13) | C25—C24—H17 | 120.3 |
C4—N2—C15 | 118.14 (16) | N5—C25—C24 | 122.78 (18) |
C4—N2—Ni1 | 128.68 (13) | N5—C25—H18 | 118.6 |
C15—N2—Ni1 | 113.07 (12) | C24—C25—H18 | 118.6 |
C13—N3—C14 | 118.13 (16) | N5—C26—C22 | 122.98 (16) |
C13—N3—Ni1 | 129.09 (13) | N5—C26—C27 | 117.26 (16) |
C14—N3—Ni1 | 112.67 (11) | C22—C26—C27 | 119.76 (16) |
C16—N4—C27 | 118.16 (15) | N4—C27—C19 | 122.76 (16) |
C16—N4—Ni1 | 129.33 (13) | N4—C27—C26 | 117.15 (15) |
C27—N4—Ni1 | 112.38 (11) | C19—C27—C26 | 120.09 (16) |
C25—N5—C26 | 117.93 (16) | F3—P1—F2 | 90.17 (8) |
C25—N5—Ni1 | 129.51 (13) | F3—P1—F4 | 90.13 (8) |
C26—N5—Ni1 | 112.56 (11) | F2—P1—F4 | 179.51 (9) |
N1—C1—S1 | 118.78 (14) | F3—P1—F5 | 90.39 (8) |
N1—C1—S2 | 111.99 (14) | F2—P1—F5 | 90.13 (8) |
S1—C1—S2 | 129.24 (11) | F4—P1—F5 | 89.48 (9) |
C3—C2—N1 | 114.64 (17) | F3—P1—F6 | 89.55 (8) |
C3—C2—H1 | 122.7 | F2—P1—F6 | 89.58 (8) |
N1—C2—H1 | 122.7 | F4—P1—F6 | 90.81 (9) |
C2—C3—S2 | 110.23 (14) | F5—P1—F6 | 179.70 (9) |
C2—C3—H2 | 124.9 | F3—P1—F1 | 179.86 (10) |
S2—C3—H2 | 124.9 | F2—P1—F1 | 89.74 (8) |
N2—C4—C5 | 122.83 (18) | F4—P1—F1 | 89.96 (8) |
N2—C4—H3 | 118.6 | F5—P1—F1 | 89.50 (8) |
C5—C4—H3 | 118.6 | F6—P1—F1 | 90.56 (8) |
C6—C5—C4 | 119.28 (18) | C29—O1—C28 | 109.56 (15) |
C6—C5—H4 | 120.4 | O1—C28—C29i | 111.04 (17) |
C4—C5—H4 | 120.4 | O1—C28—H19 | 109.4 |
C5—C6—C7 | 119.59 (18) | C29i—C28—H19 | 109.4 |
C5—C6—H5 | 120.2 | O1—C28—H20 | 109.4 |
C7—C6—H5 | 120.2 | C29i—C28—H20 | 109.4 |
C15—C7—C6 | 117.20 (18) | H19—C28—H20 | 108.0 |
C15—C7—C8 | 119.17 (18) | O1—C29—C28i | 110.46 (18) |
C6—C7—C8 | 123.63 (18) | O1—C29—H21 | 109.6 |
C9—C8—C7 | 120.92 (18) | C28i—C29—H21 | 109.6 |
C9—C8—H6 | 119.5 | O1—C29—H22 | 109.6 |
C7—C8—H6 | 119.5 | C28i—C29—H22 | 109.6 |
C8—C9—C10 | 121.29 (18) | H21—C29—H22 | 108.1 |
C8—C9—H7 | 119.4 | C30—O2—C33 | 109.66 (16) |
C10—C9—H7 | 119.4 | O2—C30—C31 | 110.18 (17) |
C14—C10—C11 | 117.21 (18) | O2—C30—H23 | 109.6 |
C14—C10—C9 | 118.94 (18) | C31—C30—H23 | 109.6 |
C11—C10—C9 | 123.85 (18) | O2—C30—H24 | 109.6 |
C12—C11—C10 | 119.52 (18) | C31—C30—H24 | 109.6 |
C12—C11—H8 | 120.2 | H23—C30—H24 | 108.1 |
C10—C11—H8 | 120.2 | O3—C31—C30 | 110.5 (2) |
C11—C12—C13 | 119.36 (18) | O3—C31—H25 | 109.5 |
C11—C12—H9 | 120.3 | C30—C31—H25 | 109.5 |
C13—C12—H9 | 120.3 | O3—C31—H26 | 109.5 |
N3—C13—C12 | 122.67 (18) | C30—C31—H26 | 109.5 |
N3—C13—H10 | 118.7 | H25—C31—H26 | 108.1 |
C12—C13—H10 | 118.7 | C31—O3—C32 | 109.84 (17) |
N3—C14—C10 | 123.10 (17) | O3—C32—C33 | 111.09 (18) |
N3—C14—C15 | 117.20 (15) | O3—C32—H27 | 109.4 |
C10—C14—C15 | 119.70 (17) | C33—C32—H27 | 109.4 |
N2—C15—C7 | 122.97 (17) | O3—C32—H28 | 109.4 |
N2—C15—C14 | 117.04 (16) | C33—C32—H28 | 109.4 |
C7—C15—C14 | 119.99 (17) | H27—C32—H28 | 108.0 |
N4—C16—C17 | 122.88 (17) | O2—C33—C32 | 110.56 (17) |
N4—C16—H11 | 118.6 | O2—C33—H29 | 109.5 |
C17—C16—H11 | 118.6 | C32—C33—H29 | 109.5 |
C18—C17—C16 | 119.20 (17) | O2—C33—H30 | 109.5 |
C18—C17—H12 | 120.4 | C32—C33—H30 | 109.5 |
C16—C17—H12 | 120.4 | H29—C33—H30 | 108.1 |
C17—C18—C19 | 119.37 (17) | ||
C2—N1—C1—S1 | 179.41 (13) | N3—C14—C15—C7 | −179.09 (16) |
Ni1—N1—C1—S1 | −1.39 (16) | C10—C14—C15—C7 | 0.0 (3) |
C2—N1—C1—S2 | −0.3 (2) | C27—N4—C16—C17 | 1.2 (3) |
Ni1—N1—C1—S2 | 178.89 (9) | Ni1—N4—C16—C17 | −174.37 (14) |
Ni1—S1—C1—N1 | 1.14 (13) | N4—C16—C17—C18 | −0.5 (3) |
Ni1—S1—C1—S2 | −179.20 (15) | C16—C17—C18—C19 | −0.8 (3) |
C3—S2—C1—N1 | 0.03 (15) | C17—C18—C19—C27 | 1.3 (3) |
C3—S2—C1—S1 | −179.65 (14) | C17—C18—C19—C20 | −178.73 (18) |
C1—N1—C2—C3 | 0.5 (2) | C27—C19—C20—C21 | −1.8 (3) |
Ni1—N1—C2—C3 | −178.06 (17) | C18—C19—C20—C21 | 178.29 (18) |
N1—C2—C3—S2 | −0.5 (2) | C19—C20—C21—C22 | 2.3 (3) |
C1—S2—C3—C2 | 0.25 (15) | C20—C21—C22—C26 | 0.0 (3) |
C15—N2—C4—C5 | −0.1 (3) | C20—C21—C22—C23 | 179.21 (18) |
Ni1—N2—C4—C5 | −175.92 (14) | C26—C22—C23—C24 | 2.7 (3) |
N2—C4—C5—C6 | 0.3 (3) | C21—C22—C23—C24 | −176.58 (18) |
C4—C5—C6—C7 | −0.3 (3) | C22—C23—C24—C25 | −0.5 (3) |
C5—C6—C7—C15 | 0.2 (3) | C26—N5—C25—C24 | 2.4 (3) |
C5—C6—C7—C8 | 179.18 (19) | Ni1—N5—C25—C24 | −176.95 (13) |
C15—C7—C8—C9 | 0.0 (3) | C23—C24—C25—N5 | −2.2 (3) |
C6—C7—C8—C9 | −179.0 (2) | C25—N5—C26—C22 | 0.0 (3) |
C7—C8—C9—C10 | 0.2 (3) | Ni1—N5—C26—C22 | 179.44 (13) |
C8—C9—C10—C14 | −0.4 (3) | C25—N5—C26—C27 | 179.54 (15) |
C8—C9—C10—C11 | 179.5 (2) | Ni1—N5—C26—C27 | −1.01 (19) |
C14—C10—C11—C12 | 0.2 (3) | C23—C22—C26—N5 | −2.5 (3) |
C9—C10—C11—C12 | −179.65 (19) | C21—C22—C26—N5 | 176.79 (16) |
C10—C11—C12—C13 | 0.6 (3) | C23—C22—C26—C27 | 177.96 (16) |
C14—N3—C13—C12 | 0.7 (3) | C21—C22—C26—C27 | −2.8 (3) |
Ni1—N3—C13—C12 | 176.59 (14) | C16—N4—C27—C19 | −0.5 (2) |
C11—C12—C13—N3 | −1.1 (3) | Ni1—N4—C27—C19 | 175.75 (13) |
C13—N3—C14—C10 | 0.1 (3) | C16—N4—C27—C26 | 179.86 (15) |
Ni1—N3—C14—C10 | −176.42 (14) | Ni1—N4—C27—C26 | −3.88 (19) |
C13—N3—C14—C15 | 179.19 (16) | C18—C19—C27—N4 | −0.7 (3) |
Ni1—N3—C14—C15 | 2.7 (2) | C20—C19—C27—N4 | 179.34 (16) |
C11—C10—C14—N3 | −0.5 (3) | C18—C19—C27—C26 | 178.90 (16) |
C9—C10—C14—N3 | 179.28 (17) | C20—C19—C27—C26 | −1.0 (2) |
C11—C10—C14—C15 | −179.60 (17) | N5—C26—C27—N4 | 3.4 (2) |
C9—C10—C14—C15 | 0.2 (3) | C22—C26—C27—N4 | −177.08 (15) |
C4—N2—C15—C7 | 0.0 (3) | N5—C26—C27—C19 | −176.28 (15) |
Ni1—N2—C15—C7 | 176.42 (14) | C22—C26—C27—C19 | 3.3 (2) |
C4—N2—C15—C14 | −178.94 (16) | C29—O1—C28—C29i | −57.7 (2) |
Ni1—N2—C15—C14 | −2.5 (2) | C28—O1—C29—C28i | 57.4 (2) |
C6—C7—C15—N2 | 0.0 (3) | C33—O2—C30—C31 | −58.8 (2) |
C8—C7—C15—N2 | −179.08 (17) | O2—C30—C31—O3 | 59.4 (2) |
C6—C7—C15—C14 | 178.90 (17) | C30—C31—O3—C32 | −57.7 (3) |
C8—C7—C15—C14 | −0.2 (3) | C31—O3—C32—C33 | 56.7 (3) |
N3—C14—C15—N2 | −0.1 (2) | C30—O2—C33—C32 | 57.7 (2) |
C10—C14—C15—N2 | 179.01 (16) | O3—C32—C33—O2 | −57.0 (2) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H1···O1ii | 0.95 | 2.42 | 3.330 (2) | 160 |
C3—H2···F6 | 0.95 | 2.47 | 3.074 (2) | 122 |
C4—H3···O2 | 0.95 | 2.51 | 3.226 (2) | 132 |
C5—H4···O1 | 0.95 | 2.63 | 3.269 (2) | 125 |
C12—H9···F4iii | 0.95 | 2.63 | 3.249 (3) | 124 |
C13—H10···F6iii | 0.95 | 2.56 | 3.412 (2) | 150 |
C24—H17···F1iv | 0.95 | 2.58 | 3.386 (3) | 143 |
C28—H20···F3iv | 0.99 | 2.50 | 3.336 (3) | 142 |
C30—H23···F1v | 0.99 | 2.44 | 3.225 (3) | 136 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z; (iv) x+1, y−1, z; (v) x, y−1, z. |
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