J. Adamko Koziskova,
Y.-S. Chen,
S.-Y. Grass,
Y.-C. Chuang,
I.-J. Hsu,
Y. Wang,
M. Lutz,
A. Volkov,
P. Herich,
B. Vénosová,
I. Jelemenská,
L. Bučinský,
M. Breza and
J. Kožíšek High-resolution X-ray diffraction experiments, theoretical calculations and atom-specific X-ray absorption experiments were used to investigate two nickel complexes, (MePh3P)2[NiII(bdtCl2)2]·2(CH3)2SO [complex (1)] and (MePh3P)[NiIII(bdtCl2)2] [complex (2)]. Combining the techniques of nickel K- and sulfur K-edge X-ray absorption spectroscopy with high-resolution X-ray charge density modeling, together with theoretical calculations, the actual oxidation states of the central Ni atoms in these two complexes are investigated. Ni ions in two complexes are clearly in different oxidation states: the Ni ion of complex (1) is formally NiII; that of complex (2) should be formally NiIII, yet it is best described as a combination of Ni2+ and Ni3+, due to the involvement of the non-innocent ligand in the Ni—L bond. A detailed description of Ni—S bond character (σ,π) is presented.
Supporting information
CCDC references: 2119610; 2122285; 2122286
For all structures, program(s) used to solve structure: ShelXT (Sheldrick, 2015); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).
Crystal data top
C12H4Cl4NiS4·2(C2H6OS)·2(C19H18P) | F(000) = 1228 |
Mr = 1187.76 | Dx = 1.494 Mg m−3 |
Monoclinic, P21/n | Ag Kα radiation, λ = 0.56083 Å |
a = 13.8788 (1) Å | Cell parameters from 564441 reflections |
b = 11.5765 (1) Å | θ = 2.1–39.7° |
c = 16.4387 (1) Å | µ = 0.47 mm−1 |
β = 90.651 (1)° | T = 100 K |
V = 2641.00 (3) Å3 | Plate, yellow-brown |
Z = 2 | 0.32 × 0.18 × 0.05 mm |
Data collection top
STOE STADIVARI diffractometer | 32089 independent reflections |
Radiation source: Incoatec HB Iµs 2.0, Incoatec Ag tube | 21588 reflections with I > 2σ(I) |
Graded multilayer mirror monochromator | Rint = 0.046 |
Detector resolution: 5.81 pixels mm-1 | θmax = 39.8°, θmin = 2.1° |
rotation method, ω scans | h = −29→31 |
Absorption correction: integration STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens, "The Evaluation of Absorption and Extinction in Single-Crystal
Structure Analysis", published in
F. R. Ahmed (Editor), "Crystallographic Computing",
Munksgaard, Copenhagen (1970), 255 - 270 | k = −26→26 |
Tmin = 0.934, Tmax = 0.985 | l = −37→34 |
423226 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0475P)2 + 0.4625P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.003 |
32089 reflections | Δρmax = 1.14 e Å−3 |
316 parameters | Δρmin = −0.76 e Å−3 |
0 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.20021 (4) | 0.88418 (5) | 0.52472 (3) | 0.01313 (7) | |
C2 | 0.13591 (4) | 0.78907 (5) | 0.52492 (3) | 0.01350 (7) | |
C3 | 0.17364 (4) | 0.67962 (5) | 0.54380 (3) | 0.01548 (8) | |
C4 | 0.27071 (4) | 0.66152 (6) | 0.56147 (4) | 0.01772 (9) | |
H4 | 0.293294 | 0.587743 | 0.573425 | 0.021* | |
C5 | 0.33352 (4) | 0.75489 (6) | 0.56106 (4) | 0.01729 (8) | |
H5 | 0.398598 | 0.744609 | 0.573057 | 0.021* | |
C6 | 0.29765 (4) | 0.86390 (5) | 0.54244 (3) | 0.01478 (7) | |
Cl1 | 0.37771 (2) | 0.98020 (2) | 0.54315 (2) | 0.01908 (3) | |
Cl2 | 0.09648 (2) | 0.56120 (2) | 0.54697 (2) | 0.02062 (3) | |
Ni1 | 0.000000 | 1.000000 | 0.500000 | 0.01174 (2) | |
S1 | 0.15530 (2) | 1.02168 (2) | 0.50391 (2) | 0.01428 (2) | |
S2 | 0.01443 (2) | 0.81311 (2) | 0.50318 (2) | 0.01503 (2) | |
C26 | 0.70855 (9) | 0.57799 (10) | 0.25536 (7) | 0.0377 (2) | |
H26A | 0.748642 | 0.545516 | 0.297481 | 0.057* | |
H26B | 0.676478 | 0.645325 | 0.275752 | 0.057* | |
H26C | 0.747625 | 0.599106 | 0.209895 | 0.057* | |
C27 | 0.70375 (7) | 0.36013 (8) | 0.20150 (5) | 0.02960 (15) | |
H27A | 0.749300 | 0.386234 | 0.162013 | 0.044* | |
H27B | 0.668811 | 0.295084 | 0.180134 | 0.044* | |
H27C | 0.737349 | 0.337784 | 0.250378 | 0.044* | |
O1 | 0.56948 (4) | 0.43752 (6) | 0.29888 (4) | 0.02617 (10) | |
S3 | 0.62136 (2) | 0.47433 (2) | 0.22379 (2) | 0.02183 (3) | |
C7 | 0.34485 (5) | 0.40980 (6) | 0.20600 (4) | 0.01922 (9) | |
H7A | 0.341593 | 0.447236 | 0.153938 | 0.029* | |
H7B | 0.303028 | 0.343740 | 0.205744 | 0.029* | |
H7C | 0.409840 | 0.385408 | 0.216875 | 0.029* | |
C8 | 0.18880 (4) | 0.56026 (5) | 0.26145 (3) | 0.01439 (7) | |
C9 | 0.12574 (5) | 0.59057 (6) | 0.32376 (4) | 0.01722 (8) | |
H9 | 0.143245 | 0.578044 | 0.377818 | 0.021* | |
C10 | 0.03684 (5) | 0.63948 (6) | 0.30458 (4) | 0.01891 (9) | |
H10 | −0.005783 | 0.658372 | 0.345749 | 0.023* | |
C11 | 0.01174 (4) | 0.66011 (6) | 0.22368 (4) | 0.01853 (9) | |
H11 | −0.047802 | 0.692634 | 0.210887 | 0.022* | |
C12 | 0.07536 (4) | 0.63228 (6) | 0.16178 (4) | 0.01774 (9) | |
H12 | 0.058522 | 0.647398 | 0.107905 | 0.021* | |
C13 | 0.16383 (4) | 0.58206 (6) | 0.18015 (3) | 0.01644 (8) | |
H13 | 0.206138 | 0.563061 | 0.138778 | 0.020* | |
C14 | 0.38485 (4) | 0.63244 (5) | 0.28524 (3) | 0.01336 (7) | |
C15 | 0.43798 (5) | 0.66269 (6) | 0.21702 (4) | 0.01766 (8) | |
H15 | 0.437323 | 0.615725 | 0.171121 | 0.021* | |
C16 | 0.49209 (5) | 0.76407 (6) | 0.21835 (4) | 0.02141 (10) | |
H16 | 0.527529 | 0.784990 | 0.172992 | 0.026* | |
C17 | 0.49346 (5) | 0.83402 (6) | 0.28689 (4) | 0.02005 (10) | |
H17 | 0.530771 | 0.900741 | 0.287689 | 0.024* | |
C18 | 0.43908 (5) | 0.80455 (6) | 0.35449 (4) | 0.01878 (9) | |
H18 | 0.439458 | 0.852076 | 0.400111 | 0.023* | |
C19 | 0.38426 (5) | 0.70411 (5) | 0.35374 (3) | 0.01654 (8) | |
H19 | 0.347354 | 0.684630 | 0.398565 | 0.020* | |
C20 | 0.31289 (4) | 0.43517 (5) | 0.37895 (3) | 0.01433 (7) | |
C21 | 0.23395 (5) | 0.37231 (6) | 0.40719 (5) | 0.02025 (10) | |
H21 | 0.176117 | 0.372486 | 0.378050 | 0.024* | |
C22 | 0.24239 (5) | 0.30956 (6) | 0.47906 (5) | 0.02388 (12) | |
H22 | 0.189787 | 0.268676 | 0.498548 | 0.029* | |
C23 | 0.32934 (6) | 0.30788 (6) | 0.52179 (4) | 0.02208 (11) | |
H23 | 0.334756 | 0.265732 | 0.569785 | 0.026* | |
C24 | 0.40817 (5) | 0.36878 (6) | 0.49318 (4) | 0.01910 (9) | |
H24 | 0.466264 | 0.366907 | 0.521912 | 0.023* | |
C25 | 0.40059 (4) | 0.43256 (5) | 0.42177 (3) | 0.01563 (8) | |
H25 | 0.453457 | 0.473226 | 0.402565 | 0.019* | |
P1 | 0.30785 (2) | 0.50825 (2) | 0.28302 (2) | 0.01294 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.01217 (15) | 0.01552 (18) | 0.01170 (15) | 0.00044 (13) | −0.00003 (12) | 0.00018 (13) |
C2 | 0.01322 (16) | 0.01449 (18) | 0.01282 (16) | 0.00049 (13) | 0.00104 (13) | 0.00047 (13) |
C3 | 0.01699 (18) | 0.01457 (18) | 0.01492 (18) | 0.00116 (15) | 0.00207 (15) | 0.00058 (14) |
C4 | 0.0186 (2) | 0.0185 (2) | 0.01606 (19) | 0.00494 (17) | 0.00119 (16) | 0.00147 (16) |
C5 | 0.01477 (18) | 0.0216 (2) | 0.01543 (19) | 0.00428 (16) | −0.00081 (14) | −0.00021 (16) |
C6 | 0.01212 (16) | 0.0188 (2) | 0.01339 (17) | 0.00089 (14) | −0.00016 (13) | −0.00081 (15) |
Cl1 | 0.01217 (4) | 0.02283 (6) | 0.02221 (6) | −0.00163 (4) | −0.00128 (4) | −0.00260 (5) |
Cl2 | 0.02347 (6) | 0.01390 (5) | 0.02461 (6) | −0.00095 (4) | 0.00527 (5) | 0.00048 (4) |
Ni1 | 0.01097 (3) | 0.01294 (3) | 0.01130 (3) | −0.00013 (3) | −0.00028 (2) | 0.00049 (3) |
S1 | 0.01211 (4) | 0.01396 (5) | 0.01675 (5) | −0.00063 (4) | −0.00073 (4) | 0.00095 (4) |
S2 | 0.01241 (4) | 0.01414 (5) | 0.01853 (5) | −0.00102 (4) | −0.00017 (4) | −0.00048 (4) |
C26 | 0.0461 (5) | 0.0327 (4) | 0.0346 (4) | −0.0137 (4) | 0.0114 (4) | −0.0004 (3) |
C27 | 0.0324 (4) | 0.0286 (4) | 0.0280 (3) | 0.0110 (3) | 0.0074 (3) | 0.0031 (3) |
O1 | 0.0229 (2) | 0.0295 (3) | 0.0263 (2) | 0.00218 (19) | 0.00738 (18) | 0.0043 (2) |
S3 | 0.02443 (7) | 0.02297 (7) | 0.01815 (6) | 0.00590 (6) | 0.00238 (5) | 0.00205 (5) |
C7 | 0.0228 (2) | 0.0166 (2) | 0.0181 (2) | 0.00303 (18) | −0.00245 (18) | −0.00430 (17) |
C8 | 0.01524 (17) | 0.01426 (18) | 0.01360 (17) | 0.00042 (14) | −0.00283 (13) | −0.00025 (14) |
C9 | 0.0190 (2) | 0.0183 (2) | 0.01426 (18) | 0.00229 (16) | −0.00122 (15) | −0.00028 (15) |
C10 | 0.0193 (2) | 0.0188 (2) | 0.0187 (2) | 0.00295 (17) | 0.00007 (17) | −0.00073 (17) |
C11 | 0.01683 (19) | 0.0176 (2) | 0.0211 (2) | 0.00211 (16) | −0.00277 (17) | 0.00089 (17) |
C12 | 0.01733 (19) | 0.0195 (2) | 0.01633 (19) | 0.00114 (16) | −0.00403 (15) | 0.00216 (16) |
C13 | 0.01614 (18) | 0.0191 (2) | 0.01403 (18) | 0.00058 (16) | −0.00239 (14) | 0.00083 (15) |
C14 | 0.01527 (17) | 0.01253 (17) | 0.01226 (16) | 0.00013 (13) | −0.00095 (13) | 0.00035 (13) |
C15 | 0.0225 (2) | 0.0164 (2) | 0.01415 (18) | −0.00095 (17) | 0.00306 (16) | 0.00018 (15) |
C16 | 0.0267 (3) | 0.0183 (2) | 0.0193 (2) | −0.0033 (2) | 0.0063 (2) | 0.00177 (18) |
C17 | 0.0234 (2) | 0.0145 (2) | 0.0223 (2) | −0.00298 (18) | 0.00232 (19) | 0.00092 (17) |
C18 | 0.0242 (2) | 0.0147 (2) | 0.0175 (2) | −0.00266 (17) | 0.00067 (18) | −0.00214 (16) |
C19 | 0.0210 (2) | 0.01515 (19) | 0.01351 (17) | −0.00224 (16) | 0.00148 (15) | −0.00133 (14) |
C20 | 0.01564 (17) | 0.01261 (17) | 0.01469 (17) | −0.00110 (14) | −0.00180 (14) | 0.00163 (14) |
C21 | 0.0173 (2) | 0.0155 (2) | 0.0279 (3) | −0.00356 (16) | −0.00173 (19) | 0.00446 (19) |
C22 | 0.0233 (3) | 0.0169 (2) | 0.0316 (3) | −0.00259 (19) | 0.0053 (2) | 0.0079 (2) |
C23 | 0.0291 (3) | 0.0179 (2) | 0.0194 (2) | 0.0019 (2) | 0.0038 (2) | 0.00657 (18) |
C24 | 0.0226 (2) | 0.0192 (2) | 0.01544 (19) | 0.00185 (18) | −0.00252 (17) | 0.00348 (17) |
C25 | 0.01590 (18) | 0.01669 (19) | 0.01426 (17) | −0.00084 (15) | −0.00139 (14) | 0.00235 (15) |
P1 | 0.01473 (5) | 0.01206 (5) | 0.01198 (5) | 0.00037 (4) | −0.00260 (4) | −0.00037 (4) |
Geometric parameters (Å, º) top
C1—C2 | 1.4173 (8) | C8—P1 | 1.7903 (6) |
C1—C6 | 1.4000 (7) | C9—C10 | 1.3906 (9) |
C1—S1 | 1.7419 (6) | C10—C11 | 1.3916 (9) |
C2—C3 | 1.4044 (8) | C11—C12 | 1.3925 (9) |
C2—S2 | 1.7418 (5) | C12—C13 | 1.3887 (8) |
C3—C4 | 1.3909 (8) | C14—C15 | 1.3938 (8) |
C3—Cl2 | 1.7407 (6) | C14—C19 | 1.3988 (8) |
C4—C5 | 1.3886 (10) | C14—P1 | 1.7915 (6) |
C5—C6 | 1.3894 (9) | C15—C16 | 1.3933 (9) |
C6—Cl1 | 1.7456 (6) | C16—C17 | 1.3874 (10) |
Ni1—S1 | 2.1702 (1) | C17—C18 | 1.3929 (9) |
Ni1—S1i | 2.1702 (1) | C18—C19 | 1.3895 (9) |
Ni1—S2i | 2.1733 (2) | C20—C21 | 1.3988 (8) |
Ni1—S2 | 2.1733 (2) | C20—C25 | 1.3996 (8) |
C26—S3 | 1.7775 (11) | C20—P1 | 1.7903 (6) |
C27—S3 | 1.7885 (8) | C21—C22 | 1.3908 (10) |
O1—S3 | 1.4980 (6) | C22—C23 | 1.3895 (11) |
C7—P1 | 1.7833 (6) | C23—C24 | 1.3881 (10) |
C8—C9 | 1.3994 (8) | C24—C25 | 1.3897 (8) |
C8—C13 | 1.3998 (8) | | |
| | | |
C2—C1—S1 | 119.10 (4) | C10—C9—C8 | 119.79 (5) |
C6—C1—C2 | 118.42 (5) | C9—C10—C11 | 119.89 (6) |
C6—C1—S1 | 122.47 (4) | C10—C11—C12 | 120.31 (6) |
C1—C2—S2 | 118.91 (4) | C13—C12—C11 | 120.29 (5) |
C3—C2—C1 | 117.92 (5) | C12—C13—C8 | 119.46 (5) |
C3—C2—S2 | 123.17 (4) | C15—C14—C19 | 120.44 (5) |
C2—C3—Cl2 | 119.29 (4) | C15—C14—P1 | 120.40 (4) |
C4—C3—C2 | 122.68 (6) | C19—C14—P1 | 118.92 (4) |
C4—C3—Cl2 | 118.02 (5) | C16—C15—C14 | 119.27 (6) |
C5—C4—C3 | 119.23 (6) | C17—C16—C15 | 120.45 (6) |
C4—C5—C6 | 119.00 (5) | C16—C17—C18 | 120.17 (6) |
C1—C6—Cl1 | 119.03 (5) | C19—C18—C17 | 119.95 (6) |
C5—C6—C1 | 122.75 (6) | C18—C19—C14 | 119.70 (5) |
C5—C6—Cl1 | 118.21 (4) | C21—C20—C25 | 120.12 (5) |
S1—Ni1—S1i | 180.0 | C21—C20—P1 | 121.01 (5) |
S1i—Ni1—S2 | 88.673 (5) | C25—C20—P1 | 118.57 (4) |
S1i—Ni1—S2i | 91.326 (5) | C22—C21—C20 | 119.66 (6) |
S1—Ni1—S2 | 91.326 (5) | C23—C22—C21 | 120.07 (6) |
S1—Ni1—S2i | 88.674 (5) | C24—C23—C22 | 120.33 (6) |
S2i—Ni1—S2 | 180.0 | C23—C24—C25 | 120.24 (6) |
C1—S1—Ni1 | 104.669 (18) | C24—C25—C20 | 119.56 (5) |
C2—S2—Ni1 | 104.64 (2) | C7—P1—C8 | 110.30 (3) |
C26—S3—C27 | 97.13 (5) | C7—P1—C14 | 110.54 (3) |
O1—S3—C26 | 106.47 (4) | C7—P1—C20 | 108.34 (3) |
O1—S3—C27 | 105.84 (4) | C8—P1—C14 | 106.45 (3) |
C9—C8—C13 | 120.23 (5) | C8—P1—C20 | 111.10 (3) |
C9—C8—P1 | 121.52 (4) | C20—P1—C14 | 110.12 (3) |
C13—C8—P1 | 117.88 (4) | | |
Symmetry code: (i) −x, −y+2, −z+1. |
Crystal data top
2(C6H2Cl2Ni0.5S2)·C19H18P | F(000) = 1532 |
Mr = 754.20 | Dx = 1.622 Mg m−3 |
Monoclinic, P21/c | Ag Kα radiation, λ = 0.56083 Å |
a = 13.3664 (1) Å | Cell parameters from 1181142 reflections |
b = 14.4849 (1) Å | θ = 2.0–39.2° |
c = 15.9712 (1) Å | µ = 0.68 mm−1 |
β = 93.054 (1)° | T = 100 K |
V = 3087.81 (4) Å3 | Plate, black-green |
Z = 4 | 0.23 × 0.16 × 0.03 mm |
Data collection top
STOE STADIVARI diffractometer | 36081 independent reflections |
Radiation source: Incoatec HB Iµs 2.0, Incoatec Ag tube | 25847 reflections with I > 2σ(I) |
Graded multilayer mirror monochromator | Rint = 0.030 |
Detector resolution: 5.81 pixels mm-1 | θmax = 39.2°, θmin = 2.0° |
rotation method, ω scans | h = −29→29 |
Absorption correction: multi-scan STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens, "The Evaluation of Absorption and Extinction in Single-Crystal
Structure Analysis", published in: F. R. Ahmed (Editor), "Crystallographic
Computing", Munksgaard, Copenhagen (1970), 255 - 270.
Afterwards scaling of reflection intensities was performed within STOE LANA.
J. Koziskova, F. Hahn, J. Richter, J. Kozisek, "Comparison of different
absorption corrections on the model structure of tetrakis(µ2-acetato)-
diaqua-di-copper(II)", Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
Finally a spherical absorption correction was done within STOE LANA. | k = −32→29 |
Tmin = 0.262, Tmax = 0.834 | l = −34→35 |
653883 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.079 | w = 1/[σ2(Fo2) + (0.0343P)2 + 0.6067P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.006 |
36081 reflections | Δρmax = 0.83 e Å−3 |
375 parameters | Δρmin = −0.74 e Å−3 |
0 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni1 | 0.500000 | 0.500000 | 1.000000 | 0.01386 (1) | |
Cl1 | 0.44153 (2) | 0.15548 (2) | 1.08435 (2) | 0.02660 (3) | |
Cl2 | 0.11275 (2) | 0.44048 (2) | 0.97156 (2) | 0.02688 (3) | |
S1 | 0.50447 (2) | 0.35367 (2) | 1.02194 (2) | 0.01689 (2) | |
S2 | 0.33996 (2) | 0.50270 (2) | 0.99057 (2) | 0.01750 (2) | |
C1 | 0.37965 (4) | 0.32298 (4) | 1.02682 (3) | 0.01685 (7) | |
C2 | 0.34982 (5) | 0.23424 (4) | 1.05051 (4) | 0.02083 (9) | |
C3 | 0.24999 (6) | 0.20960 (5) | 1.05044 (4) | 0.02665 (12) | |
H3 | 0.231881 | 0.150692 | 1.067151 | 0.032* | |
C4 | 0.17663 (5) | 0.27349 (5) | 1.02520 (4) | 0.02646 (12) | |
H4 | 0.109409 | 0.256615 | 1.022723 | 0.032* | |
C5 | 0.20406 (4) | 0.36210 (5) | 1.00384 (4) | 0.02089 (9) | |
C6 | 0.30501 (4) | 0.38957 (4) | 1.00741 (3) | 0.01693 (7) | |
Ni2 | 0.000000 | 0.500000 | 0.500000 | 0.01217 (1) | |
Cl3 | −0.05222 (2) | 0.57008 (2) | 0.81887 (2) | 0.02373 (3) | |
Cl4 | 0.13497 (2) | 0.83647 (2) | 0.56430 (2) | 0.02342 (3) | |
S3 | −0.03683 (2) | 0.50657 (2) | 0.62876 (2) | 0.01552 (2) | |
S4 | 0.06282 (2) | 0.63643 (2) | 0.50385 (2) | 0.01479 (2) | |
C7 | 0.00302 (4) | 0.61503 (4) | 0.66256 (3) | 0.01500 (6) | |
C8 | −0.00609 (4) | 0.64505 (4) | 0.74573 (3) | 0.01812 (8) | |
C9 | 0.02238 (5) | 0.73304 (5) | 0.77058 (4) | 0.02198 (9) | |
H9 | 0.014003 | 0.752279 | 0.825317 | 0.026* | |
C10 | 0.06366 (5) | 0.79287 (4) | 0.71342 (4) | 0.02200 (9) | |
H10 | 0.081829 | 0.852479 | 0.729627 | 0.026* | |
C11 | 0.07750 (4) | 0.76330 (4) | 0.63253 (4) | 0.01800 (8) | |
C12 | 0.04696 (4) | 0.67476 (4) | 0.60532 (3) | 0.01490 (6) | |
P1 | 0.38094 (2) | −0.11135 (2) | 1.18222 (2) | 0.01378 (2) | |
C13 | 0.33689 (5) | −0.12594 (5) | 1.07500 (4) | 0.02218 (10) | |
H13A | 0.368469 | −0.178969 | 1.051851 | 0.033* | |
H13B | 0.353032 | −0.072015 | 1.043483 | 0.033* | |
H13C | 0.265590 | −0.134635 | 1.072279 | 0.033* | |
C14 | 0.33966 (4) | −0.20663 (3) | 1.24227 (3) | 0.01549 (7) | |
C15 | 0.29695 (4) | −0.19089 (4) | 1.31877 (3) | 0.01739 (7) | |
H15 | 0.290091 | −0.130982 | 1.338624 | 0.021* | |
C16 | 0.26466 (5) | −0.26544 (4) | 1.36519 (4) | 0.02086 (9) | |
H16 | 0.236011 | −0.255552 | 1.416233 | 0.025* | |
C17 | 0.27529 (5) | −0.35440 (4) | 1.33518 (5) | 0.02442 (11) | |
H17 | 0.253115 | −0.404080 | 1.366085 | 0.029* | |
C18 | 0.31882 (5) | −0.37023 (4) | 1.25928 (5) | 0.02614 (12) | |
H18 | 0.326081 | −0.430301 | 1.239955 | 0.031* | |
C19 | 0.35142 (5) | −0.29653 (4) | 1.21235 (4) | 0.02137 (9) | |
H19 | 0.380711 | −0.306783 | 1.161643 | 0.026* | |
C20 | 0.51456 (3) | −0.10846 (4) | 1.18638 (3) | 0.01423 (6) | |
C21 | 0.56463 (4) | −0.07975 (4) | 1.11644 (3) | 0.01693 (7) | |
H21 | 0.528531 | −0.059751 | 1.068442 | 0.020* | |
C22 | 0.66841 (4) | −0.08122 (4) | 1.11888 (3) | 0.01796 (8) | |
H22 | 0.702069 | −0.063934 | 1.071870 | 0.022* | |
C23 | 0.72213 (4) | −0.10845 (4) | 1.19143 (4) | 0.01783 (7) | |
H23 | 0.791777 | −0.108935 | 1.192966 | 0.021* | |
C24 | 0.67249 (4) | −0.13499 (4) | 1.26180 (4) | 0.01928 (8) | |
H24 | 0.708963 | −0.151945 | 1.310602 | 0.023* | |
C25 | 0.56850 (4) | −0.13623 (4) | 1.25937 (3) | 0.01774 (8) | |
H25 | 0.535065 | −0.155391 | 1.305922 | 0.021* | |
C26 | 0.33116 (4) | −0.00789 (3) | 1.22352 (3) | 0.01579 (7) | |
C27 | 0.22827 (4) | 0.00801 (4) | 1.21151 (5) | 0.02242 (10) | |
H27 | 0.188254 | −0.033174 | 1.180105 | 0.027* | |
C28 | 0.18611 (5) | 0.08534 (5) | 1.24655 (5) | 0.02560 (11) | |
H28 | 0.117579 | 0.095898 | 1.239138 | 0.031* | |
C29 | 0.24644 (5) | 0.14719 (4) | 1.29284 (4) | 0.02289 (10) | |
H29 | 0.218048 | 0.199089 | 1.316320 | 0.027* | |
C30 | 0.34841 (5) | 0.13191 (4) | 1.30413 (4) | 0.02172 (9) | |
H30 | 0.388356 | 0.173961 | 1.334579 | 0.026* | |
C31 | 0.39149 (4) | 0.05398 (4) | 1.27017 (4) | 0.01834 (8) | |
H31 | 0.459887 | 0.043224 | 1.278489 | 0.022* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.01229 (3) | 0.01431 (3) | 0.01497 (3) | −0.00180 (2) | 0.00053 (2) | 0.00185 (3) |
Cl1 | 0.04480 (9) | 0.01647 (5) | 0.01878 (5) | −0.00133 (5) | 0.00394 (5) | 0.00278 (4) |
Cl2 | 0.01391 (5) | 0.03989 (9) | 0.02695 (6) | −0.00238 (5) | 0.00203 (4) | −0.00594 (6) |
S1 | 0.01661 (5) | 0.01574 (5) | 0.01825 (5) | −0.00083 (4) | 0.00039 (4) | 0.00264 (4) |
S2 | 0.01315 (4) | 0.01774 (5) | 0.02160 (5) | −0.00104 (4) | 0.00098 (4) | 0.00140 (4) |
C1 | 0.01978 (18) | 0.01683 (17) | 0.01413 (15) | −0.00465 (14) | 0.00279 (13) | 0.00000 (13) |
C2 | 0.0299 (3) | 0.01710 (19) | 0.01605 (17) | −0.00653 (17) | 0.00611 (17) | −0.00146 (15) |
C3 | 0.0347 (3) | 0.0227 (2) | 0.0236 (2) | −0.0142 (2) | 0.0116 (2) | −0.00559 (19) |
C4 | 0.0246 (2) | 0.0307 (3) | 0.0250 (2) | −0.0147 (2) | 0.0094 (2) | −0.0084 (2) |
C5 | 0.01665 (18) | 0.0280 (2) | 0.01835 (19) | −0.00734 (17) | 0.00420 (15) | −0.00556 (18) |
C6 | 0.01554 (16) | 0.01981 (19) | 0.01562 (16) | −0.00484 (14) | 0.00262 (13) | −0.00138 (14) |
Ni2 | 0.01024 (3) | 0.01420 (3) | 0.01220 (3) | 0.00101 (2) | 0.00178 (2) | 0.00023 (2) |
Cl3 | 0.02453 (6) | 0.03282 (7) | 0.01415 (4) | 0.00243 (5) | 0.00392 (4) | 0.00092 (4) |
Cl4 | 0.02408 (6) | 0.01630 (5) | 0.03000 (7) | −0.00139 (4) | 0.00243 (5) | 0.00118 (4) |
S3 | 0.01530 (4) | 0.01794 (5) | 0.01360 (4) | −0.00096 (3) | 0.00338 (3) | 0.00016 (3) |
S4 | 0.01415 (4) | 0.01528 (4) | 0.01515 (4) | 0.00025 (3) | 0.00261 (3) | 0.00088 (3) |
C7 | 0.01235 (14) | 0.01852 (17) | 0.01420 (15) | 0.00230 (12) | 0.00126 (11) | −0.00099 (13) |
C8 | 0.01555 (16) | 0.0240 (2) | 0.01486 (16) | 0.00296 (15) | 0.00112 (13) | −0.00222 (15) |
C9 | 0.0200 (2) | 0.0263 (2) | 0.0195 (2) | 0.00289 (18) | 0.00020 (16) | −0.00742 (18) |
C10 | 0.0202 (2) | 0.0208 (2) | 0.0248 (2) | 0.00172 (17) | −0.00049 (17) | −0.00694 (18) |
C11 | 0.01578 (16) | 0.01621 (17) | 0.0219 (2) | 0.00141 (13) | 0.00032 (14) | −0.00188 (15) |
C12 | 0.01241 (14) | 0.01575 (16) | 0.01652 (16) | 0.00195 (12) | 0.00083 (12) | −0.00071 (13) |
P1 | 0.01149 (4) | 0.01543 (5) | 0.01436 (4) | −0.00148 (3) | 0.00019 (3) | 0.00147 (4) |
C13 | 0.01776 (19) | 0.0317 (3) | 0.01672 (18) | −0.00233 (18) | −0.00282 (15) | 0.00045 (18) |
C14 | 0.01375 (15) | 0.01417 (15) | 0.01864 (17) | −0.00182 (12) | 0.00179 (13) | 0.00105 (13) |
C15 | 0.01764 (17) | 0.01682 (17) | 0.01784 (17) | −0.00248 (14) | 0.00204 (14) | 0.00150 (14) |
C16 | 0.0195 (2) | 0.0210 (2) | 0.0223 (2) | −0.00179 (16) | 0.00343 (16) | 0.00575 (17) |
C17 | 0.0203 (2) | 0.0179 (2) | 0.0354 (3) | −0.00084 (16) | 0.0048 (2) | 0.0087 (2) |
C18 | 0.0245 (2) | 0.01407 (18) | 0.0405 (4) | −0.00009 (17) | 0.0078 (2) | 0.0017 (2) |
C19 | 0.0207 (2) | 0.01561 (18) | 0.0283 (2) | −0.00043 (15) | 0.00625 (18) | −0.00154 (17) |
C20 | 0.01211 (13) | 0.01671 (16) | 0.01390 (14) | −0.00113 (12) | 0.00105 (11) | 0.00122 (12) |
C21 | 0.01548 (16) | 0.0218 (2) | 0.01361 (15) | −0.00187 (14) | 0.00165 (13) | 0.00148 (14) |
C22 | 0.01594 (17) | 0.0210 (2) | 0.01738 (17) | −0.00275 (14) | 0.00478 (14) | −0.00074 (15) |
C23 | 0.01293 (15) | 0.01821 (18) | 0.0225 (2) | −0.00043 (13) | 0.00255 (14) | 0.00026 (16) |
C24 | 0.01362 (16) | 0.0235 (2) | 0.02051 (19) | 0.00008 (15) | −0.00093 (14) | 0.00540 (17) |
C25 | 0.01391 (15) | 0.0233 (2) | 0.01594 (16) | −0.00078 (14) | 0.00063 (13) | 0.00529 (15) |
C26 | 0.01372 (15) | 0.01444 (16) | 0.01922 (18) | −0.00139 (12) | 0.00107 (13) | 0.00238 (13) |
C27 | 0.01422 (17) | 0.01721 (19) | 0.0356 (3) | 0.00002 (14) | −0.00031 (18) | −0.00130 (19) |
C28 | 0.0186 (2) | 0.0190 (2) | 0.0394 (3) | 0.00301 (17) | 0.0029 (2) | −0.0001 (2) |
C29 | 0.0266 (2) | 0.01672 (19) | 0.0259 (2) | 0.00165 (17) | 0.0061 (2) | 0.00134 (18) |
C30 | 0.0257 (2) | 0.0195 (2) | 0.0201 (2) | −0.00256 (18) | 0.00197 (18) | −0.00141 (17) |
C31 | 0.01761 (18) | 0.01937 (19) | 0.01799 (18) | −0.00242 (15) | 0.00044 (14) | 0.00024 (15) |
Geometric parameters (Å, º) top
Ni1—S1 | 2.1486 (1) | C13—H13A | 0.9600 |
Ni1—S1i | 2.1487 (1) | C13—H13B | 0.9600 |
Ni1—S2 | 2.1369 (1) | C13—H13C | 0.9600 |
Ni1—S2i | 2.1369 (1) | C14—C15 | 1.3947 (8) |
Cl1—C2 | 1.7394 (7) | C14—C19 | 1.3989 (8) |
Cl2—C5 | 1.7254 (7) | C15—H15 | 0.9300 |
S1—C1 | 1.7323 (6) | C15—C16 | 1.3914 (8) |
S2—C6 | 1.7290 (6) | C16—H16 | 0.9300 |
C1—C2 | 1.4038 (8) | C16—C17 | 1.3848 (10) |
C1—C6 | 1.4102 (8) | C17—H17 | 0.9300 |
C2—C3 | 1.3812 (10) | C17—C18 | 1.3914 (11) |
C3—H3 | 0.9300 | C18—H18 | 0.9300 |
C3—C4 | 1.3921 (12) | C18—C19 | 1.3878 (9) |
C4—H4 | 0.9300 | C19—H19 | 0.9300 |
C4—C5 | 1.3826 (10) | C20—C21 | 1.3958 (7) |
C5—C6 | 1.4051 (7) | C20—C25 | 1.3968 (7) |
Ni2—S3 | 2.1420 (1) | C21—H21 | 0.9300 |
Ni2—S3ii | 2.1421 (1) | C21—C22 | 1.3858 (8) |
Ni2—S4ii | 2.1467 (1) | C22—H22 | 0.9300 |
Ni2—S4 | 2.1467 (1) | C22—C23 | 1.3874 (8) |
Cl3—C8 | 1.7322 (6) | C23—H23 | 0.9300 |
Cl4—C11 | 1.7292 (6) | C23—C24 | 1.3895 (8) |
S3—C7 | 1.7357 (6) | C24—H24 | 0.9300 |
S4—C12 | 1.7367 (5) | C24—C25 | 1.3885 (7) |
C7—C8 | 1.4091 (7) | C25—H25 | 0.9300 |
C7—C12 | 1.4094 (7) | C26—C27 | 1.3975 (8) |
C8—C9 | 1.3823 (9) | C26—C31 | 1.3945 (8) |
C9—H9 | 0.9300 | C27—H27 | 0.9300 |
C9—C10 | 1.3937 (10) | C27—C28 | 1.3853 (9) |
C10—H10 | 0.9300 | C28—H28 | 0.9300 |
C10—C11 | 1.3827 (9) | C28—C29 | 1.3915 (10) |
C11—C12 | 1.4076 (7) | C29—H29 | 0.9300 |
P1—C13 | 1.7934 (6) | C29—C30 | 1.3831 (10) |
P1—C14 | 1.7847 (5) | C30—H30 | 0.9300 |
P1—C20 | 1.7843 (5) | C30—C31 | 1.3903 (9) |
P1—C26 | 1.7806 (6) | C31—H31 | 0.9300 |
| | | |
S1—Ni1—S1i | 180.0 | P1—C13—H13B | 109.5 |
S2i—Ni1—S1 | 87.216 (5) | P1—C13—H13C | 109.5 |
S2—Ni1—S1i | 87.216 (5) | H13A—C13—H13B | 109.5 |
S2i—Ni1—S1i | 92.784 (5) | H13A—C13—H13C | 109.5 |
S2—Ni1—S1 | 92.784 (5) | H13B—C13—H13C | 109.5 |
S2—Ni1—S2i | 180.0 | C15—C14—P1 | 119.81 (4) |
C1—S1—Ni1 | 104.00 (2) | C15—C14—C19 | 120.68 (5) |
C6—S2—Ni1 | 104.443 (19) | C19—C14—P1 | 119.52 (4) |
C2—C1—S1 | 122.35 (5) | C14—C15—H15 | 120.2 |
C2—C1—C6 | 118.54 (5) | C16—C15—C14 | 119.53 (5) |
C6—C1—S1 | 119.10 (4) | C16—C15—H15 | 120.2 |
C1—C2—Cl1 | 118.60 (5) | C15—C16—H16 | 120.1 |
C3—C2—Cl1 | 119.71 (5) | C17—C16—C15 | 119.82 (6) |
C3—C2—C1 | 121.64 (7) | C17—C16—H16 | 120.1 |
C2—C3—H3 | 120.2 | C16—C17—H17 | 119.7 |
C2—C3—C4 | 119.61 (6) | C16—C17—C18 | 120.69 (6) |
C4—C3—H3 | 120.2 | C18—C17—H17 | 119.7 |
C3—C4—H4 | 120.1 | C17—C18—H18 | 119.9 |
C5—C4—C3 | 119.78 (6) | C19—C18—C17 | 120.11 (6) |
C5—C4—H4 | 120.1 | C19—C18—H18 | 119.9 |
C4—C5—Cl2 | 119.47 (5) | C14—C19—H19 | 120.4 |
C4—C5—C6 | 121.30 (7) | C18—C19—C14 | 119.16 (6) |
C6—C5—Cl2 | 119.23 (5) | C18—C19—H19 | 120.4 |
C1—C6—S2 | 119.25 (4) | C21—C20—P1 | 119.93 (4) |
C5—C6—S2 | 121.93 (5) | C21—C20—C25 | 120.37 (4) |
C5—C6—C1 | 118.81 (5) | C25—C20—P1 | 119.70 (4) |
S3—Ni2—S3ii | 180.0 | C20—C21—H21 | 120.2 |
S3—Ni2—S4ii | 87.645 (5) | C22—C21—C20 | 119.65 (5) |
S3ii—Ni2—S4ii | 92.355 (5) | C22—C21—H21 | 120.2 |
S3—Ni2—S4 | 92.357 (5) | C21—C22—H22 | 120.0 |
S3ii—Ni2—S4 | 87.643 (5) | C21—C22—C23 | 120.04 (5) |
S4ii—Ni2—S4 | 180.0 | C23—C22—H22 | 120.0 |
C7—S3—Ni2 | 104.856 (18) | C22—C23—H23 | 119.8 |
C12—S4—Ni2 | 104.718 (18) | C22—C23—C24 | 120.40 (5) |
C8—C7—S3 | 122.14 (4) | C24—C23—H23 | 119.8 |
C8—C7—C12 | 118.82 (5) | C23—C24—H24 | 120.0 |
C12—C7—S3 | 119.04 (4) | C25—C24—C23 | 120.09 (5) |
C7—C8—Cl3 | 119.61 (5) | C25—C24—H24 | 120.0 |
C9—C8—Cl3 | 119.13 (4) | C20—C25—H25 | 120.3 |
C9—C8—C7 | 121.25 (6) | C24—C25—C20 | 119.41 (5) |
C8—C9—H9 | 120.1 | C24—C25—H25 | 120.3 |
C8—C9—C10 | 119.85 (5) | C27—C26—P1 | 118.18 (4) |
C10—C9—H9 | 120.1 | C31—C26—P1 | 121.47 (4) |
C9—C10—H10 | 120.1 | C31—C26—C27 | 120.28 (5) |
C11—C10—C9 | 119.78 (6) | C26—C27—H27 | 120.1 |
C11—C10—H10 | 120.1 | C28—C27—C26 | 119.76 (6) |
C10—C11—Cl4 | 119.01 (5) | C28—C27—H27 | 120.1 |
C10—C11—C12 | 121.31 (6) | C27—C28—H28 | 120.0 |
C12—C11—Cl4 | 119.68 (4) | C27—C28—C29 | 119.91 (6) |
C7—C12—S4 | 119.00 (4) | C29—C28—H28 | 120.0 |
C11—C12—S4 | 122.12 (4) | C28—C29—H29 | 119.8 |
C11—C12—C7 | 118.88 (5) | C30—C29—C28 | 120.36 (6) |
C14—P1—C13 | 109.08 (3) | C30—C29—H29 | 119.8 |
C20—P1—C13 | 108.38 (3) | C29—C30—H30 | 119.8 |
C20—P1—C14 | 109.61 (2) | C29—C30—C31 | 120.32 (6) |
C26—P1—C13 | 110.04 (3) | C31—C30—H30 | 119.8 |
C26—P1—C14 | 108.63 (3) | C26—C31—H31 | 120.3 |
C26—P1—C20 | 111.07 (2) | C30—C31—C26 | 119.37 (5) |
P1—C13—H13A | 109.5 | C30—C31—H31 | 120.3 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x, −y+1, −z+1. |
Crystal data top
2(C6H2Cl2Ni0.5S2)·C19H18P | F(000) = 1532 |
Mr = 754.20 | Dx = 1.628 Mg m−3 |
Monoclinic, P21/c | Synchrotron radiation, λ = 0.30996 Å |
a = 13.3785 (1) Å | Cell parameters from 590779 reflections |
b = 14.4463 (2) Å | θ = 1.5–28.0° |
c = 15.9474 (2) Å | µ = 1.33 mm−1 |
β = 93.364 (1)° | T = 15 K |
V = 3076.84 (6) Å3 | Plate, black-green |
Z = 4 | 0.09 × 0.05 × 0.03 mm |
Data collection top
Bruker D8 goniometer diffractometer | 89538 independent reflections |
Radiation source: synchrotron, Incoatec Iµs | 64088 reflections with I > 2σ(I) |
Mirror optics monochromator | Rint = 0.050 |
ω and phi scans | θmax = 28.0°, θmin = 1.5° |
Absorption correction: multi-scan SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0490 before and 0.0490 after correction.
The Ratio of minimum to maximum transmission is 0.8937.
The λ/2 correction factor is Not present. | h = −37→40 |
Tmin = 0.894, Tmax = 1.000 | k = −42→43 |
831499 measured reflections | l = −46→48 |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.085 | w = 1/[σ2(Fo2) + (0.0408P)2 + 0.1535P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.010 |
88732 reflections | Δρmax = 2.47 e Å−3 |
374 parameters | Δρmin = −3.18 e Å−3 |
0 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni1 | 0.500000 | 0.500000 | 1.000000 | 0.00407 (1) | |
Cl1 | 0.44448 (2) | 0.15373 (2) | 1.08440 (2) | 0.00792 (1) | |
Cl2 | 0.11211 (2) | 0.43810 (2) | 0.97214 (2) | 0.00817 (1) | |
S1 | 0.50536 (2) | 0.35281 (2) | 1.02086 (2) | 0.00548 (1) | |
S2 | 0.33962 (2) | 0.50202 (2) | 0.99069 (2) | 0.00584 (1) | |
C1 | 0.38065 (2) | 0.32154 (2) | 1.02661 (2) | 0.00575 (2) | |
C2 | 0.35180 (2) | 0.23228 (2) | 1.05090 (2) | 0.00678 (3) | |
C3 | 0.25192 (2) | 0.20695 (2) | 1.05173 (2) | 0.00856 (3) | |
H3 | 0.234470 | 0.147899 | 1.068908 | 0.010* | |
C4 | 0.17752 (2) | 0.27093 (2) | 1.02652 (2) | 0.00860 (3) | |
H4 | 0.110437 | 0.253741 | 1.024518 | 0.010* | |
C5 | 0.20428 (2) | 0.36009 (2) | 1.00453 (2) | 0.00686 (3) | |
C6 | 0.30529 (2) | 0.38815 (2) | 1.00754 (2) | 0.00586 (2) | |
Ni2 | 0.000000 | 0.500000 | 0.500000 | 0.00379 (1) | |
Cl3 | −0.05100 (2) | 0.57221 (2) | 0.81961 (2) | 0.00734 (1) | |
Cl4 | 0.13695 (2) | 0.83784 (2) | 0.56358 (2) | 0.00749 (1) | |
S3 | −0.03717 (2) | 0.50762 (2) | 0.62890 (2) | 0.00524 (1) | |
S4 | 0.06347 (2) | 0.63685 (2) | 0.50351 (2) | 0.00505 (1) | |
C7 | 0.04762 (2) | 0.67609 (2) | 0.60498 (2) | 0.00541 (2) | |
C8 | 0.07873 (2) | 0.76507 (2) | 0.63193 (2) | 0.00622 (3) | |
C9 | 0.06499 (2) | 0.79535 (2) | 0.71291 (2) | 0.00742 (3) | |
H9 | 0.083244 | 0.855202 | 0.728878 | 0.009* | |
C10 | 0.02350 (2) | 0.73551 (2) | 0.77062 (2) | 0.00744 (3) | |
H10 | 0.015320 | 0.755074 | 0.825352 | 0.009* | |
C11 | −0.00531 (2) | 0.64699 (2) | 0.74582 (2) | 0.00615 (3) | |
C12 | 0.00336 (2) | 0.61652 (2) | 0.66255 (2) | 0.00535 (2) | |
P13 | 0.61912 (2) | 0.11033 (2) | 0.81707 (2) | 0.00417 (1) | |
C13 | 0.66347 (2) | 0.12491 (2) | 0.92477 (2) | 0.00849 (3) | |
H13A | 0.734843 | 0.132738 | 0.927780 | 0.013* | |
H13B | 0.646554 | 0.071203 | 0.956438 | 0.013* | |
H13C | 0.632697 | 0.178590 | 0.947658 | 0.013* | |
C14 | 0.66009 (2) | 0.20604 (2) | 0.75689 (2) | 0.00562 (2) | |
C15 | 0.70290 (2) | 0.19020 (2) | 0.68028 (2) | 0.00666 (3) | |
H15 | 0.709849 | 0.130133 | 0.660462 | 0.008* | |
C16 | 0.73507 (2) | 0.26509 (2) | 0.63389 (2) | 0.00772 (3) | |
H16 | 0.763710 | 0.255168 | 0.582906 | 0.009* | |
C17 | 0.72428 (2) | 0.35477 (2) | 0.66392 (2) | 0.00842 (3) | |
H17 | 0.746445 | 0.404577 | 0.633064 | 0.010* | |
C18 | 0.68044 (2) | 0.37067 (2) | 0.74005 (2) | 0.00883 (3) | |
H18 | 0.672939 | 0.430880 | 0.759332 | 0.011* | |
C19 | 0.64806 (2) | 0.29652 (2) | 0.78694 (2) | 0.00749 (3) | |
H19 | 0.618781 | 0.306691 | 0.837605 | 0.009* | |
C20 | 0.66943 (2) | 0.00662 (2) | 0.77580 (2) | 0.00574 (2) | |
C21 | 0.77294 (2) | −0.00811 (2) | 0.78735 (2) | 0.00794 (3) | |
H21 | 0.812811 | 0.033686 | 0.818507 | 0.010* | |
C22 | 0.81564 (2) | −0.08552 (2) | 0.75200 (2) | 0.00894 (3) | |
H22 | 0.884332 | −0.095323 | 0.758923 | 0.011* | |
C23 | 0.75521 (2) | −0.14851 (2) | 0.70608 (2) | 0.00824 (3) | |
H23 | 0.783874 | −0.200285 | 0.682501 | 0.010* | |
C24 | 0.65227 (2) | −0.13436 (2) | 0.69533 (2) | 0.00790 (3) | |
H24 | 0.612402 | −0.177106 | 0.665315 | 0.009* | |
C25 | 0.60888 (2) | −0.05629 (2) | 0.72946 (2) | 0.00686 (3) | |
H25 | 0.540342 | −0.046101 | 0.721511 | 0.008* | |
C26 | 0.48528 (2) | 0.10731 (2) | 0.81253 (2) | 0.00526 (2) | |
C27 | 0.43547 (2) | 0.07903 (2) | 0.88295 (2) | 0.00651 (3) | |
H27 | 0.471783 | 0.058975 | 0.931070 | 0.008* | |
C28 | 0.33140 (2) | 0.08107 (2) | 0.88058 (2) | 0.00686 (3) | |
H28 | 0.297967 | 0.064065 | 0.927719 | 0.008* | |
C29 | 0.27730 (2) | 0.10860 (2) | 0.80754 (2) | 0.00695 (3) | |
H29 | 0.207716 | 0.109632 | 0.806067 | 0.008* | |
C30 | 0.32663 (2) | 0.13462 (2) | 0.73662 (2) | 0.00730 (3) | |
H30 | 0.289937 | 0.151580 | 0.687689 | 0.009* | |
C31 | 0.43094 (2) | 0.13522 (2) | 0.73905 (2) | 0.00674 (3) | |
H31 | 0.464180 | 0.153958 | 0.692334 | 0.008* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.00351 (1) | 0.00403 (1) | 0.00466 (1) | −0.00053 (1) | 0.00013 (1) | 0.00057 (1) |
Cl1 | 0.01165 (2) | 0.00550 (2) | 0.00665 (2) | 0.00024 (2) | 0.00098 (2) | 0.00092 (1) |
Cl2 | 0.00502 (2) | 0.01054 (2) | 0.00893 (2) | 0.00001 (2) | 0.00021 (1) | −0.00047 (2) |
S1 | 0.00488 (2) | 0.00489 (2) | 0.00665 (2) | −0.00021 (1) | 0.00025 (1) | 0.00087 (1) |
S2 | 0.00427 (2) | 0.00538 (2) | 0.00786 (2) | −0.00030 (1) | 0.00019 (1) | 0.00090 (1) |
C1 | 0.00594 (6) | 0.00544 (6) | 0.00590 (6) | −0.00113 (5) | 0.00055 (5) | 0.00039 (5) |
C2 | 0.00836 (7) | 0.00552 (6) | 0.00657 (6) | −0.00145 (5) | 0.00146 (5) | 0.00008 (5) |
C3 | 0.00945 (8) | 0.00715 (7) | 0.00930 (7) | −0.00312 (6) | 0.00245 (6) | −0.00048 (6) |
C4 | 0.00732 (7) | 0.00878 (7) | 0.00987 (8) | −0.00328 (6) | 0.00184 (6) | −0.00101 (6) |
C5 | 0.00525 (6) | 0.00796 (7) | 0.00740 (6) | −0.00157 (5) | 0.00068 (5) | −0.00058 (5) |
C6 | 0.00502 (6) | 0.00614 (6) | 0.00644 (6) | −0.00107 (5) | 0.00039 (5) | 0.00031 (5) |
Ni2 | 0.00385 (1) | 0.00406 (1) | 0.00350 (1) | 0.00000 (1) | 0.00060 (1) | −0.00027 (1) |
Cl3 | 0.00823 (2) | 0.00906 (2) | 0.00486 (2) | −0.00011 (2) | 0.00137 (1) | 0.00050 (1) |
Cl4 | 0.00864 (2) | 0.00571 (2) | 0.00823 (2) | −0.00093 (1) | 0.00135 (2) | 0.00048 (1) |
S3 | 0.00608 (2) | 0.00534 (2) | 0.00440 (2) | −0.00081 (1) | 0.00120 (1) | −0.00034 (1) |
S4 | 0.00578 (2) | 0.00493 (2) | 0.00454 (2) | −0.00042 (1) | 0.00107 (1) | −0.00015 (1) |
C7 | 0.00584 (6) | 0.00532 (6) | 0.00512 (5) | −0.00009 (5) | 0.00073 (5) | −0.00038 (4) |
C8 | 0.00683 (6) | 0.00545 (6) | 0.00641 (6) | −0.00034 (5) | 0.00068 (5) | −0.00057 (5) |
C9 | 0.00856 (7) | 0.00647 (6) | 0.00723 (6) | −0.00037 (6) | 0.00059 (6) | −0.00185 (5) |
C10 | 0.00855 (7) | 0.00775 (7) | 0.00605 (6) | −0.00018 (6) | 0.00076 (5) | −0.00187 (5) |
C11 | 0.00657 (6) | 0.00700 (6) | 0.00495 (5) | 0.00005 (5) | 0.00074 (5) | −0.00069 (5) |
C12 | 0.00567 (6) | 0.00573 (6) | 0.00470 (5) | −0.00012 (5) | 0.00080 (5) | −0.00044 (4) |
P13 | 0.00375 (2) | 0.00426 (2) | 0.00449 (2) | −0.00027 (1) | 0.00016 (1) | 0.00032 (1) |
C13 | 0.00783 (7) | 0.01123 (8) | 0.00623 (6) | −0.00066 (6) | −0.00108 (6) | −0.00009 (6) |
C14 | 0.00598 (6) | 0.00473 (5) | 0.00623 (6) | −0.00051 (5) | 0.00108 (5) | 0.00018 (5) |
C15 | 0.00797 (7) | 0.00574 (6) | 0.00639 (6) | −0.00059 (5) | 0.00151 (5) | 0.00002 (5) |
C16 | 0.00870 (7) | 0.00728 (7) | 0.00738 (7) | −0.00043 (6) | 0.00202 (6) | 0.00128 (5) |
C17 | 0.00886 (8) | 0.00616 (6) | 0.01043 (8) | −0.00026 (6) | 0.00228 (6) | 0.00216 (6) |
C18 | 0.01031 (8) | 0.00497 (6) | 0.01148 (8) | −0.00025 (6) | 0.00298 (7) | 0.00031 (6) |
C19 | 0.00899 (7) | 0.00523 (6) | 0.00851 (7) | −0.00012 (5) | 0.00260 (6) | −0.00037 (5) |
C20 | 0.00504 (6) | 0.00482 (6) | 0.00735 (6) | 0.00005 (5) | 0.00028 (5) | −0.00010 (5) |
C21 | 0.00551 (6) | 0.00646 (7) | 0.01176 (8) | 0.00024 (5) | −0.00026 (6) | −0.00154 (6) |
C22 | 0.00655 (7) | 0.00725 (7) | 0.01300 (9) | 0.00133 (6) | 0.00040 (6) | −0.00128 (6) |
C23 | 0.00895 (8) | 0.00621 (6) | 0.00964 (8) | 0.00094 (6) | 0.00135 (6) | −0.00066 (6) |
C24 | 0.00872 (7) | 0.00674 (7) | 0.00822 (7) | −0.00054 (6) | 0.00024 (6) | −0.00159 (5) |
C25 | 0.00622 (6) | 0.00664 (6) | 0.00767 (6) | −0.00043 (5) | −0.00009 (5) | −0.00080 (5) |
C26 | 0.00435 (5) | 0.00634 (6) | 0.00509 (5) | −0.00018 (5) | 0.00027 (4) | 0.00058 (5) |
C27 | 0.00576 (6) | 0.00860 (7) | 0.00521 (6) | −0.00037 (5) | 0.00058 (5) | 0.00084 (5) |
C28 | 0.00595 (6) | 0.00848 (7) | 0.00628 (6) | −0.00063 (5) | 0.00157 (5) | 0.00019 (5) |
C29 | 0.00507 (6) | 0.00789 (7) | 0.00792 (7) | −0.00012 (5) | 0.00061 (5) | 0.00027 (5) |
C30 | 0.00549 (6) | 0.00922 (7) | 0.00710 (6) | 0.00014 (6) | −0.00037 (5) | 0.00181 (6) |
C31 | 0.00536 (6) | 0.00896 (7) | 0.00590 (6) | −0.00018 (5) | 0.00029 (5) | 0.00183 (5) |
Geometric parameters (Å, º) top
Ni1—S1i | 2.1528 (1) | C13—H13A | 0.9600 |
Ni1—S1 | 2.1528 (1) | C13—H13B | 0.9600 |
Ni1—S2i | 2.1423 (1) | C13—H13C | 0.9600 |
Ni1—S2 | 2.1423 (1) | C14—C15 | 1.3982 (4) |
Cl1—C2 | 1.7415 (3) | C14—C19 | 1.4047 (4) |
Cl2—C5 | 1.7270 (3) | C15—H15 | 0.9300 |
S1—C1 | 1.7361 (3) | C15—C16 | 1.3930 (4) |
S2—C6 | 1.7332 (3) | C16—H16 | 0.9300 |
C1—C2 | 1.4068 (4) | C16—C17 | 1.3917 (4) |
C1—C6 | 1.4139 (4) | C17—H17 | 0.9300 |
C2—C3 | 1.3862 (4) | C17—C18 | 1.3979 (4) |
C3—H3 | 0.9300 | C18—H18 | 0.9300 |
C3—C4 | 1.3999 (5) | C18—C19 | 1.3901 (4) |
C4—H4 | 0.9300 | C19—H19 | 0.9300 |
C4—C5 | 1.3873 (4) | C20—C21 | 1.4026 (4) |
C5—C6 | 1.4090 (4) | C20—C25 | 1.3992 (4) |
Ni2—S3ii | 2.1458 (1) | C21—H21 | 0.9300 |
Ni2—S3 | 2.1459 (1) | C21—C22 | 1.3902 (4) |
Ni2—S4ii | 2.1510 (1) | C22—H22 | 0.9300 |
Ni2—S4 | 2.1510 (1) | C22—C23 | 1.3958 (4) |
Cl3—C11 | 1.7349 (3) | C23—H23 | 0.9300 |
Cl4—C8 | 1.7320 (3) | C23—C24 | 1.3929 (4) |
S3—C12 | 1.7387 (3) | C24—H24 | 0.9300 |
S4—C7 | 1.7392 (2) | C24—C25 | 1.3936 (4) |
C7—C8 | 1.4104 (3) | C25—H25 | 0.9300 |
C7—C12 | 1.4135 (3) | C26—C27 | 1.4001 (3) |
C8—C9 | 1.3858 (4) | C26—C31 | 1.4015 (4) |
C9—H9 | 0.9300 | C27—H27 | 0.9300 |
C9—C10 | 1.4009 (4) | C27—C28 | 1.3910 (4) |
C10—H10 | 0.9300 | C28—H28 | 0.9300 |
C10—C11 | 1.3865 (4) | C28—C29 | 1.3928 (4) |
C11—C12 | 1.4101 (3) | C29—H29 | 0.9300 |
P13—C13 | 1.7963 (3) | C29—C30 | 1.3941 (4) |
P13—C14 | 1.7875 (3) | C30—H30 | 0.9300 |
P13—C20 | 1.7840 (3) | C30—C31 | 1.3938 (4) |
P13—C26 | 1.7883 (2) | C31—H31 | 0.9300 |
| | | |
S1i—Ni1—S1 | 180.0 | P13—C13—H13B | 109.5 |
S2—Ni1—S1 | 92.772 (3) | P13—C13—H13C | 109.5 |
S2i—Ni1—S1i | 92.774 (3) | H13A—C13—H13B | 109.5 |
S2—Ni1—S1i | 87.227 (3) | H13A—C13—H13C | 109.5 |
S2i—Ni1—S1 | 87.227 (3) | H13B—C13—H13C | 109.5 |
S2i—Ni1—S2 | 180.0 | C15—C14—P13 | 119.784 (19) |
C1—S1—Ni1 | 103.988 (9) | C15—C14—C19 | 120.76 (2) |
C6—S2—Ni1 | 104.462 (9) | C19—C14—P13 | 119.455 (19) |
C2—C1—S1 | 122.22 (2) | C14—C15—H15 | 120.3 |
C2—C1—C6 | 118.64 (2) | C16—C15—C14 | 119.48 (2) |
C6—C1—S1 | 119.142 (18) | C16—C15—H15 | 120.3 |
C1—C2—Cl1 | 118.67 (2) | C15—C16—H16 | 120.0 |
C3—C2—Cl1 | 119.63 (2) | C17—C16—C15 | 119.91 (3) |
C3—C2—C1 | 121.66 (3) | C17—C16—H16 | 120.0 |
C2—C3—H3 | 120.2 | C16—C17—H17 | 119.7 |
C2—C3—C4 | 119.50 (3) | C16—C17—C18 | 120.60 (2) |
C4—C3—H3 | 120.2 | C18—C17—H17 | 119.7 |
C3—C4—H4 | 120.1 | C17—C18—H18 | 120.0 |
C5—C4—C3 | 119.73 (3) | C19—C18—C17 | 120.03 (3) |
C5—C4—H4 | 120.1 | C19—C18—H18 | 120.0 |
C4—C5—Cl2 | 119.42 (2) | C14—C19—H19 | 120.4 |
C4—C5—C6 | 121.31 (3) | C18—C19—C14 | 119.20 (2) |
C6—C5—Cl2 | 119.27 (2) | C18—C19—H19 | 120.4 |
C1—C6—S2 | 119.159 (18) | C21—C20—P13 | 118.03 (2) |
C5—C6—S2 | 122.02 (2) | C25—C20—P13 | 121.40 (2) |
C5—C6—C1 | 118.81 (2) | C25—C20—C21 | 120.48 (2) |
S3ii—Ni2—S3 | 180.0 | C20—C21—H21 | 120.2 |
S3ii—Ni2—S4ii | 92.365 (3) | C22—C21—C20 | 119.66 (3) |
S3—Ni2—S4 | 92.366 (3) | C22—C21—H21 | 120.2 |
S3ii—Ni2—S4 | 87.635 (3) | C21—C22—H22 | 120.1 |
S3—Ni2—S4ii | 87.634 (3) | C21—C22—C23 | 119.87 (3) |
S4ii—Ni2—S4 | 180.0 | C23—C22—H22 | 120.1 |
C12—S3—Ni2 | 104.862 (8) | C22—C23—H23 | 119.8 |
C7—S4—Ni2 | 104.730 (9) | C24—C23—C22 | 120.47 (3) |
C8—C7—S4 | 122.051 (19) | C24—C23—H23 | 119.8 |
C8—C7—C12 | 118.96 (2) | C23—C24—H24 | 119.9 |
C12—C7—S4 | 118.980 (18) | C23—C24—C25 | 120.14 (3) |
C7—C8—Cl4 | 119.797 (19) | C25—C24—H24 | 119.9 |
C9—C8—Cl4 | 118.95 (2) | C20—C25—H25 | 120.3 |
C9—C8—C7 | 121.25 (2) | C24—C25—C20 | 119.37 (2) |
C8—C9—H9 | 120.1 | C24—C25—H25 | 120.3 |
C8—C9—C10 | 119.79 (2) | C27—C26—P13 | 119.811 (19) |
C10—C9—H9 | 120.1 | C27—C26—C31 | 120.44 (2) |
C9—C10—H10 | 120.1 | C31—C26—P13 | 119.731 (18) |
C11—C10—C9 | 119.73 (2) | C26—C27—H27 | 120.2 |
C11—C10—H10 | 120.1 | C28—C27—C26 | 119.65 (2) |
C10—C11—Cl3 | 118.940 (19) | C28—C27—H27 | 120.2 |
C10—C11—C12 | 121.31 (2) | C27—C28—H28 | 120.0 |
C12—C11—Cl3 | 119.74 (2) | C27—C28—C29 | 119.93 (2) |
C7—C12—S3 | 119.031 (18) | C29—C28—H28 | 120.0 |
C11—C12—S3 | 122.124 (19) | C28—C29—H29 | 119.7 |
C11—C12—C7 | 118.84 (2) | C28—C29—C30 | 120.53 (2) |
C14—P13—C13 | 109.157 (14) | C30—C29—H29 | 119.7 |
C14—P13—C26 | 109.565 (12) | C29—C30—H30 | 120.0 |
C20—P13—C13 | 109.920 (14) | C31—C30—C29 | 120.00 (2) |
C20—P13—C14 | 108.500 (12) | C31—C30—H30 | 120.0 |
C20—P13—C26 | 111.293 (12) | C26—C31—H31 | 120.3 |
C26—P13—C13 | 108.380 (13) | C30—C31—C26 | 119.40 (2) |
P13—C13—H13A | 109.5 | C30—C31—H31 | 120.3 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x, −y+1, −z+1. |