Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199016078/qb0153sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016078/qb0153Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016078/qb0153IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016078/qb0153IIIsup4.hkl |
CCDC references: 140858; 140859; 140860
Complexes (I), (II) and (III) were prepared as the hexafluorophosphate salts by reaction of Ni(sacsac)2, NiCl2.6H2O and the appropriate phosphine following the method described by Cavell & Masters (1986) for the tetraphenylborate salts. Sodium hexafluorophosphate was used in place of sodium tetraphenylborate. Suitable crystals were obtained by recrystalization from acetone.
The structures were solved by Patterson and difference Fourier techniques and refined by full-matrix least squares. H atoms were placed geometrically and refined with a riding model (including free rotation about C—C bonds for methyl groups), and with Uiso constrained to be 1.2 (1.5 for methyl groups) times Ueq of the carrier atom.
Compound (III) has a mirror plane passing through the molecule and one phenyl ring shows high displacement parameters, indicative either of some disorder or deviation from true mirror symmetry. In all three complexes, the F atoms of the PF6− groups show high displacement parameters indicative of some disorder in these groups.
For (II), examination of the structure with PLATON (Spek, 1999) indicates the presence of a void of approximately 320 Å−3 between the molecules. Integration of the electron density within this void corresponds to the presence of two molecules of acetone. There are a number of small peaks of less than 2 e Å−3 within this volume indicating that the solvent is severely disordered. Application of the `squeeze' function of PLATON and further refinement reduced R[F<2σ(F)] from 0.0693 to 0.0359. A final difference map, following this refinement, contained no peaks > 0.6 e Å−3.
For all compounds, data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 Sheldrick, (1997); software used to prepare material for publication: SHELXL97.
[Ni(C25H22P2)(C5H7S2)]PF6 | F(000) = 1472 |
Mr = 719.27 | Dx = 1.483 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.8971 (1) Å | Cell parameters from 7505 reflections |
b = 17.7367 (1) Å | θ = 2–27° |
c = 16.7252 (2) Å | µ = 0.94 mm−1 |
β = 94.793 (1)° | T = 203 K |
V = 3221.32 (5) Å3 | Prism, orange |
Z = 4 | 0.50 × 0.34 × 0.28 mm |
Siemens SMART diffractometer | 7145 independent reflections |
Radiation source: fine-focus sealed tube | 6130 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
Area–detector ω scans | θmax = 27.4°, θmin = 1.7° |
Absorption correction: multi-scan (Blessing, 1995) | h = −13→13 |
Tmin = 0.652, Tmax = 0.780 | k = 0→22 |
30784 measured reflections | l = 0→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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.01 | Calculated w = 1/[σ2(Fo2) + (0.0443P)2 + 1.0272P] where P = (Fo2 + 2Fc2)/3 |
7145 reflections | (Δ/σ)max = 0.004 |
379 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
[Ni(C25H22P2)(C5H7S2)]PF6 | V = 3221.32 (5) Å3 |
Mr = 719.27 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.8971 (1) Å | µ = 0.94 mm−1 |
b = 17.7367 (1) Å | T = 203 K |
c = 16.7252 (2) Å | 0.50 × 0.34 × 0.28 mm |
β = 94.793 (1)° |
Siemens SMART diffractometer | 7145 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 6130 reflections with I > 2σ(I) |
Tmin = 0.652, Tmax = 0.780 | Rint = 0.018 |
30784 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.27 e Å−3 |
7145 reflections | Δρmin = −0.20 e Å−3 |
379 parameters |
x | y | z | Uiso*/Ueq | ||
Ni | 0.279208 (19) | 0.447682 (12) | 0.258885 (12) | 0.03983 (7) | |
P1 | 0.08592 (4) | 0.41005 (3) | 0.24260 (3) | 0.04154 (10) | |
P2 | 0.19577 (4) | 0.47619 (3) | 0.37057 (3) | 0.04210 (11) | |
S1 | 0.31493 (5) | 0.41350 (3) | 0.14117 (3) | 0.05159 (12) | |
S2 | 0.45416 (4) | 0.49097 (3) | 0.30302 (3) | 0.05657 (13) | |
C1 | 0.4856 (3) | 0.3881 (2) | 0.03745 (17) | 0.0968 (10) | |
H1A | 0.4083 | 0.3707 | 0.0109 | 0.145* | |
H1B | 0.5434 | 0.3465 | 0.0430 | 0.145* | |
H1C | 0.5190 | 0.4278 | 0.0058 | 0.145* | |
C2 | 0.4636 (2) | 0.41856 (13) | 0.12017 (13) | 0.0594 (5) | |
C3 | 0.5632 (2) | 0.44620 (14) | 0.16727 (14) | 0.0653 (6) | |
H3A | 0.6391 | 0.4426 | 0.1446 | 0.078* | |
C4 | 0.56895 (18) | 0.47843 (13) | 0.24292 (13) | 0.0597 (5) | |
C5 | 0.6924 (2) | 0.5080 (2) | 0.27811 (18) | 0.1000 (10) | |
H5A | 0.6836 | 0.5290 | 0.3309 | 0.150* | |
H5B | 0.7210 | 0.5470 | 0.2434 | 0.150* | |
H5C | 0.7517 | 0.4671 | 0.2825 | 0.150* | |
C6 | 0.03720 (16) | 0.47250 (11) | 0.32215 (11) | 0.0477 (4) | |
H6A | −0.0216 | 0.4489 | 0.3556 | 0.057* | |
H6B | 0.0066 | 0.5215 | 0.3022 | 0.057* | |
C11 | −0.01176 (16) | 0.42097 (11) | 0.15019 (10) | 0.0456 (4) | |
C12 | −0.06812 (18) | 0.48909 (12) | 0.12978 (12) | 0.0531 (4) | |
H12A | −0.0597 | 0.5300 | 0.1655 | 0.064* | |
C13 | −0.1371 (2) | 0.49691 (14) | 0.05642 (13) | 0.0633 (5) | |
H13A | −0.1760 | 0.5430 | 0.0429 | 0.076* | |
C14 | −0.1487 (2) | 0.43765 (15) | 0.00384 (13) | 0.0687 (6) | |
H14A | −0.1969 | 0.4430 | −0.0451 | 0.082* | |
C15 | −0.0903 (3) | 0.37041 (15) | 0.02223 (14) | 0.0769 (7) | |
H15A | −0.0966 | 0.3304 | −0.0147 | 0.092* | |
C16 | −0.0218 (2) | 0.36174 (13) | 0.09559 (13) | 0.0664 (6) | |
H16A | 0.0179 | 0.3157 | 0.1083 | 0.080* | |
C21 | 0.06592 (16) | 0.31433 (10) | 0.27697 (10) | 0.0443 (4) | |
C22 | −0.05090 (19) | 0.28600 (13) | 0.28734 (14) | 0.0626 (5) | |
H22A | −0.1208 | 0.3161 | 0.2745 | 0.075* | |
C23 | −0.0645 (2) | 0.21390 (14) | 0.31644 (16) | 0.0743 (7) | |
H23A | −0.1435 | 0.1952 | 0.3239 | 0.089* | |
C24 | 0.0379 (2) | 0.16915 (14) | 0.33461 (14) | 0.0681 (6) | |
H24A | 0.0285 | 0.1198 | 0.3536 | 0.082* | |
C25 | 0.1533 (2) | 0.19685 (13) | 0.32493 (15) | 0.0670 (6) | |
H25A | 0.2228 | 0.1665 | 0.3380 | 0.080* | |
C26 | 0.16826 (18) | 0.26922 (12) | 0.29607 (12) | 0.0550 (5) | |
H26A | 0.2476 | 0.2877 | 0.2894 | 0.066* | |
C31 | 0.22571 (17) | 0.56649 (11) | 0.41880 (11) | 0.0481 (4) | |
C32 | 0.2605 (3) | 0.57202 (15) | 0.50030 (14) | 0.0825 (8) | |
H32A | 0.2670 | 0.5285 | 0.5324 | 0.099* | |
C33 | 0.2858 (4) | 0.64240 (18) | 0.53400 (16) | 0.1034 (11) | |
H33A | 0.3098 | 0.6462 | 0.5891 | 0.124* | |
C34 | 0.2762 (3) | 0.70588 (15) | 0.48830 (17) | 0.0870 (8) | |
H34A | 0.2931 | 0.7533 | 0.5119 | 0.104* | |
C35 | 0.2423 (3) | 0.70070 (14) | 0.40851 (18) | 0.0895 (9) | |
H35A | 0.2351 | 0.7446 | 0.3770 | 0.107* | |
C36 | 0.2183 (3) | 0.63080 (13) | 0.37343 (14) | 0.0744 (7) | |
H36A | 0.1967 | 0.6276 | 0.3179 | 0.089* | |
C41 | 0.21143 (18) | 0.40640 (11) | 0.44968 (10) | 0.0480 (4) | |
C42 | 0.3283 (2) | 0.38055 (14) | 0.47389 (14) | 0.0684 (6) | |
H42A | 0.3957 | 0.3959 | 0.4464 | 0.082* | |
C43 | 0.3461 (3) | 0.33176 (18) | 0.53909 (17) | 0.0890 (8) | |
H43A | 0.4258 | 0.3147 | 0.5560 | 0.107* | |
C44 | 0.2476 (3) | 0.30875 (17) | 0.57835 (16) | 0.0902 (9) | |
H44A | 0.2598 | 0.2762 | 0.6226 | 0.108* | |
C45 | 0.1314 (3) | 0.33282 (18) | 0.55361 (16) | 0.0891 (8) | |
H45A | 0.0641 | 0.3157 | 0.5802 | 0.107* | |
C46 | 0.1121 (2) | 0.38206 (15) | 0.48976 (13) | 0.0690 (6) | |
H46A | 0.0322 | 0.3990 | 0.4736 | 0.083* | |
P3 | 0.54685 (5) | 0.21234 (3) | 0.29595 (3) | 0.05576 (13) | |
F1 | 0.46504 (15) | 0.24637 (9) | 0.22214 (10) | 0.0970 (5) | |
F2 | 0.65299 (14) | 0.27079 (9) | 0.28274 (11) | 0.0951 (5) | |
F3 | 0.44018 (13) | 0.15191 (9) | 0.30974 (10) | 0.0861 (4) | |
F4 | 0.62931 (14) | 0.17585 (10) | 0.36941 (9) | 0.0865 (4) | |
F5 | 0.60371 (16) | 0.15277 (9) | 0.23871 (9) | 0.0913 (5) | |
F6 | 0.48780 (17) | 0.26841 (11) | 0.35491 (12) | 0.1143 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.03590 (12) | 0.04664 (13) | 0.03674 (12) | −0.00310 (8) | 0.00178 (8) | −0.00135 (9) |
P1 | 0.0353 (2) | 0.0487 (2) | 0.0399 (2) | −0.00231 (17) | −0.00082 (16) | −0.00436 (18) |
P2 | 0.0386 (2) | 0.0512 (3) | 0.0360 (2) | 0.00002 (18) | −0.00004 (16) | −0.00394 (18) |
S1 | 0.0523 (3) | 0.0600 (3) | 0.0429 (2) | −0.0026 (2) | 0.00643 (19) | −0.0070 (2) |
S2 | 0.0414 (2) | 0.0796 (3) | 0.0486 (3) | −0.0136 (2) | 0.00268 (19) | −0.0050 (2) |
C1 | 0.092 (2) | 0.126 (3) | 0.0780 (17) | −0.0082 (18) | 0.0381 (15) | −0.0341 (17) |
C2 | 0.0623 (12) | 0.0632 (12) | 0.0550 (11) | 0.0018 (10) | 0.0186 (9) | −0.0041 (9) |
C3 | 0.0489 (11) | 0.0806 (15) | 0.0688 (13) | −0.0005 (10) | 0.0193 (10) | 0.0013 (11) |
C4 | 0.0419 (10) | 0.0760 (14) | 0.0612 (12) | −0.0064 (9) | 0.0054 (8) | 0.0075 (10) |
C5 | 0.0461 (13) | 0.166 (3) | 0.0876 (18) | −0.0282 (16) | 0.0065 (12) | −0.010 (2) |
C6 | 0.0381 (8) | 0.0597 (11) | 0.0446 (9) | 0.0020 (8) | −0.0009 (7) | −0.0088 (8) |
C11 | 0.0399 (8) | 0.0538 (10) | 0.0422 (9) | −0.0055 (7) | −0.0015 (7) | −0.0017 (7) |
C12 | 0.0524 (11) | 0.0568 (11) | 0.0495 (10) | −0.0008 (9) | 0.0008 (8) | 0.0007 (8) |
C13 | 0.0592 (12) | 0.0714 (14) | 0.0581 (12) | 0.0022 (10) | −0.0034 (9) | 0.0151 (10) |
C14 | 0.0668 (14) | 0.0892 (17) | 0.0472 (11) | −0.0147 (12) | −0.0118 (10) | 0.0104 (11) |
C15 | 0.1005 (19) | 0.0767 (16) | 0.0497 (12) | −0.0108 (14) | −0.0166 (12) | −0.0086 (11) |
C16 | 0.0826 (15) | 0.0598 (13) | 0.0537 (11) | 0.0037 (11) | −0.0129 (10) | −0.0081 (9) |
C21 | 0.0403 (8) | 0.0509 (10) | 0.0414 (8) | −0.0038 (7) | 0.0020 (7) | −0.0029 (7) |
C22 | 0.0409 (10) | 0.0674 (13) | 0.0794 (14) | −0.0037 (9) | 0.0035 (9) | 0.0077 (11) |
C23 | 0.0543 (12) | 0.0747 (15) | 0.0948 (18) | −0.0155 (11) | 0.0116 (12) | 0.0148 (13) |
C24 | 0.0777 (15) | 0.0604 (13) | 0.0673 (13) | −0.0077 (11) | 0.0123 (11) | 0.0113 (11) |
C25 | 0.0609 (13) | 0.0652 (13) | 0.0753 (14) | 0.0126 (10) | 0.0078 (11) | 0.0141 (11) |
C26 | 0.0418 (9) | 0.0611 (12) | 0.0627 (12) | 0.0013 (8) | 0.0078 (8) | 0.0050 (9) |
C31 | 0.0463 (9) | 0.0537 (10) | 0.0431 (9) | 0.0009 (8) | −0.0032 (7) | −0.0084 (8) |
C32 | 0.127 (2) | 0.0714 (15) | 0.0458 (11) | −0.0151 (15) | −0.0131 (13) | −0.0056 (10) |
C33 | 0.161 (3) | 0.087 (2) | 0.0579 (14) | −0.023 (2) | −0.0175 (17) | −0.0224 (14) |
C34 | 0.104 (2) | 0.0668 (16) | 0.0860 (18) | −0.0049 (14) | −0.0177 (16) | −0.0278 (14) |
C35 | 0.120 (2) | 0.0526 (13) | 0.0889 (18) | −0.0019 (14) | −0.0348 (17) | −0.0021 (12) |
C36 | 0.1050 (19) | 0.0574 (12) | 0.0552 (12) | 0.0003 (12) | −0.0272 (12) | −0.0028 (10) |
C41 | 0.0538 (10) | 0.0517 (10) | 0.0388 (8) | 0.0016 (8) | 0.0059 (7) | −0.0016 (7) |
C42 | 0.0619 (13) | 0.0789 (15) | 0.0655 (13) | 0.0158 (11) | 0.0121 (10) | 0.0179 (11) |
C43 | 0.0921 (19) | 0.097 (2) | 0.0783 (17) | 0.0340 (16) | 0.0072 (14) | 0.0293 (15) |
C44 | 0.122 (3) | 0.0853 (19) | 0.0642 (15) | 0.0136 (17) | 0.0146 (15) | 0.0253 (13) |
C45 | 0.100 (2) | 0.105 (2) | 0.0650 (15) | −0.0167 (17) | 0.0254 (14) | 0.0180 (14) |
C46 | 0.0609 (13) | 0.0925 (17) | 0.0548 (12) | −0.0051 (12) | 0.0110 (10) | 0.0099 (11) |
P3 | 0.0453 (3) | 0.0629 (3) | 0.0581 (3) | 0.0035 (2) | −0.0017 (2) | −0.0103 (2) |
F1 | 0.0929 (11) | 0.0858 (10) | 0.1044 (11) | 0.0044 (9) | −0.0382 (9) | 0.0154 (9) |
F2 | 0.0642 (8) | 0.0872 (10) | 0.1326 (14) | −0.0163 (8) | −0.0006 (9) | 0.0163 (10) |
F3 | 0.0584 (8) | 0.0971 (11) | 0.1013 (11) | −0.0150 (7) | −0.0012 (7) | 0.0030 (9) |
F4 | 0.0782 (9) | 0.1053 (11) | 0.0710 (9) | −0.0068 (8) | −0.0231 (7) | 0.0051 (8) |
F5 | 0.1100 (12) | 0.0903 (10) | 0.0764 (9) | 0.0232 (9) | 0.0242 (8) | −0.0145 (8) |
F6 | 0.1001 (12) | 0.1145 (14) | 0.1303 (15) | 0.0173 (11) | 0.0221 (11) | −0.0578 (12) |
Ni—S1 | 2.1269 (5) | C21—C22 | 1.393 (3) |
Ni—S2 | 2.1293 (5) | C22—C23 | 1.381 (3) |
Ni—P2 | 2.2034 (5) | C23—C24 | 1.382 (4) |
Ni—P1 | 2.2046 (5) | C24—C25 | 1.372 (3) |
P1—C21 | 1.8114 (19) | C25—C26 | 1.386 (3) |
P1—C11 | 1.8123 (17) | C31—C36 | 1.369 (3) |
P1—C6 | 1.8431 (18) | C31—C32 | 1.388 (3) |
P2—C41 | 1.8095 (19) | C32—C33 | 1.388 (4) |
P2—C31 | 1.8106 (19) | C33—C34 | 1.360 (4) |
P2—C6 | 1.8472 (17) | C34—C35 | 1.358 (4) |
S1—C2 | 1.689 (2) | C35—C36 | 1.387 (3) |
S2—C4 | 1.684 (2) | C41—C42 | 1.382 (3) |
C1—C2 | 1.523 (3) | C41—C46 | 1.388 (3) |
C2—C3 | 1.377 (3) | C42—C43 | 1.393 (3) |
C3—C4 | 1.385 (3) | C43—C44 | 1.367 (4) |
C4—C5 | 1.517 (3) | C44—C45 | 1.367 (4) |
C11—C12 | 1.385 (3) | C45—C46 | 1.382 (4) |
C11—C16 | 1.390 (3) | P3—F6 | 1.5753 (16) |
C12—C13 | 1.391 (3) | P3—F1 | 1.5808 (15) |
C13—C14 | 1.369 (3) | P3—F2 | 1.5824 (16) |
C14—C15 | 1.375 (4) | P3—F5 | 1.5862 (15) |
C15—C16 | 1.390 (3) | P3—F4 | 1.5973 (15) |
C21—C26 | 1.388 (3) | P3—F3 | 1.6120 (16) |
S1—Ni—S2 | 101.30 (2) | C22—C21—P1 | 120.87 (15) |
S1—Ni—P2 | 166.06 (2) | C23—C22—C21 | 120.3 (2) |
S2—Ni—P2 | 92.541 (19) | C22—C23—C24 | 120.1 (2) |
S1—Ni—P1 | 92.645 (19) | C25—C24—C23 | 119.9 (2) |
S2—Ni—P1 | 166.06 (2) | C24—C25—C26 | 120.6 (2) |
P2—Ni—P1 | 73.536 (17) | C25—C26—C21 | 119.90 (19) |
C21—P1—C11 | 107.05 (8) | C36—C31—C32 | 118.96 (19) |
C21—P1—C6 | 106.53 (9) | C36—C31—P2 | 119.35 (14) |
C11—P1—C6 | 111.55 (8) | C32—C31—P2 | 121.64 (17) |
C21—P1—Ni | 112.56 (6) | C31—C32—C33 | 119.4 (2) |
C11—P1—Ni | 124.06 (6) | C34—C33—C32 | 120.9 (2) |
C6—P1—Ni | 93.37 (6) | C35—C34—C33 | 119.9 (2) |
C41—P2—C31 | 106.07 (9) | C34—C35—C36 | 120.2 (2) |
C41—P2—C6 | 108.90 (9) | C31—C36—C35 | 120.7 (2) |
C31—P2—C6 | 110.72 (9) | C42—C41—C46 | 119.43 (19) |
C41—P2—Ni | 116.27 (6) | C42—C41—P2 | 118.01 (15) |
C31—P2—Ni | 120.59 (7) | C46—C41—P2 | 122.42 (16) |
C6—P2—Ni | 93.29 (6) | C41—C42—C43 | 120.1 (2) |
C2—S1—Ni | 115.49 (8) | C44—C43—C42 | 119.8 (3) |
C4—S2—Ni | 115.71 (8) | C45—C44—C43 | 120.4 (2) |
C3—C2—C1 | 118.0 (2) | C44—C45—C46 | 120.6 (3) |
C3—C2—S1 | 128.62 (17) | C45—C46—C41 | 119.7 (2) |
C1—C2—S1 | 113.37 (18) | F6—P3—F1 | 90.84 (11) |
C2—C3—C4 | 130.0 (2) | F6—P3—F2 | 90.88 (11) |
C3—C4—C5 | 117.9 (2) | F1—P3—F2 | 90.69 (9) |
C3—C4—S2 | 128.38 (16) | F6—P3—F5 | 177.37 (11) |
C5—C4—S2 | 113.70 (18) | F1—P3—F5 | 90.36 (10) |
P1—C6—P2 | 91.29 (8) | F2—P3—F5 | 91.45 (10) |
C12—C11—C16 | 119.24 (17) | F6—P3—F4 | 90.42 (10) |
C12—C11—P1 | 121.34 (14) | F1—P3—F4 | 178.50 (10) |
C16—C11—P1 | 119.19 (15) | F2—P3—F4 | 90.12 (9) |
C11—C12—C13 | 120.00 (19) | F5—P3—F4 | 88.35 (9) |
C14—C13—C12 | 120.2 (2) | F6—P3—F3 | 89.60 (10) |
C13—C14—C15 | 120.4 (2) | F1—P3—F3 | 89.95 (9) |
C14—C15—C16 | 119.9 (2) | F2—P3—F3 | 179.19 (9) |
C11—C16—C15 | 120.2 (2) | F5—P3—F3 | 88.06 (10) |
C26—C21—C22 | 119.25 (18) | F4—P3—F3 | 89.23 (9) |
C26—C21—P1 | 119.85 (14) |
[Ni(C26H24P2)(C5H7S2)]PF6 | Z = 2 |
Mr = 733.30 | F(000) = 752 |
Triclinic, P1 | Dx = 1.289 Mg m−3 |
a = 11.0458 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.4850 (2) Å | Cell parameters from 5722 reflections |
c = 14.5828 (1) Å | θ = 2–26° |
α = 67.386 (1)° | µ = 0.80 mm−1 |
β = 76.105 (1)° | T = 203 K |
γ = 72.088 (1)° | Irregular fragment, orange |
V = 1889.50 (5) Å3 | 0.58 × 0.32 × 0.10 mm |
Siemens SMART diffractometer | 7347 independent reflections |
Radiation source: fine-focus sealed tube | 5871 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
Area–detector ω scans | θmax = 26.2°, θmin = 1.5° |
Absorption correction: multi-scan (Blessing, 1995) | h = −13→13 |
Tmin = 0.654, Tmax = 0.924 | k = −15→16 |
17129 measured reflections | l = 0→18 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.04 | Calculated w = 1/[σ2(Fo2) + (0.1337P)2 + 4.2975P] where P = (Fo2 + 2Fc2)/3 |
7347 reflections | (Δ/σ)max = 0.048 |
390 parameters | Δρmax = 0.53 e Å−3 |
0 restraints | Δρmin = −0.56 e Å−3 |
[Ni(C26H24P2)(C5H7S2)]PF6 | γ = 72.088 (1)° |
Mr = 733.30 | V = 1889.50 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.0458 (2) Å | Mo Kα radiation |
b = 13.4850 (2) Å | µ = 0.80 mm−1 |
c = 14.5828 (1) Å | T = 203 K |
α = 67.386 (1)° | 0.58 × 0.32 × 0.10 mm |
β = 76.105 (1)° |
Siemens SMART diffractometer | 7347 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 5871 reflections with I > 2σ(I) |
Tmin = 0.654, Tmax = 0.924 | Rint = 0.029 |
17129 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.53 e Å−3 |
7347 reflections | Δρmin = −0.56 e Å−3 |
390 parameters |
x | y | z | Uiso*/Ueq | ||
Ni | 0.17862 (3) | 0.20322 (2) | 0.16565 (2) | 0.03164 (10) | |
P1 | 0.39122 (6) | 0.17129 (5) | 0.14343 (5) | 0.03648 (15) | |
P2 | 0.21122 (6) | 0.02000 (5) | 0.20822 (5) | 0.03521 (15) | |
S1 | 0.17338 (6) | 0.37820 (5) | 0.10715 (5) | 0.04250 (16) | |
S2 | −0.02490 (6) | 0.21214 (5) | 0.20673 (5) | 0.03737 (15) | |
C1 | 0.0351 (3) | 0.5869 (2) | 0.0929 (2) | 0.0555 (7) | |
H1A | −0.0440 | 0.6354 | 0.0679 | 0.083* | |
H1B | 0.1070 | 0.5995 | 0.0401 | 0.083* | |
H1C | 0.0468 | 0.6024 | 0.1494 | 0.083* | |
C2 | 0.0278 (2) | 0.4665 (2) | 0.1262 (2) | 0.0399 (6) | |
C3 | −0.0913 (2) | 0.4414 (2) | 0.1646 (2) | 0.0435 (6) | |
H3A | −0.1602 | 0.5017 | 0.1694 | 0.052* | |
C4 | −0.1236 (2) | 0.3400 (2) | 0.19707 (19) | 0.0391 (6) | |
C5 | −0.2661 (3) | 0.3405 (3) | 0.2304 (3) | 0.0660 (9) | |
H5A | −0.3170 | 0.4041 | 0.1846 | 0.099* | |
H5B | −0.2911 | 0.3445 | 0.2976 | 0.099* | |
H5C | −0.2805 | 0.2732 | 0.2301 | 0.099* | |
C6 | 0.4599 (2) | 0.0323 (2) | 0.1321 (2) | 0.0449 (6) | |
H6A | 0.4513 | 0.0337 | 0.0662 | 0.054* | |
H6B | 0.5513 | 0.0078 | 0.1397 | 0.054* | |
C7 | 0.3851 (2) | −0.0461 (2) | 0.2155 (2) | 0.0475 (7) | |
H7A | 0.4055 | −0.0576 | 0.2812 | 0.057* | |
H7B | 0.4074 | −0.1180 | 0.2060 | 0.057* | |
C11 | 0.4673 (2) | 0.2662 (2) | 0.0341 (2) | 0.0443 (6) | |
C12 | 0.5402 (3) | 0.3300 (2) | 0.0418 (3) | 0.0549 (7) | |
H12A | 0.5530 | 0.3240 | 0.1054 | 0.066* | |
C13 | 0.5940 (3) | 0.4025 (3) | −0.0440 (3) | 0.0732 (10) | |
H13A | 0.6442 | 0.4445 | −0.0385 | 0.088* | |
C14 | 0.5734 (4) | 0.4128 (3) | −0.1385 (3) | 0.0781 (11) | |
H14A | 0.6097 | 0.4619 | −0.1964 | 0.094* | |
C15 | 0.4999 (3) | 0.3512 (3) | −0.1474 (3) | 0.0744 (10) | |
H15A | 0.4862 | 0.3586 | −0.2112 | 0.089* | |
C16 | 0.4462 (3) | 0.2782 (3) | −0.0615 (2) | 0.0575 (7) | |
H16A | 0.3956 | 0.2368 | −0.0675 | 0.069* | |
C21 | 0.4446 (2) | 0.1655 (2) | 0.2552 (2) | 0.0412 (6) | |
C22 | 0.5562 (3) | 0.0904 (2) | 0.2915 (2) | 0.0525 (7) | |
H22A | 0.6066 | 0.0417 | 0.2572 | 0.063* | |
C23 | 0.5934 (3) | 0.0867 (3) | 0.3779 (3) | 0.0674 (9) | |
H23A | 0.6689 | 0.0361 | 0.4012 | 0.081* | |
C24 | 0.5196 (3) | 0.1575 (3) | 0.4294 (2) | 0.0676 (9) | |
H24A | 0.5441 | 0.1537 | 0.4883 | 0.081* | |
C25 | 0.4103 (4) | 0.2334 (4) | 0.3944 (3) | 0.0786 (11) | |
H25A | 0.3612 | 0.2823 | 0.4289 | 0.094* | |
C26 | 0.3723 (3) | 0.2379 (3) | 0.3076 (3) | 0.0666 (9) | |
H26A | 0.2976 | 0.2898 | 0.2842 | 0.080* | |
C31 | 0.1251 (2) | −0.0533 (2) | 0.32668 (19) | 0.0412 (6) | |
C32 | 0.1705 (3) | −0.0757 (3) | 0.4167 (2) | 0.0653 (9) | |
H32A | 0.2451 | −0.0547 | 0.4146 | 0.078* | |
C33 | 0.1059 (4) | −0.1285 (4) | 0.5085 (3) | 0.0874 (12) | |
H33A | 0.1365 | −0.1423 | 0.5681 | 0.105* | |
C34 | −0.0032 (4) | −0.1608 (3) | 0.5127 (3) | 0.0781 (10) | |
H34A | −0.0447 | −0.1987 | 0.5750 | 0.094* | |
C35 | −0.0517 (3) | −0.1376 (3) | 0.4248 (2) | 0.0630 (8) | |
H35A | −0.1273 | −0.1577 | 0.4279 | 0.076* | |
C36 | 0.0126 (3) | −0.0840 (2) | 0.3319 (2) | 0.0510 (7) | |
H36A | −0.0199 | −0.0685 | 0.2726 | 0.061* | |
C41 | 0.1825 (2) | −0.0180 (2) | 0.10884 (19) | 0.0374 (5) | |
C42 | 0.1872 (3) | −0.1290 (2) | 0.1248 (2) | 0.0489 (7) | |
H42A | 0.1985 | −0.1832 | 0.1881 | 0.059* | |
C43 | 0.1748 (3) | −0.1579 (3) | 0.0455 (3) | 0.0573 (8) | |
H43A | 0.1766 | −0.2316 | 0.0560 | 0.069* | |
C44 | 0.1600 (3) | −0.0789 (3) | −0.0480 (2) | 0.0556 (8) | |
H44A | 0.1527 | −0.0995 | −0.1008 | 0.067* | |
C45 | 0.1558 (3) | 0.0304 (3) | −0.0649 (2) | 0.0505 (7) | |
H45A | 0.1456 | 0.0838 | −0.1288 | 0.061* | |
C46 | 0.1668 (2) | 0.0610 (2) | 0.01360 (19) | 0.0414 (6) | |
H46A | 0.1637 | 0.1352 | 0.0023 | 0.050* | |
P3 | 0.72389 (9) | −0.27755 (7) | 0.31028 (6) | 0.0623 (2) | |
F1 | 0.7095 (3) | −0.15846 (19) | 0.3156 (2) | 0.1151 (9) | |
F2 | 0.6925 (3) | −0.2157 (2) | 0.19706 (16) | 0.1129 (9) | |
F3 | 0.5729 (2) | −0.2674 (2) | 0.3482 (2) | 0.1287 (11) | |
F4 | 0.7398 (3) | −0.3954 (2) | 0.3034 (2) | 0.1217 (10) | |
F5 | 0.7509 (2) | −0.3340 (2) | 0.42365 (15) | 0.1008 (8) | |
F6 | 0.8732 (2) | −0.2835 (2) | 0.27195 (18) | 0.1025 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.02854 (16) | 0.02656 (16) | 0.04205 (19) | −0.00393 (11) | −0.00582 (12) | −0.01546 (13) |
P1 | 0.0285 (3) | 0.0385 (3) | 0.0475 (4) | −0.0041 (2) | −0.0043 (3) | −0.0237 (3) |
P2 | 0.0365 (3) | 0.0262 (3) | 0.0451 (4) | −0.0021 (2) | −0.0136 (3) | −0.0138 (3) |
S1 | 0.0338 (3) | 0.0295 (3) | 0.0641 (4) | −0.0073 (2) | −0.0025 (3) | −0.0184 (3) |
S2 | 0.0315 (3) | 0.0297 (3) | 0.0485 (4) | −0.0066 (2) | −0.0058 (3) | −0.0111 (3) |
C1 | 0.0557 (17) | 0.0338 (14) | 0.080 (2) | −0.0070 (12) | −0.0090 (15) | −0.0251 (15) |
C2 | 0.0430 (14) | 0.0313 (13) | 0.0489 (15) | −0.0040 (10) | −0.0072 (11) | −0.0204 (11) |
C3 | 0.0376 (14) | 0.0369 (14) | 0.0532 (16) | 0.0009 (11) | −0.0061 (11) | −0.0201 (12) |
C4 | 0.0320 (12) | 0.0382 (14) | 0.0437 (14) | −0.0029 (10) | −0.0049 (10) | −0.0148 (11) |
C5 | 0.0329 (15) | 0.0581 (19) | 0.099 (3) | −0.0039 (13) | −0.0051 (15) | −0.0264 (18) |
C6 | 0.0342 (13) | 0.0459 (15) | 0.0624 (17) | 0.0034 (11) | −0.0101 (12) | −0.0346 (14) |
C7 | 0.0429 (14) | 0.0373 (14) | 0.0670 (18) | 0.0046 (11) | −0.0226 (13) | −0.0246 (13) |
C11 | 0.0289 (12) | 0.0466 (15) | 0.0543 (16) | −0.0061 (11) | 0.0013 (11) | −0.0202 (13) |
C12 | 0.0405 (15) | 0.0520 (17) | 0.073 (2) | −0.0108 (13) | −0.0014 (14) | −0.0264 (16) |
C13 | 0.0509 (18) | 0.0510 (19) | 0.106 (3) | −0.0145 (15) | 0.0120 (19) | −0.026 (2) |
C14 | 0.067 (2) | 0.050 (2) | 0.076 (3) | −0.0016 (16) | 0.0206 (19) | −0.0049 (18) |
C15 | 0.069 (2) | 0.074 (2) | 0.053 (2) | −0.0006 (19) | 0.0020 (16) | −0.0125 (18) |
C16 | 0.0510 (17) | 0.0628 (19) | 0.0537 (18) | −0.0077 (14) | −0.0030 (14) | −0.0215 (15) |
C21 | 0.0353 (13) | 0.0475 (15) | 0.0475 (15) | −0.0124 (11) | −0.0047 (11) | −0.0219 (12) |
C22 | 0.0531 (16) | 0.0451 (16) | 0.0632 (19) | −0.0065 (13) | −0.0193 (14) | −0.0199 (14) |
C23 | 0.069 (2) | 0.065 (2) | 0.073 (2) | −0.0144 (17) | −0.0354 (18) | −0.0143 (18) |
C24 | 0.080 (2) | 0.083 (2) | 0.0517 (19) | −0.031 (2) | −0.0186 (17) | −0.0208 (18) |
C25 | 0.074 (2) | 0.111 (3) | 0.070 (2) | −0.009 (2) | −0.0130 (19) | −0.060 (2) |
C26 | 0.0500 (17) | 0.092 (3) | 0.071 (2) | 0.0025 (16) | −0.0153 (15) | −0.054 (2) |
C31 | 0.0502 (15) | 0.0283 (12) | 0.0438 (15) | −0.0049 (11) | −0.0147 (12) | −0.0093 (11) |
C32 | 0.078 (2) | 0.070 (2) | 0.0506 (18) | −0.0245 (18) | −0.0194 (16) | −0.0111 (16) |
C33 | 0.113 (3) | 0.099 (3) | 0.049 (2) | −0.035 (3) | −0.023 (2) | −0.009 (2) |
C34 | 0.106 (3) | 0.070 (2) | 0.052 (2) | −0.037 (2) | −0.0024 (19) | −0.0057 (17) |
C35 | 0.071 (2) | 0.0532 (19) | 0.065 (2) | −0.0240 (16) | −0.0043 (16) | −0.0164 (16) |
C36 | 0.0588 (17) | 0.0431 (16) | 0.0517 (17) | −0.0134 (13) | −0.0126 (13) | −0.0128 (13) |
C41 | 0.0346 (12) | 0.0328 (13) | 0.0501 (15) | −0.0033 (10) | −0.0098 (11) | −0.0208 (11) |
C42 | 0.0518 (16) | 0.0363 (14) | 0.0649 (18) | −0.0024 (12) | −0.0173 (14) | −0.0247 (14) |
C43 | 0.0454 (16) | 0.0519 (18) | 0.091 (2) | −0.0061 (13) | −0.0094 (15) | −0.0454 (18) |
C44 | 0.0379 (14) | 0.081 (2) | 0.070 (2) | −0.0157 (14) | −0.0004 (14) | −0.0528 (19) |
C45 | 0.0416 (14) | 0.074 (2) | 0.0433 (15) | −0.0197 (14) | 0.0010 (12) | −0.0271 (15) |
C46 | 0.0369 (13) | 0.0438 (15) | 0.0460 (15) | −0.0109 (11) | −0.0041 (11) | −0.0177 (12) |
P3 | 0.0750 (6) | 0.0524 (5) | 0.0483 (5) | −0.0028 (4) | −0.0079 (4) | −0.0152 (4) |
F1 | 0.171 (3) | 0.0544 (13) | 0.1117 (19) | 0.0039 (14) | −0.0385 (18) | −0.0316 (13) |
F2 | 0.151 (2) | 0.135 (2) | 0.0630 (14) | −0.0781 (19) | −0.0371 (14) | 0.0018 (14) |
F3 | 0.0768 (16) | 0.119 (2) | 0.121 (2) | −0.0060 (14) | 0.0008 (14) | 0.0110 (17) |
F4 | 0.176 (3) | 0.0778 (17) | 0.124 (2) | −0.0400 (17) | 0.0057 (19) | −0.0558 (16) |
F5 | 0.128 (2) | 0.0852 (16) | 0.0539 (12) | 0.0173 (14) | −0.0199 (12) | −0.0149 (11) |
F6 | 0.0784 (15) | 0.112 (2) | 0.1011 (18) | −0.0113 (13) | −0.0007 (13) | −0.0343 (15) |
Ni—S2 | 2.1609 (6) | C21—C26 | 1.406 (4) |
Ni—S1 | 2.1658 (7) | C22—C23 | 1.395 (4) |
Ni—P1 | 2.2192 (6) | C23—C24 | 1.385 (5) |
Ni—P2 | 2.2361 (6) | C24—C25 | 1.379 (5) |
P1—C11 | 1.826 (3) | C25—C26 | 1.401 (4) |
P1—C21 | 1.829 (3) | C31—C36 | 1.403 (4) |
P1—C6 | 1.849 (2) | C31—C32 | 1.408 (4) |
P2—C31 | 1.828 (3) | C32—C33 | 1.389 (5) |
P2—C41 | 1.832 (2) | C33—C34 | 1.383 (5) |
P2—C7 | 1.862 (3) | C34—C35 | 1.395 (5) |
S1—C2 | 1.715 (2) | C35—C36 | 1.402 (4) |
S2—C4 | 1.707 (2) | C41—C46 | 1.399 (4) |
C1—C2 | 1.528 (4) | C41—C42 | 1.409 (3) |
C2—C3 | 1.391 (4) | C42—C43 | 1.401 (4) |
C3—C4 | 1.393 (4) | C43—C44 | 1.379 (5) |
C4—C5 | 1.530 (4) | C44—C45 | 1.387 (4) |
C6—C7 | 1.532 (4) | C45—C46 | 1.398 (4) |
C11—C12 | 1.395 (4) | P3—F4 | 1.583 (2) |
C11—C16 | 1.409 (4) | P3—F5 | 1.591 (2) |
C12—C13 | 1.391 (5) | P3—F1 | 1.595 (2) |
C13—C14 | 1.397 (6) | P3—F6 | 1.596 (2) |
C14—C15 | 1.383 (6) | P3—F2 | 1.606 (2) |
C15—C16 | 1.394 (5) | P3—F3 | 1.607 (3) |
C21—C22 | 1.399 (4) | ||
S2—Ni—S1 | 99.53 (2) | C22—C21—P1 | 122.1 (2) |
S2—Ni—P1 | 171.43 (3) | C26—C21—P1 | 119.8 (2) |
S1—Ni—P1 | 87.53 (3) | C23—C22—C21 | 120.9 (3) |
S2—Ni—P2 | 88.06 (2) | C24—C23—C22 | 120.2 (3) |
S1—Ni—P2 | 171.04 (3) | C25—C24—C23 | 120.2 (3) |
P1—Ni—P2 | 85.34 (2) | C24—C25—C26 | 120.0 (3) |
C11—P1—C21 | 108.08 (12) | C25—C26—C21 | 120.7 (3) |
C11—P1—C6 | 106.15 (12) | C36—C31—C32 | 118.6 (3) |
C21—P1—C6 | 105.96 (12) | C36—C31—P2 | 122.7 (2) |
C11—P1—Ni | 117.84 (9) | C32—C31—P2 | 118.6 (2) |
C21—P1—Ni | 109.72 (8) | C33—C32—C31 | 120.5 (3) |
C6—P1—Ni | 108.44 (8) | C34—C33—C32 | 120.4 (3) |
C31—P2—C41 | 108.07 (12) | C33—C34—C35 | 120.2 (3) |
C31—P2—C7 | 106.11 (13) | C34—C35—C36 | 119.7 (3) |
C41—P2—C7 | 102.25 (12) | C31—C36—C35 | 120.5 (3) |
C31—P2—Ni | 117.95 (8) | C46—C41—C42 | 119.2 (2) |
C41—P2—Ni | 111.76 (8) | C46—C41—P2 | 120.23 (18) |
C7—P2—Ni | 109.41 (9) | C42—C41—P2 | 120.3 (2) |
C2—S1—Ni | 116.63 (9) | C43—C42—C41 | 119.5 (3) |
C4—S2—Ni | 116.61 (9) | C44—C43—C42 | 120.5 (3) |
C3—C2—C1 | 118.6 (2) | C43—C44—C45 | 120.6 (3) |
C3—C2—S1 | 128.01 (19) | C44—C45—C46 | 119.7 (3) |
C1—C2—S1 | 113.39 (19) | C41—C46—C45 | 120.5 (3) |
C4—C3—C2 | 129.6 (2) | F4—P3—F5 | 90.19 (15) |
C3—C4—C5 | 117.1 (2) | F4—P3—F1 | 179.09 (16) |
C3—C4—S2 | 128.75 (19) | F5—P3—F1 | 90.38 (13) |
C5—C4—S2 | 114.19 (19) | F4—P3—F6 | 91.25 (15) |
C7—C6—P1 | 107.00 (17) | F5—P3—F6 | 90.83 (14) |
C6—C7—P2 | 106.99 (18) | F1—P3—F6 | 88.03 (16) |
C12—C11—C16 | 119.1 (3) | F4—P3—F2 | 92.05 (16) |
C12—C11—P1 | 122.8 (2) | F5—P3—F2 | 177.39 (15) |
C16—C11—P1 | 118.0 (2) | F1—P3—F2 | 87.40 (15) |
C13—C12—C11 | 120.3 (3) | F6—P3—F2 | 90.46 (14) |
C12—C13—C14 | 119.9 (3) | F4—P3—F3 | 90.53 (18) |
C15—C14—C13 | 120.5 (3) | F5—P3—F3 | 89.60 (15) |
C14—C15—C16 | 119.7 (3) | F1—P3—F3 | 90.19 (17) |
C15—C16—C11 | 120.4 (3) | F6—P3—F3 | 178.17 (16) |
C22—C21—C26 | 118.0 (2) | F2—P3—F3 | 89.04 (15) |
[Ni(C27H26P2)(C5H7S2)]PF6 | F(000) = 768 |
Mr = 747.32 | Dx = 1.447 Mg m−3 |
Monoclinic, P21/m | Mo Kα radiation, λ = 0.71073 Å |
a = 10.0345 (2) Å | Cell parameters from 8192 reflections |
b = 15.8632 (2) Å | θ = 2–26° |
c = 10.8058 (2) Å | µ = 0.88 mm−1 |
β = 94.14° | T = 203 K |
V = 1715.58 (5) Å3 | Prism, orange |
Z = 2 | 0.30 × 0.22 × 0.18 mm |
Siemens SMART diffractometer | 3634 independent reflections |
Radiation source: fine-focus sealed tube | 2789 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
Area–detector ω scans | θmax = 26.4°, θmin = 1.9° |
Absorption correction: multi-scan (Blessing, 1995) | h = −12→12 |
Tmin = 0.778, Tmax = 0.857 | k = −19→19 |
15834 measured reflections | l = −13→13 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.00 | Calculated w = 1/[σ2(Fo2) + (0.0472P)2 + 0.6603P] where P = (Fo2 + 2Fc2)/3 |
3634 reflections | (Δ/σ)max = 0.001 |
211 parameters | Δρmax = 0.34 e Å−3 |
72 restraints | Δρmin = −0.26 e Å−3 |
[Ni(C27H26P2)(C5H7S2)]PF6 | V = 1715.58 (5) Å3 |
Mr = 747.32 | Z = 2 |
Monoclinic, P21/m | Mo Kα radiation |
a = 10.0345 (2) Å | µ = 0.88 mm−1 |
b = 15.8632 (2) Å | T = 203 K |
c = 10.8058 (2) Å | 0.30 × 0.22 × 0.18 mm |
β = 94.14° |
Siemens SMART diffractometer | 3634 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 2789 reflections with I > 2σ(I) |
Tmin = 0.778, Tmax = 0.857 | Rint = 0.031 |
15834 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 72 restraints |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.34 e Å−3 |
3634 reflections | Δρmin = −0.26 e Å−3 |
211 parameters |
x | y | z | Uiso*/Ueq | ||
Ni | 0.38982 (4) | 0.2500 | 0.82875 (3) | 0.04148 (13) | |
S1 | 0.31573 (7) | 0.35159 (4) | 0.93587 (6) | 0.05904 (18) | |
P1 | 0.48000 (6) | 0.15051 (4) | 0.71370 (5) | 0.04412 (15) | |
C1 | 0.1797 (4) | 0.4041 (2) | 1.1268 (4) | 0.0995 (12) | |
H1A | 0.2089 | 0.4550 | 1.0870 | 0.149* | |
H1B | 0.2158 | 0.4030 | 1.2125 | 0.149* | |
H1C | 0.0828 | 0.4032 | 1.1241 | 0.149* | |
C2 | 0.2287 (3) | 0.32782 (18) | 1.0594 (2) | 0.0614 (7) | |
C3 | 0.1970 (4) | 0.2500 | 1.1021 (4) | 0.0701 (11) | |
H3 | 0.1454 | 0.2500 | 1.1713 | 0.084* | |
C4 | 0.4751 (3) | 0.16997 (16) | 0.5464 (2) | 0.0573 (6) | |
H4A | 0.5172 | 0.1220 | 0.5074 | 0.069* | |
H4B | 0.3813 | 0.1714 | 0.5141 | 0.069* | |
C5 | 0.5420 (4) | 0.2500 | 0.5057 (3) | 0.0556 (8) | |
H5A | 0.5422 | 0.2500 | 0.4150 | 0.067* | |
H5B | 0.6353 | 0.2500 | 0.5396 | 0.067* | |
C11 | 0.4021 (2) | 0.04626 (15) | 0.7167 (2) | 0.0509 (5) | |
C12 | 0.4656 (3) | −0.02166 (17) | 0.7736 (3) | 0.0662 (7) | |
H12A | 0.5515 | −0.0153 | 0.8134 | 0.079* | |
C13 | 0.4027 (4) | −0.09994 (19) | 0.7725 (3) | 0.0842 (9) | |
H13A | 0.4467 | −0.1464 | 0.8108 | 0.101* | |
C14 | 0.2783 (4) | −0.1095 (2) | 0.7162 (3) | 0.0845 (10) | |
H14A | 0.2367 | −0.1626 | 0.7155 | 0.101* | |
C15 | 0.2135 (3) | −0.0424 (2) | 0.6607 (3) | 0.0823 (9) | |
H15A | 0.1270 | −0.0493 | 0.6225 | 0.099* | |
C16 | 0.2744 (3) | 0.03590 (19) | 0.6605 (3) | 0.0708 (7) | |
H16A | 0.2292 | 0.0820 | 0.6224 | 0.085* | |
C21 | 0.6545 (2) | 0.13424 (15) | 0.7651 (3) | 0.0541 (6) | |
C22 | 0.6943 (3) | 0.1442 (2) | 0.8880 (4) | 0.0965 (12) | |
H22A | 0.6305 | 0.1570 | 0.9447 | 0.116* | |
C23 | 0.8272 (4) | 0.1356 (3) | 0.9300 (5) | 0.141 (2) | |
H23A | 0.8535 | 0.1422 | 1.0147 | 0.170* | |
C24 | 0.9187 (4) | 0.1175 (3) | 0.8481 (6) | 0.131 (2) | |
H24A | 1.0093 | 0.1130 | 0.8761 | 0.157* | |
C25 | 0.8824 (4) | 0.1061 (4) | 0.7281 (6) | 0.142 (2) | |
H25A | 0.9470 | 0.0928 | 0.6724 | 0.170* | |
C26 | 0.7489 (3) | 0.1139 (3) | 0.6855 (4) | 0.1076 (14) | |
H26A | 0.7235 | 0.1051 | 0.6011 | 0.129* | |
P2 | 0.05592 (9) | 0.2500 | 0.45600 (9) | 0.0620 (3) | |
F1 | −0.0151 (2) | 0.2500 | 0.3197 (2) | 0.1001 (10) | |
F2 | −0.0847 (3) | 0.2500 | 0.5091 (3) | 0.1087 (10) | |
F3 | 0.1291 (3) | 0.2500 | 0.5914 (2) | 0.0930 (8) | |
F4 | 0.1976 (2) | 0.2500 | 0.4005 (2) | 0.1244 (13) | |
F5 | 0.0568 (2) | 0.15064 (14) | 0.4566 (3) | 0.1275 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.0358 (2) | 0.0466 (2) | 0.0424 (2) | 0.000 | 0.00536 (16) | 0.000 |
S1 | 0.0621 (4) | 0.0539 (4) | 0.0640 (4) | −0.0058 (3) | 0.0244 (3) | −0.0084 (3) |
P1 | 0.0391 (3) | 0.0472 (3) | 0.0464 (3) | 0.0010 (2) | 0.0057 (2) | −0.0009 (2) |
C1 | 0.110 (3) | 0.085 (2) | 0.110 (3) | −0.018 (2) | 0.059 (2) | −0.040 (2) |
C2 | 0.0597 (15) | 0.0711 (17) | 0.0552 (14) | −0.0074 (13) | 0.0157 (12) | −0.0153 (13) |
C3 | 0.077 (3) | 0.078 (3) | 0.059 (2) | 0.000 | 0.0291 (19) | 0.000 |
C4 | 0.0658 (15) | 0.0615 (15) | 0.0450 (13) | −0.0015 (12) | 0.0061 (11) | −0.0054 (11) |
C5 | 0.060 (2) | 0.065 (2) | 0.0423 (17) | 0.000 | 0.0093 (15) | 0.000 |
C11 | 0.0500 (13) | 0.0496 (13) | 0.0540 (13) | −0.0025 (10) | 0.0104 (10) | −0.0055 (11) |
C12 | 0.0674 (16) | 0.0549 (16) | 0.0757 (18) | −0.0021 (13) | 0.0028 (14) | 0.0038 (13) |
C13 | 0.098 (2) | 0.0538 (17) | 0.102 (2) | −0.0060 (16) | 0.0096 (19) | 0.0056 (16) |
C14 | 0.096 (2) | 0.0600 (19) | 0.100 (2) | −0.0255 (18) | 0.022 (2) | −0.0142 (17) |
C15 | 0.0680 (18) | 0.082 (2) | 0.097 (2) | −0.0243 (17) | 0.0032 (17) | −0.0141 (18) |
C16 | 0.0554 (15) | 0.0674 (18) | 0.088 (2) | −0.0092 (13) | −0.0026 (14) | −0.0030 (15) |
C21 | 0.0400 (12) | 0.0479 (13) | 0.0752 (16) | 0.0014 (10) | 0.0087 (11) | 0.0090 (12) |
C22 | 0.0629 (18) | 0.112 (3) | 0.110 (3) | 0.0295 (18) | −0.0289 (18) | −0.046 (2) |
C23 | 0.085 (3) | 0.138 (4) | 0.190 (5) | 0.042 (3) | −0.069 (3) | −0.069 (4) |
C24 | 0.047 (2) | 0.104 (3) | 0.236 (6) | −0.0044 (19) | −0.017 (3) | 0.051 (4) |
C25 | 0.062 (2) | 0.193 (5) | 0.178 (5) | 0.047 (3) | 0.058 (3) | 0.119 (4) |
C26 | 0.0673 (19) | 0.159 (4) | 0.100 (2) | 0.047 (2) | 0.0360 (18) | 0.062 (2) |
P2 | 0.0480 (5) | 0.0877 (7) | 0.0500 (5) | 0.000 | 0.0014 (4) | 0.000 |
F1 | 0.0494 (12) | 0.196 (3) | 0.0543 (13) | 0.000 | −0.0042 (10) | 0.000 |
F2 | 0.0692 (16) | 0.177 (3) | 0.0839 (18) | 0.000 | 0.0311 (14) | 0.000 |
F3 | 0.1046 (19) | 0.119 (2) | 0.0529 (13) | 0.000 | −0.0154 (13) | 0.000 |
F4 | 0.0436 (13) | 0.255 (4) | 0.0738 (16) | 0.000 | 0.0017 (12) | 0.000 |
F5 | 0.1328 (19) | 0.0891 (15) | 0.153 (2) | 0.0085 (13) | −0.0389 (16) | −0.0239 (14) |
Ni—S1 | 2.1479 (7) | C11—C16 | 1.388 (3) |
Ni—S1i | 2.1479 (7) | C12—C13 | 1.393 (4) |
Ni—P1 | 2.2401 (6) | C13—C14 | 1.357 (5) |
Ni—P1i | 2.2401 (6) | C14—C15 | 1.364 (5) |
S1—C2 | 1.690 (3) | C15—C16 | 1.384 (4) |
S1—P1i | 3.0088 (8) | C21—C26 | 1.363 (4) |
S1—S1i | 3.2230 (13) | C21—C22 | 1.368 (4) |
P1—C21 | 1.816 (2) | C22—C23 | 1.384 (5) |
P1—C11 | 1.830 (2) | C23—C24 | 1.352 (7) |
P1—C4 | 1.832 (2) | C24—C25 | 1.334 (7) |
P1—P1i | 3.1565 (12) | C25—C26 | 1.391 (5) |
C1—C2 | 1.513 (4) | P2—F2 | 1.561 (3) |
C2—C3 | 1.364 (3) | P2—F5i | 1.576 (2) |
C3—C2i | 1.364 (3) | P2—F5 | 1.576 (2) |
C4—C5 | 1.516 (3) | P2—F4 | 1.582 (3) |
C5—C4i | 1.516 (3) | P2—F3 | 1.589 (2) |
C11—C12 | 1.375 (4) | P2—F1 | 1.589 (2) |
S1—Ni—S1i | 97.23 (4) | C16—C11—P1 | 118.8 (2) |
S1—Ni—P1 | 175.62 (3) | C11—C12—C13 | 120.0 (3) |
S1i—Ni—P1 | 86.55 (2) | C14—C13—C12 | 120.4 (3) |
S1—Ni—P1i | 86.55 (2) | C13—C14—C15 | 120.2 (3) |
S1i—Ni—P1i | 175.62 (3) | C14—C15—C16 | 120.3 (3) |
P1—Ni—P1i | 89.59 (3) | C15—C16—C11 | 120.0 (3) |
C2—S1—Ni | 118.49 (10) | C26—C21—C22 | 118.1 (3) |
C2—S1—P1i | 166.42 (10) | C26—C21—P1 | 122.6 (2) |
Ni—S1—P1i | 48.001 (18) | C22—C21—P1 | 119.2 (2) |
C2—S1—S1i | 77.11 (10) | C21—C22—C23 | 121.0 (4) |
Ni—S1—S1i | 41.388 (19) | C24—C23—C22 | 119.3 (4) |
P1i—S1—S1i | 89.368 (16) | C25—C24—C23 | 121.0 (4) |
C21—P1—C11 | 105.64 (11) | C24—C25—C26 | 119.9 (4) |
C21—P1—C4 | 106.40 (12) | C21—C26—C25 | 120.6 (4) |
C11—P1—C4 | 100.86 (11) | F2—P2—F5i | 90.21 (11) |
C21—P1—Ni | 110.46 (9) | F2—P2—F5 | 90.21 (11) |
C11—P1—Ni | 115.90 (8) | F5i—P2—F5 | 179.21 (18) |
C4—P1—Ni | 116.49 (9) | F2—P2—F4 | 179.28 (15) |
C21—P1—P1i | 98.17 (8) | F5i—P2—F4 | 89.79 (11) |
C11—P1—P1i | 154.63 (7) | F5—P2—F4 | 89.79 (11) |
C4—P1—P1i | 80.30 (8) | F2—P2—F3 | 91.81 (16) |
Ni—P1—P1i | 45.206 (16) | F5i—P2—F3 | 89.66 (9) |
C3—C2—C1 | 118.0 (3) | F5—P2—F3 | 89.66 (9) |
C3—C2—S1 | 128.0 (2) | F4—P2—F3 | 88.91 (15) |
C1—C2—S1 | 114.0 (2) | F2—P2—F1 | 89.06 (14) |
C2i—C3—C2 | 129.7 (4) | F5i—P2—F1 | 90.34 (9) |
C5—C4—P1 | 116.51 (19) | F5—P2—F1 | 90.34 (9) |
C4—C5—C4i | 113.7 (3) | F4—P2—F1 | 90.22 (13) |
C12—C11—C16 | 119.1 (2) | F3—P2—F1 | 179.13 (15) |
C12—C11—P1 | 122.10 (19) |
Symmetry code: (i) x, −y+1/2, z. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | [Ni(C25H22P2)(C5H7S2)]PF6 | [Ni(C26H24P2)(C5H7S2)]PF6 | [Ni(C27H26P2)(C5H7S2)]PF6 |
Mr | 719.27 | 733.30 | 747.32 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 | Monoclinic, P21/m |
Temperature (K) | 203 | 203 | 203 |
a, b, c (Å) | 10.8971 (1), 17.7367 (1), 16.7252 (2) | 11.0458 (2), 13.4850 (2), 14.5828 (1) | 10.0345 (2), 15.8632 (2), 10.8058 (2) |
α, β, γ (°) | 90, 94.793 (1), 90 | 67.386 (1), 76.105 (1), 72.088 (1) | 90, 94.14, 90 |
V (Å3) | 3221.32 (5) | 1889.50 (5) | 1715.58 (5) |
Z | 4 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.94 | 0.80 | 0.88 |
Crystal size (mm) | 0.50 × 0.34 × 0.28 | 0.58 × 0.32 × 0.10 | 0.30 × 0.22 × 0.18 |
Data collection | |||
Diffractometer | Siemens SMART diffractometer | Siemens SMART diffractometer | Siemens SMART diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) | Multi-scan (Blessing, 1995) | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.652, 0.780 | 0.654, 0.924 | 0.778, 0.857 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 30784, 7145, 6130 | 17129, 7347, 5871 | 15834, 3634, 2789 |
Rint | 0.018 | 0.029 | 0.031 |
(sin θ/λ)max (Å−1) | 0.648 | 0.620 | 0.625 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.083, 1.01 | 0.039, 0.104, 1.04 | 0.035, 0.095, 1.00 |
No. of reflections | 7145 | 7347 | 3634 |
No. of parameters | 379 | 390 | 211 |
No. of restraints | 0 | 0 | 72 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.20 | 0.53, −0.56 | 0.34, −0.26 |
Computer programs: SMART (Siemens, 1995), SMART, SAINT (Siemens, 1995), SHELXS (Sheldrick, 1990), SHELXL97 Sheldrick, (1997), SHELXL97.
Although pentane-2,4-dithione (sacsac) is not stable in isolation many examples are known where the ligand is coordinated to a metal atom (Lockyer & Martin, 1980). The bis(sacsac) CoII and NiII complexes (Beckett & Hoskins, 1974) both show a square-planar arrangement about the metal atom. Planar NiII mixed-ligand complexes containing phosphine and/or halide ligands have been found to act as effective catalyst precursors for olefin oligomerization and isomerization (Cavell, 1994; Cavell & Masters, 1986). Structures of two such complexes, related to the present study, are (sacsac)(PBu3)ClNi (Cavell et al., 1985) and (asacsac)(PEt3)ClNi (Cavell et al., 1984) (asacsac is 3-allylpentane-2,4-dithione), both of which have square-planar geometry.
We describe here the structures of the hexafluorophosphate salts of pentane-2,4-dithione[bis(diphenylphosphino)methane]nickel(II), (I), [Ni(sacac)(dppm)][PF6] pentane-2,4-dithione[bis-1,2-(diphenylphosphino)ethane]nickel(II), (II), [Ni(sacac)(dppe)][PF6] and pentane-2,4-dithione[bis-1,3-(diphenylphosphino)propane]nickel(II), (III), [Ni(sacac)(dppp)][PF6]. In each case, the arrangement of the S and P atoms about nickel is a distorted square plane with a high degree of planarity. The maximum deviation from the mean plane being 0.03 Å. The distortion from rectangular symmetry in the angles around the Ni atom arises from the variation of the size of the chelate ring increasing from four to six in the chelating phosphine ligand. Thus the P—Ni—P angles increase from 73.52 (6) in (I) to 85.39 (5) in (II) and 89.59 (3)° in (III) as the chelate ring size increases. This variation is similar to that found for other (P—P)M complexes from the Cambridge Crystallographic Database (Dierkes and van Leeuwen, 1999). The S—Ni—S angles show the opposite trend, decreasing from 101.29 (2) for (I) to 99.53 (5) in (II) and 97.22 (4)° in (III) as the strain imposed by the small chelate ring is eased.
The Ni—S distances are all comparable and average 2.146 Å which is in good agreement with other Ni(sacsac) complexes. The Ni—P distances show some variation, with those involving the smaller chelate ring being significantly smaller than those of the larger rings, average 2.204 for (I) and 2.228 and 2.237 Å for (II) and (III), respectively. The non-bonded S—P distances are all shorter than the sum of the van der Waals radii and average 3.073 Å, an effect also observed for the interligand S—S distances in Ni(sacsac)2. The corresponding S—P distances in the other known phosphine complexes are comparable. An explanation for this phenomenon has been advanced in terms of the planar nature of the six-membered chelate ring formed by the sacsac ligand (Beckett & Hoskins, 1974)
The sacsac ligands are all planar with maximum deviations from the mean plane being 0.06 Å for (II). The folding along the S—S vector, which has been observed for other complexes, is shown for (I) and (II) where the interplanar angles are 5.43 (6) and 7.22 (9)° respectively. For (III), the ligand is coplanar with the coordination plane. The methylene C atom of the dppm ligand lies 0.649 (2) Å from the mean plane of the Ni and P atoms in (I). In (II), the five membered ring formed by the dppe ligand has the gauche conformation with the two carbon atoms located 0.488 (6) and 0.185 (6) Å either side of the Ni—P plane. For (III), the six-membered ring formed by the dppe ligand has the chair conformation with the Ni atom 0.937 (2) Å below the plane defined by P1, C4 and their mirror related atoms and C5 is 0.678 (5) Å above the same plane.