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The structures of a series of four-coordinate nickel(II) complexes of the form [Ni(sacsac)L] PF6 (sacsac = pentane-2,4-di­thione anion; L = (Ph2P)2(CH2)n, n = 1,2,3) have beendetermined. These are [bis­(di­phenyl­phosphino)­methane](pentane-2,4-di­thionato-S,S')­nickel(II) hexa­fluoro­phosphate, [Ni(C25H22P2)(C5H7S2)]PF6, [1,2-bis­(di­phenylphosphino)­ethane](pentane-2,4-di­thionato-S,S')­nickel(II) hexa­fluoro­phosphate, [Ni(C26H24P2)(C5H7S2)]PF6, and [1,3-bis­(di­phenyl­phosphino)­propane](pentane-2,4-di­thionato-S,S')­nickel(II) hexa­fluoro­phosphate, [Ni(C27H26P2)(C5H7S2)]PF6. All have a distorted square-planar arrangement about Ni with angles around Ni varying with the length of the hydro­carbon chain.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199016078/qb0153sup1.cif
Contains datablocks I, II, III, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016078/qb0153Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016078/qb0153IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016078/qb0153IIIsup4.hkl
Contains datablock III

CCDC references: 140858; 140859; 140860

Comment top

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.

Experimental top

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.

Refinement top

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.

Computing details top

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.

(I) [bis(diphenylphosphino)methane](pentane-2,4-dithionato-S,S')nickel(II) hexafluorophosphate top
Crystal data top
[Ni(C25H22P2)(C5H7S2)]PF6F(000) = 1472
Mr = 719.27Dx = 1.483 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 10.8971 (1) ÅCell parameters from 7505 reflections
b = 17.7367 (1) Åθ = 2–27°
c = 16.7252 (2) ŵ = 0.94 mm1
β = 94.793 (1)°T = 203 K
V = 3221.32 (5) Å3Prism, orange
Z = 40.50 × 0.34 × 0.28 mm
Data collection top
Siemens SMART
diffractometer
7145 independent reflections
Radiation source: fine-focus sealed tube6130 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
Area–detector ω scansθmax = 27.4°, θmin = 1.7°
Absorption correction: multi-scan
(Blessing, 1995)
h = 1313
Tmin = 0.652, Tmax = 0.780k = 022
30784 measured reflectionsl = 021
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H-atom parameters constrained
S = 1.01Calculated w = 1/[σ2(Fo2) + (0.0443P)2 + 1.0272P]
where P = (Fo2 + 2Fc2)/3
7145 reflections(Δ/σ)max = 0.004
379 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
[Ni(C25H22P2)(C5H7S2)]PF6V = 3221.32 (5) Å3
Mr = 719.27Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.8971 (1) ŵ = 0.94 mm1
b = 17.7367 (1) ÅT = 203 K
c = 16.7252 (2) Å0.50 × 0.34 × 0.28 mm
β = 94.793 (1)°
Data collection top
Siemens SMART
diffractometer
7145 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
6130 reflections with I > 2σ(I)
Tmin = 0.652, Tmax = 0.780Rint = 0.018
30784 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.083H-atom parameters constrained
S = 1.01Δρmax = 0.27 e Å3
7145 reflectionsΔρmin = 0.20 e Å3
379 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni0.279208 (19)0.447682 (12)0.258885 (12)0.03983 (7)
P10.08592 (4)0.41005 (3)0.24260 (3)0.04154 (10)
P20.19577 (4)0.47619 (3)0.37057 (3)0.04210 (11)
S10.31493 (5)0.41350 (3)0.14117 (3)0.05159 (12)
S20.45416 (4)0.49097 (3)0.30302 (3)0.05657 (13)
C10.4856 (3)0.3881 (2)0.03745 (17)0.0968 (10)
H1A0.40830.37070.01090.145*
H1B0.54340.34650.04300.145*
H1C0.51900.42780.00580.145*
C20.4636 (2)0.41856 (13)0.12017 (13)0.0594 (5)
C30.5632 (2)0.44620 (14)0.16727 (14)0.0653 (6)
H3A0.63910.44260.14460.078*
C40.56895 (18)0.47843 (13)0.24292 (13)0.0597 (5)
C50.6924 (2)0.5080 (2)0.27811 (18)0.1000 (10)
H5A0.68360.52900.33090.150*
H5B0.72100.54700.24340.150*
H5C0.75170.46710.28250.150*
C60.03720 (16)0.47250 (11)0.32215 (11)0.0477 (4)
H6A0.02160.44890.35560.057*
H6B0.00660.52150.30220.057*
C110.01176 (16)0.42097 (11)0.15019 (10)0.0456 (4)
C120.06812 (18)0.48909 (12)0.12978 (12)0.0531 (4)
H12A0.05970.53000.16550.064*
C130.1371 (2)0.49691 (14)0.05642 (13)0.0633 (5)
H13A0.17600.54300.04290.076*
C140.1487 (2)0.43765 (15)0.00384 (13)0.0687 (6)
H14A0.19690.44300.04510.082*
C150.0903 (3)0.37041 (15)0.02223 (14)0.0769 (7)
H15A0.09660.33040.01470.092*
C160.0218 (2)0.36174 (13)0.09559 (13)0.0664 (6)
H16A0.01790.31570.10830.080*
C210.06592 (16)0.31433 (10)0.27697 (10)0.0443 (4)
C220.05090 (19)0.28600 (13)0.28734 (14)0.0626 (5)
H22A0.12080.31610.27450.075*
C230.0645 (2)0.21390 (14)0.31644 (16)0.0743 (7)
H23A0.14350.19520.32390.089*
C240.0379 (2)0.16915 (14)0.33461 (14)0.0681 (6)
H24A0.02850.11980.35360.082*
C250.1533 (2)0.19685 (13)0.32493 (15)0.0670 (6)
H25A0.22280.16650.33800.080*
C260.16826 (18)0.26922 (12)0.29607 (12)0.0550 (5)
H26A0.24760.28770.28940.066*
C310.22571 (17)0.56649 (11)0.41880 (11)0.0481 (4)
C320.2605 (3)0.57202 (15)0.50030 (14)0.0825 (8)
H32A0.26700.52850.53240.099*
C330.2858 (4)0.64240 (18)0.53400 (16)0.1034 (11)
H33A0.30980.64620.58910.124*
C340.2762 (3)0.70588 (15)0.48830 (17)0.0870 (8)
H34A0.29310.75330.51190.104*
C350.2423 (3)0.70070 (14)0.40851 (18)0.0895 (9)
H35A0.23510.74460.37700.107*
C360.2183 (3)0.63080 (13)0.37343 (14)0.0744 (7)
H36A0.19670.62760.31790.089*
C410.21143 (18)0.40640 (11)0.44968 (10)0.0480 (4)
C420.3283 (2)0.38055 (14)0.47389 (14)0.0684 (6)
H42A0.39570.39590.44640.082*
C430.3461 (3)0.33176 (18)0.53909 (17)0.0890 (8)
H43A0.42580.31470.55600.107*
C440.2476 (3)0.30875 (17)0.57835 (16)0.0902 (9)
H44A0.25980.27620.62260.108*
C450.1314 (3)0.33282 (18)0.55361 (16)0.0891 (8)
H45A0.06410.31570.58020.107*
C460.1121 (2)0.38206 (15)0.48976 (13)0.0690 (6)
H46A0.03220.39900.47360.083*
P30.54685 (5)0.21234 (3)0.29595 (3)0.05576 (13)
F10.46504 (15)0.24637 (9)0.22214 (10)0.0970 (5)
F20.65299 (14)0.27079 (9)0.28274 (11)0.0951 (5)
F30.44018 (13)0.15191 (9)0.30974 (10)0.0861 (4)
F40.62931 (14)0.17585 (10)0.36941 (9)0.0865 (4)
F50.60371 (16)0.15277 (9)0.23871 (9)0.0913 (5)
F60.48780 (17)0.26841 (11)0.35491 (12)0.1143 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni0.03590 (12)0.04664 (13)0.03674 (12)0.00310 (8)0.00178 (8)0.00135 (9)
P10.0353 (2)0.0487 (2)0.0399 (2)0.00231 (17)0.00082 (16)0.00436 (18)
P20.0386 (2)0.0512 (3)0.0360 (2)0.00002 (18)0.00004 (16)0.00394 (18)
S10.0523 (3)0.0600 (3)0.0429 (2)0.0026 (2)0.00643 (19)0.0070 (2)
S20.0414 (2)0.0796 (3)0.0486 (3)0.0136 (2)0.00268 (19)0.0050 (2)
C10.092 (2)0.126 (3)0.0780 (17)0.0082 (18)0.0381 (15)0.0341 (17)
C20.0623 (12)0.0632 (12)0.0550 (11)0.0018 (10)0.0186 (9)0.0041 (9)
C30.0489 (11)0.0806 (15)0.0688 (13)0.0005 (10)0.0193 (10)0.0013 (11)
C40.0419 (10)0.0760 (14)0.0612 (12)0.0064 (9)0.0054 (8)0.0075 (10)
C50.0461 (13)0.166 (3)0.0876 (18)0.0282 (16)0.0065 (12)0.010 (2)
C60.0381 (8)0.0597 (11)0.0446 (9)0.0020 (8)0.0009 (7)0.0088 (8)
C110.0399 (8)0.0538 (10)0.0422 (9)0.0055 (7)0.0015 (7)0.0017 (7)
C120.0524 (11)0.0568 (11)0.0495 (10)0.0008 (9)0.0008 (8)0.0007 (8)
C130.0592 (12)0.0714 (14)0.0581 (12)0.0022 (10)0.0034 (9)0.0151 (10)
C140.0668 (14)0.0892 (17)0.0472 (11)0.0147 (12)0.0118 (10)0.0104 (11)
C150.1005 (19)0.0767 (16)0.0497 (12)0.0108 (14)0.0166 (12)0.0086 (11)
C160.0826 (15)0.0598 (13)0.0537 (11)0.0037 (11)0.0129 (10)0.0081 (9)
C210.0403 (8)0.0509 (10)0.0414 (8)0.0038 (7)0.0020 (7)0.0029 (7)
C220.0409 (10)0.0674 (13)0.0794 (14)0.0037 (9)0.0035 (9)0.0077 (11)
C230.0543 (12)0.0747 (15)0.0948 (18)0.0155 (11)0.0116 (12)0.0148 (13)
C240.0777 (15)0.0604 (13)0.0673 (13)0.0077 (11)0.0123 (11)0.0113 (11)
C250.0609 (13)0.0652 (13)0.0753 (14)0.0126 (10)0.0078 (11)0.0141 (11)
C260.0418 (9)0.0611 (12)0.0627 (12)0.0013 (8)0.0078 (8)0.0050 (9)
C310.0463 (9)0.0537 (10)0.0431 (9)0.0009 (8)0.0032 (7)0.0084 (8)
C320.127 (2)0.0714 (15)0.0458 (11)0.0151 (15)0.0131 (13)0.0056 (10)
C330.161 (3)0.087 (2)0.0579 (14)0.023 (2)0.0175 (17)0.0224 (14)
C340.104 (2)0.0668 (16)0.0860 (18)0.0049 (14)0.0177 (16)0.0278 (14)
C350.120 (2)0.0526 (13)0.0889 (18)0.0019 (14)0.0348 (17)0.0021 (12)
C360.1050 (19)0.0574 (12)0.0552 (12)0.0003 (12)0.0272 (12)0.0028 (10)
C410.0538 (10)0.0517 (10)0.0388 (8)0.0016 (8)0.0059 (7)0.0016 (7)
C420.0619 (13)0.0789 (15)0.0655 (13)0.0158 (11)0.0121 (10)0.0179 (11)
C430.0921 (19)0.097 (2)0.0783 (17)0.0340 (16)0.0072 (14)0.0293 (15)
C440.122 (3)0.0853 (19)0.0642 (15)0.0136 (17)0.0146 (15)0.0253 (13)
C450.100 (2)0.105 (2)0.0650 (15)0.0167 (17)0.0254 (14)0.0180 (14)
C460.0609 (13)0.0925 (17)0.0548 (12)0.0051 (12)0.0110 (10)0.0099 (11)
P30.0453 (3)0.0629 (3)0.0581 (3)0.0035 (2)0.0017 (2)0.0103 (2)
F10.0929 (11)0.0858 (10)0.1044 (11)0.0044 (9)0.0382 (9)0.0154 (9)
F20.0642 (8)0.0872 (10)0.1326 (14)0.0163 (8)0.0006 (9)0.0163 (10)
F30.0584 (8)0.0971 (11)0.1013 (11)0.0150 (7)0.0012 (7)0.0030 (9)
F40.0782 (9)0.1053 (11)0.0710 (9)0.0068 (8)0.0231 (7)0.0051 (8)
F50.1100 (12)0.0903 (10)0.0764 (9)0.0232 (9)0.0242 (8)0.0145 (8)
F60.1001 (12)0.1145 (14)0.1303 (15)0.0173 (11)0.0221 (11)0.0578 (12)
Geometric parameters (Å, º) top
Ni—S12.1269 (5)C21—C221.393 (3)
Ni—S22.1293 (5)C22—C231.381 (3)
Ni—P22.2034 (5)C23—C241.382 (4)
Ni—P12.2046 (5)C24—C251.372 (3)
P1—C211.8114 (19)C25—C261.386 (3)
P1—C111.8123 (17)C31—C361.369 (3)
P1—C61.8431 (18)C31—C321.388 (3)
P2—C411.8095 (19)C32—C331.388 (4)
P2—C311.8106 (19)C33—C341.360 (4)
P2—C61.8472 (17)C34—C351.358 (4)
S1—C21.689 (2)C35—C361.387 (3)
S2—C41.684 (2)C41—C421.382 (3)
C1—C21.523 (3)C41—C461.388 (3)
C2—C31.377 (3)C42—C431.393 (3)
C3—C41.385 (3)C43—C441.367 (4)
C4—C51.517 (3)C44—C451.367 (4)
C11—C121.385 (3)C45—C461.382 (4)
C11—C161.390 (3)P3—F61.5753 (16)
C12—C131.391 (3)P3—F11.5808 (15)
C13—C141.369 (3)P3—F21.5824 (16)
C14—C151.375 (4)P3—F51.5862 (15)
C15—C161.390 (3)P3—F41.5973 (15)
C21—C261.388 (3)P3—F31.6120 (16)
S1—Ni—S2101.30 (2)C22—C21—P1120.87 (15)
S1—Ni—P2166.06 (2)C23—C22—C21120.3 (2)
S2—Ni—P292.541 (19)C22—C23—C24120.1 (2)
S1—Ni—P192.645 (19)C25—C24—C23119.9 (2)
S2—Ni—P1166.06 (2)C24—C25—C26120.6 (2)
P2—Ni—P173.536 (17)C25—C26—C21119.90 (19)
C21—P1—C11107.05 (8)C36—C31—C32118.96 (19)
C21—P1—C6106.53 (9)C36—C31—P2119.35 (14)
C11—P1—C6111.55 (8)C32—C31—P2121.64 (17)
C21—P1—Ni112.56 (6)C31—C32—C33119.4 (2)
C11—P1—Ni124.06 (6)C34—C33—C32120.9 (2)
C6—P1—Ni93.37 (6)C35—C34—C33119.9 (2)
C41—P2—C31106.07 (9)C34—C35—C36120.2 (2)
C41—P2—C6108.90 (9)C31—C36—C35120.7 (2)
C31—P2—C6110.72 (9)C42—C41—C46119.43 (19)
C41—P2—Ni116.27 (6)C42—C41—P2118.01 (15)
C31—P2—Ni120.59 (7)C46—C41—P2122.42 (16)
C6—P2—Ni93.29 (6)C41—C42—C43120.1 (2)
C2—S1—Ni115.49 (8)C44—C43—C42119.8 (3)
C4—S2—Ni115.71 (8)C45—C44—C43120.4 (2)
C3—C2—C1118.0 (2)C44—C45—C46120.6 (3)
C3—C2—S1128.62 (17)C45—C46—C41119.7 (2)
C1—C2—S1113.37 (18)F6—P3—F190.84 (11)
C2—C3—C4130.0 (2)F6—P3—F290.88 (11)
C3—C4—C5117.9 (2)F1—P3—F290.69 (9)
C3—C4—S2128.38 (16)F6—P3—F5177.37 (11)
C5—C4—S2113.70 (18)F1—P3—F590.36 (10)
P1—C6—P291.29 (8)F2—P3—F591.45 (10)
C12—C11—C16119.24 (17)F6—P3—F490.42 (10)
C12—C11—P1121.34 (14)F1—P3—F4178.50 (10)
C16—C11—P1119.19 (15)F2—P3—F490.12 (9)
C11—C12—C13120.00 (19)F5—P3—F488.35 (9)
C14—C13—C12120.2 (2)F6—P3—F389.60 (10)
C13—C14—C15120.4 (2)F1—P3—F389.95 (9)
C14—C15—C16119.9 (2)F2—P3—F3179.19 (9)
C11—C16—C15120.2 (2)F5—P3—F388.06 (10)
C26—C21—C22119.25 (18)F4—P3—F389.23 (9)
C26—C21—P1119.85 (14)
(II) Pentane-2,4-dithione[bis(diphenylphosphino)ethane]nickel(II) hexafluorophosphate. top
Crystal data top
[Ni(C26H24P2)(C5H7S2)]PF6Z = 2
Mr = 733.30F(000) = 752
Triclinic, P1Dx = 1.289 Mg m3
a = 11.0458 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 13.4850 (2) ÅCell parameters from 5722 reflections
c = 14.5828 (1) Åθ = 2–26°
α = 67.386 (1)°µ = 0.80 mm1
β = 76.105 (1)°T = 203 K
γ = 72.088 (1)°Irregular fragment, orange
V = 1889.50 (5) Å30.58 × 0.32 × 0.10 mm
Data collection top
Siemens SMART
diffractometer
7347 independent reflections
Radiation source: fine-focus sealed tube5871 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
Area–detector ω scansθmax = 26.2°, θmin = 1.5°
Absorption correction: multi-scan
(Blessing, 1995)
h = 1313
Tmin = 0.654, Tmax = 0.924k = 1516
17129 measured reflectionsl = 018
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104H-atom parameters constrained
S = 1.04Calculated w = 1/[σ2(Fo2) + (0.1337P)2 + 4.2975P]
where P = (Fo2 + 2Fc2)/3
7347 reflections(Δ/σ)max = 0.048
390 parametersΔρmax = 0.53 e Å3
0 restraintsΔρmin = 0.56 e Å3
Crystal data top
[Ni(C26H24P2)(C5H7S2)]PF6γ = 72.088 (1)°
Mr = 733.30V = 1889.50 (5) Å3
Triclinic, P1Z = 2
a = 11.0458 (2) ÅMo Kα radiation
b = 13.4850 (2) ŵ = 0.80 mm1
c = 14.5828 (1) ÅT = 203 K
α = 67.386 (1)°0.58 × 0.32 × 0.10 mm
β = 76.105 (1)°
Data collection top
Siemens SMART
diffractometer
7347 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
5871 reflections with I > 2σ(I)
Tmin = 0.654, Tmax = 0.924Rint = 0.029
17129 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.104H-atom parameters constrained
S = 1.04Δρmax = 0.53 e Å3
7347 reflectionsΔρmin = 0.56 e Å3
390 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni0.17862 (3)0.20322 (2)0.16565 (2)0.03164 (10)
P10.39122 (6)0.17129 (5)0.14343 (5)0.03648 (15)
P20.21122 (6)0.02000 (5)0.20822 (5)0.03521 (15)
S10.17338 (6)0.37820 (5)0.10715 (5)0.04250 (16)
S20.02490 (6)0.21214 (5)0.20673 (5)0.03737 (15)
C10.0351 (3)0.5869 (2)0.0929 (2)0.0555 (7)
H1A0.04400.63540.06790.083*
H1B0.10700.59950.04010.083*
H1C0.04680.60240.14940.083*
C20.0278 (2)0.4665 (2)0.1262 (2)0.0399 (6)
C30.0913 (2)0.4414 (2)0.1646 (2)0.0435 (6)
H3A0.16020.50170.16940.052*
C40.1236 (2)0.3400 (2)0.19707 (19)0.0391 (6)
C50.2661 (3)0.3405 (3)0.2304 (3)0.0660 (9)
H5A0.31700.40410.18460.099*
H5B0.29110.34450.29760.099*
H5C0.28050.27320.23010.099*
C60.4599 (2)0.0323 (2)0.1321 (2)0.0449 (6)
H6A0.45130.03370.06620.054*
H6B0.55130.00780.13970.054*
C70.3851 (2)0.0461 (2)0.2155 (2)0.0475 (7)
H7A0.40550.05760.28120.057*
H7B0.40740.11800.20600.057*
C110.4673 (2)0.2662 (2)0.0341 (2)0.0443 (6)
C120.5402 (3)0.3300 (2)0.0418 (3)0.0549 (7)
H12A0.55300.32400.10540.066*
C130.5940 (3)0.4025 (3)0.0440 (3)0.0732 (10)
H13A0.64420.44450.03850.088*
C140.5734 (4)0.4128 (3)0.1385 (3)0.0781 (11)
H14A0.60970.46190.19640.094*
C150.4999 (3)0.3512 (3)0.1474 (3)0.0744 (10)
H15A0.48620.35860.21120.089*
C160.4462 (3)0.2782 (3)0.0615 (2)0.0575 (7)
H16A0.39560.23680.06750.069*
C210.4446 (2)0.1655 (2)0.2552 (2)0.0412 (6)
C220.5562 (3)0.0904 (2)0.2915 (2)0.0525 (7)
H22A0.60660.04170.25720.063*
C230.5934 (3)0.0867 (3)0.3779 (3)0.0674 (9)
H23A0.66890.03610.40120.081*
C240.5196 (3)0.1575 (3)0.4294 (2)0.0676 (9)
H24A0.54410.15370.48830.081*
C250.4103 (4)0.2334 (4)0.3944 (3)0.0786 (11)
H25A0.36120.28230.42890.094*
C260.3723 (3)0.2379 (3)0.3076 (3)0.0666 (9)
H26A0.29760.28980.28420.080*
C310.1251 (2)0.0533 (2)0.32668 (19)0.0412 (6)
C320.1705 (3)0.0757 (3)0.4167 (2)0.0653 (9)
H32A0.24510.05470.41460.078*
C330.1059 (4)0.1285 (4)0.5085 (3)0.0874 (12)
H33A0.13650.14230.56810.105*
C340.0032 (4)0.1608 (3)0.5127 (3)0.0781 (10)
H34A0.04470.19870.57500.094*
C350.0517 (3)0.1376 (3)0.4248 (2)0.0630 (8)
H35A0.12730.15770.42790.076*
C360.0126 (3)0.0840 (2)0.3319 (2)0.0510 (7)
H36A0.01990.06850.27260.061*
C410.1825 (2)0.0180 (2)0.10884 (19)0.0374 (5)
C420.1872 (3)0.1290 (2)0.1248 (2)0.0489 (7)
H42A0.19850.18320.18810.059*
C430.1748 (3)0.1579 (3)0.0455 (3)0.0573 (8)
H43A0.17660.23160.05600.069*
C440.1600 (3)0.0789 (3)0.0480 (2)0.0556 (8)
H44A0.15270.09950.10080.067*
C450.1558 (3)0.0304 (3)0.0649 (2)0.0505 (7)
H45A0.14560.08380.12880.061*
C460.1668 (2)0.0610 (2)0.01360 (19)0.0414 (6)
H46A0.16370.13520.00230.050*
P30.72389 (9)0.27755 (7)0.31028 (6)0.0623 (2)
F10.7095 (3)0.15846 (19)0.3156 (2)0.1151 (9)
F20.6925 (3)0.2157 (2)0.19706 (16)0.1129 (9)
F30.5729 (2)0.2674 (2)0.3482 (2)0.1287 (11)
F40.7398 (3)0.3954 (2)0.3034 (2)0.1217 (10)
F50.7509 (2)0.3340 (2)0.42365 (15)0.1008 (8)
F60.8732 (2)0.2835 (2)0.27195 (18)0.1025 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni0.02854 (16)0.02656 (16)0.04205 (19)0.00393 (11)0.00582 (12)0.01546 (13)
P10.0285 (3)0.0385 (3)0.0475 (4)0.0041 (2)0.0043 (3)0.0237 (3)
P20.0365 (3)0.0262 (3)0.0451 (4)0.0021 (2)0.0136 (3)0.0138 (3)
S10.0338 (3)0.0295 (3)0.0641 (4)0.0073 (2)0.0025 (3)0.0184 (3)
S20.0315 (3)0.0297 (3)0.0485 (4)0.0066 (2)0.0058 (3)0.0111 (3)
C10.0557 (17)0.0338 (14)0.080 (2)0.0070 (12)0.0090 (15)0.0251 (15)
C20.0430 (14)0.0313 (13)0.0489 (15)0.0040 (10)0.0072 (11)0.0204 (11)
C30.0376 (14)0.0369 (14)0.0532 (16)0.0009 (11)0.0061 (11)0.0201 (12)
C40.0320 (12)0.0382 (14)0.0437 (14)0.0029 (10)0.0049 (10)0.0148 (11)
C50.0329 (15)0.0581 (19)0.099 (3)0.0039 (13)0.0051 (15)0.0264 (18)
C60.0342 (13)0.0459 (15)0.0624 (17)0.0034 (11)0.0101 (12)0.0346 (14)
C70.0429 (14)0.0373 (14)0.0670 (18)0.0046 (11)0.0226 (13)0.0246 (13)
C110.0289 (12)0.0466 (15)0.0543 (16)0.0061 (11)0.0013 (11)0.0202 (13)
C120.0405 (15)0.0520 (17)0.073 (2)0.0108 (13)0.0014 (14)0.0264 (16)
C130.0509 (18)0.0510 (19)0.106 (3)0.0145 (15)0.0120 (19)0.026 (2)
C140.067 (2)0.050 (2)0.076 (3)0.0016 (16)0.0206 (19)0.0049 (18)
C150.069 (2)0.074 (2)0.053 (2)0.0006 (19)0.0020 (16)0.0125 (18)
C160.0510 (17)0.0628 (19)0.0537 (18)0.0077 (14)0.0030 (14)0.0215 (15)
C210.0353 (13)0.0475 (15)0.0475 (15)0.0124 (11)0.0047 (11)0.0219 (12)
C220.0531 (16)0.0451 (16)0.0632 (19)0.0065 (13)0.0193 (14)0.0199 (14)
C230.069 (2)0.065 (2)0.073 (2)0.0144 (17)0.0354 (18)0.0143 (18)
C240.080 (2)0.083 (2)0.0517 (19)0.031 (2)0.0186 (17)0.0208 (18)
C250.074 (2)0.111 (3)0.070 (2)0.009 (2)0.0130 (19)0.060 (2)
C260.0500 (17)0.092 (3)0.071 (2)0.0025 (16)0.0153 (15)0.054 (2)
C310.0502 (15)0.0283 (12)0.0438 (15)0.0049 (11)0.0147 (12)0.0093 (11)
C320.078 (2)0.070 (2)0.0506 (18)0.0245 (18)0.0194 (16)0.0111 (16)
C330.113 (3)0.099 (3)0.049 (2)0.035 (3)0.023 (2)0.009 (2)
C340.106 (3)0.070 (2)0.052 (2)0.037 (2)0.0024 (19)0.0057 (17)
C350.071 (2)0.0532 (19)0.065 (2)0.0240 (16)0.0043 (16)0.0164 (16)
C360.0588 (17)0.0431 (16)0.0517 (17)0.0134 (13)0.0126 (13)0.0128 (13)
C410.0346 (12)0.0328 (13)0.0501 (15)0.0033 (10)0.0098 (11)0.0208 (11)
C420.0518 (16)0.0363 (14)0.0649 (18)0.0024 (12)0.0173 (14)0.0247 (14)
C430.0454 (16)0.0519 (18)0.091 (2)0.0061 (13)0.0094 (15)0.0454 (18)
C440.0379 (14)0.081 (2)0.070 (2)0.0157 (14)0.0004 (14)0.0528 (19)
C450.0416 (14)0.074 (2)0.0433 (15)0.0197 (14)0.0010 (12)0.0271 (15)
C460.0369 (13)0.0438 (15)0.0460 (15)0.0109 (11)0.0041 (11)0.0177 (12)
P30.0750 (6)0.0524 (5)0.0483 (5)0.0028 (4)0.0079 (4)0.0152 (4)
F10.171 (3)0.0544 (13)0.1117 (19)0.0039 (14)0.0385 (18)0.0316 (13)
F20.151 (2)0.135 (2)0.0630 (14)0.0781 (19)0.0371 (14)0.0018 (14)
F30.0768 (16)0.119 (2)0.121 (2)0.0060 (14)0.0008 (14)0.0110 (17)
F40.176 (3)0.0778 (17)0.124 (2)0.0400 (17)0.0057 (19)0.0558 (16)
F50.128 (2)0.0852 (16)0.0539 (12)0.0173 (14)0.0199 (12)0.0149 (11)
F60.0784 (15)0.112 (2)0.1011 (18)0.0113 (13)0.0007 (13)0.0343 (15)
Geometric parameters (Å, º) top
Ni—S22.1609 (6)C21—C261.406 (4)
Ni—S12.1658 (7)C22—C231.395 (4)
Ni—P12.2192 (6)C23—C241.385 (5)
Ni—P22.2361 (6)C24—C251.379 (5)
P1—C111.826 (3)C25—C261.401 (4)
P1—C211.829 (3)C31—C361.403 (4)
P1—C61.849 (2)C31—C321.408 (4)
P2—C311.828 (3)C32—C331.389 (5)
P2—C411.832 (2)C33—C341.383 (5)
P2—C71.862 (3)C34—C351.395 (5)
S1—C21.715 (2)C35—C361.402 (4)
S2—C41.707 (2)C41—C461.399 (4)
C1—C21.528 (4)C41—C421.409 (3)
C2—C31.391 (4)C42—C431.401 (4)
C3—C41.393 (4)C43—C441.379 (5)
C4—C51.530 (4)C44—C451.387 (4)
C6—C71.532 (4)C45—C461.398 (4)
C11—C121.395 (4)P3—F41.583 (2)
C11—C161.409 (4)P3—F51.591 (2)
C12—C131.391 (5)P3—F11.595 (2)
C13—C141.397 (6)P3—F61.596 (2)
C14—C151.383 (6)P3—F21.606 (2)
C15—C161.394 (5)P3—F31.607 (3)
C21—C221.399 (4)
S2—Ni—S199.53 (2)C22—C21—P1122.1 (2)
S2—Ni—P1171.43 (3)C26—C21—P1119.8 (2)
S1—Ni—P187.53 (3)C23—C22—C21120.9 (3)
S2—Ni—P288.06 (2)C24—C23—C22120.2 (3)
S1—Ni—P2171.04 (3)C25—C24—C23120.2 (3)
P1—Ni—P285.34 (2)C24—C25—C26120.0 (3)
C11—P1—C21108.08 (12)C25—C26—C21120.7 (3)
C11—P1—C6106.15 (12)C36—C31—C32118.6 (3)
C21—P1—C6105.96 (12)C36—C31—P2122.7 (2)
C11—P1—Ni117.84 (9)C32—C31—P2118.6 (2)
C21—P1—Ni109.72 (8)C33—C32—C31120.5 (3)
C6—P1—Ni108.44 (8)C34—C33—C32120.4 (3)
C31—P2—C41108.07 (12)C33—C34—C35120.2 (3)
C31—P2—C7106.11 (13)C34—C35—C36119.7 (3)
C41—P2—C7102.25 (12)C31—C36—C35120.5 (3)
C31—P2—Ni117.95 (8)C46—C41—C42119.2 (2)
C41—P2—Ni111.76 (8)C46—C41—P2120.23 (18)
C7—P2—Ni109.41 (9)C42—C41—P2120.3 (2)
C2—S1—Ni116.63 (9)C43—C42—C41119.5 (3)
C4—S2—Ni116.61 (9)C44—C43—C42120.5 (3)
C3—C2—C1118.6 (2)C43—C44—C45120.6 (3)
C3—C2—S1128.01 (19)C44—C45—C46119.7 (3)
C1—C2—S1113.39 (19)C41—C46—C45120.5 (3)
C4—C3—C2129.6 (2)F4—P3—F590.19 (15)
C3—C4—C5117.1 (2)F4—P3—F1179.09 (16)
C3—C4—S2128.75 (19)F5—P3—F190.38 (13)
C5—C4—S2114.19 (19)F4—P3—F691.25 (15)
C7—C6—P1107.00 (17)F5—P3—F690.83 (14)
C6—C7—P2106.99 (18)F1—P3—F688.03 (16)
C12—C11—C16119.1 (3)F4—P3—F292.05 (16)
C12—C11—P1122.8 (2)F5—P3—F2177.39 (15)
C16—C11—P1118.0 (2)F1—P3—F287.40 (15)
C13—C12—C11120.3 (3)F6—P3—F290.46 (14)
C12—C13—C14119.9 (3)F4—P3—F390.53 (18)
C15—C14—C13120.5 (3)F5—P3—F389.60 (15)
C14—C15—C16119.7 (3)F1—P3—F390.19 (17)
C15—C16—C11120.4 (3)F6—P3—F3178.17 (16)
C22—C21—C26118.0 (2)F2—P3—F389.04 (15)
(III) Pentane-2,4-dithione[bis(diphenylphosphino)propane]nickel(II) hexafluorophosphate. top
Crystal data top
[Ni(C27H26P2)(C5H7S2)]PF6F(000) = 768
Mr = 747.32Dx = 1.447 Mg m3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
a = 10.0345 (2) ÅCell parameters from 8192 reflections
b = 15.8632 (2) Åθ = 2–26°
c = 10.8058 (2) ŵ = 0.88 mm1
β = 94.14°T = 203 K
V = 1715.58 (5) Å3Prism, orange
Z = 20.30 × 0.22 × 0.18 mm
Data collection top
Siemens SMART
diffractometer
3634 independent reflections
Radiation source: fine-focus sealed tube2789 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Area–detector ω scansθmax = 26.4°, θmin = 1.9°
Absorption correction: multi-scan
(Blessing, 1995)
h = 1212
Tmin = 0.778, Tmax = 0.857k = 1919
15834 measured reflectionsl = 1313
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095H-atom parameters constrained
S = 1.00Calculated w = 1/[σ2(Fo2) + (0.0472P)2 + 0.6603P]
where P = (Fo2 + 2Fc2)/3
3634 reflections(Δ/σ)max = 0.001
211 parametersΔρmax = 0.34 e Å3
72 restraintsΔρmin = 0.26 e Å3
Crystal data top
[Ni(C27H26P2)(C5H7S2)]PF6V = 1715.58 (5) Å3
Mr = 747.32Z = 2
Monoclinic, P21/mMo Kα radiation
a = 10.0345 (2) ŵ = 0.88 mm1
b = 15.8632 (2) ÅT = 203 K
c = 10.8058 (2) Å0.30 × 0.22 × 0.18 mm
β = 94.14°
Data collection top
Siemens SMART
diffractometer
3634 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
2789 reflections with I > 2σ(I)
Tmin = 0.778, Tmax = 0.857Rint = 0.031
15834 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03572 restraints
wR(F2) = 0.095H-atom parameters constrained
S = 1.00Δρmax = 0.34 e Å3
3634 reflectionsΔρmin = 0.26 e Å3
211 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni0.38982 (4)0.25000.82875 (3)0.04148 (13)
S10.31573 (7)0.35159 (4)0.93587 (6)0.05904 (18)
P10.48000 (6)0.15051 (4)0.71370 (5)0.04412 (15)
C10.1797 (4)0.4041 (2)1.1268 (4)0.0995 (12)
H1A0.20890.45501.08700.149*
H1B0.21580.40301.21250.149*
H1C0.08280.40321.12410.149*
C20.2287 (3)0.32782 (18)1.0594 (2)0.0614 (7)
C30.1970 (4)0.25001.1021 (4)0.0701 (11)
H30.14540.25001.17130.084*
C40.4751 (3)0.16997 (16)0.5464 (2)0.0573 (6)
H4A0.51720.12200.50740.069*
H4B0.38130.17140.51410.069*
C50.5420 (4)0.25000.5057 (3)0.0556 (8)
H5A0.54220.25000.41500.067*
H5B0.63530.25000.53960.067*
C110.4021 (2)0.04626 (15)0.7167 (2)0.0509 (5)
C120.4656 (3)0.02166 (17)0.7736 (3)0.0662 (7)
H12A0.55150.01530.81340.079*
C130.4027 (4)0.09994 (19)0.7725 (3)0.0842 (9)
H13A0.44670.14640.81080.101*
C140.2783 (4)0.1095 (2)0.7162 (3)0.0845 (10)
H14A0.23670.16260.71550.101*
C150.2135 (3)0.0424 (2)0.6607 (3)0.0823 (9)
H15A0.12700.04930.62250.099*
C160.2744 (3)0.03590 (19)0.6605 (3)0.0708 (7)
H16A0.22920.08200.62240.085*
C210.6545 (2)0.13424 (15)0.7651 (3)0.0541 (6)
C220.6943 (3)0.1442 (2)0.8880 (4)0.0965 (12)
H22A0.63050.15700.94470.116*
C230.8272 (4)0.1356 (3)0.9300 (5)0.141 (2)
H23A0.85350.14221.01470.170*
C240.9187 (4)0.1175 (3)0.8481 (6)0.131 (2)
H24A1.00930.11300.87610.157*
C250.8824 (4)0.1061 (4)0.7281 (6)0.142 (2)
H25A0.94700.09280.67240.170*
C260.7489 (3)0.1139 (3)0.6855 (4)0.1076 (14)
H26A0.72350.10510.60110.129*
P20.05592 (9)0.25000.45600 (9)0.0620 (3)
F10.0151 (2)0.25000.3197 (2)0.1001 (10)
F20.0847 (3)0.25000.5091 (3)0.1087 (10)
F30.1291 (3)0.25000.5914 (2)0.0930 (8)
F40.1976 (2)0.25000.4005 (2)0.1244 (13)
F50.0568 (2)0.15064 (14)0.4566 (3)0.1275 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni0.0358 (2)0.0466 (2)0.0424 (2)0.0000.00536 (16)0.000
S10.0621 (4)0.0539 (4)0.0640 (4)0.0058 (3)0.0244 (3)0.0084 (3)
P10.0391 (3)0.0472 (3)0.0464 (3)0.0010 (2)0.0057 (2)0.0009 (2)
C10.110 (3)0.085 (2)0.110 (3)0.018 (2)0.059 (2)0.040 (2)
C20.0597 (15)0.0711 (17)0.0552 (14)0.0074 (13)0.0157 (12)0.0153 (13)
C30.077 (3)0.078 (3)0.059 (2)0.0000.0291 (19)0.000
C40.0658 (15)0.0615 (15)0.0450 (13)0.0015 (12)0.0061 (11)0.0054 (11)
C50.060 (2)0.065 (2)0.0423 (17)0.0000.0093 (15)0.000
C110.0500 (13)0.0496 (13)0.0540 (13)0.0025 (10)0.0104 (10)0.0055 (11)
C120.0674 (16)0.0549 (16)0.0757 (18)0.0021 (13)0.0028 (14)0.0038 (13)
C130.098 (2)0.0538 (17)0.102 (2)0.0060 (16)0.0096 (19)0.0056 (16)
C140.096 (2)0.0600 (19)0.100 (2)0.0255 (18)0.022 (2)0.0142 (17)
C150.0680 (18)0.082 (2)0.097 (2)0.0243 (17)0.0032 (17)0.0141 (18)
C160.0554 (15)0.0674 (18)0.088 (2)0.0092 (13)0.0026 (14)0.0030 (15)
C210.0400 (12)0.0479 (13)0.0752 (16)0.0014 (10)0.0087 (11)0.0090 (12)
C220.0629 (18)0.112 (3)0.110 (3)0.0295 (18)0.0289 (18)0.046 (2)
C230.085 (3)0.138 (4)0.190 (5)0.042 (3)0.069 (3)0.069 (4)
C240.047 (2)0.104 (3)0.236 (6)0.0044 (19)0.017 (3)0.051 (4)
C250.062 (2)0.193 (5)0.178 (5)0.047 (3)0.058 (3)0.119 (4)
C260.0673 (19)0.159 (4)0.100 (2)0.047 (2)0.0360 (18)0.062 (2)
P20.0480 (5)0.0877 (7)0.0500 (5)0.0000.0014 (4)0.000
F10.0494 (12)0.196 (3)0.0543 (13)0.0000.0042 (10)0.000
F20.0692 (16)0.177 (3)0.0839 (18)0.0000.0311 (14)0.000
F30.1046 (19)0.119 (2)0.0529 (13)0.0000.0154 (13)0.000
F40.0436 (13)0.255 (4)0.0738 (16)0.0000.0017 (12)0.000
F50.1328 (19)0.0891 (15)0.153 (2)0.0085 (13)0.0389 (16)0.0239 (14)
Geometric parameters (Å, º) top
Ni—S12.1479 (7)C11—C161.388 (3)
Ni—S1i2.1479 (7)C12—C131.393 (4)
Ni—P12.2401 (6)C13—C141.357 (5)
Ni—P1i2.2401 (6)C14—C151.364 (5)
S1—C21.690 (3)C15—C161.384 (4)
S1—P1i3.0088 (8)C21—C261.363 (4)
S1—S1i3.2230 (13)C21—C221.368 (4)
P1—C211.816 (2)C22—C231.384 (5)
P1—C111.830 (2)C23—C241.352 (7)
P1—C41.832 (2)C24—C251.334 (7)
P1—P1i3.1565 (12)C25—C261.391 (5)
C1—C21.513 (4)P2—F21.561 (3)
C2—C31.364 (3)P2—F5i1.576 (2)
C3—C2i1.364 (3)P2—F51.576 (2)
C4—C51.516 (3)P2—F41.582 (3)
C5—C4i1.516 (3)P2—F31.589 (2)
C11—C121.375 (4)P2—F11.589 (2)
S1—Ni—S1i97.23 (4)C16—C11—P1118.8 (2)
S1—Ni—P1175.62 (3)C11—C12—C13120.0 (3)
S1i—Ni—P186.55 (2)C14—C13—C12120.4 (3)
S1—Ni—P1i86.55 (2)C13—C14—C15120.2 (3)
S1i—Ni—P1i175.62 (3)C14—C15—C16120.3 (3)
P1—Ni—P1i89.59 (3)C15—C16—C11120.0 (3)
C2—S1—Ni118.49 (10)C26—C21—C22118.1 (3)
C2—S1—P1i166.42 (10)C26—C21—P1122.6 (2)
Ni—S1—P1i48.001 (18)C22—C21—P1119.2 (2)
C2—S1—S1i77.11 (10)C21—C22—C23121.0 (4)
Ni—S1—S1i41.388 (19)C24—C23—C22119.3 (4)
P1i—S1—S1i89.368 (16)C25—C24—C23121.0 (4)
C21—P1—C11105.64 (11)C24—C25—C26119.9 (4)
C21—P1—C4106.40 (12)C21—C26—C25120.6 (4)
C11—P1—C4100.86 (11)F2—P2—F5i90.21 (11)
C21—P1—Ni110.46 (9)F2—P2—F590.21 (11)
C11—P1—Ni115.90 (8)F5i—P2—F5179.21 (18)
C4—P1—Ni116.49 (9)F2—P2—F4179.28 (15)
C21—P1—P1i98.17 (8)F5i—P2—F489.79 (11)
C11—P1—P1i154.63 (7)F5—P2—F489.79 (11)
C4—P1—P1i80.30 (8)F2—P2—F391.81 (16)
Ni—P1—P1i45.206 (16)F5i—P2—F389.66 (9)
C3—C2—C1118.0 (3)F5—P2—F389.66 (9)
C3—C2—S1128.0 (2)F4—P2—F388.91 (15)
C1—C2—S1114.0 (2)F2—P2—F189.06 (14)
C2i—C3—C2129.7 (4)F5i—P2—F190.34 (9)
C5—C4—P1116.51 (19)F5—P2—F190.34 (9)
C4—C5—C4i113.7 (3)F4—P2—F190.22 (13)
C12—C11—C16119.1 (2)F3—P2—F1179.13 (15)
C12—C11—P1122.10 (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
Mr719.27733.30747.32
Crystal system, space groupMonoclinic, P21/nTriclinic, P1Monoclinic, P21/m
Temperature (K)203203203
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), 9067.386 (1), 76.105 (1), 72.088 (1)90, 94.14, 90
V3)3221.32 (5)1889.50 (5)1715.58 (5)
Z422
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.940.800.88
Crystal size (mm)0.50 × 0.34 × 0.280.58 × 0.32 × 0.100.30 × 0.22 × 0.18
Data collection
DiffractometerSiemens SMART
diffractometer
Siemens SMART
diffractometer
Siemens SMART
diffractometer
Absorption correctionMulti-scan
(Blessing, 1995)
Multi-scan
(Blessing, 1995)
Multi-scan
(Blessing, 1995)
Tmin, Tmax0.652, 0.7800.654, 0.9240.778, 0.857
No. of measured, independent and
observed [I > 2σ(I)] reflections
30784, 7145, 6130 17129, 7347, 5871 15834, 3634, 2789
Rint0.0180.0290.031
(sin θ/λ)max1)0.6480.6200.625
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 reflections714573473634
No. of parameters379390211
No. of restraints0072
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.200.53, 0.560.34, 0.26

Computer programs: SMART (Siemens, 1995), SMART, SAINT (Siemens, 1995), SHELXS (Sheldrick, 1990), SHELXL97 Sheldrick, (1997), SHELXL97.

 

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