Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005475/cv6016sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005475/cv6016Isup2.hkl |
CCDC reference: 165629
The title compound was prepared according to the literature method of Klaui et al. (1983). A mixture of (η5-C5H5)2Ni (189 mg, 1.0 mmol) and Ph2P(S)H (218 mg, 1.0 mmol) was dissolved in 20 ml toluene and refluxed for 2 h, during which time the solution color changed from green to brown. The solvent was pumped off and residue was washed with hexane and chilled Et2O. Single crystals suitable for X-ray analysis were obtained by recrystallization from CH2Cl2/Et2O.
After checking their presence in the difference map, all H atoms were geometrically fixed and allowed to ride on their attached atoms with Uiso = 1.2Ueq for the attached atoms.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 1990).
Fig. 1. The structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme. |
[Ni2(C5H5)2(C12H10PS)2] | F(000) = 1408 |
Mr = 682.06 | Dx = 1.493 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4231 (2) Å | Cell parameters from 7990 reflections |
b = 14.5514 (2) Å | θ = 2.7–28.4° |
c = 22.2014 (4) Å | µ = 1.51 mm−1 |
β = 94.560 (1)° | T = 293 K |
V = 3034.60 (9) Å3 | Block, black |
Z = 4 | 0.48 × 0.42 × 0.38 mm |
Siemens SMART CCD area-detector diffractometer | 7506 independent reflections |
Radiation source: fine-focus sealed tube | 6064 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.3°, θmin = 2.7° |
ω scans | h = −11→12 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −19→18 |
Tmin = 0.532, Tmax = 0.598 | l = −25→29 |
21461 measured reflections |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0384P)2] where P = (Fo2 + 2Fc2)/3 |
7506 reflections | (Δ/σ)max = 0.001 |
361 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.66 e Å−3 |
[Ni2(C5H5)2(C12H10PS)2] | V = 3034.60 (9) Å3 |
Mr = 682.06 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.4231 (2) Å | µ = 1.51 mm−1 |
b = 14.5514 (2) Å | T = 293 K |
c = 22.2014 (4) Å | 0.48 × 0.42 × 0.38 mm |
β = 94.560 (1)° |
Siemens SMART CCD area-detector diffractometer | 7506 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 6064 reflections with I > 2σ(I) |
Tmin = 0.532, Tmax = 0.598 | Rint = 0.059 |
21461 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.67 e Å−3 |
7506 reflections | Δρmin = −0.66 e Å−3 |
361 parameters |
Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Coverage of the unique set is over 99.5% complete. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the duplicate reflections, and was found to be negligible. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.00860 (3) | 0.765748 (17) | 0.265393 (11) | 0.02894 (8) | |
Ni2 | 0.14754 (3) | 0.857248 (17) | 0.129241 (12) | 0.03275 (8) | |
P1 | 0.23685 (5) | 0.77299 (3) | 0.26430 (2) | 0.02669 (11) | |
P2 | 0.03117 (5) | 0.73131 (3) | 0.11593 (2) | 0.02759 (11) | |
S1 | 0.32078 (5) | 0.78440 (4) | 0.18150 (2) | 0.03468 (12) | |
S2 | −0.00701 (6) | 0.66130 (3) | 0.19366 (2) | 0.03298 (12) | |
C1 | −0.0988 (3) | 0.88358 (17) | 0.29932 (12) | 0.0517 (6) | |
H1A | −0.0816 | 0.9481 | 0.2897 | 0.062* | |
C2 | −0.0240 (3) | 0.83053 (18) | 0.34565 (11) | 0.0493 (6) | |
H2A | 0.0512 | 0.8538 | 0.3747 | 0.059* | |
C3 | −0.0875 (3) | 0.74286 (18) | 0.34768 (12) | 0.0518 (6) | |
H3A | −0.0633 | 0.6943 | 0.3773 | 0.062* | |
C4 | −0.1908 (3) | 0.73878 (19) | 0.29959 (13) | 0.0539 (7) | |
H4A | −0.2517 | 0.6856 | 0.2890 | 0.065* | |
C5 | −0.2009 (3) | 0.8262 (2) | 0.27049 (13) | 0.0549 (7) | |
H5A | −0.2676 | 0.8429 | 0.2361 | 0.066* | |
C6 | 0.3084 (2) | 0.66720 (14) | 0.29887 (9) | 0.0333 (4) | |
C7 | 0.2946 (3) | 0.65205 (17) | 0.36019 (11) | 0.0475 (6) | |
H7A | 0.2550 | 0.6971 | 0.3834 | 0.057* | |
C8 | 0.3400 (3) | 0.5698 (2) | 0.38650 (13) | 0.0612 (7) | |
H8A | 0.3299 | 0.5595 | 0.4273 | 0.073* | |
C9 | 0.4002 (3) | 0.50293 (19) | 0.35259 (16) | 0.0667 (8) | |
H9A | 0.4312 | 0.4480 | 0.3706 | 0.080* | |
C10 | 0.4142 (3) | 0.51732 (17) | 0.29292 (15) | 0.0613 (7) | |
H10A | 0.4548 | 0.4721 | 0.2702 | 0.074* | |
C11 | 0.3684 (3) | 0.59867 (16) | 0.26571 (11) | 0.0460 (5) | |
H11A | 0.3779 | 0.6075 | 0.2247 | 0.055* | |
C12 | 0.3322 (2) | 0.86217 (13) | 0.30955 (9) | 0.0311 (4) | |
C13 | 0.2751 (3) | 0.94973 (15) | 0.31157 (10) | 0.0427 (5) | |
H13A | 0.1850 | 0.9612 | 0.2929 | 0.051* | |
C14 | 0.3511 (3) | 1.02067 (17) | 0.34110 (12) | 0.0534 (6) | |
H14A | 0.3116 | 1.0792 | 0.3424 | 0.064* | |
C15 | 0.4858 (3) | 1.00388 (18) | 0.36867 (11) | 0.0521 (6) | |
H15A | 0.5372 | 1.0511 | 0.3884 | 0.063* | |
C16 | 0.5429 (3) | 0.91733 (19) | 0.36669 (11) | 0.0526 (6) | |
H16A | 0.6332 | 0.9060 | 0.3852 | 0.063* | |
C17 | 0.4672 (2) | 0.84680 (16) | 0.33741 (11) | 0.0413 (5) | |
H17A | 0.5071 | 0.7884 | 0.3364 | 0.050* | |
C18 | 0.1195 (2) | 0.64806 (14) | 0.06970 (9) | 0.0319 (4) | |
C19 | 0.0930 (2) | 0.55496 (15) | 0.07462 (9) | 0.0389 (5) | |
H19A | 0.0311 | 0.5346 | 0.1024 | 0.047* | |
C20 | 0.1571 (3) | 0.49152 (17) | 0.03896 (11) | 0.0485 (6) | |
H20A | 0.1383 | 0.4291 | 0.0428 | 0.058* | |
C21 | 0.2484 (3) | 0.5214 (2) | −0.00200 (11) | 0.0559 (7) | |
H21A | 0.2916 | 0.4790 | −0.0260 | 0.067* | |
C22 | 0.2765 (3) | 0.6130 (2) | −0.00789 (11) | 0.0579 (7) | |
H22A | 0.3380 | 0.6326 | −0.0360 | 0.070* | |
C23 | 0.2128 (3) | 0.67745 (18) | 0.02829 (11) | 0.0485 (6) | |
H23A | 0.2330 | 0.7397 | 0.0246 | 0.058* | |
C24 | −0.1427 (2) | 0.74582 (14) | 0.07261 (9) | 0.0312 (4) | |
C25 | −0.1497 (2) | 0.75894 (17) | 0.01078 (10) | 0.0439 (5) | |
H25A | −0.0668 | 0.7564 | −0.0093 | 0.053* | |
C26 | −0.2793 (3) | 0.7760 (2) | −0.02175 (11) | 0.0532 (6) | |
H26A | −0.2827 | 0.7848 | −0.0633 | 0.064* | |
C27 | −0.4024 (3) | 0.77968 (19) | 0.00756 (12) | 0.0530 (6) | |
H27A | −0.4891 | 0.7912 | −0.0141 | 0.064* | |
C28 | −0.3969 (3) | 0.76636 (18) | 0.06869 (12) | 0.0503 (6) | |
H28A | −0.4804 | 0.7682 | 0.0884 | 0.060* | |
C29 | −0.2676 (2) | 0.75001 (15) | 0.10176 (10) | 0.0387 (5) | |
H29A | −0.2649 | 0.7419 | 0.1434 | 0.046* | |
C30 | 0.0648 (4) | 0.99068 (17) | 0.14935 (16) | 0.0686 (8) | |
H30A | 0.0177 | 1.0088 | 0.1853 | 0.082* | |
C31 | 0.0002 (3) | 0.95247 (18) | 0.09495 (15) | 0.0650 (8) | |
H31A | −0.1019 | 0.9413 | 0.0860 | 0.078* | |
C32 | 0.1063 (4) | 0.9431 (2) | 0.05350 (14) | 0.0684 (8) | |
H32A | 0.0903 | 0.9225 | 0.0115 | 0.082* | |
C33 | 0.2336 (4) | 0.9705 (2) | 0.08129 (17) | 0.0733 (9) | |
H33A | 0.3251 | 0.9712 | 0.0632 | 0.088* | |
C34 | 0.2105 (3) | 0.99707 (17) | 0.14044 (17) | 0.0694 (9) | |
H34A | 0.2843 | 1.0195 | 0.1705 | 0.083* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.02630 (13) | 0.03423 (14) | 0.02678 (14) | 0.00279 (10) | 0.00512 (10) | −0.00403 (9) |
Ni2 | 0.03323 (15) | 0.02987 (14) | 0.03444 (15) | −0.00260 (10) | −0.00172 (11) | 0.00501 (10) |
P1 | 0.0262 (2) | 0.0300 (2) | 0.0238 (2) | 0.00320 (18) | 0.00158 (18) | −0.00211 (18) |
P2 | 0.0286 (2) | 0.0305 (2) | 0.0235 (2) | −0.00106 (19) | 0.00148 (19) | 0.00002 (18) |
S1 | 0.0290 (2) | 0.0482 (3) | 0.0273 (3) | 0.0043 (2) | 0.00517 (19) | 0.0019 (2) |
S2 | 0.0434 (3) | 0.0312 (2) | 0.0246 (2) | −0.0054 (2) | 0.0043 (2) | −0.00016 (18) |
C1 | 0.0543 (15) | 0.0420 (13) | 0.0612 (16) | 0.0121 (11) | 0.0206 (12) | −0.0092 (11) |
C2 | 0.0492 (14) | 0.0626 (15) | 0.0380 (13) | 0.0019 (12) | 0.0148 (11) | −0.0187 (11) |
C3 | 0.0586 (16) | 0.0595 (15) | 0.0408 (14) | 0.0033 (12) | 0.0260 (12) | 0.0003 (11) |
C4 | 0.0374 (13) | 0.0601 (16) | 0.0678 (18) | −0.0048 (11) | 0.0272 (13) | −0.0148 (13) |
C5 | 0.0353 (13) | 0.0705 (17) | 0.0596 (16) | 0.0182 (12) | 0.0078 (11) | −0.0119 (13) |
C6 | 0.0277 (10) | 0.0346 (10) | 0.0364 (11) | −0.0001 (8) | −0.0040 (8) | 0.0014 (8) |
C7 | 0.0492 (14) | 0.0506 (14) | 0.0421 (13) | 0.0009 (11) | 0.0005 (10) | 0.0068 (10) |
C8 | 0.0576 (16) | 0.0692 (19) | 0.0548 (16) | −0.0083 (14) | −0.0087 (13) | 0.0300 (14) |
C9 | 0.0539 (16) | 0.0415 (14) | 0.101 (2) | −0.0015 (12) | −0.0182 (16) | 0.0241 (15) |
C10 | 0.0572 (17) | 0.0383 (13) | 0.086 (2) | 0.0131 (12) | −0.0071 (14) | −0.0002 (13) |
C11 | 0.0472 (13) | 0.0401 (12) | 0.0499 (14) | 0.0083 (10) | 0.0003 (10) | −0.0036 (10) |
C12 | 0.0302 (10) | 0.0348 (10) | 0.0285 (10) | −0.0003 (8) | 0.0031 (8) | −0.0027 (8) |
C13 | 0.0412 (12) | 0.0377 (12) | 0.0479 (13) | 0.0028 (9) | −0.0040 (10) | −0.0058 (10) |
C14 | 0.0606 (17) | 0.0379 (13) | 0.0611 (16) | −0.0007 (11) | 0.0014 (13) | −0.0115 (11) |
C15 | 0.0558 (16) | 0.0510 (14) | 0.0490 (15) | −0.0181 (12) | 0.0007 (11) | −0.0157 (11) |
C16 | 0.0365 (13) | 0.0649 (17) | 0.0546 (15) | −0.0083 (11) | −0.0069 (11) | −0.0084 (12) |
C17 | 0.0322 (11) | 0.0453 (12) | 0.0459 (13) | −0.0003 (9) | −0.0013 (9) | −0.0074 (10) |
C18 | 0.0314 (10) | 0.0399 (11) | 0.0241 (10) | 0.0027 (8) | 0.0001 (8) | −0.0027 (8) |
C19 | 0.0425 (12) | 0.0404 (12) | 0.0337 (11) | 0.0045 (9) | 0.0019 (9) | −0.0021 (9) |
C20 | 0.0556 (15) | 0.0440 (13) | 0.0447 (13) | 0.0115 (11) | −0.0041 (11) | −0.0097 (10) |
C21 | 0.0533 (15) | 0.0692 (18) | 0.0448 (14) | 0.0226 (13) | 0.0016 (11) | −0.0181 (12) |
C22 | 0.0530 (16) | 0.0782 (19) | 0.0454 (15) | 0.0044 (14) | 0.0209 (12) | −0.0069 (13) |
C23 | 0.0494 (14) | 0.0535 (14) | 0.0448 (14) | −0.0033 (11) | 0.0170 (11) | −0.0015 (11) |
C24 | 0.0288 (10) | 0.0343 (10) | 0.0303 (10) | −0.0019 (8) | 0.0014 (8) | −0.0021 (8) |
C25 | 0.0348 (12) | 0.0673 (15) | 0.0297 (11) | 0.0009 (11) | 0.0022 (9) | −0.0002 (10) |
C26 | 0.0440 (14) | 0.0832 (19) | 0.0315 (13) | 0.0037 (12) | −0.0033 (10) | 0.0028 (11) |
C27 | 0.0323 (12) | 0.0752 (18) | 0.0501 (15) | 0.0037 (11) | −0.0055 (10) | 0.0004 (12) |
C28 | 0.0293 (11) | 0.0674 (17) | 0.0548 (16) | 0.0040 (10) | 0.0078 (10) | 0.0010 (12) |
C29 | 0.0358 (11) | 0.0472 (12) | 0.0334 (12) | −0.0001 (9) | 0.0053 (9) | −0.0007 (9) |
C30 | 0.088 (2) | 0.0308 (12) | 0.088 (2) | 0.0150 (14) | 0.0138 (18) | 0.0019 (13) |
C31 | 0.0478 (15) | 0.0393 (14) | 0.104 (2) | 0.0055 (11) | −0.0179 (15) | 0.0222 (15) |
C32 | 0.085 (2) | 0.0577 (17) | 0.0596 (18) | 0.0043 (15) | −0.0096 (16) | 0.0279 (14) |
C33 | 0.073 (2) | 0.0574 (18) | 0.090 (2) | −0.0133 (15) | 0.0079 (18) | 0.0343 (17) |
C34 | 0.068 (2) | 0.0304 (12) | 0.105 (3) | −0.0106 (12) | −0.0218 (18) | 0.0064 (14) |
Ni1—C2 | 2.060 (2) | C12—C17 | 1.387 (3) |
Ni1—C4 | 2.119 (2) | C13—C14 | 1.390 (3) |
Ni1—C3 | 2.129 (2) | C13—H13A | 0.9300 |
Ni1—P1 | 2.1555 (6) | C14—C15 | 1.386 (4) |
Ni1—C1 | 2.157 (2) | C14—H14A | 0.9300 |
Ni1—C5 | 2.173 (2) | C15—C16 | 1.372 (4) |
Ni1—S2 | 2.1979 (5) | C15—H15A | 0.9300 |
Ni2—C31 | 2.064 (2) | C16—C17 | 1.382 (3) |
Ni2—C32 | 2.106 (3) | C16—H16A | 0.9300 |
Ni2—C34 | 2.128 (3) | C17—H17A | 0.9300 |
Ni2—P2 | 2.1440 (6) | C18—C19 | 1.383 (3) |
Ni2—C30 | 2.153 (3) | C18—C23 | 1.390 (3) |
Ni2—C33 | 2.155 (3) | C19—C20 | 1.385 (3) |
Ni2—S1 | 2.1986 (6) | C19—H19A | 0.9300 |
P1—C6 | 1.825 (2) | C20—C21 | 1.371 (4) |
P1—C12 | 1.832 (2) | C20—H20A | 0.9300 |
P1—S1 | 2.0648 (7) | C21—C22 | 1.368 (4) |
P2—C18 | 1.830 (2) | C21—H21A | 0.9300 |
P2—C24 | 1.845 (2) | C22—C23 | 1.400 (3) |
P2—S2 | 2.0600 (7) | C22—H22A | 0.9300 |
C1—C5 | 1.390 (4) | C23—H23A | 0.9300 |
C1—C2 | 1.427 (4) | C24—C25 | 1.382 (3) |
C1—H1A | 0.9800 | C24—C29 | 1.389 (3) |
C2—C3 | 1.411 (4) | C25—C26 | 1.391 (3) |
C2—H2A | 0.9800 | C25—H25A | 0.9300 |
C3—C4 | 1.388 (4) | C26—C27 | 1.376 (3) |
C3—H3A | 0.9800 | C26—H26A | 0.9300 |
C4—C5 | 1.427 (4) | C27—C28 | 1.368 (4) |
C4—H4A | 0.9800 | C27—H27A | 0.9300 |
C5—H5A | 0.9800 | C28—C29 | 1.392 (3) |
C6—C11 | 1.387 (3) | C28—H28A | 0.9300 |
C6—C7 | 1.395 (3) | C29—H29A | 0.9300 |
C7—C8 | 1.385 (3) | C30—C34 | 1.406 (5) |
C7—H7A | 0.9300 | C30—C31 | 1.422 (4) |
C8—C9 | 1.379 (4) | C30—H30A | 0.9800 |
C8—H8A | 0.9300 | C31—C32 | 1.419 (4) |
C9—C10 | 1.358 (4) | C31—H31A | 0.9800 |
C9—H9A | 0.9300 | C32—C33 | 1.364 (5) |
C10—C11 | 1.382 (3) | C32—H32A | 0.9800 |
C10—H10A | 0.9300 | C33—C34 | 1.403 (5) |
C11—H11A | 0.9300 | C33—H33A | 0.9800 |
C12—C13 | 1.385 (3) | C34—H34A | 0.9800 |
C2—Ni1—C4 | 64.99 (11) | C7—C8—H8A | 119.8 |
C2—Ni1—C3 | 39.33 (10) | C10—C9—C8 | 120.0 (2) |
C4—Ni1—C3 | 38.15 (11) | C10—C9—H9A | 120.0 |
C2—Ni1—P1 | 101.82 (8) | C8—C9—H9A | 120.0 |
C4—Ni1—P1 | 158.03 (9) | C9—C10—C11 | 120.5 (3) |
C3—Ni1—P1 | 120.67 (9) | C9—C10—H10A | 119.8 |
C2—Ni1—C1 | 39.46 (10) | C11—C10—H10A | 119.8 |
C4—Ni1—C1 | 64.40 (10) | C10—C11—C6 | 120.7 (2) |
C3—Ni1—C1 | 65.25 (10) | C10—C11—H11A | 119.7 |
P1—Ni1—C1 | 117.47 (8) | C6—C11—H11A | 119.7 |
C2—Ni1—C5 | 64.59 (10) | C13—C12—C17 | 118.6 (2) |
C4—Ni1—C5 | 38.82 (11) | C13—C12—P1 | 119.64 (16) |
C3—Ni1—C5 | 64.44 (11) | C17—C12—P1 | 121.50 (16) |
P1—Ni1—C5 | 153.17 (8) | C12—C13—C14 | 120.8 (2) |
C1—Ni1—C5 | 37.46 (10) | C12—C13—H13A | 119.6 |
C2—Ni1—S2 | 159.56 (8) | C14—C13—H13A | 119.6 |
C4—Ni1—S2 | 96.98 (7) | C15—C14—C13 | 119.7 (2) |
C3—Ni1—S2 | 120.34 (8) | C15—C14—H14A | 120.1 |
P1—Ni1—S2 | 92.01 (2) | C13—C14—H14A | 120.1 |
C1—Ni1—S2 | 142.80 (8) | C16—C15—C14 | 119.7 (2) |
C5—Ni1—S2 | 108.01 (8) | C16—C15—H15A | 120.1 |
C31—Ni2—C32 | 39.76 (12) | C14—C15—H15A | 120.1 |
C31—Ni2—C34 | 64.81 (11) | C15—C16—C17 | 120.5 (2) |
C32—Ni2—C34 | 63.79 (13) | C15—C16—H16A | 119.8 |
C31—Ni2—P2 | 101.61 (8) | C17—C16—H16A | 119.8 |
C32—Ni2—P2 | 109.70 (10) | C16—C17—C12 | 120.7 (2) |
C34—Ni2—P2 | 165.46 (9) | C16—C17—H17A | 119.6 |
C31—Ni2—C30 | 39.34 (12) | C12—C17—H17A | 119.6 |
C32—Ni2—C30 | 65.40 (13) | C19—C18—C23 | 118.76 (19) |
C34—Ni2—C30 | 38.35 (13) | C19—C18—P2 | 120.73 (15) |
P2—Ni2—C30 | 127.57 (10) | C23—C18—P2 | 120.50 (17) |
C31—Ni2—C33 | 64.73 (12) | C18—C19—C20 | 121.2 (2) |
C32—Ni2—C33 | 37.32 (13) | C18—C19—H19A | 119.4 |
C34—Ni2—C33 | 38.22 (13) | C20—C19—H19A | 119.4 |
P2—Ni2—C33 | 142.56 (11) | C21—C20—C19 | 119.5 (2) |
C30—Ni2—C33 | 64.51 (13) | C21—C20—H20A | 120.2 |
C31—Ni2—S1 | 165.45 (9) | C19—C20—H20A | 120.2 |
C32—Ni2—S1 | 142.13 (10) | C22—C21—C20 | 120.6 (2) |
C34—Ni2—S1 | 102.17 (9) | C22—C21—H21A | 119.7 |
P2—Ni2—S1 | 90.62 (2) | C20—C21—H21A | 119.7 |
C30—Ni2—S1 | 126.27 (10) | C21—C22—C23 | 120.2 (2) |
C33—Ni2—S1 | 109.67 (10) | C21—C22—H22A | 119.9 |
C6—P1—C12 | 102.60 (9) | C23—C22—H22A | 119.9 |
C6—P1—S1 | 106.70 (7) | C18—C23—C22 | 119.8 (2) |
C12—P1—S1 | 103.02 (7) | C18—C23—H23A | 120.1 |
C6—P1—Ni1 | 106.83 (7) | C22—C23—H23A | 120.1 |
C12—P1—Ni1 | 118.35 (7) | C25—C24—C29 | 118.8 (2) |
S1—P1—Ni1 | 117.85 (3) | C25—C24—P2 | 120.27 (15) |
C18—P2—C24 | 102.00 (9) | C29—C24—P2 | 120.84 (16) |
C18—P2—S2 | 105.07 (7) | C24—C25—C26 | 120.7 (2) |
C24—P2—S2 | 106.65 (7) | C24—C25—H25A | 119.6 |
C18—P2—Ni2 | 113.12 (7) | C26—C25—H25A | 119.6 |
C24—P2—Ni2 | 113.41 (7) | C27—C26—C25 | 120.0 (2) |
S2—P2—Ni2 | 115.39 (3) | C27—C26—H26A | 120.0 |
P1—S1—Ni2 | 100.82 (3) | C25—C26—H26A | 120.0 |
P2—S2—Ni1 | 105.01 (2) | C28—C27—C26 | 119.8 (2) |
C5—C1—C2 | 106.9 (2) | C28—C27—H27A | 120.1 |
C5—C1—Ni1 | 71.87 (13) | C26—C27—H27A | 120.1 |
C2—C1—Ni1 | 66.61 (12) | C27—C28—C29 | 120.7 (2) |
C5—C1—H1A | 126.5 | C27—C28—H28A | 119.7 |
C2—C1—H1A | 126.5 | C29—C28—H28A | 119.7 |
Ni1—C1—H1A | 126.5 | C24—C29—C28 | 120.0 (2) |
C3—C2—C1 | 109.0 (3) | C24—C29—H29A | 120.0 |
C3—C2—Ni1 | 72.95 (13) | C28—C29—H29A | 120.0 |
C1—C2—Ni1 | 73.93 (13) | C34—C30—C31 | 105.3 (3) |
C3—C2—H2A | 125.3 | C34—C30—Ni2 | 69.89 (15) |
C1—C2—H2A | 125.3 | C31—C30—Ni2 | 66.96 (14) |
Ni1—C2—H2A | 125.3 | C34—C30—H30A | 127.4 |
C4—C3—C2 | 106.7 (2) | C31—C30—H30A | 127.4 |
C4—C3—Ni1 | 70.55 (13) | Ni2—C30—H30A | 127.4 |
C2—C3—Ni1 | 67.72 (12) | C32—C31—C30 | 108.2 (3) |
C4—C3—H3A | 126.6 | C32—C31—Ni2 | 71.71 (15) |
C2—C3—H3A | 126.6 | C30—C31—Ni2 | 73.70 (16) |
Ni1—C3—H3A | 126.6 | C32—C31—H31A | 125.7 |
C3—C4—C5 | 109.1 (2) | C30—C31—H31A | 125.7 |
C3—C4—Ni1 | 71.30 (14) | Ni2—C31—H31A | 125.7 |
C5—C4—Ni1 | 72.62 (13) | C33—C32—C31 | 108.6 (3) |
C3—C4—H4A | 125.4 | C33—C32—Ni2 | 73.30 (17) |
C5—C4—H4A | 125.4 | C31—C32—Ni2 | 68.53 (15) |
Ni1—C4—H4A | 125.4 | C33—C32—H32A | 125.7 |
C1—C5—C4 | 108.0 (3) | C31—C32—H32A | 125.7 |
C1—C5—Ni1 | 70.66 (14) | Ni2—C32—H32A | 125.7 |
C4—C5—Ni1 | 68.56 (13) | C32—C33—C34 | 107.9 (3) |
C1—C5—H5A | 126.0 | C32—C33—Ni2 | 69.38 (16) |
C4—C5—H5A | 126.0 | C34—C33—Ni2 | 69.86 (15) |
Ni1—C5—H5A | 126.0 | C32—C33—H33A | 126.0 |
C11—C6—C7 | 118.6 (2) | C34—C33—H33A | 126.0 |
C11—C6—P1 | 122.40 (17) | Ni2—C33—H33A | 126.0 |
C7—C6—P1 | 118.93 (16) | C33—C34—C30 | 109.9 (3) |
C8—C7—C6 | 119.9 (2) | C33—C34—Ni2 | 71.91 (16) |
C8—C7—H7A | 120.0 | C30—C34—Ni2 | 71.76 (15) |
C6—C7—H7A | 120.0 | C33—C34—H34A | 125.0 |
C9—C8—C7 | 120.4 (3) | C30—C34—H34A | 125.0 |
C9—C8—H8A | 119.8 | Ni2—C34—H34A | 125.0 |
C2—Ni1—P1—C6 | 92.35 (10) | S1—P1—C6—C11 | −17.7 (2) |
C4—Ni1—P1—C6 | 41.8 (2) | Ni1—P1—C6—C11 | 109.15 (18) |
C3—Ni1—P1—C6 | 54.97 (11) | C12—P1—C6—C7 | 58.29 (19) |
C1—Ni1—P1—C6 | 131.07 (11) | S1—P1—C6—C7 | 166.23 (16) |
C5—Ni1—P1—C6 | 148.47 (18) | Ni1—P1—C6—C7 | −66.87 (18) |
S2—Ni1—P1—C6 | −72.51 (7) | C11—C6—C7—C8 | −0.2 (4) |
C2—Ni1—P1—C12 | −22.62 (11) | P1—C6—C7—C8 | 175.94 (19) |
C4—Ni1—P1—C12 | −73.2 (2) | C6—C7—C8—C9 | 0.7 (4) |
C3—Ni1—P1—C12 | −60.00 (11) | C7—C8—C9—C10 | −0.5 (4) |
C1—Ni1—P1—C12 | 16.10 (11) | C8—C9—C10—C11 | 0.0 (4) |
C5—Ni1—P1—C12 | 33.50 (19) | C9—C10—C11—C6 | 0.4 (4) |
S2—Ni1—P1—C12 | 172.52 (8) | C7—C6—C11—C10 | −0.3 (4) |
C2—Ni1—P1—S1 | −147.69 (8) | P1—C6—C11—C10 | −176.3 (2) |
C4—Ni1—P1—S1 | 161.76 (19) | C6—P1—C12—C13 | −157.88 (17) |
C3—Ni1—P1—S1 | 174.93 (8) | S1—P1—C12—C13 | 91.39 (17) |
C1—Ni1—P1—S1 | −108.97 (9) | Ni1—P1—C12—C13 | −40.64 (19) |
C5—Ni1—P1—S1 | −91.56 (17) | C6—P1—C12—C17 | 28.4 (2) |
S2—Ni1—P1—S1 | 47.45 (3) | S1—P1—C12—C17 | −82.38 (18) |
C31—Ni2—P2—C18 | 122.28 (12) | Ni1—P1—C12—C17 | 145.59 (16) |
C32—Ni2—P2—C18 | 81.74 (12) | C17—C12—C13—C14 | −0.3 (3) |
C34—Ni2—P2—C18 | 142.5 (4) | P1—C12—C13—C14 | −174.25 (18) |
C30—Ni2—P2—C18 | 155.34 (14) | C12—C13—C14—C15 | 0.3 (4) |
C33—Ni2—P2—C18 | 58.93 (18) | C13—C14—C15—C16 | −0.2 (4) |
S1—Ni2—P2—C18 | −65.66 (7) | C14—C15—C16—C17 | 0.0 (4) |
C31—Ni2—P2—C24 | 6.74 (12) | C15—C16—C17—C12 | 0.0 (4) |
C32—Ni2—P2—C24 | −33.80 (12) | C13—C12—C17—C16 | 0.2 (3) |
C34—Ni2—P2—C24 | 27.0 (4) | P1—C12—C17—C16 | 173.99 (18) |
C30—Ni2—P2—C24 | 39.80 (14) | C24—P2—C18—C19 | −82.40 (18) |
C33—Ni2—P2—C24 | −56.61 (17) | S2—P2—C18—C19 | 28.73 (19) |
S1—Ni2—P2—C24 | 178.80 (7) | Ni2—P2—C18—C19 | 155.43 (15) |
C31—Ni2—P2—S2 | −116.69 (10) | C24—P2—C18—C23 | 96.6 (2) |
C32—Ni2—P2—S2 | −157.23 (10) | S2—P2—C18—C23 | −152.27 (18) |
C34—Ni2—P2—S2 | −96.5 (4) | Ni2—P2—C18—C23 | −25.6 (2) |
C30—Ni2—P2—S2 | −83.64 (12) | C23—C18—C19—C20 | −0.4 (3) |
C33—Ni2—P2—S2 | 179.96 (16) | P2—C18—C19—C20 | 178.66 (18) |
S1—Ni2—P2—S2 | 55.37 (3) | C18—C19—C20—C21 | 0.0 (4) |
C6—P1—S1—Ni2 | 149.26 (7) | C19—C20—C21—C22 | 0.0 (4) |
C12—P1—S1—Ni2 | −103.10 (7) | C20—C21—C22—C23 | 0.5 (4) |
Ni1—P1—S1—Ni2 | 29.23 (4) | C19—C18—C23—C22 | 0.8 (4) |
C31—Ni2—S1—P1 | 67.8 (4) | P2—C18—C23—C22 | −178.2 (2) |
C32—Ni2—S1—P1 | 156.06 (16) | C21—C22—C23—C18 | −0.8 (4) |
C34—Ni2—S1—P1 | 93.36 (11) | C18—P2—C24—C25 | −46.4 (2) |
P2—Ni2—S1—P1 | −79.68 (3) | S2—P2—C24—C25 | −156.36 (17) |
C30—Ni2—S1—P1 | 60.17 (11) | Ni2—P2—C24—C25 | 75.54 (19) |
C33—Ni2—S1—P1 | 132.43 (11) | C18—P2—C24—C29 | 137.96 (18) |
C18—P2—S2—Ni1 | 147.84 (7) | S2—P2—C24—C29 | 28.02 (19) |
C24—P2—S2—Ni1 | −104.39 (7) | Ni2—P2—C24—C29 | −100.08 (17) |
Ni2—P2—S2—Ni1 | 22.54 (4) | C29—C24—C25—C26 | −0.1 (4) |
C2—Ni1—S2—P2 | 154.1 (2) | P2—C24—C25—C26 | −175.8 (2) |
C4—Ni1—S2—P2 | 127.17 (9) | C24—C25—C26—C27 | −0.1 (4) |
C3—Ni1—S2—P2 | 159.34 (10) | C25—C26—C27—C28 | −0.2 (4) |
P1—Ni1—S2—P2 | −72.92 (3) | C26—C27—C28—C29 | 0.7 (4) |
C1—Ni1—S2—P2 | 71.14 (12) | C25—C24—C29—C28 | 0.6 (3) |
C5—Ni1—S2—P2 | 88.94 (9) | P2—C24—C29—C28 | 176.24 (18) |
C2—Ni1—C1—C5 | −118.4 (2) | C27—C28—C29—C24 | −0.9 (4) |
C4—Ni1—C1—C5 | −37.33 (17) | C31—Ni2—C30—C34 | −117.4 (3) |
C3—Ni1—C1—C5 | −79.66 (18) | C32—Ni2—C30—C34 | −78.2 (2) |
P1—Ni1—C1—C5 | 167.17 (14) | P2—Ni2—C30—C34 | −174.85 (16) |
S2—Ni1—C1—C5 | 28.6 (2) | C33—Ni2—C30—C34 | −36.86 (19) |
C4—Ni1—C1—C2 | 81.05 (18) | S1—Ni2—C30—C34 | 59.6 (2) |
C3—Ni1—C1—C2 | 38.73 (16) | C32—Ni2—C30—C31 | 39.18 (18) |
P1—Ni1—C1—C2 | −74.44 (16) | C34—Ni2—C30—C31 | 117.4 (3) |
C5—Ni1—C1—C2 | 118.4 (2) | P2—Ni2—C30—C31 | −57.5 (2) |
S2—Ni1—C1—C2 | 146.95 (13) | C33—Ni2—C30—C31 | 80.5 (2) |
C5—C1—C2—C3 | −4.1 (2) | S1—Ni2—C30—C31 | 177.00 (14) |
Ni1—C1—C2—C3 | −65.03 (15) | C34—C30—C31—C32 | −4.1 (3) |
C5—C1—C2—Ni1 | 60.93 (16) | Ni2—C30—C31—C32 | −63.86 (18) |
C4—Ni1—C2—C3 | 36.88 (17) | C34—C30—C31—Ni2 | 59.79 (18) |
P1—Ni1—C2—C3 | −124.53 (16) | C34—Ni2—C31—C32 | 78.6 (2) |
C1—Ni1—C2—C3 | 116.3 (2) | P2—Ni2—C31—C32 | −106.92 (18) |
C5—Ni1—C2—C3 | 79.98 (18) | C30—Ni2—C31—C32 | 116.1 (3) |
S2—Ni1—C2—C3 | 7.1 (3) | C33—Ni2—C31—C32 | 36.1 (2) |
C4—Ni1—C2—C1 | −79.43 (18) | S1—Ni2—C31—C32 | 106.4 (4) |
C3—Ni1—C2—C1 | −116.3 (2) | C32—Ni2—C31—C30 | −116.1 (3) |
P1—Ni1—C2—C1 | 119.16 (14) | C34—Ni2—C31—C30 | −37.50 (19) |
C5—Ni1—C2—C1 | −36.33 (16) | P2—Ni2—C31—C30 | 137.00 (17) |
S2—Ni1—C2—C1 | −109.2 (2) | C33—Ni2—C31—C30 | −79.9 (2) |
C1—C2—C3—C4 | 5.6 (2) | S1—Ni2—C31—C30 | −9.7 (5) |
Ni1—C2—C3—C4 | −60.09 (16) | C30—C31—C32—C33 | 2.4 (3) |
C1—C2—C3—Ni1 | 65.67 (15) | Ni2—C31—C32—C33 | −62.7 (2) |
C2—Ni1—C3—C4 | 118.3 (2) | C30—C31—C32—Ni2 | 65.16 (18) |
P1—Ni1—C3—C4 | −172.07 (13) | C31—Ni2—C32—C33 | 118.4 (3) |
C1—Ni1—C3—C4 | 79.44 (17) | C34—Ni2—C32—C33 | 37.0 (2) |
C5—Ni1—C3—C4 | 37.89 (16) | P2—Ni2—C32—C33 | −157.1 (2) |
S2—Ni1—C3—C4 | −58.84 (17) | C30—Ni2—C32—C33 | 79.6 (2) |
C4—Ni1—C3—C2 | −118.3 (2) | S1—Ni2—C32—C33 | −38.5 (3) |
P1—Ni1—C3—C2 | 69.64 (17) | C34—Ni2—C32—C31 | −81.4 (2) |
C1—Ni1—C3—C2 | −38.85 (16) | P2—Ni2—C32—C31 | 84.49 (19) |
C5—Ni1—C3—C2 | −80.41 (18) | C30—Ni2—C32—C31 | −38.77 (19) |
S2—Ni1—C3—C2 | −177.14 (14) | C33—Ni2—C32—C31 | −118.4 (3) |
C2—C3—C4—C5 | −4.9 (3) | S1—Ni2—C32—C31 | −156.88 (14) |
Ni1—C3—C4—C5 | −63.20 (16) | C31—C32—C33—C34 | 0.3 (3) |
C2—C3—C4—Ni1 | 58.28 (15) | Ni2—C32—C33—C34 | −59.5 (2) |
C2—Ni1—C4—C3 | −38.01 (16) | C31—C32—C33—Ni2 | 59.74 (19) |
P1—Ni1—C4—C3 | 18.5 (3) | C31—Ni2—C33—C32 | −38.5 (2) |
C1—Ni1—C4—C3 | −81.85 (17) | C34—Ni2—C33—C32 | −119.2 (3) |
C5—Ni1—C4—C3 | −117.9 (2) | P2—Ni2—C33—C32 | 37.0 (3) |
S2—Ni1—C4—C3 | 131.93 (14) | C30—Ni2—C33—C32 | −82.2 (2) |
C2—Ni1—C4—C5 | 79.89 (17) | S1—Ni2—C33—C32 | 156.06 (19) |
C3—Ni1—C4—C5 | 117.9 (2) | C31—Ni2—C33—C34 | 80.7 (2) |
P1—Ni1—C4—C5 | 136.40 (18) | C32—Ni2—C33—C34 | 119.2 (3) |
C1—Ni1—C4—C5 | 36.04 (15) | P2—Ni2—C33—C34 | 156.22 (15) |
S2—Ni1—C4—C5 | −110.18 (15) | C30—Ni2—C33—C34 | 37.0 (2) |
C2—C1—C5—C4 | 1.0 (2) | S1—Ni2—C33—C34 | −84.73 (19) |
Ni1—C1—C5—C4 | 58.60 (15) | C32—C33—C34—C30 | −2.9 (3) |
C2—C1—C5—Ni1 | −57.57 (15) | Ni2—C33—C34—C30 | −62.09 (19) |
C3—C4—C5—C1 | 2.4 (3) | C32—C33—C34—Ni2 | 59.2 (2) |
Ni1—C4—C5—C1 | −59.92 (16) | C31—C30—C34—C33 | 4.3 (3) |
C3—C4—C5—Ni1 | 62.37 (16) | Ni2—C30—C34—C33 | 62.2 (2) |
C2—Ni1—C5—C1 | 38.24 (16) | C31—C30—C34—Ni2 | −57.88 (17) |
C4—Ni1—C5—C1 | 119.3 (2) | C31—Ni2—C34—C33 | −80.5 (2) |
C3—Ni1—C5—C1 | 82.02 (17) | C32—Ni2—C34—C33 | −36.1 (2) |
P1—Ni1—C5—C1 | −25.9 (3) | P2—Ni2—C34—C33 | −102.5 (4) |
S2—Ni1—C5—C1 | −162.30 (14) | C30—Ni2—C34—C33 | −118.9 (3) |
C2—Ni1—C5—C4 | −81.02 (18) | S1—Ni2—C34—C33 | 106.41 (19) |
C3—Ni1—C5—C4 | −37.24 (16) | C31—Ni2—C34—C30 | 38.46 (19) |
P1—Ni1—C5—C4 | −145.13 (16) | C32—Ni2—C34—C30 | 82.8 (2) |
C1—Ni1—C5—C4 | −119.3 (2) | P2—Ni2—C34—C30 | 16.5 (5) |
S2—Ni1—C5—C4 | 78.44 (16) | C33—Ni2—C34—C30 | 118.9 (3) |
C12—P1—C6—C11 | −125.69 (19) | S1—Ni2—C34—C30 | −134.65 (18) |
Experimental details
Crystal data | |
Chemical formula | [Ni2(C5H5)2(C12H10PS)2] |
Mr | 682.06 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.4231 (2), 14.5514 (2), 22.2014 (4) |
β (°) | 94.560 (1) |
V (Å3) | 3034.60 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.51 |
Crystal size (mm) | 0.48 × 0.42 × 0.38 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.532, 0.598 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21461, 7506, 6064 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.092, 0.98 |
No. of reflections | 7506 |
No. of parameters | 361 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.66 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL and PLATON (Spek, 1990).
Ni1—C2 | 2.060 (2) | Ni2—P2 | 2.1440 (6) |
Ni1—C4 | 2.119 (2) | Ni2—C30 | 2.153 (3) |
Ni1—C3 | 2.129 (2) | Ni2—C33 | 2.155 (3) |
Ni1—P1 | 2.1555 (6) | Ni2—S1 | 2.1986 (6) |
Ni1—C1 | 2.157 (2) | P1—C6 | 1.825 (2) |
Ni1—C5 | 2.173 (2) | P1—C12 | 1.832 (2) |
Ni1—S2 | 2.1979 (5) | P1—S1 | 2.0648 (7) |
Ni2—C31 | 2.064 (2) | P2—C18 | 1.830 (2) |
Ni2—C32 | 2.106 (3) | P2—C24 | 1.845 (2) |
Ni2—C34 | 2.128 (3) | P2—S2 | 2.0600 (7) |
P1—Ni1—S2 | 92.01 (2) | S1—P1—Ni1 | 117.85 (3) |
P2—Ni2—S1 | 90.62 (2) | S2—P2—Ni2 | 115.39 (3) |
Organometallic compounds play an increasingly important role as homogeneous catalysts and model systems for biologically active compounds. These very specific applications create a need for chemically robust systems, the properties of which can be varied by functionalization and derivatization (Cotton & Wilkinson, 1988). Recently, the coordination chemistry of tridentate oxygen ligands [CpCo{P(O)RR'}]- (Cp = C5H5, R, R' = alkyl, aryl, O-alkyl, O-aryl) has been extensively investigated (Klaui, 1990), the corresponding ligands with sulfur donor atoms are less common. Klaui and co-workers have reported an interesting example for organometallic S,S'-ligands with π-donor properties, [(η5-C5H5)Ni{P(S)(OCH3)2}2]-, which was obtained from the reaction of the intermediate dimer [(η5-C5H5)Ni(S)P(OCH3)2]2 with excess HP(S)(OCH3)2 in the presence of Zn(OOCH3)2 (Klaui et al., 1983). Compared with the air-sensitive methoxy compound, the medium soluble and air-stable phenyl compound is expected to be of more practical application. Thus, current research interest is directed towards to the synthesis of the analogous phenyl S,S'-ligand [(η5-C5H5)Ni{P(S)Ph2]-. Herein, we report the crystal structure of an intermediate dimer [(η5-C5H5)Ni(S)PPh2]2, (I), containing a six-membered twist-boat shape heterocycle.
The structure of (I) (Fig. 1) is very similar to that of [η5-C5H5)Ni(S)P(CH3)2]2 (Lindner et al., 1981). The two [PhP(S)]- ligands are coordinated to the Ni atoms of the two (η5-C5H5)Ni moieties, forming a six-membered heterocycle. This Ni—S—P—Ni—S—P heterocycle is obviously non-planar, the conformation is in a twist-boat form, indicated by the P—Ni—S [average 91.32 (2)°], Ni—P—S [average 116.62 (3)°] and Ni—S—P [average 102.92 (3)°] ring angles. The (η5-C5H5)Ni moiety in (I) resembles those reported for [(η5-C5H5)Ni(S)P(CH3)2]2 (Lindner et al., 1981) and [(η5-C5H5)NiPPh2]2 (Coleman & Dahl, 1967); that is, the C atoms C2 and C4, and C31 and C32, which are closest to the Ni—S—P plane, form shorter Ni—C bonds [average 2.087 (2) Å] than the other carbons [2.128 (2)–2.173 (2)°]. The trend in the ring bond distances is also compatible with the Ni—C interactions being relatively stronger at C2, C4, C31 and C32. The average Ni—P and Ni—S bond lengths are 2.1498 (6) and 2.1983 (5)°, respectively, in (I), which compare reasonably well with the corresponding distances in [{(η5-C5H5)Ni(S)P(OCH3)2}2Ni] (Klaui et al., 1986) and [(η5-C5H5)Ni(S)P(CH3)2]2 (Lindner et al., 1981). The mean P—S bond length of 2.0624 (7)° in (I) is normal, and also compares excellently with those in other related compounds (Churchill et al., 1971; Lindner et al., 1981; Klaui et al., 1986).