Bis(μ-di­phenyl­thio­phosphinito-S:P)­bis­[(η5-cyclo­penta­dienyl)­nickel(II)]

Fun, H.-K.; Chantrapromma, S.; Razak, I.A.; Zhang, Q.-F.; Xin, X.-Q.

doi:10.1107/S1600536801005475

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Bis(μ-diphenylthiophosphinito-S:P)bis[(η⁵-cyclopentadienyl)nickel(II)]

H.-K. Fun, S. Chantrapromma, I. A. Razak, Q.-F. Zhang and X.-Q. Xin

The title compound, [(η⁵-C₅H₅)Ni(S)PPh₂]₂ or [Ni₂(C₅H₅)₂(C₁₂H₁₀PS)₂], consists of two (η⁵-C₅H₅)Ni moieties bridged by the P and S atoms of two [Ph₂P(S)]⁻ ligands, forming a non-planar Ni—S—P—Ni—S—P twist-boat heterocycle. The average Ni—P and Ni—S bond lengths are 2.1498 (6) and 2.1983 (5) Å, respectively.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005475/cv6016sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005475/cv6016Isup2.hkl Contains datablock I

CCDC reference: 165629

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.004 Å
R factor = 0.036
wR factor = 0.092
Data-to-parameter ratio = 20.8

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No syntax errors found

ADDSYM reports no extra symmetry

General Notes



ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      0.943
          Tmax scaled      0.564 Tmin scaled      0.501

Comment top

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).

Experimental top

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.

Computing details top

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).

Figures top

Fig. 1. The structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme.

Bis(µ-diphenylthiophosphinito-S:P)bis[(η⁵-cyclopentadienyl)nickel(II)] top

Crystal data top

[Ni₂(C₅H₅)₂(C₁₂H₁₀PS)₂]	F(000) = 1408
M_r = 682.06	D_x = 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

Data collection top

Siemens SMART CCD area-detector diffractometer	7506 independent reflections
Radiation source: fine-focus sealed tube	6064 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
Detector resolution: 8.33 pixels mm^-1	θ_max = 28.3°, θ_min = 2.7°
ω scans	h = −11→12
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −19→18
T_min = 0.532, T_max = 0.598	l = −25→29
21461 measured reflections

Refinement top

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(F_o²) + (0.0384P)²] where P = (F_o² + 2F_c²)/3
7506 reflections	(Δ/σ)_max = 0.001
361 parameters	Δρ_max = 0.67 e Å⁻³
0 restraints	Δρ_min = −0.66 e Å⁻³

Crystal data top

[Ni₂(C₅H₅)₂(C₁₂H₁₀PS)₂]	V = 3034.60 (9) Å³
M_r = 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)°

Data collection top

Siemens SMART CCD area-detector diffractometer	7506 independent reflections
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	6064 reflections with I > 2σ(I)
T_min = 0.532, T_max = 0.598	R_int = 0.059
21461 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 0.98	Δρ_max = 0.67 e Å⁻³
7506 reflections	Δρ_min = −0.66 e Å⁻³
361 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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]
M_r	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)
T_min, T_max	0.532, 0.598
No. of measured, independent and observed [I > 2σ(I)] reflections	21461, 7506, 6064
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.66

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL and PLATON (Spek, 1990).

Selected geometric parameters (Å, º) top

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)

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