trans-Bis(thioacetato-S)bis(triphenylphosphine-P)nickel(II)

In the title compound, [Ni(C₂H₃OS)₂(C₁₈H₁₅P)₂], the Ni atom lies on an inversion centre and the tri­phenyl phosphine and thio­acetate ligands are bonded to the central Ni^II atom in a trans fashion, with Ni-S = 2.2020 (8) and Ni-P = 2.2528 (8) Å, and angle S-Ni-P = 92.47 (3)°.

S1. Comment

We have been pursuing a systematic research into the chemistry of the thiocarboxylates (Deivaraj & Vittal, 2000; Sampanthar et al., 1999, and references therein). This ligand belongs to an interesting class of ligands that contain both soft and hard donor sites. Further, the chemistry of the thiocarboxylates has been relatively unexplored when compared with thiolates or the analogous monochalcogenato ligands, such as monothiocarbamates. We have synthesized and determined the crystal structures of the anionic metal complexes of Mn, Co and Ni (Devy et al., 1998). The synthesis of the neutral nickel thiobenzoate compound, Ni(S{O}CPh)₂, was reported three decades ago (Savant & Gopalakrishnan, 1970; Melson, Crawford & Geddes, 1970) and the structure of [Ni(SC{O}Ph)₂]₂·2EtOH determined (Melson, Greene & Bryan, 1970). The neutral phosphine adducts of the corresponding nickel thiocarboxylates were synthesized by Goodfellow & Stephenson (1980) but no crystal structures have been reported. In this communication, we report the crystal structure of the title compound, (I). \sch

In the structure of the neutral compound, the central Ni^II atom lies on an inversion centre and is bonded to two PPh₃ and two CH₃C{O}S⁻ anions in a trans fashion; the NiP₂S₂ moiety is necessarily planar, but is not exactly square [P—Ni—S 92.47 (3)°]. A view of the molecule is shown in Fig. 1 and selected bond distances and angles are given in Table 1. The Ni—P bond distance is normal. However, the Ni—S bond distance of 2.2020 (8) Å is shorter than the values of 2.419 (1) Å observed in (Ph₄P)[Ni(SC{O}Ph)₃], (II) (Devy et al., 1998), and 2.221 (5) to 2.230 (5) Å found in [Ni(SC{O}Ph)₂]₂·2EtOH, (III) (Melson, Greene & Bryan, 1970). In the latter compounds, the Ph{O}CS⁻ anions act as a chelating ligand and in addition the C—S and C—O bonds acquire partial double-bond character. On the other hand, no such delocalization occurs in (I). This is reflected in the Ni—S, C—S and C—O bond distances. The S—C distance of 1.756 (4) Å is longer than those found in (II) [1.705 (4) Å] and (III) [1.70 (1)–1.72 (1) Å], and the C—O distance of 1.215 (4) Å is shorter than those found in (II) and (III). There appear to be no interactions between Ni^II and the O atoms of the thioacetato ligands [Ni1···O1 3.312 (3) Å].

The non-H atoms in the thioacetato ligand are planar [r.m.s. deviation 0.0006 (8) Å] and the thioacetato plane makes an angle of 67.42 (8)° with the NiP₂S₂ plane. It is interesting to note that the C3—P1—C9 and C3—P1—C15 angles are shorter than C9—P1—C15 angle. Further, the Ni1—P1—C3 angle is larger than the other two Ni—P—C angles. It is evident that the phenyl ring with the ipso carbon C3 in PPh₃ is pushed away in order to minimize contacts with the thioacetato ligand.

S2. Experimental

Compound (I) was obtained by reacting Ni(SC{O}Me)₂ with 2 molar equivalents of PPh₃ in CH₂Cl₂ solution. Single crystals of (I) were obtained by slow diffusion of diethyl ether into a dichloromethane solution of (I).

S3. Refinement

Please provide details of H-atom refinement.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A view of the structure of (I) showing the labelling of the non-H atoms. Displacement ellipsoids are shown at the 50% probability level and H atoms are drawn as spheres of arbitrary radii.

trans-Bis(thioacetato-S)bis(triphenylphosphine-P)nickel(II)

Crystal data

[Ni(C2H3OS)2(C18H15P)2]	Z = 1
Mr = 733.46	F(000) = 382
Triclinic, P1	Dx = 1.398 Mg m^−3
a = 9.7364 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.2509 (5) Å	Cell parameters from 2519 reflections
c = 10.9197 (6) Å	θ = 2.2–29.3°
α = 106.1411 (13)°	µ = 0.80 mm^−1
β = 111.2595 (14)°	T = 293 K
γ = 107.593 (2)°	Block, red
V = 871.18 (13) Å^3	0.20 × 0.18 × 0.09 mm

Data collection

Siemens SMART CCD area detector diffractometer	2969 independent reflections
Radiation source: fine-focus sealed tube	2347 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ϕ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −9→11
Tmin = 0.848, Tmax = 0.930	k = −10→12
4485 measured reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H-atom parameters not refined
S = 1.03	w = 1/[σ^2(Fo^2) + (0.05P)^2 + 0.3131P] where P = (Fo^2 + 2Fc^2)/3
2969 reflections	(Δ/σ)max < 0.001
215 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

Experimental. The diffraction experiments were carried out on a Siemens SMART CCD diffractometer with a Mo K alpha sealed tube at 20°C. Preliminary cell constants were obtained from 45 frames (width of 0.3deg in omega). Final cell parameters were obtained by global refinements of reflections obtained from integration of all the frame data. A frame width of 0.3° in omega and a counting time of 20 s per frame at a crystal-to-detector distance of 5.0 cm. The collected frames were integrated using the preliminary cell-orientation matrix. The hydrogen atoms were placed in the calculated positions for the purpose of structure factor calculations only.

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 (Ų)

	x	y	z	Uiso*/Ueq
Ni1	1/2	0	1/2	0.02548 (18)
S1	0.56373 (11)	−0.10213 (10)	0.33588 (9)	0.0335 (2)
O1	0.4430 (3)	−0.3553 (3)	0.3610 (3)	0.0504 (7)
C1	0.5240 (4)	−0.2876 (4)	0.3164 (4)	0.0383 (8)
C2	0.5999 (5)	−0.3593 (5)	0.2365 (4)	0.0561 (11)
H2A	0.6158	−0.3124	0.1748	0.084*
H2B	0.5277	−0.4662	0.1780	0.084*
H2C	0.7045	−0.3449	0.3061	0.084*
P1	0.69276 (10)	−0.01848 (9)	0.67677 (9)	0.0279 (2)
C3	0.7946 (4)	−0.1377 (4)	0.6415 (3)	0.0309 (7)
C4	0.9254 (4)	−0.0849 (4)	0.6133 (4)	0.0416 (9)
H4	0.9589	0.0095	0.6118	0.050*
C5	1.0049 (5)	−0.1724 (5)	0.5878 (4)	0.0512 (10)
H5	1.0915	−0.1366	0.5693	0.061*
C6	0.9561 (5)	−0.3120 (5)	0.5899 (5)	0.0542 (11)
H6	1.0106	−0.3699	0.5738	0.065*
C7	0.8272 (5)	−0.3661 (5)	0.6156 (4)	0.0516 (10)
H7	0.7936	−0.4612	0.6156	0.062*
C8	0.7477 (4)	−0.2805 (4)	0.6412 (4)	0.0400 (8)
H8	0.6607	−0.3184	0.6588	0.048*
C9	0.8721 (4)	0.1681 (4)	0.7930 (3)	0.0325 (7)
C10	0.8746 (4)	0.2874 (4)	0.7555 (4)	0.0407 (8)
H10	0.7827	0.2734	0.6759	0.049*
C11	1.0135 (5)	0.4271 (4)	0.8361 (4)	0.0518 (10)
H11	1.0147	0.5065	0.8105	0.062*
C12	1.1497 (5)	0.4486 (5)	0.9540 (5)	0.0545 (11)
H12	1.2423	0.5428	1.0084	0.065*
C13	1.1493 (5)	0.3311 (5)	0.9915 (4)	0.0532 (10)
H13	1.2413	0.3464	1.0718	0.064*
C14	1.0138 (4)	0.1913 (4)	0.9108 (4)	0.0437 (9)
H14	1.0161	0.1114	0.9345	0.052*
C15	0.6149 (4)	−0.0832 (4)	0.7898 (3)	0.0313 (7)
C16	0.4612 (4)	−0.2104 (4)	0.7130 (4)	0.0418 (9)
H16	0.4032	−0.2533	0.6115	0.050*
C17	0.3945 (5)	−0.2733 (5)	0.7885 (5)	0.0502 (10)
H17	0.2930	−0.3592	0.7376	0.060*
C18	0.4803 (5)	−0.2069 (5)	0.9392 (5)	0.0538 (11)
H18	0.4358	−0.2476	0.9901	0.065*
C19	0.6312 (5)	−0.0809 (5)	1.0143 (4)	0.0516 (10)
H19	0.6886	−0.0371	1.1158	0.062*
C20	0.6981 (5)	−0.0190 (4)	0.9398 (4)	0.0416 (9)
H20	0.8000	0.0666	0.9915	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0253 (3)	0.0299 (3)	0.0240 (3)	0.0130 (3)	0.0120 (3)	0.0145 (3)
S1	0.0407 (5)	0.0401 (5)	0.0330 (5)	0.0229 (4)	0.0232 (4)	0.0212 (4)
O1	0.0437 (15)	0.0455 (15)	0.0583 (17)	0.0148 (13)	0.0198 (14)	0.0307 (14)
C1	0.0323 (19)	0.040 (2)	0.0316 (19)	0.0173 (17)	0.0072 (16)	0.0118 (16)
C2	0.058 (3)	0.054 (3)	0.054 (3)	0.037 (2)	0.021 (2)	0.016 (2)
P1	0.0268 (5)	0.0322 (5)	0.0267 (5)	0.0136 (4)	0.0119 (4)	0.0167 (4)
C3	0.0292 (17)	0.0391 (19)	0.0287 (18)	0.0193 (15)	0.0116 (15)	0.0194 (15)
C4	0.039 (2)	0.041 (2)	0.050 (2)	0.0175 (17)	0.0251 (18)	0.0236 (18)
C5	0.040 (2)	0.059 (3)	0.058 (3)	0.026 (2)	0.027 (2)	0.021 (2)
C6	0.048 (2)	0.055 (3)	0.067 (3)	0.036 (2)	0.024 (2)	0.026 (2)
C7	0.051 (2)	0.049 (2)	0.065 (3)	0.029 (2)	0.027 (2)	0.032 (2)
C8	0.037 (2)	0.044 (2)	0.045 (2)	0.0208 (17)	0.0186 (17)	0.0253 (18)
C9	0.0278 (17)	0.0377 (19)	0.0304 (18)	0.0142 (15)	0.0126 (15)	0.0156 (15)
C10	0.036 (2)	0.043 (2)	0.045 (2)	0.0184 (17)	0.0166 (17)	0.0238 (18)
C11	0.046 (2)	0.039 (2)	0.057 (3)	0.0127 (19)	0.016 (2)	0.023 (2)
C12	0.038 (2)	0.042 (2)	0.061 (3)	0.0051 (18)	0.018 (2)	0.014 (2)
C13	0.030 (2)	0.060 (3)	0.045 (2)	0.011 (2)	0.0040 (18)	0.022 (2)
C14	0.034 (2)	0.050 (2)	0.041 (2)	0.0180 (18)	0.0101 (17)	0.0244 (19)
C15	0.0344 (19)	0.0368 (19)	0.0322 (18)	0.0198 (16)	0.0181 (16)	0.0208 (15)
C16	0.040 (2)	0.050 (2)	0.037 (2)	0.0186 (18)	0.0178 (17)	0.0242 (18)
C17	0.047 (2)	0.055 (2)	0.071 (3)	0.026 (2)	0.037 (2)	0.043 (2)
C18	0.070 (3)	0.071 (3)	0.064 (3)	0.044 (3)	0.049 (3)	0.053 (3)
C19	0.063 (3)	0.073 (3)	0.040 (2)	0.037 (2)	0.032 (2)	0.035 (2)
C20	0.044 (2)	0.051 (2)	0.035 (2)	0.0217 (19)	0.0217 (18)	0.0240 (18)

Geometric parameters (Å, º)

Ni1—S1^i	2.2020 (8)	C7—C8	1.370 (5)
Ni1—S1	2.2020 (8)	C9—C10	1.390 (5)
Ni1—P1	2.2528 (8)	C9—C14	1.399 (5)
Ni1—P1^i	2.2528 (8)	C10—C11	1.385 (5)
S1—C1	1.756 (4)	C11—C12	1.375 (5)
O1—C1	1.215 (4)	C12—C13	1.376 (5)
C1—C2	1.512 (5)	C13—C14	1.372 (5)
P1—C3	1.837 (3)	C15—C20	1.374 (5)
P1—C9	1.828 (3)	C15—C16	1.395 (5)
P1—C15	1.835 (3)	C16—C17	1.396 (5)
C3—C8	1.394 (5)	C17—C18	1.381 (6)
C3—C4	1.402 (4)	C18—C19	1.375 (6)
C4—C5	1.386 (5)	C19—C20	1.382 (5)
C5—C6	1.374 (5)	Ni1—O1	3.312 (3)
C6—C7	1.373 (5)
S1^i—Ni1—S1	180.0	C6—C5—C4	120.1 (4)
S1^i—Ni1—P1	87.53 (3)	C7—C6—C5	120.1 (4)
S1—Ni1—P1	92.47 (3)	C8—C7—C6	120.3 (4)
S1^i—Ni1—P1^i	92.47 (3)	C7—C8—C3	121.3 (3)
S1—Ni1—P1^i	87.53 (3)	C10—C9—C14	118.6 (3)
P1—Ni1—P1^i	180.0	C10—C9—P1	119.1 (3)
C1—S1—Ni1	107.37 (12)	C14—C9—P1	122.0 (3)
O1—C1—C2	121.8 (3)	C11—C10—C9	120.2 (3)
O1—C1—S1	124.5 (3)	C12—C11—C10	120.2 (4)
C2—C1—S1	113.7 (3)	C11—C12—C13	120.1 (4)
C9—P1—C15	108.98 (15)	C14—C13—C12	120.2 (4)
C9—P1—C3	100.30 (15)	C13—C14—C9	120.6 (3)
C15—P1—C3	101.98 (14)	C20—C15—C16	119.6 (3)
C3—P1—Ni1	123.81 (10)	C20—C15—P1	125.1 (3)
C9—P1—Ni1	108.91 (11)	C16—C15—P1	115.4 (3)
C15—P1—Ni1	111.73 (11)	C15—C16—C17	119.9 (4)
C8—C3—C4	117.7 (3)	C18—C17—C16	119.5 (4)
C8—C3—P1	122.8 (3)	C19—C18—C17	120.3 (3)
C4—C3—P1	119.5 (2)	C18—C19—C20	120.4 (4)
C5—C4—C3	120.4 (3)	C15—C20—C19	120.3 (4)
S1^i—Ni1—S1—C1	−98 (100)	C15—P1—C9—C10	−127.0 (3)
P1—Ni1—S1—C1	62.24 (12)	C3—P1—C9—C10	126.5 (3)
P1^i—Ni1—S1—C1	−117.76 (12)	Ni1—P1—C9—C10	−4.8 (3)
Ni1—S1—C1—O1	14.7 (3)	C15—P1—C9—C14	59.4 (3)
Ni1—S1—C1—C2	−165.7 (2)	C3—P1—C9—C14	−47.2 (3)
S1^i—Ni1—P1—C9	−78.27 (11)	Ni1—P1—C9—C14	−178.5 (3)
S1—Ni1—P1—C9	101.73 (11)	C14—C9—C10—C11	−1.7 (5)
P1^i—Ni1—P1—C9	−58 (100)	P1—C9—C10—C11	−175.6 (3)
S1^i—Ni1—P1—C15	42.16 (12)	C9—C10—C11—C12	−0.1 (6)
S1—Ni1—P1—C15	−137.84 (12)	C10—C11—C12—C13	0.7 (6)
P1^i—Ni1—P1—C15	63 (100)	C11—C12—C13—C14	0.6 (6)
S1^i—Ni1—P1—C3	164.55 (13)	C12—C13—C14—C9	−2.5 (6)
S1—Ni1—P1—C3	−15.45 (13)	C10—C9—C14—C13	3.0 (5)
P1^i—Ni1—P1—C3	−175 (100)	P1—C9—C14—C13	176.7 (3)
C9—P1—C3—C8	138.8 (3)	C9—P1—C15—C20	−13.2 (3)
C15—P1—C3—C8	26.7 (3)	C3—P1—C15—C20	92.2 (3)
Ni1—P1—C3—C8	−100.0 (3)	Ni1—P1—C15—C20	−133.6 (3)
C9—P1—C3—C4	−41.2 (3)	C9—P1—C15—C16	168.8 (2)
C15—P1—C3—C4	−153.3 (3)	C3—P1—C15—C16	−85.8 (3)
Ni1—P1—C3—C4	80.0 (3)	Ni1—P1—C15—C16	48.4 (3)
C8—C3—C4—C5	−0.6 (5)	C20—C15—C16—C17	−1.2 (5)
P1—C3—C4—C5	179.4 (3)	P1—C15—C16—C17	176.9 (3)
C3—C4—C5—C6	0.0 (6)	C15—C16—C17—C18	1.2 (5)
C4—C5—C6—C7	0.7 (6)	C16—C17—C18—C19	−0.8 (6)
C5—C6—C7—C8	−0.9 (6)	C17—C18—C19—C20	0.3 (6)
C6—C7—C8—C3	0.2 (6)	C16—C15—C20—C19	0.8 (5)
C4—C3—C8—C7	0.5 (5)	P1—C15—C20—C19	−177.1 (3)
P1—C3—C8—C7	−179.5 (3)	C18—C19—C20—C15	−0.4 (6)

Symmetry code: (i) −x+1, −y, −z+1.