Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100004893/fg1594sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100004893/fg1594Isup2.hkl |
CCDC reference: 147617
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).
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.
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. |
[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) Å3 | 0.20 × 0.18 × 0.09 mm |
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 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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H-atom parameters not refined |
S = 1.03 | w = 1/[σ2(Fo2) + (0.05P)2 + 0.3131P] where P = (Fo2 + 2Fc2)/3 |
2969 reflections | (Δ/σ)max < 0.001 |
215 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
[Ni(C2H3OS)2(C18H15P)2] | γ = 107.593 (2)° |
Mr = 733.46 | V = 871.18 (13) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.7364 (5) Å | Mo Kα radiation |
b = 10.2509 (5) Å | µ = 0.80 mm−1 |
c = 10.9197 (6) Å | T = 293 K |
α = 106.1411 (13)° | 0.20 × 0.18 × 0.09 mm |
β = 111.2595 (14)° |
Siemens SMART CCD area detector diffractometer | 2969 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2347 reflections with I > 2σ(I) |
Tmin = 0.848, Tmax = 0.930 | Rint = 0.024 |
4485 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters not refined |
S = 1.03 | Δρmax = 0.38 e Å−3 |
2969 reflections | Δρmin = −0.31 e Å−3 |
215 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Ni1—S1i | 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—P1i | 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) | ||
S1i—Ni1—S1 | 180.0 | C6—C5—C4 | 120.1 (4) |
S1i—Ni1—P1 | 87.53 (3) | C7—C6—C5 | 120.1 (4) |
S1—Ni1—P1 | 92.47 (3) | C8—C7—C6 | 120.3 (4) |
S1i—Ni1—P1i | 92.47 (3) | C7—C8—C3 | 121.3 (3) |
S1—Ni1—P1i | 87.53 (3) | C10—C9—C14 | 118.6 (3) |
P1—Ni1—P1i | 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) |
S1i—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) |
P1i—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) |
S1i—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) |
P1i—Ni1—P1—C9 | −58 (100) | P1—C9—C10—C11 | −175.6 (3) |
S1i—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) |
P1i—Ni1—P1—C15 | 63 (100) | C11—C12—C13—C14 | 0.6 (6) |
S1i—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) |
P1i—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. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C2H3OS)2(C18H15P)2] |
Mr | 733.46 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.7364 (5), 10.2509 (5), 10.9197 (6) |
α, β, γ (°) | 106.1411 (13), 111.2595 (14), 107.593 (2) |
V (Å3) | 871.18 (13) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.80 |
Crystal size (mm) | 0.20 × 0.18 × 0.09 |
Data collection | |
Diffractometer | Siemens SMART CCD area detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.848, 0.930 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4485, 2969, 2347 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.106, 1.03 |
No. of reflections | 2969 |
No. of parameters | 215 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.38, −0.31 |
Computer programs: SMART (Siemens, 1996), SMART, SHELXTL (Siemens, 1994), SHELXTL.
Ni1—S1 | 2.2020 (8) | P1—C3 | 1.837 (3) |
Ni1—P1 | 2.2528 (8) | P1—C9 | 1.828 (3) |
S1—C1 | 1.756 (4) | P1—C15 | 1.835 (3) |
O1—C1 | 1.215 (4) | Ni1—O1 | 3.312 (3) |
C1—C2 | 1.512 (5) | ||
S1—Ni1—P1 | 92.47 (3) | C9—P1—C3 | 100.30 (15) |
C1—S1—Ni1 | 107.37 (12) | C15—P1—C3 | 101.98 (14) |
O1—C1—C2 | 121.8 (3) | C3—P1—Ni1 | 123.81 (10) |
O1—C1—S1 | 124.5 (3) | C9—P1—Ni1 | 108.91 (11) |
C2—C1—S1 | 113.7 (3) | C15—P1—Ni1 | 111.73 (11) |
C9—P1—C15 | 108.98 (15) |
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 NiII 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 NiII 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.