Transition-metal complexes bearing fluorinated phosphane and thiolate ligands has been an area of study in recent years and the chemical context of the current work is related to the metal-assisted functionalization of fluorinated derivatives. The
cis and
trans isomers of the square-planar complex bis[(pentafluorophenyl)diphenylphosphane-κ
P]bis(2,3,5,6-tetrafluorobenzenethiolato-κ
S)platinum(II), [Pt(C
6HF
4S)
2{P(C
6H
5)
2(C
6F
5)}
2], have been crystallized from a single chromatographic fraction and characterized by X-ray diffraction analysis. The stabilization of the
cis isomer results from weak intramolecular π-stacking interactions and possibly from the formation of a C—F
Pt contact, characterized by an F
Pt separation of 2.957 (6) Å. The natural bond orbital analysis (NBO) for this isomer confirms that the corresponding F → Pt charge transfer accounts for 6.92 kcal mol
−1 in the isomer stabilization. Such interactions are not present in the centrosymmetric
trans isomer.
Supporting information
CCDC references: 1455146; 1455145
For both compounds, data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS (Bruker, 1997); data reduction: XSCANS (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).
(trans) Bis[(pentafluorophenyl)diphenylphosphane-
κP]bis(2,3,5,6-tetrafluorophenylthiolato-
κS)platinum(II)
top
Crystal data top
[Pt(C6HF4S)2(C18H10F5P)2] | Z = 1 |
Mr = 1261.80 | F(000) = 612 |
Triclinic, P1 | Dx = 1.826 Mg m−3 |
a = 10.3553 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.5983 (10) Å | Cell parameters from 81 reflections |
c = 12.4594 (8) Å | θ = 4.0–13.8° |
α = 114.574 (6)° | µ = 3.33 mm−1 |
β = 104.400 (6)° | T = 298 K |
γ = 99.442 (5)° | Irregular_block, yellow |
V = 1147.61 (17) Å3 | 0.6 × 0.5 × 0.4 mm |
Data collection top
Bruker P4 diffractometer | 6346 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube, FN4 | Rint = 0.019 |
Graphite monochromator | θmax = 30.0°, θmin = 1.9° |
2θ/ω scans | h = −14→9 |
Absorption correction: ψ scan (XSCANS; Bruker, 1997) | k = −13→13 |
Tmin = 0.468, Tmax = 0.730 | l = −17→17 |
11452 measured reflections | 3 standard reflections every 97 reflections |
6346 independent reflections | intensity decay: 1% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.022 | H-atom parameters constrained |
wR(F2) = 0.057 | w = 1/[σ2(Fo2) + (0.0356P)2 + 0.248P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
6346 reflections | Δρmax = 0.88 e Å−3 |
323 parameters | Δρmin = −0.91 e Å−3 |
0 restraints | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 constraints | Extinction coefficient: 0.0105 (6) |
Primary atom site location: structure-invariant direct methods | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pt1 | 0.0000 | 0.0000 | 0.0000 | 0.02829 (4) | |
S1 | 0.03421 (6) | −0.05262 (6) | 0.16714 (5) | 0.04019 (11) | |
P1 | 0.19274 (5) | 0.20958 (6) | 0.10904 (5) | 0.03178 (9) | |
C1 | −0.0125 (3) | 0.0703 (3) | 0.2857 (2) | 0.0461 (5) | |
C2 | 0.0583 (4) | 0.1060 (5) | 0.4105 (3) | 0.0650 (8) | |
F2 | 0.1579 (2) | 0.0446 (3) | 0.4353 (2) | 0.0817 (7) | |
C3 | 0.0297 (5) | 0.2023 (7) | 0.5090 (3) | 0.0982 (17) | |
F3 | 0.1059 (4) | 0.2318 (6) | 0.6266 (2) | 0.1498 (18) | |
C4 | −0.0725 (7) | 0.2667 (8) | 0.4909 (4) | 0.115 (2) | |
H4A | −0.0905 | 0.3329 | 0.5584 | 0.137* | |
C5 | −0.1465 (5) | 0.2292 (6) | 0.3690 (4) | 0.0885 (14) | |
F5 | −0.2516 (4) | 0.2847 (5) | 0.3432 (3) | 0.1268 (14) | |
C6 | −0.1182 (3) | 0.1334 (4) | 0.2680 (3) | 0.0544 (6) | |
F6 | −0.1969 (2) | 0.1017 (2) | 0.15250 (17) | 0.0601 (4) | |
C7 | 0.2938 (2) | 0.2328 (3) | 0.2635 (2) | 0.0418 (5) | |
C8 | 0.3523 (3) | 0.1231 (3) | 0.2635 (3) | 0.0508 (6) | |
F8 | 0.3361 (2) | 0.0103 (2) | 0.1539 (2) | 0.0627 (4) | |
C9 | 0.4262 (4) | 0.1256 (4) | 0.3736 (4) | 0.0707 (10) | |
F9 | 0.4791 (3) | 0.0165 (4) | 0.3672 (3) | 0.1100 (10) | |
C10 | 0.4413 (5) | 0.2366 (5) | 0.4876 (4) | 0.0830 (13) | |
F10 | 0.5074 (4) | 0.2374 (4) | 0.5942 (3) | 0.1328 (15) | |
C11 | 0.3849 (5) | 0.3451 (4) | 0.4919 (3) | 0.0738 (11) | |
F11 | 0.3970 (4) | 0.4534 (3) | 0.6030 (2) | 0.1135 (12) | |
C12 | 0.3114 (3) | 0.3428 (3) | 0.3809 (2) | 0.0544 (6) | |
F12 | 0.2578 (3) | 0.4521 (2) | 0.39420 (18) | 0.0784 (6) | |
C13 | 0.3279 (2) | 0.2361 (3) | 0.0427 (2) | 0.0400 (4) | |
C14 | 0.4620 (3) | 0.2315 (4) | 0.0897 (4) | 0.0657 (9) | |
H14A | 0.4880 | 0.2162 | 0.1592 | 0.079* | |
C15 | 0.5581 (4) | 0.2500 (6) | 0.0323 (6) | 0.0942 (16) | |
H15A | 0.6476 | 0.2454 | 0.0636 | 0.113* | |
C16 | 0.5244 (5) | 0.2743 (6) | −0.0670 (5) | 0.0870 (13) | |
H16A | 0.5899 | 0.2859 | −0.1041 | 0.104* | |
C17 | 0.3932 (4) | 0.2819 (5) | −0.1133 (4) | 0.0788 (11) | |
H17A | 0.3694 | 0.2990 | −0.1820 | 0.095* | |
C18 | 0.2956 (3) | 0.2642 (4) | −0.0579 (3) | 0.0613 (8) | |
H18A | 0.2072 | 0.2714 | −0.0890 | 0.074* | |
C19 | 0.1348 (2) | 0.3693 (2) | 0.1374 (2) | 0.0351 (4) | |
C20 | 0.2282 (3) | 0.5031 (3) | 0.1751 (3) | 0.0493 (5) | |
H20A | 0.3219 | 0.5118 | 0.1856 | 0.059* | |
C21 | 0.1806 (3) | 0.6235 (3) | 0.1970 (3) | 0.0538 (6) | |
H21A | 0.2431 | 0.7133 | 0.2231 | 0.065* | |
C22 | 0.0423 (3) | 0.6110 (3) | 0.1804 (3) | 0.0519 (6) | |
H22A | 0.0115 | 0.6922 | 0.1952 | 0.062* | |
C23 | −0.0513 (3) | 0.4787 (3) | 0.1419 (3) | 0.0527 (6) | |
H23A | −0.1450 | 0.4707 | 0.1308 | 0.063* | |
C24 | −0.0055 (3) | 0.3573 (3) | 0.1196 (2) | 0.0428 (5) | |
H24A | −0.0688 | 0.2678 | 0.0928 | 0.051* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pt1 | 0.03238 (6) | 0.02482 (6) | 0.02739 (5) | 0.01034 (3) | 0.00919 (3) | 0.01241 (4) |
S1 | 0.0497 (3) | 0.0372 (3) | 0.0370 (2) | 0.0137 (2) | 0.0120 (2) | 0.0224 (2) |
P1 | 0.0324 (2) | 0.0285 (2) | 0.0324 (2) | 0.01009 (17) | 0.00848 (17) | 0.01415 (17) |
C1 | 0.0512 (12) | 0.0526 (13) | 0.0355 (10) | 0.0127 (10) | 0.0166 (9) | 0.0223 (9) |
C2 | 0.0610 (17) | 0.095 (3) | 0.0398 (12) | 0.0242 (16) | 0.0171 (12) | 0.0338 (15) |
F2 | 0.0718 (13) | 0.134 (2) | 0.0564 (11) | 0.0433 (14) | 0.0199 (9) | 0.0576 (13) |
C3 | 0.098 (3) | 0.154 (5) | 0.0358 (14) | 0.054 (3) | 0.0247 (17) | 0.033 (2) |
F3 | 0.147 (3) | 0.255 (5) | 0.0391 (11) | 0.101 (3) | 0.0306 (15) | 0.0491 (19) |
C4 | 0.133 (4) | 0.164 (6) | 0.0507 (19) | 0.088 (4) | 0.046 (3) | 0.032 (3) |
C5 | 0.099 (3) | 0.118 (4) | 0.0577 (19) | 0.066 (3) | 0.039 (2) | 0.032 (2) |
F5 | 0.146 (3) | 0.172 (3) | 0.0840 (18) | 0.119 (3) | 0.0565 (19) | 0.046 (2) |
C6 | 0.0622 (16) | 0.0645 (17) | 0.0420 (12) | 0.0261 (13) | 0.0223 (11) | 0.0255 (12) |
F6 | 0.0706 (11) | 0.0722 (11) | 0.0492 (8) | 0.0377 (9) | 0.0231 (8) | 0.0325 (8) |
C7 | 0.0400 (10) | 0.0398 (11) | 0.0370 (10) | 0.0059 (8) | 0.0035 (8) | 0.0186 (8) |
C8 | 0.0435 (12) | 0.0508 (14) | 0.0547 (14) | 0.0114 (10) | 0.0045 (10) | 0.0305 (11) |
F8 | 0.0654 (11) | 0.0580 (10) | 0.0738 (12) | 0.0347 (9) | 0.0230 (9) | 0.0346 (9) |
C9 | 0.0613 (17) | 0.069 (2) | 0.075 (2) | 0.0117 (15) | −0.0053 (15) | 0.0482 (18) |
F9 | 0.113 (2) | 0.107 (2) | 0.119 (2) | 0.0505 (18) | 0.0016 (17) | 0.0782 (19) |
C10 | 0.086 (2) | 0.074 (2) | 0.0580 (18) | −0.0091 (19) | −0.0195 (17) | 0.0417 (17) |
F10 | 0.160 (3) | 0.108 (2) | 0.0763 (16) | −0.003 (2) | −0.0426 (18) | 0.0597 (17) |
C11 | 0.094 (3) | 0.0574 (17) | 0.0368 (12) | −0.0106 (17) | −0.0045 (14) | 0.0207 (12) |
F11 | 0.179 (3) | 0.0762 (15) | 0.0353 (9) | 0.0007 (17) | 0.0061 (13) | 0.0145 (9) |
C12 | 0.0680 (17) | 0.0428 (12) | 0.0376 (11) | 0.0034 (11) | 0.0078 (11) | 0.0171 (10) |
F12 | 0.127 (2) | 0.0553 (11) | 0.0442 (9) | 0.0364 (12) | 0.0261 (11) | 0.0147 (8) |
C13 | 0.0351 (9) | 0.0382 (10) | 0.0454 (11) | 0.0107 (8) | 0.0148 (8) | 0.0185 (8) |
C14 | 0.0433 (13) | 0.086 (2) | 0.095 (2) | 0.0274 (14) | 0.0295 (15) | 0.063 (2) |
C15 | 0.058 (2) | 0.130 (4) | 0.159 (5) | 0.051 (2) | 0.064 (3) | 0.103 (4) |
C16 | 0.074 (2) | 0.109 (3) | 0.120 (4) | 0.038 (2) | 0.067 (3) | 0.070 (3) |
C17 | 0.070 (2) | 0.105 (3) | 0.078 (2) | 0.016 (2) | 0.0378 (19) | 0.056 (2) |
C18 | 0.0445 (13) | 0.086 (2) | 0.0656 (17) | 0.0137 (13) | 0.0196 (12) | 0.0488 (17) |
C19 | 0.0385 (9) | 0.0281 (9) | 0.0375 (9) | 0.0120 (7) | 0.0115 (7) | 0.0151 (7) |
C20 | 0.0493 (13) | 0.0339 (11) | 0.0621 (15) | 0.0101 (9) | 0.0204 (11) | 0.0211 (10) |
C21 | 0.0694 (17) | 0.0317 (11) | 0.0635 (16) | 0.0150 (11) | 0.0276 (13) | 0.0233 (11) |
C22 | 0.0755 (18) | 0.0395 (12) | 0.0534 (13) | 0.0307 (12) | 0.0282 (13) | 0.0255 (10) |
C23 | 0.0528 (14) | 0.0510 (14) | 0.0602 (15) | 0.0280 (12) | 0.0223 (12) | 0.0261 (12) |
C24 | 0.0412 (10) | 0.0348 (10) | 0.0508 (12) | 0.0131 (8) | 0.0160 (9) | 0.0184 (9) |
Geometric parameters (Å, º) top
Pt1—S1i | 2.3318 (5) | C10—C11 | 1.360 (7) |
Pt1—S1 | 2.3318 (5) | C11—F11 | 1.339 (5) |
Pt1—P1 | 2.3345 (6) | C11—C12 | 1.391 (4) |
Pt1—P1i | 2.3345 (6) | C12—F12 | 1.332 (4) |
S1—C1 | 1.753 (3) | C13—C18 | 1.381 (4) |
P1—C19 | 1.814 (2) | C13—C14 | 1.384 (4) |
P1—C13 | 1.833 (2) | C14—C15 | 1.395 (5) |
P1—C7 | 1.838 (2) | C14—H14A | 0.9300 |
C1—C6 | 1.392 (4) | C15—C16 | 1.341 (7) |
C1—C2 | 1.397 (4) | C15—H15A | 0.9300 |
C2—F2 | 1.346 (4) | C16—C17 | 1.368 (6) |
C2—C3 | 1.369 (5) | C16—H16A | 0.9300 |
C3—F3 | 1.354 (4) | C17—C18 | 1.388 (4) |
C3—C4 | 1.372 (7) | C17—H17A | 0.9300 |
C4—C5 | 1.368 (6) | C18—H18A | 0.9300 |
C4—H4A | 0.9300 | C19—C24 | 1.390 (3) |
C5—F5 | 1.352 (5) | C19—C20 | 1.392 (3) |
C5—C6 | 1.385 (4) | C20—C21 | 1.389 (4) |
C6—F6 | 1.332 (3) | C20—H20A | 0.9300 |
C7—C12 | 1.383 (4) | C21—C22 | 1.371 (5) |
C7—C8 | 1.397 (4) | C21—H21A | 0.9300 |
C8—F8 | 1.335 (4) | C22—C23 | 1.378 (4) |
C8—C9 | 1.382 (4) | C22—H22A | 0.9300 |
C9—F9 | 1.340 (5) | C23—C24 | 1.387 (4) |
C9—C10 | 1.367 (6) | C23—H23A | 0.9300 |
C10—F10 | 1.330 (4) | C24—H24A | 0.9300 |
| | | |
S1i—Pt1—S1 | 180.0 | F11—C11—C10 | 120.3 (3) |
S1i—Pt1—P1 | 85.67 (2) | F11—C11—C12 | 119.4 (4) |
S1—Pt1—P1 | 94.33 (2) | C10—C11—C12 | 120.3 (3) |
S1i—Pt1—P1i | 94.33 (2) | F12—C12—C7 | 121.8 (2) |
S1—Pt1—P1i | 85.67 (2) | F12—C12—C11 | 116.1 (3) |
P1—Pt1—P1i | 180.0 | C7—C12—C11 | 122.0 (3) |
C1—S1—Pt1 | 109.92 (9) | C18—C13—C14 | 118.1 (3) |
C19—P1—C13 | 102.55 (11) | C18—C13—P1 | 118.7 (2) |
C19—P1—C7 | 107.31 (11) | C14—C13—P1 | 123.2 (2) |
C13—P1—C7 | 103.00 (11) | C13—C14—C15 | 119.7 (3) |
C19—P1—Pt1 | 110.04 (7) | C13—C14—H14A | 120.1 |
C13—P1—Pt1 | 121.48 (8) | C15—C14—H14A | 120.1 |
C7—P1—Pt1 | 111.35 (8) | C16—C15—C14 | 121.6 (4) |
C6—C1—C2 | 115.5 (3) | C16—C15—H15A | 119.2 |
C6—C1—S1 | 126.4 (2) | C14—C15—H15A | 119.2 |
C2—C1—S1 | 118.1 (2) | C15—C16—C17 | 119.6 (3) |
F2—C2—C3 | 118.7 (3) | C15—C16—H16A | 120.2 |
F2—C2—C1 | 119.4 (3) | C17—C16—H16A | 120.2 |
C3—C2—C1 | 121.9 (4) | C16—C17—C18 | 120.1 (4) |
F3—C3—C2 | 117.4 (4) | C16—C17—H17A | 120.0 |
F3—C3—C4 | 120.5 (4) | C18—C17—H17A | 120.0 |
C2—C3—C4 | 122.1 (4) | C13—C18—C17 | 120.9 (3) |
C5—C4—C3 | 116.9 (4) | C13—C18—H18A | 119.5 |
C5—C4—H4A | 121.5 | C17—C18—H18A | 119.5 |
C3—C4—H4A | 121.5 | C24—C19—C20 | 119.5 (2) |
F5—C5—C4 | 120.5 (4) | C24—C19—P1 | 119.44 (16) |
F5—C5—C6 | 117.6 (4) | C20—C19—P1 | 121.09 (18) |
C4—C5—C6 | 121.9 (4) | C21—C20—C19 | 119.6 (3) |
F6—C6—C5 | 117.7 (3) | C21—C20—H20A | 120.2 |
F6—C6—C1 | 120.7 (2) | C19—C20—H20A | 120.2 |
C5—C6—C1 | 121.5 (3) | C22—C21—C20 | 120.5 (3) |
C12—C7—C8 | 115.7 (2) | C22—C21—H21A | 119.8 |
C12—C7—P1 | 127.2 (2) | C20—C21—H21A | 119.8 |
C8—C7—P1 | 116.92 (19) | C21—C22—C23 | 120.4 (2) |
F8—C8—C9 | 118.1 (3) | C21—C22—H22A | 119.8 |
F8—C8—C7 | 119.6 (2) | C23—C22—H22A | 119.8 |
C9—C8—C7 | 122.4 (3) | C22—C23—C24 | 119.9 (3) |
F9—C9—C10 | 120.6 (3) | C22—C23—H23A | 120.0 |
F9—C9—C8 | 119.5 (4) | C24—C23—H23A | 120.0 |
C10—C9—C8 | 119.9 (3) | C23—C24—C19 | 120.2 (2) |
F10—C10—C11 | 119.8 (4) | C23—C24—H24A | 119.9 |
F10—C10—C9 | 120.5 (4) | C19—C24—H24A | 119.9 |
C11—C10—C9 | 119.7 (3) | | |
| | | |
Pt1—S1—C1—C6 | 33.1 (3) | F10—C10—C11—F11 | 0.7 (7) |
Pt1—S1—C1—C2 | −149.4 (2) | C9—C10—C11—F11 | 179.0 (4) |
C6—C1—C2—F2 | 177.1 (3) | F10—C10—C11—C12 | −177.8 (4) |
S1—C1—C2—F2 | −0.7 (5) | C9—C10—C11—C12 | 0.5 (6) |
C6—C1—C2—C3 | −3.1 (6) | C8—C7—C12—F12 | −178.3 (3) |
S1—C1—C2—C3 | 179.2 (4) | P1—C7—C12—F12 | −2.7 (4) |
F2—C2—C3—F3 | 1.1 (8) | C8—C7—C12—C11 | 1.1 (4) |
C1—C2—C3—F3 | −178.8 (5) | P1—C7—C12—C11 | 176.7 (3) |
F2—C2—C3—C4 | −178.5 (6) | F11—C11—C12—F12 | 0.3 (5) |
C1—C2—C3—C4 | 1.7 (9) | C10—C11—C12—F12 | 178.8 (4) |
F3—C3—C4—C5 | −178.8 (6) | F11—C11—C12—C7 | −179.1 (3) |
C2—C3—C4—C5 | 0.7 (11) | C10—C11—C12—C7 | −0.6 (6) |
C3—C4—C5—F5 | 178.1 (6) | C19—P1—C13—C18 | −51.8 (3) |
C3—C4—C5—C6 | −1.5 (10) | C7—P1—C13—C18 | −163.2 (2) |
F5—C5—C6—F6 | −0.4 (7) | Pt1—P1—C13—C18 | 71.4 (3) |
C4—C5—C6—F6 | 179.2 (6) | C19—P1—C13—C14 | 127.2 (3) |
F5—C5—C6—C1 | −179.6 (4) | C7—P1—C13—C14 | 15.8 (3) |
C4—C5—C6—C1 | 0.0 (8) | Pt1—P1—C13—C14 | −109.6 (3) |
C2—C1—C6—F6 | −176.9 (3) | C18—C13—C14—C15 | −2.2 (6) |
S1—C1—C6—F6 | 0.6 (4) | P1—C13—C14—C15 | 178.8 (4) |
C2—C1—C6—C5 | 2.3 (5) | C13—C14—C15—C16 | 0.9 (8) |
S1—C1—C6—C5 | 179.8 (4) | C14—C15—C16—C17 | 0.3 (9) |
C19—P1—C7—C12 | 6.2 (3) | C15—C16—C17—C18 | −0.2 (8) |
C13—P1—C7—C12 | 114.0 (3) | C14—C13—C18—C17 | 2.4 (5) |
Pt1—P1—C7—C12 | −114.3 (2) | P1—C13—C18—C17 | −178.6 (3) |
C19—P1—C7—C8 | −178.2 (2) | C16—C17—C18—C13 | −1.2 (7) |
C13—P1—C7—C8 | −70.4 (2) | C13—P1—C19—C24 | 144.19 (19) |
Pt1—P1—C7—C8 | 61.3 (2) | C7—P1—C19—C24 | −107.7 (2) |
C12—C7—C8—F8 | 177.8 (3) | Pt1—P1—C19—C24 | 13.6 (2) |
P1—C7—C8—F8 | 1.7 (3) | C13—P1—C19—C20 | −35.0 (2) |
C12—C7—C8—C9 | −1.5 (4) | C7—P1—C19—C20 | 73.1 (2) |
P1—C7—C8—C9 | −177.6 (3) | Pt1—P1—C19—C20 | −165.59 (19) |
F8—C8—C9—F9 | 0.2 (5) | C24—C19—C20—C21 | 1.3 (4) |
C7—C8—C9—F9 | 179.6 (3) | P1—C19—C20—C21 | −179.5 (2) |
F8—C8—C9—C10 | −177.9 (3) | C19—C20—C21—C22 | −0.7 (5) |
C7—C8—C9—C10 | 1.5 (5) | C20—C21—C22—C23 | 0.0 (5) |
F9—C9—C10—F10 | −0.8 (7) | C21—C22—C23—C24 | 0.0 (5) |
C8—C9—C10—F10 | 177.3 (4) | C22—C23—C24—C19 | 0.7 (4) |
F9—C9—C10—C11 | −179.0 (4) | C20—C19—C24—C23 | −1.3 (4) |
C8—C9—C10—C11 | −0.9 (6) | P1—C19—C24—C23 | 179.5 (2) |
Symmetry code: (i) −x, −y, −z. |
(cis) Bis[(pentafluorophenyl)diphenylphosphane-
κP]bis(2,3,5,6-tetrafluorophenylthiolato-
κS)platinum(II)
top
Crystal data top
[Pt(C6HF4S)2(C18H10F5P)2] | Dx = 1.868 Mg m−3 |
Mr = 1261.80 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 84 reflections |
a = 20.348 (3) Å | θ = 3.4–13.0° |
b = 19.511 (2) Å | µ = 3.40 mm−1 |
c = 22.6059 (18) Å | T = 298 K |
V = 8974.7 (17) Å3 | Plate, yellow |
Z = 8 | 0.65 × 0.26 × 0.08 mm |
F(000) = 4896 | |
Data collection top
Bruker P4 diffractometer | 4829 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube, FN4 | Rint = 0.049 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
ω scans | h = −24→1 |
Absorption correction: ψ scan (XSCANS; Bruker, 1997) | k = −23→4 |
Tmin = 0.200, Tmax = 0.339 | l = −1→26 |
10953 measured reflections | 3 standard reflections every 97 reflections |
7858 independent reflections | intensity decay: 1% |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0758P)2 + 28.3359P] where P = (Fo2 + 2Fc2)/3 |
7858 reflections | (Δ/σ)max = 0.002 |
640 parameters | Δρmax = 1.73 e Å−3 |
0 restraints | Δρmin = −2.06 e Å−3 |
0 constraints | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pt1 | 0.26305 (2) | 0.32364 (2) | 0.50273 (2) | 0.03623 (14) | |
S1 | 0.15478 (13) | 0.35885 (15) | 0.52803 (10) | 0.0550 (7) | |
S2 | 0.29034 (13) | 0.31330 (13) | 0.60341 (9) | 0.0468 (6) | |
P1 | 0.37043 (12) | 0.28949 (12) | 0.49139 (10) | 0.0413 (5) | |
P2 | 0.22397 (12) | 0.31423 (12) | 0.40789 (9) | 0.0392 (5) | |
C1 | 0.1419 (5) | 0.3411 (5) | 0.6032 (4) | 0.049 (2) | |
C2 | 0.1361 (5) | 0.2751 (5) | 0.6260 (4) | 0.052 (2) | |
F2 | 0.1439 (3) | 0.2211 (3) | 0.5893 (2) | 0.0713 (17) | |
C3 | 0.1280 (5) | 0.2630 (5) | 0.6860 (4) | 0.051 (2) | |
F3 | 0.1270 (3) | 0.1965 (3) | 0.7042 (3) | 0.0726 (17) | |
C4 | 0.1207 (5) | 0.3157 (6) | 0.7255 (4) | 0.057 (3) | |
H4A | 0.1142 | 0.3074 | 0.7655 | 0.069* | |
C5 | 0.1234 (6) | 0.3803 (6) | 0.7040 (4) | 0.064 (3) | |
F5 | 0.1163 (4) | 0.4329 (3) | 0.7414 (3) | 0.094 (2) | |
C6 | 0.1341 (5) | 0.3927 (5) | 0.6453 (4) | 0.050 (2) | |
F6 | 0.1396 (3) | 0.4591 (3) | 0.6282 (3) | 0.0753 (18) | |
C7 | 0.3001 (5) | 0.3947 (5) | 0.6347 (4) | 0.052 (2) | |
C8 | 0.3125 (6) | 0.3967 (7) | 0.6951 (5) | 0.075 (3) | |
F8 | 0.3159 (5) | 0.3371 (5) | 0.7252 (3) | 0.119 (3) | |
C9 | 0.3247 (8) | 0.4561 (9) | 0.7238 (5) | 0.102 (5) | |
F9 | 0.3368 (7) | 0.4541 (6) | 0.7826 (4) | 0.193 (6) | |
C10 | 0.3241 (8) | 0.5183 (8) | 0.6959 (7) | 0.104 (5) | |
H10A | 0.3329 | 0.5589 | 0.7160 | 0.125* | |
C11 | 0.3102 (6) | 0.5176 (6) | 0.6378 (6) | 0.079 (4) | |
F11 | 0.3085 (4) | 0.5774 (4) | 0.6063 (4) | 0.117 (3) | |
C12 | 0.2994 (5) | 0.4586 (5) | 0.6075 (5) | 0.059 (3) | |
F12 | 0.2867 (4) | 0.4635 (3) | 0.5484 (3) | 0.0784 (19) | |
C13 | 0.4221 (4) | 0.3448 (5) | 0.5380 (4) | 0.044 (2) | |
C14 | 0.4516 (5) | 0.3260 (6) | 0.5908 (5) | 0.062 (3) | |
F14 | 0.4503 (3) | 0.2616 (3) | 0.6104 (3) | 0.0717 (18) | |
C15 | 0.4809 (5) | 0.3732 (6) | 0.6289 (5) | 0.062 (3) | |
F15 | 0.5071 (4) | 0.3522 (4) | 0.6802 (3) | 0.102 (3) | |
C16 | 0.4810 (5) | 0.4416 (6) | 0.6142 (5) | 0.066 (3) | |
F16 | 0.5095 (4) | 0.4873 (4) | 0.6506 (4) | 0.102 (3) | |
C17 | 0.4532 (5) | 0.4624 (5) | 0.5622 (5) | 0.057 (3) | |
F17 | 0.4529 (3) | 0.5290 (3) | 0.5481 (3) | 0.0813 (19) | |
C18 | 0.4253 (5) | 0.4147 (5) | 0.5264 (4) | 0.050 (2) | |
F18 | 0.3962 (3) | 0.4391 (3) | 0.4758 (2) | 0.0571 (14) | |
C19 | 0.3851 (5) | 0.2014 (5) | 0.5145 (4) | 0.043 (2) | |
C20 | 0.3359 (6) | 0.1593 (5) | 0.5321 (5) | 0.068 (3) | |
H20A | 0.2937 | 0.1768 | 0.5371 | 0.081* | |
C21 | 0.3478 (7) | 0.0907 (6) | 0.5429 (5) | 0.082 (4) | |
H21A | 0.3140 | 0.0619 | 0.5552 | 0.099* | |
C22 | 0.4121 (7) | 0.0648 (6) | 0.5351 (5) | 0.080 (4) | |
H22A | 0.4207 | 0.0186 | 0.5416 | 0.096* | |
C23 | 0.4614 (6) | 0.1078 (6) | 0.5179 (5) | 0.068 (3) | |
H23A | 0.5039 | 0.0909 | 0.5137 | 0.081* | |
C24 | 0.4493 (6) | 0.1743 (5) | 0.5070 (4) | 0.059 (3) | |
H24B | 0.4832 | 0.2028 | 0.4946 | 0.070* | |
C25 | 0.4118 (5) | 0.2879 (4) | 0.4200 (4) | 0.043 (2) | |
C26 | 0.3930 (5) | 0.2365 (5) | 0.3816 (4) | 0.055 (3) | |
H26B | 0.3618 | 0.2046 | 0.3935 | 0.066* | |
C27 | 0.4205 (6) | 0.2318 (6) | 0.3247 (5) | 0.072 (3) | |
H27A | 0.4070 | 0.1977 | 0.2987 | 0.087* | |
C28 | 0.4677 (7) | 0.2784 (7) | 0.3081 (5) | 0.081 (4) | |
H28A | 0.4852 | 0.2763 | 0.2702 | 0.097* | |
C29 | 0.4889 (6) | 0.3271 (7) | 0.3458 (6) | 0.079 (4) | |
H29A | 0.5217 | 0.3573 | 0.3339 | 0.095* | |
C30 | 0.4624 (5) | 0.3328 (5) | 0.4024 (5) | 0.066 (3) | |
H30A | 0.4780 | 0.3660 | 0.4284 | 0.079* | |
C31 | 0.1518 (4) | 0.3691 (5) | 0.3918 (4) | 0.041 (2) | |
C32 | 0.1571 (5) | 0.4378 (6) | 0.4037 (4) | 0.054 (3) | |
F32 | 0.2117 (3) | 0.4642 (3) | 0.4288 (3) | 0.0704 (16) | |
C33 | 0.1096 (6) | 0.4858 (6) | 0.3878 (4) | 0.063 (3) | |
F33 | 0.1189 (4) | 0.5523 (4) | 0.3988 (3) | 0.092 (2) | |
C34 | 0.0540 (6) | 0.4630 (7) | 0.3592 (5) | 0.076 (4) | |
F34 | 0.0078 (4) | 0.5082 (4) | 0.3440 (4) | 0.125 (3) | |
C35 | 0.0466 (5) | 0.3949 (7) | 0.3476 (5) | 0.068 (3) | |
F35 | −0.0071 (3) | 0.3726 (5) | 0.3192 (3) | 0.115 (3) | |
C36 | 0.0949 (5) | 0.3498 (6) | 0.3626 (4) | 0.060 (3) | |
F36 | 0.0857 (3) | 0.2837 (4) | 0.3474 (3) | 0.0768 (19) | |
C37 | 0.1969 (4) | 0.2253 (5) | 0.4026 (4) | 0.044 (2) | |
C38 | 0.1514 (5) | 0.2021 (6) | 0.4433 (5) | 0.065 (3) | |
H38A | 0.1316 | 0.2334 | 0.4687 | 0.078* | |
C39 | 0.1349 (7) | 0.1345 (7) | 0.4473 (6) | 0.089 (4) | |
H39A | 0.1041 | 0.1196 | 0.4748 | 0.106* | |
C40 | 0.1651 (8) | 0.0882 (7) | 0.4092 (7) | 0.099 (5) | |
H40A | 0.1545 | 0.0419 | 0.4118 | 0.119* | |
C41 | 0.2093 (7) | 0.1087 (6) | 0.3686 (6) | 0.088 (4) | |
H41A | 0.2279 | 0.0770 | 0.3428 | 0.105* | |
C42 | 0.2273 (5) | 0.1779 (5) | 0.3652 (4) | 0.056 (3) | |
H42A | 0.2591 | 0.1921 | 0.3384 | 0.067* | |
C43 | 0.2708 (4) | 0.3379 (5) | 0.3423 (4) | 0.043 (2) | |
C44 | 0.2544 (5) | 0.3149 (5) | 0.2866 (4) | 0.050 (2) | |
H44A | 0.2211 | 0.2825 | 0.2826 | 0.060* | |
C45 | 0.2860 (6) | 0.3387 (6) | 0.2369 (4) | 0.063 (3) | |
H45A | 0.2764 | 0.3207 | 0.1998 | 0.075* | |
C46 | 0.3330 (5) | 0.3904 (6) | 0.2436 (5) | 0.067 (3) | |
H46A | 0.3542 | 0.4078 | 0.2104 | 0.080* | |
C47 | 0.3480 (5) | 0.4155 (6) | 0.2976 (5) | 0.067 (3) | |
H47A | 0.3795 | 0.4498 | 0.3013 | 0.080* | |
C48 | 0.3168 (5) | 0.3903 (5) | 0.3473 (4) | 0.052 (2) | |
H48A | 0.3266 | 0.4085 | 0.3843 | 0.062* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pt1 | 0.0366 (2) | 0.0371 (2) | 0.03498 (19) | −0.00151 (15) | −0.00225 (14) | 0.00068 (15) |
S1 | 0.0498 (15) | 0.0742 (18) | 0.0411 (12) | 0.0151 (14) | 0.0052 (11) | 0.0123 (12) |
S2 | 0.0508 (14) | 0.0511 (15) | 0.0385 (11) | −0.0005 (12) | −0.0058 (10) | 0.0047 (10) |
P1 | 0.0386 (13) | 0.0376 (13) | 0.0476 (13) | −0.0030 (11) | −0.0040 (10) | 0.0017 (11) |
P2 | 0.0414 (14) | 0.0416 (13) | 0.0346 (11) | −0.0047 (11) | −0.0030 (9) | −0.0009 (10) |
C1 | 0.042 (6) | 0.066 (7) | 0.039 (5) | 0.005 (5) | 0.008 (4) | −0.004 (5) |
C2 | 0.056 (7) | 0.044 (6) | 0.055 (6) | 0.009 (5) | 0.004 (5) | −0.005 (5) |
F2 | 0.094 (5) | 0.058 (4) | 0.062 (3) | 0.004 (4) | 0.005 (3) | −0.006 (3) |
C3 | 0.051 (6) | 0.044 (6) | 0.056 (6) | −0.006 (5) | 0.000 (5) | 0.015 (5) |
F3 | 0.076 (4) | 0.064 (4) | 0.078 (4) | −0.004 (3) | −0.007 (3) | 0.016 (3) |
C4 | 0.061 (7) | 0.072 (8) | 0.039 (5) | 0.001 (6) | 0.004 (5) | −0.005 (5) |
C5 | 0.088 (9) | 0.052 (7) | 0.053 (6) | 0.008 (6) | 0.011 (6) | −0.006 (5) |
F5 | 0.135 (7) | 0.082 (5) | 0.063 (4) | 0.013 (5) | 0.016 (4) | −0.020 (4) |
C6 | 0.055 (6) | 0.042 (6) | 0.053 (6) | 0.000 (5) | 0.012 (5) | 0.008 (5) |
F6 | 0.100 (5) | 0.059 (4) | 0.067 (4) | 0.010 (4) | 0.010 (3) | 0.003 (3) |
C7 | 0.049 (6) | 0.064 (7) | 0.042 (5) | 0.002 (5) | 0.001 (4) | −0.005 (5) |
C8 | 0.092 (9) | 0.081 (9) | 0.052 (6) | −0.010 (8) | −0.014 (6) | −0.011 (6) |
F8 | 0.173 (9) | 0.133 (7) | 0.050 (4) | −0.028 (6) | −0.032 (5) | 0.014 (4) |
C9 | 0.137 (14) | 0.117 (12) | 0.053 (7) | −0.020 (11) | −0.024 (8) | −0.029 (8) |
F9 | 0.291 (15) | 0.221 (11) | 0.067 (5) | −0.069 (11) | −0.047 (7) | −0.045 (6) |
C10 | 0.113 (12) | 0.101 (12) | 0.099 (11) | −0.004 (10) | −0.021 (9) | −0.057 (10) |
C11 | 0.078 (9) | 0.049 (8) | 0.109 (10) | −0.002 (7) | −0.005 (7) | −0.012 (7) |
F11 | 0.127 (7) | 0.063 (5) | 0.161 (8) | −0.003 (5) | −0.021 (6) | −0.030 (5) |
C12 | 0.061 (7) | 0.047 (6) | 0.068 (7) | 0.001 (5) | −0.013 (5) | −0.010 (5) |
F12 | 0.105 (5) | 0.057 (4) | 0.073 (4) | −0.002 (4) | −0.015 (4) | 0.000 (3) |
C13 | 0.028 (5) | 0.049 (6) | 0.056 (5) | −0.004 (4) | −0.006 (4) | 0.003 (4) |
C14 | 0.052 (7) | 0.054 (7) | 0.080 (7) | 0.003 (6) | −0.015 (6) | 0.006 (6) |
F14 | 0.075 (4) | 0.061 (4) | 0.079 (4) | 0.011 (3) | −0.032 (3) | 0.006 (3) |
C15 | 0.052 (7) | 0.068 (8) | 0.065 (6) | −0.006 (6) | −0.023 (5) | 0.000 (6) |
F15 | 0.113 (6) | 0.104 (6) | 0.088 (5) | 0.002 (5) | −0.060 (4) | −0.003 (4) |
C16 | 0.048 (6) | 0.072 (8) | 0.079 (7) | −0.013 (6) | −0.006 (6) | −0.022 (6) |
F16 | 0.098 (6) | 0.091 (5) | 0.117 (6) | −0.023 (5) | −0.047 (4) | −0.034 (4) |
C17 | 0.046 (6) | 0.046 (6) | 0.079 (7) | −0.008 (5) | −0.008 (5) | −0.001 (5) |
F17 | 0.090 (5) | 0.054 (4) | 0.100 (5) | −0.017 (4) | −0.008 (4) | −0.005 (3) |
C18 | 0.038 (5) | 0.052 (6) | 0.059 (6) | −0.006 (5) | −0.010 (5) | 0.010 (5) |
F18 | 0.058 (4) | 0.048 (3) | 0.065 (3) | −0.001 (3) | −0.002 (3) | 0.009 (3) |
C19 | 0.049 (6) | 0.040 (5) | 0.040 (4) | −0.004 (5) | −0.003 (4) | 0.001 (4) |
C20 | 0.075 (8) | 0.046 (7) | 0.082 (8) | −0.014 (6) | 0.012 (6) | 0.007 (6) |
C21 | 0.114 (11) | 0.043 (7) | 0.090 (9) | −0.018 (7) | 0.017 (8) | 0.015 (6) |
C22 | 0.111 (11) | 0.054 (8) | 0.075 (8) | 0.024 (8) | 0.007 (8) | 0.015 (6) |
C23 | 0.073 (8) | 0.061 (8) | 0.070 (7) | 0.027 (7) | −0.007 (6) | 0.003 (6) |
C24 | 0.051 (6) | 0.049 (6) | 0.077 (7) | 0.007 (5) | −0.009 (5) | 0.005 (6) |
C25 | 0.044 (6) | 0.033 (5) | 0.053 (5) | −0.003 (5) | −0.007 (4) | 0.004 (4) |
C26 | 0.045 (6) | 0.055 (7) | 0.065 (6) | −0.003 (5) | −0.008 (5) | −0.003 (5) |
C27 | 0.073 (8) | 0.080 (9) | 0.064 (7) | 0.005 (7) | −0.014 (6) | −0.023 (6) |
C28 | 0.085 (10) | 0.091 (10) | 0.066 (7) | 0.014 (8) | 0.016 (7) | −0.006 (7) |
C29 | 0.065 (8) | 0.076 (9) | 0.096 (9) | 0.003 (7) | 0.038 (7) | 0.015 (8) |
C30 | 0.055 (7) | 0.051 (7) | 0.092 (8) | −0.003 (6) | 0.008 (6) | 0.003 (6) |
C31 | 0.036 (5) | 0.048 (6) | 0.039 (5) | −0.002 (5) | 0.006 (4) | 0.002 (4) |
C32 | 0.060 (7) | 0.067 (7) | 0.035 (5) | −0.001 (6) | −0.001 (5) | 0.005 (5) |
F32 | 0.082 (4) | 0.054 (4) | 0.075 (4) | −0.004 (4) | −0.004 (3) | 0.002 (3) |
C33 | 0.074 (9) | 0.062 (8) | 0.054 (6) | 0.013 (7) | 0.016 (6) | 0.012 (5) |
F33 | 0.118 (6) | 0.075 (5) | 0.083 (4) | 0.030 (4) | 0.012 (4) | 0.014 (4) |
C34 | 0.062 (8) | 0.092 (10) | 0.073 (7) | 0.036 (8) | 0.011 (6) | 0.026 (7) |
F34 | 0.100 (6) | 0.143 (8) | 0.133 (7) | 0.068 (6) | −0.001 (5) | 0.036 (6) |
C35 | 0.044 (7) | 0.098 (10) | 0.063 (6) | 0.007 (7) | −0.007 (5) | 0.010 (7) |
F35 | 0.066 (5) | 0.165 (8) | 0.115 (6) | 0.024 (5) | −0.033 (4) | −0.012 (6) |
C36 | 0.059 (7) | 0.074 (8) | 0.045 (5) | −0.005 (7) | −0.002 (5) | 0.001 (5) |
F36 | 0.051 (4) | 0.096 (5) | 0.083 (4) | −0.012 (4) | −0.019 (3) | −0.013 (4) |
C37 | 0.037 (5) | 0.047 (6) | 0.049 (5) | −0.011 (5) | −0.010 (4) | 0.006 (4) |
C38 | 0.066 (7) | 0.060 (7) | 0.068 (7) | −0.023 (6) | −0.005 (6) | 0.000 (6) |
C39 | 0.099 (11) | 0.081 (10) | 0.087 (9) | −0.031 (9) | 0.010 (8) | 0.010 (8) |
C40 | 0.101 (12) | 0.060 (9) | 0.137 (13) | −0.021 (9) | −0.014 (10) | 0.014 (9) |
C41 | 0.087 (10) | 0.049 (7) | 0.126 (12) | −0.003 (7) | −0.021 (9) | −0.017 (8) |
C42 | 0.061 (7) | 0.052 (6) | 0.056 (6) | 0.004 (6) | −0.012 (5) | −0.006 (5) |
C43 | 0.038 (6) | 0.050 (6) | 0.041 (5) | 0.002 (5) | −0.006 (4) | −0.001 (4) |
C44 | 0.049 (6) | 0.056 (6) | 0.045 (5) | 0.001 (5) | −0.002 (4) | 0.000 (4) |
C45 | 0.076 (8) | 0.075 (8) | 0.037 (5) | 0.013 (7) | 0.007 (5) | −0.001 (5) |
C46 | 0.061 (7) | 0.083 (8) | 0.056 (6) | −0.008 (7) | 0.007 (5) | 0.027 (6) |
C47 | 0.056 (7) | 0.077 (8) | 0.067 (7) | −0.012 (6) | 0.000 (5) | 0.014 (6) |
C48 | 0.053 (6) | 0.052 (6) | 0.050 (5) | 0.003 (5) | −0.013 (5) | 0.004 (5) |
Geometric parameters (Å, º) top
Pt1—P2 | 2.294 (2) | C21—H21A | 0.9300 |
Pt1—P1 | 2.299 (2) | C22—C23 | 1.365 (16) |
Pt1—S2 | 2.352 (2) | C22—H22A | 0.9300 |
Pt1—S1 | 2.377 (3) | C23—C24 | 1.344 (14) |
S1—C1 | 1.753 (9) | C23—H23A | 0.9300 |
S2—C7 | 1.749 (10) | C24—H24B | 0.9300 |
P1—C25 | 1.821 (9) | C25—C26 | 1.380 (12) |
P1—C19 | 1.821 (9) | C25—C30 | 1.408 (13) |
P1—C13 | 1.840 (9) | C26—C27 | 1.405 (14) |
P2—C43 | 1.822 (9) | C26—H26B | 0.9300 |
P2—C37 | 1.825 (9) | C27—C28 | 1.374 (16) |
P2—C31 | 1.853 (9) | C27—H27A | 0.9300 |
C1—C2 | 1.393 (13) | C28—C29 | 1.347 (17) |
C1—C6 | 1.394 (13) | C28—H28A | 0.9300 |
C2—F2 | 1.349 (10) | C29—C30 | 1.393 (15) |
C2—C3 | 1.386 (13) | C29—H29A | 0.9300 |
C3—F3 | 1.362 (10) | C30—H30A | 0.9300 |
C3—C4 | 1.370 (13) | C31—C32 | 1.373 (13) |
C4—C5 | 1.350 (13) | C31—C36 | 1.384 (13) |
C4—H4A | 0.9300 | C32—F32 | 1.349 (11) |
C5—F5 | 1.337 (11) | C32—C33 | 1.392 (15) |
C5—C6 | 1.368 (13) | C33—F33 | 1.336 (13) |
C6—F6 | 1.355 (11) | C33—C34 | 1.376 (17) |
C7—C8 | 1.390 (13) | C34—F34 | 1.334 (12) |
C7—C12 | 1.391 (14) | C34—C35 | 1.364 (17) |
C8—F8 | 1.350 (13) | C35—F35 | 1.340 (12) |
C8—C9 | 1.351 (17) | C35—C36 | 1.361 (15) |
C9—F9 | 1.352 (14) | C36—F36 | 1.348 (12) |
C9—C10 | 1.368 (19) | C37—C38 | 1.383 (13) |
C10—C11 | 1.343 (17) | C37—C42 | 1.396 (13) |
C10—H10A | 0.9300 | C38—C39 | 1.365 (16) |
C11—C12 | 1.358 (15) | C38—H38A | 0.9300 |
C11—F11 | 1.366 (14) | C39—C40 | 1.392 (18) |
C12—F12 | 1.363 (11) | C39—H39A | 0.9300 |
C13—C14 | 1.385 (13) | C40—C41 | 1.346 (18) |
C13—C18 | 1.390 (13) | C40—H40A | 0.9300 |
C14—F14 | 1.333 (11) | C41—C42 | 1.400 (15) |
C14—C15 | 1.394 (14) | C41—H41A | 0.9300 |
C15—F15 | 1.340 (11) | C42—H42A | 0.9300 |
C15—C16 | 1.375 (15) | C43—C44 | 1.377 (12) |
C16—F16 | 1.346 (11) | C43—C48 | 1.391 (13) |
C16—C17 | 1.368 (14) | C44—C45 | 1.376 (13) |
C17—F17 | 1.337 (11) | C44—H44A | 0.9300 |
C17—C18 | 1.358 (13) | C45—C46 | 1.399 (14) |
C18—F18 | 1.372 (10) | C45—H45A | 0.9300 |
C19—C20 | 1.354 (14) | C46—C47 | 1.350 (14) |
C19—C24 | 1.419 (15) | C46—H46A | 0.9300 |
C20—C21 | 1.383 (15) | C47—C48 | 1.382 (13) |
C20—H20A | 0.9300 | C47—H47A | 0.9300 |
C21—C22 | 1.413 (17) | C48—H48A | 0.9300 |
| | | |
P2—Pt1—P1 | 101.66 (8) | C22—C21—H21A | 120.5 |
P2—Pt1—S2 | 168.40 (9) | C23—C22—C21 | 119.8 (11) |
P1—Pt1—S2 | 81.87 (8) | C23—C22—H22A | 120.1 |
P2—Pt1—S1 | 85.80 (8) | C21—C22—H22A | 120.1 |
P1—Pt1—S1 | 172.47 (8) | C24—C23—C22 | 120.7 (12) |
S2—Pt1—S1 | 90.61 (8) | C24—C23—H23A | 119.6 |
C1—S1—Pt1 | 108.3 (3) | C22—C23—H23A | 119.6 |
C7—S2—Pt1 | 109.9 (3) | C23—C24—C19 | 120.5 (11) |
C25—P1—C19 | 99.4 (4) | C23—C24—H24B | 119.8 |
C25—P1—C13 | 104.6 (4) | C19—C24—H24B | 119.8 |
C19—P1—C13 | 107.2 (4) | C26—C25—C30 | 118.4 (9) |
C25—P1—Pt1 | 122.9 (3) | C26—C25—P1 | 116.2 (7) |
C19—P1—Pt1 | 113.4 (3) | C30—C25—P1 | 125.4 (8) |
C13—P1—Pt1 | 108.0 (3) | C25—C26—C27 | 120.8 (10) |
C43—P2—C37 | 110.2 (4) | C25—C26—H26B | 119.6 |
C43—P2—C31 | 96.2 (4) | C27—C26—H26B | 119.6 |
C37—P2—C31 | 107.3 (4) | C28—C27—C26 | 119.0 (10) |
C43—P2—Pt1 | 124.0 (3) | C28—C27—H27A | 120.5 |
C37—P2—Pt1 | 104.0 (3) | C26—C27—H27A | 120.5 |
C31—P2—Pt1 | 114.3 (3) | C29—C28—C27 | 121.2 (11) |
C2—C1—C6 | 113.9 (8) | C29—C28—H28A | 119.4 |
C2—C1—S1 | 123.6 (7) | C27—C28—H28A | 119.4 |
C6—C1—S1 | 122.4 (8) | C28—C29—C30 | 120.8 (12) |
F2—C2—C3 | 118.8 (9) | C28—C29—H29A | 119.6 |
F2—C2—C1 | 119.0 (8) | C30—C29—H29A | 119.6 |
C3—C2—C1 | 122.0 (9) | C29—C30—C25 | 119.6 (11) |
F3—C3—C4 | 121.1 (9) | C29—C30—H30A | 120.2 |
F3—C3—C2 | 117.4 (9) | C25—C30—H30A | 120.2 |
C4—C3—C2 | 121.5 (9) | C32—C31—C36 | 115.2 (10) |
C5—C4—C3 | 117.5 (9) | C32—C31—P2 | 117.6 (8) |
C5—C4—H4A | 121.2 | C36—C31—P2 | 126.8 (8) |
C3—C4—H4A | 121.2 | F32—C32—C31 | 121.3 (9) |
F5—C5—C4 | 119.0 (9) | F32—C32—C33 | 115.1 (10) |
F5—C5—C6 | 119.6 (10) | C31—C32—C33 | 123.4 (11) |
C4—C5—C6 | 121.4 (9) | F33—C33—C34 | 121.1 (11) |
F6—C6—C5 | 117.4 (9) | F33—C33—C32 | 120.4 (11) |
F6—C6—C1 | 119.0 (8) | C34—C33—C32 | 118.4 (11) |
C5—C6—C1 | 123.5 (9) | F34—C34—C35 | 121.1 (13) |
C8—C7—C12 | 114.2 (10) | F34—C34—C33 | 119.2 (13) |
C8—C7—S2 | 116.4 (8) | C35—C34—C33 | 119.7 (11) |
C12—C7—S2 | 129.4 (7) | F35—C35—C36 | 119.9 (12) |
F8—C8—C9 | 119.2 (11) | F35—C35—C34 | 119.8 (12) |
F8—C8—C7 | 118.7 (10) | C36—C35—C34 | 120.2 (11) |
C9—C8—C7 | 122.0 (12) | F36—C36—C35 | 117.0 (10) |
C8—C9—F9 | 118.6 (15) | F36—C36—C31 | 119.9 (10) |
C8—C9—C10 | 122.5 (11) | C35—C36—C31 | 123.1 (11) |
F9—C9—C10 | 118.8 (14) | C38—C37—C42 | 118.9 (9) |
C11—C10—C9 | 116.3 (12) | C38—C37—P2 | 117.9 (8) |
C11—C10—H10A | 121.8 | C42—C37—P2 | 122.5 (7) |
C9—C10—H10A | 121.8 | C39—C38—C37 | 121.6 (11) |
C10—C11—C12 | 122.5 (13) | C39—C38—H38A | 119.2 |
C10—C11—F11 | 120.3 (12) | C37—C38—H38A | 119.2 |
C12—C11—F11 | 117.1 (12) | C38—C39—C40 | 118.6 (12) |
C11—C12—F12 | 117.8 (10) | C38—C39—H39A | 120.7 |
C11—C12—C7 | 122.4 (10) | C40—C39—H39A | 120.7 |
F12—C12—C7 | 119.8 (9) | C41—C40—C39 | 121.6 (13) |
C14—C13—C18 | 113.8 (9) | C41—C40—H40A | 119.2 |
C14—C13—P1 | 125.9 (8) | C39—C40—H40A | 119.2 |
C18—C13—P1 | 119.6 (7) | C40—C41—C42 | 119.9 (13) |
F14—C14—C13 | 121.8 (9) | C40—C41—H41A | 120.0 |
F14—C14—C15 | 115.2 (9) | C42—C41—H41A | 120.0 |
C13—C14—C15 | 122.9 (10) | C37—C42—C41 | 119.4 (11) |
F15—C15—C16 | 120.3 (10) | C37—C42—H42A | 120.3 |
F15—C15—C14 | 120.2 (10) | C41—C42—H42A | 120.3 |
C16—C15—C14 | 119.5 (10) | C44—C43—C48 | 118.5 (9) |
F16—C16—C17 | 120.4 (11) | C44—C43—P2 | 122.3 (7) |
F16—C16—C15 | 119.8 (10) | C48—C43—P2 | 118.2 (7) |
C17—C16—C15 | 119.7 (10) | C45—C44—C43 | 121.5 (10) |
F17—C17—C18 | 121.5 (9) | C45—C44—H44A | 119.2 |
F17—C17—C16 | 119.7 (10) | C43—C44—H44A | 119.2 |
C18—C17—C16 | 118.8 (10) | C44—C45—C46 | 118.4 (9) |
C17—C18—F18 | 116.1 (9) | C44—C45—H45A | 120.8 |
C17—C18—C13 | 125.4 (9) | C46—C45—H45A | 120.8 |
F18—C18—C13 | 118.5 (8) | C47—C46—C45 | 120.9 (9) |
C20—C19—C24 | 119.3 (10) | C47—C46—H46A | 119.6 |
C20—C19—P1 | 122.4 (8) | C45—C46—H46A | 119.6 |
C24—C19—P1 | 117.9 (7) | C46—C47—C48 | 120.2 (10) |
C19—C20—C21 | 120.6 (12) | C46—C47—H47A | 119.9 |
C19—C20—H20A | 119.7 | C48—C47—H47A | 119.9 |
C21—C20—H20A | 119.7 | C47—C48—C43 | 120.3 (9) |
C20—C21—C22 | 119.1 (12) | C47—C48—H48A | 119.9 |
C20—C21—H21A | 120.5 | C43—C48—H48A | 119.9 |
| | | |
Pt1—S1—C1—C2 | −69.7 (9) | C24—C19—C20—C21 | 0.1 (16) |
Pt1—S1—C1—C6 | 112.7 (8) | P1—C19—C20—C21 | 172.6 (9) |
C6—C1—C2—F2 | −178.9 (9) | C19—C20—C21—C22 | −0.2 (18) |
S1—C1—C2—F2 | 3.3 (14) | C20—C21—C22—C23 | 0.9 (19) |
C6—C1—C2—C3 | −4.3 (15) | C21—C22—C23—C24 | −1.5 (18) |
S1—C1—C2—C3 | 177.9 (8) | C22—C23—C24—C19 | 1.4 (16) |
F2—C2—C3—F3 | −1.4 (14) | C20—C19—C24—C23 | −0.6 (15) |
C1—C2—C3—F3 | −176.1 (9) | P1—C19—C24—C23 | −173.5 (8) |
F2—C2—C3—C4 | 179.2 (9) | C19—P1—C25—C26 | 53.1 (8) |
C1—C2—C3—C4 | 4.6 (16) | C13—P1—C25—C26 | 163.8 (7) |
F3—C3—C4—C5 | 179.0 (10) | Pt1—P1—C25—C26 | −72.8 (8) |
C2—C3—C4—C5 | −1.7 (16) | C19—P1—C25—C30 | −124.3 (9) |
C3—C4—C5—F5 | 179.8 (10) | C13—P1—C25—C30 | −13.6 (10) |
C3—C4—C5—C6 | −1.0 (18) | Pt1—P1—C25—C30 | 109.8 (8) |
F5—C5—C6—F6 | 2.7 (16) | C30—C25—C26—C27 | −4.2 (15) |
C4—C5—C6—F6 | −176.5 (10) | P1—C25—C26—C27 | 178.2 (8) |
F5—C5—C6—C1 | −179.8 (10) | C25—C26—C27—C28 | 1.4 (16) |
C4—C5—C6—C1 | 1.1 (18) | C26—C27—C28—C29 | 1.7 (19) |
C2—C1—C6—F6 | 179.1 (9) | C27—C28—C29—C30 | −2 (2) |
S1—C1—C6—F6 | −3.1 (14) | C28—C29—C30—C25 | −1.2 (18) |
C2—C1—C6—C5 | 1.6 (15) | C26—C25—C30—C29 | 4.2 (15) |
S1—C1—C6—C5 | 179.4 (9) | P1—C25—C30—C29 | −178.5 (8) |
Pt1—S2—C7—C8 | 176.3 (8) | C43—P2—C31—C32 | −78.3 (7) |
Pt1—S2—C7—C12 | −6.1 (11) | C37—P2—C31—C32 | 168.3 (7) |
C12—C7—C8—F8 | −178.2 (11) | Pt1—P2—C31—C32 | 53.5 (7) |
S2—C7—C8—F8 | −0.2 (16) | C43—P2—C31—C36 | 93.8 (8) |
C12—C7—C8—C9 | −1.9 (19) | C37—P2—C31—C36 | −19.6 (9) |
S2—C7—C8—C9 | 176.1 (12) | Pt1—P2—C31—C36 | −134.4 (7) |
F8—C8—C9—F9 | −3 (2) | C36—C31—C32—F32 | −175.9 (8) |
C7—C8—C9—F9 | −179.5 (13) | P2—C31—C32—F32 | −2.9 (12) |
F8—C8—C9—C10 | 178.0 (15) | C36—C31—C32—C33 | −0.4 (14) |
C7—C8—C9—C10 | 2 (3) | P2—C31—C32—C33 | 172.6 (7) |
C8—C9—C10—C11 | 0 (3) | F32—C32—C33—F33 | −1.7 (13) |
F9—C9—C10—C11 | −178.4 (14) | C31—C32—C33—F33 | −177.5 (9) |
C9—C10—C11—C12 | −2 (2) | F32—C32—C33—C34 | 176.7 (9) |
C9—C10—C11—F11 | −180.0 (14) | C31—C32—C33—C34 | 0.9 (15) |
C10—C11—C12—F12 | −179.0 (12) | F33—C33—C34—F34 | −2.0 (16) |
F11—C11—C12—F12 | −1.2 (17) | C32—C33—C34—F34 | 179.6 (9) |
C10—C11—C12—C7 | 2 (2) | F33—C33—C34—C35 | 178.7 (10) |
F11—C11—C12—C7 | 179.8 (10) | C32—C33—C34—C35 | 0.3 (16) |
C8—C7—C12—C11 | 0.1 (17) | F34—C34—C35—F35 | 1.6 (18) |
S2—C7—C12—C11 | −177.6 (9) | C33—C34—C35—F35 | −179.2 (9) |
C8—C7—C12—F12 | −178.9 (10) | F34—C34—C35—C36 | 178.7 (10) |
S2—C7—C12—F12 | 3.5 (16) | C33—C34—C35—C36 | −2.0 (17) |
C25—P1—C13—C14 | −121.6 (9) | F35—C35—C36—F36 | 0.1 (15) |
C19—P1—C13—C14 | −16.7 (10) | C34—C35—C36—F36 | −177.0 (10) |
Pt1—P1—C13—C14 | 105.8 (9) | F35—C35—C36—C31 | 179.8 (9) |
C25—P1—C13—C18 | 69.3 (9) | C34—C35—C36—C31 | 2.7 (17) |
C19—P1—C13—C18 | 174.1 (8) | C32—C31—C36—F36 | 178.3 (8) |
Pt1—P1—C13—C18 | −63.3 (8) | P2—C31—C36—F36 | 6.0 (13) |
C18—C13—C14—F14 | 176.6 (9) | C32—C31—C36—C35 | −1.4 (14) |
P1—C13—C14—F14 | 7.0 (15) | P2—C31—C36—C35 | −173.7 (8) |
C18—C13—C14—C15 | 0.7 (16) | C43—P2—C37—C38 | −169.1 (7) |
P1—C13—C14—C15 | −169.0 (9) | C31—P2—C37—C38 | −65.4 (8) |
F14—C14—C15—F15 | 2.0 (16) | Pt1—P2—C37—C38 | 56.1 (8) |
C13—C14—C15—F15 | 178.2 (10) | C43—P2—C37—C42 | 20.7 (9) |
F14—C14—C15—C16 | −176.0 (10) | C31—P2—C37—C42 | 124.4 (8) |
C13—C14—C15—C16 | 0.2 (18) | Pt1—P2—C37—C42 | −114.1 (7) |
F15—C15—C16—F16 | 2.4 (18) | C42—C37—C38—C39 | −1.0 (15) |
C14—C15—C16—F16 | −179.6 (10) | P2—C37—C38—C39 | −171.5 (9) |
F15—C15—C16—C17 | −179.0 (10) | C37—C38—C39—C40 | 0.2 (19) |
C14—C15—C16—C17 | −1.0 (18) | C38—C39—C40—C41 | −1 (2) |
F16—C16—C17—F17 | −1.8 (16) | C39—C40—C41—C42 | 2 (2) |
C15—C16—C17—F17 | 179.6 (10) | C38—C37—C42—C41 | 2.2 (14) |
F16—C16—C17—C18 | 179.4 (10) | P2—C37—C42—C41 | 172.3 (8) |
C15—C16—C17—C18 | 0.9 (17) | C40—C41—C42—C37 | −2.6 (18) |
F17—C17—C18—F18 | −1.1 (15) | C37—P2—C43—C44 | 37.8 (9) |
C16—C17—C18—F18 | 177.7 (9) | C31—P2—C43—C44 | −73.3 (8) |
F17—C17—C18—C13 | −178.6 (10) | Pt1—P2—C43—C44 | 161.7 (6) |
C16—C17—C18—C13 | 0.2 (17) | C37—P2—C43—C48 | −154.2 (7) |
C14—C13—C18—C17 | −0.9 (15) | C31—P2—C43—C48 | 94.8 (8) |
P1—C13—C18—C17 | 169.5 (8) | Pt1—P2—C43—C48 | −30.2 (9) |
C14—C13—C18—F18 | −178.4 (8) | C48—C43—C44—C45 | 5.2 (14) |
P1—C13—C18—F18 | −8.0 (13) | P2—C43—C44—C45 | 173.2 (8) |
C25—P1—C19—C20 | −127.4 (9) | C43—C44—C45—C46 | −4.0 (15) |
C13—P1—C19—C20 | 124.0 (9) | C44—C45—C46—C47 | 1.4 (16) |
Pt1—P1—C19—C20 | 4.8 (9) | C45—C46—C47—C48 | −0.3 (17) |
C25—P1—C19—C24 | 45.3 (8) | C46—C47—C48—C43 | 1.6 (16) |
C13—P1—C19—C24 | −63.3 (8) | C44—C43—C48—C47 | −4.0 (14) |
Pt1—P1—C19—C24 | 177.5 (6) | P2—C43—C48—C47 | −172.5 (8) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···F36i | 0.93 | 2.63 | 3.444 (12) | 147 |
C30—H30A···F17ii | 0.93 | 2.54 | 3.391 (13) | 152 |
C30—H30A···F18 | 0.93 | 2.44 | 2.979 (12) | 117 |
C38—H38A···S1 | 0.93 | 2.83 | 3.608 (12) | 142 |
C48—H48A···F18 | 0.93 | 2.58 | 3.457 (11) | 158 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y+1, −z+1. |
Comparison of key geometric parameters (Å, °)
for the trans and cis
complexes [Pt(SC6HF4-4)2{P(C6H5)2(C6F5)}2]. topParameter | trans isomer a | cis isomer |
Pt1—S1 | 2.3318 (5) | 2.377 (3) |
Pt1—S2 | - | 2.352 (2) |
Pt1—P1 | 2.3345 (6) | 2.299 (2) |
Pt1—P2 | - | 2.294 (2) |
| | |
S1—Pt1—S2 | 180 | 90.61 (8) |
P1—Pt1—P2 | 180 | 101.66 (8) |
S1—Pt1—P1 | 94.33 (2) | 172.47 (8) |
S1—Pt1—P2 | - | 85.80 (8) |
S2—Pt1—P1 | 85.67 (2) | 81.87 (8) |
S2—Pt1—P2 | - | 168.40 (9) |
Pt1—S1—C1 | 109.92 (9) | 108.3 (3) |
Pt1—S2—C7 | - | 109.9 (3) |
| | |
Average angle at P1 | 109 (6) | 109 (7) |
Average angle at P2 | - | 109 (9) |
Note: (a) for the trans isomer, the S2 and P2 sites are equivalent
by symmetry to the S1 and P1 sites, respectively. |
Mulliken atomic charges and dipole moment calculated at B3LYP/6-31+G(d)
level, employing an effective core potential for Pt and the Lanl2DZ basis set
(Hay and Wadt type) for isomers trans and cis, in the gas phase.
Only atoms close to Pt are reported. topAtom | trans isomer | cis isomer |
Pt1 | 0.784 | -0.320 |
S1 | 0.046 | -0.475 |
S2 | 0.046 | -0.279 |
P1 | 0.741 | 1.008 |
P2 | 0.741 | 0.631 |
F2 | -0.146 | -0.225 |
F18 | -0.178 | -0.173 |
F32 | -0.178 | -0.170 |
F12 | -0.146 | -0.150 |
H20 | 0.238 | 0.258 |
H38 | 0.238 | 0.239 |
µ (Debye) | 0.000 | 13.551 |
Occupancy of natural bond orbitals and second order perturbation theory analysis
of Fock matrix in NBO basis for F···Pt pairs in isomer cis. topNBOa | Occupancy | Atomic orbitals |
LP(1) F2 | 1.98318 | s(65.82%) p(34.17%) d(0.01%) |
LP(1) F18 | 1.98297 | s(65.23%) p(34.76%) d(0.01%) |
LP(1) F32 | 1.98350 | s(67.84%) p(32.16%) d(0.01%) |
LP(1) F12 | 1.97987 | s(61.17%) p(38.81%) d(0.02%) |
RY*(7) Pt | 0.03585 | s(50.23%) p(41.59%) d(0.18%) |
| | |
Donor (i) | Acceptor (j) | E(2) stabilization energy |
F2 LP(1) | Pt RY*(7) | 2.77 kcal mol-1 |
F18 LP(1) | Pt RY*(7) | 2.50 kcal mol-1 |
F32 LP(1) | Pt RY*(7) | 2.47 kcal mol-1 |
F12 LP(1) | Pt RY*(7) | 6.92 kcal mol-1 |
Note: (a) occupied Lewis and unoccupied non-Lewis types NBO
are considered. |