The title compound, trans-[PdCl2{P(C6H4F)3}2]·C7H8, where P(C6H4F)3 is tris(4-fluorophenyl)phosphine, crystallizes with both molecules in special positions. The trans-[PdCl2{P(C6H4F)3}2] molecule lies on an inversion centre, resulting in a distorted trans square-planar geometry. The Pd—P and Pd—Cl distances are 2.3398 (12) and 2.2955 (13) Å, respectively, and the P—Pd—Cl angle is 87.58 (5)°. The effective cone angle for the tris(4-fluorophenyl)phosphine group was calculated to be 152°. The toluene molecule lies on a twofold rotation axis.
Supporting information
CCDC reference: 605083
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.007 Å
- R factor = 0.052
- wR factor = 0.150
- Data-to-parameter ratio = 19.6
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT221_ALERT_4_C Large Solvent/Anion C Ueq(max)/Ueq(min) ... 3.10 Ratio
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C2
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
2 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).
trans-Dichlorobis[tri(4-fluorophenyl)phosphine]palladium(II) toluene
solvate
top
Crystal data top
[PdCl2{P(C6H4F)3}2]·C7H8 | F(000) = 1816 |
Mr = 901.93 | Dx = 1.531 Mg m−3 |
Orthorhombic, Pccn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ab 2ac | Cell parameters from 6262 reflections |
a = 29.215 (5) Å | θ = 2.4–24.2° |
b = 7.856 (5) Å | µ = 0.75 mm−1 |
c = 17.051 (5) Å | T = 100 K |
V = 3913 (3) Å3 | Plate, yellow |
Z = 4 | 0.32 × 0.12 × 0.04 mm |
Data collection top
Bruker X8 APEXII 4K KappaCCD diffractometer | 4842 independent reflections |
Radiation source: fine-focus sealed tube | 3479 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.086 |
Detector resolution: 512 pixels mm-1 | θmax = 28.2°, θmin = 1.4° |
ω and ψ scans | h = −38→38 |
Absorption correction: multi-scan SADABS (Bruker, 1998) | k = −9→10 |
Tmin = 0.795, Tmax = 0.971 | l = −22→22 |
52873 measured reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.052 | w = 1/[σ2(Fo2) + (0.0553P)2 + 10.4167P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.15 | (Δ/σ)max = 0.009 |
S = 1.21 | Δρmax = 1.22 e Å−3 |
4842 reflections | Δρmin = −0.88 e Å−3 |
247 parameters | |
Special details top
Experimental. 1H NMR (CDCl3, 300 MHz, p.p.m.): 7.7–7.5 (m), 7.2–7.0 (m);
13C{H} NMR (CDCl3, 75.5 MHz, p.p.m.): 164.8 (d, 1JF—C
= 253 Hz), 137.4, 125.1, 116.3; 31P{H} NMR (CDCl3, 121.4 MHz, p.p.m.):
21.55. The intensity data was collected on a Bruker X8 Apex II 4 K Kappa CCD
diffractometer using an exposure time of 10 s/frame. A total of 1689 frames
were collected with a frame width of 0.5° covering up to θ = 28.24° with
100% completeness accomplished. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Pd | 1 | 0.5 | 0 | 0.01186 (13) | |
Cl | 0.97155 (4) | 0.29053 (13) | −0.08021 (6) | 0.0186 (2) | |
P | 0.93002 (4) | 0.64112 (13) | −0.01509 (6) | 0.0128 (2) | |
C2 | 0.75 | 0.75 | 0.6241 (4) | 0.0305 (17) | |
C3 | 0.73621 (19) | 0.6079 (8) | 0.6658 (4) | 0.0478 (17) | |
H3 | 0.7269 | 0.5105 | 0.6393 | 0.057* | |
C4 | 0.7363 (2) | 0.6103 (13) | 0.7465 (5) | 0.078 (3) | |
H4 | 0.7267 | 0.5143 | 0.7739 | 0.094* | |
C5 | 0.75 | 0.75 | 0.7868 (7) | 0.093 (6) | |
H5 | 0.75 | 0.75 | 0.8414 | 0.111* | |
C11 | 0.91269 (15) | 0.7894 (5) | 0.0614 (2) | 0.0146 (9) | |
C12 | 0.93860 (15) | 0.9368 (5) | 0.0735 (2) | 0.0154 (9) | |
H12 | 0.9633 | 0.9604 | 0.0408 | 0.018* | |
C13 | 0.92788 (16) | 1.0482 (6) | 0.1340 (3) | 0.0182 (9) | |
H13 | 0.9455 | 1.1449 | 0.143 | 0.022* | |
C14 | 0.89062 (16) | 1.0120 (6) | 0.1801 (3) | 0.0192 (9) | |
C15 | 0.86344 (16) | 0.8710 (6) | 0.1696 (3) | 0.0199 (9) | |
H15 | 0.8381 | 0.8519 | 0.2014 | 0.024* | |
C16 | 0.87501 (15) | 0.7579 (6) | 0.1104 (2) | 0.0176 (9) | |
H16 | 0.8576 | 0.6601 | 0.103 | 0.021* | |
C21 | 0.88171 (15) | 0.4970 (5) | −0.0273 (2) | 0.0125 (8) | |
C22 | 0.87552 (16) | 0.3660 (6) | 0.0269 (3) | 0.0197 (9) | |
H22 | 0.894 | 0.3619 | 0.0714 | 0.024* | |
C23 | 0.84232 (16) | 0.2418 (6) | 0.0158 (3) | 0.0200 (10) | |
H23 | 0.8378 | 0.1559 | 0.0525 | 0.024* | |
C24 | 0.81626 (15) | 0.2503 (6) | −0.0519 (3) | 0.0208 (10) | |
C25 | 0.82055 (16) | 0.3784 (6) | −0.1058 (3) | 0.0230 (10) | |
H25 | 0.8017 | 0.3826 | −0.1496 | 0.028* | |
C26 | 0.85356 (15) | 0.5014 (5) | −0.0935 (2) | 0.0172 (9) | |
H26 | 0.8571 | 0.5886 | −0.1299 | 0.021* | |
C31 | 0.93143 (15) | 0.7689 (5) | −0.1038 (2) | 0.0148 (8) | |
C32 | 0.95982 (15) | 0.7189 (6) | −0.1655 (3) | 0.0195 (9) | |
H32 | 0.9779 | 0.6223 | −0.16 | 0.023* | |
C33 | 0.96147 (15) | 0.8107 (6) | −0.2349 (3) | 0.0195 (10) | |
H33 | 0.9803 | 0.7777 | −0.2761 | 0.023* | |
C34 | 0.93394 (16) | 0.9529 (6) | −0.2401 (3) | 0.0194 (10) | |
C35 | 0.90526 (17) | 1.0069 (5) | −0.1813 (3) | 0.0215 (10) | |
H35 | 0.8872 | 1.1035 | −0.1875 | 0.026* | |
C36 | 0.90396 (16) | 0.9130 (6) | −0.1124 (3) | 0.0194 (9) | |
H36 | 0.8847 | 0.9462 | −0.0718 | 0.023* | |
F1 | 0.87928 (10) | 1.1238 (3) | 0.23807 (16) | 0.0295 (7) | |
F3 | 0.93550 (10) | 1.0457 (3) | −0.30777 (15) | 0.0251 (6) | |
F2 | 0.78548 (9) | 0.1241 (3) | −0.06494 (18) | 0.0308 (7) | |
C1 | 0.75 | 0.75 | 0.5353 (5) | 0.059 (3) | |
H1A | 0.7605 | 0.8584 | 0.5165 | 0.089* | 0.25 |
H1B | 0.7195 | 0.7297 | 0.5165 | 0.089* | 0.25 |
H1C | 0.77 | 0.6619 | 0.5165 | 0.089* | 0.25 |
H1D | 0.7395 | 0.6416 | 0.5165 | 0.089* | 0.25 |
H1E | 0.7805 | 0.7703 | 0.5165 | 0.089* | 0.25 |
H1F | 0.73 | 0.8381 | 0.5165 | 0.089* | 0.25 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pd | 0.0164 (2) | 0.0094 (2) | 0.0097 (2) | 0.00012 (17) | −0.00014 (17) | −0.00067 (17) |
Cl | 0.0216 (5) | 0.0156 (5) | 0.0185 (5) | −0.0003 (4) | −0.0015 (4) | −0.0065 (4) |
P | 0.0187 (5) | 0.0099 (5) | 0.0097 (5) | −0.0003 (4) | 0.0001 (4) | 0.0003 (4) |
C2 | 0.030 (4) | 0.040 (4) | 0.021 (4) | 0.016 (3) | 0 | 0 |
C3 | 0.031 (3) | 0.045 (4) | 0.068 (5) | 0.011 (3) | −0.005 (3) | 0.014 (3) |
C4 | 0.038 (4) | 0.125 (8) | 0.071 (6) | 0.029 (5) | 0.012 (4) | 0.059 (6) |
C5 | 0.049 (7) | 0.199 (18) | 0.030 (6) | 0.063 (10) | 0 | 0 |
C11 | 0.023 (2) | 0.013 (2) | 0.0077 (19) | 0.0006 (17) | −0.0032 (16) | 0.0006 (16) |
C12 | 0.020 (2) | 0.014 (2) | 0.012 (2) | 0.0021 (17) | −0.0013 (17) | 0.0020 (16) |
C13 | 0.023 (2) | 0.014 (2) | 0.018 (2) | −0.0004 (18) | −0.0018 (18) | −0.0009 (17) |
C14 | 0.030 (3) | 0.017 (2) | 0.011 (2) | 0.0051 (19) | 0.0005 (18) | −0.0058 (17) |
C15 | 0.025 (2) | 0.020 (2) | 0.015 (2) | −0.0004 (19) | 0.0053 (18) | −0.0016 (18) |
C16 | 0.024 (2) | 0.015 (2) | 0.014 (2) | −0.0027 (18) | 0.0001 (18) | −0.0008 (17) |
C21 | 0.020 (2) | 0.0073 (19) | 0.0105 (18) | 0.0004 (16) | −0.0001 (16) | −0.0032 (15) |
C22 | 0.022 (2) | 0.021 (2) | 0.016 (2) | −0.0022 (19) | −0.0036 (18) | −0.0016 (18) |
C23 | 0.026 (2) | 0.014 (2) | 0.020 (2) | −0.0035 (18) | −0.0012 (19) | 0.0036 (17) |
C24 | 0.020 (2) | 0.016 (2) | 0.027 (3) | −0.0048 (17) | −0.0008 (19) | −0.0042 (19) |
C25 | 0.022 (2) | 0.027 (3) | 0.020 (2) | −0.002 (2) | −0.0055 (19) | −0.001 (2) |
C26 | 0.026 (2) | 0.015 (2) | 0.010 (2) | 0.0001 (18) | −0.0020 (17) | 0.0011 (16) |
C31 | 0.021 (2) | 0.0116 (19) | 0.012 (2) | −0.0027 (17) | −0.0016 (17) | −0.0008 (16) |
C32 | 0.019 (2) | 0.018 (2) | 0.022 (2) | 0.0003 (18) | 0.0017 (18) | 0.0006 (19) |
C33 | 0.024 (2) | 0.021 (2) | 0.014 (2) | −0.0016 (19) | 0.0036 (18) | 0.0011 (17) |
C34 | 0.029 (3) | 0.015 (2) | 0.014 (2) | −0.0078 (18) | −0.0059 (19) | 0.0075 (17) |
C35 | 0.032 (3) | 0.013 (2) | 0.020 (2) | 0.002 (2) | −0.0021 (19) | 0.0020 (18) |
C36 | 0.027 (2) | 0.019 (2) | 0.012 (2) | 0.0029 (19) | 0.0026 (18) | −0.0009 (17) |
F1 | 0.0466 (18) | 0.0219 (14) | 0.0201 (14) | −0.0018 (13) | 0.0094 (13) | −0.0127 (12) |
F3 | 0.0416 (17) | 0.0209 (13) | 0.0128 (13) | −0.0032 (12) | −0.0020 (12) | 0.0093 (11) |
F2 | 0.0302 (16) | 0.0220 (15) | 0.0403 (18) | −0.0099 (12) | −0.0093 (13) | 0.0016 (13) |
C1 | 0.068 (7) | 0.072 (7) | 0.037 (5) | 0.026 (6) | 0 | 0 |
Geometric parameters (Å, º) top
Pd—Cli | 2.2955 (13) | C22—C23 | 1.389 (6) |
Pd—Pi | 2.3398 (12) | C22—H22 | 0.93 |
Cl—Pd | 2.2955 (13) | C23—C24 | 1.384 (6) |
P—Pd | 2.3398 (12) | C23—H23 | 0.93 |
C2—C3 | 1.384 (7) | C24—F2 | 1.357 (5) |
C2—C3ii | 1.384 (7) | C24—C25 | 1.369 (7) |
C2—C1 | 1.515 (11) | C25—C26 | 1.381 (6) |
C3—C4 | 1.375 (10) | C25—H25 | 0.93 |
C3—H3 | 0.93 | C26—H26 | 0.93 |
C4—C5 | 1.356 (11) | C31—C32 | 1.396 (6) |
C4—H4 | 0.93 | C31—C36 | 1.396 (6) |
C5—C4ii | 1.356 (11) | C31—P | 1.816 (4) |
C5—H5 | 0.93 | C32—C33 | 1.386 (6) |
C11—C12 | 1.399 (6) | C32—H32 | 0.93 |
C11—C16 | 1.404 (6) | C33—C34 | 1.380 (6) |
C11—P | 1.820 (4) | C33—H33 | 0.93 |
C12—C13 | 1.388 (6) | C34—F3 | 1.366 (5) |
C12—H12 | 0.93 | C34—C35 | 1.373 (7) |
C13—C14 | 1.373 (6) | C35—C36 | 1.388 (6) |
C13—H13 | 0.93 | C35—H35 | 0.93 |
C14—F1 | 1.363 (5) | C36—H36 | 0.93 |
C14—C15 | 1.375 (6) | C1—H1A | 0.96 |
C15—C16 | 1.387 (6) | C1—H1B | 0.96 |
C15—H15 | 0.93 | C1—H1C | 0.96 |
C16—H16 | 0.93 | C1—H1D | 0.96 |
C21—C22 | 1.395 (6) | C1—H1E | 0.96 |
C21—C26 | 1.396 (6) | C1—H1F | 0.96 |
C21—P | 1.822 (4) | | |
| | | |
Cl—Pd—Cli | 180.00 (6) | C26—C25—H25 | 120.8 |
Cl—Pd—Pi | 92.42 (5) | C25—C26—C21 | 121.1 (4) |
Cli—Pd—Pi | 87.58 (5) | C25—C26—H26 | 119.5 |
Cl—Pd—P | 87.58 (5) | C21—C26—H26 | 119.5 |
Cli—Pd—P | 92.42 (5) | C32—C31—C36 | 119.4 (4) |
Pi—Pd—P | 180.00 (3) | C32—C31—P | 119.1 (3) |
C3—C2—C3ii | 118.1 (8) | C36—C31—P | 121.5 (3) |
C3—C2—C1 | 120.9 (4) | C33—C32—C31 | 121.2 (4) |
C3ii—C2—C1 | 120.9 (4) | C33—C32—H32 | 119.4 |
C4—C3—C2 | 120.2 (8) | C31—C32—H32 | 119.4 |
C4—C3—H3 | 119.9 | C34—C33—C32 | 117.1 (4) |
C2—C3—H3 | 119.9 | C34—C33—H33 | 121.4 |
C5—C4—C3 | 121.3 (9) | C32—C33—H33 | 121.4 |
C5—C4—H4 | 119.4 | F3—C34—C35 | 118.2 (4) |
C3—C4—H4 | 119.4 | F3—C34—C33 | 117.9 (4) |
C4—C5—C4ii | 119.0 (11) | C35—C34—C33 | 124.0 (4) |
C4—C5—H5 | 120.5 | C34—C35—C36 | 118.1 (4) |
C4ii—C5—H5 | 120.5 | C34—C35—H35 | 121 |
C12—C11—C16 | 118.8 (4) | C36—C35—H35 | 121 |
C12—C11—P | 119.0 (3) | C35—C36—C31 | 120.3 (4) |
C16—C11—P | 122.1 (3) | C35—C36—H36 | 119.8 |
C13—C12—C11 | 120.6 (4) | C31—C36—H36 | 119.8 |
C13—C12—H12 | 119.7 | C31—P—C11 | 104.42 (19) |
C11—C12—H12 | 119.7 | C31—P—C21 | 105.40 (19) |
C14—C13—C12 | 118.3 (4) | C11—P—C21 | 105.3 (2) |
C14—C13—H13 | 120.9 | C31—P—Pd | 109.49 (15) |
C12—C13—H13 | 120.9 | C11—P—Pd | 117.88 (14) |
F1—C14—C13 | 118.4 (4) | C21—P—Pd | 113.27 (14) |
F1—C14—C15 | 118.2 (4) | C2—C1—H1A | 109.5 |
C13—C14—C15 | 123.4 (4) | C2—C1—H1B | 109.5 |
C14—C15—C16 | 118.0 (4) | H1A—C1—H1B | 109.5 |
C14—C15—H15 | 121 | C2—C1—H1C | 109.5 |
C16—C15—H15 | 121 | H1A—C1—H1C | 109.5 |
C15—C16—C11 | 120.8 (4) | H1B—C1—H1C | 109.5 |
C15—C16—H16 | 119.6 | C2—C1—H1D | 109.5 |
C11—C16—H16 | 119.6 | H1A—C1—H1D | 141.1 |
C22—C21—C26 | 118.5 (4) | H1B—C1—H1D | 56.3 |
C22—C21—P | 118.9 (3) | H1C—C1—H1D | 56.3 |
C26—C21—P | 122.2 (3) | C2—C1—H1E | 109.5 |
C23—C22—C21 | 121.2 (4) | H1A—C1—H1E | 56.3 |
C23—C22—H22 | 119.4 | H1B—C1—H1E | 141.1 |
C21—C22—H22 | 119.4 | H1C—C1—H1E | 56.3 |
C24—C23—C22 | 117.7 (4) | H1D—C1—H1E | 109.5 |
C24—C23—H23 | 121.2 | C2—C1—H1F | 109.5 |
C22—C23—H23 | 121.2 | H1A—C1—H1F | 56.3 |
F2—C24—C25 | 119.2 (4) | H1B—C1—H1F | 56.3 |
F2—C24—C23 | 117.8 (4) | H1C—C1—H1F | 141.1 |
C25—C24—C23 | 123.0 (4) | H1D—C1—H1F | 109.5 |
C24—C25—C26 | 118.5 (4) | H1E—C1—H1F | 109.5 |
C24—C25—H25 | 120.8 | | |
| | | |
Cl—Pd—P—C11 | 155.65 (16) | Cl—Pd—P—C31 | −85.26 (15) |
Cl—Pd—P—C21 | 32.06 (15) | | |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+3/2, −y+3/2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···Cli | 0.93 | 2.82 | 3.177 (4) | 104 |
C22—H22···F3iii | 0.93 | 2.50 | 3.391 (5) | 161 |
C33—H33···Cliv | 0.93 | 2.83 | 3.714 (5) | 160 |
C35—H35···F1v | 0.93 | 2.50 | 3.299 (5) | 144 |
Symmetry codes: (i) −x+2, −y+1, −z; (iii) x, −y+3/2, z+1/2; (iv) −x+2, y+1/2, −z−1/2; (v) x, −y+5/2, z−1/2. |
Comparative bond distances (Å) for selected
trans-[PdCl2(L)2]
(L = tertiary phosphine ligand) complexes topL | Pd-P (Å) | Pd-Cl (Å) | Notes |
PPh3 | 2.337 (1) | 2.290 (1) | i |
PPh3 | 2.345 (1) | 2.296 (1) | ii |
| 2.353 (1) | 2.281 (1) | |
P(C6H4F)3 | 2.3398 (12) | 2.2955 (13) | TW |
P(m-tol)3 | 2.3289 (4) | 2.2897 (4) | iii |
PPh(tBu)2 | 2.398 (2) | 2.301 (2) | iv |
PPh2Cy | 2.3257 (9) | 2.2995 (9) | v |
PPh2[p-(tBuNO)Ph] | 2.3298 (6) | 2.2865 (7) | vi |
PPh2CHCO2H | 2.326 (1) | 2.305 (1) | vii |
PPh2(NC5H10) | 2.324 (2) | 2.289 (2) | viii |
PCy3 | 2.3628 (9) | 2.3012 (9) | ix |
Notes: Cy is cyclohexyl; TW is this work; (i) Ferguson et al.
(1982);
(ii) Kitano et al. (1983); (iii) Meijboom et al.
(2006b); (iv) DiMeglio et al.
(1990); (v) Meij et al. (2003); (vi) Leznoff et
al. (1999); (vii) Edwards et al. (1998); (viii)
Burrow et al. (1994); (ix) Grushin et al.
(1994). |