trans-Dichloro­bis[tris(4-fluoro­phen­yl)­phosphine]palladium(II) toluene solvate

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.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](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

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Computing details

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

Crystal data

[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) Å^3	Plate, yellow
Z = 4	0.32 × 0.12 × 0.04 mm

Data collection

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

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.052	w = 1/[σ^2(Fo^2) + (0.0553P)^2 + 10.4167P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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

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, ¹J_F—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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Pd—Cl^i	2.2955 (13)	C22—C23	1.389 (6)
Pd—P^i	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—C3^ii	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—C4^ii	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—Cl^i	180.00 (6)	C26—C25—H25	120.8
Cl—Pd—P^i	92.42 (5)	C25—C26—C21	121.1 (4)
Cl^i—Pd—P^i	87.58 (5)	C25—C26—H26	119.5
Cl—Pd—P	87.58 (5)	C21—C26—H26	119.5
Cl^i—Pd—P	92.42 (5)	C32—C31—C36	119.4 (4)
P^i—Pd—P	180.00 (3)	C32—C31—P	119.1 (3)
C3—C2—C3^ii	118.1 (8)	C36—C31—P	121.5 (3)
C3—C2—C1	120.9 (4)	C33—C32—C31	121.2 (4)
C3^ii—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—C4^ii	119.0 (11)	C35—C34—C33	124.0 (4)
C4—C5—H5	120.5	C34—C35—C36	118.1 (4)
C4^ii—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)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Cl^i	0.93	2.82	3.177 (4)	104
C22—H22···F3^iii	0.93	2.50	3.391 (5)	161
C33—H33···Cl^iv	0.93	2.83	3.714 (5)	160
C35—H35···F1^v	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.