trans-Dichloro­bis[N-(3,5-difluoro­phen­yl)isopropyl­ideneamine]palladium(II)

The title compound, [PdCl₂(C₉H₉F₂N)₂], was obtained from the condensation reaction of acetone with trans-dichloro­bis(3,5-difluoro­aniline)palladium(II) under crystallization conditions. The Pd atom lies on an inversion centre and shows a square-planar geometry. The mol­ecules are linked via non-classical C—H...Cl and C—H...F inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.027
• wR factor = 0.059
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT027_ALERT_3_B _diffrn_reflns_theta_full (too) Low ............      24.99 Deg.

Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.03

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   1 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
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

Palladium complexes have acquired tremendous importance in recent years due to the main role that palladium has gained in the realm of metal-mediated organic synthesis (Negishi & De Meijere, 2002), becoming a keystone in processes otherwise difficult to achieve or even impossible without the presence of the metal complex, such as the arylation of olefins (Heck reaction; Beletskaya & Cheprakov, 2000). In fact, similar complexes have been successfully employed in this process allowing fine-tuning of electronic effects (Baldovino-Pantaleón et al., 2005b), given the facility of modifying the number and disposition of the F atoms in the aromatic ring of the aniline. In this paper, we report the crystal structure of the title compound, (I), as one of a series of compounds we have studied in the course of our research into the synthesis of transition metal complexes bearing fluorinated ligands (Redón et al., 2003, 2002, 2001; Arroyo et al., 2003; Morales-Morales et al., 2001; García et al., 1993, Herrera-Alvarez et al., 2004; Fierro-Arias et al., 2005; Baldovino-Pantaleón et al., 2005a or b?).

Fig. 1 shows the Pd metal centre of (I) to be in a centrosymmetric square-planar environment, with the 3,5-difluorophenylisopropylideneamine and Cl ligands in trans positions. The isopropylideneamine group [r.m.s. deviation 0.0011 (2) Å] makes a dihedral angle of 83.8 (1)° with the plane formed by atoms Pd1/Cl1/N1/Cl1ⁱ/N1ⁱ [symmetry code: (i) 1 − x, 1 − y, 1 − z], and the 3,5-difluorophenyl substituent (r.m.s. deviation 0.0054 Å) makes an angle of 73.55 (9)° with the coordination plane. The corresponding angles in dichlorobis(N-isopropylideneaniline-N)palladium(II) are 88.1 and 66.8°, respectively (Clegg et al., 1987).

The crystal packing of (I) (Fig. 2) shows non-classical C—H···Cl/F hydrogen bonds (Table 2).

S2. Experimental

Compound (I) was obtained from the condensation reaction of the bis(3,5-difluoroaniline) complex trans-[PdCl₂(C₉H₉F₂N)₂] (Baldovino-Pantaleón et al., 2005b) with acetone, after standing for 4 d under crystallization conditions.

S3. Refinement

H atoms were included in calculated positions, with C—H = 0.96–0.98 Å, and refined using a riding model, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL/PC (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL/PC.

Figures

	Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Unlabelled atoms are related to labelled atoms by the symmetry operator (1 − x, 1 − y, 1 − z).
	Fig. 2. The crystal packing of (I). Dashed lines indicate C—H···Cl/F interactions.

trans-Dichlorobis[N-(3,5-difluorophenyl)isopropylideneamine]palladium(II)

Crystal data

[PdCl2(C9H9F2N)2]	Z = 1
Mr = 515.64	F(000) = 256
Triclinic, P1	Dx = 1.702 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7654 (7) Å	Cell parameters from 3473 reflections
b = 7.9246 (7) Å	θ = 2.5–30.7°
c = 9.3977 (8) Å	µ = 1.23 mm^−1
α = 113.735 (2)°	T = 291 K
β = 105.458 (2)°	Prism, yellow
γ = 92.253 (2)°	0.12 × 0.10 × 0.08 mm
V = 503.15 (8) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	1781 independent reflections
Radiation source: fine-focus sealed tube	1710 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 0.661 pixels mm^-1	θmax = 25.0°, θmin = 2.5°
ω scans	h = −9→9
Absorption correction: analytical (SHELXTL; Sheldrick, 1997b)	k = −9→9
Tmin = 0.867, Tmax = 0.908	l = −11→11
4178 measured reflections

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.059	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0285P)^2] where P = (Fo^2 + 2Fc^2)/3
1781 reflections	(Δ/σ)max = 0.004
126 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

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
Pd1	0.5000	0.5000	0.5000	0.04124 (12)
Cl1	0.27632 (10)	0.25261 (10)	0.42028 (11)	0.0658 (2)
F1	0.1188 (3)	0.7515 (3)	0.9420 (3)	0.1045 (8)
F2	0.3931 (3)	1.2686 (3)	0.9185 (3)	0.1016 (7)
N1	0.3120 (3)	0.6651 (3)	0.4810 (3)	0.0416 (5)
C1	0.2884 (3)	0.7856 (4)	0.6344 (3)	0.0442 (6)
C2	0.2123 (4)	0.7065 (4)	0.7143 (4)	0.0572 (8)
H2	0.1728	0.5784	0.6697	0.069*
C3	0.1972 (4)	0.8258 (5)	0.8634 (4)	0.0660 (9)
C4	0.2568 (4)	1.0135 (5)	0.9365 (4)	0.0660 (9)
H4	0.2463	1.0899	1.0381	0.079*
C5	0.3329 (4)	1.0831 (4)	0.8517 (4)	0.0619 (8)
C6	0.3501 (4)	0.9744 (4)	0.7011 (3)	0.0548 (7)
H6	0.4017	1.0267	0.6464	0.066*
C7	0.2639 (5)	0.5535 (4)	0.1944 (3)	0.0651 (8)
H7A	0.3689	0.4989	0.2210	0.078*
H7B	0.2877	0.6316	0.1436	0.078*
H7C	0.1630	0.4562	0.1206	0.078*
C8	0.2205 (4)	0.6680 (4)	0.3465 (3)	0.0477 (7)
C9	0.0712 (4)	0.7783 (4)	0.3312 (4)	0.0619 (8)
H9A	0.0293	0.8126	0.4249	0.074*
H9B	−0.0270	0.7043	0.2340	0.074*
H9C	0.1151	0.8892	0.3248	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.04240 (19)	0.03710 (18)	0.04577 (19)	0.01298 (13)	0.01555 (13)	0.01749 (13)
Cl1	0.0551 (5)	0.0475 (4)	0.0936 (6)	0.0061 (4)	0.0236 (4)	0.0287 (4)
F1	0.140 (2)	0.1195 (18)	0.0966 (16)	0.0315 (16)	0.0734 (15)	0.0640 (15)
F2	0.139 (2)	0.0571 (13)	0.0893 (15)	0.0078 (13)	0.0595 (15)	−0.0015 (11)
N1	0.0433 (12)	0.0374 (12)	0.0446 (12)	0.0128 (10)	0.0151 (10)	0.0165 (10)
C1	0.0421 (15)	0.0478 (16)	0.0451 (15)	0.0186 (13)	0.0153 (12)	0.0201 (13)
C2	0.064 (2)	0.0526 (18)	0.0610 (19)	0.0168 (15)	0.0239 (16)	0.0270 (15)
C3	0.070 (2)	0.087 (3)	0.064 (2)	0.0291 (19)	0.0337 (18)	0.046 (2)
C4	0.070 (2)	0.077 (2)	0.0513 (18)	0.0292 (19)	0.0271 (16)	0.0200 (18)
C5	0.068 (2)	0.0507 (19)	0.0591 (19)	0.0156 (16)	0.0243 (16)	0.0123 (15)
C6	0.0637 (19)	0.0479 (17)	0.0562 (18)	0.0150 (15)	0.0289 (15)	0.0186 (14)
C7	0.083 (2)	0.0613 (19)	0.0472 (17)	0.0192 (18)	0.0189 (16)	0.0201 (15)
C8	0.0532 (17)	0.0386 (15)	0.0511 (16)	0.0102 (13)	0.0163 (14)	0.0188 (13)
C9	0.0625 (19)	0.0564 (19)	0.0654 (19)	0.0208 (16)	0.0121 (16)	0.0285 (16)

Geometric parameters (Å, º)

Pd1—N1^i	2.0185 (19)	C4—C5	1.366 (5)
Pd1—N1	2.0185 (19)	C4—H4	0.9300
Pd1—Cl1^i	2.2974 (7)	C5—C6	1.376 (4)
Pd1—Cl1	2.2974 (7)	C6—H6	0.9300
F1—C3	1.351 (4)	C7—C8	1.488 (4)
F2—C5	1.349 (3)	C7—H7A	0.9600
N1—C8	1.285 (3)	C7—H7B	0.9600
N1—C1	1.438 (3)	C7—H7C	0.9600
C1—C6	1.375 (4)	C8—C9	1.490 (4)
C1—C2	1.375 (4)	C9—H9A	0.9600
C2—C3	1.379 (4)	C9—H9B	0.9600
C2—H2	0.9300	C9—H9C	0.9600
C3—C4	1.362 (4)
N1^i—Pd1—N1	180.000 (1)	F2—C5—C4	118.4 (3)
N1^i—Pd1—Cl1^i	90.49 (6)	F2—C5—C6	118.1 (3)
N1—Pd1—Cl1^i	89.51 (6)	C4—C5—C6	123.5 (3)
N1^i—Pd1—Cl1	89.51 (6)	C1—C6—C5	117.6 (3)
N1—Pd1—Cl1	90.49 (6)	C1—C6—H6	121.2
Cl1^i—Pd1—Cl1	180.000 (1)	C5—C6—H6	121.2
C8—N1—C1	121.3 (2)	C8—C7—H7A	109.5
C8—N1—Pd1	124.61 (18)	C8—C7—H7B	109.5
C1—N1—Pd1	114.09 (15)	H7A—C7—H7B	109.5
C6—C1—C2	121.7 (3)	C8—C7—H7C	109.5
C6—C1—N1	119.5 (2)	H7A—C7—H7C	109.5
C2—C1—N1	118.7 (2)	H7B—C7—H7C	109.5
C1—C2—C3	117.0 (3)	N1—C8—C7	118.6 (2)
C1—C2—H2	121.5	N1—C8—C9	124.3 (3)
C3—C2—H2	121.5	C7—C8—C9	117.1 (2)
F1—C3—C4	118.0 (3)	C8—C9—H9A	109.5
F1—C3—C2	117.9 (3)	C8—C9—H9B	109.5
C4—C3—C2	124.1 (3)	H9A—C9—H9B	109.5
C3—C4—C5	116.1 (3)	C8—C9—H9C	109.5
C3—C4—H4	122.0	H9A—C9—H9C	109.5
C5—C4—H4	122.0	H9B—C9—H9C	109.5
Cl1^i—Pd1—N1—C8	99.0 (2)	F1—C3—C4—C5	−179.1 (3)
Cl1—Pd1—N1—C8	−81.0 (2)	C2—C3—C4—C5	1.1 (5)
Cl1^i—Pd1—N1—C1	−80.18 (17)	C3—C4—C5—F2	179.6 (3)
Cl1—Pd1—N1—C1	99.82 (17)	C3—C4—C5—C6	0.2 (5)
C8—N1—C1—C6	−70.9 (3)	C2—C1—C6—C5	−0.1 (4)
Pd1—N1—C1—C6	108.3 (2)	N1—C1—C6—C5	−176.8 (2)
C8—N1—C1—C2	112.3 (3)	F2—C5—C6—C1	179.9 (3)
Pd1—N1—C1—C2	−68.5 (3)	C4—C5—C6—C1	−0.6 (5)
C6—C1—C2—C3	1.3 (4)	C1—N1—C8—C7	174.2 (2)
N1—C1—C2—C3	178.0 (2)	Pd1—N1—C8—C7	−5.0 (4)
C1—C2—C3—F1	178.4 (3)	C1—N1—C8—C9	−6.2 (4)
C1—C2—C3—C4	−1.8 (5)	Pd1—N1—C8—C9	174.6 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···F1^ii	0.96	2.54	3.327 (5)	140
C7—H7C···F1^iii	0.96	2.47	3.351 (4)	153
C9—H9C···Cl1^iv	0.96	2.78	3.694 (3)	161

Symmetry codes: (ii) x, y, z−1; (iii) −x, −y+1, −z+1; (iv) x, y+1, z.