(4-Fluoro-phen-yl-κC)(N,N,N',N'-tetra-methyl-ethylenedi-amine-κ(2) N,N')(tri-fluoro-meth-yl-κC)palladium(II).

In the title compound, [Pd(CF3)(C6H4F)(C6H16N2)], the Pd(II) cation is four-coordinated by the two N atoms of the N,N,N',N'-tetra-methyl-ethylenedi-amine ligand and by one C atom each from a 4-fluoro-phenyl and a tri-fluoro-methyl ligand, in a distorted rectangular-planar geometry, with an average deviation from the least-squares plane of 0.066 (2) Å. The central coordination angles with the Pd(II) atom range from 83.14 (10) to 97.25 (12)°.

Related literature

For metal-mediated C—F bond-breaking and C—C bond-formation reactions in similar compounds, see: Maleckis & Sanford (2011 ▶); Ball et al. (2010 ▶, 2011 ▶); Ye et al. (2010 ▶); Racowski et al. (2011 ▶). For similar PdII—CF3 bonds, see: Grushin & Marshall (2006 ▶).

Experimental

Crystal data

[Pd(CF3)(C6H4F)(C6H8N2)]

M = 386.71

Monoclinic,

a = 16.6651 (19) Å

b = 8.3464 (9) Å

c = 11.4710 (13) Å

β = 103.063 (2)°

V = 1554.3 (3) Å3

Z = 4

Mo Kα radiation

μ = 1.23 mm−1

T = 296 K

0.29 × 0.27 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.717, T max = 0.800

8555 measured reflections

2875 independent reflections

2628 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.067

S = 1.04

2875 reflections

180 parameters

H-atom parameters constrained

Δρmax = 0.56 e Å−3

Δρmin = −0.42 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814007855/vn2082sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814007855/vn2082Isup2.hkl

CCDC reference: 996158

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Pd(CF3)(C6H4F)(C6H16N2)]	F(000) = 776
Mr = 386.71	Dx = 1.653 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6327 reflections
a = 16.6651 (19) Å	θ = 2.5–28.3°
b = 8.3464 (9) Å	µ = 1.23 mm−1
c = 11.4710 (13) Å	T = 296 K
β = 103.063 (2)°	Block, colourless
V = 1554.3 (3) Å3	0.29 × 0.27 × 0.19 mm
Z = 4

Bruker APEXII CCD diffractometer	2875 independent reflections
Radiation source: fine-focus sealed tube	2628 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
φ and ω scans	θmax = 25.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −20→19
Tmin = 0.717, Tmax = 0.800	k = −7→10
8555 measured reflections	l = −13→13

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)] = 0.026	H-atom parameters constrained
wR(F2) = 0.067	w = 1/[σ2(Fo2) + (0.0257P)2 + 1.3072P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
2875 reflections	Δρmax = 0.56 e Å−3
180 parameters	Δρmin = −0.42 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0130 (7)

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
C1	0.1947 (3)	0.3541 (4)	−0.1824 (3)	0.0676 (10)
H1A	0.1625	0.2614	−0.2124	0.101*
H1B	0.2458	0.3510	−0.2077	0.101*
H1C	0.1649	0.4492	−0.2130	0.101*
C2	0.1308 (2)	0.3660 (4)	−0.0178 (4)	0.0697 (10)
H2A	0.1389	0.3639	0.0677	0.104*
H2B	0.0969	0.2770	−0.0517	0.104*
H2C	0.1041	0.4643	−0.0482	0.104*
C3	0.2600 (3)	0.4968 (4)	−0.0004 (4)	0.0770 (12)
H3A	0.2441	0.5870	−0.0539	0.092*
H3B	0.2472	0.5237	0.0757	0.092*
C4	0.3477 (2)	0.4711 (5)	0.0176 (5)	0.0831 (13)
H4A	0.3763	0.5657	0.0548	0.100*
H4B	0.3611	0.4580	−0.0599	0.100*
C5	0.3906 (3)	0.3625 (5)	0.2209 (4)	0.0832 (14)
H5A	0.4169	0.2726	0.2661	0.125*
H5B	0.3382	0.3815	0.2399	0.125*
H5C	0.4247	0.4558	0.2406	0.125*
C6	0.4590 (2)	0.2862 (5)	0.0683 (4)	0.0691 (10)
H6A	0.4948	0.3776	0.0825	0.104*
H6B	0.4514	0.2533	−0.0137	0.104*
H6C	0.4831	0.2000	0.1199	0.104*
C7	0.12779 (18)	−0.0466 (4)	−0.0076 (3)	0.0492 (7)
H7	0.1232	−0.0043	0.0656	0.059*
C8	0.0662 (2)	−0.1472 (4)	−0.0689 (4)	0.0658 (10)
H8	0.0208	−0.1718	−0.0378	0.079*
C9	0.0738 (2)	−0.2090 (4)	−0.1757 (4)	0.0658 (10)
C10	0.1397 (3)	−0.1777 (4)	−0.2232 (3)	0.0675 (11)
H10	0.1438	−0.2216	−0.2961	0.081*
C11	0.2004 (2)	−0.0786 (4)	−0.1598 (3)	0.0557 (8)
H11	0.2465	−0.0585	−0.1904	0.067*
C12	0.19541 (17)	−0.0076 (3)	−0.0519 (2)	0.0389 (6)
C13	0.34552 (19)	−0.0443 (4)	0.1069 (3)	0.056
F1	0.30400 (16)	−0.1597 (3)	0.1466 (3)	0.0905 (8)
F2	0.40331 (16)	−0.0049 (3)	0.2069 (3)	0.1081 (10)
F3	0.3877 (2)	−0.1208 (3)	0.0386 (3)	0.1207 (12)
F4	0.01374 (16)	−0.3096 (3)	−0.2362 (3)	0.1088 (10)
N1	0.21161 (16)	0.3549 (3)	−0.0509 (2)	0.0455 (6)
N2	0.37856 (16)	0.3287 (3)	0.0931 (2)	0.0483 (6)
Pd1	0.282550 (12)	0.14760 (2)	0.027333 (17)	0.03517 (11)

	U11	U22	U33	U12	U13	U23
C1	0.092 (3)	0.062 (2)	0.0461 (18)	0.0159 (19)	0.0097 (18)	0.0128 (15)
C2	0.070 (2)	0.062 (2)	0.082 (3)	0.0226 (18)	0.027 (2)	0.0115 (19)
C3	0.080 (3)	0.0372 (19)	0.101 (3)	−0.0030 (18)	−0.006 (2)	0.0041 (19)
C4	0.071 (3)	0.045 (2)	0.132 (4)	−0.0135 (18)	0.019 (2)	0.009 (2)
C5	0.076 (3)	0.109 (4)	0.067 (2)	−0.034 (2)	0.022 (2)	−0.039 (2)
C6	0.0481 (19)	0.087 (3)	0.075 (2)	−0.0154 (19)	0.0203 (17)	−0.011 (2)
C7	0.0449 (16)	0.0494 (18)	0.0536 (17)	−0.0037 (14)	0.0119 (13)	−0.0032 (14)
C8	0.0386 (17)	0.060 (2)	0.097 (3)	−0.0064 (15)	0.0099 (18)	0.0007 (19)
C9	0.056 (2)	0.0447 (19)	0.079 (2)	−0.0073 (16)	−0.0217 (19)	−0.0024 (18)
C10	0.099 (3)	0.0480 (19)	0.0467 (18)	−0.0103 (19)	−0.0019 (19)	−0.0066 (15)
C11	0.074 (2)	0.0457 (18)	0.0504 (17)	−0.0156 (16)	0.0212 (16)	−0.0048 (15)
C12	0.0413 (14)	0.0342 (14)	0.0388 (13)	−0.0015 (11)	0.0038 (11)	0.0021 (11)
C13	0.044	0.049	0.072	−0.003	0.008	−0.006
F1	0.0801 (16)	0.0650 (15)	0.118 (2)	0.0029 (11)	0.0049 (14)	0.0432 (13)
F2	0.0912 (18)	0.0810 (17)	0.119 (2)	0.0006 (14)	−0.0460 (16)	0.0218 (15)
F3	0.129 (2)	0.098 (2)	0.154 (3)	0.0678 (19)	0.071 (2)	0.0274 (19)
F4	0.0831 (17)	0.0773 (16)	0.135 (2)	−0.0264 (14)	−0.0406 (16)	−0.0194 (16)
N1	0.0537 (15)	0.0382 (14)	0.0420 (13)	0.0000 (10)	0.0050 (11)	0.0040 (10)
N2	0.0434 (13)	0.0466 (14)	0.0544 (15)	−0.0089 (11)	0.0100 (11)	−0.0056 (12)
Pd1	0.03454 (14)	0.03201 (14)	0.03823 (14)	−0.00229 (8)	0.00669 (9)	−0.00038 (8)

C1—N1	1.471 (4)	C6—H6B	0.9600
C1—H1A	0.9600	C6—H6C	0.9600
C1—H1B	0.9600	C7—C12	1.375 (4)
C1—H1C	0.9600	C7—C8	1.388 (5)
C2—N1	1.483 (5)	C7—H7	0.9300
C2—H2A	0.9600	C8—C9	1.361 (6)
C2—H2B	0.9600	C8—H8	0.9300
C2—H2C	0.9600	C9—C10	1.357 (6)
C3—C4	1.446 (6)	C9—F4	1.369 (4)
C3—N1	1.475 (4)	C10—C11	1.379 (5)
C3—H3A	0.9700	C10—H10	0.9300
C3—H3B	0.9700	C11—C12	1.392 (4)
C4—N2	1.492 (5)	C11—H11	0.9300
C4—H4A	0.9700	Pd1—C12	2.004 (3)
C4—H4B	0.9700	C13—F1	1.325 (4)
C5—N2	1.462 (5)	C13—F3	1.329 (4)
C5—H5A	0.9600	C13—F2	1.361 (4)
C5—H5B	0.9600	Pd1—C13	2.017 (3)
C5—H5C	0.9600	Pd1—N1	2.172 (2)
C6—N2	1.475 (4)	Pd1—N2	2.206 (2)
C6—H6A	0.9600
N1—C1—H1A	109.5	C9—C8—C7	118.5 (4)
N1—C1—H1B	109.5	C9—C8—H8	120.8
H1A—C1—H1B	109.5	C7—C8—H8	120.8
N1—C1—H1C	109.5	C10—C9—C8	122.4 (3)
H1A—C1—H1C	109.5	C10—C9—F4	118.7 (4)
H1B—C1—H1C	109.5	C8—C9—F4	118.9 (4)
N1—C2—H2A	109.5	C9—C10—C11	117.9 (3)
N1—C2—H2B	109.5	C9—C10—H10	121.1
H2A—C2—H2B	109.5	C11—C10—H10	121.1
N1—C2—H2C	109.5	C10—C11—C12	122.7 (3)
H2A—C2—H2C	109.5	C10—C11—H11	118.7
H2B—C2—H2C	109.5	C12—C11—H11	118.7
C4—C3—N1	112.4 (3)	C7—C12—C11	116.5 (3)
C4—C3—H3A	109.1	C7—C12—Pd1	123.8 (2)
N1—C3—H3A	109.1	C11—C12—Pd1	119.7 (2)
C4—C3—H3B	109.1	F1—C13—F3	103.9 (3)
N1—C3—H3B	109.1	F1—C13—F2	102.2 (3)
H3A—C3—H3B	107.8	F3—C13—F2	104.2 (3)
C3—C4—N2	113.9 (3)	F1—C13—Pd1	118.3 (2)
C3—C4—H4A	108.8	F3—C13—Pd1	113.9 (3)
N2—C4—H4A	108.8	F2—C13—Pd1	112.8 (2)
C3—C4—H4B	108.8	C1—N1—C3	111.6 (3)
N2—C4—H4B	108.8	C1—N1—C2	106.8 (3)
H4A—C4—H4B	107.7	C3—N1—C2	107.2 (3)
N2—C5—H5A	109.5	C1—N1—Pd1	112.3 (2)
N2—C5—H5B	109.5	C3—N1—Pd1	106.2 (2)
H5A—C5—H5B	109.5	C2—N1—Pd1	112.7 (2)
N2—C5—H5C	109.5	C5—N2—C6	108.4 (3)
H5A—C5—H5C	109.5	C5—N2—C4	112.3 (3)
H5B—C5—H5C	109.5	C6—N2—C4	106.8 (3)
N2—C6—H6A	109.5	C5—N2—Pd1	113.6 (2)
N2—C6—H6B	109.5	C6—N2—Pd1	112.9 (2)
H6A—C6—H6B	109.5	C4—N2—Pd1	102.7 (2)
N2—C6—H6C	109.5	C12—Pd1—C13	86.65 (12)
H6A—C6—H6C	109.5	C12—Pd1—N1	93.25 (10)
H6B—C6—H6C	109.5	C13—Pd1—N1	177.08 (12)
C12—C7—C8	122.0 (3)	C12—Pd1—N2	173.23 (10)
C12—C7—H7	119.0	C13—Pd1—N2	97.25 (12)
C8—C7—H7	119.0	N1—Pd1—N2	83.14 (10)
N1—C3—C4—N2	−55.4 (5)	C11—C12—Pd1—N1	95.3 (2)
C12—C7—C8—C9	0.3 (5)	F1—C13—Pd1—C12	−40.6 (3)
C7—C8—C9—C10	1.0 (6)	F3—C13—Pd1—C12	81.9 (3)
C7—C8—C9—F4	179.4 (3)	F2—C13—Pd1—C12	−159.6 (3)
C8—C9—C10—C11	−0.3 (6)	F1—C13—Pd1—N2	145.0 (3)
F4—C9—C10—C11	−178.7 (3)	F3—C13—Pd1—N2	−92.6 (3)
C9—C10—C11—C12	−1.6 (5)	F2—C13—Pd1—N2	25.9 (3)
C8—C7—C12—C11	−2.1 (5)	C1—N1—Pd1—C12	−61.5 (2)
C8—C7—C12—Pd1	176.0 (2)	C3—N1—Pd1—C12	176.3 (2)
C10—C11—C12—C7	2.8 (5)	C2—N1—Pd1—C12	59.1 (2)
C10—C11—C12—Pd1	−175.4 (3)	C1—N1—Pd1—N2	112.8 (2)
C4—C3—N1—C1	−87.2 (4)	C3—N1—Pd1—N2	−9.5 (2)
C4—C3—N1—C2	156.3 (4)	C2—N1—Pd1—N2	−126.6 (2)
C4—C3—N1—Pd1	35.5 (4)	C5—N2—Pd1—C13	−71.4 (3)
C3—C4—N2—C5	−80.8 (4)	C6—N2—Pd1—C13	52.6 (3)
C3—C4—N2—C6	160.5 (4)	C4—N2—Pd1—C13	167.1 (3)
C3—C4—N2—Pd1	41.5 (4)	C5—N2—Pd1—N1	105.7 (3)
C7—C12—Pd1—C13	94.4 (3)	C6—N2—Pd1—N1	−130.4 (2)
C11—C12—Pd1—C13	−87.6 (3)	C4—N2—Pd1—N1	−15.8 (2)
C7—C12—Pd1—N1	−82.7 (3)

Table 1

Selected bond lengths (Å)

Pd1—C12	2.004 (3)
Pd1—C13	2.017 (3)
Pd1—N1	2.172 (2)
Pd1—N2	2.206 (2)