Crystal structure of (4-fluoro-phenyl-κC (1))iodido-(N,N,N',N'-tetra-methyl-ethylenedi-amine-κ(2) N,N')palladium(II).

In the title compound, [Pd(C6H4F)I(C6H16N2)], the Pd(II) atom is coordinated by two N atoms from the N,N,N',N'-tetra-methyl-ethylenedi-amine ligand, a C atom of the 4-fluoro-phenyl group and an iodide ligand in a distorted square-planar geometry, with an average deviation from the least-squares plane through the ligand donor atoms of 0.0159 (2) Å. The angles about the Pd(II) atom range from 83.35 (16) to 178.59 (11)°. In the crystal, weak C-H⋯F and C-H⋯I hydrogen bonds link the mol-ecules into sheets in the bc plane.

Related literature

For related palladium complexes with PdII—I bonds, see: Racowski et al. (2011 ▸); Grushin & Marshall (2006 ▸); Ball et al. (2010 ▸). For the role of iodido palladium aryl complexes in coupling reactions, see: Hartwig (2008 ▸); Wu et al. (2010 ▸); and as precursors to tri­fluoro­methyl palladium aryl complexes, see: Maleckis & Sanford (2011 ▸); Ball et al. (2010 ▸); Ye et al. (2010 ▸); Racowski et al. (2011 ▸); Ball et al. (2011 ▸); Grushin & Marshall (2006 ▸); Du & Zheng (2014 ▸). For a related palladium complex with a PdII—C bond, see: Du & Zheng (2014 ▸).

Experimental

Crystal data

[Pd(C6H4F)I(C6H16N2)]

M = 444.60

Monoclinic,

a = 9.456 (2) Å

b = 12.802 (3) Å

c = 24.953 (5) Å

β = 93.152 (2)°

V = 3015.9 (11) Å3

Z = 8

Mo Kα radiation

μ = 3.27 mm−1

T = 296 K

0.26 × 0.24 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▸) T min = 0.483, T max = 0.561

10757 measured reflections

2827 independent reflections

2736 reflections with I > 2σ(I)

R int = 0.058

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.120

S = 1.00

2827 reflections

158 parameters

H-atom parameters constrained

Δρmax = 1.15 e Å−3

Δρmin = −1.76 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/S2056989015008014/sj5451sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015008014/sj5451Isup2.hkl

Click here for additional data file.

p . DOI: 10.1107/S2056989015008014/sj5451fig1.tif

The mol­ecular structure of [(tmeda)Pd(p-FPh)(I)], with the atom-numbering scheme and 30% probability displacement ellipsoids.

Click here for additional data file.

p a . DOI: 10.1107/S2056989015008014/sj5451fig2.tif

The mol­ecular packing of [(tmeda)Pd(p-FPh)(I)] viewed along the a axis showing C—H⋯F and C—H⋯I inter­actions as dashed lines.

CCDC reference: 1061123

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

[Pd(C6H4F)I(C6H16N2)]	F(000) = 1712
Mr = 444.60	Dx = 1.958 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8524 reflections
a = 9.456 (2) Å	θ = 2.7–28.3°
b = 12.802 (3) Å	µ = 3.27 mm−1
c = 24.953 (5) Å	T = 296 K
β = 93.152 (2)°	Block, colorless
V = 3015.9 (11) Å3	0.26 × 0.24 × 0.20 mm
Z = 8

Bruker APEXII CCD diffractometer	2827 independent reflections
Radiation source: fine-focus sealed tube	2736 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
φ and ω scans	θmax = 25.6°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −11→11
Tmin = 0.483, Tmax = 0.561	k = −15→11
10757 measured reflections	l = −30→30

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0848P)2 + 14.1377P] where P = (Fo2 + 2Fc2)/3
2827 reflections	(Δ/σ)max = 0.001
158 parameters	Δρmax = 1.15 e Å−3
0 restraints	Δρmin = −1.76 e Å−3

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
Pd1	0.26525 (4)	0.69994 (3)	0.390741 (13)	0.01328 (16)
I1	0.52911 (4)	0.74248 (3)	0.412548 (15)	0.02671 (17)
N2	0.2556 (4)	0.5701 (3)	0.44807 (16)	0.0182 (8)
N1	0.0479 (4)	0.6607 (3)	0.37289 (17)	0.0182 (9)
C4	0.1050 (6)	0.5433 (4)	0.4489 (2)	0.0273 (12)
H4A	0.0597	0.5893	0.4737	0.033*
H4B	0.0956	0.4722	0.4617	0.033*
C7	0.2585 (5)	0.8106 (4)	0.3346 (2)	0.0188 (10)
C9	0.2906 (6)	0.8594 (5)	0.2421 (2)	0.0304 (12)
H9	0.3254	0.8453	0.2087	0.036*
C5	0.3356 (6)	0.4817 (4)	0.4266 (2)	0.0243 (11)
H5A	0.3259	0.4216	0.4491	0.036*
H5B	0.4339	0.5002	0.4258	0.036*
H5C	0.2990	0.4659	0.3908	0.036*
C12	0.1910 (5)	0.9053 (4)	0.3415 (2)	0.0206 (10)
H12	0.1600	0.9221	0.3751	0.025*
C11	0.1680 (6)	0.9762 (4)	0.2996 (2)	0.0245 (11)
H11	0.1202	1.0386	0.3047	0.029*
C8	0.3101 (6)	0.7898 (4)	0.2838 (2)	0.0260 (12)
H8	0.3584	0.7277	0.2783	0.031*
C1	−0.0461 (6)	0.7340 (5)	0.3997 (3)	0.0280 (12)
H1A	−0.0455	0.8004	0.3819	0.042*
H1B	−0.0130	0.7425	0.4365	0.042*
H1C	−0.1407	0.7066	0.3982	0.042*
C2	0.0035 (6)	0.6583 (5)	0.3150 (2)	0.0296 (12)
H2A	0.0678	0.6153	0.2963	0.044*
H2B	0.0045	0.7280	0.3008	0.044*
H2C	−0.0905	0.6301	0.3105	0.044*
C10	0.2174 (6)	0.9516 (4)	0.2509 (2)	0.0256 (11)
C6	0.3130 (7)	0.5902 (5)	0.5036 (2)	0.0298 (12)
H6A	0.2608	0.6459	0.5190	0.045*
H6B	0.4110	0.6094	0.5030	0.045*
H6C	0.3043	0.5281	0.5248	0.045*
C3	0.0317 (6)	0.5531 (4)	0.3942 (2)	0.0258 (11)
H3A	0.0719	0.5033	0.3700	0.031*
H3B	−0.0681	0.5371	0.3964	0.031*
F1	0.1947 (4)	1.0191 (3)	0.20905 (13)	0.0387 (9)

	U11	U22	U33	U12	U13	U23
Pd1	0.0155 (2)	0.0132 (2)	0.0113 (2)	0.00004 (12)	0.00249 (15)	0.00002 (12)
I1	0.0180 (2)	0.0254 (2)	0.0364 (3)	−0.00383 (12)	−0.00055 (17)	0.00083 (14)
N2	0.024 (2)	0.017 (2)	0.014 (2)	0.0018 (17)	0.0023 (16)	−0.0014 (16)
N1	0.017 (2)	0.015 (2)	0.022 (2)	0.0013 (16)	0.0000 (16)	−0.0027 (17)
C4	0.036 (3)	0.024 (3)	0.024 (3)	0.002 (2)	0.016 (2)	0.004 (2)
C7	0.021 (2)	0.022 (2)	0.014 (2)	−0.002 (2)	0.0019 (19)	−0.0040 (19)
C9	0.038 (3)	0.034 (3)	0.020 (3)	−0.004 (3)	0.007 (2)	0.003 (2)
C5	0.035 (3)	0.018 (2)	0.020 (3)	0.001 (2)	0.000 (2)	−0.001 (2)
C12	0.024 (2)	0.021 (3)	0.017 (2)	−0.006 (2)	0.0037 (19)	−0.002 (2)
C11	0.027 (3)	0.023 (3)	0.024 (3)	0.001 (2)	0.000 (2)	0.006 (2)
C8	0.035 (3)	0.025 (3)	0.019 (3)	0.003 (2)	0.010 (2)	0.001 (2)
C1	0.021 (3)	0.026 (3)	0.038 (3)	0.004 (2)	0.011 (2)	−0.003 (2)
C2	0.034 (3)	0.037 (3)	0.018 (3)	−0.003 (3)	−0.005 (2)	0.000 (2)
C10	0.037 (3)	0.025 (3)	0.015 (2)	−0.009 (2)	−0.001 (2)	0.009 (2)
C6	0.047 (3)	0.028 (3)	0.014 (3)	0.004 (3)	0.001 (2)	0.000 (2)
C3	0.024 (3)	0.021 (3)	0.032 (3)	−0.004 (2)	0.003 (2)	0.000 (2)
F1	0.053 (2)	0.039 (2)	0.0244 (18)	−0.0003 (17)	0.0019 (15)	0.0191 (15)

Pd1—C7	1.990 (5)	C5—H5B	0.9600
Pd1—N1	2.138 (4)	C5—H5C	0.9600
Pd1—N2	2.198 (4)	C12—C11	1.393 (7)
Pd1—I1	2.5823 (7)	C12—H12	0.9300
N2—C4	1.466 (7)	C11—C10	1.361 (8)
N2—C5	1.479 (6)	C11—H11	0.9300
N2—C6	1.482 (7)	C8—H8	0.9300
N1—C1	1.477 (7)	C1—H1A	0.9600
N1—C2	1.482 (7)	C1—H1B	0.9600
N1—C3	1.488 (7)	C1—H1C	0.9600
C4—C3	1.501 (8)	C2—H2A	0.9600
C4—H4A	0.9700	C2—H2B	0.9600
C4—H4B	0.9700	C2—H2C	0.9600
C7—C12	1.385 (8)	C10—F1	1.364 (6)
C7—C8	1.410 (7)	C6—H6A	0.9600
C9—C8	1.376 (8)	C6—H6B	0.9600
C9—C10	1.392 (9)	C6—H6C	0.9600
C9—H9	0.9300	C3—H3A	0.9700
C5—H5A	0.9600	C3—H3B	0.9700
C7—Pd1—N1	91.56 (19)	C7—C12—C11	122.2 (5)
C7—Pd1—N2	174.34 (18)	C7—C12—H12	118.9
N1—Pd1—N2	83.35 (16)	C11—C12—H12	118.9
C7—Pd1—I1	89.51 (15)	C10—C11—C12	118.1 (5)
N1—Pd1—I1	178.59 (11)	C10—C11—H11	120.9
N2—Pd1—I1	95.55 (11)	C12—C11—H11	120.9
C4—N2—C5	110.1 (4)	C9—C8—C7	121.4 (5)
C4—N2—C6	109.4 (4)	C9—C8—H8	119.3
C5—N2—C6	107.6 (4)	C7—C8—H8	119.3
C4—N2—Pd1	105.2 (3)	N1—C1—H1A	109.5
C5—N2—Pd1	107.6 (3)	N1—C1—H1B	109.5
C6—N2—Pd1	116.8 (3)	H1A—C1—H1B	109.5
C1—N1—C2	108.0 (4)	N1—C1—H1C	109.5
C1—N1—C3	110.4 (4)	H1A—C1—H1C	109.5
C2—N1—C3	107.5 (4)	H1B—C1—H1C	109.5
C1—N1—Pd1	110.6 (3)	N1—C2—H2A	109.5
C2—N1—Pd1	115.2 (3)	N1—C2—H2B	109.5
C3—N1—Pd1	105.0 (3)	H2A—C2—H2B	109.5
N2—C4—C3	111.5 (4)	N1—C2—H2C	109.5
N2—C4—H4A	109.3	H2A—C2—H2C	109.5
C3—C4—H4A	109.3	H2B—C2—H2C	109.5
N2—C4—H4B	109.3	C11—C10—F1	119.3 (5)
C3—C4—H4B	109.3	C11—C10—C9	122.4 (5)
H4A—C4—H4B	108.0	F1—C10—C9	118.3 (5)
C12—C7—C8	117.4 (5)	N2—C6—H6A	109.5
C12—C7—Pd1	122.3 (4)	N2—C6—H6B	109.5
C8—C7—Pd1	120.0 (4)	H6A—C6—H6B	109.5
C8—C9—C10	118.4 (5)	N2—C6—H6C	109.5
C8—C9—H9	120.8	H6A—C6—H6C	109.5
C10—C9—H9	120.8	H6B—C6—H6C	109.5
N2—C5—H5A	109.5	N1—C3—C4	110.6 (5)
N2—C5—H5B	109.5	N1—C3—H3A	109.5
H5A—C5—H5B	109.5	C4—C3—H3A	109.5
N2—C5—H5C	109.5	N1—C3—H3B	109.5
H5A—C5—H5C	109.5	C4—C3—H3B	109.5
H5B—C5—H5C	109.5	H3A—C3—H3B	108.1
C7—Pd1—N2—C4	−35.7 (19)	N1—Pd1—C7—C12	74.4 (4)
N1—Pd1—N2—C4	−9.8 (3)	N2—Pd1—C7—C12	100.1 (18)
I1—Pd1—N2—C4	171.0 (3)	I1—Pd1—C7—C12	−106.5 (4)
C7—Pd1—N2—C5	81.7 (18)	N1—Pd1—C7—C8	−98.7 (4)
N1—Pd1—N2—C5	107.5 (3)	N2—Pd1—C7—C8	−73.0 (19)
I1—Pd1—N2—C5	−71.6 (3)	I1—Pd1—C7—C8	80.4 (4)
C7—Pd1—N2—C6	−157.2 (17)	C8—C7—C12—C11	3.0 (8)
N1—Pd1—N2—C6	−131.4 (4)	Pd1—C7—C12—C11	−170.3 (4)
I1—Pd1—N2—C6	49.5 (4)	C7—C12—C11—C10	−1.7 (8)
C7—Pd1—N1—C1	−81.4 (4)	C10—C9—C8—C7	−0.3 (9)
N2—Pd1—N1—C1	101.0 (4)	C12—C7—C8—C9	−1.9 (8)
I1—Pd1—N1—C1	139 (4)	Pd1—C7—C8—C9	171.5 (5)
C7—Pd1—N1—C2	41.4 (4)	C12—C11—C10—F1	179.1 (5)
N2—Pd1—N1—C2	−136.1 (4)	C12—C11—C10—C9	−0.7 (8)
I1—Pd1—N1—C2	−98 (5)	C8—C9—C10—C11	1.7 (9)
C7—Pd1—N1—C3	159.5 (3)	C8—C9—C10—F1	−178.1 (5)
N2—Pd1—N1—C3	−18.1 (3)	C1—N1—C3—C4	−75.3 (6)
I1—Pd1—N1—C3	20 (5)	C2—N1—C3—C4	167.1 (4)
C5—N2—C4—C3	−78.6 (5)	Pd1—N1—C3—C4	43.9 (5)
C6—N2—C4—C3	163.2 (5)	N2—C4—C3—N1	−57.3 (6)
Pd1—N2—C4—C3	37.0 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···F1i	0.96	2.57	3.445 (6)	151
C5—H5C···F1i	0.96	2.59	3.412 (5)	144
C1—H1C···I1ii	0.96	3.19	4.050 (5)	150
C4—H4B···I1iii	0.97	3.24	4.017 (5)	138

Table 1

Selected bond lengths ()

Pd1C7	1.990(5)
Pd1N1	2.138(4)
Pd1N2	2.198(4)
Pd1I1	2.5823(7)

Table 2

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C2H2AF1i	0.96	2.57	3.445(6)	151
C5H5CF1i	0.96	2.59	3.412(5)	144
C1H1CI1ii	0.96	3.19	4.050(5)	150
C4H4BI1iii	0.97	3.24	4.017(5)	138

Symmetry codes: (i) ; (ii) ; (iii) .