Bromido{dicyclo­hexyl[2′-(dimethyl­amino)biphenyl-2-yl]phosphine-κP}[2-(4,6-dimethyl­pyrimidin-2-yl)ferrocenyl-κ2 C 1,N]palladium(II) dichloro­methane solvate

Xin-Qi Hao; Hong-Mei Li; Hui Jiang; Yong-Tao Ma; Mao-Ping Song

doi:10.1107/S1600536809012884

. 2009 Apr 18;65(Pt 5):m529–m530. doi: 10.1107/S1600536809012884

Bromido{dicyclohexyl[2′-(dimethylamino)biphenyl-2-yl]phosphine-κP}[2-(4,6-dimethylpyrimidin-2-yl)ferrocenyl-κ² C ¹,N]palladium(II) dichloromethane solvate

Xin-Qi Hao ^a, Hong-Mei Li ^b, Hui Jiang ^a, Yong-Tao Ma ^a, Mao-Ping Song ^a,^*

PMCID: PMC2977585 PMID: 21583771

Abstract

In the title compound, [FePdBr(C₅H₅)(C₁₁H₁₀N₂)(C₂₆H₃₆NP)]·CH₂Cl₂, the Pd atom displays a distorted square-planar coordination environment. The five-membered metallacycle adopts an envelope conformation with the coordinated cyclopentadienyl C atom 0.4222 (4) Å out of plane. The dihedral angle between the pyrimidinyl ring and substituted cyclopentadienyl ring is 21.47 (2)°. In the crystal structure, the dimeric unit is generated through the C—H⋯π contact via a crystallographic inversion centre, while the C—H⋯Cl contacts in the dimeric centre link the dichlormethane molecules with the Pd complex molecules.

Related literature

For historical background of cyclopalladated compounds, see: Cope & Sickman (1965 ▶). For the properties of cyclopalladated compounds, see: Dupont et al. (2005 ▶); Gong et al. (2007 ▶); Xu et al. (2007 ▶). For related structures, see: Xu et al. (2008 ▶, 2009 ▶).

Experimental

Crystal data

[FePdBr(C₅H₅)(C₁₁H₁₀N₂)(C₂₆H₃₆NP)]·CH₂Cl₂
M _r = 955.91
Triclinic,
a = 10.2059 (9) Å
b = 10.3637 (9) Å
c = 21.900 (2) Å
α = 81.195 (1)°
β = 76.590 (1)°
γ = 72.647 (1)°
V = 2141.9 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.89 mm⁻¹
T = 293 K
0.37 × 0.24 × 0.21 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.540, T _max = 0.697
16458 measured reflections
7919 independent reflections
6716 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.099
S = 1.08
7919 reflections
473 parameters
H-atom parameters constrained
Δρ_max = 1.03 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809012884/si2165sup1.cif

e-65-0m529-sup1.cif^{(43.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809012884/si2165Isup2.hkl

e-65-0m529-Isup2.hkl^{(387.4KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Pd1—C1	1.997 (3)
Pd1—N1	2.192 (3)
Pd1—P1	2.2654 (9)
Pd1—Br1	2.6585 (6)

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N1—Pd1—P1	173.00 (9)
C1—Pd1—Br1	160.40 (10)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cl2ⁱ	0.98	2.78	3.671 (5)	151
C16—H16C⋯Cg1ⁱⁱ	0.96	2.68	3.544 (6)	151

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1 is the centroid of the C6–C10 Cp ring.

Acknowledgments

This work was supported by the National Science Foundation of China (No. 20872133) and the Innovation Fund for Outstanding Scholars of Henan Province (No. 074200510005).

supplementary crystallographic information

Comment

Cyclopalladated compounds containing a Pd—C bond intramolecularly stabilized by one donor atom were first reported in the middle 1960's (Cope & Sickman, 1965). Forty years later, the chemistry of these compound has developed into one of the most fruitful fields in organometallic chemistry (Dupont et al., 2005). In the palladium-catalyzed coupling reactions, palladacycles have shown enormous superiority in many respects (Gong et al., 2007; Xu et al., 2007).

The Pd atom in the title complex is in a distorted square-planar environment bonded to the atoms shown in Fig. 1: the Br atom,the pyrimidinyl nitrogen atom and the carbon atom of the ferrocenyl moiety. The Pd—C1 (N1,P1,Br1) bond lengths and the P1—Pd1—N1 and C1—Pd1—Br1 bond angles (Table 1) are within comparable ranges of 162.08 (7) ° - 174.76 (7) ° and 162.27 (9) ° - 166.04 (8) ° (C—Pd—Cl), respectively (Xu et al., 2009). The five-membered metallacycle (containing atoms C1/C2/C11/N1/Pd1) adopts an envelope conformation, with the C1 atom 0.4222 (4) Å out of plane. The dihedral angle between the pyrimidinyl ring and substituted cyclopentadienyl ring is 21.47 (2)°. In the crystal structure, the dimeric unit (Fig.2) is generated through the C—H···π contacts via a crystallographic inversion centre, and the C—H···Cl contact (Table 2) connects a symmetry-related dichlormethane molecule with the Pd complex (Table 2).This hydrogen bonding motif is different from those of related cyclopalladated ferrocene derivatives (Xu et al., 2008; Xu et al., 2009), in which C—H···Cl hydrogen bonds construct the one-dimensional chain structures.

Experimental

The title compound was prepared as described in literature (Xu et al., 2009), using Li₂PdBr₄ instead of Li₂PdCl₄ and recrystallized from dichloromethane-petroleum ether solution at room temperature to give the desired product as red crystals suitable for single-crystal X-ray diffraction.