Bis(diphenyl-p-tolyl­phosphane-κP)(2-hy­droxy-3,5,7-bromo­cyclo­hepta-2,4,6-trienonato-κ2 O,O′)copper(I)

Nicola I Barnard; Tania N Hill

doi:10.1107/S1600536812042286

. 2012 Oct 13;68(Pt 11):m1354–m1355. doi: 10.1107/S1600536812042286

Bis(diphenyl-p-tolylphosphane-κP)(2-hydroxy-3,5,7-bromocyclohepta-2,4,6-trienonato-κ² O,O′)copper(I)

Nicola I Barnard ^a,^*, Tania N Hill ^a

PMCID: PMC3515112 PMID: 23284339

Abstract

The Cu^I atom in the title compund, [Cu(C₇H₂Br₃O₂)(C₁₉H₁₇P)₂], is located on a twofold rotation axis; the 3,5,7-tribromotropolonate anion coordinates as a bidentate ligand with a bite angle of 76.42 (9)°. An intramolecular C—H⋯O interaction occurs. Within the crystal, extensive weak C—H⋯π interactions contribute to the herringbone pattern observed in the packing of the molecules.

Related literature

For background to tropolone and its derivatives, see: Dewar (1945 ▶); Hill & Steyl (2008 ▶); Crous et al. (2005 ▶). For bis-troplolonato–copper(II) complexes, see: Chipperfield et al. (1998 ▶); Hasegawa et al. (1997 ▶); Ho (2010 ▶); Ho et al. (2009 ▶). For work on the effect the troplonato ligand has on the solid state and chemical behaviour of copper(I) phosphine metal complexes, see: Roodt et al. (2003 ▶); Steyl (2007 ▶, 2009 ▶); Steyl & Hill (2009 ▶); Steyl & Roodt (2006 ▶).

Experimental

Crystal data

[Cu(C₇H₂Br₃O₂)(C₁₉H₁₇P)₂]
M _r = 973.95
Monoclinic,
a = 15.4522 (8) Å
b = 13.9073 (8) Å
c = 19.3269 (10) Å
β = 103.862 (3)°
V = 4032.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 3.63 mm⁻¹
T = 100 K
0.18 × 0.09 × 0.06 mm

Data collection

Bruker X8 APEXII 4K Kappa CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.686, T _max = 0.746
27602 measured reflections
5022 independent reflections
3970 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.130
S = 1.04
5022 reflections
241 parameters
H-atom parameters constrained
Δρ_max = 1.51 e Å⁻³
Δρ_min = −1.57 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Click here for additional data file.^{(21.6KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812042286/ng5299sup1.cif

e-68-m1354-sup1.cif^{(21.6KB, cif)}

Click here for additional data file.^{(241.1KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812042286/ng5299Isup2.hkl

e-68-m1354-Isup2.hkl^{(241.1KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg2 and Cg3 are the centroids of the C121–C126 and C131–C136 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C136—H136⋯O2	0.95	2.52	3.365 (4)	149
C115—H115⋯Cg3ⁱ	0.95	2.86	3.621 (4)	138
C137—H13A⋯Cg2ⁱⁱ	0.98	3.18	4.144 (6)	168

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

Professors G. Steyland and A. Roodt, University of the Free State, and Mr Renier Koen are thanked for the data collection. Financial assistance from the University of the Free State Strategic Academic Cluster Initiative, SASOL, the South African NationalResearch Foundation (SA–NRF/THRIP) and the Inkaba yeAfrika Research Initiative is gratefully acknowledged. Part of this material is based on work supported by the SA–NRF/THRIP under grant No. GUN 2068915. Opinions, findings,conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the SA–NRF.

supplementary crystallographic information

Comment

Tropolone and its derivatives have been of interest ever since their first discovery in the early 1940's (Dewar, 1945); they are known to have applications in both pharmacology (Hill & Steyl, 2008) and catalysis (Crous et al., 2005). Bis troplolonato copper(II) complexes are most frequently reported (Ho, 2010; Ho et al., 2009; Chipperfield et al., 1998; Hasegawa et al., 1997). Recently, reseach in this area has been extended to include copper(I) phosphine metal complexes and the effect the troplonato ligand has on the solid state and chemical behaviour of these complexes (Steyl, 2007; Steyl & Roodt, 2006; Roodt et al., 2003). In this paper, the structure of the tropolonato-bis[diphenyl(p-tolyl)-phosphine]copper(I) complex is reported (Fig. 1).

The Cu—O and Cu—P bond distances were found to be 2.090 (1) Å and 2.229 (1) Å respectively and are well within comparable ranges for copper(I) phosphine complexes. the bond angles about the Cu atom show significantly distorted tetrahedral coordination (Table 1). The bidentate bite angle O2—Cu—O2ⁱ observed at 76.42 (9)° is close to analogous angles in previously reported structures (Steyl, 2009).

The title compound (I) displays intramolecular C—H···Br interactions with a distance of 3.4666 (5) Å as seen in Figure 2. Figure 3 illustrates the packing diagram for compound (I), a zigzag pattern is adopted with inverted repeating units creating diagonals in all directions. This intricate design is achieved though numerous C—H···π itermolecular interactions see Figure 4. These interactions occur between methyl H atoms of the p-tolyl and phenyl π, phenyl H to p-tolyl π, phenyl H to phenyl π and p-tolyl π to p-tolyl The C—H···π itermolecular interactions range from 3.1816 (1) Å - 3.7267 (2) Å.

Experimental

3,5,7-Tribomotropolone (0.3 mmol) was dissolved in methanol (20 ml). To this solution was added Bis(diphenyl(p-tolyl)-phosphine) copper nitrate (0.3 mmol). The resulting mixture was stirred at room temperature for 30 minutes before filtering. The filtrate was then slowly evaporated yielding crystals siutable for X-ray diffraction after 48 h.