(Nitrato-κO)tris­[tris­(4-fluoro­phen­yl)phosphane-κP]copper(I)

Tania N Hill; Andreas Roodt

doi:10.1107/S1600536812043346

. 2012 Oct 24;68(Pt 11):m1396–m1397. doi: 10.1107/S1600536812043346

(Nitrato-κO)tris[tris(4-fluorophenyl)phosphane-κP]copper(I)

Tania N Hill ^a,^*, Andreas Roodt ^a

PMCID: PMC3515141 PMID: 23284368

Abstract

In the title complex, [Cu(NO₃)(C₁₈H₁₂F₃P)₃], the ligating atoms define a distorted tetrahedon with the three tris(4-fluorophenyl)phosphane ligands in the basal positions and the nitrate ligand in the axial position. The intramolecular π–π interaction [centroid–centroid distance = 3.6113 (11) Å] between two of the 4-fluorophenyl groups is complemented by both C—H⋯F and C—H⋯O interactions with distances in the range 2.51–2.60 Å, resulting in a tight head-to-tail packing.

Related literature

For related complexes, see: Hanna et al. (2005 ▶); Steyl (2009 ▶); Saravanabharathi et al. (2002 ▶); Dyason et al. (1986 ▶); Matthew et al. (1971 ▶).

Experimental

Crystal data

[Cu(NO₃)(C₁₈H₁₂F₃P)₃]
M _r = 1074.29
Triclinic,
a = 9.3861 (3) Å
b = 12.2552 (4) Å
c = 21.4820 (7) Å
α = 85.274 (2)°
β = 86.843 (1)°
γ = 74.954 (1)°
V = 2376.76 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.64 mm⁻¹
T = 100 K
0.38 × 0.11 × 0.08 mm

Data collection

Bruker X8 APEXII 4K KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.792, T _max = 0.950
28458 measured reflections
11760 independent reflections
9439 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.085
S = 1.05
11760 reflections
640 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2004 ▶); 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.^{(51.2KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812043346/mw2090sup1.cif

e-68-m1396-sup1.cif^{(51.2KB, cif)}

Click here for additional data file.^{(563.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812043346/mw2090Isup2.hkl

e-68-m1396-Isup2.hkl^{(563.4KB, hkl)}

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

Table 1. Selected bond lengths (Å).

O1—Cu1	2.1182 (12)
P1—Cu1	2.2901 (5)
P2—Cu1	2.2840 (5)
P3—Cu1	2.3256 (5)

Open in a new tab

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C122—H122⋯O2	0.95	2.30	3.224 (2)	163
C336—H336⋯O1	0.95	2.17	3.037 (2)	151
C126—H126⋯F22ⁱ	0.95	2.40	3.281 (2)	154
C136—H136⋯O3ⁱⁱ	0.95	2.53	3.223 (2)	130
C215—H215⋯F13ⁱⁱⁱ	0.95	2.51	3.301 (2)	141
C315—H315⋯F33^iv	0.95	2.50	3.403 (2)	159
C332—H332⋯F32^v	0.95	2.48	3.131 (2)	125
C326—H326⋯F33^vi	0.95	2.36	3.150 (2)	141

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Acknowledgments

Financial assistance from the University of the Free State is gratefully acknowledged. We also express our gratitude towards SASOL and the South African National Research Foundation (SA-NRF/THRIP) for financial support of this project. 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

The title compound (I) has a copper(I) metal center co-ordinated by three tris-4-fluorophenylphosphane ligands ((p-FPh)₃P) and a nitrato ligand. The ligating atoms define a distorted trigonal pyramid which is similar to what was found for [Cu(PPh₃)₃(X)] X = ClO₄^-, BF₄^-,NO₃^-, HCO₂^- (Hanna et al., 2005) complexes, where the average P—Cu—P angles are in the range 112.29 (4)° - 121.37 (6)°. While markedly different, the P—Cu—P bond angles for for I (Table 1) fall within this range with an average of 116 (2)°. The dissimilarity observed for the O—Cu—P bond angles (Table 1) are as a result of C—H···O (Figure 4) and O2···π (centroid C221-C226) interactions contributing to the non-linearity of the N1—O1—Cu1 angle and the deviation (14.39 (5)°) of the nitrato ligand from the axial position. The average Cu—P bond lengths for [Cu(PPh₃)₃(NO₃)].EtOH (Dyason et al., 1986), [Cu(PPh₃)₃(NO₃)].MeOH (Steyl, 2009) and I were observed to be 2.329 (9) Å, 2.326 (10) Å and 2.300 (13) Å respectively.

An intermolecular π–π interaction is observed for A (centroid C131—C136)···B (centroid C211—C216) with a distance of 3.6113 (11) Å and is stabilized by the bifurcated hydrogen fluorine interaction C215—H215···F21ⁱⁱⁱ and C215—H215···F13ⁱⁱⁱ with H···F distances of 2.61 Å and 2.51 Å respectively (see Figure 2). An additional stabilizing effect arises from the C135ⁱⁱ—H135ⁱⁱ···O2 and C136ⁱⁱ—H136ⁱⁱ···O3 interactions (Figure 4) with H···O distances of 2.58 Å and 2.53 Å. Additional C—H···F interactions are illustrated in Figure 3. All of these interactions contribute to tight packing of I.

Experimental

tris-4-fluorophenylphosphane (2 mmol) was added to a solution of CuNO₃ (1 mmol) in warm MeOH (15 ml, 70 °C) and the resulting solution was stirred for c.a. 1 h. The solution was filtered and allowed to cool slowly. Crystals suitable for single-crystal X-ray diffraction were obtained from the slow evaporation of the solution.