A new heteroleptic cuprous complex with strong yellow photoluminescence

In the title heteroleptic cuprous complex, (aceto­nitrile-κN)({2-[2-(di­phenyl­phosphan­yl)phen­oxy]phen­yl}di­phenyl­phos­phane-κ²P,P′)[2-(pyridin-4-yl-κN)-1,3-benzoxazole]copper(I) hexa­fluorido­phosphate, [Cu(C₃₆H₂₈OP₂)(CH₃CN)(C₁₂H₈N₂O)]PF₆, conventionally abbreviated [Cu(POP)(CH₃CN)(4-PBO)]PF₆, where POP is the diphosphane ligand {2-[2-(di­phenyl­phosphan­yl)phen­oxy]phen­yl}di­phenyl­phosphane and 4-PBO is the N-containing ligand 2-(pyridin-4-yl)-1,3-benzoxazole, the asymmetric unit consists of a hexa­fluorido­phosphate anion and a whole mononuclear cation, where the Cu^I centre is coordinated by two P atoms from the POP ligand, by one N atom from the 4-PBO ligand and by the N atom of the coordinated aceto­nitrile mol­ecule, giving rise to a CuP₂N₂ distorted tetra­hedral coordination geometry. The electronic absorption, photoluminescence and thermal stability properties of this complex have been studied on as-synthesized samples, which had previously been examined by powder X-ray diffraction. A yellow emission signal is attributed to an excited state arising from metal-to-ligand charge transfer (MLCT).

S1. Introduction

Highly luminescent transition-metal complexes have a wide range of potential applications, such as biological imaging (McMillin & McNett, 1998), photochemical catalysis (Kuramochi et al., 2014), chemical sensors/probes (Zhao et al., 2010), sensitizers in photovoltaic devices (Robertson, 2008) and emitters in organic light-emitting diodes (OLEDs) (Xiao et al., 2011). Now, OLEDs are considered to be the next generation of flat panel displays because of their numerous advantages (Xiao et al., 2011). OLED technology offers the distinctive possibility of fabricating lightweight, large area and also flexible and transparent light-emitting devices by low-cost processing based on various thin-film deposition techniques, such as vacuum thermal evaporation, spin coating or casting from solution. Based on these attractive properties, sources for general lighting based on white organic light-emitting diodes (WOLEDs) are also being actively investigated (Farinola & Ragni, 2011; Dawson, 2010). To overcome the 25% inter­nal quantum efficiency limit in fluorescent OLEDs (Baldo et al., 1998), phospho­rescent heavy metal complex emitters based on Ir, Pt and Os have been developed to achieve high efficiency with colour tuning emission (Zhang et al., 2004). Nowadays, an excellent external quantum efficiency (EQE, photons per electron) has been reached based on cyclo­metalated iridium(III) complexes (Hashimoto et al., 2011). Unfortunately, iridium and other heavy metal are low in natural abundance, so there has been an increasing inter­est in luminescent copper(I) complexes for use in high-efficiency OLEDs due to their advantages including abundant resource, low cost and nontoxic properties compared to noble metal complexes, e.g. Re, Os, Ir, Pt and Rh (Liu et al., 2011).

Among all the luminescent copper(I) complexes, cationic Cu^I complexes have attracted much attention over the past two decades because of their available metal-to-ligand charge transfer (MLCT) excited state and good solubility for fabricating luminescent devices (Zhang et al., 2004). Originally, the research was focused on the [Cu(N–N)₂]⁺ complexes, and McMillin group's systematic studies revealed that the luminescence intensity of complexes markedly depends on the substituent at 2,9-positions of the phenanthroline ligand (McMillin & McNett, 1998). However, the [Cu(N–N)₂]⁺ systems still exhibits week emission. Fortunately, when one di­imine ligand is replaced by one diphosphane ligand, the derivative complexes, called heteroleptic [Cu(N–N)(P–P)]⁺ complexes, shows an unprecedented lifetime and high luminescence (Cuttell et al., 2002). In this study, we have focused on the construction of a novel heteroleptic cuprous complex by utilizing {2-[2-(di­phenyl­phosphanyl)phen­oxy]­phenyl}­diphenyl­phosphane (POP) as the P-containing ligand and 2-(pyridin-4-yl)-1,3-benzoxazole (4-PBO) as the N-containing ligand, and the title complex, [Cu(POP)(CH₃CN)(4-PBO)]PF₆, (I), with a strong yellow luminescence, has been successfully synthesized and characterized.

S2. Experimental

S2.1. Synthesis and crystallization

The title complex, (I), was synthesized by a successive-assembly reaction with mixed solvents. Cu(CH₃CN)₄·(PF₆) (0.1 mmol) and 4-PBO (0.1 mmol) were dissolved in aceto­nitrile (10 ml) under stirring at room temperature. And then, di­chloro­methane solution (5 ml) containing POP (0.1 mmol) was added to the resulting solution dropwise under stirring. The mixture solution was stirred at room temperature for an additional 30 min. The crude complex was collected after rotary evaporation under reduced pressure, washed with ethanol and dried to obtain a pure yellow product. Single crystals suitable for X-ray analysis were obtained by dissolving this powder product in aceto­nitrile (4 ml) and covering with a layer of propan-2-ol. IR (KBr, cm^-1): 3050 (m), 2962 (w), 2922 (w), 2300 (w), 2270 (w), 1954 (w), 1892 (w), 1812 (w), 1576 (m), 1434 (s), 1213 (s), 1090 (m), 885 (vs), 745 (s), 700 (s), 560 (s), 515 (ms).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms bounded to C atoms were added at calculated positions and refined using a riding model, with C—H = 0.93–0.97 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for all others.

S3. Results and discussion

Compound (I) is a ionic mononuclear structure (Fig. 1) made up of an hexafluoridophosphate anion and a complex cation, consisting of one Cu^I centre, one diphosphane POP ligand acting in a chelated fashion, one N-containing 4-PBO ligand and one N-coordinated aceto­nitrile molecule. The Cu^I centre exhibits a [CuP₂N₂] distorted tetra­hedral coordination geometry with a large P1—Cu1—P2 bite angle of 114.28 (3)°, which is similar to previous reports (Cuttell et al., 2002; Zhang et al., 2007; Czerwieniec et al., 2013). Within this CuP₂N₂ tetra­hedron, the Cu—P and Cu—N bond lengths (Table 2) are similar to those in analogous heteroleptic structures containing the POP ligand (Cuttell et al., 2002; Zhang et al., 2007; Hsu et al., 2011; Femoni et al., 2013). It is worth noting that the Cu—N bond length in aceto­nitrile is smaller than that in the 4-PBO ligand, indicating that the coordination of aceto­nitrile to copper is slightly stronger than that of 4-PBO. And this actual coordination also brings about good thermal stability against the escape of volatile aceto­nitrile (see TG–DSC measurement below). There are no obvious supra­molecular inter­actions, such as hydrogen bonding or π–π stacking inter­actions, to give rise to a supra­molecular structure, and so the complex is stabilzed by weak van der Waals forces and electrostatic attractions between the ionic moieties.

Before measureing some physicochemical properties of this complex, a powder X-ray diffraction (PXRD) experiment has been performed in order to check the purity of the powder sample. As shown in Fig. 2, the experimental peaks overlap well with those calculated from the single-crystal data. The UV–Vis absorption spectrum of (I) in di­chloro­methane (c = 1.0 × 10^-5 M) solution is compared with those of the free ligands in Fig. 3. There is a π–π* transition band centred at 270 and 300 nm in the spectra of the POP and 4-PBO ligands, respectively, while a new broadened band centreed at 290 nm appears in the spectrum of (I) due to a mixture of the π–π* transition from POP and 4-PBO, or between them. In the low-energy region, an additional tail could be easily seen beyond this π–π* transition band, even expanding to the visible region. According to previous reports on similar heteroleptic structures (Zhang et al., 2007; Hsu et al., 2011; Femoni et al., 2013), this weak absorption band should be assigned as a MLCT absorption band, that is a charge transfer primarily from the Cu centre to the N-containing ligand 4-PBO.

The solid-state emission and excitation spectra have been recorded at room temperature on as-synthesized powder samples (Fig. 4). Under irradiation with wavelengths varying from 330 to 520 nm (the full width at half-maximum of the excitation spectrum), the complex emits strong yellow phospho­rescence all along, and its photoluminescence (PL) emission spectrum is broad with the λ_max value at ~570 nm and without any observed vibronic fine structures. It is worth mentioning that the shockes shift herein of 150 nm is smaller than the great majority of similar luminescent Cu^I complexes, and this small shift should benefit the high efficiency of the energy utilization. These PL emissions should be derived from some MLCT excited states on the basis of relevant reports (Zhang et al., 2007; Hsu et al., 2011; Femoni et al., 2013).

For investigating the thermal stability of (I), simultaneous thermogravimetric (TG) and differential scanning calorimetry (DSC) measurements were carried out on the as-synthesized powder sample. As shown in Fig. 5, there are three obvious weight-loss steps. The weight loss in the range ~373–433 K (4%) corresponds to the release of the coordinated aceto­nitrile molecule (calculated value 4.16%). Above 473 K, the second third weight-loss steps are two sequential process, they could be assigned as the decomposition of 4-PBO and POP ligands. After 773 K, the weight loss is completely finished and the (not analyzed) final residuals (11%) should be ascribable to inorganic residues (copper oxide etc.).

Related literature

For related literature, see: Baldo et al. (1998); Cuttell et al. (2002); Czerwieniec et al. (2013); Dawson (2010); Farinola & Ragni (2011); Femoni et al. (2013); Hashimoto et al. (2011); Hsu et al. (2011); Kuramochi et al. (2014); Liu et al. (2011); McMillin & McNett (1998); Robertson (2008); Xiao et al. (2011); Zhang et al. (2004, 2007); Zhao et al. (2010).

Computing details

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: OLEX2.SOLVE (Bourhis et al., 2014); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures

	Fig. 1. The molecular structure and atom-labelling scheme of (I), with displacement ellipsoids drawn at the 30% probability level. H atoms have been omitted for clarity.
	Fig. 2. XRD patterns for complex (I), showing (a) the pattern calculated from the single-crystal data and (b) the pattern observed at room temperature.
	Fig. 3. The UV absorption spectra of 4-PBO, POP and complex (I) in CH2Cl2.
	Fig. 4. The photoluminescent emission (λex = 420 nm) and excitation (λex = 570 nm) spectra recorded on powder samples of complex (I) at room temperature.
	Fig. 5. The TG and DSC curves of complex (I).

(Acetonitrile-κN)({2-[2-(diphenylphosphanyl)phenoxy]phenyl}diphenylphosphane- κ²P,P')[2-(pyridin-4-yl-κN)-1,3-benzoxazole]copper(I) hexafluoridophosphate

Crystal data

[Cu(C36H28OP2)(C12H8N2O)(C2H3N)]PF6	F(000) = 2016
Mr = 984.29	Dx = 1.402 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.0913 (11) Å	Cell parameters from 5004 reflections
b = 14.9503 (9) Å	θ = 3.1–29.5°
c = 22.6588 (15) Å	µ = 0.64 mm^−1
β = 102.300 (7)°	T = 293 K
V = 4663.9 (6) Å^3	Block, clear light yellow
Z = 4	0.37 × 0.33 × 0.23 mm

Data collection

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer	11077 independent reflections
Radiation source: Enhance (Mo) X-ray Source	6452 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 10.3592 pixels mm^-1	θmax = 29.5°, θmin = 3.1°
ω scans	h = −19→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −13→20
Tmin = 0.870, Tmax = 1.000	l = −30→31
21816 measured reflections

Refinement

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.160	w = 1/[σ^2(Fo^2) + (0.073P)^2 + 0.912P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
11077 reflections	Δρmax = 0.58 e Å^−3
587 parameters	Δρmin = −0.37 e Å^−3
0 restraints

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.18529 (3)	0.59979 (2)	0.36705 (2)	0.04349 (13)
P1	0.11829 (6)	0.65930 (5)	0.27563 (4)	0.0434 (2)
P2	0.28434 (6)	0.69491 (5)	0.43039 (4)	0.0426 (2)
O1	0.32207 (16)	0.70864 (14)	0.30386 (9)	0.0480 (5)
O2	0.4279 (2)	0.18489 (17)	0.39991 (12)	0.0750 (8)
N1	0.0772 (2)	0.5419 (2)	0.40123 (13)	0.0574 (7)
N2	0.26887 (19)	0.48612 (17)	0.36248 (11)	0.0467 (6)
N3	0.4854 (2)	0.2289 (2)	0.32100 (15)	0.0688 (9)
C1	−0.0831 (3)	0.4764 (3)	0.4213 (2)	0.0854 (13)
H1A	−0.1379	0.5079	0.3959	0.128*
H1B	−0.0854	0.4844	0.4639	0.128*
H1C	−0.0870	0.4126	0.4113	0.128*
C2	0.0081 (3)	0.5128 (3)	0.41054 (16)	0.0583 (9)
C3	−0.0133 (2)	0.6750 (2)	0.25994 (14)	0.0484 (8)
C4	−0.0722 (3)	0.6661 (3)	0.20214 (16)	0.0625 (9)
H4	−0.0440	0.6547	0.1683	0.075*
C5	−0.1718 (3)	0.6739 (3)	0.1947 (2)	0.0774 (12)
H5	−0.2119	0.6677	0.1555	0.093*
C6	−0.2134 (3)	0.6904 (3)	0.2427 (2)	0.0738 (11)
H6	−0.2820	0.6958	0.2367	0.089*
C7	−0.1567 (3)	0.6991 (3)	0.29967 (19)	0.0687 (10)
H7	−0.1858	0.7105	0.3331	0.082*
C8	−0.0570 (3)	0.6912 (2)	0.30830 (16)	0.0584 (9)
H8	−0.0179	0.6970	0.3478	0.070*
C9	0.1364 (2)	0.5982 (2)	0.20903 (14)	0.0472 (7)
C10	0.1320 (3)	0.5052 (2)	0.21047 (16)	0.0585 (9)
H10	0.1239	0.4757	0.2462	0.070*
C11	0.1392 (3)	0.4556 (3)	0.15997 (19)	0.0723 (11)
H11	0.1367	0.3922	0.1613	0.087*
C12	0.1501 (3)	0.4979 (3)	0.10823 (19)	0.0770 (12)
H12	0.1550	0.4638	0.0736	0.092*
C13	0.1539 (3)	0.5890 (3)	0.10635 (18)	0.0789 (13)
H13	0.1608	0.6180	0.0702	0.095*
C14	0.1479 (3)	0.6395 (3)	0.15633 (16)	0.0644 (10)
H14	0.1517	0.7029	0.1546	0.077*
C15	0.1667 (2)	0.7712 (2)	0.26777 (14)	0.0474 (7)
C16	0.1088 (3)	0.8462 (2)	0.24916 (16)	0.0625 (9)
H16	0.0407	0.8391	0.2351	0.075*
C17	0.1495 (4)	0.9306 (3)	0.25100 (19)	0.0759 (12)
H17	0.1091	0.9810	0.2389	0.091*
C18	0.2470 (4)	0.9420 (2)	0.27002 (19)	0.0769 (12)
H18	0.2742	1.0002	0.2708	0.092*
C19	0.3067 (3)	0.8694 (2)	0.28821 (17)	0.0646 (10)
H19	0.3748	0.8772	0.3015	0.078*
C20	0.2657 (3)	0.7850 (2)	0.28683 (14)	0.0475 (8)
C21	0.4069 (2)	0.7172 (2)	0.34871 (15)	0.0468 (7)
C22	0.4947 (3)	0.7258 (2)	0.33098 (18)	0.0613 (9)
H22	0.4962	0.7289	0.2893	0.074*
C23	0.5800 (3)	0.7297 (3)	0.3744 (2)	0.0687 (11)
H23	0.6404	0.7354	0.3625	0.082*
C24	0.5780 (3)	0.7254 (3)	0.4347 (2)	0.0679 (10)
H24	0.6367	0.7286	0.4644	0.081*
C25	0.4903 (3)	0.7163 (2)	0.45177 (17)	0.0590 (9)
H25	0.4895	0.7135	0.4935	0.071*
C26	0.4021 (2)	0.7112 (2)	0.40919 (15)	0.0469 (7)
C27	0.3184 (2)	0.6530 (2)	0.50841 (14)	0.0496 (8)
C28	0.2960 (3)	0.6975 (3)	0.55681 (16)	0.0718 (11)
H28	0.2685	0.7557	0.5514	0.086*
C29	0.3134 (3)	0.6576 (4)	0.61387 (19)	0.0920 (15)
H29	0.2965	0.6885	0.6468	0.110*
C30	0.3539 (4)	0.5759 (4)	0.6225 (2)	0.0885 (14)
H30	0.3656	0.5493	0.6614	0.106*
C31	0.3783 (4)	0.5311 (3)	0.5750 (2)	0.0915 (14)
H31	0.4074	0.4736	0.5811	0.110*
C32	0.3606 (3)	0.5695 (3)	0.51831 (18)	0.0757 (12)
H32	0.3777	0.5380	0.4857	0.091*
C33	0.2419 (2)	0.8091 (2)	0.43750 (14)	0.0464 (7)
C34	0.3010 (3)	0.8821 (3)	0.4488 (3)	0.109 (2)
H34	0.3693	0.8745	0.4544	0.131*
C35	0.2633 (4)	0.9669 (3)	0.4522 (3)	0.126 (2)
H35	0.3061	1.0165	0.4605	0.151*
C36	0.1680 (4)	0.9801 (3)	0.4439 (2)	0.0834 (14)
H36	0.1426	1.0387	0.4451	0.100*
C37	0.1079 (4)	0.9083 (3)	0.4337 (2)	0.0894 (15)
H37	0.0398	0.9167	0.4287	0.107*
C38	0.1446 (3)	0.8231 (3)	0.43064 (19)	0.0707 (11)
H38	0.1014	0.7735	0.4237	0.085*
C39	0.4833 (3)	0.1154 (2)	0.38473 (18)	0.0620 (9)
C40	0.5025 (4)	0.0336 (3)	0.4108 (3)	0.1077 (18)
H40	0.4774	0.0161	0.4448	0.129*
C41	0.5603 (4)	−0.0224 (3)	0.3853 (3)	0.1027 (17)
H41	0.5758	−0.0801	0.4023	0.123*
C42	0.5953 (4)	0.0029 (3)	0.3367 (3)	0.0990 (16)
H42	0.6332	−0.0381	0.3195	0.119*
C43	0.5776 (4)	0.0856 (4)	0.3117 (2)	0.1072 (19)
H43	0.6044	0.1039	0.2786	0.129*
C44	0.5188 (3)	0.1419 (3)	0.33668 (17)	0.0622 (9)
C45	0.4338 (2)	0.2496 (2)	0.35919 (15)	0.0508 (8)
C46	0.3792 (2)	0.3322 (2)	0.36147 (14)	0.0459 (7)
C47	0.3881 (3)	0.4042 (2)	0.32433 (16)	0.0561 (9)
H47	0.4319	0.4016	0.2978	0.067*
C48	0.3329 (3)	0.4792 (2)	0.32642 (16)	0.0550 (8)
H48	0.3403	0.5284	0.3013	0.066*
C49	0.2612 (3)	0.4167 (2)	0.39775 (16)	0.0572 (9)
H49	0.2165	0.4207	0.4237	0.069*
C50	0.3147 (3)	0.3387 (2)	0.39882 (16)	0.0578 (9)
H50	0.3068	0.2908	0.4249	0.069*
P3	0.11093 (9)	0.25787 (7)	0.49916 (5)	0.0694 (3)
F1	0.0341 (3)	0.3072 (2)	0.5262 (2)	0.1609 (16)
F2	0.1811 (3)	0.34119 (19)	0.51479 (16)	0.1303 (12)
F3	0.0746 (3)	0.2990 (3)	0.43509 (17)	0.1642 (16)
F4	0.1942 (2)	0.2102 (2)	0.47340 (17)	0.1264 (11)
F5	0.0488 (3)	0.1722 (2)	0.4840 (2)	0.1476 (14)
F6	0.1540 (4)	0.2181 (3)	0.56213 (16)	0.186 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0424 (2)	0.0414 (2)	0.0459 (2)	−0.00026 (16)	0.00771 (16)	−0.00045 (16)
P1	0.0420 (5)	0.0432 (4)	0.0432 (4)	−0.0008 (4)	0.0047 (3)	−0.0009 (3)
P2	0.0381 (5)	0.0444 (4)	0.0438 (4)	0.0009 (3)	0.0056 (3)	−0.0046 (3)
O1	0.0459 (13)	0.0451 (12)	0.0511 (12)	−0.0045 (10)	0.0058 (10)	−0.0049 (10)
O2	0.098 (2)	0.0617 (16)	0.0758 (17)	0.0216 (15)	0.0411 (16)	0.0081 (14)
N1	0.0486 (18)	0.0623 (18)	0.0639 (18)	−0.0006 (14)	0.0181 (15)	0.0057 (15)
N2	0.0470 (16)	0.0440 (14)	0.0513 (15)	0.0039 (12)	0.0152 (12)	0.0021 (12)
N3	0.075 (2)	0.067 (2)	0.075 (2)	0.0268 (17)	0.0394 (18)	0.0150 (16)
C1	0.056 (3)	0.100 (3)	0.105 (3)	−0.018 (2)	0.030 (2)	0.000 (3)
C2	0.057 (2)	0.063 (2)	0.054 (2)	0.0001 (18)	0.0121 (17)	0.0032 (17)
C3	0.0467 (19)	0.0458 (17)	0.0496 (18)	0.0025 (14)	0.0032 (15)	0.0024 (14)
C4	0.052 (2)	0.078 (2)	0.052 (2)	0.0068 (19)	−0.0016 (17)	0.0045 (18)
C5	0.056 (3)	0.095 (3)	0.069 (3)	0.005 (2)	−0.013 (2)	0.005 (2)
C6	0.042 (2)	0.081 (3)	0.091 (3)	0.0107 (19)	−0.002 (2)	0.010 (2)
C7	0.050 (2)	0.077 (3)	0.079 (3)	0.0122 (19)	0.013 (2)	0.005 (2)
C8	0.049 (2)	0.066 (2)	0.056 (2)	0.0101 (17)	0.0026 (17)	−0.0018 (17)
C9	0.0430 (18)	0.0491 (17)	0.0480 (18)	−0.0062 (14)	0.0063 (14)	−0.0025 (15)
C10	0.063 (2)	0.0513 (19)	0.059 (2)	−0.0060 (17)	0.0079 (17)	−0.0069 (17)
C11	0.080 (3)	0.056 (2)	0.077 (3)	−0.010 (2)	0.009 (2)	−0.019 (2)
C12	0.082 (3)	0.087 (3)	0.065 (3)	−0.015 (2)	0.024 (2)	−0.029 (2)
C13	0.095 (3)	0.092 (3)	0.055 (2)	−0.023 (3)	0.028 (2)	−0.010 (2)
C14	0.077 (3)	0.059 (2)	0.061 (2)	−0.0114 (19)	0.022 (2)	−0.0057 (19)
C15	0.053 (2)	0.0432 (17)	0.0449 (17)	−0.0014 (15)	0.0073 (15)	−0.0039 (14)
C16	0.069 (3)	0.051 (2)	0.063 (2)	0.0070 (18)	0.0045 (19)	0.0067 (17)
C17	0.092 (4)	0.047 (2)	0.083 (3)	0.014 (2)	0.005 (2)	0.009 (2)
C18	0.095 (4)	0.043 (2)	0.088 (3)	−0.008 (2)	0.008 (3)	0.005 (2)
C19	0.070 (3)	0.052 (2)	0.069 (2)	−0.0146 (19)	0.0081 (19)	−0.0006 (18)
C20	0.060 (2)	0.0399 (16)	0.0415 (16)	−0.0027 (15)	0.0088 (15)	−0.0003 (14)
C21	0.0422 (19)	0.0411 (16)	0.057 (2)	−0.0006 (14)	0.0116 (15)	−0.0070 (15)
C22	0.052 (2)	0.065 (2)	0.071 (2)	−0.0036 (18)	0.0237 (19)	−0.0045 (19)
C23	0.041 (2)	0.069 (2)	0.101 (3)	−0.0021 (18)	0.024 (2)	−0.003 (2)
C24	0.041 (2)	0.074 (3)	0.084 (3)	0.0057 (18)	0.0022 (19)	−0.002 (2)
C25	0.045 (2)	0.067 (2)	0.062 (2)	0.0004 (17)	0.0037 (17)	−0.0043 (18)
C26	0.0410 (18)	0.0450 (17)	0.0543 (19)	0.0019 (14)	0.0096 (15)	−0.0097 (15)
C27	0.0434 (19)	0.0542 (19)	0.0482 (18)	−0.0022 (15)	0.0032 (14)	−0.0034 (15)
C28	0.075 (3)	0.087 (3)	0.053 (2)	0.023 (2)	0.0106 (19)	−0.002 (2)
C29	0.081 (3)	0.143 (5)	0.052 (2)	0.024 (3)	0.014 (2)	−0.002 (3)
C30	0.076 (3)	0.123 (4)	0.061 (3)	−0.008 (3)	0.001 (2)	0.023 (3)
C31	0.113 (4)	0.074 (3)	0.076 (3)	0.003 (3)	−0.007 (3)	0.013 (2)
C32	0.099 (3)	0.062 (2)	0.057 (2)	0.015 (2)	−0.002 (2)	−0.0029 (19)
C33	0.0451 (19)	0.0471 (17)	0.0469 (17)	0.0030 (14)	0.0093 (14)	−0.0056 (14)
C34	0.061 (3)	0.056 (2)	0.219 (6)	−0.008 (2)	0.046 (3)	−0.038 (3)
C35	0.104 (4)	0.053 (3)	0.240 (7)	−0.009 (3)	0.080 (5)	−0.037 (4)
C36	0.118 (4)	0.057 (3)	0.083 (3)	0.032 (3)	0.040 (3)	0.004 (2)
C37	0.066 (3)	0.094 (4)	0.102 (4)	0.038 (3)	0.002 (2)	−0.018 (3)
C38	0.049 (2)	0.067 (2)	0.092 (3)	0.0100 (19)	0.003 (2)	−0.020 (2)
C39	0.066 (3)	0.0479 (19)	0.073 (2)	0.0093 (17)	0.017 (2)	−0.0018 (18)
C40	0.141 (5)	0.067 (3)	0.129 (4)	0.026 (3)	0.060 (4)	0.026 (3)
C41	0.119 (5)	0.054 (3)	0.129 (5)	0.022 (3)	0.013 (4)	0.001 (3)
C42	0.100 (4)	0.082 (3)	0.114 (4)	0.042 (3)	0.022 (3)	−0.014 (3)
C43	0.123 (5)	0.103 (4)	0.108 (4)	0.063 (3)	0.053 (3)	0.013 (3)
C44	0.058 (2)	0.066 (2)	0.065 (2)	0.0144 (19)	0.0160 (19)	0.0004 (19)
C45	0.0446 (19)	0.0516 (18)	0.0540 (19)	−0.0005 (15)	0.0060 (15)	−0.0020 (16)
C46	0.0428 (18)	0.0471 (17)	0.0471 (17)	0.0026 (14)	0.0080 (14)	−0.0032 (15)
C47	0.050 (2)	0.061 (2)	0.063 (2)	0.0068 (17)	0.0255 (17)	0.0048 (17)
C48	0.054 (2)	0.0513 (19)	0.064 (2)	0.0002 (16)	0.0220 (17)	0.0106 (16)
C49	0.065 (2)	0.053 (2)	0.060 (2)	0.0067 (17)	0.0269 (18)	0.0034 (17)
C50	0.073 (3)	0.0464 (18)	0.060 (2)	0.0101 (17)	0.0261 (19)	0.0087 (16)
P3	0.0842 (8)	0.0573 (6)	0.0738 (7)	−0.0058 (5)	0.0325 (6)	−0.0005 (5)
F1	0.146 (3)	0.125 (3)	0.249 (5)	0.001 (2)	0.125 (3)	−0.035 (3)
F2	0.153 (3)	0.0830 (19)	0.169 (3)	−0.0405 (19)	0.066 (2)	−0.029 (2)
F3	0.184 (4)	0.177 (4)	0.116 (3)	0.032 (3)	−0.003 (2)	0.042 (2)
F4	0.116 (3)	0.100 (2)	0.183 (3)	−0.0060 (18)	0.077 (2)	−0.025 (2)
F5	0.111 (3)	0.110 (2)	0.238 (4)	−0.052 (2)	0.075 (3)	−0.061 (3)
F6	0.316 (6)	0.143 (3)	0.091 (2)	−0.009 (3)	0.026 (3)	0.035 (2)

Geometric parameters (Å, º)

Cu1—P1	2.2674 (9)	C21—C26	1.389 (4)
Cu1—P2	2.2752 (9)	C22—H22	0.9500
Cu1—N1	2.042 (3)	C22—C23	1.384 (5)
Cu1—N2	2.083 (3)	C23—H23	0.9500
P1—C3	1.827 (3)	C23—C24	1.373 (6)
P1—C9	1.828 (3)	C24—H24	0.9500
P1—C15	1.830 (3)	C24—C25	1.379 (5)
P2—C26	1.839 (3)	C25—H25	0.9500
P2—C27	1.841 (3)	C25—C26	1.404 (5)
P2—C33	1.827 (3)	C27—C28	1.376 (5)
O1—C20	1.398 (4)	C27—C32	1.380 (5)
O1—C21	1.400 (4)	C28—H28	0.9500
O2—C39	1.386 (4)	C28—C29	1.397 (6)
O2—C45	1.351 (4)	C29—H29	0.9500
N1—C2	1.127 (4)	C29—C30	1.345 (7)
N2—C48	1.344 (4)	C30—H30	0.9500
N2—C49	1.329 (4)	C30—C31	1.372 (7)
N3—C44	1.402 (5)	C31—H31	0.9500
N3—C45	1.281 (4)	C31—C32	1.380 (6)
C1—H1A	0.9800	C32—H32	0.9500
C1—H1B	0.9800	C33—C34	1.363 (5)
C1—H1C	0.9800	C33—C38	1.363 (5)
C1—C2	1.462 (5)	C34—H34	0.9500
C3—C4	1.400 (5)	C34—C35	1.384 (6)
C3—C8	1.388 (5)	C35—H35	0.9500
C4—H4	0.9500	C35—C36	1.330 (7)
C4—C5	1.383 (5)	C36—H36	0.9500
C5—H5	0.9500	C36—C37	1.357 (7)
C5—C6	1.364 (6)	C37—H37	0.9500
C6—H6	0.9500	C37—C38	1.383 (5)
C6—C7	1.372 (6)	C38—H38	0.9500
C7—H7	0.9500	C39—C40	1.360 (6)
C7—C8	1.382 (5)	C39—C44	1.351 (5)
C8—H8	0.9500	C40—H40	0.9500
C9—C10	1.392 (4)	C40—C41	1.378 (7)
C9—C14	1.385 (5)	C41—H41	0.9500
C10—H10	0.9500	C41—C42	1.355 (7)
C10—C11	1.385 (5)	C42—H42	0.9500
C11—H11	0.9500	C42—C43	1.360 (7)
C11—C12	1.369 (6)	C43—H43	0.9500
C12—H12	0.9500	C43—C44	1.383 (5)
C12—C13	1.364 (6)	C45—C46	1.462 (4)
C13—H13	0.9500	C46—C47	1.388 (5)
C13—C14	1.379 (5)	C46—C50	1.371 (4)
C14—H14	0.9500	C47—H47	0.9500
C15—C16	1.399 (5)	C47—C48	1.370 (5)
C15—C20	1.385 (5)	C48—H48	0.9500
C16—H16	0.9500	C49—H49	0.9500
C16—C17	1.383 (5)	C49—C50	1.385 (5)
C17—H17	0.9500	C50—H50	0.9500
C17—C18	1.360 (6)	P3—F1	1.540 (3)
C18—H18	0.9500	P3—F2	1.583 (3)
C18—C19	1.381 (6)	P3—F3	1.559 (4)
C19—H19	0.9500	P3—F4	1.586 (3)
C19—C20	1.384 (5)	P3—F5	1.549 (3)
C21—C22	1.385 (5)	P3—F6	1.546 (4)
P1—Cu1—P2	114.28 (3)	C23—C24—C25	119.6 (4)
N1—Cu1—P1	108.28 (9)	C25—C24—H24	120.2
N1—Cu1—P2	115.62 (9)	C24—C25—H25	119.1
N1—Cu1—N2	98.54 (11)	C24—C25—C26	121.8 (3)
N2—Cu1—P1	113.86 (7)	C26—C25—H25	119.1
N2—Cu1—P2	105.30 (8)	C21—C26—P2	120.2 (2)
C3—P1—Cu1	115.86 (11)	C21—C26—C25	116.9 (3)
C3—P1—C9	102.59 (15)	C25—C26—P2	122.9 (3)
C3—P1—C15	104.34 (15)	C28—C27—P2	122.9 (3)
C9—P1—Cu1	117.01 (11)	C28—C27—C32	118.2 (3)
C9—P1—C15	104.83 (14)	C32—C27—P2	118.7 (3)
C15—P1—Cu1	110.87 (11)	C27—C28—H28	119.8
C26—P2—Cu1	112.60 (10)	C27—C28—C29	120.4 (4)
C26—P2—C27	103.32 (15)	C29—C28—H28	119.8
C27—P2—Cu1	113.10 (11)	C28—C29—H29	119.8
C33—P2—Cu1	118.13 (11)	C30—C29—C28	120.5 (4)
C33—P2—C26	103.28 (15)	C30—C29—H29	119.8
C33—P2—C27	104.90 (14)	C29—C30—H30	120.0
C20—O1—C21	118.2 (2)	C29—C30—C31	119.9 (4)
C45—O2—C39	104.3 (3)	C31—C30—H30	120.0
C2—N1—Cu1	168.1 (3)	C30—C31—H31	120.0
C48—N2—Cu1	123.6 (2)	C30—C31—C32	120.1 (4)
C49—N2—Cu1	119.2 (2)	C32—C31—H31	120.0
C49—N2—C48	117.2 (3)	C27—C32—C31	120.9 (4)
C45—N3—C44	105.1 (3)	C27—C32—H32	119.5
H1A—C1—H1B	109.5	C31—C32—H32	119.5
H1A—C1—H1C	109.5	C34—C33—P2	124.5 (3)
H1B—C1—H1C	109.5	C34—C33—C38	117.3 (3)
C2—C1—H1A	109.5	C38—C33—P2	118.2 (3)
C2—C1—H1B	109.5	C33—C34—H34	119.4
C2—C1—H1C	109.5	C33—C34—C35	121.2 (5)
N1—C2—C1	178.5 (4)	C35—C34—H34	119.4
C4—C3—P1	123.0 (3)	C34—C35—H35	119.5
C8—C3—P1	118.1 (3)	C36—C35—C34	121.1 (5)
C8—C3—C4	118.7 (3)	C36—C35—H35	119.5
C3—C4—H4	120.3	C35—C36—H36	120.6
C5—C4—C3	119.4 (4)	C35—C36—C37	118.8 (4)
C5—C4—H4	120.3	C37—C36—H36	120.6
C4—C5—H5	119.5	C36—C37—H37	119.7
C6—C5—C4	121.1 (4)	C36—C37—C38	120.7 (4)
C6—C5—H5	119.5	C38—C37—H37	119.7
C5—C6—H6	119.9	C33—C38—C37	120.9 (4)
C5—C6—C7	120.2 (4)	C33—C38—H38	119.5
C7—C6—H6	119.9	C37—C38—H38	119.5
C6—C7—H7	120.1	C40—C39—O2	129.5 (4)
C6—C7—C8	119.8 (4)	C44—C39—O2	107.8 (3)
C8—C7—H7	120.1	C44—C39—C40	122.7 (4)
C3—C8—H8	119.6	C39—C40—H40	121.8
C7—C8—C3	120.8 (3)	C39—C40—C41	116.4 (5)
C7—C8—H8	119.6	C41—C40—H40	121.8
C10—C9—P1	117.7 (2)	C40—C41—H41	119.3
C14—C9—P1	123.5 (3)	C42—C41—C40	121.4 (5)
C14—C9—C10	118.7 (3)	C42—C41—H41	119.3
C9—C10—H10	119.9	C41—C42—H42	119.1
C11—C10—C9	120.2 (3)	C43—C42—C41	121.7 (4)
C11—C10—H10	119.9	C43—C42—H42	119.1
C10—C11—H11	119.9	C42—C43—H43	121.4
C12—C11—C10	120.1 (4)	C42—C43—C44	117.2 (5)
C12—C11—H11	119.9	C44—C43—H43	121.4
C11—C12—H12	120.0	C39—C44—N3	108.3 (3)
C13—C12—C11	120.0 (4)	C39—C44—C43	120.5 (4)
C13—C12—H12	120.0	C43—C44—N3	131.2 (4)
C12—C13—H13	119.6	O2—C45—C46	118.1 (3)
C12—C13—C14	120.8 (4)	N3—C45—O2	114.5 (3)
C14—C13—H13	119.6	N3—C45—C46	127.3 (3)
C9—C14—H14	119.9	C47—C46—C45	121.2 (3)
C13—C14—C9	120.2 (4)	C50—C46—C45	120.3 (3)
C13—C14—H14	119.9	C50—C46—C47	118.4 (3)
C16—C15—P1	123.8 (3)	C46—C47—H47	120.4
C20—C15—P1	118.6 (2)	C48—C47—C46	119.2 (3)
C20—C15—C16	117.3 (3)	C48—C47—H47	120.4
C15—C16—H16	119.6	N2—C48—C47	122.9 (3)
C17—C16—C15	120.7 (4)	N2—C48—H48	118.5
C17—C16—H16	119.6	C47—C48—H48	118.5
C16—C17—H17	119.7	N2—C49—H49	118.2
C18—C17—C16	120.5 (4)	N2—C49—C50	123.6 (3)
C18—C17—H17	119.7	C50—C49—H49	118.2
C17—C18—H18	119.8	C46—C50—C49	118.6 (3)
C17—C18—C19	120.4 (4)	C46—C50—H50	120.7
C19—C18—H18	119.8	C49—C50—H50	120.7
C18—C19—H19	120.5	F1—P3—F2	89.6 (2)
C18—C19—C20	119.0 (4)	F1—P3—F3	93.6 (3)
C20—C19—H19	120.5	F1—P3—F4	177.1 (2)
C15—C20—O1	116.1 (3)	F1—P3—F5	94.2 (2)
C15—C20—C19	122.0 (3)	F1—P3—F6	89.3 (3)
C19—C20—O1	121.9 (3)	F2—P3—F4	87.75 (18)
C22—C21—O1	118.4 (3)	F3—P3—F2	87.9 (2)
C22—C21—C26	121.8 (3)	F3—P3—F4	87.5 (2)
C26—C21—O1	119.7 (3)	F5—P3—F2	175.9 (2)
C21—C22—H22	120.3	F5—P3—F3	93.5 (3)
C23—C22—C21	119.5 (4)	F5—P3—F4	88.46 (17)
C23—C22—H22	120.3	F5—P3—F6	88.8 (2)
C22—C23—H23	119.8	F6—P3—F2	89.6 (2)
C24—C23—C22	120.4 (4)	F6—P3—F3	176.2 (3)
C24—C23—H23	119.8	F6—P3—F4	89.5 (3)
C23—C24—H24	120.2
Cu1—P1—C3—C4	−146.4 (3)	C17—C18—C19—C20	−0.1 (6)
Cu1—P1—C3—C8	29.6 (3)	C18—C19—C20—O1	179.1 (3)
Cu1—P1—C9—C10	39.1 (3)	C18—C19—C20—C15	0.0 (5)
Cu1—P1—C9—C14	−145.2 (3)	C20—O1—C21—C22	−98.1 (3)
Cu1—P1—C15—C16	−129.6 (3)	C20—O1—C21—C26	86.0 (3)
Cu1—P1—C15—C20	43.8 (3)	C20—C15—C16—C17	−1.1 (5)
Cu1—P2—C26—C21	38.7 (3)	C21—O1—C20—C15	−149.2 (3)
Cu1—P2—C26—C25	−140.0 (2)	C21—O1—C20—C19	31.6 (4)
Cu1—P2—C27—C28	−119.3 (3)	C21—C22—C23—C24	−0.2 (6)
Cu1—P2—C27—C32	54.7 (3)	C22—C21—C26—P2	−177.3 (3)
Cu1—P2—C33—C34	−148.5 (4)	C22—C21—C26—C25	1.5 (5)
Cu1—P2—C33—C38	31.0 (3)	C22—C23—C24—C25	0.5 (6)
Cu1—N2—C48—C47	179.4 (3)	C23—C24—C25—C26	0.1 (6)
Cu1—N2—C49—C50	−178.9 (3)	C24—C25—C26—P2	177.7 (3)
P1—C3—C4—C5	176.2 (3)	C24—C25—C26—C21	−1.1 (5)
P1—C3—C8—C7	−176.6 (3)	C26—P2—C27—C28	118.7 (3)
P1—C9—C10—C11	176.1 (3)	C26—P2—C27—C32	−67.3 (3)
P1—C9—C14—C13	−175.1 (3)	C26—P2—C33—C34	−23.5 (4)
P1—C15—C16—C17	172.3 (3)	C26—P2—C33—C38	156.0 (3)
P1—C15—C20—O1	7.6 (4)	C26—C21—C22—C23	−0.9 (5)
P1—C15—C20—C19	−173.2 (3)	C27—P2—C26—C21	161.1 (3)
P2—C27—C28—C29	172.4 (3)	C27—P2—C26—C25	−17.6 (3)
P2—C27—C32—C31	−173.2 (4)	C27—P2—C33—C34	84.5 (4)
P2—C33—C34—C35	178.5 (5)	C27—P2—C33—C38	−96.1 (3)
P2—C33—C38—C37	−178.1 (3)	C27—C28—C29—C30	1.2 (7)
O1—C21—C22—C23	−176.7 (3)	C28—C27—C32—C31	1.1 (6)
O1—C21—C26—P2	−1.5 (4)	C28—C29—C30—C31	−0.1 (8)
O1—C21—C26—C25	177.3 (3)	C29—C30—C31—C32	−0.5 (8)
O2—C39—C40—C41	179.6 (5)	C30—C31—C32—C27	0.0 (7)
O2—C39—C44—N3	−0.2 (5)	C32—C27—C28—C29	−1.7 (6)
O2—C39—C44—C43	179.8 (4)	C33—P2—C26—C21	−89.8 (3)
O2—C45—C46—C47	174.7 (3)	C33—P2—C26—C25	91.5 (3)
O2—C45—C46—C50	−8.1 (5)	C33—P2—C27—C28	10.8 (4)
N2—C49—C50—C46	−0.1 (6)	C33—P2—C27—C32	−175.2 (3)
N3—C45—C46—C47	−8.0 (6)	C33—C34—C35—C36	−0.7 (10)
N3—C45—C46—C50	169.2 (4)	C34—C33—C38—C37	1.4 (6)
C3—P1—C9—C10	−88.9 (3)	C34—C35—C36—C37	1.9 (9)
C3—P1—C9—C14	86.9 (3)	C35—C36—C37—C38	−1.4 (8)
C3—P1—C15—C16	−4.2 (3)	C36—C37—C38—C33	−0.3 (7)
C3—P1—C15—C20	169.2 (2)	C38—C33—C34—C35	−1.0 (8)
C3—C4—C5—C6	0.1 (6)	C39—O2—C45—N3	0.1 (4)
C4—C3—C8—C7	−0.5 (5)	C39—O2—C45—C46	177.7 (3)
C4—C5—C6—C7	−0.3 (7)	C39—C40—C41—C42	−0.4 (9)
C5—C6—C7—C8	0.1 (6)	C40—C39—C44—N3	179.9 (5)
C6—C7—C8—C3	0.3 (6)	C40—C39—C44—C43	−0.2 (7)
C8—C3—C4—C5	0.3 (5)	C40—C41—C42—C43	1.9 (9)
C9—P1—C3—C4	−17.7 (3)	C41—C42—C43—C44	−2.5 (9)
C9—P1—C3—C8	158.3 (3)	C42—C43—C44—N3	−178.4 (5)
C9—P1—C15—C16	103.3 (3)	C42—C43—C44—C39	1.6 (8)
C9—P1—C15—C20	−83.3 (3)	C44—N3—C45—O2	−0.2 (5)
C9—C10—C11—C12	−0.5 (6)	C44—N3—C45—C46	−177.6 (3)
C10—C9—C14—C13	0.6 (6)	C44—C39—C40—C41	−0.5 (8)
C10—C11—C12—C13	0.1 (7)	C45—O2—C39—C40	180.0 (5)
C11—C12—C13—C14	0.7 (7)	C45—O2—C39—C44	0.1 (4)
C12—C13—C14—C9	−1.0 (7)	C45—N3—C44—C39	0.3 (5)
C14—C9—C10—C11	0.1 (5)	C45—N3—C44—C43	−179.7 (5)
C15—P1—C3—C4	91.5 (3)	C45—C46—C47—C48	177.7 (3)
C15—P1—C3—C8	−92.6 (3)	C45—C46—C50—C49	−177.2 (3)
C15—P1—C9—C10	162.4 (3)	C46—C47—C48—N2	−1.0 (6)
C15—P1—C9—C14	−21.9 (3)	C47—C46—C50—C49	0.1 (5)
C15—C16—C17—C18	1.1 (6)	C48—N2—C49—C50	−0.4 (5)
C16—C15—C20—O1	−178.6 (3)	C49—N2—C48—C47	0.9 (5)
C16—C15—C20—C19	0.6 (5)	C50—C46—C47—C48	0.4 (5)
C16—C17—C18—C19	−0.5 (7)