A new phospho­rescent heteroleptic cuprous complex with a neutral 2-methyl­quinolin-8-ol ligand: synthesis, structure characterization, properties and TD–DFT calculations

Luminescent Cu^I complexes have emerged as promising substitutes for phos­phorescent emitters based on Ir, Pt and Os due to their abundance and low cost. The title heteroleptic cuprous complex, [9,9-dimethyl-4,5-bis­(di­phenyl­phos­phan­yl)-9H-xanthene-κ²P,P](2-methyl­quinolin-8-ol-κ²N,O)copper(I) hexa­fluoro­phosphate, [Cu(C₁₀H₉NO)(C₃₉H₃₂OP₂)]PF₆, conventionally abbreviated as [Cu(Xantphos)(8-HOXQ)]PF₆, where Xantphos is the chelating diphosphine ligand 9,9-dimethyl-4,5-bis­(di­phenyl­phosphan­yl)-9H-xanthene and 8-HOXQ is the N,O-chelating ligand 2-methyl­quinolin-8-ol that remains protonated at the hy­droxy O atom, is described. In this complex, the asymmetric unit consists of a hexa­fluoro­phosphate anion and a whole mononuclear cation, where the Cu^I atom is coordinated by two P atoms from the Xantphos ligand and by the N and O atoms from the 8-HOXQ ligand, giving rise to a tetra­hedral CuP₂NO coordination geometry. The electronic absorption and photoluminescence properties of this complex have been studied on as-synthesized samples, whose purity had been determined by powder X-ray diffraction. In the detailed TD–DFT (time-dependent density functional theory) studies, the yellow emission appears to be derived from the inter-ligand charge transfer and metal-to-ligand charge transfer (M+L′)→LCT excited state (LCT is ligand charge transfer).

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: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

[9,9-Dimethyl-4,5-bis(diphenylphosphanyl)-9H-xanthene-κ²P,P](2-methylquinolin-8-ol-κ²N,O)copper(I) hexafluorophosphate

Crystal data

[Cu(C10H9NO)(C39H32OP2)]PF6	F(000) = 1944
Mr = 946.28	Dx = 1.408 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.5376 (6) Å	Cell parameters from 3939 reflections
b = 21.5025 (14) Å	θ = 3.0–29.5°
c = 19.9462 (19) Å	µ = 0.66 mm^−1
β = 99.079 (7)°	T = 273 K
V = 4462.9 (6) Å^3	Plate, brown–yellow
Z = 4	0.49 × 0.4 × 0.29 mm

Data collection

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer	10570 independent reflections
Radiation source: Enhance (Mo) X-ray Source	6277 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
Detector resolution: 10.3592 pixels mm^-1	θmax = 29.6°, θmin = 3.0°
ω scans	h = −10→14
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −28→18
Tmin = 0.758, Tmax = 1.000	l = −25→20
20841 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.064	H-atom parameters constrained
wR(F^2) = 0.198	w = 1/[σ^2(Fo^2) + (0.087P)^2 + 3.132P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
10570 reflections	Δρmax = 0.71 e Å^−3
563 parameters	Δρmin = −0.64 e Å^−3
3 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Cu1	0.35844 (4)	0.24536 (2)	0.48474 (2)	0.04201 (16)
P1	0.18848 (9)	0.20212 (4)	0.52757 (5)	0.0399 (2)
P2	0.31549 (8)	0.32818 (5)	0.41537 (5)	0.0390 (2)
O1	0.4361 (3)	0.16039 (15)	0.43613 (17)	0.0664 (9)
H1	0.4187	0.1374	0.4011	0.100*
O2	0.1577 (2)	0.33440 (12)	0.51944 (12)	0.0439 (6)
N1	0.5361 (3)	0.23085 (17)	0.54151 (17)	0.0501 (8)
C1	0.5897 (3)	0.1733 (2)	0.5344 (2)	0.0517 (10)
C2	0.5345 (4)	0.1345 (2)	0.4804 (2)	0.0549 (11)
C3	0.5800 (5)	0.0765 (2)	0.4733 (3)	0.0757 (14)
H3	0.5437	0.0514	0.4374	0.091*
C4	0.6839 (6)	0.0543 (3)	0.5214 (4)	0.0945 (19)
H4	0.7135	0.0139	0.5177	0.113*
C5	0.7401 (5)	0.0909 (3)	0.5724 (3)	0.0851 (17)
H5	0.8092	0.0758	0.6027	0.102*
C6	0.6961 (4)	0.1514 (3)	0.5802 (3)	0.0677 (14)
C7	0.7517 (5)	0.1927 (3)	0.6313 (3)	0.0818 (16)
H7	0.8228	0.1803	0.6621	0.098*
C8	0.7018 (5)	0.2506 (3)	0.6357 (3)	0.0812 (17)
H8	0.7404	0.2785	0.6683	0.097*
C9	0.5915 (4)	0.2680 (2)	0.5904 (2)	0.0595 (11)
C10	0.5292 (6)	0.3297 (2)	0.5979 (3)	0.0898 (18)
H10A	0.5196	0.3516	0.5554	0.135*
H10B	0.5819	0.3537	0.6321	0.135*
H10C	0.4462	0.3234	0.6108	0.135*
C11	0.2076 (4)	0.12609 (18)	0.5690 (2)	0.0454 (9)
C12	0.3279 (4)	0.1089 (2)	0.6028 (2)	0.0519 (10)
H12	0.3971	0.1358	0.6031	0.062*
C13	0.3460 (5)	0.0525 (2)	0.6356 (2)	0.0658 (13)
H13	0.4270	0.0414	0.6581	0.079*
C14	0.2442 (6)	0.0129 (2)	0.6352 (3)	0.0725 (14)
H14	0.2562	−0.0252	0.6574	0.087*
C15	0.1252 (5)	0.0289 (2)	0.6025 (3)	0.0743 (14)
H15	0.0569	0.0015	0.6022	0.089*
C16	0.1051 (4)	0.0852 (2)	0.5698 (2)	0.0595 (11)
H16	0.0233	0.0959	0.5482	0.071*
C17	0.0411 (3)	0.19129 (18)	0.4671 (2)	0.0446 (9)
C18	0.0448 (4)	0.1507 (2)	0.4136 (2)	0.0560 (11)
H18	0.1218	0.1312	0.4091	0.067*
C19	−0.0643 (5)	0.1386 (2)	0.3666 (3)	0.0712 (14)
H19	−0.0607	0.1110	0.3310	0.085*
C20	−0.1769 (5)	0.1677 (3)	0.3732 (3)	0.0771 (16)
H20	−0.2502	0.1600	0.3417	0.093*
C21	−0.1830 (4)	0.2078 (3)	0.4251 (3)	0.0757 (15)
H21	−0.2603	0.2274	0.4287	0.091*
C22	−0.0743 (4)	0.2201 (2)	0.4731 (2)	0.0598 (11)
H22	−0.0794	0.2474	0.5088	0.072*
C23	0.1407 (3)	0.25128 (17)	0.59370 (19)	0.0415 (8)
C24	0.1136 (4)	0.2307 (2)	0.6556 (2)	0.0535 (10)
H24	0.1138	0.1882	0.6645	0.064*
C25	0.0864 (5)	0.2715 (2)	0.7042 (2)	0.0625 (12)
H25	0.0665	0.2565	0.7451	0.075*
C26	0.0885 (4)	0.3351 (2)	0.6925 (2)	0.0596 (11)
H26	0.0722	0.3624	0.7263	0.072*
C27	0.1144 (4)	0.35883 (19)	0.6311 (2)	0.0477 (9)
C28	0.1379 (3)	0.31585 (17)	0.58318 (19)	0.0406 (8)
C29	0.1099 (4)	0.4276 (2)	0.6129 (2)	0.0561 (11)
C30	0.1478 (7)	0.4687 (3)	0.6763 (3)	0.102 (2)
H30A	0.2355	0.4606	0.6956	0.153*
H30B	0.0929	0.4594	0.7091	0.153*
H30C	0.1385	0.5117	0.6636	0.153*
C31	−0.0285 (4)	0.4433 (2)	0.5803 (3)	0.0793 (16)
H31A	−0.0347	0.4869	0.5699	0.119*
H31B	−0.0864	0.4332	0.6113	0.119*
H31C	−0.0509	0.4197	0.5392	0.119*
C32	0.1990 (4)	0.43880 (18)	0.5609 (2)	0.0470 (9)
C33	0.2156 (3)	0.39230 (16)	0.51543 (19)	0.0408 (8)
C34	0.2892 (3)	0.39792 (16)	0.4638 (2)	0.0398 (8)
C35	0.3452 (4)	0.45553 (19)	0.4563 (2)	0.0526 (10)
H35	0.3929	0.4619	0.4215	0.063*
C36	0.3303 (4)	0.5034 (2)	0.5006 (3)	0.0611 (12)
H36	0.3680	0.5418	0.4952	0.073*
C37	0.2607 (4)	0.4950 (2)	0.5523 (2)	0.0583 (11)
H37	0.2543	0.5274	0.5824	0.070*
C38	0.4366 (3)	0.35287 (18)	0.3645 (2)	0.0445 (9)
C39	0.5612 (4)	0.3338 (2)	0.3840 (2)	0.0556 (11)
H39	0.5819	0.3086	0.4221	0.067*
C40	0.6559 (4)	0.3517 (2)	0.3476 (3)	0.0668 (13)
H40	0.7403	0.3389	0.3615	0.080*
C41	0.6265 (4)	0.3878 (2)	0.2918 (3)	0.0616 (12)
H41	0.6908	0.3993	0.2673	0.074*
C42	0.5038 (4)	0.4077 (2)	0.2713 (3)	0.0665 (13)
H42	0.4843	0.4331	0.2333	0.080*
C43	0.4083 (4)	0.3896 (2)	0.3075 (2)	0.0597 (12)
H43	0.3241	0.4023	0.2932	0.072*
C44	0.1699 (3)	0.32183 (18)	0.35321 (19)	0.0419 (8)
C45	0.1440 (4)	0.2647 (2)	0.3219 (2)	0.0584 (11)
H45	0.1991	0.2312	0.3334	0.070*
C46	0.0346 (5)	0.2577 (2)	0.2730 (3)	0.0719 (14)
H46	0.0162	0.2194	0.2521	0.086*
C47	−0.0451 (5)	0.3068 (3)	0.2557 (3)	0.0770 (15)
H47	−0.1183	0.3018	0.2234	0.092*
C48	−0.0179 (4)	0.3633 (3)	0.2858 (3)	0.0790 (16)
H48	−0.0718	0.3970	0.2729	0.095*
C49	0.0874 (4)	0.3710 (2)	0.3345 (2)	0.0600 (12)
H49	0.1038	0.4095	0.3552	0.072*
P3	0.27828 (15)	0.06274 (7)	0.27776 (8)	0.0782 (4)
F1	0.2925 (5)	0.0686 (3)	0.3584 (2)	0.167 (2)
F2	0.2978 (8)	−0.0060 (3)	0.2826 (4)	0.246 (4)
F3	0.4268 (5)	0.0636 (3)	0.2922 (3)	0.199 (3)
F4	0.2743 (8)	0.0649 (5)	0.2037 (3)	0.288 (5)
F5	0.2625 (11)	0.1297 (3)	0.2790 (4)	0.308 (6)
F6	0.1407 (5)	0.0530 (5)	0.2722 (5)	0.293 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0389 (2)	0.0410 (3)	0.0447 (3)	0.00433 (18)	0.00251 (19)	0.0008 (2)
P1	0.0416 (5)	0.0346 (5)	0.0438 (6)	0.0031 (4)	0.0079 (4)	0.0018 (4)
P2	0.0375 (5)	0.0393 (5)	0.0401 (5)	0.0031 (4)	0.0062 (4)	0.0016 (4)
O1	0.0641 (18)	0.066 (2)	0.063 (2)	0.0211 (16)	−0.0087 (15)	−0.0183 (16)
O2	0.0615 (15)	0.0358 (15)	0.0356 (14)	−0.0015 (11)	0.0114 (12)	−0.0013 (11)
N1	0.0438 (17)	0.060 (2)	0.0451 (19)	−0.0009 (15)	0.0023 (14)	0.0039 (17)
C1	0.0405 (19)	0.059 (3)	0.057 (3)	0.0065 (18)	0.0120 (18)	0.012 (2)
C2	0.050 (2)	0.056 (3)	0.060 (3)	0.0101 (19)	0.0143 (19)	0.004 (2)
C3	0.085 (3)	0.059 (3)	0.087 (4)	0.025 (3)	0.024 (3)	0.001 (3)
C4	0.090 (4)	0.083 (4)	0.116 (5)	0.040 (3)	0.030 (4)	0.026 (4)
C5	0.068 (3)	0.100 (5)	0.086 (4)	0.035 (3)	0.007 (3)	0.025 (4)
C6	0.047 (2)	0.088 (4)	0.069 (3)	0.016 (2)	0.009 (2)	0.023 (3)
C7	0.054 (3)	0.115 (5)	0.069 (4)	0.014 (3)	−0.009 (2)	0.016 (3)
C8	0.064 (3)	0.112 (5)	0.058 (3)	−0.010 (3)	−0.017 (2)	−0.003 (3)
C9	0.054 (2)	0.067 (3)	0.052 (3)	−0.007 (2)	−0.0055 (19)	−0.004 (2)
C10	0.110 (4)	0.069 (4)	0.078 (4)	0.004 (3)	−0.023 (3)	−0.015 (3)
C11	0.053 (2)	0.034 (2)	0.049 (2)	0.0071 (17)	0.0097 (17)	0.0002 (17)
C12	0.058 (2)	0.045 (2)	0.053 (3)	0.0091 (18)	0.0112 (19)	0.006 (2)
C13	0.080 (3)	0.056 (3)	0.059 (3)	0.024 (2)	0.006 (2)	0.005 (2)
C14	0.115 (4)	0.040 (3)	0.062 (3)	0.015 (3)	0.015 (3)	0.012 (2)
C15	0.093 (4)	0.047 (3)	0.082 (4)	−0.010 (2)	0.009 (3)	0.016 (3)
C16	0.064 (3)	0.049 (3)	0.066 (3)	−0.003 (2)	0.011 (2)	0.006 (2)
C17	0.046 (2)	0.038 (2)	0.049 (2)	−0.0022 (16)	0.0062 (17)	0.0067 (18)
C18	0.056 (2)	0.058 (3)	0.055 (3)	−0.007 (2)	0.0083 (19)	0.001 (2)
C19	0.084 (3)	0.071 (3)	0.055 (3)	−0.026 (3)	−0.002 (2)	−0.001 (2)
C20	0.066 (3)	0.080 (4)	0.076 (4)	−0.015 (3)	−0.016 (3)	0.020 (3)
C21	0.050 (3)	0.080 (4)	0.093 (4)	0.008 (2)	−0.002 (2)	0.025 (3)
C22	0.056 (2)	0.057 (3)	0.066 (3)	0.012 (2)	0.006 (2)	0.009 (2)
C23	0.0450 (19)	0.040 (2)	0.040 (2)	0.0022 (16)	0.0075 (15)	0.0040 (17)
C24	0.067 (3)	0.047 (2)	0.048 (2)	0.006 (2)	0.015 (2)	0.010 (2)
C25	0.089 (3)	0.060 (3)	0.041 (2)	0.012 (2)	0.021 (2)	0.013 (2)
C26	0.075 (3)	0.064 (3)	0.041 (2)	0.010 (2)	0.014 (2)	−0.005 (2)
C27	0.055 (2)	0.047 (2)	0.041 (2)	0.0068 (18)	0.0068 (17)	−0.0019 (18)
C28	0.0455 (19)	0.039 (2)	0.037 (2)	0.0008 (16)	0.0048 (15)	0.0010 (16)
C29	0.078 (3)	0.046 (2)	0.046 (2)	0.004 (2)	0.013 (2)	−0.006 (2)
C30	0.178 (6)	0.069 (4)	0.070 (4)	−0.018 (4)	0.049 (4)	−0.029 (3)
C31	0.075 (3)	0.072 (3)	0.098 (4)	0.032 (3)	0.033 (3)	0.022 (3)
C32	0.055 (2)	0.037 (2)	0.048 (2)	0.0037 (17)	0.0035 (17)	−0.0056 (18)
C33	0.0449 (19)	0.0312 (19)	0.044 (2)	0.0014 (15)	−0.0008 (16)	0.0013 (16)
C34	0.0367 (17)	0.035 (2)	0.046 (2)	0.0049 (15)	0.0029 (15)	−0.0009 (16)
C35	0.046 (2)	0.047 (2)	0.065 (3)	−0.0036 (18)	0.0086 (18)	0.001 (2)
C36	0.058 (2)	0.038 (2)	0.087 (4)	−0.0096 (19)	0.012 (2)	−0.005 (2)
C37	0.066 (3)	0.040 (2)	0.066 (3)	−0.0028 (19)	0.003 (2)	−0.010 (2)
C38	0.046 (2)	0.041 (2)	0.048 (2)	0.0031 (16)	0.0105 (16)	−0.0032 (18)
C39	0.048 (2)	0.058 (3)	0.063 (3)	0.0124 (19)	0.0136 (19)	0.005 (2)
C40	0.045 (2)	0.073 (3)	0.086 (4)	0.003 (2)	0.022 (2)	−0.001 (3)
C41	0.059 (3)	0.058 (3)	0.074 (3)	−0.011 (2)	0.030 (2)	−0.009 (3)
C42	0.067 (3)	0.074 (3)	0.062 (3)	−0.004 (2)	0.021 (2)	0.011 (3)
C43	0.047 (2)	0.073 (3)	0.060 (3)	0.001 (2)	0.0112 (19)	0.015 (2)
C44	0.0390 (18)	0.048 (2)	0.039 (2)	−0.0012 (16)	0.0081 (15)	0.0014 (17)
C45	0.069 (3)	0.053 (3)	0.051 (3)	−0.004 (2)	0.000 (2)	0.004 (2)
C46	0.088 (4)	0.072 (3)	0.052 (3)	−0.028 (3)	−0.002 (2)	−0.006 (2)
C47	0.053 (3)	0.110 (5)	0.062 (3)	−0.013 (3)	−0.008 (2)	0.009 (3)
C48	0.054 (3)	0.099 (4)	0.077 (4)	0.023 (3)	−0.012 (2)	−0.004 (3)
C49	0.049 (2)	0.062 (3)	0.066 (3)	0.011 (2)	−0.002 (2)	−0.009 (2)
P3	0.0936 (10)	0.0697 (10)	0.0739 (10)	0.0095 (7)	0.0213 (8)	−0.0098 (7)
F1	0.202 (5)	0.200 (5)	0.099 (3)	0.000 (4)	0.026 (3)	−0.026 (3)
F2	0.337 (9)	0.091 (4)	0.279 (9)	0.008 (5)	−0.047 (7)	−0.040 (4)
F3	0.113 (3)	0.269 (8)	0.217 (6)	0.010 (4)	0.034 (4)	0.062 (6)
F4	0.297 (8)	0.502 (14)	0.071 (3)	0.181 (9)	0.046 (4)	0.042 (6)
F5	0.576 (17)	0.086 (4)	0.250 (9)	0.110 (7)	0.031 (10)	0.011 (4)
F6	0.106 (4)	0.399 (13)	0.377 (12)	−0.061 (6)	0.046 (5)	−0.139 (10)

Geometric parameters (Å, º)

Cu1—P1	2.2989 (10)	C23—C24	1.384 (6)
Cu1—P2	2.2569 (11)	C23—C28	1.404 (5)
Cu1—O1	2.280 (3)	C24—H24	0.9300
Cu1—N1	2.053 (3)	C24—C25	1.371 (6)
P1—C11	1.829 (4)	C25—H25	0.9300
P1—C17	1.825 (4)	C25—C26	1.388 (6)
P1—C23	1.822 (4)	C26—H26	0.9300
P2—C34	1.828 (4)	C26—C27	1.392 (6)
P2—C38	1.829 (4)	C27—C28	1.380 (5)
P2—C44	1.819 (4)	C27—C29	1.522 (6)
O1—H1	0.8515	C29—C30	1.543 (7)
O1—C2	1.371 (5)	C29—C31	1.538 (6)
O2—C28	1.380 (4)	C29—C32	1.523 (6)
O2—C33	1.394 (4)	C30—H30A	0.9600
N1—C1	1.376 (5)	C30—H30B	0.9600
N1—C9	1.323 (5)	C30—H30C	0.9600
C1—C2	1.414 (6)	C31—H31A	0.9600
C1—C6	1.410 (6)	C31—H31B	0.9600
C2—C3	1.352 (6)	C31—H31C	0.9600
C3—H3	0.9300	C32—C33	1.380 (5)
C3—C4	1.419 (8)	C32—C37	1.395 (6)
C4—H4	0.9300	C33—C34	1.389 (5)
C4—C5	1.346 (9)	C34—C35	1.390 (5)
C5—H5	0.9300	C35—H35	0.9300
C5—C6	1.398 (8)	C35—C36	1.382 (6)
C6—C7	1.407 (8)	C36—H36	0.9300
C7—H7	0.9300	C36—C37	1.368 (6)
C7—C8	1.361 (8)	C37—H37	0.9300
C8—H8	0.9300	C38—C39	1.372 (5)
C8—C9	1.405 (6)	C38—C43	1.377 (6)
C9—C10	1.498 (7)	C39—H39	0.9300
C10—H10A	0.9600	C39—C40	1.379 (6)
C10—H10B	0.9600	C40—H40	0.9300
C10—H10C	0.9600	C40—C41	1.352 (7)
C11—C12	1.388 (5)	C41—H41	0.9300
C11—C16	1.395 (6)	C41—C42	1.362 (6)
C12—H12	0.9300	C42—H42	0.9300
C12—C13	1.377 (6)	C42—C43	1.384 (6)
C13—H13	0.9300	C43—H43	0.9300
C13—C14	1.370 (7)	C44—C45	1.386 (6)
C14—H14	0.9300	C44—C49	1.382 (6)
C14—C15	1.363 (7)	C45—H45	0.9300
C15—H15	0.9300	C45—C46	1.396 (6)
C15—C16	1.375 (6)	C46—H46	0.9300
C16—H16	0.9300	C46—C47	1.358 (7)
C17—C18	1.383 (6)	C47—H47	0.9300
C17—C22	1.388 (6)	C47—C48	1.366 (8)
C18—H18	0.9300	C48—H48	0.9300
C18—C19	1.389 (6)	C48—C49	1.365 (6)
C19—H19	0.9300	C49—H49	0.9300
C19—C20	1.367 (7)	P3—F1	1.596 (5)
C20—H20	0.9300	P3—F2	1.493 (6)
C20—C21	1.356 (8)	P3—F3	1.546 (5)
C21—H21	0.9300	P3—F4	1.472 (5)
C21—C22	1.398 (7)	P3—F5	1.449 (6)
C22—H22	0.9300	P3—F6	1.452 (5)
P2—Cu1—P1	117.03 (4)	C24—C25—H25	120.0
P2—Cu1—O1	114.98 (9)	C24—C25—C26	120.0 (4)
O1—Cu1—P1	100.77 (10)	C26—C25—H25	120.0
N1—Cu1—P1	115.44 (10)	C25—C26—H26	119.3
N1—Cu1—P2	122.36 (10)	C25—C26—C27	121.4 (4)
N1—Cu1—O1	75.86 (12)	C27—C26—H26	119.3
C11—P1—Cu1	119.54 (13)	C26—C27—C29	124.3 (4)
C17—P1—Cu1	115.93 (13)	C28—C27—C26	116.4 (4)
C17—P1—C11	101.92 (17)	C28—C27—C29	119.1 (4)
C23—P1—Cu1	110.78 (12)	O2—C28—C23	114.9 (3)
C23—P1—C11	102.39 (18)	O2—C28—C27	121.0 (3)
C23—P1—C17	104.43 (18)	C27—C28—C23	124.1 (4)
C34—P2—Cu1	110.85 (13)	C27—C29—C30	111.5 (4)
C34—P2—C38	103.41 (17)	C27—C29—C31	107.9 (4)
C38—P2—Cu1	118.62 (13)	C27—C29—C32	108.5 (3)
C44—P2—Cu1	115.12 (13)	C31—C29—C30	109.1 (4)
C44—P2—C34	103.86 (16)	C32—C29—C30	111.1 (4)
C44—P2—C38	103.36 (17)	C32—C29—C31	108.8 (4)
Cu1—O1—H1	140.2	C29—C30—H30A	109.5
C2—O1—Cu1	109.7 (3)	C29—C30—H30B	109.5
C2—O1—H1	109.7	C29—C30—H30C	109.5
C28—O2—C33	116.2 (3)	H30A—C30—H30B	109.5
C1—N1—Cu1	115.7 (3)	H30A—C30—H30C	109.5
C9—N1—Cu1	125.0 (3)	H30B—C30—H30C	109.5
C9—N1—C1	118.5 (4)	C29—C31—H31A	109.5
N1—C1—C2	118.9 (4)	C29—C31—H31B	109.5
N1—C1—C6	122.1 (4)	C29—C31—H31C	109.5
C6—C1—C2	119.0 (4)	H31A—C31—H31B	109.5
O1—C2—C1	115.4 (4)	H31A—C31—H31C	109.5
C3—C2—O1	123.5 (4)	H31B—C31—H31C	109.5
C3—C2—C1	121.0 (4)	C33—C32—C29	119.3 (4)
C2—C3—H3	120.4	C33—C32—C37	115.8 (4)
C2—C3—C4	119.1 (6)	C37—C32—C29	124.8 (4)
C4—C3—H3	120.4	C32—C33—O2	120.5 (3)
C3—C4—H4	119.5	C32—C33—C34	124.6 (3)
C5—C4—C3	121.0 (6)	C34—C33—O2	114.9 (3)
C5—C4—H4	119.5	C33—C34—P2	118.0 (3)
C4—C5—H5	119.5	C33—C34—C35	116.9 (4)
C4—C5—C6	120.9 (5)	C35—C34—P2	124.9 (3)
C6—C5—H5	119.5	C34—C35—H35	119.9
C5—C6—C1	118.8 (5)	C36—C35—C34	120.2 (4)
C5—C6—C7	124.0 (5)	C36—C35—H35	119.9
C7—C6—C1	117.1 (5)	C35—C36—H36	119.6
C6—C7—H7	119.9	C37—C36—C35	120.7 (4)
C8—C7—C6	120.2 (4)	C37—C36—H36	119.6
C8—C7—H7	119.9	C32—C37—H37	119.2
C7—C8—H8	120.3	C36—C37—C32	121.6 (4)
C7—C8—C9	119.4 (5)	C36—C37—H37	119.2
C9—C8—H8	120.3	C39—C38—P2	118.5 (3)
N1—C9—C8	122.5 (5)	C39—C38—C43	118.5 (4)
N1—C9—C10	117.3 (4)	C43—C38—P2	123.0 (3)
C8—C9—C10	120.2 (4)	C38—C39—H39	119.8
C9—C10—H10A	109.5	C38—C39—C40	120.5 (4)
C9—C10—H10B	109.5	C40—C39—H39	119.8
C9—C10—H10C	109.5	C39—C40—H40	119.9
H10A—C10—H10B	109.5	C41—C40—C39	120.2 (4)
H10A—C10—H10C	109.5	C41—C40—H40	119.9
H10B—C10—H10C	109.5	C40—C41—H41	119.6
C12—C11—P1	118.9 (3)	C40—C41—C42	120.7 (4)
C12—C11—C16	118.4 (4)	C42—C41—H41	119.6
C16—C11—P1	122.6 (3)	C41—C42—H42	120.4
C11—C12—H12	119.6	C41—C42—C43	119.2 (5)
C13—C12—C11	120.8 (4)	C43—C42—H42	120.4
C13—C12—H12	119.6	C38—C43—C42	120.8 (4)
C12—C13—H13	120.1	C38—C43—H43	119.6
C14—C13—C12	119.7 (4)	C42—C43—H43	119.6
C14—C13—H13	120.1	C45—C44—P2	117.3 (3)
C13—C14—H14	119.8	C49—C44—P2	123.6 (3)
C15—C14—C13	120.4 (4)	C49—C44—C45	119.1 (4)
C15—C14—H14	119.8	C44—C45—H45	120.3
C14—C15—H15	119.6	C44—C45—C46	119.5 (4)
C14—C15—C16	120.7 (5)	C46—C45—H45	120.3
C16—C15—H15	119.6	C45—C46—H46	119.9
C11—C16—H16	120.0	C47—C46—C45	120.2 (5)
C15—C16—C11	119.9 (4)	C47—C46—H46	119.9
C15—C16—H16	120.0	C46—C47—H47	119.9
C18—C17—P1	117.7 (3)	C46—C47—C48	120.1 (4)
C18—C17—C22	118.8 (4)	C48—C47—H47	119.9
C22—C17—P1	123.4 (3)	C47—C48—H48	119.6
C17—C18—H18	119.4	C49—C48—C47	120.7 (5)
C17—C18—C19	121.2 (4)	C49—C48—H48	119.6
C19—C18—H18	119.4	C44—C49—H49	119.8
C18—C19—H19	120.4	C48—C49—C44	120.4 (4)
C20—C19—C18	119.2 (5)	C48—C49—H49	119.8
C20—C19—H19	120.4	F2—P3—F1	91.3 (4)
C19—C20—H20	119.6	F2—P3—F3	82.8 (4)
C21—C20—C19	120.7 (5)	F3—P3—F1	83.1 (3)
C21—C20—H20	119.6	F4—P3—F1	172.7 (5)
C20—C21—H21	119.6	F4—P3—F2	94.4 (5)
C20—C21—C22	120.8 (5)	F4—P3—F3	93.1 (4)
C22—C21—H21	119.6	F5—P3—F1	84.1 (4)
C17—C22—C21	119.3 (5)	F5—P3—F2	175.4 (5)
C17—C22—H22	120.4	F5—P3—F3	95.8 (5)
C21—C22—H22	120.4	F5—P3—F4	90.0 (5)
C24—C23—P1	125.5 (3)	F5—P3—F6	91.6 (6)
C24—C23—C28	116.6 (4)	F6—P3—F1	91.3 (4)
C28—C23—P1	117.9 (3)	F6—P3—F2	89.3 (5)
C23—C24—H24	119.3	F6—P3—F3	170.2 (6)
C25—C24—C23	121.5 (4)	F6—P3—F4	93.3 (5)
C25—C24—H24	119.3
Cu1—P1—C11—C12	30.5 (4)	C18—C19—C20—C21	−0.3 (8)
Cu1—P1—C11—C16	−151.3 (3)	C19—C20—C21—C22	−0.2 (8)
Cu1—P1—C17—C18	63.6 (3)	C20—C21—C22—C17	0.6 (7)
Cu1—P1—C17—C22	−118.3 (3)	C22—C17—C18—C19	0.0 (6)
Cu1—P1—C23—C24	−135.0 (3)	C23—P1—C11—C12	−92.4 (3)
Cu1—P1—C23—C28	41.2 (3)	C23—P1—C11—C16	85.8 (4)
Cu1—P2—C34—C33	−42.4 (3)	C23—P1—C17—C18	−174.2 (3)
Cu1—P2—C34—C35	132.5 (3)	C23—P1—C17—C22	3.9 (4)
Cu1—P2—C38—C39	−19.4 (4)	C23—C24—C25—C26	−1.5 (7)
Cu1—P2—C38—C43	160.4 (3)	C24—C23—C28—O2	−176.2 (3)
Cu1—P2—C44—C45	−40.5 (3)	C24—C23—C28—C27	2.3 (6)
Cu1—P2—C44—C49	141.6 (3)	C24—C25—C26—C27	1.8 (7)
Cu1—O1—C2—C1	−17.5 (4)	C25—C26—C27—C28	−0.1 (6)
Cu1—O1—C2—C3	164.1 (4)	C25—C26—C27—C29	175.9 (4)
Cu1—N1—C1—C2	12.9 (5)	C26—C27—C28—O2	176.5 (3)
Cu1—N1—C1—C6	−165.7 (3)	C26—C27—C28—C23	−2.0 (6)
Cu1—N1—C9—C8	168.3 (4)	C26—C27—C29—C30	31.5 (6)
Cu1—N1—C9—C10	−9.6 (6)	C26—C27—C29—C31	−88.2 (5)
P1—C11—C12—C13	178.9 (3)	C26—C27—C29—C32	154.1 (4)
P1—C11—C16—C15	−179.2 (4)	C27—C29—C32—C33	31.7 (5)
P1—C17—C18—C19	178.1 (3)	C27—C29—C32—C37	−152.7 (4)
P1—C17—C22—C21	−178.5 (3)	C28—O2—C33—C32	−29.2 (4)
P1—C23—C24—C25	175.7 (3)	C28—O2—C33—C34	150.2 (3)
P1—C23—C28—O2	7.3 (4)	C28—C23—C24—C25	−0.5 (6)
P1—C23—C28—C27	−174.2 (3)	C28—C27—C29—C30	−152.6 (4)
P2—C34—C35—C36	−172.8 (3)	C28—C27—C29—C31	87.7 (5)
P2—C38—C39—C40	−179.4 (4)	C28—C27—C29—C32	−30.0 (5)
P2—C38—C43—C42	179.2 (4)	C29—C27—C28—O2	0.3 (5)
P2—C44—C45—C46	−178.9 (4)	C29—C27—C28—C23	−178.2 (4)
P2—C44—C49—C48	177.8 (4)	C29—C32—C33—O2	−3.8 (5)
O1—C2—C3—C4	178.9 (5)	C29—C32—C33—C34	176.8 (4)
O2—C33—C34—P2	−6.8 (4)	C29—C32—C37—C36	−174.1 (4)
O2—C33—C34—C35	177.9 (3)	C30—C29—C32—C33	154.5 (4)
N1—C1—C2—O1	4.7 (6)	C30—C29—C32—C37	−29.9 (6)
N1—C1—C2—C3	−176.8 (4)	C31—C29—C32—C33	−85.4 (5)
N1—C1—C6—C5	175.9 (4)	C31—C29—C32—C37	90.2 (5)
N1—C1—C6—C7	−4.3 (7)	C32—C33—C34—P2	172.6 (3)
C1—N1—C9—C8	−0.7 (7)	C32—C33—C34—C35	−2.7 (5)
C1—N1—C9—C10	−178.6 (4)	C33—O2—C28—C23	−150.3 (3)
C1—C2—C3—C4	0.7 (8)	C33—O2—C28—C27	31.2 (5)
C1—C6—C7—C8	0.9 (8)	C33—C32—C37—C36	1.6 (6)
C2—C1—C6—C5	−2.7 (7)	C33—C34—C35—C36	2.2 (6)
C2—C1—C6—C7	177.1 (4)	C34—P2—C38—C39	103.7 (3)
C2—C3—C4—C5	−2.3 (9)	C34—P2—C38—C43	−76.4 (4)
C3—C4—C5—C6	1.3 (9)	C34—P2—C44—C45	−161.9 (3)
C4—C5—C6—C1	1.2 (8)	C34—P2—C44—C49	20.2 (4)
C4—C5—C6—C7	−178.6 (6)	C34—C35—C36—C37	0.1 (6)
C5—C6—C7—C8	−179.3 (5)	C35—C36—C37—C32	−2.1 (7)
C6—C1—C2—O1	−176.6 (4)	C37—C32—C33—O2	−179.8 (3)
C6—C1—C2—C3	1.8 (7)	C37—C32—C33—C34	0.8 (6)
C6—C7—C8—C9	2.4 (9)	C38—P2—C34—C33	−170.6 (3)
C7—C8—C9—N1	−2.6 (8)	C38—P2—C34—C35	4.3 (4)
C7—C8—C9—C10	175.2 (6)	C38—P2—C44—C45	90.4 (3)
C9—N1—C1—C2	−177.1 (4)	C38—P2—C44—C49	−87.5 (4)
C9—N1—C1—C6	4.3 (6)	C38—C39—C40—C41	−0.7 (7)
C11—P1—C17—C18	−67.9 (4)	C39—C38—C43—C42	−1.0 (7)
C11—P1—C17—C22	110.2 (4)	C39—C40—C41—C42	0.8 (8)
C11—P1—C23—C24	−6.4 (4)	C40—C41—C42—C43	−1.1 (8)
C11—P1—C23—C28	169.7 (3)	C41—C42—C43—C38	1.2 (8)
C11—C12—C13—C14	−0.1 (7)	C43—C38—C39—C40	0.7 (7)
C12—C11—C16—C15	−1.0 (7)	C44—P2—C34—C33	81.8 (3)
C12—C13—C14—C15	0.0 (8)	C44—P2—C34—C35	−103.4 (3)
C13—C14—C15—C16	−0.4 (8)	C44—P2—C38—C39	−148.2 (3)
C14—C15—C16—C11	1.0 (8)	C44—P2—C38—C43	31.6 (4)
C16—C11—C12—C13	0.6 (6)	C44—C45—C46—C47	0.7 (7)
C17—P1—C11—C12	159.7 (3)	C45—C44—C49—C48	−0.1 (7)
C17—P1—C11—C16	−22.1 (4)	C45—C46—C47—C48	0.6 (8)
C17—P1—C23—C24	99.5 (4)	C46—C47—C48—C49	−1.6 (9)
C17—P1—C23—C28	−84.3 (3)	C47—C48—C49—C44	1.4 (8)
C17—C18—C19—C20	0.4 (7)	C49—C44—C45—C46	−0.9 (6)
C18—C17—C22—C21	−0.5 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···F1	0.85	2.08	2.802 (6)	142