A novel luminescent ionic trinuclear Cu₃I₂ cluster cuprous complex supported by a P^N ligand: synthesis, structure characterization, properties and TD–DFT calculations

Luminescent cuprous complexes are an important class of coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The title ionic trinuclear Cu₃I₂ complex, tris­[μ₂-diphen­yl(pyridin-2-yl)phosphane-κ²P:N]di-μ₃-iodido-tricopper(I)(3 Cu—Cu) hexa­fluorido­phosphate, [Cu₃I₂(C₃₉H₃₂NP)₃]PF₆, conventionally abbreviated as [Cu₃I₂(Ph₂PPy)₃]PF₆, is described. Each Cu^I atom is coordinated by two μ₃-iodide ligands and by a P and an N atom from two Ph₂PPy ligands, giving rise to a CuI₂PN tetra­hedral coordination geometry about each Cu^I centre. The electronic absorption and photoluminescence properties of this trinuclear cluster have been studied on as-synthesized samples, which had been examined previously by powder X-ray diffraction. A detailed time-dependent density functional theory (TD–DFT) study was carried out and showed a green emission derived from a halide-to-ligand charge transfer and metal-to-ligand charge transfer ³(X+M)LCT excited state.

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).

Tris[µ-diphenyl(pyridin-2-yl)phosphane-κ²P:N]di-µ₃-iodido-tricopper(I)(3 Cu—Cu) hexafluoridophosphate

Crystal data

[Cu3I2(C39H32NP)3]PF6	F(000) = 2704
Mr = 1379.17	Dx = 1.804 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 18.9310 (13) Å	Cell parameters from 5956 reflections
b = 12.4391 (6) Å	θ = 3.0–29.6°
c = 21.7800 (11) Å	µ = 2.65 mm^−1
β = 98.012 (5)°	T = 172 K
V = 5078.8 (5) Å^3	Plate, yellow
Z = 4	0.48 × 0.23 × 0.17 mm

Data collection

Agilent Xcalibur Atlas Gemini ultra diffractometer	10513 independent reflections
Radiation source: Enhance (Mo) X-ray Source	7796 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
Detector resolution: 10.3592 pixels mm^-1	θmax = 26.5°, θmin = 3.0°
ω scans	h = −23→19
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −12→15
Tmin = 0.665, Tmax = 1.000	l = −21→27
24864 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.094	w = 1/[σ^2(Fo^2) + (0.042P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
10513 reflections	Δρmax = 0.90 e Å^−3
622 parameters	Δρmin = −0.73 e Å^−3
0 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
I1	0.48055 (2)	0.13500 (2)	0.17740 (2)	0.03011 (9)
I2	0.35643 (2)	0.44129 (2)	0.17126 (2)	0.02628 (8)
Cu1	0.48447 (3)	0.33329 (4)	0.22300 (2)	0.03014 (14)
Cu2	0.36046 (3)	0.22783 (4)	0.20357 (2)	0.02705 (13)
Cu3	0.41757 (3)	0.29998 (4)	0.10209 (2)	0.02646 (13)
P1	0.56213 (6)	0.43590 (8)	0.18218 (5)	0.0225 (2)
P2	0.36674 (6)	0.22381 (8)	0.30709 (5)	0.0219 (2)
P3	0.32268 (6)	0.22050 (8)	0.04475 (5)	0.0232 (2)
N1	0.48872 (19)	0.3428 (2)	0.31697 (16)	0.0256 (8)
N2	0.27172 (18)	0.1634 (2)	0.15217 (15)	0.0205 (7)
N3	0.50364 (18)	0.3669 (2)	0.06687 (15)	0.0227 (7)
C1	0.5448 (2)	0.3946 (4)	0.3488 (2)	0.0337 (11)
H1	0.5813	0.4174	0.3274	0.040*
C2	0.5504 (3)	0.4156 (3)	0.4114 (2)	0.0353 (11)
H2	0.5905	0.4503	0.4318	0.042*
C3	0.4964 (3)	0.3847 (4)	0.4431 (2)	0.0400 (12)
H3	0.4987	0.3989	0.4852	0.048*
C4	0.4383 (3)	0.3316 (3)	0.4111 (2)	0.0318 (10)
H4	0.4005	0.3110	0.4316	0.038*
C5	0.4364 (2)	0.3093 (3)	0.34875 (19)	0.0252 (9)
C6	0.3929 (2)	0.0936 (3)	0.3425 (2)	0.0280 (10)
C7	0.4603 (3)	0.0745 (4)	0.3711 (4)	0.079 (2)
H7	0.4939	0.1295	0.3747	0.095*
C8	0.4792 (4)	−0.0273 (4)	0.3950 (4)	0.105 (3)
H8	0.5250	−0.0394	0.4155	0.126*
C9	0.4308 (3)	−0.1084 (4)	0.3885 (3)	0.0566 (16)
H9	0.4432	−0.1760	0.4049	0.068*
C10	0.3643 (3)	−0.0907 (4)	0.3581 (3)	0.0462 (14)
H10	0.3314	−0.1465	0.3524	0.055*
C11	0.3459 (3)	0.0100 (3)	0.3359 (2)	0.0422 (13)
H11	0.3000	0.0216	0.3157	0.051*
C12	0.2869 (2)	0.2630 (3)	0.33949 (19)	0.0262 (9)
C13	0.2720 (2)	0.2301 (3)	0.3975 (2)	0.0328 (10)
H13	0.3021	0.1819	0.4210	0.039*
C14	0.2120 (3)	0.2693 (4)	0.4201 (2)	0.0447 (13)
H14	0.2022	0.2475	0.4588	0.054*
C15	0.1665 (3)	0.3410 (4)	0.3851 (3)	0.0471 (13)
H15	0.1271	0.3686	0.4009	0.056*
C16	0.1801 (3)	0.3707 (4)	0.3274 (3)	0.0452 (13)
H16	0.1486	0.4165	0.3034	0.054*
C17	0.2399 (2)	0.3336 (3)	0.3043 (2)	0.0317 (10)
H17	0.2490	0.3556	0.2653	0.038*
C18	0.2225 (2)	0.1242 (3)	0.1846 (2)	0.0294 (10)
H18	0.2353	0.1157	0.2271	0.035*
C19	0.1540 (2)	0.0953 (3)	0.1595 (2)	0.0315 (10)
H19	0.1226	0.0644	0.1836	0.038*
C20	0.1340 (2)	0.1143 (3)	0.0968 (2)	0.0329 (10)
H20	0.0878	0.0993	0.0781	0.040*
C21	0.1834 (2)	0.1557 (3)	0.0626 (2)	0.0281 (10)
H21	0.1705	0.1691	0.0205	0.034*
C22	0.2523 (2)	0.1774 (3)	0.09051 (18)	0.0214 (9)
C23	0.2696 (2)	0.2998 (3)	−0.0158 (2)	0.0273 (9)
C24	0.2359 (3)	0.3921 (3)	0.0017 (2)	0.0362 (11)
H24	0.2399	0.4104	0.0435	0.043*
C25	0.1965 (3)	0.4572 (4)	−0.0423 (3)	0.0482 (14)
H25	0.1739	0.5184	−0.0301	0.058*
C26	0.1912 (3)	0.4302 (4)	−0.1040 (3)	0.0540 (15)
H26	0.1654	0.4741	−0.1336	0.065*
C27	0.2233 (3)	0.3395 (5)	−0.1224 (2)	0.0585 (16)
H27	0.2189	0.3217	−0.1642	0.070*
C28	0.2626 (3)	0.2741 (4)	−0.0784 (2)	0.0410 (12)
H28	0.2843	0.2124	−0.0910	0.049*
C29	0.3413 (2)	0.0977 (3)	0.00340 (19)	0.0264 (9)
C30	0.4084 (3)	0.0880 (3)	−0.0128 (2)	0.0354 (11)
H30	0.4430	0.1386	0.0013	0.043*
C31	0.4258 (3)	0.0035 (4)	−0.0501 (2)	0.0424 (12)
H31	0.4708	0.0000	−0.0625	0.051*
C32	0.3758 (3)	−0.0742 (4)	−0.0683 (2)	0.0382 (12)
H32	0.3872	−0.1321	−0.0921	0.046*
C33	0.3097 (3)	−0.0661 (4)	−0.0515 (2)	0.0479 (14)
H33	0.2756	−0.1182	−0.0645	0.058*
C34	0.2921 (3)	0.0185 (4)	−0.0152 (2)	0.0439 (13)
H34	0.2468	0.0218	−0.0033	0.053*
C35	0.5021 (3)	0.3538 (3)	0.0051 (2)	0.0292 (10)
H35	0.4609	0.3258	−0.0175	0.035*
C36	0.5582 (3)	0.3796 (3)	−0.0262 (2)	0.0334 (11)
H36	0.5550	0.3678	−0.0686	0.040*
C37	0.6192 (3)	0.4233 (3)	0.0066 (2)	0.0345 (11)
H37	0.6579	0.4413	−0.0133	0.041*
C38	0.6215 (2)	0.4398 (3)	0.0695 (2)	0.0301 (10)
H38	0.6620	0.4696	0.0924	0.036*
C39	0.5634 (2)	0.4117 (3)	0.09875 (19)	0.0235 (9)
C40	0.6570 (2)	0.4268 (3)	0.21294 (19)	0.0258 (9)
C41	0.6956 (3)	0.3361 (4)	0.2024 (2)	0.0454 (13)
H41	0.6728	0.2790	0.1802	0.054*
C42	0.7668 (3)	0.3291 (4)	0.2240 (3)	0.0523 (15)
H42	0.7928	0.2695	0.2145	0.063*
C43	0.7999 (3)	0.4111 (5)	0.2601 (3)	0.0573 (16)
H43	0.8482	0.4065	0.2753	0.069*
C44	0.7617 (3)	0.4977 (4)	0.2731 (3)	0.0546 (15)
H44	0.7839	0.5522	0.2980	0.066*
C45	0.6904 (3)	0.5066 (4)	0.2500 (2)	0.0389 (11)
H45	0.6648	0.5668	0.2594	0.047*
C46	0.5447 (2)	0.5804 (3)	0.1873 (2)	0.0263 (9)
C47	0.5723 (3)	0.6567 (3)	0.1503 (2)	0.0353 (11)
H47	0.6007	0.6351	0.1210	0.042*
C48	0.5577 (3)	0.7639 (3)	0.1571 (2)	0.0437 (13)
H48	0.5756	0.8145	0.1318	0.052*
C49	0.5170 (3)	0.7969 (4)	0.2007 (3)	0.0452 (13)
H49	0.5070	0.8696	0.2045	0.054*
C50	0.4906 (3)	0.7232 (4)	0.2391 (3)	0.0465 (13)
H50	0.4639	0.7457	0.2695	0.056*
C51	0.5048 (2)	0.6149 (3)	0.2315 (2)	0.0336 (11)
H51	0.4869	0.5646	0.2569	0.040*
P4	0.88084 (7)	0.22006 (9)	0.08383 (6)	0.0344 (3)
F1	0.90245 (17)	0.3067 (2)	0.13641 (13)	0.0530 (8)
F2	0.85547 (18)	0.1395 (2)	0.13312 (13)	0.0532 (8)
F3	0.95930 (16)	0.1698 (2)	0.09602 (14)	0.0530 (8)
F4	0.85893 (15)	0.13212 (19)	0.03046 (12)	0.0420 (7)
F5	0.90578 (17)	0.2993 (2)	0.03318 (13)	0.0506 (8)
F6	0.80253 (16)	0.2699 (2)	0.07082 (15)	0.0530 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.03098 (18)	0.02678 (14)	0.03441 (17)	0.00432 (12)	0.01101 (13)	−0.00115 (12)
I2	0.02629 (16)	0.02566 (14)	0.02779 (16)	0.00023 (11)	0.00690 (12)	−0.00261 (11)
Cu1	0.0313 (3)	0.0369 (3)	0.0241 (3)	−0.0117 (2)	0.0103 (2)	−0.0021 (2)
Cu2	0.0249 (3)	0.0350 (3)	0.0218 (3)	−0.0050 (2)	0.0052 (2)	−0.0020 (2)
Cu3	0.0234 (3)	0.0318 (3)	0.0254 (3)	−0.0065 (2)	0.0074 (2)	−0.0036 (2)
P1	0.0219 (6)	0.0266 (5)	0.0203 (5)	−0.0043 (4)	0.0071 (5)	−0.0020 (4)
P2	0.0217 (6)	0.0244 (5)	0.0205 (5)	−0.0015 (4)	0.0058 (4)	0.0007 (4)
P3	0.0225 (6)	0.0272 (5)	0.0205 (5)	−0.0035 (4)	0.0055 (5)	−0.0017 (4)
N1	0.025 (2)	0.0279 (17)	0.0243 (19)	−0.0078 (15)	0.0059 (16)	0.0005 (15)
N2	0.0209 (19)	0.0196 (16)	0.0219 (18)	−0.0021 (13)	0.0063 (15)	−0.0030 (14)
N3	0.022 (2)	0.0260 (16)	0.0202 (18)	−0.0037 (14)	0.0055 (15)	−0.0029 (14)
C1	0.028 (3)	0.045 (2)	0.028 (2)	−0.015 (2)	0.001 (2)	0.002 (2)
C2	0.042 (3)	0.033 (2)	0.028 (2)	−0.011 (2)	−0.005 (2)	0.004 (2)
C3	0.047 (3)	0.050 (3)	0.022 (2)	−0.010 (2)	0.001 (2)	−0.008 (2)
C4	0.033 (3)	0.041 (2)	0.022 (2)	−0.008 (2)	0.006 (2)	−0.004 (2)
C5	0.026 (2)	0.026 (2)	0.025 (2)	0.0066 (17)	0.0036 (18)	0.0038 (18)
C6	0.032 (3)	0.022 (2)	0.033 (2)	−0.0004 (18)	0.012 (2)	0.0032 (19)
C7	0.036 (4)	0.027 (3)	0.165 (8)	0.000 (2)	−0.022 (4)	0.016 (3)
C8	0.045 (4)	0.040 (3)	0.213 (10)	0.001 (3)	−0.040 (5)	0.031 (4)
C9	0.048 (4)	0.024 (2)	0.096 (5)	0.003 (2)	0.005 (3)	0.009 (3)
C10	0.050 (4)	0.029 (2)	0.058 (4)	−0.013 (2)	0.002 (3)	0.003 (2)
C11	0.032 (3)	0.038 (3)	0.052 (3)	−0.010 (2)	−0.011 (2)	0.009 (2)
C12	0.028 (3)	0.028 (2)	0.025 (2)	−0.0013 (18)	0.0096 (19)	−0.0011 (18)
C13	0.031 (3)	0.037 (2)	0.032 (3)	−0.003 (2)	0.009 (2)	0.004 (2)
C14	0.035 (3)	0.062 (3)	0.042 (3)	−0.005 (3)	0.021 (2)	−0.009 (3)
C15	0.032 (3)	0.060 (3)	0.054 (3)	0.003 (2)	0.021 (3)	−0.009 (3)
C16	0.030 (3)	0.046 (3)	0.061 (4)	0.008 (2)	0.010 (3)	0.002 (3)
C17	0.027 (3)	0.034 (2)	0.036 (3)	0.0002 (19)	0.007 (2)	0.004 (2)
C18	0.031 (3)	0.030 (2)	0.028 (2)	−0.0075 (19)	0.005 (2)	0.0002 (19)
C19	0.029 (3)	0.034 (2)	0.034 (3)	−0.0071 (19)	0.010 (2)	0.002 (2)
C20	0.023 (3)	0.039 (2)	0.036 (3)	−0.0085 (19)	0.001 (2)	−0.002 (2)
C21	0.023 (2)	0.037 (2)	0.024 (2)	−0.0053 (18)	0.0014 (19)	−0.0009 (19)
C22	0.022 (2)	0.0223 (19)	0.021 (2)	−0.0038 (16)	0.0060 (17)	−0.0021 (17)
C23	0.022 (2)	0.032 (2)	0.028 (2)	−0.0049 (18)	0.0042 (19)	0.0035 (19)
C24	0.039 (3)	0.034 (2)	0.035 (3)	0.001 (2)	0.003 (2)	0.002 (2)
C25	0.047 (4)	0.040 (3)	0.058 (4)	0.005 (2)	0.012 (3)	0.013 (3)
C26	0.046 (4)	0.066 (3)	0.048 (3)	0.006 (3)	0.000 (3)	0.030 (3)
C27	0.062 (4)	0.084 (4)	0.028 (3)	0.012 (3)	0.002 (3)	0.013 (3)
C28	0.041 (3)	0.057 (3)	0.026 (2)	0.003 (2)	0.009 (2)	0.002 (2)
C29	0.033 (3)	0.027 (2)	0.021 (2)	−0.0041 (18)	0.0107 (19)	−0.0007 (18)
C30	0.033 (3)	0.028 (2)	0.046 (3)	−0.0057 (19)	0.009 (2)	−0.003 (2)
C31	0.038 (3)	0.045 (3)	0.048 (3)	0.000 (2)	0.017 (2)	−0.010 (2)
C32	0.044 (3)	0.038 (2)	0.034 (3)	0.001 (2)	0.011 (2)	−0.016 (2)
C33	0.051 (4)	0.047 (3)	0.050 (3)	−0.019 (3)	0.021 (3)	−0.024 (3)
C34	0.034 (3)	0.049 (3)	0.053 (3)	−0.012 (2)	0.022 (3)	−0.013 (3)
C35	0.030 (3)	0.033 (2)	0.025 (2)	−0.0078 (19)	0.0048 (19)	−0.0057 (19)
C36	0.037 (3)	0.040 (2)	0.025 (2)	−0.002 (2)	0.010 (2)	−0.002 (2)
C37	0.032 (3)	0.044 (2)	0.031 (3)	−0.002 (2)	0.015 (2)	0.000 (2)
C38	0.029 (3)	0.038 (2)	0.027 (2)	−0.0092 (19)	0.013 (2)	−0.007 (2)
C39	0.025 (2)	0.0225 (19)	0.024 (2)	−0.0047 (17)	0.0062 (18)	−0.0014 (18)
C40	0.020 (2)	0.034 (2)	0.024 (2)	0.0014 (18)	0.0056 (18)	0.0045 (19)
C41	0.041 (3)	0.047 (3)	0.046 (3)	0.008 (2)	0.002 (3)	−0.002 (2)
C42	0.044 (4)	0.061 (3)	0.052 (3)	0.029 (3)	0.008 (3)	0.009 (3)
C43	0.026 (3)	0.085 (4)	0.058 (4)	0.006 (3)	−0.005 (3)	0.021 (3)
C44	0.038 (3)	0.061 (3)	0.059 (4)	−0.008 (3)	−0.016 (3)	−0.004 (3)
C45	0.029 (3)	0.049 (3)	0.037 (3)	−0.002 (2)	−0.001 (2)	−0.007 (2)
C46	0.022 (2)	0.028 (2)	0.028 (2)	−0.0027 (17)	0.0009 (19)	−0.0016 (18)
C47	0.037 (3)	0.039 (3)	0.030 (2)	−0.011 (2)	0.006 (2)	−0.001 (2)
C48	0.059 (4)	0.030 (2)	0.040 (3)	−0.011 (2)	−0.001 (3)	0.008 (2)
C49	0.039 (3)	0.028 (2)	0.064 (4)	−0.002 (2)	−0.009 (3)	−0.005 (2)
C50	0.032 (3)	0.043 (3)	0.066 (4)	−0.003 (2)	0.008 (3)	−0.017 (3)
C51	0.030 (3)	0.031 (2)	0.041 (3)	−0.0046 (19)	0.011 (2)	−0.009 (2)
P4	0.0352 (7)	0.0392 (6)	0.0303 (6)	−0.0044 (5)	0.0094 (6)	−0.0004 (5)
F1	0.057 (2)	0.0627 (17)	0.0393 (17)	−0.0068 (15)	0.0080 (15)	−0.0192 (14)
F2	0.062 (2)	0.0599 (17)	0.0415 (17)	−0.0063 (15)	0.0214 (15)	0.0152 (14)
F3	0.0327 (18)	0.0619 (17)	0.065 (2)	0.0025 (14)	0.0087 (15)	−0.0056 (16)
F4	0.0499 (19)	0.0396 (14)	0.0375 (15)	−0.0095 (13)	0.0094 (14)	−0.0051 (12)
F5	0.067 (2)	0.0463 (15)	0.0409 (16)	−0.0191 (15)	0.0147 (15)	0.0022 (13)
F6	0.0389 (18)	0.0464 (15)	0.072 (2)	0.0015 (13)	0.0030 (16)	−0.0052 (15)

Geometric parameters (Å, º)

Cu1—I1	2.6561 (6)	C19—C20	1.385 (6)
Cu2—I1	2.6810 (6)	C20—H20	0.9300
Cu3—I1	2.7889 (6)	C20—C21	1.373 (6)
Cu1—I2	2.8616 (7)	C21—H21	0.9300
Cu2—I2	2.7453 (6)	C21—C22	1.388 (6)
Cu3—I2	2.6807 (6)	C23—C24	1.392 (6)
Cu1—N1	2.040 (3)	C23—C28	1.388 (6)
Cu2—N2	2.048 (3)	C24—H24	0.9300
Cu3—N3	2.070 (3)	C24—C25	1.390 (7)
Cu1—P1	2.2238 (11)	C25—H25	0.9300
Cu2—P2	2.2418 (11)	C25—C26	1.377 (8)
Cu3—P3	2.2669 (12)	C26—H26	0.9300
Cu1—Cu2	2.6711 (7)	C26—C27	1.367 (8)
Cu1—Cu3	2.7893 (8)	C27—H27	0.9300
Cu2—Cu3	2.7433 (7)	C27—C28	1.392 (7)
P1—C39	1.845 (4)	C28—H28	0.9300
P1—C40	1.831 (4)	C29—C30	1.370 (6)
P1—C46	1.833 (4)	C29—C34	1.378 (6)
P2—C5	1.832 (4)	C30—H30	0.9300
P2—C6	1.832 (4)	C30—C31	1.395 (6)
P2—C12	1.822 (4)	C31—H31	0.9300
P3—C22	1.851 (4)	C31—C32	1.372 (7)
P3—C23	1.831 (4)	C32—H32	0.9300
P3—C29	1.832 (4)	C32—C33	1.357 (7)
N1—C1	1.348 (5)	C33—H33	0.9300
N1—C5	1.352 (5)	C33—C34	1.384 (6)
N2—C18	1.338 (5)	C34—H34	0.9300
N2—C22	1.353 (5)	C35—H35	0.9300
N3—C35	1.351 (5)	C35—C36	1.377 (6)
N3—C39	1.361 (5)	C36—H36	0.9300
C1—H1	0.9300	C36—C37	1.383 (6)
C1—C2	1.378 (6)	C37—H37	0.9300
C2—H2	0.9300	C37—C38	1.379 (6)
C2—C3	1.366 (7)	C38—H38	0.9300
C3—H3	0.9300	C38—C39	1.391 (6)
C3—C4	1.385 (6)	C40—C41	1.381 (6)
C4—H4	0.9300	C40—C45	1.377 (6)
C4—C5	1.382 (6)	C41—H41	0.9300
C6—C7	1.360 (7)	C41—C42	1.367 (7)
C6—C11	1.363 (6)	C42—H42	0.9300
C7—H7	0.9300	C42—C43	1.383 (8)
C7—C8	1.397 (7)	C43—H43	0.9300
C8—H8	0.9300	C43—C44	1.350 (8)
C8—C9	1.357 (8)	C44—H44	0.9300
C9—H9	0.9300	C44—C45	1.378 (7)
C9—C10	1.356 (7)	C45—H45	0.9300
C10—H10	0.9300	C46—C47	1.393 (6)
C10—C11	1.370 (6)	C46—C51	1.373 (6)
C11—H11	0.9300	C47—H47	0.9300
C12—C13	1.393 (6)	C47—C48	1.375 (6)
C12—C17	1.399 (6)	C48—H48	0.9300
C13—H13	0.9300	C48—C49	1.367 (7)
C13—C14	1.386 (6)	C49—H49	0.9300
C14—H14	0.9300	C49—C50	1.380 (7)
C14—C15	1.391 (7)	C50—H50	0.9300
C15—H15	0.9300	C50—C51	1.388 (6)
C15—C16	1.369 (7)	C51—H51	0.9300
C16—H16	0.9300	P4—F1	1.584 (3)
C16—C17	1.382 (7)	P4—F2	1.591 (3)
C17—H17	0.9300	P4—F3	1.599 (3)
C18—H18	0.9300	P4—F4	1.608 (3)
C18—C19	1.383 (6)	P4—F5	1.599 (3)
C19—H19	0.9300	P4—F6	1.595 (3)
I1—Cu1—I2	108.10 (2)	C16—C15—H15	120.2
I1—Cu2—I2	110.866 (19)	C15—C16—H16	119.6
I2—Cu3—I1	109.551 (19)	C15—C16—C17	120.8 (5)
P1—Cu1—I1	111.66 (3)	C17—C16—H16	119.6
P1—Cu1—I2	98.28 (3)	C12—C17—H17	120.0
P2—Cu2—I1	106.05 (3)	C16—C17—C12	120.0 (4)
P2—Cu2—I2	105.96 (3)	C16—C17—H17	120.0
P3—Cu3—I1	104.13 (3)	N2—C18—H18	117.6
P3—Cu3—I2	102.97 (3)	N2—C18—C19	124.7 (4)
N1—Cu1—I1	115.08 (9)	C19—C18—H18	117.6
N1—Cu1—I2	106.29 (10)	C18—C19—H19	121.4
N2—Cu2—I1	111.75 (9)	C18—C19—C20	117.2 (4)
N2—Cu2—I2	104.30 (9)	C20—C19—H19	121.4
N3—Cu3—I1	102.70 (9)	C19—C20—H20	120.5
N3—Cu3—I2	111.61 (9)	C21—C20—C19	119.1 (4)
N1—Cu1—P1	115.59 (10)	C21—C20—H20	120.5
N2—Cu2—P2	117.75 (10)	C20—C21—H21	119.8
N3—Cu3—P3	125.14 (10)	C20—C21—C22	120.3 (4)
Cu1—I1—Cu2	60.062 (17)	C22—C21—H21	119.8
Cu1—I1—Cu3	61.574 (17)	N2—C22—P3	117.1 (3)
Cu2—I1—Cu3	60.163 (16)	N2—C22—C21	121.2 (4)
Cu2—I2—Cu1	56.855 (16)	C21—C22—P3	121.6 (3)
Cu3—I2—Cu1	60.330 (17)	C24—C23—P3	118.2 (3)
Cu3—I2—Cu2	60.726 (16)	C28—C23—P3	123.4 (3)
I1—Cu1—Cu2	60.432 (17)	C28—C23—C24	118.3 (4)
I1—Cu1—Cu3	61.557 (16)	C23—C24—H24	119.5
Cu2—Cu1—I2	59.377 (17)	C25—C24—C23	120.9 (4)
Cu2—Cu1—Cu3	60.270 (19)	C25—C24—H24	119.5
Cu3—Cu1—I2	56.619 (17)	C24—C25—H25	120.3
P1—Cu1—Cu2	146.51 (4)	C26—C25—C24	119.3 (5)
P1—Cu1—Cu3	86.92 (3)	C26—C25—H25	120.3
N1—Cu1—Cu2	95.64 (10)	C25—C26—H26	119.6
N1—Cu1—Cu3	154.79 (10)	C27—C26—C25	120.9 (5)
I1—Cu2—Cu3	61.869 (17)	C27—C26—H26	119.6
Cu1—Cu2—I1	59.506 (17)	C26—C27—H27	120.1
Cu1—Cu2—I2	63.768 (17)	C26—C27—C28	119.8 (5)
Cu1—Cu2—Cu3	62.001 (19)	C28—C27—H27	120.1
Cu3—Cu2—I2	58.472 (15)	C23—C28—C27	120.7 (5)
P2—Cu2—Cu1	85.95 (3)	C23—C28—H28	119.7
P2—Cu2—Cu3	147.78 (4)	C27—C28—H28	119.7
N2—Cu2—Cu1	156.17 (9)	C30—C29—P3	116.7 (3)
N2—Cu2—Cu3	94.19 (9)	C30—C29—C34	118.3 (4)
I1—Cu3—Cu1	56.868 (16)	C34—C29—P3	124.9 (4)
I2—Cu3—Cu1	63.051 (17)	C29—C30—H30	119.4
I2—Cu3—Cu2	60.802 (16)	C29—C30—C31	121.3 (4)
Cu2—Cu3—I1	57.968 (16)	C31—C30—H30	119.4
Cu2—Cu3—Cu1	57.730 (18)	C30—C31—H31	120.3
P3—Cu3—Cu1	143.66 (4)	C32—C31—C30	119.3 (5)
P3—Cu3—Cu2	85.99 (3)	C32—C31—H31	120.3
N3—Cu3—I1	102.70 (9)	C31—C32—H32	120.2
N3—Cu3—I2	111.61 (9)	C33—C32—C31	119.6 (4)
N3—Cu3—Cu1	90.73 (9)	C33—C32—H32	120.2
N3—Cu3—Cu2	148.12 (10)	C32—C33—H33	119.5
C39—P1—Cu1	113.56 (13)	C32—C33—C34	121.0 (5)
C40—P1—Cu1	119.18 (13)	C34—C33—H33	119.5
C40—P1—C39	101.75 (19)	C29—C34—C33	120.3 (5)
C40—P1—C46	102.38 (19)	C29—C34—H34	119.9
C46—P1—Cu1	113.82 (15)	C33—C34—H34	119.9
C46—P1—C39	104.29 (18)	N3—C35—H35	118.2
C5—P2—Cu2	114.76 (14)	N3—C35—C36	123.6 (4)
C6—P2—Cu2	114.58 (14)	C36—C35—H35	118.2
C6—P2—C5	99.85 (19)	C35—C36—H36	120.6
C12—P2—Cu2	116.94 (14)	C35—C36—C37	118.8 (4)
C12—P2—C5	103.38 (19)	C37—C36—H36	120.6
C12—P2—C6	105.31 (19)	C36—C37—H37	120.6
C22—P3—Cu3	113.84 (13)	C38—C37—C36	118.7 (4)
C23—P3—Cu3	118.35 (13)	C38—C37—H37	120.6
C23—P3—C22	100.37 (19)	C37—C38—H38	120.0
C23—P3—C29	102.65 (19)	C37—C38—C39	120.0 (4)
C29—P3—Cu3	116.24 (15)	C39—C38—H38	120.0
C29—P3—C22	103.05 (18)	N3—C39—P1	116.5 (3)
C1—N1—Cu1	117.5 (3)	N3—C39—C38	121.6 (4)
C1—N1—C5	117.7 (4)	C38—C39—P1	122.0 (3)
C5—N1—Cu1	124.5 (3)	C41—C40—P1	120.3 (4)
C18—N2—Cu2	115.6 (3)	C45—C40—P1	121.1 (3)
C18—N2—C22	117.3 (4)	C45—C40—C41	118.5 (4)
C22—N2—Cu2	125.5 (3)	C40—C41—H41	119.6
C35—N3—Cu3	114.3 (3)	C42—C41—C40	120.9 (5)
C35—N3—C39	117.3 (4)	C42—C41—H41	119.6
C39—N3—Cu3	128.1 (3)	C41—C42—H42	120.1
N1—C1—H1	118.4	C41—C42—C43	119.7 (5)
N1—C1—C2	123.1 (4)	C43—C42—H42	120.1
C2—C1—H1	118.4	C42—C43—H43	120.2
C1—C2—H2	120.5	C44—C43—C42	119.7 (5)
C3—C2—C1	119.1 (4)	C44—C43—H43	120.2
C3—C2—H2	120.5	C43—C44—H44	119.6
C2—C3—H3	120.7	C43—C44—C45	120.8 (5)
C2—C3—C4	118.6 (4)	C45—C44—H44	119.6
C4—C3—H3	120.7	C40—C45—C44	120.2 (5)
C3—C4—H4	120.0	C40—C45—H45	119.9
C5—C4—C3	120.0 (4)	C44—C45—H45	119.9
C5—C4—H4	120.0	C47—C46—P1	123.2 (3)
N1—C5—P2	117.0 (3)	C51—C46—P1	118.1 (3)
N1—C5—C4	121.4 (4)	C51—C46—C47	118.6 (4)
C4—C5—P2	121.5 (3)	C46—C47—H47	119.9
C7—C6—P2	121.9 (3)	C48—C47—C46	120.1 (5)
C7—C6—C11	118.2 (4)	C48—C47—H47	119.9
C11—C6—P2	119.7 (4)	C47—C48—H48	119.7
C6—C7—H7	119.9	C49—C48—C47	120.5 (5)
C6—C7—C8	120.3 (5)	C49—C48—H48	119.7
C8—C7—H7	119.9	C48—C49—H49	119.7
C7—C8—H8	120.0	C48—C49—C50	120.6 (4)
C9—C8—C7	120.1 (6)	C50—C49—H49	119.7
C9—C8—H8	120.0	C49—C50—H50	120.7
C8—C9—H9	120.1	C49—C50—C51	118.6 (5)
C10—C9—C8	119.8 (5)	C51—C50—H50	120.7
C10—C9—H9	120.1	C46—C51—C50	121.5 (5)
C9—C10—H10	120.2	C46—C51—H51	119.3
C9—C10—C11	119.7 (5)	C50—C51—H51	119.3
C11—C10—H10	120.2	F1—P4—F2	90.71 (16)
C6—C11—C10	122.0 (5)	F1—P4—F3	90.30 (17)
C6—C11—H11	119.0	F1—P4—F4	180.0 (3)
C10—C11—H11	119.0	F1—P4—F5	90.46 (16)
C13—C12—P2	123.8 (3)	F1—P4—F6	90.24 (17)
C13—C12—C17	119.2 (4)	F2—P4—F3	90.14 (17)
C17—C12—P2	117.0 (3)	F2—P4—F4	89.28 (15)
C12—C13—H13	120.1	F2—P4—F5	178.83 (17)
C14—C13—C12	119.8 (4)	F2—P4—F6	90.24 (17)
C14—C13—H13	120.1	F3—P4—F4	89.67 (16)
C13—C14—H14	119.8	F3—P4—F5	89.93 (17)
C13—C14—C15	120.4 (4)	F5—P4—F4	89.55 (14)
C15—C14—H14	119.8	F6—P4—F3	179.34 (19)
C14—C15—H15	120.2	F6—P4—F4	89.79 (16)
C16—C15—C14	119.6 (5)	F6—P4—F5	89.67 (17)
Cu1—P1—C39—N3	22.6 (3)	C13—C12—C17—C16	0.7 (7)
Cu1—P1—C39—C38	−158.8 (3)	C13—C14—C15—C16	1.7 (8)
Cu1—P1—C40—C41	70.3 (4)	C14—C15—C16—C17	−2.5 (8)
Cu1—P1—C40—C45	−105.8 (4)	C15—C16—C17—C12	1.3 (7)
Cu1—P1—C46—C47	−161.0 (3)	C17—C12—C13—C14	−1.4 (6)
Cu1—P1—C46—C51	21.8 (4)	C18—N2—C22—P3	−174.9 (3)
Cu1—N1—C1—C2	173.6 (4)	C18—N2—C22—C21	2.3 (5)
Cu1—N1—C5—P2	14.0 (4)	C18—C19—C20—C21	2.9 (6)
Cu1—N1—C5—C4	−170.8 (3)	C19—C20—C21—C22	0.3 (6)
Cu2—P2—C5—N1	−17.5 (3)	C20—C21—C22—P3	173.9 (3)
Cu2—P2—C5—C4	167.4 (3)	C20—C21—C22—N2	−3.1 (6)
Cu2—P2—C6—C7	102.0 (5)	C22—P3—C23—C24	63.6 (4)
Cu2—P2—C6—C11	−72.5 (4)	C22—P3—C23—C28	−117.9 (4)
Cu2—P2—C12—C13	156.0 (3)	C22—P3—C29—C30	−152.8 (4)
Cu2—P2—C12—C17	−26.5 (4)	C22—P3—C29—C34	30.8 (5)
Cu2—N2—C18—C19	167.7 (3)	C22—N2—C18—C19	1.2 (6)
Cu2—N2—C22—P3	20.1 (4)	C23—P3—C22—N2	−148.7 (3)
Cu2—N2—C22—C21	−162.7 (3)	C23—P3—C22—C21	34.2 (4)
Cu3—P3—C22—N2	−21.2 (3)	C23—P3—C29—C30	103.2 (4)
Cu3—P3—C22—C21	161.7 (3)	C23—P3—C29—C34	−73.1 (4)
Cu3—P3—C23—C24	−60.9 (4)	C23—C24—C25—C26	−0.5 (7)
Cu3—P3—C23—C28	117.6 (4)	C24—C23—C28—C27	0.6 (7)
Cu3—P3—C29—C30	−27.6 (4)	C24—C25—C26—C27	1.0 (8)
Cu3—P3—C29—C34	156.1 (4)	C25—C26—C27—C28	−0.7 (9)
Cu3—N3—C35—C36	−171.3 (3)	C26—C27—C28—C23	−0.1 (8)
Cu3—N3—C39—P1	−10.7 (4)	C28—C23—C24—C25	−0.3 (7)
Cu3—N3—C39—C38	170.7 (3)	C29—P3—C22—N2	105.6 (3)
P1—C40—C41—C42	178.7 (4)	C29—P3—C22—C21	−71.5 (4)
P1—C40—C45—C44	179.4 (4)	C29—P3—C23—C24	169.6 (3)
P1—C46—C47—C48	−179.3 (4)	C29—P3—C23—C28	−11.9 (4)
P1—C46—C51—C50	178.6 (4)	C29—C30—C31—C32	−3.3 (7)
P2—C6—C7—C8	−177.1 (6)	C30—C29—C34—C33	−2.6 (7)
P2—C6—C11—C10	175.9 (4)	C30—C31—C32—C33	2.1 (8)
P2—C12—C13—C14	176.0 (3)	C31—C32—C33—C34	−1.2 (8)
P2—C12—C17—C16	−176.9 (4)	C32—C33—C34—C29	1.5 (8)
P3—C23—C24—C25	178.3 (4)	C34—C29—C30—C31	3.6 (7)
P3—C23—C28—C27	−177.9 (4)	C35—N3—C39—P1	176.6 (3)
P3—C29—C30—C31	−173.0 (4)	C35—N3—C39—C38	−2.0 (6)
P3—C29—C34—C33	173.7 (4)	C35—C36—C37—C38	−0.2 (6)
N1—C1—C2—C3	−1.4 (7)	C36—C37—C38—C39	0.5 (6)
N2—C18—C19—C20	−3.8 (7)	C37—C38—C39—P1	−177.9 (3)
N3—C35—C36—C37	−1.3 (7)	C37—C38—C39—N3	0.6 (6)
C1—N1—C5—P2	−172.1 (3)	C39—P1—C40—C41	−55.4 (4)
C1—N1—C5—C4	3.0 (6)	C39—P1—C40—C45	128.5 (4)
C1—C2—C3—C4	1.1 (7)	C39—P1—C46—C47	−36.7 (4)
C2—C3—C4—C5	1.2 (7)	C39—P1—C46—C51	146.1 (4)
C3—C4—C5—P2	171.6 (3)	C39—N3—C35—C36	2.3 (6)
C3—C4—C5—N1	−3.3 (6)	C40—P1—C39—N3	152.0 (3)
C5—P2—C6—C7	−21.2 (5)	C40—P1—C39—C38	−29.5 (4)
C5—P2—C6—C11	164.3 (4)	C40—P1—C46—C47	69.0 (4)
C5—P2—C12—C13	−76.8 (4)	C40—P1—C46—C51	−108.2 (4)
C5—P2—C12—C17	100.6 (3)	C40—C41—C42—C43	3.8 (8)
C5—N1—C1—C2	−0.7 (6)	C41—C40—C45—C44	3.2 (7)
C6—P2—C5—N1	105.6 (3)	C41—C42—C43—C44	−0.6 (9)
C6—P2—C5—C4	−69.6 (4)	C42—C43—C44—C45	−1.2 (9)
C6—P2—C12—C13	27.5 (4)	C43—C44—C45—C40	−0.1 (8)
C6—P2—C12—C17	−155.0 (3)	C45—C40—C41—C42	−5.1 (7)
C6—C7—C8—C9	1.6 (14)	C46—P1—C39—N3	−101.8 (3)
C7—C6—C11—C10	1.2 (8)	C46—P1—C39—C38	76.7 (4)
C7—C8—C9—C10	0.7 (13)	C46—P1—C40—C41	−163.1 (4)
C8—C9—C10—C11	−2.0 (10)	C46—P1—C40—C45	20.8 (4)
C9—C10—C11—C6	1.0 (9)	C46—C47—C48—C49	1.1 (8)
C11—C6—C7—C8	−2.5 (11)	C47—C46—C51—C50	1.3 (7)
C12—P2—C5—N1	−146.0 (3)	C47—C48—C49—C50	0.8 (8)
C12—P2—C5—C4	38.9 (4)	C48—C49—C50—C51	−1.6 (8)
C12—P2—C6—C7	−128.1 (5)	C49—C50—C51—C46	0.6 (7)
C12—P2—C6—C11	57.4 (4)	C51—C46—C47—C48	−2.1 (7)
C12—C13—C14—C15	0.3 (7)