Synthesis, crystal structure, DFT studies and photophysical properties of a copper(I)–tri­phenyl­phosphane complex based on trans-(±)-2,4,5-tris­(pyridin-2-yl)-2-imidazoline

The possibility of using less expensive and nontoxic metals, such as copper, as substitutes for more expensive heavy metals in the synthesis of new transition-metal complexes to be used as sensitizers in dye-sensitized solar cells (DSSCs) has stimulated research in this field. The novel photoluminescent cop­per(I) com­plex bis­(tri­phenyl­phosphane-κP)[trans-(±)-2,4,5-tris­(pyridin-2-yl)-2-imidazo­line-κ²N²,N³]copper(I) hexafluorophosphate, [Cu^I(C₁₈H₁₅N₅)(C₁₈H₁₅P)₂]PF₆, has been successfully synthesized and characterized by IR and ¹H NMR spectroscopy, as well as by single-crystal X-ray diffraction and thermogravimetric analysis. The complex showed inter­esting photophysical properties, which were studied experimentally in solution and in the solid state by UV–Vis and fluorescence spectroscopy. Density functional theory (DFT) calculations with di­chloro­methane as solvent reproduced reasonably well the HOMO and LUMO orbitals of the title compound.

Computing details

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Bis(triphenylphosphane-κP)[trans-(±)-2,4,5-tris(pyridin-2-yl)-2-imidazoline-κ²N²,N³]copper(I) hexafluorophosphate

Crystal data

[Cu(C18H15N5)(C18H15P)2]PF6	F(000) = 2128
Mr = 1034.40	Dx = 1.433 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.0725 (7) Å	Cell parameters from 9963 reflections
b = 12.3992 (6) Å	θ = 3.2–28.7°
c = 30.0047 (16) Å	µ = 0.62 mm^−1
β = 99.734 (5)°	T = 100 K
V = 4793.4 (4) Å^3	Block, translucent yellow
Z = 4	0.25 × 0.25 × 0.2 mm

Data collection

SuperNova, Dual, Cu at zero, EosS2 diffractometer	8448 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	6739 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.098
Detector resolution: 8.0769 pixels mm^-1	θmax = 25.0°, θmin = 2.6°
ω scans	h = −15→15
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −14→14
Tmin = 0.004, Tmax = 1.000	l = −35→35
29729 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.050	H-atom parameters constrained
wR(F^2) = 0.127	w = 1/[σ^2(Fo^2) + (0.057P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
8448 reflections	Δρmax = 0.64 e Å^−3
616 parameters	Δρmin = −1.17 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.

Refinement. The single-crystal X-ray diffraction study was carried out on an Agilent Technologies Super Nova diffractometer equipped with a CCD area detector (EosS2) using Mo Kα radiation (λ = 0.71073 Å) from a microfocus X-ray source and an Oxford Instruments Cryojet cooler. Frames were collected at T = 100 K. The measured intensities were reduced to F² and corrected for absorption using spherical harmonics (CrysAlis PRO; Agilent, 2014). Intensities were corrected for Lorentz and polarization effects. Structure solution, refinement, and data output were performed with the OLEX2 (Dolomanov et al., 2009) program package using SHELXL2014 (Sheldrick, 2015) for the refinement. Non-H atoms were refined anisotropically.

Hydrogen-bonding interactions in the crystal lattice were calculated with the Mercury program package (Macrae et al., 2008). Figures were created with ORTEP (Farrugia, 1999) and Mercury (Macrae et al., 2008).

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

	x	y	z	Uiso*/Ueq
C1	0.5407 (3)	0.7706 (2)	0.61013 (9)	0.0135 (7)
C2	0.6176 (2)	0.7035 (2)	0.67708 (9)	0.0127 (6)
H2	0.6226	0.6251	0.6808	0.015*
C3	0.5047 (2)	0.7392 (2)	0.68150 (9)	0.0145 (7)
H3	0.5076	0.8001	0.7025	0.017*
C4	0.7041 (3)	0.7544 (2)	0.70930 (9)	0.0173 (5)
C5	0.7179 (3)	0.8659 (2)	0.71014 (9)	0.0173 (5)
H5	0.6703	0.9102	0.6922	0.021*
C6	0.8027 (3)	0.9101 (3)	0.73792 (10)	0.0283 (8)
H6	0.8138	0.9843	0.7386	0.034*
C7	0.8705 (3)	0.8421 (3)	0.76462 (11)	0.0321 (9)
H7	0.9286	0.8691	0.7835	0.039*
C8	0.8502 (3)	0.7325 (3)	0.76270 (10)	0.0266 (8)
H8	0.8953	0.6871	0.7813	0.032*
C9	0.4419 (2)	0.6489 (2)	0.69710 (9)	0.0165 (7)
C10	0.4036 (3)	0.5651 (2)	0.66822 (12)	0.0323 (9)
H10	0.4137	0.5650	0.6383	0.039*
C11	0.3506 (3)	0.4821 (3)	0.68462 (13)	0.0415 (10)
H11	0.3236	0.4255	0.6659	0.050*
C12	0.3382 (3)	0.4845 (3)	0.72900 (12)	0.0334 (9)
H12	0.3037	0.4289	0.7411	0.040*
C13	0.3778 (3)	0.5705 (3)	0.75542 (11)	0.0319 (9)
H13	0.3686	0.5716	0.7855	0.038*
C14	0.5277 (3)	0.8039 (2)	0.56194 (9)	0.0132 (7)
C15	0.4368 (3)	0.8465 (2)	0.53832 (9)	0.0185 (7)
H15	0.3796	0.8574	0.5525	0.022*
C16	0.4324 (3)	0.8729 (2)	0.49277 (10)	0.0200 (7)
H16	0.3720	0.9009	0.4759	0.024*
C17	0.5194 (3)	0.8567 (2)	0.47326 (9)	0.0173 (7)
H17	0.5190	0.8745	0.4431	0.021*
C18	0.6071 (3)	0.8135 (2)	0.49923 (9)	0.0148 (7)
H18	0.6654	0.8026	0.4858	0.018*
C19	0.8504 (2)	0.9632 (2)	0.61919 (9)	0.0136 (6)
C20	0.7495 (3)	1.0029 (2)	0.61330 (10)	0.0198 (7)
H20	0.6954	0.9626	0.5973	0.024*
C21	0.7292 (3)	1.1029 (2)	0.63128 (10)	0.0234 (8)
H21	0.6616	1.1291	0.6272	0.028*
C22	0.8091 (3)	1.1629 (2)	0.65503 (10)	0.0239 (8)
H22	0.7953	1.2293	0.6671	0.029*
C23	0.9095 (3)	1.1244 (2)	0.66086 (10)	0.0226 (8)
H23	0.9633	1.1652	0.6768	0.027*
C24	0.9304 (3)	1.0254 (2)	0.64311 (9)	0.0184 (7)
H24	0.9983	1.0001	0.6472	0.022*
C25	0.9056 (2)	0.8583 (2)	0.54088 (9)	0.0142 (6)
C26	0.8558 (3)	0.9423 (2)	0.51449 (10)	0.0194 (7)
H26	0.8143	0.9909	0.5269	0.023*
C27	0.8686 (3)	0.9527 (3)	0.46964 (10)	0.0259 (8)
H27	0.8345	1.0079	0.4521	0.031*
C28	0.9308 (3)	0.8831 (3)	0.45083 (10)	0.0276 (8)
H28	0.9382	0.8904	0.4207	0.033*
C29	0.9826 (3)	0.8015 (2)	0.47724 (10)	0.0268 (8)
H29	1.0267	0.7554	0.4650	0.032*
C30	0.9688 (3)	0.7884 (2)	0.52183 (10)	0.0201 (7)
H30	1.0022	0.7322	0.5390	0.024*
C31	0.9923 (3)	0.7856 (2)	0.63231 (9)	0.0138 (7)
C32	1.0903 (3)	0.8207 (2)	0.62730 (10)	0.0191 (7)
H32	1.0985	0.8645	0.6030	0.023*
C33	1.1766 (3)	0.7907 (2)	0.65861 (11)	0.0252 (8)
H33	1.2425	0.8137	0.6551	0.030*
C34	1.1642 (3)	0.7264 (2)	0.69503 (11)	0.0244 (8)
H34	1.2218	0.7068	0.7161	0.029*
C35	1.0677 (3)	0.6915 (2)	0.70019 (11)	0.0247 (8)
H35	1.0600	0.6481	0.7247	0.030*
C36	0.9811 (3)	0.7205 (2)	0.66907 (10)	0.0179 (7)
H36	0.9157	0.6965	0.6727	0.021*
C37	0.6357 (2)	0.4693 (2)	0.58529 (9)	0.0127 (6)
C38	0.5459 (2)	0.5102 (2)	0.55872 (9)	0.0158 (7)
H38	0.5504	0.5701	0.5405	0.019*
C39	0.4509 (3)	0.4629 (2)	0.55929 (9)	0.0173 (7)
H39	0.3921	0.4900	0.5409	0.021*
C40	0.4423 (3)	0.3756 (2)	0.58697 (9)	0.0158 (7)
H40	0.3779	0.3441	0.5874	0.019*
C41	0.5301 (3)	0.3351 (2)	0.61404 (10)	0.0191 (7)
H41	0.5245	0.2767	0.6329	0.023*
C42	0.6261 (3)	0.3812 (2)	0.61321 (10)	0.0172 (7)
H42	0.6847	0.3533	0.6314	0.021*
C43	0.7830 (2)	0.4903 (2)	0.52609 (9)	0.0124 (6)
C44	0.7699 (3)	0.3833 (2)	0.51195 (10)	0.0205 (7)
H44	0.7482	0.3322	0.5310	0.025*
C45	0.7888 (3)	0.3526 (2)	0.46974 (10)	0.0248 (8)
H45	0.7806	0.2808	0.4609	0.030*
C46	0.8196 (3)	0.4274 (3)	0.44059 (10)	0.0256 (8)
H46	0.8312	0.4064	0.4121	0.031*
C47	0.8330 (3)	0.5340 (2)	0.45413 (10)	0.0228 (7)
H47	0.8546	0.5848	0.4349	0.027*
C48	0.8140 (2)	0.5650 (2)	0.49662 (10)	0.0177 (7)
H48	0.8221	0.6369	0.5054	0.021*
C49	0.8566 (2)	0.4747 (2)	0.62242 (9)	0.0136 (6)
C50	0.9451 (3)	0.4282 (2)	0.61068 (10)	0.0201 (7)
H50	0.9523	0.4235	0.5804	0.024*
C51	1.0230 (3)	0.3889 (3)	0.64409 (11)	0.0266 (8)
H51	1.0816	0.3573	0.6359	0.032*
C52	1.0146 (3)	0.3959 (2)	0.68910 (10)	0.0237 (8)
H52	1.0673	0.3695	0.7111	0.028*
C53	0.9274 (3)	0.4424 (2)	0.70135 (10)	0.0212 (8)
H53	0.9213	0.4473	0.7317	0.025*
C54	0.8484 (3)	0.4822 (2)	0.66836 (9)	0.0185 (7)
H54	0.7901	0.5138	0.6768	0.022*
Cu1	0.73795 (3)	0.71671 (2)	0.58958 (2)	0.01164 (12)
N1	0.6278 (2)	0.73058 (17)	0.62984 (7)	0.0133 (6)
N2	0.4633 (2)	0.77549 (18)	0.63520 (8)	0.0150 (6)
H2A	0.4007	0.7963	0.6256	0.018*
N3	0.7693 (2)	0.68814 (19)	0.73561 (8)	0.0213 (6)
N4	0.4286 (2)	0.6523 (2)	0.74022 (8)	0.0233 (6)
N5	0.6124 (2)	0.78650 (16)	0.54293 (7)	0.0118 (5)
P1	0.87253 (6)	0.82966 (5)	0.59659 (2)	0.01125 (18)
P2	0.75691 (6)	0.53821 (5)	0.58069 (2)	0.01199 (18)
F1	0.32492 (15)	0.96571 (13)	0.61410 (5)	0.0263 (5)
F2	0.38070 (18)	0.98443 (15)	0.68944 (6)	0.0394 (6)
F3	0.47607 (17)	1.05230 (18)	0.63983 (7)	0.0460 (6)
F4	0.33648 (16)	1.14638 (13)	0.60541 (6)	0.0302 (5)
F5	0.24040 (17)	1.07849 (15)	0.65432 (7)	0.0387 (5)
F6	0.3923 (2)	1.16595 (16)	0.68074 (7)	0.0512 (7)
P3	0.35805 (7)	1.06711 (6)	0.64800 (3)	0.0209 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0218 (19)	0.0103 (13)	0.0098 (14)	−0.0017 (12)	0.0061 (13)	−0.0013 (11)
C2	0.0152 (17)	0.0129 (13)	0.0113 (14)	0.0014 (12)	0.0060 (13)	0.0035 (11)
C3	0.0188 (18)	0.0154 (14)	0.0104 (14)	0.0030 (13)	0.0058 (13)	0.0007 (11)
C4	0.0207 (13)	0.0238 (10)	0.0096 (10)	−0.0004 (10)	0.0086 (10)	−0.0015 (8)
C5	0.0207 (13)	0.0238 (10)	0.0096 (10)	−0.0004 (10)	0.0086 (10)	−0.0015 (8)
C6	0.036 (2)	0.0329 (18)	0.0194 (17)	−0.0127 (17)	0.0152 (16)	−0.0075 (14)
C7	0.024 (2)	0.056 (2)	0.0161 (17)	−0.0133 (18)	0.0035 (16)	−0.0090 (16)
C8	0.020 (2)	0.048 (2)	0.0112 (16)	0.0048 (17)	−0.0007 (15)	−0.0012 (14)
C9	0.0133 (17)	0.0236 (15)	0.0139 (15)	0.0051 (13)	0.0055 (13)	0.0049 (12)
C10	0.045 (3)	0.0285 (18)	0.0275 (19)	−0.0058 (17)	0.0185 (18)	−0.0059 (14)
C11	0.047 (3)	0.0313 (19)	0.051 (2)	−0.0102 (19)	0.023 (2)	−0.0067 (17)
C12	0.025 (2)	0.0326 (19)	0.044 (2)	−0.0032 (16)	0.0089 (18)	0.0201 (17)
C13	0.024 (2)	0.052 (2)	0.0189 (17)	−0.0040 (18)	0.0016 (16)	0.0187 (16)
C14	0.0197 (18)	0.0091 (13)	0.0106 (14)	−0.0018 (12)	0.0021 (13)	−0.0013 (11)
C15	0.0169 (18)	0.0220 (15)	0.0165 (16)	0.0049 (13)	0.0027 (14)	−0.0023 (12)
C16	0.0189 (19)	0.0238 (16)	0.0156 (15)	0.0052 (14)	−0.0024 (14)	0.0046 (12)
C17	0.028 (2)	0.0152 (14)	0.0084 (14)	−0.0010 (13)	0.0016 (14)	−0.0003 (11)
C18	0.0222 (19)	0.0143 (13)	0.0092 (14)	−0.0054 (13)	0.0060 (13)	−0.0022 (11)
C19	0.0186 (18)	0.0129 (13)	0.0101 (14)	0.0002 (12)	0.0045 (13)	0.0033 (11)
C20	0.0202 (19)	0.0162 (14)	0.0208 (16)	−0.0007 (13)	−0.0026 (14)	−0.0004 (12)
C21	0.0218 (19)	0.0198 (15)	0.0277 (18)	0.0084 (14)	0.0015 (15)	−0.0036 (13)
C22	0.033 (2)	0.0138 (15)	0.0229 (17)	0.0074 (14)	0.0001 (16)	−0.0029 (12)
C23	0.027 (2)	0.0164 (15)	0.0207 (16)	0.0001 (14)	−0.0067 (15)	−0.0020 (12)
C24	0.0176 (18)	0.0176 (15)	0.0190 (16)	0.0034 (13)	−0.0003 (14)	−0.0009 (12)
C25	0.0155 (17)	0.0130 (13)	0.0140 (14)	−0.0072 (12)	0.0025 (13)	0.0005 (11)
C26	0.0172 (19)	0.0227 (15)	0.0178 (16)	−0.0006 (13)	0.0016 (14)	0.0042 (12)
C27	0.022 (2)	0.0321 (18)	0.0216 (17)	−0.0070 (15)	−0.0019 (15)	0.0090 (14)
C28	0.031 (2)	0.043 (2)	0.0104 (15)	−0.0157 (17)	0.0088 (15)	0.0009 (14)
C29	0.031 (2)	0.0276 (17)	0.0237 (18)	−0.0057 (16)	0.0112 (16)	−0.0092 (14)
C30	0.025 (2)	0.0164 (14)	0.0198 (16)	−0.0052 (14)	0.0059 (15)	−0.0011 (12)
C31	0.0174 (18)	0.0088 (13)	0.0154 (15)	−0.0010 (12)	0.0037 (13)	−0.0033 (11)
C32	0.0184 (18)	0.0151 (14)	0.0244 (17)	−0.0009 (13)	0.0057 (14)	0.0038 (12)
C33	0.0129 (19)	0.0218 (16)	0.039 (2)	−0.0010 (13)	−0.0010 (16)	0.0009 (14)
C34	0.019 (2)	0.0202 (16)	0.0303 (19)	0.0033 (14)	−0.0065 (16)	0.0012 (13)
C35	0.026 (2)	0.0222 (16)	0.0232 (17)	−0.0001 (15)	−0.0032 (16)	0.0088 (13)
C36	0.0150 (18)	0.0211 (15)	0.0182 (16)	−0.0039 (13)	0.0044 (14)	0.0020 (12)
C37	0.0128 (17)	0.0138 (13)	0.0117 (14)	0.0006 (12)	0.0027 (12)	−0.0034 (11)
C38	0.0205 (19)	0.0155 (14)	0.0116 (14)	−0.0026 (13)	0.0032 (13)	−0.0020 (11)
C39	0.0182 (18)	0.0206 (15)	0.0119 (14)	−0.0023 (13)	−0.0008 (13)	−0.0024 (12)
C40	0.0175 (18)	0.0169 (14)	0.0141 (14)	−0.0068 (13)	0.0057 (13)	−0.0067 (12)
C41	0.028 (2)	0.0108 (14)	0.0193 (16)	−0.0039 (13)	0.0049 (15)	0.0010 (12)
C42	0.0155 (17)	0.0143 (14)	0.0209 (16)	−0.0005 (12)	0.0004 (14)	−0.0007 (12)
C43	0.0102 (16)	0.0153 (14)	0.0109 (14)	0.0028 (12)	−0.0004 (12)	−0.0024 (11)
C44	0.0216 (19)	0.0157 (15)	0.0240 (17)	0.0018 (13)	0.0036 (15)	0.0001 (12)
C45	0.026 (2)	0.0270 (16)	0.0216 (17)	0.0032 (15)	0.0062 (15)	−0.0129 (14)
C46	0.024 (2)	0.041 (2)	0.0118 (15)	0.0016 (16)	0.0039 (15)	−0.0081 (14)
C47	0.0209 (19)	0.0321 (17)	0.0171 (16)	−0.0050 (15)	0.0079 (14)	−0.0003 (13)
C48	0.0122 (17)	0.0223 (15)	0.0184 (16)	−0.0014 (13)	0.0018 (14)	−0.0015 (12)
C49	0.0158 (17)	0.0116 (13)	0.0129 (14)	−0.0029 (12)	0.0013 (13)	0.0016 (11)
C50	0.0182 (19)	0.0253 (16)	0.0176 (16)	0.0038 (14)	0.0056 (14)	0.0016 (12)
C51	0.0140 (18)	0.0384 (18)	0.0281 (18)	0.0090 (15)	0.0054 (15)	0.0079 (15)
C52	0.0155 (19)	0.0312 (17)	0.0227 (17)	−0.0004 (15)	−0.0018 (15)	0.0113 (14)
C53	0.025 (2)	0.0224 (15)	0.0158 (16)	−0.0056 (14)	0.0016 (15)	0.0053 (12)
C54	0.0218 (19)	0.0156 (14)	0.0177 (15)	−0.0023 (13)	0.0022 (14)	−0.0002 (12)
Cu1	0.0124 (2)	0.01264 (19)	0.01029 (19)	−0.00038 (14)	0.00297 (16)	−0.00059 (13)
N1	0.0170 (15)	0.0141 (12)	0.0085 (12)	0.0000 (10)	0.0013 (11)	−0.0011 (9)
N2	0.0101 (14)	0.0248 (13)	0.0112 (12)	0.0060 (11)	0.0046 (11)	0.0075 (10)
N3	0.0223 (16)	0.0300 (14)	0.0115 (13)	0.0043 (12)	0.0026 (12)	0.0018 (11)
N4	0.0175 (16)	0.0402 (15)	0.0122 (13)	−0.0026 (13)	0.0024 (12)	0.0096 (11)
N5	0.0156 (14)	0.0107 (11)	0.0099 (12)	−0.0032 (10)	0.0041 (11)	−0.0026 (9)
P1	0.0118 (4)	0.0117 (3)	0.0107 (4)	−0.0001 (3)	0.0031 (3)	−0.0001 (3)
P2	0.0137 (4)	0.0128 (4)	0.0099 (4)	−0.0003 (3)	0.0030 (3)	−0.0006 (3)
F1	0.0317 (12)	0.0222 (9)	0.0235 (10)	0.0048 (8)	0.0001 (9)	−0.0017 (7)
F2	0.0518 (15)	0.0451 (11)	0.0190 (10)	−0.0083 (11)	−0.0010 (10)	0.0137 (8)
F3	0.0190 (12)	0.0648 (14)	0.0534 (14)	−0.0035 (11)	0.0043 (11)	0.0143 (11)
F4	0.0384 (13)	0.0257 (9)	0.0273 (10)	−0.0047 (9)	0.0074 (9)	0.0101 (8)
F5	0.0358 (13)	0.0454 (12)	0.0410 (12)	0.0060 (11)	0.0236 (10)	0.0031 (9)
F6	0.075 (2)	0.0413 (12)	0.0340 (12)	−0.0179 (12)	−0.0010 (12)	−0.0124 (10)
P3	0.0246 (5)	0.0239 (4)	0.0150 (4)	−0.0044 (4)	0.0059 (4)	0.0011 (3)

Geometric parameters (Å, º)

C1—C14	1.486 (4)	C29—C30	1.390 (4)
C1—N1	1.290 (4)	C30—H30	0.9300
C1—N2	1.360 (4)	C31—C32	1.386 (4)
C2—H2	0.9800	C31—C36	1.395 (4)
C2—C3	1.567 (4)	C31—P1	1.825 (3)
C2—C4	1.498 (4)	C32—H32	0.9300
C2—N1	1.484 (3)	C32—C33	1.391 (4)
C3—H3	0.9800	C33—H33	0.9300
C3—C9	1.509 (4)	C33—C34	1.384 (5)
C3—N2	1.474 (3)	C34—H34	0.9300
C4—C5	1.393 (4)	C34—C35	1.367 (5)
C4—N3	1.340 (4)	C35—H35	0.9300
C5—H5	0.9300	C35—C36	1.387 (4)
C5—C6	1.384 (4)	C36—H36	0.9300
C6—H6	0.9300	C37—C38	1.399 (4)
C6—C7	1.378 (5)	C37—C42	1.395 (4)
C7—H7	0.9300	C37—P2	1.826 (3)
C7—C8	1.384 (5)	C38—H38	0.9300
C8—H8	0.9300	C38—C39	1.376 (4)
C8—N3	1.338 (4)	C39—H39	0.9300
C9—C10	1.391 (4)	C39—C40	1.381 (4)
C9—N4	1.335 (4)	C40—H40	0.9300
C10—H10	0.9300	C40—C41	1.383 (4)
C10—C11	1.378 (5)	C41—H41	0.9300
C11—H11	0.9300	C41—C42	1.383 (4)
C11—C12	1.369 (5)	C42—H42	0.9300
C12—H12	0.9300	C43—C44	1.394 (4)
C12—C13	1.376 (5)	C43—C48	1.388 (4)
C13—H13	0.9300	C43—P2	1.828 (3)
C13—N4	1.335 (4)	C44—H44	0.9300
C14—C15	1.382 (4)	C44—C45	1.384 (4)
C14—N5	1.346 (4)	C45—H45	0.9300
C15—H15	0.9300	C45—C46	1.381 (5)
C15—C16	1.397 (4)	C46—H46	0.9300
C16—H16	0.9300	C46—C47	1.385 (4)
C16—C17	1.379 (5)	C47—H47	0.9300
C17—H17	0.9300	C47—C48	1.393 (4)
C17—C18	1.380 (4)	C48—H48	0.9300
C18—H18	0.9300	C49—C50	1.390 (4)
C18—N5	1.344 (3)	C49—C54	1.403 (4)
C19—C20	1.391 (4)	C49—P2	1.826 (3)
C19—C24	1.396 (4)	C50—H50	0.9300
C19—P1	1.831 (3)	C50—C51	1.390 (4)
C20—H20	0.9300	C51—H51	0.9300
C20—C21	1.396 (4)	C51—C52	1.376 (4)
C21—H21	0.9300	C52—H52	0.9300
C21—C22	1.379 (4)	C52—C53	1.382 (5)
C22—H22	0.9300	C53—H53	0.9300
C22—C23	1.379 (5)	C53—C54	1.394 (4)
C23—H23	0.9300	C54—H54	0.9300
C23—C24	1.383 (4)	Cu1—N1	2.038 (3)
C24—H24	0.9300	Cu1—N5	2.150 (2)
C25—C26	1.400 (4)	Cu1—P1	2.2306 (8)
C25—C30	1.387 (4)	Cu1—P2	2.2479 (8)
C25—P1	1.831 (3)	N2—H2A	0.8600
C26—H26	0.9300	F1—P3	1.6292 (18)
C26—C27	1.390 (4)	F2—P3	1.6000 (18)
C27—H27	0.9300	F3—P3	1.613 (2)
C27—C28	1.371 (5)	F4—P3	1.5990 (17)
C28—H28	0.9300	F5—P3	1.587 (2)
C28—C29	1.388 (4)	F6—P3	1.587 (2)
C29—H29	0.9300
N1—C1—C14	120.0 (3)	C35—C34—C33	120.3 (3)
N1—C1—N2	116.4 (2)	C35—C34—H34	119.8
N2—C1—C14	123.5 (3)	C34—C35—H35	119.8
C3—C2—H2	108.5	C34—C35—C36	120.3 (3)
C4—C2—H2	108.5	C36—C35—H35	119.8
C4—C2—C3	116.5 (2)	C31—C36—H36	120.0
N1—C2—H2	108.5	C35—C36—C31	120.0 (3)
N1—C2—C3	104.8 (2)	C35—C36—H36	120.0
N1—C2—C4	109.9 (2)	C38—C37—P2	116.3 (2)
C2—C3—H3	109.7	C42—C37—C38	118.3 (3)
C9—C3—C2	112.7 (2)	C42—C37—P2	125.4 (2)
C9—C3—H3	109.7	C37—C38—H38	119.7
N2—C3—C2	102.0 (2)	C39—C38—C37	120.7 (3)
N2—C3—H3	109.7	C39—C38—H38	119.7
N2—C3—C9	112.8 (2)	C38—C39—H39	119.8
C5—C4—C2	120.7 (3)	C38—C39—C40	120.5 (3)
N3—C4—C2	117.2 (2)	C40—C39—H39	119.8
N3—C4—C5	122.0 (3)	C39—C40—H40	120.2
C4—C5—H5	120.3	C39—C40—C41	119.6 (3)
C6—C5—C4	119.5 (3)	C41—C40—H40	120.2
C6—C5—H5	120.3	C40—C41—H41	119.8
C5—C6—H6	120.7	C42—C41—C40	120.3 (3)
C7—C6—C5	118.6 (3)	C42—C41—H41	119.8
C7—C6—H6	120.7	C37—C42—H42	119.7
C6—C7—H7	120.8	C41—C42—C37	120.6 (3)
C6—C7—C8	118.5 (3)	C41—C42—H42	119.7
C8—C7—H7	120.8	C44—C43—P2	123.3 (2)
C7—C8—H8	118.1	C48—C43—C44	118.4 (3)
N3—C8—C7	123.7 (3)	C48—C43—P2	118.2 (2)
N3—C8—H8	118.1	C43—C44—H44	119.7
C10—C9—C3	121.2 (3)	C45—C44—C43	120.5 (3)
N4—C9—C3	116.3 (3)	C45—C44—H44	119.7
N4—C9—C10	122.4 (3)	C44—C45—H45	119.6
C9—C10—H10	120.5	C46—C45—C44	120.7 (3)
C11—C10—C9	119.0 (3)	C46—C45—H45	119.6
C11—C10—H10	120.5	C45—C46—H46	120.3
C10—C11—H11	120.6	C45—C46—C47	119.4 (3)
C12—C11—C10	118.8 (3)	C47—C46—H46	120.3
C12—C11—H11	120.6	C46—C47—H47	120.1
C11—C12—H12	120.6	C46—C47—C48	119.9 (3)
C11—C12—C13	118.8 (3)	C48—C47—H47	120.1
C13—C12—H12	120.6	C43—C48—C47	121.0 (3)
C12—C13—H13	118.2	C43—C48—H48	119.5
N4—C13—C12	123.6 (3)	C47—C48—H48	119.5
N4—C13—H13	118.2	C50—C49—C54	118.8 (3)
C15—C14—C1	123.5 (3)	C50—C49—P2	122.2 (2)
N5—C14—C1	113.6 (3)	C54—C49—P2	118.7 (2)
N5—C14—C15	122.8 (3)	C49—C50—H50	119.9
C14—C15—H15	120.6	C49—C50—C51	120.1 (3)
C14—C15—C16	118.7 (3)	C51—C50—H50	119.9
C16—C15—H15	120.6	C50—C51—H51	119.5
C15—C16—H16	120.6	C52—C51—C50	121.0 (3)
C17—C16—C15	118.8 (3)	C52—C51—H51	119.5
C17—C16—H16	120.6	C51—C52—H52	120.2
C16—C17—H17	120.6	C51—C52—C53	119.6 (3)
C16—C17—C18	118.9 (3)	C53—C52—H52	120.2
C18—C17—H17	120.6	C52—C53—H53	119.9
C17—C18—H18	118.4	C52—C53—C54	120.3 (3)
N5—C18—C17	123.2 (3)	C54—C53—H53	119.9
N5—C18—H18	118.4	C49—C54—H54	119.9
C20—C19—C24	118.8 (3)	C53—C54—C49	120.3 (3)
C20—C19—P1	118.6 (2)	C53—C54—H54	119.9
C24—C19—P1	122.6 (2)	N1—Cu1—N5	79.26 (9)
C19—C20—H20	119.9	N1—Cu1—P1	121.09 (7)
C19—C20—C21	120.3 (3)	N1—Cu1—P2	104.87 (7)
C21—C20—H20	119.9	N5—Cu1—P1	108.16 (6)
C20—C21—H21	120.0	N5—Cu1—P2	113.97 (6)
C22—C21—C20	120.1 (3)	P1—Cu1—P2	121.89 (3)
C22—C21—H21	120.0	C1—N1—C2	108.1 (3)
C21—C22—H22	120.0	C1—N1—Cu1	114.70 (19)
C21—C22—C23	120.1 (3)	C2—N1—Cu1	137.18 (19)
C23—C22—H22	120.0	C1—N2—C3	108.6 (2)
C22—C23—H23	119.9	C1—N2—H2A	125.7
C22—C23—C24	120.2 (3)	C3—N2—H2A	125.7
C24—C23—H23	119.9	C8—N3—C4	117.6 (3)
C19—C24—H24	119.7	C9—N4—C13	117.4 (3)
C23—C24—C19	120.6 (3)	C14—N5—Cu1	112.38 (17)
C23—C24—H24	119.7	C18—N5—C14	117.6 (3)
C26—C25—P1	120.1 (2)	C18—N5—Cu1	130.0 (2)
C30—C25—C26	119.0 (3)	C19—P1—Cu1	115.57 (11)
C30—C25—P1	120.3 (2)	C25—P1—C19	103.81 (13)
C25—C26—H26	120.1	C25—P1—Cu1	109.87 (9)
C27—C26—C25	119.7 (3)	C31—P1—C19	103.10 (12)
C27—C26—H26	120.1	C31—P1—C25	106.44 (14)
C26—C27—H27	119.4	C31—P1—Cu1	116.88 (9)
C28—C27—C26	121.1 (3)	C37—P2—C43	102.20 (13)
C28—C27—H27	119.4	C37—P2—C49	105.90 (13)
C27—C28—H28	120.3	C37—P2—Cu1	109.73 (9)
C27—C28—C29	119.3 (3)	C43—P2—Cu1	117.87 (9)
C29—C28—H28	120.3	C49—P2—C43	104.74 (13)
C28—C29—H29	119.8	C49—P2—Cu1	115.06 (9)
C28—C29—C30	120.3 (3)	F2—P3—F1	89.17 (10)
C30—C29—H29	119.8	F2—P3—F3	89.38 (12)
C25—C30—C29	120.4 (3)	F3—P3—F1	88.70 (12)
C25—C30—H30	119.8	F4—P3—F1	89.02 (9)
C29—C30—H30	119.8	F4—P3—F2	177.93 (12)
C32—C31—C36	119.4 (3)	F4—P3—F3	89.57 (12)
C32—C31—P1	124.0 (2)	F5—P3—F1	88.99 (11)
C36—C31—P1	116.3 (2)	F5—P3—F2	91.14 (12)
C31—C32—H32	119.9	F5—P3—F3	177.62 (12)
C31—C32—C33	120.1 (3)	F5—P3—F4	89.84 (11)
C33—C32—H32	119.9	F6—P3—F1	178.97 (15)
C32—C33—H33	120.1	F6—P3—F2	91.03 (11)
C34—C33—C32	119.9 (3)	F6—P3—F3	90.30 (14)
C34—C33—H33	120.1	F6—P3—F4	90.76 (11)
C33—C34—H34	119.8	F6—P3—F5	92.01 (14)
C1—C14—C15—C16	−178.6 (2)	C34—C35—C36—C31	0.0 (5)
C1—C14—N5—C18	179.4 (2)	C36—C31—C32—C33	0.3 (4)
C1—C14—N5—Cu1	−0.3 (3)	C36—C31—P1—C19	95.7 (2)
C2—C3—C9—C10	−73.9 (4)	C36—C31—P1—C25	−155.4 (2)
C2—C3—C9—N4	103.9 (3)	C36—C31—P1—Cu1	−32.3 (2)
C2—C3—N2—C1	−4.5 (3)	C37—C38—C39—C40	1.5 (4)
C2—C4—C5—C6	−175.4 (3)	C38—C37—C42—C41	0.8 (4)
C2—C4—N3—C8	176.4 (3)	C38—C37—P2—C43	−75.5 (2)
C3—C2—C4—C5	−59.7 (4)	C38—C37—P2—C49	175.1 (2)
C3—C2—C4—N3	122.9 (3)	C38—C37—P2—Cu1	50.4 (2)
C3—C2—N1—C1	−1.3 (3)	C38—C39—C40—C41	−0.4 (4)
C3—C2—N1—Cu1	−178.93 (19)	C39—C40—C41—C42	−0.5 (4)
C3—C9—C10—C11	177.2 (3)	C40—C41—C42—C37	0.3 (5)
C3—C9—N4—C13	−176.7 (3)	C42—C37—C38—C39	−1.7 (4)
C4—C2—C3—C9	−113.7 (3)	C42—C37—P2—C43	105.4 (3)
C4—C2—C3—N2	125.1 (2)	C42—C37—P2—C49	−4.0 (3)
C4—C2—N1—C1	−127.2 (2)	C42—C37—P2—Cu1	−128.8 (2)
C4—C2—N1—Cu1	55.2 (3)	C43—C44—C45—C46	−0.9 (5)
C4—C5—C6—C7	−1.1 (5)	C44—C43—C48—C47	−0.9 (4)
C5—C4—N3—C8	−1.0 (5)	C44—C43—P2—C37	−42.4 (3)
C5—C6—C7—C8	−0.5 (5)	C44—C43—P2—C49	67.9 (3)
C6—C7—C8—N3	1.5 (5)	C44—C43—P2—Cu1	−162.7 (2)
C7—C8—N3—C4	−0.7 (5)	C44—C45—C46—C47	0.9 (5)
C9—C3—N2—C1	−125.7 (3)	C45—C46—C47—C48	−0.9 (5)
C9—C10—C11—C12	−0.7 (6)	C46—C47—C48—C43	0.9 (5)
C10—C9—N4—C13	1.0 (5)	C48—C43—C44—C45	0.9 (5)
C10—C11—C12—C13	1.0 (6)	C48—C43—P2—C37	135.2 (2)
C11—C12—C13—N4	−0.4 (6)	C48—C43—P2—C49	−114.5 (2)
C12—C13—N4—C9	−0.6 (5)	C48—C43—P2—Cu1	14.9 (3)
C14—C1—N1—C2	−179.2 (2)	C49—C50—C51—C52	−0.6 (5)
C14—C1—N1—Cu1	−1.0 (3)	C50—C49—C54—C53	−0.8 (4)
C14—C1—N2—C3	−178.4 (2)	C50—C49—P2—C37	123.5 (2)
C14—C15—C16—C17	−0.8 (4)	C50—C49—P2—C43	15.9 (3)
C15—C14—N5—C18	0.8 (4)	C50—C49—P2—Cu1	−115.1 (2)
C15—C14—N5—Cu1	−178.9 (2)	C50—C51—C52—C53	0.2 (5)
C15—C16—C17—C18	0.9 (4)	C51—C52—C53—C54	−0.1 (5)
C16—C17—C18—N5	−0.2 (4)	C52—C53—C54—C49	0.4 (4)
C17—C18—N5—C14	−0.7 (4)	C54—C49—C50—C51	0.9 (4)
C17—C18—N5—Cu1	179.00 (19)	C54—C49—P2—C37	−62.8 (2)
C19—C20—C21—C22	−0.1 (5)	C54—C49—P2—C43	−170.4 (2)
C20—C19—C24—C23	0.4 (4)	C54—C49—P2—Cu1	58.6 (2)
C20—C19—P1—C25	94.5 (3)	N1—C1—C14—C15	179.4 (3)
C20—C19—P1—C31	−154.7 (2)	N1—C1—C14—N5	0.8 (4)
C20—C19—P1—Cu1	−25.9 (3)	N1—C1—N2—C3	4.3 (3)
C20—C21—C22—C23	0.4 (5)	N1—C2—C3—C9	124.6 (2)
C21—C22—C23—C24	−0.3 (5)	N1—C2—C3—N2	3.5 (3)
C22—C23—C24—C19	−0.1 (5)	N1—C2—C4—C5	59.2 (4)
C24—C19—C20—C21	−0.3 (5)	N1—C2—C4—N3	−118.2 (3)
C24—C19—P1—C25	−87.3 (3)	N2—C1—C14—C15	2.2 (4)
C24—C19—P1—C31	23.5 (3)	N2—C1—C14—N5	−176.4 (2)
C24—C19—P1—Cu1	152.3 (2)	N2—C1—N1—C2	−1.8 (3)
C25—C26—C27—C28	−1.1 (5)	N2—C1—N1—Cu1	176.45 (18)
C26—C25—C30—C29	0.1 (4)	N2—C3—C9—C10	40.9 (4)
C26—C25—P1—C19	−37.0 (3)	N2—C3—C9—N4	−141.3 (3)
C26—C25—P1—C31	−145.5 (2)	N3—C4—C5—C6	1.9 (5)
C26—C25—P1—Cu1	87.1 (2)	N4—C9—C10—C11	−0.4 (5)
C26—C27—C28—C29	−0.7 (5)	N5—C14—C15—C16	−0.1 (4)
C27—C28—C29—C30	2.1 (5)	P1—C19—C20—C21	178.0 (2)
C28—C29—C30—C25	−1.8 (5)	P1—C19—C24—C23	−177.8 (2)
C30—C25—C26—C27	1.4 (4)	P1—C25—C26—C27	−169.7 (2)
C30—C25—P1—C19	152.0 (2)	P1—C25—C30—C29	171.1 (2)
C30—C25—P1—C31	43.6 (3)	P1—C31—C32—C33	174.1 (2)
C30—C25—P1—Cu1	−83.8 (2)	P1—C31—C36—C35	−174.2 (2)
C31—C32—C33—C34	−0.6 (5)	P2—C37—C38—C39	179.1 (2)
C32—C31—C36—C35	0.0 (4)	P2—C37—C42—C41	180.0 (2)
C32—C31—P1—C19	−78.3 (3)	P2—C43—C44—C45	178.5 (2)
C32—C31—P1—C25	30.7 (3)	P2—C43—C48—C47	−178.7 (2)
C32—C31—P1—Cu1	153.8 (2)	P2—C49—C50—C51	174.6 (2)
C32—C33—C34—C35	0.6 (5)	P2—C49—C54—C53	−174.7 (2)
C33—C34—C35—C36	−0.2 (5)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the C9–C13/N4 ring and Cg2 is the centroid of the C43–C48 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···F5^i	0.93	2.48	3.339 (4)	153
C15—H15···F1	0.93	2.49	3.259 (4)	141
C17—H17···F4^ii	0.93	2.59	3.260 (4)	130
C17—H17···F3^ii	0.93	2.66	3.586 (4)	174
C27—H27···F1^ii	0.93	2.65	3.404 (4)	139
C33—H33···F1^iii	0.93	2.58	3.336 (4)	138
C34—H34···Cg1^iii	0.93	2.82	3.517	133
C39—H39···Cg2^iv	0.93	2.59	3.467 (4)	158
C40—H40···F4^v	0.93	2.59	3.249 (3)	129
N2—H2A···F1	0.86	2.32	2.975 (3)	133

Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x+1, −y+2, −z+1; (iii) x+1, y, z; (iv) −x+1, −y+1, −z+1; (v) x, y−1, z.