A new heteroleptic cuprous polymer constructed by a cyano­pyridine ligand exhibiting a supra­molecular framework structure and luminescence

Luminescent cuprous com­plexes are of great importance among coordination com­pounds due to their relative abundance, low cost and ability to display excellent luminescence. The title heteroleptic cuprous polymer solvate, catena-poly[[[(9,9-dimethyl-9H-xanthene-4,5-di­yl)bis­(di­phenyl­phosphane)-κ²P,P′](μ-pyri­dine-3-carbo­nitrile-κ²N¹:N³)copper(I)] hexa­fluoro­phosphate di­chloro­methane tri­solvate], {[Cu(C₆H₄N₂)(C₃₉H₃₂OP₂)]PF₆·3CH₂Cl₂}_n, conventionally abbreviated as {[Cu(3-PyCN)(Xantphos)]PF₆·3CH₂Cl₂}_n, where Xantphos and 3-PyCN re­present (9,9-dimethyl-9H-xanthene-4,5-di­yl)bis­(di­phenyl­phosphane) and pyridine-3-carbo­nitrile, respectively, has been described. In this polymer solvate, the asymmetric unit consists of three di­chloro­methane solvent mol­ecules, a hexa­fluoro­phosphate anion and a polymeric heteroleptic cuprous com­plex cation, in which the cuprous centre is in a CuP₂N₂ tetrahedral coordination and is coordinated by two P atoms from the Xantphos ligand and two N atoms from two 3-PyCN ligands (the pyridyl and cyano N atoms). It is through the connection of the μ₂-bridging 3-PyCN ligand that these cuprous centres are linked into a one-dimensional helical chain structure. The chains are further assembled through C—H...π inter­actions to form a supra­molecular metal–organic framework containing solvent-accessible channels. The UV–Vis absorption and photoluminescence properties of this heteroleptic cuprous polymer have been studied on as-synthesized samples. Its luminescence emission should mainly originate from the metal-to-ligand charge transfer 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: SHELXL2018 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

catena-Poly[[[(9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane)-κ²P,P'](pyridine-3-carbonitrile-κN³)copper(I)] hexafluorophosphate dichloromethane trisolvate]

Crystal data

[Cu(C6H4N2)(C39H32OP2)]PF6·3CH2Cl2	F(000) = 2328
Mr = 1145.98	Dx = 1.512 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.0438 (7) Å	Cell parameters from 4906 reflections
b = 13.4200 (5) Å	θ = 2.9–29.5°
c = 25.3937 (9) Å	µ = 0.91 mm^−1
β = 100.933 (4)°	T = 174 K
V = 5033.6 (3) Å^3	Needle, colourless
Z = 4	0.49 × 0.36 × 0.3 mm

Data collection

Agilent Xcalibur Gemini ultra diffractometer with an Atlas detector	10993 independent reflections
Radiation source: Enhance (Mo) X-ray Source	7551 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
Detector resolution: 10.3592 pixels mm^-1	θmax = 27.0°, θmin = 2.9°
ω scans	h = −14→19
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −17→16
Tmin = 0.786, Tmax = 1.000	l = −32→28
22749 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)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.146	w = 1/[σ^2(Fo^2) + (0.0634P)^2 + 0.8921P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
10993 reflections	Δρmax = 0.61 e Å^−3
616 parameters	Δρmin = −0.76 e Å^−3
2 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	Occ. (<1)
Cu1	0.16585 (2)	0.25474 (2)	0.28100 (2)	0.02295 (11)
P1	0.24972 (5)	0.36313 (5)	0.33962 (3)	0.02223 (18)
P2	0.20860 (5)	0.23639 (5)	0.20026 (3)	0.02247 (18)
O1	0.23653 (14)	0.43915 (14)	0.23142 (8)	0.0227 (4)
N1	0.12634 (17)	0.12360 (18)	0.31193 (10)	0.0256 (5)
N2	−0.04654 (18)	−0.16452 (19)	0.24208 (11)	0.0298 (6)
C1	0.0747 (2)	0.0567 (2)	0.28148 (12)	0.0259 (7)
H1	0.054130	0.070910	0.245384	0.031*
C2	0.0504 (2)	−0.0333 (2)	0.30158 (12)	0.0252 (6)
C3	0.0783 (2)	−0.0551 (2)	0.35522 (13)	0.0335 (8)
H3	0.061736	−0.114439	0.369663	0.040*
C4	0.1315 (3)	0.0139 (3)	0.38666 (14)	0.0396 (8)
H4	0.152142	0.001710	0.422964	0.048*
C5	0.1536 (2)	0.1006 (2)	0.36407 (12)	0.0292 (7)
H5	0.189672	0.146260	0.385975	0.035*
C6	−0.0042 (2)	−0.1044 (2)	0.26696 (13)	0.0278 (7)
C7	0.2280 (2)	0.3635 (2)	0.40782 (12)	0.0255 (6)
C8	0.1431 (2)	0.3363 (2)	0.41521 (13)	0.0306 (7)
H8	0.099883	0.316077	0.385949	0.037*
C9	0.1211 (3)	0.3387 (3)	0.46602 (14)	0.0393 (8)
H9	0.063483	0.320494	0.470698	0.047*
C10	0.1852 (3)	0.3683 (3)	0.50930 (14)	0.0433 (9)
H10	0.170773	0.370819	0.543295	0.052*
C11	0.2701 (3)	0.3939 (3)	0.50233 (13)	0.0461 (10)
H11	0.313220	0.412879	0.531881	0.055*
C12	0.2929 (2)	0.3920 (2)	0.45220 (13)	0.0356 (8)
H12	0.350959	0.409516	0.448006	0.043*
C13	0.3726 (2)	0.3568 (2)	0.34805 (12)	0.0259 (7)
C14	0.4219 (2)	0.4255 (2)	0.32479 (15)	0.0368 (8)
H14	0.392505	0.478233	0.305020	0.044*
C15	0.5150 (3)	0.4156 (3)	0.33095 (18)	0.0522 (10)
H15	0.547777	0.461783	0.315100	0.063*
C16	0.5590 (3)	0.3387 (3)	0.36014 (17)	0.0503 (10)
H16	0.621593	0.333331	0.364719	0.060*
C17	0.5108 (3)	0.2695 (3)	0.38260 (16)	0.0470 (10)
H17	0.540606	0.216483	0.401930	0.056*
C18	0.4177 (3)	0.2781 (3)	0.37669 (14)	0.0379 (8)
H18	0.385225	0.230732	0.392023	0.046*
C19	0.2213 (2)	0.4909 (2)	0.31782 (12)	0.0234 (6)
C20	0.2015 (2)	0.5657 (2)	0.35142 (13)	0.0296 (7)
H20	0.208363	0.553830	0.388047	0.036*
C21	0.1718 (2)	0.6578 (2)	0.33101 (13)	0.0355 (8)
H21	0.158171	0.707144	0.353921	0.043*
C22	0.1623 (2)	0.6770 (2)	0.27691 (13)	0.0323 (8)
H22	0.141102	0.738985	0.263750	0.039*
C23	0.1839 (2)	0.6055 (2)	0.24150 (11)	0.0241 (6)
C24	0.2125 (2)	0.5139 (2)	0.26349 (11)	0.0214 (6)
C25	0.1886 (2)	0.4370 (2)	0.17910 (11)	0.0224 (6)
C26	0.1742 (2)	0.3424 (2)	0.15639 (11)	0.0230 (6)
C27	0.1288 (2)	0.3382 (2)	0.10334 (12)	0.0314 (7)
H27	0.117715	0.276777	0.086416	0.038*
C28	0.1001 (2)	0.4243 (2)	0.07560 (13)	0.0353 (8)
H28	0.070858	0.420023	0.039949	0.042*
C29	0.1138 (2)	0.5166 (2)	0.09965 (12)	0.0307 (7)
H29	0.092873	0.573483	0.080295	0.037*
C30	0.1589 (2)	0.5252 (2)	0.15293 (12)	0.0246 (6)
C31	0.1817 (2)	0.6231 (2)	0.18225 (12)	0.0269 (7)
C32	0.2777 (2)	0.6545 (3)	0.17542 (14)	0.0401 (9)
H32A	0.320009	0.602621	0.188686	0.060*
H32B	0.294793	0.714701	0.195216	0.060*
H32C	0.278075	0.665782	0.138126	0.060*
C33	0.1147 (3)	0.7053 (2)	0.15961 (13)	0.0399 (9)
H33A	0.133383	0.767132	0.177351	0.060*
H33B	0.055405	0.688112	0.165434	0.060*
H33C	0.113367	0.712330	0.121840	0.060*
C34	0.1640 (2)	0.1285 (2)	0.15984 (11)	0.0248 (6)
C35	0.0703 (2)	0.1207 (2)	0.14226 (12)	0.0304 (7)
H35	0.032643	0.171614	0.149842	0.037*
C36	0.0332 (2)	0.0384 (2)	0.11381 (14)	0.0363 (8)
H36	−0.029128	0.033944	0.102196	0.044*
C37	0.0884 (3)	−0.0371 (2)	0.10265 (15)	0.0411 (9)
H37	0.063434	−0.092342	0.083159	0.049*
C38	0.1805 (3)	−0.0311 (2)	0.12026 (15)	0.0414 (9)
H38	0.217603	−0.082739	0.113043	0.050*
C39	0.2182 (2)	0.0515 (2)	0.14867 (13)	0.0331 (7)
H39	0.280608	0.055129	0.160313	0.040*
C40	0.3290 (2)	0.2264 (2)	0.20243 (12)	0.0274 (7)
C41	0.3693 (3)	0.2567 (3)	0.16043 (15)	0.0410 (9)
H41	0.334636	0.287393	0.130620	0.049*
C42	0.4610 (3)	0.2414 (3)	0.16263 (18)	0.0555 (11)
H42	0.487688	0.261542	0.134212	0.067*
C43	0.5127 (3)	0.1965 (3)	0.20683 (17)	0.0506 (10)
H43	0.574257	0.186527	0.208253	0.061*
C44	0.4736 (3)	0.1667 (3)	0.24865 (15)	0.0444 (9)
H44	0.508551	0.136187	0.278425	0.053*
C45	0.3828 (2)	0.1816 (2)	0.24669 (13)	0.0330 (7)
H45	0.356890	0.161505	0.275408	0.040*
P3	0.16281 (7)	0.76254 (6)	0.48517 (3)	0.0334 (2)
F1	0.24368 (18)	0.7780 (2)	0.53419 (9)	0.0680 (7)
F2	0.22599 (16)	0.79945 (18)	0.44468 (9)	0.0585 (6)
F3	0.13302 (17)	0.87603 (15)	0.48996 (9)	0.0568 (6)
F4	0.08193 (16)	0.74881 (16)	0.43523 (8)	0.0512 (6)
F5	0.09861 (18)	0.73188 (18)	0.52491 (9)	0.0644 (7)
F6	0.19283 (19)	0.65160 (16)	0.47919 (10)	0.0681 (7)
Cl3	0.29178 (9)	0.12774 (8)	0.50002 (5)	0.0696 (3)
Cl4	0.4125 (10)	0.0036 (5)	0.5741 (7)	0.086 (3)	0.64 (4)
C47	0.3199 (4)	0.0072 (3)	0.5236 (2)	0.0841 (17)
H47A	0.268721	−0.021502	0.536317	0.101*	0.64 (4)
H47B	0.331537	−0.033588	0.494057	0.101*	0.64 (4)
H47C	0.264818	−0.030539	0.523238	0.101*	0.36 (4)
H47D	0.353797	−0.025706	0.499636	0.101*	0.36 (4)
Cl1	0.46396 (11)	0.78439 (10)	0.47403 (6)	0.0849 (4)
Cl2	0.46180 (12)	0.58156 (11)	0.43504 (6)	0.0979 (5)
C46	0.4231 (4)	0.6642 (4)	0.4786 (2)	0.0731 (14)
H46A	0.357473	0.665541	0.470470	0.088*
H46B	0.441715	0.640420	0.515070	0.088*
Cl5	0.27845 (10)	−0.08039 (10)	0.26988 (6)	0.0840 (4)
Cl6	0.36805 (10)	0.00116 (11)	0.37195 (7)	0.0959 (5)
C48	0.3274 (4)	−0.1060 (4)	0.3385 (3)	0.102 (2)
H48A	0.282021	−0.135787	0.356142	0.122*
H48B	0.376469	−0.153414	0.339998	0.122*
Cl4A	0.3818 (19)	0.0071 (10)	0.5860 (4)	0.078 (3)	0.36 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0277 (2)	0.01939 (19)	0.02133 (19)	−0.00195 (14)	0.00374 (16)	0.00040 (14)
P1	0.0274 (4)	0.0199 (4)	0.0190 (4)	−0.0018 (3)	0.0033 (3)	0.0001 (3)
P2	0.0272 (4)	0.0198 (4)	0.0199 (4)	0.0001 (3)	0.0035 (3)	−0.0012 (3)
O1	0.0285 (11)	0.0202 (10)	0.0187 (10)	0.0015 (9)	0.0026 (9)	−0.0011 (8)
N1	0.0279 (14)	0.0217 (12)	0.0263 (13)	−0.0017 (11)	0.0028 (11)	0.0018 (11)
N2	0.0288 (15)	0.0265 (14)	0.0338 (15)	−0.0011 (12)	0.0054 (12)	−0.0013 (12)
C1	0.0305 (17)	0.0234 (15)	0.0229 (15)	−0.0008 (13)	0.0030 (13)	0.0016 (12)
C2	0.0223 (16)	0.0233 (15)	0.0298 (16)	−0.0001 (12)	0.0044 (13)	0.0004 (13)
C3	0.0369 (19)	0.0236 (15)	0.0376 (18)	−0.0051 (14)	0.0009 (16)	0.0073 (14)
C4	0.051 (2)	0.0366 (19)	0.0269 (17)	−0.0062 (17)	−0.0027 (16)	0.0057 (15)
C5	0.0361 (19)	0.0245 (15)	0.0243 (15)	−0.0052 (14)	−0.0014 (14)	0.0004 (13)
C6	0.0269 (17)	0.0232 (15)	0.0335 (17)	0.0005 (13)	0.0064 (14)	0.0055 (14)
C7	0.0321 (17)	0.0215 (14)	0.0222 (14)	0.0015 (13)	0.0037 (13)	0.0024 (12)
C8	0.0298 (18)	0.0357 (17)	0.0266 (16)	0.0013 (14)	0.0059 (14)	0.0048 (14)
C9	0.042 (2)	0.044 (2)	0.0365 (19)	0.0075 (16)	0.0181 (17)	0.0105 (16)
C10	0.065 (3)	0.043 (2)	0.0271 (18)	0.0076 (19)	0.0194 (19)	0.0082 (16)
C11	0.065 (3)	0.049 (2)	0.0221 (17)	−0.010 (2)	0.0043 (18)	−0.0044 (16)
C12	0.040 (2)	0.0380 (19)	0.0287 (17)	−0.0073 (16)	0.0060 (15)	−0.0030 (15)
C13	0.0298 (17)	0.0262 (15)	0.0216 (14)	−0.0016 (13)	0.0045 (13)	−0.0055 (12)
C14	0.0283 (18)	0.0333 (18)	0.049 (2)	−0.0028 (14)	0.0070 (16)	0.0024 (16)
C15	0.036 (2)	0.049 (2)	0.075 (3)	−0.0083 (18)	0.019 (2)	−0.001 (2)
C16	0.029 (2)	0.052 (2)	0.068 (3)	0.0081 (18)	0.005 (2)	−0.014 (2)
C17	0.046 (2)	0.043 (2)	0.049 (2)	0.0177 (18)	−0.0002 (19)	−0.0052 (18)
C18	0.042 (2)	0.0341 (18)	0.0358 (19)	0.0052 (16)	0.0031 (17)	0.0021 (15)
C19	0.0232 (15)	0.0196 (14)	0.0269 (15)	−0.0012 (12)	0.0039 (13)	−0.0024 (12)
C20	0.0396 (19)	0.0248 (15)	0.0266 (16)	0.0005 (14)	0.0117 (15)	−0.0012 (13)
C21	0.050 (2)	0.0281 (17)	0.0314 (17)	0.0033 (15)	0.0157 (17)	−0.0081 (14)
C22	0.044 (2)	0.0179 (14)	0.0367 (18)	0.0070 (14)	0.0117 (16)	0.0019 (13)
C23	0.0273 (16)	0.0208 (14)	0.0240 (15)	−0.0027 (12)	0.0048 (13)	−0.0004 (12)
C24	0.0230 (15)	0.0199 (14)	0.0219 (14)	−0.0011 (12)	0.0055 (12)	−0.0038 (12)
C25	0.0229 (16)	0.0258 (15)	0.0181 (14)	0.0016 (12)	0.0029 (12)	0.0002 (12)
C26	0.0276 (17)	0.0204 (14)	0.0206 (14)	0.0014 (12)	0.0036 (13)	0.0020 (12)
C27	0.044 (2)	0.0241 (15)	0.0260 (16)	−0.0013 (14)	0.0054 (15)	−0.0011 (13)
C28	0.048 (2)	0.0360 (18)	0.0194 (15)	0.0003 (16)	0.0009 (15)	0.0005 (14)
C29	0.0353 (19)	0.0286 (16)	0.0273 (16)	0.0017 (14)	0.0038 (14)	0.0086 (14)
C30	0.0260 (16)	0.0225 (14)	0.0257 (15)	0.0009 (13)	0.0063 (13)	0.0033 (12)
C31	0.0321 (18)	0.0202 (14)	0.0289 (16)	0.0001 (13)	0.0072 (14)	0.0037 (13)
C32	0.050 (2)	0.0383 (19)	0.0355 (19)	−0.0153 (17)	0.0164 (18)	−0.0034 (15)
C33	0.062 (3)	0.0244 (16)	0.0328 (18)	0.0092 (16)	0.0080 (18)	0.0070 (14)
C34	0.0331 (18)	0.0198 (14)	0.0219 (14)	−0.0010 (13)	0.0068 (13)	0.0004 (12)
C35	0.0354 (19)	0.0259 (16)	0.0313 (17)	0.0029 (14)	0.0097 (15)	−0.0042 (14)
C36	0.0339 (19)	0.0335 (18)	0.0402 (19)	−0.0038 (15)	0.0033 (16)	−0.0045 (15)
C37	0.047 (2)	0.0300 (18)	0.042 (2)	−0.0086 (16)	−0.0007 (18)	−0.0105 (16)
C38	0.048 (2)	0.0246 (16)	0.050 (2)	0.0073 (16)	0.0048 (19)	−0.0108 (16)
C39	0.0340 (19)	0.0273 (16)	0.0364 (18)	0.0010 (14)	0.0027 (15)	−0.0059 (14)
C40	0.0305 (18)	0.0243 (15)	0.0268 (16)	−0.0038 (13)	0.0041 (14)	−0.0064 (13)
C41	0.038 (2)	0.050 (2)	0.037 (2)	0.0006 (17)	0.0135 (17)	0.0067 (16)
C42	0.045 (2)	0.071 (3)	0.056 (3)	−0.005 (2)	0.022 (2)	0.008 (2)
C43	0.031 (2)	0.057 (2)	0.063 (3)	0.0005 (18)	0.010 (2)	−0.008 (2)
C44	0.037 (2)	0.048 (2)	0.044 (2)	0.0057 (17)	−0.0023 (18)	−0.0043 (17)
C45	0.0350 (19)	0.0317 (17)	0.0319 (17)	−0.0003 (15)	0.0054 (15)	−0.0029 (14)
P3	0.0434 (5)	0.0325 (5)	0.0244 (4)	−0.0028 (4)	0.0066 (4)	0.0004 (3)
F1	0.0708 (18)	0.0825 (17)	0.0407 (13)	−0.0071 (14)	−0.0148 (12)	−0.0022 (12)
F2	0.0573 (15)	0.0736 (16)	0.0501 (13)	−0.0132 (12)	0.0241 (12)	−0.0031 (12)
F3	0.0883 (18)	0.0350 (11)	0.0497 (13)	0.0031 (11)	0.0196 (13)	−0.0022 (10)
F4	0.0523 (14)	0.0579 (14)	0.0382 (12)	−0.0086 (10)	−0.0047 (11)	−0.0052 (10)
F5	0.0871 (19)	0.0658 (15)	0.0483 (14)	−0.0199 (13)	0.0331 (14)	0.0093 (11)
F6	0.094 (2)	0.0380 (12)	0.0685 (16)	0.0148 (12)	0.0060 (15)	−0.0012 (11)
Cl3	0.0781 (8)	0.0545 (6)	0.0661 (7)	0.0026 (6)	−0.0120 (6)	0.0044 (5)
Cl4	0.075 (4)	0.0541 (16)	0.108 (5)	−0.0025 (19)	−0.034 (3)	0.008 (2)
C47	0.096 (4)	0.050 (3)	0.092 (4)	0.003 (3)	−0.019 (3)	−0.009 (3)
Cl1	0.1132 (12)	0.0678 (8)	0.0818 (9)	−0.0204 (8)	0.0392 (9)	−0.0136 (7)
Cl2	0.1323 (14)	0.0730 (9)	0.1017 (11)	−0.0392 (9)	0.0556 (10)	−0.0242 (8)
C46	0.073 (3)	0.076 (3)	0.074 (3)	−0.015 (3)	0.025 (3)	0.001 (3)
Cl5	0.0869 (10)	0.0683 (8)	0.0981 (10)	−0.0066 (7)	0.0208 (8)	−0.0053 (7)
Cl6	0.0721 (9)	0.0880 (10)	0.1178 (13)	−0.0015 (7)	−0.0072 (9)	−0.0023 (9)
C48	0.114 (5)	0.056 (3)	0.134 (6)	0.026 (3)	0.018 (4)	−0.003 (3)
Cl4A	0.090 (7)	0.068 (3)	0.069 (4)	0.006 (4)	−0.005 (4)	0.016 (2)

Geometric parameters (Å, º)

Cu1—P1	2.2827 (8)	C27—H27	0.9300
Cu1—P2	2.2757 (8)	C27—C28	1.379 (4)
Cu1—N1	2.060 (2)	C28—H28	0.9300
Cu1—N2^i	2.083 (3)	C28—C29	1.379 (4)
P1—C7	1.822 (3)	C29—H29	0.9300
P1—C13	1.823 (3)	C29—C30	1.399 (4)
P1—C19	1.828 (3)	C30—C31	1.516 (4)
P2—C26	1.820 (3)	C31—C32	1.546 (4)
P2—C34	1.827 (3)	C31—C33	1.531 (4)
P2—C40	1.807 (3)	C32—H32A	0.9600
O1—C24	1.383 (3)	C32—H32B	0.9600
O1—C25	1.386 (3)	C32—H32C	0.9600
N1—C1	1.335 (4)	C33—H33A	0.9600
N1—C5	1.346 (4)	C33—H33B	0.9600
N2—C6	1.141 (4)	C33—H33C	0.9600
C1—H1	0.9300	C34—C35	1.399 (4)
C1—C2	1.386 (4)	C34—C39	1.379 (4)
C2—C3	1.379 (4)	C35—H35	0.9300
C2—C6	1.444 (4)	C35—C36	1.379 (4)
C3—H3	0.9300	C36—H36	0.9300
C3—C4	1.376 (5)	C36—C37	1.372 (5)
C4—H4	0.9300	C37—H37	0.9300
C4—C5	1.365 (4)	C37—C38	1.376 (5)
C5—H5	0.9300	C38—H38	0.9300
C7—C8	1.376 (4)	C38—C39	1.384 (5)
C7—C12	1.397 (4)	C39—H39	0.9300
C8—H8	0.9300	C40—C41	1.383 (4)
C8—C9	1.392 (4)	C40—C45	1.391 (5)
C9—H9	0.9300	C41—H41	0.9300
C9—C10	1.376 (5)	C41—C42	1.385 (5)
C10—H10	0.9300	C42—H42	0.9300
C10—C11	1.365 (5)	C42—C43	1.377 (6)
C11—H11	0.9300	C43—H43	0.9300
C11—C12	1.380 (5)	C43—C44	1.368 (5)
C12—H12	0.9300	C44—H44	0.9300
C13—C14	1.383 (4)	C44—C45	1.371 (5)
C13—C18	1.384 (5)	C45—H45	0.9300
C14—H14	0.9300	P3—F1	1.581 (2)
C14—C15	1.385 (5)	P3—F2	1.605 (2)
C15—H15	0.9300	P3—F3	1.599 (2)
C15—C16	1.367 (6)	P3—F4	1.593 (2)
C16—H16	0.9300	P3—F5	1.578 (2)
C16—C17	1.367 (6)	P3—F6	1.572 (2)
C17—H17	0.9300	Cl3—C47	1.749 (5)
C17—C18	1.385 (5)	Cl4—C47	1.705 (8)
C18—H18	0.9300	C47—H47A	0.9700
C19—C20	1.386 (4)	C47—H47B	0.9700
C19—C24	1.395 (4)	C47—H47C	0.9700
C20—H20	0.9300	C47—H47D	0.9700
C20—C21	1.381 (4)	C47—Cl4A	1.679 (12)
C21—H21	0.9300	Cl1—C46	1.738 (5)
C21—C22	1.378 (4)	Cl2—C46	1.742 (5)
C22—H22	0.9300	C46—H46A	0.9700
C22—C23	1.394 (4)	C46—H46B	0.9700
C23—C24	1.385 (4)	Cl5—C48	1.793 (7)
C23—C31	1.517 (4)	Cl6—C48	1.722 (6)
C25—C26	1.394 (4)	C48—H48A	0.9700
C25—C30	1.390 (4)	C48—H48B	0.9700
C26—C27	1.391 (4)
P2—Cu1—P1	116.15 (3)	C27—C28—H28	119.3
N1—Cu1—P1	117.36 (7)	C29—C28—C27	121.3 (3)
N1—Cu1—P2	113.72 (7)	C29—C28—H28	119.3
N1—Cu1—N2^i	104.84 (10)	C28—C29—H29	119.8
N2^i—Cu1—P1	101.08 (7)	C28—C29—C30	120.5 (3)
N2^i—Cu1—P2	100.27 (8)	C30—C29—H29	119.8
C7—P1—Cu1	116.43 (10)	C25—C30—C29	116.4 (3)
C7—P1—C13	104.43 (14)	C25—C30—C31	118.7 (3)
C7—P1—C19	102.20 (13)	C29—C30—C31	124.8 (3)
C13—P1—Cu1	118.01 (10)	C23—C31—C32	108.0 (3)
C13—P1—C19	104.70 (14)	C23—C31—C33	111.9 (3)
C19—P1—Cu1	109.36 (10)	C30—C31—C23	108.2 (2)
C26—P2—Cu1	111.77 (10)	C30—C31—C32	108.1 (2)
C26—P2—C34	104.11 (14)	C30—C31—C33	111.6 (3)
C34—P2—Cu1	117.08 (10)	C33—C31—C32	108.9 (3)
C40—P2—Cu1	115.69 (10)	C31—C32—H32A	109.5
C40—P2—C26	104.10 (14)	C31—C32—H32B	109.5
C40—P2—C34	102.57 (14)	C31—C32—H32C	109.5
C24—O1—C25	115.7 (2)	H32A—C32—H32B	109.5
C1—N1—Cu1	122.2 (2)	H32A—C32—H32C	109.5
C1—N1—C5	116.8 (3)	H32B—C32—H32C	109.5
C5—N1—Cu1	121.0 (2)	C31—C33—H33A	109.5
C6—N2—Cu1^ii	152.1 (3)	C31—C33—H33B	109.5
N1—C1—H1	118.7	C31—C33—H33C	109.5
N1—C1—C2	122.5 (3)	H33A—C33—H33B	109.5
C2—C1—H1	118.7	H33A—C33—H33C	109.5
C1—C2—C6	120.7 (3)	H33B—C33—H33C	109.5
C3—C2—C1	119.8 (3)	C35—C34—P2	118.6 (2)
C3—C2—C6	119.5 (3)	C39—C34—P2	122.7 (2)
C2—C3—H3	121.2	C39—C34—C35	118.6 (3)
C4—C3—C2	117.7 (3)	C34—C35—H35	119.7
C4—C3—H3	121.2	C36—C35—C34	120.6 (3)
C3—C4—H4	120.3	C36—C35—H35	119.7
C5—C4—C3	119.4 (3)	C35—C36—H36	120.0
C5—C4—H4	120.3	C37—C36—C35	120.0 (3)
N1—C5—C4	123.8 (3)	C37—C36—H36	120.0
N1—C5—H5	118.1	C36—C37—H37	120.0
C4—C5—H5	118.1	C36—C37—C38	120.1 (3)
N2—C6—C2	175.9 (3)	C38—C37—H37	120.0
C8—C7—P1	117.9 (2)	C37—C38—H38	119.8
C8—C7—C12	119.2 (3)	C37—C38—C39	120.3 (3)
C12—C7—P1	123.0 (2)	C39—C38—H38	119.8
C7—C8—H8	119.7	C34—C39—C38	120.4 (3)
C7—C8—C9	120.7 (3)	C34—C39—H39	119.8
C9—C8—H8	119.7	C38—C39—H39	119.8
C8—C9—H9	120.2	C41—C40—P2	122.5 (3)
C10—C9—C8	119.6 (3)	C41—C40—C45	118.5 (3)
C10—C9—H9	120.2	C45—C40—P2	118.9 (2)
C9—C10—H10	120.0	C40—C41—H41	119.9
C11—C10—C9	120.0 (3)	C40—C41—C42	120.2 (4)
C11—C10—H10	120.0	C42—C41—H41	119.9
C10—C11—H11	119.4	C41—C42—H42	119.9
C10—C11—C12	121.2 (4)	C43—C42—C41	120.1 (4)
C12—C11—H11	119.4	C43—C42—H42	119.9
C7—C12—H12	120.3	C42—C43—H43	120.0
C11—C12—C7	119.4 (3)	C44—C43—C42	120.1 (4)
C11—C12—H12	120.3	C44—C43—H43	120.0
C14—C13—P1	122.1 (2)	C43—C44—H44	120.0
C14—C13—C18	119.0 (3)	C43—C44—C45	120.0 (4)
C18—C13—P1	118.8 (3)	C45—C44—H44	120.0
C13—C14—H14	120.0	C40—C45—H45	119.5
C13—C14—C15	120.0 (3)	C44—C45—C40	121.0 (3)
C15—C14—H14	120.0	C44—C45—H45	119.5
C14—C15—H15	119.7	F1—P3—F2	90.18 (14)
C16—C15—C14	120.5 (4)	F1—P3—F3	90.01 (14)
C16—C15—H15	119.7	F1—P3—F4	178.91 (14)
C15—C16—H16	120.0	F3—P3—F2	87.90 (13)
C15—C16—C17	119.9 (4)	F4—P3—F2	88.94 (13)
C17—C16—H16	120.0	F4—P3—F3	89.31 (12)
C16—C17—H17	119.9	F5—P3—F1	90.20 (14)
C16—C17—C18	120.3 (4)	F5—P3—F2	177.03 (15)
C18—C17—H17	119.9	F5—P3—F3	89.16 (13)
C13—C18—C17	120.3 (3)	F5—P3—F4	90.64 (14)
C13—C18—H18	119.9	F6—P3—F1	90.45 (14)
C17—C18—H18	119.9	F6—P3—F2	90.84 (14)
C20—C19—P1	124.0 (2)	F6—P3—F3	178.65 (14)
C20—C19—C24	117.2 (3)	F6—P3—F4	90.21 (13)
C24—C19—P1	118.7 (2)	F6—P3—F5	92.10 (14)
C19—C20—H20	119.7	Cl3—C47—H47A	108.9
C21—C20—C19	120.6 (3)	Cl3—C47—H47B	108.9
C21—C20—H20	119.7	Cl3—C47—H47C	109.2
C20—C21—H21	119.8	Cl3—C47—H47D	109.2
C22—C21—C20	120.4 (3)	Cl4—C47—Cl3	113.2 (3)
C22—C21—H21	119.8	Cl4—C47—H47A	108.9
C21—C22—H22	119.3	Cl4—C47—H47B	108.9
C21—C22—C23	121.4 (3)	H47A—C47—H47B	107.8
C23—C22—H22	119.3	H47C—C47—H47D	107.9
C22—C23—C31	124.7 (3)	Cl4A—C47—Cl3	112.2 (5)
C24—C23—C22	116.3 (3)	Cl4A—C47—H47C	109.2
C24—C23—C31	119.0 (3)	Cl4A—C47—H47D	109.2
O1—C24—C19	115.8 (2)	Cl1—C46—Cl2	112.6 (3)
O1—C24—C23	120.2 (2)	Cl1—C46—H46A	109.1
C23—C24—C19	124.0 (3)	Cl1—C46—H46B	109.1
O1—C25—C26	115.3 (2)	Cl2—C46—H46A	109.1
O1—C25—C30	120.1 (3)	Cl2—C46—H46B	109.1
C30—C25—C26	124.6 (3)	H46A—C46—H46B	107.8
C25—C26—P2	117.0 (2)	Cl5—C48—H48A	109.4
C27—C26—P2	126.3 (2)	Cl5—C48—H48B	109.4
C27—C26—C25	116.5 (3)	Cl6—C48—Cl5	111.2 (3)
C26—C27—H27	119.7	Cl6—C48—H48A	109.4
C28—C27—C26	120.6 (3)	Cl6—C48—H48B	109.4
C28—C27—H27	119.7	H48A—C48—H48B	108.0
Cu1—P1—C7—C8	−27.7 (3)	C19—P1—C13—C18	164.3 (3)
Cu1—P1—C7—C12	153.7 (2)	C19—C20—C21—C22	−0.7 (5)
Cu1—P1—C13—C14	103.2 (3)	C20—C19—C24—O1	177.2 (3)
Cu1—P1—C13—C18	−73.9 (3)	C20—C19—C24—C23	−1.3 (5)
Cu1—P1—C19—C20	131.8 (3)	C20—C21—C22—C23	−1.3 (5)
Cu1—P1—C19—C24	−43.6 (3)	C21—C22—C23—C24	1.9 (5)
Cu1—P2—C26—C25	44.3 (3)	C21—C22—C23—C31	−175.4 (3)
Cu1—P2—C26—C27	−130.5 (3)	C22—C23—C24—O1	−179.0 (3)
Cu1—P2—C34—C35	62.4 (3)	C22—C23—C24—C19	−0.6 (5)
Cu1—P2—C34—C39	−113.6 (2)	C22—C23—C31—C30	−149.9 (3)
Cu1—P2—C40—C41	−151.8 (2)	C22—C23—C31—C32	93.3 (4)
Cu1—P2—C40—C45	31.8 (3)	C22—C23—C31—C33	−26.5 (4)
Cu1—N1—C1—C2	177.7 (2)	C24—O1—C25—C26	−146.8 (3)
Cu1—N1—C5—C4	−178.5 (3)	C24—O1—C25—C30	33.4 (4)
P1—C7—C8—C9	−177.5 (2)	C24—C19—C20—C21	1.9 (5)
P1—C7—C12—C11	177.6 (3)	C24—C23—C31—C30	32.9 (4)
P1—C13—C14—C15	−177.9 (3)	C24—C23—C31—C32	−84.0 (3)
P1—C13—C18—C17	178.2 (3)	C24—C23—C31—C33	156.2 (3)
P1—C19—C20—C21	−173.5 (3)	C25—O1—C24—C19	148.1 (3)
P1—C19—C24—O1	−7.1 (4)	C25—O1—C24—C23	−33.3 (4)
P1—C19—C24—C23	174.4 (2)	C25—C26—C27—C28	−0.1 (5)
P2—C26—C27—C28	174.8 (3)	C25—C30—C31—C23	−32.7 (4)
P2—C34—C35—C36	−176.9 (3)	C25—C30—C31—C32	84.0 (3)
P2—C34—C39—C38	176.5 (3)	C25—C30—C31—C33	−156.2 (3)
P2—C40—C41—C42	−175.8 (3)	C26—P2—C34—C35	−61.5 (3)
P2—C40—C45—C44	175.9 (3)	C26—P2—C34—C39	122.5 (3)
O1—C25—C26—P2	6.6 (3)	C26—P2—C40—C41	−28.7 (3)
O1—C25—C26—C27	−178.0 (3)	C26—P2—C40—C45	154.8 (2)
O1—C25—C30—C29	177.9 (3)	C26—C25—C30—C29	−1.9 (5)
O1—C25—C30—C31	1.4 (4)	C26—C25—C30—C31	−178.4 (3)
N1—C1—C2—C3	1.5 (5)	C26—C27—C28—C29	−1.2 (5)
N1—C1—C2—C6	−178.8 (3)	C27—C28—C29—C30	1.1 (5)
C1—N1—C5—C4	0.0 (5)	C28—C29—C30—C25	0.4 (5)
C1—C2—C3—C4	−1.3 (5)	C28—C29—C30—C31	176.7 (3)
C2—C3—C4—C5	0.6 (5)	C29—C30—C31—C23	151.1 (3)
C3—C4—C5—N1	0.0 (6)	C29—C30—C31—C32	−92.1 (4)
C5—N1—C1—C2	−0.8 (4)	C29—C30—C31—C33	27.6 (4)
C6—C2—C3—C4	179.0 (3)	C30—C25—C26—P2	−173.6 (2)
C7—P1—C13—C14	−125.7 (3)	C30—C25—C26—C27	1.7 (5)
C7—P1—C13—C18	57.2 (3)	C31—C23—C24—O1	−1.6 (4)
C7—P1—C19—C20	7.8 (3)	C31—C23—C24—C19	176.9 (3)
C7—P1—C19—C24	−167.5 (2)	C34—P2—C26—C25	171.6 (2)
C7—C8—C9—C10	−0.3 (5)	C34—P2—C26—C27	−3.2 (3)
C8—C7—C12—C11	−1.1 (5)	C34—P2—C40—C41	79.6 (3)
C8—C9—C10—C11	−0.8 (5)	C34—P2—C40—C45	−96.9 (3)
C9—C10—C11—C12	0.9 (6)	C34—C35—C36—C37	0.2 (5)
C10—C11—C12—C7	0.1 (5)	C35—C34—C39—C38	0.6 (5)
C12—C7—C8—C9	1.2 (5)	C35—C36—C37—C38	0.6 (6)
C13—P1—C7—C8	−159.7 (2)	C36—C37—C38—C39	−0.9 (6)
C13—P1—C7—C12	21.6 (3)	C37—C38—C39—C34	0.3 (5)
C13—P1—C19—C20	−100.8 (3)	C39—C34—C35—C36	−0.8 (5)
C13—P1—C19—C24	83.8 (3)	C40—P2—C26—C25	−81.2 (3)
C13—C14—C15—C16	−0.3 (6)	C40—P2—C26—C27	103.9 (3)
C14—C13—C18—C17	1.1 (5)	C40—P2—C34—C35	−169.8 (2)
C14—C15—C16—C17	1.3 (6)	C40—P2—C34—C39	14.2 (3)
C15—C16—C17—C18	−1.1 (6)	C40—C41—C42—C43	−0.4 (6)
C16—C17—C18—C13	−0.1 (6)	C41—C40—C45—C44	−0.7 (5)
C18—C13—C14—C15	−0.9 (5)	C41—C42—C43—C44	0.2 (6)
C19—P1—C7—C8	91.4 (3)	C42—C43—C44—C45	−0.2 (6)
C19—P1—C7—C12	−87.2 (3)	C43—C44—C45—C40	0.5 (5)
C19—P1—C13—C14	−18.6 (3)	C45—C40—C41—C42	0.7 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···F4^iii	0.93	2.46	3.318 (4)	154
C4—H4···F3^iii	0.93	2.45	3.207 (4)	139
C33—H33C···F5^iv	0.96	2.54	3.486 (4)	168
C37—H37···F5^v	0.93	2.50	3.297 (4)	143
C47—H47C···F3^iii	0.97	2.36	3.290 (6)	160
C46—H46A···F6	0.97	2.54	3.472 (6)	162

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