The first di-[mu]-hydro­xo-bridged binuclear copper complex containing a bis-guanidine ligand

The present structure determination of di-[mu]-hydroxo-bis{[N,N'-bis­(dipiperidino­methyl­ene)­propane-1,3-di­amine-[kappa]²N,N']copper(II)} bis­(hexa­fluoro­phosphate), [Cu₂(OH)₂(C₂₅H₄₆N₆)₂](PF₆)₂, is the first to crystallographically characterize a Cu₂([mu]-OH)₂ complex with a bidentate guanidine ligand. The cation lies on a crystallographic inversion centre and shows planar fourfold coordination of the copper centres. The Cu₂([mu]-OH)₂ species can be distinguished from Cu₂([mu]-O)₂ by the Cu-O bond lengths. The packing is determined by strong intermolecular anion-cation hydrogen bonds.

S1. Comment

The activation of dioxygen by tyrosinase-like Cu^I complexes plays an important role in biological and synthetic oxidation processes. Recent efforts have been directed towards elucidating the structure–reactivity relationship of the underlying Cu₂O₂ species through synthetic model systems (Tolman, 1997; Que & Tolman, 2002). In search of bifunctional N-atom donor ligands able to stabilize unusually high metal oxidation states, we extended our interests towards guanidyl-type systems (Herres et al., 2004a). The first derivative, the bis-tetramethylguanidinopropylen ligand (btmgp), and its complexes with copper, iron and nickel were investigated with regard to their coordination chemistry (Harmjanz, 1997; Waden, 1999; Pohl et al., 2000; Schneider, 2000; Herres, 2002). We have now examined the reaction behaviour of mono- and binuclear copper(I) complexes containing the (DPipG₂p) ligand towards molecular oxygen. The reaction products have been identified as rare examples of alkoxo-bridged binuclear copper complexes, demonstrating that the bidentate ligand has been hydroxylated in an unprecedented manner (Herres et al., 2004b). Another product, the bishydroxo-bridged binuclear copper title complex, [Cu₂(DPipG₂p)₂(µ-OH)₂][PF₆]₂, will be discussed here.

The geometric centre of the cation lies on a crystallographic inversion centre, and thus the resulting Cu₂O₂ core is strictly planar. The Cu atom is coordinated in a planar quadratic manner by two guanidinyl N atoms and the two bridging O atoms. The deviation of the Cu atom from the N₂O₂ plane is 0.036 (1) Å, and the chelate heterocycle adopts a chair conformation. The presence of the hydroxo H atom was confirmed from Fourier maps. According to the existing (\-OH) bridges the Cu.·Cu and Cu—O distances of 3.0740 (6) and av. 1.935 (2) Å are clearly elongated compared with those of bis-µ-oxo-bridged Cu₂O₂ moieties, which range from 2.743 (1) to 2.906 (1) Å, and from 1.796 (6) to 1.865 (3) Å, respectively. Similar observations hold for related Fe complexes (Que & Tolman, 2002). As pointed out by Que & Tolman (2002), the significant differences between the short [in M₂(µ-O)₂] and long [in M₂(µ-OH)₂] M—O distances are obviously a suitable measure to distinguish between these two species. The N6 piperidine group is disordered over two sites with occupation factors 0.823 (6) and 0.177 (6). Fig. 1 displays only the major position. The packing is determined by intermolecular hydrogen bonds between the cation and the hexafluorophosphate anions [C14—H14A.·F16(-x + 2, −y + 2, −z + 1) with H···F = 2.275 (4) Å and C—H···F = 170.4 (2)°, C3—H3A···F12(x, y, z) with H···F = 2.384 (5) Å and C—H···F = 160.7 (3)°, and C251—H25A.·F15(x − 0.5, −y + 0.5 + 1, z − 0.5) with H···F = 2.406 (4) Å and C—H···F = 142.9 (3)°]. The shortest intramolecular interaction is C241—H125D.·N6 [H.·N = 2.124 (3) Å]. All these values are normalized for a C—H distance of 1.08 Å.

S2. Experimental

A solution of [Cu₂(DPipG₂p)]₂[PF₆]₂ (262 mg, 0.2 mmol) (Herres et al., 2004b) in MeCN (50 ml) was treated at room temperature with pure dioxygen. After the mixture had been left to stand for one week, dark-blue crystals suitable for X-ray diffraction were obtained. IR (KBr, cm⁻¹): 3446 [vw, ν(O–H)], 2937 (s), 2852 (s), 1533 [versus, ν(C═N)], 1495 [s, ν(C═N)], 1446 (versus), 1371 (s), 1335 (m), 1253 (m), 1226 (m), 1205 (m), 1164 (w), 1141 (m), 1110 (m), 1070 (w), 1020 (m), 948 (m), 917 (w), 839 [versus, ν(P–F)], 744 (m), 622 (w), 597 (w), 557 (m), 487 (w).

S3. Refinement

H atoms attached to C atoms were placed at idealized positions, riding on their attached C atoms, with U_iso(H) values of 1.2U_eq(C) and 1.5U_eq(C_methyl). All CH₃ groups were allowed to rotate but not to tip. The O—H distance of the hydroxo group was restrained to 0.84 (1) Å. The disordered piperidine group at N6 was treated with a split model. Geometric parameters derived for the isotropically refined minor positions are less reliable.

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2002); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted, and only the major position of the disordered piperidine group at atom N6 is shown. Atoms labelled with the suffix A are at the symmetry position (-x + 1, −y + 1, −z + 1).
	Fig. 2. The crystal packing, viewed along [010], with the hydrogen-bonding pattern indicated by dashed lines. H atoms not involved in hydrogen bonding have been omitted.

di-µ-hydroxo-bis{[N,N'-bis(di-1-piperidylmethylene)propane-1,3-diamine- κ²N,N']copper(II)} bis(hexafluorophosphate)

Crystal data

[Cu2(OH)2(C25H46N6)2](PF6)2	F(000) = 1380
Mr = 1312.39	Dx = 1.431 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8806 reflections
a = 12.3581 (9) Å	θ = 2.4–28.1°
b = 16.7472 (13) Å	µ = 0.84 mm^−1
c = 14.7430 (11) Å	T = 120 K
β = 93.156 (2)°	Block, blue
V = 3046.6 (4) Å^3	0.40 × 0.35 × 0.25 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	7264 independent reflections
Radiation source: sealed tube	4803 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
ϕ and ω scans	θmax = 27.9°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −14→16
Tmin = 0.715, Tmax = 0.810	k = −22→22
35133 measured reflections	l = −19→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: difference Fourier map
wR(F^2) = 0.161	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0709P)^2 + 4.1986P] where P = (Fo^2 + 2Fc^2)/3
7264 reflections	(Δ/σ)max = 0.005
382 parameters	Δρmax = 0.97 e Å^−3
44 restraints	Δρmin = −0.85 e Å^−3

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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.53416 (3)	0.54633 (2)	0.41625 (2)	0.03176 (14)
P1	0.83493 (16)	0.38477 (9)	0.70159 (11)	0.0877 (6)
O1	0.4677 (2)	0.44706 (15)	0.45377 (15)	0.0361 (6)
N1	0.7136 (2)	0.67510 (17)	0.51160 (17)	0.0319 (6)
N2	0.6176 (2)	0.78515 (17)	0.45698 (18)	0.0333 (6)
N3	0.5816 (2)	0.65741 (17)	0.39426 (17)	0.0313 (6)
N4	0.5330 (2)	0.51195 (17)	0.28853 (17)	0.0335 (6)
N5	0.4762 (2)	0.40347 (16)	0.19772 (17)	0.0304 (6)
N6	0.6168 (3)	0.38962 (18)	0.3085 (2)	0.0412 (7)
F16	0.7644 (3)	0.3787 (3)	0.7871 (2)	0.1211 (16)
F15	0.9257 (3)	0.3359 (3)	0.7555 (4)	0.1394 (18)
F14	0.7404 (4)	0.4324 (3)	0.6507 (2)	0.140 (2)
F13	0.7797 (5)	0.3030 (3)	0.6684 (4)	0.1536 (19)
F12	0.8819 (6)	0.4640 (3)	0.7403 (4)	0.190 (3)
F11	0.8954 (4)	0.3845 (4)	0.6141 (4)	0.184 (3)
C1	0.7765 (3)	0.6045 (2)	0.4905 (2)	0.0403 (8)
H1A	0.7713	0.5948	0.4242	0.048*
H1B	0.7470	0.5572	0.5210	0.048*
C2	0.8946 (3)	0.6169 (3)	0.5226 (3)	0.0509 (10)
H2A	0.9359	0.5673	0.5126	0.061*
H2B	0.9262	0.6600	0.4865	0.061*
C3	0.9043 (4)	0.6387 (3)	0.6227 (3)	0.0587 (12)
H3A	0.8809	0.5928	0.6591	0.070*
H3B	0.9812	0.6501	0.6407	0.070*
C4	0.8366 (3)	0.7103 (3)	0.6427 (3)	0.0468 (10)
H4A	0.8665	0.7581	0.6136	0.056*
H4B	0.8389	0.7197	0.7091	0.056*
C5	0.7208 (3)	0.6978 (2)	0.6078 (2)	0.0391 (8)
H5A	0.6876	0.6554	0.6439	0.047*
H5B	0.6793	0.7476	0.6158	0.047*
C6	0.7055 (3)	0.8417 (2)	0.4797 (2)	0.0384 (8)
H6A	0.7761	0.8140	0.4784	0.046*
H6B	0.6980	0.8627	0.5419	0.046*
C7	0.7017 (3)	0.9107 (2)	0.4119 (3)	0.0436 (9)
H7A	0.7592	0.9498	0.4295	0.052*
H7B	0.7155	0.8902	0.3507	0.052*
C8	0.5916 (4)	0.9518 (3)	0.4096 (3)	0.0571 (11)
H8A	0.5811	0.9772	0.4691	0.069*
H8B	0.5891	0.9943	0.3627	0.069*
C9	0.5009 (3)	0.8921 (3)	0.3883 (3)	0.0535 (11)
H9A	0.5048	0.8730	0.3250	0.064*
H9B	0.4300	0.9187	0.3937	0.064*
C10	0.5096 (3)	0.8210 (3)	0.4532 (3)	0.0467 (10)
H10A	0.4925	0.8388	0.5148	0.056*
H10B	0.4555	0.7802	0.4331	0.056*
C11	0.6339 (3)	0.7047 (2)	0.4536 (2)	0.0297 (7)
C12	0.5350 (3)	0.6946 (2)	0.3103 (2)	0.0358 (8)
H12A	0.5648	0.7492	0.3046	0.043*
H12B	0.4555	0.6991	0.3137	0.043*
C13	0.5606 (3)	0.6461 (2)	0.2275 (2)	0.0363 (8)
H13A	0.6389	0.6333	0.2309	0.044*
H13B	0.5453	0.6791	0.1725	0.044*
C14	0.4969 (3)	0.5691 (2)	0.2176 (2)	0.0351 (8)
H14A	0.4188	0.5803	0.2222	0.042*
H14B	0.5071	0.5456	0.1570	0.042*
C15	0.5396 (3)	0.4368 (2)	0.2663 (2)	0.0340 (8)
C16	0.3604 (3)	0.4228 (2)	0.1861 (2)	0.0342 (7)
H16A	0.3434	0.4667	0.2279	0.041*
H16B	0.3172	0.3756	0.2022	0.041*
C17	0.3289 (3)	0.4475 (2)	0.0896 (2)	0.0350 (7)
H17A	0.3652	0.4983	0.0754	0.042*
H17B	0.2496	0.4560	0.0827	0.042*
C18	0.3622 (3)	0.3829 (2)	0.0245 (2)	0.0383 (8)
H18A	0.3469	0.4011	−0.0388	0.046*
H18B	0.3189	0.3341	0.0339	0.046*
C19	0.4823 (3)	0.3635 (2)	0.0392 (2)	0.0388 (8)
H19A	0.5009	0.3190	−0.0013	0.047*
H19B	0.5257	0.4106	0.0231	0.047*
C20	0.5107 (3)	0.3402 (2)	0.1374 (2)	0.0355 (8)
H20A	0.4740	0.2896	0.1517	0.043*
H20B	0.5899	0.3320	0.1464	0.043*
C23	0.7741 (4)	0.2946 (3)	0.4075 (4)	0.0720 (15)
H23C	0.8035	0.2840	0.3476	0.086*	0.181 (6)
H23D	0.8178	0.2656	0.4552	0.086*	0.181 (6)
H23A	0.7505	0.2981	0.4705	0.086*	0.819 (6)
H23B	0.8399	0.2609	0.4079	0.086*	0.819 (6)
C211	0.6996 (4)	0.4282 (3)	0.3667 (3)	0.0369 (11)	0.819 (6)
H21A	0.6733	0.4355	0.4283	0.044*	0.819 (6)
H21B	0.7167	0.4814	0.3419	0.044*	0.819 (6)
C212	0.7481 (15)	0.4170 (10)	0.3300 (10)	0.022 (4)*	0.181 (6)
H21C	0.7967	0.3890	0.2893	0.027*	0.181 (6)
H21D	0.7576	0.4753	0.3235	0.027*	0.181 (6)
C221	0.7999 (4)	0.3765 (3)	0.3712 (3)	0.0455 (13)	0.819 (6)
H22A	0.8569	0.4019	0.4112	0.055*	0.819 (6)
H22B	0.8278	0.3714	0.3098	0.055*	0.819 (6)
C222	0.7685 (17)	0.3903 (8)	0.4290 (11)	0.036 (5)*	0.181 (6)
H22C	0.7079	0.4043	0.4672	0.044*	0.181 (6)
H22D	0.8375	0.4112	0.4568	0.044*	0.181 (6)
C241	0.6831 (4)	0.2559 (3)	0.3429 (3)	0.0476 (13)	0.819 (6)
H24A	0.7091	0.2500	0.2810	0.057*	0.819 (6)
H24B	0.6643	0.2023	0.3656	0.057*	0.819 (6)
C242	0.6549 (10)	0.2730 (11)	0.4084 (10)	0.031 (4)*	0.181 (6)
H24C	0.6141	0.3068	0.4497	0.037*	0.181 (6)
H24D	0.6421	0.2157	0.4202	0.037*	0.181 (6)
C251	0.5841 (4)	0.3098 (3)	0.3407 (3)	0.0374 (11)	0.819 (6)
H25A	0.5261	0.2874	0.2992	0.045*	0.819 (6)
H25B	0.5562	0.3140	0.4022	0.045*	0.819 (6)
C252	0.6367 (17)	0.2961 (11)	0.3078 (10)	0.026 (4)*	0.181 (6)
H25C	0.5729	0.2679	0.2797	0.031*	0.181 (6)
H25D	0.7010	0.2828	0.2736	0.031*	0.181 (6)
H1	0.525 (3)	0.421 (3)	0.454 (5)	0.11 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0395 (3)	0.0379 (2)	0.01733 (18)	−0.01106 (19)	−0.00355 (15)	0.00224 (16)
O1	0.0446 (15)	0.0437 (14)	0.0198 (10)	−0.0146 (13)	0.0008 (10)	0.0020 (10)
N1	0.0345 (16)	0.0394 (15)	0.0216 (12)	−0.0059 (12)	−0.0016 (11)	−0.0027 (11)
N2	0.0300 (15)	0.0385 (16)	0.0313 (14)	−0.0024 (12)	0.0003 (12)	−0.0098 (12)
N3	0.0378 (16)	0.0357 (15)	0.0199 (12)	−0.0081 (12)	−0.0025 (11)	0.0009 (11)
N4	0.0476 (18)	0.0354 (15)	0.0166 (12)	−0.0074 (13)	−0.0049 (11)	0.0049 (11)
N5	0.0367 (16)	0.0324 (14)	0.0215 (12)	−0.0053 (12)	−0.0023 (11)	−0.0011 (10)
N6	0.053 (2)	0.0355 (16)	0.0334 (15)	−0.0051 (14)	−0.0150 (14)	0.0075 (12)
C1	0.050 (2)	0.0362 (19)	0.0338 (18)	0.0004 (16)	−0.0030 (16)	−0.0005 (15)
C2	0.042 (2)	0.051 (2)	0.059 (3)	0.0060 (19)	−0.0070 (19)	−0.006 (2)
C3	0.053 (3)	0.064 (3)	0.057 (3)	−0.002 (2)	−0.023 (2)	0.001 (2)
C4	0.049 (2)	0.056 (2)	0.0338 (19)	−0.0162 (19)	−0.0091 (17)	0.0010 (17)
C5	0.046 (2)	0.049 (2)	0.0222 (15)	−0.0142 (17)	−0.0007 (14)	−0.0020 (14)
C6	0.041 (2)	0.0376 (19)	0.0354 (18)	−0.0058 (16)	−0.0032 (15)	−0.0070 (15)
C7	0.050 (2)	0.0352 (19)	0.045 (2)	−0.0018 (17)	−0.0077 (17)	−0.0062 (16)
C8	0.065 (3)	0.040 (2)	0.066 (3)	0.015 (2)	−0.004 (2)	−0.012 (2)
C9	0.043 (2)	0.053 (2)	0.063 (3)	0.0190 (19)	−0.003 (2)	−0.010 (2)
C10	0.035 (2)	0.062 (3)	0.043 (2)	0.0040 (18)	0.0073 (17)	−0.0157 (19)
C11	0.0298 (18)	0.0398 (18)	0.0198 (14)	−0.0074 (14)	0.0060 (12)	−0.0028 (12)
C12	0.048 (2)	0.0344 (18)	0.0235 (15)	−0.0068 (16)	−0.0062 (14)	0.0009 (13)
C13	0.054 (2)	0.0329 (17)	0.0210 (14)	−0.0058 (16)	−0.0038 (14)	0.0034 (13)
C14	0.051 (2)	0.0336 (17)	0.0200 (14)	−0.0061 (15)	−0.0067 (14)	0.0037 (12)
C15	0.044 (2)	0.0370 (19)	0.0203 (14)	−0.0081 (15)	−0.0043 (13)	0.0056 (12)
C16	0.038 (2)	0.0384 (18)	0.0265 (15)	−0.0088 (15)	0.0052 (14)	−0.0030 (14)
C17	0.0305 (18)	0.0418 (19)	0.0321 (16)	−0.0045 (15)	−0.0025 (14)	0.0001 (14)
C18	0.045 (2)	0.045 (2)	0.0244 (15)	−0.0047 (16)	−0.0057 (14)	−0.0031 (14)
C19	0.045 (2)	0.047 (2)	0.0243 (16)	0.0047 (17)	0.0008 (14)	−0.0052 (14)
C20	0.044 (2)	0.0342 (18)	0.0283 (16)	−0.0002 (15)	−0.0021 (14)	−0.0013 (13)
C211	0.038 (3)	0.043 (2)	0.029 (2)	0.0041 (19)	−0.0061 (19)	0.0005 (18)
C221	0.038 (3)	0.064 (3)	0.034 (2)	0.013 (2)	−0.0055 (19)	0.000 (2)
C23	0.057 (3)	0.066 (3)	0.092 (4)	0.022 (2)	−0.010 (3)	0.027 (3)
C241	0.060 (3)	0.041 (3)	0.042 (3)	0.018 (2)	0.007 (2)	0.008 (2)
C251	0.047 (3)	0.036 (2)	0.029 (2)	0.006 (2)	0.003 (2)	0.0063 (17)
P1	0.1251 (14)	0.0593 (8)	0.0842 (10)	0.0352 (9)	0.0554 (10)	0.0207 (7)
F16	0.131 (3)	0.162 (4)	0.074 (2)	0.077 (3)	0.036 (2)	0.045 (2)
F15	0.113 (3)	0.126 (3)	0.185 (5)	0.064 (3)	0.054 (3)	0.046 (3)
F14	0.220 (5)	0.134 (3)	0.069 (2)	0.093 (4)	0.029 (3)	0.035 (2)
F13	0.194 (5)	0.099 (3)	0.172 (5)	0.001 (3)	0.047 (4)	−0.002 (3)
F12	0.291 (8)	0.082 (3)	0.188 (6)	−0.030 (4)	−0.065 (5)	0.022 (3)
F11	0.162 (5)	0.271 (7)	0.129 (4)	0.020 (5)	0.095 (4)	0.031 (4)

Geometric parameters (Å, º)

Cu1—O1^i	1.921 (2)	C12—H12B	0.9900
Cu1—O1	1.948 (2)	C13—C14	1.514 (5)
Cu1—N4	1.968 (3)	C13—H13A	0.9900
Cu1—N3	1.982 (3)	C13—H13B	0.9900
O1—Cu1^i	1.921 (2)	C14—H14A	0.9900
O1—H1	0.83 (4)	C14—H14B	0.9900
N1—C11	1.362 (4)	C16—C17	1.512 (5)
N1—C1	1.458 (5)	C16—H16A	0.9900
N1—C5	1.466 (4)	C16—H16B	0.9900
N2—C11	1.364 (4)	C17—C18	1.518 (5)
N2—C10	1.462 (5)	C17—H17A	0.9900
N2—C6	1.465 (4)	C17—H17B	0.9900
N3—C11	1.322 (4)	C18—C19	1.524 (5)
N3—C12	1.474 (4)	C18—H18A	0.9900
N4—C15	1.304 (4)	C18—H18B	0.9900
N4—C14	1.468 (4)	C19—C20	1.522 (5)
N5—C15	1.364 (4)	C19—H19A	0.9900
N5—C20	1.462 (4)	C19—H19B	0.9900
N5—C16	1.468 (5)	C20—H20A	0.9900
N6—C15	1.363 (4)	C20—H20B	0.9900
N6—C211	1.450 (5)	C211—C221	1.510 (6)
N6—C251	1.483 (5)	C211—H21A	0.9900
N6—C252	1.586 (18)	C211—H21B	0.9900
N6—C212	1.699 (18)	C221—C23	1.513 (6)
C1—C2	1.523 (5)	C221—H22A	0.9900
C1—H1A	0.9900	C221—H22B	0.9900
C1—H1B	0.9900	C23—C242	1.517 (12)
C2—C3	1.519 (6)	C23—C241	1.572 (7)
C2—H2A	0.9900	C23—C222	1.636 (13)
C2—H2B	0.9900	C23—H23C	0.9900
C3—C4	1.502 (6)	C23—H23D	0.9900
C3—H3A	0.9900	C23—H23A	0.9900
C3—H3B	0.9900	C23—H23B	0.9899
C4—C5	1.508 (5)	C241—C251	1.519 (6)
C4—H4A	0.9900	C241—H24A	0.9900
C4—H4B	0.9900	C241—H24B	0.9900
C5—H5A	0.9900	C251—H25A	0.9900
C5—H5B	0.9900	C251—H25B	0.9900
C6—C7	1.527 (5)	C212—C222	1.535 (14)
C6—H6A	0.9900	C212—H21C	0.9900
C6—H6B	0.9900	C212—H21D	0.9900
C7—C8	1.525 (6)	C222—H22C	0.9900
C7—H7A	0.9900	C222—H22D	0.9900
C7—H7B	0.9900	C242—C252	1.537 (14)
C8—C9	1.521 (6)	C242—H24C	0.9900
C8—H8A	0.9900	C242—H24D	0.9900
C8—H8B	0.9900	C252—H25C	0.9900
C9—C10	1.528 (6)	C252—H25D	0.9900
C9—H9A	0.9900	P1—F11	1.526 (4)
C9—H9B	0.9900	P1—F12	1.544 (5)
C10—H10A	0.9900	P1—F15	1.569 (4)
C10—H10B	0.9900	P1—F14	1.570 (4)
C12—C13	1.514 (5)	P1—F16	1.575 (4)
C12—H12A	0.9900	P1—F13	1.595 (5)
O1^i—Cu1—O1	74.78 (11)	N5—C16—H16B	109.3
O1^i—Cu1—N4	166.25 (11)	C17—C16—H16B	109.3
O1—Cu1—N4	92.34 (11)	H16A—C16—H16B	107.9
O1^i—Cu1—N3	97.40 (10)	C16—C17—C18	109.6 (3)
O1—Cu1—N3	168.62 (12)	C16—C17—H17A	109.8
N4—Cu1—N3	96.02 (11)	C18—C17—H17A	109.8
Cu1^i—O1—Cu1	105.22 (11)	C16—C17—H17B	109.8
Cu1^i—O1—H1	95 (5)	C18—C17—H17B	109.8
Cu1—O1—H1	94 (5)	H17A—C17—H17B	108.2
C11—N1—C1	122.5 (3)	C17—C18—C19	110.9 (3)
C11—N1—C5	121.1 (3)	C17—C18—H18A	109.5
C1—N1—C5	114.3 (3)	C19—C18—H18A	109.5
C11—N2—C10	122.7 (3)	C17—C18—H18B	109.5
C11—N2—C6	122.5 (3)	C19—C18—H18B	109.5
C10—N2—C6	114.0 (3)	H18A—C18—H18B	108.0
C11—N3—C12	117.1 (3)	C20—C19—C18	111.2 (3)
C11—N3—Cu1	126.3 (2)	C20—C19—H19A	109.4
C12—N3—Cu1	115.4 (2)	C18—C19—H19A	109.4
C15—N4—C14	118.1 (3)	C20—C19—H19B	109.4
C15—N4—Cu1	121.7 (2)	C18—C19—H19B	109.4
C14—N4—Cu1	118.5 (2)	H19A—C19—H19B	108.0
C15—N5—C20	124.9 (3)	N5—C20—C19	109.5 (3)
C15—N5—C16	120.9 (3)	N5—C20—H20A	109.8
C20—N5—C16	113.8 (3)	C19—C20—H20A	109.8
C15—N6—C211	117.8 (3)	N5—C20—H20B	109.8
C15—N6—C251	118.2 (3)	C19—C20—H20B	109.8
C211—N6—C251	114.1 (3)	H20A—C20—H20B	108.2
C15—N6—C252	132.4 (7)	N6—C211—C221	108.8 (4)
C211—N6—C252	109.9 (7)	N6—C211—H21A	109.9
C15—N6—C212	124.5 (6)	C221—C211—H21A	109.9
C251—N6—C212	117.3 (6)	N6—C211—H21B	109.9
C252—N6—C212	97.0 (10)	C221—C211—H21B	109.9
N1—C1—C2	109.7 (3)	H21A—C211—H21B	108.3
N1—C1—H1A	109.7	C211—C221—C23	110.3 (4)
C2—C1—H1A	109.7	C211—C221—H22A	109.6
N1—C1—H1B	109.7	C23—C221—H22A	109.6
C2—C1—H1B	109.7	C211—C221—H22B	109.6
H1A—C1—H1B	108.2	C23—C221—H22B	109.6
C3—C2—C1	111.0 (4)	H22A—C221—H22B	108.1
C3—C2—H2A	109.4	C221—C23—C242	116.3 (7)
C1—C2—H2A	109.4	C221—C23—C241	108.5 (4)
C3—C2—H2B	109.4	C242—C23—C222	100.4 (11)
C1—C2—H2B	109.4	C241—C23—C222	119.0 (7)
H2A—C2—H2B	108.0	C221—C23—H23C	75.6
C4—C3—C2	111.6 (3)	C242—C23—H23C	111.7
C4—C3—H3A	109.3	C241—C23—H23C	70.8
C2—C3—H3A	109.3	C222—C23—H23C	111.7
C4—C3—H3B	109.3	C221—C23—H23D	125.3
C2—C3—H3B	109.3	C242—C23—H23D	111.7
H3A—C3—H3B	108.0	C241—C23—H23D	124.9
C3—C4—C5	110.5 (3)	C222—C23—H23D	111.7
C3—C4—H4A	109.5	H23C—C23—H23D	109.5
C5—C4—H4A	109.5	C221—C23—H23A	110.9
C3—C4—H4B	109.5	C242—C23—H23A	70.8
C5—C4—H4B	109.5	C241—C23—H23A	110.8
H4A—C4—H4B	108.1	C222—C23—H23A	75.1
N1—C5—C4	111.8 (3)	H23C—C23—H23A	171.6
N1—C5—H5A	109.2	H23D—C23—H23A	62.6
C4—C5—H5A	109.2	C221—C23—H23B	109.2
N1—C5—H5B	109.2	C242—C23—H23B	131.5
C4—C5—H5B	109.2	C241—C23—H23B	109.2
H5A—C5—H5B	107.9	C222—C23—H23B	126.9
N2—C6—C7	110.1 (3)	H23C—C23—H23B	63.9
N2—C6—H6A	109.6	H23D—C23—H23B	45.6
C7—C6—H6A	109.6	H23A—C23—H23B	108.3
N2—C6—H6B	109.6	C251—C241—C23	108.5 (4)
C7—C6—H6B	109.6	C251—C241—H24A	110.0
H6A—C6—H6B	108.2	C23—C241—H24A	110.0
C8—C7—C6	110.6 (4)	C251—C241—H24B	110.0
C8—C7—H7A	109.5	C23—C241—H24B	110.0
C6—C7—H7A	109.5	H24A—C241—H24B	108.4
C8—C7—H7B	109.5	N6—C251—C241	108.0 (4)
C6—C7—H7B	109.5	N6—C251—H25A	110.1
H7A—C7—H7B	108.1	C241—C251—H25A	110.1
C9—C8—C7	110.7 (3)	N6—C251—H25B	110.1
C9—C8—H8A	109.5	C241—C251—H25B	110.1
C7—C8—H8A	109.5	H25A—C251—H25B	108.4
C9—C8—H8B	109.5	C222—C212—N6	101.8 (12)
C7—C8—H8B	109.5	C222—C212—H21C	111.4
H8A—C8—H8B	108.1	N6—C212—H21C	111.4
C8—C9—C10	111.0 (4)	C222—C212—H21D	111.4
C8—C9—H9A	109.4	N6—C212—H21D	111.4
C10—C9—H9A	109.4	H21C—C212—H21D	109.3
C8—C9—H9B	109.4	C212—C222—C23	96.2 (10)
C10—C9—H9B	109.4	C212—C222—H22C	112.5
H9A—C9—H9B	108.0	C23—C222—H22C	112.5
N2—C10—C9	112.1 (3)	C212—C222—H22D	112.5
N2—C10—H10A	109.2	C23—C222—H22D	112.5
C9—C10—H10A	109.2	H22C—C222—H22D	110.0
N2—C10—H10B	109.2	C23—C242—C252	91.4 (11)
C9—C10—H10B	109.2	C252—C242—H23A	125.6
H10A—C10—H10B	107.9	C23—C242—H24C	113.4
N3—C11—N1	120.6 (3)	C252—C242—H24C	113.4
N3—C11—N2	123.3 (3)	H23A—C242—H24C	82.9
N1—C11—N2	116.1 (3)	C23—C242—H24D	113.4
N3—C12—C13	111.2 (3)	C252—C242—H24D	113.4
N3—C12—H12A	109.4	H23A—C242—H24D	106.8
C13—C12—H12A	109.4	H24C—C242—H24D	110.7
N3—C12—H12B	109.4	C242—C252—N6	104.8 (12)
C13—C12—H12B	109.4	C242—C252—H25C	110.8
H12A—C12—H12B	108.0	N6—C252—H25C	110.8
C12—C13—C14	113.9 (3)	C242—C252—H25D	110.8
C12—C13—H13A	108.8	N6—C252—H25D	110.8
C14—C13—H13A	108.8	H25C—C252—H25D	108.9
C12—C13—H13B	108.8	F11—P1—F12	97.1 (4)
C14—C13—H13B	108.8	F11—P1—F15	93.3 (3)
H13A—C13—H13B	107.7	F12—P1—F15	91.0 (3)
N4—C14—C13	110.5 (3)	F11—P1—F14	89.0 (3)
N4—C14—H14A	109.5	F12—P1—F14	89.7 (3)
C13—C14—H14A	109.5	F15—P1—F14	177.5 (3)
N4—C14—H14B	109.5	F11—P1—F16	174.1 (4)
C13—C14—H14B	109.5	F12—P1—F16	88.5 (4)
H14A—C14—H14B	108.1	F15—P1—F16	88.4 (2)
N4—C15—N6	119.8 (3)	F14—P1—F16	89.2 (2)
N4—C15—N5	122.7 (3)	F11—P1—F13	87.6 (3)
N6—C15—N5	117.4 (3)	F12—P1—F13	175.2 (4)
N5—C16—C17	111.7 (3)	F15—P1—F13	89.4 (3)
N5—C16—H16A	109.3	F14—P1—F13	89.7 (3)
C17—C16—H16A	109.3	F16—P1—F13	86.8 (3)
O1^i—Cu1—O1—Cu1^i	0.0	C211—N6—C15—N4	−9.5 (5)
N4—Cu1—O1—Cu1^i	175.09 (14)	C251—N6—C15—N4	134.2 (4)
N3—Cu1—O1—Cu1^i	−47.6 (6)	C252—N6—C15—N4	170.4 (10)
O1^i—Cu1—N3—C11	22.5 (3)	C212—N6—C15—N4	−43.9 (9)
O1—Cu1—N3—C11	68.4 (7)	C211—N6—C15—N5	166.5 (3)
N4—Cu1—N3—C11	−154.5 (3)	C251—N6—C15—N5	−49.8 (5)
O1^i—Cu1—N3—C12	−144.9 (2)	C252—N6—C15—N5	−13.6 (11)
O1—Cu1—N3—C12	−98.9 (6)	C212—N6—C15—N5	132.2 (8)
N4—Cu1—N3—C12	38.2 (3)	C20—N5—C15—N4	145.3 (3)
O1^i—Cu1—N4—C15	−9.1 (7)	C16—N5—C15—N4	−42.3 (5)
O1—Cu1—N4—C15	−29.4 (3)	C20—N5—C15—N6	−30.6 (5)
N3—Cu1—N4—C15	158.3 (3)	C16—N5—C15—N6	141.8 (3)
O1^i—Cu1—N4—C14	155.5 (4)	C15—N5—C16—C17	129.2 (3)
O1—Cu1—N4—C14	135.1 (3)	C20—N5—C16—C17	−57.7 (4)
N3—Cu1—N4—C14	−37.1 (3)	N5—C16—C17—C18	55.0 (4)
C11—N1—C1—C2	140.4 (3)	C16—C17—C18—C19	−54.6 (4)
C5—N1—C1—C2	−56.0 (4)	C17—C18—C19—C20	55.6 (4)
N1—C1—C2—C3	54.7 (4)	C15—N5—C20—C19	−130.6 (3)
C1—C2—C3—C4	−55.0 (5)	C16—N5—C20—C19	56.6 (4)
C2—C3—C4—C5	53.5 (5)	C18—C19—C20—N5	−55.0 (4)
C11—N1—C5—C4	−140.2 (3)	C15—N6—C211—C221	−154.3 (4)
C1—N1—C5—C4	55.9 (4)	C251—N6—C211—C221	60.6 (5)
C3—C4—C5—N1	−53.0 (4)	C252—N6—C211—C221	25.8 (9)
C11—N2—C6—C7	132.8 (3)	C212—N6—C211—C221	−42.7 (11)
C10—N2—C6—C7	−56.7 (4)	N6—C211—C221—C23	−58.7 (5)
N2—C6—C7—C8	56.6 (4)	C211—C221—C23—C242	15.3 (9)
C6—C7—C8—C9	−55.8 (5)	C211—C221—C23—C241	59.0 (5)
C7—C8—C9—C10	53.0 (5)	C211—C221—C23—C222	−55.1 (12)
C11—N2—C10—C9	−134.8 (3)	C221—C23—C241—C251	−59.2 (5)
C6—N2—C10—C9	54.8 (4)	C242—C23—C241—C251	49.9 (10)
C8—C9—C10—N2	−51.9 (4)	C222—C23—C241—C251	−21.3 (9)
C12—N3—C11—N1	−153.3 (3)	C15—N6—C251—C241	153.6 (4)
Cu1—N3—C11—N1	39.5 (4)	C211—N6—C251—C241	−61.4 (5)
C12—N3—C11—N2	22.3 (5)	C252—N6—C251—C241	28.0 (11)
Cu1—N3—C11—N2	−144.8 (3)	C212—N6—C251—C241	−28.2 (8)
C1—N1—C11—N3	26.2 (5)	C23—C241—C251—N6	58.3 (5)
C5—N1—C11—N3	−136.4 (3)	C15—N6—C212—C222	134.2 (8)
C1—N1—C11—N2	−149.8 (3)	C211—N6—C212—C222	47.6 (9)
C5—N1—C11—N2	47.7 (4)	C251—N6—C212—C222	−43.9 (13)
C10—N2—C11—N3	46.0 (5)	C252—N6—C212—C222	−70.6 (12)
C6—N2—C11—N3	−144.3 (3)	N6—C212—C222—C23	73.8 (12)
C10—N2—C11—N1	−138.2 (3)	C221—C23—C222—C212	33.8 (8)
C6—N2—C11—N1	31.5 (4)	C242—C23—C222—C212	−87.0 (13)
C11—N3—C12—C13	133.8 (3)	C241—C23—C222—C212	−47.9 (14)
Cu1—N3—C12—C13	−57.7 (3)	C221—C23—C242—C252	51.6 (13)
N3—C12—C13—C14	73.0 (4)	C241—C23—C242—C252	−36.7 (8)
C15—N4—C14—C13	−141.0 (3)	C222—C23—C242—C252	86.0 (12)
Cu1—N4—C14—C13	53.9 (4)	C23—C242—C252—N6	−84.6 (13)
C12—C13—C14—N4	−69.6 (4)	C15—N6—C252—C242	−131.8 (8)
C14—N4—C15—N6	147.6 (3)	C211—N6—C252—C242	48.1 (13)
Cu1—N4—C15—N6	−47.8 (4)	C251—N6—C252—C242	−55.8 (10)
C14—N4—C15—N5	−28.2 (5)	C212—N6—C252—C242	76.1 (13)
Cu1—N4—C15—N5	136.4 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.