Copper(I) and copper(II) complexes of an ethylene cross-bridged cyclam

The preparation and crystal structures of (4,11-di­benzyl-1,4,8,11-tetra­aza­bi­cyclo­[6.6.2]­hexa­decane-κ⁴N)copper(I) hexa-fluorophosphate, [Cu(C₂₆H₃₈N₄)]PF₆, and acetonitrile(4,11-dibenzyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane-κ⁴N)-copper(II) bis(hexafluorophosphate), [Cu(C₂H₃N)(C₂₆H₃₈-N₄)](PF₆)₂, are described. The Cu^I ion is tetracoordinated in a very distorted tetrahedron, while the Cu^II analogue is pentacoordinated in a square pyramid.

S1. Comment

Ethylene cross-bridged tetraazamacrocycles have recently gained popularity as proton sponges (Weisman et al., 1990; Bencini et al., 1994; Miyahara et al., 1999) but have been less well exploited as ligands for the coordination of transition metal ions (Weisman et al., 1996; Hubin et al., 1998). The short two-carbon cross-bridge imparts additional rigidity as well as topological constraints (Busch, 1993) to the parent macrocycle ligand. The resulting ligands are strongly basic, which causes coordination to transition metal ions to be difficult (Hubin et al., 1998). However, these same properties give the complexes valuable properties, such as remarkable kinetic stability in harsh aqueous conditions (Hubin et al., 1998) and useful oxidizing ability (Busch et al., 1998).

In further investigations of the properties of these interesting ligands, the copper(I) and copper(II) complexes of the benzyldisubstituted cross-bridged cyclam 4,11-dibenzyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane, (4,11-dibenzyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane-κ⁴N)copper(I) hexafluorophosphate, (I), and [acetonitrile(4,11-dibenzyl-1,4,8,11- tetraazabicyclo[6.6.2]hexadecane-κ⁴N)]copper(II), (II), were prepared and then examined by X-ray crystallography, and their crystal structures are presented here.

In the Cu^I complex, (I), (Fig. 1) the Cu⁺ ion was found to coordinate to all four tertiary N atoms of the bicyclic ligand, in what is best described as octahedral geometry with two vacant positions; the pendant benzyl groups appear to block the approach of ligands to these positions, with comparatively short Cu···C distances (Cu···C18, C19, C25 and C26 in the range 3.24–3.37 Å). The trans angle at Cu, N8—Cu1—N1, is 171.85 (5)°, with the other N—Cu—N bond angles in the range 85.17 (5)–97.96 (5)°. The N1—Cu1 and N8—Cu1 bond lengths [2.0204 (13) and 2.0105 (13) Å] are short compared with the other Cu—N bond lengths [N4—Cu1 2.1608 (13) and N11—Cu1 2.1715 (13) Å] and with the average four-coordinate copper(I) to tertiary N bond length of 2.139 Å (Orpen et al., 1989; Allen & Kennard, 1993). This short bond length indicates how difficult it is for the ligand cavity to accomodate Cu⁺ in something approaching its preferred tetrahedral geometry.

Finally, it should be noted that (I) is the first structure of an ethylene cross-bridged cyclam in which the metal ion is completely enclosed within the ligand cavity (the Cu atom lies inside the N atoms subtending 172°), as opposed to the many other complexes (Hubin, 1999) with this size of cross-bridged ligand and small metal ions, such as Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Zn²⁺, Mn³⁺ and Fe³⁺, in which the metal ion is situated outside the ligand cavity (axial N—M—N bond angles < 180°, bent away from the ligand cavity). We believe the geometric preferences of the various metal ions underlie this difference.

The product of the air oxidation of (I) in acetonitrile is the green Cu²⁺ complex, (II), in which an acetonitrile molecule takes up a fifth position around the metal. This complex is similar to previous Cu²⁺ complexes of ethylene cross-bridged ligands, which tend to have square pyramidal coordination geometries, as does (II) (Fig. 2). The acetonitrile ligand and three of the macrobicyclic N atoms are the equatorial ligands, with one bridgehead N of the ligand acting as the axial ligand. The flexibility of the benzyl groups of this ligand is demonstrated in this structure, as one has been forced to rotate, folding away from the Cu^II ion, in order for the acetonitrile ligand to coordinate. In the Cu⁺ complex, (I), both benzyl groups are folded towards the metal ion, essentially occupying the empty fifth coordination site. Similarly, complex (II) has the metal ion completely engulfed, with an N1—Cu1—N8 bond angle of 177.34 (9)°.

S2. Experimental

To prepare complex (I), Cu(CH₃CN)·PF₆ (0.373 g; 0.001 mol) dissolved in pyridine (10 ml) was added to the ligand (0.406 g; 0.001 mol) dissolved in pyridine (10 ml) under a nitrogen atmosphere. The reaction mixture was stirred for 20 h, giving a clear pale-yellow solution. Filtration followed by solvent evaporation yielded pale green-yellow crystalline blocks of (I). To prepare complex (II), a solution of complex (I) in MeOH (15 ml) was stirred overnight while air was gently bubbled through it. The solution quickly turned dark green. Filtration followed by evaporation of the solvent yielded a dark green crude product. Pure (II) was obtained on addition of excess NH₄PF₆ to an acetonitrile solution of the crude product. Ether diffusion into this solution yielded X-ray quality crystals.

Computing details

For both compounds, data collection: SMART (Siemens, 1994); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT. Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) for (I); SHELXTL (Sheldrick, 1997b) for (II). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a) for (I); SHELXTL for (II). Molecular graphics: SHELXTL (Sheldrick, 1997b) for (I); SHELXTL for (II). For both compounds, software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. View of the cation of (I) showing the atomic numbering. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as spheres of arbitrary radii.
	Fig. 2. View of the cation of (II) showing the atomic numbering. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as spheres of arbitrary radii.

(I) (4,11-dibenzyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane-κ⁴N)copper(I) hexafluorophosphate

Crystal data

[Cu(C26H38N4)]PF6	F(000) = 1280
Mr = 615.11	Dx = 1.491 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.5684 (2) Å	Cell parameters from 5967 reflections
b = 11.7898 (2) Å	θ = 3–20°
c = 24.294 (1) Å	µ = 0.92 mm^−1
β = 90.684 (1)°	T = 180 K
V = 2740.4 (7) Å^3	Irregular block, pale green-yellow
Z = 4	0.6 × 0.5 × 0.4 mm

Data collection

Siemens SMART diffractometer	6434 independent reflections
Radiation source: normal-focus sealed tube	5449 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 8.192 pixels mm^-1	θmax = 28.6°, θmin = 1.7°
ω scans	h = −12→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −11→15
Tmin = 0.544, Tmax = 0.692	l = −27→32
15900 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.078	w = 1/[σ^2(Fo^2) + (0.036P)^2 + 1.26P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.003
6434 reflections	Δρmax = 0.52 e Å^−3
344 parameters	Δρmin = −0.37 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0023 (2)

Special details

Experimental. The temperature of the crystal was controlled using the Oxford Cryosystem Cryostream Cooler (Cosier & Glazer, 1986). The data collection nominally covered over a hemisphere of reciprocal space, by a combination of three sets of exposures with different ϕ angles for the crystal; each 10 s exposure covered 0.3° in ω. The crystal-to-detector distance was 5.0 cm. Coverage of the unique set is over 97% complete to at least 26° in θ. Crystal decay was found to be negligible by repeating the initial frames at the end of data collection and analyzing the duplicate reflections. H atoms were added at calculated positions and refined using a riding model. Anisotropic displacement parameters were used for all non-H atoms; H-atoms were given isotropic displacement parameters equal to 1.2 (or 1.5 for methyl-H atoms) times the equivalent isotropic displacement parameter of the atom to which they are attached.

Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107.

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.

H atoms were added at calculated positions and refined using a riding model, including free rotation about C—C bonds for methyl groups. H atoms were given isotropic displacement parameters equal to 1.2 (or 1.5 for methyl-H) times the equivalent isotropic displacement parameter of the carrier atom.

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

	x	y	z	Uiso*/Ueq
Cu1	0.780138 (18)	0.257611 (15)	0.115967 (7)	0.01941 (6)
N1	0.65259 (14)	0.26321 (11)	0.04914 (5)	0.0233 (3)
C2	0.68360 (18)	0.37327 (14)	0.02103 (7)	0.0292 (3)
H2A	0.6018	0.3960	−0.0017	0.035*
H2B	0.7639	0.3629	−0.0038	0.035*
C3	0.71718 (19)	0.46683 (14)	0.06210 (7)	0.0312 (4)
H3A	0.7476	0.5352	0.0418	0.037*
H3B	0.6313	0.4866	0.0823	0.037*
N4	0.82715 (14)	0.43448 (11)	0.10201 (6)	0.0254 (3)
C5	0.81184 (19)	0.50028 (14)	0.15369 (7)	0.0309 (4)
H5A	0.7118	0.5015	0.1636	0.037*
H5B	0.8408	0.5795	0.1467	0.037*
C6	0.89563 (19)	0.45513 (14)	0.20263 (7)	0.0311 (4)
H6A	0.9954	0.4542	0.1923	0.037*
H6B	0.8862	0.5099	0.2332	0.037*
C7	0.85880 (18)	0.33822 (14)	0.22446 (7)	0.0283 (3)
H7A	0.9119	0.3262	0.2592	0.034*
H7B	0.7583	0.3382	0.2337	0.034*
N8	0.88559 (14)	0.23885 (11)	0.18746 (5)	0.0223 (3)
C9	1.03752 (16)	0.23467 (14)	0.17293 (7)	0.0265 (3)
H9A	1.0885	0.1906	0.2014	0.032*
H9B	1.0754	0.3128	0.1733	0.032*
C10	1.06476 (16)	0.18163 (15)	0.11668 (7)	0.0267 (3)
H10A	1.1631	0.1962	0.1067	0.032*
H10B	1.0525	0.0985	0.1195	0.032*
N11	0.97259 (14)	0.22480 (11)	0.07225 (6)	0.0233 (3)
C12	0.95237 (18)	0.13633 (14)	0.02968 (7)	0.0279 (3)
H12A	0.9362	0.0629	0.0483	0.033*
H12B	1.0399	0.1292	0.0087	0.033*
C13	0.83242 (18)	0.15706 (15)	−0.01087 (7)	0.0311 (4)
H13A	0.8332	0.0952	−0.0384	0.037*
H13B	0.8519	0.2285	−0.0307	0.037*
C14	0.68460 (18)	0.16500 (14)	0.01220 (7)	0.0286 (3)
H14A	0.6180	0.1673	−0.0193	0.034*
H14B	0.6659	0.0943	0.0328	0.034*
C15	1.01834 (18)	0.33389 (14)	0.04855 (7)	0.0292 (3)
H15A	0.9820	0.3393	0.0103	0.035*
H15B	1.1217	0.3342	0.0469	0.035*
C16	0.97059 (18)	0.43962 (14)	0.08060 (7)	0.0309 (4)
H16A	1.0359	0.4517	0.1120	0.037*
H16B	0.9778	0.5064	0.0561	0.037*
C17	0.50020 (17)	0.26185 (14)	0.06178 (7)	0.0283 (3)
H17A	0.4472	0.2473	0.0272	0.034*
H17B	0.4730	0.3379	0.0752	0.034*
C18	0.45796 (16)	0.17515 (14)	0.10382 (7)	0.0261 (3)
C19	0.45210 (17)	0.20569 (16)	0.15913 (7)	0.0304 (4)
H19A	0.4783	0.2802	0.1700	0.037*
C20	0.40847 (19)	0.12876 (17)	0.19856 (7)	0.0360 (4)
H20A	0.4034	0.1510	0.2361	0.043*
C21	0.37232 (19)	0.01967 (17)	0.18320 (8)	0.0370 (4)
H21A	0.3437	−0.0333	0.2103	0.044*
C22	0.37759 (18)	−0.01281 (16)	0.12859 (8)	0.0343 (4)
H22A	0.3531	−0.0879	0.1181	0.041*
C23	0.41908 (17)	0.06531 (15)	0.08907 (7)	0.0297 (3)
H23A	0.4209	0.0434	0.0515	0.036*
C24	0.84474 (18)	0.13664 (14)	0.22006 (7)	0.0281 (3)
H24A	0.7456	0.1443	0.2306	0.034*
H24B	0.9017	0.1345	0.2543	0.034*
C25	0.86281 (18)	0.02626 (14)	0.18998 (7)	0.0289 (3)
C26	0.76459 (19)	−0.00868 (15)	0.15140 (8)	0.0339 (4)
H26A	0.6830	0.0356	0.1450	0.041*
C27	0.7847 (2)	−0.10845 (18)	0.12196 (9)	0.0475 (5)
H27A	0.7169	−0.1324	0.0955	0.057*
C28	0.9039 (3)	−0.17285 (17)	0.13123 (10)	0.0521 (6)
H28A	0.9190	−0.2398	0.1103	0.063*
C29	1.0000 (2)	−0.14036 (17)	0.17041 (10)	0.0484 (5)
H29A	1.0809	−0.1853	0.1770	0.058*
C30	0.9793 (2)	−0.04218 (16)	0.20032 (9)	0.0385 (4)
H30A	1.0449	−0.0211	0.2281	0.046*
P1	0.32707 (5)	0.59307 (4)	0.143834 (18)	0.03149 (11)
F6	0.31406 (13)	0.50136 (10)	0.09562 (5)	0.0439 (3)
F5	0.33857 (16)	0.68426 (13)	0.19194 (5)	0.0652 (4)
F4	0.18627 (17)	0.64902 (13)	0.12183 (7)	0.0778 (5)
F2	0.23928 (15)	0.51241 (14)	0.18269 (6)	0.0656 (4)
F3	0.46584 (13)	0.53303 (14)	0.16510 (6)	0.0639 (4)
F1	0.4150 (2)	0.67196 (14)	0.10468 (6)	0.0821 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02024 (10)	0.01963 (10)	0.01840 (10)	0.00113 (7)	0.00165 (7)	−0.00011 (7)
N1	0.0256 (7)	0.0247 (7)	0.0195 (6)	0.0033 (5)	−0.0003 (5)	−0.0008 (5)
C2	0.0335 (9)	0.0300 (8)	0.0241 (8)	0.0057 (7)	0.0011 (7)	0.0059 (7)
C3	0.0389 (9)	0.0227 (8)	0.0321 (9)	0.0049 (7)	0.0025 (7)	0.0063 (7)
N4	0.0299 (7)	0.0207 (6)	0.0259 (7)	0.0003 (5)	0.0051 (5)	−0.0003 (5)
C5	0.0374 (9)	0.0210 (8)	0.0344 (9)	−0.0003 (7)	0.0059 (7)	−0.0068 (7)
C6	0.0336 (9)	0.0284 (8)	0.0315 (9)	−0.0041 (7)	0.0043 (7)	−0.0119 (7)
C7	0.0307 (8)	0.0334 (9)	0.0209 (8)	0.0014 (7)	0.0026 (6)	−0.0071 (7)
N8	0.0215 (6)	0.0249 (7)	0.0206 (6)	0.0020 (5)	0.0031 (5)	−0.0012 (5)
C9	0.0202 (7)	0.0341 (9)	0.0252 (8)	0.0025 (6)	−0.0002 (6)	−0.0013 (6)
C10	0.0215 (7)	0.0317 (8)	0.0269 (8)	0.0046 (6)	0.0046 (6)	−0.0006 (6)
N11	0.0248 (6)	0.0229 (6)	0.0223 (6)	0.0006 (5)	0.0053 (5)	−0.0007 (5)
C12	0.0307 (8)	0.0274 (8)	0.0257 (8)	0.0032 (6)	0.0073 (6)	−0.0048 (6)
C13	0.0365 (9)	0.0331 (9)	0.0238 (8)	0.0027 (7)	0.0036 (7)	−0.0075 (7)
C14	0.0328 (9)	0.0309 (8)	0.0219 (8)	0.0019 (7)	−0.0018 (6)	−0.0072 (6)
C15	0.0302 (8)	0.0295 (8)	0.0283 (8)	−0.0029 (7)	0.0103 (7)	0.0026 (7)
C16	0.0349 (9)	0.0255 (8)	0.0324 (9)	−0.0066 (7)	0.0090 (7)	0.0019 (7)
C17	0.0249 (8)	0.0322 (9)	0.0277 (8)	0.0051 (6)	−0.0037 (6)	−0.0014 (7)
C18	0.0170 (7)	0.0337 (9)	0.0275 (8)	0.0030 (6)	−0.0014 (6)	−0.0036 (7)
C19	0.0263 (8)	0.0349 (9)	0.0301 (9)	0.0031 (7)	−0.0007 (7)	−0.0068 (7)
C20	0.0321 (9)	0.0507 (11)	0.0252 (9)	0.0044 (8)	0.0014 (7)	−0.0028 (8)
C21	0.0284 (9)	0.0474 (11)	0.0351 (10)	−0.0011 (8)	0.0001 (7)	0.0088 (8)
C22	0.0292 (9)	0.0356 (9)	0.0382 (10)	−0.0040 (7)	−0.0016 (7)	−0.0012 (8)
C23	0.0250 (8)	0.0362 (9)	0.0280 (8)	−0.0007 (7)	−0.0008 (6)	−0.0062 (7)
C24	0.0293 (8)	0.0324 (9)	0.0225 (8)	0.0032 (7)	0.0037 (6)	0.0050 (6)
C25	0.0297 (8)	0.0268 (8)	0.0303 (9)	0.0020 (6)	0.0071 (7)	0.0082 (7)
C26	0.0347 (9)	0.0291 (9)	0.0381 (10)	−0.0014 (7)	0.0039 (7)	0.0046 (7)
C27	0.0586 (13)	0.0348 (10)	0.0491 (12)	−0.0124 (9)	0.0043 (10)	−0.0030 (9)
C28	0.0720 (16)	0.0229 (9)	0.0621 (15)	−0.0002 (9)	0.0267 (12)	−0.0005 (9)
C29	0.0515 (12)	0.0327 (10)	0.0614 (14)	0.0134 (9)	0.0183 (11)	0.0114 (10)
C30	0.0361 (10)	0.0351 (10)	0.0445 (11)	0.0077 (8)	0.0049 (8)	0.0115 (8)
P1	0.0326 (2)	0.0385 (3)	0.0233 (2)	0.00352 (19)	−0.00192 (17)	−0.00251 (18)
F6	0.0562 (7)	0.0384 (6)	0.0371 (6)	0.0049 (5)	−0.0016 (5)	−0.0093 (5)
F5	0.0814 (10)	0.0734 (10)	0.0405 (7)	0.0005 (8)	−0.0079 (7)	−0.0275 (7)
F4	0.0823 (11)	0.0691 (10)	0.0809 (11)	0.0464 (8)	−0.0411 (9)	−0.0288 (8)
F2	0.0549 (8)	0.0958 (11)	0.0466 (8)	−0.0204 (8)	0.0160 (6)	0.0082 (7)
F3	0.0352 (7)	0.1018 (12)	0.0545 (8)	0.0187 (7)	−0.0106 (6)	−0.0054 (8)
F1	0.1319 (15)	0.0738 (10)	0.0406 (8)	−0.0551 (10)	0.0057 (8)	0.0039 (7)

Geometric parameters (Å, º)

Cu1—N8	2.0105 (13)	C15—C16	1.542 (2)
Cu1—N1	2.0204 (13)	C17—C18	1.504 (2)
Cu1—N4	2.1608 (13)	C18—C23	1.393 (2)
Cu1—N11	2.1715 (13)	C18—C19	1.393 (2)
N1—C17	1.494 (2)	C19—C20	1.387 (3)
N1—C2	1.498 (2)	C20—C21	1.382 (3)
N1—C14	1.499 (2)	C21—C22	1.382 (3)
C2—C3	1.519 (2)	C22—C23	1.392 (3)
C3—N4	1.472 (2)	C24—C25	1.504 (2)
N4—C16	1.475 (2)	C25—C26	1.382 (3)
N4—C5	1.485 (2)	C25—C30	1.397 (2)
C5—C6	1.522 (3)	C26—C27	1.391 (3)
C6—C7	1.520 (2)	C27—C28	1.386 (3)
C7—N8	1.500 (2)	C28—C29	1.370 (3)
N8—C24	1.496 (2)	C29—C30	1.382 (3)
N8—C9	1.501 (2)	P1—F1	1.5802 (15)
C9—C10	1.528 (2)	P1—F3	1.5857 (13)
C10—N11	1.476 (2)	P1—F4	1.5870 (13)
N11—C15	1.478 (2)	P1—F2	1.5875 (14)
N11—C12	1.480 (2)	P1—F5	1.5908 (13)
C12—C13	1.523 (2)	P1—F6	1.5978 (12)
C13—C14	1.530 (2)
N8—Cu1—N1	171.85 (5)	C12—C13—C14	117.74 (14)
N8—Cu1—N4	97.96 (5)	N1—C14—C13	117.57 (14)
N1—Cu1—N4	88.12 (5)	N11—C15—C16	114.58 (13)
N8—Cu1—N11	89.04 (5)	N4—C16—C15	115.31 (13)
N1—Cu1—N11	96.92 (5)	N1—C17—C18	114.70 (13)
N4—Cu1—N11	85.17 (5)	C23—C18—C19	118.34 (16)
C17—N1—C2	107.59 (12)	C23—C18—C17	122.03 (15)
C17—N1—C14	108.76 (13)	C19—C18—C17	119.59 (15)
C2—N1—C14	110.68 (13)	C20—C19—C18	120.87 (17)
C17—N1—Cu1	114.60 (10)	C21—C20—C19	119.90 (17)
C2—N1—Cu1	105.89 (10)	C20—C21—C22	120.34 (18)
C14—N1—Cu1	109.28 (10)	C21—C22—C23	119.52 (17)
N1—C2—C3	111.78 (13)	C22—C23—C18	121.02 (16)
N4—C3—C2	112.85 (13)	N8—C24—C25	114.05 (13)
C3—N4—C16	114.70 (14)	C26—C25—C30	118.99 (17)
C3—N4—C5	110.15 (13)	C26—C25—C24	120.42 (15)
C16—N4—C5	112.24 (13)	C30—C25—C24	120.59 (17)
C3—N4—Cu1	101.82 (10)	C25—C26—C27	120.21 (18)
C16—N4—Cu1	106.94 (10)	C28—C27—C26	119.9 (2)
C5—N4—Cu1	110.41 (10)	C29—C28—C27	120.2 (2)
N4—C5—C6	114.93 (14)	C28—C29—C30	120.0 (2)
C7—C6—C5	117.87 (14)	C29—C30—C25	120.5 (2)
N8—C7—C6	117.20 (13)	F1—P1—F3	90.52 (10)
C24—N8—C7	105.32 (12)	F1—P1—F4	90.49 (11)
C24—N8—C9	110.97 (12)	F3—P1—F4	178.01 (9)
C7—N8—C9	109.84 (12)	F1—P1—F2	179.24 (10)
C24—N8—Cu1	114.47 (10)	F3—P1—F2	89.19 (8)
C7—N8—Cu1	110.12 (10)	F4—P1—F2	89.78 (10)
C9—N8—Cu1	106.13 (9)	F1—P1—F5	90.68 (8)
N8—C9—C10	113.57 (13)	F3—P1—F5	90.69 (8)
N11—C10—C9	113.96 (13)	F4—P1—F5	91.01 (8)
C10—N11—C15	114.07 (13)	F2—P1—F5	90.03 (8)
C10—N11—C12	109.87 (12)	F1—P1—F6	89.68 (7)
C15—N11—C12	112.22 (13)	F3—P1—F6	89.67 (7)
C10—N11—Cu1	101.91 (9)	F4—P1—F6	88.62 (7)
C15—N11—Cu1	107.00 (9)	F2—P1—F6	89.62 (8)
C12—N11—Cu1	111.27 (10)	F5—P1—F6	179.49 (8)
N11—C12—C13	115.47 (13)

(II) [acetonitrile(4,11-dibenzyl-1,4,8,11- tetraazabicyclo[6.6.2]hexadecane-κ⁴N)]copper(II) bis(hexafluorophosphate)

Crystal data

[Cu(C2H3N)(C26H38N4)]2PF6	Z = 2
Mr = 801.14	F(000) = 822
Triclinic, P1	Dx = 1.598 Mg m^−3
a = 9.9695 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.5610 (5) Å	Cell parameters from 7334 reflections
c = 17.7607 (8) Å	θ = 3–20°
α = 101.236 (1)°	µ = 0.85 mm^−1
β = 101.105 (1)°	T = 180 K
γ = 109.157 (1)°	Block, dark green
V = 1664.83 (13) Å^3	0.4 × 0.2 × 0.2 mm

Data collection

Siemens SMART diffractometer	7384 independent reflections
Radiation source: normal-focus sealed tube	6457 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
Detector resolution: 8.192 pixels mm^-1	θmax = 28.5°, θmin = 1.2°
ω scans	h = −12→13
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −14→13
Tmin = 0.774, Tmax = 0.881	l = −20→23
10176 measured reflections

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: inferred from neighbouring sites
wR(F^2) = 0.146	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0648P)^2 + 3.3905P] where P = (Fo^2 + 2Fc^2)/3
7384 reflections	(Δ/σ)max = 0.006
434 parameters	Δρmax = 1.09 e Å^−3
0 restraints	Δρmin = −0.88 e Å^−3

Special details

Experimental. The temperature of the crystal was controlled using the Oxford Cryosystem Cryostream Cooler (Cosier & Glazer, 1986). The data collection nominally covered over a hemisphere of reciprocal space, by a combination of three sets of exposures with different ϕ angles for the crystal; each 10 s exposure covered 0.3° in ω. The crystal-to-detector distance was 5.0 cm. Coverage of the unique set is over 90% complete to at least 25° in θ (though slightly lower to the highest angle used. Crystal decay was found to be negligible by by repeating the initial frames at the end of data collection and analyzing the duplicate reflections. H atoms were added at calculated positions and refined using a riding model. Anisotropic displacement parameters were used for all non-H atoms; H atoms were given isotropic displacement parameters equal to 1.2 (or 1.5 for methyl-H atoms) times the equivalent isotropic displacement parameter of the atom to which they are attached.

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
Cu1	0.72383 (4)	0.64532 (4)	0.74953 (2)	0.02522 (11)
N1	0.6664 (3)	0.7778 (2)	0.83199 (14)	0.0254 (5)
N4	0.9319 (3)	0.7114 (3)	0.83699 (15)	0.0297 (5)
N8	0.7695 (3)	0.5127 (3)	0.66624 (15)	0.0307 (5)
N11	0.6508 (3)	0.4772 (3)	0.79689 (15)	0.0292 (5)
N31	0.7844 (3)	0.7929 (3)	0.68970 (15)	0.0337 (6)
C2	0.7868 (3)	0.8212 (3)	0.90787 (17)	0.0298 (6)
H2A	0.7629	0.7494	0.9370	0.036*
H2B	0.7932	0.9100	0.9423	0.036*
C3	0.9367 (3)	0.8403 (3)	0.89103 (19)	0.0328 (6)
H3A	0.9648	0.9179	0.8663	0.039*
H3B	1.0131	0.8656	0.9421	0.039*
C5	1.0591 (3)	0.7446 (4)	0.8024 (2)	0.0372 (7)
H5A	1.1508	0.7707	0.8454	0.045*
H5B	1.0662	0.8269	0.7822	0.045*
C6	1.0512 (4)	0.6258 (4)	0.7343 (2)	0.0414 (8)
H6A	1.0460	0.5447	0.7553	0.050*
H6B	1.1448	0.6559	0.7192	0.050*
C7	0.9233 (4)	0.5763 (4)	0.6582 (2)	0.0376 (7)
H7A	0.9291	0.6571	0.6366	0.045*
H7B	0.9384	0.5068	0.6181	0.045*
C9	0.7521 (4)	0.3819 (3)	0.6913 (2)	0.0363 (7)
H9A	0.8473	0.3926	0.7266	0.044*
H9B	0.7251	0.3028	0.6435	0.044*
C10	0.6337 (4)	0.3503 (3)	0.73505 (19)	0.0363 (7)
H10A	0.5351	0.3145	0.6961	0.044*
H10B	0.6396	0.2767	0.7610	0.044*
C12	0.5035 (4)	0.4523 (3)	0.8130 (2)	0.0344 (7)
H12A	0.4777	0.3708	0.8348	0.041*
H12B	0.4283	0.4278	0.7616	0.041*
C13	0.4946 (4)	0.5740 (3)	0.8702 (2)	0.0348 (7)
H13A	0.5697	0.5981	0.9216	0.042*
H13B	0.3964	0.5433	0.8804	0.042*
C14	0.5177 (3)	0.7054 (3)	0.84260 (19)	0.0310 (6)
H14A	0.4428	0.6807	0.7910	0.037*
H14B	0.4980	0.7728	0.8818	0.037*
C15	0.9249 (4)	0.5980 (3)	0.87599 (19)	0.0338 (7)
H15A	0.9829	0.6404	0.9327	0.041*
H15B	0.9723	0.5395	0.8502	0.041*
C16	0.7673 (4)	0.5035 (3)	0.87228 (18)	0.0332 (6)
H16A	0.7684	0.4126	0.8783	0.040*
H16B	0.7392	0.5466	0.9183	0.040*
C17	0.6631 (3)	0.9067 (3)	0.80587 (18)	0.0297 (6)
H17A	0.7649	0.9633	0.8067	0.036*
H17B	0.6017	0.8750	0.7498	0.036*
C18	0.6056 (3)	1.0007 (3)	0.85457 (18)	0.0307 (6)
C19	0.6980 (4)	1.1081 (3)	0.9225 (2)	0.0365 (7)
H19A	0.7990	1.1209	0.9401	0.044*
C20	0.6445 (5)	1.1971 (4)	0.9650 (2)	0.0463 (8)
H20A	0.7085	1.2693	1.0115	0.056*
C21	0.4983 (5)	1.1801 (4)	0.9392 (2)	0.0480 (9)
H21A	0.4611	1.2397	0.9683	0.058*
C22	0.4066 (4)	1.0765 (4)	0.8712 (3)	0.0487 (9)
H22A	0.3064	1.0660	0.8531	0.058*
C23	0.4590 (4)	0.9872 (4)	0.8287 (2)	0.0413 (8)
H23A	0.3946	0.9164	0.7818	0.050*
C24	0.6646 (4)	0.4814 (3)	0.58505 (17)	0.0333 (6)
H24A	0.6931	0.5655	0.5657	0.040*
H24B	0.6763	0.4060	0.5473	0.040*
C25	0.5041 (4)	0.4379 (3)	0.58379 (18)	0.0332 (6)
C26	0.4082 (4)	0.2973 (4)	0.5560 (2)	0.0416 (8)
H26A	0.4442	0.2279	0.5370	0.050*
C27	0.2610 (5)	0.2586 (4)	0.5560 (2)	0.0495 (9)
H27A	0.1974	0.1628	0.5378	0.059*
C28	0.2062 (4)	0.3584 (4)	0.5825 (2)	0.0489 (9)
H28A	0.1056	0.3312	0.5829	0.059*
C29	0.2987 (4)	0.4981 (4)	0.6083 (2)	0.0402 (7)
H29A	0.2612	0.5671	0.6257	0.048*
C30	0.4456 (4)	0.5372 (3)	0.60880 (18)	0.0343 (7)
H30A	0.5079	0.6334	0.6265	0.041*
C32	0.8336 (5)	0.8881 (4)	0.6642 (2)	0.0450 (8)
C33	0.8972 (7)	1.0057 (5)	0.6355 (3)	0.0739 (16)
H33A	0.9590	0.9848	0.6020	0.111*
H33B	0.9578	1.0875	0.6809	0.111*
H33C	0.8181	1.0252	0.6038	0.111*
P1	0.25685 (13)	0.86859 (11)	0.57564 (6)	0.0501 (3)
P2	1.09189 (9)	0.28008 (9)	0.86784 (5)	0.03456 (19)
F11	0.1276 (4)	0.9107 (3)	0.53289 (18)	0.0757 (8)
F12	0.3798 (4)	0.8247 (3)	0.6198 (3)	0.1284 (19)
F13	0.1839 (5)	0.8581 (5)	0.6465 (2)	0.1230 (16)
F14	0.3239 (6)	0.8803 (7)	0.5041 (3)	0.164 (2)
F15	0.1558 (5)	0.7101 (3)	0.5317 (3)	0.1265 (18)
F16	0.3562 (4)	1.0242 (3)	0.6212 (2)	0.0884 (10)
F21	1.1366 (3)	0.3811 (5)	0.8157 (3)	0.1260 (18)
F22	1.0440 (3)	0.1769 (3)	0.92155 (19)	0.0792 (9)
F23	1.2569 (3)	0.3287 (3)	0.92069 (18)	0.0769 (9)
F24	0.9256 (3)	0.2306 (3)	0.81601 (16)	0.0666 (7)
F25	1.0655 (5)	0.3923 (4)	0.92798 (19)	0.1120 (15)
F26	1.1094 (6)	0.1584 (5)	0.81033 (19)	0.143 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02845 (19)	0.02773 (19)	0.02295 (18)	0.01262 (14)	0.00828 (13)	0.01013 (13)
N1	0.0266 (12)	0.0274 (11)	0.0231 (11)	0.0104 (9)	0.0061 (9)	0.0096 (9)
N4	0.0273 (12)	0.0354 (13)	0.0297 (12)	0.0134 (10)	0.0076 (10)	0.0144 (10)
N8	0.0383 (14)	0.0356 (13)	0.0268 (12)	0.0208 (11)	0.0125 (10)	0.0121 (10)
N11	0.0344 (13)	0.0272 (12)	0.0267 (12)	0.0108 (10)	0.0088 (10)	0.0103 (10)
N31	0.0383 (14)	0.0406 (15)	0.0269 (13)	0.0184 (12)	0.0123 (11)	0.0102 (11)
C2	0.0329 (15)	0.0301 (14)	0.0257 (14)	0.0123 (12)	0.0062 (11)	0.0074 (11)
C3	0.0280 (14)	0.0345 (15)	0.0309 (15)	0.0088 (12)	0.0024 (12)	0.0091 (12)
C5	0.0262 (15)	0.0499 (19)	0.0401 (18)	0.0156 (14)	0.0093 (13)	0.0200 (15)
C6	0.0362 (17)	0.058 (2)	0.0452 (19)	0.0275 (16)	0.0189 (15)	0.0238 (17)
C7	0.0396 (17)	0.0505 (19)	0.0366 (17)	0.0264 (15)	0.0186 (14)	0.0187 (15)
C9	0.052 (2)	0.0336 (16)	0.0328 (16)	0.0244 (15)	0.0141 (14)	0.0126 (13)
C10	0.0507 (19)	0.0280 (15)	0.0326 (16)	0.0159 (14)	0.0116 (14)	0.0120 (12)
C12	0.0352 (16)	0.0314 (15)	0.0356 (16)	0.0073 (13)	0.0123 (13)	0.0138 (13)
C13	0.0348 (16)	0.0338 (16)	0.0385 (17)	0.0101 (13)	0.0174 (13)	0.0140 (13)
C14	0.0289 (14)	0.0334 (15)	0.0326 (15)	0.0119 (12)	0.0116 (12)	0.0099 (12)
C15	0.0366 (16)	0.0391 (16)	0.0305 (15)	0.0182 (14)	0.0070 (12)	0.0155 (13)
C16	0.0404 (17)	0.0356 (16)	0.0276 (15)	0.0170 (13)	0.0079 (12)	0.0147 (12)
C17	0.0335 (15)	0.0314 (15)	0.0291 (14)	0.0150 (12)	0.0103 (12)	0.0125 (12)
C18	0.0318 (15)	0.0308 (14)	0.0331 (15)	0.0141 (12)	0.0080 (12)	0.0140 (12)
C19	0.0341 (16)	0.0358 (16)	0.0389 (17)	0.0152 (13)	0.0044 (13)	0.0106 (13)
C20	0.062 (2)	0.0433 (19)	0.0355 (18)	0.0280 (18)	0.0082 (16)	0.0060 (15)
C21	0.062 (2)	0.052 (2)	0.050 (2)	0.0378 (19)	0.0265 (19)	0.0194 (17)
C22	0.0392 (19)	0.050 (2)	0.066 (3)	0.0264 (17)	0.0140 (17)	0.0183 (19)
C23	0.0352 (17)	0.0372 (17)	0.049 (2)	0.0173 (14)	0.0034 (14)	0.0091 (15)
C24	0.0451 (18)	0.0367 (16)	0.0219 (14)	0.0218 (14)	0.0087 (12)	0.0061 (12)
C25	0.0439 (17)	0.0339 (15)	0.0233 (14)	0.0180 (13)	0.0065 (12)	0.0086 (12)
C26	0.052 (2)	0.0339 (16)	0.0356 (17)	0.0185 (15)	0.0042 (15)	0.0072 (14)
C27	0.052 (2)	0.0361 (18)	0.048 (2)	0.0073 (16)	0.0037 (17)	0.0102 (16)
C28	0.0412 (19)	0.057 (2)	0.046 (2)	0.0144 (17)	0.0091 (16)	0.0188 (18)
C29	0.0449 (19)	0.0478 (19)	0.0339 (17)	0.0249 (16)	0.0112 (14)	0.0112 (14)
C30	0.0422 (17)	0.0349 (16)	0.0256 (14)	0.0172 (14)	0.0060 (12)	0.0068 (12)
C32	0.066 (2)	0.0421 (19)	0.0302 (17)	0.0238 (18)	0.0144 (16)	0.0099 (14)
C33	0.120 (4)	0.040 (2)	0.049 (2)	0.009 (2)	0.035 (3)	0.0118 (19)
P1	0.0671 (7)	0.0408 (5)	0.0444 (5)	0.0240 (5)	0.0115 (5)	0.0136 (4)
P2	0.0318 (4)	0.0406 (4)	0.0357 (4)	0.0172 (3)	0.0076 (3)	0.0160 (4)
F11	0.087 (2)	0.0622 (16)	0.0802 (19)	0.0358 (15)	0.0076 (16)	0.0268 (15)
F12	0.107 (3)	0.0627 (19)	0.168 (4)	0.0461 (19)	−0.058 (3)	−0.002 (2)
F13	0.109 (3)	0.168 (4)	0.075 (2)	0.011 (3)	0.032 (2)	0.065 (3)
F14	0.124 (4)	0.296 (7)	0.080 (3)	0.081 (4)	0.059 (3)	0.036 (4)
F15	0.117 (3)	0.0535 (17)	0.149 (4)	0.0393 (19)	−0.062 (3)	−0.018 (2)
F16	0.087 (2)	0.0399 (14)	0.116 (3)	0.0120 (14)	0.0046 (19)	0.0169 (15)
F21	0.0527 (17)	0.195 (4)	0.151 (3)	0.019 (2)	0.0186 (19)	0.150 (3)
F22	0.0538 (15)	0.089 (2)	0.094 (2)	0.0122 (14)	0.0057 (14)	0.0635 (18)
F23	0.0324 (12)	0.104 (2)	0.093 (2)	0.0111 (13)	0.0021 (12)	0.0673 (18)
F24	0.0387 (12)	0.0864 (18)	0.0653 (16)	0.0186 (12)	−0.0064 (11)	0.0298 (14)
F25	0.175 (4)	0.109 (3)	0.0598 (18)	0.114 (3)	−0.020 (2)	−0.0127 (17)
F26	0.206 (5)	0.212 (5)	0.0520 (18)	0.183 (4)	−0.007 (2)	−0.011 (2)

Geometric parameters (Å, º)

Cu1—N31	2.049 (3)	C18—C19	1.394 (5)
Cu1—N8	2.056 (3)	C18—C23	1.395 (5)
Cu1—N11	2.088 (2)	C19—C20	1.395 (5)
Cu1—N1	2.116 (2)	C20—C21	1.380 (6)
Cu1—N4	2.142 (3)	C21—C22	1.377 (6)
N1—C2	1.497 (4)	C22—C23	1.389 (5)
N1—C14	1.496 (4)	C24—C25	1.507 (5)
N1—C17	1.530 (4)	C25—C30	1.399 (4)
N4—C15	1.485 (4)	C25—C26	1.402 (5)
N4—C3	1.486 (4)	C26—C27	1.388 (6)
N4—C5	1.485 (4)	C27—C28	1.383 (6)
N8—C9	1.499 (4)	C28—C29	1.385 (5)
N8—C7	1.507 (4)	C29—C30	1.383 (5)
N8—C24	1.513 (4)	C32—C33	1.435 (6)
N11—C10	1.495 (4)	P1—F14	1.552 (4)
N11—C12	1.498 (4)	P1—F16	1.562 (3)
N11—C16	1.504 (4)	P1—F12	1.574 (3)
N31—C32	1.182 (5)	P1—F13	1.575 (4)
C2—C3	1.536 (4)	P1—F15	1.584 (3)
C5—C6	1.532 (5)	P1—F11	1.602 (3)
C6—C7	1.533 (5)	P2—F21	1.557 (3)
C9—C10	1.518 (5)	P2—F26	1.559 (3)
C12—C13	1.514 (4)	P2—F25	1.560 (3)
C13—C14	1.523 (4)	P2—F23	1.586 (2)
C15—C16	1.541 (5)	P2—F24	1.589 (2)
C17—C18	1.514 (4)	P2—F22	1.602 (3)
N31—Cu1—N8	88.19 (10)	C19—C18—C23	118.2 (3)
N31—Cu1—N11	173.04 (10)	C19—C18—C17	121.7 (3)
N8—Cu1—N11	86.28 (10)	C23—C18—C17	119.9 (3)
N31—Cu1—N1	91.98 (10)	C18—C19—C20	121.0 (3)
N8—Cu1—N1	177.33 (10)	C21—C20—C19	119.8 (4)
N11—Cu1—N1	93.35 (9)	C22—C21—C20	119.9 (3)
N31—Cu1—N4	97.76 (10)	C21—C22—C23	120.7 (3)
N8—Cu1—N4	95.25 (10)	C22—C23—C18	120.5 (3)
N11—Cu1—N4	86.96 (10)	C25—C24—N8	114.5 (2)
N1—Cu1—N4	87.37 (10)	C30—C25—C26	117.9 (3)
C2—N1—C14	111.7 (2)	C30—C25—C24	121.0 (3)
C2—N1—C17	109.7 (2)	C26—C25—C24	121.1 (3)
C14—N1—C17	107.1 (2)	C27—C26—C25	120.5 (3)
C2—N1—Cu1	104.17 (17)	C28—C27—C26	120.5 (3)
C14—N1—Cu1	112.26 (18)	C27—C28—C29	119.7 (4)
C17—N1—Cu1	111.96 (17)	C30—C29—C28	120.1 (3)
C15—N4—C3	113.3 (2)	C29—C30—C25	121.3 (3)
C15—N4—C5	111.2 (2)	N31—C32—C33	178.2 (5)
C3—N4—C5	110.1 (2)	F14—P1—F16	90.9 (3)
C15—N4—Cu1	107.17 (19)	F14—P1—F12	92.7 (3)
C3—N4—Cu1	102.02 (17)	F16—P1—F12	88.65 (18)
C5—N4—Cu1	112.85 (19)	F14—P1—F13	177.8 (3)
C9—N8—C7	109.6 (2)	F16—P1—F13	89.3 (2)
C9—N8—C24	111.0 (3)	F12—P1—F13	89.4 (3)
C7—N8—C24	106.5 (2)	F14—P1—F15	90.5 (3)
C9—N8—Cu1	108.14 (18)	F16—P1—F15	178.4 (3)
C7—N8—Cu1	112.3 (2)	F12—P1—F15	90.66 (18)
C24—N8—Cu1	109.31 (18)	F13—P1—F15	89.3 (3)
C10—N11—C12	107.0 (2)	F14—P1—F11	89.5 (3)
C10—N11—C16	111.3 (2)	F16—P1—F11	92.07 (17)
C12—N11—C16	110.6 (2)	F12—P1—F11	177.7 (3)
C10—N11—Cu1	106.24 (18)	F13—P1—F11	88.4 (2)
C12—N11—Cu1	114.11 (19)	F15—P1—F11	88.57 (17)
C16—N11—Cu1	107.55 (18)	F21—P2—F26	92.8 (3)
C32—N31—Cu1	171.3 (3)	F21—P2—F25	91.7 (3)
N1—C2—C3	111.2 (2)	F26—P2—F25	175.1 (3)
N4—C3—C2	111.7 (2)	F21—P2—F23	92.98 (15)
N4—C5—C6	114.8 (3)	F26—P2—F23	90.9 (2)
C5—C6—C7	117.4 (3)	F25—P2—F23	90.7 (2)
N8—C7—C6	116.8 (3)	F21—P2—F24	87.86 (16)
N8—C9—C10	111.2 (3)	F26—P2—F24	89.5 (2)
N11—C10—C9	111.6 (3)	F25—P2—F24	88.87 (19)
N11—C12—C13	115.2 (3)	F23—P2—F24	179.09 (16)
C12—C13—C14	115.8 (3)	F21—P2—F22	179.2 (2)
N1—C14—C13	116.9 (3)	F26—P2—F22	87.7 (3)
N4—C15—C16	114.4 (2)	F25—P2—F22	87.8 (2)
N11—C16—C15	115.1 (2)	F23—P2—F22	87.57 (14)
C18—C17—N1	117.0 (2)	F24—P2—F22	91.60 (15)