Bis(tert-butyl isocyanide-[kappa]C)[4-fluoro-N-({2-[N-(4-fluoro­phenyl)­carbox­imido­yl]­cyclo­penta-2,4-dien-1-yl­idene}­methyl)­anilinido-[kappa]²N,N']copper(I)

The solid-state structure of the title compound, [Cu(C₁₉H₁₃F₂N₂)(C₅H₉N)₂], shows that the Cu^I centre adopts a distorted tetra­hedral coordination geometry, being coordinated by two N atoms of the 6-amino­fulvene-2-aldimine (AFA) chelating ligand and by the bridgehead C atoms of the two isocyanide ligands. The cyclo­penta­dienyl and imine components of the AFA ligand are approximately coplanar, with an angle between the planes of 5.00 (3)°. The Cu atom lies 0.6460 (3) Å above the imine plane defined by the N and C atoms of the seven-membered metallocycle. There is also an uncommon C-H...Cu anagostic inter­action, with an intra­molecular Cu...H distance of 2.67 Å, which is less than the sum of the van der Waals radii.

S1. Comment

The diimine-substituted cyclopentadienyl 6-aminofulvene-2-aldimines (AFAs) have recently attracted attention as ligands for a variety of metals because of both their similarity to well established ligand systems such as β-diketiminate, aminotroponiminate or anilidoiminate ligands (Willcocks et al., 2011; Bailey et al., 2003, 2007, 2010) and their ability to bind to metal centres via the diimine donor groups or via the cyclopentadienyl unit (Bailey et al., 2003, 2007).

As part of a wider study into the coordination chemistry of Cu^I complexes, we have recently reported the double migratory insertion of phenyl isocyanide (Ph—NC) into two vicinal sp² C—H bonds of the η⁵-coordinated cyclopentadienyl group in the complex [(η⁵-C₅H₅)Cu(CNPh)], resulting in the formation and isolation of the AFA complexes [(Ph₂–AFA)Cu(CNPh)] and [(Ph₂-AFA)Cu(CNPh)₂}] (Johnson et al., 2009).

In an attempt to elucidate the mechanism by which the AFA complexes are formed and, more specifically, to better understand the effect that the isocyanide substituent has on the insertion reaction, we investigated a series of reactions between the complex [(η⁵-C₅H₅)Cu(CN^tBu)] and varying amounts of alkyl and aryl isocyanides. The reaction of both [(η⁵-C₅H₅)Cu(CN^tBu)] and [(η⁵-C₅H₅)Cu(CNPh)] with an excess of the alkyl isocyanide, CN^tBu (ca 4 equivalents) was studied, but ¹H NMR spectroscopic studies failed to establish any evidence of reaction. However, the analogous reaction of [(η⁵-C₅H₅)Cu(CN^tBu)] (Kruck et al., 1993) with an excess (4 equivalents) of CNPh has been shown to produce the AFA complex, [(Ph₂–AFA)Cu(CNPh)₂], as evidenced by the appearance of indicative resonances for the ligand system in the ¹H NMR spectra, and provides an alternative route for the synthesis of the complex (Johnson et al., 2009). We previously noted that the reaction of [(η⁵-C₅H₅)Cu(CN^tBu)] with the electron-withdrawing isocyanides CN(p-C₆H₄F) and CN(p-C₆H₄NO₂) shows a much more rapid production of AFA complexes (<< 12 h), indicating that the electronic nature of the isocyanide is a significant factor in the migratory insertion of isocyanides into C—H bonds of the Cu—C₅H₅ systems (Johnson et al., 2009).

The title complex, (I), was formed by the reaction of 4-fluorophenyl isocyanide with [(η⁵-C₅H₅)Cu(CN^tBu)] in tetrahydrofuran in a copper-mediated insertion of two equivalents of CN(4-C₆H₄F) into two vicinal C—H bonds of the cyclopentadienyl moiety of the complex [(η⁵-C₅H₅)Cu(CN^tBu)].

Complex (I) crystallizes in the monoclinic space group P2₁/n (Fig. 1) and an examination of the crystal packing shows no abnormally short intermolecular contacts. The shortest intermolecular interaction is 2.29 Å between atoms F1 and H20(x + 1/2, -y + 1/2, z + 1/2).

The molecular structure of (I) (Fig. 1) shows the Cu^I centre to be coordinated by the two N atoms of the AFA ligand and the two divalent C atoms of the isocyanide ligands (Table 1), which are comparable with the Cu^I–AFA and Cu^I–isocyanide interactions in related complexes (Willcocks et al., 2011), resulting in a coordination environment about the Cu^I centre that is best described as approximately tetrahedral. The cyclopentadienyl and imine portions of the AFA ligand are approximately coplanar. The dihedral angle between the C7–C11 and N2/C6/C7/C11/C12/N3 planes is 5.00 (3)°. The Cu^I atom is located 0.6460 (3) Å above the imine portion of the AFA ligand (N2/C6/C7/C11/C12/N3). As with related (AFA)Cu(CNR)₂ complexes (Willcocks et al., 2011), the bite angle of the AFA ligand in (I) [N2—Cu1—N3 = 106.60 (9)°] is compressed, as a result of pyramidalization at the metal centre.

An interesting feature of this structure is the presence of an intramolecular C—H···Cu anagostic interaction in the solid state. The distance between the H atom and the Cu^I ion (Cu1···H24 = 2.67 Å and Cu1···H24—C24 = 114°) is shorter than the sum of their van der Waals radii (Nag et al., 2007). Similar interactions do not only represent a structural curiosity, but these largely electrostatic interactions are believed to have considerable relevance to many catalytic processes (Brookhart et al., 2007). The weak interaction between the ortho-CH group of one of the AFA imine substituents and the metal centre is facilitated by a concomitant re-orientation of the fluorophenyl imine substituent, such that the angle subtended between the phenyl ring and the plane defined by the backbone atoms of the AFA ligand, [C₅(CN)₂], is considerably closer to coplanarity [37.69 (4)°] than the aryl substituent, which does not engage in an additional interaction with the Cu^I centre [67.36 (4)°].

Both isocyanide ligands are distorted away from linearity, such that the isocyanide ligand C1 is oriented, or bent, towards the imine substituent on N2, and similarly the isocyanide ligand C25 is oriented towards the imine substituent on N3. Density functional theory calculations on related systems have suggested there is considerable flexibility in the coordination geometry about the copper centres in these systems, with only small energy differences between potential geometric isomers (Willcocks et al., 2011).

Related literature

For related literature, see: Bailey et al. (2003, 2007, 2010); Brookhart et al. (2007); Johnson et al. (2009); Kruck & Terfloth (1993); Nag et al. (2007); Willcocks et al. (2011).

S2. Experimental

To a solution of CpCuCN^tBu (0.21 g, 1.0 mmol) in tetrahydrofuran (10 ml), p-FPhNC (0.27 g, 2.20 mmol) was added. The reaction mixture was stirred for 16 h and the volatiles were then removed under reduced pressure. The resultant solid was extracted with warm hexane (3 × 20 ml) and filtered. Further concentration and storage at 245 K resulted in the formation of (I) as dark-yellow crystals suitable for a crystallographic investigation (yield 0.25 g, 47%). Analysis, calculated for C₂₉H₃₁CuF₂N₄: C 64.85, H 5.82, N 10.43%; found: C 65.01, H 5.84, N 10.35%. Spectroscopic analysis: ¹H NMR (300 MHz, 296 K, CDCl₃, δ, p.p.m.): 1.26 (singlet, 18H, ^tBu), 6.19 (triplet, J = 3.60 Hz, 1H, CHCHCH), 6.78 (doublet, J = 3.54 Hz, 2H, CHCHCH), 6.86–7.20 (complex multiplet, 8H, Ph—F), 8.08 (singlet, 2H, ArNCH).

S3. Refinement

Methyl H atoms were located in circular difference Fourier syntheses and thereafter refined as part of a rigid rotating group, with C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C). The aromatic H atoms were placed geometrically and refined with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level. The double-dashed line indicates the intramolecular C—H···Cu anagostic interaction.

Bis(tert-butyl isocyanide-κC)[4-fluoro-N-({2- [N-(4-fluorophenyl)carboximidoyl]cyclopenta-2,4-dien-1- ylidene}methyl)anilinido-κ²N,N']copper(I)

Crystal data

[Cu(C19H13F2N2)(C5H9N)2]	F(000) = 1120
Mr = 537.12	Dx = 1.29 Mg m^−3
Monoclinic, P21/n	Synchrotron radiation, λ = 0.6939 Å
Hall symbol: -P 2yn	Cell parameters from 31260 reflections
a = 13.943 (4) Å	θ = 1.9–31.6°
b = 9.240 (2) Å	µ = 0.79 mm^−1
c = 21.642 (5) Å	T = 150 K
β = 97.462 (5)°	Needle, yellow
V = 2764.6 (12) Å^3	0.08 × 0.03 × 0.02 mm
Z = 4

Data collection

Bruker APEXII diffractometer	5331 reflections with I > 2σ(I)
ω scans	Rint = 0.083
Absorption correction: multi-scan (Blessing, 1995)	θmax = 28.0°, θmin = 1.9°
Tmin = 0.937, Tmax = 0.985	h = −18→18
27368 measured reflections	k = −12→12
7148 independent reflections	l = −29→29

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.058	w = 1/[σ^2(Fo^2) + (0.P)^2 + 0.6015P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.165	(Δ/σ)max = 0.002
S = 1.13	Δρmax = 0.47 e Å^−3
7148 reflections	Δρmin = −0.70 e Å^−3
331 parameters

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
Cu1	0.33358 (2)	0.06340 (3)	0.615672 (15)	0.02938 (13)
N1	0.32502 (17)	−0.2651 (3)	0.59309 (11)	0.0340 (5)
N2	0.27499 (17)	0.1278 (2)	0.69276 (11)	0.0309 (5)
N3	0.24473 (16)	0.1421 (2)	0.53987 (11)	0.0310 (5)
N4	0.53299 (18)	0.2028 (3)	0.65100 (11)	0.0362 (5)
F1	0.51405 (14)	0.1533 (2)	0.91771 (9)	0.0534 (5)
F2	0.41146 (16)	0.2517 (2)	0.32463 (9)	0.0614 (6)
C1	0.3296 (2)	−0.1435 (3)	0.60434 (13)	0.0342 (6)
C2	0.3143 (2)	−0.4177 (3)	0.57546 (15)	0.0374 (7)
C3	0.3080 (3)	−0.5068 (4)	0.63403 (17)	0.0520 (9)
H3A	0.3660	−0.4901	0.6640	0.078*
H3B	0.3035	−0.6097	0.6232	0.078*
H3C	0.2505	−0.4778	0.6527	0.078*
C4	0.4034 (3)	−0.4599 (3)	0.54540 (18)	0.0487 (8)
H4A	0.4081	−0.3977	0.5092	0.073*
H4B	0.3978	−0.5611	0.5319	0.073*
H4C	0.4615	−0.4480	0.5757	0.073*
C5	0.2220 (3)	−0.4296 (4)	0.53027 (19)	0.0562 (10)
H5A	0.1675	−0.3935	0.5502	0.084*
H5B	0.2106	−0.5312	0.5184	0.084*
H5C	0.2282	−0.3720	0.4930	0.084*
C6	0.1844 (2)	0.1535 (3)	0.69761 (14)	0.0319 (6)
H6	0.1709	0.1793	0.7381	0.038*
C7	0.1034 (2)	0.1483 (3)	0.65107 (15)	0.0359 (6)
C8	0.0097 (2)	0.1472 (3)	0.67007 (16)	0.0407 (7)
H8	−0.0035	0.1532	0.7120	0.049*
C9	−0.0599 (2)	0.1361 (4)	0.61805 (17)	0.0471 (8)
H9	−0.1279	0.1314	0.6183	0.057*
C10	−0.0124 (2)	0.1330 (4)	0.56595 (17)	0.0458 (8)
H10	−0.0432	0.1281	0.5242	0.055*
C11	0.0894 (2)	0.1382 (3)	0.58380 (14)	0.0354 (6)
C12	0.1501 (2)	0.1428 (3)	0.53613 (14)	0.0333 (6)
H12	0.1170	0.1471	0.4949	0.040*
C13	0.3399 (2)	0.1400 (3)	0.74892 (13)	0.0311 (6)
C14	0.4021 (2)	0.0253 (3)	0.76791 (14)	0.0349 (6)
H14	0.4041	−0.0566	0.7415	0.042*
C15	0.4606 (2)	0.0292 (3)	0.82437 (15)	0.0391 (7)
H15	0.5010	−0.0505	0.8380	0.047*
C16	0.4591 (2)	0.1518 (4)	0.86056 (14)	0.0395 (7)
C17	0.4027 (2)	0.2704 (3)	0.84252 (14)	0.0391 (7)
H17	0.4048	0.3545	0.8679	0.047*
C18	0.3431 (2)	0.2638 (3)	0.78656 (14)	0.0353 (6)
H18	0.3036	0.3445	0.7733	0.042*
C19	0.2841 (2)	0.1669 (3)	0.48297 (12)	0.0299 (6)
C20	0.2373 (2)	0.2516 (3)	0.43439 (14)	0.0385 (7)
H20	0.1753	0.2907	0.4381	0.046*
C21	0.2794 (2)	0.2794 (4)	0.38117 (14)	0.0430 (7)
H21	0.2469	0.3365	0.3484	0.052*
C22	0.3689 (2)	0.2230 (4)	0.37666 (14)	0.0426 (7)
C23	0.4184 (2)	0.1402 (3)	0.42303 (14)	0.0411 (7)
H23	0.4809	0.1034	0.4191	0.049*
C24	0.3746 (2)	0.1117 (3)	0.47591 (14)	0.0354 (6)
H24	0.4074	0.0529	0.5080	0.042*
C25	0.4588 (2)	0.1541 (3)	0.63213 (13)	0.0347 (6)
C26	0.6265 (2)	0.2550 (3)	0.68062 (14)	0.0395 (7)
C27	0.6071 (3)	0.3603 (4)	0.73152 (19)	0.0609 (10)
H27A	0.5720	0.4446	0.7127	0.091*
H27B	0.6687	0.3918	0.7546	0.091*
H27C	0.5681	0.3124	0.7601	0.091*
C28	0.6846 (3)	0.1236 (4)	0.70834 (18)	0.0524 (9)
H28A	0.6486	0.0745	0.7382	0.079*
H28B	0.7473	0.1561	0.7296	0.079*
H28C	0.6951	0.0563	0.6748	0.079*
C29	0.6779 (3)	0.3242 (5)	0.63055 (19)	0.0613 (10)
H29A	0.6809	0.2551	0.5965	0.092*
H29B	0.7436	0.3516	0.6483	0.092*
H29C	0.6423	0.4106	0.6145	0.092*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0285 (2)	0.02564 (19)	0.0345 (2)	0.00214 (12)	0.00608 (14)	−0.00189 (13)
N1	0.0385 (13)	0.0275 (12)	0.0376 (13)	0.0028 (10)	0.0110 (10)	−0.0023 (10)
N2	0.0316 (12)	0.0258 (11)	0.0359 (12)	0.0000 (9)	0.0069 (10)	0.0001 (9)
N3	0.0286 (12)	0.0293 (12)	0.0357 (12)	0.0021 (9)	0.0068 (9)	−0.0024 (9)
N4	0.0320 (13)	0.0390 (14)	0.0375 (13)	−0.0033 (10)	0.0045 (10)	−0.0022 (11)
F1	0.0462 (11)	0.0677 (14)	0.0434 (11)	−0.0123 (9)	−0.0045 (8)	−0.0039 (9)
F2	0.0739 (15)	0.0712 (14)	0.0441 (11)	0.0071 (11)	0.0268 (10)	0.0127 (10)
C1	0.0357 (15)	0.0330 (15)	0.0356 (15)	0.0014 (11)	0.0113 (12)	0.0000 (11)
C2	0.0439 (17)	0.0261 (14)	0.0446 (17)	0.0018 (12)	0.0143 (13)	−0.0081 (12)
C3	0.070 (2)	0.0310 (16)	0.061 (2)	0.0061 (16)	0.0317 (19)	0.0058 (15)
C4	0.055 (2)	0.0339 (16)	0.062 (2)	0.0045 (14)	0.0265 (17)	−0.0084 (15)
C5	0.054 (2)	0.055 (2)	0.061 (2)	−0.0077 (17)	0.0142 (18)	−0.0219 (17)
C6	0.0329 (14)	0.0241 (13)	0.0402 (15)	0.0024 (10)	0.0111 (12)	0.0008 (11)
C7	0.0336 (15)	0.0281 (14)	0.0481 (17)	0.0007 (11)	0.0140 (13)	0.0016 (12)
C8	0.0325 (15)	0.0377 (16)	0.0542 (19)	0.0054 (12)	0.0145 (14)	0.0028 (14)
C9	0.0275 (15)	0.0497 (19)	0.066 (2)	−0.0028 (13)	0.0111 (14)	−0.0015 (16)
C10	0.0312 (15)	0.0492 (19)	0.057 (2)	−0.0030 (14)	0.0072 (14)	−0.0016 (16)
C11	0.0313 (14)	0.0314 (14)	0.0438 (16)	0.0003 (11)	0.0062 (12)	0.0017 (12)
C12	0.0316 (14)	0.0292 (14)	0.0383 (15)	−0.0004 (11)	0.0019 (11)	−0.0026 (11)
C13	0.0338 (14)	0.0277 (13)	0.0334 (14)	−0.0029 (11)	0.0095 (11)	0.0002 (11)
C14	0.0360 (15)	0.0301 (14)	0.0393 (16)	0.0014 (12)	0.0082 (12)	−0.0027 (12)
C15	0.0349 (15)	0.0376 (16)	0.0447 (17)	0.0002 (12)	0.0046 (13)	0.0019 (13)
C16	0.0352 (15)	0.0483 (18)	0.0349 (15)	−0.0116 (13)	0.0041 (12)	−0.0038 (13)
C17	0.0461 (17)	0.0346 (16)	0.0389 (16)	−0.0099 (13)	0.0142 (13)	−0.0075 (12)
C18	0.0428 (16)	0.0266 (14)	0.0389 (15)	−0.0017 (12)	0.0140 (12)	−0.0019 (11)
C19	0.0308 (14)	0.0282 (13)	0.0310 (13)	−0.0015 (10)	0.0044 (11)	−0.0046 (10)
C20	0.0391 (16)	0.0375 (16)	0.0388 (16)	0.0047 (13)	0.0040 (13)	0.0007 (13)
C21	0.0530 (19)	0.0423 (17)	0.0332 (15)	0.0045 (14)	0.0031 (14)	0.0028 (13)
C22	0.0508 (19)	0.0440 (18)	0.0343 (15)	−0.0022 (14)	0.0107 (14)	−0.0003 (13)
C23	0.0389 (16)	0.0446 (18)	0.0423 (17)	0.0085 (13)	0.0144 (13)	0.0024 (14)
C24	0.0372 (15)	0.0350 (15)	0.0346 (15)	0.0056 (12)	0.0074 (12)	0.0030 (12)
C25	0.0370 (16)	0.0316 (15)	0.0361 (15)	0.0030 (12)	0.0070 (12)	−0.0012 (11)
C26	0.0330 (15)	0.0433 (17)	0.0416 (16)	−0.0047 (13)	0.0024 (12)	−0.0026 (13)
C27	0.053 (2)	0.061 (2)	0.067 (2)	−0.0072 (18)	0.0002 (18)	−0.026 (2)
C28	0.048 (2)	0.047 (2)	0.058 (2)	−0.0005 (16)	−0.0055 (17)	0.0024 (16)
C29	0.0386 (19)	0.070 (3)	0.076 (3)	−0.0130 (17)	0.0099 (18)	0.015 (2)

Geometric parameters (Å, º)

Cu1—C1	1.927 (3)	C10—H10	0.9500
Cu1—C25	1.928 (3)	C11—C12	1.418 (4)
Cu1—N2	2.039 (2)	C12—H12	0.9500
Cu1—N3	2.056 (2)	C13—C14	1.398 (4)
Cu1—H24	2.6692	C13—C18	1.401 (4)
N1—C1	1.150 (4)	C14—C15	1.379 (4)
N1—C2	1.463 (4)	C14—H14	0.9500
N2—C6	1.303 (3)	C15—C16	1.379 (4)
N2—C13	1.422 (4)	C15—H15	0.9500
N3—C12	1.311 (4)	C16—C17	1.375 (5)
N3—C19	1.431 (3)	C17—C18	1.378 (4)
N4—C25	1.153 (4)	C17—H17	0.9500
N4—C26	1.458 (4)	C18—H18	0.9500
F1—C16	1.368 (3)	C19—C24	1.387 (4)
F2—C22	1.365 (3)	C19—C20	1.402 (4)
C2—C5	1.516 (5)	C20—C21	1.384 (4)
C2—C3	1.523 (4)	C20—H20	0.9500
C2—C4	1.525 (4)	C21—C22	1.367 (5)
C3—H3A	0.9800	C21—H21	0.9500
C3—H3B	0.9800	C22—C23	1.374 (4)
C3—H3C	0.9800	C23—C24	1.391 (4)
C4—H4A	0.9800	C23—H23	0.9500
C4—H4B	0.9800	C24—H24	0.9500
C4—H4C	0.9800	C26—C29	1.516 (5)
C5—H5A	0.9800	C26—C27	1.520 (5)
C5—H5B	0.9800	C26—C28	1.538 (5)
C5—H5C	0.9800	C27—H27A	0.9800
C6—C7	1.413 (4)	C27—H27B	0.9800
C6—H6	0.9500	C27—H27C	0.9800
C7—C8	1.420 (4)	C28—H28A	0.9800
C7—C11	1.447 (4)	C28—H28B	0.9800
C8—C9	1.391 (5)	C28—H28C	0.9800
C8—H8	0.9500	C29—H29A	0.9800
C9—C10	1.380 (5)	C29—H29B	0.9800
C9—H9	0.9500	C29—H29C	0.9800
C10—C11	1.422 (4)
C1—Cu1—C25	117.70 (12)	C14—C13—N2	119.5 (2)
C1—Cu1—N2	112.67 (10)	C18—C13—N2	122.1 (3)
C25—Cu1—N2	99.89 (11)	C15—C14—C13	120.9 (3)
C1—Cu1—N3	104.18 (11)	C15—C14—H14	119.5
C25—Cu1—N3	115.54 (11)	C13—C14—H14	119.5
N2—Cu1—N3	106.60 (9)	C16—C15—C14	118.3 (3)
C1—N1—C2	176.3 (3)	C16—C15—H15	120.9
C6—N2—C13	115.6 (2)	C14—C15—H15	120.9
C6—N2—Cu1	127.9 (2)	F1—C16—C17	118.8 (3)
C13—N2—Cu1	116.40 (17)	F1—C16—C15	118.2 (3)
C12—N3—C19	116.2 (2)	C17—C16—C15	123.0 (3)
C12—N3—Cu1	123.2 (2)	C16—C17—C18	118.1 (3)
C19—N3—Cu1	118.97 (17)	C16—C17—H17	120.9
C25—N4—C26	174.0 (3)	C18—C17—H17	120.9
N1—C1—Cu1	175.0 (3)	C17—C18—C13	121.2 (3)
N1—C2—C5	106.7 (3)	C17—C18—H18	119.4
N1—C2—C3	108.6 (3)	C13—C18—H18	119.4
C5—C2—C3	111.2 (3)	C24—C19—C20	117.7 (3)
N1—C2—C4	107.2 (2)	C24—C19—N3	119.5 (2)
C5—C2—C4	112.1 (3)	C20—C19—N3	122.7 (2)
C3—C2—C4	110.8 (3)	C21—C20—C19	121.4 (3)
C2—C3—H3A	109.5	C21—C20—H20	119.3
C2—C3—H3B	109.5	C19—C20—H20	119.3
H3A—C3—H3B	109.5	C22—C21—C20	118.6 (3)
C2—C3—H3C	109.5	C22—C21—H21	120.7
H3A—C3—H3C	109.5	C20—C21—H21	120.7
H3B—C3—H3C	109.5	F2—C22—C21	118.9 (3)
C2—C4—H4A	109.5	F2—C22—C23	118.7 (3)
C2—C4—H4B	109.5	C21—C22—C23	122.4 (3)
H4A—C4—H4B	109.5	C22—C23—C24	118.3 (3)
C2—C4—H4C	109.5	C22—C23—H23	120.9
H4A—C4—H4C	109.5	C24—C23—H23	120.9
H4B—C4—H4C	109.5	C19—C24—C23	121.6 (3)
C2—C5—H5A	109.5	C19—C24—H24	119.2
C2—C5—H5B	109.5	C23—C24—H24	119.2
H5A—C5—H5B	109.5	N4—C25—Cu1	169.9 (3)
C2—C5—H5C	109.5	N4—C26—C29	107.7 (3)
H5A—C5—H5C	109.5	N4—C26—C27	107.3 (3)
H5B—C5—H5C	109.5	C29—C26—C27	113.2 (3)
N2—C6—C7	129.0 (3)	N4—C26—C28	107.9 (3)
N2—C6—H6	115.5	C29—C26—C28	109.8 (3)
C7—C6—H6	115.5	C27—C26—C28	110.9 (3)
C6—C7—C8	118.3 (3)	C26—C27—H27A	109.5
C6—C7—C11	135.3 (3)	C26—C27—H27B	109.5
C8—C7—C11	106.4 (3)	H27A—C27—H27B	109.5
C9—C8—C7	109.7 (3)	C26—C27—H27C	109.5
C9—C8—H8	125.1	H27A—C27—H27C	109.5
C7—C8—H8	125.1	H27B—C27—H27C	109.5
C10—C9—C8	107.7 (3)	C26—C28—H28A	109.5
C10—C9—H9	126.1	C26—C28—H28B	109.5
C8—C9—H9	126.1	H28A—C28—H28B	109.5
C9—C10—C11	110.2 (3)	C26—C28—H28C	109.5
C9—C10—H10	124.9	H28A—C28—H28C	109.5
C11—C10—H10	124.9	H28B—C28—H28C	109.5
C12—C11—C10	118.2 (3)	C26—C29—H29A	109.5
C12—C11—C7	135.6 (3)	C26—C29—H29B	109.5
C10—C11—C7	106.0 (3)	H29A—C29—H29B	109.5
N3—C12—C11	130.3 (3)	C26—C29—H29C	109.5
N3—C12—H12	114.9	H29A—C29—H29C	109.5
C11—C12—H12	114.9	H29B—C29—H29C	109.5
C14—C13—C18	118.4 (3)
C1—Cu1—N2—C6	−85.4 (3)	C19—N3—C12—C11	−172.1 (3)
C25—Cu1—N2—C6	148.8 (2)	Cu1—N3—C12—C11	22.3 (4)
N3—Cu1—N2—C6	28.2 (3)	C10—C11—C12—N3	−176.9 (3)
C1—Cu1—N2—C13	91.5 (2)	C6—N2—C13—C14	127.1 (3)
C25—Cu1—N2—C13	−34.3 (2)	Cu1—N2—C13—C14	−50.2 (3)
N3—Cu1—N2—C13	−154.86 (18)	C6—N2—C13—C18	−52.4 (3)
C1—Cu1—N3—C12	79.4 (2)	Cu1—N2—C13—C18	130.3 (2)
C25—Cu1—N3—C12	−149.9 (2)	N2—C13—C14—C15	−175.1 (3)
N2—Cu1—N3—C12	−40.0 (2)	C14—C15—C16—F1	177.3 (3)
H24—Cu1—N3—C12	153.3	C14—C15—C16—C17	−0.7 (5)
C1—Cu1—N3—C19	−85.8 (2)	F1—C16—C17—C18	−176.0 (3)
C25—Cu1—N3—C19	44.9 (2)	N2—C13—C18—C17	176.4 (3)
N2—Cu1—N3—C19	154.84 (18)	C12—N3—C19—C24	−153.6 (3)
C13—N2—C6—C7	−179.1 (3)	Cu1—N3—C19—C24	12.6 (3)
Cu1—N2—C6—C7	−2.2 (4)	C12—N3—C19—C20	29.7 (4)
N2—C6—C7—C8	165.4 (3)	Cu1—N3—C19—C20	−164.0 (2)
N2—C6—C7—C11	−11.9 (5)	N3—C19—C20—C21	176.8 (3)
C6—C7—C8—C9	−177.6 (3)	C20—C21—C22—F2	−179.1 (3)
C8—C7—C11—C12	175.2 (3)	F2—C22—C23—C24	179.9 (3)
C6—C7—C11—C10	178.1 (3)	N3—C19—C24—C23	−176.1 (3)
C8—C7—C11—C10	0.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C20—H20···F1^i	0.95	2.29	3.209 (4)	162

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.