Tris(2,2′-bipyridine-κ²N,N′)copper(II) bis­(tetra­fluorido­borate)

The title compound, [Cu(C₁₀H₈N₂)₃](BF₄)₂, shows the expected Jahn–Teller distortion at the pseudo-octa­hedrally coordinated Cu^II atom. Each Cu^II complex cation is surrounded by six BF₄⁻ anions and each anion by three cations with weak C—H...F hydrogen bonds between them. One of the two BF₄⁻ anions exhibits a rotational disorder (0.6:0.4) around one of the B—F bonds.

Key indicators

• Single-crystal X-ray study
• T = 203 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in solvent or counterion
• R factor = 0.036
• wR factor = 0.088
• Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.28
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          4
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         B2
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         B1
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      23.00 Perc.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Metal complexes with three (modified) 2,2'-bipyridine ligands are of continous interest (Janiak et al., 1999; Wu et al., 2003; Yang et al., 2004a,b). Tris(2,2'-bipyridine)copper structure are known with the anions tris(oxalato)chromate(III) (Juric et al., 2006), polyoxovanadate (Dong et al., 2006), polyoxotungstate (Niu et al., 2004), bis(bis(2-thioxo-1,3-dithiole-4,5-dithiolato)- nickelate(II) (Faulmann et al., 1998), tetraphenylborate (Murphy et al., 2006) and perchlorate (Anderson, 1972; Liu et al., 1991; Majumdar et al., 1998; Pavlishchuk et al., 1999). The closely related tris(5,5'-dimethyl-2,2'-bipyridine)copper(II) complexes have been reported as the hexafluorophosphate (Perkins et al., 2006) and tetrafluoroborate salt (van Albada et al., 2004).

The asymmetric unit of the title complex is shown in Fig. 1. The cation-anion packing view projected onto the bc plane is given in Fig. 2. Bond lengths and angles in the title complex (Table 1) are as expected from the related [Cu(2,2'-bipy)₃]-compounds with other anions. The crystal packing is primarily governed by the electrostatic cation-anion interaction and separation. Some weak C—H···F interactions from the bipyridine to the BF₄-anion can be discerned (Althoff et al., 2006). No relevant π—π or C—H···π interactions were found (Janiak, 2000; Nishio, 2004).

Noteworthy, the long Cu···N5 distortion apparently leads to a sizable tilt angle between the pyridyl ring planes of N5 and N6 of 32.1 (1)°, while the other two ring planes show tilt angles of 14.5 (1)° (N1,N2) or 11.0 (1)° (N3,N4).

Related literature

For related literature, see: Althoff et al. (2006); Anderson (1972); Dong et al. (2006); Faulmann et al. (1998); Janiak et al. (1999); Janiak (2000); Juric et al. (2006); Liu et al. (1991); Majumdar et al. (1998); Murphy et al. (2006); Nishio (2004); Niu et al. (2004); Pavlishchuk et al. (1999); Perkins et al. (2006); van Albada et al. (2004); Yang et al. (2004a,b); Wu et al. (2003).

S2. Experimental

A methanol solution (30 ml) of Cu(BF₄)₂.6H₂O (5 mmol, 1.726 g) was mixed with L-glutamic acid (5 mmol, 0.781 g) and the mixture was warmed on a water bath for 5 minutes. The resulting blue solution was added to a methanol solution (10 ml) of 2,2'-bipyridine (5 mmol, 0.780 g). The dark blue solution was stirred for 15 min. Blue crystals were obtained by slow evaporation of the mother liquor after two days. The crystals were analyzed as the title compound. For a direct preparation an aqueous solution (10 ml) of Cu(BF₄)₂.6H₂O (2 mmol, 0.690 g) was mixed with a methanol solution (5 ml) of 2,2'-bipyridine (6 mmol, 0.937 g) and the mixture was refluxed for approximately 2 h. After two days at room temperature long light blue crystals were obtained (yield 68%). Analysis calculated for C₃₀H₂₄CuB₂F₈N₆ (705.72): C 51.06, H 3.43, N 11.91%; found: C 51.30, H, 3.15, N 11.73%.

S3. Refinement

H atoms were positioned geometrically (C—H = 0.94 Å) and refined using a riding model (AFIX 43), with U_iso(H) = 1.2U_eq(C). The disordered F atoms on B2 were refined anisotropically by assigning them to different PART numbers of a disordered group. The atoms of PART 1 (F6A, F7A and F8) were found to have an occupation factor (sof) of 0.4. The atoms of PART 2 (F6B, F7B, F8B) had an occupation factor of 0.6. These occupation factors were initially found upon refinement and then fixed in subsequent refinement cycles.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Crystal Impact, 2006); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures

	Fig. 1. : Asymmetric unit of [Cu(2,2'-bipy)3](BF4)2, also showing the rotational disorder of one BF4 anion.
	Fig. 2. : Crystal packing projected onto the bc plane, illustrating the cation-anion separation.

Tris(2,2'-bipyridine-κ²N,N')copper(II) bis(tetrafluoridoborate)

Crystal data

[Cu(C10H8N2)3](BF4)2	Z = 2
Mr = 705.72	F(000) = 714
Triclinic, P1	Dx = 1.555 Mg m^−3
a = 7.8633 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.7810 (2) Å	Cell parameters from 9932 reflections
c = 18.3211 (4) Å	θ = 4.9–57.9°
α = 101.118 (1)°	µ = 0.81 mm^−1
β = 90.750 (1)°	T = 203 K
γ = 98.091 (1)°	Needle, blue
V = 1507.54 (6) Å^3	0.29 × 0.09 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer	6145 independent reflections
Radiation source: fine-focus sealed tube	4809 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.081
ω scans	θmax = 26.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.799, Tmax = 0.955	k = −13→13
35533 measured reflections	l = −22→22

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0432P)^2 + 0.2354P] where P = (Fo^2 + 2Fc^2)/3
6145 reflections	(Δ/σ)max = 0.001
451 parameters	Δρmax = 0.68 e Å^−3
0 restraints	Δρmin = −0.30 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)
Cu	0.49641 (3)	0.26662 (2)	0.259958 (10)	0.02981 (9)
N1	0.6154 (2)	0.14377 (15)	0.18640 (7)	0.0324 (4)
N2	0.6720 (2)	0.39431 (15)	0.22253 (7)	0.0323 (4)
N3	0.6455 (2)	0.23049 (16)	0.35676 (8)	0.0362 (4)
N4	0.3385 (2)	0.12645 (15)	0.29363 (8)	0.0351 (4)
N5	0.3100 (2)	0.30720 (16)	0.16155 (8)	0.0356 (4)
N6	0.3548 (2)	0.39973 (15)	0.31069 (7)	0.0317 (4)
C1	0.5892 (3)	0.0164 (2)	0.17581 (10)	0.0410 (5)
H1A	0.5004	−0.0236	0.2009	0.049*
C2	0.6876 (3)	−0.0589 (2)	0.12940 (11)	0.0506 (6)
H2A	0.6664	−0.1484	0.1233	0.061*
C3	0.8163 (3)	−0.0012 (3)	0.09252 (12)	0.0569 (7)
H3A	0.8854	−0.0507	0.0610	0.068*
C4	0.8438 (3)	0.1303 (2)	0.10199 (11)	0.0507 (6)
H4A	0.9316	0.1713	0.0769	0.061*
C5	0.7400 (3)	0.2015 (2)	0.14913 (9)	0.0354 (5)
C6	0.7582 (3)	0.3416 (2)	0.16347 (9)	0.0355 (5)
C7	0.8520 (3)	0.4170 (2)	0.12031 (10)	0.0489 (6)
H7A	0.9077	0.3790	0.0786	0.059*
C8	0.8627 (3)	0.5479 (3)	0.13910 (12)	0.0543 (6)
H8A	0.9243	0.6002	0.1100	0.065*
C9	0.7822 (3)	0.6010 (2)	0.20101 (12)	0.0489 (6)
H9B	0.7917	0.6903	0.2158	0.059*
C10	0.6867 (3)	0.5218 (2)	0.24154 (11)	0.0397 (5)
H10A	0.6307	0.5587	0.2835	0.048*
C11	0.1779 (3)	0.0876 (2)	0.26544 (11)	0.0454 (5)
H11A	0.1367	0.1283	0.2292	0.055*
C12	0.0703 (3)	−0.0097 (2)	0.28738 (12)	0.0560 (6)
H12A	−0.0427	−0.0343	0.2671	0.067*
C13	0.1320 (4)	−0.0700 (2)	0.33951 (13)	0.0621 (7)
H13A	0.0619	−0.1370	0.3554	0.074*
C14	0.2974 (4)	−0.0314 (2)	0.36820 (11)	0.0552 (7)
H14A	0.3413	−0.0731	0.4033	0.066*
C15	0.3999 (3)	0.06876 (18)	0.34562 (9)	0.0391 (5)
C16	0.5772 (3)	0.12056 (19)	0.37568 (9)	0.0390 (5)
C17	0.6688 (4)	0.0604 (2)	0.42061 (11)	0.0513 (6)
H17A	0.6200	−0.0173	0.4329	0.062*
C18	0.8314 (4)	0.1164 (3)	0.44662 (12)	0.0572 (7)
H18A	0.8949	0.0773	0.4771	0.069*
C19	0.9016 (3)	0.2303 (2)	0.42800 (11)	0.0515 (6)
H19A	1.0126	0.2701	0.4455	0.062*
C20	0.8033 (3)	0.2841 (2)	0.38278 (10)	0.0436 (5)
H20A	0.8499	0.3617	0.3698	0.052*
C21	0.2698 (3)	0.46343 (18)	0.26934 (9)	0.0335 (4)
C22	0.1715 (3)	0.5548 (2)	0.30129 (11)	0.0462 (5)
H22A	0.1144	0.5991	0.2715	0.055*
C23	0.1587 (3)	0.5800 (2)	0.37805 (11)	0.0517 (6)
H23A	0.0922	0.6414	0.4009	0.062*
C24	0.2440 (3)	0.5144 (2)	0.42011 (10)	0.0449 (5)
H24A	0.2360	0.5298	0.4721	0.054*
C25	0.3416 (3)	0.4256 (2)	0.38535 (9)	0.0375 (5)
H25A	0.4010	0.3816	0.4145	0.045*
C26	0.2875 (3)	0.5179 (2)	0.14170 (10)	0.0401 (5)
H26A	0.2726	0.6026	0.1616	0.048*
C27	0.3104 (3)	0.4783 (2)	0.06585 (11)	0.0462 (5)
H27A	0.3122	0.5363	0.0335	0.055*
C28	0.3300 (3)	0.3536 (2)	0.03931 (10)	0.0454 (5)
H28A	0.3433	0.3246	−0.0118	0.054*
C29	0.3300 (3)	0.2709 (2)	0.08831 (10)	0.0405 (5)
H29A	0.3447	0.1857	0.0695	0.049*
C30	0.2876 (2)	0.42833 (19)	0.18674 (9)	0.0321 (4)
B1	0.2109 (4)	0.8267 (2)	0.08406 (13)	0.0473 (6)
F1	0.3396 (2)	0.77651 (16)	0.04220 (9)	0.0756 (5)
F2	0.05285 (19)	0.76224 (13)	0.05089 (7)	0.0608 (4)
F3	0.21961 (19)	0.95517 (12)	0.08408 (7)	0.0577 (4)
F4	0.2248 (3)	0.80748 (14)	0.15576 (7)	0.0805 (5)
B2	0.3042 (3)	0.2767 (2)	0.57012 (12)	0.0416 (6)
F5	0.2891 (2)	0.40217 (15)	0.57208 (9)	0.0755 (5)
F6A	0.3457 (11)	0.2434 (5)	0.6377 (3)	0.103 (3)	0.40
F7A	0.4247 (8)	0.2392 (6)	0.5222 (4)	0.097 (2)	0.40
F8A	0.1552 (8)	0.1886 (6)	0.5459 (4)	0.099 (2)	0.40
F6B	0.4403 (5)	0.2725 (4)	0.6134 (2)	0.0805 (12)	0.60
F7B	0.3161 (7)	0.2142 (5)	0.50027 (17)	0.1027 (16)	0.60
F8B	0.1604 (5)	0.2332 (4)	0.5983 (3)	0.1105 (16)	0.60

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.03426 (15)	0.02520 (13)	0.03177 (11)	0.00620 (10)	0.00703 (9)	0.00832 (8)
N1	0.0350 (10)	0.0322 (9)	0.0305 (6)	0.0084 (7)	0.0020 (6)	0.0053 (6)
N2	0.0315 (9)	0.0327 (9)	0.0338 (7)	0.0015 (7)	−0.0009 (6)	0.0116 (6)
N3	0.0471 (11)	0.0314 (9)	0.0332 (7)	0.0103 (8)	0.0042 (7)	0.0108 (6)
N4	0.0413 (11)	0.0275 (9)	0.0374 (7)	0.0060 (8)	0.0106 (7)	0.0073 (6)
N5	0.0382 (10)	0.0329 (9)	0.0358 (7)	0.0054 (8)	−0.0022 (7)	0.0072 (6)
N6	0.0346 (9)	0.0276 (9)	0.0333 (7)	0.0062 (7)	0.0036 (6)	0.0060 (6)
C1	0.0488 (14)	0.0369 (12)	0.0385 (9)	0.0126 (10)	0.0031 (9)	0.0057 (8)
C2	0.0652 (17)	0.0406 (13)	0.0471 (10)	0.0237 (12)	−0.0017 (11)	0.0003 (9)
C3	0.0567 (16)	0.0674 (18)	0.0480 (11)	0.0321 (14)	0.0063 (11)	−0.0022 (11)
C4	0.0393 (13)	0.0699 (17)	0.0436 (10)	0.0148 (12)	0.0114 (9)	0.0076 (10)
C5	0.0298 (11)	0.0486 (12)	0.0296 (7)	0.0096 (9)	−0.0003 (7)	0.0090 (8)
C6	0.0272 (11)	0.0484 (13)	0.0314 (8)	0.0016 (9)	−0.0012 (7)	0.0122 (8)
C7	0.0403 (13)	0.0667 (16)	0.0397 (9)	−0.0062 (12)	0.0034 (9)	0.0204 (10)
C8	0.0478 (15)	0.0636 (17)	0.0539 (11)	−0.0126 (12)	−0.0048 (10)	0.0330 (11)
C9	0.0442 (14)	0.0379 (12)	0.0645 (12)	−0.0063 (11)	−0.0150 (11)	0.0199 (10)
C10	0.0373 (12)	0.0354 (12)	0.0470 (9)	0.0006 (9)	−0.0055 (9)	0.0132 (8)
C11	0.0485 (14)	0.0379 (12)	0.0482 (10)	0.0035 (11)	0.0108 (10)	0.0058 (9)
C12	0.0567 (16)	0.0459 (14)	0.0581 (12)	−0.0090 (12)	0.0134 (11)	0.0033 (10)
C13	0.076 (2)	0.0440 (14)	0.0608 (13)	−0.0149 (13)	0.0203 (13)	0.0121 (11)
C14	0.082 (2)	0.0408 (13)	0.0459 (10)	0.0038 (13)	0.0152 (11)	0.0188 (9)
C15	0.0572 (14)	0.0269 (10)	0.0346 (8)	0.0085 (10)	0.0158 (9)	0.0072 (7)
C16	0.0556 (15)	0.0344 (11)	0.0313 (8)	0.0154 (10)	0.0138 (8)	0.0099 (7)
C17	0.0686 (18)	0.0457 (14)	0.0507 (11)	0.0240 (13)	0.0144 (11)	0.0251 (10)
C18	0.0683 (19)	0.0680 (17)	0.0495 (11)	0.0368 (15)	0.0094 (11)	0.0269 (11)
C19	0.0518 (15)	0.0650 (16)	0.0429 (10)	0.0210 (13)	0.0015 (10)	0.0144 (10)
C20	0.0500 (15)	0.0440 (13)	0.0385 (9)	0.0088 (11)	0.0007 (9)	0.0107 (8)
C21	0.0329 (11)	0.0309 (10)	0.0366 (8)	0.0065 (9)	0.0008 (8)	0.0052 (7)
C22	0.0461 (14)	0.0461 (13)	0.0483 (10)	0.0203 (11)	−0.0029 (9)	0.0046 (9)
C23	0.0513 (15)	0.0514 (14)	0.0517 (11)	0.0233 (12)	0.0061 (10)	−0.0036 (10)
C24	0.0497 (14)	0.0462 (13)	0.0372 (9)	0.0125 (11)	0.0082 (9)	0.0004 (9)
C25	0.0398 (12)	0.0376 (11)	0.0355 (8)	0.0053 (9)	0.0045 (8)	0.0082 (8)
C26	0.0428 (13)	0.0332 (11)	0.0464 (9)	0.0099 (10)	−0.0024 (9)	0.0097 (8)
C27	0.0496 (14)	0.0498 (14)	0.0446 (10)	0.0083 (11)	0.0005 (9)	0.0216 (9)
C28	0.0494 (14)	0.0519 (14)	0.0344 (8)	0.0071 (11)	−0.0007 (9)	0.0077 (9)
C29	0.0457 (13)	0.0370 (12)	0.0367 (8)	0.0078 (10)	−0.0033 (8)	0.0013 (8)
C30	0.0270 (11)	0.0324 (11)	0.0368 (8)	0.0057 (8)	−0.0022 (7)	0.0062 (7)
B1	0.0596 (18)	0.0304 (13)	0.0518 (12)	0.0077 (12)	−0.0008 (12)	0.0069 (10)
F1	0.0628 (11)	0.0641 (11)	0.0981 (11)	0.0240 (9)	0.0108 (8)	0.0003 (8)
F2	0.0574 (9)	0.0529 (9)	0.0687 (8)	−0.0077 (7)	0.0027 (7)	0.0154 (7)
F3	0.0666 (10)	0.0331 (7)	0.0749 (8)	0.0067 (7)	0.0047 (7)	0.0149 (6)
F4	0.1436 (17)	0.0460 (9)	0.0540 (7)	0.0211 (10)	−0.0122 (9)	0.0108 (6)
B2	0.0395 (15)	0.0437 (15)	0.0414 (10)	0.0055 (12)	−0.0028 (10)	0.0091 (10)
F5	0.0962 (13)	0.0488 (9)	0.0854 (9)	0.0195 (9)	−0.0092 (9)	0.0170 (8)
F6A	0.209 (9)	0.056 (4)	0.047 (2)	0.057 (4)	−0.040 (4)	−0.008 (2)
F7A	0.084 (4)	0.084 (4)	0.116 (5)	0.009 (4)	0.064 (4)	0.003 (4)
F8A	0.075 (4)	0.072 (4)	0.147 (5)	−0.023 (3)	−0.056 (5)	0.046 (4)
F6B	0.064 (2)	0.063 (2)	0.114 (3)	0.0096 (17)	−0.045 (2)	0.021 (2)
F7B	0.159 (5)	0.103 (3)	0.0495 (14)	0.061 (4)	0.004 (2)	−0.0062 (16)
F8B	0.051 (2)	0.096 (3)	0.206 (5)	0.010 (2)	0.051 (3)	0.079 (3)

Geometric parameters (Å, º)

Cu—N4	2.0144 (16)	C13—H13A	0.9400
Cu—N2	2.0309 (16)	C14—C15	1.387 (3)
Cu—N6	2.0313 (16)	C14—H14A	0.9400
Cu—N1	2.0347 (15)	C15—C16	1.483 (3)
Cu—N3	2.2388 (16)	C16—C17	1.392 (3)
Cu—N5	2.4506 (16)	C17—C18	1.372 (4)
N1—C1	1.335 (3)	C17—H17A	0.9400
N1—C5	1.350 (2)	C18—C19	1.380 (3)
N2—C10	1.339 (3)	C18—H18A	0.9400
N2—C6	1.358 (2)	C19—C20	1.383 (3)
N3—C20	1.333 (3)	C19—H19A	0.9400
N3—C16	1.341 (3)	C20—H20A	0.9400
N4—C11	1.337 (3)	C21—C22	1.383 (3)
N4—C15	1.352 (3)	C21—C30	1.501 (2)
N5—C30	1.336 (2)	C22—C23	1.388 (3)
N5—C29	1.341 (2)	C22—H22A	0.9400
N6—C21	1.345 (3)	C23—C24	1.369 (3)
N6—C25	1.351 (2)	C23—H23A	0.9400
C1—C2	1.381 (3)	C24—C25	1.377 (3)
C1—H1A	0.9400	C24—H24A	0.9400
C2—C3	1.368 (4)	C25—H25A	0.9400
C2—H2A	0.9400	C26—C30	1.386 (3)
C3—C4	1.380 (4)	C26—C27	1.395 (3)
C3—H3A	0.9400	C26—H26A	0.9400
C4—C5	1.393 (3)	C27—C28	1.370 (3)
C4—H4A	0.9400	C27—H27A	0.9400
C5—C6	1.468 (3)	C28—C29	1.382 (3)
C6—C7	1.387 (3)	C28—H28A	0.9400
C7—C8	1.377 (3)	C29—H29A	0.9400
C7—H7A	0.9400	B1—F4	1.374 (3)
C8—C9	1.373 (3)	B1—F3	1.377 (3)
C8—H8A	0.9400	B1—F1	1.386 (3)
C9—C10	1.387 (3)	B1—F2	1.404 (3)
C9—H9B	0.9400	B2—F8B	1.313 (4)
C10—H10A	0.9400	B2—F6B	1.334 (4)
C11—C12	1.379 (3)	B2—F7B	1.337 (4)
C11—H11A	0.9400	B2—F7A	1.351 (5)
C12—C13	1.373 (4)	B2—F5	1.368 (3)
C12—H12A	0.9400	B2—F6A	1.402 (5)
C13—C14	1.373 (4)	B2—F8A	1.409 (6)
N4—Cu—N2	174.08 (6)	C12—C13—H13A	120.3
N4—Cu—N6	91.04 (6)	C13—C14—C15	120.3 (2)
N2—Cu—N6	94.81 (6)	C13—C14—H14A	119.8
N4—Cu—N1	94.04 (6)	C15—C14—H14A	119.8
N2—Cu—N1	80.47 (6)	N4—C15—C14	119.9 (2)
N6—Cu—N1	166.16 (6)	N4—C15—C16	115.94 (17)
N4—Cu—N3	77.31 (7)	C14—C15—C16	124.2 (2)
N2—Cu—N3	100.51 (6)	N3—C16—C17	121.4 (2)
N6—Cu—N3	101.71 (6)	N3—C16—C15	115.58 (18)
N1—Cu—N3	91.97 (6)	C17—C16—C15	123.0 (2)
N4—Cu—N5	99.13 (6)	C18—C17—C16	118.8 (2)
N2—Cu—N5	83.42 (6)	C18—C17—H17A	120.6
N6—Cu—N5	74.14 (6)	C16—C17—H17A	120.6
N1—Cu—N5	92.33 (6)	C17—C18—C19	120.0 (2)
N3—Cu—N5	174.61 (6)	C17—C18—H18A	120.0
C1—N1—C5	119.01 (17)	C19—C18—H18A	120.0
C1—N1—Cu	126.67 (13)	C18—C19—C20	117.9 (2)
C5—N1—Cu	114.18 (13)	C18—C19—H19A	121.0
C10—N2—C6	118.84 (17)	C20—C19—H19A	121.0
C10—N2—Cu	126.24 (13)	N3—C20—C19	122.8 (2)
C6—N2—Cu	113.80 (13)	N3—C20—H20A	118.6
C20—N3—C16	119.03 (18)	C19—C20—H20A	118.6
C20—N3—Cu	128.30 (13)	N6—C21—C22	121.80 (16)
C16—N3—Cu	110.50 (13)	N6—C21—C30	115.75 (17)
C11—N4—C15	119.49 (18)	C22—C21—C30	122.44 (18)
C11—N4—Cu	122.36 (14)	C21—C22—C23	119.0 (2)
C15—N4—Cu	118.14 (14)	C21—C22—H22A	120.5
C30—N5—C29	117.54 (18)	C23—C22—H22A	120.5
C30—N5—Cu	102.31 (11)	C24—C23—C22	119.2 (2)
C29—N5—Cu	124.94 (14)	C24—C23—H23A	120.4
C21—N6—C25	118.56 (17)	C22—C23—H23A	120.4
C21—N6—Cu	119.66 (11)	C23—C24—C25	119.25 (18)
C25—N6—Cu	121.77 (14)	C23—C24—H24A	120.4
N1—C1—C2	122.5 (2)	C25—C24—H24A	120.4
N1—C1—H1A	118.8	N6—C25—C24	122.2 (2)
C2—C1—H1A	118.8	N6—C25—H25A	118.9
C3—C2—C1	119.0 (2)	C24—C25—H25A	118.9
C3—C2—H2A	120.5	C30—C26—C27	117.9 (2)
C1—C2—H2A	120.5	C30—C26—H26A	121.1
C2—C3—C4	119.4 (2)	C27—C26—H26A	121.1
C2—C3—H3A	120.3	C28—C27—C26	118.9 (2)
C4—C3—H3A	120.3	C28—C27—H27A	120.5
C3—C4—C5	119.2 (2)	C26—C27—H27A	120.5
C3—C4—H4A	120.4	C27—C28—C29	119.40 (18)
C5—C4—H4A	120.4	C27—C28—H28A	120.3
N1—C5—C4	120.9 (2)	C29—C28—H28A	120.3
N1—C5—C6	115.26 (16)	N5—C29—C28	122.7 (2)
C4—C5—C6	123.83 (19)	N5—C29—H29A	118.7
N2—C6—C7	121.2 (2)	C28—C29—H29A	118.7
N2—C6—C5	114.73 (16)	N5—C30—C26	123.60 (16)
C7—C6—C5	124.03 (18)	N5—C30—C21	114.84 (17)
C8—C7—C6	119.5 (2)	C26—C30—C21	121.51 (18)
C8—C7—H7A	120.3	F4—B1—F3	110.12 (18)
C6—C7—H7A	120.3	F4—B1—F1	110.1 (2)
C9—C8—C7	119.1 (2)	F3—B1—F1	110.5 (2)
C9—C8—H8A	120.5	F4—B1—F2	109.4 (2)
C7—C8—H8A	120.5	F3—B1—F2	109.2 (2)
C8—C9—C10	119.4 (2)	F1—B1—F2	107.39 (18)
C8—C9—H9B	120.3	F8B—B2—F6B	111.3 (3)
C10—C9—H9B	120.3	F8B—B2—F7B	110.6 (4)
N2—C10—C9	121.8 (2)	F6B—B2—F7B	112.2 (3)
N2—C10—H10A	119.1	F8B—B2—F5	103.0 (3)
C9—C10—H10A	119.1	F6B—B2—F5	108.2 (3)
N4—C11—C12	122.6 (2)	F7B—B2—F5	111.2 (3)
N4—C11—H11A	118.7	F7A—B2—F5	110.5 (4)
C12—C11—H11A	118.7	F7A—B2—F6A	106.7 (5)
C13—C12—C11	118.4 (2)	F5—B2—F6A	116.9 (3)
C13—C12—H12A	120.8	F7A—B2—F8A	104.6 (4)
C11—C12—H12A	120.8	F5—B2—F8A	115.6 (3)
C14—C13—C12	119.3 (2)	F6A—B2—F8A	101.4 (4)
C14—C13—H13A	120.3

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···F2^i	0.94	2.54	3.342 (3)	144
C8—H8A···F2^ii	0.94	2.35	3.274 (3)	169
C10—H10A···F6B^iii	0.94	2.49	3.376 (4)	158
C13—H13A···F8B^iv	0.94	2.17	3.063 (5)	158
C26—H26A···F4	0.94	2.31	3.191 (3)	155
C27—H27A···F1	0.94	2.54	3.303 (3)	138

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