Tris[N-(4-fluorophenyl)pyridine-2-carboxamidato-κ²N,N′]cobalt(III) trihydrate: a novel meridional complex

The title complex, [Co(C₁₂H₈FN₂O)₃]·3H₂O, has been synthesized for the first time. The complex comprises three bidentate ligands containing the pyridine-2-carbox­amide stem. The distorted octahedral coordination around the Co atom is formed via the pyridine (py) N atom and the deprotonated amide N atom of each ligand, with the three pyridine rings in a meridional arrangement. For each ligand, the pyridine ring and the carbonyl group are nearly coplanar, with torsion angles in the range 0.4 (3)–4.8 (4)°. The Co—N_py distances [1.9258 (16)–1.9656 (17) Å] are shorter than the corresponding Co—N_amide distances [1.9372 (17)–1.9873 (15) Å]. In addition, the Co—N_py distances are closely related to the magnitudes of the chelate angles, a shorter Co—N_py distance corresponding to a larger angle. Five intermolecular hydrogen bonds, involving carbonyl O atoms of the ligands and lattice water mol­ecules, lead to the formation of a mesh structure.

S1. Comment

The selective oxidation of hydrocarbons using molecular oxygen as the primary oxidant is an important technology and is an area of continued research and development because of the low cost and environmentally friendly nature of the oxidant (Bolm et al., 1994; Neumann & Dahan, 1998; Brink et al., 2000). Much effort has been made in the past to activate dioxygen by metal complexes (Shilov & Shul'pin, 2000). Ishii et al. (1996) reported a novel catalytic system using N-hydroxyphthalimide combined with Co(acac)_n (n = 2 or 3) as catalysts in the oxidation of alkylbenzene; thus ethylbenzene was successfully oxidized to acetophenone in excellent yield. However, this method has a corrosive and environmentally unfriendly nature because of the use of acetic acid as solvent. We recently found in our laboratory that the title complex, (I), is an efficient catalyst for the direct oxidation of ethylbenzene with dioxygen, without the need of any solvent and reducing reagent, giving 86.0% acetophenone selectivity on 65.7% conversion under moderate conditions. This economical and environmentally friendly system shows excellent potential for industrial application. The synthesis and structure of complex (I) are described here.

Complex (I) contains three ligands, coordinated via the pyridine N atom and the negatively charged amide nitrogen ion instead of the neutral amide N atom or the carbonyl O atom. There are two possible geometric isomers for this compound. One is facial, having all three pyridine rings in a cis confromation. The other is meridional, having two of the pyridine rings in trans positions. The crystal structure shows that this complex is the latter isomer; two pyridine rings are mutually trans, two amide groups are mutually trans and one pyridine ring is trans to one amide group. Therefore, various situations exist for competitive trans effects. For each of the three ligands, the Co—py distance [1.9258 (16)–1.9656 (17) Å] is always shorter than the corresponding Co—amide distance [1.9372 (17)–1.9873 (15) Å], while the Co–py distance for one ligand can be longer than the Co—amide distance for another; for instance, the Co—N3 distance [1.9656 (17) Å] is longer than the Co—N6 distance [1.9372 (17) Å]. Moreover, the Co—py distances depend on the size of the chelate angles; the longer the Co–py distance, the smaller the corresponding chelate angle. In (I), the Co—N3 distance is the longest distance and the N3—Co—N4 angle [81.92 (7) °] is the smallest angle. Since the distances of the six coordination bonds are not equal, the complex has the form of a distorted octahedron. The structural features described above have been reported in analogous complexes (Qi et al., 2003).

For every ligand in (I), the pyridine ring and the carbonyl group are nearly coplanar, with C4—C5—C6—O1, C16—C17—C18—O2 and C28—C29—C30—O3 torsion angles of 0.4 (3), 4.8 (3) and 3.2 (3)°, respectively. In addition, the deprotonated amide N atom facilitates the aerobic oxidation of Co^II to Co^III during the formation of the complex. The three anionic ligands neutralize the trivalent cationic cobalt.

There are four intermolecular hydrogen bonds in the crystal structure of (I) (Fig. 1); (i) carbonyl atom O2 of one molecule interacts with the O1W/H11W group of a lattice water molecule, (ii) the O3W/H3WA lattice water group interacts with water atom O1W, (iii) carbonyl atom O1 interacts with the O2W/H21W group of an adjacent water molecule and (iv) carbonyl atom O3 interacts with the O2W/H22W group of another lattice water molecule. Through these intermolecular hydrogen-bonding interactions, every molecule of (I) is linked to adjacent molecules, thus forming a mesh structure.

S2. Experimental

The ligand of the complex was synthesized from 2-pyridinecarboxylic acid and 4-fluoroaniline, according a published procedure (Ray et al., 1997). The ligand was dissolved in EtOH under ambient conditions and to it was added cobalt dichloride dissolved in EtOH and 25% NH₃. The mixture was stirred magnetically for 0.5 h. The precipitate was filtered off, washed with ethanol and air-dried, yielding a deep-red powder. Single crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent from an ethanol–water saturated solution at room temperature.

S3. Refinement

The C-bound H atoms were placed in calculated positions, with C—H distances of 0.93 Å, and were thereafter treated as riding. Water H atoms were positioned from difference maps, and their coordinates were refined with the O—H distance constrained (0.8500–0.8501 Å). U_iso(H) values were set at 1.2U_eq of the attached atom.

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SMART (Siemens, 1995); data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures

Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 30% probability level H atoms have been omitted for clarity.

Tris[N-(4-fluorophenyl)pyridine-2-carboxamide-κ²N,N']cobalt(III)

Crystal data

[Co(C12H8FN2O)3]·3H2O	Z = 2
Mr = 758.59	F(000) = 780
Triclinic, P1	Dx = 1.433 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.1443 (12) Å	Cell parameters from 7832 reflections
b = 12.2258 (12) Å	θ = 1.5–27.5°
c = 14.5543 (14) Å	µ = 0.56 mm^−1
α = 99.774 (2)°	T = 294 K
β = 103.547 (2)°	Prism, red
γ = 117.775 (2)°	0.22 × 0.20 × 0.14 mm
V = 1758.3 (3) Å^3

Data collection

Bruker SMART CCD diffractometer	6160 independent reflections
Radiation source: fine-focus sealed tube	4984 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ϕ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
Tmin = 0.727, Tmax = 0.925	k = −14→12
9817 measured reflections	l = −15→17

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.112	w = 1/[σ^2(Fo^2) + (0.05P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
6160 reflections	Δρmax = 0.49 e Å^−3
469 parameters	Δρmin = −0.24 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
Co1	0.65600 (2)	0.33221 (2)	0.233184 (17)	0.03153 (7)
O1	0.64059 (13)	0.22152 (13)	−0.04717 (9)	0.0433 (4)
O2	0.78001 (18)	0.37694 (15)	0.52705 (11)	0.0667 (5)
O3	0.52826 (14)	0.56670 (14)	0.16405 (12)	0.0555 (4)
F1	0.04920 (14)	−0.02300 (16)	−0.15903 (15)	0.0999 (6)
F2	0.8768 (2)	0.92416 (16)	0.57240 (17)	0.1195 (7)
F3	1.07569 (17)	0.83193 (17)	0.10861 (16)	0.1147 (7)
N1	0.82092 (14)	0.37289 (15)	0.21231 (11)	0.0346 (4)
N2	0.57750 (14)	0.23586 (14)	0.09039 (11)	0.0333 (4)
N3	0.65447 (14)	0.18670 (15)	0.27448 (11)	0.0350 (4)
N4	0.73645 (15)	0.42153 (15)	0.38002 (11)	0.0371 (4)
N5	0.48520 (14)	0.29329 (14)	0.23882 (11)	0.0340 (4)
N6	0.66030 (14)	0.48086 (14)	0.20033 (11)	0.0341 (4)
C1	0.94494 (19)	0.4376 (2)	0.28074 (16)	0.0483 (6)
H1	0.9567	0.4608	0.3481	0.058*
C2	1.0546 (2)	0.4706 (2)	0.25433 (18)	0.0606 (7)
H2	1.1390	0.5132	0.3034	0.073*
C3	1.0395 (2)	0.4404 (2)	0.15529 (18)	0.0587 (7)
H3	1.1135	0.4674	0.1363	0.070*
C4	0.91268 (19)	0.3696 (2)	0.08444 (16)	0.0480 (6)
H4	0.8995	0.3443	0.0169	0.058*
C5	0.80565 (17)	0.33682 (18)	0.11516 (14)	0.0359 (5)
C6	0.66487 (18)	0.25882 (18)	0.04359 (14)	0.0346 (5)
C7	0.43945 (17)	0.16983 (17)	0.02821 (13)	0.0336 (5)
C8	0.3482 (2)	0.0513 (2)	0.03171 (16)	0.0471 (6)
H8	0.3753	0.0144	0.0760	0.056*
C9	0.2154 (2)	−0.0137 (2)	−0.03061 (19)	0.0600 (7)
H9	0.1528	−0.0936	−0.0282	0.072*
C10	0.1787 (2)	0.0424 (2)	−0.09563 (19)	0.0562 (7)
C11	0.26577 (19)	0.1595 (2)	−0.10090 (17)	0.0488 (6)
H11	0.2380	0.1949	−0.1462	0.059*
C12	0.39739 (18)	0.22495 (18)	−0.03676 (14)	0.0385 (5)
H12	0.4582	0.3069	−0.0373	0.046*
C13	0.61678 (19)	0.06900 (19)	0.21601 (15)	0.0419 (5)
H13	0.5852	0.0495	0.1470	0.050*
C14	0.6232 (2)	−0.0241 (2)	0.25453 (17)	0.0482 (6)
H14	0.5953	−0.1053	0.2118	0.058*
C15	0.6706 (2)	0.0029 (2)	0.35592 (17)	0.0520 (6)
H15	0.6751	−0.0591	0.3831	0.062*
C16	0.7119 (2)	0.1255 (2)	0.41676 (16)	0.0490 (6)
H16	0.7462	0.1476	0.4859	0.059*
C17	0.70193 (18)	0.21373 (19)	0.37464 (14)	0.0387 (5)
C18	0.74311 (19)	0.3470 (2)	0.43487 (14)	0.0412 (5)
C19	0.77190 (19)	0.54975 (19)	0.43328 (14)	0.0397 (5)
C20	0.9036 (2)	0.6473 (2)	0.48549 (17)	0.0532 (6)
H20	0.9698	0.6283	0.4881	0.064*
C21	0.9390 (3)	0.7724 (2)	0.5339 (2)	0.0713 (8)
H21	1.0280	0.8372	0.5696	0.086*
C22	0.8418 (3)	0.7991 (2)	0.5286 (2)	0.0735 (8)
C23	0.7108 (3)	0.7065 (3)	0.4813 (2)	0.0724 (8)
H23	0.6460	0.7272	0.4803	0.087*
C24	0.6749 (2)	0.5798 (2)	0.43401 (17)	0.0577 (7)
H24	0.5852	0.5145	0.4026	0.069*
C25	0.40191 (19)	0.19465 (19)	0.26476 (15)	0.0433 (5)
H25	0.4260	0.1369	0.2821	0.052*
C26	0.2820 (2)	0.1774 (2)	0.26620 (18)	0.0546 (6)
H26	0.2256	0.1084	0.2839	0.066*
C27	0.2464 (2)	0.2623 (2)	0.2414 (2)	0.0602 (7)
H27	0.1658	0.2519	0.2423	0.072*
C28	0.33148 (19)	0.3635 (2)	0.21509 (18)	0.0513 (6)
H28	0.3093	0.4227	0.1984	0.062*
C29	0.44957 (18)	0.37580 (19)	0.21383 (14)	0.0376 (5)
C30	0.55064 (19)	0.48499 (19)	0.18905 (14)	0.0384 (5)
C31	0.76441 (18)	0.57498 (18)	0.17570 (15)	0.0370 (5)
C32	0.8829 (2)	0.6731 (2)	0.24968 (19)	0.0631 (7)
H32	0.8924	0.6811	0.3162	0.076*
C33	0.9876 (3)	0.7597 (3)	0.2274 (2)	0.0776 (9)
H33	1.0673	0.8253	0.2781	0.093*
C34	0.9726 (2)	0.7476 (2)	0.1316 (2)	0.0680 (7)
C35	0.8561 (3)	0.6546 (2)	0.0554 (2)	0.0713 (8)
H35	0.8474	0.6500	−0.0106	0.086*
C36	0.7509 (2)	0.5669 (2)	0.07777 (17)	0.0522 (6)
H36	0.6711	0.5026	0.0266	0.063*
O1W	0.5907 (2)	0.2122 (2)	−0.39759 (16)	0.1023 (8)
H11W	0.6591	0.2672	−0.4069	0.123*
H12W	0.5700	0.2544	−0.3597	0.123*
O2W	0.63547 (15)	0.34223 (15)	−0.19797 (13)	0.0644 (4)
H21W	0.6402	0.2980	−0.1597	0.077*
H22W	0.5736	0.3561	−0.1958	0.077*
O3W	0.3761 (2)	0.0140 (2)	−0.59594 (19)	0.1196 (9)
H31W	0.4362	0.0692	−0.5403	0.144*
H32W	0.3665	−0.0601	−0.5988	0.144*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.03386 (12)	0.03209 (12)	0.02335 (12)	0.01353 (10)	0.00992 (10)	0.00935 (9)
O1	0.0456 (7)	0.0540 (8)	0.0236 (7)	0.0240 (6)	0.0101 (6)	0.0072 (6)
O2	0.0997 (12)	0.0521 (9)	0.0246 (7)	0.0268 (8)	0.0134 (8)	0.0118 (6)
O3	0.0584 (7)	0.0597 (8)	0.0748 (10)	0.0379 (6)	0.0364 (7)	0.0435 (7)
F1	0.0372 (7)	0.0857 (11)	0.1170 (14)	0.0073 (7)	−0.0124 (8)	0.0302 (10)
F2	0.1562 (14)	0.0562 (9)	0.1365 (16)	0.0501 (9)	0.0722 (13)	0.0003 (10)
F3	0.1059 (10)	0.0911 (11)	0.1641 (15)	0.0309 (9)	0.1050 (10)	0.0653 (11)
N1	0.0354 (7)	0.0357 (8)	0.0266 (8)	0.0159 (6)	0.0093 (6)	0.0073 (6)
N2	0.0344 (7)	0.0336 (8)	0.0248 (7)	0.0134 (6)	0.0091 (6)	0.0096 (6)
N3	0.0368 (7)	0.0359 (8)	0.0272 (8)	0.0163 (6)	0.0100 (6)	0.0098 (6)
N4	0.0419 (8)	0.0372 (8)	0.0244 (8)	0.0172 (7)	0.0103 (7)	0.0054 (6)
N5	0.0351 (7)	0.0342 (8)	0.0265 (8)	0.0129 (6)	0.0122 (6)	0.0105 (6)
N6	0.0372 (7)	0.0321 (7)	0.0320 (8)	0.0153 (6)	0.0149 (6)	0.0138 (6)
C1	0.0402 (10)	0.0588 (13)	0.0321 (11)	0.0220 (9)	0.0087 (9)	0.0023 (9)
C2	0.0351 (10)	0.0769 (16)	0.0439 (13)	0.0222 (10)	0.0049 (10)	−0.0036 (12)
C3	0.0390 (10)	0.0747 (15)	0.0496 (13)	0.0251 (10)	0.0179 (10)	0.0037 (11)
C4	0.0441 (10)	0.0587 (12)	0.0362 (11)	0.0251 (9)	0.0168 (9)	0.0071 (9)
C5	0.0371 (9)	0.0364 (9)	0.0311 (10)	0.0185 (8)	0.0113 (8)	0.0084 (8)
C6	0.0402 (9)	0.0323 (9)	0.0267 (9)	0.0179 (7)	0.0089 (8)	0.0073 (7)
C7	0.0343 (9)	0.0324 (9)	0.0252 (9)	0.0126 (7)	0.0093 (7)	0.0063 (7)
C8	0.0469 (11)	0.0410 (11)	0.0429 (12)	0.0159 (9)	0.0125 (9)	0.0172 (9)
C9	0.0425 (12)	0.0411 (12)	0.0670 (15)	0.0019 (10)	0.0142 (11)	0.0197 (11)
C10	0.0320 (10)	0.0519 (13)	0.0594 (15)	0.0119 (9)	0.0032 (10)	0.0105 (11)
C11	0.0421 (10)	0.0521 (12)	0.0482 (12)	0.0240 (9)	0.0105 (10)	0.0180 (10)
C12	0.0376 (9)	0.0341 (9)	0.0380 (10)	0.0146 (8)	0.0123 (8)	0.0133 (8)
C13	0.0491 (10)	0.0391 (10)	0.0335 (10)	0.0213 (8)	0.0142 (9)	0.0095 (8)
C14	0.0521 (11)	0.0413 (11)	0.0525 (13)	0.0250 (9)	0.0200 (10)	0.0154 (9)
C15	0.0584 (12)	0.0493 (11)	0.0549 (13)	0.0299 (9)	0.0201 (10)	0.0281 (10)
C16	0.0557 (12)	0.0540 (12)	0.0362 (11)	0.0263 (10)	0.0145 (9)	0.0228 (9)
C17	0.0392 (9)	0.0413 (10)	0.0311 (10)	0.0169 (8)	0.0122 (8)	0.0157 (8)
C18	0.0433 (10)	0.0436 (10)	0.0254 (10)	0.0161 (8)	0.0085 (8)	0.0115 (8)
C19	0.0499 (10)	0.0405 (10)	0.0235 (9)	0.0202 (8)	0.0145 (8)	0.0083 (8)
C20	0.0511 (11)	0.0489 (12)	0.0465 (13)	0.0198 (10)	0.0186 (10)	0.0044 (10)
C21	0.0650 (14)	0.0503 (14)	0.0679 (17)	0.0127 (12)	0.0293 (13)	−0.0037 (12)
C22	0.0978 (17)	0.0483 (14)	0.0680 (17)	0.0341 (13)	0.0393 (15)	0.0042 (12)
C23	0.0862 (14)	0.0786 (16)	0.0624 (16)	0.0557 (13)	0.0275 (14)	0.0072 (13)
C24	0.0570 (12)	0.0632 (14)	0.0435 (13)	0.0313 (11)	0.0156 (11)	0.0009 (11)
C25	0.0466 (10)	0.0373 (10)	0.0439 (11)	0.0158 (8)	0.0223 (9)	0.0189 (8)
C26	0.0457 (11)	0.0474 (12)	0.0654 (14)	0.0139 (10)	0.0298 (10)	0.0255 (10)
C27	0.0403 (10)	0.0596 (14)	0.0816 (17)	0.0212 (10)	0.0309 (11)	0.0284 (12)
C28	0.0406 (10)	0.0540 (12)	0.0640 (14)	0.0252 (9)	0.0208 (10)	0.0261 (10)
C29	0.0378 (9)	0.0375 (10)	0.0321 (10)	0.0156 (8)	0.0120 (8)	0.0129 (8)
C30	0.0416 (10)	0.0376 (10)	0.0354 (10)	0.0185 (8)	0.0157 (8)	0.0156 (8)
C31	0.0419 (9)	0.0352 (9)	0.0406 (10)	0.0200 (8)	0.0218 (8)	0.0187 (8)
C32	0.0496 (12)	0.0610 (14)	0.0507 (13)	0.0075 (11)	0.0132 (11)	0.0277 (11)
C33	0.0463 (13)	0.0680 (16)	0.087 (2)	0.0059 (12)	0.0170 (13)	0.0379 (15)
C34	0.0674 (13)	0.0549 (13)	0.1023 (19)	0.0291 (11)	0.0581 (13)	0.0431 (13)
C35	0.1085 (16)	0.0598 (14)	0.0679 (14)	0.0412 (13)	0.0670 (13)	0.0311 (11)
C36	0.0695 (13)	0.0394 (11)	0.0466 (12)	0.0220 (10)	0.0331 (10)	0.0148 (9)
O1W	0.1224 (15)	0.0712 (13)	0.0905 (14)	0.0245 (12)	0.0631 (13)	0.0208 (11)
O2W	0.0768 (9)	0.0678 (9)	0.0765 (10)	0.0441 (8)	0.0478 (8)	0.0400 (8)
O3W	0.1352 (18)	0.1281 (17)	0.1273 (19)	0.0765 (14)	0.0550 (15)	0.0806 (14)

Geometric parameters (Å, º)

Co1—N5	1.9258 (16)	C13—H13	0.9300
Co1—N6	1.9372 (17)	C14—C15	1.370 (3)
Co1—N1	1.9388 (16)	C14—H14	0.9300
Co1—N2	1.9518 (15)	C15—C16	1.387 (3)
Co1—N3	1.9656 (17)	C15—H15	0.9300
Co1—N4	1.9873 (15)	C16—C17	1.366 (3)
O1—C6	1.236 (2)	C16—H16	0.9300
O2—C18	1.238 (2)	C17—C18	1.491 (3)
O3—C30	1.239 (3)	C19—C20	1.379 (3)
F1—C10	1.364 (2)	C19—C24	1.389 (3)
F2—C22	1.364 (3)	C20—C21	1.379 (3)
F3—C34	1.361 (3)	C20—H20	0.9300
N1—C1	1.344 (2)	C21—C22	1.352 (4)
N1—C5	1.348 (2)	C21—H21	0.9300
N2—C6	1.340 (3)	C22—C23	1.353 (4)
N2—C7	1.436 (2)	C23—C24	1.390 (4)
N3—C13	1.339 (2)	C23—H23	0.9300
N3—C17	1.353 (2)	C24—H24	0.9300
N4—C18	1.327 (3)	C25—C26	1.377 (3)
N4—C19	1.430 (3)	C25—H25	0.9300
N5—C29	1.340 (3)	C26—C27	1.366 (4)
N5—C25	1.348 (2)	C26—H26	0.9300
N6—C30	1.329 (3)	C27—C28	1.379 (3)
N6—C31	1.431 (2)	C27—H27	0.9300
C1—C2	1.370 (3)	C28—C29	1.375 (3)
C1—H1	0.9300	C28—H28	0.9300
C2—C3	1.371 (3)	C29—C30	1.504 (3)
C2—H2	0.9300	C31—C36	1.377 (3)
C3—C4	1.376 (3)	C31—C32	1.377 (3)
C3—H3	0.9300	C32—C33	1.378 (3)
C4—C5	1.378 (3)	C32—H32	0.9300
C4—H4	0.9300	C33—C34	1.336 (4)
C5—C6	1.492 (2)	C33—H33	0.9300
C7—C8	1.373 (3)	C34—C35	1.364 (4)
C7—C12	1.386 (3)	C35—C36	1.388 (3)
C8—C9	1.389 (3)	C35—H35	0.9300
C8—H8	0.9300	C36—H36	0.9300
C9—C10	1.369 (4)	O1W—H11W	0.8500
C9—H9	0.9300	O1W—H12W	0.8501
C10—C11	1.356 (3)	O2W—H21W	0.8501
C11—C12	1.386 (3)	O2W—H22W	0.8500
C11—H11	0.9300	O3W—H31W	0.8500
C12—H12	0.9300	O3W—H32W	0.8500
C13—C14	1.376 (3)
N5—Co1—N6	82.94 (7)	C15—C14—C13	119.9 (2)
N5—Co1—N1	173.35 (7)	C15—C14—H14	120.0
N6—Co1—N1	92.93 (7)	C13—C14—H14	120.0
N5—Co1—N2	91.91 (6)	C14—C15—C16	118.0 (2)
N6—Co1—N2	88.43 (7)	C14—C15—H15	121.0
N1—Co1—N2	82.74 (6)	C16—C15—H15	121.0
N5—Co1—N3	96.43 (7)	C17—C16—C15	119.7 (2)
N6—Co1—N3	176.77 (6)	C17—C16—H16	120.2
N1—Co1—N3	87.98 (7)	C15—C16—H16	120.2
N2—Co1—N3	94.76 (7)	N3—C17—C16	122.26 (19)
N5—Co1—N4	88.83 (6)	N3—C17—C18	114.86 (18)
N6—Co1—N4	94.88 (7)	C16—C17—C18	122.87 (18)
N1—Co1—N4	96.74 (6)	O2—C18—N4	127.4 (2)
N2—Co1—N4	176.67 (7)	O2—C18—C17	119.1 (2)
N3—Co1—N4	81.92 (7)	N4—C18—C17	113.51 (16)
C1—N1—C5	118.06 (17)	C20—C19—C24	118.0 (2)
C1—N1—Co1	128.35 (14)	C20—C19—N4	120.9 (2)
C5—N1—Co1	113.45 (12)	C24—C19—N4	121.06 (18)
C6—N2—C7	116.67 (15)	C21—C20—C19	121.3 (2)
C6—N2—Co1	115.07 (11)	C21—C20—H20	119.4
C7—N2—Co1	126.51 (13)	C19—C20—H20	119.4
C13—N3—C17	117.89 (18)	C22—C21—C20	118.8 (2)
C13—N3—Co1	127.88 (14)	C22—C21—H21	120.6
C17—N3—Co1	114.19 (13)	C20—C21—H21	120.6
C18—N4—C19	116.25 (16)	C21—C22—C23	122.5 (3)
C18—N4—Co1	115.21 (13)	C21—C22—F2	119.0 (2)
C19—N4—Co1	128.03 (14)	C23—C22—F2	118.5 (3)
C29—N5—C25	118.84 (18)	C22—C23—C24	118.7 (3)
C29—N5—Co1	114.14 (13)	C22—C23—H23	120.7
C25—N5—Co1	127.03 (15)	C24—C23—H23	120.7
C30—N6—C31	118.61 (17)	C19—C24—C23	120.6 (2)
C30—N6—Co1	116.15 (13)	C19—C24—H24	119.7
C31—N6—Co1	124.75 (13)	C23—C24—H24	119.7
N1—C1—C2	122.0 (2)	N5—C25—C26	121.5 (2)
N1—C1—H1	119.0	N5—C25—H25	119.3
C2—C1—H1	119.0	C26—C25—H25	119.3
C1—C2—C3	119.7 (2)	C27—C26—C25	119.6 (2)
C1—C2—H2	120.1	C27—C26—H26	120.2
C3—C2—H2	120.1	C25—C26—H26	120.2
C2—C3—C4	118.8 (2)	C26—C27—C28	119.1 (2)
C2—C3—H3	120.6	C26—C27—H27	120.4
C4—C3—H3	120.6	C28—C27—H27	120.4
C3—C4—C5	119.0 (2)	C29—C28—C27	119.1 (2)
C3—C4—H4	120.5	C29—C28—H28	120.4
C5—C4—H4	120.5	C27—C28—H28	120.4
N1—C5—C4	122.21 (17)	N5—C29—C28	121.87 (19)
N1—C5—C6	115.27 (17)	N5—C29—C30	114.99 (17)
C4—C5—C6	122.52 (18)	C28—C29—C30	123.1 (2)
O1—C6—N2	127.79 (16)	O3—C30—N6	127.64 (18)
O1—C6—C5	120.12 (18)	O3—C30—C29	120.81 (18)
N2—C6—C5	112.08 (16)	N6—C30—C29	111.53 (18)
C8—C7—C12	119.36 (17)	C36—C31—C32	118.4 (2)
C8—C7—N2	120.56 (18)	C36—C31—N6	121.07 (17)
C12—C7—N2	120.07 (16)	C32—C31—N6	120.50 (19)
C7—C8—C9	120.3 (2)	C31—C32—C33	121.5 (2)
C7—C8—H8	119.9	C31—C32—H32	119.3
C9—C8—H8	119.9	C33—C32—H32	119.3
C10—C9—C8	118.5 (2)	C34—C33—C32	118.8 (2)
C10—C9—H9	120.7	C34—C33—H33	120.6
C8—C9—H9	120.7	C32—C33—H33	120.6
C11—C10—F1	118.4 (2)	C33—C34—F3	119.3 (2)
C11—C10—C9	122.9 (2)	C33—C34—C35	122.2 (2)
F1—C10—C9	118.7 (2)	F3—C34—C35	118.5 (3)
C10—C11—C12	118.1 (2)	C34—C35—C36	119.0 (2)
C10—C11—H11	121.0	C34—C35—H35	120.5
C12—C11—H11	121.0	C36—C35—H35	120.5
C7—C12—C11	120.82 (18)	C31—C36—C35	120.1 (2)
C7—C12—H12	119.6	C31—C36—H36	120.0
C11—C12—H12	119.6	C35—C36—H36	120.0
N3—C13—C14	122.24 (19)	H11W—O1W—H12W	108.1
N3—C13—H13	118.9	H21W—O2W—H22W	108.3
C14—C13—H13	118.9	H31W—O3W—H32W	108.3
N6—Co1—N1—C1	97.26 (19)	N4—Co1—N5—C29	98.49 (13)
N3—Co1—N1—C1	−79.63 (19)	N2—Co1—N5—C25	95.36 (16)
N6—Co1—N1—C5	−78.36 (14)	N4—Co1—N5—C25	−81.39 (16)
N2—Co1—N1—C5	9.68 (14)	N2—Co1—N6—C30	87.26 (14)
N3—Co1—N1—C5	104.75 (14)	N4—Co1—N6—C30	−93.07 (14)
N6—Co1—N2—C6	82.28 (15)	N2—Co1—N6—C31	−84.61 (14)
N1—Co1—N2—C6	−10.88 (14)	N4—Co1—N6—C31	95.06 (14)
N3—Co1—N2—C6	−98.23 (15)	C6—N2—C7—C8	119.4 (2)
N6—Co1—N2—C7	−82.04 (16)	Co1—N2—C7—C8	−76.5 (2)
N3—Co1—N2—C7	97.45 (16)	C6—N2—C7—C12	−60.0 (3)
N5—Co1—N3—C13	95.80 (17)	Co1—N2—C7—C12	104.15 (19)
N1—Co1—N3—C13	−79.21 (17)	C18—N4—C19—C20	76.0 (3)
N5—Co1—N3—C17	−86.51 (14)	Co1—N4—C19—C20	−112.8 (2)
N1—Co1—N3—C17	98.49 (14)	C18—N4—C19—C24	−104.0 (2)
N5—Co1—N4—C18	92.24 (15)	Co1—N4—C19—C24	67.3 (3)
N1—Co1—N4—C18	−91.40 (15)	C30—N6—C31—C36	−73.1 (3)
N5—Co1—N4—C19	−79.11 (16)	Co1—N6—C31—C36	98.6 (2)
N1—Co1—N4—C19	97.24 (16)	C30—N6—C31—C32	109.5 (2)
N2—Co1—N5—C29	−84.76 (13)	Co1—N6—C31—C32	−78.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O2^i	0.85	2.04	2.856 (3)	162
O1W—H12W···O2W	0.85	2.19	2.855 (3)	135
O2W—H21W···O1	0.85	2.02	2.850 (2)	165
O2W—H22W···O3^ii	0.85	1.96	2.788 (2)	164
O3W—H31W···O1W	0.85	2.19	3.035 (3)	180

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