[2-(2-{Bis[2-(1H-imidazol-2-ylmethyl­eneamino)eth­yl]amino}ethyl­imino­meth­yl)imidazolido]cobalt(III) bis­(tetra­fluoridoborate) monohydrate

The title compound, [Co(C₁₈H₂₃N₁₀)](BF₄)₂·H₂O, is the result of complexing a Co cation (initially in a Co^II state) with tris­[2-(1H-imidazol-2-ylmethyl­eneamino)eth­yl]amine (L), obtained by a condensation process involving imidazole-2-carbaldehyde and tris­(2-amino­ethyl)amine. Both the Co cation and the ligand were modified in the synthesis process, the cation via oxidation to Co^III, and the ligand via deprotonation to convert it into the 2-(2-{bis­[2-(1H-imidazol-2-ylmethyl­eneamino)eth­yl]amino}ethyl­imino­meth­yl)imidazolide anion (L⁻). The ligand chelates the metal centre in a hexa­dentate fashion, forming a slightly distorted octa­hedral CoN₆ chromophore. Packing is governed by N—H...N hydrogen bonds defining zigzag chains. A similar structure in the literature is discussed, and the wrong assignment of the oxidation state, given therein to the Co cation, is corrected.

S1. Comment

It is well known (see e.g. Cotton & Wilkinson, 1988) that in the absence of complexing agents the Co^III species is usually not favoured in aqueous solutions containing the metal, while its stability is greatly increased when complexing agents containing nitrogen are present. Thus, it is not unusual to obtain Co^IIIN₆ chromophores via a synthesis procedure which starts with Co^II as the initial cation, and which transforms into Co^III through an unwitting oxidation process. In such conditions, these tranformations do not require much energy and can be spontaneous and perfectly feasible, even at room temperature. We present herein the result of one such transformation, where an intended complexation of a Co^II cation with tris[2-(1H-imidazol-2-ylmethyleneamino)ethyl]amine (L) obtained by condensation of imidazole-2-carbaldehyde and tris(2-aminoethyl)amine (see Experimental) resulted in the generation of the [Co^III(L^-)]²⁺ cation through the oxidation of the metal and the simultaneous loss of an imidazole H atom. The resulting ionic species was [2-(2-{bis[2-(1H-imidazol-2-ylmethyleneamino)ethyl]amino}ethyliminomethyl) imidazolido]cobalt(III) bis(tetrafluoridoborate) monohydrate, (I), and the structure is reported herein.

Fig. 1 shows a view of (I). The Co^III centre is octahedrally surrounded by a chelating L^- ligand acting in a µ₁-κ⁶N,N',N'',N''',N'''',N''''' mode through three of its imidazolyl and three imine N atoms. The resulting coordination polyhedron is rather regular in spite of the restraints imposed by chelation, with trans angles spanning the range 173.27 (14)–176.19 (14)° and cis ones 82.49 (14)–94.80 (14)° (Table 1). Co—N distances are also in a tight range, 1.898 (3)–1.950 (3) Å, with a mean of 1.927 (24) Å, well within the expected values for Co^III—N distances reported in the literature [mean value in Co^IIIN₆ chromophores for 1220 cases in the 2008 version of the CSD (Allen, 2002): 1.955 (25) Å]. The cation has approximate non-crystallographic C₃ symmetry, as assessed by the least-squares fit between one cation and its 120° rotated image, resulting in a mean deviation of 0.12 (1) Å (Fig. 2). The structure is completed by two well resolved, though strongly vibrating, BF₄^- counteranions, and a water molecule of crystallization.

From a crystallographic point of view, the most interesting feature of the structure is the formation of strong N—H···N hydrogen bonds between adjacent imidazole groups, which involves the deprotonated N22 as an acceptor and one of the protonated ones, N23, as a donor, and which appears as a distinctive feature for the Co^III presence (see discussion below). Fig. 3 shows the way in which this interaction threads a zigzag chain along [001]. The remaining imidazolyl nitrogen (N12), in turn, interacts with the pendant `water molecule + 2(BF₄^-) counteranions' hydrogen-bonded system shown in Fig. 1; the counterions stretch out at both sides of the [001] chains and their F atoms have weak C—H···F interactions (Table 2) between chains.

While searching in the literature for related structures, we came across a very similar Co compound (He, 2007) reported as a Co^II complex with the fully protonated tris-(2-aminoethyl)amine (ligand L) in the scheme, but reported in the crystal-data text as [Co(C₁₈H₂₃N₁₀)₂](ClO₄)₂.0.5H₂O, hereafter (II). This was described in the title, scheme and text as a Co^II complex having two independent [Co^IIL]²⁺ cationic groups in the asymmetric unit with charge balance provided by a four [ClO₄^1-] counteranions; there was also one water molecule in the asymmetric unit. To our surprise, the reported Co—N distances and angles in this (He, 2007) structure were in complete agreement with those in (I) and in principle totally ascribable to a Co^III cationic centre instead of the reported Co^II one. This misfit was also apparent in the reported formula, ORTEP plots and CIF coordinates, all of which confirmed that only two imidazole groups in the presumed L ligand were protonated, thus turning it into a L^- anion and thus enforcing the need for a 3+ cation at the central core. All these facts support the contention that the composite cationic groups in both compounds are completely equivalent, and should have been reported as [Co^IIIL^-]²⁺ in the He (2007) paper.

While a table of hydrogen-bond data is provided in the He (2007) paper, there is no discussion or description of the hydrogen bonding in the structure of (II). Inspection of the CIF for (II) shows that the packing is defined by parallel chains extending along [100] [in this case of two different types, corresponding to the two independent cation moieties in (II)], organized through the characteristic N—H···N synthon, a fingerprint disclosing the presence of the L^- ligand (and concomitantly, the Co^III cation) in these types of structures.

Related literature

For related literature, see: Allen (2002); Cotton & Wilkinson (1988); He (2007); He et al. (2004).

S2. Experimental

Tris-(2-aminoethylamine) (0.0748 ml, 0.5 mmol) and imidazol-2-carbaldehyde (0.14135 g, 1.5 mmol) were dissolved in 10 ml of methanol and the solution kept at reflux while stirring for half an hour. A solution of CoCl₂.6H₂O, (0.11897 g, 0.5 mmol) in 10 ml of water was added to this mixture, and the composite became deep red. Finally, 0.15726 g (1.5 mmol) of NH₄BF₄ was added to the solution while kept at reflux for another 7 h. Slow evaporation at room temperature for 2 weeks yielded single crystals suitable for X-ray diffraction. For an alternative synthesis, see He et al. (2004).

S3. Refinement

All the H atoms were found in a difference Fourier, and positioned afterwards at their expected positions, while allowed to ride both in coordinates (C—H = 0.93–0.97 Å, N—H = 0.86 Å and O—H = 0.85 Å), as well as in their isotropic displacement parameters [U_iso(H) = 1.2 or 1.5U_eq(host)].

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2003).

Figures

	Fig. 1. The asymmetric unit of (I), with displacement ellipsoids at the 30% level. Hydrogen bonds are shown by broken lines.
	Fig. 2. A least-squares fit between one cation and its 120° rotated image, showing the non-crystallographic pseudo C3 symmetry, viewed down the pseudo C3 axis.
	Fig. 3. Packing view of (I) projected down [100]. Only the zigzag chains running along [001] are shown (without counterions and solvates), for clarity. N—H···H [N—H···N?] bonds are shown as dashed lines.

[2-(2-{Bis[2-(1H-imidazol-2- ylmethyleneamino)ethyl]amino}ethyliminomethyl)imidazolido]cobalt(III) bis(tetrafluoridoborate) monohydrate

Crystal data

[Co(C18H23N10)](BF4)2·H2O	F(000) = 1280
Mr = 630.03	Dx = 1.636 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9999 reflections
a = 9.1704 (9) Å	θ = 2.1–26.2°
b = 18.2328 (19) Å	µ = 0.76 mm^−1
c = 15.3594 (15) Å	T = 298 K
β = 93.843 (2)°	Plate, red
V = 2562.3 (4) Å^3	0.44 × 0.31 × 0.11 mm
Z = 4

Data collection

Bruker SMART CCD area detector diffractometer	5778 independent reflections
Radiation source: fine-focus sealed tube	3528 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.076
CCD rotation images, thin slices scans	θmax = 28.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002)	h = −11→11
Tmin = 0.70, Tmax = 0.92	k = −23→23
21379 measured reflections	l = −20→20

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.194	H-atom parameters constrained
S = 0.93	w = 1/[σ^2(Fo^2) + (0.1166P)^2 + 0.6005P] where P = (Fo^2 + 2Fc^2)/3
5778 reflections	(Δ/σ)max = 0.001
361 parameters	Δρmax = 0.58 e Å^−3
0 restraints	Δρmin = −0.42 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.

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

	x	y	z	Uiso*/Ueq
Co1	0.86211 (5)	0.40146 (3)	0.76323 (3)	0.0392 (2)
N1	1.2341 (4)	0.4155 (2)	0.7710 (3)	0.0643 (11)
N11	0.7339 (3)	0.46309 (18)	0.6917 (2)	0.0432 (8)
N21	0.6739 (4)	0.5723 (2)	0.6461 (3)	0.0594 (10)
H21N	0.6759	0.6189	0.6378	0.071*
N31	0.9598 (4)	0.49463 (19)	0.7897 (2)	0.0462 (8)
C11	0.6112 (5)	0.4580 (3)	0.6388 (3)	0.0570 (12)
H11	0.5616	0.4149	0.6236	0.068*
C21	0.5724 (6)	0.5253 (3)	0.6117 (4)	0.0696 (14)
H21	0.4904	0.5374	0.5757	0.084*
C31	0.7723 (5)	0.5327 (2)	0.6963 (3)	0.0486 (10)
C41	0.8989 (5)	0.5501 (2)	0.7512 (3)	0.0523 (11)
H41	0.9343	0.5976	0.7585	0.063*
C51	1.0876 (5)	0.5046 (3)	0.8506 (3)	0.0606 (12)
H51A	1.0789	0.4730	0.9008	0.073*
H51B	1.0910	0.5550	0.8709	0.073*
C61	1.2281 (5)	0.4868 (3)	0.8083 (4)	0.0686 (14)
H61A	1.2418	0.5227	0.7630	0.082*
H61B	1.3090	0.4919	0.8519	0.082*
N12	0.7513 (3)	0.41238 (17)	0.8624 (2)	0.0426 (8)
N22	0.7126 (4)	0.3694 (2)	0.9951 (2)	0.0515 (9)
N32	0.9849 (3)	0.34084 (18)	0.8425 (2)	0.0418 (8)
C12	0.6230 (4)	0.4403 (2)	0.8854 (3)	0.0487 (10)
H12	0.5616	0.4715	0.8521	0.058*
C22	0.6001 (5)	0.4141 (2)	0.9674 (3)	0.0517 (11)
H22	0.5199	0.4252	0.9990	0.062*
C32	0.8005 (4)	0.3704 (2)	0.9299 (3)	0.0431 (9)
C42	0.9340 (5)	0.3319 (2)	0.9168 (3)	0.0484 (10)
H42	0.9801	0.3024	0.9597	0.058*
C52	1.1176 (4)	0.3018 (2)	0.8222 (3)	0.0559 (12)
H52A	1.1036	0.2804	0.7644	0.067*
H52B	1.1356	0.2622	0.8636	0.067*
C62	1.2495 (5)	0.3524 (3)	0.8254 (4)	0.0669 (14)
H62A	1.2701	0.3683	0.8852	0.080*
H62B	1.3333	0.3245	0.8087	0.080*
N13	0.7542 (3)	0.31638 (17)	0.7277 (2)	0.0414 (8)
N23	0.7170 (4)	0.22856 (19)	0.6331 (2)	0.0525 (9)
H23N	0.7258	0.2006	0.5886	0.063*
N33	0.9679 (4)	0.37837 (19)	0.6608 (2)	0.0460 (8)
C13	0.6387 (4)	0.2769 (3)	0.7513 (3)	0.0517 (11)
H13	0.5843	0.2856	0.7992	0.062*
C23	0.6169 (5)	0.2226 (2)	0.6923 (3)	0.0544 (11)
H23	0.5445	0.1869	0.6927	0.065*
C33	0.8004 (5)	0.2863 (2)	0.6565 (3)	0.0445 (9)
C43	0.9209 (4)	0.3221 (2)	0.6188 (3)	0.0497 (10)
H43	0.9608	0.3056	0.5683	0.060*
C53	1.0864 (5)	0.4212 (3)	0.6274 (3)	0.0613 (13)
H53A	1.0630	0.4730	0.6306	0.074*
H53B	1.0956	0.4089	0.5665	0.074*
C63	1.2313 (5)	0.4068 (3)	0.6788 (4)	0.0706 (15)
H63A	1.2613	0.3570	0.6666	0.085*
H63B	1.3040	0.4394	0.6569	0.085*
B1	0.7715 (8)	0.8259 (5)	0.3985 (5)	0.087 (2)
F21	0.9170 (5)	0.8209 (3)	0.3895 (3)	0.1396 (17)
F31	0.7555 (14)	0.8841 (4)	0.4361 (6)	0.325 (7)
F41	0.7158 (5)	0.8278 (5)	0.3177 (4)	0.226 (4)
F11	0.7348 (8)	0.7692 (4)	0.4460 (3)	0.199 (3)
B2	0.1760 (11)	0.6332 (4)	0.5975 (6)	0.100 (3)
F42	0.2207 (12)	0.6219 (5)	0.6738 (4)	0.328 (7)
F12	0.2469 (4)	0.6922 (2)	0.5603 (2)	0.1057 (12)
F22	0.0329 (6)	0.6413 (3)	0.5845 (3)	0.1455 (17)
F32	0.2023 (6)	0.5722 (3)	0.5468 (4)	0.162 (2)
O1W	0.5670 (5)	0.7015 (2)	0.5700 (3)	0.1080 (15)
H1WB	0.4743	0.7046	0.5664	0.162*
H1WA	0.5937	0.7263	0.5271	0.162*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0321 (3)	0.0440 (3)	0.0414 (3)	0.0004 (2)	0.0011 (2)	−0.0010 (2)
N1	0.043 (2)	0.067 (3)	0.082 (3)	−0.0013 (18)	0.003 (2)	0.003 (2)
N11	0.0355 (18)	0.052 (2)	0.0418 (19)	0.0035 (15)	−0.0017 (14)	0.0007 (15)
N21	0.058 (2)	0.054 (2)	0.066 (3)	0.0107 (19)	−0.001 (2)	0.0164 (19)
N31	0.0380 (18)	0.048 (2)	0.053 (2)	−0.0042 (15)	0.0062 (16)	−0.0049 (16)
C11	0.043 (2)	0.070 (3)	0.056 (3)	−0.004 (2)	−0.009 (2)	0.005 (2)
C21	0.052 (3)	0.085 (4)	0.070 (3)	0.003 (3)	−0.015 (3)	0.018 (3)
C31	0.046 (2)	0.050 (3)	0.051 (3)	0.003 (2)	0.007 (2)	0.007 (2)
C41	0.053 (3)	0.042 (2)	0.061 (3)	0.001 (2)	0.005 (2)	−0.004 (2)
C51	0.052 (3)	0.064 (3)	0.064 (3)	−0.003 (2)	−0.014 (2)	−0.005 (2)
C61	0.037 (3)	0.072 (3)	0.096 (4)	−0.007 (2)	−0.007 (3)	−0.003 (3)
N12	0.0362 (18)	0.049 (2)	0.0429 (19)	0.0067 (14)	0.0038 (14)	−0.0036 (15)
N22	0.052 (2)	0.058 (2)	0.044 (2)	0.0092 (17)	0.0026 (17)	−0.0027 (17)
N32	0.0363 (17)	0.0471 (19)	0.0415 (19)	0.0069 (14)	−0.0008 (14)	−0.0014 (15)
C12	0.041 (2)	0.058 (3)	0.048 (2)	0.017 (2)	0.0095 (19)	−0.003 (2)
C22	0.052 (3)	0.054 (3)	0.049 (3)	0.013 (2)	0.011 (2)	−0.005 (2)
C32	0.040 (2)	0.052 (2)	0.037 (2)	0.0043 (18)	0.0003 (18)	0.0039 (18)
C42	0.045 (2)	0.048 (2)	0.051 (3)	0.0018 (19)	−0.0090 (19)	0.0039 (19)
C52	0.040 (2)	0.060 (3)	0.070 (3)	0.020 (2)	0.010 (2)	0.011 (2)
C62	0.036 (2)	0.073 (3)	0.092 (4)	0.013 (2)	0.001 (2)	0.005 (3)
N13	0.0382 (18)	0.0433 (18)	0.0427 (19)	−0.0054 (14)	0.0021 (14)	−0.0040 (15)
N23	0.058 (2)	0.056 (2)	0.044 (2)	−0.0156 (18)	0.0010 (17)	−0.0075 (16)
N33	0.0400 (19)	0.050 (2)	0.049 (2)	−0.0073 (15)	0.0063 (15)	−0.0065 (16)
C13	0.037 (2)	0.063 (3)	0.055 (3)	−0.005 (2)	0.010 (2)	−0.001 (2)
C23	0.052 (3)	0.056 (3)	0.056 (3)	−0.014 (2)	0.001 (2)	0.003 (2)
C33	0.046 (2)	0.046 (2)	0.041 (2)	−0.0057 (18)	0.0019 (18)	0.0010 (18)
C43	0.043 (2)	0.058 (3)	0.050 (2)	0.001 (2)	0.0173 (19)	−0.004 (2)
C53	0.052 (3)	0.065 (3)	0.069 (3)	−0.017 (2)	0.018 (2)	−0.001 (2)
C63	0.051 (3)	0.070 (3)	0.094 (4)	−0.009 (2)	0.032 (3)	−0.002 (3)
B1	0.065 (4)	0.104 (6)	0.091 (5)	0.005 (4)	−0.002 (4)	0.034 (5)
F21	0.114 (3)	0.176 (5)	0.127 (3)	0.016 (3)	−0.004 (3)	0.045 (3)
F31	0.603 (19)	0.121 (5)	0.284 (10)	0.134 (8)	0.269 (12)	0.033 (5)
F41	0.115 (4)	0.418 (11)	0.139 (4)	−0.124 (5)	−0.050 (3)	0.140 (6)
F11	0.259 (7)	0.205 (6)	0.135 (4)	−0.099 (5)	0.022 (4)	0.082 (4)
B2	0.127 (7)	0.067 (5)	0.096 (6)	−0.042 (5)	−0.060 (5)	0.029 (4)
F42	0.530 (15)	0.283 (8)	0.145 (5)	−0.272 (10)	−0.178 (8)	0.122 (6)
F12	0.115 (3)	0.087 (2)	0.113 (3)	−0.034 (2)	−0.011 (2)	0.023 (2)
F22	0.121 (4)	0.160 (4)	0.159 (4)	−0.014 (3)	0.030 (3)	0.033 (3)
F32	0.169 (5)	0.084 (3)	0.236 (6)	−0.010 (3)	0.038 (4)	0.005 (4)
O1W	0.102 (3)	0.090 (3)	0.132 (4)	0.000 (2)	0.007 (3)	0.052 (3)

Geometric parameters (Å, º)

Co1—N12	1.898 (3)	C32—C42	1.438 (6)
Co1—N13	1.901 (3)	C42—H42	0.9300
Co1—N11	1.918 (3)	C52—C62	1.519 (6)
Co1—N32	1.946 (3)	C52—H52A	0.9700
Co1—N33	1.948 (3)	C52—H52B	0.9700
Co1—N31	1.950 (3)	C62—H62A	0.9700
N1—C61	1.422 (6)	C62—H62B	0.9700
N1—C63	1.424 (7)	N13—C33	1.319 (5)
N1—C62	1.425 (6)	N13—C13	1.350 (5)
N11—C31	1.318 (5)	N23—C33	1.337 (5)
N11—C11	1.346 (5)	N23—C23	1.339 (6)
N21—C21	1.347 (6)	N23—H23N	0.8600
N21—C31	1.354 (5)	N33—C43	1.271 (5)
N21—H21N	0.8600	N33—C53	1.460 (5)
N31—C41	1.280 (5)	C13—C23	1.348 (6)
N31—C51	1.461 (5)	C13—H13	0.9300
C11—C21	1.335 (7)	C23—H23	0.9300
C11—H11	0.9300	C33—C43	1.438 (6)
C21—H21	0.9300	C43—H43	0.9300
C31—C41	1.424 (6)	C53—C63	1.523 (7)
C41—H41	0.9300	C53—H53A	0.9700
C51—C61	1.516 (7)	C53—H53B	0.9700
C51—H51A	0.9700	C63—H63A	0.9700
C51—H51B	0.9700	C63—H63B	0.9700
C61—H61A	0.9700	B1—F31	1.222 (11)
C61—H61B	0.9700	B1—F41	1.311 (9)
N12—C32	1.342 (5)	B1—F11	1.320 (8)
N12—C12	1.350 (5)	B1—F21	1.354 (8)
N22—C32	1.327 (5)	B2—F42	1.233 (8)
N22—C22	1.360 (5)	B2—F22	1.323 (10)
N32—C42	1.272 (5)	B2—F32	1.388 (10)
N32—C52	1.461 (5)	B2—F12	1.398 (8)
C12—C22	1.376 (6)	O1W—H1WB	0.8500
C12—H12	0.9300	O1W—H1WA	0.8497
C22—H22	0.9300
N12—Co1—N13	91.13 (14)	N22—C32—N12	113.6 (4)
N12—Co1—N11	93.33 (14)	N22—C32—C42	131.7 (4)
N13—Co1—N11	91.50 (14)	N12—C32—C42	114.5 (4)
N12—Co1—N32	82.88 (13)	N32—C42—C32	115.5 (4)
N13—Co1—N32	89.10 (14)	N32—C42—H42	122.3
N11—Co1—N32	176.18 (14)	C32—C42—H42	122.3
N12—Co1—N33	173.26 (14)	N32—C52—C62	111.8 (4)
N13—Co1—N33	82.49 (14)	N32—C52—H52A	109.3
N11—Co1—N33	89.03 (14)	C62—C52—H52A	109.3
N32—Co1—N33	94.79 (14)	N32—C52—H52B	109.3
N12—Co1—N31	90.27 (14)	C62—C52—H52B	109.3
N13—Co1—N31	173.63 (14)	H52A—C52—H52B	107.9
N11—Co1—N31	82.21 (14)	N1—C62—C52	115.1 (4)
N32—Co1—N31	97.24 (14)	N1—C62—H62A	108.5
N33—Co1—N31	96.31 (14)	C52—C62—H62A	108.5
C61—N1—C63	120.3 (5)	N1—C62—H62B	108.5
C61—N1—C62	120.5 (5)	C52—C62—H62B	108.5
C63—N1—C62	119.2 (4)	H62A—C62—H62B	107.5
C31—N11—C11	107.9 (4)	C33—N13—C13	107.6 (3)
C31—N11—Co1	112.5 (3)	C33—N13—Co1	112.8 (3)
C11—N11—Co1	139.5 (3)	C13—N13—Co1	139.5 (3)
C21—N21—C31	107.5 (4)	C33—N23—C23	106.7 (4)
C21—N21—H21N	126.2	C33—N23—H23N	126.7
C31—N21—H21N	126.2	C23—N23—H23N	126.7
C41—N31—C51	120.3 (4)	C43—N33—C53	119.2 (4)
C41—N31—Co1	114.3 (3)	C43—N33—Co1	114.5 (3)
C51—N31—Co1	125.4 (3)	C53—N33—Co1	126.2 (3)
C21—C11—N11	108.6 (4)	C23—C13—N13	107.1 (4)
C21—C11—H11	125.7	C23—C13—H13	126.4
N11—C11—H11	125.7	N13—C13—H13	126.4
C11—C21—N21	107.4 (4)	N23—C23—C13	108.7 (4)
C11—C21—H21	126.3	N23—C23—H23	125.7
N21—C21—H21	126.3	C13—C23—H23	125.7
N11—C31—N21	108.5 (4)	N13—C33—N23	109.9 (4)
N11—C31—C41	116.7 (4)	N13—C33—C43	116.3 (4)
N21—C31—C41	134.8 (4)	N23—C33—C43	133.7 (4)
N31—C41—C31	114.3 (4)	N33—C43—C33	113.9 (4)
N31—C41—H41	122.8	N33—C43—H43	123.0
C31—C41—H41	122.8	C33—C43—H43	123.0
N31—C51—C61	111.6 (4)	N33—C53—C63	111.7 (4)
N31—C51—H51A	109.3	N33—C53—H53A	109.3
C61—C51—H51A	109.3	C63—C53—H53A	109.3
N31—C51—H51B	109.3	N33—C53—H53B	109.3
C61—C51—H51B	109.3	C63—C53—H53B	109.3
H51A—C51—H51B	108.0	H53A—C53—H53B	107.9
N1—C61—C51	115.1 (4)	N1—C63—C53	117.0 (4)
N1—C61—H61A	108.5	N1—C63—H63A	108.1
C51—C61—H61A	108.5	C53—C63—H63A	108.1
N1—C61—H61B	108.5	N1—C63—H63B	108.1
C51—C61—H61B	108.5	C53—C63—H63B	108.1
H61A—C61—H61B	107.5	H63A—C63—H63B	107.3
C32—N12—C12	105.5 (3)	F31—B1—F41	111.8 (9)
C32—N12—Co1	112.9 (3)	F31—B1—F11	112.1 (8)
C12—N12—Co1	140.6 (3)	F41—B1—F11	116.5 (8)
C32—N22—C22	104.0 (3)	F31—B1—F21	104.9 (9)
C42—N32—C52	119.3 (3)	F41—B1—F21	103.2 (7)
C42—N32—Co1	113.7 (3)	F11—B1—F21	107.1 (7)
C52—N32—Co1	126.8 (3)	F42—B2—F22	115.2 (11)
N12—C12—C22	107.3 (4)	F42—B2—F32	109.8 (9)
N12—C12—H12	126.4	F22—B2—F32	102.3 (6)
C22—C12—H12	126.4	F42—B2—F12	112.6 (6)
N22—C22—C12	109.6 (4)	F22—B2—F12	109.7 (6)
N22—C22—H22	125.2	F32—B2—F12	106.5 (8)
C12—C22—H22	125.2	H1WB—O1W—H1WA	104.6

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···F11	0.85	2.01	2.814 (6)	157
O1W—H1WB···F12	0.85	2.09	2.934 (6)	170
N21—H21N···O1W	0.86	2.05	2.779 (5)	142
N23—H23N···N22^i	0.86	1.92	2.770 (5)	170
C23—H23···F41^ii	0.93	2.40	3.181 (6)	142
C41—H41···F21^iii	0.93	2.51	3.166 (6)	127
C42—H42···F21^iv	0.93	2.47	3.197 (6)	136
C43—H43···F22^ii	0.93	2.54	3.248 (7)	133
C61—H61A···F42^v	0.97	2.27	3.213 (8)	164

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z+1; (iii) x, −y+3/2, z+1/2; (iv) −x+2, y−1/2, −z+3/2; (v) x+1, y, z.