trans-Bis­(di­methyl­glyoximato-[kappa]²N,N')­(1-hexenyl)(pyridine-[kappa]N)­cobalt(III): a cobaloxime-substituted terminal alkene that rapidly isomerizes to a cobaloxime-substituted internal alkenyl complex

An unusual cobaloxime-substituted terminal alkene, [Co(C₆H₁₁)(C₄H₇N₂O₂)₂(C₅H₅N)], has been isolated and characterized by X-ray crystallography. The double bond in the alkene readily isomerizes, but the title compound could be isolated and structurally characterized at low temperature.

S1. Comment

We have been interested in the preparation of cobaloxime complexes [cobaloxime is (pyridine)(dimethylglyoxime)₂cobalt] that contain cobalt-sp² carbon bonds and the use of these complexes in cycloaddition chemistry (Welker, 2001). In 2000, we reported a new method for the preparation of cobalt-sp² carbon bonds, which involved a zinc-mediated coupling of alkenyl halides and trifluoromethanesulfonates, (II), to (py)₂(dmg)₂Co (Pickin & Welker, 2000). One of the coupling products prepared, a 2-cobaloxime-substituted 1-hexene complex, (III), isomerized readily to (E)-2-cobaloxime-2-hexene, (IV). The 2-cobaloxime 1-hexenyl complex (III) has now been crystallized at low temperature and its structure is reported here.

The molecular structure of (III) is depicted in Fig. 1, and selected geometric parameters are given in Table 1. The Co atom in III is coordinated in a slightly distorted octahedral geometry. The Co—N bond distances in the equatorial plane (Co—N1, Co—N2, Co—N3 and Co—N4) are 1.871 (5), 1.877 (5), 1.881 (5) and 1.903 (5) Å, resepctively. The Co—N5 (pyridine nitrogen) bond length is 2.089 (4) Å and the Co—C10 distance is 1.994 (5) Å. The Co atom and atoms N1–N4 are coplanar within 0.016 Å. The nearly coplanar Co1/C9/C10/C11/C12 (to within 0.05 Å) and Co1/N5/C15/C16/ C17/C18/C19 (to within 0.03 Å) groups are nearly parallel (5.2°) and are oriented so that they bisect the N4—Co—N1 and N2—Co—N3 angles. This arrangement minimizes the interligand steric interaction of the axial ligands with the dimethylglyoximes. The Co—C10 bond [1.994 (5) Å] falls in the range of other Cosp²–C bond lengths that we have reported previously for cobaloxime dienyl complexes [1.954 (15)–2.019 (6) Å; Stokes et al., 1995; Wright, et al., 1994]. This bond length is significantly longer than those reported previously for cobaloxime ethenyl complexes [1.945 (5)–1.953 (3) Å; McCauley et al., 2002) but comparable to Cosp² carbon bond lengths in cobaloxime complexes containing longer carbon chains in the alkenyl fragment [1.971 (13), 1.972 (7) and 1.976 (4) Å; Stolter et al., 1975; Adams et al., 1998; Adams et al., 1997). Previously reported Cosp³—C bond lengths in cobaloxime complexes range from 1.998 (5) Å for the cobaloxime methyl complex to 2.085 (3) Å for the isopropyl complex (Brescani-Pahor et al., 1985). The C9═C10 double bond in the hexenyl ligand [1.324 (7) Å] is largely unaffected by the presence of the cobaloxime, and this observation has also been true of the other cobaloxime- substituted alkenyl complexes referenced above. The Co—C10—C9 and Co—C10—C11 bond angles are 119.3 (4) and 117.5 (4)°, respectively. Most Co—CAsp²—CBsp² bond angles reported previously have been larger than 120°, but we have reported two other examples of cobaloxime alkenyl and dienyl complexes in which these angles were 118.3 (3)° and 116.7 (5)° (Adams et al., 1997; Stokes et al., 1995). Intramolecular hydrogen-bonding interactions involving equatorial dimethylglyoximate ligands are described in Table 2. The values reported here agree with corresponding values reported for 200 compounds with 269 relevant bonds in the Cambridge Structural Database (Allen, 2002), with average O···O contacts and O—H···O angles of 2.488 Å and 168.2°, respectively.

The cobaloxime alkenyl complex (III), which contains a terminal alkene, underwent facile double-bond isomerization upon attempted silica chromatography or simply upon standing in CDCl₃. The rate constant for isomerization was determined by analysis of the appearance of the alkenyl methyl signal, and this analysis was carried out for several half lives. A rate constant of 3.9 x 10⁻² min⁻¹ (R = 0.9707) with a half life of 18 min was calculated. The alkenyl complex to which (III) isomerized was demonstrated to contain the E alkene geometry shown in (IV), on the basis of the observation of a strong nOe from the alkenyl proton to the dimethylglyoxime ligand methyls and the absence of a nOe from those same ligand methyl groups to the methyl or methylene protons α to the alkene in the hexenyl ligand.

S2. Experimental

Complex (III) (1-hexen-2-yl)pyridinebis(dimethylglyoximato)cobalt(III) was prepared as described by Pickin & Welker (2000). Crystals of (III) were grown by slow diffusion of pentane into a 1,2- dichloroethane solution of (III) at 253 K. The isomerization kinetics experiment was carried out in CDCl₃. The rate constant was determined by analysis of the appearance of the alkenyl methyl signal, and this analysis was carried out for several half lives. An array of ¹H spectra (acquisition time of 1.0 min) were acquired every 10.0 min for 170 min (nine half lives). All spectra were processed and phased with the same parameters. The appearance of the alkenyl methyl was integrated relative to the ortho-pyridine signal. SigmaPlot 2000 (SPSS Science Inc. Chicago, IL) was used to determine the rate constant for an integration versus time plot. The equation for an exponentially rising peak with a maximum of I = I_o(1 − e^-kt) was used to fit the data. A rate constant of 3.9 x 10⁻² min⁻¹ (R = 0.9707) with a half life of 18 min was calculated.

S3. Refinement

Atoms H3O, H4O, H9A and H9B were located from a difference Fourier map and refined as independent isotropic atoms. The methyl groups (C5, C6, C7, C8, C14 and their H atoms) were refined as rigid rotors, with idealized sp³-hybridized geometry and a C—H bond length of 0.97 Å. The remaining H atoms were included in the structure-factor calculations as idealized atoms (assuming sp²– or sp³-hybridization of the C atoms and C—H bond lengths of 0.94–0.98 Å) riding on their respective C atoms. The isotropic displacement parameters for atoms H3O, H4O, H9A and H9B refined to final U_iso values of 0.07 (3), 0.02 (1), 0.05 (2) and 0.03 (1) Ų, respectively. The U_iso parameters of the remaining H atoms were fixed at 1.2 (non-methyl) or 1.5 (methyl) times the U_eq values of the C atoms to which they are covalently bonded.

Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: Bruker SHELXTL-NT (Bruker, 2001); program(s) used to solve structure: Bruker SHELXTL-NT; program(s) used to refine structure: Bruker SHELXTL-NT; molecular graphics: Bruker SHELXTL-NT; software used to prepare material for publication: Bruker SHELXTL-NT.

Figures

Fig. 1. The molecular structure of (III). All non-H atoms are represented by displacement ellipsoids at the 50% probability level. H atoms are represented by spheres of arbitrarily radii, which are in no way representative of their true thermal motion. Hydrogen-bonding interactions are represented by dashed lines.

(III)

Crystal data

[Co(C6H11)(C4H7N2O2)2(C5H5N)]	F(000) = 476
Mr = 451.41	Dx = 1.402 Mg m^−3
Monoclinic, Pn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yac	Cell parameters from 39 reflections
a = 8.268 (3) Å	θ = 3.0–12.0°
b = 11.757 (3) Å	µ = 0.84 mm^−1
c = 11.0253 (19) Å	T = 228 K
β = 93.721 (18)°	Chunk, orange
V = 1069.5 (4) Å^3	0.45 × 0.24 × 0.18 mm
Z = 2

Data collection

Bruker P4 diffractometer	2660 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.034
Graphite monochromator	θmax = 27.5°, θmin = 2.5°
ω scans	h = −1→10
Absorption correction: ψ-scan North et al, 1968	k = −15→1
Tmin = 0.151, Tmax = 0.187	l = −14→14
3254 measured reflections	3 standard reflections every 197 reflections
2971 independent reflections	intensity decay: none

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)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.065P)^2 + 0.1117P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
2971 reflections	Δρmax = 0.65 e Å^−3
278 parameters	Δρmin = −0.24 e Å^−3
2 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.09 (2)

Special details

Experimental. 'North, A. C. T., Phillips, D. C. & Mathews, F. S.(1968) Acta Cryst. A24, 351 − 359.' ?

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.

Mean-plane data from final SHELXL refinement run:

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

7.6344 (0.0044) x + 0.1455 (0.0317) y − 4.8822 (0.0115) z = 0.7147 (0.0090)

* −0.0325 (0.0026) Co1 * 0.0320 (0.0045) N5 * 0.0165 (0.0047) C15 * −0.0033 (0.0045) C16 * −0.0260 (0.0053) C17 * −0.0071 (0.0044) C18 * 0.0204 (0.0044) C19 − 1.3599 (0.0069) N1 − 1.5311 (0.0064) N2 1.3006 (0.0068) N3 1.4951 (0.0067) N4 − 0.1043 (0.0063) C10

Rms deviation of fitted atoms = 0.0224

3.5592 (0.0052) x + 1.3958 (0.0068) y + 9.5362 (0.0048) z = 3.9570 (0.0024)

Angle to previous plane (with approximate e.s.d.) = 86.81 (0.07)

* 0.0186 (0.0016) Co1 * −0.0167 (0.0038) N1 * 0.0083 (0.0037) N2 * 0.0031 (0.0039) N3 * 0.0327 (0.0040) N4 * −0.0027 (0.0037) O1 * 0.0678 (0.0035) O2 * 0.0226 (0.0036) O3 * 0.0853 (0.0040) O4 * −0.0468 (0.0047) C1 * −0.0400 (0.0043) C2 * −0.0780 (0.0042) C3 * −0.0541 (0.0045) C4 2.1066 (0.0048) N5 − 1.9754 (0.0055) C10

Rms deviation of fitted atoms = 0.0455

7.4086 (0.0069) x + 1.3277 (0.0389) y − 5.3646 (0.0150) z = 0.7645 (0.0097)

Angle to previous plane (with approximate e.s.d.) = 89.14 (0.09)

* −0.0018 (0.0013) Co1 * −0.0028 (0.0020) C9 * 0.0070 (0.0050) C10 * −0.0025 (0.0018) C11 − 1.4621 (0.0066) N1 − 1.3739 (0.0069) N2 1.4668 (0.0065) N3 1.3986 (0.0067) N4 0.1274 (0.0093) C12 1.5361 (0.0095) C13 1.5814 (0.0122) C14

Rms deviation of fitted atoms = 0.0041

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.

The top 3 peaks (0.65 − 0.39 e/ų) in the final difference Fourier map were within 0.86 Å of the Co atom.

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

	x	y	z	Uiso*/Ueq
Co1	0.26605 (9)	0.23452 (4)	0.28328 (7)	0.02091 (14)
O1	0.1761 (6)	0.0104 (3)	0.3474 (3)	0.0387 (10)
O2	0.1011 (6)	0.4426 (3)	0.3195 (3)	0.0368 (10)
O3	0.3598 (6)	0.4588 (3)	0.2159 (4)	0.0390 (10)
H3O	0.263 (11)	0.461 (6)	0.251 (6)	0.07 (3)*
O4	0.4415 (6)	0.0283 (3)	0.2550 (4)	0.0417 (10)
H4O	0.358 (7)	0.018 (4)	0.279 (5)	0.020 (14)*
N1	0.1340 (6)	0.1222 (4)	0.3453 (4)	0.0270 (11)
N2	0.0984 (6)	0.3290 (4)	0.3309 (4)	0.0262 (10)
N3	0.3960 (6)	0.3468 (4)	0.2167 (4)	0.0278 (11)
N4	0.4370 (6)	0.1398 (4)	0.2348 (4)	0.0277 (11)
N5	0.3841 (6)	0.2545 (3)	0.4553 (4)	0.0241 (10)
C1	−0.0014 (8)	0.1559 (5)	0.3877 (5)	0.0324 (13)
C2	−0.0216 (7)	0.2788 (5)	0.3780 (4)	0.0321 (13)
C3	0.5241 (7)	0.3126 (6)	0.1654 (4)	0.0336 (13)
C4	0.5483 (7)	0.1910 (6)	0.1767 (5)	0.0323 (13)
C5	−0.1183 (9)	0.0761 (6)	0.4390 (5)	0.0531 (19)
H5A	−0.0765	−0.0009	0.4357	0.080*
H5B	−0.2214	0.0805	0.3919	0.080*
H5C	−0.1334	0.0964	0.5228	0.080*
C6	−0.1647 (8)	0.3395 (6)	0.4217 (5)	0.0520 (17)
H6A	−0.1542	0.4204	0.4068	0.078*
H6B	−0.1707	0.3264	0.5081	0.078*
H6C	−0.2626	0.3114	0.3785	0.078*
C7	0.6314 (9)	0.3922 (6)	0.1004 (6)	0.0590 (19)
H7A	0.5899	0.4691	0.1051	0.089*
H7B	0.6329	0.3697	0.0158	0.089*
H7C	0.7405	0.3891	0.1382	0.089*
C8	0.6881 (8)	0.1285 (6)	0.1277 (6)	0.0500 (17)
H8A	0.6793	0.0481	0.1457	0.075*
H8B	0.7890	0.1579	0.1653	0.075*
H8C	0.6866	0.1392	0.0404	0.075*
C9	0.1361 (8)	0.1106 (5)	0.0733 (5)	0.0369 (12)
H9A	0.079 (8)	0.107 (5)	−0.012 (5)	0.049 (17)*
H9B	0.171 (7)	0.041 (4)	0.111 (4)	0.027 (13)*
C10	0.1523 (7)	0.2142 (4)	0.1196 (5)	0.0260 (11)
C11	0.0870 (7)	0.3174 (4)	0.0566 (4)	0.0326 (12)
H11A	0.1749	0.3731	0.0549	0.039*
H11B	0.0040	0.3500	0.1058	0.039*
C12	0.0116 (7)	0.3030 (5)	−0.0752 (4)	0.0352 (12)
H12A	−0.0595	0.2362	−0.0783	0.042*
H12B	−0.0554	0.3697	−0.0965	0.042*
C13	0.1364 (7)	0.2890 (5)	−0.1689 (4)	0.0467 (15)
H13A	0.2015	0.3585	−0.1719	0.056*
H13B	0.2093	0.2261	−0.1449	0.056*
C14	0.0563 (9)	0.2653 (5)	−0.2939 (5)	0.0547 (16)
H14A	0.1388	0.2568	−0.3519	0.082*
H14B	−0.0146	0.3282	−0.3184	0.082*
H14C	−0.0067	0.1959	−0.2915	0.082*
C15	0.4282 (7)	0.1650 (4)	0.5247 (4)	0.0363 (12)
H15A	0.4096	0.0916	0.4929	0.044*
C16	0.4991 (8)	0.1753 (5)	0.6400 (5)	0.0465 (14)
H16A	0.5296	0.1101	0.6854	0.056*
C17	0.5250 (8)	0.2813 (5)	0.6882 (5)	0.0465 (15)
H17A	0.5719	0.2906	0.7676	0.056*
C18	0.4802 (8)	0.3744 (5)	0.6172 (5)	0.0441 (13)
H18A	0.4974	0.4484	0.6475	0.053*
C19	0.4112 (7)	0.3583 (4)	0.5030 (5)	0.0322 (12)
H19A	0.3812	0.4223	0.4558	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0224 (2)	0.0222 (2)	0.0184 (2)	−0.0006 (4)	0.00348 (16)	−0.0002 (3)
O1	0.058 (3)	0.0241 (17)	0.0341 (19)	−0.0064 (18)	0.004 (2)	0.0034 (14)
O2	0.051 (3)	0.0305 (19)	0.0283 (17)	0.0132 (19)	−0.0001 (18)	−0.0032 (14)
O3	0.052 (3)	0.0228 (18)	0.042 (2)	−0.0070 (19)	0.001 (2)	0.0050 (14)
O4	0.047 (3)	0.029 (2)	0.049 (2)	0.0070 (19)	0.003 (2)	−0.0085 (17)
N1	0.034 (3)	0.028 (2)	0.0191 (19)	−0.0042 (19)	−0.0022 (19)	0.0011 (16)
N2	0.028 (3)	0.032 (2)	0.0192 (18)	0.0082 (19)	0.0024 (18)	0.0022 (15)
N3	0.030 (3)	0.031 (2)	0.022 (2)	−0.0022 (18)	0.0031 (19)	0.0003 (15)
N4	0.029 (3)	0.027 (2)	0.026 (2)	0.0047 (19)	−0.002 (2)	−0.0044 (16)
N5	0.023 (2)	0.029 (2)	0.0198 (19)	0.0026 (18)	0.0023 (17)	0.0000 (16)
C1	0.033 (3)	0.042 (3)	0.022 (2)	−0.008 (2)	0.003 (2)	0.002 (2)
C2	0.026 (3)	0.051 (4)	0.019 (2)	0.005 (3)	0.001 (2)	0.001 (2)
C3	0.026 (3)	0.050 (4)	0.025 (3)	−0.007 (3)	0.005 (2)	0.003 (2)
C4	0.020 (3)	0.051 (4)	0.027 (2)	0.003 (3)	0.003 (2)	−0.009 (2)
C5	0.044 (4)	0.085 (5)	0.032 (3)	−0.018 (4)	0.010 (3)	0.014 (3)
C6	0.034 (3)	0.089 (5)	0.033 (3)	0.020 (3)	0.003 (3)	−0.008 (3)
C7	0.054 (4)	0.066 (4)	0.058 (4)	−0.021 (3)	0.015 (4)	0.016 (3)
C8	0.034 (3)	0.069 (4)	0.048 (3)	0.007 (3)	0.011 (3)	−0.013 (3)
C9	0.047 (3)	0.037 (3)	0.026 (2)	−0.002 (3)	−0.005 (2)	−0.004 (2)
C10	0.023 (3)	0.032 (3)	0.023 (2)	0.000 (2)	0.003 (2)	−0.001 (2)
C11	0.041 (3)	0.034 (3)	0.022 (2)	0.004 (2)	0.001 (2)	−0.0015 (19)
C12	0.040 (3)	0.041 (3)	0.024 (2)	0.001 (2)	−0.005 (2)	−0.004 (2)
C13	0.051 (4)	0.060 (4)	0.029 (2)	−0.005 (3)	0.006 (3)	0.004 (2)
C14	0.075 (4)	0.064 (4)	0.026 (2)	−0.003 (4)	0.009 (3)	−0.002 (2)
C15	0.046 (3)	0.034 (3)	0.029 (2)	0.009 (2)	−0.002 (2)	0.000 (2)
C16	0.059 (4)	0.049 (3)	0.029 (2)	0.017 (3)	−0.010 (3)	0.002 (2)
C17	0.051 (3)	0.057 (4)	0.029 (2)	0.005 (3)	−0.015 (3)	−0.010 (3)
C18	0.053 (4)	0.041 (3)	0.037 (3)	−0.009 (3)	0.000 (3)	−0.010 (2)
C19	0.035 (3)	0.026 (3)	0.035 (3)	−0.001 (2)	−0.002 (2)	−0.003 (2)

Geometric parameters (Å, º)

Co1—N1	1.871 (5)	C7—H7B	0.9700
Co1—N2	1.877 (5)	C7—H7C	0.9700
Co1—N3	1.881 (5)	C8—H8A	0.9700
Co1—N4	1.903 (5)	C8—H8B	0.9700
Co1—C10	1.994 (5)	C8—H8C	0.9700
Co1—N5	2.089 (4)	C9—C10	1.324 (7)
O1—N1	1.360 (6)	C9—H9A	1.02 (6)
O2—N2	1.342 (6)	C9—H9B	0.95 (5)
O3—N3	1.349 (6)	C10—C11	1.482 (7)
O3—H3O	0.91 (9)	C11—C12	1.553 (6)
O4—N4	1.330 (6)	C11—H11A	0.9800
O4—H4O	0.77 (5)	C11—H11B	0.9800
N1—C1	1.303 (8)	C12—C13	1.516 (7)
N2—C2	1.292 (7)	C12—H12A	0.9800
N3—C3	1.297 (7)	C12—H12B	0.9800
N4—C4	1.303 (8)	C13—C14	1.515 (7)
N5—C15	1.338 (6)	C13—H13A	0.9800
N5—C19	1.342 (6)	C13—H13B	0.9800
C1—C2	1.458 (8)	C14—H14A	0.9700
C1—C5	1.485 (8)	C14—H14B	0.9700
C2—C6	1.488 (8)	C14—H14C	0.9700
C3—C4	1.448 (10)	C15—C16	1.370 (7)
C3—C7	1.503 (8)	C15—H15A	0.9400
C4—C8	1.499 (9)	C16—C17	1.366 (8)
C5—H5A	0.9700	C16—H16A	0.9400
C5—H5B	0.9700	C17—C18	1.382 (8)
C5—H5C	0.9700	C17—H17A	0.9400
C6—H6A	0.9700	C18—C19	1.361 (7)
C6—H6B	0.9700	C18—H18A	0.9400
C6—H6C	0.9700	C19—H19A	0.9400
C7—H7A	0.9700
N1—Co1—N2	81.7 (2)	C3—C7—H7B	109.5
N1—Co1—N3	178.4 (2)	H7A—C7—H7B	109.5
N2—Co1—N3	98.31 (19)	C3—C7—H7C	109.5
N1—Co1—N4	98.70 (19)	H7A—C7—H7C	109.5
N2—Co1—N4	179.6 (2)	H7B—C7—H7C	109.5
N3—Co1—N4	81.3 (2)	C4—C8—H8A	109.5
N1—Co1—C10	89.7 (2)	C4—C8—H8B	109.5
N2—Co1—C10	90.6 (2)	H8A—C8—H8B	109.5
N3—Co1—C10	88.8 (2)	C4—C8—H8C	109.5
N4—Co1—C10	89.5 (2)	H8A—C8—H8C	109.5
N1—Co1—N5	89.82 (18)	H8B—C8—H8C	109.5
N2—Co1—N5	89.40 (18)	C10—C9—H9A	115 (3)
N3—Co1—N5	91.74 (19)	C10—C9—H9B	127 (3)
N4—Co1—N5	90.50 (19)	H9A—C9—H9B	119 (4)
C10—Co1—N5	179.5 (2)	C9—C10—C11	123.2 (5)
N3—O3—H3O	103 (4)	C9—C10—Co1	119.3 (4)
N4—O4—H4O	102 (4)	C11—C10—Co1	117.5 (4)
C1—N1—O1	120.9 (5)	C10—C11—C12	117.5 (4)
C1—N1—Co1	116.9 (4)	C10—C11—H11A	107.9
O1—N1—Co1	122.3 (4)	C12—C11—H11A	107.9
C2—N2—O2	120.7 (5)	C10—C11—H11B	107.9
C2—N2—Co1	116.3 (4)	C12—C11—H11B	107.9
O2—N2—Co1	123.0 (4)	H11A—C11—H11B	107.2
C3—N3—O3	119.1 (5)	C13—C12—C11	113.6 (5)
C3—N3—Co1	117.1 (4)	C13—C12—H12A	108.8
O3—N3—Co1	123.8 (4)	C11—C12—H12A	108.8
C4—N4—O4	121.6 (5)	C13—C12—H12B	108.8
C4—N4—Co1	115.4 (4)	C11—C12—H12B	108.8
O4—N4—Co1	122.9 (4)	H12A—C12—H12B	107.7
C15—N5—C19	117.3 (4)	C14—C13—C12	111.3 (5)
C15—N5—Co1	121.7 (4)	C14—C13—H13A	109.4
C19—N5—Co1	121.0 (3)	C12—C13—H13A	109.4
N1—C1—C2	111.9 (5)	C14—C13—H13B	109.4
N1—C1—C5	122.7 (6)	C12—C13—H13B	109.4
C2—C1—C5	125.5 (6)	H13A—C13—H13B	108.0
N2—C2—C1	113.2 (5)	C13—C14—H14A	109.5
N2—C2—C6	124.0 (6)	C13—C14—H14B	109.5
C1—C2—C6	122.8 (6)	H14A—C14—H14B	109.5
N3—C3—C4	112.4 (5)	C13—C14—H14C	109.5
N3—C3—C7	122.6 (6)	H14A—C14—H14C	109.5
C4—C3—C7	125.0 (5)	H14B—C14—H14C	109.5
N4—C4—C3	113.6 (5)	N5—C15—C16	123.1 (5)
N4—C4—C8	122.5 (6)	N5—C15—H15A	118.5
C3—C4—C8	123.9 (5)	C16—C15—H15A	118.5
C1—C5—H5A	109.5	C17—C16—C15	119.2 (5)
C1—C5—H5B	109.5	C17—C16—H16A	120.4
H5A—C5—H5B	109.5	C15—C16—H16A	120.4
C1—C5—H5C	109.5	C16—C17—C18	118.2 (5)
H5A—C5—H5C	109.5	C16—C17—H17A	120.9
H5B—C5—H5C	109.5	C18—C17—H17A	120.9
C2—C6—H6A	109.5	C19—C18—C17	119.6 (5)
C2—C6—H6B	109.5	C19—C18—H18A	120.2
H6A—C6—H6B	109.5	C17—C18—H18A	120.2
C2—C6—H6C	109.5	N5—C19—C18	122.6 (5)
H6A—C6—H6C	109.5	N5—C19—H19A	118.7
H6B—C6—H6C	109.5	C18—C19—H19A	118.7
C3—C7—H7A	109.5
N2—Co1—N1—C1	0.8 (4)	O1—N1—C1—C5	−0.8 (8)
N4—Co1—N1—C1	−179.3 (4)	Co1—N1—C1—C5	179.6 (4)
C10—Co1—N1—C1	−89.9 (4)	O2—N2—C2—C1	−177.7 (4)
N5—Co1—N1—C1	90.2 (4)	Co1—N2—C2—C1	1.3 (6)
N2—Co1—N1—O1	−178.8 (4)	O2—N2—C2—C6	0.6 (7)
N4—Co1—N1—O1	1.1 (4)	Co1—N2—C2—C6	179.6 (4)
C10—Co1—N1—O1	90.5 (4)	N1—C1—C2—N2	−0.7 (7)
N5—Co1—N1—O1	−89.4 (4)	C5—C1—C2—N2	179.4 (5)
N1—Co1—N2—C2	−1.2 (4)	N1—C1—C2—C6	−179.0 (5)
N3—Co1—N2—C2	177.2 (4)	C5—C1—C2—C6	1.1 (8)
C10—Co1—N2—C2	88.4 (4)	O3—N3—C3—C4	178.5 (4)
N5—Co1—N2—C2	−91.1 (4)	Co1—N3—C3—C4	−3.8 (6)
N1—Co1—N2—O2	177.8 (4)	O3—N3—C3—C7	−2.4 (8)
N3—Co1—N2—O2	−3.8 (4)	Co1—N3—C3—C7	175.2 (4)
C10—Co1—N2—O2	−92.6 (4)	O4—N4—C4—C3	−179.1 (5)
N5—Co1—N2—O2	87.9 (4)	Co1—N4—C4—C3	2.9 (6)
N2—Co1—N3—C3	−175.8 (4)	O4—N4—C4—C8	0.4 (8)
N4—Co1—N3—C3	4.3 (4)	Co1—N4—C4—C8	−177.6 (4)
C10—Co1—N3—C3	−85.4 (4)	N3—C3—C4—N4	0.5 (6)
N5—Co1—N3—C3	94.5 (4)	C7—C3—C4—N4	−178.5 (6)
N2—Co1—N3—O3	1.7 (4)	N3—C3—C4—C8	−179.0 (5)
N4—Co1—N3—O3	−178.2 (4)	C7—C3—C4—C8	2.0 (8)
C10—Co1—N3—O3	92.2 (4)	N1—Co1—C10—C9	−50.7 (5)
N5—Co1—N3—O3	−87.9 (4)	N2—Co1—C10—C9	−132.4 (5)
N1—Co1—N4—C4	174.5 (4)	N3—Co1—C10—C9	129.3 (5)
N3—Co1—N4—C4	−3.9 (4)	N4—Co1—C10—C9	48.0 (5)
C10—Co1—N4—C4	84.9 (4)	N1—Co1—C10—C11	128.1 (4)
N5—Co1—N4—C4	−95.6 (4)	N2—Co1—C10—C11	46.4 (4)
N1—Co1—N4—O4	−3.5 (5)	N3—Co1—C10—C11	−51.9 (4)
N3—Co1—N4—O4	178.1 (4)	N4—Co1—C10—C11	−133.2 (4)
C10—Co1—N4—O4	−93.0 (4)	C9—C10—C11—C12	−6.3 (9)
N5—Co1—N4—O4	86.4 (4)	Co1—C10—C11—C12	174.9 (4)
N1—Co1—N5—C15	43.4 (5)	C10—C11—C12—C13	−75.9 (7)
N2—Co1—N5—C15	125.1 (5)	C11—C12—C13—C14	175.2 (5)
N3—Co1—N5—C15	−136.6 (5)	C19—N5—C15—C16	−0.3 (9)
N4—Co1—N5—C15	−55.3 (5)	Co1—N5—C15—C16	−177.0 (5)
N1—Co1—N5—C19	−133.1 (5)	N5—C15—C16—C17	0.9 (10)
N2—Co1—N5—C19	−51.4 (5)	C15—C16—C17—C18	−1.0 (10)
N3—Co1—N5—C19	46.9 (5)	C16—C17—C18—C19	0.6 (10)
N4—Co1—N5—C19	128.2 (5)	C15—N5—C19—C18	−0.1 (9)
O1—N1—C1—C2	179.3 (4)	Co1—N5—C19—C18	176.6 (4)
Co1—N1—C1—C2	−0.3 (6)	C17—C18—C19—N5	−0.1 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O2	0.91 (9)	1.59 (9)	2.497 (7)	170 (7)
O4—H4O···O1	0.77 (5)	1.73 (5)	2.487 (6)	172 (6)