An unexpected chelate conformation in trans-[(R)-N,N′-bis(α-phenyl­salicyl­idene)­propane-1,2-diaminato(2–)]­bis(1-methyl-1H-imidazole-κN³)­cobalt(III) perchlorate

The title compound, [Co(C₂₉H₂₄N₂O₂)(C₄H₆N₂)₂]ClO₄, contains an optically active tetradentate Schiff base ligand in an equatorial plane and two 1-methyl­imidazole ligands at apical positions. The central N—C—C—N chelate ring of the Schiff base ligand has an envelope structure with a λ conformation, which is different from the solution structure predicted from circular dichroism and ¹H NMR spectra.

S1. Comment

Cobalt(II) schiff base complexes have been extensively utilized as catalysts for the oxidation reaction of organic molecules (Mukaiyama & Yamada, 1995; Fiammengo et al., 2002). It has been recognized that the formal potential of the Co^III/Co^II couple is an important factor which determines the catalytic activity (Förster et al., 1996). The redox potential of a Co^II or Co^III Schiff base complex is affected not only by the electronic effect, but also by the steric effect of the substituent on the Schiff base ligand (Kitaura et al., 1987; Nishinaga et al., 1991; Hirotsu et al., 1994, 1996). In Co^II complexes with N,N'-bis(salicylidene)-1,2-ethanediamine derivatives, an axially oriented substituent on the central ethylene backbone affords a more positive value of the redox potential compared with a complex with an equatorially oriented one. This was rationally demonstrated by investigating the intramolecular steric interactions of the related Co^III Schiff base complexes with two apical ligands, L, [Co(Schiff base)(L)₂]⁺ (Hirotsu et al., 1996). For the title complex, (I), [Co{7-Phsal-(R)-pn}(Meim)₂]ClO₄ [H₂{7-Phsal-(R)-pn} is (R)—N,N'-bis(α-phenylsalicylidene)-1,2-propanediamine and Meim is 1-methylimidazole], it has been reported that the central N—N chelate adopts the δ gauche conformation and the methyl group on the ethylene backbone is axially oriented, on the basis of circular dichroism and ¹H NMR spectra in an acetonitrile solution. To clarify the intramolecular steric interactions, we have determined the single-crystal structure of (I) by X-ray analysis and present the results here. \sch

The X-ray analysis of (I) confirmed the presence of a univalent [Co{7-Phsal-(R)-pn}(Meim)₂]⁺ complex cation and a perchlorate anion. The space group P2₁2₁2₁ is consistent with the fact that the complex has an optically active ligand derived from (R)-1,2-propanediamine. The absolute structure was chosen on the basis of the R configuration of the optically pure diamine employed.

In the complex cation, the Co^III ion is bound to two O and two N atoms of a Schiff base dianion, to form the equatorial plane. Two apical sites are occupied by N atoms of two 1-methylimidazole ligands, to complete the six-coordinate octahedral structure. The Co^III ion is in the equatorial coordination plane with no significant deviation. The coordination bond distances are comparable with those in the related Co^III Schiff base complex with two 1-methylimidazole ligands, [Co{sal-(meso)-stien}(Meim)₂]ClO₄ [mean Co—O 1.898 (4), Co—N_equatorial 1.903 (4) and Co—N_apical 1.957 (4) Å; Hirotsu et al., 1996].

The central N—N chelate ring has an envelope-type structure with an N1—C27—C28—N2 torsion angle of −14.4 (5)°, which is much smaller than the corresponding angle in [Co{sal-(meso)-stien}(Meim)₂]⁺ [42.5 (6)°]. The negative sign of this torsion angle in the cation of (I) is indicative of the λ conformation, which differs from the predominant solution structure containing the δ gauche conformation with the axially disposed methyl group. This suggests that the chelate conformation inverts rapidly in solution. The envelope structure and the δ gauche conformation are probably in equilibrium. A λ gauche conformation is unfavourable because of the steric repulsion between the equatorially disposed methyl group on the ethylene backbone and the phenyl group. The envelope structure may have a slightly higher energy than that of the δ gauche conformation, which largely contributes to the circular dichroism and ¹H NMR spectra in solution.

S2. Experimental

The title complex was prepared using the method previously reported by Hirotsu et al. (1996). Single crystals of (I) were obtained by slow evaporation of a dichloromethane-ethanol solution (Ratio?).

S3. Refinement

The H atoms of the three methyl groups were refined as idealized CH₃ groups with a rotating motion. All other H atoms were placed in fixed positions by assuming C—H distances of 0.97 (CH₂), 0.98 (CH) or 0.93 Å (imidazole CH). All H atoms were treated as riding, with U_iso(H) = 1.2U_eq(C). Please check added text. The absolute structure was set by reference to the known chirality of the enantiopure diamine employed.

Computing details

Data collection: Rigaku/AFC Diffractometer Control Software (Rigaku, 1995); cell refinement: Rigaku/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: TEXSAN.

Figures

Fig. 1. A drawing of the cation of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.

trans-bis(1-methylimidazole)[(R)—N,N'-bis(alpha-phenylsalicylidene)-1,2- propanediaminato]cobalt(III) perchlorate

Crystal data

[Co(C29H24N2O2)(C4H6N2)2]ClO4	Dx = 1.422 Mg m^−3
Mr = 755.10	Mo Kα radiation, λ = 0.71069 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 14.334 (2) Å	θ = 14.7–15.0°
b = 17.766 (3) Å	µ = 0.62 mm^−1
c = 13.849 (2) Å	T = 298 K
V = 3526.9 (9) Å^3	Prism, red
Z = 4	0.62 × 0.45 × 0.23 mm
F(000) = 1568.00

Data collection

Rigaku AFC-7S diffractometer	4120 reflections with F > 4σ(F)
Radiation source: sealed X-ray tube	Rint = 0.012
Graphite monochromator	θmax = 30.0°, θmin = 4.1°
ω/2θ scans	h = 0→20
Absorption correction: ψ scan (North et al., 1968)	k = −12→24
Tmin = 0.783, Tmax = 0.867	l = −10→19
6564 measured reflections	3 standard reflections every 150 reflections
5671 independent reflections	intensity decay: 0.0%

Refinement

Refinement on F^2	w = 1/[σ^2(Fo^2) + (0.0589P)^2 + 0.3625P] where P = (Fo^2 + 2Fc^2)/3
Least-squares matrix: full	(Δ/σ)max = −0.007
R[F^2 > 2σ(F^2)] = 0.038	Δρmax = 0.31 e Å^−3
wR(F^2) = 0.115	Δρmin = −0.52 e Å^−3
S = 1.04	Extinction correction: SHELXL97 (Sheldrick, 1997)
5671 reflections	Extinction coefficient: 0.0011
464 parameters	Absolute structure: Flack (1983)
H-atom parameters constrained	Absolute structure parameter: −0.01 (3)

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

	x	y	z	Uiso*/Ueq
Co1	0.41553 (2)	0.49768 (3)	0.22197 (2)	0.0294 (1)
Cl1	0.59513 (8)	0.5028 (1)	0.79937 (7)	0.0793 (3)
O1	0.3563 (2)	0.4238 (1)	0.2975 (2)	0.0356 (6)
O2	0.3522 (2)	0.5702 (1)	0.2970 (2)	0.0376 (7)
O3	0.5016 (3)	0.5009 (3)	0.8335 (3)	0.105 (1)
O4	0.6102 (6)	0.4371 (3)	0.7454 (4)	0.154 (3)
O5	0.6051 (5)	0.5648 (3)	0.7354 (4)	0.140 (3)
O6	0.6536 (3)	0.5101 (6)	0.8777 (3)	0.199 (4)
N1	0.4788 (2)	0.4260 (2)	0.1442 (3)	0.0322 (8)
N2	0.4755 (2)	0.5711 (2)	0.1452 (3)	0.0324 (8)
N3	0.5164 (2)	0.5004 (2)	0.3165 (2)	0.0354 (4)
N4	0.3118 (2)	0.4965 (2)	0.1334 (1)	0.0330 (4)
N5	0.6147 (3)	0.4666 (2)	0.4300 (3)	0.0431 (9)
N6	0.1680 (2)	0.4977 (3)	0.0821 (2)	0.0424 (5)
C1	0.3301 (3)	0.3591 (2)	0.2622 (3)	0.0342 (9)
C2	0.2578 (3)	0.3200 (2)	0.3116 (4)	0.045 (1)
C3	0.2294 (4)	0.2494 (2)	0.2823 (5)	0.059 (1)
C4	0.2675 (4)	0.2161 (3)	0.2018 (5)	0.061 (2)
C5	0.3364 (3)	0.2533 (2)	0.1521 (4)	0.050 (1)
C6	0.3698 (3)	0.3247 (2)	0.1796 (3)	0.0379 (10)
C7	0.4492 (3)	0.3582 (2)	0.1278 (3)	0.0337 (9)
C8	0.4931 (3)	0.3104 (2)	0.0510 (3)	0.038 (1)
C9	0.5472 (4)	0.2479 (2)	0.0758 (4)	0.048 (1)
C10	0.5852 (5)	0.2027 (2)	0.0055 (4)	0.059 (1)
C11	0.5694 (5)	0.2182 (3)	−0.0896 (4)	0.065 (2)
C12	0.5185 (4)	0.2799 (3)	−0.1153 (4)	0.061 (2)
C13	0.4790 (4)	0.3263 (2)	−0.0462 (3)	0.050 (1)
C14	0.3258 (3)	0.6354 (2)	0.2617 (3)	0.0368 (10)
C15	0.2544 (3)	0.6743 (2)	0.3112 (3)	0.048 (1)
C16	0.2248 (4)	0.7437 (2)	0.2829 (5)	0.054 (1)
C17	0.2611 (3)	0.7774 (3)	0.2007 (5)	0.057 (1)
C18	0.3294 (3)	0.7411 (2)	0.1498 (4)	0.050 (1)
C19	0.3650 (3)	0.6700 (2)	0.1787 (3)	0.0359 (9)
C20	0.4446 (3)	0.6385 (2)	0.1271 (3)	0.0333 (9)
C21	0.4906 (3)	0.6864 (2)	0.0517 (3)	0.036 (1)
C22	0.5456 (4)	0.7463 (2)	0.0779 (4)	0.046 (1)
C23	0.5817 (5)	0.7935 (2)	0.0071 (4)	0.059 (1)
C24	0.5657 (5)	0.7799 (3)	−0.0883 (4)	0.060 (2)
C25	0.5112 (5)	0.7181 (3)	−0.1147 (4)	0.072 (2)
C26	0.4746 (4)	0.6717 (3)	−0.0450 (3)	0.053 (1)
C27	0.5607 (3)	0.4574 (2)	0.0906 (3)	0.0354 (9)
C28	0.5632 (4)	0.5425 (2)	0.1057 (4)	0.046 (1)
C29	0.6525 (3)	0.4234 (2)	0.1236 (4)	0.069 (1)
C30	0.5500 (3)	0.4432 (2)	0.3663 (4)	0.041 (1)
C31	0.6230 (4)	0.5426 (3)	0.4180 (4)	0.054 (1)
C32	0.5616 (4)	0.5626 (2)	0.3501 (4)	0.049 (1)
C33	0.6651 (3)	0.4207 (3)	0.4992 (3)	0.060 (1)
C34	0.2239 (2)	0.4963 (3)	0.1597 (2)	0.0374 (6)
C35	0.2231 (2)	0.4977 (3)	0.0014 (2)	0.0473 (7)
C36	0.3120 (2)	0.4979 (3)	0.0339 (2)	0.0411 (6)
C37	0.0658 (2)	0.4975 (3)	0.0841 (3)	0.0632 (9)
H1	0.6521	0.3702	0.1115	0.0694*
H2	0.6605	0.4322	0.1915	0.0694*
H3	0.7030	0.4462	0.0888	0.0694*
H4	0.6348	0.3727	0.5054	0.0603*
H5	0.6658	0.4455	0.5608	0.0603*
H6	0.7279	0.4134	0.4773	0.0603*
H7	0.0433	0.5484	0.0844	0.0632*
H8	0.0446	0.4721	0.1412	0.0632*
H9	0.0425	0.4718	0.0281	0.0632*
H10	0.2291	0.3425	0.3646	0.0545*
H11	0.1840	0.2240	0.3174	0.0705*
H12	0.2469	0.1691	0.1813	0.0738*
H13	0.3622	0.2303	0.0979	0.0595*
H14	0.5576	0.2368	0.1406	0.0573*
H15	0.6218	0.1616	0.0227	0.0703*
H16	0.5934	0.1866	−0.1370	0.0775*
H17	0.5102	0.2910	−0.1804	0.0726*
H18	0.4433	0.3676	−0.0646	0.0604*
H19	0.2268	0.6519	0.3647	0.0577*
H20	0.1799	0.7688	0.3190	0.0645*
H21	0.2392	0.8241	0.1805	0.0689*
H22	0.3532	0.7638	0.0945	0.0603*
H23	0.5586	0.7552	0.1427	0.0555*
H24	0.6172	0.8349	0.0252	0.0705*
H25	0.5907	0.8114	−0.1353	0.0722*
H26	0.4997	0.7082	−0.1796	0.0865*
H27	0.4389	0.6302	−0.0628	0.0638*
H28	0.5526	0.4470	0.0216	0.0424*
H29	0.5748	0.5667	0.0440	0.0550*
H30	0.6134	0.5545	0.1500	0.0550*
H31	0.5314	0.3934	0.3584	0.0491*
H32	0.6636	0.5744	0.4509	0.0648*
H33	0.5513	0.6116	0.3289	0.0593*
H34	0.2032	0.4954	0.2234	0.0448*
H35	0.2034	0.4976	−0.0625	0.0568*
H36	0.3650	0.4988	−0.0048	0.0493*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0318 (2)	0.0317 (2)	0.0246 (2)	−0.0016 (3)	0.0009 (1)	0.0008 (3)
Cl1	0.0819 (7)	0.1039 (9)	0.0523 (5)	−0.001 (1)	−0.0008 (5)	−0.006 (1)
O1	0.041 (2)	0.039 (1)	0.027 (1)	−0.007 (1)	0.005 (1)	0.002 (1)
O2	0.046 (2)	0.037 (1)	0.030 (1)	0.002 (1)	0.001 (1)	0.000 (1)
O3	0.086 (2)	0.124 (3)	0.105 (3)	0.004 (4)	0.007 (2)	−0.006 (4)
O4	0.218 (8)	0.132 (4)	0.113 (4)	0.074 (5)	0.036 (5)	−0.020 (4)
O5	0.158 (6)	0.142 (4)	0.119 (4)	−0.048 (4)	−0.025 (5)	0.038 (4)
O6	0.102 (3)	0.43 (1)	0.066 (2)	−0.009 (8)	−0.021 (2)	−0.021 (7)
N1	0.033 (2)	0.034 (1)	0.029 (2)	0.000 (1)	0.000 (2)	0.003 (1)
N2	0.034 (2)	0.034 (1)	0.030 (2)	−0.002 (1)	0.003 (2)	0.000 (1)
N3	0.038 (1)	0.037 (1)	0.0315 (10)	−0.001 (2)	−0.0022 (8)	−0.002 (2)
N4	0.037 (1)	0.036 (1)	0.0260 (9)	0.004 (2)	−0.0011 (8)	0.001 (2)
N5	0.041 (2)	0.051 (2)	0.038 (2)	0.000 (2)	−0.008 (2)	−0.002 (1)
N6	0.037 (1)	0.048 (1)	0.042 (1)	−0.001 (2)	−0.0065 (10)	−0.004 (2)
C1	0.033 (2)	0.037 (2)	0.033 (2)	−0.001 (2)	0.003 (2)	0.005 (2)
C2	0.035 (3)	0.048 (2)	0.053 (3)	−0.007 (2)	0.009 (3)	0.008 (2)
C3	0.044 (3)	0.048 (2)	0.084 (4)	−0.015 (2)	0.016 (3)	0.006 (3)
C4	0.047 (3)	0.040 (2)	0.097 (5)	−0.005 (2)	0.006 (4)	−0.006 (3)
C5	0.047 (3)	0.042 (2)	0.060 (3)	−0.008 (2)	0.002 (3)	−0.009 (2)
C6	0.032 (2)	0.040 (2)	0.041 (2)	0.002 (2)	−0.003 (2)	0.000 (2)
C7	0.037 (2)	0.034 (2)	0.030 (2)	0.002 (2)	0.000 (2)	0.000 (2)
C8	0.038 (3)	0.039 (2)	0.037 (3)	0.002 (2)	0.002 (2)	−0.003 (2)
C9	0.057 (3)	0.039 (2)	0.047 (3)	0.006 (2)	−0.006 (3)	0.004 (2)
C10	0.060 (4)	0.047 (2)	0.068 (4)	0.019 (3)	−0.002 (4)	−0.013 (2)
C11	0.080 (5)	0.056 (3)	0.058 (3)	0.009 (3)	0.019 (4)	−0.019 (3)
C12	0.089 (4)	0.064 (3)	0.029 (3)	0.000 (3)	0.009 (3)	−0.009 (2)
C13	0.064 (3)	0.047 (2)	0.041 (3)	0.002 (2)	−0.015 (3)	−0.004 (2)
C14	0.037 (2)	0.032 (2)	0.041 (2)	−0.002 (2)	−0.007 (2)	−0.006 (2)
C15	0.047 (3)	0.049 (2)	0.048 (3)	0.004 (2)	0.007 (3)	−0.003 (2)
C16	0.045 (3)	0.048 (2)	0.068 (3)	0.005 (2)	0.004 (3)	−0.010 (2)
C17	0.051 (3)	0.042 (2)	0.079 (4)	0.013 (2)	0.005 (3)	0.008 (2)
C18	0.045 (3)	0.041 (2)	0.065 (3)	0.000 (2)	0.000 (3)	0.009 (2)
C19	0.039 (2)	0.030 (2)	0.038 (2)	0.003 (2)	0.000 (2)	−0.001 (2)
C20	0.036 (2)	0.033 (2)	0.031 (2)	−0.006 (2)	−0.006 (2)	0.001 (2)
C21	0.045 (3)	0.030 (2)	0.033 (2)	0.000 (2)	0.001 (2)	0.005 (2)
C22	0.058 (3)	0.047 (2)	0.034 (2)	−0.014 (2)	0.006 (2)	0.007 (2)
C23	0.068 (4)	0.051 (2)	0.057 (3)	−0.016 (3)	0.016 (4)	0.005 (2)
C24	0.076 (4)	0.054 (2)	0.050 (3)	0.005 (3)	0.017 (4)	0.016 (2)
C25	0.108 (6)	0.065 (3)	0.043 (3)	−0.008 (3)	−0.009 (4)	0.010 (3)
C26	0.071 (4)	0.052 (2)	0.037 (3)	−0.016 (3)	0.004 (3)	0.004 (2)
C27	0.033 (2)	0.034 (2)	0.039 (2)	0.001 (2)	0.013 (2)	0.001 (1)
C28	0.049 (3)	0.042 (2)	0.046 (2)	0.000 (2)	0.008 (2)	0.005 (2)
C29	0.038 (2)	0.052 (2)	0.118 (4)	0.003 (2)	0.011 (2)	0.015 (3)
C30	0.047 (2)	0.035 (2)	0.041 (2)	−0.004 (2)	−0.004 (2)	0.003 (2)
C31	0.052 (3)	0.050 (2)	0.060 (3)	−0.014 (2)	−0.018 (2)	−0.003 (2)
C32	0.054 (3)	0.040 (2)	0.054 (3)	−0.006 (2)	−0.018 (2)	0.003 (2)
C33	0.065 (3)	0.066 (3)	0.049 (2)	0.010 (2)	−0.019 (2)	0.003 (2)
C34	0.038 (1)	0.043 (1)	0.031 (1)	0.001 (2)	−0.0012 (10)	0.004 (2)
C35	0.056 (2)	0.054 (2)	0.032 (1)	0.004 (3)	−0.010 (1)	−0.003 (3)
C36	0.050 (1)	0.047 (1)	0.027 (1)	−0.001 (3)	0.001 (1)	−0.007 (2)
C37	0.038 (2)	0.076 (2)	0.075 (2)	0.006 (3)	−0.013 (2)	−0.005 (4)

Geometric parameters (Å, º)

Co1—O1	1.880 (3)	C20—C21	1.501 (6)
Co1—O2	1.887 (3)	C21—C22	1.372 (6)
Co1—N1	1.898 (3)	C21—C26	1.383 (6)
Co1—N2	1.889 (3)	C22—C23	1.390 (7)
Co1—N3	1.950 (2)	C23—C24	1.364 (8)
Co1—N4	1.927 (2)	C24—C25	1.396 (8)
Cl1—O3	1.421 (4)	C25—C26	1.373 (8)
Cl1—O4	1.402 (6)	C27—C28	1.527 (6)
Cl1—O5	1.421 (6)	C27—C29	1.519 (6)
Cl1—O6	1.377 (4)	C31—C32	1.336 (8)
O1—C1	1.305 (4)	C35—C36	1.351 (4)
O2—C14	1.314 (4)	C2—H10	0.930
N1—C7	1.298 (5)	C3—H11	0.930
N1—C27	1.497 (6)	C4—H12	0.930
N2—C20	1.300 (4)	C5—H13	0.930
N2—C28	1.464 (6)	C9—H14	0.930
N3—C30	1.320 (5)	C10—H15	0.930
N3—C32	1.363 (6)	C11—H16	0.930
N4—C34	1.312 (4)	C12—H17	0.930
N4—C36	1.378 (3)	C13—H18	0.930
N5—C30	1.346 (6)	C15—H19	0.930
N5—C31	1.366 (6)	C16—H20	0.930
N5—C33	1.452 (6)	C17—H21	0.930
N6—C34	1.342 (4)	C18—H22	0.930
N6—C35	1.368 (4)	C22—H23	0.930
N6—C37	1.465 (4)	C23—H24	0.930
C1—C2	1.422 (6)	C24—H25	0.930
C1—C6	1.417 (6)	C25—H26	0.930
C2—C3	1.380 (6)	C26—H27	0.930
C3—C4	1.376 (9)	C27—H28	0.980
C4—C5	1.373 (8)	C28—H29	0.970
C5—C6	1.408 (6)	C28—H30	0.970
C6—C7	1.471 (6)	C29—H1	0.960
C7—C8	1.498 (6)	C29—H2	0.960
C8—C9	1.397 (6)	C29—H3	0.960
C8—C13	1.391 (7)	C30—H31	0.930
C9—C10	1.375 (8)	C31—H32	0.930
C10—C11	1.364 (9)	C32—H33	0.930
C11—C12	1.363 (8)	C33—H4	0.960
C12—C13	1.385 (7)	C33—H5	0.960
C14—C15	1.412 (6)	C33—H6	0.960
C14—C19	1.420 (6)	C34—H34	0.930
C15—C16	1.362 (6)	C35—H35	0.930
C16—C17	1.386 (9)	C36—H36	0.930
C17—C18	1.367 (7)	C37—H7	0.960
C18—C19	1.421 (6)	C37—H8	0.960
C19—C20	1.458 (6)	C37—H9	0.960
O1···C35^i	3.349 (4)	N5···C37^i	3.414 (6)
O2···C35^i	3.261 (4)	C1···C22^iv	3.478 (6)
O3···C26^ii	3.491 (7)	C2···C23^iv	3.438 (8)
O3···C13^ii	3.537 (7)	C2···C22^iv	3.465 (7)
O3···C37^i	3.586 (6)	C3···C11^v	3.566 (9)
O4···C37^i	3.564 (8)	C4···C11^v	3.441 (9)
O5···C37^i	3.408 (8)	C9···C15^iv	3.499 (7)
O6···C33^iii	3.332 (7)	C9···C14^iv	3.518 (7)
O6···C27^ii	3.368 (7)	C10···C15^iv	3.462 (8)
O6···C31^iii	3.383 (8)	C16···C24^vi	3.555 (9)
O6···N5^iii	3.425 (6)	C17···C24^vi	3.362 (8)
O6···C28^ii	3.460 (7)
O1—Co1—O2	87.3 (1)	N1—C27—C29	112.5 (3)
O1—Co1—N1	93.6 (1)	C28—C27—C29	109.4 (4)
O1—Co1—N2	179.4 (1)	N2—C28—C27	112.0 (4)
O1—Co1—N3	88.8 (1)	N3—C30—N5	110.8 (3)
O1—Co1—N4	89.9 (1)	N5—C31—C32	106.9 (4)
O2—Co1—N1	178.8 (1)	N3—C32—C31	109.8 (4)
O2—Co1—N2	93.3 (1)	N4—C34—N6	110.6 (2)
O2—Co1—N3	88.3 (1)	N6—C35—C36	105.8 (2)
O2—Co1—N4	89.3 (1)	N4—C36—C35	109.4 (2)
N1—Co1—N2	85.8 (1)	C1—C2—H10	119.5
N1—Co1—N3	92.5 (1)	C3—C2—H10	119.4
N1—Co1—N4	90.0 (1)	C2—C3—H11	119.6
N2—Co1—N3	91.3 (1)	C4—C3—H11	119.6
N2—Co1—N4	90.0 (1)	C3—C4—H12	120.5
N3—Co1—N4	177.25 (10)	C5—C4—H12	120.5
O3—Cl1—O4	107.7 (4)	C4—C5—H13	118.6
O3—Cl1—O5	108.6 (4)	C6—C5—H13	118.6
O3—Cl1—O6	108.3 (2)	C8—C9—H14	119.7
O4—Cl1—O5	107.3 (3)	C10—C9—H14	119.7
O4—Cl1—O6	113.9 (5)	C9—C10—H15	120.0
O5—Cl1—O6	110.9 (5)	C11—C10—H15	120.0
Co1—O1—C1	122.5 (3)	C10—C11—H16	119.9
Co1—O2—C14	122.4 (3)	C12—C11—H16	119.9
Co1—N1—C7	124.5 (3)	C11—C12—H17	119.4
Co1—N1—C27	114.0 (2)	C13—C12—H17	119.4
C7—N1—C27	121.0 (3)	C8—C13—H18	120.4
Co1—N2—C20	126.1 (3)	C12—C13—H18	120.4
Co1—N2—C28	111.2 (2)	C14—C15—H19	119.0
C20—N2—C28	122.7 (3)	C16—C15—H19	119.0
Co1—N3—C30	127.0 (3)	C15—C16—H20	119.7
Co1—N3—C32	127.0 (3)	C17—C16—H20	119.7
C30—N3—C32	105.8 (3)	C16—C17—H21	120.4
Co1—N4—C34	124.3 (2)	C18—C17—H21	120.4
Co1—N4—C36	129.4 (2)	C17—C18—H22	119.0
C34—N4—C36	106.2 (2)	C19—C18—H22	119.0
C30—N5—C31	106.7 (4)	C21—C22—H23	120.2
C30—N5—C33	127.0 (3)	C23—C22—H23	120.2
C31—N5—C33	126.3 (4)	C22—C23—H24	119.5
C34—N6—C35	108.0 (2)	C24—C23—H24	119.5
C34—N6—C37	125.6 (3)	C23—C24—H25	120.4
C35—N6—C37	126.4 (3)	C25—C24—H25	120.4
O1—C1—C2	117.4 (4)	C24—C25—H26	119.9
O1—C1—C6	124.5 (4)	C26—C25—H26	119.9
C2—C1—C6	118.1 (3)	C21—C26—H27	119.9
C1—C2—C3	121.1 (4)	C25—C26—H27	119.9
C2—C3—C4	120.9 (5)	N1—C27—H28	108.7
C3—C4—C5	118.9 (4)	C28—C27—H28	108.7
C4—C5—C6	122.9 (5)	C29—C27—H28	108.7
C1—C6—C5	118.0 (4)	N2—C28—H29	108.8
C1—C6—C7	122.1 (3)	N2—C28—H30	108.8
C5—C6—C7	119.7 (4)	C27—C28—H29	108.8
N1—C7—C6	122.8 (4)	C27—C28—H30	108.8
N1—C7—C8	120.9 (4)	H29—C28—H30	109.5
C6—C7—C8	116.3 (3)	C27—C29—H1	109.5
C7—C8—C9	120.6 (4)	C27—C29—H2	109.5
C7—C8—C13	120.7 (4)	C27—C29—H3	109.5
C9—C8—C13	118.7 (4)	H1—C29—H2	109.5
C8—C9—C10	120.7 (5)	H1—C29—H3	109.5
C9—C10—C11	120.0 (5)	H2—C29—H3	109.5
C10—C11—C12	120.2 (5)	N3—C30—H31	124.6
C11—C12—C13	121.1 (5)	N5—C30—H31	124.6
C8—C13—C12	119.2 (4)	N5—C31—H32	126.6
O2—C14—C15	117.4 (4)	C32—C31—H32	126.6
O2—C14—C19	124.7 (4)	N3—C32—H33	125.1
C15—C14—C19	117.9 (3)	C31—C32—H33	125.1
C14—C15—C16	121.9 (4)	N5—C33—H4	109.5
C15—C16—C17	120.7 (5)	N5—C33—H5	109.5
C16—C17—C18	119.3 (4)	N5—C33—H6	109.5
C17—C18—C19	122.0 (5)	H4—C33—H5	109.5
C14—C19—C18	118.1 (4)	H4—C33—H6	109.5
C14—C19—C20	122.7 (3)	H5—C33—H6	109.5
C18—C19—C20	119.0 (4)	N4—C34—H34	124.7
N2—C20—C19	121.7 (4)	N6—C34—H34	124.7
N2—C20—C21	120.4 (4)	N6—C35—H35	127.1
C19—C20—C21	117.8 (3)	C36—C35—H35	127.1
C20—C21—C22	120.6 (4)	N4—C36—H36	125.3
C20—C21—C26	119.5 (4)	C35—C36—H36	125.3
C22—C21—C26	119.9 (4)	N6—C37—H7	109.5
C21—C22—C23	119.7 (5)	N6—C37—H8	109.5
C22—C23—C24	120.9 (5)	N6—C37—H9	109.5
C23—C24—C25	119.1 (5)	H7—C37—H8	109.5
C24—C25—C26	120.1 (5)	H7—C37—H9	109.5
C21—C26—C25	120.2 (5)	H8—C37—H9	109.5
N1—C27—C28	108.6 (4)
Co1—O1—C1—C2	−157.1 (3)	N3—C32—C31—N5	−1.8 (6)
Co1—O1—C1—C6	24.1 (5)	N4—Co1—O1—C1	56.3 (3)
Co1—O2—C14—C15	159.7 (3)	N4—Co1—O2—C14	−58.4 (3)
Co1—O2—C14—C19	−21.6 (6)	N4—Co1—N1—C7	−63.0 (3)
Co1—N1—C7—C6	−9.6 (6)	N4—Co1—N1—C27	108.8 (3)
Co1—N1—C7—C8	168.1 (3)	N4—Co1—N2—C20	62.3 (4)
Co1—N1—C27—C28	−6.5 (4)	N4—Co1—N2—C28	−116.8 (3)
Co1—N1—C27—C29	114.8 (3)	N4—C34—N6—C35	0.8 (6)
Co1—N2—C20—C19	10.7 (6)	N4—C34—N6—C37	179.5 (5)
Co1—N2—C20—C21	−169.5 (3)	N4—C36—C35—N6	1.2 (6)
Co1—N2—C28—C27	29.3 (4)	N5—C30—N3—C32	0.0 (5)
Co1—N3—C30—N5	−175.5 (3)	N6—C34—N4—C36	−0.1 (5)
Co1—N3—C32—C31	176.6 (3)	C1—C2—C3—C4	−2.9 (8)
Co1—N4—C34—N6	178.1 (3)	C1—C6—C5—C4	0.0 (7)
Co1—N4—C36—C35	−178.8 (3)	C1—C6—C7—C8	171.2 (4)
O1—Co1—O2—C14	−148.3 (3)	C2—C1—C6—C5	−1.0 (6)
O1—Co1—N1—C7	26.8 (4)	C2—C1—C6—C7	−175.7 (4)
O1—Co1—N1—C27	−161.4 (3)	C2—C3—C4—C5	1.8 (8)
O1—Co1—N3—C30	35.4 (3)	C3—C2—C1—C6	2.5 (7)
O1—Co1—N3—C32	−139.1 (3)	C3—C4—C5—C6	−0.4 (8)
O1—Co1—N4—C34	44.6 (4)	C4—C5—C6—C7	174.8 (5)
O1—Co1—N4—C36	−137.7 (4)	C5—C6—C7—C8	−3.4 (6)
O1—C1—C2—C3	−176.4 (4)	C6—C7—N1—C27	179.2 (4)
O1—C1—C6—C5	177.8 (4)	C6—C7—C8—C9	−72.1 (6)
O1—C1—C6—C7	3.1 (6)	C6—C7—C8—C13	106.2 (5)
O2—Co1—O1—C1	145.5 (3)	C7—N1—C27—C28	165.7 (4)
O2—Co1—N2—C20	−27.0 (4)	C7—N1—C27—C29	−73.1 (5)
O2—Co1—N2—C28	153.9 (3)	C7—C8—C9—C10	178.0 (5)
O2—Co1—N3—C30	122.7 (3)	C7—C8—C13—C12	−178.3 (5)
O2—Co1—N3—C32	−51.8 (3)	C8—C7—N1—C27	−3.1 (6)
O2—Co1—N4—C34	−42.7 (4)	C8—C9—C10—C11	−0.8 (9)
O2—Co1—N4—C36	135.1 (4)	C8—C13—C12—C11	1.3 (9)
O2—C14—C15—C16	177.1 (4)	C9—C8—C13—C12	0.1 (7)
O2—C14—C19—C18	−179.5 (4)	C9—C10—C11—C12	2.2 (10)
O2—C14—C19—C20	−4.4 (7)	C10—C9—C8—C13	−0.4 (7)
N1—Co1—O1—C1	−33.7 (3)	C10—C11—C12—C13	−2.5 (10)
N1—Co1—N2—C20	152.3 (4)	C14—C15—C16—C17	3.2 (8)
N1—Co1—N2—C28	−26.8 (3)	C14—C19—C18—C17	1.9 (7)
N1—Co1—N3—C30	−58.2 (3)	C14—C19—C20—C21	−169.3 (4)
N1—Co1—N3—C32	127.3 (3)	C15—C14—C19—C18	−0.8 (6)
N1—Co1—N4—C34	138.2 (4)	C15—C14—C19—C20	174.3 (4)
N1—Co1—N4—C36	−44.0 (4)	C15—C16—C17—C18	−2.1 (8)
N1—C7—C6—C1	−11.0 (6)	C16—C15—C14—C19	−1.7 (7)
N1—C7—C6—C5	174.4 (4)	C16—C17—C18—C19	−0.4 (8)
N1—C7—C8—C9	110.0 (5)	C17—C18—C19—C20	−173.4 (4)
N1—C7—C8—C13	−71.6 (6)	C18—C19—C20—C21	5.7 (6)
N1—C27—C28—N2	−14.4 (5)	C19—C20—N2—C28	−170.3 (4)
N2—Co1—O2—C14	31.6 (3)	C19—C20—C21—C22	73.5 (6)
N2—Co1—N1—C7	−153.1 (4)	C19—C20—C21—C26	−104.1 (5)
N2—Co1—N1—C27	18.7 (3)	C20—N2—C28—C27	−149.8 (4)
N2—Co1—N3—C30	−144.0 (3)	C20—C21—C22—C23	−175.0 (5)
N2—Co1—N3—C32	41.5 (3)	C20—C21—C26—C25	175.7 (5)
N2—Co1—N4—C34	−136.0 (4)	C21—C20—N2—C28	9.5 (6)
N2—Co1—N4—C36	41.8 (4)	C21—C22—C23—C24	−2.1 (9)
N2—C20—C19—C14	10.5 (6)	C21—C26—C25—C24	0.7 (9)
N2—C20—C19—C18	−174.4 (4)	C22—C21—C26—C25	−1.9 (8)
N2—C20—C21—C22	−106.3 (5)	C22—C23—C24—C25	0.8 (9)
N2—C20—C21—C26	76.1 (6)	C23—C22—C21—C26	2.6 (7)
N2—C28—C27—C29	−137.6 (4)	C23—C24—C25—C26	−0.1 (10)
N3—Co1—O1—C1	−126.1 (3)	C30—N3—C32—C31	1.2 (5)
N3—Co1—O2—C14	122.8 (3)	C30—N5—C31—C32	1.8 (6)
N3—Co1—N1—C7	115.8 (3)	C32—C31—N5—C33	−177.4 (4)
N3—Co1—N1—C27	−72.4 (3)	C34—N4—C36—C35	−0.7 (5)
N3—Co1—N2—C20	−115.3 (4)	C34—N6—C35—C36	−1.2 (6)
N3—Co1—N2—C28	65.6 (3)	C36—C35—N6—C37	−179.9 (5)
N3—C30—N5—C31	−1.1 (5)	C36—C35—N6—C37	−179.9 (5)
N3—C30—N5—C33	178.0 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C33^iii—H6^iii···O6	0.96	2.58	3.332 (7)	136
C37^i—H8^i···O5	0.96	2.60	3.408 (8)	143

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