Bis{2,6-bis[3-(2,4,6-trimethylphenyl)pyrazol-1-yl-κN²]pyridine-κN}cobalt(II) dinitrate at 290 and 150 K

The title compound, [Co(C₂₉H₂₉N₅)₂](NO₃)₂, contains a six-coordinate high-spin Co^II ion with approximate local D_2d symmetry. The bond lengths and angles at cobalt undergo only small changes between the two temperatures, which confirms that the Co^II ion does not undergo a spin-state transition over this temperature range.

S1. Comment

We have recently reported a synthetic and structural study of a series of complexes [Co(L^R)₂]²⁺ [R is H, ⁱPr, Ph or mesityl (Mes); Holland et al., 2001]. As part of this study, we described the crystal structure of [Co(L^Mes)₂](ClO₄)₂·2CH₃NO₂, which we obtained at 150 K to prevent desolvation of the crystals. Unfortunately, it was not possible to interpret this structure meaningfully because, although the complex is in a high-spin form at 290 K, in the absence of variable-temperature magnetic data, it was unclear whether the Co ion had undergone a spin-state transition upon cooling (see e.g. Figgis et al., 1983; Gaspar et al., 2001). We now report structure determinations of the title unsolvated salt [Co(L^Mes)₂](NO₃)₂, (I), at 290 K and 150 K, which are intended to address this ambiguity. \sch

Compound (I) crystallizes in the orthorhombic space group Pca2₁, with one complex dication and two anions per asymmetric unit, all lying on general positions. The Co^II ion has a distorted octahedral stereochemistry with approximate D_{2 d} local symmetry, which resembles those of other [M(L^R)₂]²⁺ (M is Fe, Co, Ni, Cu or Zn) complexes that we have characterized crystallographically (Solanki et al., 1998, 2001; Halcrow et al., 2000; Holland et al., 2001, 2002). As in these other compounds, the coordination sphere at Co in (I) is substantially distorted from an ideal octahedron by the restricted bite angle of the L^Mes ligand; the average of the four angles N2—Co1—N9, N2—Co1—N23, N36—Co1—N43 and N2—Co1—N57 is 77.09 (13)° at 150 K, compared with the ideal octahedral angle of 90°. While five of the six Co—N bonds in (I) are identical at the two temperatures to within experimental error, the Co1—N36 bond is 0.013 (2) Å longer at 150 K than at 290 K. This cannot reflect the existence of a partial spin-state transition upon cooling, since that would give rise to a shortening of this bond at lower temperature (Figgis et al., 1983; Holland et al., 2001), the opposite trend to that observed. Hence, the origin of this effect is uncertain, although librational shortening of the Co—N bonds at 290 K may contribute to it. All N—Co—N angles are identical in the two structures to within three s.u.s, except for N9—Co1—N57, which is 0.44 (8)° larger at 150 K than at 290 K, and N23—Co1—N57, which has contracted by 0.63 (8)° in the low-temperature structure. The significance of these small differences is also unclear.

The effective magnetic moment of (I) at 290 K is 4.2 µ_B, which is identical, within experimental error, to that exhibited by [Co(L^Mes)₂](ClO₄)₂ (Holland et al., 2001), and is consistent with (I) being completely high-spin at this temperature (O'Connor, 1982). The almost identical molecular structures of (I) at 290 K and 150 K also demonstrate that (I) is still in a high-spin state at 150 K. That being the case, it is interesting that all the Co—N bonds in (I) are shorter than the corresponding bonds in [Co(L^Mes)₂](ClO₄)₂·2CH₃NO₂ at 150 K, by between 0.017 (2) and 0.035 (2) Å. Despite this, the Co—N distances in (I) are within the range previously observed for high-spin Co^II complexes with a hexa-nitrogen donor set (tabulated in Holland et al., 2001). In particular, the Co—N(pyridine) bond lengths, which are the most sensitive to the spin state of a Co^II ion in this type of complex (Figgis et al., 1983), are within the range expected from a high-spin Co^II compound. Hence, this study emphasizes that the coordination sphere in six-coordinate high-spin Co^II complexes is rather plastic, and that structural data can only be related to the spin state in these compounds with care (Holland et al., 2001).

S2. Experimental

A mixture of Co(NO₃)₂·6H₂O (0.16 g, 0.55 mmol) and L^Mes (0.50 g, 1.11 mmol) in MeCN (50 ml) was stirred at 323 K until all the solid had dissolved. The resultant orange solution was filtered, and then concentrated in vacuo until orange-yellow microcrystals began to form. After overnight storage of the mixture at 243 K, the product was filtered, washed with Et₂O and dried in vacuo. Diffusion of Et₂O vapour into a dilute MeCN solution of the sparingly soluble complex yielded small, strongly diffracting rectangular prisms of (I). The same crystal was used for data collection at both 290 K and 150 K.

S3. Refinement

At both temperatures, one of the two nitrate ions was disordered and was modelled over three orientations. At 290 K, these were refined with occupancies of 0.40, 0.30 and 0.30, the latter two orientations sharing a common N atom. At 150 K, three distinct partial NO₃⁻ moieties were detected, with occupancies of 0.40, 0.40 and 0.20. The N—O distances within the disordered anion at 290 K were restrained to 1.25 (1) Å, and non-bonded O···O distances within a given disorder orientation to 2.17 (1) Å. At 150 K, corresponding restraints of 1.26 (1) and 2.18 (1) Å, respectively, were applied. At both temperatures, all non-H atoms with occupancy >0.5 were refined anisotropically, and all H atoms were placed in calculated positions and refined using a riding model. The torsion angles of all the CH₃ groups in the molecule were allowed to refine freely except that, at both temperatures, antibumping restraints were applied to individual H atoms attached to atoms C21 and C53, and to C35 and C55. Even with these restraints, there is one abnormally short intermolecular H···H contact of H11···H35Cⁱ 2.06–2.10 Å [symmetry code: (i) x, y − 1, z]. Introduction of additional antibumping restraints between H11 and the C35ⁱ methyl group prevented the refinements from converging, so these were omitted from the final models. However, for this reason, the refined methyl group torsions on C35 at the two temperatures probably do not correspond to the `true' equilibrium positions. The fixed C—H distances were as follows: at 290 K, C—H(aryl) = 0.93 and C—H(methyl) = 0.96 Å; at 150 K, C—H(aryl) = 0.95 and C—H(methyl) = 0.98 Å. At both temperatures, the H-atom U_iso parameters were fixed at 1.2U_eq(C) for C—H(aryl), and 1.5U_eq(C) for C—H(methyl). The Flack parameters (Flack, 1983) were calculated using 5661 (290 K) and 5773 (150 K) Friedel pairs.

Computing details

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: local program.

Figures

Fig. 1. A view of the molecular structure of the [Co(L^Mes)2]^2+ dication in (I) at 150 K, with 35% probability displacement ellipsoids, showing the atom-numbering scheme employed. H atoms have been omitted for clarity.

(I) Bis{2,6-bis[3-(2,4,6-trimethylphenyl)pyrazol- 1-yl-κN²]pyridine-κN}cobalt(II) dinitrate

Crystal data

[Co(C29H29N5)2](NO3)2	Dx = 1.329 Mg m^−3
Mr = 1078.09	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca21	Cell parameters from 59607 reflections
a = 22.3350 (1) Å	θ = 2.6–27.5°
b = 10.9094 (2) Å	µ = 0.38 mm^−1
c = 22.1061 (2) Å	T = 290 K
V = 5386.40 (11) Å^3	Rectangular prism, orange
Z = 4	0.45 × 0.35 × 0.28 mm
F(000) = 2260

Data collection

Nonius KappaCCD area-detector diffractometer	11975 independent reflections
Radiation source: fine-focus sealed tube	10665 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.6°
type of scans	h = −29→27
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −12→14
Tmin = 0.847, Tmax = 0.901	l = −28→28
59607 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.061P)^2 + 0.6652P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.104	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.26 e Å^−3
11975 reflections	Δρmin = −0.28 e Å^−3
721 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
21 restraints	Extinction coefficient: 0.0083 (8)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.004 (9)

Special details

Experimental. Detector set at 30 mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings

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.

One nitrate anion is disordered over three orientations: N74A—O77A, occupancy 0.30 N74A, O75B—O77B, occupancy 0.30 (i.e N74A has total occupancy 0.60) N74C—O77C, occupancy 0.40. A ttempts to refine a distinct N atom for disorder orientation 'B' were unsuccessful. The N—O distances within the disordered anion were restrained to 1.25 (2) Å, and non-bonded O···O distances within a given disorder orientation to 2.17 (2) Å. All non-H atoms with occupancy >0.5 were refined anisotropically, and all H atoms were placed in calculated positions and refined using a riding model. The torsions of all the methyl groups were allowed to refine freely, except that anti-bumping restraints were applied to H35A and H55A, and to H21B and H53B, to prevent abnormally short intramolecular H···H contacts in the final model. Even with these restraints, there is one abnormally short intermolecular H···H contact of H11···H35Cⁱ 2.10 Å (related by x, y − 1, z). Introduction of additional antibumping restraints between H11 and the C35ⁱ methyl group prevented the refinement from converging, so that these were omitted from the final model. However, for this reason the refined methyl group torsion on C35 probably does not correspond to the 'true' equilibrium position.

The Flack parameters was calculated using 5661 Friedel pairs.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.607489 (10)	0.76851 (2)	0.680880 (14)	0.03987 (8)
N2	0.57191 (8)	0.74731 (15)	0.76390 (8)	0.0446 (4)
C3	0.55530 (10)	0.6364 (2)	0.78252 (10)	0.0489 (4)
C4	0.53254 (11)	0.6152 (2)	0.83960 (11)	0.0580 (5)
H4	0.5217	0.5370	0.8524	0.070*
C5	0.52679 (11)	0.7160 (2)	0.87670 (11)	0.0594 (5)
H5	0.5117	0.7053	0.9156	0.071*
C6	0.54270 (10)	0.8327 (2)	0.85814 (11)	0.0554 (5)
H6	0.5380	0.9006	0.8832	0.066*
C7	0.56580 (9)	0.84295 (19)	0.80055 (10)	0.0456 (4)
N8	0.56316 (9)	0.54573 (17)	0.73743 (9)	0.0564 (4)
N9	0.58487 (7)	0.57989 (14)	0.68215 (9)	0.0483 (3)
C10	0.58058 (13)	0.4814 (2)	0.64692 (12)	0.0646 (6)
C11	0.5552 (2)	0.3850 (2)	0.68054 (18)	0.1089 (14)
H11	0.5468	0.3065	0.6665	0.131*
C12	0.54517 (19)	0.4278 (3)	0.73672 (16)	0.0948 (11)
H12	0.5289	0.3842	0.7689	0.114*
C13	0.59768 (12)	0.4863 (2)	0.58140 (11)	0.0600 (6)
C14	0.65777 (13)	0.4790 (2)	0.56409 (12)	0.0635 (6)
C15	0.67262 (13)	0.4905 (3)	0.50323 (13)	0.0678 (7)
H15	0.7126	0.4856	0.4918	0.081*
C16	0.62930 (13)	0.5090 (3)	0.45922 (12)	0.0678 (6)
C17	0.57040 (13)	0.5119 (3)	0.47714 (13)	0.0715 (7)
H17	0.5409	0.5225	0.4479	0.086*
C18	0.55331 (12)	0.4996 (3)	0.53682 (13)	0.0695 (7)
C19	0.70679 (16)	0.4563 (3)	0.60912 (15)	0.0844 (9)
H19A	0.7043	0.3735	0.6236	0.127*
H19B	0.7025	0.5119	0.6425	0.127*
H19C	0.7449	0.4690	0.5901	0.127*
C20	0.64758 (18)	0.5258 (4)	0.39392 (14)	0.0957 (11)
H20A	0.6132	0.5159	0.3683	0.144*
H20B	0.6773	0.4658	0.3835	0.144*
H20C	0.6639	0.6065	0.3885	0.144*
C21	0.48794 (15)	0.5013 (5)	0.55272 (19)	0.1132 (15)
H21A	0.4645	0.4925	0.5166	0.170*
H21B	0.4783	0.5776	0.5720	0.170*
H21C	0.4792	0.4348	0.5798	0.170*
N22	0.58671 (8)	0.95299 (16)	0.77437 (8)	0.0468 (4)
N23	0.61361 (7)	0.94846 (16)	0.71854 (8)	0.0434 (3)
C24	0.63490 (9)	1.06095 (19)	0.70766 (11)	0.0488 (4)
C25	0.62093 (13)	1.1370 (2)	0.75783 (13)	0.0624 (6)
H25	0.6305	1.2195	0.7620	0.075*
C26	0.59119 (12)	1.0673 (2)	0.79821 (12)	0.0608 (6)
H26	0.5765	1.0927	0.8355	0.073*
C27	0.67046 (9)	1.09025 (18)	0.65231 (11)	0.0496 (4)
C28	0.73324 (10)	1.0974 (2)	0.65716 (12)	0.0581 (5)
C29	0.76674 (11)	1.1237 (3)	0.60657 (15)	0.0692 (7)
H29	0.8082	1.1272	0.6103	0.083*
C30	0.74159 (12)	1.1450 (3)	0.55046 (14)	0.0714 (7)
C31	0.67956 (12)	1.1402 (2)	0.54673 (12)	0.0624 (6)
H31	0.6614	1.1558	0.5096	0.075*
C32	0.64328 (10)	1.1130 (2)	0.59637 (11)	0.0531 (5)
C33	0.76527 (12)	1.0772 (3)	0.71653 (14)	0.0752 (8)
H33A	0.7686	0.9908	0.7242	0.113*
H33B	0.7430	1.1152	0.7486	0.113*
H33C	0.8046	1.1126	0.7145	0.113*
C34	0.77911 (17)	1.1722 (5)	0.4957 (2)	0.1076 (13)
H34A	0.8105	1.2283	0.5064	0.161*
H34B	0.7545	1.2082	0.4648	0.161*
H34C	0.7964	1.0975	0.4808	0.161*
C35	0.57717 (10)	1.1124 (2)	0.58626 (13)	0.0629 (6)
H35A	0.5585	1.0588	0.6151	0.094*
H35B	0.5688	1.0841	0.5460	0.094*
H35C	0.5618	1.1940	0.5912	0.094*
N36	0.64243 (7)	0.79238 (16)	0.59803 (8)	0.0437 (3)
C37	0.60653 (8)	0.8124 (2)	0.55128 (10)	0.0450 (4)
C38	0.62794 (10)	0.8306 (2)	0.49313 (10)	0.0547 (5)
H38	0.6023	0.8424	0.4605	0.066*
C39	0.68920 (12)	0.8302 (3)	0.48635 (11)	0.0625 (6)
H39	0.7052	0.8421	0.4479	0.075*
C40	0.72801 (10)	0.8129 (3)	0.53452 (11)	0.0583 (5)
H40	0.7693	0.8155	0.5296	0.070*
C41	0.70184 (9)	0.79158 (19)	0.59044 (10)	0.0462 (4)
N42	0.54538 (8)	0.81694 (17)	0.56736 (8)	0.0462 (4)
N43	0.53080 (7)	0.81276 (15)	0.62770 (8)	0.0442 (3)
C44	0.47234 (9)	0.8388 (2)	0.63077 (10)	0.0517 (5)
C45	0.44993 (10)	0.8589 (3)	0.57238 (12)	0.0673 (7)
H45	0.4106	0.8778	0.5623	0.081*
C46	0.49617 (10)	0.8457 (3)	0.53343 (11)	0.0602 (6)
H46	0.4948	0.8546	0.4916	0.072*
C47	0.44206 (8)	0.8464 (2)	0.69096 (11)	0.0546 (5)
C48	0.41866 (12)	0.7403 (2)	0.71846 (14)	0.0637 (6)
C49	0.39602 (13)	0.7501 (3)	0.77725 (16)	0.0747 (8)
H49	0.3821	0.6797	0.7963	0.090*
C50	0.39348 (11)	0.8585 (3)	0.80785 (13)	0.0720 (7)
C51	0.41353 (11)	0.9626 (3)	0.77896 (13)	0.0683 (6)
H51	0.4113	1.0374	0.7990	0.082*
C52	0.43717 (9)	0.9590 (2)	0.72048 (11)	0.0585 (5)
C53	0.41764 (16)	0.6195 (3)	0.6862 (2)	0.0937 (10)
H53A	0.3981	0.5595	0.7111	0.141*
H53B	0.4579	0.5937	0.6780	0.141*
H53C	0.3962	0.6279	0.6488	0.141*
C54	0.36962 (19)	0.8661 (5)	0.87150 (16)	0.1073 (12)
H54A	0.3761	0.7894	0.8917	0.161*
H54B	0.3275	0.8836	0.8704	0.161*
H54C	0.3900	0.9302	0.8929	0.161*
C55	0.45633 (12)	1.0771 (3)	0.69217 (17)	0.0799 (8)
H55A	0.4975	1.0927	0.7019	0.120*
H55B	0.4319	1.1426	0.7074	0.120*
H55C	0.4519	1.0717	0.6491	0.120*
N56	0.73330 (8)	0.76534 (17)	0.64401 (9)	0.0493 (4)
N57	0.70164 (7)	0.73378 (15)	0.69457 (8)	0.0462 (4)
C58	0.74179 (9)	0.7006 (2)	0.73604 (11)	0.0542 (5)
C59	0.80006 (11)	0.7140 (3)	0.71203 (14)	0.0674 (7)
H59	0.8360	0.6986	0.7319	0.081*
C60	0.79328 (11)	0.7540 (3)	0.65399 (13)	0.0616 (6)
H60	0.8237	0.7703	0.6265	0.074*
C61	0.72196 (9)	0.6563 (2)	0.79660 (11)	0.0558 (5)
C62	0.71531 (12)	0.5299 (3)	0.80706 (13)	0.0663 (6)
C63	0.69156 (14)	0.4917 (3)	0.86212 (17)	0.0809 (9)
H63	0.6859	0.4083	0.8687	0.097*
C64	0.67597 (13)	0.5735 (4)	0.90752 (15)	0.0829 (9)
C65	0.68537 (12)	0.6981 (3)	0.89752 (13)	0.0737 (7)
H65	0.6758	0.7544	0.9276	0.088*
C66	0.70900 (11)	0.7393 (3)	0.84285 (12)	0.0619 (6)
C67	0.7346 (2)	0.4340 (3)	0.76170 (17)	0.0933 (10)
H67A	0.7516	0.3653	0.7826	0.140*
H67B	0.7639	0.4685	0.7349	0.140*
H67C	0.7004	0.4074	0.7388	0.140*
C68	0.6485 (2)	0.5272 (6)	0.9655 (2)	0.1256 (17)
H68A	0.6226	0.4592	0.9568	0.188*
H68B	0.6257	0.5917	0.9841	0.188*
H68C	0.6796	0.5012	0.9926	0.188*
C69	0.72050 (15)	0.8746 (3)	0.83585 (14)	0.0756 (7)
H69A	0.7045	0.9175	0.8702	0.113*
H69B	0.7015	0.9036	0.7996	0.113*
H69C	0.7628	0.8889	0.8333	0.113*
N70	0.51618 (19)	0.7544 (3)	0.36273 (14)	0.0915 (9)
O71	0.52326 (14)	0.8553 (2)	0.38852 (10)	0.0991 (8)
O72	0.5505 (2)	0.7169 (4)	0.3250 (2)	0.1495 (14)
O73	0.47080 (19)	0.6941 (3)	0.37401 (18)	0.1396 (13)
N74A	0.59323 (14)	0.8685 (5)	1.0120 (2)	0.0738 (14)	0.60
O75A	0.6265 (3)	0.9284 (7)	0.9786 (4)	0.083 (2)*	0.30
O76A	0.6201 (4)	0.7880 (9)	1.0457 (4)	0.106 (3)*	0.30
O77A	0.5393 (2)	0.8447 (9)	1.0021 (4)	0.0541 (15)*	0.30
O75B	0.6308 (3)	0.8734 (9)	1.0520 (4)	0.091 (2)*	0.30
O76B	0.5459 (4)	0.8113 (11)	1.0125 (5)	0.111 (4)*	0.30
O77B	0.6003 (4)	0.9536 (8)	0.9694 (4)	0.104 (3)*	0.30
N74C	0.5932 (5)	0.8383 (15)	1.0211 (8)	0.182 (8)*	0.40
O75C	0.5873 (6)	0.7684 (10)	1.0657 (6)	0.170 (4)*	0.40
O76C	0.6388 (4)	0.9051 (9)	1.0220 (5)	0.135 (3)*	0.40
O77C	0.5468 (3)	0.8841 (8)	0.9965 (4)	0.098 (3)*	0.40

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.04282 (12)	0.04065 (12)	0.03614 (12)	0.00026 (8)	0.00090 (11)	−0.00076 (14)
N2	0.0495 (9)	0.0424 (9)	0.0421 (9)	0.0018 (6)	0.0021 (7)	−0.0010 (7)
C3	0.0550 (11)	0.0476 (11)	0.0441 (11)	0.0023 (8)	0.0029 (8)	0.0019 (8)
C4	0.0689 (13)	0.0573 (13)	0.0479 (12)	−0.0014 (10)	0.0089 (10)	0.0065 (10)
C5	0.0660 (13)	0.0679 (15)	0.0444 (12)	0.0016 (10)	0.0084 (10)	0.0035 (10)
C6	0.0610 (12)	0.0610 (13)	0.0441 (11)	0.0039 (10)	0.0042 (9)	−0.0076 (9)
C7	0.0462 (10)	0.0472 (11)	0.0435 (10)	0.0025 (8)	−0.0014 (8)	−0.0019 (8)
N8	0.0748 (12)	0.0430 (9)	0.0513 (10)	−0.0026 (8)	0.0116 (9)	0.0031 (8)
N9	0.0606 (8)	0.0423 (7)	0.0419 (8)	0.0001 (6)	0.0015 (9)	−0.0017 (9)
C10	0.0906 (17)	0.0439 (12)	0.0595 (15)	−0.0054 (11)	0.0113 (13)	−0.0050 (10)
C11	0.204 (4)	0.0410 (12)	0.0815 (19)	−0.0303 (17)	0.047 (3)	−0.0130 (16)
C12	0.163 (3)	0.0423 (13)	0.0789 (19)	−0.0194 (16)	0.040 (2)	0.0010 (13)
C13	0.0827 (15)	0.0448 (12)	0.0526 (13)	−0.0061 (10)	0.0093 (11)	−0.0139 (10)
C14	0.0822 (16)	0.0506 (12)	0.0575 (13)	0.0088 (11)	−0.0024 (12)	−0.0078 (10)
C15	0.0741 (16)	0.0705 (16)	0.0588 (15)	0.0054 (12)	0.0058 (12)	−0.0097 (12)
C16	0.0819 (16)	0.0675 (16)	0.0539 (14)	0.0007 (13)	0.0024 (13)	−0.0111 (12)
C17	0.0778 (16)	0.0779 (17)	0.0588 (15)	−0.0048 (13)	−0.0102 (13)	−0.0200 (13)
C18	0.0739 (15)	0.0669 (15)	0.0678 (16)	−0.0102 (12)	0.0073 (13)	−0.0265 (13)
C19	0.100 (2)	0.086 (2)	0.0679 (18)	0.0235 (17)	−0.0134 (16)	−0.0090 (15)
C20	0.107 (3)	0.123 (3)	0.0574 (18)	0.006 (2)	0.0064 (16)	−0.0076 (18)
C21	0.0744 (19)	0.167 (4)	0.098 (3)	−0.027 (2)	0.0113 (18)	−0.047 (3)
N22	0.0523 (9)	0.0439 (9)	0.0443 (9)	0.0004 (7)	0.0008 (7)	−0.0070 (7)
N23	0.0468 (8)	0.0422 (9)	0.0411 (9)	−0.0008 (6)	−0.0024 (6)	−0.0021 (7)
C24	0.0498 (10)	0.0408 (10)	0.0558 (11)	−0.0010 (8)	−0.0078 (9)	−0.0013 (8)
C25	0.0757 (15)	0.0421 (12)	0.0693 (16)	−0.0052 (10)	0.0022 (12)	−0.0114 (11)
C26	0.0733 (14)	0.0495 (12)	0.0594 (14)	0.0025 (10)	0.0007 (12)	−0.0158 (10)
C27	0.0503 (10)	0.0378 (10)	0.0607 (12)	−0.0031 (8)	−0.0041 (9)	0.0026 (8)
C28	0.0518 (11)	0.0501 (12)	0.0724 (15)	−0.0038 (9)	−0.0059 (10)	0.0078 (10)
C29	0.0506 (12)	0.0694 (16)	0.0877 (19)	−0.0018 (10)	0.0004 (12)	0.0148 (14)
C30	0.0665 (15)	0.0687 (16)	0.0790 (18)	−0.0042 (11)	0.0119 (13)	0.0123 (13)
C31	0.0689 (14)	0.0596 (13)	0.0587 (14)	−0.0015 (10)	−0.0029 (11)	0.0061 (11)
C32	0.0560 (11)	0.0407 (11)	0.0626 (13)	−0.0013 (8)	−0.0054 (10)	−0.0028 (9)
C33	0.0595 (14)	0.086 (2)	0.0805 (19)	−0.0064 (13)	−0.0158 (13)	0.0154 (16)
C34	0.089 (2)	0.136 (4)	0.098 (3)	−0.001 (2)	0.025 (2)	0.035 (2)
C35	0.0575 (12)	0.0622 (14)	0.0689 (16)	0.0004 (10)	−0.0089 (11)	0.0005 (12)
N36	0.0459 (8)	0.0446 (9)	0.0406 (8)	−0.0012 (6)	0.0020 (7)	−0.0006 (7)
C37	0.0485 (10)	0.0444 (10)	0.0419 (10)	−0.0018 (7)	−0.0001 (8)	−0.0046 (8)
C38	0.0573 (11)	0.0664 (14)	0.0402 (10)	−0.0024 (10)	0.0014 (9)	−0.0005 (9)
C39	0.0668 (13)	0.0777 (16)	0.0429 (12)	−0.0027 (12)	0.0113 (10)	0.0036 (11)
C40	0.0525 (11)	0.0714 (15)	0.0511 (12)	−0.0013 (11)	0.0112 (9)	0.0036 (11)
C41	0.0466 (10)	0.0478 (10)	0.0441 (10)	0.0017 (7)	0.0025 (8)	−0.0013 (8)
N42	0.0465 (8)	0.0542 (10)	0.0380 (8)	−0.0033 (7)	−0.0022 (7)	−0.0014 (7)
N43	0.0452 (8)	0.0487 (9)	0.0386 (9)	−0.0023 (6)	0.0004 (6)	0.0003 (7)
C44	0.0434 (10)	0.0596 (12)	0.0522 (12)	−0.0010 (8)	−0.0009 (8)	0.0053 (10)
C45	0.0449 (11)	0.099 (2)	0.0577 (14)	−0.0010 (11)	−0.0074 (10)	0.0089 (13)
C46	0.0518 (11)	0.0809 (16)	0.0479 (12)	−0.0038 (10)	−0.0100 (10)	0.0051 (11)
C47	0.0402 (9)	0.0693 (13)	0.0541 (14)	0.0052 (8)	0.0000 (9)	0.0056 (10)
C48	0.0542 (13)	0.0727 (16)	0.0642 (15)	0.0040 (10)	0.0096 (11)	0.0075 (12)
C49	0.0649 (16)	0.091 (2)	0.0683 (19)	0.0079 (12)	0.0129 (13)	0.0175 (15)
C50	0.0589 (14)	0.103 (2)	0.0543 (14)	0.0112 (13)	0.0061 (11)	0.0011 (15)
C51	0.0539 (12)	0.0849 (18)	0.0661 (16)	0.0062 (12)	0.0023 (11)	−0.0088 (13)
C52	0.0435 (10)	0.0731 (15)	0.0589 (14)	0.0061 (9)	−0.0006 (9)	0.0015 (11)
C53	0.104 (2)	0.0738 (17)	0.103 (2)	−0.0111 (14)	0.035 (2)	−0.001 (2)
C54	0.109 (3)	0.147 (4)	0.066 (2)	0.013 (2)	0.0246 (19)	0.006 (2)
C55	0.0778 (16)	0.0675 (15)	0.094 (2)	0.0045 (12)	0.0165 (16)	0.0025 (15)
N56	0.0434 (9)	0.0560 (10)	0.0485 (10)	0.0017 (7)	0.0015 (7)	0.0045 (8)
N57	0.0455 (8)	0.0478 (9)	0.0452 (11)	0.0023 (6)	−0.0003 (7)	0.0021 (7)
C58	0.0480 (10)	0.0590 (12)	0.0556 (13)	0.0036 (9)	−0.0083 (10)	0.0043 (10)
C59	0.0441 (11)	0.0891 (19)	0.0689 (17)	0.0063 (11)	−0.0045 (11)	0.0116 (14)
C60	0.0418 (11)	0.0784 (16)	0.0647 (15)	0.0019 (10)	0.0045 (10)	0.0072 (12)
C61	0.0485 (10)	0.0647 (14)	0.0543 (12)	0.0024 (9)	−0.0096 (9)	0.0097 (10)
C62	0.0634 (13)	0.0716 (16)	0.0639 (15)	−0.0015 (11)	−0.0141 (12)	0.0152 (12)
C63	0.0764 (17)	0.084 (2)	0.083 (2)	−0.0054 (14)	−0.0101 (15)	0.0322 (17)
C64	0.0628 (15)	0.113 (2)	0.0732 (19)	0.0058 (15)	0.0049 (13)	0.0332 (18)
C65	0.0589 (13)	0.104 (2)	0.0587 (15)	0.0137 (14)	−0.0018 (11)	0.0101 (14)
C66	0.0533 (12)	0.0770 (16)	0.0553 (13)	0.0066 (11)	−0.0102 (10)	0.0092 (11)
C67	0.130 (3)	0.070 (2)	0.079 (2)	−0.0036 (18)	−0.017 (2)	0.0070 (16)
C68	0.099 (3)	0.172 (4)	0.105 (3)	0.018 (3)	0.038 (2)	0.061 (3)
C69	0.0882 (18)	0.0721 (17)	0.0665 (17)	0.0042 (14)	−0.0181 (14)	−0.0012 (14)
N70	0.140 (3)	0.0681 (16)	0.0661 (16)	0.0111 (17)	−0.0375 (18)	−0.0001 (13)
O71	0.154 (2)	0.0782 (14)	0.0655 (13)	−0.0208 (14)	−0.0310 (14)	−0.0047 (11)
O72	0.163 (3)	0.135 (3)	0.151 (3)	0.041 (2)	−0.015 (3)	−0.034 (3)
O73	0.195 (4)	0.0941 (19)	0.130 (3)	−0.048 (2)	−0.031 (3)	0.0052 (18)
N74A	0.0384 (15)	0.102 (3)	0.081 (3)	0.0166 (17)	−0.0128 (17)	−0.050 (2)

Geometric parameters (Å, º)

Co1—N2	2.0132 (18)	C37—N42	1.412 (3)
Co1—N9	2.1190 (15)	C38—C39	1.376 (3)
Co1—N23	2.1368 (17)	C38—H38	0.9300
Co1—N36	2.0077 (17)	C39—C40	1.386 (4)
Co1—N43	2.1327 (17)	C39—H39	0.9300
Co1—N57	2.1581 (16)	C40—C41	1.387 (3)
N2—C7	1.328 (3)	C40—H40	0.9300
N2—C3	1.331 (3)	C41—N56	1.406 (3)
C3—C4	1.380 (3)	N42—C46	1.367 (3)
C3—N8	1.415 (3)	N42—N43	1.374 (2)
C4—C5	1.378 (4)	N43—C44	1.338 (3)
C4—H4	0.9300	C44—C45	1.402 (3)
C5—C6	1.384 (4)	C44—C47	1.495 (3)
C5—H5	0.9300	C45—C46	1.352 (4)
C6—C7	1.378 (3)	C45—H45	0.9300
C6—H6	0.9300	C46—H46	0.9300
C7—N22	1.412 (3)	C47—C52	1.395 (3)
N8—C12	1.348 (3)	C47—C48	1.409 (3)
N8—N9	1.366 (3)	C48—C49	1.399 (4)
N9—C10	1.330 (3)	C48—C53	1.498 (4)
C10—C11	1.407 (4)	C49—C50	1.363 (5)
C10—C13	1.499 (3)	C49—H49	0.9300
C11—C12	1.345 (5)	C50—C51	1.378 (5)
C11—H11	0.9300	C50—C54	1.507 (4)
C12—H12	0.9300	C51—C52	1.397 (4)
C13—C14	1.398 (4)	C51—H51	0.9300
C13—C18	1.405 (4)	C52—C55	1.495 (4)
C14—C15	1.391 (4)	C53—H53A	0.9600
C14—C19	1.500 (4)	C53—H53B	0.9600
C15—C16	1.387 (4)	C53—H53C	0.9600
C15—H15	0.9300	C54—H54A	0.9600
C16—C17	1.374 (4)	C54—H54B	0.9600
C16—C20	1.512 (4)	C54—H54C	0.9600
C17—C18	1.380 (4)	C55—H55A	0.9600
C17—H17	0.9300	C55—H55B	0.9600
C18—C21	1.502 (4)	C55—H55C	0.9600
C19—H19A	0.9600	N56—C60	1.363 (3)
C19—H19B	0.9600	N56—N57	1.366 (2)
C19—H19C	0.9600	N57—C58	1.332 (3)
C20—H20A	0.9600	C58—C59	1.413 (4)
C20—H20B	0.9600	C58—C61	1.490 (3)
C20—H20C	0.9600	C59—C60	1.363 (4)
C21—H21A	0.9600	C59—H59	0.9300
C21—H21B	0.9600	C60—H60	0.9300
C21—H21C	0.9600	C61—C66	1.396 (4)
N22—C26	1.357 (3)	C61—C62	1.407 (4)
N22—N23	1.373 (2)	C62—C63	1.391 (4)
N23—C24	1.338 (3)	C62—C67	1.511 (5)
C24—C25	1.419 (3)	C63—C64	1.388 (5)
C24—C27	1.493 (3)	C63—H63	0.9300
C25—C26	1.348 (4)	C64—C65	1.393 (5)
C25—H25	0.9300	C64—C68	1.509 (5)
C26—H26	0.9300	C65—C66	1.393 (4)
C27—C32	1.400 (3)	C65—H65	0.9300
C27—C28	1.408 (3)	C66—C69	1.506 (4)
C28—C29	1.376 (4)	C67—H67A	0.9600
C28—C33	1.511 (4)	C67—H67B	0.9600
C29—C30	1.381 (4)	C67—H67C	0.9600
C29—H29	0.9300	C68—H68A	0.9600
C30—C31	1.389 (4)	C68—H68B	0.9600
C30—C34	1.502 (4)	C68—H68C	0.9600
C31—C32	1.396 (4)	C69—H69A	0.9600
C31—H31	0.9300	C69—H69B	0.9600
C32—C35	1.493 (3)	C69—H69C	0.9600
C33—H33A	0.9600	N70—O72	1.204 (5)
C33—H33B	0.9600	N70—O73	1.234 (5)
C33—H33C	0.9600	N70—O71	1.249 (4)
C34—H34A	0.9600	N74A—O75A	1.234 (7)
C34—H34B	0.9600	N74A—O77A	1.251 (6)
C34—H34C	0.9600	N74A—O76A	1.298 (8)
C35—H35A	0.9600	N74A—O75B	1.220 (6)
C35—H35B	0.9600	N74A—O76B	1.227 (7)
C35—H35C	0.9600	N74A—O77B	1.332 (7)
N36—C37	1.326 (3)	N74C—O75C	1.253 (9)
N36—C41	1.338 (3)	N74C—O76C	1.253 (9)
C37—C38	1.386 (3)	N74C—O77C	1.272 (9)
N2—Co1—N9	77.42 (7)	H35B—C35—H35C	109.5
N2—Co1—N23	77.03 (7)	C37—N36—C41	120.21 (18)
N2—Co1—N36	179.08 (7)	C37—N36—Co1	119.81 (13)
N2—Co1—N43	102.21 (7)	C41—N36—Co1	119.95 (14)
N2—Co1—N57	103.69 (7)	N36—C37—C38	122.54 (18)
N9—Co1—N36	103.34 (7)	N36—C37—N42	113.23 (18)
N9—Co1—N23	154.45 (7)	C38—C37—N42	124.20 (19)
N9—Co1—N43	92.04 (7)	C39—C38—C37	116.3 (2)
N9—Co1—N57	93.44 (6)	C39—C38—H38	121.8
N23—Co1—N36	102.20 (7)	C37—C38—H38	121.8
N23—Co1—N43	93.34 (6)	C38—C39—C40	122.6 (2)
N23—Co1—N57	92.54 (6)	C38—C39—H39	118.7
N36—Co1—N43	77.29 (7)	C40—C39—H39	118.7
N36—Co1—N57	76.81 (6)	C39—C40—C41	116.4 (2)
N43—Co1—N57	154.10 (6)	C39—C40—H40	121.8
C7—N2—C3	119.80 (19)	C41—C40—H40	121.8
C7—N2—Co1	120.43 (14)	N36—C41—C40	121.9 (2)
C3—N2—Co1	119.76 (14)	N36—C41—N56	113.03 (18)
N2—C3—C4	122.5 (2)	C40—C41—N56	125.04 (18)
N2—C3—N8	112.52 (19)	C46—N42—N43	110.48 (18)
C4—C3—N8	124.9 (2)	C46—N42—C37	130.4 (2)
C5—C4—C3	116.4 (2)	N43—N42—C37	118.19 (16)
C5—C4—H4	121.8	C44—N43—N42	105.87 (17)
C3—C4—H4	121.8	C44—N43—Co1	143.50 (15)
C4—C5—C6	122.3 (2)	N42—N43—Co1	110.63 (12)
C4—C5—H5	118.9	N43—C44—C45	109.6 (2)
C6—C5—H5	118.9	N43—C44—C47	119.90 (19)
C7—C6—C5	116.4 (2)	C45—C44—C47	130.49 (19)
C7—C6—H6	121.8	C46—C45—C44	107.3 (2)
C5—C6—H6	121.8	C46—C45—H45	126.4
N2—C7—C6	122.6 (2)	C44—C45—H45	126.4
N2—C7—N22	112.57 (19)	C45—C46—N42	106.8 (2)
C6—C7—N22	124.8 (2)	C45—C46—H46	126.6
C12—N8—N9	110.8 (2)	N42—C46—H46	126.6
C12—N8—C3	129.7 (2)	C52—C47—C48	119.5 (2)
N9—N8—C3	118.91 (17)	C52—C47—C44	120.1 (2)
C10—N9—N8	106.14 (18)	C48—C47—C44	120.4 (2)
C10—N9—Co1	142.51 (17)	C49—C48—C47	118.2 (3)
N8—N9—Co1	111.18 (13)	C49—C48—C53	120.3 (3)
N9—C10—C11	108.9 (2)	C47—C48—C53	121.6 (3)
N9—C10—C13	121.3 (2)	C50—C49—C48	122.9 (3)
C11—C10—C13	129.7 (2)	C50—C49—H49	118.6
C12—C11—C10	107.2 (2)	C48—C49—H49	118.6
C12—C11—H11	126.4	C49—C50—C51	118.1 (3)
C10—C11—H11	126.4	C49—C50—C54	121.8 (3)
C11—C12—N8	107.0 (3)	C51—C50—C54	120.1 (3)
C11—C12—H12	126.5	C50—C51—C52	121.9 (3)
N8—C12—H12	126.5	C50—C51—H51	119.1
C14—C13—C18	119.4 (2)	C52—C51—H51	119.1
C14—C13—C10	120.5 (2)	C47—C52—C51	119.2 (2)
C18—C13—C10	120.1 (2)	C47—C52—C55	122.7 (2)
C15—C14—C13	119.3 (2)	C51—C52—C55	118.1 (3)
C15—C14—C19	118.8 (3)	C48—C53—H53A	109.5
C13—C14—C19	121.9 (3)	C48—C53—H53B	109.5
C16—C15—C14	121.7 (3)	H53A—C53—H53B	109.5
C16—C15—H15	119.2	C48—C53—H53C	109.5
C14—C15—H15	119.2	H53A—C53—H53C	109.5
C17—C16—C15	118.0 (3)	H53B—C53—H53C	109.5
C17—C16—C20	122.1 (3)	C50—C54—H54A	109.5
C15—C16—C20	120.0 (3)	C50—C54—H54B	109.5
C16—C17—C18	122.6 (3)	H54A—C54—H54B	109.5
C16—C17—H17	118.7	C50—C54—H54C	109.5
C18—C17—H17	118.7	H54A—C54—H54C	109.5
C17—C18—C13	119.0 (3)	H54B—C54—H54C	109.5
C17—C18—C21	119.4 (3)	C52—C55—H55A	109.5
C13—C18—C21	121.5 (3)	C52—C55—H55B	109.5
C14—C19—H19A	109.5	H55A—C55—H55B	109.5
C14—C19—H19B	109.5	C52—C55—H55C	109.5
H19A—C19—H19B	109.5	H55A—C55—H55C	109.5
C14—C19—H19C	109.5	H55B—C55—H55C	109.5
H19A—C19—H19C	109.5	C60—N56—N57	110.67 (19)
H19B—C19—H19C	109.5	C60—N56—C41	130.2 (2)
C16—C20—H20A	109.5	N57—N56—C41	118.78 (15)
C16—C20—H20B	109.5	C58—N57—N56	106.44 (17)
H20A—C20—H20B	109.5	C58—N57—Co1	143.11 (15)
C16—C20—H20C	109.5	N56—N57—Co1	110.20 (12)
H20A—C20—H20C	109.5	N57—C58—C59	109.5 (2)
H20B—C20—H20C	109.5	N57—C58—C61	120.40 (19)
C18—C21—H21A	109.5	C59—C58—C61	130.1 (2)
C18—C21—H21B	109.5	C60—C59—C58	106.5 (2)
H21A—C21—H21B	109.5	C60—C59—H59	126.7
C18—C21—H21C	109.5	C58—C59—H59	126.7
H21A—C21—H21C	109.5	C59—C60—N56	106.9 (2)
H21B—C21—H21C	109.5	C59—C60—H60	126.6
C26—N22—N23	110.47 (19)	N56—C60—H60	126.6
C26—N22—C7	130.2 (2)	C66—C61—C62	119.6 (2)
N23—N22—C7	118.84 (16)	C66—C61—C58	120.6 (2)
C24—N23—N22	106.50 (17)	C62—C61—C58	119.8 (2)
C24—N23—Co1	142.70 (15)	C63—C62—C61	118.5 (3)
N22—N23—Co1	110.80 (12)	C63—C62—C67	118.8 (3)
N23—C24—C25	108.5 (2)	C61—C62—C67	122.6 (3)
N23—C24—C27	122.18 (19)	C64—C63—C62	122.4 (3)
C25—C24—C27	129.2 (2)	C64—C63—H63	118.8
C26—C25—C24	107.2 (2)	C62—C63—H63	118.8
C26—C25—H25	126.4	C63—C64—C65	118.4 (3)
C24—C25—H25	126.4	C63—C64—C68	120.1 (4)
C25—C26—N22	107.3 (2)	C65—C64—C68	121.6 (4)
C25—C26—H26	126.4	C66—C65—C64	120.6 (3)
N22—C26—H26	126.4	C66—C65—H65	119.7
C32—C27—C28	119.3 (2)	C64—C65—H65	119.7
C32—C27—C24	122.08 (18)	C65—C66—C61	120.3 (3)
C28—C27—C24	118.6 (2)	C65—C66—C69	118.0 (3)
C29—C28—C27	119.4 (2)	C61—C66—C69	121.6 (2)
C29—C28—C33	118.6 (2)	C62—C67—H67A	109.5
C27—C28—C33	122.0 (2)	C62—C67—H67B	109.5
C28—C29—C30	122.9 (2)	H67A—C67—H67B	109.5
C28—C29—H29	118.5	C62—C67—H67C	109.5
C30—C29—H29	118.5	H67A—C67—H67C	109.5
C29—C30—C31	116.9 (2)	H67B—C67—H67C	109.5
C29—C30—C34	122.0 (3)	C64—C68—H68A	109.5
C31—C30—C34	121.1 (3)	C64—C68—H68B	109.5
C30—C31—C32	122.7 (2)	H68A—C68—H68B	109.5
C30—C31—H31	118.6	C64—C68—H68C	109.5
C32—C31—H31	118.6	H68A—C68—H68C	109.5
C31—C32—C27	118.7 (2)	H68B—C68—H68C	109.5
C31—C32—C35	117.2 (2)	C66—C69—H69A	109.5
C27—C32—C35	124.1 (2)	C66—C69—H69B	109.5
C28—C33—H33A	109.5	H69A—C69—H69B	109.5
C28—C33—H33B	109.5	C66—C69—H69C	109.5
H33A—C33—H33B	109.5	H69A—C69—H69C	109.5
C28—C33—H33C	109.5	H69B—C69—H69C	109.5
H33A—C33—H33C	109.5	O72—N70—O73	118.8 (4)
H33B—C33—H33C	109.5	O72—N70—O71	122.3 (4)
C30—C34—H34A	109.5	O73—N70—O71	118.8 (4)
C30—C34—H34B	109.5	O75A—N74A—O77A	125.8 (6)
H34A—C34—H34B	109.5	O75A—N74A—O76A	115.0 (6)
C30—C34—H34C	109.5	O77A—N74A—O76A	113.9 (7)
H34A—C34—H34C	109.5	O75B—N74A—O76B	127.5 (7)
H34B—C34—H34C	109.5	O75B—N74A—O77B	113.6 (6)
C32—C35—H35A	109.5	O76B—N74A—O77B	117.6 (6)
C32—C35—H35B	109.5	O75C—N74C—O76C	115.3 (10)
H35A—C35—H35B	109.5	O75C—N74C—O77C	119.4 (11)
C32—C35—H35C	109.5	O76C—N74C—O77C	116.1 (10)
H35A—C35—H35C	109.5

(II) Bis{2,6-bis[3-(2,4,6-trimethylphenyl)pyrazol- 1-yl-κN²]pyridine-κN}cobalt(II) dinitrate

Crystal data

[Co(C29H29N5)2](NO3)2	Dx = 1.358 Mg m^−3
Mr = 1078.09	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca21	Cell parameters from 86435 reflections
a = 22.1974 (2) Å	θ = 2.6–27.5°
b = 10.7761 (1) Å	µ = 0.39 mm^−1
c = 22.0365 (1) Å	T = 150 K
V = 5271.16 (7) Å^3	Rectangular prism, orange
Z = 4	0.45 × 0.35 × 0.28 mm
F(000) = 2260

Data collection

Nonius KappaCCD area-detector diffractometer	11941 independent reflections
Radiation source: fine-focus sealed tube	11339 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.6°
type of scans	h = −28→28
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −13→13
Tmin = 0.844, Tmax = 0.899	l = −27→28
86435 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.0591P)^2 + 1.4056P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.099	(Δ/σ)max = 0.001
S = 1.06	Δρmax = 0.68 e Å^−3
11941 reflections	Δρmin = −0.35 e Å^−3
720 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
20 restraints	Extinction coefficient: 0.0124 (9)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack, 1983
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.001 (8)

Special details

Experimental. Detector set at 30 mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings

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.

One nitrate anion is disordered over three orientations: N74A—O77A, occupancy 0.40 N74B—O77B, occupancy 0.40 N74C—O77C, occupancy 0.20. The N—O distances within the disordered anion were restrained to 1.26 (1) Å, and non-bonded O···O distances within a given disorder orientation to 2.18 (1) Å. All non-H atoms except the disordered anion were refined anisotropically, and all H atoms were placed in calculated positions and refined using a riding model. The torsions of all the methyl groups were allowed to refine freely, except that anti-bumping restraints were applied to H21B and H53B, and to H35A and H55C, to prevent abnormally short H···H contacts in the final model. Even with these restraints, there is one abnormally short intermolecular H···H contact of H11···H35Cⁱ = 2.06 Å (related by x, y − 1, z). Introduction of additional antibumping restraints between H11 and the C35ⁱ methyl group prevented the refinement from converging, so that these were omitted from the final model. However, for this reason the refined methyl group torsion on C35 probably does not correspond to the 'true' equilibrium position.

The Flack parameter was calculated using 5773 Friedel pairs.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.607483 (10)	0.76975 (2)	0.680922 (13)	0.02464 (7)
N2	0.57123 (7)	0.74756 (15)	0.76429 (8)	0.0281 (3)
C3	0.55503 (9)	0.63473 (18)	0.78297 (9)	0.0301 (4)
C4	0.53155 (10)	0.6123 (2)	0.84023 (9)	0.0352 (4)
H4	0.5206	0.5313	0.8532	0.042*
C5	0.52497 (10)	0.7152 (2)	0.87759 (9)	0.0357 (4)
H5	0.5092	0.7040	0.9173	0.043*
C6	0.54073 (9)	0.83395 (19)	0.85877 (9)	0.0331 (4)
H6	0.5353	0.9043	0.8842	0.040*
C7	0.56472 (8)	0.84434 (18)	0.80124 (9)	0.0281 (4)
N8	0.56351 (8)	0.54347 (15)	0.73779 (8)	0.0345 (4)
N9	0.58603 (7)	0.57828 (14)	0.68231 (8)	0.0297 (3)
C10	0.58181 (11)	0.4787 (2)	0.64691 (10)	0.0409 (5)
C11	0.55647 (15)	0.3800 (2)	0.68013 (15)	0.0638 (8)
H11	0.5488	0.2984	0.6657	0.077*
C12	0.54501 (15)	0.4237 (2)	0.73680 (13)	0.0576 (7)
H12	0.5274	0.3789	0.7694	0.069*
C13	0.59955 (10)	0.48487 (19)	0.58112 (10)	0.0357 (4)
C14	0.66054 (10)	0.48227 (19)	0.56414 (10)	0.0368 (4)
C15	0.67532 (11)	0.4956 (2)	0.50319 (10)	0.0393 (5)
H15	0.7165	0.4935	0.4916	0.047*
C16	0.63138 (11)	0.5121 (2)	0.45859 (10)	0.0394 (5)
C17	0.57203 (11)	0.5102 (2)	0.47650 (11)	0.0445 (5)
H17	0.5416	0.5194	0.4465	0.053*
C18	0.55488 (11)	0.4955 (2)	0.53677 (11)	0.0448 (5)
C19	0.70979 (12)	0.4623 (3)	0.60964 (11)	0.0494 (6)
H19A	0.7076	0.3772	0.6253	0.074*
H19B	0.7050	0.5210	0.6432	0.074*
H19C	0.7490	0.4754	0.5902	0.074*
C20	0.64952 (14)	0.5315 (3)	0.39335 (11)	0.0545 (6)
H20A	0.6135	0.5321	0.3677	0.082*
H20B	0.6763	0.4642	0.3806	0.082*
H20C	0.6706	0.6111	0.3894	0.082*
C21	0.48908 (13)	0.4904 (4)	0.55213 (15)	0.0800 (12)
H21A	0.4675	0.4443	0.5205	0.120*
H21B	0.4730	0.5749	0.5547	0.120*
H21C	0.4837	0.4486	0.5913	0.120*
N22	0.58580 (7)	0.95625 (15)	0.77489 (7)	0.0287 (3)
N23	0.61243 (7)	0.95166 (15)	0.71863 (7)	0.0271 (3)
C24	0.63397 (8)	1.06557 (18)	0.70815 (9)	0.0302 (4)
C25	0.62097 (11)	1.1421 (2)	0.75897 (11)	0.0387 (5)
H25	0.6313	1.2271	0.7636	0.046*
C26	0.59097 (10)	1.0707 (2)	0.79975 (10)	0.0369 (4)
H26	0.5764	1.0961	0.8383	0.044*
C27	0.66972 (8)	1.09596 (17)	0.65263 (9)	0.0303 (4)
C28	0.73288 (9)	1.10644 (18)	0.65803 (10)	0.0341 (4)
C29	0.76708 (9)	1.1349 (2)	0.60707 (11)	0.0400 (5)
H29	0.8096	1.1407	0.6111	0.048*
C30	0.74144 (11)	1.1551 (2)	0.55075 (11)	0.0419 (5)
C31	0.67913 (10)	1.1464 (2)	0.54624 (10)	0.0383 (4)
H31	0.6607	1.1613	0.5080	0.046*
C32	0.64259 (9)	1.11676 (18)	0.59568 (10)	0.0332 (4)
C33	0.76537 (10)	1.0852 (2)	0.71726 (11)	0.0432 (5)
H33A	0.7714	0.9960	0.7234	0.065*
H33B	0.7413	1.1189	0.7507	0.065*
H33C	0.8046	1.1270	0.7161	0.065*
C34	0.77921 (13)	1.1854 (3)	0.49596 (14)	0.0605 (7)
H34A	0.8086	1.2496	0.5065	0.091*
H34B	0.7532	1.2156	0.4633	0.091*
H34C	0.8004	1.1106	0.4824	0.091*
C35	0.57606 (9)	1.1107 (2)	0.58448 (10)	0.0380 (4)
H35A	0.5573	1.0558	0.6145	0.057*
H35B	0.5686	1.0784	0.5436	0.057*
H35C	0.5588	1.1941	0.5880	0.057*
N36	0.64347 (7)	0.79509 (15)	0.59762 (7)	0.0271 (3)
C37	0.60724 (8)	0.81419 (18)	0.55053 (9)	0.0281 (4)
C38	0.62918 (9)	0.8346 (2)	0.49242 (9)	0.0334 (4)
H38	0.6030	0.8458	0.4587	0.040*
C39	0.69119 (10)	0.8379 (2)	0.48616 (9)	0.0379 (4)
H39	0.7079	0.8525	0.4471	0.045*
C40	0.72998 (9)	0.8205 (2)	0.53495 (9)	0.0341 (4)
H40	0.7725	0.8243	0.5304	0.041*
C41	0.70324 (8)	0.79730 (18)	0.59060 (9)	0.0284 (4)
N42	0.54568 (7)	0.81622 (16)	0.56628 (7)	0.0289 (3)
N43	0.53070 (7)	0.81183 (15)	0.62690 (7)	0.0283 (3)
C44	0.47155 (9)	0.83587 (19)	0.62977 (9)	0.0328 (4)
C45	0.44863 (10)	0.8535 (2)	0.57075 (10)	0.0414 (5)
H45	0.4080	0.8702	0.5600	0.050*
C46	0.49620 (9)	0.8421 (2)	0.53201 (10)	0.0371 (4)
H46	0.4950	0.8506	0.4891	0.044*
C47	0.44084 (8)	0.84210 (19)	0.69011 (9)	0.0338 (4)
C48	0.41819 (10)	0.7339 (2)	0.71740 (11)	0.0392 (5)
C49	0.39541 (10)	0.7422 (3)	0.77652 (12)	0.0445 (5)
H49	0.3812	0.6689	0.7957	0.053*
C50	0.39285 (9)	0.8527 (3)	0.80795 (10)	0.0431 (5)
C51	0.41233 (10)	0.9592 (2)	0.77899 (10)	0.0405 (5)
H51	0.4096	1.0363	0.7997	0.049*
C52	0.43600 (9)	0.9571 (2)	0.72006 (10)	0.0357 (4)
C53	0.41821 (13)	0.6117 (2)	0.68511 (15)	0.0551 (6)
H53A	0.4002	0.5483	0.7113	0.083*
H53B	0.4597	0.5882	0.6752	0.083*
H53C	0.3947	0.6186	0.6476	0.083*
C54	0.36921 (14)	0.8583 (3)	0.87202 (12)	0.0610 (7)
H54A	0.3793	0.7812	0.8933	0.091*
H54B	0.3254	0.8687	0.8712	0.091*
H54C	0.3876	0.9287	0.8933	0.091*
C55	0.45583 (10)	1.0768 (2)	0.69173 (12)	0.0449 (5)
H55A	0.4310	1.1449	0.7073	0.067*
H55B	0.4512	1.0715	0.6476	0.067*
H55C	0.4982	1.0922	0.7018	0.067*
N56	0.73443 (7)	0.77133 (15)	0.64470 (8)	0.0295 (3)
N57	0.70228 (7)	0.73903 (15)	0.69539 (7)	0.0286 (3)
C58	0.74248 (9)	0.70686 (19)	0.73734 (9)	0.0326 (4)
C59	0.80142 (10)	0.7207 (2)	0.71390 (11)	0.0387 (5)
H59	0.8382	0.7052	0.7346	0.046*
C60	0.79488 (10)	0.7607 (2)	0.65539 (11)	0.0367 (4)
H60	0.8264	0.7779	0.6275	0.044*
C61	0.72184 (9)	0.6618 (2)	0.79812 (9)	0.0345 (4)
C62	0.71419 (10)	0.5345 (2)	0.80860 (11)	0.0424 (5)
C63	0.68995 (11)	0.4961 (3)	0.86429 (13)	0.0517 (6)
H63	0.6838	0.4100	0.8712	0.062*
C64	0.67487 (11)	0.5793 (3)	0.90920 (12)	0.0549 (7)
C65	0.68519 (10)	0.7055 (3)	0.89887 (11)	0.0473 (5)
H65	0.6759	0.7637	0.9299	0.057*
C66	0.70876 (10)	0.7479 (2)	0.84414 (10)	0.0386 (5)
C67	0.73200 (15)	0.4374 (2)	0.76289 (13)	0.0566 (7)
H67A	0.6968	0.4142	0.7386	0.085*
H67B	0.7474	0.3641	0.7841	0.085*
H67C	0.7634	0.4708	0.7362	0.085*
C68	0.64717 (16)	0.5360 (5)	0.96787 (17)	0.0824 (12)
H68A	0.6213	0.4641	0.9600	0.124*
H68B	0.6231	0.6032	0.9855	0.124*
H68C	0.6791	0.5125	0.9963	0.124*
C69	0.72065 (12)	0.8842 (2)	0.83607 (11)	0.0439 (5)
H69A	0.7037	0.9300	0.8705	0.066*
H69B	0.7018	0.9129	0.7984	0.066*
H69C	0.7642	0.8986	0.8341	0.066*
N70	0.51919 (13)	0.75660 (19)	0.36134 (10)	0.0542 (6)
O71	0.52663 (9)	0.85955 (16)	0.38760 (8)	0.0525 (4)
O72	0.55433 (14)	0.7221 (3)	0.32174 (13)	0.0835 (8)
O73	0.47400 (13)	0.6926 (2)	0.37436 (11)	0.0805 (8)
N74A	0.5923 (2)	0.8629 (6)	1.0099 (3)	0.0338 (14)*	0.40
O75A	0.6257 (2)	0.9362 (5)	0.9804 (2)	0.0557 (12)*	0.40
O76A	0.6165 (2)	0.7954 (6)	1.0479 (3)	0.0628 (13)*	0.40
O77A	0.5372 (2)	0.8588 (7)	0.9998 (3)	0.0338 (13)*	0.40
N74B	0.5933 (2)	0.8979 (5)	1.0041 (2)	0.0318 (12)*	0.40
O75B	0.6296 (3)	0.8728 (7)	1.0473 (3)	0.0668 (15)*	0.40
O76B	0.5439 (3)	0.8336 (6)	1.0060 (3)	0.059 (2)*	0.40
O77B	0.6062 (2)	0.9703 (5)	0.9640 (2)	0.0522 (11)*	0.40
N74C	0.5882 (5)	0.8510 (12)	1.0266 (6)	0.059 (4)*	0.20
O75C	0.5813 (7)	0.7676 (13)	1.0650 (7)	0.103 (5)*	0.20
O76C	0.6370 (4)	0.9143 (12)	1.0287 (6)	0.072 (3)*	0.20
O77C	0.5447 (4)	0.8923 (10)	0.9950 (5)	0.045 (3)*	0.20

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.02629 (11)	0.02474 (12)	0.02291 (11)	0.00012 (8)	0.00073 (10)	−0.00009 (11)
N2	0.0291 (7)	0.0279 (8)	0.0271 (8)	0.0006 (6)	0.0020 (6)	0.0001 (6)
C3	0.0336 (9)	0.0282 (9)	0.0286 (9)	0.0027 (7)	0.0024 (7)	0.0009 (7)
C4	0.0412 (10)	0.0344 (10)	0.0299 (9)	0.0018 (8)	0.0054 (8)	0.0036 (8)
C5	0.0362 (10)	0.0429 (11)	0.0280 (9)	0.0020 (8)	0.0038 (8)	0.0012 (8)
C6	0.0329 (9)	0.0361 (10)	0.0302 (9)	0.0039 (8)	0.0004 (8)	−0.0037 (8)
C7	0.0273 (8)	0.0287 (9)	0.0285 (9)	0.0026 (7)	−0.0007 (7)	−0.0020 (7)
N8	0.0452 (9)	0.0267 (8)	0.0315 (8)	−0.0009 (7)	0.0093 (7)	0.0019 (6)
N9	0.0349 (7)	0.0286 (7)	0.0257 (7)	0.0014 (6)	0.0024 (8)	0.0007 (7)
C10	0.0554 (13)	0.0289 (10)	0.0384 (11)	−0.0019 (9)	0.0104 (10)	−0.0033 (8)
C11	0.109 (2)	0.0281 (10)	0.0545 (14)	−0.0149 (12)	0.0323 (17)	−0.0090 (12)
C12	0.095 (2)	0.0263 (10)	0.0517 (14)	−0.0101 (12)	0.0278 (14)	−0.0012 (10)
C13	0.0481 (11)	0.0265 (9)	0.0324 (10)	−0.0038 (8)	0.0058 (8)	−0.0076 (8)
C14	0.0457 (11)	0.0287 (9)	0.0360 (10)	0.0048 (8)	0.0012 (9)	−0.0033 (8)
C15	0.0447 (11)	0.0388 (11)	0.0343 (10)	0.0040 (9)	0.0050 (9)	−0.0032 (9)
C16	0.0482 (12)	0.0375 (11)	0.0326 (10)	−0.0017 (9)	0.0005 (9)	−0.0059 (8)
C17	0.0437 (12)	0.0506 (13)	0.0392 (11)	−0.0035 (10)	−0.0051 (10)	−0.0152 (10)
C18	0.0432 (11)	0.0480 (12)	0.0433 (12)	−0.0074 (10)	0.0047 (10)	−0.0186 (10)
C19	0.0578 (14)	0.0523 (14)	0.0380 (12)	0.0164 (11)	−0.0055 (11)	−0.0021 (10)
C20	0.0627 (16)	0.0663 (17)	0.0345 (12)	0.0000 (13)	0.0008 (11)	−0.0026 (12)
C21	0.0423 (14)	0.141 (3)	0.0571 (18)	−0.0179 (17)	0.0059 (13)	−0.038 (2)
N22	0.0298 (7)	0.0269 (8)	0.0294 (8)	0.0001 (6)	0.0013 (6)	−0.0050 (6)
N23	0.0270 (7)	0.0273 (8)	0.0270 (7)	−0.0006 (6)	−0.0007 (6)	−0.0005 (6)
C24	0.0278 (8)	0.0263 (9)	0.0365 (9)	0.0011 (7)	−0.0045 (8)	−0.0006 (7)
C25	0.0429 (11)	0.0282 (10)	0.0449 (12)	−0.0038 (8)	0.0012 (9)	−0.0072 (8)
C26	0.0416 (10)	0.0299 (10)	0.0391 (11)	0.0007 (8)	0.0008 (9)	−0.0105 (8)
C27	0.0295 (9)	0.0233 (8)	0.0381 (10)	−0.0018 (7)	−0.0029 (8)	0.0027 (7)
C28	0.0313 (9)	0.0281 (9)	0.0431 (10)	−0.0020 (7)	−0.0024 (8)	0.0033 (8)
C29	0.0324 (9)	0.0375 (11)	0.0501 (12)	−0.0019 (8)	0.0033 (9)	0.0066 (9)
C30	0.0424 (11)	0.0378 (11)	0.0453 (12)	−0.0016 (9)	0.0056 (9)	0.0058 (9)
C31	0.0442 (11)	0.0353 (10)	0.0355 (10)	0.0002 (8)	−0.0040 (9)	0.0019 (8)
C32	0.0354 (9)	0.0251 (9)	0.0390 (10)	−0.0003 (7)	−0.0034 (8)	−0.0007 (8)
C33	0.0337 (10)	0.0476 (13)	0.0483 (13)	−0.0045 (9)	−0.0074 (9)	0.0071 (10)
C34	0.0551 (15)	0.0708 (18)	0.0557 (16)	−0.0037 (14)	0.0114 (12)	0.0155 (14)
C35	0.0353 (10)	0.0352 (10)	0.0434 (11)	0.0008 (8)	−0.0068 (9)	−0.0011 (9)
N36	0.0284 (7)	0.0269 (7)	0.0259 (7)	−0.0010 (6)	0.0014 (6)	−0.0007 (6)
C37	0.0299 (9)	0.0258 (9)	0.0285 (9)	−0.0012 (7)	−0.0005 (7)	−0.0034 (7)
C38	0.0370 (10)	0.0368 (10)	0.0264 (9)	−0.0023 (8)	−0.0010 (8)	−0.0002 (7)
C39	0.0421 (11)	0.0421 (11)	0.0295 (9)	−0.0019 (9)	0.0060 (8)	0.0014 (8)
C40	0.0335 (9)	0.0375 (11)	0.0311 (9)	−0.0022 (8)	0.0059 (8)	0.0030 (8)
C41	0.0287 (8)	0.0278 (8)	0.0286 (9)	0.0001 (7)	0.0004 (7)	−0.0022 (7)
N42	0.0302 (8)	0.0332 (8)	0.0234 (7)	−0.0034 (6)	−0.0008 (6)	−0.0009 (6)
N43	0.0284 (7)	0.0308 (8)	0.0255 (8)	−0.0010 (6)	0.0015 (6)	0.0003 (6)
C44	0.0271 (8)	0.0374 (10)	0.0338 (10)	−0.0013 (7)	−0.0010 (7)	0.0024 (8)
C45	0.0290 (9)	0.0586 (14)	0.0365 (11)	−0.0037 (9)	−0.0051 (8)	0.0063 (10)
C46	0.0329 (9)	0.0489 (12)	0.0294 (9)	−0.0055 (8)	−0.0056 (8)	0.0027 (8)
C47	0.0250 (8)	0.0426 (10)	0.0338 (11)	0.0027 (7)	−0.0005 (7)	0.0042 (8)
C48	0.0331 (10)	0.0442 (12)	0.0402 (12)	−0.0001 (8)	0.0047 (9)	0.0058 (9)
C49	0.0394 (12)	0.0526 (14)	0.0415 (13)	0.0050 (9)	0.0076 (9)	0.0114 (10)
C50	0.0336 (10)	0.0638 (15)	0.0319 (11)	0.0069 (9)	0.0034 (8)	0.0032 (10)
C51	0.0325 (9)	0.0509 (12)	0.0380 (11)	0.0055 (9)	−0.0006 (9)	−0.0029 (9)
C52	0.0268 (9)	0.0440 (11)	0.0365 (10)	0.0041 (8)	−0.0006 (8)	0.0033 (8)
C53	0.0643 (14)	0.0455 (12)	0.0554 (14)	−0.0077 (10)	0.0173 (14)	−0.0002 (13)
C54	0.0595 (16)	0.085 (2)	0.0383 (13)	0.0085 (14)	0.0121 (12)	0.0059 (13)
C55	0.0412 (10)	0.0410 (11)	0.0527 (15)	0.0030 (9)	0.0073 (10)	0.0027 (10)
N56	0.0267 (7)	0.0324 (8)	0.0294 (8)	0.0008 (6)	0.0020 (6)	0.0018 (6)
N57	0.0281 (7)	0.0298 (8)	0.0281 (9)	0.0012 (6)	0.0004 (6)	0.0017 (6)
C58	0.0321 (9)	0.0325 (9)	0.0331 (10)	0.0016 (8)	−0.0047 (8)	0.0027 (8)
C59	0.0270 (9)	0.0473 (13)	0.0417 (12)	0.0025 (8)	−0.0017 (8)	0.0053 (9)
C60	0.0278 (9)	0.0417 (11)	0.0405 (11)	0.0003 (8)	0.0028 (9)	0.0037 (9)
C61	0.0283 (9)	0.0421 (11)	0.0331 (10)	0.0002 (8)	−0.0035 (8)	0.0078 (8)
C62	0.0380 (10)	0.0453 (12)	0.0438 (12)	−0.0038 (9)	−0.0105 (9)	0.0127 (9)
C63	0.0418 (12)	0.0587 (15)	0.0547 (14)	−0.0043 (11)	−0.0050 (11)	0.0256 (13)
C64	0.0352 (11)	0.0808 (19)	0.0487 (14)	0.0067 (11)	0.0058 (10)	0.0276 (13)
C65	0.0326 (10)	0.0742 (16)	0.0350 (11)	0.0104 (11)	0.0017 (9)	0.0061 (11)
C66	0.0301 (10)	0.0525 (12)	0.0331 (10)	0.0045 (9)	−0.0047 (8)	0.0056 (9)
C67	0.0810 (19)	0.0390 (13)	0.0499 (14)	−0.0063 (12)	−0.0112 (14)	0.0063 (11)
C68	0.0573 (17)	0.119 (3)	0.071 (2)	0.0193 (19)	0.0248 (16)	0.048 (2)
C69	0.0479 (12)	0.0469 (12)	0.0368 (11)	0.0053 (10)	−0.0082 (10)	−0.0035 (10)
N70	0.0860 (17)	0.0379 (11)	0.0387 (11)	0.0078 (10)	−0.0246 (12)	−0.0001 (8)
O71	0.0796 (13)	0.0426 (9)	0.0351 (8)	−0.0100 (8)	−0.0165 (8)	−0.0031 (7)
O72	0.0990 (19)	0.0764 (16)	0.0753 (16)	0.0301 (14)	−0.0128 (14)	−0.0190 (13)
O73	0.126 (2)	0.0449 (11)	0.0709 (15)	−0.0322 (13)	−0.0262 (14)	0.0072 (10)

Geometric parameters (Å, º)

Co1—N2	2.0199 (17)	C37—N42	1.410 (2)
Co1—N9	2.1177 (15)	C38—C39	1.384 (3)
Co1—N23	2.1320 (17)	C38—H38	0.9500
Co1—N36	2.0206 (16)	C39—C40	1.390 (3)
Co1—N43	2.1279 (16)	C39—H39	0.9500
Co1—N57	2.1538 (16)	C40—C41	1.385 (3)
N2—C7	1.331 (3)	C40—H40	0.9500
N2—C3	1.333 (2)	C41—N56	1.407 (3)
C3—C4	1.386 (3)	N42—C46	1.362 (3)
C3—N8	1.412 (3)	N42—N43	1.377 (2)
C4—C5	1.388 (3)	N43—C44	1.340 (2)
C4—H4	0.9500	C44—C45	1.410 (3)
C5—C6	1.390 (3)	C44—C47	1.496 (3)
C5—H5	0.9500	C45—C46	1.363 (3)
C6—C7	1.380 (3)	C45—H45	0.9500
C6—H6	0.9500	C46—H46	0.9500
C7—N22	1.418 (3)	C47—C48	1.405 (3)
N8—C12	1.355 (3)	C47—C52	1.408 (3)
N8—N9	1.373 (2)	C48—C49	1.400 (4)
N9—C10	1.330 (3)	C48—C53	1.497 (3)
C10—C11	1.408 (3)	C49—C50	1.379 (4)
C10—C13	1.504 (3)	C49—H49	0.9500
C11—C12	1.359 (4)	C50—C51	1.382 (4)
C11—H11	0.9500	C50—C54	1.508 (3)
C12—H12	0.9500	C51—C52	1.401 (3)
C13—C18	1.397 (3)	C51—H51	0.9500
C13—C14	1.405 (3)	C52—C55	1.499 (3)
C14—C15	1.390 (3)	C53—H53A	0.9800
C14—C19	1.499 (3)	C53—H53B	0.9800
C15—C16	1.396 (3)	C53—H53C	0.9800
C15—H15	0.9500	C54—H54A	0.9800
C16—C17	1.375 (3)	C54—H54B	0.9800
C16—C20	1.508 (3)	C54—H54C	0.9800
C17—C18	1.391 (3)	C55—H55A	0.9800
C17—H17	0.9500	C55—H55B	0.9800
C18—C21	1.500 (4)	C55—H55C	0.9800
C19—H19A	0.9800	N56—C60	1.367 (3)
C19—H19B	0.9800	N56—N57	1.370 (2)
C19—H19C	0.9800	N57—C58	1.331 (3)
C20—H20A	0.9800	C58—C59	1.415 (3)
C20—H20B	0.9800	C58—C61	1.496 (3)
C20—H20C	0.9800	C59—C60	1.367 (3)
C21—H21A	0.9800	C59—H59	0.9500
C21—H21B	0.9800	C60—H60	0.9500
C21—H21C	0.9800	C61—C62	1.402 (3)
N22—C26	1.354 (3)	C61—C66	1.404 (3)
N22—N23	1.374 (2)	C62—C63	1.403 (4)
N23—C24	1.337 (2)	C62—C67	1.505 (4)
C24—C25	1.420 (3)	C63—C64	1.377 (4)
C24—C27	1.495 (3)	C63—H63	0.9500
C25—C26	1.358 (3)	C64—C65	1.398 (4)
C25—H25	0.9500	C64—C68	1.506 (4)
C26—H26	0.9500	C65—C66	1.392 (3)
C27—C32	1.410 (3)	C65—H65	0.9500
C27—C28	1.411 (3)	C66—C69	1.503 (3)
C28—C29	1.390 (3)	C67—H67A	0.9800
C28—C33	1.509 (3)	C67—H67B	0.9800
C29—C30	1.383 (3)	C67—H67C	0.9800
C29—H29	0.9500	C68—H68A	0.9800
C30—C31	1.390 (3)	C68—H68B	0.9800
C30—C34	1.505 (4)	C68—H68C	0.9800
C31—C32	1.395 (3)	C69—H69A	0.9800
C31—H31	0.9500	C69—H69B	0.9800
C32—C35	1.499 (3)	C69—H69C	0.9800
C33—H33A	0.9800	N70—O72	1.228 (4)
C33—H33B	0.9800	N70—O73	1.250 (4)
C33—H33C	0.9800	N70—O71	1.262 (3)
C34—H34A	0.9800	N74A—O76A	1.231 (7)
C34—H34B	0.9800	N74A—O77A	1.243 (6)
C34—H34C	0.9800	N74A—O75A	1.265 (7)
C35—H35A	0.9800	N74B—O77B	1.213 (6)
C35—H35B	0.9800	N74B—O75B	1.275 (6)
C35—H35C	0.9800	N74B—O76B	1.299 (6)
N36—C37	1.329 (3)	N74C—O75C	1.243 (9)
N36—C41	1.336 (2)	N74C—O77C	1.271 (8)
C37—C38	1.388 (3)	N74C—O76C	1.281 (9)
N2—Co1—N9	77.41 (7)	H35B—C35—H35C	109.5
N2—Co1—N23	76.99 (6)	C37—N36—C41	120.53 (17)
N2—Co1—N36	179.02 (7)	C37—N36—Co1	119.41 (12)
N2—Co1—N43	102.41 (6)	C41—N36—Co1	120.02 (13)
N2—Co1—N57	103.68 (6)	N36—C37—C38	122.18 (17)
N9—Co1—N23	154.39 (6)	N36—C37—N42	113.38 (17)
N9—Co1—N36	103.52 (7)	C38—C37—N42	124.40 (18)
N9—Co1—N43	92.04 (6)	C39—C38—C37	116.43 (18)
N9—Co1—N57	93.88 (6)	C39—C38—H38	121.8
N23—Co1—N36	102.09 (6)	C37—C38—H38	121.8
N23—Co1—N43	93.63 (6)	C38—C39—C40	122.39 (19)
N23—Co1—N57	91.91 (6)	C38—C39—H39	118.8
N36—Co1—N43	77.27 (6)	C40—C39—H39	118.8
N36—Co1—N57	76.64 (6)	C41—C40—C39	116.33 (18)
N43—Co1—N57	153.91 (6)	C41—C40—H40	121.8
C7—N2—C3	119.77 (17)	C39—C40—H40	121.8
C7—N2—Co1	120.46 (13)	N36—C41—C40	122.10 (18)
C3—N2—Co1	119.75 (13)	N36—C41—N56	112.77 (16)
N2—C3—C4	122.76 (18)	C40—C41—N56	125.12 (17)
N2—C3—N8	112.43 (17)	C46—N42—N43	110.49 (16)
C4—C3—N8	124.79 (18)	C46—N42—C37	130.41 (17)
C3—C4—C5	116.13 (19)	N43—N42—C37	118.18 (15)
C3—C4—H4	121.9	C44—N43—N42	106.01 (15)
C5—C4—H4	121.9	C44—N43—Co1	143.10 (14)
C4—C5—C6	122.10 (19)	N42—N43—Co1	110.88 (11)
C4—C5—H5	118.9	N43—C44—C45	109.65 (18)
C6—C5—H5	118.9	N43—C44—C47	119.82 (17)
C7—C6—C5	116.49 (19)	C45—C44—C47	130.52 (18)
C7—C6—H6	121.8	C46—C45—C44	106.62 (18)
C5—C6—H6	121.8	C46—C45—H45	126.7
N2—C7—C6	122.72 (18)	C44—C45—H45	126.7
N2—C7—N22	112.33 (17)	N42—C46—C45	107.22 (19)
C6—C7—N22	124.94 (18)	N42—C46—H46	126.4
C12—N8—N9	110.87 (18)	C45—C46—H46	126.4
C12—N8—C3	129.39 (19)	C48—C47—C52	120.16 (19)
N9—N8—C3	119.09 (15)	C48—C47—C44	120.42 (19)
C10—N9—N8	106.03 (16)	C52—C47—C44	119.40 (18)
C10—N9—Co1	142.52 (15)	C49—C48—C47	118.3 (2)
N8—N9—Co1	111.15 (12)	C49—C48—C53	119.9 (2)
N9—C10—C11	109.4 (2)	C47—C48—C53	121.8 (2)
N9—C10—C13	120.74 (19)	C50—C49—C48	122.5 (2)
C11—C10—C13	129.7 (2)	C50—C49—H49	118.7
C12—C11—C10	106.9 (2)	C48—C49—H49	118.7
C12—C11—H11	126.5	C49—C50—C51	118.2 (2)
C10—C11—H11	126.5	C49—C50—C54	121.3 (3)
N8—C12—C11	106.8 (2)	C51—C50—C54	120.5 (3)
N8—C12—H12	126.6	C50—C51—C52	122.1 (2)
C11—C12—H12	126.6	C50—C51—H51	118.9
C18—C13—C14	120.0 (2)	C52—C51—H51	118.9
C18—C13—C10	119.5 (2)	C51—C52—C47	118.5 (2)
C14—C13—C10	120.6 (2)	C51—C52—C55	118.8 (2)
C15—C14—C13	118.9 (2)	C47—C52—C55	122.65 (19)
C15—C14—C19	119.3 (2)	C48—C53—H53A	109.5
C13—C14—C19	121.8 (2)	C48—C53—H53B	109.5
C14—C15—C16	121.9 (2)	H53A—C53—H53B	109.5
C14—C15—H15	119.0	C48—C53—H53C	109.5
C16—C15—H15	119.0	H53A—C53—H53C	109.5
C17—C16—C15	117.7 (2)	H53B—C53—H53C	109.5
C17—C16—C20	122.1 (2)	C50—C54—H54A	109.5
C15—C16—C20	120.2 (2)	C50—C54—H54B	109.5
C16—C17—C18	122.6 (2)	H54A—C54—H54B	109.5
C16—C17—H17	118.7	C50—C54—H54C	109.5
C18—C17—H17	118.7	H54A—C54—H54C	109.5
C17—C18—C13	118.9 (2)	H54B—C54—H54C	109.5
C17—C18—C21	119.1 (2)	C52—C55—H55A	109.5
C13—C18—C21	122.0 (2)	C52—C55—H55B	109.5
C14—C19—H19A	109.5	H55A—C55—H55B	109.5
C14—C19—H19B	109.5	C52—C55—H55C	109.5
H19A—C19—H19B	109.5	H55A—C55—H55C	109.5
C14—C19—H19C	109.5	H55B—C55—H55C	109.5
H19A—C19—H19C	109.5	C60—N56—N57	110.45 (16)
H19B—C19—H19C	109.5	C60—N56—C41	130.22 (18)
C16—C20—H20A	109.5	N57—N56—C41	119.01 (15)
C16—C20—H20B	109.5	C58—N57—N56	106.45 (16)
H20A—C20—H20B	109.5	C58—N57—Co1	142.93 (14)
C16—C20—H20C	109.5	N56—N57—Co1	110.44 (11)
H20A—C20—H20C	109.5	N57—C58—C59	109.82 (18)
H20B—C20—H20C	109.5	N57—C58—C61	120.07 (17)
C18—C21—H21A	109.5	C59—C58—C61	130.10 (18)
C18—C21—H21B	109.5	C60—C59—C58	106.22 (19)
H21A—C21—H21B	109.5	C60—C59—H59	126.9
C18—C21—H21C	109.5	C58—C59—H59	126.9
H21A—C21—H21C	109.5	N56—C60—C59	107.05 (19)
H21B—C21—H21C	109.5	N56—C60—H60	126.5
C26—N22—N23	111.18 (17)	C59—C60—H60	126.5
C26—N22—C7	129.54 (17)	C62—C61—C66	120.2 (2)
N23—N22—C7	118.74 (15)	C62—C61—C58	120.1 (2)
C24—N23—N22	106.05 (15)	C66—C61—C58	119.71 (19)
C24—N23—Co1	142.66 (14)	C61—C62—C63	118.7 (2)
N22—N23—Co1	111.25 (11)	C61—C62—C67	122.6 (2)
N23—C24—C25	108.91 (18)	C63—C62—C67	118.7 (2)
N23—C24—C27	122.15 (17)	C64—C63—C62	122.0 (3)
C25—C24—C27	128.77 (18)	C64—C63—H63	119.0
C26—C25—C24	107.00 (19)	C62—C63—H63	119.0
C26—C25—H25	126.5	C63—C64—C65	118.5 (2)
C24—C25—H25	126.5	C63—C64—C68	120.9 (3)
N22—C26—C25	106.85 (19)	C65—C64—C68	120.6 (3)
N22—C26—H26	126.6	C66—C65—C64	121.5 (3)
C25—C26—H26	126.6	C66—C65—H65	119.3
C32—C27—C28	119.12 (19)	C64—C65—H65	119.3
C32—C27—C24	122.45 (16)	C65—C66—C61	119.1 (2)
C28—C27—C24	118.42 (18)	C65—C66—C69	119.3 (2)
C29—C28—C27	119.5 (2)	C61—C66—C69	121.6 (2)
C29—C28—C33	118.12 (18)	C62—C67—H67A	109.5
C27—C28—C33	122.39 (19)	C62—C67—H67B	109.5
C30—C29—C28	122.36 (19)	H67A—C67—H67B	109.5
C30—C29—H29	118.8	C62—C67—H67C	109.5
C28—C29—H29	118.8	H67A—C67—H67C	109.5
C29—C30—C31	117.6 (2)	H67B—C67—H67C	109.5
C29—C30—C34	121.7 (2)	C64—C68—H68A	109.5
C31—C30—C34	120.8 (2)	C64—C68—H68B	109.5
C30—C31—C32	122.5 (2)	H68A—C68—H68B	109.5
C30—C31—H31	118.7	C64—C68—H68C	109.5
C32—C31—H31	118.7	H68A—C68—H68C	109.5
C31—C32—C27	118.89 (18)	H68B—C68—H68C	109.5
C31—C32—C35	117.01 (19)	C66—C69—H69A	109.5
C27—C32—C35	124.10 (19)	C66—C69—H69B	109.5
C28—C33—H33A	109.5	H69A—C69—H69B	109.5
C28—C33—H33B	109.5	C66—C69—H69C	109.5
H33A—C33—H33B	109.5	H69A—C69—H69C	109.5
C28—C33—H33C	109.5	H69B—C69—H69C	109.5
H33A—C33—H33C	109.5	O72—N70—O73	120.4 (3)
H33B—C33—H33C	109.5	O72—N70—O71	120.6 (3)
C30—C34—H34A	109.5	O73—N70—O71	119.0 (3)
C30—C34—H34B	109.5	O76A—N74A—O77A	122.1 (7)
H34A—C34—H34B	109.5	O76A—N74A—O75A	117.5 (5)
C30—C34—H34C	109.5	O77A—N74A—O75A	120.4 (6)
H34A—C34—H34C	109.5	O77B—N74B—O75B	122.2 (5)
H34B—C34—H34C	109.5	O77B—N74B—O76B	124.3 (5)
C32—C35—H35A	109.5	O75B—N74B—O76B	113.4 (6)
C32—C35—H35B	109.5	O75C—N74C—O77C	122.2 (9)
H35A—C35—H35B	109.5	O75C—N74C—O76C	117.7 (9)
C32—C35—H35C	109.5	O77C—N74C—O76C	118.3 (9)
H35A—C35—H35C	109.5