The Co^III-C bond in (1-thia-4,7-diazacyclodecyl-[kappa]³N⁴,N⁷,C¹⁰)(1,4,7-triazacyclononane-[kappa]³N¹,N⁴,N⁷)cobalt(III) dithionate hydrate

In the title compound, [Co(C₆H₁₅N₃)(C₇H₁₅N₂S)]S₂O₆·H₂O, the Co-C bond distance is 1.9930 (13) Å, which is shorter than for related compounds with the linear 1,6-di­amino-3-thia­hexan-4-ide anion in place of the macrocyclic 1-thia-4,7-diazacyclo­decan-8-ide anion. The coordinated carbanion produces an elongation of 0.102 (7) Å of the Co-N bond to the 1,4,7-tri­aza­cyclo­nonane N atom in the trans position. This relatively small trans influence is presumably a result of the tri­amine ligand forming strong bonds to the Co^III atom.

S1. Comment

An unusual route for the preparation of alkylcobalt(III) compounds is the coordination of the carbanion formed by the reversible deprotonation of an S-bonded methylene group in thioethercobalt(III) compounds (Scheme 1). This method has proved feasible in a number of cases where aminoethyl aminopropyl sulfide (aeaps, 3-thiahexane-1,6-diamine) occupies one face of the octahedron in six-coordinate cobalt(III) compounds (Bjerrum et al., 1988; Kofod, Larsen, Larsen et al., 1992; Kofod, Larsen, Petersen & Springborg, 1992; Kofod et al., 1994). The opposite face of the octahedron was blocked by the neutral amine ligands 1,4,7-triazacyclononane (tacn) or 1,1,1-tris(aminomethyl)ethane (tame), or by a second aeaps ligand. Subsequently, the cyclic thioether 1,4-diaza-7-thiacyclodecane (dathicd) was shown to react in a similar manner to aeaps (Song et al., 1996). This route for the formation of alkylcobalt(III) compounds is not restricted to coordination compounds with solely saturated amine ligands, but also applies to Schiff base ligands (Chakraborty et al., 1994). \sch

A small number of X-ray crystal structures of cobalt(III) complexes with the C-bonded form of aeaps, i.e. the 1,6-diamino-3-thiahexan-4-ide anion, C-aeaps, have been reported. The X-ray crystal structures of [Co(tame)(C-aeaps)]S₂O₆ and [Co(tacn)(C-aeaps)](ClO₄)₂ both suffered from severe disorder of the cation (Kofod, Larsen, Larsen et al., 1992; Kofod et al., 1994). In both cases, the disorder was explained by the two chelate rings of C-aeaps being partly interchanged·The X-ray crystal structure of [Co(aeaps)(C-aeaps)]S₂O₆ was performed on a twin crystal containing both enantiomeric forms of the complex cation (Bjerrum et al., 1988). In this paper, we report the crystal structure of [Co(tacn)(C-dathicd)]S₂O₆, (I) (C-dathicd is the 1,4-diaza-7-thiacyclodecan-8-ide anion).

The cyclic thioether dathicd is closely related to the linear thioether aeaps, in that dathicd can be seen as aeaps with the two primary amine groups being linked by a two-carbon chain. This linkage introduces a rigidity to the coordinated ligand, which is not present in the analogous compounds with aeaps. This rigidity may be the reason for the better quality of the single crystals.

The [Co(tacn)(C-dathicd)]²⁺ cation of (I) is shown in Fig. 1. In the crystal of (I), the cation packs with layers of S₂O₆²⁻ anions and H₂O molecules in between. There are hydrogen bonds from all possible donors. Atoms N22, N11 and N13 are hydrogen-bonded to one end of the S₂O₆²⁻ anion, the other end being hydrogen-bonded to atom N21 and to the water molecule, which is in turn hydrogen-bonded to atom N12.

The average Co—N distance of the tacn amine groups cis to the coordinated carbanion (atoms N11 and N12) is 1.977 (7) Å. The Co—N distance for atom N13, which is trans to the alkyl group, is 2.079 (1) Å. Hence, the trans influence induced by the alkyl group is 0.102 (7) Å. This is somewhat shorter than but comparable to the trans influence we observed in [Co(NH₃)₅(CH₃)]²⁺ (0.13 Å; Kofod et al., 1997). The smaller trans influence in (I) may be a result of the tacn ligand forming strong bonds to the Co^III, but it could also reflect a difference between a secondary amine and an ammine ligand. The Co—C bond distance in (I) is slightly longer than in [Co(NH₃)₅(CH₃)]²⁺, by 0.013 (2) Å, and this might also result in a smaller trans influence.

Table 3 compares the metal-ligand bond distances in Co^III compounds with C-aeaps or C-dathicd. Although the quality of some of the structures prevents an accurate comparison, it is evident that the Co—C bond distance in (I) is shorter than in the compounds with C-aeaps. On the other hand, the Co—N distances in the complexes with the C-dathicd ligand are no different from those in the complexes with C-aeaps, which in turn display quite some variation. It can also be seen that the trans influence tends to become larger on going from a secondary to a primary amine.

S2. Experimental

[Co(tacn)(C-dathicd)](ClO₄)₂ was prepared by the addition of aqueous NaOH (Quantity?) to a solution of [Co(tacn)(S-dathicd)]Cl₃·5H₂O In which solvent? (Quantities?), followed by precipitation with sodium perchlorate, as described previously by Song et al. (1996). The sparingly soluble title dithionate salt, (I), was obtained by precipitation of what? with aqueous sodium dithionate. Single crystals of (I) were grown by slow cooling of a saturated solution in warm water.

S3. Refinement

The H atoms appeared clearly in the Δρ map calculated after the U_aniso parameters had been introduced for all non-H atoms. The positions of all H atoms were refined. U_iso(H) was constrained to 1.2U_eq(C) for H atoms on C atoms, and to 1.5U_eq(N, O) for H atoms on N or O atoms. The refined C—H distances are in the range 0.93 (2)–1.00 (2) Å, the N—H distances are in the range 0.83 (2)–0.90 (2) Å and the O—H distances are in the range 0.75 (3)–0.82 (3) Å. The maximum and minimum difference densities were found to be 0.65 and −0.51 e Å⁻³, respectively, both in close vicinity of the Co atom.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: DREADD (Blessing, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976).

Figures

Fig. 1. A view of the cation of (I) including the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

(1-thia-4,7-diazacyclodecyl-κ³N⁴,N⁷,C¹⁰)(1,4,7-triazacyclononane- κ³N¹,N⁴,N⁷)cobalt(III) dithionate hydrate

Crystal data

[Co(C6H15N3)(C7H15N2S)]S2O6·H2O	Z = 2
Mr = 525.54	F(000) = 552
Triclinic, P1	Dx = 1.753 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.837 (2) Å	Cell parameters from 25 reflections
b = 9.135 (2) Å	θ = 15.9–21.4°
c = 15.649 (3) Å	µ = 1.23 mm^−1
α = 89.65 (2)°	T = 122 K
β = 76.04 (2)°	Rod, red
γ = 66.99 (2)°	0.22 × 0.12 × 0.08 mm
V = 995.8 (4) Å^3

Data collection

Enraf-Nonius CAD-4 diffractometer	7372 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 35.0°, θmin = 1.4°
ω/2θ scans	h = −12→12
Absorption correction: integration (Coppens, 1970)	k = −14→14
Tmin = 0.816, Tmax = 0.904	l = 0→25
12912 measured reflections	5 standard reflections every 166.7 min
8747 independent reflections	intensity decay: 3.3%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0286P)^2 + 0.502P] where P = (Fo^2 + 2Fc^2)/3
8747 reflections	(Δ/σ)max = 0.001
358 parameters	Δρmax = 0.66 e Å^−3
0 restraints	Δρmin = −0.51 e Å^−3

Special details

Experimental. (Coppens, 1970)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Co	0.02824 (2)	0.32651 (2)	0.242059 (11)	0.00683 (4)
N12	−0.03313 (16)	0.40556 (13)	0.36726 (7)	0.01056 (18)
H12	−0.014 (3)	0.330 (2)	0.3980 (14)	0.016*
C27	−0.05690 (18)	0.14963 (15)	0.27342 (8)	0.0097 (2)
H27	−0.128 (3)	0.176 (2)	0.3322 (13)	0.012*
N22	0.10587 (15)	0.25574 (13)	0.11274 (7)	0.00914 (17)
H22	0.131 (3)	0.333 (2)	0.0872 (13)	0.014*
N11	−0.23341 (16)	0.48668 (13)	0.24658 (8)	0.01131 (19)
H11	−0.285 (3)	0.454 (2)	0.2094 (14)	0.017*
N13	0.10608 (17)	0.51874 (14)	0.21715 (8)	0.01139 (19)
H13	0.214 (3)	0.497 (2)	0.1830 (14)	0.017*
S1	−0.22609 (5)	0.13561 (4)	0.21806 (2)	0.01297 (6)
C12	−0.2403 (2)	0.51656 (17)	0.40187 (9)	0.0144 (2)
H12A	−0.253 (3)	0.628 (2)	0.4065 (13)	0.017*
H12B	−0.291 (3)	0.486 (2)	0.4579 (14)	0.017*
C15	0.0967 (2)	0.48531 (16)	0.37506 (9)	0.0138 (2)
H15A	0.226 (3)	0.400 (2)	0.3698 (13)	0.017*
H15B	0.053 (3)	0.548 (2)	0.4295 (14)	0.017*
C22	0.29566 (18)	0.11724 (16)	0.08842 (9)	0.0114 (2)
H22A	0.365 (3)	0.117 (2)	0.0270 (13)	0.014*
H22B	0.279 (3)	0.019 (2)	0.0911 (13)	0.014*
C25	−0.03107 (19)	0.23164 (16)	0.06829 (8)	0.0109 (2)
H25A	0.033 (3)	0.202 (2)	0.0060 (13)	0.013*
H25B	−0.130 (3)	0.325 (2)	0.0739 (13)	0.013*
C11	−0.35324 (19)	0.50114 (17)	0.33893 (9)	0.0143 (2)
H11A	−0.382 (3)	0.409 (3)	0.3425 (13)	0.017*
H11B	−0.475 (3)	0.596 (2)	0.3482 (14)	0.017*
C13	−0.2346 (2)	0.64606 (16)	0.22203 (10)	0.0141 (2)
H13A	−0.281 (3)	0.717 (2)	0.2744 (14)	0.017*
H13B	−0.322 (3)	0.693 (2)	0.1857 (14)	0.017*
C14	−0.0350 (2)	0.62874 (16)	0.17261 (9)	0.0143 (2)
H14A	−0.030 (3)	0.735 (2)	0.1693 (14)	0.017*
H14B	−0.005 (3)	0.586 (2)	0.1124 (14)	0.017*
N21	0.28881 (16)	0.17096 (13)	0.24274 (8)	0.01060 (18)
H21	0.347 (3)	0.206 (2)	0.2716 (13)	0.016*
C26	−0.0939 (2)	0.10036 (17)	0.10315 (9)	0.0127 (2)
H26A	0.013 (3)	−0.001 (2)	0.0909 (13)	0.015*
H26B	−0.183 (3)	0.093 (2)	0.0717 (13)	0.015*
C23	0.2751 (2)	0.03044 (16)	0.28864 (9)	0.0135 (2)
H23A	0.245 (3)	0.062 (2)	0.3518 (13)	0.016*
H23B	0.397 (3)	−0.056 (2)	0.2719 (13)	0.016*
C24	0.1188 (2)	−0.00767 (16)	0.26608 (9)	0.0128 (2)
H24A	0.163 (3)	−0.068 (2)	0.2062 (14)	0.015*
H24B	0.085 (3)	−0.078 (2)	0.3100 (13)	0.015*
C21	0.41027 (18)	0.13130 (16)	0.14993 (9)	0.0121 (2)
H21A	0.450 (3)	0.215 (2)	0.1351 (13)	0.015*
H21B	0.526 (3)	0.030 (2)	0.1431 (13)	0.015*
C16	0.1001 (2)	0.59590 (16)	0.30222 (10)	0.0139 (2)
H16A	−0.011 (3)	0.692 (2)	0.3164 (13)	0.017*
H16B	0.216 (3)	0.620 (2)	0.2932 (13)	0.017*
S2	−0.41901 (5)	0.06142 (4)	0.46381 (2)	0.01131 (6)
S3	0.50546 (5)	0.58303 (4)	0.04624 (2)	0.01084 (6)
O1	−0.24469 (15)	−0.06625 (13)	0.41176 (7)	0.01699 (19)
O2	−0.38524 (16)	0.14718 (13)	0.53215 (8)	0.0181 (2)
O3	−0.53934 (16)	0.16539 (13)	0.41216 (7)	0.0182 (2)
O4	0.69292 (15)	0.58814 (13)	0.01147 (7)	0.01649 (19)
O5	0.49037 (15)	0.50972 (13)	0.12947 (7)	0.01533 (19)
O6	0.34434 (17)	0.73161 (13)	0.04632 (8)	0.0201 (2)
O7	0.04974 (18)	−0.19943 (15)	0.49732 (8)	0.0202 (2)
H7A	0.130 (4)	−0.173 (3)	0.4856 (16)	0.030*
H7B	−0.034 (4)	−0.143 (3)	0.4745 (16)	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.00656 (7)	0.00609 (7)	0.00751 (7)	−0.00213 (5)	−0.00192 (5)	0.00005 (5)
N12	0.0117 (5)	0.0094 (4)	0.0106 (4)	−0.0040 (4)	−0.0033 (4)	0.0001 (3)
C27	0.0113 (5)	0.0097 (5)	0.0096 (5)	−0.0057 (4)	−0.0030 (4)	0.0008 (4)
N22	0.0085 (4)	0.0083 (4)	0.0098 (4)	−0.0029 (3)	−0.0015 (3)	0.0005 (3)
N11	0.0096 (4)	0.0107 (5)	0.0123 (5)	−0.0021 (4)	−0.0037 (4)	−0.0008 (4)
N13	0.0118 (5)	0.0101 (4)	0.0118 (5)	−0.0047 (4)	−0.0016 (4)	0.0003 (4)
S1	0.01221 (13)	0.01796 (15)	0.01152 (13)	−0.00915 (12)	−0.00271 (11)	0.00018 (11)
C12	0.0124 (5)	0.0153 (6)	0.0118 (5)	−0.0030 (5)	−0.0007 (4)	−0.0022 (4)
C15	0.0167 (6)	0.0118 (5)	0.0152 (6)	−0.0065 (5)	−0.0071 (5)	−0.0005 (4)
C22	0.0087 (5)	0.0099 (5)	0.0126 (5)	−0.0016 (4)	−0.0009 (4)	−0.0018 (4)
C25	0.0124 (5)	0.0110 (5)	0.0090 (5)	−0.0038 (4)	−0.0037 (4)	0.0009 (4)
C11	0.0100 (5)	0.0159 (6)	0.0134 (5)	−0.0028 (4)	−0.0007 (4)	−0.0023 (4)
C13	0.0143 (6)	0.0098 (5)	0.0158 (6)	−0.0012 (4)	−0.0061 (5)	0.0011 (4)
C14	0.0180 (6)	0.0096 (5)	0.0142 (6)	−0.0044 (5)	−0.0044 (5)	0.0034 (4)
N21	0.0098 (4)	0.0102 (4)	0.0121 (5)	−0.0036 (4)	−0.0040 (4)	0.0006 (4)
C26	0.0127 (5)	0.0159 (6)	0.0110 (5)	−0.0071 (5)	−0.0033 (4)	−0.0010 (4)
C23	0.0139 (6)	0.0109 (5)	0.0160 (6)	−0.0034 (4)	−0.0067 (5)	0.0042 (4)
C24	0.0159 (6)	0.0098 (5)	0.0135 (5)	−0.0057 (4)	−0.0045 (4)	0.0023 (4)
C21	0.0077 (5)	0.0117 (5)	0.0155 (6)	−0.0030 (4)	−0.0016 (4)	−0.0008 (4)
C16	0.0160 (6)	0.0106 (5)	0.0169 (6)	−0.0069 (5)	−0.0046 (5)	−0.0013 (4)
S2	0.00917 (12)	0.01120 (13)	0.01260 (13)	−0.00366 (10)	−0.00184 (10)	0.00178 (10)
S3	0.01060 (13)	0.01036 (13)	0.01167 (13)	−0.00382 (10)	−0.00374 (10)	0.00152 (10)
O1	0.0120 (4)	0.0174 (5)	0.0164 (5)	−0.0033 (4)	0.0012 (4)	−0.0003 (4)
O2	0.0175 (5)	0.0191 (5)	0.0203 (5)	−0.0098 (4)	−0.0052 (4)	−0.0017 (4)
O3	0.0173 (5)	0.0180 (5)	0.0193 (5)	−0.0056 (4)	−0.0074 (4)	0.0083 (4)
O4	0.0157 (5)	0.0199 (5)	0.0179 (5)	−0.0115 (4)	−0.0042 (4)	0.0051 (4)
O5	0.0150 (4)	0.0220 (5)	0.0111 (4)	−0.0091 (4)	−0.0044 (3)	0.0041 (4)
O6	0.0202 (5)	0.0110 (4)	0.0252 (5)	0.0005 (4)	−0.0105 (4)	−0.0016 (4)
O7	0.0220 (5)	0.0228 (5)	0.0239 (6)	−0.0141 (5)	−0.0119 (5)	0.0109 (4)

Geometric parameters (Å, º)

Co—N12	1.9705 (12)	C25—H25B	0.89 (2)
Co—N21	1.9827 (13)	C11—H11A	0.95 (2)
Co—N11	1.9840 (13)	C11—H11B	0.98 (2)
Co—C27	1.9930 (13)	C13—C14	1.514 (2)
Co—N22	1.9995 (12)	C13—H13A	0.95 (2)
Co—N13	2.0790 (12)	C13—H13B	0.96 (2)
N12—C15	1.4907 (18)	C14—H14A	0.98 (2)
N12—C12	1.5009 (19)	C14—H14B	0.96 (2)
N12—H12	0.83 (2)	N21—C21	1.4889 (18)
C27—C24	1.5338 (19)	N21—C23	1.4950 (18)
C27—S1	1.7926 (13)	N21—H21	0.85 (2)
C27—H27	0.930 (19)	C26—H26A	0.96 (2)
N22—C22	1.4898 (17)	C26—H26B	0.97 (2)
N22—C25	1.4936 (17)	C23—C24	1.513 (2)
N22—H22	0.87 (2)	C23—H23A	0.98 (2)
N11—C11	1.4962 (19)	C23—H23B	0.95 (2)
N11—C13	1.5006 (18)	C24—H24A	1.00 (2)
N11—H11	0.90 (2)	C24—H24B	1.00 (2)
N13—C14	1.4875 (18)	C21—H21A	0.94 (2)
N13—C16	1.4922 (18)	C21—H21B	0.99 (2)
N13—H13	0.83 (2)	C16—H16A	0.94 (2)
S1—C26	1.8050 (15)	C16—H16B	0.99 (2)
C12—C11	1.514 (2)	S2—O3	1.4501 (12)
C12—H12A	0.98 (2)	S2—O1	1.4557 (12)
C12—H12B	0.96 (2)	S2—O2	1.4615 (12)
C15—C16	1.521 (2)	S2—S2^i	2.1349 (8)
C15—H15A	0.99 (2)	S3—O6	1.4477 (12)
C15—H15B	0.94 (2)	S3—O4	1.4575 (12)
C22—C21	1.5029 (19)	S3—O5	1.4614 (11)
C22—H22A	0.99 (2)	S3—S3^ii	2.1427 (8)
C22—H22B	0.95 (2)	O7—H7A	0.75 (3)
C25—C26	1.5172 (19)	O7—H7B	0.82 (3)
C25—H25A	0.97 (2)
N12—Co—N21	92.89 (5)	H25A—C25—H25B	108.1 (17)
N12—Co—N11	84.60 (5)	N11—C11—C12	107.79 (11)
N21—Co—N11	177.43 (5)	N11—C11—H11A	105.4 (12)
N12—Co—C27	92.31 (5)	C12—C11—H11A	115.2 (13)
N21—Co—C27	86.30 (5)	N11—C11—H11B	109.7 (12)
N11—Co—C27	94.32 (5)	C12—C11—H11B	110.6 (12)
N12—Co—N22	175.10 (5)	H11A—C11—H11B	107.9 (17)
N21—Co—N22	85.55 (5)	N11—C13—C14	110.44 (11)
N11—Co—N22	96.91 (5)	N11—C13—H13A	108.6 (12)
C27—Co—N22	92.22 (5)	C14—C13—H13A	111.0 (12)
N12—Co—N13	84.31 (5)	N11—C13—H13B	110.7 (12)
N21—Co—N13	95.26 (5)	C14—C13—H13B	109.3 (12)
N11—Co—N13	83.98 (5)	H13A—C13—H13B	106.7 (17)
C27—Co—N13	176.34 (5)	N13—C14—C13	108.83 (11)
N22—Co—N13	91.20 (5)	N13—C14—H14A	112.9 (12)
C15—N12—C12	111.45 (11)	C13—C14—H14A	109.7 (12)
C15—N12—Co	107.88 (9)	N13—C14—H14B	109.2 (12)
C12—N12—Co	112.03 (9)	C13—C14—H14B	110.6 (12)
C15—N12—H12	109.1 (14)	H14A—C14—H14B	105.6 (17)
C12—N12—H12	106.6 (14)	C21—N21—C23	114.71 (11)
Co—N12—H12	109.7 (14)	C21—N21—Co	108.26 (8)
C24—C27—S1	113.80 (9)	C23—N21—Co	109.59 (8)
C24—C27—Co	109.69 (9)	C21—N21—H21	105.7 (14)
S1—C27—Co	115.32 (7)	C23—N21—H21	104.1 (14)
C24—C27—H27	109.0 (12)	Co—N21—H21	114.5 (14)
S1—C27—H27	102.8 (12)	C25—C26—S1	115.22 (10)
Co—C27—H27	105.5 (12)	C25—C26—H26A	110.6 (12)
C22—N22—C25	110.95 (10)	S1—C26—H26A	111.4 (12)
C22—N22—Co	110.67 (8)	C25—C26—H26B	108.4 (12)
C25—N22—Co	121.12 (8)	S1—C26—H26B	104.1 (12)
C22—N22—H22	103.1 (13)	H26A—C26—H26B	106.5 (17)
C25—N22—H22	104.7 (13)	N21—C23—C24	109.44 (11)
Co—N22—H22	104.3 (13)	N21—C23—H23A	105.9 (12)
C11—N11—C13	110.68 (11)	C24—C23—H23A	111.6 (12)
C11—N11—Co	106.85 (9)	N21—C23—H23B	108.4 (12)
C13—N11—Co	112.44 (9)	C24—C23—H23B	113.0 (12)
C11—N11—H11	108.4 (13)	H23A—C23—H23B	108.3 (17)
C13—N11—H11	107.5 (13)	C23—C24—C27	108.20 (11)
Co—N11—H11	110.9 (13)	C23—C24—H24A	111.9 (12)
C14—N13—C16	112.04 (11)	C27—C24—H24A	112.0 (12)
C14—N13—Co	105.64 (8)	C23—C24—H24B	108.1 (12)
C16—N13—Co	109.57 (8)	C27—C24—H24B	109.4 (12)
C14—N13—H13	106.5 (14)	H24A—C24—H24B	107.2 (16)
C16—N13—H13	107.9 (14)	N21—C21—C22	110.02 (11)
Co—N13—H13	115.3 (14)	N21—C21—H21A	107.9 (12)
C27—S1—C26	102.53 (6)	C22—C21—H21A	109.3 (12)
N12—C12—C11	109.61 (11)	N21—C21—H21B	111.7 (11)
N12—C12—H12A	110.1 (12)	C22—C21—H21B	109.4 (12)
C11—C12—H12A	108.5 (12)	H21A—C21—H21B	108.4 (16)
N12—C12—H12B	108.8 (12)	N13—C16—C15	110.45 (11)
C11—C12—H12B	107.7 (12)	N13—C16—H16A	107.4 (12)
H12A—C12—H12B	112.1 (17)	C15—C16—H16A	110.8 (12)
N12—C15—C16	109.32 (11)	N13—C16—H16B	108.4 (12)
N12—C15—H15A	107.2 (12)	C15—C16—H16B	109.9 (12)
C16—C15—H15A	111.4 (12)	H16A—C16—H16B	109.8 (17)
N12—C15—H15B	111.4 (13)	O3—S2—O1	114.65 (7)
C16—C15—H15B	107.4 (12)	O3—S2—O2	113.73 (7)
H15A—C15—H15B	110.1 (17)	O1—S2—O2	113.16 (7)
N22—C22—C21	108.03 (11)	O3—S2—S2^i	105.74 (5)
N22—C22—H22A	110.7 (11)	O1—S2—S2^i	103.93 (5)
C21—C22—H22A	109.3 (11)	O2—S2—S2^i	104.21 (5)
N22—C22—H22B	110.3 (12)	O6—S3—O4	114.48 (7)
C21—C22—H22B	112.2 (12)	O6—S3—O5	114.46 (7)
H22A—C22—H22B	106.3 (16)	O4—S3—O5	112.66 (7)
N22—C25—C26	113.50 (11)	O6—S3—S3^ii	105.34 (6)
N22—C25—H25A	107.8 (12)	O4—S3—S3^ii	104.44 (6)
C26—C25—H25A	107.8 (12)	O5—S3—S3^ii	104.01 (5)
N22—C25—H25B	107.7 (13)	H7A—O7—H7B	107 (2)
C26—C25—H25B	111.7 (13)
N21—Co—N12—C15	65.43 (9)	C24—C27—S1—C26	−66.83 (11)
N11—Co—N12—C15	−114.03 (9)	Co—C27—S1—C26	61.21 (8)
C27—Co—N12—C15	151.84 (9)	C15—N12—C12—C11	136.14 (12)
N13—Co—N12—C15	−29.57 (9)	Co—N12—C12—C11	15.15 (14)
N21—Co—N12—C12	−171.54 (9)	C12—N12—C15—C16	−76.86 (14)
N11—Co—N12—C12	9.00 (9)	Co—N12—C15—C16	46.53 (12)
C27—Co—N12—C12	−85.13 (10)	C25—N22—C22—C21	−167.53 (10)
N13—Co—N12—C12	93.46 (9)	Co—N22—C22—C21	−30.15 (12)
N12—Co—C27—C24	−101.74 (9)	C22—N22—C25—C26	69.26 (14)
N21—Co—C27—C24	−9.00 (9)	Co—N22—C25—C26	−63.00 (13)
N11—Co—C27—C24	173.50 (9)	C13—N11—C11—C12	−75.95 (14)
N22—Co—C27—C24	76.39 (9)	Co—N11—C11—C12	46.77 (12)
N12—Co—C27—S1	128.20 (7)	N12—C12—C11—N11	−40.30 (15)
N21—Co—C27—S1	−139.05 (8)	C11—N11—C13—C14	137.76 (12)
N11—Co—C27—S1	43.45 (8)	Co—N11—C13—C14	18.35 (13)
N22—Co—C27—S1	−53.66 (7)	C16—N13—C14—C13	−73.97 (14)
N21—Co—N22—C22	7.19 (8)	Co—N13—C14—C13	45.29 (12)
N11—Co—N22—C22	−173.55 (8)	N11—C13—C14—N13	−42.70 (15)
C27—Co—N22—C22	−78.92 (9)	N12—Co—N21—C21	−157.70 (8)
N13—Co—N22—C22	102.37 (9)	C27—Co—N21—C21	110.17 (9)
N21—Co—N22—C25	139.57 (10)	N22—Co—N21—C21	17.65 (8)
N11—Co—N22—C25	−41.17 (10)	N13—Co—N21—C21	−73.15 (9)
C27—Co—N22—C25	53.46 (10)	N12—Co—N21—C23	76.52 (9)
N13—Co—N22—C25	−125.25 (10)	C27—Co—N21—C23	−15.62 (9)
N12—Co—N11—C11	−31.12 (9)	N22—Co—N21—C23	−108.13 (9)
C27—Co—N11—C11	60.80 (9)	N13—Co—N21—C23	161.07 (9)
N22—Co—N11—C11	153.56 (9)	N22—C25—C26—S1	63.18 (13)
N13—Co—N11—C11	−115.95 (9)	C27—S1—C26—C25	−60.98 (11)
N12—Co—N11—C13	90.49 (9)	C21—N21—C23—C24	−84.58 (14)
C27—Co—N11—C13	−177.59 (9)	Co—N21—C23—C24	37.42 (13)
N22—Co—N11—C13	−84.82 (9)	N21—C23—C24—C27	−44.79 (14)
N13—Co—N11—C13	5.66 (9)	S1—C27—C24—C23	162.25 (9)
N12—Co—N13—C14	−113.51 (9)	Co—C27—C24—C23	31.38 (13)
N21—Co—N13—C14	154.10 (9)	C23—N21—C21—C22	83.28 (13)
N11—Co—N13—C14	−28.36 (9)	Co—N21—C21—C22	−39.44 (12)
N22—Co—N13—C14	68.46 (9)	N22—C22—C21—N21	45.70 (14)
N12—Co—N13—C16	7.36 (9)	C14—N13—C16—C15	133.23 (12)
N21—Co—N13—C16	−85.02 (9)	Co—N13—C16—C15	16.32 (13)
N11—Co—N13—C16	92.51 (9)	N12—C15—C16—N13	−41.00 (15)
N22—Co—N13—C16	−170.67 (9)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N12—H12···O7^iii	0.83 (2)	2.05 (2)	2.8396 (18)	160 (2)
N22—H22···O4^ii	0.87 (2)	2.13 (2)	2.9230 (16)	150.4 (18)
N11—H11···O5^iv	0.90 (2)	2.30 (2)	3.1052 (17)	150.0 (17)
N13—H13···O5	0.83 (2)	2.17 (2)	2.9620 (18)	157.8 (19)
N21—H21···O3^v	0.85 (2)	2.54 (2)	3.2424 (17)	140.4 (17)
O7—H7A···O2^iii	0.75 (3)	2.05 (3)	2.7835 (18)	166 (3)
O7—H7B···O1	0.82 (3)	2.01 (3)	2.8059 (18)	163 (2)

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