Tris(2-sulfido­pyridine N-oxide-κ²O,S)cobalt(III)

The title compound, [tri(2-sulfido­pyridine N-oxide-O,S)cobalt(III)], [Co(C₅H₄NSO)₃], was synthesized and its structure characterized by X-ray crystallographic techniques. Three mpo⁻ (Hmpo = 2-mercapto­pyridine-N-oxide) ligands chelate the Co atom, forming a distorted octahedral O₃S₃ coordin­ation environment around Co. The asymmetric unit contains two mol­ecules of Co(C₅H₄NOS)₃.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.040
• wR factor = 0.059
• Data-to-parameter ratio = 13.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSTM_02  Alert C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
          Tmin and Tmax reported:      0.800     0.990
          Tmin and Tmax expected:      0.622     0.873
          RR =      1.135
          Please check that your absorption correction is appropriate.

General Notes



FORMU_01  There is a discrepancy between the atom counts in the
          _chemical_formula_sum and _chemical_formula_moiety. This is
          usually due to the moiety formula being in the wrong format.
          Atom count from _chemical_formula_sum:   C15 H12 Co1 N3 O3 S3
          Atom count from _chemical_formula_moiety:

ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      0.882
          Tmax scaled      0.873 Tmin scaled      0.706


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

Metal thiolate complexes are important analogues of metal enzymes and are known as biological electron-transfer mediators (Dance, 1986). We are interested in investigating cobalt complexes with thiolate because of the multifunctional nature of thiolates and their intriguing structure variations, and the electron-transfer properties of cobalt complexes (Kang et al., 1996; Chen et al., 1998). The single-crystal structures of numerous cobalt complexes with Hmpo (Hmpo= 2-mercaptopyridine-N-oxide) have been reported (Hu et al., 1991; Kang et al., 1993; Xu et al., 1995), but the title compound is reported first.

The title compound contains a distorted octahedral Co(III) ion which is chelated by three bidentate mpo⁻¹ ligands through their S and O atoms. Its structure is similar to those reported earlier (Hu et al., 1991; Xu et al., 1995). The average Co—S and Co—O bond distances and the average O—Co—S bite angle (2.199 and 1.947 Å, and 87.85°, respectively) agree well with those of Co(mpo)₃·CH₃CN (2.194 and 1.933 Å, and 88.00°, respectively; Hu et al., 1991).

The X-ray structure shows that the asymmetric unit contains two molecules of Co(mpo)₃. Between the two molecules, there is a π–π stack of pyridines; the distance between the centres of the pyridines is 3.577 Å. The three dimensional arrangement of molecules within the crystal lattice is determined by the interactions between the stacks.

S2. Experimental

To a methanol solution (20 ml) containing CoCl₂(PPh₃)₂ (0.654 g, 1 mmol) was added Nampo (0.447 g, 3 mmol), with stirring, at room temperature. The resulting dark solution, after stirring for 2 h, was reduced to dry in vacuo and then extracted with 20 ml CH₂Cl₂. The resulting solution evaporated at room temperature to give black crystalline blocks of the title compound in 5% yield. Analysis calculated for C₁₅H₁₂N₃CoO₃S₃: C, 41.19; H, 2.77; N, 9.61; S, 21.99%. Found: C, 41.45; H, 2.92; N, 9.40; S, 22.42%.

Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A View of the two independent molecules of the title compound showing 50% probability displacement ellipsoids. H atoms are omitted for clarity.

'tri(2-sulfidopyridine N-oxide-O,S)-Cobalt(III)'

Crystal data

[Co(C5H4NSO)3]	F(000) = 1776
Mr = 437.39	Dx = 1.656 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.480 (2) Å	Cell parameters from 28 reflections
b = 26.303 (5) Å	θ = 2.7–13.7°
c = 14.437 (4) Å	µ = 1.36 mm^−1
β = 102.90 (2)°	T = 296 K
V = 3509.0 (14) Å^3	Block, black
Z = 8	0.50 × 0.30 × 0.10 mm

Data collection

Siemens P4 diffractometer	3363 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.028
Graphite monochromator	θmax = 25.0°, θmin = 1.6°
ω scans	h = 0→11
Absorption correction: empirical (using intensity measurements) (North et al., 1968)	k = −1→31
Tmin = 0.800, Tmax = 0.990	l = −17→16
7223 measured reflections	3 standard reflections every 97 reflections
6188 independent reflections	intensity decay: 1.9%

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.059	H-atom parameters constrained
S = 0.80	w = 1/[σ^2(Fo^2) + (0.013P)^2] where P = (Fo^2 + 2Fc^2)/3
6188 reflections	(Δ/σ)max = 0.001
451 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

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

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
Co1	0.61927 (6)	0.564809 (19)	0.79993 (4)	0.03953 (16)
Co2	0.17803 (6)	0.686194 (19)	0.30228 (4)	0.03941 (16)
S1	0.51683 (13)	0.63919 (4)	0.80197 (8)	0.0489 (3)
S2	0.65118 (13)	0.58108 (4)	0.65687 (8)	0.0525 (3)
S3	0.83205 (14)	0.59760 (4)	0.86475 (9)	0.0598 (4)
S4	0.29945 (12)	0.69721 (4)	0.44990 (8)	0.0467 (3)
S5	0.03926 (13)	0.75289 (4)	0.30874 (8)	0.0522 (3)
S6	0.33873 (13)	0.73256 (4)	0.25227 (8)	0.0524 (3)
O1	0.5683 (3)	0.54966 (9)	0.91996 (18)	0.0505 (8)
O2	0.4399 (3)	0.53026 (9)	0.74094 (18)	0.0444 (7)
O3	0.7134 (3)	0.49881 (9)	0.80694 (18)	0.0469 (8)
O4	0.0517 (3)	0.63989 (9)	0.35079 (19)	0.0458 (7)
O5	0.0620 (3)	0.67315 (10)	0.17621 (19)	0.0524 (8)
O6	0.2924 (3)	0.62727 (9)	0.28373 (18)	0.0412 (7)
N1	0.4825 (4)	0.58464 (12)	0.9493 (2)	0.0393 (9)
N2	0.3985 (4)	0.53605 (11)	0.6449 (2)	0.0392 (9)
N3	0.8594 (4)	0.49929 (12)	0.8327 (2)	0.0419 (9)
N4	0.0702 (4)	0.63969 (12)	0.4466 (3)	0.0412 (9)
N5	−0.0391 (4)	0.70853 (13)	0.1403 (2)	0.0464 (10)
N6	0.4290 (4)	0.63745 (12)	0.2754 (2)	0.0356 (8)
C1	0.4517 (4)	0.62886 (14)	0.9019 (3)	0.0376 (11)
C2	0.3663 (5)	0.66376 (15)	0.9374 (3)	0.0514 (13)
H2	0.3458	0.6951	0.9075	0.062*
C3	0.3119 (5)	0.65282 (17)	1.0154 (3)	0.0575 (13)
H3	0.2545	0.6762	1.0382	0.069*
C4	0.3441 (5)	0.60654 (16)	1.0594 (3)	0.0510 (12)
H4	0.3068	0.5983	1.1118	0.061*
C5	0.4301 (4)	0.57268 (15)	1.0266 (3)	0.0455 (12)
H5	0.4528	0.5416	1.0570	0.055*
C6	0.4866 (4)	0.55914 (14)	0.5956 (3)	0.0387 (10)
C7	0.4363 (5)	0.56309 (15)	0.4976 (3)	0.0535 (12)
H7	0.4929	0.5799	0.4623	0.064*
C8	0.3076 (6)	0.54334 (16)	0.4521 (3)	0.0625 (15)
H8	0.2773	0.5455	0.3863	0.075*
C9	0.2223 (5)	0.51986 (16)	0.5054 (4)	0.0586 (14)
H9	0.1336	0.5060	0.4755	0.070*
C10	0.2674 (5)	0.51697 (14)	0.6013 (3)	0.0489 (12)
H10	0.2085	0.5019	0.6371	0.059*
C11	0.9300 (5)	0.54321 (16)	0.8629 (3)	0.0502 (12)
C12	1.0788 (5)	0.54025 (18)	0.8902 (4)	0.0882 (19)
H12	1.1307	0.5697	0.9105	0.106*
C13	1.1534 (5)	0.4957 (2)	0.8887 (4)	0.110 (2)
H13	1.2536	0.4946	0.9087	0.133*
C14	1.0751 (5)	0.45235 (18)	0.8564 (3)	0.0755 (16)
H14	1.1225	0.4215	0.8546	0.091*
C15	0.9296 (5)	0.45485 (15)	0.8278 (3)	0.0514 (12)
H15	0.8773	0.4259	0.8045	0.062*
C16	0.1851 (4)	0.66352 (14)	0.5025 (3)	0.0417 (11)
C17	0.2021 (5)	0.65905 (15)	0.6007 (3)	0.0554 (13)
H17	0.2810	0.6743	0.6410	0.067*
C18	0.1041 (6)	0.63246 (18)	0.6386 (4)	0.0704 (16)
H18	0.1172	0.6290	0.7041	0.085*
C19	−0.0151 (6)	0.61070 (18)	0.5778 (4)	0.0669 (15)
H19	−0.0843	0.5935	0.6024	0.080*
C20	−0.0299 (5)	0.61462 (15)	0.4834 (4)	0.0561 (13)
H20	−0.1096	0.6000	0.4428	0.067*
C21	−0.0633 (4)	0.74820 (15)	0.1949 (3)	0.0480 (12)
C22	−0.1735 (5)	0.78210 (17)	0.1537 (4)	0.0610 (14)
H22	−0.1931	0.8099	0.1885	0.073*
C23	−0.2524 (6)	0.7749 (2)	0.0636 (4)	0.0842 (18)
H23	−0.3266	0.7974	0.0381	0.101*
C24	−0.2229 (6)	0.7345 (2)	0.0097 (4)	0.0880 (19)
H24	−0.2753	0.7296	−0.0522	0.106*
C25	−0.1151 (5)	0.70201 (19)	0.0499 (3)	0.0689 (15)
H25	−0.0931	0.6748	0.0146	0.083*
C26	0.4673 (5)	0.68623 (15)	0.2609 (3)	0.0446 (11)
C27	0.6092 (5)	0.69368 (18)	0.2527 (3)	0.0687 (15)
H27	0.6409	0.7265	0.2444	0.082*
C28	0.7033 (5)	0.6538 (2)	0.2567 (3)	0.0735 (16)
H28	0.7981	0.6596	0.2517	0.088*
C29	0.6570 (5)	0.60502 (18)	0.2680 (3)	0.0606 (14)
H29	0.7196	0.5776	0.2698	0.073*
C30	0.5177 (4)	0.59740 (15)	0.2766 (3)	0.0429 (11)
H30	0.4844	0.5646	0.2832	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0435 (4)	0.0329 (3)	0.0436 (4)	0.0036 (3)	0.0126 (3)	−0.0019 (3)
Co2	0.0417 (4)	0.0310 (3)	0.0462 (4)	−0.0019 (3)	0.0113 (3)	−0.0050 (3)
S1	0.0656 (9)	0.0371 (6)	0.0477 (7)	0.0141 (6)	0.0202 (7)	0.0093 (6)
S2	0.0554 (8)	0.0549 (7)	0.0537 (8)	−0.0140 (7)	0.0263 (7)	−0.0084 (6)
S3	0.0598 (9)	0.0368 (6)	0.0761 (9)	−0.0002 (6)	0.0009 (7)	−0.0159 (6)
S4	0.0465 (8)	0.0414 (6)	0.0510 (7)	−0.0127 (6)	0.0083 (6)	−0.0042 (6)
S5	0.0566 (8)	0.0415 (7)	0.0586 (8)	0.0086 (6)	0.0128 (7)	−0.0080 (6)
S6	0.0636 (9)	0.0305 (6)	0.0690 (9)	−0.0027 (6)	0.0274 (7)	0.0031 (6)
O1	0.074 (2)	0.0358 (16)	0.0464 (18)	0.0248 (16)	0.0231 (17)	0.0098 (14)
O2	0.045 (2)	0.0467 (17)	0.0412 (18)	−0.0008 (14)	0.0087 (15)	0.0073 (14)
O3	0.0276 (18)	0.0367 (16)	0.074 (2)	−0.0015 (14)	0.0062 (16)	−0.0100 (15)
O4	0.0409 (19)	0.0463 (17)	0.0489 (19)	−0.0094 (15)	0.0075 (16)	−0.0041 (15)
O5	0.058 (2)	0.0418 (17)	0.053 (2)	0.0110 (16)	0.0048 (17)	−0.0069 (15)
O6	0.0363 (18)	0.0318 (15)	0.0593 (19)	−0.0082 (14)	0.0188 (15)	−0.0055 (14)
N1	0.049 (2)	0.036 (2)	0.032 (2)	0.0049 (18)	0.0081 (18)	0.0004 (17)
N2	0.041 (2)	0.0284 (19)	0.050 (2)	0.0033 (17)	0.014 (2)	0.0013 (18)
N3	0.036 (2)	0.039 (2)	0.049 (2)	−0.0012 (19)	0.0058 (19)	−0.0091 (18)
N4	0.036 (2)	0.040 (2)	0.052 (2)	0.0017 (18)	0.019 (2)	−0.0005 (19)
N5	0.048 (3)	0.047 (2)	0.043 (3)	0.000 (2)	0.008 (2)	0.006 (2)
N6	0.033 (2)	0.037 (2)	0.037 (2)	−0.0040 (18)	0.0063 (17)	0.0008 (17)
C1	0.045 (3)	0.030 (2)	0.036 (3)	0.004 (2)	0.004 (2)	0.001 (2)
C2	0.063 (3)	0.033 (2)	0.058 (3)	0.013 (2)	0.016 (3)	0.001 (2)
C3	0.066 (4)	0.059 (3)	0.053 (3)	0.011 (3)	0.024 (3)	−0.010 (3)
C4	0.058 (3)	0.063 (3)	0.034 (3)	−0.008 (3)	0.016 (2)	−0.008 (2)
C5	0.055 (3)	0.051 (3)	0.028 (2)	−0.001 (2)	0.003 (2)	0.003 (2)
C6	0.046 (3)	0.031 (2)	0.043 (3)	0.005 (2)	0.017 (2)	−0.001 (2)
C7	0.063 (4)	0.050 (3)	0.049 (3)	0.001 (3)	0.017 (3)	0.006 (3)
C8	0.090 (5)	0.049 (3)	0.046 (3)	0.013 (3)	0.010 (3)	0.002 (3)
C9	0.052 (3)	0.048 (3)	0.065 (4)	0.002 (3)	−0.009 (3)	−0.008 (3)
C10	0.038 (3)	0.037 (3)	0.069 (4)	−0.006 (2)	0.006 (3)	0.009 (2)
C11	0.040 (3)	0.047 (3)	0.056 (3)	−0.003 (2)	−0.007 (2)	−0.010 (2)
C12	0.047 (4)	0.053 (3)	0.142 (5)	−0.001 (3)	−0.026 (4)	−0.029 (3)
C13	0.036 (4)	0.079 (4)	0.193 (7)	0.002 (3)	−0.024 (4)	−0.040 (5)
C14	0.044 (3)	0.060 (3)	0.117 (5)	0.015 (3)	0.006 (3)	−0.022 (3)
C15	0.044 (3)	0.033 (3)	0.080 (4)	0.000 (2)	0.021 (3)	−0.012 (2)
C16	0.040 (3)	0.033 (2)	0.053 (3)	0.001 (2)	0.013 (2)	−0.008 (2)
C17	0.072 (4)	0.042 (3)	0.051 (3)	0.006 (3)	0.011 (3)	−0.005 (2)
C18	0.095 (5)	0.066 (4)	0.059 (4)	0.011 (3)	0.035 (4)	−0.001 (3)
C19	0.065 (4)	0.067 (4)	0.084 (4)	0.004 (3)	0.049 (4)	0.010 (3)
C20	0.040 (3)	0.052 (3)	0.082 (4)	−0.001 (2)	0.028 (3)	0.005 (3)
C21	0.040 (3)	0.037 (2)	0.069 (3)	−0.001 (2)	0.016 (3)	0.009 (3)
C22	0.046 (3)	0.048 (3)	0.089 (4)	−0.002 (3)	0.017 (3)	0.007 (3)
C23	0.069 (4)	0.073 (4)	0.100 (5)	0.006 (3)	−0.004 (4)	0.024 (4)
C24	0.091 (5)	0.098 (5)	0.057 (4)	−0.002 (4)	−0.021 (3)	0.011 (4)
C25	0.074 (4)	0.084 (4)	0.042 (3)	−0.009 (3)	−0.001 (3)	−0.007 (3)
C26	0.048 (3)	0.040 (3)	0.048 (3)	−0.011 (2)	0.014 (2)	0.002 (2)
C27	0.052 (4)	0.062 (3)	0.096 (4)	−0.012 (3)	0.025 (3)	0.017 (3)
C28	0.041 (3)	0.089 (4)	0.096 (4)	0.002 (3)	0.025 (3)	0.024 (4)
C29	0.037 (3)	0.064 (3)	0.080 (4)	0.011 (3)	0.011 (3)	0.019 (3)
C30	0.044 (3)	0.041 (3)	0.043 (3)	0.007 (2)	0.007 (2)	0.006 (2)

Geometric parameters (Å, º)

Co1—O1	1.941 (3)	C4—H4	0.9300
Co1—O3	1.944 (3)	C5—H5	0.9300
Co1—O2	1.948 (3)	C6—C7	1.392 (5)
Co1—S1	2.1873 (12)	C7—C8	1.354 (5)
Co1—S2	2.1953 (13)	C7—H7	0.9300
Co1—S3	2.2013 (14)	C8—C9	1.381 (6)
Co2—O5	1.936 (3)	C8—H8	0.9300
Co2—O6	1.944 (2)	C9—C10	1.356 (5)
Co2—O4	1.945 (3)	C9—H9	0.9300
Co2—S6	2.1956 (13)	C10—H10	0.9300
Co2—S4	2.2036 (13)	C11—C12	1.379 (6)
Co2—S5	2.2073 (12)	C12—C13	1.372 (6)
S1—C1	1.713 (4)	C12—H12	0.9300
S2—C6	1.713 (4)	C13—C14	1.383 (6)
S3—C11	1.709 (4)	C13—H13	0.9300
S4—C16	1.704 (4)	C14—C15	1.350 (5)
S5—C21	1.717 (4)	C14—H14	0.9300
S6—C26	1.709 (4)	C15—H15	0.9300
O1—N1	1.357 (3)	C16—C17	1.397 (5)
O2—N2	1.363 (4)	C17—C18	1.370 (6)
O3—N3	1.350 (4)	C17—H17	0.9300
O4—N4	1.355 (4)	C18—C19	1.390 (6)
O5—N5	1.353 (4)	C18—H18	0.9300
O6—N6	1.353 (3)	C19—C20	1.343 (5)
N1—C1	1.348 (4)	C19—H19	0.9300
N1—C5	1.355 (4)	C20—H20	0.9300
N2—C6	1.356 (4)	C21—C22	1.401 (5)
N2—C10	1.358 (5)	C22—C23	1.360 (6)
N3—C15	1.355 (4)	C22—H22	0.9300
N3—C11	1.358 (4)	C23—C24	1.384 (6)
N4—C16	1.355 (5)	C23—H23	0.9300
N4—C20	1.358 (5)	C24—C25	1.359 (6)
N5—C25	1.354 (5)	C24—H24	0.9300
N5—C21	1.357 (5)	C25—H25	0.9300
N6—C30	1.346 (4)	C26—C27	1.390 (5)
N6—C26	1.363 (4)	C27—C28	1.370 (6)
C1—C2	1.395 (5)	C27—H27	0.9300
C2—C3	1.369 (5)	C28—C29	1.378 (5)
C2—H2	0.9300	C28—H28	0.9300
C3—C4	1.375 (5)	C29—C30	1.369 (5)
C3—H3	0.9300	C29—H29	0.9300
C4—C5	1.362 (5)	C30—H30	0.9300
O1—Co1—O3	88.46 (11)	N2—C6—C7	117.1 (4)
O1—Co1—O2	85.85 (12)	N2—C6—S2	118.5 (3)
O3—Co1—O2	87.24 (11)	C7—C6—S2	124.5 (4)
O1—Co1—S1	88.38 (8)	C8—C7—C6	122.2 (4)
O3—Co1—S1	176.34 (9)	C8—C7—H7	118.9
O2—Co1—S1	94.38 (9)	C6—C7—H7	118.9
O1—Co1—S2	173.62 (10)	C7—C8—C9	118.5 (5)
O3—Co1—S2	93.73 (9)	C7—C8—H8	120.7
O2—Co1—S2	88.27 (8)	C9—C8—H8	120.7
S1—Co1—S2	89.60 (5)	C10—C9—C8	120.2 (5)
O1—Co1—S3	95.05 (9)	C10—C9—H9	119.9
O3—Co1—S3	87.78 (8)	C8—C9—H9	119.9
O2—Co1—S3	174.92 (9)	C9—C10—N2	120.0 (4)
S1—Co1—S3	90.65 (5)	C9—C10—H10	120.0
S2—Co1—S3	91.03 (5)	N2—C10—H10	120.0
O5—Co2—O6	86.94 (11)	N3—C11—C12	116.3 (4)
O5—Co2—O4	87.78 (12)	N3—C11—S3	119.1 (3)
O6—Co2—O4	87.58 (11)	C12—C11—S3	124.6 (4)
O5—Co2—S6	94.57 (9)	C13—C12—C11	122.8 (5)
O6—Co2—S6	87.03 (8)	C13—C12—H12	118.6
O4—Co2—S6	174.00 (9)	C11—C12—H12	118.6
O5—Co2—S4	175.76 (9)	C12—C13—C14	118.0 (5)
O6—Co2—S4	92.92 (8)	C12—C13—H13	121.0
O4—Co2—S4	87.98 (9)	C14—C13—H13	121.0
S6—Co2—S4	89.66 (5)	C15—C14—C13	119.9 (5)
O5—Co2—S5	87.80 (9)	C15—C14—H14	120.1
O6—Co2—S5	174.58 (9)	C13—C14—H14	120.1
O4—Co2—S5	93.54 (9)	C14—C15—N3	120.4 (4)
S6—Co2—S5	92.08 (5)	C14—C15—H15	119.8
S4—Co2—S5	92.42 (5)	N3—C15—H15	119.8
C1—S1—Co1	96.56 (13)	N4—C16—C17	117.4 (4)
C6—S2—Co1	96.86 (15)	N4—C16—S4	118.8 (3)
C11—S3—Co1	96.60 (15)	C17—C16—S4	123.7 (4)
C16—S4—Co2	96.63 (16)	C18—C17—C16	120.9 (5)
C21—S5—Co2	96.77 (16)	C18—C17—H17	119.5
C26—S6—Co2	96.67 (14)	C16—C17—H17	119.5
N1—O1—Co1	115.2 (2)	C17—C18—C19	119.1 (5)
N2—O2—Co1	114.7 (2)	C17—C18—H18	120.5
N3—O3—Co1	115.9 (2)	C19—C18—H18	120.5
N4—O4—Co2	114.8 (2)	C20—C19—C18	119.7 (5)
N5—O5—Co2	116.3 (2)	C20—C19—H19	120.2
N6—O6—Co2	115.4 (2)	C18—C19—H19	120.2
C1—N1—C5	122.7 (4)	C19—C20—N4	120.7 (5)
C1—N1—O1	120.2 (3)	C19—C20—H20	119.6
C5—N1—O1	117.1 (3)	N4—C20—H20	119.6
C6—N2—C10	122.0 (4)	N5—C21—C22	116.8 (4)
C6—N2—O2	120.9 (3)	N5—C21—S5	118.5 (3)
C10—N2—O2	117.1 (4)	C22—C21—S5	124.7 (4)
O3—N3—C15	117.6 (3)	C23—C22—C21	121.1 (5)
O3—N3—C11	119.9 (3)	C23—C22—H22	119.5
C15—N3—C11	122.5 (4)	C21—C22—H22	119.5
O4—N4—C16	120.7 (3)	C22—C23—C24	120.5 (5)
O4—N4—C20	117.3 (4)	C22—C23—H23	119.8
C16—N4—C20	122.1 (4)	C24—C23—H23	119.8
O5—N5—C25	117.5 (4)	C25—C24—C23	118.1 (5)
O5—N5—C21	120.3 (4)	C25—C24—H24	121.0
C25—N5—C21	122.3 (4)	C23—C24—H24	121.0
C30—N6—O6	116.9 (3)	N5—C25—C24	121.3 (5)
C30—N6—C26	123.5 (4)	N5—C25—H25	119.3
O6—N6—C26	119.6 (3)	C24—C25—H25	119.3
N1—C1—C2	117.3 (4)	N6—C26—C27	116.3 (4)
N1—C1—S1	119.1 (3)	N6—C26—S6	118.2 (3)
C2—C1—S1	123.6 (3)	C27—C26—S6	125.6 (4)
C3—C2—C1	121.3 (4)	C28—C27—C26	121.5 (5)
C3—C2—H2	119.4	C28—C27—H27	119.3
C1—C2—H2	119.4	C26—C27—H27	119.3
C2—C3—C4	118.7 (4)	C27—C28—C29	119.8 (5)
C2—C3—H3	120.6	C27—C28—H28	120.1
C4—C3—H3	120.6	C29—C28—H28	120.1
C5—C4—C3	120.5 (4)	C30—C29—C28	119.1 (4)
C5—C4—H4	119.8	C30—C29—H29	120.4
C3—C4—H4	119.8	C28—C29—H29	120.4
N1—C5—C4	119.5 (4)	N6—C30—C29	119.8 (4)
N1—C5—H5	120.3	N6—C30—H30	120.1
C4—C5—H5	120.3	C29—C30—H30	120.1
O1—Co1—S1—C1	−4.89 (16)	C1—N1—C5—C4	−0.8 (6)
O2—Co1—S1—C1	80.83 (16)	O1—N1—C5—C4	179.6 (3)
S2—Co1—S1—C1	169.06 (14)	C3—C4—C5—N1	−0.9 (6)
S3—Co1—S1—C1	−99.92 (14)	C10—N2—C6—C7	0.7 (5)
O3—Co1—S2—C6	94.22 (15)	O2—N2—C6—C7	179.5 (3)
O2—Co1—S2—C6	7.09 (15)	C10—N2—C6—S2	−179.0 (3)
S1—Co1—S2—C6	−87.30 (13)	O2—N2—C6—S2	−0.2 (5)
S3—Co1—S2—C6	−177.94 (13)	Co1—S2—C6—N2	−5.7 (3)
O1—Co1—S3—C11	94.44 (17)	Co1—S2—C6—C7	174.6 (3)
O3—Co1—S3—C11	6.18 (18)	N2—C6—C7—C8	−2.3 (6)
S1—Co1—S3—C11	−177.13 (16)	S2—C6—C7—C8	177.4 (3)
S2—Co1—S3—C11	−87.51 (16)	C6—C7—C8—C9	1.9 (7)
O6—Co2—S4—C16	−94.09 (15)	C7—C8—C9—C10	0.2 (7)
O4—Co2—S4—C16	−6.62 (15)	C8—C9—C10—N2	−1.7 (6)
S6—Co2—S4—C16	178.90 (14)	C6—N2—C10—C9	1.3 (6)
S5—Co2—S4—C16	86.83 (14)	O2—N2—C10—C9	−177.6 (3)
O5—Co2—S5—C21	−4.09 (16)	O3—N3—C11—C12	178.4 (4)
O4—Co2—S5—C21	−91.72 (16)	C15—N3—C11—C12	−1.0 (7)
S6—Co2—S5—C21	90.41 (14)	O3—N3—C11—S3	−1.7 (5)
S4—Co2—S5—C21	−179.85 (14)	C15—N3—C11—S3	178.9 (3)
O5—Co2—S6—C26	−100.42 (16)	Co1—S3—C11—N3	−4.3 (4)
O6—Co2—S6—C26	−13.73 (16)	Co1—S3—C11—C12	175.7 (4)
S4—Co2—S6—C26	79.21 (14)	N3—C11—C12—C13	−0.8 (9)
S5—Co2—S6—C26	171.62 (14)	S3—C11—C12—C13	179.2 (5)
O3—Co1—O1—N1	−174.7 (2)	C11—C12—C13—C14	1.3 (10)
O2—Co1—O1—N1	−87.3 (2)	C12—C13—C14—C15	0.0 (9)
S1—Co1—O1—N1	7.2 (2)	C13—C14—C15—N3	−1.8 (8)
S3—Co1—O1—N1	97.7 (2)	O3—N3—C15—C14	−177.1 (4)
O1—Co1—O2—N2	168.8 (2)	C11—N3—C15—C14	2.4 (7)
O3—Co1—O2—N2	−102.6 (2)	O4—N4—C16—C17	−176.1 (3)
S1—Co1—O2—N2	80.7 (2)	C20—N4—C16—C17	3.5 (6)
S2—Co1—O2—N2	−8.7 (2)	O4—N4—C16—S4	4.2 (5)
O1—Co1—O3—N3	−103.6 (2)	C20—N4—C16—S4	−176.2 (3)
O2—Co1—O3—N3	170.5 (2)	Co2—S4—C16—N4	3.4 (3)
S2—Co1—O3—N3	82.4 (2)	Co2—S4—C16—C17	−176.3 (3)
S3—Co1—O3—N3	−8.5 (2)	N4—C16—C17—C18	−1.4 (6)
O5—Co2—O4—N4	−169.8 (2)	S4—C16—C17—C18	178.3 (3)
O6—Co2—O4—N4	103.1 (2)	C16—C17—C18—C19	−1.4 (7)
S4—Co2—O4—N4	10.1 (2)	C17—C18—C19—C20	2.2 (7)
S5—Co2—O4—N4	−82.2 (2)	C18—C19—C20—N4	−0.1 (7)
O6—Co2—O5—N5	−173.0 (3)	O4—N4—C20—C19	176.8 (4)
S6—Co2—O5—N5	−86.2 (2)	C16—N4—C20—C19	−2.8 (6)
S5—Co2—O5—N5	5.7 (2)	O5—N5—C21—C22	−177.6 (3)
O5—Co2—O6—N6	111.3 (2)	C25—N5—C21—C22	1.1 (6)
O4—Co2—O6—N6	−160.8 (2)	O5—N5—C21—S5	1.3 (5)
S6—Co2—O6—N6	16.6 (2)	C25—N5—C21—S5	180.0 (3)
S4—Co2—O6—N6	−72.9 (2)	Co2—S5—C21—N5	2.7 (3)
Co1—O1—N1—C1	−7.3 (4)	Co2—S5—C21—C22	−178.5 (3)
Co1—O1—N1—C5	172.3 (3)	N5—C21—C22—C23	0.5 (7)
Co1—O2—N2—C6	7.4 (4)	S5—C21—C22—C23	−178.3 (4)
Co1—O2—N2—C10	−173.8 (2)	C21—C22—C23—C24	−1.5 (8)
Co1—O3—N3—C15	−172.5 (3)	C22—C23—C24—C25	1.0 (9)
Co1—O3—N3—C11	8.0 (4)	O5—N5—C25—C24	177.1 (4)
Co2—O4—N4—C16	−10.8 (4)	C21—N5—C25—C24	−1.7 (7)
Co2—O4—N4—C20	169.5 (3)	C23—C24—C25—N5	0.6 (8)
Co2—O5—N5—C25	175.7 (3)	C30—N6—C26—C27	−3.9 (6)
Co2—O5—N5—C21	−5.5 (4)	O6—N6—C26—C27	−179.8 (3)
Co2—O6—N6—C30	170.5 (3)	C30—N6—C26—S6	175.1 (3)
Co2—O6—N6—C26	−13.3 (4)	O6—N6—C26—S6	−0.8 (5)
C5—N1—C1—C2	2.3 (6)	Co2—S6—C26—N6	11.7 (3)
O1—N1—C1—C2	−178.2 (3)	Co2—S6—C26—C27	−169.4 (4)
C5—N1—C1—S1	−177.2 (3)	N6—C26—C27—C28	1.6 (7)
O1—N1—C1—S1	2.4 (5)	S6—C26—C27—C28	−177.2 (4)
Co1—S1—C1—N1	2.9 (3)	C26—C27—C28—C29	0.7 (8)
Co1—S1—C1—C2	−176.5 (3)	C27—C28—C29—C30	−1.0 (8)
N1—C1—C2—C3	−2.1 (6)	O6—N6—C30—C29	179.7 (3)
S1—C1—C2—C3	177.3 (3)	C26—N6—C30—C29	3.7 (6)
C1—C2—C3—C4	0.5 (7)	C28—C29—C30—N6	−1.1 (7)
C2—C3—C4—C5	1.0 (7)