A new polymorph of fac-tris(4,6-di­methyl­pyrimidine-2-thiol­ato-κ²N,S)­cobalt(III) monohydrate

A new polymorph of the title compound, [Co(C₆H₇N₂S)₃]·H₂O, was obtained by slow evaporation of the compound from tetra­hydro­furan. The structure is almost exactly the same as that of the first polymorph [Seth (1994). Acta Cryst. C50, 1196–1199]. The packing arrangement and position of the water mol­ecule differ in the two forms.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.011 Å
• R factor = 0.061
• wR factor = 0.139
• Data-to-parameter ratio = 19.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



RINTA_01  Alert C The value of Rint is greater than 0.10
          Rint given   0.103

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           28.08
         From the CIF: _reflns_number_total               5124
         Count of symmetry unique reflns         2844
         Completeness (_total/calc)            180.17%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      2280
         Fraction of Friedel pairs measured     0.802
         Are heavy atom types Z>Si present          yes
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

As part of our systematic work on the coordination mode of the potential ambidentate ligand 4,6-dimethylpirimidine-2(1H)-thione (4,6-Me₂pymSH) (Lang et al., 2002; Fernandes et al., 2002; Oliveira et al., 2002), we studied the reaction of the ligand with the cobalt(II) acetate tetrahydrate. Aerial oxidization with slow evaporation of tetrahydrofuran produced the crystals of the blue Co^III title compound, (I), in the acentric orthorhombic space group Pca2₁ (Fig. 1). The selected crystal showed only the Δ optical isomer with no racemic twinning. Seth (1994) reported the first polymorph of the title compound in the acentric monoclinic space group P2₁; racemic twinning was not reported.

The Co(4,6-Me₂pymS)₃ molecule of (I) shows almost the same strongly distorted fac-octahedral geometry, due to the small bite angle of the three bidentate 4,6-Me₂pymS ligands, as that reported in the earlier polymorph. The planes formed by each of the three ligands are mutually perpendicular, with angles of 85.82 (12), 87.35 (12) and 86.19 (13)° between them. The Co atom is situated 0.1322 Å from the point defined by the intersection of the three planes. The bond distances and angles within the ligands are close to those reported for similar compounds.

The difference between the two polymorphs lies in the packing and the position of the water solvate molecule. The packing diagram of the title compound is shown in Fig. 2. In the unit cell of the first polymorph, the water molecule forms a hydrogen bond to only one imidizolium N atom with a O···N distance of 2.969 (7) Å. In the new polymorph, the water molecule bridges between two neighbouring Co(4,6-Me₂pymS)₃ molecules, forming hydrogen bonding to two different N atoms, as shown in Table 4. Comparing the volume of the asymmetric units, the first polymorph occupies a slightly larger volume, 572.6 (1) Å⁻³, than the new polymorph, 564.8 (1) Å⁻³, implying a greater packing efficiency in the latter.

S2. Experimental

The compound 4,6-dimethylpirimidine-2(1H)-thione (4,6-Me₂pymSH) was prepared according to a literature method (Nigam et al., 1983). The title complex was synthesized by the following procedure: 0.42 g (3 mmol) of 4,6-Me₂pymSH was dissolved in 20 ml of thf (freshly distilled) in a Schlenk tube kept under N₂ atmosphere. To this solution, 0.25 g (1 mmol) of the [Co(O₂CCH₃)₂]·4H₂O dissolved in 10 ml of THF was added over 10 min, and the mixture was stirred for about 2 h. Slow evaporation of the solvent in air led to the appearance of a blue microcrystalline solid. Yield: ~96% (0.45 g). Elemental analysis: calculated for C₁₈H₂₃CoN₆S₃: C 43.71, H 4.68, N 16.99%; found: C 43.69, H 4.64, N 17.1%. FAB MS: m/z 476.0 (14%, M), m/z 337.0 (32%,{Co[4,6-Me₂pymS]₂}), m/z 198.0 (15%,{Co[4,6-Me₂pymS]}).

S3. Refinement

The intensities of the measured reflections were, in general, weak leading to a slightly high value of R_int. The H atoms of the methyl groups were refined as riding atoms with ideal tetrahedral geometry [d(C—H) = 0.96 Å] allowed to rotate to fit the electron density; the isotropic displacement parameters were fixed to be 50% larger than those of the atoms to which the H atoms were bonded. The aromatic H atoms were constrained to ideal trigonal planar geometry [d(C—H) = 0.93 Å]; their isotropic displacement parameters were set to be 20% larger than the those of the atoms to which the h ATOMS were bonded. H atoms were located in A difference Fourier map and refined freely with isotropic displacement parameters 50% larger than that of the parent O atom. A total of 2326 Friedel pairs were measured.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. View of molecule with atomic labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing diagram of the title compound.

fac-tris(4,6-dimethylpyrimidine-2-thiolato-N,S)cobalt(III) monohydrate

Crystal data

[Co(C6H7N2S)3]·H2O	F(000) = 1024
Mr = 494.56	Dx = 1.454 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 3091 reflections
a = 16.969 (2) Å	θ = 5.5–54.7°
b = 8.0436 (11) Å	µ = 1.06 mm^−1
c = 16.552 (2) Å	T = 293 K
V = 2259.2 (5) Å^3	Block, blue
Z = 4	0.19 × 0.17 × 0.17 mm

Data collection

Bruker SMART area-detector diffractometer	2380 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.103
ϕ and ω scans	θmax = 28.1°, θmin = 2.4°
Absorption correction: multi-scan (DENZO-SMN, Otwinowski & Minor, 1997)	h = −22→22
Tmin = 0.824, Tmax = 0.841	k = −10→5
12629 measured reflections	l = −21→21
5124 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.061	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.139	w = 1/[σ^2(Fo^2) + (0.0482P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.85	(Δ/σ)max = 0.001
5124 reflections	Δρmax = 0.76 e Å^−3
269 parameters	Δρmin = −0.33 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (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	0.53579 (5)	0.53650 (11)	0.01650 (5)	0.0410 (3)
S1	0.63209 (13)	0.4715 (3)	−0.07154 (12)	0.0565 (6)
C11	0.6524 (4)	0.3403 (9)	0.0069 (5)	0.0422 (18)
N12	0.6033 (3)	0.3685 (7)	0.0686 (3)	0.0379 (14)
C13	0.6098 (4)	0.2789 (9)	0.1352 (4)	0.0397 (18)
C131	0.5523 (5)	0.3071 (9)	0.2026 (4)	0.059 (2)
H13A	0.4996	0.2978	0.1821	0.088*
H13B	0.5601	0.4161	0.2247	0.088*
H13C	0.5605	0.2253	0.2440	0.088*
C14	0.6696 (4)	0.1607 (9)	0.1408 (5)	0.048 (2)
H14	0.6761	0.0983	0.1876	0.058*
C15	0.7186 (4)	0.1381 (9)	0.0756 (5)	0.053 (2)
C151	0.7819 (5)	0.0085 (9)	0.0770 (5)	0.071 (2)
H15A	0.8314	0.0584	0.0631	0.106*
H15B	0.7695	−0.0772	0.0387	0.106*
H15C	0.7853	−0.0388	0.1302	0.106*
N16	0.7110 (3)	0.2289 (8)	0.0068 (4)	0.0508 (16)
S2	0.60312 (12)	0.7456 (3)	0.07469 (12)	0.0508 (5)
C21	0.5206 (4)	0.7431 (9)	0.1355 (4)	0.0417 (18)
N22	0.4711 (4)	0.6204 (7)	0.1075 (3)	0.0379 (15)
C23	0.4030 (5)	0.6024 (9)	0.1453 (5)	0.047 (2)
C231	0.3464 (5)	0.4733 (10)	0.1127 (5)	0.065 (2)
H23A	0.3723	0.3673	0.1104	0.098*
H23B	0.3296	0.5049	0.0595	0.098*
H23C	0.3013	0.4658	0.1476	0.098*
C24	0.3829 (5)	0.7049 (10)	0.2081 (5)	0.054 (2)
H24	0.3344	0.6945	0.2339	0.064*
C25	0.4375 (6)	0.8259 (10)	0.2321 (4)	0.055 (2)
C251	0.4176 (6)	0.9406 (11)	0.2992 (4)	0.070 (3)
H25A	0.3894	1.0346	0.2783	0.104*
H25B	0.4652	0.9780	0.3248	0.104*
H25C	0.3855	0.8836	0.3380	0.104*
N26	0.5049 (4)	0.8462 (8)	0.1947 (4)	0.0483 (17)
S3	0.46723 (15)	0.6945 (2)	−0.07179 (13)	0.0582 (6)
C31	0.4263 (5)	0.5012 (9)	−0.0891 (5)	0.048 (2)
N32	0.4607 (4)	0.3891 (7)	−0.0399 (3)	0.0426 (15)
C33	0.4395 (5)	0.2275 (9)	−0.0462 (4)	0.0432 (19)
C331	0.4786 (4)	0.1058 (8)	0.0058 (5)	0.052 (2)
H33A	0.4706	0.1354	0.0614	0.078*
H33B	0.5340	0.1045	−0.0058	0.078*
H33C	0.4568	−0.0025	−0.0040	0.078*
C34	0.3826 (5)	0.1887 (10)	−0.1014 (4)	0.049 (2)
H34	0.3671	0.0785	−0.1072	0.059*
C35	0.3477 (5)	0.3089 (11)	−0.1490 (5)	0.053 (2)
C351	0.2844 (5)	0.2726 (11)	−0.2079 (5)	0.077 (3)
H35A	0.2947	0.3313	−0.2573	0.115*
H35B	0.2347	0.3077	−0.1862	0.115*
H35C	0.2829	0.1553	−0.2184	0.115*
N36	0.3698 (4)	0.4699 (9)	−0.1418 (4)	0.0512 (17)
O1	0.2188 (3)	0.8035 (7)	0.3419 (3)	0.0757 (18)
H1A	0.2407	0.8092	0.3967	0.113*
H1B	0.2009	0.7349	0.3205	0.113*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0494 (6)	0.0323 (5)	0.0413 (5)	−0.0056 (5)	0.0001 (6)	0.0000 (6)
S1	0.0701 (15)	0.0526 (13)	0.0468 (11)	−0.0030 (12)	0.0136 (11)	0.0044 (13)
C11	0.037 (4)	0.045 (4)	0.045 (5)	−0.007 (4)	0.014 (4)	−0.007 (4)
N12	0.043 (4)	0.037 (3)	0.034 (3)	−0.001 (3)	−0.003 (3)	−0.002 (3)
C13	0.043 (4)	0.040 (5)	0.036 (4)	−0.011 (4)	−0.010 (4)	−0.002 (4)
C131	0.089 (7)	0.048 (5)	0.039 (4)	−0.006 (5)	−0.007 (5)	0.005 (4)
C14	0.049 (5)	0.044 (5)	0.052 (5)	0.009 (4)	−0.008 (4)	0.000 (4)
C15	0.047 (5)	0.046 (5)	0.066 (5)	0.003 (4)	−0.006 (5)	−0.017 (5)
C151	0.051 (5)	0.068 (6)	0.093 (6)	0.009 (4)	−0.002 (5)	−0.005 (6)
N16	0.046 (4)	0.047 (4)	0.060 (5)	−0.003 (3)	0.012 (4)	−0.006 (4)
S2	0.0527 (13)	0.0428 (11)	0.0569 (12)	−0.0115 (10)	0.0027 (11)	−0.0063 (10)
C21	0.051 (5)	0.031 (4)	0.043 (4)	0.006 (4)	−0.006 (4)	0.005 (3)
N22	0.037 (4)	0.034 (4)	0.043 (3)	−0.005 (3)	−0.003 (3)	0.003 (3)
C23	0.048 (5)	0.033 (5)	0.060 (5)	−0.004 (4)	−0.007 (5)	0.013 (4)
C231	0.052 (5)	0.050 (5)	0.094 (6)	−0.021 (5)	0.022 (5)	−0.011 (5)
C24	0.053 (5)	0.055 (6)	0.053 (5)	0.007 (5)	0.012 (4)	−0.007 (4)
C25	0.085 (7)	0.037 (5)	0.043 (5)	0.010 (5)	−0.012 (5)	−0.006 (4)
C251	0.081 (7)	0.068 (6)	0.060 (6)	0.009 (6)	−0.005 (5)	−0.013 (5)
N26	0.057 (4)	0.040 (4)	0.048 (4)	−0.002 (3)	0.013 (4)	−0.002 (3)
S3	0.0856 (17)	0.0330 (12)	0.0560 (12)	−0.0059 (12)	−0.0200 (14)	0.0052 (11)
C31	0.067 (6)	0.036 (5)	0.040 (4)	0.003 (4)	0.008 (4)	−0.005 (4)
N32	0.062 (4)	0.035 (3)	0.030 (3)	−0.002 (3)	−0.009 (3)	0.000 (3)
C33	0.056 (5)	0.032 (5)	0.042 (4)	0.004 (4)	0.008 (4)	−0.004 (4)
C331	0.065 (5)	0.029 (4)	0.061 (5)	−0.006 (4)	−0.002 (5)	0.000 (4)
C34	0.066 (6)	0.046 (5)	0.035 (4)	−0.013 (4)	−0.003 (4)	−0.011 (4)
C35	0.055 (6)	0.059 (6)	0.044 (5)	−0.014 (5)	−0.011 (4)	−0.005 (5)
C351	0.070 (6)	0.089 (7)	0.072 (6)	−0.002 (6)	−0.021 (5)	−0.017 (5)
N36	0.055 (4)	0.052 (5)	0.047 (4)	0.002 (4)	−0.011 (3)	−0.001 (4)
O1	0.076 (4)	0.085 (4)	0.066 (4)	−0.007 (3)	−0.017 (3)	0.008 (3)

Geometric parameters (Å, º)

Co1—N12	1.970 (6)	C231—H23A	0.9600
Co1—N32	1.975 (6)	C231—H23B	0.9600
Co1—N22	1.982 (6)	C231—H23C	0.9600
Co1—S2	2.250 (2)	C24—C25	1.402 (11)
Co1—S1	2.251 (2)	C24—H24	0.9300
Co1—S3	2.259 (2)	C25—N26	1.310 (10)
S1—C11	1.708 (8)	C25—C251	1.483 (10)
C11—N12	1.338 (8)	C251—H25A	0.9600
C11—N16	1.339 (8)	C251—H25B	0.9600
N12—C13	1.322 (8)	C251—H25C	0.9600
C13—C14	1.393 (9)	S3—C31	1.727 (7)
C13—C131	1.498 (10)	C31—N36	1.321 (9)
C131—H13A	0.9600	C31—N32	1.348 (9)
C131—H13B	0.9600	N32—C33	1.353 (8)
C131—H13C	0.9600	C33—C34	1.365 (9)
C14—C15	1.374 (10)	C33—C331	1.463 (9)
C14—H14	0.9300	C331—H33A	0.9600
C15—N16	1.359 (10)	C331—H33B	0.9600
C15—C151	1.497 (9)	C331—H33C	0.9600
C151—H15A	0.9600	C34—C35	1.380 (10)
C151—H15B	0.9600	C34—H34	0.9300
C151—H15C	0.9600	C35—N36	1.354 (9)
S2—C21	1.724 (7)	C35—C351	1.479 (10)
C21—N26	1.311 (9)	C351—H35A	0.9600
C21—N22	1.377 (8)	C351—H35B	0.9600
N22—C23	1.322 (9)	C351—H35C	0.9600
C23—C24	1.369 (10)	O1—H1A	0.9821
C23—C231	1.515 (10)	O1—H1B	0.7228
N12—Co1—N32	99.8 (2)	N22—C23—C231	117.4 (7)
N12—Co1—N22	102.8 (2)	C24—C23—C231	121.6 (8)
N32—Co1—N22	101.9 (3)	C23—C231—H23A	109.5
N12—Co1—S2	91.73 (17)	C23—C231—H23B	109.5
N32—Co1—S2	168.17 (19)	H23A—C231—H23B	109.5
N22—Co1—S2	72.63 (18)	C23—C231—H23C	109.5
N12—Co1—S1	72.69 (18)	H23A—C231—H23C	109.5
N32—Co1—S1	91.30 (19)	H23B—C231—H23C	109.5
N22—Co1—S1	166.66 (19)	C23—C24—C25	117.9 (8)
S2—Co1—S1	94.71 (8)	C23—C24—H24	121.1
N12—Co1—S3	165.56 (18)	C25—C24—H24	121.1
N32—Co1—S3	72.53 (18)	N26—C25—C24	122.0 (7)
N22—Co1—S3	90.86 (17)	N26—C25—C251	118.4 (8)
S2—Co1—S3	96.77 (8)	C24—C25—C251	119.6 (9)
S1—Co1—S3	94.92 (9)	C25—C251—H25A	109.5
C11—S1—Co1	78.3 (3)	C25—C251—H25B	109.5
N12—C11—N16	125.2 (7)	H25A—C251—H25B	109.5
N12—C11—S1	110.5 (5)	C25—C251—H25C	109.5
N16—C11—S1	124.2 (6)	H25A—C251—H25C	109.5
C13—N12—C11	119.5 (6)	H25B—C251—H25C	109.5
C13—N12—Co1	142.0 (5)	C25—N26—C21	116.9 (7)
C11—N12—Co1	98.3 (4)	C31—S3—Co1	78.9 (3)
N12—C13—C14	119.2 (7)	N36—C31—N32	125.9 (7)
N12—C13—C131	118.9 (7)	N36—C31—S3	125.0 (6)
C14—C13—C131	121.9 (7)	N32—C31—S3	109.1 (6)
C13—C131—H13A	109.5	C31—N32—C33	118.7 (6)
C13—C131—H13B	109.5	C31—N32—Co1	99.4 (5)
H13A—C131—H13B	109.5	C33—N32—Co1	141.7 (5)
C13—C131—H13C	109.5	N32—C33—C34	117.4 (7)
H13A—C131—H13C	109.5	N32—C33—C331	118.5 (7)
H13B—C131—H13C	109.5	C34—C33—C331	124.1 (7)
C15—C14—C13	118.7 (7)	C33—C331—H33A	109.5
C15—C14—H14	120.7	C33—C331—H33B	109.5
C13—C14—H14	120.7	H33A—C331—H33B	109.5
N16—C15—C14	121.9 (7)	C33—C331—H33C	109.5
N16—C15—C151	117.1 (8)	H33A—C331—H33C	109.5
C14—C15—C151	120.9 (8)	H33B—C331—H33C	109.5
C15—C151—H15A	109.5	C33—C34—C35	121.7 (7)
C15—C151—H15B	109.5	C33—C34—H34	119.2
H15A—C151—H15B	109.5	C35—C34—H34	119.2
C15—C151—H15C	109.5	N36—C35—C34	120.0 (7)
H15A—C151—H15C	109.5	N36—C35—C351	116.6 (8)
H15B—C151—H15C	109.5	C34—C35—C351	123.3 (8)
C11—N16—C15	115.5 (7)	C35—C351—H35A	109.5
C21—S2—Co1	80.1 (3)	C35—C351—H35B	109.5
N26—C21—N22	125.5 (7)	H35A—C351—H35B	109.5
N26—C21—S2	126.5 (6)	C35—C351—H35C	109.5
N22—C21—S2	107.9 (5)	H35A—C351—H35C	109.5
C23—N22—C21	116.9 (6)	H35B—C351—H35C	109.5
C23—N22—Co1	143.8 (5)	C31—N36—C35	116.2 (7)
C21—N22—Co1	99.3 (5)	H1A—O1—H1B	130.3
N22—C23—C24	120.8 (7)
N12—Co1—S1—C11	2.6 (3)	N32—Co1—N22—C21	−169.6 (4)
N32—Co1—S1—C11	−97.2 (3)	S2—Co1—N22—C21	−0.5 (4)
N22—Co1—S1—C11	74.9 (8)	S1—Co1—N22—C21	18.5 (10)
S2—Co1—S1—C11	93.0 (2)	S3—Co1—N22—C21	−97.3 (4)
S3—Co1—S1—C11	−169.8 (2)	C21—N22—C23—C24	1.5 (10)
Co1—S1—C11—N12	−3.9 (4)	Co1—N22—C23—C24	−176.4 (6)
Co1—S1—C11—N16	178.0 (6)	C21—N22—C23—C231	177.2 (7)
N16—C11—N12—C13	−1.9 (10)	Co1—N22—C23—C231	−0.8 (12)
S1—C11—N12—C13	−180.0 (5)	N22—C23—C24—C25	−1.7 (11)
N16—C11—N12—Co1	−177.5 (6)	C231—C23—C24—C25	−177.2 (7)
S1—C11—N12—Co1	4.5 (5)	C23—C24—C25—N26	2.4 (12)
N32—Co1—N12—C13	−88.8 (8)	C23—C24—C25—C251	179.3 (8)
N22—Co1—N12—C13	16.0 (8)	C24—C25—N26—C21	−2.9 (11)
S2—Co1—N12—C13	88.5 (7)	C251—C25—N26—C21	−179.8 (7)
S1—Co1—N12—C13	−177.1 (8)	N22—C21—N26—C25	2.8 (11)
S3—Co1—N12—C13	−145.3 (6)	S2—C21—N26—C25	178.1 (6)
N32—Co1—N12—C11	85.0 (4)	N12—Co1—S3—C31	59.2 (8)
N22—Co1—N12—C11	−170.3 (4)	N32—Co1—S3—C31	−0.3 (3)
S2—Co1—N12—C11	−97.7 (4)	N22—Co1—S3—C31	−102.5 (3)
S1—Co1—N12—C11	−3.3 (4)	S2—Co1—S3—C31	−175.1 (3)
S3—Co1—N12—C11	28.4 (10)	S1—Co1—S3—C31	89.5 (3)
C11—N12—C13—C14	2.2 (9)	Co1—S3—C31—N36	179.8 (7)
Co1—N12—C13—C14	175.1 (6)	Co1—S3—C31—N32	0.4 (5)
C11—N12—C13—C131	−177.6 (6)	N36—C31—N32—C33	3.4 (11)
Co1—N12—C13—C131	−4.7 (11)	S3—C31—N32—C33	−177.2 (5)
N12—C13—C14—C15	−1.7 (10)	N36—C31—N32—Co1	−179.9 (7)
C131—C13—C14—C15	178.0 (6)	S3—C31—N32—Co1	−0.5 (5)
C13—C14—C15—N16	0.8 (11)	N12—Co1—N32—C31	−167.0 (4)
C13—C14—C15—C151	−177.7 (6)	N22—Co1—N32—C31	87.5 (4)
N12—C11—N16—C15	0.9 (10)	S2—Co1—N32—C31	26.2 (11)
S1—C11—N16—C15	178.8 (5)	S1—Co1—N32—C31	−94.4 (4)
C14—C15—N16—C11	−0.4 (10)	S3—Co1—N32—C31	0.4 (4)
C151—C15—N16—C11	178.2 (6)	N12—Co1—N32—C33	8.3 (9)
N12—Co1—S2—C21	−102.5 (3)	N22—Co1—N32—C33	−97.2 (8)
N32—Co1—S2—C21	64.4 (9)	S2—Co1—N32—C33	−158.4 (7)
N22—Co1—S2—C21	0.4 (3)	S1—Co1—N32—C33	81.0 (8)
S1—Co1—S2—C21	−175.3 (2)	S3—Co1—N32—C33	175.7 (8)
S3—Co1—S2—C21	89.2 (2)	C31—N32—C33—C34	−1.4 (10)
Co1—S2—C21—N26	−176.5 (7)	Co1—N32—C33—C34	−176.1 (6)
Co1—S2—C21—N22	−0.6 (4)	C31—N32—C33—C331	178.4 (6)
N26—C21—N22—C23	−2.1 (10)	Co1—N32—C33—C331	3.6 (12)
S2—C21—N22—C23	−178.1 (5)	N32—C33—C34—C35	−0.3 (10)
N26—C21—N22—Co1	176.7 (6)	C331—C33—C34—C35	180.0 (7)
S2—C21—N22—Co1	0.6 (5)	C33—C34—C35—N36	0.3 (12)
N12—Co1—N22—C23	−94.6 (8)	C33—C34—C35—C351	−178.3 (7)
N32—Co1—N22—C23	8.5 (9)	N32—C31—N36—C35	−3.3 (11)
S2—Co1—N22—C23	177.7 (9)	S3—C31—N36—C35	177.4 (6)
S1—Co1—N22—C23	−163.4 (6)	C34—C35—N36—C31	1.4 (11)
S3—Co1—N22—C23	80.8 (8)	C351—C35—N36—C31	−179.9 (7)
N12—Co1—N22—C21	87.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N16^i	0.98	2.02	2.990 (8)	168
O1—H1A···S1^i	0.98	3.17	3.654 (6)	112
O1—H1B···N36^ii	0.72	2.52	3.088 (8)	137

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