The varied structures of cobalt(II)–pyridine (py)–sulfate: [Co(SO4)(py)4]n, [Co2(SO4)2(py)6]n, and [Co3(SO4)3(py)11]n

Park, A.M.; Pham, D.N.K.; Golen, J.A.; Manke, D.R.

doi:10.1107/S205698901901538X

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ISSN: 2056-9890

Volume 75| Part 12| December 2019| Pages 1888-1891

https://doi.org/10.1107/S205698901901538X

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The varied structures of cobalt(II)–pyridine (py)–sulfate: [Co(SO₄)(py)₄]_n, [Co₂(SO₄)₂(py)₆]_n, and [Co₃(SO₄)₃(py)₁₁]_n

Ava M. Park,^a Duyen N. K. Pham,^b James A. Golen ^b and David R. Manke ^b ^*

^aPortsmouth Abbey School, 285 Cory's Lane, Portsmouth, RI, 02871, USA, and ^bUniversity of Massachusetts Dartmouth, 285 Old Westport Rd., North Dartmouth, MA, 02747, USA
^*Correspondence e-mail: dmanke@umassd.edu

Edited by J. Simpson, University of Otago, New Zealand (Received 11 November 2019; accepted 14 November 2019; online 19 November 2019)

The solid-state structures of two cobalt–pyridine–sulfate compounds, namely catena-poly[[tetrakis(pyridine-κN)cobalt(II)]-μ-sulfato-κ²O:O′], [Co(SO₄)(C₅H₅N)₄]_n, (1), and catena-poly[[tetrakis(pyridine-κN)cobalt(II)]-μ-sulfato-κ³O:O′,O′′-[bis(pyridine-κN)cobalt(II)]-μ-sulfato-κ³O,O′:O′′]_n, [Co₂(SO₄)₂(C₅H₅N)₆]_n, (2), are reported. Compound (1) displays a polymeric structure, with infinite chains of Co^II cations adopting octahedral N₄O₂ coordination environments that involve four pyridine ligands and two bridging sulfate ions. Compound (2) is also polymeric with infinite chains of Co^II cations. The first Co center has an octahedral N₄O₂ coordination environment that involves four pyridine ligands and two bridging sulfate ligands. The second Co center has an octahedral N₂O₄ coordination environment that involves two pyridine ligands and two bridging sulfate ions that chelate the Co atom. The structure of (2) was refined as a two-component inversion twin.

Keywords: crystal structure; pyridine; sulfate; transition metals; crystal field theory; coordination chemistry; cobalt complexes.

CCDC references: 1965662; 1965663; 1965662; 1965663

1. Chemical context

The synthesis of metal–pyrdine–sulfates has been reported since the 19th century, when Jørgensen's chain theory was still the prevailing hypothesis (Reitzenstein, 1894 ; Howe, 1898 ). Since that time, the structural understanding of metal complexes has greatly increased, first with the acceptance of Werner's coordination theory (Werner, 1893 ), with crystal field theory from Bethe in 1929 (Bethe, 1929 ), and the modifications of theory in the ninety years since. Despite the long history of these compounds, their crystallographic study is rather limited. Before we began a crystallographic examination of metal–pyridine–sulfates in 2018, there were only two examples of such complexes without other ligands or components reported in the literature (Cotton & Reid, 1984 ; Memon et al., 2006 ).

Since we began studying the structural chemistry of metal–pyridine–sulfates, we have observed many different structural motifs in the complexes. The coordination environment of each compound can usually be predicted with crystal field theory, although the exact nature is dependent upon the number of pyridines bound and the binding mode of the sulfate anion. The sulfate anion can have a number of different coordination modes, including μ-sulfato-κ²-O:O, μ-sulfato-κ²-O:O′ and μ-sulfato-κ³-O:O′:O". Herein we report two new structures of cobalt–pyridine–sulfates formed by altering the growth conditions and compare these structures with the previously reported structure of a cobalt–pyridine–sulfate and the structures of related complexes.

2. Structural commentary

The asymmetric unit of the pink crystals of (1) consists of two pyridine molecules and one half of a sulfate anion coordinated to a cobalt atom sitting on an inversion center (Fig. 1a). When grown out, the cobalt ion shows an octahedral coordination environment (Fig. 1b). The equatorial positions of the octahedron are occupied by four pyridine ligands in a square-planar arrangement. The CoN₄ unit exhibits planarity enforced by symmetry, with cis N—Co—N angles of 86.45 (6) and 93.55 (6)°. To complete the octahedron, the axial positions are occupied by two sulfate ions, with an inversion enforced O—Co—O angle of 180° and cis O—Co—N angles of 88.87 (6) and 91.67 (6)°. The pyridine rings are rotated from the CoN₄ plane by dihedral angles of 47.30 (10) and 78.33 (9)°. The 78.33 (9)° angles are constrained by two C—H⋯O interactions between the ortho hydrogen atoms and the two trans sulfates (Table 1).

Table 1
Hydrogen-bond geometry (Å, °) for (1)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯O1ⁱ	0.93	2.51	3.106 (2)	122
C6—H6A⋯O2ⁱ	0.93	2.51	3.429 (3)	171
C10—H10A⋯O1	0.93	2.48	3.046 (2)	120
C10—H10A⋯O2ⁱⁱ	0.93	2.43	3.353 (3)	171
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+1, y, -z+{\script{3\over 2}}]$ .

Figure 1
The molecular structure of compound (1), including (a) the asymmetric unit and (b) the coordination environment around Co1. Displacement ellipsoids are drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radius. C—H⋯O interactions (Table 1

) are shown as dashed lines. [Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) x, 1 − y, − $[{1\over 2}]$ + z; (iii) 1 − x, y, $[{3\over 2}]$ − z].

The asymmetric unit of the purple crystals of (2) consists of two cobalt atoms, six coordinated pyridines and two sulfate anions (Fig. 2a). There are two crystallographically unique cobalt atoms, with Co1 (Fig. 2b) displaying an octahedral N₄O₂ coordination environment and Co2 (Fig. 2c) exhibiting an octahedral N₂O₄ coordination geometry.

Figure 2
The molecular structure of compound (2), including (a) the asymmetric unit, (b) the coordination environment around Co1, and (c) the coordination environment around Co2. Displacement ellipsoids are drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radius. C—H⋯O interactions (Table 2

) are shown as dashed lines. [Symmetry code: (i) −1 + x, −1 + y, −1 + z].

Co1 has four pyridine ligands occupying the equatorial positions of an octahedron, with the CoN₄ plane showing a maximum deviation from planarity of 0.018 Å. Two sulfate anions occupy the axial positions to complete the octahedral coordination. The cis N—Co—N angles have values ranging from 87.48 (13) to 93.18 (12)°, and the trans O—Co—O angle is 173.43 (12)°. The planes of the four pyridine rings are rotated from the equatorial CoN₄ plane by dihedral angles of 58.6 (2), 64.6 (2), 65.6 (2), and 73.1 (2)°. Two of the rings show one C—H⋯O interaction with an ortho hydrogen atom, one ring shows two C—H⋯O interactions with two ortho hydrogen atoms, and the fourth ring shows no C—H⋯O interactions (Table 2).

Table 2
Hydrogen-bond geometry (Å, °) for (2)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O6	0.95	2.63	3.563 (6)	167
C2—H2A⋯O2ⁱ	0.95	2.52	3.219 (5)	131
C5—H5A⋯O4	0.95	2.42	3.009 (5)	120
C6—H6A⋯O5	0.95	2.56	3.054 (5)	112
C6—H6A⋯O7	0.95	2.47	3.322 (6)	149
C10—H10A⋯O4	0.95	2.53	3.010 (5)	112
C12—H12A⋯O7ⁱⁱ	0.95	2.60	3.271 (5)	128
C15—H15A⋯O5	0.95	2.45	3.017 (5)	118
C16—H16A⋯O2	0.95	2.19	3.139 (6)	176
C20—H20A⋯O5	0.95	2.51	3.091 (5)	119
C20—H20A⋯O6	0.95	2.32	3.272 (5)	175
C25—H25A⋯O8	0.95	2.55	3.162 (5)	123
C30—H30A⋯O7	0.95	2.54	3.116 (5)	119
Symmetry codes: (i) x-1, y-1, z; (ii) x+1, y+1, z.

Co2 is bound by two pyridine ligands and two chelating sulfate anions to give an octahedral coordination environment. The pyridine rings adopt a cis configuration, with an N—Co—N angle of 93.63 (13)°. The two sulfate ligands exhibit O—Co—O bite angles of 65.90 (10) and 66.37 (10)°. The other cis O—Co—O angles are 86.87 (11), 98.98 (11), and 102.84 (11)°, and the six cis N—Co—O angles range from 92.49 (12) to 98.33 (13)°. Each pyridine ring is involved in ortho C—H⋯O interactions (Table 2).

3. Supramolecular features

The Co^II atoms in compound (1) are linked together into infinite chains along the [001] direction through sulfate anions with O—S—O bridges (Figs. 3a, 4a). Between each successive tetrapyridine cobalt unit, there are parallel slipped π–π interactions [inter-centroid distance: 3.637 (1) Å, inter-planar distance: 3.611 (1) Å, slippage: 0.435 (1) Å].

Figure 3
The infinite chains of (a) compound (1) along [001], (b) compound (2) along [111], and (c) the previously reported cobalt–pyridine-sulfate complex [Co₃(SO₄)₃(C₅H₅N)₁₁]_n along [001] (Pham et al., 2019

). Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity. The π–π interactions in (1) are shown as dashed lines.

Figure 4
The packing of (a) compound (1) along the c-axis and (b) compound (2) along the b-axis. Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity.

The Co^II atoms in compound (2) are linked together into infinite chains along the [111] direction through the sulfate anions (Figs. 3b, 4b). The chain alternates between tetrapyridine cobalt units and dipyridine cobalt units. No π–π interactions are observed in the crystal.

4. Database survey

In a prior publication, we reported the structure of another cobalt–pyridine–sulfate [Co₃(SO₄)₃(C₅H₅N)₁₁)]_n, which was grown at a lower concentration of cobalt. This structure shows two successive octahedral cobalt atoms with N₄O₂ coordination, where each atom is coordinated to four pyridines and two bridging sulfates. The third cobalt atom in the chain shows N₃O₃ coordination where three pyridines are bound and there are two sulfates bound, one of which is chelating to the cobalt (Pham et al., 2018 ). Fig. 3 compares the chain structure of this complex with those of compounds (1) and (2). In compound (1), every cobalt atom possesses an octahedral N₄O₂ coordination. This complex is isostructural with the structure observed for the iron and nickel pyridine–sulfate complexes (Roy et al., 2018 ). This structural motif is also consistent with that observed for the 4-picoline–sulfate structures of iron, cobalt, nickel and cadmium (Pham et al., 2019 ). In compound (2), the cobalt atoms alternate between N₄O₂ coordination and N₂O₄ coordination. This tetrapyridine/bipyridine alternation is similar to what is observed in the zinc–pyridine–sulfate structure, which alternates between octahedral and tetrahedral zinc centers. In the case of cobalt, the bis(pyridine) cobalt center is still octahedral because the two coordinated sulfates both chelate to the cobalt. The end result is an infinite chain of octahedral cobalt atoms, which is true in compound (1) and the previously reported cobalt–pyridine–sulfate complex. The methanesulfato complexes of cobalt (II) have also been reported as octahedral tetrakis(pyridine), [Co(SO₃CH₃)₂(py)₄], and octahedral bis(pyridine), [Co(SO₃CH₃)₂(py)₂], compounds, consistent with the two independent cobalt centers observed in (2) (Johnson et al., 1977 ).

5. Synthesis and crystallization

For compound (1), 40 mg of cobalt sulfate heptahydrate (J. T. Baker) was dissolved in pyridine (2 mL, Fischer Chemical) and distilled water (100 µL) in a 20 mL vial. The vial was heated to 338 K for 48 h, after which single crystals suitable for X-ray diffraction studies were isolated from the reaction mixture.

For compound (2), 48 mg of cobalt sulfate heptahydrate (J. T. Baker) was dissolved in pyridine (2 mL, Fischer Chemical) and distilled water (30 µL) in a 20 mL vial. The vial was heated to 358 K for 48 h, after which single crystals suitable for X-ray diffraction studies were isolated from the reaction mixture.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All structure solutions were obtained by intrinsic phasing. All non-hydrogen atoms were refined anisotropically (SHELXL) by full-matrix least squares on F². Hydrogen atoms were placed in calculated positions and then refined with a riding model with C—H bond lengths of 0.95 Å and with isotropic displacement parameters set to 1.20 U_eq of the parent C atom. The structre of (2) was refined as a two-component inversion twin, BASF = 0.165 (13).

Table 3
Experimental details

	(1)	(2)
Crystal data
Chemical formula	[Co(SO₄)(C₅H₅N)₄]	[Co₂(SO₄)₂(C₅H₅N)₆]
M_r	471.39	784.58
Crystal system, space group	Monoclinic, C2/c	Triclinic, P1
Temperature (K)	295	200
a, b, c (Å)	18.6323 (18), 10.0803 (9), 11.9403 (11)	9.5795 (6), 9.7612 (5), 10.7219 (6)
α, β, γ (°)	90, 115.945 (3), 90	98.488 (2), 107.697 (2), 115.948 (2)
V (Å³)	2016.6 (3)	811.46 (8)
Z	4	1
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.99	1.21
Crystal size (mm)	0.28 × 0.13 × 0.06	0.25 × 0.20 × 0.02

Data collection
Diffractometer	Bruker APEXIII CMOS	Bruker APEXIII photon2
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )	Multi-scan (SADABS; Bruker, 2016)
T_min, T_max	0.667, 0.745	0.661, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	20212, 1854, 1572	22679, 6013, 5906
R_int	0.071	0.026
(sin θ/λ)_max (Å⁻¹)	0.604	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.063, 1.02	0.026, 0.072, 1.03
No. of reflections	1854	6013
No. of parameters	139	434
No. of restraints	0	3
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.24	0.79, −0.30
Absolute structure	–	Refined as an inversion twin
Absolute structure parameter	–	0.165 (13)
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ), SHELXTL (Sheldrick, 2008 ), and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 1965662; 1965663; 1965662; 1965663

Crystal structure: contains datablocks 1, 2, I. DOI: https://doi.org/10.1107/S205698901901538X/sj5586sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S205698901901538X/sj55861sup2.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S205698901901538X/sj55862sup3.hkl

checkCIF report

Computing details top

For both structures, data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b) and OLEX2 (Dolomanov et al., 2009). Molecular graphics: SHELXTL (Sheldrick, 2008) for (1); SHELXTL (Sheldrick 2008) for (2). For both structures, software used to prepare material for publication: SHELXTL (Sheldrick 2008) and publCIF (Westrip, 2010).

catena-Poly[[tetrakis(pyridine-κN)cobalt(II)]-µ-sulfato-κ²O:O'] (1) top

Crystal data top

[Co(SO₄)(C₅H₅N)₄]	F(000) = 972
M_r = 471.39	D_x = 1.553 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.6323 (18) Å	Cell parameters from 8333 reflections
b = 10.0803 (9) Å	θ = 3.3–25.3°
c = 11.9403 (11) Å	µ = 0.99 mm⁻¹
β = 115.945 (3)°	T = 295 K
V = 2016.6 (3) Å³	BLOCK, pink
Z = 4	0.28 × 0.13 × 0.06 mm

Data collection top

Bruker APEXIII CMOS diffractometer	1572 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.071
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 25.4°, θ_min = 3.3°
T_min = 0.667, T_max = 0.745	h = −22→22
20212 measured reflections	k = −12→12
1854 independent reflections	l = −14→14

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.027	w = 1/[σ²(F_o²) + (0.0254P)² + 2.4084P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.063	(Δ/σ)_max < 0.001
S = 1.02	Δρ_max = 0.24 e Å⁻³
1854 reflections	Δρ_min = −0.24 e Å⁻³
139 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0019 (3)

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co1	0.5000	0.5000	0.5000	0.02070 (13)
O1	0.49333 (8)	0.59836 (16)	0.64714 (13)	0.0406 (4)
O2	0.57186 (9)	0.76549 (16)	0.79112 (15)	0.0433 (4)
N1	0.45647 (10)	0.32138 (17)	0.55318 (15)	0.0305 (4)
N2	0.37320 (9)	0.55056 (17)	0.38523 (14)	0.0257 (4)
C1	0.39850 (16)	0.3286 (3)	0.5901 (2)	0.0503 (7)
H1A	0.3780	0.4116	0.5942	0.060*
C2	0.36775 (18)	0.2191 (3)	0.6224 (3)	0.0649 (8)
H2A	0.3265	0.2285	0.6457	0.078*
C3	0.39806 (18)	0.0971 (3)	0.6200 (2)	0.0594 (8)
H3A	0.3780	0.0216	0.6410	0.071*
C4	0.45897 (19)	0.0885 (3)	0.5858 (3)	0.0582 (7)
H4A	0.4823	0.0069	0.5857	0.070*
C5	0.48541 (15)	0.2016 (2)	0.5514 (2)	0.0448 (6)
H5A	0.5257	0.1937	0.5257	0.054*
C6	0.33165 (12)	0.4887 (2)	0.2775 (2)	0.0360 (5)
H6A	0.3577	0.4259	0.2513	0.043*
C7	0.25194 (13)	0.5129 (3)	0.2028 (2)	0.0469 (6)
H7A	0.2255	0.4687	0.1274	0.056*
C8	0.21197 (12)	0.6030 (2)	0.2410 (2)	0.0404 (6)
H8A	0.1584	0.6218	0.1919	0.048*
C9	0.25326 (12)	0.6644 (2)	0.3534 (2)	0.0370 (5)
H9A	0.2276	0.7240	0.3832	0.044*
C10	0.33304 (12)	0.6372 (2)	0.42193 (19)	0.0331 (5)
H10A	0.3605	0.6809	0.4974	0.040*
S1	0.5000	0.68569 (6)	0.7500	0.01886 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0187 (2)	0.0246 (2)	0.0198 (2)	0.00353 (15)	0.00935 (15)	−0.00111 (15)
O1	0.0358 (8)	0.0582 (11)	0.0268 (8)	0.0111 (8)	0.0128 (6)	−0.0138 (7)
O2	0.0303 (8)	0.0391 (9)	0.0562 (10)	−0.0150 (7)	0.0148 (7)	0.0026 (8)
N1	0.0321 (9)	0.0314 (10)	0.0290 (9)	0.0009 (8)	0.0141 (8)	0.0004 (8)
N2	0.0212 (8)	0.0300 (9)	0.0261 (9)	0.0040 (7)	0.0105 (7)	0.0013 (7)
C1	0.0583 (16)	0.0482 (16)	0.0638 (16)	0.0080 (13)	0.0445 (14)	0.0116 (13)
C2	0.0691 (19)	0.070 (2)	0.079 (2)	−0.0043 (16)	0.0536 (17)	0.0158 (16)
C3	0.083 (2)	0.0493 (17)	0.0534 (16)	−0.0231 (15)	0.0364 (15)	0.0029 (13)
C4	0.085 (2)	0.0324 (14)	0.0665 (18)	−0.0050 (13)	0.0420 (16)	−0.0024 (13)
C5	0.0510 (14)	0.0351 (13)	0.0563 (15)	−0.0006 (11)	0.0309 (12)	0.0000 (11)
C6	0.0268 (11)	0.0426 (13)	0.0359 (11)	0.0071 (10)	0.0114 (9)	−0.0080 (10)
C7	0.0286 (12)	0.0580 (16)	0.0401 (13)	0.0042 (11)	0.0021 (10)	−0.0160 (12)
C8	0.0214 (11)	0.0496 (14)	0.0440 (13)	0.0096 (10)	0.0085 (10)	0.0030 (11)
C9	0.0304 (11)	0.0438 (14)	0.0399 (12)	0.0135 (10)	0.0183 (10)	0.0025 (10)
C10	0.0282 (11)	0.0406 (12)	0.0289 (11)	0.0058 (9)	0.0110 (9)	−0.0033 (9)
S1	0.0181 (3)	0.0204 (3)	0.0206 (3)	0.000	0.0108 (3)	0.000

Geometric parameters (Å, º) top

Co1—O1ⁱ	2.0679 (13)	C3—C4	1.367 (4)
Co1—O1	2.0679 (13)	C3—H3A	0.9300
Co1—N1	2.1803 (17)	C4—C5	1.373 (3)
Co1—N1ⁱ	2.1803 (17)	C4—H4A	0.9300
Co1—N2	2.2105 (15)	C5—H5A	0.9300
Co1—N2ⁱ	2.2105 (15)	C6—C7	1.379 (3)
O1—S1	1.4715 (14)	C6—H6A	0.9300
O2—S1	1.4511 (14)	C7—C8	1.373 (3)
N1—C5	1.327 (3)	C7—H7A	0.9300
N1—C1	1.335 (3)	C8—C9	1.368 (3)
N2—C6	1.331 (3)	C8—H8A	0.9300
N2—C10	1.342 (2)	C9—C10	1.375 (3)
C1—C2	1.373 (4)	C9—H9A	0.9300
C1—H1A	0.9300	C10—H10A	0.9300
C2—C3	1.359 (4)	S1—O2ⁱⁱ	1.4511 (14)
C2—H2A	0.9300	S1—O1ⁱⁱ	1.4715 (14)

O1ⁱ—Co1—O1	180.0	C2—C3—H3A	121.0
O1ⁱ—Co1—N1	91.13 (6)	C4—C3—H3A	121.0
O1—Co1—N1	88.87 (6)	C3—C4—C5	119.3 (3)
O1ⁱ—Co1—N1ⁱ	88.87 (6)	C3—C4—H4A	120.3
O1—Co1—N1ⁱ	91.13 (6)	C5—C4—H4A	120.3
N1—Co1—N1ⁱ	180.0	N1—C5—C4	123.3 (2)
O1ⁱ—Co1—N2	91.66 (6)	N1—C5—H5A	118.3
O1—Co1—N2	88.34 (6)	C4—C5—H5A	118.3
N1—Co1—N2	86.45 (6)	N2—C6—C7	123.24 (19)
N1ⁱ—Co1—N2	93.55 (6)	N2—C6—H6A	118.4
O1ⁱ—Co1—N2ⁱ	88.33 (6)	C7—C6—H6A	118.4
O1—Co1—N2ⁱ	91.67 (6)	C8—C7—C6	119.3 (2)
N1—Co1—N2ⁱ	93.55 (6)	C8—C7—H7A	120.3
N1ⁱ—Co1—N2ⁱ	86.45 (6)	C6—C7—H7A	120.3
N2—Co1—N2ⁱ	180.0	C9—C8—C7	118.1 (2)
S1—O1—Co1	168.95 (11)	C9—C8—H8A	120.9
C5—N1—C1	116.6 (2)	C7—C8—H8A	120.9
C5—N1—Co1	122.80 (14)	C8—C9—C10	119.39 (19)
C1—N1—Co1	120.61 (16)	C8—C9—H9A	120.3
C6—N2—C10	116.66 (17)	C10—C9—H9A	120.3
C6—N2—Co1	120.20 (13)	N2—C10—C9	123.22 (19)
C10—N2—Co1	123.03 (13)	N2—C10—H10A	118.4
N1—C1—C2	123.1 (2)	C9—C10—H10A	118.4
N1—C1—H1A	118.5	O2—S1—O2ⁱⁱ	112.67 (14)
C2—C1—H1A	118.5	O2—S1—O1	110.03 (9)
C3—C2—C1	119.5 (2)	O2ⁱⁱ—S1—O1	108.71 (8)
C3—C2—H2A	120.2	O2—S1—O1ⁱⁱ	108.71 (8)
C1—C2—H2A	120.2	O2ⁱⁱ—S1—O1ⁱⁱ	110.03 (9)
C2—C3—C4	118.1 (2)	O1—S1—O1ⁱⁱ	106.52 (14)

C5—N1—C1—C2	−1.5 (4)	N2—C6—C7—C8	−1.4 (4)
Co1—N1—C1—C2	178.7 (2)	C6—C7—C8—C9	−0.7 (4)
N1—C1—C2—C3	1.5 (5)	C7—C8—C9—C10	1.9 (3)
C1—C2—C3—C4	0.4 (5)	C6—N2—C10—C9	−0.8 (3)
C2—C3—C4—C5	−2.1 (4)	Co1—N2—C10—C9	−176.96 (16)
C1—N1—C5—C4	−0.3 (4)	C8—C9—C10—N2	−1.2 (3)
Co1—N1—C5—C4	179.4 (2)	Co1—O1—S1—O2	−16.8 (5)
C3—C4—C5—N1	2.2 (4)	Co1—O1—S1—O2ⁱⁱ	107.0 (5)
C10—N2—C6—C7	2.1 (3)	Co1—O1—S1—O1ⁱⁱ	−134.5 (5)
Co1—N2—C6—C7	178.36 (19)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O1ⁱ	0.93	2.51	3.106 (2)	122
C6—H6A···O2ⁱ	0.93	2.51	3.429 (3)	171
C10—H10A···O1	0.93	2.48	3.046 (2)	120
C10—H10A···O2ⁱⁱ	0.93	2.43	3.353 (3)	171

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

(2) top

Crystal data top

[Co(SO₄)₂(C₅H₆N)₆]	Z = 1
M_r = 784.58	F(000) = 402
Triclinic, P1	D_x = 1.606 Mg m⁻³
a = 9.5795 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7612 (5) Å	Cell parameters from 9920 reflections
c = 10.7219 (6) Å	θ = 2.6–25.7°
α = 98.488 (2)°	µ = 1.21 mm⁻¹
β = 107.697 (2)°	T = 200 K
γ = 115.948 (2)°	PLATE, purple
V = 811.46 (8) Å³	0.25 × 0.20 × 0.02 mm

Data collection top

Bruker APEXIII photon2 diffractometer	5906 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.026
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 25.7°, θ_min = 3.1°
T_min = 0.661, T_max = 0.745	h = −11→11
22679 measured reflections	k = −11→11
6013 independent reflections	l = −13→13

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.026	w = 1/[σ²(F_o²) + (0.0524P)² + 0.1142P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.072	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 0.79 e Å⁻³
6013 reflections	Δρ_min = −0.29 e Å⁻³
434 parameters	Absolute structure: Refined as an inversion twin
3 restraints	Absolute structure parameter: 0.165 (13)

Special details top

Refinement. Refined as a 2-component inversion twin. BASF 0.16482

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co1	0.84425 (5)	0.55261 (5)	0.61510 (4)	0.01356 (12)
Co2	0.24785 (6)	0.13866 (6)	0.10725 (5)	0.01665 (13)
S1	1.17468 (11)	0.89862 (10)	0.89114 (9)	0.01596 (19)
S2	0.51931 (11)	0.19943 (10)	0.33225 (9)	0.0164 (2)
O1	1.1869 (4)	0.8903 (3)	1.0308 (3)	0.0257 (6)
O2	1.3166 (4)	0.9028 (4)	0.8658 (4)	0.0307 (7)
O3	1.1721 (4)	1.0501 (3)	0.8887 (3)	0.0241 (6)
O4	1.0118 (3)	0.7597 (3)	0.7855 (3)	0.0244 (6)
O5	0.6576 (4)	0.3553 (3)	0.4393 (3)	0.0217 (6)
O6	0.5406 (4)	0.0691 (4)	0.3655 (3)	0.0301 (7)
O7	0.3509 (3)	0.1777 (3)	0.3224 (3)	0.0223 (6)
O8	0.5184 (4)	0.2064 (4)	0.1943 (3)	0.0230 (6)
N1	0.7283 (4)	0.4360 (4)	0.7445 (4)	0.0204 (7)
N2	0.6741 (4)	0.6487 (4)	0.5820 (4)	0.0215 (7)
N3	0.9613 (4)	0.6672 (4)	0.4849 (3)	0.0200 (7)
N4	1.0052 (4)	0.4460 (4)	0.6447 (3)	0.0176 (7)
N5	0.3110 (5)	0.3784 (4)	0.1165 (4)	0.0246 (7)
N6	0.0033 (4)	0.0704 (4)	0.0989 (4)	0.0229 (7)
C1	0.6334 (6)	0.2757 (5)	0.7094 (5)	0.0272 (9)
H1A	0.6163	0.2109	0.6247	0.033*
C2	0.5587 (6)	0.1993 (6)	0.7905 (5)	0.0336 (10)
H2A	0.4927	0.0850	0.7619	0.040*
C3	0.5820 (6)	0.2929 (7)	0.9138 (5)	0.0369 (11)
H3A	0.5347	0.2447	0.9728	0.044*
C4	0.6773 (6)	0.4601 (7)	0.9487 (5)	0.0370 (11)
H4A	0.6929	0.5281	1.0310	0.044*
C5	0.7486 (6)	0.5257 (5)	0.8629 (4)	0.0286 (9)
H5A	0.8152	0.6397	0.8889	0.034*
C6	0.5027 (6)	0.5482 (6)	0.5237 (5)	0.0306 (10)
H6A	0.4581	0.4352	0.4991	0.037*
C7	0.3906 (7)	0.6036 (7)	0.4988 (6)	0.0488 (15)
H7A	0.2711	0.5296	0.4589	0.059*
C8	0.4526 (8)	0.7670 (8)	0.5321 (7)	0.0532 (16)
H8A	0.3771	0.8074	0.5150	0.064*
C9	0.6240 (8)	0.8687 (7)	0.5899 (6)	0.0464 (14)
H9A	0.6701	0.9819	0.6137	0.056*
C10	0.7326 (6)	0.8065 (6)	0.6143 (5)	0.0296 (10)
H10A	0.8524	0.8793	0.6554	0.036*
C11	1.0601 (5)	0.8273 (5)	0.5168 (4)	0.0246 (9)
H11A	1.0821	0.8958	0.6019	0.030*
C12	1.1313 (6)	0.8974 (6)	0.4317 (5)	0.0316 (10)
H12A	1.1984	1.0113	0.4572	0.038*
C13	1.1031 (6)	0.7992 (7)	0.3097 (5)	0.0355 (11)
H13A	1.1498	0.8437	0.2491	0.043*
C14	1.0062 (6)	0.6355 (6)	0.2778 (5)	0.0354 (11)
H14A	0.9873	0.5649	0.1953	0.042*
C15	0.9365 (5)	0.5741 (5)	0.3658 (5)	0.0277 (9)
H15A	0.8676	0.4604	0.3410	0.033*
C16	1.1720 (6)	0.5345 (6)	0.7278 (6)	0.0349 (11)
H16A	1.2212	0.6471	0.7689	0.042*
C17	1.2763 (6)	0.4698 (7)	0.7568 (6)	0.0461 (14)
H17A	1.3939	0.5371	0.8169	0.055*
C18	1.2079 (7)	0.3067 (7)	0.6978 (6)	0.0444 (13)
H18A	1.2760	0.2588	0.7180	0.053*
C19	1.0382 (7)	0.2158 (6)	0.6090 (6)	0.0429 (13)
H19A	0.9879	0.1040	0.5632	0.051*
C20	0.9411 (6)	0.2882 (5)	0.5866 (5)	0.0295 (10)
H20A	0.8230	0.2227	0.5272	0.035*
C21	0.1897 (7)	0.4092 (6)	0.0510 (6)	0.0390 (11)
H21A	0.0781	0.3207	−0.0062	0.047*
C22	0.2193 (8)	0.5635 (7)	0.0626 (7)	0.0458 (13)
H22A	0.1299	0.5798	0.0139	0.055*
C23	0.3786 (8)	0.6921 (6)	0.1451 (6)	0.0475 (15)
H23A	0.4017	0.7994	0.1571	0.057*
C24	0.5055 (8)	0.6619 (6)	0.2107 (6)	0.0456 (13)
H24A	0.6186	0.7487	0.2666	0.055*
C25	0.4666 (6)	0.5049 (5)	0.1944 (5)	0.0337 (10)
H25A	0.5548	0.4861	0.2408	0.040*
C26	−0.1383 (6)	−0.0208 (6)	−0.0188 (5)	0.0321 (10)
H26A	−0.1291	−0.0677	−0.0979	0.039*
C27	−0.2969 (6)	−0.0497 (6)	−0.0301 (5)	0.0384 (11)
H27A	−0.3944	−0.1150	−0.1154	0.046*
C28	−0.3120 (6)	0.0175 (6)	0.0842 (6)	0.0368 (11)
H28A	−0.4192	0.0019	0.0782	0.044*
C29	−0.1684 (7)	0.1076 (7)	0.2070 (6)	0.0441 (13)
H29A	−0.1751	0.1530	0.2882	0.053*
C30	−0.0132 (6)	0.1308 (6)	0.2096 (5)	0.0338 (10)
H30A	0.0855	0.1927	0.2945	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0131 (2)	0.0118 (2)	0.0131 (2)	0.00517 (18)	0.00466 (18)	0.00285 (17)
Co2	0.0152 (2)	0.0145 (2)	0.0156 (2)	0.00629 (19)	0.00422 (19)	0.00207 (18)
S1	0.0135 (4)	0.0128 (4)	0.0152 (4)	0.0041 (3)	0.0040 (3)	0.0009 (3)
S2	0.0148 (4)	0.0132 (4)	0.0148 (4)	0.0049 (4)	0.0032 (4)	0.0021 (4)
O1	0.0351 (17)	0.0227 (15)	0.0163 (14)	0.0150 (13)	0.0074 (13)	0.0052 (12)
O2	0.0177 (14)	0.0232 (15)	0.0453 (19)	0.0067 (12)	0.0157 (14)	0.0028 (14)
O3	0.0320 (16)	0.0164 (14)	0.0256 (15)	0.0124 (13)	0.0133 (13)	0.0082 (12)
O4	0.0158 (13)	0.0201 (14)	0.0213 (15)	0.0030 (12)	0.0036 (12)	−0.0055 (11)
O5	0.0182 (14)	0.0174 (14)	0.0173 (14)	0.0036 (11)	0.0036 (12)	0.0004 (11)
O6	0.0295 (16)	0.0180 (15)	0.0332 (18)	0.0114 (13)	0.0037 (14)	0.0064 (13)
O7	0.0165 (14)	0.0273 (15)	0.0192 (14)	0.0085 (12)	0.0073 (11)	0.0066 (12)
O8	0.0239 (14)	0.0275 (15)	0.0170 (14)	0.0131 (13)	0.0092 (12)	0.0045 (12)
N1	0.0187 (16)	0.0204 (17)	0.0201 (17)	0.0082 (14)	0.0082 (14)	0.0073 (14)
N2	0.0273 (18)	0.0250 (18)	0.0211 (17)	0.0173 (15)	0.0134 (15)	0.0102 (14)
N3	0.0195 (16)	0.0214 (17)	0.0191 (17)	0.0099 (14)	0.0084 (14)	0.0073 (14)
N4	0.0171 (16)	0.0174 (16)	0.0188 (17)	0.0083 (13)	0.0093 (14)	0.0052 (13)
N5	0.0304 (19)	0.0205 (18)	0.0229 (18)	0.0129 (16)	0.0116 (15)	0.0061 (15)
N6	0.0189 (17)	0.0236 (17)	0.0243 (18)	0.0103 (14)	0.0092 (14)	0.0038 (14)
C1	0.031 (2)	0.026 (2)	0.033 (2)	0.0157 (19)	0.0180 (19)	0.0152 (19)
C2	0.031 (2)	0.028 (2)	0.040 (3)	0.0087 (19)	0.018 (2)	0.020 (2)
C3	0.029 (2)	0.052 (3)	0.034 (3)	0.016 (2)	0.020 (2)	0.026 (2)
C4	0.034 (3)	0.047 (3)	0.023 (2)	0.014 (2)	0.015 (2)	0.008 (2)
C5	0.029 (2)	0.029 (2)	0.020 (2)	0.0102 (19)	0.0091 (18)	0.0037 (18)
C6	0.023 (2)	0.029 (2)	0.036 (3)	0.0144 (19)	0.0078 (19)	0.0027 (19)
C7	0.024 (2)	0.052 (3)	0.055 (4)	0.024 (2)	0.001 (2)	−0.004 (3)
C8	0.046 (3)	0.056 (4)	0.061 (4)	0.043 (3)	0.005 (3)	0.007 (3)
C9	0.053 (3)	0.039 (3)	0.058 (4)	0.037 (3)	0.017 (3)	0.012 (3)
C10	0.036 (2)	0.028 (2)	0.029 (2)	0.022 (2)	0.010 (2)	0.0090 (19)
C11	0.031 (2)	0.022 (2)	0.026 (2)	0.0147 (18)	0.0138 (18)	0.0113 (17)
C12	0.033 (2)	0.032 (2)	0.041 (3)	0.018 (2)	0.022 (2)	0.023 (2)
C13	0.032 (2)	0.049 (3)	0.032 (3)	0.019 (2)	0.020 (2)	0.025 (2)
C14	0.030 (2)	0.043 (3)	0.025 (2)	0.012 (2)	0.015 (2)	0.006 (2)
C15	0.025 (2)	0.026 (2)	0.029 (2)	0.0082 (18)	0.0159 (19)	0.0061 (18)
C16	0.023 (2)	0.026 (2)	0.047 (3)	0.0133 (19)	0.008 (2)	−0.001 (2)
C17	0.024 (2)	0.043 (3)	0.055 (3)	0.021 (2)	0.000 (2)	−0.001 (3)
C18	0.042 (3)	0.045 (3)	0.060 (4)	0.035 (3)	0.018 (3)	0.017 (3)
C19	0.038 (3)	0.028 (2)	0.064 (4)	0.022 (2)	0.016 (3)	0.013 (2)
C20	0.024 (2)	0.024 (2)	0.037 (2)	0.0139 (18)	0.0080 (19)	0.0077 (19)
C21	0.035 (3)	0.036 (3)	0.051 (3)	0.020 (2)	0.017 (2)	0.024 (2)
C22	0.057 (3)	0.048 (3)	0.069 (4)	0.041 (3)	0.041 (3)	0.037 (3)
C23	0.079 (4)	0.030 (3)	0.058 (4)	0.035 (3)	0.045 (3)	0.023 (3)
C24	0.055 (3)	0.025 (2)	0.045 (3)	0.011 (2)	0.020 (3)	0.010 (2)
C25	0.038 (3)	0.021 (2)	0.032 (2)	0.011 (2)	0.010 (2)	0.0063 (19)
C26	0.024 (2)	0.035 (2)	0.030 (2)	0.013 (2)	0.0077 (19)	0.004 (2)
C27	0.020 (2)	0.041 (3)	0.039 (3)	0.012 (2)	0.003 (2)	0.004 (2)
C28	0.023 (2)	0.044 (3)	0.051 (3)	0.020 (2)	0.019 (2)	0.020 (2)
C29	0.038 (3)	0.060 (3)	0.046 (3)	0.031 (3)	0.025 (2)	0.013 (3)
C30	0.021 (2)	0.044 (3)	0.030 (2)	0.017 (2)	0.0062 (18)	0.004 (2)

Geometric parameters (Å, º) top

Co1—O4	2.070 (3)	C6—C7	1.376 (7)
Co1—O5	2.080 (3)	C6—H6A	0.9500
Co1—N2	2.179 (3)	C7—C8	1.377 (9)
Co1—N1	2.180 (3)	C7—H7A	0.9500
Co1—N4	2.183 (3)	C8—C9	1.356 (9)
Co1—N3	2.185 (3)	C8—H8A	0.9500
Co2—N6	2.104 (3)	C9—C10	1.398 (6)
Co2—O7	2.113 (3)	C9—H9A	0.9500
Co2—N5	2.123 (3)	C10—H10A	0.9500
Co2—O3ⁱ	2.141 (3)	C11—C12	1.385 (6)
Co2—O1ⁱ	2.185 (3)	C11—H11A	0.9500
Co2—O8	2.208 (3)	C12—C13	1.375 (7)
Co2—S1ⁱ	2.7061 (11)	C12—H12A	0.9500
Co2—S2	2.7107 (10)	C13—C14	1.370 (7)
S1—O2	1.450 (3)	C13—H13A	0.9500
S1—O4	1.476 (3)	C14—C15	1.378 (7)
S1—O1	1.483 (3)	C14—H14A	0.9500
S1—O3	1.493 (3)	C15—H15A	0.9500
S1—Co2ⁱⁱ	2.7062 (11)	C16—C17	1.384 (7)
S2—O6	1.451 (3)	C16—H16A	0.9500
S2—O5	1.477 (3)	C17—C18	1.379 (8)
S2—O8	1.488 (3)	C17—H17A	0.9500
S2—O7	1.500 (3)	C18—C19	1.372 (8)
O1—Co2ⁱⁱ	2.185 (3)	C18—H18A	0.9500
O3—Co2ⁱⁱ	2.141 (3)	C19—C20	1.383 (6)
N1—C5	1.337 (6)	C19—H19A	0.9500
N1—C1	1.337 (6)	C20—H20A	0.9500
N2—C10	1.333 (6)	C21—C22	1.383 (7)
N2—C6	1.355 (6)	C21—H21A	0.9500
N3—C15	1.340 (5)	C22—C23	1.364 (9)
N3—C11	1.344 (5)	C22—H22A	0.9500
N4—C16	1.339 (6)	C23—C24	1.383 (9)
N4—C20	1.340 (6)	C23—H23A	0.9500
N5—C25	1.331 (6)	C24—C25	1.379 (7)
N5—C21	1.344 (6)	C24—H24A	0.9500
N6—C30	1.331 (6)	C25—H25A	0.9500
N6—C26	1.340 (6)	C26—C27	1.381 (7)
C1—C2	1.388 (6)	C26—H26A	0.9500
C1—H1A	0.9500	C27—C28	1.380 (8)
C2—C3	1.384 (8)	C27—H27A	0.9500
C2—H2A	0.9500	C28—C29	1.378 (8)
C3—C4	1.395 (8)	C28—H28A	0.9500
C3—H3A	0.9500	C29—C30	1.393 (7)
C4—C5	1.378 (7)	C29—H29A	0.9500
C4—H4A	0.9500	C30—H30A	0.9500
C5—H5A	0.9500

O4—Co1—O5	173.43 (12)	C2—C1—H1A	118.3
O4—Co1—N2	85.60 (13)	C3—C2—C1	118.7 (4)
O5—Co1—N2	87.84 (12)	C3—C2—H2A	120.6
O4—Co1—N1	89.17 (13)	C1—C2—H2A	120.6
O5—Co1—N1	90.86 (12)	C2—C3—C4	117.9 (4)
N2—Co1—N1	87.48 (13)	C2—C3—H3A	121.0
O4—Co1—N4	96.45 (12)	C4—C3—H3A	121.0
O5—Co1—N4	90.12 (12)	C5—C4—C3	119.4 (5)
N2—Co1—N4	177.57 (14)	C5—C4—H4A	120.3
N1—Co1—N4	91.24 (12)	C3—C4—H4A	120.3
O4—Co1—N3	91.19 (13)	N1—C5—C4	122.9 (4)
O5—Co1—N3	88.85 (12)	N1—C5—H5A	118.5
N2—Co1—N3	93.18 (12)	C4—C5—H5A	118.5
N1—Co1—N3	179.27 (14)	N2—C6—C7	122.5 (5)
N4—Co1—N3	88.08 (12)	N2—C6—H6A	118.8
N6—Co2—O7	92.49 (12)	C7—C6—H6A	118.8
N6—Co2—N5	93.63 (13)	C6—C7—C8	119.6 (5)
O7—Co2—N5	98.33 (13)	C6—C7—H7A	120.2
N6—Co2—O3ⁱ	96.90 (13)	C8—C7—H7A	120.2
O7—Co2—O3ⁱ	162.62 (11)	C9—C8—C7	118.4 (5)
N5—Co2—O3ⁱ	95.64 (12)	C9—C8—H8A	120.8
N6—Co2—O1ⁱ	93.88 (13)	C7—C8—H8A	120.8
O7—Co2—O1ⁱ	98.98 (11)	C8—C9—C10	119.8 (5)
N5—Co2—O1ⁱ	160.79 (12)	C8—C9—H9A	120.1
O3ⁱ—Co2—O1ⁱ	65.90 (10)	C10—C9—H9A	120.1
N6—Co2—O8	158.65 (12)	N2—C10—C9	122.3 (5)
O7—Co2—O8	66.37 (10)	N2—C10—H10A	118.8
N5—Co2—O8	92.48 (13)	C9—C10—H10A	118.8
O3ⁱ—Co2—O8	102.84 (11)	N3—C11—C12	123.2 (4)
O1ⁱ—Co2—O8	86.87 (11)	N3—C11—H11A	118.4
N6—Co2—S1ⁱ	101.38 (10)	C12—C11—H11A	118.4
O7—Co2—S1ⁱ	130.13 (8)	C13—C12—C11	118.9 (4)
N5—Co2—S1ⁱ	127.73 (10)	C13—C12—H12A	120.6
O3ⁱ—Co2—S1ⁱ	33.37 (7)	C11—C12—H12A	120.6
O1ⁱ—Co2—S1ⁱ	33.18 (8)	C14—C13—C12	118.5 (4)
O8—Co2—S1ⁱ	90.91 (8)	C14—C13—H13A	120.8
N6—Co2—S2	125.39 (10)	C12—C13—H13A	120.8
O7—Co2—S2	33.41 (8)	C13—C14—C15	119.6 (5)
N5—Co2—S2	99.84 (10)	C13—C14—H14A	120.2
O3ⁱ—Co2—S2	133.35 (8)	C15—C14—H14A	120.2
O1ⁱ—Co2—S2	90.12 (8)	N3—C15—C14	123.0 (4)
O8—Co2—S2	33.27 (7)	N3—C15—H15A	118.5
S1ⁱ—Co2—S2	110.52 (3)	C14—C15—H15A	118.5
O2—S1—O4	110.31 (18)	N4—C16—C17	123.2 (4)
O2—S1—O1	112.58 (19)	N4—C16—H16A	118.4
O4—S1—O1	109.17 (18)	C17—C16—H16A	118.4
O2—S1—O3	111.06 (18)	C18—C17—C16	119.4 (5)
O4—S1—O3	109.08 (18)	C18—C17—H17A	120.3
O1—S1—O3	104.45 (16)	C16—C17—H17A	120.3
O2—S1—Co2ⁱⁱ	117.43 (14)	C19—C18—C17	117.9 (4)
O4—S1—Co2ⁱⁱ	132.24 (12)	C19—C18—H18A	121.1
O1—S1—Co2ⁱⁱ	53.72 (11)	C17—C18—H18A	121.1
O3—S1—Co2ⁱⁱ	52.05 (12)	C18—C19—C20	119.5 (5)
O6—S2—O5	110.02 (17)	C18—C19—H19A	120.2
O6—S2—O8	112.20 (18)	C20—C19—H19A	120.2
O5—S2—O8	109.12 (17)	N4—C20—C19	123.2 (4)
O6—S2—O7	111.68 (18)	N4—C20—H20A	118.4
O5—S2—O7	108.93 (17)	C19—C20—H20A	118.4
O8—S2—O7	104.72 (17)	N5—C21—C22	123.3 (5)
O6—S2—Co2	120.94 (13)	N5—C21—H21A	118.4
O5—S2—Co2	128.99 (12)	C22—C21—H21A	118.4
O8—S2—Co2	54.46 (11)	C23—C22—C21	119.1 (5)
O7—S2—Co2	50.87 (11)	C23—C22—H22A	120.5
S1—O1—Co2ⁱⁱ	93.10 (14)	C21—C22—H22A	120.5
S1—O3—Co2ⁱⁱ	94.57 (14)	C22—C23—C24	118.2 (4)
S1—O4—Co1	159.38 (19)	C22—C23—H23A	120.9
S2—O5—Co1	169.67 (19)	C24—C23—H23A	120.9
S2—O7—Co2	95.72 (15)	C25—C24—C23	119.5 (5)
S2—O8—Co2	92.27 (14)	C25—C24—H24A	120.3
C5—N1—C1	117.6 (4)	C23—C24—H24A	120.3
C5—N1—Co1	119.9 (3)	N5—C25—C24	123.0 (5)
C1—N1—Co1	122.6 (3)	N5—C25—H25A	118.5
C10—N2—C6	117.3 (4)	C24—C25—H25A	118.5
C10—N2—Co1	122.1 (3)	N6—C26—C27	122.9 (5)
C6—N2—Co1	120.6 (3)	N6—C26—H26A	118.5
C15—N3—C11	116.8 (4)	C27—C26—H26A	118.5
C15—N3—Co1	119.0 (3)	C28—C27—C26	119.1 (4)
C11—N3—Co1	124.2 (3)	C28—C27—H27A	120.4
C16—N4—C20	116.7 (4)	C26—C27—H27A	120.4
C16—N4—Co1	121.3 (3)	C29—C28—C27	118.7 (4)
C20—N4—Co1	121.9 (3)	C29—C28—H28A	120.7
C25—N5—C21	117.0 (4)	C27—C28—H28A	120.7
C25—N5—Co2	122.4 (3)	C28—C29—C30	118.5 (5)
C21—N5—Co2	120.4 (3)	C28—C29—H29A	120.7
C30—N6—C26	117.5 (4)	C30—C29—H29A	120.7
C30—N6—Co2	119.9 (3)	N6—C30—C29	123.2 (4)
C26—N6—Co2	122.3 (3)	N6—C30—H30A	118.4
N1—C1—C2	123.4 (4)	C29—C30—H30A	118.4
N1—C1—H1A	118.3

O2—S1—O1—Co2ⁱⁱ	108.27 (16)	Co1—N2—C10—C9	178.3 (4)
O4—S1—O1—Co2ⁱⁱ	−128.88 (15)	C8—C9—C10—N2	0.4 (9)
O3—S1—O1—Co2ⁱⁱ	−12.33 (17)	C15—N3—C11—C12	1.7 (6)
O2—S1—O3—Co2ⁱⁱ	−109.00 (18)	Co1—N3—C11—C12	−179.2 (3)
O4—S1—O3—Co2ⁱⁱ	129.22 (15)	N3—C11—C12—C13	−1.4 (7)
O1—S1—O3—Co2ⁱⁱ	12.61 (17)	C11—C12—C13—C14	−0.4 (7)
O2—S1—O4—Co1	1.7 (7)	C12—C13—C14—C15	1.6 (7)
O1—S1—O4—Co1	−122.5 (6)	C11—N3—C15—C14	−0.3 (6)
O3—S1—O4—Co1	124.0 (6)	Co1—N3—C15—C14	−179.5 (4)
Co2ⁱⁱ—S1—O4—Co1	179.6 (5)	C13—C14—C15—N3	−1.4 (7)
O6—S2—O5—Co1	−43.6 (11)	C20—N4—C16—C17	−1.2 (8)
O8—S2—O5—Co1	−167.1 (11)	Co1—N4—C16—C17	175.5 (4)
O7—S2—O5—Co1	79.2 (11)	N4—C16—C17—C18	0.4 (9)
Co2—S2—O5—Co1	133.7 (10)	C16—C17—C18—C19	1.7 (9)
O6—S2—O7—Co2	−112.94 (17)	C17—C18—C19—C20	−2.8 (9)
O5—S2—O7—Co2	125.34 (15)	C16—N4—C20—C19	0.0 (7)
O8—S2—O7—Co2	8.72 (18)	Co1—N4—C20—C19	−176.7 (4)
O6—S2—O8—Co2	113.01 (16)	C18—C19—C20—N4	2.0 (8)
O5—S2—O8—Co2	−124.80 (14)	C25—N5—C21—C22	−0.8 (8)
O7—S2—O8—Co2	−8.31 (17)	Co2—N5—C21—C22	174.2 (4)
C5—N1—C1—C2	−1.2 (6)	N5—C21—C22—C23	−0.5 (8)
Co1—N1—C1—C2	180.0 (3)	C21—C22—C23—C24	1.8 (8)
N1—C1—C2—C3	0.4 (7)	C22—C23—C24—C25	−1.9 (8)
C1—C2—C3—C4	1.2 (7)	C21—N5—C25—C24	0.7 (7)
C2—C3—C4—C5	−2.1 (7)	Co2—N5—C25—C24	−174.2 (4)
C1—N1—C5—C4	0.3 (7)	C23—C24—C25—N5	0.6 (8)
Co1—N1—C5—C4	179.2 (4)	C30—N6—C26—C27	2.0 (7)
C3—C4—C5—N1	1.3 (7)	Co2—N6—C26—C27	−171.6 (4)
C10—N2—C6—C7	−0.5 (7)	N6—C26—C27—C28	−0.1 (8)
Co1—N2—C6—C7	−178.9 (4)	C26—C27—C28—C29	−1.8 (8)
N2—C6—C7—C8	0.8 (9)	C27—C28—C29—C30	1.8 (8)
C6—C7—C8—C9	−0.5 (10)	C26—N6—C30—C29	−2.1 (7)
C7—C8—C9—C10	−0.1 (10)	Co2—N6—C30—C29	171.7 (4)
C6—N2—C10—C9	−0.1 (7)	C28—C29—C30—N6	0.2 (8)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O6	0.95	2.63	3.563 (6)	167
C2—H2A···O2ⁱⁱⁱ	0.95	2.52	3.219 (5)	131
C5—H5A···O4	0.95	2.42	3.009 (5)	120
C6—H6A···O5	0.95	2.56	3.054 (5)	112
C6—H6A···O7	0.95	2.47	3.322 (6)	149
C10—H10A···O4	0.95	2.53	3.010 (5)	112
C12—H12A···O7^iv	0.95	2.60	3.271 (5)	128
C15—H15A···O5	0.95	2.45	3.017 (5)	118
C16—H16A···O2	0.95	2.19	3.139 (6)	176
C20—H20A···O5	0.95	2.51	3.091 (5)	119
C20—H20A···O6	0.95	2.32	3.272 (5)	175
C25—H25A···O8	0.95	2.55	3.162 (5)	123
C30—H30A···O7	0.95	2.54	3.116 (5)	119

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

Funding information

Funding for this research was provided by: National Science Foundation, Directorate for Mathematical and Physical Sciences (grant No. CHE-1429086).

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