Synthesis and structure of hexa­aqua­cobalt bis­(2-methyl-1H-imidazol-3-ium) tetra­aqua­bis­(benzene-1,3,5-tri­carboxyl­ato-κO)cobalt

Velazquez-Garcia, J. de J.; Techert, S.

doi:10.1107/S2056989022007046

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 78| Part 8| August 2022| Pages 814-817

https://doi.org/10.1107/S2056989022007046

Open

access

Synthesis and structure of hexaaquacobalt bis(2-methyl-1H-imidazol-3-ium) tetraaquabis(benzene-1,3,5-tricarboxylato-κO)cobalt

Jose de Jesus Velazquez-Garcia ^a ^* and Simone Techert ^a,^b

^aDeutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22607 Hamburg, Germany, and ^bInstitut für Röntgenphysik, Georg-August-Universität Göttingen, Friedrich-Hund-Platz 1, Göttingen, 37077, Germany
^*Correspondence e-mail: jose.velazquez@desy.de

Edited by V. Jancik, Universidad Nacional Autónoma de México, México (Received 24 February 2022; accepted 9 July 2022; online 19 July 2022)

The title compound, (C₄H₇N₂)₂[Co(H₂O)₆][Co(C₉H₃O₆)₂(H₂O)₄] (1), was synthesized from cobalt(II) chloride, 1,3,5-benzene tricarboxylic acid (Hbtc) and 2-methyl-imidazole (H-2mIm) under ambient conditions. The structure of 1 is here reported and compared with the parent complex hexaaquacobalt bis(1H-imidazol-3-ium) tetraaquabis(benzene-1,3,5-tricarboxylato)cobalt (2).

Keywords: crystal structure; hexaaqua-cobalt; 2-methylimidazole; 1,3,5-benzene tricarboxylic acid.

CCDC reference: 2129637

1. Chemical context

Effective bifunctional electrocatalysts for oxygen reduction/evolution reactions (ORR/OER) are indispensable for the development of energy storage and conversion systems, such as fuel cells and rechargeable metal–air batteries (Cai et al., 2017 ; Wang et al., 2014 ). Currently, platinum-based materials are considered the most effective due to their superior catalytic activity and stability. However, their high cost, caused by the scarcity of the metal, rules them out for scale-up development. Therefore, a great deal of effort has been devoted to the development of cost-effective and earth-abundant replacements for platinum-based catalysts. Among the different substitute materials, a hexaaquacobalt bis(1H-imidazol-3-ium) tetraaquabis(benzene-1,3,5-tricarboxylato)cobalt complex, 2, has shown excellent bifunctional catalytic activity and durability for both the oxygen-reduction reaction and oxygen-evolution reaction in alkaline media (Wang et al., 2020 ). Unfortunately, the solvothermal synthesis required to produce the material hinders its implementation on a large scale.

Herein, we present the synthesis and structure of a hexaaquacobalt bis(1H-2-methyl-imidazol-3-ium) tetraaquabis(benzene-1,3,5-tricarboxylato)cobalt complex, a related material with the imidazolium cations replaced by 2-methylimidazolium, which can be obtained under ambient conditions. The introduction of the methyl substituent to the C₂ position of the imidazolium ring induces only small structural changes, when compared to 2, and therefore, the title compound could be a promising material for ORR and OER.

2. Structural commentary

The complete molecule of 1 (Fig. 1) is generated by a crystallographic centre of symmetry. Both Co-containing ions lie about an inversion centre, and therefore only half of the coordinating ions and molecules are crystallographically independent. One of the two metal centres (Co1) is coordinated by six water molecules to constitute a hexaaquacobalt cation, while the second (Co2) binds with four water molecules and two carboxylate oxygen atoms from two btc³⁻ ligands to form a [Co(H₂O)₄(btc)₂]⁴⁻ anion. Charge neutrality of the molecule is provided by the presence of two 1-H-2-methyl-imidazol-3-ium cations. The observed Co—O_carboxylate bond length is 2.0835 (9) Å and the C—O_water bond lengths are in the range 2.0576 (9)–2.1196 (9) Å. To estimate the distortion from the ideal octahedral geometry, the parameters Σ (Halcrow, 2011 ) and Θ (Marchivie et al., 2005 ) were calculated using the OctaDist program (Ketkaew et al., 2021 ). While Σ summarizes the deviation of the cis O—Cu—O angles from 90°, Θ indicates the degree of twist from a perfect octahedron towards a trigonal prism. Both parameters are equal to zero for an ideal octahedron. The calculated values of the distortion parameters Σ/Θ for Co1 and Co2 are equal to 19°/62° and 11°/31°, respectively. Both parameters indicate a slight distortion of the coordination environment of both metal centres.

Figure 1
The molecular structure of 1 with displacement ellipsoids drawn at the 50% probability level. Symmetry codes: (_a) 2 − x, −y, 2 − z; (_b) 2 − x, 1 − y, 1 − z.

3. Supramolecular features

A packing diagram of the compound as viewed down [ $[\overline{1}]$ 01] is shown in Fig. 2. The figure shows layers parallel to the (111) plane formed by all ions. Each ion interacts with others via hydrogen bonds of the O—H⋯O or N—H⋯O type. A summary of the hydrogen-bonding interactions is given in Table 1. The table demonstrates that all possible donor and acceptor groups are involved in moderate hydrogen bonds. The presence of various hydrogen bonds in 1 results in characteristic arrays that may be described by graph-set analysis (Etter et al., 1990 ; Bernstein et al., 1995 ). In the structure of 1, there are 27 possible motifs involved in discrete D (types a–f and k–l) and intermolecular S (type h) motifs, as well as rings R (types g, i and j) and chains C (types a–f). It is worth noting that while hydrogen bonds b, c and i hold the aforementioned layers together through C₂²(20) and D arrays, other hydrogen bonds, such as type a and e, form C₂²(20) arrays, which generates a three-dimensional network with channels along the a and c axes in which the imidazolium ions are located (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	Type	Graph-set	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9A⋯O4	a	DC²₂(20)	0.785 (12)	1.850 (12)	2.6339 (12)	176.4 (19)
O9—H9B⋯O7^iv	b	DC²₂(20)	0.775 (12)	1.957 (12)	2.7150 (13)	165.9 (18)
O10—H10A⋯O7ⁱⁱ	c	DC²₂(20)	0.791 (12)	2.085 (12)	2.8592 (13)	166.1 (17)
O10—H10B⋯O6ⁱⁱⁱ	d	DC²₂(20)	0.793 (12)	1.891 (12)	2.6835 (12)	176.3 (18)
O11—H11A⋯O8^v	e	DC²₂(20)	0.778 (12)	1.919 (13)	2.6911 (13)	171.6 (18)
O11—H11B⋯O5^vi	f	DC²₂(20)	0.809 (17)	1.896 (18)	2.6989 (13)	172.0 (17)
O1—H1A⋯O7ⁱ	g	C(10) C₂²(20) R₂²(20)	0.787 (12)	2.096 (12)	2.8789 (13)	173.5 (19)
O1—H1B⋯O4	h	S(6)	0.785 (12)	1.904 (13)	2.6401 (13)	155.8 (18)
O2—H2A⋯O5ⁱⁱ	i	C(10) C₂²(20) R₂²(20)	0.778 (12)	2.175 (13)	2.9371 (13)	166.5 (19)
O2—H2B⋯O6ⁱⁱⁱ	j	C(10) C₂²(20) R₂²(20)	0.783 (12)	1.965 (12)	2.7458 (13)	175 (2)
N1—H1⋯O8^iv	k	DD²₂(17)	0.913 (15)	1.811 (15)	2.7214 (13)	174.6 (16)
N2—H2⋯O5^vii	l	DD²₂(17)	0.890 (15)	1.931 (15)	2.8206 (14)	178.0 (17)
Symmetry codes: (i) x + 1, y − 1, z; (ii) x + 1, y, z; (iii) −x + 1, −y + 1, −z + 2; (iv) −x + 1, −y + 1, −z + 1; (v) −x + 2, −y + 1, −z + 1; (vi) x + 1, y, z − 1; (vii) −x + 1, −y, −z + 2.

Figure 2
Packing diagram of 1 down the [ $[\overline{1}]$ 01] direction. O—H⋯O hydrogen bonds of type b, c and i are shown in the magnified region.

Figure 3
The three-dimensional supramolecular network with one-dimensional channels along the (a) a and (b) c axes showing O—H⋯O hydrogen bonds of type a and e in the magnified area. Imidazolium ions are drawn in green for clarity.

4. Database survey

A search of the Cambridge Structural Database (CSD version 5.41, update of August 2020; Groom et al., 2016 ) for hexaaquacobalt and the ditrimesate tetraaquacobalt moiety revealed only one hit, namely refcode: VUHQIA (imidazolium)₂[Co(H₂O)₆][Co(H₂O)₄(btc)₂], 2, (Wang et al., 2020). Compounds 1 and 2 crystallize in the triclinic system, space group P $[\overline{1}]$ . The Co—O_carboxylate and C—O_water bond lengths are similar in both complexes. The coordination polyhedra of compound 2 are slightly more distorted. The calculated values of Σ/Θ for compound 2 are equal to 21°/63° for Co1 and 10°/39° for Co2 – that is, the trigonal distortion (Θ) in 2 is higher by 1 and 8° for Co1 and Co2, respectively. The slightly different distortion of the metal centres in 2 and the introduction of the imidazolium allow for shorter hydrogen bonds with distances between 1.73 and 2.00 Å. Other complexes with a low degree of similarity to the title compound were also found, for example refcodes DOWFUS (Clegg & Holcroft, 2014 ), IQOZUK (Li et al., 2011 ) and SETQOX (Wolodkiewicz et al., 1996 ). However, these compounds are polymeric and/or incorporate a different organic ligand than btc. Additionally, none of them contain the imidazolium anion. These changes in chemical composition may provide them with totally different properties than those desired for ORR and OER, and therefore, they will not be discussed further.

5. Synthesis and crystallization

In a typical synthesis, H-2mIm (160 mg, 1.96 mmol), Hbtc (412, 1.96 mmol) and cobalt chloride (127 mg, 0.95mmol) were dissolved in 160 ml of a 1:1:1 mixture of deionized water, ethanol and dimethylformamide by stirring for 10 min at room temperature. After 5 minutes, light-pink crystals of 1 were obtained. The product was collected by filtration and washed three times with ethanol.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Positions of remaining non-H atoms were found from the electron density difference maps. The positions of hydrogen atoms were refined with U_iso(H) = 1.5U_eq(C or N) for CH and NH groups and U_iso(H) = 1.5U_eq(C or O) for others. The O—H and H⋯H distances in the water molecules as well as the N—H distances were restrained to be approximately equal within each type (SHELXL instruction SADI). The protons of the methyl group were refined as disordered over two geometrically idealized positions.

Table 2
Experimental details

Crystal data
Chemical formula	(C₄H₇N₂)₂[Co(H₂O)₆][Co(C₉H₃O₆)₂(H₂O)₄]
M_r	878.48
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	9.2008 (4), 9.3137 (4), 10.6470 (4)
α, β, γ (°)	86.551 (2), 79.378 (2), 72.369 (2)
V (Å³)	854.61 (6)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	1.07
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker CCD area detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.699, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	26203, 5250, 4605
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.719

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.069, 1.04
No. of reflections	5250
No. of parameters	285
No. of restraints	47
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.42
Computer programs: APEX2 and SAINT (Bruker, 2016 ), SHELXT2018/2 (Sheldrick, 2018 ), SHELXL2019/2 (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2129637

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022007046/jq2016sup1.cif

checkcif file. DOI: https://doi.org/10.1107/S2056989022007046/jq2016sup4.pdf

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022007046/jq2016Isup6.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2018); program(s) used to refine structure: SHELXL2019/2 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Hexaaquacobalt bis(2-methyl-1H-imidazol-3-ium) tetraaquabis(benzene-1,3,5-tricarboxylato-κO)cobalt top

Crystal data top

(C₄H₇N₂)₂[Co(H₂O)₆][Co(C₉H₃O₆)₂(H₂O)₄]	Z = 1
M_r = 878.48	F(000) = 454
Triclinic, P1	D_x = 1.707 Mg m⁻³
a = 9.2008 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.3137 (4) Å	Cell parameters from 9913 reflections
c = 10.6470 (4) Å	θ = 2.3–30.6°
α = 86.551 (2)°	µ = 1.07 mm⁻¹
β = 79.378 (2)°	T = 296 K
γ = 72.369 (2)°	Prism, clear light pink
V = 854.61 (6) Å³	0.20 × 0.10 × 0.10 mm

Data collection top

Bruker CCD area detector diffractometer	4605 reflections with I > 2σ(I)
phi and ω scans	R_int = 0.026
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 30.7°, θ_min = 2.0°
T_min = 0.699, T_max = 0.746	h = −13→13
26203 measured reflections	k = −13→12
5250 independent reflections	l = −15→14

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	Secondary atom site location: dual
R[F² > 2σ(F²)] = 0.026	Hydrogen site location: mixed
wR(F²) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0331P)² + 0.4935P] where P = (F_o² + 2F_c²)/3
5250 reflections	(Δ/σ)_max < 0.001
285 parameters	Δρ_max = 0.60 e Å⁻³
47 restraints	Δρ_min = −0.42 e Å⁻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	Occ. (<1)
Co1	1.000000	0.500000	0.500000	0.00661 (6)
Co2	1.000000	0.000000	1.000000	0.00734 (6)
O1	1.09226 (11)	−0.04186 (11)	0.80639 (9)	0.01446 (19)
H1A	1.128 (2)	−0.1158 (16)	0.7654 (16)	0.022*
H1B	1.0319 (19)	0.0150 (17)	0.7699 (17)	0.022*
O2	1.06874 (11)	0.19677 (11)	0.98183 (10)	0.01395 (18)
H2A	1.107 (2)	0.215 (2)	1.0361 (15)	0.021*
H2B	1.0153 (19)	0.2726 (17)	0.9590 (17)	0.021*
O3	0.78549 (10)	0.12296 (10)	0.95554 (8)	0.01077 (17)
O4	0.85774 (10)	0.18407 (10)	0.75266 (8)	0.01246 (18)
O5	0.23219 (10)	0.29950 (10)	1.15378 (8)	0.01007 (16)
O6	0.10354 (10)	0.53500 (10)	1.10793 (8)	0.01151 (17)
O7	0.24698 (10)	0.69230 (10)	0.65394 (8)	0.00982 (16)
O8	0.49974 (10)	0.65513 (10)	0.58167 (8)	0.01243 (18)
O9	0.91967 (10)	0.31282 (10)	0.53041 (9)	0.01031 (17)
H9A	0.898 (2)	0.278 (2)	0.5975 (12)	0.015*
H9B	0.8655 (19)	0.302 (2)	0.4862 (14)	0.015*
O10	1.09204 (10)	0.46619 (10)	0.67157 (8)	0.00996 (16)
H10A	1.1344 (18)	0.5265 (17)	0.6797 (16)	0.015*
H10B	1.0313 (17)	0.4689 (19)	0.7355 (13)	0.015*
O11	1.20606 (10)	0.36656 (11)	0.40161 (9)	0.01061 (17)
H11A	1.2898 (16)	0.368 (2)	0.4028 (16)	0.016*
H11B	1.2048 (19)	0.350 (2)	0.3281 (17)	0.016*
N1	0.50458 (13)	0.14060 (12)	0.61249 (10)	0.0119 (2)
H1	0.510 (2)	0.2077 (18)	0.5469 (15)	0.014*
N2	0.57535 (12)	−0.03974 (12)	0.74458 (10)	0.0119 (2)
H2	0.6351 (19)	−0.1208 (18)	0.7785 (16)	0.014*
C1	0.76058 (13)	0.19797 (13)	0.85484 (11)	0.0081 (2)
C2	0.60272 (13)	0.31087 (13)	0.85916 (11)	0.0074 (2)
C3	0.57120 (13)	0.41453 (13)	0.76032 (11)	0.0082 (2)
H3	0.647875	0.413232	0.689599	0.010*
C4	0.42546 (13)	0.52015 (13)	0.76680 (11)	0.0079 (2)
C5	0.31078 (13)	0.52211 (13)	0.87313 (11)	0.0082 (2)
H5	0.213899	0.593210	0.878284	0.010*
C6	0.34094 (13)	0.41785 (13)	0.97165 (11)	0.0076 (2)
C7	0.48664 (13)	0.31248 (13)	0.96411 (11)	0.0081 (2)
H7	0.506641	0.242605	1.029673	0.010*
C8	0.21698 (13)	0.41903 (13)	1.08554 (11)	0.0078 (2)
C9	0.38899 (13)	0.63054 (13)	0.65934 (11)	0.0081 (2)
C10	0.37595 (15)	0.14698 (15)	0.70562 (13)	0.0143 (2)
H10	0.277987	0.216042	0.710213	0.017*
C11	0.42065 (15)	0.03308 (15)	0.78863 (12)	0.0137 (2)
H11	0.359239	0.008535	0.861228	0.016*
C12	0.62411 (14)	0.02705 (14)	0.63723 (12)	0.0110 (2)
C13	0.78039 (15)	−0.01811 (15)	0.55720 (13)	0.0156 (2)
H13A	0.806962	−0.121788	0.533113	0.023*	0.58 (5)
H13B	0.854729	−0.005633	0.604826	0.023*	0.58 (5)
H13C	0.780728	0.043824	0.481802	0.023*	0.58 (5)
H13D	0.804580	0.069870	0.519273	0.023*	0.42 (5)
H13E	0.782325	−0.084695	0.491083	0.023*	0.42 (5)
H13F	0.855513	−0.068771	0.609385	0.023*	0.42 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.00602 (10)	0.00746 (11)	0.00589 (10)	−0.00185 (8)	−0.00054 (7)	0.00102 (7)
Co2	0.00718 (10)	0.00685 (11)	0.00737 (10)	−0.00111 (8)	−0.00184 (7)	0.00140 (8)
O1	0.0144 (4)	0.0133 (5)	0.0109 (4)	0.0036 (4)	−0.0031 (3)	−0.0002 (3)
O2	0.0155 (4)	0.0092 (4)	0.0193 (5)	−0.0037 (3)	−0.0097 (4)	0.0036 (3)
O3	0.0100 (4)	0.0115 (4)	0.0088 (4)	−0.0005 (3)	−0.0021 (3)	0.0035 (3)
O4	0.0111 (4)	0.0131 (4)	0.0089 (4)	0.0006 (3)	0.0006 (3)	0.0034 (3)
O5	0.0123 (4)	0.0081 (4)	0.0085 (4)	−0.0021 (3)	−0.0008 (3)	0.0027 (3)
O6	0.0101 (4)	0.0103 (4)	0.0105 (4)	0.0001 (3)	0.0013 (3)	0.0021 (3)
O7	0.0078 (4)	0.0110 (4)	0.0099 (4)	−0.0013 (3)	−0.0029 (3)	0.0019 (3)
O8	0.0091 (4)	0.0151 (4)	0.0116 (4)	−0.0030 (3)	−0.0012 (3)	0.0066 (3)
O9	0.0123 (4)	0.0129 (4)	0.0077 (4)	−0.0067 (3)	−0.0029 (3)	0.0038 (3)
O10	0.0089 (4)	0.0138 (4)	0.0077 (4)	−0.0047 (3)	−0.0011 (3)	0.0016 (3)
O11	0.0077 (4)	0.0144 (4)	0.0092 (4)	−0.0028 (3)	−0.0006 (3)	−0.0009 (3)
N1	0.0147 (5)	0.0096 (5)	0.0111 (5)	−0.0029 (4)	−0.0036 (4)	0.0030 (4)
N2	0.0116 (5)	0.0096 (5)	0.0127 (5)	−0.0012 (4)	−0.0017 (4)	0.0031 (4)
C1	0.0081 (5)	0.0075 (5)	0.0086 (5)	−0.0020 (4)	−0.0021 (4)	0.0009 (4)
C2	0.0073 (5)	0.0067 (5)	0.0080 (5)	−0.0016 (4)	−0.0021 (4)	0.0004 (4)
C3	0.0082 (5)	0.0083 (5)	0.0079 (5)	−0.0026 (4)	−0.0014 (4)	0.0011 (4)
C4	0.0089 (5)	0.0084 (5)	0.0068 (5)	−0.0033 (4)	−0.0020 (4)	0.0018 (4)
C5	0.0081 (5)	0.0082 (5)	0.0082 (5)	−0.0022 (4)	−0.0018 (4)	0.0005 (4)
C6	0.0084 (5)	0.0079 (5)	0.0066 (5)	−0.0028 (4)	−0.0010 (4)	0.0007 (4)
C7	0.0095 (5)	0.0073 (5)	0.0074 (5)	−0.0022 (4)	−0.0024 (4)	0.0014 (4)
C8	0.0086 (5)	0.0094 (5)	0.0067 (5)	−0.0039 (4)	−0.0027 (4)	0.0005 (4)
C9	0.0099 (5)	0.0072 (5)	0.0077 (5)	−0.0025 (4)	−0.0026 (4)	0.0003 (4)
C10	0.0121 (5)	0.0126 (6)	0.0171 (6)	−0.0020 (4)	−0.0028 (4)	0.0015 (5)
C11	0.0123 (5)	0.0136 (6)	0.0134 (6)	−0.0030 (5)	0.0000 (4)	0.0017 (4)
C12	0.0140 (5)	0.0082 (5)	0.0113 (5)	−0.0042 (4)	−0.0022 (4)	0.0005 (4)
C13	0.0148 (6)	0.0137 (6)	0.0168 (6)	−0.0046 (5)	0.0023 (5)	−0.0015 (5)

Geometric parameters (Å, º) top

Co1—O11	2.0576 (9)	N1—C12	1.3289 (16)
Co1—O11ⁱ	2.0576 (9)	N1—C10	1.3854 (16)
Co1—O9ⁱ	2.0772 (9)	N1—H1	0.913 (15)
Co1—O9	2.0772 (9)	N2—C12	1.3375 (15)
Co1—O10	2.1196 (9)	N2—C11	1.3832 (16)
Co1—O10ⁱ	2.1196 (9)	N2—H2	0.890 (15)
Co2—O3ⁱⁱ	2.0835 (9)	C1—C2	1.5078 (16)
Co2—O3	2.0835 (9)	C2—C7	1.3934 (15)
Co2—O1ⁱⁱ	2.0912 (9)	C2—C3	1.3944 (16)
Co2—O1	2.0912 (9)	C3—C4	1.3948 (16)
Co2—O2ⁱⁱ	2.1000 (9)	C3—H3	0.9300
Co2—O2	2.1000 (9)	C4—C5	1.3949 (15)
O1—H1A	0.787 (12)	C4—C9	1.5066 (16)
O1—H1B	0.785 (12)	C5—C6	1.3934 (15)
O2—H2A	0.778 (12)	C5—H5	0.9300
O2—H2B	0.783 (12)	C6—C7	1.3926 (16)
O3—C1	1.2624 (14)	C6—C8	1.5019 (15)
O4—C1	1.2601 (14)	C7—H7	0.9300
O5—C8	1.2777 (14)	C10—C11	1.3537 (17)
O6—C8	1.2526 (15)	C10—H10	0.9300
O7—C9	1.2687 (14)	C11—H11	0.9300
O8—C9	1.2580 (14)	C12—C13	1.4818 (17)
O9—H9A	0.785 (12)	C13—H13A	0.9600
O9—H9B	0.775 (12)	C13—H13B	0.9600
O10—H10A	0.791 (12)	C13—H13C	0.9600
O10—H10B	0.793 (12)	C13—H13D	0.9600
O11—H11A	0.778 (12)	C13—H13E	0.9600
O11—H11B	0.809 (17)	C13—H13F	0.9600

O11—Co1—O11ⁱ	180.0	C7—C2—C3	119.40 (10)
O11—Co1—O9ⁱ	90.60 (4)	C7—C2—C1	119.49 (10)
O11ⁱ—Co1—O9ⁱ	89.40 (4)	C3—C2—C1	121.11 (10)
O11—Co1—O9	89.40 (4)	C2—C3—C4	120.45 (10)
O11ⁱ—Co1—O9	90.60 (4)	C2—C3—H3	119.8
O9ⁱ—Co1—O9	180.0	C4—C3—H3	119.8
O11—Co1—O10	90.76 (4)	C3—C4—C5	119.66 (10)
O11ⁱ—Co1—O10	89.24 (4)	C3—C4—C9	120.93 (10)
O9ⁱ—Co1—O10	86.64 (3)	C5—C4—C9	119.40 (10)
O9—Co1—O10	93.36 (4)	C6—C5—C4	120.20 (11)
O11—Co1—O10ⁱ	89.24 (4)	C6—C5—H5	119.9
O11ⁱ—Co1—O10ⁱ	90.76 (4)	C4—C5—H5	119.9
O9ⁱ—Co1—O10ⁱ	93.36 (3)	C7—C6—C5	119.71 (10)
O9—Co1—O10ⁱ	86.64 (4)	C7—C6—C8	120.09 (10)
O10—Co1—O10ⁱ	180.0	C5—C6—C8	120.19 (10)
O3ⁱⁱ—Co2—O3	180.00 (5)	C6—C7—C2	120.56 (10)
O3ⁱⁱ—Co2—O1ⁱⁱ	90.97 (4)	C6—C7—H7	119.7
O3—Co2—O1ⁱⁱ	89.03 (4)	C2—C7—H7	119.7
O3ⁱⁱ—Co2—O1	89.03 (4)	O6—C8—O5	123.36 (11)
O3—Co2—O1	90.97 (4)	O6—C8—C6	118.94 (10)
O1ⁱⁱ—Co2—O1	180.0	O5—C8—C6	117.70 (10)
O3ⁱⁱ—Co2—O2ⁱⁱ	89.79 (4)	O8—C9—O7	124.60 (11)
O3—Co2—O2ⁱⁱ	90.21 (4)	O8—C9—C4	118.45 (10)
O1ⁱⁱ—Co2—O2ⁱⁱ	88.38 (4)	O7—C9—C4	116.95 (10)
O1—Co2—O2ⁱⁱ	91.62 (4)	C11—C10—N1	106.62 (11)
O3ⁱⁱ—Co2—O2	90.21 (4)	C11—C10—H10	126.7
O3—Co2—O2	89.79 (4)	N1—C10—H10	126.7
O1ⁱⁱ—Co2—O2	91.62 (4)	C10—C11—N2	106.72 (11)
O1—Co2—O2	88.38 (4)	C10—C11—H11	126.6
O2ⁱⁱ—Co2—O2	180.0	N2—C11—H11	126.6
Co2—O1—H1A	133.6 (14)	N1—C12—N2	107.33 (11)
Co2—O1—H1B	104.8 (13)	N1—C12—C13	125.58 (11)
H1A—O1—H1B	107.5 (16)	N2—C12—C13	127.07 (11)
Co2—O2—H2A	117.6 (14)	C12—C13—H13A	109.5
Co2—O2—H2B	121.0 (13)	C12—C13—H13B	109.5
H2A—O2—H2B	108.3 (16)	H13A—C13—H13B	109.5
C1—O3—Co2	126.90 (8)	C12—C13—H13C	109.5
Co1—O9—H9A	125.1 (13)	H13A—C13—H13C	109.5
Co1—O9—H9B	117.8 (13)	H13B—C13—H13C	109.5
H9A—O9—H9B	108.5 (16)	C12—C13—H13D	109.5
Co1—O10—H10A	111.8 (12)	H13A—C13—H13D	135.3
Co1—O10—H10B	115.7 (13)	H13B—C13—H13D	76.7
H10A—O10—H10B	106.0 (15)	H13C—C13—H13D	35.5
Co1—O11—H11A	128.6 (13)	C12—C13—H13E	109.5
Co1—O11—H11B	114.9 (12)	H13A—C13—H13E	35.5
H11A—O11—H11B	105.6 (16)	H13B—C13—H13E	135.3
C12—N1—C10	109.77 (10)	H13C—C13—H13E	76.7
C12—N1—H1	124.4 (11)	H13D—C13—H13E	109.5
C10—N1—H1	125.7 (11)	C12—C13—H13F	109.5
C12—N2—C11	109.55 (11)	H13A—C13—H13F	76.7
C12—N2—H2	123.4 (11)	H13B—C13—H13F	35.5
C11—N2—H2	127.0 (11)	H13C—C13—H13F	135.3
O4—C1—O3	124.51 (11)	H13D—C13—H13F	109.5
O4—C1—C2	118.73 (10)	H13E—C13—H13F	109.5
O3—C1—C2	116.76 (10)

Co2—O3—C1—O4	16.76 (18)	C1—C2—C7—C6	178.56 (11)
Co2—O3—C1—C2	−163.49 (8)	C7—C6—C8—O6	161.30 (11)
O4—C1—C2—C7	170.61 (11)	C5—C6—C8—O6	−18.68 (17)
O3—C1—C2—C7	−9.15 (17)	C7—C6—C8—O5	−19.76 (17)
O4—C1—C2—C3	−9.89 (17)	C5—C6—C8—O5	160.27 (11)
O3—C1—C2—C3	170.35 (11)	C3—C4—C9—O8	−19.45 (17)
C7—C2—C3—C4	0.72 (18)	C5—C4—C9—O8	161.70 (11)
C1—C2—C3—C4	−178.78 (11)	C3—C4—C9—O7	160.47 (11)
C2—C3—C4—C5	0.16 (18)	C5—C4—C9—O7	−18.38 (17)
C2—C3—C4—C9	−178.68 (11)	C12—N1—C10—C11	−0.03 (15)
C3—C4—C5—C6	−0.83 (18)	N1—C10—C11—N2	0.19 (15)
C9—C4—C5—C6	178.03 (11)	C12—N2—C11—C10	−0.29 (15)
C4—C5—C6—C7	0.61 (18)	C10—N1—C12—N2	−0.15 (15)
C4—C5—C6—C8	−179.42 (11)	C10—N1—C12—C13	178.19 (12)
C5—C6—C7—C2	0.29 (18)	C11—N2—C12—N1	0.27 (15)
C8—C6—C7—C2	−179.69 (11)	C11—N2—C12—C13	−178.04 (13)
C3—C2—C7—C6	−0.95 (18)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O7ⁱⁱⁱ	0.79 (1)	2.10 (1)	2.8789 (13)	174 (2)
O1—H1B···O4	0.79 (1)	1.90 (1)	2.6401 (13)	156 (2)
O2—H2A···O5^iv	0.78 (1)	2.17 (1)	2.9371 (13)	167 (2)
O2—H2B···O6^v	0.78 (1)	1.97 (1)	2.7458 (13)	175 (2)
O9—H9A···O4	0.79 (1)	1.85 (1)	2.6339 (12)	176 (2)
O9—H9B···O7^vi	0.78 (1)	1.96 (1)	2.7150 (13)	166 (2)
O10—H10A···O7^iv	0.79 (1)	2.09 (1)	2.8592 (13)	166 (2)
O10—H10B···O6^v	0.79 (1)	1.89 (1)	2.6835 (12)	176 (2)
O11—H11A···O8ⁱ	0.78 (1)	1.92 (1)	2.6911 (13)	172 (2)
O11—H11B···O5^vii	0.81 (2)	1.90 (2)	2.6989 (13)	172 (2)
N1—H1···O8^vi	0.91 (2)	1.81 (2)	2.7214 (13)	175 (2)
N2—H2···O5^viii	0.89 (2)	1.93 (2)	2.8206 (14)	178 (2)

Symmetry codes: (i) −x+2, −y+1, −z+1; (iii) x+1, y−1, z; (iv) x+1, y, z; (v) −x+1, −y+1, −z+2; (vi) −x+1, −y+1, −z+1; (vii) x+1, y, z−1; (viii) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, °) top

D—H···A	Type	Graph-set	D—H	H···A	D···A	D—H···A
O9—H9A···O4	a	DC²₂(20)	0.785 (12)	1.850 (12)	2.6339 (12)	176.4 (19)
O9—H9B···O7^iv	b	DC²₂(20)	0.775 (12)	1.957 (12)	2.7150 (13)	165.9 (18)
O10—H10A···O7ⁱⁱ	c	DC²₂(20)	0.791 (12)	2.085 (12)	2.8592 (13)	166.1 (17)
O10—H10B···O6ⁱⁱⁱ	d	DC²₂(20)	0.793 (12)	1.891 (12)	2.6835 (12)	176.3 (18)
O11—H11A···O8^v	e	DC²₂(20)	0.778 (12)	1.919 (13)	2.6911 (13)	171.6 (18)
O11—H11B···O5^vi	f	DC²₂(20)	0.809 (17)	1.896 (18)	2.6989 (13)	172.0 (17)
O1—H1A···O7ⁱ	g	C(10)C²₂(20)R²₂(20)	0.787 (12)	2.096 (12)	2.8789 (13)	173.5 (19)
O1—H1B···O4	h	S(6)	0.785 (12)	1.904 (13)	2.6401 (13)	155.8 (18)
O2—H2A···O5ⁱⁱ	i	C(10)C²₂(20)R²₂(20)	0.778 (12)	2.175 (13)	2.9371 (13)	166.5 (19)
O2—H2B···O6ⁱⁱⁱ	j	C(10)C²₂(20)R²₂(20)	0.783 (12)	1.965 (12)	2.7458 (13)	175 (2)
N1—H1···O8^iv	k	DD²₂(17)	0.913 (15)	1.811 (15)	2.7214 (13)	174.6 (16)
N2—H2···O5^vii	l	DD²₂(17)	0.890 (15)	1.931 (15)	2.8206 (14)	178.0 (17)

Symmetry codes: (i) x + 1, y - 1, z; (ii) x + 1, y, z; (iii) -x + 1, -y + 1, -z + 2; (iv) -x + 1, -y + 1, -z + 1; (v) -x + 2, -y + 1, -z + 1; (vi) x + 1, y, z - 1; (vii) -x + 1, -y, -z + 2.

Funding information

Funding for this research was provided by: HG-recruitment, HG-Innovation "ECRAPS", HG-Innovation DSF, DASHH, DGP and CMWS (grant to Simone Techert).

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2016). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cai, X., Lai, L., Lin, J. & Shen, Z. (2017). Mater. Horiz. 4, 945–976. CrossRef CAS Google Scholar
Clegg, W. & Holcroft, J. M. (2014). Cryst. Growth Des. 14, 6282–6293. Web of Science CrossRef CAS Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef ICSD CAS Web of Science IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Halcrow, M. A. (2011). Chem. Soc. Rev. 40, 4119–4142. Web of Science CrossRef CAS PubMed Google Scholar
Ketkaew, R., Tantirungrotechai, Y., Harding, P., Chastanet, G., Guionneau, P., Marchivie, M. & Harding, D. J. (2021). Dalton Trans. 50, 1086–1096. CrossRef CAS PubMed Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Li, Y., Zou, W.-Q., Wu, M.-F., Lin, J.-D., Zheng, F.-K., Liu, Z.-F., Wang, S.-H., Guo, G.-C. & Huang, J.-S. (2011). CrystEngComm, 13, 3868–3877. CSD CrossRef CAS Google Scholar
Marchivie, M., Guionneau, P., Létard, J.-F. & Chasseau, D. (2005). Acta Cryst. B61, 25–28. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. (2018). Acta Cryst. A74, a353. CrossRef IUCr Journals Google Scholar
Wang, H., Zhang, X., Yin, F., Chu, W. & Chen, B. (2020). J. Mater. Chem. A, 8, 22111–22123. CSD CrossRef CAS Google Scholar
Wang, Z.-L., Xu, D., Xu, J.-J. & Zhang, X.-B. (2014). Chem. Soc. Rev. 43, 7746–7786. CrossRef CAS PubMed Google Scholar
Wolodkiewicz, W., Brzyska, W. & Glowiak, T. (1996). Pol. J. Chem. 70, 409–416. CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.