Crystal structure of tris­[hexa­kis­(imidazole)cobalt(II)] bis­(benzene-1,3,5-tri­carboxyl­ate)

Velazquez-Garcia, J. de J.; Bintas, C.; Khademhir, F.; Knjo, B.; Ekineken, A.; Hain, F.; Techert, S.

doi:10.1107/S2056989025010060

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ISSN: 2056-9890

Volume 81| Part 12| December 2025| Pages 1186-1188

https://doi.org/10.1107/S2056989025010060

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Crystal structure of tris[hexakis(imidazole)cobalt(II)] bis(benzene-1,3,5-tricarboxylate)

Jose de Jesus Velazquez-Garcia,^a ^* Christos Bintas,^a,^b Faegheh Khademhir,^a,^c Bassima Knjo,^a,^c Aliyenur Ekineken,^a,^c Fabienne Hain ^a,^c and Simone Techert ^a,^d

^aDeutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22607 Hamburg, Germany, ^bDepartment of Chemistry, National and Kapodistrian University of Athens (NKUA), Zografou 157 72, Greece, ^cBS 06 Berufliche Schule Chemie, Biologie, Pharmazie, Agrarwirtschaft, Ladenbeker, Furtweg 151, 21033 Hamburg, Germany, and ^dInstitut für Röntgenphysik, Georg-August-Universität Göttingen, Friedrich-Hund-Platz 1, 37077 Göttingen, Germany
^*Correspondence e-mail: [email protected]

Edited by V. Jancik, Universidad Nacional Autónoma de México, México (Received 24 September 2025; accepted 11 November 2025; online 25 November 2025)

The title compound, [Co^II(C₃H₄N₂)₆]₃(C₉H₃O₆)₂ (1), was synthesized from cobalt chloride(II), benzene-1,3,5-tricarboxylic acid (H₃btc) and imidazole (Im) in an ethanol/DMF mixture via slow evaporation at room temperature. This compound consists of three hexakis(imidazole)cobalt(II) cations and two trimesate anions. Examination of the crystal packing shows the formation of one-dimensional stacks of ions propagating along the c axis. The packing interactions are primarily driven by N—H⋯O hydrogen bonding between anions and cations.

Keywords: crystal structure; trimesate; imidazole.

CCDC reference: 2502103

1. Chemical context

Benzene-1,3,5-tricarboxylic acid (trimesic acid, H₃btc) and imidazole derivatives are typically used in the synthesis of metal–organic frameworks (MOFs). For example, imidazole (Im) and 2-methylimidazole (2mIm) serve as ligands in the synthesis of the reported zeolitic imidazolate frameworks ZIF-4 and ZIF-8, respectively (Park et al., 2006 ). Likewise, H₃btc is a key precursor in the synthesis of the well-known MOFs MIL-100 (Férey et al., 2004 ) and HKUST-1 (Chui et al., 1999 ). In previous work, we have employed 2-methylimidazole and H₃btc to synthesize a small coordination complex (Velazquez-Garcia & Techert, 2022 ), various organic salts (Baletska et al., 2023 ; Asprilla-Herrera et al., 2025 ; Łukaszczyk et al., 2025 ) and two mixed-ligand MOFs (Velazquez Garcia et al., 2025 ). In the present study, we substituted 2-methylimidazole with imidazole to synthesize the title compound (1).

2. Structural commentary

Compound 1 (Fig. 1) crystallizes in the trigonal R $[\overline{3}]$ space group. The complete group contains three hexakis(imidazole)cobalt(II) cations and two fully deprotonated btc³⁻ anions. The asymmetric unit comprises one third of a btc³⁻ anion and two crystallographically independent metal centres (Co1 and Co2) – one third of Co1 coordinated by two Im ligands and one sixth of Co2 coordinated by a single Im ligand. Both metal centres and the centre of mass of the btc³⁻ ion lie on the $[\overline{3}]$ rotoinversion axis, while Co2 is located exactly on the inversion centre.

Figure 1
Crystal structure of 1 with displacement ellipsoids drawn at the 50% probability level. Atoms labelled by group are generated by the following symmetry operations: 1 − y, 1 + x − y, z for groups a, c and e; −x + y, 1 − x, z for groups b, d and f; $[{2\over 3}]$ − x, $[{4\over 3}]$ − y, $[{1\over 3}]$ − z for fractions g and i; − $[{1\over 3}]$ + y, $[{1\over 3}]$ − x + y, $[{1\over 3}]$ − z for group h.

To estimate the distortion from the ideal octahedral geometry of the cations, 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 N—Co—N angles from 90°, Θ indicates the degree of twist from a perfect octahedron towards a trigonal prism. In an ideal octahedron, both parameters are equal to zero, whereas Θ reaches 1140° for a perfect trigonal prism. The calculated values of the distortion parameters Σ/Θ for Co1 and Co2 are equal to 13°/27° and 10°/23°, respectively. Both parameters exhibit a slight distortion of the coordination environment of both metal centres.

3. Supramolecular features

Crystal packing diagrams of compound 1 as viewed down the c and a axes are shown in Figs. 2 and 3, respectively. The figures show columns of ions stacked along the c axis, following a repeating polar arrangement: anion – cation – cation – anion – cation. Each column interacts with others via hydrogen bonding of the N—H⋯O type (Fig. 3), summarized in Table 1. The table demonstrates that all possible donor and acceptor groups are involved in moderate hydrogen bonds. The presence of different 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 ten motifs involved in discrete D (all types), ring R (all types) and chains C (types b and d). Notably, hydrogen bonds b and d hold the aforementioned columns together, whereas a and c strengthen the interaction between ions within the columns.

Table 1
Hydrogen-bond geometry (Å,°)

D—H⋯A	Type	Graph-set	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯O1	a	DR²₂(16)	0.856 (14)	1.908 (14)	2.7282 (17)	160.0 (4)
N2—H2⋯O1ⁱ	b	DC²₂(16) R₆⁶(48)	0.835 (13)	1.991 (13)	2.7661 (18)	154.0 (12)
N6—H6A⋯O2	c	DR²₂(16)	0.841 (14)	2.075 (12)	2.8161 (17)	146.8 (4)
N6—H6A⋯O2ⁱⁱ	d	DC²₂(16) R₄⁴(32) R₆⁶(48)	0.841 (14)	2.446 (9)	3.0298 (17)	127.2 (3)
Symmetry codes: (i) $[{2\over 3}]$ − x + y, 4/3 − x, $[{1\over 3}]$ + z; (ii) 4/3 − x, $[{5\over 3}]$ − y, $[{2\over 3}]$ − z.

Figure 2
Packing diagram of 1 down the c axis.

Figure 3
Crystal packing of 1 viewed along the a axis, showing only two representative stacks for clarity. Only discrete graph-set motifs are highlighted (a–d).

4. Database survey

No reported structures of the title compound were found in the Cambridge Structural Database (CSD version 5.45, update of November 2023; Groom et al., 2016 ). Some structures containing the hexakis(imidazole)cobalt(II) cation and polycarboxylate anions were reported under the refcodes AGAXIS (Jyai & Srinivasan, 2019 ), BOVMIJ (Nie et al., 2009 ) and EFIVOE (Tong et al., 2002 ). However, none of them include btc³⁻ as counter-ion but benzene-1,2-dicarboxylate, bis(naphthalene-1,4-dicarboxylate) and 1,4-benzenedicarboxylate, respectively.

5. Synthesis and crystallization

In a typical synthesis, 100 µL of a 0.11 M ethanolic solution of CoCl₂·6H₂O was diluted with 100 µL of N,N-dimethylformamide, followed by the addition of 120 µL of a 1.58 M ethanolic solution of imidazole. Then, 100 µL of a 0.12 M ethanolic solution of H₃btc was added to the mixture. The resulting mixture was gently shaken and allowed to dry slowly at room temperature. After three weeks, red crystals of 1 were obtained.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The positions of hydrogen atoms were refined with U_iso(H) = 1.2U_eq(C or N) for CH and NH groups. Hydrogen atoms bonded to nitrogen atoms (N—H) were treated with free refinement of bond distances. The most disagreeable reflections ( $[\overline{4}]$ 50 and 244) with error/s.u. of more than ten were omitted using the OMIT instruction in SHELXL (Sheldrick, 2015b ).

Table 2
Experimental details

Crystal data
Chemical formula	[Co(C₃H₄N₂)₆]₃(C₉H₃O₆)₂
M_r	1816.49
Crystal system, space group	Trigonal, R $[\overline{3}]$
Temperature (K)	100
a, c (Å)	15.215 (2), 30.494 (6)
V (Å³)	6113 (2)
Z	3
Radiation type	Mo Kα
μ (mm⁻¹)	0.69
Crystal size (mm)	0.6 × 0.4 × 0.2

Data collection
Diffractometer	Bruker P4
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.690, 0.748
No. of measured, independent and observed [I > 2σ(I)] reflections	28365, 3380, 3106
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.076, 1.04
No. of reflections	3380
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.33
Computer programs: APEX2 and APEX2 (Bruker, 2016 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2502103

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025010060/jq2041sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025010060/jq2041Isup2.hkl

checkCIF report

Computing details top

Tris[hexakis(imidazole)cobalt(II)] bis(benzene-1,3,5-tricarboxylate) top

Crystal data top

[Co(C₃H₄N₂)₆]₃(C₉H₃O₆)₂	D_x = 1.480 Mg m⁻³
M_r = 1816.49	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 9869 reflections
a = 15.215 (2) Å	θ = 2.7–39.6°
c = 30.494 (6) Å	µ = 0.69 mm⁻¹
V = 6113 (2) Å³	T = 100 K
Z = 3	Rhombohedral, red
F(000) = 2817	0.6 × 0.4 × 0.2 mm

Data collection top

Bruker P4 diffractometer	R_int = 0.031
ω scans	θ_max = 28.3°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −20→20
T_min = 0.690, T_max = 0.748	k = −20→20
28365 measured reflections	l = −40→40
3380 independent reflections	Standard reflections: not measured; every not measured reflections
3106 reflections with I > 2σ(I)	intensity decay: not measured

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.076	w = 1/[σ²(F_o²) + (0.0345P)² + 12.840P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
3380 reflections	Δρ_max = 0.45 e Å⁻³
199 parameters	Δρ_min = −0.32 e Å⁻³
0 restraints

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	0.333333	0.666667	0.55111 (2)	0.00919 (8)
Co2	0.333333	0.666667	0.166667	0.00965 (10)
O2	0.59402 (7)	0.71916 (7)	0.34095 (3)	0.01540 (19)
O1	0.50598 (7)	0.56614 (7)	0.37221 (3)	0.01563 (19)
N1	0.46175 (8)	0.69448 (8)	0.59020 (3)	0.0127 (2)
N3	0.35884 (8)	0.56677 (8)	0.50903 (3)	0.0129 (2)
N5	0.46325 (8)	0.75844 (8)	0.20837 (3)	0.0131 (2)
N4	0.40359 (9)	0.51431 (9)	0.44997 (4)	0.0165 (2)
H4	0.4338 (7)	0.51618 (10)	0.4260 (5)	0.020*
N2	0.58846 (8)	0.75732 (9)	0.63733 (4)	0.0160 (2)
H2	0.6292 (9)	0.7952 (9)	0.6564 (4)	0.019*
N6	0.56893 (9)	0.80854 (9)	0.26463 (4)	0.0163 (2)
H6A	0.5978 (7)	0.80585 (11)	0.2877 (5)	0.020*
C11	0.42044 (9)	0.65755 (9)	0.35769 (4)	0.0121 (2)
C12	0.32434 (9)	0.57106 (9)	0.35767 (4)	0.0128 (2)
H12	0.31828 (15)	0.5068 (12)	0.35765 (4)	0.015*
C10	0.51488 (9)	0.64817 (9)	0.35684 (4)	0.0122 (2)
C4	0.41613 (10)	0.59442 (10)	0.47339 (4)	0.0153 (2)
H4A	0.4609 (9)	0.6629 (13)	0.46533 (16)	0.018*
C7	0.49165 (10)	0.72946 (10)	0.24412 (4)	0.0152 (2)
H7	0.4615 (6)	0.6621 (13)	0.25389 (19)	0.018*
C1	0.51171 (10)	0.76558 (10)	0.61989 (4)	0.0170 (2)
H1	0.4959 (3)	0.8149 (10)	0.62771 (16)	0.020*
C9	0.52659 (10)	0.86245 (10)	0.20645 (4)	0.0184 (3)
H9	0.52491 (11)	0.9039 (9)	0.1851 (4)	0.022*
C8	0.59212 (11)	0.89424 (11)	0.24123 (5)	0.0202 (3)
H8	0.6424 (10)	0.9607 (14)	0.24769 (14)	0.024*
C2	0.58792 (11)	0.67609 (11)	0.61821 (5)	0.0211 (3)
H2A	0.6330 (9)	0.6514 (5)	0.62393 (13)	0.025*
C3	0.50915 (11)	0.63748 (11)	0.58913 (5)	0.0201 (3)
H3	0.4896 (4)	0.5789 (12)	0.5706 (4)	0.024*
C6	0.30649 (11)	0.46203 (10)	0.50802 (4)	0.0200 (3)
H6	0.2597 (10)	0.4201 (9)	0.5291 (4)	0.024*
C5	0.33334 (12)	0.42898 (11)	0.47158 (5)	0.0243 (3)
H5	0.3089 (5)	0.3622 (15)	0.46314 (19)	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.00977 (10)	0.00977 (10)	0.00803 (13)	0.00488 (5)	0.000	0.000
Co2	0.01060 (13)	0.01060 (13)	0.00775 (18)	0.00530 (6)	0.000	0.000
O2	0.0124 (4)	0.0163 (4)	0.0162 (4)	0.0061 (4)	−0.0005 (3)	0.0012 (3)
O1	0.0194 (4)	0.0169 (4)	0.0148 (4)	0.0122 (4)	0.0048 (3)	0.0028 (3)
N1	0.0134 (5)	0.0136 (5)	0.0114 (5)	0.0069 (4)	0.0001 (4)	0.0005 (4)
N3	0.0138 (5)	0.0136 (5)	0.0121 (5)	0.0074 (4)	−0.0003 (4)	−0.0004 (4)
N5	0.0135 (5)	0.0142 (5)	0.0114 (5)	0.0067 (4)	−0.0001 (4)	−0.0002 (4)
N4	0.0216 (6)	0.0174 (5)	0.0128 (5)	0.0116 (5)	0.0047 (4)	0.0000 (4)
N2	0.0133 (5)	0.0196 (5)	0.0125 (5)	0.0062 (4)	−0.0026 (4)	−0.0019 (4)
N6	0.0161 (5)	0.0218 (6)	0.0118 (5)	0.0101 (5)	−0.0037 (4)	−0.0026 (4)
C11	0.0132 (5)	0.0151 (6)	0.0093 (5)	0.0080 (5)	0.0003 (4)	0.0000 (4)
C12	0.0153 (6)	0.0127 (6)	0.0109 (5)	0.0074 (5)	−0.0005 (4)	−0.0003 (4)
C10	0.0139 (5)	0.0150 (6)	0.0091 (5)	0.0082 (5)	−0.0012 (4)	−0.0030 (4)
C4	0.0167 (6)	0.0143 (6)	0.0151 (6)	0.0079 (5)	0.0023 (5)	0.0002 (5)
C7	0.0150 (6)	0.0174 (6)	0.0131 (6)	0.0080 (5)	−0.0008 (4)	0.0003 (4)
C1	0.0175 (6)	0.0205 (6)	0.0148 (6)	0.0109 (5)	−0.0021 (5)	−0.0039 (5)
C9	0.0191 (6)	0.0149 (6)	0.0171 (6)	0.0053 (5)	−0.0035 (5)	0.0009 (5)
C8	0.0190 (6)	0.0166 (6)	0.0204 (6)	0.0055 (5)	−0.0053 (5)	−0.0022 (5)
C2	0.0182 (6)	0.0241 (7)	0.0246 (7)	0.0133 (6)	−0.0062 (5)	−0.0036 (5)
C3	0.0201 (6)	0.0211 (7)	0.0238 (7)	0.0138 (6)	−0.0074 (5)	−0.0060 (5)
C6	0.0262 (7)	0.0140 (6)	0.0179 (6)	0.0087 (5)	0.0081 (5)	0.0017 (5)
C5	0.0334 (8)	0.0139 (6)	0.0228 (7)	0.0098 (6)	0.0106 (6)	0.0000 (5)

Geometric parameters (Å, º) top

Co1—N1	2.1426 (11)	N2—H2	0.836 (19)
Co1—N1ⁱ	2.1426 (11)	N2—C1	1.3448 (17)
Co1—N1ⁱⁱ	2.1426 (11)	N2—C2	1.3629 (18)
Co1—N3	2.1673 (11)	N6—H6A	0.840 (19)
Co1—N3ⁱⁱ	2.1673 (11)	N6—C7	1.3441 (17)
Co1—N3ⁱ	2.1673 (11)	N6—C8	1.3689 (18)
Co2—N5ⁱⁱⁱ	2.1710 (11)	C11—C12ⁱ	1.3965 (17)
Co2—N5ⁱⁱ	2.1712 (11)	C11—C12	1.3948 (17)
Co2—N5	2.1711 (11)	C11—C10	1.5136 (17)
Co2—N5^iv	2.1711 (11)	C12—H12	0.935 (18)
Co2—N5ⁱ	2.1711 (11)	C4—H4A	0.949 (18)
Co2—N5^v	2.1711 (11)	C7—H7	0.938 (18)
O2—C10	1.2452 (16)	C1—H1	0.927 (18)
O1—C10	1.2755 (15)	C9—H9	0.917 (19)
N1—C1	1.3212 (17)	C9—C8	1.3679 (18)
N1—C3	1.3780 (17)	C8—H8	0.935 (19)
N3—C4	1.3233 (16)	C2—H2A	0.948 (19)
N3—C6	1.3805 (17)	C2—C3	1.3652 (19)
N5—C7	1.3269 (16)	C3—H3	0.968 (19)
N5—C9	1.3826 (17)	C6—H6	0.935 (19)
N4—H4	0.855 (18)	C6—C5	1.3637 (19)
N4—C4	1.3413 (17)	C5—H5	0.93 (2)
N4—C5	1.3690 (18)

N1—Co1—N1ⁱ	92.04 (4)	C1—N2—H2	126.2
N1—Co1—N1ⁱⁱ	92.04 (4)	C1—N2—C2	107.69 (11)
N1ⁱ—Co1—N1ⁱⁱ	92.04 (4)	C2—N2—H2	126.2
N1ⁱ—Co1—N3ⁱⁱ	89.24 (4)	C7—N6—H6A	126.2
N1ⁱⁱ—Co1—N3ⁱ	177.42 (4)	C7—N6—C8	107.68 (11)
N1—Co1—N3ⁱ	89.24 (4)	C8—N6—H6A	126.2
N1ⁱⁱ—Co1—N3ⁱⁱ	90.15 (4)	C12—C11—C12ⁱ	119.40 (12)
N1—Co1—N3	90.15 (4)	C12—C11—C10	120.52 (11)
N1ⁱ—Co1—N3ⁱ	90.15 (4)	C12ⁱ—C11—C10	120.07 (11)
N1ⁱ—Co1—N3	177.42 (4)	C11—C12—C11ⁱⁱ	120.60 (12)
N1ⁱⁱ—Co1—N3	89.24 (4)	C11—C12—H12	119.7
N1—Co1—N3ⁱⁱ	177.42 (4)	C11ⁱⁱ—C12—H12	119.7
N3—Co1—N3ⁱ	88.52 (4)	O2—C10—O1	125.12 (11)
N3—Co1—N3ⁱⁱ	88.52 (4)	O2—C10—C11	118.48 (11)
N3ⁱⁱ—Co1—N3ⁱ	88.52 (4)	O1—C10—C11	116.40 (11)
N5ⁱⁱⁱ—Co2—N5^iv	89.17 (4)	N3—C4—N4	112.12 (12)
N5^v—Co2—N5	90.83 (4)	N3—C4—H4A	123.9
N5^v—Co2—N5ⁱⁱ	180.00 (6)	N4—C4—H4A	123.9
N5ⁱⁱⁱ—Co2—N5ⁱ	180.0	N5—C7—N6	111.68 (12)
N5^iv—Co2—N5ⁱⁱ	90.83 (4)	N5—C7—H7	124.2
N5^iv—Co2—N5ⁱ	90.83 (4)	N6—C7—H7	124.2
N5ⁱ—Co2—N5	89.17 (4)	N1—C1—N2	111.44 (12)
N5ⁱⁱⁱ—Co2—N5^v	89.17 (4)	N1—C1—H1	124.3
N5ⁱⁱⁱ—Co2—N5ⁱⁱ	90.83 (4)	N2—C1—H1	124.3
N5^iv—Co2—N5^v	89.17 (4)	N5—C9—H9	125.1
N5ⁱ—Co2—N5ⁱⁱ	89.17 (4)	C8—C9—N5	109.85 (12)
N5ⁱⁱⁱ—Co2—N5	90.83 (4)	C8—C9—H9	125.1
N5—Co2—N5ⁱⁱ	89.17 (4)	N6—C8—H8	127.1
N5^iv—Co2—N5	180.00 (4)	C9—C8—N6	105.80 (12)
N5ⁱ—Co2—N5^v	90.83 (4)	C9—C8—H8	127.1
C1—N1—Co1	129.61 (9)	N2—C2—H2A	127.1
C1—N1—C3	105.28 (11)	N2—C2—C3	105.89 (12)
C3—N1—Co1	125.11 (9)	C3—C2—H2A	127.1
C4—N3—Co1	125.72 (9)	N1—C3—H3	125.2
C4—N3—C6	104.88 (11)	C2—C3—N1	109.70 (12)
C6—N3—Co1	128.35 (9)	C2—C3—H3	125.2
C7—N5—Co2	127.63 (9)	N3—C6—H6	125.1
C7—N5—C9	105.00 (11)	C5—C6—N3	109.72 (12)
C9—N5—Co2	126.92 (9)	C5—C6—H6	125.1
C4—N4—H4	126.4	N4—C5—H5	126.9
C4—N4—C5	107.12 (11)	C6—C5—N4	106.16 (12)
C5—N4—H4	126.4	C6—C5—H5	126.9

Co1—N1—C1—N2	179.95 (8)	C10—C11—C12—C11ⁱⁱ	−178.88 (8)
Co1—N1—C3—C2	−179.87 (10)	C4—N3—C6—C5	−0.21 (16)
Co1—N3—C4—N4	−169.11 (8)	C4—N4—C5—C6	−0.41 (17)
Co1—N3—C6—C5	168.45 (10)	C7—N5—C9—C8	−0.03 (16)
Co2—N5—C7—N6	−172.93 (8)	C7—N6—C8—C9	−0.42 (15)
Co2—N5—C9—C8	172.72 (9)	C1—N1—C3—C2	−0.46 (16)
N3—C6—C5—N4	0.39 (18)	C1—N2—C2—C3	0.16 (16)
N5—C9—C8—N6	0.28 (16)	C9—N5—C7—N6	−0.24 (15)
N2—C2—C3—N1	0.18 (17)	C8—N6—C7—N5	0.42 (15)
C12ⁱ—C11—C12—C11ⁱⁱ	−0.1 (2)	C2—N2—C1—N1	−0.47 (16)
C12ⁱ—C11—C10—O2	−25.08 (17)	C3—N1—C1—N2	0.57 (15)
C12—C11—C10—O2	153.71 (12)	C6—N3—C4—N4	−0.05 (15)
C12—C11—C10—O1	−25.38 (17)	C5—N4—C4—N3	0.30 (16)
C12ⁱ—C11—C10—O1	155.82 (11)

Symmetry codes: (i) −y+1, x−y+1, z; (ii) −x+y, −x+1, z; (iii) y−1/3, −x+y+1/3, −z+1/3; (iv) −x+2/3, −y+4/3, −z+1/3; (v) x−y+2/3, x+1/3, −z+1/3.

Hydrogen-bond geometry (Å,°) top

D—H···A	Type	Graph-set	D—H	H···A	D···A	D—H···A
N4—H4···O1	a	DR²₂(16)	0.856 (14)	1.908 (14)	2.7282 (17)	160.0 (4)
N2—H2···O1ⁱ	b	DC²₂(16)R⁶₆(48)	0.835 (13)	1.991 (13)	2.7661 (18)	154.0 (12)
N6—H6A···O2	c	DR²₂(16)	0.841 (14)	2.075 (12)	2.8161 (17)	146.8 (4)
N6—H6A···O2ⁱⁱ	d	DC²₂(16)R⁴₄(32)R⁶₆(48)	0.841 (14)	2.446 (9)	3.0298 (17)	127.2 (3)

Symmetry codes: (i) 2/3 - x + y, 4/3 - x, 1/3 + z; (ii) 4/3 - x, 5/3 - y, 2/3 - z.

Funding information

Funding for this research was provided by: HG-recruitment, HG-Innovation "FISCOV", "FISVIR" and the CMWS (grant to ST). CB thanks the DESY-Helmholtz-Summer student fund for financial support.

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