Crystal structure of tetra­kis­(imidazolium) hexa­kis­(imidazole-κN)cobalt(II) bis­(benzene-1,3,5-tri­carboxyl­ate) dihydrate

Velazquez Garcia, J. de J.; Pujol, E.N.; Khademhir, F.; Knjo, B.; Ekineken, A.; Hain, F.; Techert, S.

doi:10.1107/S2056989026001660

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ISSN: 2056-9890

Volume 82| Part 3| March 2026| Pages 286-288

https://doi.org/10.1107/S2056989026001660

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Crystal structure of tetrakis(imidazolium) hexakis(imidazole-κN)cobalt(II) bis(benzene-1,3,5-tricarboxylate) dihydrate

Jose de Jesus Velazquez Garcia,^a ^* Edwige Nadia Pujol,^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, ^bFaculty of Science and Engineering, Sorbonne Université, 4 Place Jussieu, 75005, Paris, France, ^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 A. S. Batsanov, University of Durham, United Kingdom (Received 7 October 2025; accepted 16 February 2026; online 20 February 2026)

The title compound, (C₃H₅N₂)₄[Co(C₃H₄N₂)₆](C₉H₃O₆)₂·2H₂O (1), was synthesized by slow evaporation of mixed ethanolic solutions of CoCl₂, benzene-1,3,5-tricarboxylic acid (H₃btc) and imidazole (Im) at room temperature. The crystal structure comprises [Co(Im)₆]²⁺ cations, btc³⁻ anions, Im⁺ cations and water molecules in a 1:2:4:2 ratio. The crystal packing shows alternating layers stacked along the c-axis direction, linked primarily by hydrogen bonds of the types N—H⋯O (between cations and anions) and O—H⋯O (between anions and water molecules).

Keywords: crystal structure; imidazol-1-ium; hexakis(imidazole)cobalt; benzene-1,3,5-tricarboxylate.

CCDC reference: 2531427

1. Chemical context

Rigid benzene di-, tri, and tetra-carboxylic acid, azolate-based ligands, as well as their derivatives are commonly employed as organic building blocks in the synthesis of metal–organic frameworks (MOFs) (Lin et al., 2014 ). For example, benzene-1,3,5-tricarboxylic acid (trimesic acid, H₃btc) serves as a precursor in the synthesis of the well-known MOFs MIL-100 (Férey et al., 2004 ) and HKUST-1 (Chui et al., 1999 ). Azolate-based ligands, such as imidazole (Im) and 2-methylimidazole (2mIm), are key ligands in the synthesis of the zeolitic imidazolate frameworks (ZIFs), such as ZIF-4 and ZIF-8 (Park et al., 2006 ). Over the last few years, we have used H₃btc and 2mIm to synthesize a small coordination complex (de 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 this work, we used H₃btc and Im to synthesize the title compound (1).

2. Structural commentary

Compound 1 (Fig. 1) crystallizes in space group P $[\overline{1}]$ . The complete formula unit comprises one hexakis(imidazole)cobalt(II) cation, four Im⁺ cations, two fully deprotonated btc³⁻ anions and two water molecules. The asymmetric unit comprises one half of the formula unit (Z′ = 0.5) with the Co-containing cation lying about an inversion centre (Fig. 1). The Co—N bond lengths range from 2.1408 (10) to 2.1660 (10) Å.

Figure 1
The molecular structure of 1 with displacement ellipsoids drawn at the 50% probability level. Primed atoms are generated by the inversion operation 2 − x, −y, 1 − z

The distortion from the ideal octahedral geometry of the Co-containing cation was quantified using the parameters Σ (Halcrow, 2011 ) and Θ (Marchivie et al., 2005 ), obtained via 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. Both parameters are equal to zero in an ideal octahedron. The calculated values of the distortion parameters Σ and Θ for Co1 are equal to 12 and 36°, respectively. Both parameters indicate a slight distortion of the coordination environment of the metal centre.

3. Supramolecular features

A packing diagram of the compound as viewed down the b axis is shown in Fig. 2. The figure shows a layered arrangement with all layers parallel to the ab plane. Three types of layers are observed: Plane A, formed by HIm⁺ cations and btc³⁻ anions; Plane B, consisting of hexakis(imidazole)cobalt(II) cations; and Plane C, composed of HIm⁺ cations and water molecules. These layers stack in a repeating A–B–A–C sequence along the c-axis direction. Each layer interacts with others via hydrogen bonding of the N—H⋯O and O—H⋯O types. A summary of the hydrogen-bonding interactions is given in Table 1, showing that all possible donor and acceptor groups are involved in moderately strong hydrogen bonds. The latter form distinct patterns determined by graph-set analysis (Etter et al., 1990 ; Bernstein et al., 1995 ), which shows that structure 1 features only 12 discrete motifs.

Table 1
Hydrogen-bond geometry (Å,°)

D—H⋯A	Type	Graph-set	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2ⁱ	a	D, D²₂(11)	0.860 (11)	1.888 (11)	2.7294 (15)	165.5 (7)
N4—H4⋯O2ⁱⁱ	b	D, D²₂(11)	0.854 (12)	1.898 (11)	2.7336 (15)	165.9 (9)
N6—H6⋯O1	c	D, D²₂(11)	0.872 (12)	1.834 (12)	2.6949 (15)	168.9 (7)
O7—H7B⋯O6	d	D	0.875 (18)	1.894 (18)	2.7558 (15)	167.9 (17)
O7—H7C⋯O4ⁱⁱⁱ	e	D	0.900 (15)	1.947 (16)	2.8456 (15)	175.3 (16)
N7—H7A⋯O4	f	D	0.892 (13)	1.806 (14)	2.6932 (16)	172.6 (8)
N8—H8A⋯O6^v	g	D	0.880 (10)	1.861 (10)	2.7350 (15)	172.1 (8)
N10—H10A⋯O3^iv	h	D	0.881 (14)	1.791 (14)	2.6492 (15)	164.2 (5)
N9—H9A⋯O5	i	D	0.889 (12)	1.706 (12)	2.6031 (16)	174.6 (10)
Symmetry codes: (1) 1 − x, −y, 1 − z; (ii) 1 − x, 1 − y, 1 − z; (iii) 2 − x, 2 − y, −z; (iv) 1 + x, 1 + y, z; (v) 1 − x, 2 − y, −z.

Figure 2
Packing diagram of 1 viewed down the b axis.

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 anion.

5. Synthesis and crystallization

In a 4 mL vial, 100 µL of a 0.11 M ethanolic solution of cobalt CoCl₂·6H₂O was mixed with 120 µL of a 1.58 M ethanolic solution of Im. 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 evaporate slowly at room temperature. After three weeks, crystals of 1 were obtained.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Imidazole H atoms were refined using a riding model with variable C—H or N—H distances and U_iso(H) = 1.2U_eq(C or N), water H atoms were refined with DFIX 0.87 and DANG 1.38 restraints and U_iso(H) = 1.5U_eq(O).

Table 2
Experimental details

Crystal data
Chemical formula	(C₃H₅N₂)₄[Co(C₃H₄N₂)₆](C₉H₃O₆)₂·2H₂O
M_r	1194.04
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	8.2752 (4), 8.8586 (4), 19.4212 (8)
α, β, γ (°)	95.310 (2), 101.624 (2), 102.854 (2)
V (Å³)	1345.42 (11)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.41
Crystal size (mm)	1.0 × 0.6 × 0.3

Data collection
Diffractometer	Bruker APEXII CCD area detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.696, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	41855, 6749, 6210
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.078, 1.05
No. of reflections	6749
No. of parameters	407
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.36
Computer programs: APEX2 (and SAINT (Bruker, 2016 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2531427

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989026001660/zv2041sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989026001660/zv2041Isup2.hkl

checkCIF report

Computing details top

Tetrakis(imidazolium) hexakis(imidazole-κN)cobalt(II) bis(benzene-1,3,5-tricarboxylate) dihydrate top

Crystal data top

(C₃H₅N₂)₄[Co(C₃H₄N₂)₆](C₉H₃O₆)₂·2H₂O	Z = 1
M_r = 1194.04	F(000) = 621
Triclinic, P1	D_x = 1.474 Mg m⁻³
a = 8.2752 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.8586 (4) Å	Cell parameters from 9831 reflections
c = 19.4212 (8) Å	θ = 2.4–28.4°
α = 95.310 (2)°	µ = 0.41 mm⁻¹
β = 101.624 (2)°	T = 100 K
γ = 102.854 (2)°	Irregular, red
V = 1345.42 (11) Å³	1.0 × 0.6 × 0.3 mm

Data collection top

Bruker APEXII CCD area detector diffractometer	6210 reflections with I > 2σ(I)
phi and ω scans	R_int = 0.027
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 28.4°, θ_min = 2.2°
T_min = 0.696, T_max = 0.746	h = −11→11
41855 measured reflections	k = −11→11
6749 independent reflections	l = −26→25

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.078	w = 1/[σ²(F_o²) + (0.0329P)² + 0.8481P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
6749 reflections	Δρ_max = 0.43 e Å⁻³
407 parameters	Δρ_min = −0.36 e Å⁻³
3 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	1.000000	0.000000	0.500000	0.00894 (6)
O2	0.39146 (12)	0.54791 (11)	0.32042 (5)	0.01739 (19)
O3	0.94002 (12)	0.63711 (11)	0.12979 (5)	0.01620 (18)
O4	0.87107 (12)	0.82054 (11)	0.06753 (5)	0.01915 (19)
O5	0.29103 (12)	1.00222 (11)	0.20174 (5)	0.01881 (19)
O6	0.44531 (12)	1.09291 (11)	0.12540 (5)	0.01906 (19)
O1	0.58037 (13)	0.42621 (11)	0.28993 (5)	0.0215 (2)
O7	0.32574 (14)	1.33180 (13)	0.06869 (6)	0.0242 (2)
H7B	0.357 (2)	1.259 (2)	0.0918 (10)	0.036*
H7C	0.266 (2)	1.279 (2)	0.0260 (8)	0.036*
N5	0.79448 (13)	0.06066 (12)	0.42876 (5)	0.01174 (19)
N1	0.83209 (13)	−0.21112 (12)	0.51648 (5)	0.01251 (19)
N3	0.94168 (13)	0.12759 (12)	0.58700 (5)	0.01188 (19)
N2	0.70821 (14)	−0.38463 (13)	0.57651 (6)	0.0165 (2)
H2	0.6676 (8)	−0.4237 (8)	0.6102 (7)	0.020*
N4	0.80835 (14)	0.25934 (12)	0.64879 (5)	0.0144 (2)
H4	0.7336 (15)	0.3052 (9)	0.6586 (2)	0.017*
N7	1.13972 (14)	0.77292 (13)	0.01793 (6)	0.0164 (2)
H7A	1.0560 (17)	0.7887 (3)	0.0381 (4)	0.020*
N6	0.64139 (13)	0.19585 (13)	0.36508 (6)	0.0149 (2)
H6	0.6141 (6)	0.2733 (16)	0.3448 (4)	0.018*
N10	−0.03117 (14)	1.38098 (13)	0.18656 (6)	0.0164 (2)
H10A	−0.0542 (5)	1.4673 (18)	0.1727 (3)	0.020*
N8	1.33265 (14)	0.80451 (13)	−0.04292 (6)	0.0164 (2)
H8A	1.3993 (13)	0.8447 (8)	−0.0701 (5)	0.020*
N9	0.09204 (14)	1.19201 (13)	0.20257 (6)	0.0173 (2)
H9A	0.1651 (15)	1.1309 (12)	0.20117 (6)	0.021*
C16	0.49883 (15)	0.52867 (14)	0.28451 (6)	0.0125 (2)
C24	0.44916 (15)	0.75867 (14)	0.22124 (6)	0.0122 (2)
H24	0.3629 (15)	0.76491 (18)	0.2442 (4)	0.015*
C17	0.84952 (15)	0.73004 (14)	0.11361 (6)	0.0132 (2)
C21	0.70671 (15)	0.73746 (14)	0.15060 (6)	0.0119 (2)
C19	0.53436 (15)	0.64081 (14)	0.23185 (6)	0.0114 (2)
C5	0.95059 (16)	0.24602 (15)	0.69538 (7)	0.0160 (2)
H5	0.9847 (6)	0.2846 (7)	0.7439 (9)	0.019*
C23	0.49277 (15)	0.86762 (14)	0.17627 (6)	0.0123 (2)
C7	0.79417 (15)	0.19669 (14)	0.40538 (6)	0.0139 (2)
H7	0.8902 (17)	0.2840 (15)	0.41584 (19)	0.017*
C18	0.40284 (15)	0.99806 (14)	0.16688 (6)	0.0139 (2)
C22	0.62126 (15)	0.85571 (14)	0.14128 (6)	0.0130 (2)
H22	0.6507 (5)	0.9277 (13)	0.1112 (5)	0.016*
C20	0.66138 (15)	0.63031 (14)	0.19548 (6)	0.0122 (2)
H20	0.7174 (10)	0.5491 (14)	0.20144 (12)	0.015*
C6	1.03247 (16)	0.16504 (14)	0.65676 (6)	0.0143 (2)
H6A	1.1383 (18)	0.1379 (5)	0.6754 (3)	0.017*
C8	0.53656 (16)	0.05072 (15)	0.36181 (7)	0.0167 (2)
H8	0.426 (2)	0.0163 (7)	0.3381 (5)	0.020*
C4	0.80784 (16)	0.18688 (14)	0.58473 (6)	0.0139 (2)
H4A	0.7219 (15)	0.1792 (2)	0.5430 (7)	0.017*
C9	0.63174 (16)	−0.03136 (15)	0.40138 (7)	0.0153 (2)
H9	0.5925 (7)	−0.1351 (19)	0.40891 (15)	0.018*
C1	0.78258 (15)	−0.23377 (15)	0.57635 (7)	0.0143 (2)
H1	0.7975 (3)	−0.1552 (14)	0.6134 (7)	0.017*
C11	1.33407 (17)	0.66799 (15)	−0.01452 (7)	0.0176 (2)
H11	1.4046 (14)	0.6019 (13)	−0.02044 (13)	0.021*
C2	0.70918 (17)	−0.46475 (15)	0.51278 (7)	0.0193 (3)
H2A	0.6658 (8)	−0.573 (2)	0.4975 (3)	0.023*
C14	−0.12181 (18)	1.28397 (16)	0.22441 (7)	0.0209 (3)
H14	−0.2210 (19)	1.2975 (3)	0.2406 (3)	0.025*
C3	0.78548 (16)	−0.35705 (15)	0.47609 (7)	0.0158 (2)
H3	0.8036 (4)	−0.3788 (4)	0.4303 (8)	0.019*
C13	0.09671 (17)	1.32276 (16)	0.17442 (7)	0.0180 (2)
H13	0.1751 (15)	1.3660 (8)	0.1505 (5)	0.022*
C12	1.21281 (17)	0.64859 (15)	0.02371 (7)	0.0179 (2)
H12	1.1845 (6)	0.5667 (16)	0.0490 (5)	0.022*
C15	−0.04403 (18)	1.16575 (17)	0.23437 (8)	0.0214 (3)
H15	−0.0766 (7)	1.0822 (17)	0.2583 (5)	0.026*
C10	1.21386 (17)	0.86566 (15)	−0.02249 (7)	0.0175 (2)
H10	1.1871 (5)	0.9587 (18)	−0.0347 (2)	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01030 (11)	0.00904 (11)	0.00936 (10)	0.00363 (8)	0.00425 (8)	0.00344 (8)
O2	0.0221 (5)	0.0178 (4)	0.0205 (4)	0.0104 (4)	0.0140 (4)	0.0104 (4)
O3	0.0195 (4)	0.0167 (4)	0.0194 (4)	0.0109 (3)	0.0108 (4)	0.0083 (3)
O4	0.0234 (5)	0.0221 (5)	0.0223 (5)	0.0133 (4)	0.0152 (4)	0.0141 (4)
O5	0.0210 (5)	0.0209 (5)	0.0242 (5)	0.0140 (4)	0.0136 (4)	0.0124 (4)
O6	0.0228 (5)	0.0199 (5)	0.0235 (5)	0.0127 (4)	0.0128 (4)	0.0140 (4)
O1	0.0282 (5)	0.0215 (5)	0.0275 (5)	0.0170 (4)	0.0177 (4)	0.0164 (4)
O7	0.0294 (5)	0.0264 (5)	0.0259 (5)	0.0166 (4)	0.0119 (4)	0.0133 (4)
N5	0.0134 (5)	0.0128 (5)	0.0112 (4)	0.0052 (4)	0.0046 (4)	0.0035 (4)
N1	0.0130 (5)	0.0124 (5)	0.0138 (5)	0.0038 (4)	0.0048 (4)	0.0046 (4)
N3	0.0139 (5)	0.0111 (5)	0.0127 (5)	0.0040 (4)	0.0057 (4)	0.0042 (4)
N2	0.0190 (5)	0.0153 (5)	0.0190 (5)	0.0043 (4)	0.0101 (4)	0.0084 (4)
N4	0.0166 (5)	0.0154 (5)	0.0155 (5)	0.0082 (4)	0.0083 (4)	0.0039 (4)
N7	0.0176 (5)	0.0174 (5)	0.0183 (5)	0.0065 (4)	0.0098 (4)	0.0060 (4)
N6	0.0173 (5)	0.0155 (5)	0.0157 (5)	0.0083 (4)	0.0053 (4)	0.0075 (4)
N10	0.0210 (5)	0.0152 (5)	0.0180 (5)	0.0101 (4)	0.0077 (4)	0.0065 (4)
N8	0.0178 (5)	0.0175 (5)	0.0178 (5)	0.0057 (4)	0.0097 (4)	0.0069 (4)
N9	0.0193 (5)	0.0172 (5)	0.0200 (5)	0.0108 (4)	0.0067 (4)	0.0058 (4)
C16	0.0138 (5)	0.0117 (5)	0.0140 (5)	0.0041 (4)	0.0055 (4)	0.0046 (4)
C24	0.0132 (5)	0.0136 (5)	0.0127 (5)	0.0056 (4)	0.0063 (4)	0.0042 (4)
C17	0.0151 (5)	0.0135 (5)	0.0136 (5)	0.0054 (4)	0.0066 (4)	0.0036 (4)
C21	0.0130 (5)	0.0131 (5)	0.0120 (5)	0.0055 (4)	0.0053 (4)	0.0036 (4)
C19	0.0132 (5)	0.0111 (5)	0.0116 (5)	0.0040 (4)	0.0048 (4)	0.0043 (4)
C5	0.0183 (6)	0.0182 (6)	0.0125 (5)	0.0058 (5)	0.0043 (4)	0.0014 (4)
C23	0.0136 (5)	0.0128 (5)	0.0130 (5)	0.0059 (4)	0.0046 (4)	0.0043 (4)
C7	0.0147 (5)	0.0139 (6)	0.0157 (5)	0.0058 (4)	0.0056 (4)	0.0056 (4)
C18	0.0149 (5)	0.0144 (6)	0.0154 (5)	0.0068 (4)	0.0049 (4)	0.0059 (4)
C22	0.0161 (5)	0.0130 (5)	0.0132 (5)	0.0055 (4)	0.0067 (4)	0.0061 (4)
C20	0.0141 (5)	0.0115 (5)	0.0134 (5)	0.0056 (4)	0.0047 (4)	0.0039 (4)
C6	0.0155 (6)	0.0155 (6)	0.0133 (5)	0.0054 (4)	0.0046 (4)	0.0033 (4)
C8	0.0149 (6)	0.0160 (6)	0.0193 (6)	0.0052 (5)	0.0018 (5)	0.0038 (5)
C4	0.0159 (6)	0.0149 (6)	0.0137 (5)	0.0061 (4)	0.0059 (4)	0.0042 (4)
C9	0.0153 (6)	0.0127 (6)	0.0184 (6)	0.0042 (4)	0.0034 (4)	0.0042 (4)
C1	0.0149 (5)	0.0150 (6)	0.0154 (5)	0.0048 (4)	0.0062 (4)	0.0053 (4)
C11	0.0194 (6)	0.0159 (6)	0.0212 (6)	0.0075 (5)	0.0076 (5)	0.0061 (5)
C2	0.0238 (6)	0.0124 (6)	0.0228 (6)	0.0024 (5)	0.0096 (5)	0.0040 (5)
C14	0.0222 (6)	0.0227 (7)	0.0251 (7)	0.0109 (5)	0.0128 (5)	0.0104 (5)
C3	0.0193 (6)	0.0139 (6)	0.0153 (6)	0.0032 (5)	0.0066 (5)	0.0030 (4)
C13	0.0204 (6)	0.0188 (6)	0.0193 (6)	0.0092 (5)	0.0082 (5)	0.0065 (5)
C12	0.0208 (6)	0.0150 (6)	0.0210 (6)	0.0057 (5)	0.0079 (5)	0.0077 (5)
C15	0.0229 (7)	0.0205 (7)	0.0263 (7)	0.0091 (5)	0.0102 (5)	0.0117 (5)
C10	0.0207 (6)	0.0167 (6)	0.0202 (6)	0.0078 (5)	0.0102 (5)	0.0079 (5)

Geometric parameters (Å, º) top

Co1—N5ⁱ	2.1660 (10)	N8—C10	1.3309 (16)
Co1—N5	2.1660 (10)	N9—H9A	0.899 (18)
Co1—N1ⁱ	2.1598 (10)	N9—C13	1.3220 (17)
Co1—N1	2.1598 (10)	N9—C15	1.3762 (17)
Co1—N3ⁱ	2.1408 (10)	C16—C19	1.5161 (15)
Co1—N3	2.1408 (10)	C24—H24	0.923 (16)
O2—C16	1.2649 (14)	C24—C19	1.3923 (16)
O3—C17	1.2509 (15)	C24—C23	1.3973 (16)
O4—C17	1.2684 (15)	C17—C21	1.5117 (15)
O5—C18	1.2565 (15)	C21—C22	1.3940 (16)
O6—C18	1.2596 (15)	C21—C20	1.3884 (16)
O1—C16	1.2457 (15)	C19—C20	1.3940 (15)
O7—H7B	0.875 (15)	C5—H5	0.935 (17)
O7—H7C	0.899 (14)	C5—C6	1.3630 (17)
N5—C7	1.3268 (16)	C23—C18	1.5129 (16)
N5—C9	1.3797 (16)	C23—C22	1.3898 (16)
N1—C1	1.3261 (15)	C7—H7	0.950 (16)
N1—C3	1.3798 (16)	C22—H22	0.930 (16)
N3—C6	1.3806 (15)	C20—H20	0.942 (16)
N3—C4	1.3221 (15)	C6—H6A	0.969 (16)
N2—H2	0.861 (17)	C8—H8	0.907 (17)
N2—C1	1.3418 (16)	C8—C9	1.3616 (17)
N2—C2	1.3709 (17)	C4—H4A	0.951 (16)
N4—H4	0.853 (17)	C9—H9	0.939 (17)
N4—C5	1.3677 (17)	C1—H1	0.923 (17)
N4—C4	1.3449 (15)	C11—H11	0.930 (18)
N7—H7A	0.891 (17)	C11—C12	1.3547 (17)
N7—C12	1.3724 (17)	C2—H2A	0.939 (18)
N7—C10	1.3255 (16)	C2—C3	1.3623 (17)
N6—H6	0.872 (17)	C14—H14	0.964 (18)
N6—C7	1.3443 (16)	C14—C15	1.3549 (19)
N6—C8	1.3696 (17)	C3—H3	0.940 (16)
N10—H10A	0.881 (18)	C13—H13	0.909 (17)
N10—C14	1.3761 (16)	C12—H12	0.928 (17)
N10—C13	1.3275 (16)	C15—H15	0.928 (18)
N8—H8A	0.880 (17)	C10—H10	0.939 (18)
N8—C11	1.3762 (16)

N5—Co1—N5ⁱ	180.00 (5)	C24—C19—C20	119.02 (10)
N1—Co1—N5	91.95 (4)	C20—C19—C16	119.09 (10)
N1—Co1—N5ⁱ	88.05 (4)	N4—C5—H5	127.0
N1ⁱ—Co1—N5ⁱ	91.95 (4)	C6—C5—N4	106.05 (11)
N1ⁱ—Co1—N5	88.05 (4)	C6—C5—H5	127.0
N1ⁱ—Co1—N1	180.0	C24—C23—C18	120.25 (10)
N3ⁱ—Co1—N5	91.00 (4)	C22—C23—C24	119.09 (11)
N3ⁱ—Co1—N5ⁱ	89.00 (4)	C22—C23—C18	120.66 (10)
N3—Co1—N5	89.00 (4)	N5—C7—N6	111.70 (11)
N3—Co1—N5ⁱ	91.00 (4)	N5—C7—H7	124.1
N3ⁱ—Co1—N1ⁱ	89.89 (4)	N6—C7—H7	124.1
N3ⁱ—Co1—N1	90.12 (4)	O5—C18—O6	125.43 (11)
N3—Co1—N1ⁱ	90.11 (4)	O5—C18—C23	116.47 (10)
N3—Co1—N1	89.88 (4)	O6—C18—C23	118.10 (10)
N3—Co1—N3ⁱ	180.0	C21—C22—H22	119.5
H7B—O7—H7C	103.7 (17)	C23—C22—C21	121.00 (11)
C7—N5—Co1	127.69 (8)	C23—C22—H22	119.5
C7—N5—C9	105.05 (10)	C21—C20—C19	121.11 (11)
C9—N5—Co1	127.16 (8)	C21—C20—H20	119.4
C1—N1—Co1	125.01 (9)	C19—C20—H20	119.4
C1—N1—C3	105.20 (10)	N3—C6—H6A	125.2
C3—N1—Co1	128.38 (8)	C5—C6—N3	109.68 (11)
C6—N3—Co1	128.28 (8)	C5—C6—H6A	125.2
C4—N3—Co1	126.51 (8)	N6—C8—H8	126.9
C4—N3—C6	105.22 (10)	C9—C8—N6	106.17 (11)
C1—N2—H2	126.5	C9—C8—H8	126.9
C1—N2—C2	107.03 (10)	N3—C4—N4	111.62 (11)
C2—N2—H2	126.5	N3—C4—H4A	124.2
C5—N4—H4	126.3	N4—C4—H4A	124.2
C4—N4—H4	126.3	N5—C9—H9	125.1
C4—N4—C5	107.43 (10)	C8—C9—N5	109.80 (11)
C12—N7—H7A	125.6	C8—C9—H9	125.1
C10—N7—H7A	125.6	N1—C1—N2	111.87 (11)
C10—N7—C12	108.89 (11)	N1—C1—H1	124.1
C7—N6—H6	126.4	N2—C1—H1	124.1
C7—N6—C8	107.28 (10)	N8—C11—H11	126.6
C8—N6—H6	126.4	C12—C11—N8	106.76 (11)
C14—N10—H10A	125.7	C12—C11—H11	126.6
C13—N10—H10A	125.7	N2—C2—H2A	126.8
C13—N10—C14	108.63 (11)	C3—C2—N2	106.45 (11)
C11—N8—H8A	125.6	C3—C2—H2A	126.8
C10—N8—H8A	125.6	N10—C14—H14	126.8
C10—N8—C11	108.75 (10)	C15—C14—N10	106.46 (11)
C13—N9—H9A	126.0	C15—C14—H14	126.8
C13—N9—C15	108.09 (11)	N1—C3—H3	125.3
C15—N9—H9A	126.0	C2—C3—N1	109.45 (11)
O2—C16—C19	117.73 (10)	C2—C3—H3	125.3
O1—C16—O2	125.05 (11)	N10—C13—H13	125.4
O1—C16—C19	117.21 (10)	N9—C13—N10	109.25 (11)
C19—C24—H24	119.6	N9—C13—H13	125.4
C19—C24—C23	120.75 (11)	N7—C12—H12	126.4
C23—C24—H24	119.6	C11—C12—N7	107.12 (11)
O3—C17—O4	123.53 (11)	C11—C12—H12	126.4
O3—C17—C21	119.16 (10)	N9—C15—H15	126.2
O4—C17—C21	117.31 (10)	C14—C15—N9	107.58 (12)
C22—C21—C17	119.91 (10)	C14—C15—H15	126.2
C20—C21—C17	121.05 (11)	N7—C10—N8	108.48 (11)
C20—C21—C22	119.01 (11)	N7—C10—H10	125.8
C24—C19—C16	121.82 (10)	N8—C10—H10	125.8

Co1—N5—C7—N6	−176.37 (8)	C5—N4—C4—N3	−0.13 (14)
Co1—N5—C9—C8	176.64 (8)	C23—C24—C19—C16	175.32 (11)
Co1—N1—C1—N2	−167.16 (8)	C23—C24—C19—C20	−1.64 (18)
Co1—N1—C3—C2	166.60 (9)	C7—N5—C9—C8	0.21 (14)
Co1—N3—C6—C5	−179.36 (8)	C7—N6—C8—C9	0.39 (14)
Co1—N3—C4—N4	179.56 (8)	C18—C23—C22—C21	178.90 (11)
O2—C16—C19—C24	−1.86 (17)	C22—C21—C20—C19	−0.97 (18)
O2—C16—C19—C20	175.09 (11)	C22—C23—C18—O5	−178.40 (12)
O3—C17—C21—C22	170.38 (12)	C22—C23—C18—O6	1.51 (18)
O3—C17—C21—C20	−7.97 (18)	C20—C21—C22—C23	0.19 (18)
O4—C17—C21—C22	−9.28 (17)	C6—N3—C4—N4	−0.07 (14)
O4—C17—C21—C20	172.38 (12)	C8—N6—C7—N5	−0.27 (14)
O1—C16—C19—C24	179.43 (12)	C4—N3—C6—C5	0.26 (14)
O1—C16—C19—C20	−3.62 (17)	C4—N4—C5—C6	0.28 (14)
N2—C2—C3—N1	0.12 (15)	C9—N5—C7—N6	0.04 (13)
N4—C5—C6—N3	−0.34 (14)	C1—N1—C3—C2	−0.20 (14)
N6—C8—C9—N5	−0.38 (14)	C1—N2—C2—C3	0.00 (15)
N10—C14—C15—N9	−0.07 (16)	C11—N8—C10—N7	0.04 (15)
N8—C11—C12—N7	0.07 (15)	C2—N2—C1—N1	−0.14 (15)
C16—C19—C20—C21	−175.35 (11)	C14—N10—C13—N9	0.26 (16)
C24—C19—C20—C21	1.69 (18)	C3—N1—C1—N2	0.21 (14)
C24—C23—C18—O5	0.63 (17)	C13—N10—C14—C15	−0.11 (16)
C24—C23—C18—O6	−179.45 (12)	C13—N9—C15—C14	0.23 (16)
C24—C23—C22—C21	−0.15 (18)	C12—N7—C10—N8	0.01 (15)
C17—C21—C22—C23	−178.19 (11)	C15—N9—C13—N10	−0.30 (15)
C17—C21—C20—C19	177.39 (11)	C10—N7—C12—C11	−0.05 (15)
C19—C24—C23—C18	−178.17 (11)	C10—N8—C11—C12	−0.07 (15)
C19—C24—C23—C22	0.88 (18)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7B···O6	0.88 (2)	1.89 (2)	2.7558 (14)	168 (2)
O7—H7C···O4ⁱⁱ	0.90 (1)	1.95 (2)	2.8455 (15)	175 (2)
N2—H2···O2ⁱⁱⁱ	0.86	1.89	2.7295 (14)	166
N4—H4···O2^iv	0.85	1.90	2.7337 (14)	166
N7—H7A···O4	0.89	1.81	2.6931 (14)	173
N6—H6···O1	0.87	1.83	2.6948 (14)	169
N10—H10A···O3^v	0.88	1.79	2.6492 (14)	164
N8—H8A···O6^vi	0.88	1.86	2.7351 (14)	172
N9—H9A···O5	0.90	1.71	2.6030 (14)	175

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

Hydrogen-bond geometry (Å,°) top

D—H···A	Type	Graph-set	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	a	D, D²₂(11)	0.860 (11)	1.888 (11)	2.7294 (15)	165.5 (7)
N4—H4···O2ⁱⁱ	b	D, D²₂(11)	0.854 (12)	1.898 (11)	2.7336 (15)	165.9 (9)
N6—H6···O1	c	D, D²₂(11)	0.872 (12)	1.834 (12)	2.6949 (15)	168.9 (7)
O7—H7B···O6	d	D	0.875 (18)	1.894 (18)	2.7558 (15)	167.9 (17)
O7—H7C···O4ⁱⁱⁱ	e	D	0.900 (15)	1.947 (16)	2.8456 (15)	175.3 (16)
N7—H7A···O4	f	D	0.892 (13)	1.806 (14)	2.6932 (16)	172.6 (8)
N8—H8A···O6^v	g	D	0.880 (10)	1.861 (10)	2.7350 (15)	172.1 (8)
N10—H10A···O3^iv	h	D	0.881 (14)	1.791 (14)	2.6492 (15)	164.2 (5)
N9—H9A···O5	i	D	0.889 (12)	1.706 (12)	2.6031 (16)	174.6 (10)

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

Funding information

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

References

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