Synthesis and structure of tris­(2-methyl-1H-imidazol-3-ium) 5-carb­oxy­benzene-1,3-di­carboxyl­ate 3,5-di­carb­oxy­benzoate

Asprilla-Herrera, L.M.; Techert, S.; Velazquez-Garcia, J. de J.

doi:10.1107/S2056989025002063

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 81| Part 4| April 2025| Pages 303-309

https://doi.org/10.1107/S2056989025002063

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Synthesis and structure of tris(2-methyl-1H-imidazol-3-ium) 5-carboxybenzene-1,3-dicarboxylate 3,5-dicarboxybenzoate

Lina Maria Asprilla-Herrera,^a Simone Techert ^b,^c and Jose de Jesus Velazquez-Garcia ^c ^*

^aDepartment of Chemistry, Faculty of Natural and Exact Sciences, Universidad del, Valle, Calle 13 No. 100-00, 760042 Cali, Colombia, ^bInstitut für Röntgenphysik, Georg-August-Universität Göttingen, Friedrich-Hund-Platz 1, 37077 Göttingen, Germany, and ^cDeutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22607 Hamburg, Germany
^*Correspondence e-mail: jose.velazquez@desy.de

Edited by V. Jancik, Universidad Nacional Autónoma de México, México (Received 21 October 2024; accepted 4 March 2025; online 11 March 2025)

The structure of the title salt, 3C₄H₇N₂⁺·C₉H₅O₆⁻·C₉H₄O₆²⁻, 1, consists of three 2-methyl-imidazolium cations and both a single and a doubly deprotonated form of trimesic acid as anions. A detailed analysis of the bond lengths and angles reveals both differences and similarities between compound 1 and the previously reported 2-methyl-1H-imidazol-3-ium 3,5-dicarboxybenzoate structure [Baletska et al. (2023). Acta Cryst. E79, 1088–109], as well as the neutral counterpart of the ions. Examination of the crystal packing shows the formation of infinite chains by the anions, which, along with the cations, form zigzag planes parallel to the ab plane. The packing interactions are primarily driven by π–π interactions and hydrogen bonding between anions.

Keywords: crystal structure; 2-methylimidazole; trimesic acid.

CCDC reference: 2428811

1. Chemical context

Trimesic acid (H₃btc, or benzene-1,2,3-tricarboxylic acid) and 2-methylimidazole (2-mIm) are two well-known organic compounds with a wide range of applications. Trimesic acid, a planar and highly symmetrical trifunctional compound, has been used for self-assembled molecular monolayers and surface functionalization (Ha et al., 2010 ; Lin et al., 2023 ; Chen et al., 2014 ; Korolkov et al., 2012 ; MacLeod, 2019 ; Iancu et al., 2013 ). Additionally, H₃btc, along with dendrimers based on it, has been employed in biomolecular delivery systems (Salamończyk, 2011 ; Mat Yusuf et al., 2017 ; Emani et al., 2023 ). On the other hand, 2-mIm, a nitrogen-containing heterocyclic organic compound, is widely used in the preparation of pharmaceuticals, photographic and photothermographic chemicals, dyes and pigments, agricultural chemicals, and in rubber production (Hachuła et al., 2010 ; Chan, 2004 ). Both H₃btc and 2-mIm are also well-known ligands in the syntheses of metal–organic frameworks (MOFs), such as HKUST-1 (Chui et al., 1999 ), MIL-100 (Férey et al., 2004 ), ZIF-8 (Park et al., 2006 ), and ZIF-67 (Banerjee et al., 2008 ), which have applications in gas adsorption, catalysis, and drug delivery, among others (Zhong et al., 2018a ,b ; Zhao et al., 2024 ; Huang et al., 2011 ; Song et al., 2024 ; Abdelhamid, 2021 ; Sun et al., 2012 ).

In our previous studies, we synthesised hexaaquacobalt bis(2-methyl-1H-imidazol-3-ium) tetraaquabis(benzene-1,3,5-tricarboxylato-κO)cobalt (Velazquez-Garcia & Techert, 2022 ) and 2-methyl-1H-imidazol-3-ium 3,5-dicarboxybenzoate (Baletska et al., 2023 ) using 2-mIm and H₃btc as organic compounds. In this work, we used the same organic compounds to synthesise the title compound, 1.

2. Structural commentary

Compound 1 crystallizes with one H₂btc⁻, one Hbtc²⁻, and three H2-mIm⁺ ions in the asymmetric unit, space group P2₁/n. An ellipsoid plot illustrating these ionic species is shown in Fig. 1. For clarity, the three crystallographically independent cations are labelled as A, B, and C to facilitate their identification.

Figure 1
Single-crystal X-ray structure of 1 with displacement ellipsoids drawn at the 50% probability level.

Table 1 presents selected bond distances and angles of the H₂btc⁻ ion, while Table 2 shows those for the Hbtc²⁻ ion. The shortest bond in the H₂btc⁻ ion is between C21 and O1 at 1.214 (2) Å, while the longest is between C9 and C20 at 1.519 (2) Å. In the Hbtc²⁻ ion, the shortest bond is C18—O9 at 1.214 (2) Å, and the longest is C6—C17 at 1.510 (2) Å.

Table 1
Selected bond lengths (Å), angles (°) and torsion angles (°) of the H₂btc⁻ anion in 1

C10—C11	1.392 (2)	C7—C12	1.391 (2)	C8—C9	1.389 (2)
C11—C12	1.393 (2)	C7—C8	1.394 (2)	C9—C10	1.394 (2)
C11—C21	1.499 (2)	C7—C22	1.492 (2)	C9—C20	1.519 (2)
O1—C21	1.214 (2)	O3—C20	1.247 (2)	O5—C22	1.218 (2)
O2—C21	1.303 (2)	O4—C20	1.258 (2)	O6—C22	1.318 (2)
C10—C11—C12	119.68 (15)	C7—C12—C11	119.86 (16)	O1—C21—O2	124.30 (16)
C9—C8—C7	120.68 (15)	C12—C7—C8	119.93 (15)	O3—C20—O4	126.76 (17)
C8—C9—C10	118.98 (16)	C11—C10—C9	120.84 (15)	O5—C22—O6	124.31 (15)
C10—C11—C21—O1	−4.4 (2)	C10—C9—C20—O4	−173.05 (15)	C10—C11—C12—-C7	2.3 (2)
C12—C11—C21—O1	174.23 (16)	C8—C9—C20—O4	5.4 (2)	C12—C7—C8—C9	0.0 (2)
C10—C11—C21—O2	176.85 (15)	C12—C7—C22—O5	−177.56 (16)	C7—C8—C9—C10	1.5 (2)
C12—C11—C21—O2	−4.5 (2)	C8—C7—C22—O5	1.9 (2)	C8—C9—C10—C11	−1.2 (2)
C10—C9—C20—O3	6.0 (2)	C12—C7—C22—O6	1.2 (2)	C8—C7—C12—C11	−1.9 (2)
C8—C9—C20—O3	−175.60 (15)	C8—C7—C22—O6	−179.37 (15)	C9—C10—C11—C12	−0.7 (2)

Table 2
Selected bond lengths (Å), angles (°) and torsion angles (°) of the Hbtc²⁻ anion in 1

C1—C6	1.393 (2)	C2—C3	1.39 (2)	C4—C5	1.392 (2)
C1—C2	1.398 (2)	C3—C4	1.391 (2)	C5—C6	1.388 (2)
C2—C19	1.504 (2)	C4—C18	1.486 (2)	C6—C17	1.510 (2)
O7—C17	1.255 (2)	O9—C18	1.214 (2)	O11—C19	1.2555 (19)
O8—C17	1.2650 (19)	O10—C18	1.338 (2)	O12—C19	1.263 (2)
C2—C3—C4	119.79 (15)	C6—C1—C2	120.38 (16)	O7—C17—O8	125.41 (15)
C6—C5—C4	120.39 (15)	C3—C2—C1	119.79 (14)	O9—C18—O10	123.24 (16)
C3—C4—C5	120.21 (16)	C5—C6—C1	119.38 (15)	O11—C19—O12	124.16 (15)
C1—C6—C17—O7	15.5 (2)	C3—C4—C18—O10	17.1 (2)	C1—C2—C3—C4	2.5 (2)
C5—C6—C17—O7	167.31 (14)	C5—C4—C18—O10	164.63 (14)	C2—C3—C4—C5	−0.5 (2)
C1—C6—C17—O8	163.84 (15)	C1—C2—C19—O11	−163.18 (15)	C2—C1—C6—C5	−0.4 (2)
C5—C6—C17—O8	−13.4 (2)	C3—C2—C19—O11	13.5 (2)	C3—C4—C5—C6	−1.5 (2)
C3—C4—C18—O9	−163.64 (16)	C1—C2—C19—O12	15.8 (2)	C4—C5—C6—C1	1.6 (2)
C5—C4—C18—O9	14.6 (2)	C3—C2—C19—O12	−167.44 (15)	C6—C1—C2—C3	−2.4 (2)

The C—C and C—O bond lengths in the H₂btc⁻ ion range from 1.389 (2) to 1.519 (2) Å and 1.214 (2) to 1.318 (2) Å, respectively. For the Hbtc²⁻ ion, the C—C bond lengths span 1.388 (2) to 1.510 (2) Å, while the C—O bonds range from 1.214 (2) to 1.338 (2) Å. These values are comparable to those in the neutral H₃btc molecule (Tothadi et al., 2020 ), where the C—C bond lengths range from 1.381 (6) to 1.494 (9) Å, and C—O bonds range from 1.229 (5) to 1.303 (5) Å. They are also consistent with the bond lengths observed in the H₂btc⁻ anion reported in our previous work (Baletska et al., 2023), and featuring ranges of 1.388 (2)–1.511 (2) Å for C—C bonds and 1.224 (2)–1.320 (2) Å for C—O bonds.

The C—C—C angles in H₂btc⁻ in 1 range from 118.9 (2) to 120.8 (2)°, while in the Hbtc²⁻ ion, they fall between 119.4 (2) and 120.4 (2)°. These values are comparable to the corresponding angles in H₃btc [119.0 (4)–121.1 (4)°] and H₂btc⁻ reported by Baletska et al. (2023) [118.9 (2)–121.4 (4)°]. The O—C—O angles in the H₂btc⁻ ion in complex 1 span 124.3 (2) to 126.8 (2)°, and in the Hbtc²⁻ ion, they range from 123.2 (2) to 125.4 (2)°. These values are also consistent with those found in neutral H₃btc [124.4 (4)–125.0 (4)°] and in H₂btc⁻ from [123.9 (2)–126.1 (2)°; Baletska et al., 2023].

The main difference between the anions in 1, the neutral H₃btc molecule, and the H₂btc⁻ ion (Baletska et al., 2023) lies in their torsion angles. In the H₃btc molecule, the oxygen atoms are nearly coplanar with the aromatic ring, with torsion angles deviating from 0 or 180° by no more than 4.2 (4)°. H₂btc⁻ (Baletska et al., 2023) shows a wider deviation range, from 4.2 (2) to 16.6 (2)°. In comparison, the H₂btc⁻ ion in 1 exhibits intermediate values, ranging from 0.6 (2) to 7.0 (2)°, whereas the Hbtc²⁻ ion shows the largest torsion angles, ranging from 12.6 (2) to 17.1 (2)°.

These differences are further emphasised through molecular overlays generated using Mercury software (Macrae et al., 2020 ). The overlays (Fig. 2) show that the H₂btc⁻ ion in 1 resembles the neutral H₃btc more closely (root-mean-square deviation, r.m.s.d. = 0.0683 Å; maximal deviation, max. d. = 0.1257 Å) than the H₂btc⁻ ion) (r.m.s.d. = 0.1039 Å; max. d. = 0.2189 Å; Baletska et al., 2023). On the other hand, the Hbtc²⁻ ion in 1 shows a lower resemblance to H₃btc (r.m.s.d. = 0.1856 Å; max. d. = 0.3985 Å) compared to the H₂btc⁻ ion (r.m.s.d. = 0.09 Å; max. d. = 0.2344 Å; Baletska et al., 2023). Note that hydrogen atoms were excluded from the model during the overlay process.

Figure 2
Overlay plot comparing the H₂btc⁻ (dark blue) and Hbtc²⁻ (light blue) ions in 1 with (a) H₃btc (red; Tothadi et al. 2020

) and (b) H₂btc⁻ (green; Baletska et al., 2023

). Hydrogen atoms are omitted for clarity.

Table 3 presents selected bond lengths, angles, and torsions for the H2-mIm⁺ cations. The C—C bond distances fall in the range 1.339 (3)–1.483 (3) Å, while the C—N bonds vary from 1.323 (2) to 1.383 (2) Å. These values are comparable to the corresponding distances observed in the neutral 2-mIm⁺ molecule reported by Hachuła et al. (2010) [C—C = 1.367 (1)–1.488 (1) Å, C—N = 1.329 (1)–1.385 (1) Å] and in the H2-mIm⁺ ion reported by Baletska et al. (2023) [C—C = 1.345 (3)–1.481 (3) Å, C—N = 1.327 (2)–1.377 (2) Å].

Table 3
Selected bond lengths (Å), angles (°) and torsion angles (°) of the H2-mIm⁺ cations in 1

A		B		C
C13—C16	1.483 (3)	C23—C24	1.482 (3)	C27—C30	1.482 (3)
C14—C15	1.348 (2)	C25—C26	1.339 (3)	C28—C29	1.346 (3)
N1—C13	1.326 (2)	N3—C24	1.332 (2)	N5—C30	1.330 (2)
N1—C14	1.370 (2)	N3—C25	1.383 (2)	N5—C28	1.380 (2)
N2—C13	1.330 (2)	N4—C24	1.323 (2)	N6—C30	1.335 (2)
N2—C15	1.371 (2)	N4—C26	1.380 (2)	N6—C29	1.380 (2)
C13—N2—C15	109.13 (14)	C28—C29—N6	106.06 (17)	C24—N4—C26	108.48 (16)
C13—N1—C14	109.87 (15)	C29—C28—N5	107.12 (17)	C24—N3—C25	109.08 (15)
C14—C15—N2	107.24 (16)	C30—N5—C28	109.18 (16)	C25—C26—N4	107.85 (16)
C15—C14—N1	106.39 (15)	C30—N6—C29	108.92 (16)	C26—C25—N3	106.35 (17)
N1—C13—N2	107.36 (16)	N4—C24—N3	108.31 (16)	N5—C30—N6	107.91 (16)
N1—C14—C15—N2	0.1 (2)	N3—C25—C26—N4	0.0 (2)	N5—C28—C29—N6	−0.5 (2)
C13—N1—C14—C15	0.4 (2)	C24—N3—C25—C26	0.4 (2)	C30—N5—C28—C29	0.5 (2)
C14—N1—C13—N2	−0.8 (2)	C25—N3—C24—N4	0.7 (2)	C28—N5—C30—N6	−0.2 (2)
C13—N2—C15—C14	−0.5 (2)	C24—N4—C26—C25	−0.5 (2)	C30—N6—C29—C28	0.4 (2)
C15—N2—C13—N1	0.8 (2)	C26—N4—C24—N3	0.7 (2)	C29—N6—C30—N5	0.0 (2)
C14—N1—C13—C16	177.8 (2)	C26—N4—C24—C23	179.13 (18)	C28—N5—C30—C27	−179.94 (17)
C15—N2—C13—C16	−177.7 (2)	C25—N3—C24—C23	179.12 (18)	C29—N6—C30—C27	179.67 (18)

Imidazole derivatives often exhibit an asymmetry in the two endocyclic N—C bonds (Hachuła et al., 2010). However, this asymmetry is minimal in all three cations of 1, with differences between the two N—C bond lengths of 0.001 (3), 0.003 (3), and 0.0 (3) Å for cations A, B, and C, respectively. These values are comparable with the asymmetry found in the H2-mIm⁺ ion [0.008 (3) Å; Baletska et al., 2023] and are significantly smaller than that reported for the neutral molecule [0.022 (1) Å]. This increased symmetry supports the idea that protonation of the imidazole reduces the disparity between the two endocyclic N—C bonds.

Protonation to an H2-mIm⁺ ion also leads to a more symmetrical heterocyclic ring. In the H2-mIm⁺ ion (Baletska et al., 2023), this increased symmetry is observed in the C—C—N and N—C—N angles of the heterocyclic ring, which closely approach the ideal pentagon angle of 108°, with a maximum deviation of 1.6 (2)°. In contrast, the neutral 2-mIm molecule shows a larger deviation of 3.4 (1)°. In compound 1, the maximum deviations from the ideal angles of a pentagon are 1.9 (2), 1.9 (2), and 1.7 (2)° for cations A, B, and C, respectively. These values confirm that the protonated imidazole exhibits a more symmetrical ring structure than its neutral counterpart.

An analysis of the torsion angles in all cations in compound 1 reveals that the methyl group in cation A is less coplanar to the ring than in other cations. This is evident from the maximum deviation from 180° of the C—N—C—C^Me torsion angles (where C^Me represents the carbon from the methyl group). Cation A shows a deviation of 2.3 (2)°, while cations B and C exhibit smaller deviations of 0.9 (2) and 0.3 (2)°, respectively. The deviation in cation A is also larger than that observed in the neutral molecule [0.7 (1)°] and the H2-mIm⁺ ion [0.5 (2)°; Baletska et al., 2023]. The root-mean-squared deviation (r. m. s. d.) and maximal deviation (max. d.) values, calculated by Mercury software for the molecular overlays of the three H2-mIm⁺ cations in 1 with the H2-mIm⁺ cation (Baletska et al., 2023) and the neutral molecule (Fig. 3), show a greater similarity between the protonated forms compared to the neutral molecule. The r. m. s. d. and max. d. values for the cations of 1 and the protonated H2-mIm⁺ (Baletska et al., 2023) range from 0.0067 to 0.0140 Å and 0.0092 to 0.0201 Å, respectively, indicating a close resemblance. On the other hand, the values for the neutral molecule are notably higher, ranging from 0.0269 to 0.0297 Å (r.m.s.d.) and 0.0402 to 0.0474 Å (max. d.). In all cases, hydrogen atoms were omitted from the model during the overlay process.

Figure 3
Overlay plot comparing the three H2-mIm⁺ ions (dark blue - A, B and C) in 1 with (a) 2-mIm (pink; Hachułaet al., 2010) and (b) H2-mIm⁺ ion (green; Baletska et al.,, 2023

). Hydrogen atoms are omitted for clarity.

3. Supramolecular features

The primary intermolecular interaction contributing to the crystal packing includes hydrogen bonds between all ions, along with π–π stacking between anions. Table 4 provides a summary of the hydrogen bonds found within the compound. As shown in Fig. 4a, infinite chains are formed along the a axis through hydrogen bonding between H₂btc⁻ and Hbtc²⁻ anions. These chains are further linked, via hydrogen bonding, with all of the cations, forming zigzag planes parallel to the ab plane (Fig. 4b,c). Each plane interacts with two types of neighbouring planes: one with a parallel zigzag pattern, interacting via π–π stacking between H₂btc⁻ and Hbtc²⁻ ions [centroid-to-centroid distance of 3.5663 (12) Å, perpendicular distance between planes ∼3.3 Å and offset of 1.249 Å], and another arranged in an antiparallel configuration, with the zigzag pattern running in the opposite direction. This antiparallel plane interacts via hydrogen bonding between Hbtc²⁻ ions (Fig. 5). Note that the spaces observed in the planes in Fig. 4b are filled by counter-ions from the adjacent planes with a parallel zigzag pattern, ensuring no voids within compound 1.

Table 4
Hydrogen-bond geometry (Å, °).

	Graph-set descriptor	type	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O8^V	D(2)	d	0.86 (2)	1.911 (18)	2.737 (2)	160.8 (7)
O2—H2⋯O7ⁱ	D(2)	a	0.96 (3)	1.57 (2)	2.5222 (19)	170.7 (17)
N2—H2A⋯O11^iv	D(2)	e	0.88 (3)	1.93 (2)	2.806 (2)	172.5 (13)
N3—H3A⋯O11	D(2)	f	0.935 (19)	1.874 (19)	2.778 (2)	162.1 (18)
N4—H4⋯O4^vi	D(2)	g	1.01 (2)	1.59 (2)	2.593 (2)	172.6 (9)
N5—H5A⋯O3^vii	D(2)	h	1.01 (2)	1.69 (2)	2.655 (2)	159.9 (5)
O6—H6⋯O12ⁱⁱ	D(2)	b	0.93 (3)	1.69 (2)	2.6189 (19)	171.7 (16)
N6—H6A⋯O8	D(2)	i	0.921 (17)	1.886 (19)	2.800 (2)	170.9 (13)
O10—H10A⋯O12ⁱⁱⁱ	C(8)	c	0.93 (3)	1.71 (3)	2.6156 (18)	162 (2)

C14—H14⋯O1^v			0.95	2.52	3.098 (2)	119
C15—H15⋯O10			0.95	2.46	3.280 (2)	144
C15—H15⋯O5^iv			0.95	2.38	3.038 (2)	126
C25—H25⋯O5			0.95	2.55	3.292 (2)	135
C27—H27B⋯O9			0.98	2.41	3.380 (3)	168
C28—H28⋯O9^vii			0.95	2.39	2.990 (2)	121
C29—H29⋯O1			0.95	2.33	3.108 (2)	138
(i) 1 − x, 1 − y, 1 − z; (ii) 2 − x, 1 − y, 1 − z; (iii) $[{3\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (iv) − $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z; (v) $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z; (vi) 2 − x, 2 − y, 1 − z; (vii 1 − x, 2 − y, 1 − z.

Figure 4
(a) View down the c axis showing an infinite chain of H₂btc⁻–Hbtc²⁻ anions running along the a axis. A plane formed by the H2-mIm⁺ ions (green) and the H₂btc⁻-Hbtc²⁻ chains, view down (b) the c axis and (c) the a axis.

Figure 5
Crystal packing in compound 1 viewed down the a axis showing the π–π interactions and hydrogen bonding connecting the 2H-mim⁺–H₂btc⁻–Hbtc²⁻ planes that run parallel to the ab plane. The H2-mIm⁺ ions are highlighted in green.

A graph-set analysis (Etter et al., 1990 ; Bernstein et al., 1995 ) allows a more detailed examination of the intermolecular interaction patterns within 1. The analysis reveals that 1 contains nine motifs at the first-level graph set, including eight discrete D(2) motifs and one chain motif C(8), labelled as type c in Table 4. The second-level graph set (Table 5) reveals a complex network of intermolecular interactions within 1, featuring various patterns: C₂²(16) >a<b, C₂²(12) >d<e, several D₃³ such as >a>c<a, >d>c<d, >e>c<e, >f>c<f, >i>c<I and many D₂², for example >a<d, >a<e and >a<f. A different pattern, rather than discrete and chain, appears in the third order graph set with formation of the rings R₅⁶(42) >a>c〈b〉a<c<b (Fig. 6a) and R₃⁶(36) >c<d>e<c<d>e (Fig. 6b).

Table 5
Second- and third-level graph sets

	Second-level		Third-level
C₂²(16)	>a<b	C₂³(18)	>a>c<b	D₃³(17)	>d<b<h
D₃³(17)	>a>c<a	C₃³(24)	>a<c<b	D₃³(13)	>e<b<g
D₂²(5)	>a<d	R₅⁶(42)	>a>c〈b〉a<c<b	D₃³(13)	>e<b<h
D₂²(9)	>a<e	D₃³(17)	>a<c<d	C₃³(16)	>b<f>g
D₂²(9)	>a<f	D₃³(17)	>a>c<d	D₃³(13)	>f<b<h
D₂²(10)	>g>a	D₃³(13)	>a>c<e	D₃³(17)	>g>b<i
D₂²(10)	>h>a	D₃³(17)	>a<c<e	C₃³(20)	>b〈i〉h
D₂²(5)	>a<i	D₃³(13)	>a>c<f	C₃³(16)	>c<e>d
D₂³ (11)	>b>c<b	D₃³(17)	>a<c<f	C₃³(20)	>c<d>e
D₂²(9)	>b<d	D₃³(17)	>a<c<i	R₆⁶(36)	>c<d>e<c<d>e
D₂²(5)	>b<e	D₃³(17)	>a>c<i	D₃³(13)	>d>c<f
D₂²(5)	>b<f	D₃³(13)	>d<a<g	D₃³(17)	>d<c<f
D₂²(10)	>g>b	D₃³(13)	>d<a<h	D₃³(17)	>d<c<i
D₂²(10)	>h>b	D₃³(17)	>e<a<g	D₃³(17)	>d>c<i
D₂²(9)	>b<i	D₃³(17)	>e<a<h	D₃³(13)	>e<c<f
D₃³(17)	>d>c<d	C₃³(20)	>a<f>g	D₃³(13)	>e>c<f
D₃³(13)	>e>c<e	D₃³(17)	>f<a<h	D₃³(13)	>e<c<i
D₃³(13)	>f>c<f	D₃³(13)	>g>a<i	D₃³(17)	>e>c<i
D₃³(17)	>i>c<i	C₃³(16)	>a〈i〉h	D₃³(13)	>f<c<i
C₂²(12)	>d<e	D₂³(11)	>b<c<d	D₃³(17)	>f>c<i
D₂²(9)	>d<f	D₃³(17)	>b>c<d	D₃³(14)	>d<f>g
D₁²(3)	>d<i	D₂³(11)	>b<c<e	D₂³(8)	>d〈i〉h
D₁²(3)	>e<f	D₃³(13)	>b>c<e	D₂³(8)	>e<f>g
D₂²(9)	>e<i	D₂³(11)	>b<c<f	D₃³(14)	>e〈i〉h
D₂²(7)	<f>g	D₃³(13)	>b>c<f	D₃³(10)	>h<g>f
D₂²(9)	>f<i	D₂³(11)	>b<c<i	D₃³(14)	>i<f>g
D₂²(5)	>g<h	D₃³(17)	>b>c<i	D₃³(14)	>f〈i〉h
D₂²(7)	<h>i	D₃³ (17)	>d<b<g	D₃³(10)	>g<h>i

Figure 6
View along the c axis showing the formation of hydrogen-bonded ring patterns with the graph-set descriptors: (a) R₅⁶(42) and (b) R₆⁶(36).

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 ). The closest to 1 is the previously mentioned structure reported under the refcode LODSUW (Baletska et al., 2023).

Among the various reported structures containing the H2-mIm⁺ cation, we highlight those with the following refcodes: BEZGEU (Dhanabal et al., 2013 ), BOTTEK, BOTTIO, BOTTOU (Meng et al., 2009 ), BOTTEK01, BOTTIO01, BOTTOU01, VURBUG, VURCAN, VURFAQ (Callear et al., 2010 ), DAMGIL (Hinokimoto et al., 2021 ), DOWVUI (Shi et al., 2014 ), FAMFIL, FAMFOR, FAMFUX (Zhang & Zhang, 2017 ), FETDAK (Aakeröy et al., 2005 ), and HILSOL (Qu, 2007 ).

Organic compounds containing both H₂btc⁻ and Hbtc²- were found with the refcodes: RAVPOV (Arunachalam et al., 2012 ), SADKUE (Fan et al., 2003 ), and TUBBAT (Melendez et al., 1996 ). Some compounds with low resemblance to the title compound were reported under the refcodes CUMQUX (Basu et al., 2009 ), HICSUJ (Lie et al., 2013 ), ILELAO (Li & Li, 2016 ), JOCBAH (Falek et al., 2019 ), LUBGUM, LUBHAT, LUBHEX, LUBHIB, LUBHOH, LUBHUN, LUBJAV (Singh et al., 2015 ), SUHRAR (Rajkumar et al., 2020 ), YOCSIT (Habib & Janiak, 2008 ), and WOGBED (Sosa-Rivadeneyra et al., 2024 ).

5. Synthesis and crystallization

To obtain the title compound, 800 µl of an ethanolic solution of 2-mlm (1.57 M) was diluted in 20 ml of ethanol, followed by the addition of 1 ml of an ethanolic solution of H₃btc (0.12 M). The mixture was shaken gently, but no visible changes were observed after 5 min. Crystals of 1 were obtained after 24 h.

6. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 6. The positions of hydrogen atoms were refined with U_iso(H) = 1.2U_eq(C) for CH. Hydrogen atoms bonded to nitrogen atoms (N—H) and oxygen atoms (O—H) were treated with free refinement of bond distances and isotropic displacement parameters (U_iso).

Table 6
Experimental details

Crystal data
Chemical formula	3C₄H₇N₂⁺·C₉H₄O₆²⁻·C₉H₅O₆⁻
M_r	666.60
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	14.172 (3), 15.902 (3), 14.644 (3)
β (°)	110.46 (3)
V (Å³)	3092.0 (12)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.08 × 0.07 × 0.05

Data collection
Diffractometer	Bruker P4
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.695, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	36740, 7127, 5287
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.119, 1.05
No. of reflections	7127
No. of parameters	457
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.27
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: 2428811

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025002063/jq2038sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S2056989025002063/jq2038Isup2.cml

checkCIF report

Computing details top

Tris(2-methyl-1H-imidazol-3-ium) 5-carboxybenzene-1,3-dicarboxylate 3,5-dicarboxybenzoate top

Crystal data top

3C₄H₇N₂⁺·C₉H₄O₆²⁻·C₉H₅O₆⁻	F(000) = 1392
M_r = 666.60	D_x = 1.432 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 14.172 (3) Å	Cell parameters from 5589 reflections
b = 15.902 (3) Å	θ = 2.5–26.9°
c = 14.644 (3) Å	µ = 0.11 mm⁻¹
β = 110.46 (3)°	T = 100 K
V = 3092.0 (12) Å³	Irregular, clear light colourless
Z = 4	0.08 × 0.07 × 0.05 mm

Data collection top

Bruker P4 diffractometer	R_int = 0.052
ω scans	θ_max = 27.6°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −18→18
T_min = 0.695, T_max = 0.746	k = −17→20
36740 measured reflections	l = −19→19
7127 independent reflections	Standard reflections: not measured; every not measured reflections
5287 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)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.0496P)² + 1.5554P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
7127 reflections	Δρ_max = 0.35 e Å⁻³
457 parameters	Δρ_min = −0.27 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.

Refinement. Hydrogen atoms bonded to nitrogen and oxygen were refined with free isotropic displacement parameters and bond lengths (AFIX 44/148)

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

	x	y	z	U_iso*/U_eq
O1	0.53578 (9)	0.64000 (8)	0.61849 (11)	0.0259 (3)
O2	0.61872 (9)	0.52011 (8)	0.62429 (10)	0.0220 (3)
H2	0.5602 (19)	0.4963 (7)	0.6328 (19)	0.053 (8)*
O3	0.68318 (10)	0.90396 (8)	0.54264 (10)	0.0241 (3)
O4	0.83140 (9)	0.89827 (8)	0.52006 (10)	0.0234 (3)
O5	1.02817 (8)	0.63301 (8)	0.58809 (9)	0.0180 (3)
O6	0.95050 (9)	0.51574 (8)	0.60965 (10)	0.0190 (3)
H6	1.0140 (19)	0.4921 (7)	0.6229 (19)	0.051 (7)*
C7	0.86039 (11)	0.64249 (11)	0.58751 (11)	0.0121 (3)
C8	0.85460 (12)	0.72890 (11)	0.57047 (11)	0.0129 (3)
H8	0.910200	0.757596	0.562900	0.015*
C9	0.76831 (12)	0.77347 (11)	0.56445 (11)	0.0128 (3)
C10	0.68832 (11)	0.73080 (11)	0.57804 (11)	0.0124 (3)
H10	0.629504	0.760943	0.575260	0.015*
C11	0.69353 (11)	0.64458 (11)	0.59565 (11)	0.0119 (3)
C12	0.77922 (11)	0.60010 (11)	0.59865 (11)	0.0121 (3)
H12	0.782241	0.540944	0.608288	0.015*
C20	0.76001 (12)	0.86677 (11)	0.54084 (12)	0.0152 (4)
C21	0.60758 (12)	0.60123 (11)	0.61338 (12)	0.0140 (3)
C22	0.95475 (12)	0.59710 (11)	0.59439 (12)	0.0137 (3)
O7	0.52944 (8)	0.55672 (8)	0.35759 (9)	0.0170 (3)
O8	0.45915 (8)	0.67838 (8)	0.37705 (9)	0.0168 (3)
O9	0.60022 (9)	0.94414 (8)	0.30521 (9)	0.0191 (3)
O10	0.73044 (8)	0.93889 (8)	0.25158 (9)	0.0168 (3)
H10A	0.7044 (12)	0.9897 (17)	0.2214 (19)	0.054 (8)*
O11	0.95291 (8)	0.68773 (7)	0.35827 (8)	0.0146 (3)
O12	0.87752 (8)	0.56353 (7)	0.34820 (9)	0.0168 (3)
C1	0.69841 (11)	0.64122 (11)	0.34545 (11)	0.0110 (3)
H1	0.704556	0.582377	0.357238	0.013*
C2	0.77796 (11)	0.68585 (10)	0.33282 (11)	0.0105 (3)
C3	0.76750 (11)	0.77131 (10)	0.31188 (11)	0.0114 (3)
H3	0.820330	0.801448	0.300719	0.014*
C4	0.67944 (12)	0.81258 (11)	0.30732 (11)	0.0121 (3)
C5	0.60164 (11)	0.76843 (11)	0.32292 (11)	0.0120 (3)
H5	0.542357	0.797249	0.321299	0.014*
C6	0.61016 (11)	0.68255 (10)	0.34084 (11)	0.0108 (3)
C17	0.52617 (11)	0.63554 (11)	0.35966 (11)	0.0120 (3)
C18	0.66564 (12)	0.90441 (11)	0.28876 (12)	0.0140 (3)
C19	0.87669 (11)	0.64296 (11)	0.34702 (11)	0.0116 (3)
N1	0.81021 (10)	0.86622 (9)	−0.05350 (11)	0.0158 (3)
H1A	0.8634 (15)	0.86270 (13)	−0.0687 (4)	0.036 (6)*
N2	0.65710 (10)	0.85634 (9)	−0.06081 (11)	0.0169 (3)
H2A	0.5919 (19)	0.8450 (3)	−0.0820 (6)	0.047 (7)*
C13	0.71886 (12)	0.84187 (12)	−0.10972 (13)	0.0180 (4)
C14	0.80713 (13)	0.89782 (12)	0.03242 (13)	0.0191 (4)
H14	0.862098	0.919778	0.085000	0.023*
C15	0.71066 (13)	0.89158 (12)	0.02759 (13)	0.0202 (4)
H15	0.684631	0.908466	0.076363	0.024*
C16	0.69127 (17)	0.80710 (16)	−0.20962 (16)	0.0405 (6)
H16A	0.652114	0.848892	−0.256907	0.061*
H16B	0.650842	0.756108	−0.215027	0.061*
H16C	0.752612	0.793341	−0.222948	0.061*
N3	1.04278 (11)	0.82926 (10)	0.46433 (11)	0.0190 (3)
H3A	1.0001 (13)	0.7868 (13)	0.4287 (11)	0.054 (8)*
N4	1.12129 (11)	0.94728 (10)	0.50099 (11)	0.0194 (3)
H4	1.1453 (6)	1.0059 (16)	0.49572 (18)	0.051 (7)*
C23	1.00047 (15)	0.93620 (14)	0.33006 (14)	0.0280 (5)
H23A	0.928518	0.941715	0.319353	0.042*
H23B	1.009719	0.896478	0.282717	0.042*
H23C	1.027755	0.991192	0.321944	0.042*
C24	1.05406 (13)	0.90477 (11)	0.43016 (13)	0.0177 (4)
C25	1.10444 (14)	0.82389 (12)	0.56105 (14)	0.0231 (4)
H25	1.111071	0.777215	0.603334	0.028*
C26	1.15295 (15)	0.89749 (12)	0.58330 (14)	0.0253 (4)
H26	1.200691	0.912727	0.644847	0.030*
N5	0.38559 (11)	0.94219 (10)	0.51325 (11)	0.0194 (3)
H5A	0.3614 (7)	1.0020 (16)	0.50764 (19)	0.054 (8)*
N6	0.43032 (11)	0.82074 (10)	0.47674 (12)	0.0203 (3)
H6A	0.4446 (4)	0.7773 (13)	0.4420 (10)	0.049 (7)*
C27	0.37791 (15)	0.92675 (15)	0.34081 (14)	0.0313 (5)
H27A	0.343417	0.882455	0.294699	0.047*
H27B	0.441827	0.940409	0.332440	0.047*
H27C	0.335313	0.977045	0.328545	0.047*
C28	0.41150 (14)	0.89349 (12)	0.59641 (14)	0.0223 (4)
H28	0.410189	0.910375	0.658189	0.027*
C29	0.43899 (13)	0.81759 (12)	0.57354 (13)	0.0213 (4)
H29	0.460320	0.770711	0.616009	0.026*
C30	0.39781 (13)	0.89704 (12)	0.44175 (13)	0.0195 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0182 (6)	0.0143 (7)	0.0524 (9)	0.0038 (5)	0.0212 (6)	0.0053 (6)
O2	0.0198 (6)	0.0087 (7)	0.0457 (8)	−0.0005 (5)	0.0219 (6)	0.0028 (6)
O3	0.0297 (7)	0.0136 (7)	0.0334 (7)	0.0068 (5)	0.0167 (6)	0.0054 (6)
O4	0.0255 (6)	0.0112 (7)	0.0367 (8)	−0.0038 (5)	0.0149 (6)	0.0028 (6)
O5	0.0141 (5)	0.0155 (7)	0.0271 (7)	0.0002 (5)	0.0105 (5)	0.0017 (5)
O6	0.0120 (5)	0.0089 (7)	0.0361 (7)	0.0021 (5)	0.0083 (5)	0.0016 (5)
C7	0.0131 (7)	0.0112 (9)	0.0118 (7)	0.0003 (6)	0.0039 (6)	−0.0007 (6)
C8	0.0134 (7)	0.0120 (9)	0.0137 (8)	−0.0024 (6)	0.0054 (6)	−0.0006 (7)
C9	0.0156 (7)	0.0103 (9)	0.0117 (7)	−0.0005 (6)	0.0037 (6)	−0.0003 (6)
C10	0.0117 (7)	0.0121 (9)	0.0132 (7)	0.0019 (6)	0.0042 (6)	−0.0017 (6)
C11	0.0124 (7)	0.0110 (9)	0.0127 (7)	0.0003 (6)	0.0048 (6)	0.0008 (6)
C12	0.0141 (7)	0.0088 (9)	0.0133 (7)	0.0001 (6)	0.0046 (6)	0.0001 (6)
C20	0.0198 (8)	0.0107 (9)	0.0156 (8)	−0.0004 (7)	0.0066 (6)	−0.0006 (7)
C21	0.0144 (7)	0.0108 (9)	0.0176 (8)	0.0004 (6)	0.0066 (6)	−0.0004 (7)
C22	0.0145 (7)	0.0114 (9)	0.0153 (8)	0.0001 (6)	0.0051 (6)	−0.0008 (7)
O7	0.0164 (6)	0.0090 (7)	0.0297 (7)	−0.0022 (5)	0.0131 (5)	−0.0004 (5)
O8	0.0149 (5)	0.0150 (7)	0.0255 (6)	0.0011 (5)	0.0134 (5)	0.0003 (5)
O9	0.0242 (6)	0.0121 (7)	0.0263 (7)	0.0059 (5)	0.0155 (5)	0.0020 (5)
O10	0.0162 (6)	0.0102 (7)	0.0252 (7)	0.0003 (5)	0.0086 (5)	0.0046 (5)
O11	0.0092 (5)	0.0118 (6)	0.0223 (6)	−0.0014 (4)	0.0050 (5)	−0.0006 (5)
O12	0.0129 (5)	0.0075 (6)	0.0304 (7)	0.0010 (5)	0.0080 (5)	−0.0024 (5)
C1	0.0130 (7)	0.0089 (9)	0.0112 (7)	−0.0005 (6)	0.0045 (6)	−0.0009 (6)
C2	0.0112 (7)	0.0086 (9)	0.0118 (7)	−0.0002 (6)	0.0041 (6)	−0.0020 (6)
C3	0.0105 (7)	0.0111 (9)	0.0131 (7)	−0.0027 (6)	0.0047 (6)	−0.0006 (6)
C4	0.0143 (7)	0.0101 (9)	0.0119 (7)	0.0012 (6)	0.0044 (6)	0.0004 (6)
C5	0.0114 (7)	0.0127 (9)	0.0130 (7)	0.0021 (6)	0.0058 (6)	−0.0001 (6)
C6	0.0117 (7)	0.0101 (9)	0.0118 (7)	−0.0004 (6)	0.0055 (6)	−0.0008 (6)
C17	0.0132 (7)	0.0126 (9)	0.0115 (7)	−0.0011 (6)	0.0060 (6)	0.0010 (6)
C18	0.0151 (7)	0.0120 (9)	0.0145 (8)	−0.0007 (6)	0.0046 (6)	0.0000 (7)
C19	0.0121 (7)	0.0108 (9)	0.0122 (7)	0.0000 (6)	0.0046 (6)	−0.0010 (6)
N1	0.0130 (6)	0.0137 (8)	0.0243 (8)	0.0002 (6)	0.0111 (6)	0.0004 (6)
N2	0.0105 (6)	0.0143 (8)	0.0263 (8)	−0.0011 (6)	0.0071 (6)	0.0015 (6)
C13	0.0175 (8)	0.0144 (10)	0.0233 (9)	0.0017 (7)	0.0088 (7)	−0.0002 (7)
C14	0.0162 (8)	0.0208 (10)	0.0194 (9)	0.0005 (7)	0.0051 (7)	−0.0016 (7)
C15	0.0200 (8)	0.0229 (11)	0.0210 (9)	0.0012 (7)	0.0114 (7)	−0.0002 (8)
C16	0.0375 (12)	0.0498 (16)	0.0311 (12)	0.0013 (11)	0.0079 (9)	−0.0155 (11)
N3	0.0185 (7)	0.0134 (8)	0.0254 (8)	−0.0034 (6)	0.0081 (6)	−0.0021 (6)
N4	0.0237 (7)	0.0116 (8)	0.0232 (8)	−0.0034 (6)	0.0087 (6)	−0.0001 (6)
C23	0.0291 (10)	0.0294 (12)	0.0227 (10)	−0.0011 (9)	0.0055 (8)	0.0049 (8)
C24	0.0187 (8)	0.0143 (10)	0.0225 (9)	−0.0010 (7)	0.0102 (7)	−0.0013 (7)
C25	0.0250 (9)	0.0177 (10)	0.0246 (9)	−0.0021 (8)	0.0061 (7)	0.0048 (8)
C26	0.0306 (10)	0.0203 (11)	0.0203 (9)	−0.0054 (8)	0.0030 (8)	0.0027 (8)
N5	0.0235 (7)	0.0125 (8)	0.0245 (8)	0.0036 (6)	0.0113 (6)	−0.0008 (6)
N6	0.0194 (7)	0.0152 (9)	0.0276 (8)	0.0025 (6)	0.0096 (6)	−0.0050 (7)
C27	0.0305 (10)	0.0392 (14)	0.0256 (10)	0.0070 (9)	0.0115 (8)	0.0062 (9)
C28	0.0266 (9)	0.0191 (11)	0.0226 (9)	0.0031 (8)	0.0105 (7)	−0.0009 (8)
C29	0.0222 (8)	0.0171 (10)	0.0247 (9)	0.0045 (7)	0.0083 (7)	0.0019 (8)
C30	0.0165 (8)	0.0196 (10)	0.0234 (9)	0.0021 (7)	0.0082 (7)	−0.0009 (8)

Geometric parameters (Å, º) top

O1—C21	1.214 (2)	N1—H1A	0.86 (2)
O2—H2	0.96 (3)	N1—C13	1.326 (2)
O2—C21	1.303 (2)	N1—C14	1.370 (2)
O3—C20	1.247 (2)	N2—H2A	0.89 (3)
O4—C20	1.258 (2)	N2—C13	1.330 (2)
O5—C22	1.218 (2)	N2—C15	1.371 (2)
O6—H6	0.93 (3)	C13—C16	1.483 (3)
O6—C22	1.318 (2)	C14—H14	0.9500
C7—C8	1.394 (2)	C14—C15	1.348 (2)
C7—C12	1.391 (2)	C15—H15	0.9500
C7—C22	1.492 (2)	C16—H16A	0.9800
C8—H8	0.9500	C16—H16B	0.9800
C8—C9	1.389 (2)	C16—H16C	0.9800
C9—C10	1.394 (2)	N3—H3A	0.93 (3)
C9—C20	1.519 (2)	N3—C24	1.332 (2)
C10—H10	0.9500	N3—C25	1.383 (2)
C10—C11	1.392 (2)	N4—H4	1.00 (3)
C11—C12	1.393 (2)	N4—C24	1.323 (2)
C11—C21	1.499 (2)	N4—C26	1.380 (2)
C12—H12	0.9500	C23—H23A	0.9800
O7—C17	1.255 (2)	C23—H23B	0.9800
O8—C17	1.2650 (19)	C23—H23C	0.9800
O9—C18	1.214 (2)	C23—C24	1.482 (3)
O10—H10A	0.93 (3)	C25—H25	0.9500
O10—C18	1.338 (2)	C25—C26	1.339 (3)
O11—C19	1.2555 (19)	C26—H26	0.9500
O12—C19	1.263 (2)	N5—H5A	1.01 (3)
C1—H1	0.9500	N5—C28	1.380 (2)
C1—C2	1.398 (2)	N5—C30	1.330 (2)
C1—C6	1.393 (2)	N6—H6A	0.92 (3)
C2—C3	1.390 (2)	N6—C29	1.380 (2)
C2—C19	1.504 (2)	N6—C30	1.335 (2)
C3—H3	0.9500	C27—H27A	0.9800
C3—C4	1.391 (2)	C27—H27B	0.9800
C4—C5	1.392 (2)	C27—H27C	0.9800
C4—C18	1.486 (2)	C27—C30	1.482 (3)
C5—H5	0.9500	C28—H28	0.9500
C5—C6	1.388 (2)	C28—C29	1.346 (3)
C6—C17	1.510 (2)	C29—H29	0.9500

C21—O2—H2	109.5	C13—N2—H2A	125.4
C22—O6—H6	109.5	C13—N2—C15	109.13 (14)
C8—C7—C22	118.97 (14)	C15—N2—H2A	125.4
C12—C7—C8	119.95 (15)	N1—C13—N2	107.36 (16)
C12—C7—C22	121.07 (15)	N1—C13—C16	125.80 (17)
C7—C8—H8	119.7	N2—C13—C16	126.82 (17)
C9—C8—C7	120.64 (15)	N1—C14—H14	126.8
C9—C8—H8	119.7	C15—C14—N1	106.39 (15)
C8—C9—C10	118.98 (16)	C15—C14—H14	126.8
C8—C9—C20	120.62 (15)	N2—C15—H15	126.4
C10—C9—C20	120.39 (15)	C14—C15—N2	107.24 (16)
C9—C10—H10	119.6	C14—C15—H15	126.4
C11—C10—C9	120.84 (15)	C13—C16—H16A	109.5
C11—C10—H10	119.6	C13—C16—H16B	109.5
C10—C11—C12	119.68 (15)	C13—C16—H16C	109.5
C10—C11—C21	119.43 (14)	H16A—C16—H16B	109.5
C12—C11—C21	120.88 (15)	H16A—C16—H16C	109.5
C7—C12—C11	119.86 (16)	H16B—C16—H16C	109.5
C7—C12—H12	120.1	C24—N3—H3A	125.5
C11—C12—H12	120.1	C24—N3—C25	108.95 (15)
O3—C20—O4	126.72 (17)	C25—N3—H3A	125.5
O3—C20—C9	117.21 (15)	C24—N4—H4	125.8
O4—C20—C9	116.06 (15)	C24—N4—C26	108.48 (16)
O1—C21—O2	124.30 (16)	C26—N4—H4	125.8
O1—C21—C11	121.75 (16)	H23A—C23—H23B	109.5
O2—C21—C11	113.94 (14)	H23A—C23—H23C	109.5
O5—C22—O6	124.31 (15)	H23B—C23—H23C	109.5
O5—C22—C7	122.51 (16)	C24—C23—H23A	109.5
O6—C22—C7	113.17 (14)	C24—C23—H23B	109.5
C18—O10—H10A	109.5	C24—C23—H23C	109.5
C2—C1—H1	119.8	N3—C24—C23	126.04 (17)
C6—C1—H1	119.8	N4—C24—N3	108.31 (16)
C6—C1—C2	120.38 (16)	N4—C24—C23	125.65 (17)
C1—C2—C19	120.38 (15)	N3—C25—H25	126.8
C3—C2—C1	119.79 (14)	C26—C25—N3	106.40 (17)
C3—C2—C19	119.76 (14)	C26—C25—H25	126.8
C2—C3—H3	120.1	N4—C26—H26	126.1
C2—C3—C4	119.79 (15)	C25—C26—N4	107.85 (16)
C4—C3—H3	120.1	C25—C26—H26	126.1
C3—C4—C5	120.21 (16)	C28—N5—H5A	125.5
C3—C4—C18	122.08 (15)	C30—N5—H5A	125.5
C5—C4—C18	117.69 (14)	C30—N5—C28	108.92 (16)
C4—C5—H5	119.8	C29—N6—H6A	125.6
C6—C5—C4	120.39 (15)	C30—N6—H6A	125.6
C6—C5—H5	119.8	C30—N6—C29	108.78 (16)
C1—C6—C17	120.59 (15)	H27A—C27—H27B	109.5
C5—C6—C1	119.38 (15)	H27A—C27—H27C	109.5
C5—C6—C17	119.97 (14)	H27B—C27—H27C	109.5
O7—C17—O8	125.41 (15)	C30—C27—H27A	109.5
O7—C17—C6	116.86 (14)	C30—C27—H27B	109.5
O8—C17—C6	117.73 (15)	C30—C27—H27C	109.5
O9—C18—O10	123.24 (16)	N5—C28—H28	126.4
O9—C18—C4	122.42 (15)	C29—C28—N5	107.12 (17)
O10—C18—C4	114.33 (14)	C29—C28—H28	126.4
O11—C19—O12	124.16 (14)	N6—C29—H29	126.5
O11—C19—C2	118.50 (15)	C28—C29—N6	107.06 (17)
O12—C19—C2	117.33 (14)	C28—C29—H29	126.5
C13—N1—H1A	125.1	N5—C30—N6	108.11 (16)
C13—N1—C14	109.87 (15)	N5—C30—C27	125.55 (18)
C14—N1—H1A	125.1	N6—C30—C27	126.33 (17)

C7—C8—C9—C10	1.5 (2)	C3—C4—C5—C6	−1.5 (2)
C7—C8—C9—C20	−176.91 (14)	C3—C4—C18—O9	−163.64 (16)
C8—C7—C12—C11	−1.9 (2)	C3—C4—C18—O10	17.1 (2)
C8—C7—C22—O5	1.9 (2)	C4—C5—C6—C1	1.6 (2)
C8—C7—C22—O6	−179.37 (14)	C4—C5—C6—C17	178.78 (14)
C8—C9—C10—C11	−1.2 (2)	C5—C4—C18—O9	14.6 (2)
C8—C9—C20—O3	−175.60 (15)	C5—C4—C18—O10	−164.63 (14)
C8—C9—C20—O4	5.4 (2)	C5—C6—C17—O7	167.31 (14)
C9—C10—C11—C12	−0.7 (2)	C5—C6—C17—O8	−13.4 (2)
C9—C10—C11—C21	177.89 (14)	C6—C1—C2—C3	−2.4 (2)
C10—C9—C20—O3	6.0 (2)	C6—C1—C2—C19	174.27 (14)
C10—C9—C20—O4	−173.05 (15)	C18—C4—C5—C6	−179.87 (14)
C10—C11—C12—C7	2.3 (2)	C19—C2—C3—C4	−174.28 (14)
C10—C11—C21—O1	−4.4 (2)	N1—C14—C15—N2	0.1 (2)
C10—C11—C21—O2	176.85 (15)	C13—N1—C14—C15	0.4 (2)
C12—C7—C8—C9	0.0 (2)	C13—N2—C15—C14	−0.5 (2)
C12—C7—C22—O5	−177.56 (16)	C14—N1—C13—N2	−0.8 (2)
C12—C7—C22—O6	1.2 (2)	C14—N1—C13—C16	177.78 (19)
C12—C11—C21—O1	174.23 (16)	C15—N2—C13—N1	0.8 (2)
C12—C11—C21—O2	−4.5 (2)	C15—N2—C13—C16	−177.7 (2)
C20—C9—C10—C11	177.28 (14)	N3—C25—C26—N4	0.0 (2)
C21—C11—C12—C7	−176.33 (14)	C24—N3—C25—C26	−0.4 (2)
C22—C7—C8—C9	−179.44 (14)	C24—N4—C26—C25	0.5 (2)
C22—C7—C12—C11	177.51 (14)	C25—N3—C24—N4	0.7 (2)
C1—C2—C3—C4	2.5 (2)	C25—N3—C24—C23	−179.16 (18)
C1—C2—C19—O11	−163.18 (15)	C26—N4—C24—N3	−0.7 (2)
C1—C2—C19—O12	15.8 (2)	C26—N4—C24—C23	179.13 (18)
C1—C6—C17—O7	−15.5 (2)	N5—C28—C29—N6	0.4 (2)
C1—C6—C17—O8	163.84 (14)	C28—N5—C30—N6	0.3 (2)
C2—C1—C6—C5	0.4 (2)	C28—N5—C30—C27	179.94 (17)
C2—C1—C6—C17	−176.77 (14)	C29—N6—C30—N5	0.0 (2)
C2—C3—C4—C5	−0.5 (2)	C29—N6—C30—C27	−179.67 (18)
C2—C3—C4—C18	177.76 (14)	C30—N5—C28—C29	−0.5 (2)
C3—C2—C19—O11	13.5 (2)	C30—N6—C29—C28	−0.2 (2)
C3—C2—C19—O12	−167.44 (15)

Selected bond lengths (Å), angles (°) and torsion angles (°) of the H₂btc^- anion in 1 top

C10—C11	1.392 (2)	C7—C12	1.391 (2)	C8—C9	1.389 (2)
C11—C12	1.393 (2)	C7—C8	1.394 (2)	C9—C10	1.394 (2)
C11—C21	1.499 (2)	C7—C22	1.492 (2)	C9—C20	1.519 (2)
O1—C21	1.214 (2)	O3—C20	1.247 (2)	O5—C22	1.218 (2)
O2—C21	1.303 (2)	O4—C20	1.258 (2)	O6—C22	1.318 (2)
C10—C11—C12	119.68 (15)	C7—C12—C11	119.86 (16)	O1—C21—O2	124.30 (16)
C9—C8—C7	120.68 (15)	C12—C7—C8	119.93 (15)	O3—C20—O4	126.76 (17)
C8—C9—C10	118.98 (16)	C11—C10—C9	120.84 (15)	O5—C22—O6	124.31 (15)
C10—C11—C21—O1	-4.4 (2)	C10—C9—C20—O4	-173.05 (15)	C10—C11—C12—-C7	2.3 (2)
C12—C11—C21—O1	174.23 (16)	C8—C9—C20—O4	5.4 (2)	C12—C7—C8—C9	0.0 (2)
C10—C11—C21—O2	176.85 (15)	C12—C7—C22—O5	-177.56 (16)	C7—C8—C9—C10	1.5 (2)
C12—C11—C21—O2	-4.5 (2)	C8—C7—C22—O5	1.9 (2)	C8—C9—C10—C11	-1.2 (2)
C10—C9—C20—O3	6.0 (2)	C12—C7—C22—O6	1.2 (2)	C8—C7—C12—C11	-1.9 (2)
C8—C9—C20—O3	-175.60 (15)	C8—C7—C22—O6	-179.37 (15)	C9—C10—C11—C12	-0.7 (2)

Selected bond lengths (Å), angles (°) and torsion angles (°) of the Hbtc^2- anion in 1 top

C1—C6	1.393 (2)	C2—C3	1.39 (2)	C4—C5	1.392 (2)
C1—C2	1.398 (2)	C3—C4	1.391 (2)	C5—C6	1.388 (2)
C2—C19	1.504 (2)	C4—C18	1.486 (2)	C6—C17	1.510 (2)
O7—C17	1.255 (2)	O9—C18	1.214 (2)	O11—C19	1.2555 (19)
O8—C17	1.2650 (19)	O10—C18	1.338 (2)	O12—C19	1.263 (2)
C2—C3—C4	119.79 (15)	C6—C1—C2	120.38 (16)	O7—C17—O8	125.41 (15)
C6—C5—C4	120.39 (15)	C3—C2—C1	119.79 (14)	O9—C18—O10	123.24 (16)
C3—C4—C5	120.21 (16)	C5—C6—C1	119.38 (15)	O11—C19—O12	124.16 (15)
C1—C6—C17—O7	15.5 (2)	C3—C4—C18—O10	17.1 (2)	C1—C2—C3—C4	2.5 (2)
C5—C6—C17—O7	167.31 (14)	C5—C4—C18—O10	164.63 (14)	C2—C3—C4—C5	-0.5 (2)
C1—C6—C17—O8	163.84 (15)	C1—C2—C19—O11	-163.18 (15)	C2—C1—C6—C5	-0.4 (2)
C5—C6—C17—O8	-13.4 (2)	C3—C2—C19—O11	13.5 (2)	C3—C4—C5—C6	-1.5 (2)
C3—C4—C18—O9	-163.64 (16)	C1—C2—C19—O12	15.8 (2)	C4—C5—C6—C1	1.6 (2)
C5—C4—C18—O9	14.6 (2)	C3—C2—C19—O12	-167.44 (15)	C6—C1—C2—C3	-2.4 (2)

Selected bond lengths (Å), angles (°) and torsion angles (°) of the H2-mIm⁺ cations in 1 top

A		B		C
C13—C16	1.483 (3)	C23—C24	1.482 (3)	C27—C30	1.482 (3)
C14—C15	1.348 (2)	C25—C26	1.339 (3)	C28—C29	1.346 (3)
N1—C13	1.326 (2)	N3—C24	1.332 (2)	N5—C30	1.330 (2)
N1—C14	1.370 (2)	N3—C25	1.383 (2)	N5—C28	1.380 (2)
N2—C13	1.330 (2)	N4—C24	1.323 (2)	N6—C30	1.335 (2)
N2—C15	1.371 (2)	N4—C26	1.380 (2)	N6—C29	1.380 (2)
C13—N2—C15	109.13 (14)	C28—C29—N6	106.06 (17)	C24—N4—C26	108.48 (16)
C13—N1—C14	109.87 (15)	C29—C28—N5	107.12 (17)	C24—N3—C25	109.08 (15)
C14—C15—N2	107.24 (16)	C30—N5—C28	109.18 (16)	C25—C26—N4	107.85 (16)
C15—C14—N1	106.39 (15)	C30—N6—C29	108.92 (16)	C26—C25—N3	106.35 (17)
N1—C13—N2	107.36 (16)	N4—C24—N3	108.31 (16)	N5—C30—N6	107.91 (16)
N1—C14—C15—N2	0.1 (2)	N3—C25—C26—N4	0.0 (2)	N5—C28—C29—N6	-0.5 (2)
C13—N1—C14—C15	0.4 (2)	C24—N3—C25—C26	0.4 (2)	C30—N5—C28—C29	0.5 (2)
C14—N1—C13—N2	-0.8 (2)	C25—N3—C24—N4	0.7 (2)	C28—N5—C30—N6	-0.2 (2)
C13—N2—C15—C14	-0.5 (2)	C24—N4—C26—C25	-0.5 (2)	C30—N6—C29—C28	0.4 (2)
C15—N2—C13—N1	0.8 (2)	C26—N4—C24—N3	0.7 (2)	C29—N6—C30—N5	0.0 (2)
C14—N1—C13—C16	177.8 (2)	C26—N4—C24—C23	179.13 (18)	C28—N5—C30—C27	-179.94 (17)
C15—N2—C13—C16	-177.7 (2)	C25—N3—C24—C23	179.12 (18)	C29—N6—C30—C27	179.67 (18)

Hydrogen-bond geometry (Å, °). top

	Graph-set descriptor	type	D—H	H···A	D···A	D—H···A
N1—H1A···O8^V	D(2)	d	0.86 (2)	1.911 (18)	2.737 (2)	160.8 (7)
O2—H2···O7ⁱ	D(2)	a	0.96 (3)	1.57 (2)	2.5222 (19)	170.7 (17)
N2—H2A···O11^iv	D(2)	e	0.88 (3)	1.93 (2)	2.806 (2)	172.5 (13)
N3—H3A···O11	D(2)	f	0.935 (19)	1.874 (19)	2.778 (2)	162.1 (18)
N4—H4···O4^vi	D(2)	g	1.01 (2)	1.59 (2)	2.593 (2)	172.6 (9)
N5—H5A···O3^vii	D(2)	h	1.01 (2)	1.69 (2)	2.655 (2)	159.9 (5)
O6—H6···O12ⁱⁱ	D(2)	b	0.93 (3)	1.69 (2)	2.6189 (19)	171.7 (16)
N6—H6A···O8	D(2)	i	0.921 (17)	1.886 (19)	2.800 (2)	170.9 (13)
O10—H10A···O12ⁱⁱⁱ	C(8)	c	0.93 (3)	1.71 (3)	2.6156 (18)	162 (2)

C14—H14···O1^v			0.95	2.52	3.098 (2)	119
C15—H15···O10			0.95	2.46	3.280 (2)	144
C15—H15···O5^iv			0.95	2.38	3.038 (2)	126
C25—H25···O5			0.95	2.55	3.292 (2)	135
C27—H27B···O9			0.98	2.41	3.380 (3)	168
C28—H28···O9^vii			0.95	2.39	2.990 (2)	121
C29—H29···O1			0.95	2.33	3.108 (2)	138

(i) 1 - x, 1 - y, 1 - z; (ii) 2 - x, 1 - y, 1 - z; (iii) 3/2 - x, 1/2 + y, 1/2 - z; (iv) -1/2 + x, 3/2 - y, -1/2 + z; (v) 1/2 + x, 3/2 - y, -1/2 + z; (vi) 2 - x, 2 - y, 1 - z; (vii 1 - x, 2 - y, 1 - z.

Second- and third-level graph sets top

	Second-level		Third-level
C₂²(16)	>a<b	C₂³(18)	>a>c<b	D₃³(17)	>d<b<h
D₃³(17)	>a>c<a	C₃³(24)	>a<c<b	D₃³(13)	>e<b<g
D₂²(5)	>a<d	R₅⁶(42)	>a>c〈b〉a<c<b	D₃³(13)	>e<b<h
D₂²(9)	>a<e	D₃³(17)	>a<c<d	C₃³(16)	>b<f>g
D₂²(9)	>a<f	D₃³(17)	>a>c<d	D₃³(13)	>f<b<h
D₂²(10)	>g>a	D₃³(13)	>a>c<e	D₃³(17)	>g>b<i
D₂²(10)	>h>a	D₃³(17)	>a<c<e	C₃³(20)	>b〈i〉h
D₂²(5)	>a<i	D₃³(13)	>a>c<f	C₃³(16)	>c<e>d
D₂³ (11)	>b>c<b	D₃³(17)	>a<c<f	C₃³(20)	>c<d>e
D₂²(9)	>b<d	D₃³(17)	>a<c<i	R₆⁶(36)	>c<d>e<c<d>e
D₂²(5)	>b<e	D₃³(17)	>a>c<i	D₃³(13)	>d>c<f
D₂²(5)	>b<f	D₃³(13)	>d<a<g	D₃³(17)	>d<c<f
D₂²(10)	>g>b	D₃³(13)	>d<a<h	D₃³(17)	>d<c<i
D₂²(10)	>h>b	D₃³(17)	>e<a<g	D₃³(17)	>d>c<i
D₂²(9)	>b<i	D₃³(17)	>e<a<h	D₃³(13)	>e<c<f
D₃³(17)	>d>c<d	C₃³(20)	>a<f>g	D₃³(13)	>e>c<f
D₃³(13)	>e>c<e	D₃³(17)	>f<a<h	D₃³(13)	>e<c<i
D₃³(13)	>f>c<f	D₃³(13)	>g>a<i	D₃³(17)	>e>c<i
D₃³(17)	>i>c<i	C₃³(16)	>a〈i〉h	D₃³(13)	>f<c<i
C₂²(12)	>d<e	D₂³(11)	>b<c<d	D₃³(17)	>f>c<i
D₂²(9)	>d<f	D₃³(17)	>b>c<d	D₃³(14)	>d<f>g
D₁²(3)	>d<i	D₂³(11)	>b<c<e	D₂³(8)	>d〈i〉h
D₁²(3)	>e<f	D₃³(13)	>b>c<e	D₂³(8)	>e<f>g
D₂²(9)	>e<i	D₂³(11)	>b<c<f	D₃³(14)	>e〈i〉h
D₂²(7)	<f>g	D₃³(13)	>b>c<f	D₃³(10)	>h<g>f
D₂²(9)	>f<i	D₂³(11)	>b<c<i	D₃³(14)	>i<f>g
D₂²(5)	>g<h	D₃³(17)	>b>c<i	D₃³(14)	>f〈i〉h
D₂²(7)	<h>i	D₃³ (17)	>d<b<g	D₃³(10)	>g<h>i

Funding information

Funding for this research was provided by: HG-recruitment, HG-Innovation ‘ECRAPS’, HG-Innovation DSF/DASHH and CMWS (grant to ST); LMAH thanks the DESY-Helmholtz-Summer student fund for financial support.

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