Crystal structure of catena-poly[[di­aqua­di­imida­zole­cobalt(II)]-μ2-2,3,5,6-tetra­bromo­benzene-1,4-di­carboxyl­ato]

Kumagai, H.; Kawata, S.; Ogihara, N.

doi:10.1107/S2056989024009915

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Volume 80| Part 11| November 2024| Pages 1217-1220

https://doi.org/10.1107/S2056989024009915

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Crystal structure of catena-poly[[diaquadiimidazolecobalt(II)]-μ₂-2,3,5,6-tetrabromobenzene-1,4-dicarboxylato]

Hitoshi Kumagai,^a ^* Satoshi Kawata ^b and Nobuhiro Ogihara ^a

^aToyota Central R&D Labs., Inc., 41-1 Yokomichi, Nagakute, Aichi 480-1192, Japan, and ^bDepartment of Chemistry, Fukuoka University, 8-19-1 Nanakuma Jonan-ku, Fukuoka, 814-0180, Japan
^*Correspondence e-mail: e1254@mosk.tytlabs.co.jp

Edited by T. Akitsu, Tokyo University of Science, Japan (Received 10 September 2024; accepted 10 October 2024; online 31 October 2024)

The asymmetric unit of the title compound, [Co(C₈Br₄O₄)(C₃H₄N₂)₂(H₂O)₂]_n or [Co(Br₄bdc)(im)₂(H₂O)₂]_n, comprises half of Co^II ion, tetrabromobenzenedicarboxylate (Br₄bdc²⁻), imidazole (im) and a water molecule. The Co^II ion exhibits a six-coordinated octahedral geometry with two oxygen atoms of the Br₄bdc²⁻ ligand, two oxygen atoms of the water molecules, and two nitrogen atoms of the im ligands. The carboxylate group is nearly perpendicular to the benzene ring and shows monodentate coordination to the Co^II ion. The Co^II ions are bridged by the Br₄bdc²⁻ ligand, forming a one-dimensional chain. The carboxylate group acts as an intermolecular hydrogen-bond acceptor toward the im ligand and a coordinated water molecule. The chains are connected by interchain N—H⋯O(carboxylate) and O—H(water)⋯O(carboxylate) hydrogen-bonding interactions and are not arranged in parallel but cross each other via interchain hydrogen bonding and π–π interactions, yielding a three-dimensional network.

Keywords: crystal structure; cobalt; hydrogen bonding; tetrabromoterephthalate; imidazole.

CCDC reference: 2391124

1. Chemical context

Infinite assemblies of metal ions bridged by organic linkers, so-called metal–organic frameworks (MOFs) or coordination polymers (CPs), are being actively investigated (Cheetham et al., 1999 ; Férey, 2008 ; Kitagawa et al., 2004 ; Rao et al., 2008 ; Yaghi, et al., 2019 ). Benzenedicarboxylate (bdc²⁻ dianion), also known as terephthalate dianion, is a well-known linker that gives functional MOFs or CPs (Eddaoudi et al., 2002 ; Kurmoo 2009 ). We have not only been preparing electrode materials using terephthalate dianion and its analogues (Ogihara et al., 2014 , 2017 , 2023 ; Yasuda et al., 2014 ; Mikita et al., 2020 ) but also fine tuning the crystal structures and properties of MOFs and CPs using R₄bdc²⁻ dianions (R = H, F, Cl, Br) in which halogen atoms and metal ions are systematically varied (Kumagai et al., 2012 , 2021 ). We have used 4,4′-bipyridine (4,4′-bpy) or pyrazine (pyz) as co-ligands and have reported on the structure, thermal stability, and water adsorption/desorption properties of the resultant materials. In this contribution, we focused on using the Br₄bdc²⁻ dianion and imidazole (im) as a co-ligand instead of a pyz ligand in the synthesis of a Co^II–Br₄bdc²⁻ dianion system to observe the structural change resulting from the substitution of im for pyz. Although the pyz ligand coordinates two metal centers linearly, one of the two nitrogen atoms of the im ligand is protonated and undergoes hydrogen-bonding interactions. Here, we report on the single-crystal structure and properties of [Co(Br₄bdc)(im)₂(H₂O)₂]. This is the first structural characterization of a metal complex having the Br₄bdc²⁻ dianion and im as a co-ligand.

2. Structural commentary

The title compound, [Co(Br₄bdc)(im)₂(H₂O)₂], consists of a Co^II ion, a tetrabromobenzenedicarboxylate dianion (Br₄bdc²⁻), two imidazole (im) molecules, and two water molecules. Its asymmetric unit consists of half of a Co^II ion, half of a Br₄bdc²⁻ dianion, an im molecule, and a water molecule. The key feature of the structure is a three-dimensional (3D) hydrogen-bonding network that consists of one-dimensional (1D) coordination chains built up by CoO₄N₂ octahedra bridged by Br₄bdc²⁻ ligands and interchain N—H⋯O and O—H⋯O hydrogen-bonding interactions. Fig. 1 shows the chain structure of [Co(Br₄bdc)(im)₂(H₂O)₂]. The Co^II ion occupies a crystallographically special position, and each pair of Br₄bdc²⁻ ligands, water molecules, and im ligands coordinates trans to each other; the coordination environment is similar to that of a two-dimensional (2D) material synthesized from Br₄bdc²⁻ and pyz ligands, [Co(Br₄bdc)(pyz)₂(H₂O)₂] (Kumagai et al., 2021). The carboxylate group exhibits a monodentate coordination, and the benzene ring and the carboxylate group are nearly perpendicular dihedral angle = 90.5 (3)°]. The im ligand coordinates to the Co^II ion via nitrogen atom N1 as a neutral imidazole ligand rather than as an imidazolate anion, and a hydrogen atom is attached to the remaining nitrogen atom N2. The Co—O3 (H₂O) and Co—O1 (carboxylate) bond lengths in the title compound are 2.1006 (16) and 2.1678 (13) Å (Table 1), respectively, which are slightly longer than those [2.032 (3) Å and 2.096 (4) Å] for [Co(Br₄bdc)(pyz)₂(H₂O)₂] (Kumagai et al., 2021). However, the Co—N bond length of 2.0850 (18) Å is shorter than that of 2.273 (4) Å for [Co(Br₄bdc)(pyz)₂(H₂O)₂], in which the Co^II ion shows an elongated octahedral environment, indicative of the compressed octahedron of the title compound (Kumagai et al., 2021). The angles around the Co^II ion lie in the range 88.31 (6)–180.0°. The Co⋯Co separation defined by the Co–Br₄bdc²⁻–Co connectivity within the chain is 11.69 Å, which is slightly longer than that for [Co(Br₄bdc)(pyz)₂(H₂O)₂] (11.24 Å; Kumagai et al., 2021).

Table 1
Selected geometric parameters (Å, °)

Co1—N1ⁱ	2.0850 (18)	Co1—O3	2.1007 (16)
Co1—N1	2.0850 (18)	Co1—O1ⁱ	2.1678 (13)
Co1—O3ⁱ	2.1006 (16)	Co1—O1	2.1678 (13)

N1ⁱ—Co1—N1	180.00 (11)	O3ⁱ—Co1—O1ⁱ	89.81 (6)
N1ⁱ—Co1—O3ⁱ	89.06 (7)	O3—Co1—O1ⁱ	90.19 (6)
N1—Co1—O3ⁱ	90.94 (7)	N1ⁱ—Co1—O1	91.69 (6)
N1ⁱ—Co1—O3	90.94 (7)	N1—Co1—O1	88.31 (6)
N1—Co1—O3	89.06 (7)	O3ⁱ—Co1—O1	90.19 (6)
O3ⁱ—Co1—O3	180.00 (4)	O3—Co1—O1	89.81 (6)
N1ⁱ—Co1—O1ⁱ	88.31 (6)	O1ⁱ—Co1—O1	180.0
N1—Co1—O1ⁱ	91.69 (6)
Symmetry code: (i) .

Figure 1
One-dimensional chain structure of title compound, along with labeling scheme and 50% probability displacement ellipsoids. [Symmetry code: (i) −x + 1, −y + 2, −z + 2.]

3. Supramolecular features

In the crystal structure, the im ligands and coordinated water molecules act as hydrogen-bond donors and the oxygen atoms of the carboxylate group of Br₄bdc²⁻ ligand act as hydrogen-bond acceptors (Fig. 2, Table 2). The coordinated water molecule exhibits not only intrachain hydrogen-bonding interactions with oxygen atom O2 of the carboxylate group not bound to a Co^II ion but also interchain hydrogen-bonding interactions with the coordinated oxygen atom O1 of carboxylate group in the adjacent chain. Further interchain hydrogen-bonding interactions between the im ligands and coordinated oxygen atoms of the carboxylate groups yield a 3D hydrogen-bonded network. The nearest centroid–centroid distance between the benzene ring and the im ligand, and the shortest C⋯C distance are 3.95 and 3.63 Å, respectively. These distances are indicative of some degree of π–π stacking interactions (Kruszynski & Sierański, 2019 ). The chains are not arranged in parallel but cross each other by hydrogen-bonding and π–π stacking interactions (Fig. 3) and appear to have a 1D-channel structure when viewed along the c axis (Fig. 4).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯O2ⁱⁱ	0.80 (3)	2.01 (3)	2.808 (2)	174 (3)
O3—H2⋯O2	0.76 (3)	1.99 (3)	2.700 (2)	155 (3)
O3—H3⋯O1ⁱⁱⁱ	0.75 (4)	2.06 (4)	2.809 (2)	176 (4)
Symmetry codes: (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x, -y+2, z+{\script{1\over 2}}]$ .

Figure 2
View of inter- and intramolecular hydrogen-bonding interactions. Dashed lines represent hydrogen bonds. Hydrogen atoms are omitted for clarity. [Symmetry code: (ii) x, −y + 2, z + $[{1\over 2}]$ , (iii) −x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{3\over 2}]$ .]

Figure 3
Two chains linked by interchain hydrogen-bonding interactions. Dashed lines represent interchain hydrogen bonds. Bromine and hydrogen atoms are omitted for clarity.

Figure 4
View of the hydrogen-bonding network along the crystallographic c axis.

4. Database survey

Although a search of the Sci Finder database for structures with a Br₄bdc²⁻ ion, an im ligand, and a Co^II ion resulted in no complete matches, nor were any partially matched structures found. They are metal complexes composed of a Br₄bdc²⁻ ligand and benzimidazole derivatives (Zhang et al., 2016 ; Hu et al., 2015 ). A search of the Web of Science database for the keyword tetrabromoterephthalate led to Ni^II compounds that also contain a Br₄bdc²⁻ ligand and benzimidazole derivatives (Liu et al., 2015 ; Hao et al., 2020 ).

5. Synthesis and crystallization

An aqueous solution (5 mL) of cobalt(II) nitrate hexahydrate (0.35 g, 1.25 mmol) was transferred to a glass tube, and an ethanol–water mixture (5 mL) of 2,3,5,6-tetrabromobenzenedicarboxylic acid (0.60 g, 1.25 mmol), NaOH (0.10 g, 2.50 mmol), and imidazole (0.10 g, 1.25 mmol) was poured into the glass tube without the two solutions being mixed. Pink crystals began to form at ambient temperature in 1 week, one of which was used for the X-ray crystallography study.

6. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 3. The non-hydrogen atoms were refined anisotropically. The hydrogen atom attached to a nitrogen atom of the im ligand and the water molecules were located in difference-Fourier maps. Other hydrogen atoms were placed in idealized positions and were refined using a riding model.

Table 3
Experimental details

Crystal data
Chemical formula	[Co(C₈Br₄O₄)(C₃H₄N₂)₂(H₂O)₂]
M_r	710.85
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	18.8050 (7), 12.2925 (6), 10.8938 (5)
β (°)	121.853 (3)
V (Å³)	2138.97 (17)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	8.31
Crystal size (mm)	0.60 × 0.60 × 0.60

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Rigaku, 1995 )
T_min, T_max	0.004, 0.007
No. of measured, independent and observed [I > 2σ(I)] reflections	10419, 2448, 2277
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.067, 1.07
No. of reflections	2448
No. of parameters	145
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.60
Computer programs: RAPID AUTO (Rigaku, 1995), SUPERFLIP (Palatinus & Chapuis, 2007 ), SHELXL2018/3 (Sheldrick, 2015 ) and CrystalStructure (Rigaku, 2019 ).

7. Additional investigations

To assess the thermal properties of the title compound, we carried out a thermogravimetric analysis (TGA) under a nitrogen atmosphere. The TGA curve is characterized by two weight-loss steps in the range 120–500°C (Fig. S1). The first weight loss of 6% was observed in the temperature range 120–160°C, and the second weight loss of 90% was observed in the range 200–470°C. The first weight loss corresponds to the loss of two coordinated water molecules to give the dehydrated phase, [Co(Br₄bdc)(im)₂]. The second weight loss is due to thermal decomposition of the compound. The DTG curve exhibited a sharp peak at 215°C. This result indicates that the compound is stable up to about 200°C. Electronic diffuse-reflectance spectra were recorded for as-synthesized [Co(Br₄bdc)(im)₂(H₂O)₂] and the dehydrated phase, [Co(Br₄bdc)(im)₂], obtained after heat treatment at 140°C. Because the compounds were not soluble in any solvent, we acquired the electronic diffuse-reflectance spectra of solid-state samples. After the heat treatment, a color change from pink to blue was observed and two strong absorption bands appeared at ∼480 nm and ∼1000 nm, indicating that the coordination environment of the six-coordinate Co^II center had changed to a four-coordinate Co^II environment as a result of the loss of coordinated water molecules (Fig. S2). In the IR spectrum, the characteristic band for the coordinated water molecules was observed as a broad band at 3340 cm⁻¹; the band disappeared after the heat treatment (Fig. S3). This result is in good agreement with the TGA and electronic diffuse-reflectance spectra measurement results. Nitrogen adsorption–desorption measurements were conducted; however, almost no nitrogen was adsorbed. This lack of nitrogen adsorption is speculatively attributed to insufficient space for nitrogen molecules because of the large ionic radius of the bromine.

Supporting information

CCDC reference: 2391124

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024009915/jp2013sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024009915/jp2013Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989024009915/jp2013Isup3.cdx

Supplementary figures. DOI: https://doi.org/10.1107/S2056989024009915/jp2013sup4.pdf

checkCIF report

Computing details top

catena-Poly[[diaquadiimidazolecobalt(II)]-µ₂-2,3,5,6-tetrabromobenzene-1,4-dicarboxylato] top

Crystal data top

[Co(C₈Br₄O₄)(C₃H₄N₂)₂(H₂O)₂]	F(000) = 1356
M_r = 710.85	D_x = 2.207 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71075 Å
a = 18.8050 (7) Å	Cell parameters from 9142 reflections
b = 12.2925 (6) Å	θ = 3.3–27.5°
c = 10.8938 (5) Å	µ = 8.31 mm⁻¹
β = 121.853 (3)°	T = 173 K
V = 2138.97 (17) Å³	Block, pink
Z = 4	0.60 × 0.60 × 0.60 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	2277 reflections with I > 2σ(I)
ω scans	R_int = 0.046
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995)	θ_max = 27.5°, θ_min = 3.3°
T_min = 0.004, T_max = 0.007	h = −22→24
10419 measured reflections	k = −15→15
2448 independent reflections	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.028	Hydrogen site location: mixed
wR(F²) = 0.067	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0356P)² + 0.8085P] where P = (F_o² + 2F_c²)/3
2448 reflections	(Δ/σ)_max = 0.002
145 parameters	Δρ_max = 0.61 e Å⁻³
0 restraints	Δρ_min = −0.59 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
Br1	0.40878 (2)	1.36557 (2)	0.78290 (2)	0.02796 (9)
Br2	0.30071 (2)	1.49911 (2)	0.46852 (3)	0.03101 (10)
Co1	0.500000	1.000000	1.000000	0.01141 (10)
O1	0.40770 (8)	1.08127 (12)	0.80246 (14)	0.0157 (3)
O2	0.31711 (10)	1.14631 (14)	0.85848 (17)	0.0282 (4)
O3	0.41853 (11)	1.01046 (14)	1.0767 (2)	0.0236 (4)
N1	0.44446 (11)	0.85236 (14)	0.90200 (19)	0.0179 (3)
N2	0.34569 (13)	0.73172 (17)	0.7762 (2)	0.0275 (4)
C1	0.34466 (12)	1.13493 (16)	0.7774 (2)	0.0159 (4)
C2	0.29633 (12)	1.19335 (16)	0.6314 (2)	0.0153 (4)
C3	0.31735 (12)	1.29953 (17)	0.6185 (2)	0.0159 (4)
C4	0.27151 (13)	1.35524 (16)	0.4882 (2)	0.0167 (4)
C5	0.47955 (14)	0.76163 (19)	0.8814 (3)	0.0254 (5)
H5	0.537318	0.752777	0.915853	0.030*
C6	0.41879 (16)	0.6861 (2)	0.8039 (3)	0.0329 (6)
H6	0.425979	0.616103	0.775114	0.039*
C7	0.36370 (14)	0.8307 (2)	0.8368 (2)	0.0257 (5)
H7	0.323364	0.879232	0.833300	0.031*
H1	0.2999 (19)	0.706 (2)	0.733 (3)	0.036 (8)*
H2	0.383 (2)	1.050 (3)	1.028 (3)	0.032 (8)*
H3	0.418 (2)	0.987 (2)	1.139 (4)	0.040 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02444 (15)	0.02595 (15)	0.01768 (14)	−0.00432 (8)	0.00031 (11)	−0.00049 (8)
Br2	0.03257 (17)	0.02081 (15)	0.02504 (16)	−0.00629 (8)	0.00522 (13)	0.00651 (8)
Co1	0.00890 (19)	0.0133 (2)	0.0105 (2)	0.00010 (12)	0.00411 (16)	0.00132 (12)
O1	0.0144 (7)	0.0176 (7)	0.0121 (7)	0.0044 (5)	0.0050 (6)	0.0030 (5)
O2	0.0253 (8)	0.0442 (10)	0.0199 (8)	0.0198 (7)	0.0153 (7)	0.0143 (7)
O3	0.0199 (8)	0.0337 (10)	0.0229 (9)	0.0100 (7)	0.0151 (8)	0.0135 (7)
N1	0.0168 (8)	0.0168 (9)	0.0171 (8)	−0.0012 (7)	0.0069 (7)	0.0008 (6)
N2	0.0229 (10)	0.0309 (11)	0.0267 (11)	−0.0149 (8)	0.0116 (9)	−0.0068 (8)
C1	0.0126 (9)	0.0171 (10)	0.0137 (10)	0.0012 (7)	0.0039 (8)	0.0018 (7)
C2	0.0128 (9)	0.0188 (10)	0.0144 (9)	0.0051 (8)	0.0073 (8)	0.0031 (7)
C3	0.0125 (9)	0.0176 (10)	0.0144 (9)	0.0013 (7)	0.0049 (8)	0.0000 (7)
C4	0.0181 (10)	0.0140 (9)	0.0175 (10)	0.0015 (7)	0.0090 (9)	0.0024 (7)
C5	0.0208 (11)	0.0230 (11)	0.0264 (12)	−0.0008 (9)	0.0084 (10)	−0.0056 (9)
C6	0.0358 (13)	0.0267 (13)	0.0335 (13)	−0.0074 (10)	0.0165 (12)	−0.0107 (10)
C7	0.0192 (11)	0.0282 (12)	0.0279 (12)	−0.0049 (9)	0.0112 (10)	−0.0022 (10)

Geometric parameters (Å, º) top

Br1—C3	1.890 (2)	N1—C5	1.373 (3)
Br2—C4	1.897 (2)	N2—C7	1.340 (3)
Co1—N1ⁱ	2.0850 (18)	N2—C6	1.363 (3)
Co1—N1	2.0850 (18)	N2—H1	0.80 (3)
Co1—O3ⁱ	2.1006 (16)	C1—C2	1.531 (3)
Co1—O3	2.1007 (16)	C2—C4ⁱⁱ	1.388 (3)
Co1—O1ⁱ	2.1678 (13)	C2—C3	1.392 (3)
Co1—O1	2.1678 (13)	C3—C4	1.392 (3)
O1—C1	1.254 (2)	C5—C6	1.364 (3)
O2—C1	1.246 (2)	C5—H5	0.9500
O3—H2	0.76 (3)	C6—H6	0.9500
O3—H3	0.75 (4)	C7—H7	0.9500
N1—C7	1.320 (3)

N1ⁱ—Co1—N1	180.00 (11)	C7—N2—H1	124 (2)
N1ⁱ—Co1—O3ⁱ	89.06 (7)	C6—N2—H1	128 (2)
N1—Co1—O3ⁱ	90.94 (7)	O2—C1—O1	127.11 (18)
N1ⁱ—Co1—O3	90.94 (7)	O2—C1—C2	116.28 (17)
N1—Co1—O3	89.06 (7)	O1—C1—C2	116.61 (16)
O3ⁱ—Co1—O3	180.00 (4)	C4ⁱⁱ—C2—C3	118.53 (18)
N1ⁱ—Co1—O1ⁱ	88.31 (6)	C4ⁱⁱ—C2—C1	121.38 (18)
N1—Co1—O1ⁱ	91.69 (6)	C3—C2—C1	120.00 (17)
O3ⁱ—Co1—O1ⁱ	89.81 (6)	C4—C3—C2	120.56 (18)
O3—Co1—O1ⁱ	90.19 (6)	C4—C3—Br1	121.29 (15)
N1ⁱ—Co1—O1	91.69 (6)	C2—C3—Br1	118.15 (14)
N1—Co1—O1	88.31 (6)	C2ⁱⁱ—C4—C3	120.90 (18)
O3ⁱ—Co1—O1	90.19 (6)	C2ⁱⁱ—C4—Br2	118.19 (15)
O3—Co1—O1	89.81 (6)	C3—C4—Br2	120.90 (15)
O1ⁱ—Co1—O1	180.0	C6—C5—N1	109.6 (2)
C1—O1—Co1	128.92 (12)	C6—C5—H5	125.2
Co1—O3—H2	109 (2)	N1—C5—H5	125.2
Co1—O3—H3	135 (3)	N2—C6—C5	106.0 (2)
H2—O3—H3	117 (3)	N2—C6—H6	127.0
C7—N1—C5	105.28 (19)	C5—C6—H6	127.0
C7—N1—Co1	125.05 (15)	N1—C7—N2	111.6 (2)
C5—N1—Co1	129.53 (14)	N1—C7—H7	124.2
C7—N2—C6	107.5 (2)	N2—C7—H7	124.2

Co1—O1—C1—O2	−6.2 (3)	Br1—C3—C4—C2ⁱⁱ	−179.05 (15)
Co1—O1—C1—C2	173.49 (12)	C2—C3—C4—Br2	−178.98 (14)
O2—C1—C2—C4ⁱⁱ	−87.3 (2)	Br1—C3—C4—Br2	1.6 (2)
O1—C1—C2—C4ⁱⁱ	93.0 (2)	C7—N1—C5—C6	−0.2 (3)
O2—C1—C2—C3	89.4 (2)	Co1—N1—C5—C6	−176.08 (16)
O1—C1—C2—C3	−90.4 (2)	C7—N2—C6—C5	−0.4 (3)
C4ⁱⁱ—C2—C3—C4	−0.3 (3)	N1—C5—C6—N2	0.4 (3)
C1—C2—C3—C4	−177.08 (16)	C5—N1—C7—N2	0.0 (3)
C4ⁱⁱ—C2—C3—Br1	179.07 (14)	Co1—N1—C7—N2	176.07 (15)
C1—C2—C3—Br1	2.3 (2)	C6—N2—C7—N1	0.3 (3)
C2—C3—C4—C2ⁱⁱ	0.4 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Br1ⁱⁱⁱ	0.95	3.10	3.946 (3)	149
N2—H1···O2^iv	0.80 (3)	2.01 (3)	2.808 (2)	174 (3)
O3—H2···O2	0.76 (3)	1.99 (3)	2.700 (2)	155 (3)
O3—H3···O1^v	0.75 (4)	2.06 (4)	2.809 (2)	176 (4)

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

References

Cheetham, A. K., Férey, G. & Loiseau, T. (1999). Angew. Chem. Int. Ed. 38, 3268–3292. Web of Science CrossRef CAS Google Scholar
Eddaoudi, M., Kim, J., Rosi, N., Vodak, D., Wachter, J., O'Keeffe, M. & Yaghi, O. M. (2002). Science, 295, 469–472. Web of Science CSD CrossRef PubMed CAS Google Scholar
Férey, G. (2008). Chem. Soc. Rev. 37, 191–214. Web of Science PubMed Google Scholar
Hao, Z.-C., Wang, S.-C., Yang, Y.-J. & Cui, G.-H. (2020). Polyhedron, 181, 114466. CSD CrossRef Google Scholar
Hu, J.-M., Liu, Y.-G., Van Hecke, K., Cui, G.-H. & Han, L.-H. (2015). Z. Anorg. Allg. Chem. 641, 1263–1268. CSD CrossRef CAS Google Scholar
Kitagawa, S., Kitaura, R. & Noro, S. (2004). Angew. Chem. Int. Ed. 43, 2334–2375. Web of Science CrossRef CAS Google Scholar
Kruszynski, R. & Sierański, T. (2019). Cryst. Growth Des. 16, 587–595. CrossRef Google Scholar
Kumagai, H., Sakamoto, Y., Kawata, S., Matsunaga, S. & Inagaki, S. (2012). Bull. Chem. Soc. Jpn, 85, 1102–1111. CSD CrossRef CAS Google Scholar
Kumagai, H., Setoyama, N., Kawata, S. & Sakamoto, Y. (2021). Bull. Chem. Soc. Jpn, 94, 1571–1578. CSD CrossRef CAS Google Scholar
Kurmoo, M. (2009). Chem. Soc. Rev. 38, 1353–1379. Web of Science CrossRef PubMed CAS Google Scholar
Liu, X.-B., Huang, C.-M., Dong, G.-Y. & Cui, G.-H. (2015). Transition Met. Chem. 40, 847–856. CSD CrossRef CAS Google Scholar
Mikita, R., Ogihara, N., Takahashi, N., Kosaka, S. & Isomura, N. (2020). Chem. Mater. 32, 3396–3404. Web of Science CrossRef CAS Google Scholar
Ogihara, N., Hasegawa, M., Kumagai, H., Mikita, R. & Nagasako, N. (2023). Nat. Commun. 14, 1–11. Web of Science CrossRef PubMed Google Scholar
Ogihara, N., Ohba, N. & Kishida, Y. (2017). Sci. Adv. 3, e1603103. Web of Science CrossRef PubMed Google Scholar
Ogihara, N., Yasuda, T., Kishida, Y., Ohsuna, T., Miyamoto, K. & Ohba, N. (2014). Angew. Chem. Int. Ed. 53, 11467–11472. Web of Science CrossRef CAS Google Scholar
Palatinus, L. & Chapuis, G. (2007). J. Appl. Cryst. 40, 786–790. Web of Science CrossRef CAS IUCr Journals Google Scholar
Rao, C. N. R., Cheetham, A. K. & Thirumurugan, A. (2008). J. Phys. Condens. Matter, 20, 083202. CrossRef Google Scholar
Rigaku (1995). ABSCOR and RAPID AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2019). Crystal Structure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Yaghi, O. M., Kalmutzki, M. J. & Diercks, C. S. (2019). Introduction to Reticular Chemistry: Metal-Organic Frameworks and Covalent Organic Frameworks. Weinheim, Germany: VCH. Google Scholar
Yasuda, T. & Ogihara, N. (2014). Chem. Commun. 50, 11565–11567. Web of Science CrossRef CAS Google Scholar
Zhang, X., Liu, Y.-G., Hao, Z. C. & Cui, G.-H. J. (2016). J. Coord. Chem. 69, 1514–1524. CSD CrossRef CAS Google Scholar

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