Poly[bis­(μ2-N,N-di­methyl­formamide-κ2O:O)bis­(μ4-thio­phene-2,5-di­carboxyl­ato-κ4O:O′:O′′:O′′′)dicobalt(II)]

Ren, J.-Y.; Huang, R.; Yin, Z.; Cao, L.-H.

doi:10.1107/S2414314622007751

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 7| Part 8| August 2022| x220775

https://doi.org/10.1107/S2414314622007751

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Poly[bis(μ₂-N,N-dimethylformamide-κ²O:O)bis(μ₄-thiophene-2,5-dicarboxylato-κ⁴O:O′:O′′:O′′′)dicobalt(II)]

Ji-Yun Ren,^a Rou Huang,^a Zheng Yin ^a ^* and Li-Hui Cao ^a

^aCollege of Chemistry and Chemical Engineering, Shaanxi University of Science and Technology, Xi'an 710021, People's Republic of China
^*Correspondence e-mail: yinzheng@sust.edu.cn

Edited by J. F. Gallagher, Dublin City University, Ireland (Received 14 June 2022; accepted 1 August 2022; online 12 August 2022)

The asymmetric unit of the title three-dimensional metal–organic hybrid compound, [Co₂(C₆H₂O₄S)₂(C₃H₇NO)₂]_n, comprises two cobalt(II) cations, one residing on a twofold axis and the other on a centre of inversion, one thiophene-2,5-dicarboxylate (tdc²⁻) ligand and one coordinating dimethylformamide (DMF) solvent molecule. Both of the cobalt(II) cations exhibit an octahedral coordination environment from the four carboxyl O atoms of the tdc²⁻ anions in a μ₄-κ¹:κ¹:κ¹:κ¹ fashion and two O atoms from DMF. A pair of carboxyl O atoms and one DMF molecule connect the adjacent cobalt(II) cations into an infinite chain, leading to a rod-spacer framework with rhombus-window channels, yet no residual solvent-accessible voids are present because the coordinating DMF molecules are oriented into the potential channels.

Keywords: crystal structure; metal–organic framework; cobalt(II); rod-spacer.

CCDC reference: 2178433

Structure description

Facing the timetable for a carbon-neutral future, electrochemical redox reactions are the cornerstones of large-scale storage and chemical conversion of renewable clean energy in the future, in which electrocatalytic water splitting plays a central role (Seh et al., 2017 ; Cheng et al., 2022 ). Metal–organic frameworks (MOFs), a class of crystalline and highly porous frameworks usually constructed from 3d metal ions and organic ligands (Yin et al., 2015 ), provide great opportunities for the preparation of new electrocatalysts for water splitting. Benefitting from outstanding designability and regulation for the composition and structure of MOFs, 3d-metal-based electrocatalysts with excellent electrocatalyst performance can be obtained from both highly stable MOFs and nanocomposites derived from the thermal or chemical reaction of the MOF precursor (Zhu et al., 2018 ). In a previous study, we discovered alkali-induced in situ formation of amorphous Ni_xFe_1–x(OH)₂ from a linear [M₃(COO)₆]-based MOF template for overall electrochemical water splitting (Yin et al., 2015).

In parallel work, thiophene-2,5-dicarboxylic acid (H₂tdc) and the cobalt ion were chosen to construct MOFs for potential electrochemical applications. The H₂tdc ligand is a typical di-topic linker comparable to terephthalic acid that has strong coordination ability. In fact, there are 366 polymeric structure records from a total of 409 compounds constructed from H₂tdc, based on a Cambridge Structural Database analysis (CSD version 5.4.1; December 2021; Groom et al., 2016 ), suggesting its suitability for MOF assembly. In addition, there are carbon and sulfur elements stemming from the thiazole ring backbone, facilitating the generation of sulfur-containing nanocomposites for electro-catalysis. On this occasion, the title compound was obtained during the synthetic exploration of new three-dimensional rod-spacer MOFs of [Co₂(tdc)₂(DMF)₂]_n in a solvothermal reaction. There have been reports about the isostructural Mn^II compound, yet no other metal-based MOF has been described (Tan et al., 2013 ).

The title compound (Fig. 1) crystallizes in the monoclinic space group C2/c. The asymmetric unit comprises two cobalt(II) cations (one resides on a twofold axis and the second on an inversion centre), one full tdc²⁻ ligand, and one coordinating DMF molecule Each of the cobalt(II) cations exhibits a octahedral coordination geometry by the four carboxyl O atoms from the tdc²⁻ anions in a μ₄-κ¹:κ¹:κ¹:κ¹ fashion and two O atoms from DMF. The calculated continuous shape measures (CShM) value for Co1 and Co2 are 0.338 and 0.240, respectively, indicating only quite a small coordination distortion from a regular octahedron. A pair of carboxyl and one DMF link adjacent cobalt(II) cations into infinite chains via C—H⋯O hydrogen bonds (Table 1, Fig. 2). In particular, the DMF ligand adopts a μ₂-bridging mode to link adjacent metal ions. Compared to its usual role as a terminally bound ligand, such coordination behaviour is rare but has been observed in some known MOFs (Fritzsche et al., 2019 ). As a result, a rod–spacer framework with rhombus-window channels is formed through the tdc²⁻ linkage of neighbouring chains. However, no solvent-accessible voids were noted because the coordinating DMF molecule is oriented into the channels and fully occupies any potential void space. The compound is thermally stable up to 260°C under an N₂ atmosphere by thermogravimetric analysis. Thermogravimetric analysis: the mass of the compound remains stable until 250°C, followed by an obvious mass loss of 23.7% corresponding to the loss of coordinating DMF (calculated 26.8%) in the range of 250–310°C, and then thermal decomposition of the framework with residuals of 34.3% from 400–800°C, much higher than the theoretical data for decomposition products of Co₃O₄ (calculated 27.7%) or CoO (calculated 26.0%), suggesting the formation of carbon- and sulfur-rich nanocomposites.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8A—H8AB⋯O4ⁱ	0.96	2.44	3.308 (6)	150
C9A—H9AA⋯O1ⁱⁱ	0.96	2.60	3.347 (6)	135
C9B—H9BB⋯O3ⁱⁱⁱ	0.96	2.58	3.42 (4)	146
Symmetry codes: (i) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x, -y+1, z+{\script{1\over 2}}]$ .

Figure 1
A view of the asymmetric unit of the title compound showing the atom labelling with displacement ellipsoids drawn at the 50% probability level.

Figure 2
(a) A view of the coordination environment of the Co²⁺ ions. Colour code: Co²⁺, light blue; O, red; C, grey; S, yellow; N, blue. (b) The coordination modes of the tdc²⁻ ligand. (c) Structural view of the chain. (d) Perspective view of the three-dimensional rod–spacer framework.

Synthesis and crystallization

A solution of H₂tdc (0.2 mmol, 34.4 mg) and CoCl₂·6H₂O (0.2 mmol, 47.6 mg) in DMF (dimethyl formamide, 15 ml) was stirred in air with a magnetic stirrer, generating a purple transparent solution after stirring for 5 min. The reaction solution was transferred to a hydrothermal reaction vessel containing 25 ml of a polytetrafluoroethylene liner, followed by heating at 140°C for 48 h. The reaction vessel was cooled to room temperature at a rate of 10°C per hour. The precipitate was washed and filtered to obtain a large amount of light-purple block-shaped crystals of the title compound with a yield of about 60% (based on Co). The obtained crystals are insoluble in common organic solvents of DMF, CH₃OH, C₂H₅OH, CH₂Cl₂ and acetone. IR (KBr pellets, cm⁻¹): 3446(bm), 2943(vs), 1654(s), 1532(s), 1370(vs), 1106(s), 1010(s), 771(m), 674(w). Elemental analysis (%), calculated: C, 39.63; H, 3.33; N, 5.14; S, 11.76; found: C, 38.83; H, 3.76; N, 4.95; S, 12.02.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Atoms C3 and C4 of the thiazole ring and the C atoms of the coordinating DMF are disordered over two sets of sites with occupancy ratios of 0.550 (17):0.450 (17) nd 0.855 (5):0.145 (5), respectively. Disorder treatment and restraints for the displacement parameters of the thiazole ring and coordinated DMF were applied. Disorder was treated as follows: two adjacent carbon atoms C3, C4 in the thiazole ring were split into two parts, and the C7, C8, C9 atoms in the DMF were split into two positions also, followed by SIMU restraints for these atoms and subsequent refinements, resulting in lower, acceptable R-factors and refinement.

Table 2
Experimental details

Crystal data
Chemical formula	[Co(C₆H₂O₄S)(C₃H₇NO)]
M_r	302.16
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	11.610 (2), 18.046 (4), 11.496 (2)
β (°)	102.35 (3)
V (Å³)	2352.9 (9)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	1.64
Crystal size (mm)	0.24 × 0.15 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.656, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	12568, 2928, 2285
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.089, 1.10
No. of reflections	2928
No. of parameters	203
No. of restraints	90
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.44
Computer programs: APEX2 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ) and DIAMOND (Brandenburg & Putz, 2019 ).

Structural data

CCDC reference: 2178433

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314622007751/gg4009sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314622007751/gg4009Isup3.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009) and DIAMOND (Brandenburg & Putz, 2019); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Poly[bis(µ₂-N,N-dimethylformamide-κ²O:O)bis(µ₄-thiophene-2,5-dicarboxylato-κ⁴O:O':O'':O''')dicobalt(II)] top

Crystal data top

[Co(C₆H₂O₄S)(C₃H₇NO)]	F(000) = 1224
M_r = 302.16	D_x = 1.706 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.610 (2) Å	Cell parameters from 4391 reflections
b = 18.046 (4) Å	θ = 3.6–27.9°
c = 11.496 (2) Å	µ = 1.64 mm⁻¹
β = 102.35 (3)°	T = 298 K
V = 2352.9 (9) Å³	Block, clear dark violet
Z = 8	0.24 × 0.15 × 0.11 mm

Data collection top

Bruker APEXII CCD diffractometer	2285 reflections with I > 2σ(I)
ω scans	R_int = 0.054
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 28.3°, θ_min = 2.5°
T_min = 0.656, T_max = 0.746	h = −15→15
12568 measured reflections	k = −20→24
2928 independent reflections	l = −13→15

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0336P)² + 4.208P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
2928 reflections	Δρ_max = 0.48 e Å⁻³
203 parameters	Δρ_min = −0.43 e Å⁻³
90 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. The single-crystal diffraction data were collected on a on a Bruker APEX-II CCD diffractometer (Mo-Kα, λ = 0.71073?Å), with the APEX-II software for data reduction and analysis (Bruker 2016). The dataset of a selected single-crystal of (I) were collected at 298?K. The structure was solved by direct methods and refined by full-matrix least-squares method on F2 using SHELX algorithms in Olex2 (Sheldrick 2008; Dolomanov et al., 2009). All non-hydrogen atoms were refined with anisotropic displacement parameters. All hydrogen atoms were generated geometrically.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.0000	0.22585 (3)	0.2500	0.01571 (14)
Co2	0.2500	0.2500	0.5000	0.01521 (13)
S1	0.28427 (7)	0.49423 (4)	0.30550 (7)	0.0294 (2)
O1	0.11164 (18)	0.30921 (11)	0.22411 (18)	0.0282 (5)
O2	0.24100 (19)	0.34160 (11)	0.39173 (18)	0.0292 (5)
O3	0.21863 (18)	0.67965 (10)	0.12859 (17)	0.0238 (4)
O4	0.38032 (18)	0.64477 (11)	0.26243 (18)	0.0266 (5)
O5	0.06101 (17)	0.22609 (11)	0.44616 (17)	0.0226 (4)
N1	−0.0669 (3)	0.2096 (2)	0.5674 (3)	0.0460 (8)
C1	0.1779 (2)	0.35367 (14)	0.2909 (2)	0.0203 (6)
C2	0.1840 (3)	0.42955 (16)	0.2402 (3)	0.0288 (7)
C3A	0.1295 (10)	0.4528 (5)	0.1270 (9)	0.035 (2)	0.550 (17)
H3A	0.0808	0.4227	0.0719	0.043*	0.550 (17)
C4A	0.1552 (10)	0.5261 (5)	0.1043 (9)	0.035 (2)	0.550 (17)
H4A	0.1262	0.5500	0.0323	0.042*	0.550 (17)
C3B	0.1167 (12)	0.5369 (7)	0.1402 (12)	0.039 (2)	0.450 (17)
H3B	0.0643	0.5678	0.0901	0.047*	0.450 (17)
C4B	0.0916 (11)	0.4632 (7)	0.1631 (12)	0.036 (2)	0.450 (17)
H4B	0.0209	0.4396	0.1302	0.043*	0.450 (17)
C5	0.2283 (3)	0.55903 (16)	0.2002 (3)	0.0285 (7)
C6	0.2810 (3)	0.63407 (15)	0.1970 (2)	0.0205 (6)
C7A	−0.0030 (3)	0.2499 (2)	0.5112 (3)	0.0309 (9)	0.855 (5)
H7A	−0.0058	0.3010	0.5208	0.037*	0.855 (5)
C8A	−0.0681 (5)	0.1296 (3)	0.5558 (5)	0.0716 (17)	0.855 (5)
H8AA	−0.1193	0.1088	0.6026	0.107*	0.855 (5)
H8AB	−0.0962	0.1164	0.4737	0.107*	0.855 (5)
H8AC	0.0103	0.1107	0.5832	0.107*	0.855 (5)
C9A	−0.1409 (5)	0.2434 (4)	0.6420 (5)	0.0772 (19)	0.855 (5)
H9AA	−0.1810	0.2052	0.6758	0.116*	0.855 (5)
H9AB	−0.0922	0.2714	0.7047	0.116*	0.855 (5)
H9AC	−0.1978	0.2756	0.5941	0.116*	0.855 (5)
C7B	0.008 (2)	0.1836 (16)	0.497 (2)	0.044 (4)	0.145 (5)
H7B	0.0183	0.1328	0.4896	0.052*	0.145 (5)
C9B	−0.078 (3)	0.291 (2)	0.591 (3)	0.072 (5)	0.145 (5)
H9BA	−0.1340	0.2977	0.6413	0.107*	0.145 (5)
H9BB	−0.0030	0.3101	0.6308	0.107*	0.145 (5)
H9BC	−0.1051	0.3165	0.5175	0.107*	0.145 (5)
C8B	−0.118 (3)	0.154 (2)	0.628 (3)	0.085 (6)	0.145 (5)
H8BA	−0.1682	0.1761	0.6743	0.128*	0.145 (5)
H8BB	−0.1631	0.1202	0.5712	0.128*	0.145 (5)
H8BC	−0.0562	0.1265	0.6802	0.128*	0.145 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0156 (3)	0.0107 (3)	0.0203 (3)	0.000	0.0029 (2)	0.000
Co2	0.0192 (3)	0.0098 (2)	0.0164 (2)	−0.0001 (2)	0.0033 (2)	−0.00102 (18)
S1	0.0331 (4)	0.0171 (4)	0.0303 (4)	−0.0084 (3)	−0.0102 (3)	0.0082 (3)
O1	0.0318 (12)	0.0204 (11)	0.0297 (11)	−0.0118 (9)	0.0004 (9)	0.0050 (8)
O2	0.0403 (13)	0.0151 (10)	0.0280 (11)	−0.0063 (9)	−0.0020 (9)	0.0069 (8)
O3	0.0254 (11)	0.0196 (10)	0.0264 (11)	−0.0019 (8)	0.0054 (8)	0.0103 (8)
O4	0.0244 (11)	0.0188 (10)	0.0335 (11)	−0.0082 (8)	−0.0009 (9)	0.0075 (8)
O5	0.0178 (10)	0.0317 (11)	0.0190 (10)	−0.0012 (8)	0.0058 (8)	−0.0002 (8)
N1	0.0297 (17)	0.083 (3)	0.0280 (15)	−0.0124 (16)	0.0124 (13)	0.0028 (15)
C1	0.0183 (14)	0.0161 (14)	0.0270 (15)	−0.0037 (11)	0.0059 (11)	0.0044 (11)
C2	0.0253 (16)	0.0224 (16)	0.0339 (17)	−0.0110 (12)	−0.0048 (13)	0.0080 (12)
C3A	0.038 (5)	0.025 (3)	0.035 (4)	−0.013 (3)	−0.012 (3)	0.008 (3)
C4A	0.040 (5)	0.027 (3)	0.032 (4)	−0.011 (3)	−0.010 (3)	0.016 (3)
C3B	0.035 (5)	0.030 (4)	0.043 (5)	−0.009 (4)	−0.013 (4)	0.018 (4)
C4B	0.030 (5)	0.029 (4)	0.042 (5)	−0.016 (4)	−0.010 (4)	0.019 (4)
C5	0.0317 (17)	0.0171 (15)	0.0309 (16)	−0.0076 (12)	−0.0062 (13)	0.0114 (11)
C6	0.0252 (16)	0.0175 (14)	0.0196 (13)	−0.0041 (11)	0.0068 (11)	0.0037 (10)
C7A	0.0246 (19)	0.042 (2)	0.0250 (18)	0.0002 (16)	0.0036 (14)	−0.0021 (15)
C8A	0.084 (4)	0.080 (4)	0.054 (3)	−0.026 (3)	0.022 (3)	0.011 (3)
C9A	0.046 (3)	0.145 (6)	0.051 (3)	0.002 (3)	0.033 (3)	−0.004 (3)
C7B	0.040 (8)	0.055 (8)	0.029 (7)	−0.009 (8)	−0.009 (7)	0.007 (7)
C9B	0.064 (10)	0.102 (10)	0.046 (9)	−0.004 (10)	0.006 (9)	−0.001 (9)
C8B	0.077 (11)	0.122 (12)	0.061 (11)	−0.021 (11)	0.027 (10)	0.004 (11)

Geometric parameters (Å, º) top

Co1—O1ⁱ	2.0485 (19)	N1—C8B	1.43 (4)
Co1—O1	2.0484 (19)	C1—C2	1.496 (4)
Co1—O4ⁱⁱ	2.0438 (19)	C2—C3A	1.385 (9)
Co1—O4ⁱⁱⁱ	2.0437 (19)	C2—C4B	1.378 (11)
Co1—O5ⁱ	2.215 (2)	C3A—H3A	0.9300
Co1—O5	2.215 (2)	C3A—C4A	1.392 (11)
Co2—O2	2.0585 (19)	C4A—H4A	0.9300
Co2—O2^iv	2.0585 (19)	C4A—C5	1.375 (9)
Co2—O3ⁱⁱ	2.0397 (18)	C3B—H3B	0.9300
Co2—O3^v	2.0396 (18)	C3B—C4B	1.399 (13)
Co2—O5^iv	2.192 (2)	C3B—C5	1.390 (12)
Co2—O5	2.192 (2)	C4B—H4B	0.9300
S1—C2	1.705 (3)	C5—C6	1.489 (4)
S1—C5	1.709 (3)	C7A—H7A	0.9300
O1—C1	1.254 (3)	C8A—H8AA	0.9600
O2—C1	1.251 (3)	C8A—H8AB	0.9600
O3—Co2^vi	2.0396 (18)	C8A—H8AC	0.9600
O3—C6	1.255 (3)	C9A—H9AA	0.9600
O4—Co1^vii	2.0438 (19)	C9A—H9AB	0.9600
O4—C6	1.250 (3)	C9A—H9AC	0.9600
O5—C7A	1.239 (4)	C7B—H7B	0.9300
O5—C7B	1.21 (3)	C9B—H9BA	0.9700
N1—C7A	1.305 (5)	C9B—H9BB	0.9600
N1—C8A	1.449 (6)	C9B—H9BC	0.9600
N1—C9A	1.469 (6)	C8B—H8BA	0.9600
N1—C7B	1.39 (3)	C8B—H8BB	0.9600
N1—C9B	1.50 (4)	C8B—H8BC	0.9700

O1—Co1—O1ⁱ	85.50 (13)	C4B—C2—S1	110.2 (5)
O1ⁱ—Co1—O5ⁱ	94.13 (8)	C4B—C2—C1	123.9 (5)
O1—Co1—O5	94.13 (8)	C2—C3A—H3A	123.5
O1—Co1—O5ⁱ	85.71 (8)	C2—C3A—C4A	113.1 (6)
O1ⁱ—Co1—O5	85.71 (8)	C4A—C3A—H3A	123.5
O4ⁱⁱ—Co1—O1ⁱ	175.30 (8)	C3A—C4A—H4A	123.8
O4ⁱⁱⁱ—Co1—O1ⁱ	93.14 (9)	C5—C4A—C3A	112.4 (6)
O4ⁱⁱ—Co1—O1	93.14 (9)	C5—C4A—H4A	123.8
O4ⁱⁱⁱ—Co1—O1	175.30 (8)	C4B—C3B—H3B	123.5
O4ⁱⁱⁱ—Co1—O4ⁱⁱ	88.56 (12)	C5—C3B—H3B	123.5
O4ⁱⁱ—Co1—O5ⁱ	90.25 (8)	C5—C3B—C4B	112.9 (8)
O4ⁱⁱⁱ—Co1—O5ⁱ	89.91 (8)	C2—C4B—C3B	112.0 (8)
O4ⁱⁱⁱ—Co1—O5	90.25 (8)	C2—C4B—H4B	124.0
O4ⁱⁱ—Co1—O5	89.91 (8)	C3B—C4B—H4B	124.0
O5ⁱ—Co1—O5	179.78 (11)	C4A—C5—S1	110.4 (4)
O2^iv—Co2—O2	180.00 (9)	C4A—C5—C6	124.1 (4)
O2^iv—Co2—O5	86.04 (8)	C3B—C5—S1	109.1 (5)
O2—Co2—O5^iv	86.04 (8)	C3B—C5—C6	126.4 (5)
O2^iv—Co2—O5^iv	93.96 (8)	C6—C5—S1	122.9 (2)
O2—Co2—O5	93.96 (8)	O3—C6—C5	115.2 (2)
O3^v—Co2—O2	86.82 (8)	O4—C6—O3	127.6 (3)
O3ⁱⁱ—Co2—O2^iv	86.83 (8)	O4—C6—C5	117.2 (2)
O3ⁱⁱ—Co2—O2	93.17 (8)	O5—C7A—N1	125.7 (4)
O3^v—Co2—O2^iv	93.18 (8)	O5—C7A—H7A	117.1
O3^v—Co2—O3ⁱⁱ	180.0	N1—C7A—H7A	117.1
O3ⁱⁱ—Co2—O5^iv	90.24 (8)	N1—C8A—H8AA	109.5
O3^v—Co2—O5^iv	89.76 (8)	N1—C8A—H8AB	109.5
O3ⁱⁱ—Co2—O5	89.76 (8)	N1—C8A—H8AC	109.5
O3^v—Co2—O5	90.24 (8)	H8AA—C8A—H8AB	109.5
O5^iv—Co2—O5	180.0	H8AA—C8A—H8AC	109.5
C2—S1—C5	92.08 (15)	H8AB—C8A—H8AC	109.5
C1—O1—Co1	134.86 (19)	N1—C9A—H9AA	109.5
C1—O2—Co2	130.09 (18)	N1—C9A—H9AB	109.5
C6—O3—Co2^vi	133.92 (19)	N1—C9A—H9AC	109.5
C6—O4—Co1^vii	128.48 (18)	H9AA—C9A—H9AB	109.5
Co2—O5—Co1	111.77 (9)	H9AA—C9A—H9AC	109.5
C7A—O5—Co1	120.9 (2)	H9AB—C9A—H9AC	109.5
C7A—O5—Co2	117.1 (2)	O5—C7B—N1	121 (2)
C7B—O5—Co1	114.2 (11)	O5—C7B—H7B	119.6
C7B—O5—Co2	124.6 (11)	N1—C7B—H7B	119.6
C7A—N1—C8A	120.3 (4)	N1—C9B—H9BA	109.5
C7A—N1—C9A	121.5 (4)	N1—C9B—H9BB	109.5
C8A—N1—C9A	118.1 (4)	N1—C9B—H9BC	109.5
C7B—N1—C9B	121.7 (18)	H9BA—C9B—H9BB	109.5
C7B—N1—C8B	115 (2)	H9BA—C9B—H9BC	109.5
C8B—N1—C9B	123 (2)	H9BB—C9B—H9BC	109.5
O1—C1—C2	114.9 (2)	N1—C8B—H8BA	109.5
O2—C1—O1	128.1 (2)	N1—C8B—H8BB	109.5
O2—C1—C2	116.9 (2)	N1—C8B—H8BC	109.5
C1—C2—S1	122.7 (2)	H8BA—C8B—H8BB	109.5
C3A—C2—S1	109.7 (4)	H8BA—C8B—H8BC	109.5
C3A—C2—C1	126.4 (4)	H8BB—C8B—H8BC	109.5

Co1—O1—C1—O2	38.9 (5)	C1—C2—C3A—C4A	−177.8 (5)
Co1—O1—C1—C2	−143.4 (2)	C1—C2—C4B—C3B	173.3 (6)
Co1^vii—O4—C6—O3	−20.0 (5)	C2—S1—C5—C4A	−14.2 (6)
Co1^vii—O4—C6—C5	160.7 (2)	C2—S1—C5—C3B	16.9 (8)
Co1—O5—C7A—N1	99.3 (4)	C2—S1—C5—C6	−176.5 (3)
Co1—O5—C7B—N1	−110.7 (16)	C2—C3A—C4A—C5	−0.6 (10)
Co2—O2—C1—O1	−8.1 (5)	C3A—C4A—C5—S1	10.9 (9)
Co2—O2—C1—C2	174.2 (2)	C3A—C4A—C5—C6	173.0 (5)
Co2^vi—O3—C6—O4	49.8 (4)	C4A—C5—C6—O3	32.4 (8)
Co2^vi—O3—C6—C5	−130.8 (2)	C4A—C5—C6—O4	−148.1 (7)
Co2—O5—C7A—N1	−118.5 (4)	C3B—C5—C6—O3	−3.5 (10)
Co2—O5—C7B—N1	105.9 (18)	C3B—C5—C6—O4	176.0 (9)
S1—C2—C3A—C4A	−10.0 (9)	C4B—C3B—C5—S1	−12.7 (11)
S1—C2—C4B—C3B	12.8 (10)	C4B—C3B—C5—C6	−178.7 (6)
S1—C5—C6—O3	−167.7 (2)	C5—S1—C2—C1	−177.9 (3)
S1—C5—C6—O4	11.8 (4)	C5—S1—C2—C3A	13.7 (6)
O1—C1—C2—S1	−170.0 (2)	C5—S1—C2—C4B	−17.2 (8)
O1—C1—C2—C3A	−3.6 (8)	C5—C3B—C4B—C2	0.0 (12)
O1—C1—C2—C4B	31.9 (9)	C8A—N1—C7A—O5	−0.7 (6)
O2—C1—C2—S1	8.0 (4)	C9A—N1—C7A—O5	−179.5 (4)
O2—C1—C2—C3A	174.4 (7)	C9B—N1—C7B—O5	−5 (3)
O2—C1—C2—C4B	−150.1 (9)	C8B—N1—C7B—O5	−176 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8A—H8AB···O4ⁱⁱⁱ	0.96	2.44	3.308 (6)	150
C9A—H9AA···O1^viii	0.96	2.60	3.347 (6)	135
C9B—H9BB···O3^v	0.96	2.58	3.42 (4)	146

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

Acknowledgements

The authors thank Shaanxi University of Science and Technology for supporting this work.

Funding information

Funding for this research was provided by: the College Students' Innovation and Entrepreneurship Training Program at Shaanxi University of Science and Technology (No. S202110708108) and the Key Research and Development Program of Shaanxi (No. 2022GY-180).

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