Synthesis and crystal structure of poly[(3-amino-1,2,4-triazole)(μ3-1H-benzimidazole-5,6-di­carboxyl­ato)cobalt(II)]

Zhao, C.; Li, Y.; Xiao, J.-S.; Zhang, P.-D.; Wu, X.-Q.; Chen, Q.

doi:10.1107/S2056989021005867

research communications

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ISSN: 2056-9890

Volume 77| Part 7| July 2021| Pages 714-717

https://doi.org/10.1107/S2056989021005867

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Synthesis and crystal structure of poly[(3-amino-1,2,4-triazole)(μ₃-1H-benzimidazole-5,6-dicarboxylato)cobalt(II)]

Chen Zhao,^a Yi Li,^a Jin-Sheng Xiao,^a Peng-Dan Zhang,^a Xue-Qian Wu ^a ^* and Qiang Chen ^a

^aBeijing Key Laboratory for Green Catalysis and Separation and Department of Environmental Chemical Engineering, Faculty of Environment and Life, Beijing University of Technology, Beijing 100124, People's Republic of China
^*Correspondence e-mail: wuxueqiansnail@emails.bjut.edu.cn

Edited by G. Díaz de Delgado, Universidad de Los Andes, Venezuela (Received 29 April 2021; accepted 6 June 2021; online 15 June 2021)

The asymmetric unit of the title coordination polymer, [Co(C₉H₄N₂O₄)(C₂H₄N₄)]_n or [Co(L₁)(L₂)]_n, consists of one crystallographically independent Co²⁺ centre, one L₁²⁻ ligand and one L₂ ligand (L₁ = 1H-benzimidazole-5,6-dicarboxylic acid, L₂ = 3-amino-1,2,4-triazole). The Co²⁺ centre is coordinated by two carboxylato-O atoms from two independent L₁²⁻ ligands and two nitrogen atoms from L₂ and another L₁ ligand. Thus, the metal center adopts a four-coordinate mode, forming a tetrahedral geometry. Interestingly, through the combination of two L₁²⁻, two L₂ ligands and two Co²⁺ ions, a basic repeating unit is constructed, resulting in the formation of a one-dimensional straight chain structure. These chains are further expanded to the final three-dimensional framework via N—H⋯O hydrogen-bonding interactions.

Keywords: crystal structure; coordination polymer; mixed-ligands synthetic strategy; imidazole; dicarboxylic acid.

CCDC reference: 1996100

1. Chemical context

Over the past two decades, coordination polymers (CPs) have been demonstrated to represent a new type of crystalline organic–inorganic hybrid materials, and are unique in terms of their potentially high porosities, tunable pores, and diverse compositions (Du et al., 2013 ; Kitagawa et al., 2007 ; Cui et al., 2016 ). These features have enabled CPs to be constructed with great potential for various applications, such as gas adsorption/separation (Zhao et al., 2018 ), chemical sensing (Huang et al., 2017 ), heterogeneous catalysis (He et al., 2020 ) and energy storage/conversion (Lu et al., 2020 ). Meanwhile, the crystalline nature of CPs allows for the accurate determination of their structures using X-ray diffraction techniques and further, the revealing of structure–property relationships. The great potential of these compounds certainly promotes the development of synthetic strategies for new CPs. It has been demonstrated that many efficient synthetic routes, including metal exchange (Wang et al., 2017 ), ligand substitution (Han et al., 2014 ), directional construction based on secondary building units (SBUs) (Zou et al., 2016 ), and topology-guided reticular chemistry principles (Wang et al., 2016 ) have shown some advantages in fabricating new CPs with multiple structures and functionalities. In addition to the methods mentioned above, the mixed-ligands strategy is also considered to be an important approach for the integration of the properties of related ligands into a single coordination polymer and hence expansion of the structural diversity of CPs (Macreadie et al., 2020 ). In this context, we report the synthesis and crystal structure of the title coordination polymer poly[(3-amino-1,2,4-triazole)(μ₃-1H-benzimidazole-5,6-dicarboxylato)cobalt(II)] (1), which was prepared by the solvothermal method using two simple ligands and a cobalt salt.

2. Structural commentary

The title coordination polymer (1) crystallizes in the monoclinic system, P2₁/c space group, and its asymmetric unit contains one Co²⁺ center, one L₁²⁻ anion and one L₂ ligand (Fig. 1). The metal center adopts a typical tetrahedral linkage geometry to coordinate with two carboxylato-O atoms from two independent L₁²⁻ ligands and two nitrogen atoms, one from L₂ and another from an L₁ ligand. Interestingly, through the combination of two L₁²⁻, two L₂ ligands and two Co²⁺ ions, a basic repeating unit is constructed, resulting in the formation of a one-dimensional straight chain structure (as shown in Fig. 2). These chains are further connected via hydrogen bonding interactions (Fig. 3), generating a three-dimensional framework.

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

Figure 2
A view of the one-dimensional straight chain structure within the coordination polymer.

Figure 3
Structure of the title coordination polymer viewed along the (a) a axis and (b) c axis, respectively.

3. Supramolecular features

As mentioned above, extensive hydrogen-bonding interactions in the crystal of the title coordination polymer are observed, the numerical values of which are presented in Table 1. As shown in Fig. 4, each chain is linked to adjacent chains by N1—H1⋯O1 hydrogen bonds into infinite layer structures parallel to the bc plane. Meanwhile, these layers are linked by other intermolecular hydrogen bonds (e.g., N3—H3⋯O3 and N6—H6A⋯O3), resulting in the formation of the final three-dimensional supramolecular network. Due to the regular distribution of Co²⁺ metal sites, the high density of nitrogen atoms in the structure, and the packing arrangement of the supramolecular network, the coordination polymer has the potential to work as a molecular catalyst or to serve as the precursor material for preparing an electrocatalyst.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	1.84	2.675 (4)	163
N3—H3⋯O1ⁱⁱ	0.86	2.48	3.104 (4)	130
N3—H3⋯O3ⁱⁱ	0.86	2.08	2.811 (4)	142
N6—H6A⋯O3ⁱⁱ	0.86	2.35	3.036 (5)	136
N6—H6B⋯O2ⁱⁱⁱ	0.86	2.23	2.946 (5)	141
C5—H5⋯O4^iv	0.93	2.58	3.312 (4)	136
C9—H9⋯N5^v	0.93	2.48	3.332 (5)	152
C11—H11⋯O1^vi	0.93	2.41	3.215 (5)	145
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) ; (iii) x, y+1, z; (iv) ; (v) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 4
A view of the hydrogen bonds in the title coordination polymer. Intramolecular hydrogen bonds are omitted for clarity [symmetry codes: (#1) −1 + x, y, z; (#2) 1 − x, 1 − y, 1 − z; (#3) −x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (#4) −1 + x, 1 + y, z; (#5) −x, 1 − y, 1 − z.

4. Database survey

A search of the Cambridge Crystallographic Database (CSD version 5.42, update of Feb 2021, Groom et al., 2016 ) for structures with 1H-benzimidazole-5,6-dicarboxylate gave 372 hits of which some are coordination polymers with prominent free pore space (also known as metal-organic frameworks, MOFs). For example, Li and co-workers reported a new three-dimensional non-interpenetrating metal–organic framework (BARKUD01), featuring one-dimensional nanotube channels and exhibiting excellent gas separation performances (Li et al., 2017 ). There are some Co²⁺ complexes containing only ligand L₁ [refcodes AJIKIO (Fu et al., 2009 ), NUCGUO (Wei et al., 2009 ), ROMRUH (Xu et al., 2009 ), ROMRUH01 (Wei et al., 2009), ROMRUH02 (Shi et al., 2012 ), SILZAP (Lo et al., 2007 ), SOGCEX (Gao et al., 2008 ), and YOTFET (Song et al., 2009 )]. However, none of these exhibit a tetrahedral geometry around the Co atom. A zinc complex (BOVQUZ; Li et al., 2009 ) displays a tetrahedral coordination around the metal center. By using cyclopentadienyliron dicarbonyl dimer as a starting material, two new Fe^II-based MOFs have been constructed (HOHBEN and HOHBIR; Li et al., 2014 ). As a typical imidazole-carboxylate ligand, 1H-benzimidazole-5,6-dicarboxylate could bind rare earth/transition-metal centers with multiple coordination modes, which provides an ideal platform for the preparation of various coordination polymers, such as BASTOG (Sun et al., 2010 ), EHETAO (Jin et al., 2016 ) and FELBAC (Chai et al., 2018 ).

5. Synthesis and crystallization

A mixture of Co(NO₃)₂·6H₂O (20 mg, 0.069 mmol), 1H-benzimidazole-5,6-dicarboxylic acid (10 mg, 0.049 mmol), 3-amino-1,2,4-triazole (10 mg, 0.119 mmol), DMA (2 mL) and H₂O (2 mL) were added to a 20 mL vial. The reaction system was then heated at 373 K for 72 h in an oven. Purple block-shaped crystals of the title compound suitable for X-ray analysis were obtained.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were placed in calculated positions (N—H = 0.86 Å, C—H = 0.93 Å) and refined as riding with U_iso(H) = 1.2U_eq(N,C)

Table 2
Experimental details

Crystal data
Chemical formula	[Co(C₉H₄N₂O₄)(C₂H₄N₄)]
M_r	347.16
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	279
a, b, c (Å)	13.3368 (8), 6.8727 (4), 13.6015 (10)
β (°)	103.478 (7)
V (Å³)	1212.38 (14)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.45
Crystal size (mm)	0.06 × 0.05 × 0.04

Data collection
Diffractometer	Rigaku Oxford Diffraction SuperNova, Dual, Cu at home/near, AtlasS2
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.979, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5618, 2475, 1839
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.098, 1.03
No. of reflections	2475
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.43
Computer programs: CrysAlis PRO (Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1996100

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021005867/dj2027sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S2056989021005867/dj2027Isup3.cdx

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021005867/dj2027Isup4.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); 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); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Poly[(3-amino-1,2,4-triazole)(µ₃-1H-benzimidazole-5,6-dicarboxylato)cobalt(II)] top

Crystal data top

[Co(C₉H₄N₂O₄)(C₂H₄N₄)]	F(000) = 700
M_r = 347.16	D_x = 1.902 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.3368 (8) Å	Cell parameters from 1697 reflections
b = 6.8727 (4) Å	θ = 4.3–26.7°
c = 13.6015 (10) Å	µ = 1.45 mm⁻¹
β = 103.478 (7)°	T = 279 K
V = 1212.38 (14) Å³	Block, purple
Z = 4	0.06 × 0.05 × 0.04 mm

Data collection top

Rigaku Oxford Diffraction SuperNova, Dual, Cu at home/near, AtlasS2 diffractometer	2475 independent reflections
Graphite monochromator	1839 reflections with I > 2σ(I)
Detector resolution: 10.3376 pixels mm^-1	R_int = 0.046
phi and ω scans	θ_max = 26.4°, θ_min = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	h = −14→16
T_min = 0.979, T_max = 1.000	k = −8→8
5618 measured reflections	l = −17→12

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)] = 0.047	H-atom parameters constrained
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.0319P)² + 0.6634P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
2475 reflections	Δρ_max = 0.45 e Å⁻³
199 parameters	Δρ_min = −0.43 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Co1	0.75360 (3)	0.69451 (6)	0.52745 (4)	0.02172 (16)
O2	0.76917 (18)	−0.1847 (3)	0.40067 (19)	0.0298 (6)
O1	0.74157 (18)	0.0171 (3)	0.27211 (19)	0.0303 (6)
O4	0.66113 (18)	0.4785 (3)	0.4920 (2)	0.0328 (6)
O3	0.77486 (18)	0.2754 (4)	0.4537 (2)	0.0418 (7)
N2	0.3154 (2)	0.1240 (4)	0.3922 (2)	0.0203 (6)
N1	0.3399 (2)	−0.1552 (4)	0.3188 (2)	0.0254 (7)
H1	0.326047	−0.266046	0.289464	0.030*
N4	0.9004 (2)	0.6928 (4)	0.6053 (2)	0.0264 (7)
C4	0.6862 (3)	0.3188 (5)	0.4544 (3)	0.0216 (8)
C7	0.4351 (2)	−0.0655 (5)	0.3432 (2)	0.0197 (7)
C6	0.4188 (2)	0.1110 (5)	0.3892 (2)	0.0190 (7)
C8	0.5319 (2)	−0.1215 (5)	0.3322 (3)	0.0223 (8)
H8	0.541882	−0.239926	0.302707	0.027*
N3	1.0667 (2)	0.7206 (5)	0.6511 (3)	0.0402 (9)
H3	1.129713	0.736543	0.647408	0.048*
C1	0.7158 (3)	−0.0546 (5)	0.3456 (3)	0.0210 (8)
C3	0.5986 (2)	0.1848 (5)	0.4132 (2)	0.0205 (7)
C9	0.2731 (3)	−0.0376 (5)	0.3493 (3)	0.0254 (8)
H9	0.203572	−0.067057	0.340978	0.031*
C2	0.6129 (2)	0.0051 (5)	0.3665 (2)	0.0198 (7)
C5	0.5008 (2)	0.2361 (5)	0.4240 (3)	0.0215 (8)
H5	0.490570	0.353422	0.454314	0.026*
N5	1.0361 (2)	0.6888 (5)	0.7393 (3)	0.0449 (9)
N6	0.9921 (3)	0.7490 (5)	0.4760 (3)	0.0491 (10)
H6A	1.051093	0.765185	0.461830	0.059*
H6B	0.936808	0.749236	0.428430	0.059*
C10	0.9863 (3)	0.7234 (5)	0.5721 (3)	0.0300 (9)
C11	0.9367 (3)	0.6734 (6)	0.7073 (3)	0.0380 (10)
H11	0.893449	0.650912	0.750793	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0156 (3)	0.0225 (3)	0.0273 (3)	−0.0014 (2)	0.00539 (19)	−0.0020 (2)
O2	0.0248 (13)	0.0346 (14)	0.0315 (15)	0.0118 (12)	0.0097 (11)	0.0126 (12)
O1	0.0273 (14)	0.0316 (14)	0.0369 (16)	0.0087 (12)	0.0178 (12)	0.0121 (12)
O4	0.0234 (14)	0.0270 (14)	0.0481 (17)	−0.0055 (12)	0.0083 (12)	−0.0114 (13)
O3	0.0146 (13)	0.0519 (18)	0.061 (2)	−0.0066 (13)	0.0135 (13)	−0.0209 (15)
N2	0.0151 (14)	0.0249 (15)	0.0214 (16)	−0.0029 (13)	0.0057 (12)	−0.0010 (13)
N1	0.0206 (15)	0.0259 (16)	0.0307 (18)	−0.0053 (13)	0.0080 (13)	−0.0088 (13)
N4	0.0142 (14)	0.0321 (17)	0.0327 (18)	−0.0010 (13)	0.0047 (13)	0.0032 (14)
C4	0.0197 (18)	0.0233 (18)	0.0228 (19)	−0.0069 (15)	0.0068 (14)	−0.0014 (15)
C7	0.0200 (18)	0.0199 (17)	0.0197 (18)	−0.0035 (15)	0.0055 (14)	−0.0002 (14)
C6	0.0175 (17)	0.0200 (17)	0.0201 (18)	−0.0007 (15)	0.0060 (14)	0.0020 (14)
C8	0.0229 (18)	0.0186 (17)	0.026 (2)	0.0030 (16)	0.0069 (15)	−0.0033 (15)
N3	0.0159 (16)	0.062 (2)	0.043 (2)	−0.0036 (16)	0.0083 (15)	0.0089 (18)
C1	0.0222 (18)	0.0175 (17)	0.0239 (19)	−0.0018 (15)	0.0067 (15)	−0.0053 (15)
C3	0.0184 (17)	0.0233 (18)	0.0199 (18)	−0.0012 (15)	0.0046 (14)	0.0005 (15)
C9	0.0190 (18)	0.0292 (19)	0.028 (2)	−0.0019 (16)	0.0052 (15)	−0.0012 (16)
C2	0.0178 (17)	0.0223 (18)	0.0187 (18)	0.0024 (15)	0.0030 (14)	0.0041 (15)
C5	0.0203 (18)	0.0196 (17)	0.0240 (19)	−0.0011 (15)	0.0041 (15)	−0.0003 (15)
N5	0.0260 (18)	0.068 (3)	0.039 (2)	−0.0059 (17)	0.0032 (16)	0.0083 (19)
N6	0.0297 (19)	0.084 (3)	0.038 (2)	0.0013 (19)	0.0161 (16)	0.010 (2)
C10	0.0228 (19)	0.031 (2)	0.038 (2)	0.0027 (17)	0.0099 (17)	0.0063 (18)
C11	0.026 (2)	0.055 (3)	0.034 (2)	−0.001 (2)	0.0066 (17)	0.010 (2)

Geometric parameters (Å, º) top

Co1—O2ⁱ	1.968 (2)	C7—C8	1.390 (4)
Co1—O4	1.919 (2)	C6—C5	1.384 (4)
Co1—N2ⁱⁱ	2.016 (3)	C8—H8	0.9300
Co1—N4	1.997 (3)	C8—C2	1.381 (5)
O2—C1	1.272 (4)	N3—H3	0.8600
O1—C1	1.234 (4)	N3—N5	1.372 (5)
O4—C4	1.287 (4)	N3—C10	1.331 (5)
O3—C4	1.222 (4)	C1—C2	1.521 (5)
N2—C6	1.392 (4)	C3—C2	1.422 (5)
N2—C9	1.319 (4)	C3—C5	1.392 (5)
N1—H1	0.8600	C9—H9	0.9300
N1—C7	1.380 (4)	C5—H5	0.9300
N1—C9	1.337 (4)	N5—C11	1.300 (5)
N4—C10	1.342 (5)	N6—H6A	0.8600
N4—C11	1.366 (5)	N6—H6B	0.8600
C4—C3	1.490 (5)	N6—C10	1.339 (5)
C7—C6	1.405 (5)	C11—H11	0.9300

O2ⁱ—Co1—N2ⁱⁱ	111.64 (11)	N5—N3—H3	124.4
O2ⁱ—Co1—N4	100.15 (11)	C10—N3—H3	124.4
O4—Co1—O2ⁱ	107.41 (11)	C10—N3—N5	111.1 (3)
O4—Co1—N2ⁱⁱ	105.49 (11)	O2—C1—C2	119.0 (3)
O4—Co1—N4	128.46 (11)	O1—C1—O2	122.3 (3)
N4—Co1—N2ⁱⁱ	103.38 (11)	O1—C1—C2	118.6 (3)
C1—O2—Co1ⁱⁱⁱ	130.8 (2)	C2—C3—C4	122.0 (3)
C4—O4—Co1	123.3 (2)	C5—C3—C4	118.4 (3)
C6—N2—Co1ⁱⁱ	129.5 (2)	C5—C3—C2	119.6 (3)
C9—N2—Co1ⁱⁱ	124.0 (2)	N2—C9—N1	113.5 (3)
C9—N2—C6	104.9 (3)	N2—C9—H9	123.2
C7—N1—H1	126.4	N1—C9—H9	123.2
C9—N1—H1	126.4	C8—C2—C1	115.8 (3)
C9—N1—C7	107.3 (3)	C8—C2—C3	121.5 (3)
C10—N4—Co1	129.0 (3)	C3—C2—C1	122.6 (3)
C10—N4—C11	103.3 (3)	C6—C5—C3	119.4 (3)
C11—N4—Co1	127.6 (3)	C6—C5—H5	120.3
O4—C4—C3	115.0 (3)	C3—C5—H5	120.3
O3—C4—O4	123.5 (3)	C11—N5—N3	102.1 (3)
O3—C4—C3	121.4 (3)	H6A—N6—H6B	120.0
N1—C7—C6	105.3 (3)	C10—N6—H6A	120.0
N1—C7—C8	132.6 (3)	C10—N6—H6B	120.0
C8—C7—C6	122.1 (3)	N3—C10—N4	108.5 (3)
N2—C6—C7	109.0 (3)	N3—C10—N6	124.8 (4)
C5—C6—N2	131.2 (3)	N6—C10—N4	126.7 (3)
C5—C6—C7	119.8 (3)	N4—C11—H11	122.5
C7—C8—H8	121.2	N5—C11—N4	115.1 (4)
C2—C8—C7	117.5 (3)	N5—C11—H11	122.5
C2—C8—H8	121.2

Co1—O4—C4—O3	13.1 (5)	C7—C8—C2—C1	−175.4 (3)
Co1—O4—C4—C3	−168.4 (2)	C5—C3—C2—C8	−0.6 (5)
C9—N1—C7—C8	178.0 (4)	C4—C3—C2—C8	177.4 (3)
C9—N1—C7—C6	−0.2 (4)	C5—C3—C2—C1	175.7 (3)
C9—N2—C6—C5	−179.1 (4)	C4—C3—C2—C1	−6.3 (5)
Co1ⁱⁱ—N2—C6—C5	−13.5 (5)	O1—C1—C2—C8	98.3 (4)
C9—N2—C6—C7	−0.3 (4)	O2—C1—C2—C8	−77.6 (4)
Co1ⁱⁱ—N2—C6—C7	165.4 (2)	O1—C1—C2—C3	−78.3 (4)
N1—C7—C6—C5	179.3 (3)	O2—C1—C2—C3	105.8 (4)
C8—C7—C6—C5	0.8 (5)	N2—C6—C5—C3	178.5 (3)
N1—C7—C6—N2	0.3 (4)	C7—C6—C5—C3	−0.2 (5)
C8—C7—C6—N2	−178.2 (3)	C2—C3—C5—C6	0.1 (5)
N1—C7—C8—C2	−179.2 (3)	C4—C3—C5—C6	−177.9 (3)
C6—C7—C8—C2	−1.2 (5)	C10—N3—N5—C11	0.2 (4)
Co1ⁱⁱⁱ—O2—C1—O1	173.7 (2)	N5—N3—C10—N6	−179.1 (4)
Co1ⁱⁱⁱ—O2—C1—C2	−10.5 (4)	N5—N3—C10—N4	−0.3 (4)
O3—C4—C3—C5	174.7 (3)	C11—N4—C10—N3	0.3 (4)
O4—C4—C3—C5	−3.8 (5)	Co1—N4—C10—N3	176.1 (2)
O3—C4—C3—C2	−3.3 (5)	C11—N4—C10—N6	179.1 (4)
O4—C4—C3—C2	178.2 (3)	Co1—N4—C10—N6	−5.1 (6)
C6—N2—C9—N1	0.2 (4)	N3—N5—C11—N4	0.0 (5)
Co1ⁱⁱ—N2—C9—N1	−166.5 (2)	C10—N4—C11—N5	−0.2 (5)
C7—N1—C9—N2	0.0 (4)	Co1—N4—C11—N5	−176.1 (3)
C7—C8—C2—C3	1.1 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^iv	0.86	1.84	2.675 (4)	163
N3—H3···O1^v	0.86	2.48	3.104 (4)	130
N3—H3···O3^v	0.86	2.08	2.811 (4)	142
N6—H6A···O3^v	0.86	2.35	3.036 (5)	136
N6—H6B···O2ⁱ	0.86	2.23	2.946 (5)	141
C5—H5···O4ⁱⁱ	0.93	2.58	3.312 (4)	136
C5—H5···O4	0.93	2.37	2.698 (4)	100
C9—H9···N5^vi	0.93	2.48	3.332 (5)	152
C11—H11···O1^vii	0.93	2.41	3.215 (5)	145

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

Funding information

The authors gratefully acknowledge financial support from the National Innovation and Entrepreneurship Training Program of Beijing University of Technology for College Students (GJDC-2019-01-43).

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