Synthesis and crystal structure of a two-dimensional CoII coordination polymer: poly[(μ3-3-carb­oxy­benzoato)[μ2-5-(pyridin-4-yl)-1H,2′H-3,3′-bi[1,2,4-triazole]]cobalt(II)]

Du, C.-J.; Zhao, X.-N.; Chen, B.-Y.

doi:10.1107/S205698901701533X

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ISSN: 2056-9890

Volume 73| Part 11| November 2017| Pages 1779-1781

https://doi.org/10.1107/S205698901701533X

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Synthesis and crystal structure of a two-dimensional Co^II coordination polymer: poly[(μ₃-3-carboxybenzoato)[μ₂-5-(pyridin-4-yl)-1H,2′H-3,3′-bi[1,2,4-triazole]]cobalt(II)]

Chao-Jun Du,^a ^* Xiao-Na Zhao ^a,^b and Bao-Yong Chen ^c

^aDepartment of Biology and Chemical Engineering, Nanyang Institute of Technology, 473004 Nanyang, Henan, People's Republic of China, ^bDepartment of Chemical and Chemical Engineering, Guang Xi University, 530000 Nanning, Guangxi, People's Republic of China, and ^cLaiwu Steel Hospital, 271126 Laiwu, Shandong, People's Republic of China
^*Correspondence e-mail: hyperchem@126.com

Edited by V. Khrustalev, Russian Academy of Sciences, Russia (Received 9 August 2017; accepted 21 October 2017; online 27 October 2017)

In the title compound, [Co(C₈H₅O₄)(C₉H₆N₇)]_n, the divalent Co^II atom is six-coordinated to three N atoms from two symmetrical 5-(pyridin-4-yl)-1H,2′H-3,3′-bi[1,2,4-triazole] (H₂pyttz) ligands and three O atoms from three symmetrical 3-carboxybenzoate (Hbdic) ligands, leading to a distorted {CoN₃O₃} octahedral coordination environment. Two Co^II cations are linked by four bridging carboxylate groups to generate a dinuclear [Co₂(CO₂)₄] unit. The dinuclear units are further connected into a chain along [010] via the Hbdic ligands. The other infinite chain, along [100], is formed through the H₂pyttz ligands. Finally, the two kinds of chains are cross-linked, by sharing the Co^II cations, into a two-dimensional network. In the crystal, adjacent layers are further linked by O—H⋯N hydrogen bonds into a three-dimensional framework.

Keywords: crystal structure; cobalt complex; 5-(pyridin-4-yl)-1H,2′H-3,3′-bi(1,2,4-triazole); benzene-1,3-dicarboxylic acid; octahedral geometry; hydrogen bond.

CCDC reference: 1498228

1. Chemical context

In recent years, the design and synthesis of coordination polymers (CPs) or metal–organic frameworks (MOFs) have attracted great interest because of their fascinating architectures and potential applications in areas such as gas storage and separation, catalysis, fluorescence, magnetism, molecular recognition, conductivity etc (Kitagawa et al., 2004 ; Zhou et al., 2012 ; Cavka et al., 2014 ; Zhang et al., 2014 ; Huang et al., 2017 ; Nath et al., 2016 ; Ni et al., 2017 ; Yi et al., 2016 ; Sun et al., 2016 ). It is well known that organic ligands play a crucial role in the rational design and synthesis of coordination polymers (Li & Sato, 2017 ; Sun & Sun, 2015 ). Among the many organonitrogen ligands, the rigid 5-(pyridin-4-yl)-1H,2′H-3,3′-bi(1,2,4-triazole) ligand (H₂pyttz) attracted our attention for the following reasons. First, the H₂pyttz ligand possesses seven potential N-donor coordination sites and can exhibit various coordination modes. Second, the uncoordinated N atoms are helpful for the construction of hydrogen bonds. The hydrogen bonds not only increase the diversity of coordination polymer structures, but also enhance their stability. With an increasing interest in H₂pyttz organometallic systems, we report herein on the synthesis and crystal structure of the title compound [Co(C₈H₅O₄)(C₉H₆N₇)]_n, (I).

2. Structural commentary

The asymmetric unit of (I) contains one independent Co^II cation, one partially deprotonated Hpyttz⁻ ligand and one partial deprotonated Hbtc⁻ ligand. Notably, the deprotonated Hbtc⁻ ligand adopts two different coordination modes. The deprotonated carboxylate group has a bis(monodentate) coordination mode to bridge two Co^II centers while the undeprotonated carboxylic group adopts a monodentate mode. As shown in Fig. 1, the Co^II cation is six-coordinated to three carboxylic oxygen atoms from three symmetrical Hbtc⁻ ligands and three nitrogen atoms from two symmetrical Hpyttz⁻ ligands in a distorted [CoN₃O₃] octahedral coordination geometry. Four bridging carboxylate groups link two Co^II cations to generate a dinuclear [Co₂(CO₂)₄] unit, which is further connected into an infinite chain along the b-axis direction. There exist eight- and 16-membered metallamacrocycles in the chain structure. In the 16-membered metallamacrocycle, the dihedral angle between the two aromatic rings is 0°, indicating the parallel orientation of the two aromatic rings.

Figure 1
Coordination environment of the Co^II cation in (I)

showing the atomic numbering scheme, with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (A) 1 − x, −y, 1 − z; (B) 1 − x, 1 − y, 1 − z; (C) −1 + x, y, z.]

The other infinite linear chain is along the a-axis direction with a Co⋯Co distance of 6.5825 (5) Å and Co—Co—Co angle of 180.00° and it is also generated through the coordination between the Hpyttz⁻ ligands and the Co^II cations. In the complex, the Hpyttz⁻ ligand is almost coplanar, with dihedral angles of 7.48 (4), 6.87 (4) and 4.43 (4) ° between the pyridine and the two triazole rings, respectively. Finally, these two kinds of chains are cross-linked, by sharing the Co^II cations, into a two-dimensional network.

3. Supramolecular features

In the crystal, adjacent two-dimensional networks are packed parallel to each other in an ⋯AAAA⋯ fashion (Fig. 2). It should be noted that the carboxylic oxygen atom O3 and the uncoordinated nitrogen atom N7 in adjacent networks interact with each other and form strong O3—H3⋯N7 hydrogen bonds (Table 1), which further link the two-dimensional networks into a three-dimensional supramolecular architecture.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯N7ⁱ	0.89 (5)	1.72 (5)	2.592 (4)	166 (5)
Symmetry code: (i) x+1, y-1, z-1.

Figure 2
The three-dimensional structure of the title complex formed by the O—H⋯N hydrogen bonds (dashed lines) between adjacent networks (depicted in different colours). H atoms not involved in hydrogen bonds have been omitted for clarity.

4. Database survey

A search of the Cambridge Structural Database (Version 5.37; Groom et al., 2016 ) for 5-(pyridin-4-yl)-1H,2′H-3,3′-bi(1,2,4-triazole) reveals five structures. Of these, there is only one Co^II coordination structure (ZOTDIX; Gong et al., 2014 ). In this structure, the pyridyl nitrogen atom is not coordinated to the Co^II cation.

5. Synthesis and crystallization

A mixture of Co(NO₃)₂^.6H₂O (0.10 mmol), 5-(pyridin-4-yl)-1H,2′H-3,3′-bi(1,2,4-triazole) (0.10 mmol), benzene-1,3-dicarboxylic acid (0.10 mmol) and H₂O (10 ml) was stirred at room temperature for 30 min. When the pH value had been adjusted to about 7.0 with 0.1 M NaOH, the mixture was sealed in a 20 ml Tefon-lined stainless-steel reactor and then heated to 433 K for 72 h under autogenous pressure, and then slowly cooled to room temperature at a rate of 5 K h⁻¹. Pink block-shaped crystals of the title complex were isolated, washed with distilled water, and dried in air (yield 52%).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms attached to C and N atoms were placed in calculated positions (C—H = 0.93 Å, N—H = 0.86 Å) and refined as riding atoms with U_iso(H) = 1.2U_eq(C,N), respectively. The carboxyl H atom was located in the difference Fourier-map and refined isotropically with U_iso(H) = 1.5U_eq(O).

Table 2
Experimental details

Crystal data
Chemical formula	[Co(C₈H₅O₄)(C₉H₆N₇)]
M_r	436.26
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	6.5825 (5), 9.0574 (12), 13.9842 (12)
α, β, γ (°)	74.214 (1), 84.690 (2), 82.303 (1)
V (Å³)	793.69 (14)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.13
Crystal size (mm)	0.20 × 0.18 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.797, 0.858
No. of measured, independent and observed [I > 2σ(I)] reflections	5565, 3507, 2338
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.113, 1.09
No. of reflections	3507
No. of parameters	265
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.59
Computer programs: SMART and SAINT (Bruker, 2008), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), SHELXTL (Sheldrick, 2008 ) and DIAMOND (Brandenburg & Putz, 2006 ).

Supporting information

CCDC reference: 1498228

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S205698901701533X/kq2016sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901701533X/kq2016Isup2.hkl

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2008); cell refinement: SMART (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: DIAMOND (Brandenburg & Putz, 2006).

Poly[(µ₃-3-carboxybenzoato)[µ₂-5-(pyridin-4-yl)-1H,2'H-3,3'-bi[1,2,4-triazole]]cobalt(II)] top

Crystal data top

[Co(C₈H₅O₄)(C₉H₆N₇)]	Z = 2
M_r = 436.26	F(000) = 442
Triclinic, P1	D_x = 1.825 Mg m⁻³
a = 6.5825 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.0574 (12) Å	Cell parameters from 1163 reflections
c = 13.9842 (12) Å	θ = 3.0–28.3°
α = 74.214 (1)°	µ = 1.13 mm⁻¹
β = 84.690 (2)°	T = 293 K
γ = 82.303 (1)°	Block, pink
V = 793.69 (14) Å³	0.20 × 0.18 × 0.15 mm

Data collection top

Bruker SMART CCD area detector diffractometer	2338 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.055
φ and ω scans	θ_max = 28.4°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −8→8
T_min = 0.797, T_max = 0.858	k = −11→12
5565 measured reflections	l = −16→18
3507 independent reflections

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.061	Hydrogen site location: mixed
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0172P)² + 0.0319P] where P = (F_o² + 2F_c²)/3
3507 reflections	(Δ/σ)_max < 0.001
265 parameters	Δρ_max = 0.49 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
Co1	0.36855 (8)	0.42648 (8)	0.65379 (5)	0.02024 (18)
N1	0.2335 (5)	0.5770 (4)	0.8362 (3)	0.0196 (9)
N2	0.3746 (5)	0.5162 (4)	0.7767 (3)	0.0182 (9)
N3	0.5482 (5)	0.6182 (4)	0.8697 (3)	0.0210 (9)
N4	0.9301 (5)	0.5039 (4)	0.7413 (3)	0.0200 (9)
H4	0.9832	0.5434	0.7811	0.024*
N5	1.0369 (5)	0.4445 (4)	0.6689 (3)	0.0197 (9)
N6	0.7019 (5)	0.4259 (4)	0.6688 (3)	0.0191 (9)
N7	0.0562 (5)	0.8553 (5)	1.1093 (3)	0.0273 (10)
O1	0.3534 (4)	0.3140 (4)	0.5493 (2)	0.0209 (7)
O2	0.6377 (4)	0.3585 (4)	0.4500 (2)	0.0209 (7)
O3	0.8393 (5)	−0.0128 (4)	0.2340 (3)	0.0342 (10)
H3	0.917 (7)	−0.071 (6)	0.200 (4)	0.051*
O4	0.6280 (4)	−0.1888 (4)	0.2391 (2)	0.0257 (8)
C1	0.5576 (6)	0.5438 (5)	0.7995 (3)	0.0180 (10)
C2	0.3424 (6)	0.6368 (5)	0.8906 (3)	0.0199 (10)
C3	0.7332 (6)	0.4911 (5)	0.7405 (3)	0.0173 (10)
C4	0.8918 (6)	0.3997 (5)	0.6277 (3)	0.0206 (11)
H4A	0.9183	0.3542	0.5751	0.025*
C5	−0.0515 (6)	0.7829 (6)	1.0630 (4)	0.0280 (12)
H5	−0.1909	0.7793	1.0807	0.034*
C6	0.0347 (6)	0.7140 (6)	0.9909 (4)	0.0282 (12)
H6	−0.0461	0.6662	0.9598	0.034*
C7	0.2431 (6)	0.7154 (5)	0.9641 (3)	0.0209 (10)
C8	0.3536 (6)	0.7892 (6)	1.0130 (4)	0.0297 (12)
H8	0.4938	0.7923	0.9977	0.036*
C9	0.2573 (7)	0.8578 (6)	1.0842 (4)	0.0300 (13)
H9	0.3342	0.9075	1.1159	0.036*
C10	0.4755 (6)	0.2952 (5)	0.4773 (3)	0.0186 (10)
C11	0.6668 (6)	−0.0715 (6)	0.2607 (3)	0.0213 (10)
C12	0.4189 (6)	0.1867 (5)	0.4224 (3)	0.0173 (10)
C13	0.5649 (6)	0.1212 (5)	0.3625 (3)	0.0191 (10)
H13	0.6973	0.1499	0.3523	0.023*
C14	0.5117 (6)	0.0126 (5)	0.3179 (3)	0.0198 (10)
C15	0.3112 (6)	−0.0227 (5)	0.3286 (3)	0.0235 (11)
H15	0.2761	−0.0946	0.2982	0.028*
C16	0.1631 (6)	0.0470 (6)	0.3834 (4)	0.0285 (12)
H16	0.0276	0.0257	0.3880	0.034*
C17	0.2189 (6)	0.1497 (6)	0.4316 (3)	0.0239 (11)
H17	0.1206	0.1943	0.4706	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0155 (3)	0.0282 (4)	0.0212 (4)	−0.0045 (3)	0.0037 (2)	−0.0142 (3)
N1	0.0152 (18)	0.027 (2)	0.019 (2)	−0.0025 (16)	0.0041 (15)	−0.0124 (19)
N2	0.0152 (17)	0.022 (2)	0.019 (2)	−0.0014 (16)	0.0029 (15)	−0.0101 (19)
N3	0.0155 (18)	0.028 (2)	0.023 (2)	−0.0047 (16)	0.0039 (15)	−0.0132 (19)
N4	0.0158 (18)	0.030 (2)	0.019 (2)	−0.0041 (16)	0.0025 (15)	−0.0150 (19)
N5	0.0120 (17)	0.024 (2)	0.025 (2)	−0.0028 (16)	0.0053 (15)	−0.0112 (19)
N6	0.0159 (17)	0.027 (2)	0.019 (2)	−0.0039 (16)	0.0009 (15)	−0.0129 (19)
N7	0.031 (2)	0.029 (3)	0.025 (2)	−0.0022 (19)	0.0044 (18)	−0.016 (2)
O1	0.0245 (16)	0.0234 (19)	0.0183 (18)	−0.0064 (14)	0.0066 (13)	−0.0120 (15)
O2	0.0201 (15)	0.0205 (18)	0.0247 (19)	−0.0065 (13)	0.0016 (13)	−0.0096 (16)
O3	0.0267 (18)	0.041 (2)	0.043 (2)	−0.0092 (17)	0.0161 (16)	−0.029 (2)
O4	0.0300 (17)	0.026 (2)	0.026 (2)	−0.0057 (15)	0.0039 (14)	−0.0147 (17)
C1	0.018 (2)	0.022 (3)	0.016 (2)	−0.0021 (19)	0.0014 (17)	−0.008 (2)
C2	0.019 (2)	0.025 (3)	0.018 (3)	−0.006 (2)	0.0003 (18)	−0.010 (2)
C3	0.015 (2)	0.020 (3)	0.018 (2)	−0.0010 (18)	0.0004 (17)	−0.008 (2)
C4	0.017 (2)	0.022 (3)	0.026 (3)	0.000 (2)	0.0024 (19)	−0.014 (2)
C5	0.020 (2)	0.038 (3)	0.027 (3)	−0.004 (2)	0.010 (2)	−0.015 (3)
C6	0.021 (2)	0.042 (3)	0.027 (3)	−0.003 (2)	0.006 (2)	−0.021 (3)
C7	0.025 (2)	0.023 (3)	0.017 (3)	0.001 (2)	0.0010 (19)	−0.011 (2)
C8	0.017 (2)	0.044 (3)	0.034 (3)	−0.004 (2)	0.003 (2)	−0.022 (3)
C9	0.031 (3)	0.037 (3)	0.032 (3)	−0.009 (2)	0.002 (2)	−0.024 (3)
C10	0.016 (2)	0.016 (3)	0.023 (3)	0.0015 (19)	0.0000 (18)	−0.004 (2)
C11	0.022 (2)	0.026 (3)	0.016 (3)	−0.001 (2)	−0.0006 (18)	−0.007 (2)
C12	0.019 (2)	0.023 (3)	0.013 (2)	−0.0060 (19)	0.0008 (17)	−0.010 (2)
C13	0.016 (2)	0.025 (3)	0.019 (3)	−0.0109 (19)	0.0068 (17)	−0.009 (2)
C14	0.025 (2)	0.019 (3)	0.017 (2)	−0.004 (2)	0.0040 (18)	−0.008 (2)
C15	0.024 (2)	0.026 (3)	0.026 (3)	−0.008 (2)	0.002 (2)	−0.016 (2)
C16	0.021 (2)	0.038 (3)	0.033 (3)	−0.007 (2)	0.003 (2)	−0.019 (3)
C17	0.025 (2)	0.027 (3)	0.022 (3)	0.002 (2)	0.0048 (19)	−0.013 (2)

Geometric parameters (Å, º) top

Co1—O1	2.012 (3)	O4—C11	1.244 (5)
Co1—O2ⁱ	2.086 (3)	O4—Co1ⁱⁱⁱ	2.262 (4)
Co1—N2	2.097 (3)	C1—C3	1.461 (5)
Co1—N5ⁱⁱ	2.162 (3)	C2—C7	1.463 (5)
Co1—N6	2.223 (3)	C4—H4A	0.9300
Co1—O4ⁱⁱⁱ	2.262 (4)	C5—C6	1.368 (5)
N1—C2	1.347 (5)	C5—H5	0.9300
N1—N2	1.352 (4)	C6—C7	1.389 (6)
N2—C1	1.345 (5)	C6—H6	0.9300
N3—C1	1.327 (5)	C7—C8	1.384 (6)
N3—C2	1.357 (5)	C8—C9	1.377 (6)
N4—C3	1.318 (5)	C8—H8	0.9300
N4—N5	1.368 (4)	C9—H9	0.9300
N4—H4	0.8600	C10—C12	1.502 (5)
N5—C4	1.320 (5)	C11—C14	1.495 (5)
N5—Co1^iv	2.162 (3)	C12—C17	1.387 (6)
N6—C3	1.338 (5)	C12—C13	1.395 (5)
N6—C4	1.345 (5)	C13—C14	1.394 (5)
N7—C5	1.339 (5)	C13—H13	0.9300
N7—C9	1.339 (5)	C14—C15	1.385 (5)
O1—C10	1.262 (5)	C15—C16	1.377 (5)
O2—C10	1.258 (5)	C15—H15	0.9300
O2—Co1ⁱ	2.086 (3)	C16—C17	1.391 (6)
O3—C11	1.299 (5)	C16—H16	0.9300
O3—H3	0.89 (5)	C17—H17	0.9300

O1—Co1—O2ⁱ	93.18 (12)	N5—C4—N6	113.9 (4)
O1—Co1—N2	172.28 (15)	N5—C4—H4A	123.1
O2ⁱ—Co1—N2	94.31 (13)	N6—C4—H4A	123.1
O1—Co1—N5ⁱⁱ	87.27 (12)	N7—C5—C6	122.8 (4)
O2ⁱ—Co1—N5ⁱⁱ	91.64 (13)	N7—C5—H5	118.6
N2—Co1—N5ⁱⁱ	90.64 (12)	C6—C5—H5	118.6
O1—Co1—N6	105.23 (11)	C5—C6—C7	119.9 (4)
O2ⁱ—Co1—N6	90.18 (13)	C5—C6—H6	120.1
N2—Co1—N6	76.64 (12)	C7—C6—H6	120.1
N5ⁱⁱ—Co1—N6	167.25 (12)	C8—C7—C6	116.9 (4)
O1—Co1—O4ⁱⁱⁱ	84.32 (12)	C8—C7—C2	121.6 (4)
O2ⁱ—Co1—O4ⁱⁱⁱ	177.47 (11)	C6—C7—C2	121.4 (4)
N2—Co1—O4ⁱⁱⁱ	88.17 (13)	C9—C8—C7	120.4 (4)
N5ⁱⁱ—Co1—O4ⁱⁱⁱ	87.82 (13)	C9—C8—H8	119.8
N6—Co1—O4ⁱⁱⁱ	90.88 (13)	C7—C8—H8	119.8
C2—N1—N2	105.2 (3)	N7—C9—C8	122.0 (4)
C1—N2—N1	105.6 (3)	N7—C9—H9	119.0
C1—N2—Co1	117.7 (3)	C8—C9—H9	119.0
N1—N2—Co1	136.0 (2)	O2—C10—O1	125.2 (4)
C1—N3—C2	100.7 (3)	O2—C10—C12	119.0 (4)
C3—N4—N5	109.5 (3)	O1—C10—C12	115.8 (4)
C3—N4—H4	125.2	O4—C11—O3	123.0 (4)
N5—N4—H4	125.2	O4—C11—C14	121.0 (4)
C4—N5—N4	103.0 (3)	O3—C11—C14	116.1 (4)
C4—N5—Co1^iv	135.8 (3)	C17—C12—C13	119.2 (4)
N4—N5—Co1^iv	121.0 (2)	C17—C12—C10	119.8 (4)
C3—N6—C4	103.5 (3)	C13—C12—C10	121.0 (4)
C3—N6—Co1	111.1 (2)	C14—C13—C12	119.8 (4)
C4—N6—Co1	144.9 (3)	C14—C13—H13	120.1
C5—N7—C9	118.1 (4)	C12—C13—H13	120.1
C10—O1—Co1	132.1 (3)	C15—C14—C13	119.8 (4)
C10—O2—Co1ⁱ	120.5 (3)	C15—C14—C11	118.3 (4)
C11—O3—H3	108 (3)	C13—C14—C11	121.9 (4)
C11—O4—Co1ⁱⁱⁱ	124.8 (3)	C16—C15—C14	120.9 (4)
N3—C1—N2	114.7 (3)	C16—C15—H15	119.5
N3—C1—C3	130.7 (4)	C14—C15—H15	119.5
N2—C1—C3	114.6 (3)	C15—C16—C17	119.1 (4)
N1—C2—N3	113.8 (3)	C15—C16—H16	120.5
N1—C2—C7	121.9 (4)	C17—C16—H16	120.5
N3—C2—C7	124.3 (4)	C12—C17—C16	121.1 (4)
N4—C3—N6	110.1 (3)	C12—C17—H17	119.5
N4—C3—C1	130.3 (4)	C16—C17—H17	119.5
N6—C3—C1	119.5 (3)

C2—N1—N2—C1	−0.1 (5)	N1—C2—C7—C8	−173.9 (5)
C2—N1—N2—Co1	−169.6 (4)	N3—C2—C7—C8	5.4 (8)
C3—N4—N5—C4	0.5 (5)	N1—C2—C7—C6	8.8 (7)
C3—N4—N5—Co1^iv	−174.9 (3)	N3—C2—C7—C6	−171.9 (5)
C2—N3—C1—N2	−0.1 (5)	C6—C7—C8—C9	−0.4 (8)
C2—N3—C1—C3	177.7 (5)	C2—C7—C8—C9	−177.8 (5)
N1—N2—C1—N3	0.1 (5)	C5—N7—C9—C8	0.2 (8)
Co1—N2—C1—N3	171.9 (3)	C7—C8—C9—N7	0.5 (8)
N1—N2—C1—C3	−178.1 (4)	Co1ⁱ—O2—C10—O1	−88.9 (5)
Co1—N2—C1—C3	−6.3 (5)	Co1ⁱ—O2—C10—C12	91.8 (4)
N2—N1—C2—N3	0.0 (5)	Co1—O1—C10—O2	−6.3 (7)
N2—N1—C2—C7	179.3 (4)	Co1—O1—C10—C12	173.1 (3)
C1—N3—C2—N1	0.1 (5)	Co1ⁱⁱⁱ—O4—C11—O3	104.3 (5)
C1—N3—C2—C7	−179.3 (5)	Co1ⁱⁱⁱ—O4—C11—C14	−77.2 (5)
N5—N4—C3—N6	−0.6 (5)	O2—C10—C12—C17	−162.0 (4)
N5—N4—C3—C1	−176.6 (5)	O1—C10—C12—C17	18.6 (6)
C4—N6—C3—N4	0.4 (5)	O2—C10—C12—C13	18.4 (7)
Co1—N6—C3—N4	−173.6 (3)	O1—C10—C12—C13	−161.0 (4)
C4—N6—C3—C1	177.0 (4)	C17—C12—C13—C14	−4.1 (7)
Co1—N6—C3—C1	3.0 (5)	C10—C12—C13—C14	175.5 (4)
N3—C1—C3—N4	−0.2 (9)	C12—C13—C14—C15	3.9 (7)
N2—C1—C3—N4	177.7 (5)	C12—C13—C14—C11	−174.3 (4)
N3—C1—C3—N6	−175.9 (5)	O4—C11—C14—C15	−13.1 (7)
N2—C1—C3—N6	1.9 (6)	O3—C11—C14—C15	165.5 (4)
N4—N5—C4—N6	−0.2 (5)	O4—C11—C14—C13	165.1 (5)
Co1^iv—N5—C4—N6	174.1 (3)	O3—C11—C14—C13	−16.3 (7)
C3—N6—C4—N5	−0.1 (5)	C13—C14—C15—C16	−0.6 (7)
Co1—N6—C4—N5	170.1 (4)	C11—C14—C15—C16	177.7 (4)
C9—N7—C5—C6	−0.9 (8)	C14—C15—C16—C17	−2.5 (7)
N7—C5—C6—C7	1.0 (8)	C13—C12—C17—C16	1.0 (7)
C5—C6—C7—C8	−0.3 (7)	C10—C12—C17—C16	−178.6 (5)
C5—C6—C7—C2	177.1 (5)	C15—C16—C17—C12	2.3 (8)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N7^v	0.89 (5)	1.72 (5)	2.592 (4)	166 (5)

Symmetry code: (v) x+1, y−1, z−1.

Funding information

We acknowledge financial support from Henan Province Project Education Fund (17 A430027).

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