Poly[[{μ2-5-[(di­methyl­amino)(thioxo)meth­oxy]benzene-1,3-di­carboxyl­ato-κ4O1,O1′:O3,O3′}(μ2-4,4′-di­pyridyl­amine-κ2N4:N4′)cobalt(II)] di­methyl­formamide hemisolvate monohydrate]

Qin, H.-Y.; Zhang, B.-G.; Sun, Q.-Z.

doi:10.1107/S2414314624004899

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 9| Part 6| June 2024| x240489

https://doi.org/10.1107/S2414314624004899

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Poly[[{μ₂-5-[(dimethylamino)(thioxo)methoxy]benzene-1,3-dicarboxylato-κ⁴O¹,O^1′:O³,O^3′}(μ_2-4,4′-dipyridylamine-κ²N⁴:N^4′)cobalt(II)] dimethylformamide hemisolvate monohydrate]

Hui-Yu Qin,^a Bing-Guang Zhang ^a ^* and Qiao-Zhen Sun ^b

^aKey Laboratory of Catalysis and Materials Sciences of the State Ethnic Affairs Commission & Ministry of Education, College of Chemistry and Material Science, South-Central Minzu University, Wuhan, 430074, People's Republic of China, and ^bSchool of Materials Science and Engineering, Central South University, Changsha, 410083, People's Republic of China
^*Correspondence e-mail: 3092809@mail.scuec.edu.cn

Edited by M. Weil, Vienna University of Technology, Austria (Received 2 April 2024; accepted 24 May 2024; online 4 June 2024)

In the crystal structure of the title compound, {[Co(C₁₁H₉NSO₅)(C₁₀H₉N₃)]0.5C₃H₇NO·H₂O}_n or {[Co(dmtb)(dpa)]·0.5DMF·H₂O}_n (dmtb^2– = 5-[(dimethylamino)thioxomethoxy]-1,3-benzenedicarboxylate and dpa = 4,4′-dipyridylamine), an assembly of periodic [Co(C₁₁H₉NSO₅)(C₁₀H₉N₃)]_n layers extending parallel to the bc plane is present. Each layer is constituted by distorted [CoO₄N₂] octahedra, which are connected through the μ₂-coordination modes of both dmtb^2– and dpa ligands. Occupationally disordered water and dimethylformamide (DMF) solvent molecules are located in the voids of the network to which they are connected through hydrogen-bonding interactions.

Keywords: crystal structure; coordination polymer; cobalt; 5-[(dimethylamino)thioxomethoxy]-1,3-benzenedicarboxylate; 4,4′-dipyridylamine; hydrogen bonding.

CCDC reference: 2247034

Structure description

The controllable synthesis of coordination polymers with desired structures is always a challenging subject in crystal engineering (Chung et al., 2023 ; Li et al., 2021 ; Yang et al., 2021 ). In many cases, it is difficult to achieve due to the complex interplay of different factors and synthesis parameters such as the preferred coordination environment of the central metal atom, the nature of ligand(s), reaction/incorporation of solvents, temperature, metal-to-ligand ratio, pH value, pressure etc. (Sun et al., 2016 , 2017 , 2018 ; Vornholt et al., 2017 ).

According to our previous studies (Gu et al., 2023 ; Sun et al., 2019 ), the configuration of the secondary ligand can effectively adjust the steric hindrance within the crystal structure. When Zn²⁺ is coordinated by dmtb²⁻ {5-[(dimethylamino)thioxomethoxy]-1,3-benzenedicarboxylate} and bipy (4,4′-bipyridine), the (dimethylamino)thioxomethoxy group of the dmtb^2– ligand increases the steric hindrance, and a di-periodic, i.e. layered, arrangement results. The rigid bipy ligand acts as a pillar in the structural organization (Gu et al., 2023). In this context and in comparison with the former synthesis, we used the slightly larger Co²⁺ cation and the more flexible 4,4′-dipyridylamine (dpa) ligand for the current study. As a result, the title compound, (1), with a likewise layered structural arrangement, was obtained.

The asymmetric unit of (1) (Fig. 1) comprises one cobalt(II) cation, one dmtb²⁻ anion, one dpa ligand, two occupationally disordered solvent water and one DMF (dimethylformamide) solvent molecules, with occupancies of 0.5 for the water molecules and of 0.25 for the DMF solvent molecule. The Co—O/N bond lengths are in the range 2.094 (3)–2.216 (3) Å, comparable with those reported for other related Co²⁺-polycarboxylate compounds (Gu et al., 2022 , 2023; Zhao et al., 2024 ). The Co²⁺ cation is six-coordinated by four oxygen atoms from two different dmtb^2– anions and two nitrogen atoms from two different dpa ligands, forming a distorted octahedral environment. The mean deviation of the equatorial plane constructed by atoms O1, O4A, O5A and N2 is 0.13 Å. The dmtb^2– ligand bridges two Co²⁺ cations in a μ₂-κ₂: κ₂ coordination mode, so that each carboxylate group of the dmtb^2– anion chelates one Co²⁺ cation. The dpa ligands connect the Co²⁺ cations as a ditopic linker. Accordingly, two dmtb^2– and two dpa ligands bridge the Co²⁺ cations into four different directions into a layered arrangement extending parallel to the bc plane (Fig. 2). The 5-(dimethylamino)thioxomethoxy groups dangling above and below a layer protrude into adjacent layers to display an interdigitated motif (Fig. 3). The disordered water and DMF molecules are located in the voids of this arrangement. Without these solvent molecules, the void volume in (1) is 19.4%. The solvent molecules are linked to the layers by classical hydrogen-bonding interactions, which includes the amino group of the dpa ligand (entries 1 and 2 in Table 1) and the water molecules (entries 4–7 in Table 1) as donor groups, and the O atoms of the DMF solvent, of the water molecules and the carboxylate O atoms as acceptor groups. A weaker non-classical hydrogen bond between a CH group of a pyridyl ring and a carboxyate O atom consolidates the crystal packing (Fig. 4).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O6	0.86	1.86	2.700 (19)	164
N3—H3⋯O8	0.86	2.13	2.979 (17)	170
C13—H13⋯O2ⁱ	0.93	2.44	3.174 (5)	135
O7—H7D⋯O4	0.84	2.16	2.992 (7)	174
O7—H7E⋯O2ⁱⁱ	0.88	2.26	3.136 (7)	173
O8—H8A⋯O7ⁱⁱⁱ	0.88	2.33	3.10 (2)	146
O8—H8B⋯O5^iv	0.85	2.28	3.102 (17)	163
Symmetry codes: (i) ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) ; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
The extended asymmetric unit of (1) showing the coordination environment of the Co²⁺ cation. Displacement ellipsoids are drawn at the 30% probability level. The solvent water and DMF molecules are not shown for clarity. [Symmetry codes: (A) −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (B) −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (C) −x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (D) −x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , –z + $[{3\over 2}]$ .]

Figure 2
The layered arrangement extending parallel to the bc plane in the crystal structure of (1).

Figure 3
5-(Dimethylamino)thioxomethoxy moieties of the dmtp^2– ligand protruding into an adjacent layer.

Figure 4
Packing diagram of (1), showing hydrogen-bonding interactions (dashed lines).

Synthesis and crystallization

A mixture of Co(NO₃)₂·6H₂O (29 mg, 0.1 mmol), H₂dmtb (20 mg, 0.07 mmol) and dpa (17 mg, 0.1 mmol) in 4 ml DMF/H₂O (v/v = 1:1) was sealed in a Teflon-lined autoclave and heated to 423 K for 72 h, then gradually cooled down to room temperature. Pink prismatic crystals were obtained. Yield: 24 mg (71%, based on H₂dmtb).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The DMF molecule was located near a symmetry center and its occupancy was fixed at 0.5. After refinement, some residual electron density peaks still existed near the DMF molecule. They were assigned to the O atoms of water molecules, both refined with occupancies of 0.5. ISOR and SIMU instructions in SHELXL (Sheldrick, 2015b ) were used for these solvent molecules. Hydrogen atoms of the water molecules were included in calculated positions for obtaining reasonable hydrogen bonds and were refined in a riding-model approximation with U_iso(H) = 1.5_eq(O).

Table 2
Experimental details

Crystal data
Chemical formula	[Co(C₁₁H₉NO₅S)(C₁₀H₉N₃)]·0.5C₃H₇NO·H₂O
M_r	551.95
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	11.2451 (14), 14.4734 (17), 15.232 (2)
β (°)	103.485 (4)
V (Å³)	2410.7 (5)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.85
Crystal size (mm)	0.32 × 0.20 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.643, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	21131, 4711, 3216
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.150, 1.04
No. of reflections	4711
No. of parameters	355
No. of restraints	64
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.76, −0.42
Computer programs: APEX2 and SAINT (Bruker, 2015 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b), OLEX2 (Dolomanov et al., 2009 ), XP (Sheldrick, 2008 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2247034

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314624004899/wm4212sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314624004899/wm4212Isup3.hkl

checkCIF report

Computing details top

Poly[[{µ₂-5-[(dimethylamino)(thioxo)methoxy]benzene-1,3-dicarboxylato-κ⁴O¹,O^1':O³,O^3'}(µ_2-4,4'-dipyridylamine-κ²N⁴:N^4')cobalt(II)] dimethylformamide hemisolvate monohydrate] top

Crystal data top

[Co(C₁₁H₉NO₅S)(C₁₀H₉N₃)]·0.5C₃H₇NO·H₂O	F(000) = 1140
M_r = 551.95	D_x = 1.521 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.2451 (14) Å	Cell parameters from 4852 reflections
b = 14.4734 (17) Å	θ = 2.9–26.3°
c = 15.232 (2) Å	µ = 0.85 mm⁻¹
β = 103.485 (4)°	T = 298 K
V = 2410.7 (5) Å³	Prism, purple
Z = 4	0.32 × 0.20 × 0.18 mm

Data collection top

Bruker APEXII CCD diffractometer	3216 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.069
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 26.0°, θ_min = 2.5°
T_min = 0.643, T_max = 0.745	h = −13→13
21131 measured reflections	k = −17→17
4711 independent reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.053	H-atom parameters constrained
wR(F²) = 0.150	w = 1/[σ²(F_o²) + (0.0742P)² + 2.1129P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
4711 reflections	Δρ_max = 0.76 e Å⁻³
355 parameters	Δρ_min = −0.42 e Å⁻³
64 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	Occ. (<1)
Co1	0.73927 (5)	0.60696 (3)	0.44875 (3)	0.03359 (18)
S1	0.21293 (14)	0.44589 (10)	0.06254 (10)	0.0733 (4)
O1	0.5793 (2)	0.53436 (19)	0.38364 (19)	0.0461 (7)
O2	0.7529 (3)	0.4927 (2)	0.3548 (2)	0.0535 (8)
O3	0.2652 (2)	0.32239 (19)	0.19296 (19)	0.0456 (7)
O4	0.5950 (3)	0.18067 (18)	0.05399 (18)	0.0460 (7)
O5	0.7602 (3)	0.2134 (2)	0.15532 (19)	0.0510 (8)
N1	0.0682 (3)	0.3554 (2)	0.1501 (2)	0.0469 (9)
N2	0.8119 (3)	0.5239 (2)	0.5610 (2)	0.0372 (7)
N3	0.9644 (3)	0.3791 (2)	0.8000 (2)	0.0412 (8)
H3	1.042657	0.385181	0.814726	0.049*
N4	0.8350 (3)	0.2025 (2)	0.9750 (2)	0.0393 (8)
C1	0.6393 (4)	0.4844 (2)	0.3406 (2)	0.0349 (8)
C2	0.5745 (3)	0.4151 (2)	0.2733 (2)	0.0327 (8)
C3	0.4479 (4)	0.4062 (2)	0.2574 (3)	0.0366 (9)
H3A	0.403355	0.444495	0.286860	0.044*
C4	0.3893 (3)	0.3402 (3)	0.1975 (3)	0.0372 (9)
C5	0.1790 (4)	0.3741 (3)	0.1362 (3)	0.0440 (10)
C6	−0.0385 (4)	0.4035 (3)	0.0981 (3)	0.0567 (12)
H6A	−0.061594	0.451505	0.134299	0.085*
H6B	−0.104911	0.360578	0.080358	0.085*
H6C	−0.019640	0.430104	0.045232	0.085*
C7	0.0470 (4)	0.2900 (4)	0.2157 (4)	0.0664 (14)
H7A	0.071609	0.229571	0.200946	0.100*
H7B	−0.038419	0.289331	0.215602	0.100*
H7C	0.093632	0.307415	0.274533	0.100*
C8	0.4527 (4)	0.2843 (3)	0.1506 (3)	0.0376 (9)
H8	0.411067	0.242145	0.108353	0.045*
C9	0.5783 (3)	0.2916 (2)	0.1671 (2)	0.0331 (8)
C10	0.6488 (4)	0.2256 (2)	0.1232 (2)	0.0359 (9)
C11	0.6394 (3)	0.3569 (2)	0.2289 (2)	0.0328 (8)
H11	0.724132	0.361467	0.240303	0.039*
C12	0.9316 (4)	0.5240 (3)	0.6018 (3)	0.0432 (10)
H12	0.983755	0.557585	0.574663	0.052*
C13	0.9820 (4)	0.4786 (3)	0.6798 (3)	0.0419 (9)
H13	1.065719	0.482183	0.704535	0.050*
C14	0.9069 (4)	0.4261 (2)	0.7228 (2)	0.0359 (9)
C15	0.9165 (4)	0.3234 (2)	0.8576 (2)	0.0374 (9)
C16	0.7984 (4)	0.3275 (3)	0.8688 (2)	0.0418 (9)
H16	0.743752	0.371028	0.837599	0.050*
C17	0.7625 (4)	0.2660 (3)	0.9269 (2)	0.0418 (9)
H17	0.682131	0.269181	0.932704	0.050*
C18	0.9509 (4)	0.2020 (3)	0.9670 (3)	0.0459 (10)
H18	1.004311	0.159659	1.001410	0.055*
C19	0.9959 (4)	0.2596 (3)	0.9116 (3)	0.0441 (10)
H19	1.077847	0.256815	0.909575	0.053*
C20	0.7837 (4)	0.4238 (3)	0.6808 (3)	0.0439 (10)
H20	0.729663	0.389357	0.705490	0.053*
C21	0.7419 (4)	0.4728 (3)	0.6025 (3)	0.0414 (9)
H21	0.658501	0.470415	0.576267	0.050*
O6	1.2102 (17)	0.3656 (14)	0.8304 (14)	0.116 (6)	0.5
O7	0.3470 (7)	0.2021 (5)	−0.0692 (5)	0.090 (3)	0.5
H7D	0.414831	0.198915	−0.032112	0.135*	0.5
H7E	0.317801	0.146795	−0.086502	0.135*	0.5
C23	1.4935 (17)	0.4546 (13)	0.9452 (13)	0.199 (8)	0.5
H23A	1.466619	0.517120	0.949026	0.298*	0.5
H23B	1.561309	0.453770	0.916886	0.298*	0.5
H23C	1.518269	0.428940	1.004746	0.298*	0.5
N5	1.4060 (15)	0.4024 (12)	0.8994 (13)	0.189 (6)	0.5
C22	1.2767 (15)	0.4296 (13)	0.8683 (16)	0.166 (6)	0.5
H22	1.247808	0.488525	0.876167	0.199*	0.5
C24	1.424 (2)	0.3087 (13)	0.8792 (19)	0.237 (9)	0.5
H24A	1.509290	0.297487	0.884281	0.356*	0.5
H24B	1.379160	0.295245	0.818744	0.356*	0.5
H24C	1.394999	0.269661	0.920830	0.356*	0.5
O8	1.2362 (15)	0.3812 (15)	0.8331 (9)	0.109 (6)	0.5
H8A	1.283550	0.349024	0.876365	0.164*	0.5
H8B	1.255520	0.363564	0.785015	0.164*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0496 (3)	0.0268 (3)	0.0268 (3)	−0.0025 (2)	0.0137 (2)	−0.0018 (2)
S1	0.0705 (9)	0.0671 (9)	0.0750 (9)	0.0037 (7)	0.0023 (7)	0.0295 (7)
O1	0.0447 (16)	0.0435 (16)	0.0524 (17)	−0.0023 (13)	0.0158 (14)	−0.0207 (13)
O2	0.0431 (18)	0.071 (2)	0.0508 (18)	−0.0167 (15)	0.0189 (14)	−0.0265 (15)
O3	0.0296 (15)	0.0517 (16)	0.0523 (17)	0.0015 (12)	0.0033 (13)	0.0137 (13)
O4	0.0552 (18)	0.0390 (15)	0.0452 (16)	−0.0038 (13)	0.0146 (14)	−0.0154 (13)
O5	0.0505 (19)	0.0645 (19)	0.0398 (16)	0.0128 (15)	0.0140 (14)	−0.0109 (14)
N1	0.035 (2)	0.049 (2)	0.049 (2)	0.0063 (16)	−0.0050 (16)	−0.0034 (17)
N2	0.053 (2)	0.0305 (16)	0.0321 (16)	−0.0019 (15)	0.0178 (15)	0.0024 (13)
N3	0.055 (2)	0.0375 (18)	0.0328 (17)	−0.0046 (15)	0.0133 (15)	0.0085 (14)
N4	0.062 (2)	0.0301 (16)	0.0278 (16)	−0.0028 (15)	0.0155 (15)	0.0016 (13)
C1	0.044 (2)	0.0323 (19)	0.0303 (19)	−0.0057 (17)	0.0131 (17)	−0.0028 (15)
C2	0.035 (2)	0.0322 (19)	0.0317 (19)	−0.0007 (15)	0.0100 (16)	−0.0002 (15)
C3	0.040 (2)	0.033 (2)	0.039 (2)	0.0070 (16)	0.0119 (17)	−0.0028 (16)
C4	0.034 (2)	0.039 (2)	0.037 (2)	0.0013 (17)	0.0052 (17)	0.0078 (17)
C5	0.046 (3)	0.037 (2)	0.040 (2)	0.0086 (18)	−0.0076 (19)	−0.0092 (17)
C6	0.043 (3)	0.057 (3)	0.059 (3)	0.015 (2)	−0.010 (2)	−0.011 (2)
C7	0.045 (3)	0.078 (3)	0.076 (3)	0.000 (2)	0.013 (2)	0.015 (3)
C8	0.042 (2)	0.034 (2)	0.034 (2)	−0.0048 (17)	0.0021 (17)	−0.0014 (16)
C9	0.039 (2)	0.0337 (19)	0.0284 (18)	−0.0011 (16)	0.0120 (16)	−0.0033 (15)
C10	0.046 (2)	0.0316 (19)	0.033 (2)	−0.0005 (17)	0.0148 (18)	0.0021 (16)
C11	0.032 (2)	0.0368 (19)	0.0307 (19)	−0.0009 (16)	0.0091 (15)	−0.0024 (16)
C12	0.052 (3)	0.042 (2)	0.043 (2)	−0.0035 (19)	0.025 (2)	0.0106 (18)
C13	0.046 (2)	0.043 (2)	0.042 (2)	−0.0049 (18)	0.0210 (19)	0.0059 (18)
C14	0.053 (2)	0.0265 (18)	0.0313 (19)	0.0003 (17)	0.0167 (18)	−0.0002 (15)
C15	0.058 (3)	0.0304 (19)	0.0250 (18)	−0.0051 (18)	0.0122 (17)	−0.0012 (15)
C16	0.059 (3)	0.036 (2)	0.031 (2)	−0.0003 (19)	0.0096 (18)	0.0046 (16)
C17	0.051 (3)	0.040 (2)	0.034 (2)	−0.0045 (19)	0.0088 (18)	0.0073 (17)
C18	0.066 (3)	0.034 (2)	0.040 (2)	0.015 (2)	0.018 (2)	0.0077 (17)
C19	0.057 (3)	0.041 (2)	0.040 (2)	0.007 (2)	0.022 (2)	0.0036 (18)
C20	0.058 (3)	0.041 (2)	0.036 (2)	−0.014 (2)	0.0167 (19)	0.0061 (17)
C21	0.049 (2)	0.039 (2)	0.036 (2)	−0.0113 (18)	0.0098 (18)	0.0028 (17)
O6	0.134 (10)	0.108 (8)	0.110 (9)	0.001 (7)	0.031 (7)	−0.003 (6)
O7	0.085 (6)	0.075 (5)	0.084 (5)	0.023 (4)	−0.034 (4)	−0.032 (4)
C23	0.166 (13)	0.206 (13)	0.211 (14)	−0.064 (11)	0.018 (11)	0.087 (11)
N5	0.190 (8)	0.193 (8)	0.179 (8)	0.003 (7)	0.031 (7)	0.030 (7)
C22	0.168 (9)	0.169 (8)	0.161 (8)	0.002 (7)	0.040 (7)	0.020 (7)
C24	0.233 (14)	0.249 (15)	0.219 (14)	0.067 (13)	0.034 (12)	−0.036 (13)
O8	0.100 (9)	0.192 (16)	0.034 (5)	−0.055 (9)	0.013 (5)	0.020 (7)

Geometric parameters (Å, º) top

Co1—O1	2.119 (3)	C8—C9	1.380 (5)
Co1—O2	2.216 (3)	C9—C10	1.496 (5)
Co1—O4ⁱ	2.156 (3)	C9—C11	1.395 (5)
Co1—O5ⁱ	2.211 (3)	C11—H11	0.9300
Co1—N2	2.094 (3)	C12—H12	0.9300
Co1—N4ⁱⁱ	2.100 (3)	C12—C13	1.361 (5)
Co1—C1	2.502 (4)	C13—H13	0.9300
S1—C5	1.638 (5)	C13—C14	1.406 (5)
O1—C1	1.271 (4)	C14—C20	1.385 (6)
O2—C1	1.251 (5)	C15—C16	1.378 (6)
O3—C4	1.404 (4)	C15—C19	1.409 (5)
O3—C5	1.363 (4)	C16—H16	0.9300
O4—C10	1.266 (4)	C16—C17	1.380 (5)
O5—C10	1.247 (5)	C17—H17	0.9300
N1—C5	1.339 (6)	C18—H18	0.9300
N1—C6	1.451 (5)	C18—C19	1.364 (6)
N1—C7	1.437 (6)	C19—H19	0.9300
N2—C12	1.345 (5)	C20—H20	0.9300
N2—C21	1.341 (5)	C20—C21	1.373 (5)
N3—H3	0.8600	C21—H21	0.9300
N3—C14	1.382 (5)	O6—C22	1.245 (17)
N3—C15	1.390 (5)	O7—H7D	0.8380
N4—C17	1.330 (5)	O7—H7E	0.8812
N4—C18	1.337 (5)	C23—H23A	0.9598
C1—C2	1.496 (5)	C23—H23B	0.9600
C2—C3	1.393 (5)	C23—H23C	0.9595
C2—C11	1.390 (5)	C23—N5	1.306 (14)
C3—H3A	0.9300	N5—C22	1.474 (15)
C3—C4	1.379 (5)	N5—C24	1.416 (15)
C4—C8	1.381 (5)	C22—H22	0.9300
C6—H6A	0.9600	C22—O8	0.93 (3)
C6—H6B	0.9600	C24—H24A	0.9600
C6—H6C	0.9600	C24—H24B	0.9600
C7—H7A	0.9600	C24—H24C	0.9600
C7—H7B	0.9600	O8—H8A	0.8784
C7—H7C	0.9600	O8—H8B	0.8500
C8—H8	0.9300

O1—Co1—O2	60.43 (10)	C4—C8—H8	120.3
O1—Co1—O4ⁱ	151.57 (11)	C9—C8—C4	119.4 (3)
O1—Co1—O5ⁱ	98.85 (11)	C9—C8—H8	120.3
O1—Co1—C1	30.50 (11)	C8—C9—C10	119.8 (3)
O2—Co1—C1	29.96 (11)	C8—C9—C11	119.8 (3)
O4ⁱ—Co1—O2	99.60 (11)	C11—C9—C10	120.3 (3)
O4ⁱ—Co1—O5ⁱ	59.65 (10)	O4—C10—C9	120.0 (4)
O4ⁱ—Co1—C1	126.57 (12)	O5—C10—O4	119.7 (4)
O5ⁱ—Co1—O2	92.57 (12)	O5—C10—C9	120.3 (3)
O5ⁱ—Co1—C1	95.62 (11)	C2—C11—C9	120.4 (3)
N2—Co1—O1	102.95 (12)	C2—C11—H11	119.8
N2—Co1—O2	91.51 (12)	C9—C11—H11	119.8
N2—Co1—O4ⁱ	97.23 (12)	N2—C12—H12	117.6
N2—Co1—O5ⁱ	156.87 (12)	N2—C12—C13	124.9 (4)
N2—Co1—N4ⁱⁱ	93.24 (12)	C13—C12—H12	117.6
N2—Co1—C1	99.22 (12)	C12—C13—H13	120.2
N4ⁱⁱ—Co1—O1	100.46 (12)	C12—C13—C14	119.6 (4)
N4ⁱⁱ—Co1—O2	160.89 (13)	C14—C13—H13	120.2
N4ⁱⁱ—Co1—O4ⁱ	98.15 (12)	N3—C14—C13	116.7 (4)
N4ⁱⁱ—Co1—O5ⁱ	90.30 (11)	N3—C14—C20	126.9 (4)
N4ⁱⁱ—Co1—C1	130.93 (14)	C20—C14—C13	116.3 (4)
C1—O1—Co1	91.7 (2)	N3—C15—C19	117.5 (4)
C1—O2—Co1	87.8 (2)	C16—C15—N3	125.5 (4)
C5—O3—C4	118.8 (3)	C16—C15—C19	117.0 (3)
C10—O4—Co1ⁱⁱⁱ	91.3 (2)	C15—C16—H16	120.5
C10—O5—Co1ⁱⁱⁱ	89.3 (2)	C15—C16—C17	119.1 (4)
C5—N1—C6	119.9 (4)	C17—C16—H16	120.5
C5—N1—C7	123.6 (3)	N4—C17—C16	124.5 (4)
C7—N1—C6	116.4 (4)	N4—C17—H17	117.8
C12—N2—Co1	122.3 (2)	C16—C17—H17	117.8
C21—N2—Co1	122.8 (3)	N4—C18—H18	117.9
C21—N2—C12	114.6 (3)	N4—C18—C19	124.3 (4)
C14—N3—H3	114.8	C19—C18—H18	117.9
C14—N3—C15	130.5 (4)	C15—C19—H19	120.5
C15—N3—H3	114.8	C18—C19—C15	119.0 (4)
C17—N4—Co1^iv	119.2 (3)	C18—C19—H19	120.5
C17—N4—C18	116.0 (3)	C14—C20—H20	120.3
C18—N4—Co1^iv	124.7 (3)	C21—C20—C14	119.5 (4)
O1—C1—Co1	57.84 (18)	C21—C20—H20	120.3
O1—C1—C2	120.2 (3)	N2—C21—C20	125.1 (4)
O2—C1—Co1	62.2 (2)	N2—C21—H21	117.5
O2—C1—O1	120.0 (3)	C20—C21—H21	117.5
O2—C1—C2	119.8 (3)	H7D—O7—H7E	111.7
C2—C1—Co1	176.8 (3)	H23A—C23—H23B	109.5
C3—C2—C1	119.7 (3)	H23A—C23—H23C	109.5
C11—C2—C1	120.9 (3)	H23B—C23—H23C	109.5
C11—C2—C3	119.4 (3)	N5—C23—H23A	111.7
C2—C3—H3A	120.3	N5—C23—H23B	109.3
C4—C3—C2	119.4 (3)	N5—C23—H23C	107.3
C4—C3—H3A	120.3	C23—N5—C22	125.5 (15)
C3—C4—O3	118.4 (3)	C23—N5—C24	122.9 (15)
C3—C4—C8	121.6 (4)	C24—N5—C22	111.4 (13)
C8—C4—O3	119.6 (3)	O6—C22—N5	113.0 (15)
O3—C5—S1	122.5 (3)	O6—C22—H22	123.5
N1—C5—S1	127.6 (3)	N5—C22—H22	123.5
N1—C5—O3	109.9 (4)	O8—C22—O6	10.1 (19)
N1—C6—H6A	109.5	O8—C22—N5	107 (2)
N1—C6—H6B	109.5	O8—C22—H22	128.6
N1—C6—H6C	109.5	N5—C24—H24A	109.5
H6A—C6—H6B	109.5	N5—C24—H24B	109.5
H6A—C6—H6C	109.5	N5—C24—H24C	109.5
H6B—C6—H6C	109.5	H24A—C24—H24B	109.5
N1—C7—H7A	109.5	H24A—C24—H24C	109.5
N1—C7—H7B	109.5	H24B—C24—H24C	109.5
N1—C7—H7C	109.5	C22—O8—H8A	80.7
H7A—C7—H7B	109.5	C22—O8—H8B	122.1
H7A—C7—H7C	109.5	H8A—O8—H8B	104.8
H7B—C7—H7C	109.5

Co1—O1—C1—O2	3.4 (4)	C5—O3—C4—C3	87.8 (4)
Co1—O1—C1—C2	−177.0 (3)	C5—O3—C4—C8	−100.0 (4)
Co1—O2—C1—O1	−3.2 (4)	C6—N1—C5—S1	−1.8 (6)
Co1—O2—C1—C2	177.2 (3)	C6—N1—C5—O3	179.0 (3)
Co1ⁱⁱⁱ—O4—C10—O5	2.2 (4)	C7—N1—C5—S1	179.1 (4)
Co1ⁱⁱⁱ—O4—C10—C9	−176.6 (3)	C7—N1—C5—O3	−0.1 (6)
Co1ⁱⁱⁱ—O5—C10—O4	−2.1 (4)	C8—C9—C10—O4	19.2 (5)
Co1ⁱⁱⁱ—O5—C10—C9	176.7 (3)	C8—C9—C10—O5	−159.6 (4)
Co1—N2—C12—C13	173.3 (3)	C8—C9—C11—C2	−0.5 (5)
Co1—N2—C21—C20	−173.9 (3)	C10—C9—C11—C2	−176.6 (3)
Co1^iv—N4—C17—C16	−174.6 (3)	C11—C2—C3—C4	−0.3 (5)
Co1^iv—N4—C18—C19	174.4 (3)	C11—C9—C10—O4	−164.7 (3)
O1—C1—C2—C3	0.7 (5)	C11—C9—C10—O5	16.5 (5)
O1—C1—C2—C11	−176.9 (3)	C12—N2—C21—C20	0.5 (6)
O2—C1—C2—C3	−179.7 (4)	C12—C13—C14—N3	177.7 (4)
O2—C1—C2—C11	2.7 (5)	C12—C13—C14—C20	0.6 (6)
O3—C4—C8—C9	−169.0 (3)	C13—C14—C20—C21	−1.2 (6)
N2—C12—C13—C14	0.6 (6)	C14—N3—C15—C16	−23.9 (6)
N3—C14—C20—C21	−178.0 (4)	C14—N3—C15—C19	158.4 (4)
N3—C15—C16—C17	178.3 (4)	C14—C20—C21—N2	0.6 (6)
N3—C15—C19—C18	−178.0 (4)	C15—N3—C14—C13	178.9 (4)
N4—C18—C19—C15	−1.1 (6)	C15—N3—C14—C20	−4.3 (6)
C1—C2—C3—C4	−177.9 (3)	C15—C16—C17—N4	1.0 (6)
C1—C2—C11—C9	179.1 (3)	C16—C15—C19—C18	4.1 (6)
C2—C3—C4—O3	170.1 (3)	C17—N4—C18—C19	−2.0 (6)
C2—C3—C4—C8	−2.0 (6)	C18—N4—C17—C16	2.0 (6)
C3—C2—C11—C9	1.5 (5)	C19—C15—C16—C17	−4.0 (5)
C3—C4—C8—C9	3.1 (6)	C21—N2—C12—C13	−1.2 (6)
C4—O3—C5—S1	8.9 (5)	C23—N5—C22—O6	−176 (2)
C4—O3—C5—N1	−171.9 (3)	C23—N5—C22—O8	175 (2)
C4—C8—C9—C10	174.4 (3)	C24—N5—C22—O6	−1 (3)
C4—C8—C9—C11	−1.8 (5)	C24—N5—C22—O8	−9 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O6	0.86	1.86	2.700 (19)	164
N3—H3···O8	0.86	2.13	2.979 (17)	170
C13—H13···O2^v	0.93	2.44	3.174 (5)	135
O7—H7D···O4	0.84	2.16	2.992 (7)	174
O7—H7E···O2^vi	0.88	2.26	3.136 (7)	173
O8—H8A···O7^vii	0.88	2.33	3.10 (2)	146
O8—H8B···O5^viii	0.85	2.28	3.102 (17)	163

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

Funding information

Funding for this research was provided by: National Natural Science Foundation of China (award No. 21271189); Natural Science Foundation of Hunan Province of China (award No. 2023JJ30685).

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