Synthesis, crystal structure and magnetic properties of poly[[diaqua{μ6-2-[bis­(carboxyl­atometh­yl)amino]­terephthalato}­dicobalt(II)] 1.6-hydrate]

Ma, J.; Zhang, W.-Z.; Liu, Y.; Yi, W.-T.

doi:10.1107/S2056989021008355

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ISSN: 2056-9890

Volume 77| Part 9| September 2021| Pages 939-943

https://doi.org/10.1107/S2056989021008355

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Synthesis, crystal structure and magnetic properties of poly[[diaqua{μ₆-2-[bis(carboxylatomethyl)amino]terephthalato}dicobalt(II)] 1.6-hydrate]

Jie Ma,^a ^* Wen-Zhi Zhang,^a Yong Liu ^a and Wen-Tao Yi ^a

^aCollege of Chemistry, Chemical Engineering and Materials Science, Zaozhuang University, Zaozhuang, Shandong, 277160, People's Republic of China
^*Correspondence e-mail: jiemacn@163.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 12 July 2021; accepted 11 August 2021; online 17 August 2021)

The asymmetric unit of the polymeric title compound {[Co₂(C₁₂H₇NO₈)(H₂O)₂]·1.6H₂O}_n comprises two Co^II ions, which are coordinated by fully deprotonated 2-aminodiacetic terephthalic acid (adtp^4–) and terminal water molecules in distorted octahedral N₁O₅ and O₆ coordination environments. The title compound features tetranuclear Co^II units bridged by κ³O:O:O′- and κ³O:O,O′-carboxylate groups, which are joined into ribbons via syn–anti carboxylate bridges. The parallel adtp^4– ligands with an alternately reversed arrangement further link adjacent Co^II ribbons into (010) layers, which are assembled into a three-dimensional supramolecular network via intermolecular hydrogen bonds. The disordered water solvent molecules are situated in channels parallel to [100]. Magnetic measurements and analyses reveal that the title compound displays antiferromagnetic behaviour. The purity of the title compound was characterized by X-ray powder diffraction.

Keywords: crystal structure; 2-aminodiacetic terephthalic acid; tetranuclear Co^II units; layered structure.

CCDC reference: 2063394

1. Chemical context

Over the last two decades, coordination polymers (CPs) have become one of the most attractive fields in chemistry because of their fascinating structures and promising applications as solid functional materials in adsorption and separation (Gan et al., 2020 ; Yang et al., 2020 ; Qian et al., 2020 ; Islamoglu et al., 2020 ), catalysis (Bavykina et al., 2020 ), sensing (Allendorf et al., 2020 ), luminescence (Rice et al., 2020 ) and magnetism (Thorarinsdottir & Harris, 2020 ; Wang et al., 2019b ). Multicarboxylic acids have been employed to synthesize compounds comprising of various dimensional structures such as chains, layers and three-dimensional frameworks. Immense efforts have been devoted to the construction of CPs for successful predictions and the rational design of definite structures; many significant advances in the construction of CPs have occurred by employing well-defined rigid multicarboxylic acids (Padial et al., 2020 ; Li et al., 2020b ; Wang et al., 2019a ; Shen et al., 2017 ; Pang et al., 2017 ). However, using semi-rigid or flexible ligands, predictions are still tricky and confusing owing to the diversity of ligand configurations, the formation of various polynuclear metal units and the influence of weak interatomic interactions.

Our previous studies have focused on the construction of CPs based on semi-rigid multicarboxylic acids with the aminodiacetate moiety such as 2-aminodiacetic terephthalic acid (H₄adtp) (Liu et al., 2009 ). The ortho-carboxylate group of H₄adtp can be regarded as three carboxylic arms attached to one amino nitrogen atom. The three arms can chelate and/or bridge metal ions through their carboxylate groups into polynuclear metal units or chains. The residual phenyl carboxylate group can cross-link the polynuclear metal units or chains into layers or three-dimensional frameworks. In previous work, we have reported the supramolecular hydrogen-bonded pillar-layered structure of [Mn(H₂adtp)(H₂O)]_n where the three arms connect Mn^II ions into layers with Mn^II chains and H₂adtp ligands joined by hydrogen bonding act as pillars (Ma et al., 2015 ). Herein we report the layer structure of the title compound, {[Co₂(C₁₂H₇NO₈)(H₂O)₂]·1.6H₂O}_n (I), based on fully deprotonated H₄adtp as one of the ligands. The crystal structure, power X-ray diffraction pattern and magnetism of (I) were also studied in detail.

2. Structural commentary

The asymmetric unit of (I) comprises two Co^II ions, one adtp^4– ligand, two terminal water ligands and 1.6 disordered solvent water molecules. Regarding the adtp^4– ligand, one carboxylate group (C12, O7, O8) of the aminodiacetate moiety adopts a κ³-O:O:O′ coordination mode and the other one (C10, O5, O6) employs a syn–anti bidentate bridging fashion, whereas the carboxylate group in the ortho-position (C1, O1, O2) coordinates in a κ³-O:O,O′ mode and that in the meta-position (C8, O3, O4) binds to one Co^II ion in monodentate fashion (see Scheme). As shown in Fig. 1, Co1 and Co2 are both six-coordinated and located in distorted octahedral environments with an N₁O₅ coordination set for Co1 and an O₆ set for Co2. The adip^4– ligand chelates Co1 with the amino nitrogen atom (N1) and carboxylate oxygen atoms (O1, O5 and O7) from the aminodiacetate moiety and its ortho-positioned carboxylate group. The residual cis-related sites are occupied by one meta-positioned carboxylate oxygen atom (O4ⁱⁱ) and one aminodiacetate oxygen atom (O7ⁱ) from two other adip^4– ligands (for symmetry codes refer to Table 1). The ortho-positioned carboxylate group (O1ⁱⁱⁱ and O2ⁱⁱⁱ) from another adip^4– ligand chelates Co2, two cis-related positions of which are occupied by two aminodiacetate oxygen atoms (O8^iv and O6) from two different adip^4– ligands. The remaining two cis-related sites of Co2 are occupied by two terminal water ligands (O9 and O10). The length of the Co—N bond is 2.241 (3) Å and the Co—O distances are between 1.992 (3) and 2.362 (3) Å, which are all in the expected ranges. As shown in Fig. 2, two inversion-related adtp^4– ligands bridge two pairs of Co^II ions (Co1, Co1ⁱⁱ, Co2ⁱ and Co2ⁱⁱⁱ) into a tetranuclear unit with their κ³O:O:O′-carboxylate groups from the aminodiacetate moieties and ortho-positioned κ³O:O,O′-carboxylate groups (Li et al., 2020a ; Zhang et al., 2019a ,b ; Liu et al., 2018 ), wherein two equivalent μ₂-oxygen atoms (O7 and O7ⁱ) from κ³O:O:O′-carboxylate groups doubly bridge Co1 and Co1ⁱⁱ into a dinuclear unit. The dinuclear unit is further joined with two equivalent Co2ⁱ and Co2ⁱⁱⁱ atoms via κ³O:O:O′-carboxylate groups and μ₂-oxygen bridges (O1 and O1ⁱ) from κ³O:O,O′-carboxylate groups. Adjacent tetranuclear units are linked into a ribbon via double syn–anti bridging carboxylate groups from the aminodiacetate moieties. The closest Co1⋯Co2 and Co1⋯Co1 distances in the ribbon are 3.7074 (8) and 3.5762 (8) Å, respectively. Parallel-aligned adtp^4– ligands with an alternately reversed arrangement bind adjacent Co^II ribbons into a layer extending parallel to (010) (Fig. 3).

Table 1
Selected bond lengths (Å)

Co1—O5	2.049 (3)	Co2—O2ⁱⁱⁱ	2.161 (2)
Co1—O7	2.033 (3)	Co2—O9	2.057 (3)
Co1—O7ⁱ	2.362 (3)	Co2—O8^iv	2.065 (3)
Co1—O4ⁱⁱ	1.992 (3)	Co2—O6	2.038 (3)
Co1—O1	2.083 (3)	Co2—O1ⁱⁱⁱ	2.212 (2)
Co1—N1	2.241 (3)	Co2—O10	2.126 (3)
Symmetry codes: (i) ; (ii) x, y, z+1; (iii) ; (iv) .

Figure 1
Coordination environments of the Co^II ions in (I) with displacement ellipsoids drawn at the 50% probability level; H atoms and the disordered lattice water molecules have been omitted for clarity. Symmetry codes refer to Table 1

Figure 2
Tetranuclear Co^II units and a Co^II ribbon in (I). Phenyl and meta-positioned carboxylate groups and the disordered lattice water molecules have been omitted for clarity. [Symmetry codes: (i) 1 + x, y, z; (ii) 1 − x, 1 − y, 1 − z; (iii) −x, 1 − y, 1 − z; (iv) −1 + x, y, z; (v) −1 − x, 1 − y, 1 − z.]

Figure 3
A view along [010], emphasizing the layered arrangement in the crystal structure of (I).

3. Supramolecular features

The (010) layers of (I) are assembled into a three-dimensional supramolecular network via intermolecular hydrogen bonds O9—H9A⋯O3^v and O9—H9B⋯O2^vi (Table 2, Fig. 4). The positionally and occupationally disordered solvent water molecules (O11–O14) are situated in channels extending parallel to [100].

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9A⋯O3^v	0.87	1.93	2.701 (4)	146
O9—H9B⋯O2^vi	0.87	2.00	2.809 (4)	153
O10—H10A⋯O12	0.89	1.98	2.849 (10)	164
O10—H10B⋯O5	0.92	2.02	2.798 (4)	141
Symmetry codes: (v) ; (vi) .

Figure 4
The three-dimensional supramolecular network of (I) constructed via intermolecular hydrogen bonds. The disordered water solvent molecules are located in channels parallel to [100].

4. Magnetic properties

The variable-temperature magnetic susceptibilities (χ_M) of (I) were measured in the range 2–300 K under 1000 Oe. The χ_M, χ_M⁻¹ and χ_MT versus T plots are shown in Fig. 5. The value of χ_MT at 300 K is 5.43 cm³ K mol⁻¹, which is much larger than the expected spin-only value (3.75 cm³ K mol⁻¹) of two isolated Co^II ions with g = 2.0, S = 3/2, which may be due to the contribution of the incompletely quenched orbital magnetic moment. As the temperature decreases, the χ_MT value decreases slowly between 300 and 50 K and then it descends more steeply to the minimum value of 0.51 cm³ K mol⁻¹ at 2 K. The curve clearly indicates that the dominant antiferromagnetic coupling is operating. The temperature dependence of χ_M⁻¹ follows the Curie–Weiss law, and the linear fit by the equation 1/χ_M = (T − θ)/C gives C = 5.76 cm⁻³ K mol⁻¹ and θ = −21.99 K, which is consistent with an antiferromagnetic behaviour.

Figure 5
χ_M and χ_MT versus. T curves for compound (I). Inset: χ_M⁻¹ versus T plot. The red solid line represents the best-fit curve.

5. Database survey

A search of the Cambridge Structural Database (CSD version 5.42, May 2021 update; Groom et al., 2016 ) for complexes with 2-aminodiacetic terephthalic acid gave 19 hits, of which three are Co^II complexes including the title compound (Refcode: CUFDIS). The other two Co^II complexes are discrete coordination molecules (Liu et al., 2012 ). Three other complexes with layer structures based on 2-aminodiacetic terephthalic acid without another organic ligand have also been reported, viz. MUMBON, an Mn^II complex (Ma et al., 2015), NEVJIJ, a Cd^II complex (Ma et al., 2013 ), and NEVJUV, a Zn^II complex (Ma et al., 2013). NEVJUV has similar cell parameters to the title compound, but similar tetranuclear metal units are not found in NEVJUV because the Zn^II atoms have lower coordination numbers and the carboxylate oxygen atoms do not bridge the Zn^II atoms as in the title compound. To the best of our knowledge, similar tetranuclear metal units have not been reported so far. Besides, one Co^II coordination polymer (CCDC reference: 2063370; Ma et al., 2021 ), {[Co₂(adtp)(H₂O)₆]·5H₂O}_n, has been synthesized, which consists of parallel stacked zigzag chains in which Co^II cations are linked together through μ₃-adtp⁴⁻ anions.

6. Synthesis and crystallization

H₄adtp was prepared using a similar protocol to that reported in the literature (Xu et al., 2006 ). The other chemicals were purchased from commercial sources and used without further purification. A solution of 0.2 mmol (0.0594 g) H₄adtp in 5.0 ml of H₂O was adjusted to a pH of 6.1 by adding a 1.0 M KHCO₃ solution drop by drop. The above solution was mixed with 0.5 mmol (0.1455 g) of Co(NO₃)₂·6H₂O and 5.0 ml of CH₃CN, then transferred into a 25.0 ml Teflon-lined stainless steel autoclave. The autoclave was sealed, heated to 393 K and held at that temperature for 72 h. The autoclave was allowed to cool to 303 K within 24 h. Plate-like pink crystals of (I) were collected in 66% yield based on H₄adtp. Analysis calculated (%) for C₁₂Co₂N₁O_11.6H_14.2 (M_r = 475.90): C 30.29, H 3.01, N, 2.94; found: C 30.18, H 3.15, N 3.06. Selected IR data (KBr pellet, cm⁻¹): 3389 (s), 1631 (s), 1570 (m), 1405 (s), 1373 (s), 1319 (b), 1111 (b), 780 (b), 712 (b).

The phase purity of compound (I) was confirmed by powder X-ray diffraction analysis (PXRD; Fig. S1 in the supporting information). The peak positions of the experimental PXRD patterns are in good agreement with those simulated on basis of the present single-crystal X-ray data, indicating that a pure phase was obtained.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The solvent water molecules (O11, O12, O13 and O14) were found to be disordered and were refined isotropically with site occupancies of 0.5, 0.5, 0.35 and 0.25, respectively. The hydrogen atoms of the non-disordered water molecules (O9, O10) were found in an difference density map and refined as riding, with U_iso(H) = 1.5 U_eq(O). Other hydrogen atoms were placed at geometrically calculated positions and treated as riding, with Csp²—H = 0.93 Å, Csp³—H = 0.97 Å and U_iso(H) = 1.2 U_eq(C). H atoms of O11, O12, O13 and O14 are not included in the model but were taken into account in the overall formula.

Table 3
Experimental details

Crystal data
Chemical formula	[Co₂(C₁₂H₇NO₈)(H₂O)₂]·1.6H₂O
M_r	475.90
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	9.0064 (9), 9.2340 (8), 9.8426 (9)
α, β, γ (°)	93.859 (3), 105.571 (4), 99.483 (5)
V (Å³)	772.37 (13)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	2.22
Crystal size (mm)	0.30 × 0.25 × 0.05

Data collection
Diffractometer	Rigaku Saturn70 (4x4 bin mode)
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2008 )
T_min, T_max	0.908, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5012, 2619, 2245
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.084, 1.04
No. of reflections	2619
No. of parameters	244
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.41
Computer programs: CrystalClear (Rigaku, 2008), SHELXS (Sheldrick, 2008 ), SHELXL (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2063394

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021008355/wm5615sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S2056989021008355/wm5615Isup3.cdx

Figure S1 The simulated and experimental PXRD patterns for compound (I). DOI: https://doi.org/10.1107/S2056989021008355/wm5615sup4.tif

checkCIF report

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Poly[[diaqua{µ₆-2-[bis(carboxylatomethyl)amino]terephthalato}dicobalt(II)] 1.6-hydrate] top

Crystal data top

[Co₂(C₁₂H₇NO₈)(H₂O)₂]·(H₂O)_1.6	Z = 2
M_r = 475.90	F(000) = 480
Triclinic, P1	D_x = 2.046 Mg m⁻³
a = 9.0064 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.2340 (8) Å	Cell parameters from 1889 reflections
c = 9.8426 (9) Å	θ = 2.3–27.5°
α = 93.859 (3)°	µ = 2.22 mm⁻¹
β = 105.571 (4)°	T = 293 K
γ = 99.483 (5)°	Plate, clear light red
V = 772.37 (13) Å³	0.30 × 0.25 × 0.05 mm

Data collection top

Rigaku Saturn70 (4x4 bin mode) diffractometer	2619 independent reflections
Radiation source: fine-focus sealed tube	2245 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.022
Detector resolution: 28.5714 pixels mm^-1	θ_max = 25.0°, θ_min = 3.0°
CCD_Profile_fitting scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	k = −10→10
T_min = 0.908, T_max = 1.000	l = −11→11
5012 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.035P)² + 1.7231P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2619 reflections	Δρ_max = 0.80 e Å⁻³
244 parameters	Δρ_min = −0.41 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	Occ. (<1)
Co1	0.29415 (6)	0.45959 (5)	0.48240 (5)	0.01675 (15)
O5	0.0863 (3)	0.3198 (3)	0.4645 (3)	0.0269 (6)
C1	0.2786 (4)	0.7012 (4)	0.3125 (4)	0.0166 (8)
O7	0.4739 (3)	0.3593 (3)	0.4646 (3)	0.0194 (6)
C2	0.2925 (4)	0.6185 (4)	0.1820 (4)	0.0163 (8)
Co2	−0.25268 (6)	0.14862 (5)	0.47212 (5)	0.01611 (15)
O2	0.3336 (3)	0.8376 (3)	0.3404 (3)	0.0213 (6)
C3	0.3371 (5)	0.7042 (4)	0.0822 (4)	0.0209 (8)
H3	0.362867	0.806555	0.103109	0.025*
C4	0.3438 (5)	0.6402 (4)	−0.0464 (4)	0.0208 (8)
H4	0.376198	0.698823	−0.110146	0.025*
C5	0.3021 (4)	0.4882 (4)	−0.0798 (4)	0.0170 (8)
C6	0.2603 (4)	0.4025 (4)	0.0199 (4)	0.0185 (8)
H6	0.232662	0.300415	−0.002608	0.022*
O9	−0.3388 (3)	−0.0735 (3)	0.4106 (3)	0.0273 (6)
H9A	−0.294396	−0.105535	0.348644	0.041*
H9B	−0.438376	−0.087425	0.364194	0.041*
C7	0.2586 (4)	0.4641 (4)	0.1514 (4)	0.0166 (8)
C8	0.2993 (4)	0.4154 (4)	−0.2221 (4)	0.0203 (8)
O8	0.5342 (3)	0.1757 (3)	0.3424 (3)	0.0214 (6)
C9	0.0396 (4)	0.3315 (4)	0.2165 (4)	0.0203 (8)
H9C	−0.000542	0.253614	0.137501	0.024*
H9D	−0.004209	0.417680	0.188115	0.024*
C10	−0.0098 (4)	0.2809 (4)	0.3444 (4)	0.0194 (8)
O4	0.3328 (3)	0.5005 (3)	−0.3085 (3)	0.0283 (7)
C13	0.2808 (4)	0.2309 (4)	0.2585 (4)	0.0195 (8)
H13A	0.285691	0.196842	0.164707	0.023*
H13B	0.212473	0.154326	0.287781	0.023*
C12	0.4434 (4)	0.2572 (4)	0.3616 (4)	0.0177 (8)
O3	0.2624 (4)	0.2777 (3)	−0.2452 (3)	0.0328 (7)
O6	−0.1453 (3)	0.2040 (3)	0.3200 (3)	0.0242 (6)
O1	0.2057 (3)	0.6374 (3)	0.3941 (3)	0.0194 (6)
O10	−0.0424 (3)	0.0957 (3)	0.6003 (3)	0.0286 (6)
H10A	−0.052816	0.076051	0.685363	0.043*
H10B	0.017174	0.187022	0.599944	0.043*
N1	0.2142 (3)	0.3688 (3)	0.2523 (3)	0.0153 (6)
O11	0.3252 (12)	0.0275 (10)	0.9277 (10)	0.069 (2)*	0.5
O12	−0.0171 (11)	0.0705 (10)	0.8922 (10)	0.074 (2)*	0.5
O13	0.2365 (15)	0.0205 (11)	0.9190 (11)	0.047 (3)*	0.35
O14	0.100 (3)	0.029 (3)	0.899 (3)	0.104 (7)*	0.25

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0195 (3)	0.0195 (3)	0.0122 (3)	0.0038 (2)	0.0062 (2)	0.00157 (19)
O5	0.0250 (16)	0.0349 (16)	0.0172 (14)	−0.0055 (13)	0.0071 (12)	0.0012 (12)
C1	0.0154 (19)	0.0204 (19)	0.0136 (18)	0.0037 (15)	0.0040 (15)	0.0008 (14)
O7	0.0190 (14)	0.0198 (13)	0.0172 (13)	0.0035 (11)	0.0026 (11)	−0.0023 (10)
C2	0.016 (2)	0.0189 (18)	0.0141 (18)	0.0026 (15)	0.0051 (15)	0.0004 (14)
Co2	0.0175 (3)	0.0160 (3)	0.0165 (3)	0.0032 (2)	0.0082 (2)	0.00012 (19)
O2	0.0288 (16)	0.0168 (13)	0.0201 (14)	0.0024 (12)	0.0116 (12)	−0.0006 (10)
C3	0.027 (2)	0.0183 (18)	0.0181 (19)	0.0059 (16)	0.0073 (16)	0.0019 (15)
C4	0.024 (2)	0.025 (2)	0.0160 (19)	0.0061 (17)	0.0090 (16)	0.0060 (15)
C5	0.0161 (19)	0.0233 (19)	0.0116 (17)	0.0038 (16)	0.0043 (14)	0.0008 (14)
C6	0.023 (2)	0.0162 (17)	0.0161 (18)	0.0024 (15)	0.0063 (15)	0.0007 (14)
O9	0.0234 (16)	0.0212 (14)	0.0379 (17)	0.0016 (12)	0.0137 (13)	−0.0051 (12)
C7	0.016 (2)	0.0223 (19)	0.0122 (18)	0.0034 (16)	0.0061 (15)	0.0028 (14)
C8	0.021 (2)	0.028 (2)	0.0118 (18)	0.0054 (17)	0.0047 (15)	−0.0001 (15)
O8	0.0198 (14)	0.0211 (13)	0.0235 (14)	0.0074 (12)	0.0054 (11)	−0.0018 (11)
C9	0.014 (2)	0.029 (2)	0.0182 (19)	0.0028 (16)	0.0050 (15)	0.0048 (16)
C10	0.016 (2)	0.0204 (19)	0.023 (2)	0.0044 (16)	0.0073 (16)	0.0028 (15)
O4	0.0367 (18)	0.0335 (16)	0.0126 (13)	−0.0052 (13)	0.0117 (12)	−0.0010 (11)
C13	0.023 (2)	0.0166 (18)	0.0173 (19)	0.0030 (16)	0.0046 (16)	0.0001 (14)
C12	0.021 (2)	0.0157 (18)	0.0188 (19)	0.0019 (16)	0.0095 (16)	0.0052 (15)
O3	0.055 (2)	0.0272 (16)	0.0197 (15)	0.0098 (14)	0.0167 (14)	−0.0012 (12)
O6	0.0177 (15)	0.0345 (15)	0.0207 (14)	0.0010 (12)	0.0085 (11)	0.0043 (12)
O1	0.0217 (14)	0.0209 (13)	0.0174 (13)	0.0021 (11)	0.0107 (11)	−0.0001 (10)
O10	0.0263 (16)	0.0333 (16)	0.0275 (15)	0.0067 (13)	0.0076 (12)	0.0101 (12)
N1	0.0157 (16)	0.0177 (15)	0.0141 (15)	0.0030 (13)	0.0063 (12)	0.0037 (12)

Geometric parameters (Å, º) top

Co1—O5	2.049 (3)	C5—C8	1.504 (5)
Co1—O7	2.033 (3)	C6—H6	0.9300
Co1—O7ⁱ	2.362 (3)	C6—C7	1.383 (5)
Co1—O4ⁱⁱ	1.992 (3)	O9—H9A	0.8744
Co1—O1	2.083 (3)	O9—H9B	0.8742
Co1—N1	2.241 (3)	C7—N1	1.461 (4)
O5—C10	1.252 (5)	C8—O4	1.258 (5)
C1—C2	1.495 (5)	C8—O3	1.249 (5)
C1—O2	1.258 (4)	O8—C12	1.240 (4)
C1—O1	1.281 (4)	C9—H9C	0.9700
O7—C12	1.276 (4)	C9—H9D	0.9700
C2—C3	1.401 (5)	C9—C10	1.521 (5)
C2—C7	1.403 (5)	C9—N1	1.491 (5)
Co2—O2ⁱⁱⁱ	2.161 (2)	C10—O6	1.259 (5)
Co2—O9	2.057 (3)	C13—H13A	0.9700
Co2—O8^iv	2.065 (3)	C13—H13B	0.9700
Co2—O6	2.038 (3)	C13—C12	1.512 (5)
Co2—O1ⁱⁱⁱ	2.212 (2)	C13—N1	1.492 (5)
Co2—O10	2.126 (3)	O10—H10A	0.8942
C3—H3	0.9300	O10—H10B	0.9225
C3—C4	1.381 (5)	O11—O13	0.771 (12)
C4—H4	0.9300	O12—O14	1.17 (3)
C4—C5	1.384 (5)	O13—O14	1.21 (3)
C5—C6	1.391 (5)

O5—Co1—O7ⁱ	170.67 (10)	C6—C5—C8	119.9 (3)
O5—Co1—O1	99.02 (11)	C5—C6—H6	118.9
O5—Co1—N1	76.91 (11)	C7—C6—C5	122.2 (3)
O7—Co1—O5	115.34 (11)	C7—C6—H6	118.9
O7—Co1—O7ⁱ	71.31 (11)	Co2—O9—H9A	109.7
O7—Co1—O1	133.46 (10)	Co2—O9—H9B	109.8
O7—Co1—N1	78.36 (10)	H9A—O9—H9B	104.3
O4ⁱⁱ—Co1—O5	91.10 (11)	C2—C7—N1	121.3 (3)
O4ⁱⁱ—Co1—O7ⁱ	80.73 (10)	C6—C7—C2	118.7 (3)
O4ⁱⁱ—Co1—O7	103.42 (11)	C6—C7—N1	119.9 (3)
O4ⁱⁱ—Co1—O1	106.43 (11)	O4—C8—C5	116.2 (3)
O4ⁱⁱ—Co1—N1	167.23 (11)	O3—C8—C5	118.0 (3)
O1—Co1—O7ⁱ	79.19 (9)	O3—C8—O4	125.8 (3)
O1—Co1—N1	80.14 (10)	C12—O8—Co2^v	130.6 (2)
N1—Co1—O7ⁱ	111.56 (10)	H9C—C9—H9D	108.2
C10—O5—Co1	119.4 (2)	C10—C9—H9C	109.6
O2—C1—C2	119.7 (3)	C10—C9—H9D	109.6
O2—C1—O1	118.9 (3)	N1—C9—H9C	109.6
O1—C1—C2	121.4 (3)	N1—C9—H9D	109.6
Co1—O7—Co1ⁱ	108.69 (10)	N1—C9—C10	110.1 (3)
C12—O7—Co1ⁱ	120.4 (2)	O5—C10—C9	117.6 (3)
C12—O7—Co1	116.8 (2)	O5—C10—O6	125.6 (3)
C3—C2—C1	116.4 (3)	O6—C10—C9	116.8 (3)
C3—C2—C7	118.8 (3)	C8—O4—Co1^vi	129.3 (2)
C7—C2—C1	124.8 (3)	H13A—C13—H13B	108.0
O2ⁱⁱⁱ—Co2—O1ⁱⁱⁱ	59.97 (9)	C12—C13—H13A	109.4
O9—Co2—O2ⁱⁱⁱ	96.68 (10)	C12—C13—H13B	109.4
O9—Co2—O8^iv	84.76 (11)	N1—C13—H13A	109.4
O9—Co2—O1ⁱⁱⁱ	156.66 (10)	N1—C13—H13B	109.4
O9—Co2—O10	89.06 (11)	N1—C13—C12	111.1 (3)
O8^iv—Co2—O2ⁱⁱⁱ	92.24 (10)	O7—C12—C13	116.7 (3)
O8^iv—Co2—O1ⁱⁱⁱ	95.29 (10)	O8—C12—O7	125.3 (3)
O8^iv—Co2—O10	173.82 (11)	O8—C12—C13	117.9 (3)
O6—Co2—O2ⁱⁱⁱ	161.71 (11)	C10—O6—Co2	124.7 (2)
O6—Co2—O9	101.55 (11)	Co1—O1—Co2ⁱⁱⁱ	119.35 (12)
O6—Co2—O8^iv	90.90 (11)	C1—O1—Co1	115.4 (2)
O6—Co2—O1ⁱⁱⁱ	101.79 (10)	C1—O1—Co2ⁱⁱⁱ	89.1 (2)
O6—Co2—O10	90.63 (11)	Co2—O10—H10A	110.5
O10—Co2—O2ⁱⁱⁱ	88.17 (11)	Co2—O10—H10B	93.8
O10—Co2—O1ⁱⁱⁱ	90.26 (10)	H10A—O10—H10B	114.8
C1—O2—Co2ⁱⁱⁱ	92.0 (2)	C7—N1—Co1	117.5 (2)
C2—C3—H3	119.3	C7—N1—C9	109.1 (3)
C4—C3—C2	121.5 (3)	C7—N1—C13	113.8 (3)
C4—C3—H3	119.3	C9—N1—Co1	105.0 (2)
C3—C4—H4	120.2	C9—N1—C13	110.2 (3)
C3—C4—C5	119.7 (3)	C13—N1—Co1	100.6 (2)
C5—C4—H4	120.2	O11—O13—O14	171 (2)
C4—C5—C6	119.0 (3)	O12—O14—O13	164 (2)
C4—C5—C8	121.1 (3)

Co1—O5—C10—C9	4.5 (4)	C4—C5—C8—O4	−1.8 (5)
Co1—O5—C10—O6	−174.9 (3)	C4—C5—C8—O3	179.1 (4)
Co1ⁱ—O7—C12—O8	51.6 (4)	C5—C6—C7—C2	3.3 (6)
Co1—O7—C12—O8	−173.0 (3)	C5—C6—C7—N1	−179.8 (3)
Co1—O7—C12—C13	4.5 (4)	C5—C8—O4—Co1^vi	−163.4 (2)
Co1ⁱ—O7—C12—C13	−130.8 (3)	C6—C5—C8—O4	177.4 (4)
O5—C10—O6—Co2	9.2 (5)	C6—C5—C8—O3	−1.7 (5)
C1—C2—C3—C4	−175.7 (3)	C6—C7—N1—Co1	158.5 (3)
C1—C2—C7—C6	173.2 (3)	C6—C7—N1—C9	−82.2 (4)
C1—C2—C7—N1	−3.7 (6)	C6—C7—N1—C13	41.4 (5)
C2—C1—O2—Co2ⁱⁱⁱ	178.1 (3)	C7—C2—C3—C4	1.9 (6)
C2—C1—O1—Co1	59.6 (4)	C8—C5—C6—C7	−179.0 (3)
C2—C1—O1—Co2ⁱⁱⁱ	−178.0 (3)	C9—C10—O6—Co2	−170.2 (2)
C2—C3—C4—C5	1.6 (6)	C10—C9—N1—Co1	−33.2 (3)
C2—C7—N1—Co1	−24.7 (4)	C10—C9—N1—C7	−160.1 (3)
C2—C7—N1—C9	94.7 (4)	C10—C9—N1—C13	74.3 (4)
C2—C7—N1—C13	−141.8 (3)	C12—C13—N1—Co1	−40.3 (3)
Co2^v—O8—C12—O7	9.3 (5)	C12—C13—N1—C7	86.3 (4)
Co2^v—O8—C12—C13	−168.3 (2)	C12—C13—N1—C9	−150.7 (3)
O2—C1—C2—C3	−13.0 (5)	O3—C8—O4—Co1^vi	15.5 (6)
O2—C1—C2—C7	169.5 (3)	O1—C1—C2—C3	164.0 (3)
O2—C1—O1—Co1	−123.4 (3)	O1—C1—C2—C7	−13.6 (6)
O2—C1—O1—Co2ⁱⁱⁱ	−1.0 (3)	O1—C1—O2—Co2ⁱⁱⁱ	1.1 (3)
C3—C2—C7—C6	−4.3 (5)	N1—C9—C10—O5	22.0 (5)
C3—C2—C7—N1	178.9 (3)	N1—C9—C10—O6	−158.6 (3)
C3—C4—C5—C6	−2.6 (6)	N1—C13—C12—O7	27.9 (4)
C3—C4—C5—C8	176.6 (3)	N1—C13—C12—O8	−154.3 (3)
C4—C5—C6—C7	0.2 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9A···O3^vii	0.87	1.93	2.701 (4)	146
O9—H9B···O2^viii	0.87	2.00	2.809 (4)	153
O10—H10A···O12	0.89	1.98	2.849 (10)	164
O10—H10B···O5	0.92	2.02	2.798 (4)	141

Symmetry codes: (vii) −x, −y, −z; (viii) x−1, y−1, z.

Funding information

Funding for this research was provided by: Natural Science Foundation of Shandong Province (grant Nos. ZR2019QB013 and ZR2018MB041).

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