Crystal structure of catena-poly[[[tetra­aquacobalt(II)]-μ2-1,5-di­hydroxy­naphthalene-2,6-di­carboxyl­ato] di­methyl­formamide disolvate]

Kumagai, H.; Kawata, S.; Ogihara, N.

doi:10.1107/S2056989025000982

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Volume 81| Part 3| March 2025|

https://doi.org/10.1107/S2056989025000982

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Crystal structure of catena-poly[[[tetraaquacobalt(II)]-μ₂-1,5-dihydroxynaphthalene-2,6-dicarboxylato] dimethylformamide disolvate]

Hitoshi Kumagai,^a ^* Satoshi Kawata ^b and Nobuhiro Ogihara ^a

^aToyota Central R&D Labs., Inc., 41-1 Yokomichi, Nagakute, Aichi 480-1192, Japan, and ^bDepartment of Chemistry, Fukuoka University, 8-19-1 Nanakuma Jonan-ku, Fukuoka, 814-0180, Japan
^*Correspondence e-mail: e1254@mosk.tytlabs.co.jp

Edited by T. Akitsu, Tokyo University of Science, Japan (Received 27 January 2025; accepted 3 February 2025; online 7 February 2025)

The asymmetric unit of the title compound, {[Co(C₁₂H₆O₆)(H₂O)₄]·2C₃H₇NO}_n or {[Co(H₂dondc)(H₂O)₄]·2DMF}_n, comprises half of a Co^II ion, half of a 1,5-dihydroxynaphthalene-2,6-dicarboxylate dianion (H₂dondc²⁻), two water molecules and a dimethylformamide (DMF) molecule. The Co^II ion, which is located on a crystallographic inversion center, exhibits a distorted six-coordinated octahedral geometry with two oxygen atoms of the H₂dondc²⁻ ligand and four oxygen atoms of the water molecules. The carboxylate group is almost coplanar with the naphthalene moiety and shows monodentate coordination to the Co^II ion. The Co^II ions are bridged by the H₂dondc²⁻ ligand to form a one-dimensional chain. The hydroxy groups of the ligand have intra-chain hydrogen bonding interactions with coordinated water molecules. The coordinated water molecules exhibit not only intra-chain hydrogen bonding interactions, but also inter-chain hydrogen-bonding interactions. The chains are connected by inter-chain hydrogen-bonding interactions and are arranged in parallel to form a two-dimensional network. The chains are further connected by inter-chain hydrogen-bonding interactions via the DMF molecules and C—H⋯π interactions to give a three-dimensional network.

Keywords: cobalt; hydrogen bonding; C—H⋯π interaction; dihydroxy-naphthalenedicarboxylate; crystal structure.

CCDC reference: 2421049

1. Chemical context

Metal–organic frameworks (MOFs) or coordination polymers (CPs) are being actively investigated due to their applications in gas adsorption, separation and catalysis (Cheetham et al., 1999 ; Eddaoudi et al., 2002 ; Kitagawa et al., 2004 ). Polycarboxylate ligands such as benzenedicarboxylate (bdc²⁻ dianion), also known as a terephthalate dianion, are well-known linkers that yield functional materials (Furukawa et al., 2010 ; Kurmoo, 2009 ). We have not only prepared electrode materials using the terephthalate dianion and its derivatives (Ogihara et al., 2014 , 2021 ,2023 ; Yasuda & Ogihara, 2014 ), but also magnetic materials that involve polycarboxylates in which the number of carboxylate groups and the distances between carboxylate groups vary systematically (Kumagai et al., 2001 , 2002 ; Kurmoo et al., 2001 , 2003 ). The functionalization of an organic ligand provides further coordination capabilities, reaction centers, and interaction sites for specific functions. The 2,5-dihydroxy-1,4-benzenedicarboxylic acid (2,5-H₄dobdc) ligand is a 1,4-benzenedicarboxylic acid derivative with two hydroxy groups introduced as functional groups and functional MOFs with this ligand have been reported (Caskey et al., 2008 ; Cozzolino et al., 2014 ; Geier et al., 2013 ; Maurice et al., 2013 ; Queen et al., 2014 ). 1,5-Dihydroxynaphthalene-2,6-dicarboxylate (H₄dondc) is an analogue of 2,5-H₄dobdc. The H₄dondc ligand can be deprotonated to give four available charges (1- to 4-); however, only metal complexes of the 4- anion have been reported (Dietzel et al., 2020 ; Yeon et al., 2015 ). In this contribution, we have focused on the use of 1,5-dihydroxynaphthalene-2,6-dicarboxylate (H₂dondc²⁻) in the synthesis of a Co^II–H₂dondc²⁻ dianion system and report on the single-crystal structure of [Co(H₂dondc)(H₂O)₄]·2DMF in which the ligand is a 2- anion. This is a new structure of the metal complex synthesized from H₄dondc.

2. Structural commentary

The title compound, [Co(H₂dondc)(H₂O)₄]·2DMF, consists of a Co^II ion, a 1,5-dihydroxynaphthalene-2,6-dicarboxylate dianion (H₂dondc²⁻), four water molecules and two DMF molecules. The Co^II ion lies on a crystallographic inversion center and its asymmetric unit consists of half of a Co^II ion, half of a H₂dondc²⁻ ligand, two water molecules and a DMF molecule. The key feature of the structure is a three-dimensional (3D) hydrogen-bonding network that consists of one-dimensional (1D) coordination chains built up by CoO₆ octahedra bridged by H₂dondc²⁻ ligands and interchain O–H⋯O hydrogen-bonding interactions. Fig. 1 shows the 1D chain structure of [Co(H₂dondc)(H₂O)₄] and DMF molecules with the numbering scheme. The Co^II ion occupies a crystallographic inversion center; therefore, each pair of H₂dondc²⁻ ligands and water molecules coordinate trans to each other to form a linear chain. The Co—O1 (carboxylate) bond length [2.0750 (9) Å] in the title compound is shorter than the Co—O (H₂O) bond lengths [2.0931 (10) and 2.1023 (10) Å], which is indicative of the compressed octahedral geometry of the Co^II ion. The Co⋯Co separation defined by Co–H₂dondc²⁻–Co connectivity within the chain is 13.27 Å. We have reported CPs that consist of tetrahalogenated terephthalate dianions as bridging ligands in which the carboxylate groups exhibited monodentate coordination similar to the title compound. The Co⋯Co separation distance (ca. 11 Å) is shorter than that observed in the title compound (Kumagai et al., 2021 ), which is due to the long naphthalene backbone. The carboxylate group exhibits monodentate coordination, and the dihedral angle between the carboxylate group and the naphthalene ring system is slightly tilted with an O1—C1—C3—C4 torsion angle of 171.94 (11)°. Non-coordinated oxygen atoms of the carboxylate groups show intra-chain hydrogen-bonding interactions with coordinated water molecules. The non-coordinated oxygen atoms of the carboxylate groups act as hydrogen-bond acceptors and coordinated water molecules act as hydrogen-bond donors. The H₂dondc²⁻ ligand binds to the Co^II ion solely through its carboxylate oxygen atoms and the phenolic hydroxyl groups show no coordination bonding to Co^II ions. The hydroxyl groups act as hydrogen-bond donors and undergo hydrogen bonding with the coordinated carboxylate oxygen atoms as hydrogen-bond acceptors. The H₄dondc ligand can be deprotonated to give four available charges (1− to 4−), although only metal complexes of the 4− anion have been reported so far. Both the hydroxy and carboxylic acid groups of the ligand are deprotonated to give a 4− anion and the resultant oxido and carboxylate groups are coordinated by metal ions to give the M₂(dondc) composition (M = Mn, Mg, Ni, Co) and a honeycomb-like structure (Dietzel et al., 2020; Yeon et al., 2015).

Figure 1
One-dimensional chain structure of the title compound with the atom-labeling scheme and 50% probability displacement ellipsoids. Hydrogen atoms are omitted for clarity. [Symmetry code: (i) −x + 1, −y + 1, −z + 1.]

3. Supramolecular features

The coordinated water molecules in the crystal structure act as hydrogen-bonding donors and the oxygen atoms of the DMF molecules act as hydrogen-bonding acceptors (Table 1). The coordinated water molecule (O4) shows two types of hydrogen-bonding interactions. One is an inter-chain hydrogen-bonding interaction between the non-coordinated oxygen atom of the adjacent chain to give a two-dimensional hydrogen-bonding network in which the chains are arranged in parallel when viewed along the b-axis direction (Fig. 2). The other is an inter-molecular hydrogen-bonding interaction between the DMF and water molecules. The coordinated water molecule (O5) exhibits not only inter-chain hydrogen-bonding interactions with the oxygen atom of a DMF molecule but also intra-chain hydrogen-bonding interactions with an oxygen atom (O2) of the carboxylate group not bound to the Co^II ions. The DMF molecule acts as a hydrogen-bond acceptor for both O4 and O5 in different chains to yield a hydrogen-bonding network (Fig. 3). The C3⋯C8 distance of 3.497 (2) Å between the carbon atoms of DMF molecules and the naphthalene ring system, and the C8⋯centroid distance of 3.53 Å are indicative of some degree of C—H⋯π interaction (Nishio, 2011 ; Nishio et al., 2009 ). Therefore, the DMF molecules are held in between the one-dimensional chains by hydrogen-bonding interactions and C—H⋯π interactions(Fig. S1 in the supporting information). The presence of DMF molecules between the chains prevents π–π stacking interactions between the planar naphthalene moieties and the two naphthalene moieties are 6.96 Å apart.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1	0.78 (2)	1.81 (2)	2.5168 (13)	149.1 (19)
O4—H1⋯O6	0.76 (2)	1.99 (2)	2.7449 (16)	178 (2)
O4—H2⋯O2ⁱ	0.78 (2)	1.96 (2)	2.7284 (15)	168 (2)
O5—H6⋯O2ⁱⁱ	0.79 (3)	2.00 (3)	2.7182 (14)	151 (2)
O5—H10⋯O6ⁱⁱⁱ	0.85 (2)	1.95 (2)	2.7836 (15)	166 (2)
C8—H8C⋯C3ⁱⁱ	0.98	2.85	3.497 (2)	124
Symmetry codes: (i) ; (ii) ; (iii) .

Figure 2
View of the two-dimensional hydrogen-bonding network with inter- and intra-chain hydrogen-bonding interactions. Dashed lines represent hydrogen bonds.

Figure 3
Inter-chain hydrogen-bonding interactions via DMF molecules. Dashed lines represent inter-chain hydrogen bonds.

4. Database survey

Although a search of the Sci Finder database for structures with a H₂dondc²⁻ and Co^II ion resulted in no complete matches, partially matched structures were found. They are metal complexes composed of a Mn^II ion and a dondc⁴⁻ ligand that form a three-dimensional network consisting of hexagonal channels (CADYOZ and CADYUF; Dietzel et al., 2020). A search of the Web of Science database for the keywords 2,6-naphthalenedicarboxylic acid and 1,5-dihydroxy- led to lanthanide-based compounds [DUDXOS (La) and DUDXUY (Ce); Mahmoud et al., 2020 ] and an Mg^II compound (Yeon et al., 2015). The structure of the Mg^II compound is similar to that of the Mn^II compound.

5. Synthesis and crystallization

Cobalt(II) nitrate hexahydrate (0.12 g, 0.4 mmol) and H₄dondc were dissolved in an ethanol (10 mL)–N,N-dimethylformamide (20 mL) mixture. The mixture was placed in the Teflon liner of an autoclave, sealed, and heated at 353 K for two days. The mixture was then cooled to room temperature. Pink crystals were obtained and one of these crystals was used for single-crystal X-ray crystallography analysis.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The non-hydrogen atoms were refined anisotropically. The hydrogen atoms attached to oxygen atoms of the ligand and water molecules were extracted from difference-Fourier maps. Other hydrogen atoms were placed in idealized positions (C—H = 0.95–0.98 Å) and refined using a riding model with U_iso(H) = 1.2U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	[Co(C₁₂H₆O₆)(H₂O)₄]·2C₃H₇NO
M_r	523.35
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	110
a, b, c (Å)	6.886 (1), 6.945 (1), 12.0366 (15)
α, β, γ (°)	85.543 (5), 84.371 (5), 83.981 (5)
V (Å³)	568.37 (14)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.82
Crystal size (mm)	0.25 × 0.25 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Rigaku, 1995 )
T_min, T_max	0.760, 0.922
No. of measured, independent and observed [I > 2σ(I)] reflections	9228, 2595, 2413
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.074, 1.11
No. of reflections	2595
No. of parameters	173
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.24
Computer programs: RAPID-AUTO (Rigaku, 2002 ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and Yadokari-XG (Wakita, 2001 ).

Supporting information

CCDC reference: 2421049

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025000982/jp2016sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025000982/jp2016Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025000982/jp2016Isup3.cdx

Supporting FigS1. View of the CH-pi interactions. Dashed lines represent CH-pi interactions. DOI: https://doi.org/10.1107/S2056989025000982/jp2016sup4.tif

Supporting FigS2. View of the CH-pi interactions along b-axis. DOI: https://doi.org/10.1107/S2056989025000982/jp2016sup5.tif

Supporting FigS3. View of the CH-pi interactions along a-axis. Dashed lines represent CH-pi interactions. DOI: https://doi.org/10.1107/S2056989025000982/jp2016sup6.tif

checkCIF report

Computing details top

catena-Poly[[[tetraaquacobalt(II)]-µ₂-1,5-dihydroxynaphthalene-2,6-dicarboxylato] dimethylformamide disolvate] top

Crystal data top

[Co(C₁₂H₆O₆)(H₂O)₄]·2C₃H₇NO	Z = 1
M_r = 523.35	F(000) = 273
Triclinic, P1	D_x = 1.529 Mg m⁻³
a = 6.886 (1) Å	Mo Kα radiation, λ = 0.71075 Å
b = 6.945 (1) Å	Cell parameters from 7544 reflections
c = 12.0366 (15) Å	θ = 3.3–27.5°
α = 85.543 (5)°	µ = 0.82 mm⁻¹
β = 84.371 (5)°	T = 110 K
γ = 83.981 (5)°	Block, orange
V = 568.37 (14) Å³	0.25 × 0.25 × 0.10 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	2413 reflections with I > 2σ(I)
ω scans	R_int = 0.027
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995)	θ_max = 27.5°, θ_min = 3.3°
T_min = 0.760, T_max = 0.922	h = −8→8
9228 measured reflections	k = −9→9
2595 independent reflections	l = −15→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.0456P)² + 0.1029P] where P = (F_o² + 2F_c²)/3
2595 reflections	(Δ/σ)_max < 0.001
173 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.24 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	0.500000	0.500000	0.500000	0.01471 (10)
O1	0.67306 (14)	0.46799 (15)	0.35020 (7)	0.0190 (2)
O2	0.96008 (13)	0.33348 (15)	0.40363 (8)	0.0210 (2)
O3	0.62385 (13)	0.54304 (15)	0.14635 (8)	0.0179 (2)
H3	0.597 (3)	0.535 (3)	0.2110 (17)	0.030 (5)*
O4	0.66579 (15)	0.72005 (16)	0.53529 (8)	0.0191 (2)
O5	0.30573 (15)	0.69999 (16)	0.41516 (8)	0.0199 (2)
O6	0.50238 (16)	0.98724 (16)	0.68258 (9)	0.0271 (2)
N1	0.22328 (19)	1.01767 (18)	0.80010 (10)	0.0243 (3)
C1	0.85613 (19)	0.41209 (19)	0.33048 (10)	0.0156 (3)
C2	0.81861 (18)	0.50097 (18)	0.12707 (10)	0.0142 (2)
C3	0.94074 (18)	0.44228 (18)	0.21177 (10)	0.0141 (2)
C4	1.14541 (18)	0.40885 (19)	0.18353 (10)	0.0161 (3)
H4	1.229079	0.371976	0.241383	0.019*
C5	1.22599 (18)	0.42820 (19)	0.07517 (11)	0.0160 (3)
H5	1.363922	0.406279	0.058549	0.019*
C6	1.10219 (17)	0.48131 (18)	−0.01250 (10)	0.0138 (2)
C7	0.3219 (2)	1.0217 (2)	0.70011 (12)	0.0250 (3)
H7	0.249193	1.053293	0.636960	0.030*
C8	0.0115 (2)	1.0587 (2)	0.81476 (16)	0.0349 (4)
H8A	−0.039095	1.089840	0.741516	0.042*
H8B	−0.022584	1.169262	0.861194	0.042*
H8C	−0.046646	0.944645	0.851466	0.042*
C9	0.3257 (3)	0.9726 (2)	0.90075 (13)	0.0345 (4)
H9A	0.299710	1.081591	0.948870	0.041*
H9B	0.466950	0.950019	0.879845	0.041*
H9C	0.279186	0.855710	0.941191	0.041*
H1	0.619 (3)	0.795 (3)	0.5747 (18)	0.034 (6)*
H2	0.769 (3)	0.690 (3)	0.5561 (16)	0.028 (5)*
H6	0.214 (4)	0.728 (4)	0.458 (2)	0.057 (7)*
H10	0.351 (3)	0.806 (3)	0.3928 (17)	0.037 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01037 (14)	0.02391 (15)	0.00905 (13)	−0.00095 (9)	0.00171 (8)	−0.00044 (9)
O1	0.0131 (4)	0.0315 (5)	0.0112 (4)	0.0002 (4)	0.0027 (3)	−0.0011 (4)
O2	0.0125 (4)	0.0359 (6)	0.0131 (4)	−0.0005 (4)	0.0008 (3)	0.0026 (4)
O3	0.0106 (4)	0.0320 (5)	0.0102 (4)	−0.0008 (4)	0.0025 (3)	−0.0015 (4)
O4	0.0128 (5)	0.0269 (5)	0.0175 (5)	−0.0001 (4)	−0.0010 (4)	−0.0032 (4)
O5	0.0142 (5)	0.0277 (5)	0.0161 (5)	−0.0004 (4)	0.0018 (4)	0.0024 (4)
O6	0.0247 (5)	0.0275 (5)	0.0273 (6)	−0.0020 (4)	0.0060 (4)	−0.0019 (4)
N1	0.0268 (7)	0.0218 (6)	0.0231 (6)	−0.0044 (5)	0.0058 (5)	−0.0024 (5)
C1	0.0133 (6)	0.0206 (6)	0.0131 (6)	−0.0046 (5)	0.0018 (4)	−0.0028 (5)
C2	0.0112 (6)	0.0176 (6)	0.0139 (6)	−0.0034 (4)	0.0025 (4)	−0.0036 (5)
C3	0.0129 (6)	0.0172 (6)	0.0121 (6)	−0.0023 (5)	0.0023 (4)	−0.0027 (4)
C4	0.0133 (6)	0.0215 (6)	0.0134 (6)	−0.0024 (5)	−0.0008 (4)	−0.0009 (5)
C5	0.0110 (6)	0.0217 (6)	0.0152 (6)	−0.0017 (5)	0.0009 (4)	−0.0027 (5)
C6	0.0122 (6)	0.0165 (6)	0.0128 (6)	−0.0028 (5)	0.0016 (4)	−0.0029 (5)
C7	0.0272 (8)	0.0252 (7)	0.0222 (7)	−0.0049 (6)	0.0021 (6)	−0.0009 (6)
C8	0.0272 (8)	0.0304 (8)	0.0463 (10)	−0.0085 (7)	0.0131 (7)	−0.0098 (7)
C9	0.0504 (11)	0.0291 (8)	0.0220 (8)	0.0001 (7)	0.0024 (7)	−0.0014 (6)

Geometric parameters (Å, º) top

Co1—O1ⁱ	2.0750 (9)	N1—C9	1.458 (2)
Co1—O1	2.0750 (9)	C1—C3	1.4969 (17)
Co1—O4ⁱ	2.0931 (10)	C2—C3	1.3945 (18)
Co1—O4	2.0931 (10)	C2—C6ⁱⁱ	1.4334 (17)
Co1—O5	2.1023 (10)	C3—C4	1.4161 (17)
Co1—O5ⁱ	2.1023 (10)	C4—C5	1.3687 (17)
O1—C1	1.2842 (16)	C4—H4	0.9500
O2—C1	1.2460 (17)	C5—C6	1.4235 (18)
O3—C2	1.3436 (15)	C5—H5	0.9500
O3—H3	0.78 (2)	C6—C6ⁱⁱ	1.411 (2)
O4—H1	0.76 (2)	C7—H7	0.9500
O4—H2	0.78 (2)	C8—H8A	0.9800
O5—H6	0.79 (3)	C8—H8B	0.9800
O5—H10	0.85 (2)	C8—H8C	0.9800
O6—C7	1.2409 (19)	C9—H9A	0.9800
N1—C7	1.3226 (19)	C9—H9B	0.9800
N1—C8	1.452 (2)	C9—H9C	0.9800

O1ⁱ—Co1—O1	180.0	O3—C2—C6ⁱⁱ	116.24 (11)
O1ⁱ—Co1—O4ⁱ	89.40 (4)	C3—C2—C6ⁱⁱ	120.54 (11)
O1—Co1—O4ⁱ	90.60 (4)	C2—C3—C4	119.02 (11)
O1ⁱ—Co1—O4	90.60 (4)	C2—C3—C1	120.40 (11)
O1—Co1—O4	89.40 (4)	C4—C3—C1	120.57 (11)
O4ⁱ—Co1—O4	180.0	C5—C4—C3	121.81 (12)
O1ⁱ—Co1—O5	91.09 (4)	C5—C4—H4	119.1
O1—Co1—O5	88.91 (4)	C3—C4—H4	119.1
O4ⁱ—Co1—O5	88.28 (4)	C4—C5—C6	119.71 (12)
O4—Co1—O5	91.72 (4)	C4—C5—H5	120.1
O1ⁱ—Co1—O5ⁱ	88.91 (4)	C6—C5—H5	120.1
O1—Co1—O5ⁱ	91.09 (4)	C6ⁱⁱ—C6—C5	120.13 (14)
O4ⁱ—Co1—O5ⁱ	91.72 (4)	C6ⁱⁱ—C6—C2ⁱⁱ	118.74 (14)
O4—Co1—O5ⁱ	88.28 (4)	C5—C6—C2ⁱⁱ	121.14 (11)
O5—Co1—O5ⁱ	180.00 (8)	O6—C7—N1	124.91 (14)
C1—O1—Co1	130.95 (8)	O6—C7—H7	117.5
C2—O3—H3	107.8 (14)	N1—C7—H7	117.5
Co1—O4—H1	118.7 (16)	N1—C8—H8A	109.5
Co1—O4—H2	117.9 (14)	N1—C8—H8B	109.5
H1—O4—H2	104 (2)	H8A—C8—H8B	109.5
Co1—O5—H6	107.4 (18)	N1—C8—H8C	109.5
Co1—O5—H10	114.6 (14)	H8A—C8—H8C	109.5
H6—O5—H10	105 (2)	H8B—C8—H8C	109.5
C7—N1—C8	122.13 (14)	N1—C9—H9A	109.5
C7—N1—C9	120.50 (14)	N1—C9—H9B	109.5
C8—N1—C9	117.37 (13)	H9A—C9—H9B	109.5
O2—C1—O1	123.35 (11)	N1—C9—H9C	109.5
O2—C1—C3	120.55 (12)	H9A—C9—H9C	109.5
O1—C1—C3	116.08 (11)	H9B—C9—H9C	109.5
O3—C2—C3	123.22 (11)

Co1—O1—C1—O2	12.6 (2)	O1—C1—C3—C4	171.94 (11)
Co1—O1—C1—C3	−168.77 (8)	C2—C3—C4—C5	−1.54 (19)
O3—C2—C3—C4	−177.43 (11)	C1—C3—C4—C5	177.49 (12)
C6ⁱⁱ—C2—C3—C4	2.82 (19)	C3—C4—C5—C6	−0.7 (2)
O3—C2—C3—C1	3.5 (2)	C4—C5—C6—C6ⁱⁱ	1.6 (2)
C6ⁱⁱ—C2—C3—C1	−176.22 (11)	C4—C5—C6—C2ⁱⁱ	−178.74 (12)
O2—C1—C3—C2	169.63 (12)	C8—N1—C7—O6	−179.71 (14)
O1—C1—C3—C2	−9.05 (18)	C9—N1—C7—O6	0.7 (2)
O2—C1—C3—C4	−9.39 (19)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1	0.78 (2)	1.81 (2)	2.5168 (13)	149.1 (19)
C7—H7···O4ⁱⁱⁱ	0.95	2.56	3.2322 (18)	128
O4—H1···O6	0.76 (2)	1.99 (2)	2.7449 (16)	178 (2)
O4—H2···O2^iv	0.78 (2)	1.96 (2)	2.7284 (15)	168 (2)
O5—H6···O2ⁱ	0.79 (3)	2.00 (3)	2.7182 (14)	151 (2)
O5—H10···O6ⁱⁱⁱ	0.85 (2)	1.95 (2)	2.7836 (15)	166 (2)
C8—H8C···C3ⁱ	0.98	2.85	3.497 (2)	124

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

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