Crystal structure of a heterometallic coordination polymer: catena-poly[[[tetra­aqua­cobalt(II)]-μ-pyridine-2,6-di­carboxyl­ato-calcium(II)-μ-pyridine-2,6-di­carboxyl­ato] dihydrate]

Lin, J.-S.; Zhang, B.-G.

doi:10.1107/S2056989018007120

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ISSN: 2056-9890

Volume 74| Part 6| June 2018| Pages 808-811

https://doi.org/10.1107/S2056989018007120

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Crystal structure of a heterometallic coordination polymer: catena-poly[[[tetraaquacobalt(II)]-μ-pyridine-2,6-dicarboxylato-calcium(II)-μ-pyridine-2,6-dicarboxylato] dihydrate]

Jie-Shuang Lin ^a and Bing-Guang Zhang ^a ^*

^aKey Laboratory of Catalysis and Materials Sciences of the State Ethnic Affairs Commission & Ministry of Education, College of Chemistry and Material Science, South-Central University for Nationalities, Wuhan 430074, People's Republic of China
^*Correspondence e-mail: zhangbg68@yahoo.com

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 2 April 2018; accepted 10 May 2018; online 18 May 2018)

In the crystal of the title polymeric complex, {[CoCa(C₇H₃NO₄)₂(H₂O)₄]·2H₂O}_n (1), the Co^II ion is N,O,O′-chelated by two pyridine-2,6-dicarboxylate anions in a distorted N₂O₄ octahedral geometry, and two carboxylate O atoms of pyridine-2,6-dicarboxylate anions bridge tetraaquacalcium(II) units to form polymeric chains propagating along the b-axis direction. In the crystal, O—H⋯O and C—H⋯O hydrogen bonds, and offset π–π stacking interactions [intercentroid distances = 3.551 (1) and 3.746 (1) Å] involving inversion-related pyridine rings link the polymeric chains and lattice water molecules to form a supramolecular three-dimensional framework.

Keywords: crystal structure; heterometallic complex; cobalt carboxylates; calcium carboxylates; pyridine-2,6-dicarboxylate anions; hydrogen bonds; offset π–π interactions.

CCDC reference: 1832782

1. Chemical context

The controllable synthesis of heterometallic polymers, with their fascinating structures and outstanding properties, is still a challenge in crystal engineering (Cai et al., 2012 ; Ma et al., 2014 ; Sun et al., 2014 ; Ward, 2007 ). The influencing factors include the coordination geometry of the metal centre, reaction of solvent, temperature, metal-to-ligand ratio, pH value, the nature of ligand, and so on (Chen et al., 2012 ; Guo & Cao, 2009 ; Ni et al., 2009 ; Yamada et al., 2011 ). According to our earlier study (Sun et al., 2016 ), heterometallic complexes containing both alkaline earth metals and d-block transition metals are available because the former are structurally malleable and they have a strong affinity to O atoms rather than N atoms (Cao et al., 2015 ; Yu et al., 2013 ), and the latter have a strong tendency to coordinate to both N- and O-atom donors (Hu et al., 2013 ; Zhang et al., 2013 ). Meanwhile, pyridinedicarboxylic acid (H₂pdc) is widely used in the construction of various metal–organic frameworks for two main reasons. Firstly, the O and N atoms in these ligands made them easy to chelate or bridge metal ions. Secondly, they can be completely or partially deprotonated to generate Hpdc⁻ or pyc²⁻, displaying a variety of coordination modes. As a part of our ongoing studies on heterometallic frameworks, we describe here the synthesis and crystal structure of the title complex,1

2. Structural commentary

The asymmetric unit of 1 contains one cobalt centre, one calcium centre, two pdc²⁻ anions, four coordinated water molecules and two lattice water molecules (Fig. 1). The Co—O(N) bond lengths are in the range 2.0172 (13)–2.2018 (12) Å and the Ca—O bond lengths are in the range 2.3358 (12)–2.3727 (12) Å (Table 1). All the data are comparable to those reported for other related Co^II–pdc and Ca^II–pdc complexes (Jung et al., 2008 ; Shi et al., 2012 ). Each Co^II centre is chelated by four O and two N atoms from two pdc²⁻ anions, forming a distorted octahedral geometry. The mean deviation of the equatorial plane constructed by atoms N1, N2, O5 and O7 is 0.02 Å. Each Ca^II centre is six-coordinated by two carboxylate O atoms from two pdc²⁻ anions and four water molecules, displaying a distorted octahedron (Fig. 1). The mean deviation of the equatorial plane constructed by atoms O4, OW1, OW3 and OW4 is 0.08 Å. The CoN₂O₄ and CaO₆ polyhedra are linked by pdc²⁻ anions to form polymeric chains along the b-axis direction (Fig. 2).

Table 1
Selected bond lengths (Å)

Co1—N1	2.0172 (13)	Ca1—O4ⁱ	2.3358 (12)
Co1—N2	2.0199 (13)	Ca1—OW4	2.3449 (13)
Co1—O5	2.1466 (12)	Ca1—O8	2.3458 (12)
Co1—O3	2.1469 (13)	Ca1—OW1	2.3476 (13)
Co1—O1	2.1643 (12)	Ca1—OW3	2.3719 (13)
Co1—O7	2.2018 (12)	Ca1—OW2	2.3727 (12)
Symmetry code: (i) x, y-1, z.

Figure 1
The coordination mode and atom-numbering scheme for the asymmetric unit of 1. Displacement ellipsoids are drawn at the 50% probability level [symmetry codes: (A) x, y − 1, z; (B) x, y + 1, z].

Figure 2
The chain formed by pdc²⁻ anions, and Co^II and Ca^II centres, propagating along the b-axis direction.

3. Supramolcular features

In the crystal of 1, the polymeric chains are linked by O—H⋯O and C—H⋯O hydrogen bonds involving the water molecules and carboxyl groups, so forming a supramolecular three-dimensional framework (Table 2 and Fig. 3). Within the framework, inversion-related pyridine rings are linked by offset π–π interactions reinforcing the framework: Cg5⋯Cg5^vii = 3.746 (1) Å, interplanar distance = 3.309 (1) Å, slippage = 1.755 Å; Cg6⋯Cg6^viii = 3.551 (1) Å, interplanar distance = 3.279 (1) Å, slippage = 1.363 Å; Cg5 and Cg6 are the centroids of pyridine rings N1/C1–C5 and N2/C8–C12, respectively; symmetry codes: (vii) −x + 1, −y + 1, −z; (viii) −x + 1, −y, −z + 1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
OW1—HW1A⋯O2ⁱⁱ	0.84 (1)	1.93 (1)	2.769 (2)	171 (3)
OW1—HW1B⋯O2ⁱⁱⁱ	0.85 (1)	2.06 (1)	2.870 (2)	161 (3)
OW2—HW2A⋯OW6	0.85 (1)	2.00 (1)	2.846 (2)	175 (3)
OW2—HW2B⋯O5^iv	0.85 (1)	1.89 (1)	2.730 (2)	173 (3)
OW3—HW3A⋯O1ⁱⁱ	0.84 (1)	1.99 (1)	2.817 (2)	172 (3)
OW3—HW3B⋯O6^v	0.84 (1)	2.12 (1)	2.923 (2)	162 (3)
OW4—HW4A⋯O6^iv	0.84 (1)	2.02 (1)	2.851 (2)	172 (3)
OW4—HW4B⋯OW5	0.84 (1)	1.90 (1)	2.741 (2)	173 (3)
OW5—HW5A⋯O8^vi	0.85 (1)	2.10 (1)	2.946 (2)	174 (3)
OW5—HW5B⋯O3^v	0.85 (1)	2.08 (2)	2.870 (2)	153 (3)
OW6—HW6A⋯O7ⁱ	0.84 (1)	2.13 (1)	2.945 (2)	163 (3)
OW6—HW6B⋯O2^iv	0.84 (1)	2.34 (1)	3.140 (2)	160 (3)
C2—H2A⋯O7ⁱⁱⁱ	0.93	2.56	3.448 (2)	160
C10—H10A⋯O3^v	0.93	2.55	3.246 (2)	132
Symmetry codes: (i) x, y-1, z; (ii) x+1, y, z; (iii) -x+1, -y, -z; (iv) x+1, y-1, z; (v) -x+1, -y, -z+1; (vi) -x+1, -y-1, -z+1.

Figure 3
A view along the c axis of the crystal packing of 1. The hydrogen bonds are shown as dashed lines (see Table 2

). For clarity, only the H atoms involved in these interactions have been included.

4. Database survey

A search of the Cambridge Structural Database (Version 5.39, last update February 2018; Groom et al., 2016 ) for cobalt complexes of the ligand pyridine-2,6-dicarboxylic acid gave 180 hits, of which 58 are polymeric complexes. They include a number of alkali metal heterometallic coordination polymes, four involving K⁺ and seven Na⁺, but no alkali earth metal heterometallic coordination polymers. Hence, the title compound 1 is the first reported heterometallic coordination polymer involving the ligand pyridine-2,6-dicarboxylic acid, Co^II and an alkali earth metal (Ca^II).

5. Synthesis and crystallization

A mixture of H₂pdc (167 mg, 1 mmol), Co(CH₃COO)₂·4H₂O (125 mg, 0.5 mmol) and CaCl₂ (110 mg, 1 mmol) in 15 ml of distilled H₂O was stirred for 10 min in air. 0.5 M NaOH was added dropwise and the mixture was turned into a Parr Teflon-lined stainless steel vessel and heated at 423 K for 3 d. Blue [purple in CIF?] block-shaped crystals of 1 were obtained in a yield of 70% (based on pyridine-2,6-dicarboxylic acid).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The H atoms of the water molecules were located from difference-Fourier maps and refined with distance restraints: O—H = 0.85 (1) Å, H⋯H = 1.34 (1) Å with U_iso(H) = 1.5U_eq(O). C-bound H atoms atoms were included in calculated positions and refined as riding: C—H = 0.93 Å with U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	[CaCo(C₇H₃NO₄)₂(H₂O)₄]·2H₂O
M_r	537.31
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	8.6299 (8), 8.7781 (8), 14.0726 (12)
α, β, γ (°)	80.683 (1), 73.602 (1), 89.568 (1)
V (Å³)	1008.38 (16)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.18
Crystal size (mm)	0.35 × 0.33 × 0.33

Data collection
Diffractometer	Bruker SMART CCD
No. of measured, independent and observed [I > 2σ(I)] reflections	7052, 3537, 3342
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.064, 1.01
No. of reflections	3537
No. of parameters	326
No. of restraints	18
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.49
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1832782

Crystal structure: contains datablocks 1, global. DOI: https://doi.org/10.1107/S2056989018007120/xu5921sup1.cif

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL97 (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

catena-Poly[[[tetraaquacobalt(II)]-µ-pyridine-2,6-dicarboxylato-\ calcium(II)-µ-pyridine-2,6-dicarboxylato] dihydrate] top

Crystal data top

[CaCo(C₇H₃NO₄)₂(H₂O)₄]·2H₂O	Z = 2
M_r = 537.31	F(000) = 550
Triclinic, P1	D_x = 1.770 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6299 (8) Å	Cell parameters from 5842 reflections
b = 8.7781 (8) Å	θ = 2.4–27.7°
c = 14.0726 (12) Å	µ = 1.18 mm⁻¹
α = 80.683 (1)°	T = 296 K
β = 73.602 (1)°	Block, purple
γ = 89.568 (1)°	0.35 × 0.33 × 0.33 mm
V = 1008.38 (16) Å³

Data collection top

Bruker SMART CCD diffractometer	3342 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.012
Graphite monochromator	θ_max = 25.0°, θ_min = 2.6°
φ and ω scans	h = −10→10
7052 measured reflections	k = −10→9
3537 independent reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.064	w = 1/[σ²(F_o²) + (0.0385P)² + 0.4728P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
3537 reflections	Δρ_max = 0.44 e Å⁻³
326 parameters	Δρ_min = −0.49 e Å⁻³
18 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0300 (14)

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Co1	0.39269 (3)	0.14153 (3)	0.252249 (15)	0.02155 (10)
Ca1	0.86691 (4)	−0.38042 (3)	0.24956 (2)	0.01922 (10)
O1	0.24638 (15)	0.02836 (14)	0.18004 (9)	0.0291 (3)
O2	0.20443 (16)	0.02565 (16)	0.03080 (10)	0.0364 (3)
O3	0.55173 (16)	0.32701 (14)	0.25445 (9)	0.0301 (3)
O4	0.73160 (16)	0.50764 (15)	0.15426 (11)	0.0351 (3)
O5	0.19108 (15)	0.25552 (15)	0.33569 (9)	0.0308 (3)
O6	0.02552 (14)	0.25623 (14)	0.48985 (9)	0.0297 (3)
O7	0.57745 (15)	−0.03428 (14)	0.24055 (9)	0.0295 (3)
O8	0.63798 (15)	−0.25231 (14)	0.32698 (10)	0.0325 (3)
N1	0.47499 (16)	0.24083 (15)	0.10671 (10)	0.0192 (3)
N2	0.33969 (16)	0.01759 (15)	0.39227 (10)	0.0192 (3)
C1	0.42012 (19)	0.18591 (18)	0.03843 (12)	0.0200 (3)
C2	0.4907 (2)	0.23423 (19)	−0.06355 (12)	0.0247 (4)
H2A	0.4515	0.1975	−0.1111	0.030*
C3	0.6221 (2)	0.3394 (2)	−0.09255 (13)	0.0280 (4)
H3A	0.6739	0.3713	−0.1604	0.034*
C4	0.6763 (2)	0.3971 (2)	−0.02081 (13)	0.0263 (4)
H4A	0.7631	0.4685	−0.0397	0.032*
C5	0.59765 (19)	0.34531 (18)	0.07952 (12)	0.0209 (3)
C6	0.27915 (19)	0.06991 (19)	0.08568 (12)	0.0226 (3)
C7	0.6325 (2)	0.39819 (19)	0.16942 (13)	0.0237 (4)
C8	0.22421 (19)	0.06489 (18)	0.46591 (12)	0.0194 (3)
C9	0.1926 (2)	−0.0107 (2)	0.56454 (12)	0.0236 (4)
H9A	0.1131	0.0227	0.6159	0.028*
C10	0.2824 (2)	−0.13715 (19)	0.58450 (12)	0.0251 (4)
H10A	0.2628	−0.1901	0.6498	0.030*
C11	0.4018 (2)	−0.18510 (19)	0.50709 (12)	0.0232 (3)
H11A	0.4627	−0.2698	0.5197	0.028*
C12	0.42759 (19)	−0.10363 (18)	0.41099 (12)	0.0200 (3)
C13	0.13795 (19)	0.20400 (19)	0.42944 (12)	0.0216 (3)
C14	0.55835 (19)	−0.13350 (19)	0.31863 (12)	0.0222 (3)
OW1	0.95691 (18)	−0.19898 (17)	0.10151 (11)	0.0404 (3)
OW2	1.02789 (16)	−0.59450 (15)	0.21033 (10)	0.0319 (3)
OW3	1.06339 (17)	−0.23885 (16)	0.29216 (10)	0.0354 (3)
OW4	0.84002 (17)	−0.51094 (15)	0.41287 (9)	0.0325 (3)
OW5	0.6149 (3)	−0.4991 (2)	0.59299 (15)	0.0782 (7)
OW6	0.8857 (2)	−0.8525 (2)	0.16230 (15)	0.0604 (5)
HW1A	1.039 (2)	−0.139 (3)	0.080 (2)	0.091*
HW4A	0.902 (3)	−0.577 (3)	0.430 (2)	0.091*
HW3A	1.126 (3)	−0.163 (2)	0.2603 (17)	0.091*
HW4B	0.771 (3)	−0.499 (3)	0.4666 (13)	0.091*
HW3B	1.060 (4)	−0.247 (3)	0.3528 (8)	0.091*
HW1B	0.898 (3)	−0.168 (3)	0.0638 (19)	0.091*
HW2A	0.985 (4)	−0.668 (2)	0.192 (2)	0.091*
HW2B	1.072 (3)	−0.639 (3)	0.2531 (18)	0.091*
HW6A	0.7978 (18)	−0.902 (3)	0.172 (2)	0.091*
HW5B	0.596 (4)	−0.447 (3)	0.6408 (17)	0.091*
HW6B	0.958 (2)	−0.907 (3)	0.134 (2)	0.091*
HW5A	0.539 (3)	−0.569 (3)	0.613 (2)	0.091*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02474 (14)	0.02310 (14)	0.01634 (14)	0.00250 (9)	−0.00629 (9)	−0.00120 (9)
Ca1	0.01825 (18)	0.01797 (18)	0.02199 (19)	0.00136 (13)	−0.00637 (13)	−0.00374 (13)
O1	0.0303 (7)	0.0314 (7)	0.0239 (6)	−0.0101 (5)	−0.0077 (5)	0.0011 (5)
O2	0.0394 (7)	0.0394 (8)	0.0349 (7)	−0.0162 (6)	−0.0220 (6)	0.0022 (6)
O3	0.0390 (7)	0.0304 (7)	0.0253 (7)	−0.0001 (6)	−0.0148 (6)	−0.0069 (5)
O4	0.0356 (7)	0.0294 (7)	0.0482 (8)	−0.0055 (6)	−0.0228 (6)	−0.0095 (6)
O5	0.0333 (7)	0.0340 (7)	0.0240 (6)	0.0140 (6)	−0.0087 (5)	−0.0014 (5)
O6	0.0273 (6)	0.0335 (7)	0.0293 (7)	0.0119 (5)	−0.0074 (5)	−0.0094 (5)
O7	0.0306 (7)	0.0314 (7)	0.0226 (6)	0.0071 (5)	−0.0027 (5)	−0.0022 (5)
O8	0.0291 (7)	0.0267 (7)	0.0385 (7)	0.0121 (5)	−0.0044 (6)	−0.0060 (6)
N1	0.0195 (7)	0.0200 (7)	0.0191 (7)	0.0001 (5)	−0.0077 (5)	−0.0025 (5)
N2	0.0193 (7)	0.0200 (7)	0.0193 (7)	0.0026 (5)	−0.0068 (5)	−0.0038 (5)
C1	0.0203 (8)	0.0204 (8)	0.0210 (8)	0.0017 (6)	−0.0089 (6)	−0.0035 (6)
C2	0.0296 (9)	0.0265 (9)	0.0205 (8)	0.0037 (7)	−0.0098 (7)	−0.0059 (7)
C3	0.0274 (9)	0.0317 (10)	0.0199 (8)	0.0013 (7)	−0.0005 (7)	−0.0008 (7)
C4	0.0204 (8)	0.0240 (9)	0.0314 (9)	−0.0025 (7)	−0.0042 (7)	−0.0014 (7)
C5	0.0181 (8)	0.0191 (8)	0.0265 (8)	0.0016 (6)	−0.0086 (6)	−0.0034 (6)
C6	0.0212 (8)	0.0206 (8)	0.0276 (9)	0.0003 (7)	−0.0096 (7)	−0.0033 (7)
C7	0.0227 (8)	0.0212 (8)	0.0328 (10)	0.0056 (7)	−0.0152 (7)	−0.0079 (7)
C8	0.0178 (7)	0.0214 (8)	0.0206 (8)	0.0005 (6)	−0.0067 (6)	−0.0059 (6)
C9	0.0230 (8)	0.0276 (9)	0.0198 (8)	0.0004 (7)	−0.0046 (7)	−0.0051 (7)
C10	0.0296 (9)	0.0252 (9)	0.0199 (8)	−0.0034 (7)	−0.0086 (7)	0.0010 (7)
C11	0.0256 (8)	0.0186 (8)	0.0268 (9)	0.0016 (7)	−0.0109 (7)	−0.0012 (7)
C12	0.0195 (8)	0.0180 (8)	0.0239 (8)	0.0007 (6)	−0.0076 (6)	−0.0050 (6)
C13	0.0206 (8)	0.0230 (8)	0.0244 (8)	0.0025 (7)	−0.0096 (7)	−0.0074 (7)
C14	0.0203 (8)	0.0215 (8)	0.0261 (9)	0.0011 (7)	−0.0073 (7)	−0.0069 (7)
OW1	0.0403 (8)	0.0436 (8)	0.0358 (8)	−0.0165 (7)	−0.0177 (6)	0.0116 (6)
OW2	0.0345 (7)	0.0307 (7)	0.0338 (7)	0.0123 (6)	−0.0144 (6)	−0.0069 (6)
OW3	0.0389 (8)	0.0386 (8)	0.0292 (7)	−0.0145 (6)	−0.0115 (6)	−0.0036 (6)
OW4	0.0392 (8)	0.0295 (7)	0.0255 (7)	0.0071 (6)	−0.0057 (6)	−0.0014 (5)
OW5	0.0881 (15)	0.0622 (12)	0.0629 (12)	−0.0295 (10)	0.0275 (10)	−0.0355 (10)
OW6	0.0414 (9)	0.0520 (10)	0.0866 (13)	−0.0007 (8)	−0.0021 (9)	−0.0370 (9)

Geometric parameters (Å, º) top

Co1—N1	2.0172 (13)	C2—H2A	0.9300
Co1—N2	2.0199 (13)	C3—C4	1.389 (3)
Co1—O5	2.1466 (12)	C3—H3A	0.9300
Co1—O3	2.1469 (13)	C4—C5	1.384 (2)
Co1—O1	2.1643 (12)	C4—H4A	0.9300
Co1—O7	2.2018 (12)	C5—C7	1.521 (2)
Ca1—O4ⁱ	2.3358 (12)	C8—C9	1.390 (2)
Ca1—OW4	2.3449 (13)	C8—C13	1.519 (2)
Ca1—O8	2.3458 (12)	C9—C10	1.386 (2)
Ca1—OW1	2.3476 (13)	C9—H9A	0.9300
Ca1—OW3	2.3719 (13)	C10—C11	1.390 (2)
Ca1—OW2	2.3727 (12)	C10—H10A	0.9300
O1—C6	1.268 (2)	C11—C12	1.382 (2)
O2—C6	1.243 (2)	C11—H11A	0.9300
O3—C7	1.266 (2)	C12—C14	1.520 (2)
O4—C7	1.242 (2)	OW1—HW1A	0.844 (10)
O4—Ca1ⁱⁱ	2.3358 (12)	OW1—HW1B	0.846 (10)
O5—C13	1.274 (2)	OW2—HW2A	0.849 (10)
O6—C13	1.236 (2)	OW2—HW2B	0.845 (10)
O7—C14	1.258 (2)	OW3—HW3A	0.838 (10)
O8—C14	1.253 (2)	OW3—HW3B	0.837 (10)
N1—C5	1.334 (2)	OW4—HW4A	0.840 (10)
N1—C1	1.338 (2)	OW4—HW4B	0.842 (10)
N2—C8	1.338 (2)	OW5—HW5B	0.854 (10)
N2—C12	1.337 (2)	OW5—HW5A	0.854 (10)
C1—C2	1.387 (2)	OW6—HW6A	0.843 (10)
C1—C6	1.517 (2)	OW6—HW6B	0.839 (10)
C2—C3	1.392 (3)

N1—Co1—N2	170.56 (5)	C4—C3—H3A	119.8
N1—Co1—O5	113.11 (5)	C2—C3—H3A	119.8
N2—Co1—O5	76.33 (5)	C5—C4—C3	118.16 (16)
N1—Co1—O3	76.31 (5)	C5—C4—H4A	120.9
N2—Co1—O3	104.44 (5)	C3—C4—H4A	120.9
O5—Co1—O3	89.74 (5)	N1—C5—C4	120.99 (15)
N1—Co1—O1	76.52 (5)	N1—C5—C7	112.31 (14)
N2—Co1—O1	103.75 (5)	C4—C5—C7	126.69 (15)
O5—Co1—O1	93.20 (5)	O2—C6—O1	125.55 (15)
O3—Co1—O1	151.54 (5)	O2—C6—C1	118.66 (15)
N1—Co1—O7	94.39 (5)	O1—C6—C1	115.77 (14)
N2—Co1—O7	76.18 (5)	O4—C7—O3	125.91 (16)
O5—Co1—O7	152.44 (5)	O4—C7—C5	118.68 (16)
O3—Co1—O7	95.18 (5)	O3—C7—C5	115.38 (14)
O1—Co1—O7	95.16 (5)	N2—C8—C9	120.75 (15)
O4ⁱ—Ca1—OW4	116.69 (5)	N2—C8—C13	113.26 (13)
O4ⁱ—Ca1—O8	92.96 (5)	C9—C8—C13	126.00 (14)
OW4—Ca1—O8	84.24 (5)	C10—C9—C8	118.39 (15)
O4ⁱ—Ca1—OW1	82.87 (5)	C10—C9—H9A	120.8
OW4—Ca1—OW1	160.32 (5)	C8—C9—H9A	120.8
O8—Ca1—OW1	97.60 (5)	C9—C10—C11	120.17 (15)
O4ⁱ—Ca1—OW3	160.85 (5)	C9—C10—H10A	119.9
OW4—Ca1—OW3	80.10 (5)	C11—C10—H10A	119.9
O8—Ca1—OW3	98.14 (5)	C12—C11—C10	118.30 (15)
OW1—Ca1—OW3	80.24 (5)	C12—C11—H11A	120.8
O4ⁱ—Ca1—OW2	78.31 (5)	C10—C11—H11A	120.8
OW4—Ca1—OW2	80.75 (5)	N2—C12—C11	121.15 (15)
O8—Ca1—OW2	156.81 (5)	N2—C12—C14	113.20 (14)
OW1—Ca1—OW2	102.49 (5)	C11—C12—C14	125.58 (14)
OW3—Ca1—OW2	96.57 (5)	O6—C13—O5	125.96 (15)
C6—O1—Co1	115.23 (10)	O6—C13—C8	119.55 (15)
C7—O3—Co1	115.79 (10)	O5—C13—C8	114.48 (14)
C7—O4—Ca1ⁱⁱ	136.36 (12)	O8—C14—O7	126.01 (15)
C13—O5—Co1	116.59 (10)	O8—C14—C12	117.73 (15)
C14—O7—Co1	114.36 (10)	O7—C14—C12	116.25 (14)
C14—O8—Ca1	144.69 (12)	Ca1—OW1—HW1A	131.0 (19)
C5—N1—C1	121.46 (14)	Ca1—OW1—HW1B	123.2 (19)
C5—N1—Co1	118.88 (11)	HW1A—OW1—HW1B	104.7 (15)
C1—N1—Co1	119.07 (11)	Ca1—OW2—HW2A	117 (2)
C8—N2—C12	121.24 (14)	Ca1—OW2—HW2B	118 (2)
C8—N2—Co1	119.12 (11)	HW2A—OW2—HW2B	104.6 (15)
C12—N2—Co1	119.49 (11)	Ca1—OW3—HW3A	132.0 (19)
N1—C1—C2	120.97 (15)	Ca1—OW3—HW3B	118.4 (19)
N1—C1—C6	112.71 (14)	HW3A—OW3—HW3B	108.0 (15)
C2—C1—C6	126.33 (15)	Ca1—OW4—HW4A	126.5 (19)
C1—C2—C3	117.92 (15)	Ca1—OW4—HW4B	128.2 (18)
C1—C2—H2A	121.0	HW4A—OW4—HW4B	105.2 (15)
C3—C2—H2A	121.0	HW5B—OW5—HW5A	103.9 (15)
C4—C3—C2	120.46 (16)	HW6A—OW6—HW6B	105.7 (15)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
OW1—HW1A···O2ⁱⁱⁱ	0.84 (1)	1.93 (1)	2.769 (2)	171 (3)
OW1—HW1B···O2^iv	0.85 (1)	2.06 (1)	2.870 (2)	161 (3)
OW2—HW2A···OW6	0.85 (1)	2.00 (1)	2.846 (2)	175 (3)
OW2—HW2B···O5^v	0.85 (1)	1.89 (1)	2.730 (2)	173 (3)
OW3—HW3A···O1ⁱⁱⁱ	0.84 (1)	1.99 (1)	2.817 (2)	172 (3)
OW3—HW3B···O6^vi	0.84 (1)	2.12 (1)	2.923 (2)	162 (3)
OW4—HW4A···O6^v	0.84 (1)	2.02 (1)	2.851 (2)	172 (3)
OW4—HW4B···OW5	0.84 (1)	1.90 (1)	2.741 (2)	173 (3)
OW5—HW5A···O8^vii	0.85 (1)	2.10 (1)	2.946 (2)	174 (3)
OW5—HW5B···O3^vi	0.85 (1)	2.08 (2)	2.870 (2)	153 (3)
OW6—HW6A···O7ⁱ	0.84 (1)	2.13 (1)	2.945 (2)	163 (3)
OW6—HW6B···O2^v	0.84 (1)	2.34 (1)	3.140 (2)	160 (3)
C2—H2A···O7^iv	0.93	2.56	3.448 (2)	160
C10—H10A···O3^vi	0.93	2.55	3.246 (2)	132

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

Funding information

This work was supported financially by the National Natural Science Foundation of China (No. 21271189).

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