English

• 0.   Introduction

  Recently the field of coordination polymers have attracted a tremendous attention not only for their intriguing varieties of molecular architectures and topologies but also for their applications in catalysis, magnetism, luminescence, and gas storage^[1-5]. Although chemists and materials scientists have devoted much effort to rational design and syntheses of coordination polymers, it is difficult to predict the structures of coordination polymers, because a lot of factors influence the construction of complex, such as the structural features of organic ligands, the coordination requirements of metal ions, solvent systems, temperatures, and pH values^[6-11].

  In this context, various types of aromatic polycarboxylic acids have been extensively utilized to synthesize various coordination polymers owing to their strong coordination ability in diverse modes and the fact that they are able to satisfy the geometric requirement of the metal centers^{[1-2, 6, 12-14]}.

  Currently, the water pollutant is becoming one serious environmental problem in the world. Much effort has been devoted to developing new photocatalytic materials for the green degradation of organic pollutants. Coordination polymers has showed good photocatalytic activities for the decomposition of organic dyes^[15-18].

  As a combination of the aforementioned aspects and our previous research work, we have selected a new asymmetric dicarboxylate ligand, 4-((carboxymethyl)thio)benzoic acid (H₂L, Scheme 1) and explored it for the construction of novel coordination polymers. The ligand will not only have the characteristic coordination chemistry of the rigid carboxylate system, but also have the peculiar coordination chemistry of the flexible carboxylate system, which may be favorable for the formation of novel structures of coordination polymers. Besides, this acid block remains poorly used for the generation of coordination polymers.

  Scheme 1

  

  Scheme 1.  Coordination modes of L^2- ligands in complexes 1 and 2

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  In this work, we report the syntheses, crystal structures, photocatalytic properties of Co(Ⅱ) and Mn(Ⅱ) coordination polymers constructed from the dicarboxylate ligand.

  1.   Experimental

  1.1   Reagents and physical measurements

  All chemicals and solvents were of AR grade and used without further purification. Carbon, hydrogen and nitrogen were determined using an Elementar Vario EL elemental analyzer. IR spectra were recorded using KBr pellets and a Bruker EQUINOX 55 spectrometer. Thermogravimetric analysis (TGA) data were collected on a LINSEIS STA PT1600 thermal analyzer with a heating rate of 10 ℃·min^-1. Powder X -ray diffraction patterns (PXRD) were measured on a RigakuDmax 2400 diffractometer using Cu Kα radiation (λ = 0.154 06 nm); the X - ray tube was operated at 40 kV and 40 mA and the data collection range was between 5° and 45°.

  1.2   Synthesis of {[Co(μ₃-L)(4, 4′-bipy)]·H₂O}_n (1)

  A mixture of CoCl₂·6H₂O (0.048 g, 0.20 mmol), H₂L (0.049 g, 0.20 mmol), 4, 4′ - bipy (0.031 g, 0.20 mmol), NaOH (0.016 g, 0.40 mmol) and H₂O (10 mL) was stirred at room temperature for 15 min. Then the mixture was sealed in a 25 mL Teflon - lined stainless steel vessel, and heated at 160 ℃ for 3 d, followed by cooling to room temperature at a rate of 10 ℃·h^-1. Pink block-shaped crystals of 1 were isolated manually, and washed with distilled water. Yield: 45% (based on H₂L). Anal. Calcd. for C₂₀H₁₈CoN₂O₅S(%): C 52.52, H 3.97, N 6.12; Found(%): C 52.78, H 3.99, N 6.10. IR (KBr, cm^-1): 3 373w, 3 059w, 1 606s, 1 550m, 1 448w, 1 408s, 1 307w, 1 279w, 1 223w, 1 172w, 1 070w, 1 015w, 935w, 845w, 817w, 772w, 733w, 693w, 631w.

  1.3   Synthesis of {[Mn(μ-L) (4, 4′-bipy) (H₂O)₂]·H₂O}_n (2)

  The preparation of 2 was similar to that of 1 except that MnCl₂·4H₂O was used instead of CoCl₂·6H₂O. After the reaction mixture was cooled to room temperature, yellow block-shaped crystals of 2 were isolated manually, washed with distilled water, and dried. Yield: 50% (based on H₂L). Anal. Calcd. for C₂₀H₂₂MnN₂O₇S(%): C 49.08, H 4.53, N 5.72; Found (%): C 48.86, H 4.56, N 5.70. IR (KBr, cm^-1): 3 160w, 2 941w, 1 699m, 1 584s, 1 532s, 1 419s, 1 369s, 1 313 w, 1 223w, 1 178w, 1 144w, 1 088w, 1 060w, 998w, 942w, 851w, 811m, 772w, 727w, 693w, 620w.

  The complex are insoluble in water and common organic solvents, such as methanol, ethanol, acetone and DMF.

  1.4   Structure determination

  Two single crystals with dimensions of 0.23 mm× 0.22 mm×0.21 mm (1) and 0.23 mm×0.22 mm×0.20 mm (2) were collected at 293(2) K on a Bruker SMART APEX Ⅱ CCD diffractometer with Mo Kα radiation (λ=0.071 073 nm). The structures were solved by direct methods and refined by full matrix least-square on F² using the SHELXTL-2014 program^[19]. All non-hydrogen atoms were refined anisotropically. All the hydrogen atoms (except those of H₂O moieties) were positioned geometrically and refined using a riding model. The H atoms of H₂O moieties were located by difference maps and constrained to ride on their parent O atoms. A summary of the crystallography data and structure refinements for 1 and 2 is given in Table 1. The selected bond lengths and angles for complexes 1 and 2 are listed in Table 2. Hydrogen bond parameters of complexes 1 and 2 are given in Table 3.

  Table 1

  

  Table 1.  Crystal data and structure refinements for complexes 1 and 2

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  Complex	1	2
  Chemical formula	C20H18CoN2O5S	C20H22MnN2O7S
  Formula weight	457.35	489.39
  Crystal system	Triclinic	Monoclinic
  Space group	P1	P21/c
  a / nm	0.962 02(11)	1.169 40(7)
  b / nm	1.033 02(9)	2.084 67(13)
  c / nm	1.167 18(12)	0.867 13(5)
  α / (°)	91.823(8)
  β / (°)	108.270(10)	100.881(5)
  γ / (°)	110.391(9)
  V / nm3	1.019 4(2)	2.075 9(2)
  Z	2	4
  F(000)	470	1 012
  θ range for data collection / (°)	3.432~25.046	3.330~25.047
  Limiting indices	-9 ≤ h ≤ 11, -12 ≤ k ≤ 12, -13 ≤ l ≤ 13	-12 ≤ h ≤ 13, -10 ≤ k ≤ 24, -10 ≤ l ≤ 5
  Reflection collected, unique (Rint)	6 536, 3 605 (0.057 0)	6 592, 3 666 (0.038 7)
  Dc / (g·cm-3)	1.490	1.566
  μ / mm-1	0.978	0.783
  Data, restraint, parameter	3 605, 0, 262	3 666, 0, 280
  Goodness-of-fit on F2	1.056	1.052
  Final R indices[I≥2σ(I)] R1, wR2	0.069 3, 0.108 9	0.047 9, 0.071 3
  R indices (all data) R1, wR2	0.163 2, 0.198 9	0.099 4, 0.117 8
  Largest diff. peak and hole / (e·nm-3)	918 and -650	376 and -389

  Table 2

  

  Table 2.  Selected bond lengths (nm) and bond angles (°) for complexes 1 and 2

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  1
  Co(1)—O(1)	0.201 0(4)	Co(1)—O(2)A	0.204 5(4)	Co(1)—O(3)B	0.223 3(4)
  Co(1)—O(4)B	0.217 1(4)	Co(1)—N(1)	0.215 1(4)	Co(1)—N(2)C	0.214 8(4)
  O(1)—Co(1)—O(2)A	119.64(18)	O(1)—Co(1)-N(2)C	91.44(17)	O(2)A—Co(1)—N(2)C	92.56(16)
  O(1)—Co(1)—N(1)	88.26(17)	O(2)A—Co(1)-N(1)	87.63(16)	N(1)—Co(1)—N(2)C	179.70(17)
  O(1)—Co(1)—O(4)B	149.45(17)	O(2)A—Co(1)-O(4)B	90.84(16)	N(2)C—Co(1)—O(4)B	89.12(17)
  N(1)—Co(1)—O(4)B	91.11(17)	O(1)—Co(1)-O(3)B	90.48(17)	O(2)A—Co(1)—O(3)B	149.38(18)
  N(2)C—Co(1)—O(3)B	91.98(17)	N(1)—Co(1)—O(3)B	87.97(17)	O(4)B—Co(1)—O(3)B	58.98(15)
  2
  Mn(1)—O(1)A	0.217 9(2)	Mn(1)—O(2)	0.213 3(2)	Mn(1)—O(5)	0.214 0(2)
  Mn(1)—O(6)	0.219 8(2)	Mn(1)—N(1)	0.230 2(3)	Mn(1)—N(2)B	0.229 0(3)
  O(2)—Mn(1)—O(5)	177.55(9)	O(2)—Mn(1)—O(1)A	81.85(9)	O(5)—Mn(1)—O(1)A	99.56(9)
  O(2)—Mn(1)—O(6)	94.18(9)	O(5)—Mn(1)—O(6)	84.59(9)	O(1)A—Mn(1)—O(6)	173.46(8)
  O(2)—Mn(1)—N(2)B	87.91(9)	O(5)-Mn(1)—N(2)B	90.15(9)	O(1)A—Mn(1)—N(2)B	87.24(9)
  O(6)—Mn(1)—N(2)B	97.85(10)	O(2)—Mn(1)—N(1)	92.29(9)	O(5)—Mn(1)—N(1)	89.66(9)
  O(1)A—Mn(1)—N(1)	91.93(10)	O(6)—Mn(1)—N(1)	83.01(10)	N(2)B—Mn(1)—N(1)	179.11(11)
  Symmetry codes: A: -x, -y+1, -z+1; B: -x, -y+1, -z+2; C: x-1, y-1, z for 1; A: x, -y+1/2, z+1/2; B: x-1, y, z for 2.

  Table 3

  

  Table 3.  Hydrogen parameters of complexes 1 and 2

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  Complex	D—H…A	d(D—H) / nm	d(H…A) / nm	d(D…A) / nm	∠DHA / (°)
  1	O(5)—H(1W)…O(3)A	0.085 0	0.203 3	0.288 3	178.91
  2	O(5)—H(1W)…O(7)B	0.082 0	0.193 9	0.271 9	158.61
  	O(5)—H(2W)…O(1)C	0.083 7	0.188 4	0.271 1	169.24
  	O(6)—H(4W)…O(3)D	0.082 0	0.182 3	0.263 6	170.87
  	O(7)—H(6W)…O(4)E	0.086 8	0.218 6	0.270 1	117.77
  Symmetry codes: A: -x, -y+1, -z+2 for 1; B: -x+1, -y+1, -z+1; C: x, y, z+1; D: -x, -y, -z+1; E: x+1, y+1, z for 2.

  CCDC: 1967233, 1; 1967234, 2.

  1.5   Photocatalytic activity studies

  Photocatalytic degradation of methylene blue (MB) in the presence of catalysts 1 and 2 was investigated using a Cary 5000 UV-Vis-NIR spectrophotometer. The catalytic reactions were performed as follows: catalyst (50 mg) was dispersed in 100 mL aqueous solution of MB (10 mg·L^-1) under stirring for 30 min in the dark, aiming to ensure an adsorption-desorption equilibrium. The obtained mixture was then exposed to a continuous UV irradiation using an Hg lamp (150 W) for 150 min with continuous stirring. The reaction samples (5 mL) were taken out every 15 min, centrifuged, and then analyzed by UV-Vis spectrophotometry, monitoring an intensity decrease of the MB absorption band at 668 nm. A control experiment was also performed under the same reaction conditions, showing that no MB degradation took place in the absence of catalyst.

  2.   Results and discussion

  2.1   Description of the structures

  2.1.1   Structure of 1

  Asymmetric unit of 1 contains a Co1 atom, a μ₃-L^2- block, a 4, 4′-bipy moiety, and one lattice water molecule (Fig. 1). The six-coordinated Co1 center displays a distorted octahedral {CoN₂O₄} environment filled by four carboxylate O atoms from three individual μ₃-L^2- blocks and two N atoms from two different 4, 4′-bipy moieties. The lengths of the Co—O and Co—N bonds are 0.201 0(4)~0.223 3(4) and 0.214 8(4)~0.215 1(4) nm, respectively; these are within the normal values for related Co (Ⅱ) derivatives^{[1, 11, 13]}. In 1, the L^2- block acts as a μ₃-ligand, wherein the COO^- groups are bidentate (mode Ⅰ, Scheme 1). Two carboxylate groups of two μ₃-L^2- blocks link the adjacent Co (Ⅱ) centers into the dicobalt (Ⅱ) motifs (Fig. 2) with a Co…Co separation of 0.409 2(4) nm. Such motifs are further assembled, via the remaining COO^- groups of μ₃-L^2- blocks and 4, 4′-bipy moieties to a 2D sheet (Fig. 3).

  Figure 1

  

  Figure 1.  Drawing of asymmetric unit of complex 1 with 30% probability thermal ellipsoids

  Lattice water molecule and H atoms are omitted for clarity; Symmetry codes: A:-x, -y+1, -z+1; B: -x, -y+1, -z+2; C: x-1, y-1, z

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  Figure 2

  

  Figure 2.  Di-cobalt(Ⅱ) motif

  Symmetry code: A:-x, -y+1, -z+1

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  Figure 3

  

  Figure 3.  View of 2D sheet in complex 1 along b axis

  Symmetry codes: A:-x, -y+1, -z+1; B: x-1, y-1, z; C: x+1, y+1, z; D: -x, -y+1, -z+2

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  2.1.2   Structure of 2

  Asymmetric unit of 2 bears one Mn1 center, one μ-L^2- linker, one μ-4, 4′-bipy, two terminal water ligands and one lattice water molecule (Fig. 4). The Mn1 center is six-coordinated and reveals a distorted octahedral {MnN₂O₄} geometry. It is completed by two carboxylate O donors from two μ-L^2- blocks, two O atoms from two H₂O ligands, and two N donors from two independent 4, 4′-bipy ligands. The Mn—O (0.21 33(2)~0.219 8(2) nm) and Mn—N (0.229 0(3)~0.230 2(3) nm) bonds are within the standard values^{[6, 11]}. The L^2- block behaves as a bidentate μ-linker (Scheme 1, mode Ⅱ) that interconnects the adjacent Mn1 atoms to form a 1D metalorganic chain subunit with a Mn1…Mn1 separation of 0.519 8(3) nm (Fig. 5). Furthermore, such 1D chains are further extended by μ-4, 4′-bipy into a 2D sheet (Fig. 5). Complexes 1 and 2 were isolated under the same conditions, except for the type of metal (Ⅱ) chloride starting material (CoCl₂·6H₂O for 1 and MnCl₂· 4H₂O for 2). Hence, the structural difference between two products indicates that the assembly process is metal ion-dependent.

  Figure 4

  

  Figure 4.  Drawing of asymmetric unit of complex 2 with 30% probability thermal ellipsoids

  Lattice water molecule and H atoms are omitted for clarity; Symmetry codes: A: x, -y+1/2, z+1/2; B: x-1, y, z

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  Figure 5

  

  Figure 5.  View of 2D metal-organic sheet of 2 along b axis

  Symmetry codes: A: x, -y+1/2, z-1/2; B: x-1, y, z; C: x+1, y, z; D: x, -y+1/2, z+1/2

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  2.2   TGA for 1 and 2

  To determine the thermal stability of complexes 1 and 2, their thermal behaviors were investigated under nitrogen atmosphere by TGA. As shown in Fig. 6, TGA curve of complex 1 shows that there was a loss of one lattice water molecule between 43 and 102 ℃ (Obsd. 3.6%, Calcd. 3.9%); further heating above 302 ℃ led to a decomposition of the dehydrated sample. Complex 2 lost its two H₂O ligands and one lattice water molecule in a range of 103~156 ℃ (Obsd. 11.3%, Calcd. 11.0%), followed by the decomposition at 158 ℃.

  Figure 6

  

  Figure 6.  TGA curves of complexes 1 and 2

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  2.3   Photocatalytic activity for dye degradation

  To study the photocatalytic activity of 1 and 2, we selected MB as a model dye contaminant in wastewater. The obtained results (Fig. 7 and 8) indicated that the MB degradation efficiency attained 86.9% after 150 min in the presence of 2 that was the most active catalyst. For 1, the MB degradation efficiency was inferior, being 66.0%. Under similar conditions, blank test showed that the MB degradation efficiency was only 11.6% after 150 min. Besides, to evaluate the stability of complex 2 during the photocatalytic experiments, the catalyst recycling tests were performed (Fig. 9). The obtained results indicate that the complex 2 preserved its original catalytic activity even after four reaction cycles, showing only a slight decline of the MB degradation efficiency from 87% to 82%. Moreover, the chemical stability of 2 after photocatalytic experiments can be confirmed by the PXRD data of the recovered catalyst (Fig. 10), which well matched those of assynthesized sample. The results demonstrate that the photocatalytic activity depends on various factors, such as number of water ligands, coordination environment of metal centers, and optical band gap^[20-22].

  Figure 7

  

  Figure 7.  Photocatalytic degradation of MB solution under UV light using catalysts 1 and 2 and the blank experiment

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  Figure 8

  

  Figure 8.  Time-dependent UV-Vis spectra of the reaction mixtures in the course of MB photodegradation catalyzed by 1 and 2

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  Figure 9

  

  Figure 9.  Catalyst 2 recycling experiments in MB photodegradation

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  Figure 10

  

  Figure 10.  PXRD patterns for 2: simulated, before and after photocatalysis

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  3.   Conclusions

  In summary, we have successfully synthesized and characterized two new cobalt and manganese coordination polymers by using one dicarboxylate acid as ligand under hydrothermal condition. Complexes 1 and 2 possess two different 2D sheet structures. The structural diversity of complexes 1 and 2 is driven by the metal (Ⅱ) node. Besides, the photocatalytic properties were also investigated and discussed. The results show that such dicarboxylic acid can be used as a versatile multifunctional building block towards the generation of new coordination polymers.

  
  
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• 

  Scheme 1  Coordination modes of L^2- ligands in complexes 1 and 2

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  Figure 1  Drawing of asymmetric unit of complex 1 with 30% probability thermal ellipsoids

  Lattice water molecule and H atoms are omitted for clarity; Symmetry codes: A:-x, -y+1, -z+1; B: -x, -y+1, -z+2; C: x-1, y-1, z

  下载: 全尺寸图片 幻灯片
  

  Figure 2  Di-cobalt(Ⅱ) motif

  Symmetry code: A:-x, -y+1, -z+1

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  Figure 3  View of 2D sheet in complex 1 along b axis

  Symmetry codes: A:-x, -y+1, -z+1; B: x-1, y-1, z; C: x+1, y+1, z; D: -x, -y+1, -z+2

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  Figure 4  Drawing of asymmetric unit of complex 2 with 30% probability thermal ellipsoids

  Lattice water molecule and H atoms are omitted for clarity; Symmetry codes: A: x, -y+1/2, z+1/2; B: x-1, y, z

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  Figure 5  View of 2D metal-organic sheet of 2 along b axis

  Symmetry codes: A: x, -y+1/2, z-1/2; B: x-1, y, z; C: x+1, y, z; D: x, -y+1/2, z+1/2

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  Figure 6  TGA curves of complexes 1 and 2

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  Figure 7  Photocatalytic degradation of MB solution under UV light using catalysts 1 and 2 and the blank experiment

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  Figure 8  Time-dependent UV-Vis spectra of the reaction mixtures in the course of MB photodegradation catalyzed by 1 and 2

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  Figure 9  Catalyst 2 recycling experiments in MB photodegradation

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  Figure 10  PXRD patterns for 2: simulated, before and after photocatalysis

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  Table 1.  Crystal data and structure refinements for complexes 1 and 2

  Complex	1	2
  Chemical formula	C20H18CoN2O5S	C20H22MnN2O7S
  Formula weight	457.35	489.39
  Crystal system	Triclinic	Monoclinic
  Space group	P1	P21/c
  a / nm	0.962 02(11)	1.169 40(7)
  b / nm	1.033 02(9)	2.084 67(13)
  c / nm	1.167 18(12)	0.867 13(5)
  α / (°)	91.823(8)
  β / (°)	108.270(10)	100.881(5)
  γ / (°)	110.391(9)
  V / nm3	1.019 4(2)	2.075 9(2)
  Z	2	4
  F(000)	470	1 012
  θ range for data collection / (°)	3.432~25.046	3.330~25.047
  Limiting indices	-9 ≤ h ≤ 11, -12 ≤ k ≤ 12, -13 ≤ l ≤ 13	-12 ≤ h ≤ 13, -10 ≤ k ≤ 24, -10 ≤ l ≤ 5
  Reflection collected, unique (Rint)	6 536, 3 605 (0.057 0)	6 592, 3 666 (0.038 7)
  Dc / (g·cm-3)	1.490	1.566
  μ / mm-1	0.978	0.783
  Data, restraint, parameter	3 605, 0, 262	3 666, 0, 280
  Goodness-of-fit on F2	1.056	1.052
  Final R indices[I≥2σ(I)] R1, wR2	0.069 3, 0.108 9	0.047 9, 0.071 3
  R indices (all data) R1, wR2	0.163 2, 0.198 9	0.099 4, 0.117 8
  Largest diff. peak and hole / (e·nm-3)	918 and -650	376 and -389

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  Table 2.  Selected bond lengths (nm) and bond angles (°) for complexes 1 and 2

  1
  Co(1)—O(1)	0.201 0(4)	Co(1)—O(2)A	0.204 5(4)	Co(1)—O(3)B	0.223 3(4)
  Co(1)—O(4)B	0.217 1(4)	Co(1)—N(1)	0.215 1(4)	Co(1)—N(2)C	0.214 8(4)
  O(1)—Co(1)—O(2)A	119.64(18)	O(1)—Co(1)-N(2)C	91.44(17)	O(2)A—Co(1)—N(2)C	92.56(16)
  O(1)—Co(1)—N(1)	88.26(17)	O(2)A—Co(1)-N(1)	87.63(16)	N(1)—Co(1)—N(2)C	179.70(17)
  O(1)—Co(1)—O(4)B	149.45(17)	O(2)A—Co(1)-O(4)B	90.84(16)	N(2)C—Co(1)—O(4)B	89.12(17)
  N(1)—Co(1)—O(4)B	91.11(17)	O(1)—Co(1)-O(3)B	90.48(17)	O(2)A—Co(1)—O(3)B	149.38(18)
  N(2)C—Co(1)—O(3)B	91.98(17)	N(1)—Co(1)—O(3)B	87.97(17)	O(4)B—Co(1)—O(3)B	58.98(15)
  2
  Mn(1)—O(1)A	0.217 9(2)	Mn(1)—O(2)	0.213 3(2)	Mn(1)—O(5)	0.214 0(2)
  Mn(1)—O(6)	0.219 8(2)	Mn(1)—N(1)	0.230 2(3)	Mn(1)—N(2)B	0.229 0(3)
  O(2)—Mn(1)—O(5)	177.55(9)	O(2)—Mn(1)—O(1)A	81.85(9)	O(5)—Mn(1)—O(1)A	99.56(9)
  O(2)—Mn(1)—O(6)	94.18(9)	O(5)—Mn(1)—O(6)	84.59(9)	O(1)A—Mn(1)—O(6)	173.46(8)
  O(2)—Mn(1)—N(2)B	87.91(9)	O(5)-Mn(1)—N(2)B	90.15(9)	O(1)A—Mn(1)—N(2)B	87.24(9)
  O(6)—Mn(1)—N(2)B	97.85(10)	O(2)—Mn(1)—N(1)	92.29(9)	O(5)—Mn(1)—N(1)	89.66(9)
  O(1)A—Mn(1)—N(1)	91.93(10)	O(6)—Mn(1)—N(1)	83.01(10)	N(2)B—Mn(1)—N(1)	179.11(11)
  Symmetry codes: A: -x, -y+1, -z+1; B: -x, -y+1, -z+2; C: x-1, y-1, z for 1; A: x, -y+1/2, z+1/2; B: x-1, y, z for 2.

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  Table 3.  Hydrogen parameters of complexes 1 and 2

  Complex	D—H…A	d(D—H) / nm	d(H…A) / nm	d(D…A) / nm	∠DHA / (°)
  1	O(5)—H(1W)…O(3)A	0.085 0	0.203 3	0.288 3	178.91
  2	O(5)—H(1W)…O(7)B	0.082 0	0.193 9	0.271 9	158.61
  	O(5)—H(2W)…O(1)C	0.083 7	0.188 4	0.271 1	169.24
  	O(6)—H(4W)…O(3)D	0.082 0	0.182 3	0.263 6	170.87
  	O(7)—H(6W)…O(4)E	0.086 8	0.218 6	0.270 1	117.77
  Symmetry codes: A: -x, -y+1, -z+2 for 1; B: -x+1, -y+1, -z+1; C: x, y, z+1; D: -x, -y, -z+1; E: x+1, y+1, z for 2.

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