Syntheses, Crystal Structures, and Photocatalytic Properties of Cobalt(Ⅱ) and Manganese(Ⅱ) Coordination Polymers Assembled from 4-((Carboxymethyl)thio)benzoic Acid

Yu LI Hui-Feng JIANG Xiao-Ling CHEN Wen-Da QIU

Citation:  Yu LI, Hui-Feng JIANG, Xiao-Ling CHEN, Wen-Da QIU. Syntheses, Crystal Structures, and Photocatalytic Properties of Cobalt(Ⅱ) and Manganese(Ⅱ) Coordination Polymers Assembled from 4-((Carboxymethyl)thio)benzoic Acid[J]. Chinese Journal of Inorganic Chemistry, 2021, 37(2): 361-367. doi: 10.11862/CJIC.2021.028 shu

由含硫二羧酸配体构筑的钴(Ⅱ)和锰(Ⅱ)配位聚合物的合成、晶体结构及光催化性质

    通讯作者: 成晓玲, ggcxl@163.com
    邱文达, qiuwd123@163.com
  • 基金项目:

    广东省高等职业院校珠江学者岗位计划资助项目 2015

    广东省高等职业院校珠江学者岗位计划资助项目 2018

    广东省高校创新团队项目 2017GKCXTD001

    广州市科技计划项目 201904010381

    广东省高校特色创新类项目 2019GKTSCX010

    广东省大学生科技创新培育专项 pdjh2019b0690

摘要: 采用水热方法,用含硫二羧酸配体4-((carboxymethyl)thio)benzoic acid(H2L)和4,4'-联吡啶(4,4'-bipy)分别与CoCl2·6H2O和MnCl2·4H2O反应,合成了2个二维配位聚合物{[Co(μ3-L)(4,4'-bipy)]·H2O}n1)和{[Mn(μ-L)(4,4'-bipy)(H2O)2]·H2O}n2),并对其结构和光催化性质进行了研究。结构分析结果表明2个配合物分别属于三斜和单斜晶系、P1P21/c空间群。配合物12分别具有基于双核Co和一维Mn链单元的二维层结构。配合物12具有不同的二维层结构是由于采用了不同的金属离子。另外,研究了2个配合物对有机染料亚甲基蓝的光催化降解性能,结果表明配合物2可以高效地降解亚甲基蓝。

English

  • 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 L2- ligands in complexes 1 and 2

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

    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 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°.

    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.

    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.

    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
    下载: 导出CSV
    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
    下载: 导出CSV
    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
    下载: 导出CSV
    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.

    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.

    2.1.1   Structure of 1

    Asymmetric unit of 1 contains a Co1 atom, a μ3-L2- 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-L2- 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 L2- block acts as a μ3-ligand, wherein the COO- groups are bidentate (mode Ⅰ, Scheme 1). Two carboxylate groups of two μ3-L2- 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-L2- 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

    Figure 2

    Figure 2.  Di-cobalt(Ⅱ) motif

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

    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

    2.1.2   Structure of 2

    Asymmetric unit of 2 bears one Mn1 center, one μ-L2- 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-L2- 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 L2- 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

    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

    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

    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

    Figure 8

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

    Figure 9

    Figure 9.  Catalyst 2 recycling experiments in MB photodegradation

    Figure 10

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

    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 L2- ligands in complexes 1 and 2

    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

    Figure 2  Di-cobalt(Ⅱ) motif

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

    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

    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

    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

    Figure 6  TGA curves of complexes 1 and 2

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

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

    Figure 9  Catalyst 2 recycling experiments in MB photodegradation

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

    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
    下载: 导出CSV

    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.
    下载: 导出CSV

    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.
    下载: 导出CSV
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  • 发布日期:  2021-02-10
  • 收稿日期:  2020-06-19
  • 修回日期:  2020-10-28
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