Synthesis, crystal structure, and properties of manganese/cobalt complexes based on 2,5-dibromoterephthalic acid ligands

Rui-Qin HUANG Zheng LIU Sheng WANG Cai-Li YU Run-Zhi WEI Qun TANG

Citation:  Rui-Qin HUANG, Zheng LIU, Sheng WANG, Cai-Li YU, Run-Zhi WEI, Qun TANG. Synthesis, crystal structure, and properties of manganese/cobalt complexes based on 2,5-dibromoterephthalic acid ligands[J]. Chinese Journal of Inorganic Chemistry, 2023, 39(1): 159-167. doi: 10.11862/CJIC.2022.277 shu

基于2,5-二溴对苯二甲酸配体的锰/钴配合物的合成、晶体结构及性质

    通讯作者: 刘峥, lisa4.6@163.com
    唐群, tangq@glut.edu.cn
  • 基金项目:

    国家自然科学基金 21501033

    广西自然科学基金 2020GXNSFAA159016

摘要: 将有机物2,5-二溴对苯二甲酸(H2L1)作为主配体,2,2'-联吡啶(L2)、1,10-菲咯啉(L3)分别作为辅配体,通过溶剂热法与一水硫酸锰、六水合硝酸钴分别反应得到配合物[Mn2(L1)2(L2)2(H2O)2]n(1)和[Co2(L1)2(L3)2(H2O)2]n(2)。通过单晶X射线衍射法、荧光光谱、热重分析等测试手段对这2种配合物进行分析研究。结果表明配合物1是由Mn2+配位连接L12-与L2形成无限延伸的二维网络状结构,各层在分子间氢键和π-π堆积作用下形成了三维网络状结构。配合物2是由Co2+配位连接L12-和L3形成的无限延伸的二维网络状结构,各层在分子间氢键和π-π堆积作用下形成三维网络状结构。且这2种配合物均具有良好的荧光性和热稳定性,配合物12的最大发射波长分别为355和365 nm。

English

  • Coordination polymers are usually obtained from multi-dentate organic ligands as building templates or assembled from connecting rods with metal ions as nodes[1-2]. Among them, multi-dentate nitrogen-containing ligands, multi-dentate carboxylic acid ligands, and multi-dentate pyridine carboxylic acid ligands are the preferred ligands for the self-assembly of organic ligands[3]. The complexes have potential applications in the fields of catalysis, ion recognition and antioxidation, electrochemistry, etc., and are one of the research hot spots in organometallic chemistry and coordination chemistry[4-7]. The synthesis of coordination polymers using ligands containing carboxyl groups is more common. In addition to structural stability, due to the multiple coordination modes and bridging modes of carboxyl-containing ligands, the complexes are easy to obtain topological diversity and excellent properties. Ligands containing nitrogen or oxygen groups can be re-introduced during the construction of the complexes to increase the active sites, form more coordination modes, diversify the pore channels and improve their luminescence performance[8-10].

    Among them, terephthalic acid-like ligands are one of the important ligands for the preparation of functional MOFs materials, because having bifunctional groups in the para-position provides the possibility of forming polymer chains of mono-and heterometallic two-or three-dimensional coordination compounds, which can be used as one of the ligands for the synthesis of bidentate, tridentate or tetradentate chelate complexes based on the characteristics of terephthalate ion structure. The presence of empty d orbitals in transition metals allows the use of hybrid orbitals to accept electrons, resulting in stable structures of 16 or 18 electrons, and thus are widely used for the preparation of complexes[11-14].

    Our group chose 2,5-dibromoterephthalic acid (H2L1) as the primary ligand and 2,2'-bipyridine (L2) and 1,10-phenanthroline (L3) as the secondary ligands and obtained complexes [Mn2(L1)2(L 2)2(H2O)2]n (1) and [Co2(L1)2(L3)2(H2O)2]n (2). The structures were characterized by single-crystal X-ray diffraction and IR spectroscopy, and their thermal stability and fluorescence properties were also investigated.

    H2L1 (Purity: 97%) was purchased from Shanghai Maclean Reagent Company; L2 (Purity: 99%), L3 (Purity: 99%), N, N-dimethylformamide (DMF, AR), manganese sulfate monohydrate (AR) and cobalt nitrate hexahydrate (AR) were purchased from Aladdin Reagent (Shanghai) Company.

    An Agilent Technologies G8910A single-crystal diffractometer was used to determine the crystal structure. A Perkin-Elmer 240Q elemental analyzer was used to determine the elemental contents (C, N, H). A Shimadzu FTIR-8400 FTIR spectrometer (with KBr compression) was used to measure the IR spectra of the complexes. A UV-5500PC double-beam UV-Vis spectrophotometer was used to determine the UV-Vis spectra of the complexes. An EDXRF-type fluorescence spectrometer was used to determine the fluorescence spectra of the complexes. An SDT-Q600 type synchronous TG/DTG analyzer was used for thermogravimetric analysis (TGA).

    DMF (6 mL), H2O (4 mL), 0.2 mmol (0.064 8 g) of H2L1, 0.2 mmol (0.031 2 g) of L2, and 0.2 mmol (0.057 5 g) of manganese sulphate monohydrate were placed in a beaker, stirred magnetically for 30 min and then placed in a reaction kettle. The reaction was carried out in an oven at 90 ℃ for 3 d, then cooled down to 50 ℃ at a rate of 10 ℃·h-1 for 6 h and then reduced to room temperature. Massive yellow crystals of complex 1 (0.014 7 g) were obtained with a yield of 43.7% (based on Mn). Elemental analysis Calcd. for C18H12Br2MnN2O5 (%): C, 39.20; N, 5.08; H, 2.18. Found(%): C, 39.52; N, 4.95; H, 2.11.

    Complex 2 was synthesized in a similar way to that of complex 1, using cobalt nitrate hexahydrate (0.058 2 g, 0.2 mmol) reacted with H2L1 (0.064 8 g, 0.2 mmol) and L3 (0.036 0 g, 0.2 mmol). The reaction gave 0.029 7 g of red massive crystals in 51.2% yield (based on Co). Elemental analysis Calcd. for C20H12Br2CoN2O5 (%): C, 41.45; N, 4.84; H, 2.07. Found(%): C, 41.08; N, 4.75; H, 2.01.

    Crystals with the sizes of 0.18 mm×0.16 mm×0.15 mm (1) and 0.19 mm×0.17 mm×0.15 mm (2) were selected and diffraction point data were collected using an Agilent Technologies G8910A single-crystal X-ray diffractometer with Mo radiation (λ=0.071 073 nm) at a temperature of 293(2) K, using φ-ω scan[15]. The raw data were reduced using the CryAlisPro program and all data were subjected to Lp factor correction and empirical absorption correction. The coarse structure was solved using the direct method in SHLEXS-97, and then the full matrix least-squares refinement of the nonhydrogen atomic coordinates and their anisotropic temperature factors was performed using the SHLEXL-97 program. All hydrogen atom coordinates were obtained using theoretical hydrogenation. The relevant crystallographic data are listed in Table 1 and the main bond lengths and bond angles are listed in Table 2.

    Table 1

    Table 1.  Crystallographic data for complexes 1 and 2
    下载: 导出CSV
    Parameter 1 2
    Empirical formula C18H12Br2MnN2O5 C20H12Br2CoN2O5
    Formula weight 551.04 579.07
    Crystal system Triclinic Triclinic
    Space group P1 P1
    a/nm 0.963 09(4) 0.958 91(3)
    b/nm 1.054 16(3) 1.064 44(4)
    c/nm 1.066 69(5) 1.076 36(3)
    α/(°) 109.841(4) 111.686(3)
    β/(°) 109.098(4) 92.367(3)
    γ/(°) 90.811(3) 108.351(3)
    V/nm3 0.953 01(7) 0.953 36(6)
    F(000) 538 566
    Z 2 2
    Dc/(g·cm-3) 1.920 2.017
    μ/mm-1 10.85 5.13
    θ range/(°) 4.5-77.3 2.1-29.3
    Reflection measured, independent 10 795, 4 052 9 861, 4 161
    Observed reflection [I≥2σ(I)] 3 670 3 220
    Rint 0.028 0.027
    R1 [I≥2σ(I)] 0.033 0.033
    wR2 (all data) 0.087 0.074
    GOF 1.04 1.05

    Table 2

    Table 2.  Selected bond lengths (nm) and angles (°) for complexes 1 and 2
    下载: 导出CSV
    1
    Mn1—O1 0.221 89(19) Mn1—O1 0.221 01(17) Mn1—O3 0.211 7(2)
    Mn1—O5 0.220 9(2) Mn1—N1 0.224 7(2) Mn1—N2 0.223 8(2)
    O1—Mn1 0.221 01(17)
    O1—Mn1—O1 77.28(7) N1—Mn1—O1 97.79(8) O1—Mn1—N1 95.38(8)
    O1—Mn1—N2 100.18(7) N2—Mn1—O1 170.69(8) O3—Mn1—O1 90.37(8)
    O3—Mn1—O1 93.92(8) O3—Mn1—O5 91.21(10) O3—Mn1—N1 167.85(10)
    O3—Mn1—N2 95.07(9) O5—Mn1—O1 168.84(8) O5—Mn1—O1 91.58(8)
    O5—Mn1—N1 85.22(9) O5—Mn1—N2 90.69(9) N2—Mn1—N1 73.41(9)
    2
    Co1—N1 0.212 0(2) Co1—N2 0.212 3(2) Co1—O1 0.212 34(18)
    Co1—O1 0.213 17(18) Co1—O3 0.207 4(2) Co1—O5 0.213 6(2)
    N1—Co1—N2 78.78(10) N1—Co1—O1 97.66(8) N1—Co1—O1 98.12(8)
    N1—Co1—O5 83.22(9) N2—Co1—O1 175.06(8) N2—Co1—O5 90.84(8)
    O1—Co1—N2 98.76(8) O1—Co1—O1 77.75(7) O1—Co1—O5 170.36(8)
    O5—Co1—O1 92.62(8) O3—Co1—N1 169.90(9) O3—Co1—N2 93.38(9)
    O3—Co1—O1 89.77(8) O3—Co1—O1 90.12(8) O3—Co1—O5 90.61(9)
    C1—N1—C12 118.0(3) C1—N1—Co1 128.7(2) C12—N1—Co1 112.7(2)
    C10—N2—C11 117.7(3) C10—N2—Co1 129.0(2) C11—N2—Co1 113.09(19)
    C13—O1—Co1 132.86(18) C13—O1—Co1 124.55(17) Co1—O1—Co1 102.26(7)
    C17—O3—Co1 130.4(2) Co1—O5—H11 109.8 Co1—O5—H12 110.2
    Symmetry codes: -x, -y+1, -z+1; -x+1, -y+1, -z+1; -x, -y+2, -z+2 for 1; -x+1, -y+1, -z+1; -x, -y+2, -z+2; -x, -y+1, -z+1 for 2.
    2.1.1   Crystal structure of complex 1

    As shown in Fig. 1a, each asymmetric unit of complex 1 consists of two Mn2+ ions, two L12- ions, two L2 molecules, and two coordinated water molecules. In the coordination environment of Mn1, O5 is an oxygen atom from the coordinated water molecule, O1 and O1 are both oxygen atoms from the carboxyl group on L12-, and N1 and N2 are nitrogen atoms from L2, where the sum of the bond angles formed by O1, O1, O5, and N2 with the central Mn1 ion is 359.74°, which is close to the ideal angle (360°), indicating that these four coordination atoms are in the equatorial plane of the tetragonal bipyramidal cone and have good coplanarity. As shown in Fig. 1b, the carboxyl oxygen atom O3 on L12- and N1 on L2 are located in axial positions with axial bond angle O3—Mn1—N1 (167.85(10)°), forming a distorted [MnO4N2] tetragonal bipyramidal geometry. The coordination environment of Mn1 is the same as that of Mn1, Mn—O (0.220 9(2)-0.221 89(19) nm), Mn—N (0.223 8(2)-0.224 7(2) nm) are in the normal range of bond lengths, the bond angles of O—Mn—O are in a range of 77.28(7)°-168.84(8)°, the bond angles of N—Mn—O are in a range of 85.22(9)°-170.69(8)°, and the bond angle of N—Mn—N is 73.41(9)°, all within the normal range[16].

    Figure 1

    Figure 1.  Crystal structure of complex 1: (a) ellipsoid diagram with 30% probability level; (b) coordination polyhedron diagram; (c) 3D stacked diagram

    Symmetry codes: -x, -y+1, -z+1; -x+1, -y+1, -z+1; -x, -y+2, -z+2

    With Mn2+ as the metal node, L12- and L2 as the coordination linkages, the Mn1 and Mn1 ions are connected by carboxyl oxygen atoms O1 and O1 on L12-, thus forming a fully symmetric bidentate chelate coordination structural unit. The intermolecular linkages through L12- bridges form an infinitely extended 2D network-like structure. As shown in Fig. 1c, a 3D network-like structure is formed between adjacent layers through intermolecular hydrogen bonding and π-π stacking. The π-π stacking is between the Cg(1) ring (a ring consisting of N2 -C5 -C4 -C3 -C2 -C1) and the Cg(2) ring (a ring consisting of C12-C14-C13-C12-C14-C13) between layer and layer molecules, where the distance from the Cg(1) ring to the center of the Cg(2) ring is 0.354 6 nm and the inter-ring dihedral angle is 5.511°. The pore size of complex 1 was calculated by the tools module of Diamond software as 0.83 nm × 2.05 nm.

    2.1.2   Crystal structure of complex 2

    As shown in Fig. 2a, each asymmetric unit of complex 2 consists of two Co2+ ions, two L12- ions, two L3 molecules, and two coordinated water molecules. In the coordination environment of Co1, O5 comes from the water molecule, O3, O1 and O1 are the carboxyl oxygen atoms on L12-, and N1 and N2 come from L3. As shown in Fig. 2b, the carboxyl oxygen atom O3 on L12-and N1 on L3 are located in the axial position with axial bond angle O3—Co1—N1 (169.90(9)°), forming a distorted [CoO4N2] tetragonal bipyramidal geometry. The coordination environment of Co1 is the same as that of Co1, Co—O (0.207 4(2) to 0.213 6(2) nm), Co—N (0.212 0(2) to 0.212 3(2) nm) are in the normal range of bond lengths, the bond angles of O—Co—O are in a range of 77.75(7)°-170.36(8)°, the bond angles of N—Co—O are in a range of 83.22(9)°-175.06(8)°, and the bond angle of N—Co—N is 78.80(10)°, all within the normal range[17].

    Figure 2

    Figure 2.  Crystal structure of complex 2: (a) ellipsoid diagram with 30% probability level; (b) coordination polyhedron diagram; (c) 3D stacked diagram

    Symmetry codes: -x, -y+1; -x+1, -y+1, -z+1; -x, -y+2, -z+2

    With Co2+ as the metal node, L12- and L3 as the coordination linkage, the Co1 and Co1 ions are connected by carboxyl oxygen atoms O1 and O1 on L12-, thus forming the coordination structural unit of the bidentate chelate. The intermolecular linkages via L12-bridges form an infinitely extended 2D network-like structure. As shown in Fig. 2c, the adjacent layers are stacked to form a 3D network-like structure through O—H⋯O intermolecular hydrogen bonding and π-π stacking. The π-π stacking is between the Cg(1) ring consisting of N2-C10-C9-C8-C7-C11 and the Cg(2) ring consisting of C14-C15-C16-C14-C15-C16 between layer and layer molecules. The distance from the Cg(1) ring to the center of the Cg(2) ring is 0.355 8 nm and the dihedral angle between the two rings is 11. 709°. The pore size of complex 2 was calculated by the tools module of Diamond software, giving 2.07 nm × 1.52 nm.

    The IR spectra of ligands H2L1, L2, L3, and complexes 1 and 2 were measured in a range of 4 000-400 cm-1 using a Shimadzu FTIR-8400 infrared spectrometer (Fig. 3). As shown in Fig. 3a, the O—H stretching vibration peak for the carboxyl group of H2L1 appeared at 3 438 cm-1, while this peak moved to 3 408 cm-1 for complex 1. The C=O stretching vibration absorption peak for the carboxyl group of H2L1 appeared at 1 709 cm-1, and this peak appeared at 1 609 cm-1 for complex 1. The O—H bending vibration absorption peak of H2L1 at 900 cm-1 did not move after the formation of complex 1. These indicate that the manganese ion is coordinated with the carboxyl group in H2L1. L2 showed a C=N bending vibration absorption peak at 1 569 cm-1, which moved to 1 609 cm-1 for complex 1; the presence of the Mn—N absorption peak at 646 cm-1 for complex 1 indicates that the nitrogen atom of L2 is coordinated to the manganese ion[18].

    Figure 3

    Figure 3.  IR spectra of complexes 1, 2, and the ligands

    The IR spectrum of complex 2 is shown in Fig. 3b. The O—H stretching vibration peaks for the carboxyl group of H2L1 shown at 3 438 and 3 093 cm-1 were shown again at both 3 403 and 3 051 cm-1 for complex 2, which indicates that the carboxyl group in H2L1 is coordinated to the cobalt ion. The C=N stretching vibration peak for L3 at 1 587 cm-1 shifted to 1 608 cm-1 after the formation of complex 2; the Co—N absorption peak shown at 534 cm-1 for complex 2 indicates that the nitrogen atom of L3 undergoes coordination with the cobalt ion[19-20].

    The UV-Vis and fluorescence spectra of complexes 1 and 2 and ligands H2L1, L2, and L3 were measureds at room temperature. The samples were dissolved in DMF at a concentration of 10 μmol·L-1 as a reference solution. The UV-Vis spectra of complexes 1 and 2 and ligands H2L1, L2, and L3 are shown in Fig. 4. Ligands H2L1, L2, and L3 and their complexes all showed an absorption peak around 270 nm, which can be attributed to the B-band where π-π* leap occurs on the intramolecular heterocyclic ring according to the molecular structure analysis.

    Figure 4

    Figure 4.  UV-Vis spectra of complexes 1, 2, and the ligands

    The fluorescence emission spectra of complexes 1 and 2 and their ligands are shown in Fig. 5. The structures of ligands H2L1, L2, L3, and complexes 1 and 2 all contain heterocyclic conjugated π-bonds and are prone to fluorescence. The wavelengths of the maximum emission peaks of ligands H2L1, L2, and L3 were 348, 341, and 362 nm (λex=305, 265, 289 nm, respectively), which are attributed to π-π* electron leap; while the wavelengths of the maximum emission peaks of complexes 1 and 2 were 355 and 365 nm (λex=322, 319 nm, respectively), which were both red-shifted compared to the ligands. This may be because the energy level of the HOMO of the complex decreases and the energy level difference between the HOMO and the LUMO becomes larger after the coordination of the ligand with the metal ion; while the metallization effect elevates the HOMO energy level of the complex and the energy level difference between the HOMO and the LUMO decreases[21]. The maximum emission wavelengths of complexes 1 and 2 were extremely similar, indicating that the fluorescence properties of both complexes are mainly based on the luminescence of L12-itself in them. The main ligand H2L1 had a maximum excitation wavelength of 305 nm with a Stokes shift (Δλ) of 43 nm; the maximum excitation wavelength of complex 1 was 322 nm with a Δλ of 33 nm; the maximum excitation wavelength of complex 2 was 319 nm with a Δλ of 46 nm. Compared with the main ligand H2L1, the Stokes shifts of complexes 1 and 2 were smaller and the fluorescence efficiency was higher.

    Figure 5

    Figure 5.  Fluorescence emission spectra of complexes 1, 2, and the ligands

    The TG and differential thermogravimetry (DTG) curves of complex 1 are shown in Fig. 6a. Complex 1 remained stable until 290 ℃, after which the skeleton began to collapse continuously as the temperature increased until about 440 ℃, when the skeleton collapsed completely, with a final residual rate of 12.91%. According to the common sense of coordination, the residue might be MnO, and the calculated value was 12.87%, which was consistent with the actual residual rate. As shown in Fig. 6b, complex 2 hardly decomposed before 130 ℃, and the first weight loss of 2. 05% occurred from 130 to 175 ℃, which is attributed to the decomposition of the coordinated water molecule and was consistent with the calculated value of 3.10%. After that, with the increase in temperature, the skeleton of the complex collapsed continuously, and at about 596 ℃, the skeleton collapsed completely. The final residual rate was 27.27%, and according to the common sense of coordination, the residue might be CoO (Calcd. 12.94%). The residual rate was greater than the calculated value, indicating that complex 2 was protected by N2. The thermal decomposition yielded N-doped carbon material, which produced the carbon accumulation effect. In summary, both two complexes have certain thermal stability.

    Figure 6

    Figure 6.  TG and DTG curves of complexes 1 and 2

    The organic 2,5-dibromoterephthalic acid was used as the primary ligand and 2,2'-bipyridine and 1,10-phenanthroline as the secondary ligands, and complexes [Mn2(L1)2(L2)2(H2O)2]n (1) and [Co2(L1)2(L 3)2(H2O)2]n (2) were synthesized with manganese sulfate monohydrate and cobalt nitrate hexahydrate, respectively, using a solvothermal method. The crystal structure analysis shows that complex 1 is an infinitely extended 2D network-like structure formed by L12- and L2 coordination linking Mn2+ ion, and each layer forms a 3D network-like structure under intermolecular hydrogen bonding and π-π stacking. Complex 2 is an infinitely extended 2D network-like structure formed by L12- and L3 coordination linking Co2+ ion, and the layers are stacked under intermolecular hydrogen bonding and π-π stacking to form a 3D network-like structure. Both 1 and 2 have good fluorescence properties and thermal stability.


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  • Figure 1  Crystal structure of complex 1: (a) ellipsoid diagram with 30% probability level; (b) coordination polyhedron diagram; (c) 3D stacked diagram

    Symmetry codes: -x, -y+1, -z+1; -x+1, -y+1, -z+1; -x, -y+2, -z+2

    Figure 2  Crystal structure of complex 2: (a) ellipsoid diagram with 30% probability level; (b) coordination polyhedron diagram; (c) 3D stacked diagram

    Symmetry codes: -x, -y+1; -x+1, -y+1, -z+1; -x, -y+2, -z+2

    Figure 3  IR spectra of complexes 1, 2, and the ligands

    Figure 4  UV-Vis spectra of complexes 1, 2, and the ligands

    Figure 5  Fluorescence emission spectra of complexes 1, 2, and the ligands

    Figure 6  TG and DTG curves of complexes 1 and 2

    Table 1.  Crystallographic data for complexes 1 and 2

    Parameter 1 2
    Empirical formula C18H12Br2MnN2O5 C20H12Br2CoN2O5
    Formula weight 551.04 579.07
    Crystal system Triclinic Triclinic
    Space group P1 P1
    a/nm 0.963 09(4) 0.958 91(3)
    b/nm 1.054 16(3) 1.064 44(4)
    c/nm 1.066 69(5) 1.076 36(3)
    α/(°) 109.841(4) 111.686(3)
    β/(°) 109.098(4) 92.367(3)
    γ/(°) 90.811(3) 108.351(3)
    V/nm3 0.953 01(7) 0.953 36(6)
    F(000) 538 566
    Z 2 2
    Dc/(g·cm-3) 1.920 2.017
    μ/mm-1 10.85 5.13
    θ range/(°) 4.5-77.3 2.1-29.3
    Reflection measured, independent 10 795, 4 052 9 861, 4 161
    Observed reflection [I≥2σ(I)] 3 670 3 220
    Rint 0.028 0.027
    R1 [I≥2σ(I)] 0.033 0.033
    wR2 (all data) 0.087 0.074
    GOF 1.04 1.05
    下载: 导出CSV

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

    1
    Mn1—O1 0.221 89(19) Mn1—O1 0.221 01(17) Mn1—O3 0.211 7(2)
    Mn1—O5 0.220 9(2) Mn1—N1 0.224 7(2) Mn1—N2 0.223 8(2)
    O1—Mn1 0.221 01(17)
    O1—Mn1—O1 77.28(7) N1—Mn1—O1 97.79(8) O1—Mn1—N1 95.38(8)
    O1—Mn1—N2 100.18(7) N2—Mn1—O1 170.69(8) O3—Mn1—O1 90.37(8)
    O3—Mn1—O1 93.92(8) O3—Mn1—O5 91.21(10) O3—Mn1—N1 167.85(10)
    O3—Mn1—N2 95.07(9) O5—Mn1—O1 168.84(8) O5—Mn1—O1 91.58(8)
    O5—Mn1—N1 85.22(9) O5—Mn1—N2 90.69(9) N2—Mn1—N1 73.41(9)
    2
    Co1—N1 0.212 0(2) Co1—N2 0.212 3(2) Co1—O1 0.212 34(18)
    Co1—O1 0.213 17(18) Co1—O3 0.207 4(2) Co1—O5 0.213 6(2)
    N1—Co1—N2 78.78(10) N1—Co1—O1 97.66(8) N1—Co1—O1 98.12(8)
    N1—Co1—O5 83.22(9) N2—Co1—O1 175.06(8) N2—Co1—O5 90.84(8)
    O1—Co1—N2 98.76(8) O1—Co1—O1 77.75(7) O1—Co1—O5 170.36(8)
    O5—Co1—O1 92.62(8) O3—Co1—N1 169.90(9) O3—Co1—N2 93.38(9)
    O3—Co1—O1 89.77(8) O3—Co1—O1 90.12(8) O3—Co1—O5 90.61(9)
    C1—N1—C12 118.0(3) C1—N1—Co1 128.7(2) C12—N1—Co1 112.7(2)
    C10—N2—C11 117.7(3) C10—N2—Co1 129.0(2) C11—N2—Co1 113.09(19)
    C13—O1—Co1 132.86(18) C13—O1—Co1 124.55(17) Co1—O1—Co1 102.26(7)
    C17—O3—Co1 130.4(2) Co1—O5—H11 109.8 Co1—O5—H12 110.2
    Symmetry codes: -x, -y+1, -z+1; -x+1, -y+1, -z+1; -x, -y+2, -z+2 for 1; -x+1, -y+1, -z+1; -x, -y+2, -z+2; -x, -y+1, -z+1 for 2.
    下载: 导出CSV
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  • 发布日期:  2023-01-10
  • 收稿日期:  2022-08-08
  • 修回日期:  2022-11-03
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