English

• The design and synthesis of coordination polymers have become the subjects of extensive investigation owing to the intriguing structures and functional properties, such as gas separation, catalysis, sensing, luminescence and magnetism^[1-8]. The applications of such functional coordination polymers largely depend on the metal ions, organic ligands, solvent systems, temperatures, and pH values^[9-14].

  In this context, semi-rigid polycarboxylate ligands have been extensively utilized to synthesize various functional 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, which leads to higher dimensional frameworks^{[10, 12, 15-19]}.

  In this context, we selected 3, 3′, 4, 5′-diphenyl ether tetracarboxylic acid (H₄L) as an organic linker owing to the following features: (1) it can twist and rotate freely to generate different angles between the two phenyl planes via the C-O_ether-C bond to furnish a subtle conformational adaptation; (2) it has nine potential coordination sites (eight carboxylate O donors and one O_ether donor), which can lead to diverse coordination patterns and high dimensionalities, especially when acting as a multiply bridging block; (3) this acid block remains poorly used for the generation of coordination polymers. Given these features, the main objective of the present study consisted in the exploration of H₄L as a novel ether-bridged tetracarboxylate block for the assembly of diverse coordination polymers.

  In this work, we report the syntheses, crystal structures, luminescent and magnetic properties of two Mn(Ⅱ) and Zn(Ⅱ) coordination polymers constructed from the ether-bridged tetracarboxylate 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. Excitation and emission spectra were recorded on an Edinburgh FLS920 fluorescence spectrometer using the solid samples at room temperature. Magnetic susceptibility data were collected in the 2~300 K temperature range on a Quantum Design SQUID Magnetometer MPMS XL-7 with a field of 0.1 T. A correction was made for the diamagnetic contribution prior to data analysis.

  1.2   Synthesis of {[Mn₂(μ₆-L)(phen)₂]·5H₂O}_n (1)

  A mixture of MnCl₂·4H₂O (0.040 g, 0.20 mmol), H₄L (0.035 g, 0.10 mmol), phen (0.040 g, 0.20 mmol), NaOH (0.016 g, 0.40 mmol) and H₂O (10 mL) was stirred at room temperature for 15 min, and then sealed in a 25 mL Teflon-lined stainless steel vessel, and heated at 160 ℃ for 3 days, followed by cooling to room temperature at a rate of 10 ℃·h^-1. Yellow block-shaped crystals of 1 were isolated manually, and washed with distilled water. Yield: 54% (based on H₄L). Anal. Calcd. for C₄₀H₃₂Mn₂N₄O₁₄(%): C 53.23, H 3.57, N 6.21; Found(%): C 53.36, H 3.58, N 6.17. IR (KBr, cm^-1): 3 389w, 3 066w, 1 610m, 1 565s, 1 515m, 1 448w, 1 427m, 1 381s, 1 258w, 1 220w, 1 142w, 1 103 w, 1 063w, 980w, 847m, 778w, 724m, 634w, 545w.

  1.3   Synthesis of {[Zn₂(μ₇-L)(py)]·H₂O}_n (2)

  A mixture of ZnCl₂ (0.027 g, 0.20 mmol), H₄L (0.035 g, 0.10 mmol), py (0.50 mL, 6.30 mmol), and H₂O (10 mL) was stirred at room temperature for 15 min, and then sealed in a 25 mL Teflon-lined stainless steel vessel, and heated at 160 ℃ for 3 days, followed by cooling to room temperature at a rate of 10 ℃·h^-1. Colorless block-shaped crystals of 2 were isolated manually, and washed with distilled water. Yield: 50% (based on H₄L). Anal. Calcd. for C₂₁H₁₃Zn₂ NO₁₀(%): C 44.24, H 2.30, N 2.46; Found(%): C 44.03, H 2.29, N 2.47. IR (KBr, cm^-1): 3 562w, 3 495w, 3 076w, 1 630s, 1 571s, 1 448m, 1 386s, 1 298w, 1 265m, 1 220 w, 1 147w, 1 103w, 1 069w, 1 047w, 985w, 935w, 901w, 851w, 834w, 795w, 767w, 718w, 662w, 644w, 584w, 534w.

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

  1.4   Structure determinations

  Two single crystals with dimensions of 0.25 mm×0.20 mm×0.19 mm (1) and 0.26 mm×0.24 mm×0.23 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^[20]. All non-hydrogen atoms were refined anisotropically. All the hydrogen atoms were positioned geometrically and refined using a riding model. Disordered solvent molecules in 1 were removed using the SQUEEZE routine in PLATON^[21]. The number of solvent water molecules was obtained on the basis of elemental and thermogravimetric analyses. 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 complex 2 are given in Table 3.

  Table 1

  

  Table 1.  Crystal data for complexes 1 and 2

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  Complex	1	2
  Chemical formula	C40H32Mn2N4O14	C21H13Zn2NO10
  Molecular weight	902.49	570.06
  Crystal system	Triclinic	Monoclinic
  Space group	P1	I2/a
  a / nm	1.087 55(9)	1.785 54(8)
  b / nm	1.182 56(11)	1.319 04(4)
  c / nm	1.420 46(11)	1.801 75(6)
  α / (°)	75.404(7)
  β / (°)	88.089(7)	92.856(3)
  γ / (°)	75.299(8)
  V / nm3	1.709 1(3)	4.238 2(3)
  Z	2	8
  F(000)	824	2 288
  θ range for data collection	3.428~25.048	3.464~25.048
  Limiting indices	-12 ≤ h≤ 9, -14 ≤ k ≤ 13, -15 ≤ l ≤ 16	-20 ≤ h ≤ 21, -15 ≤ k ≤ 11, -21 ≤ l ≤ 20
  Reflection collected, unique (Rint)	10 937, 6 032 (0.061 7)	13 704, 3 752 (0.040 9)
  Dc / (g·cm-3)	1.579	1.787
  μ / mm-1	0.806	2.324
  Data, restraint, parameter	6 032, 0, 496	3 752, 0, 307
  Goodness-of-fit on F2	0.961	1.048
  Final R indices [I≥2σ(I)] R1, wR2	0.072 1, 0.157 2	0.042 1, 0.103 7
  R indices (all data) R1, wR2	0.121 0, 0.183 6	0.056 1, 0.115 7
  Largest diff. peak and hole / (e·nm-3)	958 and -719	1 260 and -552

  Table 2

  

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

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  1
  Mn(1)-O(1)	0.214 7(4)	Mn(1)-O(6)A	0.205 8(4)	Mn(1)-O(8)B	0.203 4(4)
  Mn(1)-N(1)	0.222 3(4)	Mn(1)-N(2)	0.228 5(5)	Mn(2)-O(2)	0.216 3(4)
  Mn(2)-O(3)	0.217 5(3)	Mn(2)-O(3)C	0.217 7(4)	Mn(2)-O(9)B	0.214 3(4)
  Mn(2)-N(3)	0.229 6(4)	Mn(2)-N(4)	0.229 8(4)
  O(8)B-Mn(1)-O(6)A	110.17(16)	O(8)B-Mn(1)-O(1)	97.57(15)	O(6)A-Mn(1)-O(1)	92.25(15)
  O(8)B-Mn(1)-N(1)	122.13(17)	O(6)A-Mn(1)-N(1)	125.62(18)	O(1)-Mn(1)-N(1)	94.61(17)
  O(8)B-Mn(1)-N(2)	90.32(17)	O(6)A-Mn(1)-N(2)	93.85(19)	O(1)-Mn(1)-N(2)	167.73(17)
  N(1)-Mn(1)-N(2)	73.19(19)	O(9)B-Mn(2)-O(2)	97.62(14)	O(9)B-Mn(2)-O(3)	94.98(14)
  O(2)-Mn(2)-O(3)	80.29(14)	O(9)B-Mn(2)-O(3)C	102.45(15)	O(2)-Mn(2)-O(3)C	151.09(14)
  O(3)-Mn(2)-O(3)C	77.46(14)	O(9)B-Mn(2)-N(3)	166.85(15)	O(2)-Mn(2)-N(3)	80.40(15)
  O(3)-Mn(2)-N(3)	97.48(14)	O(3)C-Mn(2)-N(3)	84.43(15)	O(9)B-Mn(2)-N(4)	96.56(15)
  O(2)-Mn(2)-N(4)	107.21(15)	O(3)-Mn(2)-N(4)	165.22(15)	O(3)C-Mn(2)-N(4)	91.03(15)
  N(3)-Mn(2)-N(4)	71.89(16)
  2
  Zn(1)-O(1)	0.196 3(3)	Zn(1)-O(7)A	0.192 3(3)	Zn(1)-O(8)B	0.192 2(3)
  Zn(1)-N(1)	0.199 8(4)	Zn(2)-O(2)	0.195 7(3)	Zn(2)-O(6)A	0.195 0(3)
  Zn(2)-O(4)C	0.191 3(4)	Zn(2)-O(9)B	0.196 6(3)
  O(7)A-Zn(1)-O(8)B	127.52(15)	O(1)-Zn(1)-O(7)A	106.51(15)	O(1)-Zn(1)-O(8)B	106.01(15)
  N(1)-Zn(1)-O(7)A	105.44(14)	N(1)-Zn(1)-O(8)B	108.10(14)	O(1)-Zn(1)-N(1)	99.97(15)
  O(4)C-Zn(2)-O(6)A	95.08(16)	O(4)C-Zn(2)-O(2)	117.39(17)	O(6)A-Zn(2)-O(2)	112.26(15)
  O(4)C-Zn(2)-O(9)B	118.17(18)	O(6)A-Zn(2)-O(9)B	111.88(14)	O(9)B-Zn(2)-O(2)	102.42(15)
  Symmetry transformations used to generate equivalent atoms: A: -x, -y, -z+1; B: x+1, y, z; C: -x, -y+1, -z+1 for 1; A: -x+1, -y+1, -z+1; B: -x+1, y+1/2, -z+3/2; C: -x+1, -y+2, -z+1 for 2.

  Table 3

  

  Table 3.  Hydrogen bond lengths (nm) and angles (°) of complex 2

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  D-H…A	d(D-H) / nm	d(H…A) / nm	d(D…A) / nm	∠DHA / (°)
  O(10)-H(1W)…O(3)	0.085 0	0.193 7	0.278 7	178.54
  O(10)-H(2W)…O(4)A	0.098 3	0.202 9	0.300 1	169.50
  Symmetry code: A: -x+1, -y+2, -z+1.

  CCDC: 1943370, 1; 1943371, 2.

  2.   Results and discussion

  2.1   Description of the structure

  2.1.1   Crystal of {[Mn₂(μ₆-L)(phen)₂]·5H₂O}_n (1)

  An asymmetric unit of complex 1 possesses two Mn(Ⅱ) ions (Mn1 and Mn2), one μ₆-L^4- block, two phen moieties and five lattice water molecules (Fig. 1). Mn1 center is five-coordinated and reveals a trigonal pyramidal {MnN₂O₃} environment, which is completed by three carboxylate O atoms from three μ₆-L^4- blocks and a pair of N donors from the phen moiety. The six-coordinated Mn2 ion displays a distorted octahedral {MnN₂O₄} geometry filled by four carboxylate O atoms from three μ₆-L^4- blocks and a pair of N donors from the phen moiety. The lengths of the Mn-O and Mn-N bonds are 0.203 4(4)~0.217 7(4) and 0.222 3(4)~0.229 8(4) nm, respectively, which are within the normal values for related Mn(Ⅱ) derivatives^{[10, 12, 16, 19]}. The L^4- ligand behaves as a μ₆-block (mode Ⅰ, Scheme 1), wherein four deprotonated carboxylate groups adopt monodentate or μ-bridging bidentate modes. In the μ₆-L^4- block, a dihedral angle (between two benzene rings) and a C-O_ether-C angle are 66.27° and 118.88°, respe-ctively. Four carboxylate groups and two carboxylate O atoms of four different μ₆-L^4- blocks interlink four adjacent Mn(Ⅱ) centers to give a tetranuclear Mn4 unit (Fig. 2). These Mn₄ units are multiply held together by the remaining COO^- groups to generate a 2D sheet (Fig. 3).

  Figure 1

  

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

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

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  Scheme 1

  

  Scheme 1.  Coordination modes of L4- ligands in complexes 1 and 2

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  Figure 2

  

  Figure 2.  Tetra-manganese(Ⅱ) subunit in 1

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  Figure 3

  

  Figure 3.  Two dimensional sheet in complex 1 viewed along c axis

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  2.1.2   Crystal of {[Zn₂(μ₇-L)(py)]·H₂O}_n (2)

  This complex reveals a 2D metal-organic network. An asymmetric unit has two Zn(Ⅱ) ions (Zn1 and Zn2), one μ₇-L^4- block, one py ligand and one H₂O molecule of crystallization. The Zn1 center is tetra-coordinated and reveals a distorted tetrahedral {ZnNO₃} geometry. It is completed by three carboxylate O donors from three individual μ₇-L^4- moieties and one pyridyl N donor. The Zn2 ion is also tetra-coordinated and has a distorted tetrahedral {ZnO₄} environment comprising four carboxylate O atoms of three different μ₇-L^4- moieties. The Zn-O (0.191 4(4)~0.196 5(3) nm) and Zn-N (0.199 8(4) nm) bonds are within standard values^{[12, 22-23]}. The L^4- block acts as a μ₇-linker with its carboxylate groups adopting a monodentate or μ-bridging bidentate mode (mode Ⅱ, Scheme 1). Within the μ₇-L^4- block, the dihedral angle between two aromatic rings is 62.07°, whereas the C-O_ether-C angle is 118.98°. Two adjacent Zn centers are held together by means of three carboxylate groups coming from three μ₇-L^4- spacers (Fig. 4). As a result, the dizinc(Ⅱ) subunits with a Zn…Zn separation of 0.332 6(3) nm are formed and further interlinked by μ₇-L^4- blocks to produce a 2D network (Fig. 6).

  Figure 4

  

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

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  Figure 5

  

  Figure 5.  Di-zinc(Ⅱ) subunit in 2

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  Figure 6

  

  Figure 6.  Two dimensional sheet of 2 viewed along a axis

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  2.2   TGA analysis

  To determine the thermal stability of complexes 1 and 2, their thermal behaviors were investigated under nitrogen atmosphere by thermogravimetric analysis (TGA). As shown in Fig. 7, TGA curve of complex 1 shows that there was a loss of five lattice water molecules between 35 and 120 ℃ (Obsd. 9.8%, Calcd. 9.9%); further heating above 220 ℃ leads to a decomposition of the dehydrated sample. Complex 2 lost its one lattice water molecule in a range of 44~142 ℃ (Obsd. 3.1%, Calcd. 3.2%), followed by the decomposition at 392 ℃.

  Figure 7

  

  Figure 7.  TGA curves of complexes 1~2

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  2.3   Luminescent properties

  Solid-state emission spectra of H₄L and zinc(Ⅱ) complex 2 were measured at room temperature (Fig. 8). The spectrum of H₄L revealed a weak emission with a maximum at 467 nm (λ_ex=300 nm). In comparison with H₄L, complex 2 exhibited more extensive emission with a maximum at 446 nm (λ_ex=300 nm). These emissions correspond to intraligand π-π^* or n-π^* transition of H₄L^{[10, 12, 18]}. Enhancement of the lumines-cence in 2 vs H₄L can be explained by the coordina-tion of ligands to Zn(Ⅱ), because the coordination can augment a rigidity of ligands and reduce an energy loss due to radiationless decay^{[12, 18, 22]}.

  Figure 8

  

  Figure 8.  Solid-state emission spectra of H₄L and complex 2 at room temperature

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  2.4   Magnetic properties

  Variable-temperature magnetic susceptibility measurements were performed on powder samples of 1 in the 2~300 K temperature range (Fig. 9). For the 2D Mn(Ⅱ) polymer 1 at room temperature, the value of χ_MT, 8.80 cm³·mol^-1·K, was close to the value (8.76 cm³·mol^-1·K) expected for two magnetically isolated high-spin Mn(Ⅱ) ion (S=5/2, g=2.0). If temperature was lowered, the χ_MT value decreased continuously to a minimum of 1.51 cm³·mol^-1·K at 2.0 K. Between 10 and 300 K, the magnetic susceptibility can be fitted to the Curie-Weiss law with C=9.50 cm³·mol^-1·K and θ=-23.22 K. Because of the long separation between the neighboring Mn4 units, only the coupling interactions within the tetra-manganese(Ⅱ) blocks were considered. A decrease in χ_MT and a negative θ are due to an overall antiferromagnetic coupling between the manganese centers in the Mn4 subunits. According to the structure of complex 1 (Fig. 2), three are two sets of magnetic exchange pathway within the Mn4 subunit via two carboxylate O atoms and four carbo-xylate groups bridges, which could be responsible for the observed antiferromagnetic exchange.

  Figure 9

  

  Figure 9.  Temperature dependence of χ_MT (○) and 1/χ_M(□) for complex 1

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  3.   Conclusions

  In summary, we have successfully synthesized and characterized two new manganese and zinc coordination polymers by using one unexplored ether-bridged tetracarboxylic acid as ligand under hydrothermal condition. Both complexes feature a 2D sheet structure based on Mn₄ or Zn₂ subunits. Besides, the luminescent (for 2) and magnetic (for 1) properties were also investigated and discussed. The results show that such ether-bridged tetracarboxylic acid can be used as a versatile multifunctional building block toward the generation of new coordination polymers.

  
  
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• 

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

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

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  Scheme 1  Coordination modes of L4- ligands in complexes 1 and 2

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  Figure 2  Tetra-manganese(Ⅱ) subunit in 1

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  Figure 3  Two dimensional sheet in complex 1 viewed along c axis

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

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  Figure 5  Di-zinc(Ⅱ) subunit in 2

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  Figure 6  Two dimensional sheet of 2 viewed along a axis

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  Figure 7  TGA curves of complexes 1~2

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  Figure 8  Solid-state emission spectra of H₄L and complex 2 at room temperature

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  Figure 9  Temperature dependence of χ_MT (○) and 1/χ_M(□) for complex 1

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  Table 1.  Crystal data for complexes 1 and 2

  Complex	1	2
  Chemical formula	C40H32Mn2N4O14	C21H13Zn2NO10
  Molecular weight	902.49	570.06
  Crystal system	Triclinic	Monoclinic
  Space group	P1	I2/a
  a / nm	1.087 55(9)	1.785 54(8)
  b / nm	1.182 56(11)	1.319 04(4)
  c / nm	1.420 46(11)	1.801 75(6)
  α / (°)	75.404(7)
  β / (°)	88.089(7)	92.856(3)
  γ / (°)	75.299(8)
  V / nm3	1.709 1(3)	4.238 2(3)
  Z	2	8
  F(000)	824	2 288
  θ range for data collection	3.428~25.048	3.464~25.048
  Limiting indices	-12 ≤ h≤ 9, -14 ≤ k ≤ 13, -15 ≤ l ≤ 16	-20 ≤ h ≤ 21, -15 ≤ k ≤ 11, -21 ≤ l ≤ 20
  Reflection collected, unique (Rint)	10 937, 6 032 (0.061 7)	13 704, 3 752 (0.040 9)
  Dc / (g·cm-3)	1.579	1.787
  μ / mm-1	0.806	2.324
  Data, restraint, parameter	6 032, 0, 496	3 752, 0, 307
  Goodness-of-fit on F2	0.961	1.048
  Final R indices [I≥2σ(I)] R1, wR2	0.072 1, 0.157 2	0.042 1, 0.103 7
  R indices (all data) R1, wR2	0.121 0, 0.183 6	0.056 1, 0.115 7
  Largest diff. peak and hole / (e·nm-3)	958 and -719	1 260 and -552

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

  1
  Mn(1)-O(1)	0.214 7(4)	Mn(1)-O(6)A	0.205 8(4)	Mn(1)-O(8)B	0.203 4(4)
  Mn(1)-N(1)	0.222 3(4)	Mn(1)-N(2)	0.228 5(5)	Mn(2)-O(2)	0.216 3(4)
  Mn(2)-O(3)	0.217 5(3)	Mn(2)-O(3)C	0.217 7(4)	Mn(2)-O(9)B	0.214 3(4)
  Mn(2)-N(3)	0.229 6(4)	Mn(2)-N(4)	0.229 8(4)
  O(8)B-Mn(1)-O(6)A	110.17(16)	O(8)B-Mn(1)-O(1)	97.57(15)	O(6)A-Mn(1)-O(1)	92.25(15)
  O(8)B-Mn(1)-N(1)	122.13(17)	O(6)A-Mn(1)-N(1)	125.62(18)	O(1)-Mn(1)-N(1)	94.61(17)
  O(8)B-Mn(1)-N(2)	90.32(17)	O(6)A-Mn(1)-N(2)	93.85(19)	O(1)-Mn(1)-N(2)	167.73(17)
  N(1)-Mn(1)-N(2)	73.19(19)	O(9)B-Mn(2)-O(2)	97.62(14)	O(9)B-Mn(2)-O(3)	94.98(14)
  O(2)-Mn(2)-O(3)	80.29(14)	O(9)B-Mn(2)-O(3)C	102.45(15)	O(2)-Mn(2)-O(3)C	151.09(14)
  O(3)-Mn(2)-O(3)C	77.46(14)	O(9)B-Mn(2)-N(3)	166.85(15)	O(2)-Mn(2)-N(3)	80.40(15)
  O(3)-Mn(2)-N(3)	97.48(14)	O(3)C-Mn(2)-N(3)	84.43(15)	O(9)B-Mn(2)-N(4)	96.56(15)
  O(2)-Mn(2)-N(4)	107.21(15)	O(3)-Mn(2)-N(4)	165.22(15)	O(3)C-Mn(2)-N(4)	91.03(15)
  N(3)-Mn(2)-N(4)	71.89(16)
  2
  Zn(1)-O(1)	0.196 3(3)	Zn(1)-O(7)A	0.192 3(3)	Zn(1)-O(8)B	0.192 2(3)
  Zn(1)-N(1)	0.199 8(4)	Zn(2)-O(2)	0.195 7(3)	Zn(2)-O(6)A	0.195 0(3)
  Zn(2)-O(4)C	0.191 3(4)	Zn(2)-O(9)B	0.196 6(3)
  O(7)A-Zn(1)-O(8)B	127.52(15)	O(1)-Zn(1)-O(7)A	106.51(15)	O(1)-Zn(1)-O(8)B	106.01(15)
  N(1)-Zn(1)-O(7)A	105.44(14)	N(1)-Zn(1)-O(8)B	108.10(14)	O(1)-Zn(1)-N(1)	99.97(15)
  O(4)C-Zn(2)-O(6)A	95.08(16)	O(4)C-Zn(2)-O(2)	117.39(17)	O(6)A-Zn(2)-O(2)	112.26(15)
  O(4)C-Zn(2)-O(9)B	118.17(18)	O(6)A-Zn(2)-O(9)B	111.88(14)	O(9)B-Zn(2)-O(2)	102.42(15)
  Symmetry transformations used to generate equivalent atoms: A: -x, -y, -z+1; B: x+1, y, z; C: -x, -y+1, -z+1 for 1; A: -x+1, -y+1, -z+1; B: -x+1, y+1/2, -z+3/2; C: -x+1, -y+2, -z+1 for 2.

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  Table 3.  Hydrogen bond lengths (nm) and angles (°) of complex 2

  D-H…A	d(D-H) / nm	d(H…A) / nm	d(D…A) / nm	∠DHA / (°)
  O(10)-H(1W)…O(3)	0.085 0	0.193 7	0.278 7	178.54
  O(10)-H(2W)…O(4)A	0.098 3	0.202 9	0.300 1	169.50
  Symmetry code: A: -x+1, -y+2, -z+1.

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