English

• 0.   Introduction

  Polynuclear manganese complexes are attracting considerable attention in several different fields ranging from bioinorganic chemistry to solid-state physics^[1]. Low-nuclearity species have been extensively studied as models for the water oxidizing complex in photosystem Ⅱ^[2], whereas nanometer-size clusters with high-spin ground states are currently being investigated as single-molecule magnets^[3]. From a synthetic point of view, chemists have learned to exploit hydrolytic reactions, which naturally lead to insoluble metal oxides and oxohydroxides as final products. By proper use of suitable organic ligands, mainly carboxylates^[4], polyamines^[5], and polyols^[6], the "growth" of the metal cores can be controlled in such a way to obtained finite-size clusters. Some ligands have been used to synthesize the manganese complexes, such as triethanolamine^[7], salicylaldoxime^[8], Alkoxide ligands^[9], dipyridyl ketone^[10]. Due to the effect of ligand fields and different coordination modes, the complexes will excite different magnetic properties. To our best of knowledge, the Schiff-base ligand, 3-ethoxy-6-(((2-hydroxyethyl)imino)methyl) phenol(H₂L), has not been used to synthesized the manganese complexes.

  To further study the interaction between the ligand and the property, two new manganese complexes, [Na₂Mn^ⅡMn₆^ⅢO₂(L)₆(N₃)₄(CH₃COO)₂]·4DMF (1) and [Na₂Mn^ⅡMn₆^ⅢO₂(L)₆(SCN)₄(CH₃COO)₂]·2DMF (2), have been synthesized by treating H₂L with Mn(OAc)₂·4H₂O and characterized by elemental analysis, IR spectra and X-ray single crystal diffraction. The magnetic behavior of 1 and 2 indicates an antiferro-magnetic interaction between the Mn²⁺ and Mn³⁺ ions.

  1.   Experimental

  1.1   Chemicals and general instruments

  3-ethoxy-6-(((2-hydroxyethyl)imino)methyl phenol was prepared according to the published procedures^[11]. All other reagents and solvents were used as received.

  Thermogravimetric analysis (TGA) experiments were carried out on a NETZSCH STA 449F3 thermal analyzer from 40 to 800 ℃ under N₂ at a heating rate of 10 ℃·min^-1. Powder X-ray diffraction (PXRD) determinations was performed on an X-ray diffracto-meter (D/max 2500 PC, Rigaku) with Cu Kα radiation (λ=0.154 06 nm). The crushed single crystalline powder samples were scanned at 40 kV (generator voltage) and 40 mA (tube current) from 5° to 50° with a step of 0.1°·s^-1. Elemental analyses were performed on an Elementar Vario MICRO CUBE elemental analyzer. The magnetic measurements were performed on SQUID-VSM.

  1.2   Synthesis of [Na₂Mn^ⅡMn₆^ⅢO₂(L)₆(N₃)₄ (CH₃COO)₂]·4DMF (1)

  Mn(OAc)₂·4H₂O (171.5 mg, 0.7 mmol), NaN₃ (13.0 mg, 0.2 mmol) and Schiff base ligand (H₂L) (125.4 mg, 0.6 mmol) were reacted in DMF (10 mL) in the presence of tetramethyl ammonium hydroxide. The solution was stirred for 5 hours at room temperature and filtered. The filtrate was left undisturbed to allow slow evaporation of the solvent. Black single crystals suitable for X-ray diffraction were obtained after a week. Yield: 73.1 mg, 32% (based on Mn). IR (KBr, cm^-1): 3 636(br), 2 362(s), 1 678(s), 1 602(m), 1 575(s), 1 526(s), 1 440(vs), 1 381(s), 1 357(w), 1 310(m), 1 234(m), 1 201(m), 1 116(vw), 1 034(vw), 971(vw), 831(w), 786(vw), 735(w), 650(w), 612(w). Anal. Calcd. for C₈₂H₁₁₂Mn₇N₂₂Na₂O₂₈(%): C, 43.07; H, 4.90; N, 13.48. Found(%): C, 43.12; H, 4.95; N, 13.42.

  1.3   Synthesis of [Na₂Mn^ⅡMn₆^ⅢO₂(L)₆(SCN)₄ (CH₃COO)₂]·2DMF (2)

  The synthesis of 2 was same as that of 1 except that NaSCN (16.2 mg, 0.2 mmol) was used instead of NaN₃. Yield: 65.9 mg, 28% (based on Mn). IR (KBr, cm^-1): 3 652(br), 2 989(s), 1 602(s), 1 578(s), 1 524(vs), 1 440(s), 1 384(m), 1 312(m), 1 299(m), 1 183(vw), 1 116(vw), 1 029(w), 978(vw), 831(w), 755(w), 739(w), 659(w), 605(w). Anal. Calcd. for C₈₄H₁₁₀Mn₇N₁₄Na₂O₃₀S₄(%): C, 42.81; H, 4.67; N, 8.32. Found(%): C, 42.78; H, 4.65; N, 8.26.

  1.4   X-ray crystallography

  Data were collected on a Bruker SMART APEX Ⅱ diffractometer equipped with a graphite-monochro-matized Mo Kα radiation (λ=0.071 073 nm) at room temperature by using an ω-2θ scan mode. The size of the crystal 1 and 2 are 0.18 mm×0.16 mm×0.10 mm and 0.28 mm×0.15 mm×0.12 mm, respectively. The raw data frames were integrated with SAINT⁺, and the corrections were applied for Lorentz and polarization effects. There was no evidence of crystal decay during data collection in all cases. Absorption correction was applied by using the multi-scan program SADABS^[12]. The structure was solved by direct methods, and all non-hydrogen atoms were refined anisotropically by least-squares methods on F² using the SHELXLS program^[13]. The aromatic H atoms were restrained to ride 0.093 nm from the relevant C atom, with U_iso(H)=1.2U_eq(C), while the methyl H atoms were treated as rigid groups, pivoted about the attached C atom, with C-H bond lengths fixed at 0.096 nm and U_iso(H)=1.5U_eq(C). The crystallographic data and structural refinement parameters are provide in Table 1. Selected bond lengths and angles of complexes 1 and 2 are listed in Table 2.

  Table 1

  

  Table 1.  Crystallographic data for complexes 1 and 2

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  Complex	1	2
  Formula	C82H112Mn7N22Na2O28	C84H110Mn7N14Na2O30S4
  Formula weight	2 284.49	2 354.65
  Crystal system	Monoclinic	Triclinic
  Space group	P21/c	P1
  a/nm	1.339 80(5)	1.423 23(10)
  b/nm	2.207 97(7)	1.433 10(10)
  c/nm	3.348 29(8)	1.483 19(11)
  α/(°)		70.956 0(10)
  β/(°)	97.495(3)	77.596 0(10)
  γ/(°)		71.369 0(10)
  V/nm3	9.820 4(5)	2.689 0(3)
  Z	4	1
  F(000)	2 904	1 213
  Dc/(Mg·m-3)	1.545	1.454
  μ/mm-1	7.912	0.959
  θ range/(°)	3.327~67.070	3.044~25.009
  Reflection collected	33 369	39 762
  Independent reflection	17 196 (Rint=0.070 3)	9 386 (Rint=0.033 2)
  Parameter	1 293	645
  R1[1 > 2σ(I)]	0.061 2	0.053 1
  wR2[I > 2σ(I)]	0.134 3	0.158 8
  Goodness of fit	1.000	1.055

  Table 2

  

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

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  1
  Mn(l)-O(17)	0.188 1(3)	Mn(2)-O(20)	0.192 4(3)	Mn(6)-O(13)	0.220 8(4)
  Mn(l)-O(16)	0.189 3(3)	Mn(2)-N(20)	0.199 4(4)	Mn(6)-N(ll)	0.242 7(5)
  Mn(l)-O(18)	0.192 6(3)	Mn(2)-O(25)	0.215 8(4)	Mn(6)-Mn(8)	0.316 18(12)
  Mn(l)-N(22)	0.199 2(4)	Mn(2)-N(7)	0.244 2(5)	Mn(6)-Na(l)	0.342 6(2)
  Mn(l)-O(24)	0.218 0(4)	Mn(2)-Mn(4)	0.317 25(11)	Mn(5)-O(14)	0.218 2(4)
  Mn(l)-N(8)	0.236 0(5)	Mn(2)-Na(2)	0.347 4(2)	Mn(5)-O(26)	0.218 8(4)
  Mn(l)-Mn(4)	0.314 86(12)	Mn(6)-O(11)	0.187 3(3)	Mn(5)-O(28)	0.220 5(3)
  Mn(l)-Na(2)	0.340 8(2)	Mn(6)-O(28)	0.188 5(3)	Mn(5)-O(15)	0.220 4(3)
  Mn(2)-O(17)	0.188 0(3)	Mn(6)-O(8)	0.191 6(3)
  Mn(2)-O(15)	0.188 7(3)	Mn(6)-N(17)	0.198 0(4)
  O(17)-Mn(l)-O(16)	92.99(15)	O(16)-Mn(l)-O(18)	174.02(16)	O(16)-Mn(l)-N(22)	83.68(16)
  O(17)-Mn(l)-O(18)	92.98(15)	O(17)-Mn(l)-N(22)	168.27(17)	O(18)-Mn(l)-N(22)	90.38(16)
  2
  Mn(l)-O(15)	0.187 9(2)	Mn(2)-O(10)	0.187 0(2)	Mn(3)-N(6)	0.197 6(3)
  Mn(l)-O(10)	0.187 9(2)	Mn(2)-O(9)	0.188 9(2)	Mn(3)-N(3)	0.225 1(4)
  Mn(l)-O(13)	0.191 1(2)	Mn(2)-O(6)	0.199 5(3)	Mn(3)-N(4)	0.238 8(3)
  Mn(l)-N(7)	0.198 3(3)	Mn(2)-O(4)	0.214 3(3)	Mn(3)-Na(l)	0.342 10(15)
  Mn(l)-O(5)	0.215 9(3)	Mn(2)-Mn(3)	0.323 54(7)	Mn(4)-O(7)	0.217 2(2)
  Mn(l)-N(4)	0.252 4(3)	Mn(2)-Na(l)	0.344 78(15)	Mn(4)-O(8)	0.217 9(2)
  Mn(l)-Mn(3)	0.318 36(7)	Mn(3)-O(8)	0.190 1(2)	Mn(4)-O(15)	0.226 0(2)
  Mn(l)-Na(l)	0.344 89(15)	Mn(3)-O(11)	0.190 2(2)
  Mn(2)-O(7)	0.187 0(2)	Mn(3)-O(10)	0.191 0(2)
  O(15)-Mn(l)-O(10)	92.83(10)	O(15)-Mn(l)-O(5)	92.16(11)	O(13)-Mn(l)-N(7)	90.58(12)
  O(15)-Mn(l)-O(13)	173.78(10)	O(15)-Mn(l)-N(7)	84.02(12)
  O(10)-Mn(l)-O(13)	91.67(10)	O(10)-Mn(l)-N(7)	165.93(12)

  CCDC: 1849331, 1; 1849333, 2.

  2.   Results and discussion

  2.1   Structure description

  Complex 1 crystallizes in the monoclinic system, while 2 crystallizes in the triclinic system with the similar structure. Herein, the molecular structure of complex 1 is described in detail as a representative example. As shown in Fig. 1, complex 1 consists of seven Mn ions, two Na⁺ ions, six L^2- ions, four N₃^- anions and four DMF solvent molecules. The two peripheral [Mn₃^ⅢO]⁷⁺ triangles are each bonded to a central Mn²⁺ ion. This ion is linked to each triangle via the O atom of the ligand. The Mn ions in each triangle are linked to each other via one μ₄-O^2- ion, one η¹:η¹:μ-acetates, and the two N₃^- groups via the N atoms to form a [Mn₆^ⅢMn^Ⅱ(μ₄-O^2-)₂(μ-OOCCH₃)₂(μ-N₃)₄]¹⁰⁺ core. The Na⁺ ion links to the Mn via three O atoms of three L^2- ligands. The central μ₄-O atom deviates 0.222 nm from the mean plane formed by three Mn ions, which is similar with the reported structure[7a]. The angle of Mn-N(N₃)-Mn is 83.20° and 85.65°, respectively. The average distance between Na⁺ ion and μ₄-O is 0.267 7 nm. The average angle of Mn-O-Mn is 106.76°. The structure of 2 is similar with 1, except that the SCN group replaces the N₃ group. The central μ₄-O deviates 0.018 3 nm from the mean plane formed by three Mn ions, which is similar with 1. The angle of Mn-N(NCS)-Mn is 80.73° and 80.06°, respectively. The distance between Na⁺ ion and μ₄-O is 0.270 0 nm. The average angle of Mn-O-Mn is 108.13°.

  Figure 1

  

  Figure 1.  Molecular structure (a) and coordination environment (b) of complex 1 with 40% probability displacement ellipsoids

  H atoms have been omitted for clarity

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  2.2   X-ray powder diffraction analyses

  Complexes 1 and 2 were also characterized by powder X-ray diffraction (PXRD) at room temperature. The patterns calculated from the single-crystal X-ray data of 1 and 2 were in good agreement with the observed ones in almost identical peak positions (Fig. 3). The difference in reflection intensities between the simulated and experimental patterns was due to the powder size and variation in preferred orientation for the powder samples during collection of the experimental PXRD data.

  Figure 2

  

  Figure 2.  Molecular structure (a) and coordination environment(b) of complex 2 with 40% probability displacement ellipsoids

  H atoms have been omitted for clarity; Symmetry codes: ⁱ-x+1, -y, -z+1

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  Figure 3

  

  Figure 3.  XRD patterns of complex 1 (a) and 2 (b)

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  2.3   Thermal stability

  Thermal stability is an important aspect for the application of coordination compound. Thermogravi-metric analysis (TGA) experiments were carried out to determine the thermal stabilities of 1 and 2 (Fig. 4). For complex 1, there are many solvent molecules in the structure, and TG curves showed the first consecutive step of weight loss that was observed in a range of 40~250 ℃, corresponding to the release of solvent molecules. Then, the continuously weight loss corresponds to the loss of ligands (in the range of 180~750 ℃). Finally, the weight loss ended until heating to 750 ℃ and the total weight loss was about 68%. For 2, TG curves was similar with complex 1, the weight loss ended until heating to 750 ℃ and the total weight loss was about 67%.

  Figure 4

  

  Figure 4.  TGA curves of complexes 1 and 2

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  2.4   Magnetic studies

  The variable-temperature dc magnetic susceptibi-lity measurement for complexes 1 and 2 were perfo-rmed in the temperature range of 2~300 K under an applied magnetic field of 1 000 Oe. The collected data are plotted as χ_MT vs T in Fig. 5 and Fig. 6. The χ_MT value at room temperature of complex 1 was 26.13 cm³·mol^-1·K, which is higher than the theoretically predicted value(22.37 cm³·mol^-1·K) for six Mn³⁺ and one Mn²⁺ ions^[14]. With the temperature decreasing, the χ_MT product of 1 decreased until 8.5 K, and then increased rapidly to 9.89 cm³·K·mol^-1 at 2 K, suggesting the presence of intramolecular ferromag-netic coupling between the Mn³⁺ and Mn²⁺ for 1 below 8.5 K^[15]. The temperature dependence of the reciprocal susceptibility χ_M^-1 values at high temperature were fitted by the Curie-Weiss law, χ_M=C/(T-θ), with C=21.50 cm³·mol^-1·K and θ=-59.09 K. The negative θ values confirm antiferromagnetic coupling among metal centers of 1. For complex 2, the χ_MT product at 300 K are 16.14 cm³·mol^-1·K, which is lower than the theoretically predicted value for six Mn³⁺ and one Mn²⁺ ions. As the temperature decreasing, χ_MT values gradually decreased, then underwent a rapid decrease until to 2.09 cm³·mol^-1·K at 2 K, indicating the presence of intramolecular antiferromagnetic interac-tions between the Mn³⁺ and Mn²⁺ ions. The tempera-ture dependence of the reciprocal susceptibility χ_M^-1 values above 50 K were fitted by the Curie-Weiss law with the obtained constant C=21.90 cm³·mol^-1·K and θ=-103.71 K. The negative value of θ confirms an antiferromagnetic coupling among metal centers of 2.

  Figure 5

  

  Figure 5.  Temperature dependence of χ_MT at 1 000 Oe (a) and 1/χ_M vs T plot (b) for 1

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  Figure 6

  

  Figure 6.  Temperature dependence of χ_MT at 1 000 Oe (a) and 1/χ_M vs T plot (b) for 2

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  To explore the dynamic magnetic property of the complexes, the temperature dependence of the alternating-current (ac) magnetic susceptibility for 1 and 2 under a zero direct-current (dc) magnetic field oscillating at 1~320 Hz was recorded in Fig. 7 and Fig. 8. As can be seen, 1 and 2 didn′t exhibit the frequency-dependent character in out-of-phase (χ″) signals and in-phase (χ′) signals. The result shows that the complexes 1 and 2 are not single molecule magnet (SMM).

  Figure 7

  

  Figure 7.  Plots for temperature dependence of in-phase (χ′) (a) and out-of-phase (χ″) (b) ac susceptibility for 1 under zero applied dc magnetic field

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  Figure 8

  

  Figure 8.  Plots for temperature dependence of in-phase (χ′) (a) and out-of-phase (χ″) (b) ac susceptibility for 2 under zero applied dc magnetic field

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  3.   Conclusions

  In summary, two new manganese complexes with Schiff-base ligands were synthesized and characterized by elemental analysis, IR spectra, thermogravimetric analyses and single crystal X-ray diffraction analysis. The investigation of magnetic studies confirms the antiferromagnetic interactions between the Mn²⁺ and Mn³⁺ ions for complexes 1 and 2. Furthermore, the dynamic magnetic property of the complexes 1 and 2 was studied, and it is found that the complexes 1 and 2 are not SMM.

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     (b) Murugesu M, Wernsdorfer W, Abboud K A, et al. Angew. Chem., 2005, 117(6): 914-918

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     (a) Milios C J, Vinslava A, Wernsdorfer W, et al. J. Am. Chem. Soc., 2007, 129(10): 2754-2755
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     (c) Milios C J, Inglis R, Bagai R, et al. Chem. Commun., 2007(33): 3476-3478
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• 

  Figure 1  Molecular structure (a) and coordination environment (b) of complex 1 with 40% probability displacement ellipsoids

  H atoms have been omitted for clarity

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  Figure 2  Molecular structure (a) and coordination environment(b) of complex 2 with 40% probability displacement ellipsoids

  H atoms have been omitted for clarity; Symmetry codes: ⁱ-x+1, -y, -z+1

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  Figure 3  XRD patterns of complex 1 (a) and 2 (b)

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  Figure 4  TGA curves of complexes 1 and 2

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  Figure 5  Temperature dependence of χ_MT at 1 000 Oe (a) and 1/χ_M vs T plot (b) for 1

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  Figure 6  Temperature dependence of χ_MT at 1 000 Oe (a) and 1/χ_M vs T plot (b) for 2

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  Figure 7  Plots for temperature dependence of in-phase (χ′) (a) and out-of-phase (χ″) (b) ac susceptibility for 1 under zero applied dc magnetic field

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  Figure 8  Plots for temperature dependence of in-phase (χ′) (a) and out-of-phase (χ″) (b) ac susceptibility for 2 under zero applied dc magnetic field

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  Table 1.  Crystallographic data for complexes 1 and 2

  Complex	1	2
  Formula	C82H112Mn7N22Na2O28	C84H110Mn7N14Na2O30S4
  Formula weight	2 284.49	2 354.65
  Crystal system	Monoclinic	Triclinic
  Space group	P21/c	P1
  a/nm	1.339 80(5)	1.423 23(10)
  b/nm	2.207 97(7)	1.433 10(10)
  c/nm	3.348 29(8)	1.483 19(11)
  α/(°)		70.956 0(10)
  β/(°)	97.495(3)	77.596 0(10)
  γ/(°)		71.369 0(10)
  V/nm3	9.820 4(5)	2.689 0(3)
  Z	4	1
  F(000)	2 904	1 213
  Dc/(Mg·m-3)	1.545	1.454
  μ/mm-1	7.912	0.959
  θ range/(°)	3.327~67.070	3.044~25.009
  Reflection collected	33 369	39 762
  Independent reflection	17 196 (Rint=0.070 3)	9 386 (Rint=0.033 2)
  Parameter	1 293	645
  R1[1 > 2σ(I)]	0.061 2	0.053 1
  wR2[I > 2σ(I)]	0.134 3	0.158 8
  Goodness of fit	1.000	1.055

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

  1
  Mn(l)-O(17)	0.188 1(3)	Mn(2)-O(20)	0.192 4(3)	Mn(6)-O(13)	0.220 8(4)
  Mn(l)-O(16)	0.189 3(3)	Mn(2)-N(20)	0.199 4(4)	Mn(6)-N(ll)	0.242 7(5)
  Mn(l)-O(18)	0.192 6(3)	Mn(2)-O(25)	0.215 8(4)	Mn(6)-Mn(8)	0.316 18(12)
  Mn(l)-N(22)	0.199 2(4)	Mn(2)-N(7)	0.244 2(5)	Mn(6)-Na(l)	0.342 6(2)
  Mn(l)-O(24)	0.218 0(4)	Mn(2)-Mn(4)	0.317 25(11)	Mn(5)-O(14)	0.218 2(4)
  Mn(l)-N(8)	0.236 0(5)	Mn(2)-Na(2)	0.347 4(2)	Mn(5)-O(26)	0.218 8(4)
  Mn(l)-Mn(4)	0.314 86(12)	Mn(6)-O(11)	0.187 3(3)	Mn(5)-O(28)	0.220 5(3)
  Mn(l)-Na(2)	0.340 8(2)	Mn(6)-O(28)	0.188 5(3)	Mn(5)-O(15)	0.220 4(3)
  Mn(2)-O(17)	0.188 0(3)	Mn(6)-O(8)	0.191 6(3)
  Mn(2)-O(15)	0.188 7(3)	Mn(6)-N(17)	0.198 0(4)
  O(17)-Mn(l)-O(16)	92.99(15)	O(16)-Mn(l)-O(18)	174.02(16)	O(16)-Mn(l)-N(22)	83.68(16)
  O(17)-Mn(l)-O(18)	92.98(15)	O(17)-Mn(l)-N(22)	168.27(17)	O(18)-Mn(l)-N(22)	90.38(16)
  2
  Mn(l)-O(15)	0.187 9(2)	Mn(2)-O(10)	0.187 0(2)	Mn(3)-N(6)	0.197 6(3)
  Mn(l)-O(10)	0.187 9(2)	Mn(2)-O(9)	0.188 9(2)	Mn(3)-N(3)	0.225 1(4)
  Mn(l)-O(13)	0.191 1(2)	Mn(2)-O(6)	0.199 5(3)	Mn(3)-N(4)	0.238 8(3)
  Mn(l)-N(7)	0.198 3(3)	Mn(2)-O(4)	0.214 3(3)	Mn(3)-Na(l)	0.342 10(15)
  Mn(l)-O(5)	0.215 9(3)	Mn(2)-Mn(3)	0.323 54(7)	Mn(4)-O(7)	0.217 2(2)
  Mn(l)-N(4)	0.252 4(3)	Mn(2)-Na(l)	0.344 78(15)	Mn(4)-O(8)	0.217 9(2)
  Mn(l)-Mn(3)	0.318 36(7)	Mn(3)-O(8)	0.190 1(2)	Mn(4)-O(15)	0.226 0(2)
  Mn(l)-Na(l)	0.344 89(15)	Mn(3)-O(11)	0.190 2(2)
  Mn(2)-O(7)	0.187 0(2)	Mn(3)-O(10)	0.191 0(2)
  O(15)-Mn(l)-O(10)	92.83(10)	O(15)-Mn(l)-O(5)	92.16(11)	O(13)-Mn(l)-N(7)	90.58(12)
  O(15)-Mn(l)-O(13)	173.78(10)	O(15)-Mn(l)-N(7)	84.02(12)
  O(10)-Mn(l)-O(13)	91.67(10)	O(10)-Mn(l)-N(7)	165.93(12)

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