English

• 1. INTRODUCTION

  In recent years, coordination polymers have increasingly attracted considerable attention for their charming structures and potential applications, for instance, in gas absorption and separation^[1-3], luminescence^{[4, 5]}, catalysis^{[6, 7]}, molecular magnetism^{[8, 9]}, sensors^{[10, 11]}, etc. A high diversity of factors can affect the structure and functional properties of coordination polymers, such as the nature and coordination preferences of metal nodes, types of organic spacers and linkers, and various reaction conditions^[12-18].

  In this regard, an exploration of various organic ligands that combine different functional groups within the same building block molecule constitutes an interesting direction of research aiming at the design of new coordination polymers^[19-21]. Apart from multifunctional organic ligands, 1,10-phenanthroline (phen) is frequently applied as a simple secondary N-donor building block to tune the coordination environment and stabilizes structures because of its efficient π∙∙∙π stacking interaction^{[16, 18]}.

  Following our interest in the exploration of novel and poorly investigated multicarboxylic acids for the design of coordination polymers^{[6, 7, 16, 18, 22-26]}, in the present study we selected 2,3,3΄,4΄-diphenyl ether tetracarboxylic acid (H₄L) as a main building block. The selection of H₄L has been governed by the following reasons. (1) This ligand contains two phenyl rings that are interconnected by a rotatable O-ether group that can provide a subtle conformational adaptation. (2) H₄L contains two different types of functionalities (i.e., -COOH and O-ether) and has nine potential coordination sites, which can result in diverse coordination patterns and high dimensionalities, especially when acting as a multiply bridging spacer. (3) This tetracarboxylic acid block remains poorly used for the generation of coordination polymers.

  Herein, we report the synthesis, crystal structures, and magnetic properties of Mn(Ⅱ) coordination compounds with H₄L ligands.

  2. EXPERIMENTAL

  2.1 General procedures

  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) was performed under N₂ atmosphere with a heating rate of 10 K/min on a LINSEIS STA PT1600 thermal analyzer. PXRD (powder X-ray diffraction) data were obtained on a Rigaku-Dmax 2400 diffractometer (CuKα radiation, λ = 1.54060 Å). Magnetic susceptibility data were collected in the 2~300 K temperature range with 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.

  2.2 Synthesis of compound 1

  A mixture of MnCl₂⋅4H₂O (0.040 g, 0.2 mmol), H₄L (0.035 g, 0.1 mmol), phen (0.040 g, 0.2 mmol), and NaOH (0.016 g, 0.4 mmol) in distilled water (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 393 K for 3 days, followed by cooling to room temperature at a rate of 10 K·h^–1. Yellow block-shaped crystals of 1 were isolated manually, and washed with distilled water. Yield: 60% (based on phen). Anal. Calcd. (%) for C₆₄H₄₆Mn₂N₈O₁₃: C, 61.74; H, 3.72; N, 9.00. Found (%): C, 61.48; H, 3.70; N, 9.02. IR (KBr, cm^–1): 3421m, 3048w, 1608s, 1589s, 1515m, 1457w, 1422m, 1384s, 1256w, 1231w, 1144w, 1095w, 982w, 894w, 850m, 814w, 776w, 722m, 634w, 565w. ν_OH 3421 and 3048, v_as(CO₂) 1608 and 1589, v_s(CO₂) 1422 and 1384.

  2.3 Synthesis of compound 2

  Synthesis of 2 was similar to 1 except at 433 K instead of 393 K. Yellow block-shaped crystals of 2 were isolated manually, and washed with distilled water. Yield: 61% (based on H₄L). Anal. Calcd. (%) for C₄₀H₂₄Mn₂N₄O₁₀: C, 57.85; H, 2.91; N, 6.75. Found (%): C, 58.12; H, 2.93; N, 6.71. IR (KBr, cm^–1): 3410w, 3048w, 1599s, 1560m, 1535m, 1466w, 1407s, 1359m, 1256w, 1231w, 1207w, 1139w, 1099w, 1055w, 976w, 923w, 849m, 800w, 776w, 727m, 697w, 634w, 600w, 556w. ν_OH 3410 and 3048, v_as(CO₂) 1599, 1560 and 1535, v_s(CO₂) 1407 and 1359.

  2.4 Structure determination

  Two single crystals of the title compounds were mounted on a Bruker CCD diffractometer equipped with a graphite-monochromatic MoKα (λ = 0.71073 Å) radiation using a φ-ω scan mode at 293(2) K. The structures were solved by direct methods with SHELXS-97^[27] and refined by full-matrix least-squares techniques on F² with SHELXL-97^[28]. All non-hydrogen atoms were refined anisotropically. All hydrogen atoms (except those bound to water molecules) were placed in the calculated positions with fixed isotropic thermal parameters and included in structure factor calculations in the final stage of full-matrix least-squares refinement. The hydrogen atoms of water molecules were located by difference Fourier maps and constrained to ride on their parent O atoms. Some lattice solvent molecules in 1 and 2 are highly disordered and were removed using the SQUEEZE routine in PLATON^[29]. The number of solvent H₂O molecules was obtained on the basis of elemental and thermogravimetric analyses. Detailed crystallographic data and structural refinements of compounds 1 and 2 are listed in Table 1. The selected important bond parameters are given in Table 2. The hydrogen bonds and π∙∙∙π interactions in crystal packing of compounds 1 and 2 are listed in Table 3.

  Table 1

  

  Table 1.  Crystal Data and Structure Refinement for 1 and 2

  DownLoad: CSV

  Compound	1	2
  Formula	C64H46Mn2N8O13	C40H24Mn2N4O10
  Formula weight	1244.97	830.52
  Crystal system	Triclinic	Monoclinic
  Space group	P$ \overline 1 $	P21/c
  a (Å)	12.0415(8)	11.7387(15)
  b (Å)	14.2876(11)	11.6216(15)
  c (Å)	16.6562(12)	24.146(3)
  α (°)	96.645(6)	90
  β (°)	90.226(6)	90.651(11)
  γ (°)	98.319(6)	90
  V (Å3)	2815.8(4)	3293.8(7)
  Z	2	4
  Dc (g/cm3)	1.447	1.638
  µ (mm–1)	0.522	0.836
  Independent reflections	9941	5808
  Rint	0.0718	0.1065
  F(000)	1260	1648
  S	0.990	0.926
  R, wR (I > 2σ(I))	0.0722, 0.0871	0.0809, 0.1025

  Table 2

  

  Table 2.  Selected Bond Lengths (Å) and Bond Angles (°) for 1 and 2

  DownLoad: CSV

  1
  Bond	Dist.		Bond	Dist.		Bond	Dist.
  Mn(1)–O(1)	2.081(4)		Mn(1)–O(3)	2.130(3)		Mn(1)–N(1)	2.327(4)
  Mn(1)–N(2)	2.239(4)		Mn(1)–N(3)	2.277(5)		Mn(1)–N(4)	2.256(4)
  Mn(2)–O(6)	2.114(4)		Mn(2)–O(8)	2.094(3)		Mn(2)–N(5)	2.275(4)
  Mn(2)–N(6)	2.262(4)		Mn(2)–N(7)	2.284(5)		Mn(2)–N(8)	2.263(4)
  Angle	(°)		Angle	(°)		Angle	(°)
  O(1)–Mn(1)–O(3)	90.36(14)		O(1)–Mn(1)–N(2)	96.25(16)		O(3)–Mn(1)–N(2)	92.44(13)
  O(1)–Mn(1)–N(4)	98.82(17)		O(3)–Mn(1)–N(4)	100.30(14)		N(2)–Mn(1)–N(4)	160.14(16)
  O(1)–Mn(1)–N(3)	171.45(15)		O(3)–Mn(1)–N(3)	88.74(14)		N(2)–Mn(1)–N(3)	92.28(15)
  N(4)–Mn(1)–N(3)	72.99(16)		O(1)–Mn(1)–N(1)	92.91(15)		O(3)–Mn(1)–N(1)	165.11(13)
  N(2)–Mn(1)–N(1)	72.77(13)		N(4)–Mn(1)–N(1)	93.55(15)		N(3)–Mn(1)–N(1)	90.12(14)
  O(8)–Mn(2)–O(6)	86.12(14)		O(8)–Mn(2)–N(6)	166.37(15)		O(6)–Mn(2)–N(6)	90.61(15)
  O(8)–Mn(2)–N(8)	99.56(14)		O(6)–Mn(2)–N(8)	90.73(16)		N(8)–Mn(2)–N(6)	93.71(14)
  O(8)–Mn(2)–N(5)	95.16(14)		O(6)–Mn(2)–N(5)	105.42(16)		N(5)–Mn(2)–N(6)	72.94(15)
  N(8)–Mn(2)–N(5)	158.85(16)		O(8)–Mn(2)–N(7)	87.43(15)		O(6)–Mn(2)–N(7)	161.09(15)
  N(7)–Mn(2)–N(6)	99.55(15)		N(8)–Mn(2)–N(7)	72.84(17)		N(5)–Mn(2)–N(7)	92.86(17)
  2
  Bond	Dist.		Bond	Dist.		Bond	Dist.
  Mn(1)–O(2)	2.354(5)		Mn(1)–O(3)ⅱ	2.143(4)		Mn(1)–O(4)	2.164(5)
  Mn(1)–O(8)ⅰ	2.084(5)		Mn(1)–N(1)	2.309(6)		Mn(1)–N(2)	2.322(6)
  Mn(2)–O(1)	2.215(5)		Mn(2)–O(2)	2.354(5)		Mn(2)–O(6)ⅰ	2.190(5)
  Mn(2)–O(7)ⅰ	2.290(5)		Mn(2)–N(3)	2.220(6)		Mn(2)–N(4)	2.236(6)
  Angle	(°)		Angle	(°)		Angle	(°)
  O(8)ⅰ–Mn(1)–O(3)ⅱ	96.2(2)		O(8)ⅰ–Mn(1)–O(4)	160.4(2)		O(3)ⅱ–Mn(1)–O(4)	94.11(18)
  O(8)ⅰ–Mn(1)–N(1)	116.7(2)		O(3)ⅱ–Mn(1)–N(1)	85.1(2)		O(4)–Mn(1)–N(1)	80.68(19)
  O(8)ⅰ–Mn(1)–N(2)	89.2(2)		O(3)ⅱ–Mn(1)–N(2)	155.9(2)		O(4)–Mn(1)–N(2)	88.10(19)
  N(1)–Mn(1)–N(2)	71.6(2)		O(8)ⅰ–Mn(1)–O(2)	80.77(19)		O(3)ⅱ–Mn(1)–O(2)	102.36(18)
  O(4)–Mn(1)–O(2)	80.82(17)		N(1)–Mn(1)–O(2)	160.49(17)		N(2)–Mn(1)–O(2)	101.7(2)
  O(6)ⅰ–Mn(2)–O(1)	91.51(19)		O(6)ⅰ–Mn(2)–N(3)	105.0(2)		O(1)–Mn(2)–N(3)	84.22(19)
  O(6)ⅰ–Mn(2)–N(4)	137.65(19)		O(1)–Mn(2)–N(4)	129.5(2)		N(4)–Mn(2)–N(3)	73.7(2)
  O(6)ⅰ–Mn(2)–O(7)ⅰ	58.50(17)		O(7)ⅰ–Mn(2)–O(1)	144.82(19)		O(7)ⅰ–Mn(2)–N(3)	118.9(2)
  O(7)ⅰ–Mn(2)–N(4)	84.5(2)		O(6)ⅰ–Mn(2)–O(2)	97.06(18)		O(1)–Mn(2)–O(2)	57.75(16)
  N(3)–Mn(2)–O(2)	136.45(19)		N(4)–Mn(2)–O(2)	112.9(2)		O(7)ⅰ–Mn(2)–O(2)	104.61(18)
  Symmetry codes: ⅰ: x–1, y, z; ⅱ: –x, –y+1, –z+1

  Table 3

  

  Table 3.  Geometrical Parameters of Hydrogen Bonds and π∙∙∙π Interactions for 1 and 2

  DownLoad: CSV

  D–H∙∙∙A	d(D–H)/Å	d(H∙∙∙A)/Å	d(D∙∙∙A)/Å	∠DHA/º
  O(10)–H(1W)∙∙∙O(9)	0.85	1.81	2.663(7)	178
  O(10)–H(2W)∙∙∙O(11)	0.85	2.23	2.862(7)	131
  O(11)–H(3W)∙∙∙O(2)ⅰ	0.85	1.89	2.743(6)	179
  O(12)–H(5W)∙∙∙O(4)ⅰ	0.85	1.96	2.811(7)	179
  O(12)–H(6W)∙∙∙O(11)	0.84	2.14	2.943(7)	160
  Symmetry code: i: x, y+1, z
  Ring(i)→ring(j)	d(Cg(i))∙∙∙Cg(j))/Å	d(Cg(i))→ring(j))/Å	d(Cg(ji))→ring(i))/Å	Dihedral angle/º
  1
  Ring(1)→Ring(2)	3.6305(3)	3.4208(3)	3.4587(3)	1.104(3)
  Ring(3)→Ring(4)	3.6383(3)	3.3811(3)	3.4257(3)	1.225(3)
  Ring(5)→Ring(4)	3.4996(3)	3.4735(3)	3.4343(3)	0.496(3)
  Cg(1): N(2)C(24)C(25)C(26)C(27)C(28); Cg(2): N(5)ⅰC(48)ⅰC(49)ⅰC(50)ⅰC(51)Cⅰ(52)ⅰ; Cg
  Cg(3): N(6)C(48)C(49)C(50)C(51)C(52); N(6)C(48)C(49)C(50)C(51)C(52); Cg(4): C(44)ⅱC(45)ⅱC(46)ⅱC(47)ⅱC(48)ⅱC(49)ⅱ; –z+1; ii: x–1, y, z
  Cg(5): C(20)C(21)C(22)C(23)C(24)C(25). Symmetry operation: i: –x+1, –y, –z+1; ii: –x+2, –y+1, –z+1
  2
  Ring(1)→Ring(2)	3.6605(5)	3.5000(5)	3.3385(5)	1.501(5)
  Ring(3)→Ring(4)	3.5631(5)	3.3863(5)	3.3807(5)	1.125(5)
  Ring(3)→Ring(5)	3.6743(5)	3.3785(5)	3.3785(5)	1.444(5)
  Cg(1): N(1)C(17)C(18)C(19)C(20)C(21); Cg(2): N(4)ⅰC(36)ⅰC(37)ⅰC(38)ⅰC(39)ⅰC(40)ⅰ; Cg(3): C(32)C(33)C(34)C(35)C(36)C(37); Cg(4): N(3)ⅱC(29)ⅱC(30)ⅱC(31)ⅱC(32)ⅱC(33)ⅱ; Cg(5): C(32)ⅱC(33)ⅱC(34)ⅱC(35)ⅱC(36)ⅱC(37)ⅱ. Symmetry operation: i: –x, –y+1, –z+1; ii: –x–1, –y+2, –z+1

  3. RESULTS AND DISCUSSION

  3.1 Crystal structure of 1

  X-ray crystallography analysis reveals that compound 1 crystallizes in triclinic $ P\overline 1 $ space group. Compound 1 possesses a discrete dimeric structure. As shown in Fig. 1, the asymmetric unit of 1 bears two crystallographically unique Mn(Ⅱ) atoms (Mn(1) and Mn(2)), one μ-L^4– ligand, four phen moieties, and four lattice water molecules. Both Mn(1) and Mn(2) atoms are six-coordinated and feature distorted octahedral {MnN₄O₂} geometries, filled by two carboxylate O atoms of the μ-L^4– ligand and four N atoms of two phen moieties. The Mn–O and Mn–N bond distances are 2.081(4)~2.130(3) and 2.239(4)~2.327(4) Å, respectively; these are within the normal ranges observed in related Mn(Ⅱ) compounds^{[16, 18, 26]}. In 1, the L^4– ligand adopts the coordination mode Ⅰ (Scheme 1) with all carboxylate groups being monodentate. In the L^4– ligand, a dihedral angle (between two aromatic rings) and a C–O_ether–C angle are 84.20 and 117.65°, respectively. The μ-L^4– ligand connects Mn1 and Mn2 atoms to give a Mn₂ molecular unit having a Mn∙∙∙Mn distance of 9.655(3) Å (Fig. 1). The discrete dimeric units of 1 are interlinked by the O–H···O hydrogen bonds and π∙∙∙π packing interactions to generate a 3D supramolecular framework (Fig. 2 and Table 3).

  Figure 1

  

  Figure 1.  Coordination environments of the Mn(Ⅱ) atoms in compound 1. The lattice water molecules and hydrogen atoms are omitted for clarity

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  Scheme 1

  

  Scheme 1.  Coordination modes of the L^4– ligands in compounds 1 and 2

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  Figure 2

  

  Figure 2.  Perspective view of the 3D supramolecular framework along the bc plane in 1 (Blue dashed lines present the H-bonds)

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  3.2 Crystal structure of 2

  The asymmetric unit of compound 2 contains two crystallographically unique Mn(Ⅱ) atoms, one μ₅-L^4– ligand, two phen moieties, and one lattice water molecule. As depicted in Fig. 3, six-coordinate Mn(1) atom exhibits a distorted octahedral {MnN₂O₄} environment, which is occupied by four carboxylate O atoms of three L^4– blocks and two N atoms of one phen moiety. The Mn(2) center is also sixcoordinated to form a distorted octahedral {MnN₂O₄} geometry. It is completed by four carboxylate O atoms from two L^4– blocks and two N atoms of one phen moiety. The bond lengths of Mn–O are in the 2.084(5)~2.354(5) Å range, while the Mn–N bonds are 2.220(6)~2.322(6) Å, being comparable to those found in some reported Mn(Ⅱ) compounds^{[16, 18, 26]}. In 2, the L^4– block acts as a μ₅-linker (mode Ⅱ, Scheme 1), in which four carboxylate groups adopt monodentate, bidentate, μ-bridging bidentate and μ-bridging tridentate modes. Besides, μ₅-L^4– ligand is considerably bent showing a dihedral angle of 86.51° (between two aromatic rings) and the C–O_ether–C angle of 115.06°. The four adjacent Mn(Ⅱ) centers are bridged by means of four COO^– groups from two μ₅-L^4– blocks, generating a tetramanganese(Ⅱ) subunit (Fig. 4). These Mn₄ subunits are further interlinked by the remaining carboxylate functionalities of the μ₅-L^4– blocks to furnish a 1D chain (Fig. 5). The neighboring chains are assembled into a 2D sheet through the π∙∙∙π packing interaction (Table 3 and Fig. 6).

  Figure 3

  

  Figure 3.  Coordination environments of the Mn(Ⅱ) atoms in compound 2. The hydrogen atoms are omitted for clarity (Symmetry codes: ⅰ: x–1, y, z; ⅱ: –x, –y+1, –z+1)

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  Figure 4

  

  Figure 4.  Tetramanganese(Ⅱ) subunit (Symmetry code: ⅰ: –x, –y+1, –z+1)

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  Figure 5

  

  Figure 5.  View of 1D metal-organic chain along the ac plane in 2. The phen ligands are omitted for clarity

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  Figure 6

  

  Figure 6.  View of 2D metal-organic sheet along the ab plane in 2 (Green dashed lines present the π∙∙∙π interactions)

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  3.3 PXRD and thermal analyses

  The as-synthesized, microcrystalline samples of 1 and 2 were used to collect their PXRD (powder X-ray diffraction) patterns at room temperature (Figs. 7 and 8). The obtained data indicate that the experimental diffractograms are in good agreement with the plots simulated from the single-crystal X-ray diffraction data, thus affirming a phase purity of the analyzed samples of 1 and 2.

  Figure 7

  

  Figure 7.  PXRD patterns of compound 1 at room temperature. Black patterns correspond to the experimental data obtained using the as-synthesized bulk samples. Red patterns were simulated from the single crystal X-ray data

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  Figure 8

  

  Figure 8.  PXRD patterns of compound 2 at room temperature. Black patterns correspond to the experimental data obtained using the as-synthesized bulk samples. Red patterns were simulated from the single crystal X-ray data

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  To determine the thermal stability of compounds 1 and 2, their thermal behaviors were investigated under nitrogen atmosphere by thermogravimetric analysis (TGA). As shown in Fig. 9, compound 1 lost its four lattice water molecules in the 315~364 K range (exptl, 5.5%; calcd. 5.7%), followed by the decomposition at 563 K. The TGA curve of 2 reveals that one lattice water molecule is released between 353 and 382 K (exptl, 2.3%; calcd. 2.2%), and the dehydrated solid begins to decompose at 604 K. MnO is expected as final decomposition products of 1 and 2.

  Figure 9

  

  Figure 9.  TGA curves of compounds 1 and 2

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  3.4 Magnetic properties

  Variable-temperature magnetic susceptibility studies were carried out on powder samples of Mn(Ⅱ) derivative 2 in the 2~300 K temperature range. As shown in Fig. 10, χ_MT of 8.82 cm³⋅mol^–1⋅K at room temperature is close to 8.76 cm³⋅mol^–1⋅K, a value expected for two magnetically isolated Mn(Ⅱ) centers (S_Mn = 5/2, g = 2.0). On lowering the temperature, χ_MT slowly decreases until 30 K, followed by a sharp decrease to 5.73 cm³⋅mol^–1⋅K at 2.0 K (Fig. 10). In the 2~300 K range, the magnetic susceptibility can be fitted to the Curie-Weiss law with C = 9.41 cm³⋅mol^–1⋅K and θ = –16.2 K. A negative θ value points out an antiferromagnetic coupling between the neighboring Mn(Ⅱ) centers^{[30, 31]}. Because of the long separation between the adjacent Mn₄ subunits, only the coupling interactions within the tetra-manganese (Ⅱ) blocks were considered. In the structure of Mn₄ unit (Fig. 4), there are two types of magnetic exchange pathways within the tetranuclear units, namely, the μ-O atoms from the carboxylate groups and μ-carboxylate bridges.

  Figure 10

  

  Figure 10.  Temperature dependence of χ_MT (o) and 1/χ_M(□) vs. T for compound 2. The red straight line shows the Curie-Weiss fitting

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  4. CONCLUSION

  We applied unexplored 2,3,3΄,4΄-diphenyl ether tetracarboxylic acid (H₄L) as a versatile and multifunctional building block for the synthesis of two Mn(Ⅱ) coordination compounds at 120 and 160 ℃, respectively. Compound 1 discloses a discrete dimeric structure, which is assembled to a 3D supramolecular framework through O–H∙∙∙O hydrogen bond and π∙∙∙π packing interactions. Compound 2 has a chain structure. Structural differences between two compounds are attributed to the different reaction temperature. Magnetic studies for compound 2 demonstrate an antiferromagnetic coupling between the adjacent Mn(Ⅱ) centers. This work demonstrates that such ether-bridged tetracarboxylic acid can be used as a versatile multifunctional building block toward the generation of new coordination compounds and the hydrothermal reaction temperature has a significant effect on the structures of the coordination compounds.

  
  
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• 

  Figure 1  Coordination environments of the Mn(Ⅱ) atoms in compound 1. The lattice water molecules and hydrogen atoms are omitted for clarity

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  Scheme 1  Coordination modes of the L^4– ligands in compounds 1 and 2

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  Figure 2  Perspective view of the 3D supramolecular framework along the bc plane in 1 (Blue dashed lines present the H-bonds)

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  Figure 3  Coordination environments of the Mn(Ⅱ) atoms in compound 2. The hydrogen atoms are omitted for clarity (Symmetry codes: ⅰ: x–1, y, z; ⅱ: –x, –y+1, –z+1)

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  Figure 4  Tetramanganese(Ⅱ) subunit (Symmetry code: ⅰ: –x, –y+1, –z+1)

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  Figure 5  View of 1D metal-organic chain along the ac plane in 2. The phen ligands are omitted for clarity

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  Figure 6  View of 2D metal-organic sheet along the ab plane in 2 (Green dashed lines present the π∙∙∙π interactions)

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  Figure 7  PXRD patterns of compound 1 at room temperature. Black patterns correspond to the experimental data obtained using the as-synthesized bulk samples. Red patterns were simulated from the single crystal X-ray data

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  Figure 8  PXRD patterns of compound 2 at room temperature. Black patterns correspond to the experimental data obtained using the as-synthesized bulk samples. Red patterns were simulated from the single crystal X-ray data

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  Figure 9  TGA curves of compounds 1 and 2

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  Figure 10  Temperature dependence of χ_MT (o) and 1/χ_M(□) vs. T for compound 2. The red straight line shows the Curie-Weiss fitting

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  Table 1.  Crystal Data and Structure Refinement for 1 and 2

  Compound	1	2
  Formula	C64H46Mn2N8O13	C40H24Mn2N4O10
  Formula weight	1244.97	830.52
  Crystal system	Triclinic	Monoclinic
  Space group	P$ \overline 1 $	P21/c
  a (Å)	12.0415(8)	11.7387(15)
  b (Å)	14.2876(11)	11.6216(15)
  c (Å)	16.6562(12)	24.146(3)
  α (°)	96.645(6)	90
  β (°)	90.226(6)	90.651(11)
  γ (°)	98.319(6)	90
  V (Å3)	2815.8(4)	3293.8(7)
  Z	2	4
  Dc (g/cm3)	1.447	1.638
  µ (mm–1)	0.522	0.836
  Independent reflections	9941	5808
  Rint	0.0718	0.1065
  F(000)	1260	1648
  S	0.990	0.926
  R, wR (I > 2σ(I))	0.0722, 0.0871	0.0809, 0.1025

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  Table 2.  Selected Bond Lengths (Å) and Bond Angles (°) for 1 and 2

  1
  Bond	Dist.		Bond	Dist.		Bond	Dist.
  Mn(1)–O(1)	2.081(4)		Mn(1)–O(3)	2.130(3)		Mn(1)–N(1)	2.327(4)
  Mn(1)–N(2)	2.239(4)		Mn(1)–N(3)	2.277(5)		Mn(1)–N(4)	2.256(4)
  Mn(2)–O(6)	2.114(4)		Mn(2)–O(8)	2.094(3)		Mn(2)–N(5)	2.275(4)
  Mn(2)–N(6)	2.262(4)		Mn(2)–N(7)	2.284(5)		Mn(2)–N(8)	2.263(4)
  Angle	(°)		Angle	(°)		Angle	(°)
  O(1)–Mn(1)–O(3)	90.36(14)		O(1)–Mn(1)–N(2)	96.25(16)		O(3)–Mn(1)–N(2)	92.44(13)
  O(1)–Mn(1)–N(4)	98.82(17)		O(3)–Mn(1)–N(4)	100.30(14)		N(2)–Mn(1)–N(4)	160.14(16)
  O(1)–Mn(1)–N(3)	171.45(15)		O(3)–Mn(1)–N(3)	88.74(14)		N(2)–Mn(1)–N(3)	92.28(15)
  N(4)–Mn(1)–N(3)	72.99(16)		O(1)–Mn(1)–N(1)	92.91(15)		O(3)–Mn(1)–N(1)	165.11(13)
  N(2)–Mn(1)–N(1)	72.77(13)		N(4)–Mn(1)–N(1)	93.55(15)		N(3)–Mn(1)–N(1)	90.12(14)
  O(8)–Mn(2)–O(6)	86.12(14)		O(8)–Mn(2)–N(6)	166.37(15)		O(6)–Mn(2)–N(6)	90.61(15)
  O(8)–Mn(2)–N(8)	99.56(14)		O(6)–Mn(2)–N(8)	90.73(16)		N(8)–Mn(2)–N(6)	93.71(14)
  O(8)–Mn(2)–N(5)	95.16(14)		O(6)–Mn(2)–N(5)	105.42(16)		N(5)–Mn(2)–N(6)	72.94(15)
  N(8)–Mn(2)–N(5)	158.85(16)		O(8)–Mn(2)–N(7)	87.43(15)		O(6)–Mn(2)–N(7)	161.09(15)
  N(7)–Mn(2)–N(6)	99.55(15)		N(8)–Mn(2)–N(7)	72.84(17)		N(5)–Mn(2)–N(7)	92.86(17)
  2
  Bond	Dist.		Bond	Dist.		Bond	Dist.
  Mn(1)–O(2)	2.354(5)		Mn(1)–O(3)ⅱ	2.143(4)		Mn(1)–O(4)	2.164(5)
  Mn(1)–O(8)ⅰ	2.084(5)		Mn(1)–N(1)	2.309(6)		Mn(1)–N(2)	2.322(6)
  Mn(2)–O(1)	2.215(5)		Mn(2)–O(2)	2.354(5)		Mn(2)–O(6)ⅰ	2.190(5)
  Mn(2)–O(7)ⅰ	2.290(5)		Mn(2)–N(3)	2.220(6)		Mn(2)–N(4)	2.236(6)
  Angle	(°)		Angle	(°)		Angle	(°)
  O(8)ⅰ–Mn(1)–O(3)ⅱ	96.2(2)		O(8)ⅰ–Mn(1)–O(4)	160.4(2)		O(3)ⅱ–Mn(1)–O(4)	94.11(18)
  O(8)ⅰ–Mn(1)–N(1)	116.7(2)		O(3)ⅱ–Mn(1)–N(1)	85.1(2)		O(4)–Mn(1)–N(1)	80.68(19)
  O(8)ⅰ–Mn(1)–N(2)	89.2(2)		O(3)ⅱ–Mn(1)–N(2)	155.9(2)		O(4)–Mn(1)–N(2)	88.10(19)
  N(1)–Mn(1)–N(2)	71.6(2)		O(8)ⅰ–Mn(1)–O(2)	80.77(19)		O(3)ⅱ–Mn(1)–O(2)	102.36(18)
  O(4)–Mn(1)–O(2)	80.82(17)		N(1)–Mn(1)–O(2)	160.49(17)		N(2)–Mn(1)–O(2)	101.7(2)
  O(6)ⅰ–Mn(2)–O(1)	91.51(19)		O(6)ⅰ–Mn(2)–N(3)	105.0(2)		O(1)–Mn(2)–N(3)	84.22(19)
  O(6)ⅰ–Mn(2)–N(4)	137.65(19)		O(1)–Mn(2)–N(4)	129.5(2)		N(4)–Mn(2)–N(3)	73.7(2)
  O(6)ⅰ–Mn(2)–O(7)ⅰ	58.50(17)		O(7)ⅰ–Mn(2)–O(1)	144.82(19)		O(7)ⅰ–Mn(2)–N(3)	118.9(2)
  O(7)ⅰ–Mn(2)–N(4)	84.5(2)		O(6)ⅰ–Mn(2)–O(2)	97.06(18)		O(1)–Mn(2)–O(2)	57.75(16)
  N(3)–Mn(2)–O(2)	136.45(19)		N(4)–Mn(2)–O(2)	112.9(2)		O(7)ⅰ–Mn(2)–O(2)	104.61(18)
  Symmetry codes: ⅰ: x–1, y, z; ⅱ: –x, –y+1, –z+1

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  Table 3.  Geometrical Parameters of Hydrogen Bonds and π∙∙∙π Interactions for 1 and 2

  D–H∙∙∙A	d(D–H)/Å	d(H∙∙∙A)/Å	d(D∙∙∙A)/Å	∠DHA/º
  O(10)–H(1W)∙∙∙O(9)	0.85	1.81	2.663(7)	178
  O(10)–H(2W)∙∙∙O(11)	0.85	2.23	2.862(7)	131
  O(11)–H(3W)∙∙∙O(2)ⅰ	0.85	1.89	2.743(6)	179
  O(12)–H(5W)∙∙∙O(4)ⅰ	0.85	1.96	2.811(7)	179
  O(12)–H(6W)∙∙∙O(11)	0.84	2.14	2.943(7)	160
  Symmetry code: i: x, y+1, z
  Ring(i)→ring(j)	d(Cg(i))∙∙∙Cg(j))/Å	d(Cg(i))→ring(j))/Å	d(Cg(ji))→ring(i))/Å	Dihedral angle/º
  1
  Ring(1)→Ring(2)	3.6305(3)	3.4208(3)	3.4587(3)	1.104(3)
  Ring(3)→Ring(4)	3.6383(3)	3.3811(3)	3.4257(3)	1.225(3)
  Ring(5)→Ring(4)	3.4996(3)	3.4735(3)	3.4343(3)	0.496(3)
  Cg(1): N(2)C(24)C(25)C(26)C(27)C(28); Cg(2): N(5)ⅰC(48)ⅰC(49)ⅰC(50)ⅰC(51)Cⅰ(52)ⅰ; Cg
  Cg(3): N(6)C(48)C(49)C(50)C(51)C(52); N(6)C(48)C(49)C(50)C(51)C(52); Cg(4): C(44)ⅱC(45)ⅱC(46)ⅱC(47)ⅱC(48)ⅱC(49)ⅱ; –z+1; ii: x–1, y, z
  Cg(5): C(20)C(21)C(22)C(23)C(24)C(25). Symmetry operation: i: –x+1, –y, –z+1; ii: –x+2, –y+1, –z+1
  2
  Ring(1)→Ring(2)	3.6605(5)	3.5000(5)	3.3385(5)	1.501(5)
  Ring(3)→Ring(4)	3.5631(5)	3.3863(5)	3.3807(5)	1.125(5)
  Ring(3)→Ring(5)	3.6743(5)	3.3785(5)	3.3785(5)	1.444(5)
  Cg(1): N(1)C(17)C(18)C(19)C(20)C(21); Cg(2): N(4)ⅰC(36)ⅰC(37)ⅰC(38)ⅰC(39)ⅰC(40)ⅰ; Cg(3): C(32)C(33)C(34)C(35)C(36)C(37); Cg(4): N(3)ⅱC(29)ⅱC(30)ⅱC(31)ⅱC(32)ⅱC(33)ⅱ; Cg(5): C(32)ⅱC(33)ⅱC(34)ⅱC(35)ⅱC(36)ⅱC(37)ⅱ. Symmetry operation: i: –x, –y+1, –z+1; ii: –x–1, –y+2, –z+1

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