English

• 1. INTRODUCTION

  Recently, studies on coordination polymers (CPs) are of great interest owing to their potential applications in many fields such as gas storage^[1-3], catalysis^[4], magnetism^[5] and luminescence^{[6, 7]}. Much work has been focused on the rational design and synthesis of multidimensional infinite architectures by dominating the favored geometry of ligands and metals, in which the construction of polymers using O- and N-donor organic ligands as co-ligands to bridge metal ions has been proved to be a successful paradigm^[8-10]. For O-donor ligands, the carboxylate-containing ligands play an important role in coordination chemistry, up to now, generous work has been in progress using rigid carboxylate ligands to build high-dimensional structures, for example, benzoic acid^{[11, 12]} and its derivative ligands such as 1,3-benzenedicarboxylate^{[13, 14]}, 1,4-benzenedicarboxylate^{[15, 16]}, 1,3,5-benzene-tricarboxylate^{[17, 18]}, and 1,2,4,5-benzenetetracarboxylate^[19]. On the other hand, the ligands containing N-donor like imidazole, phenanthrolineand their derivatives have also attracted great attention to construct CPs^[20-23].

  Herein, we describe a new complex caused by mixed H₂DHTA and rigid bipy ligands: [Mn(DHTA)(bipy)_0.5]_n (1). It displays a one-dimensional zigzag chain-like structure. As far as we know, its structure is different from our previous report for a 2,5-dihydroxy-benzene-dicarboxylate-bridged complex^[24].

  2. EXPERIMENTAL

  2.1 General procedures

  All reagents were purchased from Jilin Chinese Academy of Sciences—Yanshen Technology Co., Ltd and used without further purification.

  Elemental analyses (C, H and N) were measured on a Vario EL(Ⅲ) Elemental Analyzer. IR spectrum was recorded in the range of 4000~400 cm^-1 on a Nicolet 6700 Spectrophotometer using a KBr pellet. Powder X-ray diffraction (PXRD) patterns were collected in the 2θ range of 5~50º with a scan speed of 0.1 º·s^-1 on a Bruker D8 Advance instrument using a CuKα radiation (λ = 1.54056 Å) at room temperature.

  2.2 Synthesis

  Crystalline products of 1 was hydrothermally synthesized by reacting of Mn(OAc)₂·4H₂O (0.2 mmol), H₂DHTA (0.2 mmol) and bipy (0.2 mmol) in the mixed solvents of DMF and H₂O. Suitable amount of NaOH was added to this solution to adjust the pH value to 7 and it was stirred at room temperature for 0.5 h until a homogeneous solution was obtained. Then it was sealed in a Parr Teflon-lined stainless-steel vessel (25 mL) under autogenous pressure at 140 ℃ for 7 days. After the reaction system was slowly cooled to room temperature, brown block crystals were obtained by filtration and dried in air with the yield of 35% (based on Mn salt). Anal. Calcd. (%) for C₂₀H₁₀MnN₂O₈: C, 59.69; H, 3.58; N, 9.94. Found (%): C, 59.03; H, 3.17; N, 9.25. IR (cm^–1): 3446(m), 1625(m), 1594(m), 1489(w), 1474(w), 1438(m), 1363(m), 1321(w), 1238(m), 1014(w), 858(w), 817(w), 785(w), 759(w), 737(w), 651(w), 544(w), 473(w).

  2.3 X-ray crystallography

  Single-crystal diffraction data of 1 were collected on a Bruker/Siemens Smart Apex Ⅱ CCD diffractometer with graphite-monochromatic MoKα radiation (λ = 0.71073 Å) at 293(2) K. Data reductions and absorption corrections were performed using the SAINT and SADABS programs, respectively. The structure was solved by direct methods with SHELXS-97 program^[25] and refined by full-matrix least-squares techniques on F² with SHELXL-97^[26]. All non-hydrogen atoms were refined anisotropically and the hydrogen atoms of organic ligands were generated geometrically. A total of 4210 reflections were collected in the range of 3.17≤θ≤28.29°, of which 2456 were independent (R_int = 0.0757). The final R = 0.0754 and wR = 0.1465 for observed reflections with I > 2σ(I), and R = 0.1206 and wR = 0.1527 for all data with (Δρ)_max = 1.778 and (Δρ)_min = –1.102 e·Å^-3. Selected bond lengths and bond angles of complex 1 are shown in Table 1.

  Table 1

  

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

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  Bond	Dist.		Bond	Dist.		Bond	Dist.
  Mn(1)–O(1)	2.088(9)		Mn(1)–O(1A)	2.088(9)		Mn(1)–N(1)	2.274(10)
  Mn(1)–N(1A)	2.274(10)		Mn(1)–N(2)	2.259(10)		Mn(1)–N(2A)	2.259(10
  Angle	(°)		Angle	(°)		Angle	(°)
  O(1A)–Mn(1)–O(1)	86.6(5)		O(1A)–Mn(1)–N(2)	86.8(4)		O(1)–Mn(1)–N(2)	109.5(4)
  O(1)–Mn(1)–N(2A)	86.8(4)		N(2)–Mn(1)–N(2A)	158.0(5)		O(1A)–Mn(1)–N(1)	92.5(3)
  O(1)–Mn(1)–N(1)	178.3(4)		N(2)–Mn(1)–N(1)	71.8(3)		N(2A)–Mn(1)–N(1)	92.2(4)
  O(1)–Mn(1)–N(1A)	92.5(3)		N(2)–Mn(1)–N(1A)	92.2(4)		N(1)–Mn(1)–N(1A)	88.4(5)
  Symmetry code: 1: A: 1–x, y, –z+1/2

  3. RESULTS AND DISCUSSION

  3.1 Description of the structure

  The single crystal X-ray analysis indicates that complex 1 contains half Mn atom, half DHTA ligand and one bipy ligand in each independent crystallographic unit. The ORTEP view of complex 1 with atom labeling is shown in Fig. 1 (H atoms were omitted for clarity). The coordination geometry around the Mn^Ⅱ center could be represented as a distorted octahedral environment caused by O(1)–N(2A)–N(1)–N(2) consisting of the basal plane, and one O atom (O(1A)) and one nitrogen atom (N(1A)) occupying the axial positions from the opposite direction. The bond distances of Mn–N in complex 1 fall in the range of 2.259(10)~2.274(10) Å, and those of Mn–O in 2.088(9) Å, all being usual for such coordination bonds^[24]. The coordination angles around the Mn atom change from 71.8(3) to 178.3(4)^o.

  Figure 1

  

  Figure 1.  ORTEP view of complex 1 with atom labeling. H atoms were omitted for clarity at 30% probability thermal ellipsoids. Symmetry code: ^A1–x, y, –z+1/2

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  In complex 1, each bipy ligand acts as a regular bidentate chelating ligand terminally coordinated to the Mn(Ⅱ) metal center, while each DHTA anion is coordinated to the Mn(Ⅱ) ion in a µ₂-bridging coordination mode in virtue of suitable amount of NaOH added to the solution (pH = 7). Thus, neighbouring Mn(Ⅱ) atoms are bridged by DHTA ligands to obtain distinctive one-dimensional zigzag chain with the Mn···Mn distance of 11.414 Å (Fig. 2).

  Figure 2

  

  Figure 2.  One-dimensional zigzag chain of complex 1

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  The connected hydrogen-bonding geometries with symmetry codes are given in Table 2. All values involved with hydrogen bonding fall in the normal range. The O–H···O and C–H···O hydrogen-bonding interactions among the carbon atoms, OH group and carboxylic oxygen atoms stabilize the structure of complex 1. In addition, there are π-π interactions in complex 1 between the pyridine rings of bipy ligands. The centroid-to-centroid distance between neighbouring rings is 3.927(9) Å for N(1)C(1)C(2)C(3)C(4)C(5) and N(1΄)C(1΄)C(2΄)C(3΄)C(4΄)C(5΄) (symmetry code: 1–x, –y, –z) pyridine rings. The perpendicular distance is 3.524(6) Å for N(1)C(1)C(2)C(3)C(4)C(5) and N(1΄)C(1΄)C(2΄)C(3΄)C(4΄)C(5΄) (symmetry code: 1–x, –y, –z) pyridine rings, with the dihedral angle to be 0.0(7)°. Thus, the one-dimensional zigzag chains are further spreaded to a three-dimensional supramolecular architecture by hydrogen bonds and π-π interactions (Fig. 3).

  Table 2

  

  Table 2.  Hydrogen Bonds for Complex 1

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  D–H···A	d(D–H)	d(H···A)	d(D···A)	∠(DHA)	Symmetry codes
  O(3)–H(3A)···O(1)	0.82	1.91	2.609(19)	143
  C(1)–H(1)···O(3)	0.93	2.55	3.36(2)	145	2/3–x, –1/2+y, 1/2–z
  C(10)–H(10)···O(2)	0.93	2.47	3.273(19)	145

  Figure 3

  

  Figure 3.  Three-dimensional supramolecular structure through hydrogen bonds and π-π interactions

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  3.2 Spectral characterization of complex 1

  The chief characteristic peaks of complex 1 are 3446, 1625, 1594, 1438, 1363, 1238, 1014, 858, 785, 737, 651 and 544 cm^-1, in which the strong peaks at 3446 cm^-1 should be tended to the stretching vibration absorption peak of O–H. The absorption peaks of asymmetric and symmetric stretching vibration are 1625 and 1363 cm^-1[27], respectively, which indicates the presence of monodentate linkage of carboxylates in the dianions^[28].

  Moreover, X-ray diffraction analysis further means the monodentate coordination manners of the carboxylate groups.

  3.3 Powder X-ray diffraction (PXRD)

  To confirm the phase purity of complex 1, powder X-ray diffraction (PXRD) patterns were recorded, and they were comparable to the corresponding simulated patterns calculated from the single-crystal diffraction data (Fig. 4), meaning a pure phase of the bulky sample.

  Figure 4

  

  Figure 4.  PXRD analyses of complex 1: bottom-simulated, top-experimental

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  4. THEORETICAL CALCULATIONS

  The presented calculations were performed with the Gaussian 03 program^[29]. Experimental data of the complex 1 provided the start geometries of the molecular structures for calculation. We analyzed the NBO by DFT^[30] with the PBE0^{[31, 32]} hybrid functional and the LANL2DZ basis set^[33-35].

  The selected natural atomic charges and natural electron configuration for complex 1 are shown in Table 3. It is indicated that the electronic configurations of Mn(Ⅱ) ion, N and O atoms are 4s^0.233d^5.614p^0.27, 2s^1.30~1.322p^4.10~4.13 and 2s^1.65~1.662p^5.05~5.06, respectively. Based on the above results, one can conclude that the Mn(Ⅱ) ion coordination with N and O atoms is mainly on the 3d, 4s and 4p orbitals. N and O atoms form coordination bonds with Mn(Ⅱ) ion using 2s and 2p orbitals. Therefore, the Mn(Ⅱ) ion obtained some electrons from four N atoms of bipy ligands and two O atoms of DHTA ligand^{[34, 35]}. Thus, according to valencebond theory, the atomic net charge distribution and NBO bond orders of 1 (Table 3) shows the obvious covalent interaction between the coordinated atoms and Mn(Ⅱ) ion. The differences of NBO bond orders for Mn–O and Mn–N make their bond lengths different^[35], which is in good agreement with the X-ray crystal structural data of complex 1.

  Table 3

  

  Table 3.  Selected Natural Atomic Charges (e) and Natural Electron Configuration for Complex 1

  DownLoad: CSV

  Atom	Net charge	Electron configuration	Bond	Wiberg bond index	NBO bond order
  Mn(1)	0.73502	[core]4s(0.23)3d(5.61)4p(0.27)
  O(1)	–0.71413	[core]2s(1.66)2p(5.05)	Mn(1)–O(1)	0.4667	0.4023
  O(1A)	–0.72449	[core]2s(1.65)2p(5.06)	Mn(1)–O(1A)	0.4447	0.3909
  N(1)	–0.43498	[core]2s(1.32)2p(4.10)	Mn(1)–N(1)	0.3370	0.3447
  N(1A)	–0.43741	[core]2s(1.32)2p(4.10)	Mn(1)–N(1A)	0.3382	0.3452
  N(2)	–0.44630	[core]2s(1.30)2p(4.12)	Mn(1)–N(2)	0.3191	0.3277
  N(2A)	–0.44943	[core]2s(1.31)2p(4.13)	Mn(1)–N(2A)	0.3094	0.3225

  As can be seen from Fig.5, both the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO) are mainly located on DHTA ligand and ILCT may be inferred from some contours of molecular orbital of complex 1.

  Figure 5

  

  Figure 5.  Frontier molecular orbitals of complex 1

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• 

  Figure 1  ORTEP view of complex 1 with atom labeling. H atoms were omitted for clarity at 30% probability thermal ellipsoids. Symmetry code: ^A1–x, y, –z+1/2

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  Figure 2  One-dimensional zigzag chain of complex 1

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  Figure 3  Three-dimensional supramolecular structure through hydrogen bonds and π-π interactions

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  Figure 4  PXRD analyses of complex 1: bottom-simulated, top-experimental

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  Figure 5  Frontier molecular orbitals of complex 1

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

  Bond	Dist.		Bond	Dist.		Bond	Dist.
  Mn(1)–O(1)	2.088(9)		Mn(1)–O(1A)	2.088(9)		Mn(1)–N(1)	2.274(10)
  Mn(1)–N(1A)	2.274(10)		Mn(1)–N(2)	2.259(10)		Mn(1)–N(2A)	2.259(10
  Angle	(°)		Angle	(°)		Angle	(°)
  O(1A)–Mn(1)–O(1)	86.6(5)		O(1A)–Mn(1)–N(2)	86.8(4)		O(1)–Mn(1)–N(2)	109.5(4)
  O(1)–Mn(1)–N(2A)	86.8(4)		N(2)–Mn(1)–N(2A)	158.0(5)		O(1A)–Mn(1)–N(1)	92.5(3)
  O(1)–Mn(1)–N(1)	178.3(4)		N(2)–Mn(1)–N(1)	71.8(3)		N(2A)–Mn(1)–N(1)	92.2(4)
  O(1)–Mn(1)–N(1A)	92.5(3)		N(2)–Mn(1)–N(1A)	92.2(4)		N(1)–Mn(1)–N(1A)	88.4(5)
  Symmetry code: 1: A: 1–x, y, –z+1/2

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  Table 2.  Hydrogen Bonds for Complex 1

  D–H···A	d(D–H)	d(H···A)	d(D···A)	∠(DHA)	Symmetry codes
  O(3)–H(3A)···O(1)	0.82	1.91	2.609(19)	143
  C(1)–H(1)···O(3)	0.93	2.55	3.36(2)	145	2/3–x, –1/2+y, 1/2–z
  C(10)–H(10)···O(2)	0.93	2.47	3.273(19)	145

  下载: 导出CSV

  Table 3.  Selected Natural Atomic Charges (e) and Natural Electron Configuration for Complex 1

  Atom	Net charge	Electron configuration	Bond	Wiberg bond index	NBO bond order
  Mn(1)	0.73502	[core]4s(0.23)3d(5.61)4p(0.27)
  O(1)	–0.71413	[core]2s(1.66)2p(5.05)	Mn(1)–O(1)	0.4667	0.4023
  O(1A)	–0.72449	[core]2s(1.65)2p(5.06)	Mn(1)–O(1A)	0.4447	0.3909
  N(1)	–0.43498	[core]2s(1.32)2p(4.10)	Mn(1)–N(1)	0.3370	0.3447
  N(1A)	–0.43741	[core]2s(1.32)2p(4.10)	Mn(1)–N(1A)	0.3382	0.3452
  N(2)	–0.44630	[core]2s(1.30)2p(4.12)	Mn(1)–N(2)	0.3191	0.3277
  N(2A)	–0.44943	[core]2s(1.31)2p(4.13)	Mn(1)–N(2A)	0.3094	0.3225

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