English

• 0.   Introduction

  The design of coordination polymers were well developed in recent years^[1-5]. The topologies and functionalities of such coordination polymers depend on the utilization of appropriate ligands as well as metal salts. The multiple coordination sites of the ligand incline towards forming higher dimensions^[6-8].The multifunctional thiodicarboxylic acid and its derivatives, which may link metal centers through both carboxylate groups and the S atom, are good ligands for the construction of different extended architecture structures^[9-11]. The carboxylate group can coordinate in multiple ways, either as a monodentate ligand, a bidentate chelating ligand or as a bridging ligand with different coordination numbers to various metal cations, resulting in the assembly of different coordination polymers^[12-13]. Now, based on the use of thiodicarboxylate as a ligand, we have chosen 3, 3′-thiodipropionic acid (DPA) to prepare the new coor-dination polymers. Additionally, N-donor ligands, such as 4, 4′-bipyridine(4, 4′-bipy) and 1, 3-bis(4-pyridyl)propane(bpp), have also been proved to exhibit remarkable properties for their excellent coordinating ability in the design of coordination polymers^[14]. In this context, we present the syntheses, crystal structures and the properties of two coordination polymers, namely {[Mn(DPA)(4, 4′-bipy)]·H₂O}_n (1) and {[Cu(DPA)(bpp)(H₂O)]·H₂O}_n (2), which incorporates 4, 4′-bipy or bpp ligands.

  1.   Experimental

  1.1   Reagents and instruments

  All the reagents were of analytical reagent grade and used without further purification. Elemental analyses were performed on a CARLO ERBA 1106 analyzer. The FT-IR spectra were recorded on a Bruker Equinox 55 FT-IR spectrometer using KBr pellet at a resolution of 0.5 cm^-1 (400~4 000 cm^-1). Thermogravimetry analyses were measured on a PERKIN ELMER TG/DTA 6300 thermogravimetric analyzer under a flowing N₂ atmosphere with a heating rate of 10 ℃·min^-1 starting at ambient temperature and heating up to 800 ℃, using sample weight of 1~5 mg. Powder X-ray diffraction (XRD) patterns were measured at 293 K on a Bruker D8 diffractometer (Cu Kα, λ=0.154 059 nm, U=40 kV, I=10 mA), scan-ning from 5° to 60°.

  1.2   Syntheses of the complexes

  1.2.1   Synthesis of {[Mn(DPA)(4, 4′-bipy)]·H₂O}_n (1)

  The complex was prepared by the addition of 4, 4′-bipyridine (1.0 mmol), 3, 3′-thiodipropionic acid (1.0mmol) and manganese nitrate tetrahydrate (1.0 mmol) to a mixing solution of water and methanol (1: 1, V/V, 20 mL), and the pH value was adjusted to 7 with 0.1 mol·L^-1 sodium hydroxide solution. The mixture was sealed in a 50 mL Teflon-lined stainless steel bomb and held at 393 K for 72 h. The bomb was cooled naturally to room temperature, and yellow crystals were obtained from the filtered solution after several days. Anal. Calcd. for C₁₆H₁₈N₂O₅SMn(%): C 47.40, H 4.48, N 6.91; Found(%): C 47.39, H 4.49, N 6.92. IR (KBr, cm^-1): 3 424(s), 3 156(s), 1 606(s), 1 567(s), 1 442(m), 1 401(s), 1 318(m), 1 215(m), 1 063(m), 994(m), 816(s), 630(m), 465(w).

  1.2.2   Synthesis of {[Cu(DPA)(bpp)(H₂O)]·H₂O}_n (2)

  The synthesis method of complex 2 is same as that of complex 1. Anal. Calcd. for C₁₉H₂₆N₂O₆SCu(%): C 48.19, H 5.54, N 5.92; Found(%): C 48.20, H 5.55, N 5.91. IR (KBr, cm^-1): 3 361(s), 2 915(m), 1 621(s), 1 586(s), 1 428(m), 1 374(m), 1 297(m), 1 077(m), 933(m), 699(m), 520(w).

  1.3   X-ray crystallographic determination

  The suitable single crystal of these complexes was employed for data collection on a Bruker P4 diffractometer with graphite monochromatized Mo Kα (λ=0.071 073 nm) radiation. All structures were solved by direct method and difference Fourier syntheses. All non-hydrogen atoms were refined by full-matrix least-squares techniques on F² with anisotropic thermal parameters. The C-H atoms were located and included at their geometrically idealized positions, with d_C-H=0.093 nm and were refined as riding, with U_iso(H)=1.2U_eq(C). Hydrogen atoms of water molecules and N-H atoms were located in difference Fourier maps and refined in the riding model approximation, with the O-H, O-H, H…H and N-H distance restrains of 0.085(1), 0.139(1) and 0.090(1) nm, respectively, and with U_iso(H)=1.5U_eq(O). All calculations were carried out with SHELXL 97 program^[15]. The summary of the crystallographic data for the complexes are provided in Table 1. The selected bond distances and angles are listed in Table 2.

  Table 1

  

  Table 1.  Crystal data and structure parameters for the complexes

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  Complex	1	2
  Formula	C16H18N2O5SMn	C19H26N2O6SCu
  Formula weight	405.32	474.02
  Temperature/K	293(2)	293(2)
  Size/mm	0.20×0.10×0.10	0.21×0.18×0.15
  θ range for data collection/(°)	2.16~25.39	2.01~25.37
  Crystal system	Monoclinic	Monoclinic
  Space group	C2/c	P21/c
  a/nm	1.626 4(3)	1.040 8(2)
  b/nm	1.163 5(2)	1.233 3(3)
  c/nm	1.861 3(4)	1.747 0(4)
  β/(°)	99.94(3)	102.99(3)
  V/nm3	3.469(1)	2.185(8)
  Z	8	4
  Dc/(g·cm-3)	1.552	1.441
  μ/mm-1	0.911	1.131
  F(000)	1 672	988
  Reflection collected	3 160	4 249
  Unique reflection (Rint)	1 551 (0.000 0)	4 017 (0.067 2)
  R1, wR2 [I > 2σ(I)]	0.079 6, 0.148 7	0.071 3, 0.197 2
  R1, wR2 (all data)	0.158 1, 0.177 4	0.121 6, 0.277 7
  Goodness-of-fit (on F2)	1.002	1.060
  (Δρ)max, (Δρ)min/(e·nm-3)	753, -691	1 024, -1 063

  Table 2

  

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

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  1
  Mn(1)-O(1)	0.216 9(5)	Mn(1)-O(2)ⅰ	0.207 8(6)	Mn(1)-O(3)ⅱ	0.246 8(5)
  Mn(1)-O(4)ⅱ	0.221 5(6)	Mn(1)-N(1)	0.226 7(5)	Mn(1)-N(2)ⅲ	0.229 1(5)
  O(1)-Mn(1)-O(3)ⅱ	84.1(2)	O(1)-Mn(1)-O(4)ⅱ	136.8(2)	O(1)-Mn(1)-N(1)	89.8(2)
  O(1)-Mn(1)-N(2)ⅲ	89.4(2)	O(2)ⅰ-Mn(1)-O(1)	125.8(3)	O(2)ⅰ-Mn(1)-O(3)ⅱ	150.0(3)
  O(2)ⅰ-Mn(1)-O(4)ⅱ	97.1(3)	O(2)ⅰ-Mn(1)-N(1)	88.9(2)	O(2)ⅰ-Mn(1)-N(2)ⅲ	88.0(2)
  O(4)ⅱ-Mn(1)-O(3)ⅱ	53.6(2)	O(4)ⅱ-Mn(1)-N(1)	85.0(2)	O(4)ⅱ-Mn(1)-N(2)ⅲ	98.5(2)
  N(1)-Mn(1)-N(2)ⅲ	175.6(2)	N(1)-Mn(1)-O(3)ⅱ	94.0(2)
  2
  Cu(1)-O(1)	0.195 1(6)	Cu(1)-O(3)ⅰ	0.200 0(5)	Cu(1)-O(4)ⅰ	0.273 0(6)
  Cu(1)-O1W	0.226 5(6)	Cu(1)-N(1)	0.200 6(6)	Cu(1)-(N2)ⅱ	0.203 1(7)
  O(1)-Cu(1)-O(3)ⅰ	159.4(2)	O(1)-Cu(1)-N(1)	95.9(2)	O(1)-Cu(1)-N(2)ⅱ	86.7(3)
  O(1)-Cu(1)-O1W	101.2(3)	O(3)ⅰ-Cu(1)-N(1)	86.3(2)	O(3)ⅰ-Cu(1)-N(2)ⅱ	90.5(2)
  O(3)-Cu(1)-O1W	99.2(2)	N(1)-Cu(1)-O1W	92.3(2)	N(1)-Cu(1)-N(2)ⅱ	176.6(3)
  N(2)ⅱ-Cu(1)-O1W	89.3(3)	O(3)ⅰ-Cu(1)-O(4)ⅰ	52.8(2)
  Symmetry codes: ⅰ -x+1, y, -z+3/2; ⅱ -x+1/2, y-1/2, -z+3/2; ⅲ x, y+1, z for 1; ⅰ x-1, y, z; ⅱ x+1, -y+1/2, z+1/2 for 2.

  CCDC: 1841409, 1; 1545628, 2.

  2.   Results and discussion

  2.1   Crystal structure of {[Mn(DPA)(4, 4′-bipy)]·H₂O}_n (1)

  Crystal data, data collection and structure refinement details are summarized in Table 1. The molecular structure of complex 1 is depicted in Fig. 1 and the selected bond distances and bond angles are given in Table 2. The asymmetric unit of 1 contains one Mn(Ⅱ) ion, one 3, 3′-thiodipropionate ligand, and one 4, 4′-bipy molecule and one free water molecule. The carboxyl groups of 3, 3′-thiodipropionate show two coordination modes: one carboxyl group is bound to two Mn(Ⅱ) ions in a double-monodentate coordination fashion; whereas the other carboxyl group is coordinated to one Mn(Ⅱ) ion in a bidentate chelating mode. Each Mn(Ⅱ) ion lies on a distorted octahedral coordination configuration, defined by four O atoms from three different 3, 3′-thiodipropionate ligands and two N atoms from two 4, 4′-bipy molecules. Atoms O1, O2^ⅰ, O3^ⅱ and O4^ⅱ comprise the equatorial plane, and N1 and N2^ⅲ atoms occupy the apical sites (N(1)-Mn(1)-N(2)^ⅲ 175.6(2)°). The Mn-O distances fall in the range of 0.207 8(6)~0.246 8(5) nm, while the Mn-N distances are 0.226 7(5) and 0.229 1(5) nm (Table 2).

  Figure 1

  

  Figure 1.  Molecular structure of 1 with ellipsoids drawn at 30% probability level

  Symmetry codes:^ⅰ-x+1, y, -z+3/2; ^ⅱ-x+1/2, y-1/2, -z+3/2; ^ⅲ x, y+1, z; v x, y-1, z

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  Adjacent Mn(Ⅱ) ions are bridged by the 4, 4′-bipy molecules in the bis-monodentate mode, with the Mn…Mn separation distance of 1.163 5 nm, resulting in a one-dimensional infinite chain structure. The chains are further connected by the O atoms of 3, 3′-thiodipropionate ligands to give a two-dimensional layer structure, with the Mn…Mn separation distance of 0.387 0 nm (Fig. 2). There exist π-π stacking interac-tions between adjacent pyridine rings (Cg1…Cg2 0.361 0 nm; Cg1: C7, C8, C9, C10, C11, N1 (Symmetry codes: 1.5-x, 0.5+y, 1.5-z); Cg2: C7, C8, C9, C10, C11, N1 (Symmetry codes: 0.5+x, 0.5+y, z); the dihedral angle=0.3°) and an intermole-cular hydrogen bond (O1W…O4^ⅳ 0.282(1) nm, Symmetry codes: ^ⅳ -x+1/2, -y+5/2, -z+2).

  Figure 2

  

  Figure 2.  Two-dimensional structure of 1

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  Furthermore, there exist other π-π stacking interactions between adjacent layers (C…Cg 0.325 6 nm), leading to the formation of a three-dimensional supramolecular network (Fig. 3).

  Figure 3

  

  Figure 3.  Three-dimensional structure of 1

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  2.2   Crystal structure of {[Cu(DPA)(bpp)(H₂O)]·H₂O}_n (2)

  As depicted in Fig. 4, the Cu(Ⅱ) ion exists in a distorted octahedral coordination configuration, defined by two N-atom donors from two monodentate 1, 3-bis(4-pyridyl)propane co-ligands, three O-atom donors from two different 3, 3′-thiodipropionate ligands, where one carboxylate group (O3^ⅰ-C-O4^ⅰ) coordinates in a bidentate mode and the other group (O1-C-O2) coordinates in a monodentate mode, as well as one coordination water molecule. Differing from 1, the carboxylate O2 of 2 is uncoordinated to Cu(Ⅱ) ion. Atoms O1, O3^ⅰ, O4^ⅰ and O1W comprise the equatorial plane, and atoms N1 and N2 occupy the axial positions (N(1)-Cu(1)-N(2) 176.6(3)°). The bond lengths of Cu-N are 0.200 6(6) and 0.203 1(7) nm, respectively, and the bond lengths of Cu-O are 0.195 1(6), 2.000(5), 0.226 5(6) and 0.273 0(6) nm, respectively (Table 2). It is noted that the Cu-O(4) distance is much longer than other Cu-O distances^[16-17]. Two kinds of intra-molecular hydrogen bonds are observed in the complex: O(1W)…O(2W) 0.276 4(1) nm and O(2W)…O(2) 0.265 2(1) nm, as shown in Table 3.

  Figure 4

  

  Figure 4.  Molecular structure of 2 with the ellipsoids drawn at the 30% probability level

  Symmetry codes:^ⅰ x-1, y, z; ^ⅱ x+1, -y+1/2, z+1/2

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  Table 3

  

  Table 3.  Hydrogen bond parameters for the complexes

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  D-H…A	d(D-H)/nm	d(H…A)/nm	d(D…A)/nm	∠D-H…A/(°)
  Complex 1
  O(1W)-HWA…O(4)ⅳ	0.085	0.237	0.281 9(1)	113.4
  Complex 2
  O(1W)-H(1WA) …O(3)ⅴ	0.085(1)	0.193(4)	0.273 9(8)	159(1)
  O(1W)-H(1WB)…O(2W)	0.085(1)	0.192(2)	0.276 4(1)	175(9)
  O(2W)-H(2WA)…O(4)ⅳ	0.085(1)	0.217(1)	0.280 1(9)	131(1)
  O(2W)-H(2WB)…O(2)	0.085(1)	0.196(1)	0.265 2(1)	138(1)
  Symmetry codes: ⅳ -x+1/2, -y+5/2, -z+2 for 1; ⅳ x-1, -y+1/2, z-1/2, ⅴ -x+2, -y, -z+1 for 2.

  Adjacent Cu(Ⅱ) ions are bridged by 1, 3-bis(4-pyridyl)propane molecules, resulting in a one-dimensional infinite chain structure. In the chain, the adjacent Cu…Cu distance is 1.211 2 nm. The adjacent chains are further linked by the 3, 3′-thiodipropionate ligands to give a two-dimensional layer structure, with the Cu…Cu separation distance of 1.040 8 nm (Fig. 5). In addition, it is observed that there exist intermolecular hydrogen bonds: O-H…O (O(1W)…O(3)^ⅴ 0.273 9(8) nm and O(2W)…O(4)^ⅳ 0.280 1(9) nm; Symmetry codes: ^ⅳ x-1, -y+1/2, z-1/2; ^ⅴ -x+2, -y, -z+1), resulting in a three-dimensional supramolecular network structure (Fig. 6).

  Figure 5

  

  Figure 5.  Two-dimensional layer structure of complex 2

  Symmetry codes: ^ⅱ x+1, -y+1/2, z+1/2; ^ⅲ x+1, y, z; iv x-1, -y+1/2, z-1/2

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  Figure 6

  

  Figure 6.  Three-dimensional structure of complex 2

  Symmetry code: ^ⅳ x-1, -y+1/2, z-1/2, ^ⅴ-x+2, -y, -z+1

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  2.3   XRD and thermogravimetric analysis

  Powder X-ray diffraction (XRD) patterns for solid samples of complexes 1 and 2 are measured at room temperature as illustrated in Fig. 7. The patterns are highly similar to their simulated ones (based on the single-crystal X-ray diffraction data), indicating that the single-crystal structures are really representative of the bulk of the corresponding samples.

  Figure 7

  

  Figure 7.  PXRD patterns for complexes 1 (a) and 2 (b)

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  From the thermal analysis curves of complex 1 (Fig. 8), we can see that there are three weight-loss steps. Above 26 ℃ up to 186 ℃, a small amount of molecular fragment is found(Obsd. 4.50%, Calcd. 4.44%), which is attributed to the dehydration of the uncoordinated water molecules. A rapid weight loss can be detected from 186 to 537 ℃, which is attributed to the dehydration of 4, 4′-bipy molecules and carboxyl groups. After gradually burning decomposi-tion, the final residue may be MnO (Obsd. 17.68%, Calcd. 17.50%).

  Figure 8

  

  Figure 8.  TG curve of complex 1

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  The result of TG analysis of complex 2 is showed in Fig. 9. The first weight loss can be detected from 33 to 168 ℃ (Obsd. 4.40%, Calcd. 7.60%), which is attributed to the dehydration of the uncoordinated and coordinated water molecules. The weight loss occurr-ing between 168 and 432 ℃ corresponds to decom-position of 1, 3-bis(4-pyridyl)propane molecules and carboxyl groups. The final residual is CuO (Obsd. 16.54, Calcd. 16.78%).

  Figure 9

  

  Figure 9.  TG curve of complex 2

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• 

  Figure 1  Molecular structure of 1 with ellipsoids drawn at 30% probability level

  Symmetry codes:^ⅰ-x+1, y, -z+3/2; ^ⅱ-x+1/2, y-1/2, -z+3/2; ^ⅲ x, y+1, z; v x, y-1, z

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  Figure 2  Two-dimensional structure of 1

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  Figure 3  Three-dimensional structure of 1

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  Figure 4  Molecular structure of 2 with the ellipsoids drawn at the 30% probability level

  Symmetry codes:^ⅰ x-1, y, z; ^ⅱ x+1, -y+1/2, z+1/2

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  Figure 5  Two-dimensional layer structure of complex 2

  Symmetry codes: ^ⅱ x+1, -y+1/2, z+1/2; ^ⅲ x+1, y, z; iv x-1, -y+1/2, z-1/2

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  Figure 6  Three-dimensional structure of complex 2

  Symmetry code: ^ⅳ x-1, -y+1/2, z-1/2, ^ⅴ-x+2, -y, -z+1

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  Figure 7  PXRD patterns for complexes 1 (a) and 2 (b)

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  Figure 8  TG curve of complex 1

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  Figure 9  TG curve of complex 2

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  Table 1.  Crystal data and structure parameters for the complexes

  Complex	1	2
  Formula	C16H18N2O5SMn	C19H26N2O6SCu
  Formula weight	405.32	474.02
  Temperature/K	293(2)	293(2)
  Size/mm	0.20×0.10×0.10	0.21×0.18×0.15
  θ range for data collection/(°)	2.16~25.39	2.01~25.37
  Crystal system	Monoclinic	Monoclinic
  Space group	C2/c	P21/c
  a/nm	1.626 4(3)	1.040 8(2)
  b/nm	1.163 5(2)	1.233 3(3)
  c/nm	1.861 3(4)	1.747 0(4)
  β/(°)	99.94(3)	102.99(3)
  V/nm3	3.469(1)	2.185(8)
  Z	8	4
  Dc/(g·cm-3)	1.552	1.441
  μ/mm-1	0.911	1.131
  F(000)	1 672	988
  Reflection collected	3 160	4 249
  Unique reflection (Rint)	1 551 (0.000 0)	4 017 (0.067 2)
  R1, wR2 [I > 2σ(I)]	0.079 6, 0.148 7	0.071 3, 0.197 2
  R1, wR2 (all data)	0.158 1, 0.177 4	0.121 6, 0.277 7
  Goodness-of-fit (on F2)	1.002	1.060
  (Δρ)max, (Δρ)min/(e·nm-3)	753, -691	1 024, -1 063

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

  1
  Mn(1)-O(1)	0.216 9(5)	Mn(1)-O(2)ⅰ	0.207 8(6)	Mn(1)-O(3)ⅱ	0.246 8(5)
  Mn(1)-O(4)ⅱ	0.221 5(6)	Mn(1)-N(1)	0.226 7(5)	Mn(1)-N(2)ⅲ	0.229 1(5)
  O(1)-Mn(1)-O(3)ⅱ	84.1(2)	O(1)-Mn(1)-O(4)ⅱ	136.8(2)	O(1)-Mn(1)-N(1)	89.8(2)
  O(1)-Mn(1)-N(2)ⅲ	89.4(2)	O(2)ⅰ-Mn(1)-O(1)	125.8(3)	O(2)ⅰ-Mn(1)-O(3)ⅱ	150.0(3)
  O(2)ⅰ-Mn(1)-O(4)ⅱ	97.1(3)	O(2)ⅰ-Mn(1)-N(1)	88.9(2)	O(2)ⅰ-Mn(1)-N(2)ⅲ	88.0(2)
  O(4)ⅱ-Mn(1)-O(3)ⅱ	53.6(2)	O(4)ⅱ-Mn(1)-N(1)	85.0(2)	O(4)ⅱ-Mn(1)-N(2)ⅲ	98.5(2)
  N(1)-Mn(1)-N(2)ⅲ	175.6(2)	N(1)-Mn(1)-O(3)ⅱ	94.0(2)
  2
  Cu(1)-O(1)	0.195 1(6)	Cu(1)-O(3)ⅰ	0.200 0(5)	Cu(1)-O(4)ⅰ	0.273 0(6)
  Cu(1)-O1W	0.226 5(6)	Cu(1)-N(1)	0.200 6(6)	Cu(1)-(N2)ⅱ	0.203 1(7)
  O(1)-Cu(1)-O(3)ⅰ	159.4(2)	O(1)-Cu(1)-N(1)	95.9(2)	O(1)-Cu(1)-N(2)ⅱ	86.7(3)
  O(1)-Cu(1)-O1W	101.2(3)	O(3)ⅰ-Cu(1)-N(1)	86.3(2)	O(3)ⅰ-Cu(1)-N(2)ⅱ	90.5(2)
  O(3)-Cu(1)-O1W	99.2(2)	N(1)-Cu(1)-O1W	92.3(2)	N(1)-Cu(1)-N(2)ⅱ	176.6(3)
  N(2)ⅱ-Cu(1)-O1W	89.3(3)	O(3)ⅰ-Cu(1)-O(4)ⅰ	52.8(2)
  Symmetry codes: ⅰ -x+1, y, -z+3/2; ⅱ -x+1/2, y-1/2, -z+3/2; ⅲ x, y+1, z for 1; ⅰ x-1, y, z; ⅱ x+1, -y+1/2, z+1/2 for 2.

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  Table 3.  Hydrogen bond parameters for the complexes

  D-H…A	d(D-H)/nm	d(H…A)/nm	d(D…A)/nm	∠D-H…A/(°)
  Complex 1
  O(1W)-HWA…O(4)ⅳ	0.085	0.237	0.281 9(1)	113.4
  Complex 2
  O(1W)-H(1WA) …O(3)ⅴ	0.085(1)	0.193(4)	0.273 9(8)	159(1)
  O(1W)-H(1WB)…O(2W)	0.085(1)	0.192(2)	0.276 4(1)	175(9)
  O(2W)-H(2WA)…O(4)ⅳ	0.085(1)	0.217(1)	0.280 1(9)	131(1)
  O(2W)-H(2WB)…O(2)	0.085(1)	0.196(1)	0.265 2(1)	138(1)
  Symmetry codes: ⅳ -x+1/2, -y+5/2, -z+2 for 1; ⅳ x-1, -y+1/2, z-1/2, ⅴ -x+2, -y, -z+1 for 2.

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