English

• 0.   Introduction

  The design and synthesis of functional coordination polymers have become the subjects of extensive investigation owing to their intriguing architectures and functional properties, such as magnetism, catalysis, luminescence, and gas storage^[1-5]. However, there still remains a great challenge for directional construction of functional coordination polymers with predictable molecular structures and expected properties, because a lot of factors influence the construction of complexes, such as the structural features of organic ligands, the coordination requirements of metal ions, solvent systems, temperatures, and pH values^[6-10].

  In this context, various types of aromatic polycarboxylic acids have been extensively utilized to synthesize various 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^{[2-3, 6, 10-14]}.

  As a combination of the aforementioned aspects and our previous research work, we have selected a new asymmetric tetracarboxylate ligand, 2, 3, 3′, 4′-diphenyl ether tetracarboxylic acid (H₄L, Scheme 1) and explored it for the construction of novel coordination polymers. 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 providing 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.

  Scheme 1

  

  Scheme 1.  Structures of H₄L and the auxiliary ligands

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  In this work, we report the syntheses, crystal structures, and luminescent properties of two Cd(Ⅱ) coordination polymers constructed from the tetracarboxylate ligand.

  1.   Experimental

  1.1   Reagents and physical measurements

  All chemicals and solvents were of AR grade and used without further purification. H₄L was acquired from Jinan Henghua Sci. & Technol. Co., Ltd. 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.

  1.2   Synthesis of [Cd₂(μ₅-L)(phen)₂]_n (1)

  A mixture of CdCl₂·H₂O (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. Colourless block - shaped crystals of 1 were isolated manually, and washed with distilled water. Yield: 43% (based on H₄L). Anal. Calcd. for C₄₀H₂₂Cd₂N₄O₉(%): C 51.80, H 2.39, N 6.04; Found(%): C 51.93, H 2.38, N 6.01. IR (KBr, cm^-1): 1 588s, 1 515w, 1 431w, 1 397s, 1 363m, 1 256w, 1 240w, 1 144w, 1 099w, 1 060w, 980w, 924w, 851m, 783w, 727m, 699w, 637w.

  1.3   Synthesis of {[Cd₂(μ₄-L)(2, 2′-bipy)₂(H₂O)₂]· 2H₂O}_n (2)

  The preparation of 2 was similar to that of 1 except 2, 2′-bipy was used instead of phen. After cooling the reaction mixture to room temperature, colourless block-shaped crystals of 2 were isolated manually, washed with distilled water, and dried. Yield: 48% (based on H₄L). Anal. Calcd. for C₃₆H₃₀Cd₂N₄O₁₃(%): C 45.44, H 3.18, N 5.89; Found(%): C 45.21, H 3.16, N 5.93. IR (KBr, cm^-1): 3 390w, 3 074w, 1 567s, 1 470w, 1 436m, 1 391s, 1 313w, 1 256w, 1 234m, 1 154w, 1 060w, 1 015w, 980w, 856w, 823w, 806w, 766m, 733w, 699w, 654w.

  The compounds 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 0.22 mm× 0.21 mm×0.19 mm (1) and 0.21 mm×0.20 mm×0.18 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^[15]. All non-hydrogen atoms were refined anisotropically. All the hydrogen atoms were positioned geometrically and refined using a riding model. 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 compounds 1 and 2 are listed in Table 2. Hydrogen bond parameters of compound 2 are given in Table 3.

  Table 1

  

  Table 1.  Crystal data for compounds 1 and 2

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  Compound	1	2
  Chemical formula	C40H22Cd2N4O9	C36H30Cd2N4O13
  Formula weight	927.41	951.44
  Crystal system	Monoclinic	Triclinic
  Space group	P21/c	P1
  a / nm	1.184 09(8)	0.930 77(8)
  b / nm	1.178 61(11)	1.191 97(11)
  c / nm	2.389 62(18)	1.713 64(11)
  α / (°)		97.116(6)
  β / (°)	91.964(6)	92.986(6)
  γ / (°)		109.187(8)
  V / nm3	3.332 9(5)	1.773 0(3)
  Z	4	2
  F(000)	1832	948
  θ range for data collection / (°)	3.412~25.042	3.389~25.050
  Limiting indices	-14 ≤ h ≤ 14, -14 ≤ k ≤ 11, -28 ≤ l ≤ 23	-11 ≤ h ≤ 11, -14 ≤ k ≤ 13, -20 ≤ l ≤ 17
  Reflection collected, unique (Rint)	20 338, 5 885 (0.107 9)	11 174, 6 248 (0.068 6)
  Dc / (Mg·m-3)	1.848	1.782
  μ / mm-1	1.345	1.274
  Data, restraint, parameter	5 885, 0, 496	6 248, 0, 496
  Goodness-of-fit on F2	0.848	1.056
  Final R indices [I≥2σ(I)] R1, wR2	0.056 7, 0.080 6	0.063 9, 0.080 4
  R indices (all data) R1, wR2	0.101 2, 0.110 8	0.103 8, 0.131 1
  Largest diff. peak and hole / (e·nm-3)	916 and -707	785 and -928

  Table 2

  

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

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  1
  Cd(1)-O(1)	0.253 3(5)	Cd(1)-O(3)	0.232 3(5)	Cd(1)-O(4)A	0.224 7(5)
  Cd(1)-O(8)B	0.218 9(6)	Cd(1)-N(1)	0.237 0(6)	Cd(1)-N(2)	0.238 1(6)
  Cd(2)-O(1)	0.233 1(5)	Cd(2)-O(2)	0.236 8(5)	Cd(2)-O(6)B	0.240 1(5)
  Cd(2)-O(7)B	0.231 8(5)	Cd(2)-N(3)	0.232 2(7)	Cd(2)-N(4)	0.228 6(6)
  O(8)B-Cd(1)-O(4)A	97.8(2)	O(8)B-Cd(1)-O(3)	151.7(2)	O(4)A-Cd(1)-O(3)	96.82(18)
  N(1)-Cd(1)-O(8)B	91.3(2)	O(4)A-Cd(1)-N(1)	151.6(2)	O(3)-Cd(1)-N(1)	87.15(19)
  O(8)B-Cd(1)-N(2)	123.8(2)	O(4)A-Cd(1)-N(2)	82.67(19)	O(3)-Cd(1)-N(2)	82.0(2)
  N(1)-Cd(1)-N(2)	70.0(2)	O(8)B-Cd(1)-O(1)	75.1(2)	O(1)-Cdo(1)-O(4)A	106.77(18)
  O(3)-Cd(1)-O(1)	77.60(18)	O(1)-Cd(1)-N(1)	101.6(2)	O(1)-Cd(1)-N(2)	158.38(17)
  O(7)B-Cd(2)-N(4)	132.1(2)	N(3)-Cd(2)-N(4)	72.2(2)	O(7)B-Cd(2)-N(3)	103.3(2)
  N(4)-Cd(2)-O(1)	117.2(2)	O(1)-Cd(2)-O(7)B	99.83(19)	O(1)-Cd(2)-N(3)	134.6(2)
  O(2)-Cd(2)-N(4)	134.2(2)	O(7)B-Cd(2)-O(2)	91.06(19)	O(2)-Cd(2)-N(3)	85.06(19)
  O(1)-Cd(2)-O(2)	55.76(17)	O(6)B-Cd(2)-N(4)	84.4(2)	O(7)B-Cd(2)-O(6)B	55.24(17)
  N(3)-Cd(2)-O(6)B	118.7(2)	O(1)-Cd(2)-O(6)B	106.64(19)	O(2)-Cd(2)-O(6)B	140.98(18)
  2
  Cd(1)-O(1)	0.256 2(6)	Cd(1)-O(2)	0.228 4(5)	Cd(1)-O(4)A	0.227 9(6)
  Cd(1)-O(10)	0.235 5(6)	Cd(1)-N(1)	0.233 3(7)	Cd(1)-N(2)	0.232 3(6)
  Cd(2)-O(6)B	0.250 0(6)	Cd(2)-O(7)B	0.236 2(7)	Cd(2)-O(8)	0.236 6(5)
  Cd(2)-O(9)	0.242 7(6)	Cd(2)-O(11)	0.238 4(6)	Cd(2)-N(3)	0.229 7(8)
  Cd(2)-N(4)	0.230 2(7)
  O(2)-Cd(1)-O(4)A	108.2(2)	O(4)A-Cd(1)-N(2)	97.8(2)	O(2)-Cd(1)-N(2)	153.9(2)
  N(1)-Cd(1)-O(4)A	117.7(2)	O(2)-Cd(1)-N(1)	97.2(2)	N(2)-Cd(1)-N(1)	69.8(2)
  O(4)A-Cd(1)-O(10)	79.0(2)	O(10)-Cd(1)-O(2)	95.0(2)	O(10)-Cd(1)-N(2)	89.9(2)
  N(1)-Cd(1)-O(10)	154.6(2)	O(4)A-Cd(1)-O(1)	149.9(2)	O(1)-Cdo(1)-O(2)	53.56(18)
  N(2)-Cd(1)-O(1)	102.6(2)	O(1)-Cd(1)-N(1)	90.2(2)	O(1)-Cd(1)-O(10)	79.3(2)
  N(3)-Cd(2)-N(4)	70.9(3)	N(3)-Cd(2)-O(7)B	96.5(3)	O(7)B-Cd(2)-N(4)	130.1(2)
  N(3)-Cd(2)-O(8)	99.3(2)	N(4)-Cd(2)-O(8)	139.7(2)	O(7)B-Cd(2)-O(8)	89.1(2)
  O(11)-Cd(2)-N(3)	165.4(3)	O(11)-Cd(2)-N(4)	95.8(3)	O(7)B-Cd(2)-O(11)	96.8(2)
  O(8)-Cd(2)-O(11)	86.9(2)	O(9)-Cd(2)-N(3)	88.5(2)	O(9)-Cd(2)-N(4)	86.4(2)
  O(7)B-Cd(2)-O(9)	142.8(2)	O(8)-Cd(2)-O(9)	53.73(19)	O(11)-Cd(2)-O(9)	84.5(2)
  N(3)-Cd(2)-O(6)B	109.5(2)	N(4)-Cd(2)-O(6)B	85.9(2)	O(7)B-Cd(2)-O(6)B	52.1(2)
  O(8)-Cd(2)-O(6)B	132.9(2)	O(11)-Cd(2)-O(6)B	74.5(2)	O(9)-Cd(2)-O(6)B	156.8(3)
  Symmetry transformations used to generate equivalent atoms: A: -x, -y+2, -z+1; B: x-1, y, z for 1; A: -x+1, -y+1, -z+1; B: -x, -y, -z+2 for 2.

  Table 3

  

  Table 3.  Hydrogen bond parameters of compound 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(1)A	0.085 0	0.196 5	0.281 5	179.74
  O(10)—H(2W)…O(12)	0.089 0	0.177 9	0.264 7	164.37
  O(11)—H(3W)…O(8)B	0.081 3	0.194 6	0.275 3	172.06
  O(11)—H(4W)…O(13)C	0.072 2	0.208 2	0.278 5	164.98
  O(12)—H(5W)…O(2)D	0.085 0	0.202 0	0.287 0	179.20
  O(12)—H(6W)…O(3)	0.085 0	0.1873	0.272 3	178.95
  O(13)—H(7W)…O(7)E	0.079 9	0.1580	0.237 2	170.57
  Symmetry codes: A: -x+2, -y+1, -z+1; B: -x, -y, -z+2; C: x, y-1, z+1; D: -x+1, -y+1, -z+1; E: x, y+1, z-1.

  CCDC: 1971327, 1; 1971328, 2.

  2.   Results and discussion

  2.1   Description of the structures

  2.1.1   [Cd₂(μ₅-L)(phen)₂]_n (1)

  The molecular structure of compound 1 is shown in Fig. 1. The asymmetric unit contains two Cd atoms (Cd1 and Cd₂), a μ₅-L^4- ligand, and two phen moieties. The six-coordinated Cd1 center displays a distorted octahedral {CdN₂O₄} environment filled by four carboxylate O atoms from three individual μ₅-L^4- blocks and two N atoms from the phen moiety. The Cd2 center is also six-coordinated and features a distorted octahedral {CdN₂O₄} geometry that is taken by four carboxylate O atoms from two different μ₅-L^4- blocks and two N atoms from the phen moiety. The lengths of the Cd-O and Cd- N bonds are 0.218 9(6)~0.253 3(5) and 0.228 6(6)~ 0.238 1(6) nm, respectively, which are within the normal values for related Cd(Ⅱ) derivatives^{[6, 10, 16]}. In 1, the L^4- block acts as a μ₅-ligand, wherein the COO^- groups are monodentate, bidentate or tridentate (mode Ⅰ, Scheme 2). The carboxylate groups of four μ₅ - L^4- blocks link the adjacent Cd(Ⅱ) centers into a Cd₄ subunit (Fig. 2). Such subunits are further assembled via the remaining COO- groups of μ₅ - L^4- blocks to a 1D chain (Fig. 2).

  Figure 1

  

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

  H atoms were omitted for clarity; Symmetry codes: A:-x, -y+2, -z+1; B: x-1, y, z

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  Scheme 2

  

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

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  Figure 2

  

  Figure 2.  View of 1D chain in compound 1 along b axis

  Phen ligands are omitted for clarity; Symmetry codes: A:-x, -y+2, -z+1; B: x-1, y, z; C: x+1, y, z

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  2.1.2   {[Cd₂(μ₄-L)(2, 2′-bipy)₂(H₂O)₂]·2H₂O}_n (2)

  The asymmetric unit of 2 bears two Cd(Ⅱ) centers (Cd1 and Cd2), one μ₄ -L^4- linker, two 2, 2′ - bipy moieties, two terminal water ligands and two lattice water molecules (Fig. 3). The seven - coordinated Cd1 center adopts a distorted pentagonal bipyramid {CdN₂O₅} environment taken by four carboxylate O atoms from two independent μ₄-L^4- blocks, one O atom from the H₂O ligand, and a pair of N atoms from the 2, 2′-bipy moiety. The Cd₂ center is six-coordinated and reveals a distort- ed octahedral {CdN₂O₄} geometry. It is completed by three carboxylate O donors from two μ₄-L^4- blocks, one O atom from the H₂O ligand, and two N donors from the 2, 2′ - bipy moiety. The Cd - O (0.227 9(6)~0.256 2(6) nm) and Cd - N (0.229 7(8)~0.233 3(7) nm) bonds are within standard values^{[14, 16-17]}. The L^4- block behaves as a heptadentate μ₄-linker (Scheme 2, mode Ⅱ). Two μ₄- L^4- blocks link adjacent Cd(Ⅱ) centers to form a Cd₂ unit (Fig. 4). Furthermore, these Cd₂ units are further extended by μ₄-L^4- blocks into a 1D chain (Fig. 4). Com- pounds 1 and 2 were obtained under similar reaction conditions except using different auxiliary ligands (phen for 1 and 2, 2′-bipy for 2), which result in differ- ent structures.

  Figure 3

  

  Figure 3.  Drawing of asymmetric unit of compound 2 with 30% probability thermal ellipsoids

  Lattice water molecule and H atoms were omitted for clarity; Symmetry codes: A:-x+1, -y+1, -z+1; B: -x, -y, -z+2

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  Figure 4

  

  Figure 4.  View of 1D chain in compound 2 along a axis

  2, 2′-Bipy ligands are omitted for clarity; Symmetry codes: A:-x+1, -y+1, -z+1; B: -x, -y, -z+2; C: x+1, y+1, z-1

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  2.2   TGA analysis

  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. 5, TGA curve of compound 1 shows that the sample remained stable until 327 ℃. Compound 2 lost its two lattice water molecules and two H₂O ligands in a range of 45~157 ℃ (Obsd. 7.2%; Calcd. 7.6%), followed by the decomposition at 254 ℃.

  Figure 5

  

  Figure 5.  TGA curves of compounds 1 and 2

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  2.3   Luminescent properties

  Solid-state emission spectra of H₄L and cadmium(Ⅱ) compounds 1 and 2 were measured at room temperature (Fig. 6). The spectrum of H₄L revealed a weak emission with a maximum at 384 nm (λ_ex=320 nm). In comparison with H₄L, compounds 1 and 2 exhibited more extensive emission with maximum at 376 and 381 nm (λ_ex=320 nm). These emissions correspond to intraligand π-π^* or n-π^* transition of H₂L^{[6, 10, 17]}. Enhancement of the luminescence in 1 and 2 compared to H₄L can be explained by the coordination of ligands to Cd(Ⅱ); the coordination can augment a rigidity of ligands and reduce an energy loss due to radiationless decay^{[10, 16-17]}.

  Figure 6

  

  Figure 6.  Solid-state emission spectra of H₄L and compounds 1 and 2 at room temperature

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  3.   Conclusions

  In summary, we have successfully synthesized and characterized two new cadmium coordination polymers by using a tetracarboxylate acid as a ligand under hydrothermal condition. Compounds 1 and 2 show 1D chains composed of Cd₄ and Cd₂ units, respectively. Besides, the luminescent properties were also investigated and discussed. The results show that such tetracarboxylic acid can be used as a versatile multifunctional building block toward the generation of new coordination polymers.

  
  
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• 

  Scheme 1  Structures of H₄L and the auxiliary ligands

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

  H atoms were omitted for clarity; Symmetry codes: A:-x, -y+2, -z+1; B: x-1, y, z

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

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  Figure 2  View of 1D chain in compound 1 along b axis

  Phen ligands are omitted for clarity; Symmetry codes: A:-x, -y+2, -z+1; B: x-1, y, z; C: x+1, y, z

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  Figure 3  Drawing of asymmetric unit of compound 2 with 30% probability thermal ellipsoids

  Lattice water molecule and H atoms were omitted for clarity; Symmetry codes: A:-x+1, -y+1, -z+1; B: -x, -y, -z+2

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  Figure 4  View of 1D chain in compound 2 along a axis

  2, 2′-Bipy ligands are omitted for clarity; Symmetry codes: A:-x+1, -y+1, -z+1; B: -x, -y, -z+2; C: x+1, y+1, z-1

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  Figure 5  TGA curves of compounds 1 and 2

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  Figure 6  Solid-state emission spectra of H₄L and compounds 1 and 2 at room temperature

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  Table 1.  Crystal data for compounds 1 and 2

  Compound	1	2
  Chemical formula	C40H22Cd2N4O9	C36H30Cd2N4O13
  Formula weight	927.41	951.44
  Crystal system	Monoclinic	Triclinic
  Space group	P21/c	P1
  a / nm	1.184 09(8)	0.930 77(8)
  b / nm	1.178 61(11)	1.191 97(11)
  c / nm	2.389 62(18)	1.713 64(11)
  α / (°)		97.116(6)
  β / (°)	91.964(6)	92.986(6)
  γ / (°)		109.187(8)
  V / nm3	3.332 9(5)	1.773 0(3)
  Z	4	2
  F(000)	1832	948
  θ range for data collection / (°)	3.412~25.042	3.389~25.050
  Limiting indices	-14 ≤ h ≤ 14, -14 ≤ k ≤ 11, -28 ≤ l ≤ 23	-11 ≤ h ≤ 11, -14 ≤ k ≤ 13, -20 ≤ l ≤ 17
  Reflection collected, unique (Rint)	20 338, 5 885 (0.107 9)	11 174, 6 248 (0.068 6)
  Dc / (Mg·m-3)	1.848	1.782
  μ / mm-1	1.345	1.274
  Data, restraint, parameter	5 885, 0, 496	6 248, 0, 496
  Goodness-of-fit on F2	0.848	1.056
  Final R indices [I≥2σ(I)] R1, wR2	0.056 7, 0.080 6	0.063 9, 0.080 4
  R indices (all data) R1, wR2	0.101 2, 0.110 8	0.103 8, 0.131 1
  Largest diff. peak and hole / (e·nm-3)	916 and -707	785 and -928

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

  1
  Cd(1)-O(1)	0.253 3(5)	Cd(1)-O(3)	0.232 3(5)	Cd(1)-O(4)A	0.224 7(5)
  Cd(1)-O(8)B	0.218 9(6)	Cd(1)-N(1)	0.237 0(6)	Cd(1)-N(2)	0.238 1(6)
  Cd(2)-O(1)	0.233 1(5)	Cd(2)-O(2)	0.236 8(5)	Cd(2)-O(6)B	0.240 1(5)
  Cd(2)-O(7)B	0.231 8(5)	Cd(2)-N(3)	0.232 2(7)	Cd(2)-N(4)	0.228 6(6)
  O(8)B-Cd(1)-O(4)A	97.8(2)	O(8)B-Cd(1)-O(3)	151.7(2)	O(4)A-Cd(1)-O(3)	96.82(18)
  N(1)-Cd(1)-O(8)B	91.3(2)	O(4)A-Cd(1)-N(1)	151.6(2)	O(3)-Cd(1)-N(1)	87.15(19)
  O(8)B-Cd(1)-N(2)	123.8(2)	O(4)A-Cd(1)-N(2)	82.67(19)	O(3)-Cd(1)-N(2)	82.0(2)
  N(1)-Cd(1)-N(2)	70.0(2)	O(8)B-Cd(1)-O(1)	75.1(2)	O(1)-Cdo(1)-O(4)A	106.77(18)
  O(3)-Cd(1)-O(1)	77.60(18)	O(1)-Cd(1)-N(1)	101.6(2)	O(1)-Cd(1)-N(2)	158.38(17)
  O(7)B-Cd(2)-N(4)	132.1(2)	N(3)-Cd(2)-N(4)	72.2(2)	O(7)B-Cd(2)-N(3)	103.3(2)
  N(4)-Cd(2)-O(1)	117.2(2)	O(1)-Cd(2)-O(7)B	99.83(19)	O(1)-Cd(2)-N(3)	134.6(2)
  O(2)-Cd(2)-N(4)	134.2(2)	O(7)B-Cd(2)-O(2)	91.06(19)	O(2)-Cd(2)-N(3)	85.06(19)
  O(1)-Cd(2)-O(2)	55.76(17)	O(6)B-Cd(2)-N(4)	84.4(2)	O(7)B-Cd(2)-O(6)B	55.24(17)
  N(3)-Cd(2)-O(6)B	118.7(2)	O(1)-Cd(2)-O(6)B	106.64(19)	O(2)-Cd(2)-O(6)B	140.98(18)
  2
  Cd(1)-O(1)	0.256 2(6)	Cd(1)-O(2)	0.228 4(5)	Cd(1)-O(4)A	0.227 9(6)
  Cd(1)-O(10)	0.235 5(6)	Cd(1)-N(1)	0.233 3(7)	Cd(1)-N(2)	0.232 3(6)
  Cd(2)-O(6)B	0.250 0(6)	Cd(2)-O(7)B	0.236 2(7)	Cd(2)-O(8)	0.236 6(5)
  Cd(2)-O(9)	0.242 7(6)	Cd(2)-O(11)	0.238 4(6)	Cd(2)-N(3)	0.229 7(8)
  Cd(2)-N(4)	0.230 2(7)
  O(2)-Cd(1)-O(4)A	108.2(2)	O(4)A-Cd(1)-N(2)	97.8(2)	O(2)-Cd(1)-N(2)	153.9(2)
  N(1)-Cd(1)-O(4)A	117.7(2)	O(2)-Cd(1)-N(1)	97.2(2)	N(2)-Cd(1)-N(1)	69.8(2)
  O(4)A-Cd(1)-O(10)	79.0(2)	O(10)-Cd(1)-O(2)	95.0(2)	O(10)-Cd(1)-N(2)	89.9(2)
  N(1)-Cd(1)-O(10)	154.6(2)	O(4)A-Cd(1)-O(1)	149.9(2)	O(1)-Cdo(1)-O(2)	53.56(18)
  N(2)-Cd(1)-O(1)	102.6(2)	O(1)-Cd(1)-N(1)	90.2(2)	O(1)-Cd(1)-O(10)	79.3(2)
  N(3)-Cd(2)-N(4)	70.9(3)	N(3)-Cd(2)-O(7)B	96.5(3)	O(7)B-Cd(2)-N(4)	130.1(2)
  N(3)-Cd(2)-O(8)	99.3(2)	N(4)-Cd(2)-O(8)	139.7(2)	O(7)B-Cd(2)-O(8)	89.1(2)
  O(11)-Cd(2)-N(3)	165.4(3)	O(11)-Cd(2)-N(4)	95.8(3)	O(7)B-Cd(2)-O(11)	96.8(2)
  O(8)-Cd(2)-O(11)	86.9(2)	O(9)-Cd(2)-N(3)	88.5(2)	O(9)-Cd(2)-N(4)	86.4(2)
  O(7)B-Cd(2)-O(9)	142.8(2)	O(8)-Cd(2)-O(9)	53.73(19)	O(11)-Cd(2)-O(9)	84.5(2)
  N(3)-Cd(2)-O(6)B	109.5(2)	N(4)-Cd(2)-O(6)B	85.9(2)	O(7)B-Cd(2)-O(6)B	52.1(2)
  O(8)-Cd(2)-O(6)B	132.9(2)	O(11)-Cd(2)-O(6)B	74.5(2)	O(9)-Cd(2)-O(6)B	156.8(3)
  Symmetry transformations used to generate equivalent atoms: A: -x, -y+2, -z+1; B: x-1, y, z for 1; A: -x+1, -y+1, -z+1; B: -x, -y, -z+2 for 2.

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  Table 3.  Hydrogen bond parameters of compound 2

  D—H…A	d(D-H) / nm	d(H…A) / nm	d(D…A) / nm	∠DHA / (°)
  O(10)—H(1W)…O(1)A	0.085 0	0.196 5	0.281 5	179.74
  O(10)—H(2W)…O(12)	0.089 0	0.177 9	0.264 7	164.37
  O(11)—H(3W)…O(8)B	0.081 3	0.194 6	0.275 3	172.06
  O(11)—H(4W)…O(13)C	0.072 2	0.208 2	0.278 5	164.98
  O(12)—H(5W)…O(2)D	0.085 0	0.202 0	0.287 0	179.20
  O(12)—H(6W)…O(3)	0.085 0	0.1873	0.272 3	178.95
  O(13)—H(7W)…O(7)E	0.079 9	0.1580	0.237 2	170.57
  Symmetry codes: A: -x+2, -y+1, -z+1; B: -x, -y, -z+2; C: x, y-1, z+1; D: -x+1, -y+1, -z+1; E: x, y+1, z-1.

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