English

• 0.   Introduction

  In recent years, coordination polymers have attracted attention due to their wide applications in gas adsorption^[1-2], dye degradation^[3-5], separation and enrichment^[6-8], electrochemical^[9-11] and fluorescence sensing^[12-14]. There are many factors that affect the properties and structures of coordination polymers, of which organic ligands have a strong influence on the complexes^[15]. At present, some amide ligands have been reported, and bispyridyl bisamide ligands are very important ones, but Ⅴ-type bispyridyl bisamide ligands containing supramolecular hydrogen bond sites (-OH) were rarely reported^[16]. In addition, the aromatic carb-oxylic acid as a co-ligand also has a certain influence on the structure and properties of the complexes^[17-18]. Therefore, it is meaningful to study the construction of complex based on Ⅴ-type bispyridyl bisamide and polycarboxylate mixed ligands.

  On the other hand, some coordination polymers based on d¹⁰ metal ions show fluorescent sensing property^[19]. However, many of them show single sensing object^[20]. In 2016, Li′s group used 1, 3-di(4-pyridyl)-propane and 1, 4-bis(1, 2, 4-triazol-l-yl)butane ligands to successfully synthesize two compounds, both of which have good fluorescence sensing properties for Fe³⁺ ions; In 2017, our group used N, N′-bis(4-methylenepyridin-4-yl)-1, 4-benzenedicarboxamide to synthesize a series of Cd-complexes which have fluorescence sensing properties for methanol^[21-22]. Therefore, the investigation on the synthesis of sensing materials with multi-functional detection is very meaningful.

  In this work, we use a Ⅴ-type bispyridyl bisamide, N, N′-bis(4-pyridin-3-yl)-5-hydroxyisophtha-lamide (L), as the neutral ligand to combine with 1, 4-benzenedicarboxylic acid (1, 4-H₂BDC) under hydro-thermal condition, a 2-fold parallel-interpenetrated coordination polymer of {[Cd(BDC)(L)]·1.5H₂O}_n (1) was obtained. The title complex shows fluorescence sensing properties for Fe³⁺ and dichloromethane, which is expected to become a new fluorescent probe material.

  1.   Experimental

  1.1   General procedures

  All chemicals purchased were of reagent grade and used without further purification. Ligand L was synthesized by the method of the literature^[23]. FT-IR spectra were taken on a Magna FT-IR 560 spectro-meter (500~4 000 cm^-1) with KBr pellet. Fluorescence spectra were performed on an F-4500 fluorescence/phosphorescence spectrophotometer at room temperature.

  1.2   Synthesis of {[Cd(BDC)(L)]·1.5H₂O}_n

  A mixture of CdCl₂ (0.1 mmol), L (0.1 mmol), H₂BDC (0.1 mmol), NaOH (0.2 mmol), H₂O (10 mL) was sealed to a Teflon-lined stainless steel autoclave (25 mL) and kept at 120 ℃ for 4 days. After the mixture was slowly cooled to room temperature, colorless block crystals of 1 suitable for X-ray diffraction were obtained in 34% yield (based on Cd). Anal. Calcd. for C₂₆H₂₁CdN₄O_8.5(%): C, 48.96; H, 3.32; N, 8.78. Found(%): C, 49.43; H, 3.14; N, 8.80. IR (KBr, cm^-1): 3 291w, 3 178w, 3 097w, 1 676m, 1 557s, 1 488s, 1 375s, 1 287 m, 1 219m, 843s, 805w, 743m, 693m.

  1.3   X-ray crystallography

  The data were collected on a Bruker Smart Apex Ⅱ CCD diffractometer with Mo Kα (λ=0.071 073 nm) at 296 K (-21 ≤ h ≤ 28, -21 ≤ k ≤ 17, -22 ≤ l ≤ 22) in the range of 1.800°~28.204° by using an ω-2θ scan mode. A total of 15 753 reflections were collected, of which 6 171 were independent (R_int=0.018 8) and 5 241 reflections were used in the succeeding refine-ment. The structure was solved by the direct method with SHELXS-2014 and refined by the Full-matrix least-squares on F² using the SHELXL-2014^[24-25]. The hydrogen atoms of the organic ligands were placed in calculated positions (C-H 0.093 nm) and treated as riding atoms, and all the non-hydrogen atoms were refined anisotropically. One of H atom in O1W is disordered in two sites, H1B and H1C with the occupancy factor of 0.5. O2W is half-occupied. The crystal data and structure refinement details for 1 are listed in Table 1. Selected bond lengths and angles are given in Table 2.

  Table 1

  

  Table 1.  Crystal data and structure refinement for the title complex

  下载: 导出CSV

  Empirical formula	C26H21CdN4O8.5		DC/(g·cm-3)	1.656
  Crystal size / mm	0.20×0.18×0.15		μ/mm-1	0.914
  Formula weight	637.87		F(000)	2 568
  Crystal system	Monoclinic		θ/(°)	1.800~28.204
  Space group	C2/c		Reflection collected	15 753
  a / nm	2.171 45(8)		Unique reflection (Rint)	6 171 (0.018 8)
  b/ nm	1.605 34(6)		Data, restraint, parameter	6 171, 0, 362
  c / nm	1.678 04(6)		Goodness-of-fit on F2	1.006
  β/(°)	118.985 0(10)		Final R indices [I > 2σ(I)]	R1=0.026 5, wR2=0.067 6
  V/nm3	5.116 8(3)		R indices (all data)	R1=0.034 3, wR2=0.071 5
  Z	8		Largest diff. peak and hole / (e · nm-3)	649 and -358

  Table 2

  

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

  下载: 导出CSV

  Cd(1)-O(2)	0.222 55(14)	Cd(1)-N(1)	0.225 36(17)	Cd(1)-O(3)ⅰ	0.257 0(2)
  Cd(1)-O(4)ⅰ	0.223 47(18)	Cd(1)-N(4)ⅱ	0.227 58(18)	Cd(1)-O(1)	0.262 66(16)
  O(2)-Cd(1)-O(4)ⅰ	82.90(6)	O(2)-Cd(1)-N(1)	137.78(6)	O(4)ⅰ-Cd(1)-N(1)	124.49(7)
  O(2)-Cd(1)-O(1)	52.89(5)	O(4)-Cd(1)-N(4)ⅱ	105.37(6)	N(1)-Cd(1)-N(4)ⅱ	95.86(6)
  O(4)-Cd(1)-O(1)	134.61(6)	O(4)ⅰ-Cd(1)-O(3)ⅰ	52.57(6)	N(1)-Cd(1)-O(3)ⅰ	81.01(6)
  O(4)ⅰ-Cd(1)-N(4)ⅱ	108.39(8)	O(2)-Cd(1)-O(3)ⅰ	135.20(6)	N(4)ⅱ-Cd(1)-O(3)ⅰ	86.87(8)
  N(1)-Cd(1)-O(1)	90.05(5)	N(4)ⅱ-Cd(1)-O(1)	94.38(6)	O(3)ⅰ-Cd(1)-O(1)	171.05(6)
  Symmetry codes: ⅰx+1/2, -y+3/2, z+1/2; ⅱ-x+1, -y+1, -z

  CCDC: 1847700.

  2.   Results and discussion

  2.1   Description of the structure

  Complex 1 belongs to the C2/c space group and the asymmetric unit contains one Cd(Ⅱ) cation, one L, one 1, 4-BDC anion, one and a half of lattice water molecules. Each Cd(Ⅱ) center is six-coordinated and possesses a distorted octahedral coordination geometry surrounded by two pyridyl N atoms belonging to two L ligands with Cd-N bond lengths of 0.225 36(17) and 0.227 58(18) nm, four O atoms from two BDC anions, respectively (Fig. 1). The bond lengths of Cd-O are in the range of 0.222 55(14)~0.262 66(16) nm.

  Figure 1

  

  Figure 1.  Coordination environment of the Cd(Ⅱ) ion in 1 with ellipsoid probability of 50%

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

  下载: 全尺寸图片 幻灯片

  In 1, each 1, 4-BDC anion connects the adjacent Cd(Ⅱ) to form a wave-like [Cd-BDC]_n chain with the Cd…Cd distance of 1.123 9 nm (Fig. 2a). A pair of μ₂-L coordinates two Cd(Ⅱ) ions to generate [Cd-L]₂ loop with the Cd…Cd distance of 1.41 nm, which links the above [Cd-BDC]_n chains forming a two-dimensional 6³ connected layer (Fig. 2b and 2c). Finally, the parallel 2D layers are extended into a 3D polycatenation array (Fig. 3). The outstanding point is the catenation fashion in such a way that each six-membered ring interlocks two six-membered rings from two adjacent parallel wave-like layer nets up and down and vice versa (Fig. 3). In addition, the polycatenation array is stabilized by the hydrogen bonding interactions between hydroxyl, carboxylic, amino groups and lattice water molecules. The corresponding hydrogen bonding parameters of the complex are listed in Table 3.

  Figure 2

  

  Figure 2.  View of 1D [Cd-BDC]_n chain (a), 2D layer (b) and simplified 2D structure (c) of 1

  下载: 全尺寸图片 幻灯片

  Figure 3

  

  Figure 3.  Details of interpenetrated structure (a), stacking structure (b) and 2-fold-interpenetrated structure (c) of 1

  下载: 全尺寸图片 幻灯片

  Table 3

  

  Table 3.  Hydrogen-bonding geometry for the title complex

  下载: 导出CSV

  D-H…A	d(D-H)/nm	d(H …A) / nm	d(D …A) / nm	∠D-H…A/(°)
  O(1W)-H(1A)…O(3)ⅰ	0.092	0.204	0.285 9(3)	148
  O(2W)-H(2B)…O(7)ⅱ	0.093	0.221	0.307 2(10)	154
  O(6)-H(6)…O(1)ⅲ	0.082	0.193	0.274 8(2)	178
  N(2)-H(2)…O(1W)	0.086	0.230	0.312 2(3)	160
  N(3)-H(3)…O(2)ⅳ	0.086	0.221	0.298 0(2)	150
  O(1W)-H(1B)…O(1W)ⅴ	0.092	0.227	0.305 5(6)	144
  O(1W)-H(1C)…O(2W)	0.092	0.223	0.296 0(10)	135
  O(2W)-H(2A)…O(7)	0.092	0.227	0.300 7(10)	137
  Symmetry codes: ⅰx+1/2, -y+3/2, z+1/2; ⅱ-x+1, -y+1, -z; ⅲ-x+1/2, -y+1/2, -z; ⅳx+1/2, y-1/2, z; ⅴ-x+1, y, -z+1/2.

  2.2   PXRD and IR spectrum

  In order to examine the phase purity of the bulk material of 1, powder X-ray diffraction (PXRD) experiment was performed at room temperature. As shown in Fig. 4, the as-synthesized sample and simulated patterns are in good agreement with each other, proving the consistency of synthesized bulk material and the measured single crystal^[26]. The slight difference in peak intensity may be due to the different orientation of the crystals in the powder sample. The IR spectrum of the title complex is shown in Fig. 5. The absorption peak at 3 178 cm^-1 should be attributed to the characteristic absorption of -OH groups of water molecules^[27]. The characteristic peaks at 1 557 and 1 488 cm^-1 indicate the ν(C-N) stretching vibrations on the pyridine rings of bipyridine ligand. The characteristic peaks of 1 219 to 843 cm^-1 are the characteristic absorption peaks of benzene rings of organic ligands^[28].

  Figure 4

  

  Figure 4.  PXRD patterns of complex 1

  下载: 全尺寸图片 幻灯片

  Figure 5

  

  Figure 5.  FT-IR spectrum of the complex 1

  下载: 全尺寸图片 幻灯片

  2.3   Thermogravimetric and photoluminescent properties of 1

  The TG curve of complex 1 is shown in Fig. 6. The weight loss of 1 happened in two steps. The first weight loss was observed in the range of 50~172 ℃ with a weight loss of approximately 4.03%, demonstra-ting the removal of lattice water molecules (Calcd. 4.23%). The second weight loss (53.28%) occurred in the range of 142~531 ℃, indicating the collapse of the organic skeleton (Calcd. 52.43%). The solid state fluorescence of the complex was studied at room temperature (Slit: 2.5 nm, Voltage: 700 V). As shown in Fig. 7, at the excitation wavelength of 310 nm, the title complex has a maximum emission peak at 375 nm. Compared with the luminescence of L, the maximum emission peak of the complex is red-shifted of 5 nm. It was considered that there is no obvious contribution for the polycarboxylate to the lumines-cence emission of the complex in the presence of the N-containing ligand. Therefore, the luminescence of the title complex can be attributed to ligand-metal charge transfer^[29].

  Figure 6

  

  Figure 6.  TGA curve of complex 1

  下载: 全尺寸图片 幻灯片

  Figure 7

  

  Figure 7.  Solid-state luminescence of complex 1

  下载: 全尺寸图片 幻灯片

  2.4   Fluorescent sensing property

  The fluorescent responses of 1 for organic solvents and metal ions were performed at same experimental conditions (Slit: 2.5 nm, Voltage: 700) according to the reported similar methods^[30-34]. To explore the fluorescent response of 1 to various organic solvents, 5 mg of 1 was ball milled and dispersed in various organic solvents (3 mL) including methanol, ethanol, ethylene glycol, n-propanol, isopropanol (IPA), butanol, dichloromethane (DCM), cyclohexane, tetrahydrofuran (THF), acetonitrile, N, N′-dimethylfor-mamide (DMF), 1, 4-dioxane. Compared to the other organic solvents, the fluorescence intensity of the suspension of 1 has been strongly enhanced by DCM in the fluorescence response (Fig. 8). This effect may be attributed to the energy transfer from the ligand to the methylene chloride molecule after excitation and the interaction between the complex skeleton and the organic small molecule^[30]. To investigate the relation-ship between fluorescence intensity and DCM concentration, we gradually added DCM in 3 mL of ethanol, adding 50 μL each time. As shown in Fig. 9, as the concentration of DCM increases, the fluore-scence intensity of the suspension of 1 also increases. In addition, we also explored the fluorescence response of 1 to different metal ions. As seen in Fig. 10, the as-synthesized sample of 1 (2 mg) was immersed in different aqueous solutions (3 mL) of containing 0.01 mol·L^-1 of metal ions (Pb²⁺, Cd²⁺, Ag⁺, Zn²⁺, Co²⁺, Cu²⁺, Fe²⁺ and Fe³⁺) to form stable suspension. The luminescence intensity of 1 suspension showed an excellent quenching effect with addition of Fe³⁺. The fluorescence quenching effect may be attributed to the electron transfer of the ligand to the metal, i.e., the interaction between the Lewis basic site of the ligand and the Fe^{3+ [35]}. In addition, with the gradual addition of Fe³⁺ from 0 to 1 700 μL (100 μL each time, 1 mmol·L^-1), the fluorescence intensity of the suspens-ion of 1 gradually decreases (Fig. 11).

  Figure 8

  

  Figure 8.  Emission spectra of 1 in different organic solvents under excitation at 310 nm

  下载: 全尺寸图片 幻灯片

  Figure 9

  

  Figure 9.  Emission spectra of DCM@1 in ethanol with gradual addition of DCM under excitation at 310 nm

  下载: 全尺寸图片 幻灯片

  Figure 10

  

  Figure 10.  Emission spectra of Mn@1 in aqueous solutions containing metal ions under excitation at 310 nm

  下载: 全尺寸图片 幻灯片

  Figure 11

  

  Figure 11.  Emission spectra of Fe³⁺@1 in H₂O with gradual addition of Fe³⁺ under excitation at 310 nm

  下载: 全尺寸图片 幻灯片

  3.   Conclusions

  In summary, a new 2-fold parallel-interpenetrated Cd(Ⅱ) coordination polymer was hydrothermally synth-esized. The obvious change of 1 in the luminescence intensities caused by Fe³⁺ and dichloromethane relative to other metal ions and organic solvents implies the possible application of 1 for recognizing and sensing Fe³⁺ ions and dichloromethane, demonstrating its potential applications in the functional material fields.

• 1. [1]

     Zhang J, Yang W, Wu X Y, et al. Cryst. Growth Des., 2016, 16(1):475-482 doi: 10.1021/acs.cgd.5b01481

  2. [2]

     Pal T K, De D, Senthilkumar S, et al. Inorg. Chem., 2016, 55(16):7835-7842 doi: 10.1021/acs.inorgchem.6b00154

  3. [3]

     Zhao H, Xia Q, Xing H, et al. ACS Sustainable Chem. Eng., 2017, 5(5):4449-4456 doi: 10.1021/acssuschemeng.7b00641

  4. [4]

     Liu M, Yang X F, Zhu H B, et al. Dalton Trans., 2018, 47:5245-5251 doi: 10.1039/C8DT00366A

  5. [5]

     Cong B, Su Z, Zhao Z, et al. New J. Chem., 2018, 42:4596-4602 doi: 10.1039/C7NJ04854H

  6. [6]

     Gu Z Y, Yan X P. Angew. Chem. Int. Ed., 2010, 49:1477-1480 doi: 10.1002/anie.200906560

  7. [7]

     Ahmad R, Wongfoy A G, Matzger A J. Langmuir, 2009, 25(20):11977-11979 doi: 10.1021/la902276a

  8. [8]

     Chang N, Gu Z Y, Yan X P. J. Am. Chem. Soc., 2010, 132(39):13645-13647 doi: 10.1021/ja1058229

  9. [9]

     Zhang H, Liu X, Wu Y, et al. Chem. Commun., 2018, 54:5268-5288 doi: 10.1039/C8CC00789F

  10. [10]

      Tao Z, Teng W, Wang X, et al. ACS Appl. Mater. Interfaces, 2016, 8(51):35390-35397 doi: 10.1021/acsami.6b13411

  11. [11]

      Zhao Y, Li X, Liu J, et al. ACS Appl. Mater. Interfaces, 2016, 8(10):6472-6480 doi: 10.1021/acsami.5b12562

  12. [12]

      Liu J J, Shan Y B, Fan C R, et al. Inorg. Chem., 2016, 55(7):3680-3684 doi: 10.1021/acs.inorgchem.6b00252

  13. [13]

      Li H Y, Wei Y L, Dong X Y, et al. Chem. Mater., 2015, 27(4):1327-1331 doi: 10.1021/cm504350q

  14. [14]

      Chen D M, Zhang N N, Liu C S, et al. ACS Appl. Mater. Interfaces, 2017, 9(29):24671-24677 doi: 10.1021/acsami.7b07901

  15. [15]

      He H Y, Hsu C H, Chang H Y, et al. Cryst. Growth Des., 2017, 17(4):1991-1998 doi: 10.1021/acs.cgd.7b00001

  16. [16]

      Ganguly S, Mukherjee S, Dastidar P. Cryst. Growth Des., 2016, 16(9):5247-5259 doi: 10.1021/acs.cgd.6b00805

  17. [17]

      Zimpel A, Preiß T, Röder R, et al. Chem. Mater., 2016, 28(10):3318-3326 doi: 10.1021/acs.chemmater.6b00180

  18. [18]

      Choi S, Kim T, Ji H, et al. J. Am. Chem. Soc., 2016, 138(43):14434-14440 doi: 10.1021/jacs.6b08821

  19. [19]

      Nowakowski A B, Meeusen J W, Menden H, et al. Inorg. Chem., 2015, 54(24):11637-11647 doi: 10.1021/acs.inorgchem.5b01535

  20. [20]

      Das A, Jana S, Ghosh A. Cryst. Growth Des., 2018, 18(4):2335-2348 doi: 10.1021/acs.cgd.7b01752

  21. [21]

      樊婷婷, 屈相龙, 李佳佳, 等.无机化学学报, 2016, 32(11):1911-1918 http://www.wjhxxb.cn/wjhxxbcn/ch/reader/view_abstract.aspx?file_no=20161104&flag=1FAN Ting-Ting, QU Xiang-Long, LI Jia-Jia, et al. Chinese J. Inorg. Chem., 2016, 32(11):1911-1918 http://www.wjhxxb.cn/wjhxxbcn/ch/reader/view_abstract.aspx?file_no=20161104&flag=1

  22. [22]

      Wang X L, Xiong Y, Sha X T, et al. Cryst. Growth Des., 2017, 17(2):483-496 doi: 10.1021/acs.cgd.6b01299

  23. [23]

      Sarkar M S, Biradha K. Cryst. Growth Des., 2006, 6(1):202-208 doi: 10.1021/cg050292l

  24. [24]

      Sheldrick G M. SHELXS-2014, Program for Crystal Structure Solution, University of Göttingen, Germany, 2014.

  25. [25]

      Sheldrick G M. SHELXL-2014, Program for X-ray Crystal Structure Refinement, University of Göttingen, Germany, 2014.

  26. [26]

      Zhou X, Liu P, Huang W H, et al. CrystEngComm, 2013, 15(40):8125-8132 doi: 10.1039/c3ce41120f

  27. [27]

      Kalsi P S. Spectroscopy of Organic Compounds. New Delhi:New Age International Publishers, 2016:592

  28. [28]

      Dolenský B, Konvalinka R, Jakubek M, et al. J. Mol. Struct., 2013, 1035:124-128 doi: 10.1016/j.molstruc.2012.09.040

  29. [29]

      Wang X L, Sha X T, Liu G C, et al. Inorg. Chim. Acta, 2015, 30(440):94-101

  30. [30]

      Li Y L, Zhao Y, Wang P, et al. Inorg. Chem., 2016, 55(22):11821-11830 doi: 10.1021/acs.inorgchem.6b01869

  31. [31]

      Lu Z Z, Zhang R, Li Y Z, et al. J. Am. Chem. Soc., 2011, 133(12):4172-4174 doi: 10.1021/ja109437d

  32. [32]

      Yan W, Zhang C, Chen S G, et al. ACS Appl. Mater. Interfaces, 2017, 9(2):1629-1634 doi: 10.1021/acsami.6b14563

  33. [33]

      Liu Z Q, Chen K, Zhao Y, et al. Cryst. Growth Des., 2018, 18(2):1136-1146 doi: 10.1021/acs.cgd.7b01572

  34. [34]

      Qin L, Zheng M X, Guo Z J, et al. Chem. Commun., 2015, 51(12):2447-2449 doi: 10.1039/C4CC08763A

  35. [35]

      Wang X L, Wu X M, Liu G C, et al. J. Solid State Chem., 2017, 249:51-57 doi: 10.1016/j.jssc.2017.02.018

• 

  Figure 1  Coordination environment of the Cd(Ⅱ) ion in 1 with ellipsoid probability of 50%

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

  下载: 全尺寸图片 幻灯片
  

  Figure 2  View of 1D [Cd-BDC]_n chain (a), 2D layer (b) and simplified 2D structure (c) of 1

  下载: 全尺寸图片 幻灯片
  

  Figure 3  Details of interpenetrated structure (a), stacking structure (b) and 2-fold-interpenetrated structure (c) of 1

  下载: 全尺寸图片 幻灯片
  

  Figure 4  PXRD patterns of complex 1

  下载: 全尺寸图片 幻灯片
  

  Figure 5  FT-IR spectrum of the complex 1

  下载: 全尺寸图片 幻灯片
  

  Figure 6  TGA curve of complex 1

  下载: 全尺寸图片 幻灯片
  

  Figure 7  Solid-state luminescence of complex 1

  下载: 全尺寸图片 幻灯片
  

  Figure 8  Emission spectra of 1 in different organic solvents under excitation at 310 nm

  下载: 全尺寸图片 幻灯片
  

  Figure 9  Emission spectra of DCM@1 in ethanol with gradual addition of DCM under excitation at 310 nm

  下载: 全尺寸图片 幻灯片
  

  Figure 10  Emission spectra of Mn@1 in aqueous solutions containing metal ions under excitation at 310 nm

  下载: 全尺寸图片 幻灯片
  

  Figure 11  Emission spectra of Fe³⁺@1 in H₂O with gradual addition of Fe³⁺ under excitation at 310 nm

  下载: 全尺寸图片 幻灯片

  Table 1.  Crystal data and structure refinement for the title complex

  Empirical formula	C26H21CdN4O8.5		DC/(g·cm-3)	1.656
  Crystal size / mm	0.20×0.18×0.15		μ/mm-1	0.914
  Formula weight	637.87		F(000)	2 568
  Crystal system	Monoclinic		θ/(°)	1.800~28.204
  Space group	C2/c		Reflection collected	15 753
  a / nm	2.171 45(8)		Unique reflection (Rint)	6 171 (0.018 8)
  b/ nm	1.605 34(6)		Data, restraint, parameter	6 171, 0, 362
  c / nm	1.678 04(6)		Goodness-of-fit on F2	1.006
  β/(°)	118.985 0(10)		Final R indices [I > 2σ(I)]	R1=0.026 5, wR2=0.067 6
  V/nm3	5.116 8(3)		R indices (all data)	R1=0.034 3, wR2=0.071 5
  Z	8		Largest diff. peak and hole / (e · nm-3)	649 and -358

  下载: 导出CSV

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

  Cd(1)-O(2)	0.222 55(14)	Cd(1)-N(1)	0.225 36(17)	Cd(1)-O(3)ⅰ	0.257 0(2)
  Cd(1)-O(4)ⅰ	0.223 47(18)	Cd(1)-N(4)ⅱ	0.227 58(18)	Cd(1)-O(1)	0.262 66(16)
  O(2)-Cd(1)-O(4)ⅰ	82.90(6)	O(2)-Cd(1)-N(1)	137.78(6)	O(4)ⅰ-Cd(1)-N(1)	124.49(7)
  O(2)-Cd(1)-O(1)	52.89(5)	O(4)-Cd(1)-N(4)ⅱ	105.37(6)	N(1)-Cd(1)-N(4)ⅱ	95.86(6)
  O(4)-Cd(1)-O(1)	134.61(6)	O(4)ⅰ-Cd(1)-O(3)ⅰ	52.57(6)	N(1)-Cd(1)-O(3)ⅰ	81.01(6)
  O(4)ⅰ-Cd(1)-N(4)ⅱ	108.39(8)	O(2)-Cd(1)-O(3)ⅰ	135.20(6)	N(4)ⅱ-Cd(1)-O(3)ⅰ	86.87(8)
  N(1)-Cd(1)-O(1)	90.05(5)	N(4)ⅱ-Cd(1)-O(1)	94.38(6)	O(3)ⅰ-Cd(1)-O(1)	171.05(6)
  Symmetry codes: ⅰx+1/2, -y+3/2, z+1/2; ⅱ-x+1, -y+1, -z

  下载: 导出CSV

  Table 3.  Hydrogen-bonding geometry for the title complex

  D-H…A	d(D-H)/nm	d(H …A) / nm	d(D …A) / nm	∠D-H…A/(°)
  O(1W)-H(1A)…O(3)ⅰ	0.092	0.204	0.285 9(3)	148
  O(2W)-H(2B)…O(7)ⅱ	0.093	0.221	0.307 2(10)	154
  O(6)-H(6)…O(1)ⅲ	0.082	0.193	0.274 8(2)	178
  N(2)-H(2)…O(1W)	0.086	0.230	0.312 2(3)	160
  N(3)-H(3)…O(2)ⅳ	0.086	0.221	0.298 0(2)	150
  O(1W)-H(1B)…O(1W)ⅴ	0.092	0.227	0.305 5(6)	144
  O(1W)-H(1C)…O(2W)	0.092	0.223	0.296 0(10)	135
  O(2W)-H(2A)…O(7)	0.092	0.227	0.300 7(10)	137
  Symmetry codes: ⅰx+1/2, -y+3/2, z+1/2; ⅱ-x+1, -y+1, -z; ⅲ-x+1/2, -y+1/2, -z; ⅳx+1/2, y-1/2, z; ⅴ-x+1, y, -z+1/2.

  下载: 导出CSV
•