Synthesis, crystal structure and thermal behavior of two Ba(II) compounds derived from tetrazole-carboxylate ligands

Accepted Manuscript Synthesis, crystal structure and thermal behavior of two Ba(II) compounds derived from tetrazole-carboxylate ligands Wanting Su, Yujie Shi, Xinyu Hao, Zhikang Wang, Zixiang Du, Qiaoyun Li, Gaowen Yang PII: DOI: Reference:

S0020-1693(19)30122-7 https://doi.org/10.1016/j.ica.2019.02.037 ICA 18800

To appear in:

Inorganica Chimica Acta

Received Date: Revised Date: Accepted Date:

23 January 2019 22 February 2019 25 February 2019

Please cite this article as: W. Su, Y. Shi, X. Hao, Z. Wang, Z. Du, Q. Li, G. Yang, Synthesis, crystal structure and thermal behavior of two Ba(II) compounds derived from tetrazole-carboxylate ligands, Inorganica Chimica Acta (2019), doi: https://doi.org/10.1016/j.ica.2019.02.037

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Synthesis, crystal structure and thermal behavior of two Ba(II) compounds derived from tetrazole-carboxylate ligands Wanting Su, Yujie Shi, Xinyu Hao, Zhikang Wang, Zixiang Du, Qiaoyun Li*, Gaowen Yang* Jiangsu Laboratory of Advanced Functional Material, Department of Chemistry and Material Engineering, Changshu Institute of Technology, Changshu 215500, Jiangsu, P. R. China *Qiao Yun Li: Tel: +86-512-52251842; Fax: +86-512-52251842 Email: [email protected] *Gao Wen Yang: Tel: +86-512-52251846; Fax: +86-512-52251842 Email: [email protected]

Abstract: Here we report two Ba(II) coordination compounds, 2D [Ba(btzphda)(H2O)4] (1) and 3D [Ba2(pytzipa)4(H2O)3]·2H2O (2) derived from 1,3-bis(tetrazol-5-yl)benzene-N2,N2′-diacetic acid (H2btzphda) and 5-(4-pyridyl)tetrazole-2-isopropionic acid (Hpytzipa). Furthermore, differential scanning calorimetry (DSC) and thermogravimetric-differential thermogravimetric (TG-DTG) analyses were applied to evaluate the thermal decomposition behavior of such compounds. The relevant thermodynamic parameters (ΔH, ΔS, and ΔG) of the decomposition process of compounds 1 and 2 were calculated, as well. Keywords: H2btzphda/Hpytzipa; Ba(II); crystal structure; thermal behavior

1. Introduction Coordination compounds are attracting increase attention due to not only their diversity in structure, but also their potential application as multifunctional materials, in the range of ferroelectrics, biology, luminescence and so on.[1-15] The design and preparation of targeted compounds with either intriguing structure or potential application most rely on the design of the ligand, from the point view of crystal engineering.[16-20] To date, tetrazole-carboxylates have been demonstrated to be outstanding ligands for the formation of coordination compounds. [21-30] On the one hand, these ligands with either rigid tetrazole rings and flexible carboxylate groups are likely to display various coordination modes and thus contribute to the formation of intriguing structures. Oxygen and nitrogen atoms are acknowledged as excellent coordination atoms. However, it is usually difficult to predict the eventual structure of the compounds since they are influenced by a number of factors, such as the

1

shape of the ligand, the pH value, and the solvent system etc [31-35]. Inspired

by

the

observations,

we

have

selected

1,3-bis(tetrazol-5-yl)benzene-N2,N2′-diacetic

acid

two

tetrazole-carboxylate

(denoted

as

ligands,

H2btzphda),

5-(4-pyridyl)tetrazole-2-isopropionicacid (denoted as Hpytzipa) (Scheme 1) and the barium salts to construct new coordination compounds. By reactions of H2btzphda, Hpytzipa with BaCl2 under solvothermal conditions, [Ba(btzphda)(H2O)4] (1) and [Ba2(pytzipa)4(H2O)3]·2H2O (2) were obtained. In addition, the thermal behavior of the two compounds were characterized by thermogravimetric analysis (TGA) and DSC (differential scanning calorimetry). And the kinetic analysis, critical temperature of thermal explosion and thermodynamic parameters in the process of thermal decomposition have been calculated, as well.

Scheme 1 Chemical structure of compounds 1 and 2.

2.Experimental Section 2.1．Materials and Apparatus General chemicals were commercially available reagents of analytical grade and were used without further purification. The IR spectra were recorded (4000–400cm-1) with a NICOLET 380 spectrometer with pressed KBr pellets. Single-crystal X-ray diffraction was carried out with a Rigaku SCXmini-CCD diffractometer. Thermogravimetric analysis (TGA) and DSC experiments were recorded on a Perkin–Elmer TGA 7 with the different heating rate of 5, 10, 15, 20 oC min-1 from 30 to 800 oC under nitrogen atmosphere.

2.2. Synthesis of the[Ba(btzphda)(H2O)4] (1) and [Ba2(pytzipa)4(H2O)3]·2H2O (2) H2btzphda (0.0328 g, 0.1mmol) was dissolved in distilled water (1.5 mL), and the pH value of the solution was adjusted to 5-6 with KOH (0.2 M). BaCl2 (0.0208g, 0.1mmol) was added to this

2

solution, finally added the methanol (4 mL). The mixture was stirred for 2h at 65°C, and then cooled to room temperature. Colorless crystals of 1 were obtained. Yield: 40% based on Ba2+. IR (KBr cm-1): 3417.26(s), 3126.93(s), 1616.72(s), 1452.46 (m), 1400.02 (m), 1119.90 (w), 1070.54(m), 954.24 (m), 862.36 (m), 615.58 (w), 518.29(m). A similar method to that of compound 1 was adopted to prepare 2 except that ligand was Hpytzipa, the temperature was 80 °C and the ethanol (3 mL) was used. Colorless crystals of 2 were obtained. Yield: 45% based on Ba2+. IR (KBr cm-1): 3433.06(s), 3132.64 (s), 1610.69 (s), 1455.75 (m), 1401.61 (m), 1221.99 (w), 1141.20 (m), 1080.49(m), 999.42 (m), 841.41 (w), 744.20 (m), 677.58 (w), 543.57(m).

2.3. X-ray Crystallography Single-crystal

X-ray

crystal

diffractometer equipped 0.71073

Å).

The

data

with

applied.

The

collected

data were

intensity

reflection

on

a

graphite-monochromated

reduced using the Crystal-Clear was

were

collected

by

Rigaku Mo-Kα the

SCX

mini

radiation

ω-scan

technique

were

also

corrected

maps

and

isotropically, with the

refined

= and

for Lorentz and polarization

effects. The structures were solved by direct methods and refined on F2 by

Fourier

(λ

program, and an absorption correction (multi-scan)

data

least-squares using SHELXTL. [36]

CCD

All

non-hydrogen atoms

anisotropically. [37]

All

full-matrix

were located from the

H

atoms

were

refined

isotropic vibration parameters related to the non-H atom to which they

were bonded.[38]

Table 1. Selected crystallographic data and structure refinement for 1 and 2 Compound

1

2

Empirical formula

C12H16BaN8O8

C36H42Ba2N20O13

Formula mass

537.66

1237.57

Crystal system

triclinic

monoclinic

Space group

Pī

C2/c

a (Å)

9.251(3)

15.781(9)

b (Å)

10.332 (3)

27.144(15)

3

c (Å)

11.637(4)

13.046(8)

α (°)

101.386(5)

90.00

 (°)

95.132 (5)

115.581(8)

 (°)

105.582(5)

90.00

V (Å3)

1038.3(6)

5041(5)

Z

2

4

T/K

296(2)

296(2)

Dcalcd (g.cm-3)

1.720

1.631

(mm-1)

1.97

1.63

Reflections collected

7008

20786

Unique Reflections(Rint)

3643(0.020)

5158(0.093)

3063

4751

No. Variables

262

337

R1[a] , wR2[b] (I>2sigma(I))

0.036, 0.124

0.055, 0.202

GOFc

1.08

1.09

Δ/ρmax (e/Å3)

2.47

2.97

Δ/ρmin (e/Å3)

-0.76

-2.46

No. Observations (I >2.00  (I))

[a]

R= ||Fo|-|Fc|/∑|Fo|. [b]Rw = {w(Fo2-Fc2)2/w(Fo2)2}1/2. [c] GOF ={w((Fo2-Fc2)2)/(n-p)}1/2,

Where n = number of reflections and p = total numbers of parameters refined.

Table 2 Selected bond distances and angles for 1-2 (Å/º) Compound 1 Ba1—O5

2.7927

Ba1—O6

2.7529

Ba1—O1A

2.9524

Ba1—O2A

2.8920

Ba1—O7A

2.9322

Ba1—O16A

3.1263

Ba1—O2B

2.7068

Ba1—O3C

2.8651

Ba1—O4C

2.9490

Ba1—O3D

2.7083

O5—Ba1—O6

76.795

O5—Ba1—O1A

71.503

4

O5—Ba1—O2A

68.654

O5—Ba1—O7A

123.570

O5—Ba1—O16A

141.734

O5—Ba1—O2B

85.082

O5—Ba1—O3C

130.728

O5—Ba1—O4C

148.643

O5—Ba1—O3D

74.399

O6—Ba1—O1A

144.745

O6—Ba1—O2A

133.247

O6—Ba1—O7A

139.930

O6—Ba1—O16A

121.317

O6—Ba1—O2B

78.023

O6—Ba1—O3C

67.675

O6—Ba1—O4C

74.291

O6—Ba1—3D

81.458

O1A—Ba1—O2A

44.795

O1A—Ba1—O7A

56.276

O1A—Ba1—O16A

93.468

O1A—Ba1—O2B

113.518

O1A—Ba1—O3C

124.612

O1A—Ba1—O4C

139.480

O1A—Ba1—O3D

75.590

O2A—Ba1—O7A

86.405

O2A—Ba1—O16A

75.934

O2A—Ba1—O2B

68.751

O2A—Ba1—O3C

158.063

O2A—Ba1—O4C

125.959

O2A—Ba1—O3D

116.560

O7A—Ba1—O16A

66.345

O7A—Ba1—O2B

132.520

O7A—Ba1—O3C

74.011

O7A—Ba1—O4C

86.953

O7A—Ba1—O3D

73.449

O16A—Ba1—O2B

68.603

O16A—Ba1—O3C

87.004

O16A—Ba1—O4C

52.574

O16A—Ba1—O3D

137.108

O2B—Ba1—O3C

117.871

O2B—Ba1—O4C

77.343

O2B—Ba1—O3D

153.771

O3C—Ba1—O4C

44.845

O3C—Ba1—O3D

67.679

O4C—Ba1—O3D

112.522

Compound 2 Ba1—O1

2.667 (3)

Ba1—O3

2.707 (3)

Ba1—O5

2.909 (4)

Ba1—O6

3.080 (3)

Ba1—O4A

2.769 (3)

Ba1—O5A

2.919 (3)

Ba1—O1B

2.796 (4)

Ba1—O2B

2.966 (4)

Ba1—N5C

2.977 (3)

O1—Ba1—O3

124.94(13)

O1—Ba1—O5

164.78(12)

5

O1—Ba1—O6

64.68(10)

O1—Ba1—O4A

75.35(10)

O1—Ba1—O5A

89.73(12)

O1—Ba1—O1B

71.25(11)

O1—Ba1—O2B

114.05(10)

O1—Ba1—N5C

82.68(14)

O3—Ba1—O5

68.41(12)

O3—Ba1—O6

61.19(12)

O3—Ba1—O4A

75.35(10)

O3—Ba1—O5A

63.28(13)

O3—Ba1—O1B

92.76(13)

O3—Ba1—O2B

79.85(12)

O3—Ba1—N5C

144.61(14)

O5—Ba1—O6

129.50(7)

O5—Ba1—O4A

89.96(11)

O5—Ba1—O5A

90.94(9)

O5—Ba1—O1B

118.26(11)

O5—Ba1—O2B

73.38(11)

O5—Ba1—N5C

88.50(11)

O6—Ba1—O4A

127.29(8)

O6—Ba1—O5A

69.26(10)

O6—Ba1—O1B

63.33(10)

O6—Ba1—O2B

94.34(7)

O6—Ba1—N5C

132.59(11)

O4A—Ba1—O5A

77.33(11)

O4A—Ba1—O1B

133.12(12)

O4A—Ba1—O2B

134.00 (10)

O4A—Ba1—N5C

69.47(13)

O5A—Ba1—O1B

33.19(11)

O5A—Ba1—O2B

43.11(9)

O5A—Ba1—N5C

46.80(11)

O1B—Ba1—O2B

45.07(9)

O1B—Ba1—N5C

74.43(14)

O2B—Ba1—N5C

67.67(12)

Symmetry code For 1: A: x, y, 1+z; B: 1−x, 1-y, 1−z; C: -x, 1+y, z; D: 2-x,-y, 2-z. For 2: A: -x+1/2,-y+1/2,-z+1; B:-x, y, -z+1/2; C: x, -y+1, z+1/2; D: x,-y+1, z-1/2.

3. Results and Discussion 3.1．Preparation and Characterization of 1–2 Compounds 1 and 2 are stable towards oxygen and water. Characteristic peaks around the region of 1616-1610cm-1 are ascribed to the asymmetric stretching vibration of the carboxylate that is coordinated to Ba(II). For compounds 1 and 2, strong peaks observed at 3132-3433cm-1 are attributed to the O-H stretching vibration of the coordination or guest water molecules. The characteristic peaks of the tetrazole ring, pyridine ring are around the range of 1455-1400cm-1.

6

3.2．Description of crystal structures of 1 and 2 Single-crystal X-ray analysis reveals that compound 1 consists of one Ba2+, one btzphda2- ligand, with space group Pī. The perspective view of 1 is shown in Fig. 1. each Ba(II) is deca-coordinated by six carboxylate-O atoms (O1A, O2A, O2B, O3C, O4C, O3D), four oxygen atoms (O5, O6, O7A, O16A) from four water molecules. The coordination arrangement can be described as a distorted bicapped square antiprism. The Ba-O bond lengths from 2.707 to 3.126Å are in good accordancewith those of the reported barium complexes[38,39]. Btzphda2- acts as a tradentate ligand to bridge four Ba(II) centers in a μ1,1,3-COO coordination mode, forming a 2D layer structure (Fig. 2). Compared with the 2D [Ba(pytza)2(H2O)2]n·nH2O (pytza = 5-(4-pyridyl)tetrazole-2-acetato) in which pytza acts as a tridentate ligand via one nitrogen atom of the pyridine ring and the oxygen atom of the carboxylate group in a μ1,3-COO bridging mode [33], the coordination mode of btzpda2is a little different in that all the nitrogen atoms of btzphda2- are uncoordinated. Neighboring two-dimensional layers are connected together by the hydrogen bonds between the coordinated water and the oxygen atom of the guest water [O(5)-H(5B)···O(16), 2.750(8)Å/155°], [O(6)-H(6C)···O(7), 2.797(7)Å/122°], the coordinated water and the nitrogen atom from the tetrazole [O(6)-H(6D)···N(4), 3.009(7)Å/165°, O(7)-H(7A)···N(8), 2.915(7)Å/146°], and the guest water and the nitrogen atom from tetrazole [O(7)-H(7A)···N(8), 2.915(7)Å/146°, O(16)-H(16B)···N(7), 3.461(8)Å/163°], to generate a 3D supramolecular network (Fig. S1).

Fig. 1. Coordination environment of Ba(II) in compound 1. Hydrogen atoms are omitted for clarity.

7

Fig. 2. 2D layer structure of 1. Hydrogen atoms are omitted for clarity.

Compound 2 crystallizes in monoclinic space group C2/c. The perspective view of 2 is shown in Fig. 3, each Ba(II) is doda-coordinated by five carboxylate-O atoms (O1, O3, O4A, O1B, O2B), three oxygen atoms (O5, O6, O5A) from three water molecules and one nitrogen atom (N5C) from one pyridine ring, forming a distorted tricapped trigon prism coordination geometry. The Ba-O bond lengths from 2.667 to 3.080Å and that of the Ba-N (2.966Å) are similar to those of the reported Ba(II) compounds[38.39]. The pytzipa ligand bridges three Ba(II) centers via the pyridine nitrogen and the carboxylate oxygen atoms in μ1,1,3-COO bridging mode, and simultaneously connect neighboring Ba(II) centers via the carboxylate oxygen atoms in μ1,3-COO bridging mode, formig a 3D network structure (Fig. 4). Compared with compound 1, the nitrogen atoms of the pyridine rings in compound 2 participate in coordination while the nitrogen atoms of the tetrazole rings are still not coordinated.

8

Fig. 3. The coordination environment of Ba(II) atom of complex 2. Hydrogen atoms are omitted for clarity.

Fig. 4. 3D network of 2. Hydrogen atoms are omitted for clarity.

3.3 Thermogravimetric analysis and differential scanning calorimetry of compounds 1 and 2 Thermogravimetric analysis (TGA) of the compounds 1 and 2 were carried out under the atmosphere of nitrogen from 30 to 800 oC. From the TG-DTG curves, compounds 1 and 2 begin to decompose at 268oC and 269oC respectively, leading to the collapse of the crystal structure.

9

Fig. 6. (a)TGA of compound 1; (b) DSC of compound 1; (c) TGA of compound 2; (d) DSC of compound 2 from 30 to 800 °C with the linear heating rate of 10 °C/min.

From the DSC curves (Fig. 4b, 4d), it can be observed that compounds 1 and 2 have endothermic peaks at 218 and 275oC, respectively. And one exothermic peaks in the range from 208.2 to 247.2 o

C for compound 1, one exothermic peaks in the range from 262.8 to 298.1 oC for compound 2

were observed. The exothermic enthalpy of decomposition of compounds 1 and 2 is calculated to be -255.3 and -82.77J/g respectively.

3.6 Kinetic analysis In the Arrhenius equation, the apparent activation energy Ea (kJ·mol-1) and pre-exponential constant (A/s-1) are important dynamic basic parameters and the intermediate bridge for solving the thermodynamic functions of the compound decomposition process. The specific values of Ea and A can be obtained. DSC analysis of compounds 1 and 2 were carried out at different linear heating rates of 5, 10, 15, 20 K·min-1, and the corresponding peak temperature, 551, 557.2, 559.3 and 555.9 for 1; 552.2, 560.7, 565.4, 568.5 for 2 were obtained. The apparent activation energy Ea

10

(kJ·mol-1) and pre-exponential constant (A/s-1)was calculated according to Kissinger's method[42] (Eq. 1) and Ozawa's method [43] (Eq. 2), respectively.

lg   0.4567

ln

 Tp

2

 ln

Ea C RTp

RA Ea  Ea RTp

(1)

(2)

Tp represents the decomposition peak temperature (K), R is the constant (8.314 J·mol-1·K-1), the β is a linear heating rate (K·min-1), and C is the constant. The peak temperature in the non-isothermal DSC curves are in accordance with the same conversion degrees at various heating rate. Eo and Ek represent the apparent activation energy obtained by the Ozawa method and the Kissinger method, and the apparent activation energy Ea in the Arrhenius equation can be calculated by the mean value of Eo and Ek. According to calculation, the apparent activation energy obtained by the Ozawa’s method of compounds 1 and 2 is 311.15 and 210.19 kJ/mol. Respectively. While that obtained by the Kissinger’s method is 315.83 and 211.90 kJ/mol, respectively. The apparent activation energy obtained by two different methods is similar to each other. The apparent activation energy, the average value of Eo and Ek, is 313.493 kJ/mol for compound 1 and 211.044 kJ/mol for compound 2, respectively. lnA=61.55. Therefore, the specific expression of the Arrhenius equation can be written as lnk = 61.55-311.493/(RT) for compound 1 and lnk = 38.35-211.044/(RT) for compound 2.

3.7 Critical temperature of thermal explosion The critical temperature (Tbp) of thermal explosion is an important parameter to measure the thermal stability of energetic materials.The specific values can be calculated by equations 3 and equation 4 [44-45].

Tp  Tp 0  b  c 2 Tbp 

EO 

EO

(3)

 4 EORTp 0  (4) 2R 2

Eo is the apparent activation energy obtained by the Ozawa method. When b and c are coefficients,

11

β is the linear heating rate, the peak temperature Tp is approximately Tp0, that is, the initial decomposition temperature of the decomposition process. The value of Tbp of thermal explosion critical temperature can be solved. They are listed in Table 3.

3.8 The thermodynamic parameters of the thermal decomposition process The entropy of activation (△S), enthalpy of activation (△H), and free energy of activation (△G) of the exothermic decomposition reaction of the two compounds can be calculated based on E a and A, when T=Tp0, Ea=Ek, and A=Ak, by the following equations.

kBTeS / R A h

(5)

H  Ea  RT

(6)

G  H  TS

(7)

Where kB is Boltzmann constant (1.3807×10-23 J·K-1), and h is the Plank constant (6.626×10-34 J·s-1). Table 3. Thermal parameters of compounds 1 and 2 during decomposition. Compound

[Ba(btzphda)(H2O)4]

[Ba2(4-pytzipa)4(H2O)3]·2H2O

Eo (kJ/mol)

311.152

210.192

Ek (kJ/mol)

315.833

211.896

Arrhenius equations

lnk = 51.47−233.52×103/(RT)

lnk = 44.96−201.52×103/(RT)

Tbp (K)

539.65

541.55

△S (J·mol-1·K-1)

261.88

68.99

△H (kJ/mol)

309.01

173.68

△G (kJ/mol)

167.69

136.32

4. Conclusion In summary, two Ba(II) compounds based on 1,3-bis(tetrazol-5-yl)benzene-N2,N2′-diacetic acid, 5-(4-pyridyl)tetrazole-2-isopropionic acid have been reported. Compound 1 is a 2D layer while compound 2 is a 3D network. The relevant thermal parameters (△S, △H, △G) of the decomposition process of the two compounds have been calculated. The critical temperature were

12

reported, as well.

Acknowledgements The authors acknowledge financial support from the Natural Science Foundation of Jiangsu Province (Grant No. BK2012210), the Natural Science Foundation of the Jiangsu Higher Education Institutions of China (Grant No. 10KJB430001) and the Opening Fund of Jiangsu Key Laboratory of Advanced Functional Materials (Grant No·12KFJJ010).

Appendix A. Supplementary material CCDC reference numbers 1560106, 1856576 contains the supplementary crystallographic data for 1–2,respectively. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12UnionRoad, Cambridge CB21EZ, UK; fax:(+44) 1223-336-033; or e-mail: deposit@ ccdc.cam.ac.uk.

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[39] G.W. Yang, Y.T. Zhang, Q. Wu, M.J. Cao, J. Wu, Q.Y. Yue, Q.Y. Li, Inorg. Chim. Acta 450 (2016) 364-371.

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Synthesis, crystal structure and thermal behavior of two Ba(II) compounds derived from tetrazole-carboxylate ligands Wanting Su, Yujie Shi, Xinyu Hao, Zhi Kang Wang, Zixiang Du, Qiaoyun Li*, Gaowen Yang* *Qiao Yun Li: Tel: +86-512-52251842; Fax: +86-512-52251842 Email: [email protected] *Gao Wen Yang: Tel: +86-512-52251846; Fax: +86-512-52251842 Email: [email protected] Jiangsu Laboratory of Advanced Functional Material, Department of Chemistry and Material Engineering, Changshu Institute of Technology, Changshu 215500, Jiangsu, P. R. China 2D [Ba(btzphda)(H2O)4] (1) and 3D [Ba2(pytzipa)4(H2O)3]·2H2O (2) were prepared. The crystal structures and thermal behavior were discussed.

Corresponding author. Tel.: +86-13915634618; fax: +86-52251842 E-mail address: [email protected] (Qiao-Yun Li); [email protected] (Gao-Wen Yang)

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Highlights

H4-pytzipa and H2btzpda were prepared. Compound 1 shows the 2D layer compound 2 is 3D network structure. The thermal behavior were investigated.

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