FENG Jin-Ling ZHANG Jian-Guo,* ZHANG Tong-Lai,* CUI Yan

(1State Key Laboratory of Explosion Science and Technology,Beijing Institute of Technology,Beijing 100081,P.R.China;2The 6th Department,Research Institute of Chemical Defense(PLA),Beijing 102205,P.R.China)

Synthesis,Crystal Structure,Thermal Behavior and Sensitivity of[Mn(AZT)2(H2O)4](HTNR)2·4H2O

FENG Jin-Ling1ZHANG Jian-Guo1,*ZHANG Tong-Lai1,*CUI Yan2

(1State Key Laboratory of Explosion Science and Technology,Beijing Institute of Technology,Beijing 100081,P.R.China;2The 6th Department,Research Institute of Chemical Defense(PLA),Beijing 102205,P.R.China)

A novel energetic coordination complex of[Mn(AZT)2(H2O)4](HTNR)2·4H2O(AZT=3-azido-1,2,4-triazole,HTNR=2,4,6-trinitro resorcinol)was prepared by the reaction between the acidic manganese(II)salt of 2,4,6-trinitro resorcinol and AZT in an aqueous solution.The complex was characterized by elemental analysis and FTIR spectroscopy.The molecular structure was determined by X-ray single crystal diffraction.The crystal belongs to the triclinic system with a P1 space group.The central manganese(II)cation has a slightly distorted octahedron feature.Three-dimension networks were formed and the layers are linked by extensive hydrogen bonding.The thermal decompositionmechanismof[Mn(AZT)2(H2O)4](HTNR)2·4H2O was predicted based on differential scanning calorimetry(DSC)and thermogravimetry-derivative thermogravimetry(TG-DTG)analyses.One endothermic peak and three exothermic peaks are present during the thermal decomposition process with the final residue at 600℃being MnO and MnO2.The kinetic parameters of the exothermic process for the complex were studied using Kissinger′s and Ozawa-Doyle′s methods.Furthermore,impact sensitivity,flame sensitivity,and friction sensitivity tests reveal that the title complex is sensitive and selective towards external stimulants.

Crystal structure;3-Azido-1,2,4-triazole;Manganese(II)complex;Sensitivity;Thermal behavior

Nitrogen-rich compounds have attracted significant attention due to their potential applications as high-energy-density materials(HEDMs)in propulsion and explosive fields[1-7].They derive most of their energies either from the oxidation of the carbon backbone,or from their high positive heats of formation[8].Good HEDMs possess high density,have a fast velocity of detonation, and are energetically unstable with respect to their reaction products.Five-member nitrogen-rich heterocyclic compounds, such as triazole series[9-15],are one of the representative candidates of HEDMs.The high positive formation enthalpy and high nitrogen content of triazole have made its complexes interesting for being used as energetic materials.The addition of azide group strongly immproves its energetic properties[16].The nitrogen content of 3-azido-1,2,4-triazole(AZT)is 76.36%,and its standard heat of formation(ΔH?f)is 458 kJ·mol-1[17].

Hydroxyl O atoms and triazolyl ring N atoms have good coordination capacities.Therefore,1,2,4-triazole has potential bridging fashions(μ1,2,μ2,4,and μ1,2,4)and strong coordination capabilities to bridge transition metal ions[18].To the best of our knowledge in published studies on 1,2,4-triazole-based energetic complexes,the ligands have been limited to 1,2,4-triazol-5-one[19-20],3-nitro-1,2,4-triazol-5-one[21-24],and 4-amino-1,2,4-triazol-5-one[25]. Thusfar,theligandsofothertriazolederivatives,suchas3-amino-1H-1,2,4-triazole[26]and 3,4,5-triamino-1,2,4-triazole[27],have been briefly studied.For the compound of AZT,main attention has been focused on its energetic ionic salts[28-32],except for our early research of using AZT as ligands for zinc(II)and cadmium(II) cations,where the structure and thermal properties were investigated[33-34].

Enlightened by previous studies,we have selected other transition metals to construct novel AZT-based coordination compounds with new structures.Herein,we report a new manganese coordination compound[Mn(AZT)2(H2O)4](HTNR)2·4H2O,with AZT and H2O molecules as ligands,acidic anion of 2,4,6-trinitro resorcinol(HTNR)as outer anion.Thermal decomposition mechanism was studied with differential scanning calorimetry(DSC), thermogravimetry-derivative thermogravimetry(TG-DTG)analyses,and Fourier transform infrared(FTIR)spectroscopy.Furthermore,the investigations of sensitivity properties revealed the potential application of the title compound as an energetic material in ammunitions.

1 Experimental

General caution:AZT and its coordination compound are energetic materials and tend to explode under certain conditions. Appropriate safety precautions,such as safety glasses,face shields,leather coat,and ear plugs,should be taken during the synthesis,test,and measurement processes,especially when these compounds are prepared on a large scale and in dry states.

1.1 Materials and instruments

All chemicals from commercial sources were of analytical pure and used without further purification.AZT was prepared according to the method literature[35]reported.

FTIR spectrum was recorded as KBr pellets on a Bruker Equinox 55 infrared spectrometer(Germany)in the range of 4000-400 cm-1with the resolution of 4 cm-1.Elemental analysis was carried out by a Flash EA 1112 full-automatic trace element analyzer(USA).

DSC studies were performed on Perkin-Elmer Pyris-1 Differential Scanning Calorimeter(USA)with heating rates of 2,5,10, 15,and 20℃·min-1,respectively.TG analysis was conducted on Perkin-Elmer Pyris-1 Thermo-gravimetric Analyzer(USA) with a heating rate of 10℃·min-1in a flow of dry oxygen-free nitrogen at 20 mL·min-1.The sample of 0.5 mg was sealed in aluminum pans for DSC and held in platinum pans for TG-DTG.

1.2 Preparation

MnCO3(2.30 g,20 mmol)was added to a suspending solution of 2,4,6-trinitro resorcinol(9.80 g,40 mmol)in 20 mL distilled water at 50℃with vigorous stirring.Mn(HTNR)2solution was obtained after filtering the mixture.AZT(4.40 g,40 mmol)was dissolved in 40 mL distilled water,and the solution was added dropwise when the temperature reached 60℃.The mixture was stirred for an additional 1 h to complete the reaction.The jacinth precipitate was collected by filtration,washed with ethanol and dried in vacuum,with a yield of 84%(based on AZT).Element analysis,Calcd.(%)for[Mn(AZT)2(H2O)4](HTNR)2·4H2O:C, 21.16;H,2.64;N,27.77;Found(%):C,21.11;H,2.62;N,27.95. IR data(KBr pellet,ν/cm-1):3394(s),2150(s),1631(s),1572(s), 1531(s),1465(s),1333(s),1272(m),1180(m),1085(s),971(w), 927(m),873(w),735(m),692(m),626(w).

1.3 X-ray crystallography

Single crystals of[Mn(AZT)2(H2O)4](HTNR)2·4H2O were obtained through slow evaporation of a saturated water solution at 15℃for 25 d(distilled water,white rods,0.22 mm×0.20 mm× 0.18 mm).A Bruker Smart 1000 CCD diffractometer(Germany) with graphite monochromatic Mo Kαradiation(λ=0.07107 nm) was used for data collection at 21℃.Intensity measurements were performed using φ and ω scan modes.A total of 2793 reflections were used to determine the lattice parameters and orientation matrix in the range of 2.38°≤θ≤26.34°.The structure was solved by direct methods using SHELXS-97[36]and refined by full-matrix least squares techniques based on F2with the SHELXL-97 program[37].All non-hydrogen atoms were obtained from the difference Fourier map and refined anisotropically.All hydrogen atoms were generated geometrically or from the difference Fourier map,and treated by a constrained refinement. Crystallographic and refinement data are listed in Table 1.

2 Results and discussion

2.1 Structure description

[Mn(AZT)2(H2O)4](HTNR)2·4H2O crystallizes with a triclinic unit cell in the space group P1.The coordination environment of themanganesecationandthemolecularunitof[Mn(AZT)2(H2O)4] (HTNR)2·4H2O,with atom labeling and the intra-molecular hydrogen bonds,are shown in Fig.1.Packing diagram of [Mn(AZT)2(H2O)4](HTNR)2·4H2O viewed along a-axis is shownin Fig.2.Selected bond data of[Mn(AZT)2(H2O)4](HTNR)2· 4H2O,compared with those in the molecular crystal of AZT[34], are listed in Table 2.The hydrogen bond lengths and bond angles are listed in Table 3.

Table 1 Crystal data and structure refinement for [Mn(AZT)2(H2O)4](HTNR)2·4H2O

As we can see from Fig.1,in the molecular unit of[Mn(AZT)2(H2O)4](HTNR)2·4H2O,each central manganese(II)ion is hexacoordinated with two N(4)atoms from two AZT molecules and four O atoms from four H2O molecules to form a centrosymmetric slightly distorted octahedron.There are three parallelogram planes in the structure,N(4)—O(9)—Mn(1)—N(4)#1—O(9)#1 (plane A),O(10)—N(4)—Mn(1)—O(10)#1—N(4)#1(plane B), and O(10)—O(9)—Mn(1)—O(10)#1—O(9)#1(plane C).The angles between plane A and plane B,plane B and plane C,plane C and plane A,all slightly derivate from 90°,are 86.0°,91.4°, and 91.2°,respectively.The bond lengths of manganese(II)centertothesixcoordinationatomscanbeobservedtobe0.2140(13) nm for Mn(1)—O(10)and Mn(1)—O(10)#1,0.2212(14)nm for Mn(1)—O(9)and Mn(1)—O(9)#1,0.2277(16)nm for Mn(1)—N(4)and Mn(1)—N(4)#1.The bond angles for O(10)—Mn(1)—O(10)#1,O(9)—Mn(1)—O(9)#1 and N(4)#1—Mn(1)—N(4)are almost the same(180°),while those around the central Mn2+derivate from 90°by the value of 1.28°,1.06°,and 3.97°,for the reason of the steric hindrance effect by the bulky AZT molecules and H2O molecules.

In the crystal structure of[Mn(AZT)2(H2O)4](HTNR)2·4H2O, thecoordinationsiteofAZTisalsoN(5)atom,whichhasthemost negative charge(-0.49387e)as calculated at the B3LYP/6-311+ G**level using the Gaussian 98 program package[34].Most of the bond lengths and bond angles for the AZT ligand differ slightly from the corresponding ones of AZT molecule(Table 2),except for the azido-group with relatively obvious changes.The bond lengths of N(6)—C(8),N(7)—C(8)and N(8)—N(9)are shortened by 0.0007,0.0012 and 0.0007 nm,respectively,the elongation of the N(4)—C(8)bond is 0.0008 nm,otherwise.The rea-son for this can be concluded as the existence of the small steric hindrance effect of four H2O molecules.Besides,the coordination of Mn—N(4)destroys the natural p-π conjugation and π-π conjugation among the crystal structure of AZT in which the triazole ring is aromatic and contains six delocalized π-electrons. Corresponding to the length changes,the bond angels of N(8)—N(7)—C(8)and N(6)—N(8)—N(7)are increased by ca 3°,while that of N(9)—N(8)—N(7)is decreased by ca 3°.This kind of arrangement can facilitate the coordinated small-sized H2O molecules and the bulky AZT molecules with central manganese(II)cation to complete the octahedral sphere figure.The bond lengths and bond angles of HTNR are usual for coordination compounds with HTNR as outer anions.

Table 2 Selected bond lengths and bond angles for[Mn(AZT)2(H2O)4](HTNR)2·4H2O and AZT

Table 3 Hydrogen bond lengths and bond angles for[Mn(AZT)2(H2O)4](HTNR)2·4H2O

There are many kinds of hydrogen bonds in the crystal structure of[Mn(AZT)2(H2O)4](HTNR)2·4H2O.Lattice and coordination H2O molecules play vital roles in the formation of the structure.Three types of intra-molecular hydrogen bonds can be observed from Fig.1.The first type is formed between the hydroxylgroup and nitro-group of the HTNR anion,O(6)—H(6)…O(5) and O(6)—H(6)…N(2).The second type occurs between the lattice H2O molecules and the adjacent nitro-group of the HTNR anion,O(11)—H(11A)…O(3).The third type takes place among the coordinated and lattice H2O molecules of O(9),O(11),and O (12).we can see from Fig.2 that all the molecular units are linked together into 3D structures by the intermolecular hydrogen bonds,which are formed among different molecular units and can be divided into two types.One type takes place between the lattice H2O molecules and coordinated H2O molecules or AZT molecule,O(12)—H(12A)…O(9)#3,O(10)—H(10A)…O (11)#2,N(5)—H(5)…O(12)#4.The similar mode occurs between the hydroxyl-group or deprotonated hydroxylgroup of the outer HTNR anion and the coordinated H2O molecules or AZT molecule,O(10)—H(10B)…O(1)#4,O(9)—H(9A)…O(4)#2, and O(6)—H(6)…N(6)#1,O(12)—H(12B)…O(1)#4.These extensive hydrogen bonds also make an important contribution totheformationandstabilityofthecrystalstructureof[Mn(AZT)2(H2O)4](HTNR)2·4H2O.

2.2 Thermal decompositions

Under the linear heating rate of 10℃·min-1,DSC and TGDTG experiments were carried out in order to investigate the thermal behaviors of[Mn(AZT)2(H2O)4](HTNR)2·4H2O.The DSC and TG-DTG curves of[Mn(AZT)2(H2O)4](HTNR)2·4H2O are illustrated in Fig.3 and Fig.4.

Fig.3 DSC curve of[Mn(AZT)2(H2O)4](HTNR)2·4H2O at a heating rate of 10℃·min-1

Fig.4 TG-DTG curves of[Mn(AZT)2(H2O)4](HTNR)2·4H2O at a heating rate of 10℃·min-1

There are one endothermic process and three exothermic peaks in the range of 45.3-600℃.A mass loss of 15.8%can be seen in the TG-DTG curves during the first stage of 45.3-176.2℃,which is in coincident with the theoretical value of losing four lattice H2O molecules and four coordination H2O molecules. The structure of the compound is unstable and begins decomposing with three steps after lossing all the H2O molecules.The first-step is a sharp exothermic decomposition occurred during the temperature range of 176.2-229.8℃,with the peak temperature at 210.9℃and the exothermic enthalpy change of 185.9 kJ·mol-1.There is a mass loss of 20.2%in the TG-DTG curve. The compound undergoes further decomposition in the range of 229.8-339.2℃,with a peak temperature at 303.9℃and a mass loss of 29.7%.The exothermic enthalpy of this process is 187.1 kJ·mol-1,the value of which is similar to the first exothermic process.The last exothermic process occurs with the onset temperature at 388.2℃and the peak temperature at 444.1℃,the mass loss corresponding to this stage in TG-DTG curves is 35.0%.The exothermic enthalpy change(1038.3 kJ·mol-1)of this process is very strong.The mass fraction of the final residue is 9.3%,which is between the theoretical values of MnO and MnO2,7.8%and 9.6%.The absorption band at 600 and 650 cm-1in the FTIR spectrum of the residue at 600℃also proves that the final residue is the mixture of MnO[38]and MnO2[39].

Based on the experimental and calculated results,the thermal decomposition processes of the complex can be proposed as follows:

2.3 Non-isothermal kinetics analysis

We can see,from the DSC and TG-DTG curves,the first exothermic process has dominant effects on the decomposition of the complex.Hence,we studied the kinetics parameters of the first exothermic process of[Mn(AZT)2(H2O)4](HTNR)2·4H2O by using the Kissinger′s[40]and Ozawa-Doyle′s[41]methods.The Kissinger equation(1)and Ozawa-Doyle equations(2)are as follows:

where Tpis the peak temperature,℃;R is the gas constant,8.314 J·mol-1·℃-1;β is the linear heating rate,℃·min-1;C is a constant.

Based on the multiple non-isothermal DSC curves obtained atfive different heating rates of 2,5,10,15,20℃·min-1,the peak temperatures Tpcan be observed as 196.5,203.3,211.1,214.8, 215.7℃.The values of apparent activation energy Ekand Eo, which are calculated by the Kissinger′s method and Ozawa-Doyle′s method,are 206.3 and 203.7 kJ·mol-1,respectively.The corresponding linear coefficients rkand roare 0.9934 and 0.9939. The pre-exponential factor Akdetermined with the Kissinger′s method is 20.55 s-1.The calculated results using both methods are similar and within the normal range of kinetic parameters of such thermal decomposition reaction[42].

The Arrhenius equation can be expressed with Ea(the average of Ekand Eo)and lnAkas follows:lnk=20.55-206.3×103/(RT). This equation can be used to estimate the rate constants of the initialthermaldecompositionprocessof[Mn(AZT)2(H2O)4](HTNR)2· 4H2O.

2.4 Sensitivitypropertiesofcomplex[Mn(AZT)2(H2O)4] (HTNR)2·4H2O

Inordertostudythestabilityandthehazardof[Mn(AZT)2(H2O)4] (HTNR)2·4H2O,we tested its sensitivity properties.The sample of 20 mg was compacted in a copper cap with a pressure of 39.2 MPa to test the impact sensitivity and flame sensitivity.The impact sensitivity was determined with a Bruceton method[43]on the standard fall hammer apparatus,and the compacted sample was hit with 0.8 kg drop hammer on the apparatus.The results of impact sensitivity showed that[Mn(AZT)2(H2O)4](HTNR)2·4H2O did not fire at the highest apparatus limitation of 53 cm.

The flame sensitivity was determined on a designed flame sensitivity apparatus,and the compacted sample was ignited by a standard black powder pellet right above the sample.The friction sensitivity was determined by using a standard pendulum apparatus.According to the standard method[44],flame sensitivity was evaluated with the height for 50%probability of explosion (h50%)of the sample.h50%of[Mn(AZT)2(H2O)4](HTNR)2·4H2O is calculated as 15.42 cm,which reveals that the compound has a moderate flame sensitivity.

The sample was compressed firmly between two steel poles with mirror surfaces at the pressure of 1.96 MPa,then it was hit horizontally with a 1 kg hammer dropping from 90°angle.The statistical firing rate about friction sensitivity of[Mn(AZT)2(H2O)4](HTNR)2·4H2O is 80%,which shows that it is relatively sensitive to friction at the testing conditions.The sensitivity testing results are related with the molecular structure and thermal stability of the compound.

3 Conclusions

A novel energetic coordination compound[Mn(AZT)2(H2O)4] (HTNR)2·4H2O was synthesized and structurally characterized. Thermal analyses show that there are one endothermic process and three exothermic decomposition stages in the temperature range of 45.3-600℃,with the final residue at 600℃being the mixture of MnO and MnO2.The sensitivity test results indicate that[Mn(AZT)2(H2O)4](HTNR)2·4H2O has relatively strong sensitivity to friction,moderate sensitivity to flame and weak sensitivity to vertically hit,which means the compound possesses sensitivity and selectivity,which is of significance interest for ammunition application.

Supporting information: CCDC No.746340 contains the supplementary crystallographic data for this article.These data can be obtained free of charge at http://www.ccdc.cam.ac.uk[or from the Cambridge Crystallographic Data Centre(CCDC),12 Union Road,Cambridge CB2 1EZ,UK;Fax:+44(0)1223-336033;Email:deposit@ccdc.cam.ac.uk].

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[Mn(AZT)2(H2O)4](HTNR)2·4H2O的合成、晶體結(jié)構(gòu)、熱行為及感度性質(zhì)

馮金玲1張建國(guó)1,*張同來1,*崔 燕2

(1北京理工大學(xué)爆炸科學(xué)與技術(shù)國(guó)家重點(diǎn)實(shí)驗(yàn)室,北京 100081;2防化研究院第六研究所,北京 102205)

通過酸性2,4,6-三硝基間苯二酚(HTNR)的錳鹽與3-疊氮-1,2,4-三唑(AZT)在水溶液中反應(yīng),制備得到一種新穎的錳配合物[Mn(AZT)2(H2O)4](HTNR)2·4H2O.通過元素分析和紅外光譜對(duì)配合物進(jìn)行了表征,用X射線單晶衍射分析確定其晶體結(jié)構(gòu).該配合物為三斜晶系,空間群為P1,中心錳(II)離子為六配位的畸變的八面體結(jié)構(gòu),分子內(nèi)和分子間強(qiáng)烈的氫鍵作用構(gòu)成了有序的三維(3D)網(wǎng)狀結(jié)構(gòu).采用差示掃描量熱(DSC)和熱重-微分熱重 (TG-DTG)分析技術(shù)研究了配合物的熱分解特性,并預(yù)測(cè)了它的熱分解反應(yīng)機(jī)理.利用Kissinger方法和Ozawa-Doyle方法研究了其第一放熱分解峰的分解動(dòng)力學(xué)過程.其分解過程包括一個(gè)吸熱峰和三個(gè)放熱峰,在600℃的分解產(chǎn)物為MnO和MnO2的混合物.同時(shí).對(duì)這個(gè)配合物進(jìn)行了感度(撞擊感度、火焰感度、摩擦感度)性能分析,結(jié)果表明,它對(duì)外界刺激具有很強(qiáng)的響應(yīng)性和選擇性.

晶體結(jié)構(gòu);3-疊氮-1,2,4-三唑;錳(II)配合物;感度;熱行為

O641;O642;O741

Received:April 1,2010;Revised:May 23,2010;Published on Web:July 15,2010.

*Corresponding authors.ZHANG Jian-Guo,Email:zhangjianguobit@yahoo.com.cn.ZHANG Tong-Lai,Email:ztlbit@bit.edu.cn;

Tel/Fax:+86-10-68913818.

The project was supported by the National Natural Science Foundation of China(20471008)and Program for New Century Excellent Talents in Universities of the Ministry of Education of China(NCET-09-0051).

國(guó)家自然科學(xué)基金(20471008)和教育部新世紀(jì)優(yōu)秀人才支持計(jì)劃（NCET-09-0051）資助項(xiàng)目

?Editorial office of Acta Physico-Chimica Sinica