（TAGH）2（TNR）的合成、晶体结构及热分析

合成了三氨基胍三硝基间苯二酚盐(TAGH)2(TNR)(TAG)三氨基胍;TNR:2,4,6-三硝基间苯二酚),并对其进行了元素分析及红外光谱表征.利用X射线单晶衍射分析测定了其晶体结构.该晶体属于单斜晶系,空间群为C2/c,晶体学数据为,a=2.2892(6)nm,b=1.2802(3)nm,c=1.3661(4)nm,β=111.174(5)°,V=3.7333(16)nm3,Z=8.该化合物是由二个C(N2H3)3+与一个(C6HN3O8)2相结合而成的离子型化合物.用差示扫描量热法、热重法和微商热重法研究了该化合物的热分解过程,研究结果表明,在10 K·min-1的升温速率下,该化合物只有一个剧烈的放热分解过程,该过程发生在450.1-477.7K之间,且分解产物主要是气体产物.     

三氨基胍三硝基间苯二酚盐的制备、晶体结构及热分解

利用三氨基胍和斯蒂芬酸制备得到了三氨基胍三硝基间苯二酚盐, 培养出了可用于X射线衍射的单晶. 利用元素分析、红外光谱、差示扫描量热法(DSC)、热重-微分热重法(TG-DTG)和X射线单晶衍射等方法对标题化合物的组成和结构进行了表征. 晶体属于三斜晶系, 空间群为P-1, 晶胞参数a＝0.75554(15) nm, b＝0.90816(18) nm, c＝1.0264(2) nm, α＝101.61(3)°, β＝91.96(3)°, γ＝107.74(3)°, V＝0.6536(2) nm3; Dc＝1.775 g/cm3; Z＝2; F(000)＝360, μ＝0.160 mm－1, R1＝0.0479, ωR2＝0.0998. 晶体结构分析结果表明, 该化合物分子式为C7N9O7H11, 是由[C(N2H3)3]＋和(C6N3O8H2)－结合成的离子化合物, 分子中含有大量的氢键, 结构较为稳定. 热分析结果表明, 在10 K/min的升温速率下, 标题化合物的热分解过程由1个吸热峰和3个放热峰组成, 分解产物大部分为气相产物, 剩余残渣量在1%左右.     

M2TNR(M=AG, CHZ)的制备和晶体结构

通过三硝基间苯二酚(TNR,斯蒂酚酸)和氨基胍(AG)重碳酸盐、碳酰肼(CHZ)反应,制备斯蒂酚酸氨基胍和斯蒂酚酸碳酰肼。并用X-射线衍射分析、元素分析、差示扫描量热法和红外光谱对其进行了结构表征。它们的分子式分别为(NH2NHCNHNHNH2)2^+[C6H(NO3)3O2]^2.0.5H2O,(NH2NHCONHNH3)2^+[C6H(NO3)3O2]^2^-,二者都属于单斜晶系,C2/c空间群。     

(AG)(DNP)的合成和结构表征

通过氨基胍(AG)重碳酸盐与2,4-二硝基苯酚(DNP)反应,制备了新型离子型化合物2,4-二硝基苯酚氨基胍(AG)-(DNP).通过X射线单晶衍射、元素分析、红外光谱和热分析对其进行了表征.测试结果表明:该晶体属于单斜晶系,空间群P21/n,a=0.4922(1)nm,b=2.3307(3)nm,c=0.9404(6)nm,β=91.621(2)°,Z=2,Dc=1.590g/cm3,F(000)=144.该化合物分子由氨基胍阳离子和2,4-二硝基苯酚阴离子以静电引力结合,分子间存在氢键.该化合物是一种具有潜在应用前景的气体发生剂.     

[Pb2(TNR)2(CHZ)2(H2O)2]·4H2O的结构及热分解机理

用碳酰肼 (CHZ ,NH2 NHCONHNH2 )、硝酸铅和三硝基间苯二酚 (TNR ,斯蒂酚酸 )的水溶液制备 [Pb2 (TNR) 2 (CHZ) 2 (H2 O) 2 ]·4H2 O .采用单晶分析的方法测定它的分子结构 ,并用TG DTG、DSC和　IR相结合的技术研究它的热分解机理 .所得晶体属单斜晶系 ,P2 1/n空间群 .晶体学参数为 :a=0 .6470 0 ( 10 )nm ,b =1.60 74 ( 3)nm ,c=1.4 883( 3)nm ,β =97.4 2 ( 2 )° ,V =1.534 9( 5)n ,Z =2 ,DC=2 .572 g·cm- 3,μ(Mo ,Kα) =11.0 80cm- 1,F( 0 0 0 ) =112 8.最终偏离因子R =0 .0 4 2 2 ,Rw=0 .0 735.该配合物分子呈中心对称 ,两个羰基O原子形成两个氧桥 ,TNR2 - ,CHZ和H2 O同时参与了与中心离子的配位     

[Ni(CHZ)_3](TNR)·5H_2O的制备、晶体结构和热分解机理

用 2 ,4,6 三硝基间苯二酚 (斯蒂芬酸 ,TNR)镍的水溶液和碳酰肼 (CHZ ,NH2 NHCONHNH2 )水溶液反应 ,制备出配合物 [Ni(CHZ) 3](TNR)·5H2 O ,测定了其晶体结构 ,并用TG DTG ,DSC和IR技术研究了其热分解机理 .该晶体属三斜晶系 ,P1空间群 ,晶胞参数a =1 0 45 40 (1 0 )nm ,b =1 1 6 71 (2 )nm ,c =1 2 2 78(2 )nm ,α=1 0 9 1 90 (1 0 )°,β=1 2 1 1 6 8(1 2 )°,γ =99 70 0 (1 0 )°,V =1 2 6 1 3(3)nm3,Z =2 ,Dc=1 744 g/cm3,μ(Mo ,Kα) =0 873mm-1,F(0 0 0 ) =6 88,R =0 0 41 9,Rw=0 1 0 5 3.在该配合物分子中 ,碳酰肼为双齿配体 ,由羰基O原子和 1位N原子与Ni2 + 离子配位 ,分子中共形成 3个五元平面螯合环 ,中心离子为六配位八面体结构 .该配合物在程序升温条件下 ,分两步脱去所含结晶水 ,第一步失去 4个结晶水 ,第二步失去 1个结晶水 ,在 5 0 0℃时的最终分解产物为Ni2 O3.     

[K(HTNR)(H_2O)]_n的制备、晶体结构和热分解机理

通过2，4，6－三硝基间苯二酚（斯蒂芬酸，TNR）与氢氧化钾在乙醇溶液中反 应，首次合成出配位聚合物[K(HINR)-(H_2O)]_n，并测定了其晶体结构。该晶体属 单斜晶系, P2_1/c空间群；晶胞参数： a = 0.7888(1)nm, b = 1.38002(2) nm, c = 0.9520(1) nm, β=8.91(1)°；V = 1.0238(2) nm~3; D_c = 1.954 g/cm~3; Z = 4; F(000) = 608; μ(MoKα) = 0.575 mm~(-1)。用DSC，TG－DTG及FT－IR 等分析方法研究了该配位聚合物的热分解机理。在线性升温条件下，该配合物的热 分解包含两个重叠的弱吸热过程和两个强放热分解过程。分解残渣的红外分析表明 ，在271.9 ℃时，分解残渣中有KNCO与羧酸钾，357.1 ℃时，残渣中只有KNC存在 。     

M(TNR)·H2O的热分解机理

本文用TG—DTA、DSC、IR和X光衍射分析考察了三硝基间苯二酚金属盐M(TNR)·H_2O(M=Pb、1/4Pb3/4Ba、Ba)的热行为及其热分解机理。结果表明,M(TNR)·H_2O晶体的热分解过程均分三个阶段进行。即脱水阶段;脱硝逸出NO_2伴随苯环碎裂成凝聚相产物的阶段和凝聚相产物分别生成PbO和少量碳;BaCO_3、PbO和少量碳;BaCO_3的阶段。     

吗啉二硫代氨基甲酸铁(Ⅲ)配合物Fe(S2CNC4H8O)3的合成、表征及晶体结构

合成了标题化合物Fe(S2CNC4H8O)3,得到黑色柱状晶体.晶体属三斜晶系,空间群为P-1,晶胞参数a=O.9300(2)nm,b=1.0490(2)nm,c=1.3710(3)nm,a=100.60(3)°,β=95.40(3)°,γ=106.60(3)°,V=1.2445(4)nm3,Mr=542.58,Z=2.中心Fe原子分别与来自三个吗啉二硫代氨基甲酸的六个硫原子配位形成八面体构型,由于四元螯合环的环张力,导致该八面体严重变形,六个Fe-S键的键长范围在0.2423(5)～O.2458(2)nm.热分析表明标题化合物在791.80℃完全分解.     

5-硝基-2H-四唑的合成、反应性及产物晶体结构的研究

5-氨基四唑(1)经过重氮化反应得到5-硝基四唑(5),5与甲醛反应得到2-羟甲基-5-硝基四唑(6),6与HCl或HBr反应分别得到5-5氯代四唑(7)和5-溴代四唑(8),采用MS,IR,1H NMR,13C NMR等技术对这些化合物进行了表征.用X射线单晶衍射法测定了化合物5-硝基四唑钠(4),5和6的晶体结构.化合物4属于三斜晶系,P-1空间群;化合物5和6均属于单斜晶系,P21空间群,化合物6的晶胞参数a=0.66131(18)nm,b=0.54905(15)nm,c=0.7566(2)nm,Z=2,V=0.27470(13)nm3,Dc=1.754g/cm3,F(000)=128,μ=0.160mm-1.     

Synthesis, Crystal Structure and Thermal Analysis of (TAGH)2(TNR)

A new energetic compound (TAGH)₂(TNR) (TAG: triaminoguanidine, TNR: 2,4,6-trinitroresorcinol) was prepared by reacting triaminoguanidine with 2,4,6-trinitroresorcinol (styphnic acid) in aqueous solution under nitrogen atmosphere, and characterized by elemental analysis and Fourier transform infrared (FTIR) spectra. Its crystal structure was determined by single crystal X-ray diffraction analysis. The crystal belonged to a monoclinic, C 2/c space group. The unit cell parameters were as follows: a=2.2892(6) nm, b=1.2802(3) nm, c=1.3661(4) nm, β=111.174(5)°, V=3.7333(16) nm³, and Z=8. The compound consisted of two cations C(N₂H₃)₃⁺ and an anion (C₆HN₃O₈)²⁻. The C(N₂H₃)₃⁺ and (C₆HN₃O₈)²⁻ were bonded together by electrostatic attraction and hydrogen bonds, and this effect made the compound more stable. The thermal analysis of the compound was studied by using differential scanning calorimetry (DSC), thermogravimetry-derivative thermogravimetry (TG-DTG). Under nitrogen atmosphere with a heating rate of 10 K·min⁻¹, the thermal decomposition of the compound contained only one intense exothermic decomposition process in the range of 450.1-477.7 K in the DSC curve, and the decomposition products were nearly gaseous products.     

Synthesis,Crystal Structure,Thermal Decomposition and Sensitivity Properties of (AIM)(HTNR) and (AIM)(PA)

Two new energetic compounds (AIM)(HTNR) and (AIM)(PA)(AIM=2-azidoimidazole, TNR=2,4,6-trinitroresorcinol, PA=picric acid) have been prepared by AIM(2-azidoimidazolium) and TNR(2,4,6-trinitroresorcinol) or PA(picric acid) and characterized by elemental analysis and FTIR spectrum. Their crystal structures were determined by X-ray single-crystal diffraction analysis. The obtained results show that (AIM)(HTNR) crystal belongs to monoclinic, P2₁/c space group, a=1.1306(2) nm, b=0.70305(14) nm, c=1.7398(4) nm, β=106.91°, V=1.3231(5) nm³, D_c=1.778 g/cm³, Z=4, R₁=0.0524, wR₂[I>2σ(I)]=0.1067 and S=1.092 and (AIM)(PA) crystal belongs to monoclinic P2₁/c space group, a=0.80303(16) nm, b=0.81395(16) nm, c=2.0471(4) nm, β=93.93(3)°, V=1.3349(5) nm³, D_c=1.683 g/cm³, Z=4, R₁=0.0784, wR₂[I>2σ(I)]=0.1814 and S=1.098. Both the compounds have electrostatic attraction and hydrogen bonds, which contribute to making the constructions more stable. The decomposition of the two compounds was studied via differential scanning calorimetry(DSC) and thermogravimetry-derivative thermogravimetry(TG-DTG) techniques at a heating rate of 10 ℃/min, and the results show that both the compounds underwent one intensive exothermic decomposition stage. Sensitivity tests reveal that the title compounds were insensitive to friction and impact and sensitive to flame and could be applied in potential pyrotechnics.     

[Pb2(TNR)2(CHZ)2(H2O)2]4H2O的结构及热分解机理

The coordination compound of [Pb 2(TNR) 2(CHZ) 2(H 2O) 2]•4H 2O was prepared by using the aqueous solution of carbohydrazide, lead nitrate and sodium styphnate. The molecular structure of [Pb 2(TNR) 2(CHZ) 2(H 2O) 2]•4H 2O(C 7H 13 N 7O 12 Pb, Mr=594.43) was determined by using a single crystal diffraction analysis .The thermal decomposition mechanism of the title compound was studied by TGDTG, DSC and IR techniques. The crystal belongs to monoclinic with space group P2 1/n.The unit cell parameters are as follows: a=0.64700(10)nm, b=1.6074(3)nm, c=1.4883(3)nm,β=97.42(2)°,V=1.5349(5)nm3, Z=2, DC=2.572g•cm -3 ,μ(Mo, Kα)=11.080cm -1 , F(000)=1128. R=0.0422, Rw=0.0735. The binuclear lead coordination compound is bridged by two carbohydrazide molecules. The molecule has a symmetrical center. TNR 2- ,CHZ and H 2O coordinate with the central ions simultaneously.     

[Sr(CHZ)(TNR)(H2O)(OH)]2·2H2O的晶体结构和热分解机理

The coordination compound of [Sr(CHZ)(TNR)(H₂O)(OH)]₂·2H₂O (TNR: 2,4,6-trinitroesorcinol, CHZ: carbohydrazide) was prepared by reacting CHZ solution and strontium styphnate solution (obtained through the reaction of strontium carbonate and styphnic acid). The molecular structure was characterized by using X-ray diffraction analysis, element analysis and FTIR analysis. The crystal belongs to triclinic with space group P1. The unit cell parameters were as follows: a=0.725 2(2) nm, b=1.021 2(2) nm, c=1.144 0(2) nm, α=69.50(3)°, β=78.82(3)°, γ=84.64(3)° and Z=2. The thermal decomposition of the compound is studied using differential scanning calorimetry (DSC) and thermogravimetry thermogravimetry-derivative (TG-DTG) techniques. CCDC: 269310.     

A new hetero-bimetallic coordination polymer, cesium, and sodium complex of styphnate trihydrate [CsNa(TNR)(H2O)3] n

A new hetero-bimetallic coordination polymer, cesium, and sodium complex of styphnate trihydrate [CsNa(TNR)(H₂O)₃] _n (TNR: 2,4,6-trinitroresorcinol dianion, the dianion of styphnic acid) was synthesized. The title complex was characterized by X-ray single crystal diffraction, element analysis, FT-IR, DSC, TG-DTG studies. In the title polymer molecule, the cesium cation is coordinated by 13 oxygen atoms: three originated from the water molecule and the others are from the nitro group and the phenolic hydroxyl group of TNR; the sodium cation is surrounded by six oxygen atoms from water molecules and TNR forming a distorted octahedron. The coordination polymer crystal was formed by the bridging ligands of water molecules and TNR connected with different cesium and sodium cations.     

含能化合物（AIM）NO3与（AIM）（HTNR）·H2O的合成、晶体结构及性质研究

利用2-叠氮咪唑(AIM)与硝酸(HNO3)和斯蒂芬酸(TNR),采用直接法合成了新型含能化合物2-叠氮咪唑硝酸盐和2-叠氮咪唑斯蒂芬酸合水,利用缓慢蒸发溶剂法培养出了可用于X射线衍射的单晶.利用X射线单晶衍射测定了标题化合物的结构,并利用元素分析和红外光谱的方法对其组成进行了表征.实验研究表明2-叠氮咪唑硝酸盐晶体属于单斜晶系,空间群为P21/c,晶胞参数为a=17.034(3),b=6.5214(13),c=13.095(3),β=111.78(3)°,V=1350.8(5)3;Dc=1.693g/cm3;分子式为C3N6O3H4,是由AIM+和NO-3结合成的离子化合物,分子中含有大量的氢键,结构较为稳定.2-叠氮咪唑斯蒂芬酸合水晶体属于三斜晶系,空间群为P1,晶胞参数为a=6.4900(13),b=7.4286(15),c=15.401(3),α=101.57(3)°,β=98.56(3)°,γ=99.89(3)°,V=703.6(2)3;Dc=1.757g/cm3;分子式为C9H8N8O9,是由AIM+和HTNR-结合成的离子合水化合物.利用差示扫描量热法(DSC)和热重-微分热重法(TG-DTG)对其热分解进行分析,结果表明,在10℃/min的升温速率下,两个化合物的热分解均出现1个放热峰,分解产物主要为气体物质.最后对标题化合物进行感度性能测试,结果表明(AIM)NO3具有一定的火焰感度,有望作为含能材料应用于相关领域.     

Preparation,Crystal Structure,Thermal Decomposition and Explosive Properties of K2（tza）2（H2O） （tza=Tetrazole-1-acetic Acid）

A new energetic compound based on the tetrazole-1-acetic acid (tza) and potassium(I) salt, K2(tza)2(H2O), was synthesized and characterized by elemental analysis and FT-IR spectrum. Its crystal structure was determined by single-crystal X-ray diffraction analysis. The results show that the crystal belongs to the orthorhombic system, space group Pna21 with a = 1.11972(17) nm, b = 0.46647(7) nm, c = 2.5158(4) nm, V = 1.3140(3) nm3, K2C6H8N8O5, Mr = 350.40 g·mol-1, Dc = 1.771 g·cm-3, μ(MoKα) = 0.759 mm-1, F(000) = 712, Z = 4, R = 0.023 and wR = 0.0527 for 2961 observed reflections (I > 2σ(I)). The K(I) cation is six-coordinated with four O atoms from three carboxylate groups, one O atom from one H2O molecule and one N atom from tetrazolyl ring, in which each tza is coordinated in a tridentate chelating bridging coordination mode. The thermal decomposition mechanism of the title complex was studied by DSC and TG-DTG techniques. Under nitrogen atmosphere at a heating rate of 10 K·min-1, the thermal decomposition of the complex contains one main exothermic process between 191.7 and 243.8 ℃ in the DSC curve. Its combustion heat was mensurated by oxygen bomb calorimetry. The non-isothermal kinetics parameters were calculated by the Kissinger's method and Ozawa-Doyle's method, respectively. The sensitivity properties of K2(tza)2(H2O) were also determined with standard methods, which was very sensitive to flame.     

Cocrystallization of energetic Mn(II) complex with nitrogen-rich ligand SCZ and oxygen-rich ligand TNR

Based on the advantages of energetic complexes and cocrystallization, a novel energetic complex cocrystal [Mn(SCZ)₃](TNR) (H₂O)?·?[Mn(SCZ)₂(H₂O)(TNR)](H₂O) (SCZ: semicarbazide, TNR: 2,4,6-trinitroresorcinol) was synthesized through a one-step reaction. This cocrystal contains equal units of [Mn(SCZ)₂(H₂O)(TNR)](H₂O) and [Mn(SCZ)₃]TNR(H₂O). The molecules of the two units arrange mutually crosswise in the cocrystal and the benzene rings of TNR can form one-dimensional self-assemblies through π-π stacking. The thermal decomposition of the cocrystal is complicated with one endothermic process and three exothermic processes in the DSC curve. The complex [Mn(SCZ)₂(H₂O)(TNR)]?·?3(H₂O) was synthesized and the temperature of the major exothermic peak of the cocrystal is higher than observed for this complex.