新型绿色起爆药硝氨基四唑钙(Ⅱ)五水化合物的晶体结构
北京理工大学爆炸科学与技术国家重点实验室, 北京 100081
收稿日期：2013-05-06；修回日期：2013-06-05
基金项目：爆炸科学与技术国家重点实验室基金(No.QNKT12-02和ZDKT10-01b)，应用物理化学重点实验室基金(No.9140C3703051105和9140C370303120C37142)
摘要：用缓慢蒸发法制备了新型绿色起爆药硝氨基四唑钙(Ⅱ)五水化合物[Ca(NATZ)(H2O)5]的单晶。用X射线衍射仪表征其单晶结构。该晶体属三斜晶系，空间群为P1，晶胞参数为: a=0.64803(13) nm，b=0.74328(16) nm，c=1.0348(2) nm，α=74.482(8)°，β=72.487(9)°，γ=74.755(9)°，V=0.44888(16) nm3，Z=4，Dc=2.050 g·cm-3。根据Ca(NATZ)(H2O)5的结构特征研究了它的分解机理。运用Gaussian 03程序，用HF6-311G和B3LYP6-311G方法对Ca(NATZ)(H2O)5进行了全优化几何构型和轨道能量分析。所得结果与前人实验研究结果一致:热稳定性差，且热分解失重主要为两个阶段。
关键词：物理化学
起爆药
五水合硝氨基四唑钙(Ⅱ)
晶体结构
理论研究
Crystal Structure of a Novel Green Initiating Explosive Calcium Nitriminotetrazolate Pentahydrate
TONG Wen-chao
,
WANG Shi-wei
,
WU Bi-dong
,
YANG Li
,
ZHANG Tong-lai
State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081, China
Abstract: The single crystal of calcium nitriminotetrazolate pentahydrate [Ca(NATZ)(H2O)5], a novel green initiating explosive was prepared by slow evaporation method. Its structure was characterized by a X-ray diffractometer. The crystal is triclinic, space group P1 with crystal parameters of a=0.64803(13)nm, b=0.74328(16) nm, c=1.0348(2) nm, α=74.482(8)°, β=72.487(9)°, γ=74.755(9)°, V=0.44888(16) nm3, Z=4, Dc=2.050 g·cm-3. On the basis of the structure characteristics of Ca(NATZ)(H2O)5, its decomposition mechanism was studied. The full optimized geometry and orbital energy analysis of Ca(NATZ)(H2O)5 were performed with the HF6-311G and B3LYP-6-311G methods using the Gaussian 03 program. Its thermal stability was studied. Rusults show there are two steps in its thermal decomposition which is agreed with expriments.
Key words:
physical chemistry initiating explosive calcium nitriminotetrazolate pentahydrate crystal structure theoretical investigation
1 引言
随着起爆药行业的不断发展，近年来推出了不少新型的起爆药品种，如叠氮肼镍(NHN)、高氯酸三碳酰肼合镉(GTG)、高氯酸三碳酰肼合锌(GTX)等，已被广泛应用于民用爆破器材的工业系列雷管中。目前，环保绿色起爆药仍是国内外学者不断研究的方向[1-3]。
Zhilin等先后报道了两种高能含能化合物高氯酸·四氨·双(5-硝基四唑)合钴(Ⅲ)[4]和高氯酸·四氨·双(1-甲基-5-氨基四唑)合钴(Ⅲ)[5]。Klapötke等合成了多种双四唑胺类和铜的配合物[6-7]，其于2009年报道合成了新型含能配合物——五水合硝氨基四唑钙(Ⅱ)[8]，经烘干后去掉结晶水，对其感度和起爆性能做了测试，0.5 g无水硝氨基四唑钙(Ⅱ)可成功起爆2.0 g六硝基茋(HNS)，认为该药是一种新型的可代替氮化铅的绿色起爆药，适合大规模生产，最具应用价值。
虽然Klapötke等对硝氨基四唑钙(Ⅱ)的合成方法和晶体结构以及热力学性质等进行了介绍，但是未对其晶体结构进行详细描述与分析。本研究合成了五水合硝氨基四唑钙(Ⅱ)(Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$)，制备了五水合硝氨基四唑钙的单晶，详细报道了它的晶体结构数据，并根据其结构特征研究了Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$的分解机理，同时运用量化计算的方法分析了它的稳定性，为该化合物的进一步应用提供基础理论。
2 实验部分
2.1 试剂
氢氧化钙为市售分析纯；5-硝氨基四唑按照文献方法自制[9]。
2.2 $\mathbf{Ca}$($\mathbf{NATZ}$)($\mathbf{H}_{\boldsymbol{2}}\mathbf{O}$)$_{\boldsymbol{5}}$的制备
称量1.30 g(0.01 mol)5-硝氨基四唑溶于10 mL蒸馏水中作为底液加入反应器。将0.74 g(0.01 mol)氢氧化钙逐滴分批加入到5-硝氨基四唑的溶液中。在恒温70 ℃的油浴条件下搅拌反应1 h。静置、过滤，得到的白色物质在热水中重结晶，过滤，乙醇洗涤得产物。
2.3 单晶的培养与结构测定
将母液置于80 mL烧杯中静置，缓慢蒸发溶液，得到无色Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$晶体。
选取尺寸为0.40 mm×0.40 mm×0.40 mm的单晶，置于Rigaku AFC-10 /Saturn 724$^{+}\text{CCD}$面探X射线单晶衍射仪上，在103(2) K下，用Mo $\text{K}_{α}$射线($λ$=0.071073 nm)，采用Multi-scan方式，$θ$为2.90°~30.02°范围内进行扫描，共收集了4870个衍射点，其中独立衍射点2541个，可观察衍射点2258个。解析之前对所有的衍射点进行$L_{\text{p}}$因子和多次扫描吸收校正。主要原子坐标用SHELXS-97 (Sheldrick，1997)程序由直接法求得，其它非氢原子坐标由差值Fourier合成法得到。用SHELXL-97(Sheldrick，1997)程序选用61个各向异性参数，由全矩阵最小二乘法对非氢原子进行结构优化。所有氢原子均为理论加氢，利用几何参数对氢原子坐标进行结构优化。分子结构用SHELXS-97程序[10]由直接法求得，在SHELXL-97程序[11]中用基于$\text{F}^{2}$的全矩阵最小二乘法进行精修。
2.4 量子化学计算
选取Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$分子作为初始模型, 运用Gaussian 03程序，用HF/6-311G，B3LYP/6-311G两种方法对所选分子体系进行几何全优化和频率计算。计算中所有收敛精度均取程序设定的缺省值。
3 结果与讨论
3.1 $\mathbf{Ca}$($\mathbf{NATZ}$)($\mathbf{H}_{\boldsymbol{2}}\mathbf{O}$)$_{\boldsymbol{5}}$的晶体结构描述
Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$的主要晶体学数据列于表 1。Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$的分子结构及堆积图分别见图 1和图 2。主要键长、键角与扭转角数据列于表 2~表 4。
表 1(Tab. 1)
表 1 Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$的晶体学参数和结构测定参数
Tab. 1 Crystallographic paramerers for Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$
| parameter |
values |
| empirical formula |
$\text{CH}_{10}\text{CaN}_{6}\text{O}_{7}$ |
| crystal description |
block |
| formula weight |
258.23 |
| crystal color |
colorless |
| $T$/K |
103(2) |
| $D_{c}$/g·$\text{m}^{-3}$ |
1.910 |
| crystal system |
Triclinic |
| θ/(°) |
2.90~30.02 |
| space group |
$P$-1 |
| $h$, $k$, $l$ |
-9~9, -8~10, -14~14 |
| $a$/nm |
0.64803(13) |
| reflections collections |
4870 |
| $b$/nm |
0.74328(16) |
| independent reflection ($R_{\text{int}}$) |
2541($R_{\text{int}}$=0.0174) |
| $c$/nm |
1.0348(2) |
| $S$ |
0.999 |
| α/(°) |
74.482(8) |
| $R_{1}$, $wR_{2}$[$I$＞2$\text{σ}$($I$)]$^{1)}$ |
$R_{1}$=0.0336, $wR_{2}$=0.0780 |
| $β$/(°) |
72.487(9) |
| $R_{1}$, $wR_{2}$(all data)$^{1)}$ |
$R_{1}$=0.0378, $wR_{2}$=0.0807 |
| γ/(°) |
74.755(9) |
| $\text{Δ}ρ_{\text{max}}$, $\text{Δ}ρ_{\text{min}}$/(e·Å$^{-3}$) |
0.827, -0.533 |
| $V$/$\text{nm}^{3}$ |
0.44889(16) |
| $μ$(Mo $\text{K}_{\mathsf{α}}$)/$\text{mm}^{-1}$ |
0.736 |
| $Z$ |
2 |
| $F$(000) |
268.0 |
| Note: 1)$w$＝1/[$σ^{2}$($F_{\text{o}}^{2}$)+(0.0429$p$)$^{2}$+0.3776$p$], $p$＝($F_{\text{o}}^{2}$+2$F_{\text{c}}^{2}$)/3 |
|
表 1 Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$的晶体学参数和结构测定参数
Tab.1 Crystallographic paramerers for Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$ |
表 2(Tab. 2)
表 2 Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$的主要键长
Tab. 2 Selected bond lengths for Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$
| bond |
lengths/Å |
bond |
lengths/Å |
bond |
lengths/Å |
bond |
lengths/Å |
| Ca(1)—O(6) |
2.3676(12) |
Ca(1)—Ca(1A) |
4.3197(10) |
O(5)—H(5A) |
0.8517 |
N(2)—N(3) |
1.3136(19) |
| Ca(1)—O(5) |
2.3983(13) |
O(1)—N(6) |
1.2761(17) |
O(5)—H(5B) |
0.8183 |
N(3)—N(4) |
1.3389(18) |
| Ca(1)—O(7) |
2.3989(13) |
O(2)—N(6) |
1.2887(17) |
O(6)—H(6A) |
0.8364 |
N(4)—C(1) |
1.340(2) |
| Ca(1)—O(1) |
2.4113(13) |
O(3)—Ca(1) |
2.6421(13) |
O(6)—H(6B) |
0.9073 |
N(5)—N(6) |
1.2767(19) |
| Ca(1)—N(1) |
2.4892(14) |
O(3)—H(3A) |
0.8813 |
O(7)—H(7A) |
0.8728 |
N(5)—C(1) |
1.3901(19) |
| Ca(1)—O(4) |
2.5128(12) |
O(3)—H(3B) |
0.8513 |
O(7)—H(7B) |
0.9739 |
|
|
| Ca(1)—O(3) |
2.5736(13) |
O(4)—H(4A) |
0.8538 |
N(1)—C(1) |
1.337(2) |
|
|
| Ca(1)—O3A) |
2.6421(13) |
O(4)—H(4B) |
0.8655 |
N(1)—N(2) |
1.3492(19) |
|
|
|
表 2 Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$的主要键长
Tab.2 Selected bond lengths for Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$ |
表 3(Tab. 3)
表 3 Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$的主要键角
Tab. 3 Selected bond angle for Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$
| bond |
angle/(°) |
bond |
angle/(°) |
bond |
angle/(°) |
bond |
angle/(°) |
| O(6)—Ca(1)—O(5) |
83.74(4) |
N(1)—Ca(1)—Ca(1) |
137.55(3) |
N(6)—O(1)—Ca(1) |
140.69(10) |
Ca(1)—O(7)—H(7B) |
118.1 |
| O(6)—Ca(1)—O(7) |
87.72(4) |
O(4)—Ca(1)—Ca(1) |
104.48(3) |
Ca(1)—O(3)—Ca(1) |
111.82(4) |
H(7A)—O(7)—H(7B) |
110.4 |
| O(5)—Ca(1)—O(7) |
72.89(4) |
O(7)—Ca(1)—O(3) |
74.07(4) |
Ca(1)—O(3)—H(3A) |
104.7 |
C(1)—N(1)—N(2) |
104.26(13) |
| O(6)—Ca(1)—O(1) |
99.76(4) |
O(1)—Ca(1)—O(3) |
78.03(4) |
Ca(1)—O(3)—H(3A) |
111.2 |
C(1)—N(1)—Ca(1) |
129.71(10) |
| O(5)—Ca(1)—O(1) |
142.62(4) |
N(1)—Ca(1)—O(3) |
136.64(4) |
Ca(1)—O(3)—H(3B) |
107.8 |
N(2)—N(1)—Ca(1) |
125.87(10) |
| O(7)—Ca(1)—O(1) |
144.01(4) |
O(4)—Ca(1)—O(3) |
71.92(4) |
Ca(1)—O(3)—H(3B) |
113.4 |
N(3)—N(2)—N(1) |
109.39(13) |
| O(6)—Ca(1)—N(1) |
73.28(4) |
O(7)—Ca(1)—O(3) |
77.74(4) |
H(3A)—O(3)—H(3B) |
107.4 |
N(2)—N(3)—N(4) |
110.00(13) |
| O(5)—Ca(1)—N(1) |
78.55(4) |
O(1)—Ca(1)—O(3) |
71.00(4) |
Ca(1)—O(4)—H(4A) |
107.4 |
N(3)—N(4)—C(1) |
104.31(13) |
| O(7)—Ca(1)—N(1) |
147.20(4) |
N(1)—Ca(1)—O(3) |
119.88(4) |
Ca(1)—O(4)—H(4B) |
116.2 |
N(6)—N(5)—C(1) |
119.47(13) |
| O(1)—Ca(1)—N(1) |
67.24(4) |
O(4)—Ca(1)—O(3) |
135.31(4) |
H(4A)—O(4)—H(4B) |
107.0 |
O(1)—N(6)—N(5) |
126.15(13) |
| O(6)—Ca(1)—O(4) |
147.85(4) |
O(3)—Ca(1)—O(3) |
68.18(4) |
Ca(1)—O(5)—H(5A) |
116.7 |
O(1)—N(6)—O(2) |
117.24(13) |
| O(5)—Ca(1)—O(4) |
76.53(4) |
O(6)—Ca(1)—Ca(1) |
106.42(3) |
Ca(1)—O(5)—H(5B) |
120.4 |
N(5)—N(6)—O(2) |
116.60(13) |
| O(7)—Ca(1)—O(4) |
109.84(4) |
O(5)—Ca(1)—Ca(1) |
143.81(3) |
H(5A)—O(5)—H(5B) |
112.5 |
N(1)—C(1)—N(4) |
112.05(13) |
| O(1)—Ca(1)—O(4) |
81.93(4) |
O(7)—Ca(1)—Ca(1) |
72.94(3) |
Ca(1)—O(6)—H(6A) |
118.0 |
N(1)—C(1)—N(5) |
131.78(14) |
| N(1)—Ca(1)—O(4) |
78.05(4) |
O(1)—Ca(1)—Ca(1) |
71.18(3) |
Ca(1)—O(6)—H(6B) |
119.4 |
N(4)—C(1)—N(5) |
116.17(14) |
| O(6)—Ca(1)—O(3) |
140.09(4) |
O(3)—Ca(1)—Ca(1) |
34.60(3) |
H(6A)—O(6)—H(6B) |
108.1 |
|
|
| O(5)—Ca(1)—O(3) |
122.11(4) |
O(3)—Ca(1)—Ca(1) |
33.58(3) |
Ca(1)—O(7)—H(7A) |
113.7 |
|
|
|
表 3 Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$的主要键角
Tab.3 Selected bond angle for Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$ |
表 4(Tab. 4)
表 4 Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$分子中键的扭转角
Tab. 4 Torsion angles for Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$
| bond |
angle/(°) |
bond |
angle/(°) |
bond |
angle/(°) |
| O(6)—Ca(1)—O(1)—N(6) |
-92.83(15) |
N(1)—Ca(1)—O(3)—Ca(1) |
110.95(6) |
O(5)—Ca(1)—N(1)—N(2) |
25.37(11) |
| O(5)—Ca(1)—O(1)—N(6) |
-0.37(18) |
O(4)—Ca(1)—O(3)—Ca(1) |
159.43(5) |
O(7)—Ca(1)—N(1)—N(2) |
-4.34(16) |
| O(7)—Ca(1)—O(1)—N(6) |
167.48(13) |
O(3)—Ca(1)—O(3)—Ca(1) |
0.0 |
O(1)—Ca(1)—N(1)—N(2) |
-170.00(12) |
| N(1)—Ca(1)—O(1)—N(6) |
-25.71(14) |
O(6)—Ca(1)—N(1)—C(1) |
123.90(13) |
O(4)—Ca(1)—N(1)—N(2) |
103.83(12) |
| O(4)—Ca(1)—O(1)—N(6) |
54.66(15) |
O(5)—Ca(1)—N(1)—C(1) |
-149.27(13) |
O(3)—Ca(1)—N(1)—N(2) |
150.50(10) |
| O(3)—Ca(1)—O(1)—N(6) |
127.78(15) |
O(7)—Ca(1)—N(1)—C(1) |
-178.97(11) |
O(3)—Ca(1)—N(1)—N(2) |
-120.41(11) |
| O(3)—Ca(1)—O(1)—N(6) |
-161.42(15) |
O(1)—Ca(1)—N(1)—C(1) |
15.36(12) |
Ca(1)—Ca(1)—N(1)—N(2) |
-157.71(9) |
| Ca(1)—Ca(1)—O(1)—N(6) |
163.02(15) |
O(4)—Ca(1)—N(1)—C(1) |
-70.81(13) |
C(1)—N(1)—N(2)—N(3) |
0.09(16) |
| O(6)—Ca(1)—O(3)—Ca(1) |
-16.83(8) |
O(3)—Ca(1)—N(1)—C(1) |
-24.13(15) |
Ca(1)—N(1)—N(2)—N(3) |
-175.66(9) |
| O(5)—Ca(1)—O(3)—Ca(1) |
-140.18(5) |
O(3)—Ca(1)—N(1)—C(1) |
64.95(14) |
N(1)—N(2)—N(3)—N(4) |
0.16(16) |
| O(7)—Ca(1)—O(3)—Ca(1) |
-82.90(5) |
Ca(1)—Ca(1)—N(1)—C(1) |
27.65(15) |
N(2)—N(3)—N(4)—C(1) |
-0.33(16) |
| O(1)—Ca(1)—O(3)—Ca(1) |
74.12(5) |
O(6)—Ca(1)—N(1)—N(2) |
-61.46(11) |
Ca(1)—O(1)—N(6)—N(5) |
21.6(2) |
| Ca(1)—O(1)—N(6)—O(2) |
-159.61(11) |
C(1)—N(5)—N(6)—O(2) |
-174.68(12) |
Ca(1)—N(1)—C(1)—N(4) |
175.21(9) |
| C(1)—N(5)—N(6)—O(1) |
4.1(2) |
N(2)—N(1)—C(1)—N(4) |
-0.30(16) |
N(2)—N(1)—C(1)—N(5) |
178.85(15) |
| N(6)—N(5)—C(1)—N(1) |
-10.3(2) |
N(6)—N(5)—C(1)—N(4) |
168.80(13) |
Ca(1)—N(1)—C(1)—N(5) |
-5.6(2) |
| N(3)—N(4)—C(1)—N(1) |
0.40(16) |
N(3)—N(4)—C(1)—N(5) |
-178.90(12) |
|
|
|
表 4 Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$分子中键的扭转角
Tab.4 Torsion angles for Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$ |
3.2 晶体结构分析与讨论
(1) 由图 1可以看出，每个最小不对称结构单元中含有1个中心$\text{Ca}^{2+}$，1个NATZ分子和6个与$\text{Ca}^{2+}$配位的水分子。$\text{Ca}^{2+}$分别与NATZ分子中四唑环上1位上的N、NATZ分子中硝氨基上的一个O原子以及6个$\text{H}_{2}\text{O}$分子中的O原子形成八配位十二面体结构。同时由于$\text{Ca}^{2+}$的3$d^{10}$构型不会发生$d$-$d$跃迁，这与所得晶体为无色的事实相符。
(2) $\text{NATZ}^{-}$阴离子中O(2)—N(6)[1.2887(17)]，N(5)—C(1)[1.3901(19)]和N(2)—N(3)[1.3136(19)]的键长比5-NATZ分子中O(2)—N(6)(1.2344)，N(5)—C(1)(1.3405)和N(2)—N(3)(1.2778)的键长稍长, 而N(3)—N(4)[1.3389(18)]和N(5)—N(6)[1.2767(19)]的键长要比5-NATZ分子中N(4)—N(3)(1.3521)和N(5)—N(6)(1.3626)的键长要短，这是由于5-硝氨基四唑分子中存在$\text{π}$电子的离域现象。
(3) 图 2为配合物晶体的晶胞堆积图，从图中可以看出，分子中配位键和分子间氢键的共同作用使得Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$以高聚形态存在，形成较稳定的三维网状结构。
(4) 从Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$的分子结构图(图 1)可以看出，有4分子水中的O与$\text{Ca}^{2+}$为$μ$1配位，1分子水中的O与$\text{Ca}^{2+}$为$μ$2配位，使得这一分子的水与$\text{Ca}^{2+}$的配位更加牢固。另外，Ca(1)—O(1)[2.4113(13)]和Ca(1)—N(1)[2.4892(14)]的键长相对于Ca(1)—O(3)[2.5736(13)]的键长要短，键合较强，说明$\text{Ca}^{2+}$与$\text{NATZ}^{-}$阴离子中的N(1)和O(1)形成的六元环更加牢固。由此可以推断Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$的热分解失重过程为，第一阶段先分解失去四分子的水，第二阶段再失去一分子的水，这与文献[8]报道的实验结果是一致的。
3.3 分子总能量及前线轨道能量分析
运用HF和B3LYP两种方法对Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$分子进行了几何全优化和频率计算。两种计算方法对Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$进行几何优化所得的键长、键角与测定结果比较，B3LYP的计算结果与实验值非常接近，表明计算结果可信，而HF与实验值存在较大偏差(大于5%)，计算结果不可靠。根据B3LYP方法计算结果，该体系共有492个分子轨道(MO)，其中134个为占据轨道。由计算得到的分子总能量、前线轨道能量($E_{\text{HOMO}}$，$E_{\text{LUMO}}$)和能差分别为-3153.70051731, -0.24522，-0.07742和0.16780Hartree。HOMO轨道和LUMO轨道如图 3所示。Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$的最高占据轨道(HOMO)主要由5-NATZ分子中原子的2$p_{\text{z}}$轨道构成，最低空轨道(LUMO)主要分布在5-NATZ的除N(3)外的原子的2$p_{\text{z}}$轨道，且由前线轨道能级差$\text{Δ}E_{\text{L}-\text{H}}$(0.16780 Hartree)较小可知，Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$分子的配位稳定性较差，因此该分子在72 ℃开始失水，150 ℃脱去5分子水，得到Ca(NATZ)[8]。
4 结论
合成了新型绿色起爆药五水合硝氨基四唑钙(Ⅱ)[Ca(NATZ)($\text{H}_{2}\text{O}$)$_{5}$]，制备了五水合硝氨基四唑钙的单晶，详细报道了它的晶体结构数据，该晶体属三斜晶系，空间群为$P\bar{1}$，晶胞参数为：$a$=0.64803(13) nm，$b$=0.74328(16) nm，$c$=1.0348(2) nm，$α$=74.482(8)°，$β$=72.487(9)°，$γ$=74.755(9)°，$V$=0.44888(16) $\text{nm}^{3}$，$Z$=4，$D_{c}$=2.050 g·$\text{cm}^{-3}$。运用量化计算对其进行了结构优化分析，所得结果与前人实验研究结果一致：热稳定性差，且热功率失重元要为两个阶段。
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图文摘要
The structure of calcium nitriminotetrazolate pentahydrate [Ca(NATZ)(H2O)5] was determined by X-ray single crystal diffraction. Theoretical investigation was carried out by HF/6-311g and B3LYP/6-311g methods. This coordination compound has lower thermal stability.
