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Dec 15, 2015 - (CdCl4)Cl2(ClO4)4}n (12), when HATr = 3-hydrazino-4-amino- ...... FS(N)c. 72. 96. 24. 80. 36. 72. 120. 6. 12. 28. 84. aDecomposition ...
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Structural Diversity and Properties of M(II) Coordination Compounds Constructed by 3‑Hydrazino-4-amino-1,2,4-triazole Dihydrochloride as Starting Material Caixia Xu,† Jianguo Zhang,*,† Xin Yin,† and Zhenxuan Cheng‡ †

State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081, P. R. China China North Industries Group Corporation, Beijing 100821, P. R. China

‡

S Supporting Information *

ABSTRACT: Twelve metal coordination compounds with two triazole derivatives, namely, {[Mn(HATr)2](ClO4)2}n (1), [Mn(HATr)3]Cl(ClO4) (2), [Co3(ATr)6(H2O)6](ClO4)6·4.5H2O (3), [Co(HATr)3]Cl(ClO4) (4), [Co2Cl2(HATr)2(H2O)2(CH3OH)2]Cl2·2H2O (5), [Ni3(ATr)6(H2O)6](ClO4)6·4.5H2O (6), [Ni(HATr)3]Cl(ClO4) (7), [Ni2Cl2(HATr)2(H2O)4](ClO4)2·4H2O (8), [Ni2(HATr)2(H2O)6](ClO4)4·2H2O (9), {[Zn(HATr)2](ClO4)2}n (10), [Zn(HATr)3]Cl(ClO4) (11), and {[Cd4(HATr)8](CdCl4)Cl2(ClO4)4}n (12), when HATr = 3-hydrazino-4-amino1,2,4-triazole and ATr = 4-amino-1,2,4-triazole, were prepared under diverse conditions and structurally characterized. Compounds 1, 10 and 12 exhibit one-dimensional zigzag chain structures; 2, 4, 7, and 11 possess mononuclear structures; 3 and 6 display trinuclear structures, while 5, 8, and 9 feature binuclear structures. Hydrogen bonds link these compounds into three-dimensional structures. The thermal stability and energetic properties also were determined.

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INTRODUCTION Energetic materials are used for a variety of military purposes and civilian applications, and seeking new energetic materials has always been a major goal for chemists.1 In addition to energetic cocrystals2 and energetic salts,3 another powerful and facile route to new energetic materials is through the formation of energetic metal−organic frameworks.4 In the crystal engineering of metal−organic frameworks, in addition to coordination bonds, hydrogen bonds, as another type of noncovalent contact, offer the most predominant organizational tool in the construction of molecular materials,5 and hydrogen bonding interactions have attracted increasing interest due to their capabilities in controlling molecular assemblies during crystallization and thereby engineering the crystal structures and the physical properties of the resulting energetic materials.6 However, the self-assembly of metal−organic complexes is mainly influenced by several factors such as central metal ions, organic ligands, counterions, metal−ligand ratio, and so on. Besides the various factors, the synthetic method also is a very important consideration. Compared with the traditional synthetic methods, hydro(solvo)thermal reactions might give more chance for unexpected in situ ligand synthesis reactions; for example, the in situ generated new triazole ligand can be achieved by the transformation of the triazole derivative in the process of hydrothermal reaction. Su and co-workers discovered that reaction of Zn(II) salts and 3-amino-1,2,4© XXXX American Chemical Society

triazole-5-carboxylic acid under solvothermal condition can give a three-dimensional (3D) framework displaying open-ended, hollow nanotubular channels, [ZnF(AmTAZ)] solvents (AmTAZ = 3-amino-1,2,4-triazole).7 Solvothermal reaction of CuI and 4-amino-3, 5-diethyl-1,2,4-triazole also can afford a 3D non-interpenetrated framework, [CuI(dtz)]n (dtz = 3, 5diethyl-1,2,4-triazole).8 Both new ligands are derived from the elimination of the carboxyl group and amino group of starting material ligands, respectively. As a triazole derivative, 3hydrazino-4-amino-1,2,4-triazole (HATr) was first reported by Ilyushin et al. in 1993;9 they deemed that HATr is a N,Nbidentate ligand with N1 and N2 atoms of the triazole ring incorporated coordination. Subsequently, they further studied the laser initiation of transition metal perchlorate complexes with HATr ligands.10 However, there are few reports available concerning the structures of coordination compounds of HATr ligands. Previously, we reported several coordination compounds with different anions.11 To further investigate the influences of the reaction system on the structures of coordination compounds, in this work, using both solvothermal and conventional synthetic methods, a series of 12 transition metal coordination compounds were synthesized: {[Mn(HATr) 2 ](ClO 4 ) 2 } n (1), [Mn(HATr) 3 ]Cl(ClO 4 ) (2), Received: October 22, 2015

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DOI: 10.1021/acs.inorgchem.5b02434 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry

Synthesis of [Co3(ATr)6(H2O)6](ClO4)6·4.5H2O (3). Compound 3 was prepared according to a procedure similar to that of 1, except Co(ClO4)2·6H2O (0.366 g, 1 mmol) was used in place of Mn(ClO4)2· 6H2O. However, the clear bright orange liquid was obtained first, and crystals were obtained by evaporation after several days. The yield was 15% based on Co. Anal. Calcd for C12H45Cl6Co3N24O34.50 (%): C, 9.82; H, 3.09; N, 22.91. Found: C, 9.85; H, 3.12; N, 22.85. IR (KBr, cm−1): 3342, 3130, 1626, 1546, 1097, 885, 692, 623. Synthesis of [Co(HATr)3]Cl(ClO4) (4). Compound 4 was prepared in the similar way as of 1 with Mn(ClO4)2·6H2O replaced by Co(ClO4)2· 6H2O (0.110 g, 0.3 mmol). Large quantities of orange block crystals were obtained in a yield of 73% based on Co. Anal. Calcd for C6H18Cl2CoN18O4 (%): C, 13.44; H, 3.38; N, 47.02. Found: C, 13.42; H, 3.32; N, 47.10. IR (KBr, cm−1): 3322, 3224, 1658, 1544, 1097, 853, 724, 624. Synthesis of [Co2Cl2(HATr)2(H2O)2(CH3OH)2]Cl2·2H2O (5). Sodium hydrogen carbonate was slowly added to an aqueous solution (5 mL) containing HATr·2HCl (0.187 g, 1 mmol) to adjust the pH value to ca. 6, and the water was evaporated under vacuum. The powder was then dissolved in 10 mL of absolute CH3OH, and the inorganic salt was removed by filtration. A solution of Co(ClO4)2·6H2O (0.183 g, 0.5 mmol) in 5 mL of H2O was added dropwise in the above filtrate, and the mixture was stirred at 50 °C for 1 h and was subsequently filtered. Rosy block crystals were formed a few days later. The yield was 51% based on Co. Anal. Calcd for C6H28Cl4Co2N12O6 (%): C, 11.55; H, 4.52; N, 26.93. Found: C, 11.52; H, 4.55; N, 26.91. IR (KBr, cm−1): 3531, 3415, 3189, 1631, 1082, 941, 802, 627. Synthesis of [Ni3(ATr)6(H2O)6](ClO4)6·4.5H2O (6). Compound 6 was prepared according to a procedure similar to that of 3, except Ni(ClO4)2·6H2O (0.366 g, 1 mmol) was used in place of Co(ClO4)2· 6H 2 O. The yield was 10% based on Ni. Anal. Calcd for C12H45Cl6N24Ni3O34.50 (%): C, 9.83; H, 3.09; N, 22.92. Found: C, 9.76; H, 3.06; N, 22.98. IR (KBr, cm−1): 3350, 3133, 1628, 1546, 1100, 879, 691, 622. Synthesis of [Ni(HATr)3]Cl(ClO4) (7). Compound 7 was prepared in the similar way as of 1 with Mn(ClO4)2·6H2O replaced by Ni(ClO4)2· 6H2O (0.110 g, 0.3 mmol). The yield was 20% based on Ni. Anal. Calcd for C6H18Cl2N18NiO4 (%): C, 13.45; H, 3.39; N, 47.04. Found: C, 13.42; H, 3.29; N, 47.01. IR (KBr, cm−1): 3322, 3218, 1656, 1562, 1097, 850, 724, 623. Synthesis of [Ni2Cl2(HATr)2(H2O)4](ClO4)2·4H2O (8). Compound 8 was prepared according to a procedure similar to that of 5, except Ni(ClO4)2·6H2O (0.183 g, 0.5 mmol) was used in place of Co(ClO4)2·6H2O. The yield was 17% based on Ni. Anal. Calcd for C4H30Cl4N12Ni2O16 (%): C, 6.31; H, 3.97; N, 22.07. Found: C, 6.35; H, 3.92; N, 22.11. IR (KBr, cm−1): 3300, 3220, 1658, 1563, 1097, 849, 724, 624. Synthesis of [Ni2(HATr)2(H2O)6](ClO4)4·2H2O (9). Compound 9 was prepared according to a procedure similar to that of 6, except the temperature was 85 °C. Blue block crystals were formed a few days later. The yield was 18% based on Ni. Anal. Calcd for C4H28Cl4N12Ni2O24 (%): C, 5.41; H, 3.18; N, 18.94. Found: C, 5.45; H, 3.22; N, 18.96. IR (KBr, cm−1): 3321, 3163, 1662, 1574, 1106, 849, 725, 624. Synthesis of {[Zn(HATr)2](ClO4)2}n (10). Compound 10 was prepared according to a procedure similar to that of 1, except Zn(ClO4)2·6H2O (0.372 g, 1 mmol) was used in place of Mn(ClO4)2· 6H2 O. The yield was 25% based on Zn. Anal. Calcd for C4H12ZnCl2N12O8 (%): C, 9.75; H, 2.46; N, 34.13. Found: C, 9.73; H, 2.43; N, 34.18. IR (KBr, cm−1): 3336, 3152, 1660, 1573, 1075, 844, 726, 619. Synthesis of [Zn(HATr)3]Cl(ClO4) (11). Compound 11 was prepared in the similar way as of 1 with Mn(ClO4)2·6H2O replaced by Zn(ClO4)2·6H2O (0.112 g, 0.3 mmol). The yield was 20% based on Zn. Anal. Calcd for C6H18ZnCl2N18O4 (%): C, 13.28; H, 3.34; N, 46.46. Found: C, 13.22; H, 3.29; N, 46.41. IR (KBr, cm−1): 3327, 3229, 1657, 1569, 1099, 856, 727,625. Synthesis of {[Cd4(HATr)8](CdCl4)Cl2(ClO4)4}n (12). Compound 12 was prepared according to a procedure similar to that of 1, except Cd(ClO4)2·6H2O (0.210 g, 0.5 mmol) was used in place of

[Co3(ATr)6(H2O)6](ClO4)6·4.5H2O (3), [Co(HATr)3]Cl(ClO4) (4), [Co2Cl2(HATr)2(H2O)2(CH3OH)2]Cl2·2H2O (5), [Ni3(ATr)6(H2O)6](ClO4)6·4.5H2O (6), [Ni(HATr)3]Cl(ClO4) (7), [Ni2Cl2(HATr)2(H2O)4](ClO4)2·4H2O (8), [Ni 2(HATr)2(H2O) 6](ClO 4) 4·2H 2O (9), {[Zn(HATr)2](ClO 4 ) 2 } n (10), [Zn(HATr) 3 ]Cl(ClO 4 ) (11), and {[Cd4(HATr)8](CdCl4)Cl2(ClO4)4}n (12). Dehydrazination occurs under solvothermal condition (100 °C), and HATr ligands transform to 4-amino-1,2,4-triazole (ATr) ligands coordinating to Co(II) and Ni(II) cations in compounds 3 and 6, respectively. As shown in Scheme 1, HATr can adopt Scheme 1. Coordination Modes of HATr (a, b) and ATr (c)

two kinds of coordination modes either tridentate bridgingchelating style or bidentate chelating fashion, while ATr can act as bidentate bridging ligand. In addition, the thermal stability and energetic properties like sensitivities toward impact and friction were also investigated.

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EXPREIMENTAL SECTION

Materials and Methods. The ligand 3-hydrazino-4-amino-1,2,4triazole itself was not stable in the air, so we directly used its dihydrochloride (HATr·2HCl) as starting material. HATr·2HCl was prepared according to previous literature.12 The ATr ligand in compounds 3 and 6 was derived from the dehydrazination of HATr in the solvothermal process. All other reactants were purchased commercially and used without further purification (Caution! Perchlorate compounds are dangerous and should be handled with care). Elemental analyses (C, H, N) were performed with a flash EA 1112 full automatic trace element analyzer. The IR spectra were recorded from KBr pellets in the range from 4000 to 400 cm−1 on a Nexus-470 FT-IR (Nicolet) spectrometer. Differential scanning calorimetry (DSC) measurements were performed on a CDR-4 (Shanghai Precision & Scientific Instrument Co., Ltd.), calibrated by standard pure indium and zinc at a heating rate of 5 °C min−1. The impact and friction sensitivities were performed on a BAM fall hammer BFH-10 and a BAM friction apparatus FSKM-10, respectively. Synthesis of {[Mn(HATr)2](ClO4)2}n (1). Sodium hydrogen carbonate was slowly added to a solution of HATr·2HCl (0.187 g, 1 mmol) in H2O (5 mL) to adjust the pH value to ca. 6, and the water was evaporated under vacuum. The powder was then dissolved in 10 mL of absolute CH3OH, and the inorganic salt was removed by filtration. A mixture of the above filtrate and Mn(ClO4)2·6H2O (0.362 g, 1 mmol) in 5 mL of H2O was placed in a Teflon reactor (20 mL) and heated at 100 °C for 24 h, and after it slowly cooled to room temperature at the rate of 5 °C·h−1, colorless needle crystals were obtained in a yield of 12% based on Mn. Anal. Calcd for C4H12Cl2MnN12O8 (%): C, 9.97; H, 2.51; N, 34.87. Found: C, 9.95; H, 2.53; N, 34.79. IR (KBr, cm−1): 3330, 3145, 1651, 1572, 1091, 840, 725, 627. Synthesis of [Mn(HATr)3]Cl(ClO4) (2). Compound 2 was prepared in the similar way as of 1 with Mn(ClO4)2·6H2O (0.109 g, 0.3 mmol). Colorless rod crystals were obtained, and the yield was 53% based on Mn. Anal. Calcd for C6H18Cl2MnN18O4 (%): C, 13.54; H, 3.41; N, 47.38. Found: C, 13.50; H, 3.43; N, 47.32. IR (KBr, cm−1): 3321, 3230, 1656, 1542, 1096, 858, 725, 623. B

DOI: 10.1021/acs.inorgchem.5b02434 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry Scheme 2. Construction of Coordination Compounds 1−12

Figure 1. (a) Coordination environment of Mn(II) in 1, thermal ellipsoids are drawn at the 30% probability level. (b) The 1D zigzag chain structure with the Mn atoms connected by the HATr ligands. The anions are omitted for clarity. Selected bond lengths (Å) and angles (deg): Mn1−N2 2.186(3), Mn1−N6 2.399(3), Mn1−N8 2.184(3), Mn1−N12 2.368(3), Mn1−N1A 2.220(3), Mn1−N7B 2.242(3), N2−Mn1−N8 168.46(10), N8−Mn1−N6 100.34(10), N1A#1−Mn1−N8 93.08(10), N8−Mn1−N12 73.18(10), N2−Mn1−N6 100.34(10), N1A#1−Mn1−N7B#2 93.44(11), N1A#1−Mn1−N2 95.60(11), N2−Mn1−N12 96.97(10), N1A#1−Mn1−N6 89.59(11), N7B#2−Mn1−N8 94.15(10), N1A#1−Mn1−N12 163.64(11), N7B#2−Mn1−N6 165.02(11), N7B#2−Mn1−N2 92.90(10), N7B#2−Mn1−N12 96.33(11), N12−Mn1−N6 84.34(11). Symmetry codes: No. 1 x, −y + 1/2, z − 1/2, No. 2 x, −y + 1/2, z + 1/2. 9.22; H, 2.29; N, 32.21. IR (KBr, cm−1): 3334, 3289, 1667, 1580, 1092, 834, 723, 623.

Mn(ClO4)2·6H2O. The yield was 43% based on Cd. Anal. Calcd for C16H48Cd5Cl10N48O16 (%): C, 9.21; H, 2.32; N, 32.24. Found: C, C

DOI: 10.1021/acs.inorgchem.5b02434 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry X-ray Crystallography. The crystallographic data were collected on a Bruker CCD area-detector diffractometer using graphitemonochromated Mo Kα radiation (λ = 0.710 73 Å) for 1, 2, 4−12, and on the same diffractometer equipped with Cu Kα radiation (λ = 1.541 78 Å) for 3 through multiscan mode. The structures were solved by directed methods and refined using full-matrix least-squares based on F2 with the programs SHELXS97 and SHELXL97.13,14 Further details of the structural analyses are summarized in Table S1. CCDC 1044965, 1044968, 1408568−1408577 contains the supplementary crystallographic data for this paper.

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RESULTS AND DISCUSSION Synthesis. Two synthetic methods were applied to achieve compounds 1−12. Compounds 1, 2, 4, 7, and 10−12 were prepared under solvothermal conditions; compounds 5 and 8 were performed in routine synthetic approach, whereas assemblies of compounds 3, 6, and 9 were obtained via solvothermal reaction combined with solvent evaporation (Scheme 2). Crystal Structures of (1) and (10). Compound 1 crystallizes in the monoclinic P2(1)/c space group, and compound 10 conforms to the space group C2/c, which possesses a similar structure to that of 1; only the crystal structure of 1 is described here in detail. The asymmetric unit contains one crystallographically unique Mn cation, two HATr ligands, and two ClO4− anions. The Mn cation adopts a distorted octahedron coordination environment in which the equatorial plane is completed by three nitrogen atoms (N2, N8, N7B) from three triazole rings and one nitrogen atom (N6) afforded by the hydrazino group, and the axial sites are occupied by two nitrogen atoms (N1A, N12) from two HATr molecules (Figure 1a). The Mn−N distances fall between 2.184(3) and 2.399(3) Å, in accordance with the reported values.15 The HATr ligands behave as bridges, forming a one-dimensional (1D) zigzag chain structure (Figure 1b) in which the Mn···Mn distance is 4.4273(9) Å. There are two kinds of hydrogen bonds of N− H···O, C−H···O between the complex unit [Mn(HATr)2]2+ and ClO4− anions. The shortest distances N···O and C···O are 2.876(5) and 3.057(5) Å, respectively. The hydrogen bonds link 1D chain structure into a 3D structure (Figure S1). Crystal Structures of (2), (4), (7), and (11). Compounds 2, 4, 7, and 11 are isomorphous, crystallize in the space group P3, and display mononuclear structures. Therefore, a full description of 2 is given as a representative example. As shown in Figure 2, the asymmetric unit contains one crystallographically independent Mn cation, one HATr ligand, one Cl− anion, and a half of one ClO4− anion. The central Mn cation, exhibiting a distorted octahedral geometry, is sixcoordinated by six nitrogen atoms from three HATr molecules. The Mn−N bond lengths are in the range of 2.1549(12)− 2.3680(13) Å, which are also comparable with the reported ones.16 The HATr ligands serve as bidentate chelating coordination modes via nitrogen atom (N2) from triazole ring and terminal nitrogen atom (N6) from the hydrazino group. Both Cl− and ClO4− anions are free, acting as counterions. The intermolecular hydrogen bonds formed between nitrogen atoms or carbon atoms from HATr ligands as hydrogen donors and Cl− anions, oxygen atoms from ClO4− anions, nitrogen atoms from another HATr molecule as acceptors, link the coordinated cations and counteranions into a stable 3D structure (Figure S2). Crystal Structures of (3) and (6). Compounds 3 and 6 were formed under solvothermal condition by dehydrazination of HATr, and the HATr ligands transformed to ATr ligands. The

Figure 2. Molecule structure of 2, thermal ellipsoids are drawn at the 30% probability level. Selected bond lengths (Å) and angles (deg): Mn1−N2 2.1549(12), Mn1−N6 2.3680(13), N2−Mn1−N2A#1 98.22(4), N2A#1−Mn1−N6 73.39(4), N6−Mn1−N6A#1 93.27(5), N2B#2−Mn1−N6 97.02(5), N2−Mn1−N6 163.54(4). Symmetry codes: No. 1 −y + 1, x − y, z, No. 2 −x + y + 1, −x + 1, z.

trinuclear compound 3 is isostructural with 6; both crystallize in the monoclinic system with C2/m space group, and the structure of 3 is described as an example. As shown in Figure 3a, The Co1 cation coordinates to three nitrogen atoms (N1, N5, and N9) from three separate ATr ligands and three oxygen atoms (O16, O17, and O18) from three aqua ligands to complete a distorted octahedral geometry. The Co2 cation also exists in a distorted octahedral geometry, being surrounded by six triazole nitrogen (N2, N6, N10, N2A, N6A, and N10A) atoms from six ATr ligands. All ATr ligands take a bidentate bridging coordination mode, and the aqua ligands act as a terminal monodentate coordination mode. The bond lengths of Co−O bond vary in the range of 2.037(10)−2.112(9) Å, and the Co−N bond distance is 2.103(13)−2.171(10) Å, which are in good agreement with those of reported studies.17 The complex unit of [Co3(ATr)6(H2O)6]6+ looks like a regular hexagon viewed along Co1−Co2−Co1A axis (Figure 3b). Three kinds of hydrogen bonds of O−H···O, N−H···O, and C−H···O are observed in 3 with the O···O, N···O, and C···O distances of 2.667(16)−3.176(6), 3.042(17)−3.19(2), and 3.06(3)−3.36(2) Å, respectively. The complex unit of [Co3(ATr)6(H2O)6]6+, ClO4− anions, and water molecules are connected together by the hydrogen bonding, resulting in a 3D structure (Figure S3). Crystal Structure of (5). Compound 5 crystallizes in the monoclinic P2(1)/n space group. As shown in Figure 4, each Co is six-coordinated to three nitrogen atoms from two HATr ligands, one Cl− anion, and two oxygen atoms from one aqua molecule and one methanol molecule to complete a distorted octahedral geometry. The centrosymmetric binuclear [Co2(HATr)2]4+ unit is composed of two Co cations bridged by four nitrogen atoms (N1, N2, N1A, and N2A) from two HATr ligands with a Co···Co distance of 4.0690(5) Å. The shortest intermolecular Co···Co distance is 7.1790(8) Å, and the adjacent binuclear units are connected by hydrogen bonding of N−H···Cl, O−H···Cl, and O−H···O, where the N···Cl, O···Cl, and O···O average distances are 3.334, 3.140, and 2.804 Å, forming a 3D structure (Figure S4). D

DOI: 10.1021/acs.inorgchem.5b02434 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

Figure 3. (a) Coordination environments of Co1(II) and Co2(II) in 3, the hydrogen atoms are omitted for clarity, thermal ellipsoids are drawn at the 30% probability level. (b) The regular hexagon viewed along Co1−Co2−Co1A axis. Selected bond lengths (Å) and angles (deg): Co1−N1 2.121(10), Co1−O17 2.074(11), Co2−N2 2.171(10), Co1−N5 2.103(13), Co1−O18 2.112(9), Co2−N2A#1 2.171(10), Co1−N9 2.143(11), Co2−N10 2.131(11), Co2−N6 2.167(11), Co1−O16 2.037(10), Co2−N10A#1 2.131(11), Co2−N6A#1 2.167(11), N1−Co1−O18 89.4(4), O17− Co1−N5 89.9(4), N1−Co1−O16 90.6(4), N1−Co1−O17 175.7(4), N1−Co1−N9 91.8(4), O18−Co1−O16 88.1(4), O18−Co1−O17 88.1(4), N9−Co1−O18 91.5(4), O17−Co1−O16 85.7(4), N1−Co1−N5 92.4(4), N9−Co1−O17 91.8(4), O16−Co1−N5 89.3(5), N5−Co1−O18 176.8(5), N5−Co1−N9 91.1(4), O16−Co1−N9 177.5(4), N10A#1−Co2−N10 180.0(6), N10A#1−Co2−N2A#1 90.3(4), N2−Co2−N2A#1 180.0(2), N10A#1−Co2−N6 89.8(4), N10−Co2−N6 90.2(4), N6−Co2−N2A#1 88.8(4), N2−Co2−N6 91.2(4), N10A#1−Co2−N6A#1 90.2(4), N10−Co2−N6A#1 89.8(4), N2A#1−Co2−N6A#1 91.2(4), N2−Co2−N6A#1 88.8(4), N6−Co2−N6A#1 180.0(1). Symmetry code: No. 1 −x + 1/2, −y + 1/2, −z + 1.

Figure 4. Coordination environment of Co(II) in 5, thermal ellipsoids are drawn at the 30% probability level. Selected bond lengths (Å) and angles (deg): Co1−N1 2.0991(16), Co1−O1 2.1122(16), Co1−N6 2.1908(17), Co1−N2 2.1005(17), Co1−O2 2.0873(17), Co1−Cl2 2.4321(6), O2−Co1−N1 89.20(7), O1−Co1−N2 89.37(7), O2− Co1−Cl2 92.21(6), O2−Co1−N2 88.98(7), O2−Co1−N6, 89.62(8), N1−Co1−Cl2 92.54(5), N1−Co1−N2 100.38(6), N1−Co1−N6 176.49(7), N2−Co1−Cl2 167.04(5).

Figure 5. Coordination environment of Ni(II) in 8, thermal ellipsoids are drawn at the 30% probability level. Selected bond lengths (Å) and angles (deg): Ni1−N1A#1 2.053(3), Ni1−O5 2.070(2), Ni1−N6 2.139(3), Ni1−N2 2.059(3), Ni1−O6 2.074(2), Ni1−Cl1 2.4768(9), N1A#1−Ni1−N2 95.74(11), O5−Ni1−O6 174.33(9), N1A#1−Ni1− Cl1 91.59(8), N1A #1 −Ni1−O5 92.43(10), N1A #1 −Ni1−N6 174.93(11), N2−Ni1−Cl1 172.51(8), N2−Ni1−O5 91.53(11), N2− Ni1−N6 79.33(11), O5−Ni1−Cl1 86.66(7), N1A#1−Ni1−O6 91.22(10), O5−Ni1−N6 88.91(11), O6−Ni1−Cl1 88.91(7), N2− Ni1−O6 92.42(10), O6−Ni1−N6 87.83(11), N6−Ni1−Cl1 93.37(8). Symmetry code: No. 1 −x + 1, −y + 1, −z + 1.

Crystal Structure of (8). Compound 8 is solved in the triclinic space group P1̅ with the asymmetric unit consisting of one Ni cation, one HATr molecule, two aqua molecules, and one Cl− anion as ligands, one free ClO4− anion, and two crystal water molecules (Figure 5). The Ni cation is coordinated by three nitrogen atoms from two HATr molecules, two oxygen atoms from two aqua molecules, and one Cl− anion affording a distorted octahedral geometry. The bond lengths of Ni−N lie E

DOI: 10.1021/acs.inorgchem.5b02434 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

Crystal Structure of (12). Compound 12 crystallizes in the tetragonal system, space group I4(1)/a, with two different central Cd cations in the asymmetric unit. As shown in Figure 7, the Cd1 cation displays a [CdN6] octahedral coordination

in the range from 2.053(3) to 2.139(3) Å, and the bond lengths of Ni−O5, Ni−O6, Ni−Cl1 are 2.070(2), 2.074(2), 2.4768(9) Å, respectively. The HATr molecule employs tridentate and bridging−chelating coordination mode with N1, N2, N1A, N2A four atoms linking two Ni cations to display a centrosymmetric binuclear unit. The six-member ring, two chelating rings, and two triazole rings are nearly coplanar (N1A−Ni1−N2−C1, 179.5°; Ni1A−N1−N2−C1, 178.6°). There exist hydrogen bonds between the nitrogen atoms of HATr ligands and the oxygen atoms of coordinated waters, crystal water molecules, ClO4− anions, coordinated Cl− anions, and between the coordinated aqua molecules and crystal water molecules, coordinated Cl− anions, and between crystal water molecules and ClO4− anions, coordinated Cl− anions, which could help connect the complex unit [Ni2Cl2(HATr)2(H2O)4]2+, free ClO4− anions, and crystal water molecules together into a 3D structure (Figure S5). Crystal Structure of (9). Compound 9 crystallizes in the monoclinic space group P2(1)/c. As shown in Figure 6, the

Figure 7. Molecule structure of 12, thermal ellipsoids are drawn at the 30% probability level. Selected bond lengths (Å) and angles (deg): Cd1−N2 2.304(6), Cd1−N12 2.416(7), Cd2−Cl1B#2 2.494(3), Cd1− N7 2.304(6), Cd1−N6 2.442(7), Cd2−Cl1C#3 2.494(3), Cd1−N1 2.310(6), Cd2−Cl1 2.494(3), Cd1−N8 2.328(6), Cd2−Cl1A#1 2.494(3), N2−Cd1−N7 96.1(2), N12−Cd1−N7 87.8(2), N12− Cd1−N6 93.0(3), N2−Cd1−N1 95.0(2), N12−Cd1−N1 166.6(2), Cl1−Cd2−Cl1A#1 101.40(6), N7−Cd1−N1 92.0(2), N8−Cd1−N12 71.5(2), Cl1−Cd2−Cl1B#2 101.40(6), N2−Cd1−N8 160.1(2), N7− Cd1−N6 167.4(2), Cl1A#1−Cd2−Cl1B#2 127.21(15), N7−Cd1−N8 100.4(2), N2−Cd1−N6 71.3(2), Cl1−Cd2−Cl1C#3 127.21(15), N1− Cd1−N8 95.3(2), N1−Cd1−N6 90.1(2), Cl1A#1−Cd2−Cl1C#3 101.40(6), N2−Cd1−N12 98.4(2), N8−Cd1−N6 91.8(2), Cl1B#2− Cd2−Cl1C#3 101.40(6). Symmetry codes: No. 1 −x + 1, −y + 3/2, z; No. 2 −y + 5/4, x + 1/4, −z + 1/4; No. 3 y − 1/4, −x + 5/4, −z + 1/ 4.

Figure 6. Molecule structure of 9, thermal ellipsoids are drawn at the 30% probability level. Selected bond lengths (Å) and angles (deg): Ni1−N1 2.057(2), Ni1−O11 2.070(2), Ni1−N6A#1 2.136(3), Ni1− N2A#1 2.033(2), Ni1−O9 2.078(2), Ni1−O10 2.088(2), N1−Ni1− N2A #1 96.64(9), O11−Ni1−O9 88.76(9), N1−Ni1−N6A #1 176.07(10), N1−Ni1−O11 90.51(9), N1−Ni1−O10 94.98(10), N2A #1 −Ni1−N6A #1 79.44(10), N2A #1 −Ni1−O11 172.78(9), N2A#1−Ni1−O10 91.57(10), O11−Ni1−N6A#1 93.41(10), N1− Ni1−O9 91.86(9), O11−Ni1−O10 88.84(9), O9−Ni1−N6A #1 87.97(10), N2A#1−Ni1−O9 89.96(9), O9−Ni1−O10 172.77(9), O10−Ni1−N6A#1 85.36(10). Symmetry code: No. 1 −x + 2, −y, −z + 1.

geometry, defined by six nitrogen atoms from four HATr ligands; a similar coordination sphere has been described for {[Cd(HATr)2](ClO4)2}n.11b The Cd2 cation is tetrahedrally coordinated by four Cl− anions, exhibiting an anionic [CdCl4]2− species. The Cd−N distances varying from 2.304(6) to 2.442(7) Å and the Cd−Cl bond length of 2.494(3) Å can be comparable with values from previous literature.19 Two kinds of hydrogen bonds of N−H···O and N− H···Cl are formed in 12 with the N···O and N···Cl distances of 2.94(2)−3.36(7) and 3.004(8)−3.340(10) Å, respectively. These hydrogen bonding interactions are responsible for the stabilization of the 3D structure (Figure S7). Effect of the Reaction System on Structural Diversity. In our previous work, it has been found that the formation of Cd(II) complexes with HATr is metal−ligand ratio-depended in starting materials under solvothermal conditions.11b In this case, analogous crystalline products were obtained, for Mn(II) and Zn(II) compounds as examples; single-crystal X-ray diffraction results indicate that they display 1D coordination frameworks (with a molar ratio of Mn/Zn to HATr·2HCl = 1:1 for compounds 1 and 10) and discrete mononuclear units (with a molar ratio of Mn/Zn to HATr·2HCl = 1:3 for compounds 2

asymmetric unit of 9 has one Ni cation, one HATr molecule, three aqua molecules as ligands, two free ClO4− anions, and one crystal water molecule. Ni1 is six-coordinated to three nitrogen atoms from two HATr ligands and three oxygen atoms from three distinct aqua molecules in a distorted octahedral geometry. Three oxygen atoms (O9, O10, O11) and one nitrogen atom (N2A) comprise the equatorial plane, while two nitrogen atoms (N1, N6A) locate the axial sites with a N1− Ni1−N6A bond angle of 176.07(10)°. The Ni−N bond distances are in the range of 2.033(2)−2.136(3) Å and the Ni−O bond lengths range from 2.070(2) to 2.088(2) Å, which fall into the normal range.18 The Ni cations are linked by HATr to generate a centrosymmetric binuclear unit, and the adjacent binuclear unit are held together to form a 3D structure via N− H···O, O−H···O, and C−H···O hydrogen bonding interactions (Figure S6). F

DOI: 10.1021/acs.inorgchem.5b02434 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry Table 1. Thermal Behavior and Sensitivities of Compounds 1−12 Tdec(°C)a IS(J)b FS(N)c a

1

2

3

4

5

6

7

8

9

10

11

12

294 4 72

269 7 96

238 3 24

292 3 80

234

375 3 36

300 3 72

255 3 120

256 3 6

300 2 12

296 3 28

268 3 84

Decomposition temperature (onset, from DSC, β = 5 °C min−1). bImpact sensitivity. cFriction sensitivity.

friction sensitivities, and they were classified according to the U.N. Recommendations on the Transport of Dangerous Goods.20 Compound 9 is classed as very sensitive toward impact and extreme sensitive toward friction. Compounds 3, 4, 6, 7, 10, 11 are very sensitive toward impact and very sensitive toward friction. Compound 1 is sensitive toward impact and very sensitive toward friction. Compound 2 is classified as sensitive toward impact and friction, while compounds 8 and 12 are classified as very sensitive toward impact and sensitive toward friction (Table 1).

and 11). However, a dissimilar structure of compound 12 can be found when an approximate molar ratio of 1:2 (Cd/HATr· 2HCl) was utilized in starting materials. It is of special interest that dehydrazination occurred under solvothermal condition (100 °C) and the HATr ligands transformed into ATr ligands in compounds 3 and 6 with the ratio of Co/Ni to HATr·2HCl of 1:1. Furthermore, in the preparation of 1−12, no ATr ligand was used, and dehydrazination occurred neither in the solvothermal reactions of Mn, Zn, Cd salts with HATr ligands nor Co, Ni salts with HATr ligands (with a ratio of Co/Ni to HATr·2HCl = 1:3) under same conditions, suggesting that metal ions and ratio of reactants may have important effect on the dehydrazination reaction. In addition, a comparison of the synthetic protocol of compounds 6 and 9 indicates that these two molecules were derived using the same metal salt, solvent, metal−ligand ratio, and synthetic condition; however, the temperature of 100 °C led to the formation of compound 6 containing ATr ligand, while the temperature of 85 °C afforded the structure of nickel dimer with HATr ligand, found in compound 9. Moreover, reactions of the same metal salts with HATr·2HCl under conventional condition can produce another kind of coordination compounds with binuclear units (compounds 5 and 8), and the Cl− anions participate in coordination in compounds 5 and 8 in contrast to compounds 4 and 7, implying that the synthetic condition can notably influence the formation of final crystalline products. Thermal Stability and Energetic Properties. The thermal stabilities of all compounds were explored by DSC experiments. Endothermic points are not observed for all compounds except 2, 5, and 9 based on their DSC curves (Figure S8). Compound 3 indicates the decomposition temperatures of 238 °C and compounds 1, 4, 8, 11−12 are thermally stable above 250 °C, while compounds 7 and 10 show decomposition at even higher temperatures up to 300 °C. Compound 6 reveals the highest decomposition temperatures of 375 °C in all compounds. For compound 5 and 9, the crystal water and coordinated water can be removed within the temperature range of 77−169 °C and 78−99 °C, they are stable up to 234 and 256 °C, respectively. Compound 2 decomposes immediately after it starts to melt at 260 °C, whereas for compounds 3, 6 and 8, no endothermic event before decomposition can be observed, although they contain coordinated water and crystal water molecules. Comparing with the same metal cation, the perchlorates have higher decomposition temperatures than those of the chloridecontained (e.g., 1: 294 °C, 2: 269 °C; 10: 300 °C, 11: 296 °C). If compounds containing the same anion are compared to each other, the nickel compound has the highest decomposition temperature (e.g., 7: 300 °C), and the zinc compound follows the nickel compound having the second highest temperature (e.g., 11: 296 °C) again followed by the cobalt compound (e.g., 4: 292 °C), and the manganese compound decomposes at relatively low temperature (e.g., 2: 269 °C). Except compound 5 bearing no energetic anion, all other synthesized compounds were tested in terms of impact and

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CONCLUSION A series of 12 metal (Mn, Co, Ni, Zn and Cd) coordination compounds have been prepared using diverse synthetic approaches with 3-hydrazino-4-amino-1,2,4-triazole dihydrochloride as starting material. On one hand, HATr may behave as either a bidentate chelating or tridentate bridging−chelating ligand to construct mononuclear, binuclear or infinite 1D chain coordination structures. On the other hand, HATr can transform to ATr by loss of the hydrazino group under solvothermal condition (100 °C), which can act as a bidentate bridging connector to build trinuclear structures. In addition, the free counterions and crystal water molecules can take part in the formation of hydrogen bonds to extend and stabilize the final 3D structures. As a whole, coordinative forces, as well as weak hydrogen bonding interactions, play a key role in structural assembly. Furthermore, the thermal analyses show that all compounds have high thermal stability, and all compounds holding energetic anions indicate strong sensitivities toward impact and friction.

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ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.5b02434. Tabulated crystallographic data for compounds 1−12, tabulated hydrogen bond data, illustrated packing diagrams, DSC curves of compounds 1−12. (PDF) Crystallographic data for compound 1. (CIF) Crystallographic data for compound 2. (CIF) Crystallographic data for compound 3. (CIF) Crystallographic data for compound 4. (CIF) Crystallographic data for compound 5. (CIF) Crystallographic data for compound 6. (CIF) Crystallographic data for compound 7. (CIF) Crystallographic data for compound 8. (CIF) Crystallographic data for compound 9. (CIF) Crystallographic data for compound 10. (CIF) Crystallographic data for compound 11. (CIF) Crystallographic data for compound 12. (CIF) G

DOI: 10.1021/acs.inorgchem.5b02434 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry

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(15) Niu, C. Y.; Zheng, X. F.; Wan, X. S.; Kou, C. H. Cryst. Growth Des. 2011, 11, 2874−2888. (16) Wang, S.; Westmoreland, T. D. Inorg. Chem. 2009, 48, 719−27. (17) (a) Du, M.; Jiang, X. J.; Zhao, X. J. Inorg. Chem. 2007, 46, 3984−3995. (b) Wang, X. L.; Sui, F. F.; Lin, H. Y.; Zhang, J. W.; Liu, G. C. Cryst. Growth Des. 2014, 14, 3438−3452. (c) Yang, Q.; Zhang, X. F.; Zhao, J. P.; Hu, B. W.; Bu, X. H. Cryst. Growth Des. 2011, 11, 2839−2845. (18) (a) Liu, L.; Huang, C.; Xue, X. N.; Li, M.; Hou, H. W.; Fan, Y. T. Cryst. Growth Des. 2015, 15, 4507−4517. (b) Chen, M.; Chen, S. S.; Okamura, T.-a.; Su, Z.; Chen, M. S.; Zhao, Y.; Sun, W. Y.; Ueyama, N. Cryst. Growth Des. 2011, 11, 1901−1912. (c) Yin, Y. Y.; Ma, J. G.; Niu, Z.; Cao, X. C.; Shi, W.; Cheng, P. Inorg. Chem. 2012, 51, 4784−90. (19) (a) Yao, Y. L.; Xue, L.; Che, Y. X.; Zheng, J. M. Cryst. Growth Des. 2009, 9, 606−610. (b) Xu, Y. Y.; Wu, X. X.; Wang, Y. Y.; Su, X. M.; Liu, S. X.; Zhu, Z. Z.; Ding, B.; Wang, Y.; Huo, J. Z.; Du, G. X. RSC Adv. 2014, 4, 25172. (c) Lama, P.; Bharadwaj, P. K. Cryst. Growth Des. 2011, 11, 5434−5440. (20) Impact: insensitive > 40 J, less sensitive ≥ 35 J, sensitive ≥ 4 J, very sensitive ≤ 3 J; Friction: insensitive > 360 N, less sensitive = 360 N, sensitive < 360 N a. > 80 N, very sensitive ≤ 80 N, extreme sensitive ≤ 10 N. According to the U.N. Recommendations on the Transport of Dangerous Goods.

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS It should be gratefully acknowledged that financial support came from the National Natural Science Foundation of China and the project of State Key Laboratory of Science and Technology (ZDKT 12-03 and YBKT16-04). The authors thank Dr. L. Liu (Institute of Process Engineering, Chinese Academy of Sciences) for help in the sensitivity testing.

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DOI: 10.1021/acs.inorgchem.5b02434 Inorg. Chem. XXXX, XXX, XXX−XXX