Molecular and Crystal Structure of a New High Energy Density Material: Aminoguanidinium-styphnate, [H2NNHC(NH2)2]2[C6HO2(NO2)3]
1
Nammo Germany GmbH, Wilhelm-Dümling-Street 12, 39218 Schönebeck, Germany
2
Chemisches Institut der Otto-von-Guericke-Universität Magdeburg, 39106 Magdeburg, Germany
*
Author to whom correspondence should be addressed.
Crystals 2012, 2(1), 34-42; https://doi.org/10.3390/cryst2010034
Submission received: 2 September 2011
/
Revised: 20 December 2011
/
Accepted: 26 December 2011
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Published: 4 January 2012
Abstract
:The title compound [H2NNHC(NH2)2]2[C6HO2(NO2)3] (2) was prepared in 85% yield by treatment of sodium styphnate with 2 equivalents of aminoguanidinium nitrate, followed by crystallization from aqueous solution. Compound 2 crystallizes in the triclinic space group Pī with unit cell dimensions a = 6.7224(3) Å, b = 10.7473(4) Å, c = 11.9604(5) Å, α = 113.212(4)°, β = 90.579(3)°, γ = 99.815(3)°, V = 779.68(6) Å3, Z = 2. In the solid state structure of 2, no water of crystallization is present. Bond angles within the aromatic ring of the styphnate anion indicate a significant distortion with larger angles (122.04(18)–125.96(18) Å) at the carbons bearing the nitro groups, and smaller ones (113.30(17) and 114.07(17) Å) at the C-O− carbon atoms. The crystal structure of 2 consists of layers formed by an extensive network of N-H...O hydrogen bonds between NH2 groups of the aminoguanidinium cation and the negatively charged oxygens of the styphnate anion. The layers are again interconnected by N-H...N hydrogen bonds between neighboring aminoguanidinium cations.
1. Introduction
High energy density materials (HEDM's) form an important class of explosive compounds. Several significant advantages such as high heats of combustion, high propulsive power, high specific impulse, as well as smokeless combustion make them highly useful as propellants, explosives, and pyrotechnics [1,2,3,4,5,6]. Besides picric acid and its salts [1,7], 2,4,6-trinitro-resorcinol (= styphnic acid, 1) is one of the polynitrophenole derivatives having industrial importance. Styphnic acid was first reported by Merz and Zetter in 1879 [8]. Its synthesis involves treatment of resorcinol with sulfuric acid followed by nitration of the intermediate resorcinoldisulfonic acid. Salts of 2,4,6-trinitro-resorcinol are commonly named styphnates or trizinates. Several styphnates have found various applications in explosive devices. Particularly important are lead(II) styphnate and basic lead(II) styphnate which are being used in primers and military ammunition [9]. A major drawback of lead(II) styphnate and related styphnates is their high static sensitivity and especially the serious heavy metal pollution associated with their use. Thus a common theme in current HEDM research is the search for environmentally friendly initiators. Styphnates of alkali and alkaline earth metals have frequently been employed in the automobile industry, e.g. as ignitors for airbags [10,11], and their structural chemistry has been thoroughly investigated. We report here the synthesis and crystal structure of a new, metal-free styphnate, namely aminoguanidinium styphnate, [H2NNHC(NH2)2]2[C6HO2(NO2)3] (2).
2. Results and Discussion
2.1. Synthesis and Characterization of [H2NNHC(NH2)2]2[C6HO2(NO2)3] (2)
The preparation of the title compound aminoguanidinium styphnate, [H2NNHC(NH2)2]2[C6HO2(NO2)3] (2) was achieved according to Equation (1) by treatment of sodium styphnate with 2 equivalents of aminoguanidinium nitrate in aqueous solution. The product was fully characterized by IR and NMR spectroscopy as well as elemental analysis.
2.2. Crystal Structure
Single crystals of 2 suitable for X-ray diffraction were obtained by recrystallization from hot water. It was observed that fast crystallization from concentrated solution afforded yellow-orange, needle-like crystals, whereas from diluted solutions more compact, block-like crystals were obtained. However, elemental analyses of the different crystalline forms revealed no difference in the analytical composition.. Figure 1 illustrates the habit of the crystals obtained from dilute aqueous solution.
Figure 1.
Compact crystals of [H2NNHC(NH2)2]2[C6HO2(NO2)3] (2) obtained by recrystallization from dilute aqueous solutions.
Figure 1.
Compact crystals of [H2NNHC(NH2)2]2[C6HO2(NO2)3] (2) obtained by recrystallization from dilute aqueous solutions.
Figure 2.
Structure of aminoguanidinium styphnate, [H2NNHC(NH2)2]2[C6HO2(NO2)3] (2) in the crystal, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
Figure 2.
Structure of aminoguanidinium styphnate, [H2NNHC(NH2)2]2[C6HO2(NO2)3] (2) in the crystal, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
Compound 2 crystallizes in the triclinic space group Pī with one styphnate anion and two aminoguanidinium cations. Crystal data and refinement parameters are summarized in Table 1. Figure 2 depicts the content of the unit cell, and selected bond lengths and angles are listed in Table 2. Surprisingly, although crystallized from aqueous solutions, the crystals of 2 contain no water of crystallization. As can be deduced from the data in Table 2, both the aminoguanidinium cation and the styphnate anion show highly delocalized π-bonding. As expected, all C-C, C-N, and N-N bond lengths show typical values intermediate between single and double bonds. Bond angles within the aromatic ring of the styphnate anion indicate a significant distortion with larger angles (122.04(18)–125.96(18) Å) at the carbons bearing the nitro groups, and smaller ones (113.30(17) and 114.07(17) Å) at the C-O− carbon atoms.
Figure 3 shows the crystal packing of compound 2 in the solid state. The crystal structure is dominated by an extensive network of N-H...O hydrogen bonds between NH2 groups of the aminoguanidinium cation and the negatively charged oxygens of the styphnate anion. This leads to the formation of layers of alternating cations and anions. The layers are again interconnected by N-H...N hydrogen bonds between neighboring aminoguanidinium cations (Table 3).
Figure 3.
Crystal packing of the title compound aminoguanidinium styphnate, [H2NNHC(NH2)2]2[C6HO2(NO2)3] (2).
Figure 3.
Crystal packing of the title compound aminoguanidinium styphnate, [H2NNHC(NH2)2]2[C6HO2(NO2)3] (2).
Table 1.
Crystal data and structure refinement for aminoguanidinium styphnate, [H2NNHC(NH2)2]2[C6HO2(NO2)3] (2).
| Identification code | magd09 |
| Empirical formula | C8H15N11O8 |
| Formula weight | 393.31 |
| Temperature | 100(2) K |
| Wavelength | 0.71073 Å |
| Crystal system | Triclinic |
| Space group | P -1 |
| Unit cell dimensions | a = 6.7224(3) Å |
| b = 10.7473(4) Å | |
| c = 11.9604(5) Å | |
| Volume | 779.68(6) Å3 |
| Z | 2 |
| Density (calculated) | 1.675 mg/m3 |
| Absorption coefficient | 0.148 mm−1 |
| F(000) | 408 |
| Crystal size | 0.26 × 0.21 × 0.13 mm3 |
| Theta range for data collection | 2.17 to 28.28° |
| Index ranges | −8 ≤ h ≤ 8, −14 ≤ k ≤ 14, −15 ≤ l ≤ 15 |
| Reflections collected | 12676 |
| Independent reflections | 3857 [R(int) = 0.0335] |
| Completeness to theta = 28.00° | 99.8% |
| Absorption correction | None |
| Refinement method | Full-matrix least-squares on F2 |
| Data/restraints/parameters | 3857/86/313 |
| Goodness-of-fit on F2 | 0.862 |
| Final R indices [I > 2sigma(I)] | R1 = 0.0398, wR2 = 0.0916 |
| R indices (all data) | R1 = 0.0627, wR2 = 0.0964 |
| Largest diff. peak and hole | 0.540 and −0.330 e.Å−3 |
Table 2.
Selected bond lengths [Å] and angles [°] for aminoguanidinium styphnate, [H2NNHC(NH2)2]2[C6HO2(NO2)3] (2).
| O(1)-C(1) | 1.2559(18) | N(5)-C(7) | 1.317(2) |
| O(2)-C(3) | 1.2394(18) | N(6)-C(7) | 1.339(2) |
| O(5)-N(2) | 1.2269(16) | N(6)-N(7) | 1.4073(19) |
| O(6)-N(2) | 1.2423(16) | N(8)-C(8) | 1.330(2) |
| O(7)-N(3) | 1.2429(16) | N(9)-C(8) | 1.320(2) |
| O(8)-N(3) | 1.2403(16) | N(10)-C(8) | 1.3343(19) |
| N(1)-O(3) | 1.220(3) | N(10)-N(11) | 1.4099(18) |
| N(1)-O(4) | 1.2646(19) | C(1)-C(2) | 1.443(2) |
| N(1)-O(3') | 1.296(14) | C(1)-C(6) | 1.455(2) |
| N(1)-C(2) | 1.4223(19) | C(2)-C(3) | 1.449(2) |
| N(1)-O(4') | 1.443(7) | C(3)-C(4) | 1.461(2) |
| N(2)-C(4) | 1.4309(19) | C(4)-C(5) | 1.376(2) |
| N(3)-C(6) | 1.4285(19) | C(5)-C(6) | 1.371(2) |
| N(4)-C(7) | 1.324(2) | ||
| O(3)-N(1)-O(4) | 117.1(3) | O(2)-C(3)-C(2) | 123.57(14) |
| O(3)-N(1)-O(3') | 7.8(16) | O(2)-C(3)-C(4) | 122.97(13) |
| O(4)-N(1)-O(3') | 124.7(14) | C(2)-C(3)-C(4) | 113.36(13) |
| O(3)-N(1)-C(2) | 123.8(3) | C(5)-C(4)-N(2) | 116.37(14) |
| O(4)-N(1)-C(2) | 118.43(14) | C(5)-C(4)-C(3) | 122.20(13) |
| O(3')-N(1)-C(2) | 116.0(13) | N(2)-C(4)-C(3) | 121.31(13) |
| O(3)-N(1)-O(4') | 99.3(4) | C(6)-C(5)-C(4) | 122.18(15) |
| O(4)-N(1)-O(4') | 65.7(3) | C(5)-C(6)-N(3) | 116.17(14) |
| O(3')-N(1)-O(4') | 103.6(13) | C(5)-C(6)-C(1) | 122.21(14) |
| C(2)-N(1)-O(4') | 110.3(3) | N(3)-C(6)-C(1) | 121.61(13) |
| O(5)-N(2)-O(6) | 120.23(13) | N(5)-C(7)-N(4) | 120.64(15) |
| O(5)-N(2)-C(4) | 121.26(13) | N(5)-C(7)-N(6) | 119.38(14) |
| O(6)-N(2)-C(4) | 118.51(12) | N(4)-C(7)-N(6) | 119.98(14) |
| O(8)-N(3)-O(7) | 120.45(12) | N(9)-C(8)-N(8) | 120.45(14) |
| O(8)-N(3)-C(6) | 120.50(13) | N(9)-C(8)-N(10) | 121.21(14) |
| O(7)-N(3)-C(6) | 119.04(12) | N(8)-C(8)-N(10) | 118.28(14) |
| C(7)-N(6)-N(7) | 118.14(13) | ||
| C(8)-N(10)-N(11) | 124.15(13) | ||
| O(1)-C(1)-C(2) | 123.60(14) | ||
| O(1)-C(1)-C(6) | 122.47(13) | ||
| C(2)-C(1)-C(6) | 113.88(13) | ||
| N(1)-C(2)-C(1) | 117.63(13) | ||
| N(1)-C(2)-C(3) | 116.48(13) | ||
| C(1)-C(2)-C(3) | 125.89(13) |
Table 3.
Hydrogen bond lengths [Å] and angles [°] for aminoguanidinium styphnate, [H2NNHC(NH2)2]2[C6HO2(NO2)3] (2).
| D-H...A | d(D-H) | d(H...A) | d(D...A) | <(DHA) |
| N(4)-H(4A)...O(2)#1 | 0.861(13) | 2.090(15) | 2.8484(18) | 146.5(18) |
| N(4)-H(4B)...O(4)#2 | 0.848(13) | 2.192(14) | 3.021(2) | 165.7(18) |
| N(5)-H(5A)...N(7)#3 | 0.872(13) | 2.302(14) | 3.0538(19) | 144.5(15) |
| N(5)-H(5B)...O(2)#1 | 0.867(13) | 1.967(15) | 2.7539(18) | 150.3(17) |
| N(5)-H(5B)...O(5)#1 | 0.867(13) | 2.244(16) | 2.8868(17) | 130.9(16) |
| N(6)-H(6)...O(3)#2 | 0.828(13) | 2.359(15) | 3.141(5) | 157.8(15) |
| N(7)-H(7A)...O(1)#3 | 0.880(13) | 2.099(14) | 2.9737(19) | 172.7(17) |
| N(7)-H(7B)...O(5)#4 | 0.876(13) | 2.614(18) | 3.0480(17) | 111.6(14) |
| N(8)-H(8A)...O(8)#5 | 0.862(13) | 2.086(13) | 2.9407(17) | 171.3(17) |
| N(8)-H(8B)...O(1) | 0.866(13) | 2.039(15) | 2.8104(18) | 147.9(17) |
| N(8)-H(8B)...O(8) | 0.866(13) | 2.203(16) | 2.8673(18) | 133.2(16) |
| N(9)-H(9A)...O(7)#5 | 0.836(13) | 2.222(13) | 3.0458(18) | 168.8(16) |
| N(9)-H(9B)...O(6)#6 | 0.825(13) | 2.110(14) | 2.9156(19) | 165.4(19) |
| N(10)-H(10)...O(1) | 0.828(13) | 2.030(15) | 2.7668(18) | 147.8(17) |
| N(10)-H(10)...O(3) | 0.828(13) | 2.371(16) | 3.029(4) | 136.9(15) |
| N(11)-H(11A)...O(6)#6 | 0.855(14) | 2.530(17) | 3.1708(19) | 132.5(16) |
Symmetry transformations used to generate equivalent atoms: #1 –x + 1, −y + 1, −z + 1; #2 x, y − 1,z; #3 –x + 1, −y + 1, −z + 2; #4 x, y, z + 1; #5 −x, −y + 1, −z + 2; #6 x, y + 1, z + 1
2.3. Sensitivity
For initial safety testing, the impact and friction sensitivities of the new styphnate was tested according to established BAM methods [1] using the BAM drophammer and BAM friction tester as well as a simple combustion test (Table 4). The title compound was found to be insensitive towards impact (<40 Nm) and friction (<360 N) and showed deflagration upon combustion. Long-term stability tests over a period of 30 days showed no changes in these data.
| Compound | 2 |
| M (g/mol) | 393.27 |
| ρ, g/cm3 | 1.844 |
| Impact/Nm | >40 |
| Friction Sensitivity (N) | >360 |
| Combustion Test | Deflagration |
| N content (%) | 39.18 |
| Ω (%) | −26.15 |
3. Experimental Section
Aminoguanidinium nitrate was obtained from Aldrich and used as received. Sodium styphnate was prepared as described in [6]. The X-ray diffraction data for compound 2 were measured at −173 °C on a Stoe IPDS diffractometer. Structure solution and refinement were carries out using the programs SHELXS-97 [12] and SHELXL-97 [13].
Preparation of Aminoguanidinium-styphnate, [H2NNHC(NH2)2]2[C6HO2(NO2)3] (2). Sodium styphnate (0.58 g, 2.0 mmol) was dissolved in a minimum amount of warm (ca. 40 °C) water and combined with an aqueous solution of aminoguanidinium nitrate (0.30 g, 2.2 mmol). Crystallization at room temperature for 24 h afforded 0.67 g (85% yield) bright yellow-orange, compact crystals of 2. m.p. 220 °C. Anal. Calcd. for C8H15N11O8 (393.27 g/mol): C 24.43, H 3.84, N 39.18%. Found: C 23.65, H 3.89, N 38.39%. IR (KBr, cm−1): vmax 3422 (m, vNH), 3128 (vs), 2232 (w), 1725 (s), 1636 (m), 1575 (vs, vC-NO2), 1539 (vs), 1515 (vs), 1417 (m), 1399 (s), 1355 (m), 1314 (vs), 1275 (m), 1231 (m), 1211 (m), 1132 (m), 1090 (m), 979 (m), 961 (m), 905 (m), 859 (w), 797 (m), 715 (m), 665 (m), 621 (m), 529 (w), 488 (m), 467 (m), 414 (w). 13C-NMR (20°C, D2O, 100 MHz): δ [ppm] 154.1 (C1), 127.2 (C2), 125.5 (C3), 135.1 (C4), 163.3 (C5) (Figure 4).
Figure 4.
Numbering scheme of the carbon atoms in aminoguanidinium styphnate, [H2NNHC(NH2)2]2[C6HO2(NO2)3] (2).
Figure 4.
Numbering scheme of the carbon atoms in aminoguanidinium styphnate, [H2NNHC(NH2)2]2[C6HO2(NO2)3] (2).
4. Conclusions
Aminoguanidinium styphnate, [H2NNHC(NH2)2]2[C6HO2(NO2)3] (2), was prepared in 85% yield by treatment of sodium styphnate with 2 equivalents of aminoguanidinium nitrate, followed by crystallization from aqueous solution. In the solid state structure of 2, no water of crystallization is present. Bond angles within the aromatic ring of the styphnate anion indicate a significant distortion with larger angles (122.04(18)–125.96(18) Å) at the carbons bearing the nitro groups, and smaller ones (113.30(17) and 114.07(17) Å) at the C-O− carbon atoms. The crystal structure of 2 consists of layers interconnected by an extensive network of N-H...O hydrogen bonds between NH2 groups of the aminoguanidinium cation and the negatively charged oxygens of the styphnate anion. The layers are again interconnected by N-H...N hydrogen bonds between neighboring aminoguanidinium cations.
Acknowledgements
This work was supported by the Otto-von-Guericke-Universität Magdeburg.
References
- Klapötke, T.M. Chemistry of High-Energy Materials; Walter de Gruyter: Berlin, Germany, 2011; and references cited therein. [Google Scholar]
- Nair, U.R.; Asthana, S.N.; Rao, A.S.; Gandhe, B.R. Advances in high energy materials. Defence Sci. J. 2010, 60, 137–151. [Google Scholar]
- Göbel, M.; Klapötke, T.M. Development and testing of energtic materials: the cooncept of high density based on the trinitroethyl functionality. Adv. Functional Mater. 2009, 19, 347–365. [Google Scholar]
- Badgujar, D.M.; Talawar, M.B.; Asthana, S.N.; Mahulikar, P.P. Advances in science and technology of modern energetic materials: an overview. J. Hazardous Mater. 2008, 151, 289–305. [Google Scholar]
- Rice, B.M.; Byrd, E.F.C.; Mattson, W.D. Computational aspects of nitrogen-rich HEDMs. Struct. Bond. 2007, 125 (High Density Materials), 153–194. [Google Scholar] [CrossRef]
- Oestmark, H.; Walin, S.; Goede, P. High energy density materials (HEDM): Overvoew, theory and synthetic efforts at FOI. Central Eur. J. Energetic Mater. 2007, 4, 83–108. [Google Scholar]
- Urbanski, T. Chemie und Technologie der Explosivstoffe; DVFG: Leipzig, Germany, 1984. [Google Scholar]
- Merz, V.; Zetter, G. Ueber einige Derivate des Resorcins und Orcins. Ber. Dtsch. Chem. Ges. 1879, 12, 2035–2049. [Google Scholar]
- Wallace, J.S. Chemical Analysis of Firearms, Ammunition and Gunshot Residue; CRC Press: Boca Raton, FL, USA, 2008. [Google Scholar]
- Bley, U.; Hagel, R.; Hoschenko, A.; Lechner, P.S. Anzündsatz. German Patent DE 10 2006 060 146 A1, 21 June 2007.
- Liu, J.-W.; Zhang, J.-G.; Zhang, T.-L.; Zheng, H.; Yu, K.-B. A new hetero-bimetallic coordination polymer, cesium, and sodium complex of styphnate trihydrate [CsNa(TNR)(H2O)3]n. Struct. Chem. 2009, 20, 387–392, and references cited therein. [Google Scholar] [CrossRef]
- Sheldrick, G.M. SHELXL-97 Program for Crystal Structure Refinement; Universität Göttingen: Göttingen, Germany, 1997. [Google Scholar]
- Sheldrick, G.M. SHELXS-97 Program for Crystal Structure Solution; Universität Göttingen: Göttingen, Germany, 1997. [Google Scholar]
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Deblitz, R.; Hrib, C.G.; Plenikowski, G.; Edelmann, F.T. Molecular and Crystal Structure of a New High Energy Density Material: Aminoguanidinium-styphnate, [H2NNHC(NH2)2]2[C6HO2(NO2)3]. Crystals 2012, 2, 34-42. https://doi.org/10.3390/cryst2010034
AMA Style
Deblitz R, Hrib CG, Plenikowski G, Edelmann FT. Molecular and Crystal Structure of a New High Energy Density Material: Aminoguanidinium-styphnate, [H2NNHC(NH2)2]2[C6HO2(NO2)3]. Crystals. 2012; 2(1):34-42. https://doi.org/10.3390/cryst2010034
Chicago/Turabian StyleDeblitz, Raik, Cristian G. Hrib, Georg Plenikowski, and Frank T. Edelmann. 2012. "Molecular and Crystal Structure of a New High Energy Density Material: Aminoguanidinium-styphnate, [H2NNHC(NH2)2]2[C6HO2(NO2)3]" Crystals 2, no. 1: 34-42. https://doi.org/10.3390/cryst2010034
