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Synthesis and supramolecular structure of [Me3Sn(μ-C2N10)SnMe3(H2O)]n, the first metal–organic azotetrazolate
Inorganic Chemistry Communications 18 (2012) 57–60
Contents lists available at SciVerse ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
Synthesis and supramolecular structure of [Me3Sn(μ-C2N10)SnMe3(H2O)]n, the first metal–organic azotetrazolate Raik Deblitz a, Cristian G. Hrib b, Georg Plenikowski a, Frank T. Edelmann b,⁎ a b
Nammo Germany GmbH, Wilhelm-Dümling-Str. 12, 39218 Schönebeck, Germany Chemisches Institut der Otto-von-Guericke-Universität Magdeburg, 39106 Magdeburg, Germany
a r t i c l e
i n f o
Article history: Received 27 October 2011 Accepted 9 January 2012 Available online 16 January 2012 Keywords: Energetic compounds Azotetrazolate dianion Tin Organotin compounds X-ray structure.
a b s t r a c t The first metal–organic azotetrazolate, [Me3Sn(μ-C2N10)SnMe3(H2O)]n (2), was prepared in 61% isolated yield by the reaction of disodium azotetrazolate (Na2AZT⋅5H2O, 1) with 2 equivalents of Me3SnCl in aqueous solution. An X-ray diffraction study revealed a novel supramolecular structure of 2 in the crystal. Two different coordination environments around tin result in the formation of an unexpected zig-zag chain structure in the solid state with H2O ligands coordinated to every second Sn atom ligands terminating the alternating corners of the zig-zag chain. Both hydrogen atoms of the coordinated water molecules are engaged in O–H⋅⋅⋅N to different azotetrazolate dianions, leading to an interlocking of the zig-zag chain in a zipper-like overall crystal structure. Despite its fairly low nitrogen content of only 27.48% the title compound was found to be sensitive to both impact and friction. © 2012 Elsevier B.V. All rights reserved.
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 very useful as propellants, explosives, and pyrotechnics [1–6]. Notable among the most promising recent developments in the chemistry of HEDM's are compounds that combine a high nitrogen content (molecular nitrogen forms the major component of the decomposition products) with a high heat of formation and insensitivity to shock, friction, and electrostatic discharge. Particularly useful in this respect are salts of the azo2− tetrazolate dianion, (C2N10 , =AZT 2 −). The disodium salt (Na2AZT⋅ 5H2O, 1) is the most readily accessible azotetrazolate described in the literature. It represents the most important starting material for all other known azotetrazolate derivatives. Na2AZT⋅ 5H2O (1) was first prepared by Thiele more than 100 years ago by oxidation of aminotetrazole with potassium permanganate in boiling sodium hydroxide solution (Eq. (1)) [7,8]. This rather brutal method produces disodium azotetrazolate as its pentahydrate in the form of large, bright yellow crystals. By now, numerous metal salts of azotetrazolate have been synthesized and studied as potential initial explosives [9–13]. An innovative approach in this field is the use of various nitrogen-based cations such as ammonium, hydrazinium, guanidinium, aminoguanidinium, diaminoguanidinium, or triaminoguanidinium, which give rise to energetic compounds with a very high nitrogen content in the range from 78.8% for the bis(guanidinium) derivative to 85.2% for the bis(hydrazinium) salt [14–20]. Also
⁎ Corresponding author. Tel.: + 49 391 6718327; fax: + 49 391 6712933. E-mail address: [email protected] (F.T. Edelmann). 1387-7003/$ – see front matter © 2012 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2012.01.009
known are a few covalent azotetrazolates such as 1,1'- and 2,2'-dimethylazotetrazolate [9,21]. Surprisingly, it appears that no metal–organic main-group or organotransition metal derivatives of the AZT dianion have thus far been reported in the literature. We describe here the synthesis and structural characterization of [Me3Sn(μ-C2N10)SnMe3(H2O)]n (2) as the first example of a metal–organic main-group metal azotetrazolate. Based on our experience with the recently reported triorganotin(IV) pentacyanopropenides [22], we investigated the reaction of Na2AZT⋅5H2O (1) with trimethyltin chloride (molar ratio 1:2) in aqueous solution. Scheme 1 illustrates the synthetic route leading to the title compound [Me3Sn(μ-C2N10)SnMe3(H2O)]n (2) [23]. The yellow reaction mixture obtained by combining aqueous solutions of the starting materials afforded bright yellow crystals of 2 upon standing at room temperature for 24 h. The isolated yield of 2 after recrystallization from a minimum amount of hot water was 61%. The compound was characterized by IR, NMR, and elemental analysis. A 1H NMR spectrum measured in D2O showed only one singlet at δ 0.47 ppm attributable to the methyl groups at tin. The corresponding methyl resonance in the 13 C NMR spectrum was found at δ 148 ppm, while the single carbon atom of the tetrazolyl rings gives rise to a peak at δ 173 ppm. The IR spectrum displays two medium strong bands at 1374 and 1406 cm − 1 resulting from the asymmetric N–C =N stretching vibration, while the band 735 cm − 1 can be assigned to the asymmetric C–N =N stretch of the azo group. These values are in good agreement with those reported in the literature [9,16,24]. In contrast to the NMR data, which suggested the formation of a symmetrically substituted species, the elemental analysis indicated the presence of a hydrate, which was not surprising in view of the fact that compound 2 was crystallized from water. Thus unambiguous
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R. Deblitz et al. / Inorganic Chemistry Communications 18 (2012) 57–60
Scheme 1. Synthesis of Na2AZT (1).
Scheme 2. Preparation of [Me3Sn(μ-C2N10)SnMe3(H2O)]n (2).
structural characterization was only possible by means of an X-ray diffraction study (Scheme 2). Bright yellow X-ray quality single-crystals of 2 were grown directly from the reaction mixture (Fig. 1) [25]. Fig. 2 depicts the supramolecular chain structure of 2, while the crystal packing is illustrated in Figs. 3 and 4. In good agreement with the elemental analysis data, the X-ray structural analysis confirmed the presence of a hydrated species in the solid state. However, instead of the symmetrically substituted compound (μ-C2N10)[Me3Sn(H2O)]2, only one water molecule is added per formula unit, resulting in a novel supramolecular structure of 2 in the crystal. An unusual structural feature is the presence of two
Fig. 1. Crystals of 2 obtained directly from the reaction mixture.
different coordination environments around tin. The coordination geometry around both Sn atoms is trigonal–bipyramidal with the three methyl groups in the equatorial positions. Surprisingly, however, the trigonal–bipyramidal coordination geometry around Sn1 arises from coordination of two tetrazole rings of opposing AZT 2 − dianions, whereas Sn2 is coordinated by only one tetrazole N atom and one water molecule. This results in the formation of an unexpected zigzag chain structure in the solid state with the H2O ligands terminating every alternating corner of the zig-zag chain. Both hydrogen atoms of the coordinated water molecules are engaged in O–H⋅⋅⋅N to different azotetrazolate dianions, leading to an interlocking of the zig-zag chain in a zipper-like overall crystal structure (Figs. 3 and 4). Bond lengths and angles in the AZT 2 − units are unexceptional and very similar to other structurally characterized azotetrazolates [9–13]. The N = N distance in the AZT 2 − ligands in 2 is 1.254 Å. All Sn–C and Sn–N distances are also in good agreement with literature values [26–35]. For initial safety testing, the impact and friction sensitivity of the new azotetrazolate 2 was tested according to established BAM methods [1] using the BAM drophammer and BAM friction tester as well as a simple combustion test. Despite its fairly low nitrogen content of only 27.48% compound 2 was found to be sensitive to both impact and friction. Combustion was vigorous and accompanied by a strong evolution of smoke. Long-term stability tests over a period of 30 days showed no changes in the data listed in Table 1. In summarizing the results reported here, first metal–organic azotetrazolate, [Me3Sn(μ-C2N10)SnMe3(H2O)]n (2), has been prepared in a straightforward manner and structurally characterized by X-ray diffraction. In the solid state, compound 2 comprises an unusual zipper-
R. Deblitz et al. / Inorganic Chemistry Communications 18 (2012) 57–60
59
Fig. 2. Supramolecular chain structure of 2 in the crystal showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
like supramolecular structure. Initial testing revealed that the title compound is sensitive to shock and friction despite its fairly low nitrogen-content. Acknowledgments This work was financially supported by the Otto-von-GuerickeUniversität Magdeburg. Appendix A. Supplementary material Crystallographic data for the crystal structure reported in this paper can be obtained from the Cambridge Crystallographic Data Center, 12 Union Road, Cambridge CB21EZ, UK (fax: +44-1223336-033; e-mail: [email protected] or http://www.ccdc.cam. ac.uk/) by referring to the CIF deposition code CCDC-821604 (2). Supplementary data to this article can be found online at doi:10.1016/j. inoche.2012.01.009.
References [1] T.M. Klapötke, Chemistry of High-Energy Materials, Walter de Gruyter, Berlin/ New York, 2011 (and references cited therein). [2] U.R. Nair, S.N. Asthana, A.S. Rao, B.R. Gandhe, Def. Sci. J. 60 (2010) 137. [3] M. Göbel, T.M. Klapötke, Adv. Funct. Mater. 19 (2009) 347. [4] D.M. Badgujar, M.B. Talawar, S.N. Asthana, P.P. Mahulikar, J. Hazard. Mater. 151 (2008) 289. [5] B.M. Rice, E.F.C. Byrd, W.D. Mattson, Struct. Bond. 125 (2007) 153 (High Density Materials). [6] H. Oestmark, S. Walin, P. Goede, Cent. Eur. J. Energetic Mater. 4 (2007) 83. [7] J. Thiele, Liebigs Annalen der Chemie 303 (1898) 57. [8] G. Singh, R. Prajapati, R. Fröhlich, J. Hazard. Mater. 118 (2005) 75. [9] A. Hammerl, G. Holl, T.M. Klapötke, P. Mayer, H. Nöth, H. Piotrowski, M. Warchhold, Eur. J. Inorg. Chem. (2002) 834 (and references cited therein). [10] Z.-J. Yan, B.-J. Jiao, S.-L. Gao, Yingyong Huaxue 26 (2009) 483. [11] G.-H. Tao, B. Twamley, J. Shreeve, Inorg. Chem. 48 (2009) 9918. [12] G. Steinhauser, G. Giester, C. Wagner, N. Leopold, J.H. Sterba, B. Lendl, M. Bichler, Helv. Chim. Acta 92 (2009) 1371. [13] B.-J. Jiao, Z.-J. Yan, G. Fan, S.-P. Chen, S.-L. Gao, Acta Cryst E: Structure Reports Online E66 (2010) m1374. [14] A. Hammerl, T.M. Klapötke, H. Nöth, M. Warchhold, G. Holl, M. Kaiser, U. Ticmanis, Inorg. Chem. 40 (2001) 3570.
Fig. 3. Crystal packing of 2.
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R. Deblitz et al. / Inorganic Chemistry Communications 18 (2012) 57–60
Fig. 4. Different view of the crystal packing of 2.
Table 1 Energetic properties of 2. Compound
2
M (g/mol) ρ, g/cm3 Impact/Nm Friction Sensitivity (N) Combustion Test N content (%) Ω (%)
509.73 1.900 10 >216 Combustion 27.48 − 87.45
[15] A. Hammerl, M.A. Hiskey, G. Holl, T.M. Klapötke, K. Polborn, J. Stiersdorfer, J.J. Weigand, Chem. Mater. 17 (2005) 3784. [16] R.P. Singh, R.D. Verma, D.T. Meshri, J.M. Shreeve, Angew. Chem. 118 (2006) 3664 (and references cited therein). [17] T.M. Klapötke, C.M. Sabaté, Chem. Mater. 20 (2008) 1750. [18] G. Bentivoglio, G. Laus, V. Kahlenberg, G. Nauer, H. Schottenberger, Z. Krist. 223 (2008) 425. [19] T.M. Klapötke, C.M. Sabaté, New J. Chem. 33 (2009) 1605. [20] K.F. Warner, R.H. Granholm, J. Energetic Mater. 29 (2011) 1. [21] R. Stollé, J. Prakt. Chem. 134 (1932) 282. [22] Asrial, F. Olbrich, M. Spoida, A. Fischer, F.T. Edelmann, Zeitschrift für Anorganische und Allgemeine Chemie 637 (2011) 190. [23] Synthesis of [Me3Sn(μ-C2N10)SnMe3(H2O)]n (2): Na2AZT⋅ 5H2O (1) (500 mg, 1.7 mmol) [7] was dissolved in a minimum amount of warm (ca. 50 °C) water and combined with an aqueous solution of Me3SnCl (720 mg, 3.6 mmol). Undisturbed standing at room temperature for 24 h afforded bright yellow, rod-like crystals of 2 in 61% yield (530 mg). For further purification, the compound can be recrystallized from hot water. M.p. 210 °C (dec.). Analysis (C8H20N10Sn2O, Mw = 509.73 g/mol): C 18.57 (calcd. 18.85), H 3.74 (3.95), N 27.39 (27.48) %. IR (KBr): νmax 3139 (m), 3000 (m), 2916 (m), 2276 (w), 2142 (w), 1640 (w), 1465 (w), 1407 (m), 1374 (m), 1209 (m), 1194 (m), 1185 (m), 1170 (m), 1097 (w), 1077 (w),
[24] [25]
[26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] [37]
1043 (w), 1004 (w), 918 (w), 787 (vs), 736 (m), 549 (m), 448 (w) cm-1. 1HNMR (20°C, D2O, 400 MHz): δ [ppm] 0.47 (s, 18 H, SnCH3). 13C-NMR (20°C, D2O, 100 MHz): δ [ppm] 158.59 ([N4C-N=N-CN4]2–), 148.78 (SnCH3). CAUTIONARY NOTE: While all hydrates of azotetrazolate salts are generally insensitive to shock and friction, the title compound 2 has been found to be sensitive to both impact and friction (cf. Table 1). Thus proper safety equipment is necessary and the compound should be handled with utmost care and only in small amounts. T.M. Klapötke, K. Karaghiosoff, P. Mayer, A. Penger, J.M. Welch, Propellants Explosives Pyrotech 31 (2006) 188. The X-ray diffraction data for compound 2 were measured at − 130 °C on a Stoe IPDS diffractometer. Structure solution and refinement were carries out using the programs SHELXS-97 [36] and SHELXL-97 [37]. Crystal data for 2: C8H20N10OSn2, M = 509.73, monoclinic, space group P21/c, T = 143(2) K, a = 6.5738(3), b = 13.0947(4), c = 20.7033(9) Å, V = 1782.17(12) Å3, Z = 2, Dc = 1.900 g cm− 3, a total of 17162 reflections were collected, 4778 of which were unique (Rint = 0.0450), final R1 = 0.0265 for I>2σ(I), wR2 = 0.0594 for all data, GOOF = 1.057. R.G. Swisher, J.F. Vallano, V. Chandrasekhar, R.O. Day, R.R. Holmes, Inorg. Chem. 23 (1984) 3147. J.F. Vallano, R.O. Day, D.N. Rau, V. Chandrasekhar, R.R. Holmes, Inorg. Chem. 23 (1984) 3153. M. Gielen, R. Willem, M. Biesemans, M. Boualam, A. El Khloufi, D. de Vos, Appl. Organomet. Chem. 6 (1992) 287. E.R.T. Tiekink, Appl. Organomet. Chem. 5 (1991) 1; E.R.T. Tiekink, Trends Organomet. Chem. 1 (1994) 71. V. Chandrasekhar, R. Boomishankar, A. Steiner, J.F. Bickley, Organometallics 22 (2003) 3342. C. Ma, Y. Han, R. Zhang, D. Wang, Eur. J. Inorg. Chem. (2005) 1649. V. Chandrasekhar, P. Thilagar, T. Senapati, Eur. J. Inorg. Chem. (2007) 1004. M. Moya-Cabrear, V. Jancik, R. Cea-Olivares, Tin Chem. (2008) 231. I. Haiduc, E.R.T. Tiekink, J. Zuckerman-Schpector, Tin Chem. (2008) 392. M. Zia-ur-Rehman, S. Niaz, S. Shuja, S. Ali, I.S. Butler, A. Meetsma, M. Khan, Polyhedron 28 (2009) 3439. G.M. Sheldrick, SHELXL-97 Program for Crystal Structure Refinement, Universität Göttingen, Germany, 1997. G.M. Sheldrick, SHELXS-97 Program for Crystal Structure Solution, Universität Göttingen, Germany, 1997.
Contents lists available at SciVerse ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
Synthesis and supramolecular structure of [Me3Sn(μ-C2N10)SnMe3(H2O)]n, the first metal–organic azotetrazolate Raik Deblitz a, Cristian G. Hrib b, Georg Plenikowski a, Frank T. Edelmann b,⁎ a b
Nammo Germany GmbH, Wilhelm-Dümling-Str. 12, 39218 Schönebeck, Germany Chemisches Institut der Otto-von-Guericke-Universität Magdeburg, 39106 Magdeburg, Germany
a r t i c l e
i n f o
Article history: Received 27 October 2011 Accepted 9 January 2012 Available online 16 January 2012 Keywords: Energetic compounds Azotetrazolate dianion Tin Organotin compounds X-ray structure.
a b s t r a c t The first metal–organic azotetrazolate, [Me3Sn(μ-C2N10)SnMe3(H2O)]n (2), was prepared in 61% isolated yield by the reaction of disodium azotetrazolate (Na2AZT⋅5H2O, 1) with 2 equivalents of Me3SnCl in aqueous solution. An X-ray diffraction study revealed a novel supramolecular structure of 2 in the crystal. Two different coordination environments around tin result in the formation of an unexpected zig-zag chain structure in the solid state with H2O ligands coordinated to every second Sn atom ligands terminating the alternating corners of the zig-zag chain. Both hydrogen atoms of the coordinated water molecules are engaged in O–H⋅⋅⋅N to different azotetrazolate dianions, leading to an interlocking of the zig-zag chain in a zipper-like overall crystal structure. Despite its fairly low nitrogen content of only 27.48% the title compound was found to be sensitive to both impact and friction. © 2012 Elsevier B.V. All rights reserved.
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 very useful as propellants, explosives, and pyrotechnics [1–6]. Notable among the most promising recent developments in the chemistry of HEDM's are compounds that combine a high nitrogen content (molecular nitrogen forms the major component of the decomposition products) with a high heat of formation and insensitivity to shock, friction, and electrostatic discharge. Particularly useful in this respect are salts of the azo2− tetrazolate dianion, (C2N10 , =AZT 2 −). The disodium salt (Na2AZT⋅ 5H2O, 1) is the most readily accessible azotetrazolate described in the literature. It represents the most important starting material for all other known azotetrazolate derivatives. Na2AZT⋅ 5H2O (1) was first prepared by Thiele more than 100 years ago by oxidation of aminotetrazole with potassium permanganate in boiling sodium hydroxide solution (Eq. (1)) [7,8]. This rather brutal method produces disodium azotetrazolate as its pentahydrate in the form of large, bright yellow crystals. By now, numerous metal salts of azotetrazolate have been synthesized and studied as potential initial explosives [9–13]. An innovative approach in this field is the use of various nitrogen-based cations such as ammonium, hydrazinium, guanidinium, aminoguanidinium, diaminoguanidinium, or triaminoguanidinium, which give rise to energetic compounds with a very high nitrogen content in the range from 78.8% for the bis(guanidinium) derivative to 85.2% for the bis(hydrazinium) salt [14–20]. Also
⁎ Corresponding author. Tel.: + 49 391 6718327; fax: + 49 391 6712933. E-mail address: [email protected] (F.T. Edelmann). 1387-7003/$ – see front matter © 2012 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2012.01.009
known are a few covalent azotetrazolates such as 1,1'- and 2,2'-dimethylazotetrazolate [9,21]. Surprisingly, it appears that no metal–organic main-group or organotransition metal derivatives of the AZT dianion have thus far been reported in the literature. We describe here the synthesis and structural characterization of [Me3Sn(μ-C2N10)SnMe3(H2O)]n (2) as the first example of a metal–organic main-group metal azotetrazolate. Based on our experience with the recently reported triorganotin(IV) pentacyanopropenides [22], we investigated the reaction of Na2AZT⋅5H2O (1) with trimethyltin chloride (molar ratio 1:2) in aqueous solution. Scheme 1 illustrates the synthetic route leading to the title compound [Me3Sn(μ-C2N10)SnMe3(H2O)]n (2) [23]. The yellow reaction mixture obtained by combining aqueous solutions of the starting materials afforded bright yellow crystals of 2 upon standing at room temperature for 24 h. The isolated yield of 2 after recrystallization from a minimum amount of hot water was 61%. The compound was characterized by IR, NMR, and elemental analysis. A 1H NMR spectrum measured in D2O showed only one singlet at δ 0.47 ppm attributable to the methyl groups at tin. The corresponding methyl resonance in the 13 C NMR spectrum was found at δ 148 ppm, while the single carbon atom of the tetrazolyl rings gives rise to a peak at δ 173 ppm. The IR spectrum displays two medium strong bands at 1374 and 1406 cm − 1 resulting from the asymmetric N–C =N stretching vibration, while the band 735 cm − 1 can be assigned to the asymmetric C–N =N stretch of the azo group. These values are in good agreement with those reported in the literature [9,16,24]. In contrast to the NMR data, which suggested the formation of a symmetrically substituted species, the elemental analysis indicated the presence of a hydrate, which was not surprising in view of the fact that compound 2 was crystallized from water. Thus unambiguous
58
R. Deblitz et al. / Inorganic Chemistry Communications 18 (2012) 57–60
Scheme 1. Synthesis of Na2AZT (1).
Scheme 2. Preparation of [Me3Sn(μ-C2N10)SnMe3(H2O)]n (2).
structural characterization was only possible by means of an X-ray diffraction study (Scheme 2). Bright yellow X-ray quality single-crystals of 2 were grown directly from the reaction mixture (Fig. 1) [25]. Fig. 2 depicts the supramolecular chain structure of 2, while the crystal packing is illustrated in Figs. 3 and 4. In good agreement with the elemental analysis data, the X-ray structural analysis confirmed the presence of a hydrated species in the solid state. However, instead of the symmetrically substituted compound (μ-C2N10)[Me3Sn(H2O)]2, only one water molecule is added per formula unit, resulting in a novel supramolecular structure of 2 in the crystal. An unusual structural feature is the presence of two
Fig. 1. Crystals of 2 obtained directly from the reaction mixture.
different coordination environments around tin. The coordination geometry around both Sn atoms is trigonal–bipyramidal with the three methyl groups in the equatorial positions. Surprisingly, however, the trigonal–bipyramidal coordination geometry around Sn1 arises from coordination of two tetrazole rings of opposing AZT 2 − dianions, whereas Sn2 is coordinated by only one tetrazole N atom and one water molecule. This results in the formation of an unexpected zigzag chain structure in the solid state with the H2O ligands terminating every alternating corner of the zig-zag chain. Both hydrogen atoms of the coordinated water molecules are engaged in O–H⋅⋅⋅N to different azotetrazolate dianions, leading to an interlocking of the zig-zag chain in a zipper-like overall crystal structure (Figs. 3 and 4). Bond lengths and angles in the AZT 2 − units are unexceptional and very similar to other structurally characterized azotetrazolates [9–13]. The N = N distance in the AZT 2 − ligands in 2 is 1.254 Å. All Sn–C and Sn–N distances are also in good agreement with literature values [26–35]. For initial safety testing, the impact and friction sensitivity of the new azotetrazolate 2 was tested according to established BAM methods [1] using the BAM drophammer and BAM friction tester as well as a simple combustion test. Despite its fairly low nitrogen content of only 27.48% compound 2 was found to be sensitive to both impact and friction. Combustion was vigorous and accompanied by a strong evolution of smoke. Long-term stability tests over a period of 30 days showed no changes in the data listed in Table 1. In summarizing the results reported here, first metal–organic azotetrazolate, [Me3Sn(μ-C2N10)SnMe3(H2O)]n (2), has been prepared in a straightforward manner and structurally characterized by X-ray diffraction. In the solid state, compound 2 comprises an unusual zipper-
R. Deblitz et al. / Inorganic Chemistry Communications 18 (2012) 57–60
59
Fig. 2. Supramolecular chain structure of 2 in the crystal showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
like supramolecular structure. Initial testing revealed that the title compound is sensitive to shock and friction despite its fairly low nitrogen-content. Acknowledgments This work was financially supported by the Otto-von-GuerickeUniversität Magdeburg. Appendix A. Supplementary material Crystallographic data for the crystal structure reported in this paper can be obtained from the Cambridge Crystallographic Data Center, 12 Union Road, Cambridge CB21EZ, UK (fax: +44-1223336-033; e-mail: [email protected] or http://www.ccdc.cam. ac.uk/) by referring to the CIF deposition code CCDC-821604 (2). Supplementary data to this article can be found online at doi:10.1016/j. inoche.2012.01.009.
References [1] T.M. Klapötke, Chemistry of High-Energy Materials, Walter de Gruyter, Berlin/ New York, 2011 (and references cited therein). [2] U.R. Nair, S.N. Asthana, A.S. Rao, B.R. Gandhe, Def. Sci. J. 60 (2010) 137. [3] M. Göbel, T.M. Klapötke, Adv. Funct. Mater. 19 (2009) 347. [4] D.M. Badgujar, M.B. Talawar, S.N. Asthana, P.P. Mahulikar, J. Hazard. Mater. 151 (2008) 289. [5] B.M. Rice, E.F.C. Byrd, W.D. Mattson, Struct. Bond. 125 (2007) 153 (High Density Materials). [6] H. Oestmark, S. Walin, P. Goede, Cent. Eur. J. Energetic Mater. 4 (2007) 83. [7] J. Thiele, Liebigs Annalen der Chemie 303 (1898) 57. [8] G. Singh, R. Prajapati, R. Fröhlich, J. Hazard. Mater. 118 (2005) 75. [9] A. Hammerl, G. Holl, T.M. Klapötke, P. Mayer, H. Nöth, H. Piotrowski, M. Warchhold, Eur. J. Inorg. Chem. (2002) 834 (and references cited therein). [10] Z.-J. Yan, B.-J. Jiao, S.-L. Gao, Yingyong Huaxue 26 (2009) 483. [11] G.-H. Tao, B. Twamley, J. Shreeve, Inorg. Chem. 48 (2009) 9918. [12] G. Steinhauser, G. Giester, C. Wagner, N. Leopold, J.H. Sterba, B. Lendl, M. Bichler, Helv. Chim. Acta 92 (2009) 1371. [13] B.-J. Jiao, Z.-J. Yan, G. Fan, S.-P. Chen, S.-L. Gao, Acta Cryst E: Structure Reports Online E66 (2010) m1374. [14] A. Hammerl, T.M. Klapötke, H. Nöth, M. Warchhold, G. Holl, M. Kaiser, U. Ticmanis, Inorg. Chem. 40 (2001) 3570.
Fig. 3. Crystal packing of 2.
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Fig. 4. Different view of the crystal packing of 2.
Table 1 Energetic properties of 2. Compound
2
M (g/mol) ρ, g/cm3 Impact/Nm Friction Sensitivity (N) Combustion Test N content (%) Ω (%)
509.73 1.900 10 >216 Combustion 27.48 − 87.45
[15] A. Hammerl, M.A. Hiskey, G. Holl, T.M. Klapötke, K. Polborn, J. Stiersdorfer, J.J. Weigand, Chem. Mater. 17 (2005) 3784. [16] R.P. Singh, R.D. Verma, D.T. Meshri, J.M. Shreeve, Angew. Chem. 118 (2006) 3664 (and references cited therein). [17] T.M. Klapötke, C.M. Sabaté, Chem. Mater. 20 (2008) 1750. [18] G. Bentivoglio, G. Laus, V. Kahlenberg, G. Nauer, H. Schottenberger, Z. Krist. 223 (2008) 425. [19] T.M. Klapötke, C.M. Sabaté, New J. Chem. 33 (2009) 1605. [20] K.F. Warner, R.H. Granholm, J. Energetic Mater. 29 (2011) 1. [21] R. Stollé, J. Prakt. Chem. 134 (1932) 282. [22] Asrial, F. Olbrich, M. Spoida, A. Fischer, F.T. Edelmann, Zeitschrift für Anorganische und Allgemeine Chemie 637 (2011) 190. [23] Synthesis of [Me3Sn(μ-C2N10)SnMe3(H2O)]n (2): Na2AZT⋅ 5H2O (1) (500 mg, 1.7 mmol) [7] was dissolved in a minimum amount of warm (ca. 50 °C) water and combined with an aqueous solution of Me3SnCl (720 mg, 3.6 mmol). Undisturbed standing at room temperature for 24 h afforded bright yellow, rod-like crystals of 2 in 61% yield (530 mg). For further purification, the compound can be recrystallized from hot water. M.p. 210 °C (dec.). Analysis (C8H20N10Sn2O, Mw = 509.73 g/mol): C 18.57 (calcd. 18.85), H 3.74 (3.95), N 27.39 (27.48) %. IR (KBr): νmax 3139 (m), 3000 (m), 2916 (m), 2276 (w), 2142 (w), 1640 (w), 1465 (w), 1407 (m), 1374 (m), 1209 (m), 1194 (m), 1185 (m), 1170 (m), 1097 (w), 1077 (w),
[24] [25]
[26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] [37]
1043 (w), 1004 (w), 918 (w), 787 (vs), 736 (m), 549 (m), 448 (w) cm-1. 1HNMR (20°C, D2O, 400 MHz): δ [ppm] 0.47 (s, 18 H, SnCH3). 13C-NMR (20°C, D2O, 100 MHz): δ [ppm] 158.59 ([N4C-N=N-CN4]2–), 148.78 (SnCH3). CAUTIONARY NOTE: While all hydrates of azotetrazolate salts are generally insensitive to shock and friction, the title compound 2 has been found to be sensitive to both impact and friction (cf. Table 1). Thus proper safety equipment is necessary and the compound should be handled with utmost care and only in small amounts. T.M. Klapötke, K. Karaghiosoff, P. Mayer, A. Penger, J.M. Welch, Propellants Explosives Pyrotech 31 (2006) 188. The X-ray diffraction data for compound 2 were measured at − 130 °C on a Stoe IPDS diffractometer. Structure solution and refinement were carries out using the programs SHELXS-97 [36] and SHELXL-97 [37]. Crystal data for 2: C8H20N10OSn2, M = 509.73, monoclinic, space group P21/c, T = 143(2) K, a = 6.5738(3), b = 13.0947(4), c = 20.7033(9) Å, V = 1782.17(12) Å3, Z = 2, Dc = 1.900 g cm− 3, a total of 17162 reflections were collected, 4778 of which were unique (Rint = 0.0450), final R1 = 0.0265 for I>2σ(I), wR2 = 0.0594 for all data, GOOF = 1.057. R.G. Swisher, J.F. Vallano, V. Chandrasekhar, R.O. Day, R.R. Holmes, Inorg. Chem. 23 (1984) 3147. J.F. Vallano, R.O. Day, D.N. Rau, V. Chandrasekhar, R.R. Holmes, Inorg. Chem. 23 (1984) 3153. M. Gielen, R. Willem, M. Biesemans, M. Boualam, A. El Khloufi, D. de Vos, Appl. Organomet. Chem. 6 (1992) 287. E.R.T. Tiekink, Appl. Organomet. Chem. 5 (1991) 1; E.R.T. Tiekink, Trends Organomet. Chem. 1 (1994) 71. V. Chandrasekhar, R. Boomishankar, A. Steiner, J.F. Bickley, Organometallics 22 (2003) 3342. C. Ma, Y. Han, R. Zhang, D. Wang, Eur. J. Inorg. Chem. (2005) 1649. V. Chandrasekhar, P. Thilagar, T. Senapati, Eur. J. Inorg. Chem. (2007) 1004. M. Moya-Cabrear, V. Jancik, R. Cea-Olivares, Tin Chem. (2008) 231. I. Haiduc, E.R.T. Tiekink, J. Zuckerman-Schpector, Tin Chem. (2008) 392. M. Zia-ur-Rehman, S. Niaz, S. Shuja, S. Ali, I.S. Butler, A. Meetsma, M. Khan, Polyhedron 28 (2009) 3439. G.M. Sheldrick, SHELXL-97 Program for Crystal Structure Refinement, Universität Göttingen, Germany, 1997. G.M. Sheldrick, SHELXS-97 Program for Crystal Structure Solution, Universität Göttingen, Germany, 1997.