untitled European Journal of Chemistry 2 (3) (2011) 314‐316 European Journal of Chemistry ISSN 2153‐2249 (Print) / ISSN 2153‐2257 (Online)  2011 EURJCHEM DOI:10.5155/eurjchem.2.3.314‐316.307 European Journal of Chemistry Journal homepage: www.eurjchem.com Crystal structure of N,N,N',N'‐tetramethylethylenediammonium dinitrate Zaouali Zgolli Donia*, Hbib Boughzala and Ahmed Driss Laboratoire des Matériaux et Cristallochimie, Département de chimie, Faculté des Sciences, El Manar, Tunis, TN‐2092, Tunisie *Corresponding author at: Laboratoire des Matériaux et Cristallochimie, Département de chimie, Faculté des Sciences, El Manar, Tunis, TN‐2092, Tunisie. Tel.: +216.98.458337; fax: +216.71.871666. E‐mail address: donia_zgolli@hotmail.com (Z. Donia). ARTICLE INFORMATION ABSTRACT Received: 15 November 2010 Received in revised form: 19 December 2010 Accepted: 19 December 2010 Online: 30 September 2011 KEYWORDS N,N,N',N'‐tetramethylethylenediammonium dinitrate has been synthesized. The crystal and molecular structure of the title compound has been determined from single crystal X‐ray diffraction data. C6H18N4O6, M =242.24, Triclinic, a = 6.040(2) Å, b = 6.834(3) Å, c = 7.867(2) Å, α = 74.1120(10)°, β = 83.700(2)°, γ = 80.314(2)°, V = 307.12(19) Å3, T = 298(2) K, space group P‐1 (no. 2), Z = 1, μ(Mo‐Kα) = 0.115, 2383 reflections measured, 1342 unique (Rint = 0.0169) which were used in all calculations. The final wR(F2) was 0.1262 (all data). In the title compound, C6H18N22+.2NO3‐, both N atoms of the cationic moiety are protonated and linked via hydrogen bonds to two trigonal planar nitrate anions. Two types of classical hydrogen bonds are observed: N1‐H…O1 and N1‐H…O2. These bonds link the cations and the anions together, forming a one‐dimensional network and reinforcing the cohesion of the ionic structure. N,N,N',N'‐tetramethylethylenediammonium dinitrate Single crystal structure Organic‐inorganic Synthesis Characterization Hydrogen‐bond 1. Introduction Due to their application in many fields of chemistry, the preparation of nitrogen‐containing ligands is still of great interest in synthetic chemistry. Recent investigations have proved the direct deprotonation of methylamines to be a synthetically very useful method for functionalizations and thus for the synthesis of nitrogen ligands [1‐3]. In addition, it is well known that organic amines, such as ethylenediamine, 1,3‐ propanediamine, N,N,N',N'‐tetramethylethylenediamine and piperazine have been widely used as structure‐directing agents for the construction of novel supramolecular assemblies [4,5]. Here, a new member of this family, N,N,N',N'‐tetramethylethyl enediammoniume dinitrate, I, is presented. The synthesis and structure of the title compound is presented here (Scheme 1). H3C N N CH3 CH3 CH3 H H 2+ 2 NO3 - Scheme 1 2. Experimental 2.1. Synthesis N,N,N',N'‐Tetramethylethylenediamine (TMEDA) (0.076 mol) and an equivalent amount of MnCl2.4H2O (1 mol) were dissolved in a mixture of methanol (5 mL) and nitric acid (2 M, 1 mL) and stored at room temperature for two month. After evaporation of the solvent, a crystalline solid which is suitable for X‐ray single crystal structure diffraction studies remained. 2.2. Instrumentation Data were collected using a crystal, size 0.03×0.02×0.01 mm, on an Enraf‐Nonius CAD4 diffractometer. The cell parameters were determined and optimized by least‐squares refinement based on 25 reflections in the range 9°≤  ≤ 15°. The crystal structure was solved and refined using full matrix least squares on F2. All calculations were performed using the SHELX‐97 [6] computer programs included in the WinGX software package [7]. Molecular graphics are made with Diamond 2.1 [8]. The relevant crystallographic data for the title compound are listed in Table 1. 3. Results and discussion The molecular structure of N,N,N',N'‐tetramethylethylene diammonium dinitrate is depicted in Figure 1. Selected bond lengths and angles of the title compound are presented in Table 2 and 3, respectively. Atomic coordinates and equivalent isotopic displacement parameters for non‐hydrogen atoms of the title compound are given in Table 4. Figure 1. The molecular structure of the title compound. Thermal ellipsoids are shown at the 50% probability level. Donia et al. / European Journal of Chemistry 2 (3) (2011) 314‐316 315 Table 1. Crystal data and structure refinement for the title compound. Empirical formula C6H18N2·2(NO3) Formula weight (g/mol) 242.24 Temperature (°C) 298 (2) Wavelength (Å) 0.71073 Crystal system Triclinic Space group P‐1 Unit cell dimensions a = 6.040 (2) Å b = 6.834 (3) Å c = 7.867 (2) Å α = 74.1120 (10)° β = 83.700 (2)° γ = 80.314 (2)° Volume 307.12 (19) Å3 Z 1 Density (calculated) (Mg m−3) 1.310 Absorption coefficient (mm−1) 0.115 F(000) 130 Crystal size (mm3) 0.03 × 0.02 × 0.01 Theta range for data collection ° 2.70 to 26.96° Index ranges ‐7  h  5 ‐8  k  8 ‐10  l  10 Reflections collected 2383 Independent reflections 1342 [R(int) = 0.0169] Absorption correction psi‐scan Max. and min. transmission 0.999 and 0.997 Refinement method Full‐matrix least‐squares on F2 Data / restraints / parameters 1342/0/80 Goodness‐of‐fit on F2 1.051 Final R indices [I>2sigma(I)] R1= 0.0429, wR2 = 0.1160 R indices (all data) R1= 0.0586, wR2 = 0.1262 Extinction coefficient 0.18 (2) Largest diff. peak and hole (e Å−3) 0.211 and −0.119 Measurement Enraf Nonius CAD4 diffractometer Program system Wingx Structure determination Direct methods (SHELXL‐97, SHELXTL) CCDC 798752 Table 2. Bond lengths for the title compound. Atom‐Atom Bond length/Å N1‐O1 1.248(2) N1‐O2 1.231(2) N1‐O3 1.222(2) N2‐C1 1.496(2) N2‐C2 1.499(2) N2‐C3 1.488(2) C1‐C1i 1.521(3) Symmetry code: (i) −x, −y, −z+1. Table 3. Bond angles for the title compound. Atom-Atom-Atom Bond Angle (°) O2‐N1‐O1 117.28(15) O3‐N1‐O1 119.69(17) O3‐N1‐O2 123.02(18) N2‐C1‐C1i 110.67(16) C1‐N2‐C2 110.83(14) C3‐N2‐C1 112.56(13) C3‐N2‐C2 110.66(13) Symmetry code: (i) −x, −y, −z+1 Table 4. Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Å2x 103) for the title compound. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. Atom x y z U(eq) N1 5332(2) ‐2342(2) 2398(2) 52.9(4) O1 5148(2) ‐1256(3) 3463(2) 75.9(5) O2 3783(3) ‐2062(3) 1425(3) 94.9(6) O3 7012(3) ‐3608(3) 2351(3) 103.8(7) N2 1241(2) 1627(2) 2854.9(17) 42.8(4) C1 218(3) 1111(2) 4715(2) 44.9(4) C2 2288(3) 3554(3) 2466(3) 62.2(5) C3 ‐401(3) 1798(3) 1525(2) 61.4(5) In the title salt, C6H18N2+.2NO3‐, (Figure 1) both N atoms of the cationic moiety are protonated and linked via hydrogen bonds to two trigonal planar nitrate anions. The components lie on centres of symmetry such that the asymmetric unit consists of half of the N,N,N',N'‐tetramethylethylenediammonium cation, which lies across an inversion center (C1‐C1i bond (i: ‐x, ‐y, ‐ z+1)) and nitrate ion. Alternating nitrate anions and cationic ligands are observed parallel to the (010) plane (Figure 2). Figure 2. A projection of the title compound C6H18N22+.2NO3‐(I) along the y direction. The structure is stabilized by two types of hydrogen‐bonding interactions: (N2‐H…O1) and (N2‐H…O2)) contacts (Table 5). Table 5. Hydrogen‐bond geometry (Å, °) D‐H...A d(D‐H) d(H..A) d(D..A)