A reaction between sulfur(IV) oxide and aqueous N(2hydroxyethyl)ethylenediamine yields
onium sulfite of composition (HOCH2CH2NH2CH2CH2NH3)SO3 ⋅ H2O, which has been characterized by
Xray diffraction, IR spectroscopy, and mass spectrometry. The threedimensional structure of the salt is stabilized by numerous hydrogen bonds, such as NH⋅⋅⋅O and OH⋅⋅⋅O

Baumer, V. N.

Ennan, A. A.

Gelmboldt, V. O.

Khoma, R. E.

Puzan, A. N.

Rakipov, I. M.

Shishkin, O. V.

English

Odessa National Medical University Institutional Repository

ISSN 00360236, Russian Journal of Inorganic Chemistry, 2014, Vol. 59, No. 6, pp. 541–544. © Pleiades Publishing, Ltd., 2014.Original Russian Text © R.E. Khoma, V.O. Gelmboldt, O.V. Shishkin, V.N. Baumer, A.N. Puzan, A.A. Ennan, I.M. Rakipov, 2014, published in Zhurnal Neorganicheskoi Khimii,2014, Vol. 59, No. 6, pp. 716–719.541N(2hydroxyethyl)ethylenediamine (HEEDA)and its derivatives are used as fuel additives [1], chelating agents [2], epoxy hardeners, emulsifiers, detergents, corrosion inhibitors [3], surfactants [4], andcomonomers in the production of polyester materialscontacting with food, enzymes, and flavorings [5]. Inreactions with acids, HEEDA can be protonated atboth primary and secondary amino groups; and acetate and formate salts of HEEDA manifest the properties of ionic liquids [6].Ethanolammonium onium sulfites and hydrosulfites of unctuous consistency have been synthesizedand spectrally characterized by us earlier [7, 8]. Thefact that the structurally studied organic sulfites areexhausted by tetramethylguanidinium hydrosulfite [9]and aminoguanidinium sulfite monohydrate [10]seems to be due to the ease for the sulfites to convertinto sulfates as a result of “autooxidation” [11, 12].In this work, we have studied the structure andspectral characteristics of N(2hydroxyethyl)ethylenediammonium sulfite monohydrate(HOCH2CH2NH2CH2CH2NH3)SO3 ⋅ H2O (I), thenew onium sulfite produced in a reaction between sulfur(IV) oxide and aqueous HEEDA.EXPERIMENTALSynthesis of compound I. A solution ofN(hydroxymethyl)ethylenediamine (0.05 mol) inwater (20 mL) was poured into a temperaturecontrolled cell, and gaseous SO2 was passed through it at0°С at a rate of 50 mL/min until pH < 1.0 was attained.The solution was allowed to stand at a temperature<15°С in air until water vaporized. The separated colorless crystalline product I (10.04 g; yield, 98.3%) was notsubjected to any additional purification.Nitrogen, carbon, and hydrogen were determinedon a CHN elemental analyzer; sulfur was determinedby the Schôniger method [13].For C4H16N2O5S, anal. calcd. (%): C, 23.52; N,13.72; S, 15.70; H, 7.90.Found (%): C, 22.81; N, 13.34; S, 16.41; H, 8.09.IR spectra were recorded on a PerkinElmer Spectrum BX II FTIR System spectrometer (range:4000–350 cm–1; KBr pellets).Electronimpact (EI) mass spectra were taken onan MX1321 mass spectrometer (direct injection;energy of ionizing electrons: 70 eV).Fast atom bombardment (FAB) mass spectra weretaken on a VG 7070 mass spectrometer (ions were desorbed from a liquid matrix using a beam of argonatoms with an energy of 8 keV).EI mass spectrum of m/z = 87, I = 6%; m/z = 75,I = 11%; [MHEEDA–CH2OH + H]+ (m/z = 74, I =56%); m/z = 65, I = 6%; [SO2]+ (m/z = 64, I = 14%);m/z = 57, I = 41%; m/z = 56, I = 24%; m/z = 45, I =52%; m/z = 46, I = 9%; m/z = 43, I = 10%; m/z = 34,I = 12%; m/z = 32, I = 100%; m/z = 30, I = 92%. Thecharacteristics of HEEDA fragmentation products inSynthesis and Structure of N(Hydroxyethyl)ethylenediammonium Sulfite MonohydrateR. E. Khomaa, b, V. O. Gelmboldtc, O. V. Shishkind, e, V. N. Baumerd, e, A. N. Puzand, A. A. Ennana, and I. M. Rakipovfa Physicochemical Institute for Human and Environment Protection, Ministry of Education and Science of Ukraine,National Academy of Sciences of Ukraine, ul. Preobrazhenskaya 3, Odessa, 65026 Ukraineb Mechnikov National University, ul. Dvoryanskaya 2, Odessa, 65025 Ukrainec Odessa National Medical University, per. Valikhovskiy 2, Odessa, 65026 Ukrained Institute for Single Crystals, National Academy of Sciences of Ukraine, pr. Lenina 60, Kharkiv, 61178 Ukrainee Kharkiv National University, pl. Svobody 4, Kharkiv, 61077 Ukrainef Bogatskii Physicochemical Institute, National Academy of Sciences of Ukraine,Lustdorfskaya doroga 86, Odessa, 65080 Ukraineemail: rek@onu.edu.ua, r_khoma@farlep.netReceived December 2, 2013Abstract—A reaction between sulfur(IV) oxide and aqueous N(2hydroxyethyl)ethylenediamine yieldsonium sulfite of composition (HOCH2CH2NH2CH2CH2NH3)SO3 ⋅ H2O, which has been characterized byXray diffraction, IR spectroscopy, and mass spectrometry. The threedimensional structure of the salt is stabilized by numerous hydrogen bonds, such as NH⋅⋅⋅O and OH⋅⋅⋅O.DOI: 10.1134/S0036023614060096COORDINATION COMPOUNDS542RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 6  2014KHOMA et al.the mass spectrum of compound I and the tabulatedHEEDA mass spectrum [14] are in good agreement.FAB mass spectrum (solution of compound I in3nitrobenzyl alcohol (m/z = 154, I = 100%): [2M +S–2H]+ dimer (m/z = 238, I = 78%); fragment ionsm/z = 165, I = 11%; m/z = 130, I = 8%; m/z = 124,I = 18%; m/z = 115, I = 20%; m/z = 107, I = 35%;m/z = 106, I = 31%; m/z = 90, I = 38%; m/z = 89, I =48%; m/z = 88, I = 16%; m/z = 77, I = 45%; m/z = 76,I = 16%; m/z = 69, I = 12%; m/z = 68, I = 25%; m/z =55, I = 19%.Xray diffraction analysis was performed on anOxford Diffraction Xcalibur 3 diffractometer (MoKαradiation, graphite monochromator, Sapphire3 CCDdetector). The structure was solved and refined usingthe SHELX97 software suite [15]. Hydrogen atomswere found from a difference Fourier synthesis andrefined in the isotropic approximation with overallthermal correction.Selected crystallographic data and refinementdetails for the structure of compound I are the following: C4H16N2O5S, monoclinic crystals, Mr = 204.25,recording at T = 293(2) K, space group P21/n, a =6.8684(11) Å, b = 5.2264(11) Å, c = 26.358(5) Å, β =91.756(14)°, V = 945.7(3) Å3, Z = 4, ρ = 1.434 g/cm3,μ = 0.334 mm–1; F(000) = 440, crystal size 0.40 ×0.20 × 0.1 mm (λ(MoKα) = 0.71073 Å), transmittancecoefficients Тmin/Тmax = 0.8780/0.9674; –8 ≤ h ≤ 5, –6 ≤k ≤ 6, ⎯32 ≤ l ≤ 28; ωscanning at 3.04° ≤ θ ≤ 25.99°;4906 measured reflections, of which 1821 reflectionsare independent (Rint = 0.0505) and 1557 reflectionsare observed with Ihkl > 2σ(I); coverage: 97.3%; fullmatrix refinement on F2, the final reliability values forthe observed reflections RF = 0.0377, wR2 = 0.0944(RF = 0.0498, wR2 = 0.1008 for all independent reflections), S = 0.967, Δρmin/Δρmax = –0.300/0.419 e/Å3.RESULTS AND DISCUSSIONThe structure of compound I was proved by singlecrystal Xray diffraction. The numbering of atoms andthe ellipsoids of thermal vibrations in the independentO(1)S(1)O(3)O(2)N(2)C(4)C(3)N(1)C(2)C(1)O(4)O(5)Fig. 1. Numbering of the basal atoms and the ellipsoids of thermal vibrations in the structure of compound I (50% probability).Table 1. Bond lengths and bond angles in the structure of compound IBond d, Å Bond d, Å Bond d, ÅS(1)–O(1) 1.5178(13) O(4)–C(1) 1.415(3) N(2)–C(4) 1.487(2)S(1)–O(2) 1.5219(13) N(1)–C(2) 1.481(2) C(1)–C(2) 1.495(3)S(1)–O(3) 1.5312(13) N(1)–C(3) 1.484(2) C(3)–C(4) 1.500(3)Angle ω, deg Angle ω, degO(1)S(1)O(2) 105.65(7) O(4)C(1)C(2) 112.95(17)O(1)S(1)O(3) 103.40(6) N(1)C(2)C(1) 111.82(16)O(2)S(1)O(3) 103.87(7) N(1)C(3)C(4) 112.81(15)C(2)N(1)C(3) 113.73(14) N(2)C(4)C(3) 112.89(15)RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 6  2014SYNTHESIS AND STRUCTURE 543cell part are shown in Fig. 1. Bond lengths and bondangles formed by nonhydrogen atoms in the structureare listed in Table 1. The independent cell part is builtof a C4H14N2O2+ cation, an  sulfite ion, and awater molecule. The packing of these basal units formsa network of hydrogen bonds in the crystal structure(Table 2). The hydrogen atoms that are bonded to oxygen or nitrogen atoms participate in the formation ofhydrogen bonds in the structure. The terminal ammonium group (N(2) atom) forms hydrogen bonds withthree nearestneighboring sulfite ions; the NH2 group(N(1) atom) forms hydrogen bonds with two sulfiteions, and its bond with one of these ions is forklike(Table 3). Water molecules form hydrogen bonds withthe hydroxy group of the cation and also with eachother. The network of hydrogen bonds observed in thestructure of compound І is threedimensional (Fig. 2).The results of analyzing the IR spectrum of compound I are given in Table 3; the assignment of vibrations was performed using published data [16–18].The intense absorption bands with smeared maxima at 3401 and 3014 cm–1 in the IR spectrum of compound I were assigned to the ν(ОН) and ν(NH)stretching vibrations of the onium cation and the watermolecules that participate in the network of hydrogenbonds. The νas,s( ) stretching vibrations of thepyramidal  anion appeared as a series of mediumintensity bands at 1004, 983, 966, and 920 cm–1, whichwere absent in the spectrum of HEEDA. The band ofδs( ) bending vibrations seemed to be incorporated into the complex intense band at 619 cm–1. Theδd( ) doubly degenerated outofplane bendingvibrations were identified in the form of lowintensitybands at 516 and 487 cm–1.23−SO23−SO 23−SO23−SO23−SO23−SOHence, the reaction product in SО2–HOCH2CH2NHCH2CH2NH2–H2O solutions isN(2hydroxyethyl)ethylenediammonium sulfite monohydrate (HOCH2CH2NH2CH2CH2NH3)SO3 ⋅ H2O,whose threedimensional structure is stabilized by anetwork of hydrogen bonds with the participation ofall the “active” hydrogen atoms of the onium cation.The effects of hydrogen bonds obviously result in theTable 2. Parameters of D–H···A hydrogen bonds in the structure of compound ID–H···A contactDistance, ÅDHA angle, deg Atom A coordinatesD–H H…A D…AO(5)–H(5B)···O(5) 0.78(2) 2.17(2) 2.938(2) 173(3) –x + 3/2, y – 1/2, –z + 1/2O(4)–H(4C)···O(2) 0.74(2) 1.92(2) 2.644(2) 170(2) x, y, zO(5)–H(5A)···O(4) 0.84(2) 1.95(2) 2.782(2) 171(2) x, y, zN(1)–H(1C)···O(3) 0.86(2) 1.88(2) 2.711(2) 160(2) x, y, zN(1)–H(1D)···O(1) 0.77(2) 2.07(2) 2.8236(19) 168(2) x, y + 1, zN(1)–H(1D)···O(3) 0.77(2) 2.50(2) 3.038(2) 128.9(19) x, y + 1, zN(2)–H(2C)···O(3) 0.88(2) 1.91(2) 2.784(2) 172(2) x, y, zN(2)–H(2D)···O(1) 0.99(2) 1.84(2) 2.784(2) 160.1(17) –x, –y, –zN(2)–H(2E)···O(2) 0.85(2) 1.89(2) 2.742(2) 175(2) x – 1, y, zTable 3. Wavenumbers (cm–1) of absorption band maximain the IR spectra of HEEDA and compound IHEEDA [16] Assignment I3170 m2828 sν(NH), ν(OH) 3401 vs. b.3014 vs. b.1602 m δ(NH2), δ(HOH), δ(CNH) 1624 s1453 m1359 mδ(CNH), ν(CN) 1496 m1454 m1329 wω(NH) 1234 w1178 m1127 s1054 vsν(CO), ν(CN), ρ(NH2), δ(CNH)1125 vsνas, s(S1004 m983 m966 m920 m771 s ω(NH2) 783 wδs(S  ρ(NH2), γ(H2O)663 sh619 vsτ(NH2), δ(CNH), δ(CN3) 579 wδd(S516 w487 wδ stands for scissoring, δd for outofplane, ω for wagging, τ fortwisting, ρ for rocking, and γ for librational vibrations.O32)O32–),O32–)544RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 6  2014KHOMA et al.observed distortions of the pyramidal geometry of thesulfite anion in the structure of the complex.REFERENCES1. J. L. Dever, M. C. Menon, S. D. Phillips, and L. J. Baldwin, US Patent 5508356 (1996).2. A. Karadag, H. Pasaoglu, G. Kastas, and O. Büyükgüngör, Zeit. Kristallogr.—Cryst. Mater. 220 (1), 74(2005).3. The Chemical Encyclopedia, Ed. by N. S. Zefirov(Bol’shaya Rossiiskaya Entsiklopediya, Moscow, 1995),p. 147 [in Russian].4. J. A. Krogh, G. N. Taylor, D. S. Treybig, and M. J. Williams, US Patent 6964940 (2005).5. EFSA J. 10, 2653 (2012). doi:10.2903/j.efsa.2012.26536. A. Destegul, J. Mol. Liq. 177, 369 (2013).7. R. E. Khoma, V. O. Gel’mbol’dt, L. V. Koroeva, et al.,Vopr. Khim. Khim. Tekhnol., No. 1, 133 (2012).8. R. E. Khoma, A. A. Ennan, A. V. Mazepa, et al., Vopr.Khim. Khim. Tekhnol., No. 1, 136 (2013).9. D. J. Heldebrant, C. R. Yonker, P. G. Jessop, andL. Phan, Chem.Eur. J. 15, 7619 (2009).10. R. E. Khoma, V. O. Gel’mbol’dt, V. N. Baumer, et al.,Russ. J. Inorg. Chem. 58, 843 (2013).11. R. E. Khoma, A. A. Ennan, O. V. Shishkin, et al., Russ.J. Inorg. Chem. 57, 1559 (2012).12. R. E. Khoma, V. O. Gel’mbol’dt, O. V. Shishkin, et al.,Russ. J. Inorg. Chem. 59, 1 (2014).13. V. A. Klimova, Major Techniques of Organic Analysis(Khimiya, Moscow, 1975) [in Russian].14. G. M. Sheldrick, Acta Crystallogr., Sect. A 64, 112(2008).15. http://webbook.nist.gov/cgi/cbook.cgi?ID=C111411&Mask=200#MassSpec16. http://ihcp.jrc.ec.europa.eu/our_databases/eurlfcmrefcoll/referencesubstances/ft/A130.pdf17. K. Nakamoto, Infrared and Raman Spectra of Inorganicand Coordination Compounds (Interscience, New York,1986).18. E. Pretsch, P. Buhlmann, and C. Affolter, StructureDetermination of Organic Compounds. Tables of Spectral Data (Springer, 2000; Mir, BINOM. Laboratoriyaznanii, Moscow, 2006).Translated by E. Glushachenkova0ab cFig. 2. Network of hydrogen bonds in the structure of compound I (hydrogen atoms are omitted).View publication stats

Synthesis and Structure of N(Hydroxyethyl)ethylenediammonium Sulfite Monohydrate

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Synthesis and Structure of N(Hydroxyethyl)ethylenediammonium Sulfite Monohydrate

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