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Sep 24, 2015 - Keywords: diethylnicotinamidium, hydrogen bond, perchlorate, structure, IR spectra. Heterocyclic nitrogen ..... cations and lead to the for-.

Chemical Papers 62 (5) 536–540 (2008) DOI: 10.2478/s11696-008-0058-3


Preparation and characterization of diethylnicotinamidium perchlorate Iveta Ondrejkovičová*, Dušan Mikloš, Silvia Štefániková Department of Inorganic Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology, SK-812 37 Bratislava, Slovakia Received 6 November 2007; Revised 13 February 2008; Accepted 5 March 2008

Dedicated to Professor Milan Melník on the occasion of his 70th birthday The title compound is the first example of N,N  -diethylnicotinamidium, [denaH]+ , salt which has been characterized by X-ray analysis and IR spectra. [denaH]ClO4 was obtained from the reaction mixture prepared from N,N  -diethylnicotinamide (dena) and Fe(ClO4 )3 in ethanol without any addition of HClO4 . The proton required for protonation of dena is produced by hydrolysis of aquairon(III) cations. In the crystal structure, cations and anions are held together by ionic interactions. The cations are linked to each other by pyridinium–carbonyl N—H· · ·O— —C hydrogen bonds and an infinite linear chain along axis a is formed. c 2008 Institute of Chemistry, Slovak Academy of Sciences  Keywords: diethylnicotinamidium, hydrogen bond, perchlorate, structure, IR spectra

Heterocyclic nitrogen compounds play a significant role in many biological systems, especially derivatives of pyridine being a component of several vitamins and drugs. Therefore, many derivatives of pyridine, their pyridinium salts, and metal complexes have been investigated (Allen, 2002; Myers, 1984; Bell et al., 1986; Cakir et al., 2006). In recent years, derivatives of pyridine such as nicotinamide (nia), diethylnicotinamide (dena), and their protonated forms ([niaH]+ and [denaH]+ ) have been studied extensively because of their potential pharmaceutical applications (Boschi-Muller et al., 1997; Wiederkehr & Scartazzini, 1982; Elkharraz et al., 2006; Athimoolam & Natarajan, 2007a, 2007b, 2007c). Nicotinamide (vitamin PP) is used as an antipelargic and antihyperlipidemic agent. Diethylnicotinamide (cardiamine) serves as an efficient stimulator of the CNS and as a component of drugs used in the treatment of brain cancer. It has been found that the compounds containing [niaH]+ and [denaH]+ have antibiotic activity and can be used for combating infections.

The basic character of the nitrogen atom of the pyridine ring makes it easily protonated. Nicotinamidium, [niaH]+ , occurs in many bio systems and forms nicotinamidium salts [niaH]X, where X− is an anion of an acid (Athimoolam & Natarajan, 2007a, 2007b, 2007c; Nurakhmetov et al., 1988; Gubin et al., 1988, 1989, 1991, 1992; Pacigová et al., 2007; Bulut et al. 2003; Koman et al., 2003; Adams et al., 2005). In literature, [niaH]X salts are often rewritten to their hydroacidic form as nia·HX (Nurakhmetov et al., 1988; Gubin et al., 1988, 1989, 1991, 1992). The nicotinamidium salts are usually prepared by a reaction of nia with the respective acid (HX). For the nicotinamidium salts, formation of several types of hydrogen bonds is characteristic. [niaH]+ has three potential sites for hydrogen-bonding interactions, viz. the pyridine N atom, the amide N atom, and the carbonyl O atom. These cations can be interconnected through N—H· · ·O hydrogen bonds involving the –CONH2 groups (Athimoolam & Natarajan, 2007a, 2007b, 2007c; Gubin et al., 1988; Pacigová et

*Corresponding author, e-mail: [email protected]

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I. Ondrejkovičová et al./Chemical Papers 62 (5) 536–540 (2008)

Table 1. Elemental analysis and IR spectra of [denaH]ClO4 wi (calc.)/% wi (found)/% Sample

[denaH]ClO4 I II


C10 H15 N2 O5 Cl

IR Spectra, ν ˜ /cm−1






43.01 43.21 43.23

5.38 5.28 5.51

10.05 9.97 10.06

2663 ν(=NH+ ) 1596, 1562 ν(C— —N) (from pyridine ring) 1093, 622 ν(ClO− 4 )

Table 2. Crystal data and structure refinement for [denaH]ClO4 (C10 H15 N2 O)+ ClO− 4

Formula Molecular mass, MW Temperature/K Wavelength/˚ A Crystal system/space group Unit cell dimensions

278.69 293(2) 0.71073 Triclinic/P -1 a = 6.995(2) ˚ A α = 100.35(1)◦ ˚ b = 8.213(2) A β = 93.37(2)◦ c = 12.055(2) ˚ A γ = 105.90(2)◦ 650.9(3) 2/1.422 0.308 0.2 × 0.2 × 1.05 2.63–29.99 –1 ≤ h ≤ 9, –11 ≤ k ≤ 11, –16 ≤ l ≤ 16 4615/3761 [R(int) = 0.0207] Full-matrix least-squares on F 2 3761/46/212 1.008 R1 = 0.0600, R2 = 0.1900 0.286 and –0.342

Unit cell volume/˚ A3 Z/Calculated density/(Mg m−3 ) Absorption coefficient/mm−1 Crystal size/mm Theta range for data collection/◦ Limiting indices Reflections collected/unique Refinement method Data/restraints/parameters Accuracy of fit on F 2 Final R indices [I > 2σ(I)] Largest diffraction peak and hole/(e ˚ A−3 )

al., 2007; Bulut et al. 2003; Koman et al., 2003). Other hydrogen bonds can be formed by the amide H atoms and the pyridine H atoms of the [niaH]+ cations, respectively, and by the O atoms of the oxoacids anions, e.g. (Athimoolam & Natarajan, 2007a, 2007b, 2007c; Gubin et al., 1988, 1992; Pacigová et al., 2007; Bulut et al. 2003; Koman et al., 2003). There are also examples of N—H· · ·Cl hydrogen bonds between amide H atoms of [niaH]+ and Cl atoms of the anions (Gubin et al., 1989; Adams et al., 2005). Some salts contain other types of hydrogen bonds, too. To the best of our knowledge, the N,N  -diethylnicotinamidium cation and free dena have not yet been characterized by X-ray structural analysis (Allen, 2002). From our point of view, it was challenging to study interactions between several bio derivatives of pyridine with iron cations also occurring in living systems (Galková & Ondrejkovičová, 2007; Fargašová et al., 2005). In this study, our attention has been focused on interactions between iron(III) perchlorate and dena. Ethanol was purified before use by standard methods. All other chemicals were purchased commercially and used without further purification. [denaH]ClO4

was prepared according to the following procedure: to a solution of Fe(ClO4 )3 · 11H2 O (1.10 g; 2.00 mmol) in ethanol (5 cm3 ), a solution of dena (1.35 cm3 ; 8.00 mmol) in ethanol (5 cm3 ) was slowly added. The resulting mixture was heated under reflux for 4 h. Then, the hot mixture containing a red-brown solid (Fe2 O3 · x H2 O) was filtered. The filtrate was cooled down to 20 ◦C and the precipitate was filtered off and recrystallized from ethanol. Crystals were obtained as colourless needles (sample I). [denaH]ClO4 was also prepared from acetonitrile solutions according to the same procedure (sample II). Samples I and II were characterized (Table 1) by elemental analysis (Flash EA 1112 analyzer) and IR spectra (Nicolet Magna 750 FTIR spectrophotometer), and sample I also by X-ray analysis. Diffraction data for [denaH]ClO4 were collected on a Siemens P4 single crystal diffractometer at room temperature. Details on data collection and structure refinement are given in Table 2. The structure was solved by direct methods using SHELXS97 (Sheldrick, 1998) and refined with SHELXL-97 (Sheldrick, 1997). The ClO− 4 anions exhibit disorder and, therefore, they were placed in calculated positions, and refined using a “riding” model although all

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I. Ondrejkovičová et al./Chemical Papers 62 (5) 536–540 (2008)

Fig. 1. An ORTEP-3 (Farrugia, 1997) view of two [denaH]+ cations and two ClO− 4 anions, illustrating the formation of infinite

chains of [denaH]+ cations by hydrogen bonds and rotational disorder of ClO− 4 . Thermal ellipsoids are drawn at the 30 % probability level.

Table 3. Selected bond lengths/˚ A and angles/◦ for [denaH]ClO4 C1—N2 N2—C3 C3—C4 C4—C5 C5—C6 C6—C1 C6—C7 C7—O8 C7—N9 N9—C11 N9—C13 C11—C12 C13—C14

1.333(3) 1.327(3) 1.371(4) 1.378(4) 1.392(3) 1.382(3) 1.499(3) 1.247(3) 1.330(3) 1.477(3) 1.471(3) 1.501(5) 1.519(4)

C1—N2—C3 N2—C3—C4 C3—C4—C5 C4—C5—C6 C5—C6—C1 C1—C6—C7 C5—C6—C7 C6—C7—O8 C6—C7—N9 C7—N9—C11 C7—N9—C13 N9—C11—C12 N9—C13—C14

123.2(2) 119.5(2) 119.2(2) 120.3(2) 117.8(2) 123.2(2) 118.8(2) 116.4(2) 120.7(2) 117.5(2) 125.3(2) 113.1(3) 112.8(3)

hydrogen atoms could be found from the difference electron density maps to keep the refinement stable. Geometrical analysis of the structure was performed using SHELXL-97 (Sheldrick, 1997). The bond lengths and angles are given in Table 3. A new salt, [denaH]ClO4 , obtained from the reaction mixture prepared from N,N  -diethylnicotinamide (dena) and iron(III) perchlorate, is presented in this study; sample I was obtained from ethanol and sample II from acetonitrile solutions (Table 1). Formation of the salt took place without any addition of perchloric or other acids. The proton required for the protonation of dena, was produced by the hydrolysis of cations [Fe(H2 O)6 ]3+ occurring in hydrates of iron(III) perchlorate, Fe(ClO4 )3 · x H2 O (where x is usually 10–12)

2+ + − → [Fe(H2 O)6 ]3++H2 O − ← − − [Fe(H2 O)5 (OH)] +H3 O (1)

In the next step, dena was protonated and the salt formed (Eq. 2) H3 O+ + ClO− 4 + dena → [denaH]ClO4 + H2 O


Similar protonation was observed in systems containing iron(III) perchlorate or iron(III) sulfate and derivatives of pyridine (Boča et al., 2004, 2002). Hydrolysis is also possible in ethanol solutions because the hydrates of Fe(III) salts contain enough water necessary for this reaction. Water molecules coordinated in [Fe(H2 O)6 ]3+ cations are difficult to be exchange by ethanol molecules (Boča et al., 2002). [denaH]ClO4 (Fig. 1) crystallizes in the triclinic system, space group P -1. The structure consists of [denaH]+ cations and ClO− 4 anions which are held together by ionic interactions. The ClO− 4 anions exhibit rotational disorder, as approximated by two ClO− 4 tetrahedral, refined with bond distances and angles restrained to values near the usual ones. The Cl—O distances range from 1.366(1) ˚ A to 1.446(11) ˚ A, the O—C—O angles from 104.6(10)◦ to 115.0(12)◦. The occupation factor for one anion was refined to 0.66(3), for the other to 0.34(3). There is also a hydrogen bond between the pyridine nitrogen atom N2 of one cation and the carbonyl oxygen atom O8 (N2a—H· · ·O8 of 2.666 ˚ A with N2a—H of 0.860 ˚ A and the angle N2a— H· · ·O8 of 174.4◦) of a neighboring [denaH]+ cation, and the corresponding equivalent hydrogen bonds in-

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I. Ondrejkovičová et al./Chemical Papers 62 (5) 536–540 (2008)


salt (where nia = nicotinamide) (Nurakhmetov et al., 1988). Acknowledgements. This work was supported by the Science and Technology Assistance Agency under the contract No. APVT-20-005504 and by the grant VEGA of the Ministry of Education of the Slovak Republic and the Slovak Academy of Science, No. 1/4454/07.


Fig. 2. Infrared spectrum of [denaH]ClO4 .

terconnect two [denaH]+ cations and lead to the formation of an infinite linear chain (Fig. 1) along axis a. No hydrogen bonds to oxygen atoms of the ClO− 4 anions were detected. The probable reason for that is that unlike in [niaH]+ cations, [denaH]+ cations exhibit only two sites potentially suitable for the formation of hydrogen bonds both being involved in forming the above mentioned chain. Consequently, the anions are not hindered in their almost free rotation around the central Cl atom, as indicated by large anisotropic thermal ellipsoids (Fig. 1). The rotational disorder is also the probable cause of slightly higher R-factors. As expected, the pyridine ring is planar (with the rms deviation of its atoms from the LSQ plane of 0.0104 ˚ A) with C—C distances ranging from 1.37 ˚ A to 1.39 ˚ A, C—N distances of 1.33 ˚ A, and inner angles near 120◦ except for C1—N2—C3 showing the slightly greater value of 123.2(2)◦ . Also the structural fragment consisting of C6—C7—O8—N9—C11—C13 atoms is planar (with the rms deviation of 0.065 ˚ A), but the corresponding LSQ planes contain an angle of 48.65(8)◦. This rotation around the C6—C7 bond, which may be characterized also by torsion angles (e.g. C1—C6—C7—O8 of –131.3(2)◦ and C1—C6—C7— N9 of 47.2(3)◦ ), is obviously caused by the hydrogen bond. The ethyl groups are pointing to the same side of the latter plane. All typical features of the IR spectrum (Table 1, Fig. 2) and the structure of [denaH]ClO4 are in obvious agreement. IR spectrum shows bands at 1093 cm−1 and 622 cm−1 characteristic of an ion-bonded ClO4 group (Nakamoto, 1997). Other bands, at 2663 cm−1 ν(=NH+ ) and 1596 cm−1 , 1562 cm−1 (ν(C—N), from the pyridine ring), confirm the presence of the diethylnicotinamidium cation (Pouchert, 1975). In the IR spectrum of the analogous salt [niaH]ClO4 , similar bands were observed at 2660 cm−1 and 2530 cm−1 ν(=NH+ ), and at 1605 cm−1 and 1595 cm−1 (ν(C—N), from the pyridine ring) confirming the presence of the nicotinamidium cation [niaH]+ in this

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