Journal of Crystallography

Volume 2014 (2014), Article ID 219828, 4 pages

http://dx.doi.org/10.1155/2014/219828

Research Article

Synthesis and Crystal Structure of 1-Methyl-3-(2-pyridyl)imidazolium Hexafluorophosphate

Elango Kandasamy

Department of Chemistry, Vel Tech University, Chennai 600062, India

Received 20 December 2013; Revised 12 May 2014; Accepted 13 May 2014; Published 17 July 2014

Academic Editor: Yan Xu

Copyright © 2014 Elango Kandasamy. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract.

Compound 1-Methyl-3-(2-pyridyl)imidazolium hexafluorophosphate was crystallized in monoclinic system with space group and unit cell parameters , , , , and  . The obtained solid state structure of 1-Methyl-3-(2-pyridyl)imidazolium hexafluorophosphate shows CH⋯ F type weak interactions and was analyzed.

1. Introduction

The chemistry of N-heterocyclic carbene (NHC) has become emerged field after the crystal structure of free 1,3-diadamantyl imidazol-2-ylidene was first reported in 1991 by Arduengo III et al. [1–3]. The chemical durability of NHC encouraged the chemist to study their reactivity with inorganic and organic compounds. The synthesis of NHC normally had been done by removal of C-2 proton of imidazolium salt with a suitable base. Many examples of imidazolium salts were synthesized and their corresponding NHC and NHC-metal compounds were studied [4, 5]. The interesting criteria of the imidazole are that, by tuning the substitution on nitrogen center at the imidazole ring, different types of functionalized imidazolium salts have been synthesized [6–9]. Herein, the modified synthesis of 1-Methyl-3-(2-pyridyl)imidazolium hexafluorophosphate (1) and its crystal structure have been discussed.

2. Materials and Methods

A mixture 2-chloropyridine (1.35 g, 10 mmole) and 1-methylimidazole (0.821 g, 10 mmole) were heated at 150°C for 20 hours. To this mixture saturated aqueous solution of KPF₆ was added, while the mixture was hot and it results in the rapid precipitation of white color substance. The obtained white color precipitate was filtrated off and dried in vacuum. The colorless block type crystals of (MeIMPy)(PF₆) were obtained after one week from methanolic solution. Yield (based on 1-methylimidazole): 1.05 g, 34%. Anal. Calcd. for C₉H₁₀N₃F₃P (305.17): C, 35.26; H, 3.42; N, 13.48. Found: C, 35.42; H, 3.30; N, 13.77. ¹H NMR (400 MHz, CD₃OD, 22°C,δ): 3.93 (s, 3H), 7.61 (m, 2H), 7.76 (d, 1H), 8.07 (m, 1H), 8.12 (m, 1H), 8.48 (m, 1H), 9.26 (s, 1H).

2-Chloropyridine (99.0%), 1-methylimidazole (99.0%), and KPF₆ (98.0%) were purchased from Sigma-Aldrich and used as received. ¹H NMR spectra were obtained on a JEOL-JNM LAMBDA 400 model spectrometer operating at 400 MHz. The spectra were recorded in CD₃OD solution, and the chemical shifts were referenced with respect to TMS.

Crystal was coated with light hydrocarbon oil and mounted in the 100 K dinitrogen stream of Bruker SMART APEX CCD diffractometer equipped with CRYO Industries low-temperature apparatus and intensity data were collected using graphite monochromated Mo Kα radiation (). The data integration and reduction were processed with SAINT software [10]. An absorption correction was applied [11]. Structure was solved by the direct method using SHELXS-97 and was refined on F² by full-matrix least-squares technique using the SHELXL-97 software package [12]. Nonhydrogen atoms were refined anisotropically. In the refinement, hydrogen atoms were treated as riding atoms using SHELXL default parameters. The crystallographic figures, except Figure 1, were generated using Diamond 3.1f software. Crystal data and data collection parameters for the compound 1 are given in Table 1. CCDC 851202 contains the supplementary crystallographic data for 1. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/Community/Requestastructure/Pages/DataRequest.aspx.

Table 1: Crystal data and data collection parameters for the compound (MeIMPy)(PF₆).

Identification code
1

Empirical formula
C₉H₁₀N₃F₆P

Formula weight
305.17

Temperature
100(2) K

Crystal system, space group
Monoclinic, 2(1)/

Unit cell dimensions
(8) Å

(16) Å

(11) Å

(2)°

Volume
1162.1(2) Å³

, calculated density
4, 1.744 mg/m³

Absorption coefficient
0.305 mm⁻¹

(000)
616

Crystal size
 mm³

range for data collection
2.40 to 28.31°

Index ranges
, ,

Reflections collected
7402

Independent reflections
2885 [(int) = 0.0189]

Completeness to theta
98.0%

Data/restraints/parameters
2826/0/173

Goodness-of-fit on F²
1.190

Final indices
1 = 0.0446a,  2 = 0.1119

indices (all data)
1 = 0.0592a, 2 = 0.1611b

Largest diff. peak and hole
0.526 and −0.691 e·Å⁻³

,  .

Figure 1: ORTEP drawings of molecular structure of (MeIMPy)(PF₆). The thermal displacement ellipsoids are drawn at the 30% probability.

3. Results and Discussion

1-Methyl-3-(2-pyridyl)imidazolium hexafluorophosphate (MeIMPy)(PF₆) has been synthesized by slight modification from reported procedure [13]. The 2-chloropyridine and 1-methylimidazole were heated for 20 hours with neat condition. During the course of reaction, the reaction mixture slowly turned into brown viscous liquid. When the reaction mixture was in hot condition, saturated solution of KPF₆ was added. Immediately, white color precipitate appeared. The precipitates were filtered and dried in high vacuum. The precipitates were filtered and dried in high vacuum (Scheme 1).

Scheme 1: Synthesis of (MeIMPy)(PF₆).

¹H-NMR of 1-Methyl-3-(2-pyridyl)imidazolium hexafluorophosphate (MeIMPy)(PF₆) has been recorded in deuterated methanol (CD₃OD). The spectra of (MeIMPy)(PF₆) show resonance peak at 9.26 ppm for –CH of 2-position of imidazolium ring and 3.93 ppm for –CH ₃. The NMR spectral analysis matches the reported NMR values (recorded in CD₃CN) and supports the molecular structure of (MeIMPy)(PF₆).

Single crystals of 1 were grown in methanolic solution at room temperature and a suitable crystal was subjected to the X-ray structural analysis. The crystal data reveals that the compound 1 crystallizes in the monoclinic system and centrosymmetric space group . The solid state structure of 1 consists of one cation and one anion (Figure 1). The unit cell contains four of each cation and anion. The important bond lengths and bond angles are shown in Tables 2 and 3.

Table 2: Bond distances and angles of hexafluorophosphate unit.

Bond distances (Å)

P(1)–F(1)
1.608(2)
P(1)–F(4)
1.606(2)

P(1)–F(2)
1.591(2)
P(1)–F(5)
1.599(2)

P(1)–F(3)
1.597(2)
P(1)–F(6)
1.603(2)

Bond angles (°)

F(2)–P(1)–F(3)
90.40(11)
F(3)–P(1)–F(5)
90.11(11)

F(2)–P(1)–F(4)
90.75(12)
F(6)–P(1)–F(1)
89.59(9)

F(4)–P(1)–F(1)
179.26(11)
F(3)–P(1)–F(1)
90.22(9)

F(5)–P(1)–F(1)
89.72(10)
F(6)–P(1)–F(4)
90.21(9)

F(2)–P(1)–F(1)
89.96(11)
F(3)–P(1)–F(4)
89.98(10)

F(5)–P(1)–F(4)
89.57(11)
F(3)–P(1)–F(6)
179.69(11)

F(2)–P(1)–F(5)
179.40(11)
F(5)–P(1)–F(6)
89.64(10)

F(2)–P(1)–F(6)
89.85(10)

Table 3: Bond distances and angles of 1-Methyl-3-(2-Pyridyl)imidazolium unit.

Bond distances (Å)

N(1)–C(2)
1.321(3)
N(3)–C(3)
1.323(3)

N(1)–C(1)
1.470(3)
N(3)–C(4)
1.343(3)

N(2)–C(8)
1.379(3)
C(3)–C(7)
1.388(4)

C(8)–C(9)

1.355(4)
C(6)–C(7)
1.383(4)

N(2)–C(2)
1.341(3)
C(4)–C(5)
1.386(4)

N(2)–C(3)
1.438(3)
C(5)–C(6)
1.382(4)

N(1)–C(9)
1.374(3)

Bond angles (°)

N(1)–C(2)–N(2)
108.3(2)
C(2)–N(1)–C(9)
109.1(2)

C(2)–N(2)–C(8)
108.7(2)
C(2)–N(2)–C(3)
124.1(2)

C(9)–C(8)–N(2)
106.6(2)
N(3)–C(3)–N(2)
114.2(2)

C(8)–C(9)–N(1)
107.3(2)
C(8)–N(2)–C(3)
127.2(2)

In the anion unit, the bond distances between phosphorous and fluorine atom are shown in the range of 1.590(19)  to 1.608(17)  and the bond angles suggest that the anion unit is almost perfect octahedron (Table 2). From the cation unit, the bond angle between (N1-C1-N2 108.3(2)°) is similar to a typical bond angle of imidazolium unit and it is in plane. The pyridyl ring has slightly twisted from plane of imidazolium moiety.

The solid state structure of 1 shows that the cations and anions are connected through intermolecular CH⋯ F type hydrogen bond interaction (Table 4). Each cation unit is hydrogen bonded to five separate anion units (Figure 2). CH⋯ F interaction between C2 position of five membered imidazolium rings and F4, C8 position of pyridyl moiety and F1 results in the 1D supramolecular polymer chains (Figures 3 and 4).

Table 4: Details of inter- and intramolecular hydrogen bond.

D–H⋯A
H⋯A Å
D–H⋯A°
D⋯A Å

C8H8⋯F1
2.31
171.17(18)
3.257(4)

C7H7⋯F2
2.66
121.27(18)
3.260(4)

C6H6⋯F2
2.62
123.89(19)
3.260(4)

C2H2⋯F4
2.27
150.07(19)
3.135(4)

C5H5⋯F4
2.52
132.72(17)
3.243(3)

C4H4⋯F5
2.60
124.51(18)
3.243(3)

C5H5⋯F5
2.59
123.27(18)
3.216(4)

Figure 2: CH⋯ F interactions in (MeIMPy)(PF₆).

Figure 3: 1D supramolecular polymer chain in (MeIMPy)(PF₆).

Figure 4: The unit cell packing of crystal of (MeIMPy)(PF₆), viewed along a-axis.

4. Summary

The solid state structure of 1-Methyl-3-(2-pyridyl)imidazolium hexafluorophosphate has been discussed by using single crystal X-ray diffraction study. The different types of CH⋯ F supramolecular interaction and the formation of 1D supramolecular polymer chain between cation and anion unit by CH⋯ F weak interaction of titled compound have been investigated.

Conflict of Interests

The author declares that there is no conflict of interests regarding the publication of this paper.

Acknowledgments

Dr. Elango Kandasamy acknowledges the DST-SERB, for financial support, Department of Chemistry, Indian Institute of Technology Kanpur for single crystal X-ray facilities, and Vel Tech Dr. RR & Dr. SR Technical University for infrastructure.

References

H. W. Wanzlick, “Aspects of nucleophilic carbene chemistry,” Angewandte Chemie International Edition, vol. 1, no. 2, pp. 75–80, 1962.

K. Öfele, “Tetracarbonylbis(1,3-dimethyl-4-imidazolin-2-ylidene)chromium(0),” Angewandte Chemie International Edition, vol. 9, no. 9, pp. 739–740, 1970.

A. J. Arduengo III, R. L. Harlow, and M. Kline, “A stable crystalline carbene,” Journal of the American Chemical Society, vol. 113, no. 1, pp. 361–363, 1991.

V. Nair, S. Bindu, and V. Sreekumar, “N-heterocyclic carbenes: reagents, not just ligands!,” Angewandte Chemie, vol. 43, no. 39, pp. 5130–5135, 2004.

E. A. B. Kantchev, C. J. O'Brien, and M. G. Organ, “Palladium complexes of N-heterocyclic carbenes as catalysts for cross-coupling reactions—a synthetic chemist's perspective,” Angewandte Chemie, vol. 46, no. 16, pp. 2768–2813, 2007.

F. E. Hahn and M. C. Jahnke, “Heterocyclic carbenes: synthesis and coordination chemistry,” Angewandte Chemie, vol. 47, no. 17, pp. 3122–3172, 2008.

P. L. Arnold and I. J. Casely, “F-block N-heterocyclic carbene complexes,” Chemical Reviews, vol. 109, no. 8, pp. 3599–3611, 2009.

O. Kuhl, Functionalised N-Heterocyclic Carbene Complexes, Wiley-InterScience, New York, NY, USA, 2010.

L. Benhamou, E. Chardon, G. Lavigne, S. Bellemin-Laponnaz, and V. César, “Synthetic routes to N-heterocyclic carbene precursors,” Chemical Reviews, vol. 111, no. 4, pp. 2705–2733, 2011.

SAINT+, 6.02 ed, Bruker AXS, Madison, Wis, USA, 1999

G. M. Sheldrick, SADABS 2.0, University of Göttingen, Göttingen, Germany, 2000.

G. M. Sheldrick, “A short history of SHELX,” Acta Crystallographica A: Foundations of Crystallography, vol. 64, part 1, pp. 112–122, 2008.

V. J. Catalano and A. O. Etogo, “Luminescent coordination polymers with extended Au(I)-Ag(I) interactions supported by a pyridyl-substituted NHC ligand,” Journal of Organometallic Chemistry, vol. 690, no. 24-25, pp. 6041–6050, 2005.