PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 March 1; 64(Pt 3): o637.
Published online 2008 February 29. doi:  10.1107/S1600536808005229
PMCID: PMC2960766

1-Methyl-1-propyl­pyrrolidinium chloride

Abstract

The aymmetric unit of the title compound, C8H18N+·Cl, consists of one crystallographically independent 1-methyl-1-propyl­pyrrolidinium cation and one chloride anion, both of which lie in general positions. Minor hydrogen-bonded C—H(...)Cl inter­actions occur. However, no classical hydrogen bonding is observed.

Related literature

For bond-length data, see: Allen et al. (1987 [triangle]). For comparative thermal and crystallographic analysis of four crystallized N-alkyl-N-methyl­pyrrolidinium and piperidinium bis­(trifluoro­methane­sulfon­yl)imide salts and an insight into why these salts form room-temperature ionic liquids, see: Henderson et al. (2006 [triangle]). For the synthesis and analysis of N-butyl-N-methyl pyrrolidinium chloride, an analogue of the title compound, see: Lancaster et al. (2002 [triangle]). For the first synthesis and analysis of the new pyrrolidinium family of molten salts, see: MacFarlane et al. (1999 [triangle]). For the quanti­tative comparison of inter­molecular inter­actions using Hirshfeld surfaces, see: McKinnon et al. (2007 [triangle]). For the first synthesis and analysis of 1-alkyl-2-methyl pyrrolidinium ionic liquids involving the bis­(trifluoro­methane­sulfon­yl)imide anion, see: Sun et al. (2003 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o637-scheme1.jpg

Experimental

Crystal data

  • C8H18N+·Cl
  • M r = 163.68
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o637-efi1.jpg
  • a = 14.5863 (5) Å
  • b = 13.2196 (4) Å
  • c = 9.9779 (3) Å
  • V = 1923.99 (11) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.33 mm−1
  • T = 123 (2) K
  • 0.30 × 0.30 × 0.30 mm

Data collection

  • Bruker Kappa APEXII diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.907, T max = 0.907
  • 11550 measured reflections
  • 1982 independent reflections
  • 1800 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.079
  • S = 1.04
  • 1982 reflections
  • 93 parameters
  • H-atom parameters constrained
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: POV-RAY (Persistence of Vision, 2003 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808005229/zl2101sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005229/zl2101Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

PMD is grateful to Monash University for the Monash Graduate Scholarship and Monash International Postgraduate Research Scholarship. The Australian Research Council is thanked for a QEII fellowship for JMP.

supplementary crystallographic information

Comment

The title compound, (I), is commonly used as a precursor in ionic liquid synthesis (MacFarlane et al., 1999, Sun et al., 2003). Pyrrolidinium-based ionic liquids have been a subject of intense investigation recently (Henderson et al., 2006), whereby with understanding of the fundamental molecular-level interactions, a desired product with predicted physico-chemical properites could be designed. Additionally, a particular emphasis has been placed on whether hydrogen bonding occurs between the cation and a potential electron-pair donor (hydrogen bond acceptor) and its influence on the ionic liquids' overall properties. This paper briefly reports the structural determination and analysis of 1-methyl-1-propyl pyrrolidinium chloride (Figure 1).

The bond distances and angles of the pyrrolidinium cation are all within normal ranges (as is tabulated in Allen et al., 1987), with the propyl substituent adopting the energetically preferred anti conformation (torsional angle N1—C6—C7—C8: -177.0 (2) °) and the ring adopting the energetically preferred envelope (Cs) conformation. The extended structure packs in layers of groups of anions and cations (Figure 2) which are interconnected by an extended network of weak hydrogen bonds (C—H···Cl interactions), where each cation is hydrogen bonded to four anions and each anion is weakly hydrogen bonded to four cations [C1—H1B···Cl1i [3.607 (2) Å], C2—H2A···Cl1ii [3.630 (2) Å], C5— H5A ··· Cl1 [3.648 (1) Å], C5—H5C···Cl1iii [3.656 (1) Å], C6—H6A···Cl1i [3.672 (2) Å] and C6— H6B···Cl1 [3.666 (1) Å] (symmetry operators: i=1/2 - x,3/2 - y,1/2 + z; ii=1 - x,y,1/2 - z; iii=x,2 - y,1/2 + z) -see Table 1]. Analysis of the salts' Hirshfeld surface, reveals that the short range inter-cationic H—H intermolecular contact contribution to the Hirshfeld surface area predominates (McKinnon et al., 2007).

Experimental

The compound was synthesized following the procedure of Lancaster et al. (2002) for the analogous N-butyl-N-methyl pyrrolidinium chloride species: 1-methyl-1-propylpyrrolidinium chloride was synthesized by heating a solution of chloropropane (28 ml, 0.315 moles) and methyl pyrrolidine (20 ml, 0.287 moles) in 2-propanol at 323 K under nitrogen for 48 h. The resultant white solid was recrystallized from 2-propanol at 273 K. Crystals resulted after 2 days. Crystals were coated with Paratone N oil (Exxon Chemical Co., TX, USA) immediately after isolation and cooled in a stream of nitrogen vapour on the diffractometer. Melting point: 323.5 K.

Refinement

All H atoms were initially located in a difference Fourier map. Thereafter, all H atoms were placed in geometrically fixed idealized positions and constrained to ride on their parent atoms with C—H distances in the range 0.95–1.00 Å and Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
Diagram of the unique component of (I) shown with 50% thermal ellipsoids and hydrogen atoms as spheres of arbitrary size.
Fig. 2.
Extended packing diagram of the unit-cell contents of (I) as viewed down the b axis.

Crystal data

C8H18N+·ClDx = 1.130 Mg m3
Mr = 163.68Melting point: 323.5 K
Orthorhombic, PbcnMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 4825 reflections
a = 14.5863 (5) Åθ = 2.8–26.4º
b = 13.2196 (4) ŵ = 0.33 mm1
c = 9.9779 (3) ÅT = 123 (2) K
V = 1923.99 (11) Å3Cubic, colourless
Z = 80.30 × 0.30 × 0.30 mm
F000 = 720

Data collection

Bruker X8 APEX KappaCCD diffractometer1982 independent reflections
Radiation source: fine-focus sealed tube1800 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.030
T = 123(2) Kθmax = 26.4º
0.5° frames in [var phi] and ω scansθmin = 2.1º
Absorption correction: multi-scan(SADABS; Bruker, 2005)h = −18→18
Tmin = 0.907, Tmax = 0.907k = −15→16
11550 measured reflectionsl = −11→12

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.079  w = 1/[σ2(Fo2) + (0.0361P)2 + 0.834P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
1982 reflectionsΔρmax = 0.25 e Å3
93 parametersΔρmin = −0.20 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cl10.36024 (2)0.82436 (2)0.05218 (3)0.02423 (12)
N10.32912 (7)0.86923 (8)0.43497 (10)0.0179 (2)
C10.35707 (9)0.75928 (10)0.41992 (14)0.0241 (3)
H1A0.39390.74960.33760.029*
H1B0.30230.71520.41520.029*
C20.41390 (11)0.73488 (12)0.54424 (15)0.0323 (3)
H2A0.47930.72680.52020.039*
H2B0.39220.67140.58630.039*
C30.40131 (10)0.82444 (12)0.64053 (15)0.0309 (3)
H3A0.38840.80040.73260.037*
H3B0.45690.86740.64230.037*
C40.32014 (9)0.88251 (11)0.58455 (13)0.0242 (3)
H4A0.26160.85400.61740.029*
H4B0.32340.95490.60970.029*
C50.40372 (8)0.93610 (10)0.38042 (13)0.0209 (3)
H5A0.40450.93150.28240.031*
H5B0.46310.91410.41610.031*
H5C0.39221.00630.40720.031*
C60.23958 (8)0.88722 (10)0.36358 (13)0.0198 (3)
H6A0.19410.83740.39620.024*
H6B0.24870.87500.26660.024*
C70.20062 (9)0.99281 (11)0.38223 (14)0.0254 (3)
H7A0.19311.00730.47890.031*
H7B0.24331.04340.34420.031*
C80.10858 (10)0.99984 (12)0.31221 (18)0.0372 (4)
H8A0.11730.99260.21530.056*
H8B0.08061.06570.33130.056*
H8C0.06830.94580.34470.056*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.02343 (18)0.02619 (19)0.02308 (18)−0.00399 (13)−0.00151 (13)−0.00178 (12)
N10.0162 (5)0.0191 (5)0.0185 (5)−0.0015 (4)−0.0013 (4)0.0004 (4)
C10.0246 (7)0.0178 (6)0.0299 (7)0.0005 (5)−0.0008 (6)0.0012 (5)
C20.0282 (7)0.0287 (8)0.0401 (9)0.0006 (6)−0.0051 (6)0.0123 (6)
C30.0273 (7)0.0406 (9)0.0247 (7)−0.0068 (6)−0.0067 (6)0.0100 (6)
C40.0232 (6)0.0322 (8)0.0172 (6)−0.0044 (6)−0.0004 (5)−0.0005 (5)
C50.0163 (6)0.0223 (7)0.0241 (6)−0.0031 (5)0.0008 (5)0.0023 (5)
C60.0157 (6)0.0231 (6)0.0206 (6)−0.0019 (5)−0.0035 (5)−0.0014 (5)
C70.0208 (6)0.0257 (7)0.0298 (7)0.0018 (5)−0.0037 (6)−0.0049 (6)
C80.0258 (7)0.0314 (8)0.0543 (10)0.0050 (6)−0.0138 (7)−0.0065 (7)

Geometric parameters (Å, °)

N1—C51.5038 (16)C4—H4B0.9900
N1—C61.5066 (16)C5—H5A0.9800
N1—C41.5085 (16)C5—H5B0.9800
N1—C11.5171 (17)C5—H5C0.9800
C1—C21.526 (2)C6—C71.5185 (18)
C1—H1A0.9900C6—H6A0.9900
C1—H1B0.9900C6—H6B0.9900
C2—C31.536 (2)C7—C81.5163 (19)
C2—H2A0.9900C7—H7A0.9900
C2—H2B0.9900C7—H7B0.9900
C3—C41.518 (2)C8—H8A0.9800
C3—H3A0.9900C8—H8B0.9800
C3—H3B0.9900C8—H8C0.9800
C4—H4A0.9900
C5—N1—C6111.31 (10)N1—C4—H4B111.0
C5—N1—C4110.64 (10)C3—C4—H4B111.0
C6—N1—C4111.98 (10)H4A—C4—H4B109.0
C5—N1—C1109.44 (10)N1—C5—H5A109.5
C6—N1—C1109.72 (10)N1—C5—H5B109.5
C4—N1—C1103.46 (10)H5A—C5—H5B109.5
N1—C1—C2105.54 (11)N1—C5—H5C109.5
N1—C1—H1A110.6H5A—C5—H5C109.5
C2—C1—H1A110.6H5B—C5—H5C109.5
N1—C1—H1B110.6N1—C6—C7114.30 (10)
C2—C1—H1B110.6N1—C6—H6A108.7
H1A—C1—H1B108.8C7—C6—H6A108.7
C1—C2—C3106.30 (12)N1—C6—H6B108.7
C1—C2—H2A110.5C7—C6—H6B108.7
C3—C2—H2A110.5H6A—C6—H6B107.6
C1—C2—H2B110.5C8—C7—C6109.34 (11)
C3—C2—H2B110.5C8—C7—H7A109.8
H2A—C2—H2B108.7C6—C7—H7A109.8
C4—C3—C2104.66 (11)C8—C7—H7B109.8
C4—C3—H3A110.8C6—C7—H7B109.8
C2—C3—H3A110.8H7A—C7—H7B108.3
C4—C3—H3B110.8C7—C8—H8A109.5
C2—C3—H3B110.8C7—C8—H8B109.5
H3A—C3—H3B108.9H8A—C8—H8B109.5
N1—C4—C3103.74 (11)C7—C8—H8C109.5
N1—C4—H4A111.0H8A—C8—H8C109.5
C3—C4—H4A111.0H8B—C8—H8C109.5
C5—N1—C1—C285.97 (12)C1—N1—C4—C340.98 (12)
C6—N1—C1—C2−151.63 (11)C2—C3—C4—N1−33.99 (14)
C4—N1—C1—C2−31.99 (13)C5—N1—C6—C7−63.82 (14)
N1—C1—C2—C310.96 (15)C4—N1—C6—C760.62 (14)
C1—C2—C3—C414.09 (15)C1—N1—C6—C7174.90 (11)
C5—N1—C4—C3−76.14 (13)N1—C6—C7—C8−177.02 (12)
C6—N1—C4—C3159.05 (10)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1B···Cl1i0.992.793.607 (1)141
C2—H2A···Cl1ii0.992.773.630 (2)146
C5—H5A···Cl10.982.773.648 (1)149
C5—H5C···Cl1iii0.982.713.656 (1)163
C6—H6A···Cl1i0.992.763.672 (1)153
C6—H6B···Cl10.992.773.666 (1)151

Symmetry codes: (i) −x+1/2, −y+3/2, z+1/2; (ii) −x+1, y, −z+1/2; (iii) x, −y+2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2101).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–S19.
  • Bruker (2005). APEX2 Bruker AXS Inc., Madison, Wisconsin, USA.
  • Henderson, W. A., Young, V. G., Pearson, W., Passerini, S., De Long, H. C. & Trulove, P. C. (2006). J. Phys. Condens. Matter, 18, 10377–10390.
  • Lancaster, N. L., Salter, P. A., Welton, T. & Young, G. B. (2002). J. Org. Chem.67, 8855–8861. [PubMed]
  • MacFarlane, D. R., Meakin, P., Sun, J., Amini, N. & Forsyth, M. (1999). J. Phys. Chem. B, 103, 4164–4170.
  • McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814–3816. [PubMed]
  • Persistence of Vision (2003). Persistence of Vision Raytracer POV-RAY Persistence of Vision Raytracer Pty Ltd, Victoria, Australia. URL: http://www.povray.org/download/.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sun, J., Forsyth, M. & MacFarlane, D. R. (2003). Electrochim. Acta, 48, 1707–1717.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography