organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

Pyrrolidinium chloride

aLudwig-Maximilians Universität, Department Chemie und Biochemie, Butenandtstrasse 5–13 (Haus D), 81377 München, Germany
*Correspondence e-mail: kluef@cup.uni-muenchen.de

(Received 29 January 2009; accepted 19 February 2009; online 25 February 2009)

The title compound, C4H10N+·Cl, was obtained as a decomposition product from 2,6-bis­(pyrrolidin­yl)pyridine. The anion lies on the same cristallographic mirror plane as the N atom of the cation, the complete cation being generated by mirror symmetry. The anions and cations are connected by N+—H⋯Cl hydrogen bonds into chains along [100]. The pyrrolidinium cation is puckered in an envelope conformation EN1.

Related literature

For details of the synthesis of 2,6-bis­(pyrrolidin­yl)pyridine, see: Folmer-Anderson et al. (2005[Folmer-Anderson, J. F., Lynch, V. M. & Anslyn, E. V. (2005). Chem. Eur. J. 11, 5319-5326.]). For related structures containing the pyrrolidinium cation, see: Kashino et al. (1978[Kashino, S., Kataoka, S. & Haisa, M. (1978). Bull. Chem. Soc. Jpn, 51, 1717-1722.]); Moritani et al. (1987[Moritani, Y., Sasahara, N., Kashino, S. & Haisa, M. (1987). Acta Cryst. C43, 154-158.]); Jakubas et al. (2005[Jakubas, R., Bednarska-Bolek, B., Zaleski, J., Medycki, W., Holderna-Natkaniec, K., Zielinski, P. & Galazka, M. (2005). Solid State Sci. 7, 381-390.]). For a description of the EN1 conformation of the five-membered ring, see: Cremer & Pople (1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]).

[Scheme 1]

Experimental

Crystal data
  • C4H10N+·Cl

  • Mr = 107.58

  • Orthorhombic, P n m a

  • a = 7.4429 (4) Å

  • b = 9.4104 (5) Å

  • c = 8.9021 (4) Å

  • V = 623.51 (5) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.48 mm−1

  • T = 200 K

  • 0.22 × 0.13 × 0.12 mm

Data collection
  • Nonius KappaCCD diffractometer

  • Absorption correction: none

  • 4239 measured reflections

  • 756 independent reflections

  • 608 reflections with I > 2σ(I)

  • Rint = 0.037

Refinement
  • R[F2 > 2σ(F2)] = 0.040

  • wR(F2) = 0.120

  • S = 1.07

  • 756 reflections

  • 31 parameters

  • H-atom parameters constrained

  • Δρmax = 0.21 e Å−3

  • Δρmin = −0.24 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H101⋯Cl1 0.92 2.17 3.091 (3) 180
N1—H102⋯Cl1i 0.92 2.18 3.097 (2) 177
Symmetry code: (i) [x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}].

Data collection: COLLECT (Nonius, 2004[Nonius (2004). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

The title compound was obtained as a decomposition product. The organic salt is composed of the pyrrolidinium cation and a chloride anion (Fig. 1). The crystal packing is shown in Fig. 2. In the crystal, both H atoms bonded to N1 of the pyrrolidinium cation are involved in hydrogen bonds with chloride as acceptor. Both can be described according to graph set analysis with a D11(2) descriptor on the unitary level. This bonding pattern leads to chains along [1 0 0] which, starting from chloride, can be described according to graph set analysis with a C21(4) descriptor on the binary level. The hydrogen bonding pattern is shown in Fig. 3.

The Cs symmetric five-membered pyrrolidinium ring can be described according to Cremer & Pople (1975) by the puckering parameters q2 = 0.3061 Å and Φ2 = 180.0000. The closest pucker descriptor is an envelope EN1.

Related literature top

For details of the synthesis of 2,6-bis(pyrrolidinyl)pyridine, see: Folmer-Anderson et al. (2005). For related structures containing the pyrrolidinium cation, see: Kashino et al. (1978); Moritani et al. (1987); Jakubas et al. (2005). For a description of the EN1 conformation of the five-membered ring, see: Cremer & Pople (1975).

Experimental top

The title compound was obtained as decomposition product of 2,6-bis(pyrrolidinyl)pyridine, which was synthesized according to Folmer-Anderson et al. (2005), after 4 months at room temperature.

Refinement top

H atoms were placed in calculated positions (C—H = 0.99 Å, N—H = 0.92 Å) and were included in the refinement in the riding model approximation with Uiso(H) = 1.2 Ueq(C/N).

Computing details top

Data collection: COLLECT (Nonius, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the Cs symmetric title compound with anisotropic displacement ellipsoids drawn at 50% probability for non-H atoms. Symmetry code: (i) x, -y + 1/2, z.
[Figure 2] Fig. 2. Packing of the title compound, viewed along [0 1 0].
[Figure 3] Fig. 3. N—H···Cl hydrogen bonds lead to chain-like structures in the crystal structure along [1 0 0], shown here normal to [0 1 0]. Symmetry codes: (i) x + 1/2, -y + 1/2, -z + 1/2; (ii) x - 1/2, -y + 1/2, -z + 1/2; (iii) x - 1, y, z.
Pyrrolidinium chloride top
Crystal data top
C4H10N+·ClF(000) = 232
Mr = 107.58Dx = 1.146 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 2321 reflections
a = 7.4429 (4) Åθ = 3.1–27.5°
b = 9.4104 (5) ŵ = 0.48 mm1
c = 8.9021 (4) ÅT = 200 K
V = 623.51 (5) Å3Block, colourless
Z = 40.22 × 0.13 × 0.12 mm
Data collection top
Nonius KappaCCD
diffractometer
608 reflections with I > 2σ(I)
Radiation source: rotating anodeRint = 0.037
MONTEL, graded multilayered X-ray optics monochromatorθmax = 27.5°, θmin = 3.2°
ϕ and ω scansh = 89
4239 measured reflectionsk = 1212
756 independent reflectionsl = 1110
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0625P)2 + 0.1854P]
where P = (Fo2 + 2Fc2)/3
756 reflections(Δ/σ)max < 0.001
31 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C4H10N+·ClV = 623.51 (5) Å3
Mr = 107.58Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 7.4429 (4) ŵ = 0.48 mm1
b = 9.4104 (5) ÅT = 200 K
c = 8.9021 (4) Å0.22 × 0.13 × 0.12 mm
Data collection top
Nonius KappaCCD
diffractometer
608 reflections with I > 2σ(I)
4239 measured reflectionsRint = 0.037
756 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.120H-atom parameters constrained
S = 1.07Δρmax = 0.21 e Å3
756 reflectionsΔρmin = 0.24 e Å3
31 parameters
Special details top

Refinement. Hydrogen atoms were placed in calculated positions (C–H 0.99 Å for methylene C atoms and N–H 0.92 Å for N atoms) and were included in the refinement in the riding model approximation with U(H) set to 1.2 Ueq(C) for C atoms and 1.2 Ueq(N) for N atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.2072 (3)0.25000.3955 (3)0.0473 (6)
H1010.23410.25000.29460.057*
H1020.08430.25000.40650.057*
C10.3204 (4)0.1712 (3)0.6283 (3)0.0781 (8)
H110.22490.13480.69540.094*
H120.43760.13480.66410.094*
C20.2871 (3)0.1242 (2)0.4702 (3)0.0623 (6)
H210.40090.09630.42080.075*
H220.20320.04270.46770.075*
Cl10.29515 (8)0.25000.05610 (7)0.0488 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0466 (12)0.0500 (13)0.0452 (12)0.0000.0007 (10)0.000
C10.102 (2)0.0775 (16)0.0553 (14)0.0109 (14)0.0060 (13)0.0106 (12)
C20.0803 (16)0.0411 (11)0.0657 (14)0.0045 (10)0.0013 (11)0.0050 (9)
Cl10.0477 (4)0.0528 (4)0.0459 (4)0.0000.0020 (3)0.000
Geometric parameters (Å, º) top
N1—C2i1.482 (3)C1—C21.495 (4)
N1—C21.482 (2)C1—H110.9900
N1—H1010.9200C1—H120.9900
N1—H1020.9200C2—H210.9900
C1—C1i1.482 (5)C2—H220.9900
C2i—N1—C2105.9 (2)C1i—C1—H12110.3
C2i—N1—H101110.5C2—C1—H12110.3
C2—N1—H101110.5H11—C1—H12108.5
C2i—N1—H102110.5N1—C2—C1104.64 (19)
C2—N1—H102110.5N1—C2—H21110.8
H101—N1—H102108.7C1—C2—H21110.8
C1i—C1—C2107.20 (13)N1—C2—H22110.8
C1i—C1—H11110.3C1—C2—H22110.8
C2—C1—H11110.3H21—C2—H22108.9
C2i—N1—C2—C131.4 (3)C1i—C1—C2—N119.16 (18)
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H101···Cl10.922.173.091 (3)180
N1—H102···Cl1ii0.922.183.097 (2)177
Symmetry code: (ii) x1/2, y, z+1/2.

Experimental details

Crystal data
Chemical formulaC4H10N+·Cl
Mr107.58
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)200
a, b, c (Å)7.4429 (4), 9.4104 (5), 8.9021 (4)
V3)623.51 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.48
Crystal size (mm)0.22 × 0.13 × 0.12
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4239, 756, 608
Rint0.037
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.120, 1.07
No. of reflections756
No. of parameters31
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.21, 0.24

Computer programs: COLLECT (Nonius, 2004), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H101···Cl10.922.173.091 (3)179.5
N1—H102···Cl1i0.922.183.097 (2)177.4
Symmetry code: (i) x1/2, y, z+1/2.
 

Acknowledgements

TK thanks the Hanns Seidel Stiftung for a personal grant funded by the German Bundesministerium für Bildung und Forschung.

References

First citationCremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.  CrossRef CAS Web of Science Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationFolmer-Anderson, J. F., Lynch, V. M. & Anslyn, E. V. (2005). Chem. Eur. J. 11, 5319–5326.  PubMed Google Scholar
First citationJakubas, R., Bednarska-Bolek, B., Zaleski, J., Medycki, W., Holderna-Natkaniec, K., Zielinski, P. & Galazka, M. (2005). Solid State Sci. 7, 381–390.  Web of Science CSD CrossRef CAS Google Scholar
First citationKashino, S., Kataoka, S. & Haisa, M. (1978). Bull. Chem. Soc. Jpn, 51, 1717–1722.  CrossRef CAS Web of Science Google Scholar
First citationMoritani, Y., Sasahara, N., Kashino, S. & Haisa, M. (1987). Acta Cryst. C43, 154–158.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationNonius (2004). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds