Pyrrolidinium chloride

Giglmeier, H.; Kerscher, T.; Klüfers, P.; Mayer, P.

doi:10.1107/S1600536809006060

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o592

doi:10.1107/S1600536809006060

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Pyrrolidinium chloride

Helene Giglmeier,^a Tobias Kerscher,^a Peter Klüfers ^a ^* and Peter Mayer ^a

^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 E_N1.

Related literature

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 E_N1 conformation of the five-membered ring, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₄H₁₀N⁺·Cl⁻
M_r = 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)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.120
S = 1.07
756 reflections
31 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809006060/bi2348sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809006060/bi2348Isup2.hkl

checkCIF report

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 C_s 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 E_N1.

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 E_N1 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.

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

	Fig. 1. The molecular structure of the C_s symmetric title compound with anisotropic displacement ellipsoids drawn at 50% probability for non-H atoms. Symmetry code: (i) x, -y + 1/2, z.
	Fig. 2. Packing of the title compound, viewed along [0 1 0].
	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⁺·Cl⁻	F(000) = 232
M_r = 107.58	D_x = 1.146 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 2321 reflections
a = 7.4429 (4) Å	θ = 3.1–27.5°
b = 9.4104 (5) Å	µ = 0.48 mm⁻¹
c = 8.9021 (4) Å	T = 200 K
V = 623.51 (5) Å³	Block, colourless
Z = 4	0.22 × 0.13 × 0.12 mm

Data collection top

Nonius KappaCCD diffractometer	608 reflections with I > 2σ(I)
Radiation source: rotating anode	R_int = 0.037
MONTEL, graded multilayered X-ray optics monochromator	θ_max = 27.5°, θ_min = 3.2°
ϕ and ω scans	h = −8→9
4239 measured reflections	k = −12→12
756 independent reflections	l = −11→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0625P)² + 0.1854P] where P = (F_o² + 2F_c²)/3
756 reflections	(Δ/σ)_max < 0.001
31 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₄H₁₀N⁺·Cl⁻	V = 623.51 (5) Å³
M_r = 107.58	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 7.4429 (4) Å	µ = 0.48 mm⁻¹
b = 9.4104 (5) Å	T = 200 K
c = 8.9021 (4) Å	0.22 × 0.13 × 0.12 mm

Data collection top

Nonius KappaCCD diffractometer	608 reflections with I > 2σ(I)
4239 measured reflections	R_int = 0.037
756 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.07	Δρ_max = 0.21 e Å⁻³
756 reflections	Δρ_min = −0.24 e Å⁻³
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 U_eq(C) for C atoms and 1.2 U_eq(N) for N atoms.

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

	x	y	z	U_iso*/U_eq
N1	0.2072 (3)	0.2500	0.3955 (3)	0.0473 (6)
H101	0.2341	0.2500	0.2946	0.057*
H102	0.0843	0.2500	0.4065	0.057*
C1	0.3204 (4)	0.1712 (3)	0.6283 (3)	0.0781 (8)
H11	0.2249	0.1348	0.6954	0.094*
H12	0.4376	0.1348	0.6641	0.094*
C2	0.2871 (3)	0.1242 (2)	0.4702 (3)	0.0623 (6)
H21	0.4009	0.0963	0.4208	0.075*
H22	0.2032	0.0427	0.4677	0.075*
Cl1	0.29515 (8)	0.2500	0.05610 (7)	0.0488 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0466 (12)	0.0500 (13)	0.0452 (12)	0.000	−0.0007 (10)	0.000
C1	0.102 (2)	0.0775 (16)	0.0553 (14)	0.0109 (14)	−0.0060 (13)	0.0106 (12)
C2	0.0803 (16)	0.0411 (11)	0.0657 (14)	0.0045 (10)	0.0013 (11)	0.0050 (9)
Cl1	0.0477 (4)	0.0528 (4)	0.0459 (4)	0.000	−0.0020 (3)	0.000

Geometric parameters (Å, º) top

N1—C2ⁱ	1.482 (3)	C1—C2	1.495 (4)
N1—C2	1.482 (2)	C1—H11	0.9900
N1—H101	0.9200	C1—H12	0.9900
N1—H102	0.9200	C2—H21	0.9900
C1—C1ⁱ	1.482 (5)	C2—H22	0.9900

C2ⁱ—N1—C2	105.9 (2)	C1ⁱ—C1—H12	110.3
C2ⁱ—N1—H101	110.5	C2—C1—H12	110.3
C2—N1—H101	110.5	H11—C1—H12	108.5
C2ⁱ—N1—H102	110.5	N1—C2—C1	104.64 (19)
C2—N1—H102	110.5	N1—C2—H21	110.8
H101—N1—H102	108.7	C1—C2—H21	110.8
C1ⁱ—C1—C2	107.20 (13)	N1—C2—H22	110.8
C1ⁱ—C1—H11	110.3	C1—C2—H22	110.8
C2—C1—H11	110.3	H21—C2—H22	108.9

C2ⁱ—N1—C2—C1	31.4 (3)	C1ⁱ—C1—C2—N1	−19.16 (18)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H101···Cl1	0.92	2.17	3.091 (3)	180
N1—H102···Cl1ⁱⁱ	0.92	2.18	3.097 (2)	177

Symmetry code: (ii) x−1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₄H₁₀N⁺·Cl⁻
M_r	107.58
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	200
a, b, c (Å)	7.4429 (4), 9.4104 (5), 8.9021 (4)
V (Å³)	623.51 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.48
Crystal size (mm)	0.22 × 0.13 × 0.12

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4239, 756, 608
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.120, 1.07
No. of reflections	756
No. of parameters	31
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
N1—H101···Cl1	0.92	2.17	3.091 (3)	179.5
N1—H102···Cl1ⁱ	0.92	2.18	3.097 (2)	177.4

Symmetry code: (i) x−1/2, 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

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