Pyrrolidinium chloride

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) ų

• 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⋯Cl1^i	0.92	2.18	3.097 (2)	177
Symmetry code: (i) .

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

S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.2 U_eq(C/N).

Computing details

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

	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.
	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

Crystal data

C4H10N^+·Cl^−	F(000) = 232
Mr = 107.58	Dx = 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) Å^3	Block, colourless
Z = 4	0.22 × 0.13 × 0.12 mm

Data collection

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

Refinement

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

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

N1—C2^i	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—C1^i	1.482 (5)	C2—H22	0.9900
C2^i—N1—C2	105.9 (2)	C1^i—C1—H12	110.3
C2^i—N1—H101	110.5	C2—C1—H12	110.3
C2—N1—H101	110.5	H11—C1—H12	108.5
C2^i—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
C1^i—C1—C2	107.20 (13)	N1—C2—H22	110.8
C1^i—C1—H11	110.3	C1—C2—H22	110.8
C2—C1—H11	110.3	H21—C2—H22	108.9
C2^i—N1—C2—C1	31.4 (3)	C1^i—C1—C2—N1	−19.16 (18)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

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···Cl1^ii	0.92	2.18	3.097 (2)	177

Symmetry code: (ii) x−1/2, y, −z+1/2.