Pyrrolidinium chloride

Abstract

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,

• 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[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 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

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.

Supplementary Material

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

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) .

supplementary crystallographic information

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.

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.

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).

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.

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) Å3	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	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 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(Fo2) + (0.0625P)2 + 0.1854P] where P = (Fo2 + 2Fc2)/3
756 reflections	(Δ/σ)max < 0.001
31 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.23 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 Ueq(C) for C atoms and 1.2 Ueq(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)

	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, °)

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 codes: (i) x, −y+1/2, z.

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···Cl1ii	0.92	2.18	3.097 (2)	177

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