2,2,6,6-Tetra­methyl-4-oxopiperidin-1-ium 4-chloro-3-nitro­benzoate

Bohari M Yamin; Norsakina Z Zulkifli

doi:10.1107/S1600536811025074

. 2011 Jul 6;67(Pt 8):o1920. doi: 10.1107/S1600536811025074

2,2,6,6-Tetramethyl-4-oxopiperidin-1-ium 4-chloro-3-nitrobenzoate

Bohari M Yamin ^a,^*, Norsakina Z Zulkifli ^a

PMCID: PMC3212310 PMID: 22090967

Abstract

The title salt, C₉H₁₈NO⁺·C₇H₃ClNO₄ ⁻, was obtained as an unexpected product of the reaction of 4-chloro-3-nitrobenzoyl isothiocyanate with pyrrolidine. The six-membered ring of the 4-oxopiperidinium cation adopts a chair conformation. In the crystal structure, two cations and three anions are linked together by intermolecular N—H⋯O and C—H⋯O hydrogen bonds and arranged diagonally along the ac face.

Related literature

For related structures, see: Wang et al. (2008 ▶); Jasinski et al. (2009 ▶), Smith & Wermuth (2011 ▶). For bond-length data, see Allen et al. (1987 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₉H₁₈NO⁺·C₇H₃ClNO₄ ⁻
M _r = 356.80
Triclinic,
a = 7.9974 (10) Å
b = 10.3267 (13) Å
c = 11.9196 (15) Å
α = 109.101 (3)°
β = 96.785 (3)°
γ = 104.720 (3)°
V = 877.58 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 298 K
0.40 × 0.14 × 0.09 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.908, T _max = 0.978
10082 measured reflections
3431 independent reflections
2268 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.126
S = 1.01
3431 reflections
229 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811025074/ff2016sup1.cif

e-67-o1920-sup1.cif^{(19.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811025074/ff2016Isup2.hkl

e-67-o1920-Isup2.hkl^{(168.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811025074/ff2016Isup3.cml

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—H1A⋯O3ⁱ	0.87 (2)	1.89 (2)	2.750 (2)	165
N1—H1B⋯O2ⁱⁱ	0.89 (1)	1.77 (1)	2.653 (2)	171
C3—H3A⋯O4ⁱⁱⁱ	0.97	2.54	3.269 (3)	132
C8—H8B⋯O3ⁱ	0.96	2.54	3.297 (3)	136

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors thank the Malaysian Government, Universiti Kebangsaan Malaysia and the Ministry of Higher Education, Malaysia, for research grants UKM-GUP-NBT– 08–27–110.

supplementary crystallographic information

Comment

The title salt is an unexpected product of the reaction of 4-chloro-3- nitro-benzoylisothiocyanate with pyrrolidine. The expected product was N-(4-chloro-3-nitrobenzoyl)-N'-(pyrrolidin-1-yl)thiourea. The salt consists of 2,2,6,6-tetramethylpiperidinium-4-one cation and 4-chloro-3-nitrobenzoate anion (Fig.1) indicating the opening of pyrrolidine ring and involvement of acetone solvent in the reaction mechanism. The piperidinium ring adopts a chair conformation with puckering parameters (Cremer & Pople, 1975) Q, θ and φ, of 0.507 (2) Å, 3.4 (3)° and 207 (6)°, respectively. The bond lengths and angles are in normal range (Allen et al., 1987) and comparable to those in piperidinium 3-hydroxy-2-naphthoate (Wang et al., 2008) and 4-carbamoylpiperidinium 5-nitrosalicylate (Smith & Wermuth, 2011). All atoms of the benzoate anion are essentially coplanar with the benzene ring except O4 and O5, which are deviated from the plane by 0.690 (2) and 0.880 (2) Å, respectively. In the crystal structure, two cations and three anions are linked together by intermolecular hydrogen bonds (symmetry codes as in Table 2) and arranged diagonally along the ac face (Fig.2).

Experimental

A solution of 4-chloro-3-nitrobenzoylisothiocyanate (2.42 g, 0.01 mol) in 30 ml acetone was added into a flask containing 30 ml acetone solution of pyyrolidine (0.71 g, 0.01 mol).The mixture was refluxed for 1 h. Then, the solution was filtered-off and left to evaporate at room temperature. The colourless solid was obtained after one day of evaporation (yield 83%, m.p 473.1–474.3 K).