4-(4-Chloro­phen­yl)-4-hy­droxy­piperidinium benzoate

Jerry P Jasinski; James A Golen; B P Siddaraju; A S Dayananda; H S Yathirajan

doi:10.1107/S1600536811017855

. 2011 May 20;67(Pt 6):o1436. doi: 10.1107/S1600536811017855

4-(4-Chlorophenyl)-4-hydroxypiperidinium benzoate

Jerry P Jasinski ^a,^*, James A Golen ^a, B P Siddaraju ^b, A S Dayananda ^b, H S Yathirajan ^b

PMCID: PMC3120431 PMID: 21754814

Abstract

In the title salt, C₁₁H₁₅ClNO⁺·C₇H₅O₂ ⁻, the dihedral angle between the mean planes of the chlorophenyl ring of the cation and the benzene ring of the anion is 74.4 (1)°. In the cation, the six-membered piperazine ring adopts a chair conformation. The crystal packing is stabilized by intermolecular N—H⋯O and O—H⋯O hydrogen bonds, and weak intermolecular C—H⋯O, C—H⋯Cl and C—H⋯π interactions.

Related literature

For the synthesis and biological activity of uncondensed cyclic derivatives of piperidine, see: Vartanyan (1984 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶) For related structures, see: Jasinski et al. (2009 ▶). For ring-motif pattterns, see: Bernstein et al. (1994 ▶).

Experimental

Crystal data

C₁₁H₁₅ClNO⁺·C₇H₅O₂ ⁻
M _r = 333.80
Triclinic,
a = 9.6235 (12) Å
b = 10.0971 (16) Å
c = 10.2251 (14) Å
α = 99.608 (12)°
β = 108.748 (13)°
γ = 113.357 (14)°
V = 812.7 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 173 K
0.34 × 0.30 × 0.13 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T _min = 0.920, T _max = 0.968
7857 measured reflections
4184 independent reflections
3222 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.125
S = 1.05
4184 reflections
217 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811017855/pv2415sup1.cif

e-67-o1436-sup1.cif^{(19.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017855/pv2415Isup2.hkl

e-67-o1436-Isup2.hkl^{(205KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811017855/pv2415Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg3 is the centroid of the C13–C18 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1NA⋯O3ⁱ	0.87 (1)	1.84 (1)	2.6964 (17)	166 (2)
O1—H1O⋯O3	0.82 (2)	2.05 (2)	2.7780 (16)	147 (2)
N1—H1NB⋯O2ⁱⁱ	0.86 (1)	1.92 (1)	2.7609 (18)	166 (2)
C16—H16A⋯Cl1ⁱⁱⁱ	0.95	2.78	3.5268 (17)	136
C9—H9B⋯O1ⁱ	0.99	2.46	3.3008 (19)	143
C1—H1A⋯Cg3^iv	0.95	2.70	3.554 (2)	150

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

Acknowledgments

BPS thanks the University of Mysore for the research facilities. HSY is grateful to RL Fine Chem., Bengaluru, India, for a pure sample of 4-(4-chlorophynyl)-piperidin-4-ol. JPJ acknowledges the NSF–MRI program (grant No. CHE1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

Comment

4-(4-Chlorophenyl)-4-hydroxypiperidine is used as an intermediate for the synthesis of pharmaceuticals such as haloperidol (a neuroleptic drug used to treat patients with psychotic illnesses, extreme agitation, or Tourette's syndrome) and loperamide (a synthetic piperidine derivative, effective against diarrhea resulting from gastroenteritis or inflammatory bowel disease). A review on the synthesis and biological activities of uncondensed cyclic derivatives of piperidine is reported (Vartanyan, 1984). The crystal structure of a related compound, 4-[(E)-(2,4-difluorophenyl) (hydroxyimino)methyl]piperidinium picrate (Jasinski et al., 2009) has been reported. In this paperwe report the crystal structure of C₁₁H₁₅ONCl⁺ . C₁₅H₁₂O₂^-.

In the title salt (Fig. 1), the 6-membered piperazine ring in the cation adopts a chair conformation with puckering parameters (Cremer & Pople, 1975) Q, θ and φ, 0.568 (2) Å, 0.00 (19)° and 278 (9)°, respectively . The dihedral angle between the mean planes of the chlorophenyl ring of the cation and the benzene ring of the anion is 74.4 (1)°. The crystal structure is stabilized by N1—H1NA···O3 and N1—H1NB···O2, hydrogen bonds forming R₄⁴(12) ring-motif patttern (Bernstein et al., 1994) and N1—H1NA···O3, O1—H10···O3 hydrogen bonds resulting in R₂⁴(16) ring-motif, generating one dimensional chains along the c axis (Fig. 2). The structure is further consolidated by weak C9—H9B···O1, C16—H16A···Cl1 and C1—H1A···Cg3 π-ring intermolecular interactions.

Experimental

Solutions of 4-(4-chlorophenyl)-piperidin-4-ol (2.12 g, 0.01 mol) in methanol (10 ml) and benzoic acid (1.226 g, 0.01 mol) in methanol (10 ml) were mixed and stirred in a beaker at 333 K for 30 minutes. The mixture was kept aside for three days at room temperature. The salt thus obtained was filtered and dried in a vaccum desiccator over phosphorous pentoxide. The compound was recrystallized from N,N-dimethylformamide by slow evaporation (m.p: 498 - 501 K).