4-(4-Chloro­phen­yl)-4-hy­droxy­piperidinium 2-(2-phenyl­eth­yl)benzoate

Hoong-Kun Fun; Madhukar Hemamalini; B P Siddaraju; H S Yathirajan; B Narayana

doi:10.1107/S1600536811023051

. 2011 Jun 18;67(Pt 7):o1726. doi: 10.1107/S1600536811023051

4-(4-Chlorophenyl)-4-hydroxypiperidinium 2-(2-phenylethyl)benzoate

Hoong-Kun Fun ^a,^*,^‡, Madhukar Hemamalini ^a, B P Siddaraju ^b, H S Yathirajan ^b, B Narayana ^c

PMCID: PMC3152132 PMID: 21837116

Abstract

In the title compound, C₁₁H₁₅ClNO⁺·C₁₅H₁₃O₂ ⁻, the piperidinium ring adopts a chair conformation. In the crystal, cations and anions are connected by intermolecular O—H⋯O and N—H⋯O hydrogen bonds, forming two-dimensional networks parallel to the bc plane. Furthermore, the crystal structure is stabilized by weak C—H⋯π interactions.

Related literature

For related structures, see: Cygler et al. (1980 ▶); Cygler & Ahmed, (1984 ▶); Dutkiewicz et al. (2010 ▶); Jasinski et al. (2009 ▶, 2010 ▶); Tomlin et al. (1996 ▶). For the synthesis and biological activity of uncondensed cyclic derivatives of piperidine, see: Vartanyan (1984 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₁H₁₅ClNO⁺·C₁₅H₁₃O₂ ⁻
M _r = 437.94
Monoclinic,
a = 13.1016 (2) Å
b = 10.2963 (2) Å
c = 16.8015 (3) Å
β = 98.234 (1)°
V = 2243.12 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 100 K
0.45 × 0.43 × 0.33 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.916, T _max = 0.938
27219 measured reflections
8207 independent reflections
6646 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.120
S = 1.03
8207 reflections
292 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811023051/rz2607sup1.cif

e-67-o1726-sup1.cif^{(23.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811023051/rz2607Isup2.hkl

e-67-o1726-Isup2.hkl^{(393.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811023051/rz2607Isup3.cml

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

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

Cg2 is the centroid of the C20–C25 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O3	0.890 (18)	1.891 (18)	2.7401 (12)	158.8 (16)
N1—H1N1⋯O3ⁱ	0.954 (16)	1.754 (16)	2.6939 (11)	167.7 (15)
N1—H2N1⋯O2ⁱⁱ	0.917 (16)	1.818 (16)	2.7223 (11)	168.6 (15)
C8—H8B⋯Cg2	0.99	2.85	3.6743 (11)	141

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

Acknowledgments

HKF and MH thank the Malaysian Government and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160. MH also thanks Universiti Sains Malaysia for a post-doctoral research fellowship. BPS thanks the University of Mysore for the research facilities.

supplementary crystallographic information

Comment

4-(4-Chlorophenyl)-4-hydroxypiperidine is used as an intermediate for the synthesis of pharmaceuticals such as haloperidol (neuroleptic drug used to treat patients with psychotic illnesses, extreme agitation, or Tourette's syndrome) and loperamide, which is a synthetic piperidine derivative, is a drug effective against diarrhea resulting from gastroenteritis or inflammatory bowel disease. A review on the synthesis and biological activity of uncondensed cyclic derivatives of piperidine has been reported (Vartanyan, 1984).

The crystal structures of 1,2,2,4,6,6-hexamethyl-4-piperidinol (Cygler et al., 1980), three isomers of (±)-1,2,3-trimethyl-4-phenyl- 4-piperidinol (Cygler & Ahmed, 1984), 1-(4-nitrophenyl)-4-piperidinol (Tomlin et al., 1996) and 4-[(E)-(2,4-difluorophenyl) (hydroxyimino)methyl]piperidinium picrate (Jasinski et al., 2009) have been reported. Also the crystal structures of 4-(4-chlorophenyl) piperidin-4-ol (Dutkiewicz et al., 2010) and 4-(4-chlorophenyl)- 4-hydroxypiperidinium maleate maleic acid solvate (Jasinski et al., 2010) have been reported. In view of the importance of the title compound (I), its crystal structure is reported herein.

The asymmetric unit of (I), (Fig.1), consists of a 4-(4-chlorophenyl)-4- hydroxypiperidinium cation and a 2-(2-phenylethyl)benzoate anion. The piperidine ring adopts a chair conformation with puckering parameters Q = 0.5678 (10) Å, θ = 1.81 (10)° and φ = 198 (3)° (Cremer & Pople, 1975). In the cation, the dihedral angle between the mean planes of the piperidinium ring (N1/C7–C11) with the benzene ring (C1–C6) is 88.12 (5)°. In the anion, the dihedral angle between the benzene (C12–C17) ring and the carboxy-subsituted phenyl (C20–C25) ring is 40.72 (5)°. In the crystal structure (Fig. 2), the cations and anions are connected by intermolecular N1—H1N1···O3, N1—H2N1···O3 and O1—H1O1···O3 hydrogen bonds, forming two-dimensional networks parallel to the bc plane. Furthermore, the crystal structure is stabilized by weak C—H···π interactions, involving the C20–C25 ring.

Experimental

4-(4-Chlorophenyl)-piperidin-4-ol (2.12 g, 0.01 mol) was dissolved in 10 ml of methanol and 2-(2-phenylethyl)benzoic acid (2.26 g, 0.01 mol) was dissolved in 10 ml of methanol. The solutions 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 formed salt was filtered and dried in vacuum desiccator over phosphorous pentoxide. Crystals suitable for X-ray analysis were obtained by slow evaporation of a N,N-dimethylformamide solution (m. p.: 445–448 K).