Zwitterionic (4-benzyl­piperidinium-1-yl­meth­yl)phospho­nate

Saeed Dehghanpour; Ali Mahmoudi; Mehdi Khalaj

doi:10.1107/S1600536807061429

. 2007 Dec 6;64(Pt 1):o19. doi: 10.1107/S1600536807061429

Zwitterionic (4-benzylpiperidinium-1-ylmethyl)phosphonate

Saeed Dehghanpour ^a,^*, Ali Mahmoudi ^b, Mehdi Khalaj ^b

PMCID: PMC2914981 PMID: 21200754

Abstract

The title compound, C₁₃H₂₀NO₃P, exists as a zwitterion: the phosphonic acid group has transferred its H atom to the amino group. The piperidine ring adopts a chair conformation. Molecules are linked via hydrogen bonding to form a linear chain.

Related literature

For similar structures, see: Kotek et al. (2000 ▶); Mao et al. (2002 ▶); Ying et al. (2007 ▶); Vivani et al. (2004 ▶).

Experimental

Crystal data

C₁₃H₂₀NO₃P
M _r = 269.27
Orthorhombic,
a = 9.2791 (6) Å
b = 11.4916 (9) Å
c = 24.915 (2) Å
V = 2656.7 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 120 (2) K
0.50 × 0.50 × 0.30 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: numerical [shape of crystal determined optically (X-RED; Stoe & Cie, 2005 ▶)] T _min = 0.900, T _max = 0.938
9369 measured reflections
3536 independent reflections
3336 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.087
S = 1.10
3536 reflections
179 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807061429/ng2383sup1.cif

e-64-00o19-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807061429/ng2383Isup2.hkl

e-64-00o19-Isup2.hkl^{(170KB, hkl)}

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—H1C⋯O2ⁱ	0.961 (16)	1.707 (16)	2.651 (1)	166 (2)
O1—H1D⋯O3ⁱ	0.877 (19)	1.682 (19)	2.549 (1)	169 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

SD acknowledges the Alzahra University Research Council for partial support of this work.

supplementary crystallographic information

Comment

Recently, an increasing attention has been focused on the synthesis and designing of aminodiphosphonic acids and new metal phosphonate inorganic–organic hybrid materials with one-, two- or three-dimensional structures due to their potential applications in porous materials, ion exchange reagents, catalysis, sensors, nonlinear optics materials, anti-tumour drugs, photovoltaic devices and biotechnologies (Kotek et al., 2000; Ying et al., 2007; Mao et al., 2002; Vivani et al., 2004). The title compounds, (I), Fig. 1, was prepared by the reaction of benzylpiperidine and formaldehyde with posphorus acid (Scheme I).

The coordination environment around the phosphorus atoms of compound (I) are approximately tetrahedral, since average of six angles involving P are 109.35°. However the coordination is clearly distorted, arising from the presence of different substituents at phosphorus center. The angles O2—P1—O3 and C1—P1—O2 have values of 104.59 (5) and 118.29 (4)°, respectively. The piperidine ring in the titled compound adopt a chair conformation similar to that of cyclohexane. Bond lengths involving phosphorus atom are in good agreement with values found in other similar compounds (Ying et al., 2007; Vivani et al., 2004). The molecules are linked via intermolecular hydrogen bonding to form a one-dimensional chain of fused rings (Fig. 2).

Experimental

A quantity of 0.33 mole of benzylpiperidne was dissolved in 75 ml of concentrated HCl and a concentrated aqueous solution of 2 moles of phosphorous acid. The resulting solution was heated to reflux temperature and 160 ml of 37% aqueous formaldehyde solution (2 moles) was added dropwise in the course of 1 hr and the reaction mixture was kept at reflux temperature for 3 additional hr. Upon cooling to room temperature the acids crystallized. Calc for C₁₃H₂₀NO₃P: C 57.99, H 7.49, N 5.20%; found C 57.96, H 7.50, N 5.21%.