4-Carbamoylpiperidinium phenyl­acetate hemihydrate

Graham Smith; Urs D Wermuth

doi:10.1107/S1600536810047872

. 2010 Nov 20;66(Pt 12):o3260. doi: 10.1107/S1600536810047872

4-Carbamoylpiperidinium phenylacetate hemihydrate

Graham Smith ^a,^*, Urs D Wermuth ^a

PMCID: PMC3011685 PMID: 21589544

Abstract

The asymmetric unit of the title compound, C₆H₁₃N₂O⁺·C₈H₇O₂ ⁻·0.5H₂O, comprises two isonipecotamide cations, two phenylacetate anions and a water molecule of solvation. The hydrogen-bonding environments for both sets of ion pairs are essentially identical with the piperidinium and amide ‘ends’ of each cation involved in lateral heteromolecular hydrogen-bonded cyclic N—H⋯O associations [graph set R ₂ ²(11)] which incorporate a single carboxyl O-atom acceptor. These cyclic motifs enclose larger R ₅ ⁵(21) cyclic systems, forming sheet substructures which lie parallel to (101) and are linked across b by the single water molecule via water O—H⋯O_c (c = carboxylate) associations, giving a duplex-sheet structure.

Related literature

For structural data on isonipecotamide salts, see: Smith et al. (2010 ▶); Smith & Wermuth (2010a ▶,b ▶,c ▶). For graph-set analysis, see Etter et al. (1990 ▶).

Experimental

Crystal data

C₆H₁₃N₂O⁺·C₈H₇O₂ ⁻·0.5H₂O
M _r = 273.33
Monoclinic,
a = 12.3107 (9) Å
b = 25.214 (2) Å
c = 9.5402 (10) Å
β = 90.469 (9)°
V = 2961.2 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 200 K
0.50 × 0.22 × 0.20 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.959, T _max = 0.979
21326 measured reflections
5802 independent reflections
4258 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.105
S = 1.05
5802 reflections
392 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) within WinGX (Farrugia, 1999 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810047872/su2230sup1.cif

e-66-o3260-sup1.cif^{(34.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810047872/su2230Isup2.hkl

e-66-o3260-Isup2.hkl^{(278.3KB, 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
N1C—H11C⋯O13Bⁱ	0.941 (18)	1.826 (18)	2.7638 (17)	174.8 (17)
N1C—H12C⋯O13Aⁱⁱ	0.93 (2)	1.85 (2)	2.7322 (18)	157.9 (18)
N1D—H11D⋯O12A	0.924 (17)	1.876 (17)	2.7871 (17)	168.4 (16)
N1D—H12D⋯O12B	0.96 (2)	1.82 (2)	2.7095 (18)	153.0 (17)
N41C—H41C⋯O12Aⁱⁱⁱ	0.86 (2)	2.03 (2)	2.8789 (19)	166.3 (16)
N41C—H42C⋯O41Dⁱⁱⁱ	0.938 (18)	1.918 (18)	2.8480 (18)	170.8 (14)
N41D—H41D⋯O13Bⁱ	0.87 (2)	2.08 (2)	2.9177 (19)	160.6 (16)
N41D—H42D⋯O41C	0.913 (19)	1.917 (19)	2.8294 (18)	176.4 (18)
O1W—H11W⋯O13A	0.85 (2)	1.95 (2)	2.7881 (19)	171 (2)
O1W—H12W⋯O12B^iv	0.84 (3)	1.99 (3)	2.8335 (19)	179 (3)

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

Acknowledgments

The authors acknowledge financial support from the Australian Research Council, the Faculty of Science and Technology and the University Library, Queensland University of Technology and the School of Biomolecular and Physical Sciences, Griffith University.

supplementary crystallographic information

Comment

The amide piperidine-4-carboxamide (isonipecotamide, INIPA) has proved to be a particularly useful synthon for the construction of hydrogen-bonded crystalline salts with a range of aromatic carboxylic acids, enabling their structure determination (Smith & Wermuth, 2010a, 2010b, 2010c; Smith et al., 2010). The title compound from the 1:1 stoichiometric reaction of phenylacetic acid with INIPA, the hemihydrate C₆H₁₃N₂O⁺ C₈H₇O₂^-. 0.5H₂O, (I) was obtained and the structure is reported on herein.

In (I) the asymmetric unit contains two phenylacetate anions (A and B), two INIPA cations (C and D) and a water molecule of solvation (O1W) (Fig. 1). The hydrogen-bonding environments for both sets of ion pairs are essentially identical with the piperidinium and amide 'ends' of each cation involved in lateral heteromolecular cyclic hydrogen-bonded associations [graph set R₂²(11) (Etter et al., 1990)] (Table 1) which incorporate a single carboxyl O-atom acceptor (Fig. 2). The rings involve (a): cation C pyrimidinium and cation D amide N—H donors and cation C amide and anion B carboxyl O-atom acceptors and (b): cation D pyrimidinium and cation C amide N—H donors and cation D amide and anion A carboxyl O-atom acceptors. These ring motifs enclose larger cyclic systems [graph set R₅⁵(21)] forming sheet substructures which lie parallel to (101) and are linked across b by the single water molecule via water O—H···O_carboxyl associations to give the two-dimensional duplex-sheet structure (Fig. 3).

In the two independent phenylacetate anions, the conformation of the acetate side chains are significantly different [comparative torsion angles (maximum) for C2/C6–C1–C11–C12, 95.07 (17)° (A) and 124.84 (17)° (B); C1–C11–C12–O12/O13, 90.43 (16)° (A) and 127.76 (16)° (B)].

Experimental

The title compound was synthesized by heating together under reflux for 10 mins, 1 mmol quantities of piperidine-4-carboxamide (isonipecotamide) and phenylacetic acid in 50 ml of 50% methanol–water. After concentration to ca 30 ml, partial room temperature evaporation of the hot-filtered solution gave colourless plates of (I) from which a specimen was cleaved for the X-ray diffraction analysis.