Crystal structure of 4-bromo-2-[(E)-N-(2,2,6,6-tetra­methyl­piperidin-4-yl)carboximido­yl]phenol dihydrate

Joel T Mague; Shaaban K Mohamed; Mehmet Akkurt; Antar A Abdelhamid; Mustafa R Albayati

doi:10.1107/S2056989015007471

. 2015 Apr 25;71(Pt 5):o349–o350. doi: 10.1107/S2056989015007471

Crystal structure of 4-bromo-2-[(E)-N-(2,2,6,6-tetramethylpiperidin-4-yl)carboximidoyl]phenol dihydrate

Joel T Mague ^a, Shaaban K Mohamed ^b,^c, Mehmet Akkurt ^d, Antar A Abdelhamid ^e, Mustafa R Albayati ^f,^*

PMCID: PMC4420100 PMID: 25995942

Abstract

In the title hydrate, C₁₆H₂₃BrN₂O·2H₂O, the organic molecule features a strong intramolecular O—H⋯N hydrogen bond. The piperidine ring, in addition, adopts a chair conformation with the exocyclic C—N bond in an equatorial orientation. The water molecules of crystallization are disordered (each over two sets of sites with half occupancy. In the crystal, they associate into corrugated (100) sheets of (H₂O)₄ tetramers linked by O—H⋯O hydrogen bonds. The organic molecules, in turn, are arranged at both sides of these sheets, linked by water–piperidine O—H⋯N hydrogen bonds.

Keywords: crystal structure, Schiff bases, piperidines, hydrogen bonding

Related literature

For various biological applications of piperidine-containing compounds, see: Sánchez-Sancho & Herrandón (1998 ▸); Nithiya et al. (2011 ▸); Adger et al. (1996 ▸); Kozikowski et al. (1998 ▸); Brau et al. (2000 ▸).

Experimental

Crystal data

C₁₆H₂₃BrN₂O·2H₂O
M _r = 375.30
Monoclinic,
a = 39.6126 (7) Å
b = 6.0497 (1) Å
c = 14.8673 (3) Å
β = 98.889 (1)°
V = 3520.07 (11) Å³
Z = 8
Cu Kα radiation
μ = 3.30 mm⁻¹
T = 150 K
0.34 × 0.09 × 0.08 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer
Absorption correction: numerical (SADABS; Bruker, 2014 ▸) T _min = 0.54, T _max = 0.77
12901 measured reflections
3428 independent reflections
3113 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.077
S = 1.10
3428 reflections
204 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Data collection: APEX2 (Bruker, 2014 ▸); cell refinement: SAINT (Bruker, 2014 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ▸); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ▸); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015007471/bg2553sup1.cif

e-71-0o349-sup1.cif^{(412.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015007471/bg2553Isup2.hkl

e-71-0o349-Isup2.hkl^{(188.3KB, hkl)}

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S2056989015007471/bg2553fig1.tif

The the asymmetric unit showing the intra- and intermolecular O—H⋯N hydrogen bonds as dotted lines. Only one set of the disordered hydrogen atoms is shown.

Click here for additional data file.^{(1.4MB, tif)}

b . DOI: 10.1107/S2056989015007471/bg2553fig2.tif

Packing viewed down the b axis with intermolecular O—H⋯N and O—H⋯O hydrogen bonds shown, respectively, as purple and red dotted lines. Only one set of the disordered hydrogen atoms is shown.

Click here for additional data file.^{(901.1KB, tif)}

. DOI: 10.1107/S2056989015007471/bg2553fig3.tif

A portion of the layer of lattice water molecules. Only one set of the disordered hydrogen atoms is shown.

CCDC reference: 1059897

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O1H1AN1	0.84	1.87	2.628(2)	149
O2H2BN2	0.84	2.02	2.861(2)	175
O3H3AO2ⁱ	0.84	2.24	3.059(2)	167
O3H3BO2ⁱⁱ	0.84	2.04	2.869(2)	168
O2AH2BAN2	0.84	2.02	2.861(2)	175
O2AH2DO3A ⁱⁱⁱ	0.84	2.04	2.869(2)	170
O3AH3AAO2A ⁱ	0.84	2.24	3.059(2)	167

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

Acknowledgments

The support of NSF–MRI grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

supplementary crystallographic information

S1. Comment

Piperidine-bearing compounds have diverse applications in commercial and medicinal fields. The piperidine nucleus is an ubiquitous structural feature of biologically active compounds and numerous secondary metabolites, for example (S)-pipecolic acid a non-proteinogenic amino acid associated with epilepsy (Sánchez-Sancho & Herrandón, 1998; Nithiya et al., 2011; Adger et al., 1996). Moreover, piperidine-containing compounds were evaluated for their effect on plasma glucose level (Kozikowski et al., 1998), insulin normalization and treatment of cocaine abuse (Brau et al., 2000). In this vein and following our strategy for synthesis of bio-active heterocyclic compounds, we report the synthesis and crystal structure of the title compound.

The conformation of the title molecule is determined in part by the strong O1—H1a···N1 hydrogen bond. The substituted piperidine ring adopts a chair conformation with puckering parameters Q = 0.503 (2) Å, θ = 12.0 (2) Å and φ = 176 (1)°. In the crystal, hydrogen bonding between the lattice water molecules generates corrugated layers approximately parallel to (100) with the piperidine nitrogen atoms (N2) hydrogen bonded to both sides (Table 1 and Fig. 2). Although the disorder in the lattice waters makes a precise description of the hydrogen bonding network in the water layer difficult (and generates apparent short H···H contacts), use of one component of the disorder indicates the presence of (H₂O)₄ units (Fig. 3) which hydrogen bond to the piperidine nitrogen atoms.

S2. Experimental

A mixture of 1 mmol (156 mg) of 2,2,6,6-tetramethylpiperidin-4-amine and 1 mmol (201 mg) of 5-bromo-2-hydroxybenzaldehyde in 30 ml ethanol was heated under reflux for 5 h. The solid product was obtained on cooling, filtered off, dried under vacuum and recrystallized from ethanol to afford pale yellow columns which were suitable for X-ray diffraction. Mp. 361 K.