1,1′-[(5-Hy­droxy­methyl-1,3-phenyl­ene)bis­(methyl­ene)]dipyridin-4(1H)-one monohydrate

José A Fernandes; Manuela E L Lago; Sandrina Silva; João P C Tomé; José A S Cavaleiro; Filipe A Almeida Paz

doi:10.1107/S1600536811024809

. 2011 Jun 30;67(Pt 7):o1859–o1860. doi: 10.1107/S1600536811024809

1,1′-[(5-Hydroxymethyl-1,3-phenylene)bis(methylene)]dipyridin-4(1H)-one monohydrate

José A Fernandes ^a, Manuela E L Lago ^b, Sandrina Silva ^b, João P C Tomé ^b, José A S Cavaleiro ^b, Filipe A Almeida Paz ^a,^*

PMCID: PMC3152136 PMID: 21837224

Abstract

The asymmetric unit of the title compound, C₁₉H₁₈N₂O₃, comprises a whole organic dipyridinone molecule plus a water molecule of crystallization. The planes of the pyridinone rings are approximately perpendicular with the plane of the central aromatic ring [dihedral angles = 80.68 (8) and 83.65 (8)°]. The C—O bond of the hydroxy group subtends an angle of 31.71 (10)° with the plane through the central aromatic ring. The crystal packing is mediated by the presence of several O—H⋯O hydrogen-bonding interactions and while the water molecules form a C ₂ ¹(4) chain parallel to the c axis of the unit cell, the pendant hydroxy groups are engaged in O—H⋯O=C hydrogen bonds described by a C ₁ ¹(12) graph-set motif which runs parallel to the a axis.

Related literature

For previous reports on the design and synthesis of molecules based on a mesitylene core, see: Reger et al. (2010 ▶); Podyachev et al. (2006 ▶); Spiccia et al.(1997 ▶); Newkome et al. (1986 ▶); Berl et al., (2002 ▶). For the crystal structure and vibrational features of the precursor, 1,3,5-tris(bromomethyl)benzene, see: Fernandes et al. (2011 ▶). For a systematization of the graph-set notation for hydrogen-bonded aggregates, see: Grell et al. (1999 ▶).

Experimental

Crystal data

C₁₉H₁₈N₂O₃·H₂O
M _r = 340.37
Monoclinic,
a = 12.2215 (8) Å
b = 14.1521 (10) Å
c = 10.3326 (7) Å
β = 114.720 (3)°
V = 1623.36 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 180 K
0.16 × 0.10 × 0.10 mm

Data collection

Bruker X8 KappaCCD APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T _min = 0.984, T _max = 0.990
79090 measured reflections
2188 independent reflections
2103 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.077
S = 1.07
2188 reflections
233 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT-Plus (Bruker, 2005 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2009 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811024809/tk2759sup1.cif

e-67-o1859-sup1.cif^{(19.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811024809/tk2759Isup2.hkl

e-67-o1859-Isup2.hkl^{(107.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811024809/tk2759Isup3.cml

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
O1W—H1X⋯O3ⁱ	0.94 (1)	1.93 (1)	2.842 (2)	164 (2)
O1W—H1Y⋯O3ⁱⁱ	0.94 (1)	2.03 (1)	2.973 (2)	174 (2)
O1—H1⋯O2ⁱⁱⁱ	0.84	1.87	2.6814 (19)	162

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

Acknowledgments

We are grateful to the Fundação para a Ciência e a Tecnologia (FCT, Portugal) for their general financial support, for the post-doctoral research grants Nos. SFRH/BPD/63736/2009 (to JAF) and SFRH/BPD/64812/2009 to (SS), and for funding toward the purchase of the single-crystal diffractometer.

supplementary crystallographic information

Comment

1,3,5-Tris(bromomethyl)benzene has been systematically employed in the preparation of many branched (Reger et al., 2010; Podyachev et al., 2006; Spiccia et al., 1997) or dendritic molecules (Newkome et al., 1986; Berl et al., 2002) with a mesitylene unit comprising the core. Our research groups have also been using this molecule as a versatile template and recently we reported its crystal structure and detailed vibrational features (Fernandes et al., 2011). During our research efforts with this molecule we have isolated the title compound, C₁₉H₁₈N₂O₃^.H₂O, as a secondary product. The title compound was obtained by the nucleophilic substitution of two bromo atoms of 1,3,5-tris(bromomethyl)benzene by 4-hydroxypyridine. Due to tautomeric equilibrium of this latter reagent, the nucleophilic attack occurred via the nitrogen atom and not via the oxygen. Spontaneous oxidation gave rise to the title compound whose crystal structure we wish to report here.

The asymmetric unit of the title compound (I) comprises a whole molecular unit, C₁₉H₁₈N₂O₃, and a water molecule of crystallization as depicted in Figure 1. The pyridone rings are almost planar (largest observed deviations of about 0.013 and 0.009 Å), and are approximately perpendicular to the plane of the central aromatic ring (dihedral angles of 80.68 (8) and 83.65 (8) °). The C—O bond belonging to the terminal hydroxy group subtends an angle of 31.71 (10)° with the plane of the central aromatic ring.

The presence of polar O—H bonds and the C═O moieties located in opposite positions of the organic moiety permits the existence of several hydrogen bonding interactions whose geometric details are tabulated in Table 1. On the one hand, the two hydrogen atoms of the water molecule of crystallization interact with neighbouring O3 atoms from adjacent organic molecules, leading to the formation of a supramolecular polymeric chain parallel to the c-axis of the unit cell, describing a C¹₂(4) graph set motif (Grell et al., 1999), Figs 2 and 3. On the other hand, the pendant hydroxy groups are engaged in O—H···O═C hydrogen bonds, Figs 2 and 3, which permits a direct connection between adjacent molecular units. In addition, this connection leads to the formation of a C¹₁(12) graph set motif parallel to the a-axis.

Experimental

All chemicals were purchased from commercial sources and were used without further purification: 4-hydroxypyridine (Fluka, 95%); potassium carbonate (Vaz Pereira); 1,3,5-tris(bromomethyl)benzene (Sigma-Aldrich, 97%).

An excess of potassium carbonate (200 mg, 1.45 mmol) was added to a solution of 4-hydroxypyridine (52.8 mg, 0.56 mmol) in dry dimethylformamide (DMF, 2.5 mL). The resulting mixture was stirred under N₂ for 30 minutes at ambient temperature. This mixture was then added drop wise to a DMF (2.5 mL) solution of 1,3,5-tris(bromomethyl)benzene (100 mg, 0.28 mmol). The new reaction mixture was maintained under constant magnetic stirring for 3 h under N₂. The resulting products were precipitated by the addition of diethyl ether, filtered and purified by column chromatography (silica gel) using a mixture of THF/MeOH (1:2) as eluent. The title compound was crystallized from a mixture of CHCl₃/MeOH (95:5). Yield: 25%.

¹H NMR (300 MHz, CDCl₃/MeOD): δ 4.51 (s, 2H, CH₂OH), 4.93 (s, 4H, CH₂N), 6.31 (d, J_o_-m= 7.6 Hz, 4H, m-H), 6.89 (s, 1H, ArH-2), 7.10 (s, 2H, ArH-4, 6), 7.44 (d, J_o_-m= 7.6 Hz, 4H, o-H).

¹³C NMR (75 MHz, CDCl₃/MeOD): δ 63.2 (CH₂N), 67.9 (CH₂OH), 118.2 (NCH₂CH₂CO), 125.3 (ArC-2), 126.2 (ArC-4, 6), 136.2 (ArC-1, 3), 141.0 (NCH₂CH₂CO), 144.6 (ArC-5), 179.4 (CO).