6-Nicotinamido-2-naphthoic acid

Yun-Sung Song; Soon W Lee

doi:10.1107/S1600536812024051

. 2012 Jun 2;68(Pt 7):o1978. doi: 10.1107/S1600536812024051

6-Nicotinamido-2-naphthoic acid

Yun-Sung Song ^a, Soon W Lee ^a,^*

PMCID: PMC3393255 PMID: 22807812

Abstract

In the title molecule, C₁₇H₁₂N₂O₃, the naphthalene ring system and the pyridin-3-yl rings are nearly coplanar with a dihedral angle between them of 2.28 (8)°. In the crystal, the hydroxy and amide N atoms participate in hydrogen bonds, which connect the molecules into a two-dimensional network parallel to (101).

Related literature

For coordination polymers based on linking ligands with O- and N-donors see: Robin & Fromm, 2006 ▶. For d–f coordination polymers based on linking ligands with pyridyl–carboxylate terminals see: Hu et al. (2012 ▶); Chen et al. (2010 ▶); Tang et al. (2010 ▶); Yue et al. (2011 ▶); Zhu et al. (2010 ▶). For related potential linking ligands see: Han & Lee, 2012 ▶; Zheng & Lee, 2012 ▶.

Experimental

Crystal data

C₁₇H₁₂N₂O₃
M _r = 292.29
Monoclinic,
a = 25.901 (3) Å
b = 6.2097 (7) Å
c = 8.6080 (9) Å
β = 103.258 (9)°
V = 1347.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.40 × 0.20 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.961, T _max = 0.992
11725 measured reflections
1693 independent reflections
2845 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.092
S = 1.05
1693 reflections
207 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: APEX2 (Bruker (2008 ▶); cell refinement: SAINT (Bruker (2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812024051/mw2071sup1.cif

e-68-o1978-sup1.cif^{(17.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812024051/mw2071Isup2.hkl

e-68-o1978-Isup2.hkl^{(83.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812024051/mw2071Isup3.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
N2—H2N⋯O1ⁱ	0.92 (3)	2.01 (3)	2.926 (2)	170 (2)
O2—H2O⋯N1ⁱⁱ	0.84 (3)	1.88 (4)	2.708 (2)	170 (3)

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

Acknowledgments

This work was supported by the Mid-career Researcher Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science, and Technology (No. 2009–0079916).

supplementary crystallographic information

Comment

Bis(pyridyl)- and dicarboxylate-type linking ligands have been typically employed for the preparation of coordination polymers (Robin & Fromm, 2006). The vast majority of known coordination polymers contain either a d- or an f-block metal. However, several research groups recently prepared polymers containing both d- and f-block metals within their frameworks by utilizing linking ligands possessing pyridyl–carboxylate terminal groups (Hu et al., 2012; Chen et al., 2010; Tang et al., 2010; Yue et al., 2011; Zhu et al., 2010). Consistent with the hard–soft acid–base concept, the harder oxygen atoms are bonded to the f-block metals and the softer nitrogen atoms are bonded to the d-block metals in these polymers. Our research group recently reported the structures of two potential linking ligands with pyridyl–carboxylate terminal groups (Han & Lee, 2012; Zheng & Lee, 2012) and here we report the structure of third.

The molecular structure of the title molecule with the atom-labeling scheme is given in Figure 1. The naphthalene and 3-pyridyl rings are nearly coplanar with a dihedral angle between them of 2.28 (8)°. The N2–C6 bond length (1.343 (2) Å) indicates a C–N single bond. The intermolecular O–H···N and N–H···O (carbonyl) hydrogen bonds (Table 1) connect the molecules along the a- and c-axes, respectively, leading to a 2-D network in the [101] direction (Figure 2).

Experimental

A stirred mixture of 6-amino-2-naphthoic acid (0.94 g, 5 mmol) and N,N-dimethyl-4-aminopyridine (0.02 g, 0.17 mmol) in dimethylacetamide (15 mL) was heated at 80 °C for 30 min under argon. The solution was cooled to 10 °C, and nicotinoyl chloride hydrochloride (0.89 g, 5 mmol) was added. The temperature was then raised slowly to 50 °C and was maintained there for 8 h. On addition of dichloromethane to the resulting mixture, a precipitate was formed, which was filtered off and dried under vacuum at 100°C. The product was recrystallized from methanol to give crystals of the title compound (1.22 g, 4.2 mmol, 83.9% yield). mp: 593–595 K (decomp). ¹H NMR (500 MHz, DMSO-d₆, d) 11.06 (s, 1H, carboxylic acid OH), 9.35 (s, 1H, amide NH), 8.93 (d, 1H, pyridine proton), 8.71 (d, 1H, pyridine proton), 8.56 (s, 2H, naphthalene proton), 8.14 (d, 1H, pyridine proton), 7.96–7.94 (m, 4H, naphthalene proton), 7.88 (t, 1H, pyridine proton). ¹³C{¹H} NMR (125 MHz, DMSO-d₆, d) 167.3, 163.1, 148.7, 145.7, 139.5, 138.4, 135.4, 131.6, 130.2, 129.9, 129.1, 127.8, 127.0, 125.75, 125.0, 121.3, 116.2. IR (KBr, cm^-1): 3623 (w), 3328 (w), 2925 (s), 2640 (s), 2372 (s), 2075 (s), 1800 (m), 1621 (m), 1551 (m), 1291 (m), 1195 (m), 1018 (m), 773 (m), 724 (m), 678 (m), 633 (m), 494 (s).