N-Methacryloyl-4-(piperidin-1-yl)-1,8-naphthalimide

Lyall R Hanton; Stephen C Moratti; Zheng Shi; Jim Simpson

doi:10.1107/S1600536810018994

. 2010 May 29;66(Pt 6):o1476–o1477. doi: 10.1107/S1600536810018994

N-Methacryloyl-4-(piperidin-1-yl)-1,8-naphthalimide

Lyall R Hanton ^a, Stephen C Moratti ^a, Zheng Shi ^a, Jim Simpson ^a,^*

PMCID: PMC2979536 PMID: 21579543

Abstract

In the title compound, C₂₁H₂₀N₂O₃, the naphthalimide unit is almost planar (r.m.s. deviation for the 15 non-H atoms = 0.059 Å). The carboximide N atom and the five C atoms of the 2-methylprop-2-enoyl substituent also lie in a plane (r.m.s. deviation = 0.009 Å), which subtends an angle of 84.34 (7)° to the naphthalamide plane. This orients the =CH₂ group of the vinyl fragment towards the naphthalimide rings, giving the molecule an extended configuration. The piperidine ring adopts a chair conformation and there is evidence for some delocalization between the naphthalene and piperidine units, the C—N_pip bond length being 1.404 (4) Å. In the crystal structure, π–π contacts with centroid–centroid distances of 3.5351 (18) and 3.7794 (18) Å supported by C—H⋯O hydrogen bonds link adjacent molecules in a head-to-tail fashion, forming dimers. These are further stabilized by other C—H⋯O contacts of varying strength, which stack the molecules down the b axis.

Related literature

For background to the applications of 1,8-naphthalamides, see: McAdam et al. (2003 ▶, 2010 ▶); Flood et al. (2007 ▶). For their incorporation into polymer systems, see: Dana et al. (2007 ▶); Munro et al. (2008 ▶). For related structures, see: McAdam et al. (2003 ▶); Easton et al. (1992 ▶); Batchelor et al. (1997 ▶); Tagg et al. (2008 ▶). For comparative bond-length data, see: Allen et al. (1987 ▶) and for ring conformations, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₂₁H₂₀N₂O₃
M _r = 348.39
Monoclinic,
a = 29.049 (3) Å
b = 6.9852 (7) Å
c = 17.1503 (17) Å
β = 102.013 (6)°
V = 3403.7 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 90 K
0.65 × 0.11 × 0.04 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T _min = 0.838, T _max = 1.000
12211 measured reflections
1843 independent reflections
1440 reflections with I > 2σ(I)
R _int = 0.075
θ_max = 21.2°

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.152
S = 1.12
1843 reflections
236 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: APEX2 and SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and TITAN2000 (Hunter & Simpson, 1999 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ▶), PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810018994/hb5457sup1.cif

e-66-o1476-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018994/hb5457Isup2.hkl

e-66-o1476-Isup2.hkl^{(90.8KB, 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
C21—H21B⋯O12ⁱ	0.99	2.54	3.485 (4)	160
C24—H24A⋯O12ⁱⁱ	0.99	2.67	3.365 (4)	127
C21—H21A⋯O11ⁱⁱⁱ	0.99	2.36	3.258 (4)	150
C25—H25B⋯O11^iv	0.99	2.72	3.278 (4)	117

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

Acknowledgments

We thank the New Economy Research Fund; grant No. UOO-X0808 for support of this work and the University of Otago for purchase of the diffractometer.

supplementary crystallographic information

Comment

We have recently been interested in naphthalimide derivatives as components of donor-acceptor arrays because, as good acceptors, they often exhibit strong fluorescence together with redox triggered LMCT transitions in the near-IR (McAdam et al. 2003, 2010; Flood et al. 2007). We have also incorporated fluorescent naphthalimides into polymer systems (Dana et al., 2007; Munro et al., 2008). Methacrylate derivatives are polymer precursors and the title compound, I, Fig 1, was synthesised to further scope the possibilities of incorporating fluorescent naphthalimide derivatives into polymers.

The title compound comprises a 1,8-naphthalimide ring system with a piperidino ring at the C4 position of the naphthalene ring and a 2-methyl-prop-2-en-1-one substituent on the N1 atom of the dicarboxamide ring. The naphthalimide unit is planar with an rms deviation from the best fit meanplane through all 15 non-hydrogen atoms of 0.0494 Å. The C13 atom of the propenone headgroup and the N2 atom of the piperidine ring are both displaced slightly from this plane with deviations 0.170 (4) and 0.004 (3) Å respectively both in the same direction. Bond lengths within the dicarboxamide ring are normal (Allen et al., 1987) and consistent with a degree of delocalisation in the naphthalimide system. In keeping with previous observations (Easton et al., 1992; Batchelor et al., 1997; Tagg et al., 2008) the N1—C13 bond is relatively long, 1.486 (4) Å, suggesting that there is a node at the N1 atom. In contrast the C4—N2 bond is short, 1.404 (4) Å, indicating a degree of delocalisation between the naphthalene and piperidine units. The piperidine ring adopts a classical chair conformation with Cremer-Pople puckering parameters [Q(2) = 0.005 (4) Å, φ(2) = 154 (5)° and Q(3) = -0.575 (43) Å (Cremer & Pople, 1975). The N1, C13, (O1), C14, C15, C16 segment of the propenone is also planar (rms deviation 0.0920 Å) and subtends an angle of 84.44 (7)° to the naphthalimide plane. This orients the =C15H₂ of the vinyl fragment towards the naphthalimide rings.

In the crystal structure intermolecular π–π contacts occur between the unsubstituted C5···C8, C9, C10 naphthalene ring of one molecule and the C1, C8, C9, C11, C12, N1 carboxamide and substituted C1···C4, C9, C10 rings of an adjacent molecule to form head to tail dimers, with centroid to centroid distances of 3.5351 (18) and 3.7794 (18) Å respectively, Fig 2. These contacts are supported by weak C25–H25B···O11 hydrogen bonds. The dimers are further aggregated by a range of additional C—H···O contacts, Table 2, to give an extensive three dimensional network structure with molecules stacked down the b axis, Fig. 3.

Experimental

4-Piperidine-1,8-naphthalic amide (200 mg, 0.72 mmol) was dissolved in distilled dichloromethane (DCM) (30 ml) under N₂, triethylamine (3 ml) and methylacryoyl chloride (0.18 ml, 1.4 mmol) were added sequentially by syringe at 273 K. The mixture was stirred overnight. The mixture was then washed with distilled water (3 times) and the organic phase dried over MgSO₄. The solvent was evaporated under reduced pressure and the crude product purified by silica gel column chromatography with hexane-ethyl acetate (50:50, v/v) to give an orange solid (168.3 mg, 0.48 mmol); yield of 67.2%. The compound was recrystallised by the slow diffusion of hexane into a concentrated solution of I in DCM to give very thin orange blades/needles of (I).