N-(1-Acryloyl-2,2,6,6-tetra­methyl­piperidin-4-yl)acryl­amide

Shailesh K Goswami; Lyall R Hanton; C John McAdam; Stephen C Moratti; Jim Simpson

doi:10.1107/S1600536811042693

. 2011 Oct 22;67(Pt 11):o3024–o3025. doi: 10.1107/S1600536811042693

N-(1-Acryloyl-2,2,6,6-tetramethylpiperidin-4-yl)acrylamide

Shailesh K Goswami ^a, Lyall R Hanton ^a, C John McAdam ^a, Stephen C Moratti ^a, Jim Simpson ^a,^*

PMCID: PMC3247421 PMID: 22220039

Abstract

The title compound, C₁₅H₂₄N₂O₂, crystallizes with two unique molecules, (I) and (II), in the asymmetric unit, differing in the orientation of the acryloyl units with respect to the piperidine rings. The acrylamide units are essentially planar in both molecules (r.m.s. deviations = 0.042 and 0.024 Å, respectively), as are the C₃N chains of the acryloyl units. The carbonyl O atoms of the acryloyl systems lie significantly out of these planes, viz. by −0.171 (9) Å for molecule (I) and by 0.33 (1) Å for molecule (II). The acrylamide and acryloyl planes are inclined at 68.7 (4)° and 59.8 (3)° in the two molecules. The piperidine rings each adopt twist boat conformations. In the crystal, strong N—H⋯O hydrogen bonds link the molecules into zigzag C(4) chains along b. Additional C—H⋯O contacts result in the formation of stacks along a.

Related literature

For the synthesis and applications, see: Murayama & Morimura (1971 ▶); Matsui et al. (1972 ▶). Very few structures of compounds similar to the title compound have been reported previously. The most closely related 2,2,6,6-tetramethylpiperidine structures are both nitroxide radicals but also have acrylamide substituents in the 4-position, see: Duskova et al. (2006 ▶); Qiu et al. (2009 ▶). For other related 2,2,6,6-tetramethylpiperidine structures, see: Cygler, Dobrynin et al. (1980 ▶); Cygler, Skarżyński et al. (1980 ▶); Cygler, Markowicz et al. (1980 ▶); Cygler (1981 ▶). For details of the Cambridge Structural Database, see: Allen (2002 ▶); and for hydrogen-bond motifs, see: Bernstein et al. (1995 ▶)

Experimental

Crystal data

C₁₅H₂₄N₂O₂
M _r = 264.36
Monoclinic,
a = 7.5810 (4) Å
b = 9.2635 (4) Å
c = 21.4193 (9) Å
β = 91.612 (2)°
V = 1503.61 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 91 K
0.65 × 0.24 × 0.14 mm

Data collection

Bruker APEXII CCD area detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.690, T _max = 0.744
9141 measured reflections
2252 independent reflections
2169 reflections with I > 2σ(I)
R _int = 0.040
θ_max = 18.6°

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.069
S = 1.12
2252 reflections
357 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.10 e Å⁻³
Δρ_min = −0.12 e Å⁻³

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

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811042693/cv5174sup1.cif

e-67-o3024-sup1.cif^{(37.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811042693/cv5174Isup2.hkl

e-67-o3024-Isup2.hkl^{(110.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811042693/cv5174Isup3.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
N22—H22N⋯O17	0.87 (3)	2.02 (3)	2.888 (4)	171 (3)
N12—H12N⋯O27ⁱ	0.87 (3)	1.98 (3)	2.841 (4)	177 (3)
C15—H15B⋯O13ⁱⁱ	0.99	2.67	3.613 (4)	159

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

Acknowledgments

The authors thank the New Economy Research Fund (grant No. UOO-X0808) for support of this work and the University of Otago for the purchase of the diffractometer.

supplementary crystallographic information

Comment

The title compound has been used for stabilization of synthetic polymers against photo and thermal deterioration (Murayama & Morimura, 1971; Matsui et al., 1972). Our synthesis and interest relates to its use as a cross-linker in our work with electroactive polymers. The title compound, crystallizes with two unique molecules (I), Fig. 1a, and (II), Fig. 1b, linked in the asymmetric unit by an N—H···O hydrogen bond. Overlaying the two molecules in Mercury (Macrae et al., 2008), Fig 2, gives an r.m.s. deviation of 0.90 Å. The major differences lie in the orientation of the acryloyl units with respect to the piperidine rings, exemplified by the torsion angles C14–N11–C13–O13, -151.1 (3)° for (I) and C24–N21–C23–O23, -20.0 (5)° for (II). Each piperidine ring adopts a twist boat conformation with the acrylamide substituents equatorial. The N12–C17(O17)–C18–C19 and N22–C27(O27)–C28–C29 acrylamide substituents are planar, r.m.s. deviations 0.043 Å and 0.024 Å respectively as are the N11–C13–C12–C11 and N21–C23–C22–C21 chains of the acryloyl units with deviations 0.030 and 0.095 Å.

A search of the Cambridge Database (version 5.32, November 2010, with 5 updates; Allen, 2002) for 2,2,6,6-tetramethylpiperidine residues with C substituents on both the 1 and 4-positions revealed only 4 piperidinol derivatives (Cygler, Dobryninet al., 1980; Cygler, Skarżyński et al., 1980; Cygler, Markowicz et al., 1980; Cygler, 1981). Only two structures with acrylamide substituents in the 4-position were found (Duskova et al., 2006); Qiu et al., 2009), both involving nitroxide radicals. Bond distances and angles in the acrylamide segments of these structures compare well with those reported here.

In the crystal, C(4) chains (Bernstein et al., 1995) of molecules form along the b axis linked by strong intermolecular N—H···O hydrogen bonds (Table 1, Fig 3). Additional C15–H15B···O13 contacts (Table 1) cause the chains to form stacks along the a axis (Fig. 4).

Experimental

The title compound was synthesized in a manner similar to that previously reported (Murayama & Morimura, 1971). Following purification by column chromatography on silica gel and recrystallization, X-ray quality crystals of the title compound, N-(1-acryloyl-2,2,6,6-tetramethylpiperidin-4-yl)acrylamide were obtained from a CDCl₃ solution layered with ethanol. M.p. 113°C. ¹H NMR (400 MHz, CDCl₃): 6.53 & 6.28 [2 × (1H, dd, J = 1, 18 Hz, trans- =CH₂)], 6.10 (2H, m, 2 × –CH=), 5.9 (1H, bs, amide NH), 5.64 & 5.49 [2 × (1H, dd, J = 1, 10 Hz, cis- =CH₂)], 4.40 (1H, m, pip CH), 2.25 & 1.77 [2 × (2H, dd, J = 8, 16 Hz, pip CH₂)], 1.53 & 1.49 [2 × (6H, s, CH₃)]. ¹³C NMR (500 MHz, CDCl₃): 169.9, 164.9, 135.5, 130.6, 126.7, 124.0, 56.1, 44.1, 40.3, 31.2, 29.7.