tert-Butyl N-{[5-(5-oxohexa­namido)­pyridin-2-yl]amino}­carbamate

Luisa Ronga; Noel Pinaud; Charlotte Rimbault; Mathieu Marchivie; Jean Guillon

doi:10.1107/S1600536813024598

. 2013 Sep 12;69(Pt 10):o1531–o1532. doi: 10.1107/S1600536813024598

tert-Butyl N-{[5-(5-oxohexanamido)pyridin-2-yl]amino}carbamate

Luisa Ronga ^a, Noel Pinaud ^b, Charlotte Rimbault ^a, Mathieu Marchivie ^a, Jean Guillon ^a,^*

PMCID: PMC3790400 PMID: 24098219

Abstract

In the crystal structure of the title compound, C₁₆H₂₄N₄O₄, molecules are linked by N—H⋯O hydrogen bonds between the carbonyl groups of the carbamoyl and amido functional groups and the amino groups, and by N—H⋯N hydrogen bonds between the amino group and the pyridine ring, forming two-dimensional networks parallel to the ab plane.

Related literature

For the synthesis, properties and biological activity of 2-hydrazinopyridine derivatives, see: Ardisson et al. (2005 ▶); Jurisson & Lydon (1999 ▶); Abrams et al. (1994 ▶); Liu et al. (2011 ▶); Lu et al. (2011 ▶); Schwartz et al. (1990 ▶). For the crystal structures of related compounds, see: Banerjee et al. (2005 ▶); Rose et al. (1998 ▶); Zora et al. (2006 ▶). For synthesis, see: Cugola et al. (1995 ▶).

Experimental

Crystal data

C₁₆H₂₄N₄O₄
M _r = 336.39
Triclinic,
a = 6.2598 (4) Å
b = 9.2822 (6) Å
c = 16.0437 (12) Å
α = 84.387 (6)°
β = 88.957 (6)°
γ = 79.358 (6)°
V = 911.79 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.84 × 0.17 × 0.06 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.928, T _max = 0.994
20299 measured reflections
3295 independent reflections
2187 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.147
S = 1.04
3295 reflections
221 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: DIRAX/LSQ (Duisenberg, 1992 ▶); data reduction: EVALCCD (Duisenberg et al., 2003 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813024598/ff2115sup1.cif

e-69-o1531-sup1.cif^{(18.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813024598/ff2115Isup2.hkl

e-69-o1531-Isup2.hkl^{(180.9KB, hkl)}

Click here for additional data file.^{(6.5KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813024598/ff2115Isup3.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
N1—H1⋯O3ⁱ	0.86	2.06	2.888 (2)	161
N3—H3⋯N2ⁱⁱ	0.86	2.21	2.957 (3)	145
N4—H4⋯O2ⁱⁱⁱ	0.86	2.06	2.827 (3)	149

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

Acknowledgments

This publication was supported by a grant from the Ligue Nationale contre le Cancer (Comité Aquitaine-Charentes, Bordeaux, France).

supplementary crystallographic information

1. Comment

Radioisotopes conjugated to proteins provide a means for imaging and treatment of disease. The bifunctional 2-hydrazinopyridine derivatives are useful linker molecules for attaching metal ions such as ⁹⁹^mTc to macromolecules (Ardisson et al., 2005; Jurisson & Lydon, 1999). Hence, this 2-hydrazinopyridinyl moiety has previously been used for labeling bioactive molecules (Abrams et al., 1994; Banerjee et al. 2005; Rose et al., 1998; Schwartz et al., 1990). Thus, the use of Tc-labeled hydrazine derivatives continues to undergo further development (Liu et al., 2011; Lu et al., 2011). The wide spectrum of medicinal applications of this class of radiolabeled chelates prompted us to work in this domain and we report herein on the synthesis and crystal structure of the title compound, designed as a potential chelate for ⁹⁹^mTc.

The title compound, C₁₆H₂₄N₄O₄, has the triclinic (P1) symmetry. It crystalizes with one molecule in the asymmetric unit. In the crystal, the molecules are linked together by N—H···O hydrogen bonding between the carbonyl groups of the carbamoyl and amido functional groups and the amino groups and by N—H···N hydrogen bonding between amino and pyridine moiety leading to a two-dimensional network within the ab plane. The network cohesion in the 3^rd direction is assured by Van der Waals interactions and H-bond like interactions between the carbonyl and the BOC group.

2. Experimental

To a stirred solution of 5-oxohexanoic acid (2.45 mmol) in 15 ml of tetrahydrofurane was added triethylamine (2.45 mmol). After 10 min of stirring at room temperature was added isobutyl chloroformate (2.45 mmol). The reaction mixture was stirred at room temperature for 5 h, then 2-(t-butoxycarbonyl hydrazine)-5-amino-pyridine (2.23 mmol) (Cugola et al.,19955) was added and the reaction stirred for 12 h. The mixture was evaporated to dryness, and the residue was triturated in water. The solid precipitate was filtered off and washed with water then with ethanol, and purified by column chromatography using CHCl₃/methanol (9/1, v/v) as eluent to give the title compound as white crystals (R_f = 1/4). Yield is 48%. The single-crystal of the title product was obtained by slow crystallization from a mixture DMSO/methanol (9/1, v/v). M.p. = 219°C. IR (KBr), ν/cm^-1: 3270, 3230, 3185, 3082, 2982, 1704, 1662, 1601, 1537, 1276, 1182. ¹H NMR (300 MHz, DMSO-d₆, 298 K): δ = 1.41 (s, 9H, 3 CH₃), 1.75 (qt, 2H, J = 6.10, CH₂), 2.09 (s, 3H, CH₃), 2.26 (t, 2H, J = 6.10, CH₂), 2.48 (t, 2H, J = 6.10, CH₂), 6.49 (d, 1H, J = 7.50, H-3), 7.71 (dd, 1H, J = 7.50 and 1.55, H-4), 7.95 (s, 1H, NH), 8.20 (d, 1H, J = 1.55, H-6), 8.75 (s, 1H, NH), 9.70 (s, 1H, NH). Anal. Calcd. for C₁₆H₂₄N₄O₄: C, 57.13; H, 7.19; N, 16.66 Found: C, 57.26; H, 7.25; N, 16.52.