21-(4-Methyl­phenyl­sulfon­yl)-4,7,13,16-tetra­oxa-1,10,21-triaza­bicyclo­[8.8.5]tricosane-19,23-dione: an N-tosyl­ated macrobicyclic dilactam

Trevor K Ellis; Stephen M Clayton, Jr; Douglas R Powell; Richard W Taylor

doi:10.1107/S1600536811018873

. 2011 May 28;67(Pt 6):o1533. doi: 10.1107/S1600536811018873

21-(4-Methylphenylsulfonyl)-4,7,13,16-tetraoxa-1,10,21-triazabicyclo[8.8.5]tricosane-19,23-dione: an N-tosylated macrobicyclic dilactam

Trevor K Ellis ^a, Stephen M Clayton Jr ^a, Douglas R Powell ^a, Richard W Taylor ^a,^*

PMCID: PMC3120313 PMID: 21754893

Abstract

The macrobicyclic title compound, C₂₃H₃₅N₃O₈S, contains two tertiary amide bridgehead N atoms and a toluenesulfonamide N atom in the center of the five-atom bridging strand. The molecule has a central cavity that is defined by the 18-membered ring identified by the N₂O₄ donor atom set and two 15-membered rings with N₃O₂ donor atom sets. The toluenesulfonamide N atom adopts an exo orientation with respect to the central cavity, and the tosyl group is oriented on one side of the aza-bridging strand that connects the bridgehead N atoms.

Related literature

For general background to bicyclic dilactams as cation receptors, see: Hourdakis & Popov (1977 ▶); Tümmler et al. (1977 ▶); Buschmann, (1986 ▶); Pietraszkiewicz et al. (1992 ▶); Wanichacheva et al. (2006a ▶,b ▶). For related structures, see: Fields et al. (1986 ▶); Tarnowska et al. (2004 ▶). For the synthesis, see: Lehn & Montavon (1976 ▶, 1978 ▶); Lehn et al. (1977 ▶); Frère & Gramain (1982 ▶); Pietraszkiewicz et al. (1992 ▶); Wanichacheva et al. (2006a ▶,b ▶).

Experimental

Crystal data

C₂₃H₃₅N₃O₈S
M _r = 513.60
Monoclinic,
a = 12.807 (2) Å
b = 20.096 (3) Å
c = 10.3305 (17) Å
β = 112.949 (3)°
V = 2448.3 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 100 K
0.45 × 0.34 × 0.02 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T _min = 0.921, T _max = 0.996
22174 measured reflections
5330 independent reflections
3651 reflections with I > 2σ(I)
R _int = 0.078

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.152
S = 1.00
5330 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.74 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811018873/pk2323sup1.cif

e-67-o1533-sup1.cif^{(23.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811018873/pk2323Isup2.hkl

e-67-o1533-Isup2.hkl^{(261KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811018873/pk2323Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the Oklahoma Center for the Advancement of Science and Technology (grant HR06–113). The authors also thank the National Science Foundation (CHE-0130835) and the University of Oklahoma for funds to acquire the diffractometer and computers used in this work.

supplementary crystallographic information

Comment

The title compound (I) was isolated as an intermediate in the synthesis of the corresponding azacryptand, 2.2.1_NH (II, see Figure 1). An analogous bicyclic diamide, 2.2.1* (III), containing only oxygen donor atoms in the bridging strands, has been reported (Tarnowska, et al., 2004). Cryptands where one or more O atoms have been replaced by N atoms are of interest because of their selectivity for transition- and heavy-metal cations (Lehn & Montavon, 1978). In addition, the nitrogen atom may serve as a point of attachment for sensor chromophores (Wanichacheva, et al., 2006a) or cryptand-based polymer resins (Frère & Gramain, 1982). The bicyclic 2.2.1*_NR dilactam with R = (CH₂)₉CH₃ (Pietraszkiewicz et al., 1992) or R = –C(=O)(CH₂)₁₅SCH₃ (Wanichacheva, et al., 2006b) has been used in the construction of ion selective electrodes.

Figure 2 shows that (I) consists of an 18-membered ring (donor atoms N1, O4, O7, N10, O13, O16) and two 15-membered rings with N₃O₂ donor atom sets (N1, O4, O7, N21, N10 and N1, O13, O16, N10, N21). With respect to the molecular cavity formed by these rings, donor atoms N1, O3, O13, O16 and N10 have an endodentate orientation, while N21, O7 and the carbonyl O atoms, O33 and O34, are exodentate. The oxygen donor atoms of the 18-membered ring (O4, O7, O13, O16) form a plane (average deviation = 0.314 Å) that is nearly perpendicular to the plane defined by nitrogen atoms N1, N10, N21 (dihedral angle = 83.7 (3)°). The toluenesulfonamide group is oriented over the face of one 15-membered ring (N1, O13, O16, N10, N21) and the plane of the benzene ring (C24—C29), average deviation = 0.0042 Å) is almost coplanar with the oxygen donor plane defined by O4, O7, O13, O16 (dihedral angle = 16.5 (3)°). The N1···N10 nonbonding distance is 5.299 (4)Å which is less than the value of 5.643 (4)Å found for 2.2.1* (Tarnowska et al., 2004). The aza bridging strand consists of three planar subunits: N1, C19, O33, C20, average deviation = 0.0021 Å; C20, N21, S1, C22, average deviation = 0.0255 Å; and C22, C23, O34, N10, average deviation = 0.0068 Å. The limited conformational freedom of this bridge may explain the shorter N1···N10 nonbonding distance compared to the more flexible 2.2.1* and the extensive splitting in the ¹H-NMR spectrum due to the non-equivalence of the methylene protons.

Experimental

The bicyclic diamide was obtained by the high-dilution condensation of 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane with 2,2'-(N-tosyl)diacetyl chloride according to reported methods (Lehn & Montavon, 1976). The N-protected diacid chloride was prepared following literature procedures (Lehn, et al., 1977). The crude dilactam was purified by flash column chromatography on silica gel using a mixture of CHCl₃ and acetone (4:1) as the eluent. Spectroscopic Analysis: ¹H-NMR (CDCl₃, 300 MHz) δ 2.38 (s, 3H), δ 2.57–2.64 (ddd, 2H), δ 2.90–3.00 (ddd, 2H), δ 3.49–3.65 (m, 10H), δ 3.67–3.80 (m, 8H), δ 4.36 (d, 4H), δ 4.53 (ddd, 2H), δ 7.25, 7.90 (q, 4H); ESI-MS: m/z = 536.2 (M + Na⁺) and 1049.5 (2M + Na⁺). Crystals suitable for X-ray crystallography were obtained by slow evaporation of a solution of the compound dissolved in toluene-methanol (1:1).