(4,7,13,16,21,24-Hexaoxa-1,10-diaza­bicyclo­[8.8.8]hexa­cosa­ne)sodium perchlorate

Ilia A Guzei; Joe W Su; Lara C Spencer; Ronald R Burnette

doi:10.1107/S1600536809039683

. 2009 Oct 17;65(Pt 11):m1381–m1382. doi: 10.1107/S1600536809039683

(4,7,13,16,21,24-Hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane)sodium perchlorate

Ilia A Guzei ^a,^*, Joe W Su ^b, Lara C Spencer ^a, Ronald R Burnette ^c

PMCID: PMC2971382 PMID: 21578130

Abstract

The title compound, [Na(C₁₈H₃₆N₂O₆)]ClO₄, was isolated and crystallized to understand more fully the ligand’s binding specificity to cations. The cation and anion reside at an intersection of crystallographic twofold and threefold axes. The carbon atoms in the cation are disordered over two positions in a 3:2 ratio, and the anion is equally disordered over two positions. The geometries of the cation and anion are typical. The compound packs in alternating sheets of discrete cations and anions stacked along the c axis, separated by a distance equal to one-sixth the length of the c axis.

Related literature

For general background to the macrocyclic polyether 4,7,13,16,21,24-hexaoxa-1,10-diaza-bicyclo[8.8.8]hexacosane, see: Izatt et al. (1985 ▶); Tait et al. (1997 ▶); Varga et al. (1994 ▶); Trend et al. (1993 ▶); Hamacher et al. (1986 ▶); Su & Burnette (2008 ▶). For related structures, see: Belaj et al. (1997 ▶); Tehan et al. (1974 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶) and for Mogul, see: Bruno et al. (2004 ▶).

Experimental

Crystal data

[Na(C₁₈H₃₆N₂O₆)]ClO₄
M _r = 498.93
Rhombohedral,
a = 8.4730 (3) Å
c = 28.220 (3) Å
V = 1754.5 (2) Å³
Z = 3
Mo- Kα radiation
μ = 0.24 mm⁻¹
T = 100 K
0.49 × 0.37 × 0.35 mm

Data collection

Bruker CCD-1000 area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.893, T _max = 0.922
6885 measured reflections
805 independent reflections
765 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.113
S = 1.11
805 reflections
85 parameters
144 restraints
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack (1983 ▶), 319 Friedel pairs
Flack parameter: 0.01 (15)

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, OLEX2 (Dolomanov et al., 2009 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL, modiCIFer (Guzei, 2007 ▶) and publCIF (Westrip, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809039683/hk2757sup1.cif

e-65-m1381-sup1.cif^{(23KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809039683/hk2757Isup2.hkl

e-65-m1381-Isup2.hkl^{(40.4KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Cl1—O2ⁱ	1.422 (4)
Cl1—O2	1.422 (4)
Cl1—O3ⁱ	1.434 (3)
Cl1—O3ⁱⁱ	1.434 (3)
Cl1—O3	1.434 (3)
Cl1—O3ⁱⁱⁱ	1.434 (3)
Cl1—O3^iv	1.434 (3)
Cl1—O3^v	1.434 (3)
Na1—O1	2.5661 (15)
Na1—N1	2.684 (2)
O2—O3ⁱⁱⁱ	1.639 (5)
O3—O3^v	1.797 (10)

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

Acknowledgments

We thank the National Science Foundation for financial support.

supplementary crystallographic information

Comment

The macrocyclic polyether 4,7,13,16,21,24-hexaoxa-1,10-diaza-bicyclo[8.8.8]hexacosane (222) is a classic example of a host molecule possessing important clinical functions. 222 encapsulates 1:1 various alkali and alkaline earth metals, and features high selectivity for K⁺ and Sr²⁺ in solution (Izatt et al., 1985). Tait et al. (1997) formulated a cation exchange resin treated with 222 that sorbed more than 95% of the fallout nuclide ⁹⁰Sr in liquid milk (295 K, pH 5.2, 4 h contact time, 1:50 resin to milk volume ratio). Varga et al. (1994) synthesized functionalized 222 for ⁸⁵Sr²⁺ decorporation in the rat and mouse. J. E. Trend and co-workers (1993) formulated 222 with a covalently bound chromophore to assay clinical blood K⁺⁴. Hamacher et al. (1986) developed the use of [K⁺(222)]¹⁸F^- as a phase transfer catalyst in synthesizing the clinically significant PET tracer 2-[¹⁸F]fluoro-2-deoxy-D-glucose. Due to 222 obvious industrial and clinical applications the relative binding characteristics of 222 to Li⁺, Na⁺ and K⁺ have been studied in order to more fully understand 222's binding specificity to cations (Su & Burnette, 2008).

In the title compound, (I), both the Na⁺(222) cation and the perchlorate anion of (I) reside at an intersection of crystallographic twofold and threefold axes. All the carbon atoms in the cation are disordered over two positions in a 3:2 ratio. The perchlorate anion is equally disordered over two positions. Multiple restraints were applied to ensure computational stability of the refinement.

The bond distances and angles within (I) are typical as confirmed by the Mogul structural check (Bruno et. al, 2004). Among 59 relevant compounds reported to the CSD (Allen, 2002), the most closely related is (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo(8.8.8)hexacosane)-sodium periodate which contains the same cation as (I) and a periodate anion instead of the perchlorate anion (Belaj et al., 1997), and sodium (2,2,2)-crypt-sodium (Tehan et al., 1974) which forms crystals in the same rhombohedral space group R32, as (I).

The packing structure of compound (I) consists of alternating sheets of cations and anions stacked along the c axis. The distance between these sheets is 4.70 Å, or one sixth of the length of the c axis.

Experimental

An equimolar mixture of 222 and NaClO₄ was prepared in acetone. The mixture was allowed to evaporate slowly at room temperature until crystallization was observed.