5-Bromo-17-nitro-26,28-prop-2-enoxy-25,27-dipropoxycalix[4]arene

Molecules of the title compound, C40H42BrNO6, are located on a crystallographic twofold rotation axis. As a result, the nitro group and bromine residue are mutually disordered with equal occupancies. The propoxy-substituted aromatic rings are close to parallel to each other [dihedral angle = 21.24 (1)°], whereas the propenoxy-substituted rings enclose a dihedral angle of 70.44 (1)°. The dihedral angles between the methylene C atoms and the aromatic rings shows that the propenoxy substituted rings are bent away from the calixarene cavity [dihedral angle between the planes = 35.22 (8)°], whereas the propoxy-substituted rings are almost perpendicular [79.38 (10)°] to the plane of the methylene C atoms.

Molecules of the title compound, C 40 H 42 BrNO 6 , are located on a crystallographic twofold rotation axis. As a result, the nitro group and bromine residue are mutually disordered with equal occupancies. The propoxy-substituted aromatic rings are close to parallel to each other [dihedral angle = 21.24 (1) ], whereas the propenoxy-substituted rings enclose a dihedral angle of 70.44 (1) . The dihedral angles between the methylene C atoms and the aromatic rings shows that the propenoxy substituted rings are bent away from the calixarene cavity [dihedral angle between the planes = 35.22 (8) ], whereas the propoxy-substituted rings are almost perpendicular [79.38 (10) ] to the plane of the methylene C atoms.
Molecules of the title compound 3 (Fig. 1) are located on a crystallographic twofold rotation axis. As a result of that, the nitro group and bromine residue are mutually disordered. The propoxy substituted aromatic rings are almost parallel to each other [dihedral angle 21.24 (1)°], whereas the propenoxy substituted rings enclose a dihedral angle of 70.44 (1)°.
The dihedral angles between the methylene C atoms and the aromatic rings shows that the propenoxy substituted rings are bent away from the calixarene cavity [dihedral angle between the planes 35.22 (8)°] whereas the propoxy substituted rings are almost perpendicular [79.38 (10)°] to the plane of the methylene C atoms. -26,28-dipropyloxycalix[4]arene was synthesized according to literature (Sansone et al., 2004). Under an argon atmosphere 29 mg (0.045 mmol, 1 equiv.) of compound 2 and 26 mg (1.12 mmol, 25 equiv.) of NaH were suspended in 2 ml of dry DMF and stirred for some minutes. Afterwards, 135 mg (1.12 mmol, 25 equiv.) of allyl bromide in 0.7 ml DMF were slowly added to the mixture and the latter stirred for additional 12 h at room temperature.

5-Mononitro
Subsequently, the reaction suspension was slowly stirred into a mixture of 20 ml CH 2 Cl 2 and 10 ml 1 N HCl. The obtained organic phase was separated, washed with water and brine and dried over MgSO 4 . The solvent was evaporated and the resulting crude product was purified by column chromatography with CH 2 Cl 2 /pentane 40:60 and subsequent crystallization from CHCl 3 /methanol. Compound 3 was obtained as white crystals (7 mg

S3. Refinement
H atoms were geometrically positioned and refined using a riding model with fixed individual displacement parameters [U(H) = 1.2 U eq (C) or U(H) = 1.5 U eq (C methyl )] using a riding model with C-H(aromatic) = 0.95 Å, C-H(methyl) = 0.98 Å, or C-H(methylene) = 0.99 Å, respectively. Due to the crystallographic symmetry of the molecule, the Br atom and the nitro group are mutually disordered with equal occupancies. The N atom of the nitro group is so close to the bromine atom that its U value could not be refined and was fixed to 0.05. The following restraints were applied to the nitro group: N-C bond distance 1.470 (1) Å, N-O bond distances 1.220 (1) Å, N···C α distances 2.450 (1) Å. The propenyloxy and propoxy groups are disordered over two sites each with site occupation factors of 0.63 (1) and 0.72 (1), respectively, for the major occupied site. Bond lengths and angles in these groups were restrained to be equal and the displacement ellipsoids of the minor occupied atoms were restrained to an isotropic behaviour.  The formation of the title compound. Special details Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > σ(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 )
x y z U iso */U eq Occ. (