N-(12-Amino-9,10-dihydro-9,10-ethanoanthracen-11-yl)-4-methylbenzenesulfonamide

The title compound, C23H22N2O2S, crystallizes with the 4-methylbenzenesulfonamide entity oriented towards the center of the bridgehead C atoms with a C—N—S—C torsion angle of −61.3 (2)°. The molecule features an intramolecular N—H⋯N hydrogen bond. Weak C—H⋯O and C—H⋯π interactions aid in forming the three-dimensional supramolecular structure.

The title compound, C 23 H 22 N 2 O 2 S, crystallizes with the 4methylbenzenesulfonamide entity oriented towards the center of the bridgehead C atoms with a C-N-S-C torsion angle of À61.3 (2) . The molecule features an intramolecular N-HÁ Á ÁN hydrogen bond. Weak C-HÁ Á ÁO and C-HÁ Á Á interactions aid in forming the three-dimensional supramolecular structure.

Synthesis and crystallization
The title compound was prepared by the literature method (Matsunaga et al., 2005) and recrystallized from CH 2 Cl 2 /EtOH as colourless plates.

Refinement
H-atoms attached to the bridgehead carbon atoms and to nitrogen were located and refined. The remainder were placed in calculated positions (C-H = 0.95 -0.98 Å) and included as riding contributions with isotropic displacement parameters 1.2-1.5 times those of the attached carbon atoms.

Results and discussion
The development of chiral ligands for asymmetric catalytic reactions is a subject of considerable interest in the field of asymmetric synthesis (Abdel-Aziz et al., 2000, 2001, 2004Matsunaga et al., 2005;Seo et al., 2001). As part of our onging program of drug design and discovery we report the structure of the title compound. Some applications of related compounds have been reported (Yamakuchi et al., 2005;Matsunaga et al., 2005;Abdel-Aziz et al., 2004). The 4-methylbenzenesulfonamide entity is oriented towards the center of the bridgehead carbon atoms (C1, C16), partly due to the N1 -H1N···N2 interaction, as indicated by the C1-N1-S1-C17 torsion angle of -61.3 (2)°. The dihedral angle between the benzene ring (C17-C22) and the mean plane of the C1/C2/C9/C16 unit is 87.78 (7)°. The packing of the molecules is aided by weak C-H···O hydrogen bonds as well as a C-H···π interaction between C11-H11 and the centroid of the C3-C8 ring at -x, -0.5 + y, 1 -z forming the three-dimensional supramolecular structure (Table 1 and Fig. 2).  Perspective view of the title molecule showing the intramolecular hydrogen bond. Displacement ellipsoids are drawn at the 50% probability level.

Special details
Experimental. The diffraction data were obtained from 8 sets of 340 frames, each of width 0.5° in ω, collected at φ = 0.00, 90.00, 180.00 and 270.00° and at 2θ = -50.00 and -90.00° and 4 sets of 340 frames, each of width 0.5° in ω collected at 2θ = -90.00° and φ = 45.00, 135.00, 225.00 and 315.00°. The scan time was 20 sec/frame. 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. H-atoms attached to the bridgehead carbon atoms and to nitrogen were located and refined. The remainder were placed in calculated positions (C-H = 0.95 -0.98 Å) and included as riding contributions with isotropic displacement parameters 1.2 -1.5 times those of the attached carbon atoms.