(R C,S Fe)-1-[3,5-Bis(trifluoromethyl)phenyl]-3-{1-[2-(diphenylphosphanyl)ferrocenyl]ethyl}thiourea (unknown solvate)

In the molecule of the the title compound, [Fe(C5H5)(C28H22F6N2PS)], the absolute configuration is R C ,SFe. The dihedral angle between the trifluoromethyl-substituted phenyl ring and the thiourea plane is 41.8 (9)°. The iron atom is bound to the cyclopentadienyl rings in the typical η5-manner in a close to eclipsed conformation. The crystal structure features N—H⋯S hydrogen bonds, with the S atom as an acceptor for both N—H groups, forming a layered arrangement parallel to (1-10). The two –CF3 groups are each disordered over two positions with refined occupancy rates for the major components of 0.66 (7) and 0.55 (5). The crystal was grown from mixed solvents (n-hexane and ethyl acetate). These solvents are disordered in the crystal and the resulting electron density was found to be uninterpretable. The solvent contribution to the structure factors was taken into account by back-Fourier transformation of all density found in the disordered solvent area using the SQUEEZE routine in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148–155]. The formula mass and density do not take account of the solvent.

In the molecule of the the title compound, [Fe(C 5 H 5 )(C 28 H 22 F 6 N 2 PS)], the absolute configuration is R C ,S Fe . The dihedral angle between the trifluoromethylsubstituted phenyl ring and the thiourea plane is 41.8 (9) . The iron atom is bound to the cyclopentadienyl rings in the typical 5 -manner in a close to eclipsed conformation. The crystal structure features N-HÁ Á ÁS hydrogen bonds, with the S atom as an acceptor for both N-H groups, forming a layered arrangement parallel to (110). The two -CF 3 groups are each disordered over two positions with refined occupancy rates for the major components of 0.66 (7) and 0.55 (5). The crystal was grown from mixed solvents (n-hexane and ethyl acetate). These solvents are disordered in the crystal and the resulting electron density was found to be uninterpretable. The solvent contribution to the structure factors was taken into account by back-Fourier transformation of all density found in the disordered solvent area using the SQUEEZE routine in PLATON [Spek (2009). Acta Cryst. D65, 148-155]. The formula mass and density do not take account of the solvent.

Related literature
For an introduction to the Morita-Baylis-Hillman reaction, see: Basavaiah et al. (2010). For the synthesis of (R C ,S Fe )-1-(2-(diphenylphosphanyl)ferrocenyl)ethanamine and structures related to the title compound, see: Chen et al. (2006). For the synthesis of the title compound, see: Sohtome et al. (2004). For refinement details concerning the use of SQUEEZE, see: Spek (2009 The iron center is bound to the cyclopentadienyl rings in the typical η 5 manner. The ferrocene group deviates ca. 5 ° from an ideal eclipsed conformation. The angle between the planes of the two cyclopentadienyl rings is 2.8 (9) °.
There are solvent acessible voids in the crystal structure that accomodate solvent molecules in a very disordered way which were corrected for by back-Fourier transformation of all density found in the disordered solvent area using the Squeeze algorithm as implemented in Platon (Spek, 2009). These solvent molecules were not included in the calculation of the overall formula weight, density and absorption coefficient (see refinement section for details).

Refinement
All H atoms were placed in idealized positions and allowed to ride on the respective parent atom with C-H distances of 0.98 Å (ferrocenyl), 0.93 Å (aromatic), 0.96 Å (CH 3 ), or 0.98 Å (CH) and N-H distance of 0.86 Å, and with U iso (H) = 1.5 U eq (C) for methyl H atoms, with U iso (H) = 1.2 U eq (C) for aromatic and methylene H atoms.
Some residual electron densities were difficult to model, therefore the SQUEEZE function of PLATON (Spek, 2009) was used to eliminate the contribution of the electron density in the solvent region from the intensity data, and the solvent-free model was employed for the final refinement. There are two cavities of 652 Å 3 per unit cell. PLATON estimated that each cavity contains 74 electrons. PLATON estimated that each single crystal molecular contains 20 residual electrons. Because single crystals were obtained from a solution of the title compound in a mixture of n-hexane and EtOAc, so we could not be sure which solvent it was. It may be n-hexane [CH 3 (CH 2 )3CH 3 ], EtOAc (CH 3 COOCH 2 CH 3 ) or water (H 2 O). The solvent is therefore not given in the formula, scheme, Mr etc. .

Figure 1
The molecular structure of the title compound, with displacement ellipsoids at the 30% probability level. All H atoms have been omitted for clarity. The disorder of the CF 3 groups has been indicated. Crystal packing in the title compound where molecules are linked via N-H···S hydrogen bonds (dashed lines). Except for those involved in hydrogen-bonding interactions, H atoms have been omitted for clarity.

(R C ,S Fe )-1-[3,5-Bis(trifluoromethyl)phenyl]-3-{1-[2-(diphenylphosphanyl)ferrocenyl]ethyl}thiourea (unknown solvate)
Crystal data  Extinction correction: SHELXL97 (Sheldrick, 2008), Fc * =kFc[1+0.001xFc 2 λ 3 /sin(2θ)] -1/4 Extinction coefficient: 0.00072 (19) Absolute structure: Flack (1983), 3680 Friedel pairs Flack parameter: 0.01 (2) 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.