Low-Valent Ene-Amido Iron Complexes for the Asymmetric Transfer Hydrogenation of Acetophenone without Base
Paraskevi O. Lagaditis; Alan J. Lough; Robert H. Morris; Journal of the American Chemical Society 133 (2011) 9662–9665; doi:10.1021/ja202375y

data_4106318
_publ_section_title
;
 Low-Valent Ene-Amido Iron Complexes for the Asymmetric Transfer
 Hydrogenation of Acetophenone without Base
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9662
_journal_page_last               9665
_journal_paper_doi               10.1021/ja202375y
_journal_volume                  133
_journal_year                    2011
_chemical_formula_moiety         'C35 H54 Br Fe N2 O P2, C24 H20 B'
_chemical_formula_sum            'C59 H74 B Br Fe N2 O P2'
_chemical_formula_weight         1035.71
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                64.1830(19)
_cell_angle_beta                 72.743(3)
_cell_angle_gamma                75.348(3)
_cell_formula_units_Z            2
_cell_length_a                   13.3469(6)
_cell_length_b                   15.7707(8)
_cell_length_c                   17.3778(9)
_cell_measurement_reflns_used    29845
_cell_measurement_temperature    150(1)
_cell_measurement_theta_max      27.5
_cell_measurement_theta_min      2.6
_cell_volume                     3111.8(3)
_computing_cell_refinement       'Denzo-SMN (Otwinowski & Minor, 1997)'
_computing_data_collection       'Collect (Nonius B.V., 1997-2002)'
_computing_data_reduction        Denzo-SMN
_computing_molecular_graphics    'PLATON (Spek, 2003)'
_computing_publication_material  'SHELXTL V6.1'
_computing_structure_refinement  'SHELXTL V6.1 (Sheldrick, 2008)'
_computing_structure_solution    'SIR-92 (Altomare et al., 1994)'
_diffrn_ambient_temperature      150(2)
_diffrn_detector_area_resol_mean 9
_diffrn_measured_fraction_theta_full 0.968
_diffrn_measured_fraction_theta_max 0.946
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_method       '\f scans and \w scans with \k offsets'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.116
_diffrn_reflns_av_sigmaI/netI    0.149
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            29845
_diffrn_reflns_theta_full        25.24
_diffrn_reflns_theta_max         27.46
_diffrn_reflns_theta_min         2.56
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.971
_exptl_absorpt_correction_T_max  0.971
_exptl_absorpt_correction_T_min  0.632
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
multi-scan from symmetry-related measurements 
 Sortav (Blessing 1995)
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.105
_exptl_crystal_description       plate
_exptl_crystal_F_000             1092
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.04
_platon_squeeze_details
;

During the
refinement of the structure, electron density peaks were located 
that were believed to be highly disordered
solvent molecules (possibly pentane and/or THF). Attempts 
made to model the solvent molecule were not successful. 
The SQUEEZE option in PLATON (Spek, 2003) indicated there were
solvent cavities with a total volume of 687.0 \%A^3^ containing 
approximately 145 electrons per unit cell.
In the final cycles of refinement, this contribution to the
electron density was removed from the observed data. The
density, the F(000) value, the molecular weight and the formula are
given without taking into account the results obtained with the
SQUEEZE option PLATON (Spek, 2003). Similar treatments of disordered
solvent molecules were carried out by St\"ahler et al. (2001), 
Cox et al. (2003), Mohamed et al. (2003) and Athimoolam et al. (2005).
References:

Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13

Athimoolam, S., Kumar, J., Ramakrishnan, V. & Rajaram, R.K. (2005).
Acta Cryst. E61, m2014-m2017.

Cox, J.P., Kumarasammy, Y., Nahar, L., Sarkar D.S. & Shoeb, M.
(2003). Acta Cryst. E59, o975-o977.

Mohamed, A.A., Krause Bauer, A.J., Bruce, E.A. & Bruce M.R.M.
(2003). Acta Cryst. C59, m84-m86.

St\"ahler, R., N\"ather, C. & Bensch, W. (2001). Acta Cryst.
C57, 26-27.
;
_refine_diff_density_max         0.533
_refine_diff_density_min         -0.569
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.892
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     604
_refine_ls_number_reflns         13485
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.892
_refine_ls_R_factor_all          0.1430
_refine_ls_R_factor_gt           0.0674
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0783P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1497
_refine_ls_wR_factor_ref         0.1720
_reflns_number_gt                6527
_reflns_number_total             13485
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            ja202375y_si_002_1.cif
_cod_data_source_block           4a
_cod_database_code               4106318