Synthesis and Chiroptical Properties of Arylimines of Cholest-4-ene-3,6-dione
Xin Geng; Joel T. Mague; Robert A. Pascal; Journal of Organic Chemistry 77 (2012) 10920–10924; doi:10.1021/jo301591g

data_4027751
_publ_section_title
;
 Synthesis and Chiroptical Properties of Arylimines of
 Cholest-4-ene-3,6-dione
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              10920
_journal_page_last               10924
_journal_paper_doi               10.1021/jo301591g
_journal_volume                  77
_journal_year                    2012
_chemical_absolute_configuration rm
_chemical_compound_source        'chemical synthesis'
_chemical_formula_moiety         'C34 H49 N O2'
_chemical_formula_sum            'C34 H49 N O2'
_chemical_formula_weight         503.74
_chemical_melting_point          421.0(5)
_chemical_name_systematic
; 
 3-(4-methoxyphenylimino)cholest-4-ene-6-one 
;
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             'September 28, 2012'
_audit_creation_method
;
 SHELXL and manual editing
;
_audit_update_record
;
 Sept. 28, 2012 rp036rf.cif       Initial CIF created by RAP.

 Sept. 29, 2012 Sent to CheckCIF  See rp036rf_checkcif.pdf for alerts  
                                  that were generated. Comments on these
                                  alerts are given below.
------------------------------------------------------------------------
                ALERT level A = In general: serious problem
                ALERT level B = Potentially serious problem
                ALERT level C = Check and explain
                ALERT level G = General alerts; check
------------------------------------------------------------------------
STRVA01_ALERT_2_C  Chirality of atom sites is inverted? 
    From the CIF: _refine_ls_abs_structure_Flack  1.620 
    From the CIF: _refine_ls_abs_structure_Flack_su  1.270
PLAT791_ALERT_4_G Note: The Model has Chirality at C8 (Verify)  S
PLAT791_ALERT_4_G Note: The Model has Chirality at C9 (Verify)  S
                     . . . etc . . .
PLAT791_ALERT_4_G Note: The Model has Chirality at C57 (Verify)  R
PLAT791_ALERT_4_G Note: The Model has Chirality at C60 (Verify)  R

Comment/explanation: The absolute configuration of the molecule is
                     CERTAIN because it was synthesized in two steps
                     from natural cholesterol!!!  (It has the natural
                     cholestane stereochemistry at every tetrahedral
                     carbon.)
------------------------------------------------------------------------
PLAT033_ALERT_4_C Flack x Parameter Value Deviates from Zero .... 1.600
PLAT032_ALERT_4_G Std. Uncertainty on Flack Parameter Value High  1.300 
REFLT03_ALERT_4_G ALERT: MoKa measured Friedel data cannot be used to 
                         determine absolute structure in a light-atom
                         study EXCEPT under VERY special conditions. 
                         It is preferred that Friedel data is merged 
                         in such cases.

Comment/explanation: These alerts are normal for a light-atom structure
                     in a chiral space group.  While CheckCIF suggests
                     that the Friedel data be merged, one should note
                     that these data are inequivalent and thus on first
                     principles should not be merged.  We have therefore
                     elected not to do so.
------------------------------------------------------------------------
PLAT220_ALERT_2_B Large Non-Solvent  C  Ueq(max)/Ueq(min) ... 4.2 Ratio
PLAT220_ALERT_2_C Large Non-Solvent  C  Ueq(max)/Ueq(min) ... 3.1 Ratio 
PLAT222_ALERT_3_C Large Non-Solvent  H  Uiso(max)/Uiso(min) . 4.9 Ratio 
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds .......... 0.0041 Ang
PLAT072_ALERT_2_G SHELXL First Parameter in WGHT Unusually Large.. 0.11

Comment/explanation: none of these minor alerts are particularly unusual
                     in a large, light-atom structure.  There would be
                     little point in applying restraints to the few 
                     elongated thermal ellipsoids, and the single "low 
                     bond precision and the "large" weight value are in
                     fact quite normal.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.406(4)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   8.752(2)
_cell_length_b                   9.601(3)
_cell_length_c                   34.398(9)
_cell_measurement_reflns_used    9875
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.23
_cell_measurement_theta_min      2.37
_cell_volume                     2890.3(14)
_computing_cell_refinement       'Bruker SAINT (Bruker-AXS, 2009)'
_computing_data_collection       'Bruker APEX2 (Bruker-AXS, 2010)'
_computing_data_reduction        'Bruker SAINT (Bruker-AXS, 2009)'
_computing_molecular_graphics    'Bruker SHELXTL (Bruker-AXS, 2008)'
_computing_publication_material  'Bruker SHELXTL (Bruker-AXS, 2008)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2008)'
_computing_structure_solution    'FLIPPER 25 (Spek, 2012)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker Smart APEX CCD'
_diffrn_measurement_method       '\f and \w scans'
_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  0.0709
_diffrn_reflns_av_sigmaI/netI    0.0693
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            49125
_diffrn_reflns_theta_full        28.23
_diffrn_reflns_theta_max         28.23
_diffrn_reflns_theta_min         2.20
_exptl_absorpt_coefficient_mu    0.070
_exptl_absorpt_correction_T_max  0.9923
_exptl_absorpt_correction_T_min  0.6632
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2009)'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.158
_exptl_crystal_description       Block
_exptl_crystal_F_000             1104
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.546
_refine_diff_density_min         -0.351
_refine_diff_density_rms         0.091
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   1.62(127)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     679
_refine_ls_number_reflns         14029
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0909
_refine_ls_R_factor_gt           0.0739
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1076P)^2^+1.1744P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1867
_refine_ls_wR_factor_ref         0.2017
_reflns_number_gt                11363
_reflns_number_total             14031
_reflns_threshold_expression     >2\s(I)
_cod_data_source_file            jo301591g_si_003.cif
_cod_data_source_block           rp036rf
_cod_original_cell_volume        2890.4(13)
_cod_database_code               4027751