Desymmetrization Reactions of Indigo with Grignard Reagents for the Synthesis of Selective Antiplasmodial [1<i>H</i>,3'<i>H</i>]-3-Aryl-2,2'-diindol-3'-ones.
Butler, Nicholas M.; Bremner, John B.; Willis, Anthony C.; Lucantoni, Leonardo; Avery, Vicky M.; Keller, Paul A.; The Journal of organic chemistry 84 (2019) 11228–11239; doi:10.1021/acs.joc.9b01442

data_4033867
_publ_section_title
;
 Desymmetrization Reactions of Indigo with Grignard Reagents for the
 Synthesis of Selective Antiplasmodial
 [1<i>H</i>,3'<i>H</i>]-3-Aryl-2,2'-diindol-3'-ones.
;
_journal_issue                   17
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              11228
_journal_page_last               11239
_journal_paper_doi               10.1021/acs.joc.9b01442
_journal_volume                  84
_journal_year                    2019
_chemical_compound_source        ' from U of Wollongong'
_chemical_formula_moiety         'C25 H20 N2 O3 S1'
_chemical_formula_sum            'C25 H20 N2 O3 S'
_chemical_formula_weight         428.51
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_audit_creation_date             17-11-28
_audit_creation_method           CRYSTALS_ver_14.40
_audit_update_record
;
2017-12-05 - Report on C25 H20 N2 O3 S 
             by Anthony C. Willis
             for Paul Keller

2017-12-05 - details of refinement in _refine_special_details below

2017-12-05 - passes checkcif tests with no significant warnings  
;
_cell_angle_alpha                90
_cell_angle_beta                 101.1492(11)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4271(1)
_cell_length_b                   10.0632(1)
_cell_length_c                   23.0963(2)
_cell_measurement_reflns_used    13392
_cell_measurement_temperature    150
_cell_measurement_theta_max      74
_cell_measurement_theta_min      4
_cell_volume                     2149.72(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2017)'
_computing_molecular_graphics    'PLATON (Spek, 2008)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.034
_diffrn_reflns_av_sigmaI/netI    0.0475
_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       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            32752
_diffrn_reflns_theta_full        73.810
_diffrn_reflns_theta_max         73.810
_diffrn_reflns_theta_min         4.781
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.579
_exptl_absorpt_correction_T_max  0.91
_exptl_absorpt_correction_T_min  0.66
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro version 1.171.38.46 (Rigaku Oxford Diffraction, 2017)
(Release 29 April 2016; compiled 27 May 2016,16:53)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_diffrn    1.324
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.186
_exptl_crystal_size_mid          0.164
_exptl_crystal_size_min          0.060
_refine_diff_density_max         0.26
_refine_diff_density_min         -0.25
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   1.0018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     326
_refine_ls_number_reflns         4347
_refine_ls_number_restraints     67
_refine_ls_R_factor_all          0.0411
_refine_ls_R_factor_gt           0.0372
_refine_ls_shift/su_max          0.0019496
_refine_ls_shift/su_mean         0.0001296
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.04P)^2^ + 1.30P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0922
_refine_ls_wR_factor_gt          0.0892
_refine_ls_wR_factor_ref         0.0922
_reflns_limit_h_max              11
_reflns_limit_h_min              -11
_reflns_limit_k_max              12
_reflns_limit_k_min              0
_reflns_limit_l_max              28
_reflns_limit_l_min              0
_reflns_number_gt                3948
_reflns_number_total             4347
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   1.99
_oxford_diffrn_Wilson_scale      0.04
_oxford_refine_ls_r_factor_ref   0.0411
_oxford_refine_ls_scale          5.50(9)
_oxford_reflns_number_all        4347
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title
'Z:\kel1710SNQ\Tony_kel1710SNQ_da At 12: 2 on'
_cod_data_source_file            jo9b01442_si_005.cif
_cod_data_source_block           kel1710SNQ
_cod_original_sg_symbol_H-M      'P 1 21/c 1 '
_cod_original_formula_sum        'C25 H20 N2 O3 S1'
_cod_database_code               4033867
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_iucr_refine_instruction_details_constraints
;
BLOCK SCALE S(1,X'S,U'S,OCC) UNTIL S(91) 
CONT O(1,X'S,U'S) UNTIL C(16) 
CONT C(17,X'S,U'S,OCC) UNTIL C(20) 
CONT C(21,X'S,U'S) UNTIL C(25) 
CONT C(917,X'S,U'S,OCC) UNTIL C(920) 
EQUIV S(1,OCC) S(91,OCC) C(17,OCC) UNTIL C(20) C(917,OCC) UNTIL C(920) 
WEIGHT -1 S(91,OCC) C(917,OCC) UNTIL  C(920) 
RIDE C ( 2,X'S) H( 21,X'S) 
RIDE C ( 3,X'S) H( 31,X'S) 
RIDE C ( 4,X'S) H( 41,X'S) 
RIDE C ( 5,X'S) H( 51,X'S) 
RIDE C ( 12,X'S) H( 121,X'S) 
RIDE C ( 13,X'S) H( 131,X'S) 
RIDE C ( 14,X'S) H( 141,X'S) 
RIDE C ( 15,X'S) H( 151,X'S) 
RIDE C ( 23,X'S) H( 231,X'S) H( 232,X'S) H( 233,X'S) 
RIDE C ( 24,X'S) H( 241,X'S) H( 242,X'S) H( 243,X'S) 
RIDE C ( 25,X'S) H( 251,X'S) H( 252,X'S) H( 253,X'S) 
RIDE C(18,X'S) H(181,X'S) 
RIDE C(19,X'S) H(191,X'S) 
RIDE C(20,X'S) H(201,X'S) 
RIDE C(918,X'S) H(9181,X'S) 
RIDE C(919,X'S) H(9191,X'S) 
RIDE C(920,X'S) H(9201,X'S) 
END                                                                             
;
_iucr_refine_instruction_details_restraints
;
U(IJ) 0.0, .0001 = C(17) TO C(917) 
U(IJ) 0.0, .001 = S(1) TO C(918) 
U(IJ) 0.0, .001 = C(18) TO S(91) 
U(IJ) 0.0, .001 = C(19) TO C(920) 
U(IJ) 0.0, .001 = C(20) TO C(919) 
DIST 0.0, .01 = MEAN C(10) TO C(17), C(10) TO C(917) 
DIST 0.0, .01 = MEAN C(17) TO C(18), C(917) TO C(918) 
DIST 0.0, .01 = MEAN C(18) TO C(19), C(918) TO C(919) 
DIST 0.0, .01 = MEAN C(19) TO C(20), C(919) TO C(920) 
DIST 0.0, .01 = MEAN C(20) TO S(1), C(920) TO S(91) 
DIST 0.0, .01 = MEAN C(17) TO S(1), C(917) TO S(91) 
ANGLE 0.0, 1 = MEAN C(10) TO C(17) TO S(1) 
CONT                  C(10) TO C(917) TO S(91) 
ANGLE 0.0, 1 = MEAN C(10) TO C(17) TO C(18) 
CONT                  C(10) TO C(917) TO C(918) 
ANGLE 0.0, 1 = MEAN S(1) TO C(17) TO C(18) 
CONT                  S(91) TO C(917) TO C(918) 
ANGLE 0.0, 1 = MEAN C(17) TO C(18) TO C(19) 
CONT                  C(917) TO C(918) TO C(919) 
ANGLE 0.0, 1 = MEAN C(18) TO C(19) TO C(20) 
CONT                  C(918) TO C(919) TO C(920) 
ANGLE 0.0, 1 = MEAN C(19) TO C(20) TO S(1) 
CONT                  C(919) TO C(920) TO S(91) 
ANGLE 0.0, 1 = MEAN C(17) TO S(1) TO C(20) 
CONT                  C(917) TO S(91) TO C(920) 
PLANAR C(10) C(17) UNTIL C(20) S(1) C(917) UNTIL C(920) S(91) 
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
END                                                                             
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