Asymmetric transfer hydrogenation by synthetic catalysts in cancer cells
James P. C. Coverdale; Isolda Romero-Canelon; Carlos Sanchez-Cano; Guy J. Clarkson; Abraha Habtemariam; Martin Wills; Peter J. Sadler; Nature Chemistry 10 (2018) 347–354; doi:10.1038/nchem.2918

data_1551834
_publ_section_title
;
 Asymmetric transfer hydrogenation by synthetic catalysts in cancer cells
;
_journal_name_full               'Nature Chemistry'
_journal_page_first              347
_journal_page_last               354
_journal_paper_doi               10.1038/nchem.2918
_journal_volume                  10
_journal_year                    2018
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C33 H30 N2 O2 Os S, 2(C H Cl3)'
_chemical_formula_sum            'C35 H32 Cl6 N2 O2 Os S'
_chemical_formula_weight         947.58
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.95564(14)
_cell_length_b                   16.3879(3)
_cell_length_c                   26.8668(5)
_cell_measurement_reflns_used    12713
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      31.2040
_cell_measurement_theta_min      2.5920
_cell_volume                     3502.79(11)
_computing_cell_refinement
'CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48)'
_computing_data_collection
'CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48)'
_computing_data_reduction
'CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2833
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_details
'#__ type_ start__ end____ width___ exp.time_ 1 omega -73.00 103.00 1.0000 75.0000 omega____ theta____ kappa____ phi______ frames - 15.2579 0.0000 -90.0000 176 #__ type_ start__ end____ width___ exp.time_ 2 omega -25.00 25.00 1.0000 75.0000 omega____ theta____ kappa____ phi______ frames - -16.1954 -99.0000 -60.0000 50 #__ type_ start__ end____ width___ exp.time_ 3 omega -9.00 90.00 1.0000 75.0000 omega____ theta____ kappa____ phi______ frames - 15.2579 38.0000 90.0000 99 #__ type_ start__ end____ width___ exp.time_ 4 omega -103.00 -63.00 1.0000 75.0000 omega____ theta____ kappa____ phi______ frames - -16.1954 178.0000 -180.0000 40 #__ type_ start__ end____ width___ exp.time_ 5 omega -44.00 57.00 1.0000 75.0000 omega____ theta____ kappa____ phi______ frames - -16.1954 57.0000 150.0000 101'
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0577067000
_diffrn_orient_matrix_UB_12      0.0112859000
_diffrn_orient_matrix_UB_13      -0.0189044000
_diffrn_orient_matrix_UB_21      0.0311911000
_diffrn_orient_matrix_UB_22      -0.0405261000
_diffrn_orient_matrix_UB_23      -0.0006578000
_diffrn_orient_matrix_UB_31      -0.0603848000
_diffrn_orient_matrix_UB_32      -0.0101592000
_diffrn_orient_matrix_UB_33      -0.0184198000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0543
_diffrn_reflns_av_unetI/netI     0.0527
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            49812
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.994
_diffrn_reflns_theta_min         2.599
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.194
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95370
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.797
_exptl_crystal_description
;
;
_exptl_crystal_F_000             1864
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.008
_refine_diff_density_min         -0.791
_refine_diff_density_rms         0.142
_refine_ls_abs_structure_details
;
 Flack x determined using 3739 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Hooft y: -0.022(3) Olex2
Flack x: -0.016(3) Shewlx2016 from 3739 selected quotients (Parsons' method)
         -0.012(6) by classical fit to all intensities
Synthesised from a molecule of know handedness
;
_refine_ls_abs_structure_Flack   -0.016(3)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     428
_refine_ls_number_reflns         10729
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0436
_refine_ls_R_factor_gt           0.0328
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0232P)^2^+0.7220P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0539
_refine_ls_wR_factor_ref         0.0570
_reflns_Friedel_coverage         0.753
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.929
_reflns_number_gt                9618
_reflns_number_total             10729
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2918-s2.cif
_cod_data_source_block           jc4
_cod_original_cell_volume        3502.80(11)
_cod_database_code               1551834
_chemical_oxdiff_formula         'C20 H20 N2 O2 F6 P Os'
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.98
_olex2_refinement_description
;
The NH was located in a difference map and refined with DFIX restraint and given a 
Uiso 1.5 times the Uequiv of the parent nitrogen. 

1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups, H11A of C35
 At 1.2 times of:
  H01 of C01, H02 of C02, H3 of C3, H4 of C4, H6 of C6, H7 of C7, H10 of C10,
  H11 of C11, H13 of C13, H14 of C14, H15 of C15, H16 of C16, H17 of C17, H19
  of C19, H20 of C20, H21 of C21, H22 of C22, H23 of C23, H24 of C24, H25 of
  C25, H26 of C26, H27 of C27, H28 of C28, H31 of C31, H32 of C32, H33 of C33,
  H34 of C34, H35 of C35
2. Restrained distances
 N11-H11A
 0.9 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C01(H01), C02(H02), C10(H10), C11(H11)
3.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C13(H13), C14(H14), C15(H15), C16(H16),
 C17(H17), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25),
  C26(H26), C27(H27), C28(H28), C31(H31), C32(H32), C33(H33), C34(H34), C35(H35)
3.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_shelx_res_checksum              20249
_shelx_hkl_checksum              65083