New activation mechanism for half-sandwich organometallic anticancer complexes.
Banerjee, Samya; Soldevila-Barreda, Joan J; Wolny, Juliusz A.; Wootton, Christopher A.; Habtemariam, Abraha; Romero-Canelón, Isolda; Chen, Feng; Clarkson, Guy J.; Prokes, Ivan; Song, Lijiang; O'Connor, Peter B; Schünemann, Volker; Sadler, Peter J.; Chemical science 9 (2018) 3177–3185; doi:10.1039/c7sc05058e

data_1549016
_publ_section_title
;
 New activation mechanism for half-sandwich organometallic anticancer
 complexes.
;
_journal_issue                   12
_journal_name_full               'Chemical science'
_journal_page_first              3177
_journal_page_last               3185
_journal_paper_doi               10.1039/c7sc05058e
_journal_volume                  9
_journal_year                    2018
_chemical_formula_moiety         'C33 H33 Cl N2 Rh, F6 P, C3 H6 O'
_chemical_formula_sum            'C36 H39 Cl F6 N2 O P Rh'
_chemical_formula_weight         799.02
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_block_doi                 10.5517/ccdc.csd.cc1jnp2y
_audit_creation_date             2014-11-24
_audit_creation_method
;
Olex2 1.2
(compiled 2014.11.21 svn.r3092 for OlexSys, GUI svn.r4949)
;
_audit_update_record
;
2015-08-22 deposited with the CCDC.
2018-02-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.393(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.0233(4)
_cell_length_b                   28.1842(13)
_cell_length_c                   16.1096(8)
_cell_measurement_reflns_used    5345
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      28.9000
_cell_measurement_theta_min      2.8730
_cell_volume                     3632.2(3)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1417
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.881
_diffrn_measurement_details
;
  1 omega  -21.00   39.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       13.4141  -99.0000   30.0000 60

  2 omega  -58.00   35.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       13.4141  -38.0000  -90.0000 93

  3 omega  -51.00   -9.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       13.4141  -38.0000 -150.0000 42

  4 omega    0.00   27.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.1954  -99.0000 -180.0000 27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0381038000
_diffrn_orient_matrix_UB_12      0.0187478000
_diffrn_orient_matrix_UB_13      0.0239180000
_diffrn_orient_matrix_UB_21      0.0222665000
_diffrn_orient_matrix_UB_22      -0.0161376000
_diffrn_orient_matrix_UB_23      0.0327678000
_diffrn_orient_matrix_UB_31      0.0769115000
_diffrn_orient_matrix_UB_32      -0.0046156000
_diffrn_orient_matrix_UB_33      -0.0174441000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0563
_diffrn_reflns_av_unetI/netI     0.0962
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.881
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            22985
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.881
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.765
_diffrn_reflns_theta_min         2.512
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.649
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.98447
_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.
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    1.461
_exptl_crystal_description       block
_exptl_crystal_F_000             1632
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.486
_refine_diff_density_min         -1.116
_refine_diff_density_rms         0.139
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     435
_refine_ls_number_reflns         9993
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.1198
_refine_ls_R_factor_gt           0.0706
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0851P)^2^+7.4806P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1633
_refine_ls_wR_factor_ref         0.1915
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6489
_reflns_number_total             9993
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc05058e2.cif
_cod_data_source_block           js15
_cod_depositor_comments
'Adding full bibliography for 1549011--1549018.cif.'
_cod_database_code               1549016
_chemical_oxdiff_formula         'C20 H20 N2 O2 F P Rh'
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;

The PF6 was very disordered. The PF6 was simply modlelled as
dioredered over two positions by a rotation about P10.
The occupancy was fixed at 50:50 and the fluorines were refined
isotropically.
DFIX and DANG restraints were used on both parts to give them appropriate
P-F and F-F bond distances and angles.
The thermal ellipsoids of the solvent acetone where large and cigar shaped 
and were refined with a SIMU restraint
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 P10-F11 = P10-F12 = P10-F13 = P10-F14 = P10-F15 = P10-F16
 1.6 with sigma of 0.02
 P10-F11A = P10-F12A = P10-F13A = P10-F14A = P10-F15A = P10-F16A
 1.6 with sigma of 0.02
 F11-F13 = F11-F14 = F11-F15 = F11-F16
 2.26 with sigma of 0.04
 F12-F13 = F12-F14 = F12-F15 = F12-F16
 2.26 with sigma of 0.04
 F13-F15 = F13-F16 = F14-F15 = F14-F16
 2.26 with sigma of 0.04
 F11A-F13A = F11A-F14A = F11A-F15A = F11A-F16A
 2.26 with sigma of 0.04
 F12A-F13A = F12A-F14A = F12A-F15A = F12A-F16A
 2.26 with sigma of 0.04
 F13A-F15A = F13A-F16A = F14A-F15A = F14A-F16A
 2.26 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C36 \\sim C37 \\sim C38 \\sim O37: within 1.7A with sigma of 0.004 and sigma
for terminal atoms of 0.008
4. Others
 Fixed Sof: F11(0.5) F12(0.5) F13(0.5) F14(0.5) F15(0.5) F16(0.5) F11A(0.5)
 F12A(0.5) F13A(0.5) F14A(0.5) F15A(0.5) F16A(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C8(H8), C10(H10), C11(H11), C15(H15), C16(H16),
 C17(H17), C18(H18), C19(H19), C22(H22), C23(H23), C25(H25), C26(H26)
5.b Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C32(H32A,H32B,H32C), C33(H33A,H33B,
 H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C38(H38A,
 H38B,H38C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'