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_1549015
_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
'C25 H28 N3 Rh, 1.15(F6 P), F4.28 P0.85, 0.5(O), 0.82(F)'
_chemical_formula_sum            'C25 H28 F12 N3 O0.5 P2 Rh'
_chemical_formula_weight         771.35
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-07-10
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_audit_update_record
;
2017-08-16 deposited with the CCDC.
2018-02-19 downloaded from the CCDC.
;
_cell_angle_alpha                101.363(2)
_cell_angle_beta                 90.9323(17)
_cell_angle_gamma                109.801(2)
_cell_formula_units_Z            2
_cell_length_a                   9.84864(19)
_cell_length_b                   10.1712(3)
_cell_length_c                   16.1627(3)
_cell_measurement_reflns_used    17759
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      77.5970
_cell_measurement_theta_min      4.6600
_cell_volume                     1487.41(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_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(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2833
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -116.00 -17.00   1.00    6.25    --  -41.71 -38.00-120.00   99
  2  \w    -66.00  33.00   1.00    6.25    --  -41.71  38.00  60.00   99
  3  \w    -70.00  31.00   1.00    6.25    --  -41.71  57.00 150.00  101
  4  \w     17.00 116.00   1.00    6.25    --   41.71  38.00-120.00   99
  5  \w     18.00  98.00   1.00    6.25    --   41.71-125.00  30.00   80
  6  \w     42.00 143.00   1.00   25.00    --  114.00 -61.00-120.00  101
  7  \w     86.00 178.00   1.00   25.00    --  114.00  30.00-150.00   92
  8  \w     38.00 116.00   1.00   25.00    --  114.00-111.00-120.00   78
  9  \w     38.00 116.00   1.00   25.00    --  114.00-111.00  60.00   78
 10  \w     38.00 147.00   1.00   25.00    --  114.00 -77.00 120.00  109
 11  \w     38.00 142.00   1.00   25.00    --  114.00 -30.00 -60.00  104
 12  \w     41.00 140.00   1.00   25.00    --  114.00 -45.00  30.00   99
 13  \w     32.00 167.00   1.00   25.00    --  114.00 -15.00-180.00  135
 14  \w   -115.00 -14.00   1.00    6.25    --  -41.71 -57.00 120.00  101
 15  \w   -118.00  -9.00   1.00    6.25    --  -41.71 -77.00  60.00  109
 16  \w     -4.00  83.00   1.00    6.25    --   41.71 -99.00 -90.00   87
 17  \w      9.00 118.00   1.00    6.25    --   41.71  77.00   0.00  109
 18  \w     85.00 178.00   1.00   25.00    --  114.00  61.00  90.00   93
 19  \w     61.00 178.00   1.00   25.00    --  114.00  15.00 120.00  117
 20  \w     86.00 178.00   1.00   25.00    --  114.00  30.00 -60.00   92
 21  \w     81.00 178.00   1.00   25.00    --  114.00  77.00 120.00   97
 22  \w     86.00 178.00   1.00   25.00    --  114.00  30.00   0.00   92
 23  \w     85.00 178.00   1.00   25.00    --  114.00  61.00 -60.00   93
 24  \w     88.00 178.00   1.00   25.00    --  114.00  45.00  30.00   90
 25  \w     88.00 178.00   1.00   25.00    --  114.00  45.00-120.00   90
 26  \w    -70.00  31.00   1.00    6.25    --  -41.71  57.00 -90.00  101
 27  \w      9.00 118.00   1.00    6.25    --   41.71  77.00  90.00  109
 28  \w      9.00 118.00   1.00    6.25    --   41.71  77.00 -90.00  109
 29  \w      9.00 118.00   1.00    6.25    --   41.71  77.00 150.00  109
 30  \w     81.00 178.00   1.00   25.00    --  114.00  77.00  30.00   97
 31  \w     85.00 178.00   1.00   25.00    --  114.00  61.00-120.00   93
 32  \w     81.00 178.00   1.00   25.00    --  114.00  77.00 -30.00   97
 33  \w     85.00 178.00   1.00   25.00    --  114.00  61.00 120.00   93
 34  \w     85.00 178.00   1.00   25.00    --  114.00  61.00 150.00   93
 35  \w     85.00 178.00   1.00   25.00    --  114.00  61.00-150.00   93
 36  \w     85.00 178.00   1.00   25.00    --  114.00  61.00  60.00   93
 37  \w     88.00 178.00   1.00   25.00    --  114.00  45.00-150.00   90
 38  \w   -115.00 -14.00   1.00    6.25    --  -41.71 -57.00 150.00  101
 39  \w    -70.00  31.00   1.00    6.25    --  -41.71  57.00-180.00  101
 40  \w     17.00 116.00   1.00    6.25    --   41.71  38.00 -60.00   99
 41  \w     14.00 115.00   1.00    6.25    --   41.71  57.00   0.00  101
 42  \w     81.00 178.00   1.00   25.00    --  114.00  77.00-120.00   97
 43  \w     32.00 109.00   1.00   25.00    --  114.00 -95.00 -30.00   77
 44  \w     81.00 178.00   1.00   25.00    --  114.00  77.00 -90.00   97
 45  \w     81.00 178.00   1.00   25.00    --  114.00  77.00 150.00   97
 46  \w     85.00 178.00   1.00   25.00    --  114.00  61.00   0.00   93
 47  \w     85.00 178.00   1.00   25.00    --  114.00  61.00  30.00   93
 48  \w     81.00 178.00   1.00   25.00    --  114.00  77.00  90.00   97
 49  \w     81.00 178.00   1.00   25.00    --  114.00  77.00  60.00   97
 50  \w     17.00 116.00   1.00    6.25    --   41.71  38.00-180.00   99
 51  \w      9.00 118.00   1.00    6.25    --   41.71  77.00-180.00  109
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0329375000
_diffrn_orient_matrix_UB_12      0.0403260000
_diffrn_orient_matrix_UB_13      -0.0831623000
_diffrn_orient_matrix_UB_21      0.1587447000
_diffrn_orient_matrix_UB_22      0.0294880000
_diffrn_orient_matrix_UB_23      -0.0198204000
_diffrn_orient_matrix_UB_31      -0.0397628000
_diffrn_orient_matrix_UB_32      -0.1570949000
_diffrn_orient_matrix_UB_33      -0.0471207000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0627
_diffrn_reflns_av_unetI/netI     0.0326
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            44172
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.018
_diffrn_reflns_theta_min         4.732
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.585
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.46587
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43d (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.722
_exptl_crystal_description       block
_exptl_crystal_F_000             772
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.348
_refine_diff_density_min         -0.618
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     518
_refine_ls_number_reflns         6273
_refine_ls_number_restraints     42
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0532
_refine_ls_R_factor_gt           0.0482
_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^)+(0.0601P)^2^+2.0805P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1226
_refine_ls_wR_factor_ref         0.1266
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5711
_reflns_number_total             6273
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc05058e2.cif
_cod_data_source_block           sb2
_cod_depositor_comments
'Adding full bibliography for 1549011--1549018.cif.'
_cod_original_formula_sum        'C25 H28 F12 N3 O0.50 P2 Rh'
_cod_database_code               1549015
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C20 H20 N2 O2 F6 P Rh'
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_olex2_refinement_description
;
The asymmetric unit contains the Rh complex, two PF6 counter ions and a partially occupied water molecule.
No hydrogens were located on the water molecule.
The complex was modeled as disordered over two closely related positions. The occupancy was originally 
linked to a free variable that settled around 85:15 and the occupancy of the components was fixed at this 
value for the rest of the refinement.
The PF6 counter ion (P20_F26) was modeled as disordered over two closely related positions again linked to 
85:15 occupancy. Additionally, the major component was also modelled as disordered where the components were 
related by a rotation about the meridian. The occupancy of these components (F23-F26 : F23A-F26A) was linked 
to a free variable which refined to 76:24 (of the 85% occupancy).
Minor components were refined isotropically and several DFIX, DANG and SIMU restraints were used to give the minor 
components reasonable bond lengths, angles and thermal parameters.

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
 P30-F31 = P30-F32 = P30-F33 = P30-F34 = P30-F35 = P30-F36
 1.58 with sigma of 0.02
 P20-F21 = P20-F22 = P20-F23A = P20-F24A = P20-F25A = P20-F26A
 1.58 with sigma of 0.02
 F31-F33 = F31-F34 = F31-F35 = F31-F36 = F32-F33 = F32-F34
 2.23 with sigma of 0.04
 F32-F35 = F32-F36 = F33-F35 = F33-F36 = F34-F35 = F34-F36
 2.23 with sigma of 0.04
 F21-F23A = F21-F24A = F21-F25A = F21-F26A = F22-F23A = F22-F24A
 2.23 with sigma of 0.04
 F22-F25A = F22-F26A = F23A-F25A = F23A-F26A = F24A-F25A = F24A-F26A
 2.23 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
P30 \\sim F35 \\sim F31 \\sim F32 \\sim F36 \\sim F34 \\sim F33: within 1.7A
with sigma of 0.008 and sigma for terminal atoms of 0.016
4. Others
 Sof(F24A)=Sof(F25A)=Sof(F23A)=Sof(F26A)=0.85*(1-FVAR(2))
 Sof(F23)=Sof(F24)=Sof(F26)=Sof(F25)=0.85*FVAR(2)
 Fixed Sof: Rh1(0.85) P20(0.85) N1(0.85) N12(0.85) C6(0.85) N13(0.85)
 F21(0.85) C7(0.85) C22(0.85) C5(0.85) H5(0.85) F22(0.85) C21(0.85) C8(0.85)
 H8(0.85) C23(0.85) C2(0.85) H2(0.85) C9(0.85) H9(0.85) C20(0.85) C27(0.85)
 H27A(0.85) H27B(0.85) H27C(0.85) C15(0.85) H15(0.85) C18(0.85) H18(0.85)
 C26(0.85) H26A(0.85) H26B(0.85) H26C(0.85) C11(0.85) H11(0.85) C4(0.85)
 H4(0.85) C19(0.85) C16(0.85) H16(0.85) C24(0.85) H24A(0.85) H24B(0.85)
 H24C(0.85) C3(0.85) H3(0.85) C17(0.85) H17(0.85) C14(0.85) H14(0.85) C10(0.85)
 H10(0.85) C28(0.85) H28A(0.85) H28B(0.85) H28C(0.85) C25(0.85) H25A(0.85)
 H25B(0.85) H25C(0.85) O1(0.5) Rh(0.15) N0AA(0.15) C2AA(0.15) H2AA(0.15)
 C6AA(0.15) H6AA(0.15) C9AA(0.15) H9AA(0.15) C0BA(0.15) H0BA(0.15) C19A(0.15)
 C20A(0.15) C21A(0.15) C22A(0.15) C23A(0.15) C24A(0.15) H24D(0.15) H24E(0.15)
 H24F(0.15) C25A(0.15) H25D(0.15) H25E(0.15) H25F(0.15) C26A(0.15) H26D(0.15)
 H26E(0.15) H26F(0.15) C27A(0.15) H27D(0.15) H27E(0.15) H27F(0.15) C28A(0.15)
 H28D(0.15) H28E(0.15) H28F(0.15) C1BA(0.15) H1BA(0.15) N1A(0.15) C2A(0.15)
 H2A(0.15) C3A(0.15) H3A(0.15) C4A(0.15) H4A(0.15) C5A(0.15) H5A(0.15)
 C6A(0.15) N12A(0.15) C7A(0.15) C8A(0.15) H8A(0.15) C9A(0.15) H9A(0.15)
 C10A(0.15) H10A(0.15) C11A(0.15) H11A(0.15) P30(0.15) F35(0.15) F31(0.15)
 F32(0.15) F36(0.15) F34(0.15) F33(0.15)
5.a Me refined with riding coordinates:
 C25A(H25D,H25E,H25F), C27A(H27D,H27E,H27F)
5.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C8(H8), C2(H2), C9(H9), C15(H15), C18(H18), C11(H11), C4(H4),
 C16(H16), C3(H3), C17(H17), C14(H14), C10(H10), C2AA(H2AA), C6AA(H6AA),
 C9AA(H9AA), C0BA(H0BA), C1BA(H1BA), C2A(H2A), C3A(H3A), C4A(H4A), C5A(H5A),
 C8A(H8A), C9A(H9A), C10A(H10A), C11A(H11A)
5.c Fitted hexagon refined as free rotating group:
 N1A(C2A,C3A,C4A,C5A,C6A), N12A(C7A,C8A,C9A,C10A,C11A)
5.d Cp* refined as free rotating group:
 C19A(C20A,C21A,C22A,C23A,C24A,C25A,C26A,C27A,C28A)
5.e Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C26(H26A,H26B,H26C), C24(H24A,H24B,H24C), C28(H28A,H28B,
 H28C), C25(H25A,H25B,H25C), C24A(H24D,H24E,H24F), C26A(H26D,H26E,H26F),
 C28A(H28D,H28E,H28F)
;
_shelx_res_checksum              65504
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.006
_oxdiff_exptl_absorpt_empirical_full_min 0.622