Hydrosulfide Adducts of Organo-Iridium Anticancer Complexes.
Štarha, Pavel; Habtemariam, Abraha; Romero-Canelón, Isolda; Clarkson, Guy J.; Sadler, Peter J.; Inorganic chemistry 55 (2016) 2324–2331; doi:10.1021/acs.inorgchem.5b02697

data_4347078
_publ_section_title
;
 Hydrosulfide Adducts of Organo-Iridium Anticancer Complexes.
;
_journal_issue                   5
_journal_name_full               'Inorganic chemistry'
_journal_page_first              2324
_journal_page_last               2331
_journal_paper_doi               10.1021/acs.inorgchem.5b02697
_journal_volume                  55
_journal_year                    2016
_chemical_formula_moiety         '1(C22 H23 Ir N2 S), C24 H20 B'
_chemical_formula_sum            'C46 H44 B Ir N2 S'
_chemical_formula_weight         859.90
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-01-29
_audit_creation_method
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Olex2 1.2
(compiled 2015.01.26 svn.r3151 for OlexSys, GUI svn.r4998)
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_cell_angle_alpha                101.8011(16)
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_cell_angle_gamma                98.4346(15)
_cell_formula_units_Z            4
_cell_length_a                   11.3760(2)
_cell_length_b                   15.3329(3)
_cell_length_c                   22.0650(4)
_cell_measurement_reflns_used    18857
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      24.1890
_cell_measurement_theta_min      2.7420
_cell_volume                     3709.89(12)
_computing_cell_refinement
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
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_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
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_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 0.952
_diffrn_measurement_details
;
  1 omega  -19.00   93.00   1.0000   42.5000
omega____ theta____ kappa____ phi______ frames
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  2 omega  -19.00   93.00   1.0000   42.5000
omega____ theta____ kappa____ phi______ frames
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  3 omega  -49.00   64.00   1.0000   42.5000
omega____ theta____ kappa____ phi______ frames
    -      -15.0968   77.0000 -120.0000 113

  4 omega   35.00  104.00   1.0000   42.5000
omega____ theta____ kappa____ phi______ frames
    -       14.3155  178.0000 -180.0000 69

  5 omega   35.00  104.00   1.0000   42.5000
omega____ theta____ kappa____ phi______ frames
    -       14.3155  178.0000  -90.0000 69

  6 omega  -25.00   56.00   1.0000   42.5000
omega____ theta____ kappa____ phi______ frames
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  7 omega  -91.00   11.00   1.0000   42.5000
omega____ theta____ kappa____ phi______ frames
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  8 omega -105.00  -57.00   1.0000   42.5000
omega____ theta____ kappa____ phi______ frames
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  9 omega -105.00  -57.00   1.0000   42.5000
omega____ theta____ kappa____ phi______ frames
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 10 omega  -25.00   56.00   1.0000   42.5000
omega____ theta____ kappa____ phi______ frames
    -       14.3155  -99.0000 -150.0000 81

 11 omega  -26.00   56.00   1.0000   42.5000
omega____ theta____ kappa____ phi______ frames
    -       14.3155  -98.0000  -30.0000 82

 12 omega  -60.00   44.00   1.0000   42.5000
omega____ theta____ kappa____ phi______ frames
    -       14.3155  -57.0000   30.0000 104

 13 omega  -91.00   11.00   1.0000   42.5000
omega____ theta____ kappa____ phi______ frames
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 14 omega  -25.00   27.00   1.0000   42.5000
omega____ theta____ kappa____ phi______ frames
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 15 omega  -57.00    5.00   1.0000   42.5000
omega____ theta____ kappa____ phi______ frames
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 16 omega  -19.00   93.00   1.0000   42.5000
omega____ theta____ kappa____ phi______ frames
    -       14.3155   77.0000  -60.0000 112

 17 omega  -25.00   56.00   1.0000   42.5000
omega____ theta____ kappa____ phi______ frames
    -       14.3155  -99.0000 -120.0000 81

 18 omega  -25.00    4.00   1.0000   42.5000
omega____ theta____ kappa____ phi______ frames
    -      -15.0968  -99.0000    0.0000 29
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0124670000
_diffrn_orient_matrix_UB_12      -0.0121667000
_diffrn_orient_matrix_UB_13      0.0285470000
_diffrn_orient_matrix_UB_21      -0.0097332000
_diffrn_orient_matrix_UB_22      0.0445587000
_diffrn_orient_matrix_UB_23      0.0123388000
_diffrn_orient_matrix_UB_31      -0.0613022000
_diffrn_orient_matrix_UB_32      -0.0126661000
_diffrn_orient_matrix_UB_33      -0.0109902000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1445
_diffrn_reflns_av_unetI/netI     0.1366
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            154705
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.661
_diffrn_reflns_theta_min         2.349
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.691
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94783
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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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,
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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    1.540
_exptl_crystal_description       block
_exptl_crystal_F_000             1728
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_exptl_crystal_size_min          0.03
_refine_diff_density_max         3.121
_refine_diff_density_min         -1.454
_refine_diff_density_rms         0.176
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     965
_refine_ls_number_reflns         21878
_refine_ls_number_restraints     154
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.1670
_refine_ls_R_factor_gt           0.0719
_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^)+(0.0744P)^2^+8.6456P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1457
_refine_ls_wR_factor_ref         0.1810
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11592
_reflns_number_total             21878
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b02697_si_002.cif
_cod_data_source_block           ps1
_cod_original_cell_volume        3709.90(12)
_cod_database_code               4347078
_chemical_oxdiff_formula         'C20 H20 N2 B S Ir'
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.02
_olex2_refinement_description
;

The thermal parameters of both the pentamethyl Cp and the phenathroline 
ligands of one of the metal complexes where very larger. 
A disordered model was refined where the entire metal complex (Ir2) 
(except the sulphur ) were refined over two closely related positions 
related by a small shift in the metal position. 
Many AFIX constraints, DFIX and DELU restraints were used to give 
the disordered components reasonable bond lengths, angles and thermal parameters. 
The occupancy of the two components with the metal and the phenanthroline were 
fixed at occupancies of 80 and 20%. The occupancy of the two disordered components 
of the pentamethyl Cp rings was fixed at 85 and 15%.  
Both disordered models shared the same sulphur.
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
 C5A-C6A = C6A-C7A = C7A-C8A
 1.39 with sigma of 0.02
 C10A-C425_$1
 -3 with sigma of 0.02
3. Restrained planarity
 C14A, C13A, C8A, C7A, C6A, C5A
 with sigma of 0.05
4. Rigid bond restraints
 C115, C116, C117, C118, C119, C120, C121, C122, C123, C124
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C24A, C15A, C18A, C19A, C16A, C20A, C17A, C23A, C21A, C22A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Uiso/Uaniso restraints and constraints
C115 \\sim C116 \\sim C117 \\sim C118 \\sim C119 \\sim C120 \\sim C121 \\sim
C122 \\sim C123 \\sim C124: within 1.7A with sigma of 0.002 and sigma for
terminal atoms of 0.004
C24A \\sim C15A \\sim C18A \\sim C19A \\sim C16A \\sim C20A \\sim C17A \\sim
C23A \\sim C21A \\sim C22A: within 1.7A with sigma of 0.001 and sigma for
terminal atoms of 0.002
N1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A \\sim C6A \\sim C7A \\sim C8A \\sim
C9A \\sim C10A \\sim C11A \\sim N12A \\sim C13A \\sim C14A: within 1.7A with
sigma of 0.004 and sigma for terminal atoms of 0.008
C19A \\sim C15A \\sim C16A \\sim C17A \\sim C18A: within 1.7A with sigma of
0.004 and sigma for terminal atoms of 0.008
Uanis(C122) \\sim Ueq, Uanis(C121) \\sim Ueq, Uanis(C120) \\sim Ueq,
Uanis(C220) \\sim Ueq, Uanis(C221) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.008
Uanis(Ir2A) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
6. Others
 Fixed Sof: Ir2(0.8) N201(0.8) N212(0.8) C210(0.8) H210(0.8) C207(0.8)
 H207(0.8) C213(0.8) C218(0.85) C209(0.8) H209(0.8) C211(0.8) H211(0.8)
 C219(0.85) C216(0.85) C223(0.85) H22A(0.85) H22B(0.85) H22C(0.85) C205(0.8)
 C215(0.85) C202(0.8) H202(0.8) C208(0.8) C214(0.8) C221(0.85) H22D(0.85)
 H22E(0.85) H22F(0.85) C224(0.85) H22G(0.85) H22H(0.85) H22I(0.85) C204(0.8)
 H204(0.8) C217(0.85) C203(0.8) H203(0.8) C222(0.85) H22J(0.85) H22K(0.85)
 H22L(0.85) C206(0.8) H206(0.8) C220(0.85) H22M(0.85) H22N(0.85) H22O(0.85)
 C15A(0.15) C16A(0.15) C17A(0.15) C18A(0.15) C19A(0.15) C20A(0.15) H20A(0.15)
 H20B(0.15) H20C(0.15) C21A(0.15) H21A(0.15) H21B(0.15) H21C(0.15) C22A(0.15)
 H22P(0.15) H22Q(0.15) H22R(0.15) C23A(0.15) H23A(0.15) H23B(0.15) H23C(0.15)
 C24A(0.15) H24A(0.15) H24B(0.15) H24C(0.15) C6A(0.2) H6A(0.2) C7A(0.2)
 H7A(0.2) Ir2A(0.2) N1A(0.2) C2A(0.2) H2A(0.2) C3A(0.2) H3A(0.2) C4A(0.2)
 H4A(0.2) C5A(0.2) C14A(0.2) N12A(0.2) C11A(0.2) H11A(0.2) C10A(0.2) H10A(0.2)
 C9A(0.2) H9A(0.2) C8A(0.2) C13A(0.2)
7.a :
 C15A(C16A,C17A,C18A,C19A,C20A,C21A,C22A,C23A,C24A,C6A,C7A,Ir2A)
7.b Me refined with riding coordinates:
 C223(H22A,H22B,H22C), C20A(H20A,H20B,H20C), C21A(H21A,H21B,H21C), C22A(H22P,
 H22Q,H22R), C23A(H23A,H23B,H23C), C24A(H24A,H24B,H24C)
7.c Aromatic/amide H refined with riding coordinates:
 C324(H324), C312(H312), C321(H321), C107(H107), C106(H106), C311(H311),
 C418(H418), C109(H109), C323(H323), C407(H407), C303(H303), C305(H305),
 C322(H322), C313(H313), C304(H304), C419(H419), C421(H421), C306(H306),
 C325(H325), C404(H404), C310(H310), C309(H309), C104(H104), C406(H406),
 C410(H410), C319(H319), C318(H318), C317(H317), C316(H316), C315(H315),
 C307(H307), C405(H405), C210(H210), C01H(H01H), C110(H110), C207(H207),
 C102(H102), C103(H103), C403(H403), C416(H416), C417(H417), C413(H413),
 C209(H209), C415(H415), C211(H211), C409(H409), C423(H423), C111(H111),
 C411(H411), C412(H412), C425(H425), C202(H202), C424(H424), C204(H204),
 C203(H203), C206(H206), C6A(H6A), C7A(H7A), C2A(H2A), C3A(H3A), C4A(H4A),
 C11A(H11A), C10A(H10A), C9A(H9A)
7.d Fitted hexagon refined as free rotating group:
 C314(C319,C318,C317,C316,C315), N1A(C2A,C3A,C4A,C5A,C14A), N12A(C11A,C10A,C9A,
 C8A,C13A)
7.e Idealised Me refined as rotating group:
 C123(H12A,H12B,H12C), C124(H12D,H12E,H12F), C221(H22D,H22E,H22F), C224(H22G,
 H22H,H22I), C120(H12G,H12H,H12I), C121(H12J,H12K,H12L), C222(H22J,H22K,H22L),
 C122(H12M,H12N,H12O), C220(H22M,H22N,H22O)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'