Platinum(iv) dihydroxido diazido N-(heterocyclic)imine complexes are potently photocytotoxic when irradiated with visible light
Shaili, Evyenia; Salassa, Luca; Woods, Julie A.; Clarkson, Guy; Sadler, Peter J.; Farrer, Nicola J.; Chemical Science  (2019) –; doi:10.1039/C9SC02644D

data_1552174
_publ_section_title
;
 Platinum(iv) dihydroxido diazido N-(heterocyclic)imine complexes are
 potently photocytotoxic when irradiated with visible light
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC02644D
_journal_year                    2019
_chemical_formula_moiety         '2(C6 H8 N4 O Pt0.5), 2(C O)'
_chemical_formula_sum            'C14 H16 N8 O4 Pt'
_chemical_formula_weight         555.44
_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             2019-04-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-04-30 deposited with the CCDC.    2019-08-08 downloaded from the CCDC.
;
_cell_angle_alpha                97.817(2)
_cell_angle_beta                 105.393(2)
_cell_angle_gamma                114.191(2)
_cell_formula_units_Z            2
_cell_length_a                   9.4521(2)
_cell_length_b                   9.5887(2)
_cell_length_c                   12.0611(2)
_cell_measurement_reflns_used    10199
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      32.1150
_cell_measurement_theta_min      3.5870
_cell_volume                     923.39(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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_temperature      100(2)
_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 0.929
_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 -40.00 16.00 1.00 10.00 -- 18.58 -38.00-180.00 56 2 \w -13.00 97.00 1.00 10.00 -- 18.58 77.00-150.00 110 3 \w -15.00 87.00 1.00 10.00 -- 18.58 77.00 0.00 102 4 \w -7.00 66.00 1.00 10.00 -- 18.58 38.00 150.00 73 5 \w -57.00 38.00 1.00 10.00 -- 18.58 -38.00 90.00 95 6 \w 37.00 108.00 1.00 10.00 -- 18.58 179.00 -30.00 71 7 \w 34.00 81.00 1.00 10.00 -- 18.58 179.00 120.00 47 8 \w -45.00 23.00 1.00 10.00 -- 18.58 -38.00 -60.00 68 9 \w -81.00 -46.00 1.00 10.00 -- -19.51 131.00 59.00 35 10 \w -90.00 -51.00 1.00 10.00 -- -19.51 146.00 -82.00 39'
_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      0.0069108000
_diffrn_orient_matrix_UB_12      -0.0712490000
_diffrn_orient_matrix_UB_13      -0.0091832000
_diffrn_orient_matrix_UB_21      0.0858235000
_diffrn_orient_matrix_UB_22      0.0449332000
_diffrn_orient_matrix_UB_23      0.0107267000
_diffrn_orient_matrix_UB_31      0.0182382000
_diffrn_orient_matrix_UB_32      0.0057505000
_diffrn_orient_matrix_UB_33      0.0619167000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0218
_diffrn_reflns_av_unetI/netI     0.0222
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.929
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            19134
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.929
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.259
_diffrn_reflns_theta_min         3.010
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    7.637
_exptl_absorpt_correction_T_max  0.328
_exptl_absorpt_correction_T_min  0.094
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
'CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Analytical numeric absorption correction using a multifaceted crystal 			model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.998
_exptl_crystal_description       block
_exptl_crystal_F_000             532
_exptl_crystal_size_max          0.562
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.244
_refine_diff_density_max         1.914
_refine_diff_density_min         -1.397
_refine_diff_density_rms         0.142
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.134
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     251
_refine_ls_number_reflns         6084
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.135
_refine_ls_R_factor_all          0.0300
_refine_ls_R_factor_gt           0.0228
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0170P)^2^+2.6874P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0547
_refine_ls_wR_factor_ref         0.0579
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4905
_reflns_number_total             6084
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc02644d2.cif
_cod_data_source_block           es4
_cod_original_cell_volume        923.38(4)
_cod_database_code               1552174
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H20 N2 O2 Pt'
_shelx_estimated_absorpt_t_max   0.257
_shelx_estimated_absorpt_t_min   0.099
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.01
_olex2_refinement_description
;
One of the methanols (O1-C2) bridges between the OHs of the different complexes. 
The other methanol (O3 C4) bridges between this methanol and other symmetry related complexes. 
It was not possible to differentiate the C from the O from examination of the thermal ellipsoids 
or from the hydrogen bonding pattern so the oxygen and the carbon of that methanol were modelled 
as 50% occupancy at either position. The hydrogens (O100 and O200) were located on the OH ligands 
on each crystallographically independent Pt complex but refined with restraints. 
No hydrogens were located for the disordered solvents

1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Shared sites
{O3, C3}
{C4, O4}
3. Uiso/Uaniso restraints and constraints
Uanis(O3) = Uanis(C3)
Uanis(C4) = Uanis(O4)
4. Rigid body (RIGU) restrains
 O1, C2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Fixed Sof: O3(0.5) C4(0.5) C3(0.5) O4(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C105(H105), C202(H202), C206(H206), C102(H102), C106(H106), C203(H203),
 C103(H103), C205(H205)
6.b Idealised Me refined as rotating group:
 C107(H10A,H10B,H10C), C207(H20A,H20B,H20C)
6.c Idealised tetrahedral OH refined as rotating group:
 O200(H200), O100(H100)
;
_shelx_res_checksum              23514
_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 1.304
_oxdiff_exptl_absorpt_empirical_full_min 0.804