Rationally Designed Long-Wavelength Absorbing Ru(II) Polypyridyl Complexes as Photosensitizers for Photodynamic Therapy.
Karges, Johannes; Heinemann, Franz; Jakubaszek, Marta; Maschietto, Federica; Subecz, Chloé; Dotou, Mazzarine; Vinck, Robin; Blacque, Olivier; Tharaud, Mickaël; Goud, Bruno; Viñuelas Zahı Nos, Emilio; Spingler, Bernhard; Ciofini, Ilaria; Gasser, Gilles; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.9b13620

data_4134554
_publ_section_title
;
 Rationally Designed Long-Wavelength Absorbing Ru(II) Polypyridyl
 Complexes as Photosensitizers for Photodynamic Therapy.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b13620
_journal_year                    2020
_chemical_formula_moiety         'C34 H22 Br2 N6 Ru, 2(F6 P), 2(C2 H3 N)'
_chemical_formula_sum            'C38 H28 Br2 F12 N8 P2 Ru'
_chemical_formula_weight         1147.51
_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     dual
_audit_creation_date             2019-12-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90.834(2)
_cell_angle_beta                 98.147(2)
_cell_angle_gamma                101.020(2)
_cell_formula_units_Z            2
_cell_length_a                   11.4219(3)
_cell_length_b                   12.3760(3)
_cell_length_c                   15.0464(4)
_cell_measurement_reflns_used    15014
_cell_measurement_temperature    183(1)
_cell_measurement_theta_max      30.2060
_cell_measurement_theta_min      2.4650
_cell_volume                     2064.73(9)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015b)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      183(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4498
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -48.00  64.00   0.80   20.00    --  -14.56  77.00-180.00  140
  2  \w    -48.00  64.00   0.80   20.00    --  -14.56  77.00  60.00  140
  3  \w    -18.00  94.00   0.80   20.00    --   15.19  77.00  90.00  140
  4  \w    -18.00  94.00   0.80   20.00    --   15.19  77.00 -30.00  140
  5  \w   -105.00 -36.20   0.80   20.00    --  -14.56-178.00-150.00   86
  6  \w   -105.00 -36.20   0.80   20.00    --  -14.56-178.00-180.00   86
  7  \w    -14.00  88.40   0.80   20.00    --   15.19  57.00-150.00  128
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0554899000
_diffrn_orient_matrix_UB_12      0.0109806000
_diffrn_orient_matrix_UB_13      -0.0173298000
_diffrn_orient_matrix_UB_21      -0.0018535000
_diffrn_orient_matrix_UB_22      -0.0574005000
_diffrn_orient_matrix_UB_23      -0.0050563000
_diffrn_orient_matrix_UB_31      -0.0317609000
_diffrn_orient_matrix_UB_32      -0.0004412000
_diffrn_orient_matrix_UB_33      -0.0441147000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0490
_diffrn_reflns_av_unetI/netI     0.0378
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            38483
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.877
_diffrn_reflns_theta_min         2.210
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.488
_exptl_absorpt_correction_T_max  0.744
_exptl_absorpt_correction_T_min  0.599
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
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            red
_exptl_crystal_density_diffrn    1.846
_exptl_crystal_description       block
_exptl_crystal_F_000             1128
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.790
_refine_diff_density_min         -0.608
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     643
_refine_ls_number_reflns         9850
_refine_ls_number_restraints     312
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0488
_refine_ls_R_factor_gt           0.0398
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0566P)^2^+1.5221P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1020
_refine_ls_wR_factor_ref         0.1096
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8411
_reflns_number_total             9850
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13620_si_004.cif
_cod_data_source_block           3
_cod_original_cell_volume        2064.73(10)
_cod_database_code               4134554
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.677
_shelx_estimated_absorpt_t_min   0.532
_olex2_refinement_description
;
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
 N8A-C37A = N8B-C37B
 1.15 with sigma of 0.01
 C37A-C38A = C37B-C38B
 1.45 with sigma of 0.01
 P1-F3A \\sim P1-F3B \\sim P1-F4A \\sim P1-F4B \\sim P1-F5A \\sim P1-F5B \\sim
P1-F6A \\sim P1-F6B
 with sigma of 0.005
 P2-F9A \\sim P2-F9B \\sim P2-F10A \\sim P2-F10B \\sim P2-F11A \\sim P2-F11B
\\sim P2-F12A \\sim P2-F12B
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(C37A) = Uanis(C38A) = Uanis(N8A) = Uanis(N8B) = Uanis(C37B) = Uanis(C38B)
4. Rigid body (RIGU) restrains
 F1, F2, F3A, F3B, F4A, F4B, F5A, F5B, F6A, F6B, P1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F7, F8, F9A, F9B, F10A, F10B, F11A, F11B, F12A, F12B, P2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C37A, C38A, N8A, C37B, C38B, N8B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Others
 Sof(C37B)=Sof(C38B)=Sof(H38D)=Sof(H38E)=Sof(H38F)=Sof(N8B)=1-FVAR(1)
 Sof(C37A)=Sof(C38A)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(N8A)=FVAR(1)
 Sof(F3B)=Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(2)
 Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(2)
 Sof(F9B)=Sof(F10B)=Sof(F11B)=Sof(F12B)=1-FVAR(3)
 Sof(F9A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(3)
6.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24),
  C25(H25), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34)
6.b Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C38A(H38A,H38B,H38C), C38B(H38D,H38E,H38F)
;
_shelx_res_checksum              6864
_shelx_hkl_checksum              42224