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_4134553
_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
'C36 H28 N6 Ru, 2(F6 P), C5 H10 O, 0.25(H2 O)'
_chemical_formula_sum            'C41 H38.5 F12 N6 O1.25 P2 Ru'
_chemical_formula_weight         1026.29
_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   mixed
_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                79.9877(16)
_cell_angle_beta                 75.692(2)
_cell_angle_gamma                62.241(2)
_cell_formula_units_Z            2
_cell_length_a                   12.8029(3)
_cell_length_b                   13.1575(2)
_cell_length_c                   16.2010(4)
_cell_measurement_reflns_used    27417
_cell_measurement_temperature    183(1)
_cell_measurement_theta_max      76.3990
_cell_measurement_theta_min      3.8000
_cell_volume                     2334.63(10)
_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, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      183(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3801
_diffrn_detector_type            Atlas
_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    -70.00  30.00   0.80    5.00    --  -41.69  57.00 -30.00  125
  2  \w    -96.00  -2.40   0.80    5.00    --  -41.69 125.00 -30.00  117
  3  \w   -116.00 -17.60   0.80    5.00    --  -41.69 -37.00  60.00  123
  4  \w    -66.00  32.40   0.80    5.00    --  -41.69  37.00-120.00  123
  5  \w     23.00  97.40   0.80    5.00    --   41.69-125.00-150.00   93
  6  \w     36.00 116.00   0.80   20.00    --  112.00-112.00 149.00  100
  7  \w    100.00 178.40   0.80   20.00    --  112.00 111.00-180.00   98
  8  \w     36.00 116.00   0.80   20.00    --  112.00-111.00   0.00  100
  9  \w     86.00 178.00   0.80   20.00    --  112.00  45.00-120.00  115
 10  \w     40.00 138.40   0.80   20.00    --  112.00 -45.00-120.00  123
 11  \w     29.00 109.00   0.80   20.00    --  112.00 -94.00-180.00  100
 12  \w     36.00 116.00   0.80   20.00    --  112.00-111.00  60.00  100
 13  \w     84.00 178.40   0.80   20.00    --  112.00  30.00   0.00  118
 14  \w     29.00 109.00   0.80   20.00    --  112.00 -94.00 150.00  100
 15  \w     29.00 109.00   0.80   20.00    --  112.00 -94.00 120.00  100
 16  \w     29.00 109.00   0.80   20.00    --  112.00 -94.00  90.00  100
 17  \w     36.00 116.00   0.80   20.00    --  112.00-111.00-120.00  100
 18  \w     84.00 178.40   0.80   20.00    --  112.00  30.00 -60.00  118
 19  \w     29.00 109.00   0.80   20.00    --  112.00 -94.00-150.00  100
 20  \w     36.00 116.00   0.80   20.00    --  112.00-111.00  30.00  100
 21  \w     36.00 116.00   0.80   20.00    --  112.00-111.00 -30.00  100
 22  \w     80.00 178.40   0.80   20.00    --  112.00  77.00-180.00  123
 23  \w     40.00 140.00   0.80   20.00    --  112.00 -61.00 150.00  125
 24  \w     58.00 150.80   0.80   20.00    --  112.00 178.00 -30.00  116
 25  \w     58.00 150.80   0.80   20.00    --  112.00 178.00-180.00  116
 26  \w     30.00 164.40   0.80   20.00    --  112.00 -15.00  30.00  168
 27  \w   -118.00 -10.00   0.80    5.00    --  -41.69 -77.00-120.00  135
 28  \w   -118.00 -10.00   0.80    5.00    --  -41.69 -77.00  60.00  135
 29  \w   -118.00 -10.00   0.80    5.00    --  -41.69 -77.00 -30.00  135
 30  \w     14.00 114.00   0.80    5.00    --   41.69  57.00-180.00  125
 31  \w      1.00  82.60   0.80    5.00    --   41.69 -99.00 120.00  102
 32  \w      9.00 117.00   0.80    5.00    --   41.69  77.00-120.00  135
 33  \w     84.00 178.40   0.80   20.00    --  112.00  30.00 120.00  118
 34  \w     80.00 178.40   0.80   20.00    --  112.00  77.00   0.00  123
 35  \w     84.00 178.40   0.80   20.00    --  112.00  61.00 150.00  118
 36  \w     83.00 103.00   0.80   20.00    --  112.00  61.00 -60.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0001455000
_diffrn_orient_matrix_UB_12      0.0124141000
_diffrn_orient_matrix_UB_13      0.0928514000
_diffrn_orient_matrix_UB_21      -0.1301644000
_diffrn_orient_matrix_UB_22      0.0147559000
_diffrn_orient_matrix_UB_23      0.0266235000
_diffrn_orient_matrix_UB_31      0.0473813000
_diffrn_orient_matrix_UB_32      -0.1312158000
_diffrn_orient_matrix_UB_33      0.0185910000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0221
_diffrn_reflns_av_unetI/netI     0.0130
_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       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            44520
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.497
_diffrn_reflns_theta_min         3.805
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.143
_exptl_absorpt_correction_T_max  0.939
_exptl_absorpt_correction_T_min  0.636
_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    1.460
_exptl_crystal_description       plate
_exptl_crystal_F_000             1037
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.361
_refine_diff_density_min         -0.352
_refine_diff_density_rms         0.129
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     627
_refine_ls_number_reflns         9539
_refine_ls_number_restraints     86
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0523
_refine_ls_R_factor_gt           0.0491
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1094P)^2^+1.6784P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1495
_refine_ls_wR_factor_ref         0.1562
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8928
_reflns_number_total             9539
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13620_si_003.cif
_cod_data_source_block           2
_cod_original_formula_sum        'C41 H38.50 F12 N6 O1.25 P2 Ru'
_cod_database_code               4134553
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.886
_shelx_estimated_absorpt_t_min   0.295
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C37A-C38A = C38A-C39A = C39A-C40A = C40A-C41A
 1.54 with sigma of 0.005
 C37B-C38B = C38B-C39B = C39B-C40B = C40B-C41B
 1.54 with sigma of 0.005
 O1B-C37B = O1B-C41B = O1A-C37A = O1A-C41A
 1.45 with sigma of 0.005
 C42A-C43A = C43A-C44A = C44A-C45A = C45A-C46A
 1.54 with sigma of 0.005
 C42B-C43B = C43B-C44B = C44B-C45B = C45B-C46B
 1.54 with sigma of 0.005
 O2B-C42B = O2B-C46B = O2A-C42A = O2A-C46A
 1.45 with sigma of 0.005
 O1B-C38B = O1B-C40B = O1A-C38A = O1A-C40A
 2.46 with sigma of 0.01
 O2B-C43B = O2B-C45B = O2A-C43A = O2A-C45A
 2.46 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uiso(C38B) = Uiso(C39A) = Uiso(C40B) = Uiso(C41A) = Uiso(C37A) = Uiso(O1B) =
Uiso(C37B) = Uiso(C38A) = Uiso(C39B) = Uiso(C40A) = Uiso(C41B) = Uiso(O1A)
Uiso(C42A) = Uiso(C43A) = Uiso(C44B) = Uiso(C45B) = Uiso(C46B) = Uiso(O2A) =
Uiso(O2B) = Uiso(C46A) = Uiso(C44A) = Uiso(C43B) = Uiso(C45A) = Uiso(C42B)
4. Rigid body (RIGU) restrains
 F10A, F10B, F11A, F11B, F12A, F12B, P3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F7, F8, F9, P2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Others
 Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(1)
 Sof(F10B)=Sof(F11B)=Sof(F12B)=FVAR(1)
 Sof(C37B)=Sof(H37C)=Sof(H37D)=Sof(C38B)=Sof(H38C)=Sof(H38D)=Sof(C39B)=
 Sof(H39C)=Sof(H39D)=Sof(C40B)=Sof(H40C)=Sof(H40D)=Sof(C41B)=Sof(H41C)=
 Sof(H41D)=Sof(O1B)=0.5*(1-FVAR(3))
 Sof(C37A)=Sof(H37A)=Sof(H37B)=Sof(C38A)=Sof(H38A)=Sof(H38B)=Sof(C39A)=
 Sof(H39A)=Sof(H39B)=Sof(C40A)=Sof(H40A)=Sof(H40B)=Sof(C41A)=Sof(H41A)=
 Sof(H41B)=Sof(O1A)=0.5*FVAR(3)
 Sof(C42B)=Sof(H42C)=Sof(H42D)=Sof(C43B)=Sof(H43C)=Sof(H43D)=Sof(C44B)=
 Sof(H44C)=Sof(H44D)=Sof(C45B)=Sof(H45C)=Sof(H45D)=Sof(C46B)=Sof(H46C)=
 Sof(H46D)=Sof(O2B)=0.5*(1-FVAR(4))
 Sof(C42A)=Sof(H42A)=Sof(H42B)=Sof(C43A)=Sof(H43A)=Sof(H43B)=Sof(C44A)=
 Sof(H44A)=Sof(H44B)=Sof(C45A)=Sof(H45A)=Sof(H45B)=Sof(C46A)=Sof(H46A)=
 Sof(H46B)=Sof(O2A)=0.5*FVAR(4)
 Fixed Sof: O3(0.25) H3A(0.25) H3B(0.25)
 Fixed X: H3A(0.20702) H3B(0.244579)
 Fixed Y: H3A(0.92809) H3B(0.9635)
 Fixed Z: H3A(0.56901) H3B(0.627331)
6.a Secondary CH2 refined with riding coordinates:
 C37A(H37A,H37B), C37B(H37C,H37D), C38A(H38A,H38B), C38B(H38C,H38D), C39A(H39A,
 H39B), C39B(H39C,H39D), C40A(H40A,H40B), C40B(H40C,H40D), C41A(H41A,H41B),
 C41B(H41C,H41D), C42A(H42A,H42B), C42B(H42C,H42D), C43A(H43A,H43B), C43B(H43C,
 H43D), C44A(H44A,H44B), C44B(H44C,H44D), C45A(H45A,H45B), C45B(H45C,H45D),
 C46A(H46A,H46B), C46B(H46C,H46D)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C7(H7), C9(H9), C10(H10), C13(H13), C14(H14),
 C15(H15), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26),
  C27(H27), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36)
6.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C)
;
_shelx_res_checksum              13646
_shelx_hkl_checksum              75490
_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 1.442
_oxdiff_exptl_absorpt_empirical_full_min 0.637