Metal dipyrrin complexes as potential photosensitizers for photodynamic therapy
Karges, Johannes; Blacque, Olivier; Gasser, Gilles; Inorganica Chimica Acta 505 (2020) 119482–; doi:10.1016/j.ica.2020.119482

data_1565207
_publ_section_title
;
 Metal dipyrrin complexes as potential photosensitizers for photodynamic
 therapy
;
_journal_name_full               'Inorganica Chimica Acta'
_journal_page_first              119482
_journal_paper_doi               10.1016/j.ica.2020.119482
_journal_volume                  505
_journal_year                    2020
_chemical_formula_moiety         'C44 H46 Cu I4 N4, 0.25(C6 H14)'
_chemical_formula_sum            'C45.5 H49.5 Cu I4 N4'
_chemical_formula_weight         1223.53
_space_group_crystal_system      tetragonal
_space_group_IT_number           88
_space_group_name_Hall           '-I 4ad'
_space_group_name_H-M_alt        'I 41/a :2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            32
_cell_length_a                   52.0433(2)
_cell_length_b                   52.0433(2)
_cell_length_c                   14.00387(10)
_cell_measurement_reflns_used    25722
_cell_measurement_temperature    160(1)
_cell_measurement_theta_max      76.7100
_cell_measurement_theta_min      3.2440
_cell_volume                     37929.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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      160(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   -124.00 -79.00   0.75    5.00    --  -38.84 -99.00   0.00   60
  2  \w    -75.00  45.00   0.75    5.00    --  -38.84  77.00-180.00  160
  3  \w    100.00 178.00   0.75   20.00    --  116.00 111.00-120.00  104
  4  \w    100.00 178.00   0.75   20.00    --  116.00 111.00 150.00  104
  5  \w     83.00 177.50   0.75   20.00    --  116.00  61.00  60.00  126
  6  \w     35.00 113.00   0.75   20.00    --  116.00-111.00   0.00  104
  7  \w    100.00 178.00   0.75   20.00    --  116.00 111.00 -30.00  104
  8  \w    100.00 178.00   0.75   20.00    --  116.00 111.00   0.00  104
  9  \w   -118.00  -7.00   0.75    5.00    --  -38.84 -37.00 150.00  148
 10  \w   -124.00 -79.00   0.75    5.00    --  -38.84 -99.00 150.00   60
 11  \w     35.00 177.50   0.75   20.00    --  116.00  15.00-120.00  190
 12  \w     85.00 110.50   0.75   20.00    --  116.00  45.00 120.00   34
 13  \w     83.00 177.50   0.75   20.00    --  116.00  61.00 -60.00  126
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0021993000
_diffrn_orient_matrix_UB_12      -0.0270952000
_diffrn_orient_matrix_UB_13      0.0435353000
_diffrn_orient_matrix_UB_21      0.0005868000
_diffrn_orient_matrix_UB_22      -0.0117880000
_diffrn_orient_matrix_UB_23      -0.1008756000
_diffrn_orient_matrix_UB_31      0.0295172000
_diffrn_orient_matrix_UB_32      -0.0017918000
_diffrn_orient_matrix_UB_33      0.0052243000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0491
_diffrn_reflns_av_unetI/netI     0.0377
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       63
_diffrn_reflns_limit_h_min       -48
_diffrn_reflns_limit_k_max       64
_diffrn_reflns_limit_k_min       -64
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            101057
_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         74.503
_diffrn_reflns_theta_min         3.268
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    21.352
_exptl_absorpt_correction_T_max  0.812
_exptl_absorpt_correction_T_min  0.133
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.714
_exptl_crystal_description       needle
_exptl_crystal_F_000             18928
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.01
_refine_diff_density_max         2.093
_refine_diff_density_min         -1.255
_refine_diff_density_rms         0.097
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     983
_refine_ls_number_reflns         19383
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0440
_refine_ls_R_factor_gt           0.0338
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0327P)^2^+133.1229P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0765
_refine_ls_wR_factor_ref         0.0811
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                16259
_reflns_number_total             19383
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ICA-2020-505-119482.cif
_cod_data_source_block           2_sq
_cod_depositor_comments
;

2022-04-19
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C91 H99 Cu2 I8 N8'
_cod_original_formula_weight         2447.06
_cod_original_formula_moiety         '2(C44 H46 Cu I4 N4), 0.5(C6 H14)'
_cod_original_formula_units_Z            16
_cod_original_cell_volume        37929.6(4)
_cod_original_sg_symbol_H-M      'I 41/a'
_cod_database_code               1565207
_shelx_estimated_absorpt_t_max   0.815
_shelx_estimated_absorpt_t_min   0.114
_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. Uiso/Uaniso restraints and constraints
C3 \\sim C11: within 2A with sigma of 0.004 and sigma for terminal atoms of
0.008
3.a Aromatic/amide H refined with riding coordinates:
 C16(H16), C18(H18), C38(H38), C40(H40), C60(H60), C62(H62), C82(H82), C84(H84)
3.b Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,
 H13C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C32(H32A,
 H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C),
 C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C54(H54A,H54B,
 H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C64(H64A,
 H64B,H64C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C76(H76A,H76B,H76C),
 C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C79(H79A,H79B,H79C), C86(H86A,H86B,
 H86C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C)
;