Rational construction of a triphenylphosphine-modified tetra-nuclear Cu(i) coordinated cluster for enhanced chemodynamic therapy
You, Xin; Hong, Zhao-Guo; Shi, Sheng-Mei; Bian, He-Dong; Zhang, Yun-Liang; Zhang, Liang-Liang; Huang, Fu-Ping; Zhao, Shu-Lin; Liang, Hong; Dalton Transactions  (2022) –; doi:10.1039/D2DT00063F

data_7709860
_publ_section_title
;
 Rational construction of a triphenylphosphine-modified tetra-nuclear
 Cu(i) coordinated cluster for enhanced chemodynamic therapy
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00063F
_journal_year                    2022
_chemical_formula_moiety         'C42 H40 Cu N6 P2 S4, N O3, C H4 O'
_chemical_formula_sum            'C43 H44 Cu N7 O4 P2 S4'
_chemical_formula_weight         976.57
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2021-07-31
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2021-11-12 deposited with the CCDC.	2022-03-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   46.0372(3)
_cell_length_b                   46.0372(3)
_cell_length_c                   11.65150(7)
_cell_measurement_reflns_used    64480
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      77.0480
_cell_measurement_theta_min      3.3090
_cell_volume                     21386.0(2)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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    105.00 176.00   0.50    1.00    --  108.56  77.00 -90.00  142
  2  \w    121.00 175.00   0.50    1.00    --  108.56  45.00   0.00  108
  3  \w     91.00 178.00   0.50    1.00    --  108.56  61.00  60.00  174
  4  \w    101.00 127.00   0.50    1.00    --  108.56  45.00 120.00   52
  5  \w    129.00 155.00   0.50    1.00    --  108.56  45.00 120.00   52
  6  \w    -26.00  27.00   0.50    0.40    --  -46.87  19.00  30.00  106
  7  \w    -51.00 -16.00   0.50    1.00    --  -88.50  45.00-180.00   70
  8  \w    -51.00 -23.00   0.50    1.00    --  -88.50  45.00  60.00   56
  9  \w    -48.00 -16.00   0.50    1.00    --  -88.50  45.00 120.00   64
 10  \w     -6.00  25.00   0.50    0.40    --   46.87 -19.00 120.00   62
 11  \w     56.00  82.00   0.50    0.40    --   46.87-125.00   0.00   52
 12  \w    -13.00  78.00   0.50    0.40    --   46.87 -93.00-163.00  182
 13  \w    -26.00  41.00   0.50    0.40    --   46.87 -37.00-150.00  134
 14  \w    104.00 178.00   0.50    1.00    --  108.56  93.00 -51.00  148
 15  \w    136.00 178.00   0.50    1.00    --  108.56 125.00-120.00   84
 16  \w     96.00 122.00   0.50    1.00    --  108.56 125.00-120.00   52
 17  \w     36.00 100.00   0.50    1.00    --  108.56-125.00   0.00  128
 18  \w     70.00 105.00   0.50    1.00    --  108.56 -94.00  60.00   70
 19  \w     37.00 106.00   0.50    1.00    --  108.56-104.00  56.10  138
 20  \w     36.00 107.00   0.50    1.00    --  108.56-113.00  39.51  142
 21  \w     66.00  92.00   0.50    1.00    --  108.56 -94.00   0.00   52
 22  \w     48.00 100.00   0.50    1.00    --  108.56 -94.00 -60.00  104
 23  \w     36.00 105.00   0.50    1.00    --  108.56 -94.00-120.00  138
 24  \w     38.00  91.00   0.50    1.00    --  108.56 -94.00-150.00  106
 25  \w     36.00 106.00   0.50    1.00    --  108.56 -93.00-163.00  140
 26  \w     48.00  79.00   0.50    1.00    --  108.56 -94.00  90.00   62
 27  \w     62.00 105.00   0.50    1.00    --  108.56 -94.00 150.00   86
 28  \w    -78.00  26.00   0.50    0.40    --  -46.87  93.00 -51.00  208
 29  \w    -46.00 -17.00   0.50    1.00    --  -88.50 125.00-150.00   58
 30  \w    -81.00 -16.00   0.50    1.00    --  -88.50 125.00 -60.00  130
 31  \w    -80.00 -15.00   0.50    1.00    --  -88.50  93.00 -51.00  130
 32  \w    -78.00 -16.00   0.50    1.00    --  -88.50 125.00 150.00  124
 33  \w   -112.00 -69.00   0.50    1.00    --  -88.50 -65.00 -96.10   86
 34  \w   -106.00 -76.00   0.50    1.00    --  -88.50 -61.00-120.00   60
 35  \w   -154.00-118.00   0.50    1.00    --  -88.50 -65.00 -96.10   72
 36  \w   -155.00-115.00   0.50    1.00    --  -88.50 -61.00-120.00   80
 37  \w   -110.00 -84.00   0.50    1.00    --  -88.50 -93.00-163.00   52
 38  \w   -142.00-115.00   0.50    1.00    --  -88.50 -93.00-163.00   54
 39  \w   -119.00 -74.00   0.50    0.40    --  -46.87-125.00 -60.00   90
 40  \w   -120.00 -75.00   0.50    0.40    --  -46.87-125.00   0.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0248065000
_diffrn_orient_matrix_UB_12      -0.0358456000
_diffrn_orient_matrix_UB_13      -0.0411409000
_diffrn_orient_matrix_UB_21      0.0296168000
_diffrn_orient_matrix_UB_22      -0.0044491000
_diffrn_orient_matrix_UB_23      -0.0378109000
_diffrn_orient_matrix_UB_31      0.0008319000
_diffrn_orient_matrix_UB_32      -0.0137293000
_diffrn_orient_matrix_UB_33      0.1197994000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0577
_diffrn_reflns_av_unetI/netI     0.0222
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       57
_diffrn_reflns_limit_h_min       -57
_diffrn_reflns_limit_k_max       58
_diffrn_reflns_limit_k_min       -57
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            96776
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.383
_diffrn_reflns_theta_min         3.326
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.319
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.365
_exptl_crystal_description       block
_exptl_crystal_F_000             9108
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.385
_refine_diff_density_min         -0.493
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     568
_refine_ls_number_reflns         9970
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0408
_refine_ls_R_factor_gt           0.0391
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0554P)^2^+33.5836P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1050
_refine_ls_wR_factor_ref         0.1062
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9367
_reflns_number_total             9970
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00063f2.cif
_cod_data_source_block           20201123-hfp-yx-qc-1
_cod_original_cell_volume        21386.0(3)
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               7709860
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C774 H612 Cu18 N90 O108 P36 S72 '
_shelx_estimated_absorpt_t_max   0.852
_shelx_estimated_absorpt_t_min   0.777
_reflns_odcompleteness_completeness 99.99
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C42(H42A,H42B), C39(H39A,H39B)
2.b Aromatic/amide H refined with riding coordinates:
 N4(H4A), N1(H1), C14(H14), C24(H24), C30(H30), C6(H6A), C8(H8), C12(H12),
 C36(H36), C2(H2A), C9(H9), C32(H32), C5(H5), C11(H11), C10(H10), C26(H26),
 C34(H34), C35(H35), C15(H15), C29(H29), C20(H20), C28(H28), C3(H3A), C33(H33),
 C18(H18), C23(H23), C16(H16), C27(H27), C4(H4B), C17(H17), C22(H22), C21(H21)
2.c Idealised Me refined as rotating group:
 C43(H43A,H43B,H43C)
2.d Idealised tetrahedral OH refined as rotating group:
 O4(H4C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              78705
_shelx_hkl_checksum              82163
_shelx_fab_checksum              25190
_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 1.873
_oxdiff_exptl_absorpt_empirical_full_min 0.529