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_7709859
_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         '2(C44 H40 Cu2 N8 O4 P2 S2)'
_chemical_formula_sum            'C88 H80 Cu4 N16 O8 P4 S4'
_chemical_formula_weight         1995.96
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yac'
_space_group_name_H-M_alt        'P 1 2/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-03-05
_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                 115.6403(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   29.17370(17)
_cell_length_b                   11.66423(5)
_cell_length_c                   29.95363(18)
_cell_measurement_reflns_used    40009
_cell_measurement_temperature    295.72(11)
_cell_measurement_theta_max      76.8960
_cell_measurement_theta_min      4.1140
_cell_volume                     9189.17(10)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      295.72(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.961
_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      4.00  29.00   0.50    1.00    --   47.12  -5.00  29.00   50
  2  \w     36.00  63.00   0.50    4.00    --  108.56 -61.00   0.00   54
  3  \w     77.00 105.00   0.50    4.00    --  108.56 -77.00 -60.00   56
  4  \w     66.00 105.00   0.50    4.00    --  108.56 -94.00-120.00   78
  5  \w     52.00  97.00   0.50    4.00    --  108.56 -77.00-180.00   90
  6  \w     59.00 177.00   0.50    4.00    --  108.56   5.00-154.00  236
  7  \w     91.00 170.00   0.50    4.00    --  108.56  15.00 -90.00  158
  8  \w     73.00 121.00   0.50    1.00    --   47.12   5.00-154.00   96
  9  \w     60.00  93.00   0.50    1.00    --   47.12-125.00-120.00   66
 10  \w     40.00  94.00   0.50    4.00    --  108.56-125.00   0.00  108
 11  \w     47.00 112.00   0.50    4.00    --  108.56-131.00  16.52  130
 12  \w     47.00 105.00   0.50    4.00    --  108.56 -94.00  60.00  116
 13  \w     40.00  66.00   0.50    4.00    --  108.56 -61.00  90.00   52
 14  \w     36.00  70.00   0.50    4.00    --  108.56 -61.00 150.00   68
 15  \w     36.00  71.00   0.50    4.00    --  108.56 -61.00-120.00   70
 16  \w      3.00  40.00   0.50    1.00    --   47.12 -37.00-180.00   74
 17  \w    -34.00  22.00   0.50    1.00    --  -47.12   5.00-154.00  112
 18  \w    -70.00 -34.00   0.50    1.00    --  -47.12 -43.00   7.71   72
 19  \w    -95.00 -45.00   0.50    4.00    --  -88.50  -5.00  29.00  100
 20  \w    -64.00 -38.00   0.50    4.00    --  -88.50  61.00 120.00   52
 21  \w   -121.00 -49.00   0.50    1.00    --  -47.12  -5.00  29.00  144
 22  \w   -104.00 -78.00   0.50    1.00    --  -47.12 -43.00   7.71   52
 23  \w   -120.00 -35.00   0.50    1.00    --  -47.12 -42.00 -52.68  170
 24  \w   -131.00-105.00   0.50    4.00    --  -88.50  -5.00  29.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0470323000
_diffrn_orient_matrix_UB_12      -0.0041084000
_diffrn_orient_matrix_UB_13      -0.0108127000
_diffrn_orient_matrix_UB_21      0.0349102000
_diffrn_orient_matrix_UB_22      0.0089340000
_diffrn_orient_matrix_UB_23      0.0558501000
_diffrn_orient_matrix_UB_31      0.0009154000
_diffrn_orient_matrix_UB_32      -0.1317031000
_diffrn_orient_matrix_UB_33      0.0041564000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0266
_diffrn_reflns_av_unetI/netI     0.0248
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            66181
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.244
_diffrn_reflns_theta_min         2.807
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.066
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76649
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic light gray'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    gray
_exptl_crystal_density_diffrn    1.443
_exptl_crystal_description       block
_exptl_crystal_F_000             4096
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.497
_refine_diff_density_min         -0.316
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1145
_refine_ls_number_reflns         18733
_refine_ls_number_restraints     61
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0405
_refine_ls_R_factor_gt           0.0345
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0469P)^2^+3.2786P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0929
_refine_ls_wR_factor_ref         0.0965
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16135
_reflns_number_total             18733
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00063f2.cif
_cod_data_source_block           20201121-hfp-yx-q3-repeat
_cod_database_code               7709859
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C86 H86 N86 O86 P86 S86 Cu86 '
_shelx_estimated_absorpt_t_max   0.526
_shelx_estimated_absorpt_t_min   0.440
_reflns_odcompleteness_completeness 99.74
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C80A-C79
 1.39 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C80) \\sim Ueq, Uanis(C80A) \\sim Ueq, Uanis(C81A) \\sim Ueq, Uanis(C81)
\\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(C82A) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(O4A) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C52)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C80) = Uanis(C80A)
Uanis(C82) = Uanis(C82A)
Uanis(C81) = Uanis(C81A)
Uanis(C66) = Uanis(C66A)
Uanis(C67) = Uanis(C67A)
Uanis(C68) = Uanis(C68A)
Uanis(O4) = Uanis(O4A)
4. Others
 Sof(H79A)=Sof(C80A)=Sof(H80A)=Sof(C81A)=Sof(H81A)=Sof(C82A)=Sof(H82A)=1-FVAR(1)
 Sof(H79)=Sof(C80)=Sof(H80)=Sof(C81)=Sof(H81)=Sof(C82)=Sof(H82)=FVAR(1)
 Sof(H69A)=Sof(C66A)=Sof(H66A)=Sof(C67A)=Sof(H67A)=Sof(C68A)=Sof(H68A)=1-FVAR(2)
 Sof(H69)=Sof(C66)=Sof(H66)=Sof(C67)=Sof(H67)=Sof(C68)=Sof(H68)=FVAR(2)
 Sof(O4A)=1-FVAR(3)
 Sof(O4)=FVAR(3)
5.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C6(H6A,H6B), C10(H10A,H10B), C14(H14A,H14B)
5.b Aromatic/amide H refined with riding coordinates:
 C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C24(H24), C25(H25),
 C26(H26), C27(H27), C28(H28), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34),
  C36(H36), C37(H37), C38(H38), C39(H39), C40(H40), C42(H42), C43(H43),
 C44(H44), C45(H45), C46(H46), C48(H48), C49(H49), C50(H50), C51(H51), C52(H52),
  C54(H54), C55(H55), C56(H56), C57(H57), C58(H58), C60(H60), C61(H61),
 C62(H62), C63(H63), C64(H64), C69(H69), C69(H69A), C70(H70), C72(H72),
 C73(H73), C74(H74), C75(H75), C76(H76), C78(H78), C79(H79), C79(H79A),
 C84(H84), C85(H85), C86(H86), C87(H87), C88(H88), C66(H66), C67(H67), C68(H68),
  C80(H80), C81(H81), C82(H82), C66A(H66A), C67A(H67A), C68A(H68A), C80A(H80A),
 C81A(H81A), C82A(H82A)
5.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C8(H8A,H8B,H8C), C12(H12A,H12B,H12C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              60834
_shelx_hkl_checksum              44817
_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 1.521
_oxdiff_exptl_absorpt_empirical_full_min 0.723