Two novel chiral tetranucleate copper-based complexes: syntheses, crystal structures, inhibition of angiogenesis and the growth of human breast cancer in vitro and in vivo
Hou, Xiao-Xiao; Ren, Ya-Ping; Luo, Zhao-Hui; Jiang, Bing-Li; Lu, Tian-Tian; Huang, Fu-Ping; Qin, Xiu-Ying; Dalton Transactions  (2021) –; doi:10.1039/D1DT02033A

data_7708460
_publ_section_title
;
 Two novel chiral tetranucleate copper-based complexes: syntheses, crystal
 structures, inhibition of angiogenesis and the growth of human breast
 cancer in vitro and in vivo
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT02033A
_journal_year                    2021
_chemical_formula_moiety         '2(C26 H34 Cu2 N2 O6 S2)'
_chemical_formula_sum            'C52 H68 Cu4 N4 O12 S4'
_chemical_formula_weight         1323.50
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'I 2y'
_space_group_name_H-M_alt        'I 1 2 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-08-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-08-28 deposited with the CCDC.	2021-09-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.730(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.0626(7)
_cell_length_b                   13.2138(3)
_cell_length_c                   19.8116(8)
_cell_measurement_reflns_used    5808
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      26.0870
_cell_measurement_theta_min      3.8550
_cell_volume                     5811.4(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0233
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.889
_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     22.00  61.00   1.00   15.00    --   18.63 -99.00 -30.00   39
  2  \w    -86.00  11.00   1.00   15.00    --  -18.94 -77.00  60.00   97
  3  \w    -30.00  -2.00   1.00   15.00    --  -18.94 -57.00-180.00   28
  4  \w    -46.00  18.00   1.00   15.00    --  -18.94  77.00-180.00   64
  5  \w     19.00  48.00   1.00   15.00    --  -18.94  77.00-180.00   29
  6  \w     14.00  43.00   1.00   15.00    --  -18.94  57.00-180.00   29
  7  \w    -88.00   8.00   1.00   15.00    --  -18.94 -19.00-120.00   96
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0183074000
_diffrn_orient_matrix_UB_12      0.0372282000
_diffrn_orient_matrix_UB_13      0.0214407000
_diffrn_orient_matrix_UB_21      -0.0258619000
_diffrn_orient_matrix_UB_22      0.0302352000
_diffrn_orient_matrix_UB_23      -0.0022144000
_diffrn_orient_matrix_UB_31      -0.0041803000
_diffrn_orient_matrix_UB_32      -0.0240860000
_diffrn_orient_matrix_UB_33      0.0303188000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0263
_diffrn_reflns_av_unetI/netI     0.0565
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.889
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            21873
_diffrn_reflns_point_group_measured_fraction_full 0.948
_diffrn_reflns_point_group_measured_fraction_max 0.800
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.166
_diffrn_reflns_theta_min         3.366
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.649
_exptl_absorpt_correction_T_max  0.662
_exptl_absorpt_correction_T_min  0.505
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark green'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.513
_exptl_crystal_description       rhombohedral
_exptl_crystal_F_000             2736
_exptl_crystal_size_max          0.43
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.747
_refine_diff_density_min         -0.497
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 2785 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.010(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     726
_refine_ls_number_reflns         12555
_refine_ls_number_restraints     92
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0974
_refine_ls_R_factor_gt           0.0522
_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^)+(0.0410P)^2^+12.9435P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1064
_refine_ls_wR_factor_ref         0.1323
_reflns_Friedel_coverage         0.728
_reflns_Friedel_fraction_full    0.894
_reflns_Friedel_fraction_max     0.703
_reflns_number_gt                8062
_reflns_number_total             12555
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt02033a2.cif
_cod_data_source_block           yy20188113
_cod_database_code               7708460
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C1 H1 O1 N1 S1 Cu1'
_shelx_estimated_absorpt_t_max   0.683
_shelx_estimated_absorpt_t_min   0.537
_reflns_odcompleteness_completeness 99.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C50-C51A
 1.43 with sigma of 0.02
 C51A-S4A
 1.8 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(S3) \\sim Ueq, Uanis(S3A) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C39A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C13) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C22) \\sim Ueq, Uanis(C22A) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C23A)
\\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C24A) \\sim Ueq, Uanis(C25A) \\sim Ueq,
Uanis(C25) \\sim Ueq, Uanis(S2A) \\sim Ueq, Uanis(S2) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(S3) = Uanis(S3A)
Uanis(C39A) = Uanis(C39)
Uanis(C38) = Uanis(C38A)
Uanis(C26) = Uanis(C26A)
Uanis(C24) = Uanis(C24A)
Uanis(C25) = Uanis(C25A)
Uanis(S2) = Uanis(S2A)
Uanis(C23) = Uanis(C23A)
Uanis(C22) = Uanis(C22A)
Uanis(S4) = Uanis(S4A)
Uanis(C52) = Uanis(C52A)
Uanis(C51) = Uanis(C51A)
4. Others
 Sof(S2A)=Sof(C24A)=Sof(H24C)=Sof(H24D)=Sof(C25A)=Sof(H25C)=Sof(H25D)=1-FVAR(1)
 Sof(S2)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(C25)=Sof(H25A)=Sof(H25B)=FVAR(1)
 Sof(C23A)=Sof(H23A)=1-FVAR(2)
 Sof(C23)=Sof(H23)=FVAR(2)
 Sof(C22A)=Sof(H22A)=Sof(H22B)=1-FVAR(3)
 Sof(C22)=Sof(H22C)=Sof(H22D)=FVAR(3)
 Sof(S4A)=1-FVAR(4)
 Sof(S4)=FVAR(4)
 Sof(C52A)=Sof(H52D)=Sof(H52E)=Sof(H52F)=1-FVAR(5)
 Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=FVAR(5)
 Sof(H37C)=Sof(H37D)=Sof(S3A)=Sof(C38A)=Sof(H38C)=Sof(H38D)=1-FVAR(6)
 Sof(H37A)=Sof(H37B)=Sof(S3)=Sof(C38)=Sof(H38A)=Sof(H38B)=FVAR(6)
 Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=1-FVAR(7)
 Sof(C39A)=Sof(H39D)=Sof(H39E)=Sof(H39F)=FVAR(7)
 Sof(H50C)=Sof(H50D)=Sof(C51A)=Sof(H51C)=Sof(H51D)=1-FVAR(8)
 Sof(H50B)=Sof(H50A)=Sof(C51)=Sof(H51B)=Sof(H51A)=FVAR(8)
 Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=1-FVAR(9)
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(9)
 Fixed X: C26(0.270269) C26A(0.285509) C38(0.64935) C39(0.66843) C38A(0.65675)
 Fixed Y: C26(-0.09136) C26A(-0.02904) C38(1.076488) C39(1.15579) C38A(1.055901)
 Fixed Z: C26(0.477789) C26A(0.478069) C38(0.112341) C39(-0.025011)
 C38A(0.127851)
5.a Ternary CH refined with riding coordinates:
 C10(H10), C23(H23), C23A(H23A), C36(H36), C49(H49)
5.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C11(H11A,H11B), C12(H12A,H12B), C22A(H22A,H22B), C24(H24A,H24B),
 C25(H25A,H25B), C22(H22C,H22D), C24A(H24C,H24D), C25A(H25C,H25D), C35(H35A,
 H35B), C37(H37A,H37B), C37(H37C,H37D), C48(H48A,H48B), C50(H50B,H50A),
 C50(H50C,H50D), C38(H38A,H38B), C51(H51B,H51A), C38A(H38C,H38D), C51A(H51C,
 H51D)
5.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C17(H17), C18(H18), C19(H19), C20(H20),
 C30(H30), C31(H31), C32(H32), C33(H33), C43(H43), C44(H44), C45(H45), C46(H46)
5.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C13(H13A,H13B,H13C), C21(H21A,H21B,H21C), C26(H26A,H26B,
 H26C), C26A(H26D,H26E,H26F), C34(H34A,H34B,H34C), C47(H47A,H47B,H47C),
 C39(H39A,H39B,H39C), C52(H52A,H52B,H52C), C39A(H39D,H39E,H39F), C52A(H52D,H52E,
 H52F)
;
_shelx_res_checksum              13905
_shelx_hkl_checksum              29255
_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 1.460
_oxdiff_exptl_absorpt_empirical_full_min 0.836