Tetranuclear Ru2Cu2 and Ru2Ni2 complexes with nanomolar anticancer activity
Alguacil, Andrés; Scalambra, Franco; Lorenzo Luiz, Pablo; Puerta, Adrián; González-Bakker , Aday; Mendoza, Zenaida; Padrón, José M.; Romerosa-Nievas, Antonio Manuel; Dalton Transactions  (2023) –; doi:10.1039/D3DT01284K

data_7713279
_publ_section_title
;
 Tetranuclear Ru2Cu2 and Ru2Ni2 complexes with nanomolar anticancer
 activity
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT01284K
_journal_year                    2023
_chemical_formula_moiety
'C97 H105 Cl3 Cu2 N6 O P6 Ru2, 2(C F3 O3 S), 4.5(C H4 O), H2 O'
_chemical_formula_sum            'C103.5 H125 Cl3 Cu2 F6 N6 O12.5 P6 Ru2 S2'
_chemical_formula_weight         2452.60
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-05-22
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-06-09 deposited with the CCDC.	2023-06-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.760(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.6659(11)
_cell_length_b                   14.3702(6)
_cell_length_c                   32.8411(15)
_cell_measurement_reflns_used    9973
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      31.450
_cell_measurement_theta_min      2.255
_cell_volume                     10673.8(8)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.00
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX2 microsource'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0538
_diffrn_reflns_av_unetI/netI     0.0420
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            139044
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.125
_diffrn_reflns_theta_min         2.054
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.948
_exptl_absorpt_correction_T_max  0.9252
_exptl_absorpt_correction_T_min  0.8630
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0880 before and 0.0736 after correction.
The Ratio of minimum to maximum transmission is 0.9328.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'light green'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.526
_exptl_crystal_description       plate
_exptl_crystal_F_000             5044
_exptl_crystal_size_max          0.117
_exptl_crystal_size_mid          0.105
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.937
_refine_diff_density_min         -0.940
_refine_diff_density_rms         0.107
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.52(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1135
_refine_ls_number_reflns         28554
_refine_ls_number_restraints     1260
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0712
_refine_ls_R_factor_gt           0.0577
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0414P)^2^+65.0471P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1237
_refine_ls_wR_factor_ref         0.1320
_reflns_Friedel_coverage         0.989
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                24193
_reflns_number_total             28554
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01284k2.cif
_cod_data_source_block           mo_aaa799_b_0m
_cod_original_formula_sum        'C103.50 H125 Cl3 Cu2 F6 N6 O12.50 P6 Ru2 S2'
_cod_database_code               7713279
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.972
_shelx_estimated_absorpt_t_min   0.897
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.48(3)
 0.52(3)
2. 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) groups, All O(H,H) groups
3. Restrained distances
 C5M-O5M
 1.38 with sigma of 0.01
 O6M-C6M
 1.42 with sigma of 0.01
 H5M-O6TB
 2.1 with sigma of 0.01
 C4M-O4M
 1.38 with sigma of 0.01
 H4M-O2MA
 2 with sigma of 0.01
 C6M-O6M
 1.43 with sigma of 0.02
 H6M-O6TA
 2.1 with sigma of 0.005
 H6M-O4T
 3.1 with sigma of 0.01
 H1M-O2T
 1.78 with sigma of 0.01
 H1M-H1WA
 2.5 with sigma of 0.05
 H1WA-O1M
 2.1 with sigma of 0.01
 O2MA-C2MA
 1.38 with sigma of 0.01
 H2ME-O3MA
 2.1 with sigma of 0.01
 F1T-S1T
 2.61 with sigma of 0.02
 F2T-S1T
 2.61 with sigma of 0.02
 F3T-S1T
 2.61 with sigma of 0.02
 C1T-S1T
 1.82 with sigma of 0.02
 S1T-O2T = S1T-O1T = S1T-O3T
 1.45 with sigma of 0.02
 O3T-C1T
 2.57 with sigma of 0.02
 O2MB-C2MB
 1.38 with sigma of 0.01
 F2T-F1T
 2.16 with sigma of 0.01
 F1T-F3T
 2.16 with sigma of 0.01
 F3T-F2T
 2.16 with sigma of 0.01
 F2T-C1T
 1.32 with sigma of 0.01
 F3T-C1T
 1.32 with sigma of 0.01
 F1T-C1T
 1.32 with sigma of 0.01
 C3MB-O3MB
 1.38 with sigma of 0.01
 C3MA-O3MA
 1.38 with sigma of 0.01
 N3-C5 = N3-C4 = N3-C3
 1.48 with sigma of 0.01
 O2T-C1T
 2.57 with sigma of 0.01
 O1T-C1T
 2.57 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
O2MA \\sim C2MA \\sim O2MB: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C3MA \\sim O3MB \\sim O3MA: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(O1W) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.01
Uanis(O5M) = Uanis(C5M)
Uanis(O6TA) = Uanis(O6TB) = Uanis(O5TA) = Uanis(O5TB) = Uanis(O4T)
Uanis(C1M) = Uanis(O1M)
Uanis(O4M) = Uanis(C4M)
Uanis(C2MA) = Uanis(O2MA)
Uanis(O3T) = Uanis(O1T) = Uanis(O2T)
Uanis(F2T) = Uanis(F1T) = Uanis(F3T)
Uanis(C2MB) = Uanis(O2MB)
Uanis(F6TB) = Uanis(F4TB) = Uanis(F5TB)
Uanis(F4TA) = Uanis(F5TA) = Uanis(F6TA)
Uanis(C92) = Uanis(C93) = Uanis(C94) = Uanis(C95) = Uanis(C96)
Uanis(C3MB) = Uanis(O3MB)
Uanis(C3MA) = Uanis(O3MA)
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 1*[Sof(C4M)+Sof(H4MA)+Sof(H4MB)+Sof(H4MC)+Sof(O4M)+Sof(H4M)]+1*[Sof(O5M)+
 Sof(H5M)+Sof(C5M)+Sof(H5MA)+Sof(H5MB)+Sof(H5MC)]+1*[Sof(O6M)+Sof(H6M)+Sof(C6M)+
 Sof(H6MA)+Sof(H6MB)+Sof(H6MC)]=1.5 with esd of 0.0001
 Sof(F4TB)=Sof(F6TB)=Sof(F5TB)=Sof(C2TB)=Sof(O6TB)=Sof(O5TB)=1-FVAR(1)
 Sof(O5TA)=Sof(O6TA)=Sof(C2TA)=Sof(F5TA)=Sof(F6TA)=Sof(F4TA)=FVAR(1)
 Sof(O2MB)=Sof(H2MB)=Sof(O3MB)=Sof(H3ME)=Sof(C3MB)=Sof(H3MF)=Sof(H3MG)=
 Sof(H3MH)=Sof(C2MB)=Sof(H2MA)=Sof(H2MC)=Sof(H2MD)=1-FVAR(2)
 Sof(O2MA)=Sof(H2ME)=Sof(C2MA)=Sof(H2MF)=Sof(H2MG)=Sof(H2MH)=Sof(C3MA)=
 Sof(H3MA)=Sof(H3MB)=Sof(H3MC)=Sof(O3MA)=Sof(H3MD)=FVAR(2)
 Sof(C4M)=Sof(H4MA)=Sof(H4MB)=Sof(H4MC)=Sof(O4M)=Sof(H4M)=FVAR(3)
 Sof(O5M)=Sof(H5M)=Sof(C5M)=Sof(H5MA)=Sof(H5MB)=Sof(H5MC)=FVAR(4)
 Sof(O6M)=Sof(H6M)=Sof(C6M)=Sof(H6MA)=Sof(H6MB)=Sof(H6MC)=FVAR(5)
7.a Free rotating group:
 O1W(H1WA,H1WB)
7.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C50(H50A,H50B), C53(H53A,H53B), C52(H52A,H52B), C49(H49A,H49B),
 C51(H51A,H51B), C3(H3A,H3B), C2(H2A,H2B), C4(H4A,H4B), C5(H5A,H5B)
7.c Aromatic/amide H refined with riding coordinates:
 C41(H41), C42(H42), C43(H43), C39(H39), C40(H40), C19(H19), C15(H15),
 C16(H16), C17(H17), C18(H18), C72(H72), C71(H71), C70(H70), C69(H69), C73(H73),
  C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C47(H47), C48(H48),
 C44(H44), C45(H45), C46(H46), C67(H67), C66(H66), C65(H65), C64(H64), C63(H63),
  C60(H60), C61(H61), C57(H57), C58(H58), C59(H59), C85(H85), C84(H84),
 C83(H83), C82(H82), C81(H81), C13(H13), C12(H12), C11(H11), C10(H10), C9(H9),
 C37(H37), C36(H36), C35(H35), C34(H34), C33(H33), C75(H75), C76(H76), C77(H77),
  C78(H78), C79(H79), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31),
 C88(H88), C89(H89), C90(H90), C91(H91), C87(H87), C94(H94), C95(H95), C96(H96),
  C92(H92), C93(H93)
7.d Fitted pentagon refined as free rotating group:
 C47(C48,C44,C45,C46), C94(C95,C96,C92,C93)
7.e Fitted hexagon refined as free rotating group:
 C41(C42,C43,C38,C39,C40), C19(C14,C15,C16,C17,C18), C72(C71,C70,C69,C68,C73),
 C21(C22,C23,C24,C25,C20), C67(C66,C65,C64,C63,C62), C60(C61,C56,C57,C58,C59),
 C85(C84,C83,C82,C81,C80), C8(C13,C12,C11,C10,C9), C32(C37,C36,C35,C34,C33),
 C74(C75,C76,C77,C78,C79), C26(C27,C28,C29,C30,C31), C88(C89,C90,C91,C86,C87)
7.f Idealised Me refined as rotating group:
 C55(H55A,H55B,H55C), C54(H54A,H54B,H54C), C6(H6A,H6B,H6C), C97(H97A,H97B,
 H97C), C7(H7A,H7B,H7C), C1M(H1MA,H1MB,H1MC), C2MA(H2MF,H2MG,H2MH), C6M(H6MA,
 H6MB,H6MC), C3MA(H3MA,H3MB,H3MC), C3MB(H3MF,H3MG,H3MH), C2MB(H2MA,H2MC,H2MD),
 C5M(H5MA,H5MB,H5MC), C4M(H4MA,H4MB,H4MC)
7.g Idealised tetrahedral OH refined as rotating group:
 O2MB(H2MB), O2MA(H2ME), O1M(H1M), O6M(H6M), O3MA(H3MD), O3MB(H3ME), O5M(H5M),
 O4M(H4M)
;
_shelx_res_checksum              3048
_shelx_hkl_checksum              19909
_olex2_submission_special_instructions 'No special instructions were received'