Synthesis and characterization of two self-assembled [Cu6Gd3] and [Cu5Dy2] complexes exhibiting magnetocaloric effect, slow relaxation of magnetization and anticancer activity
Bhanja, Avik; Roy Chaudhuri, Sangeeta; Tsanai, Angelos B.; Vyas, Shachi Pranjal; Ortu, Fabrizio; Smythe, Lucy; Murrie, Mark; Goswami, Ritobrata; Ray, Debashis; Dalton Transactions  (2023) –; doi:10.1039/D2DT03932J

data_7712279
_publ_section_title
;
 Synthesis and characterization of two self-assembled [Cu6Gd3] and
 [Cu5Dy2] complexes exhibiting magnetocaloric effect, slow relaxation of
 magnetization and anticancer activity
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT03932J
_journal_year                    2023
_chemical_formula_moiety         'C72 H100 Cl3 Cu6 Gd3 N6 O26, Cl O4, 4(H2O)'
_chemical_formula_sum            'C72 H108 Cl4 Cu6 Gd3 N6 O34'
_chemical_formula_weight         2596.48
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2020-07-14
_audit_creation_method
;
Olex2 1.3
(compiled 2020.06.28 svn.raecde09e for OlexSys, GUI svn.r6132)
;
_audit_update_record
;
2022-07-06 deposited with the CCDC.	2023-02-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.3670(16)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.5095(5)
_cell_length_b                   39.1997(8)
_cell_length_c                   26.0609(4)
_cell_measurement_reflns_used    20568
_cell_measurement_temperature    150
_cell_measurement_theta_max      27.9170
_cell_measurement_theta_min      1.6700
_cell_volume                     21838.1(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.995
_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      2.66 117.66   0.50    5.00    --   28.00  59.94 -20.34  230
  2  \w      2.66 117.66   0.50    5.00    --   28.00  59.94  69.66  230
  3  \w    -53.34  61.66   0.50    5.00    --  -28.00  59.94 159.66  230
  4  \w    -53.34  61.66   0.50    5.00    --  -28.00  59.94-110.34  230
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0100821000
_diffrn_orient_matrix_UB_12      -0.0095446000
_diffrn_orient_matrix_UB_13      -0.0225256000
_diffrn_orient_matrix_UB_21      -0.0240964000
_diffrn_orient_matrix_UB_22      0.0120689000
_diffrn_orient_matrix_UB_23      -0.0067113000
_diffrn_orient_matrix_UB_31      0.0204569000
_diffrn_orient_matrix_UB_32      0.0095174000
_diffrn_orient_matrix_UB_33      -0.0140674000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1116
_diffrn_reflns_av_unetI/netI     0.1087
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       48
_diffrn_reflns_limit_k_min       -48
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            199345
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         1.562
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.102
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39830
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.536
_exptl_crystal_description       block
_exptl_crystal_F_000             9984
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.899
_refine_diff_density_min         -1.265
_refine_diff_density_rms         0.200
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2267
_refine_ls_number_reflns         44429
_refine_ls_number_restraints     3239
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.1306
_refine_ls_R_factor_gt           0.0793
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0728P)^2^+101.5704P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1900
_refine_ls_wR_factor_ref         0.2254
_reflns_Friedel_coverage         0.000
_reflns_number_gt                24988
_reflns_number_total             44429
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03932j2.cif
_cod_data_source_block           mo_Complex1
_cod_original_cell_volume        21838.1(7)
_cod_database_code               7712279
_smtbx_masks_special_details
;
A solvent mask was calculated and 600 electrons were
found in a volume of 6020\%A^3 in 4 voids per unit cell.
This is consistent with the presence of 
7.5[H2O] per Asymmetric Unit 
which account for 603 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C72H95.5BCl3Cu6F4Gd3O31
_shelx_estimated_absorpt_t_max   0.970
_shelx_estimated_absorpt_t_min   0.576
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, H24 of O24, H23 of O23, H25 of O25, All C(H,H) groups, All
  O(H,H,H,H,H,H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, H35 of O35, H38 of O38, H51 of O51, H52 of O52, H29A
  of O29, H9 of O9, H3 of O3, H22 of O22, H6 of O6, H26 of O26
2. Restrained distances
 O21-H21
 0.82 with sigma of 0.01
 O20-H20
 0.82 with sigma of 0.02
 H19-O19
 0.82 with sigma of 0.02
 O50-H50 = O49-H49 = O48-H48 = O46-H46 = O47-H47 = O45-H45
 0.82 with sigma of 0.02
 O3-H3
 0.85 with sigma of 0.01
 O6-H6
 0.85 with sigma of 0.01
 O9-H9
 0.85 with sigma of 0.01
 O35-H35
 0.85 with sigma of 0.01
 O29-H29A
 0.85 with sigma of 0.01
 O38-H38
 0.85 with sigma of 0.01
 O23-H23 = O24-H24 = O25-H25
 0.82 with sigma of 0.02
 H21-Gd1
 2.04 with sigma of 0.02
 Cu3-H9
 2.650344 with sigma of 0.02
 Cu7-H29A
 2.637153 with sigma of 0.02
 Cu2-H6
 2.643751 with sigma of 0.02
 Cu10-H38
 2.635231 with sigma of 0.02
 Cu9-H35
 2.643788 with sigma of 0.02
 C34-H9
 1.881391 with sigma of 0.02
 C22-H6
 1.885892 with sigma of 0.02
 C82-H29A
 1.884563 with sigma of 0.02
 C10-H3
 1.888567 with sigma of 0.02
 C118-H38
 1.875701 with sigma of 0.02
 Cu1-H3
 2.6428 with sigma of 0.02
 C106-H35
 1.901661 with sigma of 0.02
3. Restrained planarity
 C74, C75, C76, C77, C78, C79
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Cl7 \\sim O53 \\sim O54 \\sim O55 \\sim O56 \\sim Cl8 \\sim O57 \\sim O58 \\sim
O59 \\sim O60: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
O27 \\sim N7 \\sim C73 \\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim
C79 \\sim C80 \\sim C81 \\sim C82 \\sim C83 \\sim C84: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
O10 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim
C44: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
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.a Ternary CH refined with riding coordinates:
 O23(H23), O24(H24), O25(H25)
6.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C22(H22A,H22B), C34(H34A,H34B), C46(H46A,H46B), C58(H58A,
 H58B), C70(H70A,H70B), C94(H94A,H94B), C106(H10C,H10D), C118(H11D,H11E),
 C130(H13D,H13E), C143(H14A,H14B)
6.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6A), C7(H7), C8(H8), C17(H17), C18(H18), C19(H19A), C29(H29),
 C30(H30), C31(H31), C32(H32), C41(H41), C42(H42), C43(H43), C44(H44), C53(H53),
  C54(H54), C55(H55), C56(H56), C65(H65), C66(H66), C67(H67), C68(H68),
 C77(H77), C78(H78), C79(H79), C80(H80), C89(H89), C90(H90), C91(H91), C92(H92),
  C101(H101), C102(H102), C103(H103), C104(H104), C113(H113), C114(H114),
 C115(H115), C116(H116), C125(H125), C126(H126), C127(H127), C128(H128),
 C137(H137), C138(H138), C139(H139), C141(H141)
6.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,
 H13C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C35(H35A,
 H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C47(H47A,H47B,H47C),
 C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C59(H59A,H59B,H59C), C60(H60A,H60B,
 H60C), C61(H61A,H61B,H61C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C73(H73A,
 H73B,H73C), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C85(H85A,H85B,H85C),
 C95(H95A,H95B,H95C), C96(H96A,H96B,H96C), C97(H97A,H97B,H97C), C107(H10E,H10F,
 H10G), C108(H10H,H10I,H10J), C109(H10K,H10L,H10M), C119(H11F,H11G,H11H),
 C120(H12D,H12E,H12F), C121(H12G,H12H,H12I), C131(H13F,H13G,H13H), C132(H13I,
 H13J,H13K), C133(H13L,H13M,H13N), C144(H14C,H14D,H14E), C145(H14F,H14G,H14H)
6.e Idealised tetrahedral OH refined as rotating group:
 O22(H22), O26(H26), O51(H51), O52(H52)
;
_shelx_res_checksum              64627
_shelx_hkl_checksum              294
_shelx_fab_checksum              97669
_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 1.726
_oxdiff_exptl_absorpt_empirical_full_min 0.635