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_7712280
_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
'C48 H78 Cl2 Cu5 Dy2 N4 O22, H2 O, 4(Cl O4), 2(C6 H16 N), 2(Cl)'
_chemical_formula_sum            'C60 H152 Cl8 Cu5 Dy2 N6 O59'
_chemical_formula_weight         2828.17
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-07-17
_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                87.63(9)
_cell_angle_beta                 68.21(7)
_cell_angle_gamma                69.24(7)
_cell_formula_units_Z            1
_cell_length_a                   14.468(15)
_cell_length_b                   15.061(13)
_cell_length_c                   15.723(14)
_cell_measurement_reflns_used    9878
_cell_measurement_temperature    299.24
_cell_measurement_theta_max      26.275
_cell_measurement_theta_min      2.813
_cell_volume                     2959(5)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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 2018/3 (Sheldrick, 2008)'
_diffrn_ambient_temperature      299.24
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0649
_diffrn_reflns_av_unetI/netI     0.0778
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            34495
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.420
_diffrn_reflns_theta_min         2.858
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    2.398
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.4021
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1424 before and 0.0702 after correction.
The Ratio of minimum to maximum transmission is 0.5394.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.587
_exptl_crystal_description       block
_exptl_crystal_F_000             1439
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.863
_refine_diff_density_min         -0.935
_refine_diff_density_rms         0.098
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     694
_refine_ls_number_reflns         11918
_refine_ls_number_restraints     975
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0803
_refine_ls_R_factor_gt           0.0467
_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^)+(0.0434P)^2^+1.8871P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1059
_refine_ls_wR_factor_ref         0.1178
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8261
_reflns_number_total             11918
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03932j2.cif
_cod_data_source_block           mo_Complex2
_cod_database_code               7712280
_smtbx_masks_special_details
;
A solvent mask was calculated and 207 electrons were 
found in a volume of 739\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
20[H2O] per Unit Cell 
which account for 200 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.778
_shelx_estimated_absorpt_t_min   0.250
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H9A,H9B} of O9, H8 of O8, {H11A,H11B} of O11, H7 of O7,
  {H10A,H10B} of O10, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, {H25G,H25H} of O25, H6 of O6
2. Restrained distances
 C28-N3
 4.4 with sigma of 0.02
 N3-C27
 2.4 with sigma of 0.02
 C27-Cu1
 0.01 with sigma of 4.8
 C27-N3
 2.4 with sigma of 0.008
 O6-H6
 0.85 with sigma of 0.01
 H7-Dy1
 2.6 with sigma of 0.02
 C27-N1
 4.45 with sigma of 0.02
 C27-C4
 3.7 with sigma of 0.02
 C27-C26 = C25-C24 = C23-C22
 1.56 with sigma of 0.02
 C22A-N3
 1.5 with sigma of 0.02
 N3-C23A
 2.5 with sigma of 0.02
 C22-N3
 1.5 with sigma of 0.02
 N3-C24
 1.5 with sigma of 0.02
 N3-C24A
 1.5 with sigma of 0.02
 Cu2-H6
 2.701334 with sigma of 0.02
 C19-H6
 1.878556 with sigma of 0.02
 Cl2-O12 \\sim Cl2-O13 \\sim Cl2-O15 \\sim Cl2-O14
 with sigma of 0.02
 Cl3-O18 \\sim Cl3-O16 \\sim Cl3-O19 \\sim Cl3-O17
 with sigma of 0.008
 Cl2-O13 \\sim Cl2-O12 \\sim Cl2-O14 \\sim Cl2-O15
 with sigma of 0.008
 Cl2-O13A \\sim Cl2-O12A \\sim Cl2-O15A \\sim Cl2-O14A
 with sigma of 0.008
 Cl3-O19A \\sim Cl3-O16A \\sim Cl3-O18A \\sim Cl3-O17A
 with sigma of 0.008
 C22-C26 \\sim C26-C24 \\sim C24-C22
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl2 \\sim O12 \\sim O14 \\sim O13 \\sim O15 \\sim O13A \\sim O15A \\sim O14A
\\sim O12A: within 2A with sigma of 0.008 and sigma for terminal atoms of 0.016
within 2A
Cl3 \\sim O19 \\sim O16 \\sim O17 \\sim O18 \\sim O18A \\sim O17A \\sim O16A
\\sim O19A: within 2A with sigma of 0.008 and sigma for terminal atoms of 0.016
within 2A
C24 \\sim N3 \\sim C26 \\sim C22 \\sim C25 \\sim C27 \\sim C23: within 2A with
sigma of 0.008 and sigma for terminal atoms of 0.016 within 2A
N3 \\sim C24 \\sim C26 \\sim C22 \\sim C26A \\sim C24A \\sim C22A \\sim C25
\\sim C27 \\sim C23 \\sim C27A \\sim C25A \\sim C23A: within 2A with sigma of
0.008 and sigma for terminal atoms of 0.016 within 2A
Uanis(N3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. 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
5. Same fragment restrains
{O12, O14, O13, O15} sigma for 1-2: 0.01, 1-3: 0.02
as in
{O13A, O15A, O14A, O12A}
{O12, O14, O13, O15} sigma for 1-2: 0.008, 1-3: 0.016
as in
{O18, O19, O16, O17}
{O12, O14, O13, O15} sigma for 1-2: 0.01, 1-3: 0.02
as in
{O18A, O17A, O16A, O19A}
{C22, C24, C26, C27, C25, C23} sigma for 1-2: 0.008, 1-3: 0.16
as in
{C22A, C24A, C26A, C27A, C25A, C23A}
6. Others
 Sof(O13A)=Sof(O15A)=Sof(O14A)=Sof(O12A)=1-FVAR(1)
 Sof(O12)=Sof(O14)=Sof(O13)=Sof(O15)=FVAR(1)
 Sof(O18A)=Sof(O17A)=Sof(O16A)=Sof(O19A)=1-FVAR(2)
 Sof(O18)=Sof(O19)=Sof(O16)=Sof(O17)=FVAR(2)
 Sof(H3B)=Sof(C22A)=Sof(H22C)=Sof(H22D)=Sof(C24A)=Sof(H24C)=Sof(H24D)=
 Sof(C26A)=Sof(H26C)=Sof(H26D)=Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=
 Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C23A)=Sof(H23D)=Sof(H23E)=
 Sof(H23F)=1-FVAR(3)
 Sof(H3A)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(C26)=
 Sof(H26A)=Sof(H26B)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C25)=Sof(H25A)=
 Sof(H25B)=Sof(H25C)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(3)
 Fixed Sof: O25(0.5) H25G(0.5) H25H(0.5)
7.a Free rotating group:
 O25(H25G,H25H)
7.b Ternary CH refined with riding coordinates:
 O7(H7), O8(H8), N3(H3A), N3(H3B)
7.c Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C7(H7A,H7B), C22(H22A,H22B), C24(H24A,H24B), C26(H26A,H26B),
 C22A(H22C,H22D), C24A(H24C,H24D), C26A(H26C,H26D)
7.d Aromatic/amide H refined with riding coordinates:
 C5(H5), C31(H31), C28(H28), C17(H17), C30(H30), C16(H16), C15(H15), C14(H14)
7.e X=CH2 refined with riding coordinates:
 O9(H9A,H9B), O10(H10A,H10B), O11(H11A,H11B)
7.f Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C21(H21A,H21B,H21C), C9(H9C,H9D,H9E), C8(H8A,H8B,H8C),
 C10(H10C,H10D,H10E), C20(H20A,H20B,H20C), C27(H27A,H27B,H27C), C25(H25A,H25B,
 H25C), C23(H23A,H23B,H23C), C27A(H27D,H27E,H27F), C25A(H25D,H25E,H25F),
 C23A(H23D,H23E,H23F)
;
_shelx_res_checksum              65633
_shelx_hkl_checksum              65536
_shelx_fab_checksum              72251
_olex2_submission_special_instructions 'No special instructions were received'