A new family of heterometallic [Cu<sub>6</sub>M<sub>4</sub>] (M = Gd, Tb, Dy and Y) clusters derived from the combined use of selected pyridyl poly-alcohol ligands.
Anastassiades, Antonis; Alexandropoulos, Dimitris I.; Buch, Christian D.; Piligkos, Stergios; Tasiopoulos, Anastasios J.; Dalton transactions (Cambridge, England : 2003) 53 (2024) 16202–16211; doi:10.1039/d4dt02054e

data_7717057
_publ_section_title
;
 A new family of heterometallic [Cu<sub>6</sub>M<sub>4</sub>] (M = Gd, Tb,
 Dy and Y) clusters derived from the combined use of selected pyridyl
 poly-alcohol ligands.
;
_journal_issue                   39
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              16202
_journal_page_last               16211
_journal_paper_doi               10.1039/d4dt02054e
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C68 H80 Cu6 Dy4 N16 O44, 4(C2 H3 N)'
_chemical_formula_sum            'C76 H92 Cu6 Dy4 N20 O44'
_chemical_formula_weight         3020.93
_space_group_crystal_system      tetragonal
_space_group_IT_number           114
_space_group_name_Hall           'P -4 2n'
_space_group_name_H-M_alt        'P -4 21 c'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2kky8c
_audit_creation_date             2024-07-13
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-07-15 deposited with the CCDC.	2024-09-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   17.45300(10)
_cell_length_b                   17.45300(10)
_cell_length_c                   16.65680(10)
_cell_measurement_reflns_used    27408
_cell_measurement_temperature    149.94(10)
_cell_measurement_theta_max      78.0810
_cell_measurement_theta_min      3.5720
_cell_volume                     5073.78(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.94(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  17.00   0.50    0.50    --  -49.93  47.00 -29.00   78
  2  \w   -114.00 -43.00   0.50    0.50    --  -49.93 -47.00-178.00  142
  3  \w     43.00  68.00   0.50    0.50    --   49.93  47.00 -29.00   50
  4  \w    -19.00  30.00   0.50    0.50    --   49.93 -47.00-178.00   98
  5  \w   -176.00 -99.00   0.50    1.50    -- -106.00 -47.00-178.00  154
  6  \w    116.00 141.00   0.50    1.50    --  111.50  47.00 -29.00   50
  7  \w   -116.00 -75.00   0.50    0.50    --  -49.93-126.00-120.00   82
  8  \w   -119.00 -73.00   0.50    0.50    --  -49.93-126.00   0.00   92
  9  \w     87.00 112.00   0.50    0.50    --   49.93  47.00 -29.00   50
 10  \w    -22.00  25.00   0.50    0.50    --   49.93 -19.00  30.00   94
 11  \w    -64.00 -34.00   0.50    1.50    -- -106.00  57.00-180.00   60
 12  \w    -63.00 -36.00   0.50    1.50    -- -106.00  57.00 -30.00   54
 13  \w    -63.00 -37.00   0.50    1.50    -- -106.00  57.00-120.00   52
 14  \w    -65.00 -40.00   0.50    1.50    -- -106.00  57.00   0.00   50
 15  \w    -62.00 -36.00   0.50    1.50    -- -106.00  57.00  90.00   52
 16  \w    -65.00 -40.00   0.50    1.50    -- -106.00  57.00 -60.00   50
 17  \w    -64.00 -39.00   0.50    1.50    -- -106.00  57.00  60.00   50
 18  \w   -146.00-103.00   0.50    1.50    -- -106.00   0.00-120.00   86
 19  \w    -65.00 -40.00   0.50    1.50    -- -106.00  57.00 120.00   50
 20  \w    -65.00 -40.00   0.50    1.50    -- -106.00  57.00 150.00   50
 21  \w     46.00 101.00   0.50    1.50    --  111.50 -77.00  30.00  110
 22  \w     59.00 102.00   0.50    1.50    --  111.50-126.00  30.00   86
 23  \w     41.00  95.00   0.50    1.50    --  111.50 -77.00 150.00  108
 24  \w     50.00  88.00   0.50    1.50    --  111.50 -77.00-180.00   76
 25  \w    115.00 141.00   0.50    1.50    --  111.50  57.00  60.00   52
 26  \w     43.00  98.00   0.50    1.50    --  111.50 -77.00 -30.00  110
 27  \w     64.00  96.00   0.50    1.50    --  111.50   0.00 150.00   64
 28  \w    147.00 178.00   0.50    1.50    --  111.50  57.00  60.00   62
 29  \w     54.00  87.00   0.50    1.50    --  111.50 -77.00-150.00   66
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0125061000
_diffrn_orient_matrix_UB_12      0.0709785000
_diffrn_orient_matrix_UB_13      0.0534677000
_diffrn_orient_matrix_UB_21      0.0495614000
_diffrn_orient_matrix_UB_22      -0.0481568000
_diffrn_orient_matrix_UB_23      0.0575302000
_diffrn_orient_matrix_UB_31      0.0719756000
_diffrn_orient_matrix_UB_32      0.0208718000
_diffrn_orient_matrix_UB_33      -0.0488093000
_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  0.0316
_diffrn_reflns_av_unetI/netI     0.0160
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            36897
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.079
_diffrn_reflns_theta_max         67.079
_diffrn_reflns_theta_min         3.581
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    17.634
_exptl_absorpt_correction_T_max  0.650
_exptl_absorpt_correction_T_min  0.363
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark blue'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.977
_exptl_crystal_description       block
_exptl_crystal_F_000             2956
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.579
_refine_diff_density_min         -0.622
_refine_diff_density_rms         0.070
_refine_ls_abs_structure_details
;
 Flack x determined using 1915 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.0006(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     369
_refine_ls_number_reflns         4526
_refine_ls_number_restraints     82
_refine_ls_restrained_S_all      1.100
_refine_ls_R_factor_all          0.0243
_refine_ls_R_factor_gt           0.0239
_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^)+(0.0405P)^2^+4.8529P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0656
_refine_ls_wR_factor_ref         0.0658
_reflns_Friedel_coverage         0.805
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                4465
_reflns_number_total             4526
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt02054e2.cif
_cod_data_source_block           at_dy4cu6_new
_cod_depositor_comments
'Adding full bibliography for 7717055--7717058.cif.'
_cod_original_cell_volume        5073.78(7)
_cod_database_code               7717057
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C72 H86 Cu6 Dy4 N18 O44'
_chemical_oxdiff_usercomment     OVEN@120for2hrs_RTdatacol
_shelx_estimated_absorpt_t_max   0.247
_shelx_estimated_absorpt_t_min   0.143
_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, All O(H) groups
2. Restrained distances
 N5-C18
 1.14 with sigma of 0.02
 C18-N5
 1.137 with sigma of 0.01
 C18-C19
 1.456 with sigma of 0.01
 C19-N5
 2.593 with sigma of 0.02
 N6-C20
 1.14 with sigma of 0.02
 C20-N6
 1.137 with sigma of 0.01
 C20-C21
 1.456 with sigma of 0.01
 C21-N6
 2.593 with sigma of 0.02
 N5-C19
 2.59 with sigma of 0.04
 N6-C21
 2.59 with sigma of 0.04
3. Rigid bond restraints
 O8, N3, O7, O6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O7, N3, O6, O8
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
N5 \\sim C18 \\sim C19: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
N6 \\sim C20 \\sim C21: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
O8 \\sim O6 \\sim O7 \\sim N3: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
Uanis(O8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 N5, C18, C19
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N6, C20, C21
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: N5(0.75) C18(0.75) C19(0.75) H19a(0.75) H19b(0.75) H19c(0.75)
 N6(0.25) C20(0.25) C21(0.25) H21a(0.25) H21b(0.25) H21c(0.25)
7.a Ternary CH refined with riding coordinates:
 C12(H12)
7.b Secondary CH2 refined with riding coordinates:
 C1(H1a,H1b), C3(H3a,H3b), C2(H2a,H2b), C10(H10a,H10b), C11(H11a,H11b)
7.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C17(H17), C7(H7), C8(H8), C9(H9), C16(H16), C14(H14), C15(H15)
7.d Idealised Me refined as rotating group:
 C19(H19a,H19b,H19c), C21(H21a,H21b,H21c)
7.e Idealised tetrahedral OH refined as rotating group:
 O5(H5)
;
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.202
_oxdiff_exptl_absorpt_empirical_full_min 0.812