Rare earth benzene tetraanion-bridged amidinate complexes.
Jin, Peng-Bo; Luo, Qian-Cheng; Gransbury, Gemma K.; Winpenny, Richard E. P.; Mills, David P.; Zheng, Yan-Zhen; Chemical science 16 (2025) 1907–1924; doi:10.1039/d4sc05982d

data_1573557
_publ_section_title
;
 Rare earth benzene tetraanion-bridged amidinate complexes.
;
_journal_issue                   4
_journal_name_full               'Chemical science'
_journal_page_first              1907
_journal_page_last               1924
_journal_paper_doi               10.1039/d4sc05982d
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C64 H92 Dy2 N4, 0.5[], 1.25[]'
_chemical_formula_sum            'C67 H99 Dy2 N4'
_chemical_formula_weight         1285.50
_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   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-10-30
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-11-13 deposited with the CCDC.	2024-12-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.063(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.83820(10)
_cell_length_b                   38.9439(5)
_cell_length_c                   15.0078(3)
_cell_measurement_reflns_used    24268
_cell_measurement_temperature    100.0(7)
_cell_measurement_theta_max      79.8040
_cell_measurement_theta_min      3.2740
_cell_volume                     6116.87(17)
_computing_cell_refinement       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(7)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -81.00  -5.00   0.50    0.56    --  -47.87 104.00 133.00  152
  2  \w     25.00  71.00   0.50    0.56    --   47.87-104.00  32.00   92
  3  \w    -74.00 -49.00   0.50    2.23    --  -91.75 104.00 133.00   50
  4  \w   -135.00 -92.00   0.50    2.23    --  -91.75-104.00  32.00   86
  5  \w    107.00 159.00   0.50    2.23    --  113.25 104.00 133.00  104
  6  \w     78.00 104.00   0.50    2.23    --  113.25-104.00  32.00   52
  7  \w   -117.00 -73.00   0.50    0.56    --  -47.87-125.00-120.00   88
  8  \w    -16.00  10.00   0.50    0.56    --  -47.87  19.00-120.00   52
  9  \w    -17.00   9.00   0.50    0.56    --  -47.87  19.00 -30.00   52
 10  \w     29.00 117.00   0.50    0.56    --   47.87  77.00 120.00  176
 11  \w    -49.00 -22.00   0.50    2.23    --  -91.75  45.00 -30.00   54
 12  \w    -51.00 -25.00   0.50    2.23    --  -91.75  45.00   0.00   52
 13  \w     44.00  71.00   0.50    2.23    --  113.25 -61.00  30.00   54
 14  \w    121.00 176.00   0.50    2.23    --  113.25  45.00 120.00  110
 15  \w     45.00  71.00   0.50    2.23    --  113.25 -61.00-180.00   52
 16  \w     42.00 106.00   0.50    2.23    --  113.25 -77.00  30.00  128
 17  \w     49.00 106.00   0.50    2.23    --  113.25 -77.00-180.00  114
 18  \w     44.00 106.00   0.50    2.23    --  113.25 -94.00 150.00  124
 19  \w     45.00  97.00   0.50    2.23    --  113.25 -77.00-120.00  104
 20  \w    100.00 174.00   0.50    2.23    --  113.25  15.00-120.00  148
 21  \w     42.00  67.00   0.50    2.23    --  113.25 -61.00 150.00   50
 22  \w    136.00 166.00   0.50    2.23    --  113.25  15.00  60.00   60
 23  \w    106.00 132.00   0.50    2.23    --  113.25  15.00  60.00   52
 24  \w     46.00  71.00   0.50    2.23    --  113.25 -61.00 -90.00   50
 25  \w     43.00  68.00   0.50    2.23    --  113.25 -77.00 150.00   50
 26  \w     81.00 106.00   0.50    2.23    --  113.25 -77.00 150.00   50
 27  \w     55.00  80.00   0.50    2.23    --  113.25 -94.00  90.00   50
 28  \w    128.00 174.00   0.50    2.23    --  113.25 125.00-150.00   92
 29  \w     42.00  81.00   0.50    2.23    --  113.25-125.00   0.00   78
 30  \w     76.00 111.00   0.50    2.23    --  113.25-125.00 150.00   70
 31  \w     77.00 105.00   0.50    2.23    --  113.25 -94.00  30.00   56
 32  \w     46.00  71.00   0.50    2.23    --  113.25-125.00 -60.00   50
 33  \w     82.00 109.00   0.50    2.23    --  113.25-125.00 -60.00   54
 34  \w     49.00 100.00   0.50    2.23    --  113.25-125.00  30.00  102
 35  \w     42.00  67.00   0.50    2.23    --  113.25 -61.00-150.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0336920000
_diffrn_orient_matrix_UB_12      -0.0046094000
_diffrn_orient_matrix_UB_13      0.1055146000
_diffrn_orient_matrix_UB_21      0.0348888000
_diffrn_orient_matrix_UB_22      -0.0378270000
_diffrn_orient_matrix_UB_23      -0.0112528000
_diffrn_orient_matrix_UB_31      0.1389903000
_diffrn_orient_matrix_UB_32      0.0106063000
_diffrn_orient_matrix_UB_33      0.0065021000
_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  0.0875
_diffrn_reflns_av_unetI/netI     0.0512
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       46
_diffrn_reflns_limit_k_min       -46
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            47345
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        66.596
_diffrn_reflns_theta_max         66.596
_diffrn_reflns_theta_min         3.254
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    13.221
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47207
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.122a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            purple
_exptl_crystal_colour_primary    purple
_exptl_crystal_density_diffrn    1.396
_exptl_crystal_description       block
_exptl_crystal_F_000             2644
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.23
_refine_diff_density_max         4.355
_refine_diff_density_min         -3.078
_refine_diff_density_rms         0.254
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.134
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     681
_refine_ls_number_reflns         10761
_refine_ls_number_restraints     1627
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0855
_refine_ls_R_factor_gt           0.0822
_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^)+(0.1085P)^2^+109.8022P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2224
_refine_ls_wR_factor_ref         0.2241
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9850
_reflns_number_total             10761
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05982d2.cif
_cod_data_source_block           crepw025_auto
_cod_depositor_comments
'Adding full bibliography for 1573553--1573561.cif.'
_cod_database_code               1573557
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.151
_shelx_estimated_absorpt_t_min   0.072
_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
2. Restrained distances
 C65-C66
 1.53 with sigma of 0.02
3. Rigid bond restraints
 C30
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C60 \\sim C26 \\sim C56 \\sim C25 \\sim C22 \\sim C39 \\sim C24 \\sim C21 \\sim
C38 \\sim C41 \\sim C13 \\sim C52 \\sim C33 \\sim C36 \\sim C34 \\sim C40 \\sim
C55 \\sim C31 \\sim C64 \\sim C9 \\sim C23 \\sim C57 \\sim C37 \\sim C14 \\sim
C51 \\sim C32 \\sim C8 \\sim C15 \\sim C2 \\sim C54 \\sim C10 \\sim C46 \\sim
C4 \\sim C11 \\sim C35 \\sim C7 \\sim C3 \\sim C30 \\sim C27 \\sim C5 \\sim C12
\\sim C43 \\sim C16 \\sim C6 \\sim C61 \\sim C20 \\sim C19 \\sim C49 \\sim C42
\\sim C45 \\sim C53 \\sim C17 \\sim C48 \\sim C29 \\sim C1 \\sim C28 \\sim C59
\\sim C18 \\sim C44 \\sim C62 \\sim C58 \\sim C47 \\sim C63 \\sim C50: within
3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3.8A
N4 \\sim N3 \\sim N2 \\sim N1: within 3.8A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 3.8A
Uanis(C22) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C55) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C35) \\sim Ueq, Uanis(C50) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C34) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C22) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C30) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C6) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(N2) \\sim Ueq, Uanis(N3) \\sim Ueq, Uanis(N4) \\sim Ueq, Uanis(N1) \\sim
Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
5.a Ternary CH refined with riding coordinates:
 C57(H57), C2(H2), C10(H10), C27(H27), C19(H19), C49(H49), C42(H42), C45(H45)
5.b Secondary CH2 refined with riding coordinates:
 C66(H66A,H66B), C67(H67A,H67B)
5.c Aromatic/amide H refined with riding coordinates:
 C22(H22), C24(H24), C41(H41), C52(H52), C33(H33), C34(H34), C35(H35),
 C30(H30), C31(H31), C32(H32), C36(H36), C23(H23), C37(H37), C54(H54), C7(H7),
 C5(H5), C6(H6), C53(H53)
5.d Idealised Me refined as rotating group:
 C64(H64A,H64B,H64C), C15(H15A,H15B,H15C), C46(H46A,H46B,H46C), C11(H11A,H11B,
 H11C), C3(H3A,H3B,H3C), C12(H12A,H12B,H12C), C43(H43A,H43B,H43C), C16(H16A,
 H16B,H16C), C20(H20A,H20B,H20C), C17(H17A,H17B,H17C), C48(H48A,H48B,H48C),
 C29(H29A,H29B,H29C), C1(H1A,H1B,H1C), C28(H28A,H28B,H28C), C59(H59A,H59B,H59C),
  C18(H18A,H18B,H18C), C44(H44A,H44B,H44C), C62(H62A,H62B,H62C), C58(H58A,H58B,
 H58C), C47(H47A,H47B,H47C), C63(H63A,H63B,H63C), C50(H50A,H50B,H50C), C65(H65A,
 H65B,H65C)
;
_shelx_res_checksum              50994
_platon_squeeze_void_probe_radius 1.20
_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 2.113
_oxdiff_exptl_absorpt_empirical_full_min 0.448