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_1573559
_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         'C65 H96 N4 Tb2, 2(C5 H12)'
_chemical_formula_sum            'C75 H120 N4 Tb2'
_chemical_formula_weight         1395.58
_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     dual
_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                97.598(2)
_cell_angle_beta                 103.094(2)
_cell_angle_gamma                112.008(2)
_cell_formula_units_Z            2
_cell_length_a                   14.4004(3)
_cell_length_b                   15.4059(3)
_cell_length_c                   18.0500(4)
_cell_measurement_reflns_used    32878
_cell_measurement_temperature    104(6)
_cell_measurement_theta_max      79.8170
_cell_measurement_theta_min      2.5750
_cell_volume                     3510.01(15)
_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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      104(6)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.975
_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    116.00 173.00   0.50    0.36    --  113.25  61.00   0.00  114
  2  \w    121.00 162.00   0.50    0.36    --  113.25  45.00-120.00   82
  3  \w    150.00 177.00   0.50    0.36    --  113.25  15.00-180.00   54
  4  \w    101.00 174.00   0.50    0.36    --  113.25  15.00  60.00  146
  5  \w    148.00 177.00   0.50    0.36    --  113.25  15.00  30.00   58
  6  \w    121.00 176.00   0.50    0.36    --  113.25  15.00 -30.00  110
  7  \w    101.00 134.00   0.50    0.36    --  113.25  15.00  30.00   66
  8  \w    115.00 165.00   0.50    0.36    --  113.25  30.00  90.00  100
  9  \w    116.00 175.00   0.50    0.36    --  113.25  30.00 120.00  118
 10  \w    100.00 177.00   0.50    0.36    --  113.25  15.00 -60.00  154
 11  \w    101.00 127.00   0.50    0.36    --  113.25  15.00-120.00   52
 12  \w    118.00 144.00   0.50    0.36    --  113.25  15.00-180.00   52
 13  \w    -18.00  27.00   0.50    0.09    --  -47.87  19.00  60.00   90
 14  \w    -23.00  24.00   0.50    0.09    --  -47.87  19.00   0.00   94
 15  \w    -21.00  28.00   0.50    0.09    --  -47.87  19.00 -60.00   98
 16  \w    -24.00  27.00   0.50    0.09    --  -47.87  19.00 -90.00  102
 17  \w    -13.00  24.00   0.50    0.09    --  -47.87  19.00-150.00   74
 18  \w     96.00 168.00   0.50    0.36    --  113.25 125.00 -60.00  144
 19  \w    127.00 153.00   0.50    0.36    --  113.25 130.00 -85.00   52
 20  \w     97.00 135.00   0.50    0.36    --  113.25 125.00-180.00   76
 21  \w    144.00 178.00   0.50    0.36    --  113.25 125.00-180.00   68
 22  \w     95.00 132.00   0.50    0.36    --  113.25 139.00  88.00   74
 23  \w     42.00  73.00   0.50    0.36    --  113.25 -77.00 -60.00   62
 24  \w     45.00  71.00   0.50    0.36    --  113.25 -61.00-150.00   52
 25  \w     42.00  70.00   0.50    0.36    --  113.25 -77.00 -90.00   56
 26  \w     46.00  71.00   0.50    0.36    --  113.25 -61.00 -60.00   50
 27  \w     42.00  71.00   0.50    0.36    --  113.25 -61.00 -30.00   58
 28  \w     42.00  69.00   0.50    0.36    --  113.25 -61.00  30.00   54
 29  \w     42.00  70.00   0.50    0.36    --  113.25 -61.00  90.00   56
 30  \w     44.00  71.00   0.50    0.36    --  113.25 -61.00 150.00   54
 31  \w      9.00  42.00   0.50    0.09    --   47.87 -37.00  90.00   66
 32  \w     42.00  71.00   0.50    0.36    --  113.25 -61.00-180.00   58
 33  \w     44.00  90.00   0.50    0.36    --  113.25 -94.00 -60.00   92
 34  \w     80.00 119.00   0.50    0.36    --  113.25-139.00  27.00   78
 35  \w     44.00 123.00   0.50    0.36    --  113.25-140.00 148.10  158
 36  \w     46.00 104.00   0.50    0.09    --   47.87-139.00  27.00  116
 37  \w     65.00 111.00   0.50    0.36    --  113.25-125.00-120.00   92
 38  \w     89.00 116.00   0.50    0.36    --  113.25-130.00-157.00   54
 39  \w     42.00  90.00   0.50    0.36    --  113.25-125.00-180.00   96
 40  \w     37.00  98.00   0.50    0.09    --   47.87-130.00-157.00  122
 41  \w     46.00 111.00   0.50    0.36    --  113.25-125.00 -60.00  130
 42  \w     81.00 106.00   0.50    0.36    --  113.25-100.00  41.27   50
 43  \w     51.00 108.00   0.50    0.36    --  113.25-110.00  60.14  114
 44  \w     46.00  75.00   0.50    0.36    --  113.25-125.00 120.00   58
 45  \w     65.00 108.00   0.50    0.36    --  113.25-125.00 150.00   86
 46  \w     44.00  72.00   0.50    0.36    --  113.25-100.00  41.27   56
 47  \w     50.00 101.00   0.50    0.36    --  113.25 -94.00   0.00  102
 48  \w     80.00 105.00   0.50    0.36    --  113.25 -94.00 -30.00   50
 49  \w     42.00  92.00   0.50    0.36    --  113.25 -94.00-120.00  100
 50  \w     77.00 104.00   0.50    0.36    --  113.25 -94.00-150.00   54
 51  \w     72.00 106.00   0.50    0.36    --  113.25 -94.00 -90.00   68
 52  \w     59.00 105.00   0.50    0.36    --  113.25 -94.00 150.00   92
 53  \w    -82.00 -57.00   0.50    0.09    --  -47.87 139.00  88.00   50
 54  \w    -71.00 -46.00   0.50    0.09    --  -47.87 130.00 -85.00   50
 55  \w    -82.00 -57.00   0.50    0.36    --  -91.75 139.00  88.00   50
 56  \w    -79.00 -54.00   0.50    0.36    --  -91.75 130.00 -85.00   50
 57  \w   -105.00 -76.00   0.50    0.36    --  -91.75 -61.00 -90.00   58
 58  \w   -120.00 -95.00   0.50    0.09    --  -47.87-125.00-150.00   50
 59  \w   -113.00 -74.00   0.50    0.09    --  -47.87-130.00-157.00   78
 60  \w   -152.00-126.00   0.50    0.36    --  -91.75 -61.00 -90.00   52
 61  \w   -105.00 -66.00   0.50    0.09    --  -47.87-139.00  27.00   78
 62  \w   -112.00 -80.00   0.50    0.09    --  -47.87-125.00 120.00   64
 63  \w   -135.00-109.00   0.50    0.36    --  -91.75-139.00  27.00   52
 64  \w   -141.00-116.00   0.50    0.36    --  -91.75-130.00-157.00   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      -0.0722922000
_diffrn_orient_matrix_UB_12      -0.1041481000
_diffrn_orient_matrix_UB_13      -0.0475109000
_diffrn_orient_matrix_UB_21      -0.0012114000
_diffrn_orient_matrix_UB_22      0.0336915000
_diffrn_orient_matrix_UB_23      -0.0767208000
_diffrn_orient_matrix_UB_31      0.0969941000
_diffrn_orient_matrix_UB_32      -0.0191090000
_diffrn_orient_matrix_UB_33      -0.0025405000
_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  0.0493
_diffrn_reflns_av_unetI/netI     0.0407
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            55907
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.165
_diffrn_reflns_theta_min         2.589
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.080
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48231
_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    1.320
_exptl_crystal_description       block
_exptl_crystal_F_000             1456
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.25
_refine_diff_density_max         2.336
_refine_diff_density_min         -1.669
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     807
_refine_ls_number_reflns         14960
_refine_ls_number_restraints     67
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0436
_refine_ls_R_factor_gt           0.0408
_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^)+(0.0734P)^2^+1.9517P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1051
_refine_ls_wR_factor_ref         0.1070
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13863
_reflns_number_total             14960
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05982d2.cif
_cod_data_source_block           crepw024_auto
_cod_depositor_comments
'Adding full bibliography for 1573553--1573561.cif.'
_cod_original_cell_volume        3510.01(14)
_cod_database_code               1573559
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.187
_shelx_estimated_absorpt_t_min   0.122
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 H2-H51A
 2.1 with sigma of 0.001
 C59-C63 \\sim C59-C0
 with sigma of 0.02
 C63-C64 \\sim C0-C02B
 with sigma of 0.02
 C63-C65 \\sim C0-C2A
 with sigma of 0.02
 C59-C64 \\sim C59-C02B
 with sigma of 0.04
 C59-C65 \\sim C59-C2A
 with sigma of 0.04
 C64-C65 \\sim C02B-C2A
 with sigma of 0.04
 C64-C63 \\sim C02B-C0
 with sigma of 0.02
 C2A-C0 \\sim C65-C63
 with sigma of 0.02
 C63-C59 \\sim C59-C0
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C2A \\sim C0 \\sim C02B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C64 \\sim C63 \\sim C65: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(C2A) \\sim Ueq, Uanis(C0) \\sim Ueq, Uanis(C02B) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C64) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C65) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C0)=Sof(H0)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=Sof(C02B)=Sof(H02G)=
 Sof(H02H)=Sof(H02I)=1-FVAR(1)
 Sof(C63)=Sof(H63)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=Sof(C65)=Sof(H65A)=
 Sof(H65B)=Sof(H65C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C15(H15), C27(H27), C19(H19), C43(H43), C46(H46), C60(H60), C12(H12),
 C63(H63), C0(H0)
5.b Secondary CH2 refined with riding coordinates:
 C69(H69A,H69B), C68(H68A,H68B), C67(H67A,H67B), C74(H74A,H74B), C73(H73A,
 H73B), C72(H72A,H72B)
5.c Aromatic/amide H refined with riding coordinates:
 N4(H4), N2(H2), C10(H10), C9(H9), C26(H26), C38(H38), C42(H42), C24(H24),
 C8(H8), C25(H25), C37(H37), C56(H56), C58(H58), C57(H57)
5.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C1(H1A,H1B,H1C), C3(H3A,H3B,H3C), C36(H36A,H36B,H36C),
 C51(H51A,H51B,H51C), C18(H18A,H18B,H18C), C47(H47A,H47B,H47C), C52(H52A,H52B,
 H52C), C16(H16A,H16B,H16C), C61(H61A,H61B,H61C), C20(H20A,H20B,H20C), C44(H44A,
 H44B,H44C), C17(H17A,H17B,H17C), C28(H28A,H28B,H28C), C48(H48A,H48B,H48C),
 C14(H14A,H14B,H14C), C53(H53A,H53B,H53C), C29(H29A,H29B,H29C), C45(H45A,H45B,
 H45C), C13(H13A,H13B,H13C), C66(H66A,H66B,H66C), C62(H62A,H62B,H62C), C70(H70A,
 H70B,H70C), C75(H75A,H75B,H75C), C71(H71A,H71B,H71C), C64(H64A,H64B,H64C),
 C65(H65A,H65B,H65C), C2A(H2AA,H2AB,H2AC), C02B(H02G,H02H,H02I)
;
_shelx_res_checksum              65471
_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 2.549
_oxdiff_exptl_absorpt_empirical_full_min 0.639