δ-Bonding modulates the electronic structure of formally divalent nd<sup>1</sup> rare earth arene complexes.
MacKenzie, Ross E.; Hajdu, Tomáš; Seed, John A.; Whitehead, George F. S.; Adams, Ralph W.; Chilton, Nicholas F.; Collison, David; McInnes, Eric J. L.; Goodwin, Conrad A. P.; Chemical science 15 (2024) 15160–15169; doi:10.1039/d4sc03005b

data_1572271
_publ_section_title
;
 &#x3b4;-Bonding modulates the electronic structure of formally divalent
 nd<sup>1</sup> rare earth arene complexes.
;
_journal_issue                   37
_journal_name_full               'Chemical science'
_journal_page_first              15160
_journal_page_last               15169
_journal_paper_doi               10.1039/d4sc03005b
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C72 H100 I N2 Y, 2(C7 H8)'
_chemical_formula_sum            'C86 H116 I N2 Y'
_chemical_formula_weight         1393.61
_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             2023-08-24
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-09-15 deposited with the CCDC.	2024-07-30 downloaded from the CCDC.
;
_cell_angle_alpha                90.423(2)
_cell_angle_beta                 110.358(2)
_cell_angle_gamma                92.402(2)
_cell_formula_units_Z            2
_cell_length_a                   13.8601(4)
_cell_length_b                   15.1451(4)
_cell_length_c                   19.2635(5)
_cell_measurement_reflns_used    21092
_cell_measurement_temperature    100.0(8)
_cell_measurement_theta_max      30.9710
_cell_measurement_theta_min      2.2520
_cell_volume                     3786.70(18)
_computing_cell_refinement       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(8)
_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 0.990
_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    -23.00  59.00   0.50   10.00    --   -8.91  77.00 -60.00  164
  2  \w     21.00  63.00   0.50   10.00    --   -8.91  77.00  60.00   84
  3  \w    -25.00  13.00   0.50   10.00    --   -8.91  77.00-180.00   76
  4  \w    -27.00  10.00   0.50   10.00    --   -8.91  77.00  60.00   74
  5  \w     -1.00  78.00   0.50   10.00    --    8.91  77.00 120.00  158
  6  \w      0.00  81.00   0.50   10.00    --    8.91  77.00-120.00  162
  7  \w      1.00  79.00   0.50   10.00    --    8.91  77.00   0.00  156
;
_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      0.0245394000
_diffrn_orient_matrix_UB_12      0.0179758000
_diffrn_orient_matrix_UB_13      -0.0238247000
_diffrn_orient_matrix_UB_21      0.0448765000
_diffrn_orient_matrix_UB_22      0.0108512000
_diffrn_orient_matrix_UB_23      0.0310714000
_diffrn_orient_matrix_UB_31      0.0192382000
_diffrn_orient_matrix_UB_32      -0.0419234000
_diffrn_orient_matrix_UB_33      -0.0032029000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0407
_diffrn_reflns_av_unetI/netI     0.0584
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            54617
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.131
_diffrn_reflns_theta_min         2.255
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.222
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.334
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.94a (Rigaku Oxford Diffraction, 2023)
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            'clear orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.222
_exptl_crystal_description       block
_exptl_crystal_F_000             1476
_exptl_crystal_size_max          0.488
_exptl_crystal_size_mid          0.177
_exptl_crystal_size_min          0.157
_refine_diff_density_max         0.764
_refine_diff_density_min         -0.437
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.007
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     841
_refine_ls_number_reflns         20193
_refine_ls_number_restraints     88
_refine_ls_restrained_S_all      1.007
_refine_ls_R_factor_all          0.0663
_refine_ls_R_factor_gt           0.0393
_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^)+(0.0417P)^2^+1.1078P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0807
_refine_ls_wR_factor_ref         0.0876
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15061
_reflns_number_total             20193
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03005b2.cif
_cod_data_source_block           ccapg101
_cod_depositor_comments
'Adding full bibliography for 1572261--1572275.cif.'
_cod_database_code               1572271
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         Y(NHC6H3(C6H2(C3H7)3)2)2I(C7H8)2
_shelx_estimated_absorpt_t_max   0.831
_shelx_estimated_absorpt_t_min   0.587
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-H1 \\sim N2-H2
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C80 \\sim C81 \\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
4. Rigid body (RIGU) restrains
 C80, C81, C82, C83, C84, C85, C86
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5.a Ternary CH refined with riding coordinates:
 C13(H13), C16(H16), C19(H19), C28(H28), C31(H31), C34(H34), C49(H49),
 C52(H52), C55(H55), C64(H64), C67(H67), C70(H70)
5.b Me refined with riding coordinates:
 C73(H73A,H73B,H73C), C80(H80A,H80B,H80C)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C9(H9), C11(H11), C24(H24), C26(H26), C39(H39),
 C40(H40), C41(H41), C45(H45), C47(H47), C60(H60), C62(H62), C75(H75), C76(H76),
  C77(H77), C78(H78), C79(H79), C82(H82), C83(H83), C84(H84), C85(H85), C86(H86)
5.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C),
 C36(H36A,H36B,H36C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C53(H53A,H53B,
 H53C), C54(H54A,H54B,H54C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C65(H65A,
 H65B,H65C), C66(H66A,H66B,H66C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C),
 C71(H71A,H71B,H71C), C72(H72A,H72B,H72C)
;
_shelx_res_checksum              97070
_shelx_hkl_checksum              48817
_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 1.453
_oxdiff_exptl_absorpt_empirical_full_min 0.721