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_1572274
_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, C3 H7'
_chemical_formula_sum            'C75 H107 I N2 Y'
_chemical_formula_weight         1252.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-09-06
_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
_cell_angle_beta                 97.2910(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.79590(10)
_cell_length_b                   23.5264(2)
_cell_length_c                   19.43130(10)
_cell_measurement_reflns_used    32050
_cell_measurement_temperature    100.0(5)
_cell_measurement_theta_max      79.3870
_cell_measurement_theta_min      2.9560
_cell_volume                     6709.23(8)
_computing_cell_refinement       'CrysAlisPro 1.171.43.88a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 41.122a 64-bit (release 06-12-2021))'
_computing_data_reduction        'CrysAlisPro 1.171.43.88a (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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(5)
_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 0.971
_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   -120.00 -58.00   0.50    8.00    --  -47.87-147.00  14.00  124
  2  \w    -87.00 -62.00   0.50    8.00    --  -47.87 147.00  64.00   50
  3  \w    -67.00 -41.00   0.50    8.00    --  -47.87 124.00-100.00   52
  4  \w   -118.00 -75.00   0.50    8.00    --  -47.87-124.00 179.00   86
  5  \w     68.00  95.00   0.50    8.00    --   47.87-124.00 179.00   54
  6  \w     53.00  78.00   0.50    8.00    --   47.87-147.00  14.00   50
  7  \w    -87.00 -62.00   0.50   30.00    --  -91.75 147.00  64.00   50
  8  \w    -76.00 -51.00   0.50   30.00    --  -91.75 124.00-100.00   50
  9  \w   -108.00 -82.00   0.50   30.00    --  -91.75-147.00  14.00   52
 10  \w    100.00 125.00   0.50   30.00    --  113.25 147.00  64.00   50
 11  \w     47.00 127.00   0.50   30.00    --  113.25-147.00  14.00  160
 12  \w    117.00 142.00   0.50   30.00    --  113.25 124.00-100.00   50
 13  \w     62.00 102.00   0.50   30.00    --  113.25-124.00 179.00   80
 14  \w    -25.00  26.00   0.50    8.00    --  -47.87  19.00-120.00  102
 15  \w    -25.00  28.00   0.50    8.00    --  -47.87  19.00  90.00  106
 16  \w    -25.00  20.00   0.50    8.00    --  -47.87  19.00-150.00   90
 17  \w    -26.00  22.00   0.50    8.00    --   47.87 -19.00 -90.00   96
 18  \w    -51.00 -21.00   0.50   30.00    --  -91.75  45.00  60.00   60
 19  \w    112.00 178.00   0.50   30.00    --  113.25  15.00 -90.00  132
 20  \w     57.00 125.00   0.50   30.00    --  113.25-144.00-123.68  136
 21  \w    101.00 130.00   0.50   30.00    --  113.25 125.00-150.00   58
 22  \w     95.00 164.00   0.50   30.00    --  113.25 125.00  90.00  138
 23  \w    101.00 161.00   0.50   30.00    --  113.25  30.00-180.00  120
 24  \w     45.00  70.00   0.50   30.00    --  113.25 -61.00 120.00   50
 25  \w     43.00 110.00   0.50   30.00    --  113.25-125.00-120.00  134
 26  \w    114.00 170.00   0.50   30.00    --  113.25  61.00   0.00  112
 27  \w     47.00 107.00   0.50   30.00    --  113.25-125.00 -90.00  120
 28  \w    141.00 166.00   0.50   30.00    --  113.25 125.00-150.00   50
 29  \w     71.00 111.00   0.50   30.00    --  113.25-125.00 -60.00   80
 30  \w     55.00 106.00   0.50   30.00    --  113.25 -77.00 -30.00  102
;
_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      0.0064061000
_diffrn_orient_matrix_UB_12      -0.0504694000
_diffrn_orient_matrix_UB_13      0.0509388000
_diffrn_orient_matrix_UB_21      -0.0213708000
_diffrn_orient_matrix_UB_22      -0.0413853000
_diffrn_orient_matrix_UB_23      -0.0613422000
_diffrn_orient_matrix_UB_31      0.1025458000
_diffrn_orient_matrix_UB_32      -0.0054532000
_diffrn_orient_matrix_UB_33      -0.0055930000
_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  0.0424
_diffrn_reflns_av_unetI/netI     0.0349
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            55670
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.124
_diffrn_reflns_theta_min         2.964
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.137
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67957
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.88a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.240
_exptl_crystal_description       block
_exptl_crystal_F_000             2652
_exptl_crystal_size_max          0.086
_exptl_crystal_size_mid          0.039
_exptl_crystal_size_min          0.025
_refine_diff_density_max         0.763
_refine_diff_density_min         -1.317
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     757
_refine_ls_number_reflns         14218
_refine_ls_number_restraints     53
_refine_ls_restrained_S_all      1.101
_refine_ls_R_factor_all          0.0404
_refine_ls_R_factor_gt           0.0355
_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^)+(0.0414P)^2^+6.0639P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0913
_refine_ls_wR_factor_ref         0.0935
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12664
_reflns_number_total             14218
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03005b2.cif
_cod_data_source_block           ccapg64
_cod_depositor_comments
'Adding full bibliography for 1572261--1572275.cif.'
_cod_database_code               1572274
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         Y(NHC6H3(C6H2(C3H7)3)2)2I
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 N1-H1 = N2-H2
 0.85 with sigma of 0.02
 C74A-C73 \\sim C74-C73 \\sim C75-C74A \\sim C75-C74
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C74A \\sim C75 \\sim C74 \\sim C73: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Uanis(Y1A) = Uanis(Y1)
4. Rigid body (RIGU) restrains
 C74A, C75, C74, C73
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Y1A)=1-FVAR(1)
 Sof(Y1)=FVAR(1)
 Sof(H75C)=Sof(H75D)=Sof(H73D)=Sof(H73E)=Sof(H73F)=Sof(C74A)=Sof(H74C)=
 Sof(H74D)=1-FVAR(2)
 Sof(H75A)=Sof(H75B)=Sof(H73A)=Sof(H73B)=Sof(H73C)=Sof(C74)=Sof(H74A)=
 Sof(H74B)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C28(H28), C34(H34), C52(H52), C13(H13), C64(H64), C16(H16), C19(H19),
 C31(H31), C55(H55), C49(H49), C67(H67), C70(H70)
6.b Secondary CH2 refined with riding coordinates:
 C75(H75A,H75B), C75(H75C,H75D), C74(H74A,H74B), C74A(H74C,H74D)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C40(H40), C11(H11), C60(H60), C62(H62), C45(H45), C4(H4), C26(H26),
 C24(H24), C41(H41), C5(H5), C39(H39), C9(H9), C47(H47)
6.d Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C17(H17A,H17B,H17C), C54(H54A,H54B,H54C), C18(H18A,H18B,
 H18C), C33(H33A,H33B,H33C), C69(H69A,H69B,H69C), C36(H36A,H36B,H36C), C72(H72A,
 H72B,H72C), C66(H66A,H66B,H66C), C68(H68A,H68B,H68C), C35(H35A,H35B,H35C),
 C15(H15A,H15B,H15C), C20(H20A,H20B,H20C), C71(H71A,H71B,H71C), C50(H50A,H50B,
 H50C), C14(H14A,H14B,H14C), C29(H29A,H29B,H29C), C21(H21A,H21B,H21C), C53(H53A,
 H53B,H53C), C57(H57A,H57B,H57C), C51(H51A,H51B,H51C), C32(H32A,H32B,H32C),
 C65(H65A,H65B,H65C), C56(H56A,H56B,H56C), C73(H73A,H73B,H73C), C73(H73D,H73E,
 H73F)
;
_shelx_res_checksum              34180
_shelx_hkl_checksum              64941
_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 1.509
_oxdiff_exptl_absorpt_empirical_full_min 0.563