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_1572266
_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 N2 Y, C4 H10 O'
_chemical_formula_sum            'C76 H110 N2 O Y'
_chemical_formula_weight         1156.56
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-09-14
_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                 107.8036(19)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.0918(3)
_cell_length_b                   16.7202(3)
_cell_length_c                   23.1781(4)
_cell_measurement_reflns_used    19330
_cell_measurement_temperature    100.01(13)
_cell_measurement_theta_max      75.8170
_cell_measurement_theta_min      5.1070
_cell_volume                     6675.6(2)
_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      100.01(13)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.987
_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    -89.00   5.00   0.50    3.00    --  -44.40  28.00  96.00  188
  2  \w   -115.00 -66.00   0.50    3.00    --  -46.40 -28.00 -65.00   98
  3  \w    -47.00 -18.00   0.50   12.00    -- -107.20  28.00  96.00   58
  4  \w   -116.00 -70.00   0.50   12.00    -- -107.20 -28.00 -65.00   92
  5  \w   -180.00-140.00   0.50   12.00    -- -107.20 -28.00 -65.00   80
  6  \w    -40.00 -15.00   0.50    3.00    --    5.00 -28.00 -65.00   50
  7  \w    -44.00 -19.00   0.50    3.00    --  -44.40  57.00-180.00   50
  8  \w      9.00  41.00   0.50    3.00    --  -44.40  28.00  96.00   64
  9  \w    -76.00  42.00   0.50    3.00    --  -44.40  57.00 150.00  236
 10  \w    -77.00 -51.00   0.50   12.00    -- -107.20  75.00 -64.39   52
 11  \w   -145.00-111.00   0.50   12.00    -- -107.20  76.00 -30.00   68
 12  \w   -135.00 -87.00   0.50   12.00    -- -107.20  34.00 -59.47   96
 13  \w   -147.00-121.00   0.50   12.00    -- -107.20  76.00 150.00   52
 14  \w   -140.00-111.00   0.50   12.00    -- -107.20  75.00 -64.39   58
 15  \w    -90.00 -18.00   0.50   12.00    -- -107.20  76.00 150.00  144
 16  \w   -148.00-119.00   0.50   12.00    -- -107.20  76.00-180.00   58
 17  \w   -100.00 -19.00   0.50   12.00    -- -107.20  76.00-180.00  162
 18  \w   -106.00 -81.00   0.50   12.00    -- -107.20  76.00-150.00   50
 19  \w    -99.00 -18.00   0.50   12.00    -- -107.20  76.00 -30.00  162
 20  \w    -75.00 -49.00   0.50   12.00    -- -107.20  67.00-143.85   52
 21  \w    -96.00 -59.00   0.50   12.00    -- -107.20  57.00  90.00   74
 22  \w    -56.00 -18.00   0.50   12.00    -- -107.20  38.00 150.00   76
 23  \w   -139.00 -61.00   0.50   12.00    -- -107.20  50.00-154.72  156
 24  \w   -158.00-106.00   0.50   12.00    -- -107.20 -59.00 107.60  104
 25  \w   -181.00-126.00   0.50   12.00    -- -107.20 -38.00   0.00  110
 26  \w   -107.00 -81.00   0.50   12.00    -- -107.20 -38.00   0.00   52
 27  \w   -133.00-100.00   0.50   12.00    -- -107.20  12.00-106.07   66
 28  \w    -57.00 -22.00   0.50   12.00    -- -107.20  12.00-106.07   70
 29  \w   -173.00-148.00   0.50   12.00    -- -107.20 -44.00 156.13   50
 30  \w   -121.00 -87.00   0.50   12.00    -- -107.20 -44.00 156.13   68
 31  \w   -140.00-115.00   0.50   12.00    -- -107.20  76.00-150.00   50
 32  \w   -145.00 -82.00   0.50   12.00    -- -107.20  38.00 150.00  126
 33  \w   -127.00-102.00   0.50   12.00    -- -107.20  57.00  90.00   50
 34  \w   -133.00 -95.00   0.50   12.00    -- -107.20  57.00 -30.00   76
 35  \w   -107.00 -82.00   0.50   12.00    -- -107.20 -61.00 178.21   50
 36  \w    -74.00 -27.00   0.50   12.00    -- -107.20  34.00 -59.47   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0782979500
_diffrn_orient_matrix_UB_12      -0.0326838500
_diffrn_orient_matrix_UB_13      -0.0029108000
_diffrn_orient_matrix_UB_21      -0.0340973000
_diffrn_orient_matrix_UB_22      -0.0094829000
_diffrn_orient_matrix_UB_23      -0.0691403000
_diffrn_orient_matrix_UB_31      0.0263620500
_diffrn_orient_matrix_UB_32      0.0857793500
_diffrn_orient_matrix_UB_33      -0.0086057000
_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  0.0266
_diffrn_reflns_av_unetI/netI     0.0234
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            34382
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.371
_diffrn_reflns_theta_min         3.684
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    1.549
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90846
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.94a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.151
_exptl_crystal_description       block
_exptl_crystal_F_000             2508
_exptl_crystal_size_max          0.107
_exptl_crystal_size_mid          0.068
_exptl_crystal_size_min          0.025
_refine_diff_density_max         0.541
_refine_diff_density_min         -0.645
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     378
_refine_ls_number_reflns         6910
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0349
_refine_ls_R_factor_gt           0.0330
_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^)+(0.0428P)^2^+7.2427P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0869
_refine_ls_wR_factor_ref         0.0879
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6491
_reflns_number_total             6910
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03005b2.cif
_cod_data_source_block           rcapg40
_cod_depositor_comments
'Adding full bibliography for 1572261--1572275.cif.'
_cod_database_code               1572266
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         Y(NHC6H3(C6H2(C3H7)3)2)2(OC4H10)
_shelx_estimated_absorpt_t_max   0.962
_shelx_estimated_absorpt_t_min   0.852
_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.a Ternary CH refined with riding coordinates:
 C19(H19), C16(H16), C13(H13), C28(H28), C31(H31), C34(H34)
2.b Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C11(H11), C9(H9), C24(H24), C26(H26)
2.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C14(H14A,H14B,H14C), 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), C38(H38A,H38B,H38C)
;
_shelx_res_checksum              17251
_shelx_hkl_checksum              81703
_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 1.165
_oxdiff_exptl_absorpt_empirical_full_min 0.862