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_1572275
_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 Yb, 2(C7 H8)'
_chemical_formula_sum            'C86 H116 I N2 Yb'
_chemical_formula_weight         1477.74
_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
_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                90.2040(15)
_cell_angle_beta                 110.2846(16)
_cell_angle_gamma                92.5150(16)
_cell_formula_units_Z            2
_cell_length_a                   13.8450(3)
_cell_length_b                   15.1906(3)
_cell_length_c                   19.2184(3)
_cell_measurement_reflns_used    30235
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      33.8830
_cell_measurement_theta_min      3.0350
_cell_volume                     3786.81(13)
_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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_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 0.998
_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     25.00  57.00   0.50   13.43    --   13.35-118.00  76.00   64
  2  \w     30.00  55.00   0.50   13.43    --   13.35-158.00 -76.00   50
  3  \w    -28.00  59.00   0.50   13.43    --  -13.35  57.00-120.00  174
  4  \w    -50.00 -16.00   0.50   13.43    --  -13.35 -57.00 -90.00   68
  5  \w    -79.00  -6.00   0.50   13.43    --  -13.35 -57.00  90.00  146
  6  \w    -85.00   2.00   0.50   13.43    --  -13.35 -57.00-180.00  174
  7  \w    -85.00 -11.00   0.50   13.43    --  -13.35 -77.00 -30.00  148
  8  \w    -79.00   8.00   0.50   13.43    --  -13.35 -77.00  60.00  174
  9  \w     43.00  73.00   0.50   13.43    --   13.35-178.00-150.00   60
 10  \w     41.00  66.00   0.50   13.43    --   13.35 178.00-120.00   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      -0.0138832000
_diffrn_orient_matrix_UB_12      0.0343373000
_diffrn_orient_matrix_UB_13      0.0192793000
_diffrn_orient_matrix_UB_21      -0.0361679000
_diffrn_orient_matrix_UB_22      0.0138636000
_diffrn_orient_matrix_UB_23      -0.0338740000
_diffrn_orient_matrix_UB_31      -0.0385917000
_diffrn_orient_matrix_UB_32      -0.0285319000
_diffrn_orient_matrix_UB_33      0.0054504000
_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  0.0366
_diffrn_reflns_av_unetI/netI     0.0426
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_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       -26
_diffrn_reflns_number            62723
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.130
_diffrn_reflns_theta_min         3.045
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.686
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75360
_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 green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.296
_exptl_crystal_description       block
_exptl_crystal_F_000             1538
_exptl_crystal_size_max          0.302
_exptl_crystal_size_mid          0.122
_exptl_crystal_size_min          0.084
_refine_diff_density_max         0.917
_refine_diff_density_min         -0.624
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     893
_refine_ls_number_reflns         20369
_refine_ls_number_restraints     313
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0418
_refine_ls_R_factor_gt           0.0295
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0263P)^2^+1.9346P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0605
_refine_ls_wR_factor_ref         0.0637
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17030
_reflns_number_total             20369
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03005b2.cif
_cod_data_source_block           ccapg114
_cod_depositor_comments
'Adding full bibliography for 1572261--1572275.cif.'
_cod_database_code               1572275
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C86 H116 I Yb N2'
_shelx_estimated_absorpt_t_max   0.871
_shelx_estimated_absorpt_t_min   0.630
_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
 C81A-C80A
 1.54 with sigma of 0.02
 N1-H1 \\sim N2-H2
 with sigma of 0.02
 C82A-C80A \\sim C80A-C86A
 with sigma of 0.02
3. Restrained planarity
 C81A, C80A, C82A, C86A, C83A, C85A, C84A
 with sigma of 0.01
4. 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
C81A \\sim C86A \\sim C82A \\sim C80A \\sim C85A \\sim C83A \\sim C84A \\sim
C86 \\sim C80 \\sim C81 \\sim C82 \\sim C83 \\sim C85 \\sim C84: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
5. 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
 C86, C80, C81, C82, C83, C85, C84, C86A, C81A, C82A, C80A, C85A, C83A, C84A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
6. Others
 Sof(C81A)=Sof(C86A)=Sof(H86A)=Sof(C85A)=Sof(H85A)=Sof(C84A)=Sof(H84A)=
 Sof(C83A)=Sof(H83A)=Sof(C82A)=Sof(H82A)=Sof(C80A)=Sof(H80D)=Sof(H80E)=
 Sof(H80F)=1-FVAR(1)
 Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(H80C)=Sof(C81)=Sof(C82)=Sof(H82)=Sof(C83)=
 Sof(H83)=Sof(C84)=Sof(H84)=Sof(C85)=Sof(H85)=Sof(C86)=Sof(H86)=FVAR(1)
7.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)
7.b Me refined with riding coordinates:
 C73(H73A,H73B,H73C), C80(H80A,H80B,H80C), C80A(H80D,H80E,H80F)
7.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), C86A(H86A), C85A(H85A), C84A(H84A), C83A(H83A), C82A(H82A)
7.d Fitted hexagon refined as free rotating group:
 C81A(C86A,C85A,C84A,C83A,C82A)
7.e 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              21971
_shelx_hkl_checksum              96944
_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 1.461
_oxdiff_exptl_absorpt_empirical_full_min 0.692