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_1572267
_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_absolute_configuration rm
_chemical_formula_moiety
'2(C37 H50 Yb0.5), 0.75[C4H10O], 0.25[C4H10O], 1[], 0.25[C4H10O]'
_chemical_formula_sum            'C78 H115 N2 O1.5 Yb'
_chemical_formula_weight         1277.75
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_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                 106.4940(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.4353(2)
_cell_length_b                   16.06930(10)
_cell_length_c                   20.02640(10)
_cell_measurement_reflns_used    38431
_cell_measurement_temperature    99(6)
_cell_measurement_theta_max      79.4280
_cell_measurement_theta_min      3.4260
_cell_volume                     6922.81(9)
_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      99(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 0.989
_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    -66.00  22.00   0.50    3.50    --  -49.43  71.00-131.00  176
  2  \w   -108.00 -40.00   0.50    3.50    --  -49.43 -71.00  97.00  136
  3  \w     51.00  76.00   0.50    3.50    --   49.43  71.00-131.00   50
  4  \w    -19.00  67.00   0.50    3.50    --   49.43 -71.00  97.00  172
  5  \w   -117.00 -77.00   0.50   13.50    --  -90.00 -71.00  97.00   80
  6  \w    -69.00 -33.00   0.50   13.50    --  -90.00  71.00-131.00   72
  7  \w     94.00 140.00   0.50   13.50    --  111.50  71.00-131.00   92
  8  \w     42.00  89.00   0.50   13.50    --  111.50 -71.00  97.00   94
  9  \w   -120.00 -92.00   0.50    3.50    --  -49.43-125.00 -90.00   56
 10  \w    -25.00  14.00   0.50    3.50    --  -49.43  19.00-120.00   78
 11  \w   -118.00 -86.00   0.50    3.50    --  -49.43-125.00 120.00   64
 12  \w    -41.00  21.00   0.50    3.50    --  -49.43  37.00 120.00  124
 13  \w   -118.00 -76.00   0.50    3.50    --  -49.43-125.00-120.00   84
 14  \w    -16.00  22.00   0.50    3.50    --   49.43 -19.00 120.00   76
 15  \w   -110.00 -83.00   0.50   13.50    --  -90.00 -61.00   0.00   54
 16  \w   -140.00 -76.00   0.50   13.50    --  -90.00 -61.00 -30.00  128
 17  \w   -109.00 -83.00   0.50   13.50    --  -90.00 -15.00 -30.00   52
 18  \w    -44.00 -19.00   0.50   13.50    --  -90.00  45.00  60.00   50
 19  \w   -161.00-136.00   0.50   13.50    --  -90.00 -77.00  60.00   50
 20  \w    -95.00 -69.00   0.50   13.50    --  -90.00 -77.00  60.00   52
 21  \w     47.00  90.00   0.50   13.50    --  111.50 -94.00  90.00   86
 22  \w    106.00 178.00   0.50   13.50    --  111.50  45.00   0.00  144
 23  \w     94.00 173.00   0.50   13.50    --  111.50  77.00 -60.00  158
 24  \w     57.00  82.00   0.50   13.50    --  111.50 -94.00 -60.00   50
 25  \w     69.00 100.00   0.50   13.50    --  111.50-125.00-150.00   62
 26  \w    116.00 177.00   0.50   13.50    --  111.50  45.00-180.00  122
 27  \w    113.00 170.00   0.50   13.50    --  111.50  30.00 150.00  114
 28  \w     50.00 110.00   0.50   13.50    --  111.50-125.00-120.00  120
 29  \w     92.00 162.00   0.50   13.50    --  111.50  77.00 -90.00  140
 30  \w    102.00 171.00   0.50   13.50    --  111.50  45.00  60.00  138
 31  \w     98.00 132.00   0.50   13.50    --  111.50  61.00 150.00   68
 32  \w    143.00 172.00   0.50   13.50    --  111.50  61.00 150.00   58
 33  \w    122.00 178.00   0.50   13.50    --  111.50 125.00-120.00  112
 34  \w     44.00  69.00   0.50   13.50    --  111.50 -61.00-150.00   50
 35  \w     96.00 171.00   0.50   13.50    --  111.50 125.00  90.00  150
 36  \w     41.00  97.00   0.50   13.50    --  111.50-125.00  90.00  112
 37  \w     49.00  77.00   0.50   13.50    --  111.50   0.00 -30.00   56
 38  \w    101.00 150.00   0.50   13.50    --  111.50   0.00 -30.00   98
 39  \w    143.00 168.00   0.50   13.50    --  111.50  45.00-150.00   50
 40  \w    111.00 166.00   0.50   13.50    --  111.50 125.00 -60.00  110
 41  \w     50.00  77.00   0.50   13.50    --  111.50 -94.00  30.00   54
 42  \w    108.00 134.00   0.50   13.50    --  111.50  45.00-150.00   52
 43  \w    111.00 150.00   0.50   13.50    --  111.50 125.00 -90.00   78
 44  \w    100.00 167.00   0.50   13.50    --  111.50  61.00 -30.00  134
 45  \w     43.00  71.00   0.50   13.50    --  111.50 -77.00-150.00   56
 46  \w    102.00 137.00   0.50   13.50    --  111.50  45.00  90.00   70
 47  \w    112.00 168.00   0.50   13.50    --  111.50  30.00  30.00  112
 48  \w     45.00  70.00   0.50   13.50    --  111.50 -61.00 -90.00   50
 49  \w     42.00 103.00   0.50   13.50    --  111.50 -94.00 150.00  122
 50  \w     64.00 109.00   0.50   13.50    --  111.50-125.00   0.00   90
 51  \w    104.00 171.00   0.50   13.50    --  111.50  77.00  90.00  134
;
_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      0.0260142000
_diffrn_orient_matrix_UB_12      -0.0728955000
_diffrn_orient_matrix_UB_13      0.0497467000
_diffrn_orient_matrix_UB_21      -0.0445349000
_diffrn_orient_matrix_UB_22      0.0223413000
_diffrn_orient_matrix_UB_23      0.0433688000
_diffrn_orient_matrix_UB_31      -0.0496775000
_diffrn_orient_matrix_UB_32      -0.0581503000
_diffrn_orient_matrix_UB_33      -0.0455694000
_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  0.0385
_diffrn_reflns_av_unetI/netI     0.0318
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            56201
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.041
_diffrn_reflns_theta_min         2.301
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.825
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54986
_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 dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.226
_exptl_crystal_description       block
_exptl_crystal_F_000             2716
_exptl_crystal_size_max          0.083
_exptl_crystal_size_mid          0.076
_exptl_crystal_size_min          0.061
_refine_diff_density_max         1.710
_refine_diff_density_min         -2.065
_refine_diff_density_rms         0.096
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.010(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.130
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     867
_refine_ls_number_reflns         14716
_refine_ls_number_restraints     342
_refine_ls_restrained_S_all      1.128
_refine_ls_R_factor_all          0.0427
_refine_ls_R_factor_gt           0.0413
_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^)+42.5799P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1016
_refine_ls_wR_factor_ref         0.1022
_reflns_Friedel_coverage         0.897
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.954
_reflns_number_gt                14210
_reflns_number_total             14716
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03005b2.cif
_cod_data_source_block           ccapg88
_cod_depositor_comments
'Adding full bibliography for 1572261--1572275.cif.'
_cod_original_cell_volume        6922.80(9)
_cod_original_formula_sum        'C78 H115 N2 O1.50 Yb'
_cod_database_code               1572267
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         Yb(NHC6H3(C6H2(C3H7)3)2)2
_shelx_estimated_absorpt_t_max   0.847
_shelx_estimated_absorpt_t_min   0.799
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.990(12)
 0.010(12)
2. 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
3. Restrained distances
 C37-C23 \\sim C28-C23
 with sigma of 0.02
 C37-C1C \\sim C29-C28 \\sim C30-C28 \\sim C37-C1B
 with sigma of 0.02
 C1C-C1B \\sim C29-C30
 with sigma of 0.02
 C4S-C3S \\sim C1S-C2S \\sim C8S-C7S \\sim C6S-C5S \\sim C11S-C12S \\sim
C9S-C10S
 with sigma of 0.02
 C10S-C11S \\sim C7S-C6S \\sim C2S-C3S
 with sigma of 0.02
 O1S-C3S \\sim O1S-C2S \\sim O2S-C7S \\sim O2S-C6S \\sim O3S-C11S \\sim O3S-C10S
 with sigma of 0.02
 O3S-C9S \\sim O3S-C12S \\sim O2S-C5S \\sim O2S-C8S \\sim O1S-C1S \\sim O1S-C4S
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C28 \\sim C29 \\sim C30 \\sim C1B \\sim C1C \\sim C37: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
O1S \\sim C1S \\sim C2S \\sim C3S \\sim C4S \\sim O2S \\sim C5S \\sim C6S \\sim
C7S \\sim C8S: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 2A
O3S \\sim C9S \\sim C10S \\sim C11S \\sim C12S: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 C28, C29, C30, C1B, C1C, C37
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1S, C1S, C2S, C3S, C4S, O2S, C5S, C6S, C7S, C8S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O3S, C9S, C10S, C11S, C12S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=Sof(C1C)=Sof(H1CA)=Sof(H1CB)=Sof(H1CC)=
 Sof(C37)=Sof(H37)=1-FVAR(1)
 Sof(C28)=Sof(H28)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(C30)=Sof(H30A)=
 Sof(H30B)=Sof(H30C)=FVAR(1)
 Fixed Sof: O1S(0.5) C1S(0.5) H1SA(0.5) H1SB(0.5) H1SC(0.5) C2S(0.5) H2SA(0.5)
 H2SB(0.5) C3S(0.5) H3SA(0.5) H3SB(0.5) C4S(0.5) H4SA(0.5) H4SB(0.5) H4SC(0.5)
 O2S(0.5) C5S(0.5) H5SA(0.5) H5SB(0.5) H5SC(0.5) C6S(0.5) H6SA(0.5) H6SB(0.5)
 C7S(0.5) H7SA(0.5) H7SB(0.5) C8S(0.5) H8SA(0.5) H8SB(0.5) H8SC(0.5) O3S(0.5)
 C9S(0.5) H9SA(0.5) H9SB(0.5) H9SC(0.5) C10S(0.5) H10A(0.5) H10B(0.5) C11S(0.5)
 H11B(0.5) H11C(0.5) C12S(0.5) H12A(0.5) H12B(0.5) H12C(0.5)
7.a Ternary CH refined with riding coordinates:
 C13(H13), C16(H16), C19(H19), C31(H31), C34(H34), C28(H28), C37(H37),
 C13A(H13A), C16A(H16A), C19A(H19A), C28A(H28A), C31A(H31A), C34A(H34A)
7.b Secondary CH2 refined with riding coordinates:
 C2S(H2SA,H2SB), C3S(H3SA,H3SB), C6S(H6SA,H6SB), C7S(H7SA,H7SB), C10S(H10A,
 H10B), C11S(H11B,H11C)
7.c Me refined with riding coordinates:
 C1S(H1SA,H1SB,H1SC), C4S(H4SA,H4SB,H4SC), C5S(H5SA,H5SB,H5SC), C8S(H8SA,H8SB,
 H8SC), C9S(H9SA,H9SB,H9SC), C12S(H12A,H12B,H12C)
7.d Aromatic/amide H refined with riding coordinates:
 N1(H1), C3(H3), C4(H4), C5(H5), C9(H9), C11(H11), C24(H24), C26(H26),
 N1A(H1A), C3A(H3A), C4A(H4A), C5A(H5A), C9A(H9A), C11A(H11A), C24A(H24A),
 C26A(H26A)
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), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C29(H29A,H29B,H29C),
 C30(H30A,H30B,H30C), C1B(H1BA,H1BB,H1BC), C1C(H1CA,H1CB,H1CC), C14A(H14D,H14E,
 H14F), C15A(H15D,H15E,H15F), C17A(H17D,H17E,H17F), C18A(H18D,H18E,H18F),
 C20A(H20D,H20E,H20F), C21A(H21D,H21E,H21F), C29A(H29D,H29E,H29F), C30A(H30D,
 H30E,H30F), C32A(H32D,H32E,H32F), C33A(H33D,H33E,H33F), C35A(H35D,H35E,H35F),
 C36A(H36D,H36E,H36F)
;
_shelx_res_checksum              7934
_shelx_hkl_checksum              15525
_platon_squeeze_void_probe_radius 1.20
_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 1.856
_oxdiff_exptl_absorpt_empirical_full_min 0.410