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_1572273
_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 Tm, C4 H10 O'
_chemical_formula_sum            'C76 H110 N2 O Tm'
_chemical_formula_weight         1236.58
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 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                 95.8291(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.1863(2)
_cell_length_b                   24.2869(3)
_cell_length_c                   21.3806(3)
_cell_measurement_reflns_used    9162
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      75.8970
_cell_measurement_theta_min      2.7500
_cell_volume                     6811.82(16)
_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      99.98(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.983
_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     37.00 100.00   0.50    1.00    --   46.08  18.00 -50.00  126
  2  \w     61.00 102.00   0.50    2.00    --  108.20  18.00 -50.00   82
  3  \w     24.00  57.00   0.50    2.00    --  108.20  18.00 -50.00   66
  4  \w    -46.00 133.00   0.50    1.00    --   43.52  60.00-150.00  358
  5  \w     19.00  44.00   0.50    1.00    --   43.52  18.00 -50.00   50
  6  \w     53.00 131.00   0.50    1.00    --   46.08  20.00-150.00  156
  7  \w     66.00 113.00   0.50    2.00    --  108.20  50.00-180.00   94
  8  \w    115.00 141.00   0.50    2.00    --  108.20  40.00  30.00   52
  9  \w     19.00 198.00   0.50    2.00    --  108.20  50.00 120.00  358
 10  \w     19.00 197.00   0.50    2.00    --  108.20  50.00  60.00  356
 11  \w    131.00 157.00   0.50    2.00    --  108.20  30.00-180.00   52
 12  \w    173.00 198.00   0.50    2.00    --  108.20  30.00-180.00   50
 13  \w     67.00  93.00   0.50    2.00    --  108.20  40.00  30.00   52
 14  \w    106.00 141.00   0.50    2.00    --  108.20  50.00   0.00   70
 15  \w     20.00  45.00   0.50    2.00    --  108.20  50.00  90.00   50
 16  \w     98.00 151.00   0.50    2.00    --  108.20  50.00  90.00  106
 17  \w    156.00 197.00   0.50    2.00    --  108.20  50.00  90.00   82
 18  \w     38.00  63.00   0.50    2.00    --  108.20  50.00   0.00   50
 19  \w     26.00 118.00   0.50    2.00    --  108.20  30.00-180.00  184
 20  \w    156.00 181.00   0.50    2.00    --  108.20  50.00   0.00   50
 21  \w    144.00 189.00   0.50    2.00    --  108.20  50.00-180.00   90
 22  \w     80.00 124.00   0.50    2.00    --  108.20  50.00 150.00   88
 23  \w    150.00 175.00   0.50    2.00    --  108.20  50.00 150.00   50
 24  \w    105.00 130.00   0.50    2.00    --  108.20  20.00 150.00   50
 25  \w    114.00 190.00   0.50    2.00    --  108.20  18.00 -50.00  152
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0996581000
_diffrn_orient_matrix_UB_12      0.0147941000
_diffrn_orient_matrix_UB_13      -0.0403647000
_diffrn_orient_matrix_UB_21      -0.0511672000
_diffrn_orient_matrix_UB_22      0.0124430000
_diffrn_orient_matrix_UB_23      0.0600814000
_diffrn_orient_matrix_UB_31      0.0350881000
_diffrn_orient_matrix_UB_32      0.0604419000
_diffrn_orient_matrix_UB_33      -0.0024347000
_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  0.0425
_diffrn_reflns_av_unetI/netI     0.0400
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            63671
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.445
_diffrn_reflns_theta_min         2.762
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    2.751
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.21568
_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    1.206
_exptl_crystal_description       block
_exptl_crystal_F_000             2628
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.075
_exptl_crystal_size_min          0.029
_refine_diff_density_max         0.746
_refine_diff_density_min         -0.876
_refine_diff_density_rms         0.067
_refine_ls_extinction_coef       0.00020(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     850
_refine_ls_number_reflns         14064
_refine_ls_number_restraints     240
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0362
_refine_ls_R_factor_gt           0.0318
_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^)+(0.0323P)^2^+4.5951P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0801
_refine_ls_wR_factor_ref         0.0823
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12567
_reflns_number_total             14064
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03005b2.cif
_cod_data_source_block           lcapg33
_cod_depositor_comments
'Adding full bibliography for 1572261--1572275.cif.'
_cod_original_cell_volume        6811.84(18)
_cod_database_code               1572273
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         Tm(NHC6H3(C6H2(C3H7)3)2)2OC4H10
_shelx_estimated_absorpt_t_max   0.924
_shelx_estimated_absorpt_t_min   0.734
_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. Restrained distances
 O1-C76 \\sim O1-C73
 with sigma of 0.02
 O1-C74 \\sim O1-C75
 with sigma of 0.02
 C76-C75 \\sim C74-C73
 with sigma of 0.02
 C16A-C10 \\sim C16-C10
 with sigma of 0.02
 C12-C20 \\sim C12-C20A
 with sigma of 0.04
 C12-C21 \\sim C12-C21A
 with sigma of 0.04
 C19-C12 \\sim C19A-C12
 with sigma of 0.02
 C12-C19 \\sim C12-C19A
 with sigma of 0.02
 C18A-C16A \\sim C18-C16 \\sim C17-C16 \\sim C17A-C16A
 with sigma of 0.02
 C19-C20 \\sim C19A-C20A
 with sigma of 0.02
 C19-C21 \\sim C19A-C21A
 with sigma of 0.02
 C21A-C19A \\sim C20-C19 \\sim C21-C19 \\sim C20A-C19A
 with sigma of 0.02
 C20-C21 \\sim C20A-C21A
 with sigma of 0.04
 C53-C52 \\sim C53A-C52 \\sim C54A-C52 \\sim C54-C52
 with sigma of 0.02
 C53-C54 \\sim C54A-C53A
 with sigma of 0.02
 C72-C70 \\sim C72A-C70 \\sim C71A-C70 \\sim C71-C70
 with sigma of 0.02
3. Restrained planarity
 C7, C8, C9, C10, C11, C12
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C16 \\sim C18A \\sim C19A \\sim C17 \\sim C72A \\sim C18 \\sim C21A \\sim C19
\\sim C53A \\sim C20 \\sim C71A \\sim C21 \\sim C20A \\sim C53 \\sim C16A \\sim
C54 \\sim C17A \\sim C71 \\sim C54A \\sim C72: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 C16, C18A, C19A, C17, C72A, C18, C21A, C19, C53A, C20, C71A, C21, C20A, C53,
 C16A, C54, C17A, C71, C54A, C72
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H70A)=Sof(C72A)=Sof(H72D)=Sof(H72E)=Sof(H72F)=Sof(C71A)=Sof(H71D)=
 Sof(H71E)=Sof(H71F)=1-FVAR(1)
 Sof(H70)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(C72)=Sof(H72A)=Sof(H72B)=
 Sof(H72C)=FVAR(1)
 Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C21A)=
 Sof(H21D)=Sof(H21E)=Sof(H21F)=1-FVAR(2)
 Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21)=Sof(H21A)=
 Sof(H21B)=Sof(H21C)=FVAR(2)
 Sof(C16A)=Sof(H16A)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C17A)=
 Sof(H17D)=Sof(H17E)=Sof(H17F)=1-FVAR(3)
 Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18)=Sof(H18A)=
 Sof(H18B)=Sof(H18C)=FVAR(3)
 Sof(H52A)=Sof(C53A)=Sof(H53D)=Sof(H53E)=Sof(H53F)=Sof(C54A)=Sof(H54D)=
 Sof(H54E)=Sof(H54F)=1-FVAR(4)
 Sof(H52)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(C54)=Sof(H54A)=Sof(H54B)=
 Sof(H54C)=FVAR(4)
7.a Ternary CH refined with riding coordinates:
 C28(H28), C31(H31), C13(H13), C16(H16), C19(H19), C34(H34), C49(H49),
 C52(H52), C52(H52A), C55(H55), C64(H64), C67(H67), C70(H70A), C70(H70),
 C19A(H19A), C16A(H16A)
7.b Secondary CH2 refined with riding coordinates:
 C74(H74A,H74B), C75(H75A,H75B)
7.c Me refined with riding coordinates:
 C73(H73A,H73B,H73C), C76(H76A,H76B,H76C), C53(H53A,H53B,H53C), C54(H54A,H54B,
 H54C), C53A(H53D,H53E,H53F), C54A(H54D,H54E,H54F)
7.d 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)
7.e Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C14(H14A,H14B,
 H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C20(H20A,
 H20B,H20C), C21(H21A,H21B,H21C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C),
 C36(H36A,H36B,H36C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), 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),
 C72A(H72D,H72E,H72F), C71A(H71D,H71E,H71F), C20A(H20D,H20E,H20F), C21A(H21D,
 H21E,H21F), C18A(H18D,H18E,H18F), C17A(H17D,H17E,H17F)
;
_shelx_res_checksum              13861
_shelx_hkl_checksum              77669
_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 8.324
_oxdiff_exptl_absorpt_empirical_full_min 0.597