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_1572264
_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 La N2, C4 H10 O'
_chemical_formula_sum            'C76 H110 La N2 O'
_chemical_formula_weight         1206.56
_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                 96.7512(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.2755(2)
_cell_length_b                   24.2918(3)
_cell_length_c                   21.4153(3)
_cell_measurement_reflns_used    29676
_cell_measurement_temperature    99.98(11)
_cell_measurement_theta_max      75.3590
_cell_measurement_theta_min      2.7260
_cell_volume                     6858.24(17)
_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(11)
_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 0.985
_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    -36.00 -11.00   0.50    0.50    --    5.00 -25.00  42.00   50
  2  \w    -28.00  30.00   0.50    0.50    --  -44.05  25.00-153.00  116
  3  \w    -76.00   7.00   0.50    0.50    --  -46.15 -25.00  42.00  166
  4  \w   -135.00 -78.00   0.50    0.50    --  -46.15 -25.00  42.00  114
  5  \w   -197.00 -92.00   0.50    1.00    -- -107.20 -25.00  42.00  210
  6  \w   -115.00 -90.00   0.50    1.00    -- -107.20  25.00-153.00   50
  7  \w      1.00  26.00   0.50    0.50    --    5.00  57.00 -60.00   50
  8  \w    -75.00  34.00   0.50    0.50    --  -44.05  57.00 -90.00  218
  9  \w    -54.00 -29.00   0.50    0.50    --  -46.15  25.00-153.00   50
 10  \w   -145.00 -34.00   0.50    1.00    -- -107.20  38.00  30.00  222
 11  \w   -125.00 -18.00   0.50    1.00    -- -107.20  57.00-120.00  214
 12  \w   -140.00 -22.00   0.50    1.00    -- -107.20  57.00-180.00  236
 13  \w    -59.00 -33.00   0.50    1.00    -- -107.20  76.00  30.00   52
 14  \w   -121.00 -87.00   0.50    1.00    -- -107.20  71.00 -17.23   68
 15  \w    -84.00 -59.00   0.50    1.00    -- -107.20  71.00 -17.23   50
 16  \w    -68.00 -28.00   0.50    1.00    -- -107.20  57.00-150.00   80
 17  \w   -112.00 -80.00   0.50    1.00    -- -107.20 -38.00  90.00   64
 18  \w   -192.00-140.00   0.50    1.00    -- -107.20 -76.00 -30.00  104
 19  \w   -101.00 -76.00   0.50    1.00    -- -107.20 -76.00 -30.00   50
 20  \w   -172.00-136.00   0.50    1.00    -- -107.20 -38.00  90.00   72
 21  \w   -131.00 -35.00   0.50    1.00    -- -107.20  76.00-120.00  192
 22  \w   -145.00 -71.00   0.50    1.00    -- -107.20  76.00  30.00  148
 23  \w    -76.00 -50.00   0.50    1.00    -- -107.20  57.00 -60.00   52
 24  \w   -194.00-159.00   0.50    1.00    -- -107.20 -76.00-180.00   70
 25  \w   -156.00-131.00   0.50    1.00    -- -107.20 -76.00-180.00   50
 26  \w   -114.00 -78.00   0.50    1.00    -- -107.20  76.00 -30.00   72
 27  \w   -108.00 -83.00   0.50    1.00    -- -107.20  76.00   0.00   50
 28  \w   -134.00 -18.00   0.50    1.00    -- -107.20  57.00  30.00  232
;
_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      -0.1055793000
_diffrn_orient_matrix_UB_12      0.0115217000
_diffrn_orient_matrix_UB_13      -0.0353959000
_diffrn_orient_matrix_UB_21      -0.0493914000
_diffrn_orient_matrix_UB_22      -0.0169167000
_diffrn_orient_matrix_UB_23      0.0586494000
_diffrn_orient_matrix_UB_31      0.0064538000
_diffrn_orient_matrix_UB_32      0.0601268000
_diffrn_orient_matrix_UB_33      0.0234342000
_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  0.0310
_diffrn_reflns_av_unetI/netI     0.0273
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            65139
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.737
_diffrn_reflns_theta_min         3.352
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    5.124
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42844
_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    1.169
_exptl_crystal_description       block
_exptl_crystal_F_000             2580
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.169
_exptl_crystal_size_min          0.092
_refine_diff_density_max         1.354
_refine_diff_density_min         -1.245
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.128
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     960
_refine_ls_number_reflns         14067
_refine_ls_number_restraints     1152
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0477
_refine_ls_R_factor_gt           0.0451
_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^)+(0.0399P)^2^+15.8785P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1151
_refine_ls_wR_factor_ref         0.1164
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13155
_reflns_number_total             14067
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03005b2.cif
_cod_data_source_block           rcapg30
_cod_depositor_comments
'Adding full bibliography for 1572261--1572275.cif.'
_cod_original_cell_volume        6858.27(18)
_cod_database_code               1572264
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         La(NHC6H3(C6H2(C3H7)3)2)2
_shelx_estimated_absorpt_t_max   0.650
_shelx_estimated_absorpt_t_min   0.328
_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. Shared sites
{C74A, C74}
3. Restrained distances
 La1-H1 \\sim La1-H2
 with sigma of 0.02
 N2-H2 \\sim N1-H1
 with sigma of 0.02
 C1-H1 \\sim C37-H2
 with sigma of 0.02
 C7A-C2 \\sim C7-C2
 with sigma of 0.02
 C70-C63 \\sim C70A-C63
 with sigma of 0.02
 C71A-C70A \\sim C71-C70 \\sim C72A-C70A \\sim C72-C70
 with sigma of 0.02
 O1A-C76A \\sim O1-C76 \\sim O1-C73 \\sim O1A-C73A
 with sigma of 0.02
 O1-C74 \\sim O1A-C74A \\sim O1-C75 \\sim O1A-C75A
 with sigma of 0.02
 C76-C75 \\sim C76A-C75A \\sim C74-C73 \\sim C74A-C73A
 with sigma of 0.02
 C75-C74 \\sim C75A-C74A
 with sigma of 0.02
4. Restrained planarity
 C7, C12, C11, C10, C9, C8
 with sigma of 0.01
 C12A, C11A, C10A, C9A, C8A, C7A
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
C70 \\sim C71A \\sim C72A \\sim C71 \\sim C70A \\sim C72: within 2A with sigma
of 0.02 and sigma for terminal atoms of 0.04 within 2A
C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim
C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C7A \\sim
C8A \\sim C9A \\sim C10A \\sim C11A \\sim C12A \\sim C13A \\sim C14A \\sim C15A
\\sim C16A \\sim C17A \\sim C18A \\sim C19A \\sim C20A \\sim C21A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim
C30 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
O1 \\sim C73 \\sim C74 \\sim C75 \\sim C76 \\sim O1A \\sim C73A \\sim C74A
\\sim C75A \\sim C76A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(C74A) = Uanis(C74)
6. Rigid body (RIGU) restrains
 C70, C71A, C72A, C71, C70A, C72
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C7A,
 C8A, C9A, C10A, C11A, C12A, C13A, C14A, C15A, C16A, C17A, C18A, C19A, C20A,
 C21A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33, C34, C35, C36
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 O1, C73, C74, C75, C76, O1A, C73A, C74A, C75A, C76A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(C7A)=Sof(C8A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=
 Sof(C13A)=Sof(H13A)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C15A)=
 Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(H17D)=
 Sof(H17E)=Sof(H17F)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19A)=
 Sof(H19A)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C21A)=Sof(H21D)=
 Sof(H21E)=Sof(H21F)=1-FVAR(1)
 Sof(C7)=Sof(C8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(C13)=
 Sof(H13)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15A)=Sof(H15B)=
 Sof(H15C)=Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18)=
 Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20A)=Sof(H20B)=
 Sof(H20C)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=FVAR(1)
 Sof(O1A)=Sof(C73A)=Sof(H73D)=Sof(H73E)=Sof(H73F)=Sof(C74A)=Sof(H74C)=
 Sof(H74D)=Sof(C75A)=Sof(H75C)=Sof(H75D)=Sof(C76A)=Sof(H76D)=Sof(H76E)=
 Sof(H76F)=1-FVAR(2)
 Sof(O1)=Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=Sof(C74)=Sof(H74A)=Sof(H74B)=
 Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=FVAR(2)
 Sof(C72A)=Sof(H72D)=Sof(H72E)=Sof(H72F)=Sof(C71A)=Sof(H71D)=Sof(H71E)=
 Sof(H71F)=Sof(C70A)=Sof(H70A)=1-FVAR(3)
 Sof(C70)=Sof(H70)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(C72)=Sof(H72A)=
 Sof(H72B)=Sof(H72C)=FVAR(3)
8.a Ternary CH refined with riding coordinates:
 C49(H49), C52(H52), C55(H55), C64(H64), C67(H67), C70(H70), C11(H11),
 C13(H13), C16(H16), C19(H19), C28(H28), C31(H31), C34(H34), C9A(H9A),
 C11A(H11A), C13A(H13A), C16A(H16A), C19A(H19A), C70A(H70A)
8.b Secondary CH2 refined with riding coordinates:
 C74(H74A,H74B), C75(H75A,H75B), C74A(H74C,H74D), C75A(H75C,H75D)
8.c Me refined with riding coordinates:
 C73(H73A,H73B,H73C), C76(H76A,H76B,H76C), C73A(H73D,H73E,H73F), C76A(H76D,
 H76E,H76F)
8.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C39(H39), C40(H40), C41(H41), C45(H45), C47(H47),
 C60(H60), C62(H62), C9(H9), C24(H24), C26(H26)
8.e Idealised Me refined as rotating group:
 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), 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), C14A(H14D,H14E,H14F), C15A(H15D,H15E,
 H15F), C17A(H17D,H17E,H17F), C18A(H18D,H18E,H18F), C20A(H20D,H20E,H20F),
 C21A(H21D,H21E,H21F), C72A(H72D,H72E,H72F), C71A(H71D,H71E,H71F)
;
_shelx_res_checksum              69372
_shelx_hkl_checksum              80317
_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 2.038
_oxdiff_exptl_absorpt_empirical_full_min 0.717