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_1572261
_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 La N2, 2(C7 H8)'
_chemical_formula_sum            'C86 H116 I La N2'
_chemical_formula_weight         1443.61
_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
_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                91.655(3)
_cell_angle_beta                 103.113(4)
_cell_angle_gamma                95.397(3)
_cell_formula_units_Z            2
_cell_length_a                   14.2175(7)
_cell_length_b                   14.8730(5)
_cell_length_c                   18.6528(7)
_cell_measurement_reflns_used    12799
_cell_measurement_temperature    99.95(13)
_cell_measurement_theta_max      28.4910
_cell_measurement_theta_min      3.6910
_cell_volume                     3819.3(3)
_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      99.95(13)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0714
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.846
_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    -47.00 -20.00   1.00   20.41    --  -18.77   0.00-120.00   27
  2  \w     12.00  38.00   1.00   20.41    --  -18.77   0.00-120.00   26
  3  \w    -11.00  25.00   1.00   20.41    --   20.49  77.00 -60.00   36
  4  \w    -10.00  40.00   1.00   20.41    --   20.49  77.00  60.00   50
  5  \w    -54.00  29.00   1.00   20.41    --   20.49 -19.00  30.00   83
  6  \w    -11.00  42.00   1.00   20.41    --   20.49  77.00 150.00   53
  7  \w    -49.00  39.00   1.00   20.41    --   20.49 -57.00-180.00   88
  8  \w    -48.00  42.00   1.00   20.41    --   20.49 -57.00 -60.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0452468000
_diffrn_orient_matrix_UB_12      -0.0095893000
_diffrn_orient_matrix_UB_13      0.0096315000
_diffrn_orient_matrix_UB_21      -0.0222770000
_diffrn_orient_matrix_UB_22      0.0262660000
_diffrn_orient_matrix_UB_23      -0.0289908000
_diffrn_orient_matrix_UB_31      -0.0104312000
_diffrn_orient_matrix_UB_32      -0.0389743000
_diffrn_orient_matrix_UB_33      -0.0243999000
_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  0.0360
_diffrn_reflns_av_unetI/netI     0.0649
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.846
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            32806
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.846
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.097
_diffrn_reflns_theta_min         3.326
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.007
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85899
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.255
_exptl_crystal_description       block
_exptl_crystal_F_000             1512
_exptl_crystal_size_max          0.191
_exptl_crystal_size_mid          0.133
_exptl_crystal_size_min          0.088
_refine_diff_density_max         1.035
_refine_diff_density_min         -0.774
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1038
_refine_ls_number_reflns         17374
_refine_ls_number_restraints     1278
_refine_ls_restrained_S_all      0.997
_refine_ls_R_factor_all          0.0619
_refine_ls_R_factor_gt           0.0381
_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^)+(0.0254P)^2^+1.1757P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0710
_refine_ls_wR_factor_ref         0.0804
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13307
_reflns_number_total             17374
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03005b2.cif
_cod_data_source_block           acapg2
_cod_depositor_comments
'Adding full bibliography for 1572261--1572275.cif.'
_cod_original_cell_volume        3819.2(3)
_cod_database_code               1572261
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'La N C H I'
_shelx_estimated_absorpt_t_max   0.917
_shelx_estimated_absorpt_t_min   0.831
_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
 N1-H1 \\sim N2-H2
 with sigma of 0.02
 C22-C6 \\sim C22A-C6
 with sigma of 0.02
 C23-C22 \\sim C23A-C22A \\sim C27A-C22A \\sim C27-C22 \\sim C27A-C26A \\sim
C27-C26 \\sim C26A-C25A ~
 C26-C25 \\sim C25A-C24A \\sim C25-C24 \\sim C24-C23 \\sim C24A-C23A
 with sigma of 0.02
 C73A-C79A \\sim C73A-C75A \\sim C73-C79 \\sim C73-C75
 with sigma of 0.02
 C73-C74 \\sim C73A-C74A
 with sigma of 0.02
 C78-C79 \\sim C78A-C79A \\sim C79A-C74A \\sim C77-C78 \\sim C76-C77 \\sim
C75A-C74A \\sim C75A-C76A ~
 C75-C76 \\sim C75-C74 \\sim C76A-C77A \\sim C77A-C78A \\sim C79-C74
 with sigma of 0.02
 C31-C25 \\sim C31A-C25A \\sim C32-C31 \\sim C33-C31 \\sim C33A-C31A \\sim
C32A-C31A \\sim C34-C27 ~
 C34A-C27A \\sim C36-C34 \\sim C36A-C34A \\sim C35-C34 \\sim C35A-C34A \\sim
C28A-C23A \\sim C28-C23 ~
 C30A-C28A \\sim C30-C28 \\sim C29-C28 \\sim C29A-C28A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C73 \\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C73A
\\sim C74A \\sim C75A \\sim C76A \\sim C77A \\sim C78A \\sim C79A: within 2A
with sigma of 0.02 and sigma for terminal atoms of 0.04 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 \\sim C22A
\\sim C23A \\sim C24A \\sim C25A \\sim C26A \\sim C27A \\sim C28A \\sim C29A
\\sim C30A \\sim C31A \\sim C32A \\sim C33A \\sim C34A \\sim C35A \\sim C36A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C73, C74, C75, C76, C77, C78, C79, C73A, C74A, C75A, C76A, C77A, C78A, C79A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33, C34, C35, C36,
 C22A, C23A, C24A, C25A, C26A, C27A, C28A, C29A, C30A, C31A, C32A, C33A, C34A,
 C35A, C36A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C22A)=Sof(C23A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=Sof(C26A)=Sof(H26A)=
 Sof(C27A)=Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(H29D)=Sof(H29E)=Sof(H29F)=
 Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C31A)=Sof(H31A)=Sof(C32A)=
 Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=
 Sof(C34A)=Sof(H34A)=Sof(C35A)=Sof(H35D)=Sof(H35E)=Sof(H35F)=Sof(C36A)=
 Sof(H36D)=Sof(H36E)=Sof(H36F)=1-FVAR(1)
 Sof(C22)=Sof(C23)=Sof(C24)=Sof(H24)=Sof(C25)=Sof(C26)=Sof(H26)=Sof(C27)=
 Sof(C28)=Sof(H28)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(C30)=Sof(H30A)=
 Sof(H30B)=Sof(H30C)=Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35A)=
 Sof(H35B)=Sof(H35C)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=FVAR(1)
 Sof(C73A)=Sof(H73D)=Sof(H73E)=Sof(H73F)=Sof(C74A)=Sof(C75A)=Sof(H75A)=
 Sof(C76A)=Sof(H76A)=Sof(C77A)=Sof(H77A)=Sof(C78A)=Sof(H78A)=Sof(C79A)=
 Sof(H79A)=1-FVAR(2)
 Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=Sof(C74)=Sof(C75)=Sof(H75)=Sof(C76)=
 Sof(H76)=Sof(C77)=Sof(H77)=Sof(C78)=Sof(H78)=Sof(C79)=Sof(H79)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C13(H13), C16(H16), C19(H19), C49(H49), C52(H52), C55(H55), C64(H64),
 C67(H67), C70(H70), C28(H28), C31(H31), C34(H34), C28A(H28A), C31A(H31A),
 C34A(H34A)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C9(H9), C11(H11), C39(H39), C40(H40), C41(H41),
 C45(H45), C47(H47), C60(H60), C62(H62), C24(H24), C26(H26), C24A(H24A),
 C26A(H26A), C82(H82), C83(H83), C84(H84), C85(H85), C86(H86), C75(H75),
 C76(H76), C77(H77), C78(H78), C79(H79), C75A(H75A), C76A(H76A), C77A(H77A),
 C78A(H78A), C79A(H79A)
6.c Fitted hexagon refined as free rotating group:
 C74A(C75A,C76A,C77A,C78A,C79A)
6.d 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), 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), C29(H29A,
 H29B,H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C),
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C29A(H29D,H29E,H29F), C30A(H30D,H30E,
 H30F), C32A(H32D,H32E,H32F), C33A(H33D,H33E,H33F), C35A(H35D,H35E,H35F),
 C36A(H36D,H36E,H36F), C80(H80A,H80B,H80C), C73(H73A,H73B,H73C), C73A(H73D,H73E,
 H73F)
;
_shelx_res_checksum              19863
_shelx_hkl_checksum              3650
_olex2_date_sample_data_collection 2023-02-02
_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 1.376
_oxdiff_exptl_absorpt_empirical_full_min 0.801