Metal-carbon bonding in early lanthanide substituted cyclopentadienyl complexes probed by pulsed EPR spectroscopy.
Nodaraki, Lydia E.; Liu, Jingjing; Ariciu, Ana-Maria; Ortu, Fabrizio; Oakley, Meagan S.; Birnoschi, Letitia; Gransbury, Gemma K.; Cobb, Philip J.; Emerson-King, Jack; Chilton, Nicholas F.; Mills, David P.; McInnes, Eric J. L.; Tuna, Floriana; Chemical science 15 (2024) 3003–3010; doi:10.1039/d3sc06175b

data_1570789
_publ_section_title
;
 Metal-carbon bonding in early lanthanide substituted cyclopentadienyl
 complexes probed by pulsed EPR spectroscopy.
;
_journal_issue                   8
_journal_name_full               'Chemical science'
_journal_page_first              3003
_journal_page_last               3010
_journal_paper_doi               10.1039/d3sc06175b
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C39 H63 La'
_chemical_formula_sum            'C39 H63 La'
_chemical_formula_weight         670.80
_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   geom
_atom_sites_solution_primary     heavy
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-06-22
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-06-22 deposited with the CCDC.	2024-01-12 downloaded from the CCDC.
;
_cell_angle_alpha                83.299(5)
_cell_angle_beta                 77.365(6)
_cell_angle_gamma                74.640(5)
_cell_formula_units_Z            4
_cell_length_a                   10.7001(8)
_cell_length_b                   18.4935(9)
_cell_length_c                   19.7113(13)
_cell_measurement_reflns_used    6487
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      27.5880
_cell_measurement_theta_min      3.6970
_cell_volume                     3662.9(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      150(2)
_diffrn_detector_area_resol_mean 8.0714
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details
;
  1 omega  -11.00   91.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -       20.1807   77.0000  120.0000 102

  2 omega   18.00   64.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -       20.1807  -99.0000  -90.0000 46

  3 omega  -26.00   92.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -       20.1807   19.0000  -60.0000 118

  4 omega   -1.00   79.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -       20.1807   57.0000   30.0000 80
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0497
_diffrn_reflns_av_unetI/netI     0.1144
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            21450
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.349
_diffrn_reflns_theta_min         3.273
_exptl_absorpt_coefficient_mu    1.189
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88006
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.216
_exptl_crystal_description       block
_exptl_crystal_F_000             1416
_exptl_crystal_size_max          0.0678
_exptl_crystal_size_mid          0.0646
_exptl_crystal_size_min          0.047
_refine_diff_density_max         1.057
_refine_diff_density_min         -1.015
_refine_diff_density_rms         0.113
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.996
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     788
_refine_ls_number_reflns         13282
_refine_ls_number_restraints     78
_refine_ls_restrained_S_all      0.997
_refine_ls_R_factor_all          0.0950
_refine_ls_R_factor_gt           0.0559
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0155P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0809
_refine_ls_wR_factor_ref         0.0926
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9013
_reflns_number_total             13282
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06175b2.cif
_cod_data_source_block           1-La
_cod_depositor_comments
'Adding full bibliography for 1570788--1570789.cif.'
_cod_original_cell_volume        3663.0(4)
_cod_database_code               1570789
_manchester_internal_diff_code   adpm426
_manchester_internal_coll_client JJL/DPM
_manchester_internal_coll_user   FO
_manchester_internal_coll_date   14/4/17
_manchester_internal_process_date 2/5/17
_manchester_internal_process_user JJL
_manchester_internal_solution_date 9/5/17
_manchester_internal_solution_user JJL
_manchester_internal_refinement_date 22/5/17
_manchester_internal_refinement_user JJL
_manchester_internal_validation_date 24/08/20
_manchester_internal_validation_user PJC
_manchester_internal_archive_date 22/06/2023
_manchester_internal_archive_user FO
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.946
_shelx_estimated_absorpt_t_min   0.924
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C8A-C6 = C8-C6 = C7A-C6 = C7-C6 = C9A-C6 = C9-C6
 1.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C6 \\sim C7 \\sim C7A \\sim C8 \\sim C8A \\sim C9 \\sim C9A \\sim C12: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=
 Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=1-FVAR(1)
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=
 Sof(H9A)=Sof(H9B)=Sof(H9C)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C15(H15), C16(H16), C18(H18), C27(H27), C28(H28),
 C30(H30), C41(H41), C42(H42), C44(H44), C54(H54), C56(H56), C57(H57), C67(H67),
  C69(H69), C70(H70)
5.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C7A(H7AA,H7AB,H7AC), C8(H8A,H8B,H8C), C8A(H8AA,H8AB,H8AC),
 C9(H9A,H9B,H9C), C9A(H9AA,H9AB,H9AC), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
  C13(H13A,H13B,H13C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C33(H33A,
 H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C37(H37A,H37B,H37C),
 C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C46(H46A,H46B,H46C), C47(H47A,H47B,
 H47C), C48(H48A,H48B,H48C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C52(H52A,
 H52B,H52C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C61(H61A,H61B,H61C),
 C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C72(H72A,H72B,
 H72C), C73(H73A,H73B,H73C), C74(H74A,H74B,H74C), C76(H76A,H76B,H76C), C77(H77A,
 H77B,H77C), C78(H78A,H78B,H78C)
;
_shelx_res_checksum              24618
_olex2_submission_special_instructions 'No special instructions were received'