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_1570788
_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 Nd'
_chemical_formula_sum            'C39 H63 Nd'
_chemical_formula_weight         676.13
_chemical_name_systematic        Nd(Cptt)3
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 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                90
_cell_angle_beta                 104.394(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.7938(3)
_cell_length_b                   19.4422(5)
_cell_length_c                   17.8596(5)
_cell_measurement_reflns_used    6725
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      27.4140
_cell_measurement_theta_min      3.6830
_cell_volume                     3630.28(18)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_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 0.998
_diffrn_measured_fraction_theta_max 0.842
_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     -2.00  91.00   1.00    1.00    --   18.86  37.00  30.00   93
  2  \w     33.00  82.00   1.00    1.00    --   18.86  37.00 120.00   49
  3  \w     34.00  60.00   1.00    1.00    --   18.86 -99.00   0.00   26
  4  \w    -20.00  61.00   1.00    1.00    --   18.86 -99.00 -90.00   81
;
_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  0.0422
_diffrn_reflns_av_unetI/netI     0.0703
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.842
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            18314
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.842
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.192
_diffrn_reflns_theta_min         3.357
_exptl_absorpt_coefficient_mu    1.453
_exptl_absorpt_correction_T_max  0.933
_exptl_absorpt_correction_T_min  0.906
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.237
_exptl_crystal_description       block
_exptl_crystal_F_000             1428
_exptl_crystal_recrystallization_method 'crystallised from hexane at -30 deg'
_exptl_crystal_size_max          0.442
_exptl_crystal_size_mid          0.309
_exptl_crystal_size_min          0.243
_refine_diff_density_max         1.736
_refine_diff_density_min         -0.441
_refine_diff_density_rms         0.115
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     379
_refine_ls_number_reflns         8287
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0650
_refine_ls_R_factor_gt           0.0451
_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^)+(0.0295P)^2^+1.9467P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0856
_refine_ls_wR_factor_ref         0.0968
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6434
_reflns_number_total             8287
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06175b2.cif
_cod_data_source_block           1-Nd
_cod_depositor_comments
'Adding full bibliography for 1570788--1570789.cif.'
_cod_database_code               1570788
_manchester_internal_diff_code   adpm387
_manchester_internal_coll_client FO/JJL/DPM
_manchester_internal_coll_date   26/10/2016
_manchester_internal_process_date 26/10/2016
_manchester_internal_process_user FO
_manchester_internal_solution_date 26/10/2016
_manchester_internal_solution_user FO
_manchester_internal_refinement_date 24/08/20
_manchester_internal_refinement_user FO/PJC
_manchester_internal_validation_date 24/08/20
_manchester_internal_validation_user FO/PJC
_manchester_internal_archive_date 22/06/2023
_manchester_internal_archive_user FO
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.719
_shelx_estimated_absorpt_t_min   0.566
_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.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C15(H15), C17(H17), C18(H18), C28(H28), C30(H30),
 C31(H31)
2.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), 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)
;
_shelx_res_checksum              86045
_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
;