Cyclopentadienyl lanthanide borohydrides derived from the unsubstituted cyclopentadienyl ligand. Unprecedented structural diversity and ε-caprolactone polymerization
Bardonov, Daniil A.; Komarov, Pavel D.; Sadrtdinova, Guzelia I.; Besprozvannyh, Viktoria K.; Lyssenko, Konstantin A.; Gudovannyy, Alexei O.; Nifant'ev, Ilya E.; Minyaev, Mikhail E.; Roitershtein, Dmitrii M.; Inorganica Chimica Acta 529 (2022) 120638–; doi:10.1016/j.ica.2021.120638

data_1565997
_publ_section_title
;
 Cyclopentadienyl lanthanide borohydrides derived from the unsubstituted
 cyclopentadienyl ligand. Unprecedented structural diversity and
 \e-caprolactone polymerization
;
_journal_name_full               'Inorganica Chimica Acta'
_journal_page_first              120638
_journal_paper_doi               10.1016/j.ica.2021.120638
_journal_volume                  529
_journal_year                    2022
_chemical_formula_moiety         'C13 H29 B2 Nd O2'
_chemical_formula_sum            'C13 H29 B2 Nd O2'
_chemical_formula_weight         383.22
_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
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90
_cell_angle_beta                 109.255(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.1747(3)
_cell_length_b                   7.94590(10)
_cell_length_c                   15.6507(3)
_cell_measurement_reflns_used    18529
_cell_measurement_temperature    249.99(10)
_cell_measurement_theta_max      36.0380
_cell_measurement_theta_min      2.6430
_cell_volume                     1781.54(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      249.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.967
_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    -54.00  32.00   0.40   13.00    --   17.87 -61.00   5.00  215
  2  \w      3.00  89.00   0.40   13.00    --   17.87  61.00 144.00  215
  3  \w    -56.00   4.00   0.40   13.00    --   17.87 -19.00  60.00  150
  4  \w    -56.00   4.00   0.40   13.00    --   17.87 -19.00-150.00  150
  5  \w     42.00  90.00   0.40   13.00    --   17.87 178.00   0.00  120
  6  \w    -89.00 -45.80   0.40   13.00    --  -17.72 -57.00-120.00  108
  7  \w      7.00  89.00   0.40   13.00    --   17.87  38.00  60.00  205
  8  \w    -56.00   4.00   0.40   13.00    --   17.87 -19.00 120.00  150
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0280574000
_diffrn_orient_matrix_UB_12      -0.0168436000
_diffrn_orient_matrix_UB_13      0.0273763000
_diffrn_orient_matrix_UB_21      0.0326847000
_diffrn_orient_matrix_UB_22      -0.0613062000
_diffrn_orient_matrix_UB_23      0.0242718000
_diffrn_orient_matrix_UB_31      0.0244112000
_diffrn_orient_matrix_UB_32      0.0626613000
_diffrn_orient_matrix_UB_33      0.0310819000
_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  0.0236
_diffrn_reflns_av_unetI/netI     0.0177
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            36553
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         34.992
_diffrn_reflns_theta_min         2.653
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.907
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52589
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.117a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'pale blue'
_exptl_crystal_density_diffrn    1.429
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             772
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.136
_refine_diff_density_min         -0.571
_refine_diff_density_rms         0.058
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     290
_refine_ls_number_reflns         7584
_refine_ls_number_restraints     306
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0365
_refine_ls_R_factor_gt           0.0264
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0316P)^2^+0.3963P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0675
_refine_ls_wR_factor_ref         0.0705
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                6000
_reflns_number_total             7584
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ICA-2022-529-120638.cif
_cod_data_source_block           Nd4
_cod_database_code               1565997
_chemical_oxdiff_formula         'Nd B2 C14 H21 O2'
_chemical_oxdiff_usercomment     Nd5
_shelx_estimated_absorpt_t_max   0.780
_shelx_estimated_absorpt_t_min   0.608
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     33.07
_olex2_refinement_description
;
1. Fixed Uiso
 At 1 times of:
  All H(H) groups, All H(H,H) groups
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 B1-H1A \\sim B1-H1B \\sim B1-H1C \\sim B1-H1D
 with sigma of 0.01
 H1A-H1B \\sim H1A-H1C \\sim H1A-H1D \\sim H1B-H1C \\sim H1B-H1D \\sim H1C-H1D
 with sigma of 0.05
 B2-H2A \\sim B2-H2B \\sim B2-H2C \\sim B2-H2D
 with sigma of 0.01
 H2A-H2B \\sim H2A-H2C \\sim H2A-H2D \\sim H2B-H2C \\sim H2B-H2D \\sim H2C-H2D
 with sigma of 0.05
 Nd1-O1A \\sim Nd1-O1B \\sim Nd1-O1C \\sim Nd1-O1D
 with sigma of 0.003
 O1A-C6A \\sim O1A-C9A \\sim O1B-C6B \\sim O1B-C9B \\sim O1C-C6C \\sim O1C-C9C
\\sim O1D-C6D \\sim O1D-C9D
 with sigma of 0.003
 C6A-C7A \\sim C8A-C9A \\sim C6B-C7B \\sim C8B-C9B \\sim C6C-C7C \\sim C8C-C9C
\\sim C6D-C7D \\sim C8D-C9D
 \\sim C7A-C8A \\sim C7B-C8B \\sim C7C-C8C \\sim C7D-C8D
 with sigma of 0.003
 C6A-C8A \\sim C7A-C9A \\sim C6B-C8B \\sim C7B-C9B \\sim C6C-C8C \\sim C7C-C9C
\\sim C6D-C8D \\sim C7D-C9D
 with sigma of 0.03
 Nd1-O2A \\sim Nd1-O2B \\sim Nd1-O2C \\sim Nd1-O2D
 with sigma of 0.003
 O2A-C10A \\sim O2A-C13A \\sim O2B-C10B \\sim O2B-C13B \\sim O2C-C10C \\sim
O2C-C13C \\sim O2D-C10D ~
 O2D-C13D
 with sigma of 0.003
 C10A-C11A \\sim C12A-C13A \\sim C10B-C11B \\sim C12B-C13B \\sim C10C-C11C
\\sim C12C-C13C \\sim C10D-
 C11D \\sim C12D-C13D \\sim C11A-C12A \\sim C11B-C12B \\sim C11C-C12C \\sim
C11D-C12D
 with sigma of 0.003
 C10A-C12A \\sim C11A-C13A \\sim C10B-C12B \\sim C11B-C13B \\sim C10C-C12C
\\sim C11C-C13C \\sim C10D-
 C12D \\sim C11D-C13D
 with sigma of 0.03
3. Uiso/Uaniso restraints and constraints
Uanis(C9A) \\sim Ueq: with sigma of 0.008 and sigma for terminal atoms of 0.016
Uanis(O1A) = Uanis(O1B) = Uanis(O1C) = Uanis(O1D)
Uanis(C6A) = Uanis(C6B) = Uanis(C6C) = Uanis(C6D)
Uanis(C7A) = Uanis(C7B) = Uanis(C7C) = Uanis(C7D)
Uanis(C8A) = Uanis(C8B) = Uanis(C8C) = Uanis(C8D)
Uanis(C9A) = Uanis(C9B) = Uanis(C9C) = Uanis(C9D)
Uanis(O2A) = Uanis(O2B) = Uanis(O2C) = Uanis(O2D)
Uanis(C10A) = Uanis(C10B) = Uanis(C10C) = Uanis(C10D)
Uanis(C11A) = Uanis(C11B) = Uanis(C11C) = Uanis(C11D)
Uanis(C12A) = Uanis(C12B) = Uanis(C12C) = Uanis(C12D)
Uanis(C13A) = Uanis(C13B) = Uanis(C13C) = Uanis(C13D)
;