Rare earth dialkyl cations and monoalkyl dications supported by a rigid neutral pincer ligand: synthesis and ethylene polymerization.
Vasanthakumar, Aathith; Price, Jeffrey S.; Emslie, David J. H.; Chemical science 14 (2023) 8514–8523; doi:10.1039/d3sc01830j

data_1569574
_publ_section_title
;
 Rare earth dialkyl cations and monoalkyl dications supported by a rigid
 neutral pincer ligand: synthesis and ethylene polymerization.
;
_journal_issue                   32
_journal_name_full               'Chemical science'
_journal_page_first              8514
_journal_page_last               8523
_journal_paper_doi               10.1039/d3sc01830j
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C49 H82 N6 O Sc Si2, B C24 F20, 2[C6H5F]'
_chemical_formula_sum            'C85 H92 B F22 N6 O Sc Si2'
_chemical_formula_weight         1743.59
_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     direct
_audit_creation_date             2023-03-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-03-08 deposited with the CCDC.	2023-07-17 downloaded from the CCDC.
;
_cell_angle_alpha                89.917(2)
_cell_angle_beta                 89.202(2)
_cell_angle_gamma                83.113(2)
_cell_formula_units_Z            2
_cell_length_a                   9.8595(12)
_cell_length_b                   20.303(3)
_cell_length_c                   21.959(3)
_cell_measurement_reflns_used    928
_cell_measurement_temperature    100
_cell_measurement_theta_max      22.59
_cell_measurement_theta_min      2.31
_cell_volume                     4363.6(10)
_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      100
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0575
_diffrn_reflns_av_unetI/netI     0.0499
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            112271
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.323
_diffrn_reflns_theta_min         1.371
_exptl_absorpt_coefficient_mu    0.206
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6759
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
'SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0533 before and 0.0429 after correction.
The Ratio of minimum to maximum transmission is 0.9064.
The \l/2 correction factor is 0.00150.'
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.327
_exptl_crystal_description       block
_exptl_crystal_F_000             1808
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.657
_refine_diff_density_min         -1.155
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     934
_refine_ls_number_reflns         21527
_refine_ls_number_restraints     61
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.1129
_refine_ls_R_factor_gt           0.0810
_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^)+(0.0509P)^2^+10.9354P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1777
_refine_ls_wR_factor_ref         0.1922
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15188
_reflns_number_total             21527
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01830j2.cif
_cod_data_source_block           XII2ScR2cation
_cod_depositor_comments
'Adding full bibliography for 1569573--1569574.cif.'
_cod_original_cell_volume        4363.5(9)
_cod_database_code               1569574
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.954
_shelx_estimated_absorpt_t_min   0.911
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C60A-C59A \\sim C60-C59
 with sigma of 0.005
 C60A-F9A \\sim C60-F9 \\sim C59A-F8A \\sim C59-F8 \\sim C61A-F10A \\sim
C61-F10 \\sim C58A-F7A \\sim C58-F7
 with sigma of 0.005
 C60A-C61A \\sim C60-C61
 with sigma of 0.005
 C58A-C59A \\sim C58-C59
 with sigma of 0.005
 Si1-C45A \\sim Si1-C43A \\sim Si1-C44A \\sim Si1-C43 \\sim Si1-C44 \\sim
Si1-C45
 with sigma of 0.005
 C45A-C43A \\sim C43A-C44A \\sim C44A-C45A \\sim C45-C43 \\sim C43-C44 \\sim
C44-C45
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(C23A) = Uanis(C22)
Uanis(C21) = Uanis(C22A)
Uanis(C23) = Uanis(C21A)
Uanis(F9A) = Uanis(F9) = Uanis(F8A) = Uanis(F8) = Uanis(F10) = Uanis(F10A) =
Uanis(F6) = Uanis(F7) = Uanis(F7A)
Uanis(C60) = Uanis(C60A) = Uanis(C59) = Uanis(C59A) = Uanis(C58) = Uanis(C61) =
Uanis(C61A) = Uanis(C58) = Uanis(C58A)
Uanis(C45A) = Uanis(C43) = Uanis(C43A)
Uanis(C44A) = Uanis(C45) = Uanis(C44)
4. Others
 Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C22A)=Sof(H22D)=Sof(H22E)=
 Sof(H22F)=Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=1-FVAR(1)
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(1)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F10A)=Sof(C58A)=Sof(C59A)=Sof(C60A)=Sof(C61A)=
 1-FVAR(2)
 Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(C58)=Sof(C59)=Sof(C60)=Sof(C61)=FVAR(2)
 Sof(C43A)=Sof(H43D)=Sof(H43E)=Sof(H43F)=Sof(C44A)=Sof(H44D)=Sof(H44E)=
 Sof(H44F)=Sof(C45A)=Sof(H45D)=Sof(H45E)=Sof(H45F)=1-FVAR(3)
 Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C27(H27), C30(H30), C36(H36), C39(H39)
5.b Secondary CH2 refined with riding coordinates:
 C42(H42A,H42B), C46(H46A,H46B)
5.c Me refined with riding coordinates:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C31(H31A,
 H31B,H31C), C32(H32A,H32B,H32C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C),
 C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C47(H47A,H47B,H47C), C48(H48A,H48B,
 H48C), C49(H49A,H49B,H49C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C),
 C21A(H21D,H21E,H21F), C22A(H22D,H22E,H22F), C23A(H23D,H23E,H23F), C43A(H43D,
 H43E,H43F), C44A(H44D,H44E,H44F), C45A(H45D,H45E,H45F)
5.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C6(H6), C8(H8), C25(H25), C26(H26), C34(H34), C35(H35)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 215 electrons were 
found in a volume of 772\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2[C6H5F] per Asymmetric Unit 
which account for 200 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              9246
_shelx_fab_checksum              79447
_olex2_submission_special_instructions 'No special instructions were received'