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_1569573
_publ_section_title
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 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 Si2 Y, B C24 F20, 2[C6H14]'
_chemical_formula_sum            'C85 H110 B F20 N6 O Si2 Y'
_chemical_formula_weight         1767.68
_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     dual
_audit_creation_date             2023-04-08
_audit_creation_method
;
Olex2 1.5
(compiled 2023.02.24 svn.rf166f9f3 for OlexSys, GUI svn.r6725)
;
_audit_update_record
;
2023-04-08 deposited with the CCDC.	2023-07-17 downloaded from the CCDC.
;
_cell_angle_alpha                89.741(3)
_cell_angle_beta                 88.847(3)
_cell_angle_gamma                83.127(3)
_cell_formula_units_Z            2
_cell_length_a                   9.9761(18)
_cell_length_b                   20.274(4)
_cell_length_c                   21.922(4)
_cell_measurement_reflns_used    6106
_cell_measurement_temperature    100
_cell_measurement_theta_max      18.81
_cell_measurement_theta_min      2.18
_cell_volume                     4401.1(14)
_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      100.00
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.994
_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  0.1464
_diffrn_reflns_av_unetI/netI     0.2600
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            42343
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         1.858
_exptl_absorpt_coefficient_mu    0.780
_exptl_absorpt_correction_T_max  0.8620
_exptl_absorpt_correction_T_min  0.7129
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0843 before and 0.0582 after correction.
The Ratio of minimum to maximum transmission is 0.8270.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.334
_exptl_crystal_description       plate
_exptl_crystal_F_000             1844
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.619
_refine_diff_density_min         -0.723
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.843
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     959
_refine_ls_number_reflns         17925
_refine_ls_number_restraints     100
_refine_ls_restrained_S_all      0.842
_refine_ls_R_factor_all          0.1826
_refine_ls_R_factor_gt           0.0682
_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^)+(0.0455P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1118
_refine_ls_wR_factor_ref         0.1358
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7281
_reflns_number_total             17925
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01830j2.cif
_cod_data_source_block           XII2YR2cation
_cod_depositor_comments
'Adding full bibliography for 1569573--1569574.cif.'
_cod_original_cell_volume        4401.0(14)
_cod_database_code               1569573
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.912
_shelx_estimated_absorpt_t_min   0.872
_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
 C23-C22 \\sim C22-C21 \\sim C21-C23 \\sim C21A-C23A \\sim C23A-C22A \\sim
C22A-C23A
 with sigma of 0.005
 C20-C21 \\sim C20-C22 \\sim C20-C23 \\sim C20-C21A \\sim C20-C23A \\sim
C20-C22A
 with sigma of 0.005
 C61-C60 \\sim C61-C60A \\sim C57-C58 \\sim C57-C58A
 with sigma of 0.005
 C58-C59 \\sim C58A-C59A \\sim C59-C60 \\sim C59A-C60A
 with sigma of 0.005
 C56-C61 \\sim C56-C61A
 with sigma of 0.005
 C60A-C61A \\sim C60-C61
 with sigma of 0.005
 C61A-C61 \\sim C58A-C58
 with sigma of 0.005
 F10-C61 \\sim F10-C61A
 with sigma of 0.005
 C16A-C19A \\sim C16A-C17A \\sim C16A-C18A \\sim C16-C17 \\sim C16-C19 \\sim
C16-C18
 with sigma of 0.005
 C19A-C18A \\sim C18A-C17A \\sim C17A-C19A \\sim C17-C19 \\sim C19-C18 \\sim
C18-C17
 with sigma of 0.005
 C2-C16A \\sim C2-C16
 with sigma of 0.005
 Si1-C45 \\sim Si1-C43 \\sim Si1-C44 \\sim Si1A-C45A \\sim Si1A-C43A \\sim
Si1A-C44A
 with sigma of 0.005
 C45-C44 \\sim C44-C43 \\sim C43-C45 \\sim C45A-C44A \\sim C44A-C43A \\sim
C43A-C45A
 with sigma of 0.005
 Si1-C42 \\sim Si1-Si1A
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(C23) = Uanis(C22A)
Uanis(C22) = Uanis(C21A)
Uanis(C21) = Uanis(C23A)
Uanis(F9A) = Uanis(F9) = Uanis(F6) = Uanis(F8) = Uanis(F8A) = Uanis(F7) =
Uanis(F7A) = Uanis(F10)
Uanis(C59A) = Uanis(C59)
Uanis(C60) = Uanis(C60A)
Uanis(C58) = Uanis(C58A)
Uanis(C61) = Uanis(C61A)
Uanis(C16) = Uanis(C16A)
Uanis(C18) = Uanis(C17) = Uanis(C17A)
Uanis(C19) = Uanis(C18A) = Uanis(C19A)
Uanis(C45) = Uanis(C44A) = Uanis(C44)
Uanis(C43) = Uanis(C45A) = Uanis(C43A)
Uanis(Si1A) = Uanis(Si1)
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(C58A)=Sof(C59A)=Sof(C60A)=Sof(C61A)=1-FVAR(2)
 Sof(F7)=Sof(F8)=Sof(F9)=Sof(C58)=Sof(C59)=Sof(C60)=Sof(C61)=FVAR(2)
 Sof(C16A)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C18A)=Sof(H18D)=
 Sof(H18E)=Sof(H18F)=Sof(C19A)=Sof(H19D)=Sof(H19E)=Sof(H19F)=1-FVAR(3)
 Sof(C16)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18)=Sof(H18A)=Sof(H18B)=
 Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=FVAR(3)
 Sof(Si1A)=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(4)
 Sof(Si1)=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(4)
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), 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), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C),
 C17A(H17D,H17E,H17F), C18A(H18D,H18E,H18F), C19A(H19D,H19E,H19F), 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 176 electrons were 
found in a volume of 851\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2[C6H14] 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              52606
_shelx_fab_checksum              64427
_olex2_submission_special_instructions 'No special instructions were received'