CO reductive oligomerization by a divalent thulium complex and CO2-induced functionalization
Simler, Thomas; McCabe, Karl Nael; Maron, Laurent; Nocton, Grégory; Chemical Science  (2022) –; doi:10.1039/D2SC01798A

data_1566938
_publ_section_title
;
 CO reductive oligomerization by a divalent thulium complex and
 CO2-induced functionalization
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC01798A
_journal_year                    2022
_chemical_formula_moiety         'C34 H58 Tm'
_chemical_formula_sum            'C34 H58 Tm'
_chemical_formula_weight         635.73
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-06-07
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_cell_angle_alpha                90
_cell_angle_beta                 109.702(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.4715(9)
_cell_length_b                   18.0905(10)
_cell_length_c                   19.5394(10)
_cell_measurement_reflns_used    6745
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      23.163
_cell_measurement_theta_min      2.397
_cell_volume                     6479.8(6)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_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  0.0736
_diffrn_reflns_av_unetI/netI     0.0784
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            54376
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.791
_diffrn_reflns_theta_min         1.579
_diffrn_source_current           31.0
_diffrn_source_power             1.705
_diffrn_source_voltage           55.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.757
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6606
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0756 before and 0.0595 after correction.
The Ratio of minimum to maximum transmission is 0.8862.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.303
_exptl_crystal_description       plate
_exptl_crystal_F_000             2648
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.481
_refine_diff_density_min         -1.422
_refine_diff_density_rms         0.113
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.006
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     729
_refine_ls_number_reflns         13780
_refine_ls_number_restraints     246
_refine_ls_restrained_S_all      1.005
_refine_ls_R_factor_all          0.0821
_refine_ls_R_factor_gt           0.0406
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0225P)^2^+0.6867P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0722
_refine_ls_wR_factor_ref         0.0833
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8969
_reflns_number_total             13780
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc01798a4.cif
_cod_data_source_block           1
_cod_database_code               1566938
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.947
_shelx_estimated_absorpt_t_min   0.733
_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
 C65-C66A \\sim C65-C66B \\sim C65-C68A \\sim C65-C68B \\sim C65-C67A \\sim
C65-C67B
 with sigma of 0.02
 C31-C32A \\sim C31-C32B \\sim C31-C33A \\sim C31-C33B \\sim C31-C34A \\sim
C31-C34B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C65 \\sim C66A \\sim C67A \\sim C68A \\sim C66B \\sim C67B \\sim C68B: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C31 \\sim C32A \\sim C33A \\sim C34A \\sim C32B \\sim C33B \\sim C34B: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C65, C66A, C67A, C68A, C66B, C67B, C68B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C31, C32A, C33A, C34A, C32B, C33B, C34B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Sof(C66B)=Sof(H66D)=Sof(H66E)=Sof(H66F)=Sof(C67B)=Sof(H67D)=Sof(H67E)=
 Sof(H67F)=Sof(C68B)=Sof(H68D)=Sof(H68E)=Sof(H68F)=1-FVAR(1)
 Sof(C66A)=Sof(H66A)=Sof(H66B)=Sof(H66C)=Sof(C67A)=Sof(H67A)=Sof(H67B)=
 Sof(H67C)=Sof(C68A)=Sof(H68A)=Sof(H68B)=Sof(H68C)=FVAR(1)
 Sof(C32B)=Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C33B)=Sof(H33D)=Sof(H33E)=
 Sof(H33F)=Sof(C34B)=Sof(H34D)=Sof(H34E)=Sof(H34F)=1-FVAR(2)
 Sof(C32A)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C33A)=Sof(H33A)=Sof(H33B)=
 Sof(H33C)=Sof(C34A)=Sof(H34A)=Sof(H34B)=Sof(H34C)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5), C20(H20), C22(H22), C36(H36), C39(H39), C53(H53), C56(H56)
6.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), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C17(H17A,H17B,H17C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C32A(H32A,H32B,H32C), C33A(H33A,H33B,H33C), C34A(H34A,H34B,H34C), C32B(H32D,
 H32E,H32F), C33B(H33D,H33E,H33F), C34B(H34D,H34E,H34F), C41(H41A,H41B,H41C),
 C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C), C46(H46A,H46B,
 H46C), C47(H47A,H47B,H47C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,
 H51B,H51C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C),
 C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C66A(H66A,H66B,
 H66C), C67A(H67A,H67B,H67C), C68A(H68A,H68B,H68C), C66B(H66D,H66E,H66F),
 C67B(H67D,H67E,H67F), C68B(H68D,H68E,H68F)
;
_shelx_res_checksum              44458
_shelx_hkl_checksum              89088
_olex2_submission_special_instructions 'No special instructions were received'