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_1566946
_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         'C122 H184 O12 Tm4, C5 H12'
_chemical_formula_sum            'C127 H196 O12 Tm4'
_chemical_formula_weight         2590.55
_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             2021-12-01
_audit_creation_method
;
Olex2 1.5
(compiled 2021.11.18 svn.ra9532c28 for OlexSys, GUI svn.r6429)
;
_cell_angle_alpha                83.851(3)
_cell_angle_beta                 83.324(3)
_cell_angle_gamma                75.907(3)
_cell_formula_units_Z            2
_cell_length_a                   17.9662(18)
_cell_length_b                   18.3952(17)
_cell_length_c                   19.4830(18)
_cell_measurement_reflns_used    9917
_cell_measurement_temperature    150.00
_cell_measurement_theta_max      22.651
_cell_measurement_theta_min      2.317
_cell_volume                     6182.0(10)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.0997
_diffrn_reflns_av_unetI/netI     0.0889
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            116323
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.022
_diffrn_reflns_theta_min         1.657
_diffrn_source_current           31.0
_diffrn_source_power             1.705
_diffrn_source_voltage           55.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.898
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5933
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0977 before and 0.0719 after correction.
The Ratio of minimum to maximum transmission is 0.7957.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.392
_exptl_crystal_description       prism
_exptl_crystal_F_000             2660
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.736
_refine_diff_density_min         -0.860
_refine_diff_density_rms         0.150
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1344
_refine_ls_number_reflns         24333
_refine_ls_number_restraints     55
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0871
_refine_ls_R_factor_gt           0.0421
_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^)+(0.0187P)^2^+10.0976P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0760
_refine_ls_wR_factor_ref         0.0932
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16278
_reflns_number_total             24333
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc01798a4.cif
_cod_data_source_block           9b
_cod_database_code               1566946
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.760
_shelx_estimated_absorpt_t_min   0.406
_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
 C123-C124 = C124-C125 = C125-C126 = C126-C127
 1.52 with sigma of 0.02
 C123-C124 \\sim C124-C125 \\sim C125-C126 \\sim C126-C127
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C123 \\sim C124 \\sim C125 \\sim C126 \\sim C127: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C123, C124, C125, C126, C127
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Secondary CH2 refined with riding coordinates:
 C124(H12M,H12N), C125(H12O,H12P), C126(H12Q,H12R)
5.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C16(H16), C17(H17), C18(H18),
 C19(H19), C20(H20), C22(H22), C24(H24), C38(H38), C41(H41), C56(H56), C59(H59),
  C72(H72), C74(H74), C89(H89), C91(H91), C107(H107), C110(H110)
5.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C31(H31A,H31B,
 H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C36(H36A,
 H36B,H36C), C37(H37A,H37B,H37C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C),
 C46(H46A,H46B,H46C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,
 H50C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C61(H61A,
 H61B,H61C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C65(H65A,H65B,H65C),
 C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C69(H69A,H69B,H69C), C70(H70A,H70B,
 H70C), C71(H71A,H71B,H71C), C78(H78A,H78B,H78C), C79(H79A,H79B,H79C), C80(H80A,
 H80B,H80C), C82(H82A,H82B,H82C), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C),
 C86(H86A,H86B,H86C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C95(H95A,H95B,
 H95C), C96(H96A,H96B,H96C), C97(H97A,H97B,H97C), C99(H99A,H99B,H99C),
 C100(H10G,H10H,H10I), C101(H10D,H10E,H10F), C103(H10M,H10N,H10O), C104(H10A,
 H10B,H10C), C105(H10J,H10K,H10L), C112(H11A,H11B,H11C), C113(H11G,H11H,H11I),
 C114(H11D,H11E,H11F), C116(H11P,H11Q,H11R), C117(H11J,H11K,H11L), C118(H11M,
 H11N,H11O), C120(H12G,H12H,H12I), C121(H12A,H12B,H12C), C122(H12D,H12E,H12F),
 C123(H12J,H12K,H12L), C127(H12S,H12T,H12U)
;
_shelx_res_checksum              30077
_shelx_hkl_checksum              31116
_olex2_submission_special_instructions 'No special instructions were received'