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_1566945
_publ_section_title
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 CO reductive oligomerization by a divalent thulium complex and
 CO2-induced functionalization
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_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC01798A
_journal_year                    2022
_chemical_formula_moiety         'C124 H188 O12 Tm4, C5 H12, 6[C5H12]'
_chemical_formula_sum            'C159 H272 O12 Tm4'
_chemical_formula_weight         3051.47
_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             2021-08-30
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_cell_angle_alpha                75.491(2)
_cell_angle_beta                 82.620(2)
_cell_angle_gamma                70.215(2)
_cell_formula_units_Z            2
_cell_length_a                   14.9953(7)
_cell_length_b                   17.8272(9)
_cell_length_c                   28.3472(16)
_cell_measurement_reflns_used    9901
_cell_measurement_temperature    150.02
_cell_measurement_theta_max      25.198
_cell_measurement_theta_min      2.229
_cell_volume                     6895.2(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      150.02
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.988
_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  0.0559
_diffrn_reflns_av_unetI/netI     0.0574
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            112106
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.333
_diffrn_reflns_theta_min         1.714
_diffrn_source_current           31.0
_diffrn_source_power             1.705
_diffrn_source_voltage           55.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.610
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.5596
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1099 before and 0.0558 after correction.
The Ratio of minimum to maximum transmission is 0.7506.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.470
_exptl_crystal_description       prism
_exptl_crystal_F_000             3196
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.38
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.343
_refine_diff_density_min         -0.717
_refine_diff_density_rms         0.115
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1364
_refine_ls_number_reflns         30786
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0531
_refine_ls_R_factor_gt           0.0350
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0353P)^2^+6.3459P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0801
_refine_ls_wR_factor_ref         0.0879
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23625
_reflns_number_total             30786
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc01798a4.cif
_cod_data_source_block           9a
_cod_database_code               1566945
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.818
_shelx_estimated_absorpt_t_min   0.422
_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. Uiso/Uaniso restraints and constraints
C125 \\sim C126 \\sim C127 \\sim C128 \\sim C129: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
3.a Secondary CH2 refined with riding coordinates:
 C126(H12T,H12U), C127(H12R,H12S), C128(H12P,H12Q)
3.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C9(H9), C10(H10), C17(H17), C18(H18), C20(H20), C21(H21),
 C24(H24), C26(H26), C40(H40), C43(H43), C57(H57), C59(H59), C75(H75), C77(H77),
  C93(H93), C95(H95), C108(H108), C110(H110)
3.c Idealised Me refined as rotating group:
 C11(H11P,H11Q,H11R), C22(H22A,H22B,H22C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,
 H35B,H35C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C),
 C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C50(H50A,H50B,
 H50C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C54(H54A,H54B,H54C), C55(H55A,
 H55B,H55C), C56(H56A,H56B,H56C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C),
 C65(H65A,H65B,H65C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C69(H69A,H69B,
 H69C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C73(H73A,H73B,H73C), C80(H80A,
 H80B,H80C), C81(H81A,H81B,H81C), C82(H82A,H82B,H82C), C84(H84A,H84B,H84C),
 C85(H85A,H85B,H85C), C86(H86A,H86B,H86C), C88(H88A,H88B,H88C), C89(H89A,H89B,
 H89C), C90(H90A,H90B,H90C), C97(H97A,H97B,H97C), C98(H98A,H98B,H98C), C99(H99A,
 H99B,H99C), C101(H10D,H10E,H10F), C102(H10J,H10K,H10L), C103(H10P,H10Q,H10R),
 C105(H10G,H10H,H10I), C106(H10A,H10B,H10C), C107(H10M,H10N,H10O), C114(H11J,
 H11K,H11L), C115(H11D,H11E,H11F), C116(H11M,H11N,H11O), C118(H11G,H11H,H11I),
 C119(H11A,H11B,H11C), C120(H12D,H12E,H12F), C122(H12G,H12H,H12I), C123(H12A,
 H12B,H12C), C124(H12J,H12K,H12L), C125(H12V,H12W,H12X), C129(H12M,H12N,H12O)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 538 electrons were 
found in a volume of 1207\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 6[C5H12] 
per Asymmetric Unit which account for 504 electrons per unit cell. 
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              51372
_shelx_hkl_checksum              86281
_shelx_fab_checksum              83821
_olex2_submission_special_instructions 'No special instructions were received'