Hydrodeoxygenative Cyclotetramerization of Carbon Monoxide by a Trinuclear Titanium Polyhydride Complex.
Hu, Shaowei; Shima, Takanori; Hou, Zhaomin; Journal of the American Chemical Society 142 (2020) 19889–19894; doi:10.1021/jacs.0c10403

data_4135354
_publ_section_title
;
 Hydrodeoxygenative Cyclotetramerization of Carbon Monoxide by a
 Trinuclear Titanium Polyhydride Complex.
;
_journal_issue                   47
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              19889
_journal_page_last               19894
_journal_paper_doi               10.1021/jacs.0c10403
_journal_volume                  142
_journal_year                    2020
_chemical_formula_moiety         'C41 H70 O5 Si3 Ti3'
_chemical_formula_sum            'C41 H70 O5 Si3 Ti3'
_chemical_formula_weight         870.94
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2020-08-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.8973(11)
_cell_length_b                   11.6751(6)
_cell_length_c                   19.2927(11)
_cell_measurement_reflns_used    9984
_cell_measurement_temperature    173.15
_cell_measurement_theta_max      32.67
_cell_measurement_theta_min      2.22
_cell_volume                     4707.0(4)
_computing_cell_refinement       'SAINT V8.40A (?, 2016)'
_computing_data_reduction        'SAINT V8.40A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      173.15
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'CMOS area detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0370
_diffrn_reflns_av_unetI/netI     0.0394
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            34914
_diffrn_reflns_point_group_measured_fraction_full 0.863
_diffrn_reflns_point_group_measured_fraction_max 0.863
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.500
_diffrn_reflns_theta_min         2.039
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.611
_exptl_absorpt_correction_T_max  0.7467
_exptl_absorpt_correction_T_min  0.5869
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1736 before and 0.0706 after correction.
The Ratio of minimum to maximum transmission is 0.7860.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.229
_exptl_crystal_description       block
_exptl_crystal_F_000             1856
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.542
_refine_diff_density_min         -1.476
_refine_diff_density_rms         0.103
_refine_ls_abs_structure_details
;
 Flack x determined using 3236 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.012(9)
_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     455
_refine_ls_number_reflns         9307
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0613
_refine_ls_R_factor_gt           0.0587
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0966P)^2^+6.0354P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1585
_refine_ls_wR_factor_ref         0.1611
_reflns_Friedel_coverage         0.681
_reflns_Friedel_fraction_full    0.722
_reflns_Friedel_fraction_max     0.721
_reflns_number_gt                8852
_reflns_number_total             9307
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c10403_si_005.cif
_cod_data_source_block           29026ts_0ma
_cod_depositor_comments
'Adding full bibliography for 4135351--4135354.cif.'
_cod_database_code               4135354
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.838
_shelx_estimated_absorpt_t_min   0.792
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C26) = Uanis(C27) = Uanis(C28) = Uanis(C29) = Uanis(C25)
Uanis(C30) = Uanis(C31) = Uanis(C32) = Uanis(C33) = Uanis(Si3)
Uanis(C34) = Uanis(C35) = Uanis(C36)
Uanis(C35A) = Uanis(C34A) = Uanis(C36A)
Uanis(C25A) = Uanis(C26A) = Uanis(C27A) = Uanis(C28A) = Uanis(C29A)
Uanis(C30A) = Uanis(C31A) = Uanis(C32A) = Uanis(C33A) = Uanis(Si3A)
Uanis(C22) = Uanis(C23) = Uanis(C22A) = Uanis(C23A)
3. Others
 Fixed Sof: C22(0.4) H22A(0.4) H22B(0.4) H22C(0.4) C23(0.6) H23A(0.6)
 H23B(0.6) H23C(0.6) C26(0.6) Si3(0.6) C25(0.6) C27(0.6) C28(0.6) C29(0.6)
 C30(0.6) C36(0.6) H30A(0.6) H30B(0.6) H30C(0.6) C31(0.6) H31A(0.6) H31B(0.6)
 H31C(0.6) C32(0.6) H32A(0.6) H32B(0.6) H32C(0.6) C33(0.6) H33A(0.6) H33B(0.6)
 H33C(0.6) C34(0.6) H34A(0.6) H34B(0.6) H34C(0.6) C35(0.6) H35A(0.6) H35B(0.6)
 H35C(0.6) H36A(0.6) H36B(0.6) H36C(0.6) C22A(0.6) H22D(0.6) H22E(0.6)
 H22F(0.6) C23A(0.4) H23D(0.4) H23E(0.4) H23F(0.4) C25A(0.4) Si3A(0.4)
 C26A(0.4) C27A(0.4) C28A(0.4) C29A(0.4) C30A(0.4) C36A(0.4) H30D(0.4)
 H30E(0.4) H30F(0.4) C31A(0.4) H31D(0.4) H31E(0.4) H31F(0.4) C32A(0.4)
 H32D(0.4) H32E(0.4) H32F(0.4) C33A(0.4) H33D(0.4) H33E(0.4) H33F(0.4)
 C34A(0.4) H34D(0.4) H34E(0.4) H34F(0.4) C35A(0.4) H35D(0.4) H35E(0.4)
 H35F(0.4) H36D(0.4) H36E(0.4) H36F(0.4)
4.a Everything fixed:
 H30A, H30B, H30C, H31A, H31B, H31C, H32A, H32B, H32C, H33A, H33B, H33C, H34A,
 H34B, H34C, H35A, H35B, H35C, H36A, H36B, H36C, H30D, H30E, H30F, H31D, H31E,
 H31F, H32D, H32E, H32F, H33D, H33E, H33F, H34D, H34E, H34F, H35D, H35E, H35F,
 H36D, H36E, H36F
4.b :
 C26(Si3,C25,C27,C28,C29,C30), C25A(Si3A,C26A,C27A,C28A,C29A,C30A)
4.c Secondary CH2 refined with riding coordinates:
 C38(H38A,H38B), C39(H39A,H39B)
4.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C37(H37A,H37B,
 H37C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C),
 C22A(H22D,H22E,H22F), C23A(H23D,H23E,H23F)
;
_shelx_res_checksum              84738
_shelx_hkl_checksum              89748
_olex2_submission_special_instructions 'No special instructions were received'