New conformationally flexible and recyclable aryl iodine catalysts from an inexpensive chiral source for asymmetric oxidations
Zhou, Hai-Jie; Yao, Yi-Ping; Zhang, Tonghui; Chen, Biao; Wang, Xu; Zhao, Hang; Zeng, Jie; Chen, Jian-Ai; Xiao, Xiao; Chen, Fen-Er; Green Chemistry 25 (2023) 10447–10457; doi:10.1039/D3GC02429F

data_7247574
_publ_section_title
;
 New conformationally flexible and recyclable aryl iodine catalysts from
 an inexpensive chiral source for asymmetric oxidations
;
_journal_issue                   24
_journal_name_full               'Green Chemistry'
_journal_page_first              10447
_journal_page_last               10457
_journal_paper_doi               10.1039/D3GC02429F
_journal_volume                  25
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C56 H60 I N4 O8 Si2'
_chemical_formula_sum            'C56 H61 I N4 O8 Si2'
_chemical_formula_weight         1101.16
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-01-04
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-01-14 deposited with the CCDC.	2023-10-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.216(9)
_cell_length_b                   13.252(2)
_cell_length_c                   14.528(3)
_cell_measurement_reflns_used    9442
_cell_measurement_temperature    170.00
_cell_measurement_theta_max      26.276
_cell_measurement_theta_min      2.535
_cell_volume                     5432(2)
_computing_cell_refinement       'SAINT V8.40B (Bruker Nano, Inc., 2019)'
_computing_data_collection       'Bruker Instrument Service vV6.2.14'
_computing_data_reduction        'SAINT V8.40B (Bruker Nano, Inc., 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      170.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'zju Bruker D8 VENTURE'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0513
_diffrn_reflns_av_unetI/netI     0.0406
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -38
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            94001
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.159
_diffrn_reflns_theta_min         2.012
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.690
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.6634
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0934 before and 0.0664 after correction.
The Ratio of minimum to maximum transmission is 0.8893.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.346
_exptl_crystal_description       block
_exptl_crystal_F_000             2280
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.737
_refine_diff_density_min         -0.771
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 4425 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.013(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     811
_refine_ls_number_reflns         15884
_refine_ls_number_restraints     585
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0724
_refine_ls_R_factor_gt           0.0439
_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^)+(0.0543P)^2^+2.2604P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1027
_refine_ls_wR_factor_ref         0.1185
_reflns_Friedel_coverage         0.813
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.976
_reflns_number_gt                11790
_reflns_number_total             15884
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3gc02429f2.cif
_cod_data_source_block           mo_230103_zhj_nh2_0m
_cod_depositor_comments
'Adding full bibliography for 7247573--7247574.cif.'
_cod_database_code               7247574
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.820
_shelx_estimated_absorpt_t_min   0.733
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 H3A-H1A_$1
 2.2 with sigma of 0.001
 C7-C26 \\sim C7-C26A
 with sigma of 0.02
 C31-C26 \\sim C31A-C26A
 with sigma of 0.02
 C31-C30 \\sim C31A-C30A
 with sigma of 0.02
 O3-N2 \\sim O3A-N2A
 with sigma of 0.02
 C7-C31 \\sim C7-C31A
 with sigma of 0.04
 C27-C29 \\sim C27A-C29A
 with sigma of 0.04
 C31-C27 \\sim C31A-C27A
 with sigma of 0.04
 C31-C29 \\sim C31A-C29A
 with sigma of 0.04
 C26-C27 \\sim C26A-C27A
 with sigma of 0.02
 C30-C29 \\sim C30A-C29A
 with sigma of 0.02
 C26-C28 \\sim C26A-C28A
 with sigma of 0.04
 C30-C28 \\sim C30A-C28A
 with sigma of 0.04
 C27-C28 \\sim C27A-C28A
 with sigma of 0.02
 C29-C28 \\sim C29A-C28A
 with sigma of 0.02
 C29-N2 \\sim C29A-N2A
 with sigma of 0.02
 C26-C30 \\sim C26A-C30A
 with sigma of 0.04
 O2-N2 \\sim O2A-N2A
 with sigma of 0.02
 C30-N2 \\sim C30A-N2A
 with sigma of 0.04
 C29-O2 \\sim C29A-O2A
 with sigma of 0.04
 C7-C27 \\sim C7-C27A
 with sigma of 0.04
 O3-C29 \\sim O3A-C29A
 with sigma of 0.04
 O3-O2 \\sim O3A-O2A
 with sigma of 0.04
 C28-N2 \\sim C28A-N2A
 with sigma of 0.04
 C39-C43 \\sim C39A-C43A
 with sigma of 0.04
 C39-C40 \\sim C39A-C40A
 with sigma of 0.02
 C39-C44 \\sim C39A-C44A
 with sigma of 0.02
 Si2-C39 \\sim Si2-C39A
 with sigma of 0.02
 Si2-C44 \\sim Si2-C44A
 with sigma of 0.04
 C40-C42 \\sim C40A-C42A
 with sigma of 0.04
 C41-C42 \\sim C41A-C42A
 with sigma of 0.02
 C40-C41 \\sim C40A-C41A
 with sigma of 0.02
 Si2-C40 \\sim Si2-C40A
 with sigma of 0.04
 C39-C41 \\sim C39A-C41A
 with sigma of 0.04
 C40-C44 \\sim C40A-C44A
 with sigma of 0.04
 C41-C43 \\sim C41A-C43A
 with sigma of 0.04
 C42-C43 \\sim C42A-C43A
 with sigma of 0.02
 C42-C44 \\sim C42A-C44A
 with sigma of 0.04
 C43-C44 \\sim C43A-C44A
 with sigma of 0.02
 O8-N4 \\sim O8A-N4A
 with sigma of 0.02
 C54-O7 \\sim C54-O7A
 with sigma of 0.04
 O8-O7 \\sim O8A-O7A
 with sigma of 0.04
 N4-O7 \\sim N4A-O7A
 with sigma of 0.02
 N4-C54 \\sim N4A-C54
 with sigma of 0.02
 O8-C54 \\sim O8A-C54
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C7 \\sim O2 \\sim O3 \\sim N2 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30
\\sim C31 \\sim O2A \\sim O3A \\sim N2A \\sim C26A \\sim C27A \\sim C28A \\sim
C29A \\sim C30A \\sim C31A: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 2A
Si2 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C39A
\\sim C40A \\sim C41A \\sim C42A \\sim C43A \\sim C44A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C54 \\sim O7 \\sim O8 \\sim N4 \\sim O7A \\sim O8A \\sim N4A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(O2A)=Sof(O3A)=Sof(N2A)=Sof(C26A)=Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(H28A)=
 Sof(C29A)=Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31A)=1-FVAR(1)
 Sof(O2)=Sof(O3)=Sof(N2)=Sof(C26)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28)=Sof(C29)=
 Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31)=FVAR(1)
 Sof(C39A)=Sof(C40A)=Sof(H40A)=Sof(C41A)=Sof(H41A)=Sof(C42A)=Sof(H42A)=
 Sof(C43A)=Sof(H43A)=Sof(C44A)=Sof(H44A)=1-FVAR(2)
 Sof(C39)=Sof(C40)=Sof(H40)=Sof(C41)=Sof(H41)=Sof(C42)=Sof(H42)=Sof(C43)=
 Sof(H43)=Sof(C44)=Sof(H44)=FVAR(2)
 Sof(O7A)=Sof(O8A)=Sof(N4A)=1-FVAR(3)
 Sof(O7)=Sof(O8)=Sof(N4)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C8(H8), C32(H32), C33(H33)
5.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C34(H34A,H34B)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19),
 C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C46(H46), C47(H47), C48(H48),
  C49(H49), C50(H50), C52(H52), C53(H53), C55(H55), C56(H56), C27(H27),
 C28(H28), C30(H30), C31(H31), C40(H40), C41(H41), C42(H42), C43(H43), C44(H44),
  C27A(H27A), C28A(H28A), C30A(H30A), C31A(H31A), C40A(H40A), C41A(H41A),
 C42A(H42A), C43A(H43A), C44A(H44A)
5.d X=CH2 refined with riding coordinates:
 N1(H1A,H1B), N3(H3A,H3B)
5.e Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C36(H36A,H36B,
 H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C)
;
_shelx_res_checksum              50889
_olex2_submission_special_instructions 'No special instructions were received'