Intramolecular Photochemical [2+1]-Cycloadditions of Nucleophilic Siloxy Carbenes
Bunyamin, Amanda; Hua, Carol; Polyzos, Anastasios; Priebbenow, Daniel; Chemical Science  (2022) –; doi:10.1039/D2SC00203E

data_1566423
_publ_section_title
;
 Intramolecular Photochemical [2+1]-Cycloadditions of Nucleophilic Siloxy
 Carbenes&#x00A0;
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC00203E
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H29 N O5 S Si'
_chemical_formula_sum            'C23 H29 N O5 S Si'
_chemical_formula_weight         459.62
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-08-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-11-14 deposited with the CCDC.	2022-02-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.61(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.9200(18)
_cell_length_b                   18.338(4)
_cell_length_c                   14.723(3)
_cell_measurement_reflns_used    2214
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.68
_cell_measurement_theta_min      2.7
_cell_volume                     2374.5(9)
_computing_cell_refinement       'XDS (Kabsch, 2010)'
_computing_data_collection       'AS QEGUI'
_computing_data_reduction        'XDS (Kabsch, 2010)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 13.3
_diffrn_measured_fraction_theta_full 0.939
_diffrn_measured_fraction_theta_max 0.756
_diffrn_measurement_device_type  'MX2 Beamline Australian Synchrotron'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  'Silicon Double Crystal'
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0702
_diffrn_reflns_av_unetI/netI     0.0688
_diffrn_reflns_Laue_measured_fraction_full 0.939
_diffrn_reflns_Laue_measured_fraction_max 0.756
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            36729
_diffrn_reflns_point_group_measured_fraction_full 0.926
_diffrn_reflns_point_group_measured_fraction_max 0.741
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.088
_diffrn_reflns_theta_min         1.789
_diffrn_source                   'MX2 Beamline Australian Synchrotron'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.220
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.286
_exptl_crystal_description       block
_exptl_crystal_F_000             976
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.491
_refine_diff_density_min         -0.539
_refine_diff_density_rms         0.098
_refine_ls_abs_structure_details
;
 Flack x determined using 5109 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     571
_refine_ls_number_reflns         12315
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0500
_refine_ls_R_factor_gt           0.0465
_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^)+(0.0843P)^2^+0.0886P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1244
_refine_ls_wR_factor_ref         0.1310
_reflns_Friedel_coverage         0.906
_reflns_Friedel_fraction_full    0.912
_reflns_Friedel_fraction_max     0.724
_reflns_number_gt                11602
_reflns_number_total             12315
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00203e2.cif
_cod_data_source_block           dp-339x
_cod_original_cell_volume        2374.5(8)
_cod_database_code               1566423
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.957
_diffrn_measurement_detector_type 'Dectris Eiger 16M'
_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.a Ternary CH refined with riding coordinates:
 C26(H26), C3(H3), C2(H2), C25(H25)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C24(H24A,H24B)
2.c Aromatic/amide H refined with riding coordinates:
 C30(H30), C40(H40), C33(H33), C9(H9), C44(H44), C15(H15), C19(H19), C43(H43),
 C32(H32), C7(H7), C10(H10), C18(H18), C41(H41), C16(H16)
2.d Idealised Me refined as rotating group:
 C46(H46A,H46B,H46C), C38(H38A,H38B,H38C), C11(H11A,H11B,H11C), C35(H35A,H35B,
 H35C), C37(H37A,H37B,H37C), C36(H36A,H36B,H36C), C13(H13A,H13B,H13C), C22(H22A,
 H22B,H22C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C45(H45A,H45B,H45C),
 C23(H23A,H23B,H23C)
;
_shelx_res_checksum              93737
_shelx_hkl_checksum              44163
_olex2_submission_special_instructions 'No special instructions were received'