Stereocontrol in an intermolecular Schmidt reaction of equilibrating hydroxyalkyl allylic azides.
Liu, Ruzhang; Wang, Juan; Wu, Hao; Quan, Xianfeng; Wang, Shilin; Guo, Jiandong; Wang, Yang; Li, Heting; Chemical communications (Cambridge, England) 60 (2024) 4362–4365; doi:10.1039/d4cc00907j

data_7132890
_publ_section_title
;
 Stereocontrol in an intermolecular Schmidt reaction of equilibrating
 hydroxyalkyl allylic azides.
;
_journal_issue                   32
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              4362
_journal_page_last               4365
_journal_paper_doi               10.1039/d4cc00907j
_journal_volume                  60
_journal_year                    2024
_chemical_absolute_configuration 17b-hydroxy-5a-androstan-3-one
_chemical_formula_moiety         'C24 H39 N O3, H2 O'
_chemical_formula_sum            'C24 H41 N O4'
_chemical_formula_weight         407.58
_chemical_name_systematic        17b-hydroxy-5a-androstan-3-one
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2021-05-07
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_audit_update_record
;
2022-06-05 deposited with the CCDC.	2024-03-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.3720(6)
_cell_length_b                   21.111(2)
_cell_length_c                   17.2221(17)
_cell_measurement_reflns_used    3478
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      20.264
_cell_measurement_theta_min      2.263
_cell_volume                     2316.7(4)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1009
_diffrn_reflns_av_unetI/netI     0.1650
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            22020
_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         27.444
_diffrn_reflns_theta_min         1.526
_exptl_absorpt_coefficient_mu    0.078
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6905
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0995 before and 0.0616 after correction.
The Ratio of minimum to maximum transmission is 0.9261.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.169
_exptl_crystal_description       block
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.162
_refine_diff_density_min         -0.150
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 707 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.6(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.977
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     292
_refine_ls_number_reflns         5292
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.977
_refine_ls_R_factor_all          0.2102
_refine_ls_R_factor_gt           0.0612
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0454P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0916
_refine_ls_wR_factor_ref         0.1196
_reflns_Friedel_coverage         0.744
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                2265
_reflns_number_total             5292
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc00907j2.cif
_cod_data_source_block           26a
_cod_depositor_comments
'Adding full bibliography for 7132889--7132892.cif.'
_cod_database_code               7132890
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.985
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C8(H8), C5(H5), C14(H14), C22(H22), C17(H17)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C11(H11A,H11B), C7(H7A,H7B), C4(H4A,H4B), C12(H12A,H12B),
 C16(H16A,H16B), C2(H2A,H2B), C6(H6A,H6B), C15(H15A,H15B), C21(H21A,H21B),
 C20(H20A,H20B)
2.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C18(H18A,H18B,H18C)
2.d Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_shelx_res_checksum              41031
_olex2_submission_special_instructions 'No special instructions were received'