Diastereoselective trifunctionalization of pyridinium salts to access structurally crowded azaheteropolycycles.
Cui, Zhaohui; Zhang, Kuan; Gu, Lijie; Bu, Zhanwei; Zhao, Junwei; Wang, Qilin; Chemical communications (Cambridge, England) 57 (2021) 9402–9405; doi:10.1039/d1cc03478b

data_7128821
_publ_section_title
;
 Diastereoselective trifunctionalization of pyridinium salts to access
 structurally crowded azaheteropolycycles.
;
_journal_issue                   74
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              9402
_journal_page_last               9405
_journal_paper_doi               10.1039/d1cc03478b
_journal_volume                  57
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C H Cl3, C30 H25 N3 O6'
_chemical_formula_sum            'C31 H26 Cl3 N3 O6'
_chemical_formula_weight         642.90
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-06-29
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.09.11 svn.r3730fd0d for OlexSys, GUI svn.r6159)
;
_audit_update_record
;
2021-06-29 deposited with the CCDC.	2021-08-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.9528(3)
_cell_length_b                   12.4499(5)
_cell_length_c                   26.0558(12)
_cell_measurement_reflns_used    2529
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      73.3600
_cell_measurement_theta_min      3.9040
_cell_volume                     2904.2(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.972
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     42.00  80.00   1.00    1.50    --   41.11  38.00 -90.00   38
  2  \w    135.00 172.00   1.00    3.00    --  107.58 125.00-150.00   37
  3  \w     56.00 175.00   1.00    3.00    --  107.58  15.00 -60.00  119
  4  \w     91.00 117.00   1.00    3.00    --  107.58 -45.00  90.00   26
  5  \w     39.00 122.00   1.00    3.00    --  107.58-125.00  30.00   83
  6  \w     34.00  77.00   1.00    1.50    --   41.11 -99.00   0.00   43
  7  \w   -113.00 -45.00   1.00    1.50    --  -41.11 -57.00-180.00   68
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0154667000
_diffrn_orient_matrix_UB_12      -0.1055389000
_diffrn_orient_matrix_UB_13      -0.0302972000
_diffrn_orient_matrix_UB_21      -0.0061738000
_diffrn_orient_matrix_UB_22      0.0641513000
_diffrn_orient_matrix_UB_23      -0.0505218000
_diffrn_orient_matrix_UB_31      0.1714777000
_diffrn_orient_matrix_UB_32      -0.0067643000
_diffrn_orient_matrix_UB_33      -0.0045392000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0526
_diffrn_reflns_av_unetI/netI     0.0819
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            7183
_diffrn_reflns_point_group_measured_fraction_full 0.882
_diffrn_reflns_point_group_measured_fraction_max 0.842
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.901
_diffrn_reflns_theta_min         3.935
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.287
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63701
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.470
_exptl_crystal_description       prism
_exptl_crystal_F_000             1328
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.501
_refine_diff_density_min         -0.391
_refine_diff_density_rms         0.072
_refine_ls_abs_structure_details
;
 Flack x determined using 1250 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     409
_refine_ls_number_reflns         4952
_refine_ls_number_restraints     38
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0721
_refine_ls_R_factor_gt           0.0624
_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^)+(0.0770P)^2^+1.3590P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1571
_refine_ls_wR_factor_ref         0.1694
_reflns_Friedel_coverage         0.527
_reflns_Friedel_fraction_full    0.728
_reflns_Friedel_fraction_max     0.671
_reflns_number_gt                4290
_reflns_number_total             4952
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc03478b2.cif
_cod_data_source_block           2109
_cod_depositor_comments
'Adding full bibliography for 7128819--7128822.cif.'
_cod_database_code               7128821
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Rigid bond restraints
 Cl2, C30
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C28B, C32
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
Cl2 \\sim C30: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004 within 2A
C28B \\sim C32: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004 within 2A
Uanis(C28B) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
4. Rigid body (RIGU) restrains
 O5, C28, H28A, H28B, C29, H29A, H29B, H29C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O5, C28B, C32, H32A, H32B, H32C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O5, C28B, C32
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O5, C28, C29
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Others
 Sof(C28B)=Sof(H28C)=Sof(H28D)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=1-FVAR(1)
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C30(H30), C9(H9), C10(H10), C11(H11), C33(H33)
6.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C28(H28A,H28B), C28B(H28C,H28D)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C14(H14), C15(H15), C16(H16), C17(H17),
 C19(H19), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26)
6.d Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              52707
_olex2_date_sample_data_collection 2021-06-28
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.313
_oxdiff_exptl_absorpt_empirical_full_min 0.634