An interrupted Corey-Chaykovsky reaction of designed azaarenium salts: synthesis of complex polycyclic spiro- and fused cyclopropanoids.
Singh, Bara; Ansari, Arshad J.; Malik, Nirmal; Ramasastry, S. S. V.; Chemical science 14 (2023) 6963–6969; doi:10.1039/d3sc01578e

data_1569274
_publ_section_title
;
 An interrupted Corey-Chaykovsky reaction of designed azaarenium salts:
 synthesis of complex polycyclic spiro- and fused cyclopropanoids.
;
_journal_issue                   25
_journal_name_full               'Chemical science'
_journal_page_first              6963
_journal_page_last               6969
_journal_paper_doi               10.1039/d3sc01578e
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration syn
_chemical_compound_source        synthesized
_chemical_formula_moiety         'C28 H27 N O2 S'
_chemical_formula_sum            'C28 H27 N O2 S'
_chemical_formula_weight         441.56
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-07-20
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.01.05 svn.r3372 for Rigaku Oxford Diffraction, GUI svn.r5289)
;
_audit_update_record
;
2022-01-20 deposited with the CCDC.	2023-05-29 downloaded from the CCDC.
;
_cell_angle_alpha                88.918(3)
_cell_angle_beta                 87.476(3)
_cell_angle_gamma                74.544(3)
_cell_formula_units_Z            2
_cell_length_a                   9.0157(3)
_cell_length_b                   11.1293(4)
_cell_length_c                   11.8264(3)
_cell_measurement_reflns_used    9567
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.1750
_cell_measurement_theta_min      3.3760
_cell_volume                     1142.59(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.934
_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    -41.00 -15.00   0.50   20.00    --   -9.95 -60.00 -76.00   52
  2  \w     22.00  54.00   0.50   20.00    --   -9.95  60.00  63.00   64
  3  \w     -1.00  55.00   0.50   20.00    --   10.22  60.00  63.00  112
  4  \w    -36.00 -11.00   0.50   20.00    --   10.22 -60.00 -76.00   50
  5  \w     14.00  59.00   0.50   20.00    --   -9.95  19.00  60.00   90
  6  \w    -55.00 -29.00   0.50   20.00    --   -9.95 125.00-150.00   52
  7  \w    -52.00  -2.00   0.50   20.00    --   -9.95 -57.00   0.00  100
  8  \w    -28.00  53.00   0.50   20.00    --   -9.95  57.00   0.00  162
  9  \w    -58.00  -3.00   0.50   20.00    --   -9.95 125.00-180.00  110
 10  \w    -26.00  53.00   0.50   20.00    --   -9.95  57.00 -60.00  158
 11  \w    -74.00  -4.00   0.50   20.00    --   -9.95 -38.00 120.00  140
 12  \w    -32.00   1.00   0.50   20.00    --   10.22 121.00 -44.02   66
 13  \w    -34.00  -3.00   0.50   20.00    --   10.22 122.00  60.46   62
 14  \w    -53.00 -21.00   0.50   20.00    --   10.22 -19.00 -90.00   64
 15  \w      7.00  59.00   0.50   20.00    --   10.22-125.00-180.00  104
 16  \w      4.00  48.00   0.50   20.00    --   10.22-125.00 150.00   88
 17  \w    -27.00   0.00   0.50   20.00    --   10.22 122.00 134.20   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0426937000
_diffrn_orient_matrix_UB_12      0.0379202000
_diffrn_orient_matrix_UB_13      0.0441646000
_diffrn_orient_matrix_UB_21      0.0511505000
_diffrn_orient_matrix_UB_22      0.0386460000
_diffrn_orient_matrix_UB_23      -0.0043821000
_diffrn_orient_matrix_UB_31      -0.0472718000
_diffrn_orient_matrix_UB_32      0.0379626000
_diffrn_orient_matrix_UB_33      -0.0404301000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0484
_diffrn_reflns_av_unetI/netI     0.0464
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.934
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            16391
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.934
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.476
_diffrn_reflns_theta_min         3.177
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.167
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68759
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.283
_exptl_crystal_description       block
_exptl_crystal_F_000             468
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.377
_refine_diff_density_min         -0.341
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.120
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     291
_refine_ls_number_reflns         4891
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.120
_refine_ls_R_factor_all          0.0743
_refine_ls_R_factor_gt           0.0502
_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^)+(0.0715P)^2^+0.0422P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1363
_refine_ls_wR_factor_ref         0.1490
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3414
_reflns_number_total             4891
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01578e2.cif
_cod_data_source_block           iiser-sam0412
_cod_depositor_comments
'Adding full bibliography for 1569272--1569274.cif.'
_cod_original_cell_volume        1142.58(6)
_cod_database_code               1569274
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C N O S H'
_diffrn_oxdiff_ac3_digest_frames
;
017c084d88baa7f1caa7443be1291d61d300025f78b
;
_diffrn_oxdiff_ac3_digest_hkl
;
0139ed00b2aeb09103be0f1621756d84eabc4f
;
_reflns_odcompleteness_completeness 99.64
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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:
 C20(H20), C19(H19), C16(H16), C21(H21)
2.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C28(H28A,H28B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C13(H13), C4(H4), C5(H5), C10(H10), C3(H3), C12(H12), C11(H11),
 C23(H23), C27(H27), C25(H25), C24(H24), C26(H26)
2.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C18(H18A,H18B,H18C)
;
_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 1.412
_oxdiff_exptl_absorpt_empirical_full_min 0.678