Regiodivergent synthesis of pyrazino-indolines <i>vs.</i> triazocines <i>via</i> α-imino carbenes addition to imidazolidines.
Guarnieri-Ibáñez, Alejandro; de Aguirre, Adiran; Besnard, Céline; Poblador-Bahamonde, Amalia I; Lacour, Jérôme; Chemical science 12 (2020) 1479–1485; doi:10.1039/d0sc05725h

data_1559635
_publ_section_title
;
 Regiodivergent synthesis of pyrazino-indolines <i>vs.</i> triazocines
 <i>via</i> \a-imino carbenes addition to imidazolidines.
;
_journal_issue                   4
_journal_name_full               'Chemical science'
_journal_page_first              1479
_journal_page_last               1485
_journal_paper_doi               10.1039/d0sc05725h
_journal_volume                  12
_journal_year                    2020
_chemical_formula_moiety         'C31 H30 N4 O5 S'
_chemical_formula_sum            'C31 H30 N4 O5 S'
_chemical_formula_weight         570.65
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-12-04
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2020-07-09 deposited with the CCDC.	2020-11-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.5221(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.14023(8)
_cell_length_b                   15.89219(10)
_cell_length_c                   18.23835(15)
_cell_measurement_reflns_used    13174
_cell_measurement_temperature    180.01(10)
_cell_measurement_theta_max      73.6670
_cell_measurement_theta_min      3.7150
_cell_volume                     2831.92(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      180.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4679
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_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     -3.00  69.00   1.00    1.00    --   38.94 -38.00  90.00   72
  2  \w      4.00  49.00   1.00    1.00    --   38.94 -99.00  90.00   45
  3  \w     37.00 133.00   1.00    1.50    --  110.40 -45.00 120.00   96
  4  \w     54.00 171.00   1.00    1.50    --  110.40 -15.00 -30.00  117
  5  \w    117.00 169.00   1.00    1.50    --  110.40  45.00-180.00   52
  6  \w    132.00 173.00   1.00    1.50    --  110.40 111.00-180.00   41
  7  \w    103.00 132.00   1.00    1.50    --  110.40 111.00-150.00   29
  8  \w     61.00 148.00   1.00    1.50    --  110.40 -30.00-180.00   87
  9  \w     79.00 114.00   1.00    1.50    --  110.40-111.00 -60.00   35
 10  \w     68.00 109.00   1.00    1.50    --  110.40 -94.00-180.00   41
 11  \w     55.00 126.00   1.00    1.50    --  110.40 -61.00-150.00   71
 12  \w     89.00 117.00   1.00    1.00    --   38.94-178.00-120.00   28
 13  \w     37.00 115.00   1.00    1.50    --  110.40-111.00  60.00   78
 14  \w     26.00  73.00   1.00    1.50    --  110.40 -77.00  90.00   47
 15  \w     28.00  89.00   1.00    1.50    --  110.40 -94.00 150.00   61
 16  \w    100.00 177.00   1.00    1.50    --  110.40 111.00 120.00   77
 17  \w     71.00 132.00   1.00    1.00    --   38.94 178.00  90.00   61
 18  \w   -114.00 -87.00   1.00    1.00    --  -38.94 -99.00-120.00   27
 19  \w   -113.00  -7.00   1.00    1.00    --  -38.94 -57.00-150.00  106
 20  \w   -111.00 -85.00   1.00    1.00    --  -38.94 -99.00 -30.00   26
 21  \w   -105.00 -80.00   1.00    1.00    --  -38.94 -99.00  30.00   25
 22  \w   -121.00 -83.00   1.00    1.00    --  -38.94 -99.00 -60.00   38
 23  \w   -114.00 -57.00   1.00    1.00    --  -38.94-151.00-142.00   57
 24  \w   -115.00 -81.00   1.00    1.00    --  -38.94 -99.00-150.00   34
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0381842000
_diffrn_orient_matrix_UB_12      0.0832339000
_diffrn_orient_matrix_UB_13      -0.0438836000
_diffrn_orient_matrix_UB_21      -0.0440069000
_diffrn_orient_matrix_UB_22      -0.0492578000
_diffrn_orient_matrix_UB_23      -0.0753442000
_diffrn_orient_matrix_UB_31      -0.1465168000
_diffrn_orient_matrix_UB_32      -0.0068359000
_diffrn_orient_matrix_UB_33      0.0088527000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0234
_diffrn_reflns_av_unetI/netI     0.0189
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            19567
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.630
_diffrn_reflns_theta_min         3.750
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.411
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.261
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.338
_exptl_crystal_description       prism
_exptl_crystal_F_000             1200
_exptl_crystal_size_max          0.426
_exptl_crystal_size_mid          0.303
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.264
_refine_diff_density_min         -0.533
_refine_diff_density_rms         0.086
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     380
_refine_ls_number_reflns         5648
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0438
_refine_ls_R_factor_gt           0.0409
_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^)+(0.0618P)^2^+0.8235P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1056
_refine_ls_wR_factor_ref         0.1083
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5173
_reflns_number_total             5648
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc05725h2.cif
_cod_data_source_block           AJGI_749_2_1
_cod_depositor_comments
;Adding full bibliography for 1559635--1559639.cif.

 Adding full bibliography for 1559635--1559639.cif.
;
_cod_database_code               1559635
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C31 H30 N4 O5 S1'
_shelx_estimated_absorpt_t_max   0.775
_shelx_estimated_absorpt_t_min   0.585
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.29
_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. Restrained distances
 O42-C37 \\sim O40-C37
 with sigma of 0.02
 O40-C41 \\sim O42-C43
 with sigma of 0.02
 C41-C37 \\sim C37-C43
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(O40) = Uanis(O42)
Uanis(C41) = Uanis(C43)
4. Others
 Sof(O40)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=1-FVAR(1)
 Sof(O42)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C17(H17A,H17B)
5.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C8(H8), C9(H9), C15(H15), C22(H22), C23(H23), C26(H26),
 C27(H27), C29(H29), C30(H30), C31(H31), C32(H32), C33(H33), C35(H35), C36(H36),
  C38(H38), C39(H39)
5.c Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C41(H41A,H41B,H41C), C43(H43A,H43B,H43C)
;
_shelx_res_checksum              1753
_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 1.283
_oxdiff_exptl_absorpt_empirical_full_min 0.770