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_1559636
_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         'C32 H33 N3 O2 S'
_chemical_formula_sum            'C32 H33 N3 O2 S'
_chemical_formula_weight         523.67
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-06-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2020-07-09 deposited with the CCDC.	2020-11-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.3559(7)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.90952(14)
_cell_length_b                   10.14583(6)
_cell_length_c                   28.4275(2)
_cell_measurement_reflns_used    15287
_cell_measurement_temperature    180.00(10)
_cell_measurement_theta_max      73.5070
_cell_measurement_theta_min      4.6030
_cell_volume                     5444.54(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      180.00(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 0.990
_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    -70.00   4.00   1.00    1.00    --  -38.94  38.00 150.00   74
  2  \w     71.00 112.00   1.00    1.00    --   38.94 178.00 120.00   41
  3  \w    100.00 178.00   1.00    5.00    --  110.40 111.00  30.00   78
  4  \w    114.00 158.00   1.00    5.00    --  110.40 111.00 -60.00   44
  5  \w     99.00 156.00   1.00    5.00    --  110.40  61.00 -60.00   57
  6  \w     79.00 155.00   1.00    5.00    --  110.40  45.00   0.00   76
  7  \w    110.00 137.00   1.00    5.00    --  110.40 -45.00 -30.00   27
  8  \w     81.00 108.00   1.00    5.00    --  110.40 -94.00  60.00   27
  9  \w     66.00 113.00   1.00    5.00    --  110.40-111.00 -30.00   47
 10  \w     35.00 142.00   1.00    5.00    --  110.40 -77.00 -30.00  107
 11  \w     75.00 173.00   1.00    5.00    --  110.40  30.00 -90.00   98
 12  \w     84.00 176.00   1.00    5.00    --  110.40  30.00  90.00   92
 13  \w     60.00 131.00   1.00    1.00    --   38.94 178.00 -90.00   71
 14  \w     26.00  99.00   1.00    5.00    --  110.40 -94.00 150.00   73
 15  \w     30.00  56.00   1.00    5.00    --  110.40-111.00 -30.00   26
 16  \w     24.00  58.00   1.00    5.00    --  110.40 -94.00 -30.00   34
 17  \w     31.00 105.00   1.00    5.00    --  110.40-111.00-120.00   74
 18  \w    -95.00 -10.00   1.00    1.00    --  -38.94 -38.00 -90.00   85
 19  \w   -111.00 -81.00   1.00    1.00    --  -38.94 -99.00  90.00   30
 20  \w   -115.00  -7.00   1.00    1.00    --  -38.94 -57.00 150.00  108
 21  \w   -123.00 -98.00   1.00    1.00    --  -38.94 -99.00  60.00   25
 22  \w   -124.00 -80.00   1.00    1.00    --  -38.94 -99.00-120.00   44
 23  \w    -62.00 -36.00   1.00    1.00    --  -38.94-178.00 -90.00   26
 24  \w   -124.00 -99.00   1.00    1.00    --  -38.94 -99.00 -30.00   25
 25  \w   -120.00 -94.00   1.00    1.00    --  -38.94-178.00 -90.00   26
 26  \w     29.00  55.00   1.00    1.00    --   38.94  38.00 -60.00   26
 27  \w     63.00  89.00   1.00    1.00    --   38.94  38.00 -60.00   26
 28  \w    110.00 154.00   1.00    5.00    --  110.40 111.00-180.00   44
 29  \w     47.00  75.00   1.00    5.00    --  110.40 -61.00-180.00   28
 30  \w    148.00 174.00   1.00    5.00    --  110.40  61.00 -30.00   26
 31  \w     83.00 109.00   1.00    5.00    --  110.40  61.00 -30.00   26
 32  \w    114.00 140.00   1.00    5.00    --  110.40 -61.00-180.00   26
 33  \w     68.00 115.00   1.00    5.00    --  110.40-111.00 120.00   47
;
_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      0.0146891000
_diffrn_orient_matrix_UB_12      -0.1246445000
_diffrn_orient_matrix_UB_13      0.0299326000
_diffrn_orient_matrix_UB_21      -0.0298941000
_diffrn_orient_matrix_UB_22      0.0691138000
_diffrn_orient_matrix_UB_23      0.0428140000
_diffrn_orient_matrix_UB_31      -0.0745196000
_diffrn_orient_matrix_UB_32      -0.0522985000
_diffrn_orient_matrix_UB_33      -0.0147620000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0202
_diffrn_reflns_av_unetI/netI     0.0136
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            23114
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.635
_diffrn_reflns_theta_min         3.114
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.322
_exptl_absorpt_correction_T_max  0.884
_exptl_absorpt_correction_T_min  0.714
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.278
_exptl_crystal_description       prism
_exptl_crystal_F_000             2224
_exptl_crystal_size_max          0.332
_exptl_crystal_size_mid          0.169
_exptl_crystal_size_min          0.104
_refine_diff_density_max         0.223
_refine_diff_density_min         -0.434
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     420
_refine_ls_number_reflns         5449
_refine_ls_number_restraints     180
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0372
_refine_ls_R_factor_gt           0.0348
_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^)+(0.0471P)^2^+3.4143P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0905
_refine_ls_wR_factor_ref         0.0926
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5075
_reflns_number_total             5449
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc05725h2.cif
_cod_data_source_block           ajgi665_2_2
_cod_depositor_comments
;Adding full bibliography for 1559635--1559639.cif.

 Adding full bibliography for 1559635--1559639.cif.
;
_cod_original_cell_volume        5444.54(7)
_cod_database_code               1559636
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C32 H33 N2 O2 S1'
_reflns_odcompleteness_completeness 99.94
_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
 C36B-C35B \\sim C38-C35
 with sigma of 0.02
 C37B-C35B \\sim C34B-C35B \\sim C35-C34 \\sim C35-C36 \\sim C38B-C37B \\sim
C34-C33 \\sim C33B-C34B ~
 C33-C32 \\sim C33B-C32 \\sim C38B-C32 \\sim C37-C32 \\sim C36-C37
 with sigma of 0.02
 C9-H9AB \\sim C9-H9BD \\sim C9-H9AC \\sim C9-H9AA \\sim C9-H9BE \\sim C9-H9BF
 with sigma of 0.02
3. Restrained planarity
 C32, C33, C34, C35, C36, C37, C38
 with sigma of 0.1
 C32, C33B, C34, C35, C36, C37, C38
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C33B) = Uanis(C33)
5. Rigid body (RIGU) restrains
 C32, C33, C34, C35, C36, C37, C38
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C32, C33B, C34B, C35B, C36B, C37B, C38B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C33B)=Sof(H33B)=Sof(C34B)=Sof(H34B)=Sof(C35B)=Sof(C36B)=Sof(H36A)=
 Sof(H36B)=Sof(H36C)=Sof(C37B)=Sof(H37B)=Sof(C38B)=Sof(H38B)=1-FVAR(1)
 Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(C36)=Sof(H36)=Sof(C37)=
 Sof(H37)=Sof(C38)=Sof(H38A)=Sof(H38C)=Sof(H38D)=FVAR(1)
 Fixed Sof: H9BD(0.5) H9BE(0.5) H9BF(0.5) H9AA(0.5) H9AB(0.5) H9AC(0.5)
7.a Ternary CH refined with riding coordinates:
 C5(H5)
7.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B), C17(H17A,H17B)
7.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C10(H10), C11(H11), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24),
 C26(H26), C27(H27), C30(H30), C31(H31), C33B(H33B), C34B(H34B), C37B(H37B),
 C38B(H38B), C33(H33), C34(H34), C36(H36), C37(H37)
7.d Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C36B(H36A,H36B,H36C), C38(H38A,H38C,H38D)
;
_shelx_res_checksum              82109
_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 1.487
_oxdiff_exptl_absorpt_empirical_full_min 0.670