Synthesis of macrocyclic and medium-sized ring thiolactones <i>via</i> the ring expansion of lactams.
Palate, Kleopas Y.; Epton, Ryan G.; Whitwood, Adrian C.; Lynam, Jason M.; Unsworth, William P.; Organic & biomolecular chemistry 19 (2021) 1404–1411; doi:10.1039/d0ob02502j

data_7157847
_publ_section_title
;
 Synthesis of macrocyclic and medium-sized ring thiolactones <i>via</i>
 the ring expansion of lactams.
;
_journal_issue                   6
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              1404
_journal_page_last               1411
_journal_paper_doi               10.1039/d0ob02502j
_journal_volume                  19
_journal_year                    2021
_chemical_formula_moiety         'C24 H36 N2 O3 S'
_chemical_formula_sum            'C24 H36 N2 O3 S'
_chemical_formula_weight         432.61
_chemical_melting_point          357
_chemical_name_systematic
5-benzyl-5,8-diaza-1-thiacycloicosane-4,7,20-trione
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc26h4mh
_audit_creation_date             2020-09-21
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2020-10-23 deposited with the CCDC.	2021-01-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.2577(14)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.65728(15)
_cell_length_b                   15.7878(3)
_cell_length_c                   31.1416(4)
_cell_measurement_reflns_used    6790
_cell_measurement_temperature    110.0(4)
_cell_measurement_theta_max      70.9900
_cell_measurement_theta_min      3.9900
_cell_volume                     4740.40(13)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (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      110.0(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -20.00  39.00   1.00   18.12    --    0.00  57.00 120.00   59
  2  \w     -6.00  24.00   1.00   18.12    --    0.00  77.00-180.00   30
  3  \w     43.00  68.00   1.00   18.12    --    0.00  57.00 120.00   25
  4  \w     74.00 116.00   1.00   72.46    --   54.00  57.00  60.00   42
  5  \w     66.00 123.00   1.00   72.46    --   54.00  57.00 120.00   57
  6  \w    -14.00  84.00   1.00   72.46    --   54.00 -77.00 -90.00   98
  7  \w    -14.00  75.00   1.00   72.46    --   54.00 -57.00 -30.00   89
  8  \w    114.00 150.00   1.00   72.46    --  108.00 111.00-150.00   36
  9  \w     53.00 107.00   1.00   72.46    --  108.00-111.00   0.00   54
 10  \w     48.00 106.00   1.00   72.46    --  108.00-111.00  90.00   58
 11  \w     75.00 178.00   1.00   72.46    --  108.00  25.00-150.00  103
 12  \w     63.00 109.00   1.00   72.46    --  108.00 178.00   0.00   46
 13  \w     63.00 103.00   1.00   72.46    --  108.00 -91.00-120.00   40
 14  \w    104.00 135.00   1.00   72.46    --  108.00 111.00   0.00   31
 15  \w    122.00 178.00   1.00   72.46    --  108.00 111.00 -90.00   56
 16  \w     62.00 131.00   1.00   72.46    --  108.00 -38.00-150.00   69
 17  \w    122.00 174.00   1.00   72.46    --  108.00 111.00-120.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0375972000
_diffrn_orient_matrix_UB_12      0.0929319000
_diffrn_orient_matrix_UB_13      0.0089228000
_diffrn_orient_matrix_UB_21      -0.1497046000
_diffrn_orient_matrix_UB_22      -0.0269426000
_diffrn_orient_matrix_UB_23      0.0080584000
_diffrn_orient_matrix_UB_31      0.0414751000
_diffrn_orient_matrix_UB_32      -0.0127588000
_diffrn_orient_matrix_UB_33      0.0480451000
_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  0.0241
_diffrn_reflns_av_unetI/netI     0.0334
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            18496
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.065
_diffrn_reflns_theta_max         67.065
_diffrn_reflns_theta_min         3.991
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.419
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.685
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.212
_exptl_crystal_description       needle
_exptl_crystal_F_000             1872
_exptl_crystal_recrystallization_method
'crystallisation from dichloromethane and hexane'
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.057
_exptl_crystal_size_min          0.032
_refine_diff_density_max         0.635
_refine_diff_density_min         -0.311
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     820
_refine_ls_number_reflns         8452
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0527
_refine_ls_R_factor_gt           0.0416
_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^)+(0.0459P)^2^+2.9922P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0983
_refine_ls_wR_factor_ref         0.1049
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7096
_reflns_number_total             8452
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ob02502j2.cif
_cod_data_source_block           wpu2009
_cod_depositor_comments
'Adding full bibliography for 7157847--7157849.cif.'
_cod_original_cell_volume        4740.42(12)
_cod_database_code               7157847
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C24 H36 N2 O2 S1'
_chemical_oxdiff_usercomment     'Kleo Palate KP208_A'
_reflns_odcompleteness_completeness 99.76
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All C(H,H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C7A) = Uanis(C7)
Uanis(C6) = Uanis(C6A)
3. Others
 Sof(H5BC)=Sof(H5BD)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=
 Sof(H8BC)=Sof(H8BD)=1-FVAR(1)
 Sof(H5AA)=Sof(H5AB)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C7)=Sof(H7A)=Sof(H7B)=
 Sof(H8AA)=Sof(H8AB)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C5(H5AA,H5AB), C5(H5BC,H5BD), C6A(H6AA,H6AB), C7A(H7AA,H7AB), C8(H8AA,H8AB),
 C8(H8BC,H8BD)
;
_shelx_res_checksum              96326
_olex2_date_sample_data_collection 2020-09-10
_olex2_date_sample_submission    2020-08-28
_olex2_exptl_crystal_mounting_method 'oil on 200 micrometre micromount'
_olex2_submission_original_sample_id KP208_A
_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 2.799
_oxdiff_exptl_absorpt_empirical_full_min 0.666