A greener approach towards the synthesis of N-heterocyclic thiones and selones using mechanochemical technique
Sanjay Kumar, Siddharth; Rangarajan, Shalini; Kunchur, Harish S.; Balakrishna, Maravanji Shivaramaiah; Dalton Transactions  (2022) –; doi:10.1039/D2DT02322A

data_7711333
_publ_section_title
;
 A greener approach towards the synthesis of N-heterocyclic thiones and
 selones using mechanochemical technique
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT02322A
_journal_year                    2022
_chemical_formula_moiety         'C20 H23 N2 O P S'
_chemical_formula_sum            'C20 H23 N2 O P S'
_chemical_formula_weight         370.43
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-07-05
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-07-12 deposited with the CCDC.	2022-09-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.860(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.6482(15)
_cell_length_b                   21.1068(17)
_cell_length_c                   9.3551(10)
_cell_measurement_reflns_used    2713
_cell_measurement_temperature    150
_cell_measurement_theta_max      28.9340
_cell_measurement_theta_min      2.2720
_cell_volume                     1937.4(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -59.00  70.00   1.00    8.00    --  -20.00  72.00 -36.00  129
  2  \w    -59.00  44.00   1.00    8.00    --  -20.00  72.00-108.00  103
  3  \w    -69.00 -21.00   1.00    8.00    --  -20.00 -72.00  36.00   48
  4  \w   -110.00 -45.00   1.00    8.00    --  -20.00 -72.00-108.00   65
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0536122000
_diffrn_orient_matrix_UB_12      -0.0005067000
_diffrn_orient_matrix_UB_13      0.0745991000
_diffrn_orient_matrix_UB_21      0.0055308000
_diffrn_orient_matrix_UB_22      0.0334498000
_diffrn_orient_matrix_UB_23      -0.0022546000
_diffrn_orient_matrix_UB_31      -0.0481381000
_diffrn_orient_matrix_UB_32      0.0032383000
_diffrn_orient_matrix_UB_33      0.0347369000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1067
_diffrn_reflns_av_unetI/netI     0.1188
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            12285
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        24.997
_diffrn_reflns_theta_max         24.997
_diffrn_reflns_theta_min         2.076
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.260
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.28802
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
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    1.270
_exptl_crystal_description       block
_exptl_crystal_F_000             784
_exptl_crystal_size_max          0.089
_exptl_crystal_size_mid          0.067
_exptl_crystal_size_min          0.058
_refine_diff_density_max         0.591
_refine_diff_density_min         -0.395
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     264
_refine_ls_number_reflns         3409
_refine_ls_number_restraints     55
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.1453
_refine_ls_R_factor_gt           0.0752
_refine_ls_shift/su_max          0.015
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0521P)^2^+1.1930P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1436
_refine_ls_wR_factor_ref         0.1860
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1921
_reflns_number_total             3409
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02322a2.cif
_cod_data_source_block           comp_5
_cod_database_code               7711333
_shelx_shelxl_version_number     2018/3
_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
 N1-C17A \\sim N1-C17B
 with sigma of 0.02
 C17A-C18A \\sim C17B-C18B
 with sigma of 0.02
 C18A-C19A \\sim C18B-C19B
 with sigma of 0.02
 C20A-C19A \\sim C20B-C19B
 with sigma of 0.02
 C18A-C20A \\sim C18B-C20B
 with sigma of 0.04
 N1-C18A \\sim N1-C18B
 with sigma of 0.04
 C17A-C19A \\sim C17B-C19B
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C18B) \\sim Ueq, Uanis(C19B) \\sim Ueq, Uanis(C20B) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.04
4. Rigid body (RIGU) restrains
 C17A, C18A, C20A, C19A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C17B, C18B, C20B, C19B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C17A(0.575) H17A(0.575) H17B(0.575) C18A(0.575) H18A(0.575)
 H18B(0.575) C20A(0.575) H20A(0.575) H20B(0.575) H20C(0.575) C19A(0.575)
 H19A(0.575) H19B(0.575) C17B(0.425) H17C(0.425) H17D(0.425) C18B(0.425)
 H18C(0.425) H18D(0.425) C19B(0.425) H19C(0.425) H19D(0.425) C20B(0.425)
 H20D(0.425) H20E(0.425) H20F(0.425)
6.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C17A(H17A,H17B), C18A(H18A,H18B), C19A(H19A,H19B), C17B(H17C,
 H17D), C18B(H18C,H18D), C19B(H19C,H19D)
6.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C10(H10), C14(H14), C16(H16), C7(H7), C3(H3), C2(H2), C12(H12),
 C8(H8), C15(H15), C13(H13), C9(H9)
6.c Idealised Me refined as rotating group:
 C20A(H20A,H20B,H20C), C20B(H20D,H20E,H20F)
;
_shelx_res_checksum              91123
_shelx_hkl_checksum              77738
_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 2.420
_oxdiff_exptl_absorpt_empirical_full_min 0.685