Manganese catalyzed chemo-selective synthesis of acyl cyclopentenes: a combined experimental and computational investigation.
Sarkar, Koushik; Behera, Prativa; Roy, Lisa; Maji, Biplab; Chemical science 15 (2024) 14287–14294; doi:10.1039/d4sc02842b

data_1572260
_publ_section_title
;
 Manganese catalyzed chemo-selective synthesis of acyl cyclopentenes: a
 combined experimental and computational investigation.
;
_journal_issue                   35
_journal_name_full               'Chemical science'
_journal_page_first              14287
_journal_page_last               14294
_journal_paper_doi               10.1039/d4sc02842b
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C23 H28 O'
_chemical_formula_sum            'C23 H28 O'
_chemical_formula_weight         320.45
_chemical_name_systematic
(S)-3-cyclopropyl-1-(2,3,4,5,6-pentamethylphenyl)-3-phenylpropan-1-one
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2022-12-30
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-01-20 deposited with the CCDC.	2024-08-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.63527(13)
_cell_length_b                   10.05280(9)
_cell_length_c                   21.90982(17)
_cell_measurement_reflns_used    27928
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      68.0660
_cell_measurement_theta_min      2.0010
_cell_volume                     3664.00(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.992
_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     14.00 109.00   0.50    0.20    --   40.33  77.00-150.00  190
  2  \w     17.00 108.00   0.50    0.20    --   40.33  64.00-180.00  182
  3  \w    100.00 167.00   0.50    0.50    --   96.67  87.00 -40.00  134
  4  \w    -35.00  24.00   0.50    0.20    --   40.33 -12.00-120.00  118
  5  \w    -26.00  47.00   0.50    0.20    --   40.33 -42.00 -31.00  146
  6  \w     24.00 107.00   0.50    0.20    --   40.33  42.00 121.00  166
  7  \w    105.00 170.00   0.50    0.50    --   96.67  96.00   0.00  130
  8  \w     73.00 165.00   0.50    0.50    --   96.67  68.00 -90.00  184
  9  \w     78.00 163.00   0.50    0.50    --   96.67  50.00-180.00  170
 10  \w     80.00 163.00   0.50    0.50    --   96.67  42.00-120.00  166
 11  \w     78.00 163.00   0.50    0.50    --   96.67  50.00  60.00  170
 12  \w     80.00 163.00   0.50    0.50    --   96.67  42.00 121.00  166
 13  \w     29.00  83.00   0.50    0.50    --   96.67 -68.00  90.00  108
 14  \w     29.00  68.00   0.50    0.50    --   96.67 -59.00   0.00   78
 15  \w     29.00  68.00   0.50    0.50    --   96.67 -59.00 -30.00   78
 16  \w     30.00  57.00   0.50    0.50    --   96.67 -50.00  90.00   54
 17  \w     29.00  68.00   0.50    0.50    --   96.67 -59.00 -90.00   78
 18  \w     30.00  57.00   0.50    0.50    --   96.67 -50.00 -90.00   54
 19  \w     30.00  57.00   0.50    0.50    --   96.67 -50.00-120.00   54
 20  \w     30.00  57.00   0.50    0.50    --   96.67 -50.00-180.00   54
 21  \w     29.00  83.00   0.50    0.50    --   96.67 -68.00-180.00  108
 22  \w     27.00 127.00   0.50    0.50    --   96.67 -87.00-158.00  200
 23  \w    -22.00  71.00   0.50    0.20    --   40.33 -87.00-158.00  186
 24  \w     41.00  99.00   0.50    0.20    --   40.33-138.00  60.00  116
 25  \w     44.00 127.00   0.50    0.50    --   96.67-145.00 120.00  166
 26  \w     26.00 108.00   0.50    0.50    --   96.67-104.00 111.00  164
 27  \w     18.00  79.00   0.50    0.20    --   40.33-104.00 111.00  122
 28  \w   -150.00 -66.00   0.50    0.50    --  -82.50 -42.00 -31.00  168
 29  \w   -109.00 -13.00   0.50    0.20    --  -40.33 -77.00  60.00  192
 30  \w   -109.00 -13.00   0.50    0.20    --  -40.33 -77.00  90.00  192
 31  \w   -109.00 -13.00   0.50    0.20    --  -40.33 -77.00   0.00  192
 32  \w   -109.00 -13.00   0.50    0.20    --  -40.33 -77.00 -60.00  192
 33  \w   -109.00 -13.00   0.50    0.20    --  -40.33 -77.00 -90.00  192
 34  \w   -109.00 -13.00   0.50    0.20    --  -40.33 -77.00-180.00  192
 35  \w   -107.00 -21.00   0.50    0.20    --  -40.33 -50.00-150.00  172
 36  \w   -106.00 -24.00   0.50    0.20    --  -40.33 -42.00 -31.00  164
 37  \w    -56.00 -16.00   0.50    0.50    --  -82.50  50.00 150.00   80
 38  \w    -47.00 -15.00   0.50    0.50    --  -82.50  42.00 121.00   64
 39  \w    -47.00  27.00   0.50    0.20    --  -40.33  42.00 121.00  148
 40  \w    -71.00  30.00   0.50    0.20    --  -40.33  87.00 -40.00  202
 41  \w   -113.00 -12.00   0.50    0.50    --  -82.50  87.00 -40.00  202
 42  \w    -78.00   4.00   0.50    0.20    --  -40.33 104.00-146.00  164
 43  \w    -82.00 -11.00   0.50    0.50    --  -82.50 104.00-146.00  142
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0133663000
_diffrn_orient_matrix_UB_12      -0.1405942000
_diffrn_orient_matrix_UB_13      0.0260046000
_diffrn_orient_matrix_UB_21      -0.0817336000
_diffrn_orient_matrix_UB_22      0.0442673000
_diffrn_orient_matrix_UB_23      0.0260980000
_diffrn_orient_matrix_UB_31      -0.0414871000
_diffrn_orient_matrix_UB_32      -0.0418961000
_diffrn_orient_matrix_UB_33      -0.0598753000
_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  0.1229
_diffrn_reflns_av_unetI/netI     0.0323
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            36854
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.407
_diffrn_reflns_theta_min         4.035
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.522
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80475
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.58a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear whiteish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.162
_exptl_crystal_description       block
_exptl_crystal_F_000             1392
_exptl_crystal_preparation       'Hexane in DCM'
_exptl_crystal_recrystallization_method 'not needed'
_exptl_crystal_size_max          0.002
_exptl_crystal_size_mid          0.002
_exptl_crystal_size_min          0.001
_refine_diff_density_max         0.326
_refine_diff_density_min         -0.249
_refine_diff_density_rms         0.044
_refine_ls_extinction_coef       0.00090(14)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     223
_refine_ls_number_reflns         3335
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0474
_refine_ls_R_factor_gt           0.0458
_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^)+(0.0647P)^2^+1.7312P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1261
_refine_ls_wR_factor_ref         0.1277
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3154
_reflns_number_total             3335
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02842b2.cif
_cod_data_source_block           ksk-kcpdt_auto
_cod_depositor_comments
'Adding full bibliography for 1572257--1572260.cif.'
_cod_database_code               1572260
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O'
_chemical_oxdiff_usercomment     100K
_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:
 C17(H17), C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C18(H18a,H18b), C19(H19a,H19b), C8(H8a,H8b)
2.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C16(H16), C15(H15), C13(H13), C14(H14)
2.d Idealised Me refined as rotating group:
 C20(H20a,H20b,H20c), C22(H22a,H22b,H22c), C23(H23a,H23b,H23c), C21(H21a,H21b,
 H21c), C24(H24a,H24b,H24c)
;
_shelx_res_checksum              36886
_shelx_hkl_checksum              23047
_olex2_exptl_crystal_mounting_method 'not needed'
_olex2_submission_original_sample_id 'KSK KC PDT_auto'
_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 1.310
_oxdiff_exptl_absorpt_empirical_full_min 0.705