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_1572258
_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 H26 O'
_chemical_formula_sum            'C23 H26 O'
_chemical_formula_weight         318.43
_chemical_name_systematic
(Z)-3-cyclopropyl-1-(2,3,4,5,6-pentamethylphenyl)-3-phenylprop-2-en-1-one
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-01-20
_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                103.7839(13)
_cell_angle_beta                 96.8936(18)
_cell_angle_gamma                92.5400(16)
_cell_formula_units_Z            4
_cell_length_a                   9.0547(2)
_cell_length_b                   10.15893(15)
_cell_length_c                   20.6100(3)
_cell_measurement_reflns_used    14418
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.1660
_cell_measurement_theta_min      2.2120
_cell_volume                     1822.69(6)
_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      100(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.989
_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      5.00  41.00   0.50    0.20    --   40.33 -38.00-150.00   72
  2  \w    -24.00   2.00   0.50    0.20    --   40.33 -38.00-150.00   52
  3  \w    -26.00  28.00   0.50    0.20    --   40.33 -25.00  60.00  108
  4  \w    -30.00   0.00   0.50    0.20    --   40.33 -25.00 150.00   60
  5  \w      3.00  29.00   0.50    0.20    --   40.33 -25.00 150.00   52
  6  \w     29.00 105.00   0.50    0.50    --   96.67 -77.00  90.00  152
  7  \w     30.00  56.00   0.50    0.50    --   96.67 -68.00 150.00   52
  8  \w     29.00  67.00   0.50    0.50    --   96.67 -59.00   0.00   76
  9  \w     36.00  62.00   0.50    0.50    --   96.67 -59.00  90.00   52
 10  \w     38.00  67.00   0.50    0.50    --   96.67 -59.00 -30.00   58
 11  \w     43.00  68.00   0.50    0.50    --   96.67 -59.00 -60.00   50
 12  \w     34.00  62.00   0.50    0.50    --   96.67 -59.00 -90.00   56
 13  \w     31.00  56.00   0.50    0.50    --   96.67 -50.00-180.00   50
 14  \w    102.00 127.00   0.50    0.50    --   96.67 -87.00-180.00   50
 15  \w    102.00 127.00   0.50    0.50    --   96.67-145.00-150.00   50
 16  \w     96.00 122.00   0.50    0.50    --   96.67-145.00 -90.00   52
 17  \w     47.00  86.00   0.50    0.50    --   96.67-145.00-150.00   78
 18  \w     45.00  88.00   0.50    0.50    --   96.67-145.00 -90.00   86
 19  \w     36.00 109.00   0.50    0.50    --   96.67-117.00 -90.00  146
 20  \w     65.00  91.00   0.50    0.50    --   96.67-149.00 -46.00   52
 21  \w     27.00  79.00   0.50    0.50    --   96.67 -87.00-180.00  104
 22  \w     53.00 117.00   0.50    0.50    --   96.67 -87.00   0.00  128
 23  \w     60.00  91.00   0.50    0.50    --   96.67 -87.00 -90.00   62
 24  \w     34.00 104.00   0.50    0.50    --   96.67-117.00   0.00  140
 25  \w     61.00 127.00   0.50    0.50    --   96.67-145.00 120.00  132
 26  \w     72.00 106.00   0.50    0.50    --   96.67-124.00 117.00   68
 27  \w     18.00  72.00   0.50    0.20    --   40.33-104.00 150.00  108
 28  \w     33.00  90.00   0.50    0.20    --   40.33-124.00 117.00  114
 29  \w     46.00 106.00   0.50    0.20    --   40.33-149.00 -46.00  120
 30  \w     93.00 157.00   0.50    0.50    --   96.67  50.00 150.00  128
 31  \w     75.00 164.00   0.50    0.50    --   96.67  59.00  90.00  178
 32  \w     81.00 164.00   0.50    0.50    --   96.67  59.00 120.00  166
 33  \w     84.00 149.00   0.50    0.50    --   96.67  42.00  60.00  130
 34  \w     83.00 166.00   0.50    0.50    --   96.67  25.00  30.00  166
 35  \w     78.00 144.00   0.50    0.50    --   96.67  59.00-180.00  132
 36  \w    100.00 125.00   0.50    0.50    --   96.67 149.00   0.00   50
 37  \w    111.00 165.00   0.50    0.50    --   96.67  96.00  60.00  108
 38  \w    102.00 164.00   0.50    0.50    --   96.67 117.00  30.00  124
 39  \w     90.00 133.00   0.50    0.50    --   96.67 145.00 -60.00   86
 40  \w    105.00 130.00   0.50    0.50    --   96.67 124.00-163.00   50
 41  \w     82.00 108.00   0.50    0.20    --   40.33  77.00 -60.00   52
 42  \w     64.00 106.00   0.50    0.20    --   40.33  25.00  60.00   84
 43  \w     27.00  56.00   0.50    0.20    --   40.33  25.00  60.00   58
 44  \w     14.00  51.00   0.50    0.20    --   40.33  77.00 -60.00   74
 45  \w     -7.00  19.00   0.50    0.20    --  -40.33  64.00  60.00   52
 46  \w    -13.00  34.00   0.50    0.20    --  -40.33  12.00  60.00   94
 47  \w    -53.00 -28.00   0.50    0.20    --  -40.33  64.00  60.00   50
 48  \w    -23.00  31.00   0.50    0.20    --  -40.33  12.00 -60.00  108
 49  \w    -51.00 -14.00   0.50    0.50    --  -82.50  59.00  30.00   74
 50  \w    -42.00 -16.00   0.50    0.50    --  -82.50  42.00 150.00   52
 51  \w    -47.00 -17.00   0.50    0.50    --  -82.50  42.00  90.00   60
 52  \w    -45.00 -19.00   0.50    0.50    --  -82.50  42.00 -90.00   52
 53  \w    -44.00 -16.00   0.50    0.50    --  -82.50  42.00-120.00   56
 54  \w    -44.00 -19.00   0.50    0.50    --  -82.50  50.00-120.00   50
 55  \w    -85.00 -15.00   0.50    0.50    --  -82.50 124.00-163.00  140
 56  \w    -86.00 -11.00   0.50    0.20    --  -40.33 124.00-163.00  150
 57  \w   -104.00 -25.00   0.50    0.20    --  -40.33 149.00   0.00  158
 58  \w   -147.00 -99.00   0.50    0.50    --  -82.50 -68.00   0.00   96
 59  \w    -91.00 -24.00   0.50    0.20    --  -40.33 -50.00 -60.00  134
 60  \w    -49.00 -23.00   0.50    0.20    --  -40.33 -77.00 -30.00   52
 61  \w   -108.00 -67.00   0.50    0.20    --  -40.33 -77.00 -30.00   82
 62  \w   -108.00 -56.00   0.50    0.20    --  -40.33-149.00 -46.00  104
 63  \w   -150.00 -56.00   0.50    0.50    --  -82.50-149.00 -46.00  188
 64  \w   -150.00 -73.00   0.50    0.50    --  -82.50-124.00 117.00  154
;
_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      -0.0466322000
_diffrn_orient_matrix_UB_12      0.0353003000
_diffrn_orient_matrix_UB_13      0.0712284000
_diffrn_orient_matrix_UB_21      -0.1633195000
_diffrn_orient_matrix_UB_22      -0.0459620000
_diffrn_orient_matrix_UB_23      -0.0303195000
_diffrn_orient_matrix_UB_31      0.0262944000
_diffrn_orient_matrix_UB_32      -0.1454723000
_diffrn_orient_matrix_UB_33      0.0063301000
_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  0.0594
_diffrn_reflns_av_unetI/netI     0.0438
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            19809
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.310
_diffrn_reflns_theta_min         2.228
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.524
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56864
_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 white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.160
_exptl_crystal_F_000             688
_exptl_crystal_preparation       'hexane in DCM'
_exptl_crystal_recrystallization_method 'hexane in DCM'
_exptl_crystal_size_max          0.002
_exptl_crystal_size_mid          0.001
_exptl_crystal_size_min          0.001
_refine_diff_density_max         0.311
_refine_diff_density_min         -0.240
_refine_diff_density_rms         0.050
_refine_ls_extinction_coef       0.0031(4)
_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   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     444
_refine_ls_number_reflns         6602
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0518
_refine_ls_R_factor_gt           0.0488
_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^)+(0.0795P)^2^+0.4615P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1357
_refine_ls_wR_factor_ref         0.1388
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5997
_reflns_number_total             6602
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02842b2.cif
_cod_data_source_block           bipksk_int_auto
_cod_depositor_comments
;
Adding full bibliography for 1572257--1572260.cif.

2025-05-14
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C46 H52 O2'
_cod_original_formula_weight         636.87
_cod_original_formula_moiety         '2(C23 H26 O)'
_cod_original_formula_units_Z            2
_cod_original_cell_volume        1822.70(6)
_cod_database_code               1572258
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O'
_chemical_oxdiff_usercomment     100K
_shelx_estimated_absorpt_t_max   0.999
_shelx_estimated_absorpt_t_min   0.999
_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:
 C35(H35), C17(H17)
2.b Secondary CH2 refined with riding coordinates:
 C19(H19a,H19b), C37(H37a,H37b), C36(H36a,H36b), C18(H18a,H18b)
2.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C12(H12), C15(H15), C32(H32), C43(H43), C42(H42), C8(H8), C40(H40),
 C41(H41), C13(H13), C39(H39), C16(H16)
2.d Idealised Me refined as rotating group:
 C22(H22a,H22b,H22c), C44(H44a,H44b,H44c), C24(H24a,H24b,H24c), C46(H46a,H46b,
 H46c), C21(H21a,H21b,H21c), C20(H20a,H20b,H20c), C47(H47a,H47b,H47c), C23(H23a,
 H23b,H23c), C48(H48a,H48b,H48c), C45(H45a,H45b,H45c)
;
_shelx_res_checksum              48133
_shelx_hkl_checksum              9546
_olex2_exptl_crystal_mounting_method Cu
_olex2_submission_original_sample_id KSK_KC_INT
_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 1.812
_oxdiff_exptl_absorpt_empirical_full_min 0.711