Stereo- and Regiocontrol in Intermolecular [2+2] Cycloadditions between Diarylketenes and Allenamides to Access Substituted α-Methylenecyclobutanones.
Liu, Rai-Shung; Kshirsagar, Akshay Suresh; More, Sayaji Arjun; Chemical Communications  (2023) –; doi:10.1039/D3CC03979J

data_7132117
_publ_section_title
;
 Stereo- and Regiocontrol in Intermolecular [2+2] Cycloadditions between
 Diarylketenes and Allenamides to Access Substituted
 \a-Methylenecyclobutanones.
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC03979J
_journal_year                    2023
_chemical_formula_moiety         'C21 H18 Br N O4'
_chemical_formula_sum            'C21 H18 Br N O4'
_chemical_formula_weight         428.27
_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     dual
_audit_creation_date             2022-04-21
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-05-11 deposited with the CCDC.	2023-09-12 downloaded from the CCDC.
;
_cell_angle_alpha                91.770(2)
_cell_angle_beta                 98.537(2)
_cell_angle_gamma                96.489(2)
_cell_formula_units_Z            2
_cell_length_a                   8.5723(2)
_cell_length_b                   10.1918(3)
_cell_length_c                   10.7219(3)
_cell_measurement_reflns_used    6642
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.7370
_cell_measurement_theta_min      4.1790
_cell_volume                     919.34(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.51a (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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.945
_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   -101.00 -40.00   0.50    0.10    --  -76.01 -15.00  60.00  122
  2  \w    -91.00 -65.00   0.50    0.10    --  -76.01 111.00  30.00   52
  3  \w    -88.00 -62.00   0.50    0.10    --  -76.01 111.00 -30.00   52
  4  \w    -56.00 -28.00   0.50    0.10    --  -76.01 111.00 -30.00   56
  5  \w    -54.00 -28.00   0.50    0.10    --  -76.01 111.00  30.00   52
  6  \w     80.00 106.00   0.50    0.10    --   56.31  15.00  30.00   52
  7  \w     59.00 120.00   0.50    0.10    --   69.43  15.00  90.00  122
  8  \w     43.00  91.00   0.50    0.10    --   76.52  15.00  60.00   96
  9  \w     59.00 134.00   0.50    0.10    --   84.37  15.00 150.00  150
 10  \w     45.00  75.00   0.50    0.10    --   56.31  15.00  30.00   60
 11  \w     52.00  77.00   0.50    0.10    --   84.37  15.00 120.00   50
 12  \w     47.00 122.00   0.50    0.10    --   76.52  15.00 -30.00  150
 13  \w     45.00 108.00   0.50    0.10    --   76.52  15.00 -90.00  126
 14  \w     63.00 134.00   0.50    0.10    --   84.37  15.00-150.00  142
 15  \w     45.00  88.00   0.50    0.10    --   84.37 -95.00 -90.00   86
 16  \w     66.00  92.00   0.50    0.10    --   76.52-111.00 -90.00   52
 17  \w     27.00  52.00   0.50    0.10    --   69.43 -95.00 -30.00   50
 18  \w     15.00  40.00   0.50    0.10    --   56.31 -95.00 -60.00   50
 19  \w     28.00  59.00   0.50    0.10    --   69.43 -95.00-180.00   62
 20  \w     37.00  62.00   0.50    0.10    --   76.52 -95.00-120.00   50
 21  \w     37.00  63.00   0.50    0.10    --   76.52 -95.00 -60.00   52
 22  \w     15.00  40.00   0.50    0.10    --   56.31 -95.00-120.00   50
 23  \w     15.00  41.00   0.50    0.10    --   56.31 -95.00 -90.00   52
 24  \w     46.00  92.00   0.50    0.10    --   84.37 -95.00  30.00   92
 25  \w     46.00  91.00   0.50    0.10    --   84.37 -95.00  60.00   90
 26  \w     19.00  53.00   0.50    0.10    --   56.31-125.00 150.00   68
 27  \w     35.00  92.00   0.50    0.10    --   80.00-101.00 174.41  114
 28  \w     37.00  92.00   0.50    0.10    --   76.52-111.00 150.00  110
 29  \w     47.00  92.00   0.50    0.10    --   84.37 -95.00  90.00   90
 30  \w     43.00  92.00   0.50    0.10    --   84.37 -95.00   0.00   98
 31  \w     51.00  92.00   0.50    0.10    --   84.37 -95.00 -30.00   82
 32  \w     66.00  92.00   0.50    0.10    --   84.37 -95.00 -60.00   52
 33  \w     42.00  89.00   0.50    0.10    --   84.37 -95.00-150.00   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1121300000
_diffrn_orient_matrix_UB_12      0.0400353000
_diffrn_orient_matrix_UB_13      0.1246685000
_diffrn_orient_matrix_UB_21      0.0996603000
_diffrn_orient_matrix_UB_22      -0.1119381000
_diffrn_orient_matrix_UB_23      -0.0250885000
_diffrn_orient_matrix_UB_31      0.1048511000
_diffrn_orient_matrix_UB_32      0.0952131000
_diffrn_orient_matrix_UB_33      -0.0706293000
_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  0.0236
_diffrn_reflns_av_unetI/netI     0.0280
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            10098
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.961
_diffrn_reflns_theta_min         4.174
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.282
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92339
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.51a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.547
_exptl_crystal_description       block
_exptl_crystal_F_000             436
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.373
_refine_diff_density_min         -0.536
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     245
_refine_ls_number_reflns         3579
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0344
_refine_ls_R_factor_gt           0.0296
_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^)+(0.0304P)^2^+0.7277P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0722
_refine_ls_wR_factor_ref         0.0743
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3203
_reflns_number_total             3579
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc03979j2.cif
_cod_data_source_block           220428lt_auto
_cod_database_code               7132117
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.880
_shelx_estimated_absorpt_t_min   0.853
_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:
 C10(H10)
2.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C21(H21A,H21B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C6(H6), C12(H12), C13(H13), C15(H15), C16(H16)
2.d X=CH2 refined with riding coordinates:
 C26(H26A,H26B)
2.e Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C)
;
_shelx_res_checksum              25882
_shelx_hkl_checksum              23116
_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 1.264
_oxdiff_exptl_absorpt_empirical_full_min 0.880