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_7132119
_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         'C29 H31 N O4 S'
_chemical_formula_sum            'C29 H31 N O4 S'
_chemical_formula_weight         489.61
_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             2022-07-29
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-08-02 deposited with the CCDC.	2023-09-12 downloaded from the CCDC.
;
_cell_angle_alpha                69.991(2)
_cell_angle_beta                 83.0268(19)
_cell_angle_gamma                79.978(2)
_cell_formula_units_Z            2
_cell_length_a                   7.73568(18)
_cell_length_b                   12.3470(3)
_cell_length_c                   14.4133(3)
_cell_measurement_reflns_used    8464
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      74.5130
_cell_measurement_theta_min      3.2570
_cell_volume                     1270.97(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    'SHELXT 2018/2 (Sheldrick, 2018)'
_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            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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     34.00  60.00   0.50    0.06    --   75.69-111.00-120.00   52
  2  \w     45.00  92.00   0.50    0.06    --   75.69-111.00 -90.00   94
  3  \w     28.00  92.00   0.50    0.06    --   75.69-111.00  60.00  128
  4  \w     36.00  65.00   0.50    0.06    --   75.69 -95.00  90.00   58
  5  \w     37.00  90.00   0.50    0.06    --   83.90-111.00 150.00  106
  6  \w     14.00  49.00   0.50    0.06    --   56.22 -95.00  90.00   70
  7  \w     31.00  57.00   0.50    0.06    --   56.22-125.00  90.00   52
  8  \w     63.00  89.00   0.50    0.06    --   83.90 -95.00  90.00   52
  9  \w     14.00  40.00   0.50    0.06    --   56.22 -95.00   0.00   52
 10  \w     15.00  58.00   0.50    0.06    --   56.22 -95.00 150.00   86
 11  \w     44.00  92.00   0.50    0.06    --   83.90-111.00 -30.00   96
 12  \w     65.00  90.00   0.50    0.06    --   83.90 -95.00  60.00   50
 13  \w     66.00  92.00   0.50    0.06    --   83.90 -95.00 -30.00   52
 14  \w     43.00  90.00   0.50    0.06    --   83.90 -95.00 -90.00   94
 15  \w     21.00  52.00   0.50    0.06    --   56.22 -95.00-120.00   62
 16  \w     16.00  42.00   0.50    0.06    --   56.22 -95.00-180.00   52
 17  \w     41.00  90.00   0.50    0.06    --   83.90 -95.00-180.00   98
 18  \w     41.00  91.00   0.50    0.06    --   83.90 -95.00-150.00  100
 19  \w     46.00  90.00   0.50    0.06    --   83.90 -95.00   0.00   88
 20  \w     61.00  92.00   0.50    0.06    --   83.90 -95.00 150.00   62
 21  \w     50.00 134.00   0.50    0.06    --   83.90  15.00  30.00  168
 22  \w     39.00 124.00   0.50    0.06    --   75.69  15.00 -30.00  170
 23  \w     40.00 126.00   0.50    0.06    --   75.69  15.00-120.00  172
 24  \w     73.00  99.00   0.50    0.06    --   69.57  15.00-180.00   52
 25  \w     40.00  65.00   0.50    0.06    --   69.57  15.00-180.00   50
 26  \w     58.00 117.00   0.50    0.06    --   83.90  15.00-180.00  118
 27  \w     48.00 113.00   0.50    0.06    --   83.90  15.00 120.00  130
 28  \w   -113.00 -55.00   0.50    0.06    --  -72.12 -15.00-180.00  116
 29  \w    -67.00 -33.00   0.50    0.06    --  -59.16 125.00-120.00   68
 30  \w    -78.00 -30.00   0.50    0.06    --  -75.04 111.00 -60.00   96
 31  \w    -63.00 -25.00   0.50    0.06    --  -72.12 125.00 -30.00   76
 32  \w    -92.00 -53.00   0.50    0.06    --  -75.04 111.00 120.00   78
;
_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      0.0934280000
_diffrn_orient_matrix_UB_12      -0.0972417000
_diffrn_orient_matrix_UB_13      0.0850820000
_diffrn_orient_matrix_UB_21      -0.1525625000
_diffrn_orient_matrix_UB_22      -0.0711004000
_diffrn_orient_matrix_UB_23      0.0158862000
_diffrn_orient_matrix_UB_31      0.0952835000
_diffrn_orient_matrix_UB_32      -0.0590276000
_diffrn_orient_matrix_UB_33      -0.0742024000
_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  0.0206
_diffrn_reflns_av_unetI/netI     0.0239
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            13857
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.019
_diffrn_reflns_theta_max         67.019
_diffrn_reflns_theta_min         3.271
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.414
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97683
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.279
_exptl_crystal_description       block
_exptl_crystal_F_000             520
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.850
_refine_diff_density_min         -0.408
_refine_diff_density_rms         0.058
_refine_ls_extinction_coef       0.0017(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     320
_refine_ls_number_reflns         4513
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0606
_refine_ls_R_factor_gt           0.0560
_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^)+(0.0702P)^2^+1.5079P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1490
_refine_ls_wR_factor_ref         0.1523
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4055
_reflns_number_total             4513
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc03979j2.cif
_cod_data_source_block           220766lt_auto
_cod_database_code               7132119
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.895
_shelx_estimated_absorpt_t_min   0.838
_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:
 C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C12(H12), C13(H13), C14(H14), C15(H15),
 C16(H16), C30(H30), C31(H31), C33(H33), C34(H34)
2.d X=CH2 refined with riding coordinates:
 C26(H26A,H26B)
2.e Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C28(H28A,H28B,H28C), C35(H35A,H35B,H35C)
;
_shelx_res_checksum              25517
_shelx_hkl_checksum              18195
_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 1.070
_oxdiff_exptl_absorpt_empirical_full_min 0.957