Ring-fused cyclobutanes via cycloisomerization of alkylidenecyclopropane acylsilanes
Eichenberger, Sarah; Hönig, Moritz; Richter, Matthieu J. R.; Gershoni-Poranne, Renana; Carreira, Erick M.; Chemical Science 11 (2020) 5294–5298; doi:10.1039/D0SC02224A

data_1557999
_publ_section_title
;
 Ring-fused cyclobutanes via cycloisomerization of alkylidenecyclopropane
 acylsilanes
;
_journal_issue                   20
_journal_name_full               'Chemical Science'
_journal_page_first              5294
_journal_page_last               5298
_journal_paper_doi               10.1039/D0SC02224A
_journal_volume                  11
_journal_year                    2020
_chemical_formula_moiety         'C28 H30 Br N O2 Si, C3 H7'
_chemical_formula_sum            'C31 H37 Br N O2 Si'
_chemical_formula_weight         563.61
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-04-17 deposited with the CCDC.	2020-05-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.5460(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.00200(10)
_cell_length_b                   8.35050(10)
_cell_length_c                   18.65040(10)
_cell_measurement_reflns_used    57270
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.3500
_cell_measurement_theta_min      2.4230
_cell_volume                     2836.83(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.42a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.42a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.42a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.986
_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      1.00  33.00   0.50    0.17    --   34.00  96.00 116.03   64
  2  \w     29.00 120.00   0.50    0.17    --   54.00  81.00 101.51  182
  3  \w    120.00 175.00   0.50    0.68    --  110.00  77.00 120.00  110
  4  \w    131.00 168.00   0.50    0.68    --  110.00  77.00  60.00   74
  5  \w    118.00 175.00   0.50    0.68    --  110.00  77.00 150.00  114
  6  \w    121.00 175.00   0.50    0.68    --  110.00  77.00  30.00  108
  7  \w    120.00 176.00   0.50    0.68    --  110.00  77.00   0.00  112
  8  \w    125.00 176.00   0.50    0.68    --  110.00  77.00 -30.00  102
  9  \w     97.00 147.00   0.50    0.68    --  110.00  56.00 -17.60  100
 10  \w     94.00 138.00   0.50    0.68    --  110.00  57.00 -60.00   88
 11  \w     97.00 127.00   0.50    0.68    --  110.00  57.00 -30.00   60
 12  \w     97.00 178.00   0.50    0.68    --  110.00  57.00 -90.00  162
 13  \w     99.00 126.00   0.50    0.68    --  110.00  57.00-150.00   54
 14  \w     98.00 151.00   0.50    0.68    --  110.00  38.00-180.00  106
 15  \w     94.00 122.00   0.50    0.68    --  110.00  57.00-120.00   56
 16  \w    100.00 126.00   0.50    0.68    --  110.00  38.00-150.00   52
 17  \w     86.00 175.00   0.50    0.68    --  110.00  77.00-180.00  178
 18  \w     88.00 176.00   0.50    0.68    --  110.00  77.00 -60.00  176
 19  \w     95.00 149.00   0.50    0.68    --  110.00  57.00  60.00  108
 20  \w     98.00 126.00   0.50    0.68    --  110.00  38.00 150.00   56
 21  \w     98.00 145.00   0.50    0.68    --  110.00  38.00 120.00   94
 22  \w     94.00 134.00   0.50    0.68    --  110.00  57.00  30.00   80
 23  \w     86.00 114.00   0.50    0.68    --  110.00  77.00 120.00   56
 24  \w     86.00 171.00   0.50    0.68    --  110.00  77.00  90.00  170
 25  \w     86.00 112.00   0.50    0.68    --  110.00  77.00 150.00   52
 26  \w     86.00 116.00   0.50    0.68    --  110.00  77.00  60.00   60
 27  \w     86.00 114.00   0.50    0.68    --  110.00  77.00   0.00   56
 28  \w     86.00 112.00   0.50    0.68    --  110.00  77.00 -30.00   52
 29  \w     87.00 113.00   0.50    0.68    --  110.00  77.00  30.00   52
 30  \w     59.00  88.00   0.50    0.17    --   78.00  66.00  29.61   58
 31  \w     34.00 121.00   0.50    0.17    --   49.37  57.00 -60.00  174
 32  \w     62.00  98.00   0.50    0.68    --   86.00  79.00 -65.63   72
 33  \w     86.00 174.00   0.50    0.68    --  110.00  77.00-120.00  176
 34  \w     86.00 176.00   0.50    0.68    --  110.00  77.00-150.00  180
 35  \w     70.00  96.00   0.50    0.68    --  110.00 -99.00-120.00   52
 36  \w     61.00 102.00   0.50    0.68    --  110.00-125.00 -90.00   82
 37  \w     83.00 108.00   0.50    0.68    --  110.00 -99.00 -30.00   50
 38  \w     79.00 110.00   0.50    0.68    --  110.00 -99.00  60.00   62
 39  \w     79.00 110.00   0.50    0.68    --  110.00 -99.00 150.00   62
 40  \w     57.00 122.00   0.50    0.17    --   49.37-178.00 120.00  130
 41  \w     44.00  97.00   0.50    0.68    --  110.00 -99.00   0.00  106
 42  \w     48.00  76.00   0.50    0.68    --  110.00 -99.00 -30.00   56
 43  \w     45.00  92.00   0.50    0.68    --  110.00 -99.00 -60.00   94
 44  \w     41.00  90.00   0.50    0.68    --  110.00 -99.00-180.00   98
 45  \w     37.00 125.00   0.50    0.17    --   49.37  38.00 -60.00  176
 46  \w     34.00 121.00   0.50    0.17    --   49.37  57.00   0.00  174
 47  \w     34.00 121.00   0.50    0.17    --   49.37  57.00  30.00  174
 48  \w     37.00 125.00   0.50    0.17    --   49.37  38.00-120.00  176
 49  \w     30.00 120.00   0.50    0.17    --   54.00  79.00  44.96  180
 50  \w     25.00 116.00   0.50    0.17    --   50.00  80.00-107.59  182
 51  \w     29.00 120.00   0.50    0.17    --   54.00  80.00 -28.26  182
 52  \w     20.00  46.00   0.50    0.17    --   50.00  90.00 -73.30   52
 53  \w    -74.00  18.00   0.50    0.17    --  -38.00 102.00 129.21  184
 54  \w     28.00 121.00   0.50    0.17    --   54.00  82.00 165.28  186
 55  \w     45.00  75.00   0.50    0.68    --  110.00 -99.00  60.00   60
 56  \w     50.00  95.00   0.50    0.68    --  110.00 -99.00  90.00   90
 57  \w     46.00  73.00   0.50    0.68    --  110.00 -99.00 150.00   54
 58  \w    -93.00 -25.00   0.50    0.17    --  -26.00 156.00 175.55  136
 59  \w    -67.00   2.00   0.50    0.68    --  -70.00  57.00  30.00  138
 60  \w    -92.00 -24.00   0.50    0.17    --  -26.00 154.00 108.86  136
 61  \w   -125.00 -37.00   0.50    0.17    --  -49.87 -38.00 -90.00  176
 62  \w    -72.00 -44.00   0.50    0.68    --  -70.00 -82.00 -33.15   56
 63  \w    -71.00 -46.00   0.50    0.68    --  -70.00 -77.00 -90.00   50
 64  \w    -70.00 -43.00   0.50    0.68    --  -70.00 -83.00 -97.07   54
 65  \w    -76.00 -46.00   0.50    0.68    --  -70.00 -77.00   0.00   60
 66  \w    -72.00 -46.00   0.50    0.68    --  -70.00 -77.00  30.00   52
 67  \w    -77.00 -46.00   0.50    0.68    --  -70.00 -77.00  90.00   62
 68  \w    -81.00 -51.00   0.50    0.68    --  -70.00 -66.00 162.40   60
 69  \w    -92.00 -46.00   0.50    0.68    --  -70.00 -80.00 168.81   92
 70  \w    -85.00 -51.00   0.50    0.68    --  -70.00 -66.00  97.05   68
 71  \w    -96.00 -50.00   0.50    0.68    --  -70.00 -67.00 124.65   92
 72  \w   -133.00-102.00   0.50    0.68    --  -70.00 -66.00  97.05   62
 73  \w   -136.00 -46.00   0.50    0.68    --  -70.00 -77.00  60.00  180
 74  \w   -127.00-101.00   0.50    0.68    --  -70.00 -83.00 -97.07   52
 75  \w    -89.00 -47.00   0.50    0.68    --  -70.00 -75.00-159.21   84
 76  \w   -125.00 -37.00   0.50    0.17    --  -49.87 -38.00-180.00  176
 77  \w   -136.00 -47.00   0.50    0.68    --  -70.00 -74.00 -74.92  178
 78  \w   -136.00 -47.00   0.50    0.68    --  -70.00 -76.00-130.42  178
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0064746000
_diffrn_orient_matrix_UB_12      -0.0009342000
_diffrn_orient_matrix_UB_13      0.0804840000
_diffrn_orient_matrix_UB_21      -0.0842810000
_diffrn_orient_matrix_UB_22      -0.0051905000
_diffrn_orient_matrix_UB_23      -0.0307914000
_diffrn_orient_matrix_UB_31      0.0024470000
_diffrn_orient_matrix_UB_32      -0.1844264000
_diffrn_orient_matrix_UB_33      0.0004909000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0475
_diffrn_reflns_av_unetI/netI     0.0173
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            84976
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.771
_diffrn_reflns_theta_min         2.426
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.589
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.640
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.42a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.320
_exptl_crystal_description       plank
_exptl_crystal_F_000             1180
_exptl_crystal_size_max          0.225
_exptl_crystal_size_mid          0.082
_exptl_crystal_size_min          0.042
_refine_diff_density_max         0.538
_refine_diff_density_min         -0.645
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     331
_refine_ls_number_reflns         6092
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0362
_refine_ls_R_factor_gt           0.0347
_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^)+(0.0445P)^2^+2.4260P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0922
_refine_ls_wR_factor_ref         0.0933
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5761
_reflns_number_total             6092
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc02224a2.cif
_cod_data_source_block           ca230619_2_1
_cod_depositor_comments
;Adding full bibliography for 1557999.cif.

 Adding full bibliography for 1557999.cif.
;
_cod_database_code               1557999
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C28H30BrNO2Si
_diffrn_oxdiff_digest_frames
;
0189204a43a5b5c0d87bd6a43b39bdbed808198dade
;
_diffrn_oxdiff_digest_hkl
;
01c4f1d5028d6304c763d8cf878e0ea407a937
;
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-H1
 0.93 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C8(H8)
3.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C13(H13A,H13B), C17(H17A,H17B), C2A(H2AA,
 H2AB), C3A(H3AA,H3AB)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C19(H19), C20(H20), C21(H21), C22(H22),
 C23(H23), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28)
3.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C1A(H1AA,H1AB,H1AC)
;
_shelx_res_checksum              91928
_olex2_date_sample_data_collection 2019-06-28
_olex2_date_sample_submission    2019-06-27
_olex2_submission_original_sample_id ca230619_2_1
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.485
_oxdiff_exptl_absorpt_empirical_full_min 0.703