Comparison of 1,2-Diarylcyclopropanecarboxylates with 1,2,2-Triarylcyclopropanecarboxylates as Chiral Ligands for Dirhodium-Catalyzed Cyclopropanation and C-H Functionalization.
Wertz, Benjamin; Ren, Zhi; Bacsa, John; Musaev, Djamaladdin G.; Davies, Huw M. L.; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c01276

data_4038760
_publ_section_title
;
 Comparison of 1,2-Diarylcyclopropanecarboxylates with
 1,2,2-Triarylcyclopropanecarboxylates as Chiral Ligands for
 Dirhodium-Catalyzed Cyclopropanation and C-H Functionalization.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c01276
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C66 H47 Br8 N O8 Rh2, 3(C7 H8)'
_chemical_formula_sum            'C87 H71 Br8 N O8 Rh2'
_chemical_formula_weight         2103.574
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_Int_Tables_number      19
_atom_sites_solution_primary     dual
_audit_creation_date             2020-05-02
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.04.02 svn.r1fbe7b6f for OlexSys, GUI svn.r6076)
;
_cell_angle_alpha                90.0
_cell_angle_beta                 90.0
_cell_angle_gamma                90.0
_cell_formula_units_Z            4
_cell_length_a                   16.2100(4)
_cell_length_b                   19.2876(4)
_cell_length_c                   25.6190(6)
_cell_measurement_reflns_used    35319
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      31.8090
_cell_measurement_theta_min      1.5280
_cell_volume                     8009.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'APEX2 v2014.11 (Bruker, 2014)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.3-alpha (Bourhis et al., 2015)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 0.9988
_diffrn_measured_fraction_theta_max 0.9851
_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     -6.76 199.24   0.50   25.00    --   30.66  73.80 -25.76  412
  2  \w    116.24 198.74   0.50   25.00    --   30.66  73.80 154.24  165
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'Bruker D8 diffractometer with APEX2 detector'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0155242000
_diffrn_orient_matrix_UB_12      0.0116096000
_diffrn_orient_matrix_UB_13      0.0243827000
_diffrn_orient_matrix_UB_21      0.0370615000
_diffrn_orient_matrix_UB_22      -0.0185224000
_diffrn_orient_matrix_UB_23      -0.0044599000
_diffrn_orient_matrix_UB_31      0.0172097000
_diffrn_orient_matrix_UB_32      0.0296098000
_diffrn_orient_matrix_UB_33      -0.0123369000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0360
_diffrn_reflns_av_unetI/netI     0.0574
_diffrn_reflns_Laue_measured_fraction_full 0.9988
_diffrn_reflns_Laue_measured_fraction_max 0.9851
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            49609
_diffrn_reflns_point_group_measured_fraction_full 0.9990
_diffrn_reflns_point_group_measured_fraction_max 0.9811
_diffrn_reflns_theta_full        26.0000
_diffrn_reflns_theta_max         30.51
_diffrn_reflns_theta_min         1.64
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_current           35
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_source_voltage           45
_exptl_absorpt_coefficient_mu    4.459
_exptl_absorpt_correction_T_max  0.20940
_exptl_absorpt_correction_T_min  0.18498
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark blue'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.744
_exptl_crystal_description       prism
_exptl_crystal_F_000             4116.595
_exptl_crystal_size_max          0.677
_exptl_crystal_size_mid          0.493
_exptl_crystal_size_min          0.464
_refine_diff_density_max         1.2283
_refine_diff_density_min         -1.2136
_refine_diff_density_rms         0.1792
_refine_ls_abs_structure_details
'Flack, H. D. (1983). Acta Cryst. A39, 876-881.'
_refine_ls_abs_structure_Flack   0.012(5)
_refine_ls_d_res_high            0.7000
_refine_ls_d_res_low             12.4094
_refine_ls_goodness_of_fit_ref   1.0386
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    12
_refine_ls_number_parameters     1771
_refine_ls_number_reflns         23988
_refine_ls_number_restraints     2355
_refine_ls_restrained_S_all      0.9876
_refine_ls_R_factor_all          0.0582
_refine_ls_R_factor_gt           0.0418
_refine_ls_shift/su_max          0.0001
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0473P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0829
_refine_ls_wR_factor_ref         0.0890
_reflns_Friedel_coverage         0.977
_reflns_limit_h_max              23
_reflns_limit_h_min              -23
_reflns_limit_k_max              27
_reflns_limit_k_min              -27
_reflns_limit_l_max              36
_reflns_limit_l_min              -36
_reflns_number_gt                20171
_reflns_number_total             23988
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            jo0c01276_si_003.cif
_cod_data_source_block           BDW-2-20-3
_cod_original_sg_symbol_Hall     ' P 2ac 2ab'
_cod_database_code               4038760
_chemical_oxdiff_formula         'C87 H71 Br8 N O8 Rh2'
_cell_oxdiff_length_a            16.2258(2)
_cell_oxdiff_length_b            19.2709(3)
_cell_oxdiff_length_c            25.6163(4)
_cell_oxdiff_angle_alpha         90.0213(12)
_cell_oxdiff_angle_beta          90.0438(12)
_cell_oxdiff_angle_gamma         90.1226(12)
_cell_oxdiff_volume              8009.8(2)
_reflns_odcompleteness_completeness 98.55
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All H(H) groups, All C(H,H) groups, All C(H,H,H) groups
2. Restrained distances
 C73-H73
 1.05 with sigma of 0.01
 H69-C69
 1.05 with sigma of 0.01
 H70-C70
 1.05 with sigma of 0.01
 C72-H72
 1.05 with sigma of 0.01
 H71-C71
 1.05 with sigma of 0.01
 C67-H67A
 1.05 with sigma of 0.01
 C13-H13 = C14-H14 = C15-H15 = C16-H16 = C12-H12
 1.05 with sigma of 0.01
 C58-H58 \\sim C57-H57A \\sim C57-H57B \\sim C3-H3B \\sim C3-H3A \\sim C4-H4
 with sigma of 0.002
 C6S-H6S \\sim C5S-H5S \\sim C4S-H4S \\sim C3S-H3S \\sim C7S-H7S
 with sigma of 0.002
 H4S-H3S \\sim H7S-H6S
 with sigma of 0.004
 H6S-H5S \\sim H5S-H4S
 with sigma of 0.002
 H1SC-H1SB \\sim H1SC-H1SA \\sim H1SB-H1SA
 with sigma of 0.002
 H67B-H67A \\sim H67C-H67A \\sim H67C-H67B
 with sigma of 0.002
 H67C-H67A \\sim H67C-H67B \\sim H67B-H67A
 with sigma of 0.0002
3. Restrained planarity
 C3S, H3S, C4S, H4S, C5S, H5S, C2S, C6S, H6S, C7S, H7S
 with sigma of 0.002
 H12, C12, C13, H13, C14
 with sigma of 0.002
4. Uiso/Uaniso restraints and constraints
Uanis(C68) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(H60) = Uanis(H61)
Uanis(H11S) = Uanis(H10S)
Uanis(H7S) = Uanis(H6S) = Uanis(H5S) = Uanis(H3S) = Uanis(H4S)
Uanis(H13) = Uanis(H14)
Uanis(H12) = Uanis(H13)
Uanis(H62) = Uanis(H63)
Uanis(H14) = Uanis(H13)
5. Rigid body (RIGU) restrains
 N1, C65, C66
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C1S, C3S, C4S, C2S, C5S, C7S, C6S
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C1S, H1SA, H1SB, H1SC
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C70, C71, C72, C69, C73, C68, C67
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C38, Rh2, O4, O2, O8, O6, Rh1, C17, C1, C33, C49, O7, O5, O1, O3, N1, C18, C2,
  C34, C50, C65, C26, C19, C25, C5, C3, C4, C41, C35, C42, C57, C51, C58, C66,
 C27, C20, C24, C6, C10, C11, C36, C40, C43, C52, C56, C59, C28, C32, C21, C23,
 C7, C9, C12, C16, C37, C39, C44, C1D, C53, C55, C60, C64, C29, C31, Br3, C22,
 Br4, Br1, C8, Br2, C13, C15, Br5, Br6, C45, C47, Br7, C54, Br8, C61, C63, C30,
 C14, C46, C62
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C36, C38, C40
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 H12, C7, C6, C8, H6, C5, H8, C9, C2, C10, C3, C4, C1, H10, H3A, H3B, H4, C11,
 O2, O1, C12, C16, C13, H16, C15, H13, C14, H15, H14
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C45, C37, C36, C38, H36, C35, H38, C39, C34, C40, C41, C42, C33, H40, H41A,
 H41B, H42, C43, O7, O8, C44, C1D, H44, C47, H1D, C46, H45, H47, H46
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C23, C22, C24, C21, H22, H24, C19, C20, C18, H20, C17, C26, C25, O3, O4, H26,
 C27, H25A, H25B, C28, C32, H28, C29, H32, C31, C30, H29, H31, H30
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 H13S, C10S, H10S, C11S, C9S, H11S, C12S, C14S, C8S, C13S, H12S, H14S, H8SA,
 H8SB, H8SC
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C55, C54, C56, H54, C53, C51, H56, C52, C50, H52, C49, C57, C58, O5, O6, H57A,
  H57B, H58, C59, C60, C64, C61, H60, H64, C63, H61, H63, H62, C62
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C66, C65, H66B, H66A, H66C, N1
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C71, H71, C70, C72, H70, C69, H72, C73, C68, H69, H73, C67, H67A, H67B, H67C
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C8S, C10S, H10S, C11S, C9S, H11S, C12S, C14S, C13S, H12S, H14S, H8SA, H8SB,
 H8SC, H13S
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C34, C41, H41A, H41B, C42, H42
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C36, H36, C37, C38, H38, C40, H40
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
6.a Aromatic/amide H refined with riding coordinates:
 C36(H36), C40(H40), C38(H38)
6.b Idealised Me refined as rotating group:
 C8S(H8SA,H8SB,H8SC), C66(H66A,H66B,H66C)
;
_olex2_submission_original_sample_id BDW-2-20-3
_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 1.398
_oxdiff_exptl_absorpt_empirical_full_min 0.692