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_4038759
_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         'C68 H58 N2 O8 Rh2, 2(C2 H3 N)'
_chemical_formula_sum            'C72 H64 N4 O8 Rh2'
_chemical_formula_weight         1319.09
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-04-05
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5332)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.901(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.8960(2)
_cell_length_b                   21.1720(4)
_cell_length_c                   14.8082(3)
_cell_measurement_reflns_used    56447
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      37.9570
_cell_measurement_theta_min      2.2830
_cell_volume                     3046.60(11)
_computing_cell_refinement       'CrysAlisPro 1.171.39.9g (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.9g (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.9g (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 HyPix
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.997
_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     52.00 104.00   0.50    7.00    --   29.51 152.00 103.00  104
  2  \w     52.00 104.00   0.50    7.00    --   29.51  77.00 120.00  104
  3  \w     62.00  88.00   0.50    7.00    --   29.51 178.00 -30.00   52
  4  \w     40.00 108.00   0.50    7.00    --   29.51 178.00-150.00  136
  5  \w     39.00  77.00   0.50    7.00    --   29.51 178.00-180.00   76
  6  \w    -82.00 -38.00   0.50    7.00    --  -29.66 122.00 -56.00   88
  7  \w    -97.00 -72.00   0.50    7.00    --  -29.66 152.00 103.00   50
  8  \w      1.00  29.00   0.50    7.00    --   29.51  77.00 120.00   56
  9  \w      8.00  82.00   0.50    7.00    --   29.51-122.00-138.00  148
 10  \w     24.00 100.00   0.50    7.00    --   29.51-152.00  61.00  152
 11  \w   -108.00 -62.00   0.50    7.00    --  -29.66-178.00 -30.00   92
 12  \w   -108.00 -61.00   0.50    7.00    --  -29.66-178.00 -90.00   94
 13  \w   -103.00  -1.00   0.50    7.00    --  -29.66 -77.00-150.00  204
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0538921000
_diffrn_orient_matrix_UB_12      0.0045679000
_diffrn_orient_matrix_UB_13      -0.0384706000
_diffrn_orient_matrix_UB_21      0.0027169000
_diffrn_orient_matrix_UB_22      0.0329913000
_diffrn_orient_matrix_UB_23      0.0082106000
_diffrn_orient_matrix_UB_31      0.0491807000
_diffrn_orient_matrix_UB_32      0.0032549000
_diffrn_orient_matrix_UB_33      -0.0288991000
_diffrn_radiation_monochromator  'multilayer mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0243
_diffrn_reflns_av_unetI/netI     0.0258
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            65165
_diffrn_reflns_point_group_measured_fraction_full 0.955
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         34.338
_diffrn_reflns_theta_min         2.096
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.603
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.404
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.9g (Rigaku Oxford Diffraction, 2015)
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            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.438
_exptl_crystal_description       prism
_exptl_crystal_F_000             1356
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.522
_exptl_crystal_size_mid          0.483
_exptl_crystal_size_min          0.23
_refine_diff_density_max         0.499
_refine_diff_density_min         -0.736
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 10662 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.015(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     822
_refine_ls_number_reflns         24058
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0197
_refine_ls_R_factor_gt           0.0192
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0280P)^2^+0.3728P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0488
_refine_ls_wR_factor_ref         0.0490
_reflns_Friedel_coverage         0.851
_reflns_Friedel_fraction_full    0.912
_reflns_Friedel_fraction_max     0.887
_reflns_number_gt                23688
_reflns_number_total             24058
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01276_si_004.cif
_cod_data_source_block           bw-04-04
_cod_database_code               4038759
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C71H64N5O8Rh2
_diffrn_oxdiff_ac3_digest_frames
;
01204dd57a4f84014d45f02fd1d64556a901356f9fd
;
_diffrn_oxdiff_ac3_digest_hkl
;
0101838c470f6b91f7f76bb161929dc9fcae9b
;
_reflns_odcompleteness_completeness 99.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     34.89
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C4-H4B = C4-H4A
 0.995 with sigma of 0.005
 C3-H3
 0.995 with sigma of 0.005
 C19-H19 = C20-H20B = C20-H20A
 0.995 with sigma of 0.005
 C52-H52B = C52-H52A = C51-H51
 0.995 with sigma of 0.005
 C36-H36A = C36-H36B = C35-H35
 0.995 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uiso(H4B) = Uiso(H4A)
Uiso(H20B) = Uiso(H20A) = Uiso(H19)
Uiso(H52A) = Uiso(H52B) = Uiso(H51)
4.a Aromatic/amide H refined with riding coordinates:
 C9(H9), C12(H12), C14(H14), C8(H8), C60(H60), C6(H6), C15(H15), C44(H44),
 C22(H22), C48(H48), C64(H64), C16(H16), C28(H28), C13(H13), C10(H10), C31(H31),
  C38(H38), C56(H56), C47(H47), C45(H45), C46(H46), C7(H7), C54(H54), C32(H32),
 C61(H61), C30(H30), C23(H23), C58(H58), C29(H29), C57(H57), C55(H55), C63(H63),
  C39(H39), C42(H42), C24(H24), C26(H26), C62(H62), C41(H41), C40(H40), C25(H25)
4.b Idealised Me refined as rotating group:
 C66(H66A,H66B,H66C), C68(H68A,H68B,H68C), C70(H70A,H70B,H70C), C72(H72A,H72B,
 H72C)
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id BW-04-04
_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 1.195
_oxdiff_exptl_absorpt_empirical_full_min 0.817