<i>In Crystallo</i> Snapshots of Rh<sub>2</sub>-Catalyzed C-H Amination.
Das, Anuvab; Wang, Chen-Hao; Van Trieste, 3rd, Gerard P; Sun, Cheng-Jun; Chen, Yu-Sheng; Reibenspies, Joseph H.; Powers, David C.; Journal of the American Chemical Society 142 (2020) 19862–19867; doi:10.1021/jacs.0c09842

data_4135363
_publ_section_title
;
 <i>In Crystallo</i> Snapshots of Rh<sub>2</sub>-Catalyzed C-H Amination.
;
_journal_issue                   47
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              19862
_journal_page_last               19867
_journal_paper_doi               10.1021/jacs.0c09842
_journal_volume                  142
_journal_year                    2020
_chemical_formula_moiety         'C56 H58 N4.28 O8 Rh2, 2(C H Cl3)'
_chemical_formula_sum            'C58 H60 Cl6 N4.28 O8 Rh2'
_chemical_formula_weight         1363.47
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-07-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.334(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.961(2)
_cell_length_b                   12.909(2)
_cell_length_c                   18.381(3)
_cell_measurement_reflns_used    9500
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      13.36
_cell_measurement_theta_min      2.22
_cell_volume                     3025.5(8)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'APEX3 (Bruker-AXS, 2015)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker PHOTON 2 area detector'
_diffrn_detector_area_resol_mean 10.5
_diffrn_detector_type            'Charge-integrating Pixel Array Detector'
_diffrn_measured_fraction_theta_full 0.945
_diffrn_measured_fraction_theta_max 0.945
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 goniometer'
_diffrn_measurement_method       'omega and phi scans'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.41328
_diffrn_reflns_av_R_equivalents  0.0887
_diffrn_reflns_av_unetI/netI     0.0441
_diffrn_reflns_Laue_measured_fraction_full 0.945
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            47513
_diffrn_reflns_point_group_measured_fraction_full 0.945
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        13.490
_diffrn_reflns_theta_max         13.490
_diffrn_reflns_theta_min         1.127
_diffrn_source                   synchrotron
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.457
_exptl_absorpt_correction_T_max  0.7437
_exptl_absorpt_correction_T_min  0.6476
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0839 before and 0.0678 after correction.
The Ratio of minimum to maximum transmission is 0.8708.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            green
_exptl_crystal_density_diffrn    1.497
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1388
_exptl_crystal_size_max          0.40
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.303
_refine_diff_density_min         -0.489
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     519
_refine_ls_number_reflns         4316
_refine_ls_number_restraints     338
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0615
_refine_ls_R_factor_gt           0.0447
_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^)+(0.0554P)^2^+6.0875P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1149
_refine_ls_wR_factor_ref         0.1242
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3424
_reflns_number_total             4316
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c09842_si_002.cif
_cod_data_source_block           5b
_cod_depositor_comments
'Adding full bibliography for 4135359--4135363.cif.'
_cod_original_cell_volume        3025.5(9)
_cod_database_code               4135363
_shelx_shelxl_version_number     2014/7
_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. Restrained distances
 C1_3-Cl1_3 \\sim C1_3-Cl2_3 \\sim C1_3-Cl3_3
 C1_4-Cl1_4 \\sim C1_4-Cl2_4 \\sim C1_4-Cl3_4
 with sigma of 0.02
 Cl1_3-Cl2_3 \\sim Cl2_3-Cl3_3 \\sim Cl3_3-Cl1_3
 Cl1_4-Cl2_4 \\sim Cl2_4-Cl3_4 \\sim Cl3_4-Cl1_4
 with sigma of 0.04
3. Rigid bond restraints
 C1_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2, C8_2, C9_2, C10_2, C11_2, C12_2
 C1_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1, C8_1, C9_1, C10_1, C11_1, C12_1
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C1_3, Cl1_3, Cl2_3, Cl3_3
 C1_4, Cl1_4, Cl2_4, Cl3_4
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 N1A, N2, N3
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
C1_2 \\sim C2_2 \\sim C3_2 \\sim C4_2 \\sim C5_2 \\sim C6_2 \\sim C7_2 \\sim
C8_2 \\sim C9_2 \\sim C10_2 \\sim C11_2 \\sim C12_2 \\sim C1_1 \\sim C2_1 \\sim
C3_1 \\sim C4_1 \\sim C5_1 \\sim C6_1 \\sim C7_1 \\sim C8_1 \\sim C9_1 \\sim
C10_1 \\sim C11_1 \\sim C12_1: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C1_3 \\sim Cl1_3 \\sim Cl2_3 \\sim Cl3_3 \\sim C1_4 \\sim Cl1_4 \\sim Cl2_4
\\sim Cl3_4: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
N1A \\sim N2 \\sim N3: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
5. Same fragment restrains
{C1_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1, C8_1, C9_1, C10_1, C11_1, C12_1}
as
{C1_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2, C8_2, C9_2, C10_2, C11_2, C12_2}
sigma for 1-2: 0.001 1-3: 0.04
6. Others
 Sof(N1B)=Sof(C1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=
 Sof(H5)=Sof(C6)=Sof(C7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=
 Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=Sof(C1)=Sof(H1)=Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=
 1-FVAR(1)
 Sof(N1A)=Sof(N2)=Sof(N3)=Sof(C1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=
 Sof(H4)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(C7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=
 Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=Sof(C1)=Sof(H1)=Sof(Cl1)=
 Sof(Cl2)=Sof(Cl3)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C1(H1), C1(H1)
7.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C12(H12A,H12B)
7.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C9(H9), C10(H10), C11(H11), C2(H2), C3(H3), C4(H4), C5(H5), C8(H8),
 C9(H9), C10(H10), C11(H11), C12(H12), C2(H2), C3(H3), C4(H4), C5(H5), C8(H8),
 C9(H9), C10(H10), C11(H11), C12(H12)
7.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              2944
_shelx_hkl_checksum              56455
_olex2_submission_special_instructions 'No special instructions were received'