Rh-Catalyzed Regioselective ortho-C-H Carbenoid Insertion of Diarylazines.
Yu, Yunliang; Kuai, Changsheng; Chauvin, Remi; Tian, Nian; Ma, Shuangshuang; Cui, Xiuling; The Journal of organic chemistry 82 (2017) 8611–8616; doi:10.1021/acs.joc.7b01472

data_4032719
_publ_section_title
;
 Rh-Catalyzed Regioselective ortho-C-H Carbenoid Insertion of
 Diarylazines.
;
_journal_issue                   16
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              8611
_journal_page_last               8616
_journal_paper_doi               10.1021/acs.joc.7b01472
_journal_volume                  82
_journal_year                    2017
_chemical_formula_moiety         'C13 H14 N O4'
_chemical_formula_sum            'C13 H14 N O4'
_chemical_formula_weight         248.25
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-05-06
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.184(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   7.9578(3)
_cell_length_b                   14.6936(5)
_cell_length_c                   24.4705(10)
_cell_measurement_reflns_used    2472
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.9110
_cell_measurement_theta_min      3.9510
_cell_volume                     2838.84(19)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1213
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.916
_diffrn_measured_fraction_theta_max 0.773
_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    -50.00  28.00   1.00   19.32    --   16.81 -57.00  90.00   78
  2  \w     50.00  83.00   1.00   19.32    --   16.81 178.00 120.00   33
  3  \w    -51.00  55.00   1.00   19.32    --   16.81 -19.00 150.00  106
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0566155000
_diffrn_orient_matrix_UB_12      0.0374065000
_diffrn_orient_matrix_UB_13      -0.0037572000
_diffrn_orient_matrix_UB_21      -0.0089745000
_diffrn_orient_matrix_UB_22      -0.0070482000
_diffrn_orient_matrix_UB_23      -0.0288985000
_diffrn_orient_matrix_UB_31      -0.0692022000
_diffrn_orient_matrix_UB_32      -0.0296580000
_diffrn_orient_matrix_UB_33      0.0020957000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0173
_diffrn_reflns_av_unetI/netI     0.0233
_diffrn_reflns_Laue_measured_fraction_full 0.916
_diffrn_reflns_Laue_measured_fraction_max 0.773
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            6453
_diffrn_reflns_point_group_measured_fraction_full 0.916
_diffrn_reflns_point_group_measured_fraction_max 0.773
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.987
_diffrn_reflns_theta_min         2.929
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.087
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92693
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
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    1.162
_exptl_crystal_description       prism
_exptl_crystal_F_000             1048
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_platon_squeeze_details
;
;
_refine_diff_density_max         0.434
_refine_diff_density_min         -0.299
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     170
_refine_ls_number_reflns         2923
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0870
_refine_ls_R_factor_gt           0.0711
_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^)+(0.1201P)^2^+2.1987P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2092
_refine_ls_wR_factor_ref         0.2257
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2215
_reflns_number_total             2923
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01472_si_002.cif
_cod_data_source_block           exp_1605
_cod_original_cell_volume        2838.83(18)
_cod_database_code               4032719
_reflns_odcompleteness_completeness 90.69
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Uiso/Uaniso restraints and constraints
Uanis(O4A) \\sim Ueq, Uanis(O4) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O4) = Uanis(O4A)
3. Others
 Sof(O4A)=1-FVAR(1)
 Sof(O4)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C9(H9)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5)
4.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C)
;
_shelx_res_checksum              13068
_shelx_hkl_checksum              80274
_shelx_shelxl_version_number     2014/7
_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 1.086
_oxdiff_exptl_absorpt_empirical_full_min 0.917