Catalyst-Controlled Selective Functionalization of Unactivated C-H Bonds in the Presence of Electronically Activated C-H Bonds.
Liu, Wenbin; Ren, Zhi; Bosse, Aaron T.; Liao, Kuangbiao; Goldstein, Elizabeth L.; Bacsa, John; Musaev, Djamaladdin G.; Stoltz, Brian M.; Davies, Huw M. L.; Journal of the American Chemical Society 140 (2018) 12247–12255; doi:10.1021/jacs.8b07534

data_4132941
_publ_section_title
;
 Catalyst-Controlled Selective Functionalization of Unactivated C-H Bonds
 in the Presence of Electronically Activated C-H Bonds.
;
_journal_issue                   38
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12247
_journal_page_last               12255
_journal_paper_doi               10.1021/jacs.8b07534
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C22 H16 Br Cl O2'
_chemical_formula_sum            'C22 H16 Br Cl O2'
_chemical_formula_weight         427.71
_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             2018-06-27
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2018.05.31 svn.r3508 for OlexSys, GUI svn.r5510)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.432(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.2116(3)
_cell_length_b                   17.9533(5)
_cell_length_c                   10.9656(4)
_cell_measurement_reflns_used    13197
_cell_measurement_temperature    105(7)
_cell_measurement_theta_max      36.5870
_cell_measurement_theta_min      2.2680
_cell_volume                     1883.87(11)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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      105(7)
_diffrn_detector                 HyPix
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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     65.00  91.00   0.50   13.80    --   22.41  77.00 -90.00   52
  2  \w     16.00  93.00   0.50   13.80    --   22.41  57.00-180.00  154
  3  \w      3.00  58.00   0.50   13.80    --   22.41  77.00 -90.00  110
  4  \w     40.00  89.00   0.50   13.80    --   22.41 178.00  60.00   98
  5  \w     28.00  88.00   0.50   13.80    --   22.41  77.00 120.00  120
  6  \w     -2.00  45.00   0.50   13.80    --  -22.41  38.00 150.00   94
  7  \w     -1.00  59.00   0.50   13.80    --   22.41-110.00 118.00  120
  8  \w    -21.00  23.00   0.50   13.80    --   22.41 -38.00-150.00   88
;
_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      -0.0221850000
_diffrn_orient_matrix_UB_12      0.0373873000
_diffrn_orient_matrix_UB_13      -0.0146275000
_diffrn_orient_matrix_UB_21      -0.0664925000
_diffrn_orient_matrix_UB_22      -0.0094951000
_diffrn_orient_matrix_UB_23      0.0024529000
_diffrn_orient_matrix_UB_31      0.0240946000
_diffrn_orient_matrix_UB_32      0.0084406000
_diffrn_orient_matrix_UB_33      0.0674521000
_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  0.0377
_diffrn_reflns_av_unetI/netI     0.0304
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            23622
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.033
_diffrn_reflns_theta_min         2.128
_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    2.337
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.424
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.508
_exptl_crystal_description       block
_exptl_crystal_F_000             864
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.377
_exptl_crystal_size_mid          0.286
_exptl_crystal_size_min          0.211
_refine_diff_density_max         1.867
_refine_diff_density_min         -1.241
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     243
_refine_ls_number_reflns         5515
_refine_ls_number_restraints     74
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0596
_refine_ls_R_factor_gt           0.0487
_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^)+(0.0522P)^2^+3.1505P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1189
_refine_ls_wR_factor_ref         0.1239
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4624
_reflns_number_total             5515
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b07534_si_003.cif
_cod_data_source_block           wl-c22h16brclo2_iso1
_cod_original_cell_volume        1883.88(11)
_cod_database_code               4132941
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C88  H60  Br4  Cl4  O8  '
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     36.23
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 O1-H1
 0.995 with sigma of 0.002
 Br1A-C8 \\sim Br1B-C8
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(Br1B) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(Br1B) \\sim Ueq, Uanis(Br1A) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(Br1A) = Uanis(Br1B)
4. Rigid body (RIGU) restrains
 C1, C4, O1, O2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C6, Cl1
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 C5, C6, C7, C8, C9, C10
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C8, Br1A
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 Br1B, C8
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C1, C4
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 O1, C4
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 O2, C4
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
5. Others
 Sof(Br1B)=1-FVAR(1)
 Sof(Br1A)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B)
6.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C12(H12), C16(H16), C15(H15), C13(H13), C10(H10), C18(H18),
 C22(H22), C9(H9), C7(H7), C19(H19), C21(H21), C20(H20)
;
_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 WL-C22H16BrClO2
_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 1.135
_oxdiff_exptl_absorpt_empirical_full_min 0.884