Ligand-promoted ruthenium-catalyzed meta C-H chlorination of arenes using N-chloro-2,10-camphorsultam.
Fan, Zhoulong; Lu, Heng; Cheng, Zhen; Zhang, Ao; Chemical communications (Cambridge, England) 54 (2018) 6008–6011; doi:10.1039/c8cc03195a

data_7121669
_publ_section_title
;
 Ligand-promoted ruthenium-catalyzed meta C-H chlorination of arenes using
 N-chloro-2,10-camphorsultam.
;
_journal_issue                   47
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              6008
_journal_page_last               6011
_journal_paper_doi               10.1039/c8cc03195a
_journal_volume                  54
_journal_year                    2018
_chemical_formula_moiety         'C18 H17 Cl N2 O'
_chemical_formula_sum            'C18 H17 Cl N2 O'
_chemical_formula_weight         312.78
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-10-25
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2017-11-16 deposited with the CCDC.
2018-05-15 downloaded from the CCDC.
;
_cell_angle_alpha                94.419(12)
_cell_angle_beta                 104.016(11)
_cell_angle_gamma                113.589(11)
_cell_formula_units_Z            2
_cell_length_a                   8.075(4)
_cell_length_b                   8.096(4)
_cell_length_c                   13.744(6)
_cell_measurement_reflns_used    273
_cell_measurement_temperature    173
_cell_measurement_theta_max      17.363
_cell_measurement_theta_min      2.84
_cell_volume                     783.5(7)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      173
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0915
_diffrn_reflns_av_unetI/netI     0.1645
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            6052
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.348
_diffrn_reflns_theta_min         1.557
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.247
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5933
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0869 before and 0.0570 after correction. The Ratio of minimum to maximum transmission is 0.7957. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.326
_exptl_crystal_description       block
_exptl_crystal_F_000             328
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: DCM/hexane'
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.255
_refine_diff_density_min         -0.270
_refine_diff_density_rms         0.072
_refine_ls_extinction_coef       0.037(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   0.966
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     222
_refine_ls_number_reflns         2837
_refine_ls_number_restraints     29
_refine_ls_restrained_S_all      0.963
_refine_ls_R_factor_all          0.1652
_refine_ls_R_factor_gt           0.0813
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0860P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1859
_refine_ls_wR_factor_ref         0.2399
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1293
_reflns_number_total             2837
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc03195a2.cif
_cod_data_source_block           mo_2017911-85-8_0m
_cod_depositor_comments
'Adding full bibliography for 7121669--7121671.cif.'
_cod_original_cell_volume        783.5(6)
_cod_database_code               7121669
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.934
_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
 C19-C13 = C18-C15
 1.54 with sigma of 0.02
 C18-C15 \\sim C19-C13
 with sigma of 0.02
3. Rigid bond restraints
 C19, C13
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C15, C18
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C13 \\sim C19: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C18 \\sim C15: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C19) \\sim Ueq, Uanis(C18) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C18) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
5. Others
 Fixed Sof: Cl1(0.6) C18(0.4) H18A(0.4) H18B(0.4) H18C(0.4) Cl2(0.4) C19(0.6)
 H19A(0.6) H19B(0.6) H19C(0.6)
6.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B)
6.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C16(H16), C4(H4), C2(H2), C1(H1), C3(H3)
6.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C17(H17A,H17B,H17C), C10(H10A,H10B,
 H10C)
;
_olex2_submission_special_instructions 'No special instructions were received'