High-valent CuIICuIII Species in Action: Demonstration of Aliphatic C—H Bond Activation at Room Temperature
Belle, Catherine; Isaac, James Alfred; Thibon-Pourret, Aurore; Durand, Amélie; Philouze, Christian; Le Poul, Nicolas; Chemical Communications  (2019) –; doi:10.1039/C9CC04422A

data_7124248
_publ_section_title
;
 High-valent CuIICuIII Species in Action: Demonstration of Aliphatic C---H
 Bond Activation at Room Temperature
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC04422A
_journal_year                    2019
_chemical_formula_moiety         'C32 H28 Cu2 N6 O2, 2(Cl O4), 6(H2 O)'
_chemical_formula_sum            'C32 H40 Cl2 Cu2 N6 O16'
_chemical_formula_weight         962.68
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2019-01-11
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_audit_update_record
;
2019-01-11 deposited with the CCDC.    2019-09-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.88(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.151(5)
_cell_length_b                   10.682(2)
_cell_length_c                   14.443(3)
_cell_measurement_reflns_used    15115
_cell_measurement_temperature    200
_cell_measurement_theta_max      27.500
_cell_measurement_theta_min      2.075
_cell_volume                     3839.7(15)
_computing_cell_refinement       EvalCCD
_computing_data_collection       Collect
_computing_data_reduction        EvalCCD
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      200
_diffrn_detector                 'CCD area detector'
_diffrn_detector_type            'APEX II'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'Bruker-AXS-enraf-nonius KappaAPEXII'
_diffrn_measurement_method       'Phi and omega scans'
_diffrn_radiation_collimation    'Montel optic'
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Multilayer mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0241
_diffrn_reflns_av_unetI/netI     0.0234
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            15115
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.499
_diffrn_reflns_theta_min         2.075
_diffrn_source                   'Incoatec ISG250'
_diffrn_source_target            Mo
_diffrn_source_type              'Microfocus sealed tube'
_exptl_absorpt_coefficient_mu    1.328
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.739298
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2004/1 (Bruker,2004) was used for absorption correction.
R(int) was 0.0909 before and 0.0281 after correction.
The Ratio of minimum to maximum transmission is 0.7393.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.665
_exptl_crystal_description       prism
_exptl_crystal_F_000             1976
_exptl_crystal_size_max          0.41
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.37
_refine_diff_density_max         0.431
_refine_diff_density_min         -0.339
_refine_diff_density_rms         0.056
_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     327
_refine_ls_number_reflns         4370
_refine_ls_number_restraints     298
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0322
_refine_ls_R_factor_gt           0.0252
_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^)+(0.0253P)^2^+6.5625P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0647
_refine_ls_wR_factor_ref         0.0708
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3885
_reflns_number_total             4370
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc04422a2.cif
_cod_data_source_block           sad
_cod_original_cell_volume        3839.9(15)
_cod_database_code               7124248
_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, All O(H) groups, All O(H,H) groups
2. Restrained distances
 H2A-H4CB
 2.7 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
5. Others
 Sof(O4C)=Sof(H4CA)=Sof(H4CB)=0.66666*(1-FVAR(2))
 Sof(O4B)=Sof(H4BA)=Sof(H4BB)=0.66666*FVAR(2)
 Sof(O6B)=Sof(O8B)=Sof(O7B)=1-FVAR(2)
 Sof(O7A)=Sof(O8A)=Sof(O6A)=FVAR(2)
 Fixed Sof: O4A(0.33333) H4AA(0.33333) H4AB(0.33333)
6.a Free rotating group:
 O2(H2A,H2B), O3(H3A,H3B), O4B(H4BA,H4BB), O4A(H4AA,H4AB), O4C(H4CA,H4CB)
6.b Rotating group:
 O1(H1)
6.c Aromatic/amide H refined with riding coordinates:
 C29(H29), C24(H24), C26(H26), C28(H28), C23(H23), C2(H2), C3(H3), C31(H31),
 C25(H25), C30(H30)
6.d Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C)
;
_shelx_res_checksum              70614
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'