Tris(imidazolyl) dicopper(i) complex and its reactivity to exert the catalytic oxidation of sterically hindered phenol substrates via a [Cu2O]2+ core
Chen, Chih-Yu; Tsai, Ming-Li; Dalton Transactions  (2022) –; doi:10.1039/D1DT04084G

data_7709343
_publ_section_title
;
 Tris(imidazolyl) dicopper(i) complex and its reactivity to exert the
 catalytic oxidation of sterically hindered phenol substrates via a
 [Cu2O]2+ core
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT04084G
_journal_year                    2022
_chemical_formula_moiety
'0.074(C28.871 H45 Cu2 N15), 0.148(C30 H45 Cu2 N15), 0.444(F6 P)'
_chemical_formula_sum            'C6.58 H10 Cu0.44 F2.67 N3.33 P0.44'
_chemical_formula_weight         228.51
_space_group_crystal_system      trigonal
_space_group_IT_number           147
_space_group_name_Hall           '-P 3'
_space_group_name_H-M_alt        'P -3'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_block_doi                 10.5517/ccdc.csd.cc27my1w
_audit_creation_date             2020-06-10
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2021-04-01 deposited with the CCDC.	2022-01-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            27
_cell_length_a                   22.8908(4)
_cell_length_b                   22.8908(4)
_cell_length_c                   13.8848(3)
_cell_measurement_reflns_used    12661
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      25.2910
_cell_measurement_theta_min      2.3020
_cell_volume                     6300.7(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.56a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.56a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.56a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      113(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.948
_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    -14.00  11.00   0.50  147.09    --   10.60 -10.00 141.00   50
  2  \w    -26.00   0.00   0.50  147.09    --  -10.90 -10.00 141.00   52
  3  \w    -15.00  99.00   0.50  147.09    --   10.60  77.00   0.00  228
  4  \w     -5.00  20.00   0.50  147.09    --   10.60  82.00  90.00   50
  5  \w    -17.00  15.00   0.50  147.09    --   10.60  82.00  60.00   64
  6  \w    -67.00  -7.00   0.50  147.09    --   10.60 -82.00  90.00  120
  7  \w      6.00  31.00   0.50  147.09    --   10.60 -82.00  90.00   50
  8  \w   -100.00 -50.00   0.50  147.09    --  -10.90 -57.00-150.00  100
  9  \w    -14.00  14.00   0.50  147.09    --  -10.90 -57.00-150.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro II AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0274956000
_diffrn_orient_matrix_UB_12      -0.0058556000
_diffrn_orient_matrix_UB_13      0.0047414000
_diffrn_orient_matrix_UB_21      0.0223409000
_diffrn_orient_matrix_UB_22      0.0351566000
_diffrn_orient_matrix_UB_23      0.0053309000
_diffrn_orient_matrix_UB_31      -0.0049453000
_diffrn_orient_matrix_UB_32      -0.0031547000
_diffrn_orient_matrix_UB_33      0.0505980000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0313
_diffrn_reflns_av_unetI/netI     0.0411
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.948
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            41314
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.948
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.044
_diffrn_reflns_theta_min         1.791
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.187
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53241
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.56a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            white
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.626
_exptl_crystal_description       block
_exptl_crystal_F_000             3142
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.882
_refine_diff_density_min         -0.861
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     646
_refine_ls_number_reflns         8745
_refine_ls_number_restraints     939
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.1380
_refine_ls_R_factor_gt           0.0874
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1089P)^2^+17.9784P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2170
_refine_ls_wR_factor_ref         0.2470
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5425
_reflns_number_total             8745
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt04084g2.cif
_cod_data_source_block           k10905-mlt-e
_cod_original_cell_volume        6300.7(3)
_cod_database_code               7709343
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.797
_shelx_estimated_absorpt_t_min   0.797
_reflns_odcompleteness_completeness 99.04
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N10-C29 \\sim N10-C31
 with sigma of 0.04
 N8-C28 \\sim N8-C33
 with sigma of 0.02
 C29-C30 \\sim C31-C32
 with sigma of 0.04
 N8-C30 \\sim N8-C32
 with sigma of 0.04
 N7-C29 \\sim N6-C31
 with sigma of 0.02
 N7-C28 \\sim N6-C33
 with sigma of 0.04
 N7-C30 \\sim N6-C32
 with sigma of 0.02
 C28-C30 \\sim C33-C32
 with sigma of 0.02
 P1-F6 \\sim P1-F13
 with sigma of 0.02
 P1-F9 \\sim P1-F18
 with sigma of 0.02
 P1-F10 \\sim P1-F17
 with sigma of 0.02
 P1-F11 \\sim P1-F16
 with sigma of 0.02
 P1-F12 \\sim P1-F14
 with sigma of 0.02
 P1-F2 \\sim P1-F15
 with sigma of 0.02
3. Rigid bond restraints
 N9, C27
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 8.2
4. Uiso/Uaniso restraints and constraints
C21 \\sim C22 \\sim C23 \\sim C24 \\sim C26 \\sim C27 \\sim C25 \\sim C28 \\sim
C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33 \\sim C7 \\sim C8 \\sim C9 \\sim
C10 \\sim C11 \\sim C12 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C1 \\sim
C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C13 \\sim C14 \\sim C15 \\sim C16:
within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3.8A
Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C24)
\\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C25) \\sim Ueq,
Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C31)
\\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C7) \\sim Ueq,
Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq,
Uanis(C19) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C2)
\\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq,
Uanis(C6) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(C16) \\sim Ueq: with sigma of 0.008 and sigma for terminal
atoms of 0.008
Uanis(N8) \\sim Ueq, Uanis(N9) \\sim Ueq, Uanis(N10) \\sim Ueq, Uanis(N11)
\\sim Ueq, Uanis(N7) \\sim Ueq, Uanis(N6) \\sim Ueq, Uanis(N12) \\sim Ueq,
Uanis(N13) \\sim Ueq, Uanis(N14) \\sim Ueq, Uanis(N15) \\sim Ueq, Uanis(N16)
\\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(N3) \\sim Ueq,
Uanis(N4) \\sim Ueq, Uanis(N5) \\sim Ueq: with sigma of 0.009 and sigma for
terminal atoms of 0.009
Uanis(F2) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F10) \\sim
Ueq, Uanis(F11) \\sim Ueq, Uanis(F12) \\sim Ueq, Uanis(F13) \\sim Ueq,
Uanis(F14) \\sim Ueq, Uanis(F15) \\sim Ueq, Uanis(F16) \\sim Ueq, Uanis(F17)
\\sim Ueq, Uanis(F18) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F3) \\sim Ueq,
Uanis(F4) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F8) \\sim
Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
5. Others
 Sof(H10)=Sof(N6)=Sof(H6)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C32)=
 Sof(H32A)=Sof(H32B)=Sof(C33)=Sof(H33A)=Sof(H33B)=1-FVAR(1)
 Sof(N7)=Sof(H7)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(C28)=Sof(H28A)=Sof(H28B)=
 Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(C30)=Sof(H30A)=Sof(H30B)=FVAR(1)
 Sof(F13)=Sof(F14)=Sof(F15)=Sof(F16)=Sof(F17)=Sof(F18)=1-FVAR(2)
 Sof(F2)=Sof(F6)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=FVAR(2)
6.a Riding coordinates:
 N1(H1A)
6.b Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B), C32(H32A,
 H32B), C33(H33A,H33B), C10(H10A,H10B), C12(H12A,H12B), C17(H17A,H17B),
 C19(H19A,H19B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B)
6.c Aromatic/amide H refined with riding coordinates:
 N10(H10), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), N7(H7),
 N6(H6), C7(H7A), C8(H8), C9(H9), C11(H11), C18(H18), C20(H20), C1(H1), C2(H2),
 C3(H3), C4(H4), C5(H5), C6(H6A)
6.d Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C)
;