Improved synthetic routes to N-heterocyclic carbene-metal-diketonato complexes of gold and copper
Ibni Hashim, Ishfaq; Tzouras, Nikolaos V.; Ma, Xinyuan; Bourda, Laurens; Van Hecke, Kristof; Nolan, Steven P.; Cazin, Catherine S. J.; Dalton Transactions  (2022) –; doi:10.1039/D2DT02276A

data_7711018
_publ_section_title
;
 Improved synthetic routes to N-heterocyclic carbene-metal-diketonato
 complexes of gold and copper
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT02276A
_journal_year                    2022
_chemical_formula_moiety         'C74 H63 Cu N2 O2'
_chemical_formula_sum            'C74 H63 Cu N2 O2'
_chemical_formula_weight         1075.82
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-08-01
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-08-02 deposited with the CCDC.	2022-08-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.44170(10)
_cell_length_b                   18.30740(10)
_cell_length_c                   34.0176(2)
_cell_measurement_reflns_used    28818
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      73.7170
_cell_measurement_theta_min      3.5130
_cell_volume                     11485.01(11)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_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_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4839
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.983
_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   -114.00 -66.00   1.00    7.00    --  -41.68-141.00   5.00   48
  2  \w    -74.00  34.00   1.00    7.00    --  -41.68  77.00  60.00  108
  3  \w     33.00 112.00   1.00   55.00    --  106.01-125.00 -30.00   79
  4  \w    103.00 178.00   1.00   55.00    --  106.01  77.00 -90.00   75
  5  \w    103.00 178.00   1.00   55.00    --  106.01  77.00  30.00   75
  6  \w    103.00 178.00   1.00   55.00    --  106.01  77.00  60.00   75
  7  \w   -115.00 -14.00   1.00    7.00    --  -41.68 -57.00  30.00  101
  8  \w   -115.00 -14.00   1.00    7.00    --  -41.68 -57.00 150.00  101
  9  \w     24.00 159.00   1.00   55.00    --  106.01 -15.00 -90.00  135
 10  \w     33.00 112.00   1.00   55.00    --  106.01-125.00 120.00   79
 11  \w     77.00 178.00   1.00   55.00    --  106.01  61.00 120.00  101
 12  \w    103.00 178.00   1.00   55.00    --  106.01  77.00 -30.00   75
 13  \w   -115.00 -79.00   1.00    7.00    --  -41.68 -57.00 -90.00   36
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0690670000
_diffrn_orient_matrix_UB_12      0.0238516000
_diffrn_orient_matrix_UB_13      -0.0219983000
_diffrn_orient_matrix_UB_21      -0.0468493000
_diffrn_orient_matrix_UB_22      -0.0406655000
_diffrn_orient_matrix_UB_23      0.0304591000
_diffrn_orient_matrix_UB_31      -0.0036736000
_diffrn_orient_matrix_UB_32      0.0696824000
_diffrn_orient_matrix_UB_33      0.0252996000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0373
_diffrn_reflns_av_unetI/netI     0.0217
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            75090
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.971
_diffrn_reflns_theta_min         2.598
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.914
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.672
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.244
_exptl_crystal_description       block
_exptl_crystal_F_000             4528
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.360
_refine_diff_density_min         -0.449
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     753
_refine_ls_number_reflns         11465
_refine_ls_number_restraints     60
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0502
_refine_ls_R_factor_gt           0.0418
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0680P)^2^+3.9857P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1130
_refine_ls_wR_factor_ref         0.1194
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9767
_reflns_number_total             11465
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02276a2.cif
_cod_data_source_block           120_0_2
_cod_database_code               7711018
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C74 H63 Cu N2 O2'
_shelx_estimated_absorpt_t_max   0.914
_shelx_estimated_absorpt_t_min   0.817
_reflns_odcompleteness_completeness 99.52
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 C58A-C59A = C59A-C60A = C60A-C61A = C61A-C62A = C62A-C63A = C63A-C58A
 1.39 with sigma of 0.01
 C58B-C59B = C59B-C60B = C60B-C61B = C61B-C62B = C62B-C63B = C63B-C58B
 1.39 with sigma of 0.01
 C64A-C65A = C65A-C66A = C66A-C67A = C67A-C68A = C68A-C69A = C69A-C64A
 1.39 with sigma of 0.01
 C64B-C65B = C65B-C66B = C66B-C67B = C67B-C68B = C68B-C69B = C69B-C64B
 1.39 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C58A) = Uanis(C58B)
Uanis(C59A) = Uanis(C59B)
Uanis(C60A) = Uanis(C60B)
Uanis(C61A) = Uanis(C61B)
Uanis(C62A) = Uanis(C62B)
Uanis(C63A) = Uanis(C63B)
Uanis(C64A) = Uanis(C64B)
Uanis(C65A) = Uanis(C65B)
Uanis(C66A) = Uanis(C66B)
Uanis(C67A) = Uanis(C67B)
Uanis(C68A) = Uanis(C68B)
Uanis(C69A) = Uanis(C69B)
4. Rigid body (RIGU) restrains
 C18, C19, C20, C21, C22, C23
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(H57A)=Sof(C58B)=Sof(C59B)=Sof(H59B)=Sof(C60B)=Sof(H60B)=Sof(C61B)=
 Sof(H61B)=Sof(C62B)=Sof(H62B)=Sof(C63B)=Sof(H63B)=Sof(C64B)=Sof(C65B)=
 Sof(H65B)=Sof(C66B)=Sof(H66B)=Sof(C67B)=Sof(H67B)=Sof(C68B)=Sof(H68B)=
 Sof(C69B)=Sof(H69B)=1-FVAR(1)
 Sof(H57)=Sof(C58A)=Sof(C59A)=Sof(H59A)=Sof(C60A)=Sof(H60A)=Sof(C61A)=
 Sof(H61A)=Sof(C62A)=Sof(H62A)=Sof(C63A)=Sof(H63A)=Sof(C64A)=Sof(C65A)=
 Sof(H65A)=Sof(C66A)=Sof(H66A)=Sof(C67A)=Sof(H67A)=Sof(C68A)=Sof(H68A)=
 Sof(C69A)=Sof(H69A)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C11(H11), C24(H24), C44(H44), C57(H57), C57(H57A)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C8(H8), C13(H13), C14(H14), C15(H15), C16(H16),
 C17(H17), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C26(H26), C27(H27),
  C28(H28), C29(H29), C30(H30), C32(H32), C33(H33), C34(H34), C35(H35),
 C36(H36), C39(H39), C41(H41), C46(H46), C47(H47), C48(H48), C49(H49), C50(H50),
  C52(H52), C53(H53), C54(H54), C55(H55), C56(H56), C59A(H59A), C60A(H60A),
 C61A(H61A), C62A(H62A), C63A(H63A), C65A(H65A), C66A(H66A), C67A(H67A),
 C68A(H68A), C69A(H69A), C72(H72), C59B(H59B), C60B(H60B), C61B(H61B),
 C62B(H62B), C63B(H63B), C65B(H65B), C66B(H66B), C67B(H67B), C68B(H68B),
 C69B(H69B)
6.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C43(H43A,H43B,H43C), C70(H70A,H70B,H70C), C74(H74A,H74B,
 H74C)
;
_shelx_res_checksum              72070
_olex2_exptl_crystal_mounting_method 'mounted on a LithoLoop'
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.249
_oxdiff_exptl_absorpt_empirical_full_min 0.795