Coordination of azol(in)ium dithiocarboxylate ligands to Au(III): unexpected formation of a novel family of cyclometallated Au(III) complexes, DFT calculations and catalytic studies.
Pérez-Ramos, Paula; Mateo, María A; Elorriaga, David; García-Vivó, Daniel; Soengas, Raquel G.; Rodríguez-Solla, Humberto; Dalton transactions (Cambridge, England : 2003) 53 (2024) 9433–9440; doi:10.1039/d4dt01184h

data_7716030
_publ_section_title
;
 Coordination of azol(in)ium dithiocarboxylate ligands to Au(III):
 unexpected formation of a novel family of cyclometallated Au(III)
 complexes, DFT calculations and catalytic studies.
;
_journal_issue                   22
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              9433
_journal_page_last               9440
_journal_paper_doi               10.1039/d4dt01184h
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C46 H59 Au Cl N3 P S3, C4 H8 O, C4 H7 O, F6 P'
_chemical_formula_sum            'C54 H74 Au Cl F6 N3 O2 P2 S3'
_chemical_formula_weight         1301.69
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-05-29
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-04-09 deposited with the CCDC.	2024-05-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.6750(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.1777(2)
_cell_length_b                   31.2292(3)
_cell_length_c                   11.99430(10)
_cell_measurement_reflns_used    20591
_cell_measurement_temperature    297(2)
_cell_measurement_theta_max      69.5380
_cell_measurement_theta_min      3.9470
_cell_volume                     6005.43(11)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      297(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.2640
_diffrn_detector_type            Onyx
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.988
_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    -68.00 -30.00   1.00    4.00    --  -43.48  37.00  60.00   38
  2  \w   -112.00 -11.00   1.00    4.00    --  -43.48 -19.00   0.00  101
  3  \w   -117.00 -79.00   1.00    4.00    --  -43.48 -99.00 150.00   38
  4  \w     21.00 121.00   1.00   16.50    --   94.50 -30.00 -30.00  100
  5  \w     69.00 104.00   1.00   16.50    --   94.50 -94.00   0.00   35
  6  \w     57.00  84.00   1.00   16.50    --   94.50 -94.00 -30.00   27
  7  \w     52.00 117.00   1.00   16.50    --   94.50 -61.00 -30.00   65
  8  \w     86.00 121.00   1.00   16.50    --   94.50 -15.00  90.00   35
  9  \w     72.00 164.00   1.00   16.50    --   94.50  45.00 -90.00   92
 10  \w     23.00  66.00   1.00   16.50    --   94.50 -15.00  90.00   43
 11  \w     19.00  45.00   1.00   16.50    --   94.50 -94.00 -30.00   26
 12  \w     12.00  65.00   1.00   16.50    --   94.50 -94.00   0.00   53
 13  \w     21.00 122.00   1.00   16.50    --   94.50 -77.00-180.00  101
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Onyx, Nova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0633979000
_diffrn_orient_matrix_UB_12      0.0111132000
_diffrn_orient_matrix_UB_13      0.0807014000
_diffrn_orient_matrix_UB_21      0.0705982000
_diffrn_orient_matrix_UB_22      0.0195154000
_diffrn_orient_matrix_UB_23      0.0834670000
_diffrn_orient_matrix_UB_31      -0.0154081000
_diffrn_orient_matrix_UB_32      0.0439230000
_diffrn_orient_matrix_UB_33      -0.0575466000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0480
_diffrn_reflns_av_unetI/netI     0.0450
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            31746
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.599
_diffrn_reflns_theta_min         2.830
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Nova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.982
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.20584
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.440
_exptl_crystal_description       plate
_exptl_crystal_F_000             2652
_exptl_crystal_size_max          0.555
_exptl_crystal_size_mid          0.497
_exptl_crystal_size_min          0.295
_refine_diff_density_max         1.608
_refine_diff_density_min         -2.396
_refine_diff_density_rms         0.156
_refine_ls_extinction_coef       0.00195(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     837
_refine_ls_number_reflns         11165
_refine_ls_number_restraints     655
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0539
_refine_ls_R_factor_gt           0.0504
_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^)+(0.1008P)^2^+0.0873P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1305
_refine_ls_wR_factor_ref         0.1362
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10045
_reflns_number_total             11165
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01184h2.cif
_cod_data_source_block           23009_rs847_b
_cod_depositor_comments
'Adding full bibliography for 7716029--7716031.cif.'
_cod_database_code               7716030
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C70H80Au1Cl1N3P3S3
_reflns_odcompleteness_completeness 99.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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
 P2-F1 = P2-F2 = P2-F3 = P2-F4 = P2-F5 = P2-F6
 1.57 with sigma of 0.02
 P2-F1A = P2-F2A = P2-F3A = P2-F4A = P2-F5A = P2-F6A
 1.57 with sigma of 0.02
 C60A-C61A = C61A-C62A = C62A-C63A
 1.5 with sigma of 0.02
 C60A-O1A = C63A-O1A
 1.42 with sigma of 0.02
 C50A-C49A = C49A-C48A = C48A-C47A
 1.5 with sigma of 0.02
 C50A-O2A = C47A-O2A
 1.42 with sigma of 0.02
 C60-C61 = C61-C62 = C62-C63
 1.5 with sigma of 0.02
 C60-O1 = C63-O1
 1.42 with sigma of 0.02
 C47-C48 = C48-C49 = C49-C50
 1.5 with sigma of 0.02
 C47-O2 = C50-O2
 1.42 with sigma of 0.02
 F5A-F1A = F5A-F2A = F5A-F3A = F5A-F4A
 2.22 with sigma of 0.04
 F6A-F2A = F6A-F3A = F6A-F4A = F6A-F1A
 2.22 with sigma of 0.04
 F2A-F3A = F3A-F4A = F4A-F1A = F1A-F2A
 2.22 with sigma of 0.04
 F5-F1 = F5-F2 = F5-F3 = F5-F4
 2.22 with sigma of 0.04
 C61A-O1A = C62A-O1A
 2.34 with sigma of 0.04
 C60A-C62A = C61A-C63A
 2.36 with sigma of 0.04
 F6-F2 = F6-F3 = F6-F4 = F6-F1
 2.22 with sigma of 0.04
 C50A-C48A = C49A-C47A
 2.36 with sigma of 0.04
 C49A-O2A = C48A-O2A
 2.34 with sigma of 0.04
 C50A-C47A
 2.32 with sigma of 0.04
 F2-F3 = F3-F4 = F4-F1 = F1-F2
 2.22 with sigma of 0.04
 C60-C61 = C62-C63
 2.36 with sigma of 0.04
 C61-O1 = C62-O1
 2.34 with sigma of 0.04
 C60-C62 = C61-C63
 2.36 with sigma of 0.04
 C47-C49 = C48-C50
 2.36 with sigma of 0.04
 C48-O2 = C49-O2
 2.34 with sigma of 0.04
 C47-C50
 2.32 with sigma of 0.04
 N1-C13 \\sim N1-C13A \\sim C13-C14 \\sim C13A-C14A \\sim C13-C15 \\sim
C13A-C15A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
F6 \\sim F6A \\sim F1 \\sim F1A \\sim F5A \\sim F5 \\sim F2A \\sim F2 \\sim F3
\\sim F3A \\sim F4A \\sim F4 \\sim P2: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C13 \\sim C13A \\sim C14 \\sim C14A \\sim C15 \\sim C15A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
O1 \\sim O1A \\sim C60 \\sim C60A \\sim C61 \\sim C61A \\sim C62 \\sim C62A
\\sim C63 \\sim C63A: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
O2 \\sim O2A \\sim C47 \\sim C47A \\sim C48 \\sim C48A \\sim C49 \\sim C49A
\\sim C50 \\sim C50A: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
4. Others
 Sof(C13A)=Sof(H13A)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C15A)=
 Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(F3A)=Sof(F1A)=Sof(F6A)=Sof(F2A)=Sof(F5A)=
 Sof(F4A)=1-FVAR(1)
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=
 Sof(C13)=Sof(H13)=Sof(F4)=Sof(F5)=Sof(F2)=Sof(F1)=Sof(F6)=Sof(F3)=FVAR(1)
 Sof(C47A)=Sof(H47C)=Sof(H47D)=Sof(C50A)=Sof(H50C)=Sof(H50D)=Sof(C49A)=
 Sof(H49C)=Sof(H49D)=Sof(O2A)=Sof(C48A)=Sof(H48C)=Sof(H48D)=Sof(C63A)=Sof(H63A)=
 Sof(C60A)=Sof(H60C)=Sof(H60D)=Sof(C61A)=Sof(H61C)=Sof(H61D)=Sof(C62A)=
 Sof(H62C)=Sof(H62D)=Sof(O1A)=1-FVAR(2)
 Sof(O2)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(O1)=Sof(C61)=Sof(H61A)=Sof(H61B)=
 Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(C63)=Sof(H63)=Sof(C62)=Sof(H62A)=Sof(H62B)=
 Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(C50)=Sof(H50A)=
 Sof(H50B)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C13A(H13A), C41(H41), C16(H16), C44(H44), C32(H32), C29(H29), C13(H13)
5.b Secondary CH2 refined with riding coordinates:
 C47A(H47C,H47D), C49(H49A,H49B), C50A(H50C,H50D), C49A(H49C,H49D), C61(H61A,
 H61B), C60(H60A,H60B), C62(H62A,H62B), C48A(H48C,H48D), C48(H48A,H48B),
 C47(H47A,H47B), C50(H50A,H50B), C60A(H60C,H60D), C61A(H61C,H61D), C62A(H62C,
 H62D)
5.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C9(H9), C12(H12), C26(H26), C21(H21), C27(H27), C4(H4), C3(H3),
 C22(H22), C39(H39), C10(H10), C8(H8), C37(H37), C5(H5), C38(H38), C6(H6),
 C25(H25), C63(H63), C63A(H63A)
5.d Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C17(H17A,H17B,H17C), C31(H31A,H31B,H31C), C46(H46A,H46B,
 H46C), C45(H45A,H45B,H45C), C43(H43A,H43B,H43C), C33(H33A,H33B,H33C), C18(H18A,
 H18B,H18C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C34(H34A,H34B,H34C),
 C42(H42A,H42B,H42C), C14A(H14D,H14E,H14F), C15A(H15D,H15E,H15F)
;
_shelx_res_checksum              81489
_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 2.523
_oxdiff_exptl_absorpt_empirical_full_min 0.268