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_7716029
_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         '2(C40 H49 Au Cl N3 P S3), 3(C4 H8 O), 2(F6 P)'
_chemical_formula_sum            'C92 H122 Au2 Cl2 F12 N6 O3 P4 S6'
_chemical_formula_weight         2369.02
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-04-09
_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                73.469(2)
_cell_angle_beta                 71.9980(10)
_cell_angle_gamma                74.327(2)
_cell_formula_units_Z            1
_cell_length_a                   12.6165(5)
_cell_length_b                   13.2076(5)
_cell_length_c                   17.0154(6)
_cell_measurement_reflns_used    9688
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      30.54
_cell_measurement_theta_min      2.72
_cell_volume                     2532.93(17)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 1.000
_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  0.0586
_diffrn_reflns_av_unetI/netI     0.0257
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            143889
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.508
_diffrn_reflns_theta_min         2.135
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.204
_exptl_absorpt_correction_T_max  0.6128
_exptl_absorpt_correction_T_min  0.5426
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0721 before and 0.0668 after correction.
The Ratio of minimum to maximum transmission is 0.8854.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.553
_exptl_crystal_description       block
_exptl_crystal_F_000             1196
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.104
_exptl_crystal_size_min          0.087
_refine_diff_density_max         1.261
_refine_diff_density_min         -1.212
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     749
_refine_ls_number_reflns         15458
_refine_ls_number_restraints     566
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0243
_refine_ls_R_factor_gt           0.0220
_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^)+(0.0223P)^2^+2.3299P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0546
_refine_ls_wR_factor_ref         0.0558
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14576
_reflns_number_total             15458
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01184h2.cif
_cod_data_source_block           23gso001
_cod_depositor_comments
'Adding full bibliography for 7716029--7716031.cif.'
_cod_database_code               7716029
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.768
_shelx_estimated_absorpt_t_min   0.681
_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
 C101-C102 = C102-C103 = C103-C104
 1.5 with sigma of 0.02
 C101-O2 = C104-O2
 1.42 with sigma of 0.02
 C101-C103 = C102-C104
 2.36 with sigma of 0.04
 C102-O2 = C103-O2
 2.34 with sigma of 0.04
 C101-C104
 2.32 with sigma of 0.04
 C33-C38 \\sim C33A-C38A \\sim C35-C39 \\sim C35A-C39A \\sim C37-C40 \\sim
C37A-C40A
 with sigma of 0.01
 O1-C42 \\sim O1A-C42A \\sim C42-C43 \\sim C42A-C43A \\sim C43-C44 \\sim
C43A-C44A \\sim C44-C45 ~
 C44A-C45A \\sim C45-O1 \\sim C45A-O1A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O2 \\sim C101 \\sim C102 \\sim C103 \\sim C104: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
O1 \\sim O1A \\sim C42 \\sim C42A \\sim C43 \\sim C43A \\sim C44 \\sim C44A
\\sim C45 \\sim C45A: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
C32 \\sim C32A \\sim C33 \\sim C33A \\sim C34 \\sim C34A \\sim C35 \\sim C35A
\\sim C36 \\sim C36A \\sim C37 \\sim C37A \\sim C38 \\sim C38A \\sim C39 \\sim
C39A \\sim C40 \\sim C40A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
F3 \\sim F3A \\sim F4 \\sim F4A \\sim F5 \\sim F5A \\sim F6 \\sim F6A: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(F5A)=Sof(F6A)=Sof(F3A)=Sof(F4A)=1-FVAR(1)
 Sof(F5)=Sof(F4)=Sof(F3)=Sof(F6)=FVAR(1)
 Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C38A)=Sof(H38A)=Sof(H38B)=
 Sof(H38C)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C32A)=Sof(C37A)=Sof(C36A)=
 Sof(H36A)=Sof(C35A)=Sof(C34A)=Sof(H34A)=Sof(C33A)=1-FVAR(2)
 Sof(C32)=Sof(C37)=Sof(C36)=Sof(H36)=Sof(C35)=Sof(C34)=Sof(H34)=Sof(C33)=
 Sof(C39A)=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C38)=Sof(H38D)=Sof(H38E)=Sof(H38F)=
 Sof(C40A)=Sof(H40D)=Sof(H40E)=Sof(H40F)=FVAR(2)
 Sof(C45A)=Sof(H45C)=Sof(H45D)=Sof(C44A)=Sof(H44C)=Sof(H44D)=Sof(C42A)=
 Sof(H42C)=Sof(H42D)=Sof(C43A)=Sof(H43C)=Sof(H43D)=Sof(O1A)=1-FVAR(3)
 Sof(O1)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C44)=
 Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=Sof(H45B)=FVAR(3)
 Fixed Sof: C103(0.5) H10A(0.5) H10B(0.5) C102(0.5) H10C(0.5) H10D(0.5)
 C104(0.5) H10E(0.5) H10F(0.5) C101(0.5) H10G(0.5) H10H(0.5) O2(0.5)
5.a Ternary CH refined with riding coordinates:
 C7(H7), C10(H10)
5.b Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C21(H21A,H21B), C45A(H45C,H45D), C43(H43A,H43B), C42(H42A,
 H42B), C44A(H44C,H44D), C103(H10A,H10B), C102(H10C,H10D), C104(H10E,H10F),
 C42A(H42C,H42D), C43A(H43C,H43D), C44(H44A,H44B), C45(H45A,H45B), C101(H10G,
 H10H)
5.c Aromatic/amide H refined with riding coordinates:
 C18(H18), C14(H14), C36(H36), C34(H34), C15(H15), C27(H27), C3(H3), C5(H5),
 C17(H17), C4(H4), C25(H25), C6(H6), C16(H16), C36A(H36A), C34A(H34A)
5.d Fitted hexagon refined as free rotating group:
 C32(C37,C36,C35,C34,C33), C32A(C37A,C36A,C35A,C34A,C33A)
5.e Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C39(H39A,H39B,H39C), C9(H9A,H9B,H9C), C31(H31A,H31B,
 H31C), C11(H11A,H11B,H11C), C38A(H38A,H38B,H38C), C40(H40A,H40B,H40C),
 C30(H30A,H30B,H30C), C8(H8A,H8B,H8C), C29(H29A,H29B,H29C), C39A(H39D,H39E,
 H39F), C38(H38D,H38E,H38F), C40A(H40D,H40E,H40F)
;
_shelx_res_checksum              65484
_olex2_submission_special_instructions 'No special instructions were received'