A cationic gold-fluorenyl complex with a dative Au → C+ bond: synthesis, structure, and carbophilic reactivity
Litle, Elishua D.; Gabbaï, François P.; Chemical Communications 59 (2023) 603–606; doi:10.1039/D2CC05436A

data_7131047
_publ_section_title
;
 A cationic gold-fluorenyl complex with a dative Au \\rightarrow C+ bond:
 synthesis, structure, and carbophilic reactivity
;
_journal_issue                   5
_journal_name_full               'Chemical Communications'
_journal_page_first              603
_journal_page_last               606
_journal_paper_doi               10.1039/D2CC05436A
_journal_volume                  59
_journal_year                    2023
_chemical_formula_moiety
'C62 H44 Au2 Cl2 P2, 2(C32 H12 B F24), C6 H4 F2, C6 H14'
_chemical_formula_sum            'C138 H86 Au2 B2 Cl2 F50 P2'
_chemical_formula_weight         3242.46
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-11-11
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-11-12 deposited with the CCDC.	2022-11-28 downloaded from the CCDC.
;
_cell_angle_alpha                63.266(4)
_cell_angle_beta                 89.509(5)
_cell_angle_gamma                87.844(4)
_cell_formula_units_Z            1
_cell_length_a                   12.836(2)
_cell_length_b                   17.581(3)
_cell_length_c                   17.820(3)
_cell_measurement_reflns_used    9788
_cell_measurement_temperature    110.00
_cell_measurement_theta_max      26.993
_cell_measurement_theta_min      2.195
_cell_volume                     3588.9(10)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      110.00
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.0911
_diffrn_reflns_av_unetI/netI     0.0749
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            85528
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         2.030
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.212
_exptl_absorpt_correction_T_max  0.3812
_exptl_absorpt_correction_T_min  0.3468
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0768 before and 0.0646 after correction.
The Ratio of minimum to maximum transmission is 0.9098.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.500
_exptl_crystal_description       block
_exptl_crystal_F_000             1596
_exptl_crystal_size_max          0.121
_exptl_crystal_size_mid          0.111
_exptl_crystal_size_min          0.098
_refine_diff_density_max         1.479
_refine_diff_density_min         -1.364
_refine_diff_density_rms         0.142
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1015
_refine_ls_number_reflns         16448
_refine_ls_number_restraints     274
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.1176
_refine_ls_R_factor_gt           0.0637
_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^)+(0.0984P)^2^+9.6977P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1642
_refine_ls_wR_factor_ref         0.1982
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10054
_reflns_number_total             16448
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc05436a2.cif
_cod_data_source_block           eli146_1_0m_a
_cod_depositor_comments
'Adding full bibliography for 7131043--7131047.cif.'
_cod_original_cell_volume        3589.0(10)
_cod_database_code               7131047
_shelxl_version_number           2013-3
_shelx_estimated_absorpt_t_max   0.812
_shelx_estimated_absorpt_t_min   0.776
_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
 C69-C64 = C69-C68 = C64-C65
 1.39 with sigma of 0.02
 C69-F26 = C64-F25
 1.35 with sigma of 0.02
 C65-C66 = C66-C67 = C67-C68
 1.4 with sigma of 0.02
 C74-C73
 1.54 with sigma of 0.02
 C73-C72
 1.54 with sigma of 0.02
 C54-F15'
 1.35 with sigma of 0.02
 C69-F25
 2.37 with sigma of 0.04
 C69-C65 = C65-C67 = C66-C68
 2.42 with sigma of 0.04
 C69-C67 = C64-C66
 2.4 with sigma of 0.04
 C69-F26 \\sim C64-F25
 with sigma of 0.02
 C69-C68 \\sim C67-C68 \\sim C69-C64 \\sim C66-C67 \\sim C65-C66 \\sim C64-C65
 with sigma of 0.02
 C69-F25 \\sim C65-F25 \\sim C64-F26 \\sim C68-F26
 with sigma of 0.04
 C66-C68 \\sim C65-C67 \\sim C64-C66 \\sim C69-C65 \\sim C64-C68 \\sim C69-C67
 with sigma of 0.04
 Au1-Cl1' \\sim Au1A-Cl1'
 with sigma of 0.02
 Au1-Cl1 \\sim Au1A-Cl1
 with sigma of 0.02
 Au1-C9 \\sim Au1A-C9
 with sigma of 0.02
 Au1-P1 \\sim Au1A-P1
 with sigma of 0.02
3. Restrained planarity
 F25, F26, C64, C65, C66, C67, C68, C69
 with sigma of 0.1
4. Rigid bond restraints
 F18', C55
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C5 \\sim C6: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
C7 \\sim C8: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
C28' \\sim C29': within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C5 \\sim C6 \\sim C7 \\sim C8: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
F18 \\sim F18': within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
F12 \\sim F12': within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
F23' \\sim C63: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
F25 \\sim F26 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
F15' \\sim C54: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C5 \\sim C6 \\sim C7 \\sim C8 \\sim C10 \\sim C11: within 2A with sigma of
0.002 and sigma for terminal atoms of 0.004 within 2A
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C12 \\sim C13: within 2A with sigma of
0.002 and sigma for terminal atoms of 0.004 within 2A
F10 \\sim C47: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(C28) = Uanis(C27)
Uanis(F6') = Uanis(F6)
Uanis(F4') = Uanis(C39)
Uanis(C70) = Uanis(C73) = Uanis(C74) = Uanis(C75)
Uanis(C70) = Uanis(C71) = Uanis(C72) = Uanis(C73) = Uanis(C74) = Uanis(C75)
Uanis(F26) = Uanis(C69) = Uanis(C68) = Uanis(C67) = Uanis(C66) = Uanis(C65) =
Uanis(C64) = Uanis(F25)
Uanis(F23') = Uanis(F23)
Uanis(F18') = Uanis(F17')
6. Rigid body (RIGU) restrains
 F25, F26, C64, C65, C66, C67, C68, C69
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(C29)=Sof(H29)=1-FVAR(1)
 Sof(C29')=Sof(H29')=FVAR(1)
 Sof(C30)=Sof(H30)=1-FVAR(2)
 Sof(C30')=Sof(H30')=FVAR(2)
 Sof(C31)=Sof(H31)=1-FVAR(3)
 Sof(C31')=Sof(H31')=FVAR(3)
 Sof(C28)=Sof(H28)=1-FVAR(4)
 Sof(C28')=Sof(H28')=FVAR(4)
 Sof(C27)=Sof(H27)=1-FVAR(5)
 Sof(C27')=Sof(H27')=FVAR(5)
 Sof(F22)=1-FVAR(6)
 Sof(F22')=FVAR(6)
 Sof(F23')=1-FVAR(7)
 Sof(F23)=FVAR(7)
 Sof(F24)=1-FVAR(8)
 Sof(F24')=FVAR(8)
 Sof(F5')=1-FVAR(9)
 Sof(F5)=FVAR(9)
 Sof(F6')=1-FVAR(10)
 Sof(F6)=FVAR(10)
 Sof(F4')=1-FVAR(11)
 Sof(F4)=FVAR(11)
 Sof(F15)=1-FVAR(12)
 Sof(F15')=FVAR(12)
 Sof(F14)=1-FVAR(13)
 Sof(F14')=FVAR(13)
 Sof(F17')=1-FVAR(14)
 Sof(F17)=FVAR(14)
 Sof(F18')=1-FVAR(15)
 Sof(F18)=FVAR(15)
 Sof(F16')=1-FVAR(16)
 Sof(F16)=FVAR(16)
 Sof(F12')=1-FVAR(17)
 Sof(F12)=FVAR(17)
 Sof(Au1A)=1-FVAR(18)
 Sof(Au1)=FVAR(18)
 Fixed Sof: Cl1(0.5) Cl1'(0.5) F25(0.5) F26(0.5) C64(0.5) C65(0.5) H65(0.5)
 C66(0.5) H66(0.5) C67(0.5) H67(0.5) C68(0.5) H68(0.5) C69(0.5) C70(0.5)
 H70A(0.5) H70B(0.5) H70C(0.5) C71(0.5) H71A(0.5) H71B(0.5) C72(0.5) H72A(0.5)
 H72B(0.5) C73(0.5) H73A(0.5) H73B(0.5) C74(0.5) H74A(0.5) H74B(0.5) C75(0.5)
 H75A(0.5) H75B(0.5) H75C(0.5)
8.a Secondary CH2 refined with riding coordinates:
 C71(H71A,H71B), C72(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B)
8.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C15(H15),
 C16(H16), C17(H17), C18(H18), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25),
  C27(H27), C28(H28), C29(H29), C29'(H29'), C28'(H28'), C27'(H27'), C31'(H31'),
 C30'(H30'), C30(H30), C31(H31), C35(H35), C37(H37), C41(H41), C43(H43),
 C45(H45), C49(H49), C51(H51), C53(H53), C57(H57), C59(H59), C61(H61), C65(H65),
  C66(H66), C67(H67), C68(H68)
8.c Fitted hexagon refined as free rotating group:
 C5(C6,C7,C8,C11,C10), C29'(C28',C27',C26,C31',C30')
8.d Idealised Me refined as rotating group:
 C70(H70A,H70B,H70C), C75(H75A,H75B,H75C)
;
_shelx_res_checksum              34294
_shelx_hkl_checksum              88138
_olex2_submission_original_sample_id C36H34AuBClF24P
_olex2_submission_special_instructions 'No special instructions were received'