Digold photosensitizer for visible light [2 + 2] cycloaddition and <i>E</i>/<i>Z</i> isomerization reactions.
Ruggiero, Tommaso; Fortwengler, James; Van Hecke, Kristof; Thompson, Mark E.; Heugebaert, Thomas S. A.; Nolan, Steven P.; Organic & biomolecular chemistry 23 (2025) 10143–10149; doi:10.1039/d5ob01503k

data_7160815
_publ_section_title
;
 Digold photosensitizer for visible light [2 + 2] cycloaddition and
 <i>E</i>/<i>Z</i> isomerization reactions.
;
_journal_issue                   44
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              10143
_journal_page_last               10149
_journal_paper_doi               10.1039/d5ob01503k
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C72 H82 Au2 N6, 2(C4 H8 O)'
_chemical_formula_sum            'C80 H98 Au2 N6 O2'
_chemical_formula_weight         1569.57
_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     dual
_audit_creation_date             2025-06-18
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-06-19 deposited with the CCDC.	2025-10-17 downloaded from the CCDC.
;
_cell_angle_alpha                87.0040(10)
_cell_angle_beta                 75.633(2)
_cell_angle_gamma                82.2730(10)
_cell_formula_units_Z            2
_cell_length_a                   13.2000(2)
_cell_length_b                   15.0050(2)
_cell_length_c                   18.9581(3)
_cell_measurement_reflns_used    31229
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.2680
_cell_measurement_theta_min      2.9510
_cell_volume                     3603.80(10)
_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 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 10.4839
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.900
_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    -67.00  32.00   1.00   70.00    --    7.68 -38.00 -90.00   99
  2  \w    -17.00  82.00   1.00   70.00    --    7.68  38.00  90.00   99
  3  \w    -16.00  47.00   1.00   70.00    --    7.68 -98.00 153.00   63
  4  \w    -17.00  82.00   1.00   70.00    --    7.68  38.00  60.00   99
  5  \w    -42.00  24.00   1.00   70.00    --   -8.85 -77.00 150.00   66
  6  \w    -67.00  32.00   1.00   70.00    --    7.68 -38.00 -30.00   99
  7  \w    -15.00  48.00   1.00   70.00    --    7.68 -99.00  30.00   63
  8  \w    -17.00  82.00   1.00   70.00    --    7.68  38.00 -30.00   99
  9  \w    -25.00  21.00   1.00   70.00    --    7.68  77.00-180.00   46
 10  \w    -41.00  21.00   1.00   70.00    --   -8.85  77.00-150.00   62
 11  \w    -41.00  21.00   1.00   70.00    --   -8.85  77.00 150.00   62
 12  \w    -41.00  21.00   1.00   70.00    --   -8.85  77.00 -90.00   62
 13  \w    -41.00  21.00   1.00   70.00    --   -8.85  77.00  30.00   62
 14  \w    -41.00 -16.00   1.00   70.00    --   -8.85  77.00  60.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0816
_diffrn_reflns_av_unetI/netI     0.0683
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.900
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            101514
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.900
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.774
_diffrn_reflns_theta_min         2.462
_exptl_absorpt_coefficient_mu    4.116
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.422
_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            'dull yellowish colourless'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.446
_exptl_crystal_description       block
_exptl_crystal_F_000             1588
_exptl_crystal_preparation       synthesis
_exptl_crystal_recrystallization_method synthesis
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.14
_refine_diff_density_max         1.977
_refine_diff_density_min         -1.115
_refine_diff_density_rms         0.138
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     831
_refine_ls_number_reflns         16897
_refine_ls_number_restraints     53
_refine_ls_restrained_S_all      1.129
_refine_ls_R_factor_all          0.0672
_refine_ls_R_factor_gt           0.0401
_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^)+(0.0279P)^2^+3.5449P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0740
_refine_ls_wR_factor_ref         0.0832
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12652
_reflns_number_total             16897
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01503k2.cif
_cod_data_source_block           tr292_2_thf_pent_mo
_cod_depositor_comments          'Adding full bibliography for 7160815.cif.'
_cod_database_code               7160815
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C80 H98 Au2 N6 O2'
_shelx_estimated_absorpt_t_max   0.596
_shelx_estimated_absorpt_t_min   0.344
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C38-C39A = C38-C39B
 1.5 with sigma of 0.01
 C40-C39A = C40-C39B
 1.5 with sigma of 0.01
 O2-C38
 2.34 with sigma of 0.02
 C37-C39A = C37-C39B
 2.35 with sigma of 0.02
 C38-C40
 2.35 with sigma of 0.02
 C39A-O2 = C39B-O2
 2.34 with sigma of 0.02
 C40-C37
 2.33 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C39A) = Uanis(C39B)
4. Rigid body (RIGU) restrains
 O2, C37, C38, C40, C39A, C39B
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
5. Others
 Sof(H38C)=Sof(H38D)=Sof(H40C)=Sof(H40D)=Sof(C39B)=Sof(H39C)=Sof(H39D)=1-FVAR(1)
 Sof(H38A)=Sof(H38B)=Sof(H40A)=Sof(H40B)=Sof(C39A)=Sof(H39A)=Sof(H39B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C10(H10), C13(H13), C22(H22), C25(H25), C50(H50), C53(H53), C62(H62), C65(H65)
6.b Secondary CH2 refined with riding coordinates:
 C77(H77A,H77B), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,H80B), C37(H37A,
 H37B), C38(H38A,H38B), C38(H38C,H38D), C40(H40A,H40B), C40(H40C,H40D),
 C39A(H39A,H39B), C39B(H39C,H39D)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C7(H7), C8(H8), C18(H18), C19(H19), C20(H20),
 C29(H29), C32(H32), C33(H33), C34(H34), C35(H35), C42(H42), C43(H43), C46(H46),
  C47(H47), C48(H48), C58(H58), C59(H59), C60(H60), C68(H68), C71(H71),
 C74(H74), C75(H75), C76(H76)
6.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,
 H27B,H27C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C54(H54A,H54B,H54C),
 C55(H55A,H55B,H55C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C66(H66A,H66B,
 H66C), C67(H67A,H67B,H67C)
;
_shelx_res_checksum              33210
_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 3.469
_oxdiff_exptl_absorpt_empirical_full_min 0.512