Molecular imine cages with π-basic Au<sub>3</sub>(pyrazolate) faces.
Eren, Noga; Fadaei-Tirani, Farzaneh; Scopelliti, Rosario; Severin, Kay; Chemical science 15 (2024) 3539–3544; doi:10.1039/d3sc06280e

data_1570862
_publ_section_title
;
 Molecular imine cages with &#x3c0;-basic Au<sub>3</sub>(pyrazolate)
 faces.
;
_journal_issue                   10
_journal_name_full               'Chemical science'
_journal_page_first              3539
_journal_page_last               3544
_journal_paper_doi               10.1039/d3sc06280e
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C120 H138 Au6 N18, 11.5[CH2Cl2], 1.25[CH2Cl2]'
_chemical_formula_sum            'C132.75 H163.5 Au6 Cl25.5 N18'
_chemical_formula_weight         4097.08
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-01-14
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-01-14 deposited with the CCDC.	2024-01-25 downloaded from the CCDC.
;
_cell_angle_alpha                96.246(2)
_cell_angle_beta                 97.033(2)
_cell_angle_gamma                105.196(3)
_cell_formula_units_Z            2
_cell_length_a                   20.8869(6)
_cell_length_b                   21.3091(7)
_cell_length_c                   21.4286(4)
_cell_measurement_reflns_used    30479
_cell_measurement_temperature    140.00
_cell_measurement_theta_max      63.0460
_cell_measurement_theta_min      2.5680
_cell_volume                     9035.4(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_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, 2015)'
_diffrn_ambient_temperature      140.00
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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     28.00  53.00   0.50    2.50    --   66.21 -95.00  60.00   50
  2  \w     30.00  57.00   0.50    2.50    --   66.21 -95.00  90.00   54
  3  \w     75.00 102.00   0.50    2.50    --   66.21  15.00 150.00   54
  4  \w     28.00  64.00   0.50    2.50    --   66.21 -95.00-180.00   72
  5  \w     29.00  74.00   0.50    2.50    --   66.21 -95.00 -60.00   90
  6  \w   -103.00 -72.00   0.50    2.50    --  -66.84   0.00 -30.00   62
  7  \w   -104.00 -72.00   0.50    2.50    --  -66.84   0.00-120.00   64
  8  \w   -103.00 -73.00   0.50    2.50    --  -66.84   0.00 -90.00   60
  9  \w    -98.00 -59.00   0.50    2.50    --  -66.84 -15.00 -60.00   78
 10  \w   -104.00 -74.00   0.50    2.50    --  -66.84   0.00-180.00   60
 11  \w    -91.00 -35.00   0.50    2.50    --  -66.84 125.00-180.00  112
 12  \w   -107.00 -72.00   0.50    2.50    --  -69.31   0.00  30.00   70
 13  \w    -73.00 -38.00   0.50    2.50    --  -69.31 -15.00-120.00   70
 14  \w   -106.00 -71.00   0.50    2.50    --  -69.31 -15.00 150.00   70
 15  \w    -69.00 -38.00   0.50    2.50    --  -69.31 -15.00 150.00   62
 16  \w    -72.00 -42.00   0.50    2.50    --  -69.31 -15.00-150.00   60
 17  \w   -106.00 -73.00   0.50    2.50    --  -69.31   0.00 -60.00   66
 18  \w     31.00  89.00   0.50    2.50    --   69.48-125.00-180.00  116
 19  \w     35.00  65.00   0.50    2.50    --   69.48 -95.00-120.00   60
 20  \w     33.00  64.00   0.50    2.50    --   69.48 -95.00 120.00   62
 21  \w     33.00  71.00   0.50    2.50    --   69.48 -95.00   0.00   76
 22  \w     33.00  78.00   0.50    2.50    --   69.48 -95.00 -90.00   90
 23  \w   -115.00 -51.00   0.50    2.50    --  -74.00 148.00 -42.15  128
 24  \w   -113.00 -40.00   0.50    2.50    --  -74.78 142.00  -1.74  146
 25  \w    -72.00 -39.00   0.50    2.50    --  -74.78 141.00 104.22   66
 26  \w   -111.00 -85.00   0.50    2.50    --  -74.78 141.00 104.22   52
 27  \w    -83.00 -36.00   0.50    2.50    --  -74.78 141.00-159.33   94
 28  \w   -112.00 -86.00   0.50    2.50    --  -74.78 141.00-159.33   52
 29  \w   -109.00 -33.00   0.50    2.50    --  -74.78 138.00 -48.06  152
 30  \w     70.00 102.00   0.50    2.50    --   78.10-125.00 120.00   64
 31  \w     62.00 120.00   0.50    2.50    --   78.10  15.00   0.00  116
 32  \w     47.00 118.00   0.50    2.50    --   78.10  15.00 120.00  142
 33  \w     72.00 105.00   0.50    2.50    --   78.10-125.00   0.00   66
 34  \w     54.00  80.00   0.50    2.50    --   78.10 -95.00 -30.00   52
 35  \w     43.00  70.00   0.50    2.50    --   78.10-125.00   0.00   54
 36  \w     50.00 120.00   0.50    2.50    --   78.10  15.00-120.00  140
 37  \w     53.00  85.00   0.50    2.50    --   78.10 -95.00-150.00   64
 38  \w     80.00 105.00   0.50    2.50    --   78.10-125.00 -90.00   50
 39  \w     39.00 105.00   0.50    2.50    --   78.10-125.00  90.00  132
 40  \w     84.00 116.00   0.50    2.50    --   78.10  15.00 150.00   64
 41  \w     80.00 105.00   0.50    2.50    --   78.10-125.00-150.00   50
 42  \w     39.00 105.00   0.50    2.50    --   78.10-125.00-180.00  132
 43  \w     80.00 105.00   0.50    2.50    --   78.10-125.00 -30.00   50
 44  \w     80.00 105.00   0.50    2.50    --   78.10-125.00  60.00   50
 45  \w     38.00  63.00   0.50    2.50    --   78.10-125.00-120.00   50
 46  \w     80.00 105.00   0.50    2.50    --   78.10-125.00 150.00   50
 47  \w     80.00 105.00   0.50    2.50    --   78.10-125.00 -60.00   50
 48  \w     57.00  84.00   0.50    2.50    --   78.10 -95.00-180.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0037439000
_diffrn_orient_matrix_UB_12      0.0425223000
_diffrn_orient_matrix_UB_13      -0.0533227000
_diffrn_orient_matrix_UB_21      0.0745370000
_diffrn_orient_matrix_UB_22      0.0378318000
_diffrn_orient_matrix_UB_23      0.0217297000
_diffrn_orient_matrix_UB_31      0.0204946000
_diffrn_orient_matrix_UB_32      -0.0499708000
_diffrn_orient_matrix_UB_33      -0.0452524000
_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  0.0771
_diffrn_reflns_av_unetI/netI     0.0633
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            94655
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        50.436
_diffrn_reflns_theta_max         50.436
_diffrn_reflns_theta_min         2.220
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.743
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.214
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.85a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on Gaussian integration over
a multifaceted crystal model.
Empirical absorption correction using spherical harmonics
as implemented in SCALE3 ABSPACK scaling algorithm
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.506
_exptl_crystal_description       needle
_exptl_crystal_F_000             3987
_exptl_crystal_size_max          0.53
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.438
_refine_diff_density_min         -0.909
_refine_diff_density_rms         0.103
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1210
_refine_ls_number_reflns         18871
_refine_ls_number_restraints     2253
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0780
_refine_ls_R_factor_gt           0.0536
_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^)+(0.0998P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1577
_refine_ls_wR_factor_ref         0.1671
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12121
_reflns_number_total             18871
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06280e2.cif
_cod_data_source_block           ne0250
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Gaussian' was
changed to 'gaussian' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1570859--1570865.cif.
;
_cod_original_formula_sum        'C132.75 H163.50 Au6 Cl25.50 N18'
_cod_database_code               1570862
_shelx_shelxl_version_number     2019/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C132.75 H163.50 Au6 Cl25.50 N18'
_shelx_estimated_absorpt_t_max   0.785
_shelx_estimated_absorpt_t_min   0.057
_exptl_absorpt_special_details
;    
There were no reflections beyond d(min)=1 Angstrom.
So, data are cut to this resolution.
;
_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
 C25-C26 = C16-C13 = C20-C24 = C17-C18
 1.5 with sigma of 0.02
 C45-C44 = C46-C44 = C49-C47 = C48-C47 = C77-C75 = C76-C75 = C80-C78 = C79-C78
 = C117-C115 = C116-C115 = C120-C118 = C119-C118 = C36-C35 = C37-C35 = C40-C38 =
  C39-C38 = C9-C7 = C8-C7 = C4-C6 = C5-C4 = C88-C87 = C89-C87 = C85-C84 = C86-
 C84
 1.54 with sigma of 0.01
 N14-C24 = N13-C17
 1.47 with sigma of 0.02
 C96-C93 = C105-C106 = C104-C100 = C97-C98
 1.5 with sigma of 0.01
 N17-C97
 1.47 with sigma of 0.01
 C56-C53 = C57-C58 = C64-C60 = C65-C66
 1.5 with sigma of 0.01
 N16-C64
 1.47 with sigma of 0.01
 N18-C104
 1.47 with sigma of 0.01
 N15-C57
 1.47 with sigma of 0.01
 C26-C25 = C16-C13 = C32-C29 = C2-C10 = C24-C20 = C18-C17 = C72-C69 = C50-C42 =
  C56-C53 = C66-C65 = C64-C60 = C58-C57 = C104-C100 = C98-C97 = C96-C93 = C106-
 C105 = C112-C109 = C90-C82
 1.5 with sigma of 0.02
 C20-C24
 1.5 with sigma of 0.01
 C56-C57
 2.45 with sigma of 0.04
 C58-N15
 2.45 with sigma of 0.04
 C53-N15
 2.45 with sigma of 0.04
 C105-C104
 2.45 with sigma of 0.04
 C106-N18
 2.45 with sigma of 0.04
 N18-C100
 2.45 with sigma of 0.04
 C16-C17
 2.45 with sigma of 0.04
 C25-C24
 2.45 with sigma of 0.04
 C26-N14
 2.45 with sigma of 0.04
 N14-C20
 2.45 with sigma of 0.04
 C13-N13
 2.45 with sigma of 0.04
 N13-C18
 2.45 with sigma of 0.04
 H24A-H21
 2 with sigma of 0.04
 H97B-H64B_$1
 2.5 with sigma of 0.04
 C117-C116 \\sim C120-C119 \\sim C85-C86 \\sim C89-C88 \\sim C49-C48 \\sim
C46-C45 \\sim C76-C77 \\sim C80-
 C79 \\sim C39-C40 \\sim C37-C36 \\sim C8-C9 \\sim C6-C5
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C19 \\sim C18 \\sim C23 \\sim C22 \\sim C21 \\sim C20 \\sim C24 \\sim C25
\\sim C29 \\sim C30 \\sim C31 \\sim C26 \\sim C27 \\sim C28 \\sim C32 \\sim C33
\\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41
\\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49
\\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57
\\sim C59 \\sim C58 \\sim C63 \\sim C62 \\sim C61 \\sim C60 \\sim C64 \\sim C65
\\sim C69 \\sim C70 \\sim C71 \\sim C66 \\sim C67 \\sim C68 \\sim C72 \\sim C73
\\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81
\\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C87 \\sim C88 \\sim C89
\\sim C93 \\sim C94 \\sim C95 \\sim C90 \\sim C91 \\sim C92 \\sim C96 \\sim C97
\\sim C99 \\sim C98 \\sim C103 \\sim C102 \\sim C101 \\sim C100 \\sim C104
\\sim C105 \\sim C106 \\sim C111 \\sim C110 \\sim C109 \\sim C108 \\sim C107
\\sim C112 \\sim C113 \\sim C114 \\sim C115 \\sim C116 \\sim C117 \\sim C118
\\sim C119 \\sim C120 \\sim N1 \\sim N2 \\sim N3 \\sim N4 \\sim N5 \\sim N6
\\sim N7 \\sim N8 \\sim N9 \\sim N10 \\sim N11 \\sim N12 \\sim N13 \\sim N14
\\sim N15 \\sim N16 \\sim N17 \\sim N18: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Y: C78(0.37731)
6.a Ternary CH refined with riding coordinates:
 C4(H4), C7(H7), C35(H35), C38(H38), C44(H44), C47(H47), C75(H75), C78(H78),
 C84(H84), C87(H87), C115(H115), C118(H118)
6.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C24(H24A,H24B), C57(H57A,H57B), C64(H64A,H64B), C97(H97A,
 H97B), C104(H10A,H10B)
6.c Me refined with riding coordinates:
 C8(H8A,H8B,H8C), C48(H48A,H48B,H48C)
6.d Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C14(H14), C15(H15), C16(H16), C19(H19), C23(H23),
 C22(H22), C21(H21), C25(H25), C30(H30), C31(H31), C27(H27), C28(H28), C51(H51),
  C52(H52), C54(H54), C55(H55), C56(H56), C59(H59), C63(H63), C62(H62),
 C61(H61), C65(H65), C70(H70), C71(H71), C67(H67), C68(H68), C94(H94), C95(H95),
  C91(H91), C92(H92), C96(H96), C99(H99), C103(H103), C102(H102), C101(H101),
 C105(H105), C111(H111), C110(H110), C108(H108), C107(H107)
6.e Fitted hexagon refined as free rotating group:
 C10(C11,C12,C13,C14,C15), C19(C18,C23,C22,C21,C20), C29(C30,C31,C26,C27,C28),
 C50(C51,C52,C53,C54,C55), C59(C58,C63,C62,C61,C60), C69(C70,C71,C66,C67,C68),
 C93(C94,C95,C90,C91,C92), C99(C98,C103,C102,C101,C100), C106(C111,C110,C109,
 C108,C107)
6.f Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C9(H9A,H9B,H9C), C36(H36A,H36B,H36C),
 C37(H37A,H37B,H37C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C45(H45A,H45B,
 H45C), C46(H46A,H46B,H46C), C49(H49A,H49B,H49C), C76(H76A,H76B,H76C), C77(H77A,
 H77B,H77C), C79(H79A,H79B,H79C), C80(H80A,H80B,H80C), C85(H85A,H85B,H85C),
 C86(H86A,H86B,H86C), C88(H88A,H88B,H88C), C89(H89A,H89B,H89C), C116(H11A,H11B,
 H11C), C117(H11D,H11E,H11F), C119(H11G,H11H,H11I), C120(H12A,H12B,H12C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              51759
_shelx_fab_checksum              82141
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 9.039
_oxdiff_exptl_absorpt_empirical_full_min 0.141