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_1570863
_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         'C216 H276 Au12 N40, 12.75[C2H2Cl4]'
_chemical_formula_sum            'C241.5 H301.5 Au12 Cl51 N40'
_chemical_formula_weight         7910.55
_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
;
2024-01-18 deposited with the CCDC.	2024-01-25 downloaded from the CCDC.
;
_cell_angle_alpha                112.4515(10)
_cell_angle_beta                 94.9615(8)
_cell_angle_gamma                119.2080(10)
_cell_formula_units_Z            2
_cell_length_a                   27.6564(2)
_cell_length_b                   27.7466(3)
_cell_length_c                   28.2657(3)
_cell_measurement_reflns_used    75502
_cell_measurement_temperature    229.99(10)
_cell_measurement_theta_max      74.1890
_cell_measurement_theta_min      1.8970
_cell_volume                     16466.2(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (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_environment      N~2~
_diffrn_ambient_temperature      229.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_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     67.00 101.00   0.50    0.20    --   69.60  15.00 120.00   68
  2  \w     54.00 102.00   0.50    0.20    --   66.15  15.00  60.00   96
  3  \w     80.00 106.00   0.50    0.20    --   69.60  15.00 -90.00   52
  4  \w     62.00  90.00   0.50    0.20    --   66.15  15.00-180.00   56
  5  \w     48.00 113.00   0.50    0.20    --   78.02  15.00-180.00  130
  6  \w     38.00 103.00   0.50    0.20    --   69.60  15.00-150.00  130
  7  \w     44.00  71.00   0.50    0.20    --   69.60  15.00 -90.00   54
  8  \w     67.00 106.00   0.50    0.20    --   78.02  15.00 -60.00   78
  9  \w     47.00  94.00   0.50    0.20    --   78.02  15.00   0.00   94
 10  \w     69.00 123.00   0.50    0.20    --   78.02  15.00  30.00  108
 11  \w     64.00 109.00   0.50    0.20    --   78.02  15.00  90.00   90
 12  \w     29.00  65.00   0.50    0.20    --   66.15 -95.00  90.00   72
 13  \w     43.00  77.00   0.50    0.20    --   78.02-125.00  60.00   68
 14  \w     74.00 104.00   0.50    0.20    --   78.02-125.00   0.00   60
 15  \w     44.00  69.00   0.50    0.20    --   78.02-125.00   0.00   50
 16  \w     29.00  63.00   0.50    0.20    --   69.60-125.00-120.00   68
 17  \w     56.00 105.00   0.50    0.20    --   78.02-125.00-180.00   98
 18  \w     38.00 105.00   0.50    0.20    --   78.02-125.00 -90.00  134
 19  \w     80.00 105.00   0.50    0.20    --   78.02-125.00 -60.00   50
 20  \w     80.00 105.00   0.50    0.20    --   78.02-125.00  30.00   50
 21  \w     80.00 105.00   0.50    0.20    --   78.02-125.00  90.00   50
 22  \w     80.00 105.00   0.50    0.20    --   78.02-125.00 120.00   50
 23  \w     47.00 105.00   0.50    0.20    --   78.02-125.00 150.00  116
 24  \w     41.00  66.00   0.50    0.20    --   78.02 -96.00  48.00   50
 25  \w     31.00  61.00   0.50    0.20    --   66.15 -96.00  48.00   60
 26  \w     32.00  57.00   0.50    0.20    --   69.60 -96.00  48.00   50
 27  \w     29.00  64.00   0.50    0.20    --   66.15 -95.00 -30.00   70
 28  \w     37.00  68.00   0.50    0.20    --   78.02-125.00 -60.00   62
 29  \w     30.00  71.00   0.50    0.20    --   66.15 -95.00   0.00   82
 30  \w     34.00  63.00   0.50    0.20    --   69.60 -95.00 -60.00   58
 31  \w     33.00  73.00   0.50    0.20    --   69.60 -95.00 150.00   80
 32  \w     80.00 105.00   0.50    0.20    --   78.02-125.00-150.00   50
 33  \w     36.00  62.00   0.50    0.20    --   78.02-125.00-150.00   52
 34  \w     43.00  69.00   0.50    0.20    --   66.15 -95.00-150.00   52
 35  \w   -103.00 -74.00   0.50    0.20    --  -66.74   0.00 -30.00   58
 36  \w   -104.00 -72.00   0.50    0.20    --  -66.74   0.00-150.00   64
 37  \w   -103.00 -72.00   0.50    0.20    --  -66.74   0.00 -60.00   62
 38  \w   -107.00 -72.00   0.50    0.20    --  -69.40   0.00   0.00   70
 39  \w   -104.00 -72.00   0.50    0.20    --  -66.74   0.00  60.00   64
 40  \w   -103.00 -72.00   0.50    0.20    --  -69.40   0.00  90.00   62
 41  \w    -78.00 -53.00   0.50    0.20    --  -69.40  96.00 157.00   50
 42  \w   -113.00 -87.00   0.50    0.20    --  -74.85 144.00 169.90   52
 43  \w    -80.00 -40.00   0.50    0.20    --  -74.85 144.00 169.90   80
 44  \w   -111.00 -85.00   0.50    0.20    --  -74.85 139.00  84.11   52
 45  \w   -112.00 -34.00   0.50    0.20    --  -74.00 146.00  15.96  156
 46  \w   -116.00 -45.00   0.50    0.20    --  -74.85 146.00 -15.63  142
 47  \w   -112.00 -76.00   0.50    0.20    --  -74.85 140.00 -63.80   72
 48  \w    -70.00 -33.00   0.50    0.20    --  -74.85 140.00 -63.80   74
 49  \w    -92.00 -32.00   0.50    0.20    --  -69.40 125.00-120.00  120
 50  \w    -92.00 -66.00   0.50    0.20    --  -74.85 111.00-114.87   52
 51  \w    -94.00 -64.00   0.50    0.20    --  -74.00 114.00 141.63   60
 52  \w    -65.00 -39.00   0.50    0.20    --  -66.74  96.00 157.00   52
;
_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      -0.0220896000
_diffrn_orient_matrix_UB_12      -0.0678892000
_diffrn_orient_matrix_UB_13      -0.0126793000
_diffrn_orient_matrix_UB_21      -0.0040151000
_diffrn_orient_matrix_UB_22      0.0157691000
_diffrn_orient_matrix_UB_23      0.0574102000
_diffrn_orient_matrix_UB_31      -0.0639902000
_diffrn_orient_matrix_UB_32      -0.0212488000
_diffrn_orient_matrix_UB_33      -0.0216876000
_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  0.0875
_diffrn_reflns_av_unetI/netI     0.0716
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            265630
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        66.599
_diffrn_reflns_theta_max         66.599
_diffrn_reflns_theta_min         1.884
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    13.966
_exptl_absorpt_correction_T_max  0.862
_exptl_absorpt_correction_T_min  0.065
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.90a (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    1.595
_exptl_crystal_description       prism
_exptl_crystal_F_000             7640
_exptl_crystal_size_max          0.47
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.12
_refine_diff_density_max         2.751
_refine_diff_density_min         -2.101
_refine_diff_density_rms         0.160
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2456
_refine_ls_number_reflns         57857
_refine_ls_number_restraints     3918
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0863
_refine_ls_R_factor_gt           0.0684
_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^)+(0.1190P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1956
_refine_ls_wR_factor_ref         0.2050
_reflns_Friedel_coverage         0.000
_reflns_number_gt                40389
_reflns_number_total             57857
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06280e2.cif
_cod_data_source_block           ne0253_3
_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_cell_volume        16466.2(3)
_cod_original_formula_sum        'C241.50 H301.5 Au12 Cl51 N40'
_cod_database_code               1570863
_shelx_shelxl_version_number     2019/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C241.50 H301.5 Au12 Cl51 N40'
_shelx_estimated_absorpt_t_max   0.285
_shelx_estimated_absorpt_t_min   0.059
_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
 C151-C150 = C152-C150
 1.54 with sigma of 0.02
 C9-C7 = C8-C7
 1.54 with sigma of 0.02
 C170-C168 = C169-C168
 1.54 with sigma of 0.02
 C38-C46
 1.5 with sigma of 0.02
 C166-C165 = C167-C165 = C169-C168 = C170-C168
 1.54 with sigma of 0.02
 C8-C7 = C9-C7
 1.54 with sigma of 0.02
 C7-C3
 1.5 with sigma of 0.02
 C4-C1
 1.5 with sigma of 0.02
 C151-C152
 2.54 with sigma of 0.04
 C8-C9
 2.54 with sigma of 0.04
 C169-C170
 2.54 with sigma of 0.04
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 C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\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 C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65
\\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\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 C90 \\sim C91 \\sim C92 \\sim C93 \\sim C94 \\sim C95 \\sim C96 \\sim C97
\\sim C98 \\sim C99 \\sim C100 \\sim C101 \\sim C102 \\sim C103 \\sim C104
\\sim C105 \\sim C106 \\sim C107 \\sim C108 \\sim C109 \\sim C110 \\sim C111
\\sim C112 \\sim C113 \\sim C114 \\sim C115 \\sim C116 \\sim C117 \\sim C118
\\sim C119 \\sim C120 \\sim C121 \\sim C122 \\sim C123 \\sim C124 \\sim C125
\\sim C126 \\sim C127 \\sim C128 \\sim C129 \\sim C130 \\sim C131 \\sim C132
\\sim C133 \\sim C134 \\sim C135 \\sim C136 \\sim C137 \\sim C138 \\sim C139
\\sim C140 \\sim C141 \\sim C142 \\sim C143 \\sim C144 \\sim C145 \\sim C146
\\sim C147 \\sim C148 \\sim C149 \\sim C150 \\sim C151 \\sim C152 \\sim C153
\\sim C154 \\sim C155 \\sim C156 \\sim C157 \\sim C158 \\sim C159 \\sim C160
\\sim C161 \\sim C162 \\sim C163 \\sim C164 \\sim C165 \\sim C166 \\sim C167
\\sim C168 \\sim C169 \\sim C170 \\sim C171 \\sim C172 \\sim C173 \\sim C174
\\sim C175 \\sim C176 \\sim C177 \\sim C178 \\sim C179 \\sim C180 \\sim C181
\\sim C182 \\sim C183 \\sim C184 \\sim C185 \\sim C186 \\sim C187 \\sim C188
\\sim C189 \\sim C190 \\sim C191 \\sim C192 \\sim C193 \\sim C194 \\sim C195
\\sim C196 \\sim C197 \\sim C198 \\sim C199 \\sim C200 \\sim C201 \\sim C202
\\sim C203 \\sim C204 \\sim C205 \\sim C206 \\sim C207 \\sim C208 \\sim C209
\\sim C210 \\sim C211 \\sim C212 \\sim C213 \\sim C214 \\sim C215 \\sim C216
\\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 \\sim N19 \\sim N20 \\sim N21 \\sim N22 \\sim N23 \\sim N24 \\sim
N25 \\sim N26 \\sim N27 \\sim N28 \\sim N29 \\sim N30 \\sim N31 \\sim N32 \\sim
N33 \\sim N34 \\sim N35 \\sim N36 \\sim N37 \\sim N38 \\sim N39 \\sim N40:
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.a Ternary CH refined with riding coordinates:
 C4(H4), C7(H7), C22(H22), C25(H25), C40(H40), C43(H43), C58(H58), C61(H61),
 C76(H76), C79(H79), C94(H94), C97(H97), C111(H111), C114(H114), C129(H129),
 C132(H132), C147(H147), C150(H150), C165(H165), C168(H168), C183(H183),
 C195(H195), C201(H201), C204(H204)
5.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C18(H18A,H18B), C35(H35A,H35B), C36(H36A,H36B), C53(H53A,
 H53B), C54(H54A,H54B), C71(H71A,H71B), C72(H72A,H72B), C89(H89A,H89B),
 C90(H90A,H90B), C106(H10A,H10B), C107(H10C,H10D), C124(H12A,H12B), C125(H12C,
 H12D), C142(H14A,H14B), C143(H14C,H14D), C160(H16A,H16B), C161(H16C,H16D),
 C178(H17F,H17G), C179(H17H,H17I), C193(H19A,H19B), C194(H19C,H19D), C214(H21A,
 H21B), C215(H21C,H21D)
5.c Me refined with riding coordinates:
 C26(H26A,H26B,H26C), C77(H77A,H77B,H77C), C80(H80A,H80B,H80C), C152(H15D,H15E,
 H15F), C196(H19E,H19F,H19G)
5.d Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C14(H14), C15(H15), C16(H16), C29(H29), C30(H30),
 C32(H32), C33(H33), C34(H34), C47(H47), C48(H48), C50(H50), C51(H51), C52(H52),
  C65(H65), C66(H66), C68(H68), C69(H69), C70(H70), C83(H83), C84(H84),
 C86(H86), C87(H87), C88(H88), C101(H101), C102(H102), C104(H104), C105(H105),
 C118(H118), C119(H119), C121(H121), C122(H122), C123(H123), C136(H136),
 C137(H137), C139(H139), C140(H140), C141(H141), C154(H154), C155(H155),
 C157(H157), C158(H158), C159(H159), C172(H172), C173(H173), C175(H175),
 C176(H176), C177(H177), C187(H187), C188(H188), C190(H190), C191(H191),
 C192(H192), C208(H208), C209(H209), C211(H211), C212(H212), C213(H213),
 C216(H216)
5.e Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C23(H23A,
 H23B,H23C), C24(H24A,H24B,H24C), C27(H27A,H27B,H27C), C41(H41A,H41B,H41C),
 C42(H42A,H42B,H42C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C59(H59A,H59B,
 H59C), C60(H60A,H60B,H60C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C78(H78A,
 H78B,H78C), C81(H81A,H81B,H81C), C95(H95A,H95B,H95C), C96(H96A,H96B,H96C),
 C98(H98A,H98B,H98C), C99(H99A,H99B,H99C), C112(H11A,H11B,H11C), C113(H11D,H11E,
 H11F), C115(H11G,H11H,H11I), C116(H11J,H11K,H11L), C130(H13A,H13B,H13C),
 C131(H13D,H13E,H13F), C133(H13G,H13H,H13I), C134(H13J,H13K,H13L), C148(H14E,
 H14F,H14G), C149(H14H,H14I,H14J), C151(H15A,H15B,H15C), C166(H16E,H16F,H16G),
 C167(H16H,H16I,H16J), C169(H16K,H16L,H16M), C170(H17C,H17D,H17E), C184(H18C,
 H18D,H18E), C185(H18F,H18G,H18H), C197(H19H,H19I,H19J), C202(H20A,H20B,H20C),
 C203(H20D,H20E,H20F), C205(H20G,H20H,H20I), C206(H20J,H20K,H20L)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 2010 electrons were 
found in a volume of 7652\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
10[C2Cl4], 2.75[C2Cl4] per Asymmetric Unit 
which account for 2040 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              94152
_shelx_fab_checksum              50419
_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 5.130
_oxdiff_exptl_absorpt_empirical_full_min 0.411