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_1570865
_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 H272 Au12 N40, C70, 13[C2H2Cl4]'
_chemical_formula_sum            'C312 H298 Au12 Cl52 N40'
_chemical_formula_weight         8788.68
_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
_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                62.4166(13)
_cell_angle_beta                 79.9283(11)
_cell_angle_gamma                72.2345(9)
_cell_formula_units_Z            2
_cell_length_a                   27.2311(3)
_cell_length_b                   27.3567(3)
_cell_length_c                   27.4198(4)
_cell_measurement_reflns_used    78413
_cell_measurement_temperature    229.99(10)
_cell_measurement_theta_max      68.2490
_cell_measurement_theta_min      1.7480
_cell_volume                     17227.7(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     65.00  94.00   0.50    0.20    --   69.60-125.00 120.00   58
  2  \w     28.00  61.00   0.50    0.20    --   69.60-125.00 120.00   66
  3  \w     52.00  96.00   0.50    0.20    --   69.60-125.00 -90.00   88
  4  \w     46.00  73.00   0.50    0.20    --   78.02-125.00-180.00   54
  5  \w     78.00 105.00   0.50    0.20    --   78.02-125.00-180.00   54
  6  \w     66.00 104.00   0.50    0.20    --   78.02-125.00-150.00   76
  7  \w     80.00 105.00   0.50    0.20    --   78.02-125.00   0.00   50
  8  \w     80.00 105.00   0.50    0.20    --   78.02-125.00 -30.00   50
  9  \w     71.00 105.00   0.50    0.20    --   78.02-125.00 -60.00   68
 10  \w     74.00 103.00   0.50    0.20    --   78.02-125.00  30.00   58
 11  \w     38.00  64.00   0.50    0.20    --   78.02-125.00  30.00   52
 12  \w     36.00 104.00   0.50    0.20    --   78.02-125.00  60.00  136
 13  \w     79.00 105.00   0.50    0.20    --   78.02-125.00 120.00   52
 14  \w     80.00 105.00   0.50    0.20    --   78.02-125.00 150.00   50
 15  \w     41.00  74.00   0.50    0.20    --   78.02-125.00 120.00   66
 16  \w     29.00  61.00   0.50    0.20    --   66.15 -95.00   0.00   64
 17  \w     40.00  72.00   0.50    0.20    --   78.02-125.00 -30.00   64
 18  \w     80.00 105.00   0.50    0.20    --   78.02-125.00 -90.00   50
 19  \w     46.00 105.00   0.50    0.20    --   78.02-125.00-120.00  118
 20  \w     29.00  71.00   0.50    0.20    --   66.15 -95.00-180.00   84
 21  \w     28.00  63.00   0.50    0.20    --   66.15 -95.00-120.00   70
 22  \w     29.00  54.00   0.50    0.20    --   66.15 -95.00  60.00   50
 23  \w     37.00  65.00   0.50    0.20    --   69.60 -95.00  60.00   56
 24  \w     32.00  78.00   0.50    0.20    --   69.60 -95.00 120.00   92
 25  \w     60.00  87.00   0.50    0.20    --   78.02 -95.00  90.00   54
 26  \w     62.00 117.00   0.50    0.20    --   78.02  15.00  30.00  110
 27  \w     48.00 123.00   0.50    0.20    --   78.02  15.00 120.00  150
 28  \w     45.00 122.00   0.50    0.20    --   78.02  18.00-131.00  154
 29  \w     89.00 116.00   0.50    0.20    --   69.60  18.00-131.00   54
 30  \w     61.00  86.00   0.50    0.20    --   66.15  18.00-131.00   50
 31  \w     42.00  69.00   0.50    0.20    --   69.60  18.00-131.00   54
 32  \w     72.00  97.00   0.50    0.20    --   78.02  15.00-120.00   50
 33  \w     49.00 123.00   0.50    0.20    --   78.02  15.00 -60.00  148
 34  \w     91.00 119.00   0.50    0.20    --   78.02  15.00 -30.00   56
 35  \w     67.00  94.00   0.50    0.20    --   78.02  15.00   0.00   54
 36  \w   -110.00 -34.00   0.50    0.20    --  -66.74 -18.00  60.00  152
 37  \w   -103.00 -73.00   0.50    0.20    --  -66.74   0.00  90.00   60
 38  \w   -103.00 -72.00   0.50    0.20    --  -66.74   0.00 150.00   62
 39  \w    -98.00 -42.00   0.50    0.20    --  -69.40 -18.00  60.00  112
 40  \w   -102.00 -73.00   0.50    0.20    --  -66.74   0.00 -60.00   58
 41  \w   -104.00 -74.00   0.50    0.20    --  -69.40   0.00 -60.00   60
 42  \w   -104.00 -73.00   0.50    0.20    --  -66.74   0.00-150.00   62
 43  \w   -104.00 -72.00   0.50    0.20    --  -66.74   0.00-180.00   64
 44  \w    -94.00 -43.00   0.50    0.20    --  -74.00 114.00-153.57  102
 45  \w   -114.00 -36.00   0.50    0.20    --  -74.00 148.00-120.68  156
 46  \w   -120.00 -88.00   0.50    0.20    --  -74.85 153.00  35.40   64
 47  \w   -108.00 -80.00   0.50    0.20    --  -74.85 141.00  56.79   56
 48  \w   -118.00 -58.00   0.50    0.20    --  -74.85 149.00 145.78  120
 49  \w    -64.00 -38.00   0.50    0.20    --  -74.85 141.00  56.79   52
 50  \w    -96.00 -27.00   0.50    0.20    --  -69.40 125.00 -30.00  138
 51  \w    -76.00 -26.00   0.50    0.20    --  -66.74 125.00 -90.00  100
 52  \w   -103.00 -73.00   0.50    0.20    --  -74.85 126.00-120.30   60
 53  \w    -74.00 -30.00   0.50    0.20    --  -66.74 125.00-150.00   88
;
_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      0.0114325000
_diffrn_orient_matrix_UB_12      -0.0655483000
_diffrn_orient_matrix_UB_13      0.0304670000
_diffrn_orient_matrix_UB_21      -0.0081984000
_diffrn_orient_matrix_UB_22      -0.0018639000
_diffrn_orient_matrix_UB_23      -0.0532389000
_diffrn_orient_matrix_UB_31      0.0577651000
_diffrn_orient_matrix_UB_32      -0.0046705000
_diffrn_orient_matrix_UB_33      -0.0161848000
_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  0.0425
_diffrn_reflns_av_unetI/netI     0.0363
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            297732
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        66.601
_diffrn_reflns_theta_max         66.600
_diffrn_reflns_theta_min         1.705
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    13.495
_exptl_absorpt_correction_T_max  0.513
_exptl_absorpt_correction_T_min  0.198
_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            'clear dark red'
_exptl_crystal_density_diffrn    1.694
_exptl_crystal_description       prism
_exptl_crystal_F_000             8512
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.16
_refine_diff_density_max         1.929
_refine_diff_density_min         -0.976
_refine_diff_density_rms         0.118
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2957
_refine_ls_number_reflns         60611
_refine_ls_number_restraints     5711
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0751
_refine_ls_R_factor_gt           0.0570
_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^)+(0.0985P)^2^+10.4690P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1642
_refine_ls_wR_factor_ref         0.1738
_reflns_Friedel_coverage         0.000
_reflns_number_gt                42884
_reflns_number_total             60611
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06280e2.cif
_cod_data_source_block           ne0277_big
_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        17227.8(4)
_cod_database_code               1570865
_shelx_shelxl_version_number     2019/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C312 H298 Au12 Cl52 N40'
_shelx_estimated_absorpt_t_max   0.221
_shelx_estimated_absorpt_t_min   0.133
_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
 C156-C274
 1.5 with sigma of 0.02
 C218-C156 = C274-C156 = C95-C276 = C95-C36 = C84-C66 = C84-C234 = C88-C107 =
 C88-C244 = C165-C142 = C280-C165 = C120-C118 = C224-C120 = C232-C194 = C194-
 C157 = C220-C11 = C181-C11 = C169-C134 = C242-C169 = C207-C103 = C34-C103 =
 C284-C167 = C167-C126 = C212-C124 = C264-C124 = C77-C252 = C92-C77 = C76-C214 =
  C214-C12 = C268-C177 = C260-C177 = C266-C193 = C193-C108 = C91-C213 = C91-C6 =
  C99-C104 = C99-C236 = C85-C198 = C198-C153 = C258-C152 = C282-C152 = C30-C166
 = C166-C14 = C190-C162 = C168-C162 = C210-C105 = C73-C210 = C80-C270 = C270-
 C201
 1.54 with sigma of 0.02
 C177-C260
 1.5 with sigma of 0.02
 C108-C193
 1.5 with sigma of 0.02
 C107-C88
 1.5 with sigma of 0.02
 C31-C259 = C247-C31 = C235-C247 = C235-C265 = C265-C33 = C259-C33
 1.39 with sigma of 0.02
 C235-C283 = C141-C283 = C141-C65 = C65-C123 = C247-C123 = C235-C247
 1.39 with sigma of 0.02
 C65-C123 = C251-C123 = C251-C267 = C267-C55 = C55-C221 = C65-C221
 1.39 with sigma of 0.02
 C233-C7 = C223-C7 = C285-C223 = C237-C285 = C237-C117 = C233-C117
 1.39 with sigma of 0.02
 C121-C119 = C275-C121 = C275-C239 = C129-C239 = C253-C129 = C253-C119
 1.39 with sigma of 0.02
 C59-C15
 1.39 with sigma of 0.02
 C125-C231 = C249-C125 = C249-C15 = C59-C29 = C29-C231 = C59-C15
 1.39 with sigma of 0.02
 C275-C243
 1.39 with sigma of 0.02
 C257-C269 \\sim C129-C257 \\sim C129-C239 \\sim C137-C239 \\sim C137-C269
 with sigma of 0.02
 C285-C223 \\sim C121-C119 \\sim C285-C119 \\sim C111-C223 \\sim C111-C121
 with sigma of 0.02
 C57-C67 \\sim C243-C241
 with sigma of 0.02
 C241-C131 \\sim C263-C57
 with sigma of 0.02
 C273-C243 \\sim C57-C275
 with sigma of 0.02
 C137-C275 \\sim C239-C273
 with sigma of 0.02
 C249-C15 \\sim C249-C31 \\sim C31-C259 \\sim C259-C63 \\sim C63-C15
 with sigma of 0.02
 C15-C29 \\sim C29-C125
 with sigma of 0.02
 C231-C249 \\sim C249-C59
 with sigma of 0.02
 C129-C275 \\sim C239-C121
 with sigma of 0.02
 C121-C253 \\sim C119-C129
 with sigma of 0.02
 C217-C255 \\sim C255-C245
 with sigma of 0.02
 C109-C2 \\sim C255-C217
 with sigma of 0.02
 C229-C219 \\sim C219-C139
 with sigma of 0.02
 C111-C275 \\sim C275-C67
 with sigma of 0.02
 C121-C227 \\sim C227-C243
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01 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 X: C156(0.39155)
 Fixed Y: C156(0.352)
6.a Riding coordinates:
 C34(H34A,H34B,H34C)
6.b Ternary CH refined with riding coordinates:
 C11(H11), C77(H77), C84(H84), C88(H88), C91(H91), C95(H95), C99(H99),
 C103(H103), C120(H120), C124(H124), C152(H152), C156(H156), C162(H162),
 C165(H165), C166(H166), C167(H167), C169(H169), C177(H177), C193(H193),
 C198(H198), C210(H210), C214(H214), C270(H270)
6.c Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C28(H28A,H28B), C58(H58A,H58B), C72(H72A,H72B), C100(H10A,
 H10B), C110(H11A,H11B), C159(H15G,H15H), C192(H19D,H19E), C195(H19F,H19G),
 C199(H19H,H19I), C203(H20D,H20E), C205(H20F,H20G), C208(H20K,H20L), C209(H20M,
 H20N), C211(H21A,H21B), C216(H21I,H21J), C226(H22G,H22H), C228(H22I,H22J),
 C240(H24C,H24D), C248(H24K,H24L), C250(H25A,H25B), C272(H27A,H27B)
6.d Me refined with riding coordinates:
 C6(H6A,H6B,H6C), C36(H36A,H36B,H36C), C66(H66A,H66B,H66C), C76(H76A,H76B,
 H76C), C85(H85A,H85B,H85C), C92(H92A,H92B,H92C), C104(H10C,H10D,H10E),
 C105(H10F,H10G,H10H), C107(H10I,H10J,H10K), C108(H10L,H10M,H10N), C118(H11C,
 H11D,H11E), C126(H12D,H12E,H12F), C134(H13A,H13B,H13C), C142(H14D,H14E,H14F),
 C157(H15D,H15E,H15F), C190(H19A,H19B,H19C), C207(H20H,H20I,H20J), C212(H21C,
 H21D,H21E), C213(H21F,H21G,H21H), C224(H22D,H22E,H22F), C232(H23A,H23B,H23C),
 C234(H23D,H23E,H23F), C236(H23G,H23H,H23I), C242(H24E,H24F,H24G), C244(H24H,
 H24I,H24J), C252(H25C,H25D,H25E), C260(H26A,H26B,H26C), C264(H26D,H26E,H26F),
 C266(H26G,H26H,H26I), C268(H26J,H26K,H26L), C276(H27E,H27F,H27G), C280(H28C,
 H28D,H28E), C282(H28F,H28G,H28H)
6.e Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C8(H8), C13(H13), C18(H18), C19(H19), C20(H20), C21(H21),
 C22(H22), C39(H39), C42(H42), C45(H45), C47(H47), C48(H48), C49(H49), C51(H51),
  C52(H52), C60(H60), C64(H64), C68(H68), C83(H83), C87(H87), C89(H89),
 C93(H93), C96(H96), C97(H97), C101(H101), C112(H112), C140(H140), C143(H143),
 C144(H144), C145(H145), C147(H147), C148(H148), C149(H149), C151(H151),
 C155(H155), C160(H160), C161(H161), C163(H163), C164(H164), C171(H171),
 C172(H172), C173(H173), C176(H176), C179(H179), C180(H180), C183(H183),
 C184(H184), C185(H185), C186(H186), C187(H187), C188(H188), C189(H189),
 C191(H191), C196(H196), C197(H197), C200(H200), C202(H202), C204(H204),
 C222(H222), C256(H256)
6.f Fitted hexagon refined as free rotating group:
 C27(C217,C109,C219,C55,C221), C111(C223,C7,C225,C113,C227), C123(C247,C31,
 C249,C125,C251), C229(C115,C231,C29,C233,C117), C253(C127,C255,C2,C257,C129),
 C261(C131,C263,C33,C265,C133), C269(C135,C271,C17,C273,C137), C279(C35,C281,
 C141,C283,C71)
6.g X=CH2 refined with riding coordinates:
 C274(H27C,H27D)
6.h Idealised Me refined with riding coordinates:
 C258(H25F,H25G,H25H)
6.i Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C30(H30A,H30B,H30C), C73(H73A,H73B,
 H73C), C80(H80A,H80B,H80C), C153(H15A,H15B,H15C), C168(H16A,H16B,H16C),
 C181(H18A,H18B,H18C), C201(H20A,H20B,H20C), C218(H21K,H21L,H21M), C220(H22A,
 H22B,H22C), C284(H28I,H28J,H28K)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              4159
_shelx_fab_checksum              23680
_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 1.689
_oxdiff_exptl_absorpt_empirical_full_min 0.712