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_1570864
_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, 2(C Cl3 D), C60, 2[CDCl3]'
_chemical_formula_sum            'C280 H276 Au12 Cl12 D4 N40'
_chemical_formula_weight         6998.45
_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             2023-10-09
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-11-22 deposited with the CCDC.	2024-01-25 downloaded from the CCDC.
;
_cell_angle_alpha                91.9058(7)
_cell_angle_beta                 104.0920(8)
_cell_angle_gamma                94.9457(7)
_cell_formula_units_Z            2
_cell_length_a                   22.16590(19)
_cell_length_b                   24.2178(2)
_cell_length_c                   26.9851(2)
_cell_measurement_reflns_used    93630
_cell_measurement_temperature    140.15
_cell_measurement_theta_max      74.0180
_cell_measurement_theta_min      2.5520
_cell_volume                     13975.5(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      140.15
_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 0.951
_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     41.00  67.00   0.50    0.20    --   78.10-125.00-150.00   52
  2  \w     35.00  91.00   0.50    0.20    --   66.21-125.00 -30.00  112
  3  \w     38.00  95.00   0.50    0.20    --   69.48-125.00   0.00  114
  4  \w     80.00 105.00   0.50    0.20    --   78.10-125.00 -30.00   50
  5  \w     79.00 104.00   0.50    0.20    --   78.10-125.00  30.00   50
  6  \w     80.00 105.00   0.50    0.20    --   78.10-125.00  90.00   50
  7  \w     80.00 105.00   0.50    0.20    --   78.10-125.00 120.00   50
  8  \w     37.00  71.00   0.50    0.20    --   78.10-125.00 150.00   68
  9  \w     48.00  73.00   0.50    0.20    --   78.10-125.00 120.00   50
 10  \w     80.00 105.00   0.50    0.20    --   78.10-125.00 150.00   50
 11  \w     44.00  71.00   0.50    0.20    --   78.10-125.00  90.00   54
 12  \w     41.00  67.00   0.50    0.20    --   74.78-117.00 -18.06   52
 13  \w     80.00 105.00   0.50    0.20    --   78.10-125.00 -60.00   50
 14  \w     54.00 105.00   0.50    0.20    --   78.10-125.00-120.00  102
 15  \w     80.00 105.00   0.50    0.20    --   78.10-125.00-150.00   50
 16  \w     33.00  63.00   0.50    0.20    --   69.48 -95.00 -90.00   60
 17  \w     28.00  55.00   0.50    0.20    --   66.21 -95.00   0.00   54
 18  \w     35.00  76.00   0.50    0.20    --   69.48 -95.00  30.00   82
 19  \w     44.00  75.00   0.50    0.20    --   66.21 -95.00  60.00   62
 20  \w     37.00  69.00   0.50    0.20    --   66.21 -95.00 150.00   64
 21  \w     42.00  78.00   0.50    0.20    --   69.48 -95.00 120.00   72
 22  \w     35.00  64.00   0.50    0.20    --   69.48 -95.00  90.00   58
 23  \w     28.00  53.00   0.50    0.20    --   66.21 -95.00-120.00   50
 24  \w     34.00  62.00   0.50    0.20    --   69.48 -95.00-180.00   56
 25  \w     52.00 121.00   0.50    0.20    --   78.10  15.00-150.00  138
 26  \w     61.00 123.00   0.50    0.20    --   78.10  15.00 -90.00  124
 27  \w     54.00  80.00   0.50    0.20    --   69.48  15.00  30.00   52
 28  \w     81.00 106.00   0.50    0.20    --   69.48  15.00  30.00   50
 29  \w     61.00 123.00   0.50    0.20    --   78.10  15.00   0.00  124
 30  \w     61.00  98.00   0.50    0.20    --   78.10  15.00 -30.00   74
 31  \w     49.00 106.00   0.50    0.20    --   78.10  15.00  90.00  114
 32  \w     55.00 107.00   0.50    0.20    --   66.21  15.00 120.00  104
 33  \w    -91.00 -45.00   0.50    0.20    --  -66.84 -15.00  60.00   92
 34  \w   -103.00 -73.00   0.50    0.20    --  -69.31   0.00  90.00   60
 35  \w   -103.00 -72.00   0.50    0.20    --  -66.84   0.00   0.00   62
 36  \w   -106.00 -75.00   0.50    0.20    --  -69.31   0.00-120.00   62
 37  \w   -103.00 -74.00   0.50    0.20    --  -66.84   0.00-150.00   58
 38  \w   -107.00 -72.00   0.50    0.20    --  -69.31   0.00 -60.00   70
 39  \w   -105.00 -72.00   0.50    0.20    --  -69.31   0.00 150.00   66
 40  \w    -66.00 -38.00   0.50    0.20    --  -74.78 145.00  38.83   56
 41  \w   -112.00 -43.00   0.50    0.20    --  -74.78 140.00 114.13  138
 42  \w   -114.00 -87.00   0.50    0.20    --  -74.78 145.00  38.83   54
 43  \w   -112.00 -49.00   0.50    0.20    --  -74.78 140.00 -59.94  126
 44  \w   -112.00 -51.00   0.50    0.20    --  -74.78 142.00-172.76  122
 45  \w    -87.00 -31.00   0.50    0.20    --  -69.31 125.00-180.00  112
;
_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      0.0396861000
_diffrn_orient_matrix_UB_12      -0.0476195000
_diffrn_orient_matrix_UB_13      0.0196454000
_diffrn_orient_matrix_UB_21      -0.0318717000
_diffrn_orient_matrix_UB_22      -0.0057748000
_diffrn_orient_matrix_UB_23      0.0445729000
_diffrn_orient_matrix_UB_31      -0.0509227000
_diffrn_orient_matrix_UB_32      -0.0422943000
_diffrn_orient_matrix_UB_33      -0.0332092000
_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  0.0614
_diffrn_reflns_av_unetI/netI     0.0394
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.951
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            204256
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.971
_diffrn_reflns_theta_min         2.323
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    13.022
_exptl_absorpt_correction_T_max  0.599
_exptl_absorpt_correction_T_min  0.009
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.89a (Rigaku Oxford Diffraction, 2023)
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            'clear intense red'
_exptl_crystal_density_diffrn    1.663
_exptl_crystal_description       plate
_exptl_crystal_F_000             6784
_exptl_crystal_size_max          0.66
_exptl_crystal_size_mid          0.489
_exptl_crystal_size_min          0.203
_refine_diff_density_max         2.366
_refine_diff_density_min         -2.133
_refine_diff_density_rms         0.151
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3131
_refine_ls_number_reflns         54774
_refine_ls_number_restraints     7430
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0669
_refine_ls_R_factor_gt           0.0598
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0941P)^2^+48.5570P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1644
_refine_ls_wR_factor_ref         0.1693
_reflns_Friedel_coverage         0.000
_reflns_number_gt                46601
_reflns_number_total             54774
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06280e2.cif
_cod_data_source_block           ne0253
_cod_depositor_comments
'Adding full bibliography for 1570859--1570865.cif.'
_cod_database_code               1570864
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C300 H300 N40 Au12'
_shelx_estimated_absorpt_t_max   0.177
_shelx_estimated_absorpt_t_min   0.042
_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
 C204-C205
 1.5 with sigma of 0.02
 C119-C118 = C120-C118
 1.54 with sigma of 0.02
 N34-C204 = N31-C181 = N33-C186
 1.28 with sigma of 0.02
 C120-C119
 2.5 with sigma of 0.02
 C187-C186
 1.5 with sigma of 0.01
 C11-C10
 2.5 with sigma of 0.02
 C346-C336 \\sim C338-C336 \\sim C336-C326 \\sim C326-C318 \\sim C328-C318
\\sim C338-C328 \\sim C348-
 C338 \\sim C356-C348 \\sim C348-C343 \\sim C343-C333 \\sim C333-C323 \\sim
C328-C323 \\sim C315-C307 ~
 C323-C315 \\sim C324-C315 \\sim C334-C324 \\sim C344-C334 \\sim C334-C333
\\sim C351-C343 \\sim C352-
 C351 \\sim C352-C344 \\sim C353-C352 \\sim C353-C345 \\sim C345-C335 \\sim
C335-C325 \\sim C342-C332 ~
 C332-C322 \\sim C332-C321 \\sim C331-C321 \\sim C321-C313 \\sim C313-C306
\\sim C313-C311 \\sim C319-
 C311 \\sim C329-C319 \\sim C331-C329 \\sim C339-C329 \\sim C341-C331 \\sim
C350-C341 \\sim C342-C341 ~
 C358-C353 \\sim C360-C358 \\sim C360-C357 \\sim C360-C359 \\sim C359-C351
\\sim C330-C319 \\sim C340-
 C330 \\sim C357-C349 \\sim C350-C349 \\sim C358-C350 \\sim C314-C306 \\sim
C306-C303 \\sim C303-C301 ~
 C312-C301 \\sim C320-C312 \\sim C347-C340 \\sim C355-C347 \\sim C347-C337
\\sim C346-C337 \\sim C355-
 C354 \\sim C354-C346 \\sim C356-C354 \\sim C357-C355 \\sim C309-C305 \\sim
C312-C309 \\sim C359-C356 ~
 C310-C305 \\sim C305-C302 \\sim C304-C302 \\sim C303-C302 \\sim C349-C339
\\sim C340-C339 \\sim C330-
 C320 \\sim C327-C320 \\sim C337-C327 \\sim C327-C317 \\sim C317-C309 \\sim
C326-C317 \\sim C318-C310 ~
 C310-C307 \\sim C307-C304 \\sim C308-C304 \\sim C314-C308 \\sim C322-C314
\\sim C325-C322 \\sim C316-
 C308 \\sim C325-C316 \\sim C324-C316 \\sim C344-C335 \\sim C345-C342 \\sim
C311-C301
 with sigma of 0.01
 C8-C4 \\sim C5-C4 \\sim C6-C4 \\sim C7-C4 \\sim C9-C10 \\sim C9-C12
 with sigma of 0.02
 C5-C6 \\sim C8-C7
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C57) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C171) \\sim Ueq, Uanis(C186) \\sim Ueq, Uanis(Au16) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C119) \\sim Ueq, Uanis(Cl4) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(Au18) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(H4B)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C8)=Sof(H8A)=Sof(H8B)=
 Sof(H8C)=1-FVAR(1)
 Sof(H4A)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C6)=Sof(H6A)=Sof(H6B)=
 Sof(H6C)=FVAR(1)
 Sof(H9B)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=1-FVAR(2)
 Sof(H9A)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(2)
 Sof(Au14)=Sof(Au15)=Sof(Au13)=1-FVAR(3)
 Sof(Au7)=Sof(Au8)=Sof(Au9)=FVAR(3)
 Sof(Au17)=Sof(Au16)=Sof(Au18)=1-FVAR(4)
 Sof(Au10)=Sof(Au11)=Sof(Au12)=FVAR(4)
 Sof(Au19)=Sof(Au20)=Sof(Au21)=1-FVAR(5)
 Sof(Au4)=Sof(Au5)=Sof(Au6)=FVAR(5)
 Sof(Au22)=Sof(Au23)=Sof(Au24)=1-FVAR(6)
 Sof(Au1)=Sof(Au2)=Sof(Au3)=FVAR(6)
6.a Ternary CH refined with riding coordinates:
 C4(H4A), C4(H4B), C9(H9A), C9(H9B), C34(H34), C38(H38), C52(H52), C55(H55),
 C61(H61), C64(H64), C88(H88), C91(H91), C106(H106), C109(H109), C115(H115),
 C118(H118), C142(H142), C145(H145), C160(H160), C163(H163), C169(H169),
 C172(H172), C196(H196), C199(H199), C214(H214), C217(H217), C361(D361),
 C362(D362)
6.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C40(H40A,
 H40B), C41(H41A,H41B), C74(H74A,H74B), C75(H75A,H75B), C76(H76A,H76B),
 C77(H77A,H77B), C94(H94A,H94B), C95(H95A,H95B), C128(H12G,H12H), C129(H12I,
 H12J), C130(H13A,H13B), C131(H13C,H13D), C148(H14M,H14N), C149(H14O,H14P),
 C182(H18A,H18B), C183(H18C,H18D), C184(H18E,H18F), C185(H18G,H18H), C202(H20I,
 H20J), C203(H20K,H20L)
6.c Me refined with riding coordinates:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C)
6.d Aromatic/amide H refined with riding coordinates:
 C18(H18), C17(H17), C15(H15), C14(H14), C19(H19), C24(H24), C27(H27),
 C26(H26), C30(H30), C29(H29), C42(H42), C300(H300), C48(H48), C44(H44),
 C45(H45), C68(H68), C69(H69), C71(H71), C72(H72), C73(H73), C78(H78), C80(H80),
  C81(H81), C83(H83), C84(H84), C96(H96), C98(H98), C99(H99), C101(H101),
 C102(H102), C126(H126), C125(H125), C123(H123), C122(H122), C127(H127),
 C132(H132), C134(H134), C135(H135), C137(H137), C138(H138), C150(H150),
 C152(H152), C153(H153), C155(H155), C156(H156), C180(H180), C179(H179),
 C177(H177), C176(H176), C181(H181), C186(H186), C191(H191), C192(H192),
 C188(H188), C189(H189), C204(H204), C209(H209), C210(H210), C206(H206),
 C207(H207)
6.e Fitted hexagon refined as free rotating group:
 C13(C18,C17,C16,C15,C14), C28(C27,C26,C25,C30,C29), C46(C300,C48,C43,C44,C45),
  C121(C126,C125,C124,C123,C122), C175(C180,C179,C178,C177,C176), C190(C191,
 C192,C187,C188,C189), C208(C209,C210,C205,C206,C207)
6.f Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C12(H12A,
 H12B,H12C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C),
 C39(H39A,H39B,H39C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C56(H56A,H56B,
 H56C), C57(H57A,H57B,H57C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C65(H65A,
 H65B,H65C), C66(H66A,H66B,H66C), C89(H89A,H89B,H89C), C90(H90A,H90B,H90C),
 C92(H92A,H92B,H92C), C93(H93A,H93B,H93C), C107(H10D,H10E,H10F), C108(H10G,H10H,
 H10I), C110(H11D,H11E,H11F), C111(H11G,H11H,H11I), C116(H11J,H11K,H11L),
 C117(H11M,H11N,H11O), C119(H11P,H11Q,H11R), C120(H12D,H12E,H12F), C143(H14A,
 H14B,H14C), C144(H14D,H14E,H14F), C146(H14G,H14H,H14I), C147(H14J,H14K,H14L),
 C161(H16A,H16B,H16C), C162(H16D,H16E,H16F), C164(H16G,H16H,H16I), C165(H16J,
 H16K,H16L), C170(H17A,H17B,H17C), C171(H17D,H17E,H17F), C173(H17G,H17H,H17I),
 C174(H17J,H17K,H17L), C197(H19A,H19B,H19C), C198(H19D,H19E,H19F), C200(H20C,
 H20D,H20E), C201(H20F,H20G,H20H), C215(H21C,H21D,H21E), C216(H21F,H21G,H21H),
 C218(H21I,H21J,H21K), C219(H21L,H21M,H21N)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 618 electrons were 
found in a volume of 2598\%A^3^ in 5 voids per unit cell. 
This is consistent with the presence of 
2[CDCl3] per Asymmetric Unit 
which account for 652 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              87295
_shelx_fab_checksum              93977
_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 3.321
_oxdiff_exptl_absorpt_empirical_full_min 0.475