Bidirectional photomagnetism, exciplex fluorescence and dielectric anomalies in a spin crossover Hofmann-type coordination polymer.
Chen, Yan-Ru; Ying, Ting-Ting; Chen, Yan-Cong; Liao, Pei-Yu; Ni, Zhao-Ping; Tong, Ming-Liang; Chemical science 15 (2024) 9240–9248; doi:10.1039/d4sc00331d

data_1571622
_publ_section_title
;
 Bidirectional photomagnetism, exciplex fluorescence and dielectric
 anomalies in a spin crossover Hofmann-type coordination polymer.
;
_journal_issue                   24
_journal_name_full               'Chemical science'
_journal_page_first              9240
_journal_page_last               9248
_journal_paper_doi               10.1039/d4sc00331d
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C32 H16 Au4 N16 O2 Zn2, 2(C16 H10)'
_chemical_formula_sum            'C64 H36 Au4 N16 O2 Zn2'
_chemical_formula_weight         1979.69
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-15
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-04-05 deposited with the CCDC.	2024-05-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.3837(10)
_cell_length_b                   27.856(2)
_cell_length_c                   28.7390(19)
_cell_measurement_reflns_used    3593
_cell_measurement_temperature    259.99(10)
_cell_measurement_theta_max      25.3870
_cell_measurement_theta_min      2.8410
_cell_volume                     12315.5(14)
_computing_cell_refinement       'CrysAlisPro 1.171.42.92a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.92a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.92a (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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      259.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2913
_diffrn_detector_type            AtlasS2
_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   -103.00 -73.00   1.00    5.00    --  -14.92 178.00-180.00   30
  2  \w     52.00  78.00   1.00    5.00    --   15.55 178.00 -60.00   26
  3  \w    -54.00  30.00   1.00    5.00    --   15.55 -57.00  30.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0281170000
_diffrn_orient_matrix_UB_12      -0.0199157000
_diffrn_orient_matrix_UB_13      -0.0031509000
_diffrn_orient_matrix_UB_21      -0.0153499000
_diffrn_orient_matrix_UB_22      -0.0027319000
_diffrn_orient_matrix_UB_23      -0.0231170000
_diffrn_orient_matrix_UB_31      0.0331325000
_diffrn_orient_matrix_UB_32      0.0156427000
_diffrn_orient_matrix_UB_33      -0.0080594000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0907
_diffrn_reflns_av_unetI/netI     0.1228
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            40458
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.499
_diffrn_reflns_theta_min         2.580
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    10.319
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72369
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.92a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.135
_exptl_crystal_description       block
_exptl_crystal_F_000             7392
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.119
_refine_diff_density_min         -1.775
_refine_diff_density_rms         0.223
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     889
_refine_ls_number_reflns         14098
_refine_ls_number_restraints     2793
_refine_ls_restrained_S_all      0.959
_refine_ls_R_factor_all          0.1751
_refine_ls_R_factor_gt           0.0692
_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^)+(0.0261P)^2^+8.8229P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1174
_refine_ls_wR_factor_ref         0.1651
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6198
_reflns_number_total             14098
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00331d2.cif
_cod_data_source_block           a24030604a0123_3_260_00_auto
_cod_depositor_comments
'Adding full bibliography for 1571621--1571630.cif.'
_cod_original_cell_volume        12315.6(15)
_cod_database_code               1571622
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         Au4C64N16O2Zn2
_shelx_estimated_absorpt_t_max   0.371
_shelx_estimated_absorpt_t_min   0.167
_reflns_odcompleteness_completeness 87.74
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.69
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C47-C36 \\sim C48-C42 \\sim C37-C34 \\sim C38-C35 \\sim C60-C57 \\sim C52-C63
\\sim C58-C64 \\sim C51-C54
 \\sim C57A-C51A \\sim C56A-C52A \\sim C58-C64 \\sim C52-C63 \\sim C50-C53
\\sim C56-C52 \\sim C55-C58 ~
 C58A-C64A \\sim C63A-C52A \\sim C62A-C59A \\sim C56A-C52A \\sim C58A-C55A
\\sim C53A-C50A
 with sigma of 0.02
 C60A-C63A \\sim C64A-C54A \\sim C50A-C55A \\sim C56A-C62A \\sim C38-C48 \\sim
C47-C44 \\sim C46-C40 ~
 C39-C34 \\sim C56-C62 \\sim C60-C63 \\sim C64-C54 \\sim C50-C55
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 3A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 3A
C35 \\sim C44 \\sim C43 \\sim C45 \\sim C47 \\sim C42 \\sim C46 \\sim C48 \\sim
C41 \\sim C36 \\sim C37 \\sim C40 \\sim C38 \\sim C39 \\sim C34 \\sim C33:
within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 1.7A
C61 \\sim C52 \\sim C51 \\sim C53 \\sim C58 \\sim C50 \\sim C55 \\sim C54 \\sim
C64 \\sim C57 \\sim C59 \\sim C49 \\sim C56 \\sim C63 \\sim C62 \\sim C60 \\sim
C55A \\sim C52A \\sim C53A \\sim C51A \\sim C58A \\sim C54A \\sim C64A \\sim
C50A \\sim C59A \\sim C57A \\sim C49A \\sim C63A \\sim C56A \\sim C60A \\sim
C62A \\sim C61A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
Uanis(C52) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C52A) \\sim Ueq, Uanis(C58A)
\\sim Ueq, Uanis(C58) \\sim Ueq: with sigma of 0.006 and sigma for terminal
atoms of 0.012
4. Others
 Fixed Sof: C52(0.5) C51(0.5) C50(0.5) H50(0.5) C49(0.5) H49(0.5) C54(0.5)
 H54(0.5) C53(0.5) C61(0.5) H61(0.5) C62(0.5) H62(0.5) C57(0.5) C58(0.5)
 C59(0.5) C60(0.5) H60(0.5) C63(0.5) H63(0.5) C64(0.5) H64(0.5) C56(0.5)
 H56(0.5) C55(0.5) H55(0.5) C52A(0.5) C53A(0.5) C54A(0.5) H54A(0.5) C49A(0.5)
 H49A(0.5) C50A(0.5) H50A(0.5) C51A(0.5) C64A(0.5) H64A(0.5) C63A(0.5)
 H63A(0.5) C55A(0.5) H55A(0.5) C56A(0.5) H56A(0.5) C61A(0.5) H61A(0.5)
 C60A(0.5) H60A(0.5) C59A(0.5) C58A(0.5) C57A(0.5) C62A(0.5) H62A(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C11(H11), C5(H5), C31(H31), C29(H29), C2(H2), C30(H30), C1(H1), C32(H32),
 C4(H4), C9(H9), C22(H22), C25(H25), C12(H12), C44(H44), C21(H21), C38(H38),
 C10(H10), C46(H46), C24(H24), C33(H33), C47(H47), C40(H40), C39(H39), C45(H45),
  C48(H48), C34(H34), C50(H50), C49(H49), C54(H54), C61(H61), C62(H62),
 C60(H60), C63(H63), C64(H64), C56(H56), C55(H55), C54A(H54A), C49A(H49A),
 C50A(H50A), C64A(H64A), C63A(H63A), C55A(H55A), C56A(H56A), C61A(H61A),
 C60A(H60A), C62A(H62A)
5.b Fitted hexagon refined as free rotating group:
 C52(C51,C50,C49,C54,C53), C61(C62,C57,C58,C59,C60), C52A(C53A,C54A,C49A,C50A,
 C51A), C61A(C60A,C59A,C58A,C57A,C62A)
;
_shelx_res_checksum              2515
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.429
_oxdiff_exptl_absorpt_empirical_full_min 0.802