Combining Ti<sub>4</sub>(embonate)<sub>6</sub> anionic cages and π-conjugated coordination cations for highly effective optical limiting.
Yuan, Yuan; Zhang, Dong-Hui; Li, Qiao-Hong; Chen, Shu-Mei; He, Yan-Ping; Zhang, Jian; Chemical communications (Cambridge, England) 60 (2024) 8748–8751; doi:10.1039/d4cc02938k

data_7133386
_publ_section_title
;
 Combining Ti<sub>4</sub>(embonate)<sub>6</sub> anionic cages and
 &#x3c0;-conjugated coordination cations for highly effective optical
 limiting.
;
_journal_issue                   66
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              8748
_journal_page_last               8751
_journal_paper_doi               10.1039/d4cc02938k
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C74 H60 Ag2 N4 P4, C138 H72 O36 Ti4'
_chemical_formula_sum            'C212 H132 Ag2 N4 O36 P4 Ti4'
_chemical_formula_weight         3842.43
_space_group_crystal_system      tetragonal
_space_group_IT_number           92
_space_group_name_Hall           'P 4abw 2nw'
_space_group_name_H-M_alt        'P 41 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-11
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-06-03 deposited with the CCDC.	2024-07-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.4503(4)
_cell_length_b                   20.4503(4)
_cell_length_c                   54.8956(15)
_cell_measurement_reflns_used    18348
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      74.9750
_cell_measurement_theta_min      2.2870
_cell_volume                     22958.2(9)
_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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.962
_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   -177.00 -86.00   0.50    0.90    -- -105.58 -67.00  32.00  182
  2  \w    -71.00 -33.00   0.50    0.90    -- -105.58  61.00 120.00   76
  3  \w    -71.00 -46.00   0.50    0.90    -- -105.58  61.00  60.00   50
  4  \w    -21.00  76.00   0.50    0.22    --   50.35 -81.00 -81.00  194
  5  \w     34.00 123.00   0.50    0.22    --   50.35  57.00-150.00  178
  6  \w     83.00 178.00   0.50    0.90    --  108.08  81.00  40.00  190
  7  \w     74.00 120.00   0.50    0.22    --   50.35 125.00 -90.00   92
  8  \w     34.00 123.00   0.50    0.22    --   50.35  57.00 -60.00  178
  9  \w     35.00  71.00   0.50    0.90    --  108.08 -61.00  90.00   72
 10  \w     35.00  71.00   0.50    0.90    --  108.08 -61.00 150.00   72
 11  \w     35.00  71.00   0.50    0.90    --  108.08 -61.00  60.00   72
 12  \w     35.00  71.00   0.50    0.90    --  108.08 -61.00-150.00   72
 13  \w     35.00  71.00   0.50    0.90    --  108.08 -61.00-180.00   72
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0092737000
_diffrn_orient_matrix_UB_12      0.0407103000
_diffrn_orient_matrix_UB_13      -0.0233539000
_diffrn_orient_matrix_UB_21      -0.0572074000
_diffrn_orient_matrix_UB_22      0.0445034000
_diffrn_orient_matrix_UB_23      0.0076369000
_diffrn_orient_matrix_UB_31      0.0481603000
_diffrn_orient_matrix_UB_32      0.0450743000
_diffrn_orient_matrix_UB_33      0.0135624000
_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  0.0893
_diffrn_reflns_av_unetI/netI     0.0628
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       69
_diffrn_reflns_limit_l_min       -53
_diffrn_reflns_number            114117
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.949
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.039
_diffrn_reflns_theta_min         2.306
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.246
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89750
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.85a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.112
_exptl_crystal_description       block
_exptl_crystal_F_000             7848
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.245
_refine_diff_density_min         -0.291
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 3554 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.016(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.933
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1157
_refine_ls_number_reflns         23543
_refine_ls_number_restraints     403
_refine_ls_restrained_S_all      0.933
_refine_ls_R_factor_all          0.1207
_refine_ls_R_factor_gt           0.0590
_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^)+(0.1084P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1631
_refine_ls_wR_factor_ref         0.2020
_reflns_Friedel_coverage         0.783
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.933
_reflns_number_gt                11017
_reflns_number_total             23543
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02938k2.cif
_cod_data_source_block           PTC-380
_cod_depositor_comments
'Adding full bibliography for 7133385--7133387.cif.'
_cod_original_cell_volume        22958.1(11)
_cod_database_code               7133386
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ti Ag C H O N P'
_shelx_estimated_absorpt_t_max   0.737
_shelx_estimated_absorpt_t_min   0.443
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C5) \\sim Ueq, Uanis(C5) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Fixed Sof: H59A(0.5) H59B(0.5) H62A(0.5) H62B(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C96(H96A,H96B), C63(H63A,H63B), C59(H59A,H59B), C74(H74A,H74B), C62(H62A,H62B)
5.b Aromatic/amide H refined with riding coordinates:
 C57(H57), C60(H60), C76(H76), C36(H36), C75(H75), C1(H1), C13(H13), C22(H22),
 C38(H38), C29(H29), C32(H32), C37(H37), C15(H15), C23(H23), C104(H104),
 C31(H31), C105(H105), C47(H47), C33(H33), C89(H89), C86(H86), C12(H12),
 C64(H64), C48(H48), C94(H94), C101(H101), C81(H81), C8(H8), C46(H46),
 C100(H100), C30(H30), C72(H72), C27(H27), C93(H93), C21(H21), C99(H99),
 C45(H45), C11(H11), C9(H9), C34(H34), C7(H7), C50(H50), C14(H14), C49(H49),
 C98(H98), C55(H55), C85(H85), C91(H91), C102(H102), C106(H106), C70(H70),
 C87(H87), C88(H88), C107(H107), C10(H10), C5(H5), C108(H108), C6(H6)
5.c Fitted hexagon refined as free rotating group:
 C94(C17,C101,C81,C8,C46), C35(C5,C108,C82,C73,C95)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              43770
_shelx_hkl_checksum              16602
_shelx_fab_checksum              9211
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.160
_oxdiff_exptl_absorpt_empirical_full_min 0.874
_publcif_funding_html
;
;