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_7133385
_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         '3(C49 H38 Ag2 N4 P2), C138 H72 O36 Ti4'
_chemical_formula_sum            'C285 H186 Ag6 N12 O36 P6 Ti4'
_chemical_formula_weight         5379.09
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-13
_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                 94.3710(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   78.8953(7)
_cell_length_b                   22.1894(2)
_cell_length_c                   35.6493(3)
_cell_measurement_reflns_used    119677
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      54.2540
_cell_measurement_theta_min      2.1210
_cell_volume                     62227.5(9)
_computing_cell_refinement       'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.116a 64-bit (release 22-03-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_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_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.978
_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   -140.00 -80.90   0.15    0.03    --  -69.88-125.00 150.00  394
  2  \w   -141.00 -87.00   0.15    0.03    --  -69.88-113.00  13.00  360
  3  \w   -141.00 -82.95   0.15    0.03    --  -69.88-125.00 -90.00  387
  4  \w   -143.00 -98.00   0.15    0.03    --  -69.88 -99.00-150.00  300
  5  \w     -8.00  37.00   0.15    0.03    --   -0.70 -99.00 120.00  300
  6  \w     -8.00  37.00   0.15    0.03    --   -0.70 -99.00-120.00  300
  7  \w     -8.00  37.00   0.15    0.03    --   -0.70 -99.00-180.00  300
  8  \w     -8.00  37.00   0.15    0.03    --   -0.70 -99.00 -60.00  300
  9  \w     -8.00  37.00   0.15    0.03    --   -0.70 -99.00  90.00  300
 10  \w   -108.00 -12.00   0.15    0.03    --  -69.88 113.00 105.00  640
 11  \w     -9.00  69.90   0.15    0.03    --   68.48 -38.00  30.00  526
 12  \w     12.00 108.00   0.15    0.03    --   68.48-113.00  13.00  640
 13  \w     20.00 110.00   0.15    0.03    --   68.48-125.00-120.00  600
 14  \w     46.00 142.00   0.15    0.03    --   68.48  57.00  90.00  640
 15  \w     46.00 142.00   0.15    0.03    --   68.48  57.00  90.00  640
 16  \w     86.00 140.00   0.15    0.03    --   68.48 113.00 105.00  360
 17  \w     79.00 139.00   0.15    0.03    --   68.48 125.00  30.00  400
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0145331000
_diffrn_orient_matrix_UB_12      0.0304571000
_diffrn_orient_matrix_UB_13      -0.0025332000
_diffrn_orient_matrix_UB_21      -0.0077243000
_diffrn_orient_matrix_UB_22      0.0509025000
_diffrn_orient_matrix_UB_23      0.0094971000
_diffrn_orient_matrix_UB_31      0.0043787000
_diffrn_orient_matrix_UB_32      -0.0111689000
_diffrn_orient_matrix_UB_33      0.0363484000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Ga K\a'
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0681
_diffrn_reflns_av_unetI/netI     0.0622
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       98
_diffrn_reflns_limit_h_min       -97
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            308129
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         56.381
_diffrn_reflns_theta_min         2.079
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    3.085
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66901
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.116a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.148
_exptl_crystal_description       block
_exptl_crystal_F_000             21824
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.602
_refine_diff_density_min         -1.269
_refine_diff_density_rms         0.126
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.373
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           fullcycle
_refine_ls_number_parameters     2989
_refine_ls_number_reflns         61135
_refine_ls_number_restraints     107
_refine_ls_restrained_S_all      1.385
_refine_ls_R_factor_all          0.1683
_refine_ls_R_factor_gt           0.1259
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3856
_refine_ls_wR_factor_ref         0.4103
_reflns_Friedel_coverage         0.000
_reflns_number_gt                33334
_reflns_number_total             61135
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02938k2.cif
_cod_data_source_block           PTC-379
_cod_depositor_comments
'Adding full bibliography for 7133385--7133387.cif.'
_cod_original_cell_volume        62227.6(9)
_cod_database_code               7133385
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ti Ag C H O N P'
_shelx_estimated_absorpt_t_max   0.748
_shelx_estimated_absorpt_t_min   0.458
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C7-C96 = C7-H7 = C7-C133
 1.4 with sigma of 0.02
 N13-C19
 1.4 with sigma of 0.01
 C285-C73
 1.5 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C133) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C265) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C259) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C91) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C67) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C46) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C136) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C126) \\sim Ueq, Uanis(C192) \\sim Ueq, Uanis(C284) \\sim Ueq, Uanis(C91)
\\sim Ueq, Uanis(C195) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C8) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C7) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(N5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C46) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C96) \\sim Ueq, Uanis(C98)
\\sim Ueq, Uanis(C133) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C259) = Uanis(C11) = Uanis(C64)
Uanis(C261) = Uanis(C130) = Uanis(C263) = Uanis(C64) = Uanis(C259) = Uanis(C11)
4.a Secondary CH2 refined with riding coordinates:
 C26(H26a,H26b), C187(H18a,H18b), C210(H21a,H21b), C59(H59a,H59b), C214(H21c,
 H21d), C198(H19a,H19b), C110(H11a,H11b), C238(H23a,H23b), C201(H20a,H20b)
4.b Aromatic/amide H refined with riding coordinates:
 C143(H143), C144(H144), C99(H99), C95(H95), C137(H137), C200(H200), C19(H19),
 C87(H87), C183(H183), C224(H224), C234(H234), C80(H80), C30(H30), C135(H135),
 C1(H1), C105(H105), C165(H165), C107(H107), C202(H202), C206(H206), C216(H216),
  C121(H121), C70(H70), C232(H232), C76(H76), C262(H262), C147(H147),
 C266(H266), C156(H156), C157(H157), C268(H268), C85(H85), C84(H84), C51(H51),
 C91(H91), C4(H4), C8(H8), C10(H10), C175(H175), C57(H57), C103(H103),
 C189(H189), C193(H193), C166(H166), C194(H194), C108(H108), C37(H37), C63(H63),
  C116(H116), C66(H66), C218(H218), C220(H220), C247(H247), C275(H275),
 C123(H123), C228(H228), C127(H127), C236(H236), C242(H242), C74(H74),
 C258(H258), C264(H264), C45(H45), C270(H270), C272(H272), C82(H82), C151(H151),
  C65(H65), C18(H18), C148(H148), C34(H34), C77(H77), C120(H120), C79(H79),
 C155(H155), C38(H38), C159(H159), C161(H161), C14(H14), C83(H83), C169(H169),
 C40(H40), C6(H6), C171(H171), C31(H31), C172(H172), C174(H174), C176(H176),
 C88(H88), C20(H20), C180(H180), C184(H184), C92(H92), C33(H33), C188(H188),
 C94(H94), C190(H190), C46(H46), C96(H96), C7(H7), C199(H199), C35(H35),
 C102(H102), C205(H205), C50(H50), C207(H207), C22(H22), C211(H211), C106(H106),
  C213(H213), C215(H215), C5(H5), C217(H217), C219(H219), C221(H221), C54(H54),
 C225(H225), C16(H16), C113(H113), C56(H56), C231(H231), C115(H115), C21(H21),
 C235(H235), C117(H117), C237(H237), C239(H239), C119(H119), C241(H241),
 C25(H25), C243(H243), C122(H122), C245(H245), C60(H60), C249(H249), C124(H124),
  C251(H251), C253(H253), C126(H126), C255(H255), C62(H62), C257(H257),
 C128(H128), C259(H259), C11(H11), C263(H263), C64(H64), C265(H265), C132(H132),
  C267(H267), C68(H68), C269(H269), C271(H271), C67(H67), C23(H23), C136(H136),
 C274(H274), C27(H27), C276(H276), C138(H138), C277(H277), C71(H71), C278(H278),
  C140(H140), C280(H280), C208(H208), C142(H142), C284(H284)
4.c Fitted hexagon refined as free rotating group:
 N13(C39,C196,C137,C200,C19), C120(C79,C155,C38,C159,C81), C192(C96,C7,C133,
 C195,C98), C54(N2,C223,C111,C225,C16), C237(C58,C239,C119,C241,C25), C124(C251,
 C118,C253,C126,C255), C259(C11,C261,C130,C263,C64), C134(C271,C67,C23,C136,
 C274), C140(C280,C208,C282,C142,C284)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              75821
_shelx_hkl_checksum              33401
_shelx_fab_checksum              86180
_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 1.445
_oxdiff_exptl_absorpt_empirical_full_min 0.737
_publcif_funding_html
;
;