Gallic acid-based dendrimers with a thiacalix[4]arene core: synthesis, aggregation and use for stabilization of Pd nanoparticles
Fatykhova, Aigul M.; Sultanova, Elza D.; Burilov, Vladimir A.; Gafiatullin, Bulat Kh.; Fedoseeva, Angelina A.; Veshta, Tatyana A.; Ziganshin, Marat A.; Ziganshina, Sufia A.; Evtugyn, Vladimir G.; Islamov, Daut R.; Usachev, Konstantin S.; Solovieva, Svetlana E.; Antipin, Igor S.; New Journal of Chemistry 47 (2023) 19223–19234; doi:10.1039/D3NJ03403H

data_7062768
_publ_section_title
;
 Gallic acid-based dendrimers with a thiacalix[4]arene core: synthesis,
 aggregation and use for stabilization of Pd nanoparticles
;
_journal_issue                   41
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              19223
_journal_page_last               19234
_journal_paper_doi               10.1039/D3NJ03403H
_journal_volume                  47
_journal_year                    2023
_chemical_formula_moiety         'C58 H76 O6 S4'
_chemical_formula_sum            'C58 H76 O6 S4'
_chemical_formula_weight         997.42
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-09-22
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-09-26 deposited with the CCDC.	2023-09-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.3359(11)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.14781(15)
_cell_length_b                   26.9146(3)
_cell_length_c                   15.17255(19)
_cell_measurement_reflns_used    45212
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      75.8610
_cell_measurement_theta_min      3.3520
_cell_volume                     5368.99(11)
_computing_cell_refinement       'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.80a (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 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.965
_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    -24.00  51.00   0.50    4.00    --   46.31 -50.00 151.00  150
  2  \w   -117.00 -91.00   0.50    4.00    --  -47.56 -50.00 151.00   52
  3  \w    -40.00 -15.00   0.50    4.00    --  -47.56  50.00 -61.00   50
  4  \w     95.00 121.00   0.50   16.00    --  103.80  50.00 -61.00   52
  5  \w    133.00 173.00   0.50   16.00    --  103.80  50.00 -61.00   80
  6  \w     31.00  57.00   0.50   16.00    --  103.80 -50.00 151.00   52
  7  \w   -135.00-108.00   0.50   16.00    -- -105.05 -50.00 151.00   54
  8  \w     33.00 119.00   0.50    4.00    --   46.31  50.00 -61.00  172
  9  \w     16.00  94.00   0.50    4.00    --   46.31-125.00 -90.00  156
 10  \w    -16.00  28.00   0.50    4.00    --  -47.56  19.00  90.00   88
 11  \w   -118.00 -33.00   0.50    4.00    --  -47.56 -57.00  30.00  170
 12  \w    -27.00  27.00   0.50    4.00    --  -47.56  19.00  30.00  108
 13  \w   -116.00 -35.00   0.50    4.00    --  -47.56 -37.00  60.00  162
 14  \w   -118.00 -73.00   0.50    4.00    --  -47.56-125.00-120.00   90
 15  \w     85.00 111.00   0.50   16.00    --  103.80  77.00  60.00   52
 16  \w     81.00 107.00   0.50   16.00    --  103.80  77.00   0.00   52
 17  \w     36.00  70.00   0.50   16.00    --  103.80 -61.00  30.00   68
 18  \w     92.00 160.00   0.50   16.00    --  103.80  30.00  30.00  136
 19  \w     91.00 118.00   0.50   16.00    --  103.80  45.00  60.00   54
 20  \w     88.00 113.00   0.50   16.00    --  103.80  61.00   0.00   50
 21  \w     87.00 130.00   0.50   16.00    --  103.80  61.00  30.00   86
 22  \w     81.00 106.00   0.50   16.00    --  103.80  77.00  30.00   50
 23  \w     98.00 177.00   0.50   16.00    --  103.80  61.00 -30.00  158
 24  \w    138.00 164.00   0.50   16.00    --  103.80  77.00   0.00   52
 25  \w     89.00 169.00   0.50   16.00    --  103.80  61.00  90.00  160
 26  \w     68.00 104.00   0.50   16.00    --  103.80 -94.00 -90.00   72
 27  \w     91.00 116.00   0.50   16.00    --  103.80  45.00  30.00   50
 28  \w     35.00  61.00   0.50   16.00    --  103.80 -61.00 -60.00   52
 29  \w    113.00 177.00   0.50   16.00    --  103.80  77.00  30.00  128
 30  \w     32.00  57.00   0.50   16.00    --  103.80 -61.00  60.00   50
 31  \w     87.00 113.00   0.50   16.00    --  103.80  61.00  60.00   52
 32  \w     37.00  68.00   0.50   16.00    --  103.80 -61.00 -30.00   62
 33  \w     31.00  67.00   0.50   16.00    --  103.80 -61.00-150.00   72
 34  \w    126.00 175.00   0.50   16.00    --  103.80  77.00  60.00   98
 35  \w     31.00  69.00   0.50   16.00    --  103.80 -61.00   0.00   76
 36  \w     31.00 112.00   0.50   16.00    --  103.80-125.00-180.00  162
 37  \w     32.00  57.00   0.50   16.00    --  103.80 -94.00 -90.00   50
 38  \w   -111.00 -86.00   0.50   16.00    -- -105.05 -67.00  49.85   50
 39  \w   -108.00 -83.00   0.50   16.00    -- -105.05 -77.00  90.00   50
 40  \w   -174.00-149.00   0.50   16.00    -- -105.05 -67.00  49.85   50
 41  \w   -112.00 -87.00   0.50   16.00    -- -105.05 -65.00  29.08   50
 42  \w   -167.00-141.00   0.50   16.00    -- -105.05 -65.00  29.08   52
 43  \w    -65.00 -37.00   0.50   16.00    -- -105.05  61.00 -30.00   56
 44  \w   -118.00 -91.00   0.50   16.00    -- -105.05 -48.00  11.40   54
 45  \w   -171.00-131.00   0.50   16.00    -- -105.05 -48.00  11.40   80
 46  \w   -177.00 -88.00   0.50   16.00    -- -105.05 -94.00 -90.00  178
 47  \w   -113.00 -88.00   0.50   16.00    -- -105.05 -63.00  68.30   50
 48  \w   -116.00 -91.00   0.50   16.00    -- -105.05 -51.00  41.05   50
 49  \w   -176.00-100.00   0.50   16.00    -- -105.05 -15.00-180.00  152
 50  \w   -135.00 -91.00   0.50   16.00    -- -105.05 -54.00  91.03   88
 51  \w   -133.00 -93.00   0.50   16.00    -- -105.05 -53.00  60.26   80
 52  \w   -116.00 -91.00   0.50   16.00    -- -105.05 -53.00  48.01   50
 53  \w    -71.00 -46.00   0.50   16.00    -- -105.05  61.00 -60.00   50
 54  \w   -111.00 -86.00   0.50   16.00    -- -105.05 -68.00  55.76   50
 55  \w   -177.00-151.00   0.50   16.00    -- -105.05 -68.00  55.76   52
 56  \w   -114.00 -89.00   0.50   16.00    -- -105.05 -67.00  47.01   50
 57  \w   -112.00 -87.00   0.50   16.00    -- -105.05 -67.00  88.91   50
 58  \w   -114.00 -89.00   0.50   16.00    -- -105.05 -61.00  90.00   50
 59  \w   -104.00 -79.00   0.50   16.00    -- -105.05 -86.00  88.50   50
 60  \w   -177.00-128.00   0.50   16.00    -- -105.05 -86.00  88.50   98
 61  \w   -122.00 -89.00   0.50   16.00    -- -105.05 -60.00  78.09   66
 62  \w    -67.00 -40.00   0.50   16.00    -- -105.05  61.00   0.00   54
 63  \w   -169.00-144.00   0.50   16.00    -- -105.05 -67.00  88.91   50
 64  \w   -111.00 -86.00   0.50   16.00    -- -105.05 -68.00  40.57   50
 65  \w   -109.00 -84.00   0.50   16.00    -- -105.05 -77.00  60.00   50
 66  \w   -111.00 -86.00   0.50   16.00    -- -105.05 -67.00 113.73   50
 67  \w    -69.00 -41.00   0.50   16.00    -- -105.05  61.00 150.00   56
;
_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      0.0178101000
_diffrn_orient_matrix_UB_12      -0.0509253000
_diffrn_orient_matrix_UB_13      0.0439689000
_diffrn_orient_matrix_UB_21      0.0974554000
_diffrn_orient_matrix_UB_22      0.0201315000
_diffrn_orient_matrix_UB_23      0.0441148000
_diffrn_orient_matrix_UB_31      -0.0625418000
_diffrn_orient_matrix_UB_32      0.0168205000
_diffrn_orient_matrix_UB_33      0.0801032000
_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  0.0504
_diffrn_reflns_av_unetI/netI     0.0253
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            97713
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.121
_diffrn_reflns_theta_min         2.913
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.009
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.775
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.80a (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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.234
_exptl_crystal_description       plate
_exptl_crystal_F_000             2144
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.701
_refine_diff_density_min         -0.505
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     715
_refine_ls_number_reflns         10834
_refine_ls_number_restraints     174
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0650
_refine_ls_R_factor_gt           0.0627
_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^)+(0.0854P)^2^+7.6789P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1662
_refine_ls_wR_factor_ref         0.1691
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10385
_reflns_number_total             10834
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3nj03403h2.cif
_cod_data_source_block           ant696_corr
_cod_depositor_comments
'Adding full bibliography for 7062767--7062768.cif.'
_cod_original_cell_volume        5368.98(11)
_cod_database_code               7062768
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         C58H76O6S4
_shelx_estimated_absorpt_t_max   0.942
_shelx_estimated_absorpt_t_min   0.753
_reflns_odcompleteness_completeness 98.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.8367(11)
 0.1633(11)
2. 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
3. Restrained distances
 C51-C20
 1.2 with sigma of 0.02
 C16-O34 \\sim O34-C35
 with sigma of 0.001
 C1C-C1B \\sim C29-C27
 with sigma of 0.001
 C96-C71 \\sim C20-C51
 with sigma of 0.001
 C1D-C1B \\sim C30-C27
 with sigma of 0.001
 C1B-C18 \\sim C18-C27
 with sigma of 0.001
 C1A-C1B \\sim C28-C27
 with sigma of 0.001
 C12-C8 \\sim C38-C37
 with sigma of 0.001
 C75-C64 \\sim C64-C65
 with sigma of 0.001
 C66-C64 \\sim C64-C76
 with sigma of 0.001
 C77-C64 \\sim C64-C67
 with sigma of 0.001
 C8-C4 \\sim C36-C38
 with sigma of 0.001
 O49-C48 \\sim C69-O2
 with sigma of 0.001
 C71-C70 \\sim C51-C50
 with sigma of 0.001
 C69-C49 \\sim C48-C47
 with sigma of 0.001
 C4-C16 \\sim C35-C36
 with sigma of 0.001
 C70-O2 \\sim C50-O49
 with sigma of 0.001
 C49-O46 \\sim O46-C47
 with sigma of 0.001
 C23-O1 \\sim C24-O23
 with sigma of 0.001
 C59-C23 \\sim C25-C24
 with sigma of 0.001
 C26-C25 \\sim C59-C68
 with sigma of 0.001
 C22-C34 \\sim C46-C21
 with sigma of 0.001
 C21-O20 \\sim O20-C34
 with sigma of 0.001
 O23-C22 \\sim O1-C46
 with sigma of 0.001
4. Rigid bond restraints
 C1A, C1B, C1C, C1D, C27, C28, C29, C30
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Uiso/Uaniso restraints and constraints
Uanis(C12) \\sim Ueq: with sigma of 0.007 and sigma for terminal atoms of 0.01
Uanis(C96) = Uanis(C20)
Uanis(C1D) = Uanis(C28)
Uanis(C29) = Uanis(C1A)
Uanis(C1C) = Uanis(C30)
Uanis(C1B) = Uanis(C27)
Uanis(C12) = Uanis(C37)
Uanis(C69) = Uanis(C48)
Uanis(O1) = Uanis(O23)
Uanis(C70) = Uanis(C50)
Uanis(C47) = Uanis(C49)
Uanis(O2) = Uanis(O49)
Uanis(C71) = Uanis(C51)
Uanis(C35) = Uanis(C16)
Uanis(C38) = Uanis(C8)
Uanis(C22) = Uanis(C46)
Uanis(C34) = Uanis(C21)
Uanis(C26) = Uanis(C68)
Uanis(C25) = Uanis(C59)
Uanis(C24) = Uanis(C23)
Uanis(C76) = Uanis(C66)
Uanis(C75) = Uanis(C65)
6. Rigid body (RIGU) restrains
 O49, C20, C47, C48, C50, C51, O2, C49, C69, C70, C71, C96
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O34, C35, C36, C37, C38, C4, C8, C12, C16
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.006
 C64, C65, C66, C67, C75, C76, C77
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
7. Others
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C12)=Sof(H12A)=
 Sof(H12B)=Sof(H12C)=Sof(C16)=Sof(H16A)=Sof(H16B)=1-FVAR(1)
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(C37)=Sof(H37A)=
 Sof(H37B)=Sof(H37C)=Sof(C38)=Sof(H38A)=Sof(H38B)=FVAR(1)
 Sof(C27)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29A)=Sof(H29B)=
 Sof(H29C)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=1-FVAR(2)
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C1B)=Sof(C1C)=Sof(H1CA)=Sof(H1CB)=
 Sof(H1CC)=Sof(C1D)=Sof(H1DA)=Sof(H1DB)=Sof(H1DC)=FVAR(2)
 Sof(O1)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(C46)=
 Sof(H46A)=Sof(H46B)=Sof(C59)=Sof(C68)=Sof(H68)=1-FVAR(3)
 Sof(O23)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(C25)=
 Sof(C26)=Sof(H26)=Sof(C34)=Sof(H34A)=Sof(H34B)=FVAR(3)
 Sof(O2)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(C70)=
 Sof(H70A)=Sof(H70B)=Sof(C71)=Sof(C96)=Sof(H96)=1-FVAR(4)
 Sof(O49)=Sof(C20)=Sof(H20)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(C48)=Sof(H48A)=
 Sof(H48B)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(C51)=FVAR(4)
 Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=
 Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(H77C)=1-FVAR(5)
 Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=
 Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(H67C)=FVAR(5)
8.a Free rotating group:
 C1A(C1B,C1C,C1D)
8.b Secondary CH2 refined with riding coordinates:
 C60(H60A,H60B), C61(H61A,H61B), C62(H62A,H62B), C22(H22A,H22B), C24(H24A,
 H24B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C38(H38A,H38B),
 C47(H47A,H47B), C48(H48A,H48B), C50(H50A,H50B), C4(H4A,H4B), C8(H8A,H8B),
 C16(H16A,H16B), C21(H21A,H21B), C23(H23A,H23B), C46(H46A,H46B), C49(H49A,H49B),
  C69(H69A,H69B), C70(H70A,H70B)
8.c Aromatic/amide H refined with riding coordinates:
 C17(H17), C19(H19), C31(H31), C33(H33), C43(H43), C45(H45), C56(H56), C58(H58)
8.d Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C63(H63A,H63B,
 H63C), C1A(H1AA,H1AB,H1AC), C1C(H1CA,H1CB,H1CC), C1D(H1DA,H1DB,H1DC), C37(H37A,
 H37B,H37C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C),
 C12(H12A,H12B,H12C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C77(H77A,H77B,H77C), C54(H54A,
 H54B,H54C), C53(H53A,H53B,H53C), C55(H55A,H55B,H55C)
8.e :
 C20(H20), C26(H26), C68(H68), C96(H96)
;
_shelx_res_checksum              30684
_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 2.747
_oxdiff_exptl_absorpt_empirical_full_min 0.573