Design and oxidative desulfurization of Ag/Ti heterometallic clusters based on Hard-Soft Acid-Base principle.
Yang, Shuyi; Fu, Yaomei; Tian, Yiran; Zhao, Liang; Wang, Xinlong; Li, Baoli; Dalton transactions (Cambridge, England : 2003)  (2023) –; doi:10.1039/d3dt02387g

data_7714486
_publ_section_title
;
 Design and oxidative desulfurization of Ag/Ti heterometallic clusters
 based on Hard-Soft Acid-Base principle.
;
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_paper_doi               10.1039/d3dt02387g
_journal_year                    2023
_chemical_formula_moiety         'C150 H121.5 Ag2 O58 Ti10, 4[CH3CN], 4[H2O]'
_chemical_formula_sum            'C158 H140 Ag2 N4 O62 Ti10'
_chemical_formula_weight         3781.47
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-23
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.17 svn.r577a77a9 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-10-23 deposited with the CCDC.	2023-11-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.0750(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.1273(9)
_cell_length_b                   23.1405(10)
_cell_length_c                   37.5489(16)
_cell_measurement_reflns_used    9872
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      25.000
_cell_measurement_theta_min      1.953
_cell_volume                     16554.6(13)
_computing_cell_refinement       'SAINT+ Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_data_collection       'APEX3 Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_data_reduction        'SAINT+ Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2015b)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      173.02
_diffrn_detector                 'charge-coupled device (CCD) area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker D8 VENTURE'
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '0.5\% \w and 0.5\% \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_detector       'Bruker D8 VENTURE'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.1568
_diffrn_reflns_av_unetI/netI     0.1515
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            117523
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.058
_diffrn_reflns_theta_max         25.058
_diffrn_reflns_theta_min         2.212
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.776
_exptl_absorpt_correction_T_max  0.86
_exptl_absorpt_correction_T_min  0.84
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Krause et al., 2015) was used for absorption correction.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.517
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             7704
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.331
_refine_diff_density_min         -0.778
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2246
_refine_ls_number_reflns         28882
_refine_ls_number_restraints     1822
_refine_ls_restrained_S_all      1.319
_refine_ls_R_factor_all          0.1734
_refine_ls_R_factor_gt           0.0846
_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^)+(0.1169P)^2^+19.5247P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1989
_refine_ls_wR_factor_ref         0.2394
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14520
_reflns_number_total             28882
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02387g2.cif
_cod_data_source_block           2277822
_cod_database_code               7714486
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.54
_shelx_estimated_absorpt_t_min   0.21
_olex2_refinement_description
;
1. Restrained distances
 C148-C149
 1.5 with sigma of 0.02
 C137-C119
 1.5 with sigma of 0.01
 C160-C158 = C149-C148 = C159-C158 = C150-C148
 1.45 with sigma of 0.01
 C150-C149
 2.45 with sigma of 0.02
 C173-C171 = C138-C136
 1.5 with sigma of 0.01
 C147-C133 = C134-C133
 1.5 with sigma of 0.01
 C88-C142 = C88-C151 = C144-C139 = C157-C155
 1.5 with sigma of 0.01
 C162-C161 = C147-C133 = C134-C133 = C163-C161
 1.5 with sigma of 0.02
 C88-C142
 1.45 with sigma of 0.02
 O56B-C141 = O56A-C152
 1.35 with sigma of 0.01
 O53-C148 = O53-C158
 1.4 with sigma of 0.01
 Ti6-O32 = Ti6-O42 = Ti6-O12 = Ti6-O4
 1.82 with sigma of 0.01
 C55-C168 = C75-C164 = C165-C164 = C167-C165 = C168-C167 = C75-C105 = C130-
 C105 = C132-C130 = C132-C106 = C55-C106
 1.38 with sigma of 0.01
 C166-C165 = C146-C130
 1.5 with sigma of 0.01
 C80-C81 = C123-C124 = C128-C136 = C169-C170 = C171-C172
 1.38 with sigma of 0.01
 C180-C177
 1.5 with sigma of 0.02
 O58A-C161
 1.4 with sigma of 0.02
 O58B-C133 \\sim O58A-C161
 with sigma of 0.02
 Ti7-O58B \\sim Ti7-O58A
 with sigma of 0.02
2. Restrained planarity
 C151, C156, C155, C154, C153, C152, O56A
 with sigma of 0.01
3. Rigid bond restraints
 C119, C137
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C148, C150
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C139, C144
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Ag1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Ti6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C111, C129
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Ag1, O56
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
C80 \\sim C124 \\sim C172 \\sim C136 \\sim C138 \\sim C171 \\sim C173 \\sim C81
\\sim C123 \\sim C128 \\sim C169 \\sim C170: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.03 within 2A
C39 \\sim C40 \\sim C87 \\sim C95 \\sim C119 \\sim C121 \\sim C137: within 3.8A
with sigma of 0.01 and sigma for terminal atoms of 0.03 within 3.8A
O53 \\sim C148 \\sim C149 \\sim C150 \\sim C158 \\sim C159 \\sim C160: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.03 within 2A
O51 \\sim O56 \\sim C14 \\sim O55 \\sim C127 \\sim C50 \\sim C126 \\sim C120
\\sim C117 \\sim C116 \\sim C107 \\sim C175 \\sim C174 \\sim C179 \\sim C178
\\sim C177 \\sim C176 \\sim C180 \\sim O57: within 3.8A with sigma of 0.01 and
sigma for terminal atoms of 0.03 within 3.8A
C139 \\sim C140 \\sim C141 \\sim C142 \\sim C143 \\sim C144 \\sim C145 \\sim
C151 \\sim C152 \\sim C153 \\sim C154 \\sim C155 \\sim C156 \\sim C157 \\sim
C88 \\sim O56B \\sim O56A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.03 within 2A
C134 \\sim C133 \\sim C147 \\sim O58A \\sim C161 \\sim C162 \\sim C163: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.03 within 2A
C55 \\sim C75 \\sim C105 \\sim C106 \\sim C130 \\sim C132 \\sim C146 \\sim C164
\\sim C165 \\sim C166 \\sim C167 \\sim C168: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.03 within 2A
C134 \\sim C133 \\sim C147 \\sim O58A \\sim C161 \\sim C162 \\sim C163 \\sim
O58B: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.03
within 3.8A
C148 \\sim C149 \\sim C150 \\sim C158 \\sim C159 \\sim C160: within 3.8A with
sigma of 0.01 and sigma for terminal atoms of 0.03 within 3.8A
Uanis(C125) \\sim Ueq, Uanis(C137) \\sim Ueq, Uanis(C131) \\sim Ueq,
Uanis(C129) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.005
Uanis(C119) \\sim Ueq, Uanis(C137) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.01
Uanis(C135) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.03
Uanis(O53) \\sim Ueq, Uanis(C148) \\sim Ueq, Uanis(C149) \\sim Ueq, Uanis(C150)
\\sim Ueq, Uanis(C158) \\sim Ueq, Uanis(C159) \\sim Ueq, Uanis(C160) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.03
Uanis(O58B) = Uanis(O58A)
5. Others
 Fixed Sof: Ag2(0.6666) Ag3(0.3333) O56B(0.5) C123(0.5) H123(0.5) C128(0.5)
 H128(0.5) C136(0.5) C124(0.5) H124(0.5) C105(0.5) H105(0.5) C106(0.5)
 H106(0.5) C130(0.5) C132(0.5) H132(0.5) C138(0.5) H13J(0.5) H13K(0.5)
 H13L(0.5) C139(0.5) H13M(0.5) H13N(0.5) H13O(0.5) C142(0.5) C143(0.5)
 H143(0.5) C144(0.5) C145(0.5) H145(0.5) C140(0.5) H140(0.5) C141(0.5)
 C146(0.5) H14A(0.5) H14B(0.5) H14C(0.5) C148(0.5) H148(0.5) C149(0.5)
 H14D(0.5) H14E(0.5) H14F(0.5) C150(0.5) H15A(0.5) H15B(0.5) H15C(0.5)
 C152(0.5) C151(0.5) C156(0.5) H156(0.5) C155(0.5) C154(0.5) H154(0.5)
 C153(0.5) H153(0.5) C157(0.5) H15D(0.5) H15E(0.5) H15F(0.5) O56A(0.5)
 C158(0.5) H158(0.5) C159(0.5) H15G(0.5) H15H(0.5) H15I(0.5) C160(0.5)
 H16A(0.5) H16B(0.5) H16C(0.5) C164(0.5) H164(0.5) C165(0.5) C166(0.5)
 H16D(0.5) H16E(0.5) H16F(0.5) C167(0.5) H167(0.5) C168(0.5) H168(0.5)
 C169(0.5) H169(0.5) C170(0.5) H170(0.5) C171(0.5) C172(0.5) H172(0.5)
 C173(0.5) H17A(0.5) H17B(0.5) H17C(0.5) C127(0.5) H12G(0.5) H12H(0.5)
 H12I(0.5) C50(0.5) C126(0.5) H126(0.5) C120(0.5) C117(0.5) H117(0.5) C116(0.5)
 H116(0.5) C107(0.5) C175(0.5) C174(0.5) C179(0.5) H179(0.5) C178(0.5)
 H178(0.5) C177(0.5) C176(0.5) H176(0.5) C180(0.5) H18A(0.5) H18B(0.5)
 H18C(0.5) C134(0.5) H13P(0.5) H13Q(0.5) H13R(0.5) C133(0.5) C147(0.5)
 H14G(0.5) H14H(0.5) H14I(0.5) O58A(0.5) C161(0.5) H161(0.5) C162(0.5)
 H16G(0.5) H16H(0.5) H16I(0.5) C163(0.5) H16J(0.5) H16K(0.5) H16L(0.5)
 O58B(0.5) O51(0.6) O57(0.4)
6.a Riding coordinates:
 C69(H69A,H69B,H69C), C149(H14D,H14E,H14F), C150(H15A,H15B,H15C), C160(H16A,
 H16B,H16C), C173(H17A,H17B,H17C)
6.b Ternary CH refined with riding coordinates:
 C148(H148), C158(H158), C161(H161)
6.c Aromatic/amide H refined with riding coordinates:
 C19(H19), C30(H30), C31(H31), C34(H34), C36(H36), C37(H37), C42(H42),
 C44(H44), C45(H45), C46(H46), C47(H47), C49(H49), C51(H51), C52(H52), C56(H56),
  C57(H57), C58(H58), C59(H59), C63(H63), C64(H64), C68(H68), C73(H73),
 C79(H79), C123(H123), C128(H128), C124(H124), C82(H82), C83(H83), C84(H84),
 C85(H85), C86(H86), C87(H87), C90(H90), C92(H92), C94(H94), C95(H95), C96(H96),
  C99(H99), C102(H102), C103(H103), C105(H105), C106(H106), C109(H109),
 C113(H113), C114(H114), C118(H118), C121(H121), C132(H132), C143(H143),
 C145(H145), C140(H140), C156(H156), C154(H154), C153(H153), C164(H164),
 C167(H167), C168(H168), C169(H169), C170(H170), C172(H172), C126(H126),
 C117(H117), C116(H116), C179(H179), C178(H178), C176(H176)
6.d Fitted hexagon refined as free rotating group:
 C80(C81,C123,C128,C136,C124), C142(C143,C144,C145,C140,C141), C152(C151,C156,
 C155,C154,C153), C50(C126,C120,C117,C116,C107), C175(C174,C179,C178,C177,C176)
6.e Idealised Me refined as rotating group:
 C65(H65A,H65B,H65C), C93(H93A,H93B,H93C), C97(H97A,H97B,H97C), C101(H10A,H10B,
 H10C), C104(H10D,H10E,H10F), C108(H10G,H10H,H10I), C110(H11A,H11B,H11C),
 C115(H11D,H11E,H11F), C125(H12A,H12B,H12C), C129(H12D,H12E,H12F), C131(H13A,
 H13B,H13C), C135(H13D,H13E,H13F), C137(H13G,H13H,H13I), C138(H13J,H13K,H13L),
 C139(H13M,H13N,H13O), C146(H14A,H14B,H14C), C157(H15D,H15E,H15F), C159(H15G,
 H15H,H15I), C166(H16D,H16E,H16F), C127(H12G,H12H,H12I), C180(H18A,H18B,H18C),
 C134(H13P,H13Q,H13R), C147(H14G,H14H,H14I), C162(H16G,H16H,H16I), C163(H16J,
 H16K,H16L)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 512 electrons were 
found in a volume of 3442\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
4[CH3CN], 4[H2O] per Asymmetric Unit 
which account for 512 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              66342
_shelx_fab_checksum              36758
_platon_squeeze_special_details
;
A solvent mask was calculated and 676 electrons were 
found in a volume of 3155\%A^3^ in 5 voids per unit cell. 
This is consistent with the presence of 
4[C3H8O], 4[H2O]per Asymmetric Unit 
which account for 312 electrons 
per unit cell.
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'