Phosphate anion-induced silver-chalcogenide cluster-based metal organic frameworks as dual-functional catalysts for detoxifying chemical warfare agent simulant
Gong, Chun-Hua; Sun, Zhi-Bing; Cao, Man; Luo, Xi-Ming; Wu, Jie; Wang, Qian-You; Zang, Shuang-Quan; Mak, Thomas C. W.; Chemical Communications  (2022) –; doi:10.1039/D2CC03120E

data_7130489
_publ_section_title
;
 Phosphate anion-induced silver-chalcogenide cluster-based metal organic
 frameworks as dual-functional catalysts for detoxifying chemical warfare
 agent simulant
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC03120E
_journal_year                    2022
_chemical_formula_moiety         'C208 H292 Ag54 F18 N10 O52 P6 S32'
_chemical_formula_sum            'C208 H292 Ag54 F18 N10 O52 P6 S32'
_chemical_formula_weight         11143.22
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2021-01-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-02-20 deposited with the CCDC.	2022-08-08 downloaded from the CCDC.
;
_cell_angle_alpha                67.507(5)
_cell_angle_beta                 70.652(5)
_cell_angle_gamma                71.542(4)
_cell_formula_units_Z            1
_cell_length_a                   20.7199(8)
_cell_length_b                   21.3162(9)
_cell_length_c                   21.6663(15)
_cell_measurement_reflns_used    10369
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      71.5800
_cell_measurement_theta_min      3.5850
_cell_volume                     8141.8(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.944
_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    -89.00  19.00   0.50    0.50    --    0.00 -38.00-150.00  216
  2  \w    -15.00  83.00   0.50    0.50    --    0.00  38.00-150.00  196
  3  \w     75.00 168.00   0.50    7.00    --   95.20  45.00  90.00  186
  4  \w     16.00 109.00   0.50    7.00    --   95.20 -82.00-150.00  186
  5  \w     20.00 119.00   0.50    7.00    --   95.20 -15.00 -90.00  198
  6  \w     34.00 120.00   0.50    7.00    --   95.20 -82.00  90.00  172
  7  \w     26.00 107.00   0.50    7.00    --   95.20 -61.00  90.00  162
  8  \w     10.00  99.00   0.50    7.00    --   95.20 -61.00-150.00  178
  9  \w     78.00 175.00   0.50    7.00    --   95.20  45.00  60.00  194
 10  \w     22.00 120.00   0.50    7.00    --   95.20 -61.00 -60.00  196
 11  \w     81.00 161.00   0.50    7.00    --   95.20  15.00-180.00  160
 12  \w     61.00 128.00   0.50    7.00    --   95.20 -82.00 -60.00  134
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0488323000
_diffrn_orient_matrix_UB_12      0.0507737000
_diffrn_orient_matrix_UB_13      -0.0445026000
_diffrn_orient_matrix_UB_21      0.0642522000
_diffrn_orient_matrix_UB_22      -0.0609613000
_diffrn_orient_matrix_UB_23      0.0074247000
_diffrn_orient_matrix_UB_31      -0.0024726000
_diffrn_orient_matrix_UB_32      -0.0113678000
_diffrn_orient_matrix_UB_33      -0.0651803000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0866
_diffrn_reflns_av_unetI/netI     0.1179
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.944
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            67854
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.944
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.486
_diffrn_reflns_theta_min         2.780
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    28.133
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.36035
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.27b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    2.273
_exptl_crystal_description       block
_exptl_crystal_F_000             5328
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.479
_refine_diff_density_min         -1.967
_refine_diff_density_rms         0.204
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1955
_refine_ls_number_reflns         31427
_refine_ls_number_restraints     564
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.1399
_refine_ls_R_factor_gt           0.0884
_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^)+(0.1357P)^2^+17.0619P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2370
_refine_ls_wR_factor_ref         0.2790
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17395
_reflns_number_total             31427
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03120e2.cif
_cod_data_source_block           ZZU_601
_cod_database_code               7130489
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_usercomment     ' '
_shelx_estimated_absorpt_t_max   0.334
_shelx_estimated_absorpt_t_min   0.283
_reflns_odcompleteness_completeness 98.75
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C100-C99
 1.51 with sigma of 0.02
 C101-C102
 1.51 with sigma of 0.02
 C73-C74
 1.5 with sigma of 0.01
 C78-C79 = C78-C77 = C76-C77 = C75-C76 = C75-C74 = C79-C74
 1.39 with sigma of 0.01
 C4-C6A = C5A-C4
 1.53 with sigma of 0.02
 C83-C82 = C83-C84
 1.39 with sigma of 0.01
 C105-N6
 1.2 with sigma of 0.02
 N6-C105
 1.15 with sigma of 0.02
 C3A-C1A = C2A-C1A
 1.53 with sigma of 0.01
 C3A-C2A
 2.4 with sigma of 0.02
 C1B-C3B = C1B-C2B = C2A-C1A = C3A-C1A
 1.53 with sigma of 0.02
 C106-C105
 1.53 with sigma of 0.01
 C105-C106
 1.51 with sigma of 0.02
 N6-C106
 2.7 with sigma of 0.01
 C6B-C5B
 2.4 with sigma of 0.02
 F9-C102 = F7-C102 = F8-C102
 1.35 with sigma of 0.02
 C9A-C7 = C9B-C7 = C8A-C7 = C8B-C7 = C30-C28 = C29-C28 = C39-C37 = C38-C37
 1.53 with sigma of 0.02
 C41-C40 = C42-C40 = C47-C46 = C48-C46 = C44-C43 = C45-C43
 1.53 with sigma of 0.02
 O25-C101 = O26-C101
 1.2 with sigma of 0.02
 O11-H11
 0.85 with sigma of 0.01
 O4-H4
 0.85 with sigma of 0.01
 P3-H11
 2.025296 with sigma of 0.02
 Ag17-H11
 3.05669 with sigma of 0.02
 P2-H4
 2.050382 with sigma of 0.02
 Ag7B-H4
 3.221688 with sigma of 0.02
3. Restrained planarity
 C74, C77, C78, C79
 with sigma of 0.1
 C74, C75, C76, C77
 with sigma of 0.1
 O17, O18, C73, C74, C75, C76, C77, C78, C79
 with sigma of 0.1
4. Rigid bond restraints
 C78, C79
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S1A, S1B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.01
C1A \\sim C1B \\sim C2A \\sim C2B \\sim C3A \\sim C3B: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.01
N6 \\sim C105 \\sim C106: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.01
Ag8A \\sim O17 \\sim O18 \\sim C73: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.01
Uanis(Ag1B) \\sim Ueq, Uanis(Ag2B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(Ag4B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C102) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O17) \\sim Ueq, Uanis(O18) \\sim Ueq, Uanis(C73) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C47) \\sim Ueq, Uanis(C48) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Ag7B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C40) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Ag6B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C75) \\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(C6A) \\sim Ueq, Uanis(C5A)
\\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq,
Uanis(C8B) \\sim Ueq, Uanis(C9B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C3B) \\sim Ueq, Uanis(C2B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C104) \\sim Ueq, Uanis(C103) \\sim Ueq, Uanis(N5) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(N6) \\sim Ueq, Uanis(C105) \\sim Ueq, Uanis(C106) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C6B) \\sim Ueq, Uanis(C5B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O7) \\sim Ueq, Uanis(O21) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(F9)
\\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(O2A) \\sim Ueq,
Uanis(C29) \\sim Ueq, Uanis(O1A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O20) \\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(F9)
\\sim Ueq, Uanis(F4) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(C36) \\sim Ueq,
Uanis(C43) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C44)
\\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C39) \\sim Ueq,
Uanis(C2A) \\sim Ueq, Uanis(C8A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F9) \\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(F7) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C9A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(S1B) \\sim Ueq, Uanis(S1A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O25) \\sim Ueq, Uanis(C101) \\sim Ueq, Uanis(O26) \\sim Ueq, Uanis(F9)
\\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F8) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
6. Others
 Sof(Ag3A)=Sof(Ag4A)=1-FVAR(1)
 Sof(Ag3B)=Sof(Ag4B)=FVAR(1)
 Sof(Ag5A)=1-FVAR(2)
 Sof(Ag5B)=FVAR(2)
 Sof(O1B)=Sof(O2B)=Sof(O3B)=1-FVAR(3)
 Sof(O1A)=Sof(O2A)=Sof(O3A)=FVAR(3)
 Sof(Ag2A)=1-FVAR(4)
 Sof(Ag2B)=FVAR(4)
 Sof(Ag1A)=1-FVAR(5)
 Sof(Ag1B)=FVAR(5)
 Sof(Ag8B)=1-FVAR(6)
 Sof(Ag8A)=FVAR(6)
 Sof(Ag7B)=1-FVAR(7)
 Sof(Ag7A)=FVAR(7)
 Sof(H7B)=Sof(C8B)=Sof(H8BA)=Sof(H8BB)=Sof(H8BC)=Sof(C9B)=Sof(H9BA)=Sof(H9BB)=
 Sof(H9BC)=1-FVAR(8)
 Sof(H7A)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=
 Sof(H9AC)=FVAR(8)
 Sof(H4B)=Sof(C5B)=Sof(H5BA)=Sof(H5BB)=Sof(H5BC)=Sof(C6B)=Sof(H6BA)=Sof(H6BB)=
 Sof(H6BC)=1-FVAR(9)
 Sof(H4AA)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=
 Sof(H6AC)=FVAR(9)
 Sof(S1A)=Sof(C1A)=Sof(H1A)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=Sof(C3A)=
 Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=1-FVAR(10)
 Sof(S1B)=Sof(C1B)=Sof(H1B)=Sof(C2B)=Sof(H2BA)=Sof(H2BB)=Sof(H2BC)=Sof(C3B)=
 Sof(H3BA)=Sof(H3BB)=Sof(H3BC)=FVAR(10)
 Fixed Sof: Ag6A(0.5) Ag6B(0.5) H1(0.5) H2(0.5) H3(0.5) H4A(0.5) N5(0.5)
 N6(0.5) C103(0.5) C104(0.5) H10A(0.5) H10B(0.5) H10C(0.5) C105(0.5) C106(0.5)
 H10D(0.5) H10E(0.5) H10F(0.5)
7.a Riding coordinates:
 O6(H6), O8(H8), O11(H11), C2A(H2AA,H2AB,H2AC), C2B(H2BA,H2BB,H2BC), C3A(H3AA,
 H3AB,H3AC), C3B(H3BA,H3BB,H3BC), C6B(H6BA,H6BB,H6BC), C9A(H9AA,H9AB,H9AC),
 C104(H10A,H10B,H10C), C106(H10D,H10E,H10F)
7.b Ternary CH refined with riding coordinates:
 C1A(H1A), C1B(H1B), C4(H4AA), C4(H4B), C7(H7A), C7(H7B), C10(H10), C13(H13),
 C16(H16A), C19(H19), C22(H22), C25(H25), C28(H28), C31(H31), C34(H34),
 C37(H37), C40(H40), C43(H43), C46(H46)
7.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), N3(H3), N4(H4A), C51(H51), C52(H52), C54(H54), C55(H55),
 C58(H58), C59(H59), C63(H63), C64(H64), C67(H67), C68(H68), C70(H70), C71(H71),
  C75(H75), C76(H76), C78(H78), C79(H79), C82(H82), C83(H83), C86(H86),
 C87(H87), C91(H91), C92(H92), C94(H94), C95(H95)
7.d Idealised Me refined as rotating group:
 C5A(H5AA,H5AB,H5AC), C5B(H5BA,H5BB,H5BC), C6A(H6AA,H6AB,H6AC), C8A(H8AA,H8AB,
 H8AC), C8B(H8BA,H8BB,H8BC), C9B(H9BA,H9BB,H9BC), C11(H11A,H11B,H11C), C12(H12A,
 H12B,H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C),
 C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,
 H29B,H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C),
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C38(H38A,H38B,H38C), C39(H39A,H39B,
 H39C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C44(H44A,H44B,H44C), C45(H45A,
 H45B,H45C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C)
7.e Idealised tetrahedral OH refined as rotating group:
 O16(H16)
;
_shelx_res_checksum              38461
_shelx_hkl_checksum              73764
_shelx_fab_checksum              96661
_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 1.986
_oxdiff_exptl_absorpt_empirical_full_min 0.541