Janus Cluster: Asymmetric Coverage of a Ag43 Cluster on the Symmetric Preyssler P5W30 Polyoxometalate
Zhang, Shan-Shan; Chen, Jing-Yi; Li, Kai; Yuan, Jun-Di; Su, Hai-Feng; Wang, Zhi; Kurmoo, Mohamedally; Li, Ying-Zhou; Gao, Zhi-Yong; Tung, Chen-Ho; Sun, Di; Zheng, Lansun; Chemistry of Materials 33 (2021) 9708–9714; doi:10.1021/acs.chemmater.1c03418

data_4004056
_publ_section_title
;
 Janus Cluster: Asymmetric Coverage of a Ag43 Cluster on the Symmetric
 Preyssler P5W30 Polyoxometalate
;
_journal_issue                   24
_journal_name_full               'Chemistry of Materials'
_journal_page_first              9708
_journal_page_last               9714
_journal_paper_doi               10.1021/acs.chemmater.1c03418
_journal_volume                  33
_journal_year                    2021
_chemical_formula_moiety         'C179 H269 Ag43 K N3 O112 P5 W30, 3(C2 H3 N)'
_chemical_formula_sum            'C185 H278 Ag43 K N6 O112 P5 W30'
_chemical_formula_weight         14725.98
_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
_atom_sites_solution_primary     direct
_audit_creation_date             2017-12-11
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                92.3510(10)
_cell_angle_beta                 98.5850(10)
_cell_angle_gamma                110.7740(10)
_cell_formula_units_Z            2
_cell_length_a                   21.7545(3)
_cell_length_b                   23.2675(4)
_cell_length_c                   35.6129(5)
_cell_measurement_reflns_used    69114
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      30.7110
_cell_measurement_theta_min      3.4140
_cell_volume                     16579.2(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.30d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.30d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.30d (Rigaku OD, 2017)'
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      172.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.993
_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    -68.00  18.00   1.00   30.00    --    5.49 -37.00 -90.00   86
  2  \w    -26.00  29.00   1.00   30.00    --   -4.48 -99.00 -30.00   55
  3  \w    -26.00  39.00   1.00   30.00    --    5.49 -99.00 -90.00   65
  4  \w    -26.00  29.00   1.00   30.00    --   -4.48 -99.00 120.00   55
  5  \w     24.00  69.00   1.00   30.00    --    5.49-153.00 131.00   45
  6  \w    -63.00  24.00   1.00   30.00    --    5.49 -77.00  30.00   87
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0052709000
_diffrn_orient_matrix_UB_12      -0.0171996000
_diffrn_orient_matrix_UB_13      -0.0178707000
_diffrn_orient_matrix_UB_21      0.0115559000
_diffrn_orient_matrix_UB_22      -0.0216174000
_diffrn_orient_matrix_UB_23      0.0092424000
_diffrn_orient_matrix_UB_31      -0.0330654000
_diffrn_orient_matrix_UB_32      -0.0176354000
_diffrn_orient_matrix_UB_33      0.0022750000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0506
_diffrn_reflns_av_unetI/netI     0.0557
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            205366
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         3.211
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    12.930
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55236
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.30d (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    2.950
_exptl_crystal_description       block
_exptl_crystal_F_000             13322
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         5.586
_refine_diff_density_min         -4.420
_refine_diff_density_rms         0.279
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3413
_refine_ls_number_reflns         67360
_refine_ls_number_restraints     165
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0669
_refine_ls_R_factor_gt           0.0500
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0001P)^2^+510.7146P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0989
_refine_ls_wR_factor_ref         0.1040
_reflns_Friedel_coverage         0.000
_reflns_number_gt                53841
_reflns_number_total             67360
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm1c03418_si_002.cif
_cod_data_source_block           p
_cod_original_cell_volume        16579.2(4)
_cod_database_code               4004056
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         AgWPOCH
_shelx_estimated_absorpt_t_max   0.424
_shelx_estimated_absorpt_t_min   0.358
_reflns_odcompleteness_completeness 99.34
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All O(H,H) groups, {H18J,H18K,H18L} of C182, {H18G,H18H,H18I} of C185, {H4A,
  H4B,H4C} of C4, {H11A,H11B,H11C} of C11, {H16A,H16B,H16C} of C16, {H6A,H6B,
  H6C} of C6, {H5A,H5B,H5C} of C5, {H17A,H17B,H17C} of C17, {H10A,H10B,H10C} of
  C10, {H12A,H12B,H12C} of C12, {H18A,H18B,H18C} of C18, {H22A,H22B,H22C} of
  C22, {H30A,H30B,H30C} of C30, {H24A,H24B,H24C} of C24, {H28A,H28B,H28C} of
  C28, {H29A,H29B,H29C} of C29, {H23A,H23B,H23C} of C23, {H52A,H52B,H52C} of
  C52, {H53A,H53B,H53C} of C53, {H36A,H36B,H36C} of C36, {H54A,H54B,H54C} of
  C54, {H35A,H35B,H35C} of C35, {H34A,H34B,H34C} of C34, {H58A,H58B,H58C} of
  C58, {H41A,H41B,H41C} of C41, {H42A,H42B,H42C} of C42, {H47A,H47B,H47C} of
  C47, {H48A,H48B,H48C} of C48, {H40A,H40B,H40C} of C40, {H46A,H46B,H46C} of
  C46, {H83A,H83B,H83C} of C83, {H64A,H64B,H64C} of C64, {H82A,H82B,H82C} of
  C82, {H72A,H72B,H72C} of C72, {H76A,H76B,H76C} of C76, {H77A,H77B,H77C} of
  C77, {H65A,H65B,H65C} of C65, {H60A,H60B,H60C} of C60, {H70A,H70B,H70C} of
  C70, {H59A,H59B,H59C} of C59, {H71A,H71B,H71C} of C71, {H66A,H66B,H66C} of
  C66, {H78A,H78B,H78C} of C78, {H17G,H17H,H17I} of C173, {H17M,H17N,H17O} of
  C176, {H17D,H17E,H17F} of C172, {H16S,H16T,H16U} of C168, {H17J,H17K,H17L} of
  C174, {H14J,H14K,H14L} of C148, {H15A,H15B,H15C} of C150, {H15J,H15K,H15L} of
  C156, {H16M,H16N,H16O} of C166, {H16P,H16Q,H16R} of C167, {H15D,H15E,H15F} of
  C154, {H14G,H14H,H14I} of C144, {H15G,H15H,H15I} of C155, {H16J,H16K,H16L} of
  C162, {H14M,H14N,H14O} of C149, {H16D,H16E,H16F} of C160, {H16G,H16H,H16I} of
  C161, {H12J,H12K,H12L} of C125, {H13A,H13B,H13C} of C130, {H14A,H14B,H14C} of
  C142, {H13P,H13Q,H13R} of C138, {H14D,H14E,H14F} of C143, {H12D,H12E,H12F} of
  C120, {H11P,H11Q,H11R} of C119, {H13M,H13N,H13O} of C137, {H13J,H13K,H13L} of
  C136, {H12G,H12H,H12I} of C124, {H12M,H12N,H12O} of C126, {H13G,H13H,H13I} of
  C132, {H13D,H13E,H13F} of C131, {H89A,H89B,H89C} of C89, {H90A,H90B,H90C} of
  C90, {H10G,H10H,H10I} of C101, {H95A,H95B,H95C} of C95, {H10D,H10E,H10F} of
  C100, {H94A,H94B,H94C} of C94, {H10M,H10N,H10O} of C106, {H10J,H10K,H10L} of
  C102, {H10P,H10Q,H10R} of C107, {H96A,H96B,H96C} of C96, {H10S,H10T,H10U} of
  C108, {H84A,H84B,H84C} of C84, {H88A,H88B,H88C} of C88, {H11M,H11N,H11O} of
  C118, {H11D,H11E,H11F} of C112, {H11J,H11K,H11L} of C114, {H11G,H11H,H11I} of
  C113
 At 1.2 times of:
  {H17P,H17Q,H17R} of C179, {H18D,H18E,H18F} of C181
2. Restrained distances
 C170-C171
 1.55 with sigma of 0.01
 C171-C173
 1.55 with sigma of 0.01
 C171-C172
 1.55 with sigma of 0.01
 C127-C128
 1.2 with sigma of 0.01
 H17E-H17H
 2.37 with sigma of 0.01
 C171-C174
 1.55 with sigma of 0.01
 C174-C170
 2.35 with sigma of 0.01
 H17H-H17K
 2.52 with sigma of 0.01
 H17G-H17K
 2.15 with sigma of 0.01
 C22-C23
 2.35 with sigma of 0.01
 C23-C24
 2.35 with sigma of 0.01
 C22-C24
 2.35 with sigma of 0.01
 H23A-H24B
 2.52 with sigma of 0.01
 C24-C20
 2.35 with sigma of 0.01
 C20-C23
 2.35 with sigma of 0.01
 C20-C22
 2.35 with sigma of 0.01
 C21-C20 \\sim C21-C22 \\sim C21-C23 \\sim C21-C24
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65 \\sim C66: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42: within 1.7A with sigma
of 0.004 and sigma for terminal atoms of 0.008
C133 \\sim C134 \\sim C135 \\sim C136 \\sim C137 \\sim C138: within 1.7A with
sigma of 0.004 and sigma for terminal atoms of 0.008
C169 \\sim C170 \\sim C171 \\sim C172 \\sim C173 \\sim C174: within 1.7A with
sigma of 0.004 and sigma for terminal atoms of 0.008
O2W \\sim K1A \\sim O2WA \\sim K1: within 1.7A with sigma of 0.004 and sigma
for terminal atoms of 0.008
C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24: within 1.7A with sigma
of 0.004 and sigma for terminal atoms of 0.008
4. Others
 Fixed Sof: K1(0.5) K1A(0.5) O2W(0.5) O2WA(0.5)
5.a Rotating group:
 O1W(H1WA,H1WB)
5.b Me refined with riding coordinates:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C10(H10A,H10B,H10C),
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,
 H24B,H24C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C40(H40A,H40B,
 H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C46(H46A,H46B,H46C), C47(H47A,
 H47B,H47C), C48(H48A,H48B,H48C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C),
 C54(H54A,H54B,H54C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,
 H60C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C70(H70A,
 H70B,H70C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C76(H76A,H76B,H76C),
 C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C82(H82A,H82B,H82C), C83(H83A,H83B,
 H83C), C84(H84A,H84B,H84C), C88(H88A,H88B,H88C), C89(H89A,H89B,H89C), C90(H90A,
 H90B,H90C), C94(H94A,H94B,H94C), C95(H95A,H95B,H95C), C96(H96A,H96B,H96C),
 C100(H10D,H10E,H10F), C101(H10G,H10H,H10I), C102(H10J,H10K,H10L), C106(H10M,
 H10N,H10O), C107(H10P,H10Q,H10R), C108(H10S,H10T,H10U), C112(H11D,H11E,H11F),
 C113(H11G,H11H,H11I), C114(H11J,H11K,H11L), C118(H11M,H11N,H11O), C119(H11P,
 H11Q,H11R), C120(H12D,H12E,H12F), C124(H12G,H12H,H12I), C125(H12J,H12K,H12L),
 C126(H12M,H12N,H12O), C130(H13A,H13B,H13C), C131(H13D,H13E,H13F), C132(H13G,
 H13H,H13I), C136(H13J,H13K,H13L), C137(H13M,H13N,H13O), C138(H13P,H13Q,H13R),
 C142(H14A,H14B,H14C), C143(H14D,H14E,H14F), C144(H14G,H14H,H14I), C148(H14J,
 H14K,H14L), C149(H14M,H14N,H14O), C150(H15A,H15B,H15C), C154(H15D,H15E,H15F),
 C155(H15G,H15H,H15I), C156(H15J,H15K,H15L), C160(H16D,H16E,H16F), C161(H16G,
 H16H,H16I), C162(H16J,H16K,H16L), C166(H16M,H16N,H16O), C167(H16P,H16Q,H16R),
 C168(H16S,H16T,H16U), C172(H17D,H17E,H17F), C173(H17G,H17H,H17I), C174(H17J,
 H17K,H17L), C176(H17M,H17N,H17O), C179(H17P,H17Q,H17R), C181(H18D,H18E,H18F),
 C185(H18G,H18H,H18I), C182(H18J,H18K,H18L)
;
_shelx_res_checksum              62843
_shelx_hkl_checksum              61917
_shelx_fab_checksum              46180
_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 1.677
_oxdiff_exptl_absorpt_empirical_full_min 0.670