Trinuclear ruthenium core-containing polyoxometalate-based hybrids: preparation, characterization and catalytic behavior.
Li, Huafeng; He, Peipei; Wan, Rong; Zou, Yan; Zhao, Xue; Ma, Pengtao; Niu, Jingyang; Wang, Jingping; Dalton transactions (Cambridge, England : 2003) 49 (2020) 2895–2904; doi:10.1039/c9dt04616j

data_7703403
_publ_section_title
;
 Trinuclear ruthenium core-containing polyoxometalate-based hybrids:
 preparation, characterization and catalytic behavior.
;
_journal_issue                   9
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              2895
_journal_page_last               2904
_journal_paper_doi               10.1039/c9dt04616j
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety         'As2 O69 W21, 2(C12 H18 Cl3 N18 O Ru3), 5(O)'
_chemical_formula_sum            'C24 H36 As2 Cl6 N36 O76 Ru6 W21'
_chemical_formula_weight         6874.70
_space_group_crystal_system      monoclinic
_space_group_IT_number           11
_space_group_name_Hall           '-P 2yb'
_space_group_name_H-M_alt        'P 1 21/m 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2019-05-31
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-08-27 deposited with the CCDC.	2020-01-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.3577(12)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   18.3691(5)
_cell_length_b                   18.3890(6)
_cell_length_c                   22.2929(6)
_cell_measurement_reflns_used    7742
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      28.012
_cell_measurement_theta_min      2.505
_cell_volume                     7147.1(4)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      149.98
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'Helios multilayer optic'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0783
_diffrn_reflns_av_unetI/netI     0.0550
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            71079
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.100
_diffrn_reflns_theta_max         25.100
_diffrn_reflns_theta_min         2.209
_diffrn_source_type              Microfocus
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    18.089
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.5601
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2016/2 - Bruker AXS area detector scaling and absorption correction 
 --------------------------------------------------------------------------

 Reference: Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D.,
 J. Appl. Cryst. 48 (2015) 3-10.

 Equivalent reflections defined by point group 2/m    for scaling

 Equivalent reflections defined by point group 2/m    for error model

 Reading file M769_01.raw
 Reading file M769_02.raw
 Reading file M769_03.raw
 Reading file M769_04.raw

 Mean and maximum errors in direction cosine check function =   0.000   0.002
 The mean error should not exceed 0.005, and is usually caused by matrix
 changes during data processing.

 Approximate wavelength, cell and maximum 2-theta (from cosines etc.):
 0.71070   18.376   18.391   22.300   90.017  108.353   89.989   56.58

 Scan  2-theta  high res  %[I>3sig(I)]
   1     0.00    0.7501       7.11
   2    13.00    0.7500      34.97
   3    12.10    0.7501      35.46
   4    12.10    0.7501      33.14

 Fast scans:  1

 These scans are used only to provide replacements for reflections missing
 in all other scans (e.g.  overloads suppressed by SAINT) and do not otherwise
 contribute to the final reflection file.

 Fast scans truncated to  1.5000 Angstroms

 ==============================================================================

 PART 1 - Refinement of parameters to model systematic errors

 Thresholds should now be specified for excluding reflections from the
 parameter refinement; these reflections may still be corrected and included
 in the final output .hkl file

   89798 Reflections of which  18298 unique;  168.16 data per frame

 Redundancy:          1     2     3     4     5     6     7     8     9+
 Number of groups:   376  1459  3187  3995  2500  2434  1968  1521   858

 Mean(I/sigma):  -inf    0     1     2     3     5    10    15    20   +inf
 Number of groups:  2620  5315  3117  1872  2295  1804   654   297   324

 Reading crystal faces from file:  D:\frames\guest\M769\work\nac_db.p4p

 Crystal faces:

     H       K       L      d(mm)

  -1.000   0.000   0.000   0.01900
   1.000   0.000   0.000   0.03700
  -1.000   0.000   1.000   0.04600
   1.000   0.000  -1.000   0.03400
  -1.000   1.000   0.000   0.02500
   1.000  -1.000   0.000   0.03800
  -1.000   1.000   1.000   0.04300
   1.000  -1.000  -1.000   0.04600
   0.000   1.000   0.000   0.03300
   0.000  -1.000   0.000   0.05300

  10 Faces  +  16 Corners  =  24 Edges  +  2

 Cycle  1     Mu   0.000 mm-1     Rint  0.13631
 Cycle  2     Mu   5.000 mm-1     Rint  0.16073
 Cycle  3     Mu   1.910 mm-1     Rint  0.14434
 Cycle  4     Mu   0.729 mm-1     Rint  0.13913
 Cycle  5     Mu   0.279 mm-1     Rint  0.13734
 Cycle  6     Mu   0.106 mm-1     Rint  0.13670
 Cycle  7     Mu   0.041 mm-1     Rint  0.13645
 Cycle  8     Mu   0.016 mm-1     Rint  0.13636
 Cycle  9     Mu   0.006 mm-1     Rint  0.13633
 All Rint values calculated using   46011 selected reflections only
 Rint 0.1363 for mu = 0 and 0.1363 for mu =   0.006 mm-1
 All Rint values calculated using   50374 selected reflections only
 Minimum and maximum transmission coefficients = 0.99942 and 0.99976
 Minimum and maximum t-bar = 0.0401 and 0.0982 mm

 Settings for parameter refinement:

 Maximum resolution =  0.1000 A
 (Intensity/sigma) threshold = 1.500
 Restraint esd for equal adjacent scale factors =  0.0050
 Maximum odd and even orders for spherical harmonics =   1   4

   50373 Reflections employed for parameter determination
 Effective data to parameter ratio =   73.71

 wR2(int) =  0.1249 (selected reflections only, before parameter refinement)

 Cycle  wR2(incid)  wR2(diffr)  Mean wt.
    1     0.0996      0.0854     0.8177
    2     0.0818      0.0799     0.8253
    3     0.0793      0.0787     0.8268
    4     0.0787      0.0784     0.8270
    5     0.0786      0.0785     0.8270
    6     0.0785      0.0784     0.8271
    7     0.0784      0.0783     0.8273
    8     0.0782      0.0782     0.8274
    9     0.0782      0.0782     0.8275
   10     0.0781      0.0782     0.8275
   11     0.0781      0.0781     0.8276
   12     0.0781      0.0781     0.8276
   13     0.0781      0.0781     0.8276
   14     0.0781      0.0781     0.8276
   15     0.0780      0.0781     0.8276
   16     0.0780      0.0781     0.8277
   17     0.0780      0.0781     0.8277
   18     0.0780      0.0781     0.8277
   19     0.0780      0.0780     0.8277
   20     0.0780      0.0780     0.8277
   21     0.0780      0.0780     0.8277
   22     0.0780      0.0780     0.8277
   23     0.0780      0.0780     0.8278
   24     0.0780      0.0780     0.8278
   25     0.0780      0.0780     0.8278
   26     0.0780      0.0780     0.8278
   27     0.0780      0.0780     0.8278
   28     0.0780      0.0780     0.8278
   29     0.0780      0.0780     0.8278
   30     0.0780      0.0780     0.8278
   31     0.0780      0.0780     0.8278
   32     0.0780      0.0780     0.8278
   33     0.0780      0.0780     0.8278
   34     0.0779      0.0780     0.8278
   35     0.0779      0.0780     0.8278
   36     0.0779      0.0780     0.8279
   37     0.0779      0.0780     0.8279
   38     0.0779      0.0780     0.8279
   39     0.0779      0.0780     0.8279
   40     0.0779      0.0780     0.8279
   41     0.0779      0.0780     0.8279
   42     0.0779      0.0780     0.8279
   43     0.0779      0.0780     0.8279
   44     0.0779      0.0780     0.8279
   45     0.0779      0.0780     0.8279
   46     0.0779      0.0780     0.8279
   47     0.0779      0.0780     0.8279
   48     0.0779      0.0780     0.8279
   49     0.0779      0.0780     0.8279
   50     0.0779      0.0780     0.8279

 wR2(int) =  0.0780 (selected reflections only, after parameter refinement)

 ==============================================================================

 PART 2 - Reject outliers and establish error model

 Rejected reflections are ignored in the statistics and Postscript plots
 (except the detector diagnostics) and in the output .hkl file
 Before applying rejections there are:

   89798 total and  18298 unique reflections assuming Friedel's law
 plus   8052 total and  2304 unique reflections in fast scans

 Reflections rejected for which |I-<I>|/su >   4.00
 where:  su^2 = sigma(I)^2 + (  0.04000 <I>)^2  (sigma(I) from SAINT)

   89589 total and  18297 unique reflections left after |I-<I>|/su test
 plus   7997 total and  2304 unique reflections in fast scans

 su^2 = [K*sigma(I)]^2 + [g<I>]^2  where sigma(I) is from SAINT

 Error model 5: refine all K and overall g

 Run 2theta R(int) Incid. factors Diffr. factors    K      g   I/s(lim) Total I>2sig(I)
   1f  0.0  0.2677  0.669 - 1.015  0.941 - 1.171  1.310  0.0373  26.8    7997    2774
   2  13.0  0.1332  0.578 - 0.871  0.940 - 1.171  0.906  0.0373  26.8   57093   28185
   3  12.1  0.1248  0.612 - 0.637  0.961 - 1.169  0.903  0.0373  26.8   14192    7006
   4  12.1  0.1453  0.629 - 0.856  0.940 - 1.169  0.924  0.0373  26.8   18304    8635

 I/s(lim) is the limiting value of I/sigma(I) for a reflection of infinite
 intensity, and may be used as a criterion for data quality (Diederichs(2010),
 Acta Cryst, D66, 733-740. The above statistics are based on all non-rejected
 data, ignoring reflections without equivalents when estimating R(int) and K.

 Scan  2-theta  high res  %[I>3sig(I)]
   1     0.00    0.7501       7.11
   2    13.00    0.7500      34.97
   3    12.10    0.7501      35.46
   4    12.10    0.7501      33.14

 Fast scans:  1

 These scans are used only to provide replacements for reflections missing
 in all other scans (e.g.  overloads suppressed by SAINT) and do not otherwise
 contribute to the final reflection file.

 Fast scans truncated to  1.5000 Angstroms

 ==============================================================================

 PART 1 - Refinement of parameters to model systematic errors

 Thresholds should now be specified for excluding reflections from the
 parameter refinement; these reflections may still be corrected and included
 in the final output .hkl file

   89798 Reflections of which  18298 unique;  168.16 data per frame

 Redundancy:          1     2     3     4     5     6     7     8     9+
 Number of groups:   376  1459  3187  3995  2500  2434  1968  1521   858

 Mean(I/sigma):  -inf    0     1     2     3     5    10    15    20   +inf
 Number of groups:  2620  5315  3117  1872  2295  1804   654   297   324

 Reading crystal faces from file:  D:\frames\guest\M769\work\nac_db.p4p

 Crystal faces:

     H       K       L      d(mm)

  -1.000   0.000   0.000   0.01900
   1.000   0.000   0.000   0.03700
  -1.000   0.000   1.000   0.04600
   1.000   0.000  -1.000   0.03400
  -1.000   1.000   0.000   0.02500
   1.000  -1.000   0.000   0.03800
  -1.000   1.000   1.000   0.04300
   1.000  -1.000  -1.000   0.04600
   0.000   1.000   0.000   0.03300
   0.000  -1.000   0.000   0.05300

  10 Faces  +  16 Corners  =  24 Edges  +  2

 Cycle  1     Mu   0.000 mm-1     Rint  0.13631
 Cycle  2     Mu   5.000 mm-1     Rint  0.16073
 Cycle  3     Mu   1.910 mm-1     Rint  0.14434
 Cycle  4     Mu   0.729 mm-1     Rint  0.13913
 Cycle  5     Mu   0.279 mm-1     Rint  0.13734
 Cycle  6     Mu   0.106 mm-1     Rint  0.13670
 Cycle  7     Mu   0.041 mm-1     Rint  0.13645
 Cycle  8     Mu   0.016 mm-1     Rint  0.13636
 Cycle  9     Mu   0.006 mm-1     Rint  0.13633
 All Rint values calculated using   46010 selected reflections only
 Rint 0.1363 for mu = 0 and 0.1363 for mu =   0.006 mm-1
 All Rint values calculated using   50373 selected reflections only
 Minimum and maximum transmission coefficients = 0.99942 and 0.99976
 Minimum and maximum t-bar = 0.0401 and 0.0982 mm

 Settings for parameter refinement:

 Maximum resolution =  0.1000 A
 (Intensity/sigma) threshold = 1.500
 Restraint esd for equal adjacent scale factors =  0.0050
 Maximum odd and even orders for spherical harmonics =   1   4

   50373 Reflections employed for parameter determination
 Effective data to parameter ratio =   73.71

 wR2(int) =  0.1249 (selected reflections only, before parameter refinement)

 Cycle  wR2(incid)  wR2(diffr)  Mean wt.
    1     0.0996      0.0854     0.8177
    2     0.0818      0.0800     0.8253
    3     0.0793      0.0787     0.8268
    4     0.0787      0.0784     0.8270
    5     0.0786      0.0785     0.8270
    6     0.0785      0.0784     0.8271
    7     0.0784      0.0783     0.8272
    8     0.0783      0.0782     0.8274
    9     0.0782      0.0782     0.8275
   10     0.0781      0.0782     0.8275
   11     0.0781      0.0781     0.8275
   12     0.0781      0.0781     0.8276
   13     0.0781      0.0781     0.8276
   14     0.0781      0.0781     0.8276
   15     0.0781      0.0781     0.8276
   16     0.0780      0.0781     0.8277
   17     0.0780      0.0781     0.8277
   18     0.0780      0.0781     0.8277
   19     0.0780      0.0780     0.8277
   20     0.0780      0.0780     0.8277
   21     0.0780      0.0780     0.8277
   22     0.0780      0.0780     0.8277
   23     0.0780      0.0780     0.8278
   24     0.0780      0.0780     0.8278
   25     0.0780      0.0780     0.8278
   26     0.0780      0.0780     0.8278
   27     0.0780      0.0780     0.8278
   28     0.0780      0.0780     0.8278
   29     0.0780      0.0780     0.8278
   30     0.0780      0.0780     0.8278
   31     0.0780      0.0780     0.8278
   32     0.0780      0.0780     0.8278
   33     0.0779      0.0780     0.8278
   34     0.0779      0.0780     0.8278
   35     0.0779      0.0780     0.8278
   36     0.0779      0.0780     0.8278
   37     0.0779      0.0780     0.8279
   38     0.0779      0.0780     0.8279
   39     0.0779      0.0780     0.8279
   40     0.0779      0.0780     0.8279
   41     0.0779      0.0780     0.8279
   42     0.0779      0.0780     0.8279
   43     0.0779      0.0780     0.8279
   44     0.0779      0.0780     0.8279
   45     0.0779      0.0780     0.8279
   46     0.0779      0.0780     0.8279
   47     0.0779      0.0780     0.8279
   48     0.0779      0.0780     0.8279
   49     0.0779      0.0780     0.8279
   50     0.0779      0.0780     0.8279

 wR2(int) =  0.0780 (selected reflections only, after parameter refinement)

 ==============================================================================

 PART 2 - Reject outliers and establish error model

 Rejected reflections are ignored in the statistics and Postscript plots
 (except the detector diagnostics) and in the output .hkl file
 Before applying rejections there are:

   89798 total and  18298 unique reflections assuming Friedel's law
 plus   8052 total and  2304 unique reflections in fast scans

 Reflections rejected for which |I-<I>|/su >   4.00
 where:  su^2 = sigma(I)^2 + (  0.04000 <I>)^2  (sigma(I) from SAINT)

   89589 total and  18297 unique reflections left after |I-<I>|/su test
 plus   7997 total and  2304 unique reflections in fast scans

 su^2 = [K*sigma(I)]^2 + [g<I>]^2  where sigma(I) is from SAINT

 Error model 5: refine all K and overall g

 Run 2theta R(int) Incid. factors Diffr. factors    K      g   I/s(lim) Total I>2sig(I)
   1f  0.0  0.2677  0.672 - 1.018  0.941 - 1.171  1.310  0.0374  26.8    7997    2774
   2  13.0  0.1332  0.570 - 0.860  0.940 - 1.171  0.906  0.0374  26.8   57093   28186
   3  12.1  0.1248  0.669 - 0.696  0.961 - 1.169  0.903  0.0374  26.8   14192    7006
   4  12.1  0.1453  0.610 - 0.830  0.940 - 1.169  0.924  0.0374  26.8   18304    8635

 I/s(lim) is the limiting value of I/sigma(I) for a reflection of infinite
 intensity, and may be used as a criterion for data quality (Diederichs(2010),
 Acta Cryst, D66, 733-740. The above statistics are based on all non-rejected
 data, ignoring reflections without equivalents when estimating R(int) and K.

 ==============================================================================

 PART 3 - Output Postscript diagnostics and corrected data

 Diagnostic plots written to Postscript file M769.eps

 ** R(int) could not be plotted for   1 scans - insufficient common reflections
 Reflections not merged
       1 Overloads replaced by fast scan measurements
   89590 Corrected reflections written to file M769_0m.hkl
 Estimated minimum and maximum transmission:  0.0006  0.0090
 The ratio of these values is more reliable than their absolute values!
 Additional spherical absorption correction applied with mu*r = 10.0000
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    3.195
_exptl_crystal_description       block
_exptl_crystal_F_000             6052
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.08
_refine_diff_density_max         3.614
_refine_diff_density_min         -2.429
_refine_diff_density_rms         0.451
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     811
_refine_ls_number_reflns         13115
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0983
_refine_ls_R_factor_gt           0.0735
_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^)+(0.1354P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1913
_refine_ls_wR_factor_ref         0.2175
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8797
_reflns_number_total             13115
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt04616j2.cif
_cod_data_source_block           njy1_a_CCDC1
_cod_depositor_comments
'Adding full bibliography for 7703402--7703403.cif.'
_cod_database_code               7703403
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.326
_shelx_estimated_absorpt_t_min   0.186
_diffrn_source_source            'Incoatc Ius 3.0 '
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2. Restrained distances
 C7-N2
 1.38 with sigma of 0.02
 C6-N2
 1.38 with sigma of 0.02
 N7-C10
 1.38 with sigma of 0.02
 N8-C10
 1.38 with sigma of 0.02
 C8-N6
 1.38 with sigma of 0.02
 C7-C6
 2.4 with sigma of 0.04
3. Rigid bond restraints
 N6, C8
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(O27) \\sim Ueq, Uanis(N16) \\sim Ueq, Uanis(N6) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
5.a Aromatic/amide H refined with riding coordinates:
 N2(H2), N6(H6), N8(H8), N10(H10), N13(H13), N16(H16), N18(H18), N20(H20),
 C1(H1), C2(H2A), C4(H4), C5(H5), C6(H6A), C7(H7), C8(H8A), C9(H9), C10(H10A),
 C25(H25), C32(H32), C33(H33)
;
_shelx_res_checksum              20705
_shelx_fab_checksum              41905
_olex2_submission_special_instructions 'No special instructions were received'