An intriguing tetranuclear Rh-based polyoxometalate for the reduction of nitroarene and oxidation of aniline.
Chen, Wenjing; Li, Huafeng; Jin, Yuzhen; Wu, Che; Yuan, Zelong; Ma, Pengtao; Wang, Jingping; Niu, Jingyang; Chemical communications (Cambridge, England) 58 (2022) 9902–9905; doi:10.1039/d2cc03076d

data_7130658
_publ_section_title
;
 An intriguing tetranuclear Rh-based polyoxometalate for the reduction of
 nitroarene and oxidation of aniline.
;
_journal_issue                   71
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              9902
_journal_page_last               9905
_journal_paper_doi               10.1039/d2cc03076d
_journal_volume                  58
_journal_year                    2022
_chemical_formula_moiety
'C12 H8 As4 N4 Na5 O146 Rh4 S2 W40, 2(C12 H12 Cl2 N4 Na0.17 Rh0.83), 2(C8 H8 N2), 46(H2 O)'
_chemical_formula_sum
'C52 H148 As4 Cl4 N16 Na5.34 O192 Rh5.66 S2 W40'
_chemical_formula_weight         12634.16
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-08-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-08-06 deposited with the CCDC.	2022-08-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.885(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   41.050(5)
_cell_length_b                   19.763(2)
_cell_length_c                   29.763(4)
_cell_measurement_reflns_used    9951
_cell_measurement_temperature    296
_cell_measurement_theta_max      28.05
_cell_measurement_theta_min      2.53
_cell_volume                     22559(5)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'BRUKE D8 VENTURE'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      296.3
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker D8 VENTURE PHOTON II'
_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  0.0482
_diffrn_reflns_av_unetI/netI     0.0424
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       48
_diffrn_reflns_limit_h_min       -48
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            84416
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.100
_diffrn_reflns_theta_max         25.100
_diffrn_reflns_theta_min         2.187
_diffrn_source_type              Microfocus
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    21.447
_exptl_absorpt_correction_T_max  0.0113
_exptl_absorpt_correction_T_min  0.0013
_exptl_absorpt_correction_type   multi-scan
_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 M5360_01.raw
 Reading file M5360_02.raw
 Reading file M5360_03.raw

 Mean and maximum errors in direction cosine check function =   0.000   0.003
 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.):
 0.71074   40.909   19.760   29.715   89.925  110.846   90.025   56.64

 Scan  2-theta  high res  %[I>3sig(I)]
   1     0.00    0.7500      28.99
   2    15.84    0.7500      52.40
   3    14.94    0.7500      48.69

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

 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

  184690 Reflections of which  28665 unique;  326.88 data per frame

 Redundancy:          1     2     3     4     5     6     7     8     9+
 Number of groups:   645  1169  2303  3615  3371  3859  3676  3869  6158

 Mean(I/sigma):  -inf    0     1     2     3     5    10    15    20   +inf
 Number of groups:  4418  7391  3798  2511  3108  3552  1427   810  1650

 Reading crystal faces from file:  D:\frames\guest\M5360\work\nac_db.p4p

 Crystal faces:

     H       K       L      d(mm)

   1.000   0.000   1.000   0.06200
  -1.000   0.000   0.000   0.10000
   1.000   0.000   0.000   0.01400
   1.000   1.000   1.000   0.12400
   0.000   1.000   1.000   0.16100
  -1.000   0.000   1.000   0.18500
   1.000   0.000  -1.000   0.03400
  -1.000  -1.000   1.000   0.09500
   1.000   1.000  -1.000   0.04800
   0.000   0.000  -1.000   0.04900
  -1.000  -1.000   0.000   0.06800

  11 Faces  +  18 Corners  =  27 Edges  +  2

 Cycle  1     Mu   0.000 mm-1     Rint  0.16945
 Cycle  2     Mu   5.000 mm-1     Rint  0.16010
 Cycle  3     Mu  13.090 mm-1     Rint  0.17267
 Cycle  4     Mu   6.076 mm-1     Rint  0.16026
 Cycle  5     Mu   5.314 mm-1     Rint  0.16008
 Cycle  6     Mu   5.277 mm-1     Rint  0.16008
 Cycle  7     Mu   5.299 mm-1     Rint  0.16008
 Cycle  8     Mu   5.341 mm-1     Rint  0.16008
 All Rint values calculated using  101683 selected reflections only
 Rint 0.1695 for mu = 0 and 0.1601 for mu =   5.315 mm-1
 All Rint values calculated using  101683 selected reflections only
 Minimum and maximum transmission coefficients = 0.39435 and 0.63139
 Minimum and maximum t-bar = 0.0841 and 0.1666 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

  101683 Reflections employed for parameter determination
 Effective data to parameter ratio =  144.67

 wR2(int) =  0.1291 (selected reflections only, before parameter refinement)

 Cycle  wR2(incid)  wR2(diffr)  Mean wt.
    1     0.1145      0.0930     0.7487
    2     0.0873      0.0818     0.7785
    3     0.0799      0.0776     0.7887
    4     0.0767      0.0756     0.7934
    5     0.0751      0.0746     0.7959
    6     0.0742      0.0740     0.7972
    7     0.0737      0.0736     0.7980
    8     0.0734      0.0734     0.7985
    9     0.0732      0.0732     0.7988
   10     0.0731      0.0731     0.7991
   11     0.0730      0.0731     0.7992
   12     0.0730      0.0730     0.7993
   13     0.0729      0.0730     0.7994
   14     0.0729      0.0730     0.7995
   15     0.0728      0.0729     0.7996
   16     0.0728      0.0729     0.7996
   17     0.0728      0.0729     0.7996
   18     0.0728      0.0729     0.7997
   19     0.0728      0.0729     0.7997
   20     0.0728      0.0729     0.7997
   21     0.0728      0.0729     0.7997
   22     0.0728      0.0729     0.7997
   23     0.0728      0.0729     0.7997
   24     0.0728      0.0729     0.7998
   25     0.0727      0.0729     0.7998
   26     0.0727      0.0729     0.7998
   27     0.0727      0.0729     0.7998
   28     0.0727      0.0729     0.7998
   29     0.0727      0.0729     0.7998
   30     0.0727      0.0729     0.7998
   31     0.0727      0.0729     0.7998
   32     0.0727      0.0729     0.7998
   33     0.0727      0.0728     0.7998
   34     0.0727      0.0728     0.7998
   35     0.0727      0.0728     0.7998
   36     0.0727      0.0728     0.7998
   37     0.0727      0.0728     0.7998
   38     0.0727      0.0728     0.7998
   39     0.0727      0.0728     0.7998
   40     0.0727      0.0728     0.7998
   41     0.0727      0.0728     0.7998
   42     0.0727      0.0728     0.7998
   43     0.0727      0.0728     0.7998
   44     0.0727      0.0728     0.7998
   45     0.0727      0.0728     0.7998
   46     0.0727      0.0728     0.7998
   47     0.0727      0.0728     0.7998
   48     0.0727      0.0728     0.7998
   49     0.0727      0.0728     0.7998
   50     0.0727      0.0728     0.7998

 wR2(int) =  0.0728 (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:

  184690 total and  28665 unique reflections assuming Friedel's law

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

  182486 total and  28664 unique reflections left after |I-<I>|/su test

 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)
   1   0.0  0.2750  0.579 - 0.774  0.834 - 1.473  1.382  0.0593  16.9   76211   23435
   2  15.8  0.0724  0.676 - 0.990  0.802 - 1.473  0.851  0.0593  16.9   67988   42778
   3  14.9  0.0810  0.700 - 0.876  0.806 - 1.396  0.861  0.0593  16.9   38287   22630

 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    0.7500      28.99
   2    15.84    0.7500      52.40
   3    14.94    0.7500      48.69

 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

  107451 Reflections of which  28586 unique;  190.52 data per frame

 Redundancy:          1     2     3     4     5     6     7     8     9+
 Number of groups:  2467  6098  5142  6708  3176  2062  1562  1038   333

 Mean(I/sigma):  -inf    0     1     2     3     5    10    15    20   +inf
 Number of groups:  4137  5898  3461  2248  3045  4390  1817  1066  2524

 Reading crystal faces from file:  D:\frames\guest\M5360\work\nac_db.p4p

 Crystal faces:

     H       K       L      d(mm)

   1.000   0.000   1.000   0.06200
  -1.000   0.000   0.000   0.10000
   1.000   0.000   0.000   0.01400
   1.000   1.000   1.000   0.12400
   0.000   1.000   1.000   0.16100
  -1.000   0.000   1.000   0.18500
   1.000   0.000  -1.000   0.03400
  -1.000  -1.000   1.000   0.09500
   1.000   1.000  -1.000   0.04800
   0.000   0.000  -1.000   0.04900
  -1.000  -1.000   0.000   0.06800

  11 Faces  +  18 Corners  =  27 Edges  +  2

 Cycle  1     Mu   0.000 mm-1     Rint  0.14047
 Cycle  2     Mu   5.000 mm-1     Rint  0.12808
 Cycle  3     Mu  13.090 mm-1     Rint  0.13561
 Cycle  4     Mu   7.257 mm-1     Rint  0.12723
 Cycle  5     Mu   6.967 mm-1     Rint  0.12719
 Cycle  6     Mu   6.826 mm-1     Rint  0.12719
 Cycle  7     Mu   6.864 mm-1     Rint  0.12719
 All Rint values calculated using   65086 selected reflections only
 Rint 0.1405 for mu = 0 and 0.1272 for mu =   6.861 mm-1
 All Rint values calculated using   75185 selected reflections only
 Minimum and maximum transmission coefficients = 0.30672 and 0.55501
 Minimum and maximum t-bar = 0.0827 and 0.1625 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

   75185 Reflections employed for parameter determination
 Effective data to parameter ratio =  102.01

 wR2(int) =  0.1214 (selected reflections only, before parameter refinement)

 Cycle  wR2(incid)  wR2(diffr)  Mean wt.
    1     0.1061      0.0816     0.8331
    2     0.0749      0.0691     0.8670
    3     0.0667      0.0644     0.8772
    4     0.0635      0.0624     0.8816
    5     0.0619      0.0613     0.8839
    6     0.0611      0.0607     0.8851
    7     0.0606      0.0604     0.8859
    8     0.0602      0.0601     0.8863
    9     0.0600      0.0599     0.8867
   10     0.0598      0.0598     0.8869
   11     0.0597      0.0597     0.8871
   12     0.0596      0.0596     0.8873
   13     0.0595      0.0595     0.8874
   14     0.0595      0.0595     0.8875
   15     0.0594      0.0594     0.8875
   16     0.0594      0.0594     0.8876
   17     0.0593      0.0593     0.8877
   18     0.0593      0.0593     0.8877
   19     0.0593      0.0593     0.8878
   20     0.0592      0.0593     0.8878
   21     0.0592      0.0592     0.8878
   22     0.0592      0.0592     0.8878
   23     0.0592      0.0592     0.8879
   24     0.0592      0.0592     0.8879
   25     0.0592      0.0592     0.8879
   26     0.0591      0.0592     0.8879
   27     0.0591      0.0591     0.8879
   28     0.0591      0.0591     0.8879
   29     0.0591      0.0591     0.8879
   30     0.0591      0.0591     0.8879
   31     0.0591      0.0591     0.8880
   32     0.0591      0.0591     0.8880
   33     0.0591      0.0591     0.8880
   34     0.0591      0.0591     0.8880
   35     0.0591      0.0591     0.8880
   36     0.0591      0.0591     0.8880
   37     0.0591      0.0591     0.8880
   38     0.0591      0.0591     0.8880
   39     0.0591      0.0591     0.8880
   40     0.0591      0.0591     0.8880
   41     0.0590      0.0591     0.8880
   42     0.0590      0.0591     0.8880
   43     0.0590      0.0591     0.8880
   44     0.0590      0.0591     0.8880
   45     0.0590      0.0591     0.8880
   46     0.0590      0.0591     0.8880
   47     0.0590      0.0591     0.8880
   48     0.0590      0.0591     0.8880
   49     0.0590      0.0591     0.8880
   50     0.0590      0.0591     0.8880

 wR2(int) =  0.0591 (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:

  107451 total and  28586 unique reflections assuming Friedel's law
 plus  12671 total and  3678 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)

  107298 total and  28585 unique reflections left after |I-<I>|/su test
 plus  12210 total and  3669 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  0.0868  0.660 - 0.873  0.849 - 1.308  1.470  0.0427  23.4   12210    8617
   2  15.8  0.0649  0.721 - 1.050  0.793 - 1.399  0.901  0.0427  23.4   68772   42464
   3  14.9  0.0722  0.794 - 0.958  0.807 - 1.311  0.866  0.0427  23.4   38526   22686

 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 M5360.eps

 Reflections not merged
       4 Overloads replaced by fast scan measurements
  107302 Corrected reflections written to file M5360_0m.hkl
 Estimated minimum and maximum transmission:  0.0013  0.0113
 The ratio of these values is more reliable than their absolute values!
 Additional spherical absorption correction applied with mu*r =  5.5700
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    3.476
_exptl_crystal_description       plate
_exptl_crystal_F_000             20614
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.300
_refine_diff_density_min         -1.254
_refine_diff_density_rms         0.227
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1245
_refine_ls_number_reflns         20002
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0579
_refine_ls_R_factor_gt           0.0402
_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^)+(0.0502P)^2^+307.7971P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0987
_refine_ls_wR_factor_ref         0.1101
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14852
_reflns_number_total             20002
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03076d2.cif
_cod_data_source_block           2153638
_cod_database_code               7130658
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.223
_shelx_estimated_absorpt_t_min   0.131
_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, All N(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{Rh3, Na3}
{Rh4, Na4}
3. Uiso/Uaniso restraints and constraints
Uanis(Na2) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O2W) \\sim Ueq, Uanis(O55) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(O3W)
\\sim Ueq, Uanis(C24) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(Rh3) = Uanis(Na3)
Uanis(Rh4) = Uanis(Na4)
4. Others
 Sof(H4BC)=Sof(H4BD)=Sof(H3BC)=Sof(H3BD)=Sof(H5BC)=Sof(H5BD)=Sof(H6BC)=
 Sof(H6BD)=Sof(Na3)=Sof(Na4)=0.5*(1-FVAR(2))
 Sof(H4AA)=Sof(H4AB)=Sof(H3AA)=Sof(H3AB)=Sof(H5AA)=Sof(H5AB)=Sof(H6AA)=
 Sof(H6AB)=Sof(Rh3)=Sof(Rh4)=0.5*FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 N4(H4AA,H4AB), N4(H4BC,H4BD), N3(H3AA,H3AB), N3(H3BC,H3BD), N5(H5AA,H5AB),
 N5(H5BC,H5BD), N6(H6AA,H6AB), N6(H6BC,H6BD)
5.b Aromatic/amide H refined with riding coordinates:
 C1W(H1W), C2W(H2W), C3(H3), C4(H4), C5(H5), C6(H6), N8(H8), C10(H10),
 C11(H11), C13(H13), C14(H14), C15(H15), C17(H17), C19(H19), C20(H20), C21(H21),
  C22(H22)
5.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C)
;
_smtbx_masks_special_details
;
 Highly disordered solvent was located in the structures.
 Reflection contributions from this solvent were removed
 using program OLEX2, function MSAKS, which determined
 there to be 1865.4 electrons in 6634.2 \%A^3^ removed per unit cell. 
 This is consistent with the presence of about 46[H2O] per formula unit
 which account for 1840 electrons. Therefore,
 there are 46[H2O] molecules were added to the chemical formulas.
 Thus all reported items that derive from the molecular formula
 (<i>e.g.</i>, <i>F</i>(000), density, molecular weight,
 <i>etc</i>.) are inconsistent with the calculated values.
;
_shelx_res_checksum              81286
_shelx_hkl_checksum              69396
_shelx_fab_checksum              78831
_olex2_submission_special_instructions 'No special instructions were received'