MMCT energy change in cyanidometal-bridged trinuclear complexes by changing the ligand electron donating ability
Qian, Wang; Liu, Xiao-Lin; Tan, Bing-Chang; Song, Ying; Jiang, Long-Long; Wu, Xin-Tao; Sheng, Tian-Lu; New Journal of Chemistry 47 (2023) 7134–7142; doi:10.1039/D2NJ06104J

data_7062367
_publ_section_title
;
 MMCT energy change in cyanidometal-bridged trinuclear complexes by
 changing the ligand electron donating ability
;
_journal_issue                   15
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              7134
_journal_page_last               7142
_journal_paper_doi               10.1039/D2NJ06104J
_journal_volume                  47
_journal_year                    2023
_chemical_formula_moiety         'C102 H114 Fe2 N6 P4 Ru, 2(F6 P)'
_chemical_formula_sum            'C102 H114 F12 Fe2 N6 P6 Ru'
_chemical_formula_weight         2050.57
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-10-10
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-12-14 deposited with the CCDC.	2023-03-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.5060(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   15.27300(10)
_cell_length_b                   17.47840(10)
_cell_length_c                   19.05300(10)
_cell_measurement_reflns_used    74982
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      60.0440
_cell_measurement_theta_min      2.0990
_cell_volume                     4901.03(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.98a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.98a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.98a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_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     47.00  91.00   0.50    0.09    --   76.11  78.00  83.00   88
  2  \w     47.00  74.00   0.50    0.09    --   76.11  77.00  60.00   54
  3  \w     47.00 107.00   0.50    0.09    --   76.11  77.00 120.00  120
  4  \w     97.00 150.00   0.50    0.09    --   76.11  77.00  60.00  106
  5  \w     47.00 149.00   0.50    0.09    --   76.11  77.00 150.00  204
  6  \w     47.00  79.00   0.50    0.09    --   76.11  77.00   0.00   64
  7  \w     89.00 115.00   0.50    0.09    --   76.11  77.00   0.00   52
  8  \w     47.00  72.00   0.50    0.09    --   76.11  77.00 -30.00   50
  9  \w     47.00  79.00   0.50    0.09    --   76.11  77.00  30.00   64
 10  \w     47.00  73.00   0.50    0.09    --   76.11  77.00 -90.00   52
 11  \w     47.00  73.00   0.50    0.09    --   76.11  77.00-120.00   52
 12  \w     47.00  72.00   0.50    0.09    --   76.11  77.00-180.00   50
 13  \w     47.00  72.00   0.50    0.09    --   76.11  77.00-150.00   50
 14  \w    109.00 150.00   0.50    0.09    --   76.11  77.00-180.00   82
 15  \w    121.00 146.00   0.50    0.09    --   76.11  77.00-150.00   50
 16  \w     53.00 149.00   0.50    0.09    --   76.11  57.00-150.00  192
 17  \w     53.00 120.00   0.50    0.09    --   76.11  57.00-120.00  134
 18  \w     53.00  96.00   0.50    0.09    --   76.11  57.00 -30.00   86
 19  \w     53.00 149.00   0.50    0.09    --   76.11  57.00   0.00  192
 20  \w     47.00  81.00   0.50    0.09    --   76.11  77.00  90.00   68
 21  \w    -30.00  73.00   0.50    0.05    --   -0.94  78.00  83.00  206
 22  \w     42.00  73.00   0.50    0.05    --   -0.94  57.00 120.00   62
 23  \w    -23.00  33.00   0.50    0.05    --   -0.94  57.00 120.00  112
 24  \w     81.00 150.00   0.50    0.09    --   76.11 125.00  60.00  138
 25  \w     31.00  79.00   0.50    0.09    --   76.11 -78.00 -41.00   96
 26  \w      2.00  96.00   0.50    0.09    --   76.11 -57.00 -30.00  188
 27  \w      5.00  39.00   0.50    0.09    --   76.11 -77.00 -90.00   68
 28  \w     58.00  93.00   0.50    0.09    --   76.11 -77.00 -90.00   70
 29  \w      3.00 100.00   0.50    0.09    --   76.11 -77.00-180.00  194
 30  \w      2.00 106.00   0.50    0.09    --   76.11 -99.00-180.00  208
 31  \w     41.00  93.00   0.50    0.09    --   76.11-125.00 -30.00  104
 32  \w     71.00 112.00   0.50    0.09    --   76.11-125.00  90.00   82
 33  \w     50.00 106.00   0.50    0.09    --   76.11-125.00 150.00  112
 34  \w     24.00  50.00   0.50    0.09    --   76.11-125.00  90.00   52
 35  \w      0.00  39.00   0.50    0.05    --   -0.94 -99.00 150.00   78
 36  \w      3.00  39.00   0.50    0.05    --   -0.94 -99.00  90.00   72
 37  \w      1.00  39.00   0.50    0.05    --   -0.94 -99.00   0.00   76
 38  \w      4.00  39.00   0.50    0.05    --   -0.94 -99.00 -30.00   70
 39  \w     -3.00  39.00   0.50    0.05    --   -0.94 -99.00 -90.00   84
 40  \w    -46.00   3.00   0.50    0.05    --   -0.94 -78.00 -41.00   98
 41  \w    -73.00  19.00   0.50    0.05    --   -0.94 -38.00 -30.00  184
 42  \w    -72.00  20.00   0.50    0.05    --   -0.94 -38.00-150.00  184
 43  \w    -73.00 -48.00   0.50    0.09    --  -77.99 -78.00 -41.00   50
 44  \w    -73.00 -48.00   0.50    0.09    --  -77.99 -78.00 -74.61   50
 45  \w    -74.00 -49.00   0.50    0.09    --  -77.99 -77.00 -30.00   50
 46  \w   -142.00-117.00   0.50    0.09    --  -77.99 -78.00 -74.61   50
 47  \w   -132.00-106.00   0.50    0.09    --  -77.99 -78.00 -41.00   52
 48  \w    -74.00 -49.00   0.50    0.09    --  -77.99 -77.00   0.00   50
 49  \w    -74.00 -49.00   0.50    0.09    --  -77.99 -77.00-120.00   50
 50  \w   -151.00 -92.00   0.50    0.09    --  -77.99 -77.00 -30.00  118
 51  \w   -152.00 -81.00   0.50    0.09    --  -77.99 -77.00 -60.00  142
 52  \w    -74.00 -49.00   0.50    0.09    --  -77.99 -77.00 -60.00   50
 53  \w    -77.00 -49.00   0.50    0.09    --  -77.99 -77.00 -90.00   56
 54  \w   -152.00-103.00   0.50    0.09    --  -77.99 -75.00-169.19   98
 55  \w    -75.00 -50.00   0.50    0.09    --  -77.99 -75.00-169.19   50
 56  \w   -151.00 -50.00   0.50    0.09    --  -77.99 -77.00  60.00  202
 57  \w    -74.00 -49.00   0.50    0.09    --  -77.99 -77.00 150.00   50
 58  \w   -133.00 -95.00   0.50    0.09    --  -77.99 -77.00 150.00   76
 59  \w    -75.00 -50.00   0.50    0.09    --  -77.99 -75.00  36.97   50
 60  \w    -83.00 -51.00   0.50    0.09    --  -77.99 -72.00 -23.27   64
 61  \w   -153.00 -56.00   0.50    0.09    --  -77.99 -48.00  62.95  194
 62  \w   -151.00-125.00   0.50    0.09    --  -77.99 -44.00  90.36   52
 63  \w    -83.00 -55.00   0.50    0.09    --  -77.99 -44.00  90.36   56
 64  \w   -140.00-101.00   0.50    0.09    --  -77.99 -72.00 -23.27   78
 65  \w   -150.00-112.00   0.50    0.09    --  -77.99 -73.00-151.55   76
 66  \w    -76.00 -51.00   0.50    0.09    --  -77.99 -73.00-151.55   50
 67  \w    -32.00  -4.00   0.50    0.09    --  -77.99  77.00-150.00   56
 68  \w   -107.00 -57.00   0.50    0.09    --  -77.99  77.00-150.00  100
 69  \w    -94.00  -5.00   0.50    0.09    --  -77.99  78.00  83.00  178
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Synergy Custom(Liquid MetalJet D2+)'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0346781000
_diffrn_orient_matrix_UB_12      -0.0024235000
_diffrn_orient_matrix_UB_13      0.0575110000
_diffrn_orient_matrix_UB_21      0.0376713000
_diffrn_orient_matrix_UB_22      0.0680190000
_diffrn_orient_matrix_UB_23      0.0222032000
_diffrn_orient_matrix_UB_31      -0.0752332000
_diffrn_orient_matrix_UB_32      0.0351608000
_diffrn_orient_matrix_UB_33      -0.0390137000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Ga K\a'
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0470
_diffrn_reflns_av_unetI/netI     0.0268
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            148502
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         60.250
_diffrn_reflns_theta_min         2.092
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    3.456
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.37385
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.98a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.390
_exptl_crystal_description       block
_exptl_crystal_F_000             2124
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.446
_refine_diff_density_min         -0.527
_refine_diff_density_rms         0.077
_refine_ls_abs_structure_details
;
 Flack x determined using 8895 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.1713(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1204
_refine_ls_number_reflns         22053
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0521
_refine_ls_R_factor_gt           0.0484
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0750P)^2^+3.8487P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1242
_refine_ls_wR_factor_ref         0.1268
_reflns_Friedel_coverage         0.926
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.982
_reflns_number_gt                20531
_reflns_number_total             22053
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj06104j2.cif
_cod_data_source_block           a_sq
_cod_depositor_comments
'Adding full bibliography for 7062365--7062373.cif.'
_cod_original_cell_volume        4901.03(5)
_cod_database_code               7062367
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O  N P F Cl Ru Fe'
_chemical_oxdiff_usercomment     'C H O  N P F Cl Ru Fe'
_shelx_estimated_absorpt_t_max   0.682
_shelx_estimated_absorpt_t_min   0.479
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     56.82
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F5-F10
 2.1 with sigma of 0.01
3. Rigid bond restraints
 Ru1
 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(Ru1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(F2)=Sof(F5)=Sof(F10)=1-FVAR(1)
 Sof(F032)=Sof(F036)=Sof(F03N)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C01L(H01N), C01T(H01U), C03B(H03G), C03M(H03Z)
6.b Secondary CH2 refined with riding coordinates:
 C028(H02G,H02H), C02A(H02I,H02J), C02P(H02Z,H), C030(H03A,H03B)
6.c Aromatic/amide H refined with riding coordinates:
 C00I(H00I), C00M(H00M), C00R(H00R), C00W(H00W), C00X(H00X), C00Z(H00Z),
 C011(H011), C013(H013), C015(H015), C016(H016), C017(H017), C01A(H01G),
 C01B(H01H), C01C(H01I), C01D(H01J), C01E(H01K), C01H(H01L), C01K(H01M),
 C01M(H01O), C01N(H01P), C01O(H01Q), C01P(H01R), C01Q(H01S), C01S(H01T),
 C01U(H01V), C01V(H01W), C01W(H01X), C01Z(H01Z), C021(H021), C022(H022),
 C026(H026), C029(H029), C02B(H02K), C02C(H02L), C02E(H02P), C02F(H02Q),
 C02G(H02R), C02H(H02S), C02I(H02T), C02K(H02U), C02L(H02V), C02M(H02W),
 C02N(H02X), C02O(H02Y), C02Q(H02), C02R(H1), C02S(H2), C02T(H3), C02V(H5),
 C02X(H7), C02Y(H8), C02Z(H9), C033(H033), C037(H037), C038(H038), C039(H039),
 C03A(H03F), C03F(H03N), C03I(H03U), C03K(H03Y)
6.d Idealised Me refined as rotating group:
 C012(H01A,H01B,H01C), C019(H01D,H01E,H01F), C023(H02A,H02B,H02C), C024(H02D,
 H02E,H02F), C02D(H02M,H02N,H02O), C02U(H4,HA,HB), C02W(H6,HC,HD), C034(H03C,
 H03D,H03E), C03D(H03H,H03I,H03J), C03E(H03K,H03L,H03M), C03G(H03O,H03P,H03Q),
 C03H(H03R,H03S,H03T), C03J(H03V,H03W,H03X), C3(H3A,H3B,H3C)
;
_shelx_res_checksum              6298
_shelx_fab_checksum              27618
_platon_squeeze_void_probe_radius 1.20
_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 1.760
_oxdiff_exptl_absorpt_empirical_full_min 0.610