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_7062369
_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         'C104 H118 Fe2 N6 P4 Ru, 2(F6 P)'
_chemical_formula_sum            'C104 H118 F12 Fe2 N6 P6 Ru'
_chemical_formula_weight         2078.63
_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                 109.935(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.2245(3)
_cell_length_b                   17.8873(3)
_cell_length_c                   19.2837(4)
_cell_measurement_reflns_used    23906
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      59.9600
_cell_measurement_theta_min      2.1180
_cell_volume                     5261.04(18)
_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      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_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     67.00 102.00   0.50    0.05    --   76.11-125.00-150.00   70
  2  \w     29.00  55.00   0.50    0.05    --   76.11-125.00-150.00   52
  3  \w     54.00 150.00   0.50    0.05    --   76.11  19.00 123.00  192
  4  \w     -3.00  36.00   0.50    0.05    --   -0.94  19.00 123.00   78
  5  \w    -53.00 -20.00   0.50    0.05    --  -77.99  57.00 -60.00   66
  6  \w   -106.00   3.00   0.50    0.05    --  -77.99  19.00 123.00  218
  7  \w     42.00  79.00   0.50    0.05    --   -0.94  19.00 123.00   74
  8  \w    -89.00  -5.00   0.50    0.05    --  -77.99  57.00 -90.00  168
  9  \w    -71.00 -27.00   0.50    0.05    --  -77.99  38.00-120.00   88
 10  \w    -67.00 -15.00   0.50    0.05    --  -77.99  38.00 -90.00  104
 11  \w   -134.00 -93.00   0.50    0.05    --  -77.99 -19.00 -43.00   82
 12  \w    -69.00 -12.00   0.50    0.05    --   -0.94 -19.00 -43.00  114
 13  \w   -111.00 -30.00   0.50    0.05    --  -77.99 125.00  90.00  162
 14  \w     -7.00  36.00   0.50    0.05    --   -0.94 -99.00-180.00   86
;
_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      -0.0857418000
_diffrn_orient_matrix_UB_12      0.0144169000
_diffrn_orient_matrix_UB_13      -0.0313846000
_diffrn_orient_matrix_UB_21      0.0114624000
_diffrn_orient_matrix_UB_22      0.0122977000
_diffrn_orient_matrix_UB_23      -0.0646672000
_diffrn_orient_matrix_UB_31      -0.0151173000
_diffrn_orient_matrix_UB_32      -0.0723895000
_diffrn_orient_matrix_UB_33      -0.0170952000
_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  0.0511
_diffrn_reflns_av_unetI/netI     0.0519
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            32694
_diffrn_reflns_point_group_measured_fraction_full 0.716
_diffrn_reflns_point_group_measured_fraction_max 0.713
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         54.820
_diffrn_reflns_theta_min         2.119
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    3.224
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.09236
_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    1.312
_exptl_crystal_description       block
_exptl_crystal_F_000             2156
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.13
_refine_diff_density_max         1.957
_refine_diff_density_min         -2.690
_refine_diff_density_rms         0.109
_refine_ls_abs_structure_details
;
 Flack x determined using 3435 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.072(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1196
_refine_ls_number_reflns         14260
_refine_ls_number_restraints     703
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0588
_refine_ls_R_factor_gt           0.0563
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1060P)^2^+0.0201P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1451
_refine_ls_wR_factor_ref         0.1467
_reflns_Friedel_coverage         0.390
_reflns_Friedel_fraction_full    0.421
_reflns_Friedel_fraction_max     0.414
_reflns_number_gt                13387
_reflns_number_total             14260
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj06104j2.cif
_cod_data_source_block           a_sq_CCDC1
_cod_depositor_comments
'Adding full bibliography for 7062365--7062373.cif.'
_cod_original_cell_volume        5261.03(18)
_cod_database_code               7062369
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C N O F Cl Ni Fe P'
_chemical_oxdiff_usercomment     'C N O F Cl Ni Fe P'
_shelx_estimated_absorpt_t_max   0.679
_shelx_estimated_absorpt_t_min   0.595
_reflns_odcompleteness_completeness 99.95
_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. Rigid bond restraints
 C013
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C013) \\sim Ueq, Uanis(C02D) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C2)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C013) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(Ru1) \\sim Ueq, Uanis(N5)
\\sim Ueq, Uanis(N4) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(N3) \\sim Ueq,
Uanis(N6) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C02Q) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C01C) \\sim Ueq, Uanis(C01H) \\sim Ueq, Uanis(N1) \\sim Ueq,
Uanis(C00R) \\sim Ueq, Uanis(C00U) \\sim Ueq, Uanis(C01T) \\sim Ueq, Uanis(N2)
\\sim Ueq, Uanis(C01K) \\sim Ueq, Uanis(C01O) \\sim Ueq, Uanis(C01D) \\sim Ueq,
Uanis(C00W) \\sim Ueq, Uanis(Fe1) \\sim Ueq, Uanis(C01N) \\sim Ueq, Uanis(C014)
\\sim Ueq, Uanis(C01J) \\sim Ueq, Uanis(C011) \\sim Ueq, Uanis(Fe2) \\sim Ueq,
Uanis(C01L) \\sim Ueq, Uanis(C01M) \\sim Ueq, Uanis(P2) \\sim Ueq, Uanis(P1)
\\sim Ueq, Uanis(C025) \\sim Ueq, Uanis(C02C) \\sim Ueq, Uanis(C02D) \\sim Ueq,
Uanis(C02N) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C02S) \\sim Ueq, Uanis(C00T)
\\sim Ueq, Uanis(P4) \\sim Ueq, Uanis(P3) \\sim Ueq, Uanis(C00V) \\sim Ueq,
Uanis(C01A) \\sim Ueq, Uanis(C01E) \\sim Ueq, Uanis(C026) \\sim Ueq,
Uanis(C02X) \\sim Ueq, Uanis(C02U) \\sim Ueq, Uanis(C03H) \\sim Ueq,
Uanis(C01F) \\sim Ueq, Uanis(C01V) \\sim Ueq, Uanis(C01X) \\sim Ueq,
Uanis(C00X) \\sim Ueq, Uanis(C010) \\sim Ueq, Uanis(C02B) \\sim Ueq, Uanis(C9)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C037) \\sim Ueq,
Uanis(C018) \\sim Ueq, Uanis(C01Y) \\sim Ueq, Uanis(C01Z) \\sim Ueq,
Uanis(C02L) \\sim Ueq, Uanis(C017) \\sim Ueq, Uanis(C01B) \\sim Ueq,
Uanis(C01I) \\sim Ueq, Uanis(C038) \\sim Ueq, Uanis(C030) \\sim Ueq,
Uanis(C02V) \\sim Ueq, Uanis(C02W) \\sim Ueq, Uanis(C036) \\sim Ueq,
Uanis(C03Q) \\sim Ueq, Uanis(C03O) \\sim Ueq, Uanis(C03S) \\sim Ueq,
Uanis(C01Q) \\sim Ueq, Uanis(C02M) \\sim Ueq, Uanis(C019) \\sim Ueq,
Uanis(C02H) \\sim Ueq, Uanis(C00Z) \\sim Ueq, Uanis(C021) \\sim Ueq,
Uanis(C023) \\sim Ueq, Uanis(C02F) \\sim Ueq, Uanis(C03E) \\sim Ueq,
Uanis(C03R) \\sim Ueq, Uanis(C02A) \\sim Ueq, Uanis(C032) \\sim Ueq,
Uanis(C02I) \\sim Ueq, Uanis(C02T) \\sim Ueq, Uanis(C01G) \\sim Ueq,
Uanis(C039) \\sim Ueq, Uanis(C01P) \\sim Ueq, Uanis(C01U) \\sim Ueq,
Uanis(C03K) \\sim Ueq, Uanis(C012) \\sim Ueq, Uanis(C02G) \\sim Ueq,
Uanis(C03B) \\sim Ueq, Uanis(C015) \\sim Ueq, Uanis(C03D) \\sim Ueq,
Uanis(C027) \\sim Ueq, Uanis(C029) \\sim Ueq, Uanis(C02Z) \\sim Ueq,
Uanis(C034) \\sim Ueq, Uanis(C033) \\sim Ueq, Uanis(C03G) \\sim Ueq,
Uanis(C01S) \\sim Ueq, Uanis(C03L) \\sim Ueq, Uanis(C02J) \\sim Ueq,
Uanis(C02R) \\sim Ueq, Uanis(C03P) \\sim Ueq, Uanis(C01R) \\sim Ueq,
Uanis(C035) \\sim Ueq, Uanis(C02Y) \\sim Ueq, Uanis(C02O) \\sim Ueq,
Uanis(C03C) \\sim Ueq, Uanis(C03J) \\sim Ueq, Uanis(C03A) \\sim Ueq,
Uanis(C024) \\sim Ueq, Uanis(C031) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C013) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C3) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
4.a Ternary CH refined with riding coordinates:
 C018(H018), C02U(H02U), C037(H037), C03H(H03U)
4.b Secondary CH2 refined with riding coordinates:
 C00X(H00A,H00B), C017(H01A,H01B), C01X(H01F,H01I), C02L(H02D,H02E)
4.c Aromatic/amide H refined with riding coordinates:
 C00R(H00R), C00U(H00U), C00W(H00W), C00Z(H00Z), C011(H011), C012(H012),
 C013(H013), C014(H014), C015(H015), C019(H019), C01C(H01C), C01D(H01D),
 C01E(H01E), C01G(H01G), C01H(H01H), C01J(H01J), C01K(H01K), C01N(H01N),
 C01O(H01O), C01P(H01P), C01Q(H01Q), C01R(H01R), C01S(H01S), C01T(H01T),
 C01U(H01U), C021(H021), C023(H023), C024(H024), C027(H027), C029(H029),
 C02F(H02F), C02G(H02G), C02H(H02H), C02I(H02I), C02J(H02J), C02M(H02M),
 C02O(H02O), C02Q(H02Q), C02R(H02R), C02T(H02T), C02Y(H02Y), C02Z(H02Z),
 C031(H031), C033(H033), C034(H034), C035(H035), C039(H039), C03A(H03M),
 C03B(H03N), C03C(H03O), C03D(H03P), C03G(H03T), C03J(H03V), C03K(H03W),
 C03L(H03X), C03P(H03Z), C3(H3), C11(H11)
4.d Idealised Me refined as rotating group:
 C02A(H02A,H02B,H02C), C02V(H02K,H02L,H02N), C02W(H02P,H02S,H02V), C030(H03A,
 H03B,H03C), C032(H03D,H03E,H03F), C036(H03G,H03H,H03I), C038(H03J,H03K,H03L),
 C03E(H03Q,H03R,H03S), C03O(H03Y,H,HA), C03Q(H03,HB,HC), C03R(H1,HD,HE),
 C03S(H2,HF,HG), C5(H5A,H5B,H5C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C6(H6A,
 H6B,H6C)
;
_shelx_res_checksum              85364
_shelx_fab_checksum              47487
_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 5.851
_oxdiff_exptl_absorpt_empirical_full_min 0.513