Predictable electronic tuning of Fe<sup>II</sup> and Ru<sup>II</sup> complexes <i>via</i> choice of azine: correlation of ligand p<i>K</i><sub>a</sub> with <i>E</i><sub>pa</sub>(M<sup>III/II</sup>) of complex.
Robb, Matthew G.; Bondì, Luca; Rodríguez-Jiménez, Santiago; Garden, Anna L.; Jerabek, Paul; Brooker, Sally; Dalton transactions (Cambridge, England : 2003) 53 (2024) 1999–2007; doi:10.1039/d3dt03484d

data_7714786
_publ_section_title
;
 Predictable electronic tuning of Fe<sup>II</sup> and Ru<sup>II</sup>
 complexes <i>via</i> choice of azine: correlation of ligand
 p<i>K</i><sub>a</sub> with <i>E</i><sub>pa</sub>(M<sup>III/II</sup>) of
 complex.
;
_journal_issue                   5
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              1999
_journal_page_last               2007
_journal_paper_doi               10.1039/d3dt03484d
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C57 H45 N15 Ru, 2(F6 P)'
_chemical_formula_sum            'C57 H45 F12 N15 P2 Ru'
_chemical_formula_weight         1331.09
_chemical_name_common            'Ru(II) complex of pyrimidine-triazole ligand'
_chemical_name_systematic        '[Ru(L4-pyrimidine)3](PF6)2.2MeCN?Et2O'
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-03-21
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-03-21 deposited with the CCDC.	2023-12-20 downloaded from the CCDC.
;
_cell_angle_alpha                103.299(6)
_cell_angle_beta                 112.553(7)
_cell_angle_gamma                105.024(6)
_cell_formula_units_Z            2
_cell_length_a                   14.4360(10)
_cell_length_b                   16.0577(10)
_cell_length_c                   17.3704(12)
_cell_measurement_reflns_used    8585
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.7560
_cell_measurement_theta_min      4.3540
_cell_volume                     3337.6(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3449
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.970
_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   -116.00 -22.00   1.00    7.50    --  -41.79 -38.00   0.00   94
  2  \w   -112.00 -21.00   1.00    7.50    --  -41.79 -38.00  90.00   91
  3  \w   -118.00 -49.00   1.00    7.50    --  -41.79 178.00-150.00   69
  4  \w    -28.00  26.00   1.00    7.50    --   41.79 -57.00-120.00   54
  5  \w     79.00 129.00   1.00    7.50    --   41.79 178.00-180.00   50
  6  \w     62.00 126.00   1.00    7.50    --   41.79 178.00 -60.00   64
  7  \w    121.00 176.00   1.00   25.00    --  112.00  45.00  90.00   55
  8  \w     40.00 133.00   1.00   25.00    --  112.00 -45.00 -30.00   93
  9  \w     42.00 138.00   1.00   25.00    --  112.00 -61.00-150.00   96
 10  \w    123.00 173.00   1.00   25.00    --  112.00 125.00-120.00   50
 11  \w     31.00 164.00   1.00   25.00    --  112.00 -15.00 -90.00  133
 12  \w     90.00 117.00   1.00   25.00    --  112.00-125.00 -30.00   27
 13  \w     30.00  79.00   1.00   25.00    --  112.00 -95.00-180.00   49
 14  \w     51.00 118.00   1.00   25.00    --  112.00-125.00  30.00   67
 15  \w     62.00 118.00   1.00   25.00    --  112.00-125.00-120.00   56
 16  \w     61.00  91.00   1.00   25.00    --  112.00 -95.00  30.00   30
 17  \w     55.00  82.00   1.00   25.00    --  112.00-125.00-180.00   27
 18  \w     86.00 116.00   1.00   25.00    --  112.00-125.00-180.00   30
 19  \w     37.00 138.00   1.00   25.00    --  112.00 -30.00 150.00  101
 20  \w     77.00 105.00   1.00   25.00    --  112.00-125.00 -90.00   28
 21  \w     31.00 128.00   1.00   25.00    --  112.00 -15.00  60.00   97
 22  \w     74.00 118.00   1.00   25.00    --  112.00-125.00 120.00   44
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0344321000
_diffrn_orient_matrix_UB_12      0.0499011000
_diffrn_orient_matrix_UB_13      -0.0563190000
_diffrn_orient_matrix_UB_21      0.1078875000
_diffrn_orient_matrix_UB_22      -0.0143589000
_diffrn_orient_matrix_UB_23      0.0352280000
_diffrn_orient_matrix_UB_31      -0.0536067000
_diffrn_orient_matrix_UB_32      -0.0934345000
_diffrn_orient_matrix_UB_33      -0.0791618000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0688
_diffrn_reflns_av_unetI/netI     0.0843
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            27976
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.683
_diffrn_reflns_theta_min         3.595
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.055
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76746
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
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    1.325
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1348
_exptl_crystal_preparation       'redox and theoretical (DFT) study'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: vapour diffusion of diethyl ether into acetonitrile solution'
_exptl_crystal_size_max          0.189
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.029
_refine_diff_density_max         1.999
_refine_diff_density_min         -1.022
_refine_diff_density_rms         0.127
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.112
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     787
_refine_ls_number_reflns         13638
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.112
_refine_ls_R_factor_all          0.1240
_refine_ls_R_factor_gt           0.0967
_refine_ls_shift/su_max          0.030
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1772P)^2^+1.7912P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2727
_refine_ls_wR_factor_ref         0.3036
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9137
_reflns_number_total             13638
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03484d3.cif
_cod_data_source_block           mgr33
_cod_depositor_comments
'Adding full bibliography for 7714784--7714786.cif.'
_cod_original_cell_volume        3337.6(4)
_cod_database_code               7714786
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         RuCHNPF
_chemical_oxdiff_usercomment     L1081
_shelx_estimated_absorpt_t_max   0.917
_shelx_estimated_absorpt_t_min   0.596
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C45(H45), C1(H1), C12(H12), C39(H39), C41(H41), C50(H50), C22(H22), C7(H7),
 C26(H26), C34(H34), C40(H40), C49(H49), C3(H3), C2(H2), C8(H8), C27(H27),
 C31(H31), C21(H21), C35(H35), C19(H19), C38(H38), C30(H30), C46(H46), C37(H37),
  C53(H53), C16(H16), C36(H36), C11(H11), C15(H15), C20(H20), C55(H55),
 C17(H17), C57(H57), C18(H18), C56(H56), C54(H54)
2.b Idealised Me refined as rotating group:
 C48(H48A,H48B,H48C), C29(H29A,H29B,H29C), C10(H10A,H10B,H10C)
;
_shelx_res_checksum              6059
_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 2.412
_oxdiff_exptl_absorpt_empirical_full_min 0.583
_platon_squeeze_void_probe_radius 1.20