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_7714784
_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         'C60 H48 N12 Ru, 2(F6 P), 2(C2 H3 N)'
_chemical_formula_sum            'C64 H54 F12 N14 P2 Ru'
_chemical_formula_weight         1410.22
_chemical_name_common            'Ru(II) complex of pyridine-triazole ligand'
_chemical_name_systematic        '[Ru(Lpyridine)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             2022-10-31
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-03-21 deposited with the CCDC.	2023-12-20 downloaded from the CCDC.
;
_cell_angle_alpha                102.239(3)
_cell_angle_beta                 112.933(3)
_cell_angle_gamma                105.195(3)
_cell_formula_units_Z            2
_cell_length_a                   14.3806(6)
_cell_length_b                   16.2266(5)
_cell_length_c                   17.3781(5)
_cell_measurement_reflns_used    13382
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.7850
_cell_measurement_theta_min      4.7470
_cell_volume                     3371.5(3)
_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 0.994
_diffrn_measured_fraction_theta_max 0.962
_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    -75.00  34.00   1.00    9.00    --  -41.92  77.00   0.00  109
  2  \w    -66.00  32.00   1.00    9.00    --  -41.92  38.00 -90.00   98
  3  \w   -116.00 -17.00   1.00    9.00    --  -41.92 -38.00  90.00   99
  4  \w     57.00 131.00   1.00    9.00    --   41.92 178.00-120.00   74
  5  \w     32.00 133.00   1.00   36.00    --  104.32 -61.00 -60.00  101
  6  \w     27.00  79.00   1.00   36.00    --  104.32 -15.00 -30.00   52
  7  \w     96.00 178.00   1.00   36.00    --  104.32 125.00-150.00   82
  8  \w     26.00 109.00   1.00   36.00    --  104.32 -95.00 150.00   83
  9  \w     47.00 106.00   1.00   36.00    --  104.32 -95.00 -90.00   59
 10  \w     28.00 129.00   1.00   36.00    --  104.32 -30.00 150.00  101
 11  \w     95.00 142.00   1.00   36.00    --  104.32 125.00 -60.00   47
 12  \w     88.00 117.00   1.00   36.00    --  104.32-125.00  90.00   29
 13  \w     98.00 125.00   1.00   36.00    --  104.32  45.00 -60.00   27
 14  \w    138.00 171.00   1.00   36.00    --  104.32  45.00 -60.00   33
 15  \w    108.00 147.00   1.00   36.00    --  104.32 -15.00 -30.00   39
 16  \w     76.00 114.00   1.00   36.00    --  104.32 -61.00 120.00   38
 17  \w     40.00 132.00   1.00   36.00    --  104.32 -30.00-120.00   92
;
_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      0.1010993000
_diffrn_orient_matrix_UB_12      0.0822517000
_diffrn_orient_matrix_UB_13      0.0756934000
_diffrn_orient_matrix_UB_21      0.0742407000
_diffrn_orient_matrix_UB_22      -0.0353845000
_diffrn_orient_matrix_UB_23      -0.0301311000
_diffrn_orient_matrix_UB_31      -0.0111666000
_diffrn_orient_matrix_UB_32      0.0551634000
_diffrn_orient_matrix_UB_33      -0.0628550000
_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  0.0376
_diffrn_reflns_av_unetI/netI     0.0392
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            24603
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.812
_diffrn_reflns_theta_min         3.613
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.052
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82767
_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 orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.389
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1436
_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          0.679
_exptl_crystal_size_mid          0.125
_exptl_crystal_size_min          0.045
_refine_diff_density_max         1.321
_refine_diff_density_min         -0.911
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     910
_refine_ls_number_reflns         12926
_refine_ls_number_restraints     252
_refine_ls_restrained_S_all      1.123
_refine_ls_R_factor_all          0.0651
_refine_ls_R_factor_gt           0.0598
_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^)+(0.0921P)^2^+3.6452P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1615
_refine_ls_wR_factor_ref         0.1662
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11417
_reflns_number_total             12926
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03484d3.cif
_cod_data_source_block           mgr26-1
_cod_depositor_comments
'Adding full bibliography for 7714784--7714786.cif.'
_cod_original_cell_volume        3371.5(2)
_cod_database_code               7714784
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.875
_shelx_estimated_absorpt_t_min   0.231
_reflns_odcompleteness_completeness 99.63
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Rigid body (RIGU) restrains
 P1, F11, F12, F13, F14, F15, F16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P1, F11, F12, F17, F18, F19, F20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P2, F21, F22, F23, F24, F25, F26
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P2, F21, F22, F27, F28, F29, F30
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
2. Same fragment restrains
{P2, F21, F22, F27, F28, F29, F30} sigma for 1-2: 0.02, 1-3: 0.04
as in
{P2, F21, F22, F23, F24, F25, F26}
{P1, F11, F12, F17, F18, F19, F20} sigma for 1-2: 0.02, 1-3: 0.04
as in
{P1, F11, F12, F13, F14, F15, F16}
3. Others
 Fixed Sof: F13(0.6) F14(0.6) F15(0.6) F16(0.6) F17(0.4) F18(0.4) F19(0.4)
 F20(0.4) F23(0.6) F24(0.6) F25(0.6) F26(0.6) F27(0.4) F28(0.4) F29(0.4)
 F30(0.4)
4.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C15(H15), C16(H16), C18(H18), C19(H19), C21(H21), C22(H22), C23(H23),
  C24(H24), C29(H29), C30(H30), C31(H31), C32(H32), C33(H33), C35(H35),
 C36(H36), C38(H38), C39(H39), C41(H41), C42(H42), C43(H43), C44(H44), C49(H49),
  C50(H50), C51(H51), C52(H52), C53(H53), C55(H55), C56(H56), C58(H58), C59(H59)
4.b Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C40(H40A,H40B,H40C), C60(H60A,H60B,H60C), C81(H81A,H81B,
 H81C), C91(H91A,H91B,H91C)
;
_shelx_res_checksum              6591
_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 2.309
_oxdiff_exptl_absorpt_empirical_full_min 0.662
_platon_squeeze_void_probe_radius 1.20