Ferrocene-containing Schiff bases and their Sn(iv) complexes with two non-conjugated redox-active fragments: dependence of spectroscopic and redox properties on complexation and solvent
Proshutinskaya, Varvara Yu.; Krylova, Irina V.; Shangin, Pavel G.; Vilman, Victoriya A.; Minyaev, Mikhail E.; Gorbunov, Dmitry E.; Gritsan, Nina P.; Nikolaevskaya, Elena N.; Egorov, Mikhail P.; Tretyakov, Evgeny V.; Syroeshkin, Mikhail A.; New Journal of Chemistry 50 (2026) 3906–3925; doi:10.1039/D5NJ04462F

data_7064256
_publ_section_title
;
 Ferrocene-containing Schiff bases and their Sn(iv) complexes with two
 non-conjugated redox-active fragments: dependence of spectroscopic and
 redox properties on complexation and solvent
;
_journal_issue                   9
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              3906
_journal_page_last               3925
_journal_paper_doi               10.1039/D5NJ04462F
_journal_volume                  50
_journal_year                    2026
_chemical_formula_moiety         'C48 H56 Fe2 N8 O4 Sn2, 4(C H4 O)'
_chemical_formula_sum            'C52 H72 Fe2 N8 O8 Sn2'
_chemical_formula_weight         1286.25
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-03-31
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2025-07-24 deposited with the CCDC.	2026-02-02 downloaded from the CCDC.
;
_cell_angle_alpha                97.9351(14)
_cell_angle_beta                 90.0735(13)
_cell_angle_gamma                104.0650(14)
_cell_formula_units_Z            1
_cell_length_a                   7.63447(12)
_cell_length_b                   10.59566(18)
_cell_length_c                   17.0440(3)
_cell_measurement_reflns_used    16194
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.5520
_cell_measurement_theta_min      4.3310
_cell_volume                     1323.72(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.109a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.92a 64-bit (release 05-10-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.109a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_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 0.999
_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    -43.00  31.00   0.50    0.16    --    0.00  95.00-165.00  148
  2  \w    -10.00  44.00   0.50    0.16    --    0.00 -95.00  85.00  108
  3  \w   -141.00 -83.00   0.50    0.64    --  -60.75 -95.00  85.00  116
  4  \w    -80.00  21.00   0.50    0.64    --  -60.75  95.00-165.00  202
  5  \w     -9.00 104.00   0.50    0.64    --   60.75 -95.00  85.00  226
  6  \w   -177.00 -83.00   0.50    0.64    -- -100.00 -95.00  85.00  188
  7  \w    -80.00 -19.00   0.50    0.64    -- -100.00  95.00-165.00  122
  8  \w     41.00 106.00   0.50    0.64    --  121.50 -95.00  85.00  130
  9  \w    105.00 178.00   0.50    0.64    --  121.50  95.00-165.00  146
 10  \w     -1.00  44.00   0.50    0.16    --    0.00 -99.00-150.00   90
 11  \w     -1.00  44.00   0.50    0.16    --    0.00 -99.00 -60.00   90
 12  \w    -75.00  35.00   0.50    0.16    --    0.00 -77.00   0.00  220
 13  \w    -75.00  35.00   0.50    0.16    --    0.00 -77.00   0.00  220
 14  \w    -43.00  20.00   0.50    0.64    --  -60.75  38.00-120.00  126
 15  \w   -140.00 -86.00   0.50    0.64    --  -60.75 -99.00   0.00  108
 16  \w    -43.00  20.00   0.50    0.64    --  -60.75  38.00 120.00  126
 17  \w   -140.00 -86.00   0.50    0.64    --  -60.75 -99.00-180.00  108
 18  \w    -25.00  27.00   0.50    0.64    --   60.75 -19.00   0.00  104
 19  \w     34.00 111.00   0.50    0.64    --   60.75-125.00  90.00  154
 20  \w    -25.00  27.00   0.50    0.64    --   60.75 -19.00 -90.00  104
 21  \w    -25.00  27.00   0.50    0.64    --   60.75 -19.00 150.00  104
 22  \w    -71.00 -24.00   0.50    0.64    -- -100.00  61.00 -30.00   94
 23  \w    -71.00 -24.00   0.50    0.64    -- -100.00  61.00-150.00   94
 24  \w    -51.00 -21.00   0.50    0.64    -- -100.00  45.00  60.00   60
 25  \w    -51.00 -21.00   0.50    0.64    -- -100.00  45.00 -30.00   60
 26  \w    -51.00 -21.00   0.50    0.64    -- -100.00  45.00  30.00   60
 27  \w   -176.00 -73.00   0.50    0.64    -- -100.00 -56.00 -16.27  206
 28  \w   -176.00 -73.00   0.50    0.64    -- -100.00 -56.00 -16.27  206
 29  \w     84.00 178.00   0.50    0.64    --  121.50  30.00-180.00  188
 30  \w     84.00 178.00   0.50    0.64    --  121.50  30.00-180.00  188
 31  \w    103.00 178.00   0.50    0.64    --  121.50 111.00 -60.00  150
 32  \w     47.00 105.00   0.50    0.64    --  121.50 -77.00-180.00  116
 33  \w     45.00 108.00   0.50    0.64    --  121.50-111.00 -30.00  126
 34  \w     87.00 178.00   0.50    0.64    --  121.50  77.00  90.00  182
 35  \w     41.00 106.00   0.50    0.64    --  121.50 -95.00  60.00  130
 36  \w    103.00 178.00   0.50    0.64    --  121.50 111.00 150.00  150
 37  \w     47.00 105.00   0.50    0.64    --  121.50 -77.00 -90.00  116
 38  \w     45.00 108.00   0.50    0.64    --  121.50-111.00 -60.00  126
 39  \w     45.00 108.00   0.50    0.64    --  121.50-111.00-150.00  126
 40  \w     42.00 131.00   0.50    0.64    --  121.50  15.00 -90.00  178
 41  \w     42.00 131.00   0.50    0.64    --  121.50  15.00 -90.00  178
 42  \w     70.00 103.00   0.50    0.64    --  121.50-111.00  30.00   66
 43  \w     45.00 108.00   0.50    0.64    --  121.50-111.00-120.00  126
 44  \w    125.00 174.00   0.50    0.64    --  121.50 111.00   0.00   98
 45  \w     59.00 104.00   0.50    0.64    --  121.50-111.00-180.00   90
 46  \w     43.00  83.00   0.50    0.64    --  121.50 -95.00-150.00   80
 47  \w     55.00  81.00   0.50    0.64    --  121.50 -95.00-180.00   52
 48  \w    109.00 176.00   0.50    0.64    --  121.50 111.00-150.00  134
 49  \w     46.00 108.00   0.50    0.64    --  121.50-111.00 150.00  124
 50  \w     41.00  80.00   0.50    0.64    --  121.50 -95.00 -90.00   78
 51  \w    129.00 155.00   0.50    0.64    --  121.50  77.00 120.00   52
 52  \w     47.00 108.00   0.50    0.64    --  121.50-111.00  90.00  122
 53  \w     79.00 105.00   0.50    0.64    --  121.50 -88.00  98.98   52
 54  \w     85.00 112.00   0.50    0.64    --  121.50 178.00-180.00   54
 55  \w     63.00 124.00   0.50    0.64    --  121.50 178.00  90.00  122
 56  \w    144.00 171.00   0.50    0.64    --  121.50  77.00-120.00   54
 57  \w     93.00 174.00   0.50    0.64    --  121.50  45.00  60.00  162
 58  \w     59.00  94.00   0.50    0.64    --  121.50 -77.00 120.00   70
 59  \w     93.00 119.00   0.50    0.64    --  121.50  77.00 -90.00   52
 60  \w    141.00 176.00   0.50    0.64    --  121.50  77.00 -90.00   70
 61  \w    141.00 168.00   0.50    0.64    --  121.50 111.00  60.00   54
 62  \w    120.00 159.00   0.50    0.64    --  121.50 -86.00 157.15   78
 63  \w     46.00 106.00   0.50    0.64    --  121.50-111.00  60.00  120
 64  \w     45.00  76.00   0.50    0.64    --  121.50 -84.00 -11.51   62
 65  \w    105.00 131.00   0.50    0.64    --  121.50 -84.00 -11.51   52
 66  \w    117.00 142.00   0.50    0.64    --  121.50  61.00-120.00   50
 67  \w     48.00  74.00   0.50    0.64    --  121.50 -77.00   0.00   52
 68  \w     69.00  95.00   0.50    0.64    --  121.50 -77.00  90.00   52
 69  \w     47.00  82.00   0.50    0.64    --  121.50 -77.00 150.00   70
 70  \w     78.00 104.00   0.50    0.64    --  121.50 -95.00 -30.00   52
 71  \w     81.00 107.00   0.50    0.64    --  121.50-111.00-150.00   52
 72  \w     42.00  67.00   0.50    0.64    --  121.50 -95.00-120.00   50
 73  \w     44.00  70.00   0.50    0.64    --  121.50 -95.00 -30.00   52
 74  \w    129.00 177.00   0.50    0.64    --  121.50  45.00 -60.00   96
 75  \w    143.00 177.00   0.50    0.64    --  121.50  17.00  46.06   68
 76  \w    111.00 139.00   0.50    0.64    --  121.50  17.00  46.06   56
 77  \w     72.00 104.00   0.50    0.64    --  121.50 -95.00-120.00   64
 78  \w     54.00  80.00   0.50    0.64    --  121.50 -95.00 150.00   52
 79  \w    134.00 160.00   0.50    0.64    --  121.50 111.00-180.00   52
 80  \w     63.00  98.00   0.50    0.64    --  121.50 178.00 -60.00   70
 81  \w     78.00 104.00   0.50    0.64    --  121.50 178.00 -30.00   52
 82  \w    122.00 148.00   0.50    0.64    --  121.50  61.00-180.00   52
 83  \w     92.00 123.00   0.50    0.64    --  121.50  45.00 -90.00   62
 84  \w     73.00  99.00   0.50    0.64    --  121.50  17.00  46.06   52
 85  \w     47.00 108.00   0.50    0.64    --  121.50-111.00   0.00  122
 86  \w    112.00 138.00   0.50    0.64    --  121.50 -88.00  98.98   52
 87  \w     42.00 128.00   0.50    0.64    --  121.50  15.00  30.00  172
 88  \w   -136.00-111.00   0.50    0.64    --  -60.75 -95.00  85.00   50
 89  \w    139.00 165.00   0.50    0.64    --  121.50  61.00 150.00   52
 90  \w    113.00 139.00   0.50    0.64    --  121.50   0.00  60.00   52
 91  \w    153.00 178.00   0.50    0.64    --  121.50   0.00  60.00   50
 92  \w     66.00  92.00   0.50    0.64    --  121.50 -77.00  90.00   52
 93  \w     50.00  76.00   0.50    0.64    --  121.50  15.00 -30.00   52
 94  \w    128.00 154.00   0.50    0.64    --  121.50  15.00 -30.00   52
 95  \w     75.00 101.00   0.50    0.64    --  121.50 178.00 -90.00   52
 96  \w    111.00 137.00   0.50    0.64    --  121.50 178.00 -60.00   52
 97  \w    102.00 128.00   0.50    0.64    --  121.50 178.00 120.00   52
 98  \w    110.00 136.00   0.50    0.64    --  121.50  61.00  30.00   52
 99  \w     71.00  97.00   0.50    0.64    --  121.50  24.00 125.54   52
100  \w    118.00 144.00   0.50    0.64    --  121.50 -84.00-119.91   52
101  \w    131.00 157.00   0.50    0.64    --  121.50 -87.00-133.58   52
102  \w    120.00 146.00   0.50    0.64    --  121.50 111.00-120.00   52
103  \w     31.00  57.00   0.50    0.16    --    0.00  77.00 -90.00   52
104  \w    -16.00  18.00   0.50    0.64    --   60.75 -19.00-150.00   68
105  \w    140.00 166.00   0.50    0.64    --  121.50  30.00 -90.00   52
106  \w    112.00 138.00   0.50    0.64    --  121.50 111.00 120.00   52
107  \w    133.00 159.00   0.50    0.64    --  121.50 -86.00-167.65   52
108  \w    105.00 131.00   0.50    0.64    --  121.50  45.00-180.00   52
109  \w     94.00 120.00   0.50    0.64    --  121.50  30.00 -60.00   52
110  \w    147.00 173.00   0.50    0.64    --  121.50  30.00 -60.00   52
111  \w     87.00 114.00   0.50    0.64    --  121.50  30.00  60.00   54
112  \w     83.00 108.00   0.50    0.64    --  121.50-111.00-180.00   50
113  \w     47.00  73.00   0.50    0.64    --  121.50-111.00 -90.00   52
114  \w     81.00 107.00   0.50    0.64    --  121.50-111.00  60.00   52
115  \w     79.00 105.00   0.50    0.64    --  121.50 -95.00-120.00   52
116  \w     52.00  78.00   0.50    0.64    --  121.50 -95.00 -60.00   52
117  \w     76.00 102.00   0.50    0.64    --  121.50 -95.00   0.00   52
118  \w     58.00  84.00   0.50    0.64    --  121.50 -77.00-120.00   52
119  \w     68.00  94.00   0.50    0.64    --  121.50 178.00-150.00   52
120  \w     88.00 114.00   0.50    0.64    --  121.50 178.00  60.00   52
121  \w     97.00 123.00   0.50    0.64    --  121.50  45.00-150.00   52
122  \w    132.00 157.00   0.50    0.64    --  121.50 -79.00-109.29   50
123  \w    114.00 140.00   0.50    0.64    --  121.50 -85.00  52.87   52
124  \w    113.00 139.00   0.50    0.64    --  121.50 -88.00  96.32   52
125  \w     78.00 104.00   0.50    0.64    --  121.50 -87.00-127.68   52
126  \w    136.00 161.00   0.50    0.64    --  121.50 -87.00-127.68   50
127  \w    116.00 142.00   0.50    0.64    --  121.50 -87.00  87.54   52
128  \w     52.00  78.00   0.50    0.64    --  121.50  12.00 153.35   52
129  \w     81.00 106.00   0.50    0.64    --  121.50 -95.00  30.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1348308000
_diffrn_orient_matrix_UB_12      0.0081291000
_diffrn_orient_matrix_UB_13      -0.0653259000
_diffrn_orient_matrix_UB_21      -0.0608466000
_diffrn_orient_matrix_UB_22      0.1084453000
_diffrn_orient_matrix_UB_23      0.0548234000
_diffrn_orient_matrix_UB_31      0.1464599000
_diffrn_orient_matrix_UB_32      0.1053892000
_diffrn_orient_matrix_UB_33      -0.0326567000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0105
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            10270
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.409
_diffrn_reflns_theta_min         4.346
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.218
_exptl_absorpt_correction_T_max  0.379
_exptl_absorpt_correction_T_min  0.200
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.109a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Spherical absorption correction
using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear pale yellow'
_exptl_crystal_density_diffrn    1.614
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             656
_exptl_crystal_size_max          0.246
_exptl_crystal_size_mid          0.187
_exptl_crystal_size_min          0.159
_refine_diff_density_max         1.787
_refine_diff_density_min         -1.108
_refine_diff_density_rms         0.137
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     346
_refine_ls_number_reflns         10270
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      2.728
_refine_ls_R_factor_all          0.0475
_refine_ls_R_factor_gt           0.0470
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0853P)^2^+2.5823P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1328
_refine_ls_wR_factor_ref         0.1331
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10122
_reflns_number_total             10270
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9720\% 
around [-0.00 0.00 1.00] (reciprocal) or [0.08 0.23 0.97] (direct)
;
_cod_data_source_file            d5nj04462f2.cif
_cod_data_source_block           V30
_cod_depositor_comments
'Adding full bibliography for 7064255--7064256.cif.'
_cod_database_code               7064256
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C52 H72 Fe2 N6 O10 Sn2'
_chemical_oxdiff_usercomment     V30
_shelx_estimated_absorpt_t_max   0.247
_shelx_estimated_absorpt_t_min   0.153
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5706(10)
 0.4294(10)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups, All O(H) groups
3. Restrained distances
 N2-H2A = O3-H3A = O3A-H3B = O4-H4A
 0.84 with sigma of 0.02
 C23-C24 \\sim C23-C24A
 with sigma of 0.003
 C25-O3 \\sim C25-O3A
 with sigma of 0.003
4. Uiso/Uaniso restraints and constraints
Uanis(C24) = Uanis(C24A)
Uanis(O3) = Uanis(O3A)
5. Others
 Sof(H23C)=Sof(H23D)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=1-FVAR(1)
 Sof(H23A)=Sof(H23B)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(1)
 Sof(O3A)=Sof(H3B)=Sof(H25D)=Sof(H25E)=Sof(H25F)=1-FVAR(2)
 Sof(O3)=Sof(H3A)=Sof(H25A)=Sof(H25B)=Sof(H25C)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2A), C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10)
6.b Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C23(H23A,H23B), C23(H23C,H23D)
6.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C17(H17), C18(H18), C19(H19), C20(H20)
6.d Aromatic/amide H refined with riding coordinates and stretchable bonds:
 N2(H2)
6.e Tetrahedral OH refined with riding coordinates and stretchable bonds:
 O3A(H3B)
6.f Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C), C24A(H24D,H24E,
 H24F), C25(H25A,H25B,H25C), C25(H25D,H25E,H25F), C26(H26A,H26B,H26C)
6.g Idealised tetrahedral OH refined as rotating group with stretchable bonds:
 O3(H3A), O4(H4A)
;
_shelx_res_checksum              42400
_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 4.772
_oxdiff_exptl_absorpt_empirical_full_min 0.429
_oxdiff_exptl_absorpt_spherical_max 0.307
_oxdiff_exptl_absorpt_spherical_min 0.215
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2