Ligand redox controlled amine dehydrogenation and imine hemilability in singlet diradical azo-aromatic Ni(II) complexes: characterization of the electron transfer series of azo-imine complexes of Ni(II).
Goswami, Bappaditya; Khatua, Manas; Devi, Ambika; Hans, Shivali; Chatterjee, Robindo; Samanta, Subhas; Dalton transactions (Cambridge, England : 2003) 53 (2024) 10250–10260; doi:10.1039/d3dt03414c

data_7716149
_publ_section_title
;
 Ligand redox controlled amine dehydrogenation and imine hemilability in
 singlet diradical azo-aromatic Ni(II) complexes: characterization of the
 electron transfer series of azo-imine complexes of Ni(II).
;
_journal_issue                   24
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10250
_journal_page_last               10260
_journal_paper_doi               10.1039/d3dt03414c
_journal_volume                  53
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety
'C38 H32 N8 Ni O2, 2(Cl O4), 0.375[C4H10O], 0.375[C4H10O]'
_chemical_formula_sum            'C38 H32 Cl2 N8 Ni O10'
_chemical_formula_weight         890.33
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-05-19
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-05-19 deposited with the CCDC.	2024-05-23 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 127.767(6)
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   40.212(8)
_cell_length_b                   8.3825(17)
_cell_length_c                   32.806(7)
_cell_measurement_reflns_used    9085
_cell_measurement_temperature    298.15
_cell_measurement_theta_max      28.096
_cell_measurement_theta_min      2.173
_cell_volume                     8742(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL n/a (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      298.15
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'D8 Venture'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0771
_diffrn_reflns_av_unetI/netI     0.0691
_diffrn_reflns_limit_h_max       53
_diffrn_reflns_limit_h_min       -53
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            107001
_diffrn_reflns_theta_full        28.35
_diffrn_reflns_theta_max         28.35
_diffrn_reflns_theta_min         2.03
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.628
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.5697
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1533 before and 0.0908 after correction.
The Ratio of minimum to maximum transmission is 0.7640.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'metallic dark red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.353
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             3664
_exptl_crystal_size_max          0.024
_exptl_crystal_size_mid          0.016
_exptl_crystal_size_min          0.012
_refine_diff_density_max         0.805
_refine_diff_density_min         -0.533
_refine_diff_density_rms         0.124
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.000(18)
_refine_ls_extinction_coef       0.0015(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1069
_refine_ls_number_reflns         21695
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.1415
_refine_ls_R_factor_gt           0.0873
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1607P)^2^+0.5380P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2226
_refine_ls_wR_factor_ref         0.2639
_reflns_number_gt                13370
_reflns_number_total             21695
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d3dt03414c2.cif
_cod_data_source_block           '[3b]_2ClO4'
_cod_depositor_comments
'Adding full bibliography for 7716146--7716150.cif.'
_cod_original_cell_volume        8741(3)
_cod_database_code               7716149
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.94039
 0.05961
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Aromatic/amide H refined with riding coordinates:
 C31a(H31a), C1A(H1A), C5(H5), C36a(H36a), C20(H20), C24a(H24a), C12(H12),
 C2A(H2A), C18(H18), C35a(H35a), C21(H21), C27(H27), C8A(H8A), C36(H36),
 C12A(H12A), C37(H37), C8(H8), C24(H24), C4(H4), C5A(H5A), C31(H31), C18A(H18A),
  C17(H17), C27a(H27a), C32a(H32a), C23a(H23a), C4A(H4A), C20a(H20a), C23(H23),
 C17A(H17A), C1(H1), C29a(H29a), C10(H10), C28(H28), C14(H14), C9(H9),
 C33a(H33a), C34a(H34a), C28a(H28a), C29(H29), C16A(H16A), C35(H35), C2(H2),
 C9A(H9A), C21a(H21a), C15(H15), C33(H33), C16(H16), C10A(H10A), C34(H34),
 C14A(H14A), C15A(H15A)
3.b Idealised Me refined as rotating group:
 C38(H38a,H38b,H38c), C19A(H19a,H19b,H19c), C38a(H38d,H38e,H38f), C19(H19d,
 H19e,H19f)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 246 electrons were 
found in a volume of 1118\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 0.375[C4H10O],
0.375[C4H10O] per Asymmetric Unit which account for 
252 electrons per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_submission_special_instructions 'No special instructions were received'