A tetradentate benzannulated P^N^N^P ligand and its Fe(II) complex: synthesis, characterization, and electrocatalytic hydrogen evolution.
Sidhu, Baldeep K.; Kacperkiewicz, Amelia; Braun, Jason D.; Herbert, David E.; Dalton transactions (Cambridge, England : 2003) 54 (2025) 17211–17220; doi:10.1039/d5dt02202a

data_7719774
_publ_section_title
;
 A tetradentate benzannulated P^N^N^P ligand and its Fe(II) complex:
 synthesis, characterization, and electrocatalytic hydrogen evolution.
;
_journal_issue                   46
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              17211
_journal_page_last               17220
_journal_paper_doi               10.1039/d5dt02202a
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety
'C56 H35 Fe N4 P2, 2(C F3 O3 S), C2 H3 N, 1[C2H3N]'
_chemical_formula_sum            'C62 H41 F6 Fe N6 O6 P2 S2'
_chemical_formula_weight         1261.92
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-08-12
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-09-12 deposited with the CCDC.	2025-10-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.553(4)
_cell_length_b                   17.050(5)
_cell_length_c                   27.154(10)
_cell_measurement_reflns_used    9515
_cell_measurement_temperature    150.00
_cell_measurement_theta_max      23.99
_cell_measurement_theta_min      2.50
_cell_volume                     5812(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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150.00
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0755
_diffrn_reflns_av_unetI/netI     0.0512
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            65845
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        24.763
_diffrn_reflns_theta_max         24.763
_diffrn_reflns_theta_min         2.512
_diffrn_source_current           20.0
_diffrn_source_power             1.0
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.463
_exptl_absorpt_correction_T_max  0.7451
_exptl_absorpt_correction_T_min  0.4600
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1020 before and 0.0802 after correction.
The Ratio of minimum to maximum transmission is 0.6174.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.442
_exptl_crystal_description       block
_exptl_crystal_F_000             2580
_exptl_crystal_size_max          0.325
_exptl_crystal_size_mid          0.117
_exptl_crystal_size_min          0.066
_refine_diff_density_max         0.944
_refine_diff_density_min         -0.695
_refine_diff_density_rms         0.102
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.30(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     709
_refine_ls_number_reflns         9932
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.1044
_refine_ls_R_factor_gt           0.0820
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1265P)^2^+13.2754P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2110
_refine_ls_wR_factor_ref         0.2316
_reflns_Friedel_coverage         0.805
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                8046
_reflns_number_total             9932
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02202a2.cif
_cod_data_source_block           deh664_ortho85
_cod_depositor_comments
'Adding full bibliography for 7719773--7719774.cif.'
_cod_database_code               7719774
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.970
_shelx_estimated_absorpt_t_min   0.864
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.70(4)
 0.30(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(F1) = Uanis(F2) = Uanis(F3) = Uanis(F6) = Uanis(F5) = Uanis(F4)
Uanis(C58) = Uanis(C57)
4.a Aromatic/amide H refined with riding coordinates:
 C46(H46), C29(H29), C30(H30), C37(H37), C11(H11), C3(H3), C45(H45), C42(H42),
 C4(H4), C39(H39), C31(H31), C5(H5), C13(H13), C32(H32), C6(H6), C20(H20),
 C26(H26), C52(H52), C43(H43), C48(H48), C16(H16), C50(H50), C24(H24), C25(H25),
  C51(H51), C49(H49), C22(H22), C18(H18), C44(H44), C17(H17), C19(H19), C23(H23)
4.b Idealised Me refined as rotating group:
 C56(H56A,H56B,H56C), C54(H54A,H54B,H54C), C14(H14A,H14B,H14C), C60(H60A,H60B,
 H60C), C40(H40A,H40B,H40C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              16597
_shelx_fab_checksum              91588
_olex2_submission_special_instructions 'No special instructions were received'