New 1,2-bis(diphenylphosphino)ethane-laden Co(iii) dithiolate anions: dithiolate-mediated tuning of electrocatalytic performance for non-aqueous hydrogen evolution reaction
Srivastava, Shreya; Srivastava, Devyani; Kushwaha, Aparna; Omoding, Daniel; Kociok-Köhn, Gabriele; Kumar, Abhinav; New Journal of Chemistry 49 (2025) 13175–13188; doi:10.1039/D5NJ02374B

data_7063869
_publ_section_title
;
 New 1,2-bis(diphenylphosphino)ethane-laden Co(iii) dithiolate anions:
 dithiolate-mediated tuning of electrocatalytic performance for
 non-aqueous hydrogen evolution reaction
;
_journal_issue                   30
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              13175
_journal_page_last               13188
_journal_paper_doi               10.1039/D5NJ02374B
_journal_volume                  49
_journal_year                    2025
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C34 H24 Co N4 P2 S4, C8 H20 N [+ solvent]'
_chemical_formula_sum            'C42 H44 Co N5 P2 S4'
_chemical_formula_weight         867.93
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
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_audit_update_record
;
2025-02-07 deposited with the CCDC.	2025-06-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
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_cell_length_c                   46.2728(7)
_cell_measurement_reflns_used    65828
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      27.5250
_cell_measurement_theta_min      3.0870
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_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics
'ORTEP3 for Windows - Farrugia, L. J. J. Appl. Crystallogr. 1997, 30, 565'
_computing_publication_material
;
 'WinGX publication routines, Farrugia, 
 L. J., J. Appl. Crystallogr., 1999, 32, 837-838
;
_computing_structure_refinement
;
 SHELXL-2018/3 (Sheldrick, 2018)
 Sheldrick GM (2008) Acta Crystallogr A64:112--122 and 
 C. B. H\"ubschle, G. M. Sheldrick and B. Dittrich
 ShelXle: a Qt graphical user interface for SHELXL
 J. Appl. Cryst., 44, (2011) 1281-1284.
;
_computing_structure_solution
; 
 SHELXT
 Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.0(2)
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_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Xcalibur, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1268
_diffrn_reflns_av_unetI/netI     0.0949
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
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_diffrn_reflns_limit_h_min       -19
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_diffrn_reflns_limit_k_min       -46
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_diffrn_reflns_limit_l_min       -57
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_diffrn_reflns_point_group_measured_fraction_full 0.998
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_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.331
_diffrn_reflns_theta_min         2.733
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.684
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_exptl_absorpt_correction_T_min  0.56402
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_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.304
_exptl_crystal_description       block
_exptl_crystal_F_000             10848
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CHCl2/EtOH'
_exptl_crystal_size_max          0.817
_exptl_crystal_size_mid          0.541
_exptl_crystal_size_min          0.307
_refine_diff_density_max         1.693
_refine_diff_density_min         -0.694
_refine_diff_density_rms         0.099
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.051(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
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_refine_ls_number_reflns         53839
_refine_ls_number_restraints     230
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.1022
_refine_ls_R_factor_gt           0.0696
_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^)+(0.0495P)^2^+52.5250P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1425
_refine_ls_wR_factor_ref         0.1605
_reflns_Friedel_coverage         0.970
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                40395
_reflns_number_total             53839
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj02374b2.cif
_cod_data_source_block           e22gkk12_sq
_cod_depositor_comments          'Adding full bibliography for 7063869.cif.'
_cod_database_code               7063869
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_shelx_estimated_absorpt_t_min   0.605
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_oxdiff_exptl_absorpt_empirical_full_min 0.774
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_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_shelx_res_checksum              91577
_shelx_fab_checksum              56857