Unravelling the role of –OCH3 positional isomerism and dihedral angle in Ni(ii)-dppe dithiolates for enhanced heterogeneous electrocatalytic oxygen evolution reaction (OER)
Srivastava, Devyani; Kushwaha, Aparna; Chauhan, Ratna; Gosavi, Suresh W.; Ahmed, Sarfaraz; Kociok-Köhn, Gabriele; Kumar, Abhinav; CrystEngComm 27 (2025) 1460–1473; doi:10.1039/D4CE01268B

data_7249840
_publ_section_title
;
 Unravelling the role of --OCH3 positional isomerism and dihedral angle in
 Ni(ii)-dppe dithiolates for enhanced heterogeneous electrocatalytic
 oxygen evolution reaction (OER)
;
_journal_issue                   10
_journal_name_full               CrystEngComm
_journal_page_first              1460
_journal_page_last               1473
_journal_paper_doi               10.1039/D4CE01268B
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C36 H31 N Ni O P2 S2, C H Cl3'
_chemical_formula_sum            'C37 H32 Cl3 N Ni O P2 S2'
_chemical_formula_weight         797.75
_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_method           SHELXL-2018/3
_audit_update_record
;
2023-02-03 deposited with the CCDC.	2025-01-27 downloaded from the CCDC.
;
_cell_angle_alpha                76.974(3)
_cell_angle_beta                 89.738(2)
_cell_angle_gamma                81.370(3)
_cell_formula_units_Z            4
_cell_length_a                   15.1870(4)
_cell_length_b                   15.6264(6)
_cell_length_c                   15.9554(5)
_cell_measurement_reflns_used    12024
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      72.6830
_cell_measurement_theta_min      4.1690
_cell_volume                     3645.6(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.56a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.56a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.56a (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      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1150
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.965
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_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  0.0341
_diffrn_reflns_av_unetI/netI     0.0527
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            26634
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.054
_diffrn_reflns_theta_min         3.595
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.938
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50970
_exptl_absorpt_correction_type   multi-scan
_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            orange
_exptl_crystal_density_diffrn    1.453
_exptl_crystal_description       needle
_exptl_crystal_F_000             1640
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: CHCl3'
_exptl_crystal_size_max          0.255
_exptl_crystal_size_mid          0.056
_exptl_crystal_size_min          0.036
_refine_diff_density_max         0.976
_refine_diff_density_min         -0.883
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     923
_refine_ls_number_reflns         14071
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0677
_refine_ls_R_factor_gt           0.0547
_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^)+(0.0669P)^2^+4.4815P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1387
_refine_ls_wR_factor_ref         0.1474
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11465
_reflns_number_total             14071
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ce01268b2.cif
_cod_data_source_block           Ni-L1
_cod_depositor_comments
'Adding full bibliography for 7249838--7249840.cif.'
_cod_database_code               7249840
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.366
_shelx_estimated_absorpt_t_max   0.842
_oxdiff_exptl_absorpt_empirical_full_min 0.599
_oxdiff_exptl_absorpt_empirical_full_max 1.707
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_shelx_res_checksum              64901