Electrocatalytic Ammonia Oxidation Mediated by a Cu(II) Complex: A Hydrazine Pathway to Hydrogen Generation
Natarajan, Thillai M.; Teja, Deewan Singh; Akhter, Sk Samim; Bhardwaj, Prabhakar; Kumar, Pankaj; Mallik, Bhabani S.; Padhi, Sumanta Kumar; Dalton Transactions  (2026) –; doi:10.1039/D6DT00268D

data_7720717
_publ_section_title
;
 Electrocatalytic ammonia oxidation mediated by a Cu(II) complex: a
 hydrazine pathway to hydrogen generation.
;
_journal_issue                   18
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              7111
_journal_page_last               7126
_journal_paper_doi               10.1039/d6dt00268d
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         '2(C27 H37 Cu N5), 3(F6 P)'
_chemical_formula_sum            'C54 H74 Cu2 F18 N10 P3'
_chemical_formula_weight         1425.241
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_Int_Tables_number      15
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2n7bmw
_audit_creation_date             2025-05-08
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-05-09 deposited with the CCDC.	2026-03-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.358(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.5811(11)
_cell_length_b                   22.9896(14)
_cell_length_c                   17.8190(12)
_cell_measurement_reflns_used    4873
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      24.0940
_cell_measurement_theta_min      2.6840
_cell_volume                     7189.8(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0303
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.9945
_diffrn_measured_fraction_theta_max 0.9945
_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     -8.00  38.00   1.00   25.00    --   14.69  77.00  90.00   46
  2  \w    -32.00  -6.00   1.00   25.00    --  -16.64 -77.00-150.00   26
  3  \w    -14.00  38.00   1.00   25.00    --  -16.64  19.00 150.00   52
  4  \w    -70.00 -43.00   1.00   25.00    --  -16.64-178.00-120.00   27
  5  \w    -27.00  50.00   1.00   25.00    --  -16.64  57.00-150.00   77
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0023148000
_diffrn_orient_matrix_UB_12      -0.0304016000
_diffrn_orient_matrix_UB_13      -0.0062654000
_diffrn_orient_matrix_UB_21      0.0401014000
_diffrn_orient_matrix_UB_22      0.0011716000
_diffrn_orient_matrix_UB_23      0.0070808000
_diffrn_orient_matrix_UB_31      -0.0045157000
_diffrn_orient_matrix_UB_32      -0.0051344000
_diffrn_orient_matrix_UB_33      0.0387299000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0547
_diffrn_reflns_av_unetI/netI     0.1349
_diffrn_reflns_Laue_measured_fraction_full 0.9945
_diffrn_reflns_Laue_measured_fraction_max 0.9945
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            17908
_diffrn_reflns_point_group_measured_fraction_full 0.9945
_diffrn_reflns_point_group_measured_fraction_max 0.9945
_diffrn_reflns_theta_full        24.9988
_diffrn_reflns_theta_max         25.00
_diffrn_reflns_theta_min         1.81
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.744
_exptl_absorpt_correction_T_max  0.875
_exptl_absorpt_correction_T_min  0.849
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.69a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.317
_exptl_crystal_description       block
_exptl_crystal_F_000             2938.507
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.9425
_refine_diff_density_min         -0.7341
_refine_diff_density_rms         0.1212
_refine_ls_d_res_high            0.8409
_refine_ls_d_res_low             11.2342
_refine_ls_goodness_of_fit_ref   1.0002
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    58
_refine_ls_number_parameters     400
_refine_ls_number_reflns         6305
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0002
_refine_ls_R_factor_all          0.1176
_refine_ls_R_factor_gt           0.0691
_refine_ls_shift/su_max          0.0011
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0700P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1590
_refine_ls_wR_factor_ref         0.1808
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              20
_reflns_limit_h_min              -20
_reflns_limit_k_max              27
_reflns_limit_k_min              0
_reflns_limit_l_max              21
_reflns_limit_l_min              0
_reflns_number_gt                3421
_reflns_number_total             6305
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d6dt00268d2.cif
_cod_data_source_block           TN_X05_A
_cod_depositor_comments          'Adding full bibliography for 7720717.cif.'
_cod_database_code               7720717
_chemical_oxdiff_formula         'C N H Cu O S F'
_diffrn_oxdiff_digest_hkl
;
01c198dd096167ec43026543944bb65dc4318f
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C18(H18a,H18b), C7(H7a,H7b), C6(H6a,H6b), C19(H19a,H19b)
2.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C12(H12), C11(H11), C10(H10), C2(H2), C13(H13), C4(H4), C3(H3),
 C16(H16), C15(H15), C14(H14)
2.c Idealised Me refined as rotating group:
 C21(H21a,H21b,H21c), C23(H23a,H23b,H23c), C22(H22a,H22b,H22c), C27(H27a,H27b,
 H27c), C25(H25a,H25b,H25c), C26(H26a,H26b,H26c)
;
_smtbx_masks_void_probe_radius   0.9
_smtbx_masks_void_truncation_radius 0.8
_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 2.049
_oxdiff_exptl_absorpt_empirical_full_min 0.595