Selective NH<sub>3</sub>-to-N<sub>2</sub>H<sub>4</sub> conversion electrocatalysed by ruthenium(ii)-cymene complexes.
Zhang, Xi; Zhao, Shan; Zhou, Chen; Chen, Guo; Cao, Liru; Lin, Jian; Tang, Chen; Liu, Zhi-Yan; He, Piao; Yi, Xiao-Yi; Chemical science 17 (2026) 5595–5603; doi:10.1039/d5sc08826g

data_1576923
_publ_section_title
;
 Selective NH<sub>3</sub>-to-N<sub>2</sub>H<sub>4</sub> conversion
 electrocatalysed by ruthenium(ii)-cymene complexes.
;
_journal_issue                   11
_journal_name_full               'Chemical science'
_journal_page_first              5595
_journal_page_last               5603
_journal_paper_doi               10.1039/d5sc08826g
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         '4(C20 H26 N3 Ru), 4(F6 P)'
_chemical_formula_sum            'C80 H104 F24 N12 P4 Ru4'
_chemical_formula_weight         2217.91
_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             2025-02-26
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2025-02-26 deposited with the CCDC.	2026-01-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.26280(10)
_cell_length_b                   14.3393(2)
_cell_length_c                   42.7074(4)
_cell_measurement_reflns_used    34807
_cell_measurement_temperature    99.98(19)
_cell_measurement_theta_max      76.8520
_cell_measurement_theta_min      3.2240
_cell_volume                     8734.46(16)
_computing_cell_refinement       'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.127a 64-bit (release 16-06-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.98(19)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_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     97.00 147.00   0.50    0.05    --   69.76  86.00 121.00  100
  2  \w    100.00 138.00   0.50    0.05    --  123.00  86.00 121.00   76
  3  \w    116.00 149.00   0.50    0.05    --  123.00  40.00 -70.00   66
  4  \w     69.00  94.00   0.50    0.05    --  123.00  40.00 -70.00   50
  5  \w      7.00  32.00   0.50    0.05    --   69.76 -30.00  90.00   50
  6  \w     40.00  72.00   0.50    0.05    --  123.00 -64.00  90.00   64
  7  \w     40.00  72.00   0.50    0.05    --  123.00 -64.00  60.00   64
  8  \w     43.00  71.00   0.50    0.05    --  123.00 -64.00 150.00   56
  9  \w     48.00 101.00   0.50    0.05    --  123.00 -77.00   0.00  106
 10  \w     46.00  71.00   0.50    0.05    --  123.00 -64.00  30.00   50
 11  \w     43.00  70.00   0.50    0.05    --  123.00 -64.00   0.00   54
 12  \w     43.00  69.00   0.50    0.05    --  123.00 -64.00 -60.00   52
 13  \w     41.00  69.00   0.50    0.05    --  123.00 -64.00 -90.00   56
 14  \w    -11.00  42.00   0.50    0.05    --   69.76 -40.00 136.00  106
 15  \w    -48.00  38.00   0.50    0.05    --   16.53 -40.00 136.00  172
 16  \w     32.00  96.00   0.50    0.05    --  123.00 -77.00 -90.00  128
 17  \w     45.00  73.00   0.50    0.05    --  123.00 -64.00-120.00   56
 18  \w     33.00  69.00   0.50    0.05    --  123.00 -92.00-150.00   72
 19  \w     72.00 100.00   0.50    0.05    --  123.00-109.00 -81.00   56
 20  \w     50.00  99.00   0.50    0.05    --  123.00 -92.00  90.00   98
 21  \w     10.00  39.00   0.50    0.05    --  -16.53 -99.00-180.00   58
 22  \w    -45.00 -19.00   0.50    0.05    --  -97.00  40.00 -70.00   52
 23  \w    -20.00  12.00   0.50    0.05    --  -69.76  40.00 -70.00   64
 24  \w    -31.00   5.00   0.50    0.05    --  -69.76  30.00  60.00   72
 25  \w   -134.00 -93.00   0.50    0.05    --  -97.00-109.00 -81.00   82
 26  \w    -78.00 -47.00   0.50    0.05    --  -15.96 179.00-120.00   62
 27  \w    -77.00  23.00   0.50    0.05    --   15.96 -19.00-120.00  200
 28  \w     46.00  86.00   0.50    0.05    --   15.96 179.00  90.00   80
 29  \w    -22.00   7.00   0.50    0.05    --   15.96 -19.00  30.00   58
 30  \w    -73.00 -47.00   0.50    0.05    --   15.96 -19.00  30.00   52
 31  \w    -27.00   4.00   0.50    0.05    --  -69.48  15.00   0.00   62
 32  \w   -151.00-108.00   0.50    0.05    --  -69.48-125.00-120.00   86
 33  \w   -101.00 -38.00   0.50    0.05    --  -69.48 125.00  30.00  126
 34  \w    -19.00   7.00   0.50    0.05    --  -69.48  15.00 150.00   52
 35  \w   -100.00 -27.00   0.50    0.05    --  -69.48 125.00-120.00  146
 36  \w    -14.00  12.00   0.50    0.05    --  -69.48  15.00  90.00   52
 37  \w     80.00 149.00   0.50    0.05    --   69.48 125.00  30.00  138
 38  \w     79.00 108.00   0.50    0.05    --   69.48 125.00 120.00   58
 39  \w    -25.00  12.00   0.50    0.05    --   69.48 -15.00-180.00   74
 40  \w    124.00 149.00   0.50    0.05    --   69.48 125.00 120.00   50
 41  \w    -23.00  17.00   0.50    0.05    --   69.48 -15.00  60.00   80
 42  \w    -23.00 101.00   0.50    0.05    --   69.48 -95.00 120.00  248
 43  \w    -17.00  16.00   0.50    0.05    --   69.48 -15.00  90.00   66
 44  \w    -46.00 -21.00   0.50    0.05    --  -97.00  38.00  90.00   50
 45  \w    -98.00 -49.00   0.50    0.05    --  -97.00  77.00 -60.00   98
 46  \w    -46.00 -21.00   0.50    0.05    --  -97.00  38.00 -90.00   50
 47  \w    -59.00 -24.00   0.50    0.05    --  -97.00  50.00-180.00   70
 48  \w   -140.00 -99.00   0.50    0.05    --  -97.00 -64.00 120.00   82
 49  \w    -46.00 -17.00   0.50    0.05    --  -97.00  38.00-120.00   58
 50  \w     83.00 108.00   0.50    0.05    --  123.00-111.00-120.00   50
 51  \w     76.00 102.00   0.50    0.05    --  123.00 -77.00 -60.00   52
 52  \w     79.00 108.00   0.50    0.05    --  123.00-111.00  30.00   58
 53  \w     38.00  71.00   0.50    0.05    --  123.00-111.00-120.00   66
 54  \w     43.00  69.00   0.50    0.05    --  123.00-111.00 -30.00   52
 55  \w     76.00 108.00   0.50    0.05    --  123.00-111.00 -30.00   64
 56  \w     43.00 105.00   0.50    0.05    --  123.00 179.00 -90.00  124
 57  \w    112.00 137.00   0.50    0.05    --  123.00 111.00  90.00   50
 58  \w     82.00 108.00   0.50    0.05    --  123.00-111.00-150.00   52
 59  \w     36.00  87.00   0.50    0.05    --  123.00 -77.00 120.00  102
 60  \w    143.00 171.00   0.50    0.05    --  123.00  12.00   0.00   56
 61  \w     82.00 108.00   0.50    0.05    --  123.00-111.00   0.00   52
 62  \w     87.00 170.00   0.50    0.05    --  123.00  64.00   0.00  166
 63  \w     84.00 138.00   0.50    0.05    --  123.00  12.00   0.00  108
 64  \w     39.00  78.00   0.50    0.05    --  123.00  12.00   0.00   78
 65  \w     36.00  65.00   0.50    0.05    --  123.00-111.00   0.00   58
 66  \w     67.00 107.00   0.50    0.05    --  123.00-111.00 -90.00   80
 67  \w     40.00  66.00   0.50    0.05    --  123.00-111.00 -90.00   52
 68  \w     61.00 108.00   0.50    0.05    --  123.00-111.00 -60.00   94
 69  \w     74.00 108.00   0.50    0.05    --  123.00-111.00 150.00   68
 70  \w     31.00  57.00   0.50    0.05    --  123.00 -92.00-180.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0454219000
_diffrn_orient_matrix_UB_12      -0.0869798000
_diffrn_orient_matrix_UB_13      0.0147712000
_diffrn_orient_matrix_UB_21      -0.0296719000
_diffrn_orient_matrix_UB_22      0.0584148000
_diffrn_orient_matrix_UB_23      0.0286174000
_diffrn_orient_matrix_UB_31      -0.0933659000
_diffrn_orient_matrix_UB_32      0.0237478000
_diffrn_orient_matrix_UB_33      -0.0162740000
_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  0.0705
_diffrn_reflns_av_unetI/netI     0.0486
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       54
_diffrn_reflns_limit_l_min       -53
_diffrn_reflns_number            81936
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.430
_diffrn_reflns_theta_min         3.251
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.090
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.37944
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.127a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.687
_exptl_crystal_description       block
_exptl_crystal_F_000             4480
_refine_diff_density_max         1.619
_refine_diff_density_min         -1.822
_refine_diff_density_rms         0.143
_refine_ls_abs_structure_details
;
 Flack x determined using 6047 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.017(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1137
_refine_ls_number_reflns         18111
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.631
_refine_ls_R_factor_all          0.0771
_refine_ls_R_factor_gt           0.0699
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0760P)^2^+60.5068P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1823
_refine_ls_wR_factor_ref         0.1873
_reflns_Friedel_coverage         0.794
_reflns_Friedel_fraction_full    0.991
_reflns_Friedel_fraction_max     0.953
_reflns_number_gt                16257
_reflns_number_total             18111
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08826g2.cif
_cod_data_source_block           1_CCDC1
_cod_database_code               1576923
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         choRuCl
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 H13-H19A
 2.45 with sigma of 0.01
 H75-H80C
 2.45 with sigma of 0.01
 H75-C75
 2.45 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C80) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4.a Ternary CH refined with riding coordinates:
 C38(H38), C18(H18), C58(H58), C78(H78)
4.b Aromatic/amide H refined with riding coordinates:
 C49(H49), C29(H29), C52(H52), C13(H13), C48(H48), C23(H23), C33(H33),
 C69(H69), C43(H43), C8(H8), C41(H41), C28(H28), C35(H35), C61(H61), C32(H32),
 C12(H12), C76(H76), C36(H36), C7(H7), C9(H9), C3(H3), C68(H68), C63(H63),
 C27(H27), C67(H67), C26(H26), C56(H56), C47(H47), C15(H15), C53(H53), C73(H73),
  C6(H6), C75(H75), C21(H21), C72(H72), C1(H1), C66(H66), C16(H16), C55(H55),
 C46(H46)
4.c Idealised Me refined as rotating group:
 N12(H12A,H12B,H12C), N9(H9A,H9B,H9C), N6(H6A,H6B,H6C), N3(H3A,H3B,H3C),
 C30(H30A,H30B,H30C), C70(H70A,H70B,H70C), C39(H39A,H39B,H39C), C57(H57A,H57B,
 H57C), C17(H17A,H17B,H17C), C60(H60A,H60B,H60C), C77(H77A,H77B,H77C), C10(H10A,
 H10B,H10C), C40(H40A,H40B,H40C), C20(H20A,H20B,H20C), C50(H50A,H50B,H50C),
 C37(H37A,H37B,H37C), C79(H79A,H79B,H79C), C59(H59A,H59B,H59C), C19(H19A,H19B,
 H19C), C80(H80A,H80B,H80C)
;
_shelx_res_checksum              68342
_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 2.363
_oxdiff_exptl_absorpt_empirical_full_min 0.582