Dehydrogenation of Ammonia-Borane Employing an Air-stable, Phosphine-free Molecular Nickel Pincer Catalyst
Mondal, Bijan; Mohanty, Aisa; Daw, Prosenjit; Dalton Transactions  (2026) –; doi:10.1039/D5DT02924D

data_7720002
_publ_section_title
;
 Dehydrogenation of Ammonia-Borane Employing an Air-stable, Phosphine-free
 Molecular Nickel Pincer Catalyst
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D5DT02924D
_journal_year                    2026
_chemical_formula_moiety         'C11.5 H12.5 Cl N2.5 Ni0.5'
_chemical_formula_sum            'C11.5 H12.5 Cl N2.5 Ni0.5'
_chemical_formula_weight         250.54
_chemical_name_systematic        NNNiCl2_pyro
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-09-20
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-10-20 deposited with the CCDC.	2025-12-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.7910(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.16250(10)
_cell_length_b                   12.33170(10)
_cell_length_c                   15.6518(2)
_cell_measurement_reflns_used    13048
_cell_measurement_temperature    99.97(19)
_cell_measurement_theta_max      76.9070
_cell_measurement_theta_min      5.3570
_cell_volume                     2109.05(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_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      100.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.983
_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    -71.00  23.00   0.50    1.48    --  -47.76  80.00  30.00  188
  2  \w    -13.00  51.00   0.50    1.48    --   47.76 -80.00 -92.00  128
  3  \w   -173.00-147.00   0.50    5.91    -- -103.00 -80.00 -92.00   52
  4  \w    -86.00 -38.00   0.50    5.91    -- -103.00  80.00  30.00   96
  5  \w   -113.00 -87.00   0.50    5.91    -- -103.00 -80.00 -92.00   52
  6  \w    131.00 174.00   0.50    5.91    --  107.18  80.00  30.00   86
  7  \w    -66.00 -27.00   0.50    1.48    --  -47.76 -77.00-120.00   78
  8  \w    -68.00 -33.00   0.50    1.48    --  -47.76 -61.00-142.45   70
  9  \w   -101.00 -72.00   0.50    1.48    --  -47.76 -77.00  60.00   58
 10  \w    -64.00 -25.00   0.50    1.48    --  -47.76 -77.00  30.00   78
 11  \w    -79.00 -25.00   0.50    1.48    --  -47.76 -77.00-180.00  108
 12  \w   -118.00 -85.00   0.50    1.48    --  -47.76 -77.00-180.00   66
 13  \w    -66.00 -25.00   0.50    1.48    --  -47.76 -77.00 -90.00   82
 14  \w    -68.00 -35.00   0.50    1.48    --  -47.76 -38.00 150.00   66
 15  \w   -109.00 -83.00   0.50    1.48    --  -47.76 -61.00-142.45   52
 16  \w    -58.00 -33.00   0.50    1.48    --  -47.76 -57.00 -90.00   50
 17  \w   -104.00 -78.00   0.50    1.48    --  -47.76 -57.00 -90.00   52
 18  \w   -113.00 -87.00   0.50    1.48    --  -47.76 -77.00  30.00   52
 19  \w    -78.00 -25.00   0.50    1.48    --  -47.76 -77.00 120.00  106
 20  \w    -60.00 -35.00   0.50    1.48    --  -47.76 -44.00  -7.02   50
 21  \w    -54.00 -25.00   0.50    1.48    --  -47.76 -77.00 -30.00   58
 22  \w    -54.00 -27.00   0.50    1.48    --  -47.76 -77.00  60.00   54
 23  \w    -63.00 -35.00   0.50    1.48    --  -47.76 -57.00 -30.00   56
 24  \w     35.00  92.00   0.50    1.48    --   47.76  19.00   0.00  114
 25  \w     19.00  94.00   0.50    1.48    --   47.76-125.00 -90.00  150
 26  \w      2.00  27.00   0.50    1.48    --   47.76 -19.00 -30.00   50
 27  \w     36.00  79.00   0.50    1.48    --   47.76  57.00  30.00   86
 28  \w     38.00  67.00   0.50    1.48    --   47.76  57.00 -30.00   58
 29  \w   -123.00 -84.00   0.50    5.91    -- -103.00 -69.00 -77.62   78
 30  \w   -166.00-119.00   0.50    5.91    -- -103.00 -65.00 109.87   94
 31  \w   -163.00-137.00   0.50    5.91    -- -103.00 -57.00 -60.00   52
 32  \w   -107.00 -82.00   0.50    5.91    -- -103.00 125.00   0.00   50
 33  \w   -118.00 -90.00   0.50    5.91    -- -103.00 -48.00 -60.23   56
 34  \w   -168.00-142.00   0.50    5.91    -- -103.00 -69.00 -77.62   52
 35  \w   -112.00 -85.00   0.50    5.91    -- -103.00 -65.00 109.87   54
 36  \w   -122.00 -86.00   0.50    5.91    -- -103.00 -61.00 -15.80   72
 37  \w   -168.00 -86.00   0.50    5.91    -- -103.00 -65.00 -16.38  164
 38  \w   -115.00 -80.00   0.50    5.91    -- -103.00 -78.00  87.02   70
 39  \w   -109.00 -84.00   0.50    5.91    -- -103.00 -67.00  88.63   50
 40  \w   -165.00-139.00   0.50    5.91    -- -103.00 -78.00  87.02   52
 41  \w   -108.00 -82.00   0.50    5.91    -- -103.00 -77.00-150.00   52
 42  \w   -107.00 -82.00   0.50    5.91    -- -103.00 -77.00 -90.00   50
 43  \w   -134.00 -86.00   0.50    5.91    -- -103.00 -63.00 118.03   96
 44  \w   -173.00 -86.00   0.50    5.91    -- -103.00 -62.00 143.90  174
 45  \w   -121.00 -84.00   0.50    5.91    -- -103.00 -68.00-145.12   74
 46  \w   -163.00-130.00   0.50    5.91    -- -103.00 -68.00-145.12   66
 47  \w    -62.00 -31.00   0.50    5.91    -- -103.00  57.00   0.00   62
 48  \w   -113.00 -81.00   0.50    5.91    -- -103.00 -77.00  60.00   64
 49  \w   -174.00-122.00   0.50    5.91    -- -103.00 -77.00  60.00  104
 50  \w   -174.00 -86.00   0.50    5.91    -- -103.00 -65.00 -26.83  176
 51  \w   -115.00 -89.00   0.50    5.91    -- -103.00 -57.00  30.00   52
 52  \w   -147.00 -85.00   0.50    5.91    -- -103.00 -67.00-172.24  124
 53  \w   -109.00 -84.00   0.50    5.91    -- -103.00 -77.00-180.00   50
 54  \w   -158.00-131.00   0.50    5.91    -- -103.00 -57.00  30.00   54
 55  \w   -174.00-113.00   0.50    5.91    -- -103.00 -77.00 -60.00  122
 56  \w   -114.00 -88.00   0.50    5.91    -- -103.00 -57.00 -60.00   52
 57  \w   -111.00 -81.00   0.50    5.91    -- -103.00 -77.00  30.00   60
 58  \w   -163.00-126.00   0.50    5.91    -- -103.00 -77.00  30.00   74
 59  \w   -140.00 -80.00   0.50    5.91    -- -103.00 -77.00-120.00  120
 60  \w   -173.00 -80.00   0.50    5.91    -- -103.00 -77.00-108.23  186
 61  \w   -173.00 -85.00   0.50    5.91    -- -103.00 -64.00 171.41  176
 62  \w   -113.00 -88.00   0.50    5.91    -- -103.00 -57.00 150.00   50
 63  \w   -123.00 -88.00   0.50    5.91    -- -103.00 -56.00  46.51   70
 64  \w   -118.00 -84.00   0.50    5.91    -- -103.00 -67.00  26.87   68
 65  \w   -106.00 -81.00   0.50    5.91    -- -103.00 -77.00 150.00   50
 66  \w   -169.00-143.00   0.50    5.91    -- -103.00 -77.00 150.00   52
 67  \w   -115.00 -90.00   0.50    5.91    -- -103.00 -57.00 120.00   50
 68  \w   -113.00 -88.00   0.50    5.91    -- -103.00 -57.00  90.00   50
 69  \w   -112.00 -87.00   0.50    5.91    -- -103.00 -60.00 -69.91   50
 70  \w   -160.00 -80.00   0.50    5.91    -- -103.00 -77.00  65.21  160
 71  \w   -115.00 -86.00   0.50    5.91    -- -103.00 -61.00 -99.18   58
 72  \w   -169.00 -85.00   0.50    5.91    -- -103.00 -66.00-156.81  168
 73  \w   -105.00 -80.00   0.50    5.91    -- -103.00 -77.00 -60.00   50
 74  \w   -166.00 -83.00   0.50    5.91    -- -103.00 -69.00   6.43  166
 75  \w     86.00 112.00   0.50    5.91    --  107.18-125.00-180.00   52
 76  \w     50.00  82.00   0.50    5.91    --  107.18-125.00-180.00   64
 77  \w     45.00  89.00   0.50    5.91    --  107.18 -99.00 120.00   88
 78  \w     39.00 102.00   0.50    5.91    --  107.18 -99.00  30.00  126
 79  \w     43.00 111.00   0.50    5.91    --  107.18-125.00 -90.00  136
 80  \w     47.00 102.00   0.50    5.91    --  107.18 -99.00 -90.00  110
 81  \w     87.00 112.00   0.50    5.91    --  107.18-125.00   0.00   50
 82  \w     41.00 112.00   0.50    5.91    --  107.18-125.00 120.00  142
 83  \w     41.00  72.00   0.50    5.91    --  107.18-125.00   0.00   62
 84  \w     39.00 101.00   0.50    5.91    --  107.18 -99.00-180.00  124
 85  \w     54.00  89.00   0.50    5.91    --  107.18 -80.00 -92.00   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0349
_diffrn_reflns_av_unetI/netI     0.0160
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            25445
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.088
_diffrn_reflns_theta_min         5.409
_exptl_absorpt_coefficient_mu    3.829
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83295
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.116a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.578
_exptl_crystal_description       needle
_exptl_crystal_F_000             1040
_exptl_crystal_preparation       'reflux condition in toluene'
_exptl_crystal_recrystallization_method
'slow vapour diffusion layered by ether and compound soluble in DCm'
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.07
_refine_diff_density_max         1.287
_refine_diff_density_min         -0.541
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     150
_refine_ls_number_reflns         2199
_refine_ls_number_restraints     234
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0465
_refine_ls_R_factor_gt           0.0433
_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^)+(0.0467P)^2^+7.7748P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1077
_refine_ls_wR_factor_ref         0.1095
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2055
_reflns_number_total             2199
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02924d2.cif
_cod_data_source_block           exp_250_auto
_cod_original_formula_sum        'C11.50 H12.50 Cl N2.50 Ni0.50'
_cod_database_code               7720002
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.775
_shelx_estimated_absorpt_t_min   0.616
_diffrn_oxdiff_ac3_digest_hkl    413cde49e2aab27110387f502bd5f908e35f29
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C12-C10
 1.51 with sigma of 0.02
 N006-C10
 1.49 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C1(H1), C6(H6), C8(H8), C9(H9)
;
_shelx_res_checksum              75736
_olex2_exptl_crystal_mounting_method 'MetiGen loop'
_olex2_submission_original_sample_id PD_BM_NiCl_pyro
_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
;