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_7720001
_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         'C16 H15 Cl2 N3 Ni O'
_chemical_formula_sum            'C16 H15 Cl2 N3 Ni O'
_chemical_formula_weight         394.92
_chemical_name_systematic        NNNNiCl2
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_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                 92.3034(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.31157(5)
_cell_length_b                   6.89229(4)
_cell_length_c                   25.41149(18)
_cell_measurement_reflns_used    21872
_cell_measurement_temperature    300.00(10)
_cell_measurement_theta_max      65.7080
_cell_measurement_theta_min      3.4790
_cell_volume                     1629.542(17)
_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      300.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_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      5.00  59.00   0.50    0.21    --    0.16  30.00 -11.00  108
  2  \w   -154.00-128.00   0.50    0.85    --  -81.86 -30.00-171.00   52
  3  \w   -124.00 -74.00   0.50    0.85    --  -81.86 -30.00-171.00  100
  4  \w    114.00 139.00   0.50    0.85    --   82.17  30.00 -11.00   50
  5  \w     11.00  38.00   0.50    0.85    --   82.17 -30.00-171.00   54
  6  \w    -12.00  29.00   0.50    0.21    --    0.16 -99.00  90.00   82
  7  \w     25.00  60.00   0.50    0.21    --    0.16  77.00  60.00   70
  8  \w     38.00  70.00   0.50    0.21    --    0.16  38.00   0.00   64
  9  \w     -4.00  42.00   0.50    0.21    --    0.16  19.00 150.00   92
 10  \w     -7.00  58.00   0.50    0.21    --    0.16  38.00 -60.00  130
 11  \w    -15.00  27.00   0.50    0.21    --    0.16 -99.00-180.00   84
 12  \w     14.00  60.00   0.50    0.21    --    0.16  77.00-120.00   92
 13  \w    -20.00  11.00   0.50    0.21    --    0.16  77.00-120.00   62
 14  \w    -67.00 -39.00   0.50    0.21    --    0.16 -30.00-171.00   56
 15  \w     -6.00  69.00   0.50    0.21    --    0.16  38.00-180.00  150
 16  \w    -20.00   5.00   0.50    0.21    --    0.16  77.00  60.00   50
 17  \w   -115.00 -68.00   0.50    0.85    --  -81.86 -60.00 132.72   94
 18  \w   -153.00-127.00   0.50    0.85    --  -81.86 -60.00 145.53   52
 19  \w   -123.00 -68.00   0.50    0.85    --  -81.86 -60.00 145.53  110
 20  \w    -94.00 -62.00   0.50    0.85    --  -81.86 -74.00-127.50   64
 21  \w    -39.00 -10.00   0.50    0.85    --  -81.86  38.00 120.00   58
 22  \w    -90.00 -65.00   0.50    0.85    --  -81.86 -68.00-179.41   50
 23  \w   -154.00-125.00   0.50    0.85    --  -81.86 -74.00-127.50   58
 24  \w   -130.00-100.00   0.50    0.85    --  -81.86 -77.00 -90.00   60
 25  \w   -150.00-124.00   0.50    0.85    --  -81.86 -68.00-179.41   52
 26  \w    -87.00 -61.00   0.50    0.85    --  -81.86 -77.00  60.00   52
 27  \w    -86.00 -61.00   0.50    0.85    --  -81.86 -77.00 -90.00   50
 28  \w    -96.00 -68.00   0.50    0.85    --  -81.86 -60.00 105.00   56
 29  \w   -154.00-105.00   0.50    0.85    --  -81.86 -77.00   0.00   98
 30  \w    -89.00 -63.00   0.50    0.85    --  -81.86 -77.00   0.00   52
 31  \w    -95.00 -62.00   0.50    0.85    --  -81.86 -75.00  80.36   66
 32  \w    -89.00 -64.00   0.50    0.85    --  -81.86 -71.00  94.10   50
 33  \w    -87.00 -61.00   0.50    0.85    --  -81.86 -77.00-180.00   52
 34  \w   -130.00-104.00   0.50    0.85    --  -81.86 -77.00 -30.00   52
 35  \w    -86.00 -61.00   0.50    0.85    --  -81.86 -77.00 -30.00   50
 36  \w   -152.00-103.00   0.50    0.85    --  -81.86 -60.00 105.00   98
 37  \w    -88.00 -63.00   0.50    0.85    --  -81.86 -73.00 113.19   50
 38  \w    -87.00 -62.00   0.50    0.85    --  -81.86 -75.00 139.37   50
 39  \w    -87.00 -61.00   0.50    0.85    --  -81.86 -77.00  30.00   52
 40  \w   -104.00 -66.00   0.50    0.85    --  -81.86 -68.00-146.08   76
 41  \w   -154.00-128.00   0.50    0.85    --  -81.86 -73.00 113.19   52
 42  \w   -123.00 -63.00   0.50    0.85    --  -81.86 -72.00-113.77  120
 43  \w   -149.00 -67.00   0.50    0.85    --  -81.86 -63.00  -0.10  164
 44  \w    -40.00 -10.00   0.50    0.85    --  -81.86  38.00   0.00   60
 45  \w    -86.00 -61.00   0.50    0.85    --  -81.86 -77.00 150.00   50
 46  \w   -136.00 -65.00   0.50    0.85    --  -81.86 -69.00  62.28  142
 47  \w    -92.00 -66.00   0.50    0.85    --  -81.86 -64.00 -63.68   52
 48  \w    -86.00 -61.00   0.50    0.85    --  -81.86 -77.00-150.00   50
 49  \w   -149.00-123.00   0.50    0.85    --  -81.86 -64.00 -63.68   52
 50  \w    -95.00 -66.00   0.50    0.85    --  -81.86 -65.00 -91.62   58
 51  \w   -154.00 -63.00   0.50    0.85    --  -81.86 -73.00  45.63  182
 52  \w    -94.00 -69.00   0.50    0.85    --  -81.86 -57.00 -90.00   50
 53  \w   -148.00-123.00   0.50    0.85    --  -81.86 -77.00-150.00   50
 54  \w    -99.00 -72.00   0.50    0.85    --  -81.86 -48.00 -36.52   54
 55  \w    -92.00 -66.00   0.50    0.85    --  -81.86 -66.00-177.12   52
 56  \w    -39.00 -10.00   0.50    0.85    --  -81.86  38.00 -30.00   58
 57  \w    -95.00 -70.00   0.50    0.85    --  -81.86 -54.00 -45.30   50
 58  \w    -94.00 -69.00   0.50    0.85    --  -81.86 -57.00-180.00   50
 59  \w   -139.00 -67.00   0.50    0.85    --  -81.86 -64.00  89.14  144
 60  \w    -86.00 -61.00   0.50    0.85    --  -81.86 -77.00 -60.00   50
 61  \w     78.00 103.00   0.50    0.85    --   82.17 -77.00  60.00   50
 62  \w     11.00  72.00   0.50    0.85    --   82.17 -77.00  60.00  122
 63  \w     10.00  63.00   0.50    0.85    --   82.17 -77.00 -90.00  106
 64  \w     11.00  95.00   0.50    0.85    --   82.17 -77.00 120.00  168
 65  \w     70.00 104.00   0.50    0.85    --   82.17  57.00-150.00   68
 66  \w     64.00 150.00   0.50    0.85    --   82.17  77.00 -90.00  172
 67  \w     64.00  89.00   0.50    0.85    --   82.17 -99.00-180.00   50
 68  \w     14.00  39.00   0.50    0.85    --   82.17 -99.00-180.00   50
 69  \w     20.00 103.00   0.50    0.85    --   82.17 -99.00   0.00  166
 70  \w     13.00  97.00   0.50    0.85    --   82.17 -99.00-150.00  168
 71  \w     16.00  92.00   0.50    0.85    --   82.17 -77.00-150.00  152
 72  \w     12.00 103.00   0.50    0.85    --   82.17 -99.00  60.00  182
 73  \w     60.00  96.00   0.50    0.85    --   82.17 -99.00 -60.00   72
 74  \w     67.00 103.00   0.50    0.85    --   82.17 -77.00 -90.00   72
;
_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  0.0225
_diffrn_reflns_av_unetI/netI     0.0095
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            33655
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        65.663
_diffrn_reflns_theta_max         65.663
_diffrn_reflns_theta_min         3.481
_exptl_absorpt_coefficient_mu    4.789
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82356
_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 greenish green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.610
_exptl_crystal_description       needle
_exptl_crystal_F_000             808
_exptl_crystal_preparation       'refluxing condition in THF'
_exptl_crystal_recrystallization_method
'slow vapour diffusion. outside ether and compound soluble in DCM'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.234
_refine_diff_density_min         -0.189
_refine_diff_density_rms         0.036
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     249
_refine_ls_number_reflns         2800
_refine_ls_number_restraints     421
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0249
_refine_ls_R_factor_gt           0.0232
_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^)+(0.0293P)^2^+0.7104P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0610
_refine_ls_wR_factor_ref         0.0621
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2646
_reflns_number_total             2800
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02924d2.cif
_cod_data_source_block           pd-bm-ni-typ_auto
_cod_original_cell_volume        1629.543(18)
_cod_database_code               7720001
_shelx_shelxl_version_number     2019/3
_diffrn_oxdiff_ac3_digest_hkl    41aa3ef31456a4b37baa680cd5a5d770571c8d
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H,H,H,H) groups, All O(H) groups
2. Restrained distances
 O2-H2
 0.85 with sigma of 0.01
 O1-H1
 0.85 with sigma of 0.01
 C16-H2
 1.90123 with sigma of 0.02
 Ni1-H2
 2.686635 with sigma of 0.02
 C16-H1
 1.884507 with sigma of 0.02
 Ni1-H1
 2.791034 with sigma of 0.02
 Ni1-Cl2 \\sim Ni1-Cl4
 with sigma of 0.02
 Ni1-Cl3 \\sim Ni1-Cl5
 with sigma of 0.02
 Ni1-O1 \\sim Ni1-O2
 with sigma of 0.02
 O1-C16 \\sim O2-C16
 with sigma of 0.02
3. Restrained planarity
 N2, C2, C9, C12, C8, C6
 with sigma of 0.1
4. Rigid bond restraints
 C8, C12, C9, C2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C2, C9
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. 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
C10 \\sim C15 \\sim C10 \\sim C15: within 0.02A with sigma of 0.02 and sigma
for terminal atoms of 0.01 within 0.02A
C2 \\sim C9: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.01
within 2A
Uanis(C9) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
6. Rigid body (RIGU) restrains
 O1, O2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(Cl4)=1-FVAR(1)
 Sof(Cl2)=FVAR(1)
 Sof(Cl5)=1-FVAR(2)
 Sof(Cl3)=FVAR(2)
 Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(O2)=Sof(H2)=1-FVAR(3)
 Sof(O1)=Sof(H1)=Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(3)
8.a Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C10(H10), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15)
8.b Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C16(H16D,H16E,H16F)
;
_shelx_res_checksum              93928
_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
;