Amidines: a deeper look at the archetypal pro-ligand.
de Vere-Tucker, Matthew; Squire, Imogen; Tritto, Michelangelo; Anandkar, Rohil; Syeda, Tayyibah; Uthayan, Divia; Aguila, Gabrielle; Silva de Moraes, Lygia; Bakewell, Clare; Dalton transactions (Cambridge, England : 2003) 55 (2026) 4977–4987; doi:10.1039/d6dt00276e

data_7720578
_publ_section_title
;
 Amidines: a deeper look at the archetypal pro-ligand.
;
_journal_issue                   12
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              4977
_journal_page_last               4987
_journal_paper_doi               10.1039/d6dt00276e
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C54 H82 Al2 N4, 1[C6H14]'
_chemical_formula_sum            'C60 H96 Al2 N4'
_chemical_formula_weight         927.36
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-12-08
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2026-01-30 deposited with the CCDC.	2026-03-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.5120(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.8685(2)
_cell_length_b                   9.27690(10)
_cell_length_c                   25.8714(3)
_cell_measurement_reflns_used    52064
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.8970
_cell_measurement_theta_min      3.4470
_cell_volume                     5665.49(10)
_computing_cell_refinement       'CrysAlisPro 1.171.44.118a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.127a 64-bit (release 27-10-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.118a (Rigaku OD, 2025)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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     33.00  58.00   0.50    0.10    --   95.64-125.00 120.00   50
  2  \w     58.00 111.00   0.50    0.10    --   95.64-125.00   0.00  106
  3  \w     44.00 111.00   0.50    0.10    --   95.64-125.00 -60.00  134
  4  \w     78.00 111.00   0.50    0.10    --   95.64-125.00-120.00   66
  5  \w     41.00 111.00   0.50    0.10    --   95.64-125.00-180.00  140
  6  \w    -13.00  91.00   0.50    0.10    --   49.24 -99.00 -60.00  208
  7  \w     67.00 103.00   0.50    0.10    --   95.64 -95.00 -30.00   72
  8  \w     77.00 105.00   0.50    0.10    --  101.75 -90.00 -57.25   56
  9  \w     33.00 106.00   0.50    0.10    --  101.75 -86.00-132.60  146
 10  \w     33.00  72.00   0.50    0.10    --  101.75 -85.00-100.93   78
 11  \w     35.00  72.00   0.50    0.10    --  101.75 -90.00 -57.25   74
 12  \w     85.00 110.00   0.50    0.10    --  101.75 -85.00-100.93   50
 13  \w     34.00 100.00   0.50    0.10    --  101.75 -85.00-177.54  132
 14  \w     33.00  69.00   0.50    0.10    --  101.75 -86.00  20.25   72
 15  \w     33.00 105.00   0.50    0.10    --  101.75 -87.00  -8.71  144
 16  \w     61.00  86.00   0.50    0.10    --  101.75 -83.00-153.72   50
 17  \w     70.00 111.00   0.50    0.10    --  101.75 -84.00  85.11   82
 18  \w     35.00  66.00   0.50    0.10    --  101.75 -84.00  85.11   62
 19  \w     37.00  68.00   0.50    0.10    --  101.75 -83.00 170.84   62
 20  \w     63.00 110.00   0.50    0.10    --   95.64-125.00 120.00   94
 21  \w     34.00  60.00   0.50    0.10    --  101.75 -83.00-153.72   52
 22  \w    110.00 135.00   0.50    0.10    --  101.75 -83.00-153.72   50
 23  \w     76.00 103.00   0.50    0.10    --  101.75 -79.00  29.22   54
 24  \w    108.00 133.00   0.50    0.10    --  101.75 -79.00 -81.39   50
 25  \w     33.00  58.00   0.50    0.10    --  101.75 -79.00 -81.39   50
 26  \w     33.00  68.00   0.50    0.10    --  101.75 -76.00 -38.88   70
 27  \w     33.00  68.00   0.50    0.10    --  101.75 -79.00  29.22   70
 28  \w     34.00  65.00   0.50    0.10    --  101.75 -78.00 118.54   62
 29  \w     34.00  81.00   0.50    0.10    --  101.75 -79.00 145.34   94
 30  \w     19.00  50.00   0.50    0.10    --   95.64 -45.00 120.00   62
 31  \w     33.00  65.00   0.50    0.10    --  101.75 -79.00 105.13   64
 32  \w     32.00  69.00   0.50    0.10    --  101.75 -75.00  52.41   74
 33  \w     22.00  50.00   0.50    0.10    --   95.64 -45.00  30.00   56
 34  \w    -26.00  29.00   0.50    0.10    --   49.24 -18.00  54.00  110
 35  \w     33.00  88.00   0.50    0.10    --  101.75 -75.00-130.16  110
 36  \w     19.00  50.00   0.50    0.10    --   95.64 -45.00-180.00   62
 37  \w     25.00  52.00   0.50    0.10    --   56.00  79.00 -11.87   54
 38  \w     25.00  52.00   0.50    0.10    --   56.00  79.00 146.09   54
 39  \w     25.00  52.00   0.50    0.10    --   56.00  79.00  92.11   54
 40  \w     22.00  52.00   0.50    0.10    --   52.00  77.00  59.25   60
 41  \w     26.00  52.00   0.50    0.10    --   56.00  78.00  28.50   52
 42  \w     26.00  52.00   0.50    0.10    --   56.00  77.00 -35.14   52
 43  \w     26.00  52.00   0.50    0.10    --   56.00  76.00 -66.50   52
 44  \w     26.00  52.00   0.50    0.10    --   56.00  78.00 -95.13   52
 45  \w     26.00  52.00   0.50    0.10    --   56.00  78.00-139.69   52
 46  \w     26.00  52.00   0.50    0.10    --   56.00  78.00-161.61   52
 47  \w     84.00 118.00   0.50    0.10    --   95.64  61.00 -60.00   68
 48  \w     81.00 110.00   0.50    0.10    --   95.64  61.00-120.00   58
 49  \w    131.00 166.00   0.50    0.10    --   95.64  61.00 -60.00   70
 50  \w    138.00 167.00   0.50    0.10    --   95.64  61.00-120.00   58
 51  \w     84.00 109.00   0.50    0.10    --   95.64  61.00  30.00   50
 52  \w     82.00 109.00   0.50    0.10    --   95.64  61.00  90.00   54
 53  \w    146.00 171.00   0.50    0.10    --   95.64  61.00  90.00   50
 54  \w    131.00 161.00   0.50    0.10    --   95.64  61.00  30.00   60
 55  \w     20.00 125.00   0.50    0.10    --   49.24  18.00-136.00  210
 56  \w     62.00 118.00   0.50    0.10    --  101.75  15.00 -58.72  112
 57  \w    149.00 176.00   0.50    0.10    --  101.75  15.00 -58.72   54
 58  \w    140.00 173.00   0.50    0.10    --  101.75  15.00-164.08   66
 59  \w     66.00 171.00   0.50    0.10    --   95.64  18.00-136.00  210
 60  \w     82.00 108.00   0.50    0.10    --  101.75  15.00-164.08   52
 61  \w     47.00  94.00   0.50    0.10    --  101.75  12.00 -99.62   94
 62  \w    126.00 173.00   0.50    0.10    --  101.75  12.00 -99.62   94
 63  \w     38.00  67.00   0.50    0.10    --  101.75  10.00  26.83   58
 64  \w     59.00 159.00   0.50    0.10    --  101.75  14.00  81.59  200
 65  \w    134.00 176.00   0.50    0.10    --  101.75  15.00 156.26   84
 66  \w     66.00 109.00   0.50    0.10    --  101.75  15.00 156.26   86
 67  \w     80.00 127.00   0.50    0.10    --  101.75   0.00  46.56   94
 68  \w     80.00 107.00   0.50    0.10    --  101.75  10.00  26.83   54
 69  \w     36.00  62.00   0.50    0.10    --  101.75   0.00  46.56   52
 70  \w    130.00 166.00   0.50    0.10    --  101.75   0.00  46.56   72
 71  \w    146.00 171.00   0.50    0.10    --  101.75   0.00-133.42   50
 72  \w    118.00 144.00   0.50    0.10    --  101.75   0.00-133.42   52
 73  \w     33.00  82.00   0.50    0.10    --  101.75   0.00-133.42   98
 74  \w     16.00  42.00   0.50    0.10    --   48.00  81.00 157.66   52
 75  \w      6.00  32.00   0.50    0.10    --   40.00  87.00 143.08   52
 76  \w    -43.00  -5.00   0.50    0.10    --   16.00 133.00   8.70   76
 77  \w    -39.00  10.00   0.50    0.10    --    8.00 111.00 -58.11   98
 78  \w     16.00  42.00   0.50    0.10    --   48.00  81.00 -81.39   52
 79  \w    -11.00  18.00   0.50    0.10    --   32.00 101.00-151.67   58
 80  \w    -23.00  25.00   0.50    0.10    --  -50.74  18.00-136.00   96
 81  \w   -113.00 -74.00   0.50    0.10    --  -96.00 -76.00 -85.40   78
 82  \w    -99.00 -73.00   0.50    0.10    --  -96.00 -75.00  33.69   52
 83  \w    -98.00 -73.00   0.50    0.10    --  -96.00 -74.00  86.56   50
 84  \w   -108.00 -74.00   0.50    0.10    --  -96.00 -76.00 165.15   68
 85  \w   -108.00 -73.00   0.50    0.10    --  -96.00 -74.00 175.11   70
 86  \w   -151.00-125.00   0.50    0.10    --  -96.00 -74.00 175.11   52
 87  \w   -157.00-131.00   0.50    0.10    --  -96.00 -74.00  86.56   52
 88  \w   -118.00 -73.00   0.50    0.10    --  -96.00 -71.00 138.95   90
 89  \w   -164.00-123.00   0.50    0.10    --  -96.00 -71.00 138.95   82
 90  \w   -121.00 -73.00   0.50    0.10    --  -96.00 -73.00  60.50   96
 91  \w   -104.00 -73.00   0.50    0.10    --  -96.00 -71.00  -3.34   62
 92  \w   -118.00 -73.00   0.50    0.10    --  -96.00 -71.00 -36.59   90
 93  \w    -98.00 -73.00   0.50    0.10    --  -96.00 -72.00 -79.30   50
 94  \w   -151.00-125.00   0.50    0.10    --  -96.00 -72.00 -79.30   52
 95  \w   -160.00-123.00   0.50    0.10    --  -96.00 -71.00 -36.59   74
 96  \w   -157.00-131.00   0.50    0.10    --  -96.00 -71.00  -3.34   52
 97  \w   -153.00-127.00   0.50    0.10    --  -96.00 -71.00 121.97   52
 98  \w   -113.00 -73.00   0.50    0.10    --  -96.00 -71.00 121.97   80
 99  \w    -99.00 -73.00   0.50    0.10    --  -96.00 -70.00 -49.18   52
100  \w   -100.00 -73.00   0.50    0.10    --  -96.00 -70.00 -58.60   54
101  \w   -117.00 -75.00   0.50    0.10    --  -96.00 -70.00-146.41   84
102  \w   -164.00-138.00   0.50    0.10    --  -96.00 -70.00-146.41   52
103  \w   -156.00-118.00   0.50    0.10    --  -96.00 -70.00-111.38   76
104  \w   -110.00 -75.00   0.50    0.10    --  -96.00 -70.00-111.38   70
105  \w   -115.00 -74.00   0.50    0.10    --  -96.00 -69.00-170.97   82
106  \w    -94.00 -62.00   0.50    0.10    --  -84.00 -69.00-123.58   64
107  \w   -101.00 -75.00   0.50    0.10    --  -96.00 -69.00 -70.28   52
108  \w   -167.00-129.00   0.50    0.10    --  -96.00 -69.00-170.97   76
109  \w   -164.00-139.00   0.50    0.10    --  -96.00 -69.00-126.91   50
110  \w   -101.00 -74.00   0.50    0.10    --  -96.00 -69.00-126.91   54
111  \w   -118.00 -74.00   0.50    0.10    --  -96.00 -69.00 -16.42   88
112  \w    -99.00 -73.00   0.50    0.10    --  -96.00 -70.00 110.80   52
113  \w    -88.00 -62.00   0.50    0.10    --  -84.00 -69.00 117.99   52
114  \w    -92.00 -66.00   0.50    0.10    --  -88.00 -69.00 167.95   52
115  \w   -152.00 -58.00   0.50    0.10    --  -80.00 -69.00 179.98  188
116  \w   -153.00 -59.00   0.50    0.10    --  -80.00 -68.00 129.53  188
117  \w    -88.00 -63.00   0.50    0.10    --  -84.00 -68.00  14.84   50
118  \w   -104.00 -75.00   0.50    0.10    --  -96.00 -68.00  10.87   58
119  \w   -144.00 -50.00   0.50    0.10    --  -72.00 -69.00 -25.03  188
120  \w   -144.00 -50.00   0.50    0.10    --  -72.00 -69.00 -25.03  188
121  \w   -149.00 -55.00   0.50    0.10    --  -76.00 -68.00 -56.12  188
122  \w   -145.00 -51.00   0.50    0.10    --  -72.00 -68.00 -44.75  188
123  \w   -145.00 -51.00   0.50    0.10    --  -72.00 -68.00-103.56  188
124  \w   -145.00 -51.00   0.50    0.10    --  -72.00 -68.00-103.56  188
125  \w    -91.00 -64.00   0.50    0.10    --  -84.00 -67.00-164.96   54
126  \w   -153.00 -60.00   0.50    0.10    --  -80.00 -67.00-115.38  186
127  \w   -145.00 -52.00   0.50    0.10    --  -72.00 -67.00-170.93  186
128  \w   -153.00 -59.00   0.50    0.10    --  -80.00 -68.00  -0.36  188
129  \w    -90.00 -62.00   0.50    0.10    --  -80.00 -67.00  54.84   56
130  \w   -104.00 -77.00   0.50    0.10    --  -96.00 -68.00  93.18   54
131  \w   -153.00 -60.00   0.50    0.10    --  -80.00 -67.00  70.17  186
132  \w   -149.00 -56.00   0.50    0.10    --  -76.00 -67.00  28.57  186
133  \w   -145.00 -53.00   0.50    0.10    --  -72.00 -65.00  69.44  184
134  \w   -145.00 -53.00   0.50    0.10    --  -72.00 -65.00  69.44  184
135  \w   -145.00 -53.00   0.50    0.10    --  -72.00 -65.00  88.04  184
136  \w   -145.00 -53.00   0.50    0.10    --  -72.00 -65.00  88.04  184
137  \w   -149.00 -57.00   0.50    0.10    --  -76.00 -65.00 141.02  184
138  \w   -168.00-115.00   0.50    0.10    --  -96.00 -62.00  34.72  106
139  \w   -108.00 -80.00   0.50    0.10    --  -96.00 -62.00  34.72   56
140  \w   -126.00 -22.00   0.50    0.10    --  -50.74 -18.00  54.00  208
141  \w   -163.00 -59.00   0.50    0.10    --  -87.86 -18.00  54.00  208
142  \w   -119.00 -79.00   0.50    0.10    --  -96.00 -63.00 -31.34   80
143  \w   -146.00 -55.00   0.50    0.10    --  -72.00 -63.00 -81.46  182
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0609703000
_diffrn_orient_matrix_UB_12      0.0274171000
_diffrn_orient_matrix_UB_13      -0.0105316000
_diffrn_orient_matrix_UB_21      0.0139419000
_diffrn_orient_matrix_UB_22      -0.1608581000
_diffrn_orient_matrix_UB_23      0.0093710000
_diffrn_orient_matrix_UB_31      -0.0186785000
_diffrn_orient_matrix_UB_32      -0.0306937000
_diffrn_orient_matrix_UB_33      -0.0585353000
_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  0.0461
_diffrn_reflns_av_unetI/netI     0.0154
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            130611
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.225
_diffrn_reflns_theta_min         3.455
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.748
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.567
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.118a (Rigaku Oxford Diffraction, 2025)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.087
_exptl_crystal_description       block
_exptl_crystal_F_000             2040
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane'
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.361
_refine_diff_density_min         -0.333
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     288
_refine_ls_number_reflns         5889
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0448
_refine_ls_R_factor_gt           0.0399
_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^)+(0.0552P)^2^+3.9076P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1084
_refine_ls_wR_factor_ref         0.1119
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5240
_reflns_number_total             5889
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00276e3.cif
_cod_data_source_block           dippdepAmtBuAlH2_15-Al
_cod_depositor_comments
'Adding full bibliography for 7720566--7720581.cif.'
_cod_database_code               7720578
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C11 H10 N O'
_cell_oxdiff_angle_alpha         90.0016(8)
_cell_oxdiff_angle_beta          98.5125(8)
_cell_oxdiff_angle_gamma         90.0123(7)
_cell_oxdiff_length_a            23.8640(2)
_cell_oxdiff_length_b            9.27834(8)
_cell_oxdiff_length_c            25.8724(2)
_cell_oxdiff_measurement_reflns_used 59134
_cell_oxdiff_volume              5665.52(9)
_shelx_estimated_absorpt_t_max   0.871
_shelx_estimated_absorpt_t_min   0.818
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name exp_70-DVT-464_full_exp.par
_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 Ternary CH refined with riding coordinates:
 C25(H25), C22(H22)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12a,H12b), C14(H14a,H14b)
2.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C19(H19), C18(H18), C10(H10), C9(H9), C8(H8)
2.d Idealised Me refined as rotating group:
 C5(H5a,H5b,H5c), C3(H3a,H3b,H3c), C26(H26a,H26b,H26c), C27(H27a,H27b,H27c),
 C4(H4a,H4b,H4c), C24(H24a,H24b,H24c), C23(H23a,H23b,H23c), C13(H13a,H13b,H13c),
  C15(H15a,H15b,H15c)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              86876
_shelx_hkl_checksum              46312
_shelx_fab_checksum              26823
_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 1.928
_oxdiff_exptl_absorpt_empirical_full_min 0.636