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_7720571
_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         'C60 H78 Al2 N4'
_chemical_formula_sum            'C60 H78 Al2 N4'
_chemical_formula_weight         909.22
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-12-17
_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                117.251(4)
_cell_angle_beta                 91.690(2)
_cell_angle_gamma                97.297(2)
_cell_formula_units_Z            1
_cell_length_a                   9.0212(2)
_cell_length_b                   12.7128(5)
_cell_length_c                   13.2559(4)
_cell_measurement_reflns_used    11533
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.0940
_cell_measurement_theta_min      3.6610
_cell_volume                     1333.93(9)
_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 0.987
_diffrn_measured_fraction_theta_max 0.987
_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    -19.00  82.00   0.50    0.70    --   48.99 -83.00  54.00  202
  2  \w    -83.00  18.00   0.50    0.70    --  -50.74  83.00 174.00  202
  3  \w   -121.00 -19.00   0.50    0.70    --  -87.86  83.00 174.00  204
  4  \w   -156.00 -82.00   0.50    0.70    --  -87.86 -83.00  54.00  148
  5  \w     27.00 129.00   0.50    0.70    --   95.64 -83.00  54.00  204
  6  \w     88.00 164.00   0.50    0.70    --   95.64  83.00 174.00  152
  7  \w    -13.00  13.00   0.50    0.70    --   32.00 107.00  25.43   52
  8  \w   -120.00 -75.00   0.50    0.70    --  -50.74 -77.00  60.00   90
  9  \w     26.00  52.00   0.50    0.70    --   56.00  78.00 -19.56   52
 10  \w     26.00  52.00   0.50    0.70    --   56.00  78.00 -49.78   52
 11  \w     26.00  52.00   0.50    0.70    --   56.00  76.00  33.45   52
 12  \w     26.00  52.00   0.50    0.70    --   56.00  77.00 -84.64   52
 13  \w     25.00  52.00   0.50    0.70    --   56.00  79.00-120.94   54
 14  \w   -147.00 -57.00   0.50    0.70    --  -72.00 -60.00 -76.75  180
 15  \w     22.00 111.00   0.50    0.70    --   95.64-125.00 -60.00  178
 16  \w     26.00 104.00   0.50    0.70    --   95.64 -95.00  30.00  156
 17  \w     22.00 111.00   0.50    0.70    --   95.64-125.00 150.00  178
 18  \w     22.00 111.00   0.50    0.70    --   95.64-125.00 150.00  178
 19  \w     22.00 111.00   0.50    0.70    --   95.64-125.00 -60.00  178
 20  \w     26.00 104.00   0.50    0.70    --   95.64 -95.00  30.00  156
 21  \w     22.00 111.00   0.50    0.70    --   95.64-125.00  60.00  178
 22  \w     22.00 111.00   0.50    0.70    --   95.64-125.00   0.00  178
 23  \w     22.00 111.00   0.50    0.70    --   95.64-125.00 -30.00  178
 24  \w     22.00 111.00   0.50    0.70    --   95.64-125.00-150.00  178
 25  \w     22.00 111.00   0.50    0.70    --   95.64-125.00-150.00  178
 26  \w   -169.00 -76.00   0.50    0.70    --  -96.00 -67.00 -14.40  186
 27  \w     62.00 171.00   0.50    0.70    --   96.00  16.00  95.60  218
 28  \w     33.00 112.00   0.50    0.70    --  101.75 -84.00-178.52  158
 29  \w     33.00 112.00   0.50    0.70    --  101.75 -84.00-178.52  158
 30  \w     33.00 107.00   0.50    0.70    --  101.75 -88.00 -44.98  148
 31  \w     62.00 177.00   0.50    0.70    --  101.75  15.00 -83.51  230
 32  \w     36.00  96.00   0.50    0.70    --  101.75 -75.00-119.00  120
 33  \w     34.00  94.00   0.50    0.70    --  101.75 -83.00 -22.80  120
 34  \w     37.00  69.00   0.50    0.70    --  101.75 -77.00-175.64   64
 35  \w    140.00 165.00   0.50    0.70    --  101.75  12.00-116.46   50
 36  \w     33.00  58.00   0.50    0.70    --  101.75 -84.00 146.21   50
 37  \w     82.00 112.00   0.50    0.70    --  101.75 -84.00-123.31   60
 38  \w     93.00 119.00   0.50    0.70    --  101.75  12.00-116.46   52
 39  \w     34.00  60.00   0.50    0.70    --  101.75 -82.00-138.89   52
 40  \w     35.00  71.00   0.50    0.70    --  101.75 -78.00  53.99   72
 41  \w     81.00 107.00   0.50    0.70    --  101.75 -88.00  40.02   52
 42  \w     33.00  74.00   0.50    0.70    --  101.75 -88.00  40.02   82
 43  \w     80.00 106.00   0.50    0.70    --  101.75 -87.00  89.38   52
 44  \w    106.00 132.00   0.50    0.70    --  101.75 -79.00   4.59   52
 45  \w     36.00  70.00   0.50    0.70    --  101.75 -79.00   4.59   68
 46  \w     75.00 104.00   0.50    0.70    --  101.75 -87.00 173.90   58
 47  \w     47.00 104.00   0.50    0.70    --  101.75  10.00-179.01  114
 48  \w    117.00 173.00   0.50    0.70    --  101.75  10.00-179.01  112
 49  \w     63.00 155.00   0.50    0.70    --  101.75  15.00 -13.57  184
 50  \w     58.00  84.00   0.50    0.70    --  101.75 -83.00 -90.43   52
 51  \w     78.00 105.00   0.50    0.70    --  101.75 -88.00   6.90   54
 52  \w     33.00  66.00   0.50    0.70    --  101.75 -84.00  87.37   66
 53  \w     34.00  63.00   0.50    0.70    --  101.75 -87.00 173.90   58
 54  \w     33.00  75.00   0.50    0.70    --  101.75 -75.00 111.35   84
 55  \w     35.00  68.00   0.50    0.70    --  101.75 -83.00 148.22   66
 56  \w     34.00  77.00   0.50    0.70    --  101.75 -79.00 -71.04   86
 57  \w     34.00  63.00   0.50    0.70    --  101.75 -90.00   4.77   58
 58  \w     34.00  70.00   0.50    0.70    --  101.75 -84.00-123.31   72
;
_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      0.0712266000
_diffrn_orient_matrix_UB_12      0.1322171000
_diffrn_orient_matrix_UB_13      0.0461197000
_diffrn_orient_matrix_UB_21      -0.0734917000
_diffrn_orient_matrix_UB_22      0.0014482000
_diffrn_orient_matrix_UB_23      -0.1056538000
_diffrn_orient_matrix_UB_31      -0.1395088000
_diffrn_orient_matrix_UB_32      0.0396693000
_diffrn_orient_matrix_UB_33      0.0630088000
_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  0.1196
_diffrn_reflns_av_unetI/netI     0.0649
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            25371
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.244
_diffrn_reflns_theta_min         3.770
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.793
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.414
_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    1.132
_exptl_crystal_description       block
_exptl_crystal_F_000             492
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane'
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.446
_refine_diff_density_min         -0.652
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     318
_refine_ls_number_reflns         4815
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0906
_refine_ls_R_factor_gt           0.0775
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1414P)^2^+0.8852P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2134
_refine_ls_wR_factor_ref         0.2251
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3879
_reflns_number_total             4815
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00276e3.cif
_cod_data_source_block           depAmmesAlH2_20-Al
_cod_depositor_comments
'Adding full bibliography for 7720566--7720581.cif.'
_cod_original_cell_volume        1333.93(8)
_cod_database_code               7720571
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C60 H78 Al2 N4'
_cell_oxdiff_angle_alpha         117.251(4)
_cell_oxdiff_angle_beta          91.690(2)
_cell_oxdiff_angle_gamma         97.296(2)
_cell_oxdiff_length_a            9.02116(18)
_cell_oxdiff_length_b            12.7128(5)
_cell_oxdiff_length_c            13.2559(4)
_cell_oxdiff_measurement_reflns_used 11533
_cell_oxdiff_volume              1333.93(7)
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.753
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name exp_69_DVT-465_full_exp.par
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C19-C20 \\sim C19-C20A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C20) = Uanis(C20A)
4. Others
 Sof(H19C)=Sof(H19D)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(1)
 Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C29(H29A,H29B), C17(H17A,H17B), C19(H19A,H19B), C19(H19C,H19D)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C23(H23), C24(H24), C25(H25), C13(H13), C15(H15), C14(H14)
5.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C8(H8A,H8B,H8C), C30(H30A,H30B,H30C), C9(H9A,H9B,H9C),
 C28(H28A,H28B,H28C), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C20A(H20D,H20E,
 H20F)
;
_shelx_res_checksum              38400
_shelx_hkl_checksum              83868
_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 2.652
_oxdiff_exptl_absorpt_empirical_full_min 0.207