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_7720580
_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         '2(C33 H45 Al N2 O0.132), C7 H8'
_chemical_formula_sum            'C73 H98 Al2 N4 O0.26'
_chemical_formula_weight         1089.73
_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             2025-12-17
_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                90
_cell_angle_beta                 90.3080(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   31.6819(3)
_cell_length_b                   12.94370(10)
_cell_length_c                   32.8715(4)
_cell_measurement_reflns_used    42144
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.7850
_cell_measurement_theta_min      2.6860
_cell_volume                     13479.8(2)
_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    -18.00  82.00   0.50    1.00    --   49.49 -82.00  82.00  200
  2  \w    -83.00  17.00   0.50    1.00    --  -51.24  82.00-155.00  200
  3  \w   -120.00 -20.00   0.50    1.00    --  -87.86  82.00-155.00  200
  4  \w   -156.00 -81.00   0.50    1.00    --  -87.86 -82.00  82.00  150
  5  \w     88.00 164.00   0.50    1.00    --   95.64  82.00-155.00  152
  6  \w     28.00 128.00   0.50    1.00    --   95.64 -82.00  82.00  200
  7  \w    -24.00   2.00   0.50    1.00    --   28.00 122.00 -78.80   52
  8  \w   -120.00 -75.00   0.50    1.00    --  -51.24 -77.00 -60.00   90
  9  \w   -120.00 -75.00   0.50    1.00    --  -51.24 -77.00  90.00   90
 10  \w   -120.00 -75.00   0.50    1.00    --  -51.24 -77.00-180.00   90
 11  \w     25.00  52.00   0.50    1.00    --   56.00  79.00 -77.17   54
 12  \w    -48.00 -10.00   0.50    1.00    --  -87.86  45.00  30.00   76
 13  \w     22.00 111.00   0.50    1.00    --   95.64-125.00-180.00  178
 14  \w     22.00  84.00   0.50    1.00    --   95.64-125.00  60.00  124
 15  \w     22.00 111.00   0.50    1.00    --   95.64-125.00 -30.00  178
 16  \w     26.00 104.00   0.50    1.00    --   95.64 -95.00  60.00  156
 17  \w     22.00 111.00   0.50    1.00    --   95.64-125.00 120.00  178
 18  \w     81.00 165.00   0.50    1.00    --   95.64  77.00  60.00  168
 19  \w     22.00 111.00   0.50    1.00    --   95.64-125.00-180.00  178
 20  \w     81.00 165.00   0.50    1.00    --   95.64  77.00-180.00  168
 21  \w     22.00 111.00   0.50    1.00    --   95.64-125.00 -60.00  178
 22  \w     22.00 111.00   0.50    1.00    --   95.64-125.00 -60.00  178
 23  \w     21.00  74.00   0.50    1.00    --   95.64 -61.00 -60.00  106
 24  \w     22.00 111.00   0.50    1.00    --   95.64-125.00-120.00  178
 25  \w     22.00  84.00   0.50    1.00    --   95.64-125.00  60.00  124
 26  \w     18.00  52.00   0.50    1.00    --   95.64 -45.00  90.00   68
 27  \w     33.00  59.00   0.50    1.00    --   95.64-125.00 -30.00   52
 28  \w     21.00  74.00   0.50    1.00    --   95.64 -61.00 150.00  106
 29  \w     94.00 171.00   0.50    1.00    --   95.64  45.00 120.00  154
 30  \w     69.00 110.00   0.50    1.00    --   95.64-125.00  90.00   82
 31  \w     64.00  99.00   0.50    1.00    --   95.64 -95.00  60.00   70
 32  \w     34.00  61.00   0.50    1.00    --  101.75 -82.00  32.32   54
 33  \w     34.00  64.00   0.50    1.00    --  101.75 -79.00-136.67   60
 34  \w     78.00 172.00   0.50    1.00    --  101.75  10.00  41.62  188
 35  \w     33.00  66.00   0.50    1.00    --  101.75 -79.00 141.05   66
 36  \w     40.00  65.00   0.50    1.00    --  101.75  10.00  41.62   50
 37  \w     50.00  88.00   0.50    1.00    --  101.75 -83.00  65.05   76
 38  \w     35.00  99.00   0.50    1.00    --  101.75 -88.00-109.24  128
 39  \w     59.00 166.00   0.50    1.00    --  101.75  14.00 132.43  214
 40  \w     44.00  70.00   0.50    1.00    --  101.75 -85.00 119.44   52
 41  \w     34.00  61.00   0.50    1.00    --  101.75 -86.00  -6.74   54
 42  \w     72.00 101.00   0.50    1.00    --  101.75 -87.00 -66.28   58
 43  \w     37.00  88.00   0.50    1.00    --  101.75 -86.00-144.43  102
 44  \w     36.00  73.00   0.50    1.00    --  101.75 -82.00  54.10   74
 45  \w     34.00  60.00   0.50    1.00    --  101.75 -80.00 -45.11   52
 46  \w     34.00  60.00   0.50    1.00    --  101.75 -78.00-169.76   52
 47  \w     63.00 106.00   0.50    1.00    --  101.75 -89.00 -21.97   86
 48  \w     33.00  94.00   0.50    1.00    --  101.75 -85.00 168.12  122
 49  \w     33.00  59.00   0.50    1.00    --  101.75 -89.00 -21.97   52
 50  \w     33.00  70.00   0.50    1.00    --  101.75 -77.00 -91.58   74
 51  \w     57.00  98.00   0.50    1.00    --  101.75  12.00 -32.37   82
 52  \w    141.00 171.00   0.50    1.00    --  101.75  12.00 -32.37   60
 53  \w     47.00  97.00   0.50    1.00    --  101.75  12.00 -91.98  100
 54  \w     32.00  68.00   0.50    1.00    --  101.75 -76.00   7.94   72
 55  \w     34.00  62.00   0.50    1.00    --  101.75 -80.00 -60.95   56
 56  \w     70.00 105.00   0.50    1.00    --  101.75 -90.00 119.84   70
 57  \w     33.00  60.00   0.50    1.00    --  101.75 -76.00-133.53   54
 58  \w     34.00  74.00   0.50    1.00    --  101.75 -81.00  99.54   80
 59  \w     35.00  60.00   0.50    1.00    --  101.75 -81.00  -1.08   50
 60  \w     46.00  72.00   0.50    1.00    --  101.75 -79.00 160.11   52
 61  \w     36.00  62.00   0.50    1.00    --  101.75 -90.00 119.84   52
 62  \w     67.00  93.00   0.50    1.00    --  101.75 -79.00 141.05   52
;
_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      -0.0305594000
_diffrn_orient_matrix_UB_12      -0.0411152000
_diffrn_orient_matrix_UB_13      -0.0328545000
_diffrn_orient_matrix_UB_21      -0.0376761000
_diffrn_orient_matrix_UB_22      0.0423996000
_diffrn_orient_matrix_UB_23      0.0242671000
_diffrn_orient_matrix_UB_31      0.0032955000
_diffrn_orient_matrix_UB_32      0.1033220000
_diffrn_orient_matrix_UB_33      -0.0229942000
_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  0.0933
_diffrn_reflns_av_unetI/netI     0.0352
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       39
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            160551
_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         76.095
_diffrn_reflns_theta_min         2.688
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.703
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67894
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.118a (Rigaku Oxford Diffraction, 2025)
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    1.074
_exptl_crystal_description       plank
_exptl_crystal_F_000             4737
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.386
_refine_diff_density_min         -0.405
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     755
_refine_ls_number_reflns         13972
_refine_ls_number_restraints     19
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0572
_refine_ls_R_factor_gt           0.0528
_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^)+(0.0615P)^2^+19.0183P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1421
_refine_ls_wR_factor_ref         0.1450
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12618
_reflns_number_total             13972
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00276e3.cif
_cod_data_source_block           dippAm24XylAlH2_9-Al
_cod_depositor_comments
'Adding full bibliography for 7720566--7720581.cif.'
_cod_database_code               7720580
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C73 H98 Al2 N4'
_cell_oxdiff_angle_alpha         90.0432(7)
_cell_oxdiff_angle_beta          90.3476(7)
_cell_oxdiff_angle_gamma         90.0005(7)
_cell_oxdiff_length_a            31.6840(3)
_cell_oxdiff_length_b            12.94436(11)
_cell_oxdiff_length_c            32.8678(2)
_cell_oxdiff_measurement_reflns_used 41821
_cell_oxdiff_volume              13479.8(2)
_shelx_estimated_absorpt_t_max   0.966
_shelx_estimated_absorpt_t_min   0.776
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name exp_48_DVT-393_full_exp.par
_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) groups, All O(H) groups
2. Restrained distances
 O1-H1
 0.87 with sigma of 0.01
 O2-H2
 0.87 with sigma of 0.01
 Al1-H1
 2.640377 with sigma of 0.02
 Al2-H2
 2.611386 with sigma of 0.02
 C70A-C71A \\sim C70-C71
 with sigma of 0.02
 C70A-C69A \\sim C70-C69
 with sigma of 0.02
 C67A-C68A \\sim C67-C68
 with sigma of 0.02
 C67A-C72A \\sim C67-C72
 with sigma of 0.02
 C67A-C73A \\sim C67-C73
 with sigma of 0.02
 C71A-C72A \\sim C71-C72
 with sigma of 0.02
 C68A-C69A \\sim C68-C69
 with sigma of 0.02
 C70A-C68A \\sim C70-C68
 with sigma of 0.04
 C70A-C72A \\sim C70-C72
 with sigma of 0.04
 C67A-C71A \\sim C67-C71
 with sigma of 0.04
 C67A-C69A \\sim C67-C69
 with sigma of 0.04
 C71A-C69A \\sim C71-C69
 with sigma of 0.04
 C68A-C72A \\sim C68-C72
 with sigma of 0.04
 C68A-C73A \\sim C68-C73
 with sigma of 0.04
 C72A-C73A \\sim C72-C73
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C73A) = Uanis(C70A) = Uanis(C71A) = Uanis(C69A) = Uanis(C72A) =
Uanis(C68A) = Uanis(C67A) = Uanis(C73) = Uanis(C67) = Uanis(C68) = Uanis(C72) =
Uanis(C69) = Uanis(C71) = Uanis(C70)
Uanis(O2) = Uanis(O1)
4. Others
 Sof(C73)=Sof(H73D)=Sof(H73E)=Sof(H73F)=Sof(C67)=Sof(C68)=Sof(H68)=Sof(C69)=
 Sof(H69)=Sof(C70)=Sof(H70)=Sof(C71)=Sof(H71)=Sof(C72)=Sof(H72)=1-FVAR(1)
 Sof(C70A)=Sof(H70A)=Sof(C67A)=Sof(C71A)=Sof(H71A)=Sof(C68A)=Sof(H68A)=
 Sof(C69A)=Sof(H69A)=Sof(C72A)=Sof(H72A)=Sof(C73A)=Sof(H73A)=Sof(H73B)=
 Sof(H73C)=FVAR(1)
 Sof(HB)=Sof(HC)=1-FVAR(2)
 Sof(O1)=Sof(H1)=Sof(O2)=Sof(H2)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C61(H61), C19(H19), C52(H52), C64(H64), C16(H16), C31(H31), C28(H28), C49(H49)
5.b Aromatic/amide H refined with riding coordinates:
 C39(H39), C40(H40), C3(H3), C12(H12), C37(H37), C57(H57), C6(H6), C4(H4),
 C14(H14), C13(H13), C59(H59), C24(H24), C58(H58), C26(H26), C25(H25), C47(H47),
  C45(H45), C46(H46), C70A(H70A), C71A(H71A), C68A(H68A), C69A(H69A),
 C72A(H72A), C68(H68), C69(H69), C70(H70), C71(H71), C72(H72)
5.c Idealised Me refined as rotating group:
 C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C9(H9A,H9B,H9C), C54(H54A,H54B,H54C), C18(H18A,H18B,H18C), C65(H65A,
 H65B,H65C), C66(H66A,H66B,H66C), C63(H63A,H63B,H63C), C30(H30A,H30B,H30C),
 C62(H62A,H62B,H62C), C51(H51A,H51B,H51C), C53(H53A,H53B,H53C), C8(H8A,H8B,H8C),
  C33(H33A,H33B,H33C), C50(H50A,H50B,H50C), C32(H32A,H32B,H32C), C17(H17A,H17B,
 H17C), C29(H29A,H29B,H29C), C73A(H73A,H73B,H73C), C73(H73D,H73E,H73F)
;
_shelx_res_checksum              55519
_shelx_hkl_checksum              64602
_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 5.161
_oxdiff_exptl_absorpt_empirical_full_min 0.394