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_7720573
_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         'C64 H80 Al2 F6 N4, 2(C7 H8)'
_chemical_formula_sum            'C78 H96 Al2 F6 N4'
_chemical_formula_weight         1257.54
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yc'
_space_group_name_H-M_alt        'P 1 2/c 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                 92.516(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.1717(2)
_cell_length_b                   15.5948(2)
_cell_length_c                   20.5002(4)
_cell_measurement_reflns_used    11638
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.8620
_cell_measurement_theta_min      3.5410
_cell_volume                     3568.11(11)
_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  'XL  (Sheldrick, 2008)'
_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 0.996
_diffrn_measured_fraction_theta_max 0.981
_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    -27.00  58.00   0.50    1.20    --   49.49 -49.00  33.00  170
  2  \w     41.00 126.00   0.50    1.20    --   49.49  49.00-179.00  170
  3  \w    -52.00  26.00   0.50    1.20    --  -51.24  49.00-179.00  156
  4  \w   -165.00 -79.00   0.50    1.20    --  -87.86 -49.00  33.00  172
  5  \w    -52.00 -11.00   0.50    1.20    --  -87.86  49.00-179.00   82
  6  \w     87.00 173.00   0.50    1.20    --   95.64  49.00-179.00  172
  7  \w     19.00  58.00   0.50    1.20    --   95.64 -49.00  33.00   78
  8  \w   -125.00 -78.00   0.50    1.20    --  -51.24-125.00 120.00   94
  9  \w     26.00  52.00   0.50    1.20    --   56.00  76.00-141.79   52
 10  \w     26.00  52.00   0.50    1.20    --   56.00  78.00 148.92   52
 11  \w    -68.00 -13.00   0.50    1.20    --  -87.86  61.00   0.00  110
 12  \w     18.00  54.00   0.50    1.20    --   95.64 -45.00-150.00   72
 13  \w     18.00  54.00   0.50    1.20    --   95.64 -45.00 -60.00   72
 14  \w     18.00  54.00   0.50    1.20    --   95.64 -45.00  90.00   72
 15  \w     18.00  54.00   0.50    1.20    --   95.64 -45.00 -90.00   72
 16  \w     18.00  54.00   0.50    1.20    --   95.64 -45.00-120.00   72
 17  \w     18.00  54.00   0.50    1.20    --   95.64 -45.00-180.00   72
 18  \w    142.00 169.00   0.50    1.20    --  101.75  -4.00 -19.57   54
 19  \w     33.00 110.00   0.50    1.20    --  101.75 -85.00 127.30  154
 20  \w     62.00 175.00   0.50    1.20    --  101.75  15.00  21.93  226
 21  \w    125.00 175.00   0.50    1.20    --  101.75  15.00  21.93  100
 22  \w     38.00  69.00   0.50    1.20    --  101.75 -76.00 159.26   62
 23  \w    128.00 173.00   0.50    1.20    --  101.75   9.00 -24.87   90
 24  \w     46.00 106.00   0.50    1.20    --  101.75 -84.00-121.93  120
 25  \w     46.00  82.00   0.50    1.20    --  101.75   9.00 -24.87   72
 26  \w     34.00  78.00   0.50    1.20    --  101.75 -77.00-157.18   88
 27  \w     34.00 104.00   0.50    1.20    --  101.75 -78.00  22.87  140
 28  \w     36.00 100.00   0.50    1.20    --  101.75 -75.00 -40.88  128
 29  \w     64.00  90.00   0.50    1.20    --  101.75 -75.00  70.93   52
 30  \w     32.00  60.00   0.50    1.20    --  101.75 -75.00  70.93   56
 31  \w     33.00  77.00   0.50    1.20    --  101.75 -77.00 -57.33   88
 32  \w     77.00 103.00   0.50    1.20    --  101.75  15.00  62.44   52
 33  \w    130.00 156.00   0.50    1.20    --  101.75  15.00  62.44   52
 34  \w     35.00  61.00   0.50    1.20    --  101.75 -75.00-108.52   52
 35  \w     71.00 105.00   0.50    1.20    --  101.75 -90.00  -5.19   68
 36  \w     41.00  98.00   0.50    1.20    --  101.75 -86.00-165.25  114
;
_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      0.1130791000
_diffrn_orient_matrix_UB_12      -0.0548441000
_diffrn_orient_matrix_UB_13      0.0129225000
_diffrn_orient_matrix_UB_21      0.0710653000
_diffrn_orient_matrix_UB_22      0.0604779000
_diffrn_orient_matrix_UB_23      -0.0434647000
_diffrn_orient_matrix_UB_31      0.0345541000
_diffrn_orient_matrix_UB_32      0.0555843000
_diffrn_orient_matrix_UB_33      0.0600866000
_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  0.0575
_diffrn_reflns_av_unetI/netI     0.0350
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            40309
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.074
_diffrn_reflns_theta_min         2.834
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.852
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.742
_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    1.170
_exptl_crystal_description       trapezoid
_exptl_crystal_F_000             1344
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.427
_refine_diff_density_min         -0.502
_refine_diff_density_rms         0.102
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.245
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     487
_refine_ls_number_reflns         7315
_refine_ls_number_restraints     272
_refine_ls_restrained_S_all      1.224
_refine_ls_R_factor_all          0.1333
_refine_ls_R_factor_gt           0.1288
_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^)+26.8872P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2790
_refine_ls_wR_factor_ref         0.2807
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6836
_reflns_number_total             7315
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00276e3.cif
_cod_data_source_block           dippAmpCF3AlH2_6-Al
_cod_depositor_comments
'Adding full bibliography for 7720566--7720581.cif.'
_cod_database_code               7720573
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C11 H10 N O'
_cell_oxdiff_angle_alpha         90.017(2)
_cell_oxdiff_angle_beta          92.476(2)
_cell_oxdiff_angle_gamma         90.071(2)
_cell_oxdiff_length_a            11.1777(3)
_cell_oxdiff_length_b            15.5978(4)
_cell_oxdiff_length_c            20.4845(5)
_cell_oxdiff_measurement_reflns_used 11638
_cell_oxdiff_volume              3568.10(16)
_shelx_estimated_absorpt_t_max   0.975
_shelx_estimated_absorpt_t_min   0.841
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name exp_43_DVT-410_full_exp.par
_olex2_refinement_description
;
1. Restrained distances
 C46-C40
 1.51 with sigma of 0.02
 C40-C45 = C40-C41 = C44-C43
 1.39 with sigma of 0.02
 C45-C44 = C43-C42 = C42-C41
 1.38 with sigma of 0.02
 C39-C33
 1.51 with sigma of 0.02
 C33-C38 = C33-C34 = C37-C36
 1.39 with sigma of 0.02
 C38-C37 = C36-C35 = C35-C34
 1.38 with sigma of 0.02
 C46-C45 = C46-C41
 2.52 with sigma of 0.04
 C40-C44
 2.42 with sigma of 0.04
 C40-C42
 2.41 with sigma of 0.04
 C45-C43
 2.39 with sigma of 0.04
 C44-C42 = C43-C41
 2.4 with sigma of 0.04
 C39-C38 = C39-C34
 2.52 with sigma of 0.04
 C33-C37
 2.42 with sigma of 0.04
 C33-C35
 2.41 with sigma of 0.04
 C38-C36
 2.39 with sigma of 0.04
 C37-C35 = C36-C34
 2.4 with sigma of 0.04
 C40-C45 \\sim C45-C44 \\sim C44-C43 \\sim C43-C42 \\sim C42-C41 \\sim C41-C40
 with sigma of 0.02
 C40-C42 \\sim C40-C44 \\sim C41-C43 \\sim C45-C41 \\sim C44-C42 \\sim C45-C43
 with sigma of 0.04
 C46-C41 \\sim C46-C45
 with sigma of 0.04
 C33-C38 \\sim C38-C37 \\sim C37-C36 \\sim C36-C35 \\sim C35-C34 \\sim C34-C33
 with sigma of 0.02
 C33-C35 \\sim C33-C37 \\sim C34-C36 \\sim C38-C34 \\sim C37-C35 \\sim C38-C36
 with sigma of 0.04
 C39-C34 \\sim C39-C38
 with sigma of 0.04
2. Restrained planarity
 C46, C40, C45, C44, C43, C42, C41
 with sigma of 0.1
 C39, C33, C38, C37, C36, C35, C34
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
C46 \\sim C40 \\sim C45 \\sim C44 \\sim C43 \\sim C42 \\sim C41: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C39 \\sim C33 \\sim C38 \\sim C37 \\sim C36 \\sim C35 \\sim C34: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 C46, C40, C45, C44, C43, C42, C41
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C39, C33, C38, C37, C36, C35, C34
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C46(0.5) H46A(0.5) H46B(0.5) H46C(0.5) C40(0.5) C45(0.5) H45(0.5)
 C44(0.5) H44(0.5) C43(0.5) H43(0.5) C42(0.5) H42(0.5) C41(0.5) H41(0.5)
 C39(0.5) H39A(0.5) H39B(0.5) H39C(0.5) C33(0.5) C38(0.5) H38(0.5) C37(0.5)
 H37(0.5) C36(0.5) H36(0.5) C35(0.5) H35(0.5) C34(0.5) H34(0.5)
6.a Ternary CH refined with riding coordinates:
 C18(H18), C30(H30), C27(H27), C15(H15)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C13(H13), C23(H23), C6(H6), C25(H25), C7(H7), C11(H11),
 C12(H12), C24(H24), C45(H45), C44(H44), C43(H43), C42(H42), C41(H41), C38(H38),
  C37(H37), C36(H36), C35(H35), C34(H34)
6.c Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C20(H20A,H20B,H20C), C29(H29A,H29B,H29C), C19(H19A,H19B,
 H19C), C17(H17A,H17B,H17C), C31(H31A,H31B,H31C), C16(H16A,H16B,H16C), C32(H32A,
 H32B,H32C), C46(H46A,H46B,H46C), C39(H39A,H39B,H39C)
;
_shelx_res_checksum              27234
_shelx_hkl_checksum              23678
_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 3.318
_oxdiff_exptl_absorpt_empirical_full_min 0.457