Green Synthesis of α-Aminophosphonates: From Hydrogen-Bonded Janus Dimers to Pharmaceutical Potential
Kholany, Rawda; Mardini, Alaa A.; Shakirova, Ksenia; Islamov, Daut; Gerasimov, Alexander; Klimovitskii, Alexander; Vavilova, Alena A.; Mostovaya, Olga; Gazizova, Asiya; Stoikov, Ivan; Organic & Biomolecular Chemistry  (2025) –; doi:10.1039/D5OB01712B

data_7160906
_publ_section_title
;
 Green Synthesis of \a-Aminophosphonates: From Hydrogen-Bonded Janus
 Dimers to Pharmaceutical Potential
;
_journal_name_full               'Organic &amp; Biomolecular Chemistry'
_journal_paper_doi               10.1039/D5OB01712B
_journal_year                    2025
_chemical_formula_moiety         'C17 H29 N2 O4 P'
_chemical_formula_sum            'C17 H29 N2 O4 P'
_chemical_formula_weight         356.39
_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             2025-10-17
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2025-10-20 deposited with the CCDC.	2025-11-28 downloaded from the CCDC.
;
_cell_angle_alpha                79.245(3)
_cell_angle_beta                 82.358(3)
_cell_angle_gamma                72.517(4)
_cell_formula_units_Z            2
_cell_length_a                   8.3755(4)
_cell_length_b                   8.9060(3)
_cell_length_c                   14.1032(5)
_cell_measurement_reflns_used    13205
_cell_measurement_temperature    303.8(9)
_cell_measurement_theta_max      75.9680
_cell_measurement_theta_min      3.2010
_cell_volume                     982.44(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      303.8(9)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.943
_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     67.00  92.00   0.50    9.00    --   46.31-150.00-151.00   50
  2  \w     20.00  52.00   0.50    9.00    --   46.31-122.00  10.00   64
  3  \w     80.00 115.00   0.50    9.00    --   46.31 150.00-106.00   70
  4  \w   -109.00 -71.00   0.50    9.00    --  -47.56 150.00-106.00   76
  5  \w    -93.00 -41.00   0.50    9.00    --  -47.56 122.00  91.00  104
  6  \w   -118.00 -56.00   0.50    9.00    --  -47.56-150.00-151.00  124
  7  \w    -36.00 -11.00   0.50    9.00    --  -47.56 122.00  91.00   50
  8  \w     33.00 126.00   0.50   25.00    --  103.80-150.00-151.00  186
  9  \w    102.00 127.00   0.50   25.00    --  103.80 122.00  91.00   50
 10  \w     87.00 112.00   0.50   25.00    --  103.80 150.00-106.00   50
 11  \w   -135.00-110.00   0.50   25.00    -- -105.05-150.00-151.00   50
 12  \w    -95.00 -70.00   0.50   25.00    -- -105.05 122.00  91.00   50
 13  \w   -129.00 -47.00   0.50   25.00    -- -105.05 150.00-106.00  164
 14  \w   -135.00-109.00   0.50   25.00    -- -105.05-122.00  10.00   52
 15  \w    -39.00 -13.00   0.50    9.00    --    8.00 125.00   4.43   52
 16  \w    -14.00  11.00   0.50    9.00    --   20.00 100.00  34.91   50
 17  \w     -5.00  25.00   0.50    9.00    --   24.00  94.00 158.20   60
 18  \w     11.00  36.00   0.50    9.00    --   40.00  91.00 130.10   50
 19  \w     11.00  36.00   0.50    9.00    --   40.00  90.00-120.98   50
 20  \w     28.00  54.00   0.50    9.00    --   46.31  77.00  30.00   52
 21  \w     24.00  50.00   0.50    9.00    --   46.31  77.00   0.00   52
 22  \w     82.00 108.00   0.50    9.00    --   46.31  77.00  30.00   52
 23  \w     86.00 112.00   0.50    9.00    --   46.31  77.00   0.00   52
 24  \w     39.00  92.00   0.50    9.00    --   46.31  19.00 -90.00  106
 25  \w    -52.00 -26.00   0.50    9.00    --  -47.56 -77.00  60.00   52
 26  \w     32.00  58.00   0.50    9.00    --   52.00  77.00-139.28   52
 27  \w     33.00  71.00   0.50    9.00    --   52.00  74.00 -47.45   76
 28  \w    -68.00 -29.00   0.50    9.00    --  -52.00 -76.00  -5.47   78
 29  \w     40.00  66.00   0.50    9.00    --   60.00  73.00   5.92   52
 30  \w     40.00  66.00   0.50    9.00    --   60.00  74.00 -83.44   52
 31  \w     38.00  63.00   0.50    9.00    --   60.00  75.00  93.13   50
 32  \w     41.00  90.00   0.50    9.00    --   60.00  76.00 166.67   98
 33  \w    -65.00 -39.00   0.50    9.00    --  -60.00 -73.00 101.61   52
 34  \w     42.00  68.00   0.50    9.00    --   60.00  72.00 147.99   52
 35  \w     42.00  72.00   0.50    9.00    --   64.00  75.00  33.88   60
 36  \w     43.00  69.00   0.50    9.00    --   64.00  73.00 -31.82   52
 37  \w     42.00  68.00   0.50    9.00    --   64.00  76.00-123.04   52
 38  \w    -74.00 -48.00   0.50    9.00    --  -64.00 -66.00  69.01   52
 39  \w    -74.00 -48.00   0.50    9.00    --  -68.00 -70.00-102.10   52
 40  \w    -86.00 -48.00   0.50    9.00    --  -68.00 -70.00  -7.17   76
 41  \w     46.00  72.00   0.50    9.00    --   68.00  75.00-159.97   52
 42  \w    -80.00 -54.00   0.50    9.00    --  -76.00 -74.00 176.82   52
 43  \w    -80.00 -55.00   0.50    9.00    --  -76.00 -73.00  59.86   50
 44  \w    -97.00 -64.00   0.50    9.00    --  -76.00 -58.00  22.89   66
 45  \w    -82.00 -56.00   0.50    9.00    --  -76.00 -72.00 -93.92   52
 46  \w    -84.00 -56.00   0.50    9.00    --  -76.00 -73.00 104.59   56
 47  \w    -83.00 -54.00   0.50    9.00    --  -76.00 -75.00 133.44   58
 48  \w    -83.00 -58.00   0.50   25.00    --  -80.00 -75.00 -37.38   50
 49  \w    -93.00 -59.00   0.50   25.00    --  -80.00 -73.00 -98.75   68
 50  \w    -87.00 -61.00   0.50   25.00    --  -80.00 -72.00  91.70   52
 51  \w    -85.00 -59.00   0.50   25.00    --  -80.00 -72.00-130.32   52
 52  \w    -89.00 -63.00   0.50   25.00    --  -84.00 -73.00 -12.72   52
 53  \w    -88.00 -63.00   0.50   25.00    --  -84.00 -72.00 160.93   50
 54  \w   -110.00 -65.00   0.50   25.00    --  -84.00 -67.00 -53.43   90
 55  \w   -144.00-118.00   0.50   25.00    --  -84.00 -72.00 160.93   52
 56  \w    -92.00 -66.00   0.50   25.00    --  -84.00 -71.00  87.51   52
 57  \w    -93.00 -62.00   0.50   25.00    --  -84.00 -75.00-169.48   62
 58  \w    -90.00 -63.00   0.50   25.00    --  -84.00 -72.00  58.90   54
 59  \w   -155.00 -97.00   0.50   25.00    --  -84.00 -72.00  58.90  116
 60  \w   -102.00 -67.00   0.50   25.00    --  -84.00 -61.00   0.66   70
 61  \w    -91.00 -66.00   0.50   25.00    --  -84.00 -65.00-164.16   50
 62  \w   -137.00-112.00   0.50   25.00    --  -84.00 -65.00-164.16   50
 63  \w    -91.00 -66.00   0.50   25.00    --  -88.00 -74.00 -52.32   50
 64  \w    -92.00 -67.00   0.50   25.00    --  -88.00 -75.00 -93.51   50
 65  \w   -152.00-126.00   0.50   25.00    --  -88.00 -75.00 -93.51   52
 66  \w   -160.00 -98.00   0.50   25.00    --  -88.00 -74.00 -52.32  124
 67  \w   -123.00 -69.00   0.50   25.00    --  -88.00 -72.00-151.63  108
 68  \w   -154.00 -71.00   0.50   25.00    --  -88.00 -64.00 -31.63  166
 69  \w   -130.00 -75.00   0.50   25.00    --  -92.00 -68.00 166.48  110
 70  \w   -135.00 -74.00   0.50   25.00    --  -92.00 -67.00  82.57  122
 71  \w    -95.00 -70.00   0.50   25.00    --  -92.00 -74.00  36.88   50
 72  \w   -140.00-114.00   0.50   25.00    --  -96.00 -56.00-119.22   52
 73  \w   -156.00 -73.00   0.50   25.00    --  -96.00 -76.00 -63.77  166
 74  \w   -168.00 -82.00   0.50   25.00    --  -96.00 -59.00 142.44  172
 75  \w   -106.00 -73.00   0.50   25.00    --  -96.00 -76.00-121.65   66
 76  \w   -162.00-136.00   0.50   25.00    --  -96.00 -76.00-121.65   52
 77  \w   -167.00 -76.00   0.50   25.00    --  -96.00 -69.00 120.72  182
 78  \w   -127.00 -79.00   0.50   25.00    --  -96.00 -65.00 -10.89   96
 79  \w   -165.00-140.00   0.50   25.00    --  -96.00 -65.00-119.17   50
 80  \w    -98.00 -73.00   0.50   25.00    --  -96.00 -77.00  13.43   50
 81  \w   -155.00-129.00   0.50   25.00    --  -96.00 -77.00  13.43   52
 82  \w   -167.00 -82.00   0.50   25.00    --  -96.00 -59.00  37.94  170
 83  \w   -106.00 -81.00   0.50   25.00    --  -96.00 -56.00-119.22   50
 84  \w   -137.00 -78.00   0.50   25.00    --  -96.00 -65.00-119.17  118
 85  \w     32.00  69.00   0.50   25.00    --  103.80 -61.00 -30.00   74
 86  \w     40.00  71.00   0.50   25.00    --  103.80 -61.00-120.00   62
 87  \w     44.00 104.00   0.50   25.00    --  103.80 -94.00-150.00  120
 88  \w     31.00  70.00   0.50   25.00    --  103.80 -61.00  60.00   78
 89  \w     31.00  70.00   0.50   25.00    --  103.80 -61.00-150.00   78
 90  \w     70.00  95.00   0.50   25.00    --  103.80-122.00  10.00   50
 91  \w     35.00  67.00   0.50   25.00    --  103.80 -61.00 -90.00   64
 92  \w     31.00  56.00   0.50   25.00    --  103.80 -61.00   0.00   50
 93  \w   -111.00 -50.00   0.50   25.00    -- -105.05 125.00 150.00  122
 94  \w    -84.00 -32.00   0.50   25.00    -- -105.05  77.00 120.00  104
 95  \w   -105.00 -80.00   0.50   25.00    -- -105.05 -83.00  85.90   50
 96  \w   -165.00-109.00   0.50   25.00    -- -105.05 -83.00  85.90  112
 97  \w   -173.00 -82.00   0.50   25.00    -- -105.05 -78.00-149.81  182
 98  \w   -167.00 -89.00   0.50   25.00    -- -105.05 -67.00  30.46  156
 99  \w   -110.00 -34.00   0.50   25.00    -- -105.05 125.00   0.00  152
100  \w    -67.00 -41.00   0.50   25.00    -- -105.05  61.00-120.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1426640000
_diffrn_orient_matrix_UB_12      0.0870019000
_diffrn_orient_matrix_UB_13      0.0683453000
_diffrn_orient_matrix_UB_21      0.0895364000
_diffrn_orient_matrix_UB_22      -0.1046959000
_diffrn_orient_matrix_UB_23      0.0881746000
_diffrn_orient_matrix_UB_31      0.0952463000
_diffrn_orient_matrix_UB_32      0.1231706000
_diffrn_orient_matrix_UB_33      0.0008766000
_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  0.0557
_diffrn_reflns_av_unetI/netI     0.0224
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.943
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            24581
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.266
_diffrn_reflns_theta_min         5.271
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.423
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.595
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.80a (Rigaku Oxford Diffraction, 2023)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.205
_exptl_crystal_description       plate
_exptl_crystal_F_000             384
_exptl_crystal_size_max          0.395
_exptl_crystal_size_mid          0.083
_exptl_crystal_size_min          0.022
_refine_diff_density_max         0.982
_refine_diff_density_min         -0.412
_refine_diff_density_rms         0.121
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.524
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     235
_refine_ls_number_reflns         3885
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.524
_refine_ls_R_factor_all          0.1116
_refine_ls_R_factor_gt           0.1057
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3349
_refine_ls_wR_factor_ref         0.3411
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3360
_reflns_number_total             3885
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01712b2.cif
_cod_data_source_block           stoi880_corr
_cod_database_code               7160906
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C17H29N2O4P
_shelx_estimated_absorpt_t_max   0.972
_shelx_estimated_absorpt_t_min   0.607
_reflns_odcompleteness_completeness 99.37
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_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
 C2A-C15 \\sim C15-C2
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C2A) = Uanis(C2)
4. Others
 Sof(H15C)=Sof(H15D)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=1-FVAR(1)
 Sof(H15A)=Sof(H15B)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C3(H3A,H3B), C13(H13A,H13B), C15(H15A,H15B), C15(H15C,H15D)
5.b Aromatic/amide H refined with riding coordinates:
 C1(H1A), C8(H8), C12(H12), C14(H14)
5.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C9(H9A,H9B,H9C), C5(H5A,H5B,H5C), C7(H7A,H7B,H7C),
 C2(H2A,H2B,H2C), C2A(H2AA,H2AB,H2AC)
;
_shelx_res_checksum              54219
_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 1.658
_oxdiff_exptl_absorpt_empirical_full_min 0.604