Observation of the solvent enantio-isotope effect in asymmetric ring-opening of cyclic diaryliodoniums with selenocyanate
Li, Yuanyuan; Tao, Chenyu; Duan, Longhui; Gu, Zhenhua; Chemical Science 16 (2025) 6488–6494; doi:10.1039/D5SC00014A

data_1574136
_publ_section_title
;
 Observation of the solvent enantio-isotope effect in asymmetric
 ring-opening of cyclic diaryliodoniums with selenocyanate
;
_journal_issue                   15
_journal_name_full               'Chemical Science'
_journal_page_first              6488
_journal_page_last               6494
_journal_paper_doi               10.1039/D5SC00014A
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H21 I N2 O Se'
_chemical_formula_sum            'C22 H21 I N2 O Se'
_chemical_formula_weight         535.27
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2024-05-18
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2024-07-27 deposited with the CCDC.	2025-03-11 downloaded from the CCDC.
;
_cell_angle_alpha                63.903(5)
_cell_angle_beta                 80.905(4)
_cell_angle_gamma                86.542(4)
_cell_formula_units_Z            2
_cell_length_a                   9.3735(5)
_cell_length_b                   11.1993(6)
_cell_length_c                   11.3482(5)
_cell_measurement_reflns_used    9374
_cell_measurement_temperature    293.3(5)
_cell_measurement_theta_max      72.8770
_cell_measurement_theta_min      4.3390
_cell_volume                     1056.34(10)
_computing_cell_refinement       'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      293.3(5)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.952
_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    -30.00  36.00   0.50    0.17    --   44.62 -29.00  11.00  132
  2  \w     22.00  61.00   0.50    0.17    --   44.62 -57.00 -60.00   78
  3  \w    -19.00  20.00   0.50    0.17    --   44.62 -57.00 -60.00   78
  4  \w    -14.00  22.00   0.50    0.17    --   44.62 -37.00-120.00   72
  5  \w     27.00  52.00   0.50    0.30    --   99.00 -45.00-180.00   50
  6  \w     26.00  71.00   0.50    0.30    --   99.00 -61.00-150.00   90
  7  \w     28.00  71.00   0.50    0.30    --   99.00 -61.00 -90.00   86
  8  \w     45.00  73.00   0.50    0.30    --   99.00 -61.00 -60.00   56
  9  \w     67.00 100.00   0.50    0.30    --   99.00 -77.00 120.00   66
 10  \w     32.00  64.00   0.50    0.30    --   99.00 -77.00 120.00   64
 11  \w     27.00  73.00   0.50    0.30    --   99.00 -61.00 150.00   92
 12  \w     63.00  89.00   0.50    0.17    --   44.62-125.00  30.00   52
 13  \w     84.00 112.00   0.50    0.30    --   99.00-125.00  60.00   56
 14  \w     39.00  69.00   0.50    0.30    --   99.00-125.00  60.00   60
 15  \w     50.00  87.00   0.50    0.30    --   99.00-125.00 120.00   74
 16  \w     31.00  76.00   0.50    0.30    --   99.00-125.00 -90.00   90
 17  \w     80.00 110.00   0.50    0.30    --   99.00-125.00 -90.00   60
 18  \w     67.00 111.00   0.50    0.30    --   99.00-125.00-120.00   88
 19  \w     36.00  91.00   0.50    0.17    --   44.62-125.00-150.00  110
 20  \w     74.00 106.00   0.50    0.30    --   99.00 -94.00-120.00   64
 21  \w     33.00 104.00   0.50    0.30    --   99.00 -94.00 -60.00  142
 22  \w     27.00  96.00   0.50    0.30    --   99.00 -94.00 120.00  138
 23  \w     83.00 172.00   0.50    0.30    --   99.00  15.00  90.00  178
 24  \w    116.00 165.00   0.50    0.30    --   99.00  29.00 172.00   98
 25  \w     30.00 119.00   0.50    0.17    --   44.62  29.00 172.00  178
 26  \w     83.00 169.00   0.50    0.30    --   99.00  15.00 -60.00  172
 27  \w    121.00 158.00   0.50    0.30    --   99.00 125.00-150.00   74
 28  \w     80.00 114.00   0.50    0.30    --   99.00 125.00-150.00   68
 29  \w     80.00 149.00   0.50    0.30    --   99.00 125.00 -90.00  138
 30  \w     84.00 114.00   0.50    0.30    --   99.00 125.00 150.00   60
 31  \w    124.00 164.00   0.50    0.30    --   99.00 125.00 150.00   80
 32  \w    -13.00  13.00   0.50    0.17    --  -44.62  29.00 172.00   52
 33  \w    -60.00 -29.00   0.50    0.30    --  -99.00 129.00  75.77   62
 34  \w   -115.00 -66.00   0.50    0.30    --  -99.00 129.00  75.77   98
 35  \w   -103.00 -53.00   0.50    0.30    --  -99.00  77.00  60.00  100
 36  \w    -63.00 -28.00   0.50    0.30    --  -99.00  61.00   0.00   70
 37  \w   -117.00 -66.00   0.50    0.17    --  -44.62 -29.00  11.00  102
 38  \w   -159.00 -84.00   0.50    0.30    --  -99.00 -29.00  11.00  150
 39  \w    -63.00 -32.00   0.50    0.17    --  -44.62 -29.00  11.00   62
 40  \w    -17.00  25.00   0.50    0.17    --  -45.87  29.00 172.00   84
 41  \w    -11.00  26.00   0.50    0.17    --   22.00  98.00  75.10   74
 42  \w    -69.00 -34.00   0.50    0.17    --  -45.87 -37.00-120.00   70
 43  \w    -67.00 -33.00   0.50    0.17    --  -45.87 -47.00 -32.92   68
 44  \w     23.00  50.00   0.50    0.17    --   45.87  77.00 150.00   54
 45  \w     94.00 119.00   0.50    0.17    --   45.87  77.00 -30.00   50
 46  \w     22.00  48.00   0.50    0.17    --   45.87  77.00  30.00   52
 47  \w     22.00  47.00   0.50    0.17    --   45.87  77.00 -30.00   50
 48  \w     23.00  48.00   0.50    0.17    --   45.87  77.00 -90.00   50
 49  \w     24.00  50.00   0.50    0.17    --   45.87  77.00-150.00   52
 50  \w     79.00 104.00   0.50    0.17    --   50.00  75.00 118.10   50
 51  \w     27.00  62.00   0.50    0.17    --   50.00  75.00 118.10   70
 52  \w     28.00  64.00   0.50    0.17    --   50.00  75.00 -21.49   72
 53  \w     34.00  60.00   0.50    0.17    --   54.00  74.00-155.17   52
 54  \w    100.00 126.00   0.50    0.17    --   54.00  76.00 166.77   52
 55  \w     81.00 106.00   0.50    0.17    --   54.00  77.00  40.82   50
 56  \w     31.00  60.00   0.50    0.17    --   54.00  77.00  40.82   58
 57  \w     34.00  60.00   0.50    0.17    --   54.00  76.00 166.77   52
 58  \w     37.00  63.00   0.50    0.17    --   58.00  73.00  99.80   52
 59  \w     34.00  63.00   0.50    0.17    --   58.00  77.00  57.24   58
 60  \w     40.00  66.00   0.50    0.17    --   62.00  76.00 -30.72   52
 61  \w     39.00  65.00   0.50    0.17    --   62.00  75.00 -82.60   52
 62  \w     40.00  66.00   0.50    0.17    --   62.00  74.00 137.32   52
 63  \w    110.00 135.00   0.50    0.17    --   62.00  76.00 -30.72   50
 64  \w     42.00  68.00   0.50    0.17    --   66.00  77.00 -72.66   52
 65  \w     42.00  68.00   0.50    0.17    --   66.00  77.00-152.93   52
 66  \w     43.00  69.00   0.50    0.17    --   66.00  77.00 -13.47   52
 67  \w     43.00  68.00   0.50    0.17    --   66.00  75.00 116.51   50
 68  \w    -75.00 -49.00   0.50    0.17    --  -70.00 -71.00  25.63   52
 69  \w     48.00  74.00   0.50    0.17    --   70.00  76.00 161.79   52
 70  \w     47.00  73.00   0.50    0.17    --   70.00  76.00-125.77   52
 71  \w     47.00  56.00   0.50    0.17    --   70.00  75.00  20.70   18
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1529807000
_diffrn_orient_matrix_UB_12      0.0445979000
_diffrn_orient_matrix_UB_13      -0.0019010000
_diffrn_orient_matrix_UB_21      0.0480575000
_diffrn_orient_matrix_UB_22      -0.1461735000
_diffrn_orient_matrix_UB_23      0.0592668000
_diffrn_orient_matrix_UB_31      0.0446600000
_diffrn_orient_matrix_UB_32      0.0104608000
_diffrn_orient_matrix_UB_33      -0.1408459000
_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  0.1189
_diffrn_reflns_av_unetI/netI     0.0745
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            14604
_diffrn_reflns_point_group_measured_fraction_full 0.777
_diffrn_reflns_point_group_measured_fraction_max 0.736
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.245
_diffrn_reflns_theta_min         4.386
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    13.981
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60486
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.92a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.683
_exptl_crystal_description       block
_exptl_crystal_F_000             524
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.094
_refine_diff_density_min         -0.916
_refine_diff_density_rms         0.209
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.007(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     493
_refine_ls_number_reflns         6247
_refine_ls_number_restraints     413
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.1086
_refine_ls_R_factor_gt           0.0917
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1992P)^2^+1.2109P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2514
_refine_ls_wR_factor_ref         0.2709
_reflns_Friedel_coverage         0.547
_reflns_Friedel_fraction_full    0.570
_reflns_Friedel_fraction_max     0.521
_reflns_number_gt                4966
_reflns_number_total             6247
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc00014a2.cif
_cod_data_source_block           6-98-1
_cod_depositor_comments
'Adding full bibliography for 1574135--1574136.cif.'
_cod_database_code               1574136
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N Se I'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C46, C34
 with sigma for 1-2 distances of 0.0008 and sigma for 1-3 distances of 0.0008
 C30, I2
 with sigma for 1-2 distances of 0.0008 and sigma for 1-3 distances of 0.0008
3. Uiso/Uaniso restraints and constraints
C34 \\sim C46: within 2A with sigma of 0.0007 and sigma for terminal atoms of
0.0014 within 2A
I2 \\sim C30: within 2A with sigma of 0.00007 and sigma for terminal atoms of
0.00014 within 2A
4. Rigid body (RIGU) restrains
 C31, I2, C30, C29, C28, C34, H31, C32, C23, C27, C33, C46, H32, C24, C22, C26,
  N3, H33, H46A, H46B, H46C, H24, C25, H22A, H22B, H22C, H26, H3A, C35, H25,
 Se2, N4, H4A, C36, C37, C41, H37, C38, C40, H41, H38, C39, H40, O2, C42, H42A,
 H42B, H42C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.008
 C15, I1, C6, C1, C5, C2, C7, C4, H5, C3, C43, C8, C12, H4, H3, H43A, H43B,
 H43C, C9, C21, N1, C11, H9, C10, H21A, H21B, H21C, H1, C13, H11, H10, Se1, N2,
 H2, C14, C19, H15, C16, C18, H19, H16, C17, H18, O1, C20, H20A, H20B, H20C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.008
 C22, I2, C30, C29, C31, C28, C34, H31, C32, C23, C27, C33, C46, H32, C24, C26,
  N3, H33, H46A, H46B, H46C, H24, C25, H22A, H22B, H22C, H26, H25, H3A, C35,
 Se2, N4, H4A, C36, C37, C41, H37, C38, C40, H41, H38, C39, H40, O2, C42, H42A,
 H42B, H42C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.008
5.a Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C11(H11), C15(H15),
 C16(H16), C18(H18), C19(H19), N3(H3A), N4(H4A), C24(H24), C25(H25), C26(H26),
 C31(H31), C32(H32), C33(H33), C37(H37), C38(H38), C40(H40), C41(H41)
5.b Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C43(H43A,H43B,H43C), C46(H46A,H46B,
 H46C), C22(H22A,H22B,H22C), C42(H42A,H42B,H42C)
;
_shelx_res_checksum              57904
_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 3.874
_oxdiff_exptl_absorpt_empirical_full_min 0.503