Chiral resolution of dl-leucine via salifying tartaric acid derivatives
Shi, Linlin; Guo, Zhiqiang; Luo, Xiaofang; Hou, Lingli; Wu, Hongchang; De, Ruiyu; Huang, Xin; Wang, Ting; Hao, Hongxun; Wang, Na; Zhou, Lina; CrystEngComm 27 (2025) 155–163; doi:10.1039/D4CE01043D

data_7249683
_publ_section_title
;
 Chiral resolution of dl-leucine via salifying tartaric acid derivatives
;
_journal_issue                   2
_journal_name_full               CrystEngComm
_journal_page_first              155
_journal_page_last               163
_journal_paper_doi               10.1039/D4CE01043D
_journal_volume                  27
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(C20 H17 O8), 2(C6 H14 N O2), H2 O'
_chemical_formula_sum            'C52 H64 N2 O21'
_chemical_formula_weight         1053.05
_chemical_name_systematic
'D-leucinium D-di-p-toluoyltartrate semihydrate'
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-02
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-09-27 deposited with the CCDC.	2024-12-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.0490(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.9114(2)
_cell_length_b                   12.85360(10)
_cell_length_c                   15.90080(10)
_cell_measurement_reflns_used    41533
_cell_measurement_temperature    128.15
_cell_measurement_theta_max      78.7260
_cell_measurement_theta_min      3.2870
_cell_volume                     5482.27(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      128.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.991
_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    -25.00  94.00   0.50    0.50    --    5.00  57.00 120.00  238
  2  \w    -28.00  94.00   0.50    0.50    --    5.00  38.00-120.00  244
  3  \w    -82.00  41.00   0.50    0.50    --  -48.80  38.00   0.00  246
  4  \w    -82.00  41.00   0.50    0.50    --  -48.80  70.00  35.83  246
  5  \w    -83.00  41.00   0.50    0.50    --  -48.80  72.00-120.00  248
  6  \w    -79.00  41.00   0.50    0.50    --  -48.80  57.00-150.00  240
  7  \w    -79.00  41.00   0.50    0.50    --  -48.80  57.00  90.00  240
  8  \w   -199.00 -80.00   0.50    0.50    -- -110.00 -50.00-167.12  238
  9  \w   -199.00 -75.00   0.50    0.50    -- -110.00 -36.00 105.63  248
 10  \w   -144.00 -21.00   0.50    0.50    -- -110.00  72.00 120.00  246
 11  \w   -144.00 -21.00   0.50    0.50    -- -110.00  72.00  60.00  246
 12  \w   -144.00 -21.00   0.50    0.50    -- -110.00  72.00  30.00  246
 13  \w   -144.00 -21.00   0.50    0.50    -- -110.00  72.00  90.00  246
 14  \w   -144.00 -21.00   0.50    0.50    -- -110.00  72.00-180.00  246
 15  \w   -199.00 -80.00   0.50    0.50    -- -110.00 -57.00  30.00  238
 16  \w   -144.00 -21.00   0.50    0.50    -- -110.00  72.00 -60.00  246
 17  \w   -112.00 -85.00   0.50    0.50    -- -110.00 -68.00 -81.40   54
 18  \w   -120.00 -94.00   0.50    0.50    -- -110.00  72.00 -30.00   52
 19  \w   -139.00 -22.00   0.50    0.50    -- -110.00  72.00 -90.00  234
 20  \w   -199.00-117.00   0.50    0.50    -- -110.00 -53.00 -47.71  164
 21  \w   -160.00-104.00   0.50    0.50    -- -110.00 -57.00-150.00  112
 22  \w    -79.00 -53.00   0.50    0.50    -- -110.00  72.00-120.00   52
 23  \w   -101.00 -75.00   0.50    0.50    -- -110.00  72.00   0.00   52
 24  \w   -198.00-138.00   0.50    0.50    -- -110.00 -72.00   0.00  120
 25  \w   -115.00 -89.00   0.50    0.50    -- -110.00 -72.00   0.00   52
 26  \w   -198.00-110.00   0.50    0.50    -- -110.00 -42.00  81.94  176
 27  \w   -141.00 -80.00   0.50    0.50    -- -110.00  72.00-120.00  122
 28  \w   -198.00-151.00   0.50    0.50    -- -110.00 -68.00 -81.40   94
 29  \w    -61.00 -35.00   0.50    0.50    -- -110.00  72.00-150.00   52
 30  \w   -196.00-146.00   0.50    0.50    -- -110.00 -28.00 -14.19  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB P200'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0237827000
_diffrn_orient_matrix_UB_12      -0.0923706000
_diffrn_orient_matrix_UB_13      -0.0585032000
_diffrn_orient_matrix_UB_21      -0.0522645000
_diffrn_orient_matrix_UB_22      0.0441264000
_diffrn_orient_matrix_UB_23      -0.0066773000
_diffrn_orient_matrix_UB_31      0.0017022000
_diffrn_orient_matrix_UB_32      0.0623589000
_diffrn_orient_matrix_UB_33      -0.0817966000
_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  0.0213
_diffrn_reflns_av_unetI/netI     0.0150
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            48515
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.971
_diffrn_reflns_theta_min         2.892
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.835
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52304
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)'
_exptl_crystal_density_diffrn    1.276
_exptl_crystal_description       block
_exptl_crystal_F_000             2232
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.284
_refine_diff_density_min         -0.248
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 5004 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.07(4)
_refine_ls_extinction_coef       0.00012(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     700
_refine_ls_number_reflns         11329
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0387
_refine_ls_R_factor_gt           0.0385
_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^)+(0.0652P)^2^+3.0644P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1079
_refine_ls_wR_factor_ref         0.1081
_reflns_Friedel_coverage         0.841
_reflns_Friedel_fraction_full    0.960
_reflns_Friedel_fraction_max     0.914
_reflns_number_gt                11216
_reflns_number_total             11329
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ce01043d2.cif
_cod_data_source_block           p20240501c
_cod_depositor_comments
'Adding full bibliography for 7249682--7249683.cif.'
_cod_database_code               7249683
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.878
_shelx_estimated_absorpt_t_min   0.818
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups
2. Restrained distances
 O6-H6 = O14-H14
 0.85 with sigma of 0.01
3.a Free rotating group:
 O21(H21D,H21E)
3.b Ternary CH refined with riding coordinates:
 C9(H9), C11(H11), C29(H29), C31(H31), C42(H42), C44(H44), C48(H48), C50(H50)
3.c Secondary CH2 refined with riding coordinates:
 C43(H43A,H43B), C49(H49A,H49B)
3.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6A), C7(H7), C15(H15), C16(H16), C18(H18), C19(H19),
 C23(H23), C24(H24), C26(H26), C27(H27), C35(H35), C36(H36), C38(H38), C39(H39)
3.e Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C40(H40A,H40B,
 H40C), N1(H1D,H1E,H1F), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), N2(H2A,H2B,
 H2C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C)
3.f Idealised tetrahedral OH refined as rotating group:
 O18(H18A), O20(H20)
;
_shelx_res_checksum              38149
_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 1.790
_oxdiff_exptl_absorpt_empirical_full_min 0.798