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_7249682
_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
'C6 H14 N O2, C20 H17 O8, 0.357(C H4 O), 0.75(H2 O)'
_chemical_formula_sum            'C26.36 H33.93 N O11.11'
_chemical_formula_weight         542.48
_chemical_name_systematic
'L-leucinium D-di-p-toluoyltartrate methanol solvate hydrate'
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'I 2y'
_space_group_name_H-M_alt        'I 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-17
_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                 106.200(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.8758(3)
_cell_length_b                   13.8581(3)
_cell_length_c                   27.1887(6)
_cell_measurement_reflns_used    15578
_cell_measurement_temperature    138.15
_cell_measurement_theta_max      77.4360
_cell_measurement_theta_min      2.9180
_cell_volume                     5744.2(2)
_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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      138.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.959
_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    -83.00  41.00   0.50    0.50    --  -48.80  72.00  30.00  248
  2  \w   -138.00 -17.00   0.50    0.50    --  -48.80 -45.00 -80.75  242
  3  \w    -79.00  41.00   0.50    0.50    --  -48.80  57.00 -30.00  240
  4  \w   -199.00 -78.00   0.50    2.50    -- -110.00 -42.00 -68.10  242
  5  \w   -199.00 -80.00   0.50    2.50    -- -110.00 -50.00-140.79  238
  6  \w   -144.00 -21.00   0.50    2.50    -- -110.00  72.00-120.00  246
  7  \w   -199.00 -79.00   0.50    2.50    -- -110.00 -44.00 -41.20  240
  8  \w   -144.00 -21.00   0.50    2.50    -- -110.00  72.00 -90.00  246
  9  \w    -81.00 -36.00   0.50    2.50    -- -110.00  72.00  30.00   90
 10  \w   -106.00 -62.00   0.50    2.50    -- -110.00  72.00-150.00   88
 11  \w   -129.00 -43.00   0.50    2.50    -- -110.00  72.00 150.00  172
 12  \w   -159.00-114.00   0.50    2.50    -- -110.00 -64.00 -84.32   90
 13  \w   -108.00 -82.00   0.50    2.50    -- -110.00 -64.00 -84.32   52
 14  \w   -142.00 -25.00   0.50    2.50    -- -110.00  72.00-180.00  234
 15  \w    -93.00 -52.00   0.50    2.50    -- -110.00  72.00 -60.00   82
 16  \w    -58.00 -21.00   0.50    2.50    -- -110.00  57.00-120.00   74
 17  \w   -114.00 -87.00   0.50    2.50    -- -110.00  72.00 120.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RCD3): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0459934000
_diffrn_orient_matrix_UB_12      0.0974022000
_diffrn_orient_matrix_UB_13      0.0013555000
_diffrn_orient_matrix_UB_21      -0.0814738000
_diffrn_orient_matrix_UB_22      -0.0533031000
_diffrn_orient_matrix_UB_23      0.0062486000
_diffrn_orient_matrix_UB_31      0.0381015000
_diffrn_orient_matrix_UB_32      0.0035847000
_diffrn_orient_matrix_UB_33      0.0587170000
_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  0.0317
_diffrn_reflns_av_unetI/netI     0.0339
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            27976
_diffrn_reflns_point_group_measured_fraction_full 0.925
_diffrn_reflns_point_group_measured_fraction_max 0.878
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.104
_diffrn_reflns_theta_min         2.920
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.827
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69226
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.255
_exptl_crystal_description       prism
_exptl_crystal_F_000             2303
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.509
_refine_diff_density_min         -0.357
_refine_diff_density_rms         0.065
_refine_ls_abs_structure_details
;
 Flack x determined using 3944 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.11(7)
_refine_ls_extinction_coef       0.00050(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     781
_refine_ls_number_reflns         10936
_refine_ls_number_restraints     52
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0659
_refine_ls_R_factor_gt           0.0618
_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^)+(0.1234P)^2^+2.2650P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1778
_refine_ls_wR_factor_ref         0.1832
_reflns_Friedel_coverage         0.756
_reflns_Friedel_fraction_full    0.861
_reflns_Friedel_fraction_max     0.790
_reflns_number_gt                9977
_reflns_number_total             10936
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ce01043d2.cif
_cod_data_source_block           p20240514d
_cod_depositor_comments
'Adding full bibliography for 7249682--7249683.cif.'
_cod_database_code               7249682
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.900
_shelx_estimated_absorpt_t_min   0.814
_reflns_odcompleteness_completeness 97.60
_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
 C12-C10 = C12A-C10
 1.54 with sigma of 0.01
 C4A-C6A = C4A-C5A = C3A-C4A = C2A-C3A
 1.54 with sigma of 0.01
 C3A-C6A = C3A-C5A = C6A-C5A
 2.52 with sigma of 0.01
 C53-O21
 1.45 with sigma of 0.01
 O1A-C1A = O2A-C1A
 1.24 with sigma of 0.01
 C1-C2 = C1A-C2A
 1.5 with sigma of 0.01
 C12-C11 \\sim C12A-C11 \\sim C9-C11 \\sim C9-C12 \\sim C9-C12A
 with sigma of 0.01
 O1-C2 \\sim O2-C2 \\sim O1A-C2A \\sim O2A-C2A
 with sigma of 0.01
 N1-C2 \\sim N1A-C2A
 with sigma of 0.01
3. Restrained planarity
 O1, O2, C1, C2
 with sigma of 0.01
 O1A, O2A, C1A, C2A
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C12 \\sim C12A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(C12) \\sim Ueq, Uanis(C12A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O1A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.2
Uanis(C6A) = Uanis(C6)
Uanis(C5A) = Uanis(C5)
Uanis(O1) = Uanis(C1A)
Uanis(O2A) = Uanis(O1) = Uanis(C1A)
Uanis(N1A) = Uanis(N1)
5. Others
 Sof(H10A)=Sof(C12A)=Sof(H12D)=Sof(H12E)=Sof(H12F)=1-FVAR(1)
 Sof(H10)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(1)
 Sof(O21)=Sof(H21)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=FVAR(2)
 Fixed Sof: O1(0.7) H1(0.7) O2(0.7) N1(0.7) H1A(0.7) H1B(0.7) H1C(0.7) C1(0.7)
 C2(0.7) H2(0.7) C3(0.7) H3A(0.7) H3B(0.7) C4(0.7) H4(0.7) C5(0.7) H5A(0.7)
 H5B(0.7) H5C(0.7) C6(0.7) H6A(0.7) H6B(0.7) H6C(0.7) O1A(0.3) H1AA(0.3)
 O2A(0.3) N1A(0.3) H1AB(0.3) H1AC(0.3) H1AD(0.3) C1A(0.3) C2A(0.3) H2AA(0.3)
 C3A(0.3) H3AA(0.3) H3AB(0.3) C4A(0.3) H4A(0.3) C5A(0.3) H5AA(0.3) H5AB(0.3)
 H5AC(0.3) C6A(0.3) H6AA(0.3) H6AB(0.3) H6AC(0.3) H23A(0.5) H23B(0.5)
6.a Riding coordinates:
 O22(H22A,H22B), O1(H1), O1A(H1AA), O23(H23A,H23B)
6.b Ternary CH refined with riding coordinates:
 C8(H8A), C10(H10), C10(H10A), C14(H14), C15(H15), C34(H34), C35(H35), C2(H2),
 C4(H4), C2A(H2AA), C4A(H4A)
6.c Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C3(H3A,H3B), C3A(H3AA,H3AB)
6.d Me refined with riding coordinates:
 C6A(H6AA,H6AB,H6AC)
6.e Aromatic/amide H refined with riding coordinates:
 C19(H19), C20(H20), C22(H22), C23(H23), C27(H27), C28(H28), C30(H30),
 C31(H31), C39(H39), C40(H40), C42(H42), C43(H43), C47(H47), C48(H48), C50(H50),
  C51(H51)
6.f Idealised Me refined as rotating group:
 N2(H2A,H2B,H2C), C11(H11A,H11B,H11C), C24(H24A,H24B,H24C), C32(H32A,H32B,
 H32C), C44(H44A,H44B,H44C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), N1(H1A,
 H1B,H1C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C12(H12A,H12B,H12C), N1A(H1AB,H1AC,
 H1AD), C5A(H5AA,H5AB,H5AC), C12A(H12D,H12E,H12F)
6.g Idealised tetrahedral OH refined as rotating group:
 O3(H3), O8(H8), O13(H13), O21(H21)
;
_shelx_res_checksum              97621
_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 1.584
_oxdiff_exptl_absorpt_empirical_full_min 0.713