Conformational Flexibility and Substitution Pattern Lead to Polymorphism of 3-Methyl-2-(phenylamino)benzoic acid
Tao, Yang; Liu, Xiaoting; Zhoujin, Yunping; Zhou, Panpan; Parkin, Sean R.; Li, Tonglei; Guo, Ju; Yu, Faquan; Long, Sihui; CrystEngComm  (2022) –; doi:10.1039/D2CE00126H

data_7244642
_publ_section_title
;
 Conformational Flexibility and Substitution Pattern Lead to Polymorphism
 of 3-Methyl-2-(phenylamino)benzoic acid
;
_journal_name_full               CrystEngComm
_journal_paper_doi               10.1039/D2CE00126H
_journal_year                    2022
_chemical_formula_moiety         'C2 H6 O S, C16 H17 N O2'
_chemical_formula_sum            'C18 H23 N O3 S'
_chemical_formula_weight         333.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-04-19
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-10-28 deposited with the CCDC.	2022-03-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.057(11)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.8712(11)
_cell_length_b                   15.0167(14)
_cell_length_c                   10.3420(11)
_cell_measurement_reflns_used    4717
_cell_measurement_temperature    300.16(10)
_cell_measurement_theta_max      73.8210
_cell_measurement_theta_min      3.6670
_cell_volume                     1852.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      300.16(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.942
_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    -70.00  30.00   1.00    1.80    --  -43.05  80.00-137.00  100
  2  \w    -54.00 -24.00   1.00    6.00    -- -100.00  45.00-120.00   30
  3  \w    -54.00 -24.00   1.00    6.00    -- -100.00  45.00-180.00   30
  4  \w    -54.00 -24.00   1.00    6.00    -- -100.00  45.00-150.00   30
  5  \w    -54.00 -24.00   1.00    6.00    -- -100.00  45.00 -60.00   30
  6  \w    -54.00 -24.00   1.00    6.00    -- -100.00  45.00   0.00   30
  7  \w    -70.00 -30.00   1.00    6.00    -- -100.00  61.00 -30.00   40
  8  \w    -54.00 -24.00   1.00    6.00    -- -100.00  45.00  90.00   30
  9  \w    -54.00 -24.00   1.00    6.00    -- -100.00  45.00 150.00   30
 10  \w   -100.00 -20.00   1.00    1.80    --  -43.05 -80.00  98.00   80
 11  \w    -37.00  23.00   1.00    1.80    --   43.05 -19.00 -60.00   60
 12  \w     38.00  68.00   1.00    6.00    --  109.26 -61.00   0.00   30
 13  \w     35.00  65.00   1.00    6.00    --  109.26 -61.00  30.00   30
 14  \w     44.00 104.00   1.00    6.00    --  109.26 -94.00 -30.00   60
 15  \w     79.00 109.00   1.00    6.00    --  109.26-125.00 -30.00   30
 16  \w    108.00 138.00   1.00    6.00    --  109.26 -80.00  98.00   30
 17  \w     52.00 112.00   1.00    6.00    --  109.26 -80.00  98.00   60
 18  \w     41.00  81.00   1.00    6.00    --  109.26-125.00 -30.00   40
 19  \w     -3.00  27.00   1.00    1.80    --   43.05 -80.00  98.00   30
 20  \w    -22.00   8.00   1.00    1.80    --   43.05 -19.00  90.00   30
 21  \w     40.00  70.00   1.00    6.00    --  109.26 -61.00 150.00   30
 22  \w     81.00 171.00   1.00    6.00    --  109.26  80.00-137.00   90
 23  \w    -61.00 -31.00   1.00    6.00    -- -100.00  61.00-180.00   30
 24  \w   -102.00 -72.00   1.00    6.00    -- -100.00  80.00-137.00   30
 25  \w   -166.00-136.00   1.00    6.00    -- -100.00-125.00-180.00   30
 26  \w   -135.00 -85.00   1.00    6.00    -- -100.00-125.00-180.00   50
 27  \w    -41.00 -15.00   1.00    1.80    --  -42.93 -80.00 101.00   26
 28  \w    -31.00  32.00   1.00    1.80    --  -42.93  37.00  90.00   63
 29  \w    -22.00  28.00   1.00    1.80    --  -42.93  19.00-120.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0462070000
_diffrn_orient_matrix_UB_12      0.0844795000
_diffrn_orient_matrix_UB_13      0.0440130000
_diffrn_orient_matrix_UB_21      0.0712088000
_diffrn_orient_matrix_UB_22      -0.0199093000
_diffrn_orient_matrix_UB_23      0.1540736000
_diffrn_orient_matrix_UB_31      0.0972628000
_diffrn_orient_matrix_UB_32      0.0547847000
_diffrn_orient_matrix_UB_33      -0.0118927000
_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  0.0498
_diffrn_reflns_av_unetI/netI     0.0418
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            12806
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.820
_diffrn_reflns_theta_min         3.705
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.660
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.46845
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.195
_exptl_crystal_description       block
_exptl_crystal_F_000             712
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.363
_refine_diff_density_min         -0.356
_refine_diff_density_rms         0.050
_refine_ls_extinction_coef       0.0028(9)
_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   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     234
_refine_ls_number_reflns         3622
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0921
_refine_ls_R_factor_gt           0.0673
_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^)+(0.1446P)^2^+0.0949P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2009
_refine_ls_wR_factor_ref         0.2317
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2322
_reflns_number_total             3622
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ce00126h2.cif
_cod_data_source_block           5-S
_cod_database_code               7244642
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.937
_shelx_estimated_absorpt_t_min   0.879
_reflns_odcompleteness_completeness 98.56
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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, All C(H,H,H,H,H,H) groups, All O(H) groups
2. Others
 Fixed Sof: S1(0.75) S1B(0.25) H17A(0.75) H17B(0.75) H17C(0.75) H17D(0.25)
 H17E(0.25) H17F(0.25) C18(0.7) H18A(0.7) H18B(0.7) H18C(0.7) C18B(0.3)
 H18D(0.3) H18E(0.3) H18F(0.3)
3.a Aromatic/amide H refined with riding coordinates:
 N1(H1), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11)
3.b Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C17(H17D,H17E,H17F), C18(H18A,H18B,H18C), C18B(H18D,H18E,
 H18F), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C)
3.c Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_shelx_res_checksum              87767
_shelx_hkl_checksum              2134
_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 2.907
_oxdiff_exptl_absorpt_empirical_full_min 0.433