Spectroscopic investigations of a pharmaceutical solid form analogue: pyrimethanil L-tartrate hemi-cocrystal
Dosanjh, Ramandeep; Patterson, Adam; Harris, Joe; Wilson, Claire; Gutmann, Matthias J.; Collier, Paul; Hyde, Tim; Johnson, Timothy; York, Andy; Parker, Stewart F.; Lennon, David; Physical Chemistry Chemical Physics  (2025) –; doi:10.1039/D5CP02802G

data_7251236
_publ_section_title
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 Spectroscopic investigations of a pharmaceutical solid form analogue:
 pyrimethanil L-tartrate hemi-cocrystal
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_journal_name_full               'Physical Chemistry Chemical Physics'
_journal_paper_doi               10.1039/D5CP02802G
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         '(C12 H13 N3)2, (C4 H6 O6)'
_chemical_formula_sum            'C28 H32 N6 O6'
_chemical_formula_weight         548.59
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-06-28
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
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2024-09-19 deposited with the CCDC.	2025-11-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.6004(7)
_cell_length_b                   18.6805(8)
_cell_length_c                   8.7346(4)
_cell_measurement_reflns_used    9879
_cell_measurement_temperature    150
_cell_measurement_theta_max      68.191
_cell_measurement_theta_min      3.562
_cell_volume                     2708.6(2)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'APEX3 Ver. 2016.9-0 (Bruker-AXS, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2015b)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'charge integrating pixel array detector'
_diffrn_detector_area_resol_mean 7.4074
_diffrn_detector_type            'Bruker PHOTON II'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  'multilayer mirror optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0383
_diffrn_reflns_av_unetI/netI     0.0246
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            23878
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.242
_diffrn_reflns_theta_min         3.562
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           1.1
_diffrn_source_power             0.05500000000000001
_diffrn_source_type              'INCOATEC I\ms 3.0'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.797
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6528
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0738 before and 0.0486 after correction.
The Ratio of minimum to maximum transmission is 0.8668.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.345
_exptl_crystal_description       block
_exptl_crystal_F_000             1160
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.186
_refine_diff_density_min         -0.169
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.03(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     408
_refine_ls_number_reflns         4929
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0302
_refine_ls_R_factor_gt           0.0285
_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^)+(0.0457P)^2^+0.3438P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0765
_refine_ls_wR_factor_ref         0.0782
_reflns_Friedel_coverage         0.752
_reflns_Friedel_fraction_full    0.989
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                4827
_reflns_number_total             4929
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cp02802g2.cif
_cod_data_source_block           cu_2021gu0033_150k
_cod_database_code               7251236
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.976
_shelx_estimated_absorpt_t_min   0.876
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.97(18)
 0.03(18)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,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
3. Others
 Sof(H4TA)=Sof(O1A)=Sof(H1A)=1-FVAR(1)
 Sof(O1)=Sof(H1)=Sof(H4T)=FVAR(1)
 Fixed Sof: H14A(0.5) H14B(0.5) H14C(0.5) H14D(0.5) H14E(0.5) H14F(0.5)
 H15A(0.5) H15B(0.5) H15C(0.5) H15D(0.5) H15E(0.5) H15F(0.5) H14G(0.5)
 H14H(0.5) H14I(0.5) H15G(0.5) H15H(0.5) H15I(0.5) H15J(0.5) H15K(0.5)
 H15L(0.5) H14J(0.5) H14K(0.5) H14L(0.5)
4.a Ternary CH refined with riding coordinates:
 C8T(H8T), C4T(H4T), C4T(H4TA)
4.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C5A(H5A), C9A(H9A),
 C10A(H10A), C11A(H11A), C12A(H12A), C13A(H13A)
4.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C14(H14D,H14E,H14F), C15(H15A,H15B,H15C), C15(H15D,H15E,
 H15F), C14A(H14G,H14H,H14I), C15A(H15G,H15H,H15I), C15A(H15J,H15K,H15L)
4.d Idealised tetrahedral OH refined as rotating group:
 O9T(H9T), O1(H1), O1A(H1A)
;
_shelx_res_checksum              13920
_olex2_submission_special_instructions 'No special instructions were received'