In the pursuit of a ‘disappearing’ anhydrous phase of the antipyrine–dipicolinic acid (ANT–DPA) co-crystal: explained through relative stability and charge density analyses
Akram, Sehrish; Mehmood, Arshad; Noureen, Sajida; Ahmed, Maqsood; CrystEngComm 25 (2023) 6478–6488; doi:10.1039/D3CE00591G

data_7247599
_publ_section_title
;
 In the pursuit of a &#x2018;disappearing&#x2019; anhydrous phase of the
 antipyrine--dipicolinic acid (ANT--DPA) co-crystal: explained through
 relative stability and charge density analyses
;
_journal_issue                   46
_journal_name_full               CrystEngComm
_journal_page_first              6478
_journal_page_last               6488
_journal_paper_doi               10.1039/D3CE00591G
_journal_volume                  25
_journal_year                    2023
_chemical_formula_moiety         'C46 H40 F6 Fe, 0.5[C6H14]'
_chemical_formula_sum            'C49 H47 F6 Fe'
_chemical_formula_weight         805.71
_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
_atom_sites_solution_secondary   difmap
_audit_block_doi                 10.5517/ccdc.csd.cc2cb9pq
_audit_creation_date             2021-05-26
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-07-07 deposited with the CCDC.	2023-10-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.4560(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.31550(10)
_cell_length_b                   17.9907(2)
_cell_length_c                   20.6727(2)
_cell_measurement_reflns_used    29830
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.7280
_cell_measurement_theta_min      4.1830
_cell_volume                     4162.67(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      'N2 gas'
_diffrn_ambient_temperature      120(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 5.2349
_diffrn_detector_type            'Agilent Diffraction Atlas S2 detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_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    -21.00  33.00   1.00    3.00    --  -41.70  38.00   0.00   54
  2  \w     -5.00  38.00   1.00    3.00    --  -41.70  19.00  30.00   43
  3  \w   -116.00 -17.00   1.00    3.00    --  -41.70 -38.00-150.00   99
  4  \w     -5.00  38.00   1.00    3.00    --  -41.70  19.00 150.00   43
  5  \w    -21.00  33.00   1.00    3.00    --  -41.70  38.00 -60.00   54
  6  \w      7.00  14.00   1.00    3.00    --   41.70  83.00-125.32    7
  7  \w     10.00  36.00   1.00    3.00    --   41.70  75.00 -40.64   26
  8  \w    -21.00  74.00   1.00    3.00    --   41.70 -77.00  90.00   95
  9  \w      8.00  36.00   1.00    3.00    --   41.70  82.00-160.99   28
 10  \w      7.00  34.00   1.00    3.00    --   41.70  83.00 -29.93   27
 11  \w     31.00  72.00   1.00   12.00    --  104.36 -45.00  30.00   41
 12  \w     22.00 106.00   1.00   12.00    --  104.36 -94.00  30.00   84
 13  \w     75.00 177.00   1.00   12.00    --  104.36  61.00 -30.00  102
 14  \w     31.00  72.00   1.00   12.00    --  104.36 -45.00  90.00   41
 15  \w     32.00  93.00   1.00   12.00    --  104.36 -61.00  60.00   61
 16  \w     31.00 112.00   1.00   12.00    --  104.36-125.00   0.00   81
 17  \w     75.00 178.00   1.00   12.00    --  104.36  60.00-101.82  103
 18  \w     31.00 112.00   1.00   12.00    --  104.36-125.00-150.00   81
 19  \w     28.00 108.00   1.00   12.00    --  104.36-110.00 107.91   80
 20  \w     75.00 177.00   1.00   12.00    --  104.36  61.00 -48.95  102
 21  \w     79.00 177.00   1.00   12.00    --  104.36  45.00-120.00   98
 22  \w     75.00 177.00   1.00   12.00    --  104.36  61.00 -60.00  102
 23  \w     28.00  57.00   1.00   12.00    --  104.36 -30.00-120.00   29
 24  \w     32.00  93.00   1.00   12.00    --  104.36 -61.00-180.00   61
 25  \w     77.00 177.00   1.00   12.00    --  104.36  54.00 -86.62  100
 26  \w     75.00 177.00   1.00   12.00    --  104.36  61.00 -90.00  102
 27  \w     31.00  72.00   1.00   12.00    --  104.36 -45.00 -60.00   41
 28  \w    103.00 178.00   1.00   12.00    --  104.36  77.00-180.00   75
 29  \w    103.00 178.00   1.00   12.00    --  104.36  77.00  90.00   75
 30  \w     75.00 177.00   1.00   12.00    --  104.36  61.00 -80.88  102
 31  \w     77.00 177.00   1.00   12.00    --  104.36  52.00 -63.23  100
 32  \w     -5.00  38.00   1.00    3.00    --  -41.70  19.00-120.00   43
 33  \w     -5.00  38.00   1.00    3.00    --  -41.70  19.00-150.00   43
 34  \w   -116.00 -17.00   1.00    3.00    --  -41.70 -38.00  60.00   99
 35  \w   -114.00 -14.00   1.00    3.00    --  -41.70 -57.00   0.00  100
 36  \w     27.00  98.00   1.00    3.00    --   41.70-125.00 -30.00   71
 37  \w      7.00  14.00   1.00    3.00    --   41.70  84.00  73.82    7
 38  \w      7.00  33.00   1.00    3.00    --   41.70  84.00 -90.54   26
 39  \w      9.00  42.00   1.00    3.00    --   41.70  76.00  19.85   33
 40  \w     10.00  36.00   1.00    3.00    --   41.70  75.00 142.11   26
 41  \w     75.00 177.00   1.00   12.00    --  104.36  61.00   0.00  102
 42  \w     74.00 178.00   1.00   12.00    --  104.36  68.00  99.30  104
 43  \w     76.00 178.00   1.00   12.00    --  104.36  30.00-180.00  102
 44  \w     76.00 178.00   1.00   12.00    --  104.36  30.00  60.00  102
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Atlas S2'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1111405000
_diffrn_orient_matrix_UB_12      0.0300285000
_diffrn_orient_matrix_UB_13      -0.0442814000
_diffrn_orient_matrix_UB_21      -0.0804975000
_diffrn_orient_matrix_UB_22      -0.0494405000
_diffrn_orient_matrix_UB_23      0.0360188000
_diffrn_orient_matrix_UB_31      -0.0101871000
_diffrn_orient_matrix_UB_32      0.0631899000
_diffrn_orient_matrix_UB_33      0.0491478000
_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  0.0331
_diffrn_reflns_av_unetI/netI     0.0146
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            76387
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.069
_diffrn_reflns_theta_min         3.272
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    3.404
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.231
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.286
_exptl_crystal_description       block
_exptl_crystal_F_000             1684
_exptl_crystal_recrystallization_method 'crystallised from hexane at -30 degC'
_exptl_crystal_size_max          0.567
_exptl_crystal_size_mid          0.363
_exptl_crystal_size_min          0.325
_refine_diff_density_max         0.314
_refine_diff_density_min         -0.411
_refine_diff_density_rms         0.037
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     589
_refine_ls_number_reflns         8270
_refine_ls_number_restraints     384
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0365
_refine_ls_R_factor_gt           0.0350
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0564P)^2^+0.9967P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0968
_refine_ls_wR_factor_ref         0.0983
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7881
_reflns_number_total             8270
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ce00591g2.cif
_cod_data_source_block           feljtb
_cod_depositor_comments
'Adding full bibliography for 7247599--7247600.cif.'
_cod_database_code               7247599
_nottingham_internal_coll_name   FELJTB
_nottingham_internal_coll_number 18657
_nottingham_internal_coll_client LJT/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '12.00, 3.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczlt
_nottingham_internal_coll_date   19/02/2020
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVB, PL13110001'
_nottingham_internal_process_date 20/02/2020
_nottingham_internal_process_user pczlt
_nottingham_internal_solution_date 02/04/2021
_nottingham_internal_solution_user pczlt
_nottingham_internal_refinement_date 02/04/2021
_nottingham_internal_refinement_user pczlt
_nottingham_internal_self_validation_date 02/04/2021
_nottingham_internal_self_validation_user pczlt
_nottingham_internal_validation_date 06/05/2022
_nottingham_internal_validation_user pczspa
_nottingham_internal_archive_date 06/05/2022
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C46 H40 Fe F6'
_chemical_oxdiff_usercomment
'FELJTB #18657 GVB-1779 for LJT/DLK in Fomblin film on a micromount'
_shelx_estimated_absorpt_t_max   0.404
_shelx_estimated_absorpt_t_min   0.248
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C28-C37B \\sim C28-C37A
 with sigma of 0.02
 C37B-C38B \\sim C37A-C38A
 with sigma of 0.02
 C37B-C42B \\sim C37A-C42A
 with sigma of 0.02
 C38B-C43B \\sim C38A-C43A
 with sigma of 0.02
 C38B-C39B \\sim C38A-C39A
 with sigma of 0.02
 C42B-C44B \\sim C42A-C44A
 with sigma of 0.02
 C42B-C41B \\sim C42A-C41A
 with sigma of 0.02
 C38B-C42B \\sim C38A-C42A
 with sigma of 0.04
 C38B-C40B \\sim C38A-C40A
 with sigma of 0.04
 C42B-C40B \\sim C42A-C40A
 with sigma of 0.04
 C41B-C39B \\sim C41A-C39A
 with sigma of 0.04
 C41B-C40B \\sim C41A-C40A
 with sigma of 0.02
 C40B-C39B \\sim C40A-C39A
 with sigma of 0.02
 C43B-C39B \\sim C43A-C39A
 with sigma of 0.04
 C44B-C41B \\sim C44A-C41A
 with sigma of 0.04
 C28-C38B \\sim C28-C38A
 with sigma of 0.04
 C28-C42B \\sim C28-C42A
 with sigma of 0.04
 C37B-C43B \\sim C37A-C43A
 with sigma of 0.04
 C37B-C44B \\sim C37A-C44A
 with sigma of 0.04
 C37B-C41B \\sim C37A-C41A
 with sigma of 0.04
 C37B-C39B \\sim C37A-C39A
 with sigma of 0.04
 F1B-C45 \\sim F1A-C45
 with sigma of 0.02
 F2B-C45 \\sim F2A-C45
 with sigma of 0.02
 F3B-C45 \\sim F3A-C45
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C37A \\sim C38A \\sim C39A \\sim C40A \\sim C41A \\sim C42A \\sim C43A \\sim
C44A \\sim H39A \\sim H40A \\sim H41A \\sim H43D \\sim H43E \\sim H43F \\sim
H44D \\sim H44E \\sim H44F: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C37B \\sim C38B \\sim C39B \\sim C40B \\sim C41B \\sim C42B \\sim C43B \\sim
C44B \\sim H39B \\sim H40B \\sim H41B \\sim H43A \\sim H43B \\sim H43C \\sim
H44A \\sim H44B \\sim H44C: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
F1B \\sim F2B \\sim F3B \\sim F1A \\sim F2A \\sim F3A: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 C37B, C38B, C39B, C40B, C41B, C42B, C43B, C44B, H39B, H40B, H41B, H43A, H43B,
 H43C, H44A, H44B, H44C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C37A, C38A, C39A, C40A, C41A, C42A, C43A, C44A, H39A, H40A, H41A, H43D, H43E,
 H43F, H44D, H44E, H44F
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1B, F2B, F3B, F1A, F2A, F3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C37A)=Sof(C38A)=Sof(C39A)=Sof(H39A)=Sof(C40A)=Sof(H40A)=Sof(C41A)=
 Sof(H41A)=Sof(C42A)=Sof(C43A)=Sof(H43D)=Sof(H43E)=Sof(H43F)=Sof(C44A)=
 Sof(H44D)=Sof(H44E)=Sof(H44F)=1-FVAR(1)
 Sof(C37B)=Sof(C38B)=Sof(C39B)=Sof(H39B)=Sof(C40B)=Sof(H40B)=Sof(C41B)=
 Sof(H41B)=Sof(C42B)=Sof(C43B)=Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(C44B)=
 Sof(H44A)=Sof(H44B)=Sof(H44C)=FVAR(1)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(2)
 Sof(F1B)=Sof(F2B)=Sof(F3B)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C9(H9), C10(H10), C11(H11), C17(H17), C18(H18), C19(H19),
 C25(H25), C27(H27), C31(H31), C32(H32), C33(H33), C39B(H39B), C40B(H40B),
 C41B(H41B), C39A(H39A), C40A(H40A), C41A(H41A)
6.b Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C43B(H43A,H43B,H43C),
 C44B(H44A,H44B,H44C), C43A(H43D,H43E,H43F), C44A(H44D,H44E,H44F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 100 electrons were 
found in a volume of 436\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
0.5[C6H14] per Formula Unit 
which account for 100 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              48329
_shelx_fab_checksum              89539
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_original_sample_id FELJTB
_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 1.914
_oxdiff_exptl_absorpt_empirical_full_min 0.774