Monitoring dynamic pre-crystallization aggregation processes in solution by VT-DOSY NMR spectroscopy
Mix, Andreas; Lamm, Jan-Hendrik; Schwabedissen, Jan; Gebel, Erich; Stammler, Georg; Mitzel, Norbert Werner; Chemical Communications  (2022) –; doi:10.1039/D1CC05925D

data_7129480
_publ_section_title
;
 Monitoring dynamic pre-crystallization aggregation processes in solution
 by VT-DOSY NMR spectroscopy
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC05925D
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C5 F4 I N, 1(C7 H8)'
_chemical_formula_sum            'C12 H8 F4 I N'
_chemical_formula_weight         369.09
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yc'
_space_group_name_H-M_alt        'P 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-10-09
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2021-10-13 deposited with the CCDC.	2021-12-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.478(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.4279(2)
_cell_length_b                   7.9778(2)
_cell_length_c                   11.0063(4)
_cell_measurement_reflns_used    7071
_cell_measurement_temperature    232.0(1)
_cell_measurement_theta_max      31.6980
_cell_measurement_theta_min      2.5410
_cell_volume                     646.67(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.15e (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.15e (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.15e (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      232.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0951
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.995
_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    -45.00  79.00   1.00    8.00    --   24.87   0.00-120.00  124
  2  \w    -38.00  45.00   1.00    8.00    --   24.87 -38.00-180.00   83
  3  \w     -4.00  91.00   1.00    8.00    --   24.87  77.00  30.00   95
  4  \w     30.00  85.00   1.00    8.00    --   24.87-134.00 158.00   55
  5  \w     -4.00  91.00   1.00    8.00    --   24.87  77.00-150.00   95
  6  \w     32.00  87.00   1.00    8.00    --   24.87-136.00 -20.00   55
  7  \w      6.00  54.00   1.00    8.00    --   24.87  57.00 -30.00   48
  8  \w      6.00  54.00   1.00    8.00    --   24.87  57.00 150.00   48
  9  \w     36.00  99.00   1.00    8.00    --   24.87 178.00 120.00   63
 10  \w    -44.00  86.00   1.00    8.00    --   24.87   0.00  30.00  130
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0061277000
_diffrn_orient_matrix_UB_12      0.0005439000
_diffrn_orient_matrix_UB_13      0.0637794000
_diffrn_orient_matrix_UB_21      0.0959931000
_diffrn_orient_matrix_UB_22      -0.0041584000
_diffrn_orient_matrix_UB_23      0.0125676000
_diffrn_orient_matrix_UB_31      0.0045637000
_diffrn_orient_matrix_UB_32      0.0888143000
_diffrn_orient_matrix_UB_33      0.0002314000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0194
_diffrn_reflns_av_unetI/netI     0.0202
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            11846
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.033
_diffrn_reflns_theta_min         2.553
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.505
_exptl_absorpt_correction_T_max  0.4345
_exptl_absorpt_correction_T_min  0.1746
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0892 before and 0.0365 after correction. The Ratio of minimum to maximum transmission is 0.4018. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.896
_exptl_crystal_description       cylindrically
_exptl_crystal_F_000             352
_exptl_crystal_size_max          0.624
_exptl_crystal_size_mid          0.39
_exptl_crystal_size_min          0.354
_refine_diff_density_max         0.555
_refine_diff_density_min         -0.335
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Refined as a perfect inversion twin.
;
_refine_ls_abs_structure_Flack   0.5
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     205
_refine_ls_number_reflns         3768
_refine_ls_number_restraints     513
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0223
_refine_ls_R_factor_gt           0.0190
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0171P)^2^+0.0827P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0432
_refine_ls_wR_factor_ref         0.0442
_reflns_Friedel_coverage         0.994
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                3385
_reflns_number_total             3768
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc05925d2.cif
_cod_data_source_block           1_232K
_cod_database_code               7129480
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'c12 h8 F4 N I'
_shelx_estimated_absorpt_t_max   0.471
_shelx_estimated_absorpt_t_min   0.304
_reflns_odcompleteness_completeness 99.56
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     29.97
_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
 C6A-C12A \\sim C6B-C12B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C6A \\sim C7A \\sim H7A \\sim C8A \\sim H8A \\sim C9A \\sim H9A \\sim C10A
\\sim H10A \\sim C11A \\sim H11A \\sim C12A \\sim H12A \\sim H12B \\sim H12C
\\sim C6B \\sim C7B \\sim H7B \\sim C8B \\sim H8B \\sim C9B \\sim H9B \\sim
C10B \\sim H10B \\sim C11B \\sim H11B \\sim C12B \\sim H12D \\sim H12E \\sim
H12F: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
4. Others
 Sof(C8B)=Sof(H8B)=Sof(C7B)=Sof(H7B)=Sof(C6B)=Sof(C11B)=Sof(H11B)=Sof(C10B)=
 Sof(H10B)=Sof(C9B)=Sof(H9B)=Sof(C12B)=Sof(H12D)=Sof(H12E)=Sof(H12F)=1-FVAR(1)
 Sof(C10A)=Sof(H10A)=Sof(C9A)=Sof(H9A)=Sof(C8A)=Sof(H8A)=Sof(C7A)=Sof(H7A)=
 Sof(C6A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C10A(H10A), C9A(H9A), C8A(H8A), C7A(H7A), C11A(H11A), C8B(H8B), C7B(H7B),
 C11B(H11B), C10B(H10B), C9B(H9B)
5.b Fitted hexagon refined as free rotating group:
 C10A(C9A,C8A,C7A,C6A,C11A), C8B(C7B,C6B,C11B,C10B,C9B)
5.c Idealised Me refined as rotating group:
 C12A(H12A,H12B,H12C), C12B(H12D,H12E,H12F)
;
_shelx_res_checksum              32382
_olex2_date_sample_data_collection 2017-10-05
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_full_max 4.544
_oxdiff_exptl_absorpt_empirical_full_min 0.666