Co-crystal formation vs. boron coordination: fluorination in azopyridines regulates supramolecular competition
Loya, Jesus Daniel; Agarwal, Sidhaesh A.; Lutz, Nicholas; Reinheimer, Eric W.; Campillo-Alvarado, Gonzalo; CrystEngComm 26 (2024) 4017–4021; doi:10.1039/D4CE00611A

data_7249001
_publ_section_title
;
 Co-crystal formation vs. boron coordination: fluorination in azopyridines
 regulates supramolecular competition
;
_journal_issue                   30
_journal_name_full               CrystEngComm
_journal_page_first              4017
_journal_page_last               4021
_journal_paper_doi               10.1039/D4CE00611A
_journal_volume                  26
_journal_year                    2024
_chemical_formula_moiety         'C34 H26 B2 N4 O4'
_chemical_formula_sum            'C34 H26 B2 N4 O4'
_chemical_formula_weight         576.21
_chemical_name_systematic
'phneylboronicacid catechol ester adduct of 4,4'-bipyridine'
_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             2024-03-11
_audit_creation_method
;
Olex2 1.5-ac6-017
(compiled 2024.02.01 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6920)
;
_audit_update_record
;
2024-04-10 deposited with the CCDC.	2024-07-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.615(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.8631(2)
_cell_length_b                   13.1490(3)
_cell_length_c                   15.7054(4)
_cell_measurement_reflns_used    5783
_cell_measurement_temperature    99.9(6)
_cell_measurement_theta_max      30.5100
_cell_measurement_theta_min      2.0560
_cell_volume                     1397.39(6)
_computing_cell_refinement       'CrysAlisPro 1.171.43.112a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.112a 64-bit (release 01-03-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.112a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac6-017 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-017 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(6)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.958
_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    -31.00 101.00   0.50   30.00    --   20.00  54.00  90.00  264
  2  \w    -74.00 106.50   0.50   30.00    --   20.00  54.00 150.00  361
  3  \w    -47.00 -22.00   0.50   30.00    --   20.00  54.00 -60.00   50
  4  \w     74.00 100.00   0.50   30.00    --   20.00  54.00 -60.00   52
  5  \w    -64.00 -39.00   0.50   30.00    --   20.00  54.00-180.00   50
  6  \w      9.00  35.00   0.50   30.00    --   20.00  54.00-180.00   52
  7  \w    -30.00  -5.00   0.50   30.00    --   20.00  54.00  30.00   50
  8  \w     32.00  57.00   0.50   30.00    --   20.00  54.00  30.00   50
  9  \w     39.00  64.00   0.50   30.00    --   20.00  54.00-120.00   50
 10  \w    -60.00 -35.00   0.50   30.00    --   20.00  54.00  90.00   50
;
_diffrn_measurement_device       'two-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Mini II'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1037949000
_diffrn_orient_matrix_UB_12      0.0010074000
_diffrn_orient_matrix_UB_13      -0.0136233000
_diffrn_orient_matrix_UB_21      -0.0065704000
_diffrn_orient_matrix_UB_22      -0.0508288000
_diffrn_orient_matrix_UB_23      0.0144133000
_diffrn_orient_matrix_UB_31      -0.0127195000
_diffrn_orient_matrix_UB_32      0.0181378000
_diffrn_orient_matrix_UB_33      0.0412671000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0275
_diffrn_reflns_av_unetI/netI     0.0320
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            12564
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.647
_diffrn_reflns_theta_min         2.032
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.090
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88930
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.112a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.369
_exptl_crystal_description       block
_exptl_crystal_F_000             600
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.609
_refine_diff_density_min         -0.220
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     222
_refine_ls_number_reflns         4129
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0669
_refine_ls_R_factor_gt           0.0543
_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^)+(0.0579P)^2^+0.8719P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1366
_refine_ls_wR_factor_ref         0.1442
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3326
_reflns_number_total             4129
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ce00611a2.cif
_cod_data_source_block           PhBE-azop
_cod_depositor_comments
'Adding full bibliography for 7248998--7249003.cif.'
_cod_database_code               7249001
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H F B N O'
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.972
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 N1-C13 \\sim N1B-C13B
 with sigma of 0.02
 N1-C17 \\sim N1B-C17B
 with sigma of 0.02
 N1-B1 \\sim N1B-B1
 with sigma of 0.02
 C13-C14 \\sim C13B-C14B
 with sigma of 0.02
 C17-C16 \\sim C17B-C16B
 with sigma of 0.02
 C15-C14 \\sim C15B-C14B
 with sigma of 0.02
 C15-C16 \\sim C15B-C16B
 with sigma of 0.02
 C15-N2B \\sim C15B-N2B
 with sigma of 0.02
 N1-C14 \\sim N1B-C14B
 with sigma of 0.04
 N1-C16 \\sim N1B-C16B
 with sigma of 0.04
 C13-C17 \\sim C13B-C17B
 with sigma of 0.04
 C13-C15 \\sim C13B-C15B
 with sigma of 0.04
 C13-B1 \\sim C13B-B1
 with sigma of 0.04
 C17-C15 \\sim C17B-C15B
 with sigma of 0.04
 C17-B1 \\sim C17B-B1
 with sigma of 0.04
 C14-C16 \\sim C14B-C16B
 with sigma of 0.04
 C14-N2B \\sim C14B-N2B
 with sigma of 0.04
 C16-N2B \\sim C16B-N2B
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(N1) = Uanis(N1B)
Uanis(C17B) = Uanis(C17)
Uanis(C16B) = Uanis(C16)
Uanis(C15B) = Uanis(C15)
Uanis(C14B) = Uanis(C14)
Uanis(C13B) = Uanis(C13)
Uanis(N2B) = Uanis(N2)
4. Others
 Sof(N2B)=1-FVAR(1)
 Sof(N2)=FVAR(1)
 Sof(C15B)=Sof(C16B)=Sof(H16B)=Sof(C17B)=Sof(H17B)=Sof(N1B)=Sof(C13B)=
 Sof(H13B)=Sof(C14B)=Sof(H14B)=1-FVAR(2)
 Sof(N1)=Sof(C13)=Sof(H13)=Sof(C17)=Sof(H17)=Sof(C15)=Sof(C14)=Sof(H14)=
 Sof(C16)=Sof(H16)=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C12(H12), C2(H2), C5(H5), C13(H13), C3(H3), C9(H9), C10(H10), C8(H8),
 C17(H17), C11(H11), C4(H4), C14(H14), C16(H16), C16B(H16B), C17B(H17B),
 C13B(H13B), C14B(H14B)
;
_shelx_res_checksum              86537
_shelx_hkl_checksum              34610
_olex2_submission_original_sample_id BE-azop
_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 1.084
_oxdiff_exptl_absorpt_empirical_full_min 0.914