Pyridinium modification of a hexaazaphenalene skeleton: structure and spectroelectrochemical analysis
Deekamwong, Krittanun; Usov, Pavel M.; Ohtsu, Hiroyoshi; Kawano, Masaki; CrystEngComm  (2020) –; doi:10.1039/D0CE00850H

data_7240993
_publ_section_title
;
 Pyridinium modification of a hexaazaphenalene skeleton: structure and
 spectroelectrochemical analysis
;
_journal_name_full               CrystEngComm
_journal_paper_doi               10.1039/D0CE00850H
_journal_year                    2020
_chemical_formula_moiety         '2(Br), 5.903(O), C49 H39 N9 O6'
_chemical_formula_sum            'C49 H39 Br2 N9 O11.9'
_chemical_formula_weight         1104.15
_chemical_name_systematic        'Methyl p-toluate TPHAP'
_chemical_properties_physical    Photo-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-05-12
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2020-06-05 deposited with the CCDC.	2020-08-04 downloaded from the CCDC.
;
_cell_angle_alpha                75.376(4)
_cell_angle_beta                 84.342(4)
_cell_angle_gamma                88.140(4)
_cell_formula_units_Z            4
_cell_length_a                   7.8313(4)
_cell_length_b                   24.9650(13)
_cell_length_c                   26.4024(13)
_cell_measurement_reflns_used    10678
_cell_measurement_temperature    123.15
_cell_measurement_theta_max      30.7430
_cell_measurement_theta_min      2.3720
_cell_volume                     4970.2(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      123.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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   -110.00  70.00   0.50   30.00    --  -20.00  45.00   0.00  360
  2  \w   -110.00  70.00   0.50   30.00    --  -20.00  45.00  90.00  360
  3  \w   -110.00  70.00   0.50   30.00    --  -20.00  45.00 180.00  360
  4  \w   -110.00  70.00   0.50   30.00    --  -20.00  45.00 240.00  360
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0513309000
_diffrn_orient_matrix_UB_12      -0.0178055000
_diffrn_orient_matrix_UB_13      0.0206818000
_diffrn_orient_matrix_UB_21      0.0704334000
_diffrn_orient_matrix_UB_22      -0.0047569000
_diffrn_orient_matrix_UB_23      0.0155682000
_diffrn_orient_matrix_UB_31      -0.0262438000
_diffrn_orient_matrix_UB_32      0.0228599000
_diffrn_orient_matrix_UB_33      0.0103709000
_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  0.1937
_diffrn_reflns_av_unetI/netI     0.2251
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            68436
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.053
_diffrn_reflns_theta_max         25.053
_diffrn_reflns_theta_min         1.601
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.702
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69034
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.43c (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.476
_exptl_crystal_description       plate
_exptl_crystal_F_000             2245
_exptl_crystal_size_max          0.046
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.008
_refine_diff_density_max         1.207
_refine_diff_density_min         -0.951
_refine_diff_density_rms         0.156
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1313
_refine_ls_number_reflns         17624
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.2463
_refine_ls_R_factor_gt           0.1177
_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^)+(0.1442P)^2^+6.4280P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2609
_refine_ls_wR_factor_ref         0.3372
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7475
_reflns_number_total             17624
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ce00850h2.cif
_cod_data_source_block           MethylptoluateTPHAP
_cod_original_formula_sum        'C49 H39 Br2 N9 O11.90'
_cod_database_code               7240993
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHNOBr
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.926
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.01
_olex2_refinement_description
;
1. 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
2. Rigid bond restraints
 C71, C66, C67, C65
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C76 \\sim C75 \\sim C74 \\sim C94: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C66 \\sim C71 \\sim C67 \\sim C65: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Uanis(O7W) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
4. Others
 Sof(Br4B)=1-FVAR(1)
 Sof(Br4A)=Sof(O2W)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B), C86(H86A,H86B), C23(H23A,H23B), C9(H9A,H9B), C72(H72A,H72B),
 C58(H58A,H58B)
5.b Aromatic/amide H refined with riding coordinates:
 C21(H21), C28(H28), C33(H33), C35(H35), C84(H84), C85(H85), C38(H38),
 C39(H39), C36(H36), C27(H27), C41(H41), C32(H32), C90(H90), C42(H42), C74(H74),
  C76(H76), C87(H87), C82(H82), C24(H24), C88(H88), C22(H22), C5(H5), C10(H10),
 C11(H11), C18(H18), C62(H62), C91(H91), C4(H4), C13(H13), C68(H68), C73(H73),
 C54(H54), C14(H14), C63(H63), C77(H77), C19(H19), C7(H7), C71(H71), C53(H53),
 C70(H70), C57(H57), C25(H25), C56(H56), C8(H8), C60(H60), C67(H67), C81(H81),
 C59(H59)
5.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C50(H50A,H50B,H50C), C29(H29A,H29B,H29C), C15(H15A,H15B,
 H15C), C64(H64A,H64B,H64C), C78(H78A,H78B,H78C)
;
_shelx_res_checksum              6438
_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 1.308
_oxdiff_exptl_absorpt_empirical_full_min 0.630