Molecular structure, optical and magnetic properties of free-base tetrapyrazinoporphyrazine in various reduction states
Konarev, Dmitri V.; Faraonov, Maxim A.; Kuz`min, Alexey V.; Osipov, Nikita G.; Khasanov, Salavat S.; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Lyubovskaya, Rimma N.; New Journal of Chemistry 43 (2019) 19214–19222; doi:10.1039/C9NJ04775A

data_7059047
_publ_section_title
;
 Molecular structure, optical and magnetic properties of free-base
 tetrapyrazinoporphyrazine in various reduction states
;
_journal_issue                   48
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              19214
_journal_page_last               19222
_journal_paper_doi               10.1039/C9NJ04775A
_journal_volume                  43
_journal_year                    2019
_chemical_formula_moiety
'3(C6 H4 Cl2), 2(C18 H36 K N2 O6), 2(C24 H10 N16)'
_chemical_formula_sum            'C102 H104 Cl6 K2 N36 O12'
_chemical_formula_weight         2317.11
_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             2019-06-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-09-08 deposited with the CCDC.	2019-11-14 downloaded from the CCDC.
;
_cell_angle_alpha                66.352(2)
_cell_angle_beta                 74.863(2)
_cell_angle_gamma                89.576(2)
_cell_formula_units_Z            2
_cell_length_a                   13.7277(3)
_cell_length_b                   19.2901(5)
_cell_length_c                   23.1243(6)
_cell_measurement_reflns_used    26138
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      29.3640
_cell_measurement_theta_min      2.0440
_cell_volume                     5381.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      113(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2283
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.850
_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    -25.00  47.00   1.00   48.00    --   11.89 -99.00-180.00   72
  2  \w   -101.00 -76.00   1.00   48.00    --  -12.20 178.00 -90.00   25
  3  \w    -27.00  -1.00   1.00   48.00    --  -12.20 -37.00-150.00   26
  4  \w    -58.00  -4.00   1.00   48.00    --  -12.20 -57.00 -30.00   54
  5  \w    -25.00   0.00   1.00   48.00    --  -12.20 -99.00-120.00   25
  6  \w    -51.00  69.00   1.00   48.00    --  -12.20  19.00 -60.00  120
  7  \w    -87.00 -58.00   1.00   48.00    --  -12.20-178.00   0.00   29
  8  \w    -52.00  12.00   1.00   48.00    --  -12.20 -57.00 -90.00   64
  9  \w    -24.00  25.00   1.00   48.00    --  -12.20 -87.00  59.00   49
 10  \w    -75.00 -65.00   1.00   48.00    --  -12.20 133.00-161.10   10
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, AtlasS2, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0334461000
_diffrn_orient_matrix_UB_12      -0.0341267000
_diffrn_orient_matrix_UB_13      0.0147302000
_diffrn_orient_matrix_UB_21      0.0216481000
_diffrn_orient_matrix_UB_22      -0.0082741000
_diffrn_orient_matrix_UB_23      -0.0276005000
_diffrn_orient_matrix_UB_31      0.0362349000
_diffrn_orient_matrix_UB_32      -0.0199491000
_diffrn_orient_matrix_UB_33      0.0154672000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0276
_diffrn_reflns_av_unetI/netI     0.0446
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.850
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            70854
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.850
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.686
_diffrn_reflns_theta_min         1.816
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.316
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90903
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark black'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.430
_exptl_crystal_description       block
_exptl_crystal_F_000             2408
_exptl_crystal_size_max          0.418
_exptl_crystal_size_mid          0.285
_exptl_crystal_size_min          0.179
_refine_diff_density_max         1.669
_refine_diff_density_min         -0.740
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1484
_refine_ls_number_reflns         25903
_refine_ls_number_restraints     192
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0902
_refine_ls_R_factor_gt           0.0627
_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^)+(0.0717P)^2^+8.1639P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1555
_refine_ls_wR_factor_ref         0.1731
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19105
_reflns_number_total             25903
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9nj04775a2.cif
_cod_data_source_block           exp_1314_int1
_cod_original_cell_volume        5381.8(2)
_cod_database_code               7059047
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C48H58N18Cl2O6K1
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2. Restrained distances
 C81-C82 \\sim C81A-C82A
 with sigma of 0.02
 C81-C86 \\sim C81A-C86A
 with sigma of 0.02
 C81-Cl81 \\sim C81A-Cl
 with sigma of 0.02
 C82-C83 \\sim C82A-C83A
 with sigma of 0.02
 C82-Cl82 \\sim C82A-Cl1
 with sigma of 0.02
 C83-C84 \\sim C83A-C84A
 with sigma of 0.02
 C84-C85 \\sim C84A-C85A
 with sigma of 0.02
 C85-C86 \\sim C85A-C86A
 with sigma of 0.02
 C81-C83 \\sim C81A-C83A
 with sigma of 0.04
 C81-C85 \\sim C81A-C85A
 with sigma of 0.04
 C81-Cl82 \\sim C81A-Cl1
 with sigma of 0.04
 C82-C84 \\sim C82A-C84A
 with sigma of 0.04
 C82-C86 \\sim C82A-C86A
 with sigma of 0.04
 C82-Cl81 \\sim C82A-Cl
 with sigma of 0.04
 C83-C85 \\sim C83A-C85A
 with sigma of 0.04
 C83-Cl82 \\sim C83A-Cl1
 with sigma of 0.04
 C84-C86 \\sim C84A-C86A
 with sigma of 0.04
 C86-Cl81 \\sim C86A-Cl
 with sigma of 0.04
3. Rigid bond restraints
 C81A, C81, C86, C82, Cl81, H86, C85, C83, Cl82, H85, C84, H83, C83A, H83A,
 C84A, Cl1, H84, C82A, H84A, C85A, H85A, C86A, Cl, H86A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C82A \\sim C81A \\sim C81 \\sim C86 \\sim C86A \\sim C85 \\sim C85A \\sim C84
\\sim C83 \\sim C84A \\sim C83A: within 1.7A with sigma of 0.002 and sigma for
terminal atoms of 0.004
Cl1 \\sim Cl82 \\sim Cl81 \\sim Cl: within 1.7A with sigma of 0.004 and sigma
for terminal atoms of 0.008
5. Others
 Sof(C81A)=Sof(C82A)=Sof(C83A)=Sof(H83A)=Sof(C84A)=Sof(H84A)=Sof(C85A)=
 Sof(H85A)=Sof(C86A)=Sof(H86A)=Sof(Cl)=Sof(Cl1)=1-FVAR(1)
 Sof(C81)=Sof(C86)=Sof(H86)=Sof(C85)=Sof(H85)=Sof(C84)=Sof(H84)=Sof(C83)=
 Sof(H83)=Sof(C82)=Sof(Cl81)=Sof(Cl82)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C101(H10A,H10B), C102(H10C,H10D), C103(H10E,H10F), C104(H10G,H10H), C105(H10I,
 H10J), C106(H10K,H10L), C107(H10M,H10N), C108(H10O,H10P), C109(H10Q,H10R),
 C110(H11A,H11B), C111(H11C,H11D), C112(H11E,H11F), C113(H11G,H11H), C114(H11I,
 H11J), C115(H11K,H11L), C116(H11M,H11N), C117(H11O,H11P), C118(H11Q,H11R),
 C201(H20A,H20B), C202(H20C,H20D), C203(H20E,H20F), C204(H20G,H20H), C205(H20I,
 H20J), C206(H20K,H20L), C207(H20M,H20N), C208(H20O,H20P), C209(H20Q,H20R),
 C210(H21A,H21B), C211(H21C,H21D), C212(H21E,H21F), C213(H21G,H21H), C214(H21I,
 H21J), C215(H21K,H21L), C216(H21M,H21N), C217(H21O,H21P), C218(H21Q,H21R)
6.b Aromatic/amide H refined with riding coordinates:
 C63(H63), C64(H64), C65(H65), C66(H66), C73(H73), C74(H74), C75(H75),
 C76(H76), C303(H303), C304(H304), C309(H309), C310(H310), C315(H315),
 C316(H316), C321(H321), C322(H322), N302(H302), N310(H31A), C404(H404),
 C405(H405), C410(H410), C411(H411), N403(H403), C504(H504), C505(H505),
 C510(H510), C511(H511), N503(H503), C86(H86), C85(H85), C84(H84), C83(H83),
 C83A(H83A), C84A(H84A), C85A(H85A), C86A(H86A)
6.c Fitted hexagon refined as free rotating group:
 C81(C86,C85,C84,C83,C82)
;
_shelx_res_checksum              76794
_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 1.235
_oxdiff_exptl_absorpt_empirical_full_min 0.919