Crystalline salts of anionic free-base tetrapyrazinoporphyrazines with alkyl-substituents or an extended π-electron system
Faraonov, Maxim A.; Osipov, Nikita G.; Romanenko, Nikita R.; Kuzmin, Alexey V.; Kornev, Alexey B.; Stuzhin, Pavel A.; Khasanov, Salavat S.; Konarev, Dmitri V.; New Journal of Chemistry 46 (2022) 22195–22202; doi:10.1039/D2NJ04578H

data_7062018
_publ_section_title
;
 Crystalline salts of anionic free-base tetrapyrazinoporphyrazines with
 alkyl-substituents or an extended \p-electron system
;
_journal_issue                   46
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              22195
_journal_page_last               22202
_journal_paper_doi               10.1039/D2NJ04578H
_journal_volume                  46
_journal_year                    2022
_chemical_formula_moiety         '3.701(C6 H4 Cl2), C36 H30 N P2, C16 H13 N8'
_chemical_formula_sum            'C74.21 H57.81 Cl7.4 N9 P2'
_chemical_formula_weight         1399.94
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-11-03
_audit_creation_method
;FinalCif V110 by Daniel Kratzert, Freiburg 2022,
https://dkratzert.de/finalcif.html
;
_audit_update_record
;
2022-09-14 deposited with the CCDC.	2022-10-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.265(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.5316(10)
_cell_length_b                   20.3754(7)
_cell_length_c                   32.1634(13)
_cell_measurement_reflns_used    6462
_cell_measurement_temperature    103(2)
_cell_measurement_theta_max      25.6990
_cell_measurement_theta_min      2.1930
_cell_volume                     14051.0(10)
_computing_cell_refinement       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      103(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2283
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.972
_diffrn_measured_fraction_theta_max 0.928
_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    -35.00  53.00   0.50   80.00    --  -10.83  19.00 -60.00  176
  2  \w    -51.00  40.50   0.50   80.00    --  -10.83  19.00-150.00  183
;
_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      -0.0161078000
_diffrn_orient_matrix_UB_12      0.0181810000
_diffrn_orient_matrix_UB_13      0.0144482000
_diffrn_orient_matrix_UB_21      0.0156801000
_diffrn_orient_matrix_UB_22      -0.0179195000
_diffrn_orient_matrix_UB_23      0.0167123000
_diffrn_orient_matrix_UB_31      0.0242678000
_diffrn_orient_matrix_UB_32      0.0236698000
_diffrn_orient_matrix_UB_33      0.0015696000
_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  0.0692
_diffrn_reflns_av_unetI/netI     0.1569
_diffrn_reflns_Laue_measured_fraction_full 0.972
_diffrn_reflns_Laue_measured_fraction_max 0.928
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            30927
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.928
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.100
_diffrn_reflns_theta_min         1.554
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.393
_exptl_absorpt_correction_T_max  0.977
_exptl_absorpt_correction_T_min  0.928
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.120a (Rigaku Oxford Diffraction, 2021)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    1.324
_exptl_crystal_description       plate
_exptl_crystal_F_000             5775
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.845
_refine_diff_density_min         -0.656
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1008
_refine_ls_number_reflns         14463
_refine_ls_number_restraints     389
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.2059
_refine_ls_R_factor_gt           0.1047
_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^)+(0.1411P)^2^+42.1183P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2479
_refine_ls_wR_factor_ref         0.3012
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7427
_reflns_number_total             14463
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj04578h2.cif
_cod_data_source_block           exp_1942_int1
_cod_depositor_comments
'Adding full bibliography for 7062016--7062018.cif.'
_cod_original_formula_sum        'C74.21 H57.81 Cl7.40 N9 P2'
_cod_database_code               7062018
_chemical_oxdiff_formula         'C624  H0  N16  P16  Cl64  '
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9059(13)
 0.0941(13)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Rigid bond restraints
 Cl72, C72, C71, Cl71
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C75 \\sim C33 \\sim C36 \\sim C71 \\sim C34 \\sim C72 \\sim C32 \\sim C76 \\sim
C35 \\sim C73 \\sim C74 \\sim C31: within 1.7A with sigma of 0.005 and sigma
for terminal atoms of 0.01 within 1.7A
C96 \\sim C86 \\sim C81 \\sim C91 \\sim C85 \\sim C92 \\sim C82 \\sim C93 \\sim
C83 \\sim C95 \\sim C84 \\sim C94: within 1.7A with sigma of 0.005 and sigma
for terminal atoms of 0.01 within 1.7A
Cl91 \\sim Cl92: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
Cl81 \\sim Cl82: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
Cl32 \\sim Cl31: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
5. Same fragment restrains
{Cl31, Cl32, C31, C32, C33, C34, C35, C36} sigma for 1-2: 0.001, 1-3: 0.001
as in
{Cl81, Cl82, C81, C82, C83, C84, C85, C86}
{Cl31, Cl32, C31, C32, C33, C34, C35, C36} sigma for 1-2: 0.001, 1-3: 0.001
as in
{Cl71, Cl72, C71, C72, C73, C74, C75, C76}
{Cl31, Cl32, C31, C32, C33, C34, C35, C36} sigma for 1-2: 0.001, 1-3: 0.001
as in
{Cl91, Cl92, C91, C92, C93, C94, C95, C96}
6. Others
 Sof(Cl81)=Sof(Cl82)=Sof(C81)=Sof(C82)=Sof(C83)=Sof(H83)=Sof(C84)=Sof(H84)=
 Sof(C85)=Sof(H85)=Sof(C86)=Sof(H86)=FVAR(1)
 Sof(Cl71)=Sof(Cl72)=Sof(C71)=Sof(C72)=Sof(C73)=Sof(H73)=Sof(C74)=Sof(H74)=
 Sof(C75)=Sof(H75)=Sof(C76)=Sof(H76)=1-FVAR(2)
 Sof(Cl31)=Sof(Cl32)=Sof(C31)=Sof(C32)=Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=
 Sof(C35)=Sof(H35)=Sof(C36)=Sof(H36)=FVAR(2)
 Sof(Cl91)=Sof(Cl92)=Sof(C91)=Sof(C92)=Sof(C93)=Sof(H93)=Sof(C94)=Sof(H94)=
 Sof(C95)=Sof(H95)=Sof(C96)=Sof(H96)=FVAR(3)
 Fixed Sof: H101(0.5) H103(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C43(H43), C44(H44), C45(H45), C46(H46), C51(H51), C52(H52), C61(H61),
 C62(H62), C202(H202), C203(H203), C204(H204), C205(H205), C206(H206),
 C208(H208), C209(H209), C210(H210), C211(H211), C212(H212), C214(H214),
 C215(H215), C216(H216), C217(H217), C218(H218), C220(H220), C221(H221),
 C222(H222), C223(H223), C224(H224), C226(H226), C227(H227), C228(H228),
 C229(H229), C230(H230), C232(H232), C233(H233), C234(H234), C235(H235),
 C236(H236), N101(H101), N103(H103), C33(H33), C34(H34), C35(H35), C36(H36),
 C83(H83), C84(H84), C85(H85), C86(H86), C73(H73), C74(H74), C75(H75), C76(H76),
  C93(H93), C94(H94), C95(H95), C96(H96)
7.b Idealised Me refined as rotating group:
 C113(H11A,H11B,H11C), C114(H11D,H11E,H11F), C115(H11G,H11H,H11I), C116(H11J,
 H11K,H11L)
;
_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 1.077
_oxdiff_exptl_absorpt_empirical_full_min 0.931
_shelx_estimated_absorpt_t_min   0.922
_shelx_estimated_absorpt_t_max   0.977
_shelx_res_checksum              47076