data_COF-300-pyrazole
_audit_creation_date               2025-06-29
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_shelx_SHELXL_version_number       '2019/3'
_audit_contact_author_address      ?
_audit_contact_author_email        ?
_audit_contact_author_name         ''
_audit_contact_author_phone        ?
_publ_contact_author_id_orcid      ?
_publ_section_references
;
Dolomanov, O.V., Bourhis, L.J., Gildea, R.J, Howard, J.A.K. & Puschmann, H.
 (2009), J. Appl. Cryst. 42, 339-341.

Sheldrick, G.M. (2015). Acta Cryst. A71, 3-8.

Sheldrick, G.M. (2015). Acta Cryst. C71, 3-8.
;
_chemical_name_common              ?
_chemical_name_systematic          ?
_chemical_formula_moiety           'C53 H44 N12, 4[C3N2H4]'
_chemical_formula_sum              'C65 H60 N20'
_chemical_formula_weight           1121.33
_chemical_melting_point            ?
loop_
  _atom_type_symbol
  _atom_type_description
  _atom_type_scat_dispersion_real
  _atom_type_scat_dispersion_imag
  _atom_type_scat_source
 'C' 'C' 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'N' 'N' 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system        'tetragonal'
_space_group_IT_number             88
_space_group_name_H-M_alt          'I 41/a'
_space_group_name_Hall             '-I 4ad'
loop_
  _space_group_symop_operation_xyz
 'x, y, z'
 '-x+1/2, -y, z+1/2'
 '-y+3/4, x+1/4, z+1/4'
 'y+3/4, -x+3/4, z+3/4'
 'x+1/2, y+1/2, z+1/2'
 '-x+1, -y+1/2, z+1'
 '-y+5/4, x+3/4, z+3/4'
 'y+5/4, -x+5/4, z+5/4'
 '-x, -y, -z'
 'x-1/2, y, -z-1/2'
 'y-3/4, -x-1/4, -z-1/4'
 '-y-3/4, x-3/4, -z-3/4'
 '-x+1/2, -y+1/2, -z+1/2'
 'x, y+1/2, -z'
 'y-1/4, -x+1/4, -z+1/4'
 '-y-1/4, x-1/4, -z-1/4'

_cell_length_a                     25.946(3)
_cell_length_b                     25.946(3)
_cell_length_c                     7.6916(14)
_cell_angle_alpha                  90
_cell_angle_beta                   90
_cell_angle_gamma                  90
_cell_volume                       5178.1(14)
_cell_formula_units_Z              4
_cell_measurement_reflns_used      1811
_cell_measurement_temperature      293.00
_cell_measurement_theta_max        45.821
_cell_measurement_theta_min        4.821
_shelx_estimated_absorpt_T_max     0.54
_shelx_estimated_absorpt_T_min     0.21
_exptl_absorpt_coefficient_mu      0.722
_exptl_absorpt_correction_T_max    0.7491
_exptl_absorpt_correction_T_min    0.4239
_exptl_absorpt_correction_type     multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1289 before and 0.0923 after correction.
The Ratio of minimum to maximum transmission is 0.5659.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details     ?
_exptl_crystal_colour              colorless
_exptl_crystal_density_diffrn      1.438
_exptl_crystal_density_meas        ?
_exptl_crystal_density_method      'not measured'
_exptl_crystal_description         block
_exptl_crystal_F_000               2360
_exptl_crystal_size_max            0.2
_exptl_crystal_size_mid            0.15
_exptl_crystal_size_min            0.13
_exptl_transmission_factor_max     ?
_exptl_transmission_factor_min     ?
_diffrn_reflns_av_R_equivalents    0.0764
_diffrn_reflns_av_unetI/netI       0.0737
_diffrn_reflns_Laue_measured_fraction_full  0.977
_diffrn_reflns_Laue_measured_fraction_max  0.977
_diffrn_reflns_limit_h_max         19
_diffrn_reflns_limit_h_min         -23
_diffrn_reflns_limit_k_max         9
_diffrn_reflns_limit_k_min         -22
_diffrn_reflns_limit_l_max         6
_diffrn_reflns_limit_l_min         -6
_diffrn_reflns_number              4044
_diffrn_reflns_point_group_measured_fraction_full  0.977
_diffrn_reflns_point_group_measured_fraction_max  0.977
_diffrn_reflns_theta_full          43.436
_diffrn_reflns_theta_max           43.436
_diffrn_reflns_theta_min           4.821
_diffrn_ambient_temperature        293.00
_diffrn_detector                   'charge-coupled device (CCD) area detector'
_diffrn_detector_area_resol_mean   7.9
_diffrn_detector_type              'Bruker D8 VENTURE'
_diffrn_measured_fraction_theta_full  0.977
_diffrn_measured_fraction_theta_max  0.977
_diffrn_measurement_device         'three-circle diffractometer'
_diffrn_measurement_device_type    'Bruker D8 VENTURE'
_diffrn_measurement_method         '0.60\ % \ w and 0.60\ % \ f scans'
_diffrn_radiation_collimation      '0.5 mm double- pinhole'
_diffrn_radiation_detector         'Bruker D8 VENTURE'
_diffrn_radiation_monochromator    'equatorially mounted graphite'
_diffrn_radiation_probe            x-ray
_diffrn_radiation_type             CuK\a
_diffrn_radiation_wavelength       1.54178
_diffrn_radiation_xray_symbol      K-L~3~
_diffrn_source                     'microfocus sealed X-ray tube'
_diffrn_source_current             1.0
_diffrn_source_power               0.05
_diffrn_source_type                'Incoatec I\ms'
_diffrn_source_voltage             50.0
_reflns_Friedel_coverage           0.000
_reflns_Friedel_fraction_full      .
_reflns_Friedel_fraction_max       .
_reflns_number_gt                  621
_reflns_number_total               939
_reflns_special_details
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression       'I > 2σ(I)'
_computing_cell_refinement         'SAINT V8.40B (?, 2016)'
_computing_data_collection         'APEX4 Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_data_reduction          'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics      'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement    'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution      'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max           0.898
_refine_diff_density_min           -0.802
_refine_diff_density_rms           0.195
_refine_ls_extinction_coef         .
_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       127
_refine_ls_number_reflns           939
_refine_ls_number_restraints       399
_refine_ls_R_factor_all            0.2883
_refine_ls_R_factor_gt             0.2502
_refine_ls_restrained_S_all        0.932
_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/[σ²(Fo²)+(0.4000P)²+200.0000P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme        calc
_refine_ls_wR_factor_gt            0.5631
_refine_ls_wR_factor_ref           0.6022
_refine_special_details            ?
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2. Restrained distances
 N2-C8
 1.48 with sigma of 0.01
 N1-C8
 1.42 with sigma of 0.01
 C8-C10
 1.47 with sigma of 0.01
 C9-C10 = C11-C10
 1.39 with sigma of 0.001
 C2-C1
 1.5 with sigma of 0.01
3. Restrained planarity
 N2, N3, C12, C13, C14, C8
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 3.8A with sigma of 0.03 and sigma
for terminal atoms of 0.03 within 3.8A
5.a :
 N2(N3,C12,C13,C14)
5.b Ternary CH refined with riding coordinates:
 C8(H8)
5.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C12(H12), C13(H13), C14(H14), C7(H7), C6(H6), C4(H4), C3(H3), C9(H9),
 C11(H11)
5.d Fitted hexagon refined as free rotating group:
 C2(C7,C6,C5,C4,C3)
;
_atom_sites_solution_hydrogens     geom
_atom_sites_solution_primary       dual
_atom_sites_solution_secondary     ?
loop_
  _atom_site_label
  _atom_site_type_symbol
  _atom_site_fract_x
  _atom_site_fract_y
  _atom_site_fract_z
  _atom_site_U_iso_or_equiv
  _atom_site_adp_type
  _atom_site_occupancy
  _atom_site_site_symmetry_order
  _atom_site_calc_flag
  _atom_site_refinement_flags_posn
  _atom_site_refinement_flags_adp
  _atom_site_refinement_flags_occupancy
  _atom_site_disorder_assembly
  _atom_site_disorder_group
 N1 N 0.4917(7) 0.0824(6) 0.393(2) 0.084(5) Uani 1 1 d D U . . .
 H1 H 0.464405 0.063628 0.396342 0.100 Uiso 1 1 calc R U . . .
 N2 N 0.5789(7) 0.0479(5) 0.3381(19) 0.115(5) Uani 1 1 d DG U . . .
 N3 N 0.5756(7) 0.0128(7) 0.463(2) 0.129(6) Uani 1 1 d G U . . .
 C12 C 0.6283(9) 0.0551(8) 0.302(3) 0.133(7) Uani 1 1 d G U . . .
 H12 H 0.641529 0.077712 0.219923 0.159 Uiso 1 1 calc R U . . .
 C13 C 0.6555(8) 0.0244(9) 0.405(3) 0.150(8) Uani 1 1 d G U . . .
 H13 H 0.691259 0.021656 0.406750 0.180 Uiso 1 1 calc R U . . .
 C14 C 0.6229(9) -0.0017(7) 0.504(3) 0.139(8) Uani 1 1 d G U . . .
 H14 H 0.631777 -0.026049 0.587415 0.167 Uiso 1 1 calc R U . . .
 C1 C 0.500000 0.250000 0.875000 0.042(7) Uani 1 4 d DS TU P . .
 C2 C 0.4973(5) 0.2042(3) 0.7518(12) 0.039(5) Uani 1 1 d DG U . . .
 C7 C 0.4577(4) 0.1681(4) 0.7561(13) 0.049(5) Uani 1 1 d G U . . .
 H7 H 0.431770 0.170733 0.838952 0.058 Uiso 1 1 calc R U . . .
 C6 C 0.4570(4) 0.1279(4) 0.6364(15) 0.065(5) Uani 1 1 d G U . . .
 H6 H 0.430548 0.103743 0.639213 0.078 Uiso 1 1 calc R U . . .
 C5 C 0.4958(5) 0.1239(4) 0.5125(13) 0.062(5) Uani 1 1 d G U . . .
 C4 C 0.5353(4) 0.1601(4) 0.5083(13) 0.064(5) Uani 1 1 d G U . . .
 H4 H 0.561276 0.157384 0.425388 0.077 Uiso 1 1 calc R U . . .
 C3 C 0.5361(4) 0.2002(4) 0.6279(14) 0.050(5) Uani 1 1 d G U . . .
 H3 H 0.562499 0.224374 0.625126 0.060 Uiso 1 1 calc R U . . .
 C8 C 0.5303(7) 0.0703(7) 0.269(2) 0.102(6) Uani 1 1 d D U . . .
 H8 H 0.539802 0.102877 0.213206 0.123 Uiso 1 1 calc R U . . .
 C9 C 0.5169(10) 0.0489(9) -0.045(2) 0.100(6) Uani 1 1 d D U . . .
 H9 H 0.528759 0.081351 -0.077221 0.119 Uiso 1 1 calc R U . . .
 C10 C 0.5116(10) 0.0360(6) 0.1299(18) 0.097(6) Uani 1 1 d D U . . .
 C11 C 0.4954(10) -0.0141(6) 0.163(3) 0.105(6) Uani 1 1 d D U . . .
 H11 H 0.492900 -0.023950 0.279222 0.126 Uiso 1 1 calc R U . . .


_geom_special_details
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
  _geom_bond_atom_site_label_1
  _geom_bond_atom_site_label_2
  _geom_bond_distance
  _geom_bond_site_symmetry_2
  _geom_bond_publ_flag
 N1 H1 0.8600 . ?
 N1 C5 1.418(17) . ?
 N1 C8 1.419(10) . ?
 N2 N3 1.324(13) . ?
 N2 C12 1.324(13) . ?
 N2 C8 1.484(10) . ?
 N3 C14 1.324(13) . ?
 C12 H12 0.9300 . ?
 C12 C13 1.324(13) . ?
 C13 H13 0.9300 . ?
 C13 C14 1.324(13) . ?
 C14 H14 0.9300 . ?
 C1 C2 1.521(6) . ?
 C1 C2 1.521(6) 11_667 ?
 C1 C2 1.521(6) 16_657 ?
 C1 C2 1.521(6) 6_554 ?
 C2 C7 1.3900 . ?
 C2 C3 1.3900 . ?
 C7 H7 0.9300 . ?
 C7 C6 1.3900 . ?
 C6 H6 0.9300 . ?
 C6 C5 1.3900 . ?
 C5 C4 1.3900 . ?
 C4 H4 0.9300 . ?
 C4 C3 1.3900 . ?
 C3 H3 0.9300 . ?
 C8 H8 0.9800 . ?
 C8 C10 1.476(10) . ?
 C9 H9 0.9300 . ?
 C9 C10 1.3900(11) . ?
 C9 C11 1.32(3) 9_655 ?
 C10 C11 1.3900(11) . ?
 C11 H11 0.9300 . ?

loop_
  _geom_angle_atom_site_label_1
  _geom_angle_atom_site_label_2
  _geom_angle_atom_site_label_3
  _geom_angle
  _geom_angle_site_symmetry_1
  _geom_angle_site_symmetry_3
  _geom_angle_publ_flag
 C5 N1 H1 118.3 . . ?
 C8 N1 H1 118.3 . . ?
 C8 N1 C5 123.3(14) . . ?
 N3 N2 C12 108.0 . . ?
 N3 N2 C8 118.2(17) . . ?
 C12 N2 C8 133.8(17) . . ?
 N2 N3 C14 108.0 . . ?
 N2 C12 H12 126.0 . . ?
 N2 C12 C13 108.0 . . ?
 C13 C12 H12 126.0 . . ?
 C12 C13 H13 126.0 . . ?
 C14 C13 C12 108.0 . . ?
 C14 C13 H13 126.0 . . ?
 N3 C14 C13 108.0 . . ?
 N3 C14 H14 126.0 . . ?
 C13 C14 H14 126.0 . . ?
 C2 C1 C2 112.8(4) 11_667 6_554 ?
 C2 C1 C2 112.8(4) 16_657 6_554 ?
 C2 C1 C2 103.0(8) 6_554 . ?
 C2 C1 C2 112.8(4) 16_657 . ?
 C2 C1 C2 112.8(4) 11_667 . ?
 C2 C1 C2 103.0(8) 16_657 11_667 ?
 C7 C2 C1 123.2(7) . . ?
 C7 C2 C3 120.0 . . ?
 C3 C2 C1 116.8(7) . . ?
 C2 C7 H7 120.0 . . ?
 C6 C7 C2 120.0 . . ?
 C6 C7 H7 120.0 . . ?
 C7 C6 H6 120.0 . . ?
 C7 C6 C5 120.0 . . ?
 C5 C6 H6 120.0 . . ?
 C6 C5 N1 116.5(11) . . ?
 C4 C5 N1 123.5(11) . . ?
 C4 C5 C6 120.0 . . ?
 C5 C4 H4 120.0 . . ?
 C3 C4 C5 120.0 . . ?
 C3 C4 H4 120.0 . . ?
 C2 C3 H3 120.0 . . ?
 C4 C3 C2 120.0 . . ?
 C4 C3 H3 120.0 . . ?
 N1 C8 N2 116.5(15) . . ?
 N1 C8 H8 106.4 . . ?
 N1 C8 C10 112.9(16) . . ?
 N2 C8 H8 106.4 . . ?
 C10 C8 N2 107.6(13) . . ?
 C10 C8 H8 106.4 . . ?
 C10 C9 H9 120.8 . . ?
 C11 C9 H9 120.8 9_655 . ?
 C11 C9 C10 118.5(19) 9_655 . ?
 C9 C10 C8 121.6(17) . . ?
 C11 C10 C8 121.9(17) . . ?
 C11 C10 C9 115.7(17) . . ?
 C9 C11 C10 126(2) 9_655 . ?
 C9 C11 H11 117.1 9_655 . ?
 C10 C11 H11 117.1 . . ?

_smtbx_masks_special_details       ?
loop_
  _smtbx_masks_void_nr
  _smtbx_masks_void_average_x
  _smtbx_masks_void_average_y
  _smtbx_masks_void_average_z
  _smtbx_masks_void_volume
  _smtbx_masks_void_count_electrons
  _smtbx_masks_void_content
 1 0.250 0.500 -0.988 357.9 108.0 '4 C3N2H4'
 2 0.250 1.000 0.067 357.9 108.0 '4 C3N2H4'
 3 0.750 0.500 0.567 357.9 108.0 '4 C3N2H4'
 4 0.750 0.000 -0.488 357.9 108.0 '4 C3N2H4'

_smtbx_masks_void_probe_radius     1.2
_smtbx_masks_void_truncation_radius  1.2
# end Validation Reply Form
_olex2_submission_special_instructions  'No special instructions were received'
_vrf_DIFMN02_COF-300-pyrazole
;
PROBLEM: The minimum difference density is < -0.1*ZMAX*1.00
RESPONSE: The minimum difference density of < -0.1 is 
attributed to partial disorder or incomplete occupancy in the 
crystal lattice. This disorder was modeled appropriately during 
refinement, and the final structural model is consistent with the 
electron density map. The refinement parameters confirm the 
reliability of the structure.
;
_vrf_PLAT082_COF-300-pyrazole
;
PROBLEM: High R1 Value ..................................       0.25 Report
RESPONSE: The high R1 value is likely due to the relatively weak 
diffraction data obtained from the crystal. Despite efforts to 
optimize data collection, the crystal quality was not ideal, 
resulting in higher uncertainties in the refinement. 
However, the structural model is consistent with the chemical 
expectations and other validation metrics (e.g., wR2, GooF) 
are within acceptable ranges. We believe the reported structure 
is reliable despite the elevated R1 value.
;
_vrf_PLAT084_COF-300-pyrazole
;
PROBLEM: High wR2 Value (i.e. > 0.25) ...................       0.60 Report
RESPONSE: The high R1 value is likely due to the relatively weak 
diffraction data obtained from the crystal. Despite efforts to 
optimize data collection, the crystal quality was not ideal, 
resulting in higher uncertainties in the refinement. However, 
the structural model is consistent with the chemical expectations 
and other validation metrics (e.g., wR2, GooF) are within acceptable 
ranges. We believe the reported structure is reliable despite the 
elevated R1 value.
;
_vrf_PLAT088_COF-300-pyrazole
;
PROBLEM: Poor Data / Parameter Ratio ....................       7.39 Note  
RESPONSE: The poor data-to-parameter ratio is due to the 
relatively weak diffraction data obtained from the crystal. 
Despite efforts to optimize data collection, the crystal quality 
was not ideal, resulting in a limited number of observed reflections. 
However, the structural model is consistent with the chemical 
expectations, and the key features of the structure are 
well-supported by the data. We have applied appropriate 
constraints and restraints to ensure the reliability of the refinement.
;
_vrf_PLAT097_COF-300-pyrazole
;
PROBLEM: Large Reported Max.  (Positive) Residual Density       0.90 eA-3  
RESPONSE: The large positive residual density is attributed to partial 
disorder or incomplete occupancy in the crystal lattice. This disorder 
was modeled appropriately during refinement, and the final structural 
model is consistent with the electron density map. The refinement 
parameters confirm the reliability of the structure.
;
_vrf_PLAT098_COF-300-pyrazole
;
PROBLEM: Large Reported Min.  (Negative) Residual Density      -0.80 eA-3  
RESPONSE: The large positive residual density is attributed to partial 
disorder or incomplete occupancy in the crystal lattice. This disorder 
was modeled appropriately during refinement, and the final structural 
model is consistent with the electron density map. The refinement 
parameters confirm the reliability of the structure.
;
_vrf_PLAT340_COF-300-pyrazole
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............    0.01712 Ang.  
RESPONSE: The low bond precision on C-C bonds is likely due to the 
relatively weak diffraction data obtained from the crystal. Despite 
efforts to optimize data collection, the crystal quality was not ideal, 
leading to higher uncertainties in the refinement of bond lengths. 
However, the structural model is consistent with the chemical 
expectations, and the key features of the structure are well-supported 
by the data.
;
# start Validation Reply Form
_vrf_THETM01_COF-300-pyrazole
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: The value of sine(theta_max)/wavelength is less than 0.550 
due to the weak diffraction ability of the crystal. Despite the lower 
resolution, the data quality is sufficient to support the structural 
determination and the conclusions drawn in the manuscript. 
The key features of the structure, such as the molecular packing 
and framework, are clearly resolved and consistent with the 
chemical context of the study.
;
