# Supplementary Information (SI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 2025

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_shelx
_database_code_depnum_ccdc_archive 'CCDC 2373968'
loop_
_audit_author_name
_audit_author_address
'Aidar Gubaidullin'
;Arbuzov Institute of Organic and Physical Chemistry of RAS
Russia
;
_audit_update_record             
;
2024-07-27 deposited with the CCDC.	2025-01-09 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        
(E)-5-oxo-6-(2-oxo-2-phenylethylidene)-1,4,5,6-tetrahydropyrazine-2,3-dicarbonitrile
_chemical_name_common            ?
_chemical_melting_point          538-539
_chemical_formula_moiety         'C14 H8 N4 O2'
_chemical_formula_sum            'C14 H8 N4 O2'
_chemical_formula_weight         264.24

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 '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 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

_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.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   13.1843(14)
_cell_length_b                   12.8448(14)
_cell_length_c                   6.8879(7)
_cell_angle_alpha                90
_cell_angle_beta                 94.584(4)
_cell_angle_gamma                90
_cell_volume                     1162.7(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9933
_cell_measurement_theta_min      2.22
_cell_measurement_theta_max      29.16
_exptl_crystal_description       plate
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.510
_exptl_crystal_F_000             544
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.383
_exptl_crystal_size_mid          0.084
_exptl_crystal_size_min          0.014
_exptl_absorpt_coefficient_mu    0.106
_shelx_estimated_absorpt_T_min   0.960
_shelx_estimated_absorpt_T_max   0.999
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6776
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_process_details   
;
 G.M. Sheldrick (1998a). SADABS v.2.01, Bruker.
 Siemens Area Detector Absorption Correction Program.
 Bruker AXS. Madison. Wisconsin. USA
  Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D.,
  SADABS-2016/2, J. Appl. Cryst. 48 (2015) 3-10. 
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'microfocus I\mS DIAMOND Mo X-ray tube'
_diffrn_radiation_monochromator  'multilayer optics'
_diffrn_detector                 'area detector PHOTON III'
_diffrn_measurement_device_type  'Bruker D8 QUEST'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            20407
_diffrn_reflns_av_unetI/netI     0.0321
_diffrn_reflns_av_R_equivalents  0.0454
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         2.217
_diffrn_reflns_theta_max         29.127
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.943
_diffrn_measured_fraction_theta_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.943
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_point_group_measured_fraction_full 0.981
_reflns_number_total             2953
_reflns_number_gt                2757
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _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.
;

_computing_data_collection       'APEX3 v2019.11-0 (Bruker AXS)'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0455P)²+4.4273P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2953
_refine_ls_number_parameters     198
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1033
_refine_ls_R_factor_gt           0.0986
_refine_ls_wR_factor_ref         0.2157
_refine_ls_wR_factor_gt          0.2134
_refine_ls_goodness_of_fit_ref   1.170
_refine_ls_restrained_S_all      1.170
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

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
C2 C 0.5144(2) 0.5064(2) 0.7665(4) 0.0134(5) Uani 1 1 d . . . . .
C3 C 0.4695(2) 0.4011(2) 0.7223(4) 0.0135(5) Uani 1 1 d . . . . .
C5 C 0.6270(2) 0.3251(2) 0.8559(4) 0.0131(5) Uani 1 1 d . . . . .
C5N C 0.6860(2) 0.2342(2) 0.9037(4) 0.0140(5) Uani 1 1 d . . . . .
C6 C 0.6688(2) 0.4204(2) 0.8926(4) 0.0128(5) Uani 1 1 d . . . . .
C6N C 0.7710(2) 0.4333(2) 0.9784(5) 0.0188(6) Uani 1 1 d . . . . .
C7 C 0.3722(2) 0.3985(2) 0.6411(4) 0.0144(6) Uani 1 1 d . . . . .
C8 C 0.3194(2) 0.3027(2) 0.5869(4) 0.0115(5) Uani 1 1 d . . . . .
C9 C 0.2126(2) 0.3065(2) 0.4976(4) 0.0142(5) Uani 1 1 d . . . . .
C10 C 0.1616(2) 0.2119(2) 0.4662(4) 0.0149(6) Uani 1 1 d . . . . .
C11 C 0.0603(2) 0.2100(2) 0.3929(4) 0.0177(6) Uani 1 1 d . . . . .
H11 H 0.0259 0.1455 0.3731 0.021 Uiso 1 1 calc R U . . .
C12 C 0.0096(2) 0.3025(3) 0.3489(4) 0.0194(6) Uani 1 1 d . . . . .
H12 H -0.0599 0.3013 0.3008 0.023 Uiso 1 1 calc R U . . .
C13 C 0.0602(2) 0.3968(2) 0.3749(5) 0.0184(6) Uani 1 1 d . . . . .
H13 H 0.0257 0.4598 0.3394 0.022 Uiso 1 1 calc R U . . .
C14 C 0.1612(2) 0.4000(2) 0.4526(4) 0.0168(6) Uani 1 1 d . . . . .
N1 N 0.61232(17) 0.50960(18) 0.8464(4) 0.0134(5) Uani 1 1 d . . . . .
H1 H 0.6410 0.5707 0.8696 0.016 Uiso 1 1 calc R U . . .
N4 N 0.52986(18) 0.31586(18) 0.7691(4) 0.0136(5) Uani 1 1 d . . . . .
N5 N 0.7370(2) 0.1641(2) 0.9488(4) 0.0201(6) Uani 1 1 d . . . . .
N6 N 0.8521(2) 0.4453(2) 1.0434(5) 0.0270(7) Uani 1 1 d . . . . .
O2 O 0.46555(16) 0.58606(16) 0.7329(3) 0.0181(5) Uani 1 1 d . . . . .
O8 O 0.36379(16) 0.21749(16) 0.6146(3) 0.0154(4) Uani 1 1 d . . . . .
H4 H 0.501(3) 0.256(3) 0.753(5) 0.015(9) Uiso 1 1 d . . . . .
H7 H 0.343(3) 0.463(3) 0.617(6) 0.021(10) Uiso 1 1 d . . . . .
H10 H 0.201(4) 0.151(4) 0.504(7) 0.038(12) Uiso 1 1 d . . . . .
H14 H 0.193(3) 0.457(4) 0.469(7) 0.035(12) Uiso 1 1 d . . . . .


_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
C2 O2 1.221(3) . ?
C2 N1 1.363(3) . ?
C2 C3 1.498(4) . ?
C3 C7 1.358(4) . ?
C3 N4 1.376(3) . ?
C5 C6 1.358(4) . ?
C5 N4 1.375(4) . ?
C5 C5N 1.426(4) . ?
C5N N5 1.152(4) . ?
C6 N1 1.389(3) . ?
C6 C6N 1.436(4) . ?
C6N N6 1.137(4) . ?
C7 C8 1.448(4) . ?
C7 H7 0.93(4) . ?
C8 O8 1.248(3) . ?
C8 C9 1.492(4) . ?
C9 C10 1.396(4) . ?
C9 C14 1.401(4) . ?
C10 C11 1.391(4) . ?
C10 H10 0.96(5) . ?
C11 C12 1.384(4) . ?
C11 H11 0.9500 . ?
C12 C13 1.388(4) . ?
C12 H12 0.9500 . ?
C13 C14 1.395(4) . ?
C13 H13 0.9500 . ?
C14 H14 0.84(5) . ?
N1 H1 0.8800 . ?
N4 H4 0.86(4) . ?

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
O2 C2 N1 121.3(3) . . ?
O2 C2 C3 121.6(2) . . ?
N1 C2 C3 117.1(2) . . ?
C7 C3 N4 125.9(3) . . ?
C7 C3 C2 116.8(2) . . ?
N4 C3 C2 117.3(2) . . ?
C6 C5 N4 120.6(2) . . ?
C6 C5 C5N 119.3(2) . . ?
N4 C5 C5N 120.1(3) . . ?
N5 C5N C5 176.3(3) . . ?
C5 C6 N1 119.9(2) . . ?
C5 C6 C6N 122.2(3) . . ?
N1 C6 C6N 117.9(2) . . ?
N6 C6N C6 178.4(3) . . ?
C3 C7 C8 123.1(3) . . ?
C3 C7 H7 115(2) . . ?
C8 C7 H7 122(2) . . ?
O8 C8 C7 119.7(2) . . ?
O8 C8 C9 120.5(2) . . ?
C7 C8 C9 119.8(2) . . ?
C10 C9 C14 119.5(3) . . ?
C10 C9 C8 117.5(2) . . ?
C14 C9 C8 122.9(3) . . ?
C11 C10 C9 120.5(3) . . ?
C11 C10 H10 124(3) . . ?
C9 C10 H10 115(3) . . ?
C12 C11 C10 119.8(3) . . ?
C12 C11 H11 120.1 . . ?
C10 C11 H11 120.1 . . ?
C11 C12 C13 120.2(3) . . ?
C11 C12 H12 119.9 . . ?
C13 C12 H12 119.9 . . ?
C12 C13 C14 120.6(3) . . ?
C12 C13 H13 119.7 . . ?
C14 C13 H13 119.7 . . ?
C13 C14 C9 119.3(3) . . ?
C13 C14 H14 122(3) . . ?
C9 C14 H14 119(3) . . ?
C2 N1 C6 122.7(2) . . ?
C2 N1 H1 118.6 . . ?
C6 N1 H1 118.6 . . ?
C5 N4 C3 122.3(2) . . ?
C5 N4 H4 121(3) . . ?
C3 N4 H4 116(3) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O2 C2 C3 C7 0.8(4) . . . . ?
N1 C2 C3 C7 -179.4(3) . . . . ?
O2 C2 C3 N4 -178.7(3) . . . . ?
N1 C2 C3 N4 1.2(4) . . . . ?
N4 C5 C6 N1 1.5(4) . . . . ?
C5N C5 C6 N1 179.9(3) . . . . ?
N4 C5 C6 C6N -178.3(3) . . . . ?
C5N C5 C6 C6N 0.0(4) . . . . ?
N4 C3 C7 C8 -1.9(5) . . . . ?
C2 C3 C7 C8 178.8(3) . . . . ?
C3 C7 C8 O8 -0.1(5) . . . . ?
C3 C7 C8 C9 -179.8(3) . . . . ?
O8 C8 C9 C10 6.6(4) . . . . ?
C7 C8 C9 C10 -173.7(3) . . . . ?
O8 C8 C9 C14 -176.1(3) . . . . ?
C7 C8 C9 C14 3.6(4) . . . . ?
C14 C9 C10 C11 -0.7(5) . . . . ?
C8 C9 C10 C11 176.6(3) . . . . ?
C9 C10 C11 C12 0.6(5) . . . . ?
C10 C11 C12 C13 1.0(5) . . . . ?
C11 C12 C13 C14 -2.5(5) . . . . ?
C12 C13 C14 C9 2.4(5) . . . . ?
C10 C9 C14 C13 -0.8(5) . . . . ?
C8 C9 C14 C13 -178.0(3) . . . . ?
O2 C2 N1 C6 177.7(3) . . . . ?
C3 C2 N1 C6 -2.1(4) . . . . ?
C5 C6 N1 C2 0.9(4) . . . . ?
C6N C6 N1 C2 -179.3(3) . . . . ?
C6 C5 N4 C3 -2.5(4) . . . . ?
C5N C5 N4 C3 179.2(3) . . . . ?
C7 C3 N4 C5 -178.3(3) . . . . ?
C2 C3 N4 C5 1.1(4) . . . . ?

_refine_diff_density_max         0.520
_refine_diff_density_min         -0.497
_refine_diff_density_rms         0.095


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: acetic acid'
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_shelx_CCDC1
_database_code_depnum_ccdc_archive 'CCDC 2373970'
loop_
_audit_author_name
_audit_author_address
'Aidar Gubaidullin'
;Arbuzov Institute of Organic and Physical Chemistry of RAS
Russia
;
_audit_update_record             
;
2024-07-27 deposited with the CCDC.	2025-01-09 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        
5,8-Diamino-5?-phenyl-1,4?-dihydrospiro[pyrazino[2,3-d]pyridazine-2,3?-pyrazol]-3(4H)-one
_chemical_name_common            ?
_chemical_melting_point          468-469
_chemical_formula_moiety         'C14 H14 N8 O, 2(C3 H7 N O)'
_chemical_formula_sum            'C20 H28 N10 O3'
_chemical_formula_weight         456.52

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 '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 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_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.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   13.4925(9)
_cell_length_b                   8.4402(5)
_cell_length_c                   20.7218(14)
_cell_angle_alpha                90
_cell_angle_beta                 103.011(3)
_cell_angle_gamma                90
_cell_volume                     2299.2(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    9911
_cell_measurement_theta_min      2.62
_cell_measurement_theta_max      29.13
_exptl_crystal_description       plate
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.319
_exptl_crystal_F_000             968
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.332
_exptl_crystal_size_mid          0.208
_exptl_crystal_size_min          0.024
_exptl_absorpt_coefficient_mu    0.094
_shelx_estimated_absorpt_T_min   0.969
_shelx_estimated_absorpt_T_max   0.998
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5260
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_process_details   
;
 G.M. Sheldrick (1998a). SADABS v.2.01, Bruker.
 Siemens Area Detector Absorption Correction Program.
 Bruker AXS. Madison. Wisconsin. USA
  Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D.,
  SADABS-2016/2, J. Appl. Cryst. 48 (2015) 3-10. 
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'microfocus I\mS DIAMOND Mo X-ray tube'
_diffrn_radiation_monochromator  'multilayer optics'
_diffrn_detector                 'area detector PHOTON III'
_diffrn_measurement_device_type  'Bruker D8 QUEST'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            23075
_diffrn_reflns_av_unetI/netI     0.1199
_diffrn_reflns_av_R_equivalents  0.1015
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_theta_min         2.030
_diffrn_reflns_theta_max         29.170
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.975
_diffrn_measured_fraction_theta_full 0.970
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_Laue_measured_fraction_full 0.970
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_point_group_measured_fraction_full 0.970
_reflns_number_total             6059
_reflns_number_gt                4120
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _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.
;

_computing_data_collection       'APEX3 v2019.11-0 (Bruker AXS)'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0243P)²+7.1136P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         6059
_refine_ls_number_parameters     331
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1777
_refine_ls_R_factor_gt           0.1221
_refine_ls_wR_factor_ref         0.2222
_refine_ls_wR_factor_gt          0.2046
_refine_ls_goodness_of_fit_ref   1.173
_refine_ls_restrained_S_all      1.173
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

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
O1S O 0.1066(3) 0.2823(6) 0.45006(18) 0.0607(12) Uani 1 1 d . . . . .
O3 O 0.4849(2) 0.1352(3) 0.56934(12) 0.0213(6) Uani 1 1 d . . . . .
O4S O 0.3330(2) 0.7847(3) 0.49922(15) 0.0297(7) Uani 1 1 d . . . . .
N1 N 0.3614(2) 0.4582(3) 0.47460(14) 0.0135(6) Uani 1 1 d . . . . .
N1S N 0.0625(3) 0.1912(5) 0.34519(19) 0.0353(9) Uani 1 1 d . . . . .
N4 N 0.4066(2) 0.1488(4) 0.46158(14) 0.0155(6) Uani 1 1 d . . . . .
N5 N 0.3384(3) 0.0016(4) 0.33433(16) 0.0206(7) Uani 1 1 d . . . . .
N4S N 0.1961(3) 0.8436(4) 0.5412(2) 0.0379(10) Uani 1 1 d . . . . .
N6 N 0.2743(2) 0.2418(3) 0.29114(15) 0.0165(7) Uani 1 1 d . . . . .
N7 N 0.2540(2) 0.3985(3) 0.29820(15) 0.0178(7) Uani 1 1 d . . . . .
N8 N 0.2557(3) 0.6293(3) 0.35703(18) 0.0198(7) Uani 1 1 d . . . . .
N21 N 0.2708(2) 0.4302(3) 0.60536(14) 0.0144(6) Uani 1 1 d . . . . .
N22 N 0.2851(2) 0.3216(3) 0.55726(14) 0.0132(6) Uani 1 1 d . . . . .
C2 C 0.3784(2) 0.3633(4) 0.53430(16) 0.0110(7) Uani 1 1 d . . . . .
C1S C 0.0762(3) 0.3010(6) 0.3908(2) 0.0393(12) Uani 1 1 d . . . . .
H1S H 0.0606 0.4066 0.3761 0.047 Uiso 1 1 calc R U . . .
C3 C 0.4299(3) 0.2068(4) 0.52358(16) 0.0131(7) Uani 1 1 d . . . . .
C2S C 0.0888(4) 0.0276(7) 0.3627(3) 0.0591(16) Uani 1 1 d . . . . .
H21S H 0.0265 -0.0355 0.3575 0.089 Uiso 1 1 calc R U . . .
H22S H 0.1272 0.0222 0.4088 0.089 Uiso 1 1 calc R U . . .
H23S H 0.1305 -0.0145 0.3335 0.089 Uiso 1 1 calc R U . . .
C3S C 0.0223(4) 0.2254(7) 0.2759(3) 0.0498(14) Uani 1 1 d . . . . .
H31S H 0.0698 0.1872 0.2499 0.075 Uiso 1 1 calc R U . . .
H32S H 0.0132 0.3401 0.2698 0.075 Uiso 1 1 calc R U . . .
H33S H -0.0435 0.1722 0.2609 0.075 Uiso 1 1 calc R U . . .
C5 C 0.3222(3) 0.1603(4) 0.34326(17) 0.0147(7) Uani 1 1 d . . . . .
C4A C 0.3524(3) 0.2320(4) 0.40634(17) 0.0127(7) Uani 1 1 d . . . . .
C4S C 0.2903(4) 0.8617(5) 0.5355(2) 0.0307(10) Uani 1 1 d . . . . .
H4S H 0.3291 0.9420 0.5618 0.037 Uiso 1 1 calc R U . . .
C5S C 0.1303(4) 0.7214(6) 0.5028(3) 0.0482(13) Uani 1 1 d . . . . .
H51S H 0.0607 0.7620 0.4891 0.072 Uiso 1 1 calc R U . . .
H52S H 0.1307 0.6267 0.5302 0.072 Uiso 1 1 calc R U . . .
H53S H 0.1557 0.6940 0.4635 0.072 Uiso 1 1 calc R U . . .
C6S C 0.1527(5) 0.9409(7) 0.5860(3) 0.0650(18) Uani 1 1 d . . . . .
H61S H 0.0948 1.0009 0.5605 0.098 Uiso 1 1 calc R U . . .
H62S H 0.2044 1.0147 0.6097 0.098 Uiso 1 1 calc R U . . .
H63S H 0.1297 0.8727 0.6181 0.098 Uiso 1 1 calc R U . . .
C8 C 0.2811(3) 0.4708(4) 0.35563(18) 0.0147(7) Uani 1 1 d . . . . .
C8A C 0.3298(2) 0.3881(4) 0.41384(16) 0.0106(7) Uani 1 1 d . . . . .
C24 C 0.4377(3) 0.4586(4) 0.59352(16) 0.0151(7) Uani 1 1 d . . . . .
H241 H 0.4906 0.3931 0.6223 0.018 Uiso 1 1 calc R U . . .
H242 H 0.4698 0.5536 0.5789 0.018 Uiso 1 1 calc R U . . .
C25 C 0.3550(3) 0.5032(4) 0.62797(16) 0.0125(7) Uani 1 1 d . . . . .
C26 C 0.3690(3) 0.6147(4) 0.68359(17) 0.0159(7) Uani 1 1 d . . . . .
C27 C 0.2920(3) 0.6411(5) 0.7174(2) 0.0244(9) Uani 1 1 d . . . . .
H27 H 0.2280 0.5905 0.7025 0.029 Uiso 1 1 calc R U . . .
C28 C 0.3068(3) 0.7395(5) 0.7721(2) 0.0277(9) Uani 1 1 d . . . . .
H28 H 0.2540 0.7548 0.7951 0.033 Uiso 1 1 calc R U . . .
C29 C 0.4007(3) 0.8163(5) 0.7933(2) 0.0309(10) Uani 1 1 d . . . . .
H29 H 0.4120 0.8837 0.8309 0.037 Uiso 1 1 calc R U . . .
C30 C 0.4763(3) 0.7940(5) 0.7595(2) 0.0320(10) Uani 1 1 d . . . . .
H30 H 0.5393 0.8480 0.7734 0.038 Uiso 1 1 calc R U . . .
C31 C 0.4614(3) 0.6939(5) 0.70543(19) 0.0215(8) Uani 1 1 d . . . . .
H31 H 0.5146 0.6786 0.6828 0.026 Uiso 1 1 calc R U . . .
H1 H 0.347(3) 0.548(5) 0.4814(19) 0.012(10) Uiso 1 1 d . . . . .
H4 H 0.427(4) 0.058(6) 0.457(2) 0.042(15) Uiso 1 1 d . . . . .
H22 H 0.230(3) 0.321(4) 0.5226(19) 0.013(9) Uiso 1 1 d . . . . .
H51 H 0.317(3) -0.024(4) 0.2945(19) 0.006(9) Uiso 1 1 d . . . . .
H52 H 0.398(3) -0.038(4) 0.3615(18) 0.010(9) Uiso 1 1 d . . . . .
H81 H 0.298(3) 0.680(5) 0.395(2) 0.017(10) Uiso 1 1 d . . . . .
H82 H 0.246(3) 0.670(5) 0.323(2) 0.014(11) Uiso 1 1 d . . . . .


_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
O1S C1S 1.214(6) . ?
O3 C3 1.224(4) . ?
O4S C4S 1.231(5) . ?
N1 C8A 1.369(4) . ?
N1 C2 1.448(4) . ?
N1 H1 0.80(4) . ?
N1S C1S 1.307(6) . ?
N1S C3S 1.445(6) . ?
N1S C2S 1.452(7) . ?
N4 C3 1.344(4) . ?
N4 C4A 1.400(4) . ?
N4 H4 0.83(5) . ?
N5 C5 1.376(4) . ?
N5 H51 0.84(4) . ?
N5 H52 0.93(4) . ?
N4S C4S 1.312(6) . ?
N4S C6S 1.458(6) . ?
N4S C5S 1.472(7) . ?
N6 C5 1.320(4) . ?
N6 N7 1.365(4) . ?
N7 C8 1.314(5) . ?
N8 C8 1.383(4) . ?
N8 H81 0.96(4) . ?
N8 H82 0.76(4) . ?
N21 C25 1.284(4) . ?
N21 N22 1.399(4) . ?
N22 C2 1.484(4) . ?
N22 H22 0.91(4) . ?
C2 C3 1.532(5) . ?
C2 C24 1.533(4) . ?
C1S H1S 0.9500 . ?
C2S H21S 0.9800 . ?
C2S H22S 0.9800 . ?
C2S H23S 0.9800 . ?
C3S H31S 0.9800 . ?
C3S H32S 0.9800 . ?
C3S H33S 0.9800 . ?
C5 C4A 1.415(5) . ?
C4A C8A 1.369(4) . ?
C4S H4S 0.9500 . ?
C5S H51S 0.9800 . ?
C5S H52S 0.9800 . ?
C5S H53S 0.9800 . ?
C6S H61S 0.9800 . ?
C6S H62S 0.9800 . ?
C6S H63S 0.9800 . ?
C8 C8A 1.420(5) . ?
C24 C25 1.501(5) . ?
C24 H241 0.9900 . ?
C24 H242 0.9900 . ?
C25 C26 1.467(5) . ?
C26 C27 1.396(5) . ?
C26 C31 1.397(5) . ?
C27 C28 1.383(5) . ?
C27 H27 0.9500 . ?
C28 C29 1.403(6) . ?
C28 H28 0.9500 . ?
C29 C30 1.374(6) . ?
C29 H29 0.9500 . ?
C30 C31 1.381(6) . ?
C30 H30 0.9500 . ?
C31 H31 0.9500 . ?

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
C8A N1 C2 120.2(3) . . ?
C8A N1 H1 122(3) . . ?
C2 N1 H1 112(3) . . ?
C1S N1S C3S 122.5(5) . . ?
C1S N1S C2S 120.5(5) . . ?
C3S N1S C2S 117.0(4) . . ?
C3 N4 C4A 124.4(3) . . ?
C3 N4 H4 116(3) . . ?
C4A N4 H4 120(3) . . ?
C5 N5 H51 111(2) . . ?
C5 N5 H52 114(2) . . ?
H51 N5 H52 124(3) . . ?
C4S N4S C6S 121.9(5) . . ?
C4S N4S C5S 120.7(4) . . ?
C6S N4S C5S 117.4(4) . . ?
C5 N6 N7 119.4(3) . . ?
C8 N7 N6 121.7(3) . . ?
C8 N8 H81 110(2) . . ?
C8 N8 H82 114(3) . . ?
H81 N8 H82 120(4) . . ?
C25 N21 N22 108.7(3) . . ?
N21 N22 C2 109.6(3) . . ?
N21 N22 H22 110(2) . . ?
C2 N22 H22 110(2) . . ?
N1 C2 N22 115.0(3) . . ?
N1 C2 C3 110.1(3) . . ?
N22 C2 C3 106.7(3) . . ?
N1 C2 C24 110.3(3) . . ?
N22 C2 C24 101.2(3) . . ?
C3 C2 C24 113.4(3) . . ?
O1S C1S N1S 126.9(5) . . ?
O1S C1S H1S 116.6 . . ?
N1S C1S H1S 116.6 . . ?
O3 C3 N4 122.1(3) . . ?
O3 C3 C2 121.9(3) . . ?
N4 C3 C2 115.9(3) . . ?
N1S C2S H21S 109.5 . . ?
N1S C2S H22S 109.5 . . ?
H21S C2S H22S 109.5 . . ?
N1S C2S H23S 109.5 . . ?
H21S C2S H23S 109.5 . . ?
H22S C2S H23S 109.5 . . ?
N1S C3S H31S 109.5 . . ?
N1S C3S H32S 109.5 . . ?
H31S C3S H32S 109.5 . . ?
N1S C3S H33S 109.5 . . ?
H31S C3S H33S 109.5 . . ?
H32S C3S H33S 109.5 . . ?
N6 C5 N5 117.4(3) . . ?
N6 C5 C4A 121.3(3) . . ?
N5 C5 C4A 121.3(3) . . ?
C8A C4A N4 118.6(3) . . ?
C8A C4A C5 119.4(3) . . ?
N4 C4A C5 122.0(3) . . ?
O4S C4S N4S 126.2(4) . . ?
O4S C4S H4S 116.9 . . ?
N4S C4S H4S 116.9 . . ?
N4S C5S H51S 109.5 . . ?
N4S C5S H52S 109.5 . . ?
H51S C5S H52S 109.5 . . ?
N4S C5S H53S 109.5 . . ?
H51S C5S H53S 109.5 . . ?
H52S C5S H53S 109.5 . . ?
N4S C6S H61S 109.5 . . ?
N4S C6S H62S 109.5 . . ?
H61S C6S H62S 109.5 . . ?
N4S C6S H63S 109.5 . . ?
H61S C6S H63S 109.5 . . ?
H62S C6S H63S 109.5 . . ?
N7 C8 N8 116.6(3) . . ?
N7 C8 C8A 121.5(3) . . ?
N8 C8 C8A 121.8(3) . . ?
C4A C8A N1 119.3(3) . . ?
C4A C8A C8 116.7(3) . . ?
N1 C8A C8 123.9(3) . . ?
C25 C24 C2 101.7(3) . . ?
C25 C24 H241 111.4 . . ?
C2 C24 H241 111.4 . . ?
C25 C24 H242 111.4 . . ?
C2 C24 H242 111.4 . . ?
H241 C24 H242 109.3 . . ?
N21 C25 C26 122.7(3) . . ?
N21 C25 C24 113.4(3) . . ?
C26 C25 C24 123.8(3) . . ?
C27 C26 C31 118.2(3) . . ?
C27 C26 C25 121.2(3) . . ?
C31 C26 C25 120.6(3) . . ?
C28 C27 C26 121.4(4) . . ?
C28 C27 H27 119.3 . . ?
C26 C27 H27 119.3 . . ?
C27 C28 C29 119.1(4) . . ?
C27 C28 H28 120.4 . . ?
C29 C28 H28 120.4 . . ?
C30 C29 C28 120.0(4) . . ?
C30 C29 H29 120.0 . . ?
C28 C29 H29 120.0 . . ?
C29 C30 C31 120.5(4) . . ?
C29 C30 H30 119.8 . . ?
C31 C30 H30 119.8 . . ?
C30 C31 C26 120.8(4) . . ?
C30 C31 H31 119.6 . . ?
C26 C31 H31 119.6 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C5 N6 N7 C8 0.2(5) . . . . ?
C25 N21 N22 C2 -17.9(4) . . . . ?
C8A N1 C2 N22 -80.4(4) . . . . ?
C8A N1 C2 C3 40.1(4) . . . . ?
C8A N1 C2 C24 165.9(3) . . . . ?
N21 N22 C2 N1 -95.6(3) . . . . ?
N21 N22 C2 C3 142.1(3) . . . . ?
N21 N22 C2 C24 23.3(3) . . . . ?
C3S N1S C1S O1S 177.7(5) . . . . ?
C2S N1S C1S O1S -3.0(7) . . . . ?
C4A N4 C3 O3 -173.6(3) . . . . ?
C4A N4 C3 C2 9.9(5) . . . . ?
N1 C2 C3 O3 152.3(3) . . . . ?
N22 C2 C3 O3 -82.4(4) . . . . ?
C24 C2 C3 O3 28.2(5) . . . . ?
N1 C2 C3 N4 -31.2(4) . . . . ?
N22 C2 C3 N4 94.2(3) . . . . ?
C24 C2 C3 N4 -155.3(3) . . . . ?
N7 N6 C5 N5 178.1(3) . . . . ?
N7 N6 C5 C4A 0.3(5) . . . . ?
C3 N4 C4A C8A 6.8(5) . . . . ?
C3 N4 C4A C5 -174.3(3) . . . . ?
N6 C5 C4A C8A 1.3(5) . . . . ?
N5 C5 C4A C8A -176.4(3) . . . . ?
N6 C5 C4A N4 -177.5(3) . . . . ?
N5 C5 C4A N4 4.8(5) . . . . ?
C6S N4S C4S O4S 179.7(5) . . . . ?
C5S N4S C4S O4S 0.4(7) . . . . ?
N6 N7 C8 N8 -179.4(3) . . . . ?
N6 N7 C8 C8A -2.3(5) . . . . ?
N4 C4A C8A N1 0.5(5) . . . . ?
C5 C4A C8A N1 -178.4(3) . . . . ?
N4 C4A C8A C8 175.7(3) . . . . ?
C5 C4A C8A C8 -3.2(5) . . . . ?
C2 N1 C8A C4A -25.9(5) . . . . ?
C2 N1 C8A C8 159.3(3) . . . . ?
N7 C8 C8A C4A 3.8(5) . . . . ?
N8 C8 C8A C4A -179.2(3) . . . . ?
N7 C8 C8A N1 178.7(3) . . . . ?
N8 C8 C8A N1 -4.3(5) . . . . ?
N1 C2 C24 C25 102.9(3) . . . . ?
N22 C2 C24 C25 -19.3(3) . . . . ?
C3 C2 C24 C25 -133.1(3) . . . . ?
N22 N21 C25 C26 -174.1(3) . . . . ?
N22 N21 C25 C24 3.9(4) . . . . ?
C2 C24 C25 N21 10.7(4) . . . . ?
C2 C24 C25 C26 -171.3(3) . . . . ?
N21 C25 C26 C27 3.5(5) . . . . ?
C24 C25 C26 C27 -174.4(3) . . . . ?
N21 C25 C26 C31 -178.5(3) . . . . ?
C24 C25 C26 C31 3.6(5) . . . . ?
C31 C26 C27 C28 -1.7(6) . . . . ?
C25 C26 C27 C28 176.4(4) . . . . ?
C26 C27 C28 C29 1.2(6) . . . . ?
C27 C28 C29 C30 0.4(7) . . . . ?
C28 C29 C30 C31 -1.3(7) . . . . ?
C29 C30 C31 C26 0.8(7) . . . . ?
C27 C26 C31 C30 0.7(6) . . . . ?
C25 C26 C31 C30 -177.3(4) . . . . ?

_refine_diff_density_max         0.458
_refine_diff_density_min         -0.398
_refine_diff_density_rms         0.082


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: acetic acid'
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_shelx_CCDC2
_database_code_depnum_ccdc_archive 'CCDC 2373969'
loop_
_audit_author_name
_audit_author_address
'Aidar Gubaidullin'
;Arbuzov Institute of Organic and Physical Chemistry of RAS
Russia
;
_audit_update_record             
;
2024-07-27 deposited with the CCDC.	2025-01-09 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        
'2-(5-Phenyl-1H-pyrazol-3-yl)-5H-imidazo[4,5-d]pyridazine-4,7-diamine hydrate'
_chemical_name_common            ?
_chemical_melting_point          495-496
_chemical_formula_moiety         '2(C14 H12 N8), 2(C3 H7 N O), H2 O'
_chemical_formula_sum            'C34 H40 N18 O3'
_chemical_formula_weight         748.84

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 '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 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'C 2/c'
_space_group_name_Hall           '-C 2yc'

_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.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y, z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, -y+1/2, z-1/2'

_cell_length_a                   24.826(3)
_cell_length_b                   10.5319(13)
_cell_length_c                   16.192(2)
_cell_angle_alpha                90
_cell_angle_beta                 117.179(4)
_cell_angle_gamma                90
_cell_volume                     3766.2(8)
_cell_formula_units_Z            4
_cell_measurement_temperature    162(2)
_cell_measurement_reflns_used    9966
_cell_measurement_theta_min      2.32
_cell_measurement_theta_max      34.66
_exptl_crystal_description       prism
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.321
_exptl_crystal_F_000             1576
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.263
_exptl_crystal_size_mid          0.201
_exptl_crystal_size_min          0.134
_exptl_absorpt_coefficient_mu    0.092
_shelx_estimated_absorpt_T_min   0.976
_shelx_estimated_absorpt_T_max   0.988
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6888
_exptl_absorpt_correction_T_max  0.7469
_exptl_absorpt_process_details   
;
 G.M. Sheldrick (1998a). SADABS v.2.01, Bruker.
 Siemens Area Detector Absorption Correction Program.
 Bruker AXS. Madison. Wisconsin. USA
  Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D.,
  SADABS-2016/2, J. Appl. Cryst. 48 (2015) 3-10. 
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      162(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'microfocus I\mS DIAMOND Mo X-ray tube'
_diffrn_radiation_monochromator  'multilayer optics'
_diffrn_detector                 'area detector PHOTON III'
_diffrn_measurement_device_type  'Bruker D8 QUEST'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            84574
_diffrn_reflns_av_unetI/netI     0.0348
_diffrn_reflns_av_R_equivalents  0.0695
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_h_max       39
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_theta_min         1.844
_diffrn_reflns_theta_max         34.804
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measured_fraction_theta_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_point_group_measured_fraction_full 0.996
_reflns_number_total             8114
_reflns_number_gt                6405
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _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.
;

_computing_data_collection       'APEX3 v2019.11-0 (Bruker AXS)'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0818P)²+0.6279P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         8114
_refine_ls_number_parameters     329
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0613
_refine_ls_R_factor_gt           0.0484
_refine_ls_wR_factor_ref         0.1438
_refine_ls_wR_factor_gt          0.1318
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_restrained_S_all      1.042
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

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
C1S C 0.38937(5) 0.24396(11) 0.42713(7) 0.0410(2) Uani 1 1 d . . . . .
C2S C 0.42386(9) 0.03486(14) 0.48955(12) 0.0655(4) Uani 1 1 d . . . . .
C3A C 0.30964(3) 0.93001(7) 0.25569(6) 0.02393(14) Uani 1 1 d . . . . .
C3S C 0.32962(9) 0.1227(2) 0.48306(15) 0.0802(6) Uani 1 1 d . . . . .
C4 C 0.25702(3) 0.99753(7) 0.24292(6) 0.02490(14) Uani 1 1 d . . . . .
C7 C 0.34552(3) 1.12000(8) 0.20925(6) 0.02695(15) Uani 1 1 d . . . . .
C7A C 0.35391(3) 0.99125(7) 0.24065(6) 0.02486(14) Uani 1 1 d . . . . .
C23 C 0.42264(3) 0.69348(7) 0.31896(6) 0.02432(14) Uani 1 1 d . . . . .
C24 C 0.48514(3) 0.69091(7) 0.34652(6) 0.02584(15) Uani 1 1 d . . . . .
C25 C 0.50245(3) 0.56644(8) 0.37248(6) 0.02535(14) Uani 1 1 d . . . . .
C26 C 0.56261(3) 0.50791(8) 0.40942(6) 0.02748(15) Uani 1 1 d . . . . .
C27 C 0.57691(4) 0.39570(9) 0.46092(7) 0.03379(18) Uani 1 1 d . . . . .
C28 C 0.63562(5) 0.34754(11) 0.49816(8) 0.0418(2) Uani 1 1 d . . . . .
C29 C 0.67971(4) 0.40848(12) 0.48361(7) 0.0437(2) Uani 1 1 d . . . . .
C30 C 0.66568(4) 0.51855(13) 0.43185(8) 0.0442(2) Uani 1 1 d . . . . .
C31 C 0.60742(4) 0.56912(11) 0.39501(7) 0.0373(2) Uani 1 1 d . . . . .
C2 C 0.38273(3) 0.80369(7) 0.28700(6) 0.02435(14) Uani 1 1 d . . . . .
N1 N 0.40090(3) 0.91044(6) 0.26041(5) 0.02650(14) Uani 1 1 d . . . . .
N1S N 0.38134(5) 0.13812(10) 0.46552(7) 0.0481(2) Uani 1 1 d . . . . .
N3 N 0.32757(3) 0.80837(6) 0.28499(5) 0.02486(13) Uani 1 1 d . . . . .
N4 N 0.21234(3) 0.95132(7) 0.25820(7) 0.03446(18) Uani 1 1 d . . . . .
N5 N 0.25472(3) 1.11846(6) 0.21621(5) 0.02693(14) Uani 1 1 d . . . . .
N6 N 0.29648(3) 1.18224(6) 0.19803(5) 0.02824(14) Uani 1 1 d . . . . .
N7 N 0.38642(4) 1.17884(8) 0.18873(7) 0.0400(2) Uani 1 1 d . . . . .
N21 N 0.45175(3) 0.50304(7) 0.35930(6) 0.02790(14) Uani 1 1 d . . . . .
N22 N 0.40236(3) 0.57859(7) 0.32657(5) 0.02768(14) Uani 1 1 d . . . . .
O1S O 0.43182(4) 0.26247(8) 0.40995(6) 0.04620(19) Uani 1 1 d . . . . .
O2S O 0.5000 0.02170(11) 0.2500 0.0527(3) Uani 1 2 d S T P . .
H1S H 0.3563(8) 0.3115(16) 0.4107(12) 0.060(4) Uiso 1 1 d . . . . .
H2S H 0.5266(8) -0.0216(18) 0.2448(13) 0.071(5) Uiso 1 1 d . . . . .
H5 H 0.2239(6) 1.1711(14) 0.2089(10) 0.047(4) Uiso 1 1 d . . . . .
H21 H 0.4467(7) 0.4213(15) 0.3718(11) 0.049(4) Uiso 1 1 d . . . . .
H21S H 0.4605(10) 0.059(2) 0.4860(15) 0.090(6) Uiso 1 1 d . . . . .
H22S H 0.4091(10) -0.042(2) 0.4599(16) 0.097(7) Uiso 1 1 d . . . . .
H23S H 0.4414(11) 0.016(2) 0.555(2) 0.112(8) Uiso 1 1 d . . . . .
H24 H 0.5112(6) 0.7642(13) 0.3485(9) 0.041(3) Uiso 1 1 d . . . . .
H27 H 0.5449(6) 0.3514(13) 0.4726(9) 0.041(3) Uiso 1 1 d . . . . .
H28 H 0.6449(6) 0.2662(16) 0.5370(11) 0.054(4) Uiso 1 1 d . . . . .
H29 H 0.7217(7) 0.3744(14) 0.5094(11) 0.054(4) Uiso 1 1 d . . . . .
H30 H 0.6975(7) 0.5620(15) 0.4216(12) 0.059(4) Uiso 1 1 d . . . . .
H31 H 0.5974(6) 0.6502(14) 0.3576(10) 0.051(4) Uiso 1 1 d . . . . .
H31S H 0.3406(10) 0.116(2) 0.5498(19) 0.107(7) Uiso 1 1 d . . . . .
H32S H 0.3038(11) 0.048(3) 0.4474(19) 0.115(8) Uiso 1 1 d . . . . .
H33S H 0.3019(9) 0.206(2) 0.4565(17) 0.093(7) Uiso 1 1 d . . . . .
H41 H 0.2117(6) 0.8697(15) 0.2752(10) 0.046(4) Uiso 1 1 d . . . . .
H42 H 0.1785(7) 0.9969(14) 0.2382(11) 0.048(4) Uiso 1 1 d . . . . .
H71 H 0.4219(7) 1.1432(14) 0.2059(10) 0.045(3) Uiso 1 1 d . . . . .
H72 H 0.3824(7) 1.2647(16) 0.1758(11) 0.056(4) Uiso 1 1 d . . . . .


_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
C1S O1S 1.2222(14) . ?
C1S N1S 1.3349(15) . ?
C1S H1S 1.025(17) . ?
C2S N1S 1.440(2) . ?
C2S H21S 0.97(2) . ?
C2S H22S 0.93(2) . ?
C2S H23S 0.97(3) . ?
C3A N3 1.3681(10) . ?
C3A C7A 1.3884(10) . ?
C3A C4 1.4171(10) . ?
C3S N1S 1.4453(19) . ?
C3S H31S 0.99(3) . ?
C3S H32S 1.01(3) . ?
C3S H33S 1.07(2) . ?
C4 N4 1.3338(10) . ?
C4 N5 1.3379(10) . ?
C7 N6 1.3201(10) . ?
C7 N7 1.3541(11) . ?
C7 C7A 1.4296(11) . ?
C7A N1 1.3589(9) . ?
C23 N22 1.3378(10) . ?
C23 C24 1.4054(10) . ?
C23 C2 1.4589(10) . ?
C24 C25 1.3838(11) . ?
C24 H24 0.998(13) . ?
C25 N21 1.3528(10) . ?
C25 C26 1.4670(10) . ?
C26 C31 1.3943(12) . ?
C26 C27 1.3956(13) . ?
C27 C28 1.3938(13) . ?
C27 H27 1.011(13) . ?
C28 C29 1.3789(17) . ?
C28 H28 1.025(16) . ?
C29 C30 1.3787(17) . ?
C29 H29 0.996(15) . ?
C30 C31 1.3941(12) . ?
C30 H30 0.990(16) . ?
C31 H31 1.009(15) . ?
C2 N1 1.3528(10) . ?
C2 N3 1.3558(9) . ?
N4 H41 0.905(15) . ?
N4 H42 0.890(15) . ?
N5 N6 1.3754(9) . ?
N5 H5 0.909(14) . ?
N7 H71 0.877(14) . ?
N7 H72 0.923(17) . ?
N21 N22 1.3505(9) . ?
N21 H21 0.906(15) . ?
O2S H2S 0.839(17) . ?

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
O1S C1S N1S 124.53(11) . . ?
O1S C1S H1S 120.1(9) . . ?
N1S C1S H1S 115.4(9) . . ?
N1S C2S H21S 112.1(13) . . ?
N1S C2S H22S 116.9(14) . . ?
H21S C2S H22S 111.1(18) . . ?
N1S C2S H23S 110.8(15) . . ?
H21S C2S H23S 98.9(17) . . ?
H22S C2S H23S 105(2) . . ?
N3 C3A C7A 109.73(6) . . ?
N3 C3A C4 130.75(7) . . ?
C7A C3A C4 119.48(7) . . ?
N1S C3S H31S 113.4(13) . . ?
N1S C3S H32S 111.3(14) . . ?
H31S C3S H32S 111(2) . . ?
N1S C3S H33S 107.1(12) . . ?
H31S C3S H33S 107.4(18) . . ?
H32S C3S H33S 106.3(19) . . ?
N4 C4 N5 119.41(7) . . ?
N4 C4 C3A 125.39(7) . . ?
N5 C4 C3A 115.16(7) . . ?
N6 C7 N7 119.12(8) . . ?
N6 C7 C7A 119.69(7) . . ?
N7 C7 C7A 121.17(7) . . ?
N1 C7A C3A 109.32(7) . . ?
N1 C7A C7 130.37(7) . . ?
C3A C7A C7 120.30(7) . . ?
N22 C23 C24 111.14(6) . . ?
N22 C23 C2 121.95(6) . . ?
C24 C23 C2 126.90(7) . . ?
C25 C24 C23 105.03(7) . . ?
C25 C24 H24 128.1(7) . . ?
C23 C24 H24 126.9(7) . . ?
N21 C25 C24 106.39(6) . . ?
N21 C25 C26 123.88(7) . . ?
C24 C25 C26 129.72(7) . . ?
C31 C26 C27 119.14(7) . . ?
C31 C26 C25 118.61(8) . . ?
C27 C26 C25 122.21(8) . . ?
C28 C27 C26 119.79(9) . . ?
C28 C27 H27 120.5(8) . . ?
C26 C27 H27 119.7(8) . . ?
C29 C28 C27 120.78(10) . . ?
C29 C28 H28 121.4(8) . . ?
C27 C28 H28 117.8(8) . . ?
C30 C29 C28 119.69(8) . . ?
C30 C29 H29 118.9(9) . . ?
C28 C29 H29 121.4(9) . . ?
C29 C30 C31 120.40(10) . . ?
C29 C30 H30 119.4(10) . . ?
C31 C30 H30 120.2(10) . . ?
C30 C31 C26 120.19(10) . . ?
C30 C31 H31 120.2(8) . . ?
C26 C31 H31 119.6(8) . . ?
N1 C2 N3 116.23(6) . . ?
N1 C2 C23 120.20(6) . . ?
N3 C2 C23 123.52(7) . . ?
C2 N1 C7A 102.73(6) . . ?
C1S N1S C2S 120.64(12) . . ?
C1S N1S C3S 121.35(14) . . ?
C2S N1S C3S 118.01(15) . . ?
C2 N3 C3A 101.97(6) . . ?
C4 N4 H41 122.3(9) . . ?
C4 N4 H42 117.5(9) . . ?
H41 N4 H42 118.7(12) . . ?
C4 N5 N6 127.53(6) . . ?
C4 N5 H5 122.2(9) . . ?
N6 N5 H5 110.3(9) . . ?
C7 N6 N5 117.77(7) . . ?
C7 N7 H71 118.9(9) . . ?
C7 N7 H72 119.2(9) . . ?
H71 N7 H72 118.7(13) . . ?
N22 N21 C25 112.56(7) . . ?
N22 N21 H21 117.0(9) . . ?
C25 N21 H21 130.3(9) . . ?
C23 N22 N21 104.87(6) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N3 C3A C4 N4 -0.05(15) . . . . ?
C7A C3A C4 N4 -177.47(9) . . . . ?
N3 C3A C4 N5 177.67(8) . . . . ?
C7A C3A C4 N5 0.25(12) . . . . ?
N3 C3A C7A N1 -0.29(10) . . . . ?
C4 C3A C7A N1 177.63(7) . . . . ?
N3 C3A C7A C7 179.80(7) . . . . ?
C4 C3A C7A C7 -2.28(12) . . . . ?
N6 C7 C7A N1 -177.26(9) . . . . ?
N7 C7 C7A N1 4.22(15) . . . . ?
N6 C7 C7A C3A 2.63(13) . . . . ?
N7 C7 C7A C3A -175.89(9) . . . . ?
N22 C23 C24 C25 -0.41(10) . . . . ?
C2 C23 C24 C25 178.69(8) . . . . ?
C23 C24 C25 N21 0.35(9) . . . . ?
C23 C24 C25 C26 -178.34(8) . . . . ?
N21 C25 C26 C31 161.38(9) . . . . ?
C24 C25 C26 C31 -20.13(14) . . . . ?
N21 C25 C26 C27 -20.82(14) . . . . ?
C24 C25 C26 C27 157.67(9) . . . . ?
C31 C26 C27 C28 0.89(14) . . . . ?
C25 C26 C27 C28 -176.90(9) . . . . ?
C26 C27 C28 C29 -0.95(16) . . . . ?
C27 C28 C29 C30 0.18(17) . . . . ?
C28 C29 C30 C31 0.65(18) . . . . ?
C29 C30 C31 C26 -0.70(18) . . . . ?
C27 C26 C31 C30 -0.08(15) . . . . ?
C25 C26 C31 C30 177.80(10) . . . . ?
N22 C23 C2 N1 -165.22(8) . . . . ?
C24 C23 C2 N1 15.76(13) . . . . ?
N22 C23 C2 N3 17.21(13) . . . . ?
C24 C23 C2 N3 -161.81(8) . . . . ?
N3 C2 N1 C7A 0.75(10) . . . . ?
C23 C2 N1 C7A -176.99(7) . . . . ?
C3A C7A N1 C2 -0.25(9) . . . . ?
C7 C7A N1 C2 179.65(9) . . . . ?
O1S C1S N1S C2S -0.34(19) . . . . ?
O1S C1S N1S C3S -179.47(13) . . . . ?
N1 C2 N3 C3A -0.92(10) . . . . ?
C23 C2 N3 C3A 176.74(8) . . . . ?
C7A C3A N3 C2 0.69(9) . . . . ?
C4 C3A N3 C2 -176.93(9) . . . . ?
N4 C4 N5 N6 179.51(8) . . . . ?
C3A C4 N5 N6 1.64(13) . . . . ?
N7 C7 N6 N5 177.67(8) . . . . ?
C7A C7 N6 N5 -0.88(12) . . . . ?
C4 N5 N6 C7 -1.33(13) . . . . ?
C24 C25 N21 N22 -0.20(10) . . . . ?
C26 C25 N21 N22 178.59(8) . . . . ?
C24 C23 N22 N21 0.29(10) . . . . ?
C2 C23 N22 N21 -178.86(8) . . . . ?
C25 N21 N22 C23 -0.06(10) . . . . ?

_refine_diff_density_max         0.473
_refine_diff_density_min         -0.242
_refine_diff_density_rms         0.051


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: acetic acid'
