# Electronic Supplementary Material (ESI) for Chemical Science.
# This journal is © The Royal Society of Chemistry 2021

####################################################################### 
# 
# 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_1_100K
_database_code_depnum_ccdc_archive 'CCDC 2047425'
loop_
_audit_author_name
_audit_author_address
'Nicholas White'
;Australian National University
Australia
;
_audit_update_record             
;
2020-12-01 deposited with the CCDC.	2021-01-13 downloaded from the CCDC.
;
#==============================================================================
# start Validation Reply Form
_vrf_PLAT029_1_100K              
;
PROBLEM: _diffrn_measured_fraction_theta_full value Low .      0.829 Why?  
RESPONSE: Low data completion ratio is due to the limitations of the instrument
available at the Australian Synchrotron operating under rotation data 
collection with a fixed detector and affects some high angle data. This is 
compounded by the triclinic space group and the weakly-diffracting crystals.
;

_exptl_special_details           
; 
 The crystal was 
placed in the cold stream of an Oxford 
Cryosystems open-flow nitrogen cryostat (Cosier & 
Glazer, 1986) with a nominal stability of 0.1K. 
 
Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107. 
;

_refine_special_details          
; 
Hydrogen atoms were  visible in the Fourier difference 
map and were initially refined with restraints on bond lengths and angles, 
after which the positions were used as the basis for a riding model.  The N-H 
hydrogen atoms were refined with restraints on bond lengths and angles. 

Apart from the restraints on N-H bond length and C-N-H bond angle, it was not 
necessary to use any crystallographic restraints during the refinement.

The room temperature collection of this crystal is of higher quality, however
this collection (100 K) is included for completeness.
;

_cell_length_a                   6.9310(14)
_cell_length_b                   7.5900(15)
_cell_length_c                   7.7350(15)
_cell_angle_alpha                60.94(3)
_cell_angle_beta                 82.44(3)
_cell_angle_gamma                75.12(3)
_cell_volume                     343.73(16)

_symmetry_cell_setting           triclinic
_symmetry_space_group_name_H-M   'P -1 '
_symmetry_space_group_name_Hall  '-P 1'

loop_
_symmetry_equiv_pos_as_xyz
x,y,z
-x,-y,-z

loop_
_atom_type_symbol
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_Cromer_Mann_a1
_atom_type_scat_Cromer_Mann_b1
_atom_type_scat_Cromer_Mann_a2
_atom_type_scat_Cromer_Mann_b2
_atom_type_scat_Cromer_Mann_a3
_atom_type_scat_Cromer_Mann_b3
_atom_type_scat_Cromer_Mann_a4
_atom_type_scat_Cromer_Mann_b4
_atom_type_scat_Cromer_Mann_c
_atom_type_scat_source
C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512
0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998
0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
N 0.0061 0.0033 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826
-11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
O 0.0106 0.0060 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089
0.2508 'International Tables Vol C 4.2.6.8 and 6.1.1.4'

_cell_formula_units_Z            2

_chemical_formula_sum            'C8 H8 N2 O2'
_chemical_formula_moiety         'C8 H8 N2 O2'
_chemical_compound_source        synthesized
_chemical_formula_weight         164.16


_cell_measurement_reflns_used    3285
_cell_measurement_theta_min      3.01
_cell_measurement_theta_max      31.9
_cell_measurement_temperature    100

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_size_min          0.01
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_max          0.01

_exptl_crystal_density_diffrn    1.586
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_density_method    'not measured'
# Non-dispersive F(000): 
_exptl_crystal_F_000             172
_exptl_absorpt_coefficient_mu    0.117

_exptl_absorpt_correction_type   None

_diffrn_radiation_type           Synchrotron
_diffrn_radiation_source         'MX1 Beamline Australian Synchrotron'
_diffrn_radiation_wavelength     0.7108
_diffrn_radiation_monochromator  'Silicon Double Crystal'
_diffrn_measurement_device_type  'ADSC Quantum 210r'
_diffrn_measurement_method       'Omega Scan'

_computing_data_collection       'AS QEGUI'
_computing_cell_refinement       'XDS (Kabsch, 1993)'
_computing_data_reduction        'XDS (Kabsch, 1993)'
_computing_structure_solution    'Superflip (Palatinus & Chapuis, 2007)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'

_diffrn_standards_interval_time  .
_diffrn_standards_interval_count .
_diffrn_standards_number         0
_diffrn_standards_decay_%        .

_diffrn_ambient_temperature      100
_diffrn_reflns_number            3285
_diffrn_reflns_av_unetI/netI     0.058
_reflns_number_total             1666
_diffrn_reflns_av_R_equivalents  0.037

_diffrn_reflns_theta_min         3.013
_diffrn_reflns_theta_max         31.923
_diffrn_measured_fraction_theta_max 0.700

_diffrn_reflns_theta_full        25.219
_diffrn_measured_fraction_theta_full 0.829

_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       10
_reflns_limit_h_min              -8
_reflns_limit_h_max              8
_reflns_limit_k_min              -8
_reflns_limit_k_max              10
_reflns_limit_l_min              0
_reflns_limit_l_max              10

_oxford_diffrn_Wilson_B_factor   0.80
_oxford_diffrn_Wilson_scale      0.17

_atom_sites_solution_primary     other
_atom_sites_solution_hydrogens   difmap

_refine_diff_density_min         -0.79
_refine_diff_density_max         0.68

# The values actually used during refinement 
_oxford_refine_reflns_threshold_expression_ref I>-3.0\s(I)
_refine_ls_number_restraints     12
_refine_ls_number_parameters     125
_refine_ls_number_reflns         1425
_oxford_refine_ls_R_factor_ref   0.0932
_refine_ls_wR_factor_ref         0.3262
_refine_ls_goodness_of_fit_ref   1.0560
_refine_ls_shift/su_max          0.0004145
_refine_ls_shift/su_mean         0.0000595

# The values computed with all filters except I/sigma 
_oxford_reflns_number_all        1666
_refine_ls_R_factor_all          0.0985
_refine_ls_wR_factor_all         0.3309

# The values computed with a 2 sigma cutoff - a la SHELX 
_reflns_threshold_expression     I>2.0σ(I)
_reflns_number_gt                1447
_refine_ls_R_factor_gt           0.0925
_refine_ls_wR_factor_gt          0.3279


_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_hydrogen_treatment    mixed
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 Method= Modified Sheldrick 
 w=1/[σ²(F²) + ( 0.13P)² + 3.05P] 
 ,where P=(max(Fo²,0) + 2Fc²)/3 
;

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_occupancy
_atom_site_adp_type
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
_atom_site_attached_hydrogens
N1 N 0.4961(7) 0.1632(6) 0.7462(5) 0.0182 1.0000 Uani D . . . . .
N2 N 0.2590(6) 0.3549(6) 0.5115(5) 0.0179 1.0000 Uani D . . . . .
C3 C 0.4423(7) 0.2587(7) 0.5615(6) 0.0150 1.0000 Uani D . . . . .
C4 C 0.5943(7) 0.2546(7) 0.4115(6) 0.0143 1.0000 Uani . . . . . .
C5 C 0.5375(8) 0.2710(7) 0.2380(6) 0.0176 1.0000 Uani . . . . . .
C6 C 0.6781(7) 0.2665(7) 0.0985(6) 0.0171 1.0000 Uani . . . . . .
C7 C 0.8756(7) 0.2461(7) 0.1272(6) 0.0164 1.0000 Uani . . . . . .
C8 C 0.9314(8) 0.2289(7) 0.3007(6) 0.0179 1.0000 Uani . . . . . .
C9 C 0.7921(8) 0.2339(7) 0.4410(6) 0.0175 1.0000 Uani . . . . . .
C10 C 1.0298(8) 0.2431(7) -0.0264(6) 0.0166 1.0000 Uani . . . . . .
O11 O 0.9681(5) 0.3161(5) -0.1975(5) 0.0193 1.0000 Uani . . . . . .
O12 O 1.2069(5) 0.1715(5) 0.0257(5) 0.0198 1.0000 Uani . . . . . .
H51 H 0.4023 0.2830 0.2180 0.0215 1.0000 Uiso R . . . . .
H61 H 0.6369 0.2794 -0.0180 0.0212 1.0000 Uiso R . . . . .
H81 H 1.0682 0.2109 0.3237 0.0215 1.0000 Uiso R . . . . .
H91 H 0.8303 0.2245 0.5581 0.0205 1.0000 Uiso R . . . . .
H22 H 0.168(4) 0.343(8) 0.602(4) 0.021(2) 1.0000 Uiso D . . . . .
H12 H 0.410(4) 0.169(8) 0.835(4) 0.021(2) 1.0000 Uiso D . . . . .
H21 H 0.229(4) 0.442(7) 0.390(3) 0.021(2) 1.0000 Uiso D . . . . .
H11 H 0.611(5) 0.078(8) 0.782(4) 0.021(2) 1.0000 Uiso D . . . . .


_refine_ls_extinction_method     None
_oxford_refine_ls_scale          2.83(17)

loop_
_geom_bond_atom_site_label_1
_geom_bond_site_symmetry_1
_geom_bond_atom_site_label_2
_geom_bond_site_symmetry_2
_geom_bond_distance
_geom_bond_publ_flag
N1 . C3 . 1.305(6) yes
N1 . H12 . 0.857(19) no
N1 . H11 . 0.865(19) no
N2 . C3 . 1.295(7) yes
N2 . H22 . 0.864(19) no
N2 . H21 . 0.863(19) no
C3 . C4 . 1.468(6) yes
C4 . C5 . 1.386(6) yes
C4 . C9 . 1.376(7) yes
C5 . C6 . 1.363(6) yes
C5 . H51 . 0.944 no
C6 . C7 . 1.373(7) yes
C6 . H61 . 0.933 no
C7 . C8 . 1.381(6) yes
C7 . C10 . 1.495(6) yes
C8 . C9 . 1.363(6) yes
C8 . H81 . 0.951 no
C9 . H91 . 0.941 no
C10 . O11 . 1.248(5) yes
C10 . O12 . 1.241(6) yes

loop_
_geom_angle_atom_site_label_1
_geom_angle_site_symmetry_1
_geom_angle_atom_site_label_2
_geom_angle_site_symmetry_2
_geom_angle_atom_site_label_3
_geom_angle_site_symmetry_3
_geom_angle
_geom_angle_publ_flag
C3 . N1 . H12 . 119.6(18) no
C3 . N1 . H11 . 120.2(18) no
H12 . N1 . H11 . 119(3) no
C3 . N2 . H22 . 120.0(18) no
C3 . N2 . H21 . 120.5(18) no
H22 . N2 . H21 . 119(3) no
N1 . C3 . N2 . 120.8(4) yes
N1 . C3 . C4 . 118.5(5) yes
N2 . C3 . C4 . 120.7(4) yes
C3 . C4 . C5 . 119.4(4) yes
C3 . C4 . C9 . 120.9(4) yes
C5 . C4 . C9 . 119.7(4) yes
C4 . C5 . C6 . 119.7(5) yes
C4 . C5 . H51 . 120.0 no
C6 . C5 . H51 . 120.3 no
C5 . C6 . C7 . 120.9(4) yes
C5 . C6 . H61 . 118.5 no
C7 . C6 . H61 . 120.6 no
C6 . C7 . C8 . 119.2(4) yes
C6 . C7 . C10 . 121.0(4) yes
C8 . C7 . C10 . 119.8(5) yes
C7 . C8 . C9 . 120.5(5) yes
C7 . C8 . H81 . 119.9 no
C9 . C8 . H81 . 119.6 no
C4 . C9 . C8 . 120.1(4) yes
C4 . C9 . H91 . 119.6 no
C8 . C9 . H91 . 120.2 no
C7 . C10 . O11 . 116.6(5) yes
C7 . C10 . O12 . 117.7(4) yes
O11 . C10 . O12 . 125.7(4) yes

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_site_symmetry_D
_geom_hbond_atom_site_label_H
_geom_hbond_site_symmetry_H
_geom_hbond_atom_site_label_A
_geom_hbond_site_symmetry_A
_geom_hbond_angle_DHA
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_publ_flag
N2 . H22 . O11 1_456 179(3) 0.864 1.907 2.772(7) yes
N1 . H12 . O12 1_456 175(5) 0.857 1.906 2.761(7) yes
N2 . H21 . O11 2_665 148(3) 0.863 2.008 2.776(7) yes
N1 . H11 . O12 2_756 153(4) 0.865 1.982 2.778(7) yes

# looking for ARCHIVE-HKL.CIF 

# end of ARCHIVE-HKL.CIF 

_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: Water/DMF'
####################################################################### 
# 
# 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_1_293K
_database_code_depnum_ccdc_archive 'CCDC 2047426'
loop_
_audit_author_name
_audit_author_address
'Nicholas White'
;Australian National University
Australia
;
_audit_update_record             
;
2020-12-01 deposited with the CCDC.	2021-01-13 downloaded from the CCDC.
;

_exptl_special_details           
; 
 The crystal was 
placed in the cold stream of an Oxford 
Cryosystems open-flow nitrogen cryostat (Cosier & 
Glazer, 1986) with a nominal stability of 0.1K. 
 
Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107. 
;

_refine_special_details          
; 
Hydrogen atoms were  visible in the Fourier difference 
map and were initially refined with restraints on bond lengths and angles, 
after which the positions were used as the basis for a riding model.  The N-H 
hydrogen atoms were refined with restraints on bond lengths and angles. 

Apart from the restraints on N-H bond length and C-N-H bond angle, it was not 
necessary to use any crystallographic restraints during the refinement.
;

_cell_length_a                   7.03480(2)
_cell_length_b                   7.85120(2)
_cell_length_c                   7.88270(2)
_cell_angle_alpha                61.268(5)
_cell_angle_beta                 74.309(4)
_cell_angle_gamma                82.320(5)
_cell_volume                     367.540(19)

_symmetry_cell_setting           triclinic
_symmetry_space_group_name_H-M   'P -1 '
_symmetry_space_group_name_Hall  '-P 1'

loop_
_symmetry_equiv_pos_as_xyz
x,y,z
-x,-y,-z

loop_
_atom_type_symbol
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_Cromer_Mann_a1
_atom_type_scat_Cromer_Mann_b1
_atom_type_scat_Cromer_Mann_a2
_atom_type_scat_Cromer_Mann_b2
_atom_type_scat_Cromer_Mann_a3
_atom_type_scat_Cromer_Mann_b3
_atom_type_scat_Cromer_Mann_a4
_atom_type_scat_Cromer_Mann_b4
_atom_type_scat_Cromer_Mann_c
_atom_type_scat_source
C 0.0181 0.0091 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512
0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998
0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
N 0.0311 0.0180 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826
-11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
O 0.0492 0.0322 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089
0.2508 'International Tables Vol C 4.2.6.8 and 6.1.1.4'

_cell_formula_units_Z            2

_chemical_formula_sum            'C8 H8 N2 O2'
_chemical_formula_moiety         'C8 H8 N2 O2'
_chemical_compound_source        synthesized
_chemical_formula_weight         164.16

_cell_measurement_reflns_used    3164
_cell_measurement_theta_min      6.72
_cell_measurement_theta_max      72.72
_cell_measurement_temperature    293

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_size_min          0.08
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_max          0.11

_exptl_crystal_density_diffrn    1.483
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_density_method    'not measured'
# Non-dispersive F(000): 
_exptl_crystal_F_000             172
_exptl_absorpt_coefficient_mu    0.913

_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrysAlisPro, (Agilent, 2011)'
_exptl_absorpt_correction_T_min  0.86
_exptl_absorpt_correction_T_max  1.00
_diffrn_measurement_device_type  'Oxford Diffraction Supernova'
_diffrn_measurement_device       Area
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_measurement_method       ω

_computing_data_collection       'CrysAlisPro, (Agilent, 2011'
_computing_cell_refinement       'CrysAlisPro, (Agilent, 2011)'
_computing_data_reduction        'CrysAlisPro, (Agilent, 2011)'
_computing_structure_solution    'Superflip (Palatinus & Chapuis, 2007)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'

_diffrn_standards_interval_time  .
_diffrn_standards_interval_count .
_diffrn_standards_number         0
_diffrn_standards_decay_%        .

_diffrn_ambient_temperature      293
_diffrn_reflns_number            6926
_diffrn_reflns_av_unetI/netI     0.037
_reflns_number_total             1434
_diffrn_reflns_av_R_equivalents  0.029

_diffrn_reflns_theta_min         6.429
_diffrn_reflns_theta_max         72.678
_diffrn_measured_fraction_theta_max 0.986

_diffrn_reflns_theta_full        69.044
_diffrn_measured_fraction_theta_full 0.996

_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       9
_reflns_limit_h_min              -8
_reflns_limit_h_max              8
_reflns_limit_k_min              -7
_reflns_limit_k_max              9
_reflns_limit_l_min              0
_reflns_limit_l_max              9

_oxford_diffrn_Wilson_B_factor   2.44
_oxford_diffrn_Wilson_scale      1.22

_atom_sites_solution_primary     other
_atom_sites_solution_hydrogens   difmap

_refine_diff_density_min         -0.37
_refine_diff_density_max         0.36

# The values actually used during refinement 
_oxford_refine_reflns_threshold_expression_ref I>-3.0\s(I)
_refine_ls_number_restraints     12
_refine_ls_number_parameters     125
_refine_ls_number_reflns         1335
_oxford_refine_ls_R_factor_ref   0.0716
_refine_ls_wR_factor_ref         0.2194
_refine_ls_goodness_of_fit_ref   1.0300
_refine_ls_shift/su_max          0.0004183
_refine_ls_shift/su_mean         0.0000698

# The values computed with all filters except I/sigma 
_oxford_reflns_number_all        1428
_refine_ls_R_factor_all          0.0810
_refine_ls_wR_factor_all         0.2542

# The values computed with a 2 sigma cutoff - a la SHELX 
_reflns_threshold_expression     I>2.0σ(I)
_reflns_number_gt                1298
_refine_ls_R_factor_gt           0.0780
_refine_ls_wR_factor_gt          0.2520

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_hydrogen_treatment    mixed
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 Method= Modified Sheldrick 
 w=1/[σ²(F²) + ( 0.12P)² + 0.53P] 
 ,where P=(max(Fo²,0) + 2Fc²)/3 
;

# Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3
# Replace last . with number of unfound hydrogen atoms attached to an atom.
# ..._refinement_flags_... 
# . no refinement constraints           S special position constraint on site
# G rigid group refinement of site      R riding atom
# D distance or angle restraint on site T thermal displacement constraints
# U Uiso or Uij restraint (rigid bond)  P partial occupancy constraint
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_occupancy
_atom_site_adp_type
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
_atom_site_attached_hydrogens
N1 N 0.5066(4) -0.2457(3) 0.3376(4) 0.0375 1.0000 Uani D . . . . .
N2 N 0.7411(3) -0.0134(3) 0.1459(4) 0.0385 1.0000 Uani D . . . . .
C3 C 0.5579(4) -0.0626(4) 0.2425(4) 0.0290 1.0000 Uani D . . . . .
C4 C 0.4077(4) 0.0884(4) 0.2454(4) 0.0288 1.0000 Uani . . . . . .
C5 C 0.2104(4) 0.0580(4) 0.2672(4) 0.0330 1.0000 Uani . . . . . .
C6 C 0.0713(4) 0.1980(4) 0.2720(5) 0.0343 1.0000 Uani . . . . . .
C7 C 0.1256(4) 0.3720(4) 0.2531(4) 0.0299 1.0000 Uani . . . . . .
C8 C 0.3230(4) 0.4003(4) 0.2324(5) 0.0353 1.0000 Uani . . . . . .
C9 C 0.4627(4) 0.2608(4) 0.2286(5) 0.0348 1.0000 Uani . . . . . .
C10 C -0.0276(4) 0.5262(4) 0.2553(4) 0.0326 1.0000 Uani . . . . . .
O11 O -0.2045(3) 0.4738(3) 0.3298(4) 0.0455 1.0000 Uani . . . . . .
O12 O 0.0327(3) 0.6967(3) 0.1808(4) 0.0448 1.0000 Uani . . . . . .
H51 H 0.1738 -0.0600 0.2798 0.0487 1.0000 Uiso R . . . . .
H61 H -0.0645 0.1778 0.2880 0.0507 1.0000 Uiso R . . . . .
H81 H 0.3597 0.5196 0.2175 0.0518 1.0000 Uiso R . . . . .
H91 H 0.5954 0.2815 0.2131 0.0508 1.0000 Uiso R . . . . .
H12 H 0.591(4) -0.334(3) 0.330(5) 0.054(2) 1.0000 Uiso D . . . . .
H22 H 0.834(3) -0.103(3) 0.157(5) 0.055(2) 1.0000 Uiso D . . . . .
H11 H 0.396(4) -0.285(3) 0.426(5) 0.054(2) 1.0000 Uiso D . . . . .
H21 H 0.773(4) 0.106(3) 0.062(5) 0.055(2) 1.0000 Uiso D . . . . .


_refine_ls_extinction_method     None
_oxford_refine_ls_scale          0.923(12)

loop_
_geom_bond_atom_site_label_1
_geom_bond_site_symmetry_1
_geom_bond_atom_site_label_2
_geom_bond_site_symmetry_2
_geom_bond_distance
_geom_bond_publ_flag
N1 . C3 . 1.310(4) yes
N1 . H12 . 0.865(18) no
N1 . H11 . 0.869(18) no
N2 . C3 . 1.307(4) yes
N2 . H22 . 0.883(18) no
N2 . H21 . 0.866(18) no
C3 . C4 . 1.483(4) yes
C4 . C5 . 1.390(4) yes
C4 . C9 . 1.392(4) yes
C5 . C6 . 1.378(4) yes
C5 . H51 . 0.947 no
C6 . C7 . 1.395(4) yes
C6 . H61 . 0.954 no
C7 . C8 . 1.390(4) yes
C7 . C10 . 1.512(4) yes
C8 . C9 . 1.376(4) yes
C8 . H81 . 0.949 no
C9 . H91 . 0.934 no
C10 . O11 . 1.254(3) yes
C10 . O12 . 1.256(3) yes

loop_
_geom_angle_atom_site_label_1
_geom_angle_site_symmetry_1
_geom_angle_atom_site_label_2
_geom_angle_site_symmetry_2
_geom_angle_atom_site_label_3
_geom_angle_site_symmetry_3
_geom_angle
_geom_angle_publ_flag
C3 . N1 . H12 . 120.4(16) no
C3 . N1 . H11 . 121.4(16) no
H12 . N1 . H11 . 117(2) no
C3 . N2 . H22 . 120.6(16) no
C3 . N2 . H21 . 121.1(16) no
H22 . N2 . H21 . 118(2) no
N1 . C3 . N2 . 120.0(2) yes
N1 . C3 . C4 . 119.8(2) yes
N2 . C3 . C4 . 120.2(2) yes
C3 . C4 . C5 . 120.3(2) yes
C3 . C4 . C9 . 120.3(2) yes
C5 . C4 . C9 . 119.4(2) yes
C4 . C5 . C6 . 119.9(3) yes
C4 . C5 . H51 . 119.0 no
C6 . C5 . H51 . 121.1 no
C5 . C6 . C7 . 121.0(3) yes
C5 . C6 . H61 . 120.4 no
C7 . C6 . H61 . 118.6 no
C6 . C7 . C8 . 118.5(3) yes
C6 . C7 . C10 . 120.6(2) yes
C8 . C7 . C10 . 120.8(2) yes
C7 . C8 . C9 . 120.8(3) yes
C7 . C8 . H81 . 118.3 no
C9 . C8 . H81 . 120.8 no
C4 . C9 . C8 . 120.3(3) yes
C4 . C9 . H91 . 119.4 no
C8 . C9 . H91 . 120.3 no
C7 . C10 . O11 . 117.4(2) yes
C7 . C10 . O12 . 117.3(2) yes
O11 . C10 . O12 . 125.3(3) yes

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_site_symmetry_D
_geom_hbond_atom_site_label_H
_geom_hbond_site_symmetry_H
_geom_hbond_atom_site_label_A
_geom_hbond_site_symmetry_A
_geom_hbond_angle_DHA
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_publ_flag
N1 . H12 . O11 1_645 174(4) 0.865 1.941 2.802(4) yes
N2 . H22 . O12 1_645 178(3) 0.883 1.932 2.814(4) yes
N1 . H11 . O11 2_556 157(3) 0.869 2.024 2.844(4) yes
N2 . H21 . O12 2_665 149(2) 0.866 2.056 2.834(4) yes



# Manually omitted reflections

loop_
_oxford_refln_omitted_index_h
_oxford_refln_omitted_index_k
_oxford_refln_omitted_index_l
_oxford_refln_omitted_flag
_oxford_refln_omitted_details
0 0 2 x .
1 1 2 x .
4 6 4 x .
6 1 4 x .
2 2 0 x .
-2 2 0 x .
1 1 0 x .
1 1 4 x .
# looking for ARCHIVE-HKL.CIF 

# end of ARCHIVE-HKL.CIF 

_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: Water/DMF'
####################################################################### 
# 
# 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_2TP293K
_database_code_depnum_ccdc_archive 'CCDC 2047427'
loop_
_audit_author_name
_audit_author_address
'Nicholas White'
;Australian National University
Australia
;
_audit_update_record             
;
2020-12-01 deposited with the CCDC.	2021-01-13 downloaded from the CCDC.
;
#==============================================================================
# start Validation Reply Form
_vrf_PLAT110_2TP293K             
;
PROBLEM: ADDSYM Detects Potential Lattice Translation ...          ? Check 
RESPONSE: This additional symmetry gives a cell with a halved volume where
the nitrogen and oxygen atoms are co-incident, i.e. the asymmetric unit
contains half a benzene ring attached to half a amidinium/carboxylate group.
This does not make chemical sense and gives an inferior refinement, i.e. this 
is additional symmetry is pseudosymmetry rather than genuine symmetry.
;
_vrf_PLAT112_2TP293K             
;
PROBLEM: ADDSYM Detects New (Pseudo) Symm. Elem         A        100 %Fit  
RESPONSE: This additional symmetry gives a cell with a halved volume where
the nitrogen and oxygen atoms are co-incident, i.e. the asymmetric unit
contains half a benzene ring attached to half a amidinium/carboxylate group.
This does not make chemical sense and gives an inferior refinement, i.e. this 
is additional symmetry is pseudosymmetry rather than genuine symmetry.
;
_vrf_PLAT113_2TP293K             
;
PROBLEM: ADDSYM Suggests Possible Pseudo/New  Space Group        P-1 Check 
RESPONSE: This additional symmetry gives a cell with a halved volume where
the nitrogen and oxygen atoms are co-incident, i.e. the asymmetric unit
contains half a benzene ring attached to half a amidinium/carboxylate group.
This does not make chemical sense and gives an inferior refinement, i.e. this 
is additional symmetry is pseudosymmetry rather than genuine symmetry.
;

_exptl_special_details           
; 
The crystal was 
placed in the cold stream of an Oxford 
Cryosystems open-flow nitrogen cryostat (Cosier & 
Glazer, 1986) with a nominal stability of 0.1K. 
 
Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107. 
;

_refine_special_details          
; 
C-H hydrogen atoms were  visible in the Fourier difference map and 
were initially refined with restraints on bond lengths and angles, after which 
the positions were used as the basis for a riding model. N-H hydrogen atoms
were visible in the difference map and were refined with restraints on bond 
lengths and angles. Other than restraints on the N-H hydrogen atoms, it was
not necessary to use any crystallographic restraints in the refinement.
;

_cell_length_a                   5.5557(5)
_cell_length_b                   7.8957(7)
_cell_length_c                   9.0549(8)
_cell_angle_alpha                71.386(8)
_cell_angle_beta                 83.555(7)
_cell_angle_gamma                74.217(7)
_cell_volume                     362.09(6)

_symmetry_cell_setting           triclinic
_symmetry_space_group_name_H-M   'P -1 '
_symmetry_space_group_name_Hall  '-P 1'

loop_
_symmetry_equiv_pos_as_xyz
x,y,z
-x,-y,-z

loop_
_atom_type_symbol
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_Cromer_Mann_a1
_atom_type_scat_Cromer_Mann_b1
_atom_type_scat_Cromer_Mann_a2
_atom_type_scat_Cromer_Mann_b2
_atom_type_scat_Cromer_Mann_a3
_atom_type_scat_Cromer_Mann_b3
_atom_type_scat_Cromer_Mann_a4
_atom_type_scat_Cromer_Mann_b4
_atom_type_scat_Cromer_Mann_c
_atom_type_scat_source
C 0.0181 0.0091 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512
0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998
0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
N 0.0311 0.0180 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826
-11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
O 0.0492 0.0322 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089
0.2508 'International Tables Vol C 4.2.6.8 and 6.1.1.4'


_cell_formula_units_Z            2

_chemical_formula_sum            'C8 H8 N2 O2'
_chemical_formula_moiety         'C4 H6 N2, C4 H2 O2'
_chemical_compound_source        synthesized
_chemical_formula_weight         164.16


_cell_measurement_reflns_used    2031
_cell_measurement_theta_min      5.15
_cell_measurement_theta_max      73.5
_cell_measurement_temperature    293

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_size_min          0.06
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_max          0.10

_exptl_crystal_density_diffrn    1.506
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_density_method    'not measured'
# Non-dispersive F(000): 
_exptl_crystal_F_000             171.999
_exptl_absorpt_coefficient_mu    0.927

_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrysAlisPro, (Agilent, 2011)'
_exptl_absorpt_correction_T_min  0.93
_exptl_absorpt_correction_T_max  1.00
_diffrn_measurement_device_type  'Oxford Diffraction Supernova'
_diffrn_measurement_device       Area
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_measurement_method       ω

_computing_data_collection       'CrysAlisPro, (Agilent, 2011'
_computing_cell_refinement       'CrysAlisPro, (Agilent, 2011)'
_computing_data_reduction        'CrysAlisPro, (Agilent, 2011)'
_computing_structure_solution    'Superflip (Palatinus & Chapuis, 2007)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'

_diffrn_standards_interval_time  .
_diffrn_standards_interval_count .
_diffrn_standards_number         0
_diffrn_standards_decay_%        .

_diffrn_ambient_temperature      293
_diffrn_reflns_number            5714
_diffrn_reflns_av_unetI/netI     0.035
_reflns_number_total             1452
_diffrn_reflns_av_R_equivalents  0.024

_diffrn_reflns_theta_min         5.156
_diffrn_reflns_theta_max         73.757
_diffrn_measured_fraction_theta_max 0.994

_diffrn_reflns_theta_full        68.037
_diffrn_measured_fraction_theta_full 1.000

_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       10
_reflns_limit_h_min              -6
_reflns_limit_h_max              6
_reflns_limit_k_min              -8
_reflns_limit_k_max              9
_reflns_limit_l_min              0
_reflns_limit_l_max              11

_oxford_diffrn_Wilson_B_factor   2.20
_oxford_diffrn_Wilson_scale      0.01

_atom_sites_solution_primary     other
_atom_sites_solution_hydrogens   difmap

_refine_diff_density_min         -0.20
_refine_diff_density_max         0.25

# The values actually used during refinement 
# These are labelled "all" for compatibility with PLATON 
_oxford_refine_reflns_threshold_expression I>-3.0\s(I)
_refine_ls_number_restraints     12
_refine_ls_number_parameters     125
_refine_ls_number_reflns         1449
_oxford_refine_ls_R_factor_ref   0.0532
_refine_ls_R_factor_all          0.0532
_refine_ls_wR_factor_ref         0.1382
_refine_ls_wR_factor_all         0.1382
_refine_ls_goodness_of_fit_ref   1.0049
_refine_ls_shift/su_max          0.0002619
_refine_ls_shift/su_mean         0.0000360

# Computed with I/sigma = -10 
_oxford_reflns_number_all        1449
_oxford_refine_ls_R_factor_all   0.0532
_oxford_refine_ls_wR_factor_all  0.1382

# Computed with no filters except I/sigma = +2 a la SHELX 
_reflns_threshold_expression     I>2.0σ(I)
_reflns_number_gt                1182
_refine_ls_R_factor_gt           0.0456
_refine_ls_wR_factor_gt          0.1277


_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_hydrogen_treatment    mixed
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 Method= Modified Sheldrick 
 w=1/[σ²(F²) + ( 0.08P)² + 0.09P] 
 ,where P=(max(Fo²,0) + 2Fc²)/3 
;

# Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3
# Replace last . with number of unfound hydrogen atoms attached to an atom.
# ..._refinement_flags_... 
# . no refinement constraints           S special position constraint on site
# G rigid group refinement of site      R riding atom
# D distance or angle restraint on site T thermal displacement constraints
# U Uiso or Uij restraint (rigid bond)  P partial occupancy constraint
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_occupancy
_atom_site_adp_type
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
_atom_site_attached_hydrogens
N1 N 0.6372(3) 0.44052(17) 0.70649(14) 0.0350 1.0000 Uani D . . . . .
N2 N 0.6733(2) 0.18957(16) 0.91982(14) 0.0336 1.0000 Uani D . . . . .
C3 C 0.7212(2) 0.34871(18) 0.84631(15) 0.0268 1.0000 Uani D . . . . .
C4 C 0.8679(2) 0.42696(18) 0.92400(15) 0.0262 1.0000 Uani . . . . . .
C5 C 1.0435(3) 0.31019(19) 1.03400(17) 0.0313 1.0000 Uani . . . . . .
C6 C 0.8248(3) 0.61696(19) 0.89087(16) 0.0311 1.0000 Uani . . . . . .
O11 O 1.2985(2) 0.31361(14) 0.59119(13) 0.0414 1.0000 Uani . . . . . .
O12 O 1.3853(2) 0.04611(15) 0.78091(12) 0.0436 1.0000 Uani . . . . . .
C13 C 1.2842(3) 0.15029(19) 0.65506(15) 0.0295 1.0000 Uani . . . . . .
C14 C 1.1359(3) 0.07228(19) 0.57487(15) 0.0275 1.0000 Uani . . . . . .
C15 C 0.9562(3) 0.18980(19) 0.46790(16) 0.0309 1.0000 Uani . . . . . .
C16 C 1.1783(3) -0.11720(19) 0.60603(16) 0.0316 1.0000 Uani . . . . . .
H51 H 1.0765 0.1825 1.0577 0.0367 1.0000 Uiso R . . . . .
H61 H 0.7065 0.6980 0.8164 0.0374 1.0000 Uiso R . . . . .
H151 H 0.9262 0.3210 0.4429 0.0355 1.0000 Uiso R . . . . .
H161 H 1.3048 -0.2003 0.6763 0.0373 1.0000 Uiso R . . . . .
H22 H 0.695(3) 0.137(2) 1.0204(17) 0.0419(19) 1.0000 Uiso D . . . . .
H12 H 0.697(3) 0.533(2) 0.6421(18) 0.0425(19) 1.0000 Uiso D . . . . .
H21 H 0.575(3) 0.147(2) 0.8745(18) 0.0420(18) 1.0000 Uiso D . . . . .
H11 H 0.535(3) 0.395(2) 0.6659(18) 0.0433(19) 1.0000 Uiso D . . . . .


_refine_ls_extinction_method     None
_oxford_refine_ls_scale          11.3(11)

loop_
_geom_bond_atom_site_label_1
_geom_bond_site_symmetry_1
_geom_bond_atom_site_label_2
_geom_bond_site_symmetry_2
_geom_bond_distance
_geom_bond_publ_flag
N1 . C3 . 1.3072(17) yes
N1 . H12 . 0.895(14) no
N1 . H11 . 0.911(14) no
N2 . C3 . 1.3043(18) yes
N2 . H22 . 0.879(14) no
N2 . H21 . 0.909(14) no
C3 . C4 . 1.4900(16) yes
C4 . C5 . 1.3916(19) yes
C4 . C6 . 1.390(2) yes
C5 . C6 2_767 1.3856(19) yes
C5 . H51 . 0.931 no
C6 . H61 . 0.944 no
O11 . C13 . 1.2542(17) yes
O12 . C13 . 1.2588(17) yes
C13 . C14 . 1.5106(16) yes
C14 . C15 . 1.3912(19) yes
C14 . C16 . 1.388(2) yes
C15 . C16 2_756 1.3874(19) yes
C15 . H151 . 0.958 no
C16 . H161 . 0.955 no

loop_
_geom_angle_atom_site_label_1
_geom_angle_site_symmetry_1
_geom_angle_atom_site_label_2
_geom_angle_site_symmetry_2
_geom_angle_atom_site_label_3
_geom_angle_site_symmetry_3
_geom_angle
_geom_angle_publ_flag
C3 . N1 . H12 . 123.1(10) no
C3 . N1 . H11 . 118.2(10) no
H12 . N1 . H11 . 117.7(14) no
C3 . N2 . H22 . 122.5(10) no
C3 . N2 . H21 . 119.1(10) no
H22 . N2 . H21 . 116.2(14) no
N1 . C3 . N2 . 120.19(11) yes
N1 . C3 . C4 . 120.22(12) yes
N2 . C3 . C4 . 119.58(12) yes
C3 . C4 . C5 . 120.20(12) yes
C3 . C4 . C6 . 120.29(12) yes
C5 . C4 . C6 . 119.48(12) yes
C4 . C5 . C6 2_767 120.19(13) yes
C4 . C5 . H51 . 121.1 no
C6 2_767 C5 . H51 . 118.7 no
C4 . C6 . C5 2_767 120.33(13) yes
C4 . C6 . H61 . 120.5 no
C5 2_767 C6 . H61 . 119.2 no
O12 . C13 . O11 . 124.82(11) yes
O12 . C13 . C14 . 117.49(12) yes
O11 . C13 . C14 . 117.69(12) yes
C13 . C14 . C15 . 120.30(12) yes
C13 . C14 . C16 . 120.49(12) yes
C15 . C14 . C16 . 119.20(12) yes
C14 . C15 . C16 2_756 119.99(13) yes
C14 . C15 . H151 . 120.7 no
C16 2_756 C15 . H151 . 119.3 no
C14 . C16 . C15 2_756 120.81(13) yes
C14 . C16 . H161 . 120.6 no
C15 2_756 C16 . H161 . 118.6 no

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_site_symmetry_D
_geom_hbond_atom_site_label_H
_geom_hbond_site_symmetry_H
_geom_hbond_atom_site_label_A
_geom_hbond_site_symmetry_A
_geom_hbond_angle_DHA
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_publ_flag
N2 . H22 . O12 2_757 148.8(14) 0.879(14) 2.008(15) 2.797(2) yes
N1 . H12 . O11 2_766 140.9(14) 0.895(14) 2.074(15) 2.825(2) yes
N2 . H21 . O12 1_455 176.8(16) 0.909(14) 1.880(14) 2.788(2) yes
N1 . H11 . O11 1_455 174.5(17) 0.911(14) 1.879(14) 2.787(2) yes


# Manually omitted reflections
loop_
_oxford_refln_omitted_index_h
_oxford_refln_omitted_index_k
_oxford_refln_omitted_index_l
_oxford_refln_omitted_flag
_oxford_refln_omitted_details
-1 0 2 x .
-1 1 1 x .
2 2 2 x .
# looking for ARCHIVE-HKL.CIF 

# end of ARCHIVE-HKL.CIF 

_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: Water'
