# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 2024

####################################################################### 
# 
# 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_B19815
_database_code_depnum_ccdc_archive 'CCDC 2310625'
loop_
_audit_author_name
_audit_author_address
'Pascal Retailleau'
;ICSN CNRS University Paris Saclay
France
;
_audit_update_record             
;
2023-11-27 deposited with the CCDC.	2024-01-10 downloaded from the CCDC.
;

# start Validation Reply Form
_vrf_PLAT089_B19815              
;
PROBLEM: Poor Data / Parameter Ratio (Zmax < 18) ........       4.21 Note  
RESPONSE: Structure model lies on a two-fold rotation axis and 
has to be split in two equal parts, so the refined parameters must 
be multiplied by 2. However, data were recorded at high resolution 
(theta_max  about 30 deg).
;
# end Validation Reply Form

_audit_creation_method           SHELXL-2019/3
_chemical_name_systematic        11-methylbenzo[a]phenazine
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C17 H12 N2'
_chemical_formula_sum            'C17 H12 N2'
_chemical_formula_weight         244.29

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'

_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_H-M_alt        'P 21'
_space_group_name_Hall           'P 2yb'

_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'

_cell_length_a                   4.3756(4)
_cell_length_b                   10.0848(9)
_cell_length_c                   14.3422(12)
_cell_angle_alpha                90
_cell_angle_beta                 98.393(8)
_cell_angle_gamma                90
_cell_volume                     626.10(10)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    4318
_cell_measurement_theta_min      3.4770
_cell_measurement_theta_max      27.1240

_exptl_crystal_description       plate
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.296
_exptl_crystal_F_000             256
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
0 1 5 0.0426
0 -1 -5 0.0243
5 -2 -2 0.2947
0 -5 -1 0.0868
0 5 1 0.0593
-2 -5 1 0.1647
4 2 -5 0.2921
-3 0 -5 0.1440
0 -4 5 0.0899
0 4 -5 0.0294
2 -5 3 0.1986
0 0 -1 0.0155
0 -1 5 0.0701
0 1 -5 0.0132
_exptl_crystal_size_max          0.514
_exptl_crystal_size_mid          0.147
_exptl_crystal_size_min          0.067
_exptl_absorpt_coefficient_mu    0.077
_exptl_absorpt_correction_T_min  0.724
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.43.98a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_diffrn_ambient_temperature      293(2)
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_monochromator  mirror
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_reflns_number            14319
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_av_R_equivalents  0.0375
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_theta_min         2.871
_diffrn_reflns_theta_max         29.566
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             3331
_reflns_number_gt                2106
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.845
_reflns_Friedel_fraction_max     0.920
_reflns_Friedel_fraction_full    0.999

_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. Completness statistics refer to single and
 composite reflections containing twin component 1 only.
;

_computing_data_collection       'CrysAlisPro system (CCD 43.98a 64-bit)'
_computing_cell_refinement       'CrysAlisPro 1.171.43.98a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.43.98a (Rigaku OD, 2023)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015a)'
_computing_structure_refinement  'SHELXL-2019/2 (Sheldrick, 2015b)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_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)+(0.0504P)²+0.0125P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     other
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0(6)
_chemical_absolute_configuration .
_refine_ls_number_reflns         3329
_refine_ls_number_parameters     346
_refine_ls_number_restraints     379
_refine_ls_R_factor_all          0.0662
_refine_ls_R_factor_gt           0.0373
_refine_ls_wR_factor_ref         0.1122
_refine_ls_wR_factor_gt          0.0967
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_restrained_S_all      0.984
_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
N1 N 0.501(3) 0.7495(10) 0.7002(6) 0.0501(16) Uani 0.5 1 d D . P A 1
C1 C 0.623(3) 0.6788(14) 0.5207(6) 0.086(3) Uani 0.5 1 d D . P A 1
H1A H 0.651950 0.634274 0.463500 0.130 Uiso 0.5 1 calc R U P A 1
H1B H 0.712000 0.765910 0.521414 0.130 Uiso 0.5 1 calc R U P A 1
H1C H 0.406310 0.685891 0.524211 0.130 Uiso 0.5 1 calc R U P A 1
N2 N 0.7597(9) 0.6142(4) 0.8656(2) 0.0565(10) Uani 0.5 1 d D . P A 1
C2 C 0.779(3) 0.6008(11) 0.6041(6) 0.069(3) Uani 0.5 1 d D . P A 1
C3 C 0.959(3) 0.4958(13) 0.6024(8) 0.082(3) Uani 0.5 1 d D . P A 1
H3 H 1.004427 0.465301 0.544761 0.099 Uiso 0.5 1 calc R U P A 1
C4 C 1.083(6) 0.4298(17) 0.6840(11) 0.086(4) Uani 0.5 1 d D . P A 1
H4A H 1.208218 0.356278 0.678930 0.103 Uiso 0.5 1 calc R U P A 1
C5 C 1.027(3) 0.4702(12) 0.7758(9) 0.068(2) Uani 0.5 1 d D . P A 1
H5 H 1.119996 0.427428 0.830100 0.081 Uiso 0.5 1 calc R U P A 1
C6 C 0.826(2) 0.5777(9) 0.7796(7) 0.0561(19) Uani 0.5 1 d D . P A 1
C7 C 0.694(3) 0.6447(11) 0.6954(7) 0.0544(19) Uani 0.5 1 d D . P A 1
C8 C 0.441(2) 0.7870(9) 0.7849(6) 0.0437(14) Uani 0.5 1 d D . P A 1
C9 C 0.5736(9) 0.7183(5) 0.8687(3) 0.0526(11) Uani 0.5 1 d D . P A 1
C10 C 0.5024(12) 0.7596(6) 0.9571(3) 0.0643(14) Uani 0.5 1 d D . P A 1
H10 H 0.587994 0.714377 1.011218 0.077 Uiso 0.5 1 calc R U P A 1
C11 C 0.311(2) 0.8641(9) 0.9649(5) 0.0607(18) Uani 0.5 1 d D . P A 1
H11 H 0.270909 0.892181 1.023639 0.073 Uiso 0.5 1 calc R U P A 1
C12 C 0.170(3) 0.9315(11) 0.8788(8) 0.0522(16) Uani 0.5 1 d D . P A 1
C13 C 0.237(2) 0.8985(7) 0.7917(6) 0.0448(14) Uani 0.5 1 d D . P A 1
C14 C 0.096(3) 0.9671(12) 0.7120(7) 0.063(2) Uani 0.5 1 d D . P A 1
H14 H 0.130572 0.940910 0.652234 0.075 Uiso 0.5 1 calc R U P A 1
C15 C -0.093(3) 1.0733(12) 0.7221(9) 0.070(2) Uani 0.5 1 d D . P A 1
H15 H -0.180494 1.120954 0.669343 0.084 Uiso 0.5 1 calc R U P A 1
C16 C -0.151(3) 1.1079(11) 0.8070(9) 0.073(2) Uani 0.5 1 d D . P A 1
H16 H -0.282283 1.179260 0.812221 0.088 Uiso 0.5 1 calc R U P A 1
C17 C -0.024(3) 1.0413(10) 0.8885(9) 0.0621(17) Uani 0.5 1 d D . P A 1
H17 H -0.065167 1.068193 0.947453 0.075 Uiso 0.5 1 calc R U P A 1
N1B N 0.489(2) 0.7559(10) 0.7977(7) 0.072(3) Uani 0.5 1 d D . P B 2
C1B C 0.364(3) 0.8298(15) 0.9775(8) 0.111(5) Uani 0.5 1 d D . P B 2
H1BA H 0.328788 0.737331 0.964288 0.166 Uiso 0.5 1 calc R U P B 2
H1BB H 0.269832 0.854374 1.031361 0.166 Uiso 0.5 1 calc R U P B 2
H1BC H 0.582512 0.846225 0.990435 0.166 Uiso 0.5 1 calc R U P B 2
N2B N 0.2297(10) 0.8942(5) 0.6334(3) 0.0736(12) Uani 0.5 1 d D . P B 2
C2B C 0.231(3) 0.9077(17) 0.8967(9) 0.086(3) Uani 0.5 1 d D . P B 2
C3B C 0.048(3) 1.0068(16) 0.8961(11) 0.101(4) Uani 0.5 1 d D . P B 2
H3B H 0.003509 1.036021 0.954150 0.122 Uiso 0.5 1 calc R U P B 2
C4B C -0.090(3) 1.0738(14) 0.8178(12) 0.108(4) Uani 0.5 1 d D . P B 2
H4BA H -0.227009 1.142146 0.825032 0.130 Uiso 0.5 1 calc R U P B 2
C5B C -0.027(3) 1.0414(14) 0.7257(11) 0.091(4) Uani 0.5 1 d D . P B 2
H5B H -0.109420 1.089305 0.672493 0.109 Uiso 0.5 1 calc R U P B 2
C6B C 0.170(3) 0.9312(13) 0.7210(8) 0.070(3) Uani 0.5 1 d D . P B 2
C7B C 0.299(3) 0.8580(10) 0.8010(7) 0.066(2) Uani 0.5 1 d D . P B 2
C8B C 0.553(4) 0.7214(17) 0.7133(10) 0.073(3) Uani 0.5 1 d D . P B 2
C9B C 0.4212(12) 0.7936(6) 0.6301(3) 0.0671(13) Uani 0.5 1 d D . P B 2
C10B C 0.4962(15) 0.7470(7) 0.5390(4) 0.0781(18) Uani 0.5 1 d D . P B 2
H10B H 0.412138 0.790400 0.484013 0.094 Uiso 0.5 1 calc R U P B 2
C11B C 0.684(3) 0.6428(14) 0.5340(9) 0.087(3) Uani 0.5 1 d D . P B 2
H11B H 0.739668 0.614533 0.477055 0.104 Uiso 0.5 1 calc R U P B 2
C12B C 0.797(3) 0.5758(16) 0.6234(8) 0.086(3) Uani 0.5 1 d D . P B 2
C13B C 0.753(4) 0.6101(14) 0.7056(9) 0.073(3) Uani 0.5 1 d D . P B 2
C14B C 0.889(3) 0.5380(11) 0.7852(10) 0.081(4) Uani 0.5 1 d D . P B 2
H14B H 0.850600 0.560820 0.845245 0.097 Uiso 0.5 1 calc R U P B 2
C15B C 1.078(4) 0.4341(17) 0.7724(14) 0.101(4) Uani 0.5 1 d D . P B 2
H15B H 1.168531 0.388172 0.825523 0.121 Uiso 0.5 1 calc R U P B 2
C16B C 1.139(6) 0.395(2) 0.6894(14) 0.095(4) Uani 0.5 1 d D . P B 2
H16B H 1.264493 0.321552 0.683358 0.114 Uiso 0.5 1 calc R U P B 2
C17B C 1.011(4) 0.4663(17) 0.6131(12) 0.101(4) Uani 0.5 1 d D . P B 2
H17B H 1.059263 0.445612 0.553777 0.121 Uiso 0.5 1 calc R U P B 2


_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 C8 1.335(8) . ?
N1 C7 1.361(10) . ?
C1 C2 1.509(11) . ?
C1 H1A 0.9600 . ?
C1 H1B 0.9600 . ?
C1 H1C 0.9600 . ?
N2 C9 1.334(6) . ?
N2 C6 1.358(10) . ?
C2 C3 1.324(15) . ?
C2 C7 1.480(12) . ?
C3 C4 1.385(14) . ?
C3 H3 0.9300 . ?
C4 C5 1.434(15) . ?
C4 H4A 0.9300 . ?
C5 C6 1.404(11) . ?
C5 H5 0.9300 . ?
C6 C7 1.429(10) . ?
C8 C9 1.435(9) . ?
C8 C13 1.447(9) . ?
C9 C10 1.412(6) . ?
C10 C11 1.360(11) . ?
C10 H10 0.9300 . ?
C11 C12 1.465(9) . ?
C11 H11 0.9300 . ?
C12 C13 1.366(13) . ?
C12 C17 1.414(11) . ?
C13 C14 1.400(8) . ?
C14 C15 1.374(12) . ?
C14 H14 0.9300 . ?
C15 C16 1.326(16) . ?
C15 H15 0.9300 . ?
C16 C17 1.392(11) . ?
C16 H16 0.9300 . ?
C17 H17 0.9300 . ?
N1B C8B 1.329(12) . ?
N1B C7B 1.330(10) . ?
C1B C2B 1.451(12) . ?
C1B H1BA 0.9600 . ?
C1B H1BB 0.9600 . ?
C1B H1BC 0.9600 . ?
N2B C9B 1.322(7) . ?
N2B C6B 1.373(12) . ?
C2B C3B 1.281(14) . ?
C2B C7B 1.529(16) . ?
C3B C4B 1.371(13) . ?
C3B H3B 0.9300 . ?
C4B C5B 1.427(18) . ?
C4B H4BA 0.9300 . ?
C5B C6B 1.413(11) . ?
C5B H5B 0.9300 . ?
C6B C7B 1.410(10) . ?
C8B C13B 1.435(13) . ?
C8B C9B 1.445(10) . ?
C9B C10B 1.469(7) . ?
C10B C11B 1.343(13) . ?
C10B H10B 0.9300 . ?
C11B C12B 1.469(11) . ?
C11B H11B 0.9300 . ?
C12B C13B 1.271(16) . ?
C12B C17B 1.469(17) . ?
C13B C14B 1.411(11) . ?
C14B C15B 1.362(13) . ?
C14B H14B 0.9300 . ?
C15B C16B 1.320(19) . ?
C15B H15B 0.9300 . ?
C16B C17B 1.363(15) . ?
C16B H16B 0.9300 . ?
C17B H17B 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
C8 N1 C7 118.2(8) . . ?
C2 C1 H1A 109.5 . . ?
C2 C1 H1B 109.5 . . ?
H1A C1 H1B 109.5 . . ?
C2 C1 H1C 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
C9 N2 C6 117.1(5) . . ?
C3 C2 C7 118.9(8) . . ?
C3 C2 C1 127.2(9) . . ?
C7 C2 C1 113.8(10) . . ?
C2 C3 C4 122.0(10) . . ?
C2 C3 H3 119.0 . . ?
C4 C3 H3 119.0 . . ?
C3 C4 C5 122.7(11) . . ?
C3 C4 H4A 118.6 . . ?
C5 C4 H4A 118.6 . . ?
C6 C5 C4 116.6(11) . . ?
C6 C5 H5 121.7 . . ?
C4 C5 H5 121.7 . . ?
N2 C6 C5 117.6(8) . . ?
N2 C6 C7 121.8(8) . . ?
C5 C6 C7 120.7(9) . . ?
N1 C7 C6 120.1(8) . . ?
N1 C7 C2 121.0(9) . . ?
C6 C7 C2 119.0(8) . . ?
N1 C8 C9 121.1(8) . . ?
N1 C8 C13 119.2(8) . . ?
C9 C8 C13 119.8(7) . . ?
N2 C9 C10 118.6(4) . . ?
N2 C9 C8 121.8(5) . . ?
C10 C9 C8 119.6(6) . . ?
C11 C10 C9 121.4(5) . . ?
C11 C10 H10 119.3 . . ?
C9 C10 H10 119.3 . . ?
C10 C11 C12 118.7(7) . . ?
C10 C11 H11 120.7 . . ?
C12 C11 H11 120.7 . . ?
C13 C12 C17 119.6(8) . . ?
C13 C12 C11 122.5(8) . . ?
C17 C12 C11 117.8(9) . . ?
C12 C13 C14 119.8(7) . . ?
C12 C13 C8 117.9(7) . . ?
C14 C13 C8 122.1(8) . . ?
C15 C14 C13 120.0(9) . . ?
C15 C14 H14 120.0 . . ?
C13 C14 H14 120.0 . . ?
C16 C15 C14 120.1(10) . . ?
C16 C15 H15 120.0 . . ?
C14 C15 H15 120.0 . . ?
C15 C16 C17 122.5(10) . . ?
C15 C16 H16 118.7 . . ?
C17 C16 H16 118.7 . . ?
C16 C17 C12 117.8(10) . . ?
C16 C17 H17 121.1 . . ?
C12 C17 H17 121.1 . . ?
C8B N1B C7B 116.9(9) . . ?
C2B C1B H1BA 109.5 . . ?
C2B C1B H1BB 109.5 . . ?
H1BA C1B H1BB 109.5 . . ?
C2B C1B H1BC 109.5 . . ?
H1BA C1B H1BC 109.5 . . ?
H1BB C1B H1BC 109.5 . . ?
C9B N2B C6B 116.6(6) . . ?
C3B C2B C1B 127.3(13) . . ?
C3B C2B C7B 116.9(11) . . ?
C1B C2B C7B 115.6(12) . . ?
C2B C3B C4B 126.1(13) . . ?
C2B C3B H3B 117.0 . . ?
C4B C3B H3B 117.0 . . ?
C3B C4B C5B 121.6(11) . . ?
C3B C4B H4BA 119.2 . . ?
C5B C4B H4BA 119.2 . . ?
C6B C5B C4B 115.1(11) . . ?
C6B C5B H5B 122.4 . . ?
C4B C5B H5B 122.4 . . ?
N2B C6B C7B 119.7(9) . . ?
N2B C6B C5B 117.1(10) . . ?
C7B C6B C5B 123.2(10) . . ?
N1B C7B C6B 123.7(9) . . ?
N1B C7B C2B 119.3(9) . . ?
C6B C7B C2B 116.8(9) . . ?
N1B C8B C13B 119.1(10) . . ?
N1B C8B C9B 120.5(11) . . ?
C13B C8B C9B 120.3(12) . . ?
N2B C9B C8B 122.5(8) . . ?
N2B C9B C10B 120.2(5) . . ?
C8B C9B C10B 117.3(8) . . ?
C11B C10B C9B 121.1(8) . . ?
C11B C10B H10B 119.5 . . ?
C9B C10B H10B 119.5 . . ?
C10B C11B C12B 116.3(12) . . ?
C10B C11B H11B 121.9 . . ?
C12B C11B H11B 121.9 . . ?
C13B C12B C11B 127.4(14) . . ?
C13B C12B C17B 118.9(12) . . ?
C11B C12B C17B 113.3(12) . . ?
C12B C13B C14B 120.5(12) . . ?
C12B C13B C8B 117.4(12) . . ?
C14B C13B C8B 122.1(12) . . ?
C15B C14B C13B 118.7(14) . . ?
C15B C14B H14B 120.6 . . ?
C13B C14B H14B 120.6 . . ?
C16B C15B C14B 124.1(17) . . ?
C16B C15B H15B 117.9 . . ?
C14B C15B H15B 117.9 . . ?
C15B C16B C17B 116.7(15) . . ?
C15B C16B H16B 121.6 . . ?
C17B C16B H16B 121.6 . . ?
C16B C17B C12B 120.8(14) . . ?
C16B C17B H17B 119.6 . . ?
C12B C17B H17B 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
C7 C2 C3 C4 -3(2) . . . . ?
C1 C2 C3 C4 -178.2(18) . . . . ?
C2 C3 C4 C5 0(3) . . . . ?
C3 C4 C5 C6 3(3) . . . . ?
C9 N2 C6 C5 178.5(8) . . . . ?
C9 N2 C6 C7 -2.0(12) . . . . ?
C4 C5 C6 N2 177.4(15) . . . . ?
C4 C5 C6 C7 -2(2) . . . . ?
C8 N1 C7 C6 0.1(19) . . . . ?
C8 N1 C7 C2 -178.0(11) . . . . ?
N2 C6 C7 N1 1.1(19) . . . . ?
C5 C6 C7 N1 -179.4(13) . . . . ?
N2 C6 C7 C2 179.3(10) . . . . ?
C5 C6 C7 C2 -1.2(18) . . . . ?
C3 C2 C7 N1 -177.9(14) . . . . ?
C1 C2 C7 N1 -2.3(19) . . . . ?
C3 C2 C7 C6 4(2) . . . . ?
C1 C2 C7 C6 179.6(12) . . . . ?
C7 N1 C8 C9 -0.4(15) . . . . ?
C7 N1 C8 C13 179.8(12) . . . . ?
C6 N2 C9 C10 -179.5(6) . . . . ?
C6 N2 C9 C8 1.7(8) . . . . ?
N1 C8 C9 N2 -0.6(11) . . . . ?
C13 C8 C9 N2 179.3(7) . . . . ?
N1 C8 C9 C10 -179.4(8) . . . . ?
C13 C8 C9 C10 0.5(11) . . . . ?
N2 C9 C10 C11 -179.2(7) . . . . ?
C8 C9 C10 C11 -0.4(10) . . . . ?
C9 C10 C11 C12 2.0(13) . . . . ?
C10 C11 C12 C13 -4.0(17) . . . . ?
C10 C11 C12 C17 -178.9(10) . . . . ?
C17 C12 C13 C14 -4.7(19) . . . . ?
C11 C12 C13 C14 -179.6(12) . . . . ?
C17 C12 C13 C8 178.9(11) . . . . ?
C11 C12 C13 C8 4.1(18) . . . . ?
N1 C8 C13 C12 177.5(11) . . . . ?
C9 C8 C13 C12 -2.3(14) . . . . ?
N1 C8 C13 C14 1.3(15) . . . . ?
C9 C8 C13 C14 -178.6(10) . . . . ?
C12 C13 C14 C15 4.4(19) . . . . ?
C8 C13 C14 C15 -179.4(11) . . . . ?
C13 C14 C15 C16 -2(2) . . . . ?
C14 C15 C16 C17 1(2) . . . . ?
C15 C16 C17 C12 -1(2) . . . . ?
C13 C12 C17 C16 3.1(19) . . . . ?
C11 C12 C17 C16 178.2(11) . . . . ?
C1B C2B C3B C4B -175.9(16) . . . . ?
C7B C2B C3B C4B -1(3) . . . . ?
C2B C3B C4B C5B -3(3) . . . . ?
C3B C4B C5B C6B 4(2) . . . . ?
C9B N2B C6B C7B -3.2(16) . . . . ?
C9B N2B C6B C5B 178.0(11) . . . . ?
C4B C5B C6B N2B 178.3(13) . . . . ?
C4B C5B C6B C7B 0(2) . . . . ?
C8B N1B C7B C6B -1.2(18) . . . . ?
C8B N1B C7B C2B -176.4(15) . . . . ?
N2B C6B C7B N1B 3(2) . . . . ?
C5B C6B C7B N1B -178.5(14) . . . . ?
N2B C6B C7B C2B 178.0(12) . . . . ?
C5B C6B C7B C2B -3(2) . . . . ?
C3B C2B C7B N1B 179.6(14) . . . . ?
C1B C2B C7B N1B -5(2) . . . . ?
C3B C2B C7B C6B 4(2) . . . . ?
C1B C2B C7B C6B 179.5(14) . . . . ?
C7B N1B C8B C13B -178.7(16) . . . . ?
C7B N1B C8B C9B 0(2) . . . . ?
C6B N2B C9B C8B 2.4(14) . . . . ?
C6B N2B C9B C10B 179.6(9) . . . . ?
N1B C8B C9B N2B -1(2) . . . . ?
C13B C8B C9B N2B 178.0(13) . . . . ?
N1B C8B C9B C10B -178.2(12) . . . . ?
C13B C8B C9B C10B 1(2) . . . . ?
N2B C9B C10B C11B -178.3(9) . . . . ?
C8B C9B C10B C11B -1.0(15) . . . . ?
C9B C10B C11B C12B 2.6(17) . . . . ?
C10B C11B C12B C13B -5(2) . . . . ?
C10B C11B C12B C17B -177.6(13) . . . . ?
C11B C12B C13B C14B -177.2(14) . . . . ?
C17B C12B C13B C14B -5(3) . . . . ?
C11B C12B C13B C8B 5(3) . . . . ?
C17B C12B C13B C8B 177.1(17) . . . . ?
N1B C8B C13B C12B 176.5(16) . . . . ?
C9B C8B C13B C12B -3(3) . . . . ?
N1B C8B C13B C14B -2(3) . . . . ?
C9B C8B C13B C14B 179.3(14) . . . . ?
C12B C13B C14B C15B 2(2) . . . . ?
C8B C13B C14B C15B -179.5(18) . . . . ?
C13B C14B C15B C16B -1(3) . . . . ?
C14B C15B C16B C17B 2(4) . . . . ?
C15B C16B C17B C12B -4(4) . . . . ?
C13B C12B C17B C16B 6(3) . . . . ?
C11B C12B C17B C16B 179(2) . . . . ?

_refine_diff_density_max         0.088
_refine_diff_density_min         -0.114
_refine_diff_density_rms         0.025



_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: deuterated chloroform'
####################################################################### 
# 
# 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_B19812
_database_code_depnum_ccdc_archive 'CCDC 2310626'
loop_
_audit_author_name
_audit_author_address
'Pascal Retailleau'
;ICSN CNRS University Paris Saclay
France
;
_audit_update_record             
;
2023-11-27 deposited with the CCDC.	2024-01-10 downloaded from the CCDC.
;

# start Validation Reply Form
_vrf_THETM01_B19812              
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: Available tiny needle-like crystal diffracted very little beyond the 
atomic resolution limit despite long exposure, Br atom and HPAD detector.
;
_vrf_PLAT088_B19812              
;
PROBLEM: Poor Data / Parameter Ratio ....................       7.42 Note  
RESPONSE: See above
;
# end Validation Reply Form

_audit_creation_method           SHELXL-2019/3
_chemical_name_systematic        9-bromobenzo[a]phenazine
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C16 H9 Br N2'
_chemical_formula_sum            'C16 H9 Br N2'
_chemical_formula_weight         309.16

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'
Br Br -0.2901 2.4595 '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                   16.013(2)
_cell_length_b                   4.6349(7)
_cell_length_c                   16.5622(19)
_cell_angle_alpha                90
_cell_angle_beta                 96.230(13)
_cell_angle_gamma                90
_cell_volume                     1222.0(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2061
_cell_measurement_theta_min      3.7200
_cell_measurement_theta_max      24.7910

_exptl_crystal_description       needle
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.681
_exptl_crystal_F_000             616
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
5 0 3 0.0234
0 -1 -1 0.1046
0 1 1 0.0866
-4 0 -5 0.0031
4 0 5 0.0223
-5 0 2 0.0180
5 0 -2 0.0213
-1 0 5 0.0207
1 0 -5 0.0170
_exptl_crystal_size_max          0.208
_exptl_crystal_size_mid          0.045
_exptl_crystal_size_min          0.025
_exptl_absorpt_coefficient_mu    3.348

_exptl_absorpt_correction_T_min  0.614
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.43.96a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_monochromator  mirror
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_ambient_temperature      293(2)
_diffrn_reflns_number            6207
_diffrn_reflns_av_unetI/netI     0.0880
_diffrn_reflns_av_R_equivalents  0.1278
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_k_min       -4
_diffrn_reflns_limit_k_max       4
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         3.362
_diffrn_reflns_theta_max         20.807
_diffrn_reflns_theta_full        20.807
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measured_fraction_theta_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_point_group_measured_fraction_full 0.992
_reflns_number_total             1276
_reflns_number_gt                1009
_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       'CrysAlisPro system (CCD 43.96a 64-bit)'
_computing_cell_refinement       'CrysAlisPro 1.171.43.96a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.43.96a (Rigaku OD, 2023)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015a)'
_computing_structure_refinement  'SHELXL-2019/2 (Sheldrick, 2015b)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_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)+(0.1132P)²+1.6583P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     other
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         1276
_refine_ls_number_parameters     172
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0882
_refine_ls_R_factor_gt           0.0723
_refine_ls_wR_factor_ref         0.1919
_refine_ls_wR_factor_gt          0.1744
_refine_ls_goodness_of_fit_ref   1.109
_refine_ls_restrained_S_all      1.109
_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 0.4800(5) 0.572(2) 0.3367(5) 0.048(2) Uani 1 1 d . . . . .
C3 C 0.5847(6) 0.2691(18) 0.3906(6) 0.042(2) Uani 1 1 d . . . . .
C4 C 0.6189(6) 0.065(2) 0.4492(5) 0.048(2) Uani 1 1 d . . . . .
H4 H 0.587093 -0.002444 0.488998 0.058 Uiso 1 1 calc R U . . .
C5 C 0.6978(5) -0.0291(18) 0.4463(5) 0.044(2) Uani 1 1 d . . . . .
C6 C 0.7462(6) 0.053(2) 0.3833(5) 0.050(2) Uani 1 1 d . . . . .
H6 H 0.799330 -0.026106 0.381196 0.060 Uiso 1 1 calc R U . . .
C7 C 0.7164(6) 0.2420(17) 0.3274(6) 0.044(2) Uani 1 1 d . . . . .
H7 H 0.749112 0.297143 0.287002 0.052 Uiso 1 1 calc R U . . .
C8 C 0.6342(5) 0.362(2) 0.3287(5) 0.043(2) Uani 1 1 d . . . . .
C9 C 0.4972(5) 0.870(2) 0.2152(5) 0.045(2) Uani 1 1 d . . . . .
C10 C 0.5430(5) 0.966(2) 0.1529(5) 0.050(2) Uani 1 1 d . . . . .
H10 H 0.596567 0.892516 0.149314 0.060 Uiso 1 1 calc R U . . .
C11 C 0.5101(7) 1.166(2) 0.0967(6) 0.062(3) Uani 1 1 d . . . . .
H11 H 0.541654 1.229581 0.056238 0.074 Uiso 1 1 calc R U . . .
C12 C 0.4299(7) 1.272(2) 0.1009(8) 0.064(3) Uani 1 1 d . . . . .
H12 H 0.407209 1.403478 0.062048 0.076 Uiso 1 1 calc R U . . .
C13 C 0.3842(7) 1.188(2) 0.1609(7) 0.062(3) Uani 1 1 d . . . . .
H13 H 0.331113 1.267005 0.163573 0.075 Uiso 1 1 calc R U . . .
C14 C 0.4156(5) 0.983(2) 0.2192(5) 0.050(2) Uani 1 1 d . . . . .
C15 C 0.3673(6) 0.889(2) 0.2830(6) 0.060(3) Uani 1 1 d . . . . .
H15 H 0.314186 0.966288 0.286054 0.072 Uiso 1 1 calc R U . . .
C16 C 0.3970(6) 0.693(2) 0.3376(7) 0.057(3) Uani 1 1 d . . . . .
H16 H 0.363634 0.633165 0.377071 0.068 Uiso 1 1 calc R U . . .
Br1 Br 0.74796(7) -0.2822(2) 0.52698(6) 0.0654(6) Uani 1 1 d . . . . .
N1 N 0.6060(4) 0.5543(15) 0.2709(4) 0.0428(18) Uani 1 1 d . . . . .
C1 C 0.5305(6) 0.6582(18) 0.2756(5) 0.042(2) Uani 1 1 d . . . . .
N2 N 0.5064(4) 0.3771(18) 0.3934(4) 0.051(2) Uani 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 N2 1.339(12) . ?
C2 C1 1.419(12) . ?
C2 C16 1.444(13) . ?
C3 N2 1.355(12) . ?
C3 C4 1.423(13) . ?
C3 C8 1.429(13) . ?
C4 C5 1.342(12) . ?
C4 H4 0.9300 . ?
C5 C6 1.419(12) . ?
C5 Br1 1.890(9) . ?
C6 C7 1.325(12) . ?
C6 H6 0.9300 . ?
C7 C8 1.431(13) . ?
C7 H7 0.9300 . ?
C8 N1 1.349(11) . ?
C9 C10 1.402(12) . ?
C9 C14 1.416(12) . ?
C9 C1 1.459(14) . ?
C10 C11 1.378(13) . ?
C10 H10 0.9300 . ?
C11 C12 1.384(15) . ?
C11 H11 0.9300 . ?
C12 C13 1.354(16) . ?
C12 H12 0.9300 . ?
C13 C14 1.410(14) . ?
C13 H13 0.9300 . ?
C14 C15 1.444(13) . ?
C15 C16 1.331(14) . ?
C15 H15 0.9300 . ?
C16 H16 0.9300 . ?
N1 C1 1.312(11) . ?

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
N2 C2 C1 121.9(8) . . ?
N2 C2 C16 118.4(8) . . ?
C1 C2 C16 119.7(9) . . ?
N2 C3 C4 120.8(8) . . ?
N2 C3 C8 120.0(9) . . ?
C4 C3 C8 119.2(8) . . ?
C5 C4 C3 119.1(8) . . ?
C5 C4 H4 120.4 . . ?
C3 C4 H4 120.4 . . ?
C4 C5 C6 122.0(8) . . ?
C4 C5 Br1 120.4(7) . . ?
C6 C5 Br1 117.5(7) . . ?
C7 C6 C5 120.4(8) . . ?
C7 C6 H6 119.8 . . ?
C5 C6 H6 119.8 . . ?
C6 C7 C8 120.6(8) . . ?
C6 C7 H7 119.7 . . ?
C8 C7 H7 119.7 . . ?
N1 C8 C3 122.6(8) . . ?
N1 C8 C7 118.9(7) . . ?
C3 C8 C7 118.4(9) . . ?
C10 C9 C14 118.4(9) . . ?
C10 C9 C1 122.5(8) . . ?
C14 C9 C1 119.1(8) . . ?
C11 C10 C9 121.3(9) . . ?
C11 C10 H10 119.4 . . ?
C9 C10 H10 119.4 . . ?
C10 C11 C12 119.7(10) . . ?
C10 C11 H11 120.2 . . ?
C12 C11 H11 120.2 . . ?
C13 C12 C11 120.9(10) . . ?
C13 C12 H12 119.6 . . ?
C11 C12 H12 119.6 . . ?
C12 C13 C14 121.0(9) . . ?
C12 C13 H13 119.5 . . ?
C14 C13 H13 119.5 . . ?
C13 C14 C9 118.8(9) . . ?
C13 C14 C15 121.7(9) . . ?
C9 C14 C15 119.5(9) . . ?
C16 C15 C14 121.6(9) . . ?
C16 C15 H15 119.2 . . ?
C14 C15 H15 119.2 . . ?
C15 C16 C2 121.2(9) . . ?
C15 C16 H16 119.4 . . ?
C2 C16 H16 119.4 . . ?
C1 N1 C8 116.2(7) . . ?
N1 C1 C2 122.6(8) . . ?
N1 C1 C9 118.5(7) . . ?
C2 C1 C9 118.9(8) . . ?
C2 N2 C3 116.7(7) . . ?

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
N2 C3 C4 C5 -177.6(8) . . . . ?
C8 C3 C4 C5 1.9(12) . . . . ?
C3 C4 C5 C6 -4.5(13) . . . . ?
C3 C4 C5 Br1 176.1(6) . . . . ?
C4 C5 C6 C7 4.2(14) . . . . ?
Br1 C5 C6 C7 -176.4(7) . . . . ?
C5 C6 C7 C8 -1.2(13) . . . . ?
N2 C3 C8 N1 -0.7(12) . . . . ?
C4 C3 C8 N1 179.8(8) . . . . ?
N2 C3 C8 C7 -179.6(7) . . . . ?
C4 C3 C8 C7 0.9(12) . . . . ?
C6 C7 C8 N1 179.8(8) . . . . ?
C6 C7 C8 C3 -1.2(13) . . . . ?
C14 C9 C10 C11 0.3(13) . . . . ?
C1 C9 C10 C11 -179.9(8) . . . . ?
C9 C10 C11 C12 -1.0(14) . . . . ?
C10 C11 C12 C13 1.9(15) . . . . ?
C11 C12 C13 C14 -2.0(15) . . . . ?
C12 C13 C14 C9 1.3(14) . . . . ?
C12 C13 C14 C15 -179.3(9) . . . . ?
C10 C9 C14 C13 -0.4(12) . . . . ?
C1 C9 C14 C13 179.8(8) . . . . ?
C10 C9 C14 C15 -179.8(8) . . . . ?
C1 C9 C14 C15 0.4(12) . . . . ?
C13 C14 C15 C16 179.4(9) . . . . ?
C9 C14 C15 C16 -1.2(14) . . . . ?
C14 C15 C16 C2 1.7(15) . . . . ?
N2 C2 C16 C15 179.7(9) . . . . ?
C1 C2 C16 C15 -1.3(14) . . . . ?
C3 C8 N1 C1 1.5(12) . . . . ?
C7 C8 N1 C1 -179.6(7) . . . . ?
C8 N1 C1 C2 -1.0(12) . . . . ?
C8 N1 C1 C9 179.3(7) . . . . ?
N2 C2 C1 N1 -0.4(13) . . . . ?
C16 C2 C1 N1 -179.3(8) . . . . ?
N2 C2 C1 C9 179.4(8) . . . . ?
C16 C2 C1 C9 0.5(12) . . . . ?
C10 C9 C1 N1 -0.1(13) . . . . ?
C14 C9 C1 N1 179.8(7) . . . . ?
C10 C9 C1 C2 -179.9(8) . . . . ?
C14 C9 C1 C2 0.0(12) . . . . ?
C1 C2 N2 C3 1.2(12) . . . . ?
C16 C2 N2 C3 -179.9(8) . . . . ?
C4 C3 N2 C2 178.8(8) . . . . ?
C8 C3 N2 C2 -0.7(12) . . . . ?

_refine_diff_density_max         1.400
_refine_diff_density_min         -0.888
_refine_diff_density_rms         0.136





_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: deuterated chloroform'
####################################################################### 
# 
# 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_CO44P1
_database_code_depnum_ccdc_archive 'CCDC 2310627'
loop_
_audit_author_name
_audit_author_address
'Pascal Retailleau'
;ICSN CNRS University Paris Saclay
France
;
_audit_update_record             
;
2023-11-27 deposited with the CCDC.	2024-01-10 downloaded from the CCDC.
;
_audit_creation_date             2023-11-26
_audit_creation_method           
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_chemical_name_systematic        6-chloro-2-phenylquinoxaline

_chemical_formula_moiety         'C14 H9 Cl N2'
_chemical_formula_sum            'C14 H9 Cl N2'
_chemical_formula_weight         240.693
_chemical_absolute_configuration .
_chemical_oxdiff_formula         'C19 H14 Cl N2'
loop_
_atom_type_symbol
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
_atom_type_scat_dispersion_source
C 0.00347 0.00161 'NoSpherA2: Chem.Sci. 2021, DOI:10.1039/D0SC05526C'
'Henke, Gullikson and Davis, At. Data and Nucl. Data Tables, 1993, 54, 2'
Cl 0.14873 0.16029 'NoSpherA2: Chem.Sci. 2021, DOI:10.1039/D0SC05526C'
'Henke, Gullikson and Davis, At. Data and Nucl. Data Tables, 1993, 54, 2'
H 0.00000 0.00000 'NoSpherA2: Chem.Sci. 2021, DOI:10.1039/D0SC05526C'
'Henke, Gullikson and Davis, At. Data and Nucl. Data Tables, 1993, 54, 2'
N 0.00653 0.00323 'NoSpherA2: Chem.Sci. 2021, DOI:10.1039/D0SC05526C'
'Henke, Gullikson and Davis, At. Data and Nucl. Data Tables, 1993, 54, 2'

_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_H-M_alt        'P 1 21 1'
_space_group_name_Hall           ' P 2yb'
loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 x,y,z
2 -x,y+1/2,-z

_symmetry_Int_Tables_number      4
_cell_length_a                   9.5508(6)
_cell_length_b                   4.7677(3)
_cell_length_c                   12.4996(9)
_cell_angle_alpha                90
_cell_angle_beta                 103.508(7)
_cell_angle_gamma                90
_cell_volume                     553.43(7)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    5027
_cell_measurement_theta_max      31.1120
_cell_measurement_theta_min      4.2660
_exptl_crystal_description       stick
_exptl_crystal_colour            colourless
_exptl_absorpt_coefficient_mu    0.319
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.650
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.42.79a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.444
_exptl_crystal_F_000             248.422
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
1 0 5 0.0291
-1 0 -5 0.0494
-5 -4 3 0.1693
5 4 -3 0.2121
-4 0 5 0.0620
4 0 -5 0.0571
0 -5 -1 0.1971
-5 0 -2 0.0577
5 0 2 0.0377
-1 -3 5 0.1665

_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.08
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
0.9768 -0.0026 5.0196 0.1486 0.2787 0.0425
-0.9768 0.0026 -5.0196 -0.1486 -0.2787 -0.0425
-5.0039 -4.0034 2.9421 -0.0543 -0.0819 0.7001
5.0039 4.0034 -2.9421 0.0543 0.0819 -0.7001
-4.0142 -0.0005 4.9845 -0.1985 0.2423 0.1972
4.0142 0.0005 -4.9845 0.1985 -0.2423 -0.1972
0.0042 -5.0048 -1.0404 0.2907 -0.3147 0.6120
-4.9824 0.0030 -2.0401 -0.3787 -0.1450 0.1253
4.9824 -0.0030 2.0401 0.3787 0.1450 -0.1253
-1.0196 -3.0049 4.9828 0.1937 0.1079 0.4804

_diffrn_reflns_av_R_equivalents  0.0383
_diffrn_reflns_av_unetI/netI     0.0374
_diffrn_reflns_Laue_measured_fraction_full 0.9956
_diffrn_reflns_Laue_measured_fraction_max 0.9707
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            10590
_diffrn_reflns_point_group_measured_fraction_full 0.9835
_diffrn_reflns_point_group_measured_fraction_max 0.9072
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         30.51
_diffrn_reflns_theta_min         3.35
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.9956
_diffrn_measured_fraction_theta_max 0.9707
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -22.00  95.00   0.50    2.50    --    6.50  43.00-143.00  234
  2  ω     -8.00  23.00   0.50    2.50    --   -7.20  43.00-143.00   62
  3  ω    -14.00  37.00   0.50    2.50    --    6.50  57.00  60.00  102
  4  ω     42.00  69.00   0.50    2.50    --    6.50  38.00 -30.00   54
  5  ω     67.00  92.00   0.50    2.50    --    6.50  57.00  60.00   50
  6  ω    -21.00   4.00   0.50    2.50    --    6.50  38.00 -30.00   50
  7  ω    -38.00  81.00   0.50    2.50    --   -7.20  38.00 150.00  238
  8  ω    -37.00  81.00   0.50    2.50    --   -7.20  38.00  60.00  236
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_ambient_temperature      293(2)
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0693978000
_diffrn_orient_matrix_UB_12      -0.0613627000
_diffrn_orient_matrix_UB_13      0.0160658000
_diffrn_orient_matrix_UB_21      0.0069423000
_diffrn_orient_matrix_UB_22      0.0516087000
_diffrn_orient_matrix_UB_23      0.0542049000
_diffrn_orient_matrix_UB_31      -0.0311482000
_diffrn_orient_matrix_UB_32      -0.1253151000
_diffrn_orient_matrix_UB_33      0.0144612000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_reflns_Friedel_coverage         0.828
_reflns_limit_h_max              13
_reflns_limit_h_min              -13
_reflns_limit_k_max              6
_reflns_limit_k_min              -6
_reflns_limit_l_max              17
_reflns_limit_l_min              -17
_reflns_number_gt                2500
_reflns_number_total             3070
_reflns_threshold_expression     I>=2u(I)
_computing_cell_refinement       'CrysAlisPro 1.171.42.79a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.79a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.79a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  
'olex2.refine 1.5-ac5-024 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         0.1845
_refine_diff_density_min         -0.2707
_refine_diff_density_rms         0.0420
_refine_ls_abs_structure_details 
'Hooft, R.W.W., Straver, L.H., Spek, A.L.(2010). J. Appl. Cryst.,43, 665-668.'
_refine_ls_abs_structure_Flack   -0.01(3)
_refine_ls_d_res_high            0.7000
_refine_ls_d_res_low             6.0769
_refine_ls_goodness_of_fit_ref   1.1208
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     235
_refine_ls_number_reflns         3070
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0427
_refine_ls_R_factor_gt           0.0295
_refine_ls_restrained_S_all      1.1208
_refine_ls_shift/su_max          -0.0002
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0104P)²+0.0100P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0539
_refine_ls_wR_factor_ref         0.0573
_refine_special_details          
;
Refinement using NoSpherA2, an implementation of
NOn-SPHERical Atom-form-factors in Olex2.
Please cite:
F. Kleemiss et al. Chem. Sci. DOI 10.1039/D0SC05526C - 2021
NoSpherA2 implementation of HAR makes use of
tailor-made aspherical atomic form factors calculated
on-the-fly from a Hirshfeld-partitioned electron density (ED) - not from
spherical-atom form factors.

The ED is calculated from a gaussian basis set single determinant SCF
wavefunction - either Hartree-Fock or DFT using selected funtionals
 - for a fragment of the crystal.
This fragment can be embedded in an electrostatic crystal field by employing cluster 
charges or modelled using implicit solvation models, depending on the software used.
The following options were used:
   SOFTWARE:       ORCA 5.0
   PARTITIONING:   NoSpherA2
   INT ACCURACY:   Normal
   METHOD:         B3LYP
   BASIS SET:      jorge-TZP
   CHARGE:         0
   MULTIPLICITY:   1
   DATE:           2023-11-26_16-33-59
;
_olex2_refinement_description    
;
;
_atom_sites_solution_primary     dual
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_refinement_flags_posn
Cl1 Cl 0.90425(3) 1.28956(7) 0.39252(3) 0.05327(11) Uani 1.000000 .
N1 N 0.44761(10) 0.4376(2) 0.30662(7) 0.0308(2) Uani 1.000000 .
N2 N 0.58132(11) 0.5961(2) 0.13809(8) 0.0386(3) Uani 1.000000 .
C8 C 0.55360(12) 0.6345(3) 0.32408(9) 0.0294(2) Uani 1.000000 .
C3 C 0.62146(12) 0.7159(2) 0.23981(9) 0.0310(3) Uani 1.000000 .
C4 C 0.73106(13) 0.9217(3) 0.26034(11) 0.0361(3) Uani 1.000000 .
H4 H 0.7837(15) 0.986(3) 0.1949(13) 0.064(5) Uani 1.000000 .
C1 C 0.40910(11) 0.3239(3) 0.20803(8) 0.0304(3) Uani 1.000000 .
C7 C 0.59714(13) 0.7621(3) 0.42852(10) 0.0366(3) Uani 1.000000 .
H7 H 0.5415(14) 0.695(3) 0.4897(12) 0.065(5) Uani 1.000000 .
C9 C 0.29312(12) 0.1115(2) 0.18794(9) 0.0317(2) Uani 1.000000 .
C6 C 0.70341(14) 0.9599(3) 0.44802(11) 0.0399(3) Uani 1.000000 .
H6 H 0.7367(15) 1.064(4) 0.5267(12) 0.065(5) Uani 1.000000 .
C5 C 0.77048(13) 1.0394(2) 0.36333(10) 0.0364(3) Uani 1.000000 .
C14 C 0.22483(14) 0.0439(3) 0.27213(12) 0.0413(3) Uani 1.000000 .
H14 H 0.2600(14) 0.153(3) 0.3510(11) 0.056(4) Uani 1.000000 .
C2 C 0.47865(14) 0.4080(3) 0.12348(10) 0.0386(3) Uani 1.000000 .
H2 H 0.4464(14) 0.317(5) 0.0413(11) 0.069(5) Uani 1.000000 .
C10 C 0.24892(15) -0.0258(3) 0.08710(11) 0.0413(3) Uani 1.000000 .
H10 H 0.2954(18) 0.023(4) 0.0216(13) 0.074(5) Uani 1.000000 .
C13 C 0.11646(15) -0.1553(3) 0.25589(13) 0.0472(4) Uani 1.000000 .
H13 H 0.0653(17) -0.202(4) 0.3209(14) 0.085(5) Uani 1.000000 .
C11 C 0.13920(15) -0.2250(4) 0.07100(12) 0.0498(3) Uani 1.000000 .
H11 H 0.1068(18) -0.334(4) -0.0091(16) 0.097(7) Uani 1.000000 .
C12 C 0.07286(16) -0.2900(3) 0.15546(13) 0.0486(4) Uani 1.000000 .
H12 H -0.0100(17) -0.450(4) 0.1442(14) 0.079(5) Uani 1.000000 .


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
Cl1 C5 1.7234(12) . ?
N1 C8 1.3603(15) . ?
N1 C1 1.3177(14) . ?
N2 C3 1.3644(14) . ?
N2 C2 1.3099(16) . ?
C8 C3 1.4138(15) . ?
C8 C7 1.4119(16) . ?
C3 C4 1.4139(16) . ?
C4 H4 1.099(14) . ?
C4 C5 1.3739(17) . ?
C1 C9 1.4782(17) . ?
C1 C2 1.4308(15) . ?
C7 H7 1.077(15) . ?
C7 C6 1.365(2) . ?
C9 C14 1.3991(17) . ?
C9 C10 1.3953(18) . ?
C6 H6 1.082(14) . ?
C6 C5 1.4113(18) . ?
C14 H14 1.095(14) . ?
C14 C13 1.3843(19) . ?
C2 H2 1.090(15) . ?
C10 H10 1.045(16) . ?
C10 C11 1.394(2) . ?
C13 H13 1.064(16) . ?
C13 C12 1.385(2) . ?
C11 H11 1.105(19) . ?
C11 C12 1.387(2) . ?
C12 H12 1.083(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
C1 N1 C8 117.96(10) . . ?
C2 N2 C3 117.04(10) . . ?
C3 C8 N1 121.54(10) . . ?
C7 C8 N1 119.55(10) . . ?
C7 C8 C3 118.91(11) . . ?
C8 C3 N2 120.11(10) . . ?
C4 C3 N2 119.63(10) . . ?
C4 C3 C8 120.26(11) . . ?
H4 C4 C3 120.5(8) . . ?
C5 C4 C3 118.87(12) . . ?
C5 C4 H4 120.7(8) . . ?
C9 C1 N1 118.37(9) . . ?
C2 C1 N1 119.94(11) . . ?
C2 C1 C9 121.68(10) . . ?
H7 C7 C8 116.1(7) . . ?
C6 C7 C8 120.59(12) . . ?
C6 C7 H7 123.3(7) . . ?
C14 C9 C1 119.51(10) . . ?
C10 C9 C1 122.10(11) . . ?
C10 C9 C14 118.39(12) . . ?
H6 C6 C7 121.9(8) . . ?
C5 C6 C7 120.03(13) . . ?
C5 C6 H6 118.0(8) . . ?
C4 C5 Cl1 120.56(10) . . ?
C6 C5 Cl1 118.10(10) . . ?
C6 C5 C4 121.34(12) . . ?
H14 C14 C9 117.9(7) . . ?
C13 C14 C9 120.79(13) . . ?
C13 C14 H14 121.3(7) . . ?
C1 C2 N2 123.40(12) . . ?
H2 C2 N2 116.1(8) . . ?
H2 C2 C1 120.5(8) . . ?
H10 C10 C9 120.6(9) . . ?
C11 C10 C9 120.58(14) . . ?
C11 C10 H10 118.8(9) . . ?
H13 C13 C14 119.4(9) . . ?
C12 C13 C14 120.49(15) . . ?
C12 C13 H13 120.1(9) . . ?
H11 C11 C10 119.5(10) . . ?
C12 C11 C10 120.28(14) . . ?
C12 C11 H11 120.2(10) . . ?
C11 C12 C13 119.48(14) . . ?
H12 C12 C13 120.0(10) . . ?
H12 C12 C11 120.5(10) . . ?

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
Cl1 C5 C4 C3 179.61(9) . . . . ?
Cl1 C5 C6 C7 -179.87(11) . . . . ?
N1 C8 C3 N2 -0.10(13) . . . . ?
N1 C8 C3 C4 179.82(10) . . . . ?
N1 C8 C7 C6 179.90(12) . . . . ?
N1 C1 C9 C14 1.97(13) . . . . ?
N1 C1 C9 C10 -177.91(11) . . . . ?
N1 C1 C2 N2 0.08(14) . . . . ?
N2 C3 C8 C7 -179.92(11) . . . . ?
N2 C3 C4 C5 -179.79(11) . . . . ?
N2 C2 C1 C9 179.71(11) . . . . ?
C8 C3 C4 C5 0.29(12) . . . . ?
C8 C7 C6 C5 0.24(16) . . . . ?
C3 C4 C5 C6 -0.33(13) . . . . ?
C4 C5 C6 C7 0.06(15) . . . . ?
C1 C9 C14 C13 -179.61(12) . . . . ?
C1 C9 C10 C11 179.98(13) . . . . ?
C9 C14 C13 C12 -0.49(15) . . . . ?
C9 C10 C11 C12 -0.26(15) . . . . ?
C14 C13 C12 C11 0.34(17) . . . . ?
C10 C11 C12 C13 0.04(19) . . . . ?


_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.915
_oxdiff_exptl_absorpt_empirical_full_min 0.503

_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: deuterated chloroform'
####################################################################### 
# 
# 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_TD55
_database_code_depnum_ccdc_archive 'CCDC 2310628'
loop_
_audit_author_name
_audit_author_address
'Pascal Retailleau'
;ICSN CNRS University Paris Saclay
France
;
_audit_update_record             
;
2023-11-27 deposited with the CCDC.	2024-01-10 downloaded from the CCDC.
;
_audit_creation_date             2023-11-26
_audit_creation_method           
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_chemical_formula_moiety         'C14 H9 Br N2'
_chemical_formula_sum            'C14 H9 Br N2'
_chemical_formula_weight         285.144
_chemical_absolute_configuration .
_chemical_oxdiff_formula         'C19 H14 Br N2'
loop_
_atom_type_symbol
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
_atom_type_scat_dispersion_source
Br -0.28346 2.55990 'NoSpherA2: Chem.Sci. 2021, DOI:10.1039/D0SC05526C'
'Henke, Gullikson and Davis, At. Data and Nucl. Data Tables, 1993, 54, 2'
C 0.00347 0.00161 'NoSpherA2: Chem.Sci. 2021, DOI:10.1039/D0SC05526C'
'Henke, Gullikson and Davis, At. Data and Nucl. Data Tables, 1993, 54, 2'
H 0.00000 0.00000 'NoSpherA2: Chem.Sci. 2021, DOI:10.1039/D0SC05526C'
'Henke, Gullikson and Davis, At. Data and Nucl. Data Tables, 1993, 54, 2'
N 0.00653 0.00323 'NoSpherA2: Chem.Sci. 2021, DOI:10.1039/D0SC05526C'
'Henke, Gullikson and Davis, At. Data and Nucl. Data Tables, 1993, 54, 2'

_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_H-M_alt        'P 1 21 1'
_space_group_name_Hall           ' P 2yb'
loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 x,y,z
2 -x,y+1/2,-z

_symmetry_Int_Tables_number      4
_cell_length_a                   9.6512(5)
_cell_length_b                   4.9125(2)
_cell_length_c                   12.4349(9)
_cell_angle_alpha                90
_cell_angle_beta                 104.633(6)
_cell_angle_gamma                90
_cell_volume                     570.43(6)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    4422
_cell_measurement_theta_max      27.6730
_cell_measurement_theta_min      3.3840
_exptl_crystal_description       stick
_exptl_crystal_colour            colourless
_exptl_absorpt_coefficient_mu    3.578
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.356
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.42.79a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.660
_exptl_crystal_F_000             283.744
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
13 1 -1 0.0408
-13 -1 1 0.0408
-1 4 5 0.2425
0 -4 -5 0.2440
0 0 1 0.0606
0 0 -1 0.0553
-12 0 11 0.0525
12 -1 -11 0.0612
12 0 4 0.0476
7 0 -17 0.0584
-1 0 0 0.0368
-3 -6 6 0.2702

_exptl_crystal_size_max          0.59
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.08
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
13.2541 0.5675 -0.7203 -0.2175 0.9350 -0.2802
-13.2541 -0.5675 0.7203 0.2175 -0.9350 0.2802
-0.9874 4.0007 4.9901 0.0295 -0.1438 -0.6269
-0.0121 -4.0003 -4.9922 -0.0072 0.0732 0.6441
-0.0014 -0.0001 1.0002 -0.0521 -0.0069 -0.0268
0.0014 0.0001 -1.0002 0.0521 0.0069 0.0268
-12.0102 0.0048 10.9758 -0.3061 -0.9223 -0.0889
12.0054 -1.0050 -10.9736 0.2392 0.9320 0.2165
11.9893 -0.0058 4.0265 -0.4753 0.8193 -0.3126
7.0207 -0.0021 -16.9875 0.7298 0.6107 0.3351
-0.9996 0.0005 -0.0022 0.0222 -0.0706 0.0171
-3.0358 -5.9999 6.0073 -0.6473 -0.1946 0.6562

_diffrn_reflns_av_R_equivalents  0.0285
_diffrn_reflns_av_unetI/netI     0.0321
_diffrn_reflns_Laue_measured_fraction_full 0.9965
_diffrn_reflns_Laue_measured_fraction_max 0.9965
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            10735
_diffrn_reflns_point_group_measured_fraction_full 0.9883
_diffrn_reflns_point_group_measured_fraction_max 0.9375
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         29.13
_diffrn_reflns_theta_min         3.39
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.9965
_diffrn_measured_fraction_theta_max 0.9965
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -24.00  90.00   0.50    3.00    --    6.50  37.00  69.00  228
  2  ω      4.00  62.00   0.50    3.00    --   -7.20  37.00  69.00  116
  3  ω     -1.00  25.00   0.50    3.00    --    6.50  57.00 -90.00   52
  4  ω    -22.00  83.00   0.50    3.00    --    6.50  57.00 120.00  210
  5  ω     29.00  95.00   0.50    3.00    --    6.50  57.00 -60.00  132
  6  ω    -21.00   5.00   0.50    3.00    --    6.50  57.00-180.00   52
  7  ω    -24.00  81.00   0.50    3.00    --   -7.20  57.00 -30.00  210
;
_diffrn_ambient_temperature      293(2)
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0221082000
_diffrn_orient_matrix_UB_12      0.0669004000
_diffrn_orient_matrix_UB_13      -0.0521083000
_diffrn_orient_matrix_UB_21      0.0706062000
_diffrn_orient_matrix_UB_22      -0.0100682000
_diffrn_orient_matrix_UB_23      -0.0067661000
_diffrn_orient_matrix_UB_31      -0.0171336000
_diffrn_orient_matrix_UB_32      -0.1275177000
_diffrn_orient_matrix_UB_33      -0.0267934000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_reflns_Friedel_coverage         0.864
_reflns_limit_h_max              13
_reflns_limit_h_min              -13
_reflns_limit_k_max              6
_reflns_limit_k_min              -6
_reflns_limit_l_max              17
_reflns_limit_l_min              -16
_reflns_number_gt                2440
_reflns_number_total             2878
_reflns_threshold_expression     I>=2u(I)
_computing_cell_refinement       'CrysAlisPro 1.171.42.79a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.79a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.79a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  
'olex2.refine 1.5-ac5-024 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         0.6002
_refine_diff_density_min         -0.4865
_refine_diff_density_rms         0.0565
_refine_ls_abs_structure_details 
'Hooft, R.W.W., Straver, L.H., Spek, A.L. (2010). J. Appl. Cryst., 43, 665-668.'
_refine_ls_abs_structure_Flack   0.002(5)
_refine_ls_d_res_high            0.7301
_refine_ls_d_res_low             6.0158
_refine_ls_extinction_coef       0.0165(14)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.0575
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     236
_refine_ls_number_reflns         2878
_refine_ls_number_restraints     13
_refine_ls_R_factor_all          0.0338
_refine_ls_R_factor_gt           0.0240
_refine_ls_restrained_S_all      1.0551
_refine_ls_shift/su_max          0.0008
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0070P)²+0.0996P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0400
_refine_ls_wR_factor_ref         0.0419
_refine_special_details          
;
Refinement using NoSpherA2, an implementation of
NOn-SPHERical Atom-form-factors in Olex2.
Please cite:
F. Kleemiss et al. Chem. Sci. DOI 10.1039/D0SC05526C - 2021
NoSpherA2 implementation of HAR makes use of
tailor-made aspherical atomic form factors calculated
on-the-fly from a Hirshfeld-partitioned electron density (ED) - not from
spherical-atom form factors.

The ED is calculated from a gaussian basis set single determinant SCF
wavefunction - either Hartree-Fock or DFT using selected funtionals
 - for a fragment of the crystal.
This fragment can be embedded in an electrostatic crystal field by employing cluster charges
or modelled using implicit solvation models, depending on the software used.
The following options were used:
   SOFTWARE:       ORCA 5.0
   PARTITIONING:   NoSpherA2
   INT ACCURACY:   Normal
   METHOD:         B3LYP
   BASIS SET:      jorge-TZP
   CHARGE:         0
   MULTIPLICITY:   1
   DATE:           2023-11-26_16-14-06
;
_olex2_refinement_description    
;
1. Uiso/Uaniso restraints and constraints
Uanis(H2) \\sim Ueq, Uanis(H10) \\sim Ueq: with sigma of 0.03 and sigma for
terminal atoms of 0.02
;
_atom_sites_solution_primary     dual
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_refinement_flags_posn
_atom_site_refinement_flags_adp
Br1 Br 0.901550(18) -0.29600(2) 0.392181(18) 0.05089(8) Uani 1.000000 . .
N1 N 0.44159(16) 0.5657(3) 0.30458(12) 0.0314(3) Uani 1.000000 . .
N2 N 0.57306(17) 0.4182(3) 0.13563(13) 0.0391(4) Uani 1.000000 . .
C4 C 0.7192(2) 0.0924(3) 0.25715(18) 0.0366(4) Uani 1.000000 . .
H4 H 0.769(3) 0.032(5) 0.1931(19) 0.070(8) Uani 1.000000 . .
C3 C 0.61145(19) 0.2963(3) 0.23691(15) 0.0311(4) Uani 1.000000 . .
C8 C 0.54543(18) 0.3718(3) 0.32160(14) 0.0291(4) Uani 1.000000 . .
C5 C 0.75763(19) -0.0255(3) 0.36003(18) 0.0363(4) Uani 1.000000 . .
C7 C 0.5888(2) 0.2434(5) 0.42631(16) 0.0365(5) Uani 1.000000 . .
H7 H 0.537(2) 0.303(4) 0.4882(17) 0.054(7) Uani 1.000000 . .
C6 C 0.6931(2) 0.0476(4) 0.4452(2) 0.0390(4) Uani 1.000000 . .
H6 H 0.724(2) -0.056(5) 0.522(2) 0.064(7) Uani 1.000000 . .
C1 C 0.40436(16) 0.6820(5) 0.20629(13) 0.0305(4) Uani 1.000000 . .
C2 C 0.4728(2) 0.6046(4) 0.12143(17) 0.0395(5) Uani 1.000000 . .
H2 H 0.446(2) 0.681(8) 0.0434(15) 0.069(7) Uani 1.000000 . U
C9 C 0.29066(19) 0.8917(3) 0.18650(16) 0.0330(4) Uani 1.000000 . .
C10 C 0.2487(2) 1.0330(4) 0.08609(18) 0.0433(5) Uani 1.000000 . .
H10 H 0.298(3) 0.993(5) 0.0199(17) 0.061(6) Uani 1.000000 . U
C13 C 0.1164(2) 1.1516(4) 0.2539(2) 0.0499(7) Uani 1.000000 . .
H13 H 0.067(2) 1.179(8) 0.323(2) 0.072(7) Uani 1.000000 . .
C14 C 0.2226(2) 0.9536(4) 0.2697(2) 0.0428(5) Uani 1.000000 . .
H14 H 0.254(3) 0.845(5) 0.346(2) 0.073(8) Uani 1.000000 . .
C11 C 0.1411(2) 1.2285(6) 0.0697(2) 0.0528(5) Uani 1.000000 . .
H11 H 0.108(3) 1.349(6) -0.007(2) 0.099(10) Uani 1.000000 . .
C12 C 0.0755(3) 1.2902(4) 0.1535(2) 0.0507(6) Uani 1.000000 . .
H12 H -0.010(3) 1.440(6) 0.140(2) 0.086(9) Uani 1.000000 . .


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
Br1 C5 1.8907(18) . ?
N1 C8 1.360(2) . ?
N1 C1 1.314(2) . ?
N2 C3 1.359(2) . ?
N2 C2 1.311(2) . ?
C4 H4 1.07(2) . ?
C4 C3 1.420(2) . ?
C4 C5 1.367(3) . ?
C3 C8 1.411(2) . ?
C8 C7 1.412(3) . ?
C5 C6 1.404(3) . ?
C7 H7 1.062(19) . ?
C7 C6 1.369(3) . ?
C6 H6 1.05(2) . ?
C1 C2 1.430(2) . ?
C1 C9 1.480(3) . ?
C2 H2 1.01(2) . ?
C9 C10 1.396(3) . ?
C9 C14 1.392(3) . ?
C10 H10 1.07(2) . ?
C10 C11 1.391(3) . ?
C13 H13 1.09(2) . ?
C13 C14 1.391(3) . ?
C13 C12 1.389(3) . ?
C14 H14 1.06(2) . ?
C11 H11 1.10(3) . ?
C11 C12 1.383(3) . ?
C12 H12 1.09(3) . ?

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
C1 N1 C8 117.83(15) . . ?
C2 N2 C3 116.86(16) . . ?
C3 C4 H4 120.6(12) . . ?
C5 C4 H4 120.8(12) . . ?
C5 C4 C3 118.57(18) . . ?
C4 C3 N2 119.44(16) . . ?
C8 C3 N2 120.46(16) . . ?
C8 C3 C4 120.10(17) . . ?
C3 C8 N1 121.46(16) . . ?
C7 C8 N1 119.46(16) . . ?
C7 C8 C3 119.08(16) . . ?
C4 C5 Br1 120.45(15) . . ?
C6 C5 Br1 117.52(15) . . ?
C6 C5 C4 122.03(18) . . ?
H7 C7 C8 117.5(11) . . ?
C6 C7 C8 120.43(19) . . ?
C6 C7 H7 122.1(11) . . ?
C7 C6 C5 119.8(2) . . ?
H6 C6 C5 118.9(13) . . ?
H6 C6 C7 121.3(13) . . ?
C2 C1 N1 120.12(19) . . ?
C9 C1 N1 118.32(15) . . ?
C9 C1 C2 121.56(16) . . ?
C1 C2 N2 123.28(19) . . ?
H2 C2 N2 112.9(17) . . ?
H2 C2 C1 123.8(17) . . ?
C10 C9 C1 122.03(17) . . ?
C14 C9 C1 119.84(16) . . ?
C14 C9 C10 118.13(18) . . ?
H10 C10 C9 120.8(13) . . ?
C11 C10 C9 120.7(2) . . ?
C11 C10 H10 118.4(13) . . ?
C14 C13 H13 115.1(17) . . ?
C12 C13 H13 124.7(16) . . ?
C12 C13 C14 120.1(2) . . ?
C13 C14 C9 121.1(2) . . ?
H14 C14 C9 118.2(13) . . ?
H14 C14 C13 120.7(13) . . ?
H11 C11 C10 122.7(15) . . ?
C12 C11 C10 120.5(2) . . ?
C12 C11 H11 116.7(15) . . ?
C11 C12 C13 119.3(2) . . ?
H12 C12 C13 120.5(16) . . ?
H12 C12 C11 120.2(16) . . ?

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
Br1 C5 C4 C3 -179.49(13) . . . . ?
Br1 C5 C6 C7 179.68(15) . . . . ?
N1 C8 C3 N2 0.45(19) . . . . ?
N1 C8 C3 C4 -179.78(15) . . . . ?
N1 C8 C7 C6 179.97(17) . . . . ?
N1 C1 C2 N2 0.3(2) . . . . ?
N1 C1 C9 C10 177.36(17) . . . . ?
N1 C1 C9 C14 -2.4(2) . . . . ?
N2 C3 C4 C5 179.17(16) . . . . ?
N2 C3 C8 C7 -179.29(17) . . . . ?
N2 C2 C1 C9 -179.45(18) . . . . ?
C4 C3 C8 C7 0.48(19) . . . . ?
C4 C5 C6 C7 -0.3(2) . . . . ?
C3 C8 C7 C6 -0.28(19) . . . . ?
C8 C7 C6 C5 0.2(2) . . . . ?
C1 C9 C10 C11 179.8(2) . . . . ?
C1 C9 C14 C13 179.34(19) . . . . ?
C9 C10 C11 C12 1.2(2) . . . . ?
C9 C14 C13 C12 0.6(2) . . . . ?
C10 C11 C12 C13 -1.0(3) . . . . ?


_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.104
_oxdiff_exptl_absorpt_empirical_full_min 0.767
loop_
_restr_U_iso_atom_site_label
_restr_U_iso_weight_param
H2 0.0200
H10 0.0200


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: deuterated chloroform'
