# Electronic Supplementary Material (ESI) for CrystEngComm.
# This journal is © The Royal Society of Chemistry 2022

####################################################################### 
# 
# 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_NCLBA
_database_code_depnum_ccdc_archive 'CCDC 2180453'
loop_
_audit_author_name
_audit_author_address
'Raffaella Soave'
;CNR SCITEC
Italy
;
_audit_update_record             
;
2022-06-20 deposited with the CCDC.	2022-08-15 downloaded from the CCDC.
;

_audit_creation_date             10/06/2022
_audit_creation_method           SHELXL-2014/4

#------------------ CHEMICAL INFORMATION ------------------------------------#


_chemical_name_systematic        
;
N-chloro-N'-(p-fluorophenyl)-benzamidine
;
_chemical_name_common            NCLBA
_chemical_melting_point          ?
_chemical_formula_moiety         'C13 H10 Cl F N2'
_chemical_formula_sum            'C13 H10 Cl F N2'
_chemical_formula_weight         248.68

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'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           144
_space_group_name_H-M_alt        'P 31'
_space_group_name_Hall           'P 31'

_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'
'-y, x-y, z+1/3'
'-x+y, -x, z+2/3'

_cell_length_a                   10.0227(3)
_cell_length_b                   10.0227(3)
_cell_length_c                   9.8795(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     859.48(6)
_cell_formula_units_Z            3
_cell_measurement_temperature    17.5(9)
_cell_measurement_reflns_used    120
_cell_measurement_theta_min      13.25
_cell_measurement_theta_max      15.58

_exptl_crystal_description       sphere
_exptl_crystal_colour            'pale yellow'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.441
_exptl_crystal_F_000             384
_exptl_crystal_size_rad          0.25
_exptl_absorpt_coefficient_mu    0.323
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   none

_exptl_special_details           
;
To determine the cell dimensions 120 reflections were centered in
both negative and positive 2theta regions. A least-square fit to the
resulting values of (sin(theta))**2 gave the reported cell parameters.
;

_diffrn_ambient_temperature      17.5(9)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Siemens P1-'
_diffrn_measurement_method       '2θ/ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         3
_diffrn_standards_interval_count 97
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        0
_diffrn_reflns_number            27709
_diffrn_reflns_av_unetI/netI     0.0237
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         2.346
_diffrn_reflns_theta_max         54.397
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_av_R_equivalents  0.0
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.708
_diffrn_reflns_point_group_measured_fraction_full 0.728
_reflns_number_total             14382
_reflns_number_gt                14309
_reflns_threshold_expression     'I > 0'
_reflns_Friedel_coverage         0.419
_reflns_Friedel_fraction_max     0.419
_reflns_Friedel_fraction_full    0.456

_reflns_special_details          
;
 Data were apparently pre-merged, so _diffrn_reflns_number
 etc. will have to be added later.
 
 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       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-2014/4 (Sheldrick, 2014)'
_computing_structure_refinement  
;
VALRAY2000 (Stewart, Spackman & Flensburg, 2000)
;
_computing_molecular_graphics    
;
ORTEPIII (Burnett & Johnson, 1996),
Brandenburg, K.; Putz, H. Diamond - Crystal and Molecular Structure
Visualization 3.1d; Crystal
Impact GbR: Bonn, 2006; http://www.crystalimpact.com/diamond.
;
_refine_special_details          
;
 Refinement of F² against ALL observed (I>0) reflections. 
 The electron  density was obtained from the diffraction 
 data by a multipolar  expansion of atom-centred functions
 according to the rigid pseudoatom formalism of Stewart 
 (Acta Cryst. (1976). A32, 565-574). The final model employed a 
 multipolar expansion up to the hexadecapole level (l = 4) on 
 C and O atoms and to the quadrupole level (l = 2) on H atoms. 
 The ADPs of the chlorine and fluorine  atoms were modified in the 
 final model with the inclusion  of the 10 third-order Gram-Charlier 
 (GC) coefficients (Cijk's) and 15 fourth-order GC coefficients 
 (Dijkl's) for a better  description of the anharmonicity of the 
 thermal motion. The software VALRAY2000 was employed throughout.
 Initial scattering factors for hydrogen were those of the H2 
 molecule, and their coordinates and isotropic U values were 
 allowed to shift; subsequently, the coordinates of hydrogen 
 atoms were kept fixed and generalized monopole and dipole 
 functions were introduced. Finally, anisotropic Uij values
 (ADPs) were introduced for hydrogen atoms based on 
 spectroscopic information and the molecular rigid-body 
 librations derived from the refined ADPs of the carbon and 
 nitrogen atoms.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1000P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   direct
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refxyz
_refine_ls_extinction_method     VALRAY2000
_refine_ls_extinction_coef       0.160(8)
_refine_ls_abs_structure_details 
;
 Flack x determined using 2780 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.019(12)
_chemical_absolute_configuration ad
_refine_ls_number_reflns         14309
_refine_ls_number_parameters     680
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0159
_refine_ls_R_factor_gt           0.0159
_refine_ls_wR_factor_ref         0.0140
_refine_ls_wR_factor_gt          0.0140
_refine_ls_goodness_of_fit_ref   0.9652
_refine_ls_restrained_S_all      0.9652
_refine_ls_shift/su_max          0.0490
_refine_ls_shift/su_mean         0.0040

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
Cl1 Cl 0.089010(4) 0.118410(4) 0.00000 0.006 Uani 1 1 d . . . . .
F1 F -0.16093(3) -0.79418(2) 0.14033(3) 0.010 Uani 1 1 d . . . . .
N1 N 0.21000(2) 0.09832(2) 0.11559(2) 0.006 Uani 1 1 d . . . . .
N2 N 0.05378(2) -0.17098(2) 0.07887(2) 0.007 Uani 1 1 d . . . . .
C1 C 0.17237(2) -0.04499(2) 0.13658(2) 0.005 Uani 1 1 d . . . . .
C2 C 0.27293(2) -0.06165(2) 0.23811(1) 0.005 Uani 1 1 d . . . . .
C3 C 0.21042(2) -0.14320(2) 0.35841(2) 0.006 Uani 1 1 d . . . . .
C4 C 0.30822(2) -0.14947(2) 0.45555(2) 0.007 Uani 1 1 d . . . . .
C5 C 0.46711(2) -0.07459(2) 0.43286(2) 0.007 Uani 1 1 d . . . . .
C6 C 0.52883(2) 0.00486(2) 0.31212(2) 0.007 Uani 1 1 d . . . . .
C7 C 0.43160(2) 0.01124(2) 0.21447(2) 0.006 Uani 1 1 d . . . . .
C8 C 0.00582(2) -0.32821(2) 0.10392(2) 0.006 Uani 1 1 d . . . . .
C9 C 0.10842(2) -0.38432(2) 0.11070(2) 0.006 Uani 1 1 d . . . . .
C10 C 0.05190(2) -0.54201(2) 0.12707(2) 0.007 Uani 1 1 d . . . . .
C11 C -0.10628(2) -0.64050(2) 0.13215(2) 0.007 Uani 1 1 d . . . . .
C12 C -0.21023(2) -0.58765(2) 0.12746(2) 0.007 Uani 1 1 d . . . . .
C13 C -0.15264(2) -0.42974(2) 0.11463(2) 0.007 Uani 1 1 d . . . . .
H3 H 0.08791 -0.19519 0.37584 0.02199 Uani 1 1 d . . . . .
H4 H 0.26149 -0.20430 0.55350 0.02404 Uani 1 1 d . . . . .
H5 H 0.54296 -0.07830 0.50922 0.02811 Uani 1 1 d . . . . .
H6 H 0.65120 0.06041 0.29437 0.02339 Uani 1 1 d . . . . .
H7 H 0.47952 0.07430 0.12175 0.02191 Uani 1 1 d . . . . .
H9 H 0.23098 -0.30812 0.10284 0.02250 Uani 1 1 d . . . . .
H10 H 0.12680 -0.59066 0.13165 0.02961 Uani 1 1 d . . . . .
H12 H -0.33369 -0.66190 0.13358 0.02559 Uani 1 1 d . . . . .
H13 H -0.22885 -0.38414 0.11088 0.02850 Uani 1 1 d . . . . .
H2N H -0.01615 -0.15598 0.01410 0.02115 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
Cl1 N1 1.7490(2) . ?
F1 C11 1.3547(2) . ?
N1 C1 1.3064(2) . ?
N2 C1 1.3533(2) . ?
N2 C8 1.4207(2) . ?
N2 H2N 1.0142 . ?
C1 C2 1.4894(2) . ?
C2 C7 1.3984(2) . ?
C2 C3 1.4003(2) . ?
C3 C4 1.3955(2) . ?
C3 H3 1.0812 . ?
C4 C5 1.3980(2) . ?
C4 H4 1.0956 . ?
C5 C6 1.3954(2) . ?
C5 H5 1.0848 . ?
C6 C7 1.3953(2) . ?
C6 H6 1.0780 . ?
C7 H7 1.0796 . ?
C8 C9 1.3987(2) . ?
C8 C13 1.3974(2) . ?
C9 C10 1.3963(2) . ?
C9 H9 1.0771 . ?
C10 C11 1.3876(2) . ?
C10 H10 1.0814 . ?
C11 C12 1.3857(2) . ?
C12 C13 1.3931(2) . ?
C12 H12 1.0807 . ?
C13 H13 1.0690 . ?

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 Cl1 113.238(2) . . ?
C1 N2 C8 127.868(2) . . ?
C1 N2 H2N 118.498 . . ?
C8 N2 H2N 113.496 . . ?
N1 C1 N2 126.517(2) . . ?
N1 C1 C2 112.995(1) . . ?
N2 C1 C2 120.465(2) . . ?
C7 C2 C3 120.448(2) . . ?
C7 C2 C1 119.045(1) . . ?
C3 C2 C1 120.442(2) . . ?
C4 C3 C2 119.381(2) . . ?
C4 C3 H3 121.518 . . ?
C2 C3 H3 119.033 . . ?
C3 C4 C5 120.183(2) . . ?
C3 C4 H4 119.755 . . ?
C5 C4 H4 119.831 . . ?
C6 C5 C4 120.296(2) . . ?
C6 C5 H5 119.717 . . ?
C4 C5 H5 119.987 . . ?
C7 C6 C5 119.782(2) . . ?
C7 C6 H6 120.276 . . ?
C5 C6 H6 119.940 . . ?
C6 C7 C2 119.896(4) . . ?
C6 C7 H7 119.803 . . ?
C2 C7 H7 120.291 . . ?
C9 C8 C13 119.998(2) . . ?
C9 C8 N2 123.041(1) . . ?
C13 C8 N2 116.870(1) . . ?
C10 C9 C8 119.794(3) . . ?
C10 C9 H9 118.967 . . ?
C8 C9 H9 121.237 . . ?
C11 C10 C9 118.816(2) . . ?
C11 C10 H10 118.786 . . ?
C9 C10 H10 122.346 . . ?
F1 C11 C12 118.866(2) . . ?
F1 C11 C10 118.660(1) . . ?
C12 C11 C10 122.469(3) . . ?
C11 C12 C13 118.279(1) . . ?
C11 C12 H12 123.764 . . ?
C13 C12 H12 117.957 . . ?
C12 C13 C8 120.570(1) . . ?
C12 C13 H13 120.673 . . ?
C8 C13 H13 118.747 . . ?

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 C1 N1 Cl1 -0.05(3) . . . . ?
C2 C1 N1 Cl1 -178.31(3) . . . . ?
C8 N2 C1 N1 -176.98(2) . . . . ?
C8 N2 C1 C2 1.16(3) . . . . ?
N1 C1 C2 C7 -58.68(2) . . . . ?
N2 C1 C2 C7 122.94(2) . . . . ?
C3 C2 C1 N1 118.40(3) . . . . ?
N2 C1 C2 C3 -59.97(3) . . . . ?
C7 C2 C3 C4 0.84(3) . . . . ?
C1 C2 C3 C4 -176.20(2) . . . . ?
C2 C3 C4 C5 0.17(3) . . . . ?
C3 C4 C5 C6 -1.02(3) . . . . ?
C4 C5 C6 C7 0.86(3) . . . . ?
C5 C6 C7 C2 0.14(3) . . . . ?
C3 C2 C7 C6 -0.99(3) . . . . ?
C1 C2 C7 C6 176.09(2) . . . . ?
C1 N2 C8 C9 -46.08(3) . . . . ?
C1 N2 C8 C13 137.39(2) . . . . ?
C13 C8 C9 C10 0.52(3) . . . . ?
N2 C8 C9 C10 -175.91(2) . . . . ?
C8 C9 C10 C11 1.94(3) . . . . ?
C9 C10 C11 F1 176.31(2) . . . . ?
C9 C10 C11 C12 -2.86(3) . . . . ?
F1 C11 C12 C13 -177.95(2) . . . . ?
C10 C11 C12 C13 1.22(3) . . . . ?
C11 C12 C13 C8 1.34(3) . . . . ?
C9 C8 C13 C12 -2.19(3) . . . . ?
N2 C8 C13 C12 174.45(2) . . . . ?

_refine_diff_density_max         0.33
_refine_diff_density_min         -0.28

_shelxl_version_number           2014/4



_vrf_CELLK01_NCLBA               
;
PROBLEM: Check that the cell measurement temperature is in Kelvin.
RESPONSE: Yes, it is true. The temeprature of the data collection 
amounted to 17.5(0.9) K.
;
_vrf_PLAT230_NCLBA               
;
PROBLEM: Hirshfeld Test Diff for    F1       --C11      .       17.6 s.u.  
RESPONSE: This problem is due to the fact that the thermal motion of 
 fluorine atom has significant anaharmonic components which are not 
 taken into accont into the Hirshfel test.
;
_vrf_PLAT085_NCLBA               
;
PROBLEM: SHELXL Default Weighting Scheme is not Optimized     Please Check 
RESPONSE: The reported weighting scheme has been optimized during the 
 multipole model refinement in VALRAY, which the code (instead of SHELX) 
 adopted for the structure refinement.	
;
_vrf_PLAT218_NCLBA               
;
PROBLEM: Constrained U(ij) Components(s) for H3         .          6 Check 
RESPONSE: Initial scattering factors for hydrogen were those of the H2 
 molecule, and their coordinates and isotropic U values were 
 allowed to shift; subsequently, the coordinates of hydrogen 
 atoms were kept fixed and generalized monopole and dipole 
 functions were introduced. Finally, anisotropic Uij values
 (ADPs) were introduced for hydrogen atoms based on 
 spectroscopic information and the molecular rigid-body 
 librations derived from the refined ADPs of the carbon and 
 nitrogen atoms. They have been kept fixed in the final refinement, 
so the reported U(ij) do not have a standard deviation
;
_vrf_PLAT250_NCLBA               
;
PROBLEM: Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.3 Note  
RESPONSE: This problem is due to the fact that the thermal motion of 
 some atoms in the NCLBA structure have significant anaharmonic 
 components in addition to the harmonic U(i,j) comnponents. 
 We are confident that our description of the thermal motion is 
 more rthan satisfactory, especially thank to the very low 
 data colection temnperature (17.5 K).
;
_vrf_PLAT353_NCLBA               
;
PROBLEM: Long   N-H (N0.87,N1.01A)  N2       - H2N      .       1.01 Ang.  
RESPONSE: Positional parameters of H atoms were evaluated with 
 the "polarized H atoms" option of  VALRAY, that is, H atoms 
 were refined by including polarization by using theoretical 
 atomic scattering factors obtained from the charge density distribution
 of the H2 molecule. Furtheromre the H2N atom is involved in an 
 intermolecular NH...N hydrogen bond which elongates the covalent N-H2N 
 bond in the direction of acceptor N atom.
;
_vrf_PLAT790_NCLBA               
;
RESPONSE: This affects neither the model nor the physics it describes.
;
