# Electronic Supplementary Material (ESI) for Green Chemistry.
# This journal is © The Royal Society of Chemistry 2018

####################################################################### 
# 
# 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_aaaa
_database_code_depnum_ccdc_archive 'CCDC 1819200'
_audit_update_record             
;
2018-01-25 deposited with the CCDC.
2018-05-08 downloaded from the CCDC.
;
_audit_creation_date             2017-11-30
_audit_creation_method           
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_chemical_name_common            ?
_chemical_name_systematic        
;
 ? 
;
_chemical_formula_moiety         'C15 H12 Br N O'
_chemical_formula_sum            'C15 H0 Br N O'
_chemical_formula_weight         290.07
_chemical_absolute_configuration ad
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 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'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_H-M_alt        'C 1 c 1'
_space_group_name_Hall           'C -2yc'
loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 'x, y, z'
2 'x, -y, z+1/2'
3 'x+1/2, y+1/2, z'
4 'x+1/2, -y+1/2, z+1/2'

_cell_length_a                   29.72(4)
_cell_length_b                   5.675(7)
_cell_length_c                   7.425(9)
_cell_angle_alpha                90.00
_cell_angle_beta                 95.29(2)
_cell_angle_gamma                90.00
_cell_volume                     1247(3)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    2326
_cell_measurement_temperature    293.15
_cell_measurement_theta_max      25.30
_cell_measurement_theta_min      2.75
_exptl_absorpt_coefficient_mu    3.280
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.10312
_exptl_absorpt_correction_type   ?
_exptl_absorpt_process_details   ?
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.545
_exptl_crystal_density_meas      .
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             560
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.17
_exptl_special_details           
;
 ? 
;
_diffrn_reflns_av_R_equivalents  0.0840
_diffrn_reflns_av_unetI/netI     0.1069
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            4021
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         25.00
_diffrn_reflns_theta_min         1.38
_diffrn_ambient_temperature      293.15
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_decay_%        ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_number         0
_reflns_number_gt                1538
_reflns_number_total             2051
_reflns_threshold_expression     >2sigma(I)
_computing_cell_refinement       'SAINT v8.27A (Bruker, 2012)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_refine_diff_density_max         1.492
_refine_diff_density_min         -0.965
_refine_diff_density_rms         0.218
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.01(3)
_refine_ls_extinction_coef       ?
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     164
_refine_ls_number_reflns         2051
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0988
_refine_ls_R_factor_gt           0.0727
_refine_ls_restrained_S_all      1.054
_refine_ls_shift/su_max          0.173
_refine_ls_shift/su_mean         0.034
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.1440P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1964
_refine_ls_wR_factor_ref         0.2171
_refine_special_details          
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.93(3)
 0.07(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3.a Ternary CH refined with riding coordinates:
 C7(H7)
3.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B)
3.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C10(H10), C13(H13), C17(H17), C28(H28), C31(H31), C35(H35),
 C41(H41)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
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_calc_flag
_atom_site_disorder_assembly
_atom_site_disorder_group
_atom_site_refinement_flags_posn
Br1 Br 0.17753(3) 0.8106(2) 0.12783(5) 0.0621(5) Uani 1 d . . .
O6 O 0.3902(2) 0.4336(12) 0.3854(10) 0.0395(15) Uani 1 d . . .
N45 N 0.4367(3) 0.4316(13) 0.3710(11) 0.0339(17) Uani 1 d . . .
C2 C 0.2388(4) 0.778(2) 0.2160(13) 0.038(2) Uani 1 d . . .
C4 C 0.2522(3) 0.5747(18) 0.3163(13) 0.036(2) Uani 1 d . . .
H4 H 0.2308 0.4624 0.3409 0.043 Uiso 1 calc . . R
C5 C 0.2695(3) 0.9462(16) 0.1909(12) 0.033(2) Uani 1 d . . .
H5 H 0.2602 1.0842 0.1309 0.040 Uiso 1 calc . . R
C6 C 0.4505(3) 0.6388(15) 0.3365(12) 0.030(2) Uani 1 d . . .
C7 C 0.3765(4) 0.6824(15) 0.4096(12) 0.030(2) Uani 1 d . . .
H7 H 0.3800 0.7176 0.5394 0.036 Uiso 1 calc . . R
C8 C 0.4967(3) 0.6917(16) 0.3093(11) 0.0296(19) Uani 1 d . . .
C10 C 0.5754(3) 0.5811(19) 0.3247(13) 0.040(2) Uani 1 d . . .
H10 H 0.5979 0.4698 0.3529 0.048 Uiso 1 calc . . R
C12 C 0.4124(3) 0.8163(15) 0.3216(15) 0.033(2) Uani 1 d . . .
H12A H 0.4208 0.9603 0.3867 0.040 Uiso 1 calc . . R
H12B H 0.4028 0.8538 0.1965 0.040 Uiso 1 calc . . R
C13 C 0.3130(3) 0.9199(16) 0.2501(12) 0.0327(19) Uani 1 d . . .
H13 H 0.3332 1.0393 0.2276 0.039 Uiso 1 calc . . R
C16 C 0.3298(4) 0.7156(15) 0.3464(12) 0.030(2) Uani 1 d . . .
C17 C 0.2961(3) 0.5428(16) 0.3769(13) 0.037(2) Uani 1 d . . .
H17 H 0.3047 0.4057 0.4397 0.045 Uiso 1 calc . . R
C28 C 0.5086(3) 0.9025(18) 0.2307(12) 0.036(2) Uani 1 d . . .
H28 H 0.4866 1.0150 0.1977 0.043 Uiso 1 calc . . R
C31 C 0.5313(3) 0.5281(17) 0.3606(14) 0.038(2) Uani 1 d . . .
H31 H 0.5248 0.3876 0.4172 0.046 Uiso 1 calc . . R
C35 C 0.5864(4) 0.781(2) 0.2531(16) 0.047(3) Uani 1 d . . .
H35 H 0.6164 0.8149 0.2362 0.057 Uiso 1 calc . . R
C41 C 0.5522(4) 0.9439(19) 0.2024(14) 0.046(2) Uani 1 d . . .
H41 H 0.5597 1.0842 0.1477 0.055 Uiso 1 calc . . R

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Br1 0.0314(6) 0.0851(9) 0.0678(7) -0.0015(8) -0.0066(4) 0.0104(8)
O6 0.035(3) 0.020(3) 0.063(4) 0.006(3) 0.000(3) 0.003(3)
N45 0.035(4) 0.020(4) 0.045(4) 0.003(3) -0.003(3) 0.005(4)
C2 0.027(5) 0.053(6) 0.035(5) -0.014(4) 0.002(4) 0.012(4)
C4 0.027(5) 0.035(5) 0.045(5) 0.007(4) 0.007(4) -0.006(4)
C5 0.039(5) 0.028(4) 0.033(5) 0.005(4) 0.010(4) 0.007(4)
C6 0.037(5) 0.027(5) 0.025(4) -0.001(3) -0.005(4) 0.001(4)
C7 0.041(6) 0.020(4) 0.028(4) -0.009(3) 0.004(4) 0.001(4)
C8 0.037(5) 0.033(5) 0.017(4) -0.009(3) -0.006(3) 0.004(4)
C10 0.034(5) 0.042(5) 0.043(5) -0.006(5) -0.002(4) 0.008(5)
C12 0.032(5) 0.023(4) 0.044(6) 0.006(4) 0.002(4) 0.001(4)
C13 0.046(6) 0.024(4) 0.029(4) 0.012(4) 0.007(4) 0.000(4)
C16 0.044(6) 0.023(4) 0.026(4) 0.001(4) 0.009(4) 0.004(4)
C17 0.049(6) 0.024(4) 0.040(5) 0.007(4) 0.007(4) -0.002(4)
C28 0.037(6) 0.031(5) 0.039(5) -0.002(4) -0.001(4) 0.002(4)
C31 0.031(5) 0.034(5) 0.049(5) 0.001(4) -0.002(4) 0.008(4)
C35 0.031(6) 0.067(7) 0.045(6) -0.014(5) 0.008(5) -0.014(5)
C41 0.059(7) 0.036(5) 0.043(5) -0.005(4) 0.003(5) -0.007(5)

_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
Br1 C2 1.887(11) . ?
O6 N45 1.397(10) . ?
O6 C7 1.484(11) . ?
N45 C6 1.279(12) . ?
C2 C4 1.408(16) . ?
C2 C5 1.348(15) . ?
C4 H4 0.9300 . ?
C4 C17 1.354(14) . ?
C5 H5 0.9300 . ?
C5 C13 1.334(13) . ?
C6 C8 1.437(15) . ?
C6 C12 1.513(14) . ?
C7 H7 0.9800 . ?
C7 C12 1.507(14) . ?
C7 C16 1.436(15) . ?
C8 C28 1.391(15) . ?
C8 C31 1.412(14) . ?
C10 H10 0.9300 . ?
C10 C31 1.395(14) . ?
C10 C35 1.309(17) . ?
C12 H12A 0.9700 . ?
C12 H12B 0.9700 . ?
C13 H13 0.9300 . ?
C13 C16 1.428(13) . ?
C16 C17 1.434(14) . ?
C17 H17 0.9300 . ?
C28 H28 0.9300 . ?
C28 C41 1.353(15) . ?
C31 H31 0.9300 . ?
C35 H35 0.9300 . ?
C35 C41 1.398(18) . ?
C41 H41 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
N45 O6 C7 107.5(7) . . ?
C6 N45 O6 110.3(8) . . ?
C4 C2 Br1 118.8(8) . . ?
C5 C2 Br1 121.7(8) . . ?
C5 C2 C4 119.4(10) . . ?
C2 C4 H4 120.0 . . ?
C17 C4 C2 120.1(9) . . ?
C17 C4 H4 119.9 . . ?
C2 C5 H5 119.2 . . ?
C13 C5 C2 121.5(9) . . ?
C13 C5 H5 119.2 . . ?
N45 C6 C8 123.3(9) . . ?
N45 C6 C12 112.0(9) . . ?
C8 C6 C12 124.7(8) . . ?
O6 C7 H7 107.9 . . ?
O6 C7 C12 102.4(7) . . ?
C12 C7 H7 107.9 . . ?
C16 C7 O6 110.6(7) . . ?
C16 C7 H7 107.9 . . ?
C16 C7 C12 119.6(8) . . ?
C28 C8 C6 121.5(9) . . ?
C28 C8 C31 118.1(9) . . ?
C31 C8 C6 120.4(8) . . ?
C31 C10 H10 118.7 . . ?
C35 C10 H10 118.7 . . ?
C35 C10 C31 122.6(10) . . ?
C6 C12 H12A 111.6 . . ?
C6 C12 H12B 111.7 . . ?
C7 C12 C6 100.8(7) . . ?
C7 C12 H12A 111.6 . . ?
C7 C12 H12B 111.6 . . ?
H12A C12 H12B 109.4 . . ?
C5 C13 H13 118.7 . . ?
C5 C13 C16 122.6(9) . . ?
C16 C13 H13 118.7 . . ?
C13 C16 C7 123.5(9) . . ?
C13 C16 C17 114.7(9) . . ?
C17 C16 C7 121.7(8) . . ?
C4 C17 C16 121.5(8) . . ?
C4 C17 H17 119.3 . . ?
C16 C17 H17 119.3 . . ?
C8 C28 H28 120.0 . . ?
C41 C28 C8 120.0(10) . . ?
C41 C28 H28 120.0 . . ?
C8 C31 H31 120.6 . . ?
C10 C31 C8 118.8(9) . . ?
C10 C31 H31 120.6 . . ?
C10 C35 H35 120.7 . . ?
C10 C35 C41 118.7(10) . . ?
C41 C35 H35 120.6 . . ?
C28 C41 C35 121.8(10) . . ?
C28 C41 H41 119.1 . . ?
C35 C41 H41 119.1 . . ?

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 C2 C4 C17 178.1(7) . . . . ?
Br1 C2 C5 C13 -178.5(7) . . . . ?
O6 N45 C6 C8 -178.3(8) . . . . ?
O6 N45 C6 C12 -0.3(12) . . . . ?
O6 C7 C12 C6 -24.0(10) . . . . ?
O6 C7 C16 C13 -140.7(9) . . . . ?
O6 C7 C16 C17 39.5(11) . . . . ?
N45 O6 C7 C12 25.7(9) . . . . ?
N45 O6 C7 C16 154.2(7) . . . . ?
N45 C6 C8 C28 164.5(9) . . . . ?
N45 C6 C8 C31 -14.9(13) . . . . ?
N45 C6 C12 C7 16.3(12) . . . . ?
C2 C4 C17 C16 2.0(14) . . . . ?
C2 C5 C13 C16 -1.3(13) . . . . ?
C4 C2 C5 C13 3.8(13) . . . . ?
C5 C2 C4 C17 -4.2(14) . . . . ?
C5 C13 C16 C7 179.3(8) . . . . ?
C5 C13 C16 C17 -0.9(12) . . . . ?
C6 C8 C28 C41 -178.1(8) . . . . ?
C6 C8 C31 C10 177.2(8) . . . . ?
C7 O6 N45 C6 -16.6(9) . . . . ?
C7 C16 C17 C4 -179.7(9) . . . . ?
C8 C6 C12 C7 -165.7(8) . . . . ?
C8 C28 C41 C35 -1.2(15) . . . . ?
C10 C35 C41 C28 2.1(16) . . . . ?
C12 C6 C8 C28 -13.3(15) . . . . ?
C12 C6 C8 C31 167.4(10) . . . . ?
C12 C7 C16 C13 -22.2(13) . . . . ?
C12 C7 C16 C17 158.0(9) . . . . ?
C13 C16 C17 C4 0.5(13) . . . . ?
C16 C7 C12 C6 -146.7(9) . . . . ?
C28 C8 C31 C10 -2.2(13) . . . . ?
C31 C8 C28 C41 1.2(13) . . . . ?
C31 C10 C35 C41 -3.2(16) . . . . ?
C35 C10 C31 C8 3.3(15) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.93(3)
2 0.07(3)
####################################################################### 
# 
# 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_aaaa_CCDC1
_database_code_depnum_ccdc_archive 'CCDC 1819201'
_audit_update_record             
;
2018-01-25 deposited with the CCDC.
2018-05-08 downloaded from the CCDC.
;
_audit_creation_date             2017-10-08
_audit_creation_method           
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_chemical_name_common            ?
_chemical_name_systematic        
;
 ? 
;
_chemical_formula_moiety         'C20 H16 F3 N'
_chemical_formula_sum            'C20 H16 F3 N'
_chemical_formula_weight         327.34
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 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'
F F 0.0171 0.0103 '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      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 'x, y, z'
2 '-x, -y, -z'

_cell_length_a                   8.5850(15)
_cell_length_b                   9.8690(17)
_cell_length_c                   10.0994(17)
_cell_angle_alpha                91.079(3)
_cell_angle_beta                 103.819(3)
_cell_angle_gamma                90.728(3)
_cell_volume                     830.6(2)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    4409
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      26.34
_cell_measurement_theta_min      2.80
_exptl_absorpt_coefficient_mu    0.100
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details   ?
_exptl_crystal_colour            'dull light colourless'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.309
_exptl_crystal_density_meas      .
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       irregular
_exptl_crystal_F_000             340
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.1
_exptl_special_details           
;
 ? 
;
_diffrn_reflns_av_R_equivalents  0.0248
_diffrn_reflns_av_unetI/netI     0.0257
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            9632
_diffrn_reflns_theta_full        26.40
_diffrn_reflns_theta_max         26.40
_diffrn_reflns_theta_min         2.06
_diffrn_ambient_temperature      296.15
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_decay_%        ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_number         0
_reflns_number_gt                2663
_reflns_number_total             3406
_reflns_threshold_expression     >2sigma(I)
_computing_cell_refinement       'SAINT v8.27A (Bruker, 2012)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_refine_diff_density_max         1.414
_refine_diff_density_min         -0.665
_refine_diff_density_rms         0.103
_refine_ls_extinction_coef       ?
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.928
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     219
_refine_ls_number_reflns         3406
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1308
_refine_ls_R_factor_gt           0.1156
_refine_ls_restrained_S_all      1.928
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.2000P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3948
_refine_ls_wR_factor_ref         0.4283
_refine_special_details          
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C12(H12), C19(H19), C15(H15), C17(H17), C16(H16), C18(H18), C11(H11), C8(H8),
 C7(H7), C10(H10)
2.b Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C1(H1A,H1B,H1C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
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_calc_flag
_atom_site_disorder_assembly
_atom_site_disorder_group
_atom_site_refinement_flags_posn
N1 N 0.1867(3) 0.8974(2) 0.9678(2) 0.0406(7) Uani 1 d . . .
C14 C 0.2127(3) 0.8194(3) 1.1970(3) 0.0393(8) Uani 1 d . . .
C4 C -0.0431(3) 0.8440(3) 0.7816(3) 0.0398(8) Uani 1 d . . .
C13 C 0.1189(3) 0.8269(3) 1.0522(3) 0.0378(8) Uani 1 d . . .
C12 C -0.0307(4) 0.7645(3) 1.0072(3) 0.0438(8) Uani 1 d . . .
H12 H -0.0760 0.7177 1.0682 0.053 Uiso 1 calc . . R
C5 C -0.1128(3) 0.7716(3) 0.8716(3) 0.0388(7) Uani 1 d . . .
C2 C 0.1079(3) 0.9053(3) 0.8370(3) 0.0390(7) Uani 1 d . . .
C19 C 0.3691(4) 0.8704(3) 1.2345(3) 0.0490(9) Uani 1 d . . .
H19 H 0.4148 0.9091 1.1692 0.059 Uiso 1 calc . . R
C6 C -0.2723(3) 0.7023(3) 0.8302(3) 0.0412(8) Uani 1 d . . .
C15 C 0.1490(4) 0.7614(3) 1.2979(3) 0.0482(8) Uani 1 d . . .
H15 H 0.0449 0.7259 1.2750 0.058 Uiso 1 calc . . R
C17 C 0.3915(4) 0.8076(3) 1.4661(3) 0.0551(9) Uani 1 d . . .
H17 H 0.4509 0.8043 1.5559 0.066 Uiso 1 calc . . R
C16 C 0.2380(4) 0.7558(3) 1.4316(3) 0.0551(9) Uani 1 d . . .
H16 H 0.1936 0.7171 1.4977 0.066 Uiso 1 calc . . R
C18 C 0.4582(4) 0.8641(4) 1.3691(3) 0.0565(9) Uani 1 d . . .
H18 H 0.5628 0.8983 1.3931 0.068 Uiso 1 calc . . R
C3 C -0.1254(4) 0.8568(4) 0.6328(3) 0.0556(9) Uani 1 d . . .
H3A H -0.2111 0.7908 0.6081 0.083 Uiso 1 calc . . GR
H3B H -0.0493 0.8417 0.5783 0.083 Uiso 1 calc . . GR
H3C H -0.1681 0.9461 0.6172 0.083 Uiso 1 calc . . GR
C11 C -0.3979(4) 0.7469(3) 0.8825(3) 0.0501(9) Uani 1 d . . .
H11 H -0.3840 0.8246 0.9378 0.060 Uiso 1 calc . . R
C8 C -0.4427(5) 0.5195(4) 0.7149(4) 0.0655(11) Uani 1 d . . .
H8 H -0.4574 0.4428 0.6581 0.079 Uiso 1 calc . . R
C7 C -0.2974(4) 0.5890(4) 0.7429(4) 0.0598(10) Uani 1 d . . .
H7 H -0.2160 0.5600 0.7033 0.072 Uiso 1 calc . . R
C1 C 0.1923(4) 0.9870(4) 0.7490(3) 0.0555(9) Uani 1 d . . .
H1A H 0.2900 1.0257 0.8045 0.083 Uiso 1 calc . . GR
H1B H 0.1239 1.0583 0.7071 0.083 Uiso 1 calc . . GR
H1C H 0.2167 0.9290 0.6796 0.083 Uiso 1 calc . . GR
C10 C -0.5444(4) 0.6776(4) 0.8540(4) 0.0596(10) Uani 1 d . . .
H10 H -0.6277 0.7078 0.8906 0.072 Uiso 1 calc . . R
C9 C -0.5645(4) 0.5620(3) 0.7694(4) 0.0541(9) Uani 1 d . . .
F3 F -0.7101(4) 0.3635(4) 0.7846(5) 0.1430(16) Uani 1 d . . .
F1 F -0.7660(6) 0.4429(7) 0.6100(5) 0.193(2) Uani 1 d . . .
C20 C -0.7197(5) 0.4848(4) 0.7398(5) 0.0743(13) Uani 1 d . . .
F0AA F -0.8345(5) 0.5438(5) 0.7588(11) 0.287(5) Uani 1 d . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
N1 0.0356(13) 0.0432(14) 0.0434(14) 0.0006(10) 0.0106(10) -0.0035(10)
C14 0.0389(16) 0.0370(14) 0.0419(15) -0.0017(11) 0.0100(12) -0.0025(11)
C4 0.0401(16) 0.0403(15) 0.0382(15) 0.0003(11) 0.0076(12) 0.0005(12)
C13 0.0352(15) 0.0387(14) 0.0402(15) -0.0005(11) 0.0107(11) -0.0019(11)
C12 0.0419(17) 0.0482(17) 0.0417(16) 0.0013(12) 0.0116(12) -0.0092(13)
C5 0.0355(15) 0.0355(14) 0.0447(15) -0.0033(11) 0.0088(11) -0.0042(11)
C2 0.0379(15) 0.0400(15) 0.0403(15) -0.0012(11) 0.0120(11) -0.0020(11)
C19 0.0434(17) 0.0610(19) 0.0397(15) 0.0075(13) 0.0044(12) -0.0125(14)
C6 0.0370(16) 0.0397(15) 0.0444(15) -0.0002(11) 0.0054(12) -0.0057(11)
C15 0.0451(17) 0.0543(18) 0.0452(16) 0.0040(13) 0.0106(13) -0.0047(13)
C17 0.057(2) 0.0568(19) 0.0437(17) 0.0026(14) -0.0030(14) 0.0010(15)
C16 0.059(2) 0.060(2) 0.0475(18) 0.0088(14) 0.0136(15) -0.0002(16)
C18 0.0479(18) 0.064(2) 0.0500(19) 0.0031(15) -0.0033(14) -0.0115(15)
C3 0.055(2) 0.066(2) 0.0426(17) 0.0037(14) 0.0057(14) -0.0087(16)
C11 0.0458(18) 0.0525(18) 0.0519(18) -0.0075(14) 0.0123(14) -0.0018(14)
C8 0.054(2) 0.0485(19) 0.089(3) -0.0157(17) 0.0104(18) -0.0148(16)
C7 0.0486(19) 0.0535(19) 0.080(2) -0.0194(16) 0.0219(17) -0.0071(15)
C1 0.054(2) 0.066(2) 0.0475(17) 0.0094(15) 0.0148(14) -0.0139(16)
C10 0.0428(18) 0.070(2) 0.067(2) 0.0058(17) 0.0147(16) 0.0001(16)
C9 0.0424(18) 0.0509(18) 0.066(2) 0.0101(15) 0.0059(14) -0.0076(14)
F3 0.088(2) 0.124(3) 0.205(4) 0.065(3) 0.008(2) -0.047(2)
F1 0.139(4) 0.272(6) 0.147(4) -0.018(4) -0.001(3) -0.138(4)
C20 0.050(2) 0.065(2) 0.101(3) 0.020(2) 0.004(2) -0.0173(18)
F0AA 0.061(2) 0.167(4) 0.644(14) -0.183(7) 0.125(4) -0.064(3)

_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 C13 1.340(4) . ?
N1 C2 1.337(4) . ?
C14 C13 1.496(4) . ?
C14 C19 1.390(4) . ?
C14 C15 1.394(4) . ?
C4 C5 1.403(4) . ?
C4 C2 1.408(4) . ?
C4 C3 1.509(4) . ?
C13 C12 1.388(4) . ?
C12 C5 1.386(4) . ?
C5 C6 1.486(4) . ?
C2 C1 1.512(4) . ?
C19 C18 1.394(4) . ?
C6 C11 1.382(4) . ?
C6 C7 1.392(4) . ?
C15 C16 1.386(4) . ?
C17 C16 1.369(5) . ?
C17 C18 1.370(5) . ?
C11 C10 1.389(5) . ?
C8 C7 1.381(5) . ?
C8 C9 1.360(6) . ?
C10 C9 1.396(5) . ?
C9 C20 1.490(5) . ?
F3 C20 1.285(5) . ?
F1 C20 1.332(6) . ?
C20 F0AA 1.203(6) . ?

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
C2 N1 C13 118.5(2) . . ?
C19 C14 C13 120.0(3) . . ?
C19 C14 C15 117.9(3) . . ?
C15 C14 C13 122.1(3) . . ?
C5 C4 C2 116.7(3) . . ?
C5 C4 C3 122.1(3) . . ?
C2 C4 C3 121.2(3) . . ?
N1 C13 C14 116.5(3) . . ?
N1 C13 C12 121.6(3) . . ?
C12 C13 C14 121.9(3) . . ?
C5 C12 C13 120.2(3) . . ?
C4 C5 C6 123.6(3) . . ?
C12 C5 C4 119.0(3) . . ?
C12 C5 C6 117.4(3) . . ?
N1 C2 C4 124.0(3) . . ?
N1 C2 C1 115.2(3) . . ?
C4 C2 C1 120.9(3) . . ?
C14 C19 C18 120.7(3) . . ?
C11 C6 C5 120.0(3) . . ?
C11 C6 C7 118.6(3) . . ?
C7 C6 C5 121.4(3) . . ?
C16 C15 C14 121.2(3) . . ?
C16 C17 C18 120.5(3) . . ?
C17 C16 C15 119.8(3) . . ?
C17 C18 C19 120.0(3) . . ?
C6 C11 C10 121.2(3) . . ?
C9 C8 C7 120.8(3) . . ?
C8 C7 C6 120.3(3) . . ?
C11 C10 C9 118.9(3) . . ?
C8 C9 C10 120.2(3) . . ?
C8 C9 C20 120.1(3) . . ?
C10 C9 C20 119.7(4) . . ?
F3 C20 C9 114.6(3) . . ?
F3 C20 F1 93.1(4) . . ?
F1 C20 C9 112.5(4) . . ?
F0AA C20 C9 116.9(4) . . ?
F0AA C20 F3 113.0(5) . . ?
F0AA C20 F1 103.6(6) . . ?

_olex2_submission_special_instructions 'No special instructions were received'
