# Electronic Supplementary Material (ESI) for New Journal of Chemistry.
# This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 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_shelx
_database_code_depnum_ccdc_archive 'CCDC 2175595'
loop_
_audit_author_name
_audit_author_address
'Luis Alves'
;Associacao do Instituto Superior Tecnico para a Investigacao e Desenvolvimento
Portugal
;
_audit_update_record             
;
2022-05-29 deposited with the CCDC.	2022-08-02 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C26 H38 Cu F6 N4 O2, 2(C2 H3 O2)'
_chemical_formula_sum            'C30 H44 Cu F6 N4 O6'
_chemical_formula_weight         734.24

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu 0.3201 1.2651 '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      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

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

_cell_length_a                   11.619(1)
_cell_length_b                   17.461(2)
_cell_length_c                   8.833(1)
_cell_angle_alpha                90
_cell_angle_beta                 107.463(5)
_cell_angle_gamma                90
_cell_volume                     1709.4(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    2217
_cell_measurement_theta_min      2.33
_cell_measurement_theta_max      21.54

_exptl_crystal_description       block
_exptl_crystal_colour            purple
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.426
_exptl_crystal_F_000             766
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.140
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.080
_exptl_absorpt_coefficient_mu    0.718
_shelx_estimated_absorpt_T_min   0.906
_shelx_estimated_absorpt_T_max   0.945
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.906
_exptl_absorpt_correction_T_max  0.945
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            11293
_diffrn_reflns_av_unetI/netI     0.0557
_diffrn_reflns_av_R_equivalents  0.0447
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_theta_min         2.684
_diffrn_reflns_theta_max         25.675
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             3242
_reflns_number_gt                2235
_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       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1669P)²+3.6919P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3231
_refine_ls_number_parameters     227
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.1234
_refine_ls_R_factor_gt           0.0920
_refine_ls_wR_factor_ref         0.2787
_refine_ls_wR_factor_gt          0.2563
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_restrained_S_all      1.078
_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
Cu1 Cu 0.5000 0.0000 0.0000 0.0298(4) Uani 1 2 d S . P . .
N1 N 0.5858(4) 0.1043(3) -0.0191(5) 0.0320(11) Uani 1 1 d . . . . .
N2 N 0.3409(5) 0.0492(3) -0.0227(6) 0.0347(12) Uani 1 1 d . . . . .
C7 C 0.6981(5) 0.2180(3) 0.1350(6) 0.0307(13) Uani 1 1 d . . . . .
C8 C 0.6454(5) 0.2876(3) 0.0729(7) 0.0312(13) Uani 1 1 d . . . . .
H8 H 0.5601 0.2912 0.0316 0.037 Uiso 1 1 calc R U . . .
C9 C 0.7142(5) 0.3504(4) 0.0705(7) 0.0337(14) Uani 1 1 d . . . . .
H9 H 0.6763 0.3972 0.0279 0.040 Uiso 1 1 calc R U . . .
F1 F 0.8666(5) 0.4593(4) -0.0013(8) 0.114(3) Uani 1 1 d . . . . .
C4 C 0.3860(6) 0.1734(4) -0.1285(8) 0.0425(16) Uani 1 1 d . . . . .
H4A H 0.3487 0.2139 -0.2060 0.051 Uiso 1 1 calc R U . . .
H4B H 0.4005 0.1953 -0.0210 0.051 Uiso 1 1 calc R U . . .
C6 C 0.6248(6) 0.1471(4) 0.1367(7) 0.0344(14) Uani 1 1 d . . . . .
H6A H 0.5519 0.1618 0.1659 0.041 Uiso 1 1 calc R U . . .
H6B H 0.6729 0.1121 0.2200 0.041 Uiso 1 1 calc R U . . .
C5 C 0.5062(6) 0.1526(4) -0.1498(7) 0.0372(14) Uani 1 1 d . . . . .
H5A H 0.4916 0.1247 -0.2514 0.045 Uiso 1 1 calc R U . . .
H5B H 0.5498 0.2004 -0.1579 0.045 Uiso 1 1 calc R U . . .
F2 F 1.0191(5) 0.4016(3) 0.1187(10) 0.107(2) Uani 1 1 d . . . . .
C12 C 0.8229(7) 0.2158(4) 0.2012(9) 0.0528(19) Uani 1 1 d . . . . .
H12 H 0.8605 0.1701 0.2502 0.063 Uiso 1 1 calc R U . . .
C3 C 0.2967(6) 0.1078(4) -0.1484(8) 0.0398(15) Uani 1 1 d . . . . .
H3A H 0.2182 0.1281 -0.1439 0.048 Uiso 1 1 calc R U . . .
H3B H 0.2840 0.0839 -0.2537 0.048 Uiso 1 1 calc R U . . .
C10 C 0.8384(5) 0.3470(3) 0.1292(7) 0.0340(14) Uani 1 1 d . . . . .
C13 C 0.9131(6) 0.4162(4) 0.1255(9) 0.0516(19) Uani 1 1 d . . . . .
C11 C 0.8931(6) 0.2796(4) 0.1965(10) 0.059(2) Uani 1 1 d . . . . .
H11 H 0.9784 0.2770 0.2394 0.070 Uiso 1 1 calc R U . . .
F3 F 0.9242(9) 0.4608(4) 0.2423(10) 0.162(5) Uani 1 1 d . . . . .
C2 C 0.2492(6) -0.0114(4) -0.0371(9) 0.0406(16) Uani 1 1 d . . . . .
H2A H 0.2166 -0.0279 -0.1492 0.049 Uiso 1 1 calc R U . . .
H2B H 0.1816 0.0083 -0.0018 0.049 Uiso 1 1 calc R U . . .
C1 C 0.6915(6) 0.0783(4) -0.0652(8) 0.0388(15) Uani 1 1 d . . . . .
H1A H 0.7500 0.1208 -0.0523 0.047 Uiso 1 1 calc R U . . .
H1B H 0.6657 0.0627 -0.1782 0.047 Uiso 1 1 calc R U . . .
O1 O 0.5505(6) 0.0129(4) 0.3065(7) 0.0516(14) Uani 1 1 d . . . . .
C14 C 0.3111(7) 0.3757(4) -0.1493(8) 0.0439(17) Uani 1 1 d . . . . .
O3 O 0.3358(9) 0.3622(5) -0.2641(10) 0.130(4) Uani 1 1 d . . . . .
O2 O 0.3785(11) 0.4123(8) -0.0502(11) 0.173(6) Uani 1 1 d . . . . .
C15 C 0.2122(14) 0.3492(10) -0.0899(18) 0.134(5) Uani 1 1 d . U . . .
H15A H 0.1477 0.3274 -0.1777 0.202 Uiso 1 1 calc R U . . .
H15B H 0.1805 0.3926 -0.0443 0.202 Uiso 1 1 calc R U . . .
H15C H 0.2427 0.3101 -0.0081 0.202 Uiso 1 1 calc R U . . .
H2N H 0.365(6) 0.077(4) 0.081(8) 0.040(18) Uiso 1 1 d . . . . .
H1O H 0.592(10) -0.012(6) 0.382(14) 0.08(4) Uiso 1 1 d . . . . .
H2O H 0.505(9) 0.047(6) 0.337(11) 0.09(3) Uiso 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Cu1 N2 1.993(5) . ?
Cu1 N2 1.993(5) 3_655 ?
Cu1 N1 2.108(5) 3_655 ?
Cu1 N1 2.108(5) . ?
N1 C1 1.477(8) . ?
N1 C5 1.503(8) . ?
N1 C6 1.511(7) . ?
N2 C2 1.481(8) . ?
N2 C3 1.485(8) . ?
N2 H2N 1.00(7) . ?
C7 C12 1.391(9) . ?
C7 C8 1.397(8) . ?
C7 C6 1.506(8) . ?
C8 C9 1.360(9) . ?
C8 H8 0.9500 . ?
C9 C10 1.381(9) . ?
C9 H9 0.9500 . ?
F1 C13 1.322(9) . ?
C4 C5 1.508(9) . ?
C4 C3 1.519(9) . ?
C4 H4A 0.9900 . ?
C4 H4B 0.9900 . ?
C6 H6A 0.9900 . ?
C6 H6B 0.9900 . ?
C5 H5A 0.9900 . ?
C5 H5B 0.9900 . ?
F2 C13 1.277(9) . ?
C12 C11 1.389(10) . ?
C12 H12 0.9500 . ?
C3 H3A 0.9900 . ?
C3 H3B 0.9900 . ?
C10 C11 1.384(9) . ?
C10 C13 1.494(9) . ?
C13 F3 1.268(9) . ?
C11 H11 0.9500 . ?
C2 C1 1.510(9) 3_655 ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C1 C2 1.510(9) 3_655 ?
C1 H1A 0.9900 . ?
C1 H1B 0.9900 . ?
O1 H1O 0.82(11) . ?
O1 H2O 0.89(11) . ?
C14 O3 1.157(9) . ?
C14 O2 1.174(12) . ?
C14 C15 1.473(16) . ?
C15 H15A 0.9800 . ?
C15 H15B 0.9800 . ?
C15 H15C 0.9800 . ?

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 Cu1 N2 180.0 . 3_655 ?
N2 Cu1 N1 86.19(19) . 3_655 ?
N2 Cu1 N1 93.81(19) 3_655 3_655 ?
N2 Cu1 N1 93.81(19) . . ?
N2 Cu1 N1 86.19(19) 3_655 . ?
N1 Cu1 N1 180.0 3_655 . ?
C1 N1 C5 109.4(5) . . ?
C1 N1 C6 110.9(5) . . ?
C5 N1 C6 111.7(5) . . ?
C1 N1 Cu1 102.1(4) . . ?
C5 N1 Cu1 110.5(4) . . ?
C6 N1 Cu1 112.0(3) . . ?
C2 N2 C3 110.5(5) . . ?
C2 N2 Cu1 108.8(4) . . ?
C3 N2 Cu1 118.3(4) . . ?
C2 N2 H2N 115(4) . . ?
C3 N2 H2N 107(4) . . ?
Cu1 N2 H2N 97(4) . . ?
C12 C7 C8 117.9(6) . . ?
C12 C7 C6 119.6(6) . . ?
C8 C7 C6 122.5(5) . . ?
C9 C8 C7 121.2(6) . . ?
C9 C8 H8 119.4 . . ?
C7 C8 H8 119.4 . . ?
C8 C9 C10 120.8(6) . . ?
C8 C9 H9 119.6 . . ?
C10 C9 H9 119.6 . . ?
C5 C4 C3 115.5(6) . . ?
C5 C4 H4A 108.4 . . ?
C3 C4 H4A 108.4 . . ?
C5 C4 H4B 108.4 . . ?
C3 C4 H4B 108.4 . . ?
H4A C4 H4B 107.5 . . ?
C7 C6 N1 114.4(5) . . ?
C7 C6 H6A 108.7 . . ?
N1 C6 H6A 108.7 . . ?
C7 C6 H6B 108.7 . . ?
N1 C6 H6B 108.7 . . ?
H6A C6 H6B 107.6 . . ?
N1 C5 C4 114.7(5) . . ?
N1 C5 H5A 108.6 . . ?
C4 C5 H5A 108.6 . . ?
N1 C5 H5B 108.6 . . ?
C4 C5 H5B 108.6 . . ?
H5A C5 H5B 107.6 . . ?
C11 C12 C7 120.9(6) . . ?
C11 C12 H12 119.6 . . ?
C7 C12 H12 119.6 . . ?
N2 C3 C4 111.2(5) . . ?
N2 C3 H3A 109.4 . . ?
C4 C3 H3A 109.4 . . ?
N2 C3 H3B 109.4 . . ?
C4 C3 H3B 109.4 . . ?
H3A C3 H3B 108.0 . . ?
C9 C10 C11 119.5(6) . . ?
C9 C10 C13 120.3(6) . . ?
C11 C10 C13 120.2(6) . . ?
F3 C13 F2 107.3(8) . . ?
F3 C13 F1 104.9(8) . . ?
F2 C13 F1 103.2(7) . . ?
F3 C13 C10 113.4(7) . . ?
F2 C13 C10 114.4(6) . . ?
F1 C13 C10 112.7(6) . . ?
C10 C11 C12 119.8(6) . . ?
C10 C11 H11 120.1 . . ?
C12 C11 H11 120.1 . . ?
N2 C2 C1 108.3(5) . 3_655 ?
N2 C2 H2A 110.0 . . ?
C1 C2 H2A 110.0 3_655 . ?
N2 C2 H2B 110.0 . . ?
C1 C2 H2B 110.0 3_655 . ?
H2A C2 H2B 108.4 . . ?
N1 C1 C2 109.9(5) . 3_655 ?
N1 C1 H1A 109.7 . . ?
C2 C1 H1A 109.7 3_655 . ?
N1 C1 H1B 109.7 . . ?
C2 C1 H1B 109.7 3_655 . ?
H1A C1 H1B 108.2 . . ?
H1O O1 H2O 112(10) . . ?
O3 C14 O2 118.6(11) . . ?
O3 C14 C15 132.3(11) . . ?
O2 C14 C15 108.8(10) . . ?
C14 C15 H15A 109.5 . . ?
C14 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C14 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?

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
C12 C7 C8 C9 3.0(9) . . . . ?
C6 C7 C8 C9 -178.9(5) . . . . ?
C7 C8 C9 C10 0.2(9) . . . . ?
C12 C7 C6 N1 -101.2(7) . . . . ?
C8 C7 C6 N1 80.6(7) . . . . ?
C1 N1 C6 C7 60.6(7) . . . . ?
C5 N1 C6 C7 -61.6(6) . . . . ?
Cu1 N1 C6 C7 173.9(4) . . . . ?
C1 N1 C5 C4 171.5(5) . . . . ?
C6 N1 C5 C4 -65.4(6) . . . . ?
Cu1 N1 C5 C4 59.9(6) . . . . ?
C3 C4 C5 N1 -70.6(7) . . . . ?
C8 C7 C12 C11 -3.9(11) . . . . ?
C6 C7 C12 C11 177.8(7) . . . . ?
C2 N2 C3 C4 176.0(5) . . . . ?
Cu1 N2 C3 C4 -57.6(7) . . . . ?
C5 C4 C3 N2 65.2(7) . . . . ?
C8 C9 C10 C11 -2.4(10) . . . . ?
C8 C9 C10 C13 179.8(6) . . . . ?
C9 C10 C13 F3 84.1(10) . . . . ?
C11 C10 C13 F3 -93.7(10) . . . . ?
C9 C10 C13 F2 -152.4(7) . . . . ?
C11 C10 C13 F2 29.8(11) . . . . ?
C9 C10 C13 F1 -34.9(10) . . . . ?
C11 C10 C13 F1 147.3(8) . . . . ?
C9 C10 C11 C12 1.4(11) . . . . ?
C13 C10 C11 C12 179.2(7) . . . . ?
C7 C12 C11 C10 1.8(13) . . . . ?
C3 N2 C2 C1 166.4(5) . . . 3_655 ?
Cu1 N2 C2 C1 34.9(6) . . . 3_655 ?
C5 N1 C1 C2 -162.4(5) . . . 3_655 ?
C6 N1 C1 C2 74.0(6) . . . 3_655 ?
Cu1 N1 C1 C2 -45.4(5) . . . 3_655 ?

_refine_diff_density_max         1.874
_refine_diff_density_min         -1.251
_refine_diff_density_rms         0.126

####################################################################### 
# 
# 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_3b
_database_code_depnum_ccdc_archive 'CCDC 2175594'
loop_
_audit_author_name
_audit_author_address
'Luis Alves'
;Associacao do Instituto Superior Tecnico para a Investigacao e Desenvolvimento
Portugal
;
_audit_update_record             
;
2022-07-26 deposited with the CCDC.	2022-08-02 downloaded from the CCDC.
;

_vrf_PLAT213_3b                  
;
RESPONSE: The compound displays slightly disordered CF3 groups resulting 
in fluorine atoms with large thermal ellipsoids. However, it does not 
indicate an incorrect atom-type assignment.  
;
_vrf_PLAT990_3b                  
;
RESPONSE: The compound crystallized with disordered molecules of the solvent 
in the asymmetric unit and thus the Squeeze/PLATON sequence was applied as 
all attempts to model the disorder did not lead to acceptable solutions.   
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C26 H36 Cu F6 N4 O, 2(C2 H3 O2), H2 O'
_chemical_formula_sum            'C30 H44 Cu F6 N4 O6'
_chemical_formula_weight         734.24

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu 0.3201 1.2651 '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'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           52
_space_group_name_H-M_alt        'P n n a'
_space_group_name_Hall           '-P 2a 2bc'

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

_cell_length_a                   9.2146(5)
_cell_length_b                   22.905(2)
_cell_length_c                   17.524(1)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3698.6(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    1703
_cell_measurement_theta_min      2.93
_cell_measurement_theta_max      21.08

_exptl_crystal_description       block
_exptl_crystal_colour            blue
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.319
_exptl_crystal_F_000             1532
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.100
_exptl_crystal_size_mid          0.080
_exptl_crystal_size_min          0.080
_exptl_absorpt_coefficient_mu    0.663
_shelx_estimated_absorpt_T_min   0.937
_shelx_estimated_absorpt_T_max   0.949
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.937
_exptl_absorpt_correction_T_max  0.949
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            14001
_diffrn_reflns_av_unetI/netI     0.0824
_diffrn_reflns_av_R_equivalents  0.0748
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_theta_min         1.463
_diffrn_reflns_theta_max         25.696
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             3512
_reflns_number_gt                2178
_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       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          SQUEEZE
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1673P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3512
_refine_ls_number_parameters     221
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1223
_refine_ls_R_factor_gt           0.0833
_refine_ls_wR_factor_ref         0.2659
_refine_ls_wR_factor_gt          0.2409
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_restrained_S_all      1.040
_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
Cu1 Cu 0.98260(9) 0.250000 0.250000 0.0269(4) Uani 1 2 d S T P . .
O1 O 1.2175(5) 0.250000 0.250000 0.0423(15) Uani 1 2 d S T P . .
N2 N 0.9775(4) 0.1722(2) 0.1974(3) 0.0309(11) Uani 1 1 d . . . . .
C12 C 1.0020(5) 0.1831(3) 0.5376(3) 0.0304(13) Uani 1 1 d . . . . .
H12 H 0.973602 0.222100 0.538920 0.037 Uiso 1 1 calc R U . . .
C6 C 1.0799(5) 0.1990(3) 0.3993(3) 0.0320(13) Uani 1 1 d . . . . .
H6A H 1.156043 0.182667 0.367606 0.038 Uiso 1 1 calc R U . . .
H6B H 1.110379 0.237787 0.414793 0.038 Uiso 1 1 calc R U . . .
N1 N 0.9424(4) 0.2042(2) 0.3522(2) 0.0299(11) Uani 1 1 d . . . . .
C2 C 0.9867(6) 0.1269(3) 0.2572(3) 0.0369(14) Uani 1 1 d . . . . .
H2A H 1.086601 0.122121 0.273521 0.044 Uiso 1 1 calc R U . . .
H2B H 0.952205 0.089866 0.237583 0.044 Uiso 1 1 calc R U . . .
C5 C 0.8212(5) 0.2320(3) 0.3964(3) 0.0334(14) Uani 1 1 d . . . . .
H5A H 0.802976 0.208831 0.441722 0.040 Uiso 1 1 calc R U . . .
H5B H 0.733948 0.230991 0.365438 0.040 Uiso 1 1 calc R U . . .
C7 C 1.0622(5) 0.1615(3) 0.4694(3) 0.0325(13) Uani 1 1 d . . . . .
C11 C 0.9829(6) 0.1505(3) 0.6014(4) 0.0405(15) Uani 1 1 d . . . . .
H11 H 0.943309 0.166605 0.645482 0.049 Uiso 1 1 calc R U . . .
C8 C 1.1071(6) 0.1032(3) 0.4695(4) 0.0382(14) Uani 1 1 d . . . . .
H8 H 1.150492 0.087489 0.426266 0.046 Uiso 1 1 calc R U . . .
C1 C 0.8932(6) 0.1463(3) 0.3243(3) 0.0360(14) Uani 1 1 d . . . . .
H1A H 0.792551 0.148653 0.308390 0.043 Uiso 1 1 calc R U . . .
H1B H 0.900128 0.117812 0.365079 0.043 Uiso 1 1 calc R U . . .
C10 C 1.0251(6) 0.0915(3) 0.5985(4) 0.0432(17) Uani 1 1 d . . . . .
C3 C 0.8501(5) 0.1619(3) 0.1462(3) 0.0341(14) Uani 1 1 d . . . . .
H3A H 0.761122 0.165751 0.175418 0.041 Uiso 1 1 calc R U . . .
H3B H 0.854254 0.122487 0.126110 0.041 Uiso 1 1 calc R U . . .
C13 C 1.0047(9) 0.0552(4) 0.6668(5) 0.069(2) Uani 1 1 d . . . . .
C9 C 1.0875(7) 0.0686(3) 0.5334(4) 0.0483(17) Uani 1 1 d . . . . .
H9 H 1.116530 0.029746 0.532547 0.058 Uiso 1 1 calc R U . . .
C4 C 0.8488(6) 0.2941(3) 0.4203(3) 0.0369(14) Uani 1 1 d . . . . .
H4A H 0.941643 0.295963 0.446324 0.044 Uiso 1 1 calc R U . . .
H4B H 0.774561 0.305713 0.456481 0.044 Uiso 1 1 calc R U . . .
O2 O 0.3985(4) 0.2062(2) 0.1465(2) 0.0471(12) Uani 1 1 d . . . . .
O3 O 0.2193(4) 0.15184(18) 0.1029(2) 0.0397(10) Uani 1 1 d . . . . .
C14 C 0.3502(6) 0.1619(3) 0.1139(3) 0.0349(14) Uani 1 1 d . . . . .
C15 C 0.4582(6) 0.1175(3) 0.0832(4) 0.0461(17) Uani 1 1 d . . . . .
H15A H 0.545538 0.137102 0.067935 0.069 Uiso 1 1 calc R U . . .
H15B H 0.416818 0.097750 0.040078 0.069 Uiso 1 1 calc R U . . .
H15C H 0.480435 0.089503 0.122343 0.069 Uiso 1 1 calc R U . . .
F2 F 1.0730(10) 0.0681(4) 0.7234(4) 0.173(4) Uani 1 1 d . . . . .
F3 F 1.0111(15) 0.0027(3) 0.6578(4) 0.278(8) Uani 1 1 d . . . . .
F1 F 0.8788(8) 0.0595(6) 0.6981(7) 0.287(9) Uani 1 1 d . . . . .
O4 O 0.5993(6) 0.250000 0.250000 0.0481(17) Uani 1 2 d S T P . .
H2N H 1.075(7) 0.162(3) 0.169(4) 0.052(18) Uiso 1 1 d . . . . .
H4O H 0.540200 0.233100 0.211000 0.13(4) Uiso 1 1 d . . . . .
H1O H 1.283699 0.233700 0.223001 0.06(2) Uiso 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Cu1 N2 2.007(5) 3 ?
Cu1 N2 2.007(5) . ?
Cu1 N1 2.109(4) . ?
Cu1 N1 2.109(4) 3 ?
Cu1 O1 2.165(5) . ?
N2 C2 1.478(7) . ?
N2 C3 1.496(6) . ?
N2 H2N 1.05(6) . ?
C12 C11 1.357(8) . ?
C12 C7 1.407(8) . ?
C12 H12 0.9300 . ?
C6 C7 1.508(8) . ?
C6 N1 1.515(6) . ?
C6 H6A 0.9700 . ?
C6 H6B 0.9700 . ?
N1 C1 1.485(7) . ?
N1 C5 1.501(7) . ?
C2 C1 1.522(8) . ?
C2 H2A 0.9700 . ?
C2 H2B 0.9700 . ?
C5 C4 1.505(8) . ?
C5 H5A 0.9700 . ?
C5 H5B 0.9700 . ?
C7 C8 1.399(8) . ?
C11 C10 1.408(9) . ?
C11 H11 0.9300 . ?
C8 C9 1.383(8) . ?
C8 H8 0.9300 . ?
C1 H1A 0.9700 . ?
C1 H1B 0.9700 . ?
C10 C9 1.381(9) . ?
C10 C13 1.468(10) . ?
C3 C4 1.541(8) 3 ?
C3 H3A 0.9700 . ?
C3 H3B 0.9700 . ?
C13 F2 1.212(9) . ?
C13 F3 1.214(11) . ?
C13 F1 1.288(12) . ?
C9 H9 0.9300 . ?
C4 H4A 0.9700 . ?
C4 H4B 0.9700 . ?
O2 C14 1.246(7) . ?
O3 C14 1.243(7) . ?
C14 C15 1.522(8) . ?
C15 H15A 0.9600 . ?
C15 H15B 0.9600 . ?
C15 H15C 0.9600 . ?

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 Cu1 N2 177.3(2) 3 . ?
N2 Cu1 N1 92.71(18) 3 . ?
N2 Cu1 N1 86.82(18) . . ?
N2 Cu1 N1 86.82(18) 3 3 ?
N2 Cu1 N1 92.71(18) . 3 ?
N1 Cu1 N1 159.8(2) . 3 ?
N2 Cu1 O1 91.34(12) 3 . ?
N2 Cu1 O1 91.34(12) . . ?
N1 Cu1 O1 100.10(11) . . ?
N1 Cu1 O1 100.10(11) 3 . ?
H1O O1 H1O 89.3(5) . 3 ?
C2 N2 C3 111.1(4) . . ?
C2 N2 Cu1 107.2(3) . . ?
C3 N2 Cu1 115.7(4) . . ?
C2 N2 H2N 98(3) . . ?
C3 N2 H2N 110(3) . . ?
Cu1 N2 H2N 113(3) . . ?
C11 C12 C7 123.9(6) . . ?
C11 C12 H12 118.1 . . ?
C7 C12 H12 118.1 . . ?
C7 C6 N1 113.4(4) . . ?
C7 C6 H6A 108.9 . . ?
N1 C6 H6A 108.9 . . ?
C7 C6 H6B 108.9 . . ?
N1 C6 H6B 108.9 . . ?
H6A C6 H6B 107.7 . . ?
C1 N1 C5 108.8(4) . . ?
C1 N1 C6 111.4(4) . . ?
C5 N1 C6 112.0(4) . . ?
C1 N1 Cu1 102.6(3) . . ?
C5 N1 Cu1 110.9(3) . . ?
C6 N1 Cu1 110.7(3) . . ?
N2 C2 C1 108.1(5) . . ?
N2 C2 H2A 110.1 . . ?
C1 C2 H2A 110.1 . . ?
N2 C2 H2B 110.1 . . ?
C1 C2 H2B 110.1 . . ?
H2A C2 H2B 108.4 . . ?
N1 C5 C4 114.8(4) . . ?
N1 C5 H5A 108.6 . . ?
C4 C5 H5A 108.6 . . ?
N1 C5 H5B 108.6 . . ?
C4 C5 H5B 108.6 . . ?
H5A C5 H5B 107.6 . . ?
C8 C7 C12 116.8(5) . . ?
C8 C7 C6 120.9(5) . . ?
C12 C7 C6 122.3(5) . . ?
C12 C11 C10 117.6(6) . . ?
C12 C11 H11 121.2 . . ?
C10 C11 H11 121.2 . . ?
C9 C8 C7 120.7(6) . . ?
C9 C8 H8 119.7 . . ?
C7 C8 H8 119.7 . . ?
N1 C1 C2 110.0(4) . . ?
N1 C1 H1A 109.7 . . ?
C2 C1 H1A 109.7 . . ?
N1 C1 H1B 109.7 . . ?
C2 C1 H1B 109.7 . . ?
H1A C1 H1B 108.2 . . ?
C9 C10 C11 120.6(6) . . ?
C9 C10 C13 120.8(7) . . ?
C11 C10 C13 118.6(7) . . ?
N2 C3 C4 110.8(4) . 3 ?
N2 C3 H3A 109.5 . . ?
C4 C3 H3A 109.5 3 . ?
N2 C3 H3B 109.5 . . ?
C4 C3 H3B 109.5 3 . ?
H3A C3 H3B 108.1 . . ?
F2 C13 F3 108.7(9) . . ?
F2 C13 F1 95.7(11) . . ?
F3 C13 F1 100.0(9) . . ?
F2 C13 C10 117.6(6) . . ?
F3 C13 C10 116.7(9) . . ?
F1 C13 C10 114.8(7) . . ?
C10 C9 C8 120.4(6) . . ?
C10 C9 H9 119.8 . . ?
C8 C9 H9 119.8 . . ?
C5 C4 C3 114.1(5) . 3 ?
C5 C4 H4A 108.7 . . ?
C3 C4 H4A 108.7 3 . ?
C5 C4 H4B 108.7 . . ?
C3 C4 H4B 108.7 3 . ?
H4A C4 H4B 107.6 . . ?
O3 C14 O2 124.7(5) . . ?
O3 C14 C15 117.1(6) . . ?
O2 C14 C15 118.2(5) . . ?
C14 C15 H15A 109.5 . . ?
C14 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C14 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?

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 C6 N1 C1 -60.7(6) . . . . ?
C7 C6 N1 C5 61.4(6) . . . . ?
C7 C6 N1 Cu1 -174.2(4) . . . . ?
C3 N2 C2 C1 -86.9(5) . . . . ?
Cu1 N2 C2 C1 40.4(5) . . . . ?
C1 N1 C5 C4 -172.9(4) . . . . ?
C6 N1 C5 C4 63.4(6) . . . . ?
Cu1 N1 C5 C4 -60.8(5) . . . . ?
C11 C12 C7 C8 -1.5(7) . . . . ?
C11 C12 C7 C6 179.2(5) . . . . ?
N1 C6 C7 C8 98.6(6) . . . . ?
N1 C6 C7 C12 -82.1(6) . . . . ?
C7 C12 C11 C10 -0.5(8) . . . . ?
C12 C7 C8 C9 2.2(7) . . . . ?
C6 C7 C8 C9 -178.5(5) . . . . ?
C5 N1 C1 C2 159.3(4) . . . . ?
C6 N1 C1 C2 -76.7(5) . . . . ?
Cu1 N1 C1 C2 41.8(5) . . . . ?
N2 C2 C1 N1 -57.4(5) . . . . ?
C12 C11 C10 C9 1.9(8) . . . . ?
C12 C11 C10 C13 -179.7(5) . . . . ?
C2 N2 C3 C4 -174.9(5) . . . 3 ?
Cu1 N2 C3 C4 62.7(5) . . . 3 ?
C9 C10 C13 F2 114.5(11) . . . . ?
C11 C10 C13 F2 -64.0(12) . . . . ?
C9 C10 C13 F3 -17.5(13) . . . . ?
C11 C10 C13 F3 164.1(10) . . . . ?
C9 C10 C13 F1 -134.0(11) . . . . ?
C11 C10 C13 F1 47.5(12) . . . . ?
C11 C10 C9 C8 -1.2(9) . . . . ?
C13 C10 C9 C8 -179.6(5) . . . . ?
C7 C8 C9 C10 -0.9(8) . . . . ?
N1 C5 C4 C3 69.6(6) . . . 3 ?

_refine_diff_density_max         1.051
_refine_diff_density_min         -0.917
_refine_diff_density_rms         0.193


# SQUEEZE RESULTS (Version = 220119)
# Note: Data are Listed for all Voids in the P1 Unit Cell
# i.e. Centre of Gravity, Solvent Accessible Volume,
# Recovered number of Electrons in the Void and
# Details about the Squeezed Material
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.014 0.000 0.000 258 112 ' '
2 -0.018 0.500 0.500 258 112 ' '
_platon_squeeze_void_probe_radius 1.20
_platon_squeeze_details          ?
