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

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_EuL2
_audit_block_doi                 10.5517/ccdc.csd.cc279tn1
_database_code_depnum_ccdc_archive 'CCDC 2065023'
_audit_update_record             
;
2021-03-20 deposited with the CCDC.	2021-03-26 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C22 H10 Br2 Eu F12 N14 O3[+ solvent]'
_chemical_formula_sum            'C22 H10 Br2 Eu F12 N14 O3[+ solvent]'
_chemical_formula_weight         1058.21

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'
Eu Eu -0.1578 3.6682 '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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_H-M_alt        'P 43 21 2'
_space_group_name_Hall           'P 4nw 2abw'

_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, z+1/2'
'-y+1/2, x+1/2, z+3/4'
'y+1/2, -x+1/2, z+1/4'
'-x+1/2, y+1/2, -z+3/4'
'x+1/2, -y+1/2, -z+1/4'
'y, x, -z'
'-y, -x, -z+1/2'

_cell_length_a                   17.598(2)
_cell_length_b                   17.598(2)
_cell_length_c                   15.093(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4673.9(13)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    5794
_cell_measurement_theta_min      2.31
_cell_measurement_theta_max      21.86

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.504
_exptl_crystal_F_000             2020
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.10
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.05
_exptl_absorpt_coefficient_mu    3.136
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.4808
_exptl_absorpt_correction_T_max  0.7447
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.40.59a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_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       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            16297
_diffrn_reflns_av_unetI/netI     0.0630
_diffrn_reflns_av_R_equivalents  0.0911
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         2.315
_diffrn_reflns_theta_max         21.724
_diffrn_reflns_theta_full        21.724
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             2763
_reflns_number_gt                2306
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.698
_reflns_Friedel_fraction_max     0.999
_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.
 
 Structure factors included contributions from the .fab file.
 
 _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    'SHELXT 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_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)+(0.1148P)²+68.1175P] 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     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_extinction_coef       0.0058(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Flack x determined using 789 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.039(13)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         2763
_refine_ls_number_parameters     234
_refine_ls_number_restraints     249
_refine_ls_R_factor_all          0.1002
_refine_ls_R_factor_gt           0.0853
_refine_ls_wR_factor_ref         0.2236
_refine_ls_wR_factor_gt          0.2123
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_restrained_S_all      1.077
_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
Eu1_1 Eu 0.58020(7) 0.58020(7) 0.500000 0.0393(8) Uani 1 2 d S T P . .
C1_1 C 0.899(2) 0.453(3) 0.559(3) 0.101(6) Uani 1 1 d . U . . .
F2_1 F 0.9323(12) 0.4072(15) 0.5342(17) 0.126(7) Uani 1 1 d . U . . .
F3_1 F 0.8914(15) 0.435(2) 0.652(2) 0.143(7) Uani 1 1 d . U . . .
F4_1 F 0.9217(18) 0.518(2) 0.589(2) 0.161(8) Uani 1 1 d . U . . .
N5_1 N 0.7736(14) 0.5267(14) 0.5453(17) 0.061(4) Uani 1 1 d . U . . .
N6_1 N 0.7043(12) 0.5097(12) 0.5046(15) 0.049(3) Uani 1 1 d . U . . .
C7_1 C 0.7135(17) 0.4428(17) 0.4692(19) 0.058(4) Uani 1 1 d . U . . .
N8_1 N 0.7811(13) 0.4088(14) 0.4854(15) 0.059(4) Uani 1 1 d . U . . .
C9_1 C 0.8126(17) 0.4644(19) 0.532(2) 0.065(4) Uani 1 1 d . U . . .
N10_1 N 0.5909(13) 0.4518(12) 0.4041(14) 0.049(3) Uani 1 1 d . U . . .
C11_1 C 0.6490(16) 0.4066(15) 0.4171(17) 0.046(4) Uani 1 1 d . U . . .
C12_1 C 0.6547(17) 0.3330(15) 0.3818(16) 0.047(4) Uani 1 1 d . U . . .
H12_1 H 0.697330 0.301261 0.392696 0.057 Uiso 1 1 calc R U . . .
C13_1 C 0.5936(16) 0.3094(15) 0.3294(17) 0.044(4) Uani 1 1 d . U . . .
C14_1 C 0.5353(17) 0.3569(15) 0.3191(17) 0.047(4) Uani 1 1 d . U . . .
H14_1 H 0.493988 0.340813 0.283222 0.056 Uiso 1 1 calc R U . . .
C15_1 C 0.5313(15) 0.4266(16) 0.3563(17) 0.046(4) Uani 1 1 d . U . . .
N16_1 N 0.4613(13) 0.5374(13) 0.4108(14) 0.046(4) Uani 1 1 d . U . . .
N17_1 N 0.3955(11) 0.5759(12) 0.3935(13) 0.047(4) Uani 1 1 d . U . . .
C18_1 C 0.3618(17) 0.5277(16) 0.3369(18) 0.047(4) Uani 1 1 d . U . . .
N19_1 N 0.4019(12) 0.4709(13) 0.3064(14) 0.048(4) Uani 1 1 d . U . . .
C20_1 C 0.4714(16) 0.4741(16) 0.3585(17) 0.045(4) Uani 1 1 d . U . . .
C21_1 C 0.2884(18) 0.547(2) 0.3020(18) 0.057(8) Uani 1 1 d . U . . .
F22_1 F 0.2497(14) 0.4833(16) 0.284(2) 0.140(11) Uani 1 1 d . . . . .
F23_1 F 0.2851(13) 0.5854(18) 0.2291(16) 0.128(7) Uani 1 1 d . . . . .
F24_1 F 0.2477(14) 0.5940(17) 0.3499(15) 0.128(7) Uani 1 1 d . U . . .
Br25_1 Br 0.5965(2) 0.2127(2) 0.2796(2) 0.0821(14) Uani 1 1 d . . . . .
O2_2 O 0.6214(10) 0.6103(10) 0.6513(10) 0.042(3) Uani 1 1 d . . . . .
H2A_2 H 0.595048 0.580626 0.703998 0.063 Uiso 1 1 d R U . . .
H2B_2 H 0.607965 0.665235 0.674017 0.063 Uiso 1 1 d R U . . .
O3_2 O 0.6797(9) 0.6797(9) 0.500000 0.042(3) Uani 1 2 d DS T P . .
H3A_2 H 0.677(5) 0.735(5) 0.522(16) 0.063 Uiso 1 1 d D U . . .


_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
Eu1_1 O2_2 2.454(15) 7_556 ?
Eu1_1 O2_2 2.454(15) . ?
Eu1_1 O3_2 2.48(2) . ?
Eu1_1 N6_1 2.51(2) 7_556 ?
Eu1_1 N6_1 2.51(2) . ?
Eu1_1 N16_1 2.60(2) . ?
Eu1_1 N16_1 2.60(2) 7_556 ?
Eu1_1 N10_1 2.689(19) . ?
Eu1_1 N10_1 2.689(19) 7_556 ?
C1_1 F2_1 1.07(4) . ?
C1_1 F4_1 1.30(5) . ?
C1_1 F3_1 1.44(5) . ?
C1_1 C9_1 1.58(5) . ?
N5_1 C9_1 1.31(4) . ?
N5_1 N6_1 1.40(3) . ?
N6_1 C7_1 1.30(3) . ?
C7_1 N8_1 1.35(3) . ?
C7_1 C11_1 1.52(4) . ?
C7_1 C9_1 2.02(4) . ?
N8_1 C9_1 1.33(4) . ?
N10_1 C11_1 1.31(3) . ?
N10_1 C15_1 1.35(3) . ?
C11_1 C12_1 1.40(4) . ?
C12_1 C13_1 1.40(4) . ?
C12_1 H12_1 0.9500 . ?
C13_1 C14_1 1.33(4) . ?
C13_1 Br25_1 1.86(2) . ?
C14_1 C15_1 1.35(4) . ?
C14_1 H14_1 0.9500 . ?
C15_1 C20_1 1.35(4) . ?
N16_1 N17_1 1.37(3) . ?
N16_1 C20_1 1.38(4) . ?
N17_1 C18_1 1.34(3) . ?
C18_1 N19_1 1.31(4) . ?
C18_1 C21_1 1.44(4) . ?
N19_1 C20_1 1.45(3) . ?
C21_1 F23_1 1.29(4) . ?
C21_1 F24_1 1.31(4) . ?
C21_1 F22_1 1.34(4) . ?
O2_2 H2A_2 1.0577 . ?
O2_2 H2B_2 1.0524 . ?
O3_2 H3A_2 1.03(3) . ?
O3_2 H3A_2 1.03(3) 7_556 ?

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
O2_2 Eu1_1 O2_2 137.6(8) 7_556 . ?
O2_2 Eu1_1 O3_2 68.8(4) 7_556 . ?
O2_2 Eu1_1 O3_2 68.8(4) . . ?
O2_2 Eu1_1 N6_1 79.9(7) 7_556 7_556 ?
O2_2 Eu1_1 N6_1 89.1(7) . 7_556 ?
O3_2 Eu1_1 N6_1 74.6(5) . 7_556 ?
O2_2 Eu1_1 N6_1 89.1(7) 7_556 . ?
O2_2 Eu1_1 N6_1 79.9(7) . . ?
O3_2 Eu1_1 N6_1 74.6(5) . . ?
N6_1 Eu1_1 N6_1 149.2(10) 7_556 . ?
O2_2 Eu1_1 N16_1 77.1(6) 7_556 . ?
O2_2 Eu1_1 N16_1 141.5(6) . . ?
O3_2 Eu1_1 N16_1 140.7(5) . . ?
N6_1 Eu1_1 N16_1 80.8(7) 7_556 . ?
N6_1 Eu1_1 N16_1 124.8(7) . . ?
O2_2 Eu1_1 N16_1 141.5(6) 7_556 7_556 ?
O2_2 Eu1_1 N16_1 77.1(6) . 7_556 ?
O3_2 Eu1_1 N16_1 140.7(5) . 7_556 ?
N6_1 Eu1_1 N16_1 124.8(7) 7_556 7_556 ?
N6_1 Eu1_1 N16_1 80.8(7) . 7_556 ?
N16_1 Eu1_1 N16_1 78.6(10) . 7_556 ?
O2_2 Eu1_1 N10_1 74.5(6) 7_556 . ?
O2_2 Eu1_1 N10_1 131.4(6) . . ?
O3_2 Eu1_1 N10_1 123.0(5) . . ?
N6_1 Eu1_1 N10_1 138.6(7) 7_556 . ?
N6_1 Eu1_1 N10_1 62.6(7) . . ?
N16_1 Eu1_1 N10_1 62.2(7) . . ?
N16_1 Eu1_1 N10_1 67.9(7) 7_556 . ?
O2_2 Eu1_1 N10_1 131.4(6) 7_556 7_556 ?
O2_2 Eu1_1 N10_1 74.4(6) . 7_556 ?
O3_2 Eu1_1 N10_1 123.0(5) . 7_556 ?
N6_1 Eu1_1 N10_1 62.6(7) 7_556 7_556 ?
N6_1 Eu1_1 N10_1 138.6(7) . 7_556 ?
N16_1 Eu1_1 N10_1 67.9(7) . 7_556 ?
N16_1 Eu1_1 N10_1 62.2(7) 7_556 7_556 ?
N10_1 Eu1_1 N10_1 114.0(10) . 7_556 ?
F2_1 C1_1 F4_1 128(4) . . ?
F2_1 C1_1 F3_1 103(4) . . ?
F4_1 C1_1 F3_1 83(3) . . ?
F2_1 C1_1 C9_1 123(4) . . ?
F4_1 C1_1 C9_1 106(4) . . ?
F3_1 C1_1 C9_1 101(3) . . ?
C9_1 N5_1 N6_1 102(2) . . ?
C7_1 N6_1 N5_1 105(2) . . ?
C7_1 N6_1 Eu1_1 122.9(18) . . ?
N5_1 N6_1 Eu1_1 131.7(15) . . ?
N6_1 C7_1 N8_1 116(3) . . ?
N6_1 C7_1 C11_1 120(2) . . ?
N8_1 C7_1 C11_1 124(2) . . ?
N6_1 C7_1 C9_1 75.3(19) . . ?
N8_1 C7_1 C9_1 40.6(15) . . ?
C11_1 C7_1 C9_1 165(2) . . ?
C9_1 N8_1 C7_1 98(2) . . ?
N5_1 C9_1 N8_1 119(3) . . ?
N5_1 C9_1 C1_1 125(3) . . ?
N8_1 C9_1 C1_1 116(3) . . ?
N5_1 C9_1 C7_1 77.1(18) . . ?
N8_1 C9_1 C7_1 41.6(14) . . ?
C1_1 C9_1 C7_1 157(3) . . ?
C11_1 N10_1 C15_1 119(2) . . ?
C11_1 N10_1 Eu1_1 119.0(17) . . ?
C15_1 N10_1 Eu1_1 120.7(17) . . ?
N10_1 C11_1 C12_1 124(3) . . ?
N10_1 C11_1 C7_1 114(2) . . ?
C12_1 C11_1 C7_1 122(2) . . ?
C13_1 C12_1 C11_1 116(3) . . ?
C13_1 C12_1 H12_1 122.1 . . ?
C11_1 C12_1 H12_1 122.1 . . ?
C14_1 C13_1 C12_1 118(2) . . ?
C14_1 C13_1 Br25_1 123(2) . . ?
C12_1 C13_1 Br25_1 119(2) . . ?
C13_1 C14_1 C15_1 124(3) . . ?
C13_1 C14_1 H14_1 117.9 . . ?
C15_1 C14_1 H14_1 117.9 . . ?
C20_1 C15_1 N10_1 113(2) . . ?
C20_1 C15_1 C14_1 128(3) . . ?
N10_1 C15_1 C14_1 119(3) . . ?
N17_1 N16_1 C20_1 114(2) . . ?
N17_1 N16_1 Eu1_1 129.5(16) . . ?
C20_1 N16_1 Eu1_1 115.4(17) . . ?
C18_1 N17_1 N16_1 100(2) . . ?
N19_1 C18_1 N17_1 118(3) . . ?
N19_1 C18_1 C21_1 123(3) . . ?
N17_1 C18_1 C21_1 119(3) . . ?
C18_1 N19_1 C20_1 104(2) . . ?
C15_1 C20_1 N16_1 128(2) . . ?
C15_1 C20_1 N19_1 128(2) . . ?
N16_1 C20_1 N19_1 103(2) . . ?
F23_1 C21_1 F24_1 97(3) . . ?
F23_1 C21_1 F22_1 104(3) . . ?
F24_1 C21_1 F22_1 111(3) . . ?
F23_1 C21_1 C18_1 118(3) . . ?
F24_1 C21_1 C18_1 116(3) . . ?
F22_1 C21_1 C18_1 110(3) . . ?
Eu1_1 O2_2 H2A_2 117.6 . . ?
Eu1_1 O2_2 H2B_2 115.8 . . ?
H2A_2 O2_2 H2B_2 96.4 . . ?
Eu1_1 O3_2 H3A_2 130(3) . . ?
Eu1_1 O3_2 H3A_2 130(3) . 7_556 ?
H3A_2 O3_2 H3A_2 100(6) . 7_556 ?

_refine_diff_density_max         2.992
_refine_diff_density_min         -2.062
_refine_diff_density_rms         0.192




# start Validation Reply Form
_vrf_THETM01_EuL2                
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: The crystals of this supramolecular assembly diffract
very weakly in nature, possibly due to a large amount of amorphous solvents
and highly-disordered counterions existing in the unit cell. There was just
no significant diffraction intensity at high angles(Theta > 22) even though
we optimized the measurement.
;
# end Validation Reply Form
