# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2019

####################################################################### 
# 
# 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_CFA-15
_database_code_depnum_ccdc_archive 'CCDC 1906421'
loop_
_audit_author_name
_audit_author_address
'Maciej Grzywa'
;Ausgburg University
Germany
;
_audit_update_record             
;
2019-03-28 deposited with the CCDC.	2019-09-25 downloaded from the CCDC.
;
_audit_creation_method           
;
Olex2 1.2-ac4
(compiled 2018.05.17 svn.r3504 for Rigaku Oxford Diffraction, GUI svn.r5492)
;
_shelx_SHELXL_version_number     2018/3
__chemical_name_common           ?
_chemical_name_systematic        ?
_chemical_formula_moiety         '0.5(C30 H18 Cu6 F24 N10 O14)'
_chemical_formula_sum            'C15 H9 Cu3 F12 N5 O7'
_chemical_formula_weight         789.89
_chemical_absolute_configuration ?
_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'
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'
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'

_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.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_H-M_alt        'C 1 2 1'
_space_group_name_Hall           'C 2y'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z'

_cell_length_a                   14.2997(4)
_cell_length_b                   9.4881(3)
_cell_length_c                   9.3862(3)
_cell_angle_alpha                90
_cell_angle_beta                 109.7120(10)
_cell_angle_gamma                90
_cell_volume                     1198.86(6)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    9955
_cell_measurement_temperature    268(2)
_cell_measurement_theta_max      28.69
_cell_measurement_theta_min      2.30
_shelx_estimated_absorpt_T_max   0.768
_shelx_estimated_absorpt_T_min   0.768
_exptl_absorpt_coefficient_mu    2.780
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6985
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS V2012/1 (Bruker AXS Inc.)'
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            blue
_exptl_crystal_colour_lustre     .
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    2.188
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             770
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0603
_diffrn_reflns_av_unetI/netI     0.0460
_diffrn_reflns_Laue_measured_fraction_full 0.967
_diffrn_reflns_Laue_measured_fraction_max 0.937
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_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            18173
_diffrn_reflns_point_group_measured_fraction_full 0.962
_diffrn_reflns_point_group_measured_fraction_max 0.920
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.480
_diffrn_reflns_theta_min         2.626
_diffrn_ambient_temperature      268.01
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.967
_diffrn_measured_fraction_theta_max 0.937
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed tube'
_reflns_Friedel_coverage         0.851
_reflns_Friedel_fraction_full    0.956
_reflns_Friedel_fraction_max     0.901
_reflns_number_gt                2385
_reflns_number_total             2536
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences. Completness statistics refer to single and
 composite reflections containing twin component 1 only.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX3'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Diamond 4.4'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  Word
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.915
_refine_diff_density_min         -1.230
_refine_diff_density_rms         0.178
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.06(4)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.147
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     211
_refine_ls_number_reflns         2536
_refine_ls_number_restraints     182
_refine_ls_R_factor_all          0.0542
_refine_ls_R_factor_gt           0.0500
_refine_ls_restrained_S_all      1.111
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0200P)²+19.8971P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1104
_refine_ls_wR_factor_ref         0.1114
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.94(4)
 0.06(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: C0AA(0.5) H0AA(0.5) C1AA(0.5) H1Aa(0.5) H1Ab(0.5) H1Ac(0.5)
 C2AA(0.5) H2Aa(0.5) H2Ab(0.5) H2Ac(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C0AA(H0AA)
5.b Idealised Me refined as rotating group:
 C1AA(H1Aa,H1Ab,H1Ac), C2AA(H2Aa,H2Ab,H2Ac)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
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 0.47751(8) 0.70260(12) 0.65923(12) 0.0108(3) Uani 1 1 d . U . . .
Cu2 Cu 0.500000 0.57392(17) 1.000000 0.0151(4) Uani 1 2 d S TU P . .
F2 F 0.2344(8) 0.3322(12) 1.0031(10) 0.054(3) Uani 1 1 d . U . . .
O2 O 0.3528(5) 0.6003(9) 0.6433(9) 0.0273(19) Uani 1 1 d . U . . .
F5 F 0.2121(7) 0.5765(10) 0.3600(8) 0.053(2) Uani 1 1 d . U . . .
N2 N 0.1071(6) 0.3227(9) 0.5109(9) 0.0126(16) Uani 1 1 d . U . . .
F6 F 0.1334(5) 0.3924(9) 0.2576(7) 0.0363(19) Uani 1 1 d . U . . .
N1 N 0.0965(6) 0.3166(9) 0.6520(9) 0.0130(16) Uani 1 1 d . U . . .
F3 F 0.1975(6) 0.5480(9) 0.9522(9) 0.045(2) Uani 1 1 d . U . . .
O3 O 0.5470(5) 0.6018(9) 0.8382(8) 0.0236(19) Uani 1 1 d . U . . .
F4 F 0.2884(6) 0.3807(12) 0.3758(10) 0.055(3) Uani 1 1 d . U . . .
O1 O 0.3656(6) 0.5268(10) 0.8738(8) 0.031(2) Uani 1 1 d . U . . .
C1 C 0.1698(7) 0.3938(11) 0.7459(10) 0.0130(19) Uani 1 1 d . U . . .
O4 O 0.500000 0.5368(11) 0.500000 0.025(2) Uani 1 2 d S TU P . .
F1 F 0.0818(6) 0.3966(10) 0.9161(9) 0.047(2) Uani 1 1 d . U . . .
C2 C 0.2301(9) 0.4531(13) 0.6695(13) 0.0140(19) Uani 1 1 d . U . . .
C6 C 0.2063(8) 0.4395(13) 0.3799(12) 0.024(2) Uani 1 1 d . U . . .
C4 C 0.3238(8) 0.5340(11) 0.7343(12) 0.018(2) Uani 1 1 d . U . . .
C5 C 0.1720(8) 0.4170(12) 0.9050(11) 0.021(2) Uani 1 1 d . U . . .
C3 C 0.1839(7) 0.4056(11) 0.5210(10) 0.0144(19) Uani 1 1 d . U . . .
ND N 0.500000 0.2973(16) 0.500000 0.041(4) Uani 1 2 d S TU P . .
C0AA C 0.5012(19) 0.418(2) 0.554(3) 0.031(5) Uani 0.5 1 d . U . A -1
H0AA H 0.503510 0.418092 0.653713 0.037 Uiso 0.5 1 calc R . . A -1
C1AA C 0.488(3) 0.292(3) 0.322(4) 0.062(9) Uani 0.5 1 d . U . A -1
H1AA H 0.464365 0.381403 0.276024 0.093 Uiso 0.5 1 calc GR . . A -1
H1AB H 0.440395 0.219955 0.272607 0.093 Uiso 0.5 1 calc GR . . A -1
H1AC H 0.550522 0.270612 0.311114 0.093 Uiso 0.5 1 calc GR . . A -1
C2AA C 0.510(3) 0.163(3) 0.560(4) 0.065(11) Uani 0.5 1 d . U . A -1
H2AA H 0.510492 0.167695 0.662587 0.098 Uiso 0.5 1 calc GR . . A -1
H2AB H 0.571223 0.122631 0.558761 0.098 Uiso 0.5 1 calc GR . . A -1
H2AC H 0.455373 0.105912 0.501050 0.098 Uiso 0.5 1 calc GR . . A -1
H3 H 0.602(14) 0.61(2) 0.87(2) 0.078 Uiso 1 1 d R . . . .


_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 O2 1.991(7) . ?
Cu1 N2 2.003(8) 4_556 ?
Cu1 N1 2.037(8) 3 ?
Cu1 O3 1.897(7) . ?
Cu1 O4 2.266(7) . ?
Cu2 O3 1.876(7) . ?
Cu2 O3 1.876(7) 2_657 ?
Cu2 O1 1.939(7) . ?
Cu2 O1 1.939(7) 2_657 ?
F2 C5 1.318(14) . ?
O2 C4 1.240(13) . ?
F5 C6 1.319(15) . ?
N2 N1 1.384(11) . ?
N2 C3 1.328(12) . ?
F6 C6 1.341(12) . ?
N1 C1 1.338(12) . ?
F3 C5 1.329(13) . ?
F4 C6 1.311(14) . ?
O1 C4 1.244(13) . ?
C1 C2 1.410(15) . ?
C1 C5 1.500(14) . ?
O4 C0AA 1.23(2) . ?
F1 C5 1.343(13) . ?
C2 C4 1.485(15) . ?
C2 C3 1.401(14) . ?
C6 C3 1.499(14) . ?
ND C0AA 1.25(3) . ?
ND C1AA 1.62(4) . ?
ND C2AA 1.38(3) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O2 Cu1 N2 86.1(3) . 4_556 ?
O2 Cu1 N1 173.5(3) . 3 ?
O2 Cu1 O4 86.3(3) . . ?
N2 Cu1 N1 87.6(3) 4_556 3 ?
N2 Cu1 O4 92.9(3) 4_556 . ?
N1 Cu1 O4 92.3(3) 3 . ?
O3 Cu1 O2 90.5(3) . . ?
O3 Cu1 N2 171.3(4) . 4_556 ?
O3 Cu1 N1 95.9(3) . 3 ?
O3 Cu1 O4 94.9(3) . . ?
O3 Cu2 O3 163.8(6) . 2_657 ?
O3 Cu2 O1 88.6(3) 2_657 . ?
O3 Cu2 O1 95.1(3) . . ?
O3 Cu2 O1 88.6(3) . 2_657 ?
O3 Cu2 O1 95.1(3) 2_657 2_657 ?
O1 Cu2 O1 153.3(6) . 2_657 ?
C4 O2 Cu1 134.0(7) . . ?
N1 N2 Cu1 120.5(6) . 4_546 ?
C3 N2 Cu1 131.0(7) . 4_546 ?
C3 N2 N1 108.2(8) . . ?
N2 N1 Cu1 114.6(6) . 3_445 ?
C1 N1 Cu1 138.3(7) . 3_445 ?
C1 N1 N2 107.0(8) . . ?
Cu2 O3 Cu1 124.3(4) . . ?
C4 O1 Cu2 131.0(7) . . ?
N1 C1 C2 111.2(9) . . ?
N1 C1 C5 119.0(9) . . ?
C2 C1 C5 129.5(9) . . ?
Cu1 O4 Cu1 92.1(4) . 2_656 ?
C0AA O4 Cu1 156.7(12) . 2_656 ?
C0AA O4 Cu1 110.6(12) . . ?
C1 C2 C4 128.3(10) . . ?
C3 C2 C1 102.3(9) . . ?
C3 C2 C4 129.1(10) . . ?
F5 C6 F6 106.0(9) . . ?
F5 C6 C3 112.2(10) . . ?
F6 C6 C3 110.4(9) . . ?
F4 C6 F5 108.4(10) . . ?
F4 C6 F6 106.2(10) . . ?
F4 C6 C3 113.2(10) . . ?
O2 C4 O1 126.8(10) . . ?
O2 C4 C2 116.5(9) . . ?
O1 C4 C2 116.7(10) . . ?
F2 C5 F3 107.0(9) . . ?
F2 C5 C1 112.8(10) . . ?
F2 C5 F1 107.5(10) . . ?
F3 C5 C1 112.4(9) . . ?
F3 C5 F1 105.7(10) . . ?
F1 C5 C1 111.0(9) . . ?
N2 C3 C2 111.2(9) . . ?
N2 C3 C6 118.9(9) . . ?
C2 C3 C6 129.9(9) . . ?
C0AA ND C1AA 115.3(18) . . ?
C0AA ND C2AA 134.1(19) . . ?
C2AA ND C1AA 111(2) . . ?
O4 C0AA ND 133(2) . . ?

_olex2_submission_special_instructions 'No special instructions were received'
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.94(4)
2 0.06(4)

_exptl_crystal_recrystallization_method solvothermal
####################################################################### 
# 
# 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_H2-tfpc
_database_code_depnum_ccdc_archive 'CCDC 1913583'
loop_
_audit_author_name
_audit_author_address
'Henning A. Hoeppe'
;Universitaet Augsburg
Germany
;
_audit_update_record             
;
2019-05-02 deposited with the CCDC.	2019-09-25 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_THETM01_H2-tfpc             
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: Crystal contains only weakly scattering atoms and apparently the mosaicity is quite large. 
;
_vrf_PLAT089_H2-tfpc             
;
PROBLEM: Poor Data / Parameter Ratio (Zmax < 18) ........       3.21 Note
RESPONSE: Crystal contains only weakly scattering atoms and apparently the mosaicity is quite large. 
;
_vrf_PLAT434_H2-tfpc             
;
PROBLEM: Short Inter HL..HL Contact F32      ..F32              2.04 Ang.
RESPONSE: Within CF3 groups typically F-F distances between 2.0 and 2.2 Ang are found, so these values are not ominous -- especially since the angles and bond-lengths are well within the so far observed regimes. 
;
_vrf_PLAT230_H2-tfpc             
;
PROBLEM: Hirshfeld Test Diff for    F51      --C51      .        7.6 s.u.
RESPONSE: see above
;
_vrf_PLAT780_H2-tfpc             
;
PROBLEM: Coordinates do not Form a Properly Connected Set     Please Do !
RESPONSE: not really necessary from our point of view
;
_vrf_PLAT936_H2-tfpc             
;
PROBLEM: The Embedded .res File Includes a DAMP Command .      400.0 Report
RESPONSE: The twin refinement ran more stable employing a DAMP command (presumably due to considerable movement of the CF3 groups)..
;
# Added during the CSD deposition process: Thursday 02 May 2019 12:50 PM
# end Validation Reply Form


_audit_creation_method           SHELXL-2013
_chemical_name_systematic        ?
_chemical_name_common            
'3,5-bis(trifluoromethyl)pyrazole-4-carboxylic acid'
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C6 H2 F6 N2 O2'
_chemical_formula_weight         248.10

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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           36
_space_group_name_H-M_alt        'C m c 21'
_space_group_name_Hall           'C 2c -2'

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

_cell_length_a                   6.7891(4)
_cell_length_b                   6.9057(3)
_cell_length_c                   17.1652(9)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     804.76(7)
_cell_formula_units_Z            4
_cell_measurement_temperature    200(2)
_cell_measurement_reflns_used    7108
_cell_measurement_theta_min      2.373
_cell_measurement_theta_max      25.242

_exptl_crystal_description       rod
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.048
_exptl_crystal_F_000             488
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.250
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.140
_exptl_absorpt_coefficient_mu    0.240
_shelx_estimated_absorpt_T_min   0.942
_shelx_estimated_absorpt_T_max   0.967
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5841
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_process_details   
; 
 multi-scan absorption correction using SADABS 
(G. M. Sheldrick, (1996). SADABS. Program for Empirical 
Absorption Correction. University of Göttingen, Germany.)
;
_exptl_special_details           ?

_diffrn_ambient_temperature      200(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       'omega scan'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            7108
_diffrn_reflns_av_unetI/netI     0.0105
_diffrn_reflns_av_R_equivalents  0.0268
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         2.373
_diffrn_reflns_theta_max         19.942
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measured_fraction_theta_full 0.530
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_Laue_measured_fraction_full 0.530
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_point_group_measured_fraction_full 0.528
_reflns_number_total             418
_reflns_number_gt                414
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.917
_reflns_Friedel_fraction_max     0.985
_reflns_Friedel_fraction_full    0.525

_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       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
 Refined as a 4-component twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0392P)²+11.1404P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refxyz
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 0 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.000
_chemical_absolute_configuration ?
_refine_ls_number_reflns         418
_refine_ls_number_parameters     68
_refine_ls_number_restraints     24
_refine_ls_R_factor_all          0.0679
_refine_ls_R_factor_gt           0.0668
_refine_ls_wR_factor_ref         0.1447
_refine_ls_wR_factor_gt          0.1437
_refine_ls_goodness_of_fit_ref   1.208
_refine_ls_restrained_S_all      1.169
_refine_ls_shift/su_max          0.040
_refine_ls_shift/su_mean         0.006

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
F51 F 0.0000 0.3485(3) 0.44545(16) 0.0458(17) Uani 1 2 d DS T P . .
F31 F 0.0000 0.3781(3) 0.0667(2) 0.0458(17) Uani 1 2 d DS T P . .
F52 F 0.3365(2) 0.4035(4) 0.9198(2) 0.0547(13) Uani 1 1 d . . . . .
F32 F 0.6505(3) 0.3980(4) 0.5771(2) 0.0547(13) Uani 1 1 d . . . . .
O1 O 0.0000 0.8148(14) 0.1818(6) 0.039(2) Uani 1 2 d DS T P . .
O2 O 0.0000 0.8122(15) 0.3107(5) 0.039(2) Uani 1 2 d DS T P . .
N1 N 0.0000 0.4175(4) 0.2904(4) 0.033(2) Uani 1 2 d DS T P . .
N2 N 0.0000 0.4226(4) 0.2131(4) 0.033(2) Uani 1 2 d DS T P . .
C41 C 0.0000 0.1004(18) 0.7465(6) 0.026(2) Uani 1 2 d DS T P . .
C4 C 0.0000 0.8890(18) 0.75139(6) 0.026(2) Uani 1 2 d DS T P . .
C5 C 0.0000 0.2349(3) 0.31545(8) 0.022(2) Uani 1 2 d DS T P . .
C3 C 0.0000 0.2394(3) 0.18879(8) 0.022(2) Uani 1 2 d DS T P . .
C51 C 0.0000 0.1914(2) 0.40074(9) 0.041(3) Uani 1 2 d DS T P . .
C31 C 0.0000 0.2076(2) 0.10268(9) 0.041(3) Uani 1 2 d DS T P . .
H1 H 0.0000 0.676(2) 0.1777(10) 0.050 Uiso 1 2 d DS U P . .
H2 H 0.0000 0.511(4) 0.3320(9) 0.050 Uiso 1 2 d DS U P . .


_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
F51 C51 1.3293(17) . ?
F31 C31 1.3294(17) . ?
F52 C51 1.3294(15) 6 ?
F32 C31 1.3294(15) 6 ?
O1 C41 1.256(11) 2_564 ?
O1 H1 0.960(14) . ?
O2 C41 1.256(11) 2_564 ?
N1 N2 1.328(9) . ?
N1 C5 1.332(3) . ?
N1 H2 0.960(13) . ?
N2 C3 1.332(3) . ?
C41 O1 1.256(11) 2_565 ?
C41 O2 1.256(11) 2_565 ?
C41 C4 1.462(18) 1_545 ?
C4 C3 1.393(8) 2_565 ?
C4 C5 1.393(8) 2_565 ?
C4 C41 1.462(18) 1_565 ?
C5 C4 1.393(8) 2_564 ?
C5 C51 1.495(2) . ?
C3 C4 1.393(8) 2_564 ?
C3 C31 1.495(2) . ?
C51 F52 1.3294(15) 7_454 ?
C51 F52 1.3294(15) 6_554 ?
C31 F32 1.3294(15) 6_554 ?
C31 F32 1.3294(15) 7_454 ?

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
C41 O1 H1 122.0(14) 2_564 . ?
N2 N1 C5 110.3(4) . . ?
N2 N1 H2 136.5(16) . . ?
C5 N1 H2 113.2(17) . . ?
N1 N2 C3 106.7(3) . . ?
O1 C41 O2 123.5(11) 2_565 2_565 ?
O1 C41 C4 121.1(9) 2_565 1_545 ?
O2 C41 C4 115.4(9) 2_565 1_545 ?
C3 C4 C5 102.6(8) 2_565 2_565 ?
C3 C4 C41 126.3(5) 2_565 1_565 ?
C5 C4 C41 131.2(6) 2_565 1_565 ?
N1 C5 C4 109.1(5) . 2_564 ?
N1 C5 C51 120.4(3) . . ?
C4 C5 C51 130.5(4) 2_564 . ?
N2 C3 C4 111.3(5) . 2_564 ?
N2 C3 C31 116.7(3) . . ?
C4 C3 C31 132.0(4) 2_564 . ?
F51 C51 F52 105.09(19) . 7_454 ?
F51 C51 F52 105.09(19) . 6_554 ?
F52 C51 F52 113.2(3) 7_454 6_554 ?
F51 C51 C5 113.66(19) . . ?
F52 C51 C5 109.9(2) 7_454 . ?
F52 C51 C5 109.9(2) 6_554 . ?
F31 C31 F32 109.42(18) . 6_554 ?
F31 C31 F32 109.42(18) . 7_454 ?
F32 C31 F32 100.4(2) 6_554 7_454 ?
F31 C31 C3 109.2(2) . . ?
F32 C31 C3 114.02(18) 6_554 . ?
F32 C31 C3 114.02(18) 7_454 . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O1 H1 N2 0.960(14) 1.853(17) 2.761(10) 156.6(16) .
N1 H2 O2 0.960(13) 2.12(3) 2.748(11) 122.1(18) .

_refine_diff_density_max         0.338
_refine_diff_density_min         -0.406
_refine_diff_density_rms         0.093

_shelxl_version_number           2013-4


loop_
_publcif_info_exptl_table_extra_item
sin_theta_over_lambda_max

loop_
_publcif_info_exptl_table_header_item
?



_publcif_funding_html            
;
;
