# 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_u16_03
_database_code_depnum_ccdc_archive 'CCDC 1909922'
loop_
_audit_author_name
_audit_author_address
'Tadeusz Lis '
;University of Wroclaw
Poland
;
_audit_update_record             
;
2019-04-13 deposited with the CCDC.	2019-06-24 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2017/1
_shelx_SHELXL_version_number     2017/1
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C14 H24 Cu2 Fe N10 O2, H2 O'
_chemical_formula_sum            'C14 H26 Cu2 Fe N10 O3'
_chemical_formula_weight         565.38

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'
Fe Fe 0.3463 0.8444 '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           12
_space_group_name_H-M_alt        'C 2/m'
_space_group_name_Hall           '-C 2y'

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

_cell_length_a                   10.895(8)
_cell_length_b                   9.354(7)
_cell_length_c                   11.045(9)
_cell_angle_alpha                90
_cell_angle_beta                 113.125(10)
_cell_angle_gamma                90
_cell_volume                     1035.2(14)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    2275
_cell_measurement_theta_min      2.98
_cell_measurement_theta_max      26.17

_exptl_crystal_description       plate
_exptl_crystal_colour            black
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.814
_exptl_crystal_F_000             576
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.420
_exptl_crystal_size_mid          0.380
_exptl_crystal_size_min          0.030
_exptl_absorpt_coefficient_mu    2.767
_shelx_estimated_absorpt_T_min   0.389
_shelx_estimated_absorpt_T_max   0.922
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Bruker, 2014)'
_exptl_absorpt_correction_T_min  0.513
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'Incoatec microsource'
_diffrn_radiation_monochromator  'multilayer optics'
_diffrn_measurement_device_type  'Bruker D8 gonimeter with APEX CCD detector'
_diffrn_measurement_method       'ω scans'
_diffrn_reflns_number            5590
_diffrn_reflns_av_unetI/netI     0.0653
_diffrn_reflns_av_R_equivalents  0.0857
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         2.979
_diffrn_reflns_theta_max         26.341
_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             1114
_reflns_number_gt                809
_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       'SMART (Bruker, 2002)'
_computing_cell_refinement       'SAINT (Bruker, 2009)'
_computing_data_reduction        'SAINT (Bruker, 2009)'
_computing_molecular_graphics    'PLATON (Spek, 2009)'
_computing_structure_solution    'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_publication_material  'SHELXL-2018/3 (Sheldrick, 2018)'
_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)+(0.1250P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         1114
_refine_ls_number_parameters     101
_refine_ls_number_restraints     24
_refine_ls_R_factor_all          0.0851
_refine_ls_R_factor_gt           0.0636
_refine_ls_wR_factor_ref         0.2010
_refine_ls_wR_factor_gt          0.1833
_refine_ls_goodness_of_fit_ref   1.117
_refine_ls_restrained_S_all      1.120
_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 0.12015(10) 0.000000 0.14912(10) 0.0324(5) Uani 1 2 d S T P . .
Fe1 Fe 0.500000 0.000000 0.000000 0.0204(5) Uani 1 4 d S T P . .
N1 N 0.2644(7) 0.000000 0.0858(7) 0.0245(15) Uani 1 2 d S T P . .
N2 N 0.6834(9) 0.000000 0.2968(8) 0.043(2) Uani 1 2 d S T P . .
N3 N 0.000000 0.1736(8) 0.000000 0.067(3) Uani 1 2 d S T P . .
N4 N -0.0294(7) 0.000000 0.2146(7) 0.0258(15) Uani 1 2 d S T P B .
H4 H -0.115623 0.000000 0.135561 0.031 Uiso 1 2 calc R U P A 1
C1 C 0.3522(8) 0.000000 0.0526(8) 0.0207(16) Uani 1 2 d S T P . .
C2 C 0.6152(9) 0.000000 0.1847(9) 0.0293(18) Uani 1 2 d S T P . .
C3 C 0.000000 0.2965(8) 0.000000 0.0301(19) Uani 1 2 d S T P . .
C4A C -0.0252(7) 0.1325(7) 0.2899(7) 0.0417(17) Uani 0.5 1 d D . P B 1
H4A H -0.088623 0.117738 0.332916 0.050 Uiso 0.5 1 calc R U P B 1
H4B H -0.063663 0.208989 0.223772 0.050 Uiso 0.5 1 calc R U P B 1
C5A C 0.0985(15) 0.1932(19) 0.3926(15) 0.042(4) Uani 0.5 1 d D U P B 1
H5A H 0.082518 0.291536 0.416368 0.050 Uiso 0.5 1 calc R U P B 1
H5B H 0.129641 0.133246 0.472920 0.050 Uiso 0.5 1 calc R U P B 1
O5A O 0.1930(11) 0.1934(12) 0.3339(11) 0.048(3) Uani 0.5 1 d D U P B 1
H5O H 0.261402 0.148197 0.382108 0.058 Uiso 0.5 1 calc R U P B 1
C4B C -0.0252(7) 0.1325(7) 0.2899(7) 0.0417(17) Uani 0.5 1 d D . P B 2
H4C H -0.074019 0.120030 0.348188 0.050 Uiso 0.5 1 calc R U P B 2
H4D H -0.064027 0.214255 0.230104 0.050 Uiso 0.5 1 calc R U P B 2
C5B C 0.1271(12) 0.1547(18) 0.3715(13) 0.031(3) Uani 0.5 1 d D U P B 2
H5C H 0.142726 0.251202 0.411586 0.038 Uiso 0.5 1 calc R U P B 2
H5D H 0.159551 0.083333 0.443313 0.038 Uiso 0.5 1 calc R U P B 2
N5B N 0.2030(12) 0.1388(13) 0.2833(11) 0.032(2) Uani 0.5 1 d D U P B 2
H5N H 0.288375 0.111687 0.332334 0.039 Uiso 0.5 1 calc R U P B 2
H5M H 0.205612 0.224558 0.245409 0.039 Uiso 0.5 1 calc R U P B 2
O1 O -0.007(3) 0.443(2) 0.544(2) 0.078(8) Uiso 0.25 1 d . . P C -1
H1O H -0.068078 0.496429 0.495870 0.094 Uiso 0.25 1 d R U P C -1
H1P H 0.066622 0.496429 0.586769 0.094 Uiso 0.25 1 d R U P C -1


_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 N5B 1.909(12) 6 ?
Cu1 N5B 1.909(12) . ?
Cu1 N1 1.956(7) . ?
Cu1 N4 2.025(6) . ?
Cu1 N3 2.317(5) 5 ?
Cu1 N3 2.317(5) . ?
Fe1 C3 1.903(8) 7 ?
Fe1 C3 1.903(8) 3_545 ?
Fe1 C1 1.914(8) 5_655 ?
Fe1 C1 1.914(8) . ?
Fe1 C2 1.930(10) . ?
Fe1 C2 1.930(10) 5_655 ?
N1 C1 1.151(11) . ?
N2 C2 1.167(11) . ?
N3 C3 1.150(11) . ?
N4 C4A 1.483(7) 6 ?
N4 C4B 1.483(7) . ?
N4 C4A 1.483(7) . ?
N4 H4 1.0000 . ?
C4A C5A 1.492(14) . ?
C4A H4A 0.9900 . ?
C4A H4B 0.9900 . ?
C5A O5A 1.416(13) . ?
C5A H5A 0.9900 . ?
C5A H5B 0.9900 . ?
O5A H5O 0.8400 . ?
C4B C5B 1.561(14) . ?
C4B H4C 0.9900 . ?
C4B H4D 0.9900 . ?
C5B N5B 1.512(12) . ?
C5B H5C 0.9900 . ?
C5B H5D 0.9900 . ?
N5B H5N 0.9100 . ?
N5B H5M 0.9100 . ?
O1 H1O 0.8336 . ?
O1 H1P 0.9106 . ?

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
N5B Cu1 N5B 85.7(7) 6 . ?
N5B Cu1 N1 94.4(3) 6 . ?
N5B Cu1 N1 94.4(3) . . ?
N5B Cu1 N4 85.7(3) 6 . ?
N5B Cu1 N4 85.7(3) . . ?
N1 Cu1 N4 179.9(3) . . ?
N1 Cu1 N3 93.14(15) . 5 ?
N4 Cu1 N3 86.82(16) . 5 ?
N5B Cu1 N3 172.3(3) 6 . ?
N5B Cu1 N3 92.2(4) . . ?
N1 Cu1 N3 93.14(15) . . ?
N4 Cu1 N3 86.82(16) . . ?
N3 Cu1 N3 89.0(3) 5 . ?
C3 Fe1 C3 180.0 7 3_545 ?
C3 Fe1 C1 90.0 7 5_655 ?
C3 Fe1 C1 90.0 3_545 5_655 ?
C3 Fe1 C1 90.0 7 . ?
C3 Fe1 C1 90.0 3_545 . ?
C1 Fe1 C1 180.0 5_655 . ?
C3 Fe1 C2 90.0 7 . ?
C3 Fe1 C2 90.0 3_545 . ?
C1 Fe1 C2 92.6(3) 5_655 . ?
C1 Fe1 C2 87.4(3) . . ?
C3 Fe1 C2 90.0 7 5_655 ?
C3 Fe1 C2 90.0 3_545 5_655 ?
C1 Fe1 C2 87.4(3) 5_655 5_655 ?
C1 Fe1 C2 92.6(3) . 5_655 ?
C2 Fe1 C2 180.0 . 5_655 ?
C1 N1 Cu1 177.8(8) . . ?
C3 N3 Cu1 134.49(13) . . ?
C3 N3 Cu1 134.49(13) . 5 ?
Cu1 N3 Cu1 91.0(3) . 5 ?
C4A N4 C4A 113.3(7) 6 . ?
C4A N4 Cu1 110.4(4) 6 . ?
C4B N4 Cu1 110.4(4) . . ?
C4A N4 Cu1 110.4(4) . . ?
C4A N4 H4 107.5 6 . ?
C4A N4 H4 107.5 . . ?
Cu1 N4 H4 107.5 . . ?
N1 C1 Fe1 179.2(8) . . ?
N2 C2 Fe1 179.1(7) . . ?
N3 C3 Fe1 180.0 . 3_455 ?
N4 C4A C5A 124.4(9) . . ?
N4 C4A H4A 106.2 . . ?
C5A C4A H4A 106.2 . . ?
N4 C4A H4B 106.2 . . ?
C5A C4A H4B 106.2 . . ?
H4A C4A H4B 106.4 . . ?
O5A C5A C4A 104.7(10) . . ?
O5A C5A H5A 110.8 . . ?
C4A C5A H5A 110.8 . . ?
O5A C5A H5B 110.8 . . ?
C4A C5A H5B 110.8 . . ?
H5A C5A H5B 108.9 . . ?
C5A O5A H5O 109.5 . . ?
N4 C4B C5B 103.1(7) . . ?
N4 C4B H4C 111.1 . . ?
C5B C4B H4C 111.1 . . ?
N4 C4B H4D 111.1 . . ?
C5B C4B H4D 111.1 . . ?
H4C C4B H4D 109.1 . . ?
N5B C5B C4B 109.9(9) . . ?
N5B C5B H5C 109.7 . . ?
C4B C5B H5C 109.7 . . ?
N5B C5B H5D 109.7 . . ?
C4B C5B H5D 109.7 . . ?
H5C C5B H5D 108.2 . . ?
C5B N5B Cu1 110.8(7) . . ?
C5B N5B H5N 109.5 . . ?
Cu1 N5B H5N 109.5 . . ?
C5B N5B H5M 109.5 . . ?
Cu1 N5B H5M 109.5 . . ?
H5N N5B H5M 108.1 . . ?
H1O O1 H1P 108.4 . . ?

_refine_diff_density_max         0.956
_refine_diff_density_min         -1.000
_refine_diff_density_rms         0.191

####################################################################### 
# 
# 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_a154a
_database_code_depnum_ccdc_archive 'CCDC 1909923'
loop_
_audit_author_name
_audit_author_address
'Tadeusz Lis '
;University of Wroclaw
Poland
;
_audit_update_record             
;
2019-04-13 deposited with the CCDC.	2019-06-24 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C4 H12 Cu3 N20 O'
_chemical_formula_sum            'C4 H12 Cu3 N20 O'
_chemical_formula_weight         546.96

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'

_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                   8.549(3)
_cell_length_b                   12.643(5)
_cell_length_c                   16.071(6)
_cell_angle_alpha                90
_cell_angle_beta                 99.20(5)
_cell_angle_gamma                90
_cell_volume                     1714.7(11)
_cell_formula_units_Z            4
_cell_measurement_temperature    85(2)
_cell_measurement_reflns_used    729
_cell_measurement_theta_min      2.9
_cell_measurement_theta_max      25

_exptl_crystal_description       block
_exptl_crystal_colour            black
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.119
_exptl_crystal_F_000             1084
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.140
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.070
_exptl_absorpt_coefficient_mu    3.737
_shelx_estimated_absorpt_T_min   0.623
_shelx_estimated_absorpt_T_max   0.780
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_correction_T_min  0.707
_exptl_absorpt_correction_T_max  0.814
_exptl_absorpt_process_details   
;
CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET)
(compiled Apr 28 2010,14:27:37)
Analytical numeric absorption correction using a multifaceted crystal
                        model based on expressions derived by R.C. Clark & J.S.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      85(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'Enhance (Mo) X-ray Source'
_diffrn_measurement_device_type  'Xcalibur, ccd camera Ruby'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            7047
_diffrn_reflns_av_unetI/netI     0.2291
_diffrn_reflns_av_R_equivalents  0.1222
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         2.902
_diffrn_reflns_theta_max         28.058
_diffrn_reflns_theta_full        25.500
_diffrn_measured_fraction_theta_max 0.974
_diffrn_measured_fraction_theta_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_point_group_measured_fraction_full 0.987
_reflns_number_total             4053
_reflns_number_gt                1880
_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       'CrysAlis CCD; Oxford-Diffraction Poland, 2003'
_computing_cell_refinement       'CrysAlis RED; Oxford-Diffraction Poland, 2003'
_computing_data_reduction        'CrysAlis RED; Oxford-Diffraction Poland, 2003'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_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)+(0.0320P)²]
 where P=(Fo²+2Fc²)/3
;
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         4053
_refine_ls_number_parameters     235
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.1947
_refine_ls_R_factor_gt           0.0965
_refine_ls_wR_factor_ref         0.2024
_refine_ls_wR_factor_gt          0.1587
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_restrained_S_all      1.013
_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 0.53921(17) 0.62323(11) 0.74623(9) 0.0259(4) Uani 1 1 d . . . . .
Cu2 Cu 0.66402(16) 0.51837(11) 0.58462(9) 0.0223(4) Uani 1 1 d . . . . .
Cu3 Cu 0.73252(16) 0.45944(11) 0.40617(8) 0.0214(4) Uani 1 1 d . . . . .
N3 N 0.4865(11) 0.5385(8) 0.3425(5) 0.021(2) Uani 1 1 d . . . . .
N4 N 0.5123(11) 0.6270(9) 0.3258(6) 0.026(2) Uani 1 1 d . . . . .
N5 N 0.5458(13) 0.7129(10) 0.3104(7) 0.043(3) Uani 1 1 d . . . . .
N6 N 0.6708(11) 0.6492(9) 0.6558(6) 0.031(3) Uani 1 1 d . . . . .
N7 N 0.7201(12) 0.7335(9) 0.6340(6) 0.030(3) Uani 1 1 d . . . . .
N8 N 0.7661(13) 0.8146(8) 0.6147(7) 0.039(3) Uani 1 1 d . . . . .
N9 N 0.6244(11) 0.4032(8) 0.4983(6) 0.0241(17) Uani 1 1 d . . . . .
N10 N 0.6176(11) 0.3108(8) 0.5116(6) 0.0241(17) Uani 1 1 d . . . . .
N11 N 0.6145(13) 0.2192(8) 0.5226(6) 0.034(3) Uani 1 1 d . . . . .
N12 N 0.7766(11) 0.5772(7) 0.4938(6) 0.025(2) Uani 1 1 d . . . . .
N13 N 0.9053(11) 0.6218(7) 0.5103(6) 0.020(2) Uani 1 1 d . . . . .
N14 N 1.0217(12) 0.6668(8) 0.5239(7) 0.033(3) Uani 1 1 d . . . . .
N15 N 0.3357(10) 0.6634(7) 0.6664(5) 0.018(2) Uani 1 1 d . . . . .
N16 N 0.2553(15) 0.7346(10) 0.6791(8) 0.052(4) Uani 1 1 d . . . . .
N17 N 0.1826(17) 0.8087(12) 0.6850(10) 0.100(6) Uani 1 1 d . . . . .
N18 N 0.8454(11) 0.5273(8) 0.3223(6) 0.032(3) Uani 1 1 d . . . . .
N19 N 0.9809(12) 0.5414(10) 0.3311(7) 0.043(2) Uani 1 1 d . . . . .
N20 N 1.1139(12) 0.5571(9) 0.3345(7) 0.043(2) Uani 1 1 d . . . . .
N1 N 0.7325(11) 0.5696(8) 0.8278(6) 0.035(3) Uani 1 1 d . . . . .
H1N H 0.7724 0.5048 0.8023 0.041 Uiso 1 1 calc R U . . .
N2 N 0.4138(11) 0.5550(7) 0.8262(5) 0.024(2) Uani 1 1 d . . . . .
H2A H 0.3717 0.6093 0.8612 0.029 Uiso 1 1 calc R U . . .
H2B H 0.3236 0.5150 0.7949 0.029 Uiso 1 1 calc R U . . .
C1 C 0.6758(13) 0.5376(10) 0.9045(7) 0.032(3) Uani 1 1 d . . . . .
H1A H 0.6615 0.6004 0.9393 0.038 Uiso 1 1 calc R U . . .
H1B H 0.7535 0.4898 0.9379 0.038 Uiso 1 1 calc R U . . .
C2 C 0.5231(16) 0.4826(10) 0.8802(8) 0.036(3) Uani 1 1 d . . . . .
H2C H 0.4780 0.4632 0.9311 0.043 Uiso 1 1 calc R U . . .
H2D H 0.5389 0.4170 0.8489 0.043 Uiso 1 1 calc R U . . .
C3 C 0.8668(14) 0.6486(11) 0.8418(8) 0.041(2) Uani 1 1 d D . . . .
H3A H 0.8342 0.7143 0.8679 0.049 Uiso 1 1 calc R U . A 1
H3B H 0.9033 0.6665 0.7881 0.049 Uiso 1 1 calc R U . A 1
C4 C 1.002(3) 0.588(2) 0.9042(16) 0.041(2) Uani 0.5 1 d D . P B 1
H4A H 1.0021 0.5139 0.8852 0.049 Uiso 0.5 1 calc R U P B 1
H4B H 1.1046 0.6195 0.8962 0.049 Uiso 0.5 1 calc R U P B 1
O1 O 0.9973(18) 0.5872(15) 0.9921(9) 0.041(2) Uani 0.5 1 d D . P B 1
H1 H 0.9825 0.6594 1.0117 0.061 Uiso 0.5 1 d R U P B 1
C5 C 1.025(2) 0.6332(19) 0.9035(16) 0.041(2) Uani 0.5 1 d D . P B 2
H5A H 1.0987 0.6934 0.9013 0.049 Uiso 0.5 1 calc R U P B 2
H5B H 1.0076 0.6223 0.9623 0.049 Uiso 0.5 1 calc R U P B 2
O2 O 1.0802(19) 0.5410(14) 0.8691(10) 0.041(2) Uani 0.5 1 d D . P B 2
H2F H 1.1284 0.4965 0.9163 0.061 Uiso 0.5 1 d R U P B 2


_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 1.997(9) . ?
Cu1 N6 2.002(9) . ?
Cu1 N1 2.053(10) . ?
Cu1 N15 2.054(9) . ?
Cu1 N5 2.312(12) 4_576 ?
Cu1 N3 2.482(9) 3_666 ?
Cu2 N9 2.002(9) . ?
Cu2 N6 2.006(10) . ?
Cu2 N3 2.006(9) 3_666 ?
Cu2 N12 2.016(9) . ?
Cu2 N20 2.327(11) 3_766 ?
Cu3 N15 1.973(9) 3_666 ?
Cu3 N18 1.975(10) . ?
Cu3 N9 1.998(9) . ?
Cu3 N12 2.043(9) . ?
Cu3 N3 2.404(9) . ?
Cu3 N14 2.733(11) 3_766 ?
N3 N4 1.180(12) . ?
N3 Cu2 2.006(9) 3_666 ?
N4 N5 1.159(13) . ?
N5 Cu1 2.312(12) 4_575 ?
N6 N7 1.219(13) . ?
N7 N8 1.158(13) . ?
N9 N10 1.190(12) . ?
N10 N11 1.172(12) . ?
N12 N13 1.226(12) . ?
N13 N14 1.137(12) . ?
N15 N16 1.170(13) . ?
N15 Cu3 1.973(9) 3_666 ?
N16 N17 1.137(15) . ?
N18 N19 1.158(13) . ?
N19 N20 1.147(13) . ?
N20 Cu2 2.327(11) 3_766 ?
N1 C1 1.452(14) . ?
N1 C3 1.511(15) . ?
N1 H1N 1.0000 . ?
N2 C2 1.485(14) . ?
N2 H2A 0.9900 . ?
N2 H2B 0.9900 . ?
C1 C2 1.476(17) . ?
C1 H1A 0.9900 . ?
C1 H1B 0.9900 . ?
C2 H2C 0.9900 . ?
C2 H2D 0.9900 . ?
C3 C5 1.56(2) . ?
C3 C4 1.59(2) . ?
C3 H3A 0.9900 . ?
C3 H3B 0.9900 . ?
C4 O1 1.42(3) . ?
C4 H4A 0.9900 . ?
C4 H4B 0.9900 . ?
O1 H1 0.9800 . ?
C5 O2 1.40(3) . ?
C5 H5A 0.9900 . ?
C5 H5B 0.9900 . ?
O2 H2F 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 N6 163.8(4) . . ?
N2 Cu1 N1 84.6(4) . . ?
N6 Cu1 N1 91.7(4) . . ?
N2 Cu1 N15 91.2(4) . . ?
N6 Cu1 N15 91.4(4) . . ?
N1 Cu1 N15 174.6(4) . . ?
N2 Cu1 N5 94.4(4) . 4_576 ?
N6 Cu1 N5 101.6(4) . 4_576 ?
N1 Cu1 N5 92.9(4) . 4_576 ?
N15 Cu1 N5 90.8(4) . 4_576 ?
N2 Cu1 N3 90.4(4) . 3_666 ?
N6 Cu1 N3 74.1(4) . 3_666 ?
N1 Cu1 N3 94.8(3) . 3_666 ?
N15 Cu1 N3 81.7(3) . 3_666 ?
N5 Cu1 N3 171.3(4) 4_576 3_666 ?
N9 Cu2 N6 168.7(4) . . ?
N9 Cu2 N3 95.2(4) . 3_666 ?
N6 Cu2 N3 85.7(4) . 3_666 ?
N9 Cu2 N12 79.3(4) . . ?
N6 Cu2 N12 97.8(4) . . ?
N3 Cu2 N12 168.6(4) 3_666 . ?
N9 Cu2 N20 97.0(4) . 3_766 ?
N6 Cu2 N20 94.2(4) . 3_766 ?
N3 Cu2 N20 94.0(4) 3_666 3_766 ?
N12 Cu2 N20 96.6(4) . 3_766 ?
N15 Cu3 N18 94.0(4) 3_666 . ?
N15 Cu3 N9 91.7(4) 3_666 . ?
N18 Cu3 N9 174.3(4) . . ?
N15 Cu3 N12 170.3(4) 3_666 . ?
N18 Cu3 N12 95.6(4) . . ?
N9 Cu3 N12 78.8(4) . . ?
N15 Cu3 N3 85.4(3) 3_666 . ?
N18 Cu3 N3 91.1(4) . . ?
N9 Cu3 N3 89.2(4) . . ?
N12 Cu3 N3 92.5(3) . . ?
N15 Cu3 N14 85.3(3) 3_666 3_766 ?
N18 Cu3 N14 96.1(4) . 3_766 ?
N9 Cu3 N14 84.5(3) . 3_766 ?
N12 Cu3 N14 95.6(3) . 3_766 ?
N3 Cu3 N14 168.6(3) . 3_766 ?
N4 N3 Cu2 129.3(8) . 3_666 ?
N4 N3 Cu3 107.9(7) . . ?
Cu2 N3 Cu3 101.6(4) 3_666 . ?
N5 N4 N3 176.6(12) . . ?
N4 N5 Cu1 161.0(10) . 4_575 ?
N7 N6 Cu1 127.8(8) . . ?
N7 N6 Cu2 122.5(8) . . ?
Cu1 N6 Cu2 108.1(5) . . ?
N8 N7 N6 178.5(12) . . ?
N10 N9 Cu3 121.6(8) . . ?
N10 N9 Cu2 126.7(8) . . ?
Cu3 N9 Cu2 102.0(4) . . ?
N11 N10 N9 177.6(11) . . ?
N13 N12 Cu2 121.9(8) . . ?
N13 N12 Cu3 123.0(8) . . ?
Cu2 N12 Cu3 100.0(4) . . ?
N14 N13 N12 177.0(13) . . ?
N16 N15 Cu3 125.7(8) . 3_666 ?
N16 N15 Cu1 122.9(8) . . ?
Cu3 N15 Cu1 108.4(4) 3_666 . ?
N17 N16 N15 173.1(18) . . ?
N19 N18 Cu3 124.9(9) . . ?
N20 N19 N18 175.6(14) . . ?
N19 N20 Cu2 132.0(10) . 3_766 ?
C1 N1 C3 113.9(9) . . ?
C1 N1 Cu1 106.9(7) . . ?
C3 N1 Cu1 113.1(8) . . ?
C1 N1 H1N 107.5 . . ?
C3 N1 H1N 107.5 . . ?
Cu1 N1 H1N 107.5 . . ?
C2 N2 Cu1 106.8(7) . . ?
C2 N2 H2A 110.4 . . ?
Cu1 N2 H2A 110.4 . . ?
C2 N2 H2B 110.4 . . ?
Cu1 N2 H2B 110.4 . . ?
H2A N2 H2B 108.6 . . ?
N1 C1 C2 107.9(10) . . ?
N1 C1 H1A 110.1 . . ?
C2 C1 H1A 110.1 . . ?
N1 C1 H1B 110.1 . . ?
C2 C1 H1B 110.1 . . ?
H1A C1 H1B 108.4 . . ?
C1 C2 N2 108.1(10) . . ?
C1 C2 H2C 110.1 . . ?
N2 C2 H2C 110.1 . . ?
C1 C2 H2D 110.1 . . ?
N2 C2 H2D 110.1 . . ?
H2C C2 H2D 108.4 . . ?
N1 C3 C5 125.1(14) . . ?
N1 C3 C4 103.6(13) . . ?
N1 C3 H3A 111.0 . . ?
C4 C3 H3A 111.0 . . ?
N1 C3 H3B 111.0 . . ?
C4 C3 H3B 111.0 . . ?
H3A C3 H3B 109.0 . . ?
O1 C4 C3 120(2) . . ?
O1 C4 H4A 107.3 . . ?
C3 C4 H4A 107.3 . . ?
O1 C4 H4B 107.3 . . ?
C3 C4 H4B 107.3 . . ?
H4A C4 H4B 106.9 . . ?
C4 O1 H1 109.6 . . ?
O2 C5 C3 99.5(16) . . ?
O2 C5 H5A 111.9 . . ?
C3 C5 H5A 111.9 . . ?
O2 C5 H5B 111.9 . . ?
C3 C5 H5B 111.9 . . ?
H5A C5 H5B 109.6 . . ?
C5 O2 H2F 107.4 . . ?

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
C3 N1 C1 C2 166.4(10) . . . . ?
Cu1 N1 C1 C2 40.7(11) . . . . ?
N1 C1 C2 N2 -56.5(12) . . . . ?
Cu1 N2 C2 C1 42.9(10) . . . . ?
C1 N1 C3 C5 54.5(19) . . . . ?
Cu1 N1 C3 C5 176.9(14) . . . . ?
C1 N1 C3 C4 59.2(16) . . . . ?
Cu1 N1 C3 C4 -178.5(12) . . . . ?
N1 C3 C4 O1 -82(2) . . . . ?
C5 C3 C4 O1 88(5) . . . . ?
N1 C3 C5 O2 59(2) . . . . ?
C4 C3 C5 O2 47(4) . . . . ?

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
N2 H2A N11 0.99 2.32 3.234(14) 153.8 2_656
N2 H2B N18 0.99 2.25 3.162(14) 153.1 3_666
C1 H1B O1 0.99 2.46 2.948(19) 110.1 .
N1 H1N N17 1.00 2.51 3.391(19) 146.4 2_646
N1 H1N N20 1.00 2.66 3.491(15) 140.7 3_766
N2 H2A N11 0.99 2.32 3.234(14) 153.8 2_656
N2 H2B N18 0.99 2.25 3.162(14) 153.1 3_666
C1 H1B O1 0.99 2.46 2.948(19) 110.1 .
C1 H1B O1 0.99 2.45 3.40(2) 162.1 3_767
C3 H3A N5 0.99 2.66 3.226(18) 116.9 4_576
C3 H3B N6 0.99 2.68 3.185(16) 112.1 .
O1 H1 N8 0.98 2.69 3.253(18) 116.6 4_576
O1 H1 N14 0.98 2.23 3.15(2) 157.2 4_576
C5 H5A N11 0.99 2.58 3.30(2) 129.8 2_756
O2 H2F N8 0.98 2.55 3.14(2) 119.0 2_746

_refine_diff_density_max         1.371
_refine_diff_density_min         -1.194
_refine_diff_density_rms         0.223

_shelxl_version_number           2013-2

