# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# 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_x2126fin
_database_code_depnum_ccdc_archive 'CCDC 1470302'
_audit_update_record             
;
2016-09-08 deposited with the CCDC.
2017-04-24 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/4
_shelx_SHELXL_version_number     2016/4
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C28 H30 Cu N14 O15'
_chemical_formula_weight         866.20

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Cu Cu 0.3201 1.2651 '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'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
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'

_space_group_crystal_system      tetragonal
_space_group_IT_number           133
_space_group_name_H-M_alt        'P 42/n b c'
_space_group_name_Hall           '-P 4ac 2b'

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

_cell_length_a                   16.3357(2)
_cell_length_b                   16.3357(2)
_cell_length_c                   12.9557(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3457.29(14)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2165
_cell_measurement_theta_min      2.9420
_cell_measurement_theta_max      25.3000

_exptl_crystal_description       prism
_exptl_crystal_colour            'clear intense green'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.664
_exptl_crystal_F_000             1780
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.2
_exptl_absorpt_coefficient_mu    0.727
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.98852
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'Enhance (Mo) X-ray Source'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 16.3560
_diffrn_reflns_number            10630
_diffrn_reflns_av_unetI/netI     0.0230
_diffrn_reflns_av_R_equivalents  0.0367
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         2.494
_diffrn_reflns_theta_max         26.365
_diffrn_reflns_theta_full        26.365
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             1778
_reflns_number_gt                1291
_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       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_cell_refinement       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction        
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_structure_solution    SHELXT-2014-5
_computing_structure_refinement  'SHELXL-2016/4 (Sheldrick, 2016)'
_computing_molecular_graphics    
;
 DIAMOND Version 3.2k
 K. Brandenburg, Crystal Impact GbR, Bonn, Germany
;
_computing_publication_material  
;
 WINGX
 L.J. Farrugia,
 J. Appl. Cryst., 2012, 45, 849-854.
;
_refine_special_details          
;
Restraints are only used to model the highly disordered nitrate anion and to
get acceptable OH distances for the water molecule O(6).
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0915P)²+2.8240P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         1778
_refine_ls_number_parameters     148
_refine_ls_number_restraints     29
_refine_ls_R_factor_all          0.0800
_refine_ls_R_factor_gt           0.0595
_refine_ls_wR_factor_ref         0.1836
_refine_ls_wR_factor_gt          0.1662
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_restrained_S_all      1.096
_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 0.250000 0.250000 0.54229(9) 0.0517(4) Uani 0.5 2 d S T P . .
O1 O 0.14021(16) 0.67969(16) 0.67446(17) 0.0610(7) Uani 1 1 d . . . . .
O2 O 0.250000 0.250000 0.7086(6) 0.091(3) Uani 0.5 2 d S T P . .
H1O2 H 0.195360 0.259183 0.733345 0.136 Uiso 0.25 1 d R U P . .
H2O2 H 0.269367 0.198089 0.733345 0.136 Uiso 0.25 1 d R U P . .
O6 O 0.04247(18) 0.81027(19) 0.6170(3) 0.0758(9) Uani 1 1 d D . . . .
N1 N 0.32505(17) 0.34089(18) 0.5351(3) 0.0684(9) Uani 1 1 d . . . . .
N2 N 0.25194(16) 0.60031(15) 0.63132(17) 0.0428(6) Uani 1 1 d . . . . .
H1N2 H 0.273636 0.595556 0.691504 0.051 Uiso 1 1 calc R U . . .
N3 N 0.15783(16) 0.62434(16) 0.51371(18) 0.0440(6) Uani 1 1 d . . . . .
H1N3 H 0.115794 0.646054 0.484613 0.053 Uiso 1 1 calc R U . . .
C1 C 0.29079(18) 0.41550(18) 0.5237(3) 0.0460(8) Uani 1 1 d . . . . .
C2 C 0.32841(17) 0.48625(18) 0.5540(2) 0.0394(7) Uani 1 1 d . . . . .
C3 C 0.40535(19) 0.4806(2) 0.6003(2) 0.0498(8) Uani 1 1 d . . . . .
H3 H 0.432508 0.527380 0.622618 0.060 Uiso 1 1 calc R U . . .
C4 C 0.4403(2) 0.4047(2) 0.6123(3) 0.0619(10) Uani 1 1 d . . . . .
H4 H 0.491659 0.399590 0.642643 0.074 Uiso 1 1 calc R U . . .
C5 C 0.3988(2) 0.3362(2) 0.5792(4) 0.0748(13) Uani 1 1 d . . . . .
H5 H 0.422847 0.285051 0.587730 0.090 Uiso 1 1 calc R U . . .
C6 C 0.28752(17) 0.56815(17) 0.53789(19) 0.0348(6) Uani 1 1 d . . . . .
C7 C 0.1797(2) 0.63916(19) 0.6124(2) 0.0440(7) Uani 1 1 d . . . . .
O3 O -0.0907(6) 0.8211(6) 0.7698(9) 0.138(3) Uiso 0.5 1 d D . P A 1
O4 O -0.0565(5) 0.9435(5) 0.750000 0.146(5) Uiso 0.5 2 d DS . P A 1
N4 N -0.1066(5) 0.8934(5) 0.750000 0.072(2) Uiso 0.5 2 d DS . P A 1
O3F O -0.1132(13) 0.8422(9) 0.6710(15) 0.138(3) Uiso 0.25 1 d D . P B 2
O4F O -0.0844(9) 0.9647(8) 0.7033(11) 0.098(4) Uiso 0.25 1 d D . P B 2
O5F O -0.1795(11) 0.9049(13) 0.7797(16) 0.138(3) Uiso 0.25 1 d D . P B 2
N4F N -0.1228(8) 0.9062(9) 0.7145(10) 0.072(2) Uiso 0.25 1 d D . P B 2
H1O6 H 0.075(2) 0.7642(18) 0.639(3) 0.076(12) Uiso 1 1 d D . . . .
H2O6 H 0.011(3) 0.835(3) 0.670(4) 0.14(2) Uiso 1 1 d 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 CU1 1.096(2) 5_556 ?
CU1 N1 1.928(3) . ?
CU1 N1 1.928(3) 2 ?
CU1 O2 2.155(8) . ?
CU1 N1 2.171(3) 6_556 ?
CU1 N1 2.171(3) 5_556 ?
O1 C7 1.225(4) . ?
O2 H1O2 0.9600 . ?
O2 H2O2 0.9600 . ?
O6 H1O6 0.964(19) . ?
O6 H2O6 0.95(2) . ?
N1 C5 1.335(5) . ?
N1 C1 1.349(4) . ?
N1 CU1 2.171(3) 5_556 ?
N2 C7 1.362(4) . ?
N2 C6 1.442(3) . ?
N2 H1N2 0.8600 . ?
N3 C7 1.350(4) . ?
N3 C6 1.444(4) 5_556 ?
N3 H1N3 0.8600 . ?
C1 C2 1.367(4) . ?
C1 C1 1.468(6) 5_556 ?
C2 C3 1.396(4) . ?
C2 C6 1.510(4) . ?
C3 C4 1.374(5) . ?
C3 H3 0.9300 . ?
C4 C5 1.377(6) . ?
C4 H4 0.9300 . ?
C5 H5 0.9300 . ?
C6 N3 1.444(4) 5_556 ?
C6 C6 1.571(5) 5_556 ?
O3a N4 1.237(8) . ?
O4a N4 1.157(11) . ?
N4a O3 1.237(8) 7_466 ?
O3Fb O5F 0.79(2) 7_466 ?
O3Fb N4F 1.199(12) . ?
O3Fb N4F 1.62(2) 7_466 ?
O4Fb N4F 1.152(12) . ?
O4Fb O4F 1.66(3) 7_466 ?
O4Fb N4F 1.790(18) 7_466 ?
O5Fb O3F 0.79(2) 7_466 ?
O5Fb N4F 1.253(12) . ?
O5Fb N4F 1.47(2) 7_466 ?
N4Fb N4F 1.14(3) 7_466 ?
N4Fb O5F 1.47(2) 7_466 ?
N4Fb O3F 1.62(2) 7_466 ?
N4Fb O4F 1.790(18) 7_466 ?

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
CU1 CU1 N1 87.22(12) 5_556 . ?
CU1 CU1 N1 87.22(12) 5_556 2 ?
N1 CU1 N1 174.4(2) . 2 ?
CU1 CU1 O2 180.0 5_556 . ?
N1 CU1 O2 92.78(12) . . ?
N1 CU1 O2 92.78(12) 2 . ?
CU1 CU1 N1 62.50(10) 5_556 6_556 ?
N1 CU1 N1 98.36(16) . 6_556 ?
N1 CU1 N1 79.04(16) 2 6_556 ?
O2 CU1 N1 117.50(10) . 6_556 ?
CU1 CU1 N1 62.50(10) 5_556 5_556 ?
N1 CU1 N1 79.04(16) . 5_556 ?
N1 CU1 N1 98.36(16) 2 5_556 ?
O2 CU1 N1 117.50(10) . 5_556 ?
N1 CU1 N1 125.00(19) 6_556 5_556 ?
CU1 O2 H1O2 109.5 . . ?
CU1 O2 H2O2 109.5 . . ?
H1O2 O2 H2O2 109.5 . . ?
H1O6 O6 H2O6 114(5) . . ?
C5 N1 C1 118.2(3) . . ?
C5 N1 CU1 120.6(3) . . ?
C1 N1 CU1 115.9(2) . . ?
C5 N1 CU1 131.9(3) . 5_556 ?
C1 N1 CU1 109.5(2) . 5_556 ?
CU1 N1 CU1 30.28(8) . 5_556 ?
C7 N2 C6 111.6(2) . . ?
C7 N2 H1N2 124.2 . . ?
C6 N2 H1N2 124.2 . . ?
C7 N3 C6 112.9(2) . 5_556 ?
C7 N3 H1N3 123.6 . . ?
C6 N3 H1N3 123.6 5_556 . ?
N1 C1 C2 123.1(3) . . ?
N1 C1 C1 114.97(19) . 5_556 ?
C2 C1 C1 121.92(17) . 5_556 ?
C1 C2 C3 118.2(3) . . ?
C1 C2 C6 120.7(3) . . ?
C3 C2 C6 121.1(3) . . ?
C4 C3 C2 118.9(3) . . ?
C4 C3 H3 120.6 . . ?
C2 C3 H3 120.6 . . ?
C3 C4 C5 119.5(3) . . ?
C3 C4 H4 120.2 . . ?
C5 C4 H4 120.2 . . ?
N1 C5 C4 122.1(3) . . ?
N1 C5 H5 119.0 . . ?
C4 C5 H5 119.0 . . ?
N2 C6 N3 114.0(2) . 5_556 ?
N2 C6 C2 112.6(2) . . ?
N3 C6 C2 110.7(2) 5_556 . ?
N2 C6 C6 102.1(3) . 5_556 ?
N3 C6 C6 101.1(2) 5_556 5_556 ?
C2 C6 C6 115.59(15) . 5_556 ?
O1 C7 N3 125.4(3) . . ?
O1 C7 N2 126.2(3) . . ?
N3 C7 N2 108.4(2) . . ?
O4a N4a O3 121.8(5) . 7_466 ?
O4a N4a O3 121.8(5) . . ?
O3a N4a O3 116.3(10) 7_466 . ?
O5Fb O3Fb N4F 93(2) 7_466 . ?
O5Fb O3Fb N4F 48.9(15) 7_466 7_466 ?
N4Fb O3Fb N4F 44.6(13) . 7_466 ?
N4Fb O4Fb O4F 76.7(11) . 7_466 ?
N4Fb O4Fb N4F 38.4(10) . 7_466 ?
O4Fb O4Fb N4F 38.8(5) 7_466 7_466 ?
O3Fb O5Fb N4F 103(2) 7_466 . ?
O3Fb O5Fb N4F 54.2(16) 7_466 7_466 ?
N4Fb O5Fb N4F 48.5(13) . 7_466 ?
N4Fb N4Fb O4F 102.7(11) 7_466 . ?
N4Fb N4Fb O3F 87.8(16) 7_466 . ?
O4Fb N4Fb O3F 126.4(13) . . ?
N4Fb N4Fb O5F 75.9(15) 7_466 . ?
O4Fb N4Fb O5F 120.1(12) . . ?
O3Fb N4Fb O5F 113.5(11) . . ?
N4Fb N4Fb O5F 55.5(11) 7_466 7_466 ?
O4Fb N4Fb O5F 128.8(16) . 7_466 ?
O3Fb N4Fb O5F 32.3(11) . 7_466 ?
O5Fb N4Fb O5F 100.2(16) . 7_466 ?
N4Fb N4Fb O3F 47.6(10) 7_466 7_466 ?
O4Fb N4Fb O3F 118.0(14) . 7_466 ?
O3Fb N4Fb O3F 107.8(16) . 7_466 ?
O5Fb N4Fb O3F 28.3(11) . 7_466 ?
O5Fb N4Fb O3F 82.8(10) 7_466 7_466 ?
N4Fb N4Fb O4F 38.9(5) 7_466 7_466 ?
O4Fb N4Fb O4F 64.5(13) . 7_466 ?
O3Fb N4Fb O4F 104.4(14) . 7_466 ?
O5Fb N4Fb O4F 101.0(14) . 7_466 ?
O5Fb N4Fb O4F 78.7(10) 7_466 7_466 ?
O3Fb N4Fb O4F 75.8(9) 7_466 7_466 ?

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 H1N2 O1_$3 0.86 2.03 2.829(3) 153.8 12_667
N3 H1N3 O6_$4 0.86 1.92 2.749(4) 162.4 6_566
O2 H1O2 O3a_$5 0.96 2.04 2.958(11) 158.9 14
O2 H2O2 O3a_$6 0.96 1.95 2.863(10) 158.7 11_557
O2 H1O2 O3a_$3 0.96 2.47 2.863(10) 104.5 12_667
O2 H2O2 O3a_$7 0.96 2.36 2.958(11) 120.3 13_665
O6 H1O6 O1 0.964(19) 1.80(2) 2.767(4) 177(4) .
O6 H2O6 O3a 0.95(2) 2.12(4) 2.947(11) 146(5) .

_refine_diff_density_max         0.291
_refine_diff_density_min         -0.435
_refine_diff_density_rms         0.059

