# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 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_cu_kk_dg_hi_101_b4_0m_a_sq
_database_code_depnum_ccdc_archive 'CCDC 2192636'
loop_
_audit_author_name
_audit_author_address
'Krishna K. Damodaran'
;University of Iceland
Iceland
;
_audit_update_record             
;
2022-09-08 deposited with the CCDC.	2022-09-26 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT084_cu_kk_dg_hi_101_b4_0m_a_sq 
;
PROBLEM: High wR2 Value (i.e. > 0.25) ...................       0.28 Report
RESPONSE: We have used SQUEEZE to remove the disordered solvent molecules, but 
this did not improve the weighted R factor and the high weighted R factor 
is due to the weak diffraction.
;
_vrf_PLAT241_cu_kk_dg_hi_101_b4_0m_a_sq 
;
PROBLEM: High   'MainMol' Ueq as Compared to Neighbors of         C8 Check 
RESPONSE: The assignment of carbon atom is correct.
;
_vrf_PLAT242_cu_kk_dg_hi_101_b4_0m_a_sq 
;
PROBLEM: Low    'MainMol' Ueq as Compared to Neighbors of         C7 Check 
RESPONSE: The assignment of carbon atom is correct.
;
_vrf_PLAT250_cu_kk_dg_hi_101_b4_0m_a_sq 
;
PROBLEM: Large U3/U1 Ratio for Average U(i,j) Tensor ....        3.4 Note  
RESPONSE: Manual inspection of the thermal ellipsoids does
not indicate any problems, probably unresolved disorder around the 
paddle-wheel cluster.
;
_vrf_PLAT341_cu_kk_dg_hi_101_b4_0m_a_sq 
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............    0.00914 Ang.  
RESPONSE: Probably an unresolved disorder due to the presence of 
the heavy atom
;
_vrf_PLAT416_cu_kk_dg_hi_101_b4_0m_a_sq 
;
PROBLEM: Short Intra D-H..H-D       H10      ..H10      .       1.97 Ang.  
RESPONSE: This is due the symmetry generated urea N-H moiety, 
the carbonyl oxygen is on a 2-fold axis.
;
_vrf_PLAT420_cu_kk_dg_hi_101_b4_0m_a_sq 
;
PROBLEM: D-H Bond Without Acceptor  N10      --H10      .     Please Check 
RESPONSE: This is due to the removal of disordered solvent molecule by SQUEEZE.
;
_vrf_PLAT906_cu_kk_dg_hi_101_b4_0m_a_sq 
;
PROBLEM: Large K Value in the Analysis of Variance ......      2.728 Check 
RESPONSE: The large K value is only for the lowest intensity group.
;
_vrf_PLAT911_cu_kk_dg_hi_101_b4_0m_a_sq 
;
PROBLEM: Missing FCF Refl Between Thmin & STh/L=    0.595         14 Report
RESPONSE: This is due to the weakly diffracting crystals and the crystals were small.
;
_vrf_PLAT913_cu_kk_dg_hi_101_b4_0m_a_sq 
;
PROBLEM: Missing # of Very Strong Reflections in FCF ....          4 Note  
RESPONSE: These low angle reflections are probably missing due to the beamstop
;
_vrf_PLAT934_cu_kk_dg_hi_101_b4_0m_a_sq 
;
PROBLEM: Number of (Iobs-Icalc)/Sigma(W) > 10 Outliers ..          1 Check 
RESPONSE: This is due to the weakly diffracting crystals and the crystals were small.
;
# end Validation Reply Form

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '[C15 H10 Cu N2 O5] [C9 H24 N3 O3]'
_chemical_formula_sum            'C24 H34 Cu N5 O8'
_chemical_formula_weight         584.10

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 -1.9646 0.5888 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      tetragonal
_space_group_IT_number           124
_space_group_name_H-M_alt        'P 4/m c c'
_space_group_name_Hall           '-P 4 2c'

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

_cell_length_a                   15.2686(3)
_cell_length_b                   15.2686(3)
_cell_length_c                   29.2342(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     6815.4(3)
_cell_formula_units_Z            8
_cell_measurement_temperature    250(2)
_cell_measurement_reflns_used    9108
_cell_measurement_theta_min      2.89
_cell_measurement_theta_max      66.55

_exptl_crystal_description       needle
_exptl_crystal_colour            green
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.139
_exptl_crystal_F_000             2448
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.130
_exptl_crystal_size_mid          0.070
_exptl_crystal_size_min          0.040
_exptl_absorpt_coefficient_mu    1.285
_shelx_estimated_absorpt_T_min   0.851
_shelx_estimated_absorpt_T_max   0.950
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6339
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_process_details   
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0966 before and 0.0599 after correction. The Ratio of minimum to maximum transmission is 0.8421. The λ/2 correction factor is Not present.'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      250(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\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            37664
_diffrn_reflns_av_unetI/netI     0.0286
_diffrn_reflns_av_R_equivalents  0.0735
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_theta_min         2.894
_diffrn_reflns_theta_max         66.614
_diffrn_reflns_theta_full        66.614
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measured_fraction_theta_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_point_group_measured_fraction_full 0.995
_reflns_number_total             3094
_reflns_number_gt                2175
_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.
 
 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       'SAINT V8.35A (Bruker, 2016)'
_computing_cell_refinement       'SAINT V8.35A (Bruker, 2016)'
_computing_data_reduction        'SAINT V8.35A (Bruker, 2016)'
_computing_structure_solution    'SAINT V8.35A (Bruker, 2016)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'MERCURY CSD 4.2.0'
_computing_publication_material  'MERCURY CSD 4.2.0'
_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)+(0.1753P)²+3.9652P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3094
_refine_ls_number_parameters     107
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1000
_refine_ls_R_factor_gt           0.0767
_refine_ls_wR_factor_ref         0.2821
_refine_ls_wR_factor_gt          0.2625
_refine_ls_goodness_of_fit_ref   1.099
_refine_ls_restrained_S_all      1.099
_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
O1 O 0.5230(3) 0.1117(3) 0.54716(12) 0.0800(10) Uani 1 1 d . . . . .
Cu1 Cu 0.57633(6) 0.03879(6) 0.5000 0.0575(4) Uani 1 2 d S T P . .
C2 C 0.4467(4) 0.0987(4) 0.56274(19) 0.0783(16) Uani 1 1 d . . . . .
O3 O 0.3918(3) 0.0431(3) 0.54821(13) 0.0820(11) Uani 1 1 d . . . . .
C4 C 0.4202(4) 0.1539(4) 0.60293(19) 0.0877(17) Uani 1 1 d . . . . .
C5 C 0.3464(5) 0.1364(5) 0.6271(2) 0.104(2) Uani 1 1 d . . . . .
H5 H 0.3101 0.0902 0.6175 0.124 Uiso 1 1 calc R U . . .
C6 C 0.3223(5) 0.1844(5) 0.6656(2) 0.109(2) Uani 1 1 d . . . . .
H6 H 0.2709 0.1709 0.6818 0.130 Uiso 1 1 calc R U . . .
C7 C 0.3758(4) 0.2522(4) 0.6795(2) 0.095(2) Uani 1 1 d . . . . .
C8 C 0.4504(5) 0.2721(5) 0.6545(2) 0.122(3) Uani 1 1 d . . . . .
H8 H 0.4853 0.3201 0.6631 0.146 Uiso 1 1 calc R U . . .
C9 C 0.4738(5) 0.2217(5) 0.6168(2) 0.110(2) Uani 1 1 d . . . . .
H9 H 0.5259 0.2337 0.6008 0.131 Uiso 1 1 calc R U . . .
N10 N 0.3596(4) 0.3050(4) 0.71744(18) 0.113(2) Uani 1 1 d . . . . .
H10 H 0.3947 0.3494 0.7207 0.136 Uiso 1 1 calc R U . . .
C11 C 0.2968(5) 0.2968(5) 0.7500 0.111(3) Uani 1 2 d S T P . .
O12 O 0.2430(3) 0.2430(3) 0.7500 0.141(3) Uani 1 2 d S T 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
O1 C2 1.266(7) . ?
O1 Cu1 1.950(3) . ?
Cu1 O3 1.945(4) 9_656 ?
Cu1 O3 1.945(4) 2_655 ?
Cu1 O1 1.950(3) 10_556 ?
Cu1 Cu1 2.6146(19) 9_656 ?
C2 O3 1.267(7) . ?
C2 C4 1.500(7) . ?
O3 Cu1 1.946(4) 9_656 ?
C4 C5 1.357(9) . ?
C4 C9 1.380(9) . ?
C5 C6 1.393(8) . ?
C5 H5 0.9400 . ?
C6 C7 1.378(9) . ?
C6 H6 0.9400 . ?
C7 C8 1.387(9) . ?
C7 N10 1.394(7) . ?
C8 C9 1.391(8) . ?
C8 H8 0.9400 . ?
C9 H9 0.9400 . ?
N10 C11 1.357(8) . ?
N10 H10 0.8700 . ?
C11 O12 1.161(11) . ?
C11 N10 1.357(8) 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
C2 O1 Cu1 123.3(4) . . ?
O3 Cu1 O3 92.8(3) 9_656 2_655 ?
O3 Cu1 O1 87.64(18) 9_656 10_556 ?
O3 Cu1 O1 169.50(19) 2_655 10_556 ?
O3 Cu1 O1 169.50(19) 9_656 . ?
O3 Cu1 O1 87.64(18) 2_655 . ?
O1 Cu1 O1 90.0(2) 10_556 . ?
O3 Cu1 Cu1 86.10(14) 9_656 9_656 ?
O3 Cu1 Cu1 86.10(14) 2_655 9_656 ?
O1 Cu1 Cu1 83.47(13) 10_556 9_656 ?
O1 Cu1 Cu1 83.46(13) . 9_656 ?
O1 C2 O3 126.3(5) . . ?
O1 C2 C4 116.2(6) . . ?
O3 C2 C4 117.4(6) . . ?
C2 O3 Cu1 120.6(4) . 9_656 ?
C5 C4 C9 119.1(5) . . ?
C5 C4 C2 121.4(6) . . ?
C9 C4 C2 119.4(5) . . ?
C4 C5 C6 122.5(6) . . ?
C4 C5 H5 118.8 . . ?
C6 C5 H5 118.8 . . ?
C7 C6 C5 118.5(6) . . ?
C7 C6 H6 120.8 . . ?
C5 C6 H6 120.8 . . ?
C6 C7 C8 119.8(5) . . ?
C6 C7 N10 124.3(5) . . ?
C8 C7 N10 115.9(5) . . ?
C7 C8 C9 120.4(6) . . ?
C7 C8 H8 119.8 . . ?
C9 C8 H8 119.8 . . ?
C4 C9 C8 119.7(6) . . ?
C4 C9 H9 120.1 . . ?
C8 C9 H9 120.1 . . ?
C11 N10 C7 129.1(6) . . ?
C11 N10 H10 115.5 . . ?
C7 N10 H10 115.5 . . ?
O12 C11 N10 124.4(4) . 7_556 ?
O12 C11 N10 124.4(4) . . ?
N10 C11 N10 111.2(9) 7_556 . ?

_refine_diff_density_max         0.436
_refine_diff_density_min         -0.992
_refine_diff_density_rms         0.085




_chemical_properties_physical    Air-sensitive,Moisture-sensitive
####################################################################### 
# 
# 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_cu_KK_DG_102_B4_0m_a
_database_code_depnum_ccdc_archive 'CCDC 2192635'
loop_
_audit_author_name
_audit_author_address
'Krishna K. Damodaran'
;University of Iceland
Iceland
;
_audit_update_record             
;
2022-09-13 deposited with the CCDC.	2022-09-26 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT242_cu_KK_DG_102_B4_0m_a 
;
PROBLEM: Low    'MainMol' Ueq as Compared to Neighbors of        N25 Check 
RESPONSE: The assignment of nitrogen atom is correct
;
_vrf_PLAT244_cu_KK_DG_102_B4_0m_a 
;
PROBLEM: Low    'Solvent' Ueq as Compared to Neighbors of        N30 Check 
RESPONSE: The assignment of nitrogen atom is correct
;
_vrf_PLAT341_cu_KK_DG_102_B4_0m_a 
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............    0.00714 Ang.  
RESPONSE: Probably an unresolved disorder due to the presence of 
the heavy atom
;
_vrf_PLAT413_cu_KK_DG_102_B4_0m_a 
;
PROBLEM: Short Inter XH3 .. XHn     H31C     ..H32A     .       2.14 Ang.  
RESPONSE: Manual inspection of the thermal ellipsoids does
not indicate any problems, probably unresolved disorder around the 
DMF solvent molecule
;
_vrf_PLAT906_cu_KK_DG_102_B4_0m_a 
;
PROBLEM: Large K Value in the Analysis of Variance ......      7.895 Check 
RESPONSE: The large K value is only for the lowest intensity group.
;
# end Validation Reply Form

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C21 H24 Cu N4 O7'
_chemical_formula_weight         507.98

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 -1.9646 0.5888 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_H-M_alt        'P b c a'
_space_group_name_Hall           '-P 2ac 2ab'

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

_cell_length_a                   18.2919(5)
_cell_length_b                   9.4420(3)
_cell_length_c                   25.3572(7)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4379.5(2)
_cell_formula_units_Z            8
_cell_measurement_temperature    240(2)
_cell_measurement_reflns_used    9996
_cell_measurement_theta_min      2.98
_cell_measurement_theta_max      69.98

_exptl_crystal_description       NEEDLE
_exptl_crystal_colour            GREEN
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.541
_exptl_crystal_F_000             2104
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.180
_exptl_crystal_size_mid          0.060
_exptl_crystal_size_min          0.030
_exptl_absorpt_coefficient_mu    1.862
_shelx_estimated_absorpt_T_min   0.730
_shelx_estimated_absorpt_T_max   0.946
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6498
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_process_details   
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0892 before and 0.0678 after correction. The Ratio of minimum to maximum transmission is 0.8626. The λ/2 correction factor is Not present.'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      240(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\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            31808
_diffrn_reflns_av_unetI/netI     0.0316
_diffrn_reflns_av_R_equivalents  0.0637
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_theta_min         3.486
_diffrn_reflns_theta_max         69.995
_diffrn_reflns_theta_full        67.679
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             4141
_reflns_number_gt                3450
_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       'SAINT V8.35A (Bruker, 2016)'
_computing_cell_refinement       'SAINT V8.35A (Bruker, 2016)'
_computing_data_reduction        'SAINT V8.35A (Bruker, 2016)'
_computing_structure_solution    'SAINT V8.35A (Bruker, 2016)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'MERCURY CSD 4.2.0'
_computing_publication_material  'MERCURY CSD 4.2.0'
_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)+(0.0688P)²+9.6954P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         4141
_refine_ls_number_parameters     302
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0759
_refine_ls_R_factor_gt           0.0632
_refine_ls_wR_factor_ref         0.1713
_refine_ls_wR_factor_gt          0.1641
_refine_ls_goodness_of_fit_ref   1.172
_refine_ls_restrained_S_all      1.172
_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 0.55148(3) 0.09046(6) 0.48659(2) 0.0304(2) Uani 1 1 d . . . . .
O1 O 0.49070(17) 0.1522(4) 0.42607(11) 0.0419(7) Uani 1 1 d . . . . .
C2 C 0.4293(3) 0.0945(5) 0.42131(16) 0.0367(10) Uani 1 1 d . . . . .
O3 O 0.40457(18) -0.0032(3) 0.44977(11) 0.0415(7) Uani 1 1 d . . . . .
C4 C 0.3800(3) 0.1461(5) 0.37791(17) 0.0389(10) Uani 1 1 d . . . . .
C5 C 0.4000(3) 0.2553(5) 0.34457(18) 0.0429(11) Uani 1 1 d . . . . .
H5 H 0.4459 0.2984 0.3488 0.051 Uiso 1 1 calc R U . . .
C6 C 0.3532(3) 0.3030(5) 0.3047(2) 0.0491(12) Uani 1 1 d . . . . .
H6 H 0.3679 0.3769 0.2822 0.059 Uiso 1 1 calc R U . . .
C7 C 0.2859(3) 0.2412(5) 0.29852(18) 0.0461(11) Uani 1 1 d . . . . .
C8 C 0.2655(3) 0.1306(6) 0.3319(2) 0.0595(15) Uani 1 1 d . . . . .
H8 H 0.2195 0.0875 0.3279 0.071 Uiso 1 1 calc R U . . .
C9 C 0.3126(3) 0.0843(6) 0.3705(2) 0.0547(13) Uani 1 1 d . . . . .
H9 H 0.2984 0.0089 0.3924 0.066 Uiso 1 1 calc R U . . .
N10 N 0.2343(2) 0.2795(5) 0.25947(17) 0.0539(11) Uani 1 1 d . . . . .
H10 H 0.1953 0.2272 0.2576 0.065 Uiso 1 1 calc R U . . .
C11 C 0.2387(3) 0.3902(6) 0.2240(2) 0.0485(12) Uani 1 1 d . . . . .
O12 O 0.2866(2) 0.4774(4) 0.22373(15) 0.0568(10) Uani 1 1 d . . . . .
N13 N 0.1828(3) 0.3830(5) 0.18772(17) 0.0548(11) Uani 1 1 d . . . . .
H13 H 0.1590 0.3033 0.1861 0.066 Uiso 1 1 calc R U . . .
C14 C 0.1597(3) 0.4910(5) 0.15288(19) 0.0466(11) Uani 1 1 d . . . . .
C15 C 0.1903(3) 0.6251(6) 0.1515(2) 0.0592(15) Uani 1 1 d . . . . .
H15 H 0.2315 0.6460 0.1723 0.071 Uiso 1 1 calc R U . . .
C16 C 0.1598(3) 0.7295(6) 0.1191(2) 0.0537(13) Uani 1 1 d . . . . .
H16 H 0.1810 0.8201 0.1181 0.064 Uiso 1 1 calc R U . . .
C17 C 0.0990(3) 0.7011(5) 0.08871(18) 0.0438(11) Uani 1 1 d . . . . .
C18 C 0.0705(3) 0.5652(5) 0.08935(19) 0.0464(12) Uani 1 1 d . . . . .
H18 H 0.0300 0.5434 0.0680 0.056 Uiso 1 1 calc R U . . .
C19 C 0.1009(3) 0.4608(5) 0.12114(19) 0.0486(12) Uani 1 1 d . . . . .
H19 H 0.0810 0.3690 0.1209 0.058 Uiso 1 1 calc R U . . .
C20 C 0.0643(2) 0.8158(5) 0.05581(16) 0.0379(10) Uani 1 1 d . . . . .
O21 O 0.09281(18) 0.9369(3) 0.05666(12) 0.0419(7) Uani 1 1 d . . . . .
O22 O 0.00817(18) 0.7816(3) 0.03094(13) 0.0454(8) Uani 1 1 d . . . . .
O23 O 0.63825(19) 0.2441(4) 0.48090(14) 0.0487(8) Uani 1 1 d . . . . .
C24 C 0.6329(4) 0.3514(7) 0.5089(2) 0.0633(15) Uani 1 1 d . . . . .
H24 H 0.5915 0.3586 0.5307 0.076 Uiso 1 1 calc R U . . .
N25 N 0.6800(3) 0.4548(5) 0.5107(2) 0.0641(13) Uani 1 1 d . . . . .
C26 C 0.7431(4) 0.4525(9) 0.4789(3) 0.085(2) Uani 1 1 d . . . . .
H26A H 0.7460 0.3626 0.4605 0.127 Uiso 1 1 calc R U . . .
H26B H 0.7860 0.4643 0.5009 0.127 Uiso 1 1 calc R U . . .
H26C H 0.7408 0.5290 0.4534 0.127 Uiso 1 1 calc R U . . .
C27 C 0.6655(5) 0.5835(8) 0.5405(4) 0.096(3) Uani 1 1 d . . . . .
H27A H 0.6715 0.6651 0.5177 0.145 Uiso 1 1 calc R U . . .
H27B H 0.6995 0.5899 0.5698 0.145 Uiso 1 1 calc R U . . .
H27C H 0.6158 0.5811 0.5539 0.145 Uiso 1 1 calc R U . . .
O28 O 0.0835(3) 0.1727(6) 0.2151(2) 0.0843(14) Uani 1 1 d . . . . .
C29 C 0.0628(4) 0.0690(7) 0.1918(3) 0.0656(16) Uani 1 1 d . . . . .
H29 H 0.0845 0.0469 0.1592 0.079 Uiso 1 1 calc R U . . .
N30 N 0.0122(3) -0.0129(6) 0.2095(2) 0.0720(15) Uani 1 1 d . . . . .
C31 C -0.0263(6) 0.0134(10) 0.2589(3) 0.109(3) Uani 1 1 d . . . . .
H31A H -0.0407 -0.0761 0.2745 0.164 Uiso 1 1 calc R U . . .
H31B H -0.0695 0.0701 0.2520 0.164 Uiso 1 1 calc R U . . .
H31C H 0.0056 0.0637 0.2830 0.164 Uiso 1 1 calc R U . . .
C32 C -0.0163(5) -0.1290(9) 0.1788(3) 0.096(2) Uani 1 1 d . . . . .
H32A H -0.0136 -0.2157 0.1993 0.145 Uiso 1 1 calc R U . . .
H32B H 0.0123 -0.1395 0.1468 0.145 Uiso 1 1 calc R U . . .
H32C H -0.0669 -0.1100 0.1697 0.145 Uiso 1 1 calc R 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
Cu1 O21 1.969(3) 6_646 ?
Cu1 O22 1.979(3) 2_565 ?
Cu1 O3 1.982(3) 5_656 ?
Cu1 O1 1.983(3) . ?
Cu1 O23 2.155(4) . ?
Cu1 Cu1 2.6322(12) 5_656 ?
O1 C2 1.254(6) . ?
C2 O3 1.256(6) . ?
C2 C4 1.505(6) . ?
O3 Cu1 1.982(3) 5_656 ?
C4 C9 1.376(7) . ?
C4 C5 1.383(7) . ?
C5 C6 1.399(6) . ?
C5 H5 0.9400 . ?
C6 C7 1.372(7) . ?
C6 H6 0.9400 . ?
C7 C8 1.395(7) . ?
C7 N10 1.414(6) . ?
C8 C9 1.375(7) . ?
C8 H8 0.9400 . ?
C9 H9 0.9400 . ?
N10 C11 1.382(6) . ?
N10 H10 0.8700 . ?
C11 O12 1.202(6) . ?
C11 N13 1.377(6) . ?
N13 C14 1.413(6) . ?
N13 H13 0.8700 . ?
C14 C19 1.373(7) . ?
C14 C15 1.386(8) . ?
C15 C16 1.399(7) . ?
C15 H15 0.9400 . ?
C16 C17 1.380(7) . ?
C16 H16 0.9400 . ?
C17 C18 1.385(7) . ?
C17 C20 1.508(6) . ?
C18 C19 1.390(6) . ?
C18 H18 0.9400 . ?
C19 H19 0.9400 . ?
C20 O22 1.248(6) . ?
C20 O21 1.257(6) . ?
O21 Cu1 1.969(3) 6_566 ?
O22 Cu1 1.979(3) 2_564 ?
O23 C24 1.241(7) . ?
C24 N25 1.302(8) . ?
C24 H24 0.9400 . ?
N25 C26 1.408(9) . ?
N25 C27 1.455(8) . ?
C26 H26A 0.9700 . ?
C26 H26B 0.9700 . ?
C26 H26C 0.9700 . ?
C27 H27A 0.9700 . ?
C27 H27B 0.9700 . ?
C27 H27C 0.9700 . ?
O28 C29 1.206(8) . ?
C29 N30 1.286(8) . ?
C29 H29 0.9400 . ?
N30 C32 1.443(9) . ?
N30 C31 1.458(9) . ?
C31 H31A 0.9700 . ?
C31 H31B 0.9700 . ?
C31 H31C 0.9700 . ?
C32 H32A 0.9700 . ?
C32 H32B 0.9700 . ?
C32 H32C 0.9700 . ?

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
O21 Cu1 O22 167.95(15) 6_646 2_565 ?
O21 Cu1 O3 89.51(13) 6_646 5_656 ?
O22 Cu1 O3 90.85(14) 2_565 5_656 ?
O21 Cu1 O1 90.04(14) 6_646 . ?
O22 Cu1 O1 87.20(14) 2_565 . ?
O3 Cu1 O1 168.44(14) 5_656 . ?
O21 Cu1 O23 100.13(14) 6_646 . ?
O22 Cu1 O23 91.89(14) 2_565 . ?
O3 Cu1 O23 92.05(14) 5_656 . ?
O1 Cu1 O23 99.40(14) . . ?
O21 Cu1 Cu1 86.60(10) 6_646 5_656 ?
O22 Cu1 Cu1 81.65(11) 2_565 5_656 ?
O3 Cu1 Cu1 79.04(10) 5_656 5_656 ?
O1 Cu1 Cu1 89.40(10) . 5_656 ?
O23 Cu1 Cu1 168.86(10) . 5_656 ?
C2 O1 Cu1 116.7(3) . . ?
O1 C2 O3 125.9(4) . . ?
O1 C2 C4 117.9(4) . . ?
O3 C2 C4 116.2(4) . . ?
C2 O3 Cu1 128.8(3) . 5_656 ?
C9 C4 C5 118.1(4) . . ?
C9 C4 C2 120.0(4) . . ?
C5 C4 C2 122.0(4) . . ?
C4 C5 C6 121.3(5) . . ?
C4 C5 H5 119.3 . . ?
C6 C5 H5 119.3 . . ?
C7 C6 C5 119.6(4) . . ?
C7 C6 H6 120.2 . . ?
C5 C6 H6 120.2 . . ?
C6 C7 C8 119.3(4) . . ?
C6 C7 N10 124.7(4) . . ?
C8 C7 N10 116.0(5) . . ?
C9 C8 C7 120.2(5) . . ?
C9 C8 H8 119.9 . . ?
C7 C8 H8 119.9 . . ?
C8 C9 C4 121.5(5) . . ?
C8 C9 H9 119.3 . . ?
C4 C9 H9 119.3 . . ?
C11 N10 C7 127.6(4) . . ?
C11 N10 H10 116.2 . . ?
C7 N10 H10 116.2 . . ?
O12 C11 N13 124.9(4) . . ?
O12 C11 N10 124.3(4) . . ?
N13 C11 N10 110.8(5) . . ?
C11 N13 C14 127.1(5) . . ?
C11 N13 H13 116.4 . . ?
C14 N13 H13 116.4 . . ?
C19 C14 C15 119.5(4) . . ?
C19 C14 N13 116.8(5) . . ?
C15 C14 N13 123.6(5) . . ?
C14 C15 C16 119.8(5) . . ?
C14 C15 H15 120.1 . . ?
C16 C15 H15 120.1 . . ?
C17 C16 C15 120.9(5) . . ?
C17 C16 H16 119.6 . . ?
C15 C16 H16 119.6 . . ?
C16 C17 C18 118.5(4) . . ?
C16 C17 C20 120.6(4) . . ?
C18 C17 C20 120.9(4) . . ?
C17 C18 C19 120.9(5) . . ?
C17 C18 H18 119.6 . . ?
C19 C18 H18 119.6 . . ?
C14 C19 C18 120.4(5) . . ?
C14 C19 H19 119.8 . . ?
C18 C19 H19 119.8 . . ?
O22 C20 O21 125.8(4) . . ?
O22 C20 C17 116.1(4) . . ?
O21 C20 C17 118.0(4) . . ?
C20 O21 Cu1 120.1(3) . 6_566 ?
C20 O22 Cu1 125.7(3) . 2_564 ?
C24 O23 Cu1 117.0(4) . . ?
O23 C24 N25 125.4(6) . . ?
O23 C24 H24 117.3 . . ?
N25 C24 H24 117.3 . . ?
C24 N25 C26 120.7(6) . . ?
C24 N25 C27 121.6(6) . . ?
C26 N25 C27 117.3(6) . . ?
N25 C26 H26A 109.5 . . ?
N25 C26 H26B 109.5 . . ?
H26A C26 H26B 109.5 . . ?
N25 C26 H26C 109.5 . . ?
H26A C26 H26C 109.5 . . ?
H26B C26 H26C 109.5 . . ?
N25 C27 H27A 109.5 . . ?
N25 C27 H27B 109.5 . . ?
H27A C27 H27B 109.5 . . ?
N25 C27 H27C 109.5 . . ?
H27A C27 H27C 109.5 . . ?
H27B C27 H27C 109.5 . . ?
O28 C29 N30 122.9(7) . . ?
O28 C29 H29 118.6 . . ?
N30 C29 H29 118.6 . . ?
C29 N30 C32 121.9(6) . . ?
C29 N30 C31 123.1(6) . . ?
C32 N30 C31 114.7(6) . . ?
N30 C31 H31A 109.5 . . ?
N30 C31 H31B 109.5 . . ?
H31A C31 H31B 109.5 . . ?
N30 C31 H31C 109.5 . . ?
H31A C31 H31C 109.5 . . ?
H31B C31 H31C 109.5 . . ?
N30 C32 H32A 109.5 . . ?
N30 C32 H32B 109.5 . . ?
H32A C32 H32B 109.5 . . ?
N30 C32 H32C 109.5 . . ?
H32A C32 H32C 109.5 . . ?
H32B C32 H32C 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
Cu1 O1 C2 O3 -3.7(6) . . . . ?
Cu1 O1 C2 C4 176.0(3) . . . . ?
O1 C2 O3 Cu1 4.5(6) . . . 5_656 ?
C4 C2 O3 Cu1 -175.2(3) . . . 5_656 ?
O1 C2 C4 C9 178.9(5) . . . . ?
O3 C2 C4 C9 -1.4(6) . . . . ?
O1 C2 C4 C5 -1.2(6) . . . . ?
O3 C2 C4 C5 178.5(4) . . . . ?
C9 C4 C5 C6 0.5(8) . . . . ?
C2 C4 C5 C6 -179.4(4) . . . . ?
C4 C5 C6 C7 0.5(8) . . . . ?
C5 C6 C7 C8 -0.7(8) . . . . ?
C5 C6 C7 N10 -179.5(5) . . . . ?
C6 C7 C8 C9 0.1(9) . . . . ?
N10 C7 C8 C9 178.9(5) . . . . ?
C7 C8 C9 C4 0.8(10) . . . . ?
C5 C4 C9 C8 -1.1(8) . . . . ?
C2 C4 C9 C8 178.8(5) . . . . ?
C6 C7 N10 C11 -5.7(9) . . . . ?
C8 C7 N10 C11 175.5(6) . . . . ?
C7 N10 C11 O12 -5.2(10) . . . . ?
C7 N10 C11 N13 172.3(5) . . . . ?
O12 C11 N13 C14 -17.2(10) . . . . ?
N10 C11 N13 C14 165.4(5) . . . . ?
C11 N13 C14 C19 -178.1(5) . . . . ?
C11 N13 C14 C15 -1.9(9) . . . . ?
C19 C14 C15 C16 1.9(9) . . . . ?
N13 C14 C15 C16 -174.2(6) . . . . ?
C14 C15 C16 C17 0.5(9) . . . . ?
C15 C16 C17 C18 -2.5(9) . . . . ?
C15 C16 C17 C20 177.2(5) . . . . ?
C16 C17 C18 C19 2.0(8) . . . . ?
C20 C17 C18 C19 -177.7(5) . . . . ?
C15 C14 C19 C18 -2.4(8) . . . . ?
N13 C14 C19 C18 174.0(5) . . . . ?
C17 C18 C19 C14 0.5(8) . . . . ?
C16 C17 C20 O22 -177.7(5) . . . . ?
C18 C17 C20 O22 1.9(7) . . . . ?
C16 C17 C20 O21 0.6(7) . . . . ?
C18 C17 C20 O21 -179.8(5) . . . . ?
O22 C20 O21 Cu1 -3.2(6) . . . 6_566 ?
C17 C20 O21 Cu1 178.7(3) . . . 6_566 ?
O21 C20 O22 Cu1 -0.5(7) . . . 2_564 ?
C17 C20 O22 Cu1 177.7(3) . . . 2_564 ?
Cu1 O23 C24 N25 179.9(5) . . . . ?
O23 C24 N25 C26 0.5(10) . . . . ?
O23 C24 N25 C27 173.3(6) . . . . ?
O28 C29 N30 C32 174.2(7) . . . . ?
O28 C29 N30 C31 1.5(11) . . . . ?

_refine_diff_density_max         0.621
_refine_diff_density_min         -0.382
_refine_diff_density_rms         0.084



