# Electronic Supplementary Material (ESI) for New Journal of Chemistry.
# This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2023

####################################################################### 
# 
# 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_shelx
_database_code_depnum_ccdc_archive 'CCDC 2285407'
loop_
_audit_author_name
_audit_author_address
'M R Prathapachandra Kurup'
;Cochin University of Science and Technology
India
;
_audit_update_record             
;
2023-07-30 deposited with the CCDC.	2023-10-16 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C14 H14 N4 O2, H2 O'
_chemical_formula_sum            'C14 H16 N4 O3'
_chemical_formula_weight         288.31

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'

_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                   7.1260(3)
_cell_length_b                   9.6741(4)
_cell_length_c                   20.5984(8)
_cell_angle_alpha                90
_cell_angle_beta                 93.455(3)
_cell_angle_gamma                90
_cell_volume                     1417.42(10)
_cell_formula_units_Z            4
_cell_measurement_temperature    299(2)
_cell_measurement_reflns_used    6092
_cell_measurement_theta_min      1.9760
_cell_measurement_theta_max      25.8270

_exptl_crystal_description       needle
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.351
_exptl_crystal_F_000             608
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.140
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    0.098
_shelx_estimated_absorpt_T_min   0.981
_shelx_estimated_absorpt_T_max   0.990
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.942
_exptl_absorpt_correction_T_max  0.984
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.40.35a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      299(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            17206
_diffrn_reflns_av_unetI/netI     0.0440
_diffrn_reflns_av_R_equivalents  0.0568
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_theta_min         1.981
_diffrn_reflns_theta_max         27.204
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.953
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             3171
_reflns_number_gt                1885
_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 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_cell_refinement       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_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)+(0.0687P)²+0.1028P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_extinction_coef       0.038(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         3023
_refine_ls_number_parameters     200
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0813
_refine_ls_R_factor_gt           0.0472
_refine_ls_wR_factor_ref         0.1503
_refine_ls_wR_factor_gt          0.1186
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_restrained_S_all      1.033
_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
C1 C 0.6225(3) 0.8544(2) 0.73468(10) 0.0572(5) Uani 1 1 d . . . . .
H1 H 0.626131 0.859496 0.779824 0.069 Uiso 1 1 calc R U . . .
C2 C 0.5770(3) 0.9707(2) 0.69954(10) 0.0590(6) Uani 1 1 d . . . . .
H2 H 0.550855 1.051954 0.721359 0.071 Uiso 1 1 calc R U . . .
C3 C 0.6067(3) 0.8501(2) 0.60653(9) 0.0509(5) Uani 1 1 d . . . . .
H3 H 0.600238 0.844922 0.561371 0.061 Uiso 1 1 calc R U . . .
C4 C 0.6549(2) 0.73200(18) 0.64223(8) 0.0404(4) Uani 1 1 d . . . . .
C5 C 0.7022(2) 0.59978(18) 0.61079(8) 0.0407(4) Uani 1 1 d . . . . .
C6 C 0.7725(2) 0.4888(2) 0.45241(8) 0.0445(5) Uani 1 1 d . . . . .
C7 C 0.8176(2) 0.35457(19) 0.42136(8) 0.0407(4) Uani 1 1 d . . . . .
C8 C 0.8678(3) 0.2352(2) 0.45480(9) 0.0509(5) Uani 1 1 d . . . . .
H8 H 0.876424 0.236400 0.500030 0.061 Uiso 1 1 calc R U . . .
C9 C 0.9054(3) 0.1139(2) 0.42245(9) 0.0524(5) Uani 1 1 d . . . . .
H9 H 0.937504 0.034207 0.445814 0.063 Uiso 1 1 calc R U . . .
C10 C 0.8951(2) 0.1117(2) 0.35554(9) 0.0447(5) Uani 1 1 d . . . . .
C11 C 0.8499(3) 0.2303(2) 0.32130(8) 0.0498(5) Uani 1 1 d . . . . .
H11 H 0.845088 0.229525 0.276087 0.060 Uiso 1 1 calc R U . . .
C12 C 0.8118(2) 0.3504(2) 0.35399(8) 0.0474(5) Uani 1 1 d . . . . .
H12 H 0.781525 0.430191 0.330418 0.057 Uiso 1 1 calc R U . . .
C13 C 0.7539(3) 0.4772(2) 0.65195(9) 0.0591(6) Uani 1 1 d . . . . .
H13A H 0.653880 0.410703 0.648457 0.089 Uiso 1 1 calc R U . . .
H13B H 0.774423 0.505675 0.696467 0.089 Uiso 1 1 calc R U . . .
H13C H 0.866839 0.436385 0.637445 0.089 Uiso 1 1 calc R U . . .
C14 C 0.9513(3) -0.1320(2) 0.35095(11) 0.0712(6) Uani 1 1 d . . . . .
H14A H 0.957347 -0.204208 0.319153 0.107 Uiso 1 1 calc R U . . .
H14B H 0.847070 -0.148546 0.377340 0.107 Uiso 1 1 calc R U . . .
H14C H 1.065854 -0.130855 0.377996 0.107 Uiso 1 1 calc R U . . .
N1 N 0.6620(2) 0.73412(16) 0.70715(7) 0.0507(4) Uani 1 1 d . . . . .
N2 N 0.5692(2) 0.97044(17) 0.63460(8) 0.0577(5) Uani 1 1 d . . . . .
N3 N 0.69997(18) 0.60436(15) 0.54822(7) 0.0431(4) Uani 1 1 d . . . . .
N4 N 0.7431(2) 0.48301(16) 0.51710(7) 0.0443(4) Uani 1 1 d D . . . .
O1 O 0.7648(2) 0.59702(14) 0.42169(7) 0.0646(4) Uani 1 1 d . . . . .
O2 O 0.92719(19) -0.00224(15) 0.31885(6) 0.0610(4) Uani 1 1 d . . . . .
O3 O 0.5505(2) 0.22413(17) 0.56077(9) 0.0779(5) Uani 1 1 d G . . . .
H3A H 0.538936 0.146552 0.579498 0.117 Uiso 1 1 d G U . . .
H3B H 0.442788 0.261502 0.561988 0.117 Uiso 1 1 d G U . . .
H4 H 0.716(3) 0.4026(13) 0.5337(9) 0.066(7) 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
C1 N1 1.332(2) . ?
C1 C2 1.366(3) . ?
C1 H1 0.9300 . ?
C2 N2 1.335(2) . ?
C2 H2 0.9300 . ?
C3 N2 1.334(2) . ?
C3 C4 1.390(2) . ?
C3 H3 0.9300 . ?
C4 N1 1.335(2) . ?
C4 C5 1.482(2) . ?
C5 N3 1.289(2) . ?
C5 C13 1.491(2) . ?
C6 O1 1.223(2) . ?
C6 N4 1.362(2) . ?
C6 C7 1.491(2) . ?
C7 C8 1.380(2) . ?
C7 C12 1.386(2) . ?
C8 C9 1.384(2) . ?
C8 H8 0.9300 . ?
C9 C10 1.376(2) . ?
C9 H9 0.9300 . ?
C10 O2 1.364(2) . ?
C10 C11 1.375(2) . ?
C11 C12 1.378(2) . ?
C11 H11 0.9300 . ?
C12 H12 0.9300 . ?
C13 H13A 0.9600 . ?
C13 H13B 0.9600 . ?
C13 H13C 0.9600 . ?
C14 O2 1.425(2) . ?
C14 H14A 0.9600 . ?
C14 H14B 0.9600 . ?
C14 H14C 0.9600 . ?
N3 N4 1.3811(19) . ?
N4 H4 0.876(9) . ?
O3 H3A 0.8501 . ?
O3 H3B 0.8499 . ?

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
N1 C1 C2 122.91(19) . . ?
N1 C1 H1 118.5 . . ?
C2 C1 H1 118.5 . . ?
N2 C2 C1 121.57(18) . . ?
N2 C2 H2 119.2 . . ?
C1 C2 H2 119.2 . . ?
N2 C3 C4 122.51(18) . . ?
N2 C3 H3 118.7 . . ?
C4 C3 H3 118.7 . . ?
N1 C4 C3 120.68(16) . . ?
N1 C4 C5 117.07(16) . . ?
C3 C4 C5 122.25(16) . . ?
N3 C5 C4 114.70(16) . . ?
N3 C5 C13 125.72(16) . . ?
C4 C5 C13 119.53(15) . . ?
O1 C6 N4 122.44(18) . . ?
O1 C6 C7 121.85(16) . . ?
N4 C6 C7 115.70(16) . . ?
C8 C7 C12 117.82(17) . . ?
C8 C7 C6 124.76(16) . . ?
C12 C7 C6 117.41(16) . . ?
C7 C8 C9 121.39(17) . . ?
C7 C8 H8 119.3 . . ?
C9 C8 H8 119.3 . . ?
C10 C9 C8 119.66(18) . . ?
C10 C9 H9 120.2 . . ?
C8 C9 H9 120.2 . . ?
O2 C10 C11 115.63(16) . . ?
O2 C10 C9 124.51(18) . . ?
C11 C10 C9 119.86(18) . . ?
C10 C11 C12 120.00(16) . . ?
C10 C11 H11 120.0 . . ?
C12 C11 H11 120.0 . . ?
C11 C12 C7 121.23(18) . . ?
C11 C12 H12 119.4 . . ?
C7 C12 H12 119.4 . . ?
C5 C13 H13A 109.5 . . ?
C5 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
C5 C13 H13C 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
O2 C14 H14A 109.5 . . ?
O2 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
O2 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C1 N1 C4 116.33(17) . . ?
C3 N2 C2 115.99(17) . . ?
C5 N3 N4 116.44(15) . . ?
C6 N4 N3 118.08(15) . . ?
C6 N4 H4 117.9(13) . . ?
N3 N4 H4 120.9(13) . . ?
C10 O2 C14 118.37(15) . . ?
H3A O3 H3B 104.5 . . ?

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
N1 C1 C2 N2 0.1(3) . . . . ?
N2 C3 C4 N1 1.4(3) . . . . ?
N2 C3 C4 C5 -178.03(15) . . . . ?
N1 C4 C5 N3 -177.60(14) . . . . ?
C3 C4 C5 N3 1.8(2) . . . . ?
N1 C4 C5 C13 0.2(2) . . . . ?
C3 C4 C5 C13 179.63(17) . . . . ?
O1 C6 C7 C8 165.52(18) . . . . ?
N4 C6 C7 C8 -13.7(2) . . . . ?
O1 C6 C7 C12 -13.3(2) . . . . ?
N4 C6 C7 C12 167.51(15) . . . . ?
C12 C7 C8 C9 -2.0(3) . . . . ?
C6 C7 C8 C9 179.20(16) . . . . ?
C7 C8 C9 C10 0.8(3) . . . . ?
C8 C9 C10 O2 -179.20(16) . . . . ?
C8 C9 C10 C11 0.8(3) . . . . ?
O2 C10 C11 C12 178.87(15) . . . . ?
C9 C10 C11 C12 -1.1(3) . . . . ?
C10 C11 C12 C7 -0.1(3) . . . . ?
C8 C7 C12 C11 1.7(3) . . . . ?
C6 C7 C12 C11 -179.44(15) . . . . ?
C2 C1 N1 C4 0.0(3) . . . . ?
C3 C4 N1 C1 -0.6(2) . . . . ?
C5 C4 N1 C1 178.79(15) . . . . ?
C4 C3 N2 C2 -1.3(3) . . . . ?
C1 C2 N2 C3 0.6(3) . . . . ?
C4 C5 N3 N4 -179.92(13) . . . . ?
C13 C5 N3 N4 2.4(2) . . . . ?
O1 C6 N4 N3 1.1(3) . . . . ?
C7 C6 N4 N3 -179.71(13) . . . . ?
C5 N3 N4 C6 -169.40(14) . . . . ?
C11 C10 O2 C14 -172.24(17) . . . . ?
C9 C10 O2 C14 7.8(3) . . . . ?

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
_geom_hbond_publ_flag
N4 H4 O3 0.876(9) 2.183(11) 3.019(2) 159.6(18) . yes
C13 H13A O3 0.96 2.63 3.361(3) 133.5 . yes
C13 H13A O3 0.96 2.63 3.361(3) 133.5 . yes
N4 H4 O3 0.876(9) 2.183(11) 3.019(2) 159.6(18) . yes

_refine_diff_density_max         0.155
_refine_diff_density_min         -0.225
_refine_diff_density_rms         0.041

####################################################################### 
# 
# 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_shelx_CCDC1
_database_code_depnum_ccdc_archive 'CCDC 2285408'
loop_
_audit_author_name
_audit_author_address
'M R Prathapachandra Kurup'
;Cochin University of Science and Technology
India
;
_audit_update_record             
;
2023-07-30 deposited with the CCDC.	2023-10-16 downloaded from the CCDC.
;
_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C14 H15 Cu N5 O6'
_chemical_formula_sum            'C14 H15 Cu N5 O6'
_chemical_formula_weight         412.86

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'
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           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                   7.0655(7)
_cell_length_b                   25.257(3)
_cell_length_c                   9.6732(10)
_cell_angle_alpha                90
_cell_angle_beta                 99.089(4)
_cell_angle_gamma                90
_cell_volume                     1704.5(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    302(2)
_cell_measurement_reflns_used    9665
_cell_measurement_theta_min      2.920
_cell_measurement_theta_max      30.624

_exptl_crystal_description       block
_exptl_crystal_colour            Green
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.609
_exptl_crystal_F_000             844
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.350
_exptl_crystal_size_mid          0.210
_exptl_crystal_size_min          0.120
_exptl_absorpt_coefficient_mu    1.324
_shelx_estimated_absorpt_T_min   0.714
_shelx_estimated_absorpt_T_max   0.857
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.734
_exptl_absorpt_correction_T_max  0.837
_exptl_absorpt_process_details   'SADABS (Bruker, 2004)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      302(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker axs kappa apex2 CCD Diffractometer'
_diffrn_measurement_method       'ω and φ scan'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            43124
_diffrn_reflns_av_unetI/netI     0.0160
_diffrn_reflns_av_R_equivalents  0.0340
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         2.920
_diffrn_reflns_theta_max         30.661
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             5269
_reflns_number_gt                4663
_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       'APEX2 (Bruker, 2004)'
_computing_cell_refinement       'APEX2/SAINT (Bruker, 2004)'
_computing_data_reduction        'SAINT/XPREP (Bruker, 2004)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    
'ORTEP3 (Farrugia, 1997) and Mercury (Bruno et al., 2002)'
_computing_publication_material  'SHELXL-2014/7 (Sheldrick, 2014)'
_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)+(0.0429P)²+0.6742P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         5248
_refine_ls_number_parameters     245
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.0394
_refine_ls_R_factor_gt           0.0334
_refine_ls_wR_factor_ref         0.0903
_refine_ls_wR_factor_gt          0.0868
_refine_ls_goodness_of_fit_ref   1.113
_refine_ls_restrained_S_all      1.113
_refine_ls_shift/su_max          0.001
_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
C1 C 0.2768(3) 0.30811(7) 0.5612(2) 0.0411(4) Uani 1 1 d . . . . .
H1 H 0.290167 0.296165 0.653136 0.049 Uiso 1 1 calc R U . . .
C2 C 0.2682(3) 0.27195(7) 0.4525(2) 0.0488(4) Uani 1 1 d . . . . .
H2 H 0.276270 0.236021 0.473714 0.059 Uiso 1 1 calc R U . . .
C3 C 0.2369(3) 0.33871(7) 0.29444(19) 0.0406(4) Uani 1 1 d . . . . .
H3 H 0.222639 0.350280 0.202101 0.049 Uiso 1 1 calc R U . . .
C4 C 0.2448(2) 0.37603(6) 0.40040(16) 0.0293(3) Uani 1 1 d . . . . .
C5 C 0.2308(2) 0.43409(6) 0.37819(16) 0.0289(3) Uani 1 1 d . . . . .
C6 C 0.2670(2) 0.52657(6) 0.64041(17) 0.0301(3) Uani 1 1 d . . . . .
C7 C 0.2735(2) 0.58328(6) 0.68075(17) 0.0314(3) Uani 1 1 d . . . . .
C8 C 0.2292(2) 0.62425(6) 0.58508(18) 0.0350(3) Uani 1 1 d . . . . .
H8 H 0.191945 0.616350 0.490802 0.042 Uiso 1 1 calc R U . . .
C9 C 0.2398(3) 0.67687(7) 0.6282(2) 0.0395(4) Uani 1 1 d . . . . .
H9 H 0.210799 0.703959 0.563142 0.047 Uiso 1 1 calc R U . . .
C10 C 0.2940(3) 0.68857(7) 0.7691(2) 0.0414(4) Uani 1 1 d . . . . .
C11 C 0.3393(3) 0.64792(8) 0.8654(2) 0.0497(5) Uani 1 1 d . . . . .
H11 H 0.377502 0.655876 0.959596 0.060 Uiso 1 1 calc R U . . .
C12 C 0.3281(3) 0.59599(7) 0.8223(2) 0.0428(4) Uani 1 1 d . . . . .
H12 H 0.357084 0.569049 0.887713 0.051 Uiso 1 1 calc R U . . .
C13 C 0.1929(3) 0.45842(7) 0.23650(18) 0.0405(4) Uani 1 1 d . . . . .
H13A H 0.110022 0.488454 0.238075 0.061 Uiso 1 1 calc R U . . .
H13B H 0.132512 0.432885 0.170318 0.061 Uiso 1 1 calc R U . . .
H13C H 0.311774 0.469620 0.209663 0.061 Uiso 1 1 calc R U . . .
C14 C 0.2647(5) 0.78130(8) 0.7299(3) 0.0757(8) Uani 1 1 d . . . . .
H14A H 0.345512 0.780194 0.658944 0.114 Uiso 1 1 calc R U . . .
H14B H 0.285035 0.814002 0.780688 0.114 Uiso 1 1 calc R U . . .
H14C H 0.132965 0.778861 0.686877 0.114 Uiso 1 1 calc R U . . .
Cu1 Cu 0.29363(3) 0.42120(2) 0.66938(2) 0.03065(7) Uani 1 1 d . . . . .
N1 N 0.26602(19) 0.35975(5) 0.53464(14) 0.0323(3) Uani 1 1 d . . . . .
N2 N 0.2491(3) 0.28667(6) 0.32024(19) 0.0495(4) Uani 1 1 d . . . . .
N3 N 0.25383(17) 0.45983(5) 0.49497(13) 0.0275(2) Uani 1 1 d . . . . .
N4 N 0.25092(18) 0.51416(5) 0.50432(14) 0.0296(2) Uani 1 1 d . . . . .
N5 N 0.1211(2) 0.37666(6) 0.86663(15) 0.0381(3) Uani 1 1 d . . . . .
O1 O 0.2795(2) 0.49294(4) 0.73991(13) 0.0394(3) Uani 1 1 d . . . . .
O2 O 0.3101(3) 0.73827(5) 0.82328(18) 0.0605(4) Uani 1 1 d . . . . .
O3 O 0.61042(19) 0.42033(6) 0.69796(17) 0.0480(3) Uani 1 1 d D . . . .
O4 O 0.29476(18) 0.38019(6) 0.84442(13) 0.0423(3) Uani 1 1 d . . . . .
O5 O -0.0030(2) 0.39654(8) 0.7782(2) 0.0686(5) Uani 1 1 d . . . . .
O6 O 0.0860(3) 0.35263(7) 0.96891(16) 0.0646(4) Uani 1 1 d . . . . .
H3A H 0.692(3) 0.4088(10) 0.761(2) 0.062(8) Uiso 1 1 d D . . . .
H3B H 0.660(3) 0.4409(9) 0.646(2) 0.058(7) 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
C1 N1 1.329(2) . ?
C1 C2 1.386(3) . ?
C1 H1 0.9300 . ?
C2 N2 1.319(3) . ?
C2 H2 0.9300 . ?
C3 N2 1.338(2) . ?
C3 C4 1.387(2) . ?
C3 H3 0.9300 . ?
C4 N1 1.348(2) . ?
C4 C5 1.483(2) . ?
C5 N3 1.291(2) . ?
C5 C13 1.487(2) . ?
C6 O1 1.2763(19) . ?
C6 N4 1.340(2) . ?
C6 C7 1.483(2) . ?
C7 C8 1.391(2) . ?
C7 C12 1.400(2) . ?
C8 C9 1.391(2) . ?
C8 H8 0.9300 . ?
C9 C10 1.389(3) . ?
C9 H9 0.9300 . ?
C10 O2 1.358(2) . ?
C10 C11 1.389(3) . ?
C11 C12 1.375(2) . ?
C11 H11 0.9300 . ?
C12 H12 0.9300 . ?
C13 H13A 0.9600 . ?
C13 H13B 0.9600 . ?
C13 H13C 0.9600 . ?
C14 O2 1.417(3) . ?
C14 H14A 0.9600 . ?
C14 H14B 0.9600 . ?
C14 H14C 0.9600 . ?
Cu1 N3 1.9307(13) . ?
Cu1 O1 1.9442(12) . ?
Cu1 O4 1.9837(13) . ?
Cu1 N1 2.0162(13) . ?
Cu1 O3 2.2116(14) . ?
N3 N4 1.3757(16) . ?
N5 O6 1.2191(19) . ?
N5 O5 1.231(2) . ?
N5 O4 1.282(2) . ?
O3 H3A 0.825(9) . ?
O3 H3B 0.836(9) . ?

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
N1 C1 C2 120.39(17) . . ?
N1 C1 H1 119.8 . . ?
C2 C1 H1 119.8 . . ?
N2 C2 C1 122.36(17) . . ?
N2 C2 H2 118.8 . . ?
C1 C2 H2 118.8 . . ?
N2 C3 C4 122.39(17) . . ?
N2 C3 H3 118.8 . . ?
C4 C3 H3 118.8 . . ?
N1 C4 C3 119.34(15) . . ?
N1 C4 C5 115.85(13) . . ?
C3 C4 C5 124.81(15) . . ?
N3 C5 C4 112.01(13) . . ?
N3 C5 C13 125.29(14) . . ?
C4 C5 C13 122.70(14) . . ?
O1 C6 N4 124.75(14) . . ?
O1 C6 C7 116.66(14) . . ?
N4 C6 C7 118.59(14) . . ?
C8 C7 C12 118.58(15) . . ?
C8 C7 C6 123.31(15) . . ?
C12 C7 C6 118.10(14) . . ?
C7 C8 C9 121.05(16) . . ?
C7 C8 H8 119.5 . . ?
C9 C8 H8 119.5 . . ?
C10 C9 C8 119.39(16) . . ?
C10 C9 H9 120.3 . . ?
C8 C9 H9 120.3 . . ?
O2 C10 C9 124.67(17) . . ?
O2 C10 C11 115.33(17) . . ?
C9 C10 C11 119.99(16) . . ?
C12 C11 C10 120.32(18) . . ?
C12 C11 H11 119.8 . . ?
C10 C11 H11 119.8 . . ?
C11 C12 C7 120.65(17) . . ?
C11 C12 H12 119.7 . . ?
C7 C12 H12 119.7 . . ?
C5 C13 H13A 109.5 . . ?
C5 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
C5 C13 H13C 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
O2 C14 H14A 109.5 . . ?
O2 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
O2 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
N3 Cu1 O1 80.05(5) . . ?
N3 Cu1 O4 171.92(5) . . ?
O1 Cu1 O4 100.40(6) . . ?
N3 Cu1 N1 80.69(5) . . ?
O1 Cu1 N1 159.91(5) . . ?
O4 Cu1 N1 97.86(6) . . ?
N3 Cu1 O3 96.84(5) . . ?
O1 Cu1 O3 94.15(6) . . ?
O4 Cu1 O3 91.18(5) . . ?
N1 Cu1 O3 93.78(6) . . ?
C1 N1 C4 118.67(15) . . ?
C1 N1 Cu1 129.34(12) . . ?
C4 N1 Cu1 111.88(10) . . ?
C2 N2 C3 116.85(16) . . ?
C5 N3 N4 123.96(13) . . ?
C5 N3 Cu1 119.40(10) . . ?
N4 N3 Cu1 116.64(10) . . ?
C6 N4 N3 107.34(12) . . ?
O6 N5 O5 123.58(18) . . ?
O6 N5 O4 119.57(16) . . ?
O5 N5 O4 116.79(15) . . ?
C6 O1 Cu1 110.92(10) . . ?
C10 O2 C14 117.80(18) . . ?
Cu1 O3 H3A 132.3(17) . . ?
Cu1 O3 H3B 115.7(16) . . ?
H3A O3 H3B 110.5(19) . . ?
N5 O4 Cu1 107.73(10) . . ?

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
N1 C1 C2 N2 -0.1(3) . . . . ?
N2 C3 C4 N1 0.2(3) . . . . ?
N2 C3 C4 C5 -179.58(17) . . . . ?
N1 C4 C5 N3 4.08(19) . . . . ?
C3 C4 C5 N3 -176.12(15) . . . . ?
N1 C4 C5 C13 -175.46(14) . . . . ?
C3 C4 C5 C13 4.3(2) . . . . ?
O1 C6 C7 C8 -168.66(15) . . . . ?
N4 C6 C7 C8 12.1(2) . . . . ?
O1 C6 C7 C12 11.8(2) . . . . ?
N4 C6 C7 C12 -167.51(15) . . . . ?
C12 C7 C8 C9 0.4(3) . . . . ?
C6 C7 C8 C9 -179.19(15) . . . . ?
C7 C8 C9 C10 -0.5(3) . . . . ?
C8 C9 C10 O2 179.71(18) . . . . ?
C8 C9 C10 C11 0.8(3) . . . . ?
O2 C10 C11 C12 180.0(2) . . . . ?
C9 C10 C11 C12 -1.0(3) . . . . ?
C10 C11 C12 C7 0.9(3) . . . . ?
C8 C7 C12 C11 -0.6(3) . . . . ?
C6 C7 C12 C11 179.03(18) . . . . ?
C2 C1 N1 C4 0.6(3) . . . . ?
C2 C1 N1 Cu1 -174.98(14) . . . . ?
C3 C4 N1 C1 -0.7(2) . . . . ?
C5 C4 N1 C1 179.11(15) . . . . ?
C3 C4 N1 Cu1 175.66(12) . . . . ?
C5 C4 N1 Cu1 -4.53(16) . . . . ?
C1 C2 N2 C3 -0.4(3) . . . . ?
C4 C3 N2 C2 0.3(3) . . . . ?
C4 C5 N3 N4 178.86(12) . . . . ?
C13 C5 N3 N4 -1.6(2) . . . . ?
C4 C5 N3 Cu1 -1.53(17) . . . . ?
C13 C5 N3 Cu1 177.99(13) . . . . ?
O1 C6 N4 N3 -1.0(2) . . . . ?
C7 C6 N4 N3 178.25(12) . . . . ?
C5 N3 N4 C6 176.09(13) . . . . ?
Cu1 N3 N4 C6 -3.52(15) . . . . ?
N4 C6 O1 Cu1 4.8(2) . . . . ?
C7 C6 O1 Cu1 -174.47(10) . . . . ?
C9 C10 O2 C14 1.3(3) . . . . ?
C11 C10 O2 C14 -179.7(2) . . . . ?
O6 N5 O4 Cu1 179.51(15) . . . . ?
O5 N5 O4 Cu1 2.3(2) . . . . ?

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
_geom_hbond_publ_flag
C1 H1 N2 0.93 2.69 3.494(2) 145.4 4_566 yes
C2 H2 O6 0.93 2.61 3.413(3) 145.1 4_565 yes
C3 H3 O6 0.93 2.31 3.180(2) 155.7 1_554 yes
O3 H3A O5 0.825(9) 2.16(2) 2.784(2) 133(2) 1_655 yes
O3 H3B N4 0.836(9) 2.024(10) 2.8515(19) 171(2) 3_666 yes

_refine_diff_density_max         0.476
_refine_diff_density_min         -0.422
_refine_diff_density_rms         0.065

