# 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 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_1
_database_code_depnum_ccdc_archive 'CCDC 1865730'
loop_
_audit_author_name
_audit_author_address
'Nora Veronika May'
;Research Centre for Natural Sciences, Hungarian Academy of Sciences
Hungary
;
_audit_update_record             
;
2019-05-15 deposited with the CCDC.	2019-06-05 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        
;
bis(3-hydroxy-1-methyl-4-pyridinecarboxylato)-monoaqua-copper(II) trihydrate
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C14 H14 Cu N2 O7, 3(H2 O)'
_chemical_formula_sum            'C14 H20 Cu N2 O10'
_chemical_formula_weight         439.86

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'
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      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_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'

_cell_length_a                   6.6329(4)
_cell_length_b                   9.5423(6)
_cell_length_c                   13.8849(9)
_cell_angle_alpha                85.573(2)
_cell_angle_beta                 89.691(2)
_cell_angle_gamma                87.100(2)
_cell_volume                     875.07(10)
_cell_formula_units_Z            2
_cell_measurement_temperature    103(2)
_cell_measurement_reflns_used    31673
_cell_measurement_theta_min      3.08
_cell_measurement_theta_max      27.49

_exptl_crystal_description       Chunk
_exptl_crystal_colour            Green
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.669
_exptl_crystal_F_000             454
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.500
_exptl_crystal_size_mid          0.300
_exptl_crystal_size_min          0.200
_exptl_absorpt_coefficient_mu    1.307
_shelx_estimated_absorpt_T_min   0.561
_shelx_estimated_absorpt_T_max   0.780
_exptl_absorpt_correction_type   Numerical
_exptl_absorpt_process_details   
;
 T.Higashi, Numerical Absorption Correction, NUMABS, 2002
;
_exptl_absorpt_correction_T_min  0.5858
_exptl_absorpt_correction_T_max  0.7669
_diffrn_ambient_temperature      103(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source_power             2.0000
_diffrn_source_voltage           50.0000
_diffrn_source_current           40.0000
_diffrn_radiation_source         'Sealed Tube'
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_detector       RX
_diffrn_measurement_device_type  'Rigaku RAXIS-RAPID II.'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measurement_method       dtprofit.ref
_diffrn_measurement_details      
;
 scan:  N=1,PHI=0.0,CHI=40.0,OMEGA=20.0,180.0,5.0,COUPLE=0.00                  
 scan:  N=2,PHI=90.0,CHI=40.0,OMEGA=20.0,165.0,5.0,COUPLE=0.00                 
 scan:  N=3,PHI=180.0,CHI=40.0,OMEGA=42.0,207.0,5.0,COUPLE=0.00                
 scan:  N=4,PHI=0.0,CHI=0.0,OMEGA=22.0,207.0,5.0,COUPLE=0.00                   
 scan:  N=5,PHI=180.0,CHI=15.0,OMEGA=22.0,207.0,5.0,COUPLE=0.00                
 scan:  N=6,PHI=90.0,CHI=15.0,OMEGA=22.0,207.0,5.0,COUPLE=0.00                 
 Orientation Matrix:
    UB11  0.0250 UB12 -0.0349 UB13  0.0689
    UB21  0.0387 UB22 -0.0958 UB23 -0.0208
    UB31  0.1438 UB32  0.0263 UB33 -0.0065
    Matrix type: 'd*Trek'
;
_diffrn_reflns_number            38334
_diffrn_reflns_av_unetI/netI     0.0178
_diffrn_reflns_av_R_equivalents  0.0400
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         3.075
_diffrn_reflns_theta_max         27.480
_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             3998
_reflns_number_gt                3710
_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       'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_cell_refinement       'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_data_reduction        'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_structure_solution    'Sir2014 (Burla, 2015)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Mercury (Macrae, 2006)'
_computing_publication_material  'Spek, A.L. (2015). Acta Cryst. C71, 9-18.'
_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)+(0.0385P)²+0.7195P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     difmap
_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         3998
_refine_ls_number_parameters     278
_refine_ls_number_restraints     8
_refine_ls_R_factor_all          0.0341
_refine_ls_R_factor_gt           0.0307
_refine_ls_wR_factor_ref         0.0826
_refine_ls_wR_factor_gt          0.0789
_refine_ls_goodness_of_fit_ref   1.120
_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 0.21760(4) 0.23931(2) 0.73271(2) 0.01894(8) Uani 1 1 d . . . . .
O12 O 0.2110(2) 0.29825(14) 0.59690(10) 0.0248(3) Uani 1 1 d . . . . .
O3 O 0.1867(2) 0.18444(14) 0.86886(9) 0.0221(3) Uani 1 1 d . . . . .
O11 O 0.2624(2) 0.27772(15) 0.44092(10) 0.0258(3) Uani 1 1 d . . . . .
O13 O 0.2035(2) 0.04352(14) 0.71314(9) 0.0252(3) Uani 1 1 d . . . . .
O2 O 0.1525(2) 0.43595(14) 0.75642(10) 0.0251(3) Uani 1 1 d . . . . .
O1 O 0.1923(3) 0.63082(15) 0.82830(11) 0.0320(4) Uani 1 1 d . . . . .
C12 C 0.2260(3) -0.15746(19) 0.62979(13) 0.0186(4) Uani 1 1 d . . . . .
H12 H 0.2142 -0.2121 0.6895 0.022 Uiso 1 1 calc R U . . .
C17 C 0.2390(3) 0.22565(19) 0.52459(13) 0.0178(3) Uani 1 1 d . . . . .
C3 C 0.2190(3) 0.2681(2) 0.93672(13) 0.0187(4) Uani 1 1 d . . . . .
N2 N 0.2454(2) -0.22347(16) 0.54843(11) 0.0183(3) Uani 1 1 d . . . . .
C13 C 0.2226(3) -0.00938(19) 0.62986(13) 0.0176(3) Uani 1 1 d . . . . .
C14 C 0.2403(3) 0.06726(19) 0.53871(12) 0.0156(3) Uani 1 1 d . . . . .
C7 C 0.1906(3) 0.5013(2) 0.83046(13) 0.0210(4) Uani 1 1 d . . . . .
O4 O 0.5508(2) 0.25707(18) 0.74536(12) 0.0335(4) Uani 1 1 d D . . . .
C15 C 0.2594(3) -0.0076(2) 0.45656(13) 0.0184(4) Uani 1 1 d . . . . .
H15 H 0.2711 0.0429 0.3953 0.022 Uiso 1 1 calc R U . . .
C18 C 0.2516(3) -0.3791(2) 0.55340(15) 0.0251(4) Uani 1 1 d . . . . .
H18A H 0.2419 -0.4162 0.6210 0.038 Uiso 1 1 calc R U . . .
H18B H 0.3788 -0.4142 0.5256 0.038 Uiso 1 1 calc R U . . .
H18C H 0.1381 -0.4099 0.5169 0.038 Uiso 1 1 calc R U . . .
C16 C 0.2618(3) -0.1518(2) 0.46132(13) 0.0198(4) Uani 1 1 d . . . . .
H16 H 0.2749 -0.2004 0.4042 0.024 Uiso 1 1 calc R U . . .
N1 N 0.2733(3) 0.27825(18) 1.10712(11) 0.0227(3) Uani 1 1 d . . . . .
C6 C 0.2835(3) 0.4199(2) 1.09733(14) 0.0238(4) Uani 1 1 d . . . . .
H6 H 0.3060 0.4711 1.1520 0.029 Uiso 1 1 calc R U . . .
C4 C 0.2275(3) 0.4162(2) 0.92559(13) 0.0185(4) Uani 1 1 d . . . . .
C5 C 0.2609(3) 0.4883(2) 1.00745(14) 0.0219(4) Uani 1 1 d . . . . .
H5 H 0.2682 0.5877 1.0005 0.026 Uiso 1 1 calc R U . . .
C2 C 0.2434(3) 0.2039(2) 1.03115(14) 0.0233(4) Uani 1 1 d . . . . .
H2 H 0.2384 0.1046 1.0411 0.028 Uiso 1 1 calc R U . . .
O6 O 0.2358(2) 0.51742(16) 0.32284(11) 0.0288(3) Uani 1 1 d D . . . .
O7 O 0.7742(3) 0.13241(19) 0.89447(12) 0.0358(4) Uani 1 1 d D . . . .
O5 O 0.2749(3) 0.87600(17) 0.91121(12) 0.0382(4) Uani 1 1 d D . . . .
C8 C 0.2911(4) 0.2038(3) 1.20428(14) 0.0331(5) Uani 1 1 d . . . . .
H8A H 0.1579 0.2027 1.2351 0.050 Uiso 1 1 calc R U . . .
H8B H 0.3835 0.2524 1.2436 0.050 Uiso 1 1 calc R U . . .
H8C H 0.3436 0.1069 1.1985 0.050 Uiso 1 1 calc R U . . .
H5W H 0.246(5) 0.946(2) 0.8746(19) 0.050(9) Uiso 1 1 d D . . . .
H5O H 0.240(4) 0.808(2) 0.883(2) 0.046(8) Uiso 1 1 d D . . . .
H4W H 0.601(4) 0.3332(18) 0.726(2) 0.043(8) Uiso 1 1 d D . . . .
H7W H 0.755(5) 0.135(4) 0.9541(9) 0.061(10) Uiso 1 1 d D . . . .
H4O H 0.612(4) 0.224(3) 0.7958(13) 0.044(8) Uiso 1 1 d D . . . .
H7O H 0.8979(19) 0.139(3) 0.881(2) 0.046(8) Uiso 1 1 d D . . . .
H6O H 0.247(4) 0.449(2) 0.3638(16) 0.041(8) Uiso 1 1 d D . . . .
H6W H 0.1127(18) 0.524(3) 0.310(2) 0.038(8) 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 O13 1.9155(14) . ?
Cu1 O12 1.9258(13) . ?
Cu1 O3 1.9349(13) . ?
Cu1 O2 1.9565(14) . ?
Cu1 O4 2.2339(16) . ?
O12 C17 1.271(2) . ?
O3 C3 1.306(2) . ?
O11 C17 1.240(2) . ?
O13 C13 1.300(2) . ?
O2 C7 1.276(2) . ?
O1 C7 1.235(2) . ?
C12 N2 1.338(2) . ?
C12 C13 1.412(3) . ?
C12 H12 0.9500 . ?
C17 C14 1.509(2) . ?
C3 C2 1.410(3) . ?
C3 C4 1.414(3) . ?
N2 C16 1.349(2) . ?
N2 C18 1.480(2) . ?
C13 C14 1.419(2) . ?
C14 C15 1.394(2) . ?
C7 C4 1.510(3) . ?
O4 H4W 0.838(10) . ?
O4 H4O 0.843(10) . ?
C15 C16 1.372(3) . ?
C15 H15 0.9500 . ?
C18 H18A 0.9800 . ?
C18 H18B 0.9800 . ?
C18 H18C 0.9800 . ?
C16 H16 0.9500 . ?
N1 C2 1.337(3) . ?
N1 C6 1.353(3) . ?
N1 C8 1.478(2) . ?
C6 C5 1.368(3) . ?
C6 H6 0.9500 . ?
C4 C5 1.397(3) . ?
C5 H5 0.9500 . ?
C2 H2 0.9500 . ?
O6 H6O 0.832(10) . ?
O6 H6W 0.836(10) . ?
O7 H7W 0.839(10) . ?
O7 H7O 0.845(10) . ?
O5 H5W 0.824(10) . ?
O5 H5O 0.831(10) . ?
C8 H8A 0.9800 . ?
C8 H8B 0.9800 . ?
C8 H8C 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
O13 Cu1 O12 94.23(6) . . ?
O13 Cu1 O3 86.24(6) . . ?
O12 Cu1 O3 172.57(6) . . ?
O13 Cu1 O2 164.38(7) . . ?
O12 Cu1 O2 87.22(6) . . ?
O3 Cu1 O2 90.36(6) . . ?
O13 Cu1 O4 100.94(7) . . ?
O12 Cu1 O4 94.13(6) . . ?
O3 Cu1 O4 93.06(6) . . ?
O2 Cu1 O4 94.46(7) . . ?
C17 O12 Cu1 129.54(12) . . ?
C3 O3 Cu1 123.22(12) . . ?
C13 O13 Cu1 124.59(12) . . ?
C7 O2 Cu1 129.05(13) . . ?
N2 C12 C13 122.22(16) . . ?
N2 C12 H12 118.9 . . ?
C13 C12 H12 118.9 . . ?
O11 C17 O12 123.60(17) . . ?
O11 C17 C14 116.89(16) . . ?
O12 C17 C14 119.51(16) . . ?
O3 C3 C2 116.44(17) . . ?
O3 C3 C4 126.77(17) . . ?
C2 C3 C4 116.78(17) . . ?
C12 N2 C16 121.68(16) . . ?
C12 N2 C18 119.59(16) . . ?
C16 N2 C18 118.72(15) . . ?
O13 C13 C12 117.01(16) . . ?
O13 C13 C14 126.34(17) . . ?
C12 C13 C14 116.66(16) . . ?
C15 C14 C13 118.39(16) . . ?
C15 C14 C17 117.45(16) . . ?
C13 C14 C17 124.16(16) . . ?
O1 C7 O2 122.90(18) . . ?
O1 C7 C4 118.77(17) . . ?
O2 C7 C4 118.29(17) . . ?
Cu1 O4 H4W 119(2) . . ?
Cu1 O4 H4O 120(2) . . ?
H4W O4 H4O 108(3) . . ?
C16 C15 C14 122.16(17) . . ?
C16 C15 H15 118.9 . . ?
C14 C15 H15 118.9 . . ?
N2 C18 H18A 109.5 . . ?
N2 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
N2 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
N2 C16 C15 118.90(16) . . ?
N2 C16 H16 120.6 . . ?
C15 C16 H16 120.6 . . ?
C2 N1 C6 121.59(17) . . ?
C2 N1 C8 119.00(18) . . ?
C6 N1 C8 119.40(17) . . ?
N1 C6 C5 118.95(17) . . ?
N1 C6 H6 120.5 . . ?
C5 C6 H6 120.5 . . ?
C5 C4 C3 118.49(17) . . ?
C5 C4 C7 118.24(17) . . ?
C3 C4 C7 123.17(16) . . ?
C6 C5 C4 121.97(18) . . ?
C6 C5 H5 119.0 . . ?
C4 C5 H5 119.0 . . ?
N1 C2 C3 122.22(18) . . ?
N1 C2 H2 118.9 . . ?
C3 C2 H2 118.9 . . ?
H6O O6 H6W 104(3) . . ?
H7W O7 H7O 111(3) . . ?
H5W O5 H5O 106(3) . . ?
N1 C8 H8A 109.5 . . ?
N1 C8 H8B 109.5 . . ?
H8A C8 H8B 109.5 . . ?
N1 C8 H8C 109.5 . . ?
H8A C8 H8C 109.5 . . ?
H8B C8 H8C 109.5 . . ?

_refine_diff_density_max         0.762
_refine_diff_density_min         -0.352
_refine_diff_density_rms         0.118


_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: water'
####################################################################### 
# 
# 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_5
_database_code_depnum_ccdc_archive 'CCDC 1865734'
loop_
_audit_author_name
_audit_author_address
'Nora Veronika May'
;Research Centre for Natural Sciences, Hungarian Academy of Sciences
Hungary
;
_audit_update_record             
;
2019-05-15 deposited with the CCDC.	2019-06-05 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT415_5                   
;
PROBLEM: Short Inter D-H..H-X       H2       ..H14      .       2.06 Ang.
RESPONSE: Both OH protons H14 and H24 could be detected on the difference Fourier map pointing towards two carboxylate oxigens O1 and O21, respectively, of a neighbouring complex. These protons were then affixed with the Shelx command 147 to avoid virtual bond shortening and resulting in a 0.84 \%A O-H distances. The obtained close distances of H14 and H24 protons with H2 and H22 pyridine ring protons is about 2.0 \%A which is relatively short, but it is not extramely short. We believe that the attractive force  established by the O14-H14?O1 and O24-H24?O21 bonds are able to exceed the repulsion forces arised between the H14?H2 and H24?H22 protons.
;
# Added during the CSD deposition process: Wednesday 15 May 2019 02:09 PM
# end Validation Reply Form


_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        
""'bis(μ2-4-hydroxy-1-(2-hydroxyethyl)-6-methyl-3-pyridinecarboxylato)-bis(μ2-4-hydroxy-1-(2-hydroxyethyl)-6-methyl-3-pyridinecarboxylato)-bis(μ2-4-hydroxy-1-(2-hydroxyethyl)-6-methyl-3-pyridinecarboxylato)-tri-copper(II) nonahydrate'""

_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C54 H60 Cu3 N6 O24, 12(H2 O), 4(H O), 2(O)'
_chemical_formula_sum            'C54 H88 Cu3 N6 O42'
_chemical_formula_weight         1683.92

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'
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'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_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'

_cell_length_a                   12.1956(4)
_cell_length_b                   12.4877(4)
_cell_length_c                   12.6185(5)
_cell_angle_alpha                98.9780(10)
_cell_angle_beta                 91.0710(10)
_cell_angle_gamma                113.1190(10)
_cell_volume                     1738.97(11)
_cell_formula_units_Z            1
_cell_measurement_temperature    103(2)
_cell_measurement_reflns_used    47047
_cell_measurement_theta_min      3.04
_cell_measurement_theta_max      27.46

_exptl_crystal_description       Chunk
_exptl_crystal_colour            Blue
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.608
_exptl_crystal_F_000             877
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.25
_exptl_absorpt_coefficient_mu    1.018
_shelx_estimated_absorpt_T_min   0.785
_shelx_estimated_absorpt_T_max   0.785
_exptl_absorpt_correction_type   Numerical
_exptl_absorpt_correction_T_min  0.6660
_exptl_absorpt_correction_T_max  0.8784
_exptl_absorpt_process_details   
;
 T.Higashi, Numerical Absorption Correction, NUMABS, 2002
;
_diffrn_ambient_temperature      103(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source_power             2.0000
_diffrn_source_voltage           50.0000
_diffrn_source_current           40.0000
_diffrn_radiation_source         'Sealed Tube'
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_detector       RX
_diffrn_measurement_device_type  'Rigaku RAXIS-RAPID II.'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measurement_method       dtprofit.ref
_diffrn_measurement_details      
;
 scan:  N=1,PHI=180.0,CHI=0.0,OMEGA=25.0,195.0,5.0,COUPLE=0.00                 
 scan:  N=2,PHI=270.0,CHI=45.0,OMEGA=26.0,216.0,5.0,COUPLE=0.00                
 scan:  N=3,PHI=90.0,CHI=45.0,OMEGA=25.0,225.0,5.0,COUPLE=0.00                 
 scan:  N=4,PHI=0.0,CHI=45.0,OMEGA=28.0,193.0,5.0,COUPLE=0.00                  
 scan:  N=5,PHI=180.0,CHI=45.0,OMEGA=60.0,200.0,5.0,COUPLE=0.00                
 scan:  N=6,PHI=90.0,CHI=0.0,OMEGA=100.0,200.0,5.0,COUPLE=0.00                 
 Orientation Matrix:
    UB11  0.0834 UB12  0.0623 UB13  0.0078
    UB21 -0.0006 UB22  0.0104 UB23  0.0802
    UB31  0.0325 UB32 -0.0620 UB33  0.0008
    Matrix type: 'd*Trek'
;
_diffrn_reflns_number            70996
_diffrn_reflns_av_unetI/netI     0.0237
_diffrn_reflns_av_R_equivalents  0.0458
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         3.034
_diffrn_reflns_theta_max         27.457
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             7929
_reflns_number_gt                6746
_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       'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_cell_refinement       'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_data_reduction        'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_structure_solution    'Sir2014 (Burla, 2015)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Mercury (Macrae, 2006)'
_computing_publication_material  'Spek, A.L. (2015). Acta Cryst. C71, 9-18.'
_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)+(0.0558P)²+2.1123P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     difmap
_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         7929
_refine_ls_number_parameters     494
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0508
_refine_ls_R_factor_gt           0.0415
_refine_ls_wR_factor_ref         0.1168
_refine_ls_wR_factor_gt          0.1063
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_restrained_S_all      1.088
_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 0.16103(2) 0.37057(2) 0.57337(2) 0.01565(9) Uani 1 1 d . . . . .
Cu2 Cu 0.5000 1.0000 0.5000 0.02261(11) Uani 1 2 d S . P . .
O3 O 0.13287(14) 0.30223(14) 0.70419(13) 0.0176(3) Uani 1 1 d . . . . .
O2 O 0.04862(15) 0.22520(14) 0.48517(13) 0.0194(3) Uani 1 1 d . . . . .
O1 O -0.11028(15) 0.05628(15) 0.44513(13) 0.0211(4) Uani 1 1 d . . . . .
O4 O -0.13960(16) -0.21207(16) 0.82124(15) 0.0246(4) Uani 1 1 d . . . . .
H4 H -0.1769 -0.2479 0.8690 0.037 Uiso 1 1 calc R U . . .
O13 O 0.19479(14) 0.42861(15) 0.44031(13) 0.0195(3) Uani 1 1 d . . . . .
O12 O 0.30330(14) 0.49533(15) 0.65161(13) 0.0198(3) Uani 1 1 d . . . . .
O11 O 0.48541(15) 0.63941(16) 0.67472(14) 0.0236(4) Uani 1 1 d . . . . .
O14 O 0.64930(15) 0.92448(15) 0.44431(14) 0.0231(4) Uani 1 1 d . . . . .
H14 H 0.7210 0.9725 0.4591 0.035 Uiso 1 1 calc R U . . .
O23 O 0.48130(16) 0.93040(15) 0.63092(14) 0.0243(4) Uani 1 1 d . . . . .
O22 O 0.37177(16) 0.86111(15) 0.41852(14) 0.0245(4) Uani 1 1 d . . . . .
O21 O 0.19316(15) 0.71457(16) 0.39389(13) 0.0231(4) Uani 1 1 d . . . . .
O24 O 0.02724(15) 0.45204(16) 0.62186(13) 0.0212(4) Uani 1 1 d . . . . .
H24 H -0.0409 0.3988 0.6008 0.032 Uiso 1 1 calc R U . . .
N1 N -0.15243(17) 0.00679(17) 0.75463(16) 0.0168(4) Uani 1 1 d . . . . .
N11 N 0.51160(17) 0.65883(17) 0.35719(16) 0.0168(4) Uani 1 1 d . . . . .
N21 N 0.16004(19) 0.70575(18) 0.71369(16) 0.0192(4) Uani 1 1 d . . . . .
C2 C -0.1318(2) 0.0277(2) 0.65389(18) 0.0168(4) Uani 1 1 d . . . . .
H2 H -0.1842 -0.0282 0.5960 0.020 Uiso 1 1 calc R U . . .
C3 C -0.03992(19) 0.1249(2) 0.62945(18) 0.0155(4) Uani 1 1 d . . . . .
C4 C 0.0419(2) 0.2083(2) 0.71575(18) 0.0162(4) Uani 1 1 d . . . . .
C5 C 0.0170(2) 0.1833(2) 0.82060(18) 0.0183(5) Uani 1 1 d . . . . .
H5 H 0.0682 0.2371 0.8802 0.022 Uiso 1 1 calc R U . . .
C6 C -0.0774(2) 0.0853(2) 0.84017(19) 0.0182(5) Uani 1 1 d . . . . .
C7 C -0.0336(2) 0.1358(2) 0.51271(18) 0.0166(4) Uani 1 1 d . . . . .
C8 C -0.2548(2) -0.1044(2) 0.7657(2) 0.0202(5) Uani 1 1 d . . . . .
H8A H -0.3237 -0.1159 0.7159 0.024 Uiso 1 1 calc R U . . .
H8B H -0.2790 -0.0977 0.8400 0.024 Uiso 1 1 calc R U . . .
C9 C -0.2229(2) -0.2113(2) 0.7409(2) 0.0214(5) Uani 1 1 d . . . . .
H9A H -0.2969 -0.2843 0.7349 0.026 Uiso 1 1 calc R U . . .
H9B H -0.1884 -0.2116 0.6705 0.026 Uiso 1 1 calc R U . . .
C10 C -0.1035(2) 0.0626(2) 0.9518(2) 0.0254(5) Uani 1 1 d . . . . .
H10A H -0.0414 0.1242 1.0037 0.038 Uiso 1 1 calc R U . . .
H10B H -0.1044 -0.0150 0.9583 0.038 Uiso 1 1 calc R U . . .
H10C H -0.1816 0.0637 0.9666 0.038 Uiso 1 1 calc R U . . .
C12 C 0.4985(2) 0.6477(2) 0.46136(19) 0.0169(4) Uani 1 1 d . . . . .
H12 H 0.5645 0.6938 0.5130 0.020 Uiso 1 1 calc R U . . .
C13 C 0.3946(2) 0.57309(19) 0.49695(18) 0.0153(4) Uani 1 1 d . . . . .
C14 C 0.2951(2) 0.5041(2) 0.41926(18) 0.0161(4) Uani 1 1 d . . . . .
C15 C 0.3116(2) 0.5218(2) 0.31100(19) 0.0181(5) Uani 1 1 d . . . . .
H15 H 0.2464 0.4795 0.2578 0.022 Uiso 1 1 calc R U . . .
C16 C 0.4167(2) 0.5967(2) 0.28005(19) 0.0174(5) Uani 1 1 d . . . . .
C17 C 0.3949(2) 0.5697(2) 0.61588(18) 0.0156(4) Uani 1 1 d . . . . .
C18 C 0.6278(2) 0.7422(2) 0.3283(2) 0.0216(5) Uani 1 1 d . . . . .
H18A H 0.6409 0.7129 0.2542 0.026 Uiso 1 1 calc R U . . .
H18B H 0.6932 0.7445 0.3776 0.026 Uiso 1 1 calc R U . . .
C19 C 0.6329(2) 0.8660(2) 0.3350(2) 0.0232(5) Uani 1 1 d . . . . .
H19A H 0.6998 0.9119 0.2955 0.028 Uiso 1 1 calc R U . . .
H19B H 0.5576 0.8620 0.3003 0.028 Uiso 1 1 calc R U . . .
C20 C 0.4332(2) 0.6119(2) 0.1649(2) 0.0231(5) Uani 1 1 d . . . . .
H20A H 0.3569 0.5672 0.1211 0.035 Uiso 1 1 calc R U . . .
H20B H 0.4929 0.5824 0.1381 0.035 Uiso 1 1 calc R U . . .
H20C H 0.4606 0.6959 0.1604 0.035 Uiso 1 1 calc R U . . .
C22 C 0.1739(2) 0.7173(2) 0.61001(19) 0.0194(5) Uani 1 1 d . . . . .
H22 H 0.1070 0.6745 0.5586 0.023 Uiso 1 1 calc R U . . .
C23 C 0.2796(2) 0.7877(2) 0.57398(19) 0.0188(5) Uani 1 1 d . . . . .
C24 C 0.3805(2) 0.8541(2) 0.65109(19) 0.0213(5) Uani 1 1 d . . . . .
C25 C 0.3628(2) 0.8321(2) 0.7586(2) 0.0251(5) Uani 1 1 d . . . . .
H25 H 0.4293 0.8691 0.8113 0.030 Uiso 1 1 calc R U . . .
C26 C 0.2565(2) 0.7612(2) 0.7896(2) 0.0232(5) Uani 1 1 d . . . . .
C27 C 0.2815(2) 0.7882(2) 0.45490(19) 0.0189(5) Uani 1 1 d . . . . .
C28 C 0.0407(2) 0.6289(2) 0.7415(2) 0.0231(5) Uani 1 1 d . . . . .
H28A H -0.0220 0.6318 0.6925 0.028 Uiso 1 1 calc R U . . .
H28B H 0.0290 0.6584 0.8161 0.028 Uiso 1 1 calc R U . . .
C29 C 0.0288(2) 0.5025(2) 0.73213(19) 0.0229(5) Uani 1 1 d . . . . .
H29A H 0.0967 0.5006 0.7748 0.027 Uiso 1 1 calc R U . . .
H29B H -0.0461 0.4552 0.7617 0.027 Uiso 1 1 calc R U . . .
C30 C 0.2408(3) 0.7419(2) 0.9038(2) 0.0298(6) Uani 1 1 d . . . . .
H30A H 0.3155 0.7907 0.9488 0.045 Uiso 1 1 calc R U . . .
H30B H 0.2202 0.6583 0.9066 0.045 Uiso 1 1 calc R U . . .
H30C H 0.1764 0.7642 0.9307 0.045 Uiso 1 1 calc R U . . .
O31 O 0.27066(17) 0.45682(17) 0.89627(14) 0.0278(4) Uani 1 1 d . . . . .
H31O H 0.3303 0.5200 0.8940 0.042 Uiso 1 1 d R U . . .
H31W H 0.2455 0.4247 0.8323 0.042 Uiso 1 1 d R U . . .
O32 O 0.08433(18) -0.08163(18) 0.77172(15) 0.0313(4) Uani 1 1 d . . . . .
H32O H 0.0944 -0.0631 0.7097 0.047 Uiso 1 1 d R U . . .
H32W H 0.0390 -0.1339 0.7929 0.047 Uiso 1 1 d R U . . .
O33 O 0.48133(18) 0.6560(2) 0.89053(15) 0.0389(5) Uani 1 1 d . . . . .
H33W H 0.5484 0.6599 0.9112 0.058 Uiso 1 1 d R U . . .
H33O H 0.4831 0.6682 0.8271 0.058 Uiso 1 1 d R U . . .
O34 O -0.1060(2) 0.5013(2) 0.95638(17) 0.0370(5) Uani 1 1 d D . . . .
O35 O 0.6013(3) 1.0752(2) 0.84006(18) 0.0603(8) Uani 1 1 d . . . . .
H35W H 0.5778 1.0413 0.7767 0.090 Uiso 1 1 d R U . . .
H35O H 0.6415 1.1464 0.8400 0.090 Uiso 1 1 d R U . . .
O37 O 0.2153(2) 0.7221(3) 0.17329(17) 0.0569(7) Uani 1 1 d . . . . .
H37O H 0.2177 0.7143 0.2376 0.085 Uiso 1 1 d R U . . .
H37W H 0.1883 0.6555 0.1349 0.085 Uiso 1 1 d R U . . .
O39 O 0.4529(3) 1.0996(3) 0.9967(2) 0.0728(9) Uani 1 1 d . . . . .
H39O H 0.4244 1.0440 1.0329 0.109 Uiso 1 1 d R U . . .
H39W H 0.4845 1.0745 0.9444 0.109 Uiso 1 1 d R U . . .
O36 O -0.28836(18) -0.3082(2) 0.97152(17) 0.0434(6) Uani 1 1 d . . . . .
H36W H -0.2815 -0.3485 1.0075 0.065 Uiso 1 1 d R U . . .
O38A O 0.2589(3) 0.1121(3) 0.8878(2) 0.0329(7) Uani 0.7 1 d . . P . .
O28B O 0.3161(8) 0.0766(8) 0.9104(6) 0.052(2) Uani 0.3 1 d . . P . .
H34O H -0.145(2) 0.514(3) 0.998(2) 0.025(8) 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 O13 1.9197(16) . ?
Cu1 O12 1.9353(16) . ?
Cu1 O2 1.9421(16) . ?
Cu1 O3 1.9499(16) . ?
Cu1 O24 2.2843(17) . ?
Cu2 O22 1.9401(17) 2_676 ?
Cu2 O22 1.9401(17) . ?
Cu2 O23 1.9604(17) . ?
Cu2 O23 1.9604(17) 2_676 ?
Cu2 O14 2.4265(19) 2_676 ?
Cu2 O14 2.4265(19) . ?
O3 C4 1.291(3) . ?
O2 C7 1.276(3) . ?
O1 C7 1.251(3) . ?
O4 C9 1.426(3) . ?
O4 H4 0.8400 . ?
O13 C14 1.281(3) . ?
O12 C17 1.284(3) . ?
O11 C17 1.241(3) . ?
O14 C19 1.427(3) . ?
O14 H14 0.8400 . ?
O23 C24 1.285(3) . ?
O22 C27 1.270(3) . ?
O21 C27 1.253(3) . ?
O24 C29 1.432(3) . ?
O24 H24 0.8400 . ?
N1 C2 1.346(3) . ?
N1 C6 1.376(3) . ?
N1 C8 1.488(3) . ?
N11 C12 1.349(3) . ?
N11 C16 1.381(3) . ?
N11 C18 1.484(3) . ?
N21 C22 1.345(3) . ?
N21 C26 1.376(3) . ?
N21 C28 1.479(3) . ?
C2 C3 1.373(3) . ?
C2 H2 0.9500 . ?
C3 C4 1.433(3) . ?
C3 C7 1.501(3) . ?
C4 C5 1.417(3) . ?
C5 C6 1.372(3) . ?
C5 H5 0.9500 . ?
C6 C10 1.496(3) . ?
C8 C9 1.520(4) . ?
C8 H8A 0.9900 . ?
C8 H8B 0.9900 . ?
C9 H9A 0.9900 . ?
C9 H9B 0.9900 . ?
C10 H10A 0.9800 . ?
C10 H10B 0.9800 . ?
C10 H10C 0.9800 . ?
C12 C13 1.379(3) . ?
C12 H12 0.9500 . ?
C13 C14 1.430(3) . ?
C13 C17 1.508(3) . ?
C14 C15 1.423(3) . ?
C15 C16 1.364(3) . ?
C15 H15 0.9500 . ?
C16 C20 1.501(3) . ?
C18 C19 1.511(4) . ?
C18 H18A 0.9900 . ?
C18 H18B 0.9900 . ?
C19 H19A 0.9900 . ?
C19 H19B 0.9900 . ?
C20 H20A 0.9800 . ?
C20 H20B 0.9800 . ?
C20 H20C 0.9800 . ?
C22 C23 1.377(4) . ?
C22 H22 0.9500 . ?
C23 C24 1.432(3) . ?
C23 C27 1.504(3) . ?
C24 C25 1.430(4) . ?
C25 C26 1.358(4) . ?
C25 H25 0.9500 . ?
C26 C30 1.501(3) . ?
C28 C29 1.513(4) . ?
C28 H28A 0.9900 . ?
C28 H28B 0.9900 . ?
C29 H29A 0.9900 . ?
C29 H29B 0.9900 . ?
C30 H30A 0.9800 . ?
C30 H30B 0.9800 . ?
C30 H30C 0.9800 . ?
O31 H31O 0.8426 . ?
O31 H31W 0.8369 . ?
O32 H32O 0.8478 . ?
O32 H32W 0.7619 . ?
O33 H33W 0.8348 . ?
O33 H33O 0.8368 . ?
O34 H34O 0.761(18) . ?
O35 H35W 0.8311 . ?
O35 H35O 0.8307 . ?
O37 H37O 0.8336 . ?
O37 H37W 0.8300 . ?
O39 H39O 0.8527 . ?
O39 H39W 0.8502 . ?
O36 H36W 0.7547 . ?
O38A O28B 1.020(11) . ?

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
O13 Cu1 O12 93.34(7) . . ?
O13 Cu1 O2 85.57(7) . . ?
O12 Cu1 O2 164.32(8) . . ?
O13 Cu1 O3 175.14(7) . . ?
O12 Cu1 O3 87.28(7) . . ?
O2 Cu1 O3 92.53(7) . . ?
O13 Cu1 O24 96.82(7) . . ?
O12 Cu1 O24 98.22(7) . . ?
O2 Cu1 O24 97.44(7) . . ?
O3 Cu1 O24 87.86(7) . . ?
O22 Cu2 O22 180.0 2_676 . ?
O22 Cu2 O23 87.41(7) 2_676 . ?
O22 Cu2 O23 92.59(7) . . ?
O22 Cu2 O23 92.59(7) 2_676 2_676 ?
O22 Cu2 O23 87.41(7) . 2_676 ?
O23 Cu2 O23 180.0 . 2_676 ?
O22 Cu2 O14 91.89(7) 2_676 2_676 ?
O22 Cu2 O14 88.11(7) . 2_676 ?
O23 Cu2 O14 88.42(7) . 2_676 ?
O23 Cu2 O14 91.58(7) 2_676 2_676 ?
O22 Cu2 O14 88.11(7) 2_676 . ?
O22 Cu2 O14 91.89(7) . . ?
O23 Cu2 O14 91.58(7) . . ?
O23 Cu2 O14 88.42(7) 2_676 . ?
O14 Cu2 O14 180.0 2_676 . ?
C4 O3 Cu1 125.17(14) . . ?
C7 O2 Cu1 129.96(15) . . ?
C9 O4 H4 109.5 . . ?
C14 O13 Cu1 126.13(15) . . ?
C17 O12 Cu1 129.62(15) . . ?
C19 O14 Cu2 115.73(15) . . ?
C19 O14 H14 109.5 . . ?
Cu2 O14 H14 115.8 . . ?
C24 O23 Cu2 122.23(15) . . ?
C27 O22 Cu2 127.20(16) . . ?
C29 O24 Cu1 119.67(14) . . ?
C29 O24 H24 109.5 . . ?
Cu1 O24 H24 106.1 . . ?
C2 N1 C6 119.42(19) . . ?
C2 N1 C8 116.73(19) . . ?
C6 N1 C8 123.82(19) . . ?
C12 N11 C16 120.13(19) . . ?
C12 N11 C18 118.8(2) . . ?
C16 N11 C18 121.05(19) . . ?
C22 N21 C26 119.9(2) . . ?
C22 N21 C28 118.1(2) . . ?
C26 N21 C28 121.9(2) . . ?
N1 C2 C3 124.2(2) . . ?
N1 C2 H2 117.9 . . ?
C3 C2 H2 117.9 . . ?
C2 C3 C4 118.5(2) . . ?
C2 C3 C7 116.7(2) . . ?
C4 C3 C7 124.8(2) . . ?
O3 C4 C5 119.4(2) . . ?
O3 C4 C3 125.0(2) . . ?
C5 C4 C3 115.7(2) . . ?
C6 C5 C4 123.2(2) . . ?
C6 C5 H5 118.4 . . ?
C4 C5 H5 118.4 . . ?
C5 C6 N1 119.1(2) . . ?
C5 C6 C10 122.1(2) . . ?
N1 C6 C10 118.8(2) . . ?
O1 C7 O2 122.0(2) . . ?
O1 C7 C3 118.4(2) . . ?
O2 C7 C3 119.6(2) . . ?
N1 C8 C9 111.68(19) . . ?
N1 C8 H8A 109.3 . . ?
C9 C8 H8A 109.3 . . ?
N1 C8 H8B 109.3 . . ?
C9 C8 H8B 109.3 . . ?
H8A C8 H8B 107.9 . . ?
O4 C9 C8 112.7(2) . . ?
O4 C9 H9A 109.1 . . ?
C8 C9 H9A 109.1 . . ?
O4 C9 H9B 109.1 . . ?
C8 C9 H9B 109.1 . . ?
H9A C9 H9B 107.8 . . ?
C6 C10 H10A 109.5 . . ?
C6 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
C6 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
N11 C12 C13 123.6(2) . . ?
N11 C12 H12 118.2 . . ?
C13 C12 H12 118.2 . . ?
C12 C13 C14 118.2(2) . . ?
C12 C13 C17 117.0(2) . . ?
C14 C13 C17 124.8(2) . . ?
O13 C14 C15 118.8(2) . . ?
O13 C14 C13 124.9(2) . . ?
C15 C14 C13 116.3(2) . . ?
C16 C15 C14 123.1(2) . . ?
C16 C15 H15 118.4 . . ?
C14 C15 H15 118.4 . . ?
C15 C16 N11 118.7(2) . . ?
C15 C16 C20 122.3(2) . . ?
N11 C16 C20 119.1(2) . . ?
O11 C17 O12 123.1(2) . . ?
O11 C17 C13 117.7(2) . . ?
O12 C17 C13 119.23(19) . . ?
N11 C18 C19 112.3(2) . . ?
N11 C18 H18A 109.1 . . ?
C19 C18 H18A 109.1 . . ?
N11 C18 H18B 109.1 . . ?
C19 C18 H18B 109.1 . . ?
H18A C18 H18B 107.9 . . ?
O14 C19 C18 111.0(2) . . ?
O14 C19 H19A 109.4 . . ?
C18 C19 H19A 109.4 . . ?
O14 C19 H19B 109.4 . . ?
C18 C19 H19B 109.4 . . ?
H19A C19 H19B 108.0 . . ?
C16 C20 H20A 109.5 . . ?
C16 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
C16 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
N21 C22 C23 123.8(2) . . ?
N21 C22 H22 118.1 . . ?
C23 C22 H22 118.1 . . ?
C22 C23 C24 118.5(2) . . ?
C22 C23 C27 117.3(2) . . ?
C24 C23 C27 124.2(2) . . ?
O23 C24 C25 119.5(2) . . ?
O23 C24 C23 125.4(2) . . ?
C25 C24 C23 115.1(2) . . ?
C26 C25 C24 123.7(2) . . ?
C26 C25 H25 118.1 . . ?
C24 C25 H25 118.1 . . ?
C25 C26 N21 118.7(2) . . ?
C25 C26 C30 122.2(2) . . ?
N21 C26 C30 119.1(2) . . ?
O21 C27 O22 121.7(2) . . ?
O21 C27 C23 118.3(2) . . ?
O22 C27 C23 120.0(2) . . ?
N21 C28 C29 110.8(2) . . ?
N21 C28 H28A 109.5 . . ?
C29 C28 H28A 109.5 . . ?
N21 C28 H28B 109.5 . . ?
C29 C28 H28B 109.5 . . ?
H28A C28 H28B 108.1 . . ?
O24 C29 C28 110.4(2) . . ?
O24 C29 H29A 109.6 . . ?
C28 C29 H29A 109.6 . . ?
O24 C29 H29B 109.6 . . ?
C28 C29 H29B 109.6 . . ?
H29A C29 H29B 108.1 . . ?
C26 C30 H30A 109.5 . . ?
C26 C30 H30B 109.5 . . ?
H30A C30 H30B 109.5 . . ?
C26 C30 H30C 109.5 . . ?
H30A C30 H30C 109.5 . . ?
H30B C30 H30C 109.5 . . ?
H31O O31 H31W 106.4 . . ?
H32O O32 H32W 133.5 . . ?
H33W O33 H33O 108.5 . . ?
H35W O35 H35O 108.2 . . ?
H37O O37 H37W 108.7 . . ?
H39O O39 H39W 107.0 . . ?

_refine_diff_density_max         0.873
_refine_diff_density_min         -0.694
_refine_diff_density_rms         0.115


_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: water'
####################################################################### 
# 
# 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_3
_database_code_depnum_ccdc_archive 'CCDC 1865732'
loop_
_audit_author_name
_audit_author_address
'Nora Veronika May'
;Research Centre for Natural Sciences, Hungarian Academy of Sciences
Hungary
;
_audit_update_record             
;
2019-05-15 deposited with the CCDC.	2019-06-05 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT029_3                   
;
PROBLEM: _diffrn_measured_fraction_theta_full value Low .      0.911 Why?
RESPONSE: The collection of the high angle data was limited because 
of the application of copper wavelength
;
_vrf_PLAT911_3                   
;
PROBLEM: Missing FCF Refl Between Thmin & STh/L=    0.600        200 Report
RESPONSE: This is the consequence of low resolution
;
# Added during the CSD deposition process: Thursday 14 March 2019 09:38 AM
# end Validation Reply Form


_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        
"'bis(μ2-4-hydroxy-1-methyl-3-pyridinecarboxylato)-bis(μ2-4-hydroxy-1-methyl-3-pyridinecarboxylato)-di-copper(II) tetrahydrate'"
_chemical_name_common            ?
_chemical_formula_moiety         'C28 H24 Cu2 N4 O12, 4(H2 O)'
_chemical_formula_sum            'C28 H32 Cu2 N4 O16'
_chemical_formula_weight         807.65

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'
O O 0.0492 0.0322 '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'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_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'

_cell_length_a                   7.9481(4)
_cell_length_b                   8.7896(4)
_cell_length_c                   11.4208(6)
_cell_angle_alpha                90.722(3)
_cell_angle_beta                 106.939(3)
_cell_angle_gamma                104.188(3)
_cell_volume                     736.92(6)
_cell_formula_units_Z            1
_cell_measurement_temperature    103(2)
_cell_measurement_reflns_used    6092
_cell_measurement_theta_min      6.87
_cell_measurement_theta_max      68.22

_exptl_crystal_description       Block
_exptl_crystal_colour            Blue
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.820
_exptl_crystal_F_000             414
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.100
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.050
_exptl_absorpt_coefficient_mu    2.583
_shelx_estimated_absorpt_T_min   0.782
_shelx_estimated_absorpt_T_max   0.882
_exptl_absorpt_correction_type   Numerical
_exptl_absorpt_correction_T_min  0.5237
_exptl_absorpt_correction_T_max  0.7734
_exptl_absorpt_process_details   
;
 T.Higashi, Numerical Absorption Correction, NUMABS, 2002

;
_diffrn_ambient_temperature      103(2)
_diffrn_radiation_wavelength     1.54187
_diffrn_radiation_type           CuK\a
_diffrn_source_power             2.0000
_diffrn_source_voltage           50.0000
_diffrn_source_current           40.0000
_diffrn_radiation_source         'Sealed Tube'
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_detector       RX
_diffrn_measurement_device_type  'Rigaku RAXIS-RAPID II.'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measurement_method       dtprofit.ref
_diffrn_measurement_details      
;
 scan:  N=1,PHI=0.0,CHI=50.0,OMEGA=-25.0,245.0,5.0,COUPLE=0.00                 
 scan:  N=2,PHI=180.0,CHI=30.0,OMEGA=-25.0,230.0,5.0,COUPLE=0.00               
 scan:  N=3,PHI=180.0,CHI=50.0,OMEGA=42.0,232.0,5.0,COUPLE=0.00                
 scan:  N=4,PHI=90.0,CHI=50.0,OMEGA=28.0,243.0,5.0,COUPLE=0.00                 
 scan:  N=5,PHI=0.0,CHI=30.0,OMEGA=13.0,48.0,5.0,COUPLE=0.00                   
 Orientation Matrix:
    UB11  0.0791 UB12 -0.0713 UB13  0.0348
    UB21  0.0995 UB22  0.0931 UB23  0.0458
    UB31 -0.0490 UB32 -0.0113 UB33  0.0716
    Matrix type: 'd*Trek'
;
_diffrn_reflns_number            8477
_diffrn_reflns_av_unetI/netI     0.0583
_diffrn_reflns_av_R_equivalents  0.0707
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         6.872
_diffrn_reflns_theta_max         68.224
_diffrn_reflns_theta_full        67.687
_diffrn_measured_fraction_theta_max 0.909
_diffrn_measured_fraction_theta_full 0.911
_diffrn_reflns_Laue_measured_fraction_max 0.909
_diffrn_reflns_Laue_measured_fraction_full 0.911
_diffrn_reflns_point_group_measured_fraction_max 0.909
_diffrn_reflns_point_group_measured_fraction_full 0.911
_reflns_number_total             2466
_reflns_number_gt                2129
_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       'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_cell_refinement       'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_data_reduction        'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_structure_solution    'Sir2014 (Burla, 2015)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Mercury (Macrae, 2006)'
_computing_publication_material  'Spek, A.L. (2015). Acta Cryst. C71, 9-18.'
_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)+(0.0715P)²+2.6446P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     difmap
_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         2466
_refine_ls_number_parameters     240
_refine_ls_number_restraints     9
_refine_ls_R_factor_all          0.0701
_refine_ls_R_factor_gt           0.0612
_refine_ls_wR_factor_ref         0.1761
_refine_ls_wR_factor_gt          0.1561
_refine_ls_goodness_of_fit_ref   1.166
_refine_ls_restrained_S_all      1.199
_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 0.50257(8) 0.29190(7) 0.44954(6) 0.0188(3) Uani 1 1 d . . . . .
O12 O 0.5992(4) 0.1678(4) 0.5788(3) 0.0206(8) Uani 1 1 d . . . . .
O11 O 0.5840(4) -0.0321(4) 0.6933(3) 0.0223(8) Uani 1 1 d . . . . .
O13 O 0.2803(4) 0.2662(4) 0.4910(3) 0.0192(7) Uani 1 1 d . . . . .
O3 O 0.7362(4) 0.3442(4) 0.4211(3) 0.0183(7) Uani 1 1 d . . . . .
O1 O 0.3726(5) 0.5451(4) 0.1571(3) 0.0272(9) Uani 1 1 d . . . . .
O2 O 0.4001(4) 0.4122(4) 0.3201(3) 0.0236(8) Uani 1 1 d . . . . .
O4 O 0.3761(5) 0.7794(4) -0.0001(4) 0.0303(9) Uani 1 1 d D . . . .
O5 O 0.6813(5) 0.9322(4) -0.0605(3) 0.0266(8) Uani 1 1 d D . . . .
N1 N 0.8952(5) 0.5972(5) 0.1577(4) 0.0190(9) Uani 1 1 d . . . . .
N11 N 0.0908(5) -0.0200(4) 0.7281(4) 0.0180(9) Uani 1 1 d . . . . .
C7 C 0.4638(6) 0.4834(5) 0.2397(5) 0.0182(10) Uani 1 1 d . . . . .
C13 C 0.3330(6) 0.0794(5) 0.6411(5) 0.0194(11) Uani 1 1 d . . . . .
C17 C 0.5149(6) 0.0708(6) 0.6376(5) 0.0201(10) Uani 1 1 d . . . . .
C4 C 0.7785(6) 0.4252(5) 0.3364(5) 0.0197(11) Uani 1 1 d . . . . .
C3 C 0.6572(6) 0.4917(5) 0.2462(5) 0.0185(10) Uani 1 1 d . . . . .
C16 C -0.0091(6) 0.0739(5) 0.6610(4) 0.0169(10) Uani 1 1 d . . . . .
H16 H -0.1258 0.0706 0.6685 0.020 Uiso 1 1 calc R U . . .
C2 C 0.7226(6) 0.5744(5) 0.1597(4) 0.0177(10) Uani 1 1 d . . . . .
H2 H 0.6418 0.6172 0.0988 0.021 Uiso 1 1 calc R U . . .
C12 C 0.2550(6) -0.0172(5) 0.7173(4) 0.0174(10) Uani 1 1 d . . . . .
H12 H 0.3212 -0.0842 0.7638 0.021 Uiso 1 1 calc R U . . .
C15 C 0.0557(6) 0.1707(5) 0.5846(4) 0.0172(10) Uani 1 1 d . . . . .
H15 H -0.0158 0.2353 0.5398 0.021 Uiso 1 1 calc R U . . .
C5 C 0.9612(6) 0.4535(5) 0.3309(5) 0.0189(11) Uani 1 1 d . . . . .
H5 H 1.0463 0.4125 0.3901 0.023 Uiso 1 1 calc R U . . .
C6 C 1.0158(6) 0.5363(5) 0.2445(5) 0.0187(10) Uani 1 1 d . . . . .
H6 H 1.1379 0.5528 0.2432 0.022 Uiso 1 1 calc R U . . .
C14 C 0.2303(6) 0.1780(5) 0.5696(4) 0.0174(10) Uani 1 1 d . . . . .
C18 C 0.0088(6) -0.1261(6) 0.8085(5) 0.0214(11) Uani 1 1 d . . . . .
H18A H 0.0923 -0.1886 0.8486 0.032 Uiso 1 1 calc R U . . .
H18B H -0.1069 -0.1967 0.7587 0.032 Uiso 1 1 calc R U . . .
H18C H -0.0132 -0.0629 0.8711 0.032 Uiso 1 1 calc R U . . .
C8 C 0.9585(7) 0.6892(6) 0.0640(5) 0.0248(11) Uani 1 1 d . . . . .
H8A H 0.9539 0.6171 -0.0037 0.037 Uiso 1 1 calc R U . . .
H8B H 1.0840 0.7526 0.1012 0.037 Uiso 1 1 calc R U . . .
H8C H 0.8796 0.7589 0.0324 0.037 Uiso 1 1 calc R U . . .
H4O H 0.392(8) 0.715(5) 0.057(3) 0.032 Uiso 1 1 d D U . . .
H5O H 0.648(7) 0.929(6) -0.1404(10) 0.032 Uiso 1 1 d D U . . .
H5W H 0.584(4) 0.871(6) -0.049(4) 0.032 Uiso 1 1 d D U . . .
H4W H 0.376(8) 0.862(3) 0.036(4) 0.032 Uiso 1 1 d D 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 O13 1.921(3) . ?
Cu1 O3 1.924(3) . ?
Cu1 O2 1.931(3) . ?
Cu1 O12 1.937(3) . ?
O12 C17 1.274(6) . ?
O11 C17 1.257(6) . ?
O13 C14 1.280(6) . ?
O3 C4 1.283(6) . ?
O1 C7 1.232(6) . ?
O2 C7 1.273(6) . ?
O4 H4O 0.870(9) . ?
O4 H4W 0.834(10) . ?
O5 H5O 0.870(9) . ?
O5 H5W 0.871(9) . ?
N1 C2 1.344(6) . ?
N1 C6 1.378(6) . ?
N1 C8 1.479(7) . ?
N11 C12 1.341(6) . ?
N11 C16 1.371(6) . ?
N11 C18 1.487(6) . ?
C7 C3 1.500(6) . ?
C13 C12 1.392(7) . ?
C13 C14 1.436(6) . ?
C13 C17 1.478(6) . ?
C4 C3 1.431(6) . ?
C4 C5 1.432(7) . ?
C3 C2 1.381(7) . ?
C16 C15 1.347(7) . ?
C16 H16 0.9500 . ?
C2 H2 0.9500 . ?
C12 H12 0.9500 . ?
C15 C14 1.433(6) . ?
C15 H15 0.9500 . ?
C5 C6 1.343(7) . ?
C5 H5 0.9500 . ?
C6 H6 0.9500 . ?
C18 H18A 0.9800 . ?
C18 H18B 0.9800 . ?
C18 H18C 0.9800 . ?
C8 H8A 0.9800 . ?
C8 H8B 0.9800 . ?
C8 H8C 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
O13 Cu1 O3 172.34(14) . . ?
O13 Cu1 O2 86.10(14) . . ?
O3 Cu1 O2 93.08(14) . . ?
O13 Cu1 O12 92.72(14) . . ?
O3 Cu1 O12 88.20(14) . . ?
O2 Cu1 O12 178.56(13) . . ?
C17 O12 Cu1 128.9(3) . . ?
C14 O13 Cu1 126.7(3) . . ?
C4 O3 Cu1 126.5(3) . . ?
C7 O2 Cu1 131.4(3) . . ?
H4O O4 H4W 104(2) . . ?
H5O O5 H5W 101(2) . . ?
C2 N1 C6 120.0(4) . . ?
C2 N1 C8 120.7(4) . . ?
C6 N1 C8 119.4(4) . . ?
C12 N11 C16 119.9(4) . . ?
C12 N11 C18 122.1(4) . . ?
C16 N11 C18 118.0(4) . . ?
O1 C7 O2 122.5(4) . . ?
O1 C7 C3 119.0(5) . . ?
O2 C7 C3 118.5(4) . . ?
C12 C13 C14 118.0(4) . . ?
C12 C13 C17 117.5(4) . . ?
C14 C13 C17 124.5(5) . . ?
O11 C17 O12 121.1(4) . . ?
O11 C17 C13 119.2(4) . . ?
O12 C17 C13 119.7(4) . . ?
O3 C4 C3 125.1(5) . . ?
O3 C4 C5 118.4(4) . . ?
C3 C4 C5 116.6(5) . . ?
C2 C3 C4 118.2(4) . . ?
C2 C3 C7 116.6(4) . . ?
C4 C3 C7 125.2(5) . . ?
C15 C16 N11 121.1(4) . . ?
C15 C16 H16 119.5 . . ?
N11 C16 H16 119.5 . . ?
N1 C2 C3 123.1(4) . . ?
N1 C2 H2 118.5 . . ?
C3 C2 H2 118.5 . . ?
N11 C12 C13 123.0(4) . . ?
N11 C12 H12 118.5 . . ?
C13 C12 H12 118.5 . . ?
C16 C15 C14 121.3(4) . . ?
C16 C15 H15 119.4 . . ?
C14 C15 H15 119.4 . . ?
C6 C5 C4 121.9(4) . . ?
C6 C5 H5 119.0 . . ?
C4 C5 H5 119.0 . . ?
C5 C6 N1 120.2(4) . . ?
C5 C6 H6 119.9 . . ?
N1 C6 H6 119.9 . . ?
O13 C14 C15 118.4(4) . . ?
O13 C14 C13 124.8(4) . . ?
C15 C14 C13 116.8(5) . . ?
N11 C18 H18A 109.5 . . ?
N11 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
N11 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
N1 C8 H8A 109.5 . . ?
N1 C8 H8B 109.5 . . ?
H8A C8 H8B 109.5 . . ?
N1 C8 H8C 109.5 . . ?
H8A C8 H8C 109.5 . . ?
H8B C8 H8C 109.5 . . ?

_refine_diff_density_max         0.665
_refine_diff_density_min         -1.232
_refine_diff_density_rms         0.135


_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: water'
####################################################################### 
# 
# 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_2
_database_code_depnum_ccdc_archive 'CCDC 1865731'
loop_
_audit_author_name
_audit_author_address
'Nora Veronika May'
;Research Centre for Natural Sciences, Hungarian Academy of Sciences
Hungary
;
_audit_update_record             
;
2019-05-15 deposited with the CCDC.	2019-06-05 downloaded from the CCDC.
;
_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        
"'bis(μ2-3-hydroxy-1,2,6-trimethyl-4-pyridinecarboxylato)-di-copper(II) hexahydrate'"
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C36 H40 Cu2 N4 O12, 6(H2 O), 6(H1.5 O)'
_chemical_formula_sum            'C36 H61 Cu2 N4 O24'
_chemical_formula_weight         1060.99

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      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_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'

_cell_length_a                   9.4860(4)
_cell_length_b                   11.1725(5)
_cell_length_c                   12.3239(5)
_cell_angle_alpha                98.4870(10)
_cell_angle_beta                 102.3390(10)
_cell_angle_gamma                106.5450(10)
_cell_volume                     1192.43(9)
_cell_formula_units_Z            1
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    34233
_cell_measurement_theta_min      3.15
_cell_measurement_theta_max      27.50

_exptl_crystal_description       Block
_exptl_crystal_colour            Green
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.477
_exptl_crystal_F_000             555
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.50
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.10
_exptl_absorpt_coefficient_mu    0.979
_shelx_estimated_absorpt_T_min   0.640
_shelx_estimated_absorpt_T_max   0.908
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.6796
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   
;
 T.Higashi, Empirical Absorption Correction, 2001
;
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source_power             2.0000
_diffrn_source_voltage           50.0000
_diffrn_source_current           40.0000
_diffrn_radiation_source         'Sealed Tube'
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_detector       RX
_diffrn_measurement_device_type  'Rigaku RAXIS-RAPID II.'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measurement_method       dtprofit.ref
_diffrn_measurement_details      
;
 scan:  N=1,PHI=0.0,CHI=40.0,OMEGA=20.0,225.0,5.0,COUPLE=0.00                  
 scan:  N=2,PHI=0.0,CHI=0.0,OMEGA=20.0,200.0,5.0,COUPLE=0.00                   
 scan:  N=3,PHI=180.0,CHI=40.0,OMEGA=85.0,215.0,5.0,COUPLE=0.00                
 scan:  N=4,PHI=90.0,CHI=0.0,OMEGA=20.0,200.0,5.0,COUPLE=0.00                  
 scan:  N=5,PHI=90.0,CHI=40.0,OMEGA=20.0,200.0,5.0,COUPLE=0.00                 
 Orientation Matrix:
    UB11 -0.0534 UB12  0.0116 UB13 -0.0750
    UB21  0.0495 UB22  0.0949 UB23  0.0265
    UB31  0.0879 UB32 -0.0057 UB33 -0.0306
    Matrix type: 'd*Trek'
;
_diffrn_reflns_number            45048
_diffrn_reflns_av_unetI/netI     0.0196
_diffrn_reflns_av_R_equivalents  0.0343
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         3.151
_diffrn_reflns_theta_max         27.481
_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             5432
_reflns_number_gt                4653
_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       'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_cell_refinement       'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_data_reduction        'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_structure_solution    'Sir2014 (Burla, 2015)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Mercury (Macrae, 2006)'
_computing_publication_material  'Spek, A.L. (2015). Acta Cryst. C71, 9-18.'
_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)+(0.0613P)²+0.2694P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     difmap
_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         5432
_refine_ls_number_parameters     330
_refine_ls_number_restraints     9
_refine_ls_R_factor_all          0.0442
_refine_ls_R_factor_gt           0.0377
_refine_ls_wR_factor_ref         0.1064
_refine_ls_wR_factor_gt          0.1021
_refine_ls_goodness_of_fit_ref   1.109
_refine_ls_restrained_S_all      1.108
_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 0.13405(3) 0.04466(2) 0.11781(2) 0.03754(10) Uani 1 1 d . . . . .
O3 O 0.09492(16) -0.08437(13) -0.01531(13) 0.0430(3) Uani 1 1 d . . . . .
O2 O 0.28100(17) 0.16716(13) 0.06912(13) 0.0447(3) Uani 1 1 d . . . . .
O1 O 0.4501(2) 0.23672(16) -0.02358(18) 0.0727(6) Uani 1 1 d . . . . .
O13 O 0.0382(2) -0.08921(13) 0.18513(14) 0.0524(4) Uani 1 1 d . . . . .
O12 O 0.16550(16) 0.17277(13) 0.25220(12) 0.0422(3) Uani 1 1 d . . . . .
O11 O 0.12543(19) 0.25910(14) 0.41032(14) 0.0537(4) Uani 1 1 d . . . . .
O4 O 0.3957(3) 0.43049(16) 0.18416(18) 0.0752(6) Uani 1 1 d . . . . .
H4O H 0.3637 0.3540 0.1508 0.090 Uiso 1 1 d R U . . .
H4W H 0.3821 0.4349 0.2489 0.090 Uiso 1 1 d R U . . .
O5 O 0.2992(2) 0.5974(2) 0.0641(2) 0.0897(7) Uani 1 1 d . . . . .
H5W H 0.3305 0.5489 0.1010 0.108 Uiso 1 1 d R U . . .
H5O H 0.3694 0.6403 0.0409 0.108 Uiso 1 1 d R U . . .
O7 O 0.2740(3) 0.6995(2) 0.4181(2) 0.0832(6) Uani 1 1 d D . . . .
O8 O 0.3659(2) 0.4794(2) 0.4136(2) 0.0758(6) Uani 1 1 d D . . . .
O6 O 0.2696(3) 0.7881(2) 0.2200(2) 0.0928(7) Uani 1 1 d . . . . .
H6W H 0.1910 0.8058 0.1950 0.111 Uiso 1 1 d R U . . .
H6O H 0.2468 0.7100 0.1883 0.111 Uiso 0.5 1 d R U P . .
N1 N 0.2739(2) -0.22244(16) -0.20370(14) 0.0415(4) Uani 1 1 d . . . . .
N12 N -0.24517(19) -0.17706(16) 0.33377(15) 0.0428(4) Uani 1 1 d . . . . .
C2 C 0.1784(2) -0.21212(19) -0.13739(17) 0.0392(4) Uani 1 1 d . . . . .
C3 C 0.1953(2) -0.08981(18) -0.07295(16) 0.0351(4) Uani 1 1 d . . . . .
C4 C 0.3162(2) 0.01596(18) -0.07569(16) 0.0356(4) Uani 1 1 d . . . . .
C5 C 0.4073(2) -0.0014(2) -0.14738(16) 0.0389(4) Uani 1 1 d . . . . .
H5 H 0.4851 0.0692 -0.1515 0.047 Uiso 1 1 calc R U . . .
C6 C 0.3861(2) -0.1195(2) -0.21240(17) 0.0425(4) Uani 1 1 d . . . . .
C7 C 0.3518(2) 0.14955(19) -0.00627(18) 0.0409(4) Uani 1 1 d . . . . .
C8 C 0.2588(4) -0.3509(2) -0.2661(3) 0.0666(7) Uani 1 1 d . . . . .
H8A H 0.3419 -0.3767 -0.2299 0.100 Uiso 1 1 calc R U . . .
H8B H 0.2609 -0.3483 -0.3433 0.100 Uiso 1 1 calc R U . . .
H8C H 0.1638 -0.4111 -0.2658 0.100 Uiso 1 1 calc R U . . .
C9 C 0.0553(3) -0.3279(2) -0.1321(2) 0.0532(5) Uani 1 1 d . . . . .
H9A H -0.0120 -0.3673 -0.2071 0.080 Uiso 1 1 calc R U . . .
H9B H -0.0015 -0.3031 -0.0823 0.080 Uiso 1 1 calc R U . . .
H9C H 0.1004 -0.3878 -0.1037 0.080 Uiso 1 1 calc R U . . .
C10 C 0.4825(3) -0.1366(3) -0.2927(2) 0.0584(6) Uani 1 1 d . . . . .
C12 C -0.1552(3) -0.18618(19) 0.26379(18) 0.0428(5) Uani 1 1 d . . . . .
C13 C -0.0408(2) -0.07429(18) 0.25712(17) 0.0386(4) Uani 1 1 d . . . . .
C14 C -0.0235(2) 0.04321(17) 0.32751(16) 0.0346(4) Uani 1 1 d . . . . .
C15 C -0.1196(2) 0.04445(19) 0.39851(17) 0.0386(4) Uani 1 1 d . . . . .
H15 H -0.1074 0.1217 0.4459 0.046 Uiso 1 1 calc R U . . .
C16 C -0.2313(2) -0.0634(2) 0.40149(18) 0.0427(4) Uani 1 1 d . . . . .
C17 C 0.0965(2) 0.16614(18) 0.33001(17) 0.0368(4) Uani 1 1 d . . . . .
C18 C -0.3664(3) -0.2952(2) 0.3356(3) 0.0630(7) Uani 1 1 d . . . . .
H18A H -0.4463 -0.3208 0.2658 0.094 Uiso 1 1 calc R U . . .
H18B H -0.4075 -0.2784 0.3987 0.094 Uiso 1 1 calc R U . . .
H18C H -0.3234 -0.3626 0.3434 0.094 Uiso 1 1 calc R U . . .
C19 C -0.3361(3) -0.0585(3) 0.4765(2) 0.0592(6) Uani 1 1 d . . . . .
H19A H -0.4396 -0.0854 0.4302 0.089 Uiso 1 1 calc R U . . .
H19B H -0.3089 0.0275 0.5196 0.089 Uiso 1 1 calc R U . . .
H19C H -0.3268 -0.1145 0.5278 0.089 Uiso 1 1 calc R U . . .
C20 C -0.1742(4) -0.3124(2) 0.1907(2) 0.0636(7) Uani 1 1 d . . . . .
H20A H -0.1306 -0.3620 0.2367 0.095 Uiso 1 1 calc R U . . .
H20B H -0.1232 -0.2982 0.1320 0.095 Uiso 1 1 calc R U . . .
H20C H -0.2809 -0.3579 0.1566 0.095 Uiso 1 1 calc R U . . .
O9 O 0.0119(3) -0.6017(2) -0.4494(2) 0.0804(6) Uani 1 1 d D . . . .
H7O H 0.268(5) 0.709(7) 0.351(2) 0.097 Uiso 0.5 1 d D U P . .
H7W H 0.1849(19) 0.666(3) 0.421(3) 0.097 Uiso 1 1 d D U . . .
H8W H 0.299(3) 0.4152(19) 0.420(3) 0.097 Uiso 1 1 d D U . . .
H8O H 0.350(4) 0.5436(19) 0.445(3) 0.097 Uiso 1 1 d D U . . .
H9O H -0.007(10) -0.553(5) -0.492(4) 0.097 Uiso 0.5 1 d D U P . .
H9W H 0.031(4) -0.658(3) -0.490(3) 0.097 Uiso 1 1 d D U . . .
H10A H 0.421(4) -0.171(3) -0.367(3) 0.097 Uiso 1 1 d . U . . .
H10C H 0.559(4) -0.051(4) -0.284(3) 0.097 Uiso 1 1 d . U . . .
H10B H 0.537(4) -0.197(4) -0.275(3) 0.097 Uiso 1 1 d . 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 O3 1.9090(14) . ?
Cu1 O13 1.9146(14) . ?
Cu1 O2 1.9209(14) . ?
Cu1 O12 1.9304(14) . ?
O3 C3 1.313(2) . ?
O2 C7 1.281(2) . ?
O1 C7 1.222(3) . ?
O13 C13 1.299(3) . ?
O12 C17 1.271(2) . ?
O11 C17 1.246(2) . ?
O4 H4O 0.8283 . ?
O4 H4W 0.8317 . ?
O5 H5W 0.8331 . ?
O5 H5O 0.8334 . ?
O7 H7O 0.842(10) . ?
O7 H7W 0.832(10) . ?
O8 H8W 0.842(10) . ?
O8 H8O 0.831(10) . ?
O6 H6W 0.8328 . ?
O6 H6O 0.8466 . ?
N1 C2 1.360(3) . ?
N1 C6 1.362(3) . ?
N1 C8 1.477(3) . ?
N12 C12 1.349(3) . ?
N12 C16 1.368(3) . ?
N12 C18 1.490(3) . ?
C2 C3 1.423(3) . ?
C2 C9 1.496(3) . ?
C3 C4 1.404(3) . ?
C4 C5 1.391(3) . ?
C4 C7 1.512(3) . ?
C5 C6 1.375(3) . ?
C5 H5 0.9300 . ?
C6 C10 1.511(3) . ?
C8 H8A 0.9600 . ?
C8 H8B 0.9600 . ?
C8 H8C 0.9600 . ?
C9 H9A 0.9600 . ?
C9 H9B 0.9600 . ?
C9 H9C 0.9600 . ?
C10 H10A 0.93(4) . ?
C10 H10C 1.00(4) . ?
C10 H10B 0.98(4) . ?
C12 C13 1.430(3) . ?
C12 C20 1.498(3) . ?
C13 C14 1.408(3) . ?
C14 C15 1.393(3) . ?
C14 C17 1.505(3) . ?
C15 C16 1.370(3) . ?
C15 H15 0.9300 . ?
C16 C19 1.502(3) . ?
C18 H18A 0.9600 . ?
C18 H18B 0.9600 . ?
C18 H18C 0.9600 . ?
C19 H19A 0.9600 . ?
C19 H19B 0.9600 . ?
C19 H19C 0.9600 . ?
C20 H20A 0.9600 . ?
C20 H20B 0.9600 . ?
C20 H20C 0.9600 . ?
O9 H9O 0.843(10) . ?
O9 H9W 0.835(10) . ?

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
O3 Cu1 O13 87.45(6) . . ?
O3 Cu1 O2 92.25(6) . . ?
O13 Cu1 O2 163.57(7) . . ?
O3 Cu1 O12 177.82(6) . . ?
O13 Cu1 O12 91.26(6) . . ?
O2 Cu1 O12 89.48(6) . . ?
C3 O3 Cu1 123.84(12) . . ?
C7 O2 Cu1 129.76(13) . . ?
C13 O13 Cu1 123.48(12) . . ?
C17 O12 Cu1 129.06(12) . . ?
H4O O4 H4W 108.1 . . ?
H5W O5 H5O 109.5 . . ?
H7O O7 H7W 106(2) . . ?
H8W O8 H8O 106(2) . . ?
H6W O6 H6O 103.9 . . ?
C2 N1 C6 122.70(17) . . ?
C2 N1 C8 118.8(2) . . ?
C6 N1 C8 118.47(19) . . ?
C12 N12 C16 122.63(17) . . ?
C12 N12 C18 118.60(19) . . ?
C16 N12 C18 118.75(19) . . ?
N1 C2 C3 119.62(18) . . ?
N1 C2 C9 120.66(18) . . ?
C3 C2 C9 119.72(19) . . ?
O3 C3 C4 124.68(17) . . ?
O3 C3 C2 117.05(17) . . ?
C4 C3 C2 118.27(18) . . ?
C5 C4 C3 118.79(17) . . ?
C5 C4 C7 117.69(17) . . ?
C3 C4 C7 123.51(17) . . ?
C6 C5 C4 122.16(19) . . ?
C6 C5 H5 118.9 . . ?
C4 C5 H5 118.9 . . ?
N1 C6 C5 118.27(18) . . ?
N1 C6 C10 120.0(2) . . ?
C5 C6 C10 121.7(2) . . ?
O1 C7 O2 122.54(19) . . ?
O1 C7 C4 117.91(19) . . ?
O2 C7 C4 119.54(17) . . ?
N1 C8 H8A 109.5 . . ?
N1 C8 H8B 109.5 . . ?
H8A C8 H8B 109.5 . . ?
N1 C8 H8C 109.5 . . ?
H8A C8 H8C 109.5 . . ?
H8B C8 H8C 109.5 . . ?
C2 C9 H9A 109.5 . . ?
C2 C9 H9B 109.5 . . ?
H9A C9 H9B 109.5 . . ?
C2 C9 H9C 109.5 . . ?
H9A C9 H9C 109.5 . . ?
H9B C9 H9C 109.5 . . ?
C6 C10 H10A 110(2) . . ?
C6 C10 H10C 107(2) . . ?
H10A C10 H10C 113(3) . . ?
C6 C10 H10B 112(2) . . ?
H10A C10 H10B 106(3) . . ?
H10C C10 H10B 109(3) . . ?
N12 C12 C13 120.21(18) . . ?
N12 C12 C20 121.05(19) . . ?
C13 C12 C20 118.7(2) . . ?
O13 C13 C14 125.11(18) . . ?
O13 C13 C12 117.01(18) . . ?
C14 C13 C12 117.87(19) . . ?
C15 C14 C13 118.45(17) . . ?
C15 C14 C17 119.22(17) . . ?
C13 C14 C17 122.32(17) . . ?
C16 C15 C14 122.78(19) . . ?
C16 C15 H15 118.6 . . ?
C14 C15 H15 118.6 . . ?
N12 C16 C15 118.02(19) . . ?
N12 C16 C19 120.37(19) . . ?
C15 C16 C19 121.6(2) . . ?
O11 C17 O12 121.95(18) . . ?
O11 C17 C14 117.92(18) . . ?
O12 C17 C14 120.13(16) . . ?
N12 C18 H18A 109.5 . . ?
N12 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
N12 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
C16 C19 H19A 109.5 . . ?
C16 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
C16 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
C12 C20 H20A 109.5 . . ?
C12 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
C12 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
H9O O9 H9W 104(2) . . ?

_refine_diff_density_max         0.432
_refine_diff_density_min         -0.365
_refine_diff_density_rms         0.084

####################################################################### 
# 
# 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_4
_database_code_depnum_ccdc_archive 'CCDC 1865733'
loop_
_audit_author_name
_audit_author_address
'Nora Veronika May'
;Research Centre for Natural Sciences, Hungarian Academy of Sciences
Hungary
;
_audit_update_record             
;
2019-05-15 deposited with the CCDC.	2019-06-05 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        
'catena-(bis(μ2-4-hydroxy-1,6-dimethyl-3-pyridinecarboxylato)-copper(II) trihydrate'
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C16 H16 Cu N2 O6, 3(H2 O)'
_chemical_formula_sum            'C16 H22 Cu N2 O9'
_chemical_formula_weight         449.89

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      orthorhombic
_space_group_IT_number           33
_space_group_name_H-M_alt        'P n a 21'
_space_group_name_Hall           'P 2c -2n'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z+1/2'
'-x+1/2, y+1/2, z+1/2'
'x+1/2, -y+1/2, z'

_cell_length_a                   13.5554(8)
_cell_length_b                   12.9227(6)
_cell_length_c                   10.2747(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1799.84(16)
_cell_formula_units_Z            4
_cell_measurement_temperature    103(2)
_cell_measurement_reflns_used    31641
_cell_measurement_theta_min      3.01
_cell_measurement_theta_max      27.46

_exptl_crystal_description       Chunk
_exptl_crystal_colour            Blue
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.660
_exptl_crystal_F_000             932
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.250
_exptl_crystal_size_mid          0.250
_exptl_crystal_size_min          0.200
_exptl_absorpt_coefficient_mu    1.269
_shelx_estimated_absorpt_T_min   0.742
_shelx_estimated_absorpt_T_max   0.785
_exptl_absorpt_correction_type   Numerical
_exptl_absorpt_correction_T_min  0.7054
_exptl_absorpt_correction_T_max  0.7496
_exptl_absorpt_process_details   
;
 T.Higashi, Numerical Absorption Correction, NUMABS, 2002
;
_diffrn_ambient_temperature      103(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source_power             2.0000
_diffrn_source_voltage           50.0000
_diffrn_source_current           40.0000
_diffrn_radiation_source         'Sealed Tube'
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_detector       RX
_diffrn_measurement_device       RAXIS-RAPID
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measurement_method       dtprofit.ref
_diffrn_measurement_details      
;
 scan:  N=1,PHI=180.0,CHI=15.0,OMEGA=25.0,225.0,5.0,COUPLE=0.00                
 scan:  N=2,PHI=90.0,CHI=40.0,OMEGA=25.0,225.0,5.0,COUPLE=0.00                 
 scan:  N=3,PHI=0.0,CHI=0.0,OMEGA=25.0,225.0,5.0,COUPLE=0.00                   
 scan:  N=4,PHI=90.0,CHI=15.0,OMEGA=25.0,50.0,5.0,COUPLE=0.00                  
 Orientation Matrix:
    UB11  0.0221 UB12 -0.0201 UB13 -0.0693
    UB21 -0.0799 UB22  0.0362 UB23 -0.0242
    UB31  0.0510 UB32  0.0654 UB33 -0.0079
    Matrix type: 'd*Trek'
;
_diffrn_reflns_number            45387
_diffrn_reflns_av_unetI/netI     0.0223
_diffrn_reflns_av_R_equivalents  0.0536
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         3.005
_diffrn_reflns_theta_max         27.467
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             4121
_reflns_number_gt                3929
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.894
_reflns_Friedel_fraction_max     0.999
_reflns_Friedel_fraction_full    0.999

_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       'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_cell_refinement       'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_data_reduction        'CrystalClear (Rigaku/MSC Inc., 2005)'
_computing_structure_solution    'Sir2014 (Burla, 2015)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Mercury (Macrae, 2006)'
_computing_publication_material  'Spek, A.L. (2015). Acta Cryst. C71, 9-18.'
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0207P)²+1.3240P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     difmap
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.477(13)
_chemical_absolute_configuration .
_refine_ls_number_reflns         4121
_refine_ls_number_parameters     264
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0298
_refine_ls_R_factor_gt           0.0270
_refine_ls_wR_factor_ref         0.0578
_refine_ls_wR_factor_gt          0.0559
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_restrained_S_all      1.093
_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
Cu1 Cu 0.61428(2) 0.53071(2) 0.46061(4) 0.01274(9) Uani 1 1 d . . . . .
O1 O 0.70025(17) 0.58374(17) 0.0914(2) 0.0173(5) Uani 1 1 d . . . . .
O2 O 0.67626(16) 0.58449(17) 0.3048(2) 0.0161(5) Uani 1 1 d . . . . .
O3 O 0.66064(17) 0.39162(16) 0.4201(2) 0.0166(5) Uani 1 1 d . . . . .
O4 O 0.7875(2) 0.7748(2) 0.1470(2) 0.0297(6) Uani 1 1 d . . . . .
H4O H 0.8148 0.8077 0.0889 0.067(19) Uiso 1 1 d R . . . .
H4W H 0.7601 0.7165 0.1207 0.036(12) Uiso 1 1 d R . . . .
O5 O 0.6524(2) 0.83383(19) 0.3336(3) 0.0292(6) Uani 1 1 d . . . . .
H5W H 0.6395 0.7765 0.3616 0.062(18) Uiso 1 1 d R . . . .
H5O H 0.6915 0.8180 0.2747 0.047(15) Uiso 1 1 d R . . . .
O6 O 0.86742(15) 0.51882(17) 0.9579(4) 0.0264(5) Uani 1 1 d . . . . .
H6W H 0.8648 0.4703 0.9214 0.06(2) Uiso 1 1 d R . . . .
H6O H 0.8156 0.5328 0.9978 0.033(12) Uiso 1 1 d R . . . .
O11 O 0.53325(16) 0.47009(16) 0.8336(2) 0.0162(4) Uani 1 1 d . . . . .
O12 O 0.56911(17) 0.47456(17) 0.6229(2) 0.0169(5) Uani 1 1 d . . . . .
O13 O 0.60286(17) 0.67151(16) 0.5186(2) 0.0160(5) Uani 1 1 d . . . . .
N1 N 0.6430(2) 0.2745(2) 0.0529(3) 0.0142(5) Uani 1 1 d . . . . .
N11 N 0.5700(2) 0.7777(2) 0.8913(3) 0.0163(6) Uani 1 1 d . . . . .
C2 C 0.6517(2) 0.3776(2) 0.0697(3) 0.0144(6) Uani 1 1 d . . . . .
H2 H 0.6493 0.4211 -0.0048 0.017 Uiso 1 1 calc R U . . .
C3 C 0.6637(2) 0.4227(2) 0.1900(3) 0.0129(6) Uani 1 1 d . . . . .
C4 C 0.6626(2) 0.3580(2) 0.3021(3) 0.0123(6) Uani 1 1 d . . . . .
C5 C 0.6629(2) 0.2496(3) 0.2792(3) 0.0150(6) Uani 1 1 d . . . . .
H5 H 0.6707 0.2041 0.3511 0.018 Uiso 1 1 calc R U . . .
C6 C 0.6526(2) 0.2084(2) 0.1576(3) 0.0146(6) Uani 1 1 d . . . . .
C7 C 0.6801(2) 0.5378(2) 0.1954(3) 0.0133(6) Uani 1 1 d . . . . .
C8 C 0.6216(3) 0.2338(2) -0.0782(3) 0.0169(7) Uani 1 1 d . . . . .
H8A H 0.6156 0.2915 -0.1396 0.025 Uiso 1 1 calc R U . . .
H8B H 0.5596 0.1949 -0.0762 0.025 Uiso 1 1 calc R U . . .
H8C H 0.6753 0.1880 -0.1058 0.025 Uiso 1 1 calc R U . . .
C9 C 0.6502(3) 0.0944(2) 0.1327(3) 0.0185(6) Uani 1 1 d . . . . .
H9A H 0.5860 0.0753 0.0958 0.028 Uiso 1 1 calc R U . . .
H9B H 0.6603 0.0572 0.2147 0.028 Uiso 1 1 calc R U . . .
H9C H 0.7026 0.0760 0.0712 0.028 Uiso 1 1 calc R U . . .
C12 C 0.5656(2) 0.6752(2) 0.8683(3) 0.0151(6) Uani 1 1 d . . . . .
H12 H 0.5560 0.6298 0.9399 0.018 Uiso 1 1 calc R U . . .
C13 C 0.5745(2) 0.6329(2) 0.7451(3) 0.0127(6) Uani 1 1 d . . . . .
C14 C 0.5916(2) 0.7004(2) 0.6378(3) 0.0130(6) Uani 1 1 d . . . . .
C15 C 0.5951(2) 0.8082(2) 0.6670(3) 0.0150(6) Uani 1 1 d . . . . .
H15 H 0.6049 0.8559 0.5978 0.018 Uiso 1 1 calc R U . . .
C16 C 0.5847(2) 0.8456(2) 0.7903(3) 0.0155(6) Uani 1 1 d . . . . .
C17 C 0.5582(2) 0.5183(2) 0.7341(3) 0.0136(6) Uani 1 1 d . . . . .
C18 C 0.5554(3) 0.8150(3) 1.0260(3) 0.0238(8) Uani 1 1 d . . . . .
H18A H 0.5455 0.7558 1.0841 0.036 Uiso 1 1 calc R U . . .
H18B H 0.4973 0.8601 1.0292 0.036 Uiso 1 1 calc R U . . .
H18C H 0.6137 0.8540 1.0539 0.036 Uiso 1 1 calc R U . . .
C19 C 0.5886(2) 0.9592(2) 0.8194(3) 0.0197(7) Uani 1 1 d . . . . .
H19A H 0.5950 0.9980 0.7379 0.030 Uiso 1 1 calc R U . . .
H19B H 0.6455 0.9738 0.8753 0.030 Uiso 1 1 calc R U . . .
H19C H 0.5279 0.9801 0.8640 0.030 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 O12 1.919(2) . ?
Cu1 O13 1.921(2) . ?
Cu1 O2 1.937(2) . ?
Cu1 O3 1.949(2) . ?
Cu1 O11 2.388(2) 2_664 ?
O1 C7 1.253(4) . ?
O2 C7 1.277(4) . ?
O3 C4 1.288(4) . ?
O4 H4O 0.8216 . ?
O4 H4W 0.8823 . ?
O5 H5W 0.8133 . ?
O5 H5O 0.8297 . ?
O6 H6W 0.7310 . ?
O6 H6O 0.8329 . ?
O11 C17 1.244(4) . ?
O11 Cu1 2.388(2) 2_665 ?
O12 C17 1.282(4) . ?
O13 C14 1.290(4) . ?
N1 C2 1.350(4) . ?
N1 C6 1.380(4) . ?
N1 C8 1.474(4) . ?
N11 C12 1.346(4) . ?
N11 C16 1.375(4) . ?
N11 C18 1.479(4) . ?
C2 C3 1.376(4) . ?
C2 H2 0.9500 . ?
C3 C4 1.424(4) . ?
C3 C7 1.505(4) . ?
C4 C5 1.421(4) . ?
C5 C6 1.365(5) . ?
C5 H5 0.9500 . ?
C6 C9 1.496(4) . ?
C8 H8A 0.9800 . ?
C8 H8B 0.9800 . ?
C8 H8C 0.9800 . ?
C9 H9A 0.9800 . ?
C9 H9B 0.9800 . ?
C9 H9C 0.9800 . ?
C12 C13 1.384(4) . ?
C12 H12 0.9500 . ?
C13 C14 1.424(4) . ?
C13 C17 1.503(4) . ?
C14 C15 1.426(4) . ?
C15 C16 1.362(5) . ?
C15 H15 0.9500 . ?
C16 C19 1.499(4) . ?
C18 H18A 0.9800 . ?
C18 H18B 0.9800 . ?
C18 H18C 0.9800 . ?
C19 H19A 0.9800 . ?
C19 H19B 0.9800 . ?
C19 H19C 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
O12 Cu1 O13 93.61(9) . . ?
O12 Cu1 O2 172.89(10) . . ?
O13 Cu1 O2 87.21(9) . . ?
O12 Cu1 O3 86.55(9) . . ?
O13 Cu1 O3 164.96(10) . . ?
O2 Cu1 O3 90.83(9) . . ?
O12 Cu1 O11 101.89(9) . 2_664 ?
O13 Cu1 O11 96.09(9) . 2_664 ?
O2 Cu1 O11 85.03(8) . 2_664 ?
O3 Cu1 O11 98.59(8) . 2_664 ?
C7 O2 Cu1 125.15(19) . . ?
C4 O3 Cu1 121.22(19) . . ?
H4O O4 H4W 114.2 . . ?
H5W O5 H5O 99.8 . . ?
H6W O6 H6O 113.4 . . ?
C17 O11 Cu1 132.8(2) . 2_665 ?
C17 O12 Cu1 130.1(2) . . ?
C14 O13 Cu1 125.3(2) . . ?
C2 N1 C6 120.2(3) . . ?
C2 N1 C8 119.1(3) . . ?
C6 N1 C8 120.7(2) . . ?
C12 N11 C16 120.1(3) . . ?
C12 N11 C18 118.7(3) . . ?
C16 N11 C18 121.2(3) . . ?
N1 C2 C3 122.9(3) . . ?
N1 C2 H2 118.5 . . ?
C3 C2 H2 118.5 . . ?
C2 C3 C4 118.5(3) . . ?
C2 C3 C7 118.0(3) . . ?
C4 C3 C7 123.5(3) . . ?
O3 C4 C5 119.2(3) . . ?
O3 C4 C3 124.4(3) . . ?
C5 C4 C3 116.4(3) . . ?
C6 C5 C4 122.4(3) . . ?
C6 C5 H5 118.8 . . ?
C4 C5 H5 118.8 . . ?
C5 C6 N1 118.9(3) . . ?
C5 C6 C9 122.9(3) . . ?
N1 C6 C9 118.3(3) . . ?
O1 C7 O2 122.4(3) . . ?
O1 C7 C3 117.9(3) . . ?
O2 C7 C3 119.6(3) . . ?
N1 C8 H8A 109.5 . . ?
N1 C8 H8B 109.5 . . ?
H8A C8 H8B 109.5 . . ?
N1 C8 H8C 109.5 . . ?
H8A C8 H8C 109.5 . . ?
H8B C8 H8C 109.5 . . ?
C6 C9 H9A 109.5 . . ?
C6 C9 H9B 109.5 . . ?
H9A C9 H9B 109.5 . . ?
C6 C9 H9C 109.5 . . ?
H9A C9 H9C 109.5 . . ?
H9B C9 H9C 109.5 . . ?
N11 C12 C13 123.0(3) . . ?
N11 C12 H12 118.5 . . ?
C13 C12 H12 118.5 . . ?
C12 C13 C14 118.7(3) . . ?
C12 C13 C17 116.4(3) . . ?
C14 C13 C17 124.7(3) . . ?
O13 C14 C13 125.2(3) . . ?
O13 C14 C15 118.6(3) . . ?
C13 C14 C15 116.1(3) . . ?
C16 C15 C14 122.6(3) . . ?
C16 C15 H15 118.7 . . ?
C14 C15 H15 118.7 . . ?
C15 C16 N11 119.4(3) . . ?
C15 C16 C19 122.0(3) . . ?
N11 C16 C19 118.7(3) . . ?
O11 C17 O12 122.9(3) . . ?
O11 C17 C13 118.1(3) . . ?
O12 C17 C13 119.0(3) . . ?
N11 C18 H18A 109.5 . . ?
N11 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
N11 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
C16 C19 H19A 109.5 . . ?
C16 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
C16 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?

_refine_diff_density_max         0.440
_refine_diff_density_min         -0.264
_refine_diff_density_rms         0.082


_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: water'
