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

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_2P
_database_code_depnum_ccdc_archive 'CCDC 1423663'
_audit_update_record             
;
2016-12-22 deposited with the CCDC.
2017-01-03 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C18 H30 Cu4 N9 O6, NO3, 3H2O'
_chemical_formula_sum            'C18 H36 Cu4 N10 O12'
_chemical_formula_weight         838.73

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'
N N 0.0061 0.0033 '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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      hexagonal
_space_group_IT_number           182
_space_group_name_H-M_alt        'P 63 2 2'
_space_group_name_Hall           'P 6c 2c'

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

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

_cell_length_a                   19.613(3)
_cell_length_b                   19.613(3)
_cell_length_c                   13.849(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     4613.6(16)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    3085
_cell_measurement_theta_min      4.795
_cell_measurement_theta_max      37.207

_exptl_crystal_description       block
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.208
_exptl_crystal_F_000             1704
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.240
_exptl_crystal_size_mid          0.180
_exptl_crystal_size_min          0.180
_exptl_absorpt_coefficient_mu    1.867
_shelx_estimated_absorpt_T_min   0.663
_shelx_estimated_absorpt_T_max   0.730
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6632
_exptl_absorpt_correction_T_max  0.7301
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX CCD area-detector'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            26991
_diffrn_reflns_av_unetI/netI     0.0487
_diffrn_reflns_av_R_equivalents  0.0909
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         1.897
_diffrn_reflns_theta_max         25.099
_diffrn_reflns_theta_full        25.099
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measured_fraction_theta_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_point_group_measured_fraction_full 0.997
_reflns_number_total             2759
_reflns_number_gt                1781
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.678
_reflns_Friedel_fraction_max     0.997
_reflns_Friedel_fraction_full    0.997

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
 Single crystals of 2 were found to be weakly 
 diffracting.Such a problem is relatively common in the 
 field of framework materials and is typical for highly 
 porous materials with extensive structural disorder. 
 Numerous attempts were made at growing the crystals under
 a variety of conditions to slow the crystallisation 
 process and give less disordered crystals. Various other 
 techniques, such as cold mounting or desolvating the 
 crystals before analysis were also attempted. Unfortunately,
 all these manipulations gave no discernible improvement in 
 data quality. All methods to obtain a better diffraction 
 pattern were unsuccessful, indicating that it is likely 
 that the limitations to the data and resulting refinement 
 model are intrinsic to the inherent structural disorder. 
 The structural model reported was refined against the best
 diffraction data obtained. When combined with the known 
 chemical composition of the ligand and other structural 
 information from related characterizations, a sound model 
 of the framework structure was obtained, albeit with no 
 information on anion location.
 During the refinement,commands 'SIMU','DELU'and 'DFIX'were 
 used to the 1-hydroxyethyl group on the 3 and 5-position of 
 triazole ring to make the thermal parameters and geometry  
 parameters of atoms crystallographically and chemically 
 reasonable. All the non-hydrogen atoms have been refined 
 anisotropically.The following reflections were omitted 
 from the refinement as they were obscured by the beam 
 stop:0 1 0, -6 9 3, -2 9 0.
 Some residual electron densities, which should be considered 
 as peaks from heavily disordered solvent molecules and 
 counterions, did not give a chemical meaningful result after 
 a careful refinement. Therefore, the contributions of the 
 disordered solvent molecules and counterions were removed 
 from the diffraction data using the SQUEEZE routine of PLATON 
 software and then final refinements were carried out. The 
 final platon.sqf file was attached to the CIF file and the 
 electron numbers in the void obtained from the platon.sqf 
 file has been used to calculate the guest solvent molecules 
 crystallizing in the pore.These molecules are further 
 estimated by TGA analysis combining with element analysis, 
 which showed that there are 4 NO3- anions and 12 free water 
 molecules in the unit cell. Since these anions and solvent 
 moleculars are absent from the model, the calculated 
 molecular formula would be incorrect.Finally,the results 
 were introduced to the formula unit directly which 
 consequently generates significant A-level and B-level 
 errors (e.g. density, chemical formula, density) in the 
 final CIF output.
;

_computing_data_collection       'SMART (Bruker, 1997)'
_computing_cell_refinement       SMART
_computing_data_reduction        'SAINT (Bruker, 1999)'
_computing_structure_solution    'SHELXS-2016/6 (Sheldrick, 2016)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    'Diamond (Brandenburg and Putz, 2008)'
_computing_publication_material  'SHELXL-2016/6 (Sheldrick, 2016)'
_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)+(0.1062P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 563 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(2)
_chemical_absolute_configuration known
_refine_ls_number_reflns         2759
_refine_ls_number_parameters     113
_refine_ls_number_restraints     66
_refine_ls_R_factor_all          0.0932
_refine_ls_R_factor_gt           0.0583
_refine_ls_wR_factor_ref         0.1785
_refine_ls_wR_factor_gt          0.1581
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_restrained_S_all      1.133
_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 0.666667 0.333333 0.60127(12) 0.0632(5) Uani 1 3 d S T P . .
Cu2 Cu 0.52268(9) 0.26134(4) 0.750000 0.0662(5) Uani 1 2 d S T P . .
Cu3 Cu 0.46153(12) 0.000000 0.500000 0.0990(8) Uani 1 2 d S T P . .
N1 N 0.5919(5) 0.2202(5) 0.6002(5) 0.072(2) Uani 1 1 d . . . . .
N2 N 0.5258(5) 0.1920(4) 0.6607(5) 0.067(2) Uani 1 1 d . . . . .
C2 C 0.5797(9) 0.1629(6) 0.5442(6) 0.081(3) Uani 1 1 d . . . . .
N3 N 0.5074(5) 0.0946(5) 0.5645(6) 0.081(2) Uani 1 1 d . . . . .
C1 C 0.4794(7) 0.1184(6) 0.6371(7) 0.079(3) Uani 1 1 d . . . . .
C4 C 0.4010(9) 0.0602(9) 0.6724(11) 0.186(8) Uani 1 1 d D U . . .
H13 H 0.373767 0.023820 0.619029 0.223 Uiso 1 1 calc R U . . .
C3 C 0.6341(10) 0.1679(10) 0.4742(8) 0.149(6) Uani 1 1 d D U . . .
H15 H 0.676585 0.222058 0.485021 0.179 Uiso 1 1 calc R U . . .
O1 O 0.3973(9) 0.0139(10) 0.7532(13) 0.307(9) Uani 1 1 d D U . . .
H1 H 0.430167 0.000054 0.747107 0.461 Uiso 1 1 calc R U . . .
C6 C 0.3543(11) 0.1007(11) 0.696(2) 0.318(11) Uani 1 1 d D U . . .
H4A H 0.303040 0.062461 0.719377 0.477 Uiso 1 1 calc R U . . .
H4B H 0.381346 0.139769 0.745268 0.477 Uiso 1 1 calc R U . . .
H4C H 0.348955 0.125558 0.639308 0.477 Uiso 1 1 calc R U . . .
C5 C 0.6148(12) 0.1735(12) 0.3693(9) 0.207(9) Uani 1 1 d D U . . .
H3A H 0.656003 0.176597 0.328740 0.311 Uiso 1 1 calc R U . . .
H3B H 0.565865 0.127669 0.352453 0.311 Uiso 1 1 calc R U . . .
H3C H 0.610528 0.219723 0.360404 0.311 Uiso 1 1 calc R U . . .
O2 O 0.6774(10) 0.1277(11) 0.4778(10) 0.275(7) Uani 1 1 d D U . . .
H2 H 0.652044 0.084670 0.451580 0.412 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 N1 1.954(8) 3_655 ?
Cu1 N1 1.955(8) . ?
Cu1 N1 1.955(8) 4_665 ?
Cu2 N2 1.863(7) 11_556 ?
Cu2 N2 1.863(7) . ?
Cu3 N3 1.839(8) . ?
Cu3 N3 1.839(8) 7_556 ?
N1 C2 1.287(11) . ?
N1 N2 1.403(11) . ?
N2 C1 1.306(12) . ?
C2 N3 1.409(14) . ?
C2 C3 1.407(17) . ?
N3 C1 1.335(13) . ?
C1 C4 1.465(16) . ?
C4 O1 1.4200(14) . ?
C4 C6 1.5195(14) . ?
C4 H13 0.9800 . ?
C3 O2 1.4193(14) . ?
C3 C5 1.5187(14) . ?
C3 H15 0.9800 . ?
O1 H1 0.8200 . ?
C6 H4A 0.9600 . ?
C6 H4B 0.9600 . ?
C6 H4C 0.9600 . ?
C5 H3A 0.9600 . ?
C5 H3B 0.9600 . ?
C5 H3C 0.9600 . ?
O2 H2 0.8200 . ?

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 Cu1 N1 119.996(7) 3_655 . ?
N1 Cu1 N1 119.993(9) 3_655 4_665 ?
N1 Cu1 N1 119.994(8) . 4_665 ?
N2 Cu2 N2 176.7(5) 11_556 . ?
N3 Cu3 N3 178.2(6) . 7_556 ?
C2 N1 N2 106.5(9) . . ?
C2 N1 Cu1 134.7(8) . . ?
N2 N1 Cu1 117.7(5) . . ?
C1 N2 N1 106.5(7) . . ?
C1 N2 Cu2 135.5(7) . . ?
N1 N2 Cu2 118.0(6) . . ?
N1 C2 N3 111.6(10) . . ?
N1 C2 C3 123.5(13) . . ?
N3 C2 C3 124.9(11) . . ?
C1 N3 C2 102.4(8) . . ?
C1 N3 Cu3 129.7(8) . . ?
C2 N3 Cu3 127.8(7) . . ?
N2 C1 N3 113.1(9) . . ?
N2 C1 C4 131.1(11) . . ?
N3 C1 C4 115.7(11) . . ?
C1 C4 O1 117.4(14) . . ?
C1 C4 C6 109.7(13) . . ?
O1 C4 C6 108.12(14) . . ?
C1 C4 H13 107.1 . . ?
O1 C4 H13 107.1 . . ?
C6 C4 H13 107.1 . . ?
C2 C3 O2 125.4(12) . . ?
C2 C3 C5 117.2(12) . . ?
O2 C3 C5 108.21(14) . . ?
C2 C3 H15 100.1 . . ?
O2 C3 H15 100.1 . . ?
C5 C3 H15 100.1 . . ?
C4 O1 H1 109.5 . . ?
C4 C6 H4A 109.5 . . ?
C4 C6 H4B 109.5 . . ?
H4A C6 H4B 109.5 . . ?
C4 C6 H4C 109.5 . . ?
H4A C6 H4C 109.5 . . ?
H4B C6 H4C 109.5 . . ?
C3 C5 H3A 109.5 . . ?
C3 C5 H3B 109.5 . . ?
H3A C5 H3B 109.5 . . ?
C3 C5 H3C 109.5 . . ?
H3A C5 H3C 109.5 . . ?
H3B C5 H3C 109.5 . . ?
C3 O2 H2 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C2 N1 N2 C1 1.3(10) . . . . ?
Cu1 N1 N2 C1 170.6(7) . . . . ?
C2 N1 N2 Cu2 -178.6(7) . . . . ?
Cu1 N1 N2 Cu2 -9.2(9) . . . . ?
N2 N1 C2 N3 -0.8(12) . . . . ?
Cu1 N1 C2 N3 -167.5(7) . . . . ?
N2 N1 C2 C3 -178.6(10) . . . . ?
Cu1 N1 C2 C3 14.7(18) . . . . ?
N1 C2 N3 C1 0.0(13) . . . . ?
C3 C2 N3 C1 177.8(11) . . . . ?
N1 C2 N3 Cu3 176.1(8) . . . . ?
C3 C2 N3 Cu3 -6.1(17) . . . . ?
N1 N2 C1 N3 -1.3(12) . . . . ?
Cu2 N2 C1 N3 178.5(8) . . . . ?
N1 N2 C1 C4 -177.1(12) . . . . ?
Cu2 N2 C1 C4 3(2) . . . . ?
C2 N3 C1 N2 0.8(13) . . . . ?
Cu3 N3 C1 N2 -175.1(8) . . . . ?
C2 N3 C1 C4 177.3(10) . . . . ?
Cu3 N3 C1 C4 1.3(16) . . . . ?
N2 C1 C4 O1 -89.4(18) . . . . ?
N3 C1 C4 O1 95.0(17) . . . . ?
N2 C1 C4 C6 35(2) . . . . ?
N3 C1 C4 C6 -141.1(14) . . . . ?
N1 C2 C3 O2 111.1(17) . . . . ?
N3 C2 C3 O2 -66(2) . . . . ?
N1 C2 C3 C5 -106.1(17) . . . . ?
N3 C2 C3 C5 76.4(18) . . . . ?

_refine_diff_density_max         0.794
_refine_diff_density_min         -0.464
_refine_diff_density_rms         0.078





# start Validation Reply Form
_vrf_CHEMW03_2P                  
;
PROBLEM: ALERT: The ratio of given/expected molecular weight as
RESPONSE: Since the anions and solvent moleculars as well as 
 the missing hydrogen atoms mentioned previously are absent 
 from the model, the calculated molecular formula would be 
 incorrect.Finally,these results were introduced to the formula 
 unit directly which consequently generates significant 
 A-level and B-level errors (e.g. density, chemical formula, 
 density) in the final CIF output.
;
_vrf_PLAT341_2P                  
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............    0.02225 Ang.  
RESPONSE: Single crystals of 2 were found to be weakly 
 diffracting and much effort to get better diffracting 
 data were failed. 
;
_vrf_PLAT420_2P                  
;
PROBLEM: D-H Without Acceptor       O1     --  H1     ...     Please Check 
RESPONSE: The free water moleculars and anions in the crystal channels 
 have been eliminated by the SQUEEZE routine of PLATON 
 software. As a result,the terminal alcohol group is isolated 
 in the structures.
;
# end Validation Reply Form
####################################################################### 
# 
# 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_1P
_database_code_depnum_ccdc_archive 'CCDC 1423661'
_audit_update_record             
;
2016-12-22 deposited with the CCDC.
2017-01-03 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C24 H48 Cu4 N10 O6'
_chemical_formula_weight         826.88

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'
N N 0.0061 0.0033 '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'
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'

_space_group_crystal_system      hexagonal
_space_group_IT_number           182
_space_group_name_H-M_alt        'P 63 2 2'
_space_group_name_Hall           'P 6c 2c'

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

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

_cell_length_a                   19.603(5)
_cell_length_b                   19.603(5)
_cell_length_c                   13.939(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     4639(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    3637
_cell_measurement_theta_min      4.797
_cell_measurement_theta_max      36.988

_exptl_crystal_description       block
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.184
_exptl_crystal_F_000             1704
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.240
_exptl_crystal_size_mid          0.180
_exptl_crystal_size_min          0.180
_exptl_absorpt_coefficient_mu    1.847
_shelx_estimated_absorpt_T_min   0.666
_shelx_estimated_absorpt_T_max   0.732
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6659
_exptl_absorpt_correction_T_max  0.7325
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71069
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX CCD area-detector'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            26376
_diffrn_reflns_av_unetI/netI     0.0373
_diffrn_reflns_av_R_equivalents  0.0701
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         1.890
_diffrn_reflns_theta_max         24.764
_diffrn_reflns_theta_full        24.764
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             2670
_reflns_number_gt                1914
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.673
_reflns_Friedel_fraction_max     0.997
_reflns_Friedel_fraction_full    0.997

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
 Single crystals of 1 were found to be weakly 
 diffracting.Such a problem is relatively common in the 
 field of framework materials and is typical for highly 
 porous materials with extensive structural disorder. 
 Numerous attempts were made at growing the crystals under
 a variety of conditions to slow the crystallisation 
 process and give less disordered crystals. Various other 
 techniques, such as cold mounting or desolvating the 
 crystals before analysis were also attempted. Unfortunately,
 all these manipulations gave no discernible improvement in 
 data quality. All methods to obtain a better diffraction 
 pattern were unsuccessful, indicating that it is likely 
 that the limitations to the data and resulting refinement 
 model are intrinsic to the inherent structural disorder. 
 The structural model reported was refined against the best
 diffraction data obtained. When combined with the known 
 chemical composition of the ligand and other structural 
 information from related characterizations, a sound model 
 of the framework structure was obtained, albeit with no 
 information on anion location.
 During the refinement,commands 'SIMU','DELU'and 'DFIX'were 
 used to the isopropyl group on the 3 and 5-position of 
 triazole ring to make the thermal parameters and geometry  
 parameters of atoms crystallographically and chemically 
 reasonable. All the non-hydrogen atoms have been refined 
 anisotropically.The following reflections were omitted 
 from the refinement as they were obscured by the beam 
 stop:0 1 0, -1 7 2.
 Some residual electron densities, which should be considered 
 as peaks from heavily disordered solvent molecules and 
 counterions, did not give a chemical meaningful result after 
 a careful refinement. Therefore, the contributions of the 
 disordered solvent molecules and counterions were removed 
 from the diffraction data using the SQUEEZE routine of PLATON 
 software and then final refinements were carried out. The 
 final platon.sqf file was attached to the CIF file and the 
 electron numbers in the void obtained from the platon.sqf 
 file has been used to calculate the guest solvent molecules 
 crystallizing in the pore.These molecules are further 
 estimated by TGA analysis combining with element analysis, 
 which showed that there are 4 NO3- anions and 12 free water 
 molecules in the unit cell. Since these anions and solvent 
 moleculars are absent from the model, the calculated 
 molecular formula would be incorrect.Finally,the results 
 were introduced to the formula unit directly which 
 consequently generates significant A-level and B-level 
 errors (e.g. density, chemical formula, density) in the 
 final CIF output.
;

_computing_data_collection       'SMART (Bruker, 1997)'
_computing_cell_refinement       SMART
_computing_data_reduction        'SAINT (Bruker, 1999)'
_computing_structure_solution    'SHELXS-2016/6 (Sheldrick, 2016)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    'Diamond (Brandenburg and Putz, 2008)'
_computing_publication_material  'SHELXL-2016/6 (Sheldrick, 2016)'
_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)+(0.0819P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 626 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.034(17)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         2670
_refine_ls_number_parameters     113
_refine_ls_number_restraints     48
_refine_ls_R_factor_all          0.0709
_refine_ls_R_factor_gt           0.0475
_refine_ls_wR_factor_ref         0.1332
_refine_ls_wR_factor_gt          0.1204
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_restrained_S_all      1.049
_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 0.666667 0.333333 0.60138(9) 0.0599(4) Uani 1 3 d S T P . .
Cu2 Cu 0.73834(3) 0.26166(3) 0.750000 0.0625(4) Uani 1 2 d S T P . .
Cu3 Cu 1.000000 0.45958(9) 0.500000 0.0936(6) Uani 1 2 d S T P . .
N2 N 0.8075(3) 0.3328(4) 0.6611(4) 0.0624(15) Uani 1 1 d . . . . .
N1 N 0.7796(3) 0.3703(3) 0.6010(4) 0.0649(17) Uani 1 1 d . . . . .
N3 N 0.9033(4) 0.4090(4) 0.5641(5) 0.0783(18) Uani 1 1 d . . . . .
C1 C 0.8377(4) 0.4157(7) 0.5443(5) 0.079(2) Uani 1 1 d . . . . .
C2 C 0.8816(5) 0.3567(5) 0.6366(5) 0.073(2) Uani 1 1 d . . . . .
C3 C 0.9295(5) 0.3339(7) 0.6885(8) 0.121(4) Uani 1 1 d D U . . .
H3 H 0.894626 0.295523 0.736116 0.145 Uiso 1 1 calc R U . . .
C4 C 0.8232(7) 0.4649(6) 0.4730(5) 0.146(5) Uani 1 1 d D U . . .
H4 H 0.769656 0.455807 0.481890 0.175 Uiso 1 1 calc R U . . .
C5 C 0.8318(8) 0.4428(7) 0.3711(7) 0.175(6) Uani 1 1 d D U . . .
H5A H 0.796883 0.387416 0.361658 0.263 Uiso 1 1 calc R U . . .
H5B H 0.818795 0.471969 0.326677 0.263 Uiso 1 1 calc R U . . .
H5C H 0.885142 0.455053 0.360690 0.263 Uiso 1 1 calc R U . . .
C8 C 1.0016(8) 0.3934(7) 0.7440(10) 0.213(6) Uani 1 1 d D U . . .
H8A H 1.026150 0.367130 0.774042 0.320 Uiso 1 1 calc R U . . .
H8B H 1.038232 0.432919 0.700750 0.320 Uiso 1 1 calc R U . . .
H8C H 0.985979 0.417890 0.792155 0.320 Uiso 1 1 calc R U . . .
C6 C 0.8812(8) 0.5528(6) 0.4768(8) 0.173(5) Uani 1 1 d D U . . .
H6A H 0.879984 0.572558 0.539436 0.260 Uiso 1 1 calc R U . . .
H6B H 0.933287 0.562308 0.463666 0.260 Uiso 1 1 calc R U . . .
H6C H 0.866940 0.579224 0.429652 0.260 Uiso 1 1 calc R U . . .
C7 C 0.9609(7) 0.2909(8) 0.6283(10) 0.215(7) Uani 1 1 d D U . . .
H7A H 0.992518 0.277449 0.667790 0.323 Uiso 1 1 calc R U . . .
H7B H 0.917534 0.243800 0.602372 0.323 Uiso 1 1 calc R U . . .
H7C H 0.992350 0.324433 0.576866 0.323 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 N1 1.956(6) . ?
Cu1 N1 1.956(6) 4_665 ?
Cu1 N1 1.956(6) 3_655 ?
Cu2 N2 1.852(6) . ?
Cu2 N2 1.852(5) 10_666 ?
Cu3 N3 1.870(6) . ?
Cu3 N3 1.870(6) 8_766 ?
N2 C2 1.328(9) . ?
N2 N1 1.393(8) . ?
N1 C1 1.304(9) . ?
N3 C2 1.348(9) . ?
N3 C1 1.383(10) . ?
C1 C4 1.507(13) . ?
C2 C3 1.423(12) . ?
C3 C8 1.5193(14) . ?
C3 C7 1.5189(14) . ?
C3 H3 0.9800 . ?
C4 C5 1.5184(15) . ?
C4 C6 1.5190(14) . ?
C4 H4 0.9800 . ?
C5 H5A 0.9600 . ?
C5 H5B 0.9600 . ?
C5 H5C 0.9600 . ?
C8 H8A 0.9600 . ?
C8 H8B 0.9600 . ?
C8 H8C 0.9600 . ?
C6 H6A 0.9600 . ?
C6 H6B 0.9600 . ?
C6 H6C 0.9600 . ?
C7 H7A 0.9600 . ?
C7 H7B 0.9600 . ?
C7 H7C 0.9600 . ?

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 Cu1 N1 119.998(2) . 4_665 ?
N1 Cu1 N1 120.001(4) . 3_655 ?
N1 Cu1 N1 119.999(3) 4_665 3_655 ?
N2 Cu2 N2 177.9(4) . 10_666 ?
N3 Cu3 N3 177.3(5) . 8_766 ?
C2 N2 N1 107.9(6) . . ?
C2 N2 Cu2 134.2(6) . . ?
N1 N2 Cu2 117.8(4) . . ?
C1 N1 N2 106.6(6) . . ?
C1 N1 Cu1 134.0(5) . . ?
N2 N1 Cu1 118.3(4) . . ?
C2 N3 C1 105.5(6) . . ?
C2 N3 Cu3 127.7(6) . . ?
C1 N3 Cu3 126.7(5) . . ?
N1 C1 N3 110.4(8) . . ?
N1 C1 C4 117.2(8) . . ?
N3 C1 C4 132.4(7) . . ?
N2 C2 N3 109.5(7) . . ?
N2 C2 C3 122.4(8) . . ?
N3 C2 C3 127.8(8) . . ?
C2 C3 C8 121.6(10) . . ?
C2 C3 C7 114.0(10) . . ?
C8 C3 C7 103.18(13) . . ?
C2 C3 H3 105.6 . . ?
C8 C3 H3 105.6 . . ?
C7 C3 H3 105.6 . . ?
C5 C4 C6 103.25(13) . . ?
C5 C4 C1 110.5(9) . . ?
C6 C4 C1 115.4(10) . . ?
C5 C4 H4 109.1 . . ?
C6 C4 H4 109.1 . . ?
C1 C4 H4 109.1 . . ?
C4 C5 H5A 109.5 . . ?
C4 C5 H5B 109.5 . . ?
H5A C5 H5B 109.5 . . ?
C4 C5 H5C 109.5 . . ?
H5A C5 H5C 109.5 . . ?
H5B C5 H5C 109.5 . . ?
C3 C8 H8A 109.5 . . ?
C3 C8 H8B 109.5 . . ?
H8A C8 H8B 109.5 . . ?
C3 C8 H8C 109.5 . . ?
H8A C8 H8C 109.5 . . ?
H8B C8 H8C 109.5 . . ?
C4 C6 H6A 109.5 . . ?
C4 C6 H6B 109.5 . . ?
H6A C6 H6B 109.5 . . ?
C4 C6 H6C 109.5 . . ?
H6A C6 H6C 109.5 . . ?
H6B C6 H6C 109.5 . . ?
C3 C7 H7A 109.5 . . ?
C3 C7 H7B 109.5 . . ?
H7A C7 H7B 109.5 . . ?
C3 C7 H7C 109.5 . . ?
H7A C7 H7C 109.5 . . ?
H7B C7 H7C 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C2 N2 N1 C1 -1.0(8) . . . . ?
Cu2 N2 N1 C1 -178.8(6) . . . . ?
C2 N2 N1 Cu1 168.5(5) . . . . ?
Cu2 N2 N1 Cu1 -9.3(7) . . . . ?
N2 N1 C1 N3 0.7(10) . . . . ?
Cu1 N1 C1 N3 -166.5(5) . . . . ?
N2 N1 C1 C4 -178.6(8) . . . . ?
Cu1 N1 C1 C4 14.3(14) . . . . ?
C2 N3 C1 N1 -0.1(11) . . . . ?
Cu3 N3 C1 N1 177.9(6) . . . . ?
C2 N3 C1 C4 179.0(10) . . . . ?
Cu3 N3 C1 C4 -3.0(16) . . . . ?
N1 N2 C2 N3 1.0(8) . . . . ?
Cu2 N2 C2 N3 178.2(5) . . . . ?
N1 N2 C2 C3 175.4(8) . . . . ?
Cu2 N2 C2 C3 -7.4(12) . . . . ?
C1 N3 C2 N2 -0.5(10) . . . . ?
Cu3 N3 C2 N2 -178.5(5) . . . . ?
C1 N3 C2 C3 -174.6(9) . . . . ?
Cu3 N3 C2 C3 7.4(13) . . . . ?
N2 C2 C3 C8 -113.9(11) . . . . ?
N3 C2 C3 C8 59.4(14) . . . . ?
N2 C2 C3 C7 121.5(10) . . . . ?
N3 C2 C3 C7 -65.2(13) . . . . ?
N1 C1 C4 C5 -118.3(10) . . . . ?
N3 C1 C4 C5 62.6(14) . . . . ?
N1 C1 C4 C6 125.0(10) . . . . ?
N3 C1 C4 C6 -54.1(15) . . . . ?

_refine_diff_density_max         0.460
_refine_diff_density_min         -0.418
_refine_diff_density_rms         0.066





# start Validation Reply Form
_vrf_CHEMW03_1P                  
;
PROBLEM: ALERT: The ratio of given/expected molecular weight as
RESPONSE: Since the anions and solvent moleculars are absent 
 from the model, the calculated molecular formula would be 
 incorrect.Finally,these results were introduced to the formula 
 unit directly which consequently generates significant 
 A-level and B-level errors (e.g. density, chemical formula, 
 density) in the final CIF output.
;
_vrf_PLAT341_1P                  
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............    0.01567 Ang.  
RESPONSE: Single crystals of 1 were found to be weakly 
 diffracting and much effort to get better diffracting 
 data were failed.
;
# end Validation Reply Form






####################################################################### 
# 
# 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_1M
_database_code_depnum_ccdc_archive 'CCDC 1423660'
_audit_update_record             
;
2016-12-22 deposited with the CCDC.
2017-01-03 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C24 H48 Cu4 N10 O6'
_chemical_formula_weight         826.88

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'
N N 0.0061 0.0033 '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'
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'

_space_group_crystal_system      hexagonal
_space_group_IT_number           182
_space_group_name_H-M_alt        'P 63 2 2'
_space_group_name_Hall           'P 6c 2c'

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

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

_cell_length_a                   19.593(4)
_cell_length_b                   19.593(4)
_cell_length_c                   13.927(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     4630(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    3777
_cell_measurement_theta_min      4.801
_cell_measurement_theta_max      37.019

_exptl_crystal_description       block
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.186
_exptl_crystal_F_000             1704
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.240
_exptl_crystal_size_mid          0.180
_exptl_crystal_size_min          0.180
_exptl_absorpt_coefficient_mu    1.850
_shelx_estimated_absorpt_T_min   0.665
_shelx_estimated_absorpt_T_max   0.732
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6650
_exptl_absorpt_correction_T_max  0.7321
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX CCD area-detector'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            27090
_diffrn_reflns_av_unetI/netI     0.0396
_diffrn_reflns_av_R_equivalents  0.0737
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         1.892
_diffrn_reflns_theta_max         25.103
_diffrn_reflns_theta_full        25.103
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             2774
_reflns_number_gt                1962
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.677
_reflns_Friedel_fraction_max     0.998
_reflns_Friedel_fraction_full    0.998

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
 Single crystals of 1 were found to be weakly 
 diffracting.Such a problem is relatively common in the 
 field of framework materials and is typical for highly 
 porous materials with extensive structural disorder. 
 Numerous attempts were made at growing the crystals under
 a variety of conditions to slow the crystallisation 
 process and give less disordered crystals. Various other 
 techniques, such as cold mounting or desolvating the 
 crystals before analysis were also attempted. Unfortunately,
 all these manipulations gave no discernible improvement in 
 data quality. All methods to obtain a better diffraction 
 pattern were unsuccessful, indicating that it is likely 
 that the limitations to the data and resulting refinement 
 model are intrinsic to the inherent structural disorder. 
 The structural model reported was refined against the best
 diffraction data obtained. When combined with the known 
 chemical composition of the ligand and other structural 
 information from related characterizations, a sound model 
 of the framework structure was obtained, albeit with no 
 information on anion location.
 During the refinement,commands 'SIMU','DELU'and 'DFIX'were 
 used to the isopropyl group on the 3 and 5-position of 
 triazole ring to make the thermal parameters and geometry  
 parameters of atoms crystallographically and chemically 
 reasonable. All the non-hydrogen atoms have been refined 
 anisotropically.The following reflections were omitted 
 from the refinement as they were obscured by the beam 
 stop:0 1 0, -1 4 0.
 Some residual electron densities, which should be considered 
 as peaks from heavily disordered solvent molecules and 
 counterions, did not give a chemical meaningful result after 
 a careful refinement. Therefore, the contributions of the 
 disordered solvent molecules and counterions were removed 
 from the diffraction data using the SQUEEZE routine of PLATON 
 software and then final refinements were carried out. The 
 final platon.sqf file was attached to the CIF file and the 
 electron numbers in the void obtained from the platon.sqf 
 file has been used to calculate the guest solvent molecules 
 crystallizing in the pore.These molecules are further 
 estimated by TGA analysis combining with element analysis, 
 which showed that there are 4 NO3- anions and 12 free water 
 molecules in the unit cell. Since these anions and solvent 
 moleculars are absent from the model, the calculated 
 molecular formula would be incorrect.Finally,the results 
 were introduced to the formula unit directly which 
 consequently generates significant A-level and B-level 
 errors (e.g. density, chemical formula, density) in the 
 final CIF output.
;

_computing_data_collection       'SMART (Bruker, 1997)'
_computing_cell_refinement       SMART
_computing_data_reduction        'SAINT (Bruker, 1999)'
_computing_structure_solution    'SHELXS-2016/6 (Sheldrick, 2016)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    'Diamond (Brandenburg and Putz, 2008)'
_computing_publication_material  'SHELXL-2016/6 (Sheldrick, 2016)'
_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)+(0.0901P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 650 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.046(18)
_chemical_absolute_configuration 'chiral topology'
_refine_ls_number_reflns         2774
_refine_ls_number_parameters     113
_refine_ls_number_restraints     48
_refine_ls_R_factor_all          0.0737
_refine_ls_R_factor_gt           0.0482
_refine_ls_wR_factor_ref         0.1416
_refine_ls_wR_factor_gt          0.1264
_refine_ls_goodness_of_fit_ref   1.006
_refine_ls_restrained_S_all      1.025
_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 0.666667 0.333333 0.10146(9) 0.0591(4) Uani 1 3 d S T P . .
Cu2 Cu 0.73831(3) 0.26169(3) 0.250000 0.0619(4) Uani 1 2 d S T P . .
Cu3 Cu 0.54023(9) 0.000000 0.000000 0.0930(6) Uani 1 2 d S T P . .
N1 N 0.6292(4) 0.2198(3) 0.1013(4) 0.0657(17) Uani 1 1 d . . . . .
N2 N 0.6670(4) 0.1924(3) 0.1610(4) 0.0603(15) Uani 1 1 d . . . . .
C1 C 0.5841(7) 0.1618(4) 0.0448(5) 0.0746(19) Uani 1 1 d . . . . .
N3 N 0.5902(4) 0.0968(4) 0.0638(5) 0.0803(19) Uani 1 1 d . . . . .
C2 C 0.6424(5) 0.1186(5) 0.1372(5) 0.073(2) Uani 1 1 d . . . . .
C3 C 0.6661(7) 0.0704(5) 0.1893(8) 0.114(3) Uani 1 1 d D U . . .
H3 H 0.703829 0.104446 0.238117 0.137 Uiso 1 1 calc R U . . .
C4 C 0.5378(6) 0.1770(7) -0.0277(6) 0.139(4) Uani 1 1 d D U . . .
H4 H 0.548670 0.231221 -0.019325 0.167 Uiso 1 1 calc R U . . .
C7 C 0.6053(7) -0.0034(8) 0.2410(10) 0.207(6) Uani 1 1 d D U . . .
H7A H 0.631079 -0.028273 0.271789 0.311 Uiso 1 1 calc R U . . .
H7B H 0.578838 0.010529 0.288446 0.311 Uiso 1 1 calc R U . . .
H7C H 0.567538 -0.039200 0.195517 0.311 Uiso 1 1 calc R U . . .
C6 C 0.5582(7) 0.1678(9) -0.1303(7) 0.178(6) Uani 1 1 d D U . . .
H6A H 0.526569 0.178298 -0.173876 0.267 Uiso 1 1 calc R U . . .
H6B H 0.612928 0.204278 -0.142025 0.267 Uiso 1 1 calc R U . . .
H6C H 0.547891 0.114951 -0.139888 0.267 Uiso 1 1 calc R U . . .
C5 C 0.4492(6) 0.1222(9) -0.0233(8) 0.181(6) Uani 1 1 d D U . . .
H5A H 0.424289 0.136333 -0.072530 0.272 Uiso 1 1 calc R U . . .
H5B H 0.437370 0.068837 -0.032931 0.272 Uiso 1 1 calc R U . . .
H5C H 0.430000 0.126697 0.038436 0.272 Uiso 1 1 calc R U . . .
C8 C 0.7093(8) 0.0406(7) 0.1268(10) 0.208(7) Uani 1 1 d D U . . .
H8A H 0.723734 0.008903 0.164879 0.312 Uiso 1 1 calc R U . . .
H8B H 0.675481 0.009360 0.075335 0.312 Uiso 1 1 calc R U . . .
H8C H 0.755897 0.084566 0.100777 0.312 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 N1 1.964(6) 3_655 ?
Cu1 N1 1.964(6) 4_665 ?
Cu1 N1 1.964(6) . ?
Cu2 N2 1.853(5) . ?
Cu2 N2 1.853(5) 10_665 ?
Cu3 N3 1.868(6) 7 ?
Cu3 N3 1.868(6) . ?
N1 C1 1.298(9) . ?
N1 N2 1.388(8) . ?
N2 C2 1.318(10) . ?
C1 N3 1.363(10) . ?
C1 C4 1.483(13) . ?
N3 C2 1.355(10) . ?
C2 C3 1.440(12) . ?
C3 C7 1.5194(14) . ?
C3 C8 1.5191(14) . ?
C3 H3 0.9800 . ?
C4 C6 1.5186(14) . ?
C4 C5 1.5190(14) . ?
C4 H4 0.9800 . ?
C7 H7A 0.9600 . ?
C7 H7B 0.9600 . ?
C7 H7C 0.9600 . ?
C6 H6A 0.9600 . ?
C6 H6B 0.9600 . ?
C6 H6C 0.9600 . ?
C5 H5A 0.9600 . ?
C5 H5B 0.9600 . ?
C5 H5C 0.9600 . ?
C8 H8A 0.9600 . ?
C8 H8B 0.9600 . ?
C8 H8C 0.9600 . ?

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 Cu1 N1 120.000(1) 3_655 4_665 ?
N1 Cu1 N1 120.000(1) 3_655 . ?
N1 Cu1 N1 120.000(2) 4_665 . ?
N2 Cu2 N2 177.9(4) . 10_665 ?
N3 Cu3 N3 178.1(5) 7 . ?
C1 N1 N2 106.7(6) . . ?
C1 N1 Cu1 134.2(5) . . ?
N2 N1 Cu1 117.9(4) . . ?
C2 N2 N1 107.4(6) . . ?
C2 N2 Cu2 134.5(6) . . ?
N1 N2 Cu2 118.0(4) . . ?
N1 C1 N3 111.1(8) . . ?
N1 C1 C4 117.0(8) . . ?
N3 C1 C4 131.9(8) . . ?
C1 N3 C2 104.9(7) . . ?
C1 N3 Cu3 127.6(5) . . ?
C2 N3 Cu3 127.4(6) . . ?
N2 C2 N3 109.9(7) . . ?
N2 C2 C3 122.1(8) . . ?
N3 C2 C3 127.9(8) . . ?
C2 C3 C7 120.4(10) . . ?
C2 C3 C8 112.9(10) . . ?
C7 C3 C8 103.16(12) . . ?
C2 C3 H3 106.5 . . ?
C7 C3 H3 106.5 . . ?
C8 C3 H3 106.5 . . ?
C1 C4 C6 113.2(10) . . ?
C1 C4 C5 115.3(10) . . ?
C6 C4 C5 103.24(12) . . ?
C1 C4 H4 108.3 . . ?
C6 C4 H4 108.3 . . ?
C5 C4 H4 108.3 . . ?
C3 C7 H7A 109.5 . . ?
C3 C7 H7B 109.5 . . ?
H7A C7 H7B 109.5 . . ?
C3 C7 H7C 109.5 . . ?
H7A C7 H7C 109.5 . . ?
H7B C7 H7C 109.5 . . ?
C4 C6 H6A 109.5 . . ?
C4 C6 H6B 109.5 . . ?
H6A C6 H6B 109.5 . . ?
C4 C6 H6C 109.5 . . ?
H6A C6 H6C 109.5 . . ?
H6B C6 H6C 109.5 . . ?
C4 C5 H5A 109.5 . . ?
C4 C5 H5B 109.5 . . ?
H5A C5 H5B 109.5 . . ?
C4 C5 H5C 109.5 . . ?
H5A C5 H5C 109.5 . . ?
H5B C5 H5C 109.5 . . ?
C3 C8 H8A 109.5 . . ?
C3 C8 H8B 109.5 . . ?
H8A C8 H8B 109.5 . . ?
C3 C8 H8C 109.5 . . ?
H8A C8 H8C 109.5 . . ?
H8B C8 H8C 109.5 . . ?

_refine_diff_density_max         0.467
_refine_diff_density_min         -0.427
_refine_diff_density_rms         0.067






# start Validation Reply Form
_vrf_CHEMW03_1M                  
;
PROBLEM: ALERT: The ratio of given/expected molecular weight as
RESPONSE: Since the anions and solvent moleculars are absent 
 from the model, the calculated molecular formula would be 
 incorrect.Finally,these results were introduced to the formula 
 unit directly which consequently generates significant 
 A-level and B-level errors (e.g. density, chemical formula, 
 density) in the final CIF output.
;
_vrf_PLAT341_1M                  
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............      0.017 Ang.  
RESPONSE: Single crystals of 1 were found to be weakly 
 diffracting and much effort to get better diffracting 
 data were failed.
;
# end Validation Reply Form

####################################################################### 
# 
# 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_2M
_database_code_depnum_ccdc_archive 'CCDC 1423662'
_audit_update_record             
;
2016-12-22 deposited with the CCDC.
2017-01-03 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C18 H30 Cu4 N9 O6, NO3, 3H2O'
_chemical_formula_sum            'C18 H30 Cu4 N10 O12'
_chemical_formula_weight         832.68

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'
N N 0.0061 0.0033 '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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      hexagonal
_space_group_IT_number           182
_space_group_name_H-M_alt        'P 63 2 2'
_space_group_name_Hall           'P 6c 2c'

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

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

_cell_length_a                   19.6977(13)
_cell_length_b                   19.6977(13)
_cell_length_c                   13.8757(10)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     4662.5(7)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    3172
_cell_measurement_theta_min      4.776
_cell_measurement_theta_max      37.014

_exptl_crystal_description       block
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.186
_exptl_crystal_F_000             1680
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.240
_exptl_crystal_size_mid          0.180
_exptl_crystal_size_min          0.180
_exptl_absorpt_coefficient_mu    1.847
_shelx_estimated_absorpt_T_min   0.665
_shelx_estimated_absorpt_T_max   0.732
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6653
_exptl_absorpt_correction_T_max  0.7321
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX CCD area-detector'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            27099
_diffrn_reflns_av_unetI/netI     0.0463
_diffrn_reflns_av_R_equivalents  0.0758
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         1.194
_diffrn_reflns_theta_max         25.067
_diffrn_reflns_theta_full        25.067
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             2785
_reflns_number_gt                1841
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.680
_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.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
 Single crystals of 2 were found to be weakly 
 diffracting.Such a problem is relatively common in the 
 field of framework materials and is typical for highly 
 porous materials with extensive structural disorder. 
 Numerous attempts were made at growing the crystals under
 a variety of conditions to slow the crystallisation 
 process and give less disordered crystals. Various other 
 techniques, such as cold mounting or desolvating the 
 crystals before analysis were also attempted. Unfortunately,
 all these manipulations gave no discernible improvement in 
 data quality. All methods to obtain a better diffraction 
 pattern were unsuccessful, indicating that it is likely 
 that the limitations to the data and resulting refinement 
 model are intrinsic to the inherent structural disorder. 
 The structural model reported was refined against the best
 diffraction data obtained. When combined with the known 
 chemical composition of the ligand and other structural 
 information from related characterizations, a sound model 
 of the framework structure was obtained, albeit with no 
 information on anion location.
 During the refinement,commands 'SIMU','DELU'and 'DFIX'were 
 used to the 1-hydroxyethyl group on the 3 and 5-position of 
 triazole ring to make the thermal parameters and geometry  
 parameters of atoms crystallographically and chemically 
 reasonable. All the non-hydrogen atoms have been refined 
 anisotropically.The following reflections were omitted 
 from the refinement as they were obscured by the beam 
 stop:0 4 3, 0 3 2, -2 4 4, 0 0 2, 0 2 1.
 Some residual electron densities, which should be considered 
 as peaks from heavily disordered solvent molecules and 
 counterions, did not give a chemical meaningful result after 
 a careful refinement. Therefore, the contributions of the 
 disordered solvent molecules and counterions were removed 
 from the diffraction data using the SQUEEZE routine of PLATON 
 software and then final refinements were carried out. The 
 final platon.sqf file was attached to the CIF file and the 
 electron numbers in the void obtained from the platon.sqf 
 file has been used to calculate the guest solvent molecules 
 crystallizing in the pore.These molecules are further 
 estimated by TGA analysis combining with element analysis, 
 which showed that there are 4 NO3- anions and 12 free water 
 molecules in the unit cell. Since these anions and solvent 
 moleculars are absent from the model, the calculated 
 molecular formula would be incorrect.Finally,the results 
 were introduced to the formula unit directly which 
 consequently generates significant A-level and B-level 
 errors (e.g. density, chemical formula, density) in the 
 final CIF output.
;

_computing_data_collection       'SMART (Bruker, 1997)'
_computing_cell_refinement       SMART
_computing_data_reduction        'SAINT (Bruker, 1999)'
_computing_structure_solution    'SHELXS-2016/6 (Sheldrick, 2016)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    'Diamond (Brandenburg and Putz, 2008)'
_computing_publication_material  'SHELXL-2016/6 (Sheldrick, 2016)'
_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)+(0.0856P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 542 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.06(2)
_chemical_absolute_configuration known
_refine_ls_number_reflns         2785
_refine_ls_number_parameters     113
_refine_ls_number_restraints     90
_refine_ls_R_factor_all          0.0782
_refine_ls_R_factor_gt           0.0566
_refine_ls_wR_factor_ref         0.1507
_refine_ls_wR_factor_gt          0.1424
_refine_ls_goodness_of_fit_ref   1.006
_refine_ls_restrained_S_all      1.049
_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 0.8391(5) 0.4312(7) 0.5381(6) 0.089(3) Uani 1 1 d . U . . .
C2 C 0.8768(6) 0.5214(6) 0.6359(6) 0.082(3) Uani 1 1 d . . . . .
C4 C 0.8305(8) 0.3738(8) 0.4595(9) 0.196(6) Uani 1 1 d D U . . .
H4 H 0.775776 0.331790 0.454263 0.236 Uiso 1 1 calc R U . A 2
O1 O 0.8804(9) 0.3416(8) 0.4715(9) 0.267(6) Uani 1 1 d D U . . .
H1 H 0.912508 0.356598 0.427580 0.400 Uiso 1 1 calc R U . . .
N1 N 0.8054(3) 0.4748(4) 0.6564(4) 0.0613(17) Uani 1 1 d . . . . .
N2 N 0.7782(4) 0.4133(4) 0.5935(5) 0.0671(18) Uani 1 1 d . . . . .
N3 N 0.9026(4) 0.4977(5) 0.5619(5) 0.082(2) Uani 1 1 d . U . . .
Cu1 Cu 0.73939(4) 0.47879(7) 0.750000 0.0722(5) Uani 1 2 d S T P . .
Cu2 Cu 0.666667 0.333333 0.59178(11) 0.0664(5) Uani 1 3 d S T P . .
Cu3 Cu 1.000000 0.54366(10) 0.500000 0.1012(6) Uani 1 2 d S T P . .
C6 C 0.8555(11) 0.4233(9) 0.3685(9) 0.260(9) Uani 1 1 d D U . B 2
H6A H 0.822419 0.445684 0.358964 0.390 Uiso 1 1 calc R U . B 2
H6B H 0.908943 0.464539 0.374738 0.390 Uiso 1 1 calc R U . B 2
H6C H 0.850738 0.391016 0.314176 0.390 Uiso 1 1 calc R U . B 2
C3 C 0.9321(7) 0.6001(8) 0.6860(8) 0.155(5) Uani 1 1 d D U . . .
H3 H 0.965345 0.639341 0.638164 0.186 Uiso 1 1 calc R U . . .
O2 O 0.9792(8) 0.5936(8) 0.7588(11) 0.278(7) Uani 1 1 d D U . . .
H2 H 0.965575 0.601139 0.811739 0.416 Uiso 1 1 calc R U . . .
C5 C 0.8780(8) 0.6244(10) 0.7338(15) 0.244(8) Uani 1 1 d D U . . .
H5A H 0.845617 0.629154 0.685734 0.366 Uiso 1 1 calc R U . . .
H5B H 0.845535 0.585398 0.780145 0.366 Uiso 1 1 calc R U . . .
H5C H 0.908834 0.673829 0.765610 0.366 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
C1 N2 1.315(10) . ?
C1 N3 1.324(12) . ?
C1 C4 1.519(16) . ?
C2 N1 1.269(10) . ?
C2 N3 1.329(10) . ?
C2 C3 1.545(14) . ?
C4 O1 1.4197(14) . ?
C4 C6 1.5194(14) . ?
C4 H4 0.9800 . ?
O1 H1 0.8200 . ?
N1 N2 1.365(8) . ?
N1 Cu1 1.868(6) . ?
N2 Cu2 1.962(6) . ?
N3 Cu3 1.872(7) . ?
C6 H6A 0.9600 . ?
C6 H6B 0.9600 . ?
C6 H6C 0.9600 . ?
C3 O2 1.4202(13) . ?
C3 C5 1.5197(13) . ?
C3 H3 0.9800 . ?
O2 H2 0.8200 . ?
C5 H5A 0.9600 . ?
C5 H5B 0.9600 . ?
C5 H5C 0.9600 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N2 C1 N3 113.7(9) . . ?
N2 C1 C4 118.3(10) . . ?
N3 C1 C4 127.9(9) . . ?
N1 C2 N3 113.5(8) . . ?
N1 C2 C3 126.6(9) . . ?
N3 C2 C3 119.9(9) . . ?
O1 C4 C6 108.12(14) . . ?
O1 C4 C1 113.9(12) . . ?
C6 C4 C1 103.8(11) . . ?
O1 C4 H4 110.3 . . ?
C6 C4 H4 110.3 . . ?
C1 C4 H4 110.3 . . ?
C4 O1 H1 109.5 . . ?
C2 N1 N2 107.5(6) . . ?
C2 N1 Cu1 131.9(6) . . ?
N2 N1 Cu1 120.6(4) . . ?
C1 N2 N1 103.6(7) . . ?
C1 N2 Cu2 135.4(6) . . ?
N1 N2 Cu2 120.3(4) . . ?
C1 N3 C2 101.7(7) . . ?
C1 N3 Cu3 126.6(6) . . ?
C2 N3 Cu3 131.6(7) . . ?
N1 Cu1 N1 175.8(4) . 12_656 ?
N2 Cu2 N2 119.985(10) 3_655 . ?
N2 Cu2 N2 119.986(10) 3_655 4_665 ?
N2 Cu2 N2 119.984(9) . 4_665 ?
N3 Cu3 N3 176.7(5) . 8_766 ?
C4 C6 H6A 109.5 . . ?
C4 C6 H6B 109.5 . . ?
H6A C6 H6B 109.5 . . ?
C4 C6 H6C 109.5 . . ?
H6A C6 H6C 109.5 . . ?
H6B C6 H6C 109.5 . . ?
O2 C3 C5 108.05(14) . . ?
O2 C3 C2 113.2(12) . . ?
C5 C3 C2 105.0(11) . . ?
O2 C3 H3 110.2 . . ?
C5 C3 H3 110.2 . . ?
C2 C3 H3 110.2 . . ?
C3 O2 H2 109.5 . . ?
C3 C5 H5A 109.5 . . ?
C3 C5 H5B 109.5 . . ?
H5A C5 H5B 109.5 . . ?
C3 C5 H5C 109.5 . . ?
H5A C5 H5C 109.5 . . ?
H5B C5 H5C 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N2 C1 C4 O1 -116.6(11) . . . . ?
N3 C1 C4 O1 60.2(16) . . . . ?
N2 C1 C4 C6 126.1(11) . . . . ?
N3 C1 C4 C6 -57.1(15) . . . . ?
N3 C2 N1 N2 0.5(10) . . . . ?
C3 C2 N1 N2 178.8(9) . . . . ?
N3 C2 N1 Cu1 -179.0(6) . . . . ?
C3 C2 N1 Cu1 -0.7(15) . . . . ?
N3 C1 N2 N1 1.4(11) . . . . ?
C4 C1 N2 N1 178.6(9) . . . . ?
N3 C1 N2 Cu2 171.9(6) . . . . ?
C4 C1 N2 Cu2 -10.8(15) . . . . ?
C2 N1 N2 C1 -1.1(9) . . . . ?
Cu1 N1 N2 C1 178.5(6) . . . . ?
C2 N1 N2 Cu2 -173.4(6) . . . . ?
Cu1 N1 N2 Cu2 6.1(8) . . . . ?
N2 C1 N3 C2 -1.1(11) . . . . ?
C4 C1 N3 C2 -178.1(11) . . . . ?
N2 C1 N3 Cu3 -179.1(6) . . . . ?
C4 C1 N3 Cu3 3.9(16) . . . . ?
N1 C2 N3 C1 0.3(11) . . . . ?
C3 C2 N3 C1 -178.1(9) . . . . ?
N1 C2 N3 Cu3 178.2(6) . . . . ?
C3 C2 N3 Cu3 -0.2(14) . . . . ?
N1 C2 C3 O2 96.0(13) . . . . ?
N3 C2 C3 O2 -85.7(12) . . . . ?
N1 C2 C3 C5 -21.6(15) . . . . ?
N3 C2 C3 C5 156.7(10) . . . . ?

_refine_diff_density_max         0.592
_refine_diff_density_min         -0.321
_refine_diff_density_rms         0.072





# start Validation Reply Form
_vrf_CHEMW03_2M                  
;
PROBLEM: ALERT: The ratio of given/expected molecular weight as
RESPONSE: Since the anions and solvent moleculars as well as 
 the missing hydrogen atoms mentioned previously are absent 
 from the model, the calculated molecular formula would be 
 incorrect.Finally,these results were introduced to the formula 
 unit directly which consequently generates significant 
 A-level and B-level errors (e.g. density, chemical formula, 
 density) in the final CIF output.
;
_vrf_PLAT341_2M                  
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............    0.01825 Ang.  
RESPONSE:Single crystals of 2 were found to be weakly 
 diffracting and much effort to get better diffracting 
 data were failed. 
;
_vrf_PLAT420_2M                  
;
PROBLEM: D-H Without Acceptor       O1     --  H1     ...     Please Check 
RESPONSE: The free water moleculars and anions in the crystal channels 
 have been eliminated by the SQUEEZE routine of PLATON 
 software. As a result,the terminal alcohol group is isolated 
 in the structures.
;
# end Validation Reply Form


