# Electronic Supplementary Material (ESI) for Energy & Environmental Science.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# 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_cuhl30
_database_code_depnum_ccdc_archive 'CCDC 1401162'
_audit_update_record             
;
2015-05-15 deposited with the CCDC.
2015-07-13 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C20 H12 Cu2 N2 O10'
_chemical_formula_weight         567.40

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu -1.9646 0.5888 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           trigonal
_symmetry_space_group_name_H-M   'R-3 m'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'x-y, -y, -z'
'-x, -x+y, -z'
'y, x, -z'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'x-y+2/3, -y+1/3, -z+1/3'
'-x+2/3, -x+y+1/3, -z+1/3'
'y+2/3, x+1/3, -z+1/3'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'x-y+1/3, -y+2/3, -z+2/3'
'-x+1/3, -x+y+2/3, -z+2/3'
'y+1/3, x+2/3, -z+2/3'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-x+y, y, z'
'x, x-y, z'
'-y, -x, z'
'-x+2/3, -y+1/3, -z+1/3'
'y+2/3, -x+y+1/3, -z+1/3'
'x-y+2/3, x+1/3, -z+1/3'
'-x+y+2/3, y+1/3, z+1/3'
'x+2/3, x-y+1/3, z+1/3'
'-y+2/3, -x+1/3, z+1/3'
'-x+1/3, -y+2/3, -z+2/3'
'y+1/3, -x+y+2/3, -z+2/3'
'x-y+1/3, x+2/3, -z+2/3'
'-x+y+1/3, y+2/3, z+2/3'
'x+1/3, x-y+2/3, z+2/3'
'-y+1/3, -x+2/3, z+2/3'

_cell_length_a                   18.7387(3)
_cell_length_b                   18.7387(3)
_cell_length_c                   37.4863(8)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     11399.4(4)
_cell_formula_units_Z            9
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       block
_exptl_crystal_colour            blue
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    0.744
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2556
_exptl_absorpt_coefficient_mu    1.274
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  0.8319
_exptl_absorpt_correction_T_max  0.8832
_exptl_absorpt_process_details   ?

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            13796
_diffrn_reflns_av_R_equivalents  0.0399
_diffrn_reflns_av_sigmaI/netI    0.0256
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_theta_min         3.60
_diffrn_reflns_theta_max         74.06
_reflns_number_total             2799
_reflns_number_gt                2376
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 

PLAT430_ALERT_2_A Short Inter D...A Contact  N1 .. N1..1.57 Ang.  
PLAT430_ALERT_2_A Short Inter D...A Contact  N1 .. N1..2.58 Ang.

Explanation: these two faults are due to the disorder of the central pyridazine ring. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0290P)²+56.6064P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         2799
_refine_ls_number_parameters     94
_refine_ls_number_restraints     70
_refine_ls_R_factor_all          0.0518
_refine_ls_R_factor_gt           0.0472
_refine_ls_wR_factor_ref         0.1035
_refine_ls_wR_factor_gt          0.1019
_refine_ls_goodness_of_fit_ref   0.943
_refine_ls_restrained_S_all      1.021
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.5120(2) 0.4880(2) 0.53467(14) 0.101(2) Uani 1 2 d SDU . .
C2 C 0.5267(2) 0.4733(2) 0.57142(12) 0.0724(17) Uani 1 2 d SU . .
C3 C 0.47021(19) 0.40133(19) 0.58897(8) 0.0603(9) Uani 1 1 d U . .
H3 H 0.4211 0.3624 0.5772 0.072 Uiso 1 1 calc R . .
C4 C 0.48540(16) 0.38656(16) 0.62322(7) 0.0402(6) Uani 1 1 d U . .
C5 C 0.55688(12) 0.44312(12) 0.64049(9) 0.0353(8) Uani 1 2 d SU . .
H5 H 0.5671 0.4329 0.6642 0.042 Uiso 1 2 calc SR . .
C6 C 0.42713(15) 0.30607(15) 0.64074(6) 0.0356(5) Uani 1 1 d U . .
C7 C 0.5432(6) 0.5672(4) 0.52306(19) 0.097(3) Uani 0.50 1 d PDU . .
H7 H 0.5683 0.6135 0.5386 0.117 Uiso 0.50 1 calc PR . .
Cu1 Cu 0.37924(3) 0.189622(13) 0.696095(11) 0.02602(15) Uani 1 2 d S . .
N1 N 0.5741(4) 0.5350(5) 0.51275(16) 0.101(3) Uani 0.50 1 d PDU . .
O1 O 0.44469(11) 0.29495(11) 0.67180(4) 0.0402(4) Uani 1 1 d . . .
O2 O 0.36607(11) 0.25636(11) 0.62271(5) 0.0434(5) Uani 1 1 d . . .
O3 O 0.4409(2) 0.22045(11) 0.74660(8) 0.0687(10) Uani 1 2 d SD . .
H3A H 0.4318 0.2535 0.7569 0.103 Uiso 1 1 d RD . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
C1 0.081(2) 0.081(2) 0.061(3) 0.034(2) -0.034(2) -0.020(3)
C2 0.0606(18) 0.0606(18) 0.046(2) 0.0231(14) -0.0231(14) -0.007(2)
C3 0.0461(16) 0.0506(17) 0.0445(16) 0.0133(14) -0.0146(13) -0.0055(14)
C4 0.0354(13) 0.0364(13) 0.0345(13) 0.0069(11) -0.0021(11) 0.0072(11)
C5 0.0359(12) 0.0359(12) 0.0279(16) 0.0002(7) -0.0002(7) 0.0133(15)
C6 0.0289(12) 0.0375(13) 0.0333(12) 0.0028(10) -0.0001(10) 0.0113(10)
C7 0.065(4) 0.112(6) 0.057(4) 0.035(4) -0.018(4) 0.001(4)
Cu1 0.0196(2) 0.0339(2) 0.0198(2) -0.00069(9) -0.00139(17) 0.00981(12)
N1 0.112(5) 0.064(4) 0.056(4) 0.016(3) -0.036(4) -0.009(3)
O1 0.0351(9) 0.0362(9) 0.0351(9) 0.0052(7) -0.0035(7) 0.0072(8)
O2 0.0344(9) 0.0431(10) 0.0327(9) 0.0076(8) -0.0060(7) 0.0043(8)
O3 0.077(2) 0.0783(17) 0.0503(18) -0.0158(9) -0.0316(17) 0.0385(12)

_geom_special_details            
; 
 All esds (except the esd in the dihedral angle between two l.s. planes) 
 are estimated using the full covariance matrix.  The cell esds are taken 
 into account individually in the estimation of esds in distances, angles 
 and torsion angles; correlations between esds in cell parameters are only 
 used when they are defined by crystal symmetry.  An approximate (isotropic) 
 treatment of cell esds is used for estimating esds involving l.s. planes. 
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 N1 1.334(6) 24_665 ?
C1 N1 1.334(6) . ?
C1 C7 1.367(6) 24_665 ?
C1 C7 1.367(6) . ?
C1 C2 1.457(6) . ?
C2 C3 1.395(3) 24_665 ?
C2 C3 1.395(3) . ?
C3 C4 1.373(4) . ?
C3 H3 0.9500 . ?
C4 C5 1.385(3) . ?
C4 C6 1.500(3) . ?
C5 C4 1.385(3) 24_665 ?
C5 H5 0.9500 . ?
C6 O2 1.252(3) . ?
C6 O1 1.255(3) . ?
C7 N1 1.365(5) 6_556 ?
C7 C7 1.897(18) 6_556 ?
C7 H7 0.9500 . ?
Cu1 O1 1.9515(17) . ?
Cu1 O1 1.9515(17) 23 ?
Cu1 O2 1.9528(18) 25_556 ?
Cu1 O2 1.9529(18) 11_556 ?
Cu1 O3 2.142(3) . ?
Cu1 Cu1 2.6623(9) 25_556 ?
N1 C7 1.365(5) 6_556 ?
N1 N1 1.590(17) 6_556 ?
O2 Cu1 1.9528(18) 25_556 ?
O3 H3A 0.8163 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 C1 N1 100.0(7) 24_665 . ?
N1 C1 C7 47.9(5) 24_665 24_665 ?
N1 C1 C7 119.2(5) . 24_665 ?
N1 C1 C7 119.2(5) 24_665 . ?
N1 C1 C7 47.9(5) . . ?
C7 C1 C7 98.3(8) 24_665 . ?
N1 C1 C2 121.5(4) 24_665 . ?
N1 C1 C2 121.5(4) . . ?
C7 C1 C2 119.2(5) 24_665 . ?
C7 C1 C2 119.2(5) . . ?
C3 C2 C3 119.3(4) 24_665 . ?
C3 C2 C1 120.32(19) 24_665 . ?
C3 C2 C1 120.32(19) . . ?
C4 C3 C2 120.2(3) . . ?
C4 C3 H3 119.9 . . ?
C2 C3 H3 119.9 . . ?
C3 C4 C5 120.1(2) . . ?
C3 C4 C6 119.5(2) . . ?
C5 C4 C6 120.3(2) . . ?
C4 C5 C4 120.1(3) . 24_665 ?
C4 C5 H5 119.9 . . ?
C4 C5 H5 119.9 24_665 . ?
O2 C6 O1 126.5(2) . . ?
O2 C6 C4 116.5(2) . . ?
O1 C6 C4 117.0(2) . . ?
N1 C7 C1 114.1(8) 6_556 . ?
N1 C7 C7 34.7(5) 6_556 6_556 ?
C1 C7 C7 93.1(7) . 6_556 ?
N1 C7 H7 122.9 6_556 . ?
C1 C7 H7 122.9 . . ?
C7 C7 H7 134.9 6_556 . ?
O1 Cu1 O1 88.41(11) . 23 ?
O1 Cu1 O2 167.52(7) . 25_556 ?
O1 Cu1 O2 89.73(8) 23 25_556 ?
O1 Cu1 O2 89.73(8) . 11_556 ?
O1 Cu1 O2 167.52(7) 23 11_556 ?
O2 Cu1 O2 89.43(12) 25_556 11_556 ?
O1 Cu1 O3 99.11(9) . . ?
O1 Cu1 O3 99.11(9) 23 . ?
O2 Cu1 O3 93.37(9) 25_556 . ?
O2 Cu1 O3 93.37(9) 11_556 . ?
O1 Cu1 Cu1 85.29(5) . 25_556 ?
O1 Cu1 Cu1 85.29(5) 23 25_556 ?
O2 Cu1 Cu1 82.26(5) 25_556 25_556 ?
O2 Cu1 Cu1 82.26(5) 11_556 25_556 ?
O3 Cu1 Cu1 173.82(10) . 25_556 ?
C1 N1 C7 125.4(7) . 6_556 ?
C1 N1 N1 102.9(7) . 6_556 ?
C7 N1 N1 42.7(5) 6_556 6_556 ?
C6 O1 Cu1 121.09(16) . . ?
C6 O2 Cu1 124.66(16) . 25_556 ?
Cu1 O3 H3A 109.4 . . ?

_diffrn_measured_fraction_theta_max 0.987
_diffrn_reflns_theta_full        74.06
_diffrn_measured_fraction_theta_full 0.987
_refine_diff_density_max         0.547
_refine_diff_density_min         -0.570
_refine_diff_density_rms         0.060
