# Electronic Supplementary Material (ESI) for Faraday Discussions.
# 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_1
_database_code_depnum_ccdc_archive 'CCDC 1527726'
_audit_update_record             
;
2017-01-16 deposited with the CCDC.
2017-02-13 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C12 H5 Cu2 N9'
_chemical_formula_weight         402.35

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'

_space_group_crystal_system      tetragonal
_space_group_IT_number           98
_space_group_name_H-M_alt        'I 41 2 2'
_space_group_name_Hall           'I 4bw 2bw'

_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'
'-y, x+1/2, z+1/4'
'-x+1/2, -y+1/2, z+1/2'
'y+1/2, -x, z+3/4'
'x, -y+1/2, -z+1/4'
'y+1/2, x+1/2, -z+1/2'
'-x+1/2, y, -z+3/4'
'-y, -x, -z'
'x+1/2, y+1/2, z+1/2'
'-y+1/2, x+1, z+3/4'
'-x+1, -y+1, z+1'
'y+1, -x+1/2, z+5/4'
'x+1/2, -y+1, -z+3/4'
'y+1, x+1, -z+1'
'-x+1, y+1/2, -z+5/4'
'-y+1/2, -x+1/2, -z+1/2'

_cell_length_a                   9.281(17)
_cell_length_b                   9.281(17)
_cell_length_c                   22.07(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1901(8)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    885
_cell_measurement_theta_min      2.38
_cell_measurement_theta_max      26.79

_exptl_crystal_description       Block
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.406
_exptl_crystal_F_000             792
_exptl_transmission_factor_min   0.864
_exptl_transmission_factor_max   0.864
_exptl_crystal_size_max          0.150
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    2.247
_shelx_estimated_absorpt_T_min   0.729
_shelx_estimated_absorpt_T_max   0.807
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   sadabs
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  CCD
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            5753
_diffrn_reflns_av_unetI/netI     0.0915
_diffrn_reflns_av_R_equivalents  0.1513
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_theta_min         3.104
_diffrn_reflns_theta_max         28.517
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             1215
_reflns_number_gt                912
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.642
_reflns_Friedel_fraction_max     0.996
_reflns_Friedel_fraction_full    1.000

_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       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_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)+(0.1167P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.46(10)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         1215
_refine_ls_number_parameters     76
_refine_ls_number_restraints     12
_refine_ls_R_factor_all          0.0993
_refine_ls_R_factor_gt           0.0721
_refine_ls_wR_factor_ref         0.1951
_refine_ls_wR_factor_gt          0.1753
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_restrained_S_all      1.051
_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
C5 C 0.739(10) 0.767(10) 0.064(5) 0.096(19) Uani 0.25 1 d . U P A -1
C4 C 0.683(7) 0.724(15) 0.110(4) 0.10(3) Uani 0.25 1 d . . P A -1
H4A H 0.7286 0.6362 0.1221 0.152 Uiso 0.25 1 calc R U P A -1
H4B H 0.5824 0.7059 0.1020 0.152 Uiso 0.25 1 calc R U P A -1
H4C H 0.6922 0.7950 0.1409 0.152 Uiso 0.25 1 calc R U P A -1
N3 N 0.781(6) 0.780(6) 0.018(2) 0.076(15) Uani 0.25 1 d . U P A -1
Cu1 Cu 0.2500 0.78923(15) 0.8750 0.0328(5) Uani 1 2 d S T P . .
N1 N 0.1623(9) 0.6769(9) 0.9409(3) 0.039(2) Uani 1 1 d . . . . .
N2 N 0.0808(8) 0.5907(8) 1.0911(3) 0.0337(19) Uani 1 1 d . . . . .
C3 C 0.1118(11) 0.6257(10) 0.9827(4) 0.036(2) Uani 1 1 d . . . . .
C2 C 0.0506(9) 0.5555(9) 1.0326(3) 0.029(2) Uani 1 1 d . . . . .
C1 C 0.0000 0.5000 1.1227(5) 0.033(3) Uani 1 2 d S T P . .
H1 H 0.0000 0.5000 1.1648 0.039 Uiso 1 2 calc R U P . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C5 C4 1.20(15) . ?
C5 N3 1.08(10) . ?
C4 H4A 0.9600 . ?
C4 H4B 0.9600 . ?
C4 H4C 0.9600 . ?
Cu1 N1 1.966(8) 7_556 ?
Cu1 N1 1.966(8) . ?
Cu1 N2 2.050(8) 8_667 ?
Cu1 N2 2.050(8) 4_464 ?
N1 C3 1.139(11) . ?
N2 C1 1.326(9) . ?
N2 C2 1.360(10) . ?
N2 Cu1 2.050(8) 2_655 ?
C3 C2 1.401(11) . ?
C2 C2 1.394(18) 11_454 ?
C1 N2 1.326(9) 11_454 ?
C1 H1 0.9300 . ?

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
C4 C5 N3 165(10) . . ?
C5 C4 H4A 109.5 . . ?
C5 C4 H4B 109.5 . . ?
H4A C4 H4B 109.5 . . ?
C5 C4 H4C 109.5 . . ?
H4A C4 H4C 109.5 . . ?
H4B C4 H4C 109.5 . . ?
N1 Cu1 N1 115.9(5) 7_556 . ?
N1 Cu1 N2 106.5(3) 7_556 8_667 ?
N1 Cu1 N2 109.9(3) . 8_667 ?
N1 Cu1 N2 109.9(3) 7_556 4_464 ?
N1 Cu1 N2 106.5(3) . 4_464 ?
N2 Cu1 N2 107.9(4) 8_667 4_464 ?
C3 N1 Cu1 172.4(8) . . ?
C1 N2 C2 103.3(8) . . ?
C1 N2 Cu1 126.8(6) . 2_655 ?
C2 N2 Cu1 129.9(6) . 2_655 ?
N1 C3 C2 177.0(10) . . ?
N2 C2 C2 108.5(5) . 11_454 ?
N2 C2 C3 123.5(8) . . ?
C2 C2 C3 128.1(5) 11_454 . ?
N2 C1 N2 116.5(10) 11_454 . ?
N2 C1 H1 121.8 11_454 . ?
N2 C1 H1 121.8 . . ?

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
C1 N2 C2 C2 0.9(11) . . . 11_454 ?
Cu1 N2 C2 C2 -176.5(7) 2_655 . . 11_454 ?
C1 N2 C2 C3 179.4(8) . . . . ?
Cu1 N2 C2 C3 2.1(13) 2_655 . . . ?
C2 N2 C1 N2 -0.3(4) . . . 11_454 ?
Cu1 N2 C1 N2 177.1(7) 2_655 . . 11_454 ?

_refine_diff_density_max         1.738
_refine_diff_density_min         -1.168
_refine_diff_density_rms         0.177



