# 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_CuBIm-Br
_database_code_depnum_ccdc_archive 'CCDC 1565655'
_audit_update_record             
;
2017-11-02 deposited with the CCDC.
2017-11-07 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2017/1
_shelx_SHELXL_version_number     2017/1
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C8 H7 Br Cu N6'
_chemical_formula_weight         330.65

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'
N N 0.0311 0.0180 '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'
Br Br -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_H-M_alt        'R -3 :H'
_space_group_name_Hall           '-R 3'

_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-y, z'
'-x+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+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, -z'
'y, -x+y, -z'
'x-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+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'

_cell_length_a                   28.5210(7)
_cell_length_b                   28.5210(7)
_cell_length_c                   9.6037(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     6765.5(4)
_cell_formula_units_Z            18
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    5003
_cell_measurement_theta_min      4.9230
_cell_measurement_theta_max      73.8000

_exptl_crystal_description       needle
_exptl_crystal_colour            green
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.461
_exptl_crystal_F_000             2898
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.290
_exptl_crystal_size_mid          0.220
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    5.064
_shelx_estimated_absorpt_T_min   0.321
_shelx_estimated_absorpt_T_max   0.631
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.67616
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            6910
_diffrn_reflns_av_unetI/netI     0.0238
_diffrn_reflns_av_R_equivalents  0.0197
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         3.099
_diffrn_reflns_theta_max         73.983
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.966
_diffrn_measured_fraction_theta_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_point_group_measured_fraction_full 0.991
_reflns_number_total             2934
_reflns_number_gt                2755
_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.
 
 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.
;

_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2017/1 (Sheldrick, 2017)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0303P)²+25.1372P] 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_number_reflns         2934
_refine_ls_number_parameters     140
_refine_ls_number_restraints     19
_refine_ls_R_factor_all          0.0370
_refine_ls_R_factor_gt           0.0350
_refine_ls_wR_factor_ref         0.0846
_refine_ls_wR_factor_gt          0.0836
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_restrained_S_all      1.106
_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 0.77577(2) 0.68260(2) 0.80962(4) 0.03511(12) Uani 1 1 d . . . . .
Br1 Br 0.78789(2) 0.76218(2) 0.99108(3) 0.05319(13) Uani 1 1 d . . . . .
C1 C 0.70342(14) 0.70706(12) 0.6274(3) 0.0436(7) Uani 1 1 d . . . . .
H1 H 0.669693 0.680339 0.664878 0.052 Uiso 1 1 calc R U . . .
C2 C 0.76298(13) 0.77509(12) 0.5071(3) 0.0393(6) Uani 1 1 d . . . . .
H2 H 0.779625 0.804915 0.444873 0.047 Uiso 1 1 calc R U . . .
C3 C 0.78938(14) 0.75510(13) 0.5861(3) 0.0429(7) Uani 1 1 d D . . . .
C4 C 0.8387(3) 0.7638(3) 0.6109(7) 0.0405(4) Uani 0.525(3) 1 d D U P A 1
H4 H 0.869157 0.790422 0.560746 0.049 Uiso 0.525(3) 1 calc R U P A 1
C5 C 0.9066(3) 0.7236(3) 0.8254(7) 0.0405(4) Uani 0.525(3) 1 d D U P A 1
H5 H 0.943612 0.734043 0.837424 0.049 Uiso 0.525(3) 1 calc R U P A 1
C6 C 0.86849(12) 0.68054(13) 0.9247(3) 0.0411(7) Uani 1 1 d D . . . .
C7 C 0.88586(13) 0.65820(14) 1.0242(3) 0.0437(7) Uani 1 1 d . . . . .
H7 H 0.922267 0.668521 1.045904 0.052 Uiso 1 1 calc R U . . .
C8 C 0.79699(14) 0.61683(14) 1.0253(3) 0.0465(7) Uani 1 1 d . . . . .
H8 H 0.760431 0.592517 1.050311 0.056 Uiso 1 1 calc R U . . .
C4A C 0.8522(3) 0.7827(3) 0.5907(7) 0.0405(4) Uani 0.475(3) 1 d D U P A 2
H4A H 0.870208 0.812499 0.528805 0.049 Uiso 0.475(3) 1 calc R U P A 2
C5A C 0.8911(3) 0.7217(3) 0.8306(8) 0.0405(4) Uani 0.475(3) 1 d D U P A 2
H5A H 0.929211 0.743490 0.820047 0.049 Uiso 0.475(3) 1 calc R U P A 2
N1 N 0.75052(12) 0.71154(11) 0.6616(2) 0.0468(6) Uani 1 1 d . . . . .
N2 N 0.70862(11) 0.74461(10) 0.5337(2) 0.0387(5) Uani 1 1 d . . . . .
N3 N 0.89743(19) 0.7488(2) 0.7263(5) 0.0405(4) Uani 0.525(3) 1 d D U P A 1
N4 N 0.8439(2) 0.7348(2) 0.7055(5) 0.0405(4) Uani 0.525(3) 1 d D U P A 1
N5 N 0.81235(11) 0.65370(11) 0.9275(3) 0.0427(6) Uani 1 1 d . . . . .
N6 N 0.84047(11) 0.61834(11) 1.0855(3) 0.0454(6) Uani 1 1 d . . . . .
H6 H 0.839557 0.597064 1.153126 0.055 Uiso 1 1 calc R U . . .
N3A N 0.8850(2) 0.7725(2) 0.6642(5) 0.0405(4) Uani 0.475(3) 1 d D U P A 2
N4A N 0.8577(2) 0.7294(2) 0.7564(6) 0.0405(4) Uani 0.475(3) 1 d D U P A 2


_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 1.953(3) . ?
Cu1 N5 1.977(2) . ?
Cu1 N2 1.984(3) 6_565 ?
Cu1 N4 2.024(5) . ?
Cu1 N4A 2.095(6) . ?
Cu1 Br1 2.7430(5) . ?
C1 N1 1.325(4) . ?
C1 N2 1.349(4) . ?
C1 H1 0.9500 . ?
C2 N2 1.370(4) . ?
C2 C3 1.377(4) . ?
C2 H2 0.9500 . ?
C3 C4 1.323(7) . ?
C3 N1 1.386(4) . ?
C3 C4A 1.556(7) . ?
C4 N4 1.286(7) . ?
C4 H4 0.9500 . ?
C5 N3 1.297(7) . ?
C5 C6 1.504(7) . ?
C5 H5 0.9500 . ?
C6 C5A 1.361(8) . ?
C6 C7 1.371(4) . ?
C6 N5 1.387(4) . ?
C7 N6 1.358(4) . ?
C7 H7 0.9500 . ?
C8 N5 1.312(4) . ?
C8 N6 1.349(4) . ?
C8 H8 0.9500 . ?
C4A N3A 1.315(8) . ?
C4A H4A 0.9500 . ?
C5A N4A 1.292(8) . ?
C5A H5A 0.9500 . ?
N3 N4 1.387(6) . ?
N6 H6 0.8800 . ?
N3A N4A 1.395(7) . ?

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 N5 167.35(12) . . ?
N1 Cu1 N2 95.60(11) . 6_565 ?
N5 Cu1 N2 92.77(11) . 6_565 ?
N1 Cu1 N4 75.55(17) . . ?
N5 Cu1 N4 94.43(16) . . ?
N2 Cu1 N4 166.46(16) 6_565 . ?
N1 Cu1 N4A 94.77(18) . . ?
N5 Cu1 N4A 75.62(17) . . ?
N2 Cu1 N4A 166.39(17) 6_565 . ?
N1 Cu1 Br1 91.91(8) . . ?
N5 Cu1 Br1 96.13(7) . . ?
N2 Cu1 Br1 99.05(7) 6_565 . ?
N4 Cu1 Br1 91.57(14) . . ?
N4A Cu1 Br1 89.39(15) . . ?
N1 C1 N2 112.6(3) . . ?
N1 C1 H1 123.7 . . ?
N2 C1 H1 123.7 . . ?
N2 C2 C3 108.3(3) . . ?
N2 C2 H2 125.8 . . ?
C3 C2 H2 125.8 . . ?
C4 C3 C2 140.5(4) . . ?
C4 C3 N1 111.9(4) . . ?
C2 C3 N1 107.6(3) . . ?
C2 C3 C4A 122.4(4) . . ?
N1 C3 C4A 129.9(4) . . ?
N4 C4 C3 117.3(5) . . ?
N4 C4 H4 121.3 . . ?
C3 C4 H4 121.3 . . ?
N3 C5 C6 130.9(5) . . ?
N3 C5 H5 114.5 . . ?
C6 C5 H5 114.5 . . ?
C5A C6 C7 137.5(4) . . ?
C5A C6 N5 114.0(4) . . ?
C7 C6 N5 108.4(3) . . ?
C7 C6 C5 122.7(3) . . ?
N5 C6 C5 128.7(3) . . ?
N6 C7 C6 106.1(3) . . ?
N6 C7 H7 127.0 . . ?
C6 C7 H7 127.0 . . ?
N5 C8 N6 110.4(3) . . ?
N5 C8 H8 124.8 . . ?
N6 C8 H8 124.8 . . ?
N3A C4A C3 132.0(6) . . ?
N3A C4A H4A 114.0 . . ?
C3 C4A H4A 114.0 . . ?
N4A C5A C6 116.1(6) . . ?
N4A C5A H5A 121.9 . . ?
C6 C5A H5A 121.9 . . ?
C1 N1 C3 105.9(3) . . ?
C1 N1 Cu1 135.2(2) . . ?
C3 N1 Cu1 117.5(2) . . ?
C1 N2 C2 105.6(3) . . ?
C1 N2 Cu1 125.9(2) . 8_654 ?
C2 N2 Cu1 127.67(19) . 8_654 ?
C5 N3 N4 116.3(5) . . ?
C4 N4 N3 112.3(5) . . ?
C4 N4 Cu1 116.5(4) . . ?
N3 N4 Cu1 130.9(4) . . ?
C8 N5 C6 106.7(3) . . ?
C8 N5 Cu1 135.2(2) . . ?
C6 N5 Cu1 117.6(2) . . ?
C8 N6 C7 108.5(3) . . ?
C8 N6 H6 125.8 . . ?
C7 N6 H6 125.8 . . ?
C4A N3A N4A 113.0(5) . . ?
C5A N4A N3A 111.5(6) . . ?
C5A N4A Cu1 116.1(5) . . ?
N3A N4A Cu1 132.0(4) . . ?

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 C2 C3 C4 179.4(6) . . . . ?
N2 C2 C3 N1 0.3(3) . . . . ?
N2 C2 C3 C4A -175.3(4) . . . . ?
C2 C3 C4 N4 175.6(4) . . . . ?
N1 C3 C4 N4 -5.3(7) . . . . ?
N3 C5 C6 C7 179.9(6) . . . . ?
N3 C5 C6 N5 5.6(10) . . . . ?
C5A C6 C7 N6 177.6(6) . . . . ?
N5 C6 C7 N6 0.1(3) . . . . ?
C5 C6 C7 N6 -175.2(4) . . . . ?
C2 C3 C4A N3A 175.1(6) . . . . ?
N1 C3 C4A N3A 0.6(10) . . . . ?
C7 C6 C5A N4A -178.5(5) . . . . ?
N5 C6 C5A N4A -1.1(8) . . . . ?
N2 C1 N1 C3 0.4(3) . . . . ?
N2 C1 N1 Cu1 165.8(2) . . . . ?
C4 C3 N1 C1 -179.8(4) . . . . ?
C2 C3 N1 C1 -0.4(3) . . . . ?
C4A C3 N1 C1 174.7(4) . . . . ?
C4 C3 N1 Cu1 11.7(4) . . . . ?
C2 C3 N1 Cu1 -168.87(19) . . . . ?
C4A C3 N1 Cu1 6.3(5) . . . . ?
N1 C1 N2 C2 -0.2(3) . . . . ?
N1 C1 N2 Cu1 -169.97(19) . . . 8_654 ?
C3 C2 N2 C1 -0.1(3) . . . . ?
C3 C2 N2 Cu1 169.44(19) . . . 8_654 ?
C6 C5 N3 N4 0.1(10) . . . . ?
C3 C4 N4 N3 -177.6(5) . . . . ?
C3 C4 N4 Cu1 -3.0(8) . . . . ?
C5 N3 N4 C4 176.3(6) . . . . ?
C5 N3 N4 Cu1 2.7(8) . . . . ?
N6 C8 N5 C6 -0.3(3) . . . . ?
N6 C8 N5 Cu1 -171.6(2) . . . . ?
C5A C6 N5 C8 -178.0(4) . . . . ?
C7 C6 N5 C8 0.1(3) . . . . ?
C5 C6 N5 C8 175.1(4) . . . . ?
C5A C6 N5 Cu1 -4.9(5) . . . . ?
C7 C6 N5 Cu1 173.2(2) . . . . ?
C5 C6 N5 Cu1 -11.9(5) . . . . ?
N5 C8 N6 C7 0.4(3) . . . . ?
C6 C7 N6 C8 -0.3(3) . . . . ?
C3 C4A N3A N4A -1.2(10) . . . . ?
C6 C5A N4A N3A 179.6(5) . . . . ?
C6 C5A N4A Cu1 6.3(9) . . . . ?
C4A N3A N4A C5A -177.6(6) . . . . ?
C4A N3A N4A Cu1 -5.7(8) . . . . ?

_refine_diff_density_max         0.557
_refine_diff_density_min         -0.683
_refine_diff_density_rms         0.063



####################################################################### 
# 
# 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_CuBIm-Cl
_database_code_depnum_ccdc_archive 'CCDC 1565656'
_audit_update_record             
;
2017-11-02 deposited with the CCDC.
2017-11-07 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2017/1
_shelx_SHELXL_version_number     2017/1
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C8 H7 Cl Cu N6'
_chemical_formula_weight         286.19

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'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.3639 0.7018 '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'

_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_H-M_alt        'R -3 :H'
_space_group_name_Hall           '-R 3'

_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-y, z'
'-x+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+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, -z'
'y, -x+y, -z'
'x-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+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'

_cell_length_a                   27.9457(7)
_cell_length_b                   27.9457(7)
_cell_length_c                   9.7132(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     6569.4(4)
_cell_formula_units_Z            18
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    4654
_cell_measurement_theta_min      4.8840
_cell_measurement_theta_max      73.7830

_exptl_crystal_description       needle
_exptl_crystal_colour            green
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.302
_exptl_crystal_F_000             2574
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.08
_exptl_absorpt_coefficient_mu    3.691
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.60531
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            7036
_diffrn_reflns_av_unetI/netI     0.0397
_diffrn_reflns_av_R_equivalents  0.0354
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         3.163
_diffrn_reflns_theta_max         73.982
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.962
_diffrn_measured_fraction_theta_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_point_group_measured_fraction_full 0.993
_reflns_number_total             2857
_reflns_number_gt                2637
_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.
 
 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.
;

_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2017/1 (Sheldrick, 2017)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0555P)²+10.1348P] 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_number_reflns         2857
_refine_ls_number_parameters     164
_refine_ls_number_restraints     15
_refine_ls_R_factor_all          0.0401
_refine_ls_R_factor_gt           0.0379
_refine_ls_wR_factor_ref         0.1077
_refine_ls_wR_factor_gt          0.1060
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_restrained_S_all      1.069
_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 0.76117(2) 0.64954(2) 0.01733(3) 0.03632(14) Uani 1 1 d . . . . .
N1 N 0.70549(9) 0.62058(9) 0.16332(19) 0.0473(5) Uani 1 1 d . . . . .
N2 N 0.62948(8) 0.58731(8) 0.29192(18) 0.0400(4) Uani 1 1 d . . . . .
N5 N 0.82908(8) 0.67890(9) -0.0960(2) 0.0422(4) Uani 1 1 d . . . . .
N6 N 0.89246(8) 0.71293(9) -0.2563(2) 0.0464(5) Uani 1 1 d . . . . .
H6 H 0.913018 0.734033 -0.324251 0.056 Uiso 1 1 calc R U . . .
C1 C 0.66168(10) 0.62469(10) 0.1959(2) 0.0442(6) Uani 1 1 d . . . . .
H1 H 0.653731 0.651008 0.156246 0.053 Uiso 1 1 calc R U . . .
C2 C 0.65458(10) 0.55765(10) 0.3212(2) 0.0404(5) Uani 1 1 d . . . . .
H2 H 0.641903 0.528044 0.385130 0.049 Uiso 1 1 calc R U . . .
C3 C 0.70164(10) 0.57798(11) 0.2421(2) 0.0454(6) Uani 1 1 d D . . . .
C6 C 0.85742(9) 0.65012(11) -0.0967(2) 0.0425(5) Uani 1 1 d D . . . .
C7 C 0.89669(10) 0.67146(12) -0.1972(2) 0.0444(6) Uani 1 1 d . . . . .
H7 H 0.922042 0.659518 -0.220902 0.053 Uiso 1 1 calc R U . . .
C8 C 0.85117(10) 0.71646(11) -0.1932(2) 0.0452(5) Uani 1 1 d . . . . .
H8 H 0.839800 0.742353 -0.215849 0.054 Uiso 1 1 calc R U . . .
Cl2 Cl 0.69759(3) 0.57472(3) -0.15757(6) 0.05115(19) Uani 1 1 d . . . . .
C4 C 0.7361(3) 0.5489(3) 0.2383(7) 0.0473(7) Uani 0.448(6) 1 d D U P A 1
H4 H 0.723387 0.518655 0.300212 0.057 Uiso 0.448(6) 1 calc R U P A 1
C5 C 0.8375(3) 0.6044(4) -0.0020(8) 0.0473(7) Uani 0.448(6) 1 d D U P A 1
H5 H 0.851950 0.580162 0.005278 0.057 Uiso 0.448(6) 1 calc R U P A 1
N3 N 0.78012(18) 0.5578(2) 0.1656(4) 0.0418(14) Uani 0.448(6) 1 d D U P A 1
N4 N 0.7970(2) 0.6008(2) 0.0725(6) 0.0399(13) Uani 0.448(6) 1 d D U P A 1
N3A N 0.81675(16) 0.58069(18) 0.1006(4) 0.0429(12) Uani 0.552(6) 1 d D U P A 2
C4A C 0.7446(2) 0.5686(3) 0.2183(6) 0.0473(7) Uani 0.552(6) 1 d D U P A 2
H4A H 0.749632 0.542912 0.271293 0.057 Uiso 0.552(6) 1 calc R U P A 2
C5A C 0.8524(2) 0.6081(3) 0.0000(6) 0.0473(7) Uani 0.552(6) 1 d D U P A 2
H5A H 0.880141 0.598198 -0.010842 0.057 Uiso 0.552(6) 1 calc R U P A 2
N4A N 0.77745(19) 0.59642(18) 0.1207(5) 0.0375(11) Uani 0.552(6) 1 d D U P A 2


_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(2) . ?
Cu1 N5 1.9824(19) . ?
Cu1 N2 1.988(2) 8_654 ?
Cu1 N4A 2.024(4) . ?
Cu1 N4 2.124(6) . ?
Cu1 Cl2 2.5884(7) . ?
N1 C1 1.324(3) . ?
N1 C3 1.373(3) . ?
N2 C1 1.353(3) . ?
N2 C2 1.357(3) . ?
N5 C8 1.314(3) . ?
N5 C6 1.382(3) . ?
N6 C7 1.351(3) . ?
N6 C8 1.353(3) . ?
N6 H6 0.8800 . ?
C1 H1 0.9500 . ?
C2 C3 1.377(3) . ?
C2 H2 0.9500 . ?
C3 C4A 1.370(7) . ?
C3 C4 1.539(8) . ?
C6 C7 1.363(3) . ?
C6 C5 1.441(10) . ?
C6 C5A 1.455(8) . ?
C7 H7 0.9500 . ?
C8 H8 0.9500 . ?
C4 N3 1.330(8) . ?
C4 H4 0.9500 . ?
C5 N4 1.303(9) . ?
C5 H5 0.9500 . ?
N3 N4 1.383(7) . ?
N3A C5A 1.330(7) . ?
N3A N4A 1.385(5) . ?
C4A N4A 1.277(8) . ?
C4A H4A 0.9500 . ?
C5A H5A 0.9500 . ?

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 N5 166.55(9) . . ?
N1 Cu1 N2 95.51(9) . 8_654 ?
N5 Cu1 N2 93.11(8) . 8_654 ?
N1 Cu1 N4A 76.17(16) . . ?
N5 Cu1 N4A 93.41(15) . . ?
N2 Cu1 N4A 166.82(14) 8_654 . ?
N1 Cu1 N4 94.83(17) . . ?
N5 Cu1 N4 75.22(17) . . ?
N2 Cu1 N4 166.50(17) 8_654 . ?
N1 Cu1 Cl2 93.37(6) . . ?
N5 Cu1 Cl2 95.63(6) . . ?
N2 Cu1 Cl2 97.97(6) 8_654 . ?
N4A Cu1 Cl2 92.77(12) . . ?
N4 Cu1 Cl2 90.05(15) . . ?
C1 N1 C3 105.5(2) . . ?
C1 N1 Cu1 135.75(19) . . ?
C3 N1 Cu1 117.62(18) . . ?
C1 N2 C2 105.6(2) . . ?
C1 N2 Cu1 125.70(18) . 6_565 ?
C2 N2 Cu1 127.97(15) . 6_565 ?
C8 N5 C6 106.5(2) . . ?
C8 N5 Cu1 134.42(18) . . ?
C6 N5 Cu1 118.05(16) . . ?
C7 N6 C8 108.3(2) . . ?
C7 N6 H6 125.9 . . ?
C8 N6 H6 125.9 . . ?
N1 C1 N2 112.6(2) . . ?
N1 C1 H1 123.7 . . ?
N2 C1 H1 123.7 . . ?
N2 C2 C3 108.0(2) . . ?
N2 C2 H2 126.0 . . ?
C3 C2 H2 126.0 . . ?
C4A C3 N1 112.0(3) . . ?
C4A C3 C2 139.7(3) . . ?
N1 C3 C2 108.3(2) . . ?
N1 C3 C4 130.2(3) . . ?
C2 C3 C4 121.0(4) . . ?
C7 C6 N5 108.6(2) . . ?
C7 C6 C5 135.6(4) . . ?
N5 C6 C5 115.6(4) . . ?
C7 C6 C5A 123.2(3) . . ?
N5 C6 C5A 127.9(3) . . ?
N6 C7 C6 106.4(2) . . ?
N6 C7 H7 126.8 . . ?
C6 C7 H7 126.8 . . ?
N5 C8 N6 110.1(2) . . ?
N5 C8 H8 124.9 . . ?
N6 C8 H8 124.9 . . ?
N3 C4 C3 132.7(6) . . ?
N3 C4 H4 113.7 . . ?
C3 C4 H4 113.7 . . ?
N4 C5 C6 111.1(7) . . ?
N4 C5 H5 124.5 . . ?
C6 C5 H5 124.5 . . ?
C4 N3 N4 113.1(6) . . ?
C5 N4 N3 109.7(6) . . ?
C5 N4 Cu1 118.6(5) . . ?
N3 N4 Cu1 131.0(4) . . ?
C5A N3A N4A 113.9(5) . . ?
N4A C4A C3 116.2(6) . . ?
N4A C4A H4A 121.9 . . ?
C3 C4A H4A 121.9 . . ?
N3A C5A C6 132.9(5) . . ?
N3A C5A H5A 113.6 . . ?
C6 C5A H5A 113.6 . . ?
C4A N4A N3A 110.8(5) . . ?
C4A N4A Cu1 117.2(4) . . ?
N3A N4A Cu1 131.8(4) . . ?

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
C3 N1 C1 N2 0.2(3) . . . . ?
Cu1 N1 C1 N2 167.02(17) . . . . ?
C2 N2 C1 N1 -0.2(3) . . . . ?
Cu1 N2 C1 N1 -170.95(15) 6_565 . . . ?
C1 N2 C2 C3 0.1(2) . . . . ?
Cu1 N2 C2 C3 170.57(16) 6_565 . . . ?
C1 N1 C3 C4A 179.6(3) . . . . ?
Cu1 N1 C3 C4A 10.0(4) . . . . ?
C1 N1 C3 C2 -0.1(3) . . . . ?
Cu1 N1 C3 C2 -169.77(15) . . . . ?
C1 N1 C3 C4 171.8(4) . . . . ?
Cu1 N1 C3 C4 2.2(5) . . . . ?
N2 C2 C3 C4A -179.6(5) . . . . ?
N2 C2 C3 N1 0.0(3) . . . . ?
N2 C2 C3 C4 -172.8(4) . . . . ?
C8 N5 C6 C7 -0.3(3) . . . . ?
Cu1 N5 C6 C7 169.91(16) . . . . ?
C8 N5 C6 C5 -176.6(4) . . . . ?
Cu1 N5 C6 C5 -6.5(5) . . . . ?
C8 N5 C6 C5A 173.4(4) . . . . ?
Cu1 N5 C6 C5A -16.5(5) . . . . ?
C8 N6 C7 C6 -0.3(3) . . . . ?
N5 C6 C7 N6 0.3(3) . . . . ?
C5 C6 C7 N6 175.7(5) . . . . ?
C5A C6 C7 N6 -173.7(4) . . . . ?
C6 N5 C8 N6 0.1(3) . . . . ?
Cu1 N5 C8 N6 -167.73(17) . . . . ?
C7 N6 C8 N5 0.1(3) . . . . ?
N1 C3 C4 N3 4.0(10) . . . . ?
C2 C3 C4 N3 175.1(6) . . . . ?
C7 C6 C5 N4 -178.2(4) . . . . ?
N5 C6 C5 N4 -3.1(8) . . . . ?
C3 C4 N3 N4 -2.1(10) . . . . ?
C6 C5 N4 N3 -177.9(5) . . . . ?
C6 C5 N4 Cu1 10.8(8) . . . . ?
C4 N3 N4 C5 -175.2(7) . . . . ?
C4 N3 N4 Cu1 -5.4(8) . . . . ?
N1 C3 C4A N4A -6.2(6) . . . . ?
C2 C3 C4A N4A 173.4(4) . . . . ?
N4A N3A C5A C6 -2.4(9) . . . . ?
C7 C6 C5A N3A -177.2(6) . . . . ?
N5 C6 C5A N3A 10.0(10) . . . . ?
C3 C4A N4A N3A -175.9(4) . . . . ?
C3 C4A N4A Cu1 0.0(7) . . . . ?
C5A N3A N4A C4A 179.9(6) . . . . ?
C5A N3A N4A Cu1 4.8(7) . . . . ?

_refine_diff_density_max         0.526
_refine_diff_density_min         -0.253
_refine_diff_density_rms         0.066



