# Electronic Supplementary Material (ESI) for Dalton Transactions.
# 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 1575140'
_audit_update_record             
;
2017-09-18 deposited with the CCDC.
2017-11-17 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C34 H24 Br2 Cu N4 O6'
_chemical_formula_weight         807.93

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'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   'C 2/c'

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

_cell_length_a                   11.154(2)
_cell_length_b                   27.447(6)
_cell_length_c                   11.822(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 118.042(6)
_cell_angle_gamma                90.00
_cell_volume                     3194.3(12)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2839
_cell_measurement_theta_min      2.20
_cell_measurement_theta_max      24.75

_exptl_crystal_description       needle
_exptl_crystal_colour            blue
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.20
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.680
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1612
_exptl_absorpt_coefficient_mu    3.238
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.3649
_exptl_absorpt_correction_T_max  0.5636
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            14105
_diffrn_reflns_av_R_equivalents  0.1085
_diffrn_reflns_av_sigmaI/netI    0.1096
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         2.20
_diffrn_reflns_theta_max         27.55
_reflns_number_total             3672
_reflns_number_gt                2147
_reflns_threshold_expression     >2sigma(I)

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

_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. 
;

_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)+(0.0623P)²+0.3940P] 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         3672
_refine_ls_number_parameters     215
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1253
_refine_ls_R_factor_gt           0.0613
_refine_ls_wR_factor_ref         0.1527
_refine_ls_wR_factor_gt          0.1300
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_restrained_S_all      1.014
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.001

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
Br1 Br 0.30377(7) 0.18998(3) 0.07553(6) 0.0797(3) Uani 1 1 d . . .
Cu1 Cu 0.5000 0.14818(3) 0.7500 0.0292(2) Uani 1 2 d S . .
O1 O 0.3532(4) 0.01149(13) 0.3912(3) 0.0644(11) Uani 1 1 d . . .
H1 H 0.3649 0.0187 0.4619 0.097 Uiso 1 1 d R . .
O2 O 0.4216(3) 0.14799(12) 0.5625(3) 0.0415(8) Uani 1 1 d . . .
O3 O 0.4031(4) 0.06802(12) 0.5809(3) 0.0518(9) Uani 1 1 d . . .
N1 N 0.3103(4) 0.14305(13) 0.7356(3) 0.0347(9) Uani 1 1 d . . .
N3 N 0.5000 0.23262(19) 0.7500 0.0385(13) Uani 1 2 d S . .
N4 N 0.5000 0.4911(4) 0.7500 0.153(7) Uani 1 2 d S . .
C1 C 0.3956(4) 0.10489(18) 0.5153(4) 0.0368(11) Uani 1 1 d . . .
C2 C 0.3597(4) 0.09926(17) 0.3776(4) 0.0380(11) Uani 1 1 d . . .
C3 C 0.3444(5) 0.05255(19) 0.3234(5) 0.0483(13) Uani 1 1 d . . .
C4 C 0.3192(6) 0.0473(2) 0.1969(5) 0.0638(17) Uani 1 1 d . . .
H4A H 0.3105 0.0164 0.1616 0.077 Uiso 1 1 calc R . .
C5 C 0.3072(6) 0.0881(2) 0.1241(5) 0.0670(18) Uani 1 1 d . . .
H5 H 0.2907 0.0848 0.0397 0.080 Uiso 1 1 calc R . .
C6 C 0.3196(6) 0.1335(2) 0.1768(5) 0.0534(14) Uani 1 1 d . . .
C7 C 0.3466(5) 0.13997(19) 0.3022(4) 0.0446(13) Uani 1 1 d . . .
H7 H 0.3560 0.1712 0.3360 0.054 Uiso 1 1 calc R . .
C15 C 0.2270(5) 0.18152(17) 0.7043(5) 0.0454(13) Uani 1 1 d . . .
H15 H 0.2528 0.2100 0.6789 0.054 Uiso 1 1 calc R . .
C16 C 0.2674(4) 0.10177(16) 0.7658(4) 0.0348(10) Uani 1 1 d . . .
H16 H 0.3222 0.0743 0.7853 0.042 Uiso 1 1 calc R . .
C17 C 0.0638(4) 0.13939(15) 0.7446(4) 0.0309(10) Uani 1 1 d . . .
C19 C 0.1456(4) 0.09820(16) 0.7692(4) 0.0341(10) Uani 1 1 d . . .
H19 H 0.1184 0.0686 0.7879 0.041 Uiso 1 1 calc R . .
C23 C 0.1067(5) 0.18138(16) 0.7076(5) 0.0437(12) Uani 1 1 d . . .
H23 H 0.0531 0.2093 0.6852 0.052 Uiso 1 1 calc R . .
C27 C 0.5000 0.3340(2) 0.7500 0.0442(18) Uani 1 2 d S . .
C28 C 0.4957(8) 0.3077(2) 0.6513(6) 0.078(2) Uani 1 1 d . . .
H28 H 0.4945 0.3237 0.5814 0.093 Uiso 1 1 calc R . .
C31 C 0.4930(7) 0.2579(2) 0.6532(5) 0.0718(19) Uani 1 1 d . . .
H31 H 0.4859 0.2411 0.5820 0.086 Uiso 1 1 calc R . .
C36 C 0.5000 0.3889(3) 0.7500 0.069(3) Uani 1 2 d S . .
C37 C 0.5416(6) 0.4148(2) 0.8633(8) 0.089(2) Uani 1 1 d . . .
H37 H 0.5695 0.3986 0.9408 0.106 Uiso 1 1 calc R . .
C40 C 0.5405(8) 0.4652(2) 0.8586(11) 0.133(4) Uani 1 1 d . . .
H40 H 0.5696 0.4822 0.9351 0.160 Uiso 1 1 calc R . .


_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
Br1 C6 1.916(5) . ?
Cu1 O2 1.963(3) . ?
Cu1 O2 1.963(3) 2_656 ?
Cu1 N1 2.046(4) 2_656 ?
Cu1 N1 2.046(4) . ?
Cu1 N3 2.318(5) . ?
O1 C3 1.360(6) . ?
O1 H1 0.8079 . ?
O2 C1 1.282(5) . ?
O3 C1 1.254(5) . ?
N1 C16 1.342(6) . ?
N1 C15 1.339(6) . ?
N3 C31 1.308(6) 2_656 ?
N3 C31 1.308(6) . ?
N4 C40 1.346(10) 2_656 ?
N4 C40 1.346(10) . ?
C1 C2 1.490(6) . ?
C2 C7 1.394(6) . ?
C2 C3 1.407(6) . ?
C3 C4 1.393(7) . ?
C4 C5 1.379(8) . ?
C4 H4A 0.9300 . ?
C5 C6 1.370(8) . ?
C5 H5 0.9300 . ?
C6 C7 1.378(7) . ?
C7 H7 0.9300 . ?
C15 C23 1.360(7) . ?
C15 H15 0.9300 . ?
C16 C19 1.382(6) . ?
C16 H16 0.9300 . ?
C17 C19 1.394(6) . ?
C17 C23 1.395(6) . ?
C17 C17 1.488(8) 2_556 ?
C19 H19 0.9300 . ?
C23 H23 0.9300 . ?
C27 C28 1.354(7) . ?
C27 C28 1.354(7) 2_656 ?
C27 C36 1.505(10) . ?
C28 C31 1.370(7) . ?
C28 H28 0.9300 . ?
C31 H31 0.9300 . ?
C36 C37 1.390(8) . ?
C36 C37 1.390(8) 2_656 ?
C37 C40 1.383(9) . ?
C37 H37 0.9300 . ?
C40 H40 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
O2 Cu1 O2 179.69(19) . 2_656 ?
O2 Cu1 N1 89.31(14) . 2_656 ?
O2 Cu1 N1 90.67(14) 2_656 2_656 ?
O2 Cu1 N1 90.67(14) . . ?
O2 Cu1 N1 89.31(14) 2_656 . ?
N1 Cu1 N1 172.1(2) 2_656 . ?
O2 Cu1 N3 90.15(10) . . ?
O2 Cu1 N3 90.15(10) 2_656 . ?
N1 Cu1 N3 93.94(11) 2_656 . ?
N1 Cu1 N3 93.94(11) . . ?
C3 O1 H1 109.8 . . ?
C1 O2 Cu1 112.6(3) . . ?
C16 N1 C15 116.8(4) . . ?
C16 N1 Cu1 121.3(3) . . ?
C15 N1 Cu1 121.7(3) . . ?
C31 N3 C31 116.1(7) 2_656 . ?
C31 N3 Cu1 122.0(3) 2_656 . ?
C31 N3 Cu1 122.0(3) . . ?
C40 N4 C40 116.3(11) 2_656 . ?
O3 C1 O2 122.7(4) . . ?
O3 C1 C2 119.8(4) . . ?
O2 C1 C2 117.5(4) . . ?
C7 C2 C3 119.0(4) . . ?
C7 C2 C1 120.6(4) . . ?
C3 C2 C1 120.3(4) . . ?
O1 C3 C4 118.0(5) . . ?
O1 C3 C2 121.8(5) . . ?
C4 C3 C2 120.2(5) . . ?
C5 C4 C3 119.8(5) . . ?
C5 C4 H4A 120.1 . . ?
C3 C4 H4A 120.1 . . ?
C6 C5 C4 119.6(5) . . ?
C6 C5 H5 120.2 . . ?
C4 C5 H5 120.2 . . ?
C5 C6 C7 122.1(5) . . ?
C5 C6 Br1 119.4(4) . . ?
C7 C6 Br1 118.4(4) . . ?
C6 C7 C2 119.2(5) . . ?
C6 C7 H7 120.4 . . ?
C2 C7 H7 120.4 . . ?
N1 C15 C23 123.8(4) . . ?
N1 C15 H15 118.1 . . ?
C23 C15 H15 118.1 . . ?
N1 C16 C19 123.1(4) . . ?
N1 C16 H16 118.4 . . ?
C19 C16 H16 118.4 . . ?
C19 C17 C23 116.6(4) . . ?
C19 C17 C17 122.7(3) . 2_556 ?
C23 C17 C17 120.6(3) . 2_556 ?
C16 C19 C17 119.5(4) . . ?
C16 C19 H19 120.3 . . ?
C17 C19 H19 120.3 . . ?
C15 C23 C17 120.0(4) . . ?
C15 C23 H23 120.0 . . ?
C17 C23 H23 120.0 . . ?
C28 C27 C28 115.5(7) . 2_656 ?
C28 C27 C36 122.2(3) . . ?
C28 C27 C36 122.2(3) 2_656 . ?
C27 C28 C31 120.7(6) . . ?
C27 C28 H28 119.6 . . ?
C31 C28 H28 119.6 . . ?
N3 C31 C28 123.4(6) . . ?
N3 C31 H31 118.3 . . ?
C28 C31 H31 118.3 . . ?
C37 C36 C37 118.4(8) . 2_656 ?
C37 C36 C27 120.8(4) . . ?
C37 C36 C27 120.8(4) 2_656 . ?
C40 C37 C36 118.7(9) . . ?
C40 C37 H37 120.7 . . ?
C36 C37 H37 120.7 . . ?
N4 C40 C37 124.0(10) . . ?
N4 C40 H40 118.0 . . ?
C37 C40 H40 118.0 . . ?

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
O2 Cu1 O2 C1 3(20) 2_656 . . . ?
N1 Cu1 O2 C1 89.5(3) 2_656 . . . ?
N1 Cu1 O2 C1 -82.6(3) . . . . ?
N3 Cu1 O2 C1 -176.6(3) . . . . ?
O2 Cu1 N1 C16 108.2(3) . . . . ?
O2 Cu1 N1 C16 -71.5(3) 2_656 . . . ?
N1 Cu1 N1 C16 18.4(3) 2_656 . . . ?
N3 Cu1 N1 C16 -161.6(3) . . . . ?
O2 Cu1 N1 C15 -76.5(4) . . . . ?
O2 Cu1 N1 C15 103.8(4) 2_656 . . . ?
N1 Cu1 N1 C15 -166.3(4) 2_656 . . . ?
N3 Cu1 N1 C15 13.7(4) . . . . ?
O2 Cu1 N3 C31 160.4(4) . . . 2_656 ?
O2 Cu1 N3 C31 -19.6(4) 2_656 . . 2_656 ?
N1 Cu1 N3 C31 -110.3(4) 2_656 . . 2_656 ?
N1 Cu1 N3 C31 69.7(4) . . . 2_656 ?
O2 Cu1 N3 C31 -19.6(4) . . . . ?
O2 Cu1 N3 C31 160.4(4) 2_656 . . . ?
N1 Cu1 N3 C31 69.7(4) 2_656 . . . ?
N1 Cu1 N3 C31 -110.3(4) . . . . ?
Cu1 O2 C1 O3 8.7(5) . . . . ?
Cu1 O2 C1 C2 -169.1(3) . . . . ?
O3 C1 C2 C7 177.9(4) . . . . ?
O2 C1 C2 C7 -4.2(7) . . . . ?
O3 C1 C2 C3 -4.8(7) . . . . ?
O2 C1 C2 C3 173.1(4) . . . . ?
C7 C2 C3 O1 -178.6(4) . . . . ?
C1 C2 C3 O1 4.1(7) . . . . ?
C7 C2 C3 C4 1.3(8) . . . . ?
C1 C2 C3 C4 -176.0(5) . . . . ?
O1 C3 C4 C5 178.9(5) . . . . ?
C2 C3 C4 C5 -1.0(9) . . . . ?
C3 C4 C5 C6 -0.3(10) . . . . ?
C4 C5 C6 C7 1.3(9) . . . . ?
C4 C5 C6 Br1 179.7(5) . . . . ?
C5 C6 C7 C2 -1.1(8) . . . . ?
Br1 C6 C7 C2 -179.4(4) . . . . ?
C3 C2 C7 C6 -0.2(7) . . . . ?
C1 C2 C7 C6 177.0(4) . . . . ?
C16 N1 C15 C23 3.2(8) . . . . ?
Cu1 N1 C15 C23 -172.3(4) . . . . ?
C15 N1 C16 C19 -2.0(7) . . . . ?
Cu1 N1 C16 C19 173.6(3) . . . . ?
N1 C16 C19 C17 -2.2(7) . . . . ?
C23 C17 C19 C16 4.9(6) . . . . ?
C17 C17 C19 C16 -175.6(5) 2_556 . . . ?
N1 C15 C23 C17 -0.3(9) . . . . ?
C19 C17 C23 C15 -3.8(7) . . . . ?
C17 C17 C23 C15 176.7(5) 2_556 . . . ?
C28 C27 C28 C31 1.3(5) 2_656 . . . ?
C36 C27 C28 C31 -178.7(5) . . . . ?
C31 N3 C31 C28 1.4(5) 2_656 . . . ?
Cu1 N3 C31 C28 -178.6(5) . . . . ?
C27 C28 C31 N3 -2.9(11) . . . . ?
C28 C27 C36 C37 -162.1(5) . . . . ?
C28 C27 C36 C37 17.9(5) 2_656 . . . ?
C28 C27 C36 C37 17.9(5) . . . 2_656 ?
C28 C27 C36 C37 -162.1(5) 2_656 . . 2_656 ?
C37 C36 C37 C40 -0.4(5) 2_656 . . . ?
C27 C36 C37 C40 179.6(5) . . . . ?
C40 N4 C40 C37 -0.4(5) 2_656 . . . ?
C36 C37 C40 N4 0.8(10) . . . . ?

_diffrn_measured_fraction_theta_max 0.993
_diffrn_reflns_theta_full        27.55
_diffrn_measured_fraction_theta_full 0.993
_refine_diff_density_max         0.549
_refine_diff_density_min         -0.492
_refine_diff_density_rms         0.091
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_2
_database_code_depnum_ccdc_archive 'CCDC 1575141'
_audit_update_record             
;
2017-09-18 deposited with the CCDC.
2017-11-17 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            'C20 H18 Br Cu N3 O4'
_chemical_formula_weight         507.82

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 '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                   32.4787(16)
_cell_length_b                   32.4787(16)
_cell_length_c                   10.5745(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     9660.2(11)
_cell_formula_units_Z            18
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    5986
_cell_measurement_theta_min      2.41
_cell_measurement_theta_max      24.67

_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.571
_exptl_crystal_F_000             4590.0
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.380
_exptl_crystal_size_mid          0.340
_exptl_crystal_size_min          0.280
_exptl_absorpt_coefficient_mu    2.909
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scans
_exptl_absorpt_correction_T_min  0.078
_exptl_absorpt_correction_T_max  0.114
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            29415
_diffrn_reflns_av_unetI/netI     0.0690
_diffrn_reflns_av_R_equivalents  0.0874
_diffrn_reflns_limit_h_min       -42
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_k_max       42
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         2.057
_diffrn_reflns_theta_max         27.502
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             4933
_reflns_number_gt                3330
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       ?
_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          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0492P)²+88.8389P] 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         4928
_refine_ls_number_parameters     264
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1089
_refine_ls_R_factor_gt           0.0642
_refine_ls_wR_factor_ref         0.1402
_refine_ls_wR_factor_gt          0.1243
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_restrained_S_all      1.033
_refine_ls_shift/su_max          0.005
_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 0.39031(2) 1.01176(2) 0.56000(5) 0.02222(16) Uani 1 1 d . . . . .
Br1 Br 0.25540(3) 0.74975(2) 0.48656(7) 0.0601(2) Uani 1 1 d . . . . .
C1 C 0.6025(2) 1.0812(2) 0.9657(6) 0.0445(14) Uani 1 1 d . . . . .
H1 H 0.5975 1.1070 0.9670 0.053 Uiso 1 1 calc R U . . .
C2 C 0.57116(16) 1.03991(17) 0.9020(4) 0.0244(10) Uani 1 1 d . . . . .
C3 C 0.5805(2) 1.0029(2) 0.9076(6) 0.0461(15) Uani 1 1 d . . . . .
H3 H 0.5599 0.9740 0.8693 0.055 Uiso 1 1 calc R U . . .
C4 C 0.4680(2) 1.0523(2) 0.7929(5) 0.0411(14) Uani 1 1 d . . . . .
H4 H 0.4523 1.0683 0.8181 0.049 Uiso 1 1 calc R U . . .
C5 C 0.5057(2) 1.0581(2) 0.8645(5) 0.0401(14) Uani 1 1 d . . . . .
H5 H 0.5150 1.0775 0.9356 0.048 Uiso 1 1 calc R U . . .
C6 C 0.52985(17) 1.03480(17) 0.8301(4) 0.0257(10) Uani 1 1 d . . . . .
C7 C 0.5140(2) 1.0067(2) 0.7226(5) 0.0413(14) Uani 1 1 d . . . . .
H7 H 0.5290 0.9902 0.6951 0.050 Uiso 1 1 calc R U . . .
C8 C 0.4760(2) 1.0034(2) 0.6572(5) 0.0418(14) Uani 1 1 d . . . . .
H8 H 0.4662 0.9846 0.5849 0.050 Uiso 1 1 calc R U . . .
C9 C 0.4169(2) 1.10921(19) 0.6396(5) 0.0414(14) Uani 1 1 d . . . . .
H9 H 0.4446 1.1167 0.5958 0.050 Uiso 1 1 calc R U . . .
C10 C 0.3419(2) 1.05466(19) 0.6967(6) 0.0416(14) Uani 1 1 d . . . . .
H10 H 0.3166 1.0236 0.6951 0.050 Uiso 1 1 calc R U . . .
C11 C 0.31971(16) 0.92217(16) 0.6760(4) 0.0228(10) Uani 1 1 d . . . . .
C12 C 0.32577(17) 0.89444(16) 0.5749(4) 0.0244(10) Uani 1 1 d . . . . .
C13 C 0.29590(19) 0.84491(17) 0.5774(5) 0.0314(11) Uani 1 1 d . . . . .
H13 H 0.2749 0.8309 0.6444 0.038 Uiso 1 1 calc R U . . .
C14 C 0.2973(2) 0.81699(18) 0.4822(5) 0.0379(13) Uani 1 1 d . . . . .
C15 C 0.3284(2) 0.8370(2) 0.3826(5) 0.0512(17) Uani 1 1 d . . . . .
H15 H 0.3291 0.8179 0.3182 0.061 Uiso 1 1 calc R U . . .
C16 C 0.3583(2) 0.8853(2) 0.3789(5) 0.0483(16) Uani 1 1 d . . . . .
H16 H 0.3792 0.8984 0.3113 0.058 Uiso 1 1 calc R U . . .
C17 C 0.35842(19) 0.91604(19) 0.4748(4) 0.0313(11) Uani 1 1 d . . . . .
C18 C 0.1684(7) 0.6076(6) 0.4630(17) 0.230(10) Uani 1 1 d . . . . .
H18A H 0.1676 0.5861 0.5267 0.345 Uiso 1 1 calc R U . . .
H18B H 0.1414 0.5912 0.4083 0.345 Uiso 1 1 calc R U . . .
H18C H 0.1677 0.6338 0.5027 0.345 Uiso 1 1 calc R U . . .
C19 C 0.2310(13) 0.6454(8) 0.277(3) 0.34(2) Uani 1 1 d . . . . .
H19 H 0.2601 0.6568 0.2367 0.405 Uiso 1 1 calc R U . . .
C20 C 0.2499(7) 0.6269(5) 0.453(2) 0.293(16) Uani 1 1 d . . . . .
H20A H 0.2609 0.6506 0.5181 0.439 Uiso 1 1 calc R U . . .
H20B H 0.2749 0.6352 0.3922 0.439 Uiso 1 1 calc R U . . .
H20C H 0.2411 0.5966 0.4894 0.439 Uiso 1 1 calc R U . . .
N1 N 0.45226(14) 1.02526(15) 0.6901(4) 0.0296(9) Uani 1 1 d . . . . .
N2 N 0.38216(13) 1.06455(13) 0.6392(3) 0.0225(8) Uani 1 1 d . . . . .
N3 N 0.2102(4) 0.6246(3) 0.3921(10) 0.108(3) Uani 1 1 d . . . . .
O1 O 0.38790(12) 0.96134(12) 0.4613(3) 0.0315(8) Uani 1 1 d . . . . .
O2 O 0.34234(11) 0.96730(11) 0.6758(3) 0.0252(7) Uani 1 1 d . . . . .
O3 O 0.29077(11) 0.89988(11) 0.7641(3) 0.0262(7) Uani 1 1 d . . . . .
O4 O 0.1839(7) 0.6404(8) 0.2517(16) 0.323(12) Uani 1 1 d . . . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Cu1 O1 1.910(3) . ?
Cu1 O2 1.940(3) . ?
Cu1 O3 1.990(3) 8_664 ?
Cu1 N2 2.041(4) . ?
Cu1 N1 2.292(4) . ?
Br1 C14 1.911(5) . ?
C1 C9 1.377(7) 18_656 ?
C1 C2 1.387(7) . ?
C1 H1 0.9300 . ?
C2 C3 1.381(7) . ?
C2 C6 1.477(6) . ?
C3 C10 1.385(7) 18_656 ?
C3 H3 0.9300 . ?
C4 N1 1.328(6) . ?
C4 C5 1.372(7) . ?
C4 H4 0.9300 . ?
C5 C6 1.382(7) . ?
C5 H5 0.9300 . ?
C6 C7 1.386(7) . ?
C7 C8 1.372(7) . ?
C7 H7 0.9300 . ?
C8 N1 1.329(6) . ?
C8 H8 0.9300 . ?
C9 N2 1.319(6) . ?
C9 C1 1.377(7) 17_456 ?
C9 H9 0.9300 . ?
C10 N2 1.328(6) . ?
C10 C3 1.385(7) 17_456 ?
C10 H10 0.9300 . ?
C11 O3 1.263(5) . ?
C11 O2 1.270(5) . ?
C11 C12 1.472(6) . ?
C12 C13 1.403(7) . ?
C12 C17 1.412(7) . ?
C13 C14 1.371(7) . ?
C13 H13 0.9300 . ?
C14 C15 1.376(8) . ?
C15 C16 1.372(8) . ?
C15 H15 0.9300 . ?
C16 C17 1.422(7) . ?
C16 H16 0.9300 . ?
C17 O1 1.301(6) . ?
C18 N3 1.398(16) . ?
C18 H18A 0.9600 . ?
C18 H18B 0.9600 . ?
C18 H18C 0.9600 . ?
C19 N3 1.39(3) . ?
C19 O4 1.48(4) . ?
C19 H19 0.9300 . ?
C20 N3 1.410(17) . ?
C20 H20A 0.9600 . ?
C20 H20B 0.9600 . ?
C20 H20C 0.9600 . ?
O3 Cu1 1.990(3) 6_465 ?

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
O1 Cu1 O2 91.92(14) . . ?
O1 Cu1 O3 88.70(14) . 8_664 ?
O2 Cu1 O3 173.41(14) . 8_664 ?
O1 Cu1 N2 167.82(15) . . ?
O2 Cu1 N2 88.44(14) . . ?
O3 Cu1 N2 89.58(14) 8_664 . ?
O1 Cu1 N1 98.50(15) . . ?
O2 Cu1 N1 93.72(14) . . ?
O3 Cu1 N1 92.68(14) 8_664 . ?
N2 Cu1 N1 93.62(15) . . ?
C9 C1 C2 119.2(5) 18_656 . ?
C9 C1 H1 120.4 18_656 . ?
C2 C1 H1 120.4 . . ?
C3 C2 C1 116.5(5) . . ?
C3 C2 C6 120.5(4) . . ?
C1 C2 C6 123.0(4) . . ?
C2 C3 C10 120.4(5) . 18_656 ?
C2 C3 H3 119.8 . . ?
C10 C3 H3 119.8 18_656 . ?
N1 C4 C5 124.4(5) . . ?
N1 C4 H4 117.8 . . ?
C5 C4 H4 117.8 . . ?
C4 C5 C6 119.5(5) . . ?
C4 C5 H5 120.3 . . ?
C6 C5 H5 120.3 . . ?
C5 C6 C7 116.8(5) . . ?
C5 C6 C2 122.3(4) . . ?
C7 C6 C2 120.8(4) . . ?
C8 C7 C6 119.1(5) . . ?
C8 C7 H7 120.4 . . ?
C6 C7 H7 120.4 . . ?
N1 C8 C7 124.5(5) . . ?
N1 C8 H8 117.7 . . ?
C7 C8 H8 117.7 . . ?
N2 C9 C1 124.0(5) . 17_456 ?
N2 C9 H9 118.0 . . ?
C1 C9 H9 118.0 17_456 . ?
N2 C10 C3 122.3(5) . 17_456 ?
N2 C10 H10 118.9 . . ?
C3 C10 H10 118.9 17_456 . ?
O3 C11 O2 119.9(4) . . ?
O3 C11 C12 118.3(4) . . ?
O2 C11 C12 121.9(4) . . ?
C13 C12 C17 120.0(4) . . ?
C13 C12 C11 117.4(4) . . ?
C17 C12 C11 122.5(4) . . ?
C14 C13 C12 120.8(5) . . ?
C14 C13 H13 119.6 . . ?
C12 C13 H13 119.6 . . ?
C13 C14 C15 120.6(5) . . ?
C13 C14 Br1 119.9(4) . . ?
C15 C14 Br1 119.5(4) . . ?
C16 C15 C14 119.7(5) . . ?
C16 C15 H15 120.2 . . ?
C14 C15 H15 120.2 . . ?
C15 C16 C17 122.3(6) . . ?
C15 C16 H16 118.9 . . ?
C17 C16 H16 118.9 . . ?
O1 C17 C12 126.1(4) . . ?
O1 C17 C16 117.3(5) . . ?
C12 C17 C16 116.6(5) . . ?
N3 C18 H18A 109.5 . . ?
N3 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
N3 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
N3 C19 O4 83(3) . . ?
N3 C19 H19 138.4 . . ?
O4 C19 H19 138.4 . . ?
N3 C20 H20A 109.5 . . ?
N3 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
N3 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
C4 N1 C8 115.7(4) . . ?
C4 N1 Cu1 128.9(3) . . ?
C8 N1 Cu1 115.4(3) . . ?
C9 N2 C10 117.5(4) . . ?
C9 N2 Cu1 121.8(3) . . ?
C10 N2 Cu1 120.7(3) . . ?
C19 N3 C18 143(2) . . ?
C19 N3 C20 99.3(19) . . ?
C18 N3 C20 117.2(16) . . ?
C17 O1 Cu1 127.0(3) . . ?
C11 O2 Cu1 130.2(3) . . ?
C11 O3 Cu1 112.6(3) . 6_465 ?

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
C9 C1 C2 C3 1.6(8) 18_656 . . . ?
C9 C1 C2 C6 -177.9(5) 18_656 . . . ?
C1 C2 C3 C10 -2.6(9) . . . 18_656 ?
C6 C2 C3 C10 176.9(5) . . . 18_656 ?
N1 C4 C5 C6 0.0(10) . . . . ?
C4 C5 C6 C7 0.3(8) . . . . ?
C4 C5 C6 C2 179.2(5) . . . . ?
C3 C2 C6 C5 149.2(6) . . . . ?
C1 C2 C6 C5 -31.3(8) . . . . ?
C3 C2 C6 C7 -32.0(8) . . . . ?
C1 C2 C6 C7 147.6(6) . . . . ?
C5 C6 C7 C8 0.0(8) . . . . ?
C2 C6 C7 C8 -178.9(5) . . . . ?
C6 C7 C8 N1 -0.7(10) . . . . ?
O3 C11 C12 C13 5.3(6) . . . . ?
O2 C11 C12 C13 -174.1(4) . . . . ?
O3 C11 C12 C17 -177.8(4) . . . . ?
O2 C11 C12 C17 2.8(7) . . . . ?
C17 C12 C13 C14 -1.2(7) . . . . ?
C11 C12 C13 C14 175.8(4) . . . . ?
C12 C13 C14 C15 0.5(8) . . . . ?
C12 C13 C14 Br1 -178.9(4) . . . . ?
C13 C14 C15 C16 0.2(9) . . . . ?
Br1 C14 C15 C16 179.6(5) . . . . ?
C14 C15 C16 C17 -0.3(10) . . . . ?
C13 C12 C17 O1 179.9(5) . . . . ?
C11 C12 C17 O1 3.1(8) . . . . ?
C13 C12 C17 C16 1.1(7) . . . . ?
C11 C12 C17 C16 -175.7(5) . . . . ?
C15 C16 C17 O1 -179.3(5) . . . . ?
C15 C16 C17 C12 -0.4(9) . . . . ?
C5 C4 N1 C8 -0.6(9) . . . . ?
C5 C4 N1 Cu1 -179.8(4) . . . . ?
C7 C8 N1 C4 1.0(9) . . . . ?
C7 C8 N1 Cu1 -179.7(5) . . . . ?
C1 C9 N2 C10 3.3(8) 17_456 . . . ?
C1 C9 N2 Cu1 -174.3(5) 17_456 . . . ?
C3 C10 N2 C9 -2.1(8) 17_456 . . . ?
C3 C10 N2 Cu1 175.4(5) 17_456 . . . ?
O4 C19 N3 C18 -2(3) . . . . ?
O4 C19 N3 C20 -175.5(14) . . . . ?
C12 C17 O1 Cu1 -8.2(7) . . . . ?
C16 C17 O1 Cu1 170.6(4) . . . . ?
O3 C11 O2 Cu1 177.5(3) . . . . ?
C12 C11 O2 Cu1 -3.1(6) . . . . ?
O2 C11 O3 Cu1 -1.6(5) . . . 6_465 ?
C12 C11 O3 Cu1 179.0(3) . . . 6_465 ?

_refine_diff_density_max         0.963
_refine_diff_density_min         -0.540
_refine_diff_density_rms         0.107

