# Electronic Supplementary Material (ESI) for Molecular Systems Design & Engineering.
# This journal is © The Royal Society of Chemistry 2020

####################################################################### 
# 
# 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_12044m
_database_code_depnum_ccdc_archive 'CCDC 1959281'
loop_
_audit_author_name
_audit_author_address
'Douglas R. Powell'
;University of Oklahoma
United States of America
;
_audit_update_record             
;
2019-12-15 deposited with the CCDC.	2020-05-06 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
#_shelx_SHELXL_version_number      '2018/3' 
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C22 H38 Br4 Cu2 N6 O2, 4(H2 O)'
_chemical_formula_sum            'C22 H46 Br4 Cu2 N6 O6'
_chemical_formula_weight         937.37

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      monoclinic
_space_group_IT_number           13
_space_group_name_H-M_alt        'P 2/c'
_space_group_name_Hall           '-P 2yc'

_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'
'-x, -y, -z'
'x, -y, z-1/2'

_cell_length_a                   8.2177(15)
_cell_length_b                   8.2395(14)
_cell_length_c                   23.750(4)
_cell_angle_alpha                90
_cell_angle_beta                 93.288(2)
_cell_angle_gamma                90
_cell_volume                     1605.5(5)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9135
_cell_measurement_theta_min      2.47
_cell_measurement_theta_max      25.83

_exptl_crystal_description       prism
_exptl_crystal_colour            blue
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.939
_exptl_crystal_F_000             932
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.500
_exptl_crystal_size_mid          0.440
_exptl_crystal_size_min          0.280
_exptl_absorpt_coefficient_mu    6.348
_shelx_estimated_absorpt_T_min   0.143
_shelx_estimated_absorpt_T_max   0.269
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.143
_exptl_absorpt_correction_T_max  0.269
_exptl_absorpt_process_details   
; 
 SADABS 2008/1 Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & 
 Stalke, D. (2015).  J. Appl.Cryst. 48, 3-10. 
;
#_exptl_absorpt_special_details    ? 
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'CCD Bruker APEX'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            16798
_diffrn_reflns_av_unetI/netI     0.0437
_diffrn_reflns_av_R_equivalents  0.0569
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_theta_min         2.472
_diffrn_reflns_theta_max         25.679
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.960
_diffrn_measured_fraction_theta_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_point_group_measured_fraction_full 0.988
_reflns_number_total             2921
_reflns_number_gt                2500
_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       'SMART (Bruker, 2012)'
_computing_cell_refinement       'SAINT (Bruker, 2012)'
_computing_data_reduction        'SAINT (Bruker, 2012)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015a)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2015b)'
_computing_molecular_graphics    'Mercury (CCDC, 2018)'
_computing_publication_material  'SHELXL-2018/3 (Sheldrick, 2015b)'
_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)+(0.0800P)²+7.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2921
_refine_ls_number_parameters     205
_refine_ls_number_restraints     18
_refine_ls_R_factor_all          0.0515
_refine_ls_R_factor_gt           0.0406
_refine_ls_wR_factor_ref         0.1283
_refine_ls_wR_factor_gt          0.1228
_refine_ls_goodness_of_fit_ref   1.005
_refine_ls_restrained_S_all      1.004
_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
Br1 Br 0.29905(7) 0.57298(7) 0.19245(2) 0.0175(2) Uani 1 1 d D . . . .
Br2 Br 0.41988(7) 0.29219(7) 0.07510(2) 0.0173(2) Uani 1 1 d . . . . .
Cu1 Cu 0.51145(9) 0.55326(8) 0.11318(3) 0.0128(2) Uani 1 1 d . . . . .
N1 N 0.6336(6) 0.7717(6) 0.1214(2) 0.0146(11) Uani 1 1 d . . . . .
C2 C 0.8080(8) 0.7237(8) 0.1203(3) 0.0244(15) Uani 1 1 d . . . . .
H2A H 0.879121 0.819440 0.127357 0.029 Uiso 1 1 calc R U . . .
H2B H 0.830302 0.678143 0.082927 0.029 Uiso 1 1 calc R U . . .
C3 C 0.8415(8) 0.5972(8) 0.1660(3) 0.0212(14) Uani 1 1 d . . . . .
H3A H 0.947695 0.544275 0.160721 0.025 Uiso 1 1 calc R U . . .
H3B H 0.847087 0.650194 0.203453 0.025 Uiso 1 1 calc DR U . . .
N4 N 0.7108(6) 0.4739(6) 0.1635(2) 0.0150(11) Uani 1 1 d D . . . .
H4 H 0.674(6) 0.478(6) 0.197(2) 0.018 Uiso 1 1 d D U . . .
C5 C 0.7753(8) 0.3061(7) 0.1563(3) 0.0205(14) Uani 1 1 d . . . . .
H5A H 0.853016 0.280742 0.188495 0.025 Uiso 1 1 calc R U . . .
H5B H 0.683881 0.227975 0.157078 0.025 Uiso 1 1 calc R U . . .
C6 C 0.8583(8) 0.2847(7) 0.1031(3) 0.0197(14) Uani 1 1 d . . . . .
O7 O 0.7915(5) 0.3606(5) 0.05545(17) 0.0184(9) Uani 1 1 d . . . . .
C8 C 0.9844(8) 0.1913(7) 0.0888(3) 0.0188(14) Uani 1 1 d . . . . .
H8 H 1.054326 0.129534 0.113855 0.023 Uiso 1 1 calc R U . . .
C9 C 0.9930(8) 0.2028(7) 0.0291(3) 0.0182(13) Uani 1 1 d . . . . .
H9 H 1.067909 0.148230 0.006655 0.022 Uiso 1 1 calc R U . . .
C10 C 0.8751(8) 0.3055(7) 0.0107(3) 0.0174(13) Uani 1 1 d . . . . .
C11 C 0.8053(7) 0.3667(7) -0.0452(3) 0.0172(13) Uani 1 1 d . . . . .
H11A H 0.820126 0.485709 -0.047275 0.021 Uiso 1 1 calc R U . . .
H11B H 0.864291 0.316514 -0.075991 0.021 Uiso 1 1 calc R U . . .
N12 N 0.6299(6) 0.3271(6) -0.0527(2) 0.0150(11) Uani 1 1 d D . . . .
H12 H 0.572(8) 0.349(8) -0.024(3) 0.018 Uiso 1 1 d D U . . .
C13 C 0.6005(8) 0.1496(7) -0.0597(3) 0.0181(13) Uani 1 1 d . . . . .
H13A H 0.637582 0.090746 -0.024933 0.022 Uiso 1 1 calc R U . . .
H13B H 0.660536 0.107001 -0.091473 0.022 Uiso 1 1 calc R U . . .
C14 C 0.4184(9) 0.1278(8) -0.0714(3) 0.0266(16) Uani 1 1 d . . . . .
H14A H 0.393017 0.012126 -0.078920 0.032 Uiso 1 1 calc R U . . .
H14B H 0.359463 0.162610 -0.038219 0.032 Uiso 1 1 calc R U . . .
C15 C 0.6072(9) 0.8627(8) 0.1740(3) 0.0254(15) Uani 1 1 d . . . . .
H15A H 0.681713 0.955629 0.176773 0.038 Uiso 1 1 d R U . . .
H15B H 0.628424 0.791329 0.206583 0.038 Uiso 1 1 d R U . . .
H15C H 0.494383 0.901469 0.173313 0.038 Uiso 1 1 d R U . . .
O1S O 0.1093(7) -0.0673(6) 0.2064(2) 0.0424(15) Uani 1 1 d D . . . .
H1SA H 0.155(9) -0.162(5) 0.202(3) 0.051 Uiso 1 1 d D U . . .
H1SB H 0.073(12) -0.089(14) 0.239(3) 0.051 Uiso 0.5 1 d D U P A 1
H1SC H 0.195(9) -0.020(8) 0.221(5) 0.051 Uiso 0.5 1 d D U P B 2
O2S O 0.3475(9) 0.1682(7) 0.2229(3) 0.0515(17) Uani 1 1 d D . . . .
H2SA H 0.321(10) 0.269(3) 0.218(4) 0.062 Uiso 1 1 d D U . . .
H2SB H 0.256(8) 0.125(9) 0.230(5) 0.062 Uiso 0.5 1 d D U P C 1
H2SC H 0.418(7) 0.180(13) 0.251(3) 0.062 Uiso 0.5 1 d D U P D 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
Br1 Cu1 2.6447(10) . ?
Br2 Cu1 2.4359(9) . ?
Cu1 N12 2.048(5) 3_665 ?
Cu1 N1 2.065(5) . ?
Cu1 N4 2.076(5) . ?
N1 C15 1.483(8) . ?
N1 C2 1.489(8) . ?
N1 C14 1.491(8) 3_665 ?
C2 C3 1.519(9) . ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C3 N4 1.477(8) . ?
C3 H3A 0.9900 . ?
C3 H3B 0.9900 . ?
N4 C5 1.494(8) . ?
N4 H4 0.87(5) . ?
C5 C6 1.481(9) . ?
C5 H5A 0.9900 . ?
C5 H5B 0.9900 . ?
C6 C8 1.350(9) . ?
C6 O7 1.379(7) . ?
O7 C10 1.376(7) . ?
C8 C9 1.429(9) . ?
C8 H8 0.9500 . ?
C9 C10 1.340(9) . ?
C9 H9 0.9500 . ?
C10 C11 1.503(8) . ?
C11 N12 1.479(8) . ?
C11 H11A 0.9900 . ?
C11 H11B 0.9900 . ?
N12 C13 1.490(7) . ?
N12 H12 0.87(5) . ?
C13 C14 1.517(9) . ?
C13 H13A 0.9900 . ?
C13 H13B 0.9900 . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C15 H15A 0.9801 . ?
C15 H15B 0.9797 . ?
C15 H15C 0.9801 . ?
O1S H1SA 0.875(18) . ?
O1S H1SB 0.87(2) . ?
O1S H1SC 0.86(2) . ?
O2S H2SA 0.862(19) . ?
O2S H2SB 0.86(2) . ?
O2S H2SC 0.86(2) . ?

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
N12 Cu1 N1 84.27(19) 3_665 . ?
N12 Cu1 N4 162.2(2) 3_665 . ?
N1 Cu1 N4 81.77(19) . . ?
N12 Cu1 Br2 90.80(14) 3_665 . ?
N1 Cu1 Br2 160.60(14) . . ?
N4 Cu1 Br2 98.74(14) . . ?
N12 Cu1 Br1 95.66(15) 3_665 . ?
N1 Cu1 Br1 102.47(14) . . ?
N4 Cu1 Br1 98.11(15) . . ?
Br2 Cu1 Br1 96.67(3) . . ?
C15 N1 C2 109.7(5) . . ?
C15 N1 C14 110.0(5) . 3_665 ?
C2 N1 C14 111.4(5) . 3_665 ?
C15 N1 Cu1 115.3(4) . . ?
C2 N1 Cu1 103.3(4) . . ?
C14 N1 Cu1 107.0(4) 3_665 . ?
N1 C2 C3 107.7(5) . . ?
N1 C2 H2A 110.2 . . ?
C3 C2 H2A 110.2 . . ?
N1 C2 H2B 110.2 . . ?
C3 C2 H2B 110.2 . . ?
H2A C2 H2B 108.5 . . ?
N4 C3 C2 110.0(5) . . ?
N4 C3 H3A 109.7 . . ?
C2 C3 H3A 109.7 . . ?
N4 C3 H3B 109.7 . . ?
C2 C3 H3B 109.7 . . ?
H3A C3 H3B 108.2 . . ?
C3 N4 C5 112.3(5) . . ?
C3 N4 Cu1 110.8(4) . . ?
C5 N4 Cu1 120.0(4) . . ?
C3 N4 H4 103(2) . . ?
C5 N4 H4 106(4) . . ?
Cu1 N4 H4 102(4) . . ?
C6 C5 N4 113.0(5) . . ?
C6 C5 H5A 109.0 . . ?
N4 C5 H5A 109.0 . . ?
C6 C5 H5B 109.0 . . ?
N4 C5 H5B 109.0 . . ?
H5A C5 H5B 107.8 . . ?
C8 C6 O7 109.2(5) . . ?
C8 C6 C5 132.8(6) . . ?
O7 C6 C5 117.7(5) . . ?
C10 O7 C6 106.9(5) . . ?
C6 C8 C9 107.1(5) . . ?
C6 C8 H8 126.5 . . ?
C9 C8 H8 126.5 . . ?
C10 C9 C8 106.8(6) . . ?
C10 C9 H9 126.6 . . ?
C8 C9 H9 126.6 . . ?
C9 C10 O7 109.9(5) . . ?
C9 C10 C11 137.0(6) . . ?
O7 C10 C11 112.9(5) . . ?
N12 C11 C10 110.6(5) . . ?
N12 C11 H11A 109.5 . . ?
C10 C11 H11A 109.5 . . ?
N12 C11 H11B 109.5 . . ?
C10 C11 H11B 109.5 . . ?
H11A C11 H11B 108.1 . . ?
C11 N12 C13 112.4(5) . . ?
C11 N12 Cu1 119.2(4) . 3_665 ?
C13 N12 Cu1 108.2(4) . 3_665 ?
C11 N12 H12 115(4) . . ?
C13 N12 H12 102(4) . . ?
Cu1 N12 H12 98(4) 3_665 . ?
N12 C13 C14 106.8(5) . . ?
N12 C13 H13A 110.4 . . ?
C14 C13 H13A 110.4 . . ?
N12 C13 H13B 110.4 . . ?
C14 C13 H13B 110.4 . . ?
H13A C13 H13B 108.6 . . ?
N1 C14 C13 108.3(5) 3_665 . ?
N1 C14 H14A 110.0 3_665 . ?
C13 C14 H14A 110.0 . . ?
N1 C14 H14B 110.0 3_665 . ?
C13 C14 H14B 110.0 . . ?
H14A C14 H14B 108.4 . . ?
N1 C15 H15A 109.3 . . ?
N1 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
N1 C15 H15C 109.6 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
H1SA O1S H1SB 96(4) . . ?
H1SA O1S H1SC 96(4) . . ?
H2SA O2S H2SB 102(5) . . ?
H2SA O2S H2SC 98(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
C15 N1 C2 C3 68.6(6) . . . . ?
C14 N1 C2 C3 -169.4(5) 3_665 . . . ?
Cu1 N1 C2 C3 -54.9(5) . . . . ?
N1 C2 C3 N4 46.2(7) . . . . ?
C2 C3 N4 C5 123.1(6) . . . . ?
C2 C3 N4 Cu1 -14.0(6) . . . . ?
C3 N4 C5 C6 -61.9(7) . . . . ?
Cu1 N4 C5 C6 70.8(6) . . . . ?
N4 C5 C6 C8 148.1(7) . . . . ?
N4 C5 C6 O7 -38.7(8) . . . . ?
C8 C6 O7 C10 2.8(7) . . . . ?
C5 C6 O7 C10 -171.9(5) . . . . ?
O7 C6 C8 C9 -2.7(7) . . . . ?
C5 C6 C8 C9 170.8(7) . . . . ?
C6 C8 C9 C10 1.6(7) . . . . ?
C8 C9 C10 O7 0.1(7) . . . . ?
C8 C9 C10 C11 -175.2(7) . . . . ?
C6 O7 C10 C9 -1.7(7) . . . . ?
C6 O7 C10 C11 174.8(5) . . . . ?
C9 C10 C11 N12 120.5(8) . . . . ?
O7 C10 C11 N12 -54.7(7) . . . . ?
C10 C11 N12 C13 -68.7(6) . . . . ?
C10 C11 N12 Cu1 163.1(4) . . . 3_665 ?
C11 N12 C13 C14 -175.7(5) . . . . ?
Cu1 N12 C13 C14 -42.0(6) 3_665 . . . ?
N12 C13 C14 N1 55.9(6) . . . 3_665 ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
C3 H3A Br1 0.99 2.95 3.782(6) 142.1 1_655 yes
C3 H3B Br1 0.99 2.88 3.622(7) 132.3 2_655 yes
N4 H4 Br1 0.87(5) 2.74(5) 3.524(5) 151(3) 2_655 yes
C5 H5B Br2 0.99 2.88 3.408(7) 114.3 . yes
C11 H11A Br2 0.99 2.74 3.418(6) 125.8 3_665 yes
N12 H12 Br2 0.87(5) 2.77(6) 3.588(5) 157(6) . yes
C14 H14A Br2 0.99 2.94 3.710(7) 135.3 3_655 yes
C14 H14B Br2 0.99 2.91 3.732(7) 140.9 . yes
C15 H15B Br1 0.98 3.03 4.009(7) 178.9 2_655 yes
O1S H1SA Br1 0.875(18) 2.500(19) 3.374(5) 177(7) 1_545 yes
O1S H1SB O1S 0.87(2) 2.04(4) 2.819(13) 148(7) 2 yes
O1S H1SC O2S 0.86(2) 1.99(4) 2.768(9) 150(8) . yes
O2S H2SA Br1 0.862(19) 2.58(2) 3.431(5) 167(7) . yes
O2S H2SB O1S 0.86(2) 2.05(4) 2.768(9) 141(6) . yes
O2S H2SC O2S 0.86(2) 1.99(4) 2.751(15) 146(7) 2_655 yes

_refine_diff_density_max         0.993
_refine_diff_density_min         -0.786
_refine_diff_density_rms         0.137

