# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2018

####################################################################### 
# 
# 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_SNNU-65-Ga-Cu
_database_code_depnum_ccdc_archive 'CCDC 1542966'
_audit_update_record             
;
2017-05-31 deposited with the CCDC.
2018-01-29 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        SNNU-65-Ga-Cu
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C90 H51 Cu6 Ga3 N0 O46'
_chemical_formula_weight         2458.71

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'
Ga Ga 0.2307 1.6083 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           hexagonal
_symmetry_space_group_name_H-M   P6(3)/mmc

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

_cell_length_a                   18.5324(10)
_cell_length_b                   18.5324(10)
_cell_length_c                   40.250(4)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     11971.7(16)
_cell_formula_units_Z            2
_cell_measurement_temperature    153(2)
_cell_measurement_reflns_used    4500
_cell_measurement_theta_min      2.388
_cell_measurement_theta_max      25.171

_exptl_crystal_description       hexagonal
_exptl_crystal_colour            blue
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.22
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    0.682
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2452
_exptl_absorpt_coefficient_mu    0.893
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6421
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      153(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            283354
_diffrn_reflns_av_R_equivalents  0.0931
_diffrn_reflns_av_sigmaI/netI    0.0228
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_limit_l_max       50
_diffrn_reflns_theta_min         2.20
_diffrn_reflns_theta_max         26.42
_reflns_number_total             4576
_reflns_number_gt                4194
_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. 
;

_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)+(0.0725P)²+44.4495P] 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         4576
_refine_ls_number_parameters     125
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0992
_refine_ls_R_factor_gt           0.0882
_refine_ls_wR_factor_ref         0.2029
_refine_ls_wR_factor_gt          0.1959
_refine_ls_goodness_of_fit_ref   1.147
_refine_ls_restrained_S_all      1.147
_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
Cu1 Cu 0.52375(2) 0.04750(4) 0.526972(17) 0.0258(2) Uani 1 2 d S . .
Ga1 Ga 0.11900(7) 0.05950(4) 0.7500 0.0409(3) Uani 1 4 d S . .
O4 O 0.41025(18) -0.02997(19) 0.54216(8) 0.0407(8) Uani 1 1 d . . .
O6 O 0.62841(18) 0.11011(18) 0.50300(8) 0.0397(8) Uani 1 1 d . . .
O5 O 0.5589(2) 0.1178(4) 0.57165(15) 0.081(2) Uani 1 2 d S . .
H5 H 0.6082 0.1573 0.5700 0.121 Uiso 0.50 1 calc PR . .
C10 C 0.3605(3) -0.0915(3) 0.52523(10) 0.0342(9) Uani 1 1 d . . .
O1 O 0.2482(6) 0.1241(3) 0.7500 0.078(3) Uani 1 4 d S . .
H1 H 0.2656 0.1623 0.7643 0.116 Uiso 0.25 1 calc PR . .
C9 C 0.2234(2) -0.2234(2) 0.52599(16) 0.0346(13) Uani 1 2 d S . .
H9 H 0.2380 -0.2380 0.5054 0.042 Uiso 1 2 calc SR . .
C8 C 0.2771(3) -0.1482(3) 0.54131(11) 0.0340(9) Uani 1 1 d . . .
C6 C 0.1790(2) -0.1790(2) 0.58653(16) 0.0388(15) Uani 1 2 d S . .
C7 C 0.2552(3) -0.1268(3) 0.57112(11) 0.0381(10) Uani 1 1 d . . .
H7 H 0.2930 -0.0752 0.5813 0.046 Uiso 1 1 calc R . .
C5 C 0.1545(2) -0.1545(2) 0.61737(16) 0.0411(15) Uani 1 2 d S . .
O3 O 0.1245(3) -0.0095(3) 0.71543(12) 0.105(2) Uani 1 1 d . . .
O2 O 0.0000 0.0000 0.7500 0.128(8) Uani 1 12 d S . .
C1 C 0.07769(19) -0.07769(19) 0.70412(15) 0.0387(15) Uani 1 2 d S . .
C2 C 0.1051(2) -0.1051(2) 0.67431(15) 0.0368(14) Uani 1 2 d S . .
C3 C 0.1762(5) -0.0577(6) 0.6605(2) 0.175(6) Uani 1 1 d . . .
H3 H 0.2131 -0.0052 0.6701 0.210 Uiso 1 1 calc R . .
C4 C 0.2006(5) -0.0819(6) 0.6313(2) 0.173(6) Uani 1 1 d . . .
H4 H 0.2525 -0.0439 0.6214 0.208 Uiso 1 1 calc R . .

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
Cu1 0.0261(3) 0.0205(4) 0.0290(4) -0.0064(3) -0.00322(14) 0.01026(18)
Ga1 0.0531(7) 0.0423(4) 0.0310(5) 0.000 0.000 0.0266(3)
O4 0.0272(15) 0.0320(16) 0.0463(18) -0.0041(14) 0.0086(14) 0.0023(13)
O6 0.0320(16) 0.0351(17) 0.0383(16) -0.0058(14) 0.0063(14) 0.0065(13)
O5 0.076(3) 0.094(5) 0.078(4) -0.060(4) -0.0298(19) 0.047(2)
C10 0.033(2) 0.029(2) 0.035(2) 0.0005(18) 0.0011(18) 0.0119(19)
O1 0.091(7) 0.070(4) 0.079(6) 0.000 0.000 0.045(3)
C9 0.030(2) 0.030(2) 0.041(3) -0.0011(14) 0.0011(14) 0.014(3)
C8 0.031(2) 0.027(2) 0.043(2) -0.0066(19) 0.0024(19) 0.0136(18)
C6 0.035(2) 0.035(2) 0.043(3) -0.0085(14) 0.0085(14) 0.016(3)
C7 0.031(2) 0.034(2) 0.043(2) -0.011(2) 0.002(2) 0.012(2)
C5 0.038(2) 0.038(2) 0.040(3) -0.0086(15) 0.0086(15) 0.012(3)
O3 0.086(3) 0.090(3) 0.095(3) -0.066(3) 0.034(3) 0.011(3)
O2 0.151(13) 0.151(13) 0.082(13) 0.000 0.000 0.075(6)
C1 0.055(3) 0.055(3) 0.025(3) 0.0024(12) -0.0024(12) 0.043(4)
C2 0.041(3) 0.041(3) 0.030(3) -0.0066(13) 0.0066(13) 0.022(3)
C3 0.102(6) 0.110(7) 0.168(9) -0.105(7) 0.089(6) -0.055(5)
C4 0.100(6) 0.111(7) 0.171(9) -0.105(7) 0.094(6) -0.051(5)

_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 O6 1.946(3) 20_655 ?
Cu1 O6 1.946(3) . ?
Cu1 O4 1.960(3) . ?
Cu1 O4 1.960(3) 20_655 ?
Cu1 O5 2.123(5) . ?
Cu1 Cu1 2.6532(13) 13_656 ?
Ga1 O2 1.9098(12) . ?
Ga1 O3 1.926(4) 12_556 ?
Ga1 O3 1.926(4) 21 ?
Ga1 O3 1.926(4) . ?
Ga1 O3 1.926(4) 16_557 ?
Ga1 O1 2.073(10) . ?
O4 C10 1.250(5) . ?
O6 C10 1.234(5) 13_656 ?
C10 O6 1.234(5) 13_656 ?
C10 C8 1.513(6) . ?
C9 C8 1.388(5) . ?
C9 C8 1.388(5) 19 ?
C8 C7 1.387(6) . ?
C6 C7 1.396(5) 19 ?
C6 C7 1.396(5) . ?
C6 C5 1.470(8) . ?
C5 C4 1.306(7) . ?
C5 C4 1.306(7) 19 ?
O3 C1 1.209(5) . ?
O2 Ga1 1.9098(12) 2 ?
O2 Ga1 1.9098(12) 3 ?
C1 O3 1.209(5) 19 ?
C1 C2 1.488(8) . ?
C2 C3 1.289(7) 19 ?
C2 C3 1.289(7) . ?
C3 C4 1.408(9) . ?

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
O6 Cu1 O6 88.6(2) 20_655 . ?
O6 Cu1 O4 89.33(14) 20_655 . ?
O6 Cu1 O4 167.45(13) . . ?
O6 Cu1 O4 167.45(13) 20_655 20_655 ?
O6 Cu1 O4 89.33(14) . 20_655 ?
O4 Cu1 O4 90.0(2) . 20_655 ?
O6 Cu1 O5 98.36(17) 20_655 . ?
O6 Cu1 O5 98.36(17) . . ?
O4 Cu1 O5 94.19(17) . . ?
O4 Cu1 O5 94.19(17) 20_655 . ?
O6 Cu1 Cu1 83.74(9) 20_655 13_656 ?
O6 Cu1 Cu1 83.74(9) . 13_656 ?
O4 Cu1 Cu1 83.72(9) . 13_656 ?
O4 Cu1 Cu1 83.72(9) 20_655 13_656 ?
O5 Cu1 Cu1 177.0(2) . 13_656 ?
O2 Ga1 O3 92.64(15) . 12_556 ?
O2 Ga1 O3 92.64(15) . 21 ?
O3 Ga1 O3 92.5(4) 12_556 21 ?
O2 Ga1 O3 92.64(15) . . ?
O3 Ga1 O3 174.7(3) 12_556 . ?
O3 Ga1 O3 87.3(4) 21 . ?
O2 Ga1 O3 92.64(15) . 16_557 ?
O3 Ga1 O3 87.3(4) 12_556 16_557 ?
O3 Ga1 O3 174.7(3) 21 16_557 ?
O3 Ga1 O3 92.5(4) . 16_557 ?
O2 Ga1 O1 180.000(2) . . ?
O3 Ga1 O1 87.36(15) 12_556 . ?
O3 Ga1 O1 87.36(15) 21 . ?
O3 Ga1 O1 87.36(15) . . ?
O3 Ga1 O1 87.36(15) 16_557 . ?
C10 O4 Cu1 122.0(3) . . ?
C10 O6 Cu1 123.0(3) 13_656 . ?
O6 C10 O4 127.4(4) 13_656 . ?
O6 C10 C8 117.0(4) 13_656 . ?
O4 C10 C8 115.6(4) . . ?
C8 C9 C8 118.7(6) . 19 ?
C7 C8 C9 120.5(4) . . ?
C7 C8 C10 121.0(4) . . ?
C9 C8 C10 118.5(4) . . ?
C7 C6 C7 117.0(5) 19 . ?
C7 C6 C5 121.5(3) 19 . ?
C7 C6 C5 121.5(3) . . ?
C8 C7 C6 121.7(4) . . ?
C4 C5 C4 114.7(8) . 19 ?
C4 C5 C6 122.5(4) . . ?
C4 C5 C6 122.5(4) 19 . ?
C1 O3 Ga1 135.8(4) . . ?
Ga1 O2 Ga1 120.0 . 2 ?
Ga1 O2 Ga1 120.0 . 3 ?
Ga1 O2 Ga1 120.0 2 3 ?
O3 C1 O3 123.7(7) . 19 ?
O3 C1 C2 118.1(3) . . ?
O3 C1 C2 118.1(3) 19 . ?
C3 C2 C3 116.8(7) 19 . ?
C3 C2 C1 121.6(4) 19 . ?
C3 C2 C1 121.6(4) . . ?
C2 C3 C4 121.7(6) . . ?
C5 C4 C3 122.5(7) . . ?

loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
1 -0.039 -0.025 0.000 8497.0 1072.6
_platon_squeeze_details          
;
;


_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        26.42
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         0.803
_refine_diff_density_min         -0.729
_refine_diff_density_rms         0.078
