# Electronic Supplementary Material (ESI) for RSC Advances.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# 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 991416'
_audit_update_record             
;
2015-03-24 deposited with the CCDC.
2015-05-07 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C36 H40 Cu4 N12 O12, 4(Cl O4), 4(H2 O)'
_chemical_formula_sum            'C36 H48 Cl4 Cu4 N12 O32'
_chemical_formula_weight         1556.82

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'
Cl Cl 0.1484 0.1585 '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           tetragonal
_symmetry_space_group_name_H-M   I41/a

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

_cell_length_a                   19.0353(6)
_cell_length_b                   19.0353(6)
_cell_length_c                   15.4705(7)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     5605.6(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    1926
_cell_measurement_theta_min      2.7250
_cell_measurement_theta_max      29.3260

_exptl_crystal_description       block
_exptl_crystal_colour            dark-blue
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.14
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.845
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             3152
_exptl_absorpt_coefficient_mu    1.795
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6232
_exptl_absorpt_correction_T_max  0.7829
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      173(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'SuperNova (Mo) X-ray Source'
_diffrn_radiation_monochromator  mirror
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean 16.0107
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            5120
_diffrn_reflns_av_R_equivalents  0.0194
_diffrn_reflns_av_sigmaI/netI    0.0295
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         2.14
_diffrn_reflns_theta_max         25.50
_reflns_number_total             2604
_reflns_number_gt                2049
_reflns_threshold_expression     >2σ(I)

_computing_data_collection       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_cell_refinement       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction        
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_structure_solution    
;
SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790
;
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_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 > 2σ(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)+(0.0716P)²+30.6684P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         2604
_refine_ls_number_parameters     237
_refine_ls_number_restraints     94
_refine_ls_R_factor_all          0.0681
_refine_ls_R_factor_gt           0.0502
_refine_ls_wR_factor_ref         0.1446
_refine_ls_wR_factor_gt          0.1274
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_restrained_S_all      1.281
_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 0.52475(3) 0.33609(3) 0.80308(4) 0.0300(3) Uani 1 1 d . . .
O1 O 0.58247(19) 0.2530(2) 0.8231(2) 0.0326(8) Uani 1 1 d . . .
O2 O 0.6672(2) 0.1570(2) 0.8835(2) 0.0391(10) Uani 1 1 d . . .
O3 O 0.4602(2) 0.4102(2) 0.7661(2) 0.0372(9) Uani 1 1 d . . .
N1 N 0.5433(2) 0.3327(2) 0.6800(3) 0.0324(10) Uani 1 1 d . . .
N2 N 0.5015(3) 0.3791(3) 0.6352(3) 0.0388(12) Uani 1 1 d . . .
H2 H 0.5019 0.3823 0.5784 0.047 Uiso 1 1 calc R . .
N3 N 0.4197(3) 0.4672(3) 0.6481(4) 0.0497(14) Uani 1 1 d . . .
H3A H 0.3922 0.4940 0.6798 0.060 Uiso 1 1 calc R . .
H3B H 0.4206 0.4724 0.5916 0.060 Uiso 1 1 calc R . .
C1 C 0.6298(3) 0.2258(3) 0.7666(3) 0.0307(11) Uani 1 1 d . . .
C2 C 0.6334(3) 0.2440(3) 0.6792(3) 0.0326(12) Uani 1 1 d . . .
C3 C 0.6839(3) 0.2108(3) 0.6257(4) 0.0425(14) Uani 1 1 d . . .
H3 H 0.6868 0.2235 0.5664 0.051 Uiso 1 1 calc R . .
C4 C 0.7282(3) 0.1613(4) 0.6577(4) 0.0475(16) Uani 1 1 d . . .
H4 H 0.7612 0.1393 0.6205 0.057 Uiso 1 1 calc R . .
C5 C 0.7256(3) 0.1425(3) 0.7444(4) 0.0422(14) Uani 1 1 d . . .
H5 H 0.7572 0.1085 0.7669 0.051 Uiso 1 1 calc R . .
C6 C 0.6762(3) 0.1739(3) 0.7978(4) 0.0348(12) Uani 1 1 d . . .
C7 C 0.7224(3) 0.1187(4) 0.9264(5) 0.0498(17) Uani 1 1 d . . .
H7A H 0.7672 0.1433 0.9183 0.075 Uiso 1 1 calc R . .
H7B H 0.7257 0.0714 0.9019 0.075 Uiso 1 1 calc R . .
H7C H 0.7119 0.1155 0.9883 0.075 Uiso 1 1 calc R . .
C8 C 0.5886(3) 0.2942(3) 0.6383(3) 0.0358(13) Uani 1 1 d . . .
H8 H 0.5921 0.2998 0.5775 0.043 Uiso 1 1 calc R . .
C9 C 0.4599(3) 0.4192(3) 0.6855(4) 0.0357(13) Uani 1 1 d . . .
O4 O 0.4724(4) 0.1392(5) 0.4571(5) 0.129(3) Uani 1 1 d U . .
H4A H 0.5019 0.1088 0.4401 0.194 Uiso 1 1 d R . .
H4B H 0.4311 0.1495 0.4427 0.194 Uiso 1 1 d R . .
Cl1 Cl 0.63145(13) 0.53944(13) 0.59062(14) 0.0797(7) Uani 1 1 d D . .
O5A O 0.6912(7) 0.5310(9) 0.6425(9) 0.109(6) Uani 0.471(12) 1 d PDU A 1
O6A O 0.5802(6) 0.5744(7) 0.6555(7) 0.076(4) Uani 0.471(12) 1 d PD A 1
O7A O 0.6441(8) 0.5968(8) 0.5329(8) 0.100(6) Uani 0.471(12) 1 d PD A 1
O8A O 0.5989(10) 0.4859(9) 0.5552(12) 0.138(8) Uani 0.471(12) 1 d PDU A 1
O5B O 0.6321(11) 0.5793(8) 0.6608(9) 0.140(7) Uani 0.529(12) 1 d PDU A 2
O6B O 0.6900(7) 0.5541(8) 0.5318(8) 0.107(5) Uani 0.529(12) 1 d PDU A 2
O7B O 0.5700(6) 0.5367(9) 0.5384(8) 0.105(5) Uani 0.529(12) 1 d PDU A 2
O8B O 0.6432(6) 0.4646(5) 0.6133(7) 0.070(4) Uani 0.529(12) 1 d PD A 2


_geom_special_details            
;
 All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell s.u.'s are taken
 into account individually in the estimation of s.u.'s in distances, angles
 and torsion angles; correlations between s.u.'s in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell s.u.'s is used for estimating s.u.'s 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 1.938(5) . ?
Cu1 O1 1.950(4) . ?
Cu1 O3 1.956(4) . ?
Cu1 O1 1.988(4) 16_657 ?
Cu1 O2 2.244(4) 16_657 ?
O1 C1 1.358(6) . ?
O1 Cu1 1.988(4) 10_667 ?
O2 C6 1.374(7) . ?
O2 C7 1.441(7) . ?
O2 Cu1 2.244(4) 10_667 ?
O3 C9 1.259(7) . ?
N1 C8 1.303(7) . ?
N1 N2 1.377(7) . ?
N2 C9 1.347(8) . ?
N2 H2 0.8800 . ?
N3 C9 1.325(8) . ?
N3 H3A 0.8800 . ?
N3 H3B 0.8800 . ?
C1 C2 1.397(7) . ?
C1 C6 1.411(8) . ?
C2 C3 1.417(8) . ?
C2 C8 1.427(8) . ?
C3 C4 1.359(9) . ?
C3 H3 0.9500 . ?
C4 C5 1.389(9) . ?
C4 H4 0.9500 . ?
C5 C6 1.387(8) . ?
C5 H5 0.9500 . ?
C7 H7A 0.9800 . ?
C7 H7B 0.9800 . ?
C7 H7C 0.9800 . ?
C8 H8 0.9500 . ?
O4 H4A 0.8494 . ?
O4 H4B 0.8409 . ?
Cl1 O8A 1.313(12) . ?
Cl1 O5B 1.324(12) . ?
Cl1 O5A 1.401(11) . ?
Cl1 O7B 1.422(11) . ?
Cl1 O7A 1.431(11) . ?
Cl1 O6B 1.465(11) . ?
Cl1 O8B 1.485(9) . ?
Cl1 O6A 1.550(10) . ?

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 O1 91.51(17) . . ?
N1 Cu1 O3 81.45(18) . . ?
O1 Cu1 O3 170.06(16) . . ?
N1 Cu1 O1 173.72(18) . 16_657 ?
O1 Cu1 O1 88.19(16) . 16_657 ?
O3 Cu1 O1 98.03(16) . 16_657 ?
N1 Cu1 O2 110.33(17) . 16_657 ?
O1 Cu1 O2 99.35(16) . 16_657 ?
O3 Cu1 O2 89.72(16) . 16_657 ?
O1 Cu1 O2 75.90(15) 16_657 16_657 ?
C1 O1 Cu1 125.4(3) . . ?
C1 O1 Cu1 119.8(3) . 10_667 ?
Cu1 O1 Cu1 112.86(18) . 10_667 ?
C6 O2 C7 118.2(5) . . ?
C6 O2 Cu1 111.8(3) . 10_667 ?
C7 O2 Cu1 126.4(4) . 10_667 ?
C9 O3 Cu1 113.0(4) . . ?
C8 N1 N2 119.6(5) . . ?
C8 N1 Cu1 128.8(4) . . ?
N2 N1 Cu1 111.6(3) . . ?
C9 N2 N1 114.4(4) . . ?
C9 N2 H2 122.8 . . ?
N1 N2 H2 122.8 . . ?
C9 N3 H3A 120.0 . . ?
C9 N3 H3B 120.0 . . ?
H3A N3 H3B 120.0 . . ?
O1 C1 C2 124.2(5) . . ?
O1 C1 C6 117.5(5) . . ?
C2 C1 C6 118.3(5) . . ?
C1 C2 C3 119.2(5) . . ?
C1 C2 C8 124.4(5) . . ?
C3 C2 C8 116.4(5) . . ?
C4 C3 C2 121.1(6) . . ?
C4 C3 H3 119.4 . . ?
C2 C3 H3 119.4 . . ?
C3 C4 C5 120.6(6) . . ?
C3 C4 H4 119.7 . . ?
C5 C4 H4 119.7 . . ?
C6 C5 C4 119.2(6) . . ?
C6 C5 H5 120.4 . . ?
C4 C5 H5 120.4 . . ?
O2 C6 C5 123.9(5) . . ?
O2 C6 C1 114.6(5) . . ?
C5 C6 C1 121.5(5) . . ?
O2 C7 H7A 109.5 . . ?
O2 C7 H7B 109.5 . . ?
H7A C7 H7B 109.5 . . ?
O2 C7 H7C 109.5 . . ?
H7A C7 H7C 109.5 . . ?
H7B C7 H7C 109.5 . . ?
N1 C8 C2 123.5(5) . . ?
N1 C8 H8 118.2 . . ?
C2 C8 H8 118.2 . . ?
O3 C9 N3 121.9(6) . . ?
O3 C9 N2 119.5(5) . . ?
N3 C9 N2 118.6(5) . . ?
H4A O4 H4B 134.2 . . ?
O8A Cl1 O5B 142.4(11) . . ?
O8A Cl1 O5A 122.2(11) . . ?
O5B Cl1 O5A 65.7(10) . . ?
O8A Cl1 O7B 49.2(10) . . ?
O5B Cl1 O7B 119.6(10) . . ?
O5A Cl1 O7B 171.3(9) . . ?
O8A Cl1 O7A 114.3(10) . . ?
O5B Cl1 O7A 94.2(10) . . ?
O5A Cl1 O7A 107.9(8) . . ?
O7B Cl1 O7A 79.2(8) . . ?
O8A Cl1 O6B 104.3(9) . . ?
O5B Cl1 O6B 113.1(9) . . ?
O5A Cl1 O6B 76.1(8) . . ?
O7B Cl1 O6B 106.2(7) . . ?
O7A Cl1 O6B 48.7(7) . . ?
O8A Cl1 O8B 54.9(10) . . ?
O5B Cl1 O8B 110.8(8) . . ?
O5A Cl1 O8B 68.4(8) . . ?
O7B Cl1 O8B 102.9(7) . . ?
O7A Cl1 O8B 148.7(8) . . ?
O6B Cl1 O8B 102.4(7) . . ?
O8A Cl1 O6A 107.9(8) . . ?
O5B Cl1 O6A 39.6(8) . . ?
O5A Cl1 O6A 100.9(7) . . ?
O7B Cl1 O6A 82.3(7) . . ?
O7A Cl1 O6A 100.5(8) . . ?
O6B Cl1 O6A 143.1(8) . . ?
O8B Cl1 O6A 110.7(7) . . ?

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
N1 Cu1 O1 C1 16.2(4) . . . . ?
O1 Cu1 O1 C1 -170.1(4) 16_657 . . . ?
O2 Cu1 O1 C1 -94.7(4) 16_657 . . . ?
N1 Cu1 O1 Cu1 -179.8(2) . . . 10_667 ?
O1 Cu1 O1 Cu1 -6.10(19) 16_657 . . 10_667 ?
O2 Cu1 O1 Cu1 69.3(2) 16_657 . . 10_667 ?
N1 Cu1 O3 C9 1.3(4) . . . . ?
O1 Cu1 O3 C9 -172.3(4) 16_657 . . . ?
O2 Cu1 O3 C9 111.9(4) 16_657 . . . ?
O1 Cu1 N1 C8 -10.3(5) . . . . ?
O3 Cu1 N1 C8 176.8(5) . . . . ?
O2 Cu1 N1 C8 90.3(5) 16_657 . . . ?
O1 Cu1 N1 N2 170.4(4) . . . . ?
O3 Cu1 N1 N2 -2.5(3) . . . . ?
O2 Cu1 N1 N2 -89.0(4) 16_657 . . . ?
C8 N1 N2 C9 -176.0(5) . . . . ?
Cu1 N1 N2 C9 3.4(6) . . . . ?
Cu1 O1 C1 C2 -14.5(7) . . . . ?
Cu1 O1 C1 C2 -177.5(4) 10_667 . . . ?
Cu1 O1 C1 C6 168.2(4) . . . . ?
Cu1 O1 C1 C6 5.2(6) 10_667 . . . ?
O1 C1 C2 C3 -178.4(5) . . . . ?
C6 C1 C2 C3 -1.1(8) . . . . ?
O1 C1 C2 C8 1.1(9) . . . . ?
C6 C1 C2 C8 178.4(5) . . . . ?
C1 C2 C3 C4 0.7(9) . . . . ?
C8 C2 C3 C4 -178.8(6) . . . . ?
C2 C3 C4 C5 -0.8(10) . . . . ?
C3 C4 C5 C6 1.2(10) . . . . ?
C7 O2 C6 C5 16.7(8) . . . . ?
Cu1 O2 C6 C5 176.6(5) 10_667 . . . ?
C7 O2 C6 C1 -164.5(5) . . . . ?
Cu1 O2 C6 C1 -4.5(6) 10_667 . . . ?
C4 C5 C6 O2 177.2(6) . . . . ?
C4 C5 C6 C1 -1.6(9) . . . . ?
O1 C1 C6 O2 0.2(7) . . . . ?
C2 C1 C6 O2 -177.3(5) . . . . ?
O1 C1 C6 C5 179.0(5) . . . . ?
C2 C1 C6 C5 1.6(8) . . . . ?
N2 N1 C8 C2 -179.0(5) . . . . ?
Cu1 N1 C8 C2 1.7(8) . . . . ?
C1 C2 C8 N1 5.8(9) . . . . ?
C3 C2 C8 N1 -174.7(6) . . . . ?
Cu1 O3 C9 N3 -179.8(5) . . . . ?
Cu1 O3 C9 N2 0.2(7) . . . . ?
N1 N2 C9 O3 -2.5(8) . . . . ?
N1 N2 C9 N3 177.6(5) . . . . ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        25.50
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         1.021
_refine_diff_density_min         -0.596
_refine_diff_density_rms         0.099
