# Electronic Supplementary Material (ESI) for Dalton Transactions.
# 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_cau14
_database_code_depnum_ccdc_archive 'CCDC 1029260'
_audit_update_record             
;
2015-01-10 deposited with the CCDC.
2015-01-19 downloaded from the CCDC.
;


_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C21 H12 Cu3 N3 O15 P3'
_chemical_formula_weight         829.87

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0029 0.0015 '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 0.0057 0.0031 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0101 0.0057 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
P P 0.0973 0.0888 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu 0.3319 1.2017 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           8
_space_group_name_H-M_alt        'C m'
_space_group_name_Hall           'C -2y'

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

_cell_length_a                   25.618(5)
_cell_length_b                   17.040(3)
_cell_length_c                   4.4322(9)
_cell_angle_alpha                90
_cell_angle_beta                 99.96(3)
_cell_angle_gamma                90
_cell_volume                     1905.6(7)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    4802
_cell_measurement_theta_min      2.7965
_cell_measurement_theta_max      31.9295

_exptl_crystal_description       needle
_exptl_crystal_colour            'light green'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.446
_exptl_crystal_F_000             822
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_exptl_absorpt_coefficient_mu    1.630
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.42305
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   ?





_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.6889
_diffrn_radiation_type           ?
_diffrn_source                   synchrotron
_diffrn_measurement_device_type  'Rigaku Saturn724+ diffractometer'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            7534
_diffrn_reflns_av_unetI/netI     0.0612
_diffrn_reflns_av_R_equivalents  0.0596
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_l_min       -5
_diffrn_reflns_limit_l_max       5
_diffrn_reflns_theta_min         2.796
_diffrn_reflns_theta_max         24.517
_diffrn_reflns_theta_full        24.415
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measured_fraction_theta_full 0.972
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_Laue_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_point_group_measured_fraction_full 0.972
_reflns_number_total             2946
_reflns_number_gt                2778
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.996
_reflns_Friedel_fraction_max     0.973
_reflns_Friedel_fraction_full    0.973

_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       'CrystalClear-SM Expert 2.0 r5 (Rigaku, 2011)'
_computing_cell_refinement       ?
_computing_data_reduction        CrysAlisPro
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'Diamond 3.2k (Brandenburg 2014)'
_computing_publication_material  none

_refine_special_details          Twin
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0996P)²] 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_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.66(4)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         2946
_refine_ls_number_parameters     228
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0532
_refine_ls_R_factor_gt           0.0500
_refine_ls_wR_factor_ref         0.1521
_refine_ls_wR_factor_gt          0.1436
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_restrained_S_all      1.091
_refine_ls_shift/su_max          0.000
_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 0.36046(7) 0.5000 0.1695(3) 0.0319(4) Uani 1 2 d S T P . .
O1 O 0.2790(5) 0.5000 0.331(3) 0.069(4) Uani 1 2 d S T P . .
Cu2 Cu 0.46865(5) 0.39272(6) 0.29599(17) 0.0339(4) Uani 1 1 d . . . . .
O2A O 0.4838(9) 0.2856(9) 0.493(5) 0.037(8) Uani 0.45(6) 1 d . . P . .
O2B O 0.5062(15) 0.2852(12) 0.349(9) 0.088(14) Uani 0.55(6) 1 d . . P . .
P1 P 0.37850(10) 0.37176(13) 0.7159(5) 0.0294(5) Uani 1 1 d . . . . .
O3 O 0.4270(3) 0.3441(3) 0.9387(13) 0.0367(15) Uani 1 1 d . . . . .
O4 O 0.3958(3) 0.4192(4) 0.4520(13) 0.0297(14) Uani 1 1 d . . . . .
O5 O 0.3388(3) 0.4184(4) 0.8631(17) 0.0387(15) Uani 1 1 d . . . . .
C1 C 0.3480(4) 0.2819(5) 0.5566(19) 0.0322(19) Uani 1 1 d . . . . .
C2 C 0.3669(5) 0.2108(6) 0.668(3) 0.046(3) Uani 1 1 d . . . . .
H2A H 0.3960 0.2091 0.8260 0.056 Uiso 1 1 calc R U . . .
C3 C 0.3436(5) 0.1399(5) 0.549(3) 0.050(3) Uani 1 1 d . . . . .
H3A H 0.3561 0.0921 0.6340 0.060 Uiso 1 1 calc R U . . .
C4 C 0.3015(4) 0.1422(5) 0.304(2) 0.035(2) Uani 1 1 d . . . . .
C5 C 0.2805(4) 0.2125(6) 0.193(3) 0.045(2) Uani 1 1 d . . . . .
H5A H 0.2514 0.2138 0.0356 0.054 Uiso 1 1 calc R U . . .
C6 C 0.3034(6) 0.2830(6) 0.321(3) 0.055(3) Uani 1 1 d . . . . .
H6A H 0.2888 0.3309 0.2492 0.066 Uiso 1 1 calc R U . . .
C7 C 0.2784(4) 0.0658(5) 0.164(2) 0.0296(18) Uani 1 1 d . . . . .
N1 N 0.3008(4) 0.0000 0.285(2) 0.031(2) Uani 1 2 d S T P . .
N2 N 0.2382(3) 0.0699(4) -0.0712(18) 0.0255(15) Uani 1 1 d . . . . .
C8 C 0.2185(5) 0.0000 -0.184(3) 0.028(2) Uani 1 2 d S T P . .
P2 P 0.01862(13) 0.0000 -1.1518(7) 0.0270(6) Uani 1 2 d S T P . .
O6 O -0.0215(4) 0.0000 -0.931(2) 0.035(2) Uani 1 2 d S T P . .
O7 O 0.0146(3) 0.0750(4) -1.3373(14) 0.0362(15) Uani 1 1 d . . . . .
C9 C 0.1734(5) 0.0000 -0.446(3) 0.026(2) Uani 1 2 d S T P . .
C10 C 0.1530(4) 0.0694(5) -0.566(2) 0.039(2) Uani 1 1 d . . . . .
H10A H 0.1688 0.1166 -0.4952 0.046 Uiso 1 1 calc R U . . .
C11 C 0.1084(5) 0.0696(5) -0.794(2) 0.045(3) Uani 1 1 d . . . . .
H11A H 0.0952 0.1170 -0.8798 0.054 Uiso 1 1 calc R U . . .
C12 C 0.0835(5) 0.0000 -0.897(3) 0.028(2) Uani 1 2 d S T P . .
O8 O 0.4780(10) 0.1292(10) 0.280(9) 0.187(11) Uani 1 1 d . . . . .
O9 O 0.4124(13) 0.0000 0.189(8) 0.152(10) Uani 1 2 d S T P . .


_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 O5 1.956(7) 1_554 ?
Cu1 O5 1.956(7) 2_564 ?
Cu1 O4 1.972(6) . ?
Cu1 O4 1.972(6) 2_565 ?
Cu1 O1 2.320(13) . ?
Cu2 O7 1.915(6) 4_557 ?
Cu2 O3 1.936(6) 1_554 ?
Cu2 O2A 2.030(14) . ?
Cu2 O2B 2.06(2) . ?
Cu2 O6 2.123(5) 3_556 ?
Cu2 O4 2.147(7) . ?
O2A O2B 0.93(3) . ?
P1 O5 1.523(7) . ?
P1 O3 1.523(8) . ?
P1 O4 1.549(6) . ?
P1 C1 1.807(9) . ?
O3 Cu2 1.936(6) 1_556 ?
O5 Cu1 1.956(7) 1_556 ?
C1 C2 1.365(14) . ?
C1 C6 1.408(16) . ?
C2 C3 1.409(14) . ?
C3 C4 1.393(16) . ?
C4 C5 1.370(14) . ?
C4 C7 1.517(12) . ?
C5 C6 1.412(15) . ?
C7 N1 1.328(11) . ?
C7 N2 1.335(12) . ?
N1 C7 1.328(11) 2 ?
N2 C8 1.355(9) . ?
C8 N2 1.355(9) 2 ?
C8 C9 1.492(18) . ?
P2 O7 1.513(6) . ?
P2 O7 1.513(6) 2 ?
P2 O6 1.536(9) . ?
P2 C12 1.840(13) . ?
O6 Cu2 2.123(5) 4_454 ?
O6 Cu2 2.123(5) 3_444 ?
O7 Cu2 1.915(6) 4_453 ?
C9 C10 1.364(11) 2 ?
C9 C10 1.364(11) . ?
C10 C11 1.387(14) . ?
C11 C12 1.386(12) . ?
C12 C11 1.386(12) 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
O5 Cu1 O5 90.6(4) 1_554 2_564 ?
O5 Cu1 O4 89.3(3) 1_554 . ?
O5 Cu1 O4 168.8(3) 2_564 . ?
O5 Cu1 O4 168.8(3) 1_554 2_565 ?
O5 Cu1 O4 89.3(3) 2_564 2_565 ?
O4 Cu1 O4 88.5(4) . 2_565 ?
O5 Cu1 O1 93.0(3) 1_554 . ?
O5 Cu1 O1 93.0(3) 2_564 . ?
O4 Cu1 O1 98.2(3) . . ?
O4 Cu1 O1 98.2(3) 2_565 . ?
O7 Cu2 O3 171.1(3) 4_557 1_554 ?
O7 Cu2 O2A 81.4(5) 4_557 . ?
O3 Cu2 O2A 90.2(6) 1_554 . ?
O7 Cu2 O2B 87.2(7) 4_557 . ?
O3 Cu2 O2B 83.9(6) 1_554 . ?
O2A Cu2 O2B 26.2(10) . . ?
O7 Cu2 O6 92.8(3) 4_557 3_556 ?
O3 Cu2 O6 94.3(3) 1_554 3_556 ?
O2A Cu2 O6 161.5(8) . 3_556 ?
O2B Cu2 O6 136.7(15) . 3_556 ?
O7 Cu2 O4 96.1(3) 4_557 . ?
O3 Cu2 O4 88.1(3) 1_554 . ?
O2A Cu2 O4 99.3(8) . . ?
O2B Cu2 O4 124.3(15) . . ?
O6 Cu2 O4 98.8(3) 3_556 . ?
O2B O2A Cu2 78.9(16) . . ?
O2A O2B Cu2 74.9(16) . . ?
O5 P1 O3 114.5(4) . . ?
O5 P1 O4 110.5(4) . . ?
O3 P1 O4 110.1(4) . . ?
O5 P1 C1 109.5(4) . . ?
O3 P1 C1 103.9(4) . . ?
O4 P1 C1 108.0(4) . . ?
P1 O3 Cu2 132.1(4) . 1_556 ?
P1 O4 Cu1 133.1(4) . . ?
P1 O4 Cu2 120.8(4) . . ?
Cu1 O4 Cu2 105.8(3) . . ?
P1 O5 Cu1 122.6(4) . 1_556 ?
C2 C1 C6 118.2(9) . . ?
C2 C1 P1 120.6(8) . . ?
C6 C1 P1 121.2(7) . . ?
C1 C2 C3 121.6(10) . . ?
C4 C3 C2 119.3(9) . . ?
C5 C4 C3 120.5(9) . . ?
C5 C4 C7 120.3(9) . . ?
C3 C4 C7 119.3(8) . . ?
C4 C5 C6 119.4(10) . . ?
C1 C6 C5 120.9(9) . . ?
N1 C7 N2 125.4(8) . . ?
N1 C7 C4 116.8(8) . . ?
N2 C7 C4 117.8(8) . . ?
C7 N1 C7 115.2(11) . 2 ?
C7 N2 C8 115.4(8) . . ?
N2 C8 N2 123.1(11) . 2 ?
N2 C8 C9 118.4(6) . . ?
N2 C8 C9 118.4(6) 2 . ?
O7 P2 O7 115.2(5) . 2 ?
O7 P2 O6 110.8(3) . . ?
O7 P2 O6 110.8(3) 2 . ?
O7 P2 C12 107.7(3) . . ?
O7 P2 C12 107.7(3) 2 . ?
O6 P2 C12 104.0(5) . . ?
P2 O6 Cu2 116.7(3) . 4_454 ?
P2 O6 Cu2 116.7(3) . 3_444 ?
Cu2 O6 Cu2 118.9(4) 4_454 3_444 ?
P2 O7 Cu2 132.7(4) . 4_453 ?
C10 C9 C10 120.4(12) 2 . ?
C10 C9 C8 119.8(6) 2 . ?
C10 C9 C8 119.8(6) . . ?
C9 C10 C11 119.8(9) . . ?
C12 C11 C10 120.8(9) . . ?
C11 C12 C11 117.6(12) . 2 ?
C11 C12 P2 121.2(6) . . ?
C11 C12 P2 121.2(6) 2 . ?

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
O5 P1 O3 Cu2 -37.3(7) . . . 1_556 ?
O4 P1 O3 Cu2 87.9(6) . . . 1_556 ?
C1 P1 O3 Cu2 -156.7(5) . . . 1_556 ?
O5 P1 O4 Cu1 -28.8(7) . . . . ?
O3 P1 O4 Cu1 -156.2(5) . . . . ?
C1 P1 O4 Cu1 91.0(6) . . . . ?
O5 P1 O4 Cu2 158.7(4) . . . . ?
O3 P1 O4 Cu2 31.3(5) . . . . ?
C1 P1 O4 Cu2 -81.5(5) . . . . ?
O3 P1 O5 Cu1 43.7(6) . . . 1_556 ?
O4 P1 O5 Cu1 -81.3(5) . . . 1_556 ?
C1 P1 O5 Cu1 159.9(4) . . . 1_556 ?
O5 P1 C1 C2 -116.3(9) . . . . ?
O3 P1 C1 C2 6.4(9) . . . . ?
O4 P1 C1 C2 123.3(8) . . . . ?
O5 P1 C1 C6 61.9(9) . . . . ?
O3 P1 C1 C6 -175.4(9) . . . . ?
O4 P1 C1 C6 -58.5(10) . . . . ?
C6 C1 C2 C3 1.2(17) . . . . ?
P1 C1 C2 C3 179.4(9) . . . . ?
C1 C2 C3 C4 2.7(18) . . . . ?
C2 C3 C4 C5 -4.7(17) . . . . ?
C2 C3 C4 C7 176.4(10) . . . . ?
C3 C4 C5 C6 2.8(17) . . . . ?
C7 C4 C5 C6 -178.3(10) . . . . ?
C2 C1 C6 C5 -3.1(18) . . . . ?
P1 C1 C6 C5 178.6(9) . . . . ?
C4 C5 C6 C1 1.2(19) . . . . ?
C5 C4 C7 N1 -179.8(10) . . . . ?
C3 C4 C7 N1 -0.9(14) . . . . ?
C5 C4 C7 N2 1.4(13) . . . . ?
C3 C4 C7 N2 -179.7(9) . . . . ?
N2 C7 N1 C7 -3.6(17) . . . 2 ?
C4 C7 N1 C7 177.6(6) . . . 2 ?
N1 C7 N2 C8 2.5(14) . . . . ?
C4 C7 N2 C8 -178.8(8) . . . . ?
C7 N2 C8 N2 -1.1(17) . . . 2 ?
C7 N2 C8 C9 179.8(9) . . . . ?
O7 P2 O6 Cu2 -40.9(7) . . . 4_454 ?
O7 P2 O6 Cu2 -170.1(4) 2 . . 4_454 ?
C12 P2 O6 Cu2 74.5(5) . . . 4_454 ?
O7 P2 O6 Cu2 170.1(4) . . . 3_444 ?
O7 P2 O6 Cu2 40.9(7) 2 . . 3_444 ?
C12 P2 O6 Cu2 -74.5(5) . . . 3_444 ?
O7 P2 O7 Cu2 43.6(9) 2 . . 4_453 ?
O6 P2 O7 Cu2 -83.2(6) . . . 4_453 ?
C12 P2 O7 Cu2 163.7(6) . . . 4_453 ?
N2 C8 C9 C10 179.5(10) . . . 2 ?
N2 C8 C9 C10 0.3(17) 2 . . 2 ?
N2 C8 C9 C10 -0.3(17) . . . . ?
N2 C8 C9 C10 -179.5(10) 2 . . . ?
C10 C9 C10 C11 5(2) 2 . . . ?
C8 C9 C10 C11 -175.0(11) . . . . ?
C9 C10 C11 C12 1.8(18) . . . . ?
C10 C11 C12 C11 -9(2) . . . 2 ?
C10 C11 C12 P2 169.9(9) . . . . ?
O7 P2 C12 C11 28.4(11) . . . . ?
O7 P2 C12 C11 153.2(10) 2 . . . ?
O6 P2 C12 C11 -89.2(10) . . . . ?
O7 P2 C12 C11 -153.2(10) . . . 2 ?
O7 P2 C12 C11 -28.4(11) 2 . . 2 ?
O6 P2 C12 C11 89.2(10) . . . 2 ?

_refine_diff_density_max         0.625
_refine_diff_density_min         -0.630
_refine_diff_density_rms         0.109

_shelxl_version_number           2013-4



# SQUEEZE RESULTS (APPEND TO CIF)
# Note: Data are Listed for all Voids in the P1 Unit Cell
# i.e. Centre of Gravity, Solvent Accessible Volume,
# Recovered number of Electrons in the Void and
# Details about the Squeezed Material
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
_platon_squeeze_void_content
1 0.627 0.000 -0.020 287 23 ' '
2 0.127 0.500 -0.246 287 23 ' '
_platon_squeeze_details          
;
;


_exptl_crystal_recrystallization_method 'hydrothermal synthesis'
