# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2021

####################################################################### 
# 
# 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_Cu-cit
_database_code_depnum_ccdc_archive 'CCDC 2070807'
_audit_update_record             
;
2021-03-16 deposited with the CCDC.	2021-06-25 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C6 H8 Cu2 O9'
_chemical_formula_weight         351.20

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'
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'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   'P 21/c'

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

_cell_length_a                   6.8900(7)
_cell_length_b                   9.7495(10)
_cell_length_c                   14.5033(16)
_cell_angle_alpha                90.00
_cell_angle_beta                 91.393(2)
_cell_angle_gamma                90.00
_cell_volume                     973.96(18)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    806
_cell_measurement_theta_min      2.52
_cell_measurement_theta_max      25.11

_exptl_crystal_description       BLOCK
_exptl_crystal_colour            BLUE
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.395
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             696
_exptl_absorpt_coefficient_mu    4.405
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.478
_exptl_absorpt_correction_T_max  0.644
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      296(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            5452
_diffrn_reflns_av_R_equivalents  0.0590
_diffrn_reflns_av_sigmaI/netI    0.0624
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         2.52
_diffrn_reflns_theta_max         25.11
_reflns_number_total             1735
_reflns_number_gt                1254
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'SMART (Bruker, 2001)'
_computing_cell_refinement       'SMART (Bruker, 2001)'
_computing_data_reduction        'SAINT+ (Bruker, 1999)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'PLATON (Spek, 2003)'
_computing_publication_material  'SHELXTL (1998)'

_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)+(0.0443P)²+3.3175P] 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         1735
_refine_ls_number_parameters     154
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0732
_refine_ls_R_factor_gt           0.0453
_refine_ls_wR_factor_ref         0.1079
_refine_ls_wR_factor_gt          0.0952
_refine_ls_goodness_of_fit_ref   1.003
_refine_ls_restrained_S_all      1.003
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu 0.80208(10) 0.74716(8) 0.33747(5) 0.0180(2) Uani 1 1 d . . .
O1 O 0.5972(7) 0.6233(6) 0.3721(4) 0.0495(16) Uani 1 1 d . . .
C1 C 0.4554(9) 0.5757(6) 0.3275(4) 0.0216(14) Uani 1 1 d . . .
O1W O 0.3432(7) 0.6139(5) 0.0645(3) 0.0395(13) Uani 1 1 d . . .
H1WA H 0.2211 0.6258 0.0662 0.047 Uiso 1 1 d R . .
H1WB H 0.3779 0.6300 0.0097 0.047 Uiso 1 1 d R . .
Cu2 Cu 0.59138(15) 0.64898(10) 0.14675(6) 0.0453(3) Uani 1 1 d . . .
O2 O 0.4254(8) 0.5905(7) 0.2438(3) 0.0603(19) Uani 1 1 d . . .
O2W O 0.6677(7) 0.4237(5) 0.1283(4) 0.0401(13) Uani 1 1 d . . .
H2WA H 0.7851 0.4191 0.1475 0.048 Uiso 1 1 d R . .
H2WB H 0.5975 0.3877 0.1692 0.048 Uiso 1 1 d R . .
C2 C 0.3110(9) 0.4984(6) 0.3829(4) 0.0210(14) Uani 1 1 d . . .
H2A H 0.2280 0.5636 0.4136 0.025 Uiso 1 1 calc R . .
H2B H 0.3800 0.4461 0.4302 0.025 Uiso 1 1 calc R . .
O3 O 0.7331(8) 0.8173(5) 0.5364(3) 0.0385(13) Uani 1 1 d . . .
C3 C 0.1848(8) 0.4013(6) 0.3256(4) 0.0177(13) Uani 1 1 d . . .
O4 O 0.9387(6) 0.7017(5) 0.4523(3) 0.0225(10) Uani 1 1 d . . .
C4 C 0.9331(9) 0.9754(7) 0.2497(4) 0.0217(14) Uani 1 1 d . . .
O5 O 0.9476(6) 0.9164(4) 0.3288(3) 0.0234(10) Uani 1 1 d . . .
C5 C 0.8749(9) 0.7339(6) 0.5285(4) 0.0201(14) Uani 1 1 d . . .
O6 O 1.0185(8) 1.0816(5) 0.2324(3) 0.0437(14) Uani 1 1 d . . .
C6 C 0.9660(9) 0.6685(6) 0.6129(4) 0.0186(14) Uani 1 1 d . . .
H6A H 1.0348 0.7381 0.6486 0.022 Uiso 1 1 calc R . .
H6B H 1.0601 0.6007 0.5940 0.022 Uiso 1 1 calc R . .
O7 O 0.6940(5) 0.7995(4) 0.2170(3) 0.0179(9) Uani 1 1 d . . .

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 0.0204(4) 0.0217(4) 0.0117(4) 0.0029(3) -0.0014(3) -0.0040(3)
O1 0.042(3) 0.075(4) 0.031(3) 0.026(3) -0.014(2) -0.038(3)
C1 0.028(4) 0.017(3) 0.021(4) -0.001(3) 0.004(3) -0.006(3)
O1W 0.030(3) 0.059(4) 0.030(3) 0.001(3) -0.001(2) 0.009(2)
Cu2 0.0699(7) 0.0518(7) 0.0148(5) -0.0111(4) 0.0153(4) -0.0417(5)
O2 0.075(4) 0.091(5) 0.015(3) 0.000(3) 0.004(3) -0.062(4)
O2W 0.031(3) 0.041(3) 0.048(3) 0.005(3) -0.010(2) -0.003(2)
C2 0.028(4) 0.019(3) 0.016(3) -0.004(3) 0.002(3) -0.011(3)
O3 0.060(3) 0.043(3) 0.013(2) 0.009(2) 0.010(2) 0.028(3)
C3 0.015(3) 0.020(3) 0.019(3) -0.003(3) 0.005(3) 0.000(3)
O4 0.028(2) 0.030(3) 0.010(2) 0.0006(19) 0.0018(18) 0.004(2)
C4 0.028(4) 0.021(4) 0.016(3) -0.001(3) 0.009(3) -0.001(3)
O5 0.030(3) 0.028(3) 0.012(2) 0.000(2) -0.0049(18) -0.011(2)
C5 0.024(3) 0.022(4) 0.015(3) -0.004(3) 0.001(3) -0.003(3)
O6 0.074(4) 0.037(3) 0.020(3) -0.001(2) 0.006(3) -0.038(3)
C6 0.022(3) 0.022(4) 0.012(3) 0.001(3) 0.005(3) -0.004(3)
O7 0.017(2) 0.021(2) 0.016(2) 0.0035(19) 0.0041(18) -0.0054(17)

_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 1.934(5) . ?
Cu1 O5 1.936(4) . ?
Cu1 O4 1.944(4) . ?
Cu1 O7 1.951(4) . ?
Cu1 O6 2.285(4) 2_745 ?
O1 C1 1.248(7) . ?
C1 O2 1.235(8) . ?
C1 C2 1.498(8) . ?
O1W Cu2 2.089(5) . ?
Cu2 O7 1.912(4) . ?
Cu2 O2 1.921(5) . ?
Cu2 O3 1.923(5) 4_575 ?
Cu2 O2W 2.275(5) . ?
C2 C3 1.520(8) . ?
O3 C5 1.278(7) . ?
O3 Cu2 1.923(4) 4_576 ?
C3 O7 1.445(7) 2_645 ?
C3 C4 1.527(9) 2_645 ?
C3 C6 1.544(8) 3_666 ?
O4 C5 1.240(7) . ?
C4 O6 1.220(8) . ?
C4 O5 1.284(7) . ?
C4 C3 1.527(9) 2_655 ?
C5 C6 1.504(8) . ?
O6 Cu1 2.285(4) 2_755 ?
C6 C3 1.544(8) 3_666 ?
O7 C3 1.445(7) 2_655 ?

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 O5 158.7(2) . . ?
O1 Cu1 O4 88.63(19) . . ?
O5 Cu1 O4 90.53(18) . . ?
O1 Cu1 O7 97.55(18) . . ?
O5 Cu1 O7 84.59(17) . . ?
O4 Cu1 O7 173.37(17) . . ?
O1 Cu1 O6 94.6(2) . 2_745 ?
O5 Cu1 O6 106.6(2) . 2_745 ?
O4 Cu1 O6 87.89(17) . 2_745 ?
O7 Cu1 O6 89.20(17) . 2_745 ?
C1 O1 Cu1 131.6(5) . . ?
O2 C1 O1 125.2(6) . . ?
O2 C1 C2 119.3(6) . . ?
O1 C1 C2 115.5(6) . . ?
O7 Cu2 O2 93.3(2) . . ?
O7 Cu2 O3 97.09(18) . 4_575 ?
O2 Cu2 O3 169.6(2) . 4_575 ?
O7 Cu2 O1W 135.79(19) . . ?
O2 Cu2 O1W 82.9(2) . . ?
O3 Cu2 O1W 88.7(2) 4_575 . ?
O7 Cu2 O2W 136.04(18) . . ?
O2 Cu2 O2W 86.7(2) . . ?
O3 Cu2 O2W 86.8(2) 4_575 . ?
O1W Cu2 O2W 87.89(18) . . ?
C1 O2 Cu2 131.8(5) . . ?
C1 C2 C3 113.5(5) . . ?
C5 O3 Cu2 126.0(4) . 4_576 ?
O7 C3 C2 109.4(5) 2_645 . ?
O7 C3 C4 108.8(5) 2_645 2_645 ?
C2 C3 C4 112.6(5) . 2_645 ?
O7 C3 C6 110.4(5) 2_645 3_666 ?
C2 C3 C6 110.0(5) . 3_666 ?
C4 C3 C6 105.6(5) 2_645 3_666 ?
C5 O4 Cu1 122.1(4) . . ?
O6 C4 O5 122.4(6) . . ?
O6 C4 C3 120.4(6) . 2_655 ?
O5 C4 C3 117.1(5) . 2_655 ?
C4 O5 Cu1 114.2(4) . . ?
O4 C5 O3 122.0(6) . . ?
O4 C5 C6 117.9(5) . . ?
O3 C5 C6 120.1(5) . . ?
C4 O6 Cu1 163.6(4) . 2_755 ?
C5 C6 C3 112.6(5) . 3_666 ?
C3 O7 Cu2 120.7(3) 2_655 . ?
C3 O7 Cu1 110.5(3) 2_655 . ?
Cu2 O7 Cu1 113.9(2) . . ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        25.11
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         0.966
_refine_diff_density_min         -1.483
_refine_diff_density_rms         0.138



