# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# 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_Cu3(CH3COO)2(OH)4
_database_code_depnum_ccdc_archive 'CCDC 1565871'
_audit_update_record             
;
2017-07-31 deposited with the CCDC.
2017-10-10 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_POWD002_Cu3(CH3COO)2(OH)4   
;
PROBLEM: _refine_ls_goodness_of_fit_all is missing (this is chi, i.e.
RESPONSE: Due to the vast peak overlap at high diffraction angle, data were only collected and used up to a diffraction angle of 60.0\%2 \q (Supporting Information, Figure S1). Accordingly the precision of the C-C bond is low. This is why the C-C bond of the acetate ion was refined within the rigid body while using restraints (see Structure Determination Section in the manuscript). 
;
_vrf_PLAT043_Cu3(CH3COO)2(OH)4   
;
PROBLEM: Calculated and Reported Mol. Weight Differ by ..      10.06 Check
RESPONSE: According to the limits of the XRPD method we did not do any attempt to determine and refine the hydrogen positions. Accordingly hydrogens were not included into the cif files. Accordingly 10 hydrogen atoms that are apparent in the solid phase are not included into the cif-file. That is why there is a difference between the reported and calculated molar mass of ca. 10 g/mol (PLAT043 ALERT 1 B).
;
_vrf_PLAT341_Cu3(CH3COO)2(OH)4   
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............      0.017 Ang.
RESPONSE: We did not report any GOF, as its definition is not suitable for up-to-date detectors. Modern point sensitive Mythen detectors (the devices we used) provide large global and local count rates, smooth intensity distribution with little statistical fluctuations and a high dynamic range; therefor weak reflections can be accurately measure in proximity of strong peaks. In addition these devices are almost noise free. Accordingly the powder pattern is treated by the software like if the scan time was far too long, although the applied scan time was moderate (see Table S1 in the supporting information). This leads to an artificial high GOF value, even for good fits. Hence we reported Rwp-, are R-F^2^- and R-p-values as well as a figure (Table S1) showing the fit of the whole powder pattern as the quality of the refinement might be better judged be these criteria. This problem is well known to powder diffractionists using a synchrotron beam line source and a 2D image plate detector or an array of Mythen detectors. 
;
# Added during the CSD deposition process: Monday 31 July 2017 03:21 PM
# end Validation Reply Form


_audit_creation_method           TOPAS

_chemical_name_common            "Cu(CH3-COO)2*2Cu'(OH)2*0H2O, 1-2-0 phase"
_chemical_formula_moiety         '2(C2 H3 O2), 4(O H), (Cu)'
_chemical_formula_sum            'C4 H10 Cu3 O8'
_chemical_formula_weight         376.75

_cell_length_a                   20.97417(14)
_cell_length_b                   7.20756(3)
_cell_length_c                   13.12202(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1983.691(18)
_symmetry_space_group_name_H-M   Pbca
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      61

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

_cell_formula_units_Z            8
_cell_measurement_temperature    303

_exptl_crystal_description       'microcrystalline powder'
_exptl_crystal_colour            blue

_exptl_crystal_density_diffrn    2.52

loop_
_atom_type_symbol
_atom_type_oxidation_number
Cu 2
C 0
O -2

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_symmetry_multiplicity
_atom_site_Wyckoff_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_B_iso_or_equiv
Cu1 Cu 8 c 0.89995(6) 0.37402(13) 0.25512(15) 1 0.828(15)
Cu2 Cu 8 c 0.00610(12) 0.2946(2) 0.63042(12) 1 0.828(15)
Cu3 Cu 8 c 0.00533(12) 0.1961(2) 0.37940(12) 1 0.828(15)
O1 O 8 c 0.9622(2) 0.1606(5) 0.2493(7) 1 0.77(7)
O2 O 8 c 0.9480(2) 0.7467(10) 0.9891(6) 1 0.77(7)
O3 O 8 c 0.5456(3) 0.9303(8) 0.1323(5) 1 0.77(7)
O4 O 8 c 0.9756(3) 0.4394(9) 0.3747(5) 1 0.77(7)
C11 C 8 c 0.1439(5) 0.6587(9) 0.0912(5) 1 2.82(8)
C12 C 8 c 0.1941(8) 0.532(2) 0.0468(9) 1 2.82(8)
O11 O 8 c 0.0899(8) 0.646(3) 0.0511(12) 1 2.82(8)
O12 O 8 c 0.1635(13) 0.764(2) 0.1652(9) 1 2.82(8)
C21 C 8 c 0.8617(5) 0.7500(10) 0.7303(4) 1 2.82(8)
C22 C 8 c 0.8143(7) 0.6196(19) 0.6856(7) 1 2.82(8)
O21 O 8 c 0.8433(11) 0.9105(17) 0.7393(10) 1 2.82(8)
O22 O 8 c 0.9143(7) 0.694(3) 0.7549(8) 1 2.82(8)

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_multiplicity
C11 O11 1.25(2) 8


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_2
_geom_angle_site_symmetry_3
O11 C11 O12 130(1) 1_555 1_555 1_555

# Powder diffraction data for histogram  1
#==============================================================================
# 4. INSTRUMENT CHARACTERIZATION

_exptl_special_details           
; ?
;

# if regions of the data are excluded, the reason(s) are supplied here:
_pd_proc_info_excluded_regions   
;
 ?
;

# The following item is used to identify the equipment used to record
# the powder pattern when the diffractogram was measured at a laboratory
# other than the authors' home institution, e.g. when neutron or synchrotron
# radiation is used.

_pd_instr_location               
; 
'SLS (Swiss Light Source)'
;
_pd_calibration_special_details  
# description of the method used
# to calibrate the instrument
; 
'Standard Reference Materials NIST SRM640c (Silicon powder)'
;

_diffrn_ambient_temperature      303
_diffrn_source                   ?
_diffrn_source_target            ?
_diffrn_source_type              'synchrotron radiation'
_diffrn_measurement_device_type  'synchrotron radiation'
_diffrn_detector                 
; 
 multi MYTHEN II (Dectris)   
;
_diffrn_detector_type            ? # make or model of detector

_pd_meas_scan_method             step
_pd_meas_special_details         
;  ?
;

# The following two items identify the program(s) used (if appropriate).
_computing_data_collection       ?
_computing_data_reduction        ?

# Describe any processing performed on the data, prior to refinement.
# For example: a manual Lp correction or a precomputed absorption correction
_pd_proc_info_data_reduction     binning

# The following items are used to define the size of the instrument.
# Not all distances are appropriate for all instrument types.

_pd_instr_dist_src/mono          ?
_pd_instr_dist_mono/spec         ?
_pd_instr_dist_src/spec          ?
_pd_instr_dist_spec/anal         ?
_pd_instr_dist_anal/detc         ?
_pd_instr_dist_spec/detc         ?

# 5. Specimen size and mounting information

# The next three fields give the specimen dimensions in mm.  The equatorial
# plane contains the incident and diffracted beam.

_pd_spec_size_axial              ? # perpendicular to
# equatorial plane

_pd_spec_size_equat              ? # parallel to
# scattering vector
# in transmission

_pd_spec_size_thick              ? # parallel to
# scattering vector
# in reflection

_pd_spec_mounting                
# This field should be
# used to give details of the
# container.
; 
'0.5 mm glass capillary'
;

_pd_spec_mount_mode              transmission

_pd_spec_shape                   cylinder

_diffrn_radiation_probe          X-ray
_diffrn_radiation_wavelength     0.8260
_diffrn_radiation_type           synchrotron
_refine_ls_number_parameters     78
_pd_proc_ls_prof_R_factor        0.0868
_pd_proc_ls_prof_wR_factor       0.0832
_pd_proc_ls_prof_wR_expected     0.0111
_refine_ls_R_Fsqd_factor         0.0412
_pd_proc_ls_background_function  
;   
'Chebyshev polynomial'
;

_exptl_absorpt_process_details   
;   
 ?
;
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?

_pd_proc_ls_profile_function     
;
 Fundamental parameters
;
_pd_proc_ls_peak_cutoff          0.00100
_pd_proc_info_datetime           ?
_pd_calc_method                  'Rietveld Refinement'

#---- raw/calc data loop -----
_pd_meas_2theta_range_min        3.0
_pd_meas_2theta_range_max        60.0
_pd_meas_2theta_range_inc        0.001
_pd_proc_2theta_range_min        3.0
_pd_proc_2theta_range_max        60.0
_pd_proc_2theta_range_inc        0.001
_chemical_melting_point          'decomposition above 160\%C'
_chemical_properties_physical    Heat-sensitive
_exptl_crystal_preparation       'Magnetic properties'
