# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2019

####################################################################### 
# 
# 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_Calciumacetatformatemonohydrate
_database_code_depnum_ccdc_archive 'CCDC 1948773'
loop_
_audit_author_name
_audit_author_address
'Sebastian Bette'
;Max Planck Institute for Solid State Research
Germany
;
_audit_update_record             
;
2019-08-22 deposited with the CCDC.	2019-10-09 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_POWD002_Calciumacetatformatemonohydrate 
;
PROBLEM: _refine_ls_goodness_of_fit_all is missing (this is chi, i.e.
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. 
;
_vrf_PLAT043_Calciumacetatformatemonohydrate 
;
PROBLEM: Calculated and Reported Mol. Weight Differ by ..       5.03 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 related to the methyl group of the acetate ion and related to the water molecules were not included into the cif files. Accordingly 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 (PLAT043 ALERT 1 B).
;
_vrf_PLAT315_Calciumacetatformatemonohydrate 
;
PROBLEM: Singly Bonded Carbon Detected (H-atoms Missing).        C2A 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 related to the methyl group of the acetate ion were not included into the cif files. Accordingly the methyl related carbon atoms appears to be singly bonded but it is not.
;
_vrf_PLAT341_Calciumacetatformatemonohydrate 
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............       0.04 Ang.
RESPONSE: Due to the vast peak overlap at high diffraction angle, data were only collected and used up to a diffraction angle of 110.0\%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_PLAT430_Calciumacetatformatemonohydrate 
;
PROBLEM: Short Inter D...A Contact  O1       ..O2A      .       2.70 Ang.
RESPONSE: Strong interactions between hydrate water or hydroxide and carboxylate ions with short O-O distances are not uncommon in this type of compounds. In compounds like Cu2(OH)3(HCOO)1 similar bond distances were observed.
;
# Added during the CSD deposition process: Thursday 22 August 2019 04:25 PM
# end Validation Reply Form


_audit_creation_method           TOPAS

_chemical_name_common            Ca(CH3-COO)(HCOO)*H2O
_chemical_formula_moiety         '(C2 H3 O2), (C H O2), (O H2), (Ca)'
_chemical_formula_sum            'C3 H6 Ca O5'
_chemical_formula_weight         162.15

_cell_length_a                   9.27289(9)
_cell_length_b                   6.80022(7)
_cell_length_c                   11.22194(17)
_cell_angle_alpha                90
_cell_angle_beta                 121.2320(8)
_cell_angle_gamma                90
_cell_volume                     605.076(14)
_symmetry_space_group_name_H-M   P21/c
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14

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

_cell_formula_units_Z            4
_cell_measurement_temperature    298

_exptl_crystal_description       'microcrystalline powder'
_exptl_crystal_colour            white

_exptl_crystal_density_diffrn    1.78

loop_
_atom_type_symbol
_atom_type_oxidation_number
Ca 2
C 0
O -2
H 1

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
Ca1 Ca+2 4 e 0.9102(3) 0.9694(4) 0.6257(2) 1 0.49(8)
O1 O-2 4 e 0.7127(6) 0.9002(10) 0.7019(6) 1 2.9(2)
C1a C 4 e 0.691(2) 1.044(8) 0.3312(16) 1 2.70(11)
C2a C 4 e 0.565(5) 1.103(14) 0.178(3) 1 2.70(11)
O1a O 4 e 0.8412(6) 0.9945(10) 0.3762(7) 1 2.70(11)
O2a O 4 e 0.621(4) 1.052(12) 0.406(3) 1 2.70(11)
C1b C 4 e 1.119(8) 0.9604(18) 0.945(3) 1 2.70(11)
O1b O 4 e 1.1037(9) 1.1360(11) 0.9052(8) 1 2.70(11)
O2b O 4 e 1.084(13) 0.807(3) 0.865(5) 1 2.70(11)
H1b H 4 e 1.160(10) 0.921(4) 1.043(3) 1 1

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_multiplicity

C1a C2a 1.55(4) 4

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
O1a C1a O2a 125(2) 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      298
_diffrn_source                   ?
_diffrn_source_target            ?
_diffrn_source_type              Cu-tube
_diffrn_measurement_device_type  Stoe-Stadi-P
_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     1.5406
_diffrn_radiation_type           'Cu K\a'
_refine_ls_number_parameters     68
_pd_proc_ls_prof_R_factor        0.0124
_pd_proc_ls_prof_wR_factor       0.0158
_pd_proc_ls_prof_wR_expected     0.0010
_refine_ls_R_Fsqd_factor         0.0085
_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        2.0
_pd_meas_2theta_range_max        110.0
_pd_meas_2theta_range_inc        0.001
_pd_proc_2theta_range_min        10.0
_pd_proc_2theta_range_max        110.0
_pd_proc_2theta_range_inc        0.001
_chemical_properties_physical    Efflorescent,Heat-sensitive
####################################################################### 
# 
# 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_Ca3Ac4For2-4H2O
_database_code_depnum_ccdc_archive 'CCDC 1948774'
loop_
_audit_author_name
_audit_author_address
'Sebastian Bette'
;Max Planck Institute for Solid State Research
Germany
;
_audit_update_record             
;
2019-08-22 deposited with the CCDC.	2019-10-09 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT430_Ca3Ac4For2-4H2O     
;
PROBLEM: Short Inter D...A Contact  O1       ..O2C      .       2.51 Ang.
RESPONSE: Strong interactions between hydrate water or hydroxide and carboxylate ions with short O-O distances are not uncommon in this type of compounds. In compounds like Cu2(OH)3(HCOO)1 similar bond distances were observed.
;
_vrf_POWD002_Ca3Ac4For2-4H2O     
;
PROBLEM: _refine_ls_goodness_of_fit_all is missing (this is chi, i.e.
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. 
;
_vrf_PLAT043_Ca3Ac4For2-4H2O     
;
PROBLEM: Calculated and Reported Mol. Weight Differ by ..      20.13 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 related to the methyl group of the acetate ion and related to the water molecules were not included into the cif files. Accordingly 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 (PLAT043 ALERT 1 B).
;
_vrf_PLAT315_Ca3Ac4For2-4H2O     
;
PROBLEM: Singly Bonded Carbon Detected (H-atoms Missing).        C2A 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 related to the methyl group of the acetate ion were not included into the cif files. Accordingly the methyl related carbon atoms appears to be singly bonded but it is not.
;
_vrf_PLAT315_Ca3Ac4For2-4H2O_2   
;
PROBLEM: Singly Bonded Carbon Detected (H-atoms Missing).        C2B 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 related to the methyl group of the acetate ion were not included into the cif files. Accordingly the methyl related carbon atoms appears to be singly bonded but it is not.
;
_vrf_PLAT341_Ca3Ac4For2-4H2O     
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............     0.0285 Ang.
RESPONSE: Due to the vast peak overlap at high diffraction angle, data were only collected and used up to a diffraction angle of 110.0\%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_PLAT430_Ca3Ac4For2-4H2O_2   
;
PROBLEM: Short Inter D...A Contact  O1       ..O2C      .       2.81 Ang.
RESPONSE: Strong interactions between hydrate water or hydroxide and carboxylate ions with short O-O distances are not uncommon in this type of compounds. In compounds like Cu2(OH)3(HCOO)1 similar bond distances were observed.
;
_vrf_PLAT430_Ca3Ac4For2-4H2O_3   
;
PROBLEM: Short Inter D...A Contact  O1C      ..O2       .       2.64 Ang.
RESPONSE: Strong interactions between hydrate water or hydroxide and carboxylate ions with short O-O distances are not uncommon in this type of compounds. In compounds like Cu2(OH)3(HCOO)1 similar bond distances were observed.
;
# Added during the CSD deposition process: Thursday 22 August 2019 04:25 PM
# end Validation Reply Form


_audit_creation_method           TOPAS

_chemical_name_common            Ca3(CH3-COO)4(HCOO)2*4H2O
_chemical_formula_moiety         '4(C2 H3 O2), 2(C H O2), 4(O H2), 3(Ca)'
_chemical_formula_sum            'C10 H22 Ca3 O16'
_chemical_formula_weight         518.49

_cell_length_a                   6.86548(5)
_cell_length_b                   6.86548(5)
_cell_length_c                   45.5454(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2146.77(4)
_symmetry_space_group_name_H-M   P41212
_symmetry_cell_setting           tetragonal
_symmetry_Int_Tables_number      92


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

_cell_formula_units_Z            4
_cell_measurement_temperature    298

_exptl_crystal_description       'microcrystalline powder'
_exptl_crystal_colour            white

_exptl_crystal_density_diffrn    1.61

loop_
_atom_type_symbol
_atom_type_oxidation_number
Ca 2
C 0
O -2
H 1

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
Ca1 Ca+2 4 a 0.2780(7) 0.2780(7) 0 1 1.76(8)
Ca2 Ca+2 8 b 0.7692(8) 0.2531(8) 0.04356(7) 1 1.76(8)
O1 O-2 8 b 0.763(2) 0.0987(13) 0.0894(2) 1 3.0(3)
O2 O-2 8 b 0.736(2) -0.0888(14) 0.02814(19) 1 3.0(3)
C1a C 8 b 0.272(3) 0.258(7) 0.0627(5) 1 2.11(12)
C2a C 8 b 0.302(7) 0.225(10) 0.0960(6) 1 2.11(12)
O1a O 8 b 0.1052(18) 0.289(3) 0.0501(3) 1 2.11(12)
O2a O 8 b 0.429(3) 0.252(12) 0.0498(8) 1 2.11(12)
C1b C 8 b 0.772(4) 0.268(4) -0.0221(3) 1 2.11(12)
C2b C 8 b 0.750(3) 0.243(3) -0.0558(2) 1 2.11(12)
O1b O 8 b 0.936(6) 0.283(6) -0.0083(7) 1 2.11(12)
O2b O 8 b 0.636(6) 0.276(5) -0.0047(5) 1 2.11(12)
C1c C 8 b 0.734(5) 0.608(4) 0.0903(3) 1 2.11(12)
H2c H 8 b 0.744(5) 0.494(8) 0.1039(5) 1 2.11(12)
O1c O 8 b 0.765(2) 0.6013(15) 0.06225(15) 1 2.11(12)
O2c O 8 b 0.687(10) 0.755(6) 0.1040(6) 1 2.11(12)

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_multiplicity

C1a C2a 1.54(4) 4

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
O1a C1a O2a 125(3) 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      298
_diffrn_source                   ?
_diffrn_source_target            ?
_diffrn_source_type              Cu-tube
_diffrn_measurement_device_type  Stoe-Stadi-P
_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     1.5406
_diffrn_radiation_type           'Cu K\a'
_refine_ls_number_parameters     62
_pd_proc_ls_prof_R_factor        0.0474
_pd_proc_ls_prof_wR_factor       0.0634
_pd_proc_ls_prof_wR_expected     0.0080
_refine_ls_R_Fsqd_factor         0.0339
_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        2.0
_pd_meas_2theta_range_max        110.0
_pd_meas_2theta_range_inc        0.001
_pd_proc_2theta_range_min        5.0
_pd_proc_2theta_range_max        105.0
_pd_proc_2theta_range_inc        0.001
_chemical_properties_physical    Efflorescent,Heat-sensitive
