# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2020

####################################################################### 
# 
# 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_FE-HPAA_700C_publ
_database_code_depnum_ccdc_archive 'CCDC 1974538'
loop_
_audit_author_name
_audit_author_address
'Aurelio Cabeza Diaz'
;Universidad de Malaga
Spain
;
_audit_update_record             
;
2019-12-28 deposited with the CCDC.	2020-01-02 downloaded from the CCDC.
;

_pd_block_id                     2019-12-19T16:06|FE-HPAA_700C|PTau-Gd|

_audit_creation_method           'from EXP file using GSAS2CIF'
_audit_creation_date             2019-12-19T16:06

#=============================================================================
# 5. OVERALL REFINEMENT & COMPUTING DETAILS

_refine_special_details          
; ?
;
_pd_proc_ls_special_details      
; ?
;

# The following items are used to identify the programs used.
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_ls_weighting_scheme      ?
_refine_ls_weighting_details     ?
_refine_ls_hydrogen_treatment    ?
_refine_ls_extinction_method     ?
_refine_ls_extinction_coef       ?
_refine_ls_number_constraints    ?

_refine_ls_restrained_S_all      ?
_refine_ls_restrained_S_obs      ?

#==============================================================================
# 6. SAMPLE PREPARATION DATA

# (In the unusual case where multiple samples are used in a single
#  Rietveld study, this information should be moved into the phase
#  blocks)

# The following three fields describe the preparation of the material.
# The cooling rate is in K/min.  The pressure at which the sample was
# prepared is in kPa.  The temperature of preparation is in K.

_pd_prep_cool_rate               ?
_pd_prep_pressure                ?
_pd_prep_temperature             ?

_pd_char_colour                  black # use ICDD colour descriptions
_refine_ls_shift/su_max          0.07
_refine_ls_shift/su_mean         0.01
_computing_structure_refinement  GSAS
_refine_ls_number_parameters     77
_refine_ls_goodness_of_fit_all   1.57
_refine_ls_number_restraints     30
_refine_ls_matrix_type           full
#==============================================================================
# 7. CHEMICAL, STRUCTURAL AND CRYSTAL DATA

_pd_char_particle_morphology     ?

_chemical_name_systematic        'iron(II) pyprophosphate'
_chemical_name_common            ?
_chemical_formula_moiety         ?
_chemical_formula_structural     ?
_chemical_formula_analytical     ?
_chemical_melting_point          ?
_chemical_compound_source        ? # for minerals and
# natural products
_symmetry_space_group_name_Hall  -b_2yab

_exptl_crystal_F_000             ?
_exptl_crystal_density_diffrn    3.889
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       powder

_cell_measurement_temperature    298

_cell_special_details            
; ?
;

_geom_special_details            ?

# The following item identifies the program(s) used (if appropriate).
_computing_structure_solution    ?

#==============================================================================

# 8. Phase information from GSAS

_pd_phase_name                   Fe06Zn04-N2-1000
_cell_length_a                   13.298(5)
_cell_length_b                   8.4370(32)
_cell_length_c                   8.9932(32)
_cell_angle_alpha                90.0
_cell_angle_beta                 104.246(12)
_cell_angle_gamma                90.0
_cell_volume                     977.9(10)
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   'B 21/c'

loop_
_symmetry_equiv_pos_site_id
_symmetry_equiv_pos_as_xyz
1 +x,+y,+z
2 -x,+y+1/2,-z+1/2
-1 -x,-y,-z
-2 +x,-y+1/2,+z+1/2
101 +x+1/2,+y,+z+1/2
102 -x+1/2,+y+1/2,-z
-101 -x+1/2,-y,-z+1/2
-102 +x+1/2,-y+1/2,+z

# ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS


loop_
_atom_site_type_symbol
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_thermal_displace_type
_atom_site_U_iso_or_equiv
_atom_site_symmetry_multiplicity
Fe Fe1 0.3901(5) 0.9451(9) 0.2411(11) 1.0 Uiso 0.0168(16) 8
Fe Fe2 0.3718(6) 0.5602(9) 0.2526(12) 1.0 Uiso 0.0168(16) 8
P P1 0.2677(7) 0.2622(12) 0.0425(11) 1.0 Uiso 0.0168(16) 8
P P2 0.4823(8) 0.2576(12) -0.0469(11) 1.0 Uiso 0.0168(16) 8
O O1 0.3705(12) 0.2854(15) -0.0167(24) 1.0 Uiso 0.0168(16) 8
O O2 0.5594(16) 0.2524(13) 0.1116(11) 1.0 Uiso 0.0168(16) 8
O O3 0.1785(14) 0.2519(13) -0.1040(13) 1.0 Uiso 0.0168(16) 8
O O4 0.2780(11) 0.1084(20) 0.1365(21) 1.0 Uiso 0.0168(16) 8
O O5 0.2539(9) 0.4055(21) 0.1416(16) 1.0 Uiso 0.0168(16) 8
O O6 0.4848(8) 0.1002(19) -0.1324(19) 1.0 Uiso 0.0168(16) 8
O O7 0.5057(8) 0.3980(19) -0.1428(18) 1.0 Uiso 0.0168(16) 8

# If you change Z, be sure to change all 3 of the following
_chemical_formula_sum            'Fe2 O7 P2'
_chemical_formula_weight         285.64
_cell_formula_units_Z            8

# MOLECULAR GEOMETRY

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_1
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Fe1 O2 2.100(7) . 2_655 N
Fe1 O3 2.111(7) . 102_555 N
Fe1 O4 2.078(7) . 1_565 N
Fe1 O6 2.160(7) . -1_665 N
Fe1 O7 2.101(7) . -2_565 N
Fe2 O2 2.099(7) . 2_655 N
Fe2 O3 2.100(7) . 102_555 N
Fe2 O5 2.095(15) . 1_555 N
Fe2 O5 2.138(7) . -101_464 N
Fe2 O6 2.096(8) . -2_555 N
Fe2 O7 2.131(7) . -1_665 N
P1 O1 1.597(4) . 1_555 N
P1 O3 1.542(4) . 1_555 N
P1 O4 1.536(4) . 1_555 N
P1 O5 1.540(4) . 1_555 N
P2 O1 1.592(4) . 1_555 N
P2 O2 1.539(4) . 1_555 N
P2 O6 1.539(4) . 1_555 N
P2 O7 1.541(4) . 1_555 N
O1 P1 1.597(4) . 1_555 N
O1 P2 1.592(4) . 1_555 N
O2 Fe1 2.100(7) . 2_645 N
O2 Fe2 2.099(7) . 2_645 N
O2 P2 1.539(4) . 1_555 N
O3 Fe1 2.111(7) . 102_545 N
O3 Fe2 2.100(7) . 102_545 N
O3 P1 1.542(4) . 1_555 N
O4 Fe1 2.078(7) . 1_545 N
O4 P1 1.536(4) . 1_555 N
O5 Fe2 2.095(15) . 1_555 N
O5 Fe2 2.138(7) . -101_464 N
O5 P1 1.540(4) . 1_555 N
O6 Fe1 2.160(7) . -1_665 N
O6 Fe2 2.096(8) . -2_554 N
O6 P2 1.539(4) . 1_555 N
O7 Fe1 2.101(7) . -2_564 N
O7 Fe2 2.131(7) . -1_665 N
O7 P2 1.541(4) . 1_555 N

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
_geom_angle_publ_flag
O2 Fe1 O3 78.21(32) 2_655 . 102_554 N
O2 Fe1 O4 151.8(10) 2_655 . 1_565 N
O2 Fe1 O6 89.2(9) 2_655 . -1_665 N
O2 Fe1 O7 95.3(7) 2_655 . -2_576 N
O3 Fe1 O4 95.1(9) 102_554 . 1_565 N
O3 Fe1 O6 82.5(7) 102_554 . -1_665 N
O3 Fe1 O7 159.2(8) 102_554 . -2_576 N
O4 Fe1 O6 117.3(8) 1_565 . -1_665 N
O4 Fe1 O7 99.4(8) 1_565 . -2_576 N
O6 Fe1 O7 77.6(4) -1_665 . -2_576 N
O2 Fe2 O3 78.48(32) 2_655 . 102_554 N
O2 Fe2 O5 157.9(9) 2_655 . 1_555 N
O2 Fe2 O5 85.0(9) 2_655 . -101_565 N
O2 Fe2 O6 93.2(7) 2_655 . -2_566 N
O2 Fe2 O7 82.5(7) 2_655 . -1_665 N
O3 Fe2 O5 95.3(8) 102_554 . 1_555 N
O3 Fe2 O5 91.0(9) 102_554 . -101_565 N
O3 Fe2 O6 152.7(8) 102_554 . -2_566 N
O3 Fe2 O7 74.8(7) 102_554 . -1_665 N
O5 Fe2 O5 73.8(5) 1_555 . -101_565 N
O5 Fe2 O6 101.2(7) 1_555 . -2_566 N
O5 Fe2 O7 116.7(8) 1_555 . -1_665 N
O5 Fe2 O6 114.3(8) -101_565 . -2_566 N
O5 Fe2 O7 162.7(7) -101_565 . -1_665 N
O6 Fe2 O7 78.4(5) -2_566 . -1_665 N
O1 P1 O3 105.3(4) 1_555 . 1_555 N
O1 P1 O4 108.6(5) 1_555 . 1_555 N
O1 P1 O5 109.2(5) 1_555 . 1_555 N
O3 P1 O4 111.61(34) 1_555 . 1_555 N
O3 P1 O5 111.25(34) 1_555 . 1_555 N
O4 P1 O5 110.6(5) 1_555 . 1_555 N
O1 P2 O2 106.5(5) 1_555 . 1_555 N
O1 P2 O6 110.4(5) 1_555 . 1_555 N
O1 P2 O7 108.0(5) 1_555 . 1_555 N
O2 P2 O6 110.2(5) 1_555 . 1_555 N
O2 P2 O7 111.1(5) 1_555 . 1_555 N
O6 P2 O7 110.6(5) 1_555 . 1_555 N
P1 O1 P2 161.9(8) 1_555 . 1_555 N
Fe1 O2 Fe2 101.9(4) 2_645 . 2_645 N
Fe1 O2 P2 126.8(7) 2_645 . 1_555 N
Fe2 O2 P2 131.0(8) 2_645 . 1_555 N
Fe1 O3 Fe2 101.5(4) 102_545 . 102_545 N
Fe1 O3 P1 125.9(7) 102_443 . 1_555 N
Fe2 O3 P1 130.1(8) 102_443 . 1_555 N
Fe1 O4 P1 140.0(10) 1_545 . 1_555 N
Fe2 O5 Fe2 106.2(5) 1_555 . -101_566 N
Fe2 O5 P1 125.7(9) 1_555 . 1_555 N
Fe2 O5 P1 125.5(8) -101_464 . 1_555 N
Fe1 O6 Fe2 101.6(5) -1_665 . -2_566 N
Fe1 O6 P2 119.5(6) -1_665 . 1_555 N
Fe2 O6 P2 134.6(8) -2_454 . 1_555 N
Fe1 O7 Fe2 102.4(5) -2_576 . -1_665 N
Fe1 O7 P2 122.5(7) -2_464 . 1_555 N
Fe2 O7 P2 132.0(6) -1_665 . 1_555 N

# Powder diffraction data for histogram  1
#==============================================================================
# 9. 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               
; ?
;
_pd_calibration_special_details  
# description of the method used
# to calibrate the instrument
; ?
;

_diffrn_ambient_temperature      298
_diffrn_source                   ?
_diffrn_source_target            ?
_diffrn_source_type              ?
_diffrn_measurement_device_type  'D8 ADVANCE'
_diffrn_detector                 ?
_diffrn_detector_type            ? # make or model of detector

_pd_meas_scan_method             ? # options are 'step', 'cont',
# 'tof', 'fixed' or
# 'disp' (= dispersive)
_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     ?

# The following item is used for angular dispersive measurements only.

_diffrn_radiation_monochromator  ?

# 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         ?

# 10. 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.
; ?
;

_pd_spec_mount_mode              ? # options are 'reflection'
# or 'transmission'

_pd_spec_shape                   ? # options are 'cylinder'
# 'flat_sheet' or 'irregular'


loop_
_atom_type_symbol
_atom_type_number_in_cell
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_Cromer_Mann_a1
_atom_type_scat_Cromer_Mann_a2
_atom_type_scat_Cromer_Mann_a3
_atom_type_scat_Cromer_Mann_a4
_atom_type_scat_Cromer_Mann_b1
_atom_type_scat_Cromer_Mann_b2
_atom_type_scat_Cromer_Mann_b3
_atom_type_scat_Cromer_Mann_b4
_atom_type_scat_Cromer_Mann_c
_atom_type_scat_source
Fe 16.0 0.000 0.000 11.7695 4.76110 7.35730 0.30720 3.52220 15.3535 2.30450
76.8805 1.03690 International_Tables_Vol_C
P 16.0 0.000 0.000 6.43450 1.90670 4.17910 27.1570 1.78000 0.52600 1.49080
68.1645 1.11490 International_Tables_Vol_C
O 56.0 0.000 0.000 3.04850 13.2771 2.28680 5.70110 1.54630 0.32390 0.86700
32.9089 0.25080 International_Tables_Vol_C
_diffrn_radiation_probe          x-ray
_diffrn_radiation_polarisn_ratio 0.81
_diffrn_radiation_wavelength     0.7093
_diffrn_radiation_type           'Mo K\a'
_pd_proc_ls_prof_R_factor        0.0378
_pd_proc_ls_prof_wR_factor       0.0486
_pd_proc_ls_prof_wR_expected     0.0347
_refine_ls_R_Fsqd_factor         0.01844

_pd_proc_ls_background_function  
;   GSAS Background function number 1 with 18 terms.
 Shifted Chebyshev function of 1st kind
      1:    26633.8     2:   -17667.8     3:    9373.68     4:   -5640.90    
      5:    2735.65     6:   -1327.15     7:    1014.48     8:   -60.6324    
      9:   -544.285    10:    655.908    11:   -286.255    12:    314.263    
     13:    574.986    14:   -467.060    15:   -647.985    16:    325.906    
     17:    126.165    18:   -207.851    
;

_exptl_absorpt_process_details   
;   GSAS Absorption/surface roughness correction: function number 0
 No correction is applied.
;
_exptl_absorpt_correction_T_min  1.00000
_exptl_absorpt_correction_T_max  1.00000
_pd_proc_ls_profile_function     
;
 CW Profile function number 4 with  21 terms
 Pseudovoigt profile coefficients as parameterized in
 P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83.
 Asymmetry correction of L.W. Finger, D.E. Cox & A. P. Jephcoat (1994).
 J. Appl. Cryst.,27,892-900.
 Microstrain broadening by P.W. Stephens,  (1999). J. Appl. Cryst.,32,281-289.
 #1(GU)   =    0.000 #2(GV)   =    0.000 #3(GW)   =   21.323
 #4(GP)   =    0.000 #5(LX)   =   10.807 #6(ptec) =     0.00
 #7(trns) =     0.00 #8(shft) =   0.0000 #9(sfec) =     0.00
 #10(S/L) =   0.0005 #11(H/L) =   0.0005 #12(eta) =   0.5099
 #13(S400 ) =  1.8E-01 #14(S040 ) =  6.3E-01 #15(S004 ) =  7.7E-01
 #16(S220 ) =  4.0E+00 #17(S202 ) =  4.3E-01 #18(S022 ) =  3.4E-01
 #19(S301 ) =  7.5E-02 #20(S103 ) =  2.2E-02 #21(S121 ) =  1.7E+00
 Peak tails are ignored  where the intensity is below 0.0030 times the peak
   Aniso. broadening axis   0.0   1.0   0.0
;
_pd_proc_ls_peak_cutoff          0.00300
_pd_proc_info_datetime           2019-12-19T16:06:39
_pd_calc_method                  'Rietveld Refinement'

#---- raw/calc data loop -----
_pd_meas_2theta_range_min        2.5
_pd_meas_2theta_range_max        35.0
_pd_meas_2theta_range_inc        0.02
_pd_proc_2theta_range_min        2.51883
_pd_proc_2theta_range_max        35.01883
_pd_proc_2theta_range_inc        0.02

loop_
_gsas_i100_meas
1.20
1.14
12.18
0.52
11.62
0.99
0.16
1.23
0.22
0.34
0.27
1.74
1.24
0.28
0.41
0.03
0.75
0.66
45.34
0.41
100.00
65.30
0.80
0.46
0.76
25.23
0.01
22.78
1.73
0.52
0.36
0.36
0.19
0.19
0.33
0.01
0.89
0.07
1.83
0.00
0.52
0.06
4.54
0.41
0.05
0.00
0.22
22.58
2.13
1.83
0.16
0.21
0.41
3.49
3.63
13.11
9.96
0.11
0.01
8.21
0.26
0.01
0.08
2.44
0.09
0.16
0.00
0.57
0.16
0.04
0.37
0.26
0.07
0.29
0.09
0.01
0.08
0.30
0.06
3.35
0.35
0.17
0.18
0.49
16.45
0.00
2.87
7.08
1.24
0.11
0.03
7.51
0.27
4.42
0.31
0.48
0.17
0.00
0.04
0.39
0.30
4.13
1.40
0.10
0.15
0.44
0.23
0.58
1.23
0.26
0.32
0.17
0.17
0.16
0.01
0.35
0.15
0.49
6.90
0.11
0.00
0.18
1.62
0.27
0.06
0.46
0.01
0.13
0.01
0.00
19.49
6.64
8.55
0.00
0.20
0.02
0.14
0.16
6.84
0.09
0.06
5.55
1.50
5.59
5.02
0.01
0.01
0.00
0.03
6.97
2.53
0.00
0.13
0.01
0.23
0.45
0.00
0.25
0.14
3.73
0.02
0.17
0.05
1.60
2.26
0.03
1.95
0.16
0.09
0.01
1.59
0.04
0.02
0.19
0.38
0.04
0.20
1.74
1.73
0.00
0.00
0.92
0.04
0.00
3.14
0.02
0.01
0.14
0.06
0.16
0.03
0.01
3.34
0.03
0.65
0.25
0.11
0.03
0.04
0.16
1.91
2.11
0.00
0.18
0.01
0.02
5.44
0.02
0.06
0.57
0.40
0.03
2.41
0.28
0.12
1.06
0.07
0.00
2.18
0.00
0.06
0.92
0.31
0.09
0.00
0.06
0.08
0.01
0.01
0.52
0.23
0.17
0.07
0.00
0.14
0.05
0.44
3.73
2.84
0.01
0.07
0.00
0.06
0.01
8.46
0.00
0.00
0.00
0.15
0.26
3.92
0.13
0.24
0.01
0.01
0.00
0.03
0.07
0.30
0.01
2.43
0.00
0.12
0.90
0.26
0.02
0.04
0.04
0.19
0.46
0.81
0.26
0.03
0.27
0.01
0.01
0.33
0.13
0.55
0.08
0.01
0.21
0.01
0.04
0.18
0.03
0.11
0.01
0.11
0.25
0.02
2.39
0.10
0.01
0.01
0.01
0.01
0.03
0.00
1.32
0.07
0.10
0.00
0.62
0.16
0.01
0.04
0.17
0.33
0.00
0.00
0.18
_reflns_number_total             312
_reflns_limit_h_min              0
_reflns_limit_h_max              14
_reflns_limit_k_min              0
_reflns_limit_k_max              9
_reflns_limit_l_min              -9
_reflns_limit_l_max              9
_reflns_d_resolution_high        1.180
_reflns_d_resolution_low         6.444
#--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--#
