# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2018

####################################################################### 
# 
# 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_PbFePO4F2
_database_code_depnum_ccdc_archive 'CCDC 1040865'
_audit_update_record             
;
2018-10-04 deposited with the CCDC.
2018-10-09 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_chemical_name_systematic        'Lead Iron Phosphate Fluoride'
_chemical_name_common            ?
_chemical_formula_moiety         'F2 Fe O4 P Pb'
_chemical_formula_sum            'F2 Fe O4 P Pb'
_chemical_melting_point          ?

_exptl_crystal_description       block
_exptl_crystal_colour            black
_diffrn_ambient_temperature      123(2)
_chemical_formula_weight         396.02

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
O O 0.0106 0.0060 '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'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Pb Pb -3.3944 10.1111 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
I I -0.4742 1.8119 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

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

_cell_length_a                   5.257(2)
_cell_length_b                   12.404(5)
_cell_length_c                   7.098(3)
_cell_angle_alpha                90
_cell_angle_beta                 102.765(9)
_cell_angle_gamma                90
_cell_volume                     451.4(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    123(2)
_cell_measurement_reflns_used    1422
_cell_measurement_theta_min      3.3
_cell_measurement_theta_max      27.5
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    5.827
_exptl_crystal_F_000             692.0
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.020
_exptl_crystal_size_mid          0.010
_exptl_crystal_size_min          0.010
_exptl_absorpt_coefficient_mu    40.791
_shelx_estimated_absorpt_T_min   0.686
_shelx_estimated_absorpt_T_max   0.822
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.619
_exptl_absorpt_correction_T_max  0.665
_exptl_absorpt_process_details   CrystalClear
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_type              graphite
_diffrn_measurement_device_type  Rigaku
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            3723
_diffrn_reflns_av_unetI/netI     0.0362
_diffrn_reflns_av_R_equivalents  0.0314
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_theta_min         3.285
_diffrn_reflns_theta_max         27.515
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measured_fraction_theta_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_point_group_measured_fraction_full 0.996
_reflns_number_total             1039
_reflns_number_gt                954
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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
_computing_cell_refinement       CrystalClear-SM
_computing_data_reduction        CrystalClear-SM
_computing_structure_solution    'SHELXT-2014/7 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 1997)'
_computing_publication_material  'WinGX publication routines (Farrugia, 2012)'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0158P)²+11.6559P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   .
_refine_ls_hydrogen_treatment    undef
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_extinction_coef       0.0020(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         1026
_refine_ls_number_parameters     60
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0394
_refine_ls_R_factor_gt           0.0367
_refine_ls_wR_factor_ref         0.0696
_refine_ls_wR_factor_gt          0.0679
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_restrained_S_all      1.010
_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
Fe1 Fe 0.0000 0.5000 0.5000 0.0089(3) Uani 1 2 d S . P . .
Fe2 Fe 0.0000 0.5000 0.0000 0.0076(3) Uani 1 2 d S . P . .
P P 0.4326(4) 0.61518(16) 0.8072(3) 0.0090(4) Uiso 1 1 d . . . . .
F1 F 0.1007(9) 0.5565(4) 0.2720(7) 0.0129(9) Uiso 1 1 d . . . . .
F2 F 0.1162(9) 0.3572(4) 0.4495(7) 0.0133(9) Uiso 1 1 d . . . . .
O1 O 0.3548(10) 0.5221(4) 0.6633(8) 0.0101(11) Uiso 1 1 d . . . . .
O2 O 0.4280(11) 0.7206(4) 0.6938(8) 0.0128(12) Uiso 1 1 d . . . . .
O3 O 0.7035(10) 0.6015(4) 0.9346(8) 0.0105(11) Uiso 1 1 d . . . . .
O4 O 0.2318(10) 0.6243(4) 0.9371(8) 0.0120(11) Uiso 1 1 d . . . . .
PbA Pb 0.5534(2) 0.28669(10) 0.65245(16) 0.0191(2) Uani 0.646 1 d . . P . .
PbB Pb 0.4932(5) 0.3010(2) 0.7056(4) 0.0653(9) Uani 0.354 1 d . . P . .

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
Fe1 0.0091(8) 0.0086(7) 0.0082(8) -0.0013(6) 0.0000(6) -0.0003(6)
Fe2 0.0077(7) 0.0067(7) 0.0076(7) 0.0005(5) 0.0000(6) 0.0002(5)
PbA 0.0264(4) 0.0137(3) 0.0156(4) 0.0013(2) 0.0012(3) -0.0055(2)
PbB 0.0694(18) 0.0311(12) 0.0653(18) 0.0306(11) -0.0499(12) -0.0305(11)

_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
Fe1 F2 1.933(5) 3_566 ?
Fe1 F2 1.933(5) . ?
Fe1 F1 1.941(5) 3_566 ?
Fe1 F1 1.941(5) . ?
Fe1 O1 1.985(5) 3_566 ?
Fe1 O1 1.985(5) . ?
Fe2 O3 1.978(5) 3_666 ?
Fe2 O3 1.978(5) 1_454 ?
Fe2 F1 2.012(5) . ?
Fe2 F1 2.012(5) 3_565 ?
Fe2 O4 2.074(5) 3_566 ?
Fe2 O4 2.074(5) 1_554 ?
P O3 1.518(6) . ?
P O2 1.533(6) . ?
P O1 1.536(6) . ?
P O4 1.552(6) . ?
F1 PbA 2.636(5) 3_666 ?
F2 PbB 2.475(5) . ?
F2 PbA 2.580(5) . ?
F2 PbB 2.601(5) 4_565 ?
F2 PbA 2.726(5) 4_565 ?
O2 PbA 2.483(6) 3_666 ?
O2 PbB 2.665(6) 2_556 ?
O3 Fe2 1.978(5) 1_656 ?
O4 Fe2 2.074(5) 1_556 ?
O4 PbA 2.508(6) 2_556 ?
O4 PbB 2.588(6) 2_556 ?
PbA PbB 0.571(4) . ?
PbA O2 2.483(6) 3_666 ?
PbA O4 2.508(6) 2_546 ?
PbA F1 2.636(5) 3_666 ?
PbA F2 2.726(5) 4_666 ?
PbB O4 2.588(6) 2_546 ?
PbB F2 2.601(5) 4_666 ?
PbB O2 2.665(6) 2_546 ?

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
F2 Fe1 F2 180.0 3_566 . ?
F2 Fe1 F1 91.17(19) 3_566 3_566 ?
F2 Fe1 F1 88.83(19) . 3_566 ?
F2 Fe1 F1 88.83(19) 3_566 . ?
F2 Fe1 F1 91.17(19) . . ?
F1 Fe1 F1 180.0 3_566 . ?
F2 Fe1 O1 86.6(2) 3_566 3_566 ?
F2 Fe1 O1 93.4(2) . 3_566 ?
F1 Fe1 O1 92.4(2) 3_566 3_566 ?
F1 Fe1 O1 87.6(2) . 3_566 ?
F2 Fe1 O1 93.4(2) 3_566 . ?
F2 Fe1 O1 86.6(2) . . ?
F1 Fe1 O1 87.6(2) 3_566 . ?
F1 Fe1 O1 92.4(2) . . ?
O1 Fe1 O1 180.0 3_566 . ?
O3 Fe2 O3 180.0 3_666 1_454 ?
O3 Fe2 F1 88.3(2) 3_666 . ?
O3 Fe2 F1 91.7(2) 1_454 . ?
O3 Fe2 F1 91.7(2) 3_666 3_565 ?
O3 Fe2 F1 88.3(2) 1_454 3_565 ?
F1 Fe2 F1 180.0 . 3_565 ?
O3 Fe2 O4 86.9(2) 3_666 3_566 ?
O3 Fe2 O4 93.1(2) 1_454 3_566 ?
F1 Fe2 O4 95.4(2) . 3_566 ?
F1 Fe2 O4 84.6(2) 3_565 3_566 ?
O3 Fe2 O4 93.1(2) 3_666 1_554 ?
O3 Fe2 O4 86.9(2) 1_454 1_554 ?
F1 Fe2 O4 84.6(2) . 1_554 ?
F1 Fe2 O4 95.4(2) 3_565 1_554 ?
O4 Fe2 O4 180.0(2) 3_566 1_554 ?
O3 P O2 108.2(3) . . ?
O3 P O1 112.9(3) . . ?
O2 P O1 108.7(3) . . ?
O3 P O4 109.0(3) . . ?
O2 P O4 108.4(3) . . ?
O1 P O4 109.5(3) . . ?
Fe1 F1 Fe2 127.7(2) . . ?
Fe1 F1 PbA 113.6(2) . 3_666 ?
Fe2 F1 PbA 118.41(19) . 3_666 ?
Fe1 F2 PbB 110.9(2) . . ?
Fe1 F2 PbA 119.1(2) . . ?
PbB F2 PbA 12.75(9) . . ?
Fe1 F2 PbB 140.5(2) . 4_565 ?
PbB F2 PbB 108.49(17) . 4_565 ?
PbA F2 PbB 100.12(17) . 4_565 ?
Fe1 F2 PbA 138.9(2) . 4_565 ?
PbB F2 PbA 108.91(18) . 4_565 ?
PbA F2 PbA 98.67(15) . 4_565 ?
PbB F2 PbA 12.01(8) 4_565 4_565 ?
P O1 Fe1 124.7(3) . . ?
P O2 PbA 119.3(3) . 3_666 ?
P O2 PbB 95.5(3) . 2_556 ?
PbA O2 PbB 119.7(2) 3_666 2_556 ?
P O3 Fe2 142.9(3) . 1_656 ?
P O4 Fe2 125.7(3) . 1_556 ?
P O4 PbA 110.8(3) . 2_556 ?
Fe2 O4 PbA 107.8(2) 1_556 2_556 ?
P O4 PbB 98.1(3) . 2_556 ?
Fe2 O4 PbB 118.3(2) 1_556 2_556 ?
PbA O4 PbB 12.74(8) 2_556 2_556 ?
PbB PbA O2 144.5(4) . 3_666 ?
PbB PbA O4 91.7(4) . 2_546 ?
O2 PbA O4 82.66(18) 3_666 2_546 ?
PbB PbA F2 73.1(4) . . ?
O2 PbA F2 71.63(17) 3_666 . ?
O4 PbA F2 73.86(16) 2_546 . ?
PbB PbA F1 95.4(4) . 3_666 ?
O2 PbA F1 92.97(16) 3_666 3_666 ?
O4 PbA F1 172.46(16) 2_546 3_666 ?
F2 PbA F1 110.66(15) . 3_666 ?
PbB PbA F2 71.5(4) . 4_666 ?
O2 PbA F2 135.82(17) 3_666 4_666 ?
O4 PbA F2 68.50(16) 2_546 4_666 ?
F2 PbA F2 126.48(17) . 4_666 ?
F1 PbA F2 111.44(15) 3_666 4_666 ?
PbA PbB F2 94.2(4) . . ?
PbA PbB O4 75.6(4) . 2_546 ?
F2 PbB O4 74.26(17) . 2_546 ?
PbA PbB F2 96.5(4) . 4_666 ?
F2 PbB F2 137.91(18) . 4_666 ?
O4 PbB F2 69.31(17) 2_546 4_666 ?
PbA PbB O2 132.4(4) . 2_546 ?
F2 PbB O2 73.99(18) . 2_546 ?
O4 PbB O2 56.85(18) 2_546 2_546 ?
F2 PbB O2 68.84(17) 4_666 2_546 ?

_refine_diff_density_max         1.498
_refine_diff_density_min         -2.942
_refine_diff_density_rms         0.312

_shelx_res_file                  
;

    shelx.res created by SHELXL-2014/7

TITL shelxt_a.res in P2(1)/n
CELL  0.71073   5.2573  12.4039   7.0975   90.000  102.765   90.000
ZERR     2.00   0.0021   0.0048   0.0029    0.000    0.009    0.000
LATT   1
SYMM  1/2 - X, 1/2 + Y, 1/2 - Z
SFAC  O    H    F    P    FE   PB   I
UNIT  8 4 4 2 2 2 0
MERG   2
FMAP   2
PLAN   20
SIZE     0.010   0.010   0.020
ACTA
BOND   $H
LIST   6
L.S.  10
TEMP   123.15
WGHT    0.015800   11.655901
EXTI    0.002021
FVAR       0.22979
FE1   5    0.000000    0.500000    0.500000    10.50000    0.00907    0.00862 =
         0.00816   -0.00131    0.00000   -0.00035
FE2   5    0.000000    0.500000    0.000000    10.50000    0.00768    0.00675 =
         0.00765    0.00047    0.00001    0.00024
P     4    0.432637    0.615176    0.807204    11.00000    0.00900
F1    3    0.100735    0.556472    0.272006    11.00000    0.01289
F2    3    0.116236    0.357182    0.449473    11.00000    0.01332
O1    1    0.354788    0.522078    0.663309    11.00000    0.01006
O2    1    0.427964    0.720594    0.693833    11.00000    0.01278
O3    1    0.703503    0.601525    0.934568    11.00000    0.01050
O4    1    0.231779    0.624253    0.937059    11.00000    0.01196
PBA   6    0.553361    0.286689    0.652452    10.64600    0.02636    0.01373 =
         0.01558    0.00130    0.00120   -0.00552
PBB   6    0.493235    0.300951    0.705599    10.35400    0.06938    0.03107 =
         0.06529    0.03061   -0.04993   -0.03053
HKLF    4

REM  shelxt_a.res in P2(1)/n
REM R1 =  0.0367 for     954 Fo > 4sig(Fo)  and  0.0394 for all    1026 data
REM     60 parameters refined using      0 restraints

END

WGHT      0.0094     10.5621

REM Highest difference peak  1.498,  deepest hole -2.942,  1-sigma level  0.312
Q1    1   0.4327  0.3210  0.7365  11.00000  0.05    1.50
Q2    1   0.9327  0.6370  0.8359  11.00000  0.05    1.41
Q3    1   0.6063  0.2872  0.7416  11.00000  0.05    1.38
Q4    1   0.2849  0.3118  0.5623  11.00000  0.05    1.37
Q5    1   0.6488  0.7073  0.9592  11.00000  0.05    1.30
Q6    1   0.7004  0.6348  0.8898  11.00000  0.05    1.24
Q7    1  -0.0937  0.4962  0.1870  11.00000  0.05    1.13
Q8    1   0.5015  0.5775  1.0010  11.00000  0.05    1.12
Q9    1   0.4821  0.5772  0.5153  11.00000  0.05    1.08
Q10   1   0.6402  0.2613  0.6233  11.00000  0.05    1.04
Q11   1   0.2497  0.3778  0.4540  11.00000  0.05    1.04
Q12   1   0.5375  0.7141  0.6774  11.00000  0.05    1.02
Q13   1   0.1138  0.5008  0.3127  11.00000  0.05    1.00
Q14   1   0.1167  0.2978  0.2839  11.00000  0.05    0.96
Q15   1   0.1406  0.4580  0.6771  11.00000  0.05    0.94
Q16   1   0.4640  0.3300  0.4876  11.00000  0.05    0.92
Q17   1   0.4481  0.6968  1.0245  11.00000  0.05    0.90
Q18   1   0.3252  0.7124  0.6431  11.00000  0.05    0.87
Q19   1   0.6215  0.3857  0.7027  11.00000  0.05    0.87
Q20   1   0.6972  0.7781  0.6164  11.00000  0.05    0.83
;
_shelx_res_checksum              88858
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_h-m   'P 21/n'
_symmetry_int_tables_number      14
_chemical_absolute_configuration ?

_exptl_crystal_preparation       'Magnetic properties'
