# 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_EtAMn
_database_code_depnum_ccdc_archive 'CCDC 2104953'
loop_
_audit_author_name
_audit_author_address
'Anna Gagor'
;ILT SR PAS Wroclaw Poland
Poland
;
_audit_update_record             
;
2021-08-23 deposited with the CCDC.	2021-11-29 downloaded from the CCDC.
;
_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C2 H14 Mn N O7 P3'
_chemical_formula_weight         311.99
_chemical_melting_point          ?

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'
Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 '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'
P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_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'
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                   9.4250(4)
_cell_length_b                   8.8692(3)
_cell_length_c                   13.4809(6)
_cell_angle_alpha                90
_cell_angle_beta                 93.142(4)
_cell_angle_gamma                90
_cell_volume                     1125.20(8)
_cell_formula_units_Z            4

_cell_measurement_temperature    295(2)
_cell_measurement_reflns_used    5745
_cell_measurement_theta_min      4.2490
_cell_measurement_theta_max      29.1220
_exptl_absorpt_coefficient_mu    1.610
_exptl_crystal_colour            ?
_exptl_crystal_density_diffrn    1.842
_exptl_crystal_description       plate
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.05
_exptl_crystal_F_000             636
_exptl_absorpt_correction_T_min  0.95338
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_oxdiff_exptl_absorpt_empirical_full_min 0.954
_oxdiff_exptl_absorpt_empirical_full_max 1.064
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas'
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            Atlas
_diffrn_detector_area_resol_mean 10.6249



_diffrn_reflns_av_R_equivalents  0.0263
_diffrn_reflns_av_unetI/netI     0.0257
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.883
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            12768
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.883
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.541
_diffrn_reflns_theta_min         2.572
_diffrn_ambient_temperature      295(2)

_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.883



_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                2303
_reflns_number_total             2774
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_refine_diff_density_max         0.418
_refine_diff_density_min         -0.320
_refine_diff_density_rms         0.074
_refine_ls_extinction_coef       0.0062(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     157
_refine_ls_number_reflns         2774
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.0377
_refine_ls_R_factor_gt           0.0282
_refine_ls_restrained_S_all      1.045
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0310P)²+0.4398P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0648
_refine_ls_wR_factor_ref         0.0692
_refine_special_details          ?
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
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
Mn1 Mn 0.000000 1.000000 0.500000 0.01615(11) Uani 1 2 d S . P . .
Mn2 Mn 0.500000 0.500000 0.500000 0.01642(11) Uani 1 2 d S . P . .
P1 P 0.24336(5) 1.25997(6) 0.47126(4) 0.02729(14) Uani 1 1 d . . . . .
H5 H 0.301(2) 1.216(3) 0.3905(18) 0.042 Uiso 1 1 d . U . . .
H6 H 0.304(2) 1.174(3) 0.5392(17) 0.042 Uiso 1 1 d . U . . .
P3 P 0.47559(6) 0.52222(6) 0.25000(4) 0.02606(13) Uani 1 1 d . . . . .
H1 H 0.343(2) 0.518(3) 0.2436(18) 0.042 Uiso 1 1 d . U . . .
H2 H 0.507(2) 0.662(3) 0.2512(16) 0.042 Uiso 1 1 d . U . . .
P21 P 0.3072(2) 0.8230(2) 0.43446(13) 0.0293(4) Uani 0.849(8) 1 d . U P . .
H3 H 0.246(2) 0.755(3) 0.3598(18) 0.042 Uiso 1 1 d . U . . .
H4 H 0.355(2) 0.937(3) 0.3795(18) 0.042 Uiso 1 1 d . U . . .
P22 P 0.3404(9) 0.8576(10) 0.4562(6) 0.0293(4) Uani 0.151(8) 1 d . U P . .
O1 O 0.08852(14) 1.21872(15) 0.46315(11) 0.0307(3) Uani 1 1 d . . . . .
O2 O 0.20464(14) 0.88282(18) 0.50447(12) 0.0374(4) Uani 1 1 d . . . . .
O3 O 0.27701(13) 1.42424(15) 0.48696(11) 0.0284(3) Uani 1 1 d . . . . .
O4 O 0.42521(15) 0.72671(16) 0.47229(13) 0.0408(4) Uani 1 1 d . . . . .
O5 O 0.52659(17) 0.45409(19) 0.34544(11) 0.0388(4) Uani 1 1 d . . . . .
O6 O 0.52865(16) 0.44919(17) 0.15867(10) 0.0340(3) Uani 1 1 d . . . . .
O1A O 0.70088(16) 0.20942(17) 0.21779(12) 0.0356(4) Uani 1 1 d . . . . .
H1A H 0.651(3) 0.269(3) 0.200(2) 0.042 Uiso 1 1 d . U . . .
N1 N 0.64162(17) -0.09746(18) 0.13039(13) 0.0289(4) Uani 1 1 d . . . . .
H1C H 0.693652 -0.038872 0.092967 0.035 Uiso 1 1 calc R U . . .
H1D H 0.592855 -0.162951 0.091882 0.035 Uiso 1 1 calc R U . . .
H1E H 0.698453 -0.147292 0.173920 0.035 Uiso 1 1 calc R U . . .
C1 C 0.6157(2) 0.0977(2) 0.26071(16) 0.0350(5) Uani 1 1 d . . . . .
H1F H 0.544990 0.146719 0.299254 0.042 Uiso 1 1 calc R U . . .
H1G H 0.675137 0.036436 0.305763 0.042 Uiso 1 1 calc R U . . .
C2 C 0.5416(2) -0.0030(2) 0.18433(18) 0.0343(5) Uani 1 1 d . . . . .
H2A H 0.475906 -0.068085 0.217012 0.041 Uiso 1 1 calc R U . . .
H2B H 0.486827 0.058805 0.136854 0.041 Uiso 1 1 calc R U . . .


_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
Mn1 O1 2.1798(13) 3_576 ?
Mn1 O1 2.1798(13) . ?
Mn1 O2 2.1889(13) 3_576 ?
Mn1 O2 2.1888(13) . ?
Mn1 O6 2.1881(14) 4_576 ?
Mn1 O6 2.1881(14) 2 ?
Mn2 O3 2.2043(12) 1_545 ?
Mn2 O3 2.2043(12) 3_676 ?
Mn2 O4 2.1565(14) 3_666 ?
Mn2 O4 2.1565(14) . ?
Mn2 O5 2.1511(15) . ?
Mn2 O5 2.1512(15) 3_666 ?
P1 H5 1.30(2) . ?
P1 H6 1.30(2) . ?
P1 O1 1.5027(14) . ?
P1 O3 1.5035(14) . ?
P3 H1 1.25(2) . ?
P3 H2 1.27(3) . ?
P3 O5 1.4777(16) . ?
P3 O6 1.5011(15) . ?
P21 H3 1.28(2) . ?
P21 H4 1.34(2) . ?
P21 O2 1.4857(17) . ?
P21 O4 1.4710(18) . ?
P22 H3 1.78(3) . ?
P22 H4 1.26(2) . ?
P22 O2 1.484(7) . ?
P22 O4 1.420(6) . ?
O1A H1A 0.74(2) . ?
O1A C1 1.419(3) . ?
N1 H1C 0.8900 . ?
N1 H1D 0.8900 . ?
N1 H1E 0.8900 . ?
N1 C2 1.481(3) . ?
C1 H1F 0.9700 . ?
C1 H1G 0.9700 . ?
C2 C1 1.505(3) . ?
C2 H2A 0.9700 . ?
C2 H2B 0.9700 . ?

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 Mn1 O1 180.0 3_576 . ?
O1 Mn1 O2 94.65(6) 3_576 3_576 ?
O1 Mn1 O2 85.35(6) . 3_576 ?
O1 Mn1 O2 85.35(6) 3_576 . ?
O1 Mn1 O2 94.65(6) . . ?
O1 Mn1 O6 89.36(5) 3_576 4_576 ?
O1 Mn1 O6 90.64(5) 3_576 2 ?
O1 Mn1 O6 89.36(5) . 2 ?
O1 Mn1 O6 90.64(5) . 4_576 ?
O2 Mn1 O2 180.0 . 3_576 ?
O6 Mn1 O2 90.55(6) 2 3_576 ?
O6 Mn1 O2 90.54(6) 4_576 . ?
O6 Mn1 O2 89.45(6) 4_576 3_576 ?
O6 Mn1 O2 89.46(6) 2 . ?
O6 Mn1 O6 180.0 4_576 2 ?
O3 Mn2 O3 180.0 3_676 1_545 ?
O4 Mn2 O3 91.76(5) 3_666 1_545 ?
O4 Mn2 O3 88.24(5) . 1_545 ?
O4 Mn2 O3 88.24(5) 3_666 3_676 ?
O4 Mn2 O3 91.76(5) . 3_676 ?
O4 Mn2 O4 180.0 3_666 . ?
O5 Mn2 O3 88.50(6) . 3_676 ?
O5 Mn2 O3 88.50(6) 3_666 1_545 ?
O5 Mn2 O3 91.50(6) 3_666 3_676 ?
O5 Mn2 O3 91.50(6) . 1_545 ?
O5 Mn2 O4 86.38(6) . 3_666 ?
O5 Mn2 O4 86.38(6) 3_666 . ?
O5 Mn2 O4 93.62(6) . . ?
O5 Mn2 O4 93.62(6) 3_666 3_666 ?
O5 Mn2 O5 180.00(8) . 3_666 ?
H5 P1 H6 103.2(14) . . ?
O1 P1 H5 108.3(10) . . ?
O1 P1 H6 107.3(10) . . ?
O1 P1 O3 116.28(8) . . ?
O3 P1 H5 108.1(10) . . ?
O3 P1 H6 112.8(10) . . ?
H2 P3 H1 105.3(14) . . ?
O5 P3 H1 108.9(11) . . ?
O5 P3 H2 108.7(10) . . ?
O5 P3 O6 115.51(9) . . ?
O6 P3 H1 107.9(11) . . ?
O6 P3 H2 110.0(10) . . ?
O4 P22 O2 123.3(5) . . ?
P1 O1 Mn1 125.62(8) . . ?
P21 O2 Mn1 139.05(12) . . ?
P22 O2 Mn1 147.1(3) . . ?
P1 O3 Mn2 119.96(7) . 1_565 ?
P21 O4 Mn2 146.63(14) . . ?
P22 O4 Mn2 164.8(4) . . ?
P3 O5 Mn2 135.75(10) . . ?
P3 O6 Mn1 133.17(9) . 2_545 ?
C1 O1A H1A 106(2) . . ?
H1C N1 H1D 109.5 . . ?
H1C N1 H1E 109.5 . . ?
H1D N1 H1E 109.5 . . ?
C2 N1 H1C 109.5 . . ?
C2 N1 H1D 109.5 . . ?
C2 N1 H1E 109.5 . . ?
O1A C1 H1F 109.0 . . ?
O1A C1 H1G 109.0 . . ?
O1A C1 C2 112.77(18) . . ?
H1F C1 H1G 107.8 . . ?
C2 C1 H1F 109.0 . . ?
C2 C1 H1G 109.0 . . ?
N1 C2 C1 112.82(17) . . ?
N1 C2 H2A 109.0 . . ?
N1 C2 H2B 109.0 . . ?
C1 C2 H2A 109.0 . . ?
C1 C2 H2B 109.0 . . ?
H2A C2 H2B 107.8 . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
O1A H1A O6 0.74(2) 2.03(2) 2.766(2) 174(3) . yes
N1 H1C O3 0.89 1.95 2.828(2) 167.1 4_675 yes
N1 H1D O1 0.89 2.11 2.942(2) 156.1 2_535 yes
N1 H1D O2 0.89 2.54 3.123(2) 123.9 4_665 yes
N1 H1E O1A 0.89 2.12 2.999(2) 169.2 2_645 yes

####################################################################### 
# 
# 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_PyrMn
_database_code_depnum_ccdc_archive 'CCDC 2104954'
loop_
_audit_author_name
_audit_author_address
'Anna Gagor'
;ILT SR PAS Wroclaw Poland
Poland
;
_audit_update_record             
;
2021-08-23 deposited with the CCDC.	2021-11-29 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C4 H16 Mn N O6 P3'
_chemical_formula_weight         322.03

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'
Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 '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'
P P 0.1023 0.0942 '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                   9.7325(3)
_cell_length_b                   9.1882(3)
_cell_length_c                   13.4223(4)
_cell_angle_alpha                90
_cell_angle_beta                 91.018(3)
_cell_angle_gamma                90
_cell_volume                     1200.09(6)
_cell_formula_units_Z            4
_cell_measurement_temperature    295(2)
_cell_measurement_reflns_used    6701
_cell_measurement_theta_min      3.3700
_cell_measurement_theta_max      29.1580

_exptl_crystal_description       plate
_exptl_crystal_colour            ?
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.782
_exptl_crystal_F_000             660
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.06
_exptl_absorpt_coefficient_mu    1.507
_diffrn_ambient_temperature      295(2)
_exptl_absorpt_correction_T_min  0.96039
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_oxdiff_exptl_absorpt_empirical_full_min 0.960
_oxdiff_exptl_absorpt_empirical_full_max 1.084
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas'
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            Atlas
_diffrn_detector_area_resol_mean 10.6249
_diffrn_reflns_number            15018
_diffrn_reflns_av_unetI/netI     0.0190
_diffrn_reflns_av_R_equivalents  0.0221
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         2.607
_diffrn_reflns_theta_max         29.296
_diffrn_reflns_theta_full        25.000
_diffrn_measured_fraction_theta_max 0.904
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.904
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.904
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             2973
_reflns_number_gt                2595
_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       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_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)+(0.0282P)²+0.5214P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2973
_refine_ls_number_parameters     157
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0313
_refine_ls_R_factor_gt           0.0250
_refine_ls_wR_factor_ref         0.0630
_refine_ls_wR_factor_gt          0.0595
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_restrained_S_all      1.054
_refine_ls_shift/su_max          0.001
_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
Mn1 Mn 0.500000 0.500000 0.500000 0.01591(8) Uani 1 2 d S . P . .
Mn2 Mn 0.000000 1.000000 0.500000 0.01592(8) Uani 1 2 d S . P . .
P1 P -0.02386(5) 1.01536(5) 0.74998(3) 0.02286(10) Uani 1 1 d . . . . .
P2 P 0.22625(4) 0.72097(5) 0.46415(3) 0.02737(11) Uani 1 1 d . . . . .
P3 P 0.80279(5) 0.70764(5) 0.56662(3) 0.02972(12) Uani 1 1 d . . . . .
O1 O 0.02468(12) 0.93915(14) 0.84298(8) 0.0285(3) Uani 1 1 d . . . . .
O2 O 0.87269(12) 0.80082(14) 0.49165(10) 0.0347(3) Uani 1 1 d . . . . .
O3 O 0.18244(12) 0.87669(14) 0.46283(10) 0.0337(3) Uani 1 1 d . . . . .
O4 O 0.35821(13) 0.68283(14) 0.51572(10) 0.0352(3) Uani 1 1 d . . . . .
O5 O 0.66881(13) 0.64295(16) 0.53950(10) 0.0409(3) Uani 1 1 d . . . . .
O6 O 0.04473(15) 0.96901(18) 0.65688(9) 0.0446(4) Uani 1 1 d . . . . .
N1 N 0.16329(14) 0.67134(16) 0.83996(10) 0.0262(3) Uani 1 1 d . . . . .
H1 H 0.131965 0.762118 0.843978 0.031 Uiso 1 1 calc R U . . .
H2 H 0.249278 0.669651 0.863625 0.031 Uiso 1 1 calc R U . . .
C1 C 0.15925(18) 0.6211(2) 0.73364(12) 0.0302(4) Uani 1 1 d . . . . .
H3 H 0.250186 0.623374 0.705257 0.036 Uiso 1 1 calc R U . . .
H4 H 0.098005 0.681382 0.693491 0.036 Uiso 1 1 calc R U . . .
C2 C 0.07474(19) 0.5708(2) 0.89971(13) 0.0320(4) Uani 1 1 d . . . . .
H5 H 0.008427 0.625584 0.937661 0.038 Uiso 1 1 calc R U . . .
H6 H 0.130473 0.512898 0.945345 0.038 Uiso 1 1 calc R U . . .
C3 C 0.1060(2) 0.4671(2) 0.73998(16) 0.0436(5) Uani 1 1 d . . . . .
H7 H 0.179659 0.399437 0.756049 0.052 Uiso 1 1 calc R U . . .
H8 H 0.061791 0.437640 0.677882 0.052 Uiso 1 1 calc R U . . .
C4 C 0.0032(2) 0.4752(2) 0.82368(17) 0.0461(5) Uani 1 1 d . . . . .
H9 H -0.082621 0.518462 0.800777 0.055 Uiso 1 1 calc R U . . .
H10 H -0.015144 0.379455 0.850769 0.055 Uiso 1 1 calc R U . . .
H11 H -0.013(2) 1.152(3) 0.7606(16) 0.055 Uiso 1 1 d . U . . .
H12 H -0.157(3) 1.002(2) 0.7411(18) 0.055 Uiso 1 1 d . U . . .
H13 H 0.230(2) 0.677(3) 0.3745(17) 0.055 Uiso 1 1 d . U . . .
H14 H 0.127(2) 0.639(3) 0.5006(17) 0.055 Uiso 1 1 d . U . . .
H15 H 0.794(2) 0.776(3) 0.6531(17) 0.055 Uiso 1 1 d . U . . .
H16 H 0.890(2) 0.607(3) 0.5931(17) 0.055 Uiso 1 1 d . U . . .


_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
Mn1 O5 2.1621(12) . ?
Mn1 O5 2.1621(12) 3_666 ?
Mn1 O4 2.1866(12) . ?
Mn1 O4 2.1866(12) 3_666 ?
Mn1 O1 2.1977(11) 2_546 ?
Mn1 O1 2.1977(11) 4_675 ?
Mn2 O6 2.1615(12) 3_576 ?
Mn2 O6 2.1615(12) . ?
Mn2 O3 2.1718(11) 3_576 ?
Mn2 O3 2.1718(11) . ?
Mn2 O2 2.2118(12) 3_676 ?
Mn2 O2 2.2118(12) 1_455 ?
P1 O6 1.4894(13) . ?
P1 O1 1.5001(12) . ?
P1 H11 1.27(3) . ?
P1 H12 1.30(2) . ?
P2 O4 1.4899(13) . ?
P2 O3 1.4930(13) . ?
P2 H13 1.27(2) . ?
P2 H14 1.32(2) . ?
P3 O5 1.4728(13) . ?
P3 O2 1.4943(13) . ?
P3 H15 1.32(2) . ?
P3 H16 1.30(2) . ?
N1 C1 1.500(2) . ?
N1 C2 1.505(2) . ?
N1 H1 0.8900 . ?
N1 H2 0.8900 . ?
C1 C3 1.510(3) . ?
C1 H3 0.9700 . ?
C1 H4 0.9700 . ?
C2 C4 1.507(3) . ?
C2 H5 0.9700 . ?
C2 H6 0.9700 . ?
C3 C4 1.520(3) . ?
C3 H7 0.9700 . ?
C3 H8 0.9700 . ?
C4 H9 0.9700 . ?
C4 H10 0.9700 . ?

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
O5 Mn1 O5 180.0 . 3_666 ?
O5 Mn1 O4 89.30(5) . . ?
O5 Mn1 O4 90.70(5) 3_666 . ?
O5 Mn1 O4 90.70(5) . 3_666 ?
O5 Mn1 O4 89.30(5) 3_666 3_666 ?
O4 Mn1 O4 180.0 . 3_666 ?
O5 Mn1 O1 90.85(5) . 2_546 ?
O5 Mn1 O1 89.15(5) 3_666 2_546 ?
O4 Mn1 O1 91.32(5) . 2_546 ?
O4 Mn1 O1 88.68(5) 3_666 2_546 ?
O5 Mn1 O1 89.15(5) . 4_675 ?
O5 Mn1 O1 90.85(5) 3_666 4_675 ?
O4 Mn1 O1 88.68(5) . 4_675 ?
O4 Mn1 O1 91.32(5) 3_666 4_675 ?
O1 Mn1 O1 180.0 2_546 4_675 ?
O6 Mn2 O6 180.0 3_576 . ?
O6 Mn2 O3 90.22(5) 3_576 3_576 ?
O6 Mn2 O3 89.78(5) . 3_576 ?
O6 Mn2 O3 89.78(5) 3_576 . ?
O6 Mn2 O3 90.22(5) . . ?
O3 Mn2 O3 180.0 3_576 . ?
O6 Mn2 O2 92.48(6) 3_576 3_676 ?
O6 Mn2 O2 87.52(6) . 3_676 ?
O3 Mn2 O2 90.93(5) 3_576 3_676 ?
O3 Mn2 O2 89.07(5) . 3_676 ?
O6 Mn2 O2 87.52(6) 3_576 1_455 ?
O6 Mn2 O2 92.48(6) . 1_455 ?
O3 Mn2 O2 89.07(5) 3_576 1_455 ?
O3 Mn2 O2 90.93(5) . 1_455 ?
O2 Mn2 O2 180.0 3_676 1_455 ?
O6 P1 O1 115.18(7) . . ?
O6 P1 H11 109.9(10) . . ?
O1 P1 H11 110.1(10) . . ?
O6 P1 H12 110.7(11) . . ?
O1 P1 H12 109.2(10) . . ?
H11 P1 H12 100.8(13) . . ?
O4 P2 O3 118.33(8) . . ?
O4 P2 H13 109.3(10) . . ?
O3 P2 H13 107.7(10) . . ?
O4 P2 H14 109.0(10) . . ?
O3 P2 H14 109.6(10) . . ?
H13 P2 H14 101.6(14) . . ?
O5 P3 O2 118.46(8) . . ?
O5 P3 H15 109.5(10) . . ?
O2 P3 H15 111.1(10) . . ?
O5 P3 H16 110.3(10) . . ?
O2 P3 H16 106.9(10) . . ?
H15 P3 H16 98.7(14) . . ?
P1 O1 Mn1 129.87(7) . 2_556 ?
P3 O2 Mn2 134.53(8) . 1_655 ?
P2 O3 Mn2 137.03(8) . . ?
P2 O4 Mn1 132.54(8) . . ?
P3 O5 Mn1 166.25(10) . . ?
P1 O6 Mn2 133.97(8) . . ?
C1 N1 C2 108.22(13) . . ?
C1 N1 H1 110.1 . . ?
C2 N1 H1 110.1 . . ?
C1 N1 H2 110.1 . . ?
C2 N1 H2 110.1 . . ?
H1 N1 H2 108.4 . . ?
N1 C1 C3 103.77(14) . . ?
N1 C1 H3 111.0 . . ?
C3 C1 H3 111.0 . . ?
N1 C1 H4 111.0 . . ?
C3 C1 H4 111.0 . . ?
H3 C1 H4 109.0 . . ?
N1 C2 C4 105.00(15) . . ?
N1 C2 H5 110.7 . . ?
C4 C2 H5 110.7 . . ?
N1 C2 H6 110.7 . . ?
C4 C2 H6 110.7 . . ?
H5 C2 H6 108.8 . . ?
C1 C3 C4 103.10(16) . . ?
C1 C3 H7 111.1 . . ?
C4 C3 H7 111.1 . . ?
C1 C3 H8 111.1 . . ?
C4 C3 H8 111.1 . . ?
H7 C3 H8 109.1 . . ?
C2 C4 C3 103.11(16) . . ?
C2 C4 H9 111.1 . . ?
C3 C4 H9 111.1 . . ?
C2 C4 H10 111.1 . . ?
C3 C4 H10 111.1 . . ?
H9 C4 H10 109.1 . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
N1 H1 O1 0.89 1.93 2.8069(19) 166.9 . yes
N1 H2 O2 0.89 2.10 2.8665(19) 144.3 4_576 yes

_refine_diff_density_max         0.307
_refine_diff_density_min         -0.469
_refine_diff_density_rms         0.068



