# Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers.
# This journal is © the Partner Organisations 2016

####################################################################### 
# 
# 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_p63mmc
_database_code_depnum_ccdc_archive 'CCDC 1441924'
_audit_update_record             
;
2015-12-11 deposited with the CCDC.
2016-04-12 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        JIS-10
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'H0.75 Mn0.17 N0.17 O0.75 P0.25'
_chemical_formula_weight         31.99

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
H H 0.0000 0.0000 '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'
Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Hexagonal
_symmetry_space_group_name_H-M   'P 63/m m c'

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

_cell_length_a                   5.46490(10)
_cell_length_b                   5.46490(10)
_cell_length_c                   19.0227(8)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     492.00(2)
_cell_formula_units_Z            24
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    4679
_cell_measurement_theta_min      2.72
_cell_measurement_theta_max      28.25

_exptl_crystal_description       schistose
_exptl_crystal_colour            pink
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.11
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.591
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             380
_exptl_absorpt_coefficient_mu    3.092
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            3354
_diffrn_reflns_av_R_equivalents  0.0336
_diffrn_reflns_av_sigmaI/netI    0.0136
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_theta_min         4.29
_diffrn_reflns_theta_max         29.13
_reflns_number_total             292
_reflns_number_gt                274
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0455P)²+8.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         292
_refine_ls_number_parameters     28
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0429
_refine_ls_R_factor_gt           0.0406
_refine_ls_wR_factor_ref         0.1196
_refine_ls_wR_factor_gt          0.1183
_refine_ls_goodness_of_fit_ref   1.009
_refine_ls_restrained_S_all      1.005
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Mn1 Mn 0.6667 0.3333 0.33035(7) 0.0107(4) Uani 1 6 d S . .
P1 P 1.3333 0.6667 0.26620(19) 0.0072(10) Uani 0.50 6 d SPD . .
H1 H 1.3333 0.6667 0.336(3) 0.009 Uiso 0.50 6 d SPD . .
P2 P 1.0000 1.0000 0.37480(12) 0.0097(5) Uani 1 6 d SD . .
H2 H 1.0000 1.0000 0.304(2) 0.012 Uiso 1 6 d SD . .
O1 O 1.0198(12) 0.5099(6) 0.2500 0.0161(11) Uani 1 4 d S . .
O2 O 0.8476(4) 0.6952(9) 0.39850(19) 0.0234(10) Uani 1 2 d S . .
N1 N 0.6667 0.3333 0.5350(5) 0.0203(19) Uani 1 6 d S . .
H3 H 0.758(8) 0.516(17) 0.558(3) 0.031 Uiso 1 2 d S . .
H4 H 0.6667 0.3333 0.484(7) 0.031 Uiso 1 6 d S . .

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
Mn1 0.0104(5) 0.0104(5) 0.0112(7) 0.000 0.000 0.0052(2)
P1 0.0067(11) 0.0067(11) 0.008(3) 0.000 0.000 0.0034(5)
P2 0.0094(7) 0.0094(7) 0.0101(10) 0.000 0.000 0.0047(3)
O1 0.007(3) 0.017(2) 0.021(2) 0.000 0.000 0.0037(13)
O2 0.037(2) 0.0068(19) 0.0166(16) -0.0007(17) -0.0003(8) 0.0034(9)
N1 0.022(3) 0.022(3) 0.017(4) 0.000 0.000 0.0110(14)

_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 O2 2.148(4) 3_665 ?
Mn1 O2 2.148(4) . ?
Mn1 O2 2.148(4) 2_655 ?
Mn1 O1 2.265(4) . ?
Mn1 O1 2.265(4) 3_665 ?
Mn1 O1 2.265(4) 2_655 ?
Mn1 Mn1 3.057(3) 16_556 ?
P1 P1 0.617(7) 16_556 ?
P1 O1 1.516(6) 3_775 ?
P1 O1 1.516(6) 2_755 ?
P1 O1 1.516(6) . ?
P1 H1 1.33(5) . ?
P2 O2 1.511(4) 2_765 ?
P2 O2 1.511(4) . ?
P2 O2 1.511(4) 3_675 ?
P2 H2 1.34(5) . ?
O1 P1 1.516(6) 16_556 ?
O1 Mn1 2.265(4) 16_556 ?
N1 H3 0.97(8) . ?
N1 H4 0.98(14) . ?

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
O2 Mn1 O2 87.34(16) 3_665 . ?
O2 Mn1 O2 87.34(16) 3_665 2_655 ?
O2 Mn1 O2 87.34(16) . 2_655 ?
O2 Mn1 O1 96.50(11) 3_665 . ?
O2 Mn1 O1 96.50(11) . . ?
O2 Mn1 O1 174.68(16) 2_655 . ?
O2 Mn1 O1 96.50(11) 3_665 3_665 ?
O2 Mn1 O1 174.68(16) . 3_665 ?
O2 Mn1 O1 96.50(11) 2_655 3_665 ?
O1 Mn1 O1 79.44(16) . 3_665 ?
O2 Mn1 O1 174.68(16) 3_665 2_655 ?
O2 Mn1 O1 96.50(11) . 2_655 ?
O2 Mn1 O1 96.50(11) 2_655 2_655 ?
O1 Mn1 O1 79.44(16) . 2_655 ?
O1 Mn1 O1 79.44(16) 3_665 2_655 ?
O2 Mn1 Mn1 127.12(11) 3_665 16_556 ?
O2 Mn1 Mn1 127.12(11) . 16_556 ?
O2 Mn1 Mn1 127.12(11) 2_655 16_556 ?
O1 Mn1 Mn1 47.55(10) . 16_556 ?
O1 Mn1 Mn1 47.55(10) 3_665 16_556 ?
O1 Mn1 Mn1 47.55(10) 2_655 16_556 ?
P1 P1 O1 78.27(14) 16_556 3_775 ?
P1 P1 O1 78.26(14) 16_556 2_755 ?
O1 P1 O1 115.97(10) 3_775 2_755 ?
P1 P1 O1 78.27(15) 16_556 . ?
O1 P1 O1 115.97(10) 3_775 . ?
O1 P1 O1 115.97(10) 2_755 . ?
P1 P1 H1 179.997(7) 16_556 . ?
O1 P1 H1 101.73(14) 3_775 . ?
O1 P1 H1 101.73(14) 2_755 . ?
O1 P1 H1 101.73(14) . . ?
O2 P2 O2 111.50(15) 2_765 . ?
O2 P2 O2 111.50(15) 2_765 3_675 ?
O2 P2 O2 111.50(15) . 3_675 ?
O2 P2 H2 107.36(17) 2_765 . ?
O2 P2 H2 107.36(16) . . ?
O2 P2 H2 107.36(16) 3_675 . ?
P1 O1 P1 23.5(3) . 16_556 ?
P1 O1 Mn1 149.3(2) . 16_556 ?
P1 O1 Mn1 125.82(14) 16_556 16_556 ?
P1 O1 Mn1 125.82(14) . . ?
P1 O1 Mn1 149.3(2) 16_556 . ?
Mn1 O1 Mn1 84.9(2) 16_556 . ?
P2 O2 Mn1 125.5(2) . . ?
H3 N1 H4 117(4) . . ?

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
N1 H3 O2 0.97(8) 2.17(6) 3.014(4) 144.8(12) 14_566
N1 H3 O2 0.97(8) 2.17(6) 3.014(4) 144.8(12) 15_656
N1 H4 O2 0.98(14) 2.36(10) 3.110(8) 133(2) 3_665
N1 H4 O2 0.98(14) 2.36(10) 3.110(8) 133(2) 2_655
N1 H4 O2 0.98(14) 2.36(10) 3.110(8) 133(2) .

_diffrn_measured_fraction_theta_max 0.967
_diffrn_reflns_theta_full        29.13
_diffrn_measured_fraction_theta_full 0.967
_refine_diff_density_max         0.510
_refine_diff_density_min         -1.054
_refine_diff_density_rms         0.183
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: '
