# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.
# 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_mo_Kbir3long_20200203_0m_a
_database_code_depnum_ccdc_archive 'CCDC 2041937'
loop_
_audit_author_name
_audit_author_address
'Liliia D. Kulish'
;Zernike Institute for Advanced Materials, University of Groningen
Netherlands
;
_audit_update_record             
;
2020-11-02 deposited with the CCDC.	2020-12-21 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        K0.31MnO2.0.41H2O
_chemical_name_common            'potassium birnessite'
_chemical_melting_point          ?
_chemical_formula_moiety         'K0.31 Mn O2 H0.82 O0.41'
_chemical_formula_sum            'K0.31 Mn O2.41 H0.82'
_chemical_formula_weight         105.62

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
K K 0.2009 0.2494 '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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           63
_space_group_name_H-M_alt        Cmcm
_space_group_name_Hall           '-C 2c 2'

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

_cell_length_a                   2.897(4)
_cell_length_b                   4.980(9)
_cell_length_c                   14.12(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     203.6(6)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    1519
_cell_measurement_theta_min      5.757
_cell_measurement_theta_max      60.285

_exptl_crystal_description       'hexagonal plate'
_exptl_crystal_colour            'Dark brown'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    3.445
_exptl_crystal_F_000             201
_exptl_transmission_factor_min   0.5072
_exptl_transmission_factor_max   0.7461
_exptl_crystal_size_max          0.160
_exptl_crystal_size_mid          0.120
_exptl_crystal_size_min          0.020
_exptl_absorpt_coefficient_mu    6.726
_shelx_estimated_absorpt_T_min   0.412
_shelx_estimated_absorpt_T_max   0.877
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   
'SAD2ABS-2014/4 - Bruker AXS area detector scaling and absorption correction'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker D8 Venture; Photon100 area detector'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            2579
_diffrn_reflns_av_unetI/netI     0.0257
_diffrn_reflns_av_R_equivalents  0.0638
_diffrn_reflns_limit_h_min       -3
_diffrn_reflns_limit_h_max       3
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         2.886
_diffrn_reflns_theta_max         28.253
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             165
_reflns_number_gt                148
_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. Completness statistics refer to single and
 composite reflections containing twin component 1 only.
;

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          
;
 Refined as a 3-component perfect twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0846P)²+6.4803P] 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-2018/3 (Sheldrick 2018)'
_refine_ls_extinction_coef       0.16(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         165
_refine_ls_number_parameters     13
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0863
_refine_ls_R_factor_gt           0.0759
_refine_ls_wR_factor_ref         0.2019
_refine_ls_wR_factor_gt          0.1924
_refine_ls_goodness_of_fit_ref   1.445
_refine_ls_restrained_S_all      1.445
_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
Mn01 Mn 1.000000 0.500000 0.500000 0.0130(19) Uani 1 4 d S T P . .
O002 O 0.500000 0.333(3) 0.4311(6) 0.017(2) Uiso 1 2 d S . P . .
O003 O 0.000000 0.228(6) 0.250000 0.029(4) Uiso 0.18(4) 4 d S . P . .
K003 K 0.000000 0.228(6) 0.250000 0.029(4) Uiso 0.17(3) 4 d S . P . .
O004 O -0.500000 0.139(7) 0.250000 0.029(4) Uiso 0.23(4) 4 d S . P . .
K004 K -0.500000 0.139(7) 0.250000 0.029(4) Uiso 0.14(3) 4 d S . 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
Mn01 0.018(11) 0.004(8) 0.0167(17) -0.0026(13) 0.000 0.000

_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
Mn01 O002 1.921(12) 13_656 ?
Mn01 O002 1.921(12) 5 ?
Mn01 O002 1.934(7) 9_766 ?
Mn01 O002 1.934(7) 9_666 ?
Mn01 O002 1.934(7) 1_655 ?
Mn01 O002 1.934(7) . ?
Mn01 Mn01 2.881(4) 5_445 ?
Mn01 Mn01 2.881(4) 5 ?
Mn01 Mn01 2.881(4) 5_455 ?
Mn01 Mn01 2.881(4) 5_545 ?
Mn01 Mn01 2.897(4) 1_455 ?
Mn01 Mn01 2.897(4) 1_655 ?
O002 K004 3.310(19) 5_655 ?
O003 O004 1.515(11) 1_655 ?
O003 O004 1.515(11) . ?

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
O002 Mn01 O002 180.0 13_656 5 ?
O002 Mn01 O002 96.7(3) 13_656 9_766 ?
O002 Mn01 O002 83.3(3) 5 9_766 ?
O002 Mn01 O002 96.7(3) 13_656 9_666 ?
O002 Mn01 O002 83.3(3) 5 9_666 ?
O002 Mn01 O002 97.0(5) 9_766 9_666 ?
O002 Mn01 O002 83.3(3) 13_656 1_655 ?
O002 Mn01 O002 96.7(3) 5 1_655 ?
O002 Mn01 O002 83.0(5) 9_766 1_655 ?
O002 Mn01 O002 180.0 9_666 1_655 ?
O002 Mn01 O002 83.3(3) 13_656 . ?
O002 Mn01 O002 96.7(3) 5 . ?
O002 Mn01 O002 180.0 9_766 . ?
O002 Mn01 O002 83.0(5) 9_666 . ?
O002 Mn01 O002 97.0(5) 1_655 . ?
O002 Mn01 Mn01 41.8(2) 13_656 5_445 ?
O002 Mn01 Mn01 138.2(2) 5 5_445 ?
O002 Mn01 Mn01 138.5(3) 9_766 5_445 ?
O002 Mn01 Mn01 89.8(3) 9_666 5_445 ?
O002 Mn01 Mn01 90.2(3) 1_655 5_445 ?
O002 Mn01 Mn01 41.5(3) . 5_445 ?
O002 Mn01 Mn01 138.2(2) 13_656 5 ?
O002 Mn01 Mn01 41.8(2) 5 5 ?
O002 Mn01 Mn01 41.5(3) 9_766 5 ?
O002 Mn01 Mn01 90.2(3) 9_666 5 ?
O002 Mn01 Mn01 89.8(3) 1_655 5 ?
O002 Mn01 Mn01 138.5(3) . 5 ?
Mn01 Mn01 Mn01 180.0 5_445 5 ?
O002 Mn01 Mn01 138.2(2) 13_656 5_455 ?
O002 Mn01 Mn01 41.8(2) 5 5_455 ?
O002 Mn01 Mn01 90.2(3) 9_766 5_455 ?
O002 Mn01 Mn01 41.5(3) 9_666 5_455 ?
O002 Mn01 Mn01 138.5(3) 1_655 5_455 ?
O002 Mn01 Mn01 89.8(3) . 5_455 ?
Mn01 Mn01 Mn01 119.63(11) 5_445 5_455 ?
Mn01 Mn01 Mn01 60.37(11) 5 5_455 ?
O002 Mn01 Mn01 41.8(2) 13_656 5_545 ?
O002 Mn01 Mn01 138.2(2) 5 5_545 ?
O002 Mn01 Mn01 89.8(3) 9_766 5_545 ?
O002 Mn01 Mn01 138.5(3) 9_666 5_545 ?
O002 Mn01 Mn01 41.5(3) 1_655 5_545 ?
O002 Mn01 Mn01 90.2(3) . 5_545 ?
Mn01 Mn01 Mn01 60.37(11) 5_445 5_545 ?
Mn01 Mn01 Mn01 119.63(11) 5 5_545 ?
Mn01 Mn01 Mn01 180.0 5_455 5_545 ?
O002 Mn01 Mn01 90.000(3) 13_656 1_455 ?
O002 Mn01 Mn01 90.000(3) 5 1_455 ?
O002 Mn01 Mn01 138.5(2) 9_766 1_455 ?
O002 Mn01 Mn01 41.5(2) 9_666 1_455 ?
O002 Mn01 Mn01 138.5(2) 1_655 1_455 ?
O002 Mn01 Mn01 41.5(2) . 1_455 ?
Mn01 Mn01 Mn01 59.81(6) 5_445 1_455 ?
Mn01 Mn01 Mn01 120.19(6) 5 1_455 ?
Mn01 Mn01 Mn01 59.81(6) 5_455 1_455 ?
Mn01 Mn01 Mn01 120.19(6) 5_545 1_455 ?
O002 Mn01 Mn01 90.000(3) 13_656 1_655 ?
O002 Mn01 Mn01 90.000(3) 5 1_655 ?
O002 Mn01 Mn01 41.5(2) 9_766 1_655 ?
O002 Mn01 Mn01 138.5(2) 9_666 1_655 ?
O002 Mn01 Mn01 41.5(2) 1_655 1_655 ?
O002 Mn01 Mn01 138.5(2) . 1_655 ?
Mn01 Mn01 Mn01 120.19(6) 5_445 1_655 ?
Mn01 Mn01 Mn01 59.81(6) 5 1_655 ?
Mn01 Mn01 Mn01 120.19(6) 5_455 1_655 ?
Mn01 Mn01 Mn01 59.81(6) 5_545 1_655 ?
Mn01 Mn01 Mn01 180.0 1_455 1_655 ?
Mn01 O002 Mn01 96.7(3) 5_445 . ?
Mn01 O002 Mn01 96.7(3) 5_445 1_455 ?
Mn01 O002 Mn01 97.0(5) . 1_455 ?
Mn01 O002 K004 142.0(6) 5_445 5_655 ?
Mn01 O002 K004 82.1(4) . 5_655 ?
Mn01 O002 K004 121.2(7) 1_455 5_655 ?
O004 O003 O004 146(3) 1_655 . ?
O003 O004 O003 146(3) . 1_455 ?

_refine_diff_density_max         1.638
_refine_diff_density_min         -1.073
_refine_diff_density_rms         0.432

_shelx_res_file                  
;
TITL mo_Kbir3long_20200203_0m_a.res in Cmcm
    mo_Kbir3long_20200203_0m_a.res
    created by SHELXL-2018/3 at 10:35:12 on 26-Oct-2020
REM Old TITL mo_Kbir3long_20200203_0m in Cmcm

REM SHELXT solution in Cmcm
REM R1 0.133,  Rweak 0.005,  Alpha 0.048,  Orientation as input
REM Formula found by SHELXT:  Mn O3

CELL  0.71073   2.8967   4.9800  14.1158   90.000   90.000   90.000
ZERR    4.000   0.0042   0.0088   0.0229    0.000    0.000    0.000
LATT  7
SYMM -X, -Y, 1/2+Z
SYMM -X, Y, 1/2-Z
SYMM X, -Y, -Z
SFAC K MN O
UNIT 1.24 4 9.64
TEMP -173.150
SIZE 0.02 0.12 0.16
TWIN -0.5 -0.5 0 1.5 -0.5 0 0 0 1 3
L.S. 30
BOND $H
ACTA
LIST 6
FMAP 2
PLAN 20
SHEL 0.75 9999
EXYZ O003 K003
EADP O003 K003 O004 K004
EXYZ O004 K004
WGHT    0.084600    6.480300
EXTI    0.156721
FVAR       1.03085   0.44741
MN01  2    1.000000    0.500000    0.500000    10.25000    0.01812    0.00424 =
         0.01672   -0.00257    0.00000    0.00000
O002  3    0.500000    0.332541    0.431089    10.50000    0.01660
O003  3    0.000000    0.227913    0.250000    20.10250    0.02943
K003  1    0.000000    0.227913    0.250000   -20.07750    0.02943
O004  3   -0.500000    0.138875    0.250000   -20.10250    0.02943
K004  1   -0.500000    0.138875    0.250000    20.07750    0.02943
HKLF 4




REM  mo_Kbir3long_20200203_0m_a.res in Cmcm
REM wR2 = 0.201851, GooF = S = 1.44528, Restrained GooF = 1.44528 for all data
REM R1 = 0.075878 for 148 Fo > 4sig(Fo) and 0.086257 for all 165 data
REM 13 parameters refined using 0 restraints

END

WGHT      0.0857      7.5208

REM Highest difference peak  1.638,  deepest hole -1.073,  1-sigma level  0.432
Q1    1   0.0000  0.3936  0.2500  10.25000  0.05    1.64
Q2    1  -0.6775  0.2658  0.2500  10.50000  0.05    1.41
Q3    1  -0.8184  0.0278  0.2500  10.50000  0.05    1.33
Q4    1  -0.5000  0.3190  0.2500  10.25000  0.05    1.29
Q5    1   0.0000  0.1619  0.2500  10.25000  0.05    1.09
Q6    1  -0.5000  0.3547  0.2991  10.50000  0.05    0.96
Q7    1  -0.5000  0.0707  0.3122  10.50000  0.05    0.93
Q8    1   0.0000  0.2740  0.3140  10.50000  0.05    0.72
Q9    1   0.5000  0.3757  0.3822  10.50000  0.05    0.50
Q10   1   0.0000  0.1692  0.4394  10.50000  0.05    0.44
Q11   1   1.0000  0.4800  0.5579  10.50000  0.05    0.43
Q12   1   0.5000  0.3316  0.4617  10.50000  0.05    0.33
Q13   1   0.5000  0.1486  0.3767  10.50000  0.05    0.29
Q14   1   0.5000  0.2479  0.4980  10.50000  0.05    0.11
Q15   1   0.0000  0.2378  0.3971  10.50000  0.05    0.06
Q16   1   0.2337  0.3255  0.4281  11.00000  0.05    0.04
Q17   1   0.3097  0.2835  0.3564  11.00000  0.05    0.03
;
_shelx_res_checksum              55310

_exptl_crystal_recrystallization_method 'flux growth'
_exptl_crystal_preparation       'Magnetic properties'
