# Electronic Supplementary Material (ESI) for New Journal of Chemistry.
# This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2024

####################################################################### 
# 
# 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_shelx
_database_code_depnum_ccdc_archive 'CCDC 2301360'
loop_
_audit_author_name
_audit_author_address
'Larisa Shvanskaya'
;Lomonosov MSU
Russia
;
_audit_update_record             
;
2023-10-16 deposited with the CCDC.	2023-12-22 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        
'Hexamanganese manganese trihydroxide dihydrogen/hydrogenvanadate divanadate'
_chemical_name_common            'Manganese hydroxide vanadate divanadate'
_chemical_melting_point          ?
_chemical_formula_moiety         'H7 Mn13.50 O37.69 V8, 1.392(H)'
_chemical_formula_sum            'H4.20 Mn6.75 O18.845 V4'
_chemical_formula_weight         880.335

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'
O O 0.0106 0.0060 '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'
V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      hexagonal
_space_group_IT_number           186
_space_group_name_H-M_alt        'P 63 m c'
_space_group_name_Hall           'P 6c -2c'

_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'
'-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                   13.1893(5)
_cell_length_b                   13.1893(5)
_cell_length_c                   5.2408(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     789.54(7)
_cell_formula_units_Z            2
_cell_measurement_temperature    120(2)
_cell_measurement_reflns_used    7817
_cell_measurement_theta_min      2.502
_cell_measurement_theta_max      30.14

_exptl_crystal_description       needle
_exptl_crystal_colour            black
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    3.706
_exptl_crystal_F_000             832
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.251
_exptl_crystal_size_mid          0.043
_exptl_crystal_size_min          0.036
_exptl_absorpt_coefficient_mu    7.549
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5105
_exptl_absorpt_correction_T_max  0.6501
_exptl_absorpt_process_details   
;
 SADABS 2016/2: Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D.,
 J. Appl. Cryst. 48 (2015) 3-10
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      120(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_measurement_device_type  'Bruker D8 Quest with Photon III detector'
_diffrn_measurement_method       'ω shutterless scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            7817
_diffrn_reflns_av_unetI/netI     0.0233
_diffrn_reflns_av_R_equivalents  0.0463
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_theta_min         3.089
_diffrn_reflns_theta_max         29.966
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.996
_reflns_number_total             858
_reflns_number_gt                816
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.810
_reflns_Friedel_fraction_max     0.997
_reflns_Friedel_fraction_full    0.996

_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       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_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)+(0.0171P)²+0.2347P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refU
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_extinction_coef       0.0019(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Flack x determined using 355 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(2)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         858
_refine_ls_number_parameters     68
_refine_ls_number_restraints     4
_refine_ls_R_factor_all          0.0199
_refine_ls_R_factor_gt           0.0180
_refine_ls_wR_factor_ref         0.0400
_refine_ls_wR_factor_gt          0.0393
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_restrained_S_all      1.077
_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
Mn1 Mn 0.42652(4) 0.34748(4) -0.02641(7) 0.00622(13) Uani 1 1 d . . . . .
Mn2 Mn 0.000000 0.000000 0.1493(4) 0.0174(6) Uani 0.749(5) 6 d S T . . .
V1 V 0.30128(6) 0.15064(3) 0.44837(16) 0.00590(17) Uani 1 2 d S T P . .
V2A V 0.666667 0.333333 -0.2884(3) 0.0066(3) Uani 0.847(3) 6 d S T P . .
V2B V 0.666667 0.333333 -0.007(2) 0.0066(3) Uani 0.153(3) 6 d S T P . .
O1 O 0.1524(3) 0.07621(14) 0.4001(7) 0.0126(7) Uani 1 2 d S T P . .
O2 O 0.3795(3) 0.18977(15) 0.1644(6) 0.0083(6) Uani 1 2 d S T P . .
O3 O 0.3420(2) 0.2747(2) 0.6222(5) 0.0084(5) Uani 1 1 d . . . . .
O4 O 0.52559(15) 0.47441(15) 0.2851(6) 0.0083(7) Uani 1 2 d DS T P . .
O5 O 0.59648(17) 0.40352(17) -0.1762(10) 0.0234(10) Uani 1 2 d DS T P . .
O6 O 0.666667 0.333333 0.375(2) 0.044(3) Uani 0.847(3) 6 d DS T P . .
H1 H 0.5566(16) 0.4434(16) 0.394(9) 0.009(13) Uiso 1 2 d DS . P . .
H2 H 0.626613 0.373(13) 0.41(2) 0.009(13) Uiso 0.232 2 d DS . P . .
H3 H 0.610(13) 0.390(13) -0.01(2) 0.009(13) Uiso 0.168 2 d DS . P . .


_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 2.1028(18) . ?
Mn1 O3 2.116(2) 10_554 ?
Mn1 O3 2.118(2) 1_554 ?
Mn1 O5 2.129(3) . ?
Mn1 O4 2.233(2) . ?
Mn1 O4 2.326(3) 4_664 ?
Mn1 Mn1 2.9808(8) 7_665 ?
Mn1 Mn1 3.1823(5) 10 ?
Mn1 Mn1 3.1823(5) 10_554 ?
Mn2 O1 2.176(4) 4_554 ?
Mn2 O1 2.176(4) 5_554 ?
Mn2 O1 2.176(4) 6_554 ?
Mn2 O1 2.182(4) . ?
Mn2 O1 2.182(4) 2 ?
Mn2 O1 2.182(4) 3 ?
Mn2 Mn2 2.62038(10) 4_554 ?
Mn2 Mn2 2.62042(10) 4 ?
V1 O3 1.708(2) 9 ?
V1 O3 1.708(2) . ?
V1 O1 1.719(3) . ?
V1 O2 1.736(3) . ?
V2A V2B 1.473(11) . ?
V2A O5 1.708(4) . ?
V2A O5 1.708(4) 3_665 ?
V2A O5 1.708(4) 2_655 ?
V2A O6 1.763(13) 1_554 ?
V2A H3 1.9(3) . ?
V2A H3 1.9(3) 2_655 ?
V2A H3 1.9(3) 3_665 ?
V2B O5 1.831(7) . ?
V2B O5 1.831(7) 2_655 ?
V2B O5 1.831(7) 3_665 ?
V2B O6 2.005(18) . ?
V2B H3 1.3(3) . ?
V2B H3 1.3(3) 2_655 ?
V2B H3 1.3(3) 3_665 ?
O4 H1 0.911(14) . ?
O5 H3 0.918(15) . ?
O6 H2 0.93(2) . ?

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 O3 89.16(10) . 10_554 ?
O2 Mn1 O3 97.88(11) . 1_554 ?
O3 Mn1 O3 91.70(9) 10_554 1_554 ?
O2 Mn1 O5 104.90(14) . . ?
O3 Mn1 O5 164.16(11) 10_554 . ?
O3 Mn1 O5 93.51(14) 1_554 . ?
O2 Mn1 O4 99.58(12) . . ?
O3 Mn1 O4 86.88(10) 10_554 . ?
O3 Mn1 O4 162.46(10) 1_554 . ?
O5 Mn1 O4 83.65(13) . . ?
O2 Mn1 O4 176.36(12) . 4_664 ?
O3 Mn1 O4 88.02(10) 10_554 4_664 ?
O3 Mn1 O4 84.50(9) 1_554 4_664 ?
O5 Mn1 O4 77.62(13) . 4_664 ?
O4 Mn1 O4 77.98(6) . 4_664 ?
O2 Mn1 Mn1 129.94(10) . 7_665 ?
O3 Mn1 Mn1 119.37(6) 10_554 7_665 ?
O3 Mn1 Mn1 119.34(6) 1_554 7_665 ?
O5 Mn1 Mn1 45.56(8) . 7_665 ?
O4 Mn1 Mn1 48.14(6) . 7_665 ?
O4 Mn1 Mn1 50.15(6) 4_664 7_665 ?
O2 Mn1 Mn1 87.12(8) . 10 ?
O3 Mn1 Mn1 41.30(7) 10_554 10 ?
O3 Mn1 Mn1 132.84(7) 1_554 10 ?
O5 Mn1 Mn1 130.58(11) . 10 ?
O4 Mn1 Mn1 46.94(7) . 10 ?
O4 Mn1 Mn1 89.24(8) 4_664 10 ?
Mn1 Mn1 Mn1 90.0 7_665 10 ?
O2 Mn1 Mn1 137.13(10) . 10_554 ?
O3 Mn1 Mn1 81.65(7) 10_554 10_554 ?
O3 Mn1 Mn1 41.24(6) 1_554 10_554 ?
O5 Mn1 Mn1 92.48(14) . 10_554 ?
O4 Mn1 Mn1 121.41(8) . 10_554 ?
O4 Mn1 Mn1 44.56(6) 4_664 10_554 ?
Mn1 Mn1 Mn1 90.0 7_665 10_554 ?
Mn1 Mn1 Mn1 110.86(3) 10 10_554 ?
O1 Mn2 O1 87.71(15) 4_554 5_554 ?
O1 Mn2 O1 87.71(15) 4_554 6_554 ?
O1 Mn2 O1 87.71(15) 5_554 6_554 ?
O1 Mn2 O1 179.81(18) 4_554 . ?
O1 Mn2 O1 92.43(7) 5_554 . ?
O1 Mn2 O1 92.43(7) 6_554 . ?
O1 Mn2 O1 92.43(7) 4_554 2 ?
O1 Mn2 O1 179.81(18) 5_554 2 ?
O1 Mn2 O1 92.43(7) 6_554 2 ?
O1 Mn2 O1 87.44(15) . 2 ?
O1 Mn2 O1 92.43(7) 4_554 3 ?
O1 Mn2 O1 92.43(7) 5_554 3 ?
O1 Mn2 O1 179.81(18) 6_554 3 ?
O1 Mn2 O1 87.44(15) . 3 ?
O1 Mn2 O1 87.44(15) 2 3 ?
O1 Mn2 Mn2 53.13(10) 4_554 4_554 ?
O1 Mn2 Mn2 53.13(10) 5_554 4_554 ?
O1 Mn2 Mn2 53.13(10) 6_554 4_554 ?
O1 Mn2 Mn2 127.06(10) . 4_554 ?
O1 Mn2 Mn2 127.06(10) 2 4_554 ?
O1 Mn2 Mn2 127.06(10) 3 4_554 ?
O1 Mn2 Mn2 126.87(10) 4_554 4 ?
O1 Mn2 Mn2 126.87(10) 5_554 4 ?
O1 Mn2 Mn2 126.87(10) 6_554 4 ?
O1 Mn2 Mn2 52.94(10) . 4 ?
O1 Mn2 Mn2 52.94(10) 2 4 ?
O1 Mn2 Mn2 52.94(10) 3 4 ?
Mn2 Mn2 Mn2 180.0 4_554 4 ?
O3 V1 O3 106.42(16) 9 . ?
O3 V1 O1 110.34(11) 9 . ?
O3 V1 O1 110.34(11) . . ?
O3 V1 O2 108.49(10) 9 . ?
O3 V1 O2 108.49(10) . . ?
O1 V1 O2 112.54(17) . . ?
V2B V2A O5 69.85(18) . . ?
V2B V2A O5 69.85(18) . 3_665 ?
O5 V2A O5 108.78(19) . 3_665 ?
V2B V2A O5 69.85(18) . 2_655 ?
O5 V2A O5 108.78(19) . 2_655 ?
O5 V2A O5 108.78(19) 3_665 2_655 ?
V2B V2A O6 180.0 . 1_554 ?
O5 V2A O6 110.15(19) . 1_554 ?
O5 V2A O6 110.15(19) 3_665 1_554 ?
O5 V2A O6 110.15(19) 2_655 1_554 ?
V2B V2A H3 42(5) . . ?
O5 V2A H3 28(4) . . ?
O5 V2A H3 93(3) 3_665 . ?
O5 V2A H3 93(3) 2_655 . ?
O6 V2A H3 138(5) 1_554 . ?
V2B V2A H3 42(4) . 2_655 ?
O5 V2A H3 93(3) . 2_655 ?
O5 V2A H3 93(3) 3_665 2_655 ?
O5 V2A H3 28(4) 2_655 2_655 ?
O6 V2A H3 138(4) 1_554 2_655 ?
H3 V2A H3 70(7) . 2_655 ?
V2B V2A H3 42(5) . 3_665 ?
O5 V2A H3 93(3) . 3_665 ?
O5 V2A H3 28(4) 3_665 3_665 ?
O5 V2A H3 93(3) 2_655 3_665 ?
O6 V2A H3 138(4) 1_554 3_665 ?
H3 V2A H3 70(7) . 3_665 ?
H3 V2A H3 70(7) 2_655 3_665 ?
V2A V2B O5 61.1(3) . . ?
V2A V2B O5 61.1(3) . 2_655 ?
O5 V2B O5 98.6(4) . 2_655 ?
V2A V2B O5 61.1(3) . 3_665 ?
O5 V2B O5 98.6(4) . 3_665 ?
O5 V2B O5 98.6(4) 2_655 3_665 ?
V2A V2B O6 180.0 . . ?
O5 V2B O6 118.9(3) . . ?
O5 V2B O6 118.9(3) 2_655 . ?
O5 V2B O6 118.9(3) 3_665 . ?
V2A V2B H3 89(5) . . ?
O5 V2B H3 28(5) . . ?
O5 V2B H3 115(3) 2_655 . ?
O5 V2B H3 115(3) 3_665 . ?
O6 V2B H3 91(5) . . ?
V2A V2B H3 89(5) . 2_655 ?
O5 V2B H3 115(3) . 2_655 ?
O5 V2B H3 28(5) 2_655 2_655 ?
O5 V2B H3 115(3) 3_665 2_655 ?
O6 V2B H3 91(5) . 2_655 ?
H3 V2B H3 120.0(4) . 2_655 ?
V2A V2B H3 89(5) . 3_665 ?
O5 V2B H3 115(3) . 3_665 ?
O5 V2B H3 115(3) 2_655 3_665 ?
O5 V2B H3 28(5) 3_665 3_665 ?
O6 V2B H3 91(5) . 3_665 ?
H3 V2B H3 120.0(4) . 3_665 ?
H3 V2B H3 120.0(4) 2_655 3_665 ?
V1 O1 Mn2 134.7(2) . 4 ?
V1 O1 Mn2 151.4(2) . . ?
Mn2 O1 Mn2 73.93(10) 4 . ?
V1 O2 Mn1 122.62(8) . 9 ?
V1 O2 Mn1 122.62(8) . . ?
Mn1 O2 Mn1 114.67(16) 9 . ?
V1 O3 Mn1 123.78(13) . 10 ?
V1 O3 Mn1 137.74(13) . 1_556 ?
Mn1 O3 Mn1 97.46(10) 10 1_556 ?
Mn1 O4 Mn1 83.72(11) . 7_665 ?
Mn1 O4 Mn1 146.02(16) . 4_665 ?
Mn1 O4 Mn1 88.51(5) 7_665 4_665 ?
Mn1 O4 Mn1 88.51(5) . 10 ?
Mn1 O4 Mn1 146.01(16) 7_665 10 ?
Mn1 O4 Mn1 79.71(11) 4_665 10 ?
Mn1 O4 H1 110(2) . . ?
Mn1 O4 H1 110(2) 7_665 . ?
Mn1 O4 H1 103(3) 4_665 . ?
Mn1 O4 H1 103(3) 10 . ?
V2A O5 V2B 49.0(3) . . ?
V2A O5 Mn1 134.50(9) . . ?
V2B O5 Mn1 110.9(3) . . ?
V2A O5 Mn1 134.50(9) . 7_665 ?
V2B O5 Mn1 110.9(3) . 7_665 ?
Mn1 O5 Mn1 88.89(15) . 7_665 ?
V2A O5 H3 90(10) . . ?
V2B O5 H3 41(10) . . ?
Mn1 O5 H3 82(10) . . ?
Mn1 O5 H3 82(10) 7_665 . ?
V2A O6 V2B 180.0 1_556 . ?
V2A O6 H2 80(7) 1_556 . ?
V2B O6 H2 100(7) . . ?

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
O4 H1 O5 0.911(14) 2.43(3) 3.255(6) 151(5) 1_556 yes
O4 H1 O6 0.911(14) 2.52(4) 3.257(4) 139(4) . yes
O6 H2 O4 0.93(2) 2.39(3) 3.257(4) 155(10) . yes
O6 H2 O5 0.93(2) 2.30(12) 2.846(11) 117(8) 1_556 yes
O5 H3 O6 0.918(15) 2.40(7) 3.304(12) 168(28) . yes

_refine_diff_density_max         0.715
_refine_diff_density_min         -0.529
_refine_diff_density_rms         0.092



