# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2016

 
data_1 
 
_audit_creation_method            SHELXL-97 
_chemical_name_systematic 
; 
 ? 
; 
_chemical_name_common             ? 
_chemical_melting_point           ? 
_chemical_formula_moiety          ? 
_chemical_formula_sum 
 'H Mn O9 Pb2 V2' 
_chemical_formula_weight          716.21 
 
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' 
 'V'  'V'   0.3005   0.5294 
 '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' 
 'Pb'  'Pb'  -3.3944  10.1111 
 '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' 
 
_symmetry_cell_setting            ��monoclinic�� 
_symmetry_space_group_name_H-M    ��P2(1)/m�� 
 
loop_ 
 _symmetry_equiv_pos_as_xyz 
 'x, y, z' 
 '-x, y+1/2, -z' 
 '-x, -y, -z' 
 'x, -y-1/2, z' 
 
_cell_length_a                    7.672(7) 
_cell_length_b                    6.168(5) 
_cell_length_c                    8.781(9) 
_cell_angle_alpha                 90.00 
_cell_angle_beta                  111.232(14) 
_cell_angle_gamma                 90.00 
_cell_volume                      387.3(6) 
_cell_formula_units_Z             2 
_cell_measurement_temperature     293(2) 
_cell_measurement_reflns_used           1205
_cell_measurement_theta_min             2.4883
_cell_measurement_theta_max             27.4276 
 
_exptl_crystal_description        ��brick�� 
_exptl_crystal_colour             ��dark-red�� 
_exptl_crystal_size_max           0.10 
_exptl_crystal_size_mid           0.08 
_exptl_crystal_size_min           0.04 
_exptl_crystal_density_meas       ? 
_exptl_crystal_density_diffrn     6.141 
_exptl_crystal_density_method     'not measured' 
_exptl_crystal_F_000              616 
_exptl_absorpt_coefficient_mu     47.256 
_exptl_absorpt_correction_type          'Multi-scan'
_exptl_absorpt_correction_T_max         1.0000
_exptl_absorpt_correction_T_min         0.6309 
_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   ��Saturn724+(2x2binmode)�� 
_diffrn_measurement_method        'CCD_Profile_fitting' 
_diffrn_detector_area_resol_mean  ? 
_diffrn_standards_number          ? 
_diffrn_standards_interval_count  ? 
_diffrn_standards_interval_time   ? 
_diffrn_standards_decay_%         ? 
_diffrn_reflns_number             3253 
_diffrn_reflns_av_R_equivalents   0.0828 
_diffrn_reflns_av_sigmaI/netI     0.0825 
_diffrn_reflns_limit_h_min        -9 
_diffrn_reflns_limit_h_max        9 
_diffrn_reflns_limit_k_min        -7 
_diffrn_reflns_limit_k_max        7 
_diffrn_reflns_limit_l_min        -10 
_diffrn_reflns_limit_l_max        11 
_diffrn_reflns_theta_min          2.85 
_diffrn_reflns_theta_max          27.45 
_reflns_number_total              949 
_reflns_number_gt                 878 
_reflns_threshold_expression      >2sigma(I) 
 
_computing_data_collection        ? 
_computing_cell_refinement        ? 
_computing_data_reduction         ? 
_computing_structure_solution     'SHELXS-97 (Sheldrick, 1990)' 
_computing_structure_refinement   'SHELXL-97 (Sheldrick, 1997)' 
_computing_molecular_graphics     ? 
_computing_publication_material   ? 
 
_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)+(0.0238P)²+0.0000P] where P=(Fo²+2Fc²)/3' 
_atom_sites_solution_primary      direct 
_atom_sites_solution_secondary    difmap 
_atom_sites_solution_hydrogens    geom 
_refine_ls_hydrogen_treatment     constr 
_refine_ls_extinction_method      SHELXL 
_refine_ls_extinction_coef        0.0010(2) 
_refine_ls_extinction_expression 
 'Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^' 
_refine_ls_number_reflns          949 
_refine_ls_number_parameters      80 
_refine_ls_number_restraints      6 
_refine_ls_R_factor_all           0.0367 
_refine_ls_R_factor_gt            0.0324 
_refine_ls_wR_factor_ref          0.0700 
_refine_ls_wR_factor_gt           0.0678 
_refine_ls_goodness_of_fit_ref    1.062 
_refine_ls_restrained_S_all       1.060 
_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_symmetry_multiplicity 
 _atom_site_calc_flag 
 _atom_site_refinement_flags 
 _atom_site_disorder_assembly 
 _atom_site_disorder_group 
Pb1 Pb 0.27022(6) 0.2500 0.75290(5) 0.01883(19) Uani 1 2 d S . . 
Pb2 Pb 0.66948(7) 0.2500 1.59343(7) 0.0259(2) Uani 1 2 d S . . 
Mn Mn 0.0000 0.0000 0.0000 0.0078(4) Uani 1 2 d S . . 
V1 V 0.0407(2) 0.2500 0.3359(2) 0.0088(5) Uani 1 2 d S . . 
V2 V 0.4495(2) 0.2500 1.1759(2) 0.0090(5) Uani 1 2 d S . . 
O1 O -0.1700(9) 0.2500 -0.0751(10) 0.0101(18) Uani 1 2 d SU . . 
H1 H -0.2312 0.2500 -0.0115 0.012 Uiso 1 2 d SR . . 
O2 O -0.0117(7) 0.0130(9) 0.2160(7) 0.0162(12) Uani 1 1 d . . . 
O3 O -0.0780(11) 0.2500 0.4597(10) 0.0209(19) Uani 1 2 d S . . 
O4 O 0.2676(10) 0.2500 0.4540(9) 0.0208(19) Uani 1 2 d S . . 
O5 O 0.5591(10) 0.2500 1.0426(10) 0.027(2) Uani 1 2 d S . . 
O6 O 0.2114(9) 0.2500 1.0589(9) 0.0122(17) Uani 1 2 d S . . 
O7 O 0.5117(7) 0.0235(9) 1.2989(7) 0.0141(12) Uani 1 1 d . . . 
 
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 
Pb1 0.0190(3) 0.0191(3) 0.0197(3) 0.000 0.0086(2) 0.000 
Pb2 0.0250(3) 0.0299(4) 0.0282(4) 0.000 0.0162(2) 0.000 
Mn 0.0062(7) 0.0097(9) 0.0082(9) 0.0007(7) 0.0035(6) 0.0023(7) 
V1 0.0087(9) 0.0108(12) 0.0083(11) 0.000 0.0047(8) 0.000 
V2 0.0028(9) 0.0116(12) 0.0128(12) 0.000 0.0031(8) 0.000 
O1 0.009(3) 0.011(3) 0.014(3) 0.000 0.008(2) 0.000 
O2 0.023(3) 0.011(3) 0.018(3) -0.003(3) 0.010(2) -0.004(2) 
O3 0.028(4) 0.019(5) 0.028(5) 0.000 0.024(4) 0.000 
O4 0.013(4) 0.028(5) 0.019(5) 0.000 0.003(3) 0.000 
O5 0.016(4) 0.041(6) 0.029(5) 0.000 0.016(4) 0.000 
O6 0.009(4) 0.012(4) 0.013(4) 0.000 0.001(3) 0.000 
O7 0.011(3) 0.008(3) 0.022(3) 0.002(2) 0.004(2) 0.002(2) 
 
_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 
Pb1 O7 2.531(5) 2_657 ? 
Pb1 O7 2.531(5) 3_657 ? 
Pb1 O4 2.618(8) . ? 
Pb1 O2 2.652(6) 3_556 ? 
Pb1 O2 2.652(5) 2_556 ? 
Pb1 O5 2.701(8) . ? 
Pb2 O7 2.573(5) 3_658 ? 
Pb2 O7 2.573(5) 2_658 ? 
Pb2 O3 2.604(8) 1_656 ? 
Pb2 O1 2.719(8) 1_657 ? 
Mn O2 1.933(6) 3 ? 
Mn O2 1.933(6) . ? 
Mn O1 1.972(4) 3 ? 
Mn O1 1.972(4) . ? 
Mn O6 2.160(5) 3_556 ? 
Mn O6 2.160(5) 1_554 ? 
Mn Mn 3.084(3) 2_545 ? 
Mn Mn 3.084(3) 2 ? 
V1 O3 1.651(8) . ? 
V1 O4 1.673(7) . ? 
V1 O2 1.761(6) . ? 
V1 O2 1.761(6) 4_565 ? 
V2 O5 1.670(8) . ? 
V2 O7 1.725(6) 4_565 ? 
V2 O7 1.725(6) . ? 
V2 O6 1.742(7) . ? 
O1 Mn 1.972(4) 2 ? 
O1 Pb2 2.719(8) 1_453 ? 
O2 Pb1 2.652(5) 3_556 ? 
O3 Pb2 2.604(8) 1_454 ? 
O6 Mn 2.160(5) 1_556 ? 
O6 Mn 2.160(5) 2_556 ? 
O7 Pb1 2.531(5) 3_657 ? 
O7 Pb2 2.573(5) 3_658 ? 
 
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 
O7 Pb1 O7 83.6(2) 2_657 3_657 ? 
O7 Pb1 O4 65.49(16) 2_657 . ? 
O7 Pb1 O4 65.49(16) 3_657 . ? 
O7 Pb1 O2 173.82(15) 2_657 3_556 ? 
O7 Pb1 O2 100.29(19) 3_657 3_556 ? 
O4 Pb1 O2 111.64(17) . 3_556 ? 
O7 Pb1 O2 100.29(19) 2_657 2_556 ? 
O7 Pb1 O2 173.82(15) 3_657 2_556 ? 
O4 Pb1 O2 111.64(17) . 2_556 ? 
O2 Pb1 O2 75.4(2) 3_556 2_556 ? 
O7 Pb1 O5 78.41(18) 2_657 . ? 
O7 Pb1 O5 78.41(18) 3_657 . ? 
O4 Pb1 O5 130.5(2) . . ? 
O2 Pb1 O5 106.99(19) 3_556 . ? 
O2 Pb1 O5 106.99(19) 2_556 . ? 
O7 Pb2 O7 81.9(2) 3_658 2_658 ? 
O7 Pb2 O3 138.99(12) 3_658 1_656 ? 
O7 Pb2 O3 138.99(12) 2_658 1_656 ? 
O7 Pb2 O1 72.68(16) 3_658 1_657 ? 
O7 Pb2 O1 72.68(16) 2_658 1_657 ? 
O3 Pb2 O1 111.1(2) 1_656 1_657 ? 
O2 Mn O2 180.0(4) 3 . ? 
O2 Mn O1 92.1(3) 3 3 ? 
O2 Mn O1 87.9(3) . 3 ? 
O2 Mn O1 87.9(3) 3 . ? 
O2 Mn O1 92.1(3) . . ? 
O1 Mn O1 180.0(3) 3 . ? 
O2 Mn O6 91.9(2) 3 3_556 ? 
O2 Mn O6 88.1(2) . 3_556 ? 
O1 Mn O6 82.5(2) 3 3_556 ? 
O1 Mn O6 97.5(2) . 3_556 ? 
O2 Mn O6 88.1(2) 3 1_554 ? 
O2 Mn O6 91.9(2) . 1_554 ? 
O1 Mn O6 97.5(2) 3 1_554 ? 
O1 Mn O6 82.5(2) . 1_554 ? 
O6 Mn O6 180.0 3_556 1_554 ? 
O2 Mn Mn 87.62(16) 3 2_545 ? 
O2 Mn Mn 92.38(16) . 2_545 ? 
O1 Mn Mn 38.58(16) 3 2_545 ? 
O1 Mn Mn 141.42(16) . 2_545 ? 
O6 Mn Mn 44.46(13) 3_556 2_545 ? 
O6 Mn Mn 135.54(13) 1_554 2_545 ? 
O2 Mn Mn 92.38(16) 3 2 ? 
O2 Mn Mn 87.62(16) . 2 ? 
O1 Mn Mn 141.42(16) 3 2 ? 
O1 Mn Mn 38.58(16) . 2 ? 
O6 Mn Mn 135.54(13) 3_556 2 ? 
O6 Mn Mn 44.46(13) 1_554 2 ? 
Mn Mn Mn 180.0 2_545 2 ? 
O3 V1 O4 106.9(4) . . ? 
O3 V1 O2 109.4(2) . . ? 
O4 V1 O2 109.4(2) . . ? 
O3 V1 O2 109.4(2) . 4_565 ? 
O4 V1 O2 109.4(2) . 4_565 ? 
O2 V1 O2 112.2(4) . 4_565 ? 
O5 V2 O7 110.1(2) . 4_565 ? 
O5 V2 O7 110.1(2) . . ? 
O7 V2 O7 108.2(4) 4_565 . ? 
O5 V2 O6 105.8(4) . . ? 
O7 V2 O6 111.3(2) 4_565 . ? 
O7 V2 O6 111.3(2) . . ? 
Mn O1 Mn 102.8(3) 2 . ? 
Mn O1 Pb2 110.3(2) 2 1_453 ? 
Mn O1 Pb2 110.3(2) . 1_453 ? 
V1 O2 Mn 122.7(3) . . ? 
V1 O2 Pb1 117.6(3) . 3_556 ? 
Mn O2 Pb1 112.2(2) . 3_556 ? 
V1 O3 Pb2 167.0(5) . 1_454 ? 
V1 O4 Pb1 104.5(3) . . ? 
V2 O5 Pb1 102.2(3) . . ? 
V2 O6 Mn 132.62(17) . 1_556 ? 
V2 O6 Mn 132.62(17) . 2_556 ? 
Mn O6 Mn 91.1(3) 1_556 2_556 ? 
V2 O7 Pb1 118.6(3) . 3_657 ? 
V2 O7 Pb2 134.2(3) . 3_658 ? 
Pb1 O7 Pb2 96.28(19) 3_657 3_658 ? 
 
_diffrn_measured_fraction_theta_max    0.985 
_diffrn_reflns_theta_full              27.45 
_diffrn_measured_fraction_theta_full   0.985 
_refine_diff_density_max    1.356 
_refine_diff_density_min   -1.983 
_refine_diff_density_rms    0.302 
