 
data_monteneroite
 
_audit_creation_method            'SHELXL-2016/6'
_shelx_SHELXL_version_number      '2016/6'
_chemical_name_mineral            'monteneroite' 
_chemical_compound_source         'Monte Nero mine, Italy'
_chemical_formula_sum
 'As2 H16 Cu0.70 Mn2.30 O16' 
_chemical_formula_weight          592.81

loop_
 _atom_type_symbol
 _atom_type_description
 _atom_type_scat_dispersion_real
 _atom_type_scat_dispersion_imag
 _atom_type_scat_source
 'As'  'As'   0.0499   2.0058
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'Cu'  'Cu'   0.3201   1.2651
 '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'
 'O'  'O'   0.0106   0.0060
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 
_space_group_crystal_system       monoclinic
_space_group_IT_number            12
_space_group_name_H-M_alt         'C 2/m'
_space_group_name_Hall            '-C 2y'
 
_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'
 'x+1/2, y+1/2, z'
 'x+1/2, -y+1/2, z'
 '-x, -y, -z'
 '-x, y, -z'
 '-x+1/2, -y+1/2, -z'
 '-x+1/2, y+1/2, -z'
 
_cell_length_a                    10.3673(14)
_cell_length_b                    13.713(2)
_cell_length_c                    4.8420(8)
_cell_angle_alpha                 90
_cell_angle_beta                  105.992(8)
_cell_angle_gamma                 90
_cell_volume                      661.72(18)
_cell_formula_units_Z             2
_cell_measurement_temperature     293(2)
_cell_measurement_reflns_used     1737
_cell_measurement_theta_min       4.1
_cell_measurement_theta_max       25.0
 
_exptl_crystal_description        'plate'
_exptl_crystal_colour             'pale green'
_exptl_crystal_density_meas       2.97
_exptl_crystal_density_method     'flotation'
_exptl_crystal_density_diffrn     2.975          
_exptl_crystal_F_000              576
_exptl_crystal_size_max           0.090
_exptl_crystal_size_mid           0.090
_exptl_crystal_size_min           0.020
_exptl_absorpt_coefficient_mu     8.324
_exptl_absorpt_correction_T_max   1.000
_exptl_absorpt_correction_T_min   0.573
_shelx_estimated_absorpt_T_min    0.521
_shelx_estimated_absorpt_T_max    0.851
_diffrn_measurement_device_type   'Rigaku R-axis RAPID II'
_exptl_absorpt_correction_type    multi-scan 
_exptl_absorpt_process_details    Higashi2001 
_diffrn_ambient_temperature       293(2)
_diffrn_radiation_wavelength      0.71075
_diffrn_radiation_type            MoK\a
_diffrn_source                    'fine-focus sealed tube'                       
_diffrn_radiation_monochromator   graphite 
_diffrn_reflns_number             2116
_diffrn_reflns_av_unetI/netI      0.0449
_diffrn_reflns_av_R_equivalents   0.0500
_diffrn_reflns_limit_h_min        -11
_diffrn_reflns_limit_h_max        11
_diffrn_reflns_limit_k_min        -16
_diffrn_reflns_limit_k_max        16
_diffrn_reflns_limit_l_min        -5
_diffrn_reflns_limit_l_max        5
_diffrn_reflns_theta_min          4.090
_diffrn_reflns_theta_max          25.014
_diffrn_reflns_theta_full         25.014
_diffrn_measured_fraction_theta_max   0.956
_diffrn_measured_fraction_theta_full  0.956
_diffrn_reflns_Laue_measured_fraction_max    0.956
_diffrn_reflns_Laue_measured_fraction_full   0.956
_diffrn_reflns_point_group_measured_fraction_max   0.956
_diffrn_reflns_point_group_measured_fraction_full  0.956
_reflns_number_total              590
_reflns_number_gt                 534
_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_structure_solution     'SHELXT 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement 'SHELXL-2016/6 (Sheldrick, 2016)'
_refine_ls_structure_factor_coef  Fsqd
_refine_ls_matrix_type            full
_refine_ls_weighting_scheme       calc
_refine_ls_weighting_details
'w=1/[σ²(Fo²)+(0.1230P)²+3.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary      ?
_atom_sites_solution_secondary    ?
_atom_sites_solution_hydrogens    difmap
_refine_ls_hydrogen_treatment     refxyz
_refine_ls_extinction_method      'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_extinction_coef        0.003(2)
_refine_ls_extinction_expression
 'Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^'
_refine_ls_number_reflns          590
_refine_ls_number_parameters      69
_refine_ls_number_restraints      6
_refine_ls_R_factor_all           0.0569
_refine_ls_R_factor_gt            0.0535
_refine_ls_wR_factor_ref          0.1646
_refine_ls_wR_factor_gt           0.1592
_refine_ls_goodness_of_fit_ref    1.096
_refine_ls_restrained_S_all       1.091
_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
As As 0.18938(10) 0.000000 0.1301(2) 0.0221(6) Uani 1 2 d S T P . .
Cu1 Cu 0.500000 0.000000 0.500000 0.0218(9) Uani 0.69(5) 4 d S T P . .
Mn1 Mn 0.500000 0.000000 0.500000 0.0218(9) Uani 0.31(5) 4 d S T P . .
Mn2 Mn 0.000000 0.11564(11) 0.500000 0.0241(7) Uani 1 2 d S T P . .
O1 O 0.3539(7) 0.000000 0.1365(14) 0.0246(17) Uani 1 2 d S T P . .
O2 O 0.1622(6) 0.1034(4) 0.2890(11) 0.0266(13) Uani 1 1 d . . . . .
O3 O 0.1012(8) 0.000000 -0.2171(15) 0.0258(17) Uani 1 2 d S T P . .
O4 O 0.4020(7) 0.1143(5) 0.6980(13) 0.0407(16) Uani 1 1 d D . . . .
H4A H 0.382(10) 0.106(8) 0.846(12) 0.049 Uiso 1 1 d D U . . .
H4B H 0.335(6) 0.121(8) 0.573(14) 0.049 Uiso 1 1 d D U . . .
O5 O 0.1019(7) 0.2286(4) 0.7954(12) 0.0376(15) Uani 1 1 d D . . . .
H5A H 0.087(10) 0.287(3) 0.795(17) 0.045 Uiso 1 1 d D U . . .
H5B H 0.127(11) 0.211(6) 0.961(9) 0.045 Uiso 1 1 d 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
As O2 1.674(5) . ?
As O2 1.674(5) 2 ?
As O3 1.678(7) . ?
As O1 1.697(7) . ?
Cu1 O1 1.981(7) 5_656 ?
Cu1 O1 1.981(7) . ?
Cu1 O4 2.223(7) . ?
Cu1 O4 2.223(7) 6_656 ?
Cu1 O4 2.223(7) 2 ?
Cu1 O4 2.223(7) 5_656 ?
Mn2 O3 2.168(5) 5 ?
Mn2 O3 2.168(5) 1_556 ?
Mn2 O5 2.175(6) . ?
Mn2 O5 2.175(6) 6_556 ?
Mn2 O2 2.201(5) . ?
Mn2 O2 2.201(5) 6_556 ?
Mn2 Mn2 3.171(3) 5_556 ?
O4 H4A 0.80(3) . ?
O4 H4B 0.79(3) . ?
O5 H5A 0.81(3) . ?
O5 H5B 0.81(3) . ?
 
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 As O2 115.8(3) . 2 ?
O2 As O3 110.3(2) . . ?
O2 As O3 110.3(2) 2 . ?
O2 As O1 106.7(2) . . ?
O2 As O1 106.7(2) 2 . ?
O3 As O1 106.6(4) . . ?
O1 Cu1 O1 180.0 5_656 . ?
O1 Cu1 O4 86.9(2) 5_656 . ?
O1 Cu1 O4 93.1(2) . . ?
O1 Cu1 O4 93.1(2) 5_656 6_656 ?
O1 Cu1 O4 86.9(2) . 6_656 ?
O4 Cu1 O4 90.4(3) . 6_656 ?
O1 Cu1 O4 86.9(2) 5_656 2 ?
O1 Cu1 O4 93.1(2) . 2 ?
O4 Cu1 O4 89.6(3) . 2 ?
O4 Cu1 O4 180.0(3) 6_656 2 ?
O1 Cu1 O4 93.1(2) 5_656 5_656 ?
O1 Cu1 O4 86.9(2) . 5_656 ?
O4 Cu1 O4 180.0 . 5_656 ?
O4 Cu1 O4 89.6(3) 6_656 5_656 ?
O4 Cu1 O4 90.4(3) 2 5_656 ?
O3 Mn2 O3 86.0(3) 5 1_556 ?
O3 Mn2 O5 178.2(2) 5 . ?
O3 Mn2 O5 92.4(2) 1_556 . ?
O3 Mn2 O5 92.4(2) 5 6_556 ?
O3 Mn2 O5 178.2(2) 1_556 6_556 ?
O5 Mn2 O5 89.1(3) . 6_556 ?
O3 Mn2 O2 87.1(2) 5 . ?
O3 Mn2 O2 86.5(2) 1_556 . ?
O5 Mn2 O2 93.7(2) . . ?
O5 Mn2 O2 92.5(2) 6_556 . ?
O3 Mn2 O2 86.5(2) 5 6_556 ?
O3 Mn2 O2 87.1(2) 1_556 6_556 ?
O5 Mn2 O2 92.5(2) . 6_556 ?
O5 Mn2 O2 93.7(2) 6_556 6_556 ?
O2 Mn2 O2 171.3(3) . 6_556 ?
O3 Mn2 Mn2 42.99(14) 5 5_556 ?
O3 Mn2 Mn2 42.99(15) 1_556 5_556 ?
O5 Mn2 Mn2 135.43(17) . 5_556 ?
O5 Mn2 Mn2 135.43(17) 6_556 5_556 ?
O2 Mn2 Mn2 85.63(14) . 5_556 ?
O2 Mn2 Mn2 85.63(14) 6_556 5_556 ?
As O1 Cu1 122.3(4) . . ?
As O2 Mn2 121.7(3) . . ?
As O3 Mn2 131.94(15) . 5 ?
As O3 Mn2 131.94(15) . 1_554 ?
Mn2 O3 Mn2 94.0(3) 5 1_554 ?
Cu1 O4 H4A 122(8) . . ?
Cu1 O4 H4B 99(8) . . ?
H4A O4 H4B 108(5) . . ?
Mn2 O5 H5A 130(6) . . ?
Mn2 O5 H5B 114(6) . . ?
H5A O5 H5B 108(5) . . ?
 
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 
O4 H4A O1  0.80(3) 2.10(7) 2.792(8) 145(10) 1_556
O4 H4B O2  0.79(3) 1.95(4) 2.722(9) 165(11) .
O5 H5A O4  0.81(3) 2.29(7) 2.936(9) 137(9) 4_455
O5 H5B O2  0.81(3) 2.12(4) 2.868(8) 153(8) 1_556
 
_refine_diff_density_max    1.190
_refine_diff_density_min   -2.368
_refine_diff_density_rms    0.280



