 
data_shelx
 
_audit_creation_method            'SHELXL-2018/1'
_shelx_SHELXL_version_number      '2018/1'
_chemical_name_mineral            'khademite'
_chemical_compound_source         'Monte Arsiccio mine, Apuan Alps, Italy'
_chemical_formula_analytical
;      
Al1.92 F1.68 H20.32 O18.32 S2.04
; 
_chemical_formula_sum
 'Al2 F2 H20 O18 S2' 
_chemical_formula_weight          464.24

loop_
 _atom_type_symbol
 _atom_type_description
 _atom_type_scat_dispersion_real
 _atom_type_scat_dispersion_imag
 _atom_type_scat_source
 'Al'  'Al'   0.0645   0.0514
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'F'  'F'   0.0171   0.0103
 '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'
 'S'  'S'   0.1246   0.1234
 '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'
 
_space_group_crystal_system       orthorhombic
_space_group_IT_number            61
_space_group_name_H-M_alt         'P c a b'
_space_group_name_Hall            '-P 2bc 2ac'
 
_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+1/2, z+1/2'
 'x+1/2, -y, -z+1/2'
 '-x+1/2, y+1/2, -z'
 '-x, -y, -z'
 'x, y-1/2, -z-1/2'
 '-x-1/2, y, z-1/2'
 'x-1/2, -y-1/2, z'
 
_cell_length_a                    11.1713(2)
_cell_length_b                    13.0432(3)
_cell_length_c                    10.8815(2)
_cell_angle_alpha                 90
_cell_angle_beta                  90
_cell_angle_gamma                 90
_cell_volume                      1585.54(5)
_cell_formula_units_Z             4
_cell_measurement_temperature     293(2)
_cell_measurement_reflns_used     9228
_cell_measurement_theta_min       2.40
_cell_measurement_theta_max       31.52
 
_exptl_crystal_description        'tabular'
_exptl_crystal_colour             'colorless'
_exptl_crystal_density_meas       'not measured'
_exptl_crystal_density_method     ?
_exptl_crystal_density_diffrn     1.945          
_exptl_crystal_F_000              960
_exptl_transmission_factor_min    ?
_exptl_transmission_factor_max    ?
_exptl_crystal_size_max           0.18
_exptl_crystal_size_mid           0.15
_exptl_crystal_size_min           0.13
_exptl_absorpt_coefficient_mu     0.561
_shelx_estimated_absorpt_T_min    ?
_shelx_estimated_absorpt_T_max    ?
_exptl_absorpt_correction_type    'multi-scan'
_exptl_absorpt_correction_T_min   0.951
_exptl_absorpt_correction_T_max   0.964
_exptl_absorpt_process_details    '(SADABS, Sheldrick, 1996)'
_exptl_absorpt_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 Smart Breeze'
_diffrn_reflns_number             16010
_diffrn_reflns_av_unetI/netI      0.0133
_diffrn_reflns_av_R_equivalents   0.0196
_diffrn_reflns_limit_h_min        -16
_diffrn_reflns_limit_h_max        16
_diffrn_reflns_limit_k_min        -19
_diffrn_reflns_limit_k_max        16
_diffrn_reflns_limit_l_min        -13
_diffrn_reflns_limit_l_max        15
_diffrn_reflns_theta_min          3.044
_diffrn_reflns_theta_max          31.522
_diffrn_reflns_theta_full         25.242
_diffrn_measured_fraction_theta_max   0.985
_diffrn_measured_fraction_theta_full  0.977
_diffrn_reflns_Laue_measured_fraction_max    0.985
_diffrn_reflns_Laue_measured_fraction_full   0.977
_diffrn_reflns_point_group_measured_fraction_max   0.985
_diffrn_reflns_point_group_measured_fraction_full  0.977
_reflns_number_total              2600
_reflns_number_gt                 2359
_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_data_collection      'Apex3 (Bruker AXS Inc., 2016)'
_computing_cell_refinement      'Apex3 (Bruker AXS Inc., 2016)'
_computing_data_reduction       'Apex3 (Bruker AXS Inc., 2016)'
_computing_structure_refinement 'SHELXL-2018/1 (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)+(0.0395P)²+0.6216P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary      ?
_atom_sites_solution_secondary    ?
_atom_sites_solution_hydrogens    difmap
_refine_ls_hydrogen_treatment     refall
_refine_ls_extinction_method      none
_refine_ls_extinction_coef        .
_refine_ls_number_reflns          2600
_refine_ls_number_parameters      152
_refine_ls_number_restraints      9
_refine_ls_R_factor_all           0.0332
_refine_ls_R_factor_gt            0.0293
_refine_ls_wR_factor_ref          0.0858
_refine_ls_wR_factor_gt           0.0834
_refine_ls_goodness_of_fit_ref    1.137
_refine_ls_restrained_S_all       1.144
_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
Al1 Al 0.000000 0.500000 0.500000 0.01120(11) Uani 1 2 d S . P . .
Al2 Al 0.000000 0.500000 0.000000 0.01252(11) Uani 1 2 d S . P . .
S S 0.23846(3) 0.24741(2) 0.24697(2) 0.01431(9) Uani 1 1 d . . . . .
O1 O 0.16892(9) 0.25489(6) 0.13246(8) 0.02521(19) Uani 1 1 d . . . . .
O2 O 0.30519(10) 0.14999(8) 0.24632(7) 0.0313(2) Uani 1 1 d . . . . .
O3 O 0.15860(9) 0.25014(6) 0.35448(8) 0.0247(2) Uani 1 1 d . . . . .
O4 O 0.32053(9) 0.33547(8) 0.25373(7) 0.0288(2) Uani 1 1 d . . . . .
F F 0.02937(7) 0.50938(5) 0.15592(6) 0.02092(15) Uani 1 1 d . . . . .
OW2 O 0.01006(7) 0.37567(6) 0.58852(7) 0.01751(16) Uani 1 1 d D . . . .
OW3 O 0.14302(7) 0.41497(6) -0.02101(7) 0.01918(16) Uani 1 1 d D . . . .
OW4 O -0.09380(8) 0.38237(6) 0.02869(8) 0.02325(18) Uani 1 1 d D . . . .
OW5 O 0.06920(8) 0.43591(6) 0.36595(7) 0.01916(17) Uani 1 1 d D . . . .
OW6 O -0.15403(7) 0.46351(7) 0.44224(7) 0.01960(17) Uani 1 1 d D . . . .
H21 H -0.0520(15) 0.3324(14) 0.6011(17) 0.042(5) Uiso 1 1 d D . . . .
H22 H 0.0662(16) 0.3610(17) 0.6476(16) 0.050(6) Uiso 1 1 d D . . . .
H31 H 0.1498(17) 0.3608(13) 0.0315(16) 0.042(5) Uiso 1 1 d D . . . .
H32 H 0.148(2) 0.3879(16) -0.0974(15) 0.054(6) Uiso 1 1 d D . . . .
H41 H -0.1181(16) 0.3395(12) -0.0305(14) 0.036(5) Uiso 1 1 d D . . . .
H42 H -0.1231(19) 0.3699(16) 0.0968(19) 0.049(6) Uiso 1 1 d . . . . .
H51 H 0.0907(19) 0.3690(13) 0.3631(19) 0.057(6) Uiso 1 1 d D . . . .
H52 H 0.0576(18) 0.4617(16) 0.2911(14) 0.045(5) Uiso 1 1 d D . . . .
H61 H -0.2242(17) 0.4922(15) 0.468(2) 0.060(7) Uiso 1 1 d D . . . .
H62 H -0.161(2) 0.4245(15) 0.3723(15) 0.055(6) Uiso 1 1 d D . . . .
 
 
_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
Al1 OW5 1.8505(7) . ?
Al1 OW5 1.8505(7) 5_566 ?
Al1 OW2 1.8895(7) 5_566 ?
Al1 OW2 1.8895(7) . ?
Al1 OW6 1.8927(8) 5_566 ?
Al1 OW6 1.8927(8) . ?
Al2 F 1.7324(6) . ?
Al2 F 1.7324(6) 5_565 ?
Al2 OW4 1.8840(8) 5_565 ?
Al2 OW4 1.8841(8) . ?
Al2 OW3 1.9583(8) 5_565 ?
Al2 OW3 1.9584(8) . ?
S O4 1.4714(9) . ?
S O1 1.4716(9) . ?
S O3 1.4717(8) . ?
S O2 1.4732(9) . ?
 
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
OW5 Al1 OW5 180.00(5) . 5_566 ?
OW5 Al1 OW2 90.62(3) . 5_566 ?
OW5 Al1 OW2 89.38(3) 5_566 5_566 ?
OW5 Al1 OW2 89.38(3) . . ?
OW5 Al1 OW2 90.62(3) 5_566 . ?
OW2 Al1 OW2 180.0 5_566 . ?
OW5 Al1 OW6 89.75(4) . 5_566 ?
OW5 Al1 OW6 90.25(4) 5_566 5_566 ?
OW2 Al1 OW6 90.43(4) 5_566 5_566 ?
OW2 Al1 OW6 89.57(4) . 5_566 ?
OW5 Al1 OW6 90.25(4) . . ?
OW5 Al1 OW6 89.75(4) 5_566 . ?
OW2 Al1 OW6 89.57(4) 5_566 . ?
OW2 Al1 OW6 90.43(4) . . ?
OW6 Al1 OW6 180.0 5_566 . ?
F Al2 F 180.0 . 5_565 ?
F Al2 OW4 89.97(3) . 5_565 ?
F Al2 OW4 90.03(3) 5_565 5_565 ?
F Al2 OW4 90.03(3) . . ?
F Al2 OW4 89.97(3) 5_565 . ?
OW4 Al2 OW4 180.0 5_565 . ?
F Al2 OW3 90.01(3) . 5_565 ?
F Al2 OW3 89.99(3) 5_565 5_565 ?
OW4 Al2 OW3 90.68(4) 5_565 5_565 ?
OW4 Al2 OW3 89.32(4) . 5_565 ?
F Al2 OW3 89.99(3) . . ?
F Al2 OW3 90.01(3) 5_565 . ?
OW4 Al2 OW3 89.32(4) 5_565 . ?
OW4 Al2 OW3 90.68(4) . . ?
OW3 Al2 OW3 180.0 5_565 . ?
O4 S O1 108.63(5) . . ?
O4 S O3 108.61(5) . . ?
O1 S O3 110.58(6) . . ?
O4 S O2 110.99(7) . . ?
O1 S O2 108.68(5) . . ?
O3 S O2 109.35(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 
 _geom_hbond_publ_flag
OW2 H21 S  0.905(14) 2.817(16) 3.6412(8) 151.9(16) 2 yes
OW2 H21 O1  0.905(14) 1.765(15) 2.6696(12) 176.9(18) 2 yes
OW2 H22 S  0.918(15) 2.851(16) 3.6965(8) 153.7(17) 7_656 yes
OW2 H22 O4  0.918(15) 1.745(15) 2.6624(11) 177(2) 7_656 yes
OW3 H31 S  0.912(14) 2.943(15) 3.7969(8) 156.4(16) . yes
OW3 H31 O1  0.912(14) 1.778(14) 2.6892(11) 177.8(19) . yes
OW3 H32 S  0.905(15) 2.800(17) 3.5921(8) 146.9(18) 7_655 yes
OW3 H32 O4  0.905(15) 1.793(15) 2.6925(11) 172(2) 7_655 yes
OW4 H41 S  0.895(14) 2.993(14) 3.8567(9) 162.7(15) 2_554 yes
OW4 H41 O3  0.895(14) 1.771(14) 2.6654(11) 176.5(18) 2_554 yes
OW4 H42 S  0.83(2) 2.72(2) 3.4667(9) 151.0(19) 8_565 yes
OW4 H42 O2  0.83(2) 1.83(2) 2.6569(12) 176(2) 8_565 yes
OW5 H51 S  0.906(16) 2.614(18) 3.3609(8) 140.2(17) . yes
OW5 H51 O3  0.906(16) 1.728(16) 2.6237(11) 169(2) . yes
OW5 H52 F  0.891(15) 1.627(15) 2.5178(10) 177(2) . yes
OW6 H61 OW3  0.912(16) 2.000(16) 2.8961(12) 166.9(19) 3_465 yes
OW6 H61 OW4  0.912(16) 2.57(2) 3.1529(13) 121.9(15) 7_556 yes
OW6 H62 S  0.919(15) 2.854(17) 3.6778(8) 149.9(17) 8_565 yes
OW6 H62 O2  0.919(15) 1.722(15) 2.6352(11) 172(2) 8_565 yes
 
_refine_diff_density_max    0.317
_refine_diff_density_min   -0.490
_refine_diff_density_rms    0.056



