# Electronic Supplementary Material (ESI) for ChemComm.
# 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_sad
_database_code_depnum_ccdc_archive 'CCDC 2109340'
loop_
_audit_author_name
_audit_author_address
'Amitava Choudhury'
;Missouri University of Science and Technology
United States of America
;
_audit_update_record             
;
2021-09-13 deposited with the CCDC.	2021-11-16 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Li Mn P S4'
_chemical_formula_weight         221.09

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Li Li -0.0003 0.0001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
P P 0.1023 0.0942 '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'
Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_H-M_alt        'P n m a'
_space_group_name_Hall           '-P 2ac 2n'

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

_cell_length_a                   12.540(3)
_cell_length_b                   7.6545(16)
_cell_length_c                   5.8345(12)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     560.0(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    300(2)
_cell_measurement_reflns_used    1423
_cell_measurement_theta_min      3.25
_cell_measurement_theta_max      27.36
_exptl_crystal_description       irregular
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      none
_exptl_crystal_density_method    none
_exptl_crystal_density_diffrn    2.622
_exptl_crystal_F_000             428
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.080
_exptl_crystal_size_mid          0.050
_exptl_crystal_size_min          0.040
_exptl_absorpt_coefficient_mu    3.971
_shelx_estimated_absorpt_T_min   0.742
_shelx_estimated_absorpt_T_max   0.857
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5701
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_process_details   '(SADABS; Bruker, 2008)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      300(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            6207
_diffrn_reflns_av_unetI/netI     0.0276
_diffrn_reflns_av_R_equivalents  0.0505
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_theta_min         3.249
_diffrn_reflns_theta_max         28.275
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             735
_reflns_number_gt                643
_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       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_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)+(0.0468P)²+0.2744P] 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     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         735
_refine_ls_number_parameters     40
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0395
_refine_ls_R_factor_gt           0.0330
_refine_ls_wR_factor_ref         0.0852
_refine_ls_wR_factor_gt          0.0806
_refine_ls_goodness_of_fit_ref   1.112
_refine_ls_restrained_S_all      1.112
_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 0.000000 0.000000 0.500000 0.0251(2) Uani 1 2 d S . P . .
P1 P 0.09106(8) 0.250000 0.10640(15) 0.0134(2) Uani 1 2 d S T P . .
S1 S 0.16492(6) 0.03569(11) 0.24284(11) 0.0182(2) Uani 1 1 d . . . . .
S2 S -0.06246(8) 0.250000 0.24092(15) 0.0159(2) Uani 1 2 d S T P . .
S3 S 0.09467(8) 0.250000 -0.24201(14) 0.0168(3) Uani 1 2 d S T P . .
Li1 Li -0.2281(7) 0.250000 -0.0109(12) 0.0302(17) Uani 1 2 d S T 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 S2 2.5613(7) . ?
Mn1 S2 2.5613(7) 5_556 ?
Mn1 S1 2.5696(8) 5_556 ?
Mn1 S1 2.5696(8) . ?
Mn1 S3 2.7087(7) 5 ?
Mn1 S3 2.7087(7) 1_556 ?
P1 S3 2.0333(13) . ?
P1 S1 2.0451(10) 7_565 ?
P1 S1 2.0451(10) . ?
P1 S2 2.0791(14) . ?
S1 Li1 2.634(6) 6_656 ?
S1 Li1 2.691(5) 5 ?
S2 Li1 2.545(8) . ?
S3 Li1 2.649(8) 6_655 ?

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
S2 Mn1 S2 180.0 . 5_556 ?
S2 Mn1 S1 100.25(3) . 5_556 ?
S2 Mn1 S1 79.75(3) 5_556 5_556 ?
S2 Mn1 S1 79.75(3) . . ?
S2 Mn1 S1 100.25(3) 5_556 . ?
S1 Mn1 S1 180.0 5_556 . ?
S2 Mn1 S3 93.78(3) . 5 ?
S2 Mn1 S3 86.22(3) 5_556 5 ?
S1 Mn1 S3 84.07(3) 5_556 5 ?
S1 Mn1 S3 95.93(3) . 5 ?
S2 Mn1 S3 86.22(3) . 1_556 ?
S2 Mn1 S3 93.78(3) 5_556 1_556 ?
S1 Mn1 S3 95.93(3) 5_556 1_556 ?
S1 Mn1 S3 84.07(3) . 1_556 ?
S3 Mn1 S3 180.00(3) 5 1_556 ?
S3 P1 S1 112.28(4) . 7_565 ?
S3 P1 S1 112.28(4) . . ?
S1 P1 S1 106.66(6) 7_565 . ?
S3 P1 S2 113.45(6) . . ?
S1 P1 S2 105.81(4) 7_565 . ?
S1 P1 S2 105.81(4) . . ?
P1 S1 Mn1 87.03(4) . . ?
P1 S1 Li1 87.83(12) . 6_656 ?
Mn1 S1 Li1 97.43(17) . 6_656 ?
P1 S1 Li1 126.12(15) . 5 ?
Mn1 S1 Li1 116.38(16) . 5 ?
Li1 S1 Li1 130.90(4) 6_656 5 ?
P1 S2 Li1 122.55(18) . . ?
P1 S2 Mn1 86.54(3) . 3_556 ?
Li1 S2 Mn1 126.19(7) . 3_556 ?
P1 S2 Mn1 86.54(3) . . ?
Li1 S2 Mn1 126.19(7) . . ?
Mn1 S2 Mn1 96.68(3) 3_556 . ?
P1 S3 Li1 124.25(18) . 6_655 ?
P1 S3 Mn1 123.08(3) . 1_554 ?
Li1 S3 Mn1 93.74(12) 6_655 1_554 ?
P1 S3 Mn1 123.08(3) . 3 ?
Li1 S3 Mn1 93.74(12) 6_655 3 ?
Mn1 S3 Mn1 89.90(3) 1_554 3 ?
S2 Li1 S1 94.2(2) . 4_455 ?
S2 Li1 S1 94.2(2) . 6_556 ?
S1 Li1 S1 77.0(2) 4_455 6_556 ?
S2 Li1 S3 177.7(3) . 6 ?
S1 Li1 S3 84.0(2) 4_455 6 ?
S1 Li1 S3 84.0(2) 6_556 6 ?
S2 Li1 S1 92.9(2) . 5 ?
S1 Li1 S1 162.7(3) 4_455 5 ?
S1 Li1 S1 86.70(4) 6_556 5 ?
S3 Li1 S1 88.48(18) 6 5 ?
S2 Li1 S1 92.9(2) . 3 ?
S1 Li1 S1 86.70(4) 4_455 3 ?
S1 Li1 S1 162.7(3) 6_556 3 ?
S3 Li1 S1 88.48(18) 6 3 ?
S1 Li1 S1 108.7(3) 5 3 ?

_refine_diff_density_max         0.895
_refine_diff_density_min         -0.699
_refine_diff_density_rms         0.181



