# Electronic Supplementary Material (ESI) for Dalton Transactions.
# 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_Cu4MnGe2S7
_database_code_depnum_ccdc_archive 'CCDC 2098932'
loop_
_audit_author_name
_audit_author_address
'Jennifer Aitken'
;Duquesne University
United States of America
;
_audit_update_record             
;
2021-07-23 deposited with the CCDC.	2021-11-08 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        
'tetracopper manganese digermanium heptasulfide'
_chemical_name_common            Cu4MnGe2S7
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Cu4 Ge2 Mn S7'
_chemical_formula_weight         678.70

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
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'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ge Ge 0.1547 1.8001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_H-M_alt        'C c'
_space_group_name_Hall           'C -2yc'

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

_cell_length_a                   16.7332(3)
_cell_length_b                   6.47600(10)
_cell_length_c                   9.8022(2)
_cell_angle_alpha                90
_cell_angle_beta                 93.1517(9)
_cell_angle_gamma                90
_cell_volume                     1060.60(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    4243
_cell_measurement_theta_min      2.4375
_cell_measurement_theta_max      32.791

_exptl_crystal_description       'irregular polyhedron'
_exptl_crystal_colour            black
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    4.250
_exptl_crystal_F_000             1268
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.180
_exptl_crystal_size_mid          0.135
_exptl_crystal_size_min          0.102
_exptl_absorpt_coefficient_mu    15.925
_shelx_estimated_absorpt_T_min   0.162
_shelx_estimated_absorpt_T_max   0.293
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.2800
_exptl_absorpt_correction_T_max  0.4352
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2002)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker SMART ApexII'
_diffrn_measurement_method       'φ and ω Scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            4396
_diffrn_reflns_av_unetI/netI     0.0392
_diffrn_reflns_av_R_equivalents  0.0154
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         2.438
_diffrn_reflns_theta_max         27.474
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_point_group_measured_fraction_full 0.986
_reflns_number_total             2405
_reflns_number_gt                2282
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.965
_reflns_Friedel_fraction_max     0.968
_reflns_Friedel_fraction_full    0.972

_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. Completness statistics refer to single and
 composite reflections containing twin component 1 only.
;

_computing_data_collection       'SMART (Bruker, 2001)'
_computing_cell_refinement       'SAINT (Bruker, 2001)'
_computing_data_reduction        'SAINT (Bruker, 2001)'
_computing_structure_solution    'SHELXS-2018/3 (Sheldrick, 2018)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    'ShelXle (Huschle 2011)'
_computing_publication_material  'publCIF (Westrip, 2010)'
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     'w=1/[σ²(Fo²)] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   .
_refine_ls_hydrogen_treatment    undef
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_extinction_coef       0.00567(18)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.063(12)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         2405
_refine_ls_number_parameters     129
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0223
_refine_ls_R_factor_gt           0.0210
_refine_ls_wR_factor_ref         0.0551
_refine_ls_wR_factor_gt          0.0521
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_restrained_S_all      1.067
_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_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
Cu1 Cu -0.00193(6) 0.18000(17) -0.00131(13) 0.0196(3) Uani 1 1 d . . . . .
Cu2 Cu 0.06549(5) 0.3393(2) 0.36035(14) 0.0190(2) Uani 1 1 d . . . . .
Cu3 Cu 0.21237(5) 0.3196(2) 0.07988(12) 0.0197(3) Uani 1 1 d . . . . .
Cu4 Cu 0.35325(4) 0.67831(12) 0.28351(9) 0.0186(3) Uani 1 1 d . . . . .
Mn Mn 0.28394(8) 0.15156(18) 0.43729(12) 0.0143(2) Uani 1 1 d . . . . .
Ge1 Ge 0.42802(3) 0.16344(7) 0.15672(6) 0.00867(19) Uani 1 1 d . . . . .
Ge2 Ge 0.63880(4) 0.32497(18) 0.22799(10) 0.00879(19) Uani 1 1 d . . . . .
S1 S 0.03322(11) 0.16743(19) 0.56571(13) 0.0090(3) Uani 1 1 d . . . . .
S2 S 0.17008(10) 0.15178(17) 0.27258(13) 0.0118(4) Uani 1 1 d . . . . .
S3 S 0.24068(10) 0.6649(2) 0.13736(14) 0.0120(4) Uani 1 1 d . . . . .
S4 S 0.32846(10) 0.19229(18) -0.00212(15) 0.0108(3) Uani 1 1 d . . . . .
S5 S 0.39302(10) 0.33995(19) 0.33827(13) 0.0107(3) Uani 1 1 d . . . . .
S6 S 0.46156(9) 0.16029(18) 0.69731(14) 0.0099(4) Uani 1 1 d . . . . .
S7 S 0.60848(10) 0.1666(2) 0.41601(15) 0.0106(3) Uani 1 1 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
Cu1 S7 2.2852(18) 4_454 ?
Cu1 S5 2.2969(17) 4_454 ?
Cu1 S6 2.3161(18) 4_454 ?
Cu1 S1 2.4077(14) 2_554 ?
Cu2 S7 2.2942(15) 3_455 ?
Cu2 S6 2.2963(16) 4_454 ?
Cu2 S2 2.3332(19) . ?
Cu2 S1 2.3879(17) . ?
Cu3 S4 2.2959(17) . ?
Cu3 S7 2.3029(16) 4_454 ?
Cu3 S2 2.3230(18) . ?
Cu3 S3 2.348(2) . ?
Cu4 S6 2.2933(18) 2_564 ?
Cu4 S3 2.3046(16) . ?
Cu4 S4 2.321(2) 2_565 ?
Cu4 S5 2.3437(16) . ?
Mn S4 2.4119(17) 2 ?
Mn S2 2.429(2) . ?
Mn S3 2.4371(18) 2_565 ?
Mn S5 2.441(2) . ?
Ge1 S6 2.2008(13) 2_554 ?
Ge1 S5 2.2207(14) . ?
Ge1 S4 2.2247(15) . ?
Ge1 S1 2.2949(16) 4_554 ?
Ge2 S7 2.1930(14) . ?
Ge2 S2 2.2179(15) 3 ?
Ge2 S3 2.2218(16) 3_545 ?
Ge2 S1 2.3120(15) 4_554 ?

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
S7 Cu1 S5 112.64(8) 4_454 4_454 ?
S7 Cu1 S6 111.09(5) 4_454 4_454 ?
S5 Cu1 S6 111.91(7) 4_454 4_454 ?
S7 Cu1 S1 108.24(7) 4_454 2_554 ?
S5 Cu1 S1 107.49(5) 4_454 2_554 ?
S6 Cu1 S1 105.05(8) 4_454 2_554 ?
S7 Cu2 S6 112.34(6) 3_455 4_454 ?
S7 Cu2 S2 109.68(7) 3_455 . ?
S6 Cu2 S2 107.38(8) 4_454 . ?
S7 Cu2 S1 108.22(9) 3_455 . ?
S6 Cu2 S1 112.92(7) 4_454 . ?
S2 Cu2 S1 106.09(5) . . ?
S4 Cu3 S7 112.99(9) . 4_454 ?
S4 Cu3 S2 114.71(6) . . ?
S7 Cu3 S2 109.47(7) 4_454 . ?
S4 Cu3 S3 105.22(6) . . ?
S7 Cu3 S3 105.37(7) 4_454 . ?
S2 Cu3 S3 108.48(9) . . ?
S6 Cu4 S3 115.07(6) 2_564 . ?
S6 Cu4 S4 110.68(6) 2_564 2_565 ?
S3 Cu4 S4 113.32(7) . 2_565 ?
S6 Cu4 S5 106.88(6) 2_564 . ?
S3 Cu4 S5 108.61(6) . . ?
S4 Cu4 S5 101.12(6) 2_565 . ?
S4 Mn S2 112.62(7) 2 . ?
S4 Mn S3 110.71(8) 2 2_565 ?
S2 Mn S3 106.13(7) . 2_565 ?
S4 Mn S5 109.38(7) 2 . ?
S2 Mn S5 108.17(7) . . ?
S3 Mn S5 109.75(6) 2_565 . ?
S6 Ge1 S5 114.92(6) 2_554 . ?
S6 Ge1 S4 112.35(5) 2_554 . ?
S5 Ge1 S4 107.29(6) . . ?
S6 Ge1 S1 109.36(6) 2_554 4_554 ?
S5 Ge1 S1 107.92(5) . 4_554 ?
S4 Ge1 S1 104.40(6) . 4_554 ?
S7 Ge2 S2 110.10(9) . 3 ?
S7 Ge2 S3 109.62(6) . 3_545 ?
S2 Ge2 S3 110.25(7) 3 3_545 ?
S7 Ge2 S1 112.63(8) . 4_554 ?
S2 Ge2 S1 106.16(6) 3 4_554 ?
S3 Ge2 S1 108.00(8) 3_545 4_554 ?
Ge1 S1 Ge2 107.21(6) 4_455 4_455 ?
Ge1 S1 Cu2 108.61(5) 4_455 . ?
Ge2 S1 Cu2 111.74(10) 4_455 . ?
Ge1 S1 Cu1 111.78(8) 4_455 2 ?
Ge2 S1 Cu1 111.93(6) 4_455 2 ?
Cu2 S1 Cu1 105.59(7) . 2 ?
Ge2 S2 Cu3 111.43(7) 3_445 . ?
Ge2 S2 Cu2 113.31(9) 3_445 . ?
Cu3 S2 Cu2 108.93(6) . . ?
Ge2 S2 Mn 107.37(6) 3_445 . ?
Cu3 S2 Mn 106.14(9) . . ?
Cu2 S2 Mn 109.40(7) . . ?
Ge2 S3 Cu4 110.65(7) 3_455 . ?
Ge2 S3 Cu3 113.03(9) 3_455 . ?
Cu4 S3 Cu3 109.41(5) . . ?
Ge2 S3 Mn 111.25(7) 3_455 2_564 ?
Cu4 S3 Mn 102.30(8) . 2_564 ?
Cu3 S3 Mn 109.66(7) . 2_564 ?
Ge1 S4 Cu3 113.62(7) . . ?
Ge1 S4 Cu4 119.99(8) . 2_564 ?
Cu3 S4 Cu4 112.59(6) . 2_564 ?
Ge1 S4 Mn 107.70(5) . 2_554 ?
Cu3 S4 Mn 99.32(10) . 2_554 ?
Cu4 S4 Mn 100.29(7) 2_564 2_554 ?
Ge1 S5 Cu1 107.10(8) . 4 ?
Ge1 S5 Cu4 112.44(7) . . ?
Cu1 S5 Cu4 113.98(6) 4 . ?
Ge1 S5 Mn 107.30(5) . . ?
Cu1 S5 Mn 105.10(6) 4 . ?
Cu4 S5 Mn 110.45(8) . . ?
Ge1 S6 Cu4 107.58(7) 2 2_565 ?
Ge1 S6 Cu2 107.62(6) 2 4 ?
Cu4 S6 Cu2 109.07(6) 2_565 4 ?
Ge1 S6 Cu1 110.48(7) 2 4 ?
Cu4 S6 Cu1 110.89(6) 2_565 4 ?
Cu2 S6 Cu1 111.09(8) 4 4 ?
Ge2 S7 Cu1 108.88(6) . 4 ?
Ge2 S7 Cu2 108.44(8) . 3_545 ?
Cu1 S7 Cu2 103.71(10) 4 3_545 ?
Ge2 S7 Cu3 111.55(12) . 4 ?
Cu1 S7 Cu3 109.25(7) 4 4 ?
Cu2 S7 Cu3 114.62(7) 3_545 4 ?

_refine_diff_density_max         0.695
_refine_diff_density_min         -0.891
_refine_diff_density_rms         0.181



