Cu4MnGe2S7 and Cu2MnGeS4: two polar thiogermanates exhibiting second harmonic generation in the infrared and structures derived from hexagonal diamond
Glenn, Jennifer R.; Cho, Jeong Bin; Wang, Yiqun; Craig, Andrew J.; Zhang, Jian-Han; Cribbs, Marvene; Stoyko, Stanislav S.; Rosello, Kate E.; Barton, Christopher; Bonnoni, Allyson; Grima-Gallardo, Pedro; MacNeil, Joseph H.; Rondinelli, James M.; Jang, Joon I.; Aitken, Jennifer A.; Dalton Transactions  (2021) –; doi:10.1039/D1DT02535J

data_7708895
_publ_section_title
;
 Cu4MnGe2S7 and Cu2MnGeS4: two polar thiogermanates exhibiting second
 harmonic generation in the infrared and structures derived from hexagonal
 diamond
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT02535J
_journal_year                    2021
_chemical_formula_sum            'Cu4 Ge2 Mn S7'
_chemical_formula_weight         678.70
_chemical_name_common            Cu4MnGe2S7
_chemical_name_systematic
'tetracopper manganese digermanium heptasulfide'
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2018/3
_audit_update_record
;
2021-07-23 deposited with the CCDC.	2021-11-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.1517(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.7332(3)
_cell_length_b                   6.47600(10)
_cell_length_c                   9.8022(2)
_cell_measurement_reflns_used    4243
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      32.791
_cell_measurement_theta_min      2.4375
_cell_volume                     1060.60(3)
_computing_cell_refinement       'SAINT (Bruker, 2001)'
_computing_data_collection       'SMART (Bruker, 2001)'
_computing_data_reduction        'SAINT (Bruker, 2001)'
_computing_molecular_graphics    'ShelXle (Huschle 2011)'
_computing_publication_material  'publCIF (Westrip, 2010)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXS-2018/3 (Sheldrick, 2018)'
_diffrn_ambient_temperature      296(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker SMART ApexII'
_diffrn_measurement_method       '\f and \w Scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0154
_diffrn_reflns_av_unetI/netI     0.0392
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            4396
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.474
_diffrn_reflns_theta_min         2.438
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    15.925
_exptl_absorpt_correction_T_max  0.4352
_exptl_absorpt_correction_T_min  0.2800
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2002)'
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    4.250
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       'irregular polyhedron'
_exptl_crystal_F_000             1268
_exptl_crystal_size_max          0.180
_exptl_crystal_size_mid          0.135
_exptl_crystal_size_min          0.102
_refine_diff_density_max         0.695
_refine_diff_density_min         -0.891
_refine_diff_density_rms         0.181
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.063(12)
_refine_ls_extinction_coef       0.00567(18)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     129
_refine_ls_number_reflns         2405
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0223
_refine_ls_R_factor_gt           0.0210
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     'w=1/[\s^2^(Fo^2^)] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0521
_refine_ls_wR_factor_ref         0.0551
_reflns_Friedel_coverage         0.965
_reflns_Friedel_fraction_full    0.972
_reflns_Friedel_fraction_max     0.968
_reflns_number_gt                2282
_reflns_number_total             2405
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt02535j2.cif
_cod_data_source_block           Cu4MnGe2S7
_cod_original_sg_symbol_H-M      'C c'
_cod_database_code               7708895
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.162
_shelx_estimated_absorpt_t_max   0.293
_shelx_res_checksum              64802
_shelx_hkl_checksum              44534