Structural Investigations of α-MnS Nanocrystals and Thin Films Synthesized from Manganese(II) Xanthates by Hot Injection, Solvent-Less Thermolysis, and Doctor Blade Routes.
Alanazi, Abdulaziz M.; McNaughter, Paul D.; Alam, Firoz; Vitorica-Yrezabal, Inigo J; Whitehead, George F. S.; Tuna, Floriana; O'Brien, Paul; Collison, David; Lewis, David J.; ACS omega 6 (2021) 27716–27725; doi:10.1021/acsomega.1c02907

data_4519114
_publ_section_title
;
 Structural Investigations of \a-MnS Nanocrystals and Thin Films
 Synthesized from Manganese(II) Xanthates by Hot Injection, Solvent-Less
 Thermolysis, and Doctor Blade Routes.
;
_journal_issue                   42
_journal_name_full               'ACS omega'
_journal_page_first              27716
_journal_page_last               27725
_journal_paper_doi               10.1021/acsomega.1c02907
_journal_volume                  6
_journal_year                    2021
_chemical_formula_moiety         'C20 H42 Mn N2 O2 S4'
_chemical_formula_sum            'C20 H42 Mn N2 O2 S4'
_chemical_formula_weight         525.73
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-09-18
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 108.507(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.6601(3)
_cell_length_b                   8.15454(13)
_cell_length_c                   23.5223(5)
_cell_measurement_reflns_used    13369
_cell_measurement_temperature    240.00(10)
_cell_measurement_theta_max      67.7170
_cell_measurement_theta_min      3.9580
_cell_volume                     2848.48(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.30c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.30c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.30c (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      240.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -81.00   8.00   1.00    1.00    --    5.00 -76.00-120.00   89
  2  \w     16.00  92.00   1.00    1.00    --    5.00  57.00-150.00   76
  3  \w    -69.00  38.00   1.00    1.00    --    5.00 -57.00  90.00  107
  4  \w     15.00  45.00   1.00    1.00    --    5.00 -76.00-120.00   30
  5  \w   -116.00 -90.00   1.00    1.00    --  -30.00 -54.00 -44.14   26
  6  \w    -42.00  -6.00   1.00    1.00    --  -30.00 -54.00 -44.14   36
  7  \w    -77.00  26.00   1.00    1.00    --  -45.10  57.00   0.00  103
  8  \w   -144.00-119.00   1.00    1.00    --  -62.00 -73.00 -25.47   25
  9  \w    -53.00 -24.00   1.00    1.00    --  -62.00 -73.00 -25.47   29
 10  \w   -133.00-107.00   1.00    1.00    --  -66.00 -75.00 137.01   26
 11  \w    -54.00 -26.00   1.00    1.00    --  -66.00 -76.00 -86.86   28
 12  \w   -146.00-120.00   1.00    1.00    --  -66.00 -76.00 -86.86   26
 13  \w    -51.00 -26.00   1.00    1.00    --  -66.00 -76.00 160.52   25
 14  \w    -75.00 -26.00   1.00    1.00    --  -66.00 -76.00-139.20   49
 15  \w    -53.00 -28.00   1.00    1.00    --  -66.00 -75.00 137.01   25
 16  \w   -152.00-126.00   1.00    1.00    --  -66.00 -71.00  83.24   26
 17  \w    -59.00 -29.00   1.00    1.00    --  -66.00 -71.00  83.24   30
 18  \w   -128.00-103.00   1.00    1.00    --  -66.00 -76.00 160.52   25
 19  \w   -109.00 -31.00   1.00    1.00    --  -70.00 -74.00  62.05   78
 20  \w    -64.00 -32.00   1.00    1.00    --  -70.00 -74.00 -30.47   32
 21  \w    -80.00 -34.00   1.00    1.00    --  -74.00 -76.00  25.46   46
 22  \w   -162.00-113.00   1.00    1.00    --  -74.00 -76.00  25.46   49
 23  \w    -71.00 -43.00   1.00    1.00    --  -78.00 -73.00 145.04   28
 24  \w    -76.00 -45.00   1.00    1.00    --  -82.00 -71.00 -12.85   31
 25  \w    -74.00 -42.00   1.00    1.00    --  -82.00 -76.00-126.69   32
 26  \w    -73.00 -48.00   1.00    1.00    --  -86.00 -73.00 -36.01   25
 27  \w    -76.00 -50.00   1.00    1.00    --  -90.00 -76.00 -48.51   26
 28  \w   -108.00 -54.00   1.00    1.00    --  -90.00 -71.00 -77.56   54
 29  \w    -81.00 -51.00   1.00    1.00    --  -90.00 -75.00-175.57   30
 30  \w   -177.00-100.00   1.00    1.00    --  -90.00 -76.00 -48.51   77
 31  \w   -135.00-107.00   1.00    1.00    --  -90.00 -75.00-175.57   28
 32  \w   -159.00-124.00   1.00    1.00    --  -94.00 -73.00-123.94   35
 33  \w    -89.00 -56.00   1.00    1.00    --  -94.00 -75.00 169.18   33
 34  \w   -141.00-115.00   1.00    1.00    --  -94.00 -75.00 169.18   26
 35  \w    -82.00 -55.00   1.00    1.00    --  -94.00 -76.00  -6.53   27
 36  \w   -130.00-104.00   1.00    1.00    --  -94.00 -76.00  -6.53   26
 37  \w    -94.00 -54.00   1.00    1.00    --  -94.00 -76.00  40.30   40
 38  \w    -89.00 -58.00   1.00    1.00    --  -94.00 -73.00-123.94   31
 39  \w   -181.00 -99.00   1.00    1.00    --  -94.00 -76.00  40.30   82
 40  \w    -81.00 -54.00   1.00    1.00    --  -94.00 -76.00 128.89   27
 41  \w   -175.00-127.00   1.00    1.00    --  -94.00 -76.00 128.89   48
 42  \w    -92.00 -59.00   1.00    1.00    --  -98.00 -74.00 -82.40   33
 43  \w   -184.00-102.00   1.00    1.00    --  -98.00 -74.00 -82.40   82
 44  \w   -185.00 -58.00   1.00    1.00    --  -98.00 -76.00-130.65  127
 45  \w   -186.00 -60.00   1.00    1.00    --  -98.00 -73.00  89.50  126
 46  \w   -170.00 -62.00   1.00    1.00    --  -98.00 -68.00-160.37  108
 47  \w   -191.00 -64.00   1.00    1.00    -- -102.00 -72.00 149.92  127
 48  \w   -120.00 -67.00   1.00    1.00    -- -107.20  76.00-150.00   53
 49  \w   -163.00 -69.00   1.00    1.00    -- -107.20 -72.00 -48.19   94
 50  \w   -123.00 -18.00   1.00    1.00    -- -107.20  76.00 -30.00  105
 51  \w   -154.00 -67.00   1.00    1.00    -- -107.20 -76.00  74.36   87
 52  \w   -194.00 -69.00   1.00    1.00    -- -107.20 -73.00 -23.05  125
 53  \w   -196.00-157.00   1.00    1.00    -- -107.20 -76.00  74.36   39
 54  \w   -159.00 -69.00   1.00    1.00    -- -107.20 -76.00 -90.00   90
 55  \w   -196.00-170.00   1.00    1.00    -- -107.20 -76.00 -90.00   26
 56  \w   -128.00 -49.00   1.00    1.00    -- -107.20  76.00 120.00   79
 57  \w   -197.00 -73.00   1.00    1.00    -- -107.20 -76.00  30.00  124
 58  \w   -154.00 -69.00   1.00    1.00    -- -107.20 -73.00 127.98   85
 59  \w   -196.00-171.00   1.00    1.00    -- -107.20 -73.00 127.98   25
 60  \w   -133.00 -58.00   1.00    1.00    -- -107.20  76.00  60.00   75
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0765049000
_diffrn_orient_matrix_UB_12      0.0805939000
_diffrn_orient_matrix_UB_13      -0.0180842000
_diffrn_orient_matrix_UB_21      -0.0685411000
_diffrn_orient_matrix_UB_22      0.0561302000
_diffrn_orient_matrix_UB_23      -0.0596553000
_diffrn_orient_matrix_UB_31      -0.0143954000
_diffrn_orient_matrix_UB_32      0.1614032000
_diffrn_orient_matrix_UB_33      0.0297705000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0415
_diffrn_reflns_av_unetI/netI     0.0182
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            29808
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.212
_diffrn_reflns_theta_min         5.777
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.636
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44512
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.30c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.226
_exptl_crystal_description       plate
_exptl_crystal_F_000             1124
_exptl_crystal_size_max          0.455
_exptl_crystal_size_mid          0.312
_exptl_crystal_size_min          0.021
_refine_diff_density_max         1.336
_refine_diff_density_min         -0.452
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.099
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     191
_refine_ls_number_reflns         2598
_refine_ls_number_restraints     264
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0709
_refine_ls_R_factor_gt           0.0679
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0850P)^2^+7.2721P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1796
_refine_ls_wR_factor_ref         0.1825
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2422
_reflns_number_total             2598
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ao1c02907_si_006.cif
_cod_data_source_block           s4957r
_cod_database_code               4519114
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_usercomment     MG
_shelx_estimated_absorpt_t_max   0.873
_shelx_estimated_absorpt_t_min   0.152
_reflns_odcompleteness_completeness 99.61
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C7A-C6A = C7-C6 = C5A-C6A = C6-C5 = C5A-C4A = C4-C5 = C4A-C3A = C4-C3 = C3-C2
 = C3A-C2A
 1.54 with sigma of 0.01
 C7-C5 \\sim C6-C4
 with sigma of 0.02
 C7A-C5A \\sim C6A-C4A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O1 \\sim C2A \\sim C5 \\sim C6A \\sim C7A \\sim C3A \\sim C4A \\sim C2 \\sim C3
\\sim C4 \\sim C5A \\sim C6 \\sim C7: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 O1, C2A, C5, C6A, C7A, C3A, C4A, C2, C3, C4, C5A, C6, C7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1, C1, S2, O1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(C7A)=Sof(H7AA)=
 Sof(H7AB)=Sof(H7AC)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=
 Sof(C5A)=Sof(H5AA)=Sof(H5AB)=1-FVAR(1)
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(H3A)=Sof(H3B)=
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C7)=Sof(H7A)=Sof(H7B)=
 Sof(H7C)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C2A(H2AA,H2AB), C5(H5A,H5B), C6A(H6AA,H6AB), C10(H10A,H10B), C3A(H3AA,H3AB),
 C4A(H4AA,H4AB), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5A(H5AA,H5AB), C6(H6A,
 H6B)
6.b Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C8(H8A,H8B,H8C), C7A(H7AA,H7AB,H7AC), C7(H7A,H7B,H7C)
;
_shelx_res_checksum              31767
_shelx_hkl_checksum              40614
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.836
_oxdiff_exptl_absorpt_empirical_full_min 0.610