Manganese(II) in Tetrahedral Halide Environment: Factors Governing Bright Green Luminescence
Morad, Viktoriia; Cherniukh, Ihor; Pöttschacher, Lena; Shynkarenko, Yevhen; Yakunin, Sergii; Kovalenko, Maksym V.; Chemistry of Materials  (2019) –; doi:10.1021/acs.chemmater.9b03782

data_4003435
_publ_section_title
;
 Manganese(II) in Tetrahedral Halide Environment: Factors Governing Bright
 Green Luminescence
;
_journal_name_full               'Chemistry of Materials'
_journal_paper_doi               10.1021/acs.chemmater.9b03782
_journal_year                    2019
_chemical_formula_moiety         'Cl4 Mn, 2(C10 H16 N)'
_chemical_formula_sum            'C20 H32 Cl4 Mn N2'
_chemical_formula_weight         497.21
_chemical_name_systematic
'N-benzyl-N,N,N-trimethylammonium tetrachloromanganate(II)'
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-06-24 deposited with the CCDC.	2019-08-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.006(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.5066(2)
_cell_length_b                   8.9878(2)
_cell_length_c                   29.1439(7)
_cell_measurement_reflns_used    12871
_cell_measurement_temperature    130.01(10)
_cell_measurement_theta_max      32.3000
_cell_measurement_theta_min      2.2370
_cell_volume                     2489.77(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28c (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28c (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28c (Rigaku OD, 2015)'
_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      130.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0839
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.947
_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    -43.00  33.00   1.00   16.59    --   25.62 -57.00-180.00   76
  2  \w      7.00  94.00   1.00   16.59    --   25.62  57.00 -30.00   87
  3  \w     34.00 100.00   1.00   16.59    --   25.62 179.00  90.00   66
  4  \w      5.00  96.00   1.00   16.59    --   25.62  38.00 -60.00   91
  5  \w      1.00  83.00   1.00   16.59    --   25.62-129.00 153.00   82
  6  \w      0.00  92.00   1.00   16.59    --   25.62  77.00  30.00   92
  7  \w     35.00  86.00   1.00   16.59    --   25.62 179.00 150.00   51
  8  \w     57.00  91.00   1.00   16.59    --   25.62-142.00 -17.00   34
  9  \w      7.00  94.00   1.00   16.59    --   25.62  57.00 150.00   87
 10  \w    -45.00  43.00   1.00   16.59    --   25.62 -38.00-120.00   88
 11  \w     -1.00  92.00   1.00   16.59    --   25.62  77.00-180.00   93
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0115122000
_diffrn_orient_matrix_UB_12      -0.0062464000
_diffrn_orient_matrix_UB_13      0.0239072000
_diffrn_orient_matrix_UB_21      0.0725306000
_diffrn_orient_matrix_UB_22      0.0132385000
_diffrn_orient_matrix_UB_23      0.0044424000
_diffrn_orient_matrix_UB_31      -0.0132967000
_diffrn_orient_matrix_UB_32      0.0775426000
_diffrn_orient_matrix_UB_33      0.0011698000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0515
_diffrn_reflns_av_unetI/netI     0.0537
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.947
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            54879
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.916
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.647
_diffrn_reflns_theta_min         2.097
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.209
_exptl_absorpt_correction_T_max  0.93985
_exptl_absorpt_correction_T_min  0.93985
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28c (Rigaku Oxford Diffraction, 2015)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.658
_exptl_crystal_description       plate
_exptl_crystal_F_000             1295
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method 'from acid'
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.05
_refine_diff_density_max         4.263
_refine_diff_density_min         -2.377
_refine_diff_density_rms         0.177
_refine_ls_abs_structure_details
;
 Flack x determined using 5302 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.41(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     500
_refine_ls_number_reflns         16722
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.1125
_refine_ls_R_factor_gt           0.1030
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1063P)^2^+22.4048P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2698
_refine_ls_wR_factor_ref         0.2797
_reflns_Friedel_coverage         0.834
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.882
_reflns_number_gt                15020
_reflns_number_total             16722
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm9b03782_si_002.cif
_cod_data_source_block           1
_cod_depositor_comments
;

2020-10-16
Z value fixed to be consistent with given formula 
                 miguel
;
_cod_original_formula_moiety         '0.8(Cl4 Mn), 1.6(C10 H16 N)'
_cod_original_formula_units_Z            5
_cod_database_code               4003435
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H32 N2 Mn Cl4'
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.94168
 0.05832
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H00Z,H,HA} of C00G, All C(H,H) groups
 At 1.5 times of:
  {H00A,H00C,H00D} of C00H, {H00P,H00Q,H00U} of C00U, {H00G,H00H,H00I} of
  C00Z, {H01J,H01K,H01L} of C015, {H01D,H01E,H01F} of C014, {H01G,H01H,H01I} of
  C016, {H01A,H01B,H01C} of C013, {H01U,H01V,H01W} of C018, {H01M,H01N,H01O} of
  C01A, {H1AA,HB,HC} of C01H, {H01P,H01Q,H01R} of C01B
3.a Secondary CH2 refined with riding coordinates:
 C00P(H00J,H00M), C00Q(H00E,H00F), C00X(H00X,H00Y), C01C(H01X,H01Y)
3.b Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00K(H00K), C00L(H00L), C00M(H00V), C00N(H00N), C00O(H00O),
 C00R(H00R), C00S(H00S), C00T(H00T), C00V(H00W), C00W(H00), C010(H010),
 C011(H011), C012(H012), C019(H019), C01D(H01S), C01E(H01Z), C01F(H01),
 C01G(H0AA), C01I(H01T)
3.c Idealised Me refined as rotating group:
 C00G(H00Z,H,HA), C00H(H00A,H00C,H00D), C00U(H00P,H00Q,H00U), C00Z(H00G,H00H,
 H00I), C013(H01A,H01B,H01C), C014(H01D,H01E,H01F), C015(H01J,H01K,H01L),
 C016(H01G,H01H,H01I), C018(H01U,H01V,H01W), C01A(H01M,H01N,H01O), C01B(H01P,
 H01Q,H01R), C01H(H1AA,HB,HC)
;
_shelx_res_checksum              23453
_shelx_hkl_checksum              38965
_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 1.287
_oxdiff_exptl_absorpt_empirical_full_min 0.724