Quaternary Charge-Transfer Solid Solutions: Electronic Tunability through Stoichiometry
Wiscons, Ren A.; Coropceanu, Veaceslav; Matzger, Adam J.; Chemistry of Materials 31 (2019) 6598–; doi:10.1021/acs.chemmater.9b00502

data_4002975
_publ_section_title
;
 Quaternary Charge-Transfer Solid Solutions: Electronic Tunability through
 Stoichiometry
;
_journal_issue                   17
_journal_name_full               'Chemistry of Materials'
_journal_page_first              6598
_journal_paper_doi               10.1021/acs.chemmater.9b00502
_journal_volume                  31
_journal_year                    2019
_chemical_formula_moiety         'Br2 C8 N2 O2, 0.5(C28 H24 S2)'
_chemical_formula_sum            'C22 H12 Br2 N2 O2 S'
_chemical_formula_weight         528.22
_chemical_name_systematic
'2,3-dibromo-5,6-dicyanobenzoquinone 4,6-dimethyldibenzothiophene'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           36
_space_group_name_Hall           'C 2c -2'
_space_group_name_H-M_alt        'C m c 21'
_symmetry_space_group_name_Hall  'C 2c -2'
_symmetry_space_group_name_H-M   'C m c 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-03-04
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.01.05 svn.r3372 for Rigaku Oxford Diffraction, GUI svn.r5289)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.60920(10)
_cell_length_b                   18.3407(2)
_cell_length_c                   16.82770(10)
_cell_measurement_reflns_used    10014
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      76.8390
_cell_measurement_theta_min      4.8110
_cell_volume                     2039.81(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (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_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -24.00  80.00   0.50    0.13    --   47.95 -96.00  48.00  208
  2  \w     95.00 178.00   0.50    0.50    --  107.75  27.00   3.00  166
  3  \w     36.00 109.00   0.50    0.50    --  107.75 -96.00  48.00  146
  4  \w     36.00 125.00   0.50    0.50    --  107.75-134.00 -20.00  178
  5  \w   -120.00 -70.00   0.50    0.13    --  -47.95-125.00 -90.00  100
  6  \w    -25.00  60.00   0.50    0.13    --   47.95 -37.00  30.00  170
  7  \w     33.00 119.00   0.50    0.13    --   47.95  57.00 150.00  172
  8  \w    -97.00  -9.00   0.50    0.50    --  -84.50  27.00   3.00  176
  9  \w     33.00 121.00   0.50    0.50    --  107.75 -30.00 -60.00  176
 10  \w     35.00 121.00   0.50    0.50    --  107.75-125.00-120.00  172
 11  \w     36.00 121.00   0.50    0.50    --  107.75 -45.00  30.00  170
 12  \w     36.00 108.00   0.50    0.50    --  107.75 -94.00 120.00  144
 13  \w     85.00 178.00   0.50    0.50    --  107.75  77.00 -60.00  186
 14  \w     95.00 178.00   0.50    0.50    --  107.75  30.00 -60.00  166
 15  \w     33.00 122.00   0.50    0.50    --  107.75 -15.00   0.00  178
 16  \w     36.00 108.00   0.50    0.50    --  107.75 -94.00 -30.00  144
 17  \w     36.00 108.00   0.50    0.50    --  107.75 -94.00-180.00  144
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0165167000
_diffrn_orient_matrix_UB_12      0.0817491000
_diffrn_orient_matrix_UB_13      -0.0199896000
_diffrn_orient_matrix_UB_21      0.0799606000
_diffrn_orient_matrix_UB_22      0.0192432000
_diffrn_orient_matrix_UB_23      0.0833890000
_diffrn_orient_matrix_UB_31      0.2183586000
_diffrn_orient_matrix_UB_32      -0.0008670000
_diffrn_orient_matrix_UB_33      -0.0320529000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0307
_diffrn_reflns_av_unetI/netI     0.0185
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            9259
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        66.503
_diffrn_reflns_theta_max         66.503
_diffrn_reflns_theta_min         4.822
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.179
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51100
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark violet'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.720
_exptl_crystal_description       block
_exptl_crystal_F_000             1040
_exptl_crystal_preparation       'solvent evaporation'
_exptl_crystal_size_max          0.542
_exptl_crystal_size_mid          0.183
_exptl_crystal_size_min          0.161
_refine_diff_density_max         0.455
_refine_diff_density_min         -0.471
_refine_diff_density_rms         0.155
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   -0.01(4)
_refine_ls_extinction_coef       0.0028(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     178
_refine_ls_number_reflns         1951
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0374
_refine_ls_R_factor_gt           0.0349
_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^)+(0.0720P)^2^+0.9702P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0819
_refine_ls_wR_factor_ref         0.0899
_reflns_Friedel_coverage         0.911
_reflns_Friedel_fraction_full    0.981
_reflns_Friedel_fraction_max     0.981
_reflns_number_gt                1923
_reflns_number_total             1951
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm9b00502_si_005.cif
_cod_data_source_block           exp_10
_cod_database_code               4002975
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C H S Br O N'
_diffrn_oxdiff_ac3_digest_frames
;
01376a5e008902ea145c727bae774fc86800110e5f2
;
_diffrn_oxdiff_ac3_digest_hkl
;
0102279dec5944fb7892b20c72bfe6eed81904
;
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: H22A(0.5) H22B(0.5) H22C(0.5) H21A(0.5) H21B(0.5) H21C(0.5)
3.a Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C18(H18), C17(H17), C11(H11), C16(H16)
3.b Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C21(H21A,H21B,H21C)
;
_olex2_exptl_crystal_mounting_method MiTGen
_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 1.426
_oxdiff_exptl_absorpt_empirical_full_min 0.614