Controllable Direct Arylation: Fast Route to Symmetrical and Unsymmetrical 4,7-Diaryl-5,6-difluoro-2,1,3-benzothiadiazole Derivatives for Organic Optoelectronic Materials
Junxiang Zhang; Wayne Chen; Anthony J. Rojas; Evgheni V. Jucov; Tatiana V. Timofeeva; Timothy C. Parker; Stephen Barlow; Seth R. Marder; Journal of the American Chemical Society 135 (2013) 16376–16379; doi:10.1021/ja4095878

data_4121100
_publ_contact_author_name
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_publ_section_title
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 Controllable Direct Arylation: Fast Route to Symmetrical and
 Unsymmetrical 4,7-Diaryl-5,6-difluoro-2,1,3-benzothiadiazole Derivatives
 for Organic Optoelectronic Materials
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_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16376
_journal_page_last               16379
_journal_paper_doi               10.1021/ja4095878
_journal_volume                  135
_journal_year                    2013
_chemical_formula_moiety         'C20 H22 F2 N2 S3 Si2'
_chemical_formula_sum            'C20 H22 F2 N2 S3 Si2'
_chemical_formula_weight         480.76
_chemical_name_systematic
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 ? 
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_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-03-21
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:17:34, GUI svn.r4385)
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_cell_angle_alpha                90.00
_cell_angle_beta                 91.104(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   6.1739(9)
_cell_length_b                   10.7483(15)
_cell_length_c                   33.914(5)
_cell_measurement_reflns_used    9037
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.59
_cell_measurement_theta_min      2.40
_cell_volume                     2250.1(6)
_computing_molecular_graphics
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O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
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_computing_publication_material
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O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0172
_diffrn_reflns_av_unetI/netI     0.0120
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            20708
_diffrn_reflns_theta_full        26.00
_diffrn_reflns_theta_max         26.00
_diffrn_reflns_theta_min         1.99
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.463
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6400
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1372 before and 0.0371 after correction.
The Ratio of minimum to maximum transmission is 0.8578.
The \l/2 correction factor is 0.0015.
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_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.419
_exptl_crystal_description       plate
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.528
_refine_diff_density_min         -0.523
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.199
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     290
_refine_ls_number_reflns         4413
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.199
_refine_ls_R_factor_all          0.0566
_refine_ls_R_factor_gt           0.0555
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0616P)^2^+5.1829P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1598
_refine_ls_wR_factor_ref         0.1610
_reflns_number_gt                4253
_reflns_number_total             4413
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja4095878_si_002.cif
_cod_data_source_block           3n
_cod_database_code               4121100
_olex2_refinement_description
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1. Fixed Uiso
 At 1.2 times of:
  H5 of C5, H6 of C6, H15 of C15, H16 of C16
 At 1.5 times of:
  {H1A,H1B,H1C} of C1, {H2A,H2B,H2C} of C2, {H3A,H3B,H3C} of C3, {H18A,H18B,
  H18C} of C18, {H19A,H19B,H19C} of C19, {H20A,H20B,H20C} of C20
2. Uiso/Uaniso restraints and constraints
Uanis(N2) = Uanis(N2A)
Uanis(N1) = Uanis(N1A)
Uanis(F1) = Uanis(F1A)
Uanis(F2) = Uanis(F2A)
3. others
 Sof(S3)=Sof(F1)=Sof(F2)=Sof(N1)=Sof(N2)=1-Sof(F1)=1-Sof(F1)=1-Sof(F1)=1-
 Sof(F1)=1-Sof(F1)
4.a Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C15(H15), C16(H16)
4.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
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