Regiocontrolled Dimerization of Asymmetric Diazaheptacene Derivatives Toward X-shaped Porous Semiconductors
Zhang , Guowei; Zhang, Lei; Lv, Aifeng; Yang, Xingzhou; Zheng, Yonghao; Gu, Wen; Xue, Ning; Chemical Science  (2020) –; doi:10.1039/D0SC03744C

data_1559104
_publ_section_title
;
 Regiocontrolled Dimerization of Asymmetric Diazaheptacene Derivatives
 Toward X-shaped Porous Semiconductors
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC03744C
_journal_year                    2020
_chemical_formula_moiety         'C140 H160 Br4 F8 N8 O8 Si4, 2(C7 H8)'
_chemical_formula_sum            'C154 H176 Br4 F8 N8 O8 Si4'
_chemical_formula_weight         2851.02
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-06-29 deposited with the CCDC.	2020-09-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 120.504(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.370(2)
_cell_length_b                   26.4347(10)
_cell_length_c                   24.2245(19)
_cell_measurement_reflns_used    13901
_cell_measurement_temperature    169.99(13)
_cell_measurement_theta_max      72.4960
_cell_measurement_theta_min      2.5610
_cell_volume                     14549(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.14e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.14e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.14e (Rigaku OD, 2018)'
_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      169.99(13)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.949
_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     -7.00  18.00   0.50    2.00    --   46.95 -34.00  52.00   50
  2  \w     65.00 116.00   0.50   19.00    --  103.25 -34.00  52.00  102
  3  \w     79.00 109.00   0.50   19.00    --  103.25 -94.00   0.00   60
  4  \w     79.00 106.00   0.50   19.00    --  103.25 -61.00 -60.00   54
  5  \w     90.00 151.00   0.50   19.00    --  103.25  34.00-150.00  122
  6  \w    144.00 169.00   0.50   19.00    --  103.25 125.00 -90.00   50
  7  \w     91.00 158.00   0.50   19.00    --  103.25  30.00-120.00  134
  8  \w     86.00 113.00   0.50   19.00    --  103.25 125.00 -90.00   54
  9  \w     35.00 116.00   0.50    2.00    --   46.95  34.00-150.00  162
 10  \w     43.00 116.00   0.50   19.00    --  103.25 -45.00-180.00  146
 11  \w     56.00 109.00   0.50   19.00    --  103.25 -94.00-180.00  106
 12  \w     31.00  96.00   0.50   19.00    --  103.25 -94.00-120.00  130
 13  \w     32.00 117.00   0.50   19.00    --  103.25-125.00  30.00  170
 14  \w     58.00 109.00   0.50   19.00    --  103.25 -94.00 120.00  102
 15  \w     31.00  99.00   0.50   19.00    --  103.25 -94.00  90.00  136
 16  \w    -17.00  74.00   0.50    2.00    --   46.95 -99.00-150.00  182
 17  \w    -59.00  12.00   0.50    2.00    --  -46.95  34.00-150.00  142
 18  \w    -58.00  14.00   0.50    2.00    --  -46.95  38.00  60.00  144
 19  \w    -58.00  26.00   0.50    2.00    --  -46.95  38.00 -30.00  168
 20  \w    -73.00 -36.00   0.50   19.00    --  -99.00  77.00  60.00   74
 21  \w   -114.00 -35.00   0.50    2.00    --  -46.95 -34.00  52.00  158
 22  \w   -106.00 -81.00   0.50    2.00    --  -46.95-125.00  30.00   50
 23  \w   -148.00 -87.00   0.50   19.00    --  -99.00 -34.00  52.00  122
 24  \w   -112.00 -55.00   0.50   19.00    --  -99.00  30.00   0.00  114
 25  \w   -107.00 -81.00   0.50   19.00    --  -99.00  77.00  60.00   52
 26  \w   -116.00 -30.00   0.50   19.00    --  -99.00 125.00 -90.00  172
 27  \w   -112.00 -71.00   0.50   19.00    --  -99.00  34.00-150.00   82
 28  \w   -111.00 -29.00   0.50   19.00    --  -99.00  15.00-150.00  164
 29  \w   -166.00 -89.00   0.50   19.00    --  -99.00 -30.00   0.00  154
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0095486000
_diffrn_orient_matrix_UB_12      -0.0559082000
_diffrn_orient_matrix_UB_13      -0.0111759000
_diffrn_orient_matrix_UB_21      -0.0681256000
_diffrn_orient_matrix_UB_22      -0.0041518000
_diffrn_orient_matrix_UB_23      -0.0431483000
_diffrn_orient_matrix_UB_31      0.0152349000
_diffrn_orient_matrix_UB_32      0.0158790000
_diffrn_orient_matrix_UB_33      -0.0510918000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0863
_diffrn_reflns_av_unetI/netI     0.0378
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.949
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            83208
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.949
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         77.845
_diffrn_reflns_theta_min         2.564
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.222
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75781
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.14e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.302
_exptl_crystal_description       needle
_exptl_crystal_F_000             5952
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.989
_refine_diff_density_min         -0.828
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   2.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     851
_refine_ls_number_reflns         14763
_refine_ls_number_restraints     504
_refine_ls_restrained_S_all      2.178
_refine_ls_R_factor_all          0.1675
_refine_ls_R_factor_gt           0.1345
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3470
_refine_ls_wR_factor_ref         0.3635
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8975
_reflns_number_total             14763
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc03744c2.cif
_cod_data_source_block           a
_cod_database_code               1559104
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHNOSiBrF
_chemical_oxdiff_usercomment     CHNOSiBrF
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C71-C72 = C73-C72 = C71-C76 = C75-C76 = C74-C75 = C74-C73
 1.39 with sigma of 0.005
 C71-C77
 1.51 with sigma of 0.02
 C52-C51 = C53-C51 = C58-C57 = C59-C57 = C55-C54 = C56-C54
 1.54 with sigma of 0.01
 C69-C68
 1.54 with sigma of 0.01
 Si2-C62A
 1.87 with sigma of 0.01
 C63A-C62A
 1.54 with sigma of 0.01
 C42-C41 = C43-C42 = C44-C43 = C45-C44 = C46-C45 = C47-C46 = C48-C47 = C34-C33
 = C35-C34 = C36-C35 = C37-C36 = C38-C37 = C39-C38 = C40-C39
 1.54 with sigma of 0.01
 C47-C45
 2.5 with sigma of 0.02
 C71-C75
 2.2 with sigma of 0.02
 C76-C74
 2.2 with sigma of 0.02
 C76-C72
 2.2 with sigma of 0.02
 C40-C38
 2.5 with sigma of 0.02
 C48-C46
 2.5 with sigma of 0.02
3. Rigid bond restraints
 C24, F2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Si2, C62A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C24, C25
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C48, C47
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F3, C23
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C45, C44
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76 \\sim C77: within 1.7A
with sigma of 0.02 and sigma for terminal atoms of 0.04
Si1 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim
C58 \\sim C59: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.04
C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim
C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48:
within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
Si2 \\sim C62A \\sim C63A \\sim C64A \\sim C65 \\sim C66 \\sim C67 \\sim C68
\\sim C69 \\sim C70: within 1.7A with sigma of 0.02 and sigma for terminal
atoms of 0.04
Uanis(C75) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C71)
\\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C76) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Si1) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C56)
\\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C59) \\sim Ueq,
Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C53) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C33) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C36)
\\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C39) \\sim Ueq,
Uanis(C40) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C43)
\\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C46) \\sim Ueq,
Uanis(C47) \\sim Ueq, Uanis(C48) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(Si2) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C67)
\\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C70) \\sim Ueq,
Uanis(C62A) \\sim Ueq, Uanis(C64A) \\sim Ueq, Uanis(C63A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
5.a Riding coordinates:
 C48(H48A,H48B,H48C), C64A(H64A,H64B,H64C)
5.b Ternary CH refined with riding coordinates:
 C16(H16), C31(H31), C51(H51), C54(H54), C57(H57), C62A(H62A), C65(H65),
 C68(H68)
5.c Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,
 H37B), C38(H38A,H38B), C39(H39A,H39B), C41(H41A,H41B), C42(H42A,H42B),
 C43(H43A,H43B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B), C47(H47A,H47B)
5.d Aromatic/amide H refined with riding coordinates:
 C20(H20), C27(H27), C72(H72), C73(H73), C74(H74), C75(H75), C76(H76)
5.e Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C55(H55A,H55B,
 H55C), C56(H56A,H56B,H56C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C),
 C63A(H63A,H63B,H63C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C69(H69A,H69B,
 H69C), C70(H70A,H70B,H70C), C77(H77A,H77B,H77C)
;
_shelx_res_checksum              22092
_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 2.461
_oxdiff_exptl_absorpt_empirical_full_min 0.318