Ambipolar conjugated ladder polymers by room-temperature Knoevenagel polymerization.
Zhao, Lingli; Wu, Zeng; Qin, Hanwen; Bin, Guangxiong; Gao, Junxiang; Zeng, Weixuan; Zhao, Yan; Chen, Huajie; Chemical science 15 (2024) 11594–11603; doi:10.1039/d4sc03222e

data_1571961
_publ_section_title
;
 Ambipolar conjugated ladder polymers by room-temperature Knoevenagel
 polymerization.
;
_journal_issue                   29
_journal_name_full               'Chemical science'
_journal_page_first              11594
_journal_page_last               11603
_journal_paper_doi               10.1039/d4sc03222e
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C112 H124 N8'
_chemical_formula_sum            'C112 H124 N8'
_chemical_formula_weight         1582.18
_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             2024-04-18
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2024-05-04 deposited with the CCDC.	2024-06-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.107(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.0671(3)
_cell_length_b                   13.6045(3)
_cell_length_c                   46.1940(9)
_cell_measurement_reflns_used    8466
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      71.9090
_cell_measurement_theta_min      3.3830
_cell_volume                     9468.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_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    -57.00 -19.00   0.50   20.00    --  -46.12 107.00 101.00   76
  2  \w     18.00  73.00   0.50   20.00    --   46.12-107.00   3.00  110
  3  \w   -129.00-103.00   0.50   10.00    --  -99.00-107.00   3.00   52
  4  \w   -107.00 -31.00   0.50   10.00    --  -99.00 107.00 101.00  152
  5  \w     73.00 102.00   0.50   10.00    --   99.00-107.00   3.00   58
  6  \w     88.00 168.00   0.50   10.00    --   99.00 107.00 101.00  160
  7  \w    -23.00  26.00   0.50   20.00    --  -46.12  19.00  90.00   98
  8  \w    -70.00 -31.00   0.50   20.00    --  -46.12 -57.00 -60.00   78
  9  \w   -117.00 -76.00   0.50   20.00    --  -46.12 -57.00 -60.00   82
 10  \w    -23.00  29.00   0.50   20.00    --  -46.12  19.00-150.00  104
 11  \w    -19.00  16.00   0.50   20.00    --   46.12 -37.00-120.00   70
 12  \w    -55.00 -29.00   0.50   10.00    --  -99.00  61.00  90.00   52
 13  \w    -55.00 -30.00   0.50   10.00    --  -99.00  61.00  60.00   50
 14  \w   -149.00 -97.00   0.50   10.00    --  -99.00 -94.00  60.00  104
 15  \w    -57.00 -31.00   0.50   10.00    --  -99.00  61.00 120.00   52
 16  \w   -169.00 -75.00   0.50   10.00    --  -99.00-125.00 -60.00  188
 17  \w   -171.00 -76.00   0.50   10.00    --  -99.00 -77.00  30.00  190
 18  \w    -99.00 -50.00   0.50   10.00    --  -99.00  77.00 120.00   98
 19  \w     27.00  52.00   0.50   10.00    --   99.00 -45.00-150.00   50
 20  \w     28.00  53.00   0.50   10.00    --   99.00 -45.00  60.00   50
 21  \w     28.00  66.00   0.50   10.00    --   99.00 -94.00 -60.00   76
 22  \w     27.00  52.00   0.50   10.00    --   99.00 -45.00   0.00   50
 23  \w     27.00  52.00   0.50   10.00    --   99.00 -45.00-180.00   50
 24  \w     74.00  99.00   0.50   10.00    --   99.00 -94.00 -60.00   50
 25  \w     28.00  53.00   0.50   10.00    --   99.00 -45.00 150.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0517465000
_diffrn_orient_matrix_UB_12      -0.0676890000
_diffrn_orient_matrix_UB_13      0.0207751000
_diffrn_orient_matrix_UB_21      -0.0134799000
_diffrn_orient_matrix_UB_22      -0.0867373000
_diffrn_orient_matrix_UB_23      -0.0209881000
_diffrn_orient_matrix_UB_31      0.0871733000
_diffrn_orient_matrix_UB_32      0.0267346000
_diffrn_orient_matrix_UB_33      -0.0154902000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0629
_diffrn_reflns_av_unetI/netI     0.0542
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       54
_diffrn_reflns_limit_l_min       -54
_diffrn_reflns_number            32783
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        66.599
_diffrn_reflns_theta_max         66.599
_diffrn_reflns_theta_min         3.387
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.487
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67344
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.92a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic light colourless'
_exptl_crystal_density_diffrn    1.110
_exptl_crystal_description       block
_exptl_crystal_F_000             3408
_exptl_crystal_size_max          0.132
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.525
_refine_diff_density_min         -0.524
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.448
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     599
_refine_ls_number_reflns         8304
_refine_ls_number_restraints     636
_refine_ls_restrained_S_all      69.141
_refine_ls_R_factor_all          0.1523
_refine_ls_R_factor_gt           0.1186
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.207
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3478
_refine_ls_wR_factor_ref         0.3787
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5448
_reflns_number_total             8304
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03222e2.cif
_cod_data_source_block           n2
_cod_depositor_comments          'Adding full bibliography for 1571961.cif.'
_cod_database_code               1571961
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N S'
_shelx_estimated_absorpt_t_max   0.962
_shelx_estimated_absorpt_t_min   0.938
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C54-C55 = C54-C53
 1.54 with sigma of 0.01
 C52-C53
 1.54 with sigma of 0.01
 C55-C56
 1.54 with sigma of 0.01
 C54-C55
 1.54 with sigma of 0.01
 C30-C31 = C30-C29
 1.54 with sigma of 0.01
 C44-C43 = C44-C45
 1.54 with sigma of 0.01
 C46-C45
 1.54 with sigma of 0.01
 C46A-C45A = C45A-C44A = C44A-C43A
 1.5 with sigma of 0.01
 C58-C57 = C62-C58 = C62-C59 = C60-C59 = C61-C60
 1.54 with sigma of 0.01
 C54-C56
 2.4 with sigma of 0.01
 C53-C51
 2.4 with sigma of 0.01
 C55-C53
 2.4 with sigma of 0.01
 C54-C52
 2.45 with sigma of 0.01
 C61-C59
 2.4 with sigma of 0.01
 C58-C50
 2.42 with sigma of 0.01
3. Rigid bond restraints
 C55, C54, C53, C52, C51
 with sigma for 1-2 distances of 0.00007 and sigma for 1-3 distances of 0.00007
 C51, C50
 with sigma for 1-2 distances of 0.006 and sigma for 1-3 distances of 0.006
 C61, C60, C59, C62, C58, C57, C50
 with sigma for 1-2 distances of 0.0008 and sigma for 1-3 distances of 0.0008
 C60, C61
 with sigma for 1-2 distances of 0.00009 and sigma for 1-3 distances of 0.00009
4. Uiso/Uaniso restraints and constraints
C44 \\sim C45 \\sim C46: within 2A with sigma of 0.0007 and sigma for terminal
atoms of 0.0014 within 2A
C55 \\sim C54 \\sim C53 \\sim C52 \\sim C51: within 2A with sigma of 0.0006 and
sigma for terminal atoms of 0.0012 within 2A
C45 \\sim C46 \\sim C44: within 2A with sigma of 0.0004 and sigma for terminal
atoms of 0.0008 within 2A
C51 \\sim C50: within 2A with sigma of 0.0004 and sigma for terminal atoms of
0.0008 within 2A
C59 \\sim C62 \\sim C58 \\sim C57 \\sim C50: within 2A with sigma of 0.0001 and
sigma for terminal atoms of 0.0002 within 2A
C59 \\sim C62: within 2A with sigma of 0.00008 and sigma for terminal atoms of
0.00016 within 2A
C60 \\sim C59: within 2A with sigma of 0.00008 and sigma for terminal atoms of
0.00016 within 2A
Uanis(C56) \\sim Ueq: with sigma of 0.0005 and sigma for terminal atoms of 0.001
Uanis(C44A) = Uanis(C45A) = Uanis(C46A) = Uanis(C43A) = Uanis(C42)
Uanis(C50) = Uanis(C49) = Uanis(C48)
5. Rigid body (RIGU) restrains
 N1, N2, N3, N4, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14,
 C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30,
  C31, C32, C33, C34, C35, C36, C37, C38, C39, C40, C41, C42, C43, C44, C45,
 C46, C47, C48, C49, C50, C51, C52, C53, C54, C55, C56
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.004
 N1, N2, N3, N4, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14,
 C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30,
  C31, C32, C33, C34, C35, C36, C37, C38, C39, C40, C41, C42, C43, C44, C45,
 C46, C47, C48, C49, C50, C51, C52, C53, C54, C55, C56
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.005
 C44, N1, C11, C10, C1, C9, C2, C6, C8, C12, C3, C5, C7, C18, C13, C17, C4,
 C32, C19, C14, C16, N2, C20, C15, C21, N3, C22, C23, C33, C24, C34, N4, C35,
 C47, C25, C36, C48, C26, C37, C49, C27, C31, C38, C50, C28, C30, C39, C51, C29,
  C40, C52, C41, C53, C42, C54, C43, C55, C56, C45, C46
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.007
 C41, C42, C43, C44, C45, C46, C44A, C45A, C46A, C43A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.005
 C41, C42, C43A, C44A, C45A, C46A, C40
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.006
 C46, N1, C11, C10, C1, C9, C2, C6, C8, C12, H2, C3, C5, C7, C18, C13, C17, H3,
  C4, H5, C32, C19, H13, C14, C16, H4, N2, H19, C20, H14, C15, C21, N3, H15,
 C22, C23, C33, C24, H33A, H33B, C34, N4, H34, C35, C47, C25, H35A, H35B, C36,
 H47A, H47B, C48, C26, H36A, H36B, C37, H48A, H48B, C49, C27, C31, H37A, H37B,
 C38, H49A, H49B, C50, H27, C28, H31, C30, H38A, H38B, C39, C51, H28, C29, H30,
 H39A, H39B, C40, C52, H29, H40A, H40B, C41, C53, H41A, H41B, C42, C54, H42A,
 H42B, H42C, H42D, C43, C43A, C55, H43A, H43B, C44, C44A, H43C, H43D, C56, H44A,
  H44B, C45, H44C, H44D, C45A, H45A, H45B, H45C, H45D, C46A, H46A, H46B, H46C,
 H46D, H46E, H46F
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.007
 C52, N1, C11, C10, C1, C9, C2, C6, C8, C12, H2, C3, C5, C7, C18, C13, C17, H3,
  C4, H5, C32, C19, H13, C14, C16, H4, N2, H19, C20, H14, C15, C21, N3, H15,
 C22, C23, C33, C24, H33A, H33B, C34, N4, H34, C35, C47, C25, H35A, H35B, C36,
 H47A, H47B, C48, C26, H36A, H36B, C37, H48A, H48B, C49, C27, C31, H37A, H37B,
 C38, H49A, H49B, C50, H27, C28, C30, H31, H38A, H38B, C39, H50B, H50A, C51,
 C57, H28, C29, H30, H39A, H39B, C40, H51A, H51B, H57A, H57B, C58, H29, H40A,
 H40B, C41, H52A, H52B, C53, C62, H41A, H41B, C42, H53A, H53B, C54, C59, H62A,
 H62B, H42A, H42B, H42C, H42D, C43, C43A, H54A, H54B, C55, C60, H43A, H43B, C44,
  C44A, H43C, H43D, H55A, H55B, C56, H60A, H60B, C61, H44A, H44B, C45, H44C,
 H44D, C45A, H56A, H56B, H56C, H45A, H45B, C46, H45C, H45D, C46A, H46A, H46B,
 H46C, H46D, H46E, H46F
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: H42A(0.5) H42B(0.5) H42C(0.5) H42D(0.5) C43(0.5) H43A(0.5)
 H43B(0.5) C44(0.5) H44A(0.5) H44B(0.5) C45(0.5) H45A(0.5) H45B(0.5) C46(0.5)
 H46A(0.5) H46B(0.5) H46C(0.5) H50A(0.5) H50B(0.5) H50C(0.5) H50D(0.5) C51(0.5)
 H51A(0.5) H51B(0.5) C52(0.5) H52A(0.5) H52B(0.5) C53(0.5) H53A(0.5) H53B(0.5)
 C54(0.5) H54A(0.5) H54B(0.5) C55(0.5) H55A(0.5) H55B(0.5) C56(0.5) H56A(0.5)
 H56B(0.5) H56C(0.5) C44A(0.5) H44C(0.5) H44D(0.5) C45A(0.5) H45C(0.5)
 H45D(0.5) C46A(0.5) H46D(0.5) H46E(0.5) H46F(0.5) C43A(0.5) H43C(0.5)
 H43D(0.5) C60(0.5) H60A(0.5) H60B(0.5) C59(0.5) H59A(0.5) H59B(0.5) C57(0.5)
 H57A(0.5) H57B(0.5) C61(0.5) H61A(0.5) H61B(0.5) H61C(0.5) C58(0.5) H58A(0.5)
 H58B(0.5) C62(0.5) H62A(0.5) H62B(0.5)
7.a Ternary CH refined with riding coordinates:
 C34(H34)
7.b Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C38(H38A,
 H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B),
 C42(H42C,H42D), C43(H43A,H43B), C44(H44A,H44B), C45(H45A,H45B), C47(H47A,H47B),
  C48(H48A,H48B), C49(H49A,H49B), C50(H50A,H50B), C50(H50C,H50D), C51(H51A,
 H51B), C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B),
 C44A(H44C,H44D), C45A(H45C,H45D), C43A(H43C,H43D), C60(H60A,H60B), C59(H59A,
 H59B), C57(H57A,H57B), C58(H58A,H58B), C62(H62A,H62B)
7.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C13(H13), C14(H14), C15(H15), C19(H19),
 C27(H27), C28(H28), C29(H29), C30(H30), C31(H31)
7.d Idealised Me refined as rotating group:
 C46(H46A,H46B,H46C), C56(H56A,H56B,H56C), C46A(H46D,H46E,H46F), C61(H61A,H61B,
 H61C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              90113
_shelx_fab_checksum              27048
_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 2.042
_oxdiff_exptl_absorpt_empirical_full_min 0.506