Unusual [4+2] Fusion Strategy to Forge meso-N/O-Heteroarene-Fused (Quinoidal) Porphyrins with Intense Near-Infrared Q-Bands
Li, Chengming; Zhu, Lei; Liang, Wenbo; Su, Rongchuan; Yin, Jiangliang; Hu, Yanmei; Lan, Yu; Wu, Di; You, Jingsong; Chemical Science  (2019) –; doi:10.1039/C9SC01596E

data_1551476
_publ_section_title
;
 Unusual [4+2] Fusion Strategy to Forge meso-N/O-Heteroarene-Fused
 (Quinoidal) Porphyrins with Intense Near-Infrared Q-Bands
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC01596E
_journal_year                    2019
_chemical_formula_moiety         'C64 H44 N4 O3 Zn'
_chemical_formula_sum            'C64 H44 N4 O3 Zn'
_chemical_formula_weight         982.40
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2017-12-06
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2018-09-05 deposited with the CCDC.    2019-06-17 downloaded from the CCDC.
;
_cell_angle_alpha                103.438(2)
_cell_angle_beta                 101.949(2)
_cell_angle_gamma                98.725(2)
_cell_formula_units_Z            2
_cell_length_a                   13.4002(4)
_cell_length_b                   13.4625(4)
_cell_length_c                   17.1704(5)
_cell_measurement_reflns_used    8982
_cell_measurement_temperature    293.75(10)
_cell_measurement_theta_max      72.1200
_cell_measurement_theta_min      4.3210
_cell_volume                     2881.75(15)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      293.75(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.974
_diffrn_measurement_details
;
  1 omega   18.00  106.00   1.0000    6.6400
omega____ theta____ kappa____ phi______ frames
    -       36.5421   38.0000  150.0000 88

  2 omega   20.00  104.00   1.0000    6.6400
omega____ theta____ kappa____ phi______ frames
    -       36.5421   57.0000   30.0000 84

  3 omega   10.00  104.00   1.0000    6.6400
omega____ theta____ kappa____ phi______ frames
    -       36.5421   77.0000  150.0000 94

  4 omega    1.00   75.00   1.0000    6.6400
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -99.0000    0.0000 74

  5 omega   23.00   90.00   1.0000    6.6400
omega____ theta____ kappa____ phi______ frames
    -       36.5421 -125.0000  120.0000 67

  6 omega   18.00  106.00   1.0000    6.6400
omega____ theta____ kappa____ phi______ frames
    -       36.5421   38.0000 -120.0000 88

  7 omega    1.00   75.00   1.0000    6.6400
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -99.0000 -150.0000 74

  8 omega  -31.00   53.00   1.0000    6.6400
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -57.0000  -90.0000 84

  9 omega   20.00  104.00   1.0000    6.6400
omega____ theta____ kappa____ phi______ frames
    -       36.5421   57.0000   90.0000 84

 10 omega   10.00  104.00   1.0000    6.6400
omega____ theta____ kappa____ phi______ frames
    -       36.5421   77.0000  -60.0000 94

 11 omega   40.00   98.00   1.0000   26.5550
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -30.0000 58

 12 omega   40.00   98.00   1.0000   26.5550
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   30.0000 58

 13 omega   38.00   91.00   1.0000   26.5550
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  150.0000 53

 14 omega   40.00   98.00   1.0000   26.5550
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -180.0000 58

 15 omega   39.00  109.00   1.0000   26.5550
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -150.0000 70

 16 omega   40.00   98.00   1.0000   26.5550
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -120.0000 58

 17 omega   39.00  109.00   1.0000   26.5550
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  120.0000 70

 18 omega   39.00  109.00   1.0000   26.5550
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   30.0000 70

 19 omega   57.00  150.00   1.0000   26.5550
omega____ theta____ kappa____ phi______ frames
    -      108.0000  178.0000   30.0000 93

 20 omega   40.00   98.00   1.0000   26.5550
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   90.0000 58

 21 omega   38.00   91.00   1.0000   26.5550
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  120.0000 53

 22 omega   38.00   91.00   1.0000   26.5550
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -180.0000 53

 23 omega   91.00  176.00   1.0000   26.5550
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000  150.0000 85

 24 omega   39.00  109.00   1.0000   26.5550
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   60.0000 70

 25 omega   70.00  178.00   1.0000   26.5550
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000   90.0000 108

 26 omega   38.00   91.00   1.0000   26.5550
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -90.0000 53

 27 omega   38.00  116.00   1.0000   26.5550
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000    0.0000 78

 28 omega   37.00  146.00   1.0000   26.5550
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -15.0000  -30.0000 109

 29 omega  -33.00   55.00   1.0000    6.6400
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -38.0000  150.0000 88

 30 omega   10.00  104.00   1.0000    6.6400
omega____ theta____ kappa____ phi______ frames
    -       36.5421   77.0000 -120.0000 94

 31 omega  -33.00   55.00   1.0000    6.6400
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -38.0000   60.0000 88
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0607250000
_diffrn_orient_matrix_UB_12      -0.0045444000
_diffrn_orient_matrix_UB_13      0.0665339000
_diffrn_orient_matrix_UB_21      0.1023694000
_diffrn_orient_matrix_UB_22      0.0073892000
_diffrn_orient_matrix_UB_23      0.0636502000
_diffrn_orient_matrix_UB_31      0.0167035000
_diffrn_orient_matrix_UB_32      0.1200247000
_diffrn_orient_matrix_UB_33      0.0246737000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0613
_diffrn_reflns_av_unetI/netI     0.0615
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            31404
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.985
_diffrn_reflns_theta_min         4.338
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.949
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51281
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dull blackish black'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   blackish
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.132
_exptl_crystal_description       block
_exptl_crystal_F_000             1020
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.2
_platon_squeeze_details
;
TITL lcm-159_a.res in P-1
CELL   13.4002   13.4625   17.1704    103.44    101.95     98.72
SPGR P-1
C101 0.628 0.291 0.093 !       1.84 eA-3
C102 0.824 0.713 0.190 !       1.75 eA-3
C103 0.611 0.245 0.143 !       1.73 eA-3
C104 0.781 0.655 0.172 !       1.70 eA-3
C105 0.675 0.308 0.216 !       1.58 eA-3
C106 0.779 0.796 0.265 !       1.58 eA-3
C107 0.717 0.330 0.234 !       1.53 eA-3
C108 0.718 0.728 0.264 !       1.43 eA-3
Q109 0.840 0.794 0.217 !       1.41 eA-3
C110 0.721 0.632 0.237 !       1.40 eA-3
C111 0.699 0.388 0.126 !       1.30 eA-3
Q112 0.808 0.935 0.091 !       1.10 eA-3
Q113 0.920 0.907 0.221 !       1.07 eA-3
Q114 0.955 0.212 0.034 !       1.02 eA-3
Q115 0.902 0.962 0.159 !       0.98 eA-3
Q116 0.348 0.234 0.347 !       0.87 eA-3
Q117 0.251 0.130 0.347 !       0.86 eA-3
Q118 0.126 0.750 0.110 !       0.86 eA-3
Q119 0.093 0.826 0.062 !       0.83 eA-3
Q120 0.113 0.670 0.095 !       0.82 eA-3
Q121 0.709 0.896 0.095 !       0.73 eA-3
Q122 0.199 0.557 0.388 !       0.62 eA-3
Q123 0.314 0.170 0.301 !       0.61 eA-3
Q124 0.142 0.169 0.218 !       0.61 eA-3
Q125 0.247 1.002 0.476 !       0.60 eA-3
Q126 0.184 0.058 0.367 !       0.59 eA-3
Q127 0.621 0.877 0.028 !       0.59 eA-3
Q128 0.221 0.221 0.253 !       0.59 eA-3
Q129 0.378 0.660 0.436 !       0.59 eA-3
Q130 0.282 0.090 0.044 !       0.58 eA-3
Q131 0.813 0.935 0.021 !       0.58 eA-3
Q132 0.376 0.158 0.473 !       0.58 eA-3
Q133 0.377 0.435 0.208 !       0.58 eA-3
Q134 0.831 0.041 0.044 !       0.55 eA-3
Q135 0.764 0.548 0.473 !       0.54 eA-3
Q136 0.972 0.047 0.170 !       0.54 eA-3
Q137 0.418 0.306 0.381 !       0.53 eA-3
Q138 0.265 0.209 0.376 !       0.53 eA-3
Q139 0.074 0.628 0.014 !       0.52 eA-3
;
_refine_diff_density_max         0.859
_refine_diff_density_min         -0.401
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     711
_refine_ls_number_reflns         11234
_refine_ls_number_restraints     237
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.1050
_refine_ls_R_factor_gt           0.0824
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1584P)^2^+0.6365P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2351
_refine_ls_wR_factor_ref         0.2705
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7927
_reflns_number_total             11234
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc01596e2.cif
_cod_data_source_block           lcm-159_sq
_cod_original_cell_volume        2881.73(15)
_cod_database_code               1551476
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 99.87
_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
2. Restrained distances
 C13S-C16S = C16S-C15S = C15S-C14S
 1.5 with sigma of 0.02
 O1-C16S
 2.35 with sigma of 0.02
 C14S-C16S
 2.4 with sigma of 0.02
3. Rigid bond restraints
 O1, C13S, C14S, C15S, C16S
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1, C2, C3, C4, C5, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C7, C8, C9, C10, C11, C12
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1A, C2A, C3A, C4A, C5A, C6A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C7A, C8A, C9A, C10A, C11A, C12A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
O1 \\sim C13S \\sim C14S \\sim C15S \\sim C16S: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
C1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A \\sim C6A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
C7A \\sim C8A \\sim C9A \\sim C10A \\sim C11A \\sim C12A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(C1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=
 Sof(C6)=Sof(H6)=1-FVAR(1)
 Sof(C1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=
 Sof(H5A)=Sof(C6A)=Sof(H6A)=FVAR(1)
 Sof(C7)=Sof(H7)=Sof(C8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=
 Sof(C12)=Sof(H12)=1-FVAR(2)
 Sof(C7A)=Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10A)=Sof(C11A)=
 Sof(H11A)=Sof(C12A)=Sof(H12A)=FVAR(2)
6.a Riding coordinates:
 C010(H010)
6.b Secondary CH2 refined with riding coordinates:
 C13S(H13A,H13B), C14S(H14A,H14B), C15S(H15A,H15B), C16S(H16A,H16B)
6.c Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A), C2(H2), C3(H3), C4(H4),
 C5(H5), C6(H6), C8A(H8A), C9A(H9A), C10A(H10A), C11A(H11A), C12A(H12A), C7(H7),
  C9(H9), C10(H10), C11(H11), C12(H12), C011(H011), C013(H013), C014(H014),
 C015(H015), C016(H016), C017(H017), C018(H018), C019(H019), C01A(H01A),
 C01B(H01B), C01C(H01C), C00D(H00D), C01D(H01D), C01G(H01G), C00I(H00I),
 C01J(H01J), C01K(H01K), C01M(H01M), C00N(H00N), C01P(H01P), C00Q(H00Q),
 C00S(H00S), C00U(H00U), C00W(H00W), C00Z(H00Z)
6.d Fitted hexagon refined as free rotating group:
 C1A(C2A,C3A,C4A,C5A,C6A), C1(C2,C3,C4,C5,C6), C7A(C8A,C9A,C10A,C11A,C12A),
 C7(C8,C9,C10,C11,C12)
;
_platon_squeeze_void_probe_radius 1.20
_olex2_date_sample_data_collection 2016-11-25
_olex2_submission_special_instructions 'No special instructions were received'