Porphyrin-Hexaphenylbenzene Conjugates via Mixed Cyclotrimerization Reactions.
Martin, Max M.; Dill, Maximilian; Langer, Jens; Jux, Norbert; The Journal of organic chemistry 84 (2019) 1489–1499; doi:10.1021/acs.joc.8b02907

data_4036031
_publ_section_title
;
 Porphyrin-Hexaphenylbenzene Conjugates via Mixed Cyclotrimerization
 Reactions.
;
_journal_issue                   3
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              1489
_journal_page_last               1499
_journal_paper_doi               10.1021/acs.joc.8b02907
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C182 H206 N8, C6 H6'
_chemical_formula_sum            'C188 H212 N8'
_chemical_formula_weight         2583.64
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-09-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                88.0850(10)
_cell_angle_beta                 82.7460(10)
_cell_angle_gamma                82.7600(10)
_cell_formula_units_Z            2
_cell_length_a                   13.98976(19)
_cell_length_b                   20.6879(3)
_cell_length_c                   34.2198(4)
_cell_measurement_reflns_used    44549
_cell_measurement_temperature    99.96(17)
_cell_measurement_theta_max      73.5740
_cell_measurement_theta_min      3.6890
_cell_volume                     9744.7(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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      99.96(17)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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   -115.00 -17.00   1.00    6.00    --  -41.15 -38.00 -30.00   98
  2  \w    -66.00  33.00   1.00    6.00    --  -41.15  38.00 150.00   99
  3  \w    -69.00  32.00   1.00    6.00    --  -41.15  57.00 -90.00  101
  4  \w     23.00  97.00   1.00    6.00    --   41.15-125.00  60.00   74
  5  \w     77.00 178.00   1.00   23.00    --  106.54  61.00-120.00  101
  6  \w     30.00 135.00   1.00   23.00    --  106.54 -30.00 -90.00  105
  7  \w     30.00 139.00   1.00   23.00    --  106.54 -77.00-180.00  109
  8  \w     24.00 109.00   1.00   23.00    --  106.54 -94.00 120.00   85
  9  \w     78.00 178.00   1.00   23.00    --  106.54  30.00 -60.00  100
 10  \w     94.00 178.00   1.00   23.00    --  106.54 125.00-180.00   84
 11  \w     25.00 159.00   1.00   23.00    --  106.54 -15.00 120.00  134
 12  \w     24.00 109.00   1.00   23.00    --  106.54 -94.00-180.00   85
 13  \w     33.00 122.00   1.00   23.00    --  106.54-125.00  30.00   89
 14  \w   -114.00 -13.00   1.00    6.00    --  -41.15 -57.00 150.00  101
 15  \w   -117.00  -9.00   1.00    6.00    --  -41.15 -77.00  90.00  108
 16  \w   -117.00  -9.00   1.00    6.00    --  -41.15 -77.00   0.00  108
 17  \w   -117.00  -9.00   1.00    6.00    --  -41.15 -77.00 -90.00  108
 18  \w     77.00 178.00   1.00   23.00    --  106.54  61.00   0.00  101
 19  \w     78.00 178.00   1.00   23.00    --  106.54  30.00-180.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0154792000
_diffrn_orient_matrix_UB_12      -0.0168155000
_diffrn_orient_matrix_UB_13      0.0431274000
_diffrn_orient_matrix_UB_21      0.0311291000
_diffrn_orient_matrix_UB_22      -0.0718595000
_diffrn_orient_matrix_UB_23      -0.0109647000
_diffrn_orient_matrix_UB_31      0.1063168000
_diffrn_orient_matrix_UB_32      0.0137843000
_diffrn_orient_matrix_UB_33      -0.0089478000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0366
_diffrn_reflns_av_unetI/netI     0.0372
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            102523
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.079
_diffrn_reflns_theta_max         67.079
_diffrn_reflns_theta_min         3.209
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.378
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68697
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    0.881
_exptl_crystal_description       plank
_exptl_crystal_F_000             2792
_exptl_crystal_size_max          0.399
_exptl_crystal_size_mid          0.118
_exptl_crystal_size_min          0.097
_refine_diff_density_max         0.428
_refine_diff_density_min         -0.321
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2226
_refine_ls_number_reflns         34648
_refine_ls_number_restraints     1489
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0797
_refine_ls_R_factor_gt           0.0687
_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^)+(0.0876P)^2^+8.6030P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1812
_refine_ls_wR_factor_ref         0.1895
_reflns_Friedel_coverage         0.000
_reflns_number_gt                29001
_reflns_number_total             34648
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02907_si_001.cif
_cod_data_source_block           compound_8
_cod_database_code               4036031
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H N'
_reflns_odcompleteness_completeness 99.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C190-C189 \\sim C67-C70 \\sim C192-C189 \\sim C68-C67 \\sim C191-C189 \\sim
C69-C67
 with sigma of 0.02
 C189-C63 \\sim C63-C67
 with sigma of 0.02
 C161-C159 \\sim C224-C222 \\sim C162-C159 \\sim C223-C222 \\sim C160-C222
\\sim C160-C159
 with sigma of 0.02
 C159-C156 \\sim C156-C222
 with sigma of 0.02
 C40-C39 \\sim C206-C204 \\sim C205-C204 \\sim C42-C39 \\sim C207-C204 \\sim
C41-C39
 with sigma of 0.02
 C35-C39 \\sim C204-C35
 with sigma of 0.02
 C135-C131 \\sim C212-C131
 with sigma of 0.02
 C142-C139 \\sim C140-C139 \\sim C141-C139 \\sim C211-C208 \\sim C210-C208
\\sim C209-C208
 with sigma of 0.02
 C133-C208 \\sim C139-C133
 with sigma of 0.02
 C227-C225 \\sim C180-C179 \\sim C181-C179 \\sim C226-C225 \\sim C182-C179
\\sim C228-C225
 with sigma of 0.02
 C176-C179 \\sim C225-C176
 with sigma of 0.02
 C121-C117 \\sim C218-C216
 with sigma of 0.02
 C117-C118 \\sim C216-C217 \\sim C215-C115 \\sim C116-C115 \\sim C116-C117
\\sim C215-C216 \\sim C118-
 C119 \\sim C217-C119
 with sigma of 0.02
 C138-C135 \\sim C138-C212 \\sim C136-C135 \\sim C214-C212 \\sim C137-C135
\\sim C213-C212
 with sigma of 0.02
 C201-C200 \\sim C46-C219 \\sim C202-C200 \\sim C44-C219 \\sim C45-C219 \\sim
C203-C200
 with sigma of 0.02
 C37-C43 \\sim C200-C37
 with sigma of 0.02
 C59-C57 \\sim C196-C193 \\sim C193-C194 \\sim C58-C57 \\sim C195-C193 \\sim
C60-C57
 with sigma of 0.02
 C193-C51 \\sim C57-C51
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C218 \\sim C219 \\sim C220 \\sim C121 \\sim C122 \\sim C123 \\sim C124: within
4A with sigma of 0.02 and sigma for terminal atoms of 0.04
C160 \\sim C222 \\sim C223 \\sim C224 \\sim C159 \\sim C161 \\sim C162: within
4A with sigma of 0.02 and sigma for terminal atoms of 0.04
C204 \\sim C205 \\sim C206 \\sim C207 \\sim C39 \\sim C40 \\sim C41 \\sim C42:
within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04
C212 \\sim C213 \\sim C214 \\sim C135 \\sim C136 \\sim C137: within 4A with
sigma of 0.02 and sigma for terminal atoms of 0.04
C208 \\sim C209 \\sim C210 \\sim C211 \\sim C139 \\sim C140 \\sim C141 \\sim
C142: within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04
C225 \\sim C226 \\sim C227 \\sim C228 \\sim C179 \\sim C180 \\sim C181 \\sim
C182: within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04
C115 \\sim C119 \\sim C215 \\sim C216 \\sim C217 \\sim C116 \\sim C117 \\sim
C118: within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04
C200 \\sim C201 \\sim C202 \\sim C203 \\sim C43 \\sim C44 \\sim C45 \\sim C46:
within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04
C193 \\sim C194 \\sim C195 \\sim C196 \\sim C57 \\sim C58 \\sim C59 \\sim C60:
within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04
4. Others
 Sof(C197)=Sof(H19D)=Sof(H19E)=Sof(H19F)=Sof(C198)=Sof(H19J)=Sof(H19K)=
 Sof(H19L)=Sof(C199)=Sof(H19G)=Sof(H19H)=Sof(H19I)=1-FVAR(1)
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=
 Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=FVAR(1)
 Sof(C116)=Sof(H116)=Sof(C117)=Sof(C118)=Sof(H118)=Sof(C121)=Sof(C122)=
 Sof(H12J)=Sof(H12K)=Sof(H12L)=Sof(C123)=Sof(H12P)=Sof(H12Q)=Sof(H12R)=
 Sof(C124)=Sof(H12O)=Sof(H12M)=Sof(H12N)=1-FVAR(2)
 Sof(C215)=Sof(H215)=Sof(C216)=Sof(C217)=Sof(H217)=Sof(C218)=Sof(C219)=
 Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C220)=Sof(H22G)=Sof(H22H)=Sof(H22I)=
 Sof(C221)=Sof(H22D)=Sof(H22E)=Sof(H22F)=FVAR(2)
 Sof(C189)=Sof(C190)=Sof(H19P)=Sof(H19Q)=Sof(H19R)=Sof(C191)=Sof(H19M)=
 Sof(H19N)=Sof(H19O)=Sof(C192)=Sof(H19A)=Sof(H19B)=Sof(H19C)=1-FVAR(3)
 Sof(C67)=Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=Sof(C69)=Sof(H69A)=Sof(H69B)=
 Sof(H69C)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=FVAR(3)
 Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C159)=Sof(C161)=Sof(H16G)=Sof(H16H)=
 Sof(H16I)=Sof(C162)=Sof(H16J)=Sof(H16K)=Sof(H16L)=1-FVAR(4)
 Sof(H7)=Sof(H10)=Sof(H13)=Sof(C222)=Sof(C223)=Sof(H22M)=Sof(H22N)=Sof(H22O)=
 Sof(C224)=Sof(H22J)=Sof(H22K)=Sof(H22L)=FVAR(4)
 Sof(C204)=Sof(C205)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C206)=Sof(H20M)=
 Sof(H20N)=Sof(H20O)=Sof(C207)=Sof(H20J)=Sof(H20K)=Sof(H20L)=1-FVAR(5)
 Sof(C39)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C41)=Sof(H41A)=Sof(H41B)=
 Sof(H41C)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=FVAR(5)
 Sof(H1)=Sof(H3)=Sof(H5)=Sof(C212)=Sof(C213)=Sof(H21G)=Sof(H21H)=Sof(H21I)=
 Sof(C214)=Sof(H21D)=Sof(H21E)=Sof(H21F)=1-FVAR(6)
 Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C135)=Sof(C136)=Sof(H13J)=Sof(H13K)=
 Sof(H13L)=Sof(C137)=Sof(H13G)=Sof(H13H)=Sof(H13I)=FVAR(6)
 Sof(C208)=Sof(C209)=Sof(H20P)=Sof(H20Q)=Sof(H20R)=Sof(C210)=Sof(H21M)=
 Sof(H21N)=Sof(H21O)=Sof(C211)=Sof(H21J)=Sof(H21K)=Sof(H21L)=1-FVAR(7)
 Sof(C139)=Sof(C140)=Sof(H14G)=Sof(H14H)=Sof(H14I)=Sof(C141)=Sof(H14D)=
 Sof(H14E)=Sof(H14F)=Sof(C142)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(7)
 Sof(C225)=Sof(C226)=Sof(H22S)=Sof(H22T)=Sof(H22U)=Sof(C227)=Sof(H22P)=
 Sof(H22Q)=Sof(H22R)=Sof(C228)=Sof(H22A)=Sof(H22B)=Sof(H22C)=1-FVAR(8)
 Sof(C179)=Sof(C180)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C181)=Sof(H18D)=
 Sof(H18E)=Sof(H18F)=Sof(C182)=Sof(H18G)=Sof(H18H)=Sof(H18I)=FVAR(8)
 Sof(C43)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=Sof(C45)=Sof(H45A)=Sof(H45B)=
 Sof(H45C)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=1-FVAR(9)
 Sof(C200)=Sof(C201)=Sof(H20S)=Sof(H20T)=Sof(H20U)=Sof(C202)=Sof(H20G)=
 Sof(H20H)=Sof(H20I)=Sof(C203)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(9)
 Sof(C193)=Sof(C194)=Sof(H19V)=Sof(H19W)=Sof(H19X)=Sof(C195)=Sof(H)=Sof(H19Y)=
 Sof(HA)=Sof(C196)=Sof(H19S)=Sof(H19T)=Sof(H19U)=1-FVAR(10)
 Sof(C57)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=Sof(C59)=Sof(H59A)=Sof(H59B)=
 Sof(H59C)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=FVAR(10)
5.a Aromatic/amide H refined with riding coordinates:
 C8(H8A), C9(H9), C11(H11), C12(H12), C15(H15), C16(H16), C20(H20), C21(H21),
 C25(H25), C26(H26), C30(H30), C31(H31), C34(H34), C36(H36), C38(H38), C48(H48),
  C50(H50), C52(H52), C62(H62), C64(H64), C66(H66), C76(H76), C77(H77),
 C79(H79), C80(H80), C83(H83), C84(H84), C88(H88), C89(H89), C93(H93), C94(H94),
  C98(H98), C99(H99), C102(H102), C104(H104), C106(H106), C120(H120),
 C130(H130), C132(H132), C134(H134), C144(H144), C145(H145), C147(H147),
 C148(H148), C154(H154), C155(H155), C157(H157), C158(H158), C164(H164),
 C165(H165), C167(H167), C168(H168), C174(H174), C175(H175), C177(H177),
 C178(H178), C215(H215), C217(H217), C183(H183), C184(H184), C185(H185),
 C186(H186), C187(H187), C188(H188), C116(H116), C118(H118)
5.b Idealised Me refined with riding coordinates:
 C138(H13A,H13B,H13C), C138(H1,H3,H5)
5.c Idealised Me refined as rotating group:
 C72(H72A,H72B,H72C), C73(H73A,H73B,H73C), C74(H74A,H74B,H74C), C108(H10A,H10B,
 H10C), C109(H10D,H10E,H10F), C110(H11D,H11E,H11F), C112(H11J,H11K,H11L),
 C113(H11G,H11H,H11I), C114(H11A,H11B,H11C), C126(H12D,H12E,H12F), C127(H12A,
 H12B,H12C), C128(H12G,H12H,H12I), C150(H15D,H15E,H15F), C151(H15G,H15H,H15I),
 C152(H15A,H15B,H15C), C160(H16A,H16B,H16C), C160(H7,H10,H13), C170(H17G,H17H,
 H17I), C171(H17A,H17B,H17C), C172(H17D,H17E,H17F), C190(H19P,H19Q,H19R),
 C191(H19M,H19N,H19O), C192(H19A,H19B,H19C), C194(H19V,H19W,H19X), C195(H,H19Y,
 HA), C196(H19S,H19T,H19U), C197(H19D,H19E,H19F), C198(H19J,H19K,H19L),
 C199(H19G,H19H,H19I), C201(H20S,H20T,H20U), C202(H20G,H20H,H20I), C203(H20A,
 H20B,H20C), C205(H20D,H20E,H20F), C206(H20M,H20N,H20O), C207(H20J,H20K,H20L),
 C209(H20P,H20Q,H20R), C210(H21M,H21N,H21O), C211(H21J,H21K,H21L), C213(H21G,
 H21H,H21I), C214(H21D,H21E,H21F), C219(H21A,H21B,H21C), C220(H22G,H22H,H22I),
 C221(H22D,H22E,H22F), C223(H22M,H22N,H22O), C224(H22J,H22K,H22L), C226(H22S,
 H22T,H22U), C227(H22P,H22Q,H22R), C228(H22A,H22B,H22C), C40(H40A,H40B,H40C),
 C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C44(H44A,H44B,H44C), C45(H45A,H45B,
 H45C), C46(H46A,H46B,H46C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C56(H56A,
 H56B,H56C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C),
 C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C122(H12J,H12K,
 H12L), C123(H12P,H12Q,H12R), C124(H12O,H12M,H12N), C136(H13J,H13K,H13L),
 C137(H13G,H13H,H13I), C140(H14G,H14H,H14I), C141(H14D,H14E,H14F), C142(H14A,
 H14B,H14C), C161(H16G,H16H,H16I), C162(H16J,H16K,H16L), C180(H18A,H18B,H18C),
 C181(H18D,H18E,H18F), C182(H18G,H18H,H18I)
;
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.888
_oxdiff_exptl_absorpt_empirical_full_min 0.254