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_4036034
_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, 6.5(C6 H6)'
_chemical_formula_sum            'C221 H245 N8'
_chemical_formula_weight         3013.24
_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   geom
_audit_creation_date             2018-09-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                98.672(10)
_cell_angle_beta                 93.842(9)
_cell_angle_gamma                105.443(11)
_cell_formula_units_Z            2
_cell_length_a                   12.5978(15)
_cell_length_b                   17.972(2)
_cell_length_c                   43.321(5)
_cell_measurement_reflns_used    1798
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      46.1420
_cell_measurement_theta_min      9.9330
_cell_volume                     9287(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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.697
_diffrn_measured_fraction_theta_max 0.697
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \f     31.00 215.50   1.50    2.55  36.06  60.56  60.00    --   123
  2  \f    215.00 359.00   1.50    2.55  36.06  60.56   0.00    --    96
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1024761000
_diffrn_orient_matrix_UB_12      0.0145580000
_diffrn_orient_matrix_UB_13      0.0145799000
_diffrn_orient_matrix_UB_21      0.0492342000
_diffrn_orient_matrix_UB_22      -0.0087643000
_diffrn_orient_matrix_UB_23      0.0323311000
_diffrn_orient_matrix_UB_31      0.0581070000
_diffrn_orient_matrix_UB_32      0.0887159000
_diffrn_orient_matrix_UB_33      0.0072646000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0671
_diffrn_reflns_av_unetI/netI     0.1435
_diffrn_reflns_Laue_measured_fraction_full 0.697
_diffrn_reflns_Laue_measured_fraction_max 0.697
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            13101
_diffrn_reflns_point_group_measured_fraction_full 0.697
_diffrn_reflns_point_group_measured_fraction_max 0.697
_diffrn_reflns_theta_full        44.491
_diffrn_reflns_theta_max         44.491
_diffrn_reflns_theta_min         10.280
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.461
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79945
_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 brownish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.078
_exptl_crystal_description       plate
_exptl_crystal_F_000             3254
_exptl_crystal_size_max          0.105
_exptl_crystal_size_mid          0.073
_exptl_crystal_size_min          0.018
_refine_diff_density_max         0.777
_refine_diff_density_min         -0.471
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.222
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2178
_refine_ls_number_reflns         10206
_refine_ls_number_restraints     2107
_refine_ls_restrained_S_all      1.119
_refine_ls_R_factor_all          0.1971
_refine_ls_R_factor_gt           0.1299
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_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          0.3234
_refine_ls_wR_factor_ref         0.3778
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5648
_reflns_number_total             10206
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02907_si_003.cif
_cod_data_source_block           compound_15
_cod_database_code               4036034
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H N'
_reflns_odcompleteness_completeness 69.67
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     44.45
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C183-C71 \\sim C73-C71 \\sim C184-C71 \\sim C74-C71 \\sim C185-C71 \\sim
C71-C72
 with sigma of 0.02
 C134-C131 \\sim C131-C133 \\sim C186-C189 \\sim C187-C186 \\sim C186-C188
 with sigma of 0.02
 C187-C186 \\sim C132-C131 \\sim C186-C188 \\sim C131-C133 \\sim C186-C189
\\sim C134-C131
 with sigma of 0.02
 C186-C127 \\sim C127-C131
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C71 \\sim C72 \\sim C73 \\sim C74 \\sim C183 \\sim C184 \\sim C185: within 4A
with sigma of 0.02 and sigma for terminal atoms of 0.04
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Sof(C183)=Sof(H18s)=Sof(H18t)=Sof(H18u)=Sof(C184)=Sof(H18m)=Sof(H18n)=
 Sof(H18o)=Sof(C185)=Sof(H18p)=Sof(H18q)=Sof(H18r)=1-FVAR(1)
 Sof(C72)=Sof(H72a)=Sof(H72b)=Sof(H72c)=Sof(C73)=Sof(H73a)=Sof(H73b)=Sof(H73c)=
 Sof(C74)=Sof(H74a)=Sof(H74b)=Sof(H74c)=FVAR(1)
 Sof(C131)=Sof(C132)=Sof(H13p)=Sof(H13q)=Sof(H13r)=Sof(C133)=Sof(H13d)=
 Sof(H13e)=Sof(H13f)=Sof(C134)=Sof(H13m)=Sof(H13n)=Sof(H13o)=1-FVAR(2)
 Sof(C186)=Sof(C187)=Sof(H18j)=Sof(H18k)=Sof(H18l)=Sof(C188)=Sof(H18v)=
 Sof(H18w)=Sof(H18x)=Sof(C189)=Sof(H18y)=Sof(H)=Sof(Ha)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 N1(H1), N3(H3), N6(H6), N8(H8), 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), C86(H86), C87(H87),
 C89(H89), C90(H90), C93(H93), C94(H94), C98(H98), C99(H99), C103(H103),
 C104(H104), C108(H108), C109(H109), C112(H112), C114(H114), C116(H116),
 C126(H126), C128(H128), C130(H130), C140(H140), C142(H142), C144(H144),
 C154(H154), C155(H155), C157(H157), C158(H158), C164(H164), C165(H165),
 C167(H167), C168(H168), C174(H174), C175(H175), C177(H177), C178(H178),
 C9OA(H9OA), C220(H220), C221(H221), C222(H222), C223(H223), C224(H224),
 C190(H190), C191(H191), C192(H192), C193(H193), C194(H194), C195(H195),
 C196(H196), C197(H197), C198(H198), C199(H199), C200(H200), C201(H201),
 C202(H202), C203(H203), C204(H204), C205(H205), C206(H206), C207(H207),
 C208(H208), C209(H209), C210(H210), C211(H211), C212(H212), C213(H213),
 C214(H214), C215(H215), C216(H216), C217(H217), C218(H218), C219(H219),
 C225(H225), C226(H226), C227(H227)
6.b Idealised Me refined with riding coordinates:
 C120(H12j,H12k,H12l), C136(H13j,H13k,H13l), C137(H13a,H13b,H13c)
6.c Idealised Me refined as rotating group:
 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), C82(H82a,H82b,H82c), C83(H83a,H83b,H83c), C84(H84a,H84b,H84c),
 C118(H11d,H11e,H11f), C119(H11a,H11b,H11c), C122(H12d,H12e,H12f), C123(H12g,
 H12h,H12i), C124(H12a,H12b,H12c), C138(H13g,H13h,H13i), C146(H14d,H14e,H14f),
 C147(H14a,H14b,H14c), C148(H14g,H14h,H14i), C150(H15g,H15h,H15i), C151(H15a,
 H15b,H15c), C152(H15d,H15e,H15f), C160(H16g,H16h,H16i), C161(H16d,H16e,H16f),
 C162(H16a,H16b,H16c), C170(H17g,H17h,H17i), C171(H17a,H17b,H17c), C172(H17d,
 H17e,H17f), C180(H18g,H18h,H18i), C181(H18a,H18b,H18c), C182(H18d,H18e,H18f),
 C72(H72a,H72b,H72c), C73(H73a,H73b,H73c), C74(H74a,H74b,H74c), C187(H18j,H18k,
 H18l), C188(H18v,H18w,H18x), C189(H18y,H,Ha), C132(H13p,H13q,H13r), C133(H13d,
 H13e,H13f), C134(H13m,H13n,H13o), C183(H18s,H18t,H18u), C184(H18m,H18n,H18o),
 C185(H18p,H18q,H18r)
;
_olex2_date_sample_data_collection 2018-01-24
_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 1.333
_oxdiff_exptl_absorpt_empirical_full_min 0.582