Functionalization of the "Bay Region" of Perylene in Reaction with 1-Arylalk-2-yn-1-ones Catalyzed by Trifluoromethanesulfonic Acid: One-Step Approach to 1-Acyl-2-alkylbenzo[ ghi]perylenes.
Głodek, Marta; Makal, Anna; Plażuk, Damian; The Journal of organic chemistry 83 (2018) 14165–14174; doi:10.1021/acs.joc.8b02280

data_4034857
_publ_section_title
;
 Functionalization of the &quot;Bay Region&quot; of Perylene in Reaction
 with 1-Arylalk-2-yn-1-ones Catalyzed by Trifluoromethanesulfonic Acid:
 One-Step Approach to 1-Acyl-2-alkylbenzo[ ghi]perylenes.
;
_journal_issue                   22
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              14165
_journal_page_last               14174
_journal_paper_doi               10.1021/acs.joc.8b02280
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety
'C44 H24 O, 0.25(C7 H8 O), 0.5(C3.25 H4 O0.5)'
_chemical_formula_sum            'C47.38 H28 O1.5'
_chemical_formula_weight         621.20
_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             2017-09-18
_audit_creation_method
;
Olex2 1.2
(compiled Aug 10 2017 17:44:14 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                94.683(14)
_cell_angle_beta                 107.646(17)
_cell_angle_gamma                90.179(10)
_cell_formula_units_Z            4
_cell_length_a                   12.6920(18)
_cell_length_b                   12.8497(14)
_cell_length_c                   19.663(5)
_cell_measurement_reflns_used    1010
_cell_measurement_temperature    100.30(10)
_cell_measurement_theta_max      46.0940
_cell_measurement_theta_min      2.3900
_cell_volume                     3044.4(10)
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      100.30(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2195
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.407
_diffrn_measured_fraction_theta_max 0.838
_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      2.00  28.00   1.00   15.00    --    0.00 -99.00 -90.00   26
  2  \w      5.00  50.00   1.00   15.00    --    0.00 -99.00 -60.00   45
  3  \w    -19.00  45.00   1.00   15.00    --    0.00  57.00  90.00   64
  4  \w     57.00  92.00   1.00   15.00    --    0.00  57.00  90.00   35
  5  \w     11.00  50.00   1.00   15.00    --    0.00 -99.00 120.00   39
  6  \w    -82.00 -45.00   1.00   50.00    --  -60.50 125.00-150.00   37
  7  \w   -142.00 -93.00   1.00   50.00    --  -60.50 -94.00 150.00   49
  8  \w   -138.00 -33.00   1.00   50.00    --  -60.50 -61.00  60.00  105
  9  \w   -136.00 -75.00   1.00   50.00    --  -60.50-125.00 120.00   61
 10  \w    -30.00  58.00   1.00   50.00    --   60.50 -45.00 -30.00   88
 11  \w    117.00 146.00   1.00   50.00    --   60.50 125.00 -90.00   29
 12  \w     79.00 157.00   1.00   50.00    --   60.50 154.00 -52.00   78
 13  \w     18.00  68.00   1.00   50.00    --   60.50 -94.00 -30.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0440351000
_diffrn_orient_matrix_UB_12      -0.0960726000
_diffrn_orient_matrix_UB_13      0.0261173000
_diffrn_orient_matrix_UB_21      -0.0427393000
_diffrn_orient_matrix_UB_22      -0.0496083000
_diffrn_orient_matrix_UB_23      -0.0777405000
_diffrn_orient_matrix_UB_31      0.1116787000
_diffrn_orient_matrix_UB_32      -0.0528376000
_diffrn_orient_matrix_UB_33      0.0092104000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0563
_diffrn_reflns_av_unetI/netI     0.1470
_diffrn_reflns_Laue_measured_fraction_full 0.407
_diffrn_reflns_Laue_measured_fraction_max 0.838
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            7026
_diffrn_reflns_point_group_measured_fraction_full 0.407
_diffrn_reflns_point_group_measured_fraction_max 0.838
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         46.743
_diffrn_reflns_theta_min         2.367
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.622
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74919
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.355
_exptl_crystal_description       plate
_exptl_crystal_F_000             1297
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.409
_refine_diff_density_min         -0.263
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     935
_refine_ls_number_reflns         4494
_refine_ls_number_restraints     1166
_refine_ls_restrained_S_all      0.918
_refine_ls_R_factor_all          0.2153
_refine_ls_R_factor_gt           0.1121
_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^)+(0.1638P)^2^+2.2163P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2665
_refine_ls_wR_factor_ref         0.3595
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1774
_reflns_number_total             4494
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02280_si_003.cif
_cod_data_source_block           sortav
_cod_original_cell_volume        3044.5(10)
_cod_original_formula_sum        'C47.38 H28 O1.50'
_cod_database_code               4034857
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 36.11
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
2. Restrained distances
 O4-C101 = O3-C107
 1.4 with sigma of 0.02
 O4-C201 = O4-C207
 1.4 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C101 \\sim C102 \\sim C103 \\sim C104 \\sim C105 \\sim C106 \\sim C107 \\sim O3
\\sim C201 \\sim C202 \\sim C203 \\sim C204 \\sim C205 \\sim C206 \\sim O4
\\sim C207: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.05
Uanis(C4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C51, C52, H52, C53, H53, C54, C55, C56, H56, C57, H57, C58, H58, C59, C60,
 H60, C61, H61, C62, H62, C63, C64, C65, H65, C66, H66, C67, H67, C68, C69, C70,
  C71, C72, C73, C74, C75, H75, C76, H76, C77, C78, H78, C79, H79, C80, H80,
 C81, C82, C83, H83, C84, H84, C85, H85, C86, C87, H87, C88, H88, C89, C90, C91,
  C92, C93, C94, H94A, H94B, H94C, O2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C1, C2, H2, C3, H3, C4, C5, C6, H6, C7, H7, C8, H8, C9, C10, H10, C11, H11,
 C12, H12, C13, C14, C15, H15, C16, H16, C17, H17, C18, C19, C20, C21, C22, C23,
  C24, C25, H25, C26, H26, C27, C28, H28, C29, H29, C30, H30, C31, C32, C33,
 H33, C34, H34, C35, H35, C36, C37, H37, C38, H38, C39, C40, C41, C42, C43, C44,
  H44A, H44B, H44C, O1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Same fragment restrains
{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, O1} sigma for 1-2: 0.02,
1-3: 0.04
as
{C51, C52, C53, C54, C55, C56, C57, C58, C59, C60, C61, C62, C63, C64, C65,
C66, C67, C68, C69, C70, C71, C72, C73, C74, C75, C76, C77, C78, C79, C80, C81,
C82, C83, C84, C85, C86, C87, C88, C89, C90, C91, C92, C93, C94, O2}
6. Others
 Fixed Sof: C101(0.5) C102(0.5) H102(0.5) C103(0.5) H103(0.5) C104(0.5)
 H104(0.5) C105(0.5) H105(0.5) C106(0.5) H106(0.5) C107(0.5) H10A(0.5)
 H10B(0.5) H10C(0.5) O3(0.5) C201(0.5) C202(0.5) H202(0.5) C203(0.5) H203(0.5)
 C204(0.5) H204(0.5) C205(0.5) H205(0.5) C206(0.25) H206(0.5) O4(0.5) C207(0.5)
 H20A(0.5) H20B(0.5) H20C(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C7(H7), C8(H8), C10(H10), C11(H11), C12(H12),
 C15(H15), C16(H16), C17(H17), C25(H25), C26(H26), C28(H28), C29(H29), C30(H30),
  C33(H33), C34(H34), C35(H35), C37(H37), C38(H38), C52(H52), C53(H53),
 C56(H56), C57(H57), C58(H58), C60(H60), C61(H61), C62(H62), C65(H65), C66(H66),
  C67(H67), C75(H75), C76(H76), C78(H78), C79(H79), C80(H80), C83(H83),
 C84(H84), C85(H85), C87(H87), C88(H88), C102(H102), C103(H103), C104(H104),
 C105(H105), C106(H106), C202(H202), C203(H203), C204(H204), C205(H205),
 C206(H206)
7.b Fitted hexagon refined as free rotating group:
 C101(C102,C103,C104,C105,C106), C201(C202,C203,C204,C205,C206)
7.c Idealised Me refined as rotating group:
 C44(H44A,H44B,H44C), C94(H94A,H94B,H94C), C107(H10A,H10B,H10C), C207(H20A,
 H20B,H20C)
;
_olex2_exptl_crystal_mounting_method oil
_olex2_submission_special_instructions 'No special instructions were received'