Facile Friedel-Crafts alkylation of arenes under solvent-free conditions.
Chen, Feijing; Zhao, Xiao-Xiao; Zhang, Hao-Tian; Ma, Yan-Na; Chen, Xuenian; Organic & biomolecular chemistry 22 (2024) 2187–2191; doi:10.1039/d4ob00162a

data_7159812
_publ_section_title
;
 Facile Friedel-Crafts alkylation of arenes under solvent-free conditions.
;
_journal_issue                   11
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2187
_journal_page_last               2191
_journal_paper_doi               10.1039/d4ob00162a
_journal_volume                  22
_journal_year                    2024
_chemical_formula_moiety         'C17 H12 F3 N O2'
_chemical_formula_sum            'C17 H12 F3 N O2'
_chemical_formula_weight         319.28
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-12-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-01-29 deposited with the CCDC.	2024-02-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.316(8)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   34.085(2)
_cell_length_b                   11.9376(5)
_cell_length_c                   15.8740(12)
_cell_measurement_reflns_used    2764
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      68.1600
_cell_measurement_theta_min      3.9460
_cell_volume                     5975.3(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_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_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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   -107.00 -45.00   1.00    3.50    --  -33.50 178.00  90.00   62
  2  \w    -55.00  26.00   1.00    3.50    --  -33.50  37.00 150.00   81
  3  \w    -64.00 -22.00   1.00    3.50    --  -33.50 -19.00-180.00   42
  4  \w   -108.00 -74.00   1.00    3.50    --  -33.50 178.00   0.00   34
  5  \w    -55.00  23.00   1.00    3.50    --  -33.50  19.00  60.00   78
  6  \w     84.00 110.00   1.00    3.50    --   36.47 178.00 -90.00   26
  7  \w     62.00 146.00   1.00   17.50    --  108.00 178.00  60.00   84
  8  \w    102.00 161.00   1.00   17.50    --  108.00  77.00 -30.00   59
  9  \w     78.00 104.00   1.00   17.50    --  108.00-111.00-180.00   26
 10  \w    106.00 164.00   1.00   17.50    --  108.00  45.00  90.00   58
 11  \w     94.00 173.00   1.00   17.50    --  108.00  61.00-150.00   79
 12  \w     40.00 126.00   1.00   17.50    --  108.00 -61.00 120.00   86
 13  \w     48.00 109.00   1.00   17.50    --  108.00-111.00  90.00   61
 14  \w     94.00 176.00   1.00   17.50    --  108.00  61.00 -90.00   82
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0043732072
_diffrn_orient_matrix_UB_12      0.1049318681
_diffrn_orient_matrix_UB_13      -0.0593686737
_diffrn_orient_matrix_UB_21      -0.0324059550
_diffrn_orient_matrix_UB_22      -0.0618900818
_diffrn_orient_matrix_UB_23      -0.0822184017
_diffrn_orient_matrix_UB_31      -0.0363056536
_diffrn_orient_matrix_UB_32      0.0427322563
_diffrn_orient_matrix_UB_33      0.0268110799
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0369
_diffrn_reflns_av_unetI/netI     0.0547
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            11015
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         3.960
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.021
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74170
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.81a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.420
_exptl_crystal_description       cube
_exptl_crystal_F_000             2624
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.414
_refine_diff_density_min         -0.291
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     437
_refine_ls_number_reflns         5333
_refine_ls_number_restraints     97
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.1073
_refine_ls_R_factor_gt           0.0739
_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^)+(0.1105P)^2^+1.0053P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1964
_refine_ls_wR_factor_ref         0.2384
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3297
_reflns_number_total             5333
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00162a2.cif
_cod_data_source_block           202312335
_cod_depositor_comments          'Adding full bibliography for 7159812.cif.'
_cod_database_code               7159812
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C17H20N3O1
_shelx_estimated_absorpt_t_max   0.932
_shelx_estimated_absorpt_t_min   0.854
_reflns_odcompleteness_completeness 99.79
_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
2. Restrained distances
 F2-F3 \\sim F2-F1 \\sim F3-F1 \\sim F2A-F3A \\sim F2A-F1A
 with sigma of 0.04
 C16-F2 \\sim C16-F3 \\sim C16-F1 \\sim C16-F2A \\sim C16-F3A \\sim C16-F1A
 with sigma of 0.02
 F1'-F3' \\sim F1'-F2' \\sim F3'-F2' \\sim F1'A-F3'A \\sim F1'A-F2'A \\sim
F3'A-F2'A
 with sigma of 0.04
 C16'-F1' \\sim C16'-F3' \\sim C16'-F2' \\sim C16'-F1'A \\sim C16'-F3'A \\sim
C16'-F2'A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(F1'A) \\sim Ueq, Uanis(F1') \\sim Ueq, Uanis(F3'A) \\sim Ueq, Uanis(F3')
\\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F2A) \\sim Ueq, Uanis(F3A) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F2) = Uanis(F2A)
Uanis(F3) = Uanis(F3A)
Uanis(F1) = Uanis(F1A)
Uanis(F1') = Uanis(F1'A)
Uanis(F3') = Uanis(F3'A)
Uanis(F2') = Uanis(F2'A)
4. Others
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
 Sof(F1'A)=Sof(F2'A)=Sof(F3'A)=1-FVAR(2)
 Sof(F1')=Sof(F2')=Sof(F3')=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C11(H11), C13(H13), C14(H14),
 C15(H15), C1'(H1'), C2'(H2'), C3'(H3'), C4'(H4'), C5'(H5'), C11'(H11'),
 C13'(H13'), C14'(H14'), C15'(H15')
5.b Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C17'(H17D,H17E,H17F)
;
_shelx_res_checksum              84825
_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 1.292
_oxdiff_exptl_absorpt_empirical_full_min 0.798