Rh-Catalyzed regioselective C‒H activation and C‒C bond formation: synthesis and photophysical studies of indazolo[2,3-a]quinolines
Vivek Kumar, Sundaravel; Ellairaja, Sundaram; Satheesh, Vanaparthi; Sivasamy Vasantha, Vairathevar; Punniyamurthy, Tharmalingam; Organic Chemistry Frontiers 5 (2018) 2630–; doi:10.1039/C8QO00557E

data_1554368
_publ_section_title
;
 Rh-Catalyzed regioselective C--H activation and C--C bond formation:
 synthesis and photophysical studies of indazolo[2,3-a]quinolines
;
_journal_issue                   18
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              2630
_journal_paper_doi               10.1039/C8QO00557E
_journal_volume                  5
_journal_year                    2018
_chemical_compound_source        Synthesis
_chemical_formula_moiety         'C28 H17 F3 N2 O'
_chemical_formula_sum            'C28 H17 F3 N2 O1.01'
_chemical_formula_weight         454.59
_chemical_melting_point          380.15
_chemical_name_common
5,6-Diphenyl-3-(trifluoromethoxy)indazolo[2,3-a]quinoline
_chemical_name_systematic
5,6-Diphenyl-3-(trifluoromethoxy)indazolo[2,3-a]quinoline
_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             2018-01-13
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-01-16 deposited with the CCDC.
2018-07-11 downloaded from the CCDC.
;
_cell_angle_alpha                72.919(6)
_cell_angle_beta                 73.841(6)
_cell_angle_gamma                84.499(5)
_cell_formula_units_Z            2
_cell_length_a                   7.9330(6)
_cell_length_b                   11.1848(7)
_cell_length_c                   13.1762(10)
_cell_measurement_reflns_used    4527
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.4300
_cell_measurement_theta_min      1.9010
_cell_volume                     1073.26(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.7b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.7b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.7b (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_temperature      100.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_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   -110.00  70.00   0.50   10.00    --  -20.00   0.00 -36.00  360
  2  \w    -78.00  19.00   0.50   10.00    --  -20.00 -72.00-180.00  194
  3  \w    -89.00   7.00   0.50   10.00    --  -20.00 -72.00 -36.00  192
  4  \w    -57.50   4.00   0.50   10.00    --  -20.00  72.00 108.00  123
  5  \w    -15.00  15.00   0.50   10.00    --  -20.00  72.00-108.00   60
  6  \w   -110.00  70.00   0.50   10.00    --  -20.00   0.00  36.00  360
  7  \w    -94.50  19.00   0.50   10.00    --  -20.00 -72.00  36.00  227
  8  \w    -76.50  19.00   0.50   10.00    --  -20.00 -72.00-108.00  191
  9  \w    -43.50   1.00   0.50   10.00    --  -20.00  72.00-180.00   89
 10  \w     -9.00  21.50   0.50   10.00    --  -20.00  72.00 -36.00   61
 11  \w    -16.00  14.50   0.50   10.00    --  -20.00 -72.00 108.00   61
 12  \w   -110.00  28.50   0.50   10.00    --  -20.00   0.00-108.00  277
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0251285000
_diffrn_orient_matrix_UB_12      0.0635073000
_diffrn_orient_matrix_UB_13      -0.0171761000
_diffrn_orient_matrix_UB_21      0.0489783000
_diffrn_orient_matrix_UB_22      -0.0133808000
_diffrn_orient_matrix_UB_23      0.0397081000
_diffrn_orient_matrix_UB_31      0.0750825000
_diffrn_orient_matrix_UB_32      -0.0137916000
_diffrn_orient_matrix_UB_33      -0.0391816000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1169
_diffrn_reflns_av_unetI/netI     0.0832
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            21709
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         2.757
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.104
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56637
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear greenish green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.407
_exptl_crystal_description       prism
_exptl_crystal_F_000             468
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Acetonitrile+Dichloromethane'
_exptl_crystal_size_max          0.164
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.516
_refine_diff_density_min         -0.644
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     339
_refine_ls_number_reflns         3751
_refine_ls_number_restraints     90
_refine_ls_restrained_S_all      1.112
_refine_ls_R_factor_all          0.1282
_refine_ls_R_factor_gt           0.0827
_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^)+(0.1078P)^2^+0.3744P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1973
_refine_ls_wR_factor_ref         0.2309
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2394
_reflns_number_total             3751
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8qo00557e2.cif
_cod_data_source_block           vk52iitb
_cod_original_cell_volume        1073.27(14)
_cod_database_code               1554368
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C20H20N2O2F2
_shelx_estimated_absorpt_t_max   0.996
_shelx_estimated_absorpt_t_min   0.983
_reflns_odcompleteness_completeness 91.07
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.30
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C0AA-F1 \\sim C0AA-F2 \\sim C0AA-F3
 with sigma of 0.02
 O1-F2A \\sim O1-F3A \\sim F2A-F3A
 with sigma of 0.04
 C0AB-O1 \\sim C0AB-F1 \\sim C0AB-F2A \\sim C0AB-F3A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C0AA) \\sim Ueq, Uanis(C0AB) \\sim Ueq, Uanis(F2A) \\sim Ueq, Uanis(F2)
\\sim Ueq, Uanis(F3A) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F1) \\sim Ueq: with
sigma of 0.001 and sigma for terminal atoms of 0.002
4. Rigid body (RIGU) restrains
 F2, F3, F1, C0AA
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F2A, F3A, F1, C0AB
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C0AB)=Sof(F2A)=Sof(F3A)=1-FVAR(1)
 Sof(F2)=Sof(F3)=Sof(C0AA)=FVAR(1)
6.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C12(H12), C13(H13), C15(H15), C18(H18),
 C19(H19), C20(H20), C21(H21), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28)
;
_shelx_res_checksum              92996
_shelx_hkl_checksum              30200
_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 4.211
_oxdiff_exptl_absorpt_empirical_full_min 0.460