Aromatic Fluorine-Induced One-Pot Synthesis of Ring-Perfluorinated Trimethine Cyanine Dye and Its Remarkable Fluorescence Properties.
Funabiki, Kazumasa; Saito, Yuki; Kikuchi, Takashi; Yagi, Kazutaka; Kubota, Yasuhiro; Inuzuka, Toshiyasu; Miwa, Yohei; Yoshida, Michiyuki; Sakurada, Osamu; Kutsumizu, Shoichi; The Journal of organic chemistry 84 (2019) 4372–4380; doi:10.1021/acs.joc.9b00378

data_4034229
_publ_section_title
;
 Aromatic Fluorine-Induced One-Pot Synthesis of Ring-Perfluorinated
 Trimethine Cyanine Dye and Its Remarkable Fluorescence Properties.
;
_journal_issue                   7
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              4372
_journal_page_last               4380
_journal_paper_doi               10.1021/acs.joc.9b00378
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C F3 O3 S, C33 H33 N2, 0.13(H4 O2)'
_chemical_formula_sum            'C34 H33.5 F3 N2 O3.25 S'
_chemical_formula_weight         611.19
_space_group_crystal_system      orthorhombic
_space_group_IT_number           34
_space_group_name_Hall           'P 2 -2n'
_space_group_name_H-M_alt        'P n n 2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-10-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.94540(10)
_cell_length_b                   19.9965(4)
_cell_length_c                   10.65780(10)
_cell_measurement_reflns_used    7236
_cell_measurement_temperature    93
_cell_measurement_theta_max      75.5370
_cell_measurement_theta_min      4.3780
_cell_volume                     1480.19(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.16a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.16a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.16a (Rigaku OD, 2018)'
_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      93
_diffrn_detector                 'Rigaku HyPix-6000 area detector'
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HPC area detector'
_diffrn_measured_fraction_theta_full 1.000
_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    -79.00  46.00   0.50    0.50    --  -43.00  57.00  60.00  250
  2  \w    -79.00  46.00   0.50    0.50    --  -43.00  57.00 -90.00  250
  3  \w   -132.00  -7.00   0.50    0.50    --  -43.00 -57.00 120.00  250
  4  \w   -146.00 -21.00   0.50    0.80    -- -110.00  57.00 120.00  250
  5  \w   -146.00 -21.00   0.50    0.80    -- -110.00  57.00-120.00  250
  6  \w   -199.00 -71.00   0.50    0.80    -- -110.00 -72.00  30.00  256
  7  \w   -149.00 -21.00   0.50    0.80    -- -110.00  72.00-180.00  256
  8  \w   -199.00 -74.00   0.50    0.80    -- -110.00 -57.00 120.00  250
  9  \w   -199.00 -71.00   0.50    0.80    -- -110.00 -72.00 150.00  256
 10  \w   -132.00 -89.00   0.50    0.50    --  -43.00 -57.00-150.00   86
 11  \w   -132.00  -4.00   0.50    0.50    --  -43.00 -72.00 -30.00  256
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB PRO'
_diffrn_measurement_method       '\\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0555240000
_diffrn_orient_matrix_UB_12      -0.0123872000
_diffrn_orient_matrix_UB_13      -0.1380356000
_diffrn_orient_matrix_UB_21      0.1863339000
_diffrn_orient_matrix_UB_22      -0.0405780000
_diffrn_orient_matrix_UB_23      -0.0189374000
_diffrn_orient_matrix_UB_31      -0.1068441000
_diffrn_orient_matrix_UB_32      -0.0642833000
_diffrn_orient_matrix_UB_33      0.0385226000
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0196
_diffrn_reflns_av_unetI/netI     0.0188
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            10507
_diffrn_reflns_point_group_measured_fraction_full 0.970
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.842
_diffrn_reflns_theta_min         4.422
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_type              FR
_exptl_absorpt_coefficient_mu    1.470
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75676
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.16a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.371
_exptl_crystal_description       plate
_exptl_crystal_F_000             641
_exptl_crystal_size_max          0.285
_exptl_crystal_size_mid          0.238
_exptl_crystal_size_min          0.034
_refine_diff_density_max         0.545
_refine_diff_density_min         -0.276
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1224 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.009(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     236
_refine_ls_number_reflns         2896
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0347
_refine_ls_R_factor_gt           0.0338
_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^)+(0.0702P)^2^+0.1772P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0965
_refine_ls_wR_factor_ref         0.0976
_reflns_Friedel_coverage         0.793
_reflns_Friedel_fraction_full    0.936
_reflns_Friedel_fraction_max     0.879
_reflns_number_gt                2822
_reflns_number_total             2896
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00378_si_003.cif
_cod_data_source_block           2b
_cod_original_formula_sum        'C34 H33.50 F3 N2 O3.25 S'
_cod_database_code               4034229
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C34H33F3O3N2S
_chemical_oxdiff_usercomment     'sample 9'
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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 O(H,H) groups
2. Restrained distances
 H4B-F1
 1.7 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(S1) = Uanis(C18)
4. Others
 Fixed Sof: S1(0.5) O3(0.5) O2(0.5) O1(0.5) F2(0.5) C18(0.5) F1(0.5) F3(0.5)
 O4(0.125) H4A(0.125) H4B(0.125)
5.a Free rotating group:
 O4(H4A,H4B)
5.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C4(H4), C8(H8), C7(H7), C13(H13), C10(H10), C3(H3), C9(H9)
5.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C16(H16A,H16B,H16C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              71714
_shelx_hkl_checksum              49121
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.394
_oxdiff_exptl_absorpt_empirical_full_min 0.789