Synthesis of 3-aminoBODIPY dyes via copper-catalyzed vicarious nucleophilic substitution of 2-halogeno derivatives.
Knight, Julian G.; Alnoman, Rua B.; Waddell, Paul G.; Organic & biomolecular chemistry 13 (2015) 3819–3829; doi:10.1039/c4ob02626h

data_7154339
_publ_section_title
;
 Synthesis of 3-aminoBODIPY dyes via copper-catalyzed vicarious
 nucleophilic substitution of 2-halogeno derivatives.
;
_journal_issue                   12
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3819
_journal_page_last               3829
_journal_paper_doi               10.1039/c4ob02626h
_journal_volume                  13
_journal_year                    2015
_chemical_formula_moiety         'C22 H25 B F2 I N3 O'
_chemical_formula_sum            'C22 H25 B F2 I N3 O'
_chemical_formula_weight         523.16
_chemical_name_systematic
3-(Hexylamino)-6-iodo-8-(4-methoxyphenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-07-17
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Olex2 1.2-alpha
(compiled 2014.06.27 svn.r2953 for OlexSys, GUI svn.r4855)
;
_audit_update_record
;
2014-12-18 deposited with the CCDC.
2015-02-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.858(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.3219(4)
_cell_length_b                   17.3301(4)
_cell_length_c                   17.5462(5)
_cell_measurement_reflns_used    45394
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      28.3800
_cell_measurement_theta_min      3.5240
_cell_volume                     4353.7(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
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_computing_structure_solution    'XT (Sheldrick, 2008)'
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector_area_resol_mean 10.3968
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.916
_diffrn_measurement_details
;
  1 omega  -35.00   66.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.8289   38.0000  120.0000 101

  2 omega  -11.00   79.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       10.4695   38.0000  -90.0000 90

  3 omega   12.00   63.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       10.4695   77.0000   90.0000 51

  4 omega  -18.00   86.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       10.4695   77.0000    0.0000 104

  5 omega  -26.00   41.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       10.4695   19.0000 -120.0000 67

  6 omega  -23.00    4.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       10.4695   77.0000   90.0000 27

  7 omega  -62.00   43.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       12.0000  -62.0000 -111.3203 105

  8 omega   -7.00   51.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       12.0000  -91.0000   10.0707 58

  9 omega   -1.00   57.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       12.0000 -104.0000  172.0170 58

 10 omega  -88.00   25.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.8289  -77.0000   30.0000 113

 11 omega  -38.00   65.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.8289   57.0000 -180.0000 103

 12 omega  -68.00   44.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       10.4695  -77.0000  -30.0000 112

 13 omega  -65.00   37.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       10.4695  -38.0000    0.0000 102

 14 omega  -68.00  -17.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       10.4695  157.0000  -90.7343 51

 15 omega    8.00   39.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       10.4695 -112.0000   74.6108 31

 16 omega   13.00   66.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       12.0000 -119.0000 -121.7898 53
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0469529000
_diffrn_orient_matrix_UB_12      -0.0111432000
_diffrn_orient_matrix_UB_13      -0.0212751000
_diffrn_orient_matrix_UB_21      -0.0011265000
_diffrn_orient_matrix_UB_22      -0.0186725000
_diffrn_orient_matrix_UB_23      0.0356181000
_diffrn_orient_matrix_UB_31      -0.0157205000
_diffrn_orient_matrix_UB_32      0.0346639000
_diffrn_orient_matrix_UB_33      0.0123574000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0493
_diffrn_reflns_av_unetI/netI     0.0376
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.916
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            141938
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.915
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.580
_diffrn_reflns_theta_min         2.799
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.507
_exptl_absorpt_correction_T_max  0.925
_exptl_absorpt_correction_T_min  0.840
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.596
_exptl_crystal_description       block
_exptl_crystal_F_000             2096
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane/chloroform'
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.902
_refine_diff_density_min         -0.610
_refine_diff_density_rms         0.086
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.328(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1090
_refine_ls_number_reflns         21418
_refine_ls_number_restraints     973
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0483
_refine_ls_R_factor_gt           0.0323
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0268P)^2^+2.0757P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0602
_refine_ls_wR_factor_ref         0.0674
_reflns_Friedel_coverage         0.939
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.915
_reflns_number_gt                18203
_reflns_number_total             21418
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4ob02626h2.cif
_cod_data_source_block           jgk140009_fa
_cod_depositor_comments
'Adding full bibliography for 7154338--7154339.cif.'
_cod_database_code               7154339
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         'C22 H25 B1 N3 O1 F2 I1'
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.30
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,
 H22B), C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B), C44(H44A,H44B),
 C45(H45A,H45B), C64(H64A,H64B), C65(H65A,H65B), C66(H66A,H66B), C67(H67A,H67B),
  C68(H68A,H68B), C87(H87A,H87B), C88(H88A,H88B), C89(H89A,H89B), C90(H90A,
 H90B), C91(H91A,H91B)
3.b Aromatic/amide H refined with riding coordinates:
 N3(H3), N6(H6), N9(H9), N12(H12A), C1(H1), C5(H5), C7(H7), C12(H12), C13(H13),
  C15(H15), C16(H16), C24(H24), C25(H25), C28(H28), C30(H30), C35(H35),
 C36(H36), C38(H38), C39(H39), C47(H47), C48(H48), C51(H51), C53(H53), C58(H58),
  C59(H59), C61(H61), C62(H62), C70(H70), C71(H71), C74(H74), C76(H76),
 C81(H81), C82(H82), C84(H84), C85(H85), C2(H2)
3.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C23(H23A,H23B,H23C), C40(H40A,H40B,H40C), C46(H46A,H46B,
 H46C), C63(H63A,H63B,H63C), C69(H69A,H69B,H69C), C86(H86A,H86B,H86C), C92(H92A,
 H92B,H92C)
;
_shelx_res_checksum              77052
_olex2_submission_special_instructions 'No special instructions were received'