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_7154338
_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 H26 B F2 N3 O'
_chemical_formula_sum            'C22 H26 B F2 N3 O'
_chemical_formula_weight         397.27
_chemical_melting_point          475
_chemical_name_systematic
3-(Hexylamino)-8-(4-methoxyphenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-05-07
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2014.03.20 svn.r2918 for OlexSys, GUI svn.r4816)
;
_audit_update_record
;
2014-12-18 deposited with the CCDC.
2015-02-16 downloaded from the CCDC.
;
_cell_angle_alpha                97.195(5)
_cell_angle_beta                 91.225(6)
_cell_angle_gamma                113.239(7)
_cell_formula_units_Z            2
_cell_length_a                   9.8145(8)
_cell_length_b                   10.0842(6)
_cell_length_c                   11.3461(7)
_cell_measurement_reflns_used    3621
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      26.2390
_cell_measurement_theta_min      3.7370
_cell_volume                     1020.62(13)
_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
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
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)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector_area_resol_mean 10.3968
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.863
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0192572000
_diffrn_orient_matrix_UB_12      0.0081199000
_diffrn_orient_matrix_UB_13      0.0618820000
_diffrn_orient_matrix_UB_21      0.0691676000
_diffrn_orient_matrix_UB_22      -0.0032511000
_diffrn_orient_matrix_UB_23      -0.0126627000
_diffrn_orient_matrix_UB_31      0.0326893000
_diffrn_orient_matrix_UB_32      0.0768756000
_diffrn_orient_matrix_UB_33      0.0021850000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0489
_diffrn_reflns_av_unetI/netI     0.0536
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.863
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_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            16496
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.863
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.924
_diffrn_reflns_theta_min         2.966
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.092
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            'light orange'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.293
_exptl_crystal_description       prism
_exptl_crystal_F_000             420
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane/chloroform'
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.223
_refine_diff_density_min         -0.219
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     284
_refine_ls_number_reflns         4654
_refine_ls_number_restraints     45
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0902
_refine_ls_R_factor_gt           0.0504
_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^)+(0.0369P)^2^+0.3233P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0951
_refine_ls_wR_factor_ref         0.1157
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3086
_reflns_number_total             4654
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4ob02626h2.cif
_cod_data_source_block           jgk140003
_cod_depositor_comments
'Adding full bibliography for 7154338--7154339.cif.'
_cod_database_code               7154338
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C22 H26 N3 O1 B1 F2'
_reflns_odcompleteness_completeness 99.84
_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 C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C20B-C19B \\sim C21B-C20B \\sim C21B-C22B \\sim C23B-C22B \\sim C20A-C19A
\\sim C21A-C20A \\sim C21A-
 C22A \\sim C23A-C22A \\sim C19A-C18 \\sim C19B-C18
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C19A) = Uanis(C19B)
Uanis(C20A) = Uanis(C20B)
Uanis(C21A) = Uanis(C21B)
Uanis(C22A) = Uanis(C22B)
Uanis(C23A) = Uanis(C23B)
4. Others
 Sof(C23B)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(H18C)=Sof(H18D)=Sof(C22B)=
 Sof(H22C)=Sof(H22D)=Sof(C19B)=Sof(H19C)=Sof(H19D)=Sof(C20B)=Sof(H20C)=
 Sof(H20D)=Sof(C21B)=Sof(H21C)=Sof(H21D)=1-FVAR(1)
 Sof(H18A)=Sof(H18B)=Sof(C22A)=Sof(H22A)=Sof(H22B)=Sof(C19A)=Sof(H19A)=
 Sof(H19B)=Sof(C20A)=Sof(H20A)=Sof(H20B)=Sof(C21A)=Sof(H21A)=Sof(H21B)=
 Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C18(H18C,H18D), C22A(H22A,H22B), C22B(H22C,H22D), C19A(H19A,
 H19B), C19B(H19C,H19D), C20A(H20A,H20B), C20B(H20C,H20D), C21A(H21A,H21B),
 C21B(H21C,H21D)
5.b Aromatic/amide H refined with riding coordinates:
 C15(H15), C12(H12), C13(H13), C16(H16), C5(H5), C1(H1), C7(H7), C6(H6), C2(H2)
5.c Idealised Me refined as rotating group:
 C23B(H23A,H23B,H23C), C17(H17A,H17B,H17C), C23A(H23D,H23E,H23F)
;
_shelx_res_checksum              99018