Phosphine-Catalyzed [3+2] Cycloaddition of Phthalazinium Dicyanomethanides with Allenoates: Highly Efficient Synthesis of 1,2,3,10b-Tetrahydropyrrolo[2,1-a]phthalazine Derivatives
Guo, Hongchao; Zhou, Leijie; Sun, Zhanhu; Yuan, Chunhao; RSC Adv.  (2016) –; doi:10.1039/C6RA13643E

data_7226217
_publ_section_title
;
 Phosphine-Catalyzed [3+2] Cycloaddition of Phthalazinium
 Dicyanomethanides with Allenoates: Highly Efficient Synthesis of
 1,2,3,10b-Tetrahydropyrrolo[2,1-a]phthalazine Derivatives
;
_journal_name_full               'RSC Adv.'
_journal_paper_doi               10.1039/C6RA13643E
_journal_year                    2016
_chemical_formula_moiety         'C24 H19 Br N4 O2'
_chemical_formula_sum            'C24 H19 Br N4 O2'
_chemical_formula_weight         475.34
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2014-09-05
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_audit_update_record
;
2016-03-12 deposited with the CCDC.
2016-08-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.444(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.775(2)
_cell_length_b                   16.891(3)
_cell_length_c                   14.538(4)
_cell_measurement_reflns_used    5740
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4822
_cell_measurement_theta_min      2.4116
_cell_volume                     2150.9(9)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2007)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2013)'
_computing_structure_solution
;
'SHELXS (Sheldrick, 2013)'

;
_diffrn_ambient_temperature      173.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device
;
Saturn724+ (2x2 bin mode)
;
_diffrn_measurement_device_details
;
AFC10: Fixed Chi 2 circle
;
_diffrn_measurement_device_type  'MM007-HF CCD(Saturn 724+)'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      -0.0134
_diffrn_orient_matrix_UB_12      0.0051
_diffrn_orient_matrix_UB_13      -0.1133
_diffrn_orient_matrix_UB_21      -0.0479
_diffrn_orient_matrix_UB_22      -0.0346
_diffrn_orient_matrix_UB_23      0.0041
_diffrn_orient_matrix_UB_31      -0.0401
_diffrn_orient_matrix_UB_32      0.0560
_diffrn_orient_matrix_UB_33      0.0031
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0368
_diffrn_reflns_av_unetI/netI     0.0321
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            15229
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.477
_diffrn_reflns_theta_min         2.412
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    1.940
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7571
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.468
_exptl_crystal_description       block
_exptl_crystal_F_000             968
_exptl_crystal_size_max          0.266
_exptl_crystal_size_mid          0.188
_exptl_crystal_size_min          0.159
_refine_diff_density_max         0.291
_refine_diff_density_min         -0.261
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.184
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     366
_refine_ls_number_reflns         4899
_refine_ls_number_restraints     306
_refine_ls_restrained_S_all      1.161
_refine_ls_R_factor_all          0.0622
_refine_ls_R_factor_gt           0.0504
_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^)+(0.0380P)^2^+1.1091P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1064
_refine_ls_wR_factor_ref         0.1130
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4187
_reflns_number_total             4899
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6ra13643e2.cif
_cod_data_source_block           sa3602
_cod_database_code               7226217
_shelxl_version_number           2013-4
_diffrn_number_total             5080
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C17A-C16 = C21A-C16 = C18A-C17A = C19A-C18A = C20A-C19A = C21A-C20A
 1.39 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O2 \\sim O2A \\sim C13A \\sim C14A \\sim C14 \\sim C13: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.04
Br1 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim Br1A \\sim C20A
\\sim C19A \\sim C18A \\sim C17A \\sim C21A: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.04
Uanis(Br1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O2) \\sim Ueq, Uanis(O2A) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C13A)
\\sim Ueq, Uanis(C14A) \\sim Ueq, Uanis(C14) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(Br1) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C19)
\\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(Br1A) \\sim Ueq,
Uanis(C20A) \\sim Ueq, Uanis(C19A) \\sim Ueq, Uanis(C18A) \\sim Ueq,
Uanis(C17A) \\sim Ueq, Uanis(C21A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Sof(O2A)=Sof(C13A)=Sof(H13C)=Sof(H13D)=Sof(C14A)=Sof(H14D)=Sof(H14E)=
 Sof(H14F)=1-FVAR(1)
 Sof(O2)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=
 FVAR(1)
 Sof(Br1A)=Sof(C20A)=Sof(H20A)=Sof(C19A)=Sof(C18A)=Sof(H18A)=1-FVAR(2)
 Sof(Br1)=Sof(C18)=Sof(H18)=Sof(C19)=Sof(C20)=Sof(H20)=FVAR(2)
 Sof(C17A)=Sof(H17A)=Sof(C21A)=Sof(H21A)=1-FVAR(3)
 Sof(C17)=Sof(H17)=Sof(C21)=Sof(H21)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C4(H4)
5.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C15(H15A,H15B), C13A(H13C,H13D)
5.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C11(H11), C17(H17), C18(H18), C20(H20),
 C21(H21), C20A(H20A), C18A(H18A), C17A(H17A), C21A(H21A)
5.d X=CH2 refined with riding coordinates:
 C22(H22A,H22B)
5.e Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C14A(H14D,H14E,H14F)
;
_shelx_res_checksum              31469