Dearomatization of Electron-Deficient Nitrogen Heterocycles via Cobalt-Catalyzed Asymmetric Cyclopropanation.
Joshi-Pangu, Amruta; Cohen, Ryan D.; Tudge, Matthew T.; Chen, Yonggang; The Journal of organic chemistry 81 (2016) 3070–3075; doi:10.1021/acs.joc.6b00322

data_4036698
_publ_section_title
;
 Dearomatization of Electron-Deficient Nitrogen Heterocycles via
 Cobalt-Catalyzed Asymmetric Cyclopropanation.
;
_journal_issue                   8
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              3070
_journal_page_last               3075
_journal_paper_doi               10.1021/acs.joc.6b00322
_journal_volume                  81
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C10 H9 Br Cl N3 O2'
_chemical_formula_sum            'C10 H9 Br Cl N3 O2'
_chemical_formula_weight         318.56
_chemical_name_systematic
; 
ethyl (6aS,7R,7aS)-3-bromo-6-chloro-6a,7a-dihydro-7H
-cyclopropa[d]imidazo[1,2-b]pyridazine-7-carboxylate
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2014
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   8.4770(3)
_cell_length_b                   10.9753(4)
_cell_length_c                   25.6472(9)
_cell_measurement_reflns_used    9831
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      66.64
_cell_measurement_theta_min      5.17
_cell_volume                     2386.15(15)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0308
_diffrn_reflns_av_unetI/netI     0.0184
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            27572
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.500
_diffrn_reflns_theta_max         66.631
_diffrn_reflns_theta_min         3.446
_diffrn_source                   'sealed-tube X-ray generator'
_exptl_absorpt_coefficient_mu    6.729
_exptl_absorpt_correction_T_max  0.817
_exptl_absorpt_correction_T_min  0.603
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
(SADABS; Sheldrick, 2003)
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.774
_exptl_crystal_description       'elongated needle'
_exptl_crystal_F_000             1264
_exptl_crystal_size_max          0.150
_exptl_crystal_size_mid          0.050
_exptl_crystal_size_min          0.030
_exptl_transmission_factor_max   0.7528
_exptl_transmission_factor_min   0.5555
_refine_diff_density_max         0.270
_refine_diff_density_min         -0.221
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
; 
 Flack x determined using 1760 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   -0.016(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     309
_refine_ls_number_reflns         4201
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0149
_refine_ls_R_factor_gt           0.0147
_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^)+(0.0190P)^2^+0.8566P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0374
_refine_ls_wR_factor_ref         0.0375
_reflns_Friedel_coverage         0.737
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                4167
_reflns_number_total             4201
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b00322_si_003.cif
_cod_data_source_block           mdj072
_cod_database_code               4036698
_shelx_estimated_absorpt_t_min   0.432
_shelx_estimated_absorpt_t_max   0.824
_shelxl_version_number           2014-3
_shelx_res_checksum              72969
_shelx_hkl_checksum              70265