#------------------------------------------------------------------------------
#$Date: 2020-09-04 03:33:35 +0300 (Fri, 04 Sep 2020) $
#$Revision: 255869 $
#$URL: file:///home/coder/svn-repositories/cod/cif/4/13/52/4135206.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_4135206
loop_
_publ_author_name
'Levin, Mark D.'
'Ovian, John M.'
'Read, Jacquelyne A.'
'Sigman, Matthew S.'
'Jacobsen, Eric N.'
_publ_section_title
;
 Catalytic Enantioselective Synthesis of Difluorinated Alkyl Bromides.
;
_journal_issue                   35
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14831
_journal_page_last               14837
_journal_paper_doi               10.1021/jacs.0c07043
_journal_volume                  142
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_sum            'C18 H15 Br F2 N4 O2'
_chemical_formula_weight         437.25
_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'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 112.3222(18)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.6771(15)
_cell_length_b                   5.6603(7)
_cell_length_c                   13.2825(15)
_cell_measurement_reflns_used    3964
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.0
_cell_measurement_theta_min      3.12
_cell_volume                     881.68(18)
_computing_cell_refinement       'SAINT 8.37A (Bruker-AXS, 2015)'
_computing_data_reduction        'SAINT 8.37A (Bruker-AXS, 2015)'
_computing_molecular_graphics    'Bruker SHELXTL (Sheldrick, 2015)'
_computing_publication_material  'Bruker SHELXTL (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT-2014 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type
;
Bruker D8 goniometer with CCD area detector  
;
_diffrn_measurement_method       'omega and phi scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'I\mS microfocus tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0299
_diffrn_reflns_av_unetI/netI     0.0652
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            5582
_diffrn_reflns_point_group_measured_fraction_full 0.956
_diffrn_reflns_point_group_measured_fraction_max 0.935
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.108
_diffrn_reflns_theta_min         1.657
_exptl_absorpt_coefficient_mu    2.373
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.5647
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.647
_exptl_crystal_description       block
_exptl_crystal_F_000             440
_exptl_crystal_size_max          0.100
_exptl_crystal_size_mid          0.040
_exptl_crystal_size_min          0.020
_refine_diff_density_max         1.127
_refine_diff_density_min         -0.381
_refine_diff_density_rms         0.100
_refine_ls_abs_structure_details
;
 Flack x determined using 1028 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.004(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     245
_refine_ls_number_reflns         3654
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0683
_refine_ls_R_factor_gt           0.0505
_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/[σ²(Fo²)+(0.0656P)²+0.0622P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1106
_refine_ls_wR_factor_ref         0.1193
_reflns_Friedel_coverage         0.708
_reflns_Friedel_fraction_full    0.907
_reflns_Friedel_fraction_max     0.864
_reflns_number_gt                2999
_reflns_number_total             3654
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            ja0c07043_si_003.cif
_cod_data_source_block           MLII-99-2
_cod_depositor_comments          'Adding full bibliography for 4135206.cif.'
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4135206
_shelx_shelxl_version_number     2014/7
_shelx_space_group_comment
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_shelx_estimated_absorpt_t_min   0.797
_shelx_estimated_absorpt_t_max   0.954
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Br1 Br 0.02969(6) 0.67683(14) 0.81272(5) 0.0293(2) Uani 1 1 d . . . . .
F1 F 0.5043(3) 0.1961(11) 0.3682(3) 0.0326(10) Uani 1 1 d . . . . .
F2 F 0.4960(4) 0.5667(8) 0.4084(3) 0.0327(11) Uani 1 1 d . . . . .
O1 O 0.7017(5) 0.5123(10) -0.0264(5) 0.0324(13) Uani 1 1 d . . . . .
O2 O 0.7271(5) 0.8668(10) 0.0409(5) 0.0381(15) Uani 1 1 d . . . . .
N1 N 0.2181(4) 0.1459(12) 0.4368(4) 0.0188(13) Uani 1 1 d . . . . .
N2 N 0.2633(5) 0.1363(10) 0.3622(4) 0.0184(14) Uani 1 1 d . . . . .
N3 N 0.2861(5) 0.3619(10) 0.3428(5) 0.0178(12) Uani 1 1 d . . . . .
N4 N 0.6953(4) 0.6660(17) 0.0389(4) 0.0238(12) Uani 1 1 d . . . . .
C1 C 0.5329(6) 0.3180(12) 0.1716(6) 0.0199(15) Uani 1 1 d . . . . .
H1 H 0.4966 0.1690 0.1657 0.024 Uiso 1 1 calc R U . . .
C2 C 0.5878(6) 0.3759(13) 0.1009(5) 0.0201(15) Uani 1 1 d . . . . .
H2 H 0.5886 0.2695 0.0459 0.024 Uiso 1 1 calc R U . . .
C3 C 0.6404(6) 0.5933(12) 0.1144(6) 0.0195(14) Uani 1 1 d . . . . .
C4 C 0.6439(6) 0.7516(13) 0.1948(6) 0.0233(16) Uani 1 1 d . . . . .
H4 H 0.6836 0.8971 0.2027 0.028 Uiso 1 1 calc R U . . .
C5 C 0.5888(5) 0.6952(18) 0.2634(5) 0.0195(13) Uani 1 1 d . . . . .
H5 H 0.5895 0.8019 0.3188 0.023 Uiso 1 1 calc R U . . .
C6 C 0.5318(6) 0.4779(13) 0.2501(6) 0.0195(15) Uani 1 1 d . . . . .
C7 C 0.4673(6) 0.4125(13) 0.3224(6) 0.0235(16) Uani 1 1 d . . . . .
C8 C 0.3387(6) 0.4091(13) 0.2631(6) 0.0210(15) Uani 1 1 d . . . . .
H8 H 0.3190 0.2750 0.2101 0.025 Uiso 1 1 calc R U . . .
C9 C 0.2909(6) 0.6357(13) 0.1994(6) 0.0226(18) Uani 1 1 d . . . . .
H9A H 0.3099 0.7702 0.2509 0.027 Uiso 1 1 calc R U . . .
H9B H 0.3289 0.6634 0.1477 0.027 Uiso 1 1 calc R U . . .
C10 C 0.1640(6) 0.6308(15) 0.1371(6) 0.030(2) Uani 1 1 d . . . . .
H10A H 0.1406 0.7730 0.0920 0.045 Uiso 1 1 calc R U . . .
H10B H 0.1251 0.6259 0.1883 0.045 Uiso 1 1 calc R U . . .
H10C H 0.1435 0.4904 0.0905 0.045 Uiso 1 1 calc R U . . .
C11 C 0.2576(5) 0.5164(11) 0.4054(5) 0.0164(14) Uani 1 1 d . . . . .
H11 H 0.2662 0.6833 0.4081 0.020 Uiso 1 1 calc R U . . .
C12 C 0.2130(5) 0.3761(12) 0.4649(5) 0.0147(13) Uani 1 1 d . . . . .
C13 C 0.1668(6) 0.4482(12) 0.5467(5) 0.0171(14) Uani 1 1 d . . . . .
C14 C 0.1934(5) 0.6682(17) 0.5970(5) 0.0189(12) Uani 1 1 d . . . . .
H14 H 0.2403 0.7742 0.5771 0.023 Uiso 1 1 calc R U . . .
C15 C 0.1524(6) 0.7343(11) 0.6757(5) 0.0193(16) Uani 1 1 d . . . . .
H15 H 0.1715 0.8838 0.7103 0.023 Uiso 1 1 calc R U . . .
C16 C 0.0837(6) 0.5806(12) 0.7031(6) 0.0202(15) Uani 1 1 d . . . . .
C17 C 0.0542(6) 0.3644(12) 0.6539(6) 0.0205(15) Uani 1 1 d . . . . .
H17 H 0.0062 0.2612 0.6736 0.025 Uiso 1 1 calc R U . . .
C18 C 0.0953(5) 0.2977(12) 0.5750(5) 0.0164(14) Uani 1 1 d . . . . .
H18 H 0.0746 0.1487 0.5401 0.020 Uiso 1 1 calc R U . . .
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N2 N1 C12 108.9(6) . . ?
N1 N2 N3 106.8(6) . . ?
C11 N3 N2 111.6(5) . . ?
C11 N3 C8 128.7(6) . . ?
N2 N3 C8 119.6(5) . . ?
O2 N4 O1 124.2(6) . . ?
O2 N4 C3 119.2(7) . . ?
O1 N4 C3 116.6(8) . . ?
C6 C1 C2 120.0(6) . . ?
C6 C1 H1 120.0 . . ?
C2 C1 H1 120.0 . . ?
C3 C2 C1 117.4(6) . . ?
C3 C2 H2 121.3 . . ?
C1 C2 H2 121.3 . . ?
C2 C3 C4 123.5(7) . . ?
C2 C3 N4 119.2(7) . . ?
C4 C3 N4 117.3(6) . . ?
C5 C4 C3 119.0(7) . . ?
C5 C4 H4 120.5 . . ?
C3 C4 H4 120.5 . . ?
C4 C5 C6 119.1(7) . . ?
C4 C5 H5 120.5 . . ?
C6 C5 H5 120.5 . . ?
C1 C6 C5 121.0(6) . . ?
C1 C6 C7 118.5(6) . . ?
C5 C6 C7 120.5(6) . . ?
F1 C7 F2 105.1(5) . . ?
F1 C7 C8 109.8(6) . . ?
F2 C7 C8 109.4(5) . . ?
F1 C7 C6 108.8(5) . . ?
F2 C7 C6 109.5(6) . . ?
C8 C7 C6 113.8(6) . . ?
N3 C8 C7 108.6(6) . . ?
N3 C8 C9 110.9(5) . . ?
C7 C8 C9 113.5(6) . . ?
N3 C8 H8 107.9 . . ?
C7 C8 H8 107.9 . . ?
C9 C8 H8 107.9 . . ?
C10 C9 C8 113.9(6) . . ?
C10 C9 H9A 108.8 . . ?
C8 C9 H9A 108.8 . . ?
C10 C9 H9B 108.8 . . ?
C8 C9 H9B 108.8 . . ?
H9A C9 H9B 107.7 . . ?
C9 C10 H10A 109.5 . . ?
C9 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
C9 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
N3 C11 C12 104.1(6) . . ?
N3 C11 H11 127.9 . . ?
C12 C11 H11 127.9 . . ?
N1 C12 C11 108.6(6) . . ?
N1 C12 C13 122.7(6) . . ?
C11 C12 C13 128.7(6) . . ?
C14 C13 C18 118.7(6) . . ?
C14 C13 C12 120.7(6) . . ?
C18 C13 C12 120.7(6) . . ?
C15 C14 C13 120.8(7) . . ?
C15 C14 H14 119.6 . . ?
C13 C14 H14 119.6 . . ?
C16 C15 C14 119.1(7) . . ?
C16 C15 H15 120.4 . . ?
C14 C15 H15 120.4 . . ?
C17 C16 C15 121.6(6) . . ?
C17 C16 Br1 120.5(6) . . ?
C15 C16 Br1 118.0(5) . . ?
C16 C17 C18 119.4(7) . . ?
C16 C17 H17 120.3 . . ?
C18 C17 H17 120.3 . . ?
C17 C18 C13 120.4(6) . . ?
C17 C18 H18 119.8 . . ?
C13 C18 H18 119.8 . . ?
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Br1 C16 1.908(7) . ?
F1 C7 1.369(9) . ?
F2 C7 1.373(8) . ?
O1 N4 1.253(9) . ?
O2 N4 1.203(10) . ?
N1 N2 1.320(7) . ?
N1 C12 1.364(9) . ?
N2 N3 1.355(8) . ?
N3 C11 1.347(8) . ?
N3 C8 1.475(8) . ?
N4 C3 1.480(8) . ?
C1 C6 1.384(10) . ?
C1 C2 1.403(9) . ?
C1 H1 0.9500 . ?
C2 C3 1.379(10) . ?
C2 H2 0.9500 . ?
C3 C4 1.381(9) . ?
C4 C5 1.379(9) . ?
C4 H4 0.9500 . ?
C5 C6 1.403(12) . ?
C5 H5 0.9500 . ?
C6 C7 1.524(10) . ?
C7 C8 1.518(10) . ?
C8 C9 1.529(10) . ?
C8 H8 1.0000 . ?
C9 C10 1.505(10) . ?
C9 H9A 0.9900 . ?
C9 H9B 0.9900 . ?
C10 H10A 0.9800 . ?
C10 H10B 0.9800 . ?
C10 H10C 0.9800 . ?
C11 C12 1.384(9) . ?
C11 H11 0.9500 . ?
C12 C13 1.473(9) . ?
C13 C14 1.393(12) . ?
C13 C18 1.396(9) . ?
C14 C15 1.384(9) . ?
C14 H14 0.9500 . ?
C15 C16 1.374(10) . ?
C15 H15 0.9500 . ?
C16 C17 1.371(10) . ?
C17 C18 1.387(9) . ?
C17 H17 0.9500 . ?
C18 H18 0.9500 . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C12 N1 N2 N3 -0.3(7) . . . . ?
N1 N2 N3 C11 0.9(7) . . . . ?
N1 N2 N3 C8 179.4(5) . . . . ?
C6 C1 C2 C3 0.9(10) . . . . ?
C1 C2 C3 C4 1.6(10) . . . . ?
C1 C2 C3 N4 -177.5(6) . . . . ?
O2 N4 C3 C2 169.8(7) . . . . ?
O1 N4 C3 C2 -7.8(9) . . . . ?
O2 N4 C3 C4 -9.4(9) . . . . ?
O1 N4 C3 C4 172.9(6) . . . . ?
C2 C3 C4 C5 -2.4(10) . . . . ?
N4 C3 C4 C5 176.8(6) . . . . ?
C3 C4 C5 C6 0.6(10) . . . . ?
C2 C1 C6 C5 -2.6(10) . . . . ?
C2 C1 C6 C7 177.6(6) . . . . ?
C4 C5 C6 C1 1.9(10) . . . . ?
C4 C5 C6 C7 -178.3(6) . . . . ?
C1 C6 C7 F1 52.7(8) . . . . ?
C5 C6 C7 F1 -127.0(7) . . . . ?
C1 C6 C7 F2 167.2(6) . . . . ?
C5 C6 C7 F2 -12.6(9) . . . . ?
C1 C6 C7 C8 -70.0(8) . . . . ?
C5 C6 C7 C8 110.2(7) . . . . ?
C11 N3 C8 C7 86.8(8) . . . . ?
N2 N3 C8 C7 -91.4(7) . . . . ?
C11 N3 C8 C9 -38.6(10) . . . . ?
N2 N3 C8 C9 143.3(6) . . . . ?
F1 C7 C8 N3 62.1(7) . . . . ?
F2 C7 C8 N3 -52.8(7) . . . . ?
C6 C7 C8 N3 -175.7(6) . . . . ?
F1 C7 C8 C9 -174.1(5) . . . . ?
F2 C7 C8 C9 71.0(7) . . . . ?
C6 C7 C8 C9 -51.9(8) . . . . ?
N3 C8 C9 C10 -59.4(8) . . . . ?
C7 C8 C9 C10 177.9(6) . . . . ?
N2 N3 C11 C12 -1.1(7) . . . . ?
C8 N3 C11 C12 -179.4(6) . . . . ?
N2 N1 C12 C11 -0.3(7) . . . . ?
N2 N1 C12 C13 -179.9(6) . . . . ?
N3 C11 C12 N1 0.9(7) . . . . ?
N3 C11 C12 C13 -179.6(6) . . . . ?
N1 C12 C13 C14 160.4(6) . . . . ?
C11 C12 C13 C14 -19.1(10) . . . . ?
N1 C12 C13 C18 -19.8(10) . . . . ?
C11 C12 C13 C18 160.7(7) . . . . ?
C18 C13 C14 C15 1.7(9) . . . . ?
C12 C13 C14 C15 -178.5(6) . . . . ?
C13 C14 C15 C16 -0.7(10) . . . . ?
C14 C15 C16 C17 -0.4(10) . . . . ?
C14 C15 C16 Br1 179.5(5) . . . . ?
C15 C16 C17 C18 0.5(10) . . . . ?
Br1 C16 C17 C18 -179.5(5) . . . . ?
C16 C17 C18 C13 0.6(10) . . . . ?
C14 C13 C18 C17 -1.7(9) . . . . ?
C12 C13 C18 C17 178.5(6) . . . . ?
