Flipping the Switch: Fast Photoisomerization in a Confined Environment.
Williams, Derek E.; Martin, Corey R.; Dolgopolova, Ekaterina A.; Swifton, Anton; Godfrey, Danielle C.; Ejegbavwo, Otega A.; Pellechia, Perry J.; Smith, Mark D.; Shustova, Natalia B.; Journal of the American Chemical Society 140 (2018) 7611–7622; doi:10.1021/jacs.8b02994

data_4132348
_publ_section_title
;
 Flipping the Switch: Fast Photoisomerization in a Confined Environment.
;
_journal_issue                   24
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7611
_journal_page_last               7622
_journal_paper_doi               10.1021/jacs.8b02994
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C19 H16 Br2 N2 O3'
_chemical_formula_sum            'C19 H16 Br2 N2 O3'
_chemical_formula_weight         480.16
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-12-13
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.7950(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.3937(3)
_cell_length_b                   33.5488(13)
_cell_length_c                   11.4358(4)
_cell_measurement_reflns_used    9121
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.940
_cell_measurement_theta_min      2.487
_cell_volume                     3599.7(2)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker APEX3 v2016.5-0 (Bruker, 2016)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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      100(2)
_diffrn_detector                 'Bruker PHOTON-100 area detector'
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 QUEST'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0551
_diffrn_reflns_av_unetI/netI     0.0274
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       47
_diffrn_reflns_limit_k_min       -47
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            177181
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        30.215
_diffrn_reflns_theta_max         30.217
_diffrn_reflns_theta_min         2.157
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.526
_exptl_absorpt_correction_T_max  0.3807
_exptl_absorpt_correction_T_min  0.2775
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0803 before and 0.0553 after correction.
The Ratio of minimum to maximum transmission is 0.7289.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.772
_exptl_crystal_description       plate
_exptl_crystal_F_000             1904
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.665
_refine_diff_density_min         -1.009
_refine_diff_density_rms         0.120
_refine_ls_extinction_coef       0.00141(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.329
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     653
_refine_ls_number_reflns         10644
_refine_ls_number_restraints     516
_refine_ls_restrained_S_all      1.299
_refine_ls_R_factor_all          0.0681
_refine_ls_R_factor_gt           0.0553
_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^)+17.9284P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1117
_refine_ls_wR_factor_ref         0.1149
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9114
_reflns_number_total             10644
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b02994_si_007.cif
_cod_data_source_block           cmr1_51
_cod_database_code               4132348
_shelx_estimated_absorpt_t_max   0.550
_shelx_estimated_absorpt_t_min   0.386
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained planarity
 C3D, C4D, C5D, C6D, C7D, C8D
 with sigma of 0.01
 C3C, C4C, C5C, C6C, C7C, C8C
 with sigma of 0.01
 C3B, C4B, C5B, C6B, C7B, C8B
 with sigma of 0.01
 O1C, N2C, C12C, C13C, C14C, C15C, C16C, C17C, C18C, C19C
 with sigma of 0.1
 O1B, N2B, C12B, C13B, C14B, C15B, C16B, C17B, C18B, C19B
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
Uanis(C19B) \\sim Ueq, Uanis(C19C) \\sim Ueq, Uanis(C19D) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C8B) \\sim Ueq, Uanis(C3C) \\sim Ueq, Uanis(C8D) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(O3B) = Uanis(O3C) = Uanis(O3D)
Uanis(N2B) = Uanis(N2C) = Uanis(N2D)
Uanis(O2B) = Uanis(O2C) = Uanis(O2D)
Uanis(C16B) = Uanis(C16C) = Uanis(C16D)
Uanis(C17B) = Uanis(C17C) = Uanis(C17D)
Uanis(C18B) = Uanis(C18C) = Uanis(C18D)
Uanis(C14B) = Uanis(C14C) = Uanis(C14D)
Uanis(C15B) = Uanis(C15C) = Uanis(C15D)
Uanis(C13B) = Uanis(C13C) = Uanis(C13D)
Uanis(C12B) = Uanis(C12C) = Uanis(C12D)
Uanis(C5C) = Uanis(C6B) = Uanis(C6D)
Uanis(C7C) = Uanis(C4B) = Uanis(C4D)
Uanis(C6C) = Uanis(C5B) = Uanis(C5D)
Uanis(C3B) = Uanis(C8C) = Uanis(C3D)
Uanis(C8B) = Uanis(C3C) = Uanis(C8D)
Uanis(N1B) = Uanis(C2C) = Uanis(N1D)
Uanis(C2B) = Uanis(N1C) = Uanis(C2D)
Uanis(C9B) = Uanis(C10B) = Uanis(C11C) = Uanis(C9D) = Uanis(C10D)
Uanis(C11B) = Uanis(C9C) = Uanis(C10C) = Uanis(C11D)
Uanis(C4C) = Uanis(C7D) = Uanis(C7B)
Uanis(C1B) = Uanis(C1C) = Uanis(C1D)
Uanis(Br1C) = Uanis(Br2D)
Uanis(O1B) = Uanis(O1C) = Uanis(O1D)
Uanis(C19B) = Uanis(C19C) = Uanis(C19D)
4. Same fragment restrains
{Br1A, Br2A, O1A, O2A, O3A, N1A, N2A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A,
C9A, C10A, C11A, C12A, C13A, C14A, C15A, C16A, C17A, C18A, C19A} sigma for 1-2:
0.01, 1-3: 0.04
as
{Br1B, Br2B, O1B, O2B, O3B, N1B, N2B, C1B, C2B, C3B, C4B, C5B, C6B, C7B, C8B,
C9B, C10B, C11B, C12B, C13B, C14B, C15B, C16B, C17B, C18B, C19B}
{Br1A, Br2A, O1A, O2A, O3A, N1A, N2A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A,
C9A, C10A, C11A, C12A, C13A, C14A, C15A, C16A, C17A, C18A, C19A} sigma for 1-2:
0.01, 1-3: 0.04
as
{Br1C, Br2C, O1C, O2C, O3C, N1C, N2C, C1C, C2C, C3C, C4C, C5C, C6C, C7C, C8C,
C9C, C10C, C11C, C12C, C13C, C14C, C15C, C16C, C17C, C18C, C19C}
{Br1A, Br2A, O1A, O2A, O3A, N1A, N2A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A,
C9A, C10A, C11A, C12A, C13A, C14A, C15A, C16A, C17A, C18A, C19A} sigma for 1-2:
0.01, 1-3: 0.04
as
{Br1D, Br2D, O1D, O2D, O3D, N1D, N2D, C1D, C2D, C3D, C4D, C5D, C6D, C7D, C8D,
C9D, C10D, C11D, C12D, C13D, C14D, C15D, C16D, C17D, C18D, C19D}
5. Others
 1*[Sof(Br1B)+Sof(Br2B)+Sof(O1B)+Sof(O2B)+Sof(O3B)+Sof(N1B)+Sof(N2B)+Sof(C1B)+
 Sof(C2B)+Sof(C3B)+Sof(C4B)+Sof(C5B)+Sof(H5B)+Sof(C6B)+Sof(H6B)+Sof(C7B)+
 Sof(C8B)+Sof(C9B)+Sof(H9BA)+Sof(H9BB)+Sof(H9BC)+Sof(C10B)+Sof(H10D)+Sof(H10E)+
 Sof(H10F)+Sof(C11B)+Sof(H11D)+Sof(H11E)+Sof(H11F)+Sof(C12B)+Sof(H12B)+
 Sof(C13B)+Sof(H13B)+Sof(C14B)+Sof(C15B)+Sof(H15B)+Sof(C16B)+Sof(C17B)+
 Sof(H17B)+Sof(C18B)+Sof(H18B)+Sof(C19B)]+1*[Sof(Br1C)+Sof(Br2C)+Sof(O1C)+
 Sof(O2C)+Sof(O3C)+Sof(N1C)+Sof(N2C)+Sof(C1C)+Sof(C2C)+Sof(C3C)+Sof(C4C)+
 Sof(C5C)+Sof(H5C)+Sof(C6C)+Sof(H6C)+Sof(C7C)+Sof(C8C)+Sof(C9C)+Sof(H9CA)+
 Sof(H9CB)+Sof(H9CC)+Sof(C10C)+Sof(H10G)+Sof(H10H)+Sof(H10I)+Sof(C11C)+
 Sof(H11G)+Sof(H11H)+Sof(H11I)+Sof(C12C)+Sof(H12C)+Sof(C13C)+Sof(H13C)+
 Sof(C14C)+Sof(C15C)+Sof(H15C)+Sof(C16C)+Sof(C17C)+Sof(H17C)+Sof(C18C)+
 Sof(H18C)+Sof(C19C)]+1*[Sof(Br1D)+Sof(Br2D)+Sof(O1D)+Sof(O2D)+Sof(O3D)+
 Sof(N1D)+Sof(N2D)+Sof(C1D)+Sof(C2D)+Sof(C3D)+Sof(C4D)+Sof(C5D)+Sof(H5D)+
 Sof(C6D)+Sof(H6D)+Sof(C7D)+Sof(C8D)+Sof(C9D)+Sof(H9DA)+Sof(H9DB)+Sof(H9DC)+
 Sof(C10D)+Sof(H10J)+Sof(H10K)+Sof(H10L)+Sof(C11D)+Sof(H11J)+Sof(H11K)+
 Sof(H11L)+Sof(C12D)+Sof(H12D)+Sof(C13D)+Sof(H13D)+Sof(C14D)+Sof(C15D)+
 Sof(H15D)+Sof(C16D)+Sof(C17D)+Sof(H17D)+Sof(C18D)+Sof(H18D)+Sof(C19D)]=1 with
 esd of 0.00001
 Sof(Br1B)=Sof(Br2B)=Sof(O1B)=Sof(O2B)=Sof(O3B)=Sof(N1B)=Sof(N2B)=Sof(C1B)=
 Sof(C2B)=Sof(C3B)=Sof(C4B)=Sof(C5B)=Sof(H5B)=Sof(C6B)=Sof(H6B)=Sof(C7B)=
 Sof(C8B)=Sof(C9B)=Sof(H9BA)=Sof(H9BB)=Sof(H9BC)=Sof(C10B)=Sof(H10D)=Sof(H10E)=
 Sof(H10F)=Sof(C11B)=Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(C12B)=Sof(H12B)=
 Sof(C13B)=Sof(H13B)=Sof(C14B)=Sof(C15B)=Sof(H15B)=Sof(C16B)=Sof(C17B)=
 Sof(H17B)=Sof(C18B)=Sof(H18B)=Sof(C19B)=FVAR(1)
 Sof(Br1C)=Sof(Br2C)=Sof(O1C)=Sof(O2C)=Sof(O3C)=Sof(N1C)=Sof(N2C)=Sof(C1C)=
 Sof(C2C)=Sof(C3C)=Sof(C4C)=Sof(C5C)=Sof(H5C)=Sof(C6C)=Sof(H6C)=Sof(C7C)=
 Sof(C8C)=Sof(C9C)=Sof(H9CA)=Sof(H9CB)=Sof(H9CC)=Sof(C10C)=Sof(H10G)=Sof(H10H)=
 Sof(H10I)=Sof(C11C)=Sof(H11G)=Sof(H11H)=Sof(H11I)=Sof(C12C)=Sof(H12C)=
 Sof(C13C)=Sof(H13C)=Sof(C14C)=Sof(C15C)=Sof(H15C)=Sof(C16C)=Sof(C17C)=
 Sof(H17C)=Sof(C18C)=Sof(H18C)=Sof(C19C)=FVAR(2)
 Sof(Br1D)=Sof(Br2D)=Sof(O1D)=Sof(O2D)=Sof(O3D)=Sof(N1D)=Sof(N2D)=Sof(C1D)=
 Sof(C2D)=Sof(C3D)=Sof(C4D)=Sof(C5D)=Sof(H5D)=Sof(C6D)=Sof(H6D)=Sof(C7D)=
 Sof(C8D)=Sof(C9D)=Sof(H9DA)=Sof(H9DB)=Sof(H9DC)=Sof(C10D)=Sof(H10J)=Sof(H10K)=
 Sof(H10L)=Sof(C11D)=Sof(H11J)=Sof(H11K)=Sof(H11L)=Sof(C12D)=Sof(H12D)=
 Sof(C13D)=Sof(H13D)=Sof(C14D)=Sof(C15D)=Sof(H15D)=Sof(C16D)=Sof(C17D)=
 Sof(H17D)=Sof(C18D)=Sof(H18D)=Sof(C19D)=FVAR(3)
6.a Aromatic/amide H refined with riding coordinates:
 C5A(H5A), C6A(H6A), C12A(H12A), C13A(H13A), C15A(H15A), C17A(H17A),
 C18A(H18A), C5B(H5B), C6B(H6B), C12B(H12B), C13B(H13B), C15B(H15B), C17B(H17B),
  C18B(H18B), C5C(H5C), C6C(H6C), C12C(H12C), C13C(H13C), C15C(H15C),
 C17C(H17C), C18C(H18C), C5D(H5D), C6D(H6D), C12D(H12D), C13D(H13D), C15D(H15D),
  C17D(H17D), C18D(H18D)
6.b Idealised Me refined as rotating group:
 C9A(H9AA,H9AB,H9AC), C10A(H10A,H10B,H10C), C11A(H11A,H11B,H11C), C9B(H9BA,
 H9BB,H9BC), C10B(H10D,H10E,H10F), C11B(H11D,H11E,H11F), C9C(H9CA,H9CB,H9CC),
 C10C(H10G,H10H,H10I), C11C(H11G,H11H,H11I), C9D(H9DA,H9DB,H9DC), C10D(H10J,
 H10K,H10L), C11D(H11J,H11K,H11L)
;
_shelx_res_checksum              6334
_shelx_hkl_checksum              61930
_shelx_shelxl_version_number     2016/6
_olex2_submission_special_instructions 'No special instructions were received'