Building Strain with Large Macrocycles and Using It To Tune the Thermal Half-Lives of Hydrazone Photochromes.
Li, Quan; Qian, Hai; Shao, Baihao; Hughes, Russell P.; Aprahamian, Ivan; Journal of the American Chemical Society 140 (2018) 11829–11835; doi:10.1021/jacs.8b07612

data_4132963
_publ_section_title
;
 Building Strain with Large Macrocycles and Using It To Tune the Thermal
 Half-Lives of Hydrazone Photochromes.
;
_journal_issue                   37
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11829
_journal_page_last               11835
_journal_paper_doi               10.1021/jacs.8b07612
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C19 H20 N2 O4'
_chemical_formula_sum            'C19 H20 N2 O4'
_chemical_formula_weight         340.37
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-04-10
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_cell_angle_alpha                90
_cell_angle_beta                 103.774(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.4635(4)
_cell_length_b                   4.98269(12)
_cell_length_c                   23.2124(6)
_cell_measurement_reflns_used    6466
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      72.7790
_cell_measurement_theta_min      2.0110
_cell_volume                     1737.08(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.20a (Rigaku OD, 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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      173(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.36
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w     91.00 264.00   1.00   30.00    --  110.00  73.83  21.73  173
  2  \w     43.72 226.72   1.00   30.00    --   72.50  73.83 126.72  183
  3  \w     81.22 264.22   1.00   30.00    --  110.00  73.83-125.78  183
  4  \f    -25.77 343.46   1.00   30.00 101.72  72.50  73.83    --   369
  5  \w    119.22 193.22   1.00   30.00    --   40.00  73.83 -48.27   74
  6  \f    -25.77 302.43   1.00   30.00 164.22 107.50  73.83    --   328
  7  \w    -29.78  44.22   1.00   30.00    --    0.00  73.83 126.72   74
  8  \w    184.22 259.22   1.00   30.00    --  105.00  73.83 134.22   75
  9  \f   -154.22 -19.14   1.00   30.00 176.72  80.00  73.83    --   135
 10  \f   -241.63 -17.50   1.00   30.00 101.72  15.00  73.83    --   224
 11  \f    -25.77 324.44   1.00   30.00  86.72 110.00  73.83    --   350
 12  \f   -322.45 -18.26   1.00   30.00-138.28 110.00  73.83    --   304
 13  \f   -279.25 -17.08   1.00   30.00 144.22 110.00  73.83    --   262
 14  \f    -25.77 343.46   1.00   30.00 116.72 110.00  73.83    --   369
 15  \w    174.14 224.14   1.00   30.00    --   87.50  73.83  39.22   50
 16  \w    178.47 228.47   1.00   30.00    --   75.00  73.83 -55.78   50
 17  \w    154.45 204.45   1.00   30.00    --   65.00  73.83-123.28   50
 18  \w    144.22 194.22   1.00   30.00    --   40.00  73.83  21.73   50
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0541261000
_diffrn_orient_matrix_UB_12      -0.2622252000
_diffrn_orient_matrix_UB_13      -0.0115340000
_diffrn_orient_matrix_UB_21      -0.0604084000
_diffrn_orient_matrix_UB_22      0.1244275000
_diffrn_orient_matrix_UB_23      -0.0561284000
_diffrn_orient_matrix_UB_31      0.0627633000
_diffrn_orient_matrix_UB_32      -0.1065236000
_diffrn_orient_matrix_UB_33      -0.0372792000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0626
_diffrn_reflns_av_unetI/netI     0.0301
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            19354
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.308
_diffrn_reflns_theta_min         3.123
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.756
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64345
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.20a (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.301
_exptl_crystal_description       needle
_exptl_crystal_F_000             720
_exptl_crystal_recrystallization_method 'used as received'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.094
_exptl_crystal_size_min          0.052
_refine_diff_density_max         0.621
_refine_diff_density_min         -0.799
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     268
_refine_ls_number_reflns         3450
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0914
_refine_ls_R_factor_gt           0.0699
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0859P)^2^+2.1180P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1750
_refine_ls_wR_factor_ref         0.1932
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2576
_reflns_number_total             3450
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b07612_si_003.cif
_cod_data_source_block           ia317c
_cod_database_code               4132963
_shelxl_version_number           2014/6
_reflns_odcompleteness_completeness 98.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     73.15
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C18-C19A
 1.48 with sigma of 0.02
 C18-C19
 1.48 with sigma of 0.02
 C18-O4
 1.48 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C18) = Uanis(C9)
Uanis(C18A) = Uanis(C9)
Uanis(O4A) = Uanis(O2)
Uanis(O4) = Uanis(O2)
4. Others
 Fixed Sof: O4(0.5) O4A(0.5) C4(0.5) H4(0.5) C4A(0.5) H4A(0.5) C5(0.5) H5(0.5)
 C5A(0.5) H5A(0.5) H6B(0.5) H6A(0.5) C7(0.5) H7(0.5) C7A(0.5) H7A(0.5) C8(0.5)
 H8(0.5) C8A(0.5) H8A(0.5) C18(0.5) H18A(0.5) H18B(0.5) C18A(0.5) H18C(0.5)
 H18D(0.5) C19(0.5) H19A(0.5) H19B(0.5) H19C(0.5) C19A(0.5) H19D(0.5) H19E(0.5)
 H19F(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C18(H18A,H18B), C18A(H18C,H18D)
5.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C4(H4), C4A(H4A), C5(H5), C5A(H5A), C6(H6B), C6(H6A), C7(H7),
 C7A(H7A), C8(H8), C8A(H8A), C12(H12), C13(H13), C14(H14), C15(H15)
5.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C19(H19A,H19B,H19C), C19A(H19D,H19E,H19F)
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a nylon loop with paratone oil'
_olex2_submission_original_sample_id 1q-270
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.568
_oxdiff_exptl_absorpt_empirical_full_min 0.763