Exploring the excited-state charge transfer fluorescence profile of 7-hydroxycoumarin and 2-methylimidazole – a combined X-ray diffraction and theoretical approach
Hawkins, Bryson A.; Najib, Elias; Du, Jonathan J.; Lai, Felcia; Platts, James A.; Groundwater, Paul W.; Hibbs, David E.; Physical Chemistry Chemical Physics  (2022) –; doi:10.1039/D2CP01235A

data_7244958
_publ_section_title
;
 Exploring the excited-state charge transfer fluorescence profile of
 7-hydroxycoumarin and 2-methylimidazole -- a combined X-ray diffraction
 and theoretical approach
;
_journal_name_full               'Physical Chemistry Chemical Physics'
_journal_paper_doi               10.1039/D2CP01235A
_journal_year                    2022
_chemical_formula_moiety         'C16 H16 N2 O5'
_chemical_formula_sum            'C16 H16 N2 O5'
_chemical_formula_weight         316.31
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     iterative
_audit_creation_date             2022-02-21
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-02-28 deposited with the CCDC.	2022-05-11 downloaded from the CCDC.
;
_cell_angle_alpha                73.303(2)
_cell_angle_beta                 82.2052(17)
_cell_angle_gamma                77.655(2)
_cell_formula_units_Z            2
_cell_length_a                   7.51259(18)
_cell_length_b                   9.8167(3)
_cell_length_c                   11.1108(2)
_cell_measurement_reflns_used    36450
_cell_measurement_temperature    120.0(3)
_cell_measurement_theta_max      65.1460
_cell_measurement_theta_min      3.1620
_cell_volume                     764.30(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.0(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4948
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.980
_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   -115.00 -14.00   1.00   15.00    --  -42.13 -57.00   0.00  101
  2  \w   -115.00 -14.00   1.00   15.00    --  -42.13 -57.00 -60.00  101
  3  \w   -115.00 -14.00   1.00   15.00    --  -42.13 -57.00-120.00  101
  4  \w   -115.00 -14.00   1.00   15.00    --  -42.13 -57.00  30.00  101
  5  \w   -115.00 -14.00   1.00   15.00    --  -42.13 -57.00-150.00  101
  6  \w   -115.00 -14.00   1.00   15.00    --  -42.13 -57.00 150.00  101
  7  \w   -115.00 -14.00   1.00   15.00    --  -42.13 -57.00  90.00  101
  8  \w     14.00 115.00   1.00   15.00    --   42.13  57.00 -60.00  101
  9  \w    -30.00  70.00   1.00   15.00    --   42.13 -57.00 -90.00  100
 10  \w    -30.00  70.00   1.00   15.00    --   42.13 -57.00 150.00  100
 11  \w    -30.00  71.00   1.00   15.00    --   42.13 -60.00   4.22  101
 12  \w     62.00 158.00   1.00   60.00    --   90.50  59.00 -66.45   96
 13  \w     62.00 158.00   1.00   60.00    --   90.50  59.00  68.63   96
 14  \w     62.00 158.00   1.00   60.00    --   90.50  59.00  25.66   96
 15  \w     63.00 158.00   1.00   60.00    --   90.50  56.00 -41.05   95
 16  \w     62.00 158.00   1.00   60.00    --   90.50  59.00  -7.79   96
 17  \w     63.00 158.00   1.00   60.00    --   90.50  56.00  61.37   95
 18  \w     62.00 158.00   1.00   60.00    --   90.50  60.00 -54.78   96
 19  \w     62.00 158.00   1.00   60.00    --   90.50  60.00  42.57   96
 20  \w     62.00 158.00   1.00   60.00    --   90.50  58.00 -15.77   96
 21  \w     62.00 158.00   1.00   60.00    --   90.50  59.00  81.58   96
 22  \w     63.00 158.00   1.00   60.00    --   90.50  55.00 133.31   95
 23  \w     62.00 158.00   1.00   60.00    --   90.50  57.00-155.76   96
 24  \w     62.00 158.00   1.00   60.00    --   90.50  58.00  10.91   96
 25  \w     63.00 158.00   1.00   60.00    --   90.50  56.00 -81.53   95
 26  \w     63.00 158.00   1.00   60.00    --   90.50  56.00 102.72   95
 27  \w     62.00 158.00   1.00   60.00    --   90.50  58.00-176.20   96
 28  \w     62.00 158.00   1.00   60.00    --   90.50  58.00-143.98   96
 29  \w     17.00 119.00   1.00   60.00    --   90.50 -60.00-157.52  102
 30  \w     62.00 158.00   1.00   60.00    --   90.50  57.00-118.90   96
 31  \w     63.00 158.00   1.00   60.00    --   90.50  55.00 176.76   95
 32  \w     62.00 158.00   1.00   60.00    --   90.50  60.00-108.03   96
 33  \w     17.00 119.00   1.00   60.00    --   90.50 -60.00 -95.91  102
 34  \w     62.00 158.00   1.00   60.00    --   90.50  60.00 153.08   96
 35  \w     17.00 119.00   1.00   60.00    --   90.50 -60.00  16.74  102
 36  \w     62.00 158.00   1.00   60.00    --   90.50  59.00 114.30   96
 37  \w     17.00 119.00   1.00   60.00    --   90.50 -60.00  48.89  102
 38  \w     17.00 119.00   1.00   60.00    --   90.50 -60.00 -50.51  102
 39  \w     17.00 119.00   1.00   60.00    --   90.50 -60.00  95.00  102
 40  \w     17.00 119.00   1.00   60.00    --   90.50 -60.00 146.57  102
 41  \w     62.00 158.00   1.00   60.00    --   90.50  60.00 144.32   96
 42  \w    -70.00  31.00   1.00   15.00    --  -42.13  57.00-120.00  101
 43  \w   -115.00 -16.00   1.00   15.00    --  -42.13 -44.00  25.39   99
 44  \w   -116.00 -17.00   1.00   15.00    --  -42.13 -42.00 162.63   99
 45  \w     14.00 115.00   1.00   15.00    --   42.13  57.00-120.00  101
 46  \w     14.00 115.00   1.00   15.00    --   42.13  57.00 150.00  101
 47  \w    -30.00  70.00   1.00   15.00    --   42.13 -57.00-180.00  100
 48  \w     14.00 115.00   1.00   15.00    --   42.13  57.00 120.00  101
 49  \w     14.00  93.00   1.00   15.00    --   42.13  57.00-150.00   79
 50  \w     14.00 115.00   1.00   15.00    --   42.13  57.00  60.00  101
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0439379000
_diffrn_orient_matrix_UB_12      0.0127079000
_diffrn_orient_matrix_UB_13      -0.0618146000
_diffrn_orient_matrix_UB_21      -0.0863282000
_diffrn_orient_matrix_UB_22      0.0257591000
_diffrn_orient_matrix_UB_23      -0.0254584000
_diffrn_orient_matrix_UB_31      0.0041386000
_diffrn_orient_matrix_UB_32      0.0711713000
_diffrn_orient_matrix_UB_33      0.0010086000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.046
_diffrn_reflns_av_unetI/netI     0.0121
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            12517
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         45.294
_diffrn_reflns_theta_min         2.507
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.104
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.348
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.105a (Rigaku Oxford Diffraction, 2021)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.374
_exptl_crystal_description       plate
_exptl_crystal_F_000             332
_exptl_crystal_preparation       'Slow evaporation from DCM'
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.612
_refine_diff_density_min         -0.239
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         12517
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0431
_refine_ls_R_factor_gt           0.0358
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0705P)^2^+0.0335P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1056
_refine_ls_wR_factor_ref         0.1137
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10519
_reflns_number_total             12517
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cp01235a2.cif
_cod_data_source_block           shelx
_cod_database_code               7244958
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C16 H16 N2 O5'
_cell_oxdiff_angle_alpha         73.303(2)
_cell_oxdiff_angle_beta          82.2052(17)
_cell_oxdiff_angle_gamma         77.655(2)
_cell_oxdiff_length_a            7.51259(18)
_cell_oxdiff_length_b            9.8167(3)
_cell_oxdiff_length_c            11.1108(2)
_cell_oxdiff_measurement_reflns_used 36450
_cell_oxdiff_volume              764.30(3)
_shelx_estimated_absorpt_t_max   0.984
_shelx_estimated_absorpt_t_min   0.940
_reflns_odcompleteness_completeness 97.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     45.18
_olex2_refinement_description
;
1. Restrained distances
 C9-H9
 1.083 with sigma of 0.02
 C11-H11
 1.083 with sigma of 0.02
 C12-H12
 1.083 with sigma of 0.02
 C1-H1A
 1.059 with sigma of 0.02
 C1-H1B
 1.059 with sigma of 0.02
 C1-H1C
 1.059 with sigma of 0.02
 C4'-H4'A
 1.059 with sigma of 0.02
 C4'-H4'B
 1.059 with sigma of 0.02
 C4'-H4'C
 1.059 with sigma of 0.02
 C1'-H1'
 1.083 with sigma of 0.02
 C2'-H2'
 1.083 with sigma of 0.02
 N1'-H1'A
 1.009 with sigma of 0.02
 O5-H5
 0.967 with sigma of 0.02
 C2-H2A
 1.092 with sigma of 0.02
 C2-H2B
 1.092 with sigma of 0.02
;
_shelx_res_checksum              43640
_ins_header
;
TITL 21BH003_CD_om75_b3_s in P-1 
REM P-1 (#2 in standard setting)
CELL 0.71073   7.512589   9.816667  11.110779  73.3031  82.2052  77.6554
ZERR    2.00   0.000185   0.000335   0.000197   0.0022   0.0017   0.0025
LATT  1
SFAC C H N O
UNIT 16 16 2 5
REM  CrysAlisPro recorded range (K): Min=119.8; max=120.3; aver:120.0
TEMP -120
SIZE 0.16 0.30 0.60
TREF
HKLF 4
END
;
_olex2_exptl_crystal_mounting_method Paratone-N
_olex2_submission_original_sample_id en092mim
_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 1.325
_oxdiff_exptl_absorpt_empirical_full_min 0.824