The impact of solid solution composition on kinetics and mechanism of [2 + 2] photodimerization of cinnamic acid derivatives
Pandolfi, Lorenzo; Giunchi, Andrea; Salzillo, Tommaso; Brillante, Aldo; Della Valle, Raffaele G.; Venuti, Elisabetta; Grepioni, Fabrizia; D'Agostino, Simone; CrystEngComm 23 (2021) 1352–1359; doi:10.1039/D0CE01718C

data_7241978
_publ_section_title
;
 The impact of solid solution composition on kinetics and mechanism of [2
 + 2] photodimerization of cinnamic acid derivatives
;
_journal_issue                   6
_journal_name_full               CrystEngComm
_journal_page_first              1352
_journal_page_last               1359
_journal_paper_doi               10.1039/D0CE01718C
_journal_volume                  23
_journal_year                    2021
_chemical_formula_moiety         'C9 H10 N1 O2, Br0.25 Cl0.75'
_chemical_formula_sum            'C9 H10 Br0.25 Cl0.75 N O2'
_chemical_formula_weight         210.74
_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     dual
_audit_creation_date             2020-06-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-10-16 deposited with the CCDC.	2020-12-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.532(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.6612(4)
_cell_length_b                   8.6217(7)
_cell_length_c                   19.164(2)
_cell_measurement_reflns_used    1126
_cell_measurement_temperature    300
_cell_measurement_theta_max      24.1800
_cell_measurement_theta_min      3.9620
_cell_volume                     935.04(14)
_computing_cell_refinement       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      300
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1340
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.838
_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    -85.00 -38.00   1.00   20.00    --  -16.20 -57.00-180.00   47
  2  \w    -20.00  52.00   1.00   20.00    --  -16.20  57.00 -30.00   72
  3  \w     -9.00  37.00   1.00   20.00    --   17.77  77.00  60.00   46
  4  \w     18.00  50.00   1.00   20.00    --   17.77 -99.00 -30.00   32
  5  \w     -7.00  18.00   1.00   20.00    --   17.77  77.00-180.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0790596000
_diffrn_orient_matrix_UB_12      0.0636778000
_diffrn_orient_matrix_UB_13      0.0018200000
_diffrn_orient_matrix_UB_21      0.0966711000
_diffrn_orient_matrix_UB_22      0.0507212000
_diffrn_orient_matrix_UB_23      0.0064997000
_diffrn_orient_matrix_UB_31      0.0098514000
_diffrn_orient_matrix_UB_32      0.0119182000
_diffrn_orient_matrix_UB_33      -0.0364217000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0405
_diffrn_reflns_av_unetI/netI     0.0760
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.838
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            4235
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.838
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         29.262
_diffrn_reflns_theta_min         3.600
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.370
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87117
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.69a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.497
_exptl_crystal_description       block
_exptl_crystal_F_000             434
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.200
_refine_diff_density_min         -0.440
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.001
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     213
_refine_ls_number_reflns         2135
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.1312
_refine_ls_R_factor_gt           0.0580
_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^)+(0.0710P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1325
_refine_ls_wR_factor_ref         0.1765
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1089
_reflns_number_total             2135
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ce01718c2.cif
_cod_data_source_block           '[1H]Br025Cl075_irrad'
_cod_depositor_comments
'Adding full bibliography for 7241976--7241984.cif.'
_cod_original_cell_volume        935.03(14)
_cod_database_code               7241978
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.986
_shelx_estimated_absorpt_t_min   0.935
_reflns_odcompleteness_completeness 99.66
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H1Aa,H1Ab,H1Ac} of N1A
 At 1.5 times of:
  All O(H) groups, {H1Ba,H1Bb,H1Bc} of N1B
2. Others
 Sof(C1B)=Sof(C2B)=Sof(H2B)=Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(C5B)=Sof(H5B)=
 Sof(C6B)=Sof(H6B)=Sof(C1)=Sof(H1)=Sof(C2)=Sof(H2)=Sof(C9B)=Sof(N1B)=Sof(H1Ba)=
 Sof(H1Bb)=Sof(H1Bc)=Sof(O1B)=Sof(O2B)=Sof(H2Ba)=1-FVAR(1)
 Sof(C1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(C5A)=Sof(H5A)=
 Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(N1A)=
 Sof(H1Aa)=Sof(H1Ab)=Sof(H1Ac)=Sof(O1A)=Sof(O2A)=Sof(H2Aa)=FVAR(1)
 Fixed Sof: Br1(0.25) Cl1(0.75)
3.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2)
3.b Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C3A(H3A), C5A(H5A), C6A(H6A), C7A(H7A), C8A(H8A), C2B(H2B),
 C3B(H3B), C5B(H5B), C6B(H6B)
3.c Fitted hexagon refined as free rotating group:
 C1B(C2B,C3B,C4B,C5B,C6B)
3.d Idealised Me refined as rotating group:
 N1A(H1Aa,H1Ab,H1Ac), N1B(H1Ba,H1Bb,H1Bc)
3.e Idealised tetrahedral OH refined as rotating group:
 O2A(H2Aa), O2B(H2Ba)
;
_shelx_res_checksum              26056
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.145
_oxdiff_exptl_absorpt_empirical_full_min 0.923