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_7241983
_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
'0.53(C9 H10 N O2), C4.3 H4.72 N0.47 O0.94, 0.5(Br Cl)'
_chemical_formula_sum            'C9 H10 Br0.5 Cl0.5 N O2'
_chemical_formula_weight         221.86
_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             2020-05-25
_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                 91.675(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.8044(7)
_cell_length_b                   8.6743(12)
_cell_length_c                   18.561(3)
_cell_measurement_reflns_used    1438
_cell_measurement_temperature    300
_cell_measurement_theta_max      23.8270
_cell_measurement_theta_min      4.0340
_cell_volume                     934.1(2)
_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 0.890
_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     12.00  86.00   1.00   20.00    --   17.77  57.00 150.00   74
  2  \w    -50.00  40.00   1.00   20.00    --   17.77 -38.00-150.00   90
  3  \w    -10.00  31.00   1.00   20.00    --   17.77  77.00 120.00   41
  4  \w      7.00  39.00   1.00   20.00    --   17.77  77.00-150.00   32
  5  \w     -1.00  27.00   1.00   20.00    --   17.77  57.00   0.00   28
  6  \w     60.00  85.00   1.00   20.00    --   17.77  57.00   0.00   25
  7  \w    -39.00  45.00   1.00   20.00    --   17.77 -77.00   0.00   84
  8  \w    -39.00 -14.00   1.00   20.00    --  -16.28 -77.00 150.00   25
  9  \w    -33.00  -6.00   1.00   20.00    --   17.77 -77.00 -60.00   27
;
_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      0.0545789000
_diffrn_orient_matrix_UB_12      -0.0728473000
_diffrn_orient_matrix_UB_13      0.0038586000
_diffrn_orient_matrix_UB_21      0.0897211000
_diffrn_orient_matrix_UB_22      0.0256450000
_diffrn_orient_matrix_UB_23      -0.0222232000
_diffrn_orient_matrix_UB_31      0.0623682000
_diffrn_orient_matrix_UB_32      0.0270376000
_diffrn_orient_matrix_UB_33      0.0308820000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0898
_diffrn_reflns_av_unetI/netI     0.0788
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.890
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            7686
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.890
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         29.372
_diffrn_reflns_theta_min         3.512
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.369
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63901
_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    1.578
_exptl_crystal_description       block
_exptl_crystal_F_000             452
_exptl_crystal_recrystallization_method 'slow evaporation'
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.497
_refine_diff_density_min         -0.317
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.153
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     228
_refine_ls_number_reflns         2276
_refine_ls_number_restraints     165
_refine_ls_restrained_S_all      1.120
_refine_ls_R_factor_all          0.1261
_refine_ls_R_factor_gt           0.0783
_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^)+(0.0518P)^2^+0.7504P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1594
_refine_ls_wR_factor_ref         0.1840
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1519
_reflns_number_total             2276
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ce01718c2.cif
_cod_data_source_block           '[1H]Br05Cl05_irradiated-2h'
_cod_depositor_comments
'Adding full bibliography for 7241976--7241984.cif.'
_cod_original_formula_sum        'C9 H10 Br0.50 Cl0.50 N O2'
_cod_database_code               7241983
_shelx_shelxl_version_number     2016/6
_reflns_odcompleteness_completeness 99.76
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 H2AA-O1A
 2.273 with sigma of 0.04
3. Restrained planarity
 H2AA, O2A, C9A, O1A, C8A
 with sigma of 0.1
4. Rigid body (RIGU) restrains
 C9A, N1A, H1AA, H1AB, H1AC, C1A, C6A, C2A, H6A, C5A, H2A, C3A, N1B, H5A, C4A,
 H3A, C1B, C7A, C2B, C6B, H7A, C8A, C3B, H2B, C5B, H6B, H8A, C4B, H3B, H5B, O2A,
  O1A, C7B, H7B, C8B, H8B, C9B, O1B, O2B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(N1B)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=Sof(C5B)=Sof(H5B)=Sof(C3B)=Sof(H3B)=
 Sof(C2B)=Sof(H2B)=Sof(C1B)=Sof(C6B)=Sof(H6B)=Sof(C7B)=Sof(H7B)=Sof(C8B)=
 Sof(H8B)=Sof(C9B)=Sof(O1B)=Sof(O2B)=Sof(H2BA)=1-FVAR(1)
 Sof(N1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C1A)=Sof(C6A)=Sof(H6A)=Sof(C2A)=
 Sof(H2A)=Sof(C5A)=Sof(H5A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(C7A)=Sof(H7A)=
 Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(O2A)=Sof(H2AA)=Sof(O1A)=Sof(C4B)=FVAR(1)
 Fixed Sof: Cl1(0.5) Br1(0.5)
6.a Ternary CH refined with riding coordinates:
 C7B(H7B), C8B(H8B)
6.b Aromatic/amide H refined with riding coordinates:
 C6A(H6A), C2A(H2A), C5A(H5A), C3A(H3A), C7A(H7A), C8A(H8A), C5B(H5B),
 C3B(H3B), C2B(H2B), C6B(H6B)
6.c Fitted hexagon refined as free rotating group:
 C5B(C4B,C3B,C2B,C1B,C6B)
6.d Idealised Me refined as rotating group:
 N1A(H1AA,H1AB,H1AC), N1B(H1BA,H1BB,H1BC)
6.e Idealised tetrahedral OH refined as rotating group:
 O2A(H2AA), O2B(H2BA)
;
_shelx_res_checksum              99852
_olex2_exptl_crystal_mounting_method 'fomblin oil'
_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 1.384
_oxdiff_exptl_absorpt_empirical_full_min 0.747