Environmentally Friendly Sunscreens: Mechanochemical Synthesis and Characterization of β-CD Inclusion Complexes of Avobenzone and Octinoxate with Improved Photostability
d’Agostino, Simone; Azzali, Alessandra; Casali, Lucia; Taddei, Paola; Grepioni, Fabrizia; ACS Sustainable Chemistry & Engineering  (2020) –; doi:10.1021/acssuschemeng.0c02735

data_4517985
_publ_section_title
;
 Environmentally Friendly Sunscreens: Mechanochemical Synthesis and
 Characterization of \b-CD Inclusion Complexes of Avobenzone and
 Octinoxate with Improved Photostability
;
_journal_name_full               'ACS Sustainable Chemistry &amp; Engineering'
_journal_paper_doi               10.1021/acssuschemeng.0c02735
_journal_year                    2020
_chemical_formula_moiety         'C20 H22 O3'
_chemical_formula_sum            'C20 H22 O3'
_chemical_formula_weight         310.37
_chemical_melting_point          350
_chemical_name_common            avobenzone_form_2
_chemical_name_systematic
1-(4-Methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-06-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   7.3175(10)
_cell_length_b                   11.8808(10)
_cell_length_c                   40.778(7)
_cell_measurement_reflns_used    596
_cell_measurement_temperature    300
_cell_measurement_theta_max      19.8010
_cell_measurement_theta_min      3.5990
_cell_volume                     3545.1(8)
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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     -8.00  18.25   0.75  275.00    --   17.92  77.00  60.00   35
  2  \w    -11.00  87.25   0.75  275.00    --   17.92   0.00  90.00  131
  3  \w    -20.00  65.50   0.75  275.00    --   17.92  19.00-180.00  114
;
_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      -0.0716861000
_diffrn_orient_matrix_UB_12      0.0257271000
_diffrn_orient_matrix_UB_13      -0.0089866000
_diffrn_orient_matrix_UB_21      -0.0428088000
_diffrn_orient_matrix_UB_22      0.0160279000
_diffrn_orient_matrix_UB_23      0.0148955000
_diffrn_orient_matrix_UB_31      0.0492025000
_diffrn_orient_matrix_UB_32      0.0514360000
_diffrn_orient_matrix_UB_33      -0.0001336000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1078
_diffrn_reflns_av_unetI/netI     0.1281
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            12729
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         3.308
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.077
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65044
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.163
_exptl_crystal_description       needle
_exptl_crystal_F_000             1328
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.102
_refine_diff_density_min         -0.086
_refine_diff_density_rms         0.025
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.960
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     247
_refine_ls_number_reflns         3124
_refine_ls_number_restraints     207
_refine_ls_restrained_S_all      0.955
_refine_ls_R_factor_all          0.2632
_refine_ls_R_factor_gt           0.0761
_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^)+(0.0229P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0928
_refine_ls_wR_factor_ref         0.1399
_reflns_Friedel_coverage         0.000
_reflns_number_gt                942
_reflns_number_total             3124
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            sc0c02735_si_002.cif
_cod_data_source_block           avo_form-2_o-pbca
_cod_database_code               4517985
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C20 H22 O3'
_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 distances
 C17-C20B
 1.5 with sigma of 0.02
 C17-C20A
 1.4 with sigma of 0.02
 C17-C18B
 1.5 with sigma of 0.02
 C17-C18A
 1.5 with sigma of 0.02
 C17-C19B
 1.4 with sigma of 0.02
 C17-C19A
 1.5 with sigma of 0.02
3. Rigid body (RIGU) restrains
 C20A, C19A, H19A, H19B, H19C, C17, C18A, C18B, C19B, C20B, C13, H20A, H20B,
 H20C, H18A, H18B, H18C, H18D, H18E, H18F, H19D, H19E, H19F, H20D, H20E, H20F,
 C14, C12, C15, H14, H12, C11, H15, C10, H11, C9, O2, C8, H8, C7, O3, C4, C5,
 C3, H5, C6, H3, C2, C1, H6, H2A, O1, C16, H16A, H16B, H16C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C18B)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19B)=Sof(H19D)=Sof(H19E)=
 Sof(H19F)=Sof(C20B)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(1)
 Sof(C19A)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C20A)=Sof(H20A)=Sof(H20B)=
 Sof(H20C)=Sof(C18A)=Sof(H18A)=Sof(H18B)=Sof(H18C)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C5(H5), C8(H8), C15(H15), C6(H6), C3(H3), C14(H14), C2(H2A), C12(H12), C11(H11)
5.b Idealised Me refined as rotating group:
 C19A(H19A,H19B,H19C), C20A(H20A,H20B,H20C), C18A(H18A,H18B,H18C), C18B(H18D,
 H18E,H18F), C19B(H19D,H19E,H19F), C20B(H20D,H20E,H20F), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              47012
_shelx_hkl_checksum              60335
_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 1.233
_oxdiff_exptl_absorpt_empirical_full_min 0.861