An unexpected chlorination of an organic sunscreen
Smith, Lydia G.; Di Leva, Dalila; Shaw, Lloyd A.; Hughes, Eric; Kenwright, Alan M.; Beeby, Andrew; Wilson, Mark R.; Mahon, Clare S.; Chemical Communications 61 (2025) 9314–9317; doi:10.1039/D5CC01593F

data_7134572
_publ_section_title
;
 An unexpected chlorination of an organic sunscreen
;
_journal_issue                   51
_journal_name_full               'Chemical Communications'
_journal_page_first              9314
_journal_page_last               9317
_journal_paper_doi               10.1039/D5CC01593F
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C24 H30.788 Cl0.212 N O4'
_chemical_formula_sum            'C24 H30.788 Cl0.212 N O4'
_chemical_formula_weight         404.837
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_symmetry_Int_Tables_number      15
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-18
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-18 deposited with the CCDC.	2025-05-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.083(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.8699(7)
_cell_length_b                   7.9825(3)
_cell_length_c                   33.9739(18)
_cell_measurement_reflns_used    9729
_cell_measurement_temperature    120.00
_cell_measurement_theta_max      27.052
_cell_measurement_theta_min      2.412
_cell_volume                     4279.6(3)
_computing_cell_refinement       'SAINT v8.40A (Bruker AXS, 2019)'
_computing_data_collection       'APEX4 v.2022.1-1 (Bruker AXS, 2022)'
_computing_data_reduction        'SAINT v8.40A (Bruker AXS, 2019)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5-beta (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      120.00
_diffrn_detector                 'Bruker PHOTON III C14 MM CPAD'
_diffrn_detector_area_resol_mean 54.4
_diffrn_detector_type            'CPA sensor'
_diffrn_measured_fraction_theta_full 0.9757
_diffrn_measured_fraction_theta_max 0.9708
_diffrn_measurement_device       '3-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture B'
_diffrn_measurement_method       '\w- and \f-scan'
_diffrn_radiation_monochromator  'focusing mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0832
_diffrn_reflns_av_unetI/netI     0.0382
_diffrn_reflns_Laue_measured_fraction_full 0.9757
_diffrn_reflns_Laue_measured_fraction_max 0.9708
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            59216
_diffrn_reflns_point_group_measured_fraction_full 0.9757
_diffrn_reflns_point_group_measured_fraction_max 0.9708
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         27.18
_diffrn_reflns_theta_min         2.41
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_type              'Incoatec I\mS 3.0 microsource'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.110
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.7012
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0892 before and 0.0647 after correction.
The Ratio of minimum to maximum transmission is 0.9406.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.257
_exptl_crystal_description       block
_exptl_crystal_F_000             1740.536
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.098
_exptl_crystal_size_min          0.051
_refine_diff_density_max         1.5298
_refine_diff_density_min         -0.5932
_refine_diff_density_rms         0.0959
_refine_ls_d_res_high            0.7778
_refine_ls_d_res_low             8.4457
_refine_ls_goodness_of_fit_ref   1.0635
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    70
_refine_ls_number_parameters     341
_refine_ls_number_reflns         4626
_refine_ls_number_restraints     867
_refine_ls_restrained_S_all      0.9639
_refine_ls_R_factor_all          0.1182
_refine_ls_R_factor_gt           0.0849
_refine_ls_shift/su_max          0.0008
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0814P)^2^+16.3754P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2011
_refine_ls_wR_factor_ref         0.2253
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              20
_reflns_limit_h_min              0
_reflns_limit_k_max              10
_reflns_limit_k_min              0
_reflns_limit_l_max              42
_reflns_limit_l_min              -43
_reflns_number_gt                3286
_reflns_number_total             4626
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5cc01593f3.cif
_cod_data_source_block           24srv092
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_atom_sites_solution_primary' value 'Dual' was changed to
'dual' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 7134571--7134572.cif.
;
_cod_database_code               7134572
_computing_bruker_data_scaling   'SADABS V2012/1 (Bruker AXS Inc.)'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O5-C25 \\sim O4-C19
 with sigma of 0.02
 O5-C18 \\sim O4-C18
 with sigma of 0.02
 C26-C25 \\sim C20-C19 \\sim C21-C20 \\sim C27-C26 \\sim C28-C27 \\sim C22-C21
\\sim C23-C22 \\sim C29-C28
 \\sim C30-C29 \\sim C24-C23
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 O3, O4, O5, C18, C19, H19a, H19b, C20, H20a, H20b, C21, H21a, H21b, C22, H22a,
  H22b, C23, H23a, H23b, C24, H24a, H24b, H24c, C25, H25a, H25b, C26, H26a,
 H26b, C27, H27a, H27b, C28, H28a, H28b, C29, H29a, H29b, C30, H30a, H30b, H30c
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O5)=Sof(C25)=Sof(H25a)=Sof(H25b)=Sof(C26)=Sof(H26a)=Sof(H26b)=Sof(C27)=
 Sof(H27a)=Sof(H27b)=Sof(C28)=Sof(H28a)=Sof(H28b)=Sof(C29)=Sof(H29a)=Sof(H29b)=
 Sof(C30)=Sof(H30a)=Sof(H30b)=Sof(H30c)=1-FVAR(1)
 Sof(O4)=Sof(C19)=Sof(H19a)=Sof(H19b)=Sof(C20)=Sof(H20a)=Sof(H20b)=Sof(C21)=
 Sof(H21a)=Sof(H21b)=Sof(C22)=Sof(H22a)=Sof(H22b)=Sof(C23)=Sof(H23a)=Sof(H23b)=
 Sof(C24)=Sof(H24a)=Sof(H24b)=Sof(H24c)=FVAR(1)
 Sof(H4)=1-FVAR(2)
 Sof(Cl1)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C8(H8a,H8b), C10(H10a,H10b), C19(H19a,H19b), C20(H20a,H20b), C21(H21a,H21b),
 C22(H22a,H22b), C23(H23a,H23b), C25(H25a,H25b), C26(H26a,H26b), C27(H27a,H27b),
  C28(H28a,H28b), C29(H29a,H29b)
6.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C7(H7), C13(H13), C14(H14), C15(H15), C16(H16)
6.c Idealised Me refined as rotating group:
 C9(H9a,H9b,H9c), C11(H11a,H11b,H11c), C24(H24a,H24b,H24c), C30(H30a,H30b,H30c)
6.d Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems 700'
_olex2_submission_original_sample_id
'Hexyl 2-(3-chloro-4-(diethylamino)-2-hydroxybenzoyl) benzoate '
_olex2_submission_special_instructions 'No special instructions were received'