Adding value to terpenes: copper-catalyzed oxidation of α-pinene in water under micellar conditions
Correia, Gilvan A.; Franco, Chris H. J.; Kirillova, Marina V.; Gallou, Fabrice; Kirillov, Alexander M.; Green Chemistry 27 (2025) 3178–3185; doi:10.1039/D4GC06525E

data_7249954
_publ_section_title
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 Adding value to terpenes: copper-catalyzed oxidation of \a-pinene in
 water under micellar conditions
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_journal_issue                   12
_journal_name_full               'Green Chemistry'
_journal_page_first              3178
_journal_page_last               3185
_journal_paper_doi               10.1039/D4GC06525E
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety
'C18 H28 Cu3 N3 O12, C8 H3 N O6, H2 O, 2.5[H2O]'
_chemical_formula_sum            'C26 H33 Cu3 N4 O19'
_chemical_formula_weight         896.18
_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   mixed
_audit_creation_date             2024-09-23
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
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_audit_update_record
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2024-09-23 deposited with the CCDC.	2025-02-14 downloaded from the CCDC.
;
_cell_angle_alpha                104.287(4)
_cell_angle_beta                 96.867(5)
_cell_angle_gamma                103.278(4)
_cell_formula_units_Z            2
_cell_length_a                   7.3749(10)
_cell_length_b                   13.1591(14)
_cell_length_c                   19.230(3)
_cell_measurement_reflns_used    5370
_cell_measurement_temperature    298
_cell_measurement_theta_max      26.352
_cell_measurement_theta_min      2.225
_cell_volume                     1729.1(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      298.00
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0804
_diffrn_reflns_av_unetI/netI     0.0498
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            35596
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.350
_diffrn_reflns_theta_min         2.368
_exptl_absorpt_coefficient_mu    1.915
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6694
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0704 before and 0.0609 after correction.
The Ratio of minimum to maximum transmission is 0.8977.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'light blue'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.721
_exptl_crystal_description       prism
_exptl_crystal_F_000             912
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.935
_refine_diff_density_min         -1.270
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     465
_refine_ls_number_reflns         6313
_refine_ls_number_restraints     19
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0956
_refine_ls_R_factor_gt           0.0648
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0996P)^2^+7.1527P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1765
_refine_ls_wR_factor_ref         0.1980
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4469
_reflns_number_total             6313
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4gc06525e2.cif
_cod_data_source_block           compound_03_micellar
_cod_depositor_comments
'Adding full bibliography for 7249952--7249954.cif.'
_cod_database_code               7249954
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.762
_shelx_estimated_absorpt_t_min   0.667
_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, All O(H,H) groups
2. Restrained distances
 O16-H16
 0.85 with sigma of 0.01
 C18-H18B
 0.95 with sigma of 0.02
 H18A-C18
 0.95 with sigma of 0.02
 H18A-H18B
 1.6 with sigma of 0.04
 H17C-C17
 1.6 with sigma of 0.04
 Cu4-H16
 2.664448 with sigma of 0.02
 C22-H16
 1.895235 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C17 \\sim C18 \\sim C19 \\sim C20: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 1.7A
Uanis(O14) = Uanis(O13) = Uanis(O15)
Uanis(Cu2) = Uanis(Cu1)
Uanis(C17) = Uanis(C18) = Uanis(C19) = Uanis(C20)
4. Others
 Sof(Cu1)=Sof(O15)=1-FVAR(1)
 Sof(Cu2)=Sof(O13)=FVAR(1)
5.a Free rotating group:
 O19(H19C,H19D)
5.b Rotating group:
 O17(H17A,H17B), O18(H18C,H18D)
5.c Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C18(H18A,H18B), C17(H17C,H17D), C25(H25A,H25B), C24(H24A,
 H24B), C22(H22A,H22B), C23(H23A,H23B)
5.d Aromatic/amide H refined with riding coordinates:
 C7(H7), C5(H5), C3(H3), C11(H11), C15(H15), C13(H13)
5.e Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              16988
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'
_publcif_funding_html
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