#------------------------------------------------------------------------------
#$Date: 2025-07-06 19:23:27 +0200 (Sun 06 de Jul de 2025) $
#$Revision: 301021 $
#$URL: svn://www.crystallography.net/cod/cif/7/24/99/7249954.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_7249954
loop_
_publ_author_name
'Correia, Gilvan A.'
'Franco, Chris H. J.'
'Kirillova, Marina V.'
'Gallou, Fabrice'
'Kirillov, Alexander M.'
_publ_section_title
;
 Adding value to terpenes: copper-catalyzed oxidation of α-pinene in
 water under micellar conditions
;
_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)
;
_audit_update_record
;
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       'φ and ω 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 λ/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/[σ²(Fo²)+(0.0996P)²+7.1527P] where P=(Fo²+2Fc²)/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 > 2σ(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_space_group_comment
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_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)
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'
_publcif_funding_html
;
;
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu3 Cu 0.000000 0.500000 0.000000 0.0276(3) Uani 1 2 d S . P . .
Cu2 Cu 0.2416(3) 0.37559(16) 0.10170(12) 0.0317(4) Uani 0.578(3) 1 d . . P . .
Cu5 Cu 1.000000 1.000000 0.500000 0.0373(3) Uani 1 2 d S . P . .
Cu4 Cu 0.80091(12) 0.74996(8) 0.48508(4) 0.0461(3) Uani 1 1 d D . . . .
O1 O 0.2278(6) 0.5983(3) 0.0715(2) 0.0340(10) Uani 1 1 d . . . . .
O2 O 0.3360(8) 0.5197(4) 0.1520(3) 0.0479(13) Uani 1 1 d . . . . .
O3 O 0.8719(7) 0.9286(4) 0.3961(2) 0.0379(11) Uani 1 1 d . . . . .
O20 O 1.0356(6) 0.8612(4) 0.5070(2) 0.0375(11) Uani 1 1 d . . . . .
O4 O 0.7205(7) 0.7559(4) 0.3879(2) 0.0386(11) Uani 1 1 d . . . . .
O5 O 0.5514(13) 0.9757(6) 0.0951(4) 0.103(3) Uani 1 1 d . . . . .
O7 O 0.7536(7) 0.5293(4) 0.0891(3) 0.0489(13) Uani 1 1 d . . . . .
O9 O 1.2583(7) 0.6728(4) 0.4071(3) 0.0463(12) Uani 1 1 d . . . . .
O8 O 0.7680(8) 0.4657(4) 0.1865(3) 0.0542(14) Uani 1 1 d . . . . .
O11 O 1.0338(14) 0.9232(6) 0.1361(4) 0.098(3) Uani 1 1 d . . . . .
O10 O 1.3836(7) 0.8505(4) 0.4234(3) 0.0451(12) Uani 1 1 d . . . . .
O19 O 0.6842(8) 0.9413(5) 0.5376(3) 0.0519(13) Uani 1 1 d G . . . .
H19C H 0.597908 0.896868 0.549136 0.078 Uiso 1 1 d G U . . .
H19D H 0.676123 1.003848 0.560352 0.078 Uiso 1 1 d G U . . .
O14 O 0.0251(7) 0.3772(4) 0.0342(3) 0.0544(13) Uani 1 1 d . . . . .
N2 N 0.8654(9) 0.7285(5) 0.5840(3) 0.0427(14) Uani 1 1 d . . . . .
O16 O 0.5468(7) 0.6619(4) 0.4869(3) 0.0471(12) Uani 1 1 d D . . . .
H16 H 0.4357(19) 0.653(5) 0.463(2) 0.071 Uiso 1 1 d D U . . .
C1 C 0.3299(8) 0.5989(5) 0.1284(3) 0.0292(13) Uani 1 1 d . . . . .
O17 O 0.4149(9) 0.3747(6) 0.0072(4) 0.081(2) Uani 1 1 d . . . . .
H17A H 0.370448 0.408243 -0.020859 0.122 Uiso 1 1 d R U . . .
H17B H 0.527742 0.415921 0.026535 0.122 Uiso 1 1 d R U . . .
N1 N 0.1068(9) 0.2286(5) 0.0966(4) 0.0568(19) Uani 1 1 d . . . . .
C21 C 0.130(4) 0.1392(13) 0.0352(12) 0.233(14) Uani 1 1 d . . . . .
H21A H 0.099068 0.154344 -0.010421 0.350 Uiso 1 1 calc R U . . .
H21B H 0.046855 0.071020 0.034673 0.350 Uiso 1 1 calc R U . . .
H21C H 0.258938 0.135060 0.042209 0.350 Uiso 1 1 calc R U . . .
C20 C 0.4075(15) 0.2394(9) 0.1681(7) 0.101(2) Uani 1 1 d . U . . .
C19 C 0.1924(15) 0.2073(10) 0.1577(7) 0.101(2) Uani 1 1 d . U . . .
H19A H 0.147960 0.130219 0.153042 0.121 Uiso 1 1 calc R U . . .
H19B H 0.154707 0.246856 0.200689 0.121 Uiso 1 1 calc R U . . .
C18 C -0.0790(15) 0.2254(10) 0.0767(8) 0.101(2) Uani 1 1 d D U . . .
H18A H -0.126535 0.250119 0.121016 0.121 Uiso 1 1 calc DR U . . .
H18B H -0.148794 0.149840 0.054134 0.121 Uiso 1 1 calc DR U . . .
C17 C -0.1252(15) 0.2873(9) 0.0278(7) 0.101(2) Uani 1 1 d D U . . .
H17C H -0.156220 0.240895 -0.022125 0.121 Uiso 1 1 calc DR U . . .
H17D H -0.235761 0.311670 0.038849 0.121 Uiso 1 1 calc R U . . .
C2 C 0.4583(8) 0.7075(5) 0.1736(3) 0.0271(13) Uani 1 1 d . . . . .
C7 C 0.5502(8) 0.7210(5) 0.2438(3) 0.0275(13) Uani 1 1 d . . . . .
H7 H 0.533915 0.661744 0.262822 0.033 Uiso 1 1 calc R U . . .
C6 C 0.6661(8) 0.8215(5) 0.2863(3) 0.0281(13) Uani 1 1 d . . . . .
C8 C 0.7628(9) 0.8373(5) 0.3638(3) 0.0297(14) Uani 1 1 d . . . . .
C25 C 1.1502(10) 0.8482(6) 0.5675(4) 0.0450(18) Uani 1 1 d . . . . .
H25A H 1.251062 0.914388 0.590332 0.054 Uiso 1 1 calc R U . . .
H25B H 1.207263 0.789150 0.551025 0.054 Uiso 1 1 calc R U . . .
C24 C 1.0268(12) 0.8231(7) 0.6218(4) 0.054(2) Uani 1 1 d . . . . .
H24A H 1.099818 0.807346 0.661283 0.065 Uiso 1 1 calc R U . . .
H24B H 0.981443 0.885527 0.642407 0.065 Uiso 1 1 calc R U . . .
C26 C 0.9171(18) 0.6237(8) 0.5817(8) 0.101(4) Uani 1 1 d . . . . .
H26A H 0.810931 0.563199 0.555417 0.151 Uiso 1 1 calc R U . . .
H26B H 0.949953 0.619665 0.630571 0.151 Uiso 1 1 calc R U . . .
H26C H 1.023280 0.621218 0.557508 0.151 Uiso 1 1 calc R U . . .
O18 O 0.8985(18) 0.5886(9) 0.4323(7) 0.146(4) Uani 1 1 d . . . . .
H18C H 1.016798 0.600181 0.408430 0.219 Uiso 1 1 d R U . . .
H18D H 0.807329 0.532109 0.387102 0.219 Uiso 1 1 d R U . . .
C22 C 0.5231(12) 0.6500(7) 0.5572(4) 0.0494(19) Uani 1 1 d D . . . .
H22A H 0.517230 0.575888 0.557975 0.059 Uiso 1 1 calc R U . . .
H22B H 0.406007 0.665658 0.568511 0.059 Uiso 1 1 calc R U . . .
C23 C 0.6910(13) 0.7290(7) 0.6130(4) 0.060(2) Uani 1 1 d . . . . .
H23A H 0.673614 0.801729 0.623858 0.072 Uiso 1 1 calc R U . . .
H23B H 0.699817 0.707843 0.657880 0.072 Uiso 1 1 calc R U . . .
C5 C 0.6911(9) 0.9095(6) 0.2579(3) 0.0370(15) Uani 1 1 d . . . . .
H5 H 0.767006 0.977640 0.285682 0.044 Uiso 1 1 calc R U . . .
C4 C 0.6010(10) 0.8943(6) 0.1873(4) 0.0390(16) Uani 1 1 d . . . . .
C3 C 0.4857(9) 0.7958(6) 0.1442(3) 0.0366(15) Uani 1 1 d . . . . .
H3 H 0.427421 0.788108 0.096845 0.044 Uiso 1 1 calc R U . . .
N3 N 0.6282(11) 0.9892(6) 0.1572(4) 0.063(2) Uani 1 1 d . . . . .
O6 O 0.7229(12) 1.0769(5) 0.1957(4) 0.092(3) Uani 1 1 d . . . . .
O12 O 1.2320(14) 1.0135(6) 0.2344(5) 0.105(3) Uani 1 1 d . . . . .
N4 N 1.1247(11) 0.9295(6) 0.1955(4) 0.0580(18) Uani 1 1 d . . . . .
C12 C 1.0943(10) 0.8314(6) 0.2204(4) 0.0368(15) Uani 1 1 d . . . . .
C11 C 0.9766(9) 0.7349(6) 0.1759(4) 0.0364(15) Uani 1 1 d . . . . .
H11 H 0.917348 0.730347 0.129316 0.044 Uiso 1 1 calc R U . . .
C10 C 0.9478(8) 0.6443(5) 0.2018(3) 0.0297(13) Uani 1 1 d . . . . .
C9 C 0.8125(10) 0.5382(6) 0.1552(4) 0.0384(16) Uani 1 1 d . . . . .
C16 C 1.2753(9) 0.7596(6) 0.3881(3) 0.0355(15) Uani 1 1 d . . . . .
C14 C 1.1620(9) 0.7513(5) 0.3154(3) 0.0304(13) Uani 1 1 d . . . . .
C15 C 1.0413(9) 0.6535(5) 0.2711(3) 0.0315(14) Uani 1 1 d . . . . .
H15 H 1.022511 0.592524 0.288330 0.038 Uiso 1 1 calc R U . . .
C13 C 1.1869(9) 0.8423(5) 0.2896(4) 0.0356(15) Uani 1 1 d . . . . .
H13 H 1.264465 0.909405 0.318433 0.043 Uiso 1 1 calc R U . . .
O13 O 0.4354(13) 0.3468(7) 0.1706(6) 0.0544(13) Uani 0.578(3) 1 d . . P . .
Cu1 Cu 0.2599(4) 0.3532(2) 0.07055(17) 0.0317(4) Uani 0.422(3) 1 d . . P . .
O15 O 0.4745(17) 0.3122(10) 0.1194(9) 0.0544(13) Uani 0.422(3) 1 d . . P . .
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 Cu3 O1 180.0 2_565 . ?
O14 Cu3 O1 91.95(19) . . ?
O2 Cu2 O14 102.1(2) . . ?
O2 Cu2 O17 97.9(3) . . ?
O2 Cu2 N1 150.6(3) . . ?
O2 Cu2 O13 87.0(3) . . ?
O2 Cu2 O15 102.9(4) . . ?
O14 Cu2 O17 87.9(3) . . ?
O14 Cu2 O13 169.4(3) . . ?
O14 Cu2 O15 147.8(5) . . ?
N1 Cu2 O14 87.3(2) . . ?
N1 Cu2 O17 110.4(3) . . ?
N1 Cu2 O13 82.1(3) . . ?
N1 Cu2 O15 80.8(4) . . ?
O13 Cu2 O17 96.4(4) . . ?
O13 Cu2 O15 30.5(4) . . ?
Cu1 Cu2 O2 124.8(5) . . ?
Cu1 Cu2 O14 77.9(4) . . ?
Cu1 Cu2 O17 27.5(4) . . ?
Cu1 Cu2 N1 84.2(5) . . ?
Cu1 Cu2 O13 101.6(6) . . ?
Cu1 Cu2 O15 71.2(6) . . ?
O15 Cu2 O17 68.8(5) . . ?
O3 Cu5 O3 180.0 2_776 . ?
O20 Cu5 O3 89.00(19) . . ?
O20 Cu4 O4 97.0(2) . . ?
O20 Cu4 N2 88.7(2) . . ?
O20 Cu4 O16 164.2(2) . . ?
O20 Cu4 O18 101.5(3) . . ?
O4 Cu4 N2 174.0(2) . . ?
O4 Cu4 O16 91.8(2) . . ?
O4 Cu4 O18 88.4(3) . . ?
N2 Cu4 O18 88.7(4) . . ?
O16 Cu4 N2 83.1(2) . . ?
O16 Cu4 O18 91.8(3) . . ?
C1 O1 Cu3 138.4(4) . . ?
Cu2 O2 Cu1 13.53(11) . . ?
C1 O2 Cu2 126.9(4) . . ?
C1 O2 Cu1 118.0(4) . . ?
C8 O3 Cu5 133.3(4) . . ?
Cu4 O20 Cu5 112.5(2) . . ?
C25 O20 Cu5 123.9(4) . . ?
C25 O20 Cu4 107.1(4) . . ?
C8 O4 Cu4 126.7(4) . . ?
H19C O19 H19D 104.5 . . ?
Cu3 O14 Cu2 125.0(3) . . ?
C17 O14 Cu3 123.9(5) . . ?
C17 O14 Cu2 109.5(5) . . ?
C17 O14 Cu1 110.4(5) . . ?
Cu1 O14 Cu3 125.2(3) . . ?
Cu1 O14 Cu2 19.22(8) . . ?
C24 N2 Cu4 103.6(5) . . ?
C24 N2 C26 111.0(7) . . ?
C26 N2 Cu4 113.8(6) . . ?
C23 N2 Cu4 103.0(4) . . ?
C23 N2 C24 114.6(6) . . ?
C23 N2 C26 110.6(8) . . ?
Cu4 O16 H16 133(2) . . ?
C22 O16 Cu4 113.8(4) . . ?
C22 O16 H16 107.1(19) . . ?
O1 C1 C2 116.4(6) . . ?
O2 C1 O1 127.1(6) . . ?
O2 C1 C2 116.4(5) . . ?
Cu2 O17 H17A 108.4 . . ?
Cu2 O17 H17B 107.0 . . ?
H17A O17 H17B 104.0 . . ?
Cu1 O17 Cu2 9.52(12) . . ?
Cu1 O17 H17A 109.3 . . ?
Cu1 O17 H17B 115.3 . . ?
Cu2 N1 Cu1 18.92(9) . . ?
C21 N1 Cu2 116.5(11) . . ?
C21 N1 Cu1 97.8(11) . . ?
C19 N1 Cu2 105.5(6) . . ?
C19 N1 C21 102.2(12) . . ?
C19 N1 Cu1 114.4(6) . . ?
C18 N1 Cu2 103.5(6) . . ?
C18 N1 C21 101.5(12) . . ?
C18 N1 C19 128.5(9) . . ?
C18 N1 Cu1 106.8(5) . . ?
N1 C21 H21A 109.5 . . ?
N1 C21 H21B 109.5 . . ?
N1 C21 H21C 109.5 . . ?
H21A C21 H21B 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
C19 C20 O15 110.5(8) . . ?
O13 C20 C19 98.5(9) . . ?
O13 C20 O15 43.2(7) . . ?
N1 C19 C20 112.7(9) . . ?
N1 C19 H19A 109.1 . . ?
N1 C19 H19B 109.1 . . ?
C20 C19 H19A 109.1 . . ?
C20 C19 H19B 109.1 . . ?
H19A C19 H19B 107.8 . . ?
N1 C18 H18A 107.7 . . ?
N1 C18 H18B 107.7 . . ?
N1 C18 C17 118.5(9) . . ?
H18A C18 H18B 107.1 . . ?
C17 C18 H18A 107.7 . . ?
C17 C18 H18B 107.7 . . ?
O14 C17 C18 111.4(8) . . ?
O14 C17 H17C 109.3 . . ?
O14 C17 H17D 109.3 . . ?
C18 C17 H17C 109.3 . . ?
C18 C17 H17D 109.3 . . ?
H17C C17 H17D 108.0 . . ?
C7 C2 C1 120.9(6) . . ?
C7 C2 C3 119.6(5) . . ?
C3 C2 C1 119.5(5) . . ?
C2 C7 H7 119.4 . . ?
C2 C7 C6 121.2(6) . . ?
C6 C7 H7 119.4 . . ?
C7 C6 C8 121.4(6) . . ?
C5 C6 C7 119.4(5) . . ?
C5 C6 C8 119.3(5) . . ?
O3 C8 O4 127.8(6) . . ?
O3 C8 C6 116.7(6) . . ?
O4 C8 C6 115.5(5) . . ?
O20 C25 H25A 110.0 . . ?
O20 C25 H25B 110.0 . . ?
O20 C25 C24 108.7(6) . . ?
H25A C25 H25B 108.3 . . ?
C24 C25 H25A 110.0 . . ?
C24 C25 H25B 110.0 . . ?
N2 C24 C25 108.8(6) . . ?
N2 C24 H24A 109.9 . . ?
N2 C24 H24B 109.9 . . ?
C25 C24 H24A 109.9 . . ?
C25 C24 H24B 109.9 . . ?
H24A C24 H24B 108.3 . . ?
N2 C26 H26A 109.5 . . ?
N2 C26 H26B 109.5 . . ?
N2 C26 H26C 109.5 . . ?
H26A C26 H26B 109.5 . . ?
H26A C26 H26C 109.5 . . ?
H26B C26 H26C 109.5 . . ?
Cu4 O18 H18C 116.5 . . ?
Cu4 O18 H18D 116.6 . . ?
H18C O18 H18D 96.8 . . ?
O16 C22 H22A 110.1 . . ?
O16 C22 H22B 110.1 . . ?
O16 C22 C23 108.2(6) . . ?
H22A C22 H22B 108.4 . . ?
C23 C22 H22A 110.1 . . ?
C23 C22 H22B 110.1 . . ?
N2 C23 C22 109.6(7) . . ?
N2 C23 H23A 109.7 . . ?
N2 C23 H23B 109.7 . . ?
C22 C23 H23A 109.7 . . ?
C22 C23 H23B 109.7 . . ?
H23A C23 H23B 108.2 . . ?
C6 C5 H5 120.6 . . ?
C6 C5 C4 118.8(6) . . ?
C4 C5 H5 120.6 . . ?
C5 C4 N3 118.4(6) . . ?
C3 C4 C5 123.0(6) . . ?
C3 C4 N3 118.6(6) . . ?
C2 C3 H3 121.0 . . ?
C4 C3 C2 118.1(6) . . ?
C4 C3 H3 121.0 . . ?
O5 N3 C4 118.4(6) . . ?
O6 N3 O5 122.5(7) . . ?
O6 N3 C4 119.0(6) . . ?
O11 N4 C12 117.8(7) . . ?
O12 N4 O11 122.5(7) . . ?
O12 N4 C12 119.6(7) . . ?
C11 C12 N4 120.1(6) . . ?
C11 C12 C13 123.0(6) . . ?
C13 C12 N4 116.9(6) . . ?
C12 C11 H11 120.7 . . ?
C12 C11 C10 118.6(6) . . ?
C10 C11 H11 120.7 . . ?
C11 C10 C9 119.6(6) . . ?
C11 C10 C15 119.2(6) . . ?
C15 C10 C9 121.2(6) . . ?
O7 C9 C10 118.5(6) . . ?
O8 C9 O7 125.4(7) . . ?
O8 C9 C10 116.0(6) . . ?
O9 C16 C14 117.2(6) . . ?
O10 C16 O9 125.4(6) . . ?
O10 C16 C14 117.3(6) . . ?
C15 C14 C16 121.9(6) . . ?
C15 C14 C13 118.6(6) . . ?
C13 C14 C16 119.4(6) . . ?
C10 C15 H15 119.1 . . ?
C14 C15 C10 121.8(6) . . ?
C14 C15 H15 119.1 . . ?
C12 C13 C14 118.8(6) . . ?
C12 C13 H13 120.6 . . ?
C14 C13 H13 120.6 . . ?
Cu2 O13 Cu1 16.51(11) . . ?
C20 O13 Cu2 114.2(7) . . ?
C20 O13 Cu1 107.2(7) . . ?
O15 O13 Cu2 80.2(8) . . ?
O15 O13 C20 77.0(11) . . ?
O15 O13 Cu1 63.7(8) . . ?
Cu2 Cu1 O2 41.7(4) . . ?
Cu2 Cu1 O14 82.9(5) . . ?
Cu2 Cu1 O17 143.0(5) . . ?
Cu2 Cu1 N1 76.8(5) . . ?
Cu2 Cu1 O13 61.9(5) . . ?
Cu2 Cu1 O15 91.0(6) . . ?
O14 Cu1 O2 88.9(2) . . ?
O14 Cu1 N1 86.9(3) . . ?
O14 Cu1 O13 143.2(4) . . ?
O14 Cu1 O15 168.9(5) . . ?
O17 Cu1 O2 101.9(3) . . ?
O17 Cu1 O14 107.3(3) . . ?
O17 Cu1 N1 137.7(4) . . ?
O17 Cu1 O13 107.3(4) . . ?
O17 Cu1 O15 83.2(5) . . ?
N1 Cu1 O2 118.4(3) . . ?
N1 Cu1 O13 75.8(3) . . ?
N1 Cu1 O15 82.7(4) . . ?
O13 Cu1 O2 72.1(3) . . ?
O15 Cu1 O2 92.7(5) . . ?
O15 Cu1 O13 29.1(5) . . ?
C20 O15 Cu2 101.6(9) . . ?
C20 O15 Cu1 111.5(8) . . ?
O13 O15 Cu2 69.4(9) . . ?
O13 O15 C20 59.8(10) . . ?
O13 O15 Cu1 87.2(10) . . ?
Cu1 O15 Cu2 17.83(13) . . ?
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Cu3 O1 1.990(4) . ?
Cu3 O14 1.927(5) . ?
Cu2 O2 1.829(5) . ?
Cu2 O14 1.941(5) . ?
Cu2 O17 2.343(7) . ?
Cu2 N1 1.933(6) . ?
Cu2 O13 1.997(9) . ?
Cu2 Cu1 0.644(2) . ?
Cu2 O15 2.102(13) . ?
Cu5 O3 1.995(4) . ?
Cu5 O20 1.939(5) . ?
Cu4 O20 1.917(5) . ?
Cu4 O4 1.918(4) . ?
Cu4 N2 2.009(6) . ?
Cu4 O16 1.973(5) . ?
Cu4 O18 2.422(10) . ?
O1 C1 1.248(7) . ?
O2 C1 1.243(8) . ?
O2 Cu1 2.259(5) . ?
O3 C8 1.242(8) . ?
O20 C25 1.423(8) . ?
O4 C8 1.260(8) . ?
O5 N3 1.210(9) . ?
O7 C9 1.260(8) . ?
O9 C16 1.267(8) . ?
O8 C9 1.252(9) . ?
O11 N4 1.227(9) . ?
O10 C16 1.249(8) . ?
O19 H19C 0.8497 . ?
O19 H19D 0.8505 . ?
O14 C17 1.391(10) . ?
O14 Cu1 1.912(6) . ?
N2 C24 1.470(10) . ?
N2 C26 1.506(11) . ?
N2 C23 1.461(11) . ?
O16 H16 0.861(10) . ?
O16 C22 1.425(9) . ?
C1 C2 1.504(8) . ?
O17 H17A 0.8566 . ?
O17 H17B 0.8625 . ?
O17 Cu1 1.797(7) . ?
N1 C21 1.505(18) . ?
N1 C19 1.386(11) . ?
N1 C18 1.366(12) . ?
N1 Cu1 1.975(7) . ?
C21 H21A 0.9600 . ?
C21 H21B 0.9600 . ?
C21 H21C 0.9600 . ?
C20 C19 1.520(15) . ?
C20 O13 1.367(13) . ?
C20 O15 1.540(16) . ?
C19 H19A 0.9700 . ?
C19 H19B 0.9700 . ?
C18 H18A 0.9700 . ?
C18 H18B 0.9700 . ?
C18 C17 1.447(12) . ?
C17 H17C 0.9700 . ?
C17 H17D 0.9700 . ?
C2 C7 1.386(8) . ?
C2 C3 1.398(9) . ?
C7 H7 0.9300 . ?
C7 C6 1.388(8) . ?
C6 C8 1.515(8) . ?
C6 C5 1.383(9) . ?
C25 H25A 0.9700 . ?
C25 H25B 0.9700 . ?
C25 C24 1.512(12) . ?
C24 H24A 0.9700 . ?
C24 H24B 0.9700 . ?
C26 H26A 0.9600 . ?
C26 H26B 0.9600 . ?
C26 H26C 0.9600 . ?
O18 H18C 1.0318 . ?
O18 H18D 1.0352 . ?
C22 H22A 0.9700 . ?
C22 H22B 0.9700 . ?
C22 C23 1.518(11) . ?
C23 H23A 0.9700 . ?
C23 H23B 0.9700 . ?
C5 H5 0.9300 . ?
C5 C4 1.383(9) . ?
C4 C3 1.373(9) . ?
C4 N3 1.485(9) . ?
C3 H3 0.9300 . ?
N3 O6 1.205(9) . ?
O12 N4 1.207(10) . ?
N4 C12 1.464(9) . ?
C12 C11 1.371(10) . ?
C12 C13 1.378(9) . ?
C11 H11 0.9300 . ?
C11 C10 1.384(9) . ?
C10 C9 1.509(9) . ?
C10 C15 1.389(9) . ?
C16 C14 1.507(9) . ?
C14 C15 1.387(9) . ?
C14 C13 1.389(9) . ?
C15 H15 0.9300 . ?
C13 H13 0.9300 . ?
O13 Cu1 2.218(9) . ?
O13 O15 1.082(17) . ?
Cu1 O15 1.991(12) . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Cu3 O1 C1 O2 15.1(11) . . . . ?
Cu3 O1 C1 C2 -164.2(4) . . . . ?
Cu3 O14 C17 C18 -162.3(9) . . . . ?
Cu2 O2 C1 O1 15.4(10) . . . . ?
Cu2 O2 C1 C2 -165.2(4) . . . . ?
Cu2 O14 C17 C18 4.0(15) . . . . ?
Cu2 O17 Cu1 O2 8.8(8) . . . . ?
Cu2 O17 Cu1 O14 101.4(9) . . . . ?
Cu2 O17 Cu1 N1 -153.7(12) . . . . ?
Cu2 O17 Cu1 O13 -66.0(9) . . . . ?
Cu2 O17 Cu1 O15 -82.5(9) . . . . ?
Cu2 N1 C19 C20 -47.4(13) . . . . ?
Cu2 N1 C18 C17 34.6(15) . . . . ?
Cu2 O13 O15 C20 -117.9(6) . . . . ?
Cu2 O13 O15 Cu1 -0.9(3) . . . . ?
Cu5 O3 C8 O4 -10.4(11) . . . . ?
Cu5 O3 C8 C6 168.7(4) . . . . ?
Cu5 O20 C25 C24 92.1(7) . . . . ?
Cu4 O20 C25 C24 -41.5(6) . . . . ?
Cu4 O4 C8 O3 4.0(10) . . . . ?
Cu4 O4 C8 C6 -175.1(4) . . . . ?
Cu4 N2 C24 C25 -37.1(7) . . . . ?
Cu4 N2 C23 C22 50.6(7) . . . . ?
Cu4 O16 C22 C23 11.4(8) . . . . ?
O1 C1 C2 C7 167.8(6) . . . . ?
O1 C1 C2 C3 -12.4(9) . . . . ?
O2 Cu2 Cu1 O14 -96.4(4) . . . . ?
O2 Cu2 Cu1 O17 13.0(11) . . . . ?
O2 Cu2 Cu1 N1 175.2(4) . . . . ?
O2 Cu2 Cu1 O13 94.5(5) . . . . ?
O2 Cu2 Cu1 O15 92.9(5) . . . . ?
O2 C1 C2 C7 -11.7(9) . . . . ?
O2 C1 C2 C3 168.1(6) . . . . ?
O20 C25 C24 N2 54.3(8) . . . . ?
O9 C16 C14 C15 1.1(9) . . . . ?
O9 C16 C14 C13 -175.1(6) . . . . ?
O11 N4 C12 C11 4.0(12) . . . . ?
O11 N4 C12 C13 -175.2(8) . . . . ?
O10 C16 C14 C15 178.3(6) . . . . ?
O10 C16 C14 C13 2.2(9) . . . . ?
O14 Cu2 O2 C1 -31.4(7) . . . . ?
O14 Cu2 O2 Cu1 -83.5(6) . . . . ?
O14 Cu2 Cu1 O2 96.4(4) . . . . ?
O14 Cu2 Cu1 O17 109.4(8) . . . . ?
O14 Cu2 Cu1 N1 -88.5(2) . . . . ?
O14 Cu2 Cu1 O13 -169.2(3) . . . . ?
O14 Cu2 Cu1 O15 -170.7(4) . . . . ?
O16 C22 C23 N2 -41.9(9) . . . . ?
C1 C2 C7 C6 -178.8(6) . . . . ?
C1 C2 C3 C4 178.9(6) . . . . ?
O17 Cu2 O2 C1 58.2(6) . . . . ?
O17 Cu2 O2 Cu1 6.0(5) . . . . ?
O17 Cu2 Cu1 O2 -13.0(11) . . . . ?
O17 Cu2 Cu1 O14 -109.4(8) . . . . ?
O17 Cu2 Cu1 N1 162.1(8) . . . . ?
O17 Cu2 Cu1 O13 81.4(9) . . . . ?
O17 Cu2 Cu1 O15 79.9(9) . . . . ?
N1 Cu2 O2 C1 -137.7(6) . . . . ?
N1 Cu2 O2 Cu1 170.2(9) . . . . ?
N1 Cu2 Cu1 O2 -175.2(5) . . . . ?
N1 Cu2 Cu1 O14 88.5(2) . . . . ?
N1 Cu2 Cu1 O17 -162.1(8) . . . . ?
N1 Cu2 Cu1 O13 -80.7(3) . . . . ?
N1 Cu2 Cu1 O15 -82.3(4) . . . . ?
N1 C18 C17 O14 -27.4(19) . . . . ?
C21 N1 C19 C20 74.9(15) . . . . ?
C21 N1 C18 C17 -86.6(16) . . . . ?
C20 O13 O15 Cu2 117.9(6) . . . . ?
C20 O13 O15 Cu1 117.0(6) . . . . ?
C19 N1 C18 C17 157.5(13) . . . . ?
C19 C20 O13 Cu2 -38.2(13) . . . . ?
C19 C20 O13 Cu1 -54.2(11) . . . . ?
C19 C20 O13 O15 -111.0(12) . . . . ?
C19 C20 O15 Cu2 22.7(14) . . . . ?
C19 C20 O15 O13 80.4(13) . . . . ?
C19 C20 O15 Cu1 7.3(16) . . . . ?
C18 N1 C19 C20 -169.5(12) . . . . ?
C2 C7 C6 C8 178.4(5) . . . . ?
C2 C7 C6 C5 -0.4(9) . . . . ?
C7 C2 C3 C4 -1.3(10) . . . . ?
C7 C6 C8 O3 176.2(6) . . . . ?
C7 C6 C8 O4 -4.6(9) . . . . ?
C7 C6 C5 C4 -0.7(10) . . . . ?
C6 C5 C4 C3 0.8(11) . . . . ?
C6 C5 C4 N3 179.9(7) . . . . ?
C8 C6 C5 C4 -179.5(6) . . . . ?
C24 N2 C23 C22 162.3(6) . . . . ?
C26 N2 C24 C25 85.4(9) . . . . ?
C26 N2 C23 C22 -71.3(9) . . . . ?
C23 N2 C24 C25 -148.5(7) . . . . ?
C5 C6 C8 O3 -5.0(9) . . . . ?
C5 C6 C8 O4 174.2(6) . . . . ?
C5 C4 C3 C2 0.2(11) . . . . ?
C5 C4 N3 O5 179.1(9) . . . . ?
C5 C4 N3 O6 -2.1(13) . . . . ?
C3 C2 C7 C6 1.4(9) . . . . ?
C3 C4 N3 O5 -1.8(13) . . . . ?
C3 C4 N3 O6 177.0(9) . . . . ?
N3 C4 C3 C2 -178.8(7) . . . . ?
O12 N4 C12 C11 -178.3(9) . . . . ?
O12 N4 C12 C13 2.5(12) . . . . ?
N4 C12 C11 C10 -178.6(6) . . . . ?
N4 C12 C13 C14 180.0(6) . . . . ?
C12 C11 C10 C9 177.4(6) . . . . ?
C12 C11 C10 C15 -1.2(9) . . . . ?
C11 C12 C13 C14 0.8(10) . . . . ?
C11 C10 C9 O7 12.0(10) . . . . ?
C11 C10 C9 O8 -167.9(6) . . . . ?
C11 C10 C15 C14 0.4(9) . . . . ?
C9 C10 C15 C14 -178.2(6) . . . . ?
C16 C14 C15 C10 -175.2(6) . . . . ?
C16 C14 C13 C12 174.7(6) . . . . ?
C15 C10 C9 O7 -169.5(6) . . . . ?
C15 C10 C9 O8 10.6(10) . . . . ?
C15 C14 C13 C12 -1.6(9) . . . . ?
C13 C12 C11 C10 0.6(10) . . . . ?
C13 C14 C15 C10 1.0(10) . . . . ?
O13 Cu2 O2 C1 154.2(7) . . . . ?
O13 Cu2 O2 Cu1 102.1(7) . . . . ?
O13 Cu2 Cu1 O2 -94.5(5) . . . . ?
O13 Cu2 Cu1 O14 169.2(3) . . . . ?
O13 Cu2 Cu1 O17 -81.4(9) . . . . ?
O13 Cu2 Cu1 N1 80.7(3) . . . . ?
O13 Cu2 Cu1 O15 -1.6(5) . . . . ?
O13 C20 C19 N1 56.8(15) . . . . ?
O13 C20 O15 Cu2 -57.6(8) . . . . ?
O13 C20 O15 Cu1 -73.1(10) . . . . ?
Cu1 Cu2 O2 C1 52.1(9) . . . . ?
Cu1 O2 C1 O1 27.5(9) . . . . ?
Cu1 O2 C1 C2 -153.1(4) . . . . ?
Cu1 O14 C17 C18 24.5(14) . . . . ?
Cu1 N1 C19 C20 -29.6(14) . . . . ?
Cu1 N1 C18 C17 15.3(15) . . . . ?
Cu1 O13 O15 Cu2 0.9(3) . . . . ?
Cu1 O13 O15 C20 -117.0(6) . . . . ?
O15 Cu2 O2 C1 128.1(7) . . . . ?
O15 Cu2 O2 Cu1 75.9(7) . . . . ?
O15 Cu2 Cu1 O2 -92.9(5) . . . . ?
O15 Cu2 Cu1 O14 170.7(4) . . . . ?
O15 Cu2 Cu1 O17 -79.9(9) . . . . ?
O15 Cu2 Cu1 N1 82.3(4) . . . . ?
O15 Cu2 Cu1 O13 1.6(5) . . . . ?
O15 C20 C19 N1 13.8(17) . . . . ?
O15 C20 O13 Cu2 72.8(10) . . . . ?
O15 C20 O13 Cu1 56.8(8) . . . . ?
