Robustness and stability of the l-carnosine copper(ii) dimer: changes in the copper coordination sphere upon heating/solvent substitution
Mrvoš-Sermek, Draginja; Tašner, Marina; Vušak, Darko; Judaš, Nenad; Wzgarda-Raj, Kinga; Đilović, Ivica; Matković-Čalogović, Dubravka; CrystEngComm 27 (2025) 356–365; doi:10.1039/D4CE01070A

data_7249643
_publ_section_title
;
 Robustness and stability of the l-carnosine copper(ii) dimer: changes in
 the copper coordination sphere upon heating/solvent substitution
;
_journal_issue                   3
_journal_name_full               CrystEngComm
_journal_page_first              356
_journal_page_last               365
_journal_paper_doi               10.1039/D4CE01070A
_journal_volume                  27
_journal_year                    2025
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C18 H28 Cu2 N8 O8, 2(H2 O)'
_chemical_formula_sum            'C18 H32 Cu2 N8 O10'
_chemical_formula_weight         647.60
_space_group_crystal_system      trigonal
_space_group_IT_number           152
_space_group_name_Hall           'P 31 2"'
_space_group_name_H-M_alt        'P 31 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-12-03
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-01-22 deposited with the CCDC.	2024-11-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   8.56884(6)
_cell_length_b                   8.56884(6)
_cell_length_c                   30.61946(18)
_cell_measurement_reflns_used    30246
_cell_measurement_temperature    169.98(10)
_cell_measurement_theta_max      74.7530
_cell_measurement_theta_min      4.3220
_cell_volume                     1947.03(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.91a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 42.53a 64-bit (release 15-04-2022))'
_computing_data_reduction        'CrysAlisPro 1.171.43.91a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      170(1)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.985
_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   -121.00 -19.00   0.50    2.00    --  -42.63 -31.00 -13.00  204
  2  \w   -124.00 -16.00   0.50    4.00    --  -90.25  87.00-105.00  216
  3  \w     33.00 107.00   0.50    4.00    --  107.81-103.00-117.00  148
  4  \w     34.00 139.00   0.50    4.00    --  107.81 -81.00 -27.00  210
  5  \w    101.00 178.00   0.50    4.00    --  107.81  81.00  95.00  154
  6  \w    -26.00  38.00   0.50    2.00    --  -42.63  19.00   0.00  128
  7  \w   -117.00 -88.00   0.50    2.00    --  -42.63 -77.00  90.00   58
  8  \w   -117.00 -88.00   0.50    2.00    --  -42.63 -77.00   0.00   58
  9  \w     21.00 117.00   0.50    2.00    --   42.63  55.00 114.00  192
 10  \w     88.00 117.00   0.50    2.00    --   42.63  77.00-120.00   58
 11  \w     88.00 117.00   0.50    2.00    --   42.63  77.00 -60.00   58
 12  \w     88.00 117.00   0.50    2.00    --   42.63  77.00-150.00   58
 13  \w    -51.00 -14.00   0.50    4.00    --  -90.25  45.00 -90.00   74
 14  \w    -86.00 -16.00   0.50    4.00    --  -90.25 125.00-120.00  140
 15  \w     34.00  71.00   0.50    4.00    --  107.81 -61.00-120.00   74
 16  \w     34.00  71.00   0.50    4.00    --  107.81 -61.00 -30.00   74
 17  \w     34.00 105.00   0.50    4.00    --  107.81 -77.00  60.00  142
 18  \w     33.00 105.00   0.50    4.00    --  107.81 -95.00 -90.00  144
 19  \w     34.00 105.00   0.50    4.00    --  107.81 -77.00 150.00  142
 20  \w     84.00 178.00   0.50    4.00    --  107.81  30.00   0.00  188
 21  \w     34.00  71.00   0.50    4.00    --  107.81 -61.00-180.00   74
 22  \w     33.00 105.00   0.50    4.00    --  107.81 -95.00 -30.00  144
 23  \w     34.00  71.00   0.50    4.00    --  107.81 -61.00 -90.00   74
 24  \w     34.00 105.00   0.50    4.00    --  107.81 -77.00 120.00  142
 25  \w     86.00 178.00   0.50    4.00    --  107.81  45.00 120.00  184
 26  \w     84.00 178.00   0.50    4.00    --  107.81  30.00 -90.00  188
 27  \w     21.00 117.00   0.50    2.00    --   42.63  57.00  30.00  192
 28  \w     61.00 122.00   0.50    2.00    --   42.63-178.00 -90.00  122
 29  \w     21.00 117.00   0.50    2.00    --   42.63  57.00 -60.00  192
 30  \w     62.00 122.00   0.50    2.00    --   42.63 178.00-180.00  120
 31  \w     21.00 117.00   0.50    2.00    --   42.63  57.00-150.00  192
 32  \w     21.00 117.00   0.50    2.00    --   42.63  57.00-180.00  192
 33  \w   -164.00 -67.00   0.50    4.00    --  -90.25 -61.00 120.00  194
 34  \w    -51.00 -14.00   0.50    4.00    --  -90.25  45.00 120.00   74
 35  \w   -164.00 -67.00   0.50    4.00    --  -90.25 -61.00 -30.00  194
 36  \w   -164.00 -67.00   0.50    4.00    --  -90.25 -61.00  60.00  194
 37  \w   -164.00 -67.00   0.50    4.00    --  -90.25 -61.00-180.00  194
 38  \w   -164.00 -67.00   0.50    4.00    --  -90.25 -61.00   0.00  194
 39  \w   -164.00 -67.00   0.50    4.00    --  -90.25 -61.00 -90.00  194
 40  \w   -164.00 -67.00   0.50    4.00    --  -90.25 -61.00-120.00  194
 41  \w   -164.00 -67.00   0.50    4.00    --  -90.25 -61.00  90.00  194
 42  \w   -164.00 -67.00   0.50    4.00    --  -90.25 -61.00-150.00  194
 43  \w   -164.00 -67.00   0.50    4.00    --  -90.25 -61.00  30.00  194
 44  \w    -51.00 -14.00   0.50    4.00    --  -90.25  45.00  60.00   74
 45  \w   -164.00 -67.00   0.50    4.00    --  -90.25 -61.00 -60.00  194
 46  \w   -164.00 -67.00   0.50    4.00    --  -90.25 -61.00 150.00  194
 47  \w     84.00 178.00   0.50    4.00    --  107.81  30.00-150.00  188
 48  \w     84.00 178.00   0.50    4.00    --  107.81  30.00-180.00  188
 49  \w     86.00 178.00   0.50    4.00    --  107.81  45.00 -60.00  184
 50  \w     84.00 178.00   0.50    4.00    --  107.81  30.00  60.00  188
 51  \w     21.00 117.00   0.50    2.00    --   42.63  57.00-120.00  192
 52  \w     62.00 122.00   0.50    2.00    --   42.63 178.00  90.00  120
 53  \w     21.00 117.00   0.50    2.00    --   42.63  57.00  60.00  192
 54  \w     21.00 117.00   0.50    2.00    --   42.63  57.00   0.00  192
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0346
_diffrn_reflns_av_unetI/netI     0.0097
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            48652
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.075
_diffrn_reflns_theta_min         4.332
_exptl_absorpt_coefficient_mu    2.620
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81939
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.91a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            blue
_exptl_crystal_density_diffrn    1.657
_exptl_crystal_description       'hexagonal plate'
_exptl_crystal_F_000             1002
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.419
_refine_diff_density_min         -0.439
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 976 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.019(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     224
_refine_ls_number_reflns         2655
_refine_ls_number_restraints     38
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0336
_refine_ls_R_factor_gt           0.0318
_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^)+(0.0304P)^2^+1.1468P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0746
_refine_ls_wR_factor_ref         0.0757
_reflns_Friedel_coverage         0.668
_reflns_Friedel_fraction_full    0.990
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                2522
_reflns_number_total             2655
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ce01070a2.cif
_cod_data_source_block           1_170k
_cod_depositor_comments
'Adding full bibliography for 7249643--7249648.cif.'
_cod_original_cell_volume        1947.03(3)
_cod_database_code               7249643
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.926
_shelx_estimated_absorpt_t_min   0.761
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 Cu1-N1A \\sim Cu1-N1B
 with sigma of 0.005
 N1A-C1A \\sim N1B-C1B
 with sigma of 0.005
 C2A-C3A \\sim C2B-C3B
 with sigma of 0.005
 C3A-O3A \\sim C3B-O3B
 with sigma of 0.005
 C3A-N2 \\sim C3B-N2
 with sigma of 0.005
 Cu1-HW1A \\sim Cu1-HW1B
 with sigma of 0.02
3. Restrained planarity
 N2, C3A, O3A, C2A
 with sigma of 0.1
 N2, C3B, O3B, C2B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
N1A \\sim N1B: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 2A
C1A \\sim C1B: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 2A
C2A \\sim C2B: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 2A
C3A \\sim C3B: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 2A
O3A \\sim O3B: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 2A
5. Others
 Sof(O3B)=Sof(N1B)=Sof(H1BA)=Sof(H1BB)=Sof(C1B)=Sof(H1BC)=Sof(H1BD)=Sof(C2B)=
 Sof(H2BA)=Sof(H2BB)=Sof(C3B)=1-FVAR(1)
 Sof(O3A)=Sof(N1A)=Sof(H1AA)=Sof(H1AB)=Sof(C1A)=Sof(H1AC)=Sof(H1AD)=Sof(C2A)=
 Sof(H2AA)=Sof(H2AB)=Sof(C3A)=FVAR(1)
6.a Free rotating group:
 OW1(HW1A,HW1B), OW2(HW2A,HW2B)
6.b Ternary CH refined with riding coordinates:
 C5(H5)
6.c Secondary CH2 refined with riding coordinates:
 N1A(H1AA,H1AB), N1B(H1BA,H1BB), C1A(H1AC,H1AD), C1B(H1BC,H1BD), C2A(H2AA,
 H2AB), C2B(H2BA,H2BB), C6(H6A,H6B)
6.d Aromatic/amide H refined with riding coordinates:
 N4(H4), C8(H8), C9(H9)
;
_shelx_res_checksum              35412
_shelx_hkl_checksum              61351
_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
- Detector area scaling
;