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_7249648
_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         'C20 H32 Cu2 N8 O8, 5.5(C H4 O)'
_chemical_formula_sum            'C25.5 H54 Cu2 N8 O13.5'
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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             2024-01-18
_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                90.0
_cell_angle_beta                 90.0
_cell_angle_gamma                120.0
_cell_formula_units_Z            6
_cell_length_a                   13.3717(9)
_cell_length_b                   13.3717(9)
_cell_length_c                   36.410(2)
_cell_measurement_reflns_used    1629
_cell_measurement_temperature    150(1)
_cell_measurement_theta_max      20.6940
_cell_measurement_theta_min      4.5220
_cell_volume                     5638.0(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_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      150(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.3426
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.859
_diffrn_measured_fraction_theta_max 0.859
_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    -57.00  60.00   1.00    1.00    --  -18.46  37.00  30.00  117
  2  \w    -45.00  59.00   1.00    1.00    --  -18.46 -19.00-120.00  104
;
_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      0.0382212000
_diffrn_orient_matrix_UB_12      -0.0110925000
_diffrn_orient_matrix_UB_13      -0.0104625000
_diffrn_orient_matrix_UB_21      0.0326825000
_diffrn_orient_matrix_UB_22      0.0062597000
_diffrn_orient_matrix_UB_23      0.0160208000
_diffrn_orient_matrix_UB_31      -0.0349846000
_diffrn_orient_matrix_UB_32      -0.0599301000
_diffrn_orient_matrix_UB_33      0.0036249000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0960
_diffrn_reflns_av_unetI/netI     0.1435
_diffrn_reflns_Laue_measured_fraction_full 0.859
_diffrn_reflns_Laue_measured_fraction_max 0.859
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            13784
_diffrn_reflns_point_group_measured_fraction_full 0.825
_diffrn_reflns_point_group_measured_fraction_max 0.825
_diffrn_reflns_theta_full        24.880
_diffrn_reflns_theta_max         24.880
_diffrn_reflns_theta_min         4.295
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.201
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66962
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_description       prism
_exptl_crystal_F_000             2574
_exptl_crystal_size_max          0.44
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.20
_refine_diff_density_max         1.111
_refine_diff_density_min         -1.020
_refine_diff_density_rms         0.155
_refine_ls_abs_structure_details
;
 Flack x determined using 918 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.022(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     306
_refine_ls_number_reflns         13784
_refine_ls_number_restraints     49
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.1463
_refine_ls_R_factor_gt           0.1068
_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^)+84.9862P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1967
_refine_ls_wR_factor_ref         0.2223
_reflns_Friedel_coverage         0.688
_reflns_Friedel_fraction_full    0.780
_reflns_Friedel_fraction_max     0.780
_reflns_number_gt                9993
_reflns_number_total             13784
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ce01070a2.cif
_cod_data_source_block           3
_cod_depositor_comments
'Adding full bibliography for 7249643--7249648.cif.'
_cod_original_cell_volume        5637.9(6)
_cod_original_formula_sum        'C25.50 H54 Cu2 N8 O13.50'
_cod_database_code               7249648
_shelx_shelxl_version_number     2018/3
_cell_oxdiff_angle_alpha         90.037(9)
_cell_oxdiff_angle_beta          89.850(9)
_cell_oxdiff_angle_gamma         120.009(15)
_cell_oxdiff_length_a            13.371(2)
_cell_oxdiff_length_b            13.3691(17)
_cell_oxdiff_length_c            36.421(3)
_cell_oxdiff_measurement_reflns_used 1629
_cell_oxdiff_volume              5638(1)
_shelx_estimated_absorpt_t_max   0.795
_shelx_estimated_absorpt_t_min   0.620
_reflns_odcompleteness_completeness 98.69
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     21.92
_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 C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O2-H2
 0.85 with sigma of 0.01
 O1-H1
 0.85 with sigma of 0.01
 O3-C3
 1.4 with sigma of 0.01
 O4-C4
 1.4 with sigma of 0.01
 O5-C5
 1.4 with sigma of 0.01
 O8-C8
 1.4 with sigma of 0.01
 O6-C6
 1.4 with sigma of 0.01
 O7-C7
 1.4 with sigma of 0.01
 O2-C2
 1.4 with sigma of 0.01
 O1-C1
 1.4 with sigma of 0.01
 Cu1-H1
 3.03 with sigma of 0.02
 Cu2-H2
 3.03 with sigma of 0.02
 C1-H1
 1.877 with sigma of 0.02
 C2-H2
 1.877 with sigma of 0.02
3. Rigid bond restraints
 Cu1, O1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 Cu1, N12
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 Cu1, N11
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.02
 Cu1, N23
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.02
 Cu1, O11
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
Cu1 \\sim O1: within 2.4A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2.4A
Cu1 \\sim N12: within 2.1A with sigma of 0.01 and sigma for terminal atoms of
0.04 within 2.1A
Cu1 \\sim N11: within 2.1A with sigma of 0.002 and sigma for terminal atoms of
0.04 within 2.1A
Cu1 \\sim N23: within 2.1A with sigma of 0.005 and sigma for terminal atoms of
0.04 within 2.1A
Cu1 \\sim O11: within 2.1A with sigma of 0.01 and sigma for terminal atoms of
0.04 within 2.1A
5. Others
 Fixed Sof: O6(0.5) H6(0.5) C6(0.5) H6A(0.5) H6B(0.5) H6C(0.5)
 Fixed X: H6A(0.678901) H6B(0.73812) H6C(0.60323)
 Fixed Y: H6A(0.68976) H6B(0.767281) H6C(0.691251)
 Fixed Z: H6A(-0.02174) H6B(0.01275) H6C(0.01091)
6.a Ternary CH refined with riding coordinates:
 C15(H15), C25(H25)
6.b Secondary CH2 refined with riding coordinates:
 N11(H11A,H11B), N21(H21A,H21B), C11(H11C,H11D), C12(H12A,H12B), C16(H16A,
 H16B), C21(H21C,H21D), C22(H22A,H22B), C26(H26A,H26B)
6.c Me refined with riding coordinates:
 C1(H1A,H1B,H1C)
6.d Aromatic/amide H refined with riding coordinates:
 N14(H14), N24(H24), C18(H18), C19(H19), C28(H28), C29(H29)
6.e Tetrahedral OH refined with riding coordinates:
 O5(H5), O8(H8), O6(H6)
6.f Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C7(H7A,
 H7B,H7C), C8(H8A,H8B,H8C)
6.g Idealised tetrahedral OH refined as rotating group:
 O3(H3), O4(H4), O7(H7)
;
_shelx_res_checksum              37313
_shelx_hkl_checksum              31687
_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 1.408
_oxdiff_exptl_absorpt_empirical_full_min 0.868