Structural and electrochemical properties of mononuclear copper(II) complexes with pentadentate ethylenediamine-based ligands with pyridine/quinoline/isoquinoline/quinoxaline binding sites.
Mikata, Yuji; Akedo, Miyu; Hamamoto, Erina; Yoshida, Shoko; Shoji, Sunao; Ohsedo, Yutaka; Matsuo, Takashi; Storr, Tim; Funahashi, Yasuhiro; Dalton transactions (Cambridge, England : 2003) 53 (2024) 16716–16732; doi:10.1039/d4dt02363c

data_7717078
_publ_section_title
;
 Structural and electrochemical properties of mononuclear copper(II)
 complexes with pentadentate ethylenediamine-based ligands with
 pyridine/quinoline/isoquinoline/quinoxaline binding sites.
;
_journal_issue                   40
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              16716
_journal_page_last               16732
_journal_paper_doi               10.1039/d4dt02363c
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C33 H31 Cu N5, 2(Cl O4), 1.75(C2 H3 N)'
_chemical_formula_sum            'C36.5 H36.25 Cl2 Cu N6.75 O8'
_chemical_formula_weight         831.91
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-07-01
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-08-06 deposited with the CCDC.	2024-09-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.7113(5)
_cell_length_b                   45.9648(14)
_cell_length_c                   8.4267(2)
_cell_measurement_reflns_used    10141
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      28.8820
_cell_measurement_theta_min      2.4070
_cell_volume                     7634.8(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.109a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.109a 64-bit (release 21-02-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.109a (Rigaku OD, 2024)'
_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      150.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -42.00  62.12   0.38   25.00    --  -19.03  37.00-100.00  274
  2  \w    -17.00  22.14   0.38   25.00    --  -19.03 -99.00 -90.00  103
  3  \w    -24.00   1.08   0.38   25.00    --  -19.03  19.00-180.00   66
  4  \w    -19.00  28.12   0.38   25.00    --  -19.03 -99.00  30.00  124
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0354
_diffrn_reflns_av_unetI/netI     0.0579
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       54
_diffrn_reflns_limit_k_min       -55
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            28038
_diffrn_reflns_point_group_measured_fraction_full 0.964
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.348
_diffrn_reflns_theta_min         2.248
_exptl_absorpt_coefficient_mu    0.772
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.730
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.109a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.447
_exptl_crystal_description       needle
_exptl_crystal_F_000             3436
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.553
_refine_diff_density_min         -0.485
_refine_diff_density_rms         0.070
_refine_ls_abs_structure_details
;
 Flack x determined using 3689 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.438(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1160
_refine_ls_number_reflns         13467
_refine_ls_number_restraints     703
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0745
_refine_ls_R_factor_gt           0.0484
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0593P)^2^+4.8732P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1139
_refine_ls_wR_factor_ref         0.1260
_reflns_Friedel_coverage         0.730
_reflns_Friedel_fraction_full    0.922
_reflns_Friedel_fraction_max     0.920
_reflns_number_gt                10247
_reflns_number_total             13467
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt02363c2.cif
_cod_data_source_block           metqen-cu(clo4)2-240522_autored
_cod_depositor_comments
'Adding full bibliography for 7717077--7717088.cif.'
_cod_original_formula_sum        'C36.50 H36.25 Cl2 Cu N6.75 O8'
_cod_database_code               7717078
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.962
_shelx_estimated_absorpt_t_min   0.848
_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
2. Restrained distances
 Cl6-O17 = Cl6-O18 = Cl6-O19 = Cl6-O1A
 1.5 with sigma of 0.02
 C1C-C1D
 1.456 with sigma of 0.01
 N14-C1C
 1.14 with sigma of 0.02
 C1D-N14
 2.593 with sigma of 0.02
 Cl4-O13 = Cl4-O14 = Cl4-O15 = Cl4-O16
 1.5 with sigma of 0.02
 C1C-N14
 1.137 with sigma of 0.01
 Cl2-O5 = Cl2-O6 = Cl2-O7 = Cl2-O8
 1.5 with sigma of 0.02
 N13-C1A
 1.14 with sigma of 0.02
 C1A-N13
 1.137 with sigma of 0.01
 C1A-C1B
 1.456 with sigma of 0.01
 C1B-N13
 2.593 with sigma of 0.02
 N14-C1D
 2.59 with sigma of 0.04
 N13-C1B
 2.59 with sigma of 0.04
 C1C-C1D \\sim C71-C1E
 with sigma of 0.02
 N14-C1D \\sim N14A-C1E
 with sigma of 0.04
 Cl4-O13 \\sim Cl4-O14 \\sim Cl4-O15 \\sim Cl4-O16
 with sigma of 0.02
 N14-C1C \\sim N14A-C71
 with sigma of 0.02
 Cl6-O17 \\sim Cl6-O18 \\sim Cl6-O19 \\sim Cl6-O1A
 with sigma of 0.02
 O13-O15 \\sim O14-O16 \\sim O13-O16 \\sim O14-O15 \\sim O13-O14 \\sim O15-O16
 with sigma of 0.04
 O17-O19 \\sim O18-O1A \\sim O17-O1A \\sim O18-O19 \\sim O17-O18 \\sim O19-O1A
 with sigma of 0.04
 Cl4-O13 \\sim Cl4A-O13A
 with sigma of 0.02
 Cl4-O14 \\sim Cl4A-O14A
 with sigma of 0.02
 Cl4-O15 \\sim Cl4A-O15A
 with sigma of 0.02
 Cl4-O16 \\sim Cl4A-O16A
 with sigma of 0.02
 O13-O14 \\sim O13A-O14A
 with sigma of 0.04
 O13-O15 \\sim O13A-O15A
 with sigma of 0.04
 O13-O16 \\sim O13A-O16A
 with sigma of 0.04
 O14-O15 \\sim O14A-O15A
 with sigma of 0.04
 Cl2-O5 \\sim Cl2-O6 \\sim Cl2-O7 \\sim Cl2-O8
 with sigma of 0.02
 O14-O16 \\sim O14A-O16A
 with sigma of 0.04
 O15-O16 \\sim O15A-O16A
 with sigma of 0.04
 O5-O7 \\sim O6-O8 \\sim O5-O8 \\sim O6-O7 \\sim O5-O6 \\sim O7-O8
 with sigma of 0.04
 Cl2-O5 \\sim Cl2A-O5A
 with sigma of 0.02
 Cl2-O6 \\sim Cl2A-O6A
 with sigma of 0.02
 Cl2-O7 \\sim Cl2A-O7A
 with sigma of 0.02
 Cl2-O8 \\sim Cl2A-O8A
 with sigma of 0.02
 O5-O6 \\sim O5A-O6A
 with sigma of 0.04
 O5-O7 \\sim O5A-O7A
 with sigma of 0.04
 O5-O8 \\sim O5A-O8A
 with sigma of 0.04
 O6-O7 \\sim O6A-O7A
 with sigma of 0.04
 O6-O8 \\sim O6A-O8A
 with sigma of 0.04
 O7-O8 \\sim O7A-O8A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C1E \\sim C71 \\sim N14A \\sim C1D \\sim N14 \\sim C1C: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 2A
Cl4 \\sim O13 \\sim O14 \\sim O15 \\sim O16: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
Cl6 \\sim O17 \\sim O18 \\sim O19 \\sim O1A: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
O13 \\sim Cl4 \\sim O14 \\sim O15 \\sim O16 \\sim O13A \\sim Cl4A \\sim O15A
\\sim O16A \\sim O14A: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 1.7A
N13 \\sim C1A \\sim C1B: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cl2 \\sim O5 \\sim O6 \\sim O7 \\sim O8: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 2A
O7A \\sim Cl2A \\sim O5A \\sim O8A \\sim O6A \\sim Cl2 \\sim O5 \\sim O6 \\sim
O7 \\sim O8: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
within 2A
4. Rigid body (RIGU) restrains
 C1D, N14, C1C, C1E, C71, N14A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl4, O13, O14, O15, O16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl6, O17, O18, O19, O1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O13, Cl4, O14, O15, O16, O15A, O13A, Cl4A, O16A, O14A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl2, O5, O6, O7, O8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N13, C1A, C1B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O8, Cl2, O5, O6, O7
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O7, Cl2, O5, O6, O8, O7A, Cl2A, O5A, O8A, O6A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(C1E)=Sof(H1EA)=Sof(H1EB)=Sof(H1EC)=Sof(N14A)=Sof(C71)=1-FVAR(1)
 Sof(N14)=Sof(C1C)=Sof(C1D)=Sof(H1DA)=Sof(H1DB)=Sof(H1DC)=FVAR(1)
 Sof(O7A)=Sof(Cl2A)=Sof(O5A)=Sof(O8A)=Sof(O6A)=1-FVAR(2)
 Sof(Cl2)=Sof(O5)=Sof(O6)=Sof(O7)=Sof(O8)=FVAR(2)
 Fixed Sof: Cl6(0.5) O17(0.5) O18(0.5) O19(0.5) O1A(0.5) Cl4(0.25) O13(0.25)
 O14(0.25) O15(0.25) O16(0.25) O13A(0.25) Cl4A(0.25) O15A(0.25) O16A(0.25)
 O14A(0.25) N13(0.5) C1A(0.5) C1B(0.5) H1BA(0.5) H1BB(0.5) H1BC(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C36(H36A,H36B), C56(H56A,H56B), C35(H35A,H35B), C34(H34A,
 H34B), C23(H23A,H23B), C3(H3A,H3B), C1(H1A,H1B), C46(H46A,H46B), C2(H2A,H2B)
6.b Me refined with riding coordinates:
 C1D(H1DA,H1DB,H1DC), C1E(H1EA,H1EB,H1EC)
6.c Aromatic/amide H refined with riding coordinates:
 C49(H49), C48(H48), C30(H30), C63(H63), C6(H6), C40(H40), C50(H50), C10(H10),
 C42(H42), C38(H38), C7(H7), C15(H15), C20(H20), C5(H5), C9(H9), C39(H39),
 C62(H62), C41(H41), C51(H51), C8(H8), C43(H43), C16(H16), C25(H25), C53(H53),
 C17(H17), C26(H26), C61(H61), C27(H27), C58(H58), C60(H60), C59(H59), C28(H28),
  C19(H19), C52(H52), C29(H29), C18(H18)
6.d Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C66(H66A,H66B,H66C), C68(H68A,H68B,H68C), C70(H70A,H70B,
 H70C), C1B(H1BA,H1BB,H1BC)
;
_shelx_res_checksum              30303
_shelx_hkl_checksum              2323
_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
;