A terpyridine-based copper complex for electrochemical reduction of nitrite to nitric oxide.
Biswas, Jyotiprokash; Sanden, Sebastian; Bhardwaj, Prabhakar; Siegmund, Daniel; Kumar, Pankaj; Apfel, Ulf-Peter; Dalton transactions (Cambridge, England : 2003) 54 (2025) 1815–1826; doi:10.1039/d4dt02777a

data_7717638
_publ_section_title
;
 A terpyridine-based copper complex for electrochemical reduction of
 nitrite to nitric oxide.
;
_journal_issue                   5
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              1815
_journal_page_last               1826
_journal_paper_doi               10.1039/d4dt02777a
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C30 H22 Cu N6, 2(Cl O4), H2 O'
_chemical_formula_sum            'C30 H24 Cl2 Cu N6 O9'
_chemical_formula_weight         746.99
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-11-01
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-11-01 deposited with the CCDC.	2024-12-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.082(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.7098(2)
_cell_length_b                   8.8878(2)
_cell_length_c                   19.9949(5)
_cell_measurement_reflns_used    5682
_cell_measurement_temperature    104.1(5)
_cell_measurement_theta_max      74.2270
_cell_measurement_theta_min      5.2800
_cell_volume                     1532.45(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      104.1(5)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -88.00 -36.00   0.50    0.69    --  -47.28 -50.00 -66.00  104
  2  \w     34.00  81.00   0.50    0.69    --   47.28  50.00  80.00   94
  3  \w    -13.00  55.00   0.50    0.69    --   47.28 -50.00 -66.00  136
  4  \w    -51.00 -21.00   0.50    2.74    --  -91.75  50.00  80.00   60
  5  \w   -163.00 -85.00   0.50    2.74    --  -91.75 -50.00 -66.00  156
  6  \w    153.00 178.00   0.50    2.74    --  105.91  50.00  80.00   50
  7  \w    111.00 137.00   0.50    2.74    --  105.91  50.00  80.00   52
  8  \w     34.00  59.00   0.50    2.74    --  105.91 -50.00 -66.00   50
  9  \w   -117.00 -73.00   0.50    0.69    --  -47.28-125.00-120.00   88
 10  \w   -113.00 -85.00   0.50    0.69    --  -47.28-125.00  60.00   56
 11  \w    -63.00 -35.00   0.50    0.69    --  -47.28 -38.00-120.00   56
 12  \w    -35.00   7.00   0.50    0.69    --  -47.28  50.00  80.00   84
 13  \w   -120.00 -88.00   0.50    0.69    --  -47.28 -38.00-120.00   64
 14  \w    -68.00 -43.00   0.50    2.74    --  -91.75  61.00 -90.00   50
 15  \w   -105.00 -76.00   0.50    2.74    --  -91.75 -61.00   0.00   58
 16  \w    -48.00 -23.00   0.50    2.74    --  -91.75  45.00-150.00   50
 17  \w   -162.00-110.00   0.50    2.74    --  -91.75 -61.00   0.00  104
 18  \w    -45.00 -19.00   0.50    2.74    --  -91.75  61.00-180.00   52
 19  \w    -47.00 -22.00   0.50    2.74    --  -91.75  45.00  60.00   50
 20  \w    -64.00 -38.00   0.50    2.74    --  -91.75  61.00 -60.00   52
 21  \w    -45.00 -20.00   0.50    2.74    --  -91.75  45.00  30.00   50
 22  \w    -48.00 -23.00   0.50    2.74    --  -91.75  45.00 -90.00   50
 23  \w     45.00  73.00   0.50    2.74    --  105.91 -61.00  30.00   56
 24  \w    101.00 173.00   0.50    2.74    --  105.91  45.00   0.00  144
 25  \w    105.00 178.00   0.50    2.74    --  105.91 125.00 -90.00  146
 26  \w     42.00  67.00   0.50    2.74    --  105.91 -61.00-180.00   50
 27  \w     40.00 112.00   0.50    2.74    --  105.91-125.00 150.00  144
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1372455000
_diffrn_orient_matrix_UB_12      0.1054577000
_diffrn_orient_matrix_UB_13      -0.0071378000
_diffrn_orient_matrix_UB_21      0.0353836000
_diffrn_orient_matrix_UB_22      0.0129312000
_diffrn_orient_matrix_UB_23      0.0774837000
_diffrn_orient_matrix_UB_31      0.1087016000
_diffrn_orient_matrix_UB_32      -0.1369767000
_diffrn_orient_matrix_UB_33      0.0018358000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0455
_diffrn_reflns_av_unetI/netI     0.0508
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            11292
_diffrn_reflns_point_group_measured_fraction_full 0.779
_diffrn_reflns_point_group_measured_fraction_max 0.779
_diffrn_reflns_theta_full        67.490
_diffrn_reflns_theta_max         67.490
_diffrn_reflns_theta_min         2.232
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.189
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81660
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.619
_exptl_crystal_description       prism
_exptl_crystal_F_000             762
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.467
_refine_diff_density_min         -0.452
_refine_diff_density_rms         0.070
_refine_ls_abs_structure_details
;
 Flack x determined using 1162 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.044(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     473
_refine_ls_number_reflns         4308
_refine_ls_number_restraints     83
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0470
_refine_ls_R_factor_gt           0.0421
_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^)+(0.0559P)^2^+1.0104P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1023
_refine_ls_wR_factor_ref         0.1050
_reflns_Friedel_coverage         0.457
_reflns_Friedel_fraction_full    0.526
_reflns_Friedel_fraction_max     0.526
_reflns_number_gt                3978
_reflns_number_total             4308
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt02777a2.cif
_cod_data_source_block           jp259
_cod_depositor_comments
'Adding full bibliography for 7717638--7717643.cif.'
_cod_database_code               7717638
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C30H22N6CuCl2O8
_shelx_estimated_absorpt_t_max   0.682
_shelx_estimated_absorpt_t_min   0.568
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 Cl2-O5 \\sim Cl2-O5A
 with sigma of 0.02
 Cl2-O6 \\sim Cl2-O6A
 with sigma of 0.02
 Cl2-O7 \\sim Cl2-O7A
 with sigma of 0.02
 Cl2-O8 \\sim Cl2-O8A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl2 \\sim O7 \\sim O5 \\sim O6 \\sim O8 \\sim O5A \\sim O6A \\sim O7A \\sim
O8A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
1.7A
4. Others
 Sof(O5A)=Sof(O6A)=Sof(O7A)=Sof(O8A)=1-FVAR(1)
 Sof(O5)=Sof(O6)=Sof(O7)=Sof(O8)=FVAR(1)
5.a Free rotating group:
 O9(H9A,H9B)
5.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C13(H13), C29(H29), C18(H18), C23(H23), C22(H22), C28(H28),
 C27(H27), C1(H1), C15(H15), C16(H16), C9(H9), C30(H30), C19(H19), C24(H24),
 C2(H2), C7(H7), C12(H12), C17(H17), C4(H4), C8(H8), C3(H3)
;
_shelx_res_checksum              92026
_shelx_hkl_checksum              62000
_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 1.346
_oxdiff_exptl_absorpt_empirical_full_min 0.793