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_7717643
_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 Cu2 N8 O4, 2(C2 H3 N)'
_chemical_formula_sum            'C34 H28 Cu2 N10 O4'
_chemical_formula_weight         767.74
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-11-02
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-11-04 deposited with the CCDC.	2024-12-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.0840(10)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   20.25610(10)
_cell_length_b                   37.4829(3)
_cell_length_c                   17.44620(10)
_cell_measurement_reflns_used    31554
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.3340
_cell_measurement_theta_min      2.7980
_cell_volume                     13171.55(15)
_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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.934
_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    -77.00 -16.00   0.50    7.08    --  -47.28 100.00  62.00  122
  2  \w      1.00  26.00   0.50    7.08    --   47.28-100.00 -42.00   50
  3  \w     40.00  65.00   0.50    7.08    --   47.28-100.00 -42.00   50
  4  \w    -79.00 -49.00   0.50   28.34    --  -91.75 100.00  62.00   60
  5  \w   -152.00 -85.00   0.50   28.34    --  -91.75-100.00 -42.00  134
  6  \w     34.00 102.00   0.50   28.34    --  105.91-100.00 -42.00  136
  7  \w   -117.00 -91.00   0.50    7.08    --  -47.28-125.00  30.00   52
  8  \w    -37.00  26.00   0.50    7.08    --  -47.28  38.00 -60.00  126
  9  \w   -119.00 -77.00   0.50    7.08    --  -47.28-125.00 120.00   84
 10  \w    -14.00  16.00   0.50    7.08    --  -47.28 100.00  62.00   60
 11  \w    -23.00  23.00   0.50    7.08    --  -47.28  19.00-180.00   92
 12  \w    -68.00 -20.00   0.50   28.34    --  -91.75  61.00 -90.00   96
 13  \w    -48.00 -21.00   0.50   28.34    --  -91.75  45.00 -90.00   54
 14  \w    -46.00 -20.00   0.50   28.34    --  -91.75  45.00 -30.00   52
 15  \w   -149.00 -85.00   0.50   28.34    --  -91.75 -94.00  90.00  128
 16  \w    -76.00 -50.00   0.50   28.34    --  -91.75 125.00 150.00   52
 17  \w    -48.00 -23.00   0.50   28.34    --  -91.75  45.00-180.00   50
 18  \w    -48.00 -23.00   0.50   28.34    --  -91.75  45.00 150.00   50
 19  \w    -47.00 -20.00   0.50   28.34    --  -91.75  45.00  60.00   54
 20  \w    -67.00 -36.00   0.50   28.34    --  -91.75  61.00-150.00   62
 21  \w     33.00  74.00   0.50   28.34    --  105.91 -61.00  90.00   82
 22  \w     74.00 100.00   0.50   28.34    --  105.91 -77.00 -30.00   52
 23  \w     33.00  63.00   0.50   28.34    --  105.91 -77.00 -30.00   60
 24  \w     33.00  60.00   0.50   28.34    --  105.91 -61.00 -30.00   54
 25  \w     34.00  69.00   0.50   28.34    --  105.91 -61.00-180.00   70
 26  \w     40.00  67.00   0.50   28.34    --  105.91 -61.00   0.00   54
 27  \w     41.00  96.00   0.50   28.34    --  105.91 -77.00   0.00  110
 28  \w     33.00  73.00   0.50   28.34    --  105.91 -61.00 150.00   80
 29  \w    119.00 144.00   0.50   28.34    --  105.91 100.00  62.00   50
;
_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      0.0220487000
_diffrn_orient_matrix_UB_12      0.0384774000
_diffrn_orient_matrix_UB_13      -0.0149725000
_diffrn_orient_matrix_UB_21      0.0112042000
_diffrn_orient_matrix_UB_22      0.0067071000
_diffrn_orient_matrix_UB_23      0.0875408000
_diffrn_orient_matrix_UB_31      0.0723680000
_diffrn_orient_matrix_UB_32      -0.0127973000
_diffrn_orient_matrix_UB_33      0.0010170000
_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  0.0423
_diffrn_reflns_av_unetI/netI     0.0364
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.934
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -47
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            99757
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.934
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.774
_diffrn_reflns_theta_min         2.490
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.060
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.41195
_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            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.549
_exptl_crystal_description       prism
_exptl_crystal_F_000             6272
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.534
_refine_diff_density_min         -0.534
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1974
_refine_ls_number_reflns         25934
_refine_ls_number_restraints     803
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.0590
_refine_ls_R_factor_gt           0.0399
_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^)+(0.0589P)^2^+5.6416P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1027
_refine_ls_wR_factor_ref         0.1132
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19454
_reflns_number_total             25934
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt02777a2.cif
_cod_data_source_block           jp320_2
_cod_depositor_comments
'Adding full bibliography for 7717638--7717643.cif.'
_cod_database_code               7717643
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C15 H11 Cu N4 O2'
_shelx_estimated_absorpt_t_max   0.886
_shelx_estimated_absorpt_t_min   0.820
_reflns_odcompleteness_completeness 99.67
_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 C(H,H,H) groups
2. Rigid bond restraints
 C53, Cu3, Cu4, N9, N10, N12, N15, N11, N13, N14, N16, C31, C35, C36, C40, O5,
 O6, C56, C60, C41, C45, C46, C50, C51, C55, O7, O8, C32, C34, C37, C39, C57,
 C59, C58, C42, C44, C47, C49, C52, C54, C33, C38, C43, C48
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
3. Uiso/Uaniso restraints and constraints
C55 \\sim Cu3 \\sim Cu4 \\sim N9 \\sim N10 \\sim N12 \\sim N15 \\sim N11 \\sim
N13 \\sim N14 \\sim N16 \\sim C31 \\sim C35 \\sim C36 \\sim C40 \\sim O5 \\sim
O6 \\sim C56 \\sim C60 \\sim C41 \\sim C45 \\sim C46 \\sim C50 \\sim C51 \\sim
O7 \\sim O8 \\sim C32 \\sim C34 \\sim C37 \\sim C39 \\sim C57 \\sim C59 \\sim
C58 \\sim C42 \\sim C44 \\sim C47 \\sim C49 \\sim C52 \\sim C54 \\sim C53 \\sim
C33 \\sim C38 \\sim C43 \\sim C48: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 1.7A
C60 \\sim Cu3 \\sim Cu4 \\sim N9 \\sim N10 \\sim N12 \\sim N15 \\sim N15A \\sim
N11 \\sim N13 \\sim N14 \\sim N16 \\sim N14A \\sim N13A \\sim C31 \\sim C35
\\sim C36 \\sim C40 \\sim O5 \\sim O6 \\sim C56 \\sim C56A \\sim C137 \\sim C41
\\sim C45 \\sim C46 \\sim C50 \\sim C51 \\sim C55 \\sim O7 \\sim O8 \\sim C51A
\\sim C55A \\sim C50A \\sim C46A \\sim C32 \\sim C34 \\sim C37 \\sim C39 \\sim
C57 \\sim C59 \\sim C57A \\sim C60A \\sim C42 \\sim C44 \\sim C47 \\sim C49
\\sim C52 \\sim C54 \\sim C52A \\sim C54A \\sim C49A \\sim C47A \\sim C33 \\sim
C38 \\sim C58 \\sim C59A \\sim C43 \\sim C48 \\sim C53 \\sim C53A \\sim C48A:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
4. Others
 Sof(N14A)=Sof(C51A)=Sof(C52A)=Sof(H52A)=Sof(C53A)=Sof(H53A)=Sof(C54A)=
 Sof(H54A)=Sof(C55A)=1-FVAR(1)
 Sof(N14)=Sof(C51)=Sof(C52)=Sof(H52)=Sof(C53)=Sof(H53)=Sof(C54)=Sof(H54)=
 Sof(C55)=FVAR(1)
 Sof(C56A)=Sof(C57A)=Sof(H57A)=Sof(C59A)=Sof(H59A)=Sof(C60A)=Sof(H60A)=
 Sof(N15A)=Sof(C137)=Sof(H137)=1-FVAR(2)
 Sof(N15)=Sof(C56)=Sof(C57)=Sof(H57)=Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=
 Sof(C60)=Sof(H60)=FVAR(2)
 Sof(C50A)=Sof(N13A)=Sof(C46A)=Sof(H46A)=Sof(C47A)=Sof(H47A)=Sof(C48A)=
 Sof(H48A)=Sof(C49A)=Sof(H49A)=1-FVAR(3)
 Sof(N13)=Sof(C46)=Sof(H46)=Sof(C47)=Sof(H47)=Sof(C48)=Sof(H48)=Sof(C49)=
 Sof(H49)=Sof(C50)=FVAR(3)
5.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C12(H12), C13(H13),
 C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C22(H22), C23(H23),
  C24(H24), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32),
 C33(H33), C34(H34), C37(H37), C38(H38), C39(H39), C42(H42), C43(H43), C44(H44),
  C45(H45), C46(H46), C47(H47), C48(H48), C49(H49), C52(H52), C53(H53),
 C54(H54), C57(H57), C58(H58), C59(H59), C60(H60), C61(H61), C62(H62), C63(H63),
  C64(H64), C67(H67), C68(H68), C69(H69), C72(H72), C73(H73), C74(H74),
 C75(H75), C76(H76), C77(H77), C78(H78), C79(H79), C82(H82), C83(H83), C84(H84),
  C87(H87), C88(H88), C89(H89), C90(H90), C91(H91), C92(H92), C93(H93),
 C94(H94), C97(H97), C98(H98), C99(H99), C102(H102), C103(H103), C104(H104),
 C105(H105), C106(H106), C107(H107), C108(H108), C109(H109), C112(H112),
 C113(H113), C114(H114), C117(H117), C118(H118), C119(H119), C120(H120),
 C52A(H52A), C53A(H53A), C54A(H54A), C57A(H57A), C59A(H59A), C60A(H60A),
 C46A(H46A), C47A(H47A), C48A(H48A), C49A(H49A), C137(H137)
5.b Idealised Me refined as rotating group:
 C121(H12A,H12B,H12C), C123(H12D,H12E,H12F), C125(H12G,H12H,H12I), C127(H12J,
 H12K,H12L), C129(H12M,H12N,H12O), C133(H13A,H13B,H13C), C135(H13D,H13E,H13F),
 C131(H13G,H13H,H13I)
;
_shelx_res_checksum              82272
_shelx_hkl_checksum              35548
_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 2.983
_oxdiff_exptl_absorpt_empirical_full_min 0.784