Two-dimensional [Co(btbH)<sub>2</sub>(dpe)<sub>2</sub>]·DMF metal-organic framework-derived low-cost nanocomposites for electrochemical nitrate reduction for ammonia production.
Praharaj, Amrutanshu; Kempasiddaiah, Manjunatha; Manna, Biplab Kumar; Samanta, Rajib; Trivedi, Ravi Kumar; Khairwal, Tushar; Barman, Sudip; Nanoscale 17 (2025) 19302–19316; doi:10.1039/d5nr02589c

data_1575341
_publ_section_title
;
 Two-dimensional [Co(btbH)<sub>2</sub>(dpe)<sub>2</sub>]&#xb7;DMF
 metal-organic framework-derived low-cost nanocomposites for
 electrochemical nitrate reduction for ammonia production.
;
_journal_issue                   33
_journal_name_full               Nanoscale
_journal_page_first              19302
_journal_page_last               19316
_journal_paper_doi               10.1039/d5nr02589c
_journal_volume                  17
_journal_year                    2025
_chemical_formula_moiety         'C39 H26 Co N2 O6, C3 H7 N O'
_chemical_formula_sum            'C42 H33 Co N3 O7'
_chemical_formula_weight         750.64
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-02-02
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-04-28 deposited with the CCDC.	2025-07-21 downloaded from the CCDC.
;
_cell_angle_alpha                85.3418(13)
_cell_angle_beta                 78.3142(13)
_cell_angle_gamma                77.3648(13)
_cell_formula_units_Z            2
_cell_length_a                   10.21433(15)
_cell_length_b                   11.54718(19)
_cell_length_c                   16.0905(3)
_cell_measurement_reflns_used    17972
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.6010
_cell_measurement_theta_min      3.9020
_cell_volume                     1812.12(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (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 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.9968
_diffrn_measured_fraction_theta_max 0.9810
_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   -102.00 -56.00   0.50    1.00    --  -38.50-156.00-161.00   92
  2  \w    -83.00  -1.00   0.50    1.00    --  -38.50 119.00  79.00  164
  3  \w   -107.00 -23.00   0.50    1.00    --  -38.50 156.00-124.00  168
  4  \w     23.00  94.00   0.50    1.00    --   49.56-119.00  -5.00  142
  5  \w     44.00 118.00   0.50    1.00    --   49.56-156.00-161.00  148
  6  \w     48.00 110.00   0.50    4.00    --  111.00-119.00  -5.00  124
  7  \w     78.00 162.00   0.50    4.00    --  111.00 156.00-124.00  168
  8  \w     47.00 133.00   0.50    4.00    --  111.00-156.00-161.00  172
  9  \w    100.00 175.00   0.50    4.00    --  111.00 119.00  79.00  150
 10  \w    -44.00  31.00   0.50    1.00    --  -38.50  19.00   0.00  150
 11  \w   -101.00 -22.00   0.50    1.00    --  -38.50 -67.00  -7.38  158
 12  \w   -101.00 -26.00   0.50    1.00    --  -38.50 -59.00-153.39  150
 13  \w   -105.00 -35.00   0.50    1.00    --  -38.50 -37.00  30.00  140
 14  \w     31.00 113.00   0.50    1.00    --   49.56  71.00-159.92  164
 15  \w     46.00 109.00   0.50    4.00    --  111.00-111.00 150.00  126
 16  \w     43.00 114.00   0.50    4.00    --  111.00 -30.00-180.00  142
 17  \w     47.00 116.00   0.50    4.00    --  111.00 -45.00 150.00  138
 18  \w     43.00 106.00   0.50    4.00    --  111.00 -94.00  30.00  126
 19  \w     43.00 106.00   0.50    4.00    --  111.00 -94.00-150.00  126
 20  \w    100.00 174.00   0.50    4.00    --  111.00  56.00 141.13  148
 21  \w     46.00 109.00   0.50    4.00    --  111.00-111.00 -60.00  126
 22  \w     43.00 119.00   0.50    4.00    --  111.00 -15.00 -90.00  152
 23  \w     48.00 124.00   0.50    4.00    --  111.00 -61.00   0.00  152
 24  \w     48.00 124.00   0.50    4.00    --  111.00 -61.00  90.00  152
 25  \w     77.00 109.00   0.50    4.00    --  111.00-111.00-150.00   64
 26  \w     46.00  72.00   0.50    4.00    --  111.00-111.00-150.00   52
 27  \w     89.00 119.00   0.50    4.00    --  111.00 -15.00   0.00   60
 28  \w     49.00 109.00   0.50    4.00    --  111.00-111.00   0.00  120
 29  \w     60.00 117.00   0.50    4.00    --  111.00 -15.00-180.00  114
 30  \w     44.00 119.00   0.50    4.00    --  111.00 -15.00 120.00  150
 31  \w     67.00 114.00   0.50    4.00    --  111.00 -45.00-150.00   94
 32  \w     43.00  75.00   0.50    4.00    --  111.00 -94.00  90.00   64
 33  \w     80.00 106.00   0.50    4.00    --  111.00 -94.00  90.00   52
 34  \w    108.00 175.00   0.50    4.00    --  111.00  30.00 120.00  134
 35  \w     44.00  84.00   0.50    4.00    --  111.00 -15.00   0.00   80
 36  \w    100.00 170.00   0.50    4.00    --  111.00  61.00 150.00  140
 37  \w     93.00 119.00   0.50    4.00    --  111.00  71.00   6.83   52
 38  \w    134.00 168.00   0.50    4.00    --  111.00  71.00   6.83   68
 39  \w     79.00 105.00   0.50    4.00    --  111.00 -94.00-120.00   52
 40  \w     53.00 115.00   0.50    4.00    --  111.00 -45.00 120.00  124
 41  \w     44.00  97.00   0.50    4.00    --  111.00 -94.00   0.00  106
 42  \w     71.00 104.00   0.50    4.00    --  111.00 -94.00  60.00   66
 43  \w     81.00 106.00   0.50    4.00    --  111.00 -94.00 150.00   50
 44  \w     46.00 113.00   0.50    4.00    --  111.00 -30.00 -30.00  134
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0364688000
_diffrn_orient_matrix_UB_12      0.0460221000
_diffrn_orient_matrix_UB_13      0.0778338000
_diffrn_orient_matrix_UB_21      -0.0725720000
_diffrn_orient_matrix_UB_22      -0.0888265000
_diffrn_orient_matrix_UB_23      0.0581738000
_diffrn_orient_matrix_UB_31      0.1348665000
_diffrn_orient_matrix_UB_32      -0.0933470000
_diffrn_orient_matrix_UB_33      -0.0114436000
_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  0.0866
_diffrn_reflns_av_unetI/netI     0.1009
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            30844
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.887
_diffrn_reflns_theta_min         3.926
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.177
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64461
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.89a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.376
_exptl_crystal_description       octahedral
_exptl_crystal_F_000             778
_exptl_crystal_preparation       'As per the reaction scheme in manuscript'
_exptl_crystal_recrystallization_method Solvothermal
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.435
_refine_diff_density_min         -0.783
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     501
_refine_ls_number_reflns         7746
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0542
_refine_ls_R_factor_gt           0.0459
_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^)+(0.0725P)^2^+0.8263P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1225
_refine_ls_wR_factor_ref         0.1251
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7263
_reflns_number_total             7746
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nr02589c2.cif
_cod_data_source_block           sb-co-h3btb-dpe-02_auto
_cod_depositor_comments          'Adding full bibliography for 1575341.cif.'
_cod_original_cell_volume        1812.13(5)
_cod_database_code               1575341
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C H N Co O'
_chemical_oxdiff_usercomment     'LIGHT RED BLOCK'
_shelx_estimated_absorpt_t_max   0.592
_shelx_estimated_absorpt_t_min   0.422
_diffrn_oxdiff_digest_frames
;
01884cbafb7c2cb143ab42f2b862925ef3000274d41
;
_diffrn_oxdiff_digest_hkl
;
01d70ae84ee957f4b997270765d60ac04c53e2
;
_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, All O(H) groups
2. Others
 Sof(C31A)=Sof(H31A)=1-FVAR(1)
 Sof(C31B)=Sof(H31B)=FVAR(1)
 Sof(C32A)=Sof(H32A)=1-FVAR(2)
 Sof(C32B)=Sof(H32B)=FVAR(2)
3.a Aromatic/amide H refined with riding coordinates:
 C36(H36), C9(H9), C38(H38), C34(H34), C37(H37), C31A(H31A), C19(H19),
 C32A(H32A), C28(H28), C7(H7), C11(H11), C26(H26), C33(H33), C13(H13), C3(H3),
 C15(H15), C4(H4), C16(H16), C18(H18), C22(H22), C29(H29), C23(H23), C25(H25),
 C31B(H31B), C6(H6), C32B(H32B), C39(H39), C40(H40)
3.b Idealised Me refined as rotating group:
 C41(H41a,H41b,H41c), C42(H42a,H42b,H42c)
3.c Idealised tetrahedral OH refined as rotating group:
 O5(H5)
;
_shelx_res_checksum              8158
_olex2_exptl_crystal_mounting_method 'Mounted on the nylon loop'
_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 2.061
_oxdiff_exptl_absorpt_empirical_full_min 0.546