Tunable Cu-Ni phosphine-thiolate complexes as water-compatible catalyst for base-free click chemistry
Chaturvedi, Nishtha; Pandey, Vinay Kumar; Tiwari, Vinod K.; Bhattacharya, Subrato; New Journal of Chemistry  (2026) –; doi:10.1039/D5NJ03825A

data_7064204
_publ_section_title
;
 Tunable Cu-Ni phosphine-thiolate complexes as water-compatible catalyst
 for base-free click chemistry
;
_journal_name_full               'New Journal of Chemistry'
_journal_paper_doi               10.1039/D5NJ03825A
_journal_year                    2026
_chemical_formula_moiety
'C60 H48 Cu4 N8 Ni P4 S12, C12 H32 N4 Ni O6, 4(C3 H7 N O), 3[H2O]'
_chemical_formula_sum            'C84 H114 Cu4 N16 Ni2 O13 P4 S12'
_chemical_formula_weight         2436.09
_space_group_crystal_system      tetragonal
_space_group_IT_number           85
_space_group_name_Hall           '-P 4a'
_space_group_name_H-M_alt        'P 4/n :2'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2025-12-09
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-12-09 deposited with the CCDC.	2025-12-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   17.9807(2)
_cell_length_b                   17.9807(2)
_cell_length_c                   16.7565(3)
_cell_measurement_reflns_used    13766
_cell_measurement_temperature    293
_cell_measurement_theta_max      72.0730
_cell_measurement_theta_min      3.4760
_cell_volume                     5417.47(13)
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_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    -97.00 -19.00   0.50    3.92    --  -40.83 138.00 106.00  156
  2  \w   -107.00 -26.00   0.50    3.92    --  -40.83 -36.00  84.00  162
  3  \w    -41.00  26.00   0.50    3.92    --  -40.83  36.00-118.00  134
  4  \w    -22.00  71.00   0.50    3.92    --   40.83 -85.00 -73.00  186
  5  \w    -26.00  41.00   0.50    3.92    --   40.83 -36.00  84.00  134
  6  \w     41.00 100.00   0.50    3.92    --   40.83-138.00  43.00  118
  7  \w   -148.00 -68.00   0.50   13.00    --  -82.50-132.00-139.00  160
  8  \w   -149.00 -68.00   0.50   13.00    --  -82.50 -36.00  84.00  162
  9  \w   -112.00 -13.00   0.50   13.00    --  -82.50  85.00  45.00  198
 10  \w   -152.00 -78.00   0.50   13.00    --  -82.50 -85.00 -73.00  148
 11  \w     89.00 171.00   0.50   13.00    --  104.00  36.00-118.00  164
 12  \w     34.00 132.00   0.50   13.00    --  104.00 -85.00 -73.00  196
 13  \w     41.00  66.00   0.50   13.00    --  104.00-138.00  43.00   50
 14  \w     90.00 115.00   0.50   13.00    --  104.00 132.00 -70.00   50
 15  \w     41.00  84.00   0.50   13.00    --  104.00-132.00-139.00   86
 16  \w     77.00 116.00   0.50   13.00    --  104.00-138.00  43.00   78
 17  \w    112.00 138.00   0.50   13.00    --  104.00  85.00  45.00   52
 18  \w    -28.00  27.00   0.50    3.92    --  -40.83  21.00 -30.00  110
 19  \w    -31.00  23.00   0.50    3.92    --   40.83 -11.00 -90.00  108
 20  \w    -30.00  16.00   0.50    3.92    --   40.83 -21.00 -90.00   92
 21  \w     43.00  68.00   0.50    3.92    --   40.83  36.00-118.00   50
 22  \w     36.00  65.00   0.50   13.00    --  104.00 -59.00   0.00   58
 23  \w     88.00 168.00   0.50   13.00    --  104.00  42.00   0.00  160
 24  \w     37.00  63.00   0.50   13.00    --  104.00 -93.00-150.00   52
 25  \w    149.00 174.00   0.50   13.00    --  104.00  25.00-150.00   50
 26  \w     90.00 123.00   0.50   13.00    --  104.00  33.00 -60.00   66
 27  \w    102.00 135.00   0.50   13.00    --  104.00 111.00  90.00   66
 28  \w     36.00  61.00   0.50   13.00    --  104.00 -59.00 -90.00   50
 29  \w     57.00  98.00   0.50   13.00    --  104.00 -77.00  60.00   82
 30  \w     97.00 124.00   0.50   13.00    --  104.00  25.00-150.00   54
 31  \w     38.00  67.00   0.50   13.00    --  104.00 -59.00 -30.00   58
 32  \w     88.00 130.00   0.50   13.00    --  104.00  42.00 -90.00   84
 33  \w     36.00  67.00   0.50   13.00    --  104.00 -59.00 120.00   62
 34  \w     38.00  68.00   0.50   13.00    --  104.00 -59.00-150.00   60
 35  \w     37.00  83.00   0.50   13.00    --  104.00 -68.00  60.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0380840000
_diffrn_orient_matrix_UB_12      0.0734967000
_diffrn_orient_matrix_UB_13      -0.0236145000
_diffrn_orient_matrix_UB_21      0.0118263000
_diffrn_orient_matrix_UB_22      -0.0186265000
_diffrn_orient_matrix_UB_23      -0.0888434000
_diffrn_orient_matrix_UB_31      -0.0758826000
_diffrn_orient_matrix_UB_32      -0.0397803000
_diffrn_orient_matrix_UB_33      -0.0020503000
_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  0.1176
_diffrn_reflns_av_unetI/netI     0.0614
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            35210
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.067
_diffrn_reflns_theta_min         2.637
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.464
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.41576
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.90a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic reddish brown'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.493
_exptl_crystal_description       block
_exptl_crystal_F_000             2516
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.07
_refine_diff_density_max         1.595
_refine_diff_density_min         -0.798
_refine_diff_density_rms         0.115
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.118
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     396
_refine_ls_number_reflns         5329
_refine_ls_number_restraints     303
_refine_ls_restrained_S_all      1.103
_refine_ls_R_factor_all          0.0985
_refine_ls_R_factor_gt           0.0871
_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^)+(0.1741P)^2^+2.5705P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2576
_refine_ls_wR_factor_ref         0.2692
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4181
_reflns_number_total             5329
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj03825a2.cif
_cod_data_source_block           ns40p_auto
_cod_original_cell_volume        5417.47(15)
_cod_original_sg_symbol_H-M      'P 4/n'
_cod_database_code               7064204
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'NI Cu P S N C H'
_shelx_estimated_absorpt_t_max   0.745
_shelx_estimated_absorpt_t_min   0.595
_diffrn_oxdiff_ac3_digest_hkl    41075dec094d5872aedd15b40e3f8681fed81b
_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, All O(H,H) groups
2. Restrained distances
 N7-C21 = N7A-C21A = N7A-C25A = N7-C25
 1.45 with sigma of 0.01
 O28A-C3A = O28-C3
 1.23 with sigma of 0.01
 N7A-C3A = N7-C3
 1.32 with sigma of 0.01
 N1A-C1A = N1-C6 = N1A-C6A = N1-C1
 1.45 with sigma of 0.01
 N1-C2 = N1A-C2A
 1.32 with sigma of 0.01
 O3-C2 = O3A-C2A
 1.23 with sigma of 0.01
 C2-C1
 2.46 with sigma of 0.04
 C2-C6
 2.45 with sigma of 0.04
 N1-C1 \\sim N1-C6
 with sigma of 0.02
 Ni2-O28 \\sim Ni2-O28A
 with sigma of 0.02
 Ni2-C3 \\sim Ni2-C3A
 with sigma of 0.04
 N7-O28 \\sim N7A-O28A
 with sigma of 0.04
 C21-C25 \\sim C21A-C25A
 with sigma of 0.04
 O3-N1 \\sim O3A-N1A
 with sigma of 0.04
 C21-C3 \\sim C21A-C3A
 with sigma of 0.04
 C25-C3 \\sim C25A-C3A
 with sigma of 0.04
 C2-C6 \\sim C2A-C6A
 with sigma of 0.04
 C2-C1 \\sim C2A-C1A
 with sigma of 0.04
 C1-C6 \\sim C1A-C6A
 with sigma of 0.04
3. Restrained planarity
 C2, O3, N1, C1, C6
 with sigma of 0.1
 N1A, C2A, O3A, C1A, C6A
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C2 \\sim O3 \\sim N1 \\sim C1 \\sim C6 \\sim O3A \\sim C2A \\sim N1A \\sim C1A
\\sim C6A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
N7 \\sim C21 \\sim C25 \\sim N7A \\sim C21A \\sim C25A \\sim O28 \\sim C3 \\sim
O28A \\sim C3A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(N1A) = Uanis(N1)
5. Others
 Sof(O3A)=Sof(C2A)=Sof(H2AA)=Sof(N1A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=
 Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=1-FVAR(1)
 Sof(C2)=Sof(H2)=Sof(O3)=Sof(N1)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C6)=
 Sof(H6C)=Sof(H6D)=Sof(H6E)=FVAR(1)
 Sof(O28A)=Sof(C3A)=Sof(H3A)=Sof(N7A)=Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=
 Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=1-FVAR(2)
 Sof(N7)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C25)=Sof(H25A)=Sof(H25B)=
 Sof(H25C)=Sof(O28)=Sof(C3)=Sof(H3)=FVAR(2)
 Fixed Sof: H6A(0.25) H6B(0.25) H2A(0.25) H2B(0.25)
6.a Rotating group:
 O6(H6A,H6B), O2(H2A,H2B)
6.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B)
6.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C9(H9), C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C20(H20),
 C23(H23), C30(H30), C3(H3), C2(H2), C2A(H2AA), C3A(H3A)
6.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C25(H25A,H25B,H25C), C1(H1A,H1B,H1C), C6(H6C,H6D,H6E),
 C1A(H1AA,H1AB,H1AC), C6A(H6AA,H6AB,H6AC), C21A(H21D,H21E,H21F), C25A(H25D,H25E,
 H25F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              40276
_shelx_fab_checksum              94229
_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 2.512
_oxdiff_exptl_absorpt_empirical_full_min 0.166